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Heterogeneous Coordination Environments in Lithium-Neutralized Ionomers Identified Using 1H and 7Li MAS NMR

Journal Article · · Materials
DOI:https://doi.org/10.3390/ma5081508· OSTI ID:1628434
 [1];  [2];  [3];  [4];  [4];  [5];  [6];  [7];  [8]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Nanostructured and Electronic Materials; DOE/OSTI
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Nanostructured and Electronic Materials
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Nanoscale and Reactive Processes
  4. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Computational Materials Science and Engineering Dept.
  5. Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemical and Biomolecular Engineering
  6. Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Material Science and Engineering
  7. DuPont Central Research and Development, Wilmington, DE (United States)
  8. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry. Center for Macromolecular Science and Engineering
The carboxylic acid proton and the lithium coordination environments for precise and random Li-neutralized polyethylene acrylic acid P(E-AA) ionomers were explored using high speed solid-state 1H and 7 Li MAS NMR. While the 7 Li NMR revealed only a single Li coordination environment, the chemical shift temperature variation was dependent on the precise or random nature of the P(E-AA) ionomer. The 1H MAS NMR revealed two different carboxylic acid proton environments in these materials. By utilizing 1H-7 Li rotational echo double resonance (REDOR) MAS NMR experiments, it was demonstrated that the proton environments correspond to different average 1H-7 Li distances, with the majority of the protonated carboxylic acids having a close through space contact with the Li. Molecular dynamics simulations suggest that the shortest 1H-7 Li distance corresponds to un-neutralized carboxylic acids directly involved in the coordination environment of Li clusters. These solid-state NMR results show that heterogeneous structural motifs need to be included when developing descriptions of these ionomer materials.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1628434
Journal Information:
Materials, Journal Name: Materials Journal Issue: 8 Vol. 5; ISSN 1996-1944; ISSN MATEG9
Publisher:
MDPICopyright Statement
Country of Publication:
United States
Language:
English

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Lithium Polyacrylate (LiPAA) as an Advanced Binder and a Passivating Agent for High-Voltage Li-Ion Batteries journal September 2015
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