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Among existing water electrolysis (WE) technologies, anion-exchange-membrane water electrolyzers (AEMWEs) show promise for low-cost operation enabled by the basic solid-polymer electrolyte used to conduct hydroxide ions. The basic environment within the electrolyzer, in principle, allows the use of non-platinum-group metal catalysts and less-expensive cell components compared to acidic-membrane systems. Nevertheless, AEMWEs are still underdeveloped, and the degradation and failure modes are not well understood. To improve performance and durability, supporting electrolytes such as KOH and K2CO3 are often added to the water feed. The effect of the anion interactions with the ionomer membrane (particularly other than OH-), however, remains poorly understood. We studied three commercial anion-exchange ionomers (Aemion, Sustainion, and PiperION) during oxygen evolution (OER) at oxidizing potentials in several supporting electrolytes and characterized their chemical stability with surface-sensitive techniques. We analyzed factors including the ionomer conductivity, redox potential, and pH tolerance to determine what governs ionomer stability during OER. Specifically, we discovered that the oxidation of Aemion at the electrode surface is favored in the presence of CO32-/HCO3- anions perhaps due to the poor conductivity of that ionomer in the carbonate/bicarbonate form. Sustainion tends to lose its charge-carrying groups as a result of electrochemical degradation favored in basic electrolytes. PiperION seems to be similarly negatively affected by a pH drop and low carbonate/bicarbonate conductivity under the applied oxidizing potential. The insight into the interactions of the supporting electrolyte anions with the ionomer/membrane helps shed light on some of the degradation pathways possible inside of the AEMWE and enables the informed design of materials for water electrolysis.

Post-operation component disassembly and observation of electrolyzer parts is useful in understanding the interactions of the components and the electrochemical environment beyond the systems electrochemical output. We report a standard protocol for post-operation component disassembly and observation, including directions for cell-component preservation, preliminary visual inspection of cell components, and a guide for the advanced inspection of specific components with suggestions for further analysis if necessary. The procedures outlined here allow for a standardized method that can be used and compared between different laboratories and for literature comparison to experimental results.

Understanding the relationships between porous transport layer (PTL) morphology and oxygen removal is essential to improve the polymer electrolyte water electrolyzer (PEWE) performance. Operando X-ray computed tomography and machine learning were performed on a model electrolyzer at different water flow rates and current densities to determine how these operating conditions alter oxygen transport in the PTLs. We report a direct observation of oxygen taking preferential pathways through the PTL, regardless of the water flow rate or current density (1-4 A/cm2). Oxygen distribution in the PTL had a periodic behavior with period of 400 μm. A computational fluid dynamics model was used to predict oxygen distribution in the PTL showing periodic oxygen front. Observed oxygen distribution is due to low in-plane PTL tortuosity and high porosity enabling merging of oxygen bubbles in the middle of the PTL and also due to aerophobicity of the layer.

Polymer electrolyte membrane (PEM) electrolyzers are electrochemical energy-conversion devices that convert electricity into hydrogen fuel at high efficiencies. The interface between the porous transport layer (PTL) and catalyst layer is of interest from a transport perspective, as this interface is rough, reducing contact between the layers. Electrons, protons, water and oxygen have to simultaneously meet at this interface and there is a need to understand the optimal morphology. In this study we use operando X-ray computed tomography (CT) and X-ray radiography to visualize the operation of PEM electrolyzers under two current densities: 500 and 800 mA cm-2. First, we compare the performance of catalyst-coated membrane (CCM) electrolyzers with porous transport electrode (PTE) electrolyzers by correlating polarization curves with interface morphology observed with X-ray CT. At 1 A cm-2, the micro-CT CCM electrolyzer showed 200 mV improvement in potential primarily due to better contact between the electrocatalyst, membrane, and PTL. From the nano-CT imaging we discovered non-homogeneous distribution of an IrOx electrocatalyst. The modeling study shows that the primary reason for performance loss in the PTE configuration is due to the low connectivity of catalyst particles with the membrane. This causes bottlenecks in proton transport and results in high ionic potential losses in the anode. Then, we compared the polarization behavior and morphology of cells with CCMs but two types of PTLs. One was made with sintered titanium and the other with titanium fiber. The Ti fiber PTL showed higher porosity and lower tortuosities, however these better morphological properties did not necessarily translate into significantly lower potentials (45 mV difference), as the electrolyzer was not operated above 1 A cm-2. This was also confirmed by radiography study, where oxygen residence time in the channels showed similar fractions for both types of PTLs.

We demonstrate the translation of a low-cost, non-precious metal cobalt phosphide (CoP) catalyst from 1 cm2 lab-scale experiments to a commercial-scale 86 cm2 polymer electrolyte membrane (PEM) electrolyser. A two-step bulk synthesis was adopted to produce CoP on a high-surface-area carbon support that was readily integrated into an industrial PEM electrolyser fabrication process. The performance of the CoP was compared head to head with a platinum-based PEM under the same operating conditions (400 psi, 50 °C). CoP was found to be active and stable, operating at 1.86 A cm-2 for >1,700 h of continuous hydrogen production while providing substantial material cost savings relative to platinum. This work illustrates a potential pathway for non-precious hydrogen evolution catalysts developed in past decades to translate to commercial applications.

Hydrogen is an important part of any discussion on sustainability and reduction in emissions across major energy sectors. In addition to being a feedstock and process gas for many industrial processes, hydrogen is emerging as a fuel alternative for transportation applications. Renewable sources of hydrogen are therefore required to increase in capacity. Low-temperature electrolysis of water is currently the most mature method for carbon-free hydrogen generation and is reaching relevant scales to impact the energy landscape. However, costs still need to be reduced to be economical with traditional hydrogen sources. Operating cost reductions are enabled by the recent availability of low-cost sources of renewable energy, and the potential exists for a large reduction in capital cost withmaterial and manufacturing optimization. This article focuses on the current status and development needs by component for the low-temperature electrolysis options.

Solar-powered electrochemical production of hydrogen through water electrolysis is an active and important research endeavor. However, technologies and roadmaps for implementation of this process do not exist. In this perspective paper, we describe potential pathways for solar-hydrogen technologies into the marketplace in the form of photoelectrochemical or photovoltaic-driven electrolysis devices and systems. We detail technical approaches for device and system architectures, economic drivers, societal perceptions, political impacts, technological challenges, and research opportunities. Implementation scenarios are broken down into short-term and long-term markets, and a specific technology roadmap is defined. In the short term, the only plausible economical option will be photovoltaic-driven electrolysis systems for niche applications. In the long term, electrochemical solar-hydrogen technologies could be deployed more broadly in energy markets but will require advances in the technology, significant cost reductions, and/or policy changes. Ultimately, a transition to a society that significantly relies on solar-hydrogen technologies will benefit from continued creativity and influence from the scientific community.