Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations
2016 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 18, no 14, 9504-9513 p.Article in journal (Refereed) Published
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 epsilon-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.
Place, publisher, year, edition, pages
2016. Vol. 18, no 14, 9504-9513 p.
Materials Chemistry Physical Chemistry Theoretical Chemistry Organic Chemistry
IdentifiersURN: urn:nbn:se:uu:diva-248057DOI: 10.1039/c6cp00757kISI: 000373570200024PubMedID: 26984668OAI: oai:DiVA.org:uu-248057DiVA: diva2:798456
FunderStandUpSwedish Research Council, 2012-3837, 2012-3244Carl Tryggers foundation Swedish Foundation for Strategic Research