Received: 23 February 2023 | Revised: 26 April 2023 | Accepted: 30 April 2023

DOI: 10.1002/bte2.20230010

REVIEW

Highly textured and crystalline materials for rechargeable

Li‐ion batteries

Min‐Ju Choi1 | Ji Hyun Baek1 | Jae Young Kim1 | Ho Won Jang1,2

1
Department of Materials Science and
Engineering, Research Institute of Abstract
Advanced Materials, Seoul National To build an environment‐friendly energy‐based society, it is important to
University, Seoul, Korea
2
develop stable and high‐performance batteries as an energy storage
Advanced Institute of Convergence
Technology, Seoul National University, system. However, there are still unresolved challenges associated with
Suwon, Korea safety issues, slow kinetics, and lifetime. To overcome these problems, it is
essential to understand the battery systems including cathode, electrolyte,
Correspondence
Ho Won Jang, Advanced Institute of and anode. Using a well‐controlled material system such as epitaxial
Convergence Technology, Seoul National films, textured films, and single crystals can be a powerful strategy to
University, Suwon 16229, Korea.
investigate the relationship between microstructural and electrochemical
Email: [email protected]
properties. In this review, we discuss the need for research with well‐
Funding information controlled materials system and recent progress in the well‐controlled
National Research Foundation of Korea
cathode, solid‐state‐electrolyte, and anode materials for Li‐ion batteries.
(NRF) grant funded by the Korea
government Ministry of Science and ICT Enhanced stability and electrochemical performance due to the facilita-
(MSIT), Grant/Award Number: tion of prolonged and endured Li‐ion transport in facet‐controlled battery
2018M3D1A1058793; Nuclear Energy
R&D Program (The National Research
materials are highlighted. Finally, the challenges and future directions
Foundation of Korea), utilizing the well‐controlled battery system for high‐performance battery
Grant/Award Number: are proposed.
2020M2D8A2069830; KRISS (Korea
Research Institute of Standards and
KEYWORDS
Science) MPI Lab. Program; SAIT,
Samsung Electronics Co., Ltd anode, cathode, facet control, lithium ion battery, solid‐state electrode

1 | INTRODUCTION rechargeable batteries, is the most practical and effective

option for a wide range of small and large‐scale storage
As the energy crisis deepens, global trends toward applications.2 Lithium‐ion batteries (LIBs) have been a
decarbonization are attempting to shift primary energy great pioneer in energy storage since being introduced to
sources away from traditional fossil fuels to renewable the market in 1991, and have continued to advance over
and environmentally friendly alternatives.1 Efficient recent decades.3 Today, LIBs not only lead the small‐size
energy storage technologies allow intermittently pro- battery industry for portable electronic devices, but are
duced green energy to transcend time and space also prominent in electric vehicles and stationary energy
restrictions. Electrochemical energy storage, such as storage technologies.4

Min‐Ju Choi, Ji Hyun Baek, and Jae Young Kim contributed equally to this study.

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.
© 2023 The Authors. Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.

Battery Energy. 2023;2:20230010. onlinelibrary.wiley.com/r/batteryenergy | 1 of 26

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Yet, traditional LIBs cannot satisfy the stringent electrical field vector.17,18 Consequently, the specific
requirements of future batteries, such as energy density, crystallographic arrangement of each ASSB component
safety, and cost standards, where the ever‐increasing becomes increasingly crucial for efficient vacancy hop-
diversity of applications necessitates greater electrochemical ping of lithium ions. In recent years, interfacial design
energy storage. Because of the electrolyte system, which and crystal engineering that control lattice orientation
utilizes extremely flammable organic liquid electrolytes or have attracted attention as a key strategy for improving
polymer electrolytes, typical LIBs may pose significant the performance of ASSBs.19–26 Building the textured,
safety issues.5 When batteries are overcharged and epitaxial, and single crystalline systems is able to refine
discharged, the poor thermal stability and low flash point and disclose the interfacial behaviors of electrochemical
of liquid electrolytes can easily result in serious accidents mechanisms as well as to improve the durability and
such as fire and explosion.6 Furthermore, liquid electrolyte energy density of solid‐state batteries.27,28 Furthermore,
systems exacerbate performance degradation and significant adverse events at interface, one of the major
electrolyte‐electrode side reactions. The unstable electrolyte obstacles to ASSBs, can be successfully suppressed by
is reductively decomposed to form a solid electrolyte optimizing the orientation order of electrodes and
interface (SEI), which generates massive numbers of SEs.29,30
inactive dead Li.7 The SEI layer becomes out of control In this review, we discuss the single crystal‐,
and eventually breaks down, substantially degrading textured‐, epitaxial growth of ASSB components, cath-
Coulombic efficiency and producing high cell impedance.8 odes, SEs, and anodes, with specific examples (Figure 1).
Meanwhile, the narrow electrochemical window of liquid First, the Li‐ion kinetics in LIB and existing issues in
electrolyte, which is incompatible with lithium metal conventional ASSBs are introduced. Second, recent
anodes, easily promotes the formation of lithium dendrites, research progress on facet‐controlled cathodes, solid‐
which lead to short‐circuit risk and capacity loss in state‐electrolytes, and anodes is reviewed. At the end of
batteries.9 Therefore, the standard liquid electrolyte is no this review, challenges and future research directions
longer suitable for the high‐power battery of the future due
to its limited operating temperature, breakdown under high
voltage, and failure to inhibit lithium dendrite.
One next‐generation battery strategy focuses on “all‐
solid‐state batteries” (ASSBs), which have generated
great promise in terms of operational safety, variable
cell design, and high‐energy density.10 Recently, there
has been a surge of interest in building a performance‐
competitive ASSBs due to the discovery of novel solid
electrolytes (SEs) with available conductivity at ambient
condition.11 The substitution of liquid electrolytes to SEs
opens up the prospect of designing advanced battery
chemistries in addition to solving the major challenges
with liquid electrolytes.12 SEs can enhance safety since
they are inflammable, heat‐resistant, and do not cause
leakages or gas production within the cell. In parallel,
SEs not only have remarkable potential to increase
energy density, but are also less likely to cause adverse
effects than liquid ones, which contribute to extending
the life expectancy of ASSBs.13 Given the tendency of
portable electronics to become increasingly downsized F I G U R E 1 Cathode, solid‐state electrolyte, and anode
and consume higher power, solid‐state batteries will play materials for highly textured and crystalline lithium‐ion batteries
(LIBs). Cathode with olivine structure: Reproduced with
a key role in future energy storage systems.
permission.31 Copyright 2010, American Chemical Society.
In contrast to semi‐infinite diffusion in the liquid
Cathode with silicate structure. Reproduced with permission.32
electric double layer, mass transfer across the entire Copyright 2013, Elsevier B.V. Cathode with spinel structure.
ASSB exclusively occurs via the vacancy‐diffusion Reproduced with permission.33 Copyright 2013, Chinese Materials
process through the solid space charge layer, in which Research Society. Cathode with layered structure. Reproduced with
kinetics is sluggish.14–16 To further shorten the migration permission.34 Copyright 2017, MDPI. Solid‐state‐electrolyte with
pathway and lower the interfacial barrier, mass‐charge garnet structure: Reproduced with permission.35 Copyright 2015,
diffusion channels should be aligned parallel to the Springer Nature. Cathode with olivine structure.
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CHOI ET AL. | 3 of 26

with a well‐defined battery system are proposed. This The diffusion rate of Li‐ions is diffusion coefficient Di
provides insights into the importance of facet control to and flux per unit concentration change. The diffusion
achieve further performance improvement in the near rate equation of Li follows the Arrhenius equation.
future as traditional methodologies of battery technology
development reach their limits. Di = D0 exp(−ΔG / KB T ), (2)

where D0 is the experimental predictor, ΔG is the

2 | THE M ER ITS O F energy potential, and KB is the Boltzmann constant.
CRYSTALLINE GROWTH C ONTROL Raising the temperature based on the formula can
IN LIB increase the diffusion rate but can cause irreversible
capacity loss due to side reactions at the interface.
LIB is basically composed of a cathode, anode, electro- Raising the temperature may not help improve the
lyte, and separator. The cathode transfers Li‐ions to the diffusion rate of Li‐ions. The diffusion rate of Li is
anode through the electrolyte, and Li‐ions are stacked on actually affected by the lattice of the material. The
the anode through a charging process. In this charging lattice difference of each material serves as a diffusion
process, the chemical potential of the anode is higher barrier, and it is preferable to construct a battery by
than that of the cathode. The Li‐ions stacked in an anode aligning the composition and topology structure of the
return to the cathode through a discharging process, and electrode. Li‐ion diffusion rate within the electrode
electrons are moved through a circuit to generate a may be described below.
current. The separator keeps the cathode and anode
materials apart.36,37 t = x 2 / qDi , (3)
Battery performance is mainly evaluated by cycle
performance stability and specific capacity. To achieve where x is diffusion distance, and q is dimensionally
high cycle performance stability and specific capacity, Li‐ constant, and depending on the sample situation, the
ions should move quickly in the electrode and the values are 2, 4 and 6, corresponding to 1D, 2D,
electrolyte, and charge transfer by solvation/desolvation and 3D. To reduce the diffusion time (t) and secure a
of Li‐ions should occur at the interface between the high dimension constant, a microstructure that can
electrode and the electrolyte.38 If the difference between cause 3D diffusion should be created. In general, by
the diffusion rate of Li‐ions at the interface and the charge reducing the material size to a nano size, the contact
transfer rate in the electrode is large, polarization occurs area is improved, and the moving distance between
in the electrode due to the distribution of nonuniform ions electrons and Li is reduced. If the electrode structure is
and electrons, causing a plating phenomenon of Li‐ions. an open pore structure, a conductive interconnection
To improve electron conductivity, it is important to network can be created in the 3D direction, which
form an electron transport path in the electrode. The increases the reaction rate by creating a transport path.
main factor in determining electron conductivity is To ensure a fast movement speed of electrons and a
electron mobility, where charge transfer by the hole is conversion speed of Li‐ions, a material for a high Di
generally considered as well. The equation related to the value should be selected, a material size should be
conductivity of the carrier's mobility is as follows: reduced, and a thin electrode should be configured to
obtain a low x value. In addition, the high q value
σ = ni eμe + pi eμh . (1) should be achieved by configuring the rational
structure at the interface.39
This equation represents conductivity by the mobility Figure 2 shows a schematic of issues for each
of electrons and holes. ni and pi are the numbers of component of the LIB. The ion mobility at the interface
electrons and holes, μe and μh are the mobility of between the electrode and the electrolyte decreases due
electrons and holes, and e is the absolute value of each to the formation of improper interphase and resistive
carrier's charge. It is important to select a material with space charge layer. This causes high resistance internally,
high mobility based on the equation. When an electrode and dendrites of Li are formed at the interface between
in a thin film state is used, electron conductivity may the electrode and the electrolyte or inside the electrolyte
be easily decreased due to a thin thickness, so it is more through plating and stripping of Li‐ions during repeated
important to ensure the mobility of the electrode. It is cycle performance of the battery.42,43 The dendrite is a
possible to improve the mobility of the electrode by protrusion of Li caused by an inhomogeneous electric
coating heat treatment, conductive agent, and conductive field between the electrolyte and the molten Li interface.
material.39–41 And it makes the ion flux nonuniform with a tip effect. Li
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
4 of 26 | CHOI ET AL.

FIGURE 2 Schematic illustration of various issues in lithium‐ion batteries (LIBs).

dendrite increases the resistance of the battery and of each part of the battery will help understand the
causes extra strain energy due to the deformation of the interfacial properties of LIBs and will be important base
electrolyte and the added interfacial energy. The driving research to improve battery performance in the future.
force of the actual electrolyte is larger than the resistance
force. A high electron conductivity moves from anode to
electrolyte, thereby reducing the total electric potential 3 | F A C E T CO N T R O L L E D LI ‐ I O N
applied to the electrolyte. As a result, during charging, BATTERIES
the electrical potential of the electrolyte is lower than
0 V, which causes nucleation and growth of Li 3.1 | Cathode
dendrite.44,45
The volume change of active material forms cracks As discussed in the previous part, research was
during a cycle and reduces the contact area at an effective conducted continuously to improve the cathode perform-
electrolyte/electrode interface.46,47 By reducing the spe- ance in a solid‐state battery through the crystallization of
cific resistance area at the interface, the charge transfer cathodes. Compared to the conventional cathode, the
through the interface slows down and increases the cathode with high crystallinity exhibits excellent
electric potential applied to the electrolyte. An mechanical strength, structure or thermal stability, and
irreversible side reaction occurs when the electrolyte cycling performance.52 For a cathode without crystallin-
exceeds the electric potential that the electrolyte can ity, the Li‐ions move to the electrolyte through grain
withstand, and the resulting reaction interferes with the boundaries (GBs) to increase the interface impedance
movement of Li‐ions at the interface. The chemical between the electrolyte and the cathode. In contrast,
potential between the electrode and the electrolyte limits a crystalline cathode has a continuous diffusion path of
the movement of Li‐ions to create a space charge layer, Li‐ions and a lower interfacial resistance than a cathode
which has a low Li‐ions diffusion coefficient.48,49 The with low crystallinity, thereby having a high diffusion
high resistance of these interfaces leads to low coulombic momentum of Li‐ions, and a cathode efficiency in a
efficiency, low power performance, and short cycling battery is higher than an amorphous state.
life.36,50 Suitable cathode materials should have low fermi
Growing a thin film by controlling the crystal levels and high potential energy. And it has a high
direction of the solid anode and the SE helps to study reversibility to the movement of Li‐ions so that Li‐ions
how mechanisms occur in atomic units during the EC can be well intercalated/deintercalated. In addition, it
process. Using transmission electron microscopy (TEM) should have a high ion diffusion rate, electron conduc-
and other neutron reflectivity equipment, it is possible to tivity, and ion conductivity inside the cathode, and
observe the movement of additional other atoms.51 thermal stability and electrolyte compatibility should be
Physical/chemical analysis according to the crystallinity good. Easy synthesis and low material prices are also
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHOI ET AL. | 5 of 26

required, and it is not easy to find cathode materials that transition metal, and representative materials include
satisfy all conditions at once. In general, lithiated nickel, cobalt, and manganese. The ratio of each element
transition metal oxide is mainly used, and the crystal is adjusted, the complementary point of the layered
structure of the cathode is divided into a layered‐type cathode is improved, and research is generally conducted
structure, spinel‐type structure, olivine‐type structure, in the direction of increasing the content of Ni and
and silicate‐type structure. Until now, the cathode decreasing the content of the Co element.58 Various
material has been studied, focusing on the electroche- experiments have been conducted on general trends.
mical performance of the cathode for the intercalation/ Mechanical strength, cycle stability, and thermal stability
deintercalation of Li.11 were measured for samples with adjusted ratios of Ni,
Studies on the performance analysis of LIB according Co, and Mn. An important factor in the problem of solid‐
to the crystallinity of the solid cathode have been actively state batteries is the negative interfacility kinetics at the
conducted. The characteristics of the heterojunction interface between SE and electrode that interfere with
interface between solids are determined by the crystal- charge/discharge. To analyze this, various variables
linity of each solid. The crystalline cathode has the (surface impurities, damage, space charge effect, inter-
following applicability to an industrial environment: high diffusion) should be considered, and variables unrelated
reaction homogeneity, small specific area, and high to crystallinity should be removed.59–61
structural and thermal stability compared to a poly- In recent years, crystallographic analysis has been
crystalline cathode. Improved battery performance may conducted, excluding other factors for cathode materials.
be determined by cycling performance.53 Differences in As shown in Figure 3, the crystallinity was controlled in
the crystallinity of cathodes make differences in the the whole battery, or half battery was tested. Sayers
physical and chemical properties of electrodes. An et al.62 confirmed that the 10‐layer cubic perovskite
electrode in a single crystal state has superior mechanical superstructure Ba1.7Ca2.4Y0.9Fe5O13 was epitaxially de-
strength, structure/thermal stability, and long cycling posited, resulting in a lower grain boundary density than
performance than in the conventional polycrystal struc- polycrystal, increasing ion conductivity. Figure 3A–C is a
ture.54,55 When the same mechanical pressure (45 MPa) cross‐section TEM image of Ba1.7Ca2.4Y0.9Fe5O13 depos-
is applied to the cathode, the single‐crystal cathode ited with 10 layers, where stacking faults are generated
maintains its morphology better than the polycrystalline by the SrTiO3 (STO) substrate (Figure 3C). In addition,
cathode. This means that morphological integrity is the ion conductivity of each temperature was compared
higher in single crystals than in polycrystalline so that with the cathode form in the thin film and bulk state, and
structural stability can be better maintained during the it was confirmed that the cathode in the thin film form
calendar or charge/discharge process.56 Under the 300‐ manifested a higher ion conductivity (Figure 3D,E).62 In
cycle performance for measuring electrochemical stabil- addition, a partial single crystal type LiMn2O4 (LMO)
ity, electrodes in polycrystalline structure, unlike single cathode electrolyte was grown on an Li0.33La0.56TiO3 SE
crystal structure, generated many cracks along the grain part to measure cycle performance in each crystal
boundary.57 The electrode in the single crystal cathode direction of the cathode (Figure 3F–H).63 LiCoO2
has high structural stability, and the specific surface area (LCO) is a cathode that has been studied steadily for
is maintained small during cycle performance, which many years, and there are many reports comparing
generates less gas generated in the battery, thereby battery performance according to the crystal direction by
suppressing side reactions occurring at the interface.53,56 controlling the crystal plane of LCO. Experiments are
continuously conducted to measure cycle performance
by crystal direction through voltammogram curve analy-
3.1.1 | Layered structure (LCO, NC, CA, sis (Figure 3I–L).64 LCO also could be deposited
NCM, and NCA) epitaxially using PLD, making it possible to research
the movement of Li‐ions by the growth direction of
The layered structure, expressed as LiMO2, is contained cathode materials. Takeuchi et al.65 deposited conductive
in the rock salt structure. MO2 is located in SrRuO3 (SRO) on the STO substrate to use it as a current
the octahedral position and forms the MO2 layer. The collector to analyze electrochemical properties, and the
Li‐ions are located between these solid layers. The STO substrate controlled the growth direction of LCO
disadvantages of a layered structure are that it actually using substrates in the directions (111), (110), and (100),
has a capacity value of half lower than the theoretical respectively. In each substrate, the LCO was deposited to
capacity value, thermal stability is low, and the price of the out‐of‐plane oriented (001), (110), and (104). When a
the cathode material is high. To compensate for this surface oriented {104} plane between LCO and liquid
disadvantage, two or three elements are added to the electrolyte, the Li diffusion rate between the electrolyte
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
6 of 26 | CHOI ET AL.

F I G U R E 3 Measurement of electrochemical properties of epitaxial cathode. (A) High angle annular dark‐field scanning transmission electron
microscopy (HAADF‐STEM) image and schematic of crystal structure, (B) simulated HAADF‐STEM image, and (C) STEM image with red line
marking stacking faults in Ba1.7Ca2.4Y0.9Fe5O13/STO structure along (0 1 0) orientation. (D) ECM arcs correspond to high‐frequency (HF) and mid‐
frequency (MF) at different temperatures. (E) Conductivity by temperature in thin film and bulk polycrystalline ceramic through Arrhenius plot.
Reproduced with permission.62 Copyright 2013, Creative Commons Attribution 3.0 Unported Licence (F) scanning electron microscopy (SEM) (top
and cross‐sectional) image and schematic image of vertically aligned nanocomposite for each Nb: STO substrate orientation (100) and (110).
(G) Changes in the capacity‐voltage curve according to the number of cycles for each substrate orientation (100) and (110). (H) Stability test against
cycle for each substrate orientation. Reproduced with permission.63 Copyright 2022, American Chemical Society (I) θ‐2θ measurement XRD pattern
at ψ = 35° and (J) out‐of‐plane direction XRD pattern for thin film LCO on Pt (110) substrate. Volammograms for cycles of the LiCoO2/Pt (110)
structure according to the orientation of LCO oriented (K) (11–20) and (L) (10–14). Reproduced with permission.64 Copyright 2016, Elsevier B.V.

and cathode was the fastest.34,65 In addition, in a solid‐ highest surface density. The LNMO in the (100) direction
state battery, the crystal direction of the cathode material has an exposed surface on a high proportion of (100)
affects battery performance more than in a liquid orientation, and the LNMO in the (100) orientation has
electrolyte.66 The size of the battery will become smaller, the lowest stability compared to the crystals in which
and the demand for high energy density and repetitive other sides are exposed. Accordingly, thick LiCO3 is
stability will increase. Researching the performance of a formed on the surface oriented (100) during the
solid‐state battery according to crystallinity is essential annealing process (Figure 4D). In the galvanostatic
because the interface between the electrolyte and the charge‐discharge (GCD) curves of the LNMO growth
electrode will have a more dominant effect on the battery direction in Figure 4E–G, the initial charge curve has a
performance. larger capacity than the theoretical capacity value due to
Lee et al.67 adjusted the growth direction of an irreversible oxidation reaction.68 Figure 4H–J is a
LiNi0.5Mn1.5O4 (LNMO) using the MgO (100), (110), graph comparing GCD curves at the 1st, 50th, and 100th
and (111) substrate orientations and the LNMO in the cycles per LNMO crystal direction. Capacities and
(100) orientation has the highest surface energy.68 As coulombic efficiencies were compared, and until the
shown in the schematic diagram of each side of initial 50 cycles, the LNMO in the (100) orientation had a
Figure 4A–C, the packing density is lowered in the order higher capacity value compared to other directions. In
of (111), (100), and (110) orientation. The (111) oriented Figure 4K, as the C‐rate increases, there is a large
plane has the lowest surface energy because it has the decrease in the capacitor in the (111) direction. In 100
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CHOI ET AL. | 7 of 26

F I G U R E 4 Layered structure epitaxial cathode material LiNi0.5Mn1.5O4. Schematic image of LNMO crystal structure for (A) (110)
orientation, (B) (100) orientation and (C) (111) orientation. (D) Schematic image of LCO film formation by surface energy during the
annealing process for each (100) and (111) crystal orientation of LNMO. Measurement of electrochemical properties according to LNMO
crystal orientation. Galvanostatic charge‐discharge (GCD) curves according to C rate for each crystal orientation (E) (100) oriented, (F) (110)
oriented and (G) (111) oriented. GCD curves for each crystal direction according to the number of cycles. (H) first cycle. (I) 50th cycles and
(J) 100th cycles. (K) Measurement results of discharge capacity and coulombic efficiency according to the number of cycles. (L) The 100th
cyclic voltammogram measurement for each (100) orientation, (110) orientation and (111) orientation. Reproduced with permission.67
Copyright 2021, Elsevier Ltd.
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8 of 26 | CHOI ET AL.

cycles, the largest decrease occurs at the cathode in the polycrystal structure. It reduces the cycle and electrical
(100) orientation (Figure 4L). The reason why the stability of the single‐crystal state cathode. As a result,
orientation (111) has the highest capacity stably in 100 the single crystal LiMn2O4 has higher specific capacity
cycles is that Li‐ion is diffused by the exposed surface of and cycle performance stability than the cracking effect
the facet, and the orientation (111) is relatively densely at polycrystal, depending on the voltage range.72,73 There
packed than the orientation (001), making it difficult is also a study that analyzed the characteristics of
to diffuse.69 cathode materials by crystal direction of LiMn2O4, and
In addition, cycling performance and thermal stabil- KC et al.74 controlled the plane direction of LiMn2O4 in
ity are important variables to actually commercialize a the out‐of‐plane direction using substrates in the (100)
battery, and Fan et al.70 tested LiNi0.83Co0.11Mn0.06O2 to and (111) directions of STO. The movement of active
confirm that a high crystalline cathode has higher cycle materials at the interface and the degree of secondary
stability than the amorphous cathode. At a specific phase formation were observed by the crystal direction of
temperature of the Li1.2Mn0.567Ni0.167Co0.067O2 cathode LiMn2O4. In the case of LiMn2O4 deposited in the
material, thermal stability was measured in the amount direction (100), it was confirmed that the cycle perform-
of energy stored per gram, and a single crystal was ance of capacity decreased sharply, and this confirmed
measured to be higher than a noncrystalline cathode.70 that the crystal direction of LiMn2O4 was a factor
affecting the performance of the cathode.74
Kim et al.75 manufactured a high‐efficiency battery by
3.1.2 | Spinel structure (LiM2O4, M = V, Ti, forming a spinel structure LiMn2O4 as a single crystal
Mn, Zn, and Ni) nanowire with a large surface part relative to volume.
The nanorod form was a one‐dimensional electron
The LiM2O4 formula indicates this, and the spinel transfer path and strain relaxation while the battery
structure corresponds to the Fd3m space group. In this was charged/discharged. Methods to synthesize LiMn2O4
structure, oxygen ions are located at the 32e position, include combination, sol‐gel, solution‐phase, template,
which consists of cubic close packing. The transition and PLD. The author used hydrothermal synthesis,
metal, expressed as M, is located at six coordination sites which synthesized beta‐MnO3 nanorods into free‐
in octahedral, and the Li‐ions are located in tetrahedral standing single‐crystalline LiMn2O4 through chemical
vacant. Tetrahedrons and octahedrons provide 3D changes. The single crystal nanorod cathode showed a
channels when Li‐ions are diffused through co‐planar higher capacity value than the charge storage of the
and coedge.33,37 commercialized 10 µm size particle and maintained 85%
The representative cathode material with the spinel of the initial charge storage capacity during 100 cycles.
structure is LiMn2O4. In the existing LixCoO2, the x value As Li is intercalated, it causes a small lattice parameter
is between 0.5 and 1, and the charge capacity was change in the cubic phase, which causes a potential
measured to be about 140 mAh/g. However, LiMn2O4 has window of 3.5–4.3 V. Figure 5A–D shows the change in
received a lot of attention as an alternative material for the lattice parameter of the spinel cubic structure due to
LCO cathodes because the cobalt used is expensive and the change in the composition ratio of Li by delithiation.
toxic. The spinel structure LiMn2O4 has a charge capacity With this change, the potential of the cathode material is
(148 mAh/g) similar to that of LCO, is economical in divided into a two‐phase domain state within 4.15 V.
material price, and is not harmful to the environment.71,72 In Figure 5E, it can be divided into three stages of
Yu et al.72 experimented with comparing the Li‐ion reaction for each voltage. The first step is to eliminate the
storage of LiMn2O4 in the single‐crystal structure and oxygen vacancies remaining in the excess lithium and
the polycrystal structure. Generally, the single‐crystal lattice up to 3.8 V, and the second step is to undergo a
cathode has higher stability in crack formation and thus lithium de‐intercalation reaction at voltages higher than
has superior cycle stability than the polycrystal structure. 3.9 V. In the LiMn2O4 cubic spinel phase, the amount of
Yu et al.72 compared and analyzed the specific capacity of Li is changed to an insufficient phase in the same state.76
the cathode according to the voltage range. In the 3 V In voltage near the 4.15 V plateau, two‐phase mixings are
range, single‐crystal LiMn2O4 has higher specific capac- present, and the reaction is completed by having a
ity and cycle performance stability than polycrystal composition of Li0.2Mn2O4. The reaction terminals can
LiMn2O4. However, unlike the Ni‐rich layered cathode, be classified by the peak value shown in Figure 5F.
Mn (Ⅱ) ion dissolution occurs in the LiMn2O4 cathode at Comparing the powder type used in the industrial field
the 4 V region, resulting in a phase transition. Because with the discharge value of the LiMn2O4 type used in this
the {110} side is exposed in the single crystal facet, Mn paper, it can be confirmed that the single crystal
dispersion occurs more easily than in the densely packed nanorods type can transport one‐dimensional electrons,
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHOI ET AL. | 9 of 26

F I G U R E 5 Spinel structure epitaxial nanorods cathode LiMn2O4. Measurement of the lattice parameter in nanorods cubic spinel
cathode according to the content of Li. (A) Low‐ and (B) high‐resolution transmission electron microscopy (TEM) images of Li0.8Mn2O4.
(C) Low‐ and (D) high‐resolution TEM images of Li0.4Mn2O4. (E) Galvanostatic curve with two domains measured in the charge/discharge
process with the first 0.1 C rate. (F) The differential value of capacity by voltage. (G) Comparison of the discharge value of commercially
used powder electrodes (white square) and nanorod‐type electrodes (black dot) by cycle number. (H) The capacity curves of a single crystal
cathode material by charge (white)/discharge (red) process cycle number. Reproduced with permission.75 Copyright 2008, American
Chemical Society.

and thus the kinetics of LiMn2O4 is improved even at a require high rates. The main purpose to overcome this
high rate (Figure 5G,H).75 disadvantage is increasing the conductivity of LiFePO4 by
coating carbon or other conductive materials and
reducing the particle size, doping ion, size reduction
3.1.3 | Olivine (LiMPO4 and Li2MSiO4) and morphology control.31,77 Unlike the conventional
method, the kinetics of the extraction/insertion process
The chemical formula for the olivine structure is of Li‐ions can be improved by controlling the orientation
LiMPO4, and the close‐packed hexagonal structure is of LiCoPO4. [010] oriented LiCoPO4 nanoplates/nano-
slightly distorted. Phosphorus ions are located in the flakes structure and [100] or [001]‐oriented nanorod and
tetrahedral vacant, and transition metal ions and Li‐ions nanowire structures have a minimum shape of crystallite
are located in the octahedral vacant. The framework of size in b‐axis, which is the diffusion direction of Li‐ions,
the crystal consists of MO6 octahedrons and PO4 and when Li‐ions are certain in this crystal direction, the
tetrahedrons. Each PO4 shares one point with MO6, diffusion rate of Li‐ions in the olivine structure can be
and PO4 is not interconnected. So far, LiFePO4 is the increased. Here, the crystal direction of the cathode in
most promising cathode material in the olivine structure the olivine structure is determined by the free surface
and has already been commercialized in the LIB. In the energy of each facet in a thermodynamic equilibrium
case of LiFeO4, ions move slowly due to a compact state.78 The preference of the crystal facet is determined
structure but have high structural stability at a low by the solvent properties, and the LiCoPO4 may form a
voltage. This is because the volume change is within 6% crystal direction in the direction (010) by using ethylene
when charged/discharged. However, since the FeO6 glycol as the solvent and solvothermal condition.79–81
octahedral network confines electrons between Fe‐O‐ Wang et al.82 made a high‐rate LIB by adjusting the
Fe, the oxygen‐metal ion combination in hexagonal close crystal direction of LiFePO4 nanoplates. As mentioned
packing reduces electron mobility. This drawback makes above, olivine LiFePO4 nanoplate is prepared using
olivine batteries unsuitable for use in environments that other precursors and other growth kinetics through a
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
10 of 26 | CHOI ET AL.

glycol‐based solvothermal process, and the nanoplates 3.2 | Solid‐state electrolyte (SE)
may adjust the crystal direction with ac facet or bc facet.
In Figure 6A,B, the difference in capacitance between the SEs are one of the most vital components of ASSBs since
two directions was not significant at a low C‐rate, but at a the performance of solid‐state batteries depends on the
high rate, the difference was significant. As the C‐rate diffusion of ions inside the electrolytes. SEs necessitate
increased, the reversible capacities of the ac‐facet crystal not only high ionic conductivity but also extremely low
orientation were higher than those of the bc‐facet crystal electronic conductivity and substantial levels of chemical
orientation. The difference is that each crystal direction stability. Unlike cathode materials, few studies have
controls only rate capability, and the defect concentra- focused on facet control in SEs; instead, the majority of
tion controls the degree of chemical availability. Using research has concentrated to investigate novel compound
this, only the rate capability of the battery can be and structure types that satisfy the requirements.85,86
adjusted without interfering with other elements.82 This is possibly because there has been far less research
In addition to the layered, spinel, and olivine and development in the field of SEs since the period of
structures mentioned above, there is a cathode with a attention on SEs is considerably shorter than that of
silicate structure. Silicate with the orthorhombic structure cathode materials.87 The SEs is a rapidly developing area
is represented by the Li2MSiO4 formula and has two that is still in the early stages of maturation. Fast ion
Li‐ions per metal to enable reversible de‐intercalation. conducting materials utilizing crystallographic advan-
This is why the cathode material with the silicate tages will be more actively developed and explored in
structure is attracting attention. Tetrahedrons of SiO4 the future.
and tetrahedrons of MoO4 form a layered‐like structure, In this section, the advantages and effects of single
and tetrahedrons of SiO4 have a structure that is crystal‐, textured‐, epitaxial‐growth are discussed for two
periodically repeated.32,84 In 2021, Du et al.83 measured representative ceramic SEs; garnet‐type Li7La3Zr2O12
charge (330 mAhg−1) and discharge (220 mAhg−1) values (LLZO) and perovskite‐type Li3xLa2/3xTiO3 (LLTO).
that were almost similar to theoretical values. In
Figure 6C, the discharge capacity differs by 30 mAhg−1
depending on electrode loading for Li2CoSiO4 cathode and 3.2.1 | Garnet type‐SEs
Li2Co1‐xMnxSiO4 cathode. However, until now, few studies
have analyzed the performance of the battery according to The traditional garnet structure has a standard chemical
the crystalline state of the silicate cathode material or the formula of A3B2(XO4)3, where cation‐filled A‐B‐X forms
characteristics of the interface according to the crystal a face‐centered cubic structure. The garnet structure
direction. Due to the various applications of solid‐state possesses Li‐ion conductivity when a Li‐ion occupies the
batteries, the demand for solid‐state batteries will increase. X position.88 The crystal structure of cubic Li7La3Zr2O12
As the battery is miniaturized and each part is solidified, (LLZO) is shown in Figure 7A.89 Since the Li7La3Zr2O12
battery performance measurement by the crystallinity of stoichiometry contains seven Li atoms per garnet
the cathode material is a part to be studied.83 formula, it is called Li7 system. The fundamental

F I G U R E 6 Olivine structure nanoplates cathode LiFePO4 and silicate structure cathode Li2Co1‐xMnxSiO4. The electrochemical
performance of nanoflakes with different crystal orientations measured at different C‐rates (0.1, 0.5, 1, 5, and 10). (A) The electrochemical
performance in ac facet crystal orientation at each C‐rates. (B) The electrochemical performance in bc facet crystal orientation at each
C‐rates. Reproduced with permission.82 Copyright 2012, American Chemical Society (C) A graph of the reversible capacity between the
Li2CoSiO4 cathode and the Li2Co1‐xMnxSiO4 cathode. Reproduced with permission.83 Copyright 2021, Wiley‐VCH GmbH.
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHOI ET AL. | 11 of 26

F I G U R E 7 Garnet‐type solid electrolyte. (A) Crystal structure of cubic Li7La3Zr2O12 and polyhedra of coordination surrounding the Li1
and Li2 sites. (B) Three‐dimensional conducting network of the Li‐ion in cubic LLZO. Reproduced with permission.89 Copyright 2011, The
Chemical Society of Japan (C) Schematic diagrams of the three symmetric tilt GBs arising from the BCC Zr sublattice (Li, La, and O atoms
not shown): Σ5(310), Σ5(210), and Σ3(112). (D) Calculated Li+ diffusivity across LLZO cells with different GBs. (E) Arrhenius plots
comparing Li‐ion diffusivity for LLZO in bulk and with GB areas. Reproduced with permission.90 Copyright 2017, American Chemical
Society (F) Arrhenius plots of DLi for single crystal and powder samples of garnet‐type solid electrolytes. Reproduced with permission.91
Copyright 2019, Royal Society of Chemistry (G) Change of the electronic conductivity of different single and polycrystalline garnet‐type solid
electrolytes as a function of temperature. (H) Total conductivities and activation energies of single and polycrystalline materials given in (G).
Reproduced with permission.92 Copyright 2020, John Wiley and Sons (I) Crystal structures of epitaxial films of LLZO(001)/GGG (001) and
LLZO(111)/GGG(111). (J) The temperature‐dependent conductivities for the [110] direction in LLZO(001) and the [11–2] direction in LLZO
(111). The insets illustrate the impedance spectra at different temperatures. Reproduced with permission.93 Copyright 2013, Royal Society of
Chemistry.

framework of garnet structure is composed of dodecahe- entire framework. The three‐dimensional pathway of
dral LaO8 and octahedral ZrO6. Within the interstices of Li‐ion migration implies an isotropic nature of ionic
the framework, the Li atoms occupy two different conduction with little dependency on crystallographic
crystallographic positions, L1 and L2, with the Li2 site orientation.94 Total ionic conductivity therefore depends
being vacant in the ideal case. Li‐ion conduction is on the contribution of GBs, which has a significant effect
primarily governed by disorder and partial Li atom on ion migration within the pellet. There will be a
occupancy at Li2 sites. As illustrated in Figure 7B, the noticeable difference in ionic conductivity between single
networks of tetrahedral and deformed octahedral, made and polycrystalline pellets as the grain boundary imped-
of Li and Li vacancies, are interconnected across the ance hinder the Li‐ion transport in LLZO.95
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12 of 26 | CHOI ET AL.

The influence of GBs on Li‐ion transport inside the conductivity. Therefore, high electronic conductivity
LLZO SEs was reported by Yu et al.90 For three GB models values obtained in nonideal systems such as poly-
with different crystallographic interfaces, the composition, crystalline may originate from the large chemical
energy, and transport characteristics were examined at the inhomogeneities of the interfacial region at GBs. Wilken-
atomic level. Figure 7C schematically shows the three ing's group analyzed the bulk electronic conductivity
symmetric tilt GBs with coincident‐site lattice classifica- (σeon) and total conductivity (σtotal) for single crystal
tions of Σ3 and Σ5. The unrelaxed structures are Li6.4Ga0.2La3Zr2O12 (Ga‐LLZO) with a variety of different
represented as a BCC Zr sublattice with Li, La, and O polycrystalline garnet‐type SEs.92 The temperature‐
atoms omitted for convenience. The formula units of dependent electronic conductivity depicted in Figure 7G
LLZO within the grains are 160 (Σ5(310)), 80 (Σ5(210)), covered various single‐ and polycrystalline SEs with
and 96 (Σ3(112)), respectively. Every grain includes different dopants. The specific electronic conductivities
stoichiometric amounts of LLZO. The calculated Li‐ion have been demonstrated to vary by several orders of
diffusivity across LLZO cells for the respective GB magnitude for polycrystalline materials even with the
configurations is presented in Figure 7D. In all types of identical composition. The Ga‐LLZO single crystal ex-
GB models, diffusivity is always higher in the bulk areas hibits the lowest electronic conductivity in the given data
and reduces in the GB region. It was discovered that the measured at low voltage. While excluding any contribu-
loss in ionic diffusivity was caused by both a rapid rise in tions from the GBs, it represents true bulk value. This
confined immobile Li‐ions near GB region as well as a supports the general observation that garnet‐type SEs
local degradation in ion mobility due to disruption of the exhibit higher electronic conductivity in polycrystalline
interconnection of ion transport channel across GBs. materials than in single crystalline. Figure 7H provides a
Although diffusion inside bulk LLZO is isotropic, it may summary of the total conductivities and activation
exhibit local anisotropy due to the unusual lattice energies for the samples displayed in Figure 7G at room
geometry around the GBs.96 As a result, the degree of temperature. Despite showing a low electronic conductiv-
diffusivity drop considerably differs amongst the distinct ity, the single crystal Ga‐LLZO has been demonstrated to
GBs. Figure 7E displays Arrhenius plots for Li‐ion have a rather high total conductivity, the sum of the ionic
diffusivity inside the bulk LLZO and three GB models and electronic conductivities. Given the negligible contri-
over a temperature range of 700–1100 K. The bulk LLZO bution of electronic conductivity to the total, it can be
has the lowest activation energy of 0.52 eV as extracted inferred that the total conductivity is driven by ionic
from the slope and has the greatest ionic diffusivity across conduction. In other words, single‐crystal Ga‐LLZO is
the entire temperature range. The variation in ionic highly ionic conductive and ion transport is not coupled
diffusivity is more pronounced at low temperatures, with with electron transport. By minimizing extrinsic factors in
the Σ5 boundary at 300 K having up to two orders of the single crystal system, it was able to achieve both high
magnitude slower diffusivity than the bulk. Hayamizu and ionic conductivity and low electronic conductivity at a
colleagues reached similar conclusions by comparing level that does not lead to lithium dendrite formation.
various garnet‐type SEs in single crystal and powder Kim et al.93 successfully synthesized Al‐doped LLZO
form.91 Arrhenius plots in Figure 7F give DLi for single epitaxial thin films on Gd3Gd5O12 (GGG) substrates by
crystal and powder samples of garnet‐type SEs with pulsed laser deposition and investigated the intragrain
various dopants. The evaluations included single crystal Li‐ion diffusion mechanism. The epitaxial LLZO thin
samples of sc‐LLZO‐Ta97 and sc‐LLZO‐Nb91 as well as films are deposited in two directions depending on the
powder samples of LLZO,98 LLZO‐Ta,99 LLZO‐Al‐Ta,100 orientation of the GGG substrate: LLZO(001)/GGG(001)
and LLZO‐Nb.91 Over the entire measured temperature and LLZO(111)/GGG (111). The schematic crystal
range, the single crystal samples clearly displayed larger structure in Figure 7I illustrates the epitaxial growth
DLi, regardless of the doping component. In garnet‐type of Al‐LLZO films in two orientations. Figure 7J shows
SEs with three‐dimensional ion transportation, it is the temperature‐dependent conductivities of the epitax-
obvious that single‐crystal materials with no GBs exhibit ial LLZO thin films obtained from 25°C to 80°C. The
higher diffusivity without suffering from a mobility ionic conductivity was measured along the in‐plane
deterioration due to transboundary penetration. pathway in the [110] direction for the LLZO(001) and
SEs demand extremely low electrical conductivity to the [11‐2] direction for the LLZO(111) thin film,
prevent systems from self‐discharging. The unintended respectively. The distinct semicircles in the impedance
production of Li dendrites may also be encouraged by a spectra depicted in the inset can be considered as the
non‐negligible electronic conductivity. Numerous external parallel coupling of a capacitance and a resistance. In
factors, including chemical inhomogeneity, impurity, and comparison to the LLZO(001) film, the epitaxial LLZO
grain boundary, can determine macroscopic electronic (111) film displayed a higher ionic conductivity as well
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHOI ET AL. | 13 of 26

as a lower activation energy. Since Li‐ions migrate have been shown to grow in different orientations
isotropically across the three‐dimensional channel of because each substrate induces a respective lattice
cubic LLZO, the disparity in ionic conductivity might mismatch and corresponding strain. For STO substrates
result from compositional or structural differences with asub > cLLTO/2, the applied tensile strain induced the
between the films. The composition of the two films is ac‐plane to deform less along the in‐plane direction,
comparable, while the (111) film was found to have less contributing to the h00 orientation. On the other hand,
lattice distortion than the (001) film. Hence, the lattice for the LSAT and NGO substrates where asub < aLLTO, the
mismatch between the substrate and film caused the compressive strain imposed on the LLTO lattice allowed
lattice to distort, which led to a discrepancy in the ab‐plane to have less strain, resulting in 00l
conductivities. The researchers demonstrated the prac- orientation. Figure 8D displays the Arrhenius plot of
tical effects of lattice distortions directly through an compressed LLTO thin film on NGO substrate. The
epitaxial film model system. anisotropic in‐plane ionic conduction across ac‐ and bc‐
planes was observed. The compressive strain of the
orthogonal lattice is stronger along the a‐axis than the b‐
3.2.2 | Perovskite type‐SEs axis. Therefore, the transmission window in the ac‐plane
is narrower than that in the bc‐plane, suggesting that
One representative ceramic SE is of the perovskite type greater compressive strains result in restricted ionic
which has ABO3 crystals structure.101 Lithium lantha- conduction requiring higher activation energy due to
num titanate (LLTO), which has a double perovskite the deepened bottleneck.109 Further, the dependence of
structure where La3+ and Li+ occupy the A site of the ionic conductivity on domain orientation was explored by
titanate compound (ATiO3),102 is a promising candidate Kuwabara's group in a single crystal LLTO system.105 In
for ASSBs applications due to fast ionic conductivity and contrast to garnet‐type LLZO, LLTO exhibits anisotropic
good chemical stability.103 Figure 8A displays the behavior in ionic conduction with the presence of ab‐
perspective views of Li3xLa2/3−xTiO3 (LLTO) crystal planes, the La‐poor layer, serving as the primary pathway
structure.104 In ABO3 perovskite structure, a portion of for Li‐ions.110 Domain orientation, hence, affects the
the A‐sites is occupied by Li‐ions, La‐ions, and vacancies, macroscopic Li‐ion conductivity. Figure 8E shows a
while Ti atoms fill the B‐sites coordinated by six O atoms bright‐field scanning transmission electron microscopy
in the TiO6 octahedral configuration. Due to its deficient (BF STEM) image of a single crystal LLTO. There are two
nature, La2/3TiO3 contains many inherent defects, almost types of lattice defects in LLTO crystal: 90° domain
1/3 of the vacancies, in the A site. At room temperature, boundaries (DBs) and antiphase boundaries (APBs). At
these La vacancies are not randomly arranged; instead, 90° DBs, each perovskite unit in one domain is joined to
they stack along the c‐axis and are divided into La‐rich units in the neighboring domain by a La‐rich layer.
and La‐poor layers, forming a partially arranged super- Lithium transmission over DBs requires higher activation
lattice structure. In the LLTO framework, Li‐ions energy, which significantly impacts ionic conductivity.
horizontally travel along the La‐poor layer, which APBs presumably exert a lesser impact on Li‐ion
contains most of the vacancies and the Li‐ions, via the conduction than 90° DB since each domain orientation
ion‐vacancy transition process.108 During migration, aligns with the conduction direction and the separation in
Li‐ions transmit through a quadrilateral window com- between La‐poor layers is only c/2 unit cell. Figure 8F,G
posed of four oxygen, and the concentration of transport is the cross‐sectional scanning electron microscopy (SEM)
window directly influences the mobility of Li‐ions. images and electron backscatter diffraction (EBSD)
The impact of the transmission window area on measurements of region A and region B, respectively,
the ionic conductivity in strain‐controlled epitaxial with different crystal orientations. The α, β, and γ regions
Li0.33La0.56TiO3 films was examined by Wei et al.106 The of the three different domains were demarcated by
schematic structures of epitaxial films with tensile and trisegmented colors. Schematic diagrams of the crystal
compressive strain are illustrated in Figure 8B. Depend- orientation models for regions α, β, and γ are depicted in
ing on the lattice mismatch with the substrate, the LLTO Figure 8H. All combinations of three domians, α and β, β
layer is subjected to either compressive or tensile stress, and γ, and γ and α, exhibit orientation relationships
which causes lattice distortion. At this time, the area of forming a 90° DBs. To figure out the relationship between
the transmission window extends under tensile strain and crystal orientation and Li‐ion conduction, it is necessary
reduces under compressive strain. Figure 8C presents out‐ to consider the degree to which each domain has been
of‐plane XRD patterns of epitaxial‐grown LLTO thin films rotated perpendicularly along the impedance measure-
on SrTiO3 (STO), (LaAlO3)0.3‐(SrAl0.5Ta0.5O3)0.7 (LSAT), ment direction. When projected from the impedance
and NdGaO3 (NGO) substrates. The LLTO epitaxial films measurement axis, the ab‐plane is tilted by about 18°
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
14 of 26 | CHOI ET AL.

F I G U R E 8 Perovskite‐type solid electrolyte. (A) Perspective views of Li3xLa2/3–xTiO3 (LLTO) perovskite network from the [100]p and
[110]p axes, where “p” represents a cubic pseudo‐perovskite structure. Reproduced with permission.104 Copyright 2013, American Chemical
Society (B) Schematic illustration of epitaxial LLTO thin films with tensile and compressive strain. A bottleneck generated by four oxygen
atoms is denoted by a red dashed square. (C) Out‐of‐plane XRD patterns of epitaxial LLTO thin films on different substrates. (D) Arrhenius
plot of anisotropic in‐plane ionic conductivity of compressed LLTO thin film across ac‐ and bc‐planes. Reproduced with permission.105
Copyright 2015, American Chemical Society (E) The BF STEM image of an LLTO single crystal with two types of lattice defects: 90° domain
boundaries and antiphase boundaries. The cross‐sectional scanning electron microscope images and EBSD measurements of (F) region A
and (G) region B. (H) Crystal orientation and structure models of regions α, β, and γ obtained from the EBSD. (I) Nyquist plots of regions A
and B at 300 K. Reproduced with permission.106 Copyright 2022, American Chemical Society (J) Schematic diagram of Li‐ion transport
channel in Vr‐LLTO LISE and LLTO Pellet. (K) The cross‐sectional transmission electron microscopy (TEM) images of Vr‐LLTO LISE.
(L) Arrhenius plots of Vr‐LLTO LISE at two different thickness and LLTO Pellet. (M) Cycling performances of batteries incorporating
Vr‐LLTO LISE and LLTO pellet at 60°C (0.1 C in the first three cycles and 0.5 C in the latter cycles). Reproduced with permission.107
Copyright 2021, John Wiley and Sons.

in the γ region, whereas it is tilted by 45° in the α and Lv et al.107 introduced highly oriented 2D LLTO
β regions. This implies that region γ carries out crystals and substantially increased ionic conductivity as
more favorable Li‐ion conduction than regions α and well as enhanced battery performance. A thin laminar
β. Area calculation revealed that region A contains 70% inorganic solid electrolyte (LISE) of perfectly aligned
γ domain of the total, while region B has 61% γ domain. LLTO flakes was applied as an interlayer channel inside
The difference in occupancy of region γ between regions the laminar architecture between vermiculite (Vr)
A and B is expected to lead to a disparity in ionic nanosheets. Based on the confinement effect that induces
conductivity. According to the Nyquist plots evaluated at oriented growth in a cramped environment, LLTO
300 K in Figure 8I, regions A and B were estimated to crystals were synthesized in continuous and regular 2D
be have ionic conductivities of 1.0 × 10−3 and 0.8 × arrangement without crystal defects.111,112 Interestingly,
10−3 S/cm, respectively. Thus, even for single‐crystal the LLTO LISE preferentially grew in the c‐axis, the
materials, it has been demonstrated that the ionic fastest path for Li+ migration, along the interlayer
conductivity changes depending on the microcrystal channel, affording considerably improved structural
orientation owing to the anisotropic conduction stability, ionic conductivity, and battery performances.
nature. The schematic diagrams of Li‐ion transport channel in
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CHOI ET AL. | 15 of 26

Vr‐LLTO LISE and LLTO Pellet are seen in Figure 8J. battery performance in the volume. To design a safe,
In contrast to Vr‐LLTO LISE, the LLTO pellets produced high‐rate, and high‐capacity anode, understanding the
in open space exhibit a complex structure with evident anode using a well‐controlled material system is impor-
crystal defects due to unrestricted growth in nonuniform tant. In this section, recent progresses for three different
directions. The TEM image in Figure 8K shows an anode material systems including carbon‐based materi-
ordered Vr‐LLTO LISE with a layered 2D structure. Vr als, IVA and VA group‐based materials, and transition
nanosheets and LLTO crystals are represented by the metal compounds using facet control will be discussed.
bright and dark regions, respectively. Importantly,
structural defects and voids are not detected even at
higher resolutions. Arrhenius plots in Figure 8L com- 3.3.1 | Carbon‐based materials
pared the conductivity of Vr‐LLTO LISE and LLTO
Pellet. It is speculated that the higher conductivity of Vr‐ Among the carbon‐based materials, graphite is the first
LLTO LISE originates from the arranged orientations material used as an anode for LIBs and also was the
that suppress the inherent structural defects of the LLTO first commercialized material.115 Graphite has a layered
crystal, thereby eliminating the grain boundary imped- structure with 0.335 nm of spacing between layers
ance. Indeed, the calculated activation energies of and charging/discharging in graphite‐based anode
0.336 eV for Vr‐LLTO LISE and 0.411 eV for LLTO Pellet occurs through the Li‐ion intercalation/deintercalation.
approximate those of bulk and grain boundary, respec- Although graphite has several advantages such as high
tively.113,114 In addition to the ionic conductivity, the capacity (372 mA·h · g−1), low cost, low overpotential,
cycling performances of Vr‐LLTO LISE and LLTO Pellet and cycle stability of graphite, there are some limitations
were further evaluated in the LFP/Li batteries. After that need to be overcome. Due to the small layer spacing,
accounting for the comprehensive consideration of the graphite has sluggish Li‐ion intercalation kinetics and
period for each charge/discharge operation and battery large Li‐ion diffusion resistance. High current over 1 C
cycling life, the cycling performance was carried out with induces lithium plating, which is the deposition of a dead
0.5 C at 60°C. As demonstrated in Figure 8M, the battery Li layer on the anode surface, resulting in an increase in
made with LLTO pellets underwent a short circuit after internal resistance and a decrease in battery capacity.
47 cycles due to its catastrophic structural flaws. On the More Li metal deposition can induce Li dendrite growth,
other hand, the batteries assembled with Vr‐LLTO LISE which can cause safety issues due to short circuits and
operated without breakdown for 150 cycles, although heat generation. To solve these problems, well‐controlled
there was a slight variance in capacity reduction based on graphite‐based anodes have been studied.
the thickness. Consequently, the exceptional perform- As part of efforts, graphite anodes with alignment
ances of Vr‐LLTO LISE suggest a strategic design for control have been explored. To control the orientation of
ultrafast Li+ conduction devices with great potential for graphite, magnetic field has been applied to the graphite
ASSB application. that is functionalized by magnetic field responding
So far, several types of research have been introduced materials. Billaud et al.116 showed the electrochemical
that investigated the effect of facet control on ionic properties of a battery with an out‐of‐plane ordered anode.
conductivity in two representative SEs, LLZO and LLTO. Graphite was coated with superparamagnetic iron oxide
Although not actively researched yet, as the progress particles and the alignment of graphite coated with iron
through composition engineering reaches its limit, it will oxide was controlled by the magnetic field during the
become more important to enhance the performance of synthesis of anode. Battery with an aligned anode
SEs by utilizing crystallographic properties such as single perpendicular to the current collector showed higher
crystal, grain, and epitaxial growth. lithium storage capacity compared to the randomly
oriented anode due to the shorter Li+ diffusion pathway.
Aligned anodes showed a lower overpotential and up to
3.3 | Anode three times higher specific charge at higher rates. Zhang
et al.117 investigated the battery performance according to
Anode has played a crucial role in battery performance. the alignment angle of the graphite anode. First, to change
The factors governing the performance of anode depend the orientation, graphite flakes were coated with ferrofluid
on where it occurs. Charge transfer ability and the of different concentrations and then an external magnetic
kinetics of Li‐ions within SEI are usually more important field was applied. Figure 9A shows the cross‐sectional
at the surface of the anode. On the other hand, the SEM images for graphite with different orientation angles
diffusion of Li‐ions such as interfaction/deintercalation, including 64°, 71°, 85°, 72°, and 66°, respectively. The
and alloying/dealloying are crucial to determine the alignment angles in SEM images show a volcano‐like
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
16 of 26 | CHOI ET AL.

F I G U R E 9 Carbon‐based anode. (A) Cross‐sectional scanning electron microscope (SEM) images and (B) XRD patterns of graphite
anode synthesized with different concentrations of ferrofluid. (C) The angle between graphite flakes and current collector according to the
concentration of ferrofluid. (D) Rate and cycle performance of graphite anode prepared under the ferrofluid concentration of 27.5, 37.5, and
47.5 μL/g, and reference electrode. Reproduced with permission.117 Copyright 2019, American Chemical Society. (E) Schematic diagram of
unaligned and aligned graphene oxide anodes. SEM cross‐sectional images of graphene oxide anodes prepared with a different flow rate of
(F) 0.2 and (G) 0.4 mL/min. (H) Comparison of rate and cycle performance of different anodes. Reproduced with permission.118 Copyright
2022, Wiley‐VCH GmbH.

trend with increasing concentrations of ferrofluid. XRD the same ferrofluid concentration of 37.5 μL·g−1. Graphite
patterns in Figure 9B exhibit that the (002) peak, which anode prepared under a rotating speed of 350 r·min−1
represents the orientation perpendicular to the hexagonal shows the highest angle of alignment and highest specific
plane of graphite, first decreases and then increases. This capacity.
implies that the graphite flakes functionalized by the In addition to graphene, graphene oxide is another
ferrofluid with a concentration of 37.5 μL·g−1 are aligned good carbon‐based anode material. Zhang et al.119
almost vertically. This trend of alignment angles is shown prepared an aligned Fe3O4 nanoparticle‐decorated gra-
in Figure 9C. The authors demonstrate that the different phene oxide anode using the ice‐templating method. The
ferrofluid concentrations cause different magnetic suscep- synthesis method is as follows: (1) Dispersing the
tibility, resulting in different alignment angles. Figure 9D graphene oxide decorated with Fe3O4 nanoparticles in
exhibits that the specific capacities increase as the H2O. (2) Keeping the copper foil current collector at a
alignment angle increases at a rate of 2C, indicating that low temperature. (3) Ice crystals begin to nucleate near
the larger angle derives the shorter ion diffusion path. the copper foil at the bottom. The temperature of copper
Furthermore, the aligned anode has high cycling stability foil is well below the freezing point of H2O. (4) Ice
at a high current rate. The authors also observed the effect crystals grow vertically toward the top surface due to
of the rotating speed of the magnetic field on alignment at their anisotropic growth. (5) Distribute Fe3O4‐decorated
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHOI ET AL. | 17 of 26

graphene oxides that are aligned. (6) Removing the ice systematically investigate the impact of strategies such as
crystal by reducing pressure. Pore size and wall doping and changing the spacing.
thickness can be controlled by cooling rates and freezing Carbon‐based anode materials are excellent anode
temperatures. The rate performance of aligned anode candidates for LIBs due to their low cost, structural
(724 mA·h·g−1) is much higher than the anode synthe- tunability, and widespread availability. However, even if
sized via the slurry‐casting method (162 mA·h·g−1) various strategies (e.g., doping) are used, there is a limit to
at 2 A·g−1. The aligned anode also shows excellent further improvement of performance due to theoretically
areal capacity (3.6 mA·h·cm−2 under 10 mA·cm−2). The low capacity (e.g., graphite) and poor initial columbic
authors demonstrate that the high areal capacity is efficiency. To this end, it is necessary to develop other
resulted from the improved transport kinetics, the anode materials with excellent performance.
presence of pores that buffer volume expansion, and
decoration of conversion‐based active material Fe3O4.
Liu et al.118 used pulse freezing method to prepare the 3.3.2 | VA and IVA‐based materials
vertically aligned graphene oxide films. Highly ordered
graphene oxide is obtained through the following VA and IVA‐based anode materials includes semi‐
process: (1) Introducing the suspensions of graphene metallic elements such as Sn, Sb, and Bi, and metallic
oxide into the two‐step polydimethylsiloxane microflui- elements such as Si and Ge. These materials store the
dic channel with various flow rates. (2) Graphene oxide multiple Li‐ions by forming the alloy (e.g., Li4.4Si, Li4.4Sn,
sheets are aligned in different directions depending on Li4.4Ge, and Li3Sb), leading to higher specific capacities
the channel region. (3) The graphene oxide suspension compared to the conventional carbon‐based anode
freezes rapidly (“Pulse Freezing”) by immersing into a materials. The theoretical specific capacities for Si, Sn,
dry‐ice ethanol bath. (4) Frozen graphene oxide film is Ge, and Sb are 4200, 994, 1625, and 665 mA·h·g−1,
pumped out of the channel after the interface part melts. respectively. Despite their advantage of excellent specific
(5) Transferring the extracted graphene oxide film back capacities, the large volume change during charging/
into a dry‐ice ethanol bath to freeze again. Multiple discharging causes several problems such as irreversible
freezing steps can maintain the vertically aligned deformation of anode material, low cycling stability,
structure of graphene oxide sheets and yield a porous limited rate capability, and loss of electrical contact.
structure. Figure 9E shows the schematic illustration of Research on orientation‐controlled VA and IVA‐based
randomly oriented and vertically aligned graphene oxide anode materials can provide in‐depth understanding to
films showing Li‐ion transmission and mobility. Cross‐ overcome these challenges.
sectional SEM images in Figure 9F,G exhibits highly Si has been regarded as a promising anode material
ordered graphene oxide sheets prepared at different flow due to its high specific capacity, abundant reserves,
rates of 0.2 and 0.4 mL/min, respectively. Graphene oxide and environmentally friendly characteristics. Despite the
sheets prepared using graphene oxide concentration high specific capacity of Si, huge volume expansion
of 9 mg·mL−1 and flow rate of 0.2 mL·min−1 have a (~440%) and low conductivity (1.56 × 10−3 S·cm−1) limit
horizontal orientation. On the other hand, graphene oxide the battery performance using Si anode. Nugroho et al.120
sheets prepared using graphene oxide concentration of fabricated vertically aligned n‐type Si nanowire array
9 mg·mL−1 and flow rate of 0.4 mL·min−1 have vertical using n‐type Si wafers via photolithography and cryo-
orientation. Electrochemical and half‐cell performance genic inductively coupled plasma‐reactive ion etching
were investigated for pristine graphene oxide, aligned process. XRD patterns displayed in Figure 10A show the
graphene oxide, freeze‐dried graphene oxide, and graph- <100> orientation of pristine Si wafer and aligned n‐type
ite. Figure 9H shows that the half‐cell with aligned Si nanowire arrays. Inset figure in Figure 10A exhibits
graphene oxide sheets exhibits 190% higher specific cross‐sectional SEM image of n‐Si nanowire arrays. The
capacity (440 mA·h·g−1) after 150 cycles compared to the diameter of the Si nanowire is ~996 nm and the distance
half‐cell with freeze‐dried graphene oxide sheets. between the closest wires is ~10.2 μm. Figure 10B,C
Based on the studies mentioned above, vertical shows the electrochemical performance of pristine n‐Si
alignment of carbon‐based anode can shorten the wafer and n‐Si nanowire arrays. Significant decrease of
Li‐ion transportation path. Although there are several specific capacities was observed for the half‐cell with
reports showing that such a short Li‐ion path can greatly pristine n‐Si wafer (0.21, 0.15, 0.13 mA·h·cm−2 at 2nd,
improve the battery performance, there is a lack of 50th, and 100th cycles) because of increase in internal
studies showing the impact of the other factors such as stress resulted from the local volume expansion. While
doping on orientation controlled carbon‐based anode. half‐cell with n‐Si nanowire arrays show higher specific
These kinds of studies can provide a good platform to capacities and stability (0.50, 0.42, and 0.43 mA·h·cm−2 at
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
18 of 26 | CHOI ET AL.

F I G U R E 10 VA and IVA material‐based anode. (A) XRD patterns of n‐Si nanowire and wafer. Inset: scanning electron microscope
(SEM) cross‐sectional image of Si nanowire. Galvanostatic charge and discharge curves of Li‐ion battery with (B) n‐Si wafer and (C) n‐Si
nanowire anodes (2nd to 100th cycles). Reproduced with permission.120 Copyright 2021, MDPI. (D) SEM image (left) and Finite element
analysis result of a lithiated p‐type Si (001) anode. Reproduced with permission.121 Copyright 2016, Nature Portfolio. (E) Transmission
electron microscopy (TEM) images of β ‐Sn nanoparticles synthesized at 0°C and 26°C. (F) SAED image of β ‐Sn nanorods. (G) Cyclic
voltammetry of low aspect ratio and high aspect ratio β ‐Sn nanoparticles. (H) Cyclic test of β ‐Sn anodes with different shapes. Reproduced
with permission.122 Copyright 2018, American Chemical Society.

2nd, 50th, and 100th cycles) than the that with pristine n‐ unit cells is completely constrained by the surrounding
Si wafer. This is due to the larger surface area for material, a large plastic deformation occurs along the
lithiation, and shorter Li‐ion diffusion path compared to (100) edges. This forms the normal stress bands along
the pristine n‐Si wafer. Shi et al.121 used the Si single the <100> directions. This study not only revealed the
crystal to reveal the fundamental fracture mechanisms fracture mechanisms of Si single crystalline anode, but
during charge/discharge cycles. The damage to the Si also presented a strategy to improve fracture resistance
anode surface occurs gradually and cumulatively. As by healing electrode cracks using electrolyte additives
shown on the left side of Figure 10D, SEM images show based on physical understanding.
the orthogonal surface cracks, which can be observed Sn is also a representative alloy‐type anode material
after 30 cycles. The authors proposed that the orthogonal same as Si. The lithiation process of Sn anode is as follows:
surface cracks originated from the orientation‐dependent (1) The formation of Li2Sn5 phase that remain crystallinity
lithiation. The mechanical and electrochemical responses with no visible phase boundaries. (2) The formation of
after long‐term cycling were investigated for the Si Li4.4Sn after further lithiation with a volume expansion of
single‐crystal anode via finite element method (left side 260%. Like Si anode, the large volume change of Sn anode
of Figure 10D). Because the lithiation in the (110) is also a barrier to overcome for high‐performance LIB.
direction is 6.4 times faster than in the (100) direction,123 Juan et al.122 investigated the electrochemical properties of
the volume expansion is anisotropic, leading to high single crystalline β ‐Sn nanorods with controlled aspect
shear stress and crack. Since the volume expansion of ratios of (001) and (100) facets. Figure 10E shows the TEM
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CHOI ET AL. | 19 of 26

image of β ‐Sn nanorods with different morphologies. The were grown on (100), (110), and (111)‐oriented Nb‐doped
spherical β ‐Sn nanoparticles with diameter of 4.5 nm were SrTiO3 single crystal substrates via pulsed laser deposi-
obtained with the synthesis temperature of 26°C. β ‐Sn tion method. XRD patterns in Figure 11A shows that out‐
nanorods with aspect ratios of 2.5 and 11.1 were formed of‐plane crystal orientation of Li4Ti5O12 films were
when the synthesis was performed at 10°C and 0°C, coherently aligned with the substrate orientation. All
respectively. The authors demonstrate that the change in Li4Ti5O12 films have surfaces with <111> crystal
aspect ratio is because of different reduction rates and facets, as this is the surface in the lowest energy
mobility of the particles in solution. Selected area state (Figure 11B). As shown in Figure 11C, (100)‐
diffraction patterns in Figure 10F exhibits that β ‐Sn oriented Li4Ti5O12 films shows the highest capacities
nanorods grow along the [001] direction, indicating the (313 mA·h·g−1), excellent rate performance, and good
tip of β ‐Sn nanorod is (001) facet. As shown in Figure 10G, cyclability with improved cycle life and doubling of
cyclic voltammetry was measured for β ‐Sn nanorods with reversible capacities compared to the polycrystalline
high and low aspect ratio. Cyclic voltammetry curves for Li4Ti5O12 in previous studies. Also, the authors observed
both high and low aspect ratio β ‐Sn nanorods have the that the lithiation waves are traveling more rapidly along
reversible and overlapping curves for the second and third the GBs before intercalating into the grains using a
cycles, indicating the stable cycling activity. However, β ‐Sn phase‐field model. Speulmanns et al.125 fabricated tex-
nanorods with high aspect ratio has a larger total current, tured Li4Ti5O12 films via atomic layer deposition followed
implying the smaller ohmic resistance and polarization by rapid thermal annealing. The pulse time of lithium
of high aspect ratio β ‐Sn nanorods. Furthermore, β ‐Sn hexamethyldisilazide precursor is an important factor to
nanorods with high aspect ratio exhibit the improved obtain the highly textured Li4Ti5O12 film. Also, annealing
cycling stability in Figure 10H. time after deposition is crucial for crystallization. XRD
Research on VA and IVA‐based anode materials using patterns show that a highly (111)‐textured film can be
facet control is lacking. To develop the anodes that take synthesized using pulse time of 5 s and annealing time of
advantage of their large specific capacities, it is necessary 8 min. The effect of orientation control on electrochemical
to deepen our understanding through well‐controlled VA performance was investigated. At an extreme rate of
and IVA‐based anode material systems. 200 C, highly (111)‐textured Li4Ti5O12 film shows capaci-
ties of 278 mA·h·cm−3. Also, the textured film exhibits
97.9% capacity retention after 1000 cycles at 100 C.
3.3.3 | Transition metal compound‐based Orthorhombic Nb2O5 (T‐Nb2O5) is another
materials intercalation‐type anode material. The multielectron
redox reaction enables a high theoretical capacity
Transition metal compounds have been one of (200 mA·h·g−1).130 Like Li4Ti5O12, high potential (1.65 V
the most studied materials for anode. They can be vs. Li+/Li) of Nb2O5 prevents the formation of lithium
divided into several categories according to the dendrites and anode/electrolyte interface layers, which is
lithium storage mechanisms: (1) intercalation and highly associated with the safety of LIB. Low electronic
(2) conversion. conductivity is a hindrance to improving the perform-
Spinel Li4Ti5O12 is a well‐studied intercalation‐type ance of batteries with Nb2O5 anode. Liu et al.131 reported
anode material. During lithiation, the phase transition F‐doped Nb2O5 microflowers with nearly 97% exposed
occurs from spinel (Li4Ti5O12) to rocksalt‐like structure (100) facets. Exposed (100) facets of Nb2O5 anode
(Li7Ti5O12) by reducing the some Ti4+ to Ti3+. Three Li‐ enhance the intercalation performance through the
ions can be stored in each unit, leading to the theoretical Li‐ion transport along the loosely packed 4 g atomic
capacity of 175 mA·h·g−1. During the phase transition, layers. F‐doped Nb2O5 anode exhibits the improved the
only 0.1% lattice shrinkage is generated due to the strong Li +/electron transfer kinetics and pseudocapacitive
Ti‐O bond.124–126 Stable Li‐ion insertion/extraction volt- performance. The F‐doped Nb2O5 anode shows capacities
age of Li4Ti5O12 (1.55 V vs. Li+/Li) prevent the formation of 210.8 and 164.9 mA·h·g−1 at 1 and 10 C, respectively
of anode/electrolyte interface layer, which promotes the and 85.1% of capacity retention after 2000 cycles at 10 C.
diffusion of Li‐ions and decreases the safety concerns MoS2 is the transition metal dichalcogenides‐based
related to lithium plating.127 In spite of merits mentioned intercalation type anode material. MoS2 has a layered
above, low conductivity (10−13 S·cm−1) hinders the structure with a layer spacing of 6.2 Å , twice as large as
further enhancement of LIB performance. Cunha graphite. Weak Van der Waals forces between the layers
et al.128 reported the electrochemical performance of facilitates the rapid insertion/extraction of Li‐ions. It
epitaxial Li4Ti5O12 films with different orientations. has been considered a good anode material due to its
Epitaxial (100), (110), and (111)‐oriented Li4Ti5O12 films long cycle life, high power density, and twice larger
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
20 of 26 | CHOI ET AL.

F I G U R E 11 TM compound‐based anode. (A) XRD patterns of (100), (110), (111)‐oriented Li4Ti5O12 epitaxial films. (B) AFM images and
schematic diagram of Li4Ti5O12 epitaxial films with different orientations. (C) Discharge capacities of (100), (110), (111)‐oriented Li4Ti5O12
films. Reproduced with permission.128 Copyright 2019, American Chemical Society. (D) XRD patterns of α‐Fe2O3 nanoparticles synthesized
with different concentrations of Al3+. (E) Transmission electron microscopy (TEM) image of α‐Fe2O3 hexagonal‐shaped nanoparticle
prepared with 48 mg of Al precursor. Inset: SAED patterns obtained from a different region of the nanoparticle. (F) Long‐term cyclability of
hexagonal‐shaped α‐Fe2O3 nanoparticle‐anode. Reproduced with permission.129 Copyright 2019, American Chemical Society.

theoretical specific capacity (~800 mA·h·g−1).130 How- Polyaniline intercalated MoS2 on r‐GO shows high
ever, there is also a disadvantage that the large volume capacity, excellent rate capability, and superior cyclic
change is large during charge/discharge. Shokhen stability. The reversible capacity of polyaniline interca-
et al.132 investigated the electrochemical performance lated MoS2/rGO retains after 200 cycles
of vertically aligned and planarly oriented MoS2 as an (1197.2 mA·h·g−1), while bare MoS2 only has capacity of
anode for LIB. Vertically aligned MoS2 was synthesized 495.4 mA·h·g−1. Furthermore, polyaniline intercalated
through the chemical vapor deposition method. Pla- MoS2/rGO exhibits reversible capacities of 1206.5,
narly oriented MoS2 was prepared by overlaying a slurry 1106.1, 1050.6, 961.1, and 786.7 mA·h·g−1 at current
of 70% of MoS2 powder, 20% of polyvinylidene fluoride, density of 0.1, 0.5, 1, 2, and 5 A·g−1, respectively.
and 10% of carbon black onto the Cu foil via hand Iron oxide, cobalt oxide, manganese oxide, copper
coater. Cross‐section TEM images and XRD patterns oxide, and nickel oxide are the conversion type anode
indicate that the MoS2 layers grow vertically along the materials. The reaction can be described as the following
(100) orientation. Both vertically aligned MoS2 and equation:
planarly oriented MoS2 show high specific capacity
reaching the theoretical value. However, vertically TMa Ob + 2bLi + +2be−  aTM + bLi2 O, (4)
aligned MoS2 has higher cycling stability and colom-
bolic efficiency than planarly oriented MoS2. Zhang where TM is transition metal (Fe, Co, Mn, Cu, and Ni).
et al.133 synthesized polyaniline intercalated MoS2 They typically have high specific capacities and
nanosheets, which are vertically grown on reduced excellent cycle stability, but they also undergo large
graphene oxide (rGO). By intercalating the polyaniline, volume changes during Li‐ion insertion/extraction. In
interlayer between MoS2 layers is extended, facilitating addition, low conductivity is unfavorable to battery
the Li‐ion insertion/extraction. XRD peak shift of polyani- performance. Among them, iron oxides including FeO,
line intercalated MoS2/rGO toward lower angle indicates Fe2O3, and Fe3O4 are earth‐abundant and environment
the interlayer expanding. Enlarged interlayer spacing can friendly anode materials. The theoretical specific
be observed in the high‐resolution TEM image. capacities of FeO, Fe2O3, and Fe3O4 are 745, 1007, and
 27681696, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/bte2.20230010 by University Of St Andrews, Wiley Online Library on [27/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHOI ET AL. | 21 of 26

928 mA·h·g−1,133 respectively. He et al.129 investigated LiCoPO4 with olivine structure is higher than that
the electrochemical performance of Fe2O3 hexagonal of (100)‐ and (001)‐oriented LiCoPO4 due to higher
single crystals with an exposed (100) facet. XRD Li‐ion diffusion.
patterns in Figure 11D exhibits that the (110)/(104) (2) Solid‐state‐electrolyte: Recent studies of facet‐
peak intensity ratio increases as the concentration controlled solid‐state‐electrolyte materials were re-
of Al3+ increases, indicating the a‐direction preferred viewed for garnet‐type Li7La3Zr2O12 (LLZO) and
orientation of α ‐Fe2O3. TEM images shown in perovskite‐type Li3xLa2/3xTiO3 (LLTO). LLZO has
Figure 11E suggest that hexagonal α ‐Fe2O3 single three‐dimensional pathway for Li‐ion transport,
crystal has the (001) facet dominant. Single crystalline implying an isotropic nature of ionic conduction.
Fe2O3 shows a high specific capacity of 1261.3 mA·h·g−1 By using the well‐controlled LLZO, influence of
at 200 mA·g−1,133 outstanding cycle stability with grain boundary on Li‐ion transport, lattice distortion
capacity of ~900 mA·h·g−1 at 500 cycles (Figure 11F), effect on conductivity, and electronic conductivity
and high‐rate capability with a reversible capacity of difference between single crystalline and poly-
~605 mA·h·g−1 at 10 A·g−1. crystalline LLZO were investigated. LLTO has been
In addition to the anode materials mentioned above, considered as promising solid‐state‐electrolyte mate-
there are several new emerging anode materials such as rial due to its good ionic conductivity and excellent
phosphorus and phosphides. Phosphorus has a suitable chemical stability. The ionic conductivity change
potential (~0.8 V vs. Li + /Li) extremely high capacity depending on the area of Li‐ion transmission
(2596 mA·h·g−1). Also, rock‐salt‐type structure Li3+xV2O5 window and the domain orientation are discussed.
is considered a promising anode material for LIB. To Additionally, the improved performance of battery
solve the facing problems, existing anode materials as systems with well‐aligned SEs was addressed.
well as newly emerging anode materials are required to (3) Anode: Three different material groups are mainly
be studied in well‐controlled material systems. discussed for anode including carbon‐based materi-
als, VA and IVA‐based materials, and transition
metal compound‐based materials. Carbon‐based
4 | SUMMARY AND anode materials, especially graphite, is the most
PERSPECTIVES used for commercial anode of LIB due to its cyclic
stability and high specific capacity. Vertical align-
As the importance of electric vehicles and renewable ment facilitates the Li‐ion transport, leading to
energy increases due to climate change, the development enhancement of electrochemical performance. Apart
of batteries with superior performance and stability is from the carbon‐based anode materials, VA and IVA‐
becoming more crucial. Understanding battery systems is based materials have attracted great attention due to
critical to improving performance and stability. In this their extremely high specific capacities. Facet depen-
paper, the overall operating process and critical issues of dent battery performance and failure mechanism
LIB are presented. And then, we review the current state have been studied with single‐crystalline system. For
of facet‐controlled cathode, solid‐state‐electrolyte, and the transition metal compound‐based anode materi-
anode materials for LIBs, including epitaxial film, als, they mainly consist of intercalation‐type material
textured film, and single crystals. The outline of this (e.g., Li4Ti5O12, Nb2O3, and MoS2) and conversion‐
review mainly focused on is as follows: type materials (TMaOb, where TM = Fe, Co, Mn, Cu,
and Ni). There are some studies on facet‐controlled
(1) Cathode: Well‐controlled cathode materials with single crystal synthesized by solution process, and
various structure including layered structure, orientation‐controlled films obtained through the
spinel structure, olivine, and silicate were discussed. pulsed laser deposition and chemical vapor deposi-
LiCoO2 is the most studied cathode materials with tion. These showed meaningful results showing
layered structure. Cahode materials with layered different electrochemical performance depending
structures like LiCoO2 shows different electrochemi- on the facet. However, only a few studies have been
cal performance depending on the crystal orienta- reported.
tion. Recently, further improved cathode materials
with layered structure has been studied (e.g., LiCoO2, In all fields of cathode, anode, and electrolyte, research
LiNi1/3Co1/3Mn1/3O2, and LiNi0.8Co0.15Al0.05O2). on the electrochemical performance of batteries in well‐
Spinel LiMn2O4 single crystal shows higher electro- defined systems using epitaxial films, single crystals, and
chemical performance than polycrystalline LiMn2O4. textured films is in the early stage. This may be because
The electrochemical performance of (010)‐oriented most of the studies so far have been conducted on a bulk
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22 of 26 | CHOI ET AL.

scale. However, as the need for a battery with a small size Research Institute of Standards and Science) MPI Lab.
and high‐performance increases, research for fundamental Program, and SAIT, Samsung Electronics Co. Ltd.
understanding is greatly required.
Significant advances have been made in improving C O NF L I C T O F I N T E R E S T S TA T E M E N T
battery performance. However, there are still many The authors declare no conflict of interest.
issues and challenges that need to be addressed.
Fundamental understanding on the battery system can ORC ID
provide important insights into the development of Ji Hyun Baek https://orcid.org/0000-0002-2538-2354
stable and high‐performance batteries. In this regard,
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Engineering at Pohang University of
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for microbatteries. ACS Appl Energy Mater. 2019;2(5): from 2006 to 2009. Before he joined Seoul National
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