Emerging membraneless electrolyzers offer an attractive approach to lowering the cost of hydrogen (H2) production from water electrolysis thanks to potential advantages in durability and manufacturability that are made possible by elimination of membranes or diaphragms from the device architecture. However, a fair comparison of the performance limits of membraneless electrolyzers to conventional electrolyzers is hindered by the early stage of research and absence of established design rules for the former. This task is made all the more difficult by the need to quantitatively describe multiphase flow between the electrodes in membraneless electrolyzers, which can have a huge impact on gas product purity. Using a parallel plate membraneless electrolyzer (PPME) as a model system, this study takes a combined experimental and modeling approach to explore its performance limits and quantitatively describe the trade-offs between efficiency, current density, electrode size, and product purity. Central to this work is the use of in situ high-speed videography (HSV) to monitor the width of H2 bubble plumes produced downstream of parallel plate electrodes as a function of current density, electrode separation distance, and the Reynolds number (Re) associated with flowing 0.5 M H2SO4 electrolyte. These measurements reveal that the HSV-derived dimensionless bubble plume width serves as an excellent descriptor for correlating the aforementioned operating conditions with H2 crossover rates. These empirical relationships, combined with electrochemical engineering design principles, provide a valuable framework for exploring performance limits and guiding the design of optimized membraneless electrolyzers. Our analysis shows that the efficiencies and current densities of optimized PPMEs constrained to H2 crossover rates of 1% can exceed those of conventional alkaline electrolyzers but are lower than the efficiencies and current densities achieved by zero-gap polymer electrolyte membrane (PEM) electrolyzers.
