Wang Sheng, Zhou Yaqing, Huang Xiao, Xu Deli, Li Minghua, Wu Guoxian, Cheng Hao, Cheng Yan, Yu Zhaozhe, Tian Bingbing
Guangxi Key Laboratory of Manufacturing Systems and Advanced Manufacturing Technology, Guilin University of Electronic Technology, Guilin 541004, Guangxi, China.
International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Shenzhen Key Laboratory of 2D Metamaterials for Information Technology, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen 518060, Guangdong, China.
ACS Appl Mater Interfaces. 2025 Aug 6;17(31):44430-44439. doi: 10.1021/acsami.5c07580. Epub 2025 Jul 23.
Halide superionic conductors have garnered considerable attention due to their high ionic conductivity, mechanical deformability, and excellent oxidative stability. However, their incompatibility with lithium metal results in a thermodynamically unstable interface that increases interfacial impedance, thereby limiting the performance of halide-based all-solid-state lithium-metal batteries (ASSLBs). In this study, we report the synthesis of a series of iodide-chloride solid electrolytes, LiZrClI (x = 0-3), designed to enhance the reduction stability of the electrolyte through the high polarizability of I. The substitution of I promotes covalent bonding with the central cation, thereby reducing its reduction tendency. The Li/LiZrClI/Li symmetric cell exhibits stable cycling for over 6000 h at 0.2 mA cm and withstands high critical current densities up to 6 mA cm. Full cells incorporating LiZrClI as the solid electrolyte exhibit enhanced cycling stability and capacity retention. Furthermore, the characterization by XPS and ToF-SIMS revealed the formation of an interfacial passivation layer composed of LiI and LiCl, which effectively stabilized the lithium-metal electrode and inhibited further electrolyte decomposition. These findings highlight the potential of iodide-substituted halide electrolytes in addressing interfacial challenges associated with lithium metal anodes, providing a promising pathway for the practical implementation of high-energy-density ASSLBs.
卤化物超离子导体因其高离子电导率、机械可变形性和出色的氧化稳定性而备受关注。然而，它们与锂金属的不相容性导致热力学不稳定的界面，增加了界面阻抗，从而限制了卤化物基全固态锂金属电池（ASSLBs）的性能。在本研究中，我们报道了一系列碘化物-氯化物固体电解质LiZrClI（x = 0 - 3）的合成，旨在通过I的高极化率提高电解质的还原稳定性。I的取代促进了与中心阳离子的共价键合，从而降低了其还原倾向。Li/LiZrClI/Li对称电池在0.2 mA cm下表现出超过6000小时的稳定循环，并能承受高达6 mA cm的高临界电流密度。以LiZrClI作为固体电解质的全电池表现出增强的循环稳定性和容量保持率。此外，通过XPS和ToF-SIMS表征揭示了由LiI和LiCl组成的界面钝化层的形成，该钝化层有效地稳定了锂金属电极并抑制了电解质的进一步分解。这些发现突出了碘化物取代的卤化物电解质在解决与锂金属阳极相关的界面挑战方面的潜力，为高能量密度ASSLBs的实际应用提供了一条有前景的途径。
