  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.
