退役锂离子电池电化学还原浸出及热力学研究

doi:10.19964/j.issn.1000-4990.2022-0389

Abstract

Abstract:

In recent years，the rapid increase of lithium-ion batteries（LIBs） demand has produced an enormous amount of spent LIBs.The recovery of spent LIBs is of great significance to securing clean energy in China.Electrochemical leaching of spent LIBs cathode materials is a green and economical method.At present，the recycling of spent LIBs with electrochemical methods are suffered from long leaching time，low current efficiency，and high cell voltage.Based on this，an electrochemical reduction for recycling of spent LIBs by sacrificing anodes was proposed.In the diluted hydrochloric acid solution，electrochemical leaching experiments were carried out with spent LIBs cathode materials as the cathodes and copper plates as the anodes.The leaching efficiencies were 99.9% for Li⁺ and Co²⁺，the current efficiency was up to 99.8%，and the cell voltage was less than 0.427 V under optimum conditions.The thermodynamic calculation methods based on Eh-pH and Matlab were utilized to study the electrochemical reduction leaching process，and the results showed that higher temperature，more complex species and more coordination species contributed to the positive shift of leaching reaction balance.

Key words: spent lithium-ion batteries, electrochemical recycling, thermodynamics, cell voltage

CLC Number:

TQ131.11

HE Ting,KONG Jiao,CUI Jingzhi,CHEN Zhihao,FU Tongtong,GUO Zirui,GU Shuai,YU Jianguo. Study on leaching and thermodynamic of spent lithium-ion batteries with electrochemical reduction[J]. Inorganic Chemicals Industry, 2022, 54(12): 34-43.

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References 50

1	WANG Yuqing, AN Ning, WEN Lei, et al. Recent progress on the recycling technology of Li-ion batteries[J]. Journal of Energy Chemistry, 2021, 55: 391-419.
2	CHANG Xin, FAN Min, GU Chaofan, et al. Selective extraction of transition metals from spent LiNi _x Co _y Mn_1- _x_- _y O₂ cathode via regulation of coordination environment[J]. Angewandte Chemie, 2022, 134(24).Doi：10.1002/ange.202202558 . doi: 10.1002/ange.202202558
3	ZHAO Yunze, LIU Bingguo, ZHANG Libo, et al. Microwave pyrolysis of macadamia shells for efficiently recycling lithium from spent lithium-ion batteries[J]. Journal of Hazardous Materials, 2020, 396.Doi：10.1016/j.jhazmat.2020.122740 . doi: 10.1016/j.jhazmat.2020.122740
4	XIAO Hougui, JI Guanjun, YE Long, et al. Efficient regeneration and reutilization of degraded graphite as advanced anode for lithi-um-ion batteries[J]. Journal of Alloys and Compounds, 2021, 888.Doi：10.1016/j.jallcom.2021.161593 . doi: 10.1016/j.jallcom.2021.161593
5	LI Jun, LAI Yiming, ZHU Xianqing, et al. Pyrolysis kinetics and reaction mechanism of the electrode materials during the spent LiCoO₂ batteries recovery process[J]. Journal of Hazardous Materials, 2020, 398.Doi：10.1016/j.jhazmat.2020.122955 . doi: 10.1016/j.jhazmat.2020.122955
6	FAN Ersha, LI Li, WANG Zhenpo, et al. Sustainable recycling technology for Li-ion batteries and beyond：Challenges and future prospects[J]. Chemical Reviews, 2020, 120(14)：7020-7063.
7	CHEN Dongdong, RAO Shuai, WANG Dongxing, et al. Synergistic leaching of valuable metals from spent Li-ion batteries using sulfuric acid-l-ascorbic acid system[J]. Chemical Engineering Journal, 2020, 388.Doi：10.1016/j.cej.2020.124321 . doi: 10.1016/j.cej.2020.124321
8	钟雪虎, 陈玲玲, 韩俊伟, 等. 废旧锂离子电池资源现状及回收利用[J]. 工程科学学报, 2021, 43(2)：161-169.
	ZHONG Xuehu, CHEN Lingling, HAN Junwei, et al. Overview of present situation and technologies for the recovery of spent lithium-ion batteries[J]. Chinese Journal of Engineering, 2021, 43(2)：161-169.
9	XIAO Jiefeng, NIU Bo, SONG Qingming, et al. Novel targetedly extracting lithium：An environmental-friendly controlled chlorinating technology and mechanism of spent lithium ion batteries reco-very[J]. Journal of Hazardous Materials, 2021, 404.Doi：10.1016/j.jhazmat.2020123947 . doi: 10.1016/j.jhazmat.2020123947
10	XIAO Jiefeng, GAO Ruitong, NIU Bo, et al. Study of reaction characteristics and controlling mechanism of chlorinating conversion of cathode materials from spent lithium-ion batteries[J]. Journal of Hazardous Materials, 2021, 407.Doi：10.1016/j.jhazmat.2020.124704 . doi: 10.1016/j.jhazmat.2020.124704
11	XIAO Jiefeng, NIU Bo, XU Zhenming. Highly efficient selective recovery of lithium from spent lithium-ion batteries by thermal reduction with cheap ammonia reagent[J]. Journal of Hazardous Materials, 2021, 418.Doi：10.1016/j.jhazmat.2021.126319 . doi: 10.1016/j.jhazmat.2021.126319
12	HU Xianfeng, MOUSA E, TIAN Yang, et al. Recovery of Co，Ni，Mn，and Li from Li-ion batteries by smelting reduction-Part I：A laboratory-scale study[J]. Journal of Power Sources, 2021, 483.Doi：10.1016/j.jpowsour.2020.228936 . doi: 10.1016/j.jpowsour.2020.228936
13	HU Xianfeng, MOUSA E, YE Guozhu. Recovery of Co，Ni，Mn，and Li from Li-ion batteries by smelting reduction-Part Ⅱ：A pilot-scale demonstration[J]. Journal of Power Sources, 2021, 483.Doi：10.1016/j.jpowsour.2020.229089 . doi: 10.1016/j.jpowsour.2020.229089
14	TANG Yiqi, QU Xin, ZHANG Beilei, et al. Recycling of spent lithium nickel cobalt manganese oxides via a low-temperature ammonium sulfation roasting approach[J]. Journal of Cleaner Production, 2021, 279.Doi：10.1016/j.jclepro.2020.123633 . doi: 10.1016/j.jclepro.2020.123633
15	HOREH N B, MOUSAVI S M, SHOJAOSADATI S A. Bioleaching of valuable metals from spent lithium-ion mobile phone batteries using Aspergillus Niger[J]. Journal of Power Sources, 2016, 320: 257-266.
16	JEGAN ROY J, SRINIVASAN M, CAO Bin. Bioleaching as an eco-friendly approach for metal recovery from spent NMC-based lithium-ion batteries at a high pulp density[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(8)：3060-3069.
17	XING Lei, BAO Jieru, ZHOU Shiyu, et al. Ultra-fast leaching of critical metals from spent lithium-ion batteries cathode materials achieved by the synergy-coordination mechanism[J]. Chemi-cal Engineering Journal, 2021, 420.Doi：10.1016/j.cej.2021.129593 . doi: 10.1016/j.cej.2021.129593
18	LI Li, ZHAI Longyu, ZHANG Xiaoxiao, et al. Recovery of valuable metals from spent lithium-ion batteries by ultrasonic-assisted leaching process[J]. Journal of Power Sources, 2014, 262: 380-385.
19	GU Shuai, KONG Jiao, XING Lei, et al. Insights into the coordination enhanced leaching mechanism of spent lithium-ion batteries cathode materials[J]. Journal of Environmental Chemical Engineering, 2022, 10(3).Doi：10.1016/j.jece.2022.107745 . doi: 10.1016/j.jece.2022.107745
20	LI Shuzhen, WU Xin, JIANG Youzhou, et al. Novel electrochemically driven and internal circulation process for valuable metals recycling from spent lithium-ion batteries[J]. Waste Management, 2021, 136: 18-27.
21	JANG Y, HOU C H, PARK S, et al. Direct electrochemical lithium recovery from acidic lithium-ion battery leachate using intercalation electrodes[J]. Resources，Conservation and Recycling, 2021, 175.Doi：10.1016/j.resconrec.2021.105837 . doi: 10.1016/j.resconrec.2021.105837
22	赵鹏飞, 尹晓莹, 满瑞林. 电解法在废旧锂电池浸出过程中的应用[J]. 中国有色冶金, 2014, 43(5)：73-78.
	ZHAO Pengfei, YIN Xiaoying, MAN Ruilin. Application of electrolytic method in spent Li-ion battery leaching process[J]. China Nonferrous Metallurgy, 2014, 43(5)：73-78.
23	MENG Qi, ZHANG Yingjie, DONG Peng. Use of electrochemical cathode-reduction method for leaching of cobalt from spent lithi-um-ion batteries[J]. Journal of Cleaner Production, 2018, 180: 64-70.
24	ZHOU Siyuan, ZHANG Yingjie, MENG Qi, et al. Recycling of spent LiCoO₂ materials by electrolytic leaching of cathode electrode plate[J]. Journal of Environmental Chemical Engineering, 2021, 9(1).Doi：10.1016/j.jece.2020.104789 . doi: 10.1016/j.jece.2020.104789
25	DANG Sen, HOU Wei, MIN Yulin, et al. Electro-oxidation：A win-win strategy for the selective recovery of Li⁺ from spent lithium-ion batteries and the preparation of highly active catalysts[J]. Chemical Engineering Journal, 2022, 435.Doi：10.1016/j.cej.2022.135169 . doi: 10.1016/j.cej.2022.135169
26	LV Hong, HUANG Haijian, HUANG Cheng, et al. Electric field driven de-lithiation：A strategy towards comprehensive and efficient recycling of electrode materials from spent lithium ion batteries[J]. Applied Catalysis B：Environmental, 2021, 283.Doi：10.1016/j.apcatb.2020.119634 . doi: 10.1016/j.apcatb.2020.119634
27	LIU Kui, YANG Shenglong, LAI Feiyan, et al. Innovative electrochemical strategy to recovery of cathode and efficient lithium leaching from spent lithium-ion batteries[J]. ACS Applied Energy Materials, 2020, 3(5)：4767-4776.
28	ZHANG Beilei, QU Xin, QU Jiakang, et al. A paired electrolysis approach for recycling spent lithium iron phosphate batteries in an undivided molten salt cell[J]. Green Chemistry, 2020, 22(24)：8633-8641.
29	HUA Yunhui, XU Zhenghe, ZHAO Baojun, et al. Electric potential-determined redox intermediates for effective recycling of spent lithium-ion batteries[J]. Green Chemistry, 2022, 24(9)：3723-3735.
30	LV Weiguang, RUAN Dingshan, ZHENG Xiaohong, et al. One-step recovery of valuable metals from spent lithium-ion batteries and synthesis of persulfate through paired electrolysis[J]. Chemical Engineering Journal, 2021, 421.Doi：10.1016/j.cej.2021.129908 . doi: 10.1016/j.cej.2021.129908
31	MIGDISOV A A, ZEZIN D, WILLIAMS-JONES A E. An experimental study of Cobalt（Ⅱ） complexation in Cl^- and H₂S-bearing hydrothermal solutions[J]. Geochimica et Cosmochimica Acta, 2011, 75(14)：4065-4079.
32	PAN Pujing, SUSAK N J. Co（Ⅱ）-chloride and-bromide complexes in aqueous solutions up to 5 m NaX and 90 ℃：Spectrophotometric study and geological implications[J]. Geochimica et Cosmochimica Acta, 1989, 53(2)：327-341.
33	LIU Weihua, BORG S J, TESTEMALE D, et al. Speciation and thermodynamic properties for cobalt chloride complexes in hydrothermal fluids at 35~440 ℃ and 600 bar：An in situ XAS study[J]. Geochimica et Cosmochimica Acta, 2011, 75(5)：1227-1248.
34	HUANG T C, TSAI T H. Extraction equilibrium of cobalt（Ⅱ） from sulphate solutions by di（2-etrylhexyl）phosphoric acid dissolved in kerosene[J]. Polyhedron, 1990, 9(9)：1147-1153.
35	GU Shuai, ZHANG Liang, FU Bitian, et al. Recycling of mixed lithium-ion battery cathode materials with spent lead-acid battery electrolyte with the assistance of thermodynamic simulations[J]. Journal of Cleaner Production, 2020, 266.Doi：10.1016/j.jclepro.2020.121827 . doi: 10.1016/j.jclepro.2020.121827
36	WANG Mengmeng, ZHANG Congcong, ZHANG Fushen. An environmental benign process for cobalt and lithium recovery from spent lithium-ion batteries by mechanochemical approach[J]. Waste Management, 2016, 51: 239-244.
37	赵中伟, 霍广生. Li-Mn-H₂O系热力学分析[J]. 中国有色金属学报, 2004, 14(11)：1926-1933.
	ZHAO Zhongwei, HUO Guangsheng. Thermodynamic analysis of Li-Mn-H₂O system[J]. The Chinese Journal of Nonferrous Metals, 2004, 14(11)：1926-1933.
38	文士美, 赵中伟, 霍广生. Li-Co-H₂O系热力学分析及E-pH图[J]. 电源技术, 2005, 29(7)：423-426.
	WEN Shimei, ZHAO Zhongwei, HUO Guangsheng. Thermodynamic analysis and potential-pH diagrams of Li-Co-H₂O system[J]. Chinese Journal of Power Sources, 2005, 29(7)：423-426.
39	郭持皓, 赵中伟, 霍广生. Li-Ni-H₂O系的热力学分析[J]. 电源技术, 2005, 29(6)：376-379.
	GUO Chihao, ZHAO Zhongwei, HUO Guangsheng. Thermodyna-mic analysis on Li-Ni-H₂O system[J]. Chinese Journal of Power Sources, 2005, 29(6)：376-379.
40	WANG Hongmin, LI Mengran, GARG S, et al. Cobalt electroche-mical recovery from lithium cobalt oxides in deep eutectic choline Chloride+Urea solvents[J]. ChemSusChem, 2021, 14(14)：2972-2983.
41	PRABAHARAN G, BARIK S P, KUMAR N, et al. Electrochemical process for electrode material of spent lithium ion batteries[J]. Waste Management, 2017, 68: 527-533.
42	HE Lipo, SUN Shuying, SONG Xingfu, et al. Leaching process for recovering valuable metals from the LiNi_1/3Co_1/3Mn_1/3O₂ cathode of lithium-ion batteries[J]. Waste Management, 2017, 64: 171- 181.
43	HE Yaqun, ZHANG Tao, WANG Fangfang, et al. Recovery of LiCoO₂ and graphite from spent lithium-ion batteries by Fenton reagent-assisted flotation[J]. Journal of Cleaner Production, 2017, 143: 319-325.
44	MAY M, KUO J, TAN C T. Vacuum electrolysis reactor technique for quantitation of 13-carbon isotope enrichment at the C1-position of formic acid and acetic acid[J]. Analytical Chemistry, 2004, 76(18)：5313-5318.
45	NAIR S M K, JAMES C. Numerical data for the commonly used solid-state reaction equations[J]. Thermochimica Acta, 1985, 83(2)：387-389.
46	DICKINSON C F, HEAL G R. Solid-liquid diffusion controlled rate equations[J]. Thermochimica Acta, 1999, 340-341: 89- 103.
47	LI Li, FAN Ersha, GUAN Yibiao, et al. Sustainable recovery of cathode materials from spent lithium-ion batteries using lactic acid leaching system[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(6)：5224-5233.
48	FEAR C, JUAREZ-ROBLES D, JEEVARAJAN J A, et al. Elucidating copper dissolution phenomenon in Li-ion cells under overdischarge extremes[J]. Journal of the Electrochemical Society, 2018, 165(9)：A1639-A1647.
49	CIFUENTES G, HERNÁNDEZ J, GUAJARDO N. Recovering scrap anode copper using reactive electrodialysis[J]. American Journal of Analytical Chemistry, 2014, 5(15)：1020-1027.
50	KOGA T, NONAKA K, SAKATA Y, et al. Electrochemical formation and accumulation of Cu（Ⅰ） in copper sulfate electroplating solution[J]. Journal of the Electrochemical Society, 2018, 165(10)：D423-D426.

阴极材料	阳极材料	浸出机理	浸出率/%	槽压/V
剥离铝箔，退役LiCoO₂通过导电胶粘接在Pt片上	Pt片	阴极：LiCoO₂+4H⁺+e^-=Li⁺+Co²⁺+2H₂O 2H⁺+2e^-=H₂ 阳极：2H₂O-4e^-=4H⁺+O₂	Li：94.2 Co：90.5	8^[23]
带有铝箔的圆形退役LiCoO₂	Pt片	阴极：LiCoO₂+4H⁺+e^-=Li⁺+Co²⁺+2H₂O 2H⁺+2e^-=H₂ 阳极：2H₂O-4e^-=4H⁺+O₂	Li：98.1 Co：97.4	8^[24]
碳布（2 cm×5 cm）	LiNi _x Co _y Mn _z O₂（NCM）（2 cm×5 cm）	阴极：4H⁺+4e^-=2H₂ 阳极：LiNi _x Co _y Mn _z O₂-εe^-=εLi⁺+Li_1-_ε Ni _x Co _y Mn _z O₂ 4OH^--4e^-=O₂+2H₂O	Li：98.7 选择性：99.2	4^[25]
钛网	退役LIBs正极材料涂覆在碳纤维布上	阴极：δH⁺+δe^-=1/2δH₂ δH₂O=δH⁺+δOH^- 阳极：LiNi _x Co _y Mn _z O₂=δLi⁺+Li_1-_δ Ni _x Co _y Mn _z O₂+δe^-	Li：99.7	2^[26]
Pt片	退役LIBs正极材料（2 cm×5 cm）	阴极：4H⁺+4e^-=2H₂ 阳极：2H₂O-4e^-=4H⁺+O₂ LiNi _x Co _y Mn _z O₂=δLi⁺+Li_1-_δ Ni _x Co _y Mn _z O₂+δe^- 4OH^--4e^-=O₂+2H₂O	Li，Co，Ni，Mn：＞98.0	25^[27]

组分	各组分质量分数		元素	各组分中主要元素质量分数
组分	质量分数/%	误差/%	元素	质量分数/%	误差/%
Co₃O₄	96.40	0.110	Co	70.80	0.080
F	1.57	0.420	F	1.57	0.420
Al₂O₃	0.15	0.008	Al	0.08	0.040
MnO	0.05	0.002	Mn	0.04	0.002
NiO	0.02	0.005	Ni	0.02	0.005
其他	1.82	—	—	—	—

温度/ K	Li		Co
温度/ K	k	R²	k	R²
303	0.076	0.999	0.085	0.999
323	0.138	0.982	0.151	0.994
343	0.182	0.986	0.186	0.996
363	0.323	0.999	0.264	0.997

元素名称	质量分数/%	物质的量分数/%
C	79.40	84.70
O	11.10	8.85
F	9.59	6.47

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Study on leaching and thermodynamic of spent lithium-ion batteries with electrochemical reduction

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