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Quantifying Small Polaron Formation and Hopping Kinetics in FePO4: First-Principles Rate Theory Calculations
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DOI：10.1021/acs.jpcc.6c02271.png)
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Abstract
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The formation and migration of small polarons are fundamental microscopic processes governing the charge transport properties of FePO4-based materials. However, as the initial step in this kinetic chain, the rate constant kform for the delocalized electron → small polaron transition lacks quantitative characterization, hindering the establishment of a complete structure-dynamics-property correlation. In this work, we systematically investigate the kinetics of delocalized electrons relaxing to form small polarons in FePO4 using first-principles calculations combined with rate theories and perform a comparative analysis with the polaron hopping rate constant khop. The results reveal that at room temperature, kform reaches as high as 1013 s–1, approximately 2 orders of magnitude faster than the small polaron hopping process. Furthermore, kform is nearly temperature-independent. This significant disparity originates from the combined effects of asymmetric energy barriers, modulation by divergent band structures, and differential dynamic lattice effects. These findings may supply possible optimization strategies to modulate the kform/khop ratio and establish a rate engineering paradigm for designing high-power FePO4-based cathode materials.
Keywords:
Batteries
Kinetic parameters
Lithium iron phosphate
Polarons
Thermodynamic properties
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