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

doi:10.6023/A21030083

Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (8): 1073-1081.DOI: 10.6023/A21030083 Previous Articles Next Articles

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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)

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

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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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Fig. & Tab. 15

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

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

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

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

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

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

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

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

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

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

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

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

Table 2. Composition of the precipitated Li2CO3 sample

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)

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

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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