744273

research-article2017
WMR0010.1177/0734242X17744273Waste Management & ResearchSun et al.

Original Article

Waste Management & Research

Sustainable recovery of valuable metals

2018, Vol. 36(2) 113­–120
© The Author(s) 2017
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DOI: 10.1177/0734242X17744273
https://doi.org/10.1177/0734242X17744273

DL-malic acid: Leaching and kinetics aspect journals.sagepub.com/home/wmr

Conghao Sun1, Liping Xu1, Xiangping Chen2, Tianyun Qiu1 and Tao Zhou1

Abstract
An eco-friendly and benign process has been investigated for the dissolution of Li, Co, Ni, and Mn from the cathode materials of spent
LiNi1/3Co1/3Mn1/3O2 batteries, using DL-malic acid as the leaching agent in this study. The leaching efficiencies of Li, Co, Ni, and Mn
can reach about 98.9%, 94.3%, 95.1%, and 96.4%, respectively, under the leaching conditions of DL-malic acid concentration of 1.2
M, hydrogen peroxide content of 1.5 vol.%, solid-to-liquid ratio of 40 g l-1, leaching temperature of 80°C, and leaching time of 30
min. In addition, the leaching kinetic was investigated based on the shrinking model and the results reveal that the leaching reaction
is controlled by chemical reactions within 10 min with activation energies (Ea) of 21.3 kJ·mol-1, 30.4 kJ·mol-1, 27.9 kJ·mol-1, and 26.2
kJ·mol-1 for Li, Co, Ni, and Mn, respectively. Diffusion process becomes the controlled step with a prolonged leaching time from 15
to 30 min, and the activation energies (Ea) are 20.2 kJ·mol-1, 28.9 kJ·mol-1, 26.3 kJ·mol-1, and 25.0 kJ·mol-1 for Li, Co, Ni, and Mn,
respectively. This hydrometallurgical route was found to be effective and environmentally friendly for leaching metals from spent
lithium batteries.

Keywords
Spent batteries, recovery, DL-malic acid, leaching, leaching kinetics

Received 27th December 2016, accepted 1st November 2017 by Associate Editor Alberto Bezama.

Introduction
Since being marketed by Sony in 1991, lithium-ion batteries 2014). Therefore, recycling of spent LIBs is not only beneficial
(LIBs) have been widely used for portable electronics such as to the environment but may also result in economic benefits (Lin
cell phones, laptops, digital cameras, etc (Bertuol et al., 2015). and Chiu, 2015).
LIBs allow a higher operating voltage, higher energy density, and Many methods have been developed for recycling spent LIBs,
longer cycle life (Chen et al., 2015b; Georgi-Maschler et al., including pyrometallurgy, biological, and hydrometallurgy pro-
2012) compared with traditional rechargeable batteries (NiCd cesses (Joo et al., 2015; Lee and Pandey, 2012; Zeng et al., 2014).
and NiMH batteries), greatly promoting the production and con- Compared with other processes, the hydrometallurgy process is
sumption of LIBs. Consumption of LIBs worldwide was about considered an ideal route due to lower energy consumption,
500 units in 2000 and 4.6 billion in 2010 (Fan et al., 2016). The higher recovery efficiency, and purity of metals (Chen et al.,
continuously increasing use of LIBs has led to increased genera- 2015c). In a typical hydrometallurgy process, the active cathodic
tion of waste LIBs, as their service life does not often last longer materials are leached by acids and reductant to transfer the target
than three years (Li et al., 2016). According to one report, the metals from the active materials to the leaching solution after
total of spent LIB batteries in China will exceed 25 billion units pretreatment. Meanwhile, high valence metals can be reduced to
in 2020 (Zeng et al., 2012).
Spent LIBs consist of metals, organic chemicals, and plastics 1Hunan Provincial Key Laboratory of Efficient and Clean Utilization
in the proportion of 5–20% cobalt, 5–10% nickel, 5–7% lithium, of Manganese Resources, College of Chemistry and Chemical
15% organic chemicals, and 7% plastics (Ferreira et al., 2009). Engineering, Central South University, PR China
2School of Environmental Science and Engineering, Shaanxi
From an economics point of view, valuable metals in the spent
University of Science & Technology, PR China
LIBs are rare and should be recycled. For example, cobalt is pre-
cious and considered as a strategic metal, and has been widely Corresponding author:
used in many fields (Kang et al., 2010). Besides, spent LIBs can Tao Zhou, College of Chemistry and Chemical Engineering, Central
South University, No. 932 Lushan South Road, Changsha, Hunan
cause potential risks for public health from both poisonous elec- Provence 410083, PR China.
trolytes and possible explosion (Wang et al., 2014; Yu et al., Email: [email protected]
114 Waste Management & Research 36(2)

more stable states, for example, Co3+ to Co2+, to increase the further purification. An electric-heated thermostatic water bath
leaching efficiency. Target metals in the leaching solution are (DK-2000, Baidianyiqi, China) equipped with a stirrer was used
then recovered by methods of chemical precipitation, solvent for the leaching process. A vacuum suction filter instrument
extraction, electrochemical processes, etc (Chen et al., 2015a, (SHB-III, Zhengzhou Du Fu Instrument, China) was used for
2015c; Li et al., 2015; Provazi et al., 2011). separating the residue from the process solution. The details of
Strong inorganic acids such as HCl (Li et al., 2009), H2SO4 the whole treatment process are reported below.
(Leea and Rhee, 2003) and HNO3 (Swain et al., 2007) have been
widely used because of their high leaching efficiency. However,
Pretreatment
due to the emitting of toxic gases as Cl2, SO3, and NOx during
leaching, the focus of research in recent years has turned to Spent LiNi1/3Co1/3Mn1/3O2 batteries were firstly discharged by
organic acids such as citric acid (Li et al., 2010b), oxalic acid soaking in NaCl solution for 24 h. The battery components (cath-
(Sun and Qiu, 2012) and DL-malic acid (Li et al., 2010a), which ode, anode, metal shell, and organic membrane) were separated
are more environmentally friendly. Li et al. (2010a) used malic from the LIBs by manual dismantlement and separation. The
acid as leaching reagent for leaching waste LiCoO2, and more cathode was bathed in NMP solvent at 90°C for 1.5 h while the
than 90% Co was obtained under optimal conditions. Citric acid anode was kept at 70°C for 15 min, after which step the mixed
and oxalic acid have also been investigated. In addition, the active materials could be peeled from the current collector. The
waste solutions containing metals can be treated by sorbent such Al and Cu foils could be recovered. The powders from the cath-
as metal-organic frameworks and graphene oxide (Rahimi and ode were calcined at 700°C for 2 h under atmosphere to remove
Mohaghegh, 2016). They can remove different kinds of organic the impurities (C and PVDF) after 2 h of drying at 80°C in an
and inorganic pollutants. oven. Then, the active materials were ball milled for 1 h to obtain
At present, commercialized cathode materials are mainly smaller particles, which will facilitate the leaching reactions (Li
LiCoO2, LiNi1/3Co1/3Mn1/3O2, LiMn2O4, and LiFePO4 (Chen et al., 2010a). A flow-chart of the pretreatment process is shown
et al., 2011, 2016, 2017; Johnson and Christopher, 2007). The in Figure 1.
LiCoO2-based battery was the most widely used type before
2016, due to its excellent electrochemical performance. Metal leaching
Therefore, the initial research on recycling was focused on the
spent LiCoO2 battery. But, the LiNi1/3Co1/3Mn1/3O2 battery is a All leaching experiments were carried out in 250 ml three-necked
promising candidate, and its market share has been increasing mechanically stirred flasks placed into a themorstatic bath
year by year (Zhang et al., 2014). Therefore, a large amount of (shown in Figure 2). Because the leaching reactions are exother-
waste LiNi1/3Co1/3Mn1/3O2, equal to other types of cathode mate- mic, a vapor condenser was employed to reduce the loss of water
rials, may be produced in the future, and should be disposed of by evaporation.
properly at end of life. However, the recycling of metals from The experiments in this work can be divided into two parts:
waste LiNi1/3Co1/3Mn1/3O2 cathodes, and kinetics and thermody- (a) determination of optimal leaching conditions; and (b) kinetic
namics investigations are scarcely reported. investigation of the leaching reaction. In the first step, a series of
Herein, the present work will focus on the leaching of waste parameters, including leaching time (5–40 min), temperature
LiNi1/3Co1/3Mn1/3O2 with DL-malic acid and H2O2 as leaching (50–90°C), acid concentration (0.5–1.5 M), H2O2 content (0–2.5
reagents. The optimal leaching conditions were obtained through vol.%), and solid/liquid ratio (20–60 g·l-1), were studied with a
a series of single-factor experiments, aimed at investigating the constant stirring speed of 300 rpm. A wine-red filtrate and a black
individual effect of the following operating conditions (factors): residue were obtained after leaching. The leaching solution and
leaching time, leaching temperature, acid concentration, solid-to- undissolved residues were filtered and washed with distilled
liquid ratio, and content of H2O2. Finally, the kinetic aspect of the water for analysis. Second, single-factor leaching experiments
leaching reaction was also investigated to determine the reaction were carried out to explore the reaction mechanism between
rate-controlled step and the apparent activation energy (Ea). waste LiNi1/3Co1/3Mn1/3O2 and DL-malic acid. The relationship
between leaching time and reaction temperature in fixed leaching
conditions will be investigated.
Materials and methods
Material and reagents Analytical procedures
In this study, spent LiNi1/3Co1/3Mn1/3O2 batteries of different To determine metal contents, quantitative cathodic active mate-
types and sizes were kindly supplied by the local recycling center. rial was dissolved completely in aqua regia (Li et al., 2010b,
The cathode materials were separated from the aluminum foil 2015) and analyzed by inductively coupled plasma atomic emis-
using N-Methyl-2-pyrrolidone (NMP) and then dissolved com- sion spectrometer (ICP-AES (Optima5300DV, Perkin EImer,
pletely in aqua regia for quantitative analysis of Li, Co, Ni, and China)). Metal contents in the leaching liquor were also identi-
Mn content. DL-malic acid was selected as the leaching agent fied through ICP-AES. The waste LiNi1/3Co1/3Mn1/3O2 samples
and hydrogen peroxide was employed as the reducing agent. All before and after calcinations, together with the residues after
the reagents were of analytical grade and used directly without leaching, were characterized by scanning electron microscopy
Sun et al. 115

Figure 1. Pretreatment of spent lithium-ion batteries (LIBs): (a) spent LIBs; (b) manual dismantling and separating: (b1) anode
of spent LIBs, (b2) cathode of spent LIBs, (b3) organic membrane of spent LIBs, (b4) battery shell materials; (c) anode and
cathode; (d) copper foil; (e) cathode active material before calcination; (f) Al foil; (g) cathode active material after calcination
and ball milling.

(SEM). The leaching efficiencies of Li, Co, Ni and Mn were cal-

culated according to equation (1) as follows
CV
η= ×100% (1)
M
Where η is the leaching efficiency, M is the initial amount of Li,
Co, Ni, or Mn in active materials (g), C is the metal (Li, Co, Ni,
or Mn) concentration in the leaching solution (g·ml-1) and V is the
total volume of the leaching solution (ml).

Results and discussion

Characterization of waste
LiNi1/3Co1/3Mn1/3O2
Figure 2. Scheme of the leaching reactor.
In this study, 1000 g cathode materials samples were completely
dissolved in aqua regia (100 ml) and analyzed by ICP-AES to
with a constant stirring speed of 300 rpm to explore the optimal
determine the contents of different metals in the calcined sam-
leaching conditions.
ples. Table 1 presents the detailed weight loss ratios before and
after calcination procedure and the contents of different metals in
Effect of malic acid concentration on leaching efficiency. The
waste cathode materials. It can be concluded that the weight loss
effect of DL-malic acid concentration was studied under the condi-
of different valuable metals can be ignored.
tions of 1.5 vol.% H2O2, S:L ratio 40 g·l-1, leaching time 30 min,
The SEM images of the active materials obtained from the
and reaction temperature 80°C. As revealed by Figure 4, the leach-
cathodes before and after calcination are shown in Figure 3(a)
ing efficiencies of different metals increase with the increase of
and (b). Apart from the active materials, a large amount of small
DL-malic acid concentration from 0.5 M to 1.5 M, and a satisfac-
particles were also observed before calcination, corresponding to
tory efficiency over 95% can be achieved for all metals. A sharp
conductive carbon and binder. The majority of these particles
increase in the leaching efficiency can be observed as the DL-malic
vanished after calcination at 700°C for 2 h (Figure 3(b)), which
acid concentration increased from 0.5 M to 0.8 M, followed by a
can be explained by the combustion of the conductor carbon and
gradual improvement in the range of 0.8–1.2 M. Further increase
binder and release in the form of gas.
of the DL-malic acid concentration does not show any significant
improvement in leaching efficiency. Hence, the optimal DL-malic
Leaching study acid concentration for the leaching process is 1.2 M.

A series of parameters, including leaching time (5–40 min), tem- Effect of time on leaching efficiency. The effect of the reaction
perature (50–90°C), acid concentration (0.5–1.5 M), H2O2 con- time (5–40 min) on the leaching of cobalt, nickel, manganese and
tent (0–2.5 vol.%) and solid/liquid ratio (20–60 g·l-1) were studied lithium was investigated under conditions of DL-malic acid
116 Waste Management & Research 36(2)

Table 1. The weight loss ratio before and after calcination

and the mass content of metals.

Metal element Weight loss ratio (%) Content (wt %)

Li 0.91 7.08
Co 0.05 20.26
Ni 0.16 20.19
Mn 0.06 18.89
Al 4.55 0.68
Others 0 0.75

Figure 5. Effect of time on leaching efficiency (DL-malic

acid=1.2 M, S:L=40 g·l-1, T=80°C, H2O2=1.5 vol.%).

Figure 3. SEM images of the cathodic active materials: (a)

waste cathodic materials before calcination; (b) cathodic
materials after calcination.

Figure 6. Effect of temperature on leaching efficiency (DL-

malic acid=1.2 M, S:L=40 g·l-1, t=30 min, H2O2=1.5 vol.%).

increased from the initial value of around 60% to above 90% as

the temperature increases from 50°C to 80°C. This may be due to
the dissociation of DL-malic acid during the endothermic pro-
cess. Elevated temperature promotes the process and allows more
Figure 4. Effect of DL-malic acid concentration on leaching H+ to present in the solution. When the dissolution was complete,
efficiency (t=30 min, S:L=40 g·l-1, T=80°C, H2O2=1.5 vol.%). a further increase in the temperature did not enhance the leaching
efficiency to greater extents. Therefore, the optimal leaching
concentration 1.2 M, S/L ratio 40 g·l-1, reaction temperature 80°C temperature was determined to be 80°C.
and peroxide amount 1.5 vol.%. As shown in Figure 5, the time
can remarkably affect the leaching efficiency. The most obvious Effect of H2O2 volume percentage on leaching efficiency. In
improvement in leaching efficiency was found in the first 10 min. this step, the effect of H2O2 concentration on the leaching effi-
As the reaction went on, the slope became less steep. The leach- ciency of the waste cathode active materials was investigated.
ing efficiency reached the maximum after 30 min (98%, 94%, The waste LiNi1/3Co1/3Mn1/3O2 material was leached with 1.2 M
95%, and 96% for Li, Co, Ni, and Mn, respectively) and did not DL-malic acid solution at a S:L of 40 g·l-1. During leaching, the
vary much afterwards. Therefore, 30 min was selected as the temperature was maintained at 80°C and the leaching time was
most suitable value for the leaching time. 30 min. The results (see Figure 7) indicate that the amount of
H2O2 plays an important role in the leaching. In the absence of
Effect of temperature on leaching efficiency. Figure 6 illus- H2O2, the leaching efficiency of the waste LiNi1/3Co1/3Mn1/3O2
trates the effect of the leaching temperature on the leaching effi- was only 41.8%, 5.6%, 7.9%, 17.3% for Li, Co, Ni, Mn, respec-
ciency of cobalt, nickel, manganese and lithium. Other leaching tively. This low leaching efficiency can be attributed to the fact
conditions remained constant in the tests. The leaching efficiency that Li+, Ni2+, and Co2+ ions can be readily leached under the
Sun et al. 117

Ni, and Mn increased with the decrease of S:L. More than 98%
lithium, 94% cobalt, 95% nickel, and 96% manganese could be
leached at 40 g·l-1. When the S:L exceeded 40 g·l-1, the leaching
efficiency decreased sharply. Taking both the chemical consump-
tion and leaching efficiency into account, the optimal solid/liquid
ratio was therefore determined to be 40 g·l-1.
Based on the discussion above, the optimal conditions for the
leaching of cobalt, nickel, manganese, and lithium from waste
LiNi1/3Co1/3Mn1/3O2 can be determined. When operated with
leaching solutions containing 1.2 M DL-malic acid, 1.2 vol.%
H2O2, and a 40 g·l-1 S:L ratio, after 30 min leaching under the
temperature of 80°C, maximum efficiency of 98.9% Li, 94.3%
Co, 95.1% Ni and 96.4% Mn can be reached.

Figure 7. Effect of H2O2 volume percent on leaching efficiency

(DL-malic acid=1.2 M, S:L=40 g·l-1, T=80°C, t=30 min). Kinetic studies
Kinetic studies were conducted to determine the reaction kinetic
of leaching lithium, nickel, manganese, and cobalt by the acid
under different leaching times (0–30 min) and temperatures (40–
80°C). Other conditions are listed as follows: peroxide content of
1.5 vol.%, DL-malic acid concentration of 1.2 M, and S/L ratio of
40 g·l-1.
The leaching of spent LIBs is a heterogeneous reaction, and
the leaching rate may be controlled by either chemical reactions
or diffusion (Li et al., 2015). When leaching is controlled by
chemical reactions, the process can be described by equation (3).
When the largest resistance to the leaching process is the diffu-
sion through the boundary layer, the shrinking-core model pre-
dicts the following expression for the leaching kinetics of
shrinking particles (equation (4)).
The chemical reaction-controlled leaching is as follows
Figure 8. Effect of solid-to-liquid ratio on the leaching
efficiency (DL-malic acid=1.2 M, t=30 min, T=80°C, H2O2=1.5 1
vol.%). 1 − (1 − X ) 3 = kct (3)

The diffusion-controlled leaching is as follows

mere presence of the acid while Ni3+, Ni4+, Co3+, and Mn4+ need
2
a reducing agent (Yao et al., 2015; Zhang et al., 2015). With the 2
1− X − (1 − X ) 3 = kd t (4)
addition of H2O2, the leaching efficiency rose remarkably and 3
reached above 95% for all four contents while the H2O2 content Where X is the conversion of reactants, kc is the rate constant of
was 1.5 vol.%. In this stage, hydrogen peroxide could be oxi- chemical reactions (min-1), kd is the apparent diffusion constant
dized by high-valent transition metal ions. There was no signifi- (min-1), t is the leaching time (min).
cant change in leaching efficiency when further increasing the As shown in Figure 9, at the beginning of the reaction (0–10
H2O2 concentration to 2.5 vol.%. Due to its low thermal stability, min), the kinetic data for all the metals fit satisfactorily to the
H2O2 can decompose under elevated temperatures according to chemical reaction model (equation (3)) regardless of operating
equation (2) (Zhang et al., 2013), lowering its effective concen- temperatures. The result indicates that the initial leaching process
tration as follows was controlled by the chemical reaction.
The values of activation energy were determined from the
H 2O 2 ( l ) → H 2O ( l ) +1/ 2O 2 ( g ) (2) Arrhenius equation (equation (5)) which describes the relation-
ship between the specific rate constant (equation (3)) and the
Effect of solid-to-liquid ratio on leaching efficiency. A high temperature as follows
solid/liquid ratio is usually more desirable in terms of the process
throughput. The effect of solid/liquid ratio (S:L), varied from 20 k = Ae− Ea / RT (5)
to 60 g·l-1, on the leaching efficiency of cobalt, nickel, manga-
nese, and lithium was studied under experimental conditions of where k is the reaction rate constant, A is the frequency factor, Ea
90°C, 1.2 M DL-malic acid, 30 min reaction time and 1.5 vol.% is the apparent activation energy, and R is the universal gas con-
H2O2. Figure 8 indicates that the leaching efficiencies of Li, Co, stant (8.314472 J·k-1·mol-1).
118 Waste Management & Research 36(2)

Figure 9. Plots of 1-(1-X)1/3 versus leaching time at temperatures (50–80°C) by 1.2 M DL-malic acid solution: (A) Li; (B) Co; (C)
Ni; (D) Mn.

is clearly indicative of a chemically reaction-control in the leach-

ing process from 0 to 10 min.
The results in Figure 11 reflect that on further increasing the
leaching time to 30 min, the kinetic conformed to diffusion con-
trol with relatively high parameters values of R2, ranging from
0.989 to 0.997 for Mn, 0.993 to 0.998 for Li, 0.991 to 0.998 for
Co, and 0.996 to 0.999 for Ni of the diffusion control model. This
indicates that the speed of ash diffusion became the limiting step
in the overall leaching rate after 15 min.
The values of the rate constants were obtained similarly as
above. Activation energy could be calculated from the Arrhenius
plot in Figure 12 and the values are 22.6 kJ·mol-1 for Li, 31.2
kJ·mol-1 for Co, 28.8 kJ·mol-1 for Ni, and 27.2 kJ·mol-1 for Mn,
Figure 10. Arrhenius plot for Mn, Ni, Co, and Li leaching in respectively, in the temperature range of 50–80°C.
1.2 M malic acid solution (0–10 min).
Conclusion
Based on the rate constants (0–10 min) calculated from Figure 9, In this paper, valuable metals in spent LiNi1/3Co1/3Mn1/3O2 batter-
the evolution of lnk with respect to the reverse of temperature 1/T ies were leached by using the environmentally friendly malic
was plotted and found to be linear for all the metals (Figure 10). The acid. The process includes two steps: (a) pretreatment, (b) reduc-
values of the apparent activation energy (Ea) for the leaching ele- tive leaching with DL-malic acid to transfer the valuable metals
ments were then determined from the slopes, corresponding to 20.3 (Li, Co, Ni, and Mn) from the cathodic material to the leaching
kJ·mol-1 for Li, 29.9 kJ·mol-1 for Co, 27.1 kJ·mol-1 for Ni, and 26.4 solution. The optimum leaching conditions were found to be 1.2
kJ·mol-1 for Mn. M DL-malic acid, 40 g·l-1 initial S:L ratio, 90°C, 1.5 vol.% H2O2
The relatively high values of activation energies obtained for and 30 min and the resulting leaching efficiencies were Li
leaching of these elements by malic acid in the presence of H2O2 (98.9%), Co (94.3%), Ni (95.1%), and Mn (96.4%).
Sun et al. 119

Figure 11. Plots of 1-2X/3-(1-X)2/3 versus Leaching time at temperatures (50–80°C) by 1.2 M DL-malic acid solution: (A) Li; (B)
Co; (C) Ni; (D) Mn.

Declaration of conflicting interests

The authors declared no potential conflicts of interest with respect to
the research, authorship, and/or publication of this article.

Funding
The authors disclosed receipt of the following financial support for
the research, authorship, and/or publication of this article: The
authors acknowledge with gratitude for financial support of the
Fundamental Research Funds for the Central Universities of Central
South University (grant number 72150050350), National Natural
Science Foundation of China (grant number 21176266) and the
Project supported by the Hunan Provincial Science and Technology
Plan, China (grant number 2016TP1007).

References
Figure 12. Arrhenius plot for Mn, Ni, Co, and Li leaching in Bertuol DA, Toniasso C, Jimenez BM, et al. (2015) Application of spouted
1.2 M malic acid solution (15–30 min). bed elutriation in the recycling of lithium ion batteries. Journal of Power
Sources 275: 627–632.
Chen L, Tang X, Zhang Y, et al. (2011) Process for the recovery of cobalt
Kinetic studies reveal that the leaching process at 0–10 min is oxalate from spent lithium-ion batteries. Hydrometallurgy 108: 80–86.
controlled by the chemical reaction and value of activation Chen XP, Chen YB, Zhou T, et al. (2015a) Hydrometallurgical recovery of
metal values from sulfuric acid leaching liquor of spent lithium-ion bat-
energy (Ea) for Li, Co, Ni, and Mn is 20.3 kJ·mol-1, 29.9 kJ·mol-1, teries. Waste Management 38: 349–356.
27.1 kJ·mol-1, and 26.4 kJ·mol-1, respectively. However, the Chen XP, Fan BL, Xu LP, et al. (2016) An atom-economic process for the
leaching process at 15–30 min is controlled by diffusion and recovery of high value-added metals from spent lithium-ion batteries.
Journal of Cleaner Production 112: 3562–3570.
value of activation energy (Ea) is 22.6 kJ·mol-1 for Li, 31.2 Chen XP, Ma HR, Luo CB, et al. (2017) Recovery of valuable metals from
kJ·mol-1 for Co, 28.8 kJ·mol-1 for Ni, and 27.2 kJ·mol-1 for Mn, waste cathode materials of spent lithium-ion batteries using mild phos-
respectively. The process may promise an effective and environ- phoric acid, Journal of Hazardous Materials 326: 77–86
Chen XP, Xu B, Zhou T, et al. (2015b) Separation and recovery of metal
mentally friendly route for the leaching of metal values from values from leaching liquor of mixed-type of spent lithium-ion batteries.
spent LIBs. Separation and Purification Technology 144: 197–205.
120 Waste Management & Research 36(2)

Chen XP, Zhou T, Kong JR, et al. (2015c) Separation and recovery of metal Provazi K, Campos BA, Espinosa DCR, et al. (2011) Metal separation from
values from leach liquor of waste lithium nickel cobalt manganese oxide mixed types of batteries using selective precipitation and liquid–liquid
based cathodes. Separation and Purification Technology 141: 76–83. extraction techniques. Waste Management 31: 59–64.
Fan BL, Chen XP, Zhou T, et al. (2016) A sustainable process for the recovery Rahimi E and Mohaghegh N (2016) Removal of toxic metal ions from sun-
of valuable metals from spent lithium-ion batteries. Waste Management gun acid rock drainage using mordenite zeolite, graphene nanosheets,
& Research 34: 474–481. and a novel metal-organic framework. Mine Water and the Environment
Ferreira DA, Prados LMZ, Majuste D, et al. (2009) Hydrometallurgical sepa- 35(1): 18–28.
ration of aluminium, cobalt, copper and lithium from spent Li-ion batter- Swain B, Jeong J, Lee J, et al. (2007) Hydrometallurgical process for recov-
ies. Journal of Power Sources 187: 238–246. ery of cobalt from waste cathodic active material generated during
Georgi-Maschler T, Friedrich B, Weyheb R, et al. (2012) Development of a recy- manufacturing of lithium ion batteries. Journal of Power Sources 167:
cling process for Li-ion batteries. Journal of Power Sources 207: 173–182. 536–544.
Johnson and Christopher S (2007) Development and utility of manganese oxides Sun L and Qiu KQ (2012) Organic oxalate as leachant and precipitant for
as cathodes in lithium batteries. Journal of Power Sources 165: 559–565. the recovery of valuable metals from spent lithium-ion batteries. Waste
Joo SH, Shin SM, Shin DJ, et al. (2015) Development of recycling technol- Management 32: 1575–1582.
ogy to recover valuable metals from lithium primary and ion batteries. Wang X, Gaustad G, Babbitt CW, et al. (2014) Economic and environmental
Journal of Engineering Manufacture 229: 212–220. characterization of an evolving Li-ion battery waste stream. Journal of
Kang J, Senanayake G, Sohn J, et al. (2010) Recovery of cobalt sulfate from Environmental Management 135: 126–134.
spent lithium ion batteries by reductive leaching and solvent extraction Yao L, Feng Y and Xi G (2015) A new method for the synthesis of
with Cyanex 272. Hydrometallurgy 100: 168–171. LiNi1/3Co1/3Mn1/3O2 from waste lithium ion batteries. RSC Advances,
Lee JC and Pandey BD (2012) Bio-processing of solid wastes and secondary 5(55): 44107–44114.
resources for metal extraction-A review. Waste Management 32: 3–18. Yu Y, Chen B, Huang K, et al. (2014) Environmental impact assessment
Leea CK and Rhee KI (2003) Reductive leaching of cathodic active materials and end-of-life treatment policy analysis for Li-ion batteries and Ni-MH
from lithium ion battery wastes. Hydrometallurgy 68: 5–10. batteries. International Journal of Environmental Research and Public
Li JH, Shi PX, Wang ZF, et al. (2009) A combined recovery process of metals Health 11: 3185–98.
in spent lithium-ion batteries. Chemosphere 77: 1132–1136. Zeng XL, Li JH and Ren Y (2012) Prediction of various discarded lithium
Li J, Wang G and Xu Z (2016) Environmentally-friendly oxygen-free roast- batteries in China. IEEE International Symposium on Sustainable Systems
ing wet magnetic separation technology for in situ recycling cobalt, lith- and Technology, Boston, 16–18 May, 2012: 1–4.
ium carbonate and graphite from spent LiCoO2 graphite lithium batteries. Zeng XL, Li JH and Singh N (2014) Recycling of spent lithium-ion bat-
Journal of Hazardous Materials 302: 97–104. tery: A critical review. Critical Reviews in Environmental Science and
Li L, Ge J, Chen R, et al. (2010a) Environmental friendly leaching reagent Technology 44: 1129–1165.
for cobalt and lithium recovery from spent lithium-ion batteries. Waste Zhang X, Cao H, Xie Y, et al. (2015) A closed-loop process for recycling
Management 30: 2615–2621. LiNi1/3Co1/3Mn1/3O2, from the cathode scraps of lithium-ion batteries:
Li L, Gea J, Wu F, et al. (2010b) Recovery of cobalt and lithium from spent Process optimization and kinetics analysis. Separation & Purification
lithium ion batteries using organic citric acid as leachant. Journal of Technology 150: 186–195.
Hazardous Materials 176: 288–293. Zhang XH, Xie YB, Cao H, et al. (2014) A novel process for recycling and
Li L, Qu W, Zhang X, et al. (2015) Succinic acid-based leaching system: a resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for
sustainable process for recovery of valuable metals from spent Li-ion bat- lithium-ion batteries. Waste Management 34: 1715–1724.
teries. Journal of Power Sources 282: 544–551. Zhang XH, Xie YB, Lin X, et al. (2013) An overview on the processes and
Lin SS and Chiu KH (2015) An evaluation of recycling schemes for waste technologies for recycling cathodic active materials from spent lithium-
dry batteries-a simulation approach. Journal of Cleaner Production 93: ion batteries. Journal of Material Cycles and Waste Management 15:
330–338. 420–430.