Hole polaron formation and migration in olivine phosphate materials

TL;DR

This study combines first principles calculations and experimental XPS to analyze hole polaron formation and migration in LiMPO4 cathode materials, revealing the influence of electronic structure features and methodology on these processes.

Contribution

It demonstrates that hybrid functional calculations better reproduce experimental spectra and clarifies how different LiMPO4 compounds support hole polarons and their migration barriers.

Findings

LiNiPO4 cannot support small hole polarons

Migration barrier varies significantly among compounds

Hybrid functional approach aligns well with experimental data

Abstract

By combining first principles calculations and experimental XPS measurements, we investigate the electronic structure of potential Li-ion battery cathode materials LiMPO4 (M=Mn,Fe,Co,Ni) to uncover the underlying mechanisms that determine small hole polaron formation and migration. We show that small hole polaron formation depends on features in the electronic structure near the valence-band maximum and that, calculationally, these features depend on the methodology chosen for dealing with the correlated nature of the transition-metal d-derived states in these systems. Comparison with experiment reveals that a hybrid functional approach is superior to GGA+U in correctly reproducing the XPS spectra. Using this approach we find that LiNiPO4 cannot support small hole polarons, but that the other three compounds can. The migration barrier is determined mainly by the strong or weak bonding nature of the states at the top of the valence band, resulting in a substantially higher barrier for LiMnPO4 than for LiCoPO4 or LiFePO4.