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

Journal Article · Sun Jul 17 00:00:00 EDT 2005 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2107387· OSTI ID:922990

Augustsson, A; Zhuang, G V; Butorin, S M; Osorio-Guillen, J M; Dong, C L; Ahuja, R; Chang, C L; Ross, P N; Nordgren, J; Guo, J -H

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: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
• Sponsoring Organization: USDOE Director. Office of Science. Basic Energy Sciences; Uppsala University/Sweden
• DOE Contract Number: DE-AC02-05CH11231
• OSTI ID: 922990
• Report Number(s): LBNL-58877; JCPSA6; R&D Project: 458111; BnR: KC0204016; TRN: US200804%%825
• Journal Information: Journal of Chemical Physics, Vol. 123, Issue 18; Related Information: Journal Publication Date: 11/08/2005; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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ABSORPTION SPECTRA
BONDING
ELECTRONIC STRUCTURE
HYBRIDIZATION
SCATTERING
SPECTROSCOPY
VALENCE
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