Determining the Role of Fe-Doping on Promoting the Thermochemical Energy Storage Performance of (Mn_{1- x} Fe_x )₃ O₄ Spinels

Mn oxides are promising materials for thermochemical heat store, but slow reoxidation of Mn₃ O₄ to Mn₂ O₃ limits efficiency. In contrast, (Mn_{1- x} Fe_x )₃ O₄ oxides show an enhanced transformation rate, but fundamental understanding of the role played by Fe cations is lacking. Here, nanoscale characterization of Fe-doped Mn oxides is performed to elucidate how Fe incorporation influences solid-state transformations. X-ray diffraction reveals the presence of two distinct spinel phases, cubic jacobsite and tetragonal hausmannite for samples with more than 10% of Fe. Chemical mapping exposes wide variation of Fe content between grains, but an even distribution within crystallites. Due to the similarities of spinels structures, high-resolution scanning transmission electron microscopy cannot discriminate unambiguously between them, but Fe-enriched crystallites likely correspond to jacobsite. In situ X-ray absorption spectroscopy confirms that increasing Fe content up to 20% boosts the reoxidation rate, leading to the transformation of Mn²⁺ in the spinel phase to Mn³⁺ in bixbyite. Extended X-ray absorption fine structure shows that FeO length is larger than MnO, but both electron energy loss spectroscopy and X-ray absorption near edge structure indicate that iron is always present as Fe³⁺ in octahedral sites. These structural modifications may facilitate ionic diffusion during bixbyite formation.