化工进展 ›› 2024, Vol. 43 ›› Issue (6): 3336-3346.DOI: 10.16085/j.issn.1000-6613.2023-0845
• 资源与环境化工 • 上一篇
王厚然1,2,3,4(), 李德念1,3,4(
), 董楠航2, 阳济章1,3,4, 倪轩辕1,3,4, 叶嘉鸿1,3,4, 袁浩然1,3,4(
), 陈勇1,3,4
收稿日期:
2023-05-22
修回日期:
2023-07-19
出版日期:
2024-06-15
发布日期:
2024-07-02
通讯作者:
袁浩然
作者简介:
王厚然(1990—),男,硕士研究生,研究方向为废旧锂离子电池资源化利用。E-mail:347619195@qq.com基金资助:
WANG Houran1,2,3,4(), LI Denian1,3,4(
), DONG Nanhang2, YANG Jizhang1,3,4, NI Xuanyuan1,3,4, YE Jiahong1,3,4, YUAN Haoran1,3,4(
), CHEN Yong1,3,4
Received:
2023-05-22
Revised:
2023-07-19
Online:
2024-06-15
Published:
2024-07-02
Contact:
YUAN Haoran
摘要:
锂电池产业的迅猛发展以及新型储能对锂离子电池需求的进一步增长预期引起了各界对相关资源与环境问题的广泛担忧,因此退役锂离子电池的回收利用已成为当前产业体系中的重要一环。锂离子电池的正极材料是锂电池中最具价值的部分,相比于目前已投入生产的湿法回收与火法回收工艺,针对退役正极材料直接修复的研究目前仍处于起步阶段,因其相比于传统回收方法具有绿色廉价等优势,未来仍然存在可观的开发空间。本文介绍了磷酸铁锂电池与三元锂电池及两种锂离子电池正极材料的主要失效原因,以及针对此两种锂离子电池退役后其正极材料的几种直接修复方法,并对不同直接修复方法存在的问题进行了梳理,进而对正极材料直接修复提出相关建议,以期直接修复可以在锂电行业有更广阔的发展。
中图分类号:
王厚然, 李德念, 董楠航, 阳济章, 倪轩辕, 叶嘉鸿, 袁浩然, 陈勇. 退役磷酸铁锂电池与三元锂电池正极材料直接修复研究进展[J]. 化工进展, 2024, 43(6): 3336-3346.
WANG Houran, LI Denian, DONG Nanhang, YANG Jizhang, NI Xuanyuan, YE Jiahong, YUAN Haoran, CHEN Yong. Advances in direct repair of cathode materials from retired lithium iron phosphate battery and ternary lithium battery[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3336-3346.
性能 | LFP | NCM |
---|---|---|
化学式 | Li(Ni x Co y Mn1-x-y )O2 | |
晶体结构 | 橄榄石结构 | 层状结构 |
空间点群 | Pmnb | R-3m |
锂离子表观扩散系数/cm2·s-1 | 1.8×10-16~2.2×10-14 | 10-1~10-11 |
理论容量/mAh·g-1 | 170 | 273~285 |
实际容量/mAh·g-1 | 130~140 | 155~220 |
平均电压/V | 3.4 | 3.6 |
循环性/次 | 2000~6000 | 800~2000 |
环保性 | 无毒 | 镍、钴有毒 |
安全性能 | 好 | 中 |
价格/104CNY·t-1 | 15~20 | 15.5~16.5 |
主要应用领域 | 电动汽车及大规模储能 | 电动工具、电动自行车、电动汽车及大规模储能 |
表 1 LFP与NCM基本构成与性能
性能 | LFP | NCM |
---|---|---|
化学式 | Li(Ni x Co y Mn1-x-y )O2 | |
晶体结构 | 橄榄石结构 | 层状结构 |
空间点群 | Pmnb | R-3m |
锂离子表观扩散系数/cm2·s-1 | 1.8×10-16~2.2×10-14 | 10-1~10-11 |
理论容量/mAh·g-1 | 170 | 273~285 |
实际容量/mAh·g-1 | 130~140 | 155~220 |
平均电压/V | 3.4 | 3.6 |
循环性/次 | 2000~6000 | 800~2000 |
环保性 | 无毒 | 镍、钴有毒 |
安全性能 | 好 | 中 |
价格/104CNY·t-1 | 15~20 | 15.5~16.5 |
主要应用领域 | 电动汽车及大规模储能 | 电动工具、电动自行车、电动汽车及大规模储能 |
项目 | LFP电池 | NCM电池 |
---|---|---|
回收方式 | 梯次利用:将剩余容量较高的退役电池在低要求的电池领域进行二次使用 | 拆解回收:对电池进行拆解处理,提取内部可回收金属 |
经济效益 | 回收材料经济效益较差 | 材料含有锂、镍、钴,回收价值高 |
表 2 退役LFP电池与NCM电池常见处理方式
项目 | LFP电池 | NCM电池 |
---|---|---|
回收方式 | 梯次利用:将剩余容量较高的退役电池在低要求的电池领域进行二次使用 | 拆解回收:对电池进行拆解处理,提取内部可回收金属 |
经济效益 | 回收材料经济效益较差 | 材料含有锂、镍、钴,回收价值高 |
正极材料 | 修复方法 | 商业正极材料实际容量/mAh·g-1 | 修复后正极材料最大放电容量/mAh·g-1 | 参考文献 |
---|---|---|---|---|
LFP | 固相烧结法 | 130~140 | 154.3(0.1C) | [ |
150.99(0.2C) | [ | |||
144(0.1C) | [ | |||
139(0.2C) | [ | |||
电化学法 | 159(0.1C) | [ | ||
135.2(1.0C) | [ | |||
水热法 | 144.02(0.1C) | [ | ||
146.2(1.0C) | [ | |||
161.4(0.2C) | [ | |||
162(0.5C) | [ | |||
化学法 | 160.1(0.5C) | [ | ||
NCM | 固相烧结法 | 155~220 | 162(0.1C) | [ |
154.87(0.2C) | [ | |||
189.8(0.1C) | [ | |||
162(0.2C) | [ | |||
水热法 | 145.1(1.0C) | [ | ||
166.1(0.1C) | [ | |||
156.6(0.1C) | [ | |||
共晶法 | 149.3(1.0C) | [ | ||
146.3(1.0C) | [ | |||
160(0.5C) | [ | |||
氧化还原法 | 182.5(1.0C) | [ |
表3 LFP和NCM电池正极材料直接修复方法
正极材料 | 修复方法 | 商业正极材料实际容量/mAh·g-1 | 修复后正极材料最大放电容量/mAh·g-1 | 参考文献 |
---|---|---|---|---|
LFP | 固相烧结法 | 130~140 | 154.3(0.1C) | [ |
150.99(0.2C) | [ | |||
144(0.1C) | [ | |||
139(0.2C) | [ | |||
电化学法 | 159(0.1C) | [ | ||
135.2(1.0C) | [ | |||
水热法 | 144.02(0.1C) | [ | ||
146.2(1.0C) | [ | |||
161.4(0.2C) | [ | |||
162(0.5C) | [ | |||
化学法 | 160.1(0.5C) | [ | ||
NCM | 固相烧结法 | 155~220 | 162(0.1C) | [ |
154.87(0.2C) | [ | |||
189.8(0.1C) | [ | |||
162(0.2C) | [ | |||
水热法 | 145.1(1.0C) | [ | ||
166.1(0.1C) | [ | |||
156.6(0.1C) | [ | |||
共晶法 | 149.3(1.0C) | [ | ||
146.3(1.0C) | [ | |||
160(0.5C) | [ | |||
氧化还原法 | 182.5(1.0C) | [ |
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