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Modulating Ionic Conductivity in Star and Linear Poly(ionic liquids) by Dipolar Interactions
Eduardo Hermosillo-Ochoa1, Jiahui Liu1, Marek W Urban1
1Department of Materials Science and Engineering, Clemson University, Clemson, South Carolina 29634, United States.
ACS Macro Letters
|March 13, 2026
Summary
Block star poly(ionic liquids) show significantly higher ionic conductivity than random star counterparts due to enhanced dipolar interactions. Molecular design of these polymers allows tuning conductivity for advanced applications.
Area of Science:
- Polymer Chemistry
- Materials Science
- Electrochemistry
Background:
- Ionic conductivity in poly(ionic liquids) (PILs) is crucial for applications but often limited.
- Understanding polar-dipolar interactions is key to enhancing PIL performance.
- Molecular design offers a pathway to tailor polymer properties.
Purpose of the Study:
- To investigate the impact of copolymer architecture and topology on PIL ionic conductivity.
- To explore the role of polar-dipolar interactions in conductivity enhancement.
- To synthesize and characterize novel PILs with controlled structures.
Main Methods:
- Reversible addition-fragmentation chain transfer (RAFT) polymerization was used to create copolymers.
- Imidazolium-based ionic monomers were copolymerized into random and block architectures.
- Spectroscopic, thermal, and conductivity measurements were employed for characterization.
Main Results:
- Block star PILs demonstrated 2-3 orders of magnitude higher ionic conductivity than random star PILs.
- Enhanced conductivity in block star PILs is attributed to inter- and intrachain dipolar interactions.
- Variable alkyl side-chain lengths allowed tuning of frequency-dependent ionic conductivity.
Conclusions:
- Copolymer topology significantly influences ionic conductivity in PILs.
- Block star architectures facilitate greater ion mobility through optimized dipolar interactions.
- Tailoring PILs via molecular design opens avenues for conductive interfaces in various applications.
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