Article(id=1222493249068060736, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1222493244286558340, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202212209, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=null, receivedDateStr=null, revisedDate=1672329600000, revisedDateStr=2022-12-30, acceptedDate=null, acceptedDateStr=null, onlineDate=1769394703404, onlineDateStr=2026-01-26, pubDate=1692892800000, pubDateStr=2023-08-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1769394703404, onlineIssueDateStr=2026-01-26, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1769394703404, creator=13701087609, updateTime=1769394703404, updator=13701087609, issue=Issue{id=1222493244286558340, tenantId=1146029695717560320, journalId=1210938733613449225, year='2023', volume='52', issue='8', pageStart='1', pageEnd='196', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1769394702264, creator=13701087609, updateTime=1769394819736, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1222493737050169898, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1222493244286558340, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1222493737050169899, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1222493244286558340, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=70, endPage=80, ext={EN=ArticleExt(id=1222493249340690511, articleId=1222493249068060736, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Experimental study on recovery of lithium cobalt oxide cathode by microwave-assisted deep eutectic solvent extraction, columnId=1211002405299294959, journalTitle=Thermal Power Generation, columnName=Thermal energy science research, runingTitle=null, highlight=null, articleAbstract=

The process of conventional hydrometallurgical recovery of lithium batteries not only consumes corrosive acid and long-time reaction, but also produces secondary wastes. In this paper, microwave-assisted deep eutectic solvent (DES) is used to leach and recover valuable metals from cathode material LiCoO2 (LCO). The leaching and recovery process is not only green and low-pollution, but also owns a fast reaction rate, good solubility stability of the valuable metal and high purity of the recovered product. Meanwhile, FT-IR, XRD, ICP-MS, SEM and electrochemical analysis methods are used to explore the mechanism of microwave-assisted DES leaching of valuable metals from LCO. The effects of experimental factors on the extraction efficiency of valuable metals are obtained by orthogonal test method. The degree of influence is DES>temperature>liquid-solid ratio>time. Afterwards, according to the results of orthogonal experiments, the single-factor experiments are successively adopted to explore the optimal experimental conditions for microwave-assisted leaching of valuable metals, 99.86%of Li and 99.05% of Co can be extracted under the condition of choline chlorine-oxalic acid (ChCl-OA), 180 ℃, 10 min and liquid/solid ratio (L/S) of 60 mL/g. At this time, Co exists in the leaching solution as formic acid cobalt. Finally, a green and efficient strategy for extraction of valuable metals from spent LiBs (LCO) through microwave-assisted DES is proposed, which provides an important reference method for recovery of valuable metals from spent lithium-ion batteries.

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传统湿法冶金回收锂电池的过程不仅消耗腐蚀性强酸、反应时间长,且产生二次污染物。使用微波辅助的低共熔溶剂(DES)浸取回收正极材料钴酸锂LiCoO2(LCO)中有价金属,浸取回收过程不仅绿色低污染,且反应速率快、有价金属溶解稳定性好、回收产物纯度较高。同时采用FT-IR、XRD、ICP-MS、SEM和电化学分析方法探究微波辅助DES浸取LCO中有价金属的机理。通过正交实验法得到各个实验因素对有价金属浸取效率的影响程度为DES种类>温度>液固比>时间。根据影响程度采用单因素实验法获得最佳浸取条件为:采用氯化胆碱-草酸在液固比为60 mL/g、温度为180 ℃、时间为10 min条件下可浸取99.86%Li和99.05%Co,此时Co以更稳定的甲酸钴形式存在。最后,提出一条绿色高效的微波辅助DES回收LCO技术路线,为废旧锂电池中有价金属的回收提供重要的参考方法。

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邹小刚(1991),男,硕士,高级工程师,主要研究方向为储能系统的回收与利用,

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邹小刚(1991),男,硕士,高级工程师,主要研究方向为储能系统的回收与利用,

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微波辅助低共熔溶剂浸取回收钴酸锂正极材料的实验研究
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邹小刚 1 , 马文君 2 , 牛国平 1 , 梁志远 2 , 周飞 1 , 赵钦新 2 , 李文锋 1
热力发电 | 热能科学研究 2023,52(8): 70-80
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热力发电 | 热能科学研究 2023, 52(8): 70-80
微波辅助低共熔溶剂浸取回收钴酸锂正极材料的实验研究
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邹小刚1 , 马文君2, 牛国平1, 梁志远2, 周飞1, 赵钦新2, 李文锋1
作者信息
  • 1.西安西热锅炉环保工程有限公司,陕西 西安 710054
  • 2.西安交通大学热流科学与工程教育部重点实验室,陕西 西安 710049
  • 邹小刚(1991),男,硕士,高级工程师,主要研究方向为储能系统的回收与利用,

Experimental study on recovery of lithium cobalt oxide cathode by microwave-assisted deep eutectic solvent extraction
Xiaogang ZOU1 , Wenjun MA2, Guoping NIU1, Zhiyuan LIANG2, Fei ZHOU1, Qinxin ZHAO2, Wenfeng LI1
Affiliations
  • 1.Xi'an TPRI Boiler and Environmental Protection Engineering Co., Ltd., Xi'an 710054, China
  • 2.Key Laboratory of Thermo-Fluid Science and Engineering of MOE, Xi'an Jiaotong University, Xi'an 710049, China
出版时间: 2023-08-25 doi: 10.19666/j.rlfd.202212209
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传统湿法冶金回收锂电池的过程不仅消耗腐蚀性强酸、反应时间长,且产生二次污染物。使用微波辅助的低共熔溶剂(DES)浸取回收正极材料钴酸锂LiCoO2(LCO)中有价金属,浸取回收过程不仅绿色低污染,且反应速率快、有价金属溶解稳定性好、回收产物纯度较高。同时采用FT-IR、XRD、ICP-MS、SEM和电化学分析方法探究微波辅助DES浸取LCO中有价金属的机理。通过正交实验法得到各个实验因素对有价金属浸取效率的影响程度为DES种类>温度>液固比>时间。根据影响程度采用单因素实验法获得最佳浸取条件为:采用氯化胆碱-草酸在液固比为60 mL/g、温度为180 ℃、时间为10 min条件下可浸取99.86%Li和99.05%Co,此时Co以更稳定的甲酸钴形式存在。最后,提出一条绿色高效的微波辅助DES回收LCO技术路线,为废旧锂电池中有价金属的回收提供重要的参考方法。

锂电池  /  低共熔溶剂  /  微波  /  湿法回收  /  钴酸锂

The process of conventional hydrometallurgical recovery of lithium batteries not only consumes corrosive acid and long-time reaction, but also produces secondary wastes. In this paper, microwave-assisted deep eutectic solvent (DES) is used to leach and recover valuable metals from cathode material LiCoO2 (LCO). The leaching and recovery process is not only green and low-pollution, but also owns a fast reaction rate, good solubility stability of the valuable metal and high purity of the recovered product. Meanwhile, FT-IR, XRD, ICP-MS, SEM and electrochemical analysis methods are used to explore the mechanism of microwave-assisted DES leaching of valuable metals from LCO. The effects of experimental factors on the extraction efficiency of valuable metals are obtained by orthogonal test method. The degree of influence is DES>temperature>liquid-solid ratio>time. Afterwards, according to the results of orthogonal experiments, the single-factor experiments are successively adopted to explore the optimal experimental conditions for microwave-assisted leaching of valuable metals, 99.86%of Li and 99.05% of Co can be extracted under the condition of choline chlorine-oxalic acid (ChCl-OA), 180 ℃, 10 min and liquid/solid ratio (L/S) of 60 mL/g. At this time, Co exists in the leaching solution as formic acid cobalt. Finally, a green and efficient strategy for extraction of valuable metals from spent LiBs (LCO) through microwave-assisted DES is proposed, which provides an important reference method for recovery of valuable metals from spent lithium-ion batteries.

lithium battery  /  deep eutectic solvent  /  microwave  /  hydrometallurgy recovery  /  lithium cobalt oxide
邹小刚, 马文君, 牛国平, 梁志远, 周飞, 赵钦新, 李文锋. 微波辅助低共熔溶剂浸取回收钴酸锂正极材料的实验研究. 热力发电, 2023 , 52 (8) : 70 -80 . DOI: 10.19666/j.rlfd.202212209
Xiaogang ZOU, Wenjun MA, Guoping NIU, Zhiyuan LIANG, Fei ZHOU, Qinxin ZHAO, Wenfeng LI. Experimental study on recovery of lithium cobalt oxide cathode by microwave-assisted deep eutectic solvent extraction[J]. Thermal Power Generation, 2023 , 52 (8) : 70 -80 . DOI: 10.19666/j.rlfd.202212209
  • 中国华能集团有限公司总部科技项目(HNKJ21-HF58)
  • 国家重点研发计划项目(2021YFC3001803)
  • 陕西省青年科技新星项目(2022KJXX-51)
2023年第52卷第8期
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doi: 10.19666/j.rlfd.202212209
  • 首发时间:2026-01-26
  • 出版时间:2023-08-25
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  • 修回日期:2022-12-30
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Science and Technology Project of China Huaneng Group Co., Ltd.(HNKJ21-HF58)
中国华能集团有限公司总部科技项目(HNKJ21-HF58)
National Key Research and Development Program(2021YFC3001803)
国家重点研发计划项目(2021YFC3001803)
Shaanxi Youth Science and Technology Nova Project(2022KJXX-51)
陕西省青年科技新星项目(2022KJXX-51)
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    1.西安西热锅炉环保工程有限公司,陕西 西安 710054
    2.西安交通大学热流科学与工程教育部重点实验室,陕西 西安 710049
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https://castjournals.cast.org.cn/joweb/rlfd/CN/10.19666/j.rlfd.202212209
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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