Proton Conducting Sulfonated Poly(Ionic Liquid) Block Copolymers

• Published in: Macromolecules Vol. 55; no. 15; pp. 6716 - 6729
• Main Authors: Sun, Rui, Agrawal, Mahesh, Neyerlin, Kenneth C., Snyder, Joshua D., Elabd, Yossef A.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 09.08.2022
• Subjects: anion exchange; composite polymers; Copolymers; Electrical conductivity; electrochemistry; Equilibrium; fuel cells; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ionic liquids; moieties; oxygen; polymerization; Polymers; relative humidity; small-angle X-ray scattering; solubility; Sorption; styrene; sulfonic acids
• ISSN: 0024-9297; 1520-5835; 1520-5835
• DOI: 10.1021/acs.macromol.2c00468

Herein, we report the synthesis of proton-conducting sulfonated poly­(ionic liquid) block copolymers (S-PILBCPs) containing one block with sulfonic acid (sulfonated styrene, SS) and the other with an IL moiety (vinylbenzylmethylimidazolium bis­(trifluoromethylsulfonyl)­imide, VBMIm-TFSI) using reversible addition–fragmentation chain-transfer (RAFT) polymerization and post-polymerization modifications (i.e., functionalization, anion exchange reactions, and sulfonation). The S-PILBCPs uniquely conjoin the SS block with mobile protons (H+) and the PIL block with mobile anions (TFSI–), where multiple highly desired properties, including high proton conductivity (from the SS block), and high IL-philicity and oxygen solubility (from the PIL block) can exist compartmentally within a microphase separated morphology (evidenced by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS)). High ion conductivity of 79.7 mS/cm at a PIL block composition of 21.6 mol % was observed at 80 °C and 90% relative humidity (RH) (comparable to the benchmark Nafion ionomer). This work successfully demonstrates the design of S-PILBCPs as a new material platform and showcases its promise as an ionomer for proton exchange membrane fuel cells (PEMFCs) as they simultaneously and compartmentally combine proton conductivity and oxygen solubility. These benefits have recently been leveraged to achieve substantial improvement in oxygen reduction reaction (ORR) activity and subsequently fuel cell performance.