Increasing the Electrolyte Salinity to Improve the Performance of Anion Exchange Membrane Water Electrolyzers

Direct operation of anion exchange membrane water electrolyzers (AEMWEs) with near-neutral pH feeds avoids the use of highly alkaline and corrosive solutions. However, using neutral pH solutions currently faces fundamental operational challenges that diminish performance and reduce long-term stability due to poor solution conductivity and low hydroxide ion concentration. Here, we showed that amending near-neutral pH solutions with low concentrations of alkali metal salts in a dry-cathode configuration substantially improved performance and stability. Adding NaClO₄ (10 mM) to the anolyte reduced the operating voltage by 0.19 to 2.58 V at 500 mA/cm² compared to non-saline solutions (2.77 V). However, further increases in the feed salt concentration (100 mM NaClO₄) reduced performance (2.64 V) due to a greater co-ion diffusion through the anion exchange membrane. Electrolyzer performance was further improved by utilizing salts with high conductivity such as KNO₃. Using a saline anolyte reduced ohmic resistance, resulting in smaller applied voltage and energy consumption for hydrogen generation, while the combined effect of the membrane charge and the electric field direction in the dry-cathode feed configuration minimized ion crossover. Thus, increasing the salinity of near-neutral pH solutions represents a cost-effective strategy to improve the performance of AEMWE compared to ultrapure electrolytes, minimizing risks and costs associated with recirculating highly alkaline solutions.