Molecular structures of residual solvent in polyacrylonitrile based electrolytes: Implications for conductivity and stability

Lin, Lu; Liu, Changhao; Sacci, Robert L.; Chen, Xi Chelsea; Doughty, Benjamin L.

doi:10.1063/5.0233578

Title: Molecular structures of residual solvent in polyacrylonitrile based electrolytes: Implications for conductivity and stability

Journal Article · 21 November 2024 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0233578 · OSTI ID:2481201

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Emory Univ., Atlanta, GA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Lithium-ion batteries increasingly play significant roles in modern technologies; however, increased energy density also raises concerns about electrolyte safety. Traditional electrolytes that use volatile organic solvents face risks of thermal runaways and fires from electrode shorting. In response, polymer-based solid electrolytes have been developed for replacement. Polyacrylonitrile (PAN) is a promising fire-resistant component for electrolyte fabrication, but its limited solubility necessitates using low-volatility solvents, which are notoriously difficult to remove in subsequent drying processes. Here, we use femtosecond two-dimensional infrared spectroscopy to provide an in-depth understanding of how residual solvent from processing affects the molecular structures and dynamics within a polymer electrolyte. To this end, linear and nonlinear infrared spectroscopies are employed to interrogate the molecular interactions in PAN-based electrolytes containing various contents of N,N-dimethylformamide (DMF). We show that the amount of DMF within the PAN electrolyte affects the Li+ structure. Further, the coordination can proceed through the carbonyl group and/or the amide nitrogen to form antiparallel structures with the nitrile groups of PAN through dipole–dipole interactions. The free motion of DMF is drastically inhibited upon interaction with Li+ and PAN, which decreases the ionic conductivity and potentially affects the stability (resistance toward removal and chemical decomposition). These findings have implications for the design and processing of solid polymer electrolytes.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2481201

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 161; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electrolytes
Infrared spectroscopy
Lithium-ion batteries
Polymers
Two-dimensional Fourier transform spectroscopy

Title: Molecular structures of residual solvent in polyacrylonitrile based electrolytes: Implications for conductivity and stability

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References (45)

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