Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 24, Issue 32, Pages 19177-19183Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cp01040b
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Funding
- JSPS KAKENHI [JP19H05717]
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The Mn 3d electronic structure change of the LiMn2O4 cathode during Li-ion extraction/insertion in an aqueous electrolyte solution was studied using operando resonant soft X-ray emission spectroscopy. The results showed that the degree of charge transfer varied significantly between the Mn3+ and Mn4+ states, indicating that the redox reaction occurs on the strongly-hybridized Mn 3d-O 2p orbital rather than the localized Mn 3d orbital.
The Mn 3d electronic-structure change of the LiMn2O4 cathode during Li-ion extraction/insertion in an aqueous electrolyte solution was studied by operando resonant soft X-ray emission spectroscopy (RXES). The Mn L-3 RXES spectra for the charged state revealed the Mn4+ state with strong charge-transfer from the O 2p to Mn 3d orbitals dominates, while for the open-circuit-voltage and discharged states it is ascribed to the mixture of sites with Mn3+ and Mn4+ states. The degree of charge transfer is significantly different between the Mn3+ and Mn4+ states, indicating that the redox reaction takes place on the strongly-hybridized Mn 3d-O 2p orbital rather than the localized Mn 3d orbital.
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