Enabling Long Cycle Life and High Rate Iron Difluoride Based Lithium Batteries by In Situ Cathode Surface Modification

Metals fluorides (MFs) are potential conversion cathodes to replace commercial intercalation cathodes. However, the application of MFs is impeded by their poor electronic/ionic conductivity and severe decomposition of electrolyte. Here, a composite cathode of FeF₂ and polymer-derived carbon (FeF₂ @PDC) with excellent cycling performance is reported. The composite cathode is composed of nanorod-shaped FeF₂ embedded in PDC matrix with excellent mechanical strength and electronic/ionic conductivity. The FeF₂ @PDC enables a reversible capacity of 500 mAh g^-1 with a record long cycle lifetime of 1900 cycles. Remarkably, the FeF₂ @PDC can be cycled at a record rate of 60 C with a reversible capacity of 107 mAh g^-1 after 500 cycles. Advanced electron microscopy reveals that the in situ formation of stable Fe₃ O₄ layers on the surface of FeF₂ prevents the electrolyte decomposition and leaching of iron (Fe), thus enhancing the cyclability. The results provide a new understanding to FeF₂ electrochemistry, and a strategy to radically improve the electrochemical performance of FeF₂ cathode for lithium-ion battery applications.