Asymmetric gas diffusion layers for improved water management in PGM-free electrodes
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Engineering topics
Weber, Adam Z. (ORCID:0000000277491624)
Publications and source records attributed to Weber, Adam Z. (ORCID:0000000277491624).
Modeling the Effect of Material Properties on Liquid-Alkaline Water Electrolysis
Liquid-alkaline water electrolyzers (LAWEs) use electricity to drive the conversion of water to H 2 and O 2 gas. These devices benefit from the use of low-cost nickel electrodes and metal-oxide separators, but suffer from lower current densities and higher cell voltages than proton-exchange-membrane water electrolyzers. Identifying the inefficiencies that result in this poor performance is key to mitigating losses and optimizing LAWEs. Here, we report an experimentally-validated 1-D continuum model of a LAWE that elucidates the gradients within the cell, simulates H 2 crossover, and projects the energy improvements made possible by modulating the properties of the electrodes and separator. The model captures the Nernstian polarization losses and the distribution of gas- and liquid-phases within the electrodes, enabling quantification of energy losses associated with kinetic, ohmic, and bubble-induced (mass-transport) resistances. Simulations demonstrate that LAWE can achieve energy intensities of 50 kWh kg −1 of H 2 at 1 A cm −2 using improved electrode and separator properties.
08 HYDROGEN↗
Co-Design of Multijunction Photoelectrochemical Devices for Unassisted CO 2 Reduction to Multicarbon Products
Photoelectrochemical (PEC) CO 2 reduction (PEC CO 2 R) is a prospective approach for utilizing solar energy to synthesize a variety of carbon-containing chemicals and fuels, the most valuable of which are multicarbon (C 2+ ) products, such as ethylene and ethanol. While these products can be produced with high faradaic efficiency using Cu, this occurs over a relatively narrow potential range, which, in turn, imposes constraints on the design of a device for PEC CO 2 R. Herein, we used continuum-scale modeling to simulate the solar-to-C 2+ (STC 2+ ) efficiency of PEC CO 2 R devices fed with CO 2 -saturated, 0.1 M CsHCO 3 . We then explored how cell architecture and the use of single or dual photoelectrode(s) alters the optimal combination of photoelectrode bandgaps for high STC 2+ efficiency. Ultimately, this work provides guidance for the co-design of the device architecture and photoelectrode bandgaps required to achieve high STC 2+ efficiency. The insights gained are then used to identify systems that yield the highest amount of C 2+ products throughout the day and year.
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Relative-Humidity Dependence of Electrochemically Active Surface Area in Porous Carbon Catalyst Layers
Polymer-electrolyte fuel cells (PEFCs) utilize porous catalyst layers (CLs) formed of carbon supports on which Pt particles are deposited and ionomer films are distributed. Carbon supports themselves have varying degrees of porosity, where high-surface-area carbon (HSC) supports possess nanometer-sized interior pores that are suitable for Pt nanoparticle deposition but prevent deleterious ionomer penetration. However, this requires protons to transport through water pathways inside the pores. To understand the generation of such pathways, we examine the various mechanisms of water uptake by PEFC CLs, and the subsequent impact of water uptake on Pt utilization through developing a multiphysics model of the water wetting phenomena as a function of relative humidity. The model details water uptake via ionomer absorption, capillary condensation in the hydrophilic pores, and surface adsorption using molecular potential that account for various water and surface dipole interactions. The results quantify how mesoporous carbons with highly hydrophilic pores increase Pt utilization through the development of wetted layers, which at the same time enable optimized gas-transport pathways. It also demonstrates the impact of pore-size distribution (PSD) and physical and chemical parameters on the water uptake phenomena, allowing for future CL particle and structure optimization.
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Electrochemical Measurement of Water Transport Numbers in Anion-Exchange Membranes
Anion-exchange membranes (AEMs) are a possible replacement for perfluorosulfonic-acid membranes in energy-conversion devices, primarily due to the hydroxide mobile ion allowing the devices to operate in alkaline conditions with less expensive electrocatalysts. However, the transport properties of AEMs remain understudied, especially electro-osmosis. In this work, an electrochemical technique, where the open-circuit voltage is measured between two ends of a membrane maintained at different relative humidities, is used to determine the water transport number of various ionomers, including Versogen and Sustainion AEMs and Nafion cation-exchange membrane (CEM), as a function of water content and temperature. In addition, the CEMs and AEMs are examined in differing single-ion forms, specifically proton and sodium (CEM) and hydroxide and carbonate (AEM). Carbonate-form AEMs have the highest transport number (∼11), followed by sodium-form CEMs (∼8), hydroxide-form AEMs (∼6), and proton-form CEMs (∼3). Finally, a multicomponent transport model based on the Stefan-Maxwell-Onsager framework of binary interactions is used to develop a link between water transport number and water-transport properties, extracting a range for the unmeasured membrane water permeability of Versogen as a function of water content.
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Tailoring the Mass Transport to Achieve High-Performing Unitized Regenerative Fuel Cells Considering Practical Operating Conditions
Unitized regenerative fuel cells (URFCs) convert electrical energy to chemical bonds in hydrogen during charge and convert chemical energy to output electricity during discharge, offering a promising solution to long-term energy storage. Recent studies indicate that the round-trip-voltaic efficiency (RTE) and longevity of URFCs are limited by complex mass transport during charging and discharging. Here, we first investigate how different porous transport layer (PTL) structures can impact URFC performance. The preferred PTL has a low tortuosity and high porosity, leading to a high RTE above 50% at 1 A cm −2 using Nafion 212. Moreover, thicker membranes, such as Solvay 90, are required to ensure mechanical stability and minimize H 2 crossover when operating under high differential pressure. Although this assembly inevitably leads to a higher ohmic loss, the RTE can be improved by further tailoring the electrode structures to facilitate mass transport by using supported catalyst, which still achieves over 50% RTEs at 1 A cm −2 . Optimization of porous structure to mitigate mass transport resistance with appropriate materials down selection considering practical application requirements can be a key design principle for achieving high-performing URFCs.
25 ENERGY STORAGE↗
Ionomer-free and recyclable porous-transport electrode for high-performing proton-exchange-membrane water electrolysis
Abstract Clean hydrogen production requires large-scale deployment of water-electrolysis technologies, particularly proton-exchange-membrane water electrolyzers (PEMWEs). However, as iridium-based electrocatalysts remain the only practical option for PEMWEs, their low abundance will become a bottleneck for a sustainable hydrogen economy. Herein, we propose high-performing and durable ionomer-free porous transport electrodes (PTEs) with facile recycling features enabling Ir thrifting and reclamation. The ionomer-free porous transport electrodes offer a practical pathway to investigate the role of ionomer in the catalyst layer and, from microelectrode measurements, point to an ionomer poisoning effect for the oxygen evolution reaction. The ionomer-free porous transport electrodes demonstrate a voltage reduction of > 600 mV compared to conventional ionomer-coated porous transport electrodes at 1.8 A cm −2 and <0.1 mg Ir cm −2 , and a voltage degradation of 29 mV at average rate of 0.58 mV per 1000-cycles after 50k cycles of accelerated-stress tests at 4 A cm −2 . Moreover, the ionomer-free feature enables facile recycling of multiple components of PEMWEs, which is critical to a circular clean hydrogen economy.
08 HYDROGEN↗
The 2022 solar fuels roadmap
Abstract Renewable fuel generation is essential for a low carbon footprint economy. Thus, over the last five decades, a significant effort has been dedicated towards increasing the performance of solar fuels generating devices. Specifically, the solar to hydrogen efficiency of photoelectrochemical cells has progressed steadily towards its fundamental limit, and the faradaic efficiency towards valuable products in CO 2 reduction systems has increased dramatically. However, there are still numerous scientific and engineering challenges that must be overcame in order to turn solar fuels into a viable technology. At the electrode and device level, the conversion efficiency, stability and products selectivity must be increased significantly. Meanwhile, these performance metrics must be maintained when scaling up devices and systems while maintaining an acceptable cost and carbon footprint. This roadmap surveys different aspects of this endeavor: system benchmarking, device scaling, various approaches for photoelectrodes design, materials discovery, and catalysis. Each of the sections in the roadmap focuses on a single topic, discussing the state of the art, the key challenges and advancements required to meet them. The roadmap can be used as a guide for researchers and funding agencies highlighting the most pressing needs of the field.
08 HYDROGEN↗
Performance and Durability of Proton Exchange Membrane Vapor-Fed Unitized Regenerative Fuel Cells
With a growing demand for electricity, clean hydrogen production and usage can be an asset not only to mitigate emissions but for long-term energy storage as well. Hydrogen gas, a high-density energy carrier, can be made through electrolysis in charging mode and generate electricity via a fuel cell in discharging mode in a unitized regenerative fuel cell (URFC). While URFCs reduce cost by combining the charging and discharging modes into a singular device, switching between modes becomes burdensome, and water management is a major challenge. One way to mitigate these issues is to operate the entire system in the vapor phase. Vapor-phase operation simplifies the physics of the system but will introduce losses within the system, primarily ohmic and mass transport during the charging mode. In this study, we explore the performance of a Proton-Exchange-Membrane (PEM)-URFC under vapor-phase conditions and the impact of different PEMs, feed gases, and relative humidity on the performance and durability. By tailoring operating conditions and membrane, the vapor-URFC achieves a roundtrip efficiency of 42% and a lifetime of 50,000 accelerated stress test cycles for fully humidified feeds. Discussion of vapor-URFC for energy storage and extensions to look at various applications shows the promise of this technology.
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Ionomer Optimization for Hydroxide-Exchange-Membrane Water Electrolyzers Operated with Distilled Water: A Modeling Study
The hydroxide-exchange-membrane water electrolyzer (HEMWE) is a promising means to store intermittent renewable energy in the form of hydrogen chemical energy. The hydroxide-exchange ionomer (HEI) in the gas-evolving electrodes and the hydroxide-exchange membrane (HEM) are key components of HEMWE. In this work, we simulate the cell and examine explicitly the impact of HEI and HEM properties with a focus on improving HEMWE performance when operated with distilled water ( i.e ., no supporting electrolyte). The tradeoff between the ionic conductivity gain and electrochemically active surface area (ECSA) loss is studied. For a constant catalyst loading, distributing more catalyst next to the HEM or making thinner but denser catalyst layer is beneficial for HEMWE performance. The results demonstrate that a higher water diffusion coefficient is desired for HEM to supply reactant water to the cathode. In contrast, a lower water diffusion coefficient is preferred for the cathode HEI to retain the water in the regions with high reaction rates. Overall, the findings provide important insights to optimizing HEI/HEM materials for improved HEMWE performance.
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