退役锂离子电池碳/硫协同选择性提锂技术

doi:10.6023/A21030083

化学学报 ›› 2021, Vol. 79 ›› Issue (8): 1073-1081.DOI: 10.6023/A21030083 上一篇下一篇

研究论文

退役锂离子电池碳/硫协同选择性提锂技术

徐平^a, 张西华^a^,^*(), 马恩^a, 饶富^a, 刘春伟^b, 姚沛帆^a, 孙峙^b^,^*(), 王景伟^a

a 上海第二工业大学电子废弃物研究中心资源循环科学与工程中心上海电子废弃物资源化协同创新中心上海 201209
b 北京市过程污染控制工程技术研究中心中国科学院过程工程研究所环境技术与工程研究部中国科学院绿色过程制造创新研究院北京 100190

投稿日期:2021-03-07 发布日期:2021-07-19
通讯作者: 张西华, 孙峙
基金资助:
国家自然科学基金(51874269); 上海第二工业大学校基金(EGD20XQD06); 上海市高原学科—环境科学与工程(资源循环科学与工程)

Selective Recovery of Lithium from Spent Lithium-ion Batteries Synergized by Carbon and Sulfur Elements

Ping Xu^a, Xihua Zhang^a(), En Ma^a, Fu Rao^a, Chunwei Liu^b, Peifan Yao^a, Zhi Sun^b(), Jingwei Wang^a

a WEEE Research Centre, Research Center of Resource Recycling Science and Engineering, Shanghai Polytechnic University; Shanghai Collaborative Innovation Centre for WEEE Recycling, Shanghai 201209, China
b Beijing Engineering Research Center of Process Pollution Control; Division of Environment Technology and Engineering, Institute of Process Engineering, Innovation Academy for Green Manufacture, Chinese Academy of Sciences, Beijing 100190, China

Received:2021-03-07 Published:2021-07-19
Contact: Xihua Zhang, Zhi Sun
Supported by:
National Natural Science Foundation of China(51874269); Research fund of Shanghai Polytechnic University(EGD20XQD06); Gaoyuan Discipline of Shanghai - Environmental Science and Engineering(Resource Recycling Science)

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摘要/Abstract

针对当前退役锂离子电池有价金属提取工艺选择性差、环境风险突出的瓶颈问题, 提出了碳/硫协同选择性提锂的新思路. 首先在系统考察(NH₄)₂SO₄、NH₄HSO₄、NaHSO₄和H₂SO₄分别作为焙烧剂对退役锂离子电池LiNi_1/3Co_1/3Mn_1/3O₂正极粉末中锂的浸出选择性、环境友好性和经济性影响的基础上, 确定H₂SO₄为最佳焙烧剂. 基于此, 研究了石墨添加量对LiNi_1/3Co_1/3Mn_1/3O₂中锂的浸出选择性的影响, 揭示了C/S协同强化锂的浸出选择性的转化路径及其机制. 结果表明, 在LiNi_1/3Co_1/3Mn_1/3O₂与H₂SO₄物质的量比为2∶1、石墨添加量为20% (w)、焙烧温度为600 ℃、焙烧时间为120 min的最优条件下, LiNi_1/3Co_1/3Mn_1/3O₂中锂的浸出率高达93%, 回收的Li₂CO₃纯度高于电池级Li₂CO₃纯度要求; Ni、Co和Mn均进入渣相, 经分离纯化后可作为合成正极材料的前驱物, 分离得到的石墨可回用于硫化焙烧过程的添加剂. 通过对LiNi_1/3Co_1/3Mn_1/3O₂混合粉末(含20 wt.%石墨)硫化焙烧热行为及其产物X射线衍射(XRD)表征表明, 石墨的添加降低了硫化焙烧的反应温度, 通过C/S协同作用强化了LiNi_1/3Co_1/3Mn_1/3O₂中锂的选择性浸出, 且不产生SO_x等有毒有害气体. 本工作结合硫化焙烧和碳热还原优势, 为退役锂离子电池正负极材料的同步循环利用开辟了新思路, 实现了LiNi_1/3Co_1/3Mn_1/3O₂中锂的高效选择性清洁提取和废石墨负极的循环利用.

关键词: 退役锂离子电池, 硫化焙烧, 废石墨, 选择性提取, 锂

Recycling of spent lithium-ion batteries (LIBs) has attracted ever-growing attention globally owing to the scarcity of critical metals and potential environmental risk. To solve the bottlenecks including poor selectivity and prominent environmental risks during the recovery of valuable metals from spent LIBs, the work proposed a novel process for selectively recovery of lithium synergized by carbon and sulfur elements. Firstly, H₂SO₄ was determined as the optimal roasting reagent by systematically investigating the effects of various roasting reagents including NaHSO₄, (NH₄)₂SO₄, NH₄HSO₄ and H₂SO₄ on the leaching selectivity of lithium from the LiNi_1/3Co_1/3Mn_1/3O₂ active material in spent LIBs, environmental impact and cost of reagents. Then, the effect of graphite dosage on the selectivity of lithium from LiNi_1/3Co_1/3Mn_1/3O₂ is investigated. Finally, the conversion path and mechanism under the synergistic effect of C and S elements for enhancing the selectivity of lithium is revealed. It is found that the leaching efficiency can achieve 93% under the following optimal conditions: the molar ratio of LiNi_1/3Co_1/3Mn_1/3O₂ to H₂SO₄ of 2∶1, graphite dosage of 20% (w), roasting temperature of 600 ℃, and roasting time of 120 min. The purity of the precipitated Li₂CO₃ from the obtained leachate is higher than that of battery grade Li₂CO₃. Ni, Co and Mn from LiNi_1/3Co_1/3Mn_1/3O₂ almost remains in the leaching residue which can be employed as the precursor materials for synthesizing cathode materials after separation and purification treatment. In addition, the separated graphite can be reused as roasting additive during the sulfation roasting of LiNi_1/3Co_1/3Mn_1/3O₂. By analyzing the thermal behavior of the mixed powder of LiNi_1/3Co_1/3Mn_1/3O₂ and graphite, along with the X-ray diffraction (XRD) characterization of the roasting products, it is found that the roasting temperature can be reduced by the addition of waste graphite, the selectivity of lithium can be enhanced under the synergistic effect of C and S elements. Most importantly, no hazardous gases such as SO_x are generated. This work proposed a new solution for simultaneous recycling of cathode and anode materials by combing the advantages of sulfation roasting and carbothermal reduction, thus the efficient, selective and cleaner extraction of lithium and the circulating utilization of waste graphite can be achieved.

Key words: spent lithium-ion battery, sulfation roasting, waste graphite, selective recovery, lithium

引用此文

徐平, 张西华, 马恩, 饶富, 刘春伟, 姚沛帆, 孙峙, 王景伟. 退役锂离子电池碳/硫协同选择性提锂技术[J]. 化学学报, 2021, 79(8): 1073-1081.

Ping Xu, Xihua Zhang, En Ma, Fu Rao, Chunwei Liu, Peifan Yao, Zhi Sun, Jingwei Wang. Selective Recovery of Lithium from Spent Lithium-ion Batteries Synergized by Carbon and Sulfur Elements[J]. Acta Chimica Sinica, 2021, 79(8): 1073-1081.

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图/表 15

Composition	Li	Ni	Co	Mn	Al	Fe
Content (w)/%	7.78	22.67	18.28	16.21	0.34	0.04

表1. 退役锂离子电池正极粉末的主要成分

Table 1. Main composition of cathode material powder from spent LIBs

图1. 退役锂离子电池NCM111正极粉末的XRD图谱

Figure 1. XRD pattern of the NCM111 cathode material powder from spent LIBs

图2. 焙烧剂添加量对NCM111正极粉末中有价金属浸出率的影响: (a)硫酸铵; (b)硫酸氢铵; (c)硫酸氢钠; (d)硫酸

Figure 2. Effects of different roasting reagents on the leaching efficiencies of valuable metals from the roasted products of NCM111 cathode material powder: (a) (NH4)2SO4; (b) NH4HSO4; (c) NaHSO4; (d) H2SO4

图3. 焙烧温度对NCM111正极粉末中有价金属浸出率的影响: (a)硫酸铵; (b)硫酸氢铵; (c)硫酸氢钠; (d)硫酸

Figure 3. Effects of different roasting temperatures on the leaching efficiencies of valuable metals from the roasted products of NCM111 cathode material powder: (a) (NH4)2SO4; (b) NH4HSO4; (c) NaHSO4; (d) H2SO4

图4. 焙烧时间对NCM111正极粉末中有价金属浸出率的影响: (a)硫酸铵; (b)硫酸氢铵; (c)硫酸氢钠; (d)硫酸

Figure 4. Effects of different roasting time on the leaching efficiencies of valuable metals from the roasted products of NCM111 cathode material powder: (a) (NH4)2SO4; (b) NH4HSO4; (c) NaHSO4; (d) H2SO4

图5. 最佳焙烧条件下不同焙烧剂对NCM111正极粉末中有价金属浸出率的影响

Figure 5. Effects of different roasting reagents on the leaching efficiencies of valuable metals from the roasted products from NCM111 cathode material powder under optimal roasting conditions

图6. 不同焙烧剂焙烧过程中SO2产生情况: (a)硫酸铵; (b)硫酸氢铵; (c)硫酸氢钠; (d)硫酸

Figure 6. The generation of SO2 during the roasting process of different roasting reagents: (a) (NH4)2SO4; (b) NH4HSO4; (c) NaHSO4; (d) H2SO4

图7. 最佳焙烧条件下不同焙烧剂的消耗量(a)与试剂成本(b)

Figure 7. Consumption of different roasting reagents (a) and the corresponding costs (b) under the optimal roasting conditions

图8. 石墨对NCM111焙烧产物物相结构的影响

Figure 8. Effect of graphite on the phase structure of the roasted products

图9. 石墨对NCM111焙烧产物中有价金属浸出率的影响

Figure 9. Effect of graphite on the leaching efficiencies of valuable metals from the roasted products

图10. 沉淀回收碳酸锂的XRD图谱(a)和SEM图谱(b)

Figure 10. XRD pattern (a) and the SEM image (b) of the precipitated Li2CO3 sample

Composition	Li	Ni	Co	Mn	Na	Others
Content (w)/%	99.64	0.01	0.03	0.02	0.08	0.22

表2. 沉淀回收Li2CO3的成分

Table 2. Composition of the precipitated Li2CO3 sample

图11. NCM111混合粉末(n(NCM111)∶n(H2SO4)=2∶1、20% (w)石墨)的TG-DTA曲线(a)及其产生气体的质谱图(m/z(H2O)=18、m/z(CO2)=44、m/z(SO2)=64) (b)

Figure 11. TG-DTA curve of the mixed NCM111 powder (n(NCM111)∶n(H2SO4)=2∶1, 20% (w) graphite) (a) and the mass spectrogram of the generated gases (m/z(H2O)=18、m/z(CO2)=44、m/z(SO2)=64) (b)

图12. NCM111混合粉末硫化焙烧过程的转化路径及机理图

Figure 12. Conversion path and mechanism for the mixed NCM111 powder during the roasting process by H2SO4

图13. NCM111硫化焙烧产物的XRD图谱

Figure 13. XRD pattern for the roasted products of the mixed NCM111 powder by H2SO4

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退役锂离子电池碳/硫协同选择性提锂技术

Selective Recovery of Lithium from Spent Lithium-ion Batteries Synergized by Carbon and Sulfur Elements

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