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org/est Article

Selective Extraction of Critical Metals from Spent Lithium-Ion

Batteries
Mengmeng Wang, Kang Liu, Zibo Xu, Shanta Dutta, Marjorie Valix, Daniel S. Alessi, Longbin Huang,
Julie B. Zimmerman, and Daniel C. W. Tsang*
Cite This: Environ. Sci. Technol. 2023, 57, 3940−3950 Read Online

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ABSTRACT: Selective and highly efficient extraction technologies for

the recovery of critical metals including lithium, nickel, cobalt, and
Downloaded via UNIV DE CORDOBA on March 21, 2024 at 08:45:30 (UTC).

manganese from spent lithium-ion battery (LIB) cathode materials are

essential in driving circularity. The tailored deep eutectic solvent (DES)
choline chloride−formic acid (ChCl−FA) demonstrated a high selectivity
and efficiency in extracting critical metals from mixed cathode materials
(LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1) under mild conditions
(80 °C, 120 min) with a solid−liquid mass ratio of 1:200. The leaching
performance of critical metals could be further enhanced by
mechanochemical processing because of particle size reduction, grain
refinement, and internal energy storage. Furthermore, mechanochemical
reactions effectively inhibited undesirable leaching of nontarget elements (iron and phosphorus), thus promoting the selectivity and
leaching efficiency of critical metals. This was achieved through the preoxidation of Fe and the enhanced stability of iron phosphate
framework, which significantly increased the separation factor of critical metals to nontarget elements from 56.9 to 1475. The
proposed combination of ChCl−FA extraction and the mechanochemical reaction can achieve a highly selective extraction of critical
metals from multisource spent LIBs under mild conditions.
KEYWORDS: Selective recovery, deep eutectic solvent, choline chloride−formic acid, mechanochemistry, sustainable waste management

1. INTRODUCTION and graphite).13 The metal oxides selected would determine

The goal of “carbon neutrality” has driven the development of the electrochemical performance of LIBs.14,15 Based on
clean and low-carbon new energy vehicles (NEVs) as an differences in the crystal structures of metal oxides, cathode
materials may include lithium iron phosphate (LiFePO4),
important approach to achieving “decarbonization” in the
ternary nickel cobalt manganese oxide (LiNixCoyMnzO2; x + y
transport industry worldwide.1,2 According to Global EV
+ z = 1), lithium cobalt oxide (LiCoO2), and lithium
Outlook 2022 released by the International Energy Agency, the
manganate (LiMnO2).16 After completing the limited life
annual global stocks of NEVs are expected to reach 200 million
cycle (6−8 years) of power LIBs, the critical metals, lithium
by 2030, 10 times more than the current stocks.3 Lithium-ion
(Li), nickel (Ni), cobalt (Co), and manganese (Mn), should
batteries (LIBs), compared to its competitors, can store a
be recycled for battery remanufacturing as a critical strategy for
greater amount of energy with a lower mass and have higher
sustainable resource circulation and minimum environmental
energy efficiency, better high-temperature performance, and
pollution.17 Battery recycling technologies vary, with pyrome-
lower self-discharge.4 They are expected to play a critical role
tallurgy and hydrometallurgy being the dominant technolo-
in the deployment of low-emission vehicles such as EVs.5
gies.18−20 Pyro- and hydrometallurgical routes with smelting
However, the price fluctuations and supply shortage of metals
followed by recovery of metals from the resulting alloys are
and raw/refined materials for LIB production severely restrict
considered proven technologies with high metal recovery.21,22
the sustainable development of the LIB industry.6−8 Consid-
However, Li recovery is difficult, and the process is
ering the mining costs and environmental burdens of primary unavoidably energy- and emission-intensive.23 In comparison,
ore and limited reserves of metal resources, it is important to
recognize that future LIB material demand must be
supplemented by efficient recycling of critical metals from Received: October 19, 2022
spent LIBs.9−12 Revised: February 5, 2023
LIBs are constructed with a shell (stainless steel or plastic Accepted: February 6, 2023
pack), current collector (copper foil and aluminum foil), Published: February 17, 2023
plastic separator, electrolyte (lithium hexafluorophosphate),
anode material (graphite), and cathode material (metal oxide

© 2023 American Chemical Society https://doi.org/10.1021/acs.est.2c07689

3940 Environ. Sci. Technol. 2023, 57, 3940−3950
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Figure 1. Flowchart for selective extraction of Li, Ni, Co, and Mn from mixed cathode materials of LIBs.
mechanical and hydrometallurgical technologies result in high
metal recovery, lower energy use, and capital expenditures but
use significant quantities of water.24,25 These issues and the
diversity of cathode materials in LIBs continue to challenge the
development of practical approaches to achieve selective
extraction of target metals from hybrid battery materials in
the recycling industry.26−29
The term solvometallurgy was coined to extend hydro-
metallurgy to the use of solvents other than water.30 As a
complementary technology to pyrometallurgy and hydro-
metallurgy, integrating solvometallurgy with metal leaching
and solvent extraction into a consolidated system can simplify
the extraction process.31 A key benefit of solvometallurgy is its
higher leaching selectivity compared to aqueous leaching
solutions, reducing reagent consumption and requiring fewer
subsequent purification steps.32,33 One such emerging system
is deep eutectic solvents (DESs), which are defined as a
eutectic mixture formed through hydrogen bonding between
two (or more) components, i.e., a hydrogen bond donor and
acceptor.34,35 Recent studies and interest in the application of
DES for extraction of metals from spent LIBs are driven by its
green attributes, high tunability, and considerable selectivity for
metal extraction.36−43 The extraction of Li and Co from spent
LIBs could be achieved using choline chloride (ChCl)−
ethylene glycol as the solvent, with extraction of 89.8 and 50.3
wt % for Li and Co, respectively, after leaching at 180 °C for
24 h.44 Wang et al. also revealed that 89.1 wt % of Co was
extracted when the LiCoO2 cathode material was leached in
ChCl−urea at 170 °C for 12 h with vigorous stirring.45 DES is
proven to be a feasible approach for extracting critical metals
from spent LIBs.46−49 However, its application is still limited
by high operation temperature (180−220 °C) and long
reaction time (18−24 h), associated with high energy
consumption and production cost.50 In addition, the diversity
of constituent elements and differences in the crystal structures
of metal compounds would limit the selectivity in extracting
critical metals from multisource and heterogeneous hybrid
cathode materials, thus lowering the feasibility of solvome-
tallurgy systems. Specifically, the concomitant extraction of
nontarget elements such as iron (Fe) and phosphorus (P)
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poses separation challenges and hinders battery remanufactur-
ing.46,50
In view of the above limitations, we designed a tailored DES,
ChCl−formic acid (ChCl−FA), to solve the current shortfalls
in solvometallurgy systems. In a tailored DES leaching system,
the collaboration of proton hydrogen in FA and chlorine in
ChCl, led to the dissolution−reduction−complexation of
critical metals in mixed cathode materials (LiFePO4:Li-
(NiCoMn)1/3O2 mass ratio of 1:1) at a low temperature of
80 °C and a time of only 120 min. Mechanochemical
processing of the cathode materials was also considered as a
preprocessing step to further enhance DES leaching. The
objectives of this study were as follows: (1) to explore the
selective extraction performance of ChCl−FA for critical
metals in single and mixed LIB cathode materials; (2) to
investigate the impact of mechanochemical processing on the
efficiency of leaching of critical metals; and (3) to clarify the
inhibition mechanisms of mechanochemical reactions with
respect to the leaching of nontarget species.
2. MATERIALS AND METHODS
2.1. Chemicals and Materials. Choline chloride
(C5H14ClNO; AR, 98%; Aladdin), formic acid (HCOOH;
AR, 88%; Aladdin), sodium hydroxide (NaOH; AR, 98%;
Accuchem), sodium carbonate (Na2CO3; AR, 98%; Fisher
Chemical), silver nitrate (AgNO3; AR, 99.8%; Accuchem),
hydrochloric acid (HCl; AR, 38%, v/v; Aladdin), and nitric
acid (HNO3; AR, 68%, v/v; Aladdin) were purchased from
various chemical reagent supply companies. Spent LiFePO4
and Li(NiCoMn)1/3O2 batteries were obtained from Dong-
jiang Electric Vehicle Co., Ltd., Shenzhen, China. The
dismantling parameters of the spent LIBs are shown in Note
S1 and Tables S1−S3. The synthesis steps of ChCl−FA are
given in Note S2. The primary functional groups of ChCl and
FA in the formed ChCl−FA DES shifted to lower wave-
numbers, confirming the formation of hydrogen bonds (Figure
S1).51,52 Deionized water was used to dilute and dissolve
samples.
2.2. Metal Leaching. The metal extraction performance of
ChCl−FA was evaluated by a batch leaching test with 0.05 g of
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Figure 2. Leaching percentages of mixed cathode materials in different solvent systems: (a) FA−H2O, (b) ChCl−H2O, and (c) ChCl−FA (FA−
H2O and ChCl−H2O represent that the ChCl or FA in the ChCl−FA system was replaced by an equal mass of deionized water; conditions:
LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1, leaching temperature of 80 °C, leaching time of 120 min, and the solid−liquid mass ratio of 1:200);
the leaching percentages of single cathode materials (d) LiFePO4 and (e) Li(NiCoMn)1/3O2 in different solvent systems (conditions: leaching
temperature of 80 °C, leaching time of 120 min, and the solid−liquid mass ratio of 1:200); (f) UV−vis results of ChCl−FA before and after use.

cathode material powder (LiFePO4:Li(NiCoMn)1/3O2 mass
ratio of 1:1) and ChCl−FA at asolid−liquid mass ratio of
1:200. The materials were weighed and placed in a glass
container. After sealing, the glass container was placed in a
stainless-steel water bath where it was heated continuously at
80 °C with a fixed stirring speed (200 rpm) and leached for
different durations (10, 20, 30, 40, and 120 min). After the
leaching, ChCl−FA and the unreacted cathode material
powder were separated using a 0.45 μm membrane. Inductively
Coupled Plasma-Optical Emission Spectrometry (ICP-OES,
Agilent 5110, USA) was used to measure the concentrations of
metals that dissolved in the DES after a quantitative acid
digestion process using 5% (v/v) HNO3.
2.3. Mechanochemical Reactions. The mechanochem-
ical pretreatment was conducted to establish its impact on DES
extraction performance. This was conducted by placing 1.0 g of
the mixed cathode materials (LiFePO4:Li(NiCoMn)1/3O2
mass ratio of 1:1) in a 100 mL ball-milling pot made of
agate with ten zirconia grinding balls (10 mm diameter).
Milling was performed in a planetary ball-milling device (ECO-
PBM-AD-0-4L, DECO Technology Development Co., Ltd.,
Changsha, China) for 30 min. The mechanochemically treated
solid materials were subjected to metal leaching using the
procedure outlined in Section 2.2. The recovery procedure of
Li, Ni, Co, and Mn in ChCl−FA is given in Note S3. The
3942
flowchart for selective extraction of Li, Ni, Co, and Mn from
mixed cathode materials is shown in Figure 1 and Figure S2.
2.4. Analytical Method. The metal content in the
digested solutions was determined using ICP-OES standard
procedures. The leaching percentages (wt %) of elements (Li,
Ni, Co, Mn, Fe, and P) in the cathode materials were
estimated using eq 1
m0 = m1/m2 × 100% (1)
where m1 is the actual mass (g) of element ions in the filtrate
after leaching, and m2 is the mass (g) of an element in the
cathode materials established after its complete digestion.
The crystalline phases of the samples were determined by X-
ray diffraction analysis (XRD; Rigaku SmartLab, Japan) in a
scanning range of 10−80° 2θ at 45 kV and 200 mA with a rate
of 5° min−1. X-ray photoelectron spectroscopy (XPS;
ESCALAB 250Xi spectrometer, U.S.A.) with Al Kα radiation
was used to investigate the chemical state of the elements on
the solid sample surfaces. Scanning electron microscopy with
energy dispersive X-ray analysis (SEM-EDAX; TESCAN
VEGA3 XM, Czech Republic) was used to identify the surface
morphology of the products. Fourier-transform infrared
spectroscopy (FT-IR, Nicolet 6700 spectrometer, U.S.A.;
range: 4000−400 cm−1, total 25 scans) was performed to
investigate changes of functional groups. Thermogravimetric
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analysis-differential scanning calorimetry (TG-DSC; Perki-
nElmer Pyris1, U.S.A.) was performed to confirm changes in
internal energy in the solid materials. Ultraviolet−visible
spectroscopy was conducted using a spectrophotometer
(UV−vis; Libra S35, Biochrom Ltd., U.K.; range: 300−800
nm with 0.5 nm interval). The 57Fe Mössbauer spectra were
recorded on a Mössbauer spectrometer (SEE Co. W304,
U.S.A.), using a 57Co/Rh source in transmission geometry.
The data were fitted by using the MossWinn 4.0 software.
High-resolution transmission electron microscopy-mapping
measurements were carried out with 200 kV electrons using
a Titan G2 60-300 (HR-TEM-Mapping; FEI, U.S.A.) device
with an image corrector. X-ray absorption fine structure
(XAFS) spectra were collected at the V K-edge at beamline
44A of the National Synchrotron Radiation Research Center
(NSRRC) Taiwan, China. The parsing method of extended X-
ray absorption fine structure (EXAFS) is provided in Note S4.
2.5. Density Functional Theory Calculations. The
structure optimization and property calculation of the
Li(NiCoMn)1/3O2 crystal were modeled and carried out
using Vienna Ab-initio Simulation Package (VASP) software.53
When the crystal structure was optimized, the interaction
between ionic solids and valence electrons was described by
the projected added wave method.54,55 The cutoff energy was
400 eV, and the exchange-correlation energy between
electron−electron was processed by the Generalized Gradient
Approximation (GGA-PBE) method. The Brillouin zone high
symmetry point spacing was 2π × 0.018 Å−1. The energy
convergence criterion was an energy difference of 10−4 eV/
atom. A 2 × 2 × 1 Li(NiCoMn)1/3O2 supercell structure was
constructed. The atoms contained in a supercell are 27 Li, 9
Ni, 9 Mn, 9 Co, and 54 O.
3. RESULTS AND DISCUSSION
3.1. Selective Extraction of Critical Metals from
Mixed Cathode Materials. The extraction effects of different
solvent systems (FA−H2O, ChCl−H2O, and ChCl−FA) on
critical metals in mixed cathode materials (LiFePO4:Li-
(NiCoMn)1/3O2; mass ratio of 1:1) were first investigated.
The results (Figure 2a−c) revealed that for the selective
extraction of critical metals (Li, Ni, Co, and Mn), ChCl−FA
exhibited better leaching performance than the FA−H2O and
ChCl−H2O. In the FA−H2O system, only 35.0 wt % of Li was
leached, while in the ChCl−H2O system, 28.4 wt % of the Li
was leached. Dissolution of Li could be attributed to the
corrosive action of hydrogen ions on oxide crystals in the
ChCl−H2O (pH = 4.23 ± 0.07), and FA−H2O (pH = 1.68 ±
0.02) systems. In contrast, ChCl−FA (pH = 0.68 ± 0.02)
showed higher efficacy and selectivity for the critical metals.
The leaching percentages of critical metals, i.e., Li, Ni, Co, and
Mn, were 97.6, 74.7, 81.2, and 75.1 wt %, respectively, while
the leaching percentages of impurities (nontarget elements),
i.e., P and Fe, were only 4.5 and 7.5 wt %, respectively (Figure
2c). The high leaching percentages of the critical metals
achieved in ChCl−FA DES indicated the essential roles of the
eutectic mixture and hydrogen bonding between ChCl
(hydrogen bond acceptor) and FA (hydrogen bond donor),
which could not be realized in the other solvent systems (FA−
H 2 O and ChCl−H 2 O) that contained the individual
components.
Dissolution of metal oxides in DES has been noted to be
dependent on the system pH and complexation ability of the
hydrogen bond donor in regulating the solubility of metal
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oxides.56 This infers the low acidity (pH) observed for the
ChCl−FA DES system may have contributed to the high
leaching performance observed in this study. The notable
performance of ChCl−FA could be attributed to the activity of
protons, which act as oxygen acceptors and alter the metal
speciation and complexes formed between metal ions and DES
components.57 In addition, ChCl−FA demonstrated consid-
erable leaching efficiency at a low temperature with a short
duration (80 °C, 120 min), suggesting a low energy barrier for
critical metal extraction in the designed DES. This could
provide significant benefits over previously reported DES
systems in the latest studies, where higher temperature and
longer duration (ranging from 170−220 °C and 12−24 h)
were required for efficient metal extraction.41,44,45
The selective leaching mechanism of critical metals was
verified by studying the single cathode materials. In a LiFePO4
crystal, Li was selectively extracted from the olivine FePO4
framework in the ChCl−H2O, FA−H2O, and ChCl−FA
leaching systems (Figure 2d). The enhanced leaching was
primarily attributed to the action of hydrogen ions in these
solvent systems through the following proposed chemical
reaction:
LiFePO4 + 2H+ + 2Cl = [LiCl 2] + Fe2 + + [H 2PO4 ]
(2)
In addition, ChCl−FA was noted to be more efficient in
extracting Li, Ni, Co, and Mn from the single Li-
(NiCoMn)1/3O2 cathode materials compared to ChCl−H2O
and FA−H2O (Figure 2e). This can be attributed to the
disruption of Me−O (Me represents Co, Ni, and Mn) bonds
by FA molecules and the subsequent complexation of leached
metal ions with ChCl molecules. The UV−vis spectrum of the
ChCl−FA leachate (Figure 2f) showed absorption peaks at
300−400 cm−1 and 600−750 cm−1, which could be assigned to
[NiCl4]2− and [CoCl4]2−, respectively.58,59 Furthermore, the
XRD results (Figure S3) indicated the integrity of the FePO4
framework in the leaching residue, confirming the selective
extraction of Li, Ni, Co, and Mn in the mixed cathode
materials.
The proposed dissolution mechanism of LiMeO2 crystals in
ChCl−FA is elucidated as follows: hydrogen in the FA
molecules attacks the layered structure of LiMeO2 by
disrupting the Li−O and Me−O bonds. The aldehyde group
(−C�O) reduces Me3+/4+ to Me2+, promoting further
leaching of Me and resulting in the collapse of the crystal
structure. Recent studies suggest that ChCl may also be
involved in reducing the metal oxides, providing more insight
into the ChCl−hydroxy acid system.60 Li and Me are first
dissolved in ChCl−FA to form the intermediates of lithium
formate (LiCHO2) and Me formate (Me(CHO2)2), which are
then combined with chlorine in ChCl to convert into stable
[LiCl2]− and [MeCl4]2− complexes.46,60−62 Possible chemical
reaction paths are described as follows:
2LiMeO2 + 7HCOOH + 12ChCl = 2[LiCl 2] + 2[MeCl4]2
+ 12Ch+ + 6COOH + CO2 (g) + 4H 2O (Me = Ni, Co, and Mn)
(3)
3.2. Enhanced Leaching Performance and Selectivity
through Mechanochemistry. To augment the DES
extraction performance, mechanochemical processing of
cathode materials was performed. Following the combined
mechanochemical reaction and DES extraction, the leaching
percentages of Ni, Co, and Mn could be significantly improved
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Figure 3. Leaching percentage of mixed cathode materials in ChCl−FA at mechanochemical reactions of (a) 0 rpm and (b) 600 rpm and (c) the
corresponding rates (slopes) of instantaneous leaching; (d) the relationship between the rotational speed and element leaching percentage, (e)
linear fitting of the rotational speed to leaching percentage (green ball: Pearson correlation coefficient; pink ball: adj. R-square), and (f) the
relationship between the rotational speed and element leaching percentage as well as the corresponding separation factor (SF = leaching
percentage(Li+Ni+Co+Mn)/leaching percentage(Fe+P); conditions: LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1, leaching temperature of 80 °C, the
solid−liquid mass ratio of 1:200, and leaching time of 20 min).

from 65.8 to 99.0 wt %, 71.2 to 98.2 wt %, and 71.2 to 98.5 wt
% (40 min), respectively (Figure 3a−b). These results suggest
the efficacy of the mechanochemical activation step in
enhancing the overall metal recovery. In addition, the rates
(slopes) of instantaneous leaching of Ni, Co, and Mn increased
significantly after the mechanochemical reaction (Figure 3c,
Table S4). The above observation was supported by the
leaching percentages of Ni, Co, and Mn in the mixed cathode
materials that increased with the increase in rotational speed
(Figure 3d). The fitting results (Figure 3e) confirmed the
positive relationship between the mechanochemical rotational
speed and Ni, Co, or Mn leaching efficiency with a Pearson
correlation coefficient greater than 0.97 (Figure 3f, Table S5).
In contrast, the mechanochemical process displayed a limited
impact on the leaching behavior of Li, owing to the ease of
leaching of Li even without mechanochemical treatment.
These results show that mechanochemical reactions can
activate and destabilize the Me−O bonds (Me = Ni, Co, and
Mn), leading to the accelerated collapse of the Li-
(NiCoMn)1/3O2 crystals.
Interestingly, the inclusion of the mechanochemical
processing manifested an opposite effect on the leaching
performance of Fe and P. There was a negative correlation of
rotational speed and the leaching for P (Pearson correlation
coefficient = −0.35) and Fe (Pearson correlation coefficient =
−0.92). As shown in Figure 3f, with the increase of the
mechanochemical rotational speed, the leaching percentages of
Fe and P presented a decreasing trend. It is noteworthy that
3944
the mechanochemical reaction inhibited the dissolution of Fe
and P in ChCl−FA. The leaching percentages of P and Fe
decreased from 0.07 and 4.3 wt % to 0.04 and 0.2 wt %,
respectively, at a mechanochemical reaction at 600 rpm. The
corresponding separation factor (SF)63 accordingly continued
to rise from 56.9 at 0 rpm to 1474.8 at 600 rpm. The leaching
percentages and SF of Fe and P under different leaching times
strongly support the above observation (Figure S4). We
speculate that LiFePO4 changed to more stable FePO4 during
mechanochemical processes, which will be demonstrated later.
3.3. Mechanisms of Mechanochemically Enhanced
Extraction of Critical Metals. Further verification of the
mechanisms involved in the mechanochemical response of
critical metals was explored from the perspectives of physical
properties, crystal structures, energy changes, and theoretical
calculations (Figure 4). Before the mechanochemical reaction,
mixed cathode materials had a broad and bimodal particle size
distribution with modes at 200 and 700 μm (Figure 4a),
belonging to LiFePO4 and Li(NiCoMn)1/3O2 cathode material
powder, respectively. After the mechanochemical reaction, the
particle size was significantly reduced and concentrated in a
region of ∼100 μm. The reduced particle size facilitated the
rapid dispersion and surface-controlled leaching of mixed
cathode material particles in ChCl−FA. In addition to the
particle size, the crystallinity of the mineral changed after ball
milling. The primary mineral speciation of mixed cathode
material before the mechanochemical reaction (0 rpm) was a
mixture of LiFePO4 and Li(NiCoMn)1/3O2 (Figure 4b). After
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Figure 4. Characterization results of mixed cathode materials before (0 rpm) and after (600 rpm) the mechanochemical reaction: (a) particle size,
(b) XRD patterns, and (c) TG-DSC curves (helium and heating rate of 5 °C/min); density of states of Li(NiCoMn)1/3O2 crystals (d) x = 0.05 and
(e) x = 0.08 (x represents the extended dimension of the crystallographic axis); (f) calculation results of EFermi (eV) and ΔETotal (eV).
milling at 600 rpm, the diffraction peaks of the LiFePO4 crystal
disappeared, and only weak diffraction peaks belonging to
Li(NiCoMn)1/3O2 were observed. This suggests that LiFePO4
was transformed from a crystalline structure to amorphous,
which may increase its susceptibility to leaching.64 The
mechanochemical reaction led to a significant reduction in
the diffraction peaks of the main planes of Li(NiCoMn)1/3O2
located at 18.6° (003), 36.7° (101), and 44.4° (104),
confirming the grain refinement (Figure S5).65 Furthermore,
the DSC curve of the mixed cathode material exhibited a
significant downward shift after the mechanochemical reaction
(Figure 4c), indicating higher internal energy with more
amorphous phases.65−67
Overall, more amorphous materials were formed during the
mechanochemical process, which may be related to the
destruction of the crystal structure by the external force.
Modeling of Li(NiCoMn)1/3O2 further verified the enhance-
ment effect of mechanochemistry on the internal energy of
crystal structures. In the Li(NiCoMn)1/3O2 crystal model, the
application of external force led to the elongation of the crystal
axis. Figure 4d−e shows that the density of states of the
Li(NiCoMn)1/3O2 crystals had changed significantly under the
action of external force when the values of x were 0.05 and
0.08, respectively (Figures S6−S7). With the increase of
external force, the ΔETotal and the Fermi level of the crystal
system increased (Table S6). At x = 0.05 and 0.08, the Fermi
levels were 8.8 and 10.2 eV, respectively, and the
corresponding ΔETotal was 18.9 and 45.6 eV, respectively.
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That is, the Li(NiCoMn)1/3O2 crystal was in a metastable state
with the action of external force, and thus its reactivity
increased.
3.4. Stabilization Mechanisms of Nontarget Ele-
ments. The stabilization mechanisms of Fe and P by the
mechanochemical reaction were further clarified. First, the
binding energy of Li was shifted to higher energy (56.2 to 57.9
eV) after the mechanochemical reaction (Figure 5a). The
binding energies of the Fe 2p (Figure 5b) were found to shift
up from 711.1 eV (0 rpm) (LiFePO4 species) to 712.4 eV (600
rpm) (FePO4 species). The above trends confirmed the
changes in the chemical coordination of Li and the oxidation of
Fe species. Before and after the mechanochemical reaction, the
P−O bond remained in the form of P2O5 (Figure S8). After
the mechanochemical reaction at 600 rpm, the band of the
symmetric stretching mode of [PO4]3− at 962 cm−1 in
LiFePO4 gradually shifted to 959 cm−1 in FePO4 (Figure
5c). A characteristic peak located at 1236 cm−1 that is unique
to FePO4 was also observed. The stretching vibration of
octahedral FeO6 bonds at 650 and 683 cm−1 and the bend
modes of tetrahedral PO4 at 576 and 532 cm−1 both appeared,
confirming the generation of FePO4. Mössbauer spectroscopy
(Figure 5d) further evidenced the Fe phase transformation
after the mechanochemical process. Isomer shifts of 0.35 mm/s
and quadrupole splitting of 1.32 mm/s attributed to Fe(III)
(high spin configuration) of FePO4 in octahedral coordination
were observed, corresponding to 37.3 wt % of the fitting area
(Table S7).68,69 The incomplete phase transition of LiFePO4
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Figure 5. XPS high-resolution spectra of (a) Li 1s and (b) Fe 2p before (0 rpm) and after (600 rpm) the mechanochemical reaction; (c) FT-IR
spectra of mixed cathode materials before (0 rpm) and after (600 rpm) the mechanochemical reaction; (d) Mössbauer spectra of Fe species after
the mechanochemical reaction; the k3-weighted Fourier transform magnitudes of the (e) Co and (f) Mn K-edge EXAFS spectra after the 600 rpm
mechanochemical reaction (conditions: LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1, and the mechanochemical reaction time of 30 min).

may be attributed to the inhomogeneity of the solid−solid
reaction. Control experiments (Figure S9) confirmed that the
mechanochemical process did not induce a significant phase
transition for the LiFePO4 cathode materials with no obvious
deintercalation of Li and appearance of PO4 bands (Area I),
compared with the FePO4 leaching residue.
This result suggested that the transformation of the Fe(II)
phase was likely to come from oxidation-induced effects of
Co(III) and Mn(IV) in the Li(NiCoMn)1/3O2 crystal.
Therefore, EXAFS was conducted to explore the valence
characteristics of Co and Mn species after the mechanochem-
ical reaction. The existing forms of Co species in the
mechanochemically processed samples were 13.9 wt %
Co2O3 and 86.1 wt % CoO, respectively (Figure 5e). In
addition, the valence state distribution of Mn species are 55.4
wt % Mn3O4 and 44.6 wt % Mn2O3 (Figure 5f).70 The
appearance of Co(II) and Mn(III) species indicated the
reduction of Co(III) and Mn(IV) after the interaction of
LiFePO4 and Li(NiCoMn)1/3O2, and the overlapping of Fe,
Ni, Co, and Mn according to the TEM mapping (Figure S10)
further supports this interaction. The Co and Mn species at the
low valence state can promote the dissolution and disintegra-
tion of the Li(NiCoMn)1/3O2 crystal faster and reduce the
consumption of FA molecules.27,71 Based on the above
findings in this study, during the mechanochemical reaction,
LiFePO4 was partially oxidized by Li(NiCoMn)1/3O2 and
converted into FePO4 which is more stable. This confirms the
3946
effectiveness of mechanochemical processing and synergistic
leaching of LiFePO4 and Li(NiCoMn)1/3O2, which supported
a similar phenomenon recently observed by Jiang et al.63
Therefore, the leaching stability of Fe and P in ChCl−FA was
enhanced. A possible chemical reaction pathway is proposed as
follows:
4LiFePO4 + 6Li(NiCoMn)1/3 O2 = 5Li 2O + 4FePO4
+ 2NiO + Mn2O3 + 2CoO (4)
After mechanochemical processing and DES leaching, the
cathode material residue still maintained the complete FePO4
structure, indicating that the critical metals had successfully
entered the ChCl−FA system (Figure S9). Finally, by chemical
precipitation, Ni, Co, and Mn were recovered as (NiCoMn)-
Ox, and Li was obtained as a Li2CO3 product (Figure S11).
The obtained (NiCoMn)Ox precursor and Li2CO3 can be
further used for the production of new LIBs.72 The migration
and transformation pathways of polyvinylidene fluoride are
illustrated in Figure S12. Polyvinylidene fluoride still existed on
the surface of the FePO4 residue after mechanochemical
processing and DES leaching. Owing to the integrity of the
olivine framework, these FePO4 residues can be used as raw
materials for the synthesis of LiFePO4 crystals.72,73
3.5. Highly Selective Extraction Mechanism for
Critical Metals. The mechanisms of the highly selective
extraction of critical metals from mixed cathode materials of
https://doi.org/10.1021/acs.est.2c07689
Environ. Sci. Technol. 2023, 57, 3940−3950
Environmental Science & Technology
spent LIBs are proposed as follows (Figure S13): for the
LiFePO4 cathode material, H+ in ChCl−FA can attack the Li−
O bond, and the released Li is complexed by Cl− in ChCl to
achieve selective extraction of Li; while the olivine framework
of FePO4 remains intact.37,61,74 For the Li(NiCoMn)1/3O2
cathode material, H+ in FA first attacks the Li−O and Me−O
bonds (Me = Ni, Co, and Mn), while the aldehyde functional
group acts as a reducing agent to reduce Co(III) and Mn(IV),
resulting in the dissolution of Li(NiCoMn)1/3O2 crystals.27
The mechanochemistry of LiFePO4 combined with Li-
(NiCoMn)1/3O2 can achieve the Fe phase transition of Fe(II)
to Fe(III) through an oxidation−reduction reaction induced
by ball milling, thereby inhibiting the leaching of Fe and P as
well as simultaneously improving the extraction selectivity of
the critical metals.
A preliminary benefit analysis was conducted to highlight the
advantages of the designed system. As shown in Table S8,
compared with pyrometallurgy and hydrometallurgy, mecha-
nochemical processing combined with DES offers considerable
potential in terms of universality for mixed cathode materials,
mild reaction temperature, and short leaching time. Our
system can simultaneously solve the recycling challenges of
spent Ni−Co−Mn and LiFePO4 batteries. Compared with the
high temperature (700 °C) of pyrometallurgy, the energy
consumption of mechanochemical processing combined with
DES would be significantly lower. Compared with hydro-
metallurgy, the leaching time of critical metals by ChCl−FA
could be shortened and rendered applicable for mixed cathode
materials. Although the environmental impact of DES system
needs to be further quantified, it has undoubtedly suggested
considerable potential for future applications.
4. ENVIRONMENTAL IMPLICATIONS
NEVs have become an important approach to achieve global
carbon neutrality. Recycling of batteries from NEVs is an
important approach required to manage the supply chain risk
for raw materials, metals, and refined elements for the
construction of LIBs. There are technical challenges in the
recycling of critical metals (Li, Ni, Co, and Mn) from
multisource end-of-life LIBs. This study tackles these
challenges by the innovative customization of ChCl−FA
DES that is demonstrated to provide an outstanding
performance for the selective extraction of critical metals
from both single and mixed cathode materials of spent LIBs.
The leaching inhibition of undesirable Fe and P by
mechanochemical oxidation of the Fe(II) phase in LiFePO4
is able to further improve the leaching selectivity and
separation efficiency of the critical metals. Therefore, our
proposed approach of ChCl−FA combined with mechano-
chemical induction provides a promising approach for
recovering critical metals from multisource spent LIBs and
supporting future energy transitions for sustainable develop-
ment.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.est.2c07689.
Dismantling of spent power lithium-ion batteries (Note
S1); synthesis of deep eutectic solvent (Note S2);
recycling of metal products (Note S3); parsing method
of EXAFS (Note S4); (a) FT-IR spectra of FA, ChCl,
3947
pubs.acs.org/est Article
and ChCl−FA, (b) molecular formula of ChCl−FA
(Figure S1); flowchart for recovery of critical metals (Li,
Ni, Co, and Mn) from mixed spent LIB cathode
materials (Figure S2); (a) XRD patterns of mixed
cathode material residues after critical metal extraction
(Figure S3); leaching percentage and separation factors
of Fe and P over time (Figure S4); height change of
different crystal planes before (0 rpm) and after (600
rpm) mechanochemical reaction (Li(NiCoMn)1/3O2)
(Figure S5); band structure of Li(NiCoMn)1/3O2
crystals at x = 0.05 (Figure S6); band structure of
Li(NiCoMn)1/3O2 crystals at x = 0.08 (Figure S7); XPS
high-resolution spectra of P 2p before and after
mechanochemical reaction (Figure S8); FT-IR spectra
of LFP, LFP-MC, and residue (Figure S9); TEM-
mapping results of mixed cathode materials after
mechanochemical reaction at 600 rpm (Figure S10);
metal recovery experiments (Figure S11); migration
path of polyvinylidene fluoride during mechanochemical
processing and DES leaching (Figure S12); mechanisms
of selective extraction of critical metals from spent LIBs
(Figure S13); weight proportion of each part of spent
LiFePO4 battery (Table S1); weight proportion of each
part of spent Li(NiCoMn)1/3O2 battery (Table S2);
element mass percentages of cathode materials of
different batteries (Table S3); fitted data of element
leaching from mixed cathode materials after mechano-
chemical reaction at 0 and 600 rpm (Table S4); fitted
data of element leaching from mixed cathode materials
after mechanochemical reaction at different rotational
speeds (Table S5); band gap Eg, Fermi energy level
(EFermi), and total energy (ETotal) and differential value of
Li(NiCoMn)1/3O2 under different deformations (Table
S6); Mö s sbauer spectroscopy of mixed cathode
materials after mechanochemical reaction (600 rpm)
(Table S7); analysis of technical benefits (Table S8)
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
Daniel C. W. Tsang − Department of Civil and
Environmental Engineering, The Hong Kong Polytechnic
University, Kowloon, Hong Kong, China; Ecological
Engineering of Mine Wastes, Sustainable Minerals Institute,
The University of Queensland, Brisbane, Queensland 4072,
Australia; orcid.org/0000-0002-6850-733X;
Email: dan.tsang@polyu.edu.hk
Authors
Mengmeng Wang − Department of Civil and Environmental
Engineering, The Hong Kong Polytechnic University,
Kowloon, Hong Kong, China; Research Centre for
Environmental Technology and Management, The Hong
Kong Polytechnic University, Kowloon, Hong Kong, China
Kang Liu − Department of Civil and Environmental
Engineering, The Hong Kong Polytechnic University,
Kowloon, Hong Kong, China; Research Centre for
Environmental Technology and Management, The Hong
Kong Polytechnic University, Kowloon, Hong Kong, China
Zibo Xu − Department of Civil and Environmental
Engineering, The Hong Kong Polytechnic University,
Kowloon, Hong Kong, China; Research Centre for
https://doi.org/10.1021/acs.est.2c07689
Environ. Sci. Technol. 2023, 57, 3940−3950
Environmental Science & Technology
Environmental Technology and Management, The Hong
Kong Polytechnic University, Kowloon, Hong Kong, China
Shanta Dutta − Department of Civil and Environmental
Engineering, The Hong Kong Polytechnic University,
Kowloon, Hong Kong, China; Research Centre for
Environmental Technology and Management, The Hong
Kong Polytechnic University, Kowloon, Hong Kong, China
Marjorie Valix − School of Chemical and Biomolecular
Engineering, University of Sydney, Sydney, New South Wales
2006, Australia
Daniel S. Alessi − Department of Earth and Atmospheric
Sciences, University of Alberta, Edmonton, Alberta T6G 2E3,
Canada; orcid.org/0000-0002-8360-8251
Longbin Huang − Ecological Engineering of Mine Wastes,
Sustainable Minerals Institute, The University of Queensland,
Brisbane, Queensland 4072, Australia; orcid.org/0000-
0001-5024-0107
Julie B. Zimmerman − Department of Forestry and
Environmental Studies, Yale University, New Haven,
Connecticut 06520, United States; orcid.org/0000-0002-
5392-312X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.est.2c07689
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors appreciate the financial support from the Hong
Kong Research Grants Council (PolyU 15222020) and the
Research Centre for Resources Engineering towards Carbon
Neutrality.
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