Low/no-corrosion leaching of spent lithium-ion battery cathode materials in hydrothermal water using amino acid or mixed organic acids as the leachant

以氨基酸或混合有机酸为浸出液对废旧锂离子电池正极材料进行低/无腐蚀热水浸出

• 批准号: 21K12302
• 负责人: 鄭 慶新
• 金额: $ 2.66万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2021
• 资助国家: 日本
• 起止时间: 2021-04-01 至 2024-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-21K12302/
• 关键词: Lithium-ion batteries; Continuous leaching; Hydrothermal leaching; Mixed organic acid; Kinetic study; Metal isolation; Metal recovery; Acid corrosion; Glycine; Citric acid; Mixed organic acids; Unreacted core model; Organic acid

Continuous hydrothermal leaching of spent LiNixCoyMn1-x-yO2 (NCM) cathode materials was successfully achieved employing a flow system and using a mixture of citric acid and glycine (10%/90%, referred to as acid X) as the leaching agent. After feeding the slurry of raw materials for 50 mins, the leaching efficiencies of Li, Co, Ni, and Mn achieved >90% and the pH value of the obtained leachate was kept at around 6.5. That was the first time to realize the continuous acid leaching of spent NCM cathode materials through a green process with high efficiency and low/no acid corrosion.A kinetic study for hydrothermal leaching of spent NCM cathode materials with acid X was conducted using a shrinking unreacted core model. Diffusion within the product layer was found to be the rate-limiting step for leaching Li, Co, Ni, and Mn. According to the determined reaction rates and Arrhenius equations, the activation energies for leaching Li, Co, Ni, and Mn were calculated.Furthermore, hydrothermal leaching of LiCoO2/LiNiO2 (LCO/LNO) cathode materials with citric acid was performed and the metal components in the obtained leachate were separated in order using a series of precipitants. Finally, the recovery rates of Ni, Co, and Li were 97.2, 96.1, and 94.1%, respectively, with the purities of Ni, Co, and Li in the corresponding precipitate being 96.3, 96.2, and 99.9%, respectively. With this success, an upgraded hydrometallurgical method, composed of hydrothermal leaching and precipitation separation steps, was officially launched for LIB recycling and is subject to further development.

采用流动系统并使用柠檬酸和甘氨酸的混合物（10%/90%，简称酸X）作为浸出剂，成功实现了废LiNixCoyMn1-x-yO2（NCM）正极材料的连续水热浸出。原料浆投入50 min后，Li、Co、Ni、Mn的浸出率均达到>90%，且浸出液的pH值保持在6.5左右。首次实现了废三元正极材料的连续酸浸，高效、低/无酸腐蚀的绿色工艺。核心模型。研究发现产物层内的扩散是浸出锂、钴、镍和锰的限速步骤。根据确定的反应速率和阿伦尼乌斯方程，计算了浸出Li、Co、Ni和Mn的活化能。此外，用柠檬酸对LiCoO2/LiNiO2（LCO/LNO）正极材料进行了水热浸出，并分析了金属成分。使用一系列沉淀剂将获得的渗滤液按顺序分离。最终，Ni、Co和Li的回收率分别为97.2、96.1和94.1%，相应沉淀物中Ni、Co和Li的纯度分别为96.3、96.2和99.9%。凭借这一成功，由水热浸出和沉淀分离步骤组成的升级湿法冶金方法正式启动用于锂离子电池回收，并有待进一步开发。

项目成果

Metal Recovery of LiCoO2/LiNiO2 Cathode Materials by Hydrothermal Leaching and Precipitation Separation

• DOI: 10.1021/acssuschemeng.2c04259
• 发表时间: 2022-09
• 期刊: ACS Sustainable Chemistry & Engineering
• 作者: Akitoshi Nakajima;Qingxin Zheng;Tetsufumi Ogawa;Seiya Hirama;Masaru Watanabe

METAL RECOVERY OF THE LEACHATE OBTAINED FROM COMMERCIAL CATHODE MATERIALS BY HYDROTHERMAL LEACHING

水热浸出商业正极材料浸出液的金属回收

• 发表时间: 2022
• 作者: NAKAJIMA Akitoshi;ZHENG Qingxin;OGAWA Tetsufumi;NAKAYASU Yuta;WATANEBE Masaru
• 通讯作者: WATANEBE Masaru

LOW/NO-CORROSION LEACHING OF SPENT LITHIUM-ION BATTERY CATHODE MATERIALS BY HYDROTHERMAL METHOD USING AMINO ACID ORMIXED ORGANIC ACIDS AS THE LEACHANT

以氨基酸或混合有机酸为浸出剂的水热法低/无腐蚀浸出废旧锂离子电池正极材料

• 发表时间: 2022
• 作者: ZHENG Qingxin;OGAWA Tetsufumi;NAKAJIMA Akitoshi;WATANABE Masaru
• 通讯作者: WATANABE Masaru

Application of Hydrothermal Leaching Technology to Spent LIB Cathode Materials withCitric Acid Using Batch-type Device and Flow System

间歇式装置和流动系统柠檬酸水热浸出锂离子电池正极材料的应用

• 发表时间: 2022
• 作者: ,Masaru Watanabe;Qingxin Zheng;Kensuke Shibazaki;Tetsufumi Ogawa;Atsushi Kishita;Yuya Hiraga
• 通讯作者: Yuya Hiraga

クエン酸マンガンの製造方法

柠檬酸锰的制造方法

• 发表时间: 2021