Recovery of Lithium, Nickel, and Cobalt from Spent Lithium-Ion Battery

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Recovery of lithium, nickel and cobalt from spent lithium-ion batteries powders by selective ammonia leaching and adsorption separation system Hongyan Wang, Kai Huang, Yang Zhang, Xin Chen, Wei Jin, Shili Zheng, Yi Zhang, and Ping Li ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b02700 • Publication Date (Web): 31 Oct 2017 Downloaded from http://pubs.acs.org on November 2, 2017

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ACS Sustainable Chemistry & Engineering

Recovery of lithium, nickel and cobalt from spent lithium-ion batteries powders by selective ammonia leaching and adsorption separation system Hongyan Wang1,2#, Kai Huang2#, Yang Zhang1, Xin Chen1, Wei Jin1, Shili Zhen g1, Yi Zhang1, Ping Li1* 1

National Engineering Laboratory for Hydrometallurgical Cleaner Production

Technology, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, 1 North 2nd Street, Zhongguancun, Haidian District, Beijing, 100190, People’s Republic of China 2

School of Metallurgical and Ecological Engineering, University of Science and

Technology Beijing, No.30 Xueyuan Road, Haidian District, Beijing 100083, People’s Republic of China *

Corresponding author, E-mail: [email protected]

Tel: +86-10-82544856; fax: +86-10-82544856 Hongyan Wang, Kai Huang, Yang Zhang, Xin Chen, Wei Jin, Shili Zheng, Yi Zhang, Ping Li

ABSTRACT A novel hydrometallurgical route was developed to recover valuable metals from spent LIBs powders. An ammonia media was utilized to selectively leach lithium, nickel and cobalt from the pretreated spent LIBs powders. Subsequently, an adsorption

method

was

adopted

to

effectively

separate

lithium

from

Co2+-Ni2+-Li+-NH4+-containing leaching solutions using manganese type lithium ion-sieves as adsorbents. The results showed that the direct recovery efficiencies of lithium, nickel and cobalt from the spent LIBs powders reached 76.19%, 96.23% and 94.57%, respectively. Besides, ammonia could be closed-loop recycled, while Li2CO3, NiSO4 and CoSO4 could be obtained as products. This study provides a new pathway for recycling utilization of spent LIBs powders. #

These authors contributed equally to this study 1

ACS Paragon Plus Environment


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KEYWORDS: Spent lithium-ion ternary batteries; Recovery; Ammonia leaching; Adsorption separation; Manganese type lithium ion-sieves

INTRODUCTION The ternary lithium ion batteries (LIBs) have become an indispensable part in electric vehicles taking advantages of their high voltage, light weight and long cycle lifetime.1-3 The fast-growing consumption generates large amount of spent LIBs owing to its short average service lifetime (1-3 years).4 In general, the main metals of spent LIBs powders (LiNixCoyMnzO2) include Li, Ni, Co, Al and Mn with the approximate contents of 5-7 wt.%, 5-10 wt.%, 5-20 wt.%, 1-3 wt.% and 10-15 wt.%, respectively, and the main residues are graphite and organics after dismantling, separating and grinding.5,6 Recovery of desired metals (Li, Ni and Co) from spent LIBs powders becomes an important issue from the viewpoint of resource conservation and hazard prevention of heavy metals pollution. The conventional technology for recovering Li, Ni and Co from the spent LIBs powders mainly involves pyrometallurgical process, hydrometallurgical process or the combination of both.7-9 The hydrometallurgical process is more positive in the reduction of hazardous gases emission and effective recovery of lithium.10 Generally, leaching agents of HCl11, HNO312, H2SO44,13, CO26 and various organic acids14-16 in the presence of H2O2 or NaHSO3, are adopted to leach Li, Ni, Co, Al and Mn from the spent LIBs powders. Then, the as-prepared Li+-Ni2+-Co2+-Al3+-Mn2+-containing leaching solutions employed the multistep chemical precipitation17-19 and solvent extraction20-23 to obtain the desired products. However, such indiscriminate leaching behavior and complex separation process caused high cost and potential heavy metal-containing hazard emission, weakening their application prospect. Selective leaching and effective separating process would be more suitable for recycling spent LIBs powders.24 Recently, ammonia leaching arouses much concern because of its selective leaching characteristics between the desired metals (Li, Ni, Co) and undesired metals (Al and Mn). In view of Eh-pH diagrams, ammonia leaching is thermodynamically feasible 2


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for transition metals such as Ni and Co which possessed high complexation ability with ammonia.25 On account of this principle, Sun et al. used ammonia-ammonium sulphate solutions to leach the pretreated spent LIBs powders in the presence of sodium sulphite.5 Kyungjung Kwon et al. investigated the leaching behavior of spent LIBs powders with ammonia, ammonium carbonate and ammonium sulfite as leaching agents, and proved that the ammonium sulfite acted as a reductant while the ammonium carbonate was a buffer solution.26 However, these methods still suffer from

the

difficulties

such

as

separation

of

valuable

metals

in

Co2+-Ni2+-Li+-NH4+-containing leaching solutions, ammonia media recycling and extra wastewater emission of sulfates produced from sulfites. In this study, a carbon reduction heating was firstly used to replace routine heating in the pretreatment of spent LIBs powders, not only eliminating the graphite and organics residues in the spent LIBs powders, but also transforming LiNixCoyMnzO2 into resources such as lithium (Li) or nickel (Ni) or cobalt (Co) compounds and evading the usage of sulfites as the reductants. Secondly, the pretreated spent LIBs powders were leached by ammonia-ammonium hydrocarbonate (NH3.H2O-NH4HCO3) solutions to form Co2+-Ni2+-Li+-NH4+-containing leaching solutions in the presence of hydrogen peroxide (H2O2) as the reductant. Thirdly, Li+ ions were preferentially separated by lithium ion-seives adsorption from the leaching solutions since adsorption has been widely investigated as a sustainable technique to separate lithium from lithium-containing solutions such as brines and sea water27-29. The NH4+ ions was further recycled into the leaching step by distillation of ammonia. After ammonia distillation, the Co2+-Ni2+-containing mixtures were collected for the following conventional solvent extraction separation method. The results showed that Ni, Co and Li of spent LIBs could be simultaneously leached by the NH3.H2ONH4HCO3-H2O2 solutions, and the leaching yields of Ni, Co and Li reached 96.4%, 96.3% and 81.2%, respectively, while the Al and Mn were hardly leached out. The prepared manganese type lithium ion-sieves can selectively adsorb Li from the Li+-Ni2+-Co2+-NH4+-containing leaching solutions, reaching the Li/Ni and Li/Co separation factors of about 212 and 983, respectively. At last, Li2CO3, NiSO4 and 3



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CoSO4 could be obtained as products. Thus, a novel integrated route were established to dispose the spent LIBs powders, realizing closed-loop recycling of leaching agents, selective leaching and effective separation of desired metals to obtain target products.

RESULTS AND DISCUSSION Carbothermal reduction pretreatment and selective ammonia leaching The spent LIBs powders were prepared by dismantling of spent LIBs to remove the plastic and steel cases, manual separating anodes and cathodes foils, and then grinding the cathodes foils which generally contained Al foils, pristine cathode materials (LiNi0.5Co0.2Mn0.3O2 powders), small amounts of graphite powders and organics residues. All the diffraction peaks of spent LIBs powders can be indexed to LiNi0.5Co0.2Mn0.3O2 as the major phase and aluminum (JCPDS-99-0005) as the minor phase (Fig. 1b), similar to the previous studies4,17. Cu and large amounts of graphite were removed in the dismantling step, compared to the pristine materials (Fig. 1a) which were obtained by directly crushing anodes and cathodes foils. SEM-EDX analysis was further used to characterize the spent LIBs powders. As shown in Fig. S1(a) and S2(a), surface morphology appeared to be agglomerated particles with 5-15 μm size, Ni, Co and Mn were evenly distributed in the particles, and their chemical contents were 18.71, 7.02 and 10.06 wt%, respectively. Differently, Al was randomly distributed in the observed area with the content of 1.36 wt%, related to dismantling and separating process of spent LIBs. Lithium content, which was separately determined by ICP-OES, was 5.52%. After carbothermal reduction heating pretreatment of spent LIBs powders, the LiNi0.5Co0.2Mn0.3O2 was found to transform to Ni and Co as major phases and MnO and Li2CO3 as minor phases (Fig. 1c). Morphology of particles, distribution and contents of Li, Ni, Co and Mn changed little (Fig. S1(b)). Ammonia leaching tests were carried out to determine the leaching efficiency. ICP-OES results showed that Li, Ni and Co could be leached out by the NH3H2O-NH4HCO3 solutions (NH3H2O: 367.5 g/L, NH4HCO3: 140 g/L) in the presence of H2O2 (63.24 g/L) with the yields of 81.2%, 96.4% and 96.3%, 4


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respectively, while Mn and Al were practically insoluble. Only 0.96% Ni, 0.40% Co and 2.82% Li existed in the residues, under the experimental conditions. SEM-EDX (Fig. S2(b)) results also verified that little Ni and Co could be found in the residues particles. Thermodynamically, the Ni and Co had stronger complexation ability with ammonia than Mn and Al.30,31 Expect for the ammonia complexation effect, the addition of H2O2 is believed to oxidize the Ni and Co metals to Ni2+ and Co2+ ions, facilitating the Ni2+ and Co2+ -ammine complexes formation, respectively. On the other hand, synergistic effect between NH3 and HCO3- can also selectively inhibit the leaching of Mn and Al. Specifically, the Mn2+, which was originated from MnO, was firstly dissolved into NH3H2O solutions to form Mn2+-ammine complexes, and then precipitated in the form of manganese carbonate (MnCO3) due to its lower solubility than manganese hydroxide (MnOH), which was further confirmed by XRD patterns of leaching residues (Fig. 1d) and previous study.32 After selective ammonia leaching, the obtained Li+-Ni2+-Co2+-NH4+-containing leaching solutions, which contain 1.04 g/L of Li+, 5.66 g/L of Ni2+, 1.91 g/L of Co2+ and 120 g/L of NH4+ ions, will be used for the following adsorption separation step.

Characteristics of lithium ion-sieves adsorbents Manganese type lithium ion-sieves were synthesized to selectively adsorb Li+ ions from the Li+-Ni2+-Co2+-NH4+-containing leaching solutions. As observed, all peaks of the precursors (Fig. 2a) were very sharp and matched with the peaks of the standard Li1.27Mn1.73O4 (JCPDS 51-1582) very well.33 Peaks of the lithium ion-sieves (Fig. 2b) were in correspondence with that of precursors, showing that such structure was stable during the process of acid treatment. Mn and O contents of precursors were measured by EDX (Fig. S3), and the mass ratio of Mn to O was 1.04, close to the theoretical mass ratio of Mn to O of Li1.27Mn1.73O4 (1.06). The FT-IR spectra of both precursors and lithium ion-sieves (Fig. S4(a)) exhibited two distinct bands at 1631 and 3400 cm-1, which could be attributed to the bending modes of water molecule and stretching modes of OH-, respectively.34 Two bands which were located at approximately 520 cm-1 and 630 cm-1 were assigned to the asymmetric stretching 5



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modes of MnO6 group.35 Different from the precursors, band at 900 cm-1, which was observed in the FT-IR spectrum of lithium ion-sieves, could be ascribed to proton coupling vibration peak,36 demonstrating that the Li+ in the precursors was exchanged with H+ during the acid treatment. SEM images of both precursors and lithium ion-sieves (Fig. S4(c) and Fig. S4(d)) indicated that the particles were agglomerated and the average diameter of the particles was in the range of 5-20 μm. The textures of precursors

and

lithium

ion-sieves

which

were

deduced

from

nitrogen

adsorption-desorption isotherms and pore size distribution (Fig. S4(b)) showed their specific surface area and average pore diameters resembled the previous reported results.37

Adsorption separation of lithium To effectively separate Li+ ions, we conducted various experiments to investigate the

adsorption

behaviors

of

lithium

ion-sieves

from

the

Li+-Ni2+-Co2+-NH4+-containing leaching solutions. The effect of Li+ ions concentration were carried out by changing the initial concentration of Li+ ions from 0.5 g/L to 2.5 g/L at constant concentration of Ni2+ (2 g/L), Co2+ (2 g/L) and NH4+ (150 g/L) at 30 oC for 6 h, considering the variation range of lithium concentration in the different leaching conditions. It could be found from Fig. 3(a) that the adsorption capacity of Li+ increased from 25.27 mg/g to 30.40 mg/g with the increase of initial concentration of Li+ from 0.5 g/L to 2.5 g/L, while the adsorption capacities of Ni2+ and Co2+ decreased from 0.76 mg/g to 0.23 mg/g and from 0.41 mg/g to 0.060 mg/g, respectively. Higher Li+ ions concentration accelerates the attainment of Li+/H+ ion-exchange equilibrium, the Li+ ions can easily get into the active sites of lithium ion-sieves leading to the increase of adsorption capacity of Li+. Meanwhile, the active sites and space are occupied by Li+ ions resulting in less space and active sites for Co2+ and Ni2+.38 Figure 3(b) showed the effect of lithium ion-sieves amounts on the adsorption capacities of Li+, Ni2+ and Co2+ under the constant concentrations of Li+-Ni2+-Co2+-NH4+-containing leaching solutions (Li+: 1 g/L, Ni2+ and Co2+: 2 g/L, and NH4+: 150 g/L) at 30 oC for 6 h, and the results showed 6


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that Li+ uptake amount decreased from 28.00 mg/g to 25.37 mg/g and adsorption capacity of Ni2+ and Co2+ changed little with the increase of amounts of lithium ion-sieves increased from 2.5 g/L to 12.5 g/L. Most of the Li+ ions in the leaching solutions had been adsorbed onto the lithium ion-sieves with the suitable amounts, and the remanent Li+ ions could no longer be removed despite the growth of unoccupied active adsorption sites number, resulting in the decrease of adsorption capacities of lithium ion-sieves.39 Lithium ion-sieves had a much higher affinity for Li+ ions than Ni2+ and Co2+, which was confirmed by the constant (KL) related to adsorption energy calculated from the following Langmuir model. The concentration of NH4+ ions from 75 g/L (pH 9.35) to 200 g/L (pH 10.89) was further changed under the constant concentrations of Li+, Ni2+ and Co2+ (Li+: 1 g/L, Ni2+ and Co2+: 2 g/L) at 30 oC for 6 h. As shown in Fig. 3(c), the Li+ adsorption capacity increased from 22.70 mg/g to 26.10 mg/g while the adsorption amount of Ni2+ decreased from 0.14 mg/g to 0.060 mg/g and the adsorption amount of Co2+ decreased from 0.030 mg/g to 0.013 mg/g, with the increase of NH4+ concentration from 75 g/L to 200 g/L. These results are closely related to higher complexation ability between NH3 and Ni2+ and Co2+ and the increased pH values. At the higher pH, lithium ion-sieves possessed the lower surface charge which brought the stronger electrostatic interactions between the Li+ and H+.40 The temperature variations results (Fig. 3(d)) also showed that the adsorption capacities of Li+, Ni2+ and Co2+ increased when the temperature increased from 20 oC to 50 oC at the constant concentrations of Li+, Ni2+ and Co2+ (Li+: 1 g/L, Ni2+ and Co2+: 2 g/L, NH4+ :150 g/L) in the leaching solutions for 6 h, similar to the previous reported results.41,42 To evaluate the adsorption behaviors of Li+ , Ni2+ and Co2+ ions onto lithium ion-sieves, Li+, Ni2+ and Co2+ ions adsorption isotherms were determined by separately altering the concentration of Li+, Ni2+ and Co2+ ions from 0.5 g/L to 2.5 g/L, 0.5 g/L to 2.0 g/L and 0.5 g/L to 2.5 g/L, respectively, under the constant NH4+ concentrations in the NH4+-containing aqueous solutions (NH4+:150 g/L) with 5 g/L of lithium ion-sieves at 30 oC for 6 h. The obtained adsorption data were simulated by 7



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Langmuir model, the Freundlich model and Temkin-Pyzhev model,43-45 as shown in the supporting information (Part 1.1). As observed, the coefficient values (Table S2 and Fig. S5-S8) suggested that the Langmuir model well described the adsorption equilibrium of Li+ , Ni2+ and Co2+ ions, indicating that the adsorption of Li+, Ni2+ and Co2+ ions in the NH4+-containing aqueous solutions belonged to dominantly monolayer adsorption.46 The maximum adsorption capacity (qm) for Li+, Ni2+ and Co2+

ions

were

38.82,

0.862

and

0.685

mg/g,

respectively.

In

the

Li+-Ni2+-Co2+-NH4+-containing leaching solutions (Li+: 1 g/L, Ni2+ and Co2+: 2 g/L, NH4+:150 g/L), the generated curves of Li+ ions confirmed that the Langmuir model still fit the experimental data well, while the curves of Ni2+ and Co2+ ions were fit the Langmuir model and Temkin-Pyzhev model moderately. The magnitude of adsorption heats (B1) results (Table S2) demonstrated that the strong affinity of the lithium ion-sieves for Li+ (B1=2.81) and the weak affinity of the lithium ion-sieves for Ni2+ (B1=0.051) and Co2+ (B1=0.159), indicating the high selectivity for Li+ ions. The maximum adsorption capacity (qm) for Li+, Ni2+ and Co2+ ions decreased to 31.63, 0.74 and 0.221 mg/g, respectively. The phenomenon of the decreased Li+ adsorption capacity may be attributed to the active adsorption sites on the lithium ion-sieves occupied by Ni2+ and Co2+ due to their competitive affinity.47 To determine the efficiency of Li+ ions adsorption onto lithium ion-sieves, the kinetics of adsorption was investigated by performing adsorption experiments onto lithium ion-sieves under the constant concentrations of Li+, Ni2+ and Co2+ (Li+: 1 g/L, Ni2+ and Co2+: 2 g/L) at 20 oC with different equilibration times. Both the pseudo-first-order model and pseudo-second-order kinetic model48-50 as shown in the supporting information (Part 1.2) were used to fit the experimental data (Fig. S9). The results suggested that pseudo-second-order kinetic model better fit to the adsorption data and was more suitable to describe the adsorption kinetics of Li+ ions by evaluating the determination coefficients (R2＞0.99, Figure S10, Table S3). This indicated that the Li+ ions adsorption onto lithium ion-sieves was a chemisorption process. Besides, the adsorption kinetics of Ni2+ and Co2+ showed the pseudo-second-order kinetic model also better fit to the adsorption data. However, the 8


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initial adsorption rates of Ni2+ ( 2.284 mg·g-1·min-1) and Co2+ ( 116.114 mg·g-1·min-1) were higher than that of Li+ ( 0.12 mg·g-1·min-1), indicating that Ni2+ and Co2+ ions adsorption onto lithium ion-sieves might be a physical adsorption in the competitive adsorption of Li+, Ni2+ and Co2+, which was similar with competitive adsorption of V(V) and Cr(VI).51,52 Thermodynamic parameter were further determined by Clausius-Clapeyron equation as shown in supporting information (Part 1.3), and the results (Table S4 and Figure S11) showed that the ΔHo of Li+, Ni2+ and Co2+ ions adsorbed were 0.332, 0.00815 and 0.0059 KJ∙mol-1, respectively, indicating that the Li+, Ni2+ and Co2+ adsorption onto lithium ion-sieves were all endothermic. Equilibrium distribution coefficients (Kd) and selectivity coefficients (αLiMe) were adopted to investigate the selective adsorption of Li+ ions since the Kd represented the adsorption affinity of ions for the lithium ion-sieves and the αLiMe was one of the important considerations for realizing the ions selectivity. The Kd and α could be estimated from the following equation:

Kd 

(C 0  Ce)V MCe

(1)

αLiMe 

KdLi KdMe

(2)

Where C0 represents the initial concentration of Li+, Ni2+ and Co2+; Ce the equilibrium concentration of Li+, Ni2+ and Co2+; V represents the volume of leaching solutions; M represents the amounts of lithium ion-sieves. Table 1 shows equilibrium adsorption capacity, Kd and αLiMe of Li+, Ni2+ and Co2+ in the Li+-Ni2+-Co2+-NH4+-containing leaching solutions (Li+: 1 g/L, Ni2+ and Co2+: 2 g/L). At the 150 g/L of NH4+, the adsorption affinity of Li+, Ni2+ and Co2+ onto lithium ion-sieves were 32.665, 0.154, and 0.0332, respectively. The Kd order of Li+＞Ni2+＞ Co2+ indicated high selectivity for Li+. More importantly, the selectivity coefficients α LiNi and α LiCo reached 212.11 and 983.89, respectively. Such excellent selectivity between Li+, Ni2+ and Co2+ could be explained by “ion memory” effect of lithium ionsieves and larger ionic radii of Ni2+ and Co2+ which hindered them access to 9



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adsorption sites.53 Selective adsorption separation and adsorbents regeneration Based on the findings above, we performed selective adsorption experiments from the actual Li+-Ni2+-Co2+-NH4+-containing leaching solutions (Li+: 1.039 g/L , Ni2+ : 5.762 g/L, Co2+: 1.948 g/L, NH4+: 120 g/L) under the optimized leaching conditions to evaluate the separation effect of Li. In the measurement, the selective adsorption experiment was carried out in 250 ml polytetrafluoroethylene bottles containing 100 ml of leaching solutions mixed with 8 g lithium ion-sieves to form suspensions. The suspensions samples were shaken in a thermostatic water bath vibrator with a speed of 150 rpm at 30 oC for 24 h to complete adsorption without pH adjustment, and then filtered through 0.22 µm filters. It was found that above 99.9% Li+ ions were adsorbed while only 0.17% Ni2+ and 1.79% Co2+ were adsorbed onto the lithium ion-sieves. After adsorption, the Li+-adsorbed leaching solutions contained only 0.18 mg/L Li+ ions, 5.662 g/L Ni2+ and 1.913 g/L Co2+, indicating that the Li+ ion could be effectively separated by lithium ion-sieves from the leaching solutions. Li+ -adsorbed lithium ion-sieves are amenable to efficient reusability by HCl solution. Reusability of the lithium ion-sieves was determined through several adsorptions-desorption cycles. The adsorption cycle experiments were the same as the above-mentioned adsorption procedure. After each cycle, 10 g lithium ion-sieves were regenerated by washing with 1 L HCl solution (0.5 mol/L) at room temperature for 24 h, and washed by distilled water and then centrifuged to remove the residual ions. The HCl solution was used for next desorption step to concentrate Li+ ions and other impurities. Five adsorption-desorption cycles results (Figure 4) showed that the Li+ adsorption capacity were kept in the range of 25～28 mg/g while Ni2+ and Co2+ adsorption capacity was kept in the range of 1.0～1.5 mg/g and 0.3～0.5 mg/g with the desorption yields of Li+, Ni2+ and Co2+ of 92.36%-95.60%, 66.20%-75.5% and 11.33%-13.95%,

respectively.

After

the

five

adsorption-desorption

cycles,

concentrations of Li+, Ni2+ and Co2+ in the HCl solution (Figure S12) increased to 0.883 g/L, 10 mg/L and 0.72 mg/L, respectively. 10


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Recovery process At last, we proposed a novel hydrometallurgical flow sheet of the recovery of Li, Ni and Co from the spent LIBs powders as presented in Fig. 5. During the selective ammonia leaching, 81.2% Li, 96.4% Ni and 96.3% Co can be leached out and diluted to a desired concentrations (1~10 g/L) without Mn and Al. After solid-liquid separation, the diluted Li+-Ni2+-Co2+-NH4+-containing leaching solutions was disposed with the lithium ion-sieves to selectively separate Li+ ions, and the lithium separation efficiency reached 99.9%. The Li+-adsorbed lithium ion-sieves were separated and desorbed by HCl solution for regeneration. The desorption solutions were then neutralized by NaOH and carbonized by Na2CO3 to obtain Li2CO3 product with more than 99.5% purity (Fig. S13, S14 and Table S5). On the other hand, the Ni2+-Co2+-NH4+-containing leaching solutions was distilled to realize closed-loop recycling of ammonia and the remanets were mixtures of NiCO3 and CoCO3 or their hydrates (Fig. S15). Under the experiment conditions, the mixtures, which contained 11.34% Co and 25.1% Ni without Mn, Al and Li, could be easily dissolved by H2SO4 and extracted by P507, cyanex 272, etc. to obtain NiSO4 and CoSO4 products.54,55 Overall, the whole process realized effective recovery of Li, Ni and Co from the spent LIBs powders with the direct recovery efficiencies of 76.19%, 96.23% and 94.57%, respectively, and closed-loop recycling of ammonia.

CONCLUSIONS A novel hydrometallurgical method was developed for recovering Li, Ni and Co from spent LIBs powders. 81.2% Li, 96.4% Ni and 96.3% Co were selectively leached from the pretreated spent LIBs powders by NH3H2O-NH4HCO3 solutions in the presence of H2O2. And then the 99.9% lithium was efficiently separated from leaching solutions using manganese type lithium ion-sieves. The maximum amount of lithium adsorbed was 31.62 mg/g, and the selectivity coefficients of Li+ to Ni2+ and Li+ to Co2+ reached 212.11 and 983.89, respectively. Furthermore, Li2CO3, NiSO4 and CoSO4 could be obtained as products and ammonia could be closed-loop recycled. 11



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This sustainable process for recovering high valued metals from the spent LIBs will enable conservation and recycling of resources. ASSOCIATED CONTENT Supporting Information Additional experiments and results as discussed in the text and shown in EXPERIMENTAL, CHARACTERIZATION, Part 1.1, Part 1.2, Part 1.3, Fig. S1-S15 and Table S1-S5.

Author information Corresponding Author *

E-mail: [email protected];

Tel: +86-10-82544856

Notes The authors declare no competing ﬁnancial interest.

Acknowledgments This work was supported by the National Nature Science Foundation of China (No.51574212, U1403195).

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Fig.1. XRD patterns of the pristine materials (a), the LIBs powders (b), carbothermal reduction heating pretreatment powders (c) and leaching residues (d).

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Fig. 2. XRD patterns of precursors (a) and lithium ion-sieves before (b) and after lithium adsorption (c).

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Fig. 3. Adsorption of Li+, Ni2+ and Co2+ ions onto lithium ion-sieves as a function of initial Li+ ions concentration (a), the amounts of lithium ion-sieves (b), initial pH (c) and temperature (d).

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Table 1

Comparison of cations uptake from Li+-Ni2+-Co2+-NH4+-containing leaching solutions by lithium ion-sieves.

Ion

C0/(g.L-1)

Ce/(g.L-1)

qe/(mg.g-1)

Kd/(mL.g-1)

αLiMe

Li

0.993

0.7485

24.45

32.665

1

Ni

2.077

2.0738

0.317

0.154

212.11

Co

2.111

2.1103

0.070

0.0332

983.89

21



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Table 2 The concentration variations of Li+, Ni2+ and Co2+ before and after adsorption in the Li+-Ni2+-Co2+-NH4+-containing leaching solutions. Ions

Concentration before

Concentration after

Adsorption

adsorption/mg L-1

adsorption/mg L-1

efficiency

Li+

1039

0.18

99.9%

Ni2+

5762

5662

0.17%

Co2+

1948

1913

1.79%

22


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Fig. 4. Cycle performance of lithium ion-sieves in actual Li+-Ni2+-Co2+-NH4+-containing leaching solutions.

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Fig. 5. Flow sheet of the recovery of Li, Ni and Co from the spent LIBs powders.

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For Table of Contents Use Only

Synopsis An ammonia leaching and adsorption separation process for recovering valued metals from spent LIBs realizes the sustainable utilization of resource

25


Recovery of Lithium, Nickel, and Cobalt from Spent Lithium-Ion Battery

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