Choline chloride-lactic acid-ascorbic acid (ChCl-LA-AA) based green deep eutectic solvent for leaching LiMn2O4 cathode material of spent Li-ion batteries

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy Pub Date : 2025-07-07 DOI:10.1016/j.hydromet.2025.106529

Jasreen Kaur Jasmel Singh , Masud Rana , Md Ishtiaq Hossain Khan , Young Tae Jo, Jeong-Hun Park

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Abstract

The application of lithium manganese oxide (LMO) as a cathode material in Li-ion batteries (LIBs) is increasing due to its affordability, safety, nontoxicity, and high energy storage capabilities. Although its use in electric vehicles (EVs) and portable devices is proliferating, research on recycling valuable metals from spent batteries of this type remains limited. Therefore, this study investigates the recycling of lithium (Li) and manganese (Mn) from spent LiMn₂O₄ cathode materials using a choline chloride and lactic acid (ChCl-LA) deep eutectic solvent (DES) in the presence of various reducing agents such as ascorbic acid (AA), glucose, and formic acid (FA). The compositions of the spent cathode LiMn₂O₄ material, solid residue, and the leachate obtained post-leaching were analyzed using ICP-OES, XPS, SEM-EDS, and XRD analyses. Results indicated that about 100 % leaching efficiencies of both Li and Mn metals were achieved at 90 °C, 1 h, 20 g/L solid-to-liquid ratio and a 1:2:1 M ratio of ChCl-LA-AA. The XRD analysis results showed the presence of minor peaks of manganese oxide in the solid residues obtained from glucose and FA leaching, while the LiMn₂O₄ peaks are absent after the treatment of AA, confirming the effective extraction of metallic elements. Meanwhile, the SEM-EDS analysis showed the raw LiMn₂O₄ material had agglomerated nanoparticles, while the solid residues exhibited increased porosity and reduced Mn content (26.1 wt% for glucose and 23.9 wt% for FA). The solid residue obtained after leaching with AA showed a significant increase in carbon content (82.1 %) and a decrease in Mn (1.42 %). The XPS spectra further confirmed the reduction of manganese (III) or manganese (IV) oxidation states into manganese (II) state and almost complete leaching of Mn and Li. Finally, a detailed mechanism for Mn and Li leaching from the spent LiMn₂O₄ was proposed. The recycling process applied in this study is shown to be feasible and promising for broader application.

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氯化胆碱-乳酸-抗坏血酸（ChCl-LA-AA）基绿色深共晶溶剂浸出废锂离子电池正极材料LiMn2O4

锂锰氧化物（LMO）作为锂离子电池（LIBs）正极材料的应用越来越多，因为它具有可负担性、安全性、无毒性和高能量存储能力。尽管它在电动汽车（ev）和便携式设备中的应用正在激增，但从这类废旧电池中回收有价值金属的研究仍然有限。因此，本研究研究了在各种还原剂如抗坏血酸（AA）、葡萄糖和甲酸（FA）的存在下，使用氯化胆碱和乳酸（ChCl-LA）深度共晶溶剂（DES）从废LiMn2O4正极材料中回收锂（Li）和锰（Mn）。利用ICP-OES、XPS、SEM-EDS和XRD分析了废阴极LiMn2O4材料、固体残渣和浸出液的组成。结果表明，在90℃、1 h、料液比20 g/L、ChCl-LA-AA浓度为1:2:1的条件下，Li和Mn金属的浸出效率均达到100%左右。XRD分析结果表明，葡萄糖和FA浸出的固体残渣中存在少量的氧化锰峰，而AA处理后没有出现LiMn2O4峰，证实了金属元素的有效提取。同时，SEM-EDS分析表明，原始LiMn2O4材料具有团聚的纳米颗粒，而固体残留物的孔隙率增加，Mn含量降低（葡萄糖为26.1% wt%， FA为23.9%）。AA浸出后得到的固体渣碳含量显著增加（82.1%），Mn含量显著降低（1.42%）。XPS光谱进一步证实锰（III）或锰（IV）氧化态还原为锰（II）态，Mn和Li几乎完全浸出。最后，提出了从废LiMn2O4中浸出Mn和Li的详细机理。本研究采用的回收工艺是可行的，具有广阔的应用前景。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Hydrometallurgy 工程技术-冶金工程

CiteScore

9.50

自引率

6.40%

发文量

144

审稿时长

3.4 months

期刊介绍： Hydrometallurgy aims to compile studies on novel processes, process design, chemistry, modelling, control, economics and interfaces between unit operations, and to provide a forum for discussions on case histories and operational difficulties. Topics covered include: leaching of metal values by chemical reagents or bacterial action at ambient or elevated pressures and temperatures; separation of solids from leach liquors; removal of impurities and recovery of metal values by precipitation, ion exchange, solvent extraction, gaseous reduction, cementation, electro-winning and electro-refining; pre-treatment of ores by roasting or chemical treatments such as halogenation or reduction; recycling of reagents and treatment of effluents.