Organic cathode materials have garnered significant attention for their potential application in lithium-ion batteries due to their lightweight nature, tunable structures, high energy density, and environmental friendliness. However, the dissolution of organic cathodes in liquid electrolytes often leads to poor cycling stability, which limits their practical application. In this study, a composite cathode was prepared by ball milling the PTCDA/CuS (perylene-3,4,9,10-tetracarboxylic dianhydride, PTCDA) with a sulfide-based electrolyte and carbon nanotubes. By optimizing the component ratios, the assembled all-solid-state batteries (ASSBs) show a high discharge capacity of 210 mA·h/g after 200 cycles without any capacity degradation at a current density of 33.0 mA/g. Through comprehensive characterization techniques including X-ray diffraction (XRD), Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), the coordination of Cu²⁺ and the formation of sulfur-linked polymers during the charge-discharge processes are elucidated, and the reversibility of the electrochemical reactions has been confirmed. This work highlights the excellent compatibility between organic cathodes and sulfide-based electrolytes, providing a new way for the development of high-performance ASSBs with high energy density and extended lifespan.

Organic electrode materials (OEMs) constitute an attractive class of energy storage materials for potassium-ion batteries, but their application is severely hindered by sluggish kinetics and limited capacities. Herein, inorganic molecules covalent combination strategy is proposed to drive advanced potassium organic batteries. Specifically, molecular selenium, possessing high potential of conductivity and electroactivity, is covalently bonded with organic matrix, that is symmetrical selenophene-annulated dipolyperylene diimide (PDI2-2Se), is designed to verify the feasibility. The inorganic-anchored OEM (PDI2-2Se) can be electrochemically activated to form organic (PDI2 matrix)–inorganic (Se) hybrids during initial cycles. Stateof-the-art 3D tomography reveals that a “mutual-accelerating” effect was realized, that is, the 10-nm Se quantum dots, possessing high conductivity, facilitate charge transfer in organics as well store K⁺-ions, and organic PDI2 matrix benefits the encapsulation of Se, thereby suppressing shuttle effect and volume fluctuation during cycling, endowing resulting PDI2/Se hybrids with both high-rate capacities and longevity. The concept of inorganicconfigurated OEM through covalent bonds, in principle, can also be extended to design novel functional organic-redox electrodes for other high-performance secondary batteries.