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Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes

Savoie, Brett M. and Webb, Michael A. and Miller, Thomas F., III (2017) Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes. Journal of Physical Chemistry Letters, 8 (3). pp. 641-646. ISSN 1948-7185. https://resolver.caltech.edu/CaltechAUTHORS:20170125-130016983

[img] PDF (1. Computational methods. 2. Results referenced in the main text. 3. Parametrization details. 4. Force-field validation for PEO. 5. Force-field parameter tables. 6. Force-field fit potentials: bonds, angles, dihedrals. 7. Force-field fit potentials: ...) - Supplemental Material
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Abstract

Solid polymer electrolytes (SPEs) have the potential to increase both the energy density and stability of lithium-based batteries, but low Li^+ conductivity remains a barrier to technological viability. SPEs are designed to maximize Li^+ diffusivity relative to the anion while maintaining sufficient salt solubility. It is thus remarkable that poly(ethylene oxide) (PEO), the most widely used SPE, exhibits Li^+ diffusivity that is an order of magnitude smaller than that of typical counterions at moderate salt concentrations. We show that Lewis-basic polymers like PEO favor slow cation and rapid anion diffusion, while this relationship can be reversed in Lewis-acidic polymers. Using molecular dynamics, polyboranes are identified that achieve up to 10-fold increases in Li^+ diffusivities and significant decreases in anion diffusivities, relative to PEO in the dilute-ion regime. These results illustrate a general principle for increasing Li^+ diffusivity and transference number with chemistries that exhibit weaker cation and stronger anion coordination.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acs.jpclett.6b02662DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.jpclett.6b02662PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.jpclett.6b02662PublisherSupporting Information
ORCID:
AuthorORCID
Savoie, Brett M.0000-0002-7039-4039
Webb, Michael A.0000-0002-7420-4474
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2017 American Chemical Society. Received: November 14, 2016; Accepted: January 11, 2017; Published: January 11, 2017. This research was supported by the National Science Foundation under DMREF Award Number NSF-CHE-1335486. M.A.W. also acknowledges support from the Resnick Sustainability Institute. This research used resources of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. This research also used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The authors declare no competing financial interest.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
NSFCHE-1335486
Resnick Sustainability InstituteUNSPECIFIED
Department of Energy (DOE)DE-AC05-00OR22725
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:3
Record Number:CaltechAUTHORS:20170125-130016983
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170125-130016983
Official Citation:Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes Brett M. Savoie, Michael A. Webb, and Thomas F. Miller, III The Journal of Physical Chemistry Letters 2017 8 (3), 641-646 DOI: 10.1021/acs.jpclett.6b02662
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:73722
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Jan 2017 23:42
Last Modified:03 Oct 2019 16:30

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