废旧三元锂电池石墨负极电化学除杂及其性能研究

张锐; 田勇; 张维丽; 宋佳音; 闵杰; 庞博; 陈建军

doi:10.1016/S1872-5805(24)60843-7

废旧三元锂电池石墨负极电化学除杂及其性能研究

doi: 10.1016/S1872-5805(24)60843-7

张锐^{1, 2,},
田勇¹,
张维丽¹,
宋佳音²,
闵杰¹,
庞博¹,
陈建军^{1, 2, ,}

1.
清华大学深圳国际研究生院, 深圳 518057
2.
深圳清研锂业科技有限公司, 深圳 518057

基金项目: 深圳市可持续发展专项项目（KCXFZ202002011006254），深圳市可持续发展专项项目（KCXFZ20201221173214040），深圳市技术攻关项目（JSGG20190822102607176）和广东省基础与应用基础研究（2020A1515011431）资助。

详细信息

作者简介:
张锐：张　锐，E-mail：zrhitsz22334@163.com

通讯作者:
陈建军，教授级高工. E-mail: chenjj08@126.com

中图分类号: TQ127.1⁺1
计量
- 文章访问数: 74
- HTML全文浏览量: 42
- PDF下载量: 18
- 被引次数: 0
出版历程
- 收稿日期: 2023-10-27
- 录用日期: 2024-02-02
- 修回日期: 2024-01-31
- 网络出版日期: 2024-02-21

Electrochemical method for impurity removal of graphite anode in spent ternary lithium-ion batteries

ZHANG Rui^{1, 2
,},
TIAN Yong¹,
ZHANG Wei-li¹,
SONG Jia-yin²,
MIN Jie¹,
PANG Bo¹,
CHEN Jian-jun^{1, 2
, ,}

1.
Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 China
2.
Shenzhen Tsingtech Lithium Technology Co., Ltd, Shenzhen 518057 China

More Information

Author Bio:
ZHANG Rui. E-mail: zrhitsz22334@163.com

Corresponding author: CHEN Jian-jun，professor. E-mail: chenjj08@126.com

摘要

摘要: 随着新能源汽车迅速发展，动力锂离子电池应用越来越广泛，大量锂电池也迎来退役高峰期，废旧锂电池的回收综合利用引起各国高度关注。废旧锂电池石墨负极层状结构基本未变化，因此回收时不需高温石墨化，只需关注其内部杂质的去除。本文将废旧石墨负极热处理、超声分离和酸浸处理后，创新性地采用电化学处理将内部金属杂质深度去除。对比不同回收阶段的石墨，发现石墨中有机杂质的存在会严重影响各项电化学性能，微量Cu、Fe等无机杂质的存在对初始放电比容量影响不大，但会降低石墨的循环稳定性。最终回收的石墨内部主要金属杂质含量低于20 mg/kg，在0.1 C倍率下放电比容量达到358.7 mAh/g，循环150圈后容量保持率为95.85%。对比已报道的废旧石墨回收方法，此方法可深度去除石墨负极内部杂质，解决了目前酸碱用量大、除杂不彻底、能耗高等问题，回收再生石墨负极电化学性能较好，为废旧锂电池石墨负极提供了一条新的回收再生路径。
- 电池回收 /
- 废旧石墨 /
- 电化学除杂 /
- 电化学性能 /
- 杂质影响
Abstract: The application of lithium-ion batteries (LIBs) is becoming increasingly widespread, and a large number of LIBs are entering the peak period of retirement. The recycling and comprehensive utilization of spent LIBs has attracted high attention from countries around the world. Due to the graphite anode in spent LIBs, it’s recycling does not require high-temperature graphitization, the unchanged layered structure of and only focuses on the removal of internal impurities. In this study, we innovatively used electrochemical treatment to deeply remove internal metal impurities after heat treatment, ultrasonic separation and acid leaching of spent graphite. By comparing and analyzing the graphite in different recovery stages, it is found that the presence of organic impurities in graphite will seriously affect the electrochemical performance. The presence of trace inorganic impurities such as Cu and Fe has little effect on the initial discharge specific capacity, but it will reduce the cycle stability of graphite. The content of main metal impurities in the final recycled graphite is less than 20 mg/kg. The discharge specific capacity reaches 358.7 mAh/g at 0.1 C, and the capacity remains 95.85% after 150 cycles. Compared with the reported methods for recycling spent graphite, this method can deeply remove impurities inside the graphite, solve the current problems of high acid and alkali consumption, incomplete impurity removal and high energy consumption. The recycled graphite anode shows good electrochemical performance, which provides, a new recycling and regeneration path for spent LIBs graphite anode.
- Battery recycling /
- Spent graphite /
- Electrochemical impurity removal /
- Electrochemical performance /
- Effect of impurities

HTML全文

图 1 (a) SG在空气气氛下的TG-DSC曲线；(b) SG、PG、AG、EG在N₂气氛下的TG曲线；(c) SG、PG、AG与EG的XRD图；(d) SG、PG、AG与EG的局部XRD图

Figure 1. (a)TG-DSC curve of SG in air atmosphere; (b)TG curves of SG, PG, AG and EG in N₂ atmosphere; (c) XRD patterns of SG, PG, AG and EG; (d) XRD patterns of SG, PG, AG and EG

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图 2 SG、PG、AG与EG的Raman谱图

Figure 2. Characterization of recycled anode graphite by Raman spectrometry

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图 3 (a,b) SG、PG、AG和(g,h) EG的SEM照片。(i) SG、(j) PG、(k) AG和EG的C、O、Cu元素分布

Figure 3. Characterization of recycled anode graphite by SEM and EDS. SEM images of (a,b) SG, (c,d) PG, (e,f) AG and (g,h) EG. (i) The distribution of C, O and Cu elements in SG、(j) PG、(k) AG and (l) EG

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图 4 (a) EG的CV曲线和及其(b)0V~0.5V局部放大

Figure 4. (a) The CV curve of EG and (b) it’s locally amplified at 0 ~ 0.5 V

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图 5 (a) SG、PG、AG和EG的循环曲线(0.1 C)；(b) SG、PG、AG和EG的首图充放电曲线；(c) AG和EG的循环曲线(1 C)；(d) EG的倍率性能

Figure 5. (a) The cycling performance of SG, PG, AG and EG at 0.1 C; (b) The first cycle charge-discharge curves of SG, PG, AG and EG; (c) The cycling performance of AG and EG at 1 C; (d) Rate performance of EG

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图 6 SG和EG的EIS测试结果

Figure 6. EIS results of SG and EG

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图 7 电化学除杂示意图

Figure 7. Schematic of the impurity remove from recycled anode graphite by electrochemical method

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表 1 SG、AG和EG的ICP检测结果/（mg/kg）

Table 1. Characterization of SG, AG and EG by ICP /(mg/kg)

Li Al Cu Ni Co Mn Fe

SG 13309 521 4860 639 231 340 219
AG 519 68 1012 8 <5 <5 116
EG 81 13 14 <5 <5 <5 13

下载: 导出CSV

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