Design of Highly Conductive PILs by Simple Modification of Poly(epichlorohydrin- co -ethylene oxide) with Monosubstituted Imidazoles.

Autor: Nosov DR; Luxembourg Institute of Science and Technology, 5 Avenue des Hauts-Fourneaux, L-4362 Esch-sur-Alzette, Luxembourg.; Department of Physics and Materials Science, University of Luxembourg, 2 Avenue de l'Université, L-4365 Esch-sur-Alzette, Luxembourg., Lozinskaya EI; A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences (INEOS RAS), Vavilov Street 28, Bld. 1, 119334 Moscow, Russia., Antonov DY; A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences (INEOS RAS), Vavilov Street 28, Bld. 1, 119334 Moscow, Russia., Ponkratov DO; A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences (INEOS RAS), Vavilov Street 28, Bld. 1, 119334 Moscow, Russia., Tyutyunov AA; A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences (INEOS RAS), Vavilov Street 28, Bld. 1, 119334 Moscow, Russia., Alaa Eddine M; Univ Lyon, Université Lyon 1, CNRS, Ingénierie des Matériaux Polymères, UMR 5223, F-69003 Lyon, France., Plesse C; CY Cergy Paris Université, Laboratoire de Physicochimie des Polymères et des Interfaces, 5 Mail Gay Lussac, F-95031 Cergy-Pontoise Cedex, France., Schmidt DF; Luxembourg Institute of Science and Technology, 5 Avenue des Hauts-Fourneaux, L-4362 Esch-sur-Alzette, Luxembourg., Shaplov AS; Luxembourg Institute of Science and Technology, 5 Avenue des Hauts-Fourneaux, L-4362 Esch-sur-Alzette, Luxembourg.
Jazyk: angličtina
Zdroj: ACS polymers Au [ACS Polym Au] 2024 Sep 12; Vol. 4 (6), pp. 512-526. Date of Electronic Publication: 2024 Sep 12 (Print Publication: 2024).
DOI: 10.1021/acspolymersau.4c00051
Abstrakt: High ionic conductivity poly(ionic liquid)s (PILs) are of growing interest for their thermal and electrochemical stability, processability, and potential in safe, flexible all-solid-state electrochemical devices. While various approaches to enhance the ionic conductivity are reported, the influence of cation substituents is rarely addressed. Moreover, some of the asymmetric anions recently developed for high-conductivity ionic liquids were never tested in PILs. We report the design and synthesis of twelve novel cationic PILs prepared via quaternization of N-substituted imidazoles by commercially available poly(epichlorohydrin- co -ethylene oxide) (poly(EPCH- r -EO)) with subsequent ion metathesis. They differ by imidazolium side chain length (C 1 -C 6 alkyl) and presence of heteroatoms (silyl, siloxane, and fluoroalkyl) and by anion type (bis(trifluoromethylsulfonyl)imide (TFSI), 2,2,2-trifluoromethylsulfonyl- N -cyanoamide (TFSAM), tetrafluoroborate (BF 4 ), trifluoro(trifluoromethyl)borate (BF 3 CF 3 ), and tricyanofluoroborate (BF(CN) 3 )). TFSI-based PILs with alkyl side chains gave lower glass transition temperatures ( T g ) and higher ionic conductivities than those bearing heteroatomic substituents, with n -butyl side chains providing a conductivity of 4.7 × 10 -6 S cm -1 at 25 °C under anhydrous conditions. This increased to 1.0 × 10 -5 and 4.5 × 10 -4 S cm -1 at 25 and 70 °C, respectively, when the TFSI anion was replaced with BF(CN) 3 . All PILs showed good electrochemical (>3.2 V vs Ag + /Ag) and thermal (>185 °C) stability, making them excellent candidates for solid-state electrolytes in electrochemical devices.
Competing Interests: The authors declare no competing financial interest.
(© 2024 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
Externí odkaz: