Feng Yitian, Zhu Zhewen, Yang Lin, Mu Yongbiao, Yan Zihan, Cui Haoting, Ye Yu, Zuo Daxian, Hu Qiwei, Zhu Yizhou, Zeng Lin, Wan Jiayu
Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen, 518055, China.
Research Center for Industries of the Future and School of Engineering, Westlake University, Hangzhou, 310030, China.
Adv Mater. 2025 Oct;37(41):e09838. doi: 10.1002/adma.202509838. Epub 2025 Jul 24.
All-solid-state lithium metal batteries offer enhanced safety and energy density by replacing flammable liquid electrolytes with solid-state electrolytes (SSEs). High-entropy (HE) SSEs, leveraging multi-principal-element compositions, present a vast design space to achieve exceptional ionic conductivity and electrochemical stability. However, the chemical complexity of HE SSEs introduces challenges in interfacial instability with lithium metal anodes due to the unavoidable inclusion of reactive elements. While conventional garnet-type SSEs are considered stable, it is revealed that five HE garnets (HE-LLZOs) undergo corrosion and partial dissolution upon lithium contact. Here, a rational design strategy is introduced to stabilize HE-LLZO by combining thermodynamic assessments of interfacial reactivity with targeted compositional engineering. Through systematic exploration of element-specific degradation mechanisms, selection criteria for lithium-compatible principal elements are established. Guided by computational screening, unstable dopants are excluded (e.g., Nb, Mo, W, Cr, Bi) that drive interfacial degradation and synthesize a novel HE-LLZO (LiLaZrSnHfScTaO) that exhibits high ionic conductivity (3.69 × 10 S cm) and stable cycling over 2,500 h. X-ray photoelectron spectroscopy confirms the interfacial stability of Zr, Sn, and Ta while identifying Nb as a destabilizing element. This work provides an integrated computational-experimental framework for understanding element-property relationships in HE oxides, advancing durable SSEs design.
全固态锂金属电池通过用固态电解质（SSE）替代易燃的液体电解质，提高了安全性和能量密度。高熵（HE）SSE利用多主元成分，提供了广阔的设计空间，以实现卓越的离子电导率和电化学稳定性。然而，由于不可避免地包含活性元素，HE SSE的化学复杂性给与锂金属负极的界面不稳定性带来了挑战。虽然传统的石榴石型SSE被认为是稳定的，但研究发现，五种HE石榴石（HE-LLZO）在与锂接触时会发生腐蚀和部分溶解。在此，引入了一种合理的设计策略，通过将界面反应性的热力学评估与有针对性的成分工程相结合，来稳定HE-LLZO。通过系统探索特定元素的降解机制，建立了与锂兼容的主元素的选择标准。在计算筛选的指导下，排除了驱动界面降解的不稳定掺杂剂（如Nb、Mo、W、Cr、Bi），并合成了一种新型的HE-LLZO（LiLaZrSnHfScTaO），其具有高离子电导率（3.69×10 S cm），并在2500小时以上实现稳定循环。X射线光电子能谱证实了Zr、Sn和Ta的界面稳定性，同时确定Nb是一种不稳定元素。这项工作提供了一个综合的计算-实验框架，用于理解HE氧化物中的元素-性质关系，推动耐用SSE的设计。
