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Lithium Carbonate Recovery from Cathode Scrap of Spent Lithium-Ion

Battery: A Closed-Loop Process

Article  in  Environmental Science & Technology · January 2017

DOI: 10.1021/acs.est.6b03320

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Lithium Carbonate Recovery from Cathode Scrap of Spent Lithium-

Ion Battery: A Closed-Loop Process
Wenfang Gao,†,‡ Xihua Zhang,‡,§ Xiaohong Zheng,‡ Xiao Lin,*,‡ Hongbin Cao,†,‡ Yi Zhang,†,‡
and Zhi Sun*,‡
†
National Engineering Research Center of Distillation Technology, School of Chemical Engineering and Technology, Tianjin
University, Tianjin 300072, China
‡
Division of Environment Technology and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing
100190, China
§
Solid Waste and Chemicals Management Center, Ministry of Environmental Protection of China, Beijing 100029, China
*
S Supporting Information

ABSTRACT: A closed-loop process to recover lithium carbonate from

cathode scrap of lithium-ion battery (LIB) is developed. Lithium could be
selectively leached into solution using formic acid while aluminum
remained as the metallic form, and most of the other metals from the
cathode scrap could be precipitated out. This phenomenon clearly
demonstrates that formic acid can be used for lithium recovery from
cathode scrap, as both leaching and separation reagent. By investigating
the effects of different parameters including temperature, formic acid
concentration, H2O2 amount, and solid to liquid ratio, the leaching rate of
Li can reach 99.93% with minor Al loss into the solution. Subsequently,
the leaching kinetics was evaluated and the controlling step as well as the
apparent activation energy could be determined. After further separation
of the remaining Ni, Co, and Mn from the leachate, Li2CO3 with the
purity of 99.90% could be obtained. The final solution after lithium
carbonate extraction can be further processed for sodium formate preparation, and Ni, Co, and Mn precipitates are ready for
precursor preparation for cathode materials. As a result, the global recovery rates of Al, Li, Ni, Co, and Mn in this process were
found to be 95.46%, 98.22%, 99.96%, 99.96%, and 99.95% respectively, achieving effective resources recycling from cathode scrap
of spent LIB.

1. INTRODUCTION to be the most valuable fraction to be recycled because of the

The demand of lithium-ion batteries (LIBs) is directly driven content of cathode materials and high purity aluminum foil.5 In
by their extensive applications on electrical and electronic the pyrometallurgical processes, for instance, in Umicore,6 the
products including laptops, mobile phones, and electric bikes spent batteries are smelted with flux to form a metal phase
and vehicles (EVs).1 In 2014, the production of LIBs had containing mostly Co, Ni, and partial Fe to be refined and a slag
reached 5.287 billion units only in China.2 It has subsequently phase containing Li and a small amount of other metals to be
resulted in a large amount of spent LIBs and production scrap further recovered. However, the recovery rate of Co is relatively
required to be treated. On one hand, this type of waste is low due to its complicated recycling route and the difficulty in
considered to be hazardous due to the high content of heavy selective recovery of Li.7−11 At the same time, its high capital
metals3 and fluoride-bearing electrolyte. On the other hand, a cost, potential hazardous gas emission, relatively high energy
significant amount of valuable metals,4 including Li, Ni, Co, Al, consumption, and rather complex extraction procedures limit
and Cu, is ready to be recycled from such waste which has the flexibility of this technology. The extraction of metals,
therefore attracted worldwide attention to develop various especially minor elements (metals), is significantly constrained
technologies, aiming to either minimize the management risks by their partitioning behavior between metal phase and molten
or maximize the recovery rate of the valuable metals. slag. Hydrometallurgy with leaching and extraction as the main
Typical recycling technologies can be classified into three steps similar to treatment of other types of waste12−14 has
categories: pyrometallurgy, hydrometallurgy, and biometallurgy.
Prior to metal recovery, spent battery is usually pretreated via Received: August 8, 2016
disassembling and/or mechanical shredding. Among different Revised: November 23, 2016
fractions of the spent LIBs after pretreatment, cobalt-based Accepted: January 12, 2017
cathode scrap together with its production scrap is considered Published: January 12, 2017

© 2017 American Chemical Society 1662 DOI: 10.1021/acs.est.6b03320

Environ. Sci. Technol. 2017, 51, 1662−1669
Environmental Science & Technology Article

therefore attracted more attention than pyrometallurgy 2. EXPERIMENTAL SECTION

recently,15 in which the inorganic acids (e.g., H2SO4,16−21
2.1. Materials and Reagents. Supplied by a local lithium-
HCl,22−24 and HNO3) and organic acids (e.g., citric acid,25−28
29 27 30,31 ion battery recycling company (Brunp Recycling Co. Ltd.), the
DL-malic acid, ascorbic acid, oxalic acid, succinic acid,32
active material of the disassembled polytetrafluoroethylene
and trichloroacetic acid33) were used as leachants. During the
(PTFE)-based cathode scrap is LiNi1/3Co1/3Mn1/3O2 (Figures
leaching process, reductants such as H2O2,19,21,22,32−35
S1 and S2).33,37 All chemicals (HCOOH-based, H2O2, NaOH,
NaHSO3,16 and glucose17,18,25 are usually added to the solution
Na2CO3) were of analytical grade, and all solutions were
to increase the recovery rate of different metals. Inorganic acids
prepared with ultrapure water (Millipore Milli-Q).
are readily leaching almost all metals from the cathode scrap
2.2. Characterization of Experimental Materials. The
with low leaching selectivity (selectively leaching the targeted
cathode scrap was cut into pieces with a size of approximately
metals), and the metal recovery depends largely on the
10 mm × 10 mm. After drying at 60 °C for 24 h, the cathode
subsequent solvent extraction steps.36 Different from inorganic
scrap pieces were dissolved in the aqua regia solution (HNO3/
acids, organic acids can be employed as leachant, reductant,
precipitant, or chelating agent during cathode scrap processing. HCl = 1:3, v/v) to determine the contents of metals by
Zeng et al.30 and Sun and Qiu31 used oxalic acid as both inductively coupled plasma-optical emission spectrometry
leachant and precipitant to recover cobalt and lithium from (ICP-OES). The metal contents were found to be 18.32%
LiCoO2. Yao et al.28 introduced citric acid as both leaching and nickel, 18.65% cobalt, 17.57% manganese, 6.15% lithium, and
chelating agents to treat the cathode material which was already 7.86% aluminum, respectively.
separated from Al foil using N-methyl pyrrolidone (NMP) 2.3. Selective Leaching of Cathode Scrap. The leaching
dissolution at 80 °C. Since NMP can only dissolve polar experiments were performed in a 1000 mL three-necked round-
organic binders (e.g., polyvinylidene fluoride, PVDF), rather bottom flask installed with a reflux condenser to avoid the loss
than the highly nonpolar binders such as polytetrafluoro- of formic acid. A heating bath with a magnetic stirrer was used
ethylene (PTFE),37 thermal treatment at 600 °C is required in to ensure optimized kinetics condition and temperature
order to reach effective separation of the aluminum foil and control. During the experiments, a certain amount of cathode
cathode material.28 However, the resulted NMP contained scrap was added into a 250 mL mixed solution including formic
solution is rather difficult to be recirculated which finally has to acid-based leaching solution and H2O2. After reacting for a
be disposed as organic liquid waste. In addition, in the preset period, the mixture (leachate and reaction residue) was
aforementioned hydrometallurgical processes, it mostly requires filtered immediately. During the leaching experiments, the
one to manually disassemble the battery and then either peel effects of a range of factors including the temperature, acid
the cathode materials off the aluminum foil or dissolve and concentration, liquid-to-solid ratio, and reductant amount were
burn the binders to obtain cathode powder for further considered.
recycling.19,21−23,32−34 Research on cathode scrap after effective 2.4. Lithium Carbonate Precipitation and Ni, Co, and
mechanical processing (e.g., shredding and separation) or such Mn Precipitation. The leachate and residue were treated
scrap from LIBs production in a practical approach with separately following the procedures outlined below. Lithium
minimized environmental impact is limited. Two aspects, carbonate was prepared after the remaining Ni, Co, and Mn
leaching selectivity and closed-materials-loop, are therefore were precipitated out from the leachate following traditional
critical to be considered in order to develop an effective near- procedures for Ni−Co−Mn hydroxide precursor preparation.21
to-industry process for spent LIBs recycling. The leachate and sodium hydroxide solution (5 M) were
In previous work,37 we have tried to close the materials loop simultaneously pumped into the reactor with the speed of 2
for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the mL/min under the protection of nitrogen at 65 °C with stirring
LIBs cathode scrap, in which trifluoroacetic acid (TFA) was speed of 1300 rpm. Afterward, the pH value of the mixture was
employed to dissolve the organic binder PTFE and then first adjusted to 6.45 in order to precipitate Al3+ by adding
separate the cathode material from Al foil. However, it is found NaOH and NH4OH solution into the reactor, and then, the pH
that considerable amount of aluminum could be coleached was further adjusted and maintained at 11 for 24 h after vacuum
during the separation of cathode material from the Al foil. The filtration. After centrifuging, the mixture of Ni, Co, and Mn
aluminum needs to be removed before further recycling of Ni, hydroxide precipitate (precipitate II) was obtained, after which
Co, Mn, and Li from the leachate. Furthermore, TFA is it was thoroughly washed with ultrapure water and dried in a
relatively expensive which might bring economic uncertainties vacuum oven at 80 °C for 10 h. The raffinate was adjusted to
to the further scaling-up of this process if the purification and neutral with formic acid, and saturated Na2CO3 of stoichio-
recirculation of TFA cannot be achieved. With this research, we metric amount was subsequently added into the raffinate at
demonstrate a process for cathode scrap recycling by designing 20−60 °C with a speed of 1−5 mL/min. The precipitated
the materials flow in order to improve the materials efficiency Li2CO3 was washed with boiling ultrapure water and dried in a
of the recycling process and minimize aluminum loss and vacuum oven for 12 h.
environmental impact, with full recycling of the cathode scrap. The leaching residue that contains Al foil, precipitates during
Formic acid, which can function both as reductant and leachant, leaching, and leaching residue of a very small amount (mainly
is introduced. The following aspects are the focus in this undissolved organic binder and conductive reagent) was sieved
research: (1) identifying the behavior of formic acid as a partial using a sieving mesh of 0.5 mm pore size. Al foil was
reductant; (2) the effects of different factors on cathode scrap subsequently collected for metal recycling. The separated
leaching and aluminum loss by considering the kinetics precipitate and Ni, Co, and Mn hydroxide precipitation
behavior; (3) characterization of the recycled products (precipitate I) were collected for Ni−Co−Mn precursor
including Li2CO3. However, the preparation of cathode preparation.21
materials as well as the electrochemical performance is not 2.5. Characterization. The concentrations of all metals in
included in this research. solutions were measured by an inductively coupled plasma
1663 DOI: 10.1021/acs.est.6b03320
Environ. Sci. Technol. 2017, 51, 1662−1669
Environmental Science & Technology Article

Figure 1. Leaching rate of metals using different acids: (a) TFA33, (b) formic acid, and (c) formic acid with H2O2.

Figure 2. Leaching rate of each metal under varying formic acid concentrations (a) and solid to liquid ratio (S/L) (b).

Figure 3. Leaching rate of (a) Al, (b) Li, (c) Co, (d) Mn, and (e) Ni from the cathode scrap under different hydrogen peroxide concentrations and
times.

optical emission spectrometer (ICP-OES, iCAP 6300, Radial, 3. RESULTS AND DISCUSSION
Thermo Scientific). The morphology was observed by a
As the simplest carboxylic acid with an aldehyde, the formic
mineral liberation analyzer (MLA 250, FEI) which contains
an energy dispersive spectrometer (EDS, EDAX GenesisSiLi) acid can be used as leachate and reductant to (1) separate the
and a scanning electron micrometer (SEM, Quanta 250). The cathode materials from aluminum foil of the cathode scrap and
crystal structures of solid materials were characterized by an X- (2) selectively recover lithium from the cathode scrap.
ray diffractmeter (X’pert PRO, PANalytical) with Cu Kα 3.1. Selective Leaching of Cathode Scrap. The acid
radiation. ionization equation of formic acid is described by
1664 DOI: 10.1021/acs.est.6b03320
Environ. Sci. Technol. 2017, 51, 1662−1669
Environmental Science & Technology Article

Figure 4. Leaching rate of (a) Al, (b) Co, (c) Li, (d) Mn, and (e) Ni from the cathode scrap under different reaction temperatures and times.

Table 1. Kinetic Parameters during the Leaching Process with H2O2 Calculated Using the Surface Chemical Control Model
Co Li Mn Ni
−1 2 −1 2 −1 2 −1
T (K) k (min ) R k (min ) R k (min ) R k (min ) R2
303.15 0.01607 0.98776 0.01995 0.98296 0.01529 0.98876 0.01595 0.98788
313.15 0.02136 0.98592 0.02621 0.98059 0.02033 0.98623 0.02118 0.98534
323.15 0.03751 0.99746 0.04831 0.9964 0.03611 0.99787 0.03795 0.99802
333.15 0.05850 0.99684 0.07810 0.99774 0.05845 0.99684 0.06033 0.99758
343.15 0.06085 0.99476 0.08129 0.9989 0.0588 0.99504 0.06143 0.99633
353.15 0.05603 0.99845 0.07078 0.99994 0.05333 0.99908 0.05615 0.99886

lithium with a lower leaching rate of the aluminum to obtain

high purity aluminum foil, while most of the nickel, cobalt, and
manganese can be precipitated out as hydroxides. The chemical
reactions during the leaching process can be described as
2Al(s) + 6HCOOH(aq) → 2C3H3AlO6 (aq) + 3H 2(g)
(2)

6LiNi1/3Co1/3Mn1/3O2 (s) + 21HCOOH(aq) → 2C2

H 2NiO4 (aq) + 2C2H 2CoO4 (aq) + 2C2H 2MnO4 (aq)
+ 6CHLiO2 (aq) + 3CO2 (g) + 12H 2O(aq) (3)

To illustrate the selectivity of formic acid to aluminum leaching,

two exploratory experiments were carried out under the
following conditions: formic acid concentration of 2 mol/L,
reaction temperature of 70 °C, solid to liquid ratio (S/L) of 50
Figure 5. Arrhenius plots for leaching of Co, Mn, Ni, and Li from the g/L, and reaction time of 120 min, while the 2 vol % of 30 wt %
cathode scrap under the surface chemical control model with the H2O2 was only added to one of the experiments. In comparison
addition of H2O2.
with TFA leaching process (Figure 1a), which had a longer
time of 240 min and the stronger acidity (pKa = 0.23, 25 °C,
HCOOH(aq) → HCOO−(aq) + H+(aq) H2O),33 the leaching rate of Ni, Co, and Mn was nearly 45% at
(pK a = 3.77, 25°C, H 2O) (1)
120 min by the formic acid process (Figure 1b) while TFA
consumed 240 min to reach the same rate, proving that the
Other than a weak acid, formic acid is also reductive to metal reduction ability of formic acid can enhance the leaching effects
ions with high oxidative potentials because of its aldehyde. of the metals of spent cathode materials. In order to improve
Different from other acids, formic acid can selectively leach the leaching rate of cathode scrap (Co3+ and Mn4+ need to be
1665 DOI: 10.1021/acs.est.6b03320
Environ. Sci. Technol. 2017, 51, 1662−1669
Environmental Science & Technology Article

Figure 6. XRD patterns of the precipitated Li2CO3 and standard powder diffraction peaks of Li2CO3 (a), SEM images of the precipitated Li2CO3
(b), particle size distribution (c).

concentration on the leaching of cathode scrap, experiments

were carried out to optimize the conditions for the extraction of
nickel, cobalt, manganese, lithium, and aluminum under the
conditions as follows: the ratio of the cathode scrap to acid
solution (S/L) of 50 g/L, formic acid concentration ranging
from 1.0 to 4.5 mol/L, acid solution volume of 250 mL,
leaching temperature of 60 °C, and reaction time of 120 min.
The leaching rate of each element under the different formic
acid concentrations is presented in Figure 2a.
When increasing the formic acid concentration from 1.0 to
4.5 mol/L, a clear increase of the leaching rates for Ni, Co, Mn,
and Li can be observed while the leaching rate of Al is always
below 10%. According to the changing leaching rate against the
dyM
acid concentration, i.e., , the concentration of formic acid
dCA
Figure 7. Simplified flow sheet of the recovery process based on
formic acid. has an insignificant effect on the leaching of Al compared with
other elements from the cathode scrap. This indicates that
Table 2. Global Recovery Rates of Different Metals from the aluminum is relatively stable in this solution of weak acid and
Cathode Scrap in This Research enables formic acid leaching to separate the Al foil from the
cathode materials. For the sake of optimized leaching
element Al Li Ni Co Mn
conditions, 2 mol/L for the formic acid concentration was
recovery rate 95.46 98.22 99.964 99.964 99.947
(wt %) chosen in the following experiments.
product form Al foil Li2CO3 precursor To investigate the effect of S/L, the leaching experiments
major loss Al(OH)3 NaCOOH Al foil were performed under the following conditions: S/L ratio of 30
solution to 90 g/L, acid concentration of 2 mol/L of 250 mL formic acid
solution, and 60 °C for 120 min. As given in Figure 2b, with the
increase of the S/L from 30 to 90 g/L, the leaching rates of Ni,
converted to Co2+ and Mn2+, respectively38), additional Co, Mn, and Li all decrease slightly with a fixed reaction time
reductant (H2O2) can be introduced.39 The leaching rates of which indicates the reaction requires sufficient formic acid to
Ni, Co, Mn, and Li increase within 20 min as Figure 1c shows, ensure the reaction speed.40 The phenomenon of insignificant
while the rates, except that of Li, decrease after 30 min because effect on the leaching rate of Al with different S/L ratios
of the formation of hydroxide precipitation. During leaching, it
indicates that the reaction between formic acid and Al is trivial.
was noticed that the solubilities of Co(COOH)2, Ni(COOH)2,
However, a large amount of S/L is usually required to facilitate
and Mn(COOH) 2 are relatively small compared with
LiCOOH, although comprehensive solubility data could not proper operational efficiency in practical applications, and
be found in the literature. At the end of leaching, amorphous therefore, the S/L was chosen to be 50 g/L in accordance to
precipitate of Co/Ni/Mn together with a small amount of Figure 2b.
organic binder and Al foil were obtained with minimized Co/ 3.1.2. Effect of Reductant Amount. In the literature, the
Ni/Mn in the solution which enables effective recovery of reducing reagents for spent lithium ion battery leaching can be
lithium in the next stage. Further investigation on the solubility sodium thiosulfate (Na 2 S 2 O 3 ), 3 3 sodium bisulfite
behavior of formic salts will be given in our future research. In (NaHSO3),16,17 and hydrogen peroxide (H2O2).19,21,22,32−34
order to find the optimized leaching conditions, the effects of According to our preliminary experiments, hydrogen peroxide
formic acid concentration, solid−liquid ratio (S/L), and was selected as the reductant in order not to introduce impure
reaction temperature were evaluated before addition of other ions.
reductants, in the first stage of the experiments. With the addition of 30 wt % hydrogen peroxide, the
3.1.1. Effect of Formic Acid Concentration and Solid to leaching reaction of cathode scrap with formic acid is shown
Liquid Ratio (S/L). To study the effect of formic acid below in addition to eq 3.
1666 DOI: 10.1021/acs.est.6b03320
Environ. Sci. Technol. 2017, 51, 1662−1669
Environmental Science & Technology Article

6LiNi1/3Co1/3Mn1/3O2 (s) + 18HCOO−(aq) + 18H+(aq) (5) product transfer through the liquid film to the bulk
solution.
+ 3H 2O2 (aq) → 2C2H 2NiO4 (aq) + 2C2H 2CoO4 (aq) Leaching of metal values from the cathode scrap is a solid−
liquid−gas heterogeneous process, and it is a combination of
+ 2C2H 2MnO4 (aq) + 6CHLiO2 (aq) + 3O2 (g)
mass transfer, diffusion, and chemical reaction;42 thus, the
+ 12H 2O(aq) (4) leaching rate can be assumed to be controlled by liquid
boundary layer mass transfer (eq 5), surface chemical reaction
Under the conditions of 2 mol/L formic acid S/L of 50 g/L, (eq 6), or residue layer diffusion (eq 7)
temperature of 60 °C, and the addition of H2O2 from 2 to 12 X = k1·t (5)
vol %, the leaching rates of different elements from the cathode
scrap are shown in Figure 3. 1

The leaching rate of Al was not obviously affected by the 1 − (1 − X )3 = k 2·t (6)
concentration of H2O2 (Figure 3a), while the leaching rate of Li
2
increased significantly and reached almost 100% within 10 min 1 − 3(1 − X )3 + 2(1 − X ) = k 3·t (7)
(Figure 3b). Different from all of the other acid leaching
processes, the leaching rate of Ni, Co, and Mn under any where k1, k2, and k3 are the slopes of the fitted lines and t is the
hydrogen peroxide concentration increased rapidly within 10 reaction time (min). As shown in Figure S5, eq 6 (surface
min and then decreased steadily before reaching certain levels. chemical reaction control) exhibits the best fitting relevance
While hydrogen peroxide as a reductant helps to dissolve among the three rate controlling assumptions (the fitting data
manganese and cobalt in crystals of LiNi1/3Co1/3Mn1/3O2, the of eqs 5 and 7 are given in Figures S6 and S7 and Tables S2 and
dissolution of lithium and nickel are at the same time S3, respectively).
promoted.29 The best condition of H2O2 (concentration of Figure S8 as well as Table 1 gives the fitting lines by
30 wt %) was chosen to be 6 vol %. A comparison of the assuming chemical reaction control leaching. It can be found
recovered Al foil with formic acid leaching with and without that two distinctive stages exist for the leaching rate against
hydrogen peroxide is given in Figure S3, indicating clean Al foil temperature in the range of 30 to 80 °C. From 60 to 80 °C, the
can be obtained by adding H2O2. values for k2 (indicating the reaction rate constant) are nearly
3.1.3. Effect of Reaction Temperature. The effect of identical proving that the temperature has insignificant effect on
reaction temperature on leaching efficiencies of metals was the leaching process when the temperature is high enough. In
investigated under the following experimental condition: 2 the range of 30−60 °C, the data can be described by the
mol/L formic acid, 6 vol % of 30 wt % H2O2, S/L ratio of 50 g/ empirical Arrhenius law as
L, and the temperature range of 30−90 °C. As shown in Figure Ea
4, the leaching rate of Al is not effectively affected by k = Ae− RT (8)
temperature and there is only a slight increment of the leaching where R is the universal gas constant, A is the pre-exponential
at 90 °C. With the increase of temperature from 30 to 60 °C, factor, Ea is the apparent activation energy, and T(K) is the
the slope of leaching curves for all the metals are noticed to be absolute temperature. The equation can be further converted
increased suggesting the fact that the leaching process is an into
endothermic reaction process.29 The leaching behavior of Ni,
Co, and Mn was found to be very different from that of Li and Ea
ln k = ln A −
Al, where peak extraction rate in the leach solution can be RT (9)
noticed at the early stage of the leaching. Afterward, the
By plotting lnk vs 1/T in Figure 5, the apparent activation
leaching rates of Ni, Co, and Mn decrease significantly energy with H2O2 for Co, Mn, Ni, and Li can be obtained as
especially at high temperatures (60 to 80 °C), which can be 37.17, 39.38, 38.47, and 38.29 kJ/mol, respectively (Table S4).
attributed to the decomposition of hydrogen peroxide when the Similarly, the apparent activation energy without H2O2 addition
reaction temperature is higher than 60 °C41 (Figure 4). It can for Co, Mn, Ni, and Li (based on the data in Figure S9) was
also be noticed that the leaching rate is not significantly 41.52, 41.64, 41.16, and 43.61 kJ/mol, respectively (as shown in
improved after 60 °C by further increasing the leaching the Figures S10 and S11 and Tables S5 and S6).
temperature (detailed leaching rate against time at the early 3.3. Recovery of Lithium Carbonate. After formic acid
stage can be found in Table S1). leaching, the Al foil in the residue can be easily separated by
3.2. Apparent Mechanisms of Metal Recovery. To sieving (Figure S3). The mass fraction of each element in the Al
identify the apparent leaching mechanisms of the cathode scrap foil can be analyzed by ICP-OES and given in Table S7 where
using formic acid, kinetics analysis was carried out in the mass fraction of Al is found to be 99.98%.
accordance with the leaching behavior of different metals. The leach solution is processed according to aforementioned
During the decomposition of the cathode materials in formic procedures to precipitate out the remaining Ni, Co, and Mn.
acid solution, the binder (PTFE) and the acetylene black Subsequently, lithium carbonate can be obtained by adding
conductive agent remain to form a gray residue layer with loose excessive (110%) saturated Na 2CO3 to obtain lithium
and porous structure after the leaching reaction is completed. carbonate which is slightly soluble in water, and the solubility
As shown in Figure S4, the dissolution of a particle of the decreases with the increasing of temperature.43 The XRD
cathode material includes the following steps: (1) mass transfer pattern of the obtained lithium carbonate is shown in Figure 6a,
of reactive ions through liquid film, (2) diffusion from the and it agrees well with the standard pattern peaks.
residue−film interface to the reaction interface through the To accurately calculate the purity of lithium carbonate, the
residue layer, (3) chemical reaction at the residue−particle precipitated Li2CO3 was further dissolved by aqua regia and its
interface, (4) product diffusion through the residue layer, and mass fraction of metals was measured by ICP-OES (Table S8).
1667 DOI: 10.1021/acs.est.6b03320
Environ. Sci. Technol. 2017, 51, 1662−1669
Environmental Science & Technology Article

From Table S8, the mass fraction of lithium is accounted for Notes
99.90 wt %. The authors declare no competing financial interest.
The SEM images of the precipitated Li2CO3 are illustrated in
Figure 6b, and it can be noticed that the precipitated Li2CO3
was presented as massive agglomerates of numerous primary
■ ACKNOWLEDGMENTS
The authors acknowledge the financial support for this research
sheets. The particle size distribution (Figure 6c) is found to be from National Science−Technology Support Plan Projects
10.64 ± 1.47 μm. (2015BAB02B05), CAS Pioneer Hundred Talents Program
The mass fraction of Na+ among the metallic ions in the (Z.S.), and project Nos. 2016M591259 (China Postdoctoral
solution after precipitation is found to be 98.20%, where the Science Foundation for X. Zhang) and ZF1224 (Shanghai
anion through the entire leaching process is mainly HCOO−. Cooperative Centre for WEEE Recycling).
The solution can be further processed to prepare NaCOOH or
directly used for leather processing after pH adjustment,44 and
the Ni−Co−Mn precipitates are ready for precursor prepara-
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ASSOCIATED CONTENT
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Details about the leaching and kinetics analyses (PDF)
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■ AUTHOR INFORMATION
Corresponding Authors
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