Toward Understanding Interfacial Phenomena of Anion Exchange Membrane Water Electrolyzers: Investigating the Role of Electrolyte pH Gradient with Operando Raman Spectroscopy

There is growing industrial appeal of anion exchange membrane water electrolyzers (AEMWEs) to produce hydrogen. A significant challenge remains that AEMWE durability testing is not standardized, and more minute interfacial degradation mechanisms between ionomer, catalyst, membrane, and electrolyte are not well characterized. Of particular interest is the impact of electrolyte selection on the polarization performance. There is a general desire to achieve reliable operation with environmentally obtained saltwater as the electrolyte, although this presents numerous challenges manifesting in typically poor long-term durability. Saltwater presents complexities in determining electrolyzer component interfacial phenomena. Performance of AEMWEs is typically benchmarked with hydroxide or carbonate solutions, therefore providing more direct opportunities to study fundamental mechanisms with regards to interactions between surfaces. Of particular interest is the presence of electrolyte anion concentration gradients that depend on the polarization state of the oxygen evolution reaction electrode (OER). We demonstrated in our early work with operando Raman probing of a custom designed spectroelectrochemical cell that there is initial evidence of spatially resolved anion gradients from the OER electrode surface into bulk electrolyte in a half cell configuration. We hypothesize that local pH changes near an electrode surface may impact the polarization via transport limited ion exchange and the relative overpotential of the overall cell, ultimately leading to an iterative and long-term contribution to decaying cell durability. We continue our work with a series of in-situ Raman experiments with a full cell configuration: OER electrode with PGM free catalyst, hydrogen evolution reaction (HER) electrode with PGM free catalyst, and anion conductive polymer membrane. Both electrodes also contain an ionically conductive polymer, or ionomer, that serves as a binder. By increasing the complexity of the system to match that of an industrially relevant configuration, we aim to probe the spatially resolved pH gradient with both potassium hydroxide and potassium carbonate solutions of varying concentrations. We utilized a custom, 3D printed, flow cell design comprising a sapphire observation window and isolated electrolyte flow chambers. Operando Raman spectroscopy measurements were conducted primarily with potassium carbonate solutions by tracking the spatially resolved changes in relative peak intensity of carbonate and bicarbonate signatures. With regards to the carbonate-bicarbonate equilibrium, we calculate changes in pH as the probe approaches the surface of an electrode. We finally connect our findings to a proposed mechanism for the interfacial phenomena relative to cell durability as a function of concentration changes and operating voltages.