Authors
Piernas-Munoz, Maria; Castillo-Martnez, Elizabeth; Goikolea, Eider; Blanco, Pablo; Legarra, Estbaliz; Garitaonandia, Jos Javier S.; Kim, Soojeong; Fister, Timothy; Johnson, Christopher; Rojo, Teofilo
Abstract
Ex situ X-ray absorption spectroscopy and in operando 57Fe-Mo??ssbauer spectroscopy measurements are conducted to examine in detail the ongoing reaction mechanism of potassium Prussian blue (K-PB) within the narrow [1.6-0.005 voltage range, and so to determine whether this material truly undergoes a conversion reaction, as we proposed elsewhere. The generation of Fe0 is confirmed by both techniques, finding that 40 to 58% of iron gets reduced to metallic iron at 5 mV. The elucidation of the mechanism by in situ 57Fe-Mo??ssbauer spectroscopy further reveals a sequential process for the reduction (lithiation) of the two different iron species initially present in Prussian blue. Both high-spin Fe2+-N first and low-spin FeII-C next go through the unusual Fe1+/I formal oxidation state during the reduction process, before forming surface Fe0 nanoparticles (NPs) below 0.48 V. Upon charge, Fe0 NPs preferentially oxidizes into Fe+ -N. Interestingly, these surprising Fe+ species play an important role in decreasing the overpotential during the charge (delithiation) process with respect to other conversion systems