First Principles Modeling of Structure and Transport in Solid Polymer Electrolytes, Ionic Liquids, and Methanol/Water Mixtures

Abstract

We have undertaken simulations and calculations on three distinct systems: (1) polyethylene oxide-alkali salts systems with the general formula: PEO6:XPF6, where X = H, Li, or Na; (2) methanol/water solution over a range of methanol mole fractions (0 to 1); and (3)electrolytes for magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group of Prof. Vito Di Noto at the University of Padua, Italy. We have sought to understand structure/function relationships using first principles based methods including ab initio molecular dynamics simulations and density functional theory based electronic structure calculations. Specifically, in crystalline PEO6:XPF6 systems we confirmed that the dynamics of the chains play an important role in the diffusion mechanism and computed diffusion barriers for H+, Li+, and Na+. In our AIMD simulations of the water-methanol mixtures we determined that at low methanol concentrations the water forms percolating hydrogen bond networks. When a moderate electric field was applied a "hollow channel" was observed in the methanol-rich mixtures. Finally, in our quantum chemical calculations of the magnesium battery electrolytes we were able to make all vibrational frequency assignments (measured in the IR and Raman spectra) and confirm the overall concatenated structure of the ionic liquids in the amorphous delta-Mg chloride/iodide.

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Document Details

Document Type
Technical Report
Publication Date
Feb 10, 2016
Accession Number
AD1037145

Entities

People

  • Stephen J Paddison

Organizations

  • University of Tennessee system

Tags

Communities of Interest

  • Air Platforms
  • C4I
  • Energy and Power Technologies

DTIC Thesaurus Topics

  • Chemistry
  • Density Functional Theory
  • Electric Fields
  • Electrons
  • Engineering
  • Frequency
  • Hydrogen Bonds
  • Ionic Liquids
  • Magnesium Batteries
  • Molecular Dynamics
  • Protons
  • Quantum Chemistry
  • Raman Spectra
  • Spectra
  • Spectroscopy
  • Storage Batteries
  • Vibrational Spectra

Fields of Study

  • Materials science

Readers

  • Electrochemical Engineering/ Fuel Cell Technologies
  • Quantum Chemistry

Technology Areas

  • Microelectronics
  • Quantum Computing