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Title: Low-Temperature Ionic Conductivity Enhanced by Disrupted Ice Formation in Polyampholyte Hydrogels

Here, the phase behavior of water in hydrogels has a broad impact on many health and energy applications. Our previous study showed that polyampholyte hydrogel has the potential to be used as an aqueous gel electrolyte in electrochemical storage devices at -30 °C due to enhanced low-temperature conductivity. In this study, we detail the impact polymer structure has on this enhanced conductivity, explaining this finding with a model charge-balanced polyampholyte, poly(4-vinylbenzenesulfonate- co-[3-(methacryloylam ino)propyl] trimethylammonium chloride), a hydrogel whose polymer and water structures are probed by variable-temperature SAXS, WAXS, and solid-state NMR spectroscopy. SAXS results at room temperature indicate a networked globule structure in the charge-balanced polyampholyte hydrogels. The globular radius of gyration is ~ 2.5 nm, whereas the globular size and its clustering structure are dependent on synthesis parameters. Variable-temperature SAXS data reveal a temperature-dependent structure evolution of the polyampholyte hydrogel. An interconnected globular network structure of polymer-rich phase at low temperature, observed by electron microscopy, is suggested to preserve ion-conducting channels of nonfrozen water molecules at low temperatures. This hypothesis is further supported by solid-state NMR spectroscopy. Together these findings provide macromolecular- and molecular-level insight that may be used to design gel electrolytes for enhanced low-temperature performance.
Authors:
ORCiD logo [1] ;  [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Univ. of Alberta, Edmonton, AB (Canada)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 7; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
University of Alberta; Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1461265

Li, Xinda, Charaya, Hemant, Bernard, Guy M., Elliott, Janet A. W., Michaelis, Vladimir K., Lee, Byeongdu, and Chung, Hyun -Joong. Low-Temperature Ionic Conductivity Enhanced by Disrupted Ice Formation in Polyampholyte Hydrogels. United States: N. p., Web. doi:10.1021/acs.macromol.7b02498.
Li, Xinda, Charaya, Hemant, Bernard, Guy M., Elliott, Janet A. W., Michaelis, Vladimir K., Lee, Byeongdu, & Chung, Hyun -Joong. Low-Temperature Ionic Conductivity Enhanced by Disrupted Ice Formation in Polyampholyte Hydrogels. United States. doi:10.1021/acs.macromol.7b02498.
Li, Xinda, Charaya, Hemant, Bernard, Guy M., Elliott, Janet A. W., Michaelis, Vladimir K., Lee, Byeongdu, and Chung, Hyun -Joong. 2018. "Low-Temperature Ionic Conductivity Enhanced by Disrupted Ice Formation in Polyampholyte Hydrogels". United States. doi:10.1021/acs.macromol.7b02498. https://www.osti.gov/servlets/purl/1461265.
@article{osti_1461265,
title = {Low-Temperature Ionic Conductivity Enhanced by Disrupted Ice Formation in Polyampholyte Hydrogels},
author = {Li, Xinda and Charaya, Hemant and Bernard, Guy M. and Elliott, Janet A. W. and Michaelis, Vladimir K. and Lee, Byeongdu and Chung, Hyun -Joong},
abstractNote = {Here, the phase behavior of water in hydrogels has a broad impact on many health and energy applications. Our previous study showed that polyampholyte hydrogel has the potential to be used as an aqueous gel electrolyte in electrochemical storage devices at -30 °C due to enhanced low-temperature conductivity. In this study, we detail the impact polymer structure has on this enhanced conductivity, explaining this finding with a model charge-balanced polyampholyte, poly(4-vinylbenzenesulfonate-co-[3-(methacryloylam ino)propyl] trimethylammonium chloride), a hydrogel whose polymer and water structures are probed by variable-temperature SAXS, WAXS, and solid-state NMR spectroscopy. SAXS results at room temperature indicate a networked globule structure in the charge-balanced polyampholyte hydrogels. The globular radius of gyration is ~ 2.5 nm, whereas the globular size and its clustering structure are dependent on synthesis parameters. Variable-temperature SAXS data reveal a temperature-dependent structure evolution of the polyampholyte hydrogel. An interconnected globular network structure of polymer-rich phase at low temperature, observed by electron microscopy, is suggested to preserve ion-conducting channels of nonfrozen water molecules at low temperatures. This hypothesis is further supported by solid-state NMR spectroscopy. Together these findings provide macromolecular- and molecular-level insight that may be used to design gel electrolytes for enhanced low-temperature performance.},
doi = {10.1021/acs.macromol.7b02498},
journal = {Macromolecules},
number = 7,
volume = 51,
place = {United States},
year = {2018},
month = {3}
}