The decoupled power and energy output of a redox flow battery (RFB) offers a key advantage in long-duration energy storage, crucial for a successful energy transition. Iodide/iodine and hydrogen/water, owing to their fast reaction kinetics, benign nature, and high solubility, provide promising battery chemistry. However, H₂-I₂ RFBs suffer from low open circuit potentials, iodine crossover, and their multiphase nature. We demonstrate a H₂-I₂ operation with a combined neutral-pH catholyte (I₃^-/I^-) and an alkaline anolyte (KOH), producing an open circuit cell voltage of 1.28 V. Additionally, we incorporate a pressure-balanced gas diffusion electrode (GDE) to mitigate mass transport limitations at the anode. These improvements result in a maximum power density of 230 W/m² when allowing a mild breakthrough of H₂ through the GDE. While minimal crossover occurs, side reactions of permeating active species were found reversible, enabling long-term operation. Future work should address the stability of the GDE and optimization of the electrolyte thickness and concentration to fully leverage the potential unlocked by balancing the pressure and pH in the H₂-I₂ RFB.

Nanofluidic membranes (NFMs) are gaining prominence as alternative ion-exchange membranes, because of their distinct selectivity mechanism, which does not rely on functional groups on a polymeric backbone but rather on charged nanopores that allow straight ion-conductive pathways for efficient ion transport. We measured the conductivity of commercial anodized aluminum oxide membranes with different pore sizes under different current densities and electrolyte concentrations. We also simulated a nanopore channel with charged walls between two electrolyte reservoirs. Our findings indicate that electrolyte concentration is the main parameter that determines NFM conductivity, with a linear dependence at least up to 1 M. Our study shows that the optimal pore length is between 0.5 and 5 μm considering the trade-off between selectivity and conductance. On the other hand, the conductance is not sensitive to the pore diameter. Conical nanopores are a way to increase conductance, but according to our results, this increase comes at the expense of selectivity. Our findings suggest that NFMs can outperform polymeric ion-exchange membranes in certain electrochemical applications, such as reverse electrodialysis, but not in applications that use low electrolyte concentrations on both sides of the membrane.

Polymeric ion-exchange membranes (IEMs) are key to many electrochemical processes, but their intrinsic selectivity limitations restrict scale-up possibilities. Nanofluidic IEMs, based on inorganic rigid materials and charged nanopores, offer a promising alternative. We present design criteria for selective nanofluidic membranes. We used commercial anodized aluminium oxide (AAO) membranes with varying pore sizes to measure permselectivity between different KCl concentrations. Our experiments reveal that membranes with 10-nm pores have permselectivities above 90%, comparable to those of polymeric IEMs, up to electrolyte concentrations of 0.15 vs. 0.75 M. To our knowledge, this is the highest reported ion selectivity for nanofluidic IEMs. Conversely, asymmetric AAO membranes featuring a thin selective layer, exhibited low permselectivity. We explored the influence of other parameters through simulations using the space-charge model. Our numerical results indicate that pore size and surface potential are the most sensitive parameters for increasing selectivity. Additionally, pore length has a minimum requirement for good performance although increasing it beyond the μm scale yields no significant result. This study highlights nanofluidic IEMs as a promising alternative to polymeric IEMs and their capability to improve performance of many electrochemical processes, especially those involving low electrolyte concentrations on at least one membrane side.

Electrochemical reduction of carbon dioxide (CO₂R) poses substantial promise to convert abundant feedstocks (water and CO₂) to value-added chemicals and fuels using solely renewable energy. However, recent membrane-electrode assembly (MEA) devices that have been demonstrated to achieve high rates of CO₂R are limited by water management within the cell, due to both consumption of water by the CO₂R reaction and electro-osmotic fluxes that transport water from the cathode to the anode. Additionally, crossover of potassium (K⁺) ions poses concern at high current densities where saturation and precipitation of the salt ions can degrade cell performance. Herein, a device architecture incorporating an anion-exchange membrane (AEM) with internal water channels to mitigate MEA dehydration is proposed and demonstrated. A macroscale, two-dimensional continuum model is used to assess water fluxes and local water content within the modified MEA, as well as to determine the optimal channel geometry and composition. The modified AEMs are then fabricated and tested experimentally, demonstrating that the internal channels can both reduce K⁺ cation crossover as well as improve AEM conductivity and therefore overall cell performance. This work demonstrates the promise of these materials, and operando water-management strategies in general, in handling some of the major hurdles in the development of MEA devices for CO₂R.

A novel ion separation methodology using a cation-exchange membrane modified with iron oxide nanoparticles (Fe3O4 NPs) coated with polyhexamethylene guanidine (PHMG) is proposed. The separation is performed in an electrodialysis cell, where firstly phosphate is electro-adsorbed to the PHMG@Fe3O4 NP coating, followed by a desorption step by applying an electric current.