Electrochemical Activation of Fe-LiF Conversion Cathodes in Thin-Film Solid-State Batteries

Transition metal fluoride (TMF) conversion-type cathodes promise up to 4 times higher gravimetric energy densities compared to those of common intercalation-type cathodes. However, TMF cathodes demonstrate sluggish kinetics, poor efficiencies, and incompatibility with many liquid electrolytes. In this work, coevaporated heterostructured iron and lithium fluoride (Fe-LiF) cathodes are investigated in thin-film solid-state batteries with a LiPON electrolyte and a lithium metal anode. The cells were cycled 2000 times at a cycling rate of 6C. They show a gradual improvement in voltaic efficiency (37–53%) and specific capacity (146–216 mAh/g) during cycling. After 2000 cycles, the cathode capacity reaches 480 mAh/g at a cycling rate of C/3.6, close to its theoretical capacity of 498 mAh/g, at room temperature conditions. This capacity gain is correlated with an observed electrochemically activated nanorestructuring of the cathode, characterized by cycling-induced coarsening (from 2.8 to 4.2 nm) of the metallic iron phase and its accumulation near the current collector interface, as well as lithium fluoride phase accumulation near the LiPON interface.