All-solid-state Li batteries (ASSLBs) with solid-state electrolytes (SSEs) are exciting candidates for next-generation energy storage and receive considerable attention owing to their reliability. Halide SSEs are promising candidates due to their excellent stability against 4 V-class layered cathodes. Compared with Li₃InCl₆ or Li₃ScCl₆, the low ionic conductivity of Li₂ZrCl₆ (LZC) is a challenge despite its low raw-material cost. Herein, we report a family of Li-Richened chloride, Li_2+2xZr_1–xM_xCl₆, which can be used in high-performance ASSLBs owing to its high ionic conductivity (up to 0.62 mS cm⁻¹). The theoretical (ab initio molecular dynamics simulations) and experimental results prove that the strategy of aliovalent substitution with divalent metals to obtain Li-Richened LZC is effective in improving Li⁺ conductivity in SSEs. By combining Li_2.1Zr_0.95Mg_0.05Cl₆ (Mg5-LZC) with a Li–In anode and a LiCoO₂ cathode, a room-temperature ASSLBs with excellent long-term cycling stability (88% capacity retention at 0.3C for 100 cycles) and high-rate capability (121 mA h g⁻¹ at 1C) is reported. This exploratory work sheds light on improving the Li⁺ conductivity of low-cost LZC-family SSEs for constructing high performance ASSLBs.

具有固态电解质（SSE）的全固态锂电池（ASSLB）是下一代储能的令人兴奋的候选者，并且由于其可靠性而受到广泛关注。卤化物 SSE 是有前途的候选者，因为它们对 4 V 级层状阴极具有出色的稳定性。与Li ₃ InCl ₆或Li ₃ ScCl _{6相比，Li 2} ZrCl ₆ (LZC)的低离子电导率是一个挑战，尽管其原材料成本低。在此，我们报告了一个富锂氯化物家族，Li _{2+2 x} Zr _{1– x} M _x Cl ₆^{，由于其高离子电导率（高达 0.62 mS cm -1}），可用于高性能 ASSLB 。理论（从头算分子动力学模拟）和实验结果证明，用二价金属进行异价取代以获得富锂 LZC 的策略可有效提高SSE 中的Li ^{+电导率。}通过将 Li _2.1 Zr _0.95 Mg _0.05 Cl ₆ (Mg5-LZC) 与 Li–In 阳极和 LiCoO ₂阴极组合，室温 ASSLBs 具有出色的长期循环稳定性（在 0.3C 下 88% 容量保持 100 个循环) 和高倍率能力 (121 mA h g ⁻¹在 1C) 被报道。这项探索性工作为提高低成本 LZC 系列 SSE 的Li ^{+电导率以构建高性能 ASSLB 提供了思路。}