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借助C600微量热仪和差示扫描量热仪研究了石榴石型氧化物固态电解质Li_7La_3Zr_2O12(LLZO)、Li6.5La_3Zr1.5Nb0.5O12(LLZNO)、不同粒径Li6.4La_3Zr1.4Ta0.6O12(LLZTO300 nm、LLZTO500 nm、LLZTO5μm)在烧结前后的热稳定性以及惰性环境下电解质/满电态电极体系的热稳定性。通过对反应热特性参数的比较，发现固态电解质的加入使满电态电极的起始反应温度提前。结果表明：Nb和Ta元素掺杂对LLZO基固态电解质的结构有一定的稳定作用，但同时Nb和Ta元素掺杂对满电态电极热稳定性影响较大，Nb元素掺杂提高了LLZO基固态电解质与正极的热稳定性；Nb和Ta元素掺杂降低了LLZO基固态电解质与石墨负极的热稳定性，但一定程度上提高了与硅碳负极和金属锂的热稳定性；对比三种粒径LLZTO电解质，LLZTO5μm/电极的热稳定性较差。结合热流曲线和多种表征技术，分析了电解质/电极体系在升温过程中可能的热反应机理。
Abstract：The use of solid electrolytes in place of traditional electrolytes is anticipated to address battery safety issues. Among these, the garnet-type electrolyte Li_7La_3Zr_2O12(LLZO) has garnered significant attention. To address the limited research on the thermal stability of LLZO-based solid electrolytes, this study utilized a C600 microcalorimeter to investigate the thermal stability of LLZO, Li6.5La_3Zr1.5Nb0.5O12(LLZNO), and Li6.4La_3Zr1.4Ta0.6O12(including variants LLZTO300 nm, LLZTO500 nm, and LLZTO5 μm) both before and after sintering. Doping with Nb and Ta elements was found to have a stabilizing effect on the structure of LLZO-based solid electrolytes. To further assess the thermal safety of these electrolytes in practical applications, we tested the thermal stability of fully charged positive electrode/electrolyte systems(LiFePO4, LiNi0.6Mn0.2Co0.2O2) and fully charged negative electrode/electrolyte systems(graphite, silicon-carbon, lithium) under inert conditions using both a DSC thermal analyzer and the C600 microcalorimeter. The incorporation of solid electrolytes lowers the initial reaction temperature of fully charged electrodes. Considering both the reaction process and thermal characteristic parameters, the thermal stability of the positive electrode/electrolyte in an inert environment ranks from high to low as follows: LiFePO4(LFP) and NCM622. In a sealed inert environment, the thermal stability of the negative electrode/electrolyte decreases in the following order: lithium, graphite, and silicon carbide. Doping with Nb and Ta elements significantly influences heat release. Specifically, Nb doping enhances thermal stability when paired with the positive electrode. Conversely, while Nb and Ta doping reduces thermal stability with the graphite anode, it improves stability with the silicon-carbon anode and metallic lithium. Among the three particle sizes of LLZTO evaluated, LLZTO5 μm/electrode exhibits the poorest thermal stability. By integrating heat flow curves, Thermogravimetric-Mass Spectrometry(TG-MS), and Scanning Electron Microscope(SEM) testing, we speculated on the potential thermal reaction mechanisms of the electrode/electrolyte during the heating process. The heat released by the fully charged positive electrode/electrolyte system primarily arises from the oxygen release phase transition of the positive electrode material during heating, while the oxygen released by the electrolyte influences this process. In the systems containing fully charged graphite/electrolyte and fully charged silicon-carbon/electrolyte, the heat generated is attributed to the collapse of the negative electrode material structure, where the released lithium reacts with the oxygen released by the electrolyte. In the Li/electrolyte system, lithium directly interacts with the oxygen released from the electrolyte, and doping with Ta significantly affects the number of exothermic peaks observed.
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基本信息:
DOI：10.13637/j.issn.1009-6094.2025.1204
中图分类号:O646;TM912
引用信息:
[1]高伟,王嘉莹,崔昊,等.LLZO基固态电解质及电极热稳定性研究[J].安全与环境学报,2026,26(07):2614-2626.DOI:10.13637/j.issn.1009-6094.2025.1204.
基金信息:
国家自然科学基金区域创新发展联合基金重点项目(U22A20168)
2026-03-17
2026-03-17
2026-03-17