Understanding the Effects of Anode Catalyst Conductivity and Loading on Catalyst Layer Utilization and Performance for Anion Exchange Membrane Water Electrolysis.

Anion exchange membrane water electrolysis (AEMWE) is a promising technology to produce hydrogen from low-cost, renewable power sources. Recently, the efficiency and durability of AEMWE have improved significantly due to advances in the anion exchange polymers and catalysts. To achieve performances and lifetimes competitive with proton exchange membrane or liquid alkaline electrolyzers, however, improvements in the integration of materials into the membrane electrode assembly (MEA) are needed. In particular, the integration of the oxygen evolution reaction (OER) catalyst, ionomer, and transport layer in the anode catalyst layer has significant impacts on catalyst utilization and voltage losses due to the transport of gases, hydroxide ions, and electrons within the anode. This study investigates the effects of the properties of the OER catalyst and the catalyst layer morphology on performance. Using cross-sectional electron microscopy and in-plane conductivity measurements for four PGM-free catalysts, we determine the catalyst layer thickness, uniformity, and electronic conductivity and further use a transmission line model to relate these properties to the catalyst layer resistance and utilization. We find that increased loading is beneficial for catalysts with high electronic conductivity and uniform catalyst layers, resulting in up to 55% increase in current density at 2 V due to decreased kinetic and catalyst layer resistance losses, while for catalysts with lower conductivity and/or less uniform catalyst layers, there is minimal impact. This work provides important insights into the role of catalyst layer properties beyond intrinsic catalyst activity in AEMWE performance.

Membranes Matter: Preventing Ammonia Crossover during Electrochemical Ammonia Synthesis.

The electrochemical nitrogen and nitrate reduction reactions (E-NRR and E-NO3RR) promise to provide decentralized and fossil-fuel-free ammonia synthesis, and as a result, E-NRR and E-NO3RR research has surged in recent years. Membrane NH3/NH4+ crossover during E-NRR and E-NO3RR decreases Faradaic efficiency and thus the overall yield. During catalyst evaluation, such unaccounted-for crossover results in measurement error. Herein, several commercially available membranes were screened and evaluated for use in ammonia-generating electrolyzers. NH3/NH4+ crossover of the commonly used cation-exchange membrane (CEM) Nafion 212 was measured in an H-cell architecture and found to be significant. Interestingly, some anion exchange membranes (AEMs) show negligible NH4+ crossover, addressing the problem of measurement error due to NH4+ crossover. Further investigation of select membranes in a zero-gap gas diffusion electrode (GDE)-cell determines that most membranes show significant NH3 crossover when the cell is in an open circuit. However, uptake and crossover of NH3 are mitigated when -1.6 V is applied across the GDE-cell. The results of this study present AEMs as a useful alternative to CEMs for H-cell E-NRR and E-NO3RR electrolyzer studies and present critical insight into membrane crossover in zero-gap GDE-cell E-NRR and E-NO3RR electrolyzers.