All-solid-state lithium sulfur batteries (ASSLSBs) are considered promising candidates for next-generation energy-storage systems due to their enhanced safety and high theoretical energy density. However, usually both solid-state electrolyte (SSE) and conductive carbon need to be incorporated into the cathode composite to provide Li⁺/electron pathways, leading to the reduced energy density and inevitable SSE decomposition. Moreover, the real electrochemical behavior of S or Li₂S cathodes can not be reflected due to the partially overlapped redox reaction of SSE. Herein, a series of unique P₄S_10+n cathodes for high-performance ASSLSBs that totally do not need any extra SSE additives are reported. Synchrotron-based X-ray absorption near edge structure coupled with other analyses confirmed that ionic conductive Li₃PS₄ together with Li₄P₂S₆ components can be electrochemically self-generated during lithiation process and partially maintained to provide fast Li⁺ transport pathways within the cathode layer. This is further evidenced by a 30–43-fold higher reversible capacity for P₄S_10+n/C cathodes compared to a S/C cathode. Bulk-type ASSLSBs based on the P₄S₃₄/C cathode show a highly reversible capacity of 883 mAh g⁻¹ and stable cycling performance over 180 cycles with a high active material content of 70 wt%. The present study provides a promising approach for generating ionic conductive components from the electrode itself to facilitate Li⁺ migration within electrodes in ASSLSBs.

全固态锂硫电池（ASSLSB）由于其增强的安全性和较高的理论能量密度，被认为是下一代储能系统的有希望的候选者。但是，通常需要将固态电解质（SSE）和导电碳都掺入阴极复合材料中以提供Li ⁺ /电子途径，从而导致能量密度降低和不可避免的SSE分解。而且，由于SSE的部分重叠的氧化还原反应，无法反映S或Li ₂ S阴极的真实电化学行为。这里，一系列独特的P ₄ S _{10 + n}据报道，完全不需要任何额外的SSE添加剂的高性能ASSLSB的阴极。基于同步加速器的近边缘结构的X射线吸收以及其他分析证实，离子导电Li ₃ PS ₄和Li ₄ P ₂ S ₆组分可以在锂化过程中通过电化学方式自生，并部分维持以提供快速的Li ⁺传输途径在阴极层内。与S / C阴极相比，P ₄ S _{10 + n} / C阴极可逆容量高30-43倍，这进一步证明了这一点。基于P ₄ S _34的批量ASSLSB/ C阴极显示出883 mAh g ^-1的高度可逆容量，并在180次循环中具有稳定的循环性能，且活性物质含量高达70 wt％。本研究提供了一种从电极本身生成离子导电成分，以促进Li ⁺在ASSLSBs电极内迁移的有希望的方法。