biostudies-literatureWang DKey Research Project of Zhejiang LabNatural Science Foundation of ShanghaiNational Natural Science Foundation of Chinanwad010https://www.ebi.ac.uk/biostudies/studies/S-EPMC9976772biostudies-literatureUnknown10(3)Pairing Li-free transition-metal-based cathodes (MX) with Li-metal anodes is an emerging trend to overcome the energy-density limitation of current rechargeable Li-ion technology. However, the development of practical Li-free MX cathodes is plagued by the existing notion of low voltage due to the long-term overlooked voltage-tuning/phase-stability competition. Here, we propose a p-type alloying strategy involving three voltage/phase-evolution stages, of which each of the varying trends are quantitated by two improved ligand-field descriptors to balance the above contradiction. Following this, an intercalation-type 2H-V_1.75Cr_0.25S₄ cathode tuned from layered MX₂ family is successfully designed, which possesses an energy density of 554.3 Wh kg<sup>National science reviewA customized strategy to design intercalation-type Li-free cathodes for all-solid-state batteries.PMC997677222ZR1424500U2030206118742542021PE0AC0222279077Yin XShi SWang DChen LLi QAvdeev MYu JWang YShao SfalseA customized strategy to design intercalation-type Li-free cathodes for all-solid-state batteries.Pairing Li-free transition-metal-based cathodes (MX) with Li-metal anodes is an emerging trend to overcome the energy-density limitation of current rechargeable Li-ion technology. However, the development of practical Li-free MX cathodes is plagued by the existing notion of low voltage due to the long-term overlooked voltage-tuning/phase-stability competition. Here, we propose a p-type alloying strategy involving three voltage/phase-evolution stages, of which each of the varying trends are quantitated by two improved ligand-field descriptors to balance the above contradiction. Following this, an intercalation-type 2H-V_1.75Cr_0.25S₄ cathode tuned from layered MX₂ family is successfully designed, which possesses an energy density of 554.3 Wh kg<sup>2023-01-01T00:00:00Z2023 Mar2025-05-18T12:54:39.928Z2025-04-05T13:01:29.083ZS-EPMC99767723687578810.1093/nsr/nwad010