新兴湿法退役锂电池正极材料回收技术研究进展

doi:10.16085/j.issn.1000-6613.2023-0547

摘要/Abstract

摘要：

退役锂电池中的钴、镍、锂等稀有金属的绿色高效回收利用逐渐成为国内外研究的重点。传统酸浸法具有能源成本低、金属回收纯度高和效率高的优点，但使用腐蚀性强酸和昂贵萃取物，反应时间长且产生废酸、污泥和高盐溶液等二次废物。本文总结了传统酸浸法中绿色浸取剂和还原剂以及低共熔溶剂（DES）和超临界流体（SCF）两种新兴的湿法冶金技术对高效绿色回收锂电池正极材料的应用。阐明了微波超声辅助手段和选择性浸取回收工艺分别对改善浸取工况和简化分离回收程序的重要作用。并重点介绍了超临界水（SCW）和超临界二氧化碳（SC-CO₂）两种超临界流体降解有机污染物、回收稀有金属并改善合成正极材料的应用，为高效、绿色、低成本回收退役锂电池中稀有金属提供了重要参考价值。

关键词: 浸取, 超临界流体, 选择性, 回收, 湿法冶金, 锂电池, 低共熔溶剂

Abstract:

The green and efficient recycling of cobalt, nickel, lithium and other rare metals in spent lithium batteries has gradually become the focus of research at home and abroad. Traditional acid leaching owns the advantages of low energy cost, high purity of metal recovery and high efficiency. However, traditional acid leaching uses caustic acids and expensive extracts, takes a long time and produces secondary waste such as waste acids, sludge and highly saline solutions. Therefore, this paper focused on the application of green leaching agent and reducing agent in traditional acid-leaching and two novel green solvents of deep eutectic solvent (DES) and supercritical fluid (SCF) in the green and efficient recovery of cathode materials of lithium batteries. The important effects of selective leaching technology on simplifying recovery procedures and assisted means like microwave or ultrasonic on improving leaching conditions were reviewed. The application of supercritical water (SCW) and supercritical carbon dioxide (SC-CO₂) to degrade organic pollutants, recover rare metals, and improve the synthesis of cathode materials was emphasized, which provided important reference value for efficient, green and low-cost recovery of valuable metals from spent lithium batteries.

Key words: leaching, supercritical fluid, selectivity, recovery, hydrometallurgy, lithium-ion batteries, deep eutectic solvent

中图分类号:

TD982

马文君, 张旭, 刘孟顺, 梁志远. 新兴湿法退役锂电池正极材料回收技术研究进展[J]. 化工进展, 2024, 43(4): 2077-2090.

MA Wenjun, ZHANG Xu, LIU Mengshun, LIANG Zhiyuan. Research progress of novel hydrometallurgy in recycling cathode materials from spent lithium-ion batteries[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 2077-2090.

图/表 10

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浸取剂	还原剂	最佳工况	浸取效率	参考文献
3mol/L硫酸	5%（体积分数）的乙醇	90℃，160min，20g/L	99%的Co和Li	[24]
1.5mol/L柠檬酸	200mg橙皮粉	100℃，4h，25g/mL	80%~99%的Li、Ni、Mn、Co	[37]
1.5mol/L苹果酸	600mg/g葡萄籽	180min，80℃，20g/L	92%的Co，99%的Li	[47]
0.5mol/L硫酸	LCO/LFP摩尔比为1∶1	20min，30g/L，50℃	99.9%的Li、Fe、P和92.4%的Co	[48]

浸取剂	还原剂	最佳工况	浸取效率	参考文献
3mol/L硫酸	5%（体积分数）的乙醇	90℃，160min，20g/L	99%的Co和Li	[24]
1.5mol/L柠檬酸	200mg橙皮粉	100℃，4h，25g/mL	80%~99%的Li、Ni、Mn、Co	[37]
1.5mol/L苹果酸	600mg/g葡萄籽	180min，80℃，20g/L	92%的Co，99%的Li	[47]
0.5mol/L硫酸	LCO/LFP摩尔比为1∶1	20min，30g/L，50℃	99.9%的Li、Fe、P和92.4%的Co	[48]

浸取剂	氧化剂	最佳工况	浸取率	参考文献
0.3mol/L硫酸	过氧化氢	H₂SO₄/Li摩尔比为0.57，60℃, 120min	96.85%的Li，0.027%的Fe，1.95%的P	[53]
1.1倍摩尔量硫酸氢钠	2%（体积分数）过氧化氢	65℃，100g/L，15min	99.84%的Li，0.048%的Fe	[54]
0.8mol/L醋酸	6%（体积分数）过氧化氢	120g/L，50℃，30min	95.05%的Li	[52]
10倍质量比的柠檬酸钠	过氧化氢	5h，500r/min	98.9%的Li	[55]
0.6mol/L硫酸	1.3MPa的O₂	H₂SO₄/Li摩尔比为0.52，90min	97%的Li和1%的Fe	[56]

浸取剂	氧化剂	最佳工况	浸取率	参考文献
0.3mol/L硫酸	过氧化氢	H₂SO₄/Li摩尔比为0.57，60℃, 120min	96.85%的Li，0.027%的Fe，1.95%的P	[53]
1.1倍摩尔量硫酸氢钠	2%（体积分数）过氧化氢	65℃，100g/L，15min	99.84%的Li，0.048%的Fe	[54]
0.8mol/L醋酸	6%（体积分数）过氧化氢	120g/L，50℃，30min	95.05%的Li	[52]
10倍质量比的柠檬酸钠	过氧化氢	5h，500r/min	98.9%的Li	[55]
0.6mol/L硫酸	1.3MPa的O₂	H₂SO₄/Li摩尔比为0.52，90min	97%的Li和1%的Fe	[56]

湿法冶金技术	设备成本	试剂成本	选择性	回收效率	污染性
传统酸浸	较低	较低	较低	时间短	腐蚀性强，排放有毒气体
低共熔溶剂	较低	较高	较低	时间中等	低污染
超临界流体	较高	极低	较高	时间极短	可有效降解有机污染物