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In situ polymerization of 1,3-dioxolane infiltrating 3D garnet framework with high ionic conductivity and excellent interfacial stability for integrated solid-state Li metal battery

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Abstract

The polymer-ceramic composite electrolyte is considered as one of promising electrolytes for solid-state battery. However, in previous research, ceramic particles are usually dispersed in polymer matrix and could not form continuous Li+ conductive channels. The agglomeration of ceramic particles could also lead to low ionic conductivity and poor interfacial electrode/electrolyte contact. In this paper, self-supported porous Li6.4La3Zr1.4Ta0.6O12 (LLZTO) electrolyte is synthesized by gelcasting process, which possesses three-dimensional (3D) interconnected pore channels and relatively high strength. The 1,3-dioxolane (DOL) could penetrate into the porous LLZTO framework for its excellent fluidity. The subsequent in situ polymerization process by thermal treatment could completely fill the internal pores and improve the interfacial contact with electrode. The resulting 3D composite electrolyte with dual continuous Li+ transport channels in ceramic and polymer components exhibits high ionic conductivity of 2.8 × 10–4 S·cm−1 at room temperature and low Li/electrolyte interfacial resistance of 94 Ω·cm2 at 40 °C. The corresponding Li/Li symmetric cell delivers stable voltage profiles for over 600 h under 0.1 and 0.2 mA·cm−2. The solid-state Li/LiFePO4 battery shows superior rate and cycling performance under 0.1C and 0.2C. This work guides the preparation of composite electrolyte with dual continuous Li+ conductive paths as well as high ceramic ratio and interface modification strategy for solid-state Li metal battery.

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摘要

聚合物-陶瓷复合电解质被认为是最有前途的固态电池电解质之一, 然而在以往的复合电解质研究中, 陶瓷颗粒通常分散在聚合物基体中, 不能形成连续的锂离子导电通道, 陶瓷颗粒的团聚也可能导致离子电导率低和电极/电解质界面接触不良。本文采用凝胶注模工艺制备了自支撑的多孔Li6.4La3Zr1.4Ta0.6O12电解质, 具有三维互连的孔道结构和较高的强度。1,3-二氧戊环 (DOL)由于具有优异的流动性, 可以轻易地渗透进多孔LLZTO的孔洞内, 随后通过热处理诱发原位聚合过程, 可完全填充内部孔隙并改善与电极的界面接触。制得的三维复合电解质在陶瓷和聚合物电解质组分中具有双连续的锂离子传输通道, 在室温下表现出3.5 × 10−4 S cm−1 的高离子电导率, 在40 °C下表现出94 Ω cm2的锂负极/电解质界面电阻。对应的锂锂对称电池在0.1和0.2 mA cm−2的电流密度下可稳定循环超过600 h, 固态Li/LiFePO4电池在0.1C和0.2C下表现出优异的倍率和循环性能。这个工作对高固相含量复合电解质的制备和固态电池界面改性提供了参考指引。

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 52173257 and 51872159).

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Authors and Affiliations

  1. State Key Lab of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China

    Lin-Hui Chen, Shi-Le Chen, Rong-Ao Tong & Chang-An Wang

  2. College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016, China

    Ze-Ya Huang

  3. School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450001, China

    Hai-Long Wang & Gang Shao

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  1. Lin-Hui Chen
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Chen, LH., Huang, ZY., Chen, SL. et al. In situ polymerization of 1,3-dioxolane infiltrating 3D garnet framework with high ionic conductivity and excellent interfacial stability for integrated solid-state Li metal battery. Rare Met. 41, 3694–3705 (2022). https://doi.org/10.1007/s12598-022-02080-4

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