Effect of Fe content on atomic and electronic structure of complex oxides Sr Ti,Fe O3 delta

Two series of SrTi1 xFexO3 amp; 948; STFO powders with different Fe content produced by two different methods, solid state reaction or modified Pechini synthesis, have been investigated by soft X ray absorption spectroscopy. The O1s K , Fe2p L2,3 and Ti2p L2,3 absorption spectra of STFO powders were analyzed. Partial substitution of Ti by Fe atoms in SrTiO3 were found to cause asymmetric distortion of TiO6 octahedrons which may violate the cubic symmetry of STFO. It was established that the distortion of TiO6 octahedrons increases with increasing Fe content. The joint analysis of the STFO spectra along with the reference compounds points to the presence mainly of Fe3 states in octahedral environment at small concentration of Fe atoms along with essentially smaller content of Fe4 states in octahedral environment where the latter contribution increases with increasing Fe content. Also a presence of Fe3 states in tetrahedral environment with Fe content higher than 50 is traced. A certain amount of Fe2 ions in an octahedral environment was also found in the STFO compound prepared by spray pyrolysis with Fe content higher than 75 . The O1s K absorption spectra point to increase in oxygen vacancy concentration with increasing Fe content. The lowest degree of structure distortions was traced in STFO35. Hence, the STFO35 compound seems to be mostly appropriate for technical application

Charge Transfer Induced Lattice Collapse in Ni Rich NCM Cathode Materials during Delithiation

Ni-rich $LiNi_xCo_yMn_zO_2$ (NCM) cathode materials have great potential for application in next-generation lithium-ion batteries owing to their high specific capacity. However, they are subjected to severe structural changes upon (de)lithiation, which adversely affects the cycling stability. Herein, we investigate changes in crystal and electronic structure of NCM811 (80% Ni) at high states of charge by a combination of operando X-ray diffraction (XRD), operando hard X-ray absorption spectroscopy (hXAS), ex situ soft X-ray absorption spectroscopy (sXAS), and density functional theory (DFT) calculations and correlate the results with data from galvanostatic cycling in coin cells. XRD reveals a large decrease in unit cell volume from 101.38(1) to 94.26(2) $A^3$ due to collapse of the interlayer spacing when x(Li) < 0.5 (decrease in c-axis from 14.469(1) A at x(Li) = 0.6 to 13.732(2) A at x(Li) = 0.25). hXAS shows that the shrinkage of the transition metal–oxygen layer mainly originates from nickel oxidation. sXAS, together with DFT-based Bader charge analysis, indicates that the shrinkage of the interlayer, which is occupied by lithium, is induced by charge transfer between O 2p and partially filled Ni $e_g$ orbitals (resulting in decrease of oxygen–oxygen repulsion). Overall, the results demonstrate that high-voltage operation of NCM811 cathodes is inevitably accompanied by charge-transfer-induced lattice collapse