Fluoride ion batteries (FIBs) are a recent alternative all-solid-state battery technology. However, the FIB systems proposed so far suffer from poor cycling performance. In this work, we report La 2 NiO 4.13 with a Ruddlesden-Popper type structure as an intercalation-based active cathode material in all solid-state FIB with excellent cycling performance. The critical charging conditions to maintain the conductivity of the cell were determined, which seems to be a major obstacle towards improving the cycling stability of FIBs. For optimized operating conditions, a cycle life of about 60 cycles and over 220 cycles for critical cutoff capacities of 50 mAh/g and 30 mAh/g, respectively, could be achieved, with average Coulombic efficiencies between 95-99%. Cycling of the cell is a result of fluorination/de-fluorination into and from the La 2 NiO 4+d cathode, and it is revealed that La 2 NiO 4.13 is a multivalent electrode material. Our findings suggest that La 2 NiO 4.13 is a promising high energy cathode for FIBs.

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