Polysilaketals: High‐Performance Polyether‐Based Electrolytes with Tunable Disubstituted Silane Linkers

Rugh, Haley J.; Lee, Jaeyong; Sun, Chenyue; Abdo, Emily E.; Bem, Juliana N.; Balsara, Nitash P.; Coates, Geoffrey W.

doi:10.1002/ange.202415069

Title: Polysilaketals: High‐Performance Polyether‐Based Electrolytes with Tunable Disubstituted Silane Linkers

Journal Article · 21 November 2024 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202415069 · OSTI ID:2530234

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Department of Chemistry and Chemical Biology Cornell University Ithaca NY 14853-1301 USA
Department of Chemical and Biomolecular Engineering University of California Berkeley Berkeley California 94720-1462 USA, Materials Sciences Division Lawrence Berkeley National Laboratory Berkeley California 94720-8099 USA

Abstract Polymer electrolytes exhibit higher energy density and improved safety in lithium‐ion batteries relative to traditionally used liquid electrolytes but are currently limited by their lower electrochemical performance. Aiming to access polymer electrolytes with competitive electrochemical properties, we developed the anionic ring‐opening polymerization (AROP) of cyclic silaketals to synthesize amorphous silicon‐containing polyether‐based electrolytes with varying substituent bulk of the general formula [OSi(R) ₂ (CH ₂ CH ₂ O) ₂ ] _n (R=alkyl, phenyl). As opposed to previously reported uncontrolled polycondensation routes toward low molecular weight polysilaketals, AROP allows access to targeted molecular weights above the entanglement threshold of the polymers. The polysilaketal with the lowest steric bulk (P(OSi ^Me,Me ‐2EO)) exceeds the conductivity of poly(ethylene oxide) (PEO), a leading polymer electrolyte. To the best of our knowledge, this is the first solid polymer electrolyte to achieve this benchmark. Steric bulk in polysilaketals was found to impart stability and two bulkier polysilaketals, P(OSi ^Et,Et ‐2EO) and P(OSi ^Me,Ph ‐2EO), exhibited higher current fractions than PEO over a wide range of salt loadings. Moreover, the efficacy of P(OSi ^Et,Et ‐2EO) was competitive with that of PEO. Taken together, the tunable and competitive electrochemical properties of polysilaketals validate the systematic incorporation of silyl groups as a strategy to access high performance polymer electrolytes.

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Sponsoring Organization:: USDOE

OSTI ID:: 2530234

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 2 Vol. 137; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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