Supporting Information

Selective Recovery of Lithium from Spent Lithium-ion

Batteries by Coupling Advanced Oxidation Processes
(AOPs) and Chemical Leaching Processes

Weiguang Lva,b,1, Zhonghang Wanga,1, Xiaohong Zhenga, Hongbin Caoa,

Mingming Hea, Yi Zhanga, Haijun Yuc, Zhi Sun*,a,b

a National Engineering Laboratory for Hydrometallurgical Cleaner Production

Technology, Institute of Process Engineering, Innovation Academy for Green

Manufacture, Chinese Academy of Sciences, Beijing 100190, China

b School of Chemical Engineering, University of Chinese Academy of

Sciences, Beijing 100190, China

c Hunan University, Changsha, Hunan 410082, China

*Corresponding author: Z. Sun (sunzhi@ipe.ac.cn)

Weiguang Lv and Zhonghang Wang contributed equally
Tel: +86 10 82544844
Fax: +86 10 82544845
No. 1 Beierjie, Zhongguancun, Beijing, China

Number of pages: 5

Number of tables: 0

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Number of figures: 5

( 001)

( 003)
Li4Mn14O27· xH2O
12000
Li( Ni0.5Co0.2Mn0.3) O2
9000

Intensity
( 104)
6000

( 101)
( 002)

( 006)
( 102)

( 110)
3000

( 018)
( 105)

( 113)
( 107)
0
18.5k
400
16.2k
350
13.8k

11.5k 300

in
m
9.1k 250

e,
m
6.8k
200

Ti
4.4k

n
150

tio
2.1k

ac
100

Re
-250.0

50
0

10 20 30 40 50 60 70 80 90

o
2θ,

Figure S1 XRD patterns variation during chemical delithiation in Na2S2O8-H2SO4

aqueous solution (W2)

Figure S2 Position shift and intensity changes of some peaks (W2)

S2
 AOPs-CLPsTechnology Traditional Technology
NCM523 Scraps NCM523 Scraps

Selective Acid Leaching

Delithiation

Residue
Separation (Ni,Co,Mn) Residue Separation

Products Precipitation
Precipitation Ni hydroxide Solvent Extraction
(Ni,Co,Mn)
Electrolysis

Precipitation Li2CO3 Evaporation

Separation Na2SO4 Li2CO3 Precipitation

Regeneration Na2SO4 Separation

Figure S3 Process flowsheet for the AOPs-CLPs technology and traditional

technology (summarized from previous researches) [1, 2]

Due to the results shown in Figure 8 are collected through sampling many times in
the one experiment, some of the samples in the end may be influenced by the previous
samples. Therefore, the experiment with an temperature of 85 oC, a [S2O82-]/[M] of 0.33,
a solid-to-liquid mass ratio of 400 g/L, a stirring speed of 300 rpm, reaction time 360
min and an solution endpoint pH of 2.9, was researched again with no sampling in the
reaction. In this reaction condition, both leaching efficiency and selectivity could reach
95.21% and 93.91%, respectively, which are far superior to the existing literature data,
as shown in Figure . The results indicated that the AOPs-CLPs is more suitable to
disposing simple scraps to obtain an excellent recycling result. However, the factors
that damage the recycling efficiency of AOPs-CLPs for the mixed waste are still unclear
and need to be further researched.

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 100 95.21 100
93.91

Leaching Selectivity of Li (XSLi)

Leaching Rate of i (Xi)

80 80

60 60

40 40

20 20
12.20

0
0.00 0.00 0
XLi XNi XCo XMn XSLi

Figure S4 Leaching rates and selectivity under the determined optimum reaction
conditions (W2, temperature 85 oC, [S2O82-]/[M] 0.30, solid-to-liquid mass ratio 400
g/L, stirring speed 300 rpm, a solution endpoint pH of 2.9, reaction time 360 min; this
result shows deviation of the leaching comparing with Figure 8 that the leaching
selectivity of lithium is highly relevant to the oxidation efficiency of S2O82-; it is
therefore important to control the behavior of the oxidant in the subsequent
optimization of this process.)

S4
 a Li2CO3( 01-087-0728) b
Intensity ( a.u.)

1µm

10 20 30 40 50 60 70 80 90
2

Figure S5 (a) The XRD pattern and (b) SEM image of Li2CO3

References
1. Yang, Y.; Xu, S.; He, Y., Lithium recycling and cathode material
regeneration from acid leach liquor of spent lithium-ion battery via facile co-
extraction and co-precipitation processes. Waste Manag 2017, 64, 219-227,
DOI 10.1016/j.wasman.2017.03.018I.
2. Yan, S.; Wang, R.; Shao, C.; Tong, Z.; Li, T.; Yuan, L.; Sheng, G.;
Xu, K., The strategy of entire recovery: From spent cathode material with high
nickel content to new LiNi0.5Co0.2Mn0.3O2 and Li2CO3 powders. J. Power
Sources 2019, 440, DOI 10.1016/j.jpowsour.2019.227140I.

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