废旧磷酸铁锂电池电极材料的硫酸化焙烧-水浸新工艺

doi:10.19799/j.cnki.2095-4239.2021.0674

摘要/Abstract

摘要：

针对目前急需解决的废旧磷酸铁锂(LiFePO₄)电池中有价金属的清洁高效提取问题，提出硫酸化焙烧脱氟-水浸新工艺。用TG-DSC和XRD表征确定了正负极片热处理的适宜条件为：空气气氛、温度575 ℃。采用正交实验和单因素实验研究了浓硫酸使用量、焙烧时间和温度。水浸液固比、温度及时间对正负极混合料粉末中Fe、P和Li元素浸出率和浸出液中F元素残存率的影响。确定了最优焙烧工艺条件为：浓硫酸使用量为理论用量的0.75倍、焙烧时间2.5 h、温度110 ℃；最优水浸工艺条件为：液固比4∶1(mL/g)、温度60 ℃、时间2 h。在此工艺条件下，P和Li的浸出率都达到100%，Fe元素的浸出率为98.85%，F元素在浸出液中的残存率仅为13.11%。

关键词: 废旧磷酸铁锂电池, 电极材料, 硫酸化焙烧, 水浸, 浸出率

Abstract:

This study proposes a novel sulfated roasting defluorination and water leaching technique to recover precious metals from wasted lithium iron phosphate (LiFePO₄) batteries cleanly and efficiently. The air atmosphere and temperature of 575 ℃ were determined as the appropriate thermal decomposition conditions of binder by TG-DSC and XRD. By using orthogonal and single-factor experiments, the effects of concentrated sulfuric acid dosage, roasting time and temperature, liquid-solid ratio, temperature, and time of water leaching on the leaching rate of Fe, P, and Li from spent lithium iron phosphate electrode mixture powder and the residual rate of F in the leaching solution were investigated. The optimal roasting process conditions were determined as follows: 0.75 times the theoretical amount of concentrated sulfuric acid, roasting time of 2.5 h, and roasting temperature of 110 ℃. The optimal water leaching process conditions were determined as follows: liquid-solid ratio of 4∶1, a temperature of 60 ℃, and time of 2 h. Under these conditions, both the leaching rates of P and Fe are up to 100%, the leaching rate of Fe is 98.85%, and the residual amount of F in the leaching solution is only 13.11%.

Key words: spent lithium iron phosphate batteries, electrode material, sulfated roasting, atmospheric water leaching, leaching rate

中图分类号:

TM 911

张肖洒, 王宏源, 李振彪, 夏志美. 废旧磷酸铁锂电池电极材料的硫酸化焙烧-水浸新工艺[J]. 储能科学与技术, 2022, 11(7): 2066-2074.

Xiaosa ZHANG, Hongyuan WANG, Zhenbiao LI, Zhimei XIA. New process of sulfated roasting-water leaching for treating electrode material of spent lithium iron phosphate batteries[J]. Energy Storage Science and Technology, 2022, 11(7): 2066-2074.

图/表 11

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水平	因素
水平	浓硫酸使用量^① (A)	焙烧时间/h (B)	焙烧温度/℃ (C)	液固比/(mL/g) (D)	水浸温度/℃ (E)	水浸时间/h (F)
1	1.0	0.5	80	4.0/1	40	0.5
2	1.1	1.0	90	4.5/1	50	1.0
3	1.2	1.5	100	5.0/1	60	1.5
4	1.3	2.0	110	5.5/1	70	2.0
5	1.4	2.5	120	6.0/1	80	2.5

实验号	A	B	C	D	E	F	Fe浸出率/%
1	1.0	0.5	80	4.0/1	40	0.5	96.73
2	1.0	1.0	90	4.5/1	50	1.0	99.82
3	1.0	1.5	100	5.0/1	60	1.5	99.89
4	1.0	2.0	110	5.5/1	70	2.0	98.52
5	1.0	2.5	120	6.0/1	80	2.5	98.14
6	1.1	0.5	90	5.0/1	70	2.5	96.93
7	1.1	1.0	100	5.5/1	80	0.5	99.12
8	1.1	1.5	110	6.0/1	40	1.0	98.87
9	1.1	2.0	120	4.0/1	50	1.5	99.25
10	1.1	2.5	80	4.5/1	60	2.0	99.35
11	1.2	0.5	100	6.0/1	50	2.0	98.29
12	1.2	1.0	110	4.0/1	60	2.5	99.38
13	1.2	1.5	120	4.5/1	70	0.5	99.25
14	1.2	2.0	80	5.0/1	80	1.0	99.62
15	1.2	2.5	90	5.5/1	40	1.5	96.99
16	1.3	0.5	110	4.5/1	80	1.5	99.72
17	1.3	1.0	120	5.0/1	40	2.0	99.34
18	1.3	1.5	80	5.5/1	50	2.5	96.56
19	1.3	2.0	90	6.0/1	60	0.5	98.21
20	1.3	2.5	100	4.0/1	70	1.0	97.92
21	1.4	0.5	120	5.5/1	60	1.0	95.87
22	1.4	1.0	80	6.0/1	70	1.5	99.75
23	1.4	1.5	90	4.0/1	80	2.0	99.82
24	1.4	2.0	100	4.5/1	40	2.5	99.62
25	1.4	2.5	110	5.0/1	50	0.5	99.21
K₁	98.62	97.508	98.402	98.62	98.31	98.504	—
K₂	98.704	99.482	98.354	99.552	98.626	98.42	—
K₃	98.706	98.878	98.968	98.998	98.54	99.12	—
K₄	98.35	99.044	99.14	97.412	98.474	99.064	—
K₅	98.854	98.322	98.37	98.652	99.284	98.126	—
R	0.504	1.974	0.786	2.14	0.974	0.994	—

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