On the mass transport phenomena in proton exchange membrane water electrolyzers

Abstract

Proton exchange membrane (PEM) water electrolysis is a technology designed to produce hydrogen using only water and electricity as inputs; it has gained increased attention in industry and academia due to its advantages over incumbent hydrogen generation processes (of which the most widely used are steam reforming and coal gasification) namely, low temperature, carbon-neutral and intermittent operation. PEM electrolysis can be instrumental for creating a hydrogen economy, although still much research needs to be carried out before widespread industrial adoption is achieved. PEM water electrolyzers suffer energy losses associated with the chemical reactions and the transport of charge and mass; of these phenomena, mass transport in PEM electrolyzers is the least understood subject, given the complex nature of the interaction of multiphase flows (mainly consisting of liquid water and evolved gases) through micrometric pores. The subject of multiphase flow in water electrolysis and its relationship with the mass transport phenomena in PEM water electrolysis has been a prevalent subject in the literature. Despite numerous attempts at pinpointing the relationship between mass transport overpotential and the operating parameters, there is no clear consensus about which transport mechanisms dominate, nor about how the component design of PEM electrolyzers affects the mass transport. While the effect of temperature and current density on mass transport losses has been extensively studied and is well understood, there are significantly fewer studies that focus on the effect of water flow and pressure. Both water flow and pressure have a direct effect on mechanisms such as bubble nucleation and two-phase flows that occur in the porous structures within a PEM electrolyzer (electrodes and porous transport layers, PTLs). In this work, I studied the effect of water flow and pressure on the mass transport phenomena in PEM electrolyzers. Chapters 1 and 2 provide an introduction to the topic as well as a description of the materials and experimental setups used. Chapter 3 of this thesis depicts the visualization and modeling of bubble nucleation in an operating PEM electrolyzer. I discovered that bubble detachment radii are largely independent of water flow and I identified two types of bubbles: bubbles that detach after reaching a critical size, and bubbles that fill up the pores of a PTL before detaching. Chapter 3 consists of the measurements I carried out regarding the transport of evolved gas through the water-filled pores of a PTL, where I observed that water flow severely impedes the gas transport through the pores and that such impediment is related to a shear stress exerted by the water flow on the pores. Chapter 5 shows the measuring of mass transport losses using electrochemical impedance spectroscopy (EIS) on an operating PEM electrolyzer; the results indicate that pressure and water flow affect the diffusion of gas in the electrode and that the mass transport overpotential depends on design parameters of the PEM electrolyzer, such as electrode thickness and hydrophobicity. Overall, I derived a theoretical framework based on the assumption that the evolved gas in a PEM electrolyzer permeates through the PTL after diffusing from the active sites to the bubble nucleation sites. Such framework, constructed on the basis of the models regarding gas transport in porous media, can be used to explain the mass transport loses in a PEM electrolyzer that arise from operating with increased water flows and pressures. The model I derived can be used in future work as a guideline to optimize the components of a PEM electrolyzer, in particular regarding the hydrophobicity and pore size distribution of PTLs as well as the composition of the catalyst ink to produce the electrodes. Moreover, this work can also be used to further understand the mass transport losses and optimize the operation of PEM electrolyzers to decrease the energy consumption of hydrogen generation.