Supporting Information

Selective Extraction of Critical Metals from Spent Lithium-ion

Batteries

Mengmeng Wang a, b, Kang Liu a, b, Zibo Xu a, b, Shanta Dutta a, b, Marjorie Valix c,

Daniel S. Alessi d, Longbin Huang e, Julie B. Zimmerman f, Daniel C. W. Tsang a, e, *

a Department of Civil and Environmental Engineering, The Hong Kong Polytechnic

University, Hung Hom, Kowloon, Hong Kong, China

b Research Centre for Environmental Technology and Management, The Hong Kong

Polytechnic University, Hung Hom, Kowloon, Hong Kong, China

c School of Chemical and Biomolecular Engineering, University of Sydney, New South

Wales 2006, Australia

d Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton,

AB T6G 2E3 Canada

e Ecological Engineering of Mine Wastes, Sustainable Minerals Institute, The

University of Queensland, Brisbane, Qld 4072, Australia

f Department of Forestry and Environmental Studies, Yale University, 195 Prospect

Street, New Haven, Connecticut 06520, United States

*E-mail: dan.tsang@polyu.edu.hk

Summary: 30 pages, 4 notes, 13 figures, and 8 tables.

S1
 Table of Contents
Table of Contents ...........................................................................................................2
Note S1. Dismantling of Spent Power Lithium-ion Batteries........................................4
Note S2. Synthesis of Deep Eutectic Solvent. ...............................................................5
Note S3. Recycling of Metal Products...........................................................................6
Note S4. Parsing method of EXAFS..............................................................................7
Figure S1. (a) FT-IR spectra of FA, ChCl, and ChCl−FA, (b) molecular formula of
ChCl−FA. .......................................................................................................................9
Figure S2. Flowchart for the recovery of critical metals (Li, Ni, Co, and Mn) from
mixed spent LIB cathode materials..............................................................................10
Figure S3. (a) XRD patterns of mixed cathode material residues after critical metal
extraction......................................................................................................................11
Figure S4. (a) leaching percentage and (b) separation factors of Fe and P over time. 12
Figure S5. Height change of different crystal planes before (0 rpm) and after (600 rpm)
mechanochemical reaction (Li(NiCoMn)1/3O2).3 .........................................................13
Figure S6. Band structure of Li(NiCoMn)1/3O2 crystals at x = 0.05. ...........................14
Figure S7. Band structure of Li(NiCoMn)1/3O2 crystals at x = 0.08. ...........................15
Figure S8. XPS high-resolution spectra of P 2p before and after mechanochemical
reaction.........................................................................................................................16
Figure S9. FT-IR spectra of LFP, LFP-MC, and residue (LFP: LiFePO4 raw materials;
LFP-MC: LiFePO4 raw materials after mechanochemical activation of 30 min at 600
rpm; residue: mixed cathode materials of LiFePO4 and Li(NiCoMn)1/3O2 after
mechanochemical reaction combined with DES leaching; conditions:
LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1, leaching temperature of 80 °C, leaching
time of 20 min, and solid-liquid ratio of 1:200)...........................................................17
Figure S10. TEM-Mapping results of mixed cathode materials after the
mechanochemical reaction at 600 rpm (conditions: LiFePO4:Li(NiCoMn)1/3O2 mass
ratio of 1:1)...................................................................................................................18
Figure S11. Metal Recovery Experiments. ..................................................................19
Figure S12. Migration path of polyvinylidene fluoride during mechanochemical
S2
processing and DES leaching.......................................................................................20
Figure S13. Mechanisms of selective extraction of critical metals from spent LIBs. .21
Table S1. Weight proportion of each part of the spent LiFePO4 battery. ....................22
Table S2. Weight proportion of each part of the spent Li(NiCoMn)1/3O2 battery. ......23
Table S3. Element mass percentages of cathode materials of different batteries. .......24
Table S4. Fitted data of element leaching from mixed cathode materials after
mechanochemical reaction at 0 rpm and 600 rpm. ......................................................25
Table S5. Fitted data of element leaching from mixed cathode materials after
mechanochemical reaction at different rotational speeds. ...........................................26
Table S6. The band gap Eg, Fermi energy level (EFermi), and total energy (ETotal) and
differential value of Li(NiCoMn)1/3O2 under different deformations. .........................27
Table S7. Mössbauer spectroscopy of the mixed cathode materials after
mechanochemical reaction (600 rpm). .........................................................................28
Table S8. Analysis of technical benefits. .....................................................................29
References ....................................................................................................................30

S3
Note S1. Dismantling of Spent Power Lithium-ion Batteries.

The spent power LIB was first fully discharged on a self-made lighting device and

dismantled in a fume hood. The components of the cathode electrode, anode electrode,

plastic separator, and shell were separated. The cathode electrode was washed, dried,

and then placed in a high-speed universal pulverizer (SS-1022, SHENG SHUN,

Nanjing, China) for mechanical and physical crushing. The curled aluminum foil and

cathode material powder were separated using a 200-mesh sieve. The separation of the

copper foil and graphite was achieved via ultrasonic treatment in an ultrasonic device

using deionized water as a medium. The component percentages of the spent power

LIBs (LiFePO4, and Li(NiCoMn)1/3O2) used in this experiment are shown in Table S1

and Table S2, respectively. The metal contents in different cathode materials were

determined by using mixed acid digestion (HCl−HNO3 mass ratio of 1:1) combined

with inductively coupled plasma optical emission spectroscopy (ICP-OES, Agilent

5110, USA) (Table S3).

S4
Note S2. Synthesis of Deep Eutectic Solvent.

The hydrogen bond acceptor (ChCl) and formic acid (FA) were first weighed with a

1/10,000 balance at a molar ratio of 1:1 and then physically mixed. Subsequently, the

mixture was heated at 80 ℃ to form a colorless and transparent viscous liquid. The

obtained DES was named ChCl−FA. Further, FA in ChCl−FA was replaced by an equal

amount of deionized water and named ChCl−H2O. The ChCl in ChCl−FA was replaced

by an equal amount of deionized water and was named FA−H2O. ChCl−H2O and

FA−H2O were set as control experiments to investigate the reaction effect of ChCl−FA.

S5
Note S3. Recycling of Metal Products.

Chemical precipitation was employed to recover the critical metals (Li, Co, Ni, and

Mn) in the ChCl−FA leachate. 1, 2 Filtered ChCl−FA DES of 50.0 g was first weighed,

and deionized water with a volume ratio (v/v) of 5 times was used to hydrolyze metal

complexes. After the color of the mixed solution of DES−deionized water changed

from blue to pink, a 0.5 mol/L NaOH solution was added dropwise to the mixed solution

to neutralize residual formic acid, and a flocculent Me(OH)2 (Me = Co, Ni, and Mn)

was obtained. The obtained floc precipitate was separated by a vacuum filtration device.

The Me oxide can be obtained after the recovered floc was calcined at a high

temperature of 500 ℃ in a muffle furnace. The residual chloride ions in the solution

were removed by silver nitrate titration, and 0.5 mol/L Na2CO3 solution was added to

precipitate and recover the Li in the solution.

S6
Note S4. Parsing method of EXAFS.

Since our research institute does not have a synchrotron radiation light source, the

following testing steps for extended X-ray absorption fine structure (EXAFS) are

provided by Muyan Testing Technology Center, Shanghai, China.

The data were collected in fluorescence mode using a Lytle detector, while the

corresponding reference sample was collected in transmission mode. Prior to analysis,

the electrode sheet was encapsulated in Kapton adhesive tape. The reference sample

was ground and uniformly daubed on the Kapton adhesive tape as well. The acquired

extended X-ray absorption fine structure (EXAFS) data were processed using the

ATHENA module of the Demeter software package. The EXAFS spectra were obtained

by subtracting the post-edge background from the overall absorption and then

normalizing with respect to the edge-jump step. Subsequently, the χ(k) data were

Fourier transformed to real (R) space using a hanging window (dk = 1.0 Å−1) to separate

the EXAFS contributions from different coordination shells. To obtain the quantitative

structural parameters around central atoms, least-squares curve parameter fitting was

performed using the ARTEMIS module of the Demeter software package.

The following EXAFS equation was used:

𝑁𝑗𝑆20𝐹𝑗(𝑘) ―2𝑅𝑗
𝜒(𝑘) = ∑
𝑗 𝑘𝑅2𝑗
⋅ exp [ ― 2𝑘2𝜎2𝑗] ⋅ exp [
𝜆(𝑘)
] ⋅ sin [2𝑘𝑅𝑗 + 𝜙𝑗(𝑘)]

The theoretical scattering amplitudes, phase shifts and the photoelectron mean free

paths for all paths were calculated. S02 is the amplitude reduction factor, Fj(k) is the

effective curved-wave backscattering amplitude, Nj is the number of neighbors in the

S7
jth atomic shell, Rj is the distance between the X-ray absorbing central atom and the

atoms in the jth atomic shell (back scatterer), λ is the mean free path in Å, ϕ j(k) is the

phase shift (including the phase shift for each shell and the total central atom phase

shift), σj is the Debye-Waller parameter of the jth atomic shell (variation of distances

around the average Rj). The functions Fj(k), λ and ϕ j(k) were calculated with the ab

initio code FEFF10.

S8
 a

3270
1695 1162
-OH
C=O C-O 1080
ChCl-FA C-N
Transmittance (%)

1638
N-H 1084
3350 C-N
ChCl -OH

2940 1695
-OH C=O 1165
FA
C-O
4000 3000 2000 1000
Wavenumber (cm1)

Figure S1. (a) FT-IR spectra of FA, ChCl, and ChCl−FA, (b) molecular formula of

ChCl−FA.

S9
Figure S2. Flowchart for the recovery of critical metals (Li, Ni, Co, and Mn) from

mixed spent LIB cathode materials.

S10
 

Intensity (a.u.)
  


  

 FePO4:31-0640

10 20 30 40 50
2 Theta (degree)

Figure S3. (a) XRD patterns of mixed cathode material residues after critical metal

extraction.

S11
 a 25 P-0rpm P-600 rpm
Fe-0 rpm Fe-600 rpm
20

m0 (wt%)
15
10
5
0
-5
10 20 30 40
Reaction Time (min)
b P-0 rpm P-600 rpm
Separation Factor

80000 Fe-0 rpm Fe-600 rpm 2000

40000 1000

0 0
10 20 30 40
Reaction Time (min)

Figure S4. (a) leaching percentage and (b) separation factors of Fe and P over time.

(conditions: LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1, mechanochemical reaction

time of 30.0 min, leaching temperature of 80 ℃, and solid-liquid ratio of 1:200).

Figure S4a show that after 600 rpm treatment, the leaching percentages of Fe and P in

the mixed cathode material were much lower than at 0 rpm. Figure S4b demonstrate

that the separation factors (SF) of the mixed cathode materials at 600 rpm were all

higher than at 0 rpm between leaching times of 0 to 40 min, confirming the inhibitory

effect of the mechanochemical reaction on P and Fe leaching.

SFP= leaching percentage (Li + Ni + Co + Mn)/ leaching percentage (P)

SFFe= leaching percentage (Li + Ni+ Co + Mn)/ leaching percentage (Fe)

S12
 1200 0 rpm
600 rpm

Intensity (a.u.)
900

600

300

0
(003) (101) (104)

Figure S5. Height change of different crystal planes before (0 rpm) and after (600 rpm)

mechanochemical reaction (Li(NiCoMn)1/3O2).3

S13
 -2.0

Energy (eV)
-2.5

-3.0
ΓA H K Γ MLH

Figure S6. Band structure of Li(NiCoMn)1/3O2 crystals at x = 0.05.

S14
 -2.0

Energy (eV)
-2.5

-3.0
ΓA HK Γ MLH

Figure S7. Band structure of Li(NiCoMn)1/3O2 crystals at x = 0.08.

S15
 P 2p P2O 5 0 rpm

Intensity (a.u.) Intensity (a.u.)

P2O 5
(135.8 eV)
(133.7 eV)

P 2p P2O5 600 rpm

(134.4 eV)

125 130 135 140 145

Binding Energy (eV)

Figure S8. XPS high-resolution spectra of P 2p before and after mechanochemical

reaction.

S16
 Residue 576

686
1236 652 532
1094 957

Transmittance (%)
LFP-MC
Area I

1049
951
LFP

1060 937
1200 1000 800 600 400
Wavenumber (cm1)

Figure S9. FT-IR spectra of LFP, LFP-MC, and residue (LFP: LiFePO4 raw materials;

LFP-MC: LiFePO4 raw materials after mechanochemical activation of 30 min at 600

rpm; residue: mixed cathode materials of LiFePO4 and Li(NiCoMn)1/3O2 after

mechanochemical reaction combined with DES leaching; conditions:

LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1, leaching temperature of 80 °C, leaching

time of 20 min, and solid-liquid ratio of 1:200).

After the leaching of ChCl−FA, the primary bonds of the leaching residue were

consistent with FePO4, confirming the integrity of the FePO4 framework. Overall, the

ChCl−FA did not destroy the FePO4 framework composed of octahedral FeO6 and

tetrahedral PO4 in the olivine structure.

S17
Figure S10. TEM-Mapping results of mixed cathode materials after the

mechanochemical reaction at 600 rpm (conditions: LiFePO4:Li(NiCoMn)1/3O2 mass

ratio of 1:1).

S18
 a 



 b

     

 NiO: 89-5881
Intensity (a.u.)
 CoMn2O4:77-0471

 MnCo O4:23-1237
2 100 μm

30 40 50 60 70
2Theta (degree)
c Li2CO3 d
Intensity (a.u.)

Li2CO3:80-1307

100 μm

10 20 30 40 50 60 70 80
2 Theta (degree)

Figure S11. Metal recovery experiments: (a) XRD patterns of calcined product of

NiCoMn(OH)x; (b) SEM image of calcined product of (NiCoMn)Ox; (c) XRD patterns

of the Li2CO3 product; (d) SEM image of the Li2CO3 product.

Figures S11a–S11b indicates that the resulting Ni-Co-Mn product was obtained as an

oxide, while the Li was recovered as a bulk Li2CO3 product (Figures S11c–S11d).

S19
 F 1s 686.0 eV 689.6 eV
LiF [CH2-CF2]
0 rpm

600 rpm
[CH2-CF2]
689.1 eV
Residue
680 685 690 695
Binding Energy (eV)

Figure S12. Migration path of polyvinylidene fluoride during mechanochemical

processing and DES leaching.

S20
Figure S13. Mechanisms of selective extraction of critical metals from spent LIBs.

S21
Table S1. Weight proportion of each part of the spent LiFePO4 battery.
Weight Percentage
Composition Weight (g)
(wt.%)
Cathode electrode 272.67 50.70

— Al foil 35.05 6.51

— Cathode materials 237.62 44.19

Anode electrode 188.76 35.11

— Cu foil 59.09 10.99

— Graphite 129.67 24.12

Soft shell 19.68 3.66

Lug 1.38 0.27

Plastic separator 55.14 10.26

Sum 537.68 100.00

S22
Table S2. Weight proportion of each part of the spent Li(NiCoMn)1/3O2 battery.
Weight Percentage
Composition Weight (g)
(wt.%)
Cathode electrode 222.60 48.84

— Al foil 21.90 4.80

— Cathode materials 200.70 44.04

Anode electrode 179.85 39.46

— Cu foil 44.98 9.87

— Graphite 134.87 29.59

Soft shell 21.98 4.82

Lug 1.89 0.41

Plastic separator 29.42 6.47

Sum 455.74 100.00

S23
Table S3. Element mass percentages of cathode materials of different batteries.

Mass percentages (wt.%)

Element
Li Fe P Ni Co Mn

LiFePO4 3.88 31.16 16.12 — — —

Li(NiCoMn)1/3O2 7.12 — — 16.51 20.62 15.96

S24
 Table S4. Fitted data of element leaching from mixed cathode materials after

mechanochemical reaction at 0 rpm and 600 rpm.

0 rpm Li P Fe Ni Co Mn

Number of Points 4 4 4 4 4 4

Degrees of Freedom 2 2 2 2 2 2

Residual Sum of Squares 38.245 16.590 2.246 2.352 29.038 32.337

Pearson's r 0.937 0.917 0.975 0.997 0.964 0.940

Adj. R-Square 0.816 0.760 0.927 0.992 0.893 0.826

600 rpm Li P Fe Ni Co Mn

Number of Points 4 4 4 4 4 4

Degrees of Freedom 2 2 2 2 2 2

Residual Sum of Squares 10.921 0.000719 0.00782 1.701 4.939 3.064

Pearson's r 0.961 0.167 0.927 0.999 0.997 0.998

Adj. R-Square 0.886 –0.458 0.789 0.997 0.991 0.993

S25
Table S5. Fitted data of element leaching from mixed cathode materials after

mechanochemical reaction at different rotational speeds.

Element Slope Standard Error Pearson's r Adj. R-Square

Li 0.00229 0.00214 0.603 0.0459

P –2.89E-04 5.52E-04 –0.347 –0.319

Fe –0.00641 0.00188 –0.924 0.780

Ni 0.0372 0.00544 0.980 0.938

Co 0.0403 0.00369 0.992 0.975

Mn 0.0379 0.00416 0.989 0.965

S26
Table S6. Band gap Eg, Fermi energy level (EFermi), and total energy (ETotal) and

differential value of Li(NiCoMn)1/3O2 under different deformations.

Parameter Change

x = 0.0

Eg/eV EFermi/eV ETotal/eV ΔETotal/eV

0.0391 6.97 –670.62 0.00

x = 0.05

Eg/eV EFermi/eV ETotal/eV ΔETotal/eV

0.005 8.81 –651.71 18.91

x = 0.08

Eg/eV EFermi/eV ETotal/eV ΔETotal/eV

0.0037 10.24 –625.03 45.58

Note:

Δ The difference between the total energy of the system, ΔETotal, is the total system

energy of the Li(NiCoMn)1/3O2 crystal when the external force is applied minus the

total system energy of the Li(NiCoMn)1/3O2 crystal when the external force is not

applied.

Δ0.05 and 0.08 are random parameters to enhance the credibility of DFT calculation

results.

S27
Table S7. Mössbauer spectroscopy of the mixed cathode materials after

mechanochemical reaction (600 rpm).

Parameter IS (mm/s) QS (mm/s) Γ(mm/s) Area (%)

Doublet1 1.13 3.05 0.34 62.70

Doublet2 0.35 1.32 0.68 37.30

Note: Line width (Γ)

S28
 Table S8. Analysis of technical and environmental benefits.
Recovery
Temperature Time
Technology Equipment Reagents Battery percentages Ref.
(℃) (min)
(wt.%)
Heating Li 81.9%,
LiMn2O4
time: 23 MnO 100%
Vacuum tube
Pyrometallurgy 700 min, Graphite LiCoO2 Li 82.7% 4
furnace
holding LiNixCoyMn
Li 66.25%
time: 30 min zO 2
Flask
installed with Li 98.22%,
Leaching Formic
condenser Li(NiCoMn Ni 99.96%,
Hydrometallurgy 60 time: 120 acid, 5
and magnetic )1/3O2 Co 99.96%,
min H2O2
stirring Mn 99.95%
device
Ball-milling Ball-milling
Choline Li 97.6%,
device & time: 30 LiFePO4 &
chloride, Ni 99.0%, This
Solvometallurgy Magnetic 80 min, Li(NiCoMn
Formic Co 98.2%, study
stirring Leaching )1/3O2
acid Mn 98.5%
device time: 40 min

S29
References

1. Wang, S.; Zhang, Z.; Lu, Z.; Xu, Z., A novel method for screening deep eutectic

solvent to recycle the cathode of Li-ion batteries. Green Chemistry 2020, 22, (14),

4473-4482.

2. Tran, M. K.; Rodrigues, M.-T. F.; Kato, K.; Babu, G.; Ajayan, P. M., Deep eutectic

solvents for cathode recycling of Li-ion batteries. Nature Energy 2019, 4, (4), 339-

345.

3. Yang, Y.; Zheng, X.; Cao, H.; Zhao, C.; Lin, X.; Ning, P.; Zhang, Y.; Jin, W.; Sun,

Z., A closed-loop process for selective metal recovery from spent lithium iron

phosphate batteries through mechanochemical activation. ACS Sustainable

Chemistry & Engineering 2017, 5, (11), 9972-9980.

4. Xiao, J.; Li, J.; Xu, Z., Novel Approach for in Situ Recovery of Lithium Carbonate

from Spent Lithium Ion Batteries Using Vacuum Metallurgy. Environmental

Science & Technology 2017, 51, (20), 11960-11966.

5. Gao, W.; Zhang, X.; Zheng, X.; Lin, X.; Cao, H.; Zhang, Y.; Sun, Z., Lithium

Carbonate Recovery from Cathode Scrap of Spent Lithium-Ion Battery: A Closed-

Loop Process. Environmental Science & Technology 2017, 51, (3), 1662-1669.

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