The development of all‐solid‐state Li metal batteries (ASSLMBs) has attracted significant attention due to their potential to maximize energy density and improved safety compared to the conventional liquid‐electrolyte‐based Li‐ion batteries. However, it is very challenging to fabricate an ideal solid‐state electrolyte (SSE) that simultaneously possesses high ionic conductivity, excellent air‐stability, and good Li metal compatibility. Herein, a new glass‐ceramic Li_3.2P_0.8Sn_0.2S₄ (gc‐Li_3.2P_0.8Sn_0.2S₄) SSE is synthesized to satisfy the aforementioned requirements, enabling high‐performance ASSLMBs at room temperature (RT). Compared with the conventional Li₃PS₄ glass‐ceramics, the present gc‐Li_3.2P_0.8Sn_0.2S₄ SSE with 12% amorphous content has an enlarged unit cell and a high Li⁺ ion concentration, which leads to 6.2‐times higher ionic conductivity (1.21 × 10⁻³ S cm⁻¹ at RT) after a simple cold sintering process. The (P/Sn)S₄ tetrahedron inside the gc‐Li_3.2P_0.8Sn_0.2S₄ SSE is verified to show a strong resistance toward reaction with H₂O in 5%‐humidity air, demonstrating excellent air‐stability. Moreover, the gc‐Li_3.2P_0.8Sn_0.2S₄ SSE triggers the formation of Li–Sn alloys at the Li/SSE interface, serving as an essential component to stabilize the interface and deliver good electrochemical performance in both symmetric and full cells. The discovery of this gc‐Li_3.2P_0.8Sn_0.2S₄ superionic conductor enriches the choice of advanced SSEs and accelerates the commercialization of ASSLMBs.

中文翻译：

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空气稳定且与锂金属兼容的玻璃陶瓷电解质，可提供高性能的全固态锂金属电池

与传统的基于液体电解质的锂离子电池相比，全固态锂金属电池（ASSLMB）的发展备受关注，因为它们具有最大化能量密度和提高安全性的潜力。但是，要制造一种理想的固态电解质（SSE），同时具有高离子电导率，出色的空气稳定性和良好的锂金属相容性，这是非常困难的。在这里，新的玻璃陶瓷Li _3.2 P _0.8 Sn _0.2 S ₄（gc-Li _3.2 P _0.8 Sn _0.2 S ₄）SSE经过合成可以满足上述要求，从而可以在室温（RT）下实现高性能的ASSLMB。与传统的Li ₃ PS ₄玻璃陶瓷相比，目前的gc-Li _3.2 P _0.8 Sn _0.2 S ₄ SSE的非晶含量为12％，具有更大的晶胞和较高的Li ⁺离子浓度，这导致其高6.2倍。简单的冷烧结过程后的离子电导率（室温下为1.21×10 ^-3 S cm ^-1）。gc-Li _3.2 P _0.8 Sn _0.2 S ₄内部的（P / Sn）S ₄四面体经验证，SSE对在5％湿度的空气中与H ₂ O的反应具有很强的抵抗力，表明其出色的空气稳定性。此外，gc-Li _3.2 P _0.8 Sn _0.2 S ₄ SSE触发了Li / SSE界面处Li-Sn合金的形成，是稳定界面并在对称电池和全电池中提供良好电化学性能的重要成分。这种gc-Li _3.2 P _0.8 Sn _0.2 S ₄超离子导体的发现丰富了高级SSE的选择，并加速了ASSLMBs的商业化。