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Title: Large Charge‐Transfer Energy in LiFePO 4 Revealed by Full‐Multiplet Calculation for the Fe L 3 ‐edge Soft X‐ray Emission Spectra

Journal Article · · ChemPhysChem
ORCiD logo [1];  [2];  [3];  [1];  [4];  [4];  [1]
  1. Research Institute for Energy Conservation National Institute of Advanced Industrial Science and Technology (AIST) 1-1-1 Umezono Tsukuba Ibaraki 305–8568 Japan
  2. Research Institute for Energy Conservation National Institute of Advanced Industrial Science and Technology (AIST) 1-1-1 Umezono Tsukuba Ibaraki 305–8568 Japan, INAMORI Frontier Research Center Kyushu University 744 Motooka Nishi-ku Fukuoka 819-0395 Japan
  3. Research Institute for Energy Conservation National Institute of Advanced Industrial Science and Technology (AIST) 1-1-1 Umezono Tsukuba Ibaraki 305–8568 Japan, Present affiliation: Interdisciplinary Graduate School of Science and Technology Shimane University 1060 Nishikawatsucho Matsue Shimane 690–8504 Japan
  4. Advanced Light Source Lawrence Berkeley National Laboratory One Cyclotron Road Berkeley CA 94720 USA
+ Show Author Affiliations

Abstract We analyzed the Fe 3d electronic structure in LiFePO 4 /FePO 4 (LFP/FP) nanowire with a high cyclability by using soft X‐ray emission spectroscopy (XES) combined with configuration‐interaction full‐multiplet (CIFM) calculation. The ex situ Fe L 2,3 ‐edge resonant XES (RXES) spectra for LFP and FP are ascribed to oxidation states of Fe 2+ and Fe 3+ , respectively. CIFM calculations for Fe 2+ and Fe 3+ states reproduced the Fe L 3 RXES spectra for LFP and FP, respectively. In the calculations for both states, the charge‐transfer energy was considerably larger than those for typical iron oxides, indicating very little electron transfer from the O 2p to Fe 3d orbitals and a weak hybridization on the Fe−O bond during the charge–discharge reactions.

Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1422842
Journal Information:
ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 8 Vol. 19; ISSN 1439-4235
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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