Reaction Mechanism of Li 2 MnO 3 Electrodes in an All-Solid-State Thin-Film Battery Analyzed by Operando Hard X-ray Photoelectron Spectroscopy.
Kazuhiro HikimaKeisuke ShimizuHisao KiuchiYoyo HinumaKota SuzukiMasaaki HirayamaEiichiro MatsubaraRyoji KannoPublished in: Journal of the American Chemical Society (2021)
Li 2 MnO 3 is a promising cathode candidate for Li-ion batteries because of its high discharge capacity; however, its reaction mechanism during cycling has not been sufficiently explicated. Observations of Mn and O binding energy shifts in operando hard X-ray photoelectron spectroscopy measurements enabled us to determine the charge-compensation mechanism of Li 2 MnO 3 . The O 1 s peak splits at an early stage during the first charge, and the concentration of lower-valence O changes reversibly with cycling, indicating the formation of a low-valence O species that intrinsically participates in the redox reaction. The O 1 s peak-splitting behavior, which indicates the number of valences of O in Li 2 MnO 3 , is supported by the computational results for an O3 to O1 structural transition. This is in agreement with the results of our previous study, wherein we confirmed this O3 to O1 transition based on in situ surface X-ray diffraction analysis, X-ray photoelectron spectroscopy, and first-principles formation energy calculations.
Keyphrases
- solid state
- ion batteries
- high resolution
- dual energy
- early stage
- electron microscopy
- high intensity
- electron transfer
- magnetic resonance imaging
- molecular dynamics simulations
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- lymph node
- room temperature
- dna binding
- magnetic resonance
- sentinel lymph node
- reduced graphene oxide