Lamellar Ionenes with Highly Dissociative, Anionic Channels Provide Lower Barriers for Cation Transport.

Solid polymer electrolytes have the potential to enable safer and more energy-dense batteries; however, a deeper understanding of their ion conduction mechanisms, and how they can be optimized by molecular design, is needed to realize this goal. Here, we investigate the impact of anion dissociation energy on ion conduction in solid polymer electrolytes via a novel class of ionenes prepared using acyclic diene metathesis (ADMET) polymerization of highly dissociative, liquid crystalline fluorinated aryl sulfonimide-tagged ("FAST") anion monomers. These ionenes with various cations (Li+, Na+, K+, and Cs+) form well-ordered lamellae that are thermally stable up to 180 °C and feature domain spacings that correlate with cation size, providing channels lined with dissociative FAST anions. Electrochemical impedance spectroscopy (EIS) and differential scanning calorimetry (DSC) experiments, along with nudged elastic band (NEB) calculations, suggest that cation motion in these materials operates via an ion-hopping mechanism. The activation energy for Li+ conduction is 59 kJ/mol, which is among the lowest for systems that are proposed to operate via an ion conduction mechanism that is decoupled from polymer segmental motion. Moreover, the addition of a cation-coordinating solvent to these materials led to a >1000-fold increase in ionic conductivity without detectable disruption of the lamellar structure, suggesting selective solvation of the lamellar ion channels. This work demonstrates that molecular design can facilitate controlled formation of dissociative anionic channels that translate to significant enhancements in ion conduction in solid polymer electrolytes.

Anhydrous Proton Transport within Phosphonic Acid Layers in Monodisperse Telechelic Polyethylenes.

Polymers bearing phosphonic acid groups have been proposed as anhydrous proton-conducting membranes at elevated operating temperatures for applications in fuel cells. However, the synthesis of phosphonated polymers and the control over the nanostructure of such polymers is challenging. Here, we report the straightforward synthesis of phosphonic acid-terminated, long-chain aliphatic materials with precisely 26 and 48 carbon atoms (C26PA2 and C48PA2). These materials combine the structuring ability of monodisperse polyethylenes with the ability of phosphonic acid groups to form strong hydrogen-bonding networks. Anhydride formation is absent so that charge carrier loss by a condensation reaction is avoided even at elevated temperatures. Below the melting temperature (Tm), both materials exhibit a crystalline polyethylene backbone and a layered morphology with planar phosphonic acid aggregates separated by 29 and 55 Å for C26PA2 and C48PA2, respectively. Above Tm, the amorphous polyethylene (PE) segments coexist with the layered aggregates. This phenomenon is especially pronounced for the C26PA2 and is identified as a thermotropic smectic liquid crystalline phase. Under these conditions, an extraordinarily high correlation length (940 Å) along the layer normal is observed, demonstrating the strength of the hydrogen bond network formed by the phosphonic acid groups. The proton conductivity in both materials in the absence of water reaches 10-4 S/cm at 150 °C. These new precise phosphonic acid-based materials illustrate the importance of controlling the chemistry to form self-assembled nanoscale aggregates that facilitate rapid proton conductivity.