Design Principles of Quinone Redox Systems for Advanced Sulfide Solid‐State Organic Lithium Metal Batteries

Abstract The emergence of solid‐state battery technology presents a potential solution to the dissolution challenges of high‐capacity small molecule quinone redox systems. Nonetheless, the successful integration of argyrodite‐type Li6PS5Cl, the most promising solid‐state electrolyte system, and quinone redox systems remains elusive due to their inherent reactivity. Here, a library of quinone derivatives is selected as model electrode materials to ascertain the critical descriptors governing the (electro)chemical compatibility and subsequently the performances of Li6PS5Cl‐based solid‐state organic lithium metal batteries (LMBs). Compatibility is attained if the lowest unoccupied molecular orbital level of the quinone derivative is sufficiently higher than the highest occupied molecular orbital level of Li6PS5Cl. The energy difference is demonstrated to be critical in ensuring chemical compatibility during composite electrode preparation and enable high‐efficiency operation of solid‐state organic LMBs. Considering these findings, a general principle is proposed for the selection of quinone derivatives to be integrated with Li6PS5Cl, and two solid‐state organic LMBs, based on 2,5‐diamino‐1,4‐benzoquinone and 2,3,5,6‐tetraamino‐1,4‐benzoquinone, are successfully developed and tested for the first time. Validating critical factors for the design of organic battery electrode materials is expected to pave the way for advancing the development of high‐efficiency and long cycle life solid‐state organic batteries based on sulfides electrolytes.