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Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks
Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.
Analysis of anion exchange membrane water electrolyzer performance and its evolution over time
Understanding water, evolved gas, and ionic transport in membrane-electrode-assemblies (MEAs) is essential for the development of high performance and durable anion exchange membrane water electrolyzers (AEMWEs). This study evaluates the MEA conditioning process, operating conditions, and short-term stability in a 1 M potassium hydroxide (KOH) electrolyte, focusing on the underlying transport phenomena. We observe a significant initial voltage loss in continuous cell operation, which could be associated with gas bubble accumulation, transport layer or flow field passivation, and changes in the catalyst oxidation state. Further, we investigate the effects of materials and operational configurations, including the membrane type and thickness, and the electrolyte flow rate, including KOH being fed to both electrodes as well as to the anode only. Furthermore, the effect of membrane drying temperature on ex situ as well as in situ electrochemical performance is evaluated. Finally, we discuss 700 h of AEMWE operation at 1 A/cm 2 , highlighting the underlying degradation phenomena.
Anion Exchange Membrane Water Electrolysis Using a Catalyst-Coated Membrane Cathode
A catalyst-coated membrane (CCM) approach to electrode fabrication for high pH water electrolysis offers enhanced interfacial contact between the catalyst layer and the membrane surface in comparison to the catalyst-coated substrate (CCS) electrode configuration. The CCM facilitates enhanced ionic and water transport between the cathode and the anion exchange membrane (AEM). This advantage is particularly significant with AEM water electrolysis (compared to proton exchange membrane water electrolysis) because the cathode typically operates under dry conditions and relies solely on diffusive water transport across the AEM from the liquid-fed anode. This study presents a direct performance comparison between CCS and CCM cathode configurations using identical hydrogen evolution reaction (HER) catalysts and other components. The use of a pseudo-reference electrode integrated into the membrane electrode assembly enabled detailed analysis of the CCM cathode polarization behavior. Surface characterization provided insight into the degradation mechanisms associated with the CCM configuration. Optimization of the cathode ionomer cross-link density improved both the cathode polarization performance and the electrolysis device durability. Further optimization of the HER catalyst loading in the CCM cathode resulted in additional gains in the electrolysis efficiency. Collectively, these findings offer valuable guidance for the design and fabrication of high-performance, durable AEM electrolysis CCMs.
Durability Optimization of CO 2 Electrolyzers for Syngas Evolution
Recently, there has been an increased interest in mitigating anthropogenic CO 2 emissions through the electrochemical conversion of CO 2 into fuels and fuel feedstocks, including hydrogen gas (H 2 ), carbon monoxide (CO), and mixtures of the two to yield syngas. Commercial applications of these systems require high catalytic selectivity for the desired products, while exhibiting operational lifetimes exceeding thousands of hours. Advancements in this field have produced systems that display high selectivity of the desired products at faradaic efficiencies exceeding 95%. Despite the advancements made in CO 2 electrolysis, system durability remains a standing challenge in the field. CO 2 electrolyzer lifetimes are often limited by carbonate fouling, catalyst degradation, detrimental flooding of electrode microporous layers and anion exchange membrane (AEM) failures. In this report, a 5 cm 2 membrane electrode assembly (MEA) device is used to investigate potential failure modes and to optimize AEM CO 2 electrolyzer operation. Key findings of this study include the importance of CO 2 flow rate, use of a thin PiperION PTFE-reinforced membrane, optimizing compression to enhance contact under 40 in-lb compression, and the effect of more compressible, commercial iridium oxide anodes on system durability.
Preparation and Evaluation of Multi-Layer Anodes of Solid Oxide Fuel Cell
The development of an energy device with abundant energy generation, ultra-high specific power density, high stability and long life is critical for enabling longer missions and for reducing mission costs. Of all different types of fuel cells, the solid oxide fuel cells (SOFC) is a promising high temperature device that can generate electricity as a byproduct of a chemical reaction in a clean way and produce high quality heat that can be used for other purposes. For aerospace applications, a power-to-weight of (is) greater than 1.0 kW/kg is required. NASA has a patented fuel cell technology under development, capable of achieving the 1.0 kW/kg figure of merit. The first step toward achieving these goals is increasing anode durability. The catalyst plays an important role in the fuel cells for power generation, stability, efficiency and long life. Not only the anode composition, but its preparation and reduction are key to achieving better cell performance. In this research, multi-layer anodes were prepared varying the chemistry of each layer to optimize the performance of the cells. Microstructure analyses were done to the new anodes before and after fuel cell operation. The cells' durability and performance were evaluated in 200 hrs life tests in hydrogen at 850 C. The chemistry of the standard nickel anode was modified successfully reducing the anode degradation from 40% to 8.4% in 1000 hrs and retaining its microstructure.
Self-adhesive ionomers for durable low-temperature anion exchange membrane electrolysis
Low-temperature water electrolysis using an anion conductive polymer electrolyte has several potential advantages over other technologies, however, the fabrication of durable alkaline electrodes remains a challenge. Detachment of catalysts results in the loss of electrochemical surface area. Simple mixtures of ionomer and catalyst can suffer from poor catalyst adhesion because only physical adhesion is used to bind the components together. A family of chemically bonded, self-adherent, hydroxide conducting ionomers were synthesized and tested under alkaline electrolysis conditions with nickel ferrite anode electrocatalysts and platinum-nickel cathode catalyst. The ionomers are based on hydroxide conducting poly(norbornene) polymers used as the solid polymer electrolyte in alkaline fuel cells and electrolyzers. The synthesized terpolymer ionomers have been functionalized to provide pendant sites for covalent chemical bonding of bis(phenyl)-A-diglycidyl ether to the ionomer, catalyst, and porous transport layer. The electrodes show excellent adhesion between the catalyst particles, porous transport layer and ionomer, as determined by adhesion measurements and electrolysis performance. As a result, the AEM electrolyzer had stable voltage performance under high current density (1 A/ cm 2 at 1.83 V (67% voltage efficiency)) for extended time periods (>600 h) without degradation.
Impact of Porous Transport Layer Morphology on the Performance of Proton Exchange Membrane Water Electrolyzers with Ultra-Low Iridium Loadings
Reducing Ir loadings in proton exchange membrane water electrolyzer anodes is critical for lowering capital expenses. Loading reduction could be achieved by improving the Ir activity via doping/alloying and/or the development of advanced microstructures. However, the anode porous transport layer (PTL) is a comparatively simple component whose properties also impact Ir utilization. Therefore, well-designed PTLs may also enable reduced Ir loadings. In this work, we survey eight PTLs from various manufacturers to observe their impact on cell performance at low (0.4 mg Ir cm -2 ) and ultralow (0.1 mg Ir cm -2 ) Ir loadings. The PTLs were characterized by their microstructural properties, including porosity, particle size distribution, and pore size distribution. Electrochemical cell performance was correlated to PTL morphology, and it was found that PTLs with lower porosities and smaller particle and pore radii enabled good performance even at ultralow Ir loadings. 1000-h durability testing indicated that using lower porosity PTLs can significantly improve durability behavior. A runaway voltage phenomenon was observed during durability testing of cells with ultralow Ir loadings, which was caused by increases in both anode and cathode overpotentials. Furthermore, we observed that the beginning of test performance of 0.1 mg Ir cm -2 cells correlates to the 1000-h degradation rates of 0.4 mg Ir cm -2 cells, suggesting that for the Ir catalyst used in this work, short-term testing at ultralow loadings can be used as an indicator of long-term degradation at higher loadings.
Long-term durability test of highly efficient membrane electrode assemblies for anion exchange membrane seawater electrolyzers
Direct seawater electrolysis faces fundamental electrochemical challenges, such as suppression of chlorine adsorption and/or evolution reactions that poison the current state-of-the-art anode catalysts and accelerate the degradation of the anion exchange membrane (AEM). The technically favored solution path for addressing these issues includes development of novel selective catalysts and implementation of limited operating conditions. Therefore, development of highly active, selective, cost-effective, and stable seawater-splitting catalysts is required for a successful commercialization of the AEM water electrolyzers (AEMWEs). In this work, we report for the first-time an extended operation for over 1000 h of advanced AEMWEs, operating directly with seawater. To fabricate the membrane electrode assemblies (MEAs), catalyst coated electrodes (CCEs) are assembled with Sustainion® X37-50 grade T anion exchange membranes. The anode CCEs are fabricated by spraying an ink prepared from nanostructured NiFe-layered double hydroxide (LDH) catalyst that are synthesized by the solvothermal method and deposited directly onto platinized titanium porous transport layers (PTLs). The cathode CCEs are prepared by spraying an ink prepared from commercial Renay-Nickel catalyst onto a nickel fiber felt. As prepared AEM electrolyzer cells operated with seawater and demonstrated better than previously reported in the literature performance of over 1000 h of operation at a constant current density of 300 mA cm –2 .
In-situ and in-operando analysis of voltage losses using sense wires for proton exchange membrane water electrolyzers
Proton exchange membrane water electrolyzer development requires understanding processes at the materials and interface levels to reach the required performance and lifetime targets for increasing market penetration. To achieve the required progress, it is critical to develop advanced in-situ diagnostics that allow observation of the changes that come with the reduction of catalyst loading combined with long-term intermittent operation. This work presents an internal voltage sensing method that enables observing internal voltage drops in an operating electrolyzer cell. It allows the total cell resistance to be separated into anode, CCM, and cathode resistance. The method is demonstrated by operating cells with different anode porous transport layers (PTLs). The changing properties of the PTLs result in significant variations of the resistances. Enhancing the PTL properties with a protective coating reduces the anode resistance significantly. In addition to these observations, the method enables a real-time monitoring of resistance related values that impact performance in water electrolyzers. Long-term experiments with the method allow us to gain insights into processes that occur during operation such as conditioning or degradation. The internal voltage sensing method presented in this study is a novel technique for diagnosing, analyzing, and optimizing water electrolyzers and other energy conversion devices.
Oxygen Electrocatalysis on Mixed-Metal Oxides/Oxyhydroxides: From Fundamentals to Membrane Electrolyzer Technology
Catalyzing the oxygen evolution reaction (OER) is important for key energy-storage technologies, particularly water electrolysis and photoelectrolysis for hydrogen fuel production. Under neutral-to-alkaline conditions, first-row transition-metal oxides/(oxy)hydroxides are the fastest-known OER catalysts and have been the subject of intense study for the past decade. Critical to their high performance is the intentional or accidental addition of Fe to Ni/Co oxides that convert to layered (oxy)hydroxide structures during the OER. Unraveling the role that Fe plays in the catalysis and the molecular identity of the true “active site” has proved challenging, however, due to the dynamics of the host structure and absorbed Fe sites as well as the diversity of local structures in these disordered active phases. In this Account, we highlight our work to understand the role of Fe in Ni/Co (oxy)hydroxide OER catalysts. We first discuss how we characterize the intrinsic activity of the first-row transition-metal (oxy)hydroxide catalysts as thin films by accounting for the contributions of the catalyst-layer thickness (mass loading) and electrical conductivity as well as the underlying substrate’s chemical interactions with the catalyst and the presence of Fe species in the electrolyte. We show how Fe-doped Ni/Co (oxy)hydroxides restructure during catalysis, absorb/desorb Fe, and in some cases degrade or regenerate their activity during electrochemical testing. We highlight the relevant techniques and procedures that allowed us to better understand the role of Fe in activating other first-row transition metals for OER. We find several modes of Fe incorporation in Ni/Co (oxy)hydroxides and show how those modes correlate with activity and durability. We also discuss how this understanding informs the incorporation of earth-abundant transition-metal OER catalysts in anion-exchange-membrane water electrolyzers (AEMWE) that provide a locally basic anode environment but run on pure water and have advantages over the more-developed proton-exchange-membrane water electrolyzers (PEMWE) that use platinum-group-metal (PGM) catalysts. We outline the key issues of introducing Fe-doped Ni/Co (oxy)hydroxide catalysts at the anode of the AEMWE, such as the oxidative processes triggered by Fe species traveling through the polymer membrane, pH-gradient effects on the catalyst stability, and possibly limited catalyst utilization in the compressed stack configuration. We also suggest possible mitigation strategies for these issues. Lastly, we summarize remaining challenges including the long-term stability of Fe-doped Ni/Co (oxy)hydroxides under OER conditions and the lack of accurate models of the dynamic active surface that hinder our understanding of, and thus ability to design, these catalysts.
Designing the Platinum Catalyst Layer for Improved Performance and Durability in Anion Exchange Membrane Water Electrolysis
To lower the cost of hydrogen produced by anion exchange membrane water electrolysis (AEMWE), it is critical to reduce the use of platinum group metal (PGM) catalysts within the device. While iridium has been successfully replaced with PGM-free catalysts at the anode, platinum-based (Pt) cathode catalysts are still required to meet the activity and durability targets. This study investigates the impact of commercial Pt/C catalyst loading, ionomer type and content, and electrode fabrication method on the cathode catalyst layer properties and AEMWE performance with the aim of determining the feasibility of reduced Pt loadings. While increased Pt loading is found to improve beginning-of-life performance, the effects are minimal above 0.6 mg/cm 2 . Ink characterization shows that ionomer type and content affect the ink stability, particle size, and percent of unbound ionomer, which further impact the homogeneity of the sprayed catalyst layers. The 5% PiperION cathode exhibited the highest performance, which may be attributed to a balance between the small particle size and the low proportion of unbound ionomer, minimizing kinetic and transport losses. Theoretical calculations show that the ionomers interact differently with the Pt surface, causing different surface charges and water adsorption strength and activating different mechanisms for hydrogen evolution. Pt-PiperION lowered the enthalpy of water-splitting by 0.1 eV compared to Pt alone and allowed for equal site access between adsorbed H* and OH* (both adsorbed at circa −2.2 eV). Although catalyst-coated membrane (CCM) fabrication techniques are desirable for scale-up, no performance enhancement is observed compared with the catalyst-coated substrate approach. Durability, as measured by degradation rates, Pt loss, and catalyst layer restructuring, was found to improve with increased Pt loadings, higher ionomer content, and CCM architectures. These findings provide important insight into the significant role of the cathode in AEMWE and strategies for maintaining the performance with low Pt loading or PGM-free catalysts.
Evaluating the Effects of Anode Porous Transport Layer on the Performance and Durability of Anion Exchange Membrane Electrolyzers
As anion exchange membrane systems have emerged as a competitive low temperature electrolysis technology, research has expanded to other components and device integration. In this study, nickel (Ni) and stainless steel (SS)-based porous transport layers (PTLs) are investigated in membrane electrode assemblies (MEAs). Compared to MEAs using Ni, the SS PTL shows higher performance due to less kinetics and residual loss and possibly due to a combination of iron mobility improving oxygen evolution reactivity and electron conduction pathways, as well as higher porosity increasing site access. Voltage decay rates of approximately 144 and 115 μV/h, respectively, for the Ni and SS PTLs are found, although the long-term durability and lifetime implications are convoluted. Voltage breakdown analysis confirms that both PTLs saw significant increases in residual loss possibly due to catalyst/PTL property changes that affected electronic, ionic, and mass transport pathways. For the Ni PTL, a higher proportion of the losses were due to cell kinetics; comparatively, more of the SS PTL losses were due to increases in the high frequency resistance. The experimental findings presented here provide insights on the impact of the PTL materials and their properties.