Waste Management 169 (2023) 32–42

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Waste Management
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Research Paper

Closed-loop recycling of spent lithium-ion batteries based on selective

sulfidation: An unconventional approach
Kunhong Gu, Xuesong Gao, Yuxin Chen, Wenqing Qin, Junwei Han *
School of Minerals Processing & Bioengineering, Central South University, Changsha 410083, China

A R T I C L E I N F O A B S T R A C T

Keywords: The facile recycling of spent lithium-ion batteries (LIBs) has attracted considerable attention because of its great
Circular economy importance to environmental protection and resource utilization. A novel process is developed for cyclic utili­
Hazardous solid waste zation of spent LiNixCoyMnzO2 (NCM) batteries. The spent NCM was converted into water-soluble Li2CO3, acid-
Regeneration of cathode material
dissolved MnO, and nickel–cobalt sulfides through selective sulfidation, based on roasting condition optimization
Selective sulfidation
and thermodynamic calculation. More than 98 % of lithium is extracted preferentially from calcined NCM
Spent lithium battery
Water leaching through water leaching, and over 99 % of manganese is extracted selectively from water leaching residue with
H2SO4 solution of 0.4 mol/L in the absence of additional reductant. The nickel and cobalt sulfides were
concentrated into the leaching residue without metal impurities. The obtained Li2CO3, MnSO4, and nickel–cobalt
sulfides can be regenerated as new NCM, showing good electrochemical performance, and its discharge capacity
is 169.8 mAh/g at 0.2C. After 100 cycles at 0.2C, the discharge specific capacity can still be maintained at 143.24
mAh/g, and its capacity retention ratio is as high as 92 %. An environmental assessment and economic eval­
uation indicate that the process is an economical and eco-friendly approach for green recycling of spent LIBs.

1. Introduction are crucial (Huang et al., 2021; Lee et al., 2018).

Current methods to recycle spent cathode materials include pyro­
Lithium-ion batteries (LIBs) have been widely used in consumer metallurgical and hydrometallurgical processes. In the pyrometallurgi­
electronics, stationary energy storage, and electric vehicles as a type of cal process, high temperature smelting is used to extract metals or alloys
excellent storage carrier of electric energy (Li et al., 2010a; Liu et al., from spent LIBs. The advantages of the smelting process include
2019b). Currently, the fast-growing market of new energy vehicles has simplicity and efficiency, but it comes with polluting gases and energy
spurred a surge in demand and output of electric vehicle batteries. consumption. In addition, a large amount of lithium is rejected to
Electrode materials experience expansion, contraction, and fragmenta­ smelting slags, causing wastage of the precious lithium resource.
tion due to repeated charge and discharge, and the electrolyte is Hydrometallurgical processes mainly include chemical leaching and
consumed, resulting in capacity attenuation and voltage drop (Miao biological leaching. Chemical leaching is the process of leaching metal
et al., 2022; Muthurasu et al., 2021; Yu et al., 2022). LIBs become ions from waste cathode materials with suitable acid or alkali in the
obsolete after several years of use. In addition, some electrode materials presence of reducing agents (Duan et al., 2016; Kim et al., 2021; Kong
and batteries will be scrapped in the production process. Spent LIBs et al., 2022). Among them, acid leaching is the most common method for
contain a large amount of valuable metals, such as Li, Co, Ni, Mn, Cu, the extraction of metal elements from spent cathode materials, where
and Al, and when handled inappropriately, the electrolyte solution they sulfuric acid, hydrochloric acid, and nitric acid are commonly used. The
contain not only causes serious damage to soil and groundwater, but also commonly used reducing agent is hydrogen peroxide (Gu et al., 2022b),
become waste metal resources (Ding et al., 2021; Wu et al., 2020; Zhong which reduces the converted Mn, Ni, Co into their low valence-state
et al., 2020). Therefore, spent LIBs recycling is greatly important from soluble compounds. At present, some scholars (Gu et al., 2023) have
the perspective of resource recovery and environmental protection proposed using more stable biomass reducing agents to replace explo­
(Chen et al., 2018; Gu et al., 2022a). However, given the high cost of sive hydrogen peroxide, but these studies are only in the laboratory
cathode materials, recycling and reuse of the materials from spent LIBs stage and have not yet been widely promoted. Joulié et al. (Joulié et al.,

* Corresponding author.
E-mail address: hanjunwei2008@[Link] (J. Han).

[Link]
Received 17 January 2023; Received in revised form 23 May 2023; Accepted 21 June 2023
Available online 30 June 2023
0956-053X/© 2023 Elsevier Ltd. All rights reserved.
K. Gu et al. Waste Management 169 (2023) 32–42

2014) reported the leaching law of LiNixCoyMnzO2 (NCM) materials 2. Experimental

with H2SO4, HNO3, and HCl, and almost all metals were leached out by
HCl solution. However, extracting cobalt with nitric acid or sulfuric acid 2.1. Materials
in the absence of reducing agent was unsatisfactory (Wang et al., 2015;
Yang et al., 2022). The leaching of cathode materials with inorganic acid The spent lithium-ion battery cathode material used in this research
has the advantage of high leaching rate, but the concentration of acid was supplied by a company in Guangdong Province. The pretreatment of
used is relatively high, causing corrosion to the equipment, complicated spent lithium-ion battery is shown in Fig. S1. According to our previous
waste acid treatment after leaching, and release of toxic gases, such as study (Zhong et al., 2022), the cathode material and aluminum foil can
Cl2, NOx, and SO3 (Cunha et al., 2013; Lei et al., 2022). In recent years, be effectively separated by effective pyrolysis. Table S1 shows the results
biological leaching has been gradually applied to the leaching research of the chemical composition analysis of the cathode material by induc­
of cathode materials due to its low cost and environmental friendliness tively coupled plasma–optical emission spectrometry (ICP-OES; Plasma
(Li et al., 2010b; Sarma & Shukla, 2018). Biological leaching utilizes the 3000). X-ray diffraction (XRD; ARLEQUINOX100) and scanning electron
redox effect of microorganisms’ metabolic processes to enhance the microscopy coupled with energy dispersive spectroscopy (SEM-EDS;
selective extraction of Co, Li, and other metal elements to achieve the QUANTA FEG 450) were used to detect the crystal phase composition
separation of target components from impurity components (Li et al., and morphology of raw materials, and the results are shown in Fig. S2.
2021; Zhong et al., 2021). The process has little pollution and low en­ According to Table S1, the molecular formula of the cathode material is
ergy consumption, and microorganisms can be reused. However, the deduced as LiNi0.5Co0.2Mn0.3O2. The XRD pattern (Fig. S2a) indicates
application of this technology on an industrial scale is hindered by long that the main characteristic peaks (0 0 3) and (1 0 4) can be retrieved in
cultivation cycle of microorganisms, poor adaptability of microorgan­ the spectrum. These peaks are used to characterize the degree of cation
isms, harsh requirements, and low leaching rate (Gao et al., 2020; mixing of ternary nickel–cobalt–lithium manganate cathode material.
Harper et al., 2019). According to the cleavage morphology of (0 0 6)/(1 0 2) and (1 0 8) /
Sulfidation is a promising generic technology for the recovery and (1 1 0) peaks in the spectrum, the cathode material has a complete and
stabilization of heavy metals from wastes, by which metal oxides and/or orderly layered structure. Fig. S2b shows the raw material as a large,
oxidized compounds are converted into sulfides, which have good smooth-surfaced spherical particle in which Ni, Co, Mn is evenly
floatability and are relatively insoluble in aqueous solutions (Chang distributed in 5:2:3 ratio. The detection results of ICP, XRD, and SEM-
et al., 2022). Recently, innovative methodology of selective sulfidation EDS indicate that the raw material is NCM523 (LiNi0.5Co0.2Mn0.3O2).
has been proposed to solve the problem of difficult separation of zinc The reducing agent used in this experiment is carbon powder, and the
and iron sulfides. Han et al. (Han et al., 2016) first reported that the zinc curing agent is sulfur powder, which were purchased from online
and iron contents in lead smelter slag were selectively converted into shopping malls. The particle size of carbon powder is 80–120 mesh, and
zinc sulfides and iron non-sulfides by regulating the conditions of sul­ the particle size of sulfur powder is − 100 mesh.
fidation roasting to completely address the problem. Harris et al. (Harris
et al., 2013) proposed a study on the selective sulfidation and flotation 2.2. Methods
recovery of nickel from lateritic nickel ores. Their research demonstrates
that selective sulfidation of nickel from laterite ores is achievable, and The overall process and experimental equipment of this research are
the overall conversion and grade of sulfidized nickel are largely influ­ shown in Fig. S3. 10 g of cathode material was mixed with a certain
enced by the addition of sulfur and reaction temperature. Stinn et al. amount of sulfur and charcoal powder for each test. The combined raw
(Stinn & Allanore, 2022) studied the recycling of spent LiNi1/3Mn1/ materials were poured into a corundum crucible, covered with a lid and
3Co1/3O2 batteries using selective sulfidation followed by flotation or tightened with an iron wire and place it in the vulcanization furnace
magnetic separation. The flotation results indicated that the grade of Ni with argon tank for roasting experiment. The water leaching and low-
and Co reached 82.8 %, but the recovery of Ni and Co was only 52.8 %. acid leaching process were carried out in thermostatically heated
The results of magnetic separation showed that the recovery of nickel water bath. Error bars was calculated in order to ensure the reliability of
and cobalt reached 84.8 %, whereas the grade was 82.1 %. Evidently, the experiment. The leaching efficiency (ξL, %) is calculated as:
these recycling results are unsatisfactory; thus, a systematic study on
selective sulfidation is necessary to effectively separate and recover ζL (%) =
cV
× 100% (1)
valuable metals from spent LIBs. mW
In this study, a novel process of selective sulfidation, stepwise c (g/L)- Concentration of metal ions in leach solution, m (g)-Mass of
leaching, and material regeneration is developed for cyclic utilization of raw material.
spent LiNixCoyMnzO2 (NCM) cathode material. Different from tradi­ V (L)-Volume of leach solution, W (%)-Content of metals in raw
tional sulfidation, the objective of selective sulfidation is to convert material.
NCM into water-soluble Li2CO3, acid-dissolved MnO, and nickel–cobalt In this experiment, thermodynamic calculations were performed
sulfides, enlarging the solubility difference of different metals contained using the thermodynamic software Factsage 8.0. The Predom module
in NCM to solve the problem of difficult separation of similar metals. The was utilized for the construction of predominance area diagrams, while
generated Li2CO3 and MnO can be selectively extracted by water the Equilib module was used for product prediction (input reactants,
leaching and low-acid leaching without additional reducing agent. output equilibrium states of products). The databases selected for the
Meanwhile, other impurities, which are insoluble compounds in weak calculations were FactPS, FToxide, and FTsalt.
acid or alkaline solution, are removed from nickel–cobalt sulfides. The Half-cell assembly: The active materials (80 wt%), carbon black
obtained Li2CO3, MnSO4, and nickel–cobalt sulfides with high purity can (conductive carbon, 10 wt%) and polyvinylidene fluoride (PVDF, 10 wt
be regenerated as new NCM. This method can achieve the priority of %) were mixed and dispersed in N-methyl-2-pyrrolidine (NMP), and
lithium extraction, maximize the recovery of high-value lithium, avoid then the electrode slurry was obtained by magnetic stirrer at 300 rpm for
the cumbersome element separation process, and finally achieve the 3 h. The slurry was uniformly coated onto aluminum foil using a coating
facile recycling of spent NCM. The selective sulfidation of spent NCM, machine, and then dried for 12 h in a 60 ◦ C vacuum drying oven. Once
stepwise leaching of Li and Mn, and regeneration of NCM material and dry, 12 mm diameter electrode sheets were cut and used for cell as­
its electrochemical performance are systematically studied via advanced sembly. The dried cathode sheets were then transferred to a glove box
analytical techniques and thermodynamic calculation. The toxicity of filled with argon gas, with water and oxygen volume fractions not
leaching residues and the economy of the entire process are analyzed. exceeding 0.00001 %. The battery assembly was conducted in a bottom-
up sequence, with the positive electrode shell, positive electrode film,

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 K. Gu et al. Waste Management 169 (2023) 32–42

Fig. 1. Thermodynamic analysis of selective sulfidation roasting: (a) equilibrium phase diagrams of LiNi0.5Co0.2Mn0.3O2 sulfidation at 800 ◦ C with different sulfur
amounts, 0.9 mol carbon; (b) equilibrium phase diagrams of LiNi0.5Co0.2Mn0.3O2 sulfidation at 800 ◦ C with different carbon amounts, 0.52 mol sulfur; (c) equilibrium
phase diagrams of LiNi0.5Co0.2Mn0.3O2 sulfidation with 0.9 mol carbon and 0.52 mol sulfur at different temperatures; (d) equilibrium phase diagrams of LiNi0.5
Co0.2Mn0.3O2 sulfidation at 800 ◦ C with different carbon amounts and 2 mol sulfur.

electrolyte droplets, separator, electrolyte droplets, lithium foil, spacer, conditions (the initial amount of cathode material is 1 mol). It can be
tab, and negative electrode shell placed in order. The electrolyte solute seen that the key to realize selective sulfurization roasting of cathode
used was 1 mol/L LiPF6. During battery assembly, all components were materials is the amount of carbon addition, the amount of sulfur addi­
arranged concentrically to avoid short circuits or increased polarization, tion and the roasting temperature. When no sulfur is added and only
and the sealed assembly was carried out using a battery sealing machine. carbon is roasted with the cathode material, the roasted products are
Electrochemical Performance: The initial charge–discharge and cy­ nickel, cobalt, manganese oxide, and lithium carbonate. When the
clic performance testing were conducted under the conditions of amount of sulfur was gradually increased, the content of Ni and Co
2.0–4.5 V, 0.2C, while the rate performance testing was performed decreased, and the content of Ni3S2 and Co9S8 increased significantly.
under the conditions of 2.0–4.5 V. The cyclic voltammetry testing The contents of Li2CO3 and MnO were almost unchanged. When the
voltage range was 2.7–4.3 V, and the alternating current impedance amount of sulfur is excessive, all the metals in the cathode material were
testing frequency range was 0.01 Hz to 100000 Hz, with an amplitude of vulcanized. When no carbon is involved, some nickel, cobalt, and
5 mV. lithium react to generate NiS, CoS, and Li2S. When the content of carbon
increased, the contents of Li2CO3, Ni3S2, Co9S8, and MnO also increase
3. Results and discussion and the composition of the product does not change. Moreover, the
addition of carbon can effectively inhibit the formation of SO2 in the
3.1. Thermodynamic study sulfidation process (Han et al., 2015; Han et al., 2016; Han et al., 2017).
The contents of Li2CO3, Ni3S2, Co9S8, and MnO increase with the in­
The possible reactions during the roasting process were outlined and crease in temperature. This finding indicates that the increase in tem­
the standard Gibbs free energy changes for these reactions were calcu­ perature is conducive to the positive progress of selective sulfidation
lated and discussed in Supporting Information. According to the analysis reaction. Factsage8.0 was used to calculate the thermodynamic equi­
of Table S2 and Fig S4, nickel sulfide and cobalt sulfide are preferentially librium diagrams of Li–Ni–Co–Mn–S–C–O systems at different temper­
generated rather than manganese sulfide during the sulfidation of atures to investigate the possibility of selective sulfidation of cathode
cathode materials. Fig. 1 shows the equilibrium phase composition of materials and the influence of reaction conditions on the sulfidation
the selective sulfidation reaction of the cathode material under different process, and the results are shown in Fig S5 indicating that increasing

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 K. Gu et al. Waste Management 169 (2023) 32–42

Fig. 2. XRD patterns of the samples roasted under various conditions: (a) different carbon dosages (n(LiNi0.3Co0.2Mn0.3O2):n(S) = 1:0.52, 800 ◦ C, 120 min); (b)
different sulfur dosages (n(LiNi0.3Co0.2Mn0.3O2):n(C) = 1:0.9, 800 ◦ C, 120 min); (c) different roasting temperatures (n(LiNi0.3Co0.2Mn0.3O2):n(C) = 1:0.9, n
(LiNi0.3Co0.2Mn0.3O2):n(S) = 1:0.52, 120 min); (d) different roasting time (n(LiNi0.3Co0.2Mn0.3O2):n(C) = 1:0.9, n(LiNi0.3Co0.2Mn0.3O2):n(S) = 1:0.52, 800 ◦ C).

the temperature is beneficial to the selective sulfidation of cathode carbon powder is 1:0.3 (n(LiNi0.5Co0.2Mn0.3O2): n(C) = 1:0.3), the
materials. Reaction Gibbs free energy and thermodynamic equilibrium diffraction peaks of LiNixCoyMnzO2 become less and weaker, and the
diagrams show that selective sulfidation of spent LIBs can be achieved diffraction peaks of nickel sulfide increase and strengthen, indicating
by sulfidation roasting at a suitable temperature and atmosphere. that the addition of carbon powder promotes the decomposition of
cathode materials. When the molar ratio of the cathode material and
3.2. Selective sulfidation of spent NCM carbon powder is 1:0.6 (n(LiNi0.5Co0.2Mn0.3O2): n(C) = 1:0.6), the
diffraction peak of LiNixCoyMnzO2 almost disappears, replaced by the
According to the analysis of roasting thermodynamics, the complete diffraction peaks of Li2CO3, Co9S8, and MnO, and the diffraction peak of
selective sulfidation roasting of cathode materials can be divided into nickel sulfide is further enhanced. In the case of n(LiNi0.5Co0.2Mn0.3O2):
two stages. First, the cathode material reacts with carbon powder to n(C) = 1:0.9 or 1:1.2, the diffraction peaks of LiNixCoyMnzO2 fully dis­
produce Li2CO3, MnO, Co and Ni. Subsequently, Co, Ni, and sulfur react appeared after the roasting, and the diffraction peaks of Li2CO3, Co9S8,
to form nickel sulfide and cobalt sulfide. The sulfidation roasting was and MnO are very evident, and those of Nix’S6 also disappear and are
carried out under the condition that the mixing molar ratios of LiNi0.3 completely converted into the diffraction peaks of Ni3S2. Therefore, n
Co0.2Mn0.3O2 and carbon powders were 0, 1:0.3, 1:0.6, 1:0.9, and 1:1.2; (LiNi0.5Co0.2Mn0.3O2): n(C) = 1:0.9 was selected as the optimum molar
the results are shown in Fig. 2a. When the carbon powder is not added ratio for selective sulfidation roasting. The condition exploration
directly for sulfidation roasting, most cathode materials do not react experiment of carbon addition indicates that the addition of carbon is
with sulfur. However, at high temperature, a small amount of cathode very important in the selective sulfidation roasting; it can reduce the
material decomposes and reacts with sulfur to produce sulfide of lithium decomposition temperature of the cathode material, promote the reac­
sulfate and nickel. When the molar ratio of the cathode material and tion between the cathode material and sulfur, and complete the selective

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K. Gu et al. Waste Management 169 (2023) 32–42

Fig. 3. XRD and SEM-EDS detection results of roasting products under the optimal selective sulfidation roasting conditions. (a) XRD pattern of roasting product; (b)
SEM image of roasting product; (c) EDS of spot A; (d) EDS of spot B; (e) EDS of spot C; (f) EDS of spot D.

sulfidation. the cathode material and carbon and also accelerate the sulfidation
Fig. 2b presents the effects of different amounts of sulfur addition on process of the reduced product. When the temperature varies from
the degree of vulcanization of cathode materials. The cathode material 800 ◦ C to 1000 ◦ C, the phase composition of the roasting product is as
undergoes a reduction reaction with carbon powder to form Li2CO3, Ni stable as Li2CO3, Ni3S2, Co9S8, and MnO. Therefore, the roasting tem­
or Co, NiO, MnO when the roasting in the absence of sulfur. When n perature of 800 ◦ C was considered suitable.
(LiNi0.5Co0.2Mn0.3O2): n(S) = 1:0.26, Ni/Co and NiO diffraction peaks Fig. 2d represents the influence of roasting time on the selective
are disappeared, and a small amount of Ni3S2, Co9S8, and NiCo2S4 began sulfidation of cathode material. When the roasting time is 30 min, the
to appear in the roasting product. When n(LiNi0.5Co0.2Mn0.3O2): n(S) = diffraction peak of LiNixCoyMnzO2 can still be found in the roasting
1:0.52, the diffraction peak of NiCo2S4, which is an intermediate product product, indicating that the chemical reactions of LiNi0.5Co0.2Mn0.3O2
of the reaction of nickel and cobalt with sulfur, has disappeared, and the would hardly occur within 30 min. When the roasting time is extended
roasting product is composed of Li2CO3, Ni3S2, Co9S8, and MnO. At this to 60 min, the diffraction peaks of LiNixCoyMnzO2, NiO, and Ni/Co
time, the selective sulfidation roasting of the cathode material is disappear and those of LiMnO2, Co9S8, and MnO appear instead.
completed. When n(LiNi0.5Co0.2Mn0.3O2): n(S) = 1:0.77, the diffraction Moreover, the diffraction peaks of Li2CO3 and Ni3S2 began to increase
peak of MnO begins to disappear gradually and is replaced by the significantly. When the sample roasting time is 90 min, the roasting
appearance of MnS, and some Ni3S2 reacts with excess sulfur to form products were Li2CO3, Ni3S2, Co9S8, and MnO. When the roasting time is
Ni3S4. When the amount of sulfur addition continues to increase and extended, the phase of the calcined product no longer changes, Li2CO3,
when n(LiNi0.5Co0.2Mn0.3O2): n(S) = 1:1.02, the diffraction peak of MnO Ni3S2, Co9S8, and MnO are maintained. The roasting product was tested
is completely replaced by the diffraction peak of MnS, the diffraction by XPS under optimal roasting conditions, and the results were as shown
peak intensity of Li2CO3 is greatly weakened, and strong Li2S diffraction in Fig [Link] results indicate that the cathode material has undergone
peaks appear. These results indicate that the amount of sulfur added is reduction reaction during selective sulfidation roasting.
very important for the selective sulfidation of the cathode material and Fig. 3 shows the XRD and SEM-EDS detection results of calcined
determination of the degree of vulcanization of the reduction products products under the optimal selective sulfidation roasting conditions:
of the cathode material. If the amount of sulfur added is insufficient, 800 ◦ C of roasting temperature, n(LiNi0.5Co0.2Mn0.3O2): n(C) = 1:0.9, n
then nickel and cobalt cannot be completely vulcanized. If the amount of (LiNi0.5Co0.2Mn0.3O2): n(S) = 1:0.52, 90 min of roasting time. Fig. 3a
sulfur added is excessive, then metal elements, such as lithium and shows that under the optimal conditions, lithium carbonate, nickel
manganese, will also form metal sulfides, and the selective sulfidation of sulfide, cobalt sulfide, and manganese oxide with relatively complete
cathode materials cannot be completed, affecting the subsequent sepa­ crystal structure and better crystal form are generated by selective sul­
ration of metal elements. Therefore, n(LiNi0.5Co0.2Mn0.3O2):n(S) = fidation roasting of the cathode material. Fig. 3b–f show the SEM-EDS
1:0.52 was selected as the optimum molar ratio for selective sulfidation results of the roasting product. Fig. 3b–c indicate that the dark gray
roasting. point A is rich in manganese and oxygen, and the main phase is man­
From Fig. 2c, it can be seen that when roasting temperature is 600 ◦ C, ganese oxide, which contains a small amount of nickel and cobalt im­
the roasting product contains LiMnO2 and Co2NiO4 in addition to purities. Fig. 3d shows that the gray point B is a nickel cobalt sulfide
Li2CO3, Ni, Co, Ni3S2, Co9S8, and MnO, indicating that the decomposi­ dominated by cobalt sulfide. Fig. 3b and e suggest that the light gray
tion of the cathode material is incomplete at this temperature. When the point C is mainly nickel sulfide, in which a small amount of cobalt sul­
roasting temperature is increased to 700 ◦ C, the diffraction peak of fide is slightly dissolved. Fig. 3f shows that bright white point D is nickel
Co2NiO4 disappears, that of LiMnO2 decreases greatly, and that of cobalt alloy dominated by nickel, and some black parts in Fig. 3b are
lithium carbonate and nickel sulfide increases. This finding shows that cavities caused by lithium carbonate dissolved in water during the
the increase in temperature can promote the reduction reaction between preparation of the polished section of the roasting sample. The SEM-EDS

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K. Gu et al. Waste Management 169 (2023) 32–42

Fig. 4. Selective leaching of lithium: (a) effect of leaching temperature and liquid–solid ratio on lithium leaching rate (400 rpm,120 min); (b) effect of leaching time
and stirring speed on lithium leaching rate (30:1, 20 ◦ C); (c) XRD pattern of the water leaching crystallization product; (d) SEM of the water leaching crystallization
product; (e) EDS of area A; (f) XRD pattern of the water leaching residue; (g) SEM of the water leaching residue; (h) EDS of area B; (i) EDS of area C.

results verified that nickel sulfide and cobalt sulfide are produced by the lithium leaching rate can reach 99.01 %. After the completion of the
reduction reaction between the cathode material and carbon to form water leaching, the obtained filtrate was evaporated and crystallized.
metal nickel and metal cobalt, and then nickel and cobalt react with The crystallized product was detected by XRD and SEM-EDS analysis to
sulfur to form nickel sulfide and cobalt sulfide, consistent with the confirm its purity and crystal form. The results are shown in Fig. 4c–e.
previous experimental results and thermodynamic inference. Compared The XRD results confirmed that the crystals obtained after water
to Stinn’s research, the differences between this study and him are leaching was lithium carbonate (Li2CO3). As shown in Fig. 4d–e, the
shown in Table S3. Due to the closed system of the selective sulfurization growth of crystal grain progresses well, and the crystal structure is
process in this study, the amount of sulfur can be accurately determined characterized as the typical oblique column shaped crystal of Li2CO3.
throughout the entire reaction process. By controlling the addition of XRD and SEM-EDS tests were carried out on the water leaching
sulfur powder before the reaction, it can be ensured that transition residue to confirm the subsequent separation and recovery process of
metals will not co sulfurize. The addition of carbon reduces the high other metal elements, and the results are shown in Fig. 4f–i. Fig. 4f
valence cathode material to metal or metal oxide, reducing the Gibbs shows that the main components of the water leaching residue are nickel
free energy of the direct reaction between the cathode material and sulfide, cobalt sulfide, and manganese oxide, and no diffraction peak of
sulfur to generate metal sulfide, thus reducing the reaction temperature. lithium carbonate is found. The results in Fig. 4f are consistent with
those in Fig. 4g–i. Lithium carbonate was not found, nickel and cobalt
3.3. Selective leaching of lithium and manganese were combined in the form of sulfide, and manganese oxide and nickel
cobalt sulfide were separated. The nickel cobalt sulfide does not react
Lithium exists in the form of lithium carbonate in the roasting with the acid, but the manganese in the manganese oxide in a low
product. Lithium carbonate is soluble in water, with a solubility of 13.3 valence state easily reacts with the acid. Therefore, in the subsequent
g/L at 20 ◦ C. The influence of different leaching conditions on selective process, sulfuric acid leaching is selected to separate and recover the
lithium leaching are shown in Fig. 4a–b. manganese.
Fig. 4a clearly shows that the liquid–solid ratio and temperature The manganese in the water leaching residue exists in the form of
have a significant effect on the lithium leaching efficiency. Under the low-valence manganese oxide. Therefore, leaching the manganese from
optimal conditions: leaching temperature of 20 ◦ C, liquid–solid ratio of water leaching residues in an H2SO4 system without using any reducing
30:1, stirring speed of 300 rpm, and leaching time of 120 min, the agent is theoretically feasible. The concentration of sulfuric acid and

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K. Gu et al. Waste Management 169 (2023) 32–42

Fig. 5. Selective leaching of manganese: (a) effect of leaching temperature and sulfuric acid concentration on manganese leaching rate (10:1, 120 min); (b) effect of
leaching time and liquid–solid ratio on manganese leaching rate (0.4 mol/L, 80 ◦ C); (c) XRD pattern of the H2SO4 leaching crystallization product; (d) SEM of the
H2SO4 leaching crystallization product; (e) EDS of area A; (f) XRD pattern of the H2SO4 leaching residue; (g) SEM of the H2SO4 leaching residue; (h) EDS of area B; (i)
EDS of area C.

liquid–solid should not be extremely large due to the subsequent need to materials is 1:1, but the decomposition reaction of lithium salt exists in
evaporate and crystallize the acid leaching solution. Fig. 5a–b shows the sintering process, thereby leading to partial lithium loss. Slightly
that the optimal conditions for selective leaching of manganese are as excessive lithium can improve the electrochemical performance of
follows: 0.4 mol/L of H2SO4 concentration, 10:1 of liquid–solid ratio, ternary materials, but excessive lithium increases the residual lithium on
80 ◦ C of temperature, 120 min of leaching time. At this time, leaching the surface of materials and reduces the specific capacity of materials
rate of manganese can reach 99.02 %. The obtained acid leaching so­ (Huang et al., 2014). In this study, lithium ratio is 1.05 (Li et al., 2018),
lution is evaporated and crystallized, and the XRD and SEM-EDS results pre-sintering temperature is 750 ◦ C, pre-sintering time is 5 h, sintering
of the crystallized product are shown in Fig. 5c–e. The figures show that temperature is 900 ◦ C, sintering time is 20 h, and heating rate is 5 ◦ C/
the obtained crystalline product is high-purity manganese sulfate min. Fig. 6 shows the XRD and SEM-EDS results of the regenerated
monohydrate, the crystal form is intact, and it presents a typical NCM523.
monoclinic bulk structure. The leaching residue obtained after acid Fig. 6a shows that the crystallinity of the regenerated cathode ma­
leaching is nickel sulfide and cobalt sulfide, and it no longer contains terial is high and no other impurity phase is generated. In addition, the
manganese (Fig. 5f–i). splitting of diffraction peaks (1 0 8)/ (1 1 0) and (0 0 6)/ (1 0 2) is very
evident, indicating that the regenerated material has a highly ordered
layered structure. I003/I104 is greater than 1.2, and I006+102/I101 is less
3.4. Regeneration of NCM material and electrochemical performance than 0.5, indicating that the regenerated materials have low cation
mixing and should have good electrochemical performance (Natarajan
The obtained nickel sulfide, cobalt sulfide, manganese sulfate, and & Aravindan, 2018). Fig. 6b–f show that the particle shape of the re­
lithium carbonate were ground and mixed in a certain proportion, and generated cathode material is spherical. Nickel, cobalt, and manganese
then placed into a tube furnace. After roasting in oxygen atmosphere for metal elements are uniformly distributed on the surface of the NCM
a certain time, the regenerated ternary materials were obtained. The particles in the form of oxides, with good dispersion and no
ratio of lithium to the total amount of transition metals in ternary

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K. Gu et al. Waste Management 169 (2023) 32–42

Fig. 6. (a) XRD pattern and (b)–(f) SEM-EDS images of regenerated NCM523.

agglomeration. curve (Zview 2.0); the results are shown in Fig. 7e. The Nyquist curve is
The 2025 button battery was prepared from the regenerated cathode composed of semicircles in the high and medium frequency regions and
material, and the electrochemical performance of the battery was oblique lines in the low frequency region (Wang et al., 2021; Yu et al.,
evaluated by electrochemical detection. Fig. 7 shows the electro­ 2021). The actual axis intercept is solution impedance (Rs), the semi­
chemical results of batteries prepared from regenerative cathode ma­ circles in the high frequency region and medium frequency region are
terials. Fig. 7a–b show that the initial charge specific capacity and initial attributed to SEI layer (RSEI) and charge transfer impedance (Rct),
discharge specific capacity of the regenerated cathode material are respectively, and the oblique lines in the low frequency region are
210.7 and 169.8 mAh/g, respectively, at the charge–discharge ratio of attributed to Warburg impedance, which is related to lithium-ion
0.2C, and the coulombic efficiency is only 80.61 % (in the voltage range diffusion. The fitting results are shown in Table S4. The lithium-ion
from 2.0 V to 4.5 V). This condition may be caused by the formation of diffusion coefficient D can be calculated as follows:
SEI film during initial charging and discharging and insufficient infil­
D = R2 T 2 /2A2 n4 F4 C2 σ2 (2)
tration of electrolyte into the cathode material (Paul et al., 2022; Tan
et al., 2021; Xu et al., 2020). Starting from the second cycle, the R is the gas constant, T is the absolute temperature, A is the surface
coulombic efficiency increases to 92.11 %. With the battery charging area of the electrode, n is the number of electrons per molecule during
and discharging cycle, although the discharge specific capacity gradu­ oxidization, and F is the Faraday constant. C is the Li+ concentration
ally decreases, the coulombic efficiency is stable at more than 90 %, with the value of 7.69 × 10− 3 mol/cm3 (Tang et al., 2018), and σ is the
which indicates that the structure of the regenerated cathode material is Warburg factor associated with Zre (Zre ∝σω− 0.5 ). The linear fitting be­
very stable, and no lattice collapse occurs during the cycle, thereby tween Zre and ω− 0.5 is shown in Fig. 7f.
decreasing the coulombic efficiency (Kim et al., 2020; Liu et al., 2019a; According to the experimental results, in the process of selective
Lv et al., 2018). After 100 cycles, the specific discharge capacity of the sulfidation roasting of cathode materials, the cathode material initially
regenerated cathode material is still 143.24 mAh/g, and the coulombic undergoes a reduction reaction with carbon to generate manganese
efficiency is 92.46 %. Fig. 7c shows the rate capability of the regener­ oxide, lithium carbonate, nickel and cobalt. Sulfur, the addition amount
ative cathode material in the voltage range from 2.0 V to 4.5 V. The of which is controlled, preferentially reacts with nickel and cobalt to
average discharge specific capacities of the regenerated cathode at 0.2, generate Ni3S2 and Co9S8, and the selective sulfidation of the cathode
0.5,1, and 2C are 173.03, 157.83, 136.03, and 119.55 mAh/g, respec­ material is completed (Fig. 8). Therefore, the key to successful
tively. When the high-rate discharge is completed, and the 0.2C rate completion of selective sulfidation lies in the control of the amount of
discharge is used, the average discharge specific capacity of the regen­ sulfur added. The experimental results are consistent with the thermo­
erated cathode material is 159.02 mAh/g, and the specific capacity of dynamic deduction. The particle sizes of raw materials, calcination
91.9 % is recovered, indicating that the structure of the regenerated products, water leaching products, and regenerated cathode materials
cathode material is well maintained under the high current density. are shown in Fig.S7. The raw materials have a uniform particle size
Cyclic voltammograms can characterize the redox reactions of materials distribution with D90 = 7.2 μm. After calcination, the particle size dis­
at different voltages, the kinetic processes, and the reversibility of tribution becomes uneven with D90 = 19.75 μm. However, the particle
electrochemical reactions of materials (Liu et al., 2021; Luo et al., 2010). size distribution of the water leaching product, after recovering lithium
Fig. 7d shows that the cyclic voltammetry curve of the regenerated carbonate through water leaching, becomes significantly more uniform
cathode material is closed, indicating that the reaction system has good compared to the calcination product, with D90 = 6.27 μm. Harris et al.
reversibility. An equivalent circuit model is established to fit the Nyquist (Harris et al., 2013) previously reported that sulfide particles generated

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 K. Gu et al. Waste Management 169 (2023) 32–42

Fig. 7. Electrochemical performance of regenerated cathode materials: (a) initial charge–discharge curve; (b) cycling performance and columbic efficiency curve; (c)
rate capabilities at various current densities in the voltage range from 2.0 V to 4.5 V; (d) cyclic voltammograms; (e) EIS plots; (f) linear fitting of Zre and ω− 0.5 .

from selective sulfidation calcination at temperatures below 950 ◦ C have balance diagram. Environmental and economic assessment are shown in
a sub-micron size range. In this study, both the sulfidation calcination Supporting Information.
product and the water leaching product have micrometer-sized parti­
cles, consistent with this conclusion. Fig. S7(d) presents the particle size 4. Conclusions
distribution results of the regenerated cathode material, showing D90 =
10.36 μm, slightly larger than that of the raw material. Combined with A novel process is developed for cyclic utilization of spent LiNix
Fig. 6(b), it can be observed that the regenerated cathode material CoyMnzO2 (NCM) batteries. Based on thermodynamic calculation and
consists of secondary growth particles, resulting in a slightly larger optimization of roasting conditions, spent NCM can be transformed into
particle size compared to the raw material. Fig. S8 represents mass water-soluble Li2CO3, acid-soluble MnO, and nickel–cobalt sulfide by

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K. Gu et al. Waste Management 169 (2023) 32–42

Fig. 8. Mechanism of selective sulfidation of spent lithium batteries.

selective sulfidation, producing Li2CO3, MnO, Ni3S2, and Co9S8. The Acknowledgements
optimum roasting conditions are n(LiNi0.3Co0.2Mn0.3O2): n(C) = 1:0.9, n
(LiNi0.3Co0.2Mn0.3O2): n(S) = 1:0.52, roasting temperature of 800 ◦ C, The authors gratefully acknowledge the financial support by Natural
roasting time of 90 min. After sulfidation, more than 98 % Li is prefer­ Science Foundation of Hunan Province (No. 2021JJ20062), the Science
entially leached from the roasting product through water leaching. More and Technology Innovation Program of Hunan Province (No.
than 99 % of Mn is selectively leached from water-leaching residue via 2022RC1123, No. 2022GK4058), National Natural Science Foundation
low-acid leaching without additional reducing agent, whereas the nickel of China (No. 52174269), Innovation Driven Project of Central South
and cobalt sulfides with high purity are concentrated into the final University (No. 2020CX038), and National Key R&D Program of China
residue. The acid leaching conditions are: H2SO4 concentration of 0.4 (No. 2019YFC1907301, 2019YFC1907802).
mol/L, leaching temperature of 80 ◦ C, liquid–solid ratio of 10:1,
leaching time of 120 min. The obtained Li2CO3, MnSO4, and nickel­ Appendix A. Supplementary material
–cobalt sulfides are regenerated as new NCM, initial discharge specific
capacity of which reaches 169.8 mAh/g under the condition of 0.2C Supplementary data to this article can be found online at [Link]
current density. After 100 cycles, the discharge specific capacity is org/10.1016/[Link].2023.06.027.
maintained at 143.24 mAh/g, and the coulombic efficiency is 92 %. The
electrochemical test results show that the regenerated cathode material References
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