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Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
KTH Royal Inst Technol, Dept Chem, Div Appl Phys Chem, Teknikringen 36, SE-10044 Stockholm, Sweden.
Univ Fed Fluminense, Inst Quim, Dept Quim Fis, Outeiro Sao Joao Batista S-N, BR-24020150 Niteroi, RJ, Brazil.
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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
Abstract [en]

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.
National Category
Materials Chemistry Physical Chemistry Theoretical Chemistry Organic Chemistry
URN: urn:nbn:se:uu:diva-248057DOI: 10.1039/c6cp00757kISI: 000373570200024PubMedID: 26984668OAI: oai:DiVA.org:uu-248057DiVA: diva2:798456
StandUpSwedish Research Council, 2012-3837, 2012-3244Carl Tryggers foundation Swedish Foundation for Strategic Research
Available from: 2015-03-26 Created: 2015-03-26 Last updated: 2016-06-08Bibliographically approved
In thesis
1. Functional Polymer Electrolytes for Multidimensional All-Solid-State Lithium Batteries
Open this publication in new window or tab >>Functional Polymer Electrolytes for Multidimensional All-Solid-State Lithium Batteries
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Pressing demands for high power and high energy densities in novel electrical energy storage units have caused reconsiderations regarding both the choice of battery chemistry and design. Practical concerns originating in the conventional use of flammable liquid electrolytes have renewed the interests of using solvent-free polymer electrolytes (SPEs) as solid ionic conductors for safer batteries.

In this thesis work, SPEs developed from two polymer host structures, polyethers and polycarbonates, have been investigated for all-solid-state Li- and Li-ion battery applications. In the first part, functional polyether-based polymer electrolytes, such as poly(propylene glycol) triamine based oligomer and poly(propylene oxide)-based acrylates, were investigated for 3D-microbattery applications. The amine end-groups were favorable for forming conformal electrolyte coatings onto 3D electrodes via self-assembly. In-situ polymerization methods such as UV-initiated and electro-initiated polymerization techniques also showed potential to deposit uniform and conformal polymer coatings with thicknesses down to nano-dimensions.

Moreover, poly(trimethylene carbonate) (PTMC), an alternative to the commonly investigated polyether host materials, was synthesized for SPE applications and showed promising functionality as battery electrolyte. High-molecular-weight PTMC was first applied in LiFePO4-based batteries. By incorporating an oligomeric PTMC as an interfacial mediator, enhanced surface contacts at the electrode/SPE interfaces and obvious improvements in initial capacities were realized. In addition, room-temperature functionality of PTMC-based SPEs was explored through copolymerization of ε-caprolactone (CL) with TMC. Stable cycling performance at ambient temperatures was confirmed in P(TMC/CL)-based LiFePO4 half cells (e.g., around 80 and 150 mAh g-1 at 22 °C and 40 °C under C/20 rate, respectively). Through functionalization, hydroxyl-capped PTMC demonstrated good surface adhesion to metal oxides and was applied on non-planar electrodes. Ionic transport behavior in polycarbonate-SPEs was examined by both experimental and computational approaches. A coupling of Li ion transport with the polymer chain motions was demonstrated.

The final part of this work has been focused on exploring the key characteristics of the electrode/SPE interfacial chemistry using PEO and PTMC host materials, respectively. X-ray photoelectron spectroscopy (XPS) was used to get insights on the compositions of the interphase layers in both graphite and LiFePO4 half cells.  

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2015. 89 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1243
Polymer electrolyte, Li-battery, 3D-microbattery, Functionalization, Polyether, Polycarbonate, Copolymer
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
urn:nbn:se:uu:diva-248084 (URN)978-91-554-9215-1 (ISBN)
Public defence
2015-05-22, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Available from: 2015-04-28 Created: 2015-03-26 Last updated: 2015-07-07

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