1. Decoding Polymer Architecture Effect on Ion Clustering, Chain Dynamics, and Ionic Conductivity in Polymer Electrolytes
- Author
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Recep Bakar, Saeid Darvishi, Umut Aydemir, Ugur Yahsi, Cumali Tav, Yusuf Ziya Menceloglu, Erkan Senses, and Bakar R., Darvishi S., Aydemir U., YAHŞİ U., TAV C., Menceloglu Y. Z., Senses E.
- Subjects
Tarımsal Bilimler ,Sinyal İşleme ,Temel Bilimler (SCI) ,Mühendislik ,Enerji Mühendisliği ve Güç Teknolojisi ,ENGINEERING ,homopolymer electrolytes ,ion pairing and clustering ,Physical Chemistry ,MATERIALS SCIENCE ,Kimya ,Ziraat ,Information Systems, Communication and Control Engineering ,Kimya Mühendisliği (çeşitli) ,CHEMISTRY ,ENERGY & FUELS ,Kimya Mühendisliği ve Teknolojisi ,Materials Chemistry ,Electrochemistry ,ELEKTROKİMYA ,Chemical Engineering (miscellaneous) ,MÜHENDİSLİK, KİMYASAL ,ENGINEERING, ELECTRICAL & ELECTRONIC ,Malzeme Kimyası ,Agricultural Sciences ,Elektrik ve Elektronik Mühendisliği ,Temel Bilimler ,ENERJİ VE YAKITLAR ,Tarımda Enerji ,Fizikokimya ,Agriculture ,phase diagram ,Energy in Agriculture ,Natural Sciences (SCI) ,Physical Sciences ,free volume ,ionic conductivity ,Engineering and Technology ,Biofuels Technology ,Bilgi Sistemleri, Haberleşme ve Kontrol Mühendisliği ,Natural Sciences ,Farm Machinery ,Energy Engineering and Power Technology ,MATERIALS SCIENCE, MULTIDISCIPLINARY ,Chemical Engineering and Technology ,Biyoyakıt Teknolojisi ,polymer architecture ,Tarım Makineleri ,poly(ethylene oxide) ,Electrical and Electronic Engineering ,MALZEME BİLİMİ, ÇOKDİSİPLİNLİ ,Engineering, Computing & Technology (ENG) ,Mühendislik, Bilişim ve Teknoloji (ENG) ,Elektrokimya ,Fizik Bilimleri ,Signal Processing ,viscosity ,MÜHENDİSLİK, ELEKTRİK VE ELEKTRONİK ,Mühendislik ve Teknoloji ,Malzeme Bilimi ,ENGINEERING, CHEMICAL - Abstract
Poly(ethylene oxide) (PEO)-based polymer electrolytes are a promising class of materials for use in lithium-ion batteries due to their high ionic conductivity and flexibility. In this study, the effects of polymer architecture including linear, star, and hyperbranched and salt (lithiumbis(trifluoromethanesulfonyl)imide (LiTFSI)) concentration on the glass transition (Tg), microstructure, phase diagram, free volume, and bulk viscosity, all of which play a significant role in determining the ionic conductivity of the electrolyte, have been systematically studied for PEO-based polymer electrolytes. The branching of PEO widens the liquid phase toward lower salt concentrations, suggesting decreased crystallization and improved ion coordination. At high salt loadings, ion clustering is common for all electrolytes, yet the cluster size and distribution appear to be strongly architecture-dependent. Also, the ionic conductivity is maximized at a salt concentration of [Li/EO ≈ 0.085] for all architectures, and the highly branched polymers displayed as much as three times higher ionic conductivity (with respect to the linear analogue) for the same total molar mass. The architecture-dependent ionic conductivity is attributed to the enhanced free volume measured by positron annihilation lifetime spectroscopy. Interestingly, despite the strong architecture dependence of ionic conductivity, the salt addition in the highly branched architectures results in accelerated yet similar monomeric friction coefficients for these polymers, offering significant potential toward decoupling of conductivity from segmental dynamics of polymer electrolytes, leading to outstanding battery performance.
- Published
- 2023