Theses Doctoral

Design Principles for Membraneless Electrolyzers for Production of Fuels and Chemicals

Pang, Xueqi

Reducing carbon emissions is a looming challenge that will be required to limit global warming. One approach is to replace energy from fossil fuels with renewable electricity that has low carbon footprints. The continuous decrease of renewable electricity prices makes electrochemical processes very promising for environmentally friendly production of fuels and chemicals. One of the mature electrochemical processes is hydrogen (H₂) production from water electrolysis. If only excess solar/wind electricity is used to power water electrolyzers to produce green H₂, the intermittency of the electricity supply will require low-cost electrolyzer technologies. Emerging membraneless water electrolyzers offer an attractive approach to lowering the cost of H₂ production by eliminating membranes or diaphragms that are used in conventional water electrolyzers.

One aim of this dissertation is to understand the performance limits of membraneless water electrolyzers compared to the conventional designs. Another key electrochemical process to reduce carbon emissions is the conversion of carbon dioxide (CO₂) to value-added fuels and chemicals. CO₂ captured from air or flue gas needs to be extracted from carbon capture solution and pressurized before feeding to a conventional CO₂ electrolyzer. In order to avoid these energy intensive steps to make pressurized CO₂, there is a growing interest in developing membrane-based electrolyzers that can directly utilize the carbon capture solution to conduct electrochemical CO₂ conversion. This dissertation also explores a scalable membrane-free electrolyzer design that can convert carbon capture solution to syngas.

In Chapter 2, a parallel plate membraneless electrolyzer is used as a model system to demonstrate a combined experimental and modeling approach to explore its performance limits. This modeling framework quantitatively describes 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. This framework shows that the efficiencies and current densities of optimized parallel plate membraneless electrolyzers 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.

Chapter 3 presents a packed bed membraneless electrolyzer (PBME) design for which liquid bicarbonate electrolyte flows sequentially through alternating porous flow-through anodes and cathodes. Within this design, hydrogen oxidation at porous anodes is used to produce protons that trigger in situ CO₂ release immediately upstream of porous cathodes, where electrochemical CO₂ reduction generates the desired product and returns the solution pH back towards its inlet value. By using the sequential flow-cell arrangement, the PBME offers the ability to mitigate large concentration overpotentials and non-uniform current distributions that naturally arise during scale-up of conventional membrane-based devices that rely on lateral flow of catholyte parallel to the surface of the electrodes. This study uses in situ colorimetric imaging to highlight the ability of PBME to rebalance pH across electrodes. In addition, results obtained with a multi-cell PBME “stack” demonstrate the scalability of this concept and reveal the ability to increase CO₂ utilization from 12.9% for a single-cell PBME up to 20.5% for a four-cell PBME operated under baseline conditions. Modeling results indicate that current utilization values >80% are theoretically possible for optimized multi-cell PBMEs operated at ambient pressure.

Chapter 4 demonstrates a stacked PBME design and an elevated pressure system. Hydrogen oxidation at the anode and hydrogen evolution at the cathode are conducted in this device at pressures up to 5 atm. The pressure of the system can be held at a constant value by the use of a back pressure regulator, and product gases can be collected with a gas sampling bag that’s directly connected to the back pressure regulator. The stereolithography 3D printing technology is used to fabricate components of the PBME from clear resin, which is suitable for the elevated pressure operation. Post-processing of the components makes surfaces transparent for imaging bubble dynamics in the device. Within this system, HOR current density of 120 mA cm-2 can be achieved at different pressures.

Finally, Chapter 5 provides concluding remarks and discusses future opportunities and challenges for membraneless electrolyzers for water electrolysis and electrochemical CO₂ conversion.


This item is currently under embargo. It will be available starting 2025-02-01.

More About This Work

Academic Units
Chemical Engineering
Thesis Advisors
Esposito, Daniel
Ph.D., Columbia University
Published Here
February 8, 2023