采用Versatic 10从废旧三元锂电池中回收锂及再生正极材料

doi:10.16085/j.issn.1000-6613.2024-1351

摘要/Abstract

摘要：

有效回收废旧锂离子电池中的有价金属，有利于资源的合理利用和环境保护。为了缩短回收过程，直接获得高纯度的再生产品，本文提出了一种基于共萃取和共沉淀的过渡金属萃取、锂回收和正极材料再生新工艺。本文采用盐酸为浸出剂，使用新癸酸（Versatic 10）直接从浸出液中共萃取过渡金属并与锂分离。首先，分别考察了盐酸浓度、固液比、浸出温度、浸出时间对各金属浸出率的影响，以及萃取剂Versatic 10浓度、pH、萃取相比（O∶A）、萃取时间对各金属萃取率的影响。结果表明，盐酸浓度3mol/L、固液比0.02g/mL、温度80℃、时间60min的条件下，Li、Ni、Co、Mn浸出率分别为100%、99.7%、99.3%和99.7%。在Versatic 10体积分数40%、pH=7、相比（O∶A）为1∶1、温度25℃、时间6min的萃取条件下，经过两级萃取镍、钴和锰的总萃取效率分别达到97.47%、96.18%和98.05%。然后，通过沉淀法从萃余液中回收Li，得到纯度为99.2%的Li₂CO₃。最后，用0.4mol/L HCl反萃有机负载相，并通过共沉淀法从反萃液中直接再生正极材料LiNi_1/3Co_1/3Mn_1/3O₂，而不单独分离金属。所制备的可再生正极材料LiNi_1/3Co_1/3Mn_1/3O₂为微球形，不含任何杂质，符合国家LiNi_1/3Co_1/3Mn_1/3O₂生产标准。

关键词: 废旧三元锂电池, 浸取, 共萃取, 新癸酸（Versatic 10）, 共沉淀, 再生, 回收

Abstract:

The effective recovery of valuable metals from waste lithium-ion batteries is beneficial to the rational utilization of resources and environmental protection. In order to shorten the recovery process and directly obtain high purity recycled products, a new process of transition metal extraction, lithium recovery and cathode material regeneration based on co-extraction and coprecipitation was proposed. In this paper, the transition metal was co-extracted from the leaching solution and separated from lithium by using hydrochloric acid as leaching agent and neo-decanoic acid (Versatic 10). The effects of hydrochloric acid concentration, solid-liquid ratio, leaching temperature and leaching time on the extraction rate of each metal were investigated, and the effects of extractant Versatic 10 concentration, pH, extraction ratio and extraction time on the extraction rate of each metal were investigated. The results showed that the leaching rates of Li, Ni, Co and Mn were 100%, 99.7%, 99.3% and 99.7%, respectively, under the conditions of hydrochloric acid concentration 3mol/L, solid-liquid ratio 0.02g/mL, acid leaching temperature 80℃ and acid leaching 60 minutes. The total extraction efficiency of cobalt, nickel and manganese after two-stage extraction was 97.47%, 96.18% and 98.05%, respectively, under the extraction conditions of 40% Versatic 10, pH=7, extraction ratio was 1∶1, temperature was 25℃ and time was 6 minutes. Then, the Li was recovered from the raffinate by precipitation method and the Li₂CO₃ with a purity of 99.2% was obtained. Finally, the organic supported phase was stripped with 0.4mol/L HCl and the cathode material LiNi_1/3Co_1/3Mn_1/3O₂ was regenerated directly from the stripping solution by coprecipitation without separate metal separation. The prepared renewable cathode material LiNi_1/3Co_1/3Mn_1/3O₂ was micro-spherical and did not contain any impurities, which met the national LiNi_1/3Co_1/3Mn_1/3O₂ production standard.

Key words: spent lithium-ion battery, leaching, co-extraction, neo-decanoic acid(Versatic 10), coprecipitation, regeneration, recovery

中图分类号:

X705

李泽鹏, 刘翔, 胡庆喜, 李金蓉, 陈伟. 采用Versatic 10从废旧三元锂电池中回收锂及再生正极材料[J]. 化工进展, 2025, 44(10): 6032-6041.

LI Zepeng, LIU Xiang, HU Qingxi, LI Jinrong, CHEN Wei. Recovery of lithium from spent lithium-ion batteries and regeneration of cathode materials by Versatic 10[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 6032-6041.

图/表 16

表1 废旧锂电池正极粉末的组成

元素	质量分数/%
Li	7.55
Ni	36.32
Co	14.61
Mn	19.54
Al	<0.01
Cu	<0.01
Fe	<0.01
非金属	平衡

图1 废旧锂电池正极粉末形貌以及元素分布

表2 LiNi0.5Co0.2Mn0.3O2正极粉末的组成

元素	质量分数/%
Li	7.60
Ni	36.48
Co	14.99
Mn	19.69
Al	<0.01
Cu	<0.01
Fe	<0.01
非金属	平衡

图2 盐酸浓度、固液比、温度和时间对浸出率的影响

图3 不同新癸酸浓度下金属的萃取率

图4 不同pH下金属的萃取率

图5 不同相比下金属的萃取率

图6 不同萃取时间下金属的萃取率

图7 Ni、Co和Mn萃取等温线及McCabe-Thiele图

表3 两级萃取实验结果

萃取级数	萃余液浓度/mg∙L^-1			萃取率/%
萃取级数	Ni	Co	Mn	Ni	Co	Mn
1	868.9	488.7	1727.1	88.05	83.21	61.28
2	183.9	111.2	87.0	97.47	96.18	98.05

图8 回收的碳酸锂的XRD图

图9 再生前体Ni1/3Co1/3Mn1/3(OH)2和再生正极材料LiNi1/3Co1/3Mn1/3O2的SEM图

图10 再生前体Ni1/3Co1/3Mn1/3(OH)2和再生正极材料LiNi1/3Co1/3Mn1/3O2的XRD图

图11 再生正极材料LiNi1/3Co1/3Mn1/3O2的EDS图

表4 再生前体Ni1/3Co1/3Mn1/3(OH)2和再生正极材料LiNi1/3Co1/3Mn1/3O2的组成（质量分数，%）

样品	组成元素
样品	Li	Ni	Co	Mn	Fe	Mg	Ca
Ni_1/3Co_1/3Mn_1/3(OH)₂	—	23.78	23.82	23.51	0.003	0.006	0.004
LiNi_1/3Co_1/3Mn_1/3O₂	7.51	19.93	19.84	19.91	0.004	0.005	0.004

图12 再生正极材料LiNi1/3Co1/3Mn1/3O2的循环性能和库仑效率

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