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Here we provide an in-depth structural characterization of the amorphous ionic glasses LiPON and LiSiPON with high Li content. Based on ab-initio molecular dynamics simulations, the structure of these materials is an inverted structure with either isolated polyanion tetrahedra or polyanion dimers suspended in a Li+ matrix. Based on neutron scattering data, this type of inverted structure leads to a significant amount of medium-range ordering in the structure, as demonstrated by two sharp diffraction peaks and a periodic structural oscillation in the density function G(r). On a local scale, adding N and Si increases the number of anion bridges and polyanion dimer structures, leading to higher ionic conductivity. In the medium range ordering, the addition of Si leads to more disorder in the polyanion substructure but a significant increase in the ordering of the O substructure. Finally, we demonstrate that this inverted structure with medium range ordering results in a glassy material that is both mechanically stiff and ductile on the nanoscale. 

Non-stoichiometric perovskite oxides have been studied as a new family of redox oxides for solar thermochemical hydrogen (STCH) production owing to their favourable thermodynamic properties. However, conventional perovskite oxides suffer from limited phase stability and kinetic properties, and poor cyclability. Here, we report a strategy of introducing A-site multi-principal-component mixing to develop a high-entropy perovskite oxide, (La1/6Pr1/6Nd1/6Gd1/6Sr1/6Ba1/6)MnO3 (LPNGSB_Mn), which shows desirable thermodynamic and kinetics properties as well as excellent phase stability and cycling durability. LPNGSB_Mn exhibits enhanced hydrogen production (∼77.5 mmol/mol-oxide) compared to (La2/3Sr1/3)MnO3 (∼53.5 mmol / mol-oxide) in a short 1 hour redox duration and high STCH and phase stability for 50 cycles. LPNGSB_Mn possesses a moderate enthalpy of reduction (252.51–296.32 kJ / mol-oxide), a high entropy of reduction (126.95–168.85 J / mol-oxide), and fast surface oxygen exchange kinetics. All A-site cations do not show observable valence changes during the reduction and oxidation processes. This research preliminarily explores the use of one A-site high-entropy perovskite oxide for STCH.