Investigation of Solvent Type and Salt Addition in High Transference Number Nonaqueous Polyelectrolyte Solutions for Lithium Ion Batteries

Diederichsen, Kyle M.; Fong, Kara D.; Terrell, Rickey C.; Persson, Kristin A.; McCloskey, Bryan D.

doi:10.1021/acs.macromol.8b01696

Title: Investigation of Solvent Type and Salt Addition in High Transference Number Nonaqueous Polyelectrolyte Solutions for Lithium Ion Batteries

Journal Article · 25 October 2018 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.8b01696 · OSTI ID:1571124

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Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

High Li⁺ transference number electrolytes have attracted recent interest as a means to improve the energy density and rate capabilities of current lithium ion batteries. Here the viscosity and transport properties of a sulfonated polysulfone/poly(ethylene glycol) copolymer that displays both high transference number and high conductivity when dissolved in dimethyl sulfoxide (DMSO) are investigated for the first time in a battery-relevant solvent of nearly equivalent dielectric constant: mixed ethylene carbonate (EC)/dimethyl carbonate (DMC). The addition of a binary salt to each solution is investigated as a means to improve conductivity, and the diffusion coefficient of each species is tracked by pulse field gradient nuclear magnetic resonance (PFG-NMR). Through the ⁷Li NMR peak width and quantum chemistry calculations of the dissociation constant, it is shown that although the two solvent systems have nearly equivalent dielectric constants, the conductivity and transference number of the EC/DMC solutions are significantly lower as a result of poor dissociation of the sulfonate group on the polymer backbone. These results are the first study of polyelectrolyte properties in a battery-relevant solvent and clearly demonstrate the need to consider solvent properties other than the dielectric constant in the design of these electrolytes.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1571124

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 21 Vol. 51; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Ion Transport and the True Transference Number in Nonaqueous Polyelectrolyte Solutions for Lithium Ion Batteries Fong, Kara D.; Self, Julian; Diederichsen, Kyle M. ACS Central Science, Vol. 5, Issue 7 https://doi.org/10.1021/acscentsci.9b00406	journal	June 2019
Difference between approximate and rigorously measured transference numbers in fluorinated electrolytes Shah, Deep B.; Nguyen, Hien Q.; Grundy, Lorena S. Physical Chemistry Chemical Physics, Vol. 21, Issue 15 https://doi.org/10.1039/c9cp00216b	journal	January 2019
Insights into the solvation and dynamic behaviors of a lithium salt in organic- and ionic liquid-based electrolytes Tong, Jiahuan; Xiao, Xingqing; Liang, Xiaodong Physical Chemistry Chemical Physics, Vol. 21, Issue 35 https://doi.org/10.1039/c9cp01848d	journal	January 2019
Electrolyte additives to enable nonaqueous polyelectrolyte solutions for lithium ion batteries Diederichsen, Kyle M.; McCloskey, Bryan D. Molecular Systems Design & Engineering, Vol. 5, Issue 1 https://doi.org/10.1039/c9me00067d	journal	January 2020

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