Solid electrolytes with high ionic conductivity and good stability are advantageous over the current liquid electrolytes in rechargeable Li-ion batteries. Argyrodites, Li₆PS₅X (X ​= ​Cl, Br, or I), with ionic conductivities on the order of mS/cm have attracted tremendous attention. However, the high potential of argyrodites in fast ion conduction is far from being reached. Significant enhancement in ion conduction relies on the fundamental understanding of the contributing factors for fast ion transport. Here, we have systematically prepared highly conductive Li-deficient Li_6−xPS_5−xCl_1+x and examined the influence of Li-deficiency and Cl substitution of S on ion transport using impedance spectroscopy, solid-state NMR, and first-principles calculations. With increased Cl content, the amount of Cl⁻ at S²⁻ (4d) sites increases, forming a dominant 1S3Cl (4d) configuration. In addition, Li⁺ redistributes with significantly higher mobility. As a result, the activation energy for Li-ion transport decreases, and the conductivity increases to 17 ​mS/cm at 25 ​°C when x equals 0.7 (Li_5.3PS_4.3Cl_1.7). This work not only reports a record ionic conductivity of Cl-containing argyrodites-type fast Li-ion conductors, but also provides new insights into anion disorder-induced ion transport, which has a wide and universal appeal in the development of fast ion conductors and mixed-anion functional materials.

具有高离子电导率和良好稳定性的固体电解质优于可再充电锂离子电池中的当前液体电解质。锂离子电导率约为mS / cm的锂₆ PS ₅ X（X = Cl，Br或I）引起了人们的极大关注。但是，远远不能达到在快速离子传导中具有高电位的银辉石。离子传导的显着增强取决于对快速离子传输的影响因素的基本理解。在这里，我们系统地准备了高导电性的缺锂Li _6−x PS _5−x Cl _{1 + x}并使用阻抗谱，固态NMR和第一性原理计算研究了Li缺乏和Cl的S取代对离子迁移的影响。具有增加的Cl含量，氯的量^-处为^2- （4 d）位点的增加，形成一个主导1S3Cl（4 d）配置。此外，Li ⁺具有更高的迁移率。结果，当x等于0.7（Li _5.3 PS _4.3 Cl _1.7时，锂离子传输的活化能降低，电导率在25°C时增加到17 mS / cm。）。这项工作不仅报告了含Cl的银离子型快Li离子导体的创纪录的离子电导率，而且为阴离子紊乱引起的离子迁移提供了新的见解，它在快速离子导体和快速离子导体的发展中具有广泛而普遍的吸引力。混合阴离子功能材料。