Hole polaron formation and migration in olivine phosphate materials

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.

References in corpus (1)

• Tailoring Native Defects in LiFePO4: Insights from First-Principles Calculations

Cited by in corpus (11)

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• Defect physics in complex energy materials
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• Universality in the Electronic Structure of 3d Transition Metal Oxides
• Synergistic Role of Transition Metals and Polyanionic Frameworks in Phosphate-Based Cathode Materials for Sodium-Ion Batteries
• High-pressure optical floating-zone growth of Li(Mn,Fe)PO${}_4$ single crystals
• Electrochemical performance and diffusion kinetics of a NASICON type Na${}_{3.3}$Mn${}_{1.2}$Ti${}_{0.75}$Mo${}_{0.05}$(PO${}_4$)${}_3$/C cathode for low-cost sodium-ion batteries
• Electronic structure and properties of lithium-rich complex oxides
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