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org/journal/acsodf Article

Ternary Deep Eutectic Solvent (DES) with a Regulated Rate-

Determining Step for Efficient Recycling of Lithium Cobalt Oxide
Fengyu Huang, Taibai Li, Xiaohui Yan, Yige Xiong, Xin Zhang, Shengtao Lu, Nana An, Wenxia Huang,
Qihui Guo, and Xiang Ge*
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ABSTRACT: Deep eutectic solvents (DESs) have attracted extensive

research for their potential applications as leaching solvent to recycle
valuable metal elements from spent lithium ion batteries (LIBs). Despite
Downloaded via SABANCI UNIV on April 15, 2025 at 08:50:42 (UTC).

various advantages like being economical and green, the full potential of
conventional binary DES has not yet been harnessed because of the kinetics
during leaching. Herein, we consider the fundamental rate-determining-step
(RDS) in conventional binary DES and attempt to design ternary DES,
within which the chemical reaction kinetics and diffusion kinetics can be
regulated to maximize the overall leaching rate. As a proof of concept, we
show that the ternary choline chloride/succinic acid/ethylene glycol
(ChCl/SA/EG) type ternary DES can completely dissolve LCO powder
at 140 °C in 16 h. By systematically studying the leaching process at various
conditions, the energy barrier during leaching can be calculated to be 11.77
kJ/mol. Furthermore, we demonstrate that the extraction of the cobalt ions from the leaching solution can be directly achieved by
adding oxalic ions without neutralizing the solution. The precipitate can be used to regenerate LCO with high purity. The recycled
materials show comparable electrochemical performance with commercial LCO. Our design strategy of ternary DES with regulated
RDS is expected to have both scientific and technological significance in the field of hydrometallurgical recycling of LIBs.

■ INTRODUCTION
The massive production and upgrading of electronic devices
leaching process, which converts the metal elements from
electrodes to ions in solutions, followed by a series of chemical
and electric vehicles have led to the rapid growth for the methods including precipitation, solvent extraction, or electro-
production of rechargeable lithium ion batteries (LIBs),1−8 lytic deposition to recover the metal resources. Various
which will translate to tremendous amounts of waste in the solvents have been studied for the leaching process.34 Still,
coming years.9−17 Direct disposal of LIBs through landfilling or the simultaneous realization of high efficiency and environ-
burning would cause severe environmental pollution and mental friendliness is challenging. Inorganic acid leaching
resource wasting,18,19 thus calling for the development of an approach involves caustic reagents, which poses potential
efficient, economical, safe, and green recycling strategy of danger to workers and the environment.35 Other mild solvents
LIBs.20−24 Among various components in LIBs, most efforts to generally have their own problems. For example, organic acids
improve recycling have focused on the extraction of valuable like malic acid or oxalic acid are less corrosive than strong
metal elements from cathodes, especially cobalt for its high inorganic acids, but additional additives are required in the
value and environmental consideration.21,25−28 Currently, leaching process to reduce the valence of metal ions and
pyrometallurgy or mixed pyro- and hydrometallury is the facilitate the leaching kinetics.34,36,37 Despite much progress, a
dominating approach used in industry (companies including relatively high temperature and high concentration of caustic
Accure GmbH, Sony. Umicore, etc.).29,30 The pyrometallurgy
leaching reagent are necessary for efficient leaching. Therefore,
process generally involves a set of high-temperature processes
searching for new green solvents and understanding the
for the extraction of metal elements, including calcination,
roasting, oxide reduction, or smelting.31 It is relatively efficient
for recycling various transition metal elements. However, the Received: February 5, 2022
combustion treatment for the battery components would Accepted: March 2, 2022
generate huge energy consumption and environmental Published: March 24, 2022
pollution. Hydrometallurgy is considered to be a promising
alternative strategy due to its potential to extract metal
elements with high purity.32,33 Hydrometallurgy involves the
© 2022 The Authors. Published by
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mechanism to optimize the reaction kinetics are of both Co. Ltd.), succinic acid (C6H10O4; 99%; Shanghai Technology
scientific and technological significance.38−40 Co. Ltd.), and ethylene glycol (C2H6O2; 99%; Shanghai Saen
Recently, deep eutectic solvents (DESs) have emerged as a Chemical Technology Co. Ltd.) were used to prepare the
new type of solvents that show unconventional interaction ChCl/SA/EG ternary DES. ChCl was mixed with SA to
toward various metal compounds.41−43 Initially, DESs are prepare binary ChCl/SA DES at 90 °C, forming a transparent
considered to be quasi-ionic liquids due to their characteristic solution. A given amount of EG was then added to obtain the
properties including low vapor pressure and high thermal and ternary DES with various ratios to investigate the DES with
chemical stability,44 as well as high viscosity,45 while further optimized extraction kinetics.
research discovered that DESs are distinguished from ionic 2.2. Leaching and Extraction of Cobalt. The leaching
liquids due to the existence of a considerable molecular efficiency was studied by adding 3 g of ternary DES in a glass
portion.46,47 This enables DESs to be more compatible in vial. Then, 10 mg of lithium cobalt oxide (LiCoO2; 99%;
practical application due to the easier preparation. Note- Guangdong Canrd New Energy Technology Co. Ltd., LCO)
worthingly, various metal oxides are reported to show high was added into the solution. The glass vial was heated in an oil
solubility in DESs,48−50 which is attributed to the breaking of bath at various temperatures and heating times. The
the metal-oxide bonds of the solid in the DESs, which have transparent solution turned blue, indicating the dissolution of
rich hydrogen bond donor (HBD) species.50 In 2019, the the LCO.
extraction of cobalt element from lithium cobalt oxides To extract the cobalt ions, 0.536 g of sodium oxalate
(LCOs) was reported in a choline chloride/ethylene glycol (Na2C2O4; 99%; Guangdong Canrd New Energy Technology
(ChCl/EG) type DES without the addition of additional Co. Ltd., LCO) solid was dissolved in 100 mL of deionized
leaching reagent,51 opening a new frontier for the search of water to prepare 0.04 mol/L sodium oxalate solution, and 5
green solvent in lithium recycling. Considering the rich variety mL was taken in ternary DES dissolved with 0.01 g of LCO.
of DESs, many follow-up steps have been taken to optimize the One can see that solids are being produced in the cloudy
leaching efficiency.52−54 Fundamentally, the efficiency of a solution. After the solid is completely precipitated, filtrate and
chemistry process involves different rate-determining steps dry, pink cobalt oxalate solid can be obtained. Black Co3O4 can
(RDSs) like reaction kinetics and mass transfer rate, thus be obtained by burning cobalt oxalate in a muffle furnace at
requiring the optimization of the DESs composition (For 400 °C for 5 h. The obtained Co3O4 and Li2CO3 were evenly
example, the use of ternary DES) to realize the full potential. mixed in a muffle furnace at 600 °C for 5 h, and then, the
However, to our knowledge, current research works mainly temperature was adjusted to 900 °C for another 10 h to obtain
focus on binary DESs, which are composed of a hydrogen the recycled LCO. The structures of the recycled materials
bond acceptor (HBA) and an HBD. The intrinsic property of were characterized by X-ray diffraction (XRD, RigakuD/Max-
the selected HBA and HBD in a binary DES often limits the 3B) and scanning electron microscopy (SEM, Hitachi S-4800)
simultaneous realization of high reaction kinetics and the mass 2.3. Electrochemical Performance of Recycled LCO.
transfer rate. Despite the fact that ternary DESs have been The electrochemical performance of the recycled LCO was
proved powerful in many applications including the dissolution tested with coin cells. The active materials were mixed with
of lignin, 55 deconstruction of wheat straw, and CO PVDF binder and carbon black with a weight ratio of 8:1:1
absorption.56,57 This design principle has not yet been studied using NMP solvent. The slurry was then coated on the
to improve the efficiency for recycling LIBs. aluminum foil and then placed in an oven at 80 °C for 1 h and
Herein, we report the use of a ternary ChCl/SA (succinic then further dried at 110 °C under a vacuum for 12 h. The
acid)/EG type DES for extracting cobalt element from LCO electrode was then cut into circular sheets with a diameter of
materials. The design consideration is based on the high 12 mm and assembled using Li foil as the counter electrode
activity of the hydrogen bond donor of SA, which provides and 1 M LiPF6 in ethylene carbonate (EC)−dimethyl
high kinetics for chemical reaction, as well as the high mobility carbonate (DME) (1:1 in volume) as the electrolyte in a
of EG, which provides better diffusivity. At an optimized molar coin cell. Finally, various performance tests of the battery were
ratio of 1 ChCl/1 SA/1 EG, a high leaching efficiency of carried out. Cyclic voltammetry (CV) was performed using a
99.62% can be realized at 140 °C for 16 h. Meanwhile, we CHI660e electrochemical workstation (Chenhua, Shanghai).
found that the precipitation process can be achieved by tuning Galvanostatic charge−discharge tests were conducted on a
the complexation environment with the addition of sodium LAND battery program-control test system.
oxalic Na2C2O4 (Na2C2O4; 99%; Shanghai Saen Chemical
Technology Co. Ltd.) The cobalt ions can precipitate in the 3. RESULTS AND DISCUSSION
form of CoC2O4 without the neutralization of excessive 3.1. Improving the Leaching Efficiency by Regulating
protons, which is more superior than conventional alkali the RDS in Ternary DES. The recycling of LIBs through a
precipitation strategy in terms of the consumption of hydrometallurgical approach based on DESs has attracted
chemicals. The precipitated cobalt compounds can be used extensive research for its potential to extract metal elements
to refabricate LCO active materials with high purity. The with high purity and environmental friendliness. Currently,
recovered LCOs show a performance of electrochemical that is considering the existence of the large variety of DESs, extensive
comparable to commercial LCO raw materials. Such a strategy researches have been devoted to search for the type of DES
of regulating the rate-determining step based on a ternary DES with optimized leaching efficiency. Still, the leaching efficiency
is expected to be a general approach for developing a green needs improvement to meet the demand for the LIBs recycling
solvent with high efficiency in LIBs recycling. at large scale. The complete leaching of cathode powders using
binary DES composed of a HBD and a HBA species generally
2. EXPERIMENTAL SECTION require tens of hours or even days.52,53,58 Fundamentally, the
2.1. Preparation of the DES. Choline chloride leaching process of the solid materials in solvents involves the
(C5H14ClNO; 98%; Shanghai Saen Chemical Technology chemical reaction process and the mass transfer process. The
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Figure 1. Schematic illustration showing the design concept based on optimizing the rate-determining-step (RDS). (a) Overall reaction kinetics of
a ternary type DES can theoretically surpass those of a binary DES due to the synergistically regulated rate-determine-step (RDS). (b) Leaching
experiment. The dissolution of LCO in ChCl/SA/EG type ternary DES is significantly faster than those of binary type DESs composed of either
ChCl/EG or ChCl/SA.

chemical reaction rate is limited by the reaction kinetics while can be prepared. Afterward, LCO powders were added into the
the mass transfer rate is limited by the mobility of the DES. The whole system was then kept at various reactions
substance. The overall leaching rate is determined by the conditions. The leaching process is accompanied by the
slowest step involved (RDS). Therefore, when a certain type of generation of the [CoCl4]2− complex, which endows the
DES is used for leaching cathode materials, the apparent solvent with blue color, thus enabling the direct estimation of
leaching rate is limited by either the chemical reaction kinetics the leaching degree by comparing the colors. As shown in the
or the diffusion capability of the solvent (Figure 1a). For inset of Figure 1a, at the same condition (90 °C, 2 h), the
example, choline chloride (ChCl) has been widely used as the leaching rate changes with the composition and was optimized
HBA species to prepare DES due to its easy availability. When when the molar ratio of the ternary ChCl/SA/EG was set as
another HBD species is mixed with ChCl, the HBD species 1:1:1. This result provides solid evidence for the feasibility of
(e.g., succinic acid) with high proton activity would promote using ternary DES to push beyond the conventional binary
the debonding between the metal and the oxygen atoms, thus whose leaching rate is limited by their RDS.
benefiting the kinetics of the chemical reaction. But, such 3.2. Leaching Kinetics of the Ternary DES. To
ChCl/SA type DES provides poor diffusion capability for mass demonstrate the superior overall reaction kinetics of the
transfer. On the contrary, when the HBD species (e.g., ternary ChCl/SA/EG system, we systematically studied the
ethylene glycol) with high molecular mobility is selected, their leaching process at various conditions (90−150 °C, 0.5−16 h)
chemical reaction kinetics toward dissolving the cathodes are using an oil bath. As shown in Figure 2b, when 10 mg of LCO
usually not satisfactory. As a result, the overall leaching rate of powder was dissolved in 3 g of DES, the color of the leaching
cathode materials in binary DES is limited even though the solution deepened with the increase of the reaction temper-
system might have one superior property in terms of chemical ature and time. When the reaction proceeded at 140 °C for 16
reaction kinetics or mass transfer capability. h, no solid residues could be observed, indicating the complete
Herein, we attempt to break through the bottleneck of dissolution. UV−vis was used to quantify the concentration of
conventional binary DES by designing ternary DES system the dissolved ions in the supernatant leaching solution. Three
with regulated RDS. The ternary DES composed of ChCl, SA, characteristic bands (630, 667, and 696 nm) were detected,
and EG was selected as a proof of concept to demonstrate the which correspond to the absorption of [CoCl4]2− complex
synergistic effect for improving the overall leaching efficiency. species.59 The peak centered at 696 nm was used to quantify
Figure 1b briefly illustrates the synthesis and comparison of the the concentration of the dissolved cobalt ion. First, solutions
DESs. By directly mixing the starting raw materials with a with a series of known concentration were prepared to obtain
known ratio, binary or ternary DES with a given composition the standard concentration curve (Figure 3a). Afterward, the
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Figure 2. Dissolution efficiency of LCO ternary ChCl/SA/EG with various reaction conditions. (a) Digital photos of the reaction solution in glass
vials. (b and c) UV−vis spectra of the supernatant leaching solutions at temperatures of 90 (b) and 150 °C (c).

UV−vis spectrum of the leaching solutions could be measured dissolution in a solid−liquid leaching process. Therefore, an
(Figure 2 and Figure S2) and used to calculate the unreacted nucleus contraction model can be used to describe
concentration of the dissolved cobalt ions at given temperature the reaction and calculate the overall leaching kinetics.60 If the
and time. To describe the progress of the leaching process, the ratio between various leached ions stays constant, the apparent
leaching efficiency (η, ratio between the dissolved and input leaching rate equation can be established as
cobalt elements) was calculated and is given in Figure 3b. The
value of η can be defined as 1 − (1 − η)1/3 = Kt (2)

CV where K is the reaction rate constant while t stands for the

η= × 100% leaching time (min). At a given temperature, the reaction rate
MCo (1)
constant can be fitted (Figure 3c). Afterward, the activation
energy (Ea) can be derived by fitting the reaction rate constant
where C is the measured concentration of the cobalt element
at various temperature using
(mg/L), V is the volume of the solution (L), and MCo is the
mass of the cobalt element in the added LCO. The leaching Ea
efficiency increases with the reaction temperature or time. −ln K = − ln A
RT (3)
When the reaction time was set as 16 h, the leaching
efficiencies at both 140 and 150 °C were close to 1.0, which where A is the pre-exponential factor, R is the molar gas
corresponds to the complete dissolution as visualized in the constant, and T is the thermodynamic temperature (K). By
digital pictures in Figure 2a. fitting the −ln K to 1000/T, the apparent activation energy Ea
On the basis of the above leaching efficiency at various can be calculated to be 11.77 kJ/mol. The low activation
reaction conditions, the leaching kinetics can be calculated for energy of the ternary DES is superior than binary DES and is
fundamental understandings. The leaching process is accom- essential for realizing efficient leaching. The above results
panied by the continuous conversion of solid cobalt in the provide solid evidence for the feasibility of our proposed
lattice to the ionic cobalt complex in the solution, during which strategy to improve leaching kinetics by regulating the RDS in
the size of the solid particle decreases until complete a ternary DES system.
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Figure 3. Leaching kinetics of the LCO in the ternary DESs. (a) Standard concentration curve used to convert the tested UV−vis to the
concentration of cobalt ions. (b) Leaching efficiency of solution under different conditions. (c and d) Kinetics fitting and the linear fitting of
activation energy of cobalt leaching in the leaching process.

3.3. Regeneration of the LCO from the Leaching

Solution. The synergistic effect in ternary DES system
improved the overall leaching efficiency by balancing the
chemical reaction kinetics and mass transfer kinetics. To
evaluate its potential for practical application, the next step is
to develop economical methods to extract the dissolved
elements and regenerate functional materials with high
performance. In the proposed ChCl/SA/EG system, we
discovered that the precipitation of the cobalt ions can be
achieved by adding sodium oxalate without neutralizing the
solution in conventional alkaline-based precipitation approach,
thus significantly simplifiying the extraction process. The
precipitate can be collected and cleaned by a repeated
centrifuging/washing process. The obtained cobalt compounds
are CoC2O4 (Figure 4a) with irregular bulk morphology
(Figure S3). By annealing the powders at 400 °C for 5 h,
CoC2O4 can be converted to Co3O4 (Figure S6) with strip-like
morphology (Figure S4), which can further be used to
regenerate LCO by annealing with Li2CO3 at 600 °C for 5 h
and 900 °C for 10 h. The regenerated LCO has high purity and
crystallinity (Figure 4a) with microscale size (Figure S5). The
structure of the regenerated LCO is expected to enable the
materials to function well in LIBs.
To verify the suitability of the regenerated LCO as potential
cathode used in LIBs, we used coin cells to compare its
electrochemical performance with commercialized microsized
LCO (morphology given in Figure S5). CV curves show that
the recycled LCO has a pair of sharp redox peak at 4.0/4.2 V
(Figure S7), which is similar to commercial LCO. The recycled
LCO shows an initial discharge capacity of 164.2 mAh/g at a Figure 4. (a) XRD of the precipitate before and after calcination after
current density of 0.2 C and a voltage range of 3.0−4.5 V. After adding excessive deionized water and recycle LCO. (b) Cycle test of
regenerated LCO materials under better conditions. (c) Rate
50 cycles, 141.7 mAh/g can be maintained (Figure 4b). The
capability test of regenerated LCO materials under better conditions.
charge/discharge curves at different cycles in the inset of
Figure 4b show a plateau at 3.7 V. The rate capability in Figure
4c shows that the discharge capacity of the recycled LCO does
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not show obvious change when the current densities are in the Nana An − Department of Materials and Metallurgy, Guizhou
range 0.1−2 C. The above results indicate that the regenerated University, Guiyang 550025, China
LCO has comparable electrochemical performance compared Wenxia Huang − Department of Materials and Metallurgy,
with commercialized LCO in terms of specific capacity, Guizhou University, Guiyang 550025, China
kinetics, and stability. The high quality of the regenerated Qihui Guo − Department of Materials and Metallurgy,
LCO proves that the ternary DES is qualified as an efficient Guizhou University, Guiyang 550025, China
solvent for the hydrometallurgical recycling of cathodes from Complete contact information is available at:
spent LIBs. https://pubs.acs.org/10.1021/acsomega.2c00742
4. CONCLUSIONS Author Contributions
This work demonstrates the successful improvement of the X.G.: Data curation; Funding acquisition; Roles/Writing-
overall leaching efficiency when using DES for cobalt recycling original draft; Supervision; Writing-review and editing. F.H.:
from spent LIBs. The rational design of ternary DES provides a Formal analysis; Methodology; Writing-review and editing;
synergistic effect to regulate the chemical reaction kinetics and Roles/Writing-original draft; Validation. T.L.: Investigation;
diffusion kinetics, which outperforms conventional binary DES Methodology; Writing-review and editing. X.Y.: Software;
whose overall leaching kinetic is limited by its RDS. For the Visualization. Y.X.: Software. X.Z,: Data curation. S.L.:
ChCl/SA/EG ternary DES system shown in this work, the Methodology. N.A.: Visualization; Methodology. W.H.:
complete dissolution of LCO can be achieved at 140 °C for 16 Software. Q.G.: Software.
h. Systematic study of the leaching experiment at various Funding
conditions show that the energy barrier during leaching is This work was supported by the support from the talent
11.77 kJ/mol. The extraction of the dissolved cobalt element program of Guizhou University (702759203301), Natural
can be simply achieved using oxalic ions. The precipitate can Science Foundation of Guizhou Science and Technology
be used to regenerate LCO, which shows comparable Department (QKHJC-ZK[2021]-YB257), and Guida SRT Zi
electrochemical performance with commercial LCO in terms (2021) 008 Hao
of discharge capacity, rate capability, and stability. The above
Notes
results prove the viability for using ternary DES with regulated
The authors declare no competing financial interest.

■
RDS to improve the leaching kinetics. The further extraction
and regeneration of valuable materials from the leaching ACKNOWLEDGMENTS
solution is easy and efficient, thus enabling the design strategy
of ternary DES to be of both scientific and technological The authors acknowledge Ao Ren and Jianglong Liu from
significance. GZU School of Mechanical Engineering for their assistance in

■
performing the experiment.

*
ASSOCIATED CONTENT
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■ REFERENCES
(1) Cao, C.; Liang, F.; Zhang, W.; Liu, H.; Liu, H.; Zhang, H.; Mao,
J.; Zhang, Y.; Feng, Y.; Yao, X.; Ge, M.; Tang, Y. Commercialization-
https://pubs.acs.org/doi/10.1021/acsomega.2c00742. Driven Electrodes Design for Lithium Batteries: Basic Guidance,
Figures of digital pictures and UV−vis spectrum of the Opportunities, and Perspectives. Small. 2021, 17 (43), 2102233.
leaching solution, SEM images of the precipitated (2) Yan, X.; Li, T.; Xiong, Y.; Ge, X. Synchronized ion and electron
CoC2O4, Co3O4, and commercial LCO at different transfer in a blue T-Nb2O5‑x with solid-solution-like process for fast
magnification rates, XRD pattern of the annealed Co3O4, and high volumetric charge storage. Energy Storage Mater. 2021, 36,
213−21.
and CV curves of cells assembled from recycled and (3) Ge, X.; Gu, C.; Yao, Z.; Sun, J.; Wang, X.; Tu, J.
commercial LCO (PDF) Pseudocapacitive material with 928 mAh cm−3 particle-level

■ AUTHOR INFORMATION
Corresponding Author
volumetric specific capacity enabled by continuous phase-transition.
Chem. Eng. J. 2018, 338, 211−7.
(4) Liu, Y.; Zhu, Y.; Cui, Y. Challenges and opportunities towards
fast-charging battery materials. Nature Energy. 2019, 4, 540.
Xiang Ge − Department of Materials and Metallurgy, Guizhou (5) Liu, J.; Bao, Z.; Cui, Y.; Dufek, E. J.; Goodenough, J. B.;
University, Guiyang 550025, China; orcid.org/0000- Khalifah, P.; Li, Q.; Liaw, B. Y.; Liu, P.; Manthiram, A.; et al.
0001-7932-5606; Email: [email protected] Pathways for practical high-energy long-cycling lithium metal
batteries. Nature Energy. 2019, 4 (3), 180.
Authors (6) Yuan, B.; Wen, K.; Chen, D.; Liu, Y.; Dong, Y.; Feng, C.; Han,
Fengyu Huang − Department of Materials and Metallurgy, Y.; Han, J.; Zhang, Y.; Xia, C.; et al. Composite separators for robust
Guizhou University, Guiyang 550025, China high rate lithium ion batteries. Adv. Funct Mater. 2021, 31 (32),
Taibai Li − Department of Materials and Metallurgy, Guizhou 2101420.
University, Guiyang 550025, China (7) Zhao, Q.; Chen, X.; Hou, W.; Ye, B.; Zhang, Y.; Xia, X.; Wang, J.
Xiaohui Yan − Department of Materials and Metallurgy, A facile, scalable, high stability Lithium metal anode. SusMat 2022, 2
Guizhou University, Guiyang 550025, China (1), 104−112.
(8) Liao, H.; Zhong, W.; Li, T.; Han, J.; Sun, X.; Tong, X.; Zhang, Y.
Yige Xiong − Department of Materials and Metallurgy, A review of self-healing electrolyte and their applications in flexible/
Guizhou University, Guiyang 550025, China stretchable energy storage devices. Electrochim. Acta 2022, 404,
Xin Zhang − Department of Materials and Metallurgy, 139730.
Guizhou University, Guiyang 550025, China (9) Zheng, X.; Zhu, Z.; Lin, X.; Zhang, Y.; He, Y.; Cao, H.; Sun, Z. A
Shengtao Lu − Department of Materials and Metallurgy, mini-review on metal recycling from spent lithium ion batteries.
Guizhou University, Guiyang 550025, China Engineering. 2018, 4 (3), 361−70.

11457 https://doi.org/10.1021/acsomega.2c00742
ACS Omega 2022, 7, 11452−11459
ACS Omega http://pubs.acs.org/journal/acsodf Article

(10) Harper, G.; Sommerville, R.; Kendrick, E.; Driscoll, L.; Slater, (28) Gangaja, B.; Nair, S.; Santhanagopalan, D. Reuse, Recycle, and
P.; Stolkin, R.; Walton, A.; Christensen, P.; Heidrich, O.; Lambert, S.; Regeneration of LiFePO4 Cathode from Spent Lithium-Ion Batteries
et al. Recycling lithium-ion batteries from electric vehicles. Nature. for Rechargeable Lithium-and Sodium-Ion Batteries. ACS Sustainable
2019, 575 (7781), 75−86. Chem. Eng. 2021, 9 (13), 4711−21.
(11) Chen, M.; Zhang, Y.; Xing, G.; Chou, S.-L.; Tang, Y. (29) Meshram, P.; Pandey, B.; Mankhand, T. Extraction of lithium
Electrochemical energy storage devices working in extreme con- from primary and secondary sources by pre-treatment, leaching and
ditions. Energy Environ. Sci. 2021, 14 (6), 3323−51. separation: A comprehensive review. Hydrometallurgy. 2014, 150,
(12) Wang, C.; Li, Y.; Zhang, Y.; Zhang, L.; Gu, C.; Wang, X.; Tu, J. 192−208.
Integrating a 3D porous carbon fiber network containing cobalt with (30) Ciez, R. E.; Whitacre, J. F. Examining different recycling
artificial solid electrolyte interphase to consummate advanced processes for lithium-ion batteries. Nature Sustainability. 2019, 2 (2),
electrodes for lithium−sulfur batteries. Materials Today Energy. 148−56.
2022, 24, 100930. (31) Piątek, J.; Afyon, S.; Budnyak, T. M.; Budnyk, S.; Sipponen, M.
(13) Zhao, Z.; Xue, Z.; Xiong, Q.; Zhang, Y.; Hu, X.; Chi, H.; Qin, H.; Slabon, A. Sustainable Li-Ion Batteries: Chemistry and Recycling.
H.; Yuan, Y.; Ni, H. Titanium niobium oxides (TiNb2O7): Design, Adv. Energy Mater. 2021, 11, 2003456.
fabrication and application in energy storage devices. Sustainable (32) Liang, Z.; Cai, C.; Peng, G.; Hu, J.; Hou, H.; Liu, B.; Liang, S.;
Materials and Technologies. 2021, 30, No. e00357. Xiao, K.; Yuan, S.; Yang, J. Hydrometallurgical Recovery of Spent
(14) Zhou, R.; Shen, S.; Zhong, Y.; Liu, P.; Zhang, Y.; Zhang, L.; Lithium Ion Batteries: Environmental Strategies and Sustainability
Wang, X.; Xia, X.; Tu, J. Co-construction of advanced sulfur host by Evaluation. ACS Sustainable Chem. Eng. 2021, 9 (17), 5750−67.
implanting titanium carbide into Aspergillus niger spore carbon. Chin. (33) Chen, W.-S.; Ho, H.-J. Recovery of valuable metals from
Chem. Lett., in press, 2021. lithium-ion batteries NMC cathode waste materials by hydro-
(15) Liang, L.; Chen, X.; Yuan, W.; Chen, H.; Liao, H.; Zhang, Y. metallurgical methods. Metals. 2018, 8 (5), 321.
Highly Conductive, Flexible, and Nonflammable Double-Network (34) Yao, Y.; Zhu, M.; Zhao, Z.; Tong, B.; Fan, Y.; Hua, Z.
Poly (ionic liquid)-Based Ionogel Electrolyte for Flexible Lithium-Ion Hydrometallurgical processes for recycling spent lithium-ion batteries:
Batteries. ACS Appl. Mater. Interfaces. 2021, 13 (21), 25410−20. a critical review. ACS Sustainable Chem. Eng. 2018, 6 (11), 13611−27.
(16) Wang, R.; Dai, X.; Qian, Z.; Sun, Y.; Fan, S.; Xiong, K.; Zhang, (35) Liu, C.; Lin, J.; Cao, H.; Zhang, Y.; Sun, Z. Recycling of spent
H.; Wu, F. In situ surface protection for enhancing stability and lithium-ion batteries in view of lithium recovery: A critical review.
performance of LiNi 0.5 Mn 0.3 Co 0.2 O2 at 4.8 V: the working Journal of Cleaner Production. 2019, 228, 801−13.
mechanisms. ACS Materials Letters. 2020, 2 (4), 280−90. (36) Yao, L.; Yao, H.; Xi, G.; Feng, Y. Recycling and synthesis of
(17) Li, T.; Li, Y.; Sun, Y.; Qian, Z.; Wang, R. New Insights on the LiNi1/3Co1/3Mn1/3O2 from waste lithium ion batteries using D,L-malic
Good Compatibility of Ether-Based Localized High-Concentration
acid. RSC Adv. 2016, 6 (22), 17947−54.
Electrolyte with Lithium Metal. ACS Materials Letters. 2021, 3 (6), (37) Sun, L.; Qiu, K. Organic oxalate as leachant and precipitant for
838−44.
the recovery of valuable metals from spent lithium-ion batteries. Waste
(18) Or, T.; Gourley, S. W. D.; Kaliyappan, K.; Yu, A.; Chen, Z.
Manage. 2012, 32 (8), 1575−82.
Recycling of mixed cathode lithium-ion batteries for electric vehicles:
(38) Nan, J.; Han, D.; Zuo, X. Recovery of metal values from spent
Current status and future outlook. Carbon Energy. 2020, 2 (1), 6−43.
lithium-ion batteries with chemical deposition and solvent extraction.
(19) Fan, E.; Li, L.; Wang, Z.; Lin, J.; Huang, Y.; Yao, Y.; Chen, R.;
J. Power Sources. 2005, 152, 278−84.
Wu, F. Sustainable recycling technology for Li-ion batteries and
(39) Zhang, L.; Li, L.; Rui, H.; Shi, D.; Peng, X.; Ji, L.; Song, X.
beyond: challenges and future prospects. Chem. Rev. 2020, 120 (14),
Lithium recovery from effluent of spent lithium battery recycling
7020−63.
(20) Natarajan, S.; Aravindan, V. An urgent call to spent LIB process using solvent extraction. J. Hazard Mater. 2020, 398, 122840.
recycling: whys and wherefores for graphite recovery. Adv. Energy (40) Punt, T.; Akdogan, G.; Bradshaw, S.; van Wyk, P. Development
Mater. 2020, 10 (37), 2002238. of a novel solvent extraction process using citric acid for lithium-ion
(21) Lv, W.; Wang, Z.; Cao, H.; Sun, Y.; Zhang, Y.; Sun, Z. A battery recycling. Miner Eng. 2021, 173, 107204.
Critical Review and Analysis on the Recycling of Spent Lithium-Ion (41) Gutiérrez, M. C.; Ferrer, M. L.; Mateo, C. R.; del Monte, F.
Batteries. ACS Sustainable Chem. Eng. 2018, 6 (2), 1504−21. Freeze-drying of aqueous solutions of deep eutectic solvents: a
(22) Yu, J.; Wang, X.; Zhou, M.; Wang, Q. A redox targeting-based suitable approach to deep eutectic suspensions of self-assembled
material recycling strategy for spent lithium ion batteries. Energy structures. Langmuir. 2009, 25 (10), 5509.
Environ. Sci. 2019, 12 (9), 2672−7. (42) Ge, X.; Gu, C. D.; Wang, X. L.; Tu, J. P. Correlation between
(23) Wang, R.; Sun, Y.; Yang, K.; Zheng, J.; Li, Y.; Qian, Z.; He, Z.; Microstructure and Electrochemical Behavior of the Mesoporous
Zhong, S. One-time sintering process to modify xLi2MnO3 (1-x) Co3O4 Sheet and Its Ionothermal Synthesized Hydrotalcite-like α-
LiMO2 hollow architecture and studying their enhanced electro- Co(OH)2 Precursor. J. Phys. Chem. C 2014, 118 (2), 911−23.
chemical performances. Journal of Energy Chemistry. 2020, 50, 271−9. (43) Ge, X.; Gu, C. D.; Wang, X. L.; Tu, J. P. Ionothermal synthesis
(24) Yang, K.; Liu, D.; Qian, Z.; Jiang, D.; Wang, R. Computational of cobalt iron layered double hydroxides (LDHs) with expanded
Auxiliary for the Progress of Sodium-Ion Solid-State Electrolytes. ACS interlayer spacing as advanced electrochemical materials. J. Mater.
Nano 2021, 15 (11), 17232−46. Chem. A 2014, 2 (40), 17066−76.
(25) Schiavi, P. G.; Altimari, P.; Branchi, M.; Zanoni, R.; Simonetti, (44) Chen, W.; Xue, Z.; Wang, J.; Jiang, J.; Zhao, X.; Mu, T.
G.; Navarra, M. A.; Pagnanelli, F. Selective recovery of cobalt from Investigation on the thermal stability of deep eutectic solvents. Acta
mixed lithium ion battery wastes using deep eutectic solvent. Chem. Phys. Chim Sin. 2018, 34, 904−11.
Eng. J. 2021, 417, 129249. (45) Zhang, C.; Zhang, L.; Yu, G. Eutectic electrolytes as a
(26) Wang, H.; Huang, K.; Zhang, Y.; Chen, X.; Jin, W.; Zheng, S.; promising platform for next-generation electrochemical energy
Zhang, Y.; Li, P. Recovery of lithium, nickel, and cobalt from spent storage. Acc. Chem. Res. 2020, 53 (8), 1648−59.
lithium-ion battery powders by selective ammonia leaching and an (46) Ge, X.; Gu, C. D.; Wang, X.; Tu, J. Deep Eutectic Solvents
adsorption separation system. ACS Sustainable Chem. Eng. 2017, 5 (DESs) Derived Advanced Functional Materials for Energy and
(12), 11489−95. Environmental Applications: Challenges, Opportunities, and Future
(27) Yang, Y.; Guo, J.-Z.; Gu, Z.-Y.; Sun, Z.-H.; Hou, B.-H.; Yang, Vision. J. Mater. Chem. A 2017, 5, 8209−29.
A.-B.; Ning, Q.-L.; Li, W.-H.; Wu, X.-L. Effective recycling of the (47) Yu, D.; Xue, Z.; Mu, T. Eutectics: formation, properties, and
whole cathode in spent lithium ion batteries: from the widely used applications. Chem. Soc. Rev. 2021, 50 (15), 8596−638.
oxides to high-energy/stable phosphates. ACS Sustainable Chem. Eng. (48) Wu, J.; Liang, Q.; Yu, X.; Lü, Q. F.; Ma, L.; Qin, X.; Chen, G.;
2019, 7 (14), 12014. Li, B. Deep Eutectic Solvents for Boosting Electrochemical Energy

11458 https://doi.org/10.1021/acsomega.2c00742
ACS Omega 2022, 7, 11452−11459
ACS Omega http://pubs.acs.org/journal/acsodf Article

Storage and Conversion: A Review and Perspective. Adv. Funct Mater.

2021, 31, 2011102.
(49) Pateli, I. M.; Abbott, A. P.; Jenkin, G. R.; Hartley, J. M.
Electrochemical oxidation as alternative for dissolution of metal
oxides in deep eutectic solvents. Green Chemistry. 2020, 22 (23),
8360−8.
(50) Pateli, I. M.; Thompson, D.; Alabdullah, S. S. M.; Abbott, A. P.;
Jenkin, G. R. T.; Hartley, J. M. The effect of pH and hydrogen bond
donor on the dissolution of metal oxides in deep eutectic solvents.
Green Chemistry. 2020, 22 (16), 5476−86.
(51) Tran, M. K.; Rodrigues, M-TF; Kato, K.; Babu, G.; Ajayan, P.
M. Deep eutectic solvents for cathode recycling of Li-ion batteries.
Nature Energy. 2019, 4, 339−45.
(52) Wang, M.; Tan, Q.; Liu, L.; Li, J. A low-toxicity and high-
efficiency deep eutectic solvent for the separation of aluminum foil
and cathode materials from spent lithium-ion batteries. J. Hazard
Mater. 2019, 380, 120846.
(53) Wang, S.; Zhang, Z.; Lu, Z.-G.; Xu, Z. A novel method for
screening deep eutectic solvent to recycle cathode of Li-ion batteries.
Green Chemistry. 2020, 22, 4473−82.
(54) Chen, Y.; Wang, Y.; Bai, Y.; Duan, Y.; Zhang, B.; Liu, C.; Sun,
X.; Feng, M.; Mu, T. Significant Improvement in Dissolving Lithium-
Ion Battery Cathodes Using Novel Deep Eutectic Solvents at Low
Temperature. ACS Sustainable Chem. Eng. 2021, 9 (38), 12940−8.
(55) Xue, B.; Yang, Y.; Tang, R.; Xue, D.; Sun, Y.; Li, X. Efficient
dissolution of lignin in novel ternary deep eutectic solvents and its
application in polyurethane. Int. J. Biol. Macromol. 2020, 164, 480−8.
(56) Ci, Y-h; Yu, F.; Zhou, C-x; Mo, H-e; Li, Z-y; Ma, Y-q; Zang, L-
h New ternary deep eutectic solvents for effective wheat straw
deconstruction into its high-value utilization under near-neutral
conditions. Green Chemistry. 2020, 22 (24), 8713−20.
(57) Tao, D. J.; Qu, F.; Li, Z. M.; Zhou, Y. Promoted absorption of
CO at high temperature by cuprous-based ternary deep eutectic
solvents. AlChE J. 2021, 67 (2), No. e17106.
(58) Padwal, C.; Pham, H. D.; Jadhav, S.; Do, T. T.; Nerkar, J.;
Hoang, L. T. M.; Kumar Nanjundan, A.; Mundree, S. G.; Dubal, D. P.
Deep Eutectic Solvents: Green Approach for Cathode Recycling of Li- Recommended by ACS
Ion Batteries. Advanced Energy and Sustainability Research 2022, 3,
2100133.
(59) Hsieh, Y.-T.; Lai, M.-C.; Huang, H.-L.; Sun, I.-W. Speciation of Direct Electrochemical Leaching Method for High-Purity
cobalt-chloride-based ionic liquids and electrodeposition of Co wires. Lithium Recovery from Spent Lithium Batteries
Electrochim. Acta 2014, 117, 217−23. Liming Yang, Xubiao Luo, et al.
(60) He, L.-P.; Sun, S.-Y.; Song, X.-F.; Yu, J.-G. Leaching process for MARCH 07, 2023
recovering valuable metals from the LiNi1/3Co1/3Mn1/3O2 cathode of ENVIRONMENTAL SCIENCE & TECHNOLOGY READ
lithium-ion batteries. Waste Manage. 2017, 64, 171−81.
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