退役三元动力锂电池全元素循环再利用工艺研究

doi:10.19964/j.issn.1006-4990.2022-0704

Abstract

Abstract:

The process of extracting Ni，Co and Mn from the filter residue of preferential extraction of lithium from retired ternary power lithium battery was studied.Using extractant（C₈H₁₇O）₂PO₂H（P204） under the following processing conditions such as extraction pH of 3，extraction V（O）∶V（A）=1∶1，extraction time of 15min，extraction order of 3，salt washing V（O）∶V（A）=1∶2，back extraction V（O）∶V（A）=1∶0.5，back extraction time of 15min，back extraction order of 3，the recycling rate of Mn was 98.6%，while the purity of MnSO₄ was 99.5%.Using extractant（（C₈H₁₇）₂PO₃H（P507） under the following processing conditions such as extraction pH of 4.5，extraction V（O）∶V（A）=1∶1，extraction time of 10 min，extraction order of 2，salt washing V（O）∶V（A）=1∶2，back extraction V（O）∶V（A）=1∶0.5，back extraction time of 10 min，back extraction order of 2，the recycling rate of Co was 96.5%，while the purity of CoSO₄ was 94.9%.After impurities in Mn，Co raffinate were removed with（C₈H₁₇）₂PO₂H（C272） extractant，the recovery rate of Ni was 96.5%，while the purity of NiSO₄ was 97.3%.The battery cathode materials was regenerated by the extracted battery raw materials and their crystal structure，physical properties，electrochemical properties were tested.The results showed that the relevant performance indexes of the synthesized cathode materials met the YS/T 798—2021“Lithium nickel cobalt manganese oxide”industry standards and were qualified to enter the battery industry.

Key words: retired ternary power lithium battery, extraction, salt washing, cathode materials

CLC Number:

TQ131.11

LU Junhao. Study on full element recycling process of retired ternary power lithium battery[J]. Inorganic Chemicals Industry, 2023, 55(6): 92-103.

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References 13

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w（Ni）	w（Co）	w（Mn）	w（Li）	w（Cu）	w（Fe）	w（Al）
35.5	10.2	11.3	N.D.	0.02	0.05	N.D.
w（Ca）	w（Mg）	w（Zn）	w（P）	w（F）	w（不溶物）
0.09	0.08	N.D.	N.D.	N.D.	0.2

测试项目	滤液中质量浓度/（g∙L^-1）	浸出率/ %	测试项目	滤液中质量浓度/（g∙L^-1）	浸出率/ %
Ni	76.18	100.0	Fe	0.11	100
Co	21.80	99.6	Al	—	—
Mn	24.20	99.8	Ca	0.19	100
Li	—	—	Mg	0.17	100
Cu	0.04	100.0	Zn	—	—

测试项目	萃余液中质量浓度/ （g∙L^-1）	除铜液中质量浓度/ （g∙L^-1）	测试项目	萃余液中质量浓度/ （g∙L^-1）	除铜液中质量浓度/ （g∙L^-1）
Ni	75.42	75.04	Fe	0.01	—
Co	21.69	21.54	Al	—	—
Mn	23.83	23.56	Ca	0.02	—
Li	—	—	Mg	0.16	0.15
Cu	0.03	—	Zn	—	—

项目	单价/ （万元∙t^-1）	数量/t	总价/ （万元∙a^-1）	规格
合计			15 702.5
三元正极粉	14	1 000	14 000
氢氧化钠	0.15	6 800	1 020	30%
碳酸钠	0.2	1 100	220
硫化钠	0.25	10	2.5
浓硫酸	0.03	4 700	141	98%
双氧水	0.2	700	140	30%
260#磺化煤油	0.65	120	78
P204	3	3	9
P507	5	2	10
C272	35	0.2	7
活性炭	0.25	300	75

项目	单价	数量	总价/ （万元∙a^-1）	备注
合计			2 484.5
电耗	1元/（kW∙h）	160万kW∙h	160
蒸汽消耗	200元/t	3 700 t	74
水消耗	2元/t	2 500 t	0.5
人工费用			2 000
设备折旧			250	按10 a年限折旧

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on full element recycling process of retired ternary power lithium battery

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序号	萃取pH	萃取相比 V（O）∶V（A）	萃取时间/ min	萃取级数	盐洗相比 V（O）∶V（A）	反萃取相比 V（O）∶V（A）	反萃取时间/ min	反萃取级数
1	变量a	0.8∶1	20	3	1∶3	1∶1	20	3
2	3	变量b	20	3	1∶3	1∶1	20	3
3	3	1∶1	变量c	3	1∶3	1∶1	20	3
4	3	1∶1	15	变量d	1∶3	1∶1	20	3
5	3	1∶1	15	3	变量e	1∶1	20	3
6	3	1∶1	15	3	1∶2	变量f	20	3
7	3	1∶1	15	3	1∶2	1∶0.5	变量g	3
8	3	1∶1	15	3	1∶2	1∶0.5	15	变量h

测试项目	萃余液中质量浓度/ （g∙L^-1）	除杂液中质量浓度/ （g∙L^-1）	测试项目	萃余液中质量浓度/ （g∙L^-1）	除杂液中质量浓度/ （g∙L^-1）
Ni	73.91	72.82	Al	—	—
Co	0.75	—	Ca	—	—
Mn	0.33	—	Mg	0.15	—
Li	—	—	Zn	—	—
Cu	—	—	Na	42.11	37.90
Fe	—	—

项目	单价/ （万元∙t^-1）	数量/ t	总价/ （万元∙a^-1）	备注
碳酸锂产品	52	255	13 260	电池级
硫酸镍产品	3.95	1 060	4 187	电池级
硫酸钴产品	5.2	470	2 444	电池级
硫酸锰产品	0.65	420	273	电池级
硫酸钠产品	0.15	3 480	522
年收入合计			20 686

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