Inorganic Chemicals Industry ›› 2023, Vol. 55 ›› Issue (6): 92-103.doi: 10.19964/j.issn.1006-4990.2022-0704
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Study on full element recycling process of retired ternary power lithium battery
LU Junhao(
)
- Central Research Institute of Shanghai Electric Group Co.，Ltd.，Shanghai 200070，China
-
Received:2022-12-01Online:2023-06-10Published:2023-06-14
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Cite this article
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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Table 1
Contents of main components of filter residue"
| 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 | |
Table 2
Contents of main components and metalleaching rate of filtrate"
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 | — | — |
Table 3
Contents of metal elements in solutionafter impurity removal"
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 | — | — |
Table 4
Experimental design of P204 extraction of Mn"
| 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 |
Fig.1
Effect of extraction pH on recovery ofMn and purity of MnSO4"
Fig.2
Effect of extraction V（O）/V（A） on recoveryof Mn and purity of MnSO4"
Fig.3
Effect of extraction time on recoveryof Mn and purity of MnSO4"
Fig.4
Effect of extraction stages on recoveryof Mn and purity of MnSO4"
Fig.5
Effect of salt washing V（O）/V（A） on recoveryof Mn and purity of MnSO4"
Fig.6
Effect of back extraction V（O）/V（A） on recoveryof Mn and purity of MnSO4"
Fig.7
Effect of back extraction time on recoveryof Mn and purity of MnSO4"
Fig.8
Effect of back extraction stages on recoveryof Mn and purity of MnSO4"
Table 5
Experimental design of P507 extraction of Co"
| 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 | 1∶1 | 15 | 3 | 1∶3 | 1∶1 | 15 | 3 |
| 2 | 4.5 | 变量b | 15 | 3 | 1∶3 | 1∶1 | 15 | 3 |
| 3 | 4.5 | 1∶1 | 变量c | 3 | 1∶3 | 1∶1 | 15 | 3 |
| 4 | 4.5 | 1∶1 | 10 | 变量d | 1∶3 | 1∶1 | 15 | 3 |
| 5 | 4.5 | 1∶1 | 10 | 2 | 变量e | 1∶1 | 15 | 3 |
| 6 | 4.5 | 1∶1 | 10 | 2 | 1∶2 | 变量f | 15 | 3 |
| 7 | 4.5 | 1∶1 | 10 | 2 | 1∶2 | 1∶0.5 | 变量g | 3 |
| 8 | 4.5 | 1∶1 | 10 | 2 | 1∶2 | 1∶0.5 | 10 | 变量h |
Fig.9
Effect of extraction pH on recoveryof Co and purity of CoSO4"
Fig.10
Effect of extraction V（O）/V（A） on recoveryof Co and purity of CoSO4"
Fig.11
Effect of extraction time on recoveryof Co and purity of CoSO4"
Fig.12
Effect of extraction stages on recoveryof Co and purity of CoSO4"
Fig.13
Effect of salt washing V（O）/V（A） on recoveryof Co and purity of CoSO4"
Fig.14
Effect of back extraction V（O）/V（A） on recovery of Co and purity of CoSO4"
Fig.15
Effect of back extraction time on recoveryof Co and purity of CoSO4"
Fig.16
Effect of back extraction stages on recoveryof Co and purity of CoSO4"
Table 6
Contents of metal elements in solutionafter impurity removal"
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 | — | — |
Table 7
Consumption of raw and auxiliary materials"
| 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 |
Table 8
Main energy consumption"
| 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 |
Table 9
Sales revenue of main products"
| 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 |
Fig.17
Comparison of crystal structure of synthetic cathodematerials and commercial cathode materials"
Fig.18
Particle size distribution curve of synthetic cathode materials"
Fig.19
Specific surface area test diagram"
Fig.20
Morphology of cathode materials"
Fig.21
Comparison of charge and discharge curves of synthetic cathode materials and commercial cathode materials"
Fig.22
Comparison of charge-discharge specific capacity of synthetic cathode materials and commercial cathode materials"
Table 10
Comparison of physical and electrochemical properties of synthetic cathode materials with industry standards"
| 项目 | 振实密度/ （g∙cm-3） | 粒度分布 | 比表面积/ （m2∙g-1） | 首次放电 比容量/ （mA∙h∙g-1） | 首次充放 电效率/% | 平台容量 比率/% |
|---|---|---|---|---|---|---|
| YS/T 798—2012《镍钴锰酸锂》 | ≥1.8 | D10≥2.0 μm；D50为5~10 μm；D90≤30.0 μm | ≤1.0 | ≥140 | ≥85 | ≥50 |
| 所合成正极材料 | 2.5 | D10为3.26 μm；D50为 5.91 μm；D90为10.2 μm | 0.872 4±0.005 1 | 156.2 | 85.2 | 93.4 |
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