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Tracking the change in electronic structure of target elements is crucial to investigate the nature of redox reactions occurring in battery electrodes. X-ray emission spectroscopy (XES) and x-ray absorption fine structure (XAFS) perform this role well with high sensitivity and throughput, but the requisite of synchrotron facilities often limits those availability for material characterization. Using a lab-scale x-ray emission/absorption spectrometer, we investigated the changes in the local structure and chemistry around the 3d transition metal elements of LiMO 2 cathodes for Li-ion batteries as a function of the battery state of charge (SoC). Ex situ measurement was prepared from the electrode samples with discrete difference in SoC. Coupled with ex situ measurement, operando measurement was performed using pouch cells with LiMO 2 cathode, which enabled a real-time monitoring of chemical shift in an element-specific manner resulted from changing electrode potential. Through the XES mode of the bench-top spectrometer, fluorescence emissions from the LiMO 2 cathode, or the cell containing it, was monochromatized by a spherically bent crystal analyzer (SBCA). The Kβ emissions of 3d transition metal elements such as cobalt display position/shape difference of spectrum with varying SoC. The trend of chemical shift and change in spectral features provided the information on the electronic structure variation, such as oxidation state change of 3d transition metals in LiMO 2 during charge and discharge (i.e., delithiation and lithiation). Furthermore, valence-to-core (VtC) emission signals helped enable in-depth analysis such as spin structure characterization. In addition to the XES analysis, we could measure K-edge XAFS for the same 3d transition metals in LiMO 2 as well. In the XAFS mode of the spectrometer, SBCA monochromatized bremsstrahlung x-ray generated from a high-power x-ray tube is used to make an incident source energy-dispersive. While Kβ XES probed occupied levels, K-edge XAFS examined unoccupied levels providing comprehensive understanding on the change in electronic structure of 3d transition metals in LiMO 2 . Figure 1
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Spherically bent mica analyzers as universal dispersing elements for X‐ray spectroscopy
Spherically‐bent crystal analyzers (SBCAs) see considerable use in very high‐resolution hard X‐ray wavelength dispersive X‐ray fluorescence spectroscopy, often called X‐ray emission spectroscopy (XES). While Si and Ge are the most frequently used diffractive components of SBCAs, we consider here the somewhat classical choice of muscovite mica as the dispersing element. We find that the various harmonics of a highest‐quality mica‐based SBCA show ~5–~40% of the integral reflectivity per unit solid angle of a typical Si or Ge SBCA in the hard X‐ray range, and that the mica SBCA have comparable energy resolution to the traditional SBCAs. Interestingly, the choice of mica comes with a practical benefit: the primary (0,0,2) reflection has sufficiently strong harmonics that are fairly tightly spaced in energy so that they span the complete energy range from ~4 to ~11 keV when used at convenient Bragg angles in a Rowland circle spectrometer. Hence, a single mica SBCA can be used for every K‐shell emission line of three dimensional transition metals and every L‐shell emission line of the lanthanide elements simply by selecting the correct mica (0,0,2) harmonic with a final energy‐dispersive solid state detector. The loss in efficiency is counteracted by an operational efficiency, i.e., the “universal” application of a single analyzer over a very large range of elements. This performance suggests future application of mica SBCAs in both laboratory‐based XES and synchrotron‐based photon‐in, photon‐out spectroscopies in the hard X‐ray range.
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- Award ID(s):
- 1904437
- PAR ID:
- 10457642
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- X-Ray Spectrometry
- Volume:
- 49
- Issue:
- 4
- ISSN:
- 0049-8246
- Format(s):
- Medium: X Size: p. 493-501
- Size(s):
- p. 493-501
- Sponsoring Org:
- National Science Foundation
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