Proceedings of MATSUS Fall 2024 Conference (MATSUSFall24)
Publication date: 28th August 2024
CO2 electrolysis is a promising technology for transitioning from fossil fuels to sustainable energy and materials, but it requires improvement. CO2 electrolysis with a bipolar membrane in forward-bias has two critical advantages over the state-of-the-art alkaline membrane-based devices: it reduces CO2 crossover, maximizing CO2 utilization, and operates with pure water as anode feed, avoiding cation crossover and precipitation in the cathode, which can cause flooding. However, using a bipolar membrane presents additional challenges. For example, the junction between the acidic and alkaline membranes creates an interface where anions recombine with protons to form water and CO2. This reaction is spontaneous and should help lower the overall cell voltage. It has been found that a thin metal oxide catalyst layer could improve the water recombination reaction [1]. Still, whether this applies to CO2 electrolyzers where both water and CO2 recombine at the junction is unclear.
Our investigation aimed to shed light on this issue. To do so, we prepared ionomer-free catalyst layers (CLs) with different loadings (ranging from 0 to 77μg/cm2) and types (TiO2, SiO2, IrO2) at the membraned junction. We characterized their loading, distribution, and thicknesses and then conducted electrochemical tests on a zero-gap cell with a hydrogen-depolarized anode. We used a reference electrode to ensure the anode didn't contribute to the overall cell potential. We also kept the current densities below 20 mA/cm2 to prevent delamination of the bipolar membrane or other mass transport limitations.
The results showed that adding TiO2 with low loading (10-30 μg/cm2) significantly improved performance (up to 54 mV at 20 mA cm-2). These loadings corresponded to a complete coverage of the CL of the junction area. Higher loading did not improve the reaction further and exhibited higher HFR values. Impedance analysis revealed that the catalyst removes one interface resistance at high frequencies. We also found that other metal oxides (IrO2 and SiO2) improved performance despite exhibiting very different particle size distributions.
This study contributed to enhancing the performance of zero-gap BPM CO2 electrolyzers in forward-bias mode. It will help to resolve one of their primary issues: the globally observed high cell voltages.
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