Re-evaluation of experimental measurements for the validation of electronic band structure calculations for LiFePO and FePO.

Experimental measurements used to validate previous electronic band structure calculations for olivine LiFePO and its delithiated phase, FePO, have been re-investigated in this study. Experimental band gaps of LiFePO and FePO have been determined to be 6.34 eV and 3.2 eV by electron energy loss spectroscopy (EELS) and UV-Vis-NIR diffusion reflectance spectroscopy, respectively. X-ray photoemission (XPS) and Raman spectroscopy show that the surfaces of very carefully synthesized LiFePO display Li-depletion, which affects optical reflectance determinations. Based on these experimental measurements, functionals for density functional theory (DFT) calculations of the electronic properties have been revisited. Overall, electronic structures of LiFePO and FePO calculated using sX-LDA show the best self-consistent match to combined experimentally determined parameters. Furthermore, the open-circuit voltages of the LiFePO half-cell have been interpreted in terms of both Fermi levels and Gibbs free energies, which provides additional support for the electronic band structures determined by this research.