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Bifunctional polymer electrolyte with higher lithium-ion transference number for lithium-sulfur batteries

新型P(VDF-HFP)基双功能高离子迁移数聚合物电解质用于锂硫电池

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Abstract

Lithium-sulfur (Li-S) batteries have attracted enormous interest due to their super-high theoretical energy density (2600 W · h/kg) in recent years. However, issues such as lithium dendrites and the shuttle effect severely hampered the large-scale application of Li-S batteries. Herein, a novel bifunctional gel polymer electrolyte, poly(N,N-diallyl-N, N-dimethylammonium bis(trifluoromethylsulfonylimide))-P(VDF-HFP) (PDDA-TFSI-P(VDF-HFP), PTP), was prepared by anion exchange reaction to tackle the above problems. Benefited from the interaction between TFSI− and quaternary ammonium ion in PTP, a higher lithium-ion transference number was obtained, which could availably protect Li metal anodes. Meanwhile, due to the adsorption interactions between PDDA-TFSI and polysulfides (LiPSs), the shuttle effect of Li-S batteries could be alleviated effectively. Consequently, the Li symmetric batteries assembled with PTP cycled more than 1000 h and lithium metal anodes were protected effectively. Li-S batteries assembled with this polymer electrolyte show a discharge specific capacity of 813 mA·h/g after 200 cycles and 467 mA·h/g at 3C, exhibiting excellent cycling stability and C-rates performance.

摘要

锂硫电池由于具有较高的理论能量密度, 价格低廉, 环境友好等特点而备受关注, 然而锂硫电 池仍然面临着锂金属负极枝晶生长造成界面不稳定, 多硫化物溶解造成穿梭效应等一系列问题。为了 解决以上问题, 使用聚二烯丙基二甲基氯化铵(PDDA-Cl)水溶液与双三氟甲磺酰亚胺锂(LiTFSI)进行阴 离子交换反应, 制备了带有大阴离子TFS 的聚合物PDDA-TFSI, 并与P(VDF-HFP)进行复合制备了聚 合物电解质PDDA-TFSI-P(VDF-HFP)。这种聚合物电解质可以通过对阴离子的吸附和阻碍作用提高锂 离子迁移数, 促进锂离子在锂负极表面的均匀沉积; 同时PDDA-TFSI中的季铵离子对多硫化物也有一 定的吸附作用, 可以有效地抑制穿梭效应。实验结果表明, 使用这种双功能聚合物电解质组装的Li-Li 对称电池在电流密度为0.5 mA/cm2, 锂剥离/沉积量为2 mA∙h/cm2 时可以稳定循环近1000 h, 明显优于 液态电解质; 此外, 使用此聚合物电解质的Li-S 电池初始放电比容量可达1241 mA∙h/g, 0.2C循环200 周之后比容量为813 mA∙h/g, 且在放电倍率为3C时仍可保持467 mA·h/g 的比容量, 相对于液态电解 质表现出更好的循环稳定性和倍率性能。

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Project(21935006) supported by the National Natural Science Foundation of China

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  1. WANG Zi-long and JIANG Jiang-hui contributed equally to this work.

Authors and Affiliations

  1. Beijing Key Laboratory of Advanced Chemical Energy Storage Technology and Materials, Research Institute of Chemical Defense, Beijing, 100191, China

    Zi-long Wang  (王子龙), Jian-hao Lu  (鲁建豪), An-bang Wang  (王安邦), Zhao-qing Jin  (金朝庆) & Wei-kun Wang  (王维坤)

  2. CATARC Automotive Test Center (Guangzhou) Co., Ltd., Guangzhou, 511300, China

    Jiang-hui Jiang  (蒋江辉)

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WANG Zi-long conducted partial experiments, performed data analysis and edited the draft of manuscript. JIANG Jiang-hui conducted partial experiments and wrote the first draft of the manuscript. LU Jian-hao performed data analysis. WANG An-bang, JIN Zhao-qing and WANG Wei-kun provided the concept and conducted the literature review.

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WANG Zi-long, JIANG Jiang-hui, LU Jian-hao, WANG An-bang, JIN Zhao-qing, WANG Wei-kun declare that they have no conflict of interest.

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Wang, Zl., Jiang, Jh., Lu, Jh. et al. Bifunctional polymer electrolyte with higher lithium-ion transference number for lithium-sulfur batteries. J. Cent. South Univ. 28, 3681–3693 (2021). https://doi.org/10.1007/s11771-021-4881-9

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