基于Li10GeP12S2 全固态电池关键材料的热稳定性

doi:10.19799/j.cnki.2095-4239.2024.1203

储能科学与技术 ›› 2025, Vol. 14 ›› Issue (6): 2193-2199.doi: 10.19799/j.cnki.2095-4239.2024.1203

基于Li₁₀GeP₁₂S₂ 全固态电池关键材料的热稳定性

张文杰¹(), 任东生², 吴宇¹(), 芮新宇²(), 刘翔³(), 冯旭宁²(), 卢兰光²()

^1.北京理工大学材料学院，北京 100081
^2.清华大学车辆与运载学院，北京 100084
^3.北京航空航天大学材料科学与工程学院，北京 100191

收稿日期:2024-12-18 修回日期:2024-12-31 出版日期:2025-06-28 发布日期:2025-06-27
通讯作者: 吴宇,芮新宇,刘翔,冯旭宁,卢兰光 E-mail:792442831@qq.com;wuyu@bit.edu.cn;rxy19@tsinghua.org.cn;xiangliu@buaa.edu.cn;fxn17@mail.tsinghua.edu.cn;lulg@mail.tsinghua.edu.cn
作者简介:张文杰（2000—），男，硕士研究生，研究方向为全固态电池关键材料的安全性，E-mail：792442831@qq.com；
基金资助:
国家重点研发计划(2022YFB3807700);国家自然科学基金(52476174)

Thermal stability of key materials in Li₁₀GeP₁₂S₂-based all-solid-state batteries

Wenjie ZHANG¹(), Dongsheng REN², Yu WU¹(), Xinyu RUI²(), Xiang LIU³(), Xuning FENG²(), Languang LU²()

^1.School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
^2.School of Vehicle and Mobility, Tsinghua University, Beijing 100084, China
^3.School of Materials Science and Engineering, Beihang University, Beijing 100191, China

Received:2024-12-18 Revised:2024-12-31 Online:2025-06-28 Published:2025-06-27
Contact: Yu WU, Xinyu RUI, Xiang LIU, Xuning FENG, Languang LU E-mail:792442831@qq.com;wuyu@bit.edu.cn;rxy19@tsinghua.org.cn;xiangliu@buaa.edu.cn;fxn17@mail.tsinghua.edu.cn;lulg@mail.tsinghua.edu.cn

摘要/Abstract

摘要：

全固态锂电池具有宽工作温域、高能量密度和高功率密度等优势，是最具有潜力的下一代储能候选电池之一。硫化物电解质Li₁₀GeP₁₂S₂(LGPS)凭借其超高的锂离子电导率(1×10^-3 S/cm)吸引了研究者的广泛关注。但是，高能量密度体系下的LGPS全固态电池关键材料的热稳定性并没有被报道。本工作研究了LGPS为固态电解质，正极为LiNi_0.92Co_0.04Mn_0.04O₂(NCM92)、负极为SiC的全固态电池的热稳定性。通过差示扫描量热法(DSC)和同步热分析-质谱联用(STA-MS)技术，分析了硫化物固态电解质、正极、负极及其混合物的产热产气特性。在产热产气分析的基础上，利用扫描电子显微镜(SEM)结合能量色散X射线谱(EDS)技术、X射线衍射(XRD)和X射线光电子能谱(XPS)对不同温度下的产物成分进行了深入分析。当温度升高至200 ℃时，NCM92正极发生相变，释放大量氧气，与硫化物电解质发生轻微反应，生成P₂S _x 和微量SO₂。当温度升高至310 ℃时，LGPS和正极混合样品发生剧烈放热反应，生成金属氧化物、金属硫化物和磷酸盐等。本研究揭示了NCM92|LGPS|SiC全固态电池关键材料的热稳定性，为全固态锂电池的材料选择和安全优化设计提供理论支持。

关键词: 全固态锂电池, Li₁₀GeP₁₂S₂, 高能量密度, 热稳定性

Abstract:

All-solid-state lithium batteries (ASSLBs) are promising candidates for next-generation energy storage systems because of their wide operating temperature range, high energy density, and high power density. The sulfide solid electrolyte Li₁₀GeP₁₂S₂ (LGPS) has attracted significant attention for its exceptionally high lithium-ion conductivity (1×10^-3 S/cm). However, the thermal stability of key materials in LGPS-based ASSLBs under high energy density configurations has not been reported. This study examines the thermal runaway mechanisms of LGPS solid electrolytes combined with a LiNi_0.92Co_0.04Mn_0.04O₂ (NCM92) cathode and silicon-carbon anode. Differential scanning calorimetry and simultaneous thermal analysis-mass spectrometry were employed to analyze heat generation and gas evolution in solid electrolytes, electrodes, and their mixtures. Following thermal analysis, scanning electron microscopy combined with energy-dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were used to characterize the reaction products at different temperatures. At 200 ℃, the NCM92 cathode undergoes a phase transition, releasing a significant amount of oxygen that reacts mildly with the sulfide electrolyte to form P₂Sₓ and trace SO₂. At 310 ℃, the LGPS and the cathode mixture exhibited exothermic reactions, producing metal oxides, sulfides, and phosphates. This study elucidates the thermal stability of key materials in NCM92|LGPS|SiC ASSLBs, providing theoretical guidance for material selection and safety-oriented design optimization.

Key words: all-solid-state lithium batteries, Li₁₀GeP₁₂S₂, high energy density, thermal stability

中图分类号:

TM 911

张文杰, 任东生, 吴宇, 芮新宇, 刘翔, 冯旭宁, 卢兰光. 基于Li₁₀GeP₁₂S₂ 全固态电池关键材料的热稳定性[J]. 储能科学与技术, 2025, 14(6): 2193-2199.

Wenjie ZHANG, Dongsheng REN, Yu WU, Xinyu RUI, Xiang LIU, Xuning FENG, Languang LU. Thermal stability of key materials in Li₁₀GeP₁₂S₂-based all-solid-state batteries[J]. Energy Storage Science and Technology, 2025, 14(6): 2193-2199.

图/表 5

参考文献 27

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基于Li₁₀GeP₁₂S₂ 全固态电池关键材料的热稳定性

Thermal stability of key materials in Li₁₀GeP₁₂S₂-based all-solid-state batteries

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