Modulating Local Structure of Amorphous Oxyhalide to Achieve High-Rate and Ultra-Stable All-Solid-State Lithium...

Halides-based all-solid-state lithium batteries (ASSLBs) attract great attention because of their wide electrochemical window and fine processibility. However, low ionic conductivity of halides and solid-solid interface incompatibility result in inferior rate capability and poor cycling stability. Herein, we modulate local structure (short-range-structure disorder degree, coordination diversity, and so forth) via a synergistic anion-cation strategy to achieve amorphous solid electrolyte 1.6Li₂O-TaCl₅-0.3MgF₂ (LTOC-M) with a high ionic conductivity (11.15 mS cm^-1) and favorable interfacial compatibility. F incorporation at Cl/O sites strengthens Ta─F bonding and Li-F interactions, enhancing long-term cycling stability, while Mg incorporation modulates the local cationic environment, increases coordination diversity, and facilitates Li⁺ transport within the amorphous matrix. ASSLBs with LiNi_0.8Co_0.1Mn_0.1O₂ or LiCoO₂ demonstrate superhigh rate capability and long-term cycling stability (LiNi_0.8Co_0.1Mn_0.1O₂:92.29%@4000cycles@5C; LiCoO₂:80.85%@5000cycles@10C). When paired with Li-rich Li_1.2Mn_0.54Ni_0.13Co_0.13O₂, the cell delivers a high initial capacity of 270.38 mAh g^-1 with a cycling stability (92.75%@120cycles@0.2C). Moreover, Li-In| Li₆PS₅Cl-LTOC-M|LiCoO₂ delivers a high discharge capacity of 128.80 mAh g^-1 at -20°C and demonstrates a cycling stability (96.62%@550cycles@0.2C), and the battery functions even at -75°C for over 400 h. The proposed strategy effectively enhances high-rate performance, long-term cycling stability and low-temperature performance of halides-based ASSLBs, accelerating their practical application.