Journal
ACS APPLIED ENERGY MATERIALS
Volume 3, Issue 9, Pages 9158-9167Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsaem.0c01536
Keywords
lithium iron phosphate; doping; surface characterization; soft X-ray absorption spectroscopy; density functional theory; electrochemical impedance spectroscopy
Funding
- CSIRO
- Australian Federal Government's Cooperative Research Centers Program
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This study investigates a series of cation dopants for LiFePO4 that are reported to be beneficial for rate performance. A solid-state synthesis has been used to be consistent with a common processing method used in prior doping investigations and in commercial processes for this compound. Increased ratios of Fe3+/Fe2+ oxidation on the particle surfaces have been determined using X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectroscopy (sXAS) for the doped LiFePO4, for all chosen dopants and valences (<, = or >2+), while the cores remain much Valence s.a.et closer to the characteristics of the pristine (undoped) material. These results indicate that the dopants are predominantly pushed to the particle surfaces during phase formation, even when the dopants are added at the initial fine mixing of precursors. The differential distribution of dopants between the cores and surface layers of the particles results in conductivity improvements and reduction of polarizations in electrochemical impedance spectroscopy measurements of the doped LiFePO4.
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