Solid Oxide Research Articles

Transitioning Low-Temperature GDC Socs: Lab to Commercialization Scale

Solid oxide fuel cells (SOFCs) electrochemically convert hydrogen and oxygen into electricity, heat, and water with high efficiency (~55%) [1], while in reverse operation, water and electricity are converted to hydrogen and oxygen in solid oxide electrolysis cells (SOECs). Appropriately designed solid oxide cells (SOCs) can operate in both SOFC and SOEC mode.Conventional SOCs typically demand elevated operating temperatures (800-1000°C), resulting in higher cost and accelerated degradation issues. Lowering operating temperatures below 600°C reduces thermal stresses, shortens start-up times, and broadens applications [2].Ce1-xGdxO2-δ (GDC), due to its superior oxygen ion conductivity at reduced temperatures, has lower ohmic losses than competing electrolyte materials. Thus, our 1.2 cm diameter circular anode supported GDC cell with 0.31 cm2 active area exhibits exceptional power densities, reaching approximately 3 watt per square centimeter at 650°C. Through optimal design, these cells exhibit exceptional performances in fuel cell mode, significantly enhancing efficiency and effectiveness when operating as an electrolyzer for fuel generation. This advance in performance is a result of mitigating the leakage current issues typical of ceria-based electrolytes through precise engineering of the cathodic microstructure and surface chemistry modification [3].The transition from lab-scale to large-scale commercialization (with active areas of 16 cm² &; 81 cm²) presents significant challenges such as tailoring material properties for large-cell versus button-cell synthesis while maintaining high performance levels.In this work we explore the challenges encountered during the scaling-up process. We report on fabrication strategies employed to achieve cell flatness, maintain high efficiency, ensure cost-effectiveness, and achieve long-term stability. Specifically, we have fabricated graded anode-supported cells [4] by developing an innovative lamination strategy involving tapes oriented perpendicular to each other. This approach notably contributed to achieving superior electrolyte densification and resulted in significantly flatter (low curvature values) with respect to both horizontal and vertical axes in cartesian coordinate space. When compared to the flatness values of 10x10 cm2 commercially available cells, our cells demonstrated remarkably flatter curvatures as shown in figure 1. This characteristic has proven highly beneficial for stack assembly, minimizing issues such as cell cracking and reducing sealing-related problems. By optimizing the cathode scaffold and infiltration process on larger area cells through a spray-coating machine, scaling up challenges are effectively mitigated compared to the button cell approach, where scaffold preparation and infiltration were performed using blade coating and a hand pipette, respectively. This approach effectively tackles electronic conduction issues in ceria-based electrolytes, leading to higher Open Circuit Voltages (OCVs) in fuel cell mode and increased efficiencies in reversible mode.

(Invited) Solid Oxide Cell Design for High Power Density and Reliability: Applications in Power and Fuels Production

Solid oxide fuel cells (SOFC) offer a carbon-neutral solution to power generation, fuel flexibility, and robust design suitable for stationary and air transportation applications. OxEon Energy developed an air electrode supported (AES) cell design that demonstrated 63% increase in power density compared with its heritage cell design in short stack tests.OxEon Energy team has been advancing solid oxide technology for over three decades and the stacks operate fully reversibly in fuel cell and electrolysis cell modes. The SOEC/SOFC technology builds on the success of the SOEC stack installed on NASA’s Mars Perseverance Rover as part of the MOXIE (Mars Oxygen In-situ resource utilization Experiment) mission. The MOXIE stack produced propellant grade, high-purity O2 by electrolyzing Mars atmosphere CO2. MOXIE stack used an electrolyte supported design to meet the reliability requirements for a space mission.An infiltrated air electrode cell design was developed to increase fuel cell stack specific power (kW/kg). Electrolyte thickness, the most resistive element of the SOFC, was reduced from ~250 microns to 70 microns. The fabrication process results in a bi-layer of dense scandia stabilized zirconia (ScSZ) electrolyte and a porous yttria stabilized zirconia (YSZ) matrix for air electrode infiltration. Fuel electrodes are screen printed. The reduced thickness of the electrolyte offers a compromise between improved performance over electrolyte supported design, while meeting robustness required for aerospace applications.Producing infiltrated electrodes with well-adhered and homogeneous distribution of active material is a challenge that requires multiple infiltration-calcination cycles to deposit sufficient material. Key variables are precursor chemistry to reduce the number of infiltrations and prevent interaction between electrode layers; intermediate calcination temperatures; and process development using infiltration equipment that enables volume production. OxEon partnered with National Energy Technology Laboratory (NETL) for electrode infiltration process development and PNNL for button cell and short stack validation testing.SOFC fuel flexibility was demonstrated in button cells and stacks previously; performance was nearly identical among hydrogen, ammonia, and reformed natural gas. Durability testing shows similarly stable performance in each fuel.A 10-cell AES stack was tested in SOFC mode at 800 °C in H2 and NH3 fuel feeds at 0.7 V/cell, and the same stack was operated in steam electrolysis to produce H2. SOFC testing demonstrated powder density of 0.35 W/ cm2 at 0.7 V/cell in the AES stack in ammonia feed; an electrolyte supported stack with equivalent materials measured 0.20 W/cm2 at 0.7 V. Long term testing in steam electrolysis showed stable performance at 800 °C and 1.2 V/ cell.Button cell tests show the thin electrolyte cell structure is capable of an area specific resistance (ASR) of 0.25 Ω-cm2 in H2- and NH3 fuel feeds. OxEon’s continued AES cell development is focused on improving manufacturability, infiltrated electrode stability, and implementing degradation mitigation strategies developed for electrolyte supported cell structures. Improved performance with AES cell design has critical implications for future integration in OxEon’s technology suite: SOEC systems to generate H2 and syngas from renewable energy, and Fischer-Tropsch to produce synthetic fuels.This material is based on research sponsored by Air Force Research Laboratory under agreement number FA8649-22-P-0792. The views expressed are those of the authors and do not necessarily reflect the official policy or position of the Department of the Air Force, the Department of Defense, or the U.S. government. Approved for public release; distribution is unlimited. Figure 1

(Invited) Novel Polymer and Membrane Development Strategies for Water Electrolysis

Water electrolysis processes play a crucial role in transitioning to a climate-friendly society. They facilitate the integration of renewable energy, offer a clean and versatile energy carrier, decarbonize industries, improve energy storage and grid stability, and support the development of sustainable transportation solutions. As technology advances and economies of scale are realized, electrolysis is expected to play an increasingly significant role in the clean energy landscape, contributing to a more sustainable and resilient future.Various water-splitting electrolysis processes currently exist, including alkaline, solid oxide, proton exchange membrane (PEM), anion exchange (AEM), acidic-alkaline amphoteric, microbial, and photoelectrochemical methods [1]. In our research group, we are actively involved in membrane development for both PEM and AEM water electrolysis.In PEM electrolysis membrane development, our group explores several approaches, such as (a) aromatic main-chain block copolymers[2],(b) acid-base blend membranes using sulfonated and partially fluorinated aromatic polyether, polybenzimidazole, and a PSU-derived basic polymer[2], (c) poly(fluorene)-based sulfonated ionomers, (d) sulfonated and phosphonated poly(pentafluorostyrene) polymers with flexible side groups, and (d) nanophase-separated block copolymers based on phosphonated[3] or sulfonated pentafluorostyrene and octylstyrene. Additionally, we investigate (e) H+-conductive fiber-mat reinforced perfluorosulfonic acid (PFSA) polymers[4].The development of anion exchange membranes in our research group includes (a) polystyrene-based side chain anion exchange polymers and their blends with polybenzimidazole[5], (b) polynorbornene-based optionally ionically and covalently crosslinked anion exchange polymers and membranes, (c) side chain anion exchange polymers and membranes prepared by polyhydroxyalkylation[6], and (d) anion exchange blend membranes made from polydiallyldimethylammonium salts and polybenzimidazole.This contribution highlights the application of two polymer types in PEM and AEM membrane water electrolysis, respectively:(A) PEM Water Electrolysis (PEMWE): Membranes from PEM types (a) and (b) demonstrated good performance. PEM (a) achieved 2.2 V@6 A/cm2, and PEM (b) reached 2.26 V@6 A/cm2 (compared to Nafion212: 2.26 V@6 A/cm2)[2]. These performances were accomplished with non-optimized membrane-electrode assemblies using Nafion as the electrode ionomer. Further performance improvements are expected with optimized electrodes containing the same ionomers as used in the membrane.(B) AEM Water Electrolysis (AEMWE): Blend membranes from AEM type (a) exhibited excellent alkali stability (no conductivity decrease after 1000 hrs of storage in 1M KOH@85°C) and good AEMWE performance (CuCo anode catalyst, 1M KOH, 70°C, 2 V@3 A/cm2)[5]. Type (c) AEMs were applied to a seawater electrolysis cell at 60°C, achieving a performance of 2 V@1 A/cm2 using completely noble metal-free catalysts in both the anode and cathode[6].[1] M. F. Ahmad Kamaroddin, N. Sabli, T. A. Tuan Abdullah, S. I. Siajam, L. C. Abdullah, A. Abdul Jalil, A. Ahmad, Membranes 2021, 11.[2] J. Bender, B. Mayerhöfer, P. Trinke, B. Bensmann, R. Hanke-Rauschenbach, K. Krajinovic, S. Thiele, J. Kerres, Polymers 2021, 13.[3] S. Auffarth, M. Wagner, A. Krieger, B. Fritsch, L. Hager, A. Hutzler, T. Böhm, S. Thiele, J. Kerres, ACS Materials Lett. 2023, 5, 2039.[4] M. S. Mu'min, M. Komma, D. Abbas, M. Wagner, A. Krieger, S. Thiele, T. Böhm, J. Kerres, Journal of Membrane Science 2023, 685, 121915.[5] L. Hager, M. Hegelheimer, J. Stonawski, A. T. S. Freiberg, C. Jaramillo-Hernández, G. Abellán, A. Hutzler, T. Böhm, S. Thiele, J. Kerres, J. Mater. Chem. A 2023.[6] M. L. Frisch, T. N. Thanh, A. Arinchtein, L. Hager, J. Schmidt, S. Brückner, J. Kerres, P. Strasser, ACS Energy Lett. 2023, 8, 2387.

Influence of Microstructure on Defect Chemistry - Transport - Chemical Strain Coupling of (Pr,Ce)O2-δ Nanoparticles

Solid oxide fuel/electrolysis cells (SOFC/SOECs) are promising and environmentally-friendly technologies for meeting ever-increasing electricity and energy storage demands. Nanostructuring of SOFC/SOEC electrodes can enable improvement of the reaction kinetics and reduction of the operating temperature, owing to factors including the enlarged surface area, short diffusion lengths, and unique surface & interface properties. While the kinetic benefit is apparent, the effect of nanostructuring on other device-relevant physico-chemical properties cannot be neglected. Especially, the coefficients of chemical expansion (CCEs) are an important metric for mixed ionic-electronic conductors that can undergo changes in oxygen stoichiometry with variations in the surrounding atmosphere, temperature, and voltages during processing/operation. Chemical strains can cause cracking of monolithic parts during fabrication and delamination of electrodes from electrolytes in operation. CCEs are typically measured on bulk, polycrystalline materials with large particle or grain sizes. Therefore, it is important to understand the coupled transport and chemical expansion behavior in nano-ionic materials with large interface/surface density. This work aims to uncover the role of microstructure and nanoscale effects on the chemical strain and transport properties, through the lens of defect chemistry, with the goal of ultimately developing design principles for zero-strain materials with improved device lifetime and performance.Pr0.2Ce0.8O2- δ (PCO20) was selected as a model system and prepared as nanoparticles by a surfactant-free, low temperature co-precipitation method. (Pr,Ce)O2-δ compositions are valuable model oxide ion conductors to study, since both Pr and Ce can undergo changes of valence states under different temperature and pO2 regimes to accommodate oxygen stoichiometry excursions. Prepared nanoparticle samples were first in-situ sintered in the dilatometer at three different temperatures (600 ⁰C, 725 ⁰C, 850 ⁰C) to induce and evaluate microstructure evolution. The chemical strain and electronic/ionic conductivity were then studied on stable microstructures with different average particle sizes at lower temperatures by simultaneous in-situ dilatometry and electrochemical impedance measurement (EIS) upon changing pO2 at different isotherms (550 to 400 ⁰C). At each isotherm, all the samples expand as pO2 decreases. From the conductivity vs. pO2 measurements, the maxima at certain pO2 indicate the dominant polaron mechanism of the electronic transport, consistent with the measured conductivity activation energy. However, samples with lower sintering temperatures exhibit less pO2 dependence of the conductivity, which implies a transition in the mixed ionic/electronic conduction behavior toward higher ionic transference numbers as particle size decreases. Correspondingly, the chemical strains associated with losing oxygen monotonically decrease with the decrease of the sintering temperature, and hence the particle size. The chemical strain vs. oxygen stoichiometry dependence and corresponding CCEs were quantified as function of particle size and temperature by combining thermogravimetric analysis (TGA) with the dilatometry results and in-situ X-ray diffraction. The particle size, chemical composition, valence states, and morphology of samples after CCEs measurements were also compared using XRD, SEM, and S/TEM-EELS, with the latter indicating the expected differences between bulk and surface defect chemistry. Implications of the results for size-dependent defect chemistry and its influence on chemical strains and redox CCEs will be further discussed. Keywords: redox, chemical expansion, defect chemistry, mixed ionic electronic conduction, ceria, chemo-mechanics, nanoparticle, thermogravimetric analysis, dilatometry, impedance

Thermo-Mechanical Properties and Benefits of Borosilicate Glass for SOEC Sealants

Boro-silicate glass materials have ideal properties for sealing oxidizing and reducing environments and electrically insulating solid oxide electrolysis cells (SOEC), while maintaining a glassy phase at high temperatures (750-900°C) to minimize chemo-mechanical degradation and gas permeability 1,2. Glass seals are typically applied as a slurry; hence, they are also expected to have non-wetting properties to prevent glass infiltration into the porous electrode structures during manufacturing 3. During the first startup, the initial temperature ramp serves to evaporate any binder in the slurry and to go through the glass transition phase, which cures the glass and increases hardness to improve resistance to creep. Typical glass materials operate in visco-plastic regimes (i.e., beyond the material’s glass transition temperature) and must be chemically stable while operating in steam-rich and oxygen-rich environments. To fully understand the performance of borosilicate glass seals, optimize the manufacturing, assembly, and maintenance of SOEC, we must be able to measure and analyze the glass material properties (i.e., glass transition temperature, coefficient of thermal expansion, modulus, creep, hardness) at the same operating conditions relevant for SOEC operation. In this work, we characterize the thermo-mechanical properties of borosilicate glass powder and sintered samples at various temperatures (ranging from ambient to 850°C), and at different aging conditions (i.e., atmosphere composition, temperature, and duration). The atmosphere composition is changed between air, steam-N2 mixtures, and H2-N2 mixtures to evaluate the chemical stability of borosilicate glass relating to the possible depletion of boron and silicon via the formation of boron hydroxide and silicon vapor when exposed to steam- and hydrogen-rich environments. The aging temperature and duration is varied to evaluate the crystallization kinetics, particle size growth, and its effect on mechanical properties. We employ a combination of Simultaneous Thermal Analysis - STA (i.e., combined Thermogravimetric Analysis - TGA, Differential Scanning Calorimetry - DSC, Fourier Transform Infrared - FT-IR spectroscopy, and Quadrupole Mass Spectroscopy - QMS), and nanoindentation as characterization techniques, while surface roughness is estimated with a 3D confocal optical microscope.Surface roughness varies between 0.83-1.38 𝜇m ± 1.1-1.76 𝜇m (Sa ± Sq). Both powder and solid samples are analyzed via STA with sequential temperature ramps (constant heating rate at 10 K/min in Ar atmosphere) up to 1500°C to estimate the effect of crystallization and particle size on the glass transition onset. For a sample aged at 850°C for 340 h, the first ramp shows typical DSC exothermic peaks (mW/mg) at around 800°C, with a midpoint glass transition occurring at 900°C. However, on the second ramps, peaks lower to around 500°C and the glass transition is estimated to be around 700°C. Subsequent tests consistently mirrored the trend of the second temperature ramp, showing minimal deviation and influence of crystallization and particle growth. Nanoindentation is performed between room temperature and 600°C to characterize both sintered glass samples “as-received” and aged at temperatures between 750-950°C for 340 h. Comparing a sample aged at 750°C with an “as-received” sample, the elastic moduli equally decreased from 100 GPa at room temperature to 40 GPa at 600°C, with comparable hardness values ranging from 10 GPa at room temperature to 0.5-0.9 GPa at 600°C, respectively. A.G. Sabato, G. Cempura, D. Montinaro, A. Chrysanthou, M. Salvo, E. Bernardo, M. Secco, F. Smeacetto, Journal of Power Sources, 328, 262-270 (2016)Dilshat U. Tulyaganov, Allu Amarnath Reddy, Vladislav V. Kharton, José M.F. Ferreira, Journal of Power Sources, 242, 486-502 (2013)S.-B. Sohn, S.-Y. Choi, G.-H. Kim, H.-S. Song, G.-D. Kim, Stable sealing glass for planar solid oxide fuel cell, J. Non. Cryst. Solids. 297 (2002) 103–112. doi:10.1016/S0022-3093(01)01042-0 Figure 1

Strategy to Enhance Air Electrode Performance and Durability in Soe and Co-Soe Modes: Composite Electrode with a Gradually Changing Composition

Among the key challenges of the Solid Oxide Cell (SOC) is stable, long-term operation in electrolysis (SOE, Solid Oxide Electrolysis), and co-electrolysis (co-SOE) modes. Many factors impact the SOC’s lifespan, i.e., the chemical composition of the fuel and air electrode, the type of the cell, and working conditions (e.g., current density, temperature). Therefore, the development of high-performance and durable cells seems to be crucial, as SOE/co-SOE systems may play an important role in the ongoing transformation toward a climate-neutral economy (low-emission hydrogen production; efficient utilization of CO2and renewable energy) [1,2].One of the crucial degradation mechanisms of SOC in electrolysis/co-electrolysis mode is the delamination of the air electrode, caused by the accumulation of high oxygen partial pressure on the interphase of the electrolyte, the formation of additional phases, and/or reaction of voids/cracks in the electrolyte or buffer layer [2,3]. A strategy to mitigate the risk of air electrode delamination is to use composite electrode based on the buffer layer material (GDC- Gd0,1Ce0,9O2) and state-of-the-art electrode – LSC (La0,6Sr0,4CoO3-δ), as it will lower the effect of the thermal expansion mismatch between the electrode and buffer layer/electrolyte. Moreover, by manipulating the microstructure of the electrode, e.g., by introducing a pore-forming agent, it is possible to ensure fast and effective collection of oxygen generated during operation in the SOE/co-SOE mode on the air side (preventing potential differences leading to the stresses on the electrode-electrolyte interface).In this study, the electrochemical performance of solid oxide cells with a modified, gradually changing composite LSC-GDC air electrode was verified in electrolysis and co-electrolysis modes. The following air electrode compositions were proposed for cell preparation: type 1: 1st layer 50LSC:50CGO, 2nd layer: 75LSC: 25GDC, 3rd layer: LSC, type 2: 1st layer 75LSC:25CGO, 2nd and 3rd layers: LSC with PMMA as a pore former; type 3: 1st layer 75LSC:25CGO, 2nd and 3rd layers: 90LSC:10GDC, and type 4: 1st layer 85LSC:15CGO, 2nd layer: 90LSC:10GDC; 3rd layer: LSC with PMMA as a pore former. The proposed air electrode was tested at the single-cell level (cells size of 50 mm x 50 mm), and the most promising solutions were implemented in the SOC stack (a stack consisting of 3-5 cells with a size of 110 mm x 110 mm). The electrochemical analysis of the developed cells includes measurements of the j-V dependences and EIS spectra under different modes (SOE and co-SOE), various temperatures, current densities, and different gas flows delivered at the air side of the cell. The microstructure, morphology, and composition of the prepared cells and samples after testing were analyzed using SEM, SEM-EDS, and, for selected samples, the FIB-SEM method. The obtained results showed that by a gradually changing the electrode composition, specifically by reducing the GDC content in the electrode, it is possible to obtain a stable electrode (a strategy to prevent air electrode delamination) with high catalytic activity in both electrolysis and co-electrolysis modes. The composite GDC-LSC electrodes with various compositions seem to be promising air electrodes for SOE and co-SOE systems. The study achieves relatively high current densities compared to the SoA cells, with only negligible degradation changes observed after long-term testing (>300 h in single cell configuration). Acknowledgments The presented research was financially supported by: the National Centre for Research and Development, Poland, within project no. LIDER/1/0003/L-12/20/NCBR/2021, which focuses on research related to composite electrodes. Anna Niemczyk acknowledges support from the Foundation for Polish Science (FNP) through a scholarship from the START program. References B. Mogensen et al., Clean Energy 3 (2019) 175; DOI: 10.1093/ce/zkz023Hauch, P. Blennow, Solid State Ionics 391 (2023) 116127; DOI: 10.1016/j.ssi.2022.116127Subotić, C. Hochenauer, Progress in Energy and Combustion Science 93 (2022) 101011; DOI: 10.1016/j.pecs.2022.101011

Synthesis and Characterization of Electrospun Ni-BZY Nano-Fiber Anodes

Solid oxide fuel cell (SOFC) and related Protonic Ceramic Fuel Cell (PCFC) technologies have demonstrated significant promise for the efficient and clean electrochemical conversion of stored energy held in a wide variety of renewable fuels, decreasing dependence on traditional fossil fuels. The high efficiencies of both devices arise from the direct chemical-to-electrical energy transformation, achieved without moving parts and the losses inherent to combustion technologies. As in all fuel cells, electrons are generated via oxidation of fuel at the anode to power an external load before returning to the cathode to reduce an oxidant, usually O2. Separating the two electrodes is a dense, gas-tight, electronically insulating electrolyte that permits ion diffusion to complete the circuit. The SOFC’s solid oxide electrolyte passes oxides from the cathode to the anode, but the large activation barrier associated with this process requires high operating temperatures (≥700 ˚C), exacerbating degradative processes and adding challenges for thermal management. In contrast, the PCFC’s perovskite electrolyte permits protonic diffusion from the anode to the cathode, with a smaller activation barrier leading to lower operating temperatures (450 – 700 ˚C). Despite recent advancements in emerging PCFC materials, the overall efficiency and long-term stability of the device is still impacted in part by the anode’s ability to catalyze fuel oxidation, generate protons, and shuttle electrons to an attached current collector. These processes in turn are strongly linked to the morphology and stability of the anode—often a cermet composed of a Ni catalyst/electronic conductor and protonic ceramic such as yttrium-doped barium zirconate (BZY). In particular, continuity is needed for the Ni, BZY, and pore networks while maximizing boundaries between each phase (three-phase boundary). Traditionally, anodes are fabricated by mixing appropriate powders together without much control over the morphology over the micron-sized components. In this study, we explore an alternative approach to systematically engineer Ni-BZY nanofibers within the anode to enhance overall device performance through improving the underlying electrochemical processes at the anode. Low nickel-content BZY anodes (<40 wt. % Ni) for PCFCs are fabricated through electrospinning, with two distinct methods evaluated for nickel loading. First, uniform BZY nanofibers are synthesized by electrospinning a gel containing BZY metal cations and 5 wt. % Polyvinylpyrrolidone (PVP) as dispersant in ethanol/acetic acid solution followed by sintering at 900°C for 3 h in air, and subsequent electroless deposition of nickel on the fiber surfaces. Second, Ni-BZY is prepared by electrospinning a polymer containing a nickel salt and the same BZY precursors followed by co-sintering at 900°C for 3 h. The Ni-BZY fibers underwent morphological, crystallinity and elemental characterization via SEM, XRD, TEM and Raman microscopy. Initial comparison of the fibers fabricated by both methods has shown that uniform nickel loading of ~35 wt. % on the fibers was achieved in the second method. Slurries containing fibers made from both methods are deposited as anodes onto BZY electrolytes, and the complete cells are tested electrochemically under hydrogen at elevated temperature and compared with a control PCFC constructed using conventional powder materials with comparable nickel loading. In summary, electrospun nanofibers, known for their excellent permeability and faster charge transfer due to their porous structure, present an intriguing alternative for high-performance PCFC anode materials. Figure 1

(Invited) Streamlined Production of Protonic Ceramic Electrochemical Cells Via Ultrasonic Spray Coating

Thin solid oxide films are crucial for developing high-performance solid oxide-based electrochemical devices aimed at decarbonizing the global energy system. This presentation introduces ultrasonic spray coating technique (USC) for producing <10 µm thin electrolyte films, as well as uniform 4×4 cm2 oxygen electrode films, with a systematic process optimization considering solid loading rates, spray passes, and annealing temperature etc. Notably, the integrated approach highlights the versatility of USC in addressing both oxygen electrode and electrolyte fabrication challenges. The resulting protonic ceramic electrochemical cells, fabricated with these optimized parameters, exhibit remarkable electrochemical performance, structural integrity, and stability in both fuel cell and electrolysis modes. This presentation provides a holistic perspective on scalable production techniques, showcasing the potential of ultrasonic spray coating for advancing large-sized solid oxide electrochemical cells.

CO2 Capture By Hybrid Electrolyte Membrane Electrode Assembly

In the pursuit of decarbonizing transportation sectors, there has been considerable enthusiasm from both industries and academia regarding the utilization of atmospheric CO2 as a chemical feedstock. To mitigate the energy requirements associated with carbon capture, utilization, and sequestration, research efforts are focused on developing and exploring electrochemical cell technologies. Here, we present an innovative solid oxide electrochemical cell configuration featuring a hybrid electrolyte membrane electrode assembly (HE-MEA) designed for efficient CO2 capture and separation. Our approach involves optimizing the process through the tuning of electrolyte and electrode compositions and operation conditions, aiming to capture CO2 effectively under various conditions. The investigation of the cathode's working mechanism, employing advanced characterization techniques, will be presented. This study marks a significant step forward in CO2 capture, particularly at elevated temperatures, and contributes to the broader effort of advancing sustainable practices in transportation and combating climate change.

Electrochemical Conversion of CO2 to Fuels and Useful Chemicals over Metal Supported Solid Oxide Electrolyzers

Electrochemical conversion of CO2 and H2O to fuels and chemicals provides a promising approach to simultaneously mitigate greenhouse emission and store surplus energy, which reduces electricity network variation due to increased intermittent renewable energy (such as solar and wind) utilization. Metal supported solid oxide electrolyzers (MS-SOEs) developed at Lawrence Berkeley National Laboratory provide advantages of rapid start-up, mechanical ruggedness, redox tolerance, dynamic operation, and low-cost materials. A relatively high operating temperature range of 600 to 750°C promotes energy efficiency and allows utilization of thermal energy such as steam.In this work, efficient and stable catalysts developed at the University of South Carolina have been infiltrated in the symmetrical and porous MS-SOE architecture. The phase purity has been analyzed by X-day diffraction. The morphologies of these infiltrated and posttest catalysts have been examined by scanning electron microscopy. Optimization of cell structure, processing temperature, cell voltage, and catalyst infiltration cycles for better cell performance will be presented. The stability of MS-SOEs has been evaluated during continuous operation for >200 hours. The cell degradation mechanisms revealed by electrochemical impedance spectroscopy and high-resolution scanning electron microscopy techniques will be presented.In addition to pure CO2 electrochemical conversion, effects of additional water and hydrogen in CO2 feedstock will be analyzed. Faradic efficiency and chemical selectivity calculated from gas chromatograph and electrochemical analyses will be presented.

Design and Performance Evaluation of a Specialized Bubbler System for Accurate and Repeatable Solid Oxide Electrolysis Cell (SOEC) Testing

Accurate assessment of Solid Oxide Electrolysis Cell (SOEC) performance demands standardized testing conditions, particularly in stable steam delivery. Fluctuations in steam concentration and flow rate can significantly impact measured open-circuit voltage (OCV) and polarization behavior. Although direct steam injection is straightforward, it is often hindered by instability resulting from intermittent liquid water flux, pressure fluctuations, and fractional distillation effects. Bubbler humidification systems have the potential to offer consistent steam, but tailored designs for SOEC testing are currently absent.This study introduces a specialized bubbler system designed to deliver stable steam to SOEC test stands accommodating both oxygen-conducting (O-SOEC) and proton-conducting (H-SOEC) cells. The bubbler components include a refill water reservoir, a level control module, heating elements, pressure relief valves, check valves, tubing, and fittings integrated with the test stand. The system humidifies the sweep gas, transporting steam to the cell test fixture situated within a high-temperature furnace.The design process involved meticulous considerations of materials compatibility, hydrogen safety, and overtemperature protection. All wetted components employ stainless steel, glass, or PTFE materials in their construction construction. Redundant thermocouples ensure safe process temperatures with automated overtemperature shut off. The refill reservoir and bubbler headspace operate near ambient pressure, facilitated by an exhaust line vent sized for minimal backpressure.In various executed O-SOEC tests, the bubbler maintained OCV stability within ±5 mV over several hundred hours for each cell operating at 750°C, eliminating spikes caused by steam fluctuations observed with direct injection methods. This facilitates precise electrochemical analysis and determination of area-specific resistance losses. Polarization curves align with expected behavior based on the Nernst equation. The system has demonstrated safe and stable functionality for over thousands of hours across various operating conditions.The bubbler design presents researchers with notable advantages over existing steam supply options for SOEC test stands, addressing performance, safety, and flexibility concerns. Online instrumentation enables closed-loop control of steam conditions, enhancing stability. Standardization of test equipment is crucial for quality results, and this work contributes progress toward reproducible protocols in the international SOEC community. The modular bubbler approach, integrated with safety features, also signifies safer methodology choices for lab-scale experimental research.

Accelerating the Development of Oxygen Electrodes for Solid Oxide Cells Using Two-Stage Machine Learning

Reversible Solid Oxide Cells (RSOCs) stand out as highly efficient and cost-effective devices for energy storage and conversion. However, the pursuit of high-performance and durable RSOCs is impeded by the lack of efficient and stable oxygen electrodes. The conventional trial-and-error approach used for the development of oxygen electrodes is resources and time-consuming. In this presentation, we introduce a novel "two-stage machine learning" approach designed to expedite the discovery of optimal oxygen electrodes for efficient oxygen reduction/evolution reaction (ORR/OER) in SOCs. In the initial stage, we employed a high-throughput calculation approach to generate four ORR/OER related descriptors (energy above the convex hull, p-band center, d-band center, and vacancy formation energy) for a set of 4455 perovskite oxide candidates. Subsequently, we successfully predicted these descriptors using machine learning techniques based on the fundamental physico-chemical features of the candidates. Moving to the second stage, we measured the polarization resistances - directly related to ORR/OER activity - of 142 oxygen electrodes and employed them as prediction targets. Through our machine learning method, we accurately predicted experimental results based on the fundamental physico-chemical features of the candidate materials. Notably, among the 4455 candidates studied, a specific oxygen electrode material is predicted to exhibit both high activity and stability. When applied to an RSOC based on a proton-conducting electrolyte operated at 600 °C, a high peak power density of >1.5 W cm−2 is demonstrated in the fuel cell mode, and a high current density of >2.5 A cm−2 is achieved at a cell voltage of 1.3 V in the water electrolysis mode while maintaining stable operation for 500 hours.

Novel Ru-Based PEM Electrolysis Catalyst – Development from the Nano- to the Industrial-Scale

For the de-fossilization of sectors like chemicals, steel, and transportation, green H2 generated via water electrolysis provides a path towards net-zero. The broad use of H2 across hard-to-abate sectors confirms the urgent need for green hydrogen at scale.Within water electrolysis, there are several competing technologies: the so-called solid oxide electrolysis cell (SOEC), alkaline water electrolysis (AEL) and polymer electrolyte membrane electrolysis (PEM EL). Here, the latter shows significant benefits, such as high current density operation (> 2 A/cm2) and thus a smaller footprint, highly dynamic operation mode, high gas purity, and generation of pressurized hydrogen. However, at present, PEM EL requires precious metal catalysts; in particular, the O2 evolution on the anode currently relies on iridium, a metal which is rather scarce and expensive [1].To meet the demand of iridium with respect to the announced increase in electrolyzer capacities in the multi-GW range, material innovation to reduce the use of this precious metal must be implemented. Successful catalyst and electrode developments have already been demonstrated in the BMBF funded project Kopernikus P2X, whereby loadings of approx. 0.3 mg/cm2 (< 0.1 g/kW1) have been achieved without any significant losses in activity over time [2, 3].Here, we present a material innovation in the form of Ru-based electrocatalysts with a significantly reduced Ir content. This ruthenium-iridium oxide can be adjusted in a wide range of Ir content down to less than 15 wt.% (Ir). Consequently, iridium-based electrode loadings of less than 0.1 mg/cm2 and mass activities of about 3,500 A/g are feasible. Moreover, in accelerated degradation tests those mixed-oxides have demonstrated the often-missing stability by showing low degradation rates, similar to that of pure IrO2, in up to 30,000 potential-induced stress cycles.This achievement stems from a remarkable screening approach that combines synthesis, characterization and testing at the nanoscale at Mattiq, and on industrial scale in the multi-gram range at Heraeus Precious Metals GmbH & Co. KG. Remarkably the alignment of degradation testing on both scales showcases the power of the applied method, providing a blueprint for high throughput screening for future material developments, both within water electrolysis and beyond.

An Analytical Model for an Anode-Supported Solid Oxide Fuel Cell

This study presents a one-dimensional, non-isothermal, steady-state model to analyze performance of an anode-supported solid oxide fuel cell (SOFC). The modeling domain encompasses components including a NiO-YSZ support and functional layer forming the anode, a YSZ electrolyte, a GDC interlayer, as well as LSCF+GDC and LSCF constituting the cathode. The model distinguishes different types of electrode polarization resistances using experimental impedance data at various temperatures under open circuit voltage (OCV), employing a detailed equivalent circuit model to determine the temperature and partial pressure dependencies of electrode exchange current densities. Moreover, this approach serves as an efficient method for estimating the conductivity of both the anode and cathode. As a result, activation energies and ohmic overpotentials are derived, considering microstructural and geometrical aspects, which allows for accurate quantification of the ohmic resistance associated with ionic conduction.The model incorporates coupled multi-physics elements, such as mass and charge transport, electrochemical reactions, and heat transfer. A notable feature of the model is its consideration of reaction zone layers near the electrolyte, where electrochemical reactions generate electrons, oxide ions, and water vapor. Enhancing prediction accuracy, the model applies multilayer discretization within the electrode and electrolyte to reflect actual material properties and localized conditions more accurately. The model predicts the performance of a single-cell SOFC using pure hydrogen at the anode and varying oxygen concentrations (100%, 50%, 20%, and 10%) at different operating temperatures (700°C, 660°C, 620°C, and 580°C) and design conditions. Simulated results are compared with experimental data, and the impact of various operating and design parameters on SOFC performance is examined. Findings indicate that kinetic and concentration overpotentials in an anode-supported SOFC are lower than ohmic overpotentials, even at higher current densities. Furthermore, ohmic overpotential is identified as the primary contributor to total cell potential loss, highlighting the need for its minimization to improve cell performance.

(Invited) Dynamic Operation of Solid Oxide Electrolyzers

Electrolysis of steam to generate hydrogen is expected to be a highly dynamic operation if renewable resources such as wind and solar are used as the electrical power input. Rapid fluctuation of input power and intermittent operation of the solid oxide electrolysis stack will result in transient operating conditions at the cell level. All operating variables such as temperature, steam content, voltage, flow rate, etc. may change rapidly in these conditions.To address this situation, this work operates Ni/YSZ-supported and metal-supported cells under highly dynamic conditions, with individual variables isolated. The cells are remarkably robust to dynamic operation. A safe range is found for each operating variable, with accelerated degradation observed outside that range in certain cases. For example, cycling Ni/YSZ-supported cells between 1.3 V and 1.6V at 750°C and 50:50 H2O:H2 is tolerated well, but increasing the upper voltage to 1.7 V and higher leads to increased degradation. Additionally, Steam:hydrogen ratio is cycled between 3:97 and 75:25. Temperature is cycled between 150 and 800°C. Operation is cycled between fuel cell and electrolysis modes, with synchronized steam content. Metal-supported cells tolerate steam cycling, voltage cycling, temperature cycling and redox cycling, and results for button cells and 50 cm2 planar cells will be reported. In many cases, hold times are 1 minute, allowing thousands of cycles to be accumulated over hundreds of hours of operation.Figure 1. Dynamic cycling of a Ni/YSZ-supported button cell at 750C. (Top) Cycling between 1.3 and 1.7V with 1 min holds and 50/50 H2/H2O. (Bottom) Cycling between various steam contents at 1.3 V. Figure 1

Long Term Durability Investigation of Cu-Doped La2NiO4 Oxygen Electrodes in Solid Oxide Electrolysis Cells

State-of-the-art oxygen electrodes in SOECs, lanthanum strontium cobalt iron oxide (LSCF) and lanthanum strontium cobalt oxide (LSC), contain strontium. Undesired reactivity and migration of Sr cations during long-term operation was found to be detrimental to the electrochemical performance as they triggered formation of multiple oxide phases, including insulating phases and electrode or barrier layer delamination. Developing alternative electrodes that are devoid of Sr is very important for long-term operation of SOECs.In this work, we synthesized and evaluated properties of La2NiO4-based compositions with a Ruddlesden-Popper structure. The Cu-doped La2NiO4 compositions made of nano-size particles exhibited an enhanced electrochemical performance when tested in SOECs during steam electrolysis for hydrogen production. Long-term durability of these electrodes was studied using planar Ni-YSZ electrode-supported cells with an active area of 1.5 (button cells) and 13 cm2 (2.5 cm x 5 cm cells). Compared to the Sr-containing electrodes, the La2Ni0.8Cu0.2O4 (LNCuO-20) demonstrated lower degradation rate at 1.3 Volt resulting in a current density over 1 A/cm2 at 750⁰C. Chrome and sulfur tolerance of these electrodes during long term operation will be discussed as well.

Enhancing Direct Eectrochemical CO2 Electrolysis By Introducing a-Site Deficiency for Dual-Phase Pr(Ca)Fe(Ni)O3-Δ Cathode

High-temperature CO2 electrolysis via solid oxide electrolysis cells (CO2-SOECs) has drawn special attention due to the high energy convention efficiency, fast electrode kinetics, and great potential in carbon cycling. However, the development of cathode materials with high catalytic activity and chemical stability for pure CO2 electrolysis is still a great challenge. In this work, A-site cation deficient dual-phase material, namely (Pr0.4Ca0.6)xFe0.8Ni0.2O3- δ (PCFN, x=1, 0.95, and 0.9), has been designed as the fuel electrode for a pure CO2-SOEC which presents superior electrochemical performance. Among all these compositions, (Pr0.4Ca0.6)0.95Fe0.8Ni0.2O3- δ (PCFN95) exhibited the lowest polarization resistance of 0.458 Ω cm2 at open circuit voltage and 800℃. The application of PCFN95 as the cathode in a single cell yields an impressive electrolysis current density of 1.76 A cm-2 at 1.5 V and 800℃, which is 76% higher than that of single cells with stoichiometric Pr0.4Ca0.6Fe0.8Ni0.2O3- δ (PCFN100) cathode. The effects of A-site deficiency on materials’ phase structure and physicochemical properties are also systematically investigated. Such an enhancement in electrochemical performance is attributed to the promotion of effective CO2 adsorption, as well as the improved electrode kinetics resulting from A-site deficiency.

Recent Advancements in Materials for Proton-Conducting Reversible Solid Oxide Cells

The escalating threats posed by climate change and environmental issues underscore the need for urgent exploration of clean energy technologies. In this context, proton-conducting reversible solid oxide cells (P-RSOCs) have emerged as promising contenders for large-scale energy storage and conversion. Their efficacy at intermediate temperatures (400 - 600 °C) is a distinctive advantage, attributed to the remarkable ionic conductivity of proton conductors within this temperature range. This feature positions P-RSOCs favorably for the efficient, cost-effective, and enduring conversion between clean electricity and green hydrogen.However, the successful commercialization of P-RSOCs hinges on the rational design of novel materials and meticulous surface/interface modifications to significantly enhance performance and durability. Achieving prolonged durability during cycling between fuel cell and electrolysis modes while maintaining high Faraday efficiency and roundtrip energy efficiency is of paramount importance. A central challenge involves the development of electrolyte materials exhibiting exceptional stability and a high ionic transference number under operating conditions. Additionally, bifunctional electrodes/catalysts, particularly for the oxygen electrode, must demonstrate elevated activity for efficient dual-mode operation.To effectively tackle these challenges, it is imperative to devise new protocols for controlling the structure, composition, and morphology of materials across multiple length scales. Equally crucial is gaining a fundamental understanding of degradation mechanisms and electrode processes. This presentation will illuminate the critical scientific challenges inherent in developing a new generation of P-RSOCs, providing insights into the latest advancements in electrolyte materials and bifunctional electrodes/catalysts. Furthermore, it will highlight strategies for enhancing durability and electrode activity through surface/interface modification, along with the latest developments in modeling, simulation, and in situ characterization techniques to deepen our understanding of the underlying mechanisms. The presentation will conclude prospects for achieving low-cost, highly efficient, and durable P-RSOCs through innovative material-based solutions.

Multi-Physics Modeling and the Sensitivity Analysis for the Critical Factors in Solid Oxide CO2-Steam Co-Electrolysis System Performances

A multi-physics modeling framework, which includes electrochemical and chemical reactions, mass transfer, and energy balance, has been developed and validated against experiment measurements to investigate the performance of solid oxide CO2-steam co-electrolysis (SOEC) under various operating conditions and cell designs. However, multi-physics modeling for complex SOEC systems can be computationally expensive and not tractable for general system design and optimization. Reduced-order models (ROMs) have been proven as a powerful tool for reducing computational costs, closely mimic the high-fidelity SOEC stack models and identify the operational condition parameters to which the SOEC stack is sensitive and needs appropriate controls for stable operation. In this study, the deep neural networks (DNN) algorithm is employed to construct ROMs according to multi-physics simulations for SOECs to systematically investigate the SOECs’ electrochemical performance and rank the contributions of operational condition parameters for both 2 cm2 button cell and 300 cm2 planar cells. Sensitivity analysis reveals that cell voltage, fuel composition (denoted by CO2/H2O ratio), and the operating temperature impact the cell performance most. The product ratio ΔCO/ΔH2 has a stronger dependence on the CO2/H2O ratio in the fuel compositions than on other operating condition parameters. The large 300 cm2 planar cells were modeled under both adiabatic and furnace environment. The simulation and sensitivity analysis indicate that the large cell operating in adiabatic environment usually provides relatively lower performances than the one in furnace environment. Additionally, the adiabatic environment also causes the cell’s performances are more sensitive to the operation conditions, such as external voltage, fuel flow rate, and fuel compositions. The large cell in adiabatic environment also leads to higher internal temperature variation, which may impact the structure reliability.

Simulation of Electrical Conductivity of Porous Composite Electrodes for Solid Oxide Cells Using a Monte Carlo 3D Equivalent Electronic Circuit Networks

Solid oxide cells (SOCs) show high potential in energy conversion applications necessary for the decarbonization of the economy. Their advantage consists in ability to operate at high temperatures, reaching up to 900 °C. Firstly, it results in accelerated electrode reactions kinetics, secondly, in favorable thermodynamic conditions decreasing the equilibrium voltage of the water splitting. As a result, SOCs are attractive candidates for both efficient electrolysis and fuel cell applications, offering a robust solution in the pursuit of clean energy. However, the elevated operational temperature also introduces material challenges that hinder the competitiveness of SOCs.Porous gas diffusion electrodes are used to accomplish the desired electrode reactions. Considering conventional exclusively electron-conductive electrode materials, triple phase boundary (TPB) is required for the reactions to take place – a simultaneous contact of electron-conductive, ion-conductive and gaseous phase. While the electrode and electrolyte phases are solid, the gaseous phase is represented by open porosity in the electrode body. TPB is located exclusively at the contact area of electrode and electrolyte components in the case of single-phase electrodes, limiting the electrode electrocatalytic performance. To avoid the limitation by TPB length, composite electrodes are frequently used. Due to the involvement of the ionically conductive phase, they exhibit improved electrocatalytic capabilities.Electrolyte phase, however, usually exhibits 4 orders of magnitude lower electrical conductivity than the electron-conductive phase, while gaseous phase is electrically non-conductive. Thus, an improper phase composition and morphology of the composites can lead to a significant drop in their electrical conductivity and thus in the cell performance. Simple and reliable method for the conductivity value prediction is up to now missing. At the same time, experimental determination is both expensive and time-consuming. The goal of this study was to develop simple, fast and reliable method for prediction of electrical conductivity of the porous electron-ion conductor composites.The key feature of the presented approach lies in the minimal requirements for input parameters. Only electrode phase composition and bulk electrical conductivity of each phase are required. Based on the input composition, the model generates a 3D artificial specimen, a domain discretized into cubic voxels each assigned randomly to a specific phase. The resulting structure is substituted with an equivalent circuit network with electric elements corresponding to the electrochemical properties of the material components: specific resistivity of electrical conductors and polarization resistance / capacitance of electrochemical reaction at material interface. In-silica electrochemical impedance spectroscopy measurement is performed by solving charge balance following Kirchhoff’s current law for multiple frequency values. Resulting impedance spectrum is fitted in order to obtain Ohmic and polarization resistance and the capacitance of the artificial specimen. This procedure is averaged over a large number of artificial specimens in a Monte Carlo manner.Conventionally used oxygen electrode composite material lanthanum strontium manganite (LSM) mixed with yttria-stabilized zirconia (YSZ) was used to produce validation dataset. LSM:YSZ powder mixtures of compositions between 1:0 and 0:1, chosen to produce samples of various degree of LSM percolation, were homogenized. The mixtures were fired at 1150 °C. Electrical conductivity of the pellets was determined at temperatures between 600 and 800 °C using electrochemical impedance spectroscopy.Experimental data obtained were confronted to the model results. The model demonstrated very good accuracy for a porosity value of up to 55%. Significant error was observed in the porosity range between 55% and 68%. Finally, the model failed to generate an artificial specimen with a porosity of 75%. As it was found, the limited applicability of the model for the materials characteristic for high porosity was caused by the coalescence of the void phase. This shortcoming of the model was solved by implementing morphological parameter describing degree of void phase coalescence in the electrode structure. Due to this modification, model allows to gain valuable information on the microstructure of the studied composite material on the base of the experimentally determined conductivity data.This work introduces a novel modelling approach with minimal amount of input parameters, streamlining the prediction of electrical conductivity of porous electron-ion conductor composites. This simplified yet effective methodology holds great promise for efficiently characterizing and optimizing materials for energy conversion applications, offering a valuable tool for advancing research in the field.This publication was supported by the project "The Energy Conversion and Storage", funded as project No. CZ.02.01.01/00/22_008/0004617 by Programme Johannes Amos Commenius, call Excellent Research.