Recovery of lithium, nickel and cobalt from spent lithium-ion. batteries powders by selective ammonia leaching and adsorption.

Transcription

1 Supporting Information for Recovery of lithium, nickel and cobalt from spent lithium-ion batteries powders by selective ammonia leaching and adsorption separation system Hongyan Wang 1,2#, Kai Huang 2#, Yang Zhang 1, Xin Chen 1, Wei Jin 1, Shili Zhe ng 1, Yi Zhang 1, Ping Li 1* 1 National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, , People s Republic of China 2 School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing , People s Republic of China * Corresponding author, lipinggnipil@ipe.ac.cn Tel: ; fax: Corresponding Author * Ping Li, phone: ; fax: lipinggnipil@ipe.ac.cn; Supporting Information: 27 pages, 15 Figures, and 5 Tables # These authors contributed equally to this study S1

2 EXPERIMENTAL Carbothermal reduction pretreatment and ammonia leaching The spent LIBs powders used in this study were provided by Henan Kelong New Energy Co., Ltd, China, and the composition of the powders was presented in Table S1. The pretreated spent LIBs powders were prepared by carbothermal reduction method as reported g spent LIBs powders thoroughly mixed with 5 g graphite in a ball mill for 1 h. Then, the mixtures, placed in a porcelain crucible, were calcined with argon atmosphere at 800 o C for 8 h using electronically controlled tube furnace. The calcination products were naturally cooled to room temperature prior to storing for selective leaching studies. Leaching experiments were carried out in a 500 ml beaker equipped with a magnetic stirrer and a sensor based temperature controller. In a typical procedure, 5 g pretreated powders, 250 ml ammonia-ammonium hydrocarbonate (NH 3 H 2 O: g/l, NH 4 HCO 3 : 140 g/l) solutions were loaded into the 500 ml beaker and kept at 60 o C for 8 h. 60 ml H 2 O 2 (30 wt%) used as reductant was added into the beaker continuously in the first 5 h. After leaching, the slurry was filtered and washed by 100 ml deionized water to obtain Li +, Ni 2+, Co 2+ and NH + 4 -containing leaching solutions, used for next adsorption separation step. Preparation of lithium ion-sieves Lithium ion-sieves as adsorbents were prepared by a high temperature calcination and acid treatment process which was reported elsewhere. 4-6 Typically, 18 g of C 4 H 6 MnO 4 4H 2 O and 2 g of Li 2 CO 3 were mixed in a mortar, followed by artificially grinding for 20 min; the mixture was put into a porcelain crucible, dried at 120 o C for 2 h and then calcined in a muffle furnace at 650 o C for 24 h. After calcination, 10 g cooled precursors was treated by 1 L HCl solutions (0.5 mol/l) for 24 h at stirring S2

3 conditions. At last, the lithium ion-sieves were obtained after filtering by funnel, washing with deionized water and drying at 100 o C for 12 h. Adsorption separation of lithium Adsorption experiments of Li +, Ni 2+ and Co 2+ ions were determined by the following procedure. A known amount of lithium ion-sieves and Co 2+ -Ni 2+ -Li + -NH + 4 -containing leaching solutions were placed in a 50 ml centrifuge tubes and the tubes were agitated in a shaking bath for a known time. After adsorption, the mixture was filtered and the filter cakes were washed several times with deionized water and dried at 100 o C for 12 h. The filter cakes were treated by 0.5 mol/l HCl solutions, and then were analyzed by ICP-OES to determine adsorption amounts of Ni 2+, Co 2+ and Li +. The experimental conditions varied with concentration of Li + ( g/l), amount of lithium ion-sieves ( g/l), initial NH + 4 concentration ( g/l) and the adsorption reaction temperature (20-50 o C). Product preparation and ammonia distillation The Li + -adsorbed lithium ion-sieves were treated by 0.5 mol/l HCl solutions to obtain Li + -containing solutions as well as small amounts of Ni 2+ and Co 2+. The Ni 2+ and Co 2+ in the solutions were further precipitated by adjusting ph with adding NaOH solution. After filtration, the filter cakes were recycled to selective ammonia leaching step, the purified Li + -containing solutions were further concentrated to produce Li 2 CO 3 by adding Na 2 CO 3 solution. 7,8 After lithium adsorption separation, the remanent Ni 2+ -Co 2+ -NH 4 + -containing leaching solutions was collected for ammonia distillation and preparation of NiSO 4 and CoSO 4 which resembled the reported process. 9,10 CHARACTERIZATION Phase of samples was determined by X-ray diffraction (XRD, APD-10X, Philips, Netherlands). The XRD analysis used CuKa radiation (k= Å) with a Rigaku S3

4 diffractometer at 40 kv and 40 ma. Composition distributions of samples were measured using mineral dissociation analyzer (FEI MLA 250). Morphologies of samples were characterized using a scanning electron microscope (JSM-7610F). Infrared spectrum was analyzed by Infrared Fourier Microscopy (T27-Hyperion-Vector22) with the range of cm -1 at a resolution of 4 cm -1. Specific surface area of precursors and lithium ion-sieves was analyzed by BET physical adsorption instrument (ASAP 2020HD88). The chemical concentrations were measured by inductively coupled plasma-optical emission spectroscopy (ICP-OES, PE Optima 7300 DV). Part 1.1 Langmuir model, Freundlich model and Temkin-Pyzhev models Langmuir model: Freundlich model: Pe 1 1 = pe+ (1) q q q K e m m L 1 log qe = log pe+ log KF (2) n Temkin-Pyzehv model: q = B1ln p + B1ln K (3) e e T Where q m donates the theoretical maximum amount of lithium adsorbed (mg/g); q e denotes the Li + equilibrium adsorption capacity (mg/g) by lithium ion-sieve at the equilibrium concentration p e (mg/l); K L represents the constant related to adsorption energy; n and K F represent the constants related to the lithium adsorption capacity, K T is the equilibrium binding constant (L/mol) corresponding to the maximum binding energy and constant B 1 is related to the heat of adsorption, respectively. Part 1.2 Pseudo-first-order model and Pseudo-second-order model k1 Pseudo-first-order model: lg( qe qt) = lg qe t (4) t 1 1 Pseudo-second-order model: = + t (5) 2 qt k 2qe qe Where k 1 and k 2 represent the constants of two models (g mg -1 min -1 ), respectively; q e represents the amount of Li +, Ni 2+ and Co 2+ adsorbed at equilibrium S4

5 (mg/g); q t represents the amount of Li +, Ni 2+ and Co 2+ adsorbed at any time (mg/g); t represents the adsorption time (min). Part 1.3 Clausius-Clapeyron equation The Clausius-Clapeyron equation: ln Ce= H / ( RT ) + ln K 0 (6) Where T is the adsorption temperature (K); K 0 is the constant (mg/l); R is the gas constant; C e is the equilibrium concentration of Li +, Ni 2+ and Co 2+. S5

6 Table S1 Main element compositions of the spent LIBs powders. Elements Ni Co Mn Li Al Cu Composition(wt.%) S6

7 Fig. S1. SEM-EDX analysis: (a) spent LIBs powders, (b) leaching residues. S7

8 Fig.S2. SEM image and EDS analysis of the spent LIBs powders before (a) and after carbothermal reduction pretreatment (b). S8

9 Fig.S3. SEM image and EDS analysis of precursor Li 1.27 Mn 1.73 O 4. S9

10 Fig. S4. (a) Infrared absorption spectra of precursors and lithium ion-sieves, (b) Pore size distribution profiles derived from BET method and nitrogen adsorption-desorption isotherms of precursors and lithium ion-sieves, (c) SEM images of precursors, (d) SEM images of lithium ion-sieves. S10

11 Table S2 Langmuir, Freundlich and Temkin-Pyzhev parameters for different ions Ions q m adsorption onto ion-sieves. Langmuir Freundlich Temkin-Pyzhev K L r 2 K F n r 2 B 1 K T r 2 Li Co Ni Li in Li + -Ni + -Co 2+ -conta ining solutions Co in Li + -Ni + -Co 2+ -conta ining solutions Ni in Li + -Ni + -Co 2+ -conta ining solutions S11

12 Fig.S5. (a) Adsorption of Li + onto lithium ion-sieves as a function of the Li + concentration in the Li + -Ni 2+ -Co 2+ -NH + 4 -containing leaching solutions (Ni 2+ and Co 2+ : 2 g/l, NH + 4 :150 g/l), (b) adsorption of Co 2+ onto lithium ion-sieves as a function of the Co 2+ concentration in the Li + -Ni 2+ -Co 2+ -NH + 4 -containing leaching solutions (Li + : 1 g/l, Ni 2+ : 2 g/l, NH + 4 :150 g/l), ) with 5 g/l of lithium ion-sieves at 30 o C for 6 h, (c) adsorption of Ni 2+ onto lithium ion-sieves as a function of the Ni 2+ concentration in the Li + -Ni 2+ -Co 2+ -NH 4 + -containing leaching solutions (Li + : 1 g/l, Co 2+ : 2 g/l, NH 4 + :150 g/l). S12

13 Fig.S6. Langmuir adsorption isotherm (a: Li +, b: Co 2+, c: Ni 2+ ), Freundlich adsorption isotherm (d: Li +, e: Co 2+, f: Ni 2+ )and Temkin-Pyzhev adsorption isotherm (g: Li +, h: Co 2+, i: Ni 2+ ) for Li +, Ni 2+, and Co 2+ ions adsorption onto lithium ion-sieves in the Li + -Ni 2+ -Co 2+ -NH + 4 -containing leaching solutions. S13

14 Fig.S7. Adsorption of Li + (a), Co 2+ (b) and Ni 2+ (c) ions onto lithium ion-sieves as a function of the concentration of single ion of Li +, Ni 2+ and Co 2+ in the NH + 4 -containing solutions (NH + 4 :150 g/l) with 5 g/l of lithium ion-sieves at 30 o C for 6 h. S14

15 Fig.S8. Langmuir adsorption isotherm (a: Li +, b: Co 2+, c: Ni 2+ ), Freundlich adsorption isotherm (d: Li +, e: Co 2+, f: Ni 2+ )and Temkin-Pyzhev adsorption isotherm (g: Li +, h: Co 2+, i: Ni 2+ ) for Li +, Ni 2+, and Co 2+ ions adsorption onto lithium ion-sieves in ammonia-containing solutions. S15

16 Fig. S9 Adsorption of Li +, Ni 2+ and Co 2+ ions onto lithium ion-sieve as a function of time. S16

17 Table S3 Adsorption rate constants obtained from the pseudo-first-order and pseudo-second-order kinetic models of Li + ions onto lithium ion-sieves. q e (exp.)/ Pseudo-first-order Pseudo-second-order (mg.g -1 ) k 1 /min -1 q e (theor.)/(mg.g 1 ) R 2 k 2 /(g mg -1 min -1 ) q e (theor.)/(mg.g 1 ) R S17

18 Fig.S10. Pseudo-first-order (a:li,b:ni,c:co) and pseudo-second-order (d:li,e:ni, f:co) kinetic plots for different ions adsorption. S18

19 Table S4 Adsorption thermodynamic parameters obtained from the Clausius-Clapeyron equation of Li +, Ni 2+ and Co 2+ ions onto ion-sieve Ion Fitting equation R 2 H/KJ.mol -1 Li lnc e =39.95/T Ni lnc e =0.98/T Co lnc e =0.71/T S19

20 Fig.S11. Relationship between lnc e and 1/T(a: Li,b:Ni,c:Co).. S20

21 Fig. S12. Concentration of Li +, Ni 2+ and Co 2+ in the HCl solution for different cycle. S21

22 Table S5 Impurity content in Li 2 CO 3. Element Na Mn Ni Co Content/% S22

23 Fig. S13. XRD patterns of the Li 2 CO 3. S23

24 Fig. S14. SEM-EDX analysis of Li 2 CO 3. S24

25 Fig. S15. XRD patterns of the Ni-Co-residues. S25

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