All‐solid‐state design is effective to address the challenges of Lithium –organic batteries, such as the dissolution of organic electrode materials (OEMs) and the safety of the Li anode. However, previous attempts, based on carbonyl‐type OEMs failed to achieve acceptable electrochemical performance in room‐temperature all‐solid‐state Li batteries (ASSLBs). Herein, the authors report the first organodisulfide cathode, poly(trithiocyanuric acid) (PTTCA), for ASSLBs. By compositing with carbon nanotubes to enhance the electronic conductivity and using the sulfide electrolyte, Li7P3S11, to build an electrochemically favorable interface, PTTCA demonstrates an electrochemical performance superior to all the OEMs reported so far in ASSLBs at room temperature, including a reversible capacity of 410 mAh g−1, an energy density of 767 Wh kg−1, and a capacity retention of 83% after 100 cycles. It is believed that this work provides new orientation and insights for the further development of both ASSLBs and OEMs.

Organic cathode materials (OCMs) for rechargeable Li and Na batteries show great advantages in resource sustainability and huge potential in electrochemical performance but suffer from dissolution problems and costly synthesis. Herein, for the first time, we investigated the copolymer of benzoquinone (BQ) and pyrrole (Py), namely, poly­(benzoquinone-pyrrole) (PBQPy), as an OCM for Li batteries. The low-cost raw materials and solvent-free synthesis provide PBQPy much brighter prospects in large-scale production compared to other carbonyl-based polymer cathode materials. Nevertheless, PBQPy showed one of the best electrochemical performances among all OCMs, including excellent energy density (2.32 V × 255 mAh g–1 = 592 Wh kg–1), rate capability (79%@2000 mA g–1), and cycling stability (81%@1000th cycle). By introducing poly­(benzoquinone-methyl pyrrole) for comparison, as well as employing density functional theory calculations and various characterizations for in-depth understanding, the synthesis mechanism, polymer structure, electrochemical behavior, and redox mechanism were clearly clarified. It is believed that this work will encourage more efforts to develop cost-effective OCMs toward practical organic batteries.

Organic cathode materials (OCMs) possess high resource sustainability, large structural diversity, high theoretical energy density, and potentially low cost, however, suffer from the dissolution problem in liquid non‐aqueous electrolyte. Solid‐state batteries (SSBs) are regarded as the final solution of Li and Na metal batteries because of the intrinsic safety, but hindered by many challenges including the poor contact with rigid inorganic cathode materials. Therefore, applying OCMs in SSBs is probably a win‐win strategy to compensate for their respective deficiency. In this review, some fundamental knowledge of OCMs and SSBs are briefly introduced at first, with emphasis on different types of solid‐state electrolytes (SSEs). Then the reported works on OCM‐based SSBs are summarized by classifying them into non‐ceramic, semi‐ceramic, and all‐ceramic ones. Finally, we conclude our understandings on the main scientific issues and possible solutions. To sum up, the combination of OCMs and SSBs brings about many new challenges but also opportunities towards their practical application.