title: Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes.
abstract: Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Michael A
authors.initials: MA
authors.lastname: Webb
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853, United States.
authors.forename: Yukyung
authors.initials: Y
authors.lastname: Jung
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley , Berkeley, California 94720, United States.
authors.forename: Danielle M
authors.initials: DM
authors.lastname: Pesko
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Brett M
authors.initials: BM
authors.lastname: Savoie
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Umi
authors.initials: U
authors.lastname: Yamamoto
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853, United States.
authors.forename: Geoffrey W
authors.initials: GW
authors.lastname: Coates
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720, United States; Materials Science Division and Environmental Energy Technology Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; Materials Science Division and Environmental Energy Technology Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
authors.forename: Nitash P
authors.initials: NP
authors.lastname: Balsara
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Zhen-Gang
authors.initials: ZG
authors.lastname: Wang
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Thomas F
authors.initials: TF
authors.lastname: Miller