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Vol. 18 (2026)

Li7La3Zr2O12/Polymethacrylate-Based Composite Electrolyte with Hybrid Solid Electrolyte Interphase for Ultra-stable Solid-State Lithium Batteries

https://doi.org/10.1007/s40820-025-02041-3
Tao Li
School of Materials and Energy, Lanzhou University, Lanzhou 730000, People’s Republic of China
Guohao Zhao
School of Materials and Energy, Lanzhou University, Lanzhou 730000, People’s Republic of China
Zhiyi Zhao
School of Materials and Energy, Lanzhou University, Lanzhou 730000, People’s Republic of China
Yaqi Xu
School of Materials and Energy, Lanzhou University, Lanzhou 730000, People’s Republic of China
Tianli Wu
Henan Key Laboratory of Quantum Materials and Quantum Energy, School of Future Technology, Henan University, Kaifeng 475004, People’s Republic of China
Dong‑Liang Peng
College of Materials, Xiamen University, Xiamen 361005, People’s Republic of China
Qingshui Xie
College of Materials, Xiamen University, Xiamen 361005, People’s Republic of China
Ying Xu
School of Materials and Energy, Lanzhou University, Lanzhou 730000, People’s Republic of China

Corresponding Author: Ying Xu

xuying@lzu.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 189

Abstract

Li7La3Zr2O12-based electrolytes have got great promise for solid-state lithium (Li) metal batteries because of their high elastic modulus and wide electrochemical stability window. However, the insufficient contact and heterogeneous Li deposition severely hinder their practical applications. Here, a flexible ternary polymethacrylate (PMA) matrix is designed to incorporate with Ta-doped Li7La3Zr2O12 (LLZTO-PMA). The PMA matrix ensures excellent interfacial contact, while the synergistic effects of its polar carbonyl groups and its interaction with LLZTO creating fast interfacial Li+ pathways yield a high ionic conductivity of 0.266 mS cm − 1 at 20 °C. Moreover, the interaction between LLZTO and PMA matrix further guides the formation of a hybrid LiF/Li3N-rich solid electrolyte interphase, which allows a fast Li+ interfacial kinetic due to its lowered Li+ diffusion barrier. Consequently, the LLZTO-PMA electrolyte contributes an ultra-stable Li anode interphase, attaining a lifespan exceeding 10,000 h in symmetric cells and retaining over 96% capacity after 600 cycles in full battery, demonstrating a breakthrough for high-performance solid-state batteries.


Highlights:
1 A molecular engineering of Ta-doped Li7La3Zr2O12 (LLZTO) incorporated with polymethacrylate-based (PMA) copolymer moves beyond simple blending to combine the polar carbonyl groups and interfacial Li⁺ transport pathways, yielding high ionic conductivity (0.266 mS cm − 1) and high Li+ transference number (0.621) at 20 °C.
2 The integration of LLZTO triggers the in situ formation of a hybrid LiF-Li3N-rich solid electrolyte interphase with a low Li+ diffusion barrier for uniform Li deposition and exceptional interfacial stability.
3 The LLZTO-PMA contributes an ultra-stable anode interphase, thus delivering symmetric cell over 10,000 h.

Keywords

LLZTO Ionic conductivity Li3N-LiF hybrid SEI Stable interphase Solid-state Li batteries
Li, Tao, Guohao Zhao, Zhiyi Zhao, Yaqi Xu, Tianli Wu, Dong‑Liang Peng, Qingshui Xie, and Ying Xu. 2026. “Li7La3Zr2O12/Polymethacrylate-Based Composite Electrolyte With Hybrid Solid Electrolyte Interphase for Ultra-Stable Solid-State Lithium Batteries”. Nano-Micro Letters 18 (January):189. https://doi.org/10.1007/s40820-025-02041-3.
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