Nanofibrillar Ionic Polymer Composites Enable High-Modulus Ion-Conducting Membranes

Polymer electrolyte membranes (PEMs) with high volume fractions of ionic liquids (IL) and high modulus show promise for enabling next-generation gas separations, and electrochemical energy storage and conversion applications. Herein, we present a conductive polymer-IL composite based on a sulfonated all-aromatic polyamide (sulfo-aramid, PBDT) and a model IL, which we term a PBDT-IL composite. The polymer forms glassy and high-aspect-ratio hierarchical nanofibrils, which enable fabrication of PEMs with both high volume fractions of IL and high elastic modulus. We report direct evidence for nanofibrillar networks that serve as matrices for dispersed ILs using atomic force microscopy and small- and wide-angle X-ray scattering. These supramolecular nanofibrils form through myriad noncovalent interactions to produce a physically cross-linked glassy network, which boasts the best combination of room-temperature modulus (0.1–2 GPa) and ionic conductivity (8–4 mS cm–1) of any polymer-IL electrolyte reported to date. The ultrahigh thermomechanical properties of our PBDT-IL composites provide high moduli (∼1 GPa) at temperatures up to 200 °C, enabling a wide device operation window with stable mechanical properties. Together, the high-performance nature of sulfo-aramids in concert with the inherent properties of ILs imparts PBDT-IL composites with nonflammability and thermal stability up to 350 °C. Thus, nanofibrillar ionic networks based on sulfo-aramids and ILs represent a new design paradigm affording PEMs with exceptionally high moduli at exceedingly low polymer concentrations. This new design strategy will drive the development of new high-performance conductive membranes that can be used for the design of gas separation membranes and in electrochemical applications, such as fuel cells and Li-metal batteries.