REVIEW

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Cobalt-Based Materials in Supercapacitors and Batteries:

A Review
Jyothi A. Goudar, Thrinethra S. N., Sharanappa Chapi,* Murugendrappa M. V.,*
Mohammad Reza Saeb, and Mehdi Salami-Kalajahi*

1. Introduction
Energy demand has become a persistent concern and high-performance energy
storage systems have increasingly undergone development. Supercapacitors and In order to lessen the reliance on fossil
batteries pose great impact on energy storage and garner a great deal of attention fuels, there is a persistent need for explor-
ing greener and more renewable alterna-
from technologies and researchers alike. The performance of energy saving
tives derived from environmentally
devices is primarily determined by the electrode material in terms of high specific friendly energy sources. This is driven by
capacitance, excellent conductivity, remarkable natural abundance, and unique the world economy’s rapid growth, massive
electrochemical qualities, also large surface area. Cobalt (Co)-based materials are fossil fuel consumption, and rising levels of
unique electrode materials widely used in energy storage devices. Nevertheless, a environmental pollution, leading to the
combination of Co and ferrite materials such as nickel, zinc, and copper, or development of storage and conversion
technologies. Additionally, there is a
Co/nonferrite materials like metal–organic frameworks and layered double
great deal of interest in researching high-
hydroxides has improved their ultimate efficiency. This review deals with energy performance devices to accelerate the
storage applications of Co-based materials, categorizing ferrites, their electro- development of electric vehicles with fewer
chemical characterization, performance, also design and manufacturing intended pollution emissions and the rising demand
to supercapacitors and batteries applications. Summarizing the main outcomes for portable electronic devices, power tools,
of the literature on batteries and supercapacitors, energy storage systems and electric automobiles. Today’s focus on
renewable and sustainable energy sources,
comprising Co-based materials combined with carbon nanotubes, graphene,
such as wind farms, solar cells, and water
silica, copper, zinc, nickel, cadmium, ferrous, and lanthanum are reviewed and
farms, along with transportations based on
discussed. Lithium-ion batteries are investigated specifically, and perspectives on sustainable loops, processes, and portfo-
Co-based ferrite development for future generations of supercapacitors and lios, has opened up new paths for innova-
batteries are outlined. tion. Nevertheless, developing technologies
that enable effective electrical energy stor-
age (ES) is still a major obstacle. In order
to solve this problem, electrochemical
energy storage (EES) systems in particular supercapacitors and
batteries have become essential technology.[1]

J. A. Goudar, Thrinethra S. N., S. Chapi, Murugendrappa M. V. M. R. Saeb

Department of Physics Department of Pharmaceutical Chemistry
B.M.S. College of Engineering Medical University of Gdańsk
Bengaluru 560019, Karnataka, India J. Hallera 107, 80-416 Gdańsk, Poland
E-mail: [email protected];
[email protected] M. Salami-Kalajahi
Faculty of Polymer Engineering
J. A. Goudar Sahand University of Technology
Department of Physics P.O. Box 51335-1996, Tabriz, Iran
Mangalore University E-mail: [email protected]
Mangalagangothri 574199, Karnataka, India
M. Salami-Kalajahi
The ORCID identification number(s) for the author(s) of this article Institute of Polymeric Materials
can be found under https://doi.org/10.1002/aesr.202400271. Sahand University of Technology
P.O. Box 51335-1996, Tabriz, Iran
© 2024 The Author(s). Advanced Energy and Sustainability Research pub-
lished by Wiley-VCH GmbH. This is an open access article under the terms
of the Creative Commons Attribution License, which permits use,
distribution and reproduction in any medium, provided the original
work is properly cited.
DOI: 10.1002/aesr.202400271

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A growing number of novel nanostructures and electrolyte high energy density, portability, long cycle life, versatility, contin-
systems are being used in the quest for the highly efficient uous power supply, and charging–discharging rates.[4] The
energy storage devices (ESDs) with extended cyclic stability. supercapacitors have lately garnered significant research interest
Hybrid ES systems, often known as supercapacitors or ultraca- because of their increased power density, quick discharge and
pacitors, satisfy these requirements. New-age electronic devices charge rate (within sec), and extended cyclic life with a wide
are being defined in large part by EES.[2] Several ES techniques range working temperature as represented in Table 1. The sim-
including thermal, mechanical (pumped hydro, flying wheel, plified Ragone plot Figure 1b illustrates the strength of ESDs
compressed air), electrical (supercapacitor, capacitors), electro- and conversion systems like combustion engines, turbines, and
chemical (battery [BT], hydrogen), and so on have been used conventional capacitors. Fuel cells are considered higher energy
in different applications, as shown in Figure 1a. systems due to their reliance on the cathode and anode for charge
The electrochemical storages (specific capacitances [SCs] and transfer, as well as fuels that perform redox reactions without
pseudocapacitor [PC]) and batteries (lithium ion, sodium ion, burning. Conversely, supercapacitors are categorized as high-
nickel-cadmium, lead acid, and lead carbon, using ferrites) are power systems that store bulk at the electrodes surface and
sophisticated ESDs that have high voltage and density. the electric charges at the electrodes surface. LIBs offer middle-
Rechargeable lithium-ion batteries (LIBs) with high voltage, high level energy and power characteristics. The most crucial part of
energy density, and good safety performance are currently in the ES and conversion system is the electrode materials, which
widespread usage. However, lithium supplies are in a very pre- typically fall into three categories: conducting polymers (CPs),
carious position due to the growing demand for LIBs. As a result, carbonaceous materials, and transition metal oxides (TMOs).[5]
sodium, an alkali metal, has garnered more attention lately Both supercapacitors and batteries are experiencing advance-
because of its cheap price and high content. Still, the biggest ment in parallel with energy density improvement, material
issue impeding the development of sodium-ion batteries is their innovation, electric vehicles, and portable electronics, preserving
poor cycle performance. Faster charging and discharging times commitment to the sustainability goals.[6] Based on statistics, it is
(SCs: 1–10 s and batteries: 0.5–5 h), better power densities estimated that investments on supercapacitor will globally exceed
(SCs: 500–10 000 W kg
1 and batteries <1000 W kg
1), longer $1.0 billion USD by 2028. In a similar manner, there has been
life spans (SCs > 500 000 h and batteries: 500–1000 h), and safer outstanding contributionn being made by LIBs to ES technolo-
operation are all advantages of SCs over rechargeable gies (>2800 GWh) by 2023, such that diverse innovative materi-
batteries.[3b] als, devices, and modern technologies have been dynamically
Electrochemical storage is often considered an enhanced stor- developing for ES needs, as illustrated in Figure 1c,d.[3,7]
age device for certain application advantages as it offers relatively a Such ascending trends in everincreasing utilization of

Figure 1. a) Different ES technologies (Reproduced with permission.[259] Copyright, John Wiley and Sons). b) ES power for the several electrochemical
energy conversion systems represented in a simplified Ragone plot (Reproduced with permission.[260] Copyright 2023, Elsevier). c) The global super-
capacitor market: industry trends and projection up to 2028 [www.databridgemarketresearch.com].[7] d) The global batteries market: industry trends and
projection through 2030 (Reproduced with permission.[3a] as an open access source).

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Table 1. Key distinctions between supercapacitors and batteries as the main ESDs.[261–264]

Feature Supercapacitor Battery

Mechanism of storage Physical Chemical
Power restriction Conductivity of electrolyte Kinetics of reaction, bulk transport
Charge rate Very high (same as discharge rate) Kinetically restricted
Internal resistance Low High
Discharge [h] ≤1 ≤10
Lifespan [years] 5–30 3–15
Self-discharge [% per day] 20–40 ≤0.3
Specific energy [Wh kg
1] ≤50 ≤265
Time of discharge s min
1 h

1
Specific power [W kg ] ≥4000 ≤3000
Operating temperature [°C]
40 to 85
20 to 60
Cycle life ≥1 000 000 500–10 000
Maximum rate potential [V] 1.2–3.3 2.5–4.3
Efficiency [%] ≥95% 80–90%
ES Restricted (surface area) Extreme (bulk)
Cycle life restrictions Consequences Chemical flexibility, mechanical stability
Environmental effect Benign Toxic
Safety consideration Not required Required
Time of charge 1–10 s 10–60 min
Cell voltage [V] 2.3–2.75 3.6–3.7

supercapacitors and batteries should principally underline their material among nanoparticles (NPs) is cobalt ferrite (CoFe2O4)
spatial roles in developing technologies grounded on ES nanostructure. As identified by formula (Fe3þ)[Co2þFe3þ]O4,
approaches, where supercapacitors and metallic nanostructures CoFe2O4 has an inverse spinal structure, with the Co2þ-ion spe-
have played crucial roles.[8] Notably, Co-based supercapacitors uti- cies found at the B-site and the Fe3þ-ion species identified simul-
lize optimized nanocomposites to enhance charge transport taneously in the A and B sites. Very recently a mesoporous
properties. These differences are summarized in Table 1. structurally engineered Co with huge surface area of 505 m2 g
1
Though commercial graphite anodes with inadequate lithium- close to the theoretical value was achieved.[13] Fascinatingly, the
ion diffusivity and restricted theoretical capacity are unable to structure of the ferrite materials is made up of positively charged
match the increasing power density and energy requirements metal ions interacting with negatively charged divalent oxygen
of future LIBs, supercapacitors exhibit great power density, ions. Furthermore, CoFe2O4 has a cubic structure and is a con-
but inadequate energy density yet.[9,10] To attain longer life, stituent of the Fd3m space group. Moreover, the unique mechan-
remarkable rate capability, and high capacity in ESDs, it is highly ical and physical characteristics of cobalt ferrites enable a wide
desirable yet challenging to explore new electrode materials that range of applications. This material is hard, magnetic, and
feature adequate ion storage capacity and superior electron–ion has several notable properties including a high anisotropy
transport rate.[10,11] In light of their exceptional inherent constant of 2.65  106–5.1  106 erg cm
3, significant magneto-
abundance, affordability, excellent catalytic efficiency, enormous restrictive property of
225  10
6, moderate saturation magne-
surface specificity, surface oxygen accessibility property, conduc- tization of about 80 emu g
1 for large quantities at room
tivity properties, and excellent chemical, mechanical, and ther- temperature, high Curie temperature of 520 °C, and high coer-
mal stability, metal ferrites (MFe2O4; M = Co, Mg, Ni, Fe, Mn, civity for the 40 nm size range of single domain at room temper-
Zn, and Cu, etc.) are drawing much attention. Additionally, ature. It also exhibits superior electrical insulation, wear
ferrites magnetic characteristics facilitate their rapid, straightfor- resistance, mechanical hardness, and chemical stability.[14]
ward, and affordable techniques for the reaction.[12a] CoFe2O4 NPs also serve an array of highly advantageous charac-
TMOs have garnered increasing interest as ultrahigh electro- teristics, including large crystal anisotropy in magnetocrystalline
chemically active electrode materials for supercapacitor applica- compounds, evaluated coercivity, moderately saturated magne-
tions in recent years. Co3O4 materials and associated composites tism, affordability, substantial magnetic isotropies, large magne-
have been extensively researched among different TMOs due to torestrictive coefficient, chemical stability, and mechanical
their low cost, high SCs, and environmental friendliness. strength.[15] Numerous techniques can be employed for fabricat-
Furthermore, the Co3O4 electrode material exhibits exceptional ing CoFe2O4 with varying diameters, ranging from the minus-
electrochemical capacitance behavior due to its unique micro- cule 2–50 nm.[16] Cobalt is a fast-relaxing ion that could
structure and morphology.[12b] One notable ferromagnetic enhance the microwave properties of memory components

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and switching devices in electronics and has a remarkably high To the best of our knowledge, most of the reviews that cur-
Curie temperature (1150 °C).[17] Ultrasmall CoFe2O4 superpara- rently exist are dealing with Co-based materials personalizing
magnetic NPs, with an average dimension of 2–8 nm and a the summarized literature to a specific subclass or are concise
substantial surface area of 140.9 m2 g
1, were created using a overviews. Moreover, there are a number of reviews that exclu-
coprecipitation process without any need for a surfactant.[18] sively highlight usage of Co based in the electrode or supercapa-
CoFe2O4 nanocatalyst is used to optimize the reaction conditions citors and batteries, which are not comprehensive enough.
with highest ranging from 40% to 90%.[19] Lately, a wide range of To encourage further advancement in this area, we convey a
sectors, including electrocatalysis,[20] thermopower,[21] ferromag- more thorough explanation of employing Co-based materials
netic characteristics, and ES applications,[22] have shown a signif- in ESDs. We have encompassed a wide range of Co-based mate-
icant deal of interest in the potential uses of Co-based materials. rials, with comprehensive exploration delved into various aspects
Specifically, LiCoO2, which may release a capacity of up to of ferrites, which include spinal, garnet, hexa-, and orthoferrites’
150 mA g
1, has proven to be a highly promising commercial- thorough examination of ferrites and their production.
ized cathode material in relation to energy conversion and Furthermore, electrochemical characterization of materials that
storage.[23] emerged as a pivotal focus are outlined, encompassing the
Metal centers have a significant impact on the rate perfor- performance of ES methods, the evaluation of electrochemical
mance, cyclic stability, and lithium storage characteristics of properties, and providing insights into diverse mechanisms
metal–organic frameworks (MOFs) and are used as electrodes governing their ES potential. The substantial proportion of this
for LIBs, Alternative metallic center-based MOFs often exhibit exploration was dedicated to Co-based ES in conjunction with
lower capacities and adequate cycle stability as compared to different ferrite and nonferrite materials. The versatile applica-
Co-based MOFs.[24] Since active cobalt sites are readily available tions of Co-based ES, particularly in supercapacitors and batter-
and facilitate electron transfer between multiple oxidation states ies, were underscored.
during the conversion reaction, the redox property of cobalt is the
primary driver behind the widespread use of cobalt-based MOFs 2. Ferrites
as electrode materials for applications using sophisticated
ES.[25–27] On the other hand, TMOs have achieved a high capaci- Ferrites are a family of magnetic oxides composed of iron oxide
tance by undergoing a chemical reaction of Faraday on the elec- as the predominant component.[33] Dark brown or gray in color,
trode materials surface. This characteristic has led to significant ferrites are frequently found in nature and have an extremely
interest in TMOs as active electrode components of supercapa- hard-to-brittle physical property[34] Ferrites as major commercial
citors. As we witnessed technological advancements in micro- materials are invented in 1947.[35] Ferrites have several character-
electronics toward the end of the 20th century, there has been istics that make them desirable candidates for various applica-
continual increase in the miniaturization of equipment. tions, including low conductivity, low eddy current, dielectric
However, the present needs for ES cannot be met by traditional losses, and high permeability. Lattice sites possess opposing spin
materials. ES has made substantial use of TMOs, which are arrangements which include oxygen ions and metal ions, uneven
known for their remarkable electrochemical qualities and large antiparallel spin moments cause them to exhibit net resultant
capacity. This has fueled further improvements in the sector.[28] magnetization. Ferrites have greater resistance than ferromag-
When it comes to application, reports witness that CoFe2O4 netic metal because of an inherent atomic-level interaction that
takes a promising position among electrode material suited exists between oxygen as well as metal ions.[36,37] For transform-
for supercapacitor, which can be ascribed to its efficient charge ers and inductor cores operating at radio frequencies, ferrites
storage mechanism and desirable properties. A number of such with narrowed hysteresis loops are clear choices of rectangular
advantageous features are including but not limited to offering hysteresis loop materials that provide switching devices with
high SCs, a wide range of operating potential, cost effectiveness, upgraded relevance for information storage. Ferrite materials
and abundance on the planet. When utilized as a negative elec- may be parted into two groups according to their coercivity: soft
trode in fabrication of asymmetric supercapacitors, CoFe2O4 has ferrites and hard ferrites. For hard ferrites coercivity is high[38]
shown high SCs values, such as 758.86 Fg
1 at 2 mV s
1 and than that of soft ferrites. Ferrites properties are affected by sev-
458 Fg
1 at 1 Ag
1, while keeping its exceptional stability over eral variables, including the type of substituent, the experiment
thousands of cycles. Thanks to preserving a high surface area, setup, and the synthesis technique.[39]
utilizing CoFe2O4 leads to enhanced electrochemical perfor-
mance (ECP) through populated active sites for surface 2.1. Spinel Ferrites
reactions.[29–31] Moreover, CoFe2O4 exhibits several more advan-
tageous features required for batteries, which arise from its The basic structural formula for spinel ferrites is MFe2O4, where
capacitance, reaching up to 1150 mAh g
1, followed by stellar M is any of the divalent metal ions (N, Mn, Mg, Co, Cu, Zn, Fe,
Coulombic efficiency ensuring efficient charge and discharge etc.) or combinations of these ions. Spinel ferrite has an face cen-
cycles. Most importantly, it is a nontoxic material and cost effec- tered cubic unit cell and eight formula units per unit cell
tive as well, while is essential for large-scale production where (M8Fe16O32). One unit cell of ferrite contains 32 octahedral,
excellent cyclic stability is required. When employed as an anode 64 tetrahedral, and 96 intersections between the closely packed
material in LIBs, CoFe2O4 materials demonstrate superior ECP oxygen atoms. Only 8 tetrahedral and 16 octahedral sites are
in terms of specific capacity, cycle performance, and rate occupied by cations. Spinal ferrites are classified according to
capability.[32] expression written as [M 2þ 3þ 3þ 2þ
1
x Fex ] [Fe2
x M x ] and used to

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characterize cation disorder based on the value of x = 0, 1 for hierarchical Co3O4@NF scanning electron microscopy (SEM)
normal and inverse spinal ferrite and 0 < x < 1 for a mixed images are displayed in Figure 2g. The Co–MOF has expanded
spin.[12] The spinal ferrites are special materials with ferrimag- evenly throughout the foam in Figure 2h, confirming the MOFs
netic and semiconductor characteristics.[40] Their unique physico- homogeneous growth. The interconnectedness and internal
chemical characteristics include a modest chemical composition, development of the structures in Figure 2i indicate that the
favorable thermal stability, an elevated magnetocrystalline anisot- MOF has completely grown throughout the foam’s 3D structure.
ropy, and a relatively high curie temperature.[41] They also have a Furthermore, as shown in Figure 2j, the Co3O4@NF has tiny
substantial amount of specific surface-active sites, excellent mag- rods across the foam in addition to a cross-like structure.
netic properties, tunable size, shape, high chemical stability, and As shown in Figure 2k, the MOF’s structure mostly remains
ease of modification or functionalization.[42] intact, with no aggregation among the structure. In addition
Pan et al. developed a porous Mn1.5Co1.5O4 (MCO) spinel thin to extending the surface area of the substance and reactive sites,
film using a combination of the electrodeposition method and the development of the framework on the NF also makes the elec-
the direct growth method. The thin film had a large surface area trode more wetable, minimizes its ionic diffusion length, and
and a layered structure as observed in Figure 2a–f. These features enhances electron transmission. The materials’ rough surface,
contributed to the reduction of Faraday charge transfer resis- as shown in Figure 2l, can provide additional active site and raise
tance, diffusion resistance, and volume change during charge the materials wettability and reactivity.[44] In 2022, Kiey et al.
and discharge cycles.[43] A Co3O4@NF hierarchical 3D electrode synthesized binary cobalt copper ferrites nanosized particles
was synthesized through the thermolysis method where and microstructural investigation validated the formation of the
Co-based MOFs were fabricated on nickel foam. The 3D single-phase cubic spinal structure using the citrate spontaneous

Figure 2. a–f ) SEM image of MCO spinal ferrites (Reproduced with permission.[43] as an open access source). g–i) SEM images of Co-MOF. j–l) SEM
images of Co3O4-350 (Reproduced with permission.[44] Copyright 2024, Elsevier).

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combustion method.[45] Furthermore, Alqarni et al., developed (a total of 160 elements): 24R3þ, 40Fe3þ, and 96O2
.
spinel ferrite NPs (Co0.5Ni0.5VxFe2
xO4) doped with vanadium Tetrahedral (24d), octahedra (16a), and dodecahedra (24c) are
at x proportions deposited onto an electrode made of activated the cations. Fe3þ ions occupy the remaining places, while R3þ
carbon.[46] The manufactured supercapacitor device demonstrated ions occupy the dodecahedral position as shown in the skeleton
cyclic stability and power density endurance at high current levels representation of the octant garnet structure in Figure 3b.[54]
without sacrificing energy density, with SE of 57.24 Wh kg
1 and Equation (1) determines the rare earth ferrite garnets’ total
excellent cyclic stability over 10 000 cycles.[47,48] magnetics moments if the impact of Mc on Ma and Md via
the a–c and d–c interactions is omitted. At the compensation
temperature of 75 K, value is the equal to zero.[55]
2.2. Garnet Ferrites
M ¼ M c
½M d
M a  (1)
Ferrite garnet is represented by R3Fe5O12 where R is one of the
rare-earth elements, such as yttrium. In 1956, Bertatut and The angles and interionic distances (Fe3þ(a)-O2-Y3þ(c) and
Forrat[49] and Pauthenet[50] found the ferromagnetic characteris- Fe (d)-O2-Y3þ(c)) varied when Fe3þ ions swapped out for
3þ

tics of ferrite garnets followed by Geller and Gilleo[51] who inde- Co3þ ions respectively. In addition, as the concentration of cobalt
pendently discovered these qualities in 1957. The garnet increases, the value of the lattice parameter drops between
structure of built-up tetrahedra, octahedral, and dodecahedra 12.3846 and 12.3830 Å. As the dopant concentration rose, the
of oxygen ions coordinates with the metal cations as shown in study using Raman and infrared spectroscopies revealed the
Figure 3a. Ferrite garnets possess a three-lattice crystal structure, forming of a band close to 530 cm
1 represented by dotted lines
composed of the Fe3þ ions found in two of the sublattices (a and and a shift to lower wavenumber with increasing dopant concen-
d) and the Re3þ ions in the third sublattice (c).[52] Since the Re3þ tration (second dotted lines). The dotted rectangle shows the
ions exhibit very weak ferromagnetism, all ferrite-garnets have increment in band intensity at 673 cm
1 as shown in
roughly equal Curie points. Since there is minimal interaction Figure 3d. Fourier-transform infrared (FTIR) spectroscopy of
between the sublattices, the interaction between Fe3þ ions is pri- Y3(Fe1
yCoy)5O12 NPs (y = 0.000 to 0.030) sintered at 900 °C
marily responsible for this variation in Curie point value.[53] Rare for 2 h was studied and the valves for different concentrations
earth ferrite garnets, which exhibit a cubic symmetry with 1a3d are shown in Figure 3e.[56]
space group at room temperature, are the subject of ferrimag- High radiation stability, the narrowest ferromagnetic line
netic research. The unit cell has eight standard elements width, high electrical resistivity, and low eddy current losses

Figure 3. a) Garnet structure of built-up tetrahedra, octahedra, and dodecahedra of oxygen ion coordinate with the metal cations. (Reproduced with
permission.[53] Copyright 1980, Elsevier). b) Skeleton representation of octant garnet structure (Reproduced with permission.[54] Copyright 2009,
Springer). c) XRD analysis of Y3(Fe1
yCoy)5O12 NPs. d) FTIR using Raman spectroscopy and e) FTIR of Y3(Fe1
yCoy)5O12 NPs. (Reproduced with
permission.[56] Copyright 2018, Elsevier).

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are characteristics of yttrium ion garnet ferrites. High surface-to- (where Me = Co2þ, Mg2þ, Zn2þor Ni2þ) presents an appealing
volume ratios in nanoscale garnets often lead to superparamag- option for microwave device applications.[61] They are highly
netic, quantum tunneling, and spin glass like behavior. Thanks renowned for both their chemical stability and uniaxialmagneto
to such improved characteristics, it would be possible to enable crystalline solid anisotropy along the hexagon c-axis; hexaferrite’s
nanoscale ferrites to perform better in industrial and technologi- crystal structure is a member of the rhombohedral space group
cal applications.[57] The garnet structure minimizes interfacial (R
3m). Three formula units (Z = 3) make up the unit cell.[62] It
resistance between solid electrolytes and electrodes, optimizing is believed that the structure is composed of two different kinds
energy transfer within the system. Moreover, garnet-based solid- of crystalline T and S blocks that are progressively staked
state batteries driven from cobalt ferrites offer enhanced safety, throughout the hexagon c-axis as (TST 0 STS 00 ), with primes denot-
higher energy density, and longer cyclic stability compared to ing rotation of 120° about the c-axis.[63] As illustrated in Figure 4a,
conventional batteries. Yet cobalt ferrites with garnet structure various lattice locations are identified by distinct symbols, the
are effective study but there is an underexplored area of research hexagonal unit cell consists of 3 T and 3 S blocks with 18 oxygen
with many conditions including complex synthesis methods’ layers.[64] The close-packing sequence consists of two barium and
demand precision due to the intricate nature of their crystal four recurrent cubic closely packed oxygen layers. The cation is
structure, posing challenges to achieve consistent and reproduc- surrounded by 6 oxygen anions which are 2 tetrahedral sites and
ible results.[58] 4 oxygen anions enveloping the cation. It has 2 spinel units com-
prising 2 layers of 4 oxygen atoms with 3 metal atoms in 4 octa-
2.3. Hexaferrites hedral sites between each layer. Consequently, metals occupy six
sites, of which two are tetrahedral and four are octahedral.[65]
Early in the 1950s, a Philips lab successfully manufactured hex- The T block (Ba2Fe8O14) is made up of 4 oxygen layers, with
aferrite for the first time.[59] Hexaferrites were one of the most 1 oxygen atom replaced by a barium atom in the inner 2 layers,
prevalent types of intriguing material structures until Jonker’s which are next to each other and produce 2 tetrahedral sites and 6
discovery in 1956.[60] Furthermore, at ambient temperature, octahedral ones. Six concrete crystallographic positions are occu-
molecules’ weight of 1410 Da, density of 5.40 g cm
3, planer pied by all the cations (Me2þ and Fe3þ: 2 tetrahedral sites (6c IV,
magnetic anisotropy of the first 2 Y-type hexaferrites, Zn2 Y-type 6c* IV) and 4 octahedral sites (3a VI, 3b VI, 6c VI, and 18 h VI).
(Ba2Zn2Fe12O22) ferrites, and Co2 Y-type (Ba2Co2Fe12O22) were 19 sites are classified as spin-down sites, 3 spin-up sites (3a VI, 3b
detected. At high frequencies, hexaferrite (Ba/Sr)2Me2Fe12O22 VI, and 18 h VI) and 3 spin-down sites (6c IV, 6c VI, and 6c *IV).

Figure 4. a) Ba2Me2Fe12O22 unit cell. These include the divalent barium cation Ba2þ, the O2
anion, and the metal ions in sublattice 3a VI, 6c VI, 3b VI,
18 h VI, and 6c IV* (Reproduced with permission.[66] Copyright 2023, Elsevier). b) Polycrystalline hexagonal structure in bulk cobalt hexaferrite sample
(SEM image of thermally etched disc). c) Large-scale, nonthermally etched disc-like sample of cobalt hexaferrite in 3D: Rz = 78.78  6.98 mm. d) Sample
in disc shaped formed by thermal etching of bulk cobalt hexaferrite in their dimension Rz = 46.71  7.77 mm (Reproduced with permission.[67] Copyright
2016, Elsevier). e) TEM image of CaFe12
2x(ZrCo)xO19 (Reproduced with permission.[68] Copyright 2017, Elsevier).

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In both the S and T blocks, the octahedral site h with the maxi- and oriented BaCo2Fe16O27 was represented by the radar loop
mum multiplicity is shared: there are 2 octahedral sites in the T (RL) curve and the RL contour maps and the quarter wavelength
block and 1 in the S block.[66] Daro et al. investigation involved as a function for the orientated and random composites.[69]
analyzing a bulk cobalt hexaferrite sample obtained through the In 2023, Wu et al. presented a nonmagnetic field orientation
solid-state reaction method, comprising the W, Y, and Z-phases. technique to achieve tuneable crystallographic texture in poly-
Cobalt hexaferrite is of thermally etched disc shape revealed by crystalline hexaferrite composites. BaM and Co2Y hexaferrite
SEM image as shown in Figure 4b. Complex impedance meas- mixtures are combined to produce tabular Co2Z hexacystallites,
urements using the transmission/ reflection method in both which are then orientated in a lamination pattern during the
radio frequency and microwave spectra, along with reflectance, grain formation step of the sintering process. The optimized
exhibited high absorption and minimal losses. Interestingly, the composition of the textured hexaferrite composite exhibited a
observed pattern resembled that of the Z-type, despite the pre- low magnetic specific loss of 0.006, high permeability of 16.6,
dominant presence of the W-phase. Magnetic force microscopy and enhanced Snoek’s product of 17.4 GHz at 200 M Hz. This
revealed the existence of narrow magnetic strength characteris- method offers an effective approach to achieving texture compo-
tics by 300–500 nm-wide parallel stripes on the crystal basal sites as shown in Figure 5.[70]
plane along with narrower 100 nm-wide parallel strip aligned In 2023, Suganya et al[71] investigated an innovative sort of
parallel to stacked crystal layers. Large-scale, nonthermally etched two-step composite electrode substance for supercapacitor imple-
disc-like samples of cobalt hexaferrite in three dimensions, mentation of M-Type BaCoFe11O19 NPs and g-C3N4 with current
Rz = 78.78  6.98 mm, are shown in Figure 4c. Sample in disc density 0.5 Ag
1 and good Cs of 314.6 Fg
1.[72–74] The hexagonal
shaped formed by thermal etching of bulk cobalt hexaferrite structure of cobalt ferrites provides a larger surface area, promot-
in their dimension Rz = 46.71  7.77 mm is shown in ing more active sites for electrochemical reactions, thus enhanc-
Figure 4d.[67] Deshpande et al. used the microwave induced ing performance, and the nanoscale cobalt ferrites retain their
sol–gel combustion route for synthesizing nanosize calcium hex- magnetic properties, facilitating efficient charge separation
aferrite with Co2þ and Zr4þ substitution, by the generic formula and storage through magnetic properties, followed by efficient
of CaFe12
2x(ZrCo)xO19. X-Ray diffraction verifies the formation charge separation and storage through magnetic interactions
of hexaferrites with hexagonal unit cell, supported by a lattice within the hexagonal lattice. To satisfy performance criteria
parameter value (a and c). Rietveld analysis established the space and fulfil the evolving requirements of ES applications, research-
group as P63/mmc. Nanorange of the particle size was revealed ers are investigating and optimizing material selection.
by transmission electron microscopy (TEM) as shown in
Figure 4e.[68] 2.4. Orthoferrites
In 2019, Wei et al. utilized the adsorption combustion method
to synthesize BaCo2Fe16O27 hexaferrite. A straightforward rota- The orthoferrites crystallize in a deformed perovskite structure of
tional orientation process was used to align the easy magnetiza- type AFeO3, space group Pnma (group 62, D16 2h ). Iron ions are
tion planes of the particles embedded in paraffin wax parallel to coupled to 6 anions in this configuration, forming an octahedral
the composite surface. Increased permeability was compared to shape with the iron ion at its core. 12 oxygen anions coordinate
its unaligned counterpart BaCo2Fe16O27. The oriented composite the cationic species A (rare earth or alkaline earth cation), which
exhibited significantly enhanced microwave-absorbing perfor- is in the space between the octahedral structures.[75] A funda-
mance, displaying stronger adsorption and a broader bandwidth mental cell is composed of four molecules: The Fe3þ(4(b)) cati-
(<
10 dB) compared to the randomly oriented composite fre- ons from a parallelepiped in which the Re3þ cations occupy
quency range of 8–18 GHz. The absorber thickness of random roughly a center location (Wyckoff position
4(c)). Six O2 and

Figure 5. Hexaferrite composite of sintering induced texture (Reproduced with permission.[70] Copyright 2023, Wiley).

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iron ions are almost octahedrally coupled. Four of the O2 are structure in a and b plane. The degree of distortion decreases
located at 8(d), while the remaining two are in 4(c) as shown as an angle approaches 90° as the difference between the lattice
Figure 6a with a lilt angle of γ, the O2(4c)-O2(4c) axes of the constants a and b approaches zero. Lattice size increases, and the
deformed octahedra are slanted alternately, creating a zigzag pat- distortion degree and tilt angle decrease as the radius of the ref-
tern along the [0 0 1] direction. In the Fe3þ parallelopiped, the erence electrode (RE)þ3 cations located in deformed dodecahe-
dihedral angle (α = 2 tan
1 a b
1) can be interpreted as a mea- dral interstices between the oxygen octahedra increases. The
surement of the orthorhombic distortion of the perovskite lattice constant of REFeO3 orthoferrites, a, b, c, and volume V

Figure 6. a) Superexchange angles θI and θII are indicated on the elementary unit cell of REFeO3. The O(4c) and O(8d) places that are lighter are in front
of the ac face, while the darker ones are behind. b) The lattice constant of REFeO3 orthoferrites: a, b, c, and volume V of the fundamental unit cell
(Reproduced with permission.[76] Copyright 2003, Elsevier). c–g) The magnetic configurations and lattice structure in orthorhombic RFeO3 with
Pbnm phase. The deformed perovskite structure’s tilting octahedral respectively (Reproduced with permission.[79] Copyright 2019, Elsevier).

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of the fundamental unit cell, is shown in Figure 6b. The major upon passing over the crucial size of around 40 nm. Excellent
magnetic interaction in the REFeO3 orthoferrites is the superex- SCs at the low scan rates was found by the cyclic voltammetry
change coupling Feþ3─O2─Feþ3, which results in a non-colinear (CV) experiment of NPs annealed at 800 °C.[80] In 2019,
antiferromagnetic ordering of the Feþ3 sublattice, which is Somvanshi et al. used the sol–gel combustion method to develop
considered a weak ferromagnetic interaction. Feþ3─O2─Feþ3 a cobalt-doped neodymium orthoferrite. The samples conform to
coupling is substantially weaker and the magnetic an orthorhombic peroviskite structure. The size range of the crys-
REþ3─O2─Feþ3 and REþ3–REþ3 coupling are of 102 –103 tallites is 12–14 nm, as shown in Figure 7a,b. According to the
orders.[76] Rare-earth orthoferrites, or RFe3 (where R stands Rietveld refinement, bond length (Fe─O) and bond angle
for rare-earth), are typical instances that have garnered a lot of (Fe─O─Fe) change with cobalt doping. The TEM combined with
attention recently. The rotation of the FeO6 octahedron and the selected-area electron diffraction (SAED) pattern demon-
the Dzyaloshinskii–Moriya interaction allowed for the experi- strated the material crystalline structure as clearly discernible
mental confirmation of the antiferromagnetic configuration in Figure 7c,d.[81] In 2019, Heydari et al. used precipitation tech-
and macroscopic magnetism of the orthoferrites RFeO3.[77] nique to produce carbon/CoFe2O4. The carbon composite NPs of
It has also been demonstrated that orthoferrites characteristics CoFe2O4 have a consistent dimension of 209 nm. Field emission
are affected by magnetic fields, pressure, and temperature.[78] scanning electron microscopy (FESEM) and TEM images
The deformed perovskite structure’s tilting octahedral is seen showed the average size of ferrite range of 35.6  7.8 nm as
in Figure 6c. The definitions of the octahedral tilting (θ) and rota- shown in Figure 7e. Electrochemical tests revealed an electrical
tion (φ) angles are as follows: θ = (180°
∠(Fe─O─Fe))/2 and double-layer approach because of a high carbon content. At an Id
φ = (90o
∠(O─O─O))/2. The Fe─O─Fe and interoctahedral of 0.16 Ag
1, high Cs of 102.5 Fg
1, excellent cyclic stability with
O─O─O angles are displayed by the conversion. The three 81.5% retention up to 6000 cycles (Figure 7f,g), and a high rate
antiferromagnetic structures are represented by Figure 6d–f: capability with 30% capacitance retention beyond 20 Ag
1 are
(d) A-atomic force microscopy (AFM), (e) C-AFM, and depicted in Figure 7h,i.[82]
(f ) G-AFM. The irreducible A2(Gz, Fx) represents the G-type The cobalt ferrites maintain their magnetic behavior, which
magnetic structure of iron in Figure 6g, where Gz and Fx are aids in efficient charge separation and storage through magnetic
the components of the ferromagnetism and antiferromagnetic interactions within the lattice. Basically, there is a correlation
vectors, respectively.[79] between the microstructure of cobalt ferrite and its performance
In 2020, Shyamaldas et al. used hydrothermal synthesis to cre- when used in the ES system. Comprehensive review of crystal
ate pure cobalt ferrite NPs. X-Ray diffraction study validated the structures of cobalt ferrites is an important factor for enhancing
cubic spinel arrangements and increased crystallinity. This can ES performance. Hexagonal cobalt ferrites provide a large
be attributed to the change from single-domain to multidomain surface area, exhibit magnetic behavior at the nanoscale, and

Figure 7. a) SEM visuals of NdFe0.7Co0.3O3 NPs, b–d) TEM combined with SAED of NdFe0.7Co0.3O3 NPs (Reproduced with permission.[81] Copyright
2019, Elsevier). e) FESEM image of uniform carbon/cobalt ferrite microsphere. f ) Profiles of GCD curve at different current densities between 0.16 and
20 Ag
1. g) At low-current infrared decrease. h,i) Stability of cycling of the two-electrode system of a CoFe2O4–carbon nanocomposite at Id of 1 mA cm
2,
along with CoFe2O4 Ragone plot (Reproduced with permission.[82] Copyright 2019, Taylor and Francis).

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enhance electrochemical properties, particularly in supercapaci- substance and electrolyte, to all in all improvement of ECP.
tors and batteries. These orthorhombic cobalt ferrites provide a The material for rod-like Co3O4 electrode was found to have a
high surface area due to their unique arrangements, enhanced Brunauer–Emmett–Teller (BET) surface dimension of
charge separation due to magnetic properties, and excellent elec- 38.6 m2 g
1 and a pore diameter of 3.45 nm.[87] Table 2 summa-
trochemical behavior.[29,83] rizes some materials synthesized through the hydrothermal
method for ECP development. Multi-walled carbon nanotube
(MWCNT), reversible hydrogen electrode as (RHE), and satu-
3. Synthesis Methods rated calomel electrode as (SCE).
This method consistently delivers cobalt ferrite NPs with dis-
There are numerous methods of synthesizing ferrites, such as
tinct crystalline phases and exceptional phase purity, resulting in
the solid-state, template method, sonochemical, electrochemical,
well-defined X-Ray diffractometer (XRD) peaks with narrow
solvothermal, coprecipitation, sol–gel, hydrothermal, thermal
width, signifying high crystallinity and crystallographic data,
decomposition, combustion technique, and microemulsion tech-
ensuring accuracy in determining lattice parameter ‘a’ and ‘c’,
niques. Nevertheless, there is currently no single technique for
typically, around ≈8.36 to 8.39 Å in a cubic spinal structure.
creating ferrites, and each synthesis method has pros and cons.
The SEM images, of cobalt NPs exhibit a uniform size ranging
The synthesis technique also has a noteworthy effect on the mor-
from 20 to 200 nm, depending on synthesis conditions. This
phological framework and properties of these magnetic ferrites,
allows for precise control over particle morphology, leading to
which may have an impact on the material catalytic activity when
the formation of spherical, rod-like, or nanoplatelets structures.
utilized as catalysts. For example, Co3O4 NPs were prepared for
Furthermore, TEM analysis revealed well-defined NPs, typically
supercapacitor application under a precise morphology control,
with average size range from 5 to 50 nm, depending on synthesis
which resulted in SCs of 166 Fg
1 when a current density of
parameter. This technique offers detailed insights into NP mor-
0.5 Ag
1 was applied.[84]
phology, including crystalline domains, surface features, and
defects. It also has some limitations including high-temperature
3.1. Hydrothermal Process and -pressure requirements, long synthesis duration, and forma-
tion of undesired phase or agglomerates.[88]
Among the most auspicious and ecologically conscious approach
for synthesis is hydrothermal method. It enables the utilization
of various solvents, either aqueous or nonaqueous, to provide 3.2. Electrochemical Deposition Method
more control over the morphology and distribution of particle
dimensions.[12] For instance, to obtain CoZnFe2O4 NPs, Metal can be deposited in layers on specific conducting sub-
high-purity zinc sulfate, cobalt sulfate, and ferric sulfate were dis- strates employing a conventional approach termed electrochem-
solved, stirred for 30 min at room temperature, and pH of solu- ical deposition or electrodeposition. The deposition technique
tion was reduced; aqueous sodium hydroxide was added followed enables employing of electric current. The readily accessible ions
by stirring for 2 h. The resulting solution was transferred into an within the electrolyte or those obtained from the anode as the
autoclave-lined Teflon to undergo hydrothermal treatment at result of the replenishment process will be deposited at the cath-
220 °C for 8 h, solution was filtered, repeatedly cleaned in deion- ode that is negatively charged in the electrochemical deposition
ized water, and dried for 24 h at 80 °C in an oven.[84] Cobalt process. The amount of charge carried by the cathode is mea-
nitrate, ferric nitrate, ammonium hydroxide, and Arabic gum sured by the current following through the external circuit.
were combined in a simple environmentally friendly hydrother- To achieve ideal grain size in the nanoscale range during the elec-
mal process that produced pure, spherical, tuneable-sized cobalt trodeposition technique, adjustments should be made concern-
ferrite NPs in less than 4 h by adjusting the reaction parameters, ing pH, bath composition, temperature, and current density of
including reaction time of 0.5–8 h, reaction temperature of various nanostructures that can be readily created using electro-
120–180 °C, 0–100% v/v ethylene glycol, and pH value of 8–9.6. chemical synthesis, including NRs. Technique is remarkably
Their results showed that an increase of the reaction time from effective and provides multiple benefits, including low cost, a
0.5 to 8 h leads to an increase in the crystallite size from 3.6 to comparatively less synthetic approach, impressive homogeneity,
8.5 nm, while increasing the temperature of the reactants from straightforwardness, and an environmentally friendly
120 to 180 °C increased it from 4.5 to 7.8 nm. In the same approach.[89] For instance, facial electrodeposition yields 2D lay-
order, increase of pH from 8 to 9.6 increased the crystallite size ered lanthanum cobalt double hydroxide (La–Co LDH) that is
from 12.3 to 12.9 nm, respectively.[85] High-porous nanorods easily able to form 2D porous films on top of the substrate as
(NRs, cobalt oxide without binders was deposited on nickel sub- shown in Figure 8a. Figure 8b–d shows a nanostructure spread
strate using hydrothermal process) were subjected to calcination throughout the 3D nickel foam, and Figure 8e displays the sim-
at 300 and 500 °C, resulting in the Co3O4 NRs electrode materi- ulated XRD pattern of the individual single-crystal data of cobalt
als. The permeable Co3O4 nanorods were separately calcinated at and lanthanum hydroxides, as verified by the JCPDs crystallo-
300 and 500 °C, revealing superior ECP at 300 °C. Specifically, graphic database. The La–Co LDH has successfully formed, as
the Cs in a 6 M aqueous mixture of electrolyte KOH was evidenced by the well-defined matching (0 1 1), (0 1 9), (1 1 10),
measured as ≈226.3 Fg
1.[86] In 2019, Venkatachalam et al. and (1 2 9) peaks. Figure 8f depicts a well-defined peak resulting
synthesized a 1D rod-shaped cubic framework. This structural from the lattice vibration of the metal oxygen bonds through
configuration offers several advantages, including an increased FTIR where peaks lie between 1000 and 1500 cm
2. An ambient
number of active sites, enhanced contact between electroactive temperature was used for the electrochemical deposition

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Table 2. The ECP of several materials using the hydrothermal method.

Electrode Potential window Cyclic stability Specific conductivity/current density References

1
1
CoFe2O4 nanowires 0–0.55 V 142% retention after 2000 cycles 428 Fg (5 mV s ) [265]
CoFe2O4 hollow microspheres 0–0.4 V (vs Ag/AgCl) 98% retention after 500 cycles 1790 Fg
1 (25 mV s
1) [266]
CoFe2O4 nanoflakes 0–2.5 V (two-electrode systems) 62.5% retention after 2500 cycles 433 Fg
1 (0.15 mV s
1) [267]
CoFe2O4 nanosheets 0–0.4 V (vs Ag/AgCl) 98% after 5000 cycles 503 Fg
1 (2 Ag
1) [268]

1
CoFe2O4 nanomesh NP 0–0.6 V (vs Ag/AgCl) 92.6% retention after 3000 cycles 1426 Fg [269]
CoFe2O4/MnO2 nanosheet arrays
0.2–0.4 V (vs Ag/AgCl) 91.5% retention after 2250 cycles 3.59 Fcm
2 (2 mA cm
2) [270]
CoFe2O4/MnO2 nanosheet arrays 0–0.045 V (vs SCE) 87.2% retention after 5000 cycles 2491.8 Fg
1 (0.5 mA cm
2) [170]
CoFe2O4/FeOOH
0.2–0.3 V (vs Hg/HgO) 91.3% retention after 1000 cycles 332.4 Fg
1 (0.5 Ag
1) [271]

1
1
FeCo2O4 nanoflakes/nickel foam (NF) 0.01–0.3 V 100% retention after 2500 cycles 1222 mAh g (800 mA g ) [272]
FeCo2O4 nanoneedles/NF 0.01–0.3 V 95% retention after 2000 cycles 875 mAh g
1 (2 Ag
1) [268]
CoFe2O4 nanowire/FCF 0.005–0.3 V 87.1% retention after 150 cycles 595.3 mAh g
1 at 3.2 Ag
1 [273,274]
Hollow CoFe2O4 nanosphere 0.01–3 V (vs Li/Liþ) 93.6% retention after 50 cycles 1000 mAh g
1 at 900 mA g
1 [275]
þ
Flower-like CoFe2O4 microsphere 0–3 V (vs Li/Li ) 77.9% retention after 50 cycles 717 mAh g
1 at 1 Ag
1 [276]
Flower-like CoFe2O4/MWCNTs 0.01–3 V (vs Li/Liþ) 85% retention after 50 cycles 359 mAh g
1 at 1.8 Ag
1 [277]
CoFe2O4/graphene nanocomposite 0.01–3 V (vs Li/Liþ) 66% retention after 50 cycles 406 mAh g
1 at 2 Ag
1 [278]

1
1
CoO/CoFe2O4/N-doped graphene 0.6–0.78 V (vs RHE) 73% retention after 100 cycles 680 mAh g at 2 Ag [96]
3D CoFe2O4 hollow nanospheres 0.78 V (vs RHE) – 33.9 mA cm
2 at 1.96 V [279]
CoFe2O4/activated carbon 0.02–3.00 V 90% retention after 5000 cycles 202 Fg
1 at 1 Ag
1 [280]
ZnO@CoFe2O4 core/shell/NF – 22% capacitance loss after 6000 cycles 857.7 Fg
1 at 0.1 Ag
1 [281]

1
1
Co3O4 0–0.5 V (vs Ag/AgCl) 93.3% after 5000 cycles 1140 Fg at 1 Ag [282]
Co (OH)2 0–0.6 V (vs Hg/HgO) 82.6% after 1500 cycles 935 Fg
1 at 2 Ag
1 [283]
Co-MnP 0–0.6 (vs Hg/HgO) 88% after 8000 cycles 571 Fg
1 at 2.2Ag
1 [184]
rGO/Co3O4 NPs 0–10 V 95.6% after 1000 cycles 82.6 (2–100 mV s
1) [284]
Co3O4 nanosheets@rGO
0.1 to 0.4 (vs SCE) 95.3% after 3000 cycles 74.3 (1–20 Ag
1) [285]

1
fCNTs-decorated Co3O4 0–0.4 (vs Hg/HgO) 100% after 1000 cycles 45 (1–100 mV s ) [286]

process, as Figure 8g represents a nickel cobalt LDH (Ni─Co Co3O4.[93] Table 3 summarizes capacitive performance of various
LDH) precursor applied using an aqueous mixed electrolyte con- materials using electrochemical deposition method. It can be
taining 1 mM nickel nitrate and 2 mM cobalt nitrate. Following inferred that electrochemical deposition emerges as a promising
electrodeposition, the nickel foams went through ultrasonic avenue for synthesizing cobalt ferrites, offering precise control
cleaning, three rounds of ethanol, distilled water rinsing, and over deposition parameters and yielding materials with well-
ambient temperature drying process, and later annealed for defined crystallographic phases and high purity. This method
2 h at 300 °C in a muffle furnace.[90] enables the growth of cobalt ferrites thin films or coatings with
In 2017, Kong et al. introduced a Co3O4 nanosheet that offers controlled morphologies and thickness, leading to uniform
easy controllability and in situ growth. The resulting materials surface morphology and well-defined grain boundaries that
possess a porous structure, effectively enhancing the region of can be observed from SEM and TEM images typically ranging
interaction between active materials and electrolytes, thereby from few nanometers to hundred nanometers.[94]
improving ECP.[91] Chloride electroplating bath has been
employed to develop CoNi–barium ferrite magnetic composites.
The granule CoNi deposits had minimal roughness around 3.3. Coprecipitation Method
4–8 nm.[92] Optimizing the design through the combination of
Co3O4 with metal oxide allows for the synergistic enhancement A simple assembly of a wet chemical process termed coprecipi-
of ECP initially, porous Co3O4 nanosheets arrays are directly tation is frequently used to create cobalt ferrite due to its numer-
synthesized on the carbon cloth followed by a thin layer of ous benefits, including ease to use, affordability, a capability to
Co3O4 nanosheets using secondary electrodeposition process. produce ultrafine particles, and exceptional stoichiometric con-
Figure 9A represents the two-step synthesis of Co3O4@CoS trol. The precipitation agent is added to create a single-phase,
core–shell nanosheet arrays on CC, and Figure 9B shows homogenous inorganic solid at the appropriate pH, heat treat-
SEM images of Co3O4/CC, inset: CoS/CC; (b–f ) Co3O4@CoS/ ment is crucial for the prepared sample crystallinity and particle
CC@1–5 cycles electrodeposition. This sequential approach development. Controlling the release of cation and anode can
ensures the building of a well-defined core–shell framework with modify the growth and nucleation kinetics. The schematic

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Figure 8. a) Diagrammatic representation of the creation of Ni foam substrate by La–Co LDH. b–d) FESEM image of the substrate. e) XRD spectra of
sample. f ) FTIR spectroscopy of the material (Reproduced with permission.[2] as an open access source). g) Schematic representation of NiCo2O4
(Reproduced with permission.[90] as an open access source).

representation is shown in Figure 10. The parameters such as organic GO and inorganic spinel ferrite as shown in Figure 10B.
temperature, the desired solution pH, the concentration of ions At a frequency of 100 Hz, with an applied magnetic field of 0.9T,
and reactants, and the kind of solution can influence the size, a capacitance of 37.27  10
6 F and a maximum dielectric
shape, and dispersion of NPs.[95] In 2023, Kenari et al. used constant of 1.12  10
8 were obtained. Along with FESEM in
graphite as a conductive material to construct electrodes for elec- Figure 10C(a–c), superparamagnetic property is the consequence
trochemical investigation. At an Id of 1 Ag
1, ZrCoFe2O4/NRGO of combining a weak and strong ferromagnetic of CF and GO
electrode showed outstanding electrochemical activity, with a and CF–GO composite respectively. Figure 10D(a–c) represents
SCs of 307 Fg
1. A stability analysis revealed that, after 5000 (a) high-resolution transmission electron microscopy (HRTEM)
cycles, the original capacity was maintained at almost 97%, images, (b) SAED pattern, and (c) energy-dispersive spectroscopy
suggesting very strong electrochemical stability.[96] In 2018, (EDS) spectrum CF-GO composite (size). The GO M–H curve
Ambikeswari et al. synthesized GO and Co–ferrite composite clearly shows that GO exhibits a weak ferromagnetic ordering
by in situ chemical coprecipitation. The magnetodielectric char- with unsaturated area at the borders and Ms of 0.37 emu g
1
acteristics were more greatly increased by the combination of an at Hc of 62 Oe. Using Hc of 1462 Oe for CF and Ms of 64 emu g
1

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Figure 9. A) Schematic representation of the two-step formation of Co3O4@CoS core–shell nanosheet arrays on CC. B) SEM pictures of a) Co3O4/CC,
inset: CoS/CC, b–f ) Co3O4@CoS/CC at 1–5 cycles electrodeposition, respectively (Reproduced with permission.[93] as an open access source).

Table 3. Capacitive performance of various materials using electrochemical deposition method.

Electrode SCs value Specific conductivity/current density Cyclic performance References

1
1
CoFe3O4 nanosheets 1033.3 Fg 20 mV s 77% retention after 3000 cycles [287]
Cobalt oxide 235 Fg
1 20 mV s
1 – [288]
Hierarchically CO3O4 film 443 Fg
1 2 Ag
1 Hierarchical structure maintains [289]
334 Fg
1
40 Ag
1 after 3000 cycles

Co3O4/Ni (OH)2 1144 Fg
1 5 mV s
1 6.6% capacitance decay after 500 cycles [290]

1
Hydrous RuO2 NP on Co3O4 flakes 905 Fg 1 Ag
1 96% retention after 5000 cycles at 10 Ag
1 [291]
Hierarchical Co3O4/Co (OH)2 nanoflakes 601 mF cm
2 2 mV s
1 92% capacitance retention [292]
for optimized sample
CoFe2O4 768 Fg
1 (1 Ag
1) 0.5 Ag
1 80% after 10 000 cycles [293]

1
1
CoFe2O4 NRs 460.5 Fg (1 Ag ) 3-5 Ag
1 95.8% after 5000 cycles [294]
CoFe2O4/Ni 9.7 C cm
2 (10 mA cm
2) 10 mA cm
2 89.7% after 5000 cycles [295]

1
1
1
Co(OH)2 609 Fg (10 mV s ) 50 mV s 94.4% after 2000 cycles [296]
NF/ CoFe2O4/PEDOT 299 mA hg
1 (1 Ag
1) 230.4 Wh g
1 91.7% after 2000 cycles [297]
Zn-doped Co (OH)2 1774 Fg
1 (1 Ag
1) 20 Ag
1 75.21% after 1000 cycles [298]
CoNiFe-LDH 360 C g
1 (0.4 Ag
1) 10 Ag
1 84% after 2000 cycles [299]
CoCl2.6H2O 878 Fg
1 (1 Ag
1) (2–7 Ag
1) 78% after 5000 cycles [300]

2
Bi2O3@Co(OH)2 947.1 mF cm 2 mA cm
2 99.8% after 1000 cycles [301]
Co-doped polyaniline (PANI) (SP-PANI) 149.3 mF cm
2 (0.5 mA cm
2) 0.5 mA cm
2 96.6% after 5000 cycles [302]
CoFe2O4 nanosphere cluster (CFNCS) 151 Fg
1 (5 mV s
1) – 87% after 1000 cycles [303]

1
1
1
NiO–CoO–PPy 1123 Fg (1 Ag ) 10 Ag 90.1% after 5000 cycles [304]
Ni–Co LDH/CoMoO4 1812 Fg
1 (1 Ag
1) – 93.7% after 5000 cycles [305]

illustrates a ferromagnetic characteristic at an elevated Hc of In 2022, Rajeevgandhi et al. prepared cobalt cadmium ferrite
22 Oe, CF–GO exhibits Ms of 53 emu g
1. The frequency- NPs by chemical coprecipitation technique as shown in
dependent value of CF is obtained by changing the magnetic Figure 11A. Figure 11B(a–e) shows HRTEM image of the sample
from 1000 to 9000 Oe.[97] where (a–c) shows the of Cd0.3Co0.7Fe2O4 NPs annealed at 600 C

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Figure 10. A) Schematic representation of the coprecipitation method. B) Schematic representation of CF NPs decorated on GO sheets and a typical
model of magnetodielectric measurement. C) FESEM micrographs for GO, CF, and CF–GO composite. D) a) HRTEM pictures. b) SAED designs. c) EDS
spectrum CF–GO composite (Reproduced with permission.[97] Copyright 2018, Elsevier).

with different magnifications, (d) SAED, and (e) corresponding CdxCo1
xFe2O4 NPs annealed at 600 °C (x = 0.3, 0.5, and 0.7),
particle size distribution represented in the form of histograms where the scan rate of 2 mV s
1 produces the excellent Cs at
with spherical and cubic NPs with size starting at 30 nm. 395 Fg
1.[98] In 2016, Sivagurunathan et al. used citrate as a
The product sample was found to be semiconductive, as evidence chelating agent in the coprecipitation technique to create cobalt
by the enhanced AC conductivity of 5.5  10
4 Sm
1 for ferrite (CoFe2O4) NPs. XRD, thermogravimetric analysis, and
Cd0.3Co0.7Fe2O4 NPs. Figure 11C(a–c) represents the CV of differential thermal analysis were used to characterize the

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Figure 11. A) Systematic representation of sample preparation. B) a–c) HRTEM micrographs of Cd0.3Co0.7Fe2O4 NPs annealed at 600 °C with different
magnifications. d) SAED. e) Corresponding particle size distribution histogram. C) CV study of CdxCo1
xFe2O4 NPs annealed at 600 °C (x = 0.3, 0.5, and
0.7) (Reproduced with permission.[98] Copyright 2022, Springer).

Co-ferrite NPs that are calcinated at 400 to 800 °C. Results 3.4. Sol–Gel Autocombustion Method
showed a uniform distribution of approximately cubical particles.
The produced NPs’ high stability is revealed by their zeta poten- A sol–gel technique is based on the burning of gel in a dissemi-
tial, the Z-average is determined to be 296.6 nm, and Cs value of nation way to generate dark brown power as a product. This pro-
609 Fg
1 was recorded at a scanning rate of 2 mV s
1.[99] Table 4 cess results in an exothermic chemical reaction and self-ignition
summarizes the capacitive performance of several materials of gel. The fact that this approach produces no intermediary
using the coprecipitation method. goods makes it very easy to use, quick, and cost-effective.
This method offers versatility but demands careful parameter Starting materials such as metal nitrate salts and organic fuels
adjustments for uniformity and distribution. The synthesized like glycine, citric acid, hydrazine, urea, and carbohydrazide
cobalt ferrite NPs dimensions typically range from a few nano- are readily accessible, and the stoichiometry and crystalline size
meters. Factors like precursor’s salt concentration, pH, reaction may be easily regulated. Colloidal gel is created by combining
temperature, and heat treatment duration influence NP size. metal nitrate with an organic solvent; NH4OH is filled in the mix-
Adjusting precursor concentration and reaction conditions can ture to bring the pH level to neutral. To get rid of the extra liquid
yield particle size ≈5–20 nm. Achieving precise size distribution in the reaction container, this solution must be heated to between
control requires meticulous parameter optimization which 80 and 100 °C and stirred constantly. It ignites and forms xerogel
includes annealing temperature. This method offers advantages after an extended time. Organic solvent, temperature, and the
including simplicity, controlled particle size, high yield, pace at which liquid is removed all have an impact on the
homogeneity and versatility for large-scale production. dimension of the ferrite power.[101] Using the citrate spontane-
However, its limits to agglomeration, surface defects, energy ous combustion method, ferrite magnetic NPs have been
intensity, and scalability constraints persist.[100] gradually produced. Nanosized particle creation is revealed by

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Table 4. The capacitive performance of several materials using coprecipitation method.

Electrode Working voltage SCs value Specific conductivity/ Cyclic performance References
current density
3D hollow fluffy Co3O4 cages From 0 to 0.45 V (Ag/AgCl) 948.9 Fg
1 (1 Ag
1) 56 (1–40 Ag
1) – [306]

1
1
3D coralloid Co3O4 From
0.2 to 0.4 V (vs SCE) 591 Fg (0.5 Ag ) 10 (0.5–4 Ag
1) 97% (2000 cycles) [307]

1
1
Co3O4/graphite From
0.3 to 0.3 V (vs SCE) 395.04 Fg (0.5 Ag ) – 97.7 (1000 cycles) [308]
Cd-doped porous Co3O4 nanosheets From 0 to 0.4 V (vs SCE) 737 Fg
1 (1 Ag
1) 36.6 (0.5–10 Ag
1) 96% (1000 cycles) [309]
CoxNix
1 LDH NPs From 0 to 0.5 V (vs Hg/HgO) 2614 Fg
1 (1 Ag
1) – 86.4% (1000 cycles) [310]
Co doped Mn3O4 spinal structure From 0.01 to 0.55 V (vs Hg/HgO) 2701 Fg
1 (5 Ag
1) 56.9 (5–30 Ag
1) 76.4 (500 cycles) [311]
Co3O4/NiO nanofilms From 0 to 0.5 V (vs Hg/HgO) 739.8 Fg
1 (5 mV s
1) 76 (5–25 mV s
1) 120 (500 cycles) [312]

1
1
Co–Ni–O/3D graphitic carbon nanosheet From 0 to 0.6 V (Ag/AgCl) 1538 Fg (1 Ag ) 40 (1–15 Ag
1) 93.6 (1000 cycles) [313]
MnCoFeO4 From 0 to 0.45 V (vs SCE) 675 Fg
1 (1 mV s
1) 1.5 Ag
1 92.86% (1000 cycles) [187]
ZrCoFe2O4//NRGO From 0 to 0.5 V (Ag/AgCl) 307 Fg
1 (1 Ag
1) 0–0.5 Ag
1 97% (5000 cycles) [96]

1
1
1
CdxCo1
xFe2O4 From 0 to 0.5 V (Ag/AgCl) 395 Fg (2 mV s ) 1.5 Ag – [98]
CoFe2O4 From 0 to 1 V (Ag/AgCl) 609 Fg
1 (2 mV s
1) 0–0.5 Ag
1 – [99]
CoxZn1
xFe2O4 From 0 to 0.5 V (Ag/AgCl) 377 Fg
1 (10 mV s
1) 0–0.5 Ag
1 – [107]
CoFe2O4 NPs From
0.6 to 0.4 V (vs Hg/Hg2SO) 466 Fg
1 (1 Ag
1) 0–0.5 Ag
1 100% (10 000 cycles) [209]
Gr/Co3O4 From 0 to 0.05 V (Ag/AgCl) 278.5 Fg
1 (1 Ag
1) (5–100 mV s
1) 84% (700 cycles) [314]

1
1
CoFe2O4/Co3O4 From 0 to 0.45 V 761.1 Fg (10 mV s ) – 92.2% (1000 cycles) [315]
CexCo2Fe2O4 From
0.1 to 0.5 V 937.50 Fg
1 (1.5 Ag
1) 82.3% (4000 cycles) [316]
CoxZn1
xFe2O4-rGO From
300 to 950 V 151.3 Fg
1 (10 mV s
1) – 75% (100 cycles) [317]
CoFe2O4/SiO2 From 0.1 to 0.5 V 316.14 Fg
1 (4 Ag
1) – 95.4% (5000 cycles) [318]

1
1
2
CoMoO4 From
0.2 to 0.6 V 133 Fg (1 mV s ) 1 mA cm 100% (1000 cycles) [319]
CoF
rGO From 0.1 to 0.5 V 551 Fg
1 (2 mV s
1) 0.25–3 Ag
1 98% (2000 cycles) [320]
CoFe2O4
graphene aerosol From
0.2 to 0.8 V 253 Fg
1 (10 mV s
1) 4 Ag
1 – [321]

morphological analysis using FESEM and HRTEM micrographs, value 637 Fg
1, indicating 98.79% Coulombic accuracy after
and microstructural investigation validates the formation of the 5000 cycles at 15 Ag
1.[103] In 2018, Aslam et al. used a conven-
single-phase cubic spinal structure.[45] tional urea combustion approach (Figure 13A) to create the
In 2023, Jeevanantham et al. prepared a robust and high- CoFe2O4 spinal NPs with a mean diameter of 80 nm
performing electrode of Co0.75Mg0.25Fe2O4 NP and annealed (Figure 13B). The CFO–NPs have outstanding initial charging
them at 200, 300, and 500 °C (Figure 12A). The lattice expands discharging and capacity capabilities of 1506 and 1524 mAh g
1.
from 8.3524 to 8.3704 Å, accompanied by an increase in temper- The discharging capacity may hold at 896 mAh g
1 almost like the
ature. A notable ES is favored by the partial occupancies, which theoretical capacity of CFO even after 50 cycles. Figure 13C rep-
shorten the charge diffusion path. Bond dissociation favoring resents (a) the CFO–NPs electrode’s CV profile scan rate at
sufficient charge separation at high temperatures and high 0.01 mV s
1, (b) electrode initial charging and discharging pro-
SCs value is shown at 500 °C of 579.3 Fg
1 at 0.5 Ag
1 and files, (e) the electrode charging/discharging profiles at various
1000 cycles at 5 Ag
1, it has cyclic stability of 96.49% and accord- cycle counts, and (d) the electrode performance at a current den-
ing to Figure 12B(a–c), increasing temperature also affects the sity of 50 mA g
1.[104] In 2020, Karthikeyan et al. prepared hier-
samples morphology and average particle size. Figure 12C(d–f ) archical porous CoFe2O4. The electrode of the supercapacitor was
shows that MCF1 direct-bandgap measurement drops to made of hierarchical porous CoFe2O4 which demonstrated favor-
1.214 eV for MCF2. The bandgap measurements start to rise able electrochemical characteristics at Id of 1 Ag
1, the Cs of the
(1.22 eV) when the annealing temperature rises because the com- CoFe2O4 electrode may reach 443.89 Fg
1 and 16 Ag
1 compared
posites’ crystalline nature decreases.[102] In 2023, Jeevanantham to 1 Ag
1, 75.12% of the capacitance was still conserved. Excellent
et al. used sol–gel combustion to create strontium-doped cobalt cycling stability lost 20.65% after 6000 cycles.[105] The optimum
ferrite NPs, which are then annealed at different temperatures of approach was employed to obtain amorphous cobalt ferrite power
200, 300, and 500 °C with sizes of 33, 36, and 35 nm, respectively. using sol–gel technique where its constituents’ NPs ranged in
A homogenous and clustered structure was demonstrated by size from 7 to 28 nm and with a saturation mass magnetization
FESEM. Using Tauc’s figure direct bandwidth, energy of 62 emug
1, samples’ ferrimagnetic behavior at ambient tem-
values from UV–vis–NIR spectroscopy are 1.24, 1.21, and perature was revealed by pertinent magnetic characteristics.[106]
1.20 eV. After 1000 cycles at 5 Ag
1 the detected specimen Metal precursors and sodium hydroxide at ambient conditions
(Co0.8Sr0.2Fe2O4@300 °C) preserved 85.5% of its supercapacitance were used to create cobalt doped zinc ferrite NPs. Zinc ferrites

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Figure 12. A) Schematic flowchart of synthesis of Co0.75Mg0.25Fe2O4 NP. B) FESEM pictures: a–c) MCF1, MCF2, MCF3. e,f ) UV–visible of MCF1, MCF2,
MCF3 (Reproduced with permission.[102] Copyright 2023, Elsevier).

doped with cobalt were produced as CoxZn0,04
xFe2O4 solids and accelerate the reaction of solid entities. Typically, an
(x = 0,0.01,0,02) in three distinct concentrations.[107] Table 5 autoclave is filled with substrates and additional reagents includ-
summarizes the capacitive performance of several materials ing the solvent, and it goes into the oven at a specific temperature
using the sol–gel combustion method. for a predetermined time. Before extracting the final product, the
The synthesized cobalt ferrite NPs with sizes typically range sample is cleaned of contaminants using deionized water and
from a few nanometers to several tens of nanometers. This alcohol and then vacuum dried. The primary benefits of this
method involves the formation of sol–gel precursor solution, fol- technique are that, by raising the temperature and pressure to a
lowed by autocombustion triggered by the addition of a fuel or critical point, practically every element can be dissolved in the
oxidizing agent. Factors such as precursor concentration, pH, solvent.[109] The CoMn2O4 microplate-structured catalyst with
gelation temperature, and the type of fuel used influence NP size. a larger specific area was successfully prepared and evaluated
Typically, cobalt ferrite NPs produced exhibit size in the range of as peroxymonosulfate activator using the solvothermal method
5–50 nm. This method offers advantageous like simplicity, scal- as shown in Figure 14A. The three catalysts, namely CoMn2O4
ability, and the ability to produce NPs with tailored properties. MD (microplate-structured), CoMn2O4 PM (powder), and
However, challenges such as control over particle size distribu- CoMn2O4 ST (spinel), exhibited distinct morphologies and
tion and potential impurity incorporation need to be addressed structures. In constant to the plate-shaped CoMn2O4 MD
for precise NP synthesis.[108] (Figure 14B(a,b), both CoMn2O4 PM and ST were fine particles
with average size ranging from 0.2 to 0.6 μm (Figure 14B(c,d)),
3.5. Solvothermal Method and CoMn2O4 also displayed a relatively rough surface
(Figure 14B(e,f )). HRTEM image of CoMn2O4 revealed crystal
With the exception of using organic solvents during the synthesis lattice fringes with calculated distance of 0.49 and 0.27 nm,
process rather than water, the solvothermal approach is compa- according to the (1 0 1) and (1 0 3) lattice planes. A SAED pattern
rable to the hydrothermal method. This synthetic technique has indicated a polycrystalline structure, with the (101) and (103) dif-
significance in producing nanocomposites with desired crystal- fuse diffraction matching the HRTEM images.[110,111] Table 6
line characteristics. By keeping the reaction mixture inside a summarizes the capacitive performance of several materials
sealed vessel (autoclave or bomb), the solvothermal approach using the solvothermal method. This method is a versatile tech-
allows the chemical reaction to proceed in a solvent at the nique for cobalt ferrite NPs that typically have sizes ranging from
temperature that is higher than its typical boiling point. 11 to 29 nm. Particle size control can be achieved by adjusting
These circumstances improve the solvents’ capacity to disperse parameters like reaction temperature, duration, precursor

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Figure 13. A) Schematic representation of the CFO–NPs preparation process. B) SEM image of CFO–NPs preparation process. a) Low resolution.
b) High resolution. e) TEM images of CFO–NPs at low resolution. d,e) HRTEM of CFO-NPs. f ) SAED designs. C) Represents a) the CFO–NPs electrode
CV profiles’ scan [email protected] mV s
1. b) Electrodes initial charging and discharging profiles. c) The electrode charging/discharging profiles at various cycle
counts. d) The electrodes performance at Id of 50 mA g
1 (Reproduced with permission.[104] Copyright 2018, Elsevier).

concentration, and solvent type. Higher temperatures and longer synthesized particles, their morphology, and elemental composi-
reaction times yield larger NPs, while lower temperatures and tion, as the key controlling parameters needed for optimizing
shorter reaction times yield lesser. Solvent choice influences ESDs. It should be specifically highlighted that the use of dopant
nucleation and growth kinetics, affecting final size. This method of different types considerably determines the ultimate conduc-
offers simplicity, high purity, and uniform particle size distribu- tivity and ECP of the material. In fact, the sol–gel method appears
tion. However, consistent results require specialized equipment as the most versatile and scalable synthesis route in producing
and precise control of reaction condition.[112] high-performance cobalt-based ferrite materials.
Overall, it can be concluded that selection of a synthesis
method to synthesize cobalt-based ferrites for ES purposes
depends on the application and device considerations should 4. Characterization Techniques for Cobalt Ferrites
be viewed from the specific requirement perspective. Analysis
Typically, a number of characteristics are by the selected synthe-
sis route, which are including but not limited to the particle size, High-precision instruments like TEM, SEM, XRD, AFM, Raman
particle size distribution, and specific capacitance, needed for spectroscopy, and FTIR are helpful in morphological studies,
optimal performance in ES applications.[113] Table 7 summarizes where XRD identifies the crystal structure, phase purity, and lat-
the main outcomes of the literature on synthesis of cobalt-based tice parameters, with use of CuKα radiation with wavelength of
ferrites applied in ES, where the sol–gel method appears as a λ = 1.5405 Å. SEM reveals surface morphology and particle size
highly effective route offering precise control over the size of distribution, showing uniformity with size ranging up to

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Table 5. The capacitive performance of several materials using the sol–gel combustion method.

Electrode Potential window Specific conductivity/current Cyclic performance References

density/rate capability
Co0.75Mg0.25Fe2O4 – 579.3 Fg
[email protected] Ag
1 96.49% after 1000 cycles [102]
Co0.8Sr0.2Fe2O4 – 637 Fg
1@5 Ag
1 85.5% after 1000 cycles [103]
CoMnFeO4 From
0.5 to 0.45 V 150 Fg
1@1 Ag
1 88% after 8000 cycles [322]
CFO-NPs From 0.001 to 3.00 V 1524 mAh g
1 Good reversibility after 50 cycles [104]
Hierarchical porous CoFe2O4 From 0 to 0.6 V 443.89 Fg
1@1 Ag
1 20.65% after 6000 cycles [105]
CoFe2O4 thin film From
1.2 to 0.5 V 396 Fg
1@2 mV cm
2 – [323]
CoFe2O4 – 79 Cg
1@1 Ag
1 98% after 1000 cycles [324]
Mn0.3Co0.2Zn0.25Fe2O4 From
0.1 to 0.3 V 281.04 Fg
1@10 mV cm
2 98% after 1000 cycles [325]
Co0.8Sr0.2Fe2O4 From 0 to 0.4 V (vs Ag/AgCl) 637 Fg
1@ 0.5 Ag
1 98.79% after 5000 cycles [326]
Co-IONPs From
0.2 to 0.5 V 214.1 Fg
[email protected] Ag
1 88.6% after 2000 cycles [327]
L-CoFe2O4 1.6 V 328 Fg
[email protected] Ag
1 80.8% after 1000 cycles [328]
Co3O4 -SG – 162 Fg
[email protected] Ag
1 85% after 5000 cycles [329]
Li2Co(WO4)2@Ag – 631 Cg
1@ 1 Ag
1 85.2% after 5000 cycles [330]
Co2.7Ag0.3O4 From 0 to 0.75 V (vs SCE) 648 Fg
[email protected] Ag
1 92.7% after 3000 cycles [331]
BaCoFe11O19/g-C3N4 – 314 Fg
[email protected] Ag
1 94.3% after 10 000 cycles [71]

nanometers, TEM provides insights into internal structure and information about the hydrodynamic diameter of scattering devi-
defects, and FTIR identifies chemical bonds and functional ces, the dimension of diffracting nanosized crystal, the solvation
groups. Electrochemical studies include electrochemical imped- sphere, and ultimately the amorphous surface layer information.
ance spectroscopy (EIS) which evaluates electrochemical behav- The histogram diameter for 110 particles from the statistical
ior, ion diffusion, and interface properties at electrode electrolyte analysis accurately matched with the mean diameter from
interphase; CV studies reveal the redox reaction occurrence, and Gaussian distribution around 5.2 nm.[115] A comparable size dis-
electrochemical cyclic stability is studied through galvanostatic tribution was reported in poly(ethylene glycol) for solid disper-
charging and discharging (GCD). Additionally, electrical studies sion. The view obtained at a reduced magnification reveals the
are carried out by IS and magnetic studies including vibrating high aggregates because dispersion stability and liquid-phase
sample magnetometry exploring magnetization and magnetic manipulation and control are easier than solid phase. This syn-
remanence. thesis approach might be easily scaled up. The quantitative
replacement of the ligand results in 33.8% uptake, according
4.1. X-Ray Diffraction Analysis to the thermal examination of dry coated particles. It is noted that
the solubility feature shifts from hydrophilic to hydrophobic
The XRD patterns revealed the spinal phase of cobalt ferrites. results. Both the adsorbed layer and the potential interpretations
The average dimension of the crystallite is determined using the of dipole magnetic coupling are confirmed by the hydrodynamic
Scherrer formula and XRD line broadening measurements. diameters drop of 13.4 nm.[116]
The mean diameter was determined to be 5.5 nm by the (3 1 1) Using an XRD, an investigation is carried out using CuKα
peak analysis. Based on inductively coupled plasma-atomic emis- radiation with a wavelength of λ = 1.5405 Å.[117] Generally,
sion spectroscopy measurements, the Fe/Co ratio was around Equation (2)–(5) are used to calculate crystallite size (D),
2.2, which is in proximity to the theoretical values of stoichiome- experimental density (Dexp), X-Ray density (Dxrd), and lattice
try of cobalt ferrite. High-temperature hydrolysis was a process in constant (a).
which one product was distilled to leave a stable inorganic com-
pound dispersion in a solvent. The final dispersion stability is 0.9λ
D¼ (2)
justified by its low ionic strength and low dielectric constant β cos θ
as reported. The homogeneous distribution of nanosized par-
ticles is revealed by dynamic light scattering (DLS) measure- mass
Dexp ¼ (3)
ments of the sample, which has an average diameter of volume
21.5 nm. The Derjaguin–Landau–Verwey–Overbeek hypothesis
predicts that the ultimate dispersion of low ionic strength and 8M
Dxrd ¼ (4)
low dielectric constant, resulting in thick double layers, enhances Na3
the force of repulsion between charged ions to avoid agglomera-
tion.[114] Using analytic methods, it is observed that there is a where N is Avogadro’s number and M: molecular mass for each
difference between the average diameter values that provide component.

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Figure 14. A) Schematic illustration of CoMn2O4 synthesis by (up) conventional solvothermal method, hierarchical microspheres precursor (middle),
and (below) using MOFs as precursor. B) SEM (a,c,e,g) and TEM (b,d,f,h) images of synthesized materials. a,b) CoMn2O4 MD. c,d) CoMn2O4 PM.
e,f ) CoMn2O4 ST. g) HRTEM image. h) Electron diffraction pattern of CoMnO4 MD (Reproduced with permission.[110] Copyright 2018, Elsevier).

a ¼ dhkl ðh2 þ k2 þ l2 Þ1=2 (5) between 550 and 600 cm
1, while the low-frequency band is
observed between 350 and 450 cm
1. If the functional groups
Here, λ = 1.5405 Å is the wavelength of X-rays, θ is Bragg’s are absent from the sample spectra, it ensures the annealing-
angle, β is full width at half maximum, h, k, and l are Miller indi- induced breakdown of organic compounds and the creation of
ces, and d is interplanar spacing. magnetically pure, spinal cobalt ferrite NPs.[119] Therefore, the
The XRD patterns explore the single-crystalline phase of cobalt presence of metal oxygen (M–O) bands; mounted samples is con-
ferrites throughout wide-ranging diffraction peaks. The cobalt firmed by FTIR spectroscopy. Nonetheless, the two frequency
ferrite standard value and the interplaner spacing and intensity bands correspond to phonon vibration starching in both tetrahe-
of all are detected in diffraction peak match precisely.[118] dral and octahedral sites.

4.2. FTIR Analysis 4.3. SEM and TEM Analyses

The FTIR spectra show a vibrational adsorption band because the Several methods, including TEM, SEM, and AFM are employed
oxygen ions among the cations vibrate in the octahedral and to examine the morphological structure of the ferrites. Cobalt fer-
tetrahedral locations. For the samples related to Fe ↔ O and rites shape appears to be spongy, and network structures are frag-
Co ↔ O with one another, the high-frequency band is detected ile as seen in SEM images; it is also found that cobalt ferrite NPs

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Table 6. The capacitive performance of several materials using solvothermal method.

Electrode Potential window SCs value Cyclic Stability References

1
1
Sandwich graphene films/Co3O4 0–0.5 (vs Ag/AgCl) 1266 Fg @1 Ag – [242]
mesoporous hollow spheres
Co–Ni(OH)2/carbon sphere 0–0.5 (vs Hg/HgO) 959.7 Fg
1@1 Ag
1 75% after 3000 cycles [332]
CoFe2O4-MNPs 0–0.4 V 429 Fg
[email protected] Ag
1 98.8% after 6000 cycles [333]
CoFe2O4 – 444.78 Fg
1@2 mV cm
2 90% after 1000 cycles [334]
CoFe2O4@CSs 0–0.5 V (vs Hg/HgO) 600 Fg
1@1 Ag
1 94.1% after 5000 cycles [335]
CFO 0–0.4 V 696 Fg
1@10 Ag
1 84.1% after 2000 cycles [243]

1
1
CoFe2O4/NF 0–0.45 V 192 Fg @1 Ag 90% after 3000 cycles [336]
CoFe2O4/GCN 0–0.45 V 524 Fg
1@2 mV cm
2 98% after 5000 cycles [337]
Ni(OH)2/Co(OH)2/ GO – 2050.6 Fg
1 @1 Ag
1 84% after 1000 cycles [338]
CFG 0.1 V (vs Ag/AgCl) 47.9 mA hg
[email protected] mV dec
1 90% after 1000 cycles [339]

1
1
CoF-NP – 594 Fg @1 Ag 98% after 5000 cycles [340]
Gycol-CoFe2O4
0.2 to 0.4 V 477 Fg
1@2 mVs
1 97% after 10 000 cycles [341]
Co9S8 – 502 Fg
1 @1 Ag
1 87% after 7000 cycles [342]
Co-Fe3O4NS@NG 1.6 V 775 Fg
1@1 Ag
1 97.1% after 10 000 cycles [343]
Ni–Co-S4 0–0.6 V 2215 Fg
[email protected] Ag
1 85.4% after 10 000 cycles [344]
Co3O4 0.1 V (vs Ag/AgCl) 718 Fg
[email protected] Ag
1 96% after 4000 cycles [345]
ZnO@Co3O4 – 4050.4 Fg
1@10 mV cm
2 90.6% after 1000 cycles [346]
FG–CoS 0.1 V (vs Ag/AgCl) 1072 Fg
1@1 mV cm
2 117% after 1000 cycles [347]

are in a cubic structure. TEM images revealed the cubic particles role in altering the dielectric constant. At higher temperature,
had several particles in a single line and very high agglomera- thermal agitation disrupts the alignment of magnetic domains,
tion.[115] An excellent correlation between the estimated value leading to variations in the dielectric constant. Within the cobalt
of 53.85 nm and the mean size of particle distribution was found ferrites, electrons hop between Fe2þ and Fe3þ, whereas holes
to be 52 nm. Heterogeneous character and nonuniform distribu- hop between Co2þ and Co3þ, contributing to polarization.[121]
tion of the particle size are also noted in the morphology. It was Cobalt ferrites exhibit stable dielectric behavior at low frequen-
noted[2] that the particle agglomeration was magnetic and exhib- cies but undergo dispersion and a decrease in dielectric constant
ited weak Van der Waals forces. For pure cobalt ferrites, the mea- at higher frequencies, while temperature fluctuations also influ-
sured particle size is around 30 nm. From the TEM micrographs, ence their dielectric properties.
it is observed that the samples are crystalline, and this crystalline
nature is due to the concentric ring among the spots above the
rings, which are due to electron diffraction patterns. Hence it can 4.4.2. AC Conductivity
be proven by the morphological study that TEM contributes to
the generating of core–shell structures and the cubic particles The AC conductivity of cobalt ferrites demonstrates frequency-
have a very high agglomeration rate, with several particles in a dependent behavior. At low frequencies, conductivity remains
single column. Hence morphology revealed the nonuniform dis- relatively constant or slightly increases due to electronic hopping
tribution of the particle size and inhomogeneous nature.[114] or tunneling processes between localized states. With increasing
frequency, conductivity rises, driven by enhanced polarization
4.4. Electrical Analysis effect facilitating charge carrier movement. However, at high fre-
quency, conductivity may plateau or decrease as material
4.4.1. Dielectric Constant response becomes constrained by factors like domain wall
motion or relaxation processes. Temperature variations also
As a function of frequency, the dielectric constant is plotted impact conductivity at higher temperature, increasing thermal
where cobalt ferrites possess intriguing dielectric properties. agitation, enhancing charge carrier mobility, and consequently
At low frequencies, their dielectric constant remains relatively conductivity.
stable, with minor fluctuations influenced by factors which At lower frequencies around 100 Hz, cobalt ferrites exhibit a
are the composition and processing methods. However, as decrease in dielectric constant ε and loss of tangent tanδ,
frequency increases, the dielectric constant experiences disper- attributed to Maxwell Wagner’s interfacial polarization. As the
sion, primarily due to domain wall motion and relaxation frequencies rises, dielectric constant and loss tangent stabilize
processes.[120] This dispersion causes a decrease in the dielectric at higher frequencies. Annealing cobalt ferrite NP at varied tem-
constant with rising frequency. Additionally, temperature plays a peratures affects their AC conductivity where polaron hopping is

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Table 7. Comparative literature outcomes among different synthesis methods, treatment temperature, the size, morphology, and ECP (in terms of SCs
value) of materials, including highlights and challenges.

Electrode Synthesis Temperature Size [nm] Morphology SCs value Highlights Challenges References
method [°C]
CoFe2O4 Hydrothermal 120–180 3.6–8.5 Spherical – Controlled particle High energy consumption, [86]
method agglomerated size, high purity long-time duration for
particles synthesis.
NixCo1
xFe2O4 Hydrothermal 200 10.91–16.76 Cubic/spherical 366-172 Fg
1 High purity, Limited control over crystal [348]
method shape versatility orientation, Environmental
concerns
CoxMn1
xFe2O4 Hydrothermal 180 16–25 Spherical- – Homogeneity, Limited reactant compatibility, [349]
method shaped NPs versatility Sensitive reaction parameters.
Gr/Co3O4 Coprecipitation 250 – Flaky-like 342.6 Fg
1 Rapid synthesis, Limited control over particle [314]
method surface compatibility with size and morphology,
doping. formation of
nonstoichiometric phases.
CoFe2O4 NRs Hydrothermal 400 0.2–200 NR structures 460.5 Fg
1 Temperature and Difficulty in product recovery, [294]
method pressure controlled, limited reactant compatibility
energy efficiency
CoFe2O4/GCN Solvothermal 200 18 Spherical in 524 Fg
1 Compatibility with Complex equipment [320]
composite method shape various solvents, requirements, limited
homogeneity scalability
CoFe2O4 nano Solvothermal 200 3.125 Spherical in 444.75 Fg
1 Compatibility with Long reaction rates, formation [334]
assemblies method shape precursor complexes, of byproducts.
versatility.
NCPC Electrochemical 80 – Distinctive 135 Fg
1 Precise control, Limited substrate [300]
deposition flower like uniform coating, high compatibility, electrolyte
purity. compatibility.
CuCo2O4 Sol–gel method 150-200 100 Hexagonal 81.72 Fg
1 Control over Limited scalability, Rick of [327]
shaped stoichiometry, nonstoichiometry.
homogeneous
mixing.
CoFe2O4-A Sol–gel method 125 12.38 Hierarchal 390.08 Fg
1 Tailored properties, Energy intensive, [350]
nanocomposites porous high purity, environmental concerns.
versatility.
CoFe2O4 nano Hydrothermal 180 24.3–25.9 Spherical- 244
273 Fg
1 Facial scale-up, Rapid Rick of corrosion, risk of [209]
particles method shaped NPs reaction rates corrosion.
CFO NPs Combustion 100 80 Spinal form – Ease of Greenhouse gas emission, [104]
synthesis implementation, health impacts
high energy density,
versatility.
CoZnFe2O4 NPs Coprecipitation 70–100 21 Spinal structure 218 Fg
1 Homogeneity, Slow reaction rate, difficulty in [191]
method Controlled controlling crystallinity.
stoichiometry
MnCoFe2O4 Coprecipitation 100 30–40 Spinal structure 675 Fg
1 Easily Scalability, low- Environmental impacts, [187]
method temperature sensitive to reaction
synthesis. parameters.
Ce0.5CoFe1.5O4 Hydrothermal 200 40–220 Spherical 937.50 Fg
1 Compatibility with Long synthesis times, limited [316]
method structure various precursors, precursor solubility
homogeneity
CoF–rGO Solvothermal 200 6.4–10 Spherical 511 Fg
1 Tuning of physical Limited compatibility with a [320]
method structure control, high reaction functional group, formation of
rates. nonstoichiometric phases.
CH-CoF Hydrothermal 180 12.06 Quasispherical 1120 Fg
1 Tuning surface Equipment complexity, [178]
method shape properties, Limited scalability
compatibility with
various precursors

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Table 7. Continued.

Electrode Synthesis Temperature Size [nm] Morphology SCs value Highlights Challenges References
method [°C]
CoFe2O4/HNTs Hydrothermal 180 200 HNTs 450 Controlled Formation of byproducts, [179]
method Crystallinity, limited scalability
uniformity in
composition
C/Co3O4 Hydrothermal 180 200–250 Hollow and 103.8 Fg
1 Facilitates Limited control over crystal [242]
method broken sphere multicomponent orientation, it required
structure reactions, facile maintenance
Scale up
CFO-Pd Coprecipitation – 5.1 Inverse spinal – Compatibility with Difficulty in washing and [351]
method structure doping, formation of purification, sensitive to
complex structures. reaction parameters.
CoNi-LDH Solvothermal 120 – 3D nanopetal 1322 Fg
1 Versatility, tailored Complex reaction kinetics, [352]
method structure morphologies. limited compatibility with
reactive species.
CoFe0-5 Coprecipitation 100 10.2 and 44 Quasispherical 77.8 Fg
1 Narrow particle size Formation of [353]
method and needle-like distribution, nonstoichiometric phases
structure controlled
stoichiometry.
Co2.16Mn0.84(PO4)2 Hydrothermal 120 19–22 Nanoflakes 571 Fg
1 Controlled Equipment complexity, [186]
method structure crystallinity, Energy precursor solubility.
efficiency
CoFe2O4–carbon Coprecipitation 100 209 Microspheres 106.5 Fg
1 High yield, versatility Complex reaction kinetics, [82]
mesosphere method limited temperature range.
Co3O4 Electrochemical – 30 Film peeled – Selective deposition, Risk of nonuniform [288]
deposition form like flakes Cost-effectiveness deposition, limited thickness
range.

the primary mechanism. Higher annealing temperatures NPs. Despite a decrease in charge transfer resistance ≈27 Ohms,
increase crystallite size, reducing surface area and defect density the nanocomposite exhibits higher corrosion current density of
and resulting in decreased in AC conductivity.[94] The conductiv- 0.387 and corrosion rates of 0.00446.[121] Section 6 includes
ity spectra are derived from Jonscher’s power law as represented detailed discussion with respect to electrochemical studies spe-
in Equation (6). cifically including CV, GCD, cyclic stability, current density, and
energy density of cobalt nanocomposites.
σðωÞ ¼ σ dc þ Aω5 (6)

where σðωÞ is AC conductivity, σ dc is DC limits of AC conduc- 5. Electrochemical Characterizations

tivity, A is variable that changes with temperature, and ω is fre-
quency. The nonlinear fitting curve is derived using Jonscher’s 5.1. Performance of Energy Saving Systems
power law for conductivity curves. Cobalt frequency exponent is
reported in the range of 0.54 and 0.93.[122] The key components of supercapacitors are an electrolyte solu-
tion, an ion-permeable separator, two parallel plate electrodes,
and electrode materials, as shown in Figure 15a. Effectively
4.5. Electrochemical Studies separating the two electrodes can stop mutual contact and avoid
short circuits.[123] Two reversible processes store energy in solid-
The studies on cobalt ferrite nanocomposites underscore their state ESDs; first one is reversible ion adsorption and desorption
potential across diverse applications. CV studies measure the through electrolytes and active materials, and second one is
SCs ranging from 100 to 500 Fg
1 where the morphology and reversible Faradaic redox reaction that occurs throughout charg-
synthesis method significantly shape these values. GCD meas- ing and discharging. Additionally, supercapacitors may be
ures affirm SCs of 50–300 Fg
1 along with exceptional cycling divided into three classes according to ES mechanism including
stability. EIS measures efficient electron transfer, with charge BT-type capacitors, electric double-layer capacitors (EDLCs), and
transfer resistance Rct ranging from 10 to 100 ohms followed PCs.[124] In reversible ion adsorption/deposition at the electrode/
by a detailed discussion of the mechanism in Section 5. electrolyte interface, ions are adsorbed physically without any
A graphene-based cobalt ferrite NPs is synthesized via a hydro- chemical reaction.[125] Charging restricts the capacitance, display-
thermal process, incorporating graphene oxide with cobalt ferrite ing a greater Pd but a reduced energy density in addition to

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Figure 15. a) Diagrammatic portrayal of the structure of supercapacitors and batteries, EDLC, surface redox capacitor, and BT-type capacitor
(Reproduced with permission.[132] as an open access source). b) Charge storage mechanism of EDLC. c) Batteries, d) PC, and e) hybrid storages
(Reproduced with permission.[139a,b] Copyright 2021, Elsevier).

capacitance since Faraday redox processes are absent for the ES phase fluctuations.[127] There are two categories of PCs, those
process. The PC provides the SCs with a greater capacity for regulated by interfering layers and those regulated by surface
charge storage depending upon the Faraday redox reaction.[126] redox process. While ions in an electrolyte solution are drawn
Accelerated reversed Faraday response that occurs close to the to or close to the surface in the case of PCs, electron transfer
surface of the material is used to drive storing of the energy takes place via the redox pseudocapacitance process. A layered
process in supercapacitors. It resembles the mechanism of electrode in order exposes a greater surface in an electrolyte
charging/discharging that occurs in batteries, without creating solution, and later PCs, electron transfer proceeds, and ions

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are moved through the separation or interface of the electrode. In general, a material can store electric charge either in its
Inadequate cycling performance is caused by electrode materials bulk (via Faradaic process) or on its surface (by double-layer
propensity to shrink and expand while charging and discharging charging).[137] Consequently, an extremely accessible effective
because of the redox process at the electrode.[128] When com- surface dimension is essential for the perfect EDLC material.
pared to EDLCs, PCs have significantly higher capacitance For instance, electrical charge at the interface of both electrolyte
and energy density instead of completely reversible physical and electrode active material results in an EDLC, as shown in
charge/discharge processes. This is mainly attributed to the dis- Figure 15b. Neither electrochemical nor Faradic reactions occur
tinct stored charge mechanism of the Faraday redox reaction.[129] inside most of the electrode active material throughout this
The process by which BT materials store charge includes reacting phase, nor do any occur across the electrode/electrolyte contact.
with OH
in an alkaline medium, and the reaction is regulated Reversible Faradic reaction occurs throughout most electrode
by the mobility of ions from the electrolyte. Materials that resem- materials in conjunction with the electrolyte in rechargeable bat-
ble batteries often have a large capacity for charge storage. teries to store charge, as shown in Figure 15c. It is necessary to
However, the materials with delayed phase shift lower their design the material so that the reactive species may be easily
kinetic functionality during charging/discharging, which results inserted and removed with no ion diffusion occurring within
in a low multiplicative performance.[130] As opposed to this, the bulk of the electrode active substance, the base for charge
BT-type materials with distinctive nanostructures have a large storage in PCs in Faradic redox response occurs on or close
surface area, which makes them excellent redox active site to the surface of materials, as shown Figure 15d. Here, the dif-
fusion length (l), the diffusion coefficient (D), and period (t) are
responses and reduces the distance over which electrolyte ions p
must diffuse. Furthermore, by constructing their nanostruc- all l ≪ 2 Dt substantially less than the diffusion layer (Ip). With
tures, materials that resemble batteries can slow down the quick a behavior halfway between EDLC and Faradic process as the two
phase shift that occurs during storage. extremes, hybrid ESDs, as they are between the supercapacitors
The electrochemical process comprises the Faraday electroly- and batteries, are termed as hybrid ESDs, as shown in
sis reaction. TMOs have a higher coefficient of energy than car- Figure 15e.[138,139b]
bon materials, leading to exactly why they have been extensively
researched as supercapacitor electrode materials. Nevertheless, 5.2. Evaluation of Energy Saving Systems
designing superstructure carbonaceous materials in supercapa-
citors would also compensate for the inadequate coefficient of 5.2.1. Cyclic Voltammetry
energy, depending on the purpose, which could be custom-
The CV is the most accepted methodology to examine the ther-
built structures or target-oriented structures with tailored
modynamic impact and transfer of electron kinetics at interphase
functionalities.[131] Among the numerous transition metal-based
involving the electrolyte and active compound in supercapacitors.
supercapacitors, cobalt nanomaterials are the most conventional
The approach is vital for accurately describing the reactions car-
material. In recent decades, there has been significant amount of
ried out on the surfaces of the active material. A specific operat-
published research on supercapacitor electrode materials, such
ing potential range is evaluated and the applied potential is
as Co3O4, Co(OH)2, MnCo2O4, NiCo2O4, ZnCo2O4, and its
scanned at different and distinct rates. The current response
derivatives.[132]
at the cathodic and anodic sweeps determines the ECP of the
The working principle of batteries revolved around the move-
electrode. As mentioned below, the SCs of a half cell, C (Fg
1),
ment of electrons and ions through a chemical reaction between
can be computed in the CV profiles using Equation (7).
anode and cathode. During discharge, the anode undergoes oxi-
R
dation, releasing electrons into the external circuit, which flow to I dE
the cathode. Concurrently, ions travel through the electrolyte C¼ D (7)
νΔE
from the anode to the cathode, completing the internal circuit
and allowing the chemical reactions.[133] In rechargeable batter- where, I D is the normalized specific current (Ag
1), ΔE is oper-
ies, this process is reversible. Applying an external electric energy ating potential (V ), and ν is the scan rate (mV s
1).[140] The sub-
source forces electrons to move from the cathode back to the sequent formula can be used to calculate the specific energy (ES)
anode, reversing the chemical reactions and restoring the and corresponding specific power (PS) of a full symmetric cell
BT to its original state. This seamless transfer of energy is what using the C obtained from Equation (8) and (9).
powers device efficiently and effectively.[116,134] For instance, dur-
1 1000  C  ΔEV 2 C  ΔE 2
ing the Liþ deinteraction process in standard LiCoO2 graphite E s ¼ CðΔVÞ2 ¼ ¼ (8)
2 2  4  3600 28.8
LIBs lithium-ion batteries, Liþ is removed from the crystalline
structure that comprises the LiCoO2 cathode to generate 3600  E S 3.6  E s
Ps ¼ ¼ (9)
CoO2.[135] The charge process is reversed by its discharge of 1000  Δt Δt
the dispersion of the cation inside the crystalline structure, in
which subsequently engaged phase transformation and alloying For asymmetric cell the equation is as follows.
processes govern the entire Faradaic process. The primary 1 1000  C  ΔE 2 C  ΔE 2
sources of capacitance are surface Faradic redox processes E s ¼ CðΔEÞ2 ¼ ¼ (10)
2 2  3600 7.2
(pseudocapacitive behavior and electrochemical adsorption and
desorption of cations and anions at the interphase of the elec- where the cell’s equivalent SCs is C, the discharge period (s) is
trode and electrolyte).[136] denoted by t, and E denotes the working potential V.

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An ideal rectangular shape in Figure 16a that indicates no sweep rate, that is, I αv (current and sweep rate), whereas peak
chemical reaction ensures a specific reversible capacitive prop- currents in diffusion-controlled processes (I = 12 v) are propor-
erty of optimal EDLC materials. The reversible oxidation and tionate to the square root of the sweep rate, as per the power
reduction peaks in the pseudocapacitive material suggest a law. 2) The peak current ratio must be 100%. 3) The oxidation
Faradaic redox mechanism. Figure 16b represents the CV curves and reduction peaks should have a small potential difference
that encapsulate the BT ES dynamics succinctly. Originating (primarily less than 59 mV n
1, here n is the number of
from the bottom left, it portrays the discharge starting with electrons). 4) The predicated peak position is unaffected by
low voltage. As the charge phase commences, an ascending line the sweep/scan rate.
signifies voltage rise, culminating in a peak denoting full charge. The properties and performance of batteries vary by
Under constant voltage conditions, a flat line at the peak exem- sweeping the potential of a working electrode cyclically while
plifies controlled voltage charging. The subsequent discharging measuring the resulting current. This process helps understand
unfolds with a descending line, illustrating energy utilization. the electrochemical reactions at electrode surface, analyzing
The descent slope characterizes the discharge rate. The mini- redox behavior, reaction kinetics, and charge storage capacity.
mum voltage at the bottom right designates full discharge, By examining current potential curves, researchers can identify
emphasizing the critical need to avoid voltage beyond this thresh- oxidation and reduction peaks, assess reaction kinetics through
old to prevent damage. Reversible electrochemical processes can peak shape and position, and determine total charge storage by
be inferred to have the following properties. 1) Peak currents in integrating the area under the curve. Additionally, CV can evalu-
mass transport processes or EDLCs are proportionate to the ate electrolyte stability by observing the potential window within

Figure 16. a,b) CV of supercapacitor and BT (a and b). c,d) GCD curves of supercapacitor and BT (c and d). e) Typical Nyquist plot for EDLC, PC, BT
along with equivalent circuit diagram (Reproduced with permission.[149a,b] Copyright 2018, Elsevier). f ) LSV plot for supercapacitor (Reproduced with
permission.[144] as an open access source).

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which the electrolyte remains stable and ion diffusion coefficient sodium-ion batteries is evaluated, enabling the development of
is calculated using the Randles–Sevcik equation.[140,141] Finally, high-performance cathode and anode. In supercapacitors, the
CV is a potent tool for analyzing ES systems, including batteries, capacitance and ES mechanism of EDLCs and PCs are analyzed,
supercapacitors, and fuel cells. By sweeping the potential of an improving their design and efficiency. In fuel cells, the charge
electrode and measuring the resulting current, CV offers valu- and discharge behavior of proton exchange membranes, solid
able insights into electrochemical behavior, reaction kinetics oxide fuel cells, and alkaline fuel cells are investigated, enhancing
and performance metrics, electrolytes, and overall design. For their efficiency, power output, and durability. GCD supports the
supercapacitors, charge storage efficiency, power density, and development of advanced ES solutions for electric vehicles,
rate capability are evaluated. In fuel cell studies, electrochemical renewable energy system, and portable electronics.[145]
reactions, catalyst stability, and overall efficiency are investigated.
By providing a comprehensive understanding of ES system, the 5.2.3. Electrochemical Impedance Spectroscopy
development of more efficient, reliable, and sustainable solutions
is supported.[142,143] EIS stands as a pivotal frequency approach for elucidating intri-
cate characteristics of batteries and ECs. Typically, low-amplitude
5.2.2. Galvanostatic Charge–Discharge substitute voltage, around 5 mV, is adeptly superimposed on a
DC potential during measurements. The resultant impedance
GCD is a dominant and fundamental technique for researching value is artfully translated into a Nyquist plot, delineated by three
the electrochemical properties of SCs: Cs, Sp, SE, power and distinctive regions: an intercept at the real axis, a semicircle in
energy densities, specific current, current densities, efficiency, the elevated frequency domain, and a linear segment in the low-
and rate capability. A steady current is applied to the electrode frequency spectrum as shown in Figure 16e, leveraging the
substance in the GCD method, and voltage fluctuations are mea- assumption that EC behavior can be encapsulated by a simplified
sured within a predetermined potential range (V1–V2 for positive RC equivalent circuit asymmetric EC. This impedance data is not
current and vice versa for negative current). This procedure is merely empirical but amenable to stimulation and numerical
known as “current reversal chronopotentiometry.” Potential analysis. The circuit parameters, including capacitance
increase is evaluated against time (t, s) from the beginning volt- (C1 and C2), Faradic resistance (R1 and R2) governing redox reac-
age V1 to the final value V2 during positive current application to tions, Warburg resistance (Rw) representing diffusion processes,
the working electrode. A negative current of the same size is then and equivalent series resistance (ESR) denoted by Rs facilitate a
used to assist with possible step-down. As with cyclic voltammo- comprehensive understanding.[146] It is paramount to acknowl-
grams, the charge storage mechanism and kinetics determine edge the adaptability of the equivalent circuit model to diverse
how GCD profiles are configured. For the duration of a whole scenarios, such as measurements conducted in both half-cell
charge–discharge cycle, the galvanostatic charging profile of and full-cell configurations.
an ideal capacitor takes on a linear shape like a triangle pattern The Nyquist plots depicted prove to be a discriminating tool,
in Figure 16c. The most reliable method, for calculating SCs (Q), unraveling distinction among EDLC, PSC), and batteries.
or the amount of charge stored per unit mass (g) of substance in Notably, EDLC manifests a characterstic-90° straight line due
each potential window (V ), is described by Equation (11)–(13), to its non-Faradic nature, through exceptions arise with conven-
where Csp is SCs, E is energy, and P is specific power. In addi- tional EDLC materials exhibiting a semicircle due to a redox
tion, GCD plays a crucial role in evaluating other important elec- semicircle succeeded by a 90° straight line. In stark contrast, a
trochemical behaviors like Columbic efficiency, cyclic stability, typical BT showcases a larger semicircle followed by a 45°
and rate capability.[144] straight line, indicative of a more sluggish diffusion process.[147]
The pivotal parameter, the peak frequency of the semicircle ( fm),
it
Csp ¼ (11) unveils critical information-relaxation time for batteries or
m  ΔV 1
charge transfer time for PCs ( 2πfm ), for accurate determination
1 of ESR. EIS measurements in a two-electrode cell or a packaged
E ¼ Csp V 2 (12)
2 device are recommended, diverging from the misjudged
E practice notes that ESR values obtained from EIS are typically
P¼ (13) smaller than those from GCD testing.[148] Furthermore, debunk-
t
ing the misconception of zero ESR in a three-electrode cell,
In Figure 16d the GCD curve provides a concise depiction of the text underscores the ESRs’ dependency on the distance
batteries energy dynamics. Originating from the bottom left, it working and RE. Despite the potency of the Nyquist plot in
indicates low voltage during discharge. The ascending line dur- dissecting electrode kinetics, it is prudent to recognize its
ing the charge phase peaks symbolizes full charge. A flat line at exceptions. Instances like SnO2 NPs and multilayer graphene/
the peak signifies controlled charging under constant current. Fe3O4 composite-based lithium-ion batteries deviate, exhibiting
Subsequent discharge is shown by a descending line, portraying a near-90 °C straight line in low-frequency value, challenging
the energy utilization rate. The bottom right denotes the full dis- conventional categorization.[149a,b]
charge states, emphasizing the importance of avoiding voltage EIS studies in LIBs provide deep insights into various accepts
exceeding this threshold to prevent damage. GCD is tool for opti- of their performance and degradation. By analyzing the imped-
mizing ES performance in various devices. In batteries, the ance spectra, the kinetics of electrochemical reactions at the
charge and discharge behavior of lithium ion, lead acid, and anode and cathode, specifically by determining the charge

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transfer resistance (Rct), indicate the efficiency of the electrode conversion reaction, Li-conversion event leads to a partially
materials and rate of electrochemical reactions. Lower Rct value collapsed framework structure in conversion-type Co-based
suggests better electrode performance and faster reaction kinet- MOFs. Through aligning reactions, these mechanisms store Li
ics, while change in Rct over time indicates the electrode material further or transform redox-active Co2þ to Co metal NPs at
degradation. EIS also sheds light on the electrolyte and ion trans- zero state.[153] Furthermore, the mechanism of reversible
port properties by measuring the electrolyte resistance, reflecting lithiation and delithiation is associated with reversible structural
how easily lithium ions move through the electrolyte. The tech- modification and interpenetrating tunnels for Liþ transport, with
nique measures double-layer capacitance (Cdl) at the electrode– around 32 mol lithium being used by a single mol active CoCOP.
electrolyte interface, with higher Cdl values indicating a larger Another extremely active B-MOF lithium storage system is
effective surface area for electrochemical reactions, beneficial also connected to the conversion reaction. Wang et al. synthe-
for BT performance.[150] EIS is a versatile technique that diver- sized the Co-Ni-BTC1 MOF (BTC1-1,3,5-benzenetricar boxylic
sifies the studies, in batteries, and helps to optimize electrode acid).[154] Ex situ X-ray absorption spectroscopy (XPS) shows that
performance, electrolyte efficiency, and overall BT life by analyz- Ni2þ did not take part in Liþ storage behavior of Ni-BTC1 MOF,
ing impedance spectra. Similar to SCs, the evaluated capacitance, it could convert both oxidized and reduction states in Co-doped
ESR, and frequency response reflect the efficiency of ES and Ni-BTC1 MOF, depending on the electrochemical behaviors of
rapid charge discharge cycles. Additionally, in fuel cells to ana- Ni components, and can be efficiently activated by the
lyze electrochemical kinetics, catalyst performance, and overall addition of Co. Furthermore, lithium-storing active sites of
efficiency, aiming in the development of more efficient and dura- Co–Ni–BTC1 MOF at the time of charging and discharging
ble fuel cell technologies.[151] operations, to shed light on more such examples of Co-BDC
MOF,[155] u-CoTDA,[156] and CO-LCP (Co(tfbdc)(4,40-
5.2.4. Linear Sweep Voltammetry bpy)(H2O)2)[157] can be explained by a mechanism analogous
to these for ES.
The electrochemically stable potential window of the electrode An insertion-type reaction is yet another sort of Li storage tech-
and electrolyte compound is the principal application of the lin- nique in Co-MOF materials, which is desirable to accommodate
ear sweep voltammetry (LSV) technology. The applied potential is reversible multielectron reactions because of electroactive func-
shown against the current response in the LSV technique, where tional groups at ligand moieties, such as nitrogen atom-based
the potential increases linearly at a steady scan rate. Two inde- groups (pyridine, amine group, imidazole, etc.) and oxygen
pendent measurements, a forward scan (zero-positive potential atom-based groups (COO–CO–). This corresponds to the reality
zone) and a reverse scan (zero-negative potential region), are that organic linkers offer abundant sites for Li-ion insertion and
used to measure the current response. A typical LSV can be split extraction, through aromatic rings with delocalized p electron
into two zones, as shown in Figure 16f, where the current clouds. As a result, reversible Liþ ion storage can happen in a
response at higher/lower potential values follows a growth/dip synergistic way at both each aromatic C6 rings and electroactive
and a plateau, respectively. A double-layer development, that functional groups. To achieve high theoretical specific capacity
is, proportionate to both the potential scan rate and the charging and exceptional cyclability, accordingly metal ions tend to
storage capacity, is indicated by the plateau of a specific potential decrease to low oxidation state to maintain the charge throughout
range. Irreversible Faradaic processes, such as electrolyte break- electrode. Organic ligands with conjugated carboxylic groups
down, are indicated by the abrupt rise or fall of current respon- exhibit strong p–p interaction and mild withdrawing electron
siveness at a higher/lower potential region. The voltage window effect in the aromatic rings. These interactions are coordinated
range where the electrolyte can function without experiencing with metal ions to produce constant insertion MOFs. In contrast
significant degradation is likewise displayed by the potential pla- to the deconstructed frameworks and MOF compositions result-
teau above.[144] For instance, LSV investigates the electrochemi- ing from the conversion process, the insertion-type MOF struc-
cal behavior of LIBs by applying a linear voltage sweep to the ture is maintained for Liþ storage, ensuring strong cyclic stability
working electrode and measuring the resulting current. LSV over continued cycle experiments. The charge storing strategy of
reveals key insights into electrode reactions and stability. The a seashell-type S–Co–MOF(Co2(OH)2BDC has been disclosed by
current voltage curves obtained will identify oxidation and reduc- Hu’s research group.[158]
tion peaks, shedding light on the reaction mechanism and kinet- The unique hierarchical geometry of S–Co MOF provides
ics at the electrode interface. Furthermore, LSV enables the many hollows for quick ion transfer and electrolyte storage.
detection of changes in electrode materials and electrolytes over When employed as a LIB anode, Co2(OH)2BCD exhibits undis-
time, highlighting issue such as degradation or instability. In bat- puted cyclic stability at 1 Ag
1 for up to 1000 cycles. The organic
teries, LSVs provide an insight to electrode material behavior, moiety dominated Liþ intercalation/deintercalation at the car-
identify redox reactions, reaction mechanism, and evaluate elec- boxyl group on the C6 rings of organic ligands, which is carried
trode performance and stability. In case of SCs, LSV determines out by the corresponding Liþ storage mechanism. This phenom-
capacitance, rate capability, and material performance. In fuel enon together with a deformed CoO6 octahedral in the absence of
cell studies, reaction kinetics, catalyst performance, and overall a conversion reaction is analyzed via high-resolution solid-state
efficiency are investigated. LSV studies enhance the advanced ES NMR and soft Co L2,3-edge and 0 K edge sXAS. Since redox
and conversion systems.[152] action ligands and variable valence metal ions are available, S–Co
Redox-based Li-ion storage is carried forwarded in either of the MOF when utilized as the anode in LIBs exhibits improved Liþ
form’s conversion reaction and insertion reaction. Through the storage behavior.[159]

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5.3. Capacitive Charge Principle reaction mostly controls the capacitive properties. The presence
of two distinct cations that are in the bimetallic CoFe2O4 and its
5.3.1. Electronic Double-layer Capacitors Principle distinct nanosheet structure is responsible for the increased elec-
trochemical characteristics of CoFe2O4 nanosheets, such as
The electrostatic accumulation of ions from the electrode exte- supercapacitors and batteries and conductivity.[171] The redox
rior, in the absence of diffusion confinement, is the framework pairings Co(III)/Co(II), Co(IV)/Co(III), and Fe(VI)/Fe(III) w
for EDLCs, popularly referred to as physical capacitors.[160] ere mostly attributed to the redox response of CoFe2O4, and
Porous carbon has been a popular choice for the electrode Equation (14)–(16) were presented as the ES mechanism of
substance of EDLCs with excellent Pd and remarkable cyclic CoFe2O4.[172]
stability.[161] Moreover, MOF families have enormous surface
areas, exceptional porosities, and well-defined pores as a novel CoFe2 O4 þ H2 O þ OH
↔ 2FeOOH þ CoOOH þ e
(14)
class of hollow substance.[162] Recently, pristine MOFs micro-
pores and mesopores have been used to generate electrical CoOOH þ OH
↔ CoO2 ↔ CoO2 þ H2 O þ e
(15)
energy in the inner surface, which results in a significant capaci- FeOOH þ H2 O ↔ FeðOH3 Þ ↔ ðFeO4 Þ
þ 3e
(16)
2
tance. With the use of PANI and known as PANI-ZIF-67-CC,
Wang et al. effectively constructed Co-MOF nanocrystals and
carbon cloth, and this blended electrode produced extremely high
EDLCs obtained from the interior surface area of MOFs.[163] 5.4. Choice of Electrochemically Efficient Materials

In both supercapacitors and batteries, one first needs to specify

5.3.2. Pseudocapacitive Principle
performance characteristic or index, in view of materials besides
manufacturing and practical considerations. For instance,
According to Gogotsi et al., the standard pseudocapacitive charge
mutual contact between two electrodes avoiding short circuits
is not constrained by cation diffusion within the crystalline struc-
provides support for greater capacity for charge storage in super-
ture of the active substance and instead involves redox reaction
capacitors, while the reaction in batteries can be regulated by the
when ions are adsorbed electrochemically from the surface or
mobility of ions from the electrolytes. Materials chosen for bat-
near the surface of the electrode-active substance. This process
is like Faradic charge transfer in general but emerges teries should provide support for quick phase shift needed for
capacitive.[164] Interestingly, PCs have been explored for ESDs long-term storage. A prominent material should store electric
in various TMO and sulfides such as MnO and rGO,[165] charge in its bulk (via Faradaic process) rather than temporarily
CoS,[166] V2O5,[167] etc. This is significantly greater capacitance on its surface (by double-layer charging). Nevertheless, an accel-
from EDLCs in carbon substances. Open crystal frameworks erated reversed Faraday response occurring in the vicinity of the
and active metal centers of MOFs may provide significant pseu- surface of chosen material plays the role of driving force to pro-
docapacitance. A hierarchical microflower-like cobalt-based MOF long the storing of energy in supercapacitors, which resembles
is utilized as an anode in LiBs. The outcome of its ECP indicated charging/discharging mechanisms based on which Batteries
that the surface capacitive-controlled behavior offers outstanding function without creating phase fluctuations. A candidate mate-
rate capacity, which is attributed to the structural hierarchy of rial is expected to enjoy an optimized electrochemical storage
H–Co–MOF. This is supported by the kinetic study reaction efficiency. There are also additional considerations, which are
and the quantitative capacity contribution.[168] mainly seen in the way ESDs work. In this regard, evaluation
of such a performance demands understanding of characteriza-
tion techniques satisfying a careful monitoring, for example, CV,
5.3.3. Intercalation Pseudocapacitor Principle GCD, EIS, and LSV. Moreover, one needs to make sure that
capacitive charge principles are well known in order to select
An innovative method of storing charge is intercalation pseudo- the most reliable electrochemically efficient materials.
capacitance which operates when cations, such as Liþ, Naþ, Hþ,
or Kþ, reversibly intercalated or deintercalated from the layered
host materials layers’ or tunnels.[130] A Faradic charge transfer
but no phase transition is present in intercalation pseudocapaci- 6. Cobalt-Based Composites as Energy Storage
tance, and the mechanism is not kinetically restricted by cations Systems
dispersion within the electrode active materials’ crystal
lattice.[139] Although it combines BT-type energy and capacitor- The cobalt-based ferrites studies have been driven by their
like rate characteristics, this phenomenon is important for the unique and versatile properties, making them valuable across
design of a single EES device. Several inorganic transition metal numerous technological applications. Cobalt ferrites exhibit high
complexes have emerged in recent years such as TiO2[169] and theoretical energy densities, making them ideal for batteries and
T-NB2O5,[170] which allow for elevated cation intercalation inside supercapacitors. These materials offer excellent cycling stability,
a huge electrode to provide a high PC character. ensuring long-term performance with minimal degradation over
Using a three-electrode step-up, CV and GCD measurements many charge–discharge cycles. Enhanced electrical conductivity,
may be used to assess the electrochemical properties of the resulting from the combination of cobalt and ferrites, facilitates
CoFe2O4 electrode. Two prominent redox peaks were found in faster charge and discharge rates, crucial for efficient ES. A few
the CV curves during the ECP test, indicating that the Faradic synergistic effects that enhance the ECP are discussed below.

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6.1. Cobalt and Carbon Nanotube Co3O4@Co/N–CNT. They were subsequently pyrolyzed in a reg-
ulated nitrogen atmosphere to produce a core–shell system of
The design and preparation of a Co9S8@carbon nanotube (CNT)- Co3O4@Co/N–CNTs. Figure 17B(a–g) represents device initial
carbon nanofiber (CNF) hybrid structure was performed success- and later deposition on the current collector, the aqueous asym-
fully. It seems easily possible to distinguish CNFs and CNTs, metric supercapacitor devices (ASC), a schematic representation
where the solid linear structures are CNFs while hallow tubular of the devices, enhancement of the device potential window, a CV
constructs contain cobalt sulfide nanowires. A Co9S8@CNT– plot at scan rate of 5–100 mV s
1 of the device, a GCD curve of
CNF has a Cs of 1656 Fg
1 at 1 Ag
1, and it has excellent the device at Id of 20–40 mA cm
2, and EIS studies of the device
electrochemical cycle stability (92.6% up to 10 000 cycles) where with an inset displaying comparison with cycle numbers 1500
semirectangular CV curves suggest that charge transfer occurs and 1000. Several compositions of Co3O4@Co/N-CNTs core–
at the interfacing of the electrodes and electrolytes. The shell structures were synthesized using ex situ techniques utiliz-
Co9S8@CNT–CNF demonstrated remarkable reversible oxida- ing Ag NPs and rGO, correspondingly revealing the excellent
tion reduction, indicating typical pseudocapacitive properties. Cs = 3393.8 Fg
1 at 5 mV s
1, among several other composites
The GCD plots of Co9S8@CNT–CNF at various Id are displayed investigated in 6 M aqueous electrolyte KOH with exceptional
by the Co9S8@CNT-CNF capacitance at various current densi- electrochemical stability with energy density of 74.1 Wh kg
1,
ties. The Co9S8@CNT–CNF composite exhibited remarkable power density of 443.7 W kg
1, Coulombic efficiency of
ECP and suggested that it has a lot of promise for use in high 101.3%, and CV curves at scan rate of 100 mVs
1, as shown
power and ESDs.[173] Square-facet nanobars of Co-MOF are in Figure 17C(a–h).[174] In 2023, Alfryan et al. used a coprecipi-
initially produced using a solvothermal process at a regulated tation method to synthesize nickel and cobalt-doped zinc ferrite.
pH of the precursor solution. Figure 17A(a–c) represents The nanocomposites, which consist of nickel and cobalt-doped
the steps implicated in the synthesis of Co-BTC, including the zinc ferrite combined with CNTs, were synthesized by the ultra-
preparation of square-facet Co-BTC and the creation of sonication process, where SEM images depicted the spinal form

Figure 17. A) A representation of steps engaged in the synthesis of Co–BTC, including the preparation of square-facet Co–BTC, and the creation of
Co3O4@Co/N–CNT. B) a) The device initial and later deposition on the current collector. b) The aqueous ASC. c) Schematic representation of the devices.
d) Enhancement of device potential window. e) CV plots@scan rate of 5–100 mV s
1 of device. f ) A GCD curve of a device at Id of 20–40 mA cm
2.
g) EIS studies of the device with an inset displaying comparison with the cycle number 1500 and 1000 of 1000 continuous CV cycles. C) Three electrodes
are used to do electrochemical analysis. a) CNC CV curves@scan rate of 5–100 mV s
1. b) CNC AgrGO CV profiles@scan rate of 5–100 mV s
1. c) The Id
of 20–40 mA cm
2. d) GCD profiles of CNC. e) GCD curves of CNC AgrGO. f ) Ragone curves of Co–BTC, CNC, and CNCAgrGO. h) EIS study of CNC and
CNCAgrGO with insets portraying a comparable circuit (Reproduced with permission.[174] Copyright 2023, American Chemical Society).

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of the NPs because CNT NPs have effective surface contact, and property and outstanding capacitance behavior. Figure 18d–f dis-
the durability of the resulting NPs is enhanced. To test the plays the CVs of CoFe2O4, reduced graphene oxide, and PANI in
effectiveness of the photocatalyst, methyl violet was subjected 1 M KOH at 1 mV s
1 where two redox peaks in the CoFe2O4
to photodegradation under solar light radiation. The photocata- show the materials pseudocapacitance characteristics and excel-
lytic studies reported exceptional specific area and effective lent capacitive performance of the ternary CGP0.345 nanocompo-
electron conductivity which make the composition better for het- sites displaying the maximum current density among all the
erogeneous catalysis.[175] The synergistic combination of cobalt electrodes. The Cs of the ternary CGP0.345 nanocomposites is
and CNTs ensures uniform dispersion of cobalt NPs on the sur- 1133.3 Fg
1 at a scan rate of 1 mV s
1 as shown in Figure 18g.
face, enhancing overall ECP and preventing agglomeration. The average particle sizes of CoFe2O4 in the binary CG0.070,
Cobalt combined with CNTs provides an exceptionally high sur- CG0.236, and CG0.345 hybrids are 11.7, 7.8, and 6.2 nm,
face area due to their cylindrical nanostructure, enabling more respectively.[176] The synthesis of material is done by molding
electrochemical reactions as reported in the above examples. and casting methods. The HRTEM images of CG0.345 demon-
Their excellent conductivity facilitates rapid electron transport, strate that the 0.25 nm fringe spacing closely matches the lattice
improving the charging and discharging rates. Additionally, space of the (3 1 1) plane of CoFe2O4. The dimension, magnetic
CNTs offer superior mechanical strength and flexibility, enhanc- coercivity, and electrical conductivity of Co-ferrite NPs grew in
ing the structural integrity and durability of the ESDs and allow- tandem with an increase in cobalt concentration (up to 25 mol%).
ing them to withstand repeated cycles. Cobalt oxides exhibit A one-step cold plasma process was used to fabricate the
excellent catalytic properties, improving the efficiency of redox Co–metal oxide framework and Co-MOF/rGO supercapacitor
reactions crucial for ES. The hybrid structure also increases electrode and Figure 19A(a–g) shows the schematic representa-
the energy density, high cyclic capacity, and stability, making tion of the DBD gas–liquid cold plasma synthesizer. MOF-71,
it a promising material for ES. Co-MOF-rGO, and Co-MOF optical images and Co-MOF-rGO
nanocomposites in an ambient environment with an average
thickness of 20 nm were proved by FESEM and elemental map-
6.2. Cobalt–Graphene ping by energy dispersive X-ray analysis. It was found that
layered Co-MOF nanosheet regularity improved with increasing
Two steps have been taken in the fabrication of ternary CoFe2O4/ plasma voltage. The addition of rGO improves the ECP
graphene/PANI nanocomposites using XRD, XPS, TG, and by enhancing the structure’s conductivity and diffusion of
morphological studies and it was discovered that excellent electrolyte, creating more conductive channels inside the
ECP is facilitated by well-designed nanostructures; the coopera- Co-MOF@rGO. The Co-MOF@rGO maintained the nanosheet
tive effects among three components are represented in shape, which exhibited the SCs of 967.68 Fg
1 at 1 Ag
1, while
Figure 18a. The CV plots for CGP0.345, binary GP, binary CP, Co-MOF showed the SCs of 651.76 Fg
1 under the same condi-
and ternary CGP0.345 are represented in Figure 18b, in which tion, as shown in Figure 19B(a–g). Every electrochemical study
CGP0.345 exhibits the maximum value. Figure 18c exhibits the was carried out in a 6 M KOH electrolyte, where the anodic and
ternary CGP0.345 CV curves at different scan rates with good rate cathodic redox peaks show that Faradic reactions make up most

Figure 18. a) Schematic representation for the preparation of ternary CGP nanocomposites. b) CV curves of two electrode system. c) CV representation of
ternary CGP0.345 at various scan rates. d) CV representation of CoFe2O4, reduced graphene oxide, and PANI in 1 M KOH@1 mV s
1. e) CV representation
of CGP0.345, binary GP, binary CP, and ternary CGP0.345 in 1 M KOH@1 mV s
1. f ) CV plots of ternary CGP0.345 nanocomposites at various scan rates.
g) Various ternary CGP SC (Reproduced with permission.[176] Copyright 2014, Elsevier).

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Figure 19. A a) Diagrammatic representation of the DBD gas–liquid cold-plasma synthesizer which is used to create MOF-71 and MOF composites and
high resolution of Co–MOF–rGO. B a) CV@scan rate of 25 mV utilizing Co–MOF–rGO as the positive electrode and activated carbon as the negative
electrode. b) The Co–MOF–rGO||AC device CVs@different scan rates ranging from 5 to 100 mV. c) GCD curves of Co–MOF–rGO||AC various Id ranging
from 1 to 10 A. d) The Co/Ni–MOF–rGO||AC Nyquist plot. e) Ragone plot. f ) The Co–MOF–rGO||AC device rate capability plot at different particular
current ranges from 1 to 20 A. Every study was carried out using an electrolyte of KOH (0.6 M). C a) The Co–MOF electrodes’ CV curves at various scan
speeds ranging from 5 to 100 mV s
1. b) Co–MOF, Co–MOF–rGO composite, and rGO CV curves @5 mV s
1. c) Co–MOF discharge patterns at various
Id. d) Capacitance retention. e) Nyquist. f ) Bode-phase plots of every synthetic electrode at an unplugged circuit potential in the frequency ranging from
100 kHz to 0.1 Hz (Reproduced with permission.[177] as an open access source).

of the charge in active material at all scanning velocities. At the to be a quasispherical structure. The halloysite substrate was
electrode–electrolyte interface, MOF interacts reversibly and adorned with cobalt ferrite NPs acting as an electrocatalyst
sequentially with dissolved anions at slower scan speeds. and green produced nitrogen and sulfur-infused graphene quan-
Three peaks were produced, one for reduction and two for oxi- tum dots (GQD) acting as conductive components. After
dation. Rapid Faraday reactions on the electrode material surface 20 cycles at a current of 1 mA using the charging–discharging
and low resistance are indicated by the scan rates; increased chronopotentiometry technique, the halloysites demonstrated
redox peak intensity. At high scan velocities, ions in active mate- hydrogen storage capacities of 300 and 600 mA g h
1 in compar-
rials cannot reach of micropores, which reduces the efficiency. ison to each other in the 2 M KOH electrolyte. Figure 20B(a–e)
Furthermore, a hybrid device composed of Co-MOF@rGO|| displays the morphologies of the intended samples at varying
AC demonstrated a noteworthy SE of 41.82 Wh Kg
1 and Sp magnifications of 1 μm and 200 nm, including S, N-GQDs,
up to 284 W kg
1. Figure 19C(a–f ) shows the Co-MOF CoFe2O4/halloysite nanotubes (HNTs), and CoFe2O4/S,
electrodes’ CV curves at various scan speeds ranging from N-GQDs/HNTs nanocomposites. Furthermore, after 20 cycles,
5 to 100 mV s
1 and Co-MOF, Co-MOF-rGO composite, and the S, N-GQDs/ HNTs displayed a discharge capacity of
rGO CV curves at 5 mV s
1. Co-MOF discharge patterns at vari- 466 mA h g
1 by applying 1 mA current density in 2 M KOH
ous Id, capacitance retentions, Nyquist, and Bode phase plots of as represented in Figure 20C(a–d).[178]
every synthetic electrode at an unplugged circuit potential in fre- Overall, it was understood that composite materials based on
quency ranging from 100 kHz to 0.1 Hz are seen.[177] cobalt and graphene exhibit enhanced conductivity due to the
When physisorption and spillover processes are combined, graphene conductive network, facilitating rapid electron trans-
halloysite nanoclay has advantageous qualities for hydrogen port and faster charging discharging rates. The increased surface
adsorption, as shown in Figure 20A(a–e). The displayed area of graphene allows for greater interaction with cobalt par-
FESEM micrographs at various magnifications of all composites ticles, providing more active sites for electrochemical reactions
demonstrated that the morphology of CoF is not significantly and significantly enhancing capacity and efficiency. The mechan-
affected by doping of Cu2þ and Ho3þ ions, the structure appears ical strength of graphene and flexibility also improve the

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Figure 20. A a–c) Decoration of CoFe2O4 and N-GQDs NPs on the HNT substrate. d–e) spillover mechanism of CoFe2O4/S, N-GQDs/HNTs for hydro-
gen storage. B a,b) FESEM images of S, N-GQDs/HNTs. c,d) CoFe2O4/HNTs. C a–c) discharge profiles of CoFe2O4/HNTs, S, N-GQDs/HNTs and
CoFe2O4/S, N-GQDs/HNTs. d) CV curves for pristine CoFe2O4/S, N-GQDs/HNTs and HNTs nanocomposites (Reproduced with permission.[178]
as an open access source).

structural integrity of the composite during repeated cycles, images show the homogeneous microplates with a thickness
enhancing the longevity and stability of the storage. This results of around 96 nm and length around 19–21 μm built up like
in higher energy density, allowing more storage, essentially com- microflower-like structures. As the concentration of these
pact for ES.[179] MXene is a novel class of 2D graphene-like car- electrodes increases, the structure shifts from microflower to
bonitrides achieved by atomic manipulation of multiple layered nanoflake-like morphology. With the exceptional capacitive
compounds through selective etching,[180] which are considered retention of 88% over 8000 cycles, the maximum Cs of
in miniaturized storage of energy.[181] Hybrid structures based 571 Fg
1 is achieved at constant Id of 2.2 Ag
1. The redox peaks
on Co and MXene are attractive these days, like core–shell struc- of H-chemical mechanical polishing electrodes are almost revers-
tures based on Co core and MXene@Bi2O3 shells as supercapa- ible, the CV curves of the composite show intercalation pseudo-
citors possessing high discharge capacitance of 646.1 Fg
1 capacitive characteristics with significantly greater stability and
(1 Ag
1) that exhibited considerable foldability and long cycling adequately fast electronic and ionic transport rates. Even at a high
stability[182] and Co3V2O8/Co3O4/Ti3C2Tx composite structures scan rate, the CV structure is maintained, demonstrating the
as electrodes of supercapacitors, which are synthesized via the material outstanding performance.[186] In 2017, Elkholy et al.
facile one-step succinct-operated hydrothermal process and used a straightforward one-pot coprecipitation technique to syn-
reveal high SCs of ≈3800 mF cm
2.[183] There are also examples thesize manganese cobalt ferrite NPs with spinal structures and
of using Co-based MXene composites for LIBs, which experience average pore diameter of 10.0 nm, while the BET surface area
early state of adolescence.[184,185] was recorded at 104.963 m
2 g
1. While CV and GCD measure-
ments were used to assess the MnCoFeO4 material as produced
6.3. Cobalt–Manganese as an electrode for supercapacitors in 6 M KOH, the supercapa-
citor was scanned at a rate of 1 mV s
1, and its maximum Cs was
Using an effective hydrothermal process at 120 °C, the nano-/ 675 Fg
1. Its power and energy densities at 1.5 Ag
1 were
microstructure Co-Mn phosphate thin film was immediately 337.50 W and 18.85 Wh kg
1, respectively, whereas outstanding
coated on the stainless steel substrate. The monoclinic structure long-term stability of 92.86% after 1000 cycles was obtained. The
is confirmed by XRD analysis and the hydrous nature of Co–Mn combined action of three TMOs is responsible for expectational
phosphate is revealed by FTIR spectroscopy and XPS, and dif- stability. MnCoFeO4 pseudocapacitive nature causes deviations
fraction peaks indicate highly crystalline material. The FESEM from linearity in its GCD curves. As the current density drops,

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it is evident that the MnCoFeO4 electrode exhibits longer The current density increased, and two of the ASCs electrodes
charging and discharging periods.[187] These results enhance had unequal charges because the carbon-based electrode ion
conductivity of cobalt, facilitate rapid electron transport exchange rate was higher than that of the pseudocapacitive elec-
and faster charging–discharging rates, increase capacity, and trode. Reduced active material consumption and Faradic process
improve stability. Additionally, composites provide high power limit at the electrode outer surface will result from the restriction
output, enhanced energy density, and cyclic stability. of the diffusion effect of a high density of current, when the cur-
rent density increases, the ASC stability decreases.[189] In 2023,
6.4. Cobalt–Silica Mandal et al. employed an in situ polymerization technique to
prepare porous binary nanocomposites, as shown in Figure 21a.
Cobalt–silica composites are primarily used in supercapacitors, According to structural characterization, the synergistic interac-
LIBs, and fuel cells. In supercapacitors, they serve as electrode tion among PANI and copper cobalt ferrite was confirmed
materials to enhance capacitive performance and energy density. through FESEM, XRD, and EDS, as shown in Figure 21b–e, lead-
In LIBs they function as anode material improving ECP and ing to the firmly established core–shell-type structure and a
cyclic stability. In fuel cells, cobalt silica composites act as cata- notable augmentation of the charge transfer mechanism and
lysts, boosting reaction efficiency. In 2023, Christopher et al. charge storage mechanism. It demonstrates the creation of a
synthesized flake-like SiO2–CoFe2O4. Within the bulk material single-phase compound, as seen by the examined samples’ XRD
in terms of shape, size, and orientation, the particles were mono- patterns that match references with cubic, tetragonal, and cubic
dispersed and evenly distributed with an average size of 14 nm. structures. The highest capacitance of PANI/CCF nanocompo-
The CV curves of fly ash were used to determine the SiO2 content site of ratio 8:1 was 408.8 Fg
1 at 0.5 mV s
1 and 460.1 Fg
1
and SCs for both CoFe2O4 and SiO2–CoFe2O4. The SiO2– at 0.5 Ag
1. Notably at 150 and 1500 W kg
1 Pd, respectively,
CoFe2O4 nanocomposites showed a high capacitance value of Ed of PANI/CCF 8:1 was 23 and 18.2 Wh kg
1, indicating
1259 Fg
1 at 1 Ag
1, which was much higher compared to that it is substantially more stable at current densities.
CoFe2O4. The CV response demonstrated that as the scan rate Furthermore, after 1500 cycles, the PANI/CCF 8:1 nanocompo-
increases, the current increases as well, indicating the capability site showed outstanding Cs retention of 91%, as shown in
of nanostructures. The CV maintained its shape even at higher Figure 21f–k, in opposition to CV curves seen at 5 mV s
1
scan rates, providing the electrode materials with outstanding a), comparative GCD plots at 0.5 Ag
1 b), cyclic stability of the
performance. These CV curves shows clear redox peaks, which PANI/CCF 8:1 nanocomposite at a constant Id of 2.5 Ag
1
illustrate the electrodes Faradic pseudocapacitive activity. These c), PANI/CCF 8:1 CV plots at various scan rates d), CD curves
nanocomposites also exhibit excellent cyclic stability and pseudo- of the PANI/CCF 8:1 at various in Id e) and Ragone plot for the
capacitance, with an efficiency of 87.9%, preserving capacitance prepared PANI & PANI/CCF hybrid electrodes f ).[190] In 2023,
over 5000 cycles.[188] Their porous structure offers a high surface Anwar et al. employed the hydrothermal approach to manufac-
area, beneficial for electrochemical reactions, while cobalt shows ture CoFe2O4 (CoF), Cu, and Ho Co-doped CoFe2O4 (CH–CoF),
excellent electrical conductivity and enhances overall perfor- a crosslinked graphene nanocomposite including Cu and
mance. The silica matrix stabilizes cobalt NPs, reducing degra- CH–CoF, as shown in Figure 22a,b. Using three-electrode con-
dation and extending device longevity. Additionally, these figurations, CV, GCD, and EIS measurements were employed to
composites provide enhanced energy density and allow for ver- evaluate the supercapacitor performance of all produced elec-
satile functionalization, enabling tailored properties for making trode substances. In contrast to CoF (Cs = 458 Fg
1), the SCs
ideal compact ES solutions. of CH–CoF and CH–CoF/CLG was 792 and 1258 Fg
1, respec-
tively, as shown in Figure 22d,g. The time versus potential graph
of CH–CoF at various Id and GCD behaviors of all produced
6.5. Cobalt–Copper
nanocomposite electrode materials in 1 M KOH is shown in
Figure 22e,h. Cs of all nanocomposite electrodes are shown in
The composite of cobalt–copper offers structural stability, reduc-
Figure 22f,i. Additionally, comparative to CoF (49.54%) and
ing material degradation and extending the device longevity. In
CH–CoF (58.46%), CH–CoF/CLG nanocomposite showed
2022, Kiey et al. developed the binary cobalt–copper via the citrate
significant capacitance retention (62.91%), as represented in
combustion method. NPs were found to have SCs of 378, 458,
Figure 22c, and superior supercapacitance performance.[191]
and 893 Fg
1 at rate of 5 mV s
1. Cobalt–copper ferrite exhibited
These composites serve as electrode materials in supercapacitors
the maximum specific capacity retention of 90% after 3000
to enhance ES capacity and power density, as anode materials in
cycles.[45] A unique yolk–shell copper cobalt selenide was made
LIBs to improve ECP and cyclic stability and as catalysts in fuel
using a simple self-templating two-step hydrothermal process.
cells to boost reaction efficiency. These composites include high
Microspheres with yolk shells were examined inside using a
electrical conductivity provided by copper and synergistic effects
TEM micrograph. The inner sphere confirmed that there exist
that enhance performance.
the differences in brightness between the black shell and pale
inner cavity. Yolk–shell copper cobalt selenide was assessed
using a variety of electrochemical techniques as new cathode 6.6. Cobalt–Zinc
electrodes with cycling stability (83.7%) after 6000 cycles, which
revealed high Cs ≈512 Fg
1 at 1.0 Ag
1, and excellent rate capa- Cobalt–zinc composites have garnered attention for their poten-
bility (70.8%) after raising the Id up to six times. The energy den- tial in ESDs, particularly in zinc–air batteries (ZABs), supercapa-
sity is ≈9.45 Wh kg
1, and the power density is up to 850 W kg
1. citors, and LIBs. In ZABs, they enhanced the efficiency of the air

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Figure 21. a) A charge compassion model and hydrogen bonding are used to illustrate a potential interaction between PANI and copper cobalt ferrite.
b–e) FESEM images of various PANI/CCF. f ) Comparative CV plots at 5 mV s
1. g) Compared GCD [email protected] Ag
1. h) Cyclic stability of the PANI/CCF
8:1 nanocomposite at steady Id of 2.5 Ag
1. i) PANI/CCF 8:1 CV plots at various scan rates. j) GCD curves of the PANI/CCF 8:1 at differences in Id, and
k) Ragone plot for the arranged PANI & PANI/CCF hybrid electrodes (Reproduced with permission.[190] Copyright 2023, Elsevier).

electrode, crucial for oxygen reduction and evolution reaction. which completely utilizes the inner active sites of cobalt-doped
Utilizing a more secure coprecipitation technique, pure and zinc ferrite and pure NPs, Furthermore, the maintenance of high
cobalt-substituted zinc–ferrite NPs were produced. Cobalt substi- capacities at high densities throughout the charging and
tution in zinc–ferrite nanostructures resulted in optical, electro- discharging process directly impacts the BT potential use and
chemical, and structural characteristics. By shifting the cation challenges.[107] The abundance of zinc and lower cost make these
vibration mode in the tetrahedral site toward a higher-order composites cost-effective and environmentally friendly, with
wavenumber (541–565 cm
1), the production of cobalt was vali- high electrical conductivity and superior electrical properties,
dated. It was found that the average crystallite size was raised increasing capacity and improving charging–discharging rates.
from 42.4 to 56.5 nm, as incremental of zinc–ferrite; this is Structural stability from composite structure helps reduce degra-
because grain growth is caused by growing molecular concentra- dation and extend device longevity.
tion and the development of small crystals at the surface. GCD of
CoxZn4
xFe2O4 electrode at various Id in a 1 M NaOH solution 6.7. Cobalt–Nickel
showed reversible charging and discharging processes with the
maximum SCs of 377.81 Fg
1. SCs at low current density with Cobalt–nickel (Co–Ni) composites offer high energy density,
high specific capacity of the sample result in low Ohmic drop, enhanced ECP, and structural stability[192] and flexibility.[193]

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Figure 22. a,b) Diagrammatic representation of the CH–CoF/CLG nanocomposites assembly and diagrammatic representation of the CH–CoF/CLG
nanocomposites effective electrochemical storage system. c) EIS spectra of the CH–CoF/CLG nanocomposites; Coulombic efficiency (%) and capacitive
retention (%) for 3000 GCD cycles. d) CV plots of CH–CoF/CLG nanocomposites at different scan rates. e) Time vs potential graph of CH–CoF at various
Id. f ) The SCs of all nanocomposite electrodes in relation to scan rates. g) Potential versus current graph of CoF at various scan rates. h) GCD behaviors
of all produced nanocomposite electrode material in 1 M KOH Id@1 Ag
1. i) Percentage of created active substance that retains capacitance
(Reproduced with permission.[191] as an open access source).

These composites improve specific capacity, cycling stability, and electrochemically activated material causes long-term CV.
charge–discharge rates due to synergistic effects, their structural Electrode has an outstanding rate performance (67.5% of initial
versatility allows researchers to obtain various nanostructures capacity under 50 mA cm
2), a long lifespan (84.8% of initial
like nanowires and nanosheets.[194] Providing a larger surface capacity after 5000 cycles), excellent areal capacity of
area for enhanced electron and ion transport, cobalt and nickel 4.186 C cm
2, cyclic stability (93.4% of original capacity after
oxides, as well as Co-Ni binary oxides, were created by the simple 8000 cycles), and a maximum Ed of 0.648 mWh cm
2.[196]
electrochemical deposition method in carbon cloth. In compari- Electrochemical deposition was successfully employed to create
son to the nickel and cobalt samples (Cs of 49 and 63 Fg
1, the Ni–Co double-hydroxide composite formed on Fe foil, which
respectively), the CoNi binary oxide sample showed a Cs of was then used as electrode for a supercapacitor. Figure 23b,c
179 Fg
1 with a capacity retention of over 83% after 5000 shows the SEM images of Ni–Co depicting that the composites
cycles.[195] An efficient electrochemical activation technique is grow on nanosheets like a flower-shape structure. The vertical
intended to improve the total ES capacity using nickel–cobalt stacking nanosheets in the Ni–Co double-hydroxide composite
hydroxide based on copper. Figure 23a shows the illustration have a network topology that promotes electrolyte transport
of NiCo–OH. The significant increase in charge storage capacity and increases the number of electroactive sites for quick ES.
and the in situ transformation from Cu-doped NiCo–OH to Ni–Co double-hydroxide composite showed excellent ECP,

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Figure 23. a) Illustration of NiCo–OH (Reproduced with permission.[196] Copyright 2021, American Chemical Society). b,c) TEM images of Ni–Co double-
hydroxide composites. d) Fe foil electrode scan rate at 20 mV s
1. e) Various scan rates of Ni–Co double hydroxides. f ) GCD curves. g) SCs of material.
h) Cyclic stability of the material (Reproduced with permission.[197] Copyright 2016, Wiley).

examined through CV and GCD curves, demonstrating long by electrodeposition on nickel foam. Superior Cs of 1734.9 and
cyclic stability and 85% of the initial capacitance after 1000 cycles 1201.8 Fg
1 were reported by NiCo2O4, with high cyclic stability
at Id of 4 Ag
1 and Cs of 853.7 Fg
1 at Id of 1 Ag
1, as shown in (only 12.7% loss after 3500 cycles) at charging and discharging
Figure 23d–h. It was reported that cobalt carbonate hydrocide rates of 2 and 50 Ag
1, respectively. On top of that, using
demonstrates the performance of capacitive behavior in solid-state poly(vinyl alcohol)-KOH gel as the electrolyte and
nickel–cobalt carbonate hydroxide.[197] NiCo2O4 has been formed NiCo2O4 and CNT as the anode and cathode respectively, a

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high-performance solid-state ASC was fabricated. At 0.5 Ag
1 in the spectrum results of γ-Fe2O3 @SiO2-2-(2-benzothiazolyl
charging/discharging, SCs was 212.47 Fg
1 at high power den- azo)-4 methoxyaniline, and the weight percentage of the detecting
sity of 5796.04 W kg
1 at 19.16 Wh kg
1 energy density, and a elements suggests that the nanocomposites are effectively con-
high energy density 42.25 Wh kg
1 at a 298.79 W kg
1 power structed. The elemental mapping picture of CoFe3O4@SiO2-2-
density.[90] These composites are highly promising for ES due (2-benothiazolyl azo)-4-methoxyaniline is displayed and it can
to their electrochemical properties. In LIBs, these composites demonstrate how the incorporation of azo ligand occurs in
are used in both cathode and anode material. Layered oxides like the N and S.[199]
LiCoO2 and LiNiO2 in in cathodes enhance energy density and
cyclic stability, while anodes achieve higher SCs and rate capa- 6.10. Cobalt–Lanthanum
bilities. In supercapacitors, these composites leverage the pseu-
docapacitive behavior with long cyclic life. The synthesis is carried out by a facile electrodeposition method
in addition to providing strong electrochemical results in alkaline
6.8. Cobalt–Cadmium Sulfide electrolytes which is a viable option for high-performance elec-
trochemical applications due to its impact on redox active spe-
The unique electrochemical characteristics and synergistic effect cies. However, some non–ferrite components may be included
of Co–CdS composite structures make them aninteresting mate- in La–Co structures, which depends on the purpose and expec-
rial for ES. With an enhanced SCs, better cycle stability, and tation of researchers. For example, Figure 24a represents the
quicker charge–discharge rates, these composites increase fabrication of a two-electrode cell using La–Co LDH/CC in an
ECP. CdS NRs-based nanocomposites were obtained by the alkaline electrolyte, and Figure 24b–e represents respective CV
hydrothermal process and further combined with cobalt ferrite curves in alkaline and redox electrolytes, redox electrolyte,
and graphene oxide. The pure CdS diffraction pattern was well GCD plots at different Id, and the comparative Ragone plot of
indexed with the hexagonal structure. The observation of all the La–Co LDH/CC gravity and volumetric capacity in redox and
peaks relating to both CdS and CoFe2O4 suggests the coexistence alkaline electrolytes, as the La–Co LDH nanosheets exhibit high
of hexagonal phase of CdS and cubic phase of CoFe2O4. The rate and stability performances up to 1000 cycles, with 91.33%
unique redox peaks in the CV plot indicate that the system exhib- capacity retention and 93.36% rate performance in the range
its a pseudocapacitive behavior, which demonstrate that binary of 10–35 Ag
1 current density. Furthermore, the La–Co LDH
composites offer an elevated pseudocapacitive behavior of achieves very low resistance in the redox electrolyte and an excel-
99.22% with limited EDLC contribution of 0.66%. Resultant lent Cs 2162 Cg
1 and high Id at 10 Ag
1 without any doubt, in a
CdS–CoFe–G showed the exceptional cyclic stability and high cell with redox electrolyte. La–Co LDH generates remarkable
Cs of 1486 Fg
1 and retention of 78% up to 5000 cycles. cyclic stability of 15 000 cycles with 96.55 capacity retention as
Additionally, the electrode material has a high Id of shown in Figure 24f and a comparison of La–Co LDH/CC
528.8 Wh kg
1 and a Pd of 4000 W kg
1 allowing for reversible specific energy and specific power is shown in Figure 24g.[2]
cyclic with a broad potential window of 0–1.6 V.[198] Co–CdS Table 8 compares various Co3O4 and its composite materials
composites offer a vast surface area and facilitate the electron for supercapacitors.
and ion transport through diverse synthesized anostructures
including nanowires and nanosheets. Co–CdS composites are 6.11. Cobalt-Polymer Composites
high-capacity anode materials used in LIBs, which improve cath-
ode materials, thereby extending cycle life, energy density, and Cobalt polymer composites are emerging as a highly effective
nanostructures that maximize surface area and improved ion solution in ES technologies, combing the electrochemical advan-
diffusion. tages of cobalt with enhanced conductivity and stability of poly-
mers to deliver superior performance across supercapacitors,
6.9. Cobalt–Ferrous batteries, and hybrid systems.[200] We know that polymers are
classified as conductive polymers (such as polyaniline (PANI),
By commencing with a solution of ferrous, ferric, and cobalt ions polypyrrole (PPy) and poly (3.4-ethylenedioxythiophene)
and then calcinating it, a controlled coprecipitation process is (PEDOT)), electroactive polymers (Poly (ethylene oxide) (PEO),
used to demonstrate viability of producing cobalt ferrites. poly (vinylidene fluoride) (PVDF)), and flexible and structural
CoFe2O4 is synthesized by calculating the molar ratio of 1:2 polymers (polyurethane (PU), poly(methyl methacrylate)
(Fe2þ/Fe3þ) and addressing the aggregation problem. There (PMMA)) used in ES systems.[201] Cobalt/polymer composites
was no discernible change in the cation distribution of the sam- are synthesized by combining cobalt oxides or salts with CPs
ples with an increase in Fe3þ. The synthesized cobalt NPs dem- such as PANI or PPy. Alternatively, polymer composites integrat-
onstrated remarkable superparamagnetic characteristics with high ing conductive polymers optimize ES performance combining
value of coercivity, saturation, and remnant magnetization.[15] enhanced conductivity, capacitance and stability.[202] Wei et al.
In 2023, Mahmoud et al. produced γ-Fe2O3 @SiO2-2-(2- synthesized supercapacitor electrode material by potentiody-
benzothiazolyl azo)-4 methoxy aniline and CoFe3O4@SiO2-2- namic electropolymerization ternary composite of cobalt oxide
(2-benothiazolyl azo)-4-methoxyaniline electrode using the Stober (Co3O4), PPy, and carbon paper (CP). PPy/f-Co3O4/CP exhibited
technique. The two electrodes demonstrated exceptional stability excellent super capacitive performance with Cs of 398.4 Fg
1
for up to 1000 charging–discharging cycles as well as elevated Cs at Id of 50 Ag
1% and 100% capacitance retention over 1000
of 640 and 580 Fg
1. Aspects such as Fe, O, Si, S, and N are visible cycles.[203] In 2022, Mohammad et al. used the hydrothermal

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Figure 24. a) The fabrication of a two-electrode cell using La–Co LDH/CC is shown schematically. b,c) Respective CV curves in alkaline and redox
electrolytes and redox electrolyte. d) GCD plots at different current densities. e) Comparative Ragone plot of La–Co LDH/CC gravity and volumetric
capacity in redox and alkaline electrolytes. f ) A capacity retention plot of La–Co LDH/CC demonstrating high cyclic stability at redox electrolyte.
g) A comparison of La–Co LDH/CC specific energy and specific power (Reproduced with permission.[2] as an open access source).

approach to synthesize dandelion-like nickel cobalt sulfide@po- 6.12. Comparative Electrochemical Performance of Different
lypyrrole microspheres, and its potential use as a binder-free elec- Materials
trode in supercapacitors was studied. With excellent SCs of
2554.9 Fg
1 at 2.54 Ag
1, this electrode demonstrates minimal Because the charge storage of electrochemical capacitors is based
charge transfer resistance and capacitance retention of almost on reversible processes on or near the surface of the electrode
92% for 10 000 cycles. Additionally, an ASC with rGO/NF serv- active materials, rather than ion diffusion throughout the bulk
ing as the negative electrode and NiCo2S4@PPy serving as of electrode active materials, they are able to attain a far better
positive electrode showed Cs of 98.9 Fg
1 at 1.84 Ag
1. The com- power density than rechargeable batteries. As a result, ECs
bined action of PPy and NiCo2S4 as direct deposition of compos- appear to be a viable supplement and substitute for rechargeable
ite in current collectors is responsible for outstanding batteries. Zhao et al. reported that the Co@Co3O4/CNTs nano-
performance.[204] a Cobalt polymer composites are utilized in composite had high conductivity by arc discharge. This nano-
a range of ESDs. In batteries, they serve as electrode materials, composite, which serves as the anode material for LIBs,
contributing to higher capacity, energy density, and improved exhibited a reversible capacity of 820 mAh g
1 at a current den-
cycling performance in Li-ion and Na-ion batteries. In superca- sity of 0.2 Ag
1 after 250 cycles, which is significantly greater
pacitors, these composites enhance SCs and power density, than its theoretical capacity. With a capacity of 760 mAh g
1 after
resulting in high-performance ES with excellent charge– 350 cycles at 1 Ag
1 (103% of the initial capacity) and
discharge rates. 529 mAh g
1 after 600 cycles at 2 Ag
1, the material’s rate

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Table 8. Comparison of various Co3O4 and its composite materials for supercapacitors.

Materials Cyclic performance SCs value References

1
1
1
Co3O4 nanowires 85% after 1000 cycles at 2 Ag 278.4 C g @1 Ag [354]
Co3O4 thin sheets 99.3% after 2000 cycles at 5 Ag
1 600 C g
1@1 Ag
1 [355]
Co3O4 nanoflakes 82% after 5000 cycles at 5 Ag
1 576.8 C g
1@1 Ag
1 [91]
CexCoFe2
xO4 82.3% after 4000 cycles at 0.5 Ag
1 937.50 Fg
1 @1 mVs
1 [316]
Porous mixed-phase CoO/Co3O4 nanocomposites 108% after 5000 cycles at 30 mVs
1 180.4 C g
1@1 Ag
1 [356]

2
Multisized nanosheet CoFe LDH a)
85.1% after 4000 cycles at 1 mA cm 3340 m Fg
1@1 mV cm
2 [357]
NiO/Co3O4 core shell composites 92% after 1000 cycles at 5 mA cm
2 363 255 Cg
1@5 Ag
1 [358]
Co0.5Ho0.5Fe2O4 92% after 1000 cycle at 1 Ag
1 590 Fg
1@20 mVs
1 [359]

1
1
1
Mesoporous Co3O4/Carbon composites 93.4% after 2000 cycles at 5 Ag 92.4 C g @2 mVs [360]
Co3O4-coated multiwalled CNT 88% after 500 cycles at 0.5 Ag
1 204.8 C g
[email protected] Ag
1 [361]
CoFe2O4/rGO 98% after 2000 cycles at 5 Ag
1 551 Fg
1@2 mVs
1 [320]
Co–Fe LDH@NiO 66.9% after 5000 cycles at 2 Ag
1 361 Cg
1@1 Ag
1 [362]

1
Mesoporous Co3O4 NPs 92% after 4000 cycles at 10 Ag 304 C g
1@1 Ag
1 [363]
Layered Co3O4 94% after 1000 cycles at 1 Ag
1 407 Fg
1@5 mVs
1 [364]
CoFe2O4/graphene NRs 87% after 10 000 cycles at 1 Ag
1 487.45 Fg
1@1 Ag
1 [253]

1
1
1
Core shell Co3O4 87.0% after 2000 cycles at 0.5 Ag 837.7 Fg @1 Ag [365]
CoFe2O4/Cu/g-C3N4 86.4% after 10 000 cycles at 10 Ag
1 1380 Fg
1@1 Ag
1 [366]
CoMn LDH@Ni foam 93.2% after 3000 cycles at 5 Ag
1 1409 Fg
1@1 Ag
1 [367]
PGNC 94% after 6000 cycles at 0.5 Ag
1 1286 Fg
[email protected] Ag
1 [368]

1
1
1
CoMn–LDH 91.6% after 2000 cycles at 5 Ag 511 Fg @2 Ag [369]
Co3O4/SiO2 80.5% after 1000 cycles at 1 Ag
1 679 Fg
1@1 Ag
1 [370]
PACOF 81% after 6000 cycles at 1 Ag
1 282.35 Fg
1@1 mA [371]
CoNi NPs@S, N-doped carbon 95.1% after 3000 cycles at 5 Ag
1 1970 Fg
1@1 Ag
1 [372]
GO/PANI/CoFe2O4 79% after 5000 cycles at 1 Ag
1 781.27 Fg
1@1 mVs
1 [373]

1
1
1
Co3O4 NPs MOF 100% after 2500 cycles at 0.5 Ag 157 Fg @0.5 Ag [374]
Ni 1
xCoxFe 2O4 82% after 1500 cycles at 0.5 Ag
1 991 Fg
[email protected] Ag
1 [375]
Co3O4@NiMoO4 89.9% after 3000 cycles at 0.5 Ag
1 931 Fg
1@10 Ag
1 [376]
Co(VO3)2–Co(OH3)2 MOF 90% after 1500 cycles at 0.5 mA cm
2 805 Fg
[email protected] mA cm
2 [377]

1
1
1
CoFe2O4 85% after 1500 cycles at 0.5 Ag 655.4 Fg @0.25 Ag [375]
Co–Ni–OH/rGO/CC 96.8% after 10 000 cycles at 10 Ag
1 400 Fg
1@10 Ag
1 [378]
Co (OH)2 MOF 94% after 5000 cycles at 0.5 mA cm
2 1044 Fg
1@2 Ag
1 [379]

1
1
1
Co3O4/rGO 96% after 1000 cycles at 1 Ag 754 Fg @1 Ag [380]
CoGa LDH 86.2% after 8000 cycles at 15 Ag
1 1431.5 Cg
1@1 Ag
1 [381]
CoV LDH 82% after 10 000 cycles at 1 Ag
1 1579 Fg
1@1 Ag
1 [382]
CoFe nanosheets LDH 93% after 2000 cycles at 1 mA cm
2 70 μ Fg
1@2 mA cm
2 [305]

1
1
1
CoF/G/PANI 98.2% after 2000 cycles at 1 Ag 1123 Fg @1 Ag [383]
Co3O4 MOF 93% after 12 000 cycles at 0.5 mA cm
2 3.7 Fg
1@2 mA cm
2 [384]
Cox-Ag/CNF 72.65% after 2000 cycles at 0.5 Ag
1 301 Fg
[email protected] Ag
1 [385]
Co3
xFexO4 79.2% after 5000 cycles at 6 Ag
1 768 Fg
1@6 Ag
1 [386]
Co3O4–CeO2 hallow polyhedrons 96.7% after 6000 cycles at 1 Ag
1 1288.3 Fg
[email protected] Ag
1 [387]

1
1
1
Co3O4 nanowires@MnO2 nanolayer 125% after 1000 cycles at 0.5 Ag 1209.4 Fg @1 Ag [388]
CoFe2O4 thin films 85% after 1500 cycles at 0.5 mA cm
2 777.4 Fg
1@1 mVs
1 [389]
1D Co3O4 NP 95.2% after 1000 cycles at 10 mVs
1 468.18 Fg
1@10 mVs
1 [390]
1D Co3O4 nanowires 90% after 2000 cycles at 2 Ag
1 977 Fg
1@2 Ag
1 [391]

2
2
2
CoAl LDH 85% after 5000 cycles at 5 mA cm 23.75 F cm @5 mV cm [392]
GO/CO3O4 96.04% after 4000 cycles at 0.6 Ag
1 778 Fg
[email protected] Ag
1 [393]
CoV LDH 85.8% after 5000 cycles at 1 Ag
1 3540 Fg
1@1 Ag
1 [394]

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Table 8. Continued.

Materials Cyclic performance SCs value References

2
1
2
CoFe2O4/MWCNTs 92% after 2000 cycles at 3 mA cm 81 Fg @3 mA cm [395]
Co0.50Ga0.50-LDH 97.5% after 5000 cycles at 6.6 mA cm
2 805Ccm
2@10 mVs
2 [396]
CoMn-LDH nanoflakes 96.3% after 5000 cycles at 5 Ag
1 1062.6 Fg
[email protected] Ag
1 [397]
Co2V2O7 93.8% after 3000 cycles at 5 Ag
1 415 Fg
1@5 Ag
1 [398]

1
1
1
NF/ C–Co3O4 76.6% after 8000 cycles at 0.5 Ag 211 Fg @0.5 Ag [249]
CoMoO4/NF 73,8% after 9500 cycles at 1 Ag
1 86 Fg
1 @1 Ag
1 [399]
COF-MCM 94.8% after 5000 cycles at 1 Ag
1 746 Fg
1@1 Ag
1 [29]
Vs-CMS 96.7% after 10 000 cycles at 1 mA cm
2 0.34 mAh cm
2@30 mA cm
2 [400]
NiCo-CH//AC 75% after 5000 cycles at 10 Ag
1 762 Fg
1@1 Ag
1 [401]

2
Ni–Co MOF/rGO 90.6% after 5000 cycles at 4 mA cm 1320 Fg
1@4 mA cm
2 [402]
Ni2Co–S/CNTA 86.5% after 5000 cycles at 1 Ag
1 1607.2 Fg
1@1 Ag
1 [403]

1
1
1
Co3O4/NiO/rGO ternary composites 86.9% after 6000 cycles at 1 Ag 121 Fg @1 Ag [404]
Co–Mn–Zn oxide ternary composites 68.9% after 2000 cycles at 0.5 Ag
1 51.42 Fg
[email protected] Ag
1 [399]
Fe2O3@NiCo2O4 composite 90% after 10 000 cycles at 1 Ag
1 116.5 Fg
1@1 Ag
1 [405]
Ni@Co@Mn MOFs 83.5% after 3000 cycles at 1 Ag
1 111.5 Fg
1@1 Ag
1 [406]

1
1
1
Ni–Co Selenide ternary composite 60.8% after 1000 cycles at 1 Ag 63.1 Fg @1 Ag [407]
Ni–Co–Mn oxide nanosheets@nickel foam 94.5% after 6000 cycles at 1 Ag
1 163.1 Fg
1@1 Ag
1 [408]
Ni-doped Co3O4@ CoMoO4 core shell 91.7% after 10 000 cycles at 1 Ag
1 1212 Fg
1 @1 Ag
1 [409]

a)
It should be highlighted that in some cases nonferrite components like LHD are among the supercapacitor structure, which was inevitable. However, the function of the
supercapacitor was mainly due to the ferrite-aided cobalt, where (e.g.,) LDH was used to enlarge ES capacity.

performance is likewise exceptional.[204]b A core@shell structure SC values of up to 571 and 675 Fg
1. Because of its distinct
comprising Co–Co3O4 core particles encased in a shell of shape, which consists of uniform microplates and nanoflakes,
nitrogen-doped carbon integrated into CNTs has been reported it has a larger surface area, which speeds up electron transport
by Zou to provide a high SCs of 823.4 Fg
1 at a current density of and charging–discharging rates.[186,187] Christopher reported
1 Ag
1 and a capacitance retention of 93.6% after 10 000 cycles. that the combination of cobalt with silica yields a high-
The asymmetric two-cell supercapacitor with a reduced graphene performance electrode material, exhibiting exceptional electro-
oxide negative electrode and a Co–Co3O4@CNT–NC positive chemical properties. Notably it achieves a remarkable capacitance
electrode demonstrated a high energy density of 46.7 Wh kg
1 of 1259 Fg
1 at 1 Ag
1, surpassing CoFe2O4, and demonstrates
at 1601.1 W kg
1. The Co–Co3O4@CNT–NC composite is a great enhanced cyclic stability and pseudocapacitive behavior. The
material for supercapacitors because of its high performance and material retains an impressive 87.9% Coulombic efficiency over
ease of preparation.[204]c Mulik and associates proved cobalt and 5000 cycles, ensuring reliable ES. The porous silica structure pro-
CNTs create an extremely effective and long-lasting electrode vides a high surface area, facilitating efficient electrochemical
material. The high surface area of CNTs’ cylindrical nanostruc- reactions, while Co enhances overall electrical conductivity.
ture promotes electrochemical reactions, and their superior Furthermore, the silica matrix stabilizes Co NPs, migrating
conductivity allows for quicker electron transport and higher degradation and promoting durability. This hybrid material also
charging/discharging rates. Rapid charge transfer is made offers versatile functionalization capabilities, allowing for
possible by the Co–CNT hybrids’ remarkable electrochemical tailored properties to suit specific applications.[188] The Co–Cu
stability (up to 10 000 cycles), high energy density, and pseudo- composite material exhibits exceptional electrochemical proper-
capacitive characteristics. These composites are perfect for high- ties, making it an ideal candidate. This hybrid material boasts
performance ES applications since they achieve remarkable enhanced structural stability, and reducing degradation and pro-
power densities of up to 443.7 W kg
1 and Coulombic efficiency moting longevity were studied by Mandal and his coworkers.
of up to 101.3%.[174] According to Elkholy, a synergistic combi- It achieves high SCs up to 1258 Fg
1, excellent cyclic stability
nation of manganese and cobalt has remarkable electrochemical up to 91% retention after 3000 cycles, impressive energy density
benefits, exhibiting improved power density, capacitance, and up to 23 Wh kg
1, and power density up to 850 W kg
1. Copper
stability. This hybrid material keeps 88% of its capacitance reten- incorporation significantly enhanced electrical conductivity,
tion over 8000 cycles and maintains 92.86% cycle stability after while the synergistic effects of cobalt and copper interactions
1000 cycles, indicating extraordinary long-term endurance. boost overall performance. These remarkable properties translate
Its notable accomplishments include a power density of to improved ECP in LIBs and fuel cells, making the Co–Cu com-
337.50 W kg
1, an energy density of 18.85 Wh kg
1, and high posite a promising solution for high-performance ESDs.[45,190]

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The integration of cobalt with zinc in ESDs yields numerous ben- glass plate, the sample showed a maximum SCs of
efits, revolutionizing the performance of ZABs. This hybrid 227 Fg
[email protected] Ag
1 but decreased to 152 Fg
1 (67%) when
material enhances energy efficiency, reduces degradation, and the current density was increased to 1.4 Ag
1. The SCs dropped
extends device longevity due to its structural stability. significantly to 66% after 500 cycles and stayed stable up to 1000
Electrical conductivity is significantly improved, increasing cycles; the loss of capacitance was thought to be related to the
capacity and enabling faster charging–discharging rates. The dissolution or detachment of active material during the
abundance of zinc ensures cost-effectiveness, while its eco- cycles.[206] Cobalt hydroxide offers excellent electrochemical
friendly nature makes it an attractive alternative. Notably, the activity, particularly in alkaline electrolytes, but structure changes
cobalt–zinc composite achieves a maximum SCs of 377.81 Fg
1, over cycles can lead to capacity fading. Kong et al. prepared
maintains high capacities at high densities, and exhibits Co(OH)2 nanoflakes by precipitation at a low temperatures.
reversible electrochemical properties. The increased average The materials were heated to 150 °C and beyond, turning them
crystallite size around 42.38–56.52 nm and shifted cation into spinel Co3O4. The as-synthesized Co(OH)2 exhibited
vibration mode validate the successful production of cobalt zinc linked and loosely packed NPs. The loss of H2O during
material.[107] annealing caused the NPs to grow into a stacking configuration
The Ni–Co composite exhibits exceptional benefits for ES after heat treatment. The Co(OH)2 and Co3O4 materials
application, surpassing individual component performance. produced at 100 and 250 °C have BET specific surface areas of
Notably, it achieves high energy density, improved specific capac- 85.4 and 71 m2 g
1 respectively. In the meanwhile, the pore
ity, and excellent cycling stability of 83% after 5000 cycles. The size distribution of Co3O4 and a Co(OH)2 was 5–50 nm and
material demonstrates high rate capability (67.5% capacity at 4–20 nm and the SCs of 609 Fg
1.[207] Cobalt sulfide combine
50 mA cm
2) and areal capacity (4.186 C cm
2), making it suit- control is paramount for desired morphologies and long-term
able for high-performance devices. Outstanding cyclic stability stability.
(93.4% after 8000 cycles) ensures a long lifespan. Abbas et al. Composite materials provide improved charge transfer kinet-
studied the synergistic effects of Ni and Co that enhance ECP, ics and stability, though optimizing composition and morphol-
while improved structural stability offers flexibility and versatil- ogy are key for maximizing performance. Wang and his
ity. Various nanostructures increase surface area for efficient colleagues were able to significantly increase the cobalt sulfur
electron and ion transport.[195,196] Adhikari et al. reported that electrodes’ cycle life using a solvothermal technique to create
Co–CdS composite exhibits remarkable benefits for ES applica- tower-like CoS1.097 hierarchical structures. When density was
tions, showcasing enhanced ECP. Notably, Co–CdS achieves a raised to 100 mA cm2, the CoS1.097 nanostructures showed a
SCs of 1486 Fg
1, cyclic stability with 78% retention up to good rate capability to maintain 86% of SCs up to 464 Fg
1.[208a]
5000 cycles, and high energy density of 528.8 Wh kg
1. The
material also demonstrates fast charging–discharging rates with
a power density of 4000 W kg
1 and operates within a broad 7.2. Electrolyte Design
potential window of 0–1.6 V. Co–CdS displays pseudocapacitive
behavior, facilitating efficient ES. The composite’s vast surface Selecting the right electrolyte for cobalt ferrite electrode in super-
area, courtesy of its nanowire and nanosheets structures, enables capacitors is crucial for achieving optimal performance.
easy electron and ion transport, improving overall performance. Compatibility with both aqueous and nonaqueous electrolytes
As an anode material in LIBs, Co–CdS boasts high capacity, allows flexibility in electrolyte selection. High ionic conducting
enhanced cycle life, and increased energy density.[198] is essential for facilitating rapid ion transport, maximizing
charge–discharge rates and power density. Electrolytes should
exhibit good electrochemical stability within the supercapacitors’
7. Design of Supercapacitors voltage window to prevent degradation of both the electrolyte and
electrode material. Redox compatibility ensures efficient utiliza-
7.1. Electrode Material Selection tion of cobalt ferrites redox reactions during charge–discharge
cycles. Electrolytes, which are ubiquitous and have a basic func-
Each cobalt-based electrode for supercapacitors has unique prop- tion independent of the chemistry or application of the device,
erties, where we mainly focused on cobalt oxide, cobalt hydrox- are necessary for and utilized by all electrochemical devices.
ide, and cobalt sulfide. Cobalt oxide stands out for its high SCs, In electrolytic cells, capacitors, fuel cells, and batteries, electro-
stability, and cost-effectiveness; however, its limited electrical lytes act as a medium for the transfer of charges in the form
conductivity poses challenges, which can be addressed through of ions between two electrodes. The electrolyte controls a super-
strategies like nanostructure or cobalt doping.[29] To create Co3O4 capacitor’s operational potential. It is therefore essential for
monolayer hollow sphere arrays, Tu et al. utilized polystyrene assessing the overall effectiveness of supercapacitors.
spheres as a template. The 600 nm hollow spheres that made Supercapacitors employ a variety of electrolytes, including
up the array’s skeleton were filled with Co3O4 NPs in the spaces solid-state, redox-active, aqueous, and nonaqueous electrolytes.
between them. Upon increasing the current density to 40 Ag
1, Energy (E) and power density (P) are two key factors that affect
the sample maintained 85% of its SCs, which was observed to be supercapacitors’ ECP, as demonstrated by Equation (17)
358 Fg
1@2 Ag
1. During cycling, the capacitance showed out- and (18).[208b]
standing stability, increasing up to 500 cycles and staying con-
stant for 4000 cycles.[205] Huanug et al. created a porous 1
E ¼ Cs V 2 (17)
Co3O4 thin film with spherical fine particles on an ITO-coated 2

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V2 8. Cobalt-Based Composites in Supercapacitors

P¼ (18)
2R and Batteries Applications
where V is the device’s operating voltage range, R is the internal In recent times, there has been a surge in research emphasizing
resistance inside the electrode and at the electrode/electrolyte the use of pristine Co-based MOFs as electrodes in EES systems.
junction, and Cs is the supercapacitors and batteries of the Although LIBs remain the prevailing power sources due to their
electrode materials. To improve E and P, the magnitudes of C high voltage and enduring cyclic properties, they encounter chal-
and V should be raised while R should be decreased. This is lenges such as inadequate percentage capability.[211] Capacitors,
achieved by correctly identifying the components of the electro- known for excellent power density, have been extensively studied,
lyte and electrode. Through the use of computational methodol- with a focus on materials like carbon-participated composites and
ogies and spectroscopic characterization techniques, it is inorganic metal oxides EDLCs, PC, and hybrid capacitance.[212]
discovered that the electrolytes are important in controlling their However, capacitors generally exhibit severe self-discharging
functioning voltage, cyclic life, operational temperature, series properties, inferior Ed, and poor reliability.[213]
resistance, life period, specific power, or power density and Hybrid electrochemical capacitors have emerged as a single
self-discharge rates. A supercapacitor’s ideal electrolyte should device capable of achieving excellent Ed with substantial power
meet the following requirements: it should have a large potential delivery as required.[214] Furthermore, cobalt-based MOFs,
window, electrochemical stability, stability across a wide leveraging their distinctive features such as increased surface
temperature range, high ionic conductance, high viscosity, high area, copious porosity, exposed metal area, and Lewis’s acid–base
flashpoint, environmental friendliness, nonflammability, afford- interactions, have been explored as sulfur hosts or modified
ability, and chemical inertness to all other supercapacitor separators in lithium–sulfur BT systems.[215] This section
components except the electrodes. The operating voltage win- emphasizes various Co-based MOFs to meet diverse electro-
dows of supercapacitors based on aqueous, organic, and ionic chemical requirements, especially in the context of supercapaci-
liquid electrolytes are 1.0–1.3, 2.5–2.7, and 3.5–4.0 V, respec- tors and batteries positioning them as promising candidates for
tively. In general, liquid electrolytes are toxic, caustic, and expen- advanced electrochemical devices (Figure 25).
sive to package. The drawbacks of organic solvents include their
high cost, flammability, and toxicity. Conversely, solid-state or 8.1. Lithium-Ion Batteries
quasi-solid-state electrolytes have good cycle stability, high con-
ductivity, and strong mechanical properties. Solid-state gel poly- The growing interest in LIBs originates from their widespread
mer electrolytes are the most interested electrolytes due to their use in mobile electronics and electric vehicles. In the discharge
high ionic mobility, conductivity, flexibility, and adhesiveness. process, lithium is intercalated or alloyed in the anode material,
undergoing oxidation to form lithium ions. These lithium ions
then migrate from the anode toward the cathode. The reverse
7.3. Electrode Fabrication procedure occurs during charging. This fundamental body of
pioneering investigations has been dedicated to developing
In symmetric supercapacitors, ferrite offers balanced perfor- excellent-performance electrode substances for advanced LIBs.[215]
mance and simplified manufacturing for both electrodes. A crystalline porous structure plays a crucial role in mitigating
However, symmetric cells typically have lower energy density volumetric changes during the cycling process, thereby address-
compared to asymmetric cells due to the similar voltage ranges ing safety concerns. Notably, pristine Co-based MOF materials
and capacitance of both electrodes. Yang et al. created a flexible have emerged prominently in recent literature as anode material
supercapacitor and 3D Cu@CoFe2O4 composite on iron foam. of LIBs. To delve into specific achievements Hu’s study stands
This substance is porous and has a high surface volume ratio. out, where the Co-BDC MOF was synthesized using a simple
After 2000 cycles, it had an 87% cyclic stability. Its porous struc- solvothermal process.[216] This material demonstrated a notewor-
ture gave it a great capacity for storing ions, raising the super- thy reversible capacity of 1090 mAh g
1 at 200 mA g
1 after 100
capacitor value.[209] Maitra et al. studied the structure of cycles. Paramasivan et al. investigated new hierarchical porous
CoFe2O4 where the positive electrode grew on stained steel fabric cobalt-based MOFs. These MOFs have been synthesized at lower
and the negative electrode grew on a composite of NPs of iron temperatures, allowing to production of binder-free electrodes
oxide and graphene oxide sheets on stain-free steel fabric using for use in secondary LIBs.[217] The research discussed above
3 M KOH electrolyte. The maximum charging duration was highlights the outstanding application of cobalt-based metal
31 min for the BT when charging at 1.6 V. After 2000 cycles, MOF in LiBs. In 2024, Lakshmi et al. successfully created a
its stability was 97.1% and its capacitance was Co3O4/rGO composite by annealing after hydrothermal synthe-
155.8 Fg
1@1 Ag
1.[210] Asymmetric supercapacitor uses cobalt sis and then carefully examined the ECP as a potential anode sub-
ferrite for one electrode and a different material, like activated stance for LIBs as shown in Figure 26a. Electron mobility inside
carbon, for others. The configuration leverages the strengths the cell was greatly increased by the composite’s integration of
of each material, achieving higher energy density and enhanced GO sheets and Co3O4 microsheets. The Co3O4/rGO compound
performance. By combining cobalt ferrites pseudocapacitance demonstrates an outstanding specific discharge capacity of
with activated carbons high surface area and conductivity, the cell 1081 mAh g
1 at 100 mAh g
1, highlighting the remarkable
can operate over a broader voltage window and balanced high capability for ES. The Co3O4/rGO composite demonstrated
capacitance with power density. remarkable cyclic stability by retaining 81% of its capacity even

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Figure 25. Applications of cobalt-based composites in various ES systems.

after 400 cycles, demonstrating its potential for reliable and long- monometallic counterparts, have been successfully synthesized.
term ES. The Co3O4/rGO/CB composites were suitable for use A pristine MnCO-BTC2 exhibits exceptionally strong ECP in
in a lithium-ion capacitor and the results are shown in rechargeable LIBs. This performance is the feature of the positive
Figure 26b–d.[218] In 2018, Yu et al. presented a solution to influence of Co doping, which enhances interlayer diffusion,
the volume fluctuation challenge in lithiation and delithiation reduces polarization on migration barriers, and improves elec-
by introducing hierarchically structured Co3O4 carbon porous tronic conductivities.[223] Furthermore, the composite anode con-
fibers (Figure 26e). ES-CNCo3O4 demonstrated an initial dis- sisting of graphite and 15% Co-MOF exhibits significantly
charge and charge capacity of 1824 and 1003 mA hg
1, with improved reaction kinetics and enhanced ECP. A noteworthy
an initial columbic efficiency of 55% as shown in Figure 26f, example of crystalline cobalt-based MOF is the Prussian
g.[219] In 2017, Sun et al. employed a straightforward approach blue analogue.[224] In 2019, Wang et al. synthesized a
to craft a 3D starfish-like porous nitrogen coated with Co3O4. Co3O4@Co3S4 nanometer array using the hydrothermal method.
Co3O4@N–C nanocomposite electrode and demonstrated highly The composite structure exhibited a synergistic effect between
reversible specific capacity, achieving 795 mAh g
1at 0.5 Ag
1 Co3O4@Co3S4, significantly contributing to enhanced EC prop-
after 3000 cycles and exceptional rate capacity, reaching erties. Notably, initial Coulombic efficiency reached up to 82.5%,
1048 mAh g
1 at 1 Ag
1. The CV curves for Co3O4@N–C voltage surpassing other composite anodes based on cobalt or sulfide.
ranging from 0.0 to 0.3 V at 0.1 mV
1 and GCD curves for This achievement highlights the positive impact of combining
Co3O4@N–C between 0.1 and 3.0 V at Id are shown in Co3O4@Co3S4 in the nanometer array for ECP.[225] In 2019,
Figure 26h–k.[220] Likewise, bimetallic supercapacitors based Yao et al. presented a copper-modified Co3O4 nanometer sheet
on nickel and cobalt nitride/nitrogen-doped carbon hollow nano- using a microwave-assisted reaction followed by chemical reduc-
flowers are reported, which resulted in an acceptable SCs of tion. The resulting materials featured a porous sheet structure
1582 Fg
1 at 1 Ag
1.[221] with a width ranging from 100 to 300 nm and thickness of
Ganjali et al. developed a Co-MOF decorated with Sn NPs ≈20 nm. The introduction of copper in the structure served
through a solvothermal method. This modified material demon- the dual purpose of enhancing surface area, reducing solid dif-
strated excellent electrochemical properties when utilized as an fusion length, ensuring stability, and improving conductivity.[226]
anode in LIB, surpassing the performance of conventional graph- In 2017, Shi et al. introduced a novel structure featuring Sn–Co
ite anodes.[222] MnCo-BTC2 (BTC2 = 1,2,4,5-benzenetetracarbox- alloy embedded in porous N-doped carbon microboxes, demon-
ylate) with an Mn/Co atom ratio of 1.7:0.3, as opposed to its strating superior ECP as an anode substance for LIBs.

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Figure 26. a) CV at different scan rates of Co3O4/rGO/CB. b) GCD curves of various Id. c) Ragone plot’s inset shows lithium-ion cell. d) Co3O4/rGO/CB
cyclic stability at high current density (Reproduced with permission.[217] Copyright 2024, Springer). e) Preparation of ES-CNCo3O4 structural growth. f ) ES-
CNCo3O4 CV curves. g) ES-CNCo3O4 GCD voltage curves at 0.1 Ag
1 (Reproduced with permission.[218] Copyright 2013, Royal Society of Chemistry).
h) Co3O4@N–C CV curves voltage range from 0 to 3 V at a scan rate of 1 mV
1. i) GCD profile of Co3O4@N–[email protected] Ag
1current density. j) Cyclic stability
over 3000 cycles. k) Co3O4@N–C rate capability test at different current densities (Reproduced with permission.[219] Copyright 2017, Springer).

Sn–Co@C
2 electrode exhibited the highest specific capacity excellent reversibility and remarkable cyclic stability, retaining
across different Id at 0.1–2 Ag
1, highlighting an excellent rate 82% of its capacity after 5000 cycles at 5 Ag
1. This exceptional
of performance. Additionally, the electrode showed remarkable performance is attained due to the unique architecture of the
capacity retention Id at 0.1 Ag
1. Ex situ analysis revealed the electrode.[91]
disappearance of CoSn2 after the first cycle, while the CoSn
phase remained stable even after 100 cycles, indicating favorable 8.2. Supercapacitors
reversibility of the Sn–Co@C
2 electrode.[227] The constructed
supercapacitors device exhibited notable ECP, characterized by Supercapacitors, in general, have gained attention as an ES
impressive areal capacitance of 35 mF cm
2 and outstanding technology that complements traditional batteries.[229]
Pd of 0.833 W cm
3 at 0.05 mA cm
2. Impressively greater than Supercapacitors, also known as electrochemical capacitors/ultra-
80% of its original capacitance was retained even after 2000 capacitors, represent sustainable and efficient energy technology
cycles marking the highest values achieved for MOFs-based that has garnered substantial attention within the last 20 years.
supercapacitors to date. The enhanced ECP of MOF composite, This enthusiasm is driven by their notable features, including
compared to bare MOFs, was attributed to higher electrical outstanding Pd, affordable, broad operating temperature ranges,
conductivity and a well-distributed pore size. Specifically, a and an exceptionally long cyclic life. The ESDs are broadly clas-
Co–MOF/PANI substance, utilizing 1,3,5-benzene tricarboxylic sified into two types based on their charge storage methods:
acid as the origin ligand, was synthesized. This substance exhib- EDLCs and PCs.[221] The conventional supercapacitors or
its a Cs of 504 Fg
1 at 1 Ag
1 and maintains 90% of its original EDLCs store electric energy through the creation of an ionic
capacitance even after 5000 subsequent discharge and charge double layer, known as double-layer capacitance, on interior sur-
cycles.[228] In 2017, Kong et al. successfully produced freestand- faces. Importantly, this process occurs through non-Faradic
ing Co3O4 nanoflakes on Ni foam through a combined method mechanisms, meaning there are no significant chemical
involving electrochemical, an in situ chemical reaction, and reactions involved at the electrode–electrolyte interface.[229]
calcination. The resulting electrode demonstrates an excellent While EDLCs boast of high power density, facilitating rapid
specific capacity of 576.8 Cg
1 at 1 Ag
1. Additionally, it exhibits charge and discharge cycles, they are noted for their relatively

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low energy density. This characteristic highlights a trade-off in Figure 27j represents the fabrication of the device schematic
the storage capacity of these devices compared to some alterna- illustration. The SCs, calculated from GCD plots at Id of 1, 2,
tive ES technologies.[230] Originally limited to routine uses like 4, 6, 8@1 Ag
1, were found to be 102.5, 96.5, 93.5, 87, 78, and
safeguarding memory and providing internal batteries, superca- 68 Fg
1, and CV plots at 200 mV s
1 reveal a symmetric rectan-
pacitors have, in recent years, seen a substantial expansion in gular shape, indicating good conductivity respectively as shown
their application. They are now widely utilized in diverse areas, in Figure 27k,l. Additionally, the symmetrical supercapacitor
including smartphones, energy harvesting, and hybrid vehicles. achieved a high Ed of 57.5 Wh kg
1. At Pd of 10 kW kg
1, energy
Anticipated advancements on the technological horizon suggest density remained substantial at around 37.9 Wh kg
1. The sym-
that supercapacitors are poised to compete extensively with metric supercapacitor of LED is shown in Figure 27m,n.[236]
rechargeable batteries, potentially revolutionizing their role in Lio et al. merged vertically aligned graphene nanosheets with
various industries. Numerous studies have explored the carbon fabric through a hydrothermal technique. This compos-
enhancements of metal oxide performance by combining it with ite, serving as backbone and current collector, was utilized to con-
Co3O4. For instance, Bhupender et al. utilized pyrolysis to create struct an supercapacitor electrode incorporating Co3O4 NPs as
porous carbon from palm kernel shells. Subsequently, they shown in Figure 28a. As a result, composites with notably high
employed a reflux method to introduce SnO2/Co3P4 composites Cs of 2480 Fg
1, closely approaching the theoretical value of
into the pores. This material design, with its enlarged surface 3560 Fg
1, demonstrated suitability for various bending angles
area, facilitates reactions.[231] Furthermore, research is extended and exhibited exceptional performance, comprising increased
to ternary composite metal oxides and ternary composite nano- Cs of 580 Fg
1, robust cycling ability with 86.2% capacitance
metal oxides. Xue et al. employed a straightforward solvent hot retention, subsequent 20 000 cycles, an increased Ed of
preparation method to create a novel zinc–nickel–cobalt trioxide 80 Wh kg
1, and excellent Pd of 20 kW kg
1 at 27 Wh kg
1, as
nanofilm. Remarkably, even after 2000 cycles, the Cs remained at represented in Figure 28b–d. This underscores the significant
an impressive rate of 97.18%, Id of 1 Ag
1, and the substance potential of the device exploration in energy management for
exhibited a capacitance of 200 Fg
1.[232] In 2017, Sun et al. syn- flexible and lightweight electronic products as shown in
thesized Co3O4 nanosubstance by annealing directly at 450 °C Figure 28e,f.[237] Li et al. effectively synthesized Ni/Co–LDH
with a Co-based zeolite imide salt skeleton initially. In the nanosheets array in situ on different substrates using a mini-
KOH electrolyte, when Id was 1 Ag
1, Cs was 706 Fg
1, and the mum temperature chemical coprecipitation technique as shown
stability was 71.5%.[233] Enhancing the Cs and Ed of Zn–Co in Figure 28g. They assembled an all-solid-state ASC, employing
oxide-based substance is crucial for achieving outstanding LDH arrays as the positive electrode and activated carbon as the
ECP in supercapacitors. Copper-doped zinc cobalt oxide negative substance. The calculated Ed for this asymmetric capac-
(Zn1
xCuxCu2O4) synthesized by hydrothermal method itor is 141.03 Wh Kg
1, with a Pd of 1.17 kW kg
1. Notably, with
achieved superior super capacitive performance. Notably, the an increased Pd of 20.52 kW kg
1, the energy density remains
introduction of copper into ZnCo2O4 resulted in a twofold high substantial at 56.99 Wh kg
1; the device exhibits outstanding
specific area of 52 m2 g
1 and reduction in charge transfer resis- cyclic stability, as the capacitance retention rate subsequent to
tance for the (Zn0.7Cu0.3Cu2O4) (x = 0.3) material. Copper-doped 1000 CV test is greater than 89.6% of the original capacitance
Zn0.7Cu0.3Cu2O4 electrode exhibited excellent Cs of 1425 Fg
1, range.[238] Yang et al. conducted the direct growth of a new
representing a 1.55-fold increase compared to the 917 Fg
1 Ni–Co hydroxide 3D nanostructure (3D CGNC) on the surface
observed in the pristine ZnCo2O4 electrode. Remarkably, the of Ni foam using an electrochemical deposition technique.
Zn0.7Cu0.3Cu2O4 maintained 96% of its capacitance after 2000 The assembled ASC was constructed with 3D CGNC serving
charge and discharge cycles. Furthermore, Zn0.7Cu0.3Cu2O4 as the cathode and conventional ketjen black as the anode.
featuring a potential window of 1.5 V and enhanced cyclic stabil- The CV plots revealed a symmetric rectangular shape, indicating
ity is represented in Figure 27a. The assembled device demon- excellent conductivity. According to GCD plots, the maximum
strated an outstanding Pd of 55 Wh kg
1 and effectively Cs is 332 Fg
1. Even under a high Id condition of 100 Ag
1,
illuminated yellow light emitting diode (LED) with a voltage of the Cs remains substantial at 187 Fg
1, showcasing excellent rate
1.5 V, as represented in Figure 27b–e.[234] Hu et al. employed stability. The asymmetric supercapacitor achieved a maximum
a two-step hydrothermal process and intermittent annealing to Ed of 103 Wh kg
1 with a corresponding Pd, as represented in
fabricate the 3D array of Co3O4@NiO core–shell nanowires sup- Figure 28h–k.[239]
ported on Ni foam, as shown in Figure 27f. These nanowire Gong et al. developed novel vertical array of CuSe@Co(OH)2
arrays were utilized as both anodic and cathodic electrodes in nanosheets and utilized them to assemble a flexible solid ASC as
a symmetric supercapacitor. The CV curves in Figure 27g exhibit shown in Figure 29a. In this configuration, CuSe@Co(OH)2
a well-defined rectangular structure at different scan rates, nanosheets array serves as the positive electrode, while activated
indicating efficient charge and electrolyte ion transferability. carbon acts as the negative electrode. ASC with the outstanding
At an Id of 1 Ag
1, the Cs of 720.71 Fg
1 is shown in Figure 27h; results of CV in Figure 29b indicating effective conductivity, and
additionally, the symmetric supercapacitor achieves a maximum GCD of 1180 Fg
1 in Figure 29c. At an Id of 0.3 mA cm
2,
Ed of 196 Wh kg
1, with a corresponding Pd of 0.7 kW kg
1. the device exhibits a high-volume Ed of 0.17 mWh cm
3 in
Figure 27i shows LED demonstration of ASC.[235] Zhang et al. Figure 29e. This result of the fabricated device was assessed
systematically fabricated a hybrid compressing Co–ferrite under a current density of 1 A cm
2, while the parallel combina-
PB-Co/rGOH through a one-step hydrothermal method. The tion of devices was evaluated under a current density of
resultant PB–Co0.3/rGOH was employed as an electrode in a 2 mA cm
2, highlighting its potential for use in flexible and
symmetric supercapacitor and its ECP was thoroughly examined. high-performance ES through demonstration of light emitting

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Figure 27. a) Fabrication of device’s schematic illustration. b) CV plots of symmetric CZCo2 at various scan rates. c) GCD plots of symmetric CZCo2 at
different Id. d) Cyclic stability of CZCo2. e) Fabrication symmetric device lighting through LED demonstration (Reproduced with permission.[234] Copyright
2020, American Chemical Society). f ) Schematic representation of Co3O4@NiO core–shell nanocomposites. g) CV plots on nickel foam Co3O4@NiO
and Co3O4 at scan rate 50 mV s
1. h) GCD plots of Co3O4@NiO at 1 Ag
1. i) Co3O4@NiO demonstration through LED (Reproduced with
permission.[235] Copyright 2016, Elsevier). j) Symmetric representation of arranged FSSC device. k) CV curves at various scan rates. l) GCD curves
at various current density. m) Cyclic stability for 10 000 GCD curves at 4 Ag
1. n) LED powered by symmetric constructed electrode (Reproduced with
permission.[236] Copyright 2018, Elsevier).

diode (LED), as shown in the inset of Figure 29d.[240] Subramani activated carbon electrode at 5 Ag
1 showcasing low resistance as
et al. synthesized the crystalline hexagonal dumb-bell-shaped represented in Figure 29g,h. Furthermore, both CoS and AC
CoS NPs demonstrated through the solvothermal decomposition electrodes demonstrated suitable potential windows for use as
of CoHCF complex and dumb-bell-shaped structure with sizes negative and positive electrodes in ASC. The fabricated flexible
ranging from 10 to 20 nm. Figure 29f represents the fabrication all solid-state ASC cell achieved a maximum cell voltage of 1.8 V,
of material. Electrochemical studies in the three-electrode config- delivering excellent Ed and Pd of 5.3 Wh kg
1 and 1800 W kg
1,
uration exhibited a Cs of 307 Fg
1 for CoS NPs and 60 Fg
1 for respectively, at a current density of 5 Ag
1. Notably, the ASC cell

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Figure 28. a) Schematic illustration of fabrication procedure. b) CV plots at various bend angles. c) GCD plots. d) Cyclic performance of device@20 Ag
1
inset GCD curves for ten cycles. e,f ) Demonstration of the glow of LED and flexibility of device (Reproduced with permission.[237] Copyright 2015,
American Chemical Society). g) Representation of formation mechanics of asymmetric supercapacitor. h) CV plots at various sweep rates,
i) comparison of rate performance. j) GCD plots at different current densities. k) Representation of cyclic stability inset GCD curves for ASCs
(Reproduced with permission.[239] Copyright 2015, Springer).

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Figure 29. a) Systemic representation asymmetric of the SCs. b) GCD curves at different current densities. c) CV plots at various sweep rates. d) SCs
(inset demonstration of LED). e) Representation current density (Reproduced with permission.[240] Copyright 2018, American Chemical Society). f ) Solid-
state asymmetric fabrication of device. g) CV plots at various sweep rates. h) GCD plots at different current densities. i) Capacitive retention and
Coulombic efficiency. j) Cyclic stability with inset LED demonstration (Reproduced with permission.[241] Copyright 2017, Royal Society of
Chemistry). k) Symmetric illustration of fabrication of ASC. l) CV plots at various scan rates. m) GCD plots at different current densities. n) Energy
density of various works. o) Cyclic stability with inset LED demonstration (Reproduced with permission.[242] Copyright 2018, Royal Society of Chemistry).

exhibited outstanding electrochemical stability, retaining 92% of mesoporous hollow sphere and graphene oxide fabrication, as
its performance even after 5000 cycles at Id of 10 Ag
1, as rep- shown in Figure 29k. The unique structure of the hybrid films
resented in Figure 29i,j.[241] In 2018, Sun et al. synthesized a provides more pathways for electrolyte transmission, resulting in
hybrid flimsy, consisting of a carbon/Co3O4 composite excellent ECP. The specific capacity of individual C/Co3O4 is

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153.9 Fg
1 and rGO films are 213.5 Fg
1 significantly more than onto CNTs using the sonochemical technique. PANI, a more
hybrid films achieving a Cs of 1266.0 Fg
1 at Id of 1 Ag
1. When pseudocapacitive substance, acted as a bridge between CNTs and
designed as ASC, it exhibits excellent Ed of 32.7 Wh kg
1, Pd of metal phosphate. Results showed Cs of 1410 Fg
1 at 0.8 Ag
1,
800 W kg
1, and high cyclic stability with 85.9% capacitance exceptional Ed of 88.5 Wh kg
1 without compromising Pd, and
retention after 5000 cycles; the CV at 2 mV s
1 scan rate and the highest value of 900 W kg
1 at 0.8 Ag
1. Nanocomposite is
GCD at different voltage windows are shown in Figure 29l–o.[242] highly suitable for potential asymmetric supercapacitor
In 2020, Gao et al. synthesized cobalt ferrite on the nickel applications due to its strong chemical bonding and ECP.
foam. By adding other template agents to alter the material’s Even after 5000 GCD cycles, the device still exhibits exceptional
structure, CoFe2O4 electrochemical characteristics can be further Coulombic efficiency (99.7%) and cyclic performance (100.11%).
enhanced. The CoFe2O4 materials’ physicochemical characteris- This nanocomposite also has a unique feature even after 5000
tics were investigated using XRD, N2 absorption–desorption, cycles, the stable chemical grafting maintained outstanding
SEM, and XPS. CV and GCD plots indicate that the respective structural stability and excellent rate (99%) following circulation
capacities of CFO-A, CFO-S, CFO-P, and CFO-C are 696.4, at an increased Id of 10 Ag
1.[248] Hydrothermal-assisted electro-
1342.2, 827.9, 1099.6, and 1148.3 Fg
1. The following charging deposition was used to create a binderless SC electrode employ-
and discharging cycles, at 2000, and the electrode specific reten- ing CoO and PANI. Several characterization methods validated
tion ratios at current densities of 10 Ag
1 were 84.1, 87.3, 64.7, the conductive PANI’s unidirectional growth on CoO. Since the
91.4, and 77.0%. Its retention rate is 56% at an Id of 10 Ag
1, and combined effects of BT-type CoO and pseudocapacitive PANI,
its Ed is 55.42 Wh kg
1.[243] An essential component of electronic the electrode demonstrated outstanding ECP, including excellent
textiles is flexible electrodes with high energy and deformability. specific capacity of 1113 C g
1 and cycling stability of 86.3% over
Ni–Co NPs (Ni–Co@PS) have been produced and applied to the 10 000 charging/discharging cycles.[249] In 2019, microporous
surface of polyaniline salphen. This nanocomposite demon- carbon-supported Co3O4 (C–Co3O4) NPs with a fine size of
strated great tolerability, a wide surface area, and outstanding ≈6 nm in diameter demonstrated a maximum Cs of 221 Fg
1,
behavior. The optimized composite, created with a 3:1 w w
1 Ed of 8.11 Wh kg
1 at Pd of 800 W kg
1, a retention rate of
Ni:Co metal ratio, has SCs of up to 549.994 Cg
1 (1447.2 Fg
1) 70.63%, and SCs over 8000 cycles.[250] The Co3O4@CoS/CC
for 0.5 Ag
1 and exhibits long-term cycling stability with 95.5% composite was synthesized through a multistep process involv-
capacity retention subsequent to 5000 cycles at Id of 9.0 Ag
1.[244] ing four cycles of CoS deposition, at relatively low scan rate of
In 2023, Gao et al. utilized the cobalt–iron MOF as the precursor 10 mV s
1. The composite exhibited a notably excellent capaci-
to create the Co–Fe–P@NiCo LDH core–shell nanostructure on tance of 887.5 Fg
1 and demonstrated impressive cycling stability
conductive Ni foam. When poly(vinyl pyrrolidone) is modulated, after undergoing 5000 charge and discharge cycles at a substantial
the morphology changes from 3D to 1D. Utilizing the substantial Id of 5.0 Ag
1 aiming for cooperative effects that led to improved
area of NiCoLDH nanosheets as the shell and the high electrochemical properties.[93] A multistage approach is used to
conductivity of Co–Fe–P nanowire as the core, the fabricated create the multilevel NiCo2O4@Co3S4@MnS@PPy core sheath
Co–Fe–P@NiCoLDH/NF electrode demonstrates exceptional nanowires on carbon cloth. Exhibiting excellent Cs of 2.67 Fcm
2
electrochemical properties, including an outstanding rate capa- at 1 mA cm
2 (2.557.58 Fg
1 at 1 Ag
1) and exceptional cyclic
bility (78.59% from 1 to 20 mA cm
2) and a specific capacity stability (83.64% capacitance retention after 20 000 cycles at
of 5.67 C cm
2 at Id of 1 mA cm
2. Additionally, it showed an 20 mA cm
2), the obtained electrode material was distinguished
exceptional cyclic life expectancy of 91.67% over 5000 cycle tests because of its electrochemical characteristics. For the ECP of
under 20 mA cm
2 and an impressive density of energy of supercapacitors, a designed three-step process for creating a
0.164 mWh cm
2.[245] In 2023, Ghahfarokhi et al. used in situ CP film coated on porous nanoflakes like NiCo2O4 was used.
polymerization to synthesize CoMnFeO4/PANI nanocomposite After the fabrication of the NiCo2O4@Co3S4@MnS@PPy
NPs with an outstanding performance as electrode substance. asymmetric device, the potential window was further expanded
Results showed excellent Cs of 1610 Fg
1 at Id of 1 Ag
1 and to 1.5 V. The obtained values of SCs increased to 406 Fg
1
capacitance retention was nearly 100% after 600 cycles at the and energy and power densities increased to 60.60 Wh kg
1 and
Id of 20 Ag
1.[122] In 2019, Deyab et al. studied the electrochemi- 2322 W kg
1, respectively.[251] In 2023, Li et al. constructed
cal stability of the supercapacitors, which was significantly CC/PCN electrode where the migration of PANI volume expan-
enhanced by the addition of Co-porphyrins NPs to polyaniline. sion during charging and discharging led to enhanced cycle
The resulting composite electrode had an exceptionally high performance, as Co2þ and Ni2þ work together to coordinate
Cs value of 823 Fg
1 at 1 Fg
1, but the Cs value decreased as the response within and between PANI’s chains. After 5000 cycles
it reached 560 Fg
1. At higher Id values above 20 Ag
1, subse- at 5 Ag
1, the supercapacitor retains 85.9% of its capacitance,
quent 1000 cycles, the capacitance retentions remained at over with a Cs of 131.8 Fg
1 at 1 Ag
1. When the supercapacitor
91%. It ended in ideal Ed and Pd between 41 and 27 Wh Kg
1 was powered at 799.89 W kg
1, it had an Ed of 46.86 Wh kg
1.[252]
and 150 and 5856 W Kg
1, respectively.[246] Using an optimum In 2023, Xia et al. fabricated a high-energy supercapacitor cell
set of experimental conditions, chemical oxidation was used to made of graphene nanoribbons and CoFe2O4 and employed as
produce both pure and Pr-doped CoFe2O4 magnetic NPs, where the electrode active substance. In a typical three-electrode setup,
5% Pr-doped CoFe2O4 MNPs had the highest Cs of 121 Fg
1 at Id the CoFe2O4/rGRs nanohybrid provided an extraordinary Cs of
of 1 Ag
1. Cyclic stability was utilized to evaluate the capacity 922 Fg
1 at 1.0 Ag
1 in 3 M KOH electrolyte. At the 10 000 cycles,
retention, and the results indicated that even after 5000 cycles this showed 87% capacitance retention and excellent cycle
CoFe2O4 MNP electrode maintained more than 97% of its origi- stability. The Ed and Pd values for this current density value were
nal capacity.[247] In 2024, Shehzad et al. grafted ZCP and PANI obtained 132.8 Wh kg
1 and 632.39 W kg
1, at 10 Ag
1, the

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maximum power of 6730.76 W kg
1 was obtained and at 9. Conclusion and Future Perspectives
this current density, the energy density, was found to be
8.75 Wh kg
1.[253] In 2024, Muhammad et al. synthesized The exceptional performance of supercapacitors is an obvious
NiCo2S4/g-C3N4/PANI exhibiting excellent Cs of 1799.07 Fg
1 choice to address the world energy issues of the present and
up to 90% retention over 2700 cycles at Id of 2 mA cm
2 where the future. Cobalt-based materials possessing an energy density
the electrode demonstrates the excellent potential for ESDs.[254] superior to a lot of its family members, favorable power density,
An unbound synthesized ternary compound electrode via layer exceptional cycle stability, high capacitance, and adequate
by layer process showed excellent Cs of 1206 Fg
1 at 5 mV s
1 multiplier capability could be created by modifying the parts
sweep rates with the potential window of 0.5 V at electrolyte and structure through various synthesis methods. The primary
6 M KOH and with 94% retention for 10 000 cycles. The obtained contribution of this review is extensive categorization and
Ed is 51.1 Wh kg
1 and Id is 4959.6 W kg
1 representing excel- assessment of electrochemical storage system applications.
lent supercapacitor behavior demonstrated through the LED The cobalt-based various ferrites which include Cu, Zn, Ni, silica,
glow of different colors, and the device withstood the flexibility lanthanum, and CdS refining the excellent ECP of composites
up to 180° even after two months of fabrication.[255] Table 9 are overviewed through cyclic CV, GCD, and LSV offering valu-
summarizes the recent progress in Co-based composites in able insights into future research directions for material design.
EES systems. Moreover, nonferrite-based materials amalgamated with cobalt

Table 9. Recent progress in co-based composites in EES systems.

Composition SCs value [Fg
1] Energy density [Wh kg
1] Power density [W kg
1] Cyclic stability and retention References
NF/C-Co3O4/PPy 695 at 0.5 Ag
1 35.2 Wh kg
1 1100 W kg
1 93% retention for 8000 cycles [250]

1
1
1
CP/f- Co3O4/PPy 398 at 1 Ag 18.4 Wh kg 2900 W kg 100% retention for 1000 cycles [358]
CoN4-PPy 721.9 at 5 mVs
1 – – 93% retention for 500 cycles [410]
NiCo2S2@PPy/NF 2554.9 Fg
1 at 2.54 Ag
1 35.17 Wh kg
1 1472 W kg
1 92% retention for 10 000 cycles [359]
ZnCo-MOF/PPy/Ag2O Ternary composites 148 Fg
1 at 1 Ag
1 33.34 Wh kg
1 500.1 W kg
1 84.5% retention for 10 000 cycles [411]

1
1
1
1
NiCo2O4/rGO/PPy 1547 Fg at 0.5 Ag 34.37 Wh kg 99.98 W kg 94.1% retention 5000 cycles [412]
PPy/cobalt oxyhydroxide/cellulose 571 at 0.2 Ag
1 – – 93.02% retention 1000 cycles [413]
fiber composite electrode
Ni–Co–Mn/PCG-40 380 Cg
1 at 0.7 Ag
1 90 Wh kg
1 1700 W kg
1 100% retention for 5000 cycles [414]

1
1
Ni–Co@PANI 1447.2 at 0.5 Ag 800 Wh kg 23.46 W kg
1 95.9% retention for 5000 cycles [248]
3D nanoflakes PANI/NiCo2O4/CF 406 at 5 mA cm
2 60.60 Wh kg
1 2322 W kg
1 94% retention for 5000 [247]
ZCP/PANI/CNT//AC 1410 at 0.8 Ag
1 88.5 Wh kg
1 900 W kg
1 100.11% retention 5000 cycles [415]

1
1
1
1
Co(OH)2@PANI 385 Fg at 1 Ag 31.2 Wh kg 1050 W kg 74.8% retention 5000 cycles [416]
PCN//MXene 131 Fg
1 at 1 Ag
1 799.89 46.86 W kg
1 85.9% retention 5000 cycles [251]
Co0.70(PO4)2/PANI0.30 638 Cg
1 at 0.8 Ag
1 53.2 Wh kg
1 432 W kg
1 87% retention 5000 cycles [417]
PANI/CoSe2/NF 1980 Fg
1 at 2 Ag
1 118 Wh kg
1 – 82% retention 10 000 cycles [418]

1
1
1
1
CCHH/PANI 1308.4 Fg at 1 Ag 35.1 Wh kg 548.24 W kg 97.2% retention 5,000 cycles [419]
CNP2 2473 Fg
1 at 3 Ag
1 35.8 Wh kg
1 – 86.3% retention 10 000 cycles [249]
CoWO4/PANI 653 Fg
1 at 5 mVs
1 32.1 Wh kg
1 – 93.3% retention 5000 cycles [420]
NiCo2O4/rGO/PANI 296 Fg
1 at 10 mVs
1 – – 99% retention 500 cycles [421]

1
1
1
1
MgCo2O4@Ppy//AC 988 Fg at 5 Ag 40 Wh kg 1544 W kg 84% retention 10 000 cycles [422]
Sr(OH)2/CoO(OH)/MnO2 1206 Fg
1 at 5 mVs
1 51.1 Wh kg
1 4959.6 W kg
1 83% retention 10 000 cycles [255]
NiCo2S4/g-C3N4/PANI 1799.07 Fg
1 at 2 mVs
1 32.6 Wh kg
1 – 90% retention 2700 cycles [254]
PPy/FeO@CVO 1202 Fg
1 at 1 Ag
1 38.2 Wh kg
1 700 W kg
1 95% retention 5000 cycles [423]

1
1
1
1
CoFe-LDH/P 1686 Fg at 1 mVs 75.9 Wh kg 1124 W kg 97.5% retention 10 000 cycles [424]
CoS2/PPy 605.2 Cg
1 at 1 Ag
1 88.07 Wh kg
1 4.95 kW kg
1 90.9% retention 5000 cycles [425]
PPy@CoS 860 Cg
1 at 20 Ag
1 51.1 Wh kg
1 800 W kg
1 92% retention 5000 cycles [426]
CuCo2S4@NMWCNT/PPy 259 Fg
1 at 1 Ag
1 28 Wh kg
1 – 90.5% retention 5000 cycles [427]

1
1
1
1
CoNb/CNT/CNT/PANI 150 Cg at 1 Ag 28.9 Wh kg 1020 W kg 80% retention 2000 cycles [428]
PPy-NCS@Ni@SiNWs 1348 Fg
1 at 30 Ag
1 131.322 Wh kg
1 1.44 kW kg
1 91.6% retention 10 000 cycles [429]
PPy@Co(OH)2 277 mAhg
1 at 2 Ag
1 54.4 Wh kg
1 800 W kg
1 92% retention 5000 cycles [430]
PANI-CoM/OMC 278 Fg
1 at 1 Ag
1 22 Wh kg
1 400 W kg
1 – [431]

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are reviewed, among which are MOF, silica, LDH, etc. When it where Co-based materials play the key role. In addition to the
comes to address the applications, the criteria that need to be aforementioned features, carbon emission reduction strategies
understand for Co-based supercapacitors and batteries are as fol- in ES systems include adopting sustainable manufacturing
lows. 1) A deep understanding of cobalt ferrite-based ES mecha- practices, increasing recycling rates, and transitioning to
nism, particularly the interfacial reaction between electrolyte and carbon-neutral energy sources for charging. The development
electrode, is needed. 2) Tailoring cobalt ferrite electrode design to of cobalt-based ES systems faces significant hurdles, including
form hierarchical porous microstructures enhances ion diffusion high cost and limited supply of cobalt, environmental and social
and electron transport, enhancing active surface area and concerns related to mining, limited recyclability, and safety con-
improving cyclic stability. 3) Precise control over interfacial inter- cerns due to thermal runaway.
actions in cobalt ferrite system, promoting favorable electro- Strategies to address these challenges would be developing
chemical reactions and enhancing structural stability, through and implementing sustainable and responsible mining practices,
the strategic synthesis methods, is studied. designing and scaling up the efficient recycling process for
It is important to note that by 2030, research has indicated that Co-based ES systems in pursue of establishing stringent safety
a cobalt supply shortfall may materialize as early. To address this standards and regulations. Finally, most important supporting
issue, the potential solutions include exploring alternative sub- research and development for new ES technologies with reduced
stances such as different ferrites, TMO, and metal oxide frame- environmental footprints is necessary.
works with favorable performance. Additionally, there is a need
to advance more efficient, cost-effective, and convenient recy-
cling technologies for supercapacitors and batteries. Future Acknowledgements
research should supervise all relevant elements to develop ideal
S.C. acknowledges the B.M.S. College of Engineering, Bengaluru, for
systems and achieve higher performance including the follow- financial support vide project no. R&D/FRPS/2023-24/PHY/01.
ing. 1) Innovative manufacturing techniques are essential for cre-
ating highly porous materials with hollow structures, enabling
enhanced charge storage and increased energy density. 2) To Conflict of Interest
boost energy density, electrode material must be complemented
by stable electrolytes with wide potential windows and high ionic The authors declare no conflict of interest.
conductivity. 3) Compatibility between pore size and ion size
should be optimized to maximize the utilization of the electrode
material. 4) Issues such as operating temperature range, self- Author Contributions
discharge rate, and stability of ES systems should be addressed. Jyothi A. Goudar: writing—original draft, formal analysis. Thrinethra S. N.:
5) The advanced supercapacitors, which offer high energy den- writing—original draft. Sharanappa Chapi: writing—original draft, concep-
sity, and power density simultaneously, aligning with growing tualization, validation, resources, writing—review & editing, supervision.
demands for ES systems, should be emphasized. Murugendrappa M. V.: conceptualization, resources, writing—review &
The use of Co-based energy materials and devices for flexible editing, visualization, supervision, Mohammad Reza Saeb: writing—
review & editing. Mehdi Salami-Kalajahi: writing—review & editing,
electronics and wearable devices should also be mentioned supervision.
herein, as this is an important future development direction.
For instance, an essential component of electronic textiles is flex-
ible electrodes with a high energy and deformability. For energy
management, flexible and lightweight electronic products are of Keywords
particular interest, such that specifications like cyclic stability and
cobalt ferrites, cobalt-based materials, energy storage, lithium-ion
porosity can be gained.[256] For example, development of super- batteries, supercapacitors
foldable materials with conductivity and biomimetic features
capable of folding for 1 000 000 times without structural damage Received: August 28, 2024
and conductivity loss should specifically be outlined.[257] Flexible Revised: November 12, 2024
supercapacitors based on Co-doped NiMoO4 nanosheets is Published online: December 1, 2024
another example of soft electronics applications of Co.[258]
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Jyothi A. Goudar is currently a Ph.D. candidate at Mangalore University, under the guidance of Dr.
Murugendrappa M V. She Holds a Master’s in Physics (2020) from Mysore University. Her research
interests are focused on the development of ferrite-based materials and polymer composites for energy
storage devices, particularly supercapacitors and batteries. She works on enhancing the performance of
supercapacitors using metal ferrites, with the goal of advancing energy storage technologies. Her work
aims to contribute to the development of more efficient and durable materials for next-generation energy
storage solutions.

Thrinethra S. N. is a Ph.D. candidate at Visvesvaraya Technological University (VTU) Belagavi, under the
guidance of Dr. Sharanappa Chapi. Holding a Master’s degree in Physics with a specialization in Solid
State Physics from Tumkur University (2018), she is dedicated to developing advanced polymer
composites for energy storage devices. Her research explores the development of high-performance
polymer composites for energy storage applications, focusing on enhancing the electrochemical
properties and efficient energy storage solutions.

Sharanappa Chapi is an assistant professor in the Dept. of Physics at B.M.S. College of Engineering,
Bengaluru, Karnataka. His research includes solid-state physics, materials science, polymer science &
engineering, energy storage devices, radiation effects, and thin films. He holds a Ph.D. in condensed
matter physics and polymer science from Mangalore University in 2016 and M.Sc. in solid-state physics
from Karnatak University, Dharward, in 2012. With 50 journal publications, 38 conference papers, 4
authored books, and 16 book chapters, he is a renowned expert in his field, contributing impactful
reviews in prestigious journals.

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Murugendrappa M. V. is an associate professor at BMS College of Engineering, Bengaluru, with a strong

background in conducting polymer composites and holds a Ph.D. in polymer composite materials and
gold medal for his masters in physics (1998). He has 75 publications in prestigious journals and 48
conference papers. With over 23 years of teaching and research experience, he is a principal investigator
for the TEQIP-funded “Centre for Excellence in Advanced Materials Research.” Under his guidance, 5
Ph.D. and 8 M.Phil. students have completed their degrees, and 4 Ph.D. students are currently working
under supervision.

Mohammad Reza Saeb is a University Professor at Department of Pharmaceutical Chemistry, Medical

University of Gdańsk, Poland. He is 1% Scientist of Materials Science and Chemistry as well (Essential
Web of Science). His research focus is on exploration and mechanistic interpretation of the relationship
between the microstructure, properties, processing/manufacturing and performance of materials,
particularly polymers, polymer blends, and polymer nanocomposites. He conceptualized two universal
dimensionless indices, namely “Cure Index” and “Flame Retardancy Index”, for qualitative cat of polymer
composites and nanocomposites in terms of crosslinking and flame retardancy performance, respectively.
He is editor-in-chief of “Polymers from Renewable Resources”.

Mehdi Salami-Kalajahi received his B.S., M.S., and Ph.D. in polymer engineering from Amirkabir
University of Technology, Tehran, Iran, in 2005, 2007, and 2011. He is a professor at Sahand University
of Technology, Tabriz, Iran, with research interests in polymer chemistry, sensors, and energy storage.
Prof. Salami-Kalajahi received the 2011 Superior Ph.D. Student of Iran Award and the 2017 Superior
Iranian Young Scientist of Chemical Engineering Award. He is a member of several scientific societies
and the National Elites Foundation of Iran. He is 1% Scientist of Chemistry (Essential Web of Science).

Adv. Energy Sustainability Res. 2025, 6, 2400271 2400271 (61 of 61) © 2024 The Author(s). Advanced Energy and Sustainability Research
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