废锂离子电池碳热还原优先提锂工艺优化

doi:10.16085/j.issn.1000-6613.2023-0539

摘要/Abstract

摘要：

对废旧三元锂离子电池正极材料采用碳热还原-通二氧化碳水浸的工艺进行优先提锂。本文采用单一变量法探究焙烧过程中焙烧温度、焙烧时长、有效加碳量及水浸过程中水浸时长、水浸固液比、二氧化碳流量、逆流水洗级数等参数改变带来的金属元素浸出率的影响。在焙烧温度700℃、焙烧时长120min、有效加碳量（75.56%含碳量的炭粉）为14%（质量分数）、液固比10mL/g、水浸时长180min、二氧化碳通入量100mL/min、三级逆流水洗的最佳条件下，可以达到锂的浸出率为96.31%，钴、镍、锰金属的浸出率均低于0.1%。同时考察了该工艺对于不同型号的废三元锂离子电池回收的适用性，发现提锂效果均在90%以上，具有良好的原料适应性。此外，通过X射线衍射、透射电子显微镜、扫描电子显微镜探究碳热还原前后的物相变化。

关键词: 废旧三元锂离子电池, 碳热还原, 优先提锂, 浸出率

Abstract:

The process of carbon thermal reduction-CO₂ water immersion was used to preferentially extract lithium from the cathode materials of spent ternary lithium ion batteries. The variables were changed individually such as roasting temperature, roasting duration, effective carbon addition, water leaching duration, solid liquid ratio, CO₂ flow rate and countercurrent water washing order to investigate the effects on the leaching rate of metal elements. When roasting temperature was 700℃, roasting time was 120min, effective carbon addition(75.56% carbon powder) was 14% (weight), liquid solid ratio was 10mL/g, water leaching time was 180min, CO₂ flow rate was 100mL/min and three stage countercurrent water washing, the leaching rate of lithium could reach 96.31%, and the leaching rates of cobalt, nickel and manganese metals were all lower than 0.1%. This process was applicable to different types of NCM batteries. In addition, the phase changes before and after carbothermal reduction were investigated by XRD, TEM and SEM-EDS.

Key words: waste ternary lithium ion batteries, carbothermal reduction, priority lithium extraction, leaching rate

中图分类号:

周铭贤, 叶小舟. 废锂离子电池碳热还原优先提锂工艺优化[J]. 化工进展, 2024, 43(4): 2174-2182.

ZHOU Mingxian, YE Xiaozhou. Optimization of preferential lithium extraction from waste ternary lithium ion batteries by carbothermal reduction[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 2174-2182.

图/表 17

参考文献 34

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材料	研究特色	参考文献
废LiCoO₂电池负极石墨	对废锂电池正极材料的碳热还原反应进行了机理研究，提出了氧八面体坍缩模型，且耦合反应理论和晶体结构分析表明，石墨确实促进了锂钴氧化物的热解	Mao等^[18]，2018
废NCM电池褐煤	用褐煤对电池正极材料进行焙烧，用碳酸化水浸出法选择性提锂，最后用硫酸浸出残渣；锂的浸出率超过80%，Ni、Co和Mn的提取率超过96%	Zhang等^[19]，2018
废NCM电池炭黑	提出了还原焙烧和分步浸出的技术路线，在最佳条件下，Li、Ni、Co和Mn的浸出率分别高达93.68%、99.56%、99.87%和99.9%，并通过收缩岩心模型分析了酸浸动力学	Liu等^[20]，2019
废NCM电池石墨粉末	提出了微波碳热还原的技术路线，结果表明在500W微波能量和30min时间的条件下，可以有效地还原过渡金属；Co、Ni和Mn的回收率达到97%，Li的回收率达到99%	Fu等^[21]，2020
废NCM电池甲烷气体	提出了甲烷还原焙烧-碳酸化水浸-酸浸的技术路线，在焙烧温度600℃、时间30min、甲烷流量300mL/min的条件下，锂的浸出率为88%，Mn、Ni和Co的浸出率均超过98%	Yang等^[22]，2021
废LiCoO₂电池废聚乙烯、生物质和煤	评估了三种不同的碳质材料与废LiCoO₂电池共热解回收金属的方法，效果依次为煤>生物质>聚乙烯；在800℃的热解温度和10min的停留时间下，获得了Co（96.8%）和Li（88.7%）的最佳回收率	Lai等^[23]，2022
废NCM电池导电剂（乙炔黑）和凝结剂（PVDF）	使用负极活性材料中含有的有机物作为还原剂，结果表明，PVDF和乙炔黑都可以将高价金属还原为低价氧化物或单质，且乙炔黑具有比PVDF更强的热还原能力	Jiang等^[24]，2022
废NCM电池炭粉	将废三元锂电池与炭粉混合进行无氧焙烧后通过酸浸出锂、钴、镍、锰，研究了该过程的焙烧热力学和酸浸动力学	Gu等^[25]，2022
废NCM电池木质纤维素	使用木质纤维素生物质产生热解气体还原废锂电池正极材料，其中CO起主要作用；例如在废LiCoO₂电池中，在500℃下锂回收效率达到99.99%，纯度达到98.3%	Zhou等^[26]，2023
废NCM电池碳质材料（煤）	提出了碳热还原与多级浸出结合的方法，电池材料中的锂被还原为Li₂CO₃和LiAlO₂，分别通过水浸、碱浸浸出；当铝为4.05%时，锂的综合回收率为87.15%	Zhang等^[27]，2023
废NCM电池和废LiCoO₂电池的混合物生物质还原剂废竹粉	使用新型还原剂废竹粉对电池正极材料进行还原，使用还原焙烧-水浸出和低浓度酸浸出的技术路线，得出最佳焙烧条件为650℃、废竹粉/废正极材料质量比为1∶1，锂的回收率超过99%	Liu等^[28]，2023

材料	研究特色	参考文献
废LiCoO₂电池负极石墨	对废锂电池正极材料的碳热还原反应进行了机理研究，提出了氧八面体坍缩模型，且耦合反应理论和晶体结构分析表明，石墨确实促进了锂钴氧化物的热解	Mao等^[18]，2018
废NCM电池褐煤	用褐煤对电池正极材料进行焙烧，用碳酸化水浸出法选择性提锂，最后用硫酸浸出残渣；锂的浸出率超过80%，Ni、Co和Mn的提取率超过96%	Zhang等^[19]，2018
废NCM电池炭黑	提出了还原焙烧和分步浸出的技术路线，在最佳条件下，Li、Ni、Co和Mn的浸出率分别高达93.68%、99.56%、99.87%和99.9%，并通过收缩岩心模型分析了酸浸动力学	Liu等^[20]，2019
废NCM电池石墨粉末	提出了微波碳热还原的技术路线，结果表明在500W微波能量和30min时间的条件下，可以有效地还原过渡金属；Co、Ni和Mn的回收率达到97%，Li的回收率达到99%	Fu等^[21]，2020
废NCM电池甲烷气体	提出了甲烷还原焙烧-碳酸化水浸-酸浸的技术路线，在焙烧温度600℃、时间30min、甲烷流量300mL/min的条件下，锂的浸出率为88%，Mn、Ni和Co的浸出率均超过98%	Yang等^[22]，2021
废LiCoO₂电池废聚乙烯、生物质和煤	评估了三种不同的碳质材料与废LiCoO₂电池共热解回收金属的方法，效果依次为煤>生物质>聚乙烯；在800℃的热解温度和10min的停留时间下，获得了Co（96.8%）和Li（88.7%）的最佳回收率	Lai等^[23]，2022
废NCM电池导电剂（乙炔黑）和凝结剂（PVDF）	使用负极活性材料中含有的有机物作为还原剂，结果表明，PVDF和乙炔黑都可以将高价金属还原为低价氧化物或单质，且乙炔黑具有比PVDF更强的热还原能力	Jiang等^[24]，2022
废NCM电池炭粉	将废三元锂电池与炭粉混合进行无氧焙烧后通过酸浸出锂、钴、镍、锰，研究了该过程的焙烧热力学和酸浸动力学	Gu等^[25]，2022
废NCM电池木质纤维素	使用木质纤维素生物质产生热解气体还原废锂电池正极材料，其中CO起主要作用；例如在废LiCoO₂电池中，在500℃下锂回收效率达到99.99%，纯度达到98.3%	Zhou等^[26]，2023
废NCM电池碳质材料（煤）	提出了碳热还原与多级浸出结合的方法，电池材料中的锂被还原为Li₂CO₃和LiAlO₂，分别通过水浸、碱浸浸出；当铝为4.05%时，锂的综合回收率为87.15%	Zhang等^[27]，2023
废NCM电池和废LiCoO₂电池的混合物生物质还原剂废竹粉	使用新型还原剂废竹粉对电池正极材料进行还原，使用还原焙烧-水浸出和低浓度酸浸出的技术路线，得出最佳焙烧条件为650℃、废竹粉/废正极材料质量比为1∶1，锂的回收率超过99%	Liu等^[28]，2023

元素	质量分数/%
Li	7.12
Co	12.26
Ni	37.72
Mn	12.34
Al	0.35
C	0.89
F	0.3

元素	质量分数/%
Li	7.12
Co	12.26
Ni	37.72
Mn	12.34
Al	0.35
C	0.89
F	0.3

名称	化学式	规格	生产商
氢氧化钠	NaOH	优级纯	通用试剂
碳酸钠	Na₂CO₃	分析纯	通用试剂
乙醇	C₂H₅OH	分析纯	阿拉丁
氮气	N₂	145bar^①	液化空气
二氧化碳	CO₂	145bar^①	液化空气
炭粉	C	58.79%	麦克林
		75.56%	阿达玛斯
		82.52%	通用试剂