DOE OSTI · 2586911
Unraveling the pathway towards superionic transport in polymer electrolytes
Abstract
Ionic transport in polymers is critical for Li-ion batteries, fuel cells, flow batteries and many other energy storage and conversion technologies. A significant enhancement of ion conductivity in polymers may be achieved through an increase in the polarity of side chains and their self-organization into specific morphologies, which can potentially act as percolated ionic structures. However, higher polarity increases attractive interactions within a polymer matrix and slows down its segmental dynamics, which conversely hinders ionic transport. To overcome this tradeoff, we designed the functionalization of a Li salt-doped polymer matrix by tailored amounts of zwitterionic (ZI) groups. Our results suggest the emergence of a self-assembled percolation conductivity regime above a specific ZI concentration, in which ion hopping decouples from segmental dynamics by up to ten orders of magnitude. Consequently, in the highly concentrated ZI regime, our polymeric materials exhibit in their glassy state energy barriers for ion hopping similar to, or even smaller than, those reported for superionic ceramics. Our study also reveals that ion dynamics in the poly(zwitterion) with all monomers carrying ZI groups is significantly faster than that of a monomeric ZI compound, although the latter has much faster structural relaxation. Furthermore, this result highlights the crucial role played by the local morphology on the ion transport of polymer electrolytes and opens a new pathway for the design of superionic polymers, significantly expanding the current limited portfolio of solid-state electrolytes for energy applications.
Explore related subjects
Keep this discovery
Explore connections, maps & timelines
Uddin, Ain [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)], Lehmann, Michelle [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000313239785), Singh, Harmandeep [University of Tennessee, Knoxville, TN (United States)] (ORCID:0009000727361411), Bocharova, Vera [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000342703866), Kearney, Logan T. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000308113483), Damron, Joshua T. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)], Liu, Yifan [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000151020552), Cooper, Valentino R. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000167144410), Kumar, Rajeev [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000194943488), Schweizer, Kenneth S. [University of Illinois, Urbana-Champaign, IL (United States)], Sokolov, Alexei P. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); University of Tennessee, Knoxville, TN (United States)] (ORCID:0000000281879445), Saito, Tomonori [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); University of Tennessee, Knoxville, TN (United States)] (ORCID:0000000245367530), Gainaru, Catalin [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)]. 2025-07-10. Unraveling the pathway towards superionic transport in polymer electrolytes. https://doi.org/10.1016/j.mattod.2025.06.043
Cite the original work for its findings. Save a collection to share your selection of sources.