The electrochemical reduction of CO₂ is a pivotal technology for the defossilization of the chemical industry. Although pilot-scale electrolyzers exist, water management and salt precipitation remain a major hurdle to long-term operation. In this work, we present high-resolution neutron imaging (6 μm) of a zero-gap CO₂ electrolyzer to uncover water distribution and salt precipitation under application-relevant operating conditions (200 mA cm⁻² at a cell voltage of 2.8 V with a Faraday efficiency for CO of 99%). Precipitated salts penetrating the cathode gas diffusion layer can be observed, which are believed to block the CO₂ gas transport and are therefore the major cause for the commonly observed decay in Faraday efficiency. Neutron imaging further shows higher salt accumulation under the cathode channel of the flow field compared to the land.

Dry cathode operation is a desired operation mode in anion-exchange membrane water electrolyzers to minimize contamination of the generated hydrogen. However, water management under such operation conditions makes it challenging to maintain reliable performance and durability. Here, we utilize high-resolution in situ neutron imaging (∼6 μm effective resolution) to analyze the water content inside the membrane-electrode-assembly of an anion-exchange membrane water electrolyzer. The ion-exchange capacity (IEC) and thus hydrophilicity of the polymer binder in the cathode catalyst layer is varied to study the influence on water content in the anode (mid IEC, 1.8–2.2 meq. g⁻¹ and high IEC, 2.3–2.6 meq. g⁻¹). The neutron radiographies show that a higher ion-exchange capacity binder allows improved water retention, which reduces the drying-out of the cathode at high current densities. Electrochemical measurements confirm a generally better efficiency for a high IEC cell above 600 mA cm⁻². At 1.5 A cm⁻² the high IEC has a 100 mV lower overpotential (2.1 V vs. 2.2 V) and a lower high frequency resistance (210 mΩ cm⁻² vs. 255 mΩ cm⁻²), which is believed to be linked to the improved cathode water retention and membrane humidification. As a consequence, the performance stability of the high IEC cell at 1 A cm⁻² is also significantly better than that of the mid IEC cell (45 mV h⁻¹ vs. 75 mV h⁻¹).

The neutron imaging facility ANTARES, operated by the Technische Universität München, is located at the cold neutron beam port SR-4a. Based on a pinhole camera principle with a variable collimator located close to the beam port, the facility provides the possibility for flexible use in high resolution and high flux imaging.