A Nuclear Magnetic Resonance Study of Cation and Anion Dynamics in Polymer–Ceramic Composite Solid Electrolytes

Peng, Jing; Xiao, Ye; Clarkson, David A.; Greenbaum, Steven G.; Zawodzinski, Thomas A.; Chen, X. Chelsea

doi:10.1021/acsapm.9b01068

A Nuclear Magnetic Resonance Study of Cation and Anion Dynamics in Polymer–Ceramic Composite Solid Electrolytes

Journal Article · Mon Mar 02 04:00:00 EST 2020 · ACS Applied Polymer Materials

DOI:https://doi.org/10.1021/acsapm.9b01068· OSTI ID:1761677

Peng, Jing ^[1]; Xiao, Ye ^[1]; Clarkson, David A. ^[2]; Greenbaum, Steven G. ^[2]; Zawodzinski, Thomas A. ^[3]; ^[4]

Beihang Univ., Beijing (China)
Hunter College of the City Univ. of New York, NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Polymer–ceramic composite electrolytes are promising for the application of all-solid-state lithium-ion batteries with high energy density and improved safety. In this work, we employ temperature-dependent ⁷Li and ¹⁹F NMR to examine the chemical environment and the dynamics of Li⁺ cation and triflate anion in poly(ethylene oxide) (PEO)–lithium triflate (LiTf) polymer electrolyte and a composite electrolyte containing 55 vol % doped lithium aluminum titanium phosphate (LICGC). The line shape analysis and spin–lattice relaxation (T₁) measurements suggest both the Li⁺ cations and the Tf^– anions reside in two distinct environment: a mobile environment and an immobile environment. In the semicrystalline state, a large ratio (>70%) of immobile Li⁺ and Tf^– is observed. In the melt state, the ratio of mobile cations and anions significantly increases. With the presence of LICGC ceramic, an increased ratio of immobile Li⁺ and Tf^– and reduced mobility of the mobile components are observed, indicating that the ceramic negatively impacts the transport of both the cations and the anions. NMR characterizations are corroborated by conductivity results, which reveal that the intrinsic ionic conductivity of the polymer phase of the composite electrolyte was only 0.15 of the ceramic-free polymer electrolyte at room temperature. These results shed light on the challenges inherent to composite electrolytes with the goal of achieving both enhanced Li⁺ transference number and ionic conductivity.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1761677

Journal Information:: ACS Applied Polymer Materials, Journal Name: ACS Applied Polymer Materials Journal Issue: 3 Vol. 2; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

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A Nuclear Magnetic Resonance Study of Cation and Anion Dynamics in Polymer–Ceramic Composite Solid Electrolytes

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