从报废NCA型锂离子动力电池中回收金属的研究
收稿日期: 2025-01-06
网络出版日期: 2025-02-17
基金资助
国家自然科学基金项目(51864032);沈阳材料科学国家（联合）实验室－有色金属加工与再利用国家重点实验室联合基金项目(18LHZD002)
Study on recovery of metals from spent NCA-type lithium-ion power batteries
Received date: 2025-01-06
Online published: 2025-02-17
鉴于NCA型锂离子动力电池在新能源领域的广泛应用及其蕴含元素的高价值性，为提高废旧电池回收技术的先进性，提出了采用“焙烧-水浸出”技术替代湿法回收工艺中的酸性浸出技术，并通过TG-DSC、XRD、XPS、SEM-EDS、热力学分析及ICP-OES等方法研究回收过程中的物相变化和影响Li、Co、Ni元素回收率的主要因素。研究结果表明，混合焙烧过程发生化学转变产生新物相，并伴随有明显的失重和吸热现象。当LiNi0.8Co0.15Al0.05O2（NCA）与KHSO4质量比从1:0.14减小到1:1.84时，物相变化规律为Li：LiNi0.8Co0.15Al0.05O2→Li0.21Co0.79O和KLiSO4；Ni：LiNi0.8Co0.15Al0.05O2→NiO和K2Ni2（SO4）3；Co：LiNi0.8Co0.15Al0.05O2→Li0.21Co0.79O和K2Co2（SO4）3。Ni、Co元素价态演变为Ni：+2，+3→+2；Co：+3→+2，+3。在NCA与KHSO4质量比为1:1.84，600 ℃下焙烧0.5 h，50 ℃下水浸0.5 h、搅拌速率为120 r/min、液固比（mL/g）为25:1的条件下，Li、Co和Ni的浸出率分别为95.10%、52.68%和10.42%。与传统湿法工艺相比，该技术避免了强酸的使用，同时通过选择性提取Li元素，提高了有价金属的整体回收率，有助于提高报废锂离子动力电池回收利用的经济性。
关键词： 报废锂离子电池; LiNi0.8Co0.15Al0.05O2; 焙烧-水浸; 物相变化; 金属回收
李彦强 , 王大辉 , 陈怀敬 , 彭小平 , 宋晓龙 . 从报废NCA型锂离子动力电池中回收金属的研究[J]. 无机盐工业, 2025 , 57(10) : 24 -31 . DOI: 10.19964/j.issn.1006-4990.2025-0019
Due to the widespread application of NCA-type lithium-ion power batteries in the new energy field and the high value of the elements they contained，in order to enhance the advancement of recycling technologies for used batteries，the "roasting-water leaching" technology was proposed to replace the acid leaching technology in the hydrometallurgical recycling process.The phase changes during the recycling process and the main factors affecting the recovery rates of Li，Co，and Ni elements were studied through TG-DSC，XRD，XPS，SEM-EDS，thermodynamic analysis，and ICP-OES.The research results showed that a chemical transformation occured during the mixed roasting process，generating new phases，accompanied by obvious weight loss and endothermic phenomena.When the mass ratio of LiNi0.8Co0.15Al0.05O2（NCA） to KHSO4 reduced from 1:0.14 to 1:1.84，the phase change rules were as follows Li：LiNi0.8Co0.15Al0.05O2→Li0.21Co0.79O and KLiSO4；Ni：LiNi0.8Co0.15Al0.05O2→NiO and K2Ni2（SO4）3；Co：LiNi0.8Co0.15Al0.05O2→Li0.21Co0.79O and K2Co2（SO4）3.The valence states of Ni and Co elements evolved as follows Ni：+2，+3→+2；Co：+3→+2，+3.Under the conditions of a mass ratio of NCA to KHSO4 of 1:1.84，roasting at 600 ℃ for 0.5 h，water leaching at 50 ℃ for 0.5 h，a stirring rate of 120 r/min，and a liquid-to-solid ratio of 25:1 （mL/g），the leaching rates of Li，Co，and Ni were 95.10%，52.68%，and 10.42%，respectively.Compared to traditional hydrometallurgical processes，this technology avoided the use of strong acids and enhanced the overall recovery rate of valuable metals through the selective extraction of lithium elements，contributing to the economic efficiency of recycling spent lithium-ion power batteries.
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