LAUSR

Abstract 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-V1.75Cr0.25S4 cathode tuned from layered MX2 family is successfully designed, which possesses an energy density of 554.3 Wh kg−1 at the electrode level accompanied by interfacial compatibility with sulfide solid-state electrolyte. The proposal of this class of materials is expected to break free from scarce or high-cost transition-metal (e.g. Co and Ni) reliance in current commercial cathodes. Our experiments further confirm the voltage and energy-density gains of 2H-V1.75Cr0.25S4. This strategy is not limited to specific Li-free cathodes and offers a solution to achieve high voltage and phase stability simultaneously.