title: Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations.
abstract: Among the alternative host materials for solid polymer electrolytes (SPEs), polycarbonates have recently shown promising functionality in all-solid-state lithium batteries from ambient to elevated temperatures. While the computational and experimental investigations of ion conduction in conventional polyethers have been extensive, the ion transport in polycarbonates has been much less studied. The present work investigates the ionic transport behavior in SPEs based on poly(trimethylene carbonate) (PTMC) and its co-polymer with ε-caprolactone (CL) via both experimental and computational approaches. FTIR spectra indicated a preferential local coordination between Li(+) and ester carbonyl oxygen atoms in the P(TMC20CL80) co-polymer SPE. Diffusion NMR revealed that the co-polymer SPE also displays higher ion mobilities than PTMC. For both systems, locally oriented polymer domains, a few hundred nanometers in size and with limited connections between them, were inferred from the NMR spin relaxation and diffusion data. Potentiostatic polarization experiments revealed notably higher cationic transference numbers in the polycarbonate based SPEs as compared to conventional polyether based SPEs. In addition, MD simulations provided atomic-scale insight into the structure-dynamics properties, including confirmation of a preferential Li(+)-carbonyl oxygen atom coordination, with a preference in coordination to the ester based monomers. A coupling of the Li-ion dynamics to the polymer chain dynamics was indicated by both simulations and experiments.
authors.affiliation: Department of Chemistry - Ångström Laboratory, Uppsala University, Box 538, SE-75121, Uppsala, Sweden. Daniel.Brandell@kemi.uu.se.
authors.forename: Bing
authors.initials: B
authors.lastname: Sun
authors.affiliation: Department of Chemistry - Ångström Laboratory, Uppsala University, Box 538, SE-75121, Uppsala, Sweden. Daniel.Brandell@kemi.uu.se.
authors.forename: Jonas
authors.initials: J
authors.lastname: Mindemark
authors.affiliation: Division of Applied Physical Chemistry, Department of Chemistry, KTH Royal Institute of Technology, Teknikringen 36, SE-10044, Stockholm, Sweden.
authors.forename: Evgeny
authors.initials: E
authors.lastname: V Morozov
authors.affiliation: Instituto de Química - Departamento de Físico-Química, Universidade Federal Fluminense, Outeiro de São João Batista s/n, CEP 24020-150 Niterói, RJ, Brazil.
authors.forename: Luciano T
authors.initials: LT
authors.lastname: Costa
authors.affiliation: Department of Physics, Chalmers University of Technology, SE-41296, Gothenburg, Sweden.
authors.forename: Martin
authors.initials: M
authors.lastname: Bergman
authors.affiliation: Department of Physics, Chalmers University of Technology, SE-41296, Gothenburg, Sweden.
authors.forename: Patrik
authors.identifier: http://orcid.org/0000-0002-9907-117X
authors.initials: P
authors.lastname: Johansson
authors.affiliation: Division of Applied Physical Chemistry, Department of Chemistry, KTH Royal Institute of Technology, Teknikringen 36, SE-10044, Stockholm, Sweden.
authors.forename: Yuan
authors.initials: Y
authors.lastname: Fang
authors.affiliation: Division of Applied Physical Chemistry, Department of Chemistry, KTH Royal Institute of Technology, Teknikringen 36, SE-10044, Stockholm, Sweden.
authors.forename: István
authors.initials: I
authors.lastname: Furó
authors.affiliation: Department of Chemistry - Ångström Laboratory, Uppsala University, Box 538, SE-75121, Uppsala, Sweden. Daniel.Brandell@kemi.uu.se.
authors.forename: Daniel
authors.initials: D
authors.lastname: Brandell