• • MMFC-400 achieves high specific capacity and rate capability, with cycling stability, attributed to multiphase interfaces that accelerate Li+ migration and provide additional active sites, overcoming the <20 nm transport limitation.
• • The hydrothermal synthesis and annealing at 400°C yield a multicomponent synergistic effect, enhancing electrochemical performance beyond single-component metal fluorides.
• • The multiphase interfacial structure provides abundant unsaturated coordinated atoms, increasing Li+ storage active sites and improving overall capacity.
• • This work introduces a novel multiphase interfacial energy storage concept for TMFs, potentially enabling higher energy density LIBs compared to traditional intercalation cathodes like LiFePO4 (~170 mAh g−1) and LiCoO2 (~274 mAh g−1).