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Solvation Structure of Methanol-in-Salt Electrolyte Revealed by Small-Angle X-ray Scattering and Simulations
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    Solvation Structure of Methanol-in-Salt Electrolyte Revealed by Small-Angle X-ray Scattering and Simulations
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    ACS Nano

    Cite this: ACS Nano 2024, 18, 9, 7037–7045
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    https://doi.org/10.1021/acsnano.3c10469
    Published February 19, 2024
    Copyright © 2024 American Chemical Society

    Abstract

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    The solvation structure of water-in-salt electrolytes was thoroughly studied, and two competing structures─anion solvated structure and anion network─were well-defined in recent publications. To further reveal the solvation structure in those highly concentrated electrolytes, particularly the influence of solvent, methanol was chosen as the solvent for this proposed study. In this work, small-angle X-ray scattering, small-angle neutron scattering, Fourier-transform infrared spectroscopy, and Raman spectroscopy were utilized to obtain the global and local structural information. With the concentration increment, the anion network formed by TFSI became the dominant structure. Meanwhile, the hydrogen bonds among methanol were interrupted by the TFSI anion and formed a new connection with them. Molecular dynamic simulations with two different force fields (GAFF and OPLS-AA) are tested, and GAFF agreed with synchrotron small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) results well and provided insightful information about molecular/ion scale solvation structure. This article not only deepens the understanding of the solvation structure in highly concentrated solutions, but more importantly, it provides additional strong evidence for utilizing SAXS/WAXS to validate molecular dynamics simulations.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.3c10469.

    • Peak positions and analysis results for SAXS/WAXS; analysis results for FTIR; comparison of peak position from MD simulations with OPLS force field and GAFF force field with experimental measurements for different concentrations; structure factor of various concentrations; neutron scattering of various concentrations calculated from MD simulations; Raman spectra and the fitting curves of LiTFSI methanol solutions; anion coordination mode obtained from Raman and MD with OPLS-AA force field, and GAFF force field (PDF)

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    Cited By

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    This article is cited by 9 publications.

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    ACS Nano

    Cite this: ACS Nano 2024, 18, 9, 7037–7045
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.3c10469
    Published February 19, 2024
    Copyright © 2024 American Chemical Society

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