废旧磷酸铁锂浸出工艺的优化及宏观动力学

doi:10.16085/j.issn.1000-6613.2023-1810

摘要/Abstract

摘要：

采取有效方法回收利用废旧磷酸铁锂中的有价组分对环境保护和资源循环具有重要意义。大量退役的磷酸铁锂电池，现有研究大多只针对其中锂的选择性浸出，并未考虑其他元素（如铁、磷、铝、铜等）的浸出行为紧密相关的问题。本文对废旧磷酸铁锂粉料的硫酸浸出过程进行了条件优化和宏观动力学研究，系统探究了温度、酸料比及反应时间对铁、磷、锂、铝和铜元素浸出过程的影响规律，讨论了以上元素浸出的宏观动力学。结果表明：优化条件下铁、磷、锂、铝和铜的浸出率分别为97.2%、96.9%、89.7%、76.1%和43.4%。其中，铁、磷、锂和铜的浸出符合内扩散模型，受扩散反应控制；铝的浸出符合混合控制模型，受扩散反应和化学反应协同控制。根据动力学模型拟合得出铁、铝和铜浸出的表观活化能分别为8.20kJ/mol、34.11kJ/mol和11.49kJ/mol。本研究明晰了废旧磷酸铁锂中各元素的浸出动力学，为元素的选择性浸出提供理论指导。

关键词: 废旧磷酸铁锂, 硫酸, 浸取, 动力学, 回收, 动力学模型

Abstract:

Employing efficient recycling techniques to recover the important components from used LiFePO₄/C powder is crucial for resource conservation and environmental preservation. Now, for a large number of retired lithium iron phosphate batteries, the majority of studies were concentrated on the selective leaching of lithium without taking into account the leaching behavior of other priceless components like iron, phosphorus, aluminum and copper. This work studied the spent LiFePO₄/C powder leaching process condition optimization and macroscopic kinetic studies. Systematically examined were the effects of temperature, acid concentration and duration on the leaching process of iron, phosphorus, lithium, aluminum and copper. The macroscopic kinetics of lithium, iron, phosphorus, aluminum and copper leaching from the powder were thoroughly investigated. The results of the experiments under optimized conditions indicated that the leaching rates of iron, phosphorus, lithium, aluminum and copper were 97.2%, 96.9%, 89.7%, 76.1% and 43.4%, respectively. The internal diffusion model predicted that iron, phosphorus, lithium and copper leached over time, and the diffusion reaction governed this process. The diffusion reaction and chemical reaction-controlled mixed control model, which governed aluminum leaching, was accurate. According to the kinetic model, the apparent activating energies of Fe, Al and Cu leaching were 8.20kJ/mol, 34.11kJ/mol and 11.49kJ/mol, respectively. This article elucidated the leaching kinetics of diverse elements in spent lithium iron phosphate offered theoretical guidance for the selective leaching of these elements.

Key words: spent lithium iron phosphate, sulphuric acid, leaching, kinetics, recovery, kinetic modeling

中图分类号:

TM912

张津榕, 彭长宏, 林金秀, 江洋, 邱在容, 周豪, 胡振光. 废旧磷酸铁锂浸出工艺的优化及宏观动力学[J]. 化工进展, 2024, 43(11): 6504-6513.

ZHANG Jinrong, PENG Changhong, LIN Jinxiu, JIANG Yang, QIU Zairong, ZHOU Hao, HU Zhenguang. Optimization of leaching conditions and macroscopic kinetics of spent LiFePO₄/C powder[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6504-6513.

图/表 10

参考文献 31

1	PENG Fangwei, MU Deying, LI Ruhong, et al. Impurity removal with highly selective and efficient methods and the recycling of transition metals from spent lithium-ion batteries[J]. RSC Advances, 2019, 9(38): 21922-21930.
2	SONG Weu, LIU Jianwen, YOU Lei, et al. Re-synthesis of nano-structured LiFePO₄/graphene composite derived from spent lithium-ion battery for booming electric vehicle application[J]. Journal of Power Sources, 2019, 419: 192-202.
3	ZHANG Xiaoxiao, LI Li, FAN Ersha, et al. Toward sustainable and systematic recycling of spent rechargeable batteries[J]. Chemical Society Reviews, 2018, 47(19): 7239-7302.
4	SONG Yingjie, ZHONG Shuqi, LI Yingjiao, et al. Study on the catalytic degradation of sodium lignosulfonate to aromatic aldehydes over nano-CuO: Process optimization and reaction kinetics[J]. Chinese Journal of Chemical Engineering, 2023, 53: 300-309.
5	张笑笑, 王鸯鸯, 刘媛, 等. 废旧锂离子电池回收处理技术与资源化再生技术进展[J]. 化工进展, 2016, 35(12): 4026-4032.
	ZHANG Xiaoxiao, WANG Yangyang, LIU Yuan, et al. Recent progress in disposal and recycling of spent lithium-ion batteries[J]. Chemical Industry and Engineering Progress, 2016, 35(12): 4026-4032.
6	RITCHIE Andrew, HOWARD Wilmont. Recent developments and likely advances in lithium-ion batteries[J]. Journal of Power Sources, 2006, 162(2): 809-812.
7	DENG Sixu, WANG Hao, LIU Hao, et al. Research progress in improving the rate performance of LiFePO₄ cathode materials[J]. Nano-Micro Letters, 2014, 6(3): 209-226.
8	曹玲, 刘雅丽, 康铎之, 等. 废旧锂电池中有价金属回收及三元正极材料的再制备[J]. 化工进展, 2019, 38(5): 2499-2505.
	CAO Ling, LIU Yali, KANG Duozhi, et al. Recovery of valuable metals from spent lithium ion battery and the resynthesis of Li(Ni_1/3Co_1/3Mn_1/3)O₂ materials[J]. Chemical Industry and Engineering Progress, 2019, 38(5): 2499-2505.
9	ZHENG Rujuan, ZHAO Li, WANG Wenjui, et al. Optimized Li and Fe recovery from spent lithium-ion batteries via a solution-precipitation method[J]. RSC Advances, 2016, 6(49): 43613-43625.
10	YUN Liu, LINH Duy, SHUI Li, et al. Metallurgical and mechanical methods for recycling of lithium-ion battery pack for electric vehicles[J]. Resources, Conservation and Recycling, 2018, 136: 198-208.
11	HE Kai, ZHANG Zhiyuan, ALAI Lagu, et al. A green process for exfoliating electrode materials and simultaneously extracting electrolyte from spent lithium-ion batteries[J]. Journal of Hazardous Materials, 2019, 375: 43-51.
12	XU Panpan, DAI Q, GAO Hongpeng, et al. Efficient direct recycling of lithium-ion battery cathodes by targeted healing[J]. Joule, 2020, 4(12): 2609-2626.
13	LIU Yan, LV Weiguang, ZHENG Xiaohong, et al. Near-to-stoichiometric acidic recovery of spent lithium-ion batteries through induced crystallization[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(8): 3183-3194.
14	LI Jingkun, MA Zifeng. Past and present of LiFePO₄: From fundamental research to industrial applications[J]. Chem, 2019, 5(1): 3-6.
15	黎华玲, 陈永珍, 宋文吉, 等. 湿法回收退役三元锂离子电池有价金属的研究进展[J]. 化工进展, 2019, 38(2): 921-932.
	LI Hualing, CHEN Yongzhen, SONG Wenji, et al. Research progress on the recovery of valuable matals in retired LiNi _x Co _y Mn _z O₂batteries by wet process[J]. Chemical Industry and Engineering Progress, 2019, 38(2): 921-932.
16	华政, 梁风, 姚耀春. 电动汽车电池的发展现状与趋势[J]. 化工进展, 2017, 36(8): 2874-2881.
	HUA Zheng, LIANG Feng, YAO Yaochun. Status and development trend for battery of electric vehicles [J]. Chemical Industry and Engineering Progress, 2017, 36(8): 2874-2881.
17	XU Xueqing, MU Wenning, XIAO Tengfei, et al. A clean and efficient process for simultaneous extraction of Li, Co, Ni and Mn from spent Lithium-ion batteries by low-temperature NH₄Cl roasting and water leaching[J]. Waste Management, 2022, 153: 61-71.
18	HARPER Gavin, SOMMERVILLE Roberto, KENDRICK Emma, et al. Recycling lithium-ion batteries from electric vehicles[J]. Nature, 2019, 575(7781): 75-86
19	YANG Yongxia, MENG Xiangqi, CAO Hongbin, et al. Selective recovery of lithium from spent lithium iron phosphate batteries: A sustainable process[J]. Green Chemistry, 2018, 20(13): 3121-3133.
20	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): 3485-3491.
21	刘肖贝, 张西华, 熊梅, 等. 退役锂电池放电废水特征有机污染物解析[J]. 化工进展, 2022, 41(10): 5619-5629.
	LIU Xiaobei, ZHANG Xihua, XIONG Mei, et al. Analysis on the characteristic organic pollutants from discharge wastewater of spent lithium batteries[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5619-5629.
22	于捷, 张文龙. 锂离子电池隔膜的发展现状与进展[J]. 化工进展, 2023, 42(4): 1760-1768.
	YU Jie, ZHANG Wenlong. Development status and progress of lithium ion battery separator[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1760-1768.
23	BIAN Doucheng, SUN Yonghui, LI Sheng, et al. A novel process to recycle spent LiFePO₄ for synthesizing LiFePO₄/C hierarchical microflowers[J]. Electrochimica Acta, 2016, 190: 134-140.
24	KUMAR Jai, SHEN Xing, LI Bo, et al. Selective recovery of Li and FePO₄from spent LiFePO₄ cathode scraps by organic acids and the properties of the regenerated LiFePO₄ [J]. Waste Management, 2020, 113: 32-40.
25	王特, 蒋立, 田晓录, 等. 锂离子电池安全材料的研究进展[J]. 化工进展, 2021, 40(6): 3132-3142.
	WANG Te, JIANG Li, TIAN Xiaolu, et al. Research progress of lithium ion batteries safety materials[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3132-3142.
26	LI Huan, XING Shengzhou, LIU Yu, et al. Recovery of lithium, iron, and phosphorus from spent LiFePO₄ batteries using stoichiometric sulfuric acid leaching system[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(9): 8017-8024.
27	WU Deyou, WANG Dongxing, LIU Zhiqiang, et al. Selective recovery of lithium from spent lithium iron phosphate batteries using oxidation pressure sulfuric acid leaching system[J]. Transactions of Nonferrous Metals Society of China, 2022, 32(6): 2071-2079.
28	周吉奎, 刘牡丹, 刘勇, 等. 硫酸-双氧水浸出废弃磷酸铁锂中锂的实验研究[J]. 矿冶工程, 2020, 40(6): 79-81.
	ZHOU Jikui, LIU Mudan, LIU Yong, et al. Experimental study on leaching of lithium from waste lithium iron phosphate with sulfuric acid and hydrogen peroxide[J]. Mining and Metallurgical Engineering, 2020, 40(6): 79-81.
29	张恒, 李海浩, 王梦娇, 等. 退役动力电池材料再生利用综述[J]. 电池, 2022, 52(1): 105-109.
	ZHANG Heng, LI Haihao, WANG Mengjiao, et al. Review on the regeneration and utilization of retired power battery[J]. Battery Bimonthly, 2022, 52(1): 105-109.
30	万青珂, 张洋, 郑诗礼, 等.废旧磷酸铁锂正极粉磷酸浸出过程的优化及宏观动力学[J]. 化工进展, 2020, 39(6): 2495-2502.
	WAN Qingke, ZHANG Yang, ZHENG Shili, et al. Process optimization and kinetics for leaching spent lithium iron phosphate cathode powder by phosphate acid[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2495-2502.
31	李劲, 邵威, 毛洪仁. 废弃锂离子电池回收处理的污染物分析[J]. 化工进展, 2016, 35(5): 1529-1538.
	LI Jin, SHAO Wei, MAO Hongren. Analysis of pollutants in the recycling of waste lithium batteries[J]. Chemical Industry and Engineering Progress, 2016, 35(5): 1529-1538.

元素	质量分数/%
Fe	21.5
P	13.7
Li	3
Al	0.9
Cu	1.6
Mn	0.0062
Ti	0.059

元素	质量分数/%
Fe	21.5
P	13.7
Li	3
Al	0.9
Cu	1.6
Mn	0.0062
Ti	0.059

元素	温度/℃	内扩散		界面化学反应
元素	温度/℃	反应速率常数k	相关系数R²	反应速率常数k	相关系数R²
Fe	30	2.22×10^-3	0.982	8.19×10^-3	0.979
	50	2.71×10^-3	0.985	8.98×10^-3	0.955
	70	3.09×10^-3	0.997	9.50×10^-3	0.918
	90	3.87×10^-3	0.970	10.88×10^-3	0.863
P	30	1.67×10^-3	0.985	23.27×10^-3	0.973
	50	1.80×10^-3	0.961	24.67×10^-3	0.910
	70	2.22×10^-3	0.957	30.73×10^-3	0.921
	90	2.57×10^-3	0.942	36.79×10^-3	0.937
Cu	30	0.47×10^-3	0.985	8.65×10^-3	0.916
	50	0.48×10^-3	0.959	8.38×10^-3	0.839
	70	0.54×10^-3	0.925	9.00×10^-3	0.807
	90	0.93×10^-3	0.980	13.73×10^-3	0.916
Al	30	1.37×10^-3	0.971	19.40×10^-3	0.948
	50	3.29×10^-3	0.945	49.80×10^-3	0.983
	70	3.58×10^-3	0.973	56.80×10^-3	0.994
	90	5.16×10^-3	0.997	112.20×10^-3	0.944

元素	温度/℃	内扩散		界面化学反应
元素	温度/℃	反应速率常数k	相关系数R²	反应速率常数k	相关系数R²
Fe	30	2.22×10^-3	0.982	8.19×10^-3	0.979
	50	2.71×10^-3	0.985	8.98×10^-3	0.955
	70	3.09×10^-3	0.997	9.50×10^-3	0.918
	90	3.87×10^-3	0.970	10.88×10^-3	0.863
P	30	1.67×10^-3	0.985	23.27×10^-3	0.973
	50	1.80×10^-3	0.961	24.67×10^-3	0.910
	70	2.22×10^-3	0.957	30.73×10^-3	0.921
	90	2.57×10^-3	0.942	36.79×10^-3	0.937
Cu	30	0.47×10^-3	0.985	8.65×10^-3	0.916
	50	0.48×10^-3	0.959	8.38×10^-3	0.839
	70	0.54×10^-3	0.925	9.00×10^-3	0.807
	90	0.93×10^-3	0.980	13.73×10^-3	0.916
Al	30	1.37×10^-3	0.971	19.40×10^-3	0.948
	50	3.29×10^-3	0.945	49.80×10^-3	0.983
	70	3.58×10^-3	0.973	56.80×10^-3	0.994
	90	5.16×10^-3	0.997	112.20×10^-3	0.944

[1]	何方, 许高洁, 裴翔, 孙德智, 宁朋歌, 曹宏斌. IPE-23萃取剂在含锂废液中回收锂的应用[J]. 化工进展, 2024, 43(S1): 627-639.
[2]	杨俊辉, 袁君, 张继达, 王金海, 乔红斌, 蔡振义, 马中成. 新型蓄热体结构设计及性能分析[J]. 化工进展, 2024, 43(S1): 282-294.
[3]	李依梦, 陈运全, 何畅, 张冰剑, 陈清林. 基于物理信息神经网络的甲烷无氧芳构化反应的正反问题[J]. 化工进展, 2024, 43(9): 4817-4823.
[4]	李红彦, 谢书涵, 张燕如, 王永净, 王永好, 吕源财, 林春香, 李小娟. 废旧锂离子电池正极材料直接再生技术研究进展[J]. 化工进展, 2024, 43(9): 5207-5216.
[5]	马红周, 党煜博, 王耀宁, 曾劲阳, 赵小军, 史建伟. 废锌基脱硫剂与铜锌基催化剂协同真空碳热提取锌[J]. 化工进展, 2024, 43(9): 5275-5281.
[6]	安芳芳, 曹少磊, 连增帅, 舒大武, 张岩, 李万新, 韩博. 十二烷基甜菜碱对热活化过硫酸钠降解C.I.活性黑5的影响[J]. 化工进展, 2024, 43(9): 5302-5308.
[7]	何海霞, 万亚萌, 李帆帆, 牛心雨, 张静雯, 李涛, 任保增. 盐酸萘甲唑啉在甲醇-乙酸乙酯体系中的动力学及结晶工艺[J]. 化工进展, 2024, 43(8): 4230-4245.
[8]	殷晨阳, 刘永峰, 陈睿哲, 张璐, 宋金瓯, 刘海峰. 基于量子化学计算的正己烷热解反应动力学模拟[J]. 化工进展, 2024, 43(8): 4273-4282.
[9]	高昕玥, 范高峰, 刘爱平, 王长安, 侯育杰, 张津铭, 徐杰, 车得福. 湿法脱硫后烟气和浆液余热回收技术研究进展[J]. 化工进展, 2024, 43(8): 4307-4319.
[10]	谢娟, 贺文, 赵勖丞, 李帅辉, 卢真真, 丁哲宇. 分子动力学模拟在沥青体系中的应用研究进展[J]. 化工进展, 2024, 43(8): 4432-4449.
[11]	李斌德, 王碧侠, 袁文龙, 党晓娥, 马红周. 钛白副产硫酸亚铁制备电池级磷酸铁[J]. 化工进展, 2024, 43(8): 4523-4533.
[12]	黎伟杰, 路蕾蕾, 李得科, 王春航, 张祖铭, 谭强. 锂离子电池拆解回收技术及进展[J]. 化工进展, 2024, 43(8): 4601-4613.
[13]	刘玉灿, 高中鲁, 徐心怡, 纪现国, 张岩, 孙洪伟, 王港. 钙改性水葫芦基生物炭吸附水中敌草隆的效能与机理[J]. 化工进展, 2024, 43(8): 4630-4641.
[14]	曾武清, 王予, 卜庆国, 马硕, 白东明, 张宗建, 张鹏, 马丹丹, 王圣博, 王润其, 武丽雯, 刘晨, 马洪亭. 陈腐垃圾掺烧对垃圾炉焚烧特性的影响[J]. 化工进展, 2024, 43(8): 4642-4653.
[15]	怀立业, 仲兆平, 杨宇轩. 脱硫石膏转化α-半水石膏的特征及机理：实验与模拟[J]. 化工进展, 2024, 43(8): 4694-4703.