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Decomposition of Carbonate-Based Electrolytes: Differences and Peculiarities for Liquids vs. Polymers Observed Using Operando Gas Analysis
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry. (Ångström Advanced Battery Centre)ORCID iD: 0000-0002-3374-2276
Paul Scherrer Institute.ORCID iD: 0000-0003-2314-6945
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0002-8019-2801
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry. Paul Scherrer Institute.ORCID iD: 0000-0001-5653-0383
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2021 (English)In: Batteries & Supercaps, E-ISSN 2566-6223, Vol. 4, no 5, p. 785-790Article in journal (Refereed) Published
Abstract [en]

Direct tracking of solid polymer electrolyte (SPE) decomposition in comparison to a liquid analogue was accomplished by monitoring the evolution of volatile species using online electrochemical mass spectrometry (OEMS). Reduction of a poly(trimethylene carbonate)-based SPE was dominated by CO2 formation. Detection of CO2 and an absence of CO confirms a preferred reduction degradation pathway involving C−O bond cleavage at the carbonyl carbon, in correlation with earlier suggestions. In contrast, the alkyl carbonate-based liquid electrolyte exhibited extensive ethylene formation. Trace quantities of H2 evolution ascribed to water impurities were also observed in both systems. During oxidation, the SPE and liquid electrolyte exhibited CO2, CO and SO2 evolution synonymous with electrolyte solvent and salt degradation, albeit at different potentials. Overall, gas evolution rates and redox currents were lower in the SPE system. OEMS revealed significant gas formation independent of current response, as such highlighting the limitations of the voltammetry technique commonly used today to assess electrochemical stability.

Place, publisher, year, edition, pages
John Wiley & Sons, 2021. Vol. 4, no 5, p. 785-790
Keywords [en]
electrochemical stability window, gas evolution, online electrochemical mass spectrometry, solid-state electrolytes, solid polymer electrolytes
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-440842DOI: 10.1002/batt.202000307ISI: 000613731100001OAI: oai:DiVA.org:uu-440842DiVA, id: diva2:1546223
Funder
StandUpEU, Horizon 2020, 875514
Note

De två första författarna delar förstaförfattarskapet

Available from: 2021-04-21 Created: 2021-04-21 Last updated: 2024-01-15Bibliographically approved
In thesis
1. Exploring the Frontiers of Polymer Electrolytes for Battery Applications: From Surface to Bulk
Open this publication in new window or tab >>Exploring the Frontiers of Polymer Electrolytes for Battery Applications: From Surface to Bulk
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Lithium-ion batteries have dominated the market since their inception in 1991 due to their unparalleled energy and power densities, but are now faced with new challenges. Growing demand for battery materials for energy intense applications and large-scale interim energy storage have emphasized the need for safe and sustainable battery electrolytes. In this context, non-flammable solid polymer electrolytes (SPEs) are a promising alternative to address the shortcomings of conventional liquid electrolytes. Despite its significance, little research has thus far been devoted to understanding the electrochemical stability of SPEs under the harsh conditions exerted by next-generation electrode materials.

In this thesis, the stability and ramifications of interfaces in polycarbonate- and polyester-based SPEs have been investigated. The polycarbonate exhibited severe degradation upon contact with lithium compared to its ester counterpart. Volatile species stemming from polycarbonate and salt decomposition were observed independent of irreversible current response, thus also highlighting the limitations of voltammetry techniques to determine the electrochemical stability. Two novel techniques were thus devised to evaluate electrochemical stability of SPEs under more realistic conditions. Characterization of the electrode−polyester interface revealed formation of highly resistive interfacial layers composed of polymer, salt and impurity derivatives. The emergence of a detrimental resistance emanating from the polymer−polymer interface was also observed, thus identifying a crucial hurdle for double-layer SPEs as a strategy to extend the stability window.

The application of polycarbonate/polyester-based polymer electrolytes for sodium-ion batteries was also studied. Sodium is far more abundant than lithium, and thereby an excellent chemistry platform to develop new sustainable battery materials. The polycarbonate exhibited an exceptional ability to dissolve large quantities of sodium salt without compromising the mechanical stability. Spectroscopic and thermal measurements revealed the emergence of an alternative ionic transport mechanism at concentrations within the polymer-in-salt regime, which was decoupled from the segmental motion of the polymer chains. By incorporating flexible polyester moieties in polycarbonates, an SPE with better transport properties compared to its individual subunits, and polyether counterparts, was obtained. Optimal salt concentration in this copolymer was dependent on the degree of crystallinity, determined by the portion of polyester. Finally, the practical application of these polymer electrolytes was demonstrated in solid-state sodium-ion batteries.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2021. p. 67
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2044
Keywords
Lithium-ion batteries, solid-state polymer electrolytes, electrochemical stability window, interfaces, ionic conductivity, polycarbonate, polyester, sustainability, sodium-ion
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-440905 (URN)978-91-513-1214-9 (ISBN)
Public defence
2021-06-11, Room Å2001, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2021-05-19 Created: 2021-04-21 Last updated: 2021-06-23

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Sångeland, ChristoferSun, BingBrandell, DanielBerg, Erik J.Mindemark, Jonas

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