机械化学法回收废旧锂离子电池正极材料中有价金属的研究进展

doi:10.11949/0438-1157.20231001

摘要/Abstract

摘要：

随着锂离子电池（LIBs）大规模退役，废旧电池对环境的二次危害已成为一个亟待解决的问题，且其中的有价金属回收受到了广泛关注和研究。针对LIBs回收工艺的最新进展进行了综述，分析总结了火法冶金、湿法冶金等回收工艺存在的问题。重点对机械化学法（MC）回收正极材料中有价金属的现状进行全面分析和梳理，包括机械化学技术回收磷酸铁锂（LFP）、钴酸锂（LCO）、镍钴锰三元锂（NCM）、锂锰氧化物（LMO）等正极材料方面的研究，为LIBs回收工艺进展提供了参考。

关键词: 锂离子电池, 机械化学, 正极材料, 有价金属

Abstract:

With the large-scale decommissioning of lithium-ion batteries (LIBs), the secondary hazards of used batteries to the environment have become an urgent problem, and the recycling of valuable metals has received widespread attention and research. This paper reviews the latest progress in LIBs recovery processes, analyzes and summarizes the problems existing in recovery processes such as pyrometallurgy and hydrometallurgy. We focus on comprehensively analyzing and sorting out the current status of mechanochemical (MC) recovery of valuable metals in cathode materials, including study of mechanochemical techniques for recycling lithium iron phosphate (LFP), lithium cobaltate (LCO), lithium nickel manganese cobalt ternary (NCM), lithium manganese oxides (LMO), and other cathode materials, which provide references to the progress of the recovery process of LIBs.

Key words: lithium-ion batteries, mechanical chemistry, cathode materials, valuable metals

中图分类号:

O 646

肖忠良, 向优涛, 宋刘斌, 匡尹杰, 赵亭亭, 夏宇博, 肖敏之, 蒋琳, 陈涛涛, 肖茜. 机械化学法回收废旧锂离子电池正极材料中有价金属的研究进展[J]. 化工学报, 2023, 74(11): 4419-4432.

Zhongliang XIAO, Youtao XIANG, Liubin SONG, Yinjie KUANG, Tingting ZHAO, Yubo XIA, Minzhi XIAO, Lin JIANG, Taotao CHEN, Qian XIAO. Progress of mechanochemical recovery of valuable metals from used lithium-ion battery cathode materials[J]. CIESC Journal, 2023, 74(11): 4419-4432.

图/表 11

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成分	所用材料	成本占比/%	化学特性	潜在危害性
正极材料	钴酸锂/锰酸锂/镍酸锂/磷酸铁锂	30~35	与水、酸、还原剂或氧化剂发生反应	重金属污染
负极材料	碳材料/石墨	10~15	遇明火或高温易爆炸	粉尘污染
电解质	LiPF₆/LiBF₄/LiAsF₆	10~15	强腐蚀性，遇水生成HF，氧化生成P₂O₅等有害物质	氟污染、有害气体污染
电解质溶剂	碳酸乙烯酯/碳酸二甲酯	10~15	水解生成醛和酸，燃烧产生CO、CO₂等	有机物污染
隔膜材料	聚丙烯/聚乙烯	20~30	燃烧可产生CO、醛等	有机物污染
黏合剂	聚偏氟乙烯/偏氟乙烯	10~15	受热分解产生HF	氟污染

成分	所用材料	成本占比/%	化学特性	潜在危害性
正极材料	钴酸锂/锰酸锂/镍酸锂/磷酸铁锂	30~35	与水、酸、还原剂或氧化剂发生反应	重金属污染
负极材料	碳材料/石墨	10~15	遇明火或高温易爆炸	粉尘污染
电解质	LiPF₆/LiBF₄/LiAsF₆	10~15	强腐蚀性，遇水生成HF，氧化生成P₂O₅等有害物质	氟污染、有害气体污染
电解质溶剂	碳酸乙烯酯/碳酸二甲酯	10~15	水解生成醛和酸，燃烧产生CO、CO₂等	有机物污染
隔膜材料	聚丙烯/聚乙烯	20~30	燃烧可产生CO、醛等	有机物污染
黏合剂	聚偏氟乙烯/偏氟乙烯	10~15	受热分解产生HF	氟污染

浸出剂	正极材料	辅助试剂	浸出条件			浸出率/%				优点	缺点
浸出剂	正极材料	辅助试剂	温度/ ℃	时间/h	固液比/ （g/L）	Li	Ni	Co	Mn	优点	缺点
硫酸^[34]	镍钴锰酸锂	Na₂S₂O₅	60	2.5	100	90	90	90	90	操作简单，浸出率高	腐蚀性强，浸出液量大
盐酸^[25]	废LIBs	NaClO	50	2	20	99	—	99	99	浸出率高，氯离子促进金属溶解	成本高，溶剂易挥发，腐蚀性大
硝酸^[35]	LiCoO₂	H₂O₂	75	1	20	95	—	95	—	浓度低	产生有毒气体
磷酸^[36]	LiCoO₂	葡萄糖	80	2	2	100	—	98	—	浸出液少，效率高	一定的腐蚀性，高温
甲磺酸+对甲苯磺酸^[37]	LiFePO₄	H₂O₂	室温	1.5	40	95	—	—	—	环保绿色，成本低	选择性低
单宁酸^[38]	废LIBs	醋酸	80	4	20	99	—	94	—	浸出液少，效率高	一定的腐蚀性，高温
柠檬酸^[39]	废LIBs	H₂O₂	80	1.5	20	100	—	99	—	绿色,操作简单	无选择性，高温
柠檬酸+DL-苹果酸^[40]	废LIBs	H₂O₂	95	0.5	—	96	—	98	—	操作简单，绿色	高温，无选择性
甲磺酸^[41]	LiCoO₂	H₂O₂	70	1	—	100	—	100	—	操作简单，成本低	腐蚀性，无选择性
柠檬酸^[42]	LiCoO₂	橘子皮	100	4	—	80.5	90.1	91.3	92.2	绿色，成本低	高温
酒石酸^[43]	LiCoO₂	抗坏血酸	80	5	2	99	—	96	—	高效，无毒气	渗滤液量大，温度高
硫酸钠^[44]	LiNi_0.5Co_0.2Mn_0.3O₂	H₂O₂	60	0.5	20	>99	—	>99	—	绿色，操作简单	高能耗
氨水硫酸铵^[45]	LiNi_0.5Co_0.2Mn_0.3O₂	亚硫酸钠	50	—	10~50	97	95	89	—	操作简单，成本低	锰的选择性低
丙醇酸^[46]	LiNi_1/3Mn_1/3Co_1/3O₂	H₂O₂	70	1/3	20	95	98	98	98	绿色，操作简单	一定的腐蚀性，高温
草酸盐^[47]	LiNi_0.5Co_0.2Mn_0.3O₂	柠檬酸	90	0.5	20	100	100	100	100	操作简单	一定的腐蚀性
乳酸^[48]	LiNi_1/3Mn_1/3Co_1/3O₂	H₂O₂	70	1/3	20	97.7	98.2	98.9	98.4	高效，无毒气	高温，成本高
硫酸+丙醇酸^[49]	LiNi _x Co _y Mn _z O₂	H₂O₂	70	1.35	61	99.8	99.5	97.2	96.9	操作简单，高效	一定的腐蚀性，高温

浸出剂	正极材料	辅助试剂	浸出条件			浸出率/%				优点	缺点
浸出剂	正极材料	辅助试剂	温度/ ℃	时间/h	固液比/ （g/L）	Li	Ni	Co	Mn	优点	缺点
硫酸^[34]	镍钴锰酸锂	Na₂S₂O₅	60	2.5	100	90	90	90	90	操作简单，浸出率高	腐蚀性强，浸出液量大
盐酸^[25]	废LIBs	NaClO	50	2	20	99	—	99	99	浸出率高，氯离子促进金属溶解	成本高，溶剂易挥发，腐蚀性大
硝酸^[35]	LiCoO₂	H₂O₂	75	1	20	95	—	95	—	浓度低	产生有毒气体
磷酸^[36]	LiCoO₂	葡萄糖	80	2	2	100	—	98	—	浸出液少，效率高	一定的腐蚀性，高温
甲磺酸+对甲苯磺酸^[37]	LiFePO₄	H₂O₂	室温	1.5	40	95	—	—	—	环保绿色，成本低	选择性低
单宁酸^[38]	废LIBs	醋酸	80	4	20	99	—	94	—	浸出液少，效率高	一定的腐蚀性，高温
柠檬酸^[39]	废LIBs	H₂O₂	80	1.5	20	100	—	99	—	绿色,操作简单	无选择性，高温
柠檬酸+DL-苹果酸^[40]	废LIBs	H₂O₂	95	0.5	—	96	—	98	—	操作简单，绿色	高温，无选择性
甲磺酸^[41]	LiCoO₂	H₂O₂	70	1	—	100	—	100	—	操作简单，成本低	腐蚀性，无选择性
柠檬酸^[42]	LiCoO₂	橘子皮	100	4	—	80.5	90.1	91.3	92.2	绿色，成本低	高温
酒石酸^[43]	LiCoO₂	抗坏血酸	80	5	2	99	—	96	—	高效，无毒气	渗滤液量大，温度高
硫酸钠^[44]	LiNi_0.5Co_0.2Mn_0.3O₂	H₂O₂	60	0.5	20	>99	—	>99	—	绿色，操作简单	高能耗
氨水硫酸铵^[45]	LiNi_0.5Co_0.2Mn_0.3O₂	亚硫酸钠	50	—	10~50	97	95	89	—	操作简单，成本低	锰的选择性低
丙醇酸^[46]	LiNi_1/3Mn_1/3Co_1/3O₂	H₂O₂	70	1/3	20	95	98	98	98	绿色，操作简单	一定的腐蚀性，高温
草酸盐^[47]	LiNi_0.5Co_0.2Mn_0.3O₂	柠檬酸	90	0.5	20	100	100	100	100	操作简单	一定的腐蚀性
乳酸^[48]	LiNi_1/3Mn_1/3Co_1/3O₂	H₂O₂	70	1/3	20	97.7	98.2	98.9	98.4	高效，无毒气	高温，成本高
硫酸+丙醇酸^[49]	LiNi _x Co _y Mn _z O₂	H₂O₂	70	1.35	61	99.8	99.5	97.2	96.9	操作简单，高效	一定的腐蚀性，高温

正极材料	共磨剂/条件	温度/℃	浸出剂/条件	沉淀剂	产品	效率/%(性能)	文献
LFP	(NH₄)₂S₂O₈∶LFP=1.4∶11，5 h， 350 r/min， BMR=30∶1	—	H₂O	—	Li₂SO₄	Li=95.3	[71]
	Na₃Cit∶LFP=10∶1，5 h， 500 r/min， H₂O₂=1 ml	—	H₂O	—	Li₂CO₃	Li=98.9	[72]
	FeCl₃∶LiFePO₄=1.2∶1， 5 h，600 r/min	95	H₂O	NaOH	Li₂CO₃	Li=97	[73]
	LFP∶EDTA-2Na=3∶1， 2 h，S∶L=50 g/L	—	0.6 mol/L H₃PO₄， 20 min	—	FePO₄·2H₂O， Li₃PO₄	Li=94.29，Fe=97.67	[62]
	柠檬酸∶LFP=20∶1， BPR=45，8 h，300 r/min	95	H₂O	NaOH	Fe(OH)₃，Li₂CO₃	Li=97.82，Fe=95.62	[74]
	LiFePO₄∶NaCl=1∶2, 500 r/min，6 h	—	H₂O	Na₂CO₃	NaFePO₄，Li₂CO₃	—	[75]
	LiFePO₄∶草酸=1∶1， 500 r/min，2 h， BMR=20∶1	—	H₂O，30 min	NaOH	FeC₂O₄·2H₂O， Li₃PO₄	Li=99，Fe=94	[76]
LCO	LCO∶GS=0.3∶1，400 r/min， 1 h，0.15 mol/L柠檬酸	—	—	Na₂CO₃	CoC₂O₄·2H₂O， Li₂CO₃	Li=99.33，Co=98.87	[77]
	120 min，500 r/min， NH₄Cl 0.03 mol/L，L∶S=15 g/L	—	1 mol/L H₂SO₄， 80℃，60 min	—	Li₂SO₄	Li=100，Co=99.22	[78]
	LiCoO₂∶EDTA=1∶4，4 h, 600 r/min，BMR=80∶1	—	H₂O	Na₂CO₃， NaOH	Li₂CO₃，Co₃O₄	Li=99，Co=98	[79]
	LiCoO₂∶Al=1∶1，2 h	—	H₂O	Na₂CO₃	Li₂CO₃	Co=90，Li=70	[70]
NCM	(NH₄)₂WO₄，300 r/min， NCM-3%(质量分数）W，1 h	800℃， 4 h	—	—	钨改性NCM	(145 mA·h/g)	[80]
	Li₂CO₃，500 r/min，4 h， Li∶TM(Ni，Co，Mn)=1.2∶1	800℃，10 h	—	—	再生NCM	(165 mA·h/g)	[81]
	Na₂S⋅9H₂O，600 r/min，15 min	—	H₂O，25℃， 30 min	Na₂CO₃	Li₂CO₃， Ni_0.5Mn_0.3Co_0.2(OH)₂	Li=95，Co=100，Ni=100，Mn=100	[82]
	LiOH，360 r/min，10 h	800℃，16 h	—	—	再生NCM	(176.8 mA·h/g)	[83]