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Solar Airplanes and Regenerative Fuel Cells

A solar electric aircraft with the potential to "fly forever" has captured NASA's interest, and the concept for such an aircraft was pursued under Aeronautics Environmental Research Aircraft and Sensor Technology (ERAST) project. Feasibility of this aircraft happens to depend on the successful development of solar power technologies critical to NASA's Exploration Initiatives; hence, there was widespread interest throughout NASA to bring these technologies to a flight demonstration. The most critical is an energy storage system to sustain mission power during night periods. For the solar airplane, whose flight capability is already limited by the diffuse nature of solar flux and subject to latitude and time of year constraints, the feasibility of long endurance flight depends on a storage density figure of merit better than 400-600 watt-hr per kilogram. This figure of merit is beyond the capability of present day storage technologies (other than nuclear) but may be achievable in the hydrogen-oxygen regenerative fuel cell (RFC). This potential has led NASA to undertake the practical development of a hydrogen-oxygen regenerative fuel cell, initially as solar energy storage for a high altitude UAV science platform but eventually to serve as the primary power source for NASAs lunar base and other planet surface installations. Potentially the highest storage capacity and lowest weight of any non-nuclear device, a flight-weight RFC aboard a solar-electric aircraft that is flown continuously through several successive day-night cycles will provide the most convincing demonstration that this technology's widespread potential has been realized. In 1998 NASA began development of a closed cycle hydrogen oxygen PEM RFC under the Aeronautics Environmental Research Aircraft and Sensor Technology (ERAST) project and continued its development, originally for a solar electric airplane flight, through FY2005 under the Low Emissions Alternative Power (LEAP) project. Construction of the closed loop system began in 2002 at the NASA Glenn Research Center in Cleveland, Ohio. System checkout was completed, and testing began, in July of 2003. The initial test sequences were done with only a fuel cell or electrolyzer in the test rig. Those tests were used to verify the test apparatus, procedures, and software. The first complete cycles of the fully closed loop, regenerative fuel cell system were successfully completed in the following September. Following some hardware upgrades to increase reactant recirculation flow, the test rig was operated at full power in December 2003 and again in January 2004. In March 2004 a newer generation of fuel cell and electrolyzer stacks was substituted for the original hardware and these stacks were successfully tested at full power under cyclic operation in June of 2004.

Bents, David J.↗

Generating Aromatics From CO2 on Mars or Natural Gas on Earth

Methane to aromatics on Mars ( METAMARS ) is the name of a process originally intended as a means of converting Martian atmospheric carbon dioxide to aromatic hydrocarbons and oxygen, which would be used as propellants for spacecraft to return to Earth. The process has been demonstrated on Earth on a laboratory scale. A truncated version of the process could be used on Earth to convert natural gas to aromatic hydrocarbon liquids. The greater (relative to natural gas) density of aromatic hydrocarbon liquids makes it more economically feasible to ship them to distant markets. Hence, this process makes it feasible to exploit some reserves of natural gas that, heretofore, have been considered as being "stranded" too far from markets to be of economic value. In the full version of METAMARS, carbon dioxide is frozen out of the atmosphere and fed to a Sabatier reactor along with hydrogen (which, on Mars, would have been brought from Earth). In the Sabatier reactor, these feedstocks are converted to methane and water. The water is condensed and electrolyzed to oxygen (which is liquefied) and hydrogen (which is recycled to the Sabatier reactor). The methane is sent to an aromatization reactor, wherein, over a molybdenum-on-zeolite catalyst at a temperature 700 C, it is partially converted into aromatic hydrocarbons (specifically, benzene, toluene, and naphthalene) along with hydrogen. The aromatics are collected by freezing, while unreacted methane and hydrogen are separated by a membrane. Most of the hydrogen is recycled to the Sabatier reactor, while the methane and a small portion of the hydrogen are recycled to the aromatization reactor. The partial recycle of hydrogen to the aromatization reactor greatly increases the catalyst lifetime and eases its regeneration by preventing the formation of graphitic carbon, which could damage the catalyst. (Moreover, if graphitic carbon were allowed to form, it would be necessary to use oxygen to remove it.) Because the aromatics contain only one hydrogen atom per carbon atom, METAMARS produces four times as much propellant from a given amount of hydrogen as does a related process that includes the Sabatier reaction and electrolysis but not aromatization. In the terrestrial version of METAMARS, the Sabatier reactor and electrolyzer would be omitted, while the hydrogen/ methane membrane-separating membrane, the aromatization reactor, and the unreacted-gas-recycling subsystem would be retained. Natural gas would be fed directly to the aromatization reactor. Because natural gas consists of higher hydrocarbons in addition to methane, the aromatization subprocess should be more efficient than it is for methane alone.

Muscatello, Anthony C.↗

Energy Storage Technology Development for Space Exploration

The National Aeronautics and Space Administration is developing battery and fuel cell technology to meet the expected energy storage needs of human exploration systems. Improving battery performance and safety for human missions enhances a number of exploration systems, including un-tethered extravehicular activity suits and transportation systems including landers and rovers. Similarly, improved fuel cell and electrolyzer systems can reduce mass and increase the reliability of electrical power, oxygen, and water generation for crewed vehicles, depots and outposts. To achieve this, NASA is developing non-flow-through proton-exchange-membrane fuel cell stacks, and electrolyzers coupled with low permeability membranes for high pressure operation. The primary advantage of this technology set is the reduction of ancillary parts in the balance-of-plant fewer pumps, separators and related components should result in fewer failure modes and hence a higher probability of achieving very reliable operation, and reduced parasitic power losses enable smaller reactant tanks and therefore systems with lower mass and volume. Key accomplishments over the past year include the fabrication and testing of several robust, small-scale non-flow-through fuel cell stacks that have demonstrated proof-of-concept. NASA is also developing advanced lithium-ion battery cells, targeting cell-level safety and very high specific energy and energy density. Key accomplishments include the development of silicon composite anodes, lithiatedmixed- metal-oxide cathodes, low-flammability electrolytes, and cell-incorporated safety devices that promise to substantially improve battery performance while providing a high level of safety.

Mercer, Carolyn R.↗

HESTIA Phase I Test Results: The Air Revitalization System

In any human spaceflight mission, a number of Environmental Control & Life Support System (ECLSS) technologies work together to provide the conditions astronauts need to live healthily, productively, and comfortably in space. In a long-duration mission, many of these ECLSS technologies may use materials supplied by In-Situ Resource Utilization (ISRU), introducing more interactions between systems. The Human Exploration Spacecraft Test-bed for Integration & Advancement (HESTIA) Project aims to create a test-bed to evaluate ECLSS and ISRU technologies and how they interact in a high-fidelity, closed-loop, human-rated analog habitat. Air purity and conditioning are essential components within any ECLSS and for HESTIA's first test they were achieved with the Air Revitalization System (ARS) described below. The ARS provided four essential functions to the test-bed chamber: cooling the air, removing humidity from the air, removing trace contaminants, and scrubbing carbon dioxide (CO2) from the air. In this case, the oxygen supply function was provided by ISRU. In the current configuration, the ARS is a collection of different subsystems. A fan circulates the air, while a condensing heat exchanger (CHX) pulls humidity out of the air. A Trace Contaminant Removal System (TCRS) filters the air of potentially harmful contaminants. Lastly, a Reactive Plastic Lithium Hydroxide (RP-LiOH) unit removes CO2 from the breathing air. During the HESTIA Phase I test in September 2015, the ARS and its individual components each functioned as expected, although further analysis is underway. During the Phase I testing and in prior bench-top tests, the energy balance of heat removed by the CHX was not equal to the cooling it received. This indicated possible instrument error and therefore recalibration of the instruments and follow-up testing is planned in 2016 to address the issue. The ARS was tested in conjunction with two other systems: the Human Metabolic Simulator (HMS) and the Electrolyzer. They behaved as anticipated as well. The HMS added humidity, CO2, and heat to the chamber while removing oxygen, and the Electrolyzer (an ISRU technology) added oxygen. The objective for HESTIA in 2015 was achieved: the creation of a high-fidelity test-bed for ECLSS and ISRU technologies. With the 'backbone' technologies installed, more technologies will be added to increase the analog habitat's fidelity over the next few years. The ARS was designed with this in mind, and as new technologies develop and mature, the strategic installation of the existing components will allow for them to be replaced with the new technologies.

Wright, Sarah E.↗

Regenerative Fuel Cell Power Systems for Lunar and Martian Surface Exploration

This paper presents the preliminary results of a recent National Aeronautics and Space Administration (NASA) study funded under the Advanced Exploration Systems (AES) Modular Power Systems (AMPS) project. This study evaluated multiple surface locations on both the Moon and Mars, with the goal of establishing a common approach towards technology development and system design for surface power systems that use Regenerative Fuel Cell (RFC) energy storage methods. One RFC design may not be applicable to all surface locations; however, AMPS seeks to find a unified architecture, or series of architectures, that leverages a single development approach to answer the technology need for RFC systems. Early system trades were performed to select the most effective fuel cell and electrolyzer architectures based on current state-of-the-art technology, whereas later trades will establish a detailed system design to enable a near-term ground (non-flight) demonstration. This paper focuses on the initial trade studies, presents the selected fuel cell and electrolyzer architectures for follow-on system design studies, and suggests areas for further technology investment.

lunar and Mars exploration↗

Benefits of using Electronic Data Sheets (EDS) with coreFlight Systems (cFS) - A Project Example

Recently there has been interest in the incorporation of core Flight Systems (cFS) with Spacecraft Onboard Interface Services (SOIS) Electronic Data Sheets (EDS) in the spaceflight software community. The Regenerative Fuel Cell project at the Glenn Research Center is using cFS architecture with EDS support for its monitoring and control software. The presentation will outline the benefits to using cFS with EDS support: First, EDS establishes a single source of truth for the definitions of data structures used throughout an entire mission that may otherwise be programmed in different languages and designed with different processor architectures. Not only does this help with inter-application communication via the software bus, but it also greatly simplifies communication between systems. An EDS Application Programming Interface (API) library allows the conversion of EDS data structures to and from native data structures. Second, bindings for other programming languages (e.g. Lua, Python, JSON) have been written to allow the creation and manipulation of EDS data objects within those languages. The RFC project uses Lua scripts to automatically generate binary configuration files at build time to be loaded into our cFS programs. We also use Python bindings in a graphical user interface (GUI) to allow an operator to send commands and view telemetry messages sent from cFS instances. Finally, using Lua scripts we can set up specific simulation scenarios to perform automatic functional testing. During the development of the RFC software, the software team put together a generic python GUI called “cFS-EDS-GroundStation” that provides a basic interface to an instance of cFS with EDS support. The GUI includes a basic telecommand and telemetry system that reads directly from the generated EDS databases. In the telecommand system, dropdown menus are populated with all user commands that are defined in EDS. In the telemetry system, telemetry messages are automatically decoded, written to the screen, and saved to a binary file. Additional Python scripts have been written to convert the binary data files into a comma separated value (CSV) format for further processing. We will demonstrate the basic use of the cFS-EDS-GroundStation software including adding additional commands and telemetry payload values in EDS and see them appear automatically in the cFS-EDS-Groundstation software. About the RFC project: The Regenerative Fuel Cell project is tasked with developing and demonstrating a power system consisting of a fuel cell and electrolyzer to provide power during a lunar day/night cycle. During the night, the fuel cell takes Hydrogen and Oxygen gasses and converts them into electricity, water, and heat. During the day, the electrolyzer takes input power (e.g. from a photovoltaic array) and converts water back into Hydrogen and Oxygen gasses.

Mathew Mccaskey↗

Thermal Management Challenges and Technology Options for Lunar Regenerative Fuel Cells

Regenerative Fuel Cells (RFCs) enable lunar surface hardware, from pressurized rovers to surface habitats, to survive the lunar night by providing the required energy storage with a lower mass than state of the art battery systems. RFCs consist of fuel cell and electrolyzer electrochemical stack(s), a fluidic balance of plant, and electrical balance of plant. Fuel cells operate by converting the stored chemical energy of reactants into DC electrical power, heat, and water. When supplied DC power from an available external source, electrolyzers regenerate the reactants through electrolysis. The balance of plant is a critical part of the integrated system consisting of many individual components and provides fluid pressure management and conditioning, fluid storage, and thermal management. Component technology development is required to create an RFC system that will be capable of surviving the harsh lunar environment and maximize specific energy (W-hr/kg). One critical component requiring development includes a kW-scale high flux thermal switch. The primary requirement for the thermal switch is the ability to maintain low thermal resistance with the RFC heat rejection interface during the lunar day to maximize heat rejection while switching to a high thermal resistance during the lunar night such that the RFC can conserve as much thermal energy as possible. Different technology including freeze tolerant pumped loop, passive louvers, and variable conductance heat pipes were assessed as potential solutions. NASA is exploring development options through internal and external partnerships to develop this technology critical for a spaceflight RFC system.

Energy Storage↗

Modeling of a Solid Oxide Fuel Cell as Part of a Predictive Functional Model for Aerospace Fuel-Cell Systems

This paper will discuss initial efforts at modeling a solid oxide fuel cell (SOFC) for aerospace applications. Fuel cells historically have been used in spacecraft from the Gemini to the Shuttle era for providing spacecraft power with the added benefit of producing water for crew use. However, there are many potential applications for fuel cells and electrolyzers in spaceflight, including oxygen generation, in-situ resource utilization (ISRU) and propellant production. This proof-of-concept model has been developed using a commercial multiphysics modeling software package. Two-dimensional and one-dimensional isothermal models were created based on a certain SOFC design and results were compared to test data from the real system. Local Butler-Volmer kinetic relations were adjusted, and an effective porous medium approach was taken in order to capture how the many interconnects between cells in the gas channels affected fluid flow. The model was able to reproduce polarization curves derived from test data within around 0.02 Volts for a given current density. This model could be adapted to model a solid oxide electrolyzer, proton exchange membrane fuel cell, or other type of fuel cell technology in order to understand how these types of technologies could fit into broader spacecraft designs and advance the capabilities of spaceflight systems.

Mary Lou Nadeau↗

Integrated Bosch Process System Models for In-Situ Oxygen and Carbon Production

In-Situ Resource Utilization (ISRU) technology is a vital component to NASA’s mission of a sustainable presence on the Moon and Mars. Local resources can be leveraged to reduce resupply frequency and mass. Elements of the Bosch process, combined with the carbothermal reduction process, can produce oxygen on the lunar surface with minimal consumables. The Bosch process can also produce oxygen on the Martian surface by using the CO 2 -rich environment. Between both systems, adsorption pump, solar thermal energy, carbon formation reactor, and water recovery subsystems are modeled and integrated to create a functional model in MATLAB software. The model is used to simulate performance of the system and reduce mass, power, and volume requirements. This integrated system model provides a tool to scale ISRU technologies for oxygen and carbon production. The MATLAB model is created by developing a system of independent subsystem models that are solved for their quasi-steady state values which can be integrated with respect to time to determine the change in current states. A flexible time stepping method is used to ensure a high level of accuracy during periods of rapid change while still making use of a simple explicit integration method. The flexible time step is calculated for each independent subsystem and the minimum value from those is used as the overall time step. A flexible time step is calculated by dividing a resolution value, or the maximum change per time step, by the variables current rate of change. The maximum value from all points in space is used for subsystem models that contain multiple values. The process is done for every variable that is being monitored in each subsystem and the global minimum is used as that iteration’s timestep. Several assumptions used in the MATLAB model for fluid flow dynamics, such as 1-D gas flow through the sorption pump, are supported by modeling in Ansys Fluent software. The Lunar oxygen production system is outlined in Fig. 1. The carbothermal reduction subsystem uses solar energy to heat a mixture of lunar regolith and carbon powder to produce carbon monoxide. To begin, the carbon monoxide feeds to the modified Bosch subsystem along with hydrogen gas. The reactants then enter the carbon formation reactor where water and carbon powder are produced. Solar thermal energy is used to add energy to the reactor, but waste heat from the carbothermal process is another potential heat source. The water is collected and electrolyzed to produce hydrogen which reenters the Bosch subsystem, and the oxygen is stored for downstream use. The carbon powder is collected and feeds back into the carbothermal subsystem. The Martian oxygen production system uses the full Bosch process and is outlined in Fig 2. A CO 2 adsorption pump thermally cycles to scrub and pressurize CO 2 from the environment. Along with an initial supply of hydrogen, the reactants enter the Reverse Water Gas Shift Reactor (RWGSR) which produces carbon monoxide and water. Carbon monoxide and unreacted hydrogen enter the carbon formation reactor to produce water and carbon powder. The water is collected from both reactors and electrolyzed to reintroduce hydrogen and store oxygen for propellant production or life support. Carbon is removed from the carbon formation reactor and stored. The adsorption pump utilizes rapid cycle temperature swings within a stack of zeolite coated surfaces. The subsystem model solves 1-D quasi-steady conservation laws of the quasi-steady form, shown in Eq. 1, for the gas stream and heat exchange liquid to predict performance parameters such as breakthrough capacity and optimum cycle time. The source term S is used to capture interactions between the fluid flows and the sorbent. A quasi-steady-state scheme is used where no time derivatives appear in the governing equations, except for those in the source terms. This results in an autonomous system, where ∂F/∂x = ƒ(F). The fluxes F are provided at the inlet, and an explicit method is used to solve for the spatial distribution of F. The heat and mass flows to the sorbent are then extracted from the source terms. These flows are numerically integrated to produce a 1-D solution for the system’s state as a function of both time and space. The body of the adsorption pump is separated into two semi-independent models: the heat exchanger fluid flow and gas flow through the zeolite coated surfaces. Both models are solved using the above-described method to find a 1-D solution as a function of space and interact only once a timestep is taken. The interaction point is the sorbent through which all heat transfer between the two models must occur. Sorbent mass adsorption is calculated using the Lagergren model, shown in Eq. 2, where the transfer coefficient, λ D , is found by solving a system of nondimensionalized equations derived by using the heat and mass transfer analogy for transport phenomena. Using Grade 544 Type 13X zeolite as the sorbent material, the equilibrium concentration, θ eq , is calculated using the k-site Langmuir isotherm and fit parameters. Additionally, the enthalpy of adsorption used in the model is computed by interpolation of available data [1]. The subsystem model was validated using the Rapid Cycle Temperature Swing Adsorption (RC-TSA) pump. The solar thermal energy subsystem focuses on a solar concentrator concept with a heat exchanger to heat the reactants before entering the carbon formation reactor. The subsystem model assumes a fixed solar flux and reflector efficiency to calculate the reactant temperature given the incoming temperature, pressure, and exchanger geometry. The receiver is a custom manufactured series of copper blocks with serpentine channels to increase its surface area and the residence time of the reactants to heat up to 550 °C. The subsystem model was validated using a heat exchanger developed at NASA Glenn Research Center (GRC). The solar thermal energy subsystem focuses on a solar concentrator concept with a heat exchanger to heat the reactants before entering the carbon formation reactor. The subsystem model assumes a fixed solar flux and reflector efficiency to calculate the reactant temperature given the incoming temperature, pressure, and exchanger geometry. The receiver is a custom manufactured series of copper blocks with serpentine channels to increase its surface area and the residence time of the reactants to heat up to 550 °C. The subsystem model was validated using a heat exchanger developed at NASA Glenn Research Center (GRC).

In situ Resource Utilization↗

Modeling of a Solid Oxide Fuel Cell as Part of a Predictive Functional Model for Aerospace Fuel-Cell Systems

This paper will discuss initial efforts at modeling a solid oxide fuel cell (SOFC) for aerospace applications. Fuel cells historically have been used in spacecraft from the Gemini to the Shuttle era for providing spacecraft power with the added benefit of producing water for crew use. However, there are many potential applications for fuel cells and electrolyzers in spaceflight, including oxygen generation, in-situ resource utilization (ISRU) and propellant production. This proof-of-concept model has been developed using a commercial multiphysics modeling software package. Two-dimensional and one-dimensional isothermal models were created based on a certain SOFC design and results were compared to test data from the real system. Local Butler-Volmer kinetic relations were adjusted, and an effective porous medium approach was taken in order to capture how the many interconnects between cells in the gas channels affected fluid flow. The model was able to reproduce polarization curves derived from test data within around 0.02 Volts for a given current density. This model could be adapted to model a solid oxide electrolyzer, proton exchange membrane fuel cell, or other type of fuel cell technology in order to understand how these types of technologies could fit into broader spacecraft designs and advance the capabilities of spaceflight systems.

Mary Lou Nadeau↗

Modeling of a Solid Oxide Fuel Cell as Part of a Predictive Functional Model for Aerospace Fuel-Cell Systems

This paper will discuss initial efforts at modeling a solid oxide fuel cell (SOFC) for aerospace applications. Fuel cells historically have been used in spacecraft from the Gemini to the Shuttle era for providing spacecraft power with the added benefit of producing water for crew use. However, there are many potential applications for fuel cells and electrolyzers in spaceflight, including oxygen generation, in-situ resource utilization (ISRU) and propellant production. This proof-of-concept model has been developed using a commercial multiphysics modeling software package. Two-dimensional and one-dimensional isothermal models were created based on a certain SOFC design and results were compared to test data from the real system. Local Butler-Volmer kinetic relations were adjusted, and an effective porous medium approach was taken in order to capture how the many interconnects between cells in the gas channels affected fluid flow. The model was able to reproduce polarization curves derived from test data within around 0.02 Volts for a given current density. This model could be adapted to model a solid oxide electrolyzer, proton exchange membrane fuel cell, or other type of fuel cell technology in order to understand how these types of technologies could fit into broader spacecraft designs and advance the capabilities of spaceflight systems.

Mary Lou Nadeau↗

Modeling of a Solid Oxide Fuel Cell as Part of a Predictive Functional Model for Aerospace Fuel-Cell Systems

This paper will discuss initial efforts at modeling a solid oxide fuel cell (SOFC) for aerospace applications. Fuel cells historically have been used in spacecraft from the Gemini to the Shuttle era for providing spacecraft power with the added benefit of producing water for crew use. However, there are many potential applications for fuel cells and electrolyzers in spaceflight, including oxygen generation, in-situ resource utilization (ISRU) and propellant production. This proof-of-concept model has been developed using a commercial multiphysics modeling software package. Two-dimensional and one-dimensional isothermal models were created based on a certain SOFC design and results were compared to test data from the real system. Local Butler-Volmer kinetic relations were adjusted, and an effective porous medium approach was taken in order to capture how the many interconnects between cells in the gas channels affected fluid flow. The model was able to reproduce polarization curves derived from test data within around 0.02 Volts for a given current density. This model could be adapted to model a solid oxide electrolyzer, proton exchange membrane fuel cell, or other type of fuel cell technology in order to understand how these types of technologies could fit into broader spacecraft designs and advance the capabilities of spaceflight systems.

Mary Lou Nadeau↗

Opportunities and Implications for Low-Cost Hydrogen Production from Water Electrolysis in a Decarbonizing Power Sector

Increased deployment of renewable power generation such as wind and solar photovoltaics along with electrification of transportation and other sectors are driving changes in the operation and economics of the electric power sector. Simultaneously, efforts to decarbonize other sectors of the economy such as steelmaking and heavy duty transportation will require significant amounts of electricity to drive electrons to molecules processes. Hydrogen production via water splitting electrolysis is a key near-term technology for decarbonization that interfaces between the power sector and decarbonization efforts in industrial sectors. This poster examines the implications for increased deployment of water electrolyzers in a rapidly evolving energy system. The economic opportunities for low-cost hydrogen production from electrolysis that are facilitated by highly renewable grids will be examined and discussed. Durability, cost, and operational strategies for electrolyzers interacting in these future energy systems are key to enabling hydrogen at scale. This poster will overview these considerations and ongoing work within the U.S. Department of Energy’s H2NEW consortium that is focused on addressing them.

electrolysis↗

Complete Phase Transformation of Ir Nanowire Network into Defect-Rich Oxide Catalyst for High-Performance PEM Water Electrolysis

Iridium-based catalysts remain the most reliable option for the oxygen evolution reaction (OER) in proton exchange membrane water electrolyzers (PEMWEs). However, their high cost and limited performance represent critical barriers to the commercialization of this green hydrogen production technology. Herein, we report the creation of a metallic Ir nanowire network (IrNWN), which exhibits superior OER performance through its in-situ transition into an oxide structure with high intrinsic activity. At a low loading of 0.25 mgIr/cm2 in PEMWEs, IrNWN achieved a current density of 3.13 A/cm2 at a cell voltage of 1.8 V, outperforming the commercial Ir-based catalyst and surpassing the Department of Energy (DOE) 2026 technical target. Moreover, the high activity of IrNWN was maintained for 900 hours in a durability test at 2 A/cm2, showing a low degradation rate of 0.042 mV/hour. Structural analysis of the electrochemically oxidized IrNWN revealed the presence of mixed Ir oxidation states and a high density of surface terminal oxygen groups (μ1-O), which contributed to a reduced energy barrier for the rate-determining O-O coupling step.

oxygen evolution reaction↗

Probing Electrode Transformation under Dynamic Operation for Alkaline Water Electrolysis

Alkaline water electrolyzers (AWEs) play a pivotal role in the realm of large-scale hydrogen production. However, AWEs face significant challenges in electrode degradation particularly under dynamic operating conditions, induced by reverse current phenomenon during frequent startup/shutdown. Herein, this study aims to rationalize the degradation mechanisms of AWEs under these conditions. A three-electrode membrane electrode assembly (MEA) setup is first utilized to decouple polarization behaviors of anode and cathode in AWEs. Following a proposed accelerated stress testing protocol, the setup allows for tracking individual electrode performance transformations during frequent reverse current operation. Integrating operando cell studies with in situ and post-mortem characterizations, it is showed that continuous formation of highly active species, nickel (oxy)hydroxides, improves the anode performance for oxygen evolution reaction. On the contrary, irreversible oxidation of nickel to β-nickel hydroxide results in a severe degradation of cathode, leading to material dissolution, poor electrical conductivity and loss of catalytic activity for hydrogen evolution reaction. These results provide insights in nickel-based electrode transformation mechanisms for alkaline water electrolysis and indicate that cathode with higher redox reversibility can potentially improve durability of AWEs under dynamic conditions.

08 HYDROGEN↗

Effect of stoichiometry and hydration level on water domain size and transport in poly(aryl piperidinium) alkaline anion-exchange membranes

Alkaline water electrolysis holds promise in decarbonizing the global economy by enabling renewable hydrogen production with non-precious group metal catalysts. Anion exchange membranes are an important component of alkaline water electrolyzers and would ideally be durable while allowing for high hydroxide conductivity. The poly(aryl piperidinium) (PAP) class of polymers has attracted recent interest due to their good mechanical robustness and high ionic conductivity. Here, in this work, we perform atomistic molecular dynamics (MD) simulations of several PAP polymers at experimentally relevant hydration levels and polymer ion exchange capacities (IECs) to gain nanoscale insight into their properties and to help elucidate the trade-offs that result from tuning the IECs through the polymer stoichiometry. Our MD-predicted macroscopic polymer properties were found to be in good agreement with experimentally available polymer swelling ratios, water-occupied volumes, X-ray scattering, and ionic conductivities. The models show that for hydration levels greater than 8H 2 O per cation a single water cluster will form that percolates through the system. The growth in water cluster size results in large polymer swelling, the creation of larger channels with widths of 7 Å or larger, and nanophase separation between the hydrophilic domains and the polymer with characteristic length scales of approximately 20–30 Å. The experimentally observed lack of a strong X-ray scattering peak at low wavevectors can be explained by a cancellation between the polymer-polymer/water-water and polymer-water correlations and not a loss in nanophase separation. The overlap in coordination environments of the hydroxide oxygen and polymer nitrogen atoms implies that vehicular diffusion between cationic groups could play a role in hydroxide transport. The polymers' hydroxide and water diffusion constants increase by approximately an order of magnitude between hydration levels of 8 and 20H 2 O per cation. However, there are diminishing returns in hydroxide diffusion constant once the IEC exceeds 2.4 meq/g.

08 HYDROGEN↗

Composition, Activity, and Stability of IrO x Oxygen Evolution Reaction Electrocatalysts

The oxygen evolution reaction (OER) is integral to several electrochemical energy conversion and storage technologies, including carbon dioxide reduction to value added fuels, nitrogen reduction to ammonia, reversible fuel cells, rechargeable metal−air batteries, and water electrolysis to produce hydrogen. Iridium oxide (IrO x ) is widely recognized as the benchmark OER catalyst for acidic environments. Despite widespread use of IrO x catalysts, most notably in proton-exchange membrane water electrolyzers (PEMWEs), a comprehensive understanding of the physicochemical properties of commercial catalysts and the impact of these properties on both the activity and stability of these catalysts is lacking. Here, we study commercial IrO x catalysts with different physicochemical properties, three nominally considered amorphous and three rutile, to elucidate how structural and compositional variations affect OER activity and stability. Utilizing standardized aqueous electrochemical protocols, time-resolved dissolution quantification using inductively-coupled plasma mass spectrometry, and physicochemical characterization, including multiple synchrotron X-ray techniques, we systematically correlate catalyst properties with OER performance and degradation behavior aided by principal component analysis (PCA). Our results demonstrate the general trend of amorphous IrO x having higher intrinsic activity but limited stability and crystalline rutile IrO 2 having lower activity but enhanced stability against dissolution. The trends within the amorphous and rutile catalyst groups correlate with inherent material properties, including phase composition and structure, crystallinity, particle size, surface area, and surface structure/chemistry. Notably, we identify a rutile catalyst with the largest crystallite/ domain sizes, moderate surface area, a small fraction of hydrous phase, and a favorable pore structure (trimodal distributions of pore sizes ranging from 2−5 nm) that exhibits the best balance between activity and stability among the six catalysts studied here. These findings illustrate a fundamental structure-governed trade-off between activity and stability and highlight the critical role of surface chemistry modification and structure engineering in IrO x catalyst optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Interposer Microstructure on Ionic Transport in Liquid-Phase Bicarbonate Electrolysis

The electrochemical reduction of CO 2 (CO 2 RR) is a potentially scalable approach for converting captured carbon dioxide into value-added products. Conventional gas-phase electrolysis systems can suffer from carbonate crossover, which limits the efficiency of the system. Liquid-phase (bi)carbonate electrolysis using bipolar membrane electrode assemblies (BPMMEA) has emerged as a promising alternative. The interposer layer, a porous mass-transport material between the BPM and the catalyst, is an essential component of the MEA, as it allows evolved CO 2 to reach the catalyst surface for reaction. In the absence of this layer, evolved CO 2 generated by the pH swing process at the BPM can be converted back into (bi)carbonate (CO 2 recapture) due to the high bulk pH. Thus, clear design guidelines are needed to maximize CO 2 conversion, minimize CO 2 recapture in the catholyte, and improve energy efficiency. Here, the transport properties of the interposer are systematically characterized by X-ray tomography and symmetric-cell impedance spectroscopy to quantify porosity, tortuosity, and the resulting MacMullin number. We then examine the correlation between these material properties and the electrolyzer performance. We focus on characterizing two commercial porous membrane filters, mixed cellulose ester (MCE) and poly(ether sulfone) (PES).

CO2 electrolysis↗