一步法回收和再生废旧钴酸锂电池中的钴酸锂

doi:10.16085/j.issn.1000-6613.2018-1937

摘要/Abstract

摘要：

采用酸浸法和溶胶-凝胶法耦合的一步法技术路线回收和再生LiCoO₂，简化了流程。先使用柠檬酸浸出正极材料中的Co和Li元素，然后采用溶胶-凝胶法从浸出液中直接再生LiCoO₂，柠檬酸在过程中起到了浸出剂和螯合剂的双重作用，简化了回收和再生流程。摸索了柠檬酸浓度、固液比、浸出温度、H₂O₂体积浓度和浸出时间对Co和Li浸出效率的影响规律，探究了煅烧温度对再生钴酸锂结构组成、颗粒形貌以及电化学性能的影响规律。结果表明，最佳浸出条件为：柠檬酸浓度为1.5mol/L，固液比为20g/L，浸出温度为80℃，H₂O₂体积分数为2%，浸出时间为60min。在此条件下，Co和Li的浸出率分别达到93.7%、98.2%。通过电化学分析表明，在700℃下煅烧得到的再生LiCoO₂电化学性能最佳，在1C下经50次循环后可逆放电比容量为118.7mA·h/g，容量保持率为93%。

关键词: 废旧钴酸锂电池, 柠檬酸, 溶胶-凝胶法

Abstract:

In this work, we developed a one-step technique coupling acid leaching and sol-gel method to recover and regenerate LiCoO₂ from the spent lithium cobalt oxide batteries. First, citric acid was used to extract the Co and Li from the cathode material, and then LiCoO₂ was directly regenerated from the leaching solution by sol-gel method. Citric acid acted both as leaching agent and chelating agent in the process, simplified the process of recovery and regeneration. The effects of citric acid concentration, solid-liquid ratio, leaching temperature, volume concentration of hydrogen peroxide and leaching time on the leaching efficiency of Co and Li were explored and the effects of calcination temperature on the structure, morphology and electrochemical properties of the reclaimed lithium cobalt oxide were investigated. The results showed that the optimum leaching conditions were citric acid concentration of 1.5mol/L, solid-liquid ratio of 20g/L, leaching temperature of 80℃, H₂O₂ content of 2%, and leaching time of 60 minutes. Under these conditions, the leaching rates of Co and Li reached 93.7% and 98.2% respectively. The electrochemical analysis indicated that the regenerated LiCoO₂ by calcination at 700℃ had the best electrochemical performance. The specific discharge capacity of the regenerated LiCoO₂ was 118.7mA·h/g, at 1C after 50 cycles, with a capacity retention of 93%.

Key words: spent lithium cobalt oxide batteries, citric acid, sol-gel method

中图分类号:

X705

张飞,陆颖舟. 一步法回收和再生废旧钴酸锂电池中的钴酸锂[J]. 化工进展, 2019, 38(08): 3874-3880.

Fei ZHANG,Yingzhou LU. One-step recovery and regeneration of LiCoO₂ from the spent lithium cobalt oxide battery[J]. Chemical Industry and Engineering Progress, 2019, 38(08): 3874-3880.

图/表 11

图1 实验流程图

图2 预处理后正极材料粉末的TG/DSC表征结果

图3 正极材料煅烧（Ⅰ）前后的XRD表征结果

图4 柠檬酸浓度对浸出效率的影响

图5 固液比对浸出效率的影响

图6 H2O2用量对浸出效率的影响

图7 温度对浸出效率的影响

图8 浸出时间对浸出效率的影响

图9 不同煅烧温度下再生LiCoO2的XRD表征结果

图11 不同煅烧温度下再生LiCoO2的首次放电曲线

图12 700℃下煅烧再生LiCoO2材料的循环性能曲线

参考文献 20

1	FERGUS J W . Recent developments in cathode materials for lithium ion batteries[J]. Power Sources, 2010, 195(4): 939-954.
2	WANG X , GAUSTAD G , BABBITT C W , et al . Economic and environmental characterization of an evolving Li-ion battery waste stream[J]. Waste Manage, 2014, 135: 126-134.
3	孟奇, 张英杰, 董鹏, 等 . 废旧锂离子电池中钴、锂的回收研究进展[J]. 化工进展, 2017, 36(9): 3485-3491.
	MENG Qi , ZHANG Yingjie , DONG Peng , et al . Recovery of Co and Li from spent lithium ion batteries[J]. Chemical Industry and Engineering Progress, 2017, 36(9): 3486-3491.
4	JOULIE M , LAUCOURNET R , BILLY E . Hydrometallurgical process for the recovery of high value metals from spent lithium nickel cobalt aluminum oxide based lithium-ion batteries[J]. Power Sources, 2014, 247: 551-555.
5	MA L, NIE Z , XI X , et al . Cobalt recovery from cobalt-bearing waste in sulphuric and citric acid systems[J]. Hydrometallurgy, 2013, 136: 1-7.
6	ZHANG X , XIE X , LIN X , et al . An overview on the processes and technologies for recycling cathodic active materials from spent lithium-ion batteries[J]. Journal of Material Cycles and Waste Management, 2013, 15: 420-430.
7	LI L , QU W , ZHANG X , et al . Succinic acid-based leaching system: a sustainable process for recovery of valuable metals from spent Li-ion batteries[J]. Power Sources, 2015, 282: 544-551.
8	CHEN X , ZHOU T , KONG J , et al . Separation and recovery of metal values from leach liquor of waste lithium nickel cobalt manganese oxide based cathodes[J]. Separation and Purification Technology, 2015, 141: 76-83.
9	LI L , DUNN J B , ZHANG X , et al . Recovery of metals from spent lithium-ion batteries with organic acids as leaching reagents and environmental assessment[J]. Power Sources, 2013, 233: 180-189.
10	LI L , LU J , REN Y , et al . Ascorbic acid assisted recovery of cobalt and lithium from spent Li-ion batteries[J]. Power Sources, 2012, 218: 21-27.
11	唐致远, 阮艳莉 . 新型锂离子电池正极材料的研究进展[J]. 化工进展, 2004, 23(8): 801-805.
	TANG Zhiyuan , RUAN Yanli . Progress in research of olivine-type cathode material in Li-ion batteries[J]. Chemical Industry and Engineering Progress, 2004, 23(8): 801-805.
12	王兴杰，杨文胜，卫敏，等 . 柠檬酸溶胶凝胶法制备LiCoO₂电极材料及其表征[J]. 无机化学学报，2003, 19(6):603-608.
	WANG Xingjie , YANG Wensheng , WEI Min , et al . Synthesis and characterization of LiCoO₂ electrode material by citrate sol-gel method[J]. Chinese Journal of Inorganic Chemistry, 2003, 19(6): 603-608.
13	CHIANG Y M , JIANG Y I , WANG H F , et al . Synthesis of LiCoO₂ by decomposition and intercation of hydroxides[J]. Power Sources, 1998, 72: 215-220.
14	Tomoaki WATANABO , Hiroyuki UONO , SONG Seung-Wan , et al . Direct fabrication of lithium cobalt oxide films on various substrates in flowing aqueous solution at 150℃[J]. Journal of Solid State Chemistry, 2001, 162(2): 364-370.
15	前知勉编 . 塑料性能应用手册(修订版)[M]. 上海: 上海科学技术文献出版社，1987: 302-306.
	QIAN Zhimian . Application manual of plastic performance (Revised Edition)[M]. Shanghai: Shanghai Science and Technology Literature Publishing House, 1987: 302-306.
16	CHUNG N H , TABATA M . Salting-out phase separation of the mixture of 2-propanol and water for selective extraction of cobalt (Ⅱ) in the presence of manganese (Ⅱ), nickel (Ⅱ) and copper (Ⅱ)[J]. Hydrometallurgy, 2004, 73(1/2): 81-89.
17	MA L, NIE Z , XI X , HAN X G . Cobalt recovery from cobalt bearing waste in sulphuric and citric acid systems[J]. Hydrometallurgy, 2013, 136: 1-7.
18	闫使建, 田文怀, 其鲁 . 不同温度下合成的LiCoO₂的晶体结构[J]. 无机化学学报, 2006, 22(2): 211-216.
	YAN Shijian , TIAN Wenhuai , QI Lu . Crystal structures of LiCoO₂ synthesized at different temperatures[J].Chinese Journal of Inorganic Chemistry, 2006, 22(2): 211-216.
19	傅秋莲, 蒋晓瑜, 陈文哲 . 柠檬酸溶胶凝胶法合成LiCoO₂的晶体结构研究[J]. 光谱学与光谱分析, 2008, 28(6):1222-1226.
	FU Qiulian , JIANG Xiaoyu , CHEN Wenzhe . Study on the structure of LiCoO₂ synthesized by sol-gel with citric acid[J]. Spectroscopy and Spectral Analysis, 2008, 28(6): 1222-1226.
20	ANTOLINI E , FERRETTI M . Synthesis and thermal stability of LiCoO₂ [J]. J. Solid State Chem., 1995, 117:1-7.

[1]	王园园, 宋华, 苑丹丹, 孙兴龙, 柳艳修. 柠檬酸改性H-beta催化甲苯和叔丁醇烷基化[J]. 化工进展, 2022, 41(1): 237-243.
[2]	潘迪, 孔江榕, 刘欣楠, 黄美琪, 周涛. 湿化学法制备石榴石型固态电解质Li₇La₃Zr₂O₁₂[J]. 化工进展, 2021, 40(S2): 334-339.
[3]	佟欣瑞, 刘彦君, 曹林峰, 毕美营, 董延甲, 吴欣瑜, 谈浚杰, 应明. 可控式citZ基因纳米盒的设计与研究[J]. 化工进展, 2021, 40(S1): 344-349.
[4]	闫晓峰, 高文桂, 毛文硕, 纳薇, 霍海辉, 常帅. 溶胶-凝胶法制备Cu-ZnO-ZrO₂催化剂：柠檬酸用量对催化剂性能的影响[J]. 化工进展, 2020, 39(10): 4032-4040.
[5]	王瑞, 归柯庭, 梁辉. Ce的掺杂对负载型催化剂LaMnO₃/赤铁矿脱硝性能的影响[J]. 化工进展, 2016, 35(S2): 192-199.
[6]	范益群, 漆虹. 陶瓷纳滤膜制备与应用研究进展[J]. 化工进展, 2016, 35(06): 1786-1793.
[7]	李静, 王乐, 孙维周, 左志军, 黄伟. 制备方法对Co-Pd/TiO₂催化剂催化CH₄-CO₂梯阶转化的影响[J]. 化工进展, 2015, 34(3): 738-744,757.
[8]	苑丹丹, 张永江, 李锋, 宋华. 制备条件对Ni₂P/TiO₂-Al₂O₃催化剂加氢脱硫性能的影响[J]. 化工进展, 2015, 34(07): 1882-1886.
[9]	苑丹丹, 张永江, 李锋, 宋华. 焙烧及还原条件对Ni₂P/TiO₂-Al₂O₃催化剂加氢脱硫性能的影响[J]. 化工进展, 2015, 34(06): 1656-1660,1689.
[10]	郭剑桥1，虞宁2，丁嘉1，黄媛媛1，汪青松1，李工1. 单核及双核叔铵盐离子液体的合成及用于柠檬酸三丁酯的制备[J]. 化工进展, 2014, 33(12): 3270-3275.
[11]	喻文昊1，张伟1，李富元2，王进2，孙晓娟1，胡雅君1，梁莎1，杨家宽1. 铅酸电池企业含铅废料湿法再生新技术[J]. 化工进展, 2014, 33(12): 3399-3404.
[12]	姜跃平1，2，李如燕1，2，孙可伟2，刘璇2. 柠檬酸交联纤维素凝胶材料的制备与性能表征[J]. 化工进展, 2014, 33(07): 1796-1802.
[13]	张青. 溶胶-凝胶法与自模板法相结合制备SiO2中空微球[J]. 化工进展, 2014, 33(06): 1517-1520.
[14]	夏海虹，蒋剑春，徐俊明，李静，刘朋. 微波加热促进离子液体催化合成柠檬酸三丁酯及其性能[J]. 化工进展, 2014, 33(04): 982-987.
[15]	王霞，吴玉娥，颜洁，陈仕学. 超声波-微波辅助柠檬酸催化纤维素水解条件[J]. 化工进展, 2014, 33(03): 634-637.