使用硫酸和草酸选择性浸出废弃锂离子电池中的锂

余海军; 王东兴; 饶帅; 段丽娟; 邵彩茹; 涂小慧; 马致远; 曹洪杨; 刘志强

doi:10.1007/s12613-023-2741-3

Volume 31 Issue 4

Apr. 2024

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文章导航 > 矿物冶金与材料学报（英文） > 2024 > 31(4): 688-696

Haijun Yu, Dongxing Wang, Shuai Rao, Lijuan Duan, Cairu Shao, Xiaohui Tu, Zhiyuan Ma, Hongyang Cao, and Zhiqiang Liu, Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid, Int. J. Miner. Metall. Mater., 31(2024), No. 4, pp. 688-696. https://doi.org/10.1007/s12613-023-2741-3

Cite this article as:

Haijun Yu, Dongxing Wang, Shuai Rao, Lijuan Duan, Cairu Shao, Xiaohui Tu, Zhiyuan Ma, Hongyang Cao, and Zhiqiang Liu, Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid, Int. J. Miner. Metall. Mater., 31(2024), No. 4, pp. 688-696. https://doi.org/10.1007/s12613-023-2741-3

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研究论文

使用硫酸和草酸选择性浸出废弃锂离子电池中的锂

1)
暨南大学先进耐磨蚀及功能材料研究院，广州 510632，中国
2)
广东省科学院资源利用与稀土开发研究所，广州 510650，中国
3)
稀有金属分离与综合利用国家重点实验室，广州 510650，中国
4)
广东省稀土开发及应用研究重点实验室，广州 510650，中国

通讯作者:
王东兴 E-mail: 710797438@qq.com

涂小慧 E-mail: 3162510484@qq.com

文章亮点

(1) 利用硫酸和草酸协同从废弃锂电池中选择性浸锂。

(2) 系统地研究了浸出条件对选择性浸锂的影响规律。

(3) 揭示了硫酸-草酸体系选择性浸锂的机理。

中文摘要

近年来，随着锂离子电池的广泛应用，未来锂离子电池退役量将剧增。考虑到环境保护和资源循环利用，废弃锂离子电池的回收利用变得迫在眉睫。现有废弃锂离子电池湿法冶金回收工艺通常采用还原酸浸法将有价金属同时提取到浸出液中，后续再通过沉淀、萃取、反萃等工艺分离各有价金属。这类工艺流程较长，且锂在流程最末端回收，锂的损失率高。本文旨在开发一种新的选择性优先浸锂工艺，利用硫酸和草酸协同作用选择性浸出废弃锂电池中的锂，有利于锂的优先回收。在最佳浸出条件下（浸出时间1.5 h、浸出温度70°C、液固比4 mL/g、硫酸配比1.3、草酸配比1.3），锂的浸出率为89.6%，选择性浸出效果较好。经ICP成分分析、XRD物相分析和SEM显微分析推断出，在硫酸体系中的草酸起到了还原剂与沉淀剂的作用。草酸可降低锂离子电池正极材料中部分镍、钴、锰的价态从而破坏正极材料的层状结构，有利于锂的浸出；同时，草酸根与溶液中的镍、钴、锰结合形成草酸盐留在渣中，从而实现选择性浸锂。

关键词:

Research Article

Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid

+ Author Affiliations

1)
Institute of Advanced Wear & Corrosion Resistant and Functional Materials, Jinan University, Guangzhou 510632, China
2)
Institute of Resources Utilization and Rare Earth Development, Guangdong Academy of Sciences, Guangzhou 510650, China
3)
State Key Laboratory of Separation and Comprehensive Utilization of Rare Metals, Guangzhou 510650, China
4)
Guangdong Province Key Laboratory of Rare Earth Development and Application, Guangzhou 510650, China

All the authors have no financial or commercial conflicts.

Corresponding authors:
Dongxing Wang E-mail: 710797438@qq.com

Xiaohui Tu E-mail: 3162510484@qq.com
Received: 13 July 2023; Revised: 5 September 2023; Accepted: 8 September 2023; Available online: 9 September 2023

Abstract

Abstract

Traditional hydrometallurgical methods for recovering spent lithium-ion batteries (LIBs) involve acid leaching to simultaneously extract all valuable metals into the leachate. These methods usually are followed by a series of separation steps such as precipitation, extraction, and stripping to separate the individual valuable metals. In this study, we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids. Under optimal leaching conditions (leaching time of 1.5 h, leaching temperature of 70°C, liquid–solid ratio of 4 mL/g, oxalic acid ratio of 1.3, and sulfuric acid ratio of 1.3), the lithium leaching efficiency reached 89.6%, and the leaching efficiencies of Ni, Co, and Mn were 12.8%, 6.5%, and 21.7%. X-ray diffraction (XRD) and inductively coupled plasma optical emission spectrometer (ICP-OES) analyses showed that most of the Ni, Co, and Mn in the raw material remained as solid residue oxides and oxalates. This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.
- selective leaching;
- oxalic acid;
- sulfuric acid;
- spent lithium-ion batteries

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