热力学研究在锂离子电池回收中的应用

doi:10.16085/j.issn.1000-6613.2021-0818

化工进展 ›› 2021, Vol. 40 ›› Issue (10): 5325-5336.DOI: 10.16085/j.issn.1000-6613.2021-0818

• 专栏：资源循环与增值利用 • 上一篇下一篇

热力学研究在锂离子电池回收中的应用

刘子潇¹^,²(), 张家靓¹^,²^,³(), 杨成¹^,², 陈永强¹^,²^,³, 王成彦¹^,²^,³^,⁴()

^1.北京科技大学钢铁冶金新技术国家重点实验室，北京 100083
^2.北京科技大学冶金与生态工程学院，北京 100083
^3.稀贵金属绿色回收与提取北京市重点实验室，北京 100083
^4.江西理工大学材料冶金化学学部，江西赣州 341000

收稿日期:2021-04-18 修回日期:2021-05-28 出版日期:2021-10-10 发布日期:2021-10-25
通讯作者: 张家靓,王成彦
作者简介:刘子潇（1997—），女，硕士研究生，研究方向为锂离子电池回收。E-mail：727439603@qq.com。
基金资助:
广东省重点领域研发计划(2020B090919003);国家自然科学基金(51834008);中央高校基本科研经费项目(FRF-TP-18-020A3)

Applications of thermodynamic research in recycling of lithium ion battery

LIU Zixiao¹^,²(), ZHANG Jialiang¹^,²^,³(), YANG Cheng¹^,², CHEN Yongqiang¹^,²^,³, WANG Chengyan¹^,²^,³^,⁴()

^1.State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
^2.School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China
^3.Beijing Key Laboratory of Green Recycling and Extraction of Metals, Beijing 100083, China
^4.Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China

Received:2021-04-18 Revised:2021-05-28 Online:2021-10-10 Published:2021-10-25
Contact: ZHANG Jialiang,WANG Chengyan

摘要/Abstract

摘要：

废旧锂离子电池的回收是近年来资源回收研究领域的热点，但相关回收体系的理论基础研究仍然较为薄弱。其中在热力学研究方面，研究者们大多仍以经典冶金物理化学理论为指导，并借助E-pH图、优势区域图等方法开展研究。本文对该领域已有的较为典型的热力学研究进行综述，详细阐述了热力学研究对废旧锂离子电池常规回收工艺的指导作用以及对三元正极废料选择性提锂、磷酸铁锂正极废料选择性提锂和失效电池材料再生修复等新技术开发的启发性作用。同时，基于对现有锂离子电池回收体系热力学研究的总结和评述，指出了未来锂离子电池回收体系热力学研究亟待解决的关键问题和发展方向。

关键词: 锂离子电池, 热力学, 回收, 再生

Abstract:

Recycling of spent lithium ion batteries has become a hot topic in the field of resource recovery recently, but the theoretical basis of related recovery system is still comparatively weak. In the aspect of thermodynamics, most researchers still take the classical theory of metallurgical physical and chemical as the guide, and carry out research with the help of E-pH diagrams, predominance diagrams and other methods. In this paper, the existing typical thermodynamic studies in this field were reviewed. The guidance of thermodynamic research on the current recovery process of spent lithium ion batteries, the inspiration for the selective extraction of lithium from spent ternary cathode materials and lithium iron phosphate cathode materials, and the development of new technologies for the regeneration of failed battery materials were described in detail. Meanwhile, based on the summary and review of the existing research on the thermodynamics of lithium ion battery recycling system, the key problems to be solved and the direction for future thermodynamic research on lithium ion battery recycling were pointed out.

Key words: lithium ion battery, thermodynamics, recovery, regeneration

中图分类号:

TF801

刘子潇, 张家靓, 杨成, 陈永强, 王成彦. 热力学研究在锂离子电池回收中的应用[J]. 化工进展, 2021, 40(10): 5325-5336.

LIU Zixiao, ZHANG Jialiang, YANG Cheng, CHEN Yongqiang, WANG Chengyan. Applications of thermodynamic research in recycling of lithium ion battery[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5325-5336.

图/表 15

图1 Li-M(Ni, Co, Mn)-H2O系E-pH图[24-26]

（25℃，[Li, M]=1mmol·L-1）

图2 有铝和无铝时不同温度下NCM三元材料还原焙烧的反应产物[28]

图3 有铝和无铝存在时不同焙烧温度下三元电池废料焙烧产物的XRD谱图[28]

图4 Li浸出率与CO2流量的关系[32]

图5 还原焙烧对Ni、Co、Mn酸浸浸出率的影响[32]

图6 Li-S-O、Ni-S-O、Co-S-O、Mn-S-O系的优势区域图以及所有优势区域图的叠加[53]

图7 (NH4)2SO4焙烧转化机理、焙烧温度对金属浸出率的影响以及不同焙烧温度下焙烧产物的XRD谱图[53]

图8 Li-Fe-P-H2O系E-pH图（298.15K）[54]

图9 Na2S2O8直接氧化选择性提锂工艺[55]

图10 Li-M(Ni, Co, Mn)-H2O系E-pH图的叠加

图11 Li-Fe-P-H2O系E-pH图（298.15～473.15K）[54]

图12 LiFePO4水热修复机理[70]

图13 修复前后LiFePO4的高分辨率TEM图谱[70]

图14 1C倍率下LiFePO4的循环性能[70]

图15 修复前后LiFePO4的倍率性能[70]

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热力学研究在锂离子电池回收中的应用

Applications of thermodynamic research in recycling of lithium ion battery

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