Aryl ether-free polymer electrolytes for electrochemical and energy devices.

Anion exchange polymers (AEPs) play a crucial role in green hydrogen production through anion exchange membrane water electrolysis. The chemical stability of AEPs is paramount for stable system operation in electrolysers and other electrochemical devices. Given the instability of aryl ether-containing AEPs under high pH conditions, recent research has focused on quaternized aryl ether-free variants. The primary goal of this review is to provide a greater depth of knowledge on the synthesis of aryl ether-free AEPs targeted for electrochemical devices. Synthetic pathways that yield polyaromatic AEPs include acid-catalysed polyhydroxyalkylation, metal-promoted coupling reactions, ionene synthesis via nucleophilic substitution, alkylation of polybenzimidazole, and Diels-Alder polymerization. Polyolefinic AEPs are prepared through addition polymerization, ring-opening metathesis, radiation grafting reactions, and anionic polymerization. Discussions cover structure-property-performance relationships of AEPs in fuel cells, redox flow batteries, and water and CO2 electrolysers, along with the current status of scale-up synthesis and commercialization.

Engineered Thin Diffusion Layers for Anion-Exchange Membrane Electrolyzer Cells with Outstanding Performance.

Anion-exchange membrane electrolyzer cells (AEMECs) are one of the most promising technologies for carbon-neutral hydrogen production. Over the past few years, the performance and durability of AEMECs have substantially improved. Herein, we report an engineered liquid/gas diffusion layer (LGDL) with tunable pore morphologies that enables the high performance of AEMECs. The comparison with a commercial titanium foam in the electrolyzer indicated that the engineered LGDL with thin-flat and straight-pore structures significantly improved the interfacial contacts, mass transport, and activation of more reaction sites, leading to outstanding performance. We obtained a current density of 2.0 A/cm2 at 1.80 V with an efficiency of up to 81.9% at 60 °C under 0.1 M NaOH-fed conditions. The as-achieved high performance in this study provides insight to design advanced LGDLs for the production of low-cost and high-efficiency AEMECs.

Synergistically integrated phosphonated poly(pentafluorostyrene) for fuel cells.

Modern electrochemical energy conversion devices require more advanced proton conductors for their broad applications. Phosphonated polymers have been proposed as anhydrous proton conductors for fuel cells. However, the anhydride formation of phosphonic acid functional groups lowers proton conductivity and this prevents the use of phosphonated polymers in fuel cell applications. Here, we report a poly(2,3,5,6-tetrafluorostyrene-4-phosphonic acid) that does not undergo anhydride formation and thus maintains protonic conductivity above 200 °C. We use the phosphonated polymer in fuel cell electrodes with an ion-pair coordinated membrane in a membrane electrode assembly. This synergistically integrated fuel cell reached peak power densities of 1,130 mW cm-2 at 160 °C and 1,740 mW cm-2 at 240 °C under H2/O2 conditions, substantially outperforming polybenzimidazole- and metal phosphate-based fuel cells. Our result indicates a pathway towards using phosphonated polymers in high-performance fuel cells under hot and dry operating conditions.

Phenyl Oxidation Impacts the Durability of Alkaline Membrane Water Electrolyzer.

The durability of alkaline anion exchange membrane (AEM) electrolyzers is a critical requirement for implementing this technology in cost-effective hydrogen production. Here, we report that the electrochemical oxidation of the adsorbed phenyl group (found in the ionomer) on oxygen evolution catalysts produces phenol, which may cause performance deterioration in AEM electrolyzers. In-line 1H NMR kinetic analyses of phenyl oxidation in a model organic cation electrolyte shows that catalyst type significantly impacts the phenyl oxidation rate at an oxygen evolution potential. Density functional theory calculations show that the phenyl adsorption is a critical factor determining the phenyl oxidation. This research provides a path for the development of more durable AEM electrolyzers with components that can minimize the adverse impact induced by the phenyl group oxidation, such as the development of novel ionomers with fewer phenyl moieties or catalysts with less phenyl-adsorbing character.