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Title: Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies

Abstract

The design and engineering of composite materials is one strategy to satisfy the materials needs of systems with multiple orthogonal property requirements. In the case of rechargeable batteries with lithium metal anodes, the system requires a separator with fast lithium ion transport and good mechanical strength. In this work, we focus on the system polystyrene-block-poly(ethylene oxide) (SEO) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Ion transport occurs in the salt-containing poly(ethylene oxide)-rich domains. Mechanical rigidity arises due to the glassy nature of polystyrene (PS). If we assume that the salt does not interact with the PS-rich domains, we can describe ion transport in the electrolyte by three transport parameters (ionic conductivity, κ, salt diffusion coefficient, D, and cation transference number, t + 0) and a thermodynamic factor, T f. By systematically varying the volume fraction of the conducting phase, Φ c between 0.29 and 1.0, and chain length, N between 80 and 8000, we elucidate the role of morphology on ion transport. We find that κ is the strongest function of morphology, varying by three full orders of magnitude, while D is a weaker function of morphology. To calculate t + 0 and T f, we measure the current fraction, ρ +,more » and the open circuit potential, U, of concentration cells. We find that ρ + and U follow universal trends as a function of salt concentration, regardless of chain length, morphology, or Φ c, allowing us to calculate t + 0 for any SEO/LiTFSI or PEO/LiTFSI mixture when κ and D are known. Finally, the framework developed in this paper enables predicting the performance of any block copolymer electrolyte in a rechargeable battery.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1604728
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 124; Journal Issue: 5; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; salts; morphology; electrolytes; lithium; polymers

Citation Formats

Galluzzo, Michael D., Loo, Whitney S., Wang, Andrew A., Walton, Amber, Maslyn, Jacqueline A., and Balsara, Nitash P. Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies. United States: N. p., 2020. Web. doi:10.1021/acs.jpcb.9b11066.
Galluzzo, Michael D., Loo, Whitney S., Wang, Andrew A., Walton, Amber, Maslyn, Jacqueline A., & Balsara, Nitash P. Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies. United States. https://doi.org/10.1021/acs.jpcb.9b11066
Galluzzo, Michael D., Loo, Whitney S., Wang, Andrew A., Walton, Amber, Maslyn, Jacqueline A., and Balsara, Nitash P. Wed . "Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies". United States. https://doi.org/10.1021/acs.jpcb.9b11066. https://www.osti.gov/servlets/purl/1604728.
@article{osti_1604728,
title = {Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies},
author = {Galluzzo, Michael D. and Loo, Whitney S. and Wang, Andrew A. and Walton, Amber and Maslyn, Jacqueline A. and Balsara, Nitash P.},
abstractNote = {The design and engineering of composite materials is one strategy to satisfy the materials needs of systems with multiple orthogonal property requirements. In the case of rechargeable batteries with lithium metal anodes, the system requires a separator with fast lithium ion transport and good mechanical strength. In this work, we focus on the system polystyrene-block-poly(ethylene oxide) (SEO) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Ion transport occurs in the salt-containing poly(ethylene oxide)-rich domains. Mechanical rigidity arises due to the glassy nature of polystyrene (PS). If we assume that the salt does not interact with the PS-rich domains, we can describe ion transport in the electrolyte by three transport parameters (ionic conductivity, κ, salt diffusion coefficient, D, and cation transference number, t+0) and a thermodynamic factor, Tf. By systematically varying the volume fraction of the conducting phase, Φc between 0.29 and 1.0, and chain length, N between 80 and 8000, we elucidate the role of morphology on ion transport. We find that κ is the strongest function of morphology, varying by three full orders of magnitude, while D is a weaker function of morphology. To calculate t+0 and Tf, we measure the current fraction, ρ+, and the open circuit potential, U, of concentration cells. We find that ρ+ and U follow universal trends as a function of salt concentration, regardless of chain length, morphology, or Φc, allowing us to calculate t+0 for any SEO/LiTFSI or PEO/LiTFSI mixture when κ and D are known. Finally, the framework developed in this paper enables predicting the performance of any block copolymer electrolyte in a rechargeable battery.},
doi = {10.1021/acs.jpcb.9b11066},
url = {https://www.osti.gov/biblio/1604728}, journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {1520-6106},
number = 5,
volume = 124,
place = {United States},
year = {2020},
month = {1}
}

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