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Electronic structure of phospho-olivines LixFePO4 (x=0,1) fromsoft-x-ray-absorption and -emission spectroscopies

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.2107387· OSTI ID:922990

The electronic structure of the phospho-olivine LixFePO4 wasstudied using soft-x-ray-absorption (XAS) and emission spectroscopies.Characteristic changes in the valence and conduction bands are observedupon delithation of LiFePO4 into FePO4. In LiFePO4, the Fe-3d states arelocalized with little overlap with the O-2p states. Delithiation ofLiFePO4 gives stronger hybridization between Fe-3d states and O-2p statesleading to delocalization of the O-2p states. The Fe L-edge absorptionspectra yield "fingerprints" of the different valence states of Fe inLiFePO4 and FePO4. Resonant soft-x-ray-emission spectroscopy at the Fe Ledge shows strong contributions from resonant inelastic soft x-rayscattering (RIXS), which is described using an ionic picture of the Fe-3dstates. Together the Fe L-edge XAS and RIXS study reveals a bondingcharacter of the Fe 3d-O2p orbitals in FePO4 in contrast to a nonbondingcharacter in LiFePO4.

Research Organization:
Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
Sponsoring Organization:
USDOE Director. Office of Science. Basic Energy Sciences; Uppsala University/Sweden
DOE Contract Number:
AC02-05CH11231
OSTI ID:
922990
Report Number(s):
LBNL--58877; BnR: KC0204016
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 123; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English

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