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At least 19 records

The Effect of Operational Temperature on the Performance and Durability of Solid Oxide Fuel Cells and Solid Oxide Electrolysis Cells

Solid oxide fuel cells (SOFC) and solid oxide electrolysis cells (SOEC) have received great interest due to their highly effective reversibility as power generation and H2 production system without releasing any greenhouse gases into environment. The LSCF electrode exhibits a higher structural and performance stability under both SOFC and SOEC operation due to its mixed ionic and electronic conductivity, and there is no immediate delamination taking place during the initial several hundred hours operation. However, the LSCF based air electrode still presents significant performance degradation (with the increased resistance) over the prolonged operation, such as over 1000 hours of operation under SOFC and SOEC. The influence factors for the cell’s performance and stability need to be optimized to improve the power generation for SOFC and H2 production for SOEC. The effects of operational temperature on the performance and durability for both SOFC and SOEC are electrochemical operation dependent. The performance and performance durability for the first 1500h were currently studied under optimized operational temperature for reversible SOFC/SOEC.

Fan, Yueying [NETL Site Support Contractor, Nation↗

Modeling Framework to Analyze Performance and Structural Reliability of Solid Oxide Electrolysis Cells

Solid oxide electrolysis cells (SOEC) have been receiving significant attention recently because of their high energy efficiency and fast hydrogen production. In this study a multi-physics model to simulate the SOEC performance and structural reliability of a state-of-the-art planar SOEC design was developed. The electrochemical reactions, fluid dynamics, species transport, electron transfer, and heat transfer were modeled in the commercial computational fluid dynamics (CFD) software STAR-CCM+. The thermomechanical analysis and the associated structural reliability evaluations were conducted using the commercial finite element analysis software ANSYS. The electrochemistry model was validated by using the experimentally obtained current-voltage (I-V) characteristics of the electrode-supported SOECs. The reliability analysis using a risk-of-rupture approach showed low failure probabilities under standard operating conditions considered in this study. For cells operated at voltages well above a thermoneutral voltage, the reliability evaluations indicated a potential risk of cell failure, but the damage was concentrated locally in specific areas of the cell which typically do not lead to total loss of cell function. The presented approach provides insights for evaluating representative cell and stack performances and structural reliability without intensive testing and for developing optimally performing and structurally reliable SOECs for efficient hydrogen generation.

25 ENERGY STORAGE↗

Dynamic oxidation of (Mn,Co) 3 O 4 -Coated interconnects for solid oxide electrolysis cells

Solid oxide electrolysis cell stacks are expected to experience dynamic conditions when using renewable electricity derived from wind or solar power. To address this scenario, (Mn,Co) 3 O 4 (MCO)-coated Crofer 22 APU interconnect coupons are subjected to thermal cycling, and intermittent current density, with gas compositions relevant to high-temperature electrolysis (elevated steam:hydrogen ratio and oxygen content). Defects are also intentionally introduced in the MCO coating, to assess whether the difference in oxidation properties of the adjacent coated and uncoated (defective) surfaces causes sufficient stress to damage the protective oxide scale. Specimens with defects are subjected to oxidation for 1000 h at 800 °C, or thermal cycling. Before thermal cycling, some specimens are pre-oxidized to create a thick oxide scale to mimic the scale thickness expected after ~30 kh operation. In all cases, the coating and oxide scale remain well adhered with no cracking observed. Area-specific resistance (ASR) is monitored in both single-atmosphere and dual-atmosphere conditions, and the ASR is stable and is not impacted by dynamic cycling of the current density. Finally, this work provides confidence that the MCO coated interconnect will function as needed in dynamic operation conditions, even with coating defects.

08 HYDROGEN↗

Voltage cycling as a dynamic operation mode for high temperature electrolysis solid oxide cells

Solid Oxide Electrolysis Cells (SOECs) have emerged as a promising technology for the efficient production of H2 via high-temperature electrolysis. However, power input from dynamic energy sources remains a significant challenge for their long-term stability. It is important to analyze the tolerance of cells under dynamic operation conditions. This study focuses on evaluating the impact of voltage cycling on the performance and durability of electrode-supported SOECs. We explore the operational limits and degradation mechanisms of SOECs subjected to various voltage conditions and find that the cells have high tolerance for dynamic voltage. Voltage cycling between 1.3 V and 1.5 V for 9000 cycles does not damage the cell. Conversely, cycling to higher voltages (≥1.7 V) results in accelerated degradation. Advanced characterization is used to screen for various degradation modes post operation. Within the oxygen electrode, XRD and STEM EDS find compositional and phase evolution in all voltage cycled samples including increased decomposition of the air electrode resulting in cation migration. Microstructural analysis of the fuel electrode from nano-CT data shows minimal change throughout the sample set and no evidence of Ni migration, indicating the fuel electrode is stable and not impacted by cycling to higher voltages within the timeframe studied.

Zhu, Zhikuan↗

Evaluation of a 5kW Solid Oxide Electrolysis Cell Stack

Solid oxide electrolysis cells (SOECs) are a developing technology for hydrogen production. They are promising due to their utilization of thermal energy to reduce their electricity consumption. The Department of Energy (DOE) has set goals to reduce the price per kilogram of hydrogen, and Idaho National Laboratory (INL) is conducting research to develop and demonstrate advanced methods and technologies to achieve making hydrogen a more affordable, efficient, and sustainable energy source. In this project, INL is collaborating with a vendor to evaluate and validate the design of a 5kW SOEC stack. The test aims to demonstrate a safe startup, operation, and shutdown on INL’s 5kW test stand, providing third-party validation in a different environment. A successful 50-hour test with stable hydrogen production will pave the way for a subsequent 1000-hour test. This project emphasized learning about electrolysis and the various support systems, referred to as balance of plant (BOP) equipment. These systems required modification while swapping to the vendor 5kW SOEC stack, most prominently the furnace door design and the controls system. It also included gaining skills in creating computer-aided design (CAD) drawings for the new door while using available materials and ensuring it met high-temperature requirements. Upon completion of modifications to the test stand, the SOEC will be test-fitted with respective wiring and piping. Instrumentation and piping will be checked for leaks and quality. This must be completed before the vendor’s engineers arrive to observe the test plan, startup, and a collection of 50 hours of data. The vendor’s engineers will ensure their stack performed sufficiently in the 50-hour test to enable the progression to a 1000-hour test.

08 - HYDROGEN↗

NMPC for Setpoint Tracking Operation of a Solid Oxide Electrolysis Cell System

Solid oxide electrolysis cells (SOECs) are a promising technology to generate hydrogen through water electrolysis. However, intermittent renewable energy requires SOECs to transition between hydrogen production setpoints as the price of electricity fluctuates. A well-functioning control system is important to avoid cell degradation during setpoint tracking operation. In this work, we apply nonlinear model predictive control (NMPC) to an SOEC module and supporting equipment and compare NMPC performance to classical PI control while ramping between hydrogen production setpoints. We find that these control methods provide similar performance in many metrics, but NMPC significantly reduces cell thermal gradients during the setpoint transition.

Allan, Douglas↗

Conditions for stable operation of solid oxide electrolysis cells: oxygen electrode effects

Solid oxide electrolysis cells (SOECs) convert renewable electricity to fuels with efficiency substantially higher than other electrolysis technologies. However, questions remain regarding degradation mechanisms that limit SOEC long-term stability. One of the key degradation mechanisms is oxygen electrode delamination; although prior studies have improved the understanding of this mechanism, it is still difficult to predict how degradation depends on SOEC materials and operating conditions, i.e., temperature, voltage, and current density. Here we present a study aimed at developing a quantitative understanding of oxygen electrode delamination. Experimentally, a life test study of symmetric and full cells with yttria-stabilized zirconia (YSZ) electrolytes and Gd-doped ceria (GDC) barrier layers was done with three different perovskite oxygen electrode materials. Fracture was observed at the perovskite–GDC interface above a critical current density and below a critical operating temperature. A theory is presented that combines a calculation of the effective oxygen pressure across the electrolyte with an estimation of the pressure required for fracture. Fracture is correctly predicted for a critical oxygen partial pressure of ~7200 atm and an associated electrode overpotential of ~0.2 V, occurring at the electrode/GDC interface because of the relatively low perovskite fracture toughness. As a result, damage at the GDC/YSZ interface was also observed in some cases and explained by a peak in the oxygen pressure at this interface.

30 DIRECT ENERGY CONVERSION↗

Development of Stable Solid Oxide Electrolysis Cells for Low-Cost Hydrogen Production

The project objective was to demonstrate a solid oxide cell-based steam electrolysis stack that exhibits robustness, reliability, endurance, hydrogen purity, and produces hydrogen at elevated pressure of 2 to 3 bar. Innovative materials and processing methods were evaluated to improve degradation characteristics. Performance improvement focused on nearly all layers involved in the cell and stack assembly. Primary attention was paid to zirconia-ceria interface resistance control via sintering optimization and decrease in degradation from the oxygen electrode by evaluating low strontium (Sr) or Sr-free composition for both the oxygen electrode and current collection layer. Stack robustness was addressed by validating redox tolerance of fuel electrode, confirming capability of cells to survive repeated thermal cycles, studying the effect of pressure on performance and degradation, evaluating the effect of contamination on fuel and oxygen electrode performance and degradation, and identifying mitigation strategies to improve performance. The characterization included evaluation of electrochemical performance and stability followed by microstructural analysis. At the cell level, performance and stability improvements were achieved by incorporating a Sr-free oxygen electrode and a denser oxygen electrode barrier layer. At the stack level, pressurized operation reduces demand on first stage compression, the redox tolerant fuel electrode mitigates risk from service interruptions, and improvements to interconnect coating alleviate chromium (Cr) contamination effects. The denser barrier layer was achieved by adding a sintering aid to the samaria-doped ceria (SDC) composition that reduced sintering temperature by 150 °C. The resulting density was on par with the baseline SDC barrier layer density and the lower sintering temperature resulted in less resistive phase formation during sintering. Button cell tests did not demonstrate a change in performance when exposed to silicon (Si) or manganese (Mn) impurities to the fuel electrode and Cr impurity to the oxygen electrode. More detailed study however is warranted. The project addressed SOEC performance and stability at the cell and stack levels through a systematic approach to known sources of degradation that were combined and tested in three stack tests using an electrolyte supported cell design to allow for evaluation of a variety of fuel and oxygen electrode compositions. STK-82 and STK-83 had identical compositions. STK-100 incorporated the best materials and processing variables developed under this and concurrent projects, and was tested at elevated pressure in steam electrolysis. • STK-82 recovered performance after redox and thermal cycling, demonstrating the robustness of the stack and seals. It exhibited stable performance in testing for 500 hours in SOEC mode, followed by 300 hours of cycling between SOEC and SOFC tests. Degradation during SOEC operation was 1.8 %/ 1,000 hours. • STK-83 generated hydrogen at >80% steam conversion, and oxygen above 98.5 % purity during pressurized operation. Both hydrogen and oxygen were generated at 3 barg pressure without the use of a pressure vessel. In addition to balanced pressure, electrolysis operation at 1 bar differential pressure across anode and cathode was also demonstrated to substantial the robustness of the cell and seal. • STK-100 measured at initial ambient pressure conditions showed an area specific resistance of 1.1 ohm-cm 2 , and STK-83 had 1.3 ohm-cm 2 .

08 HYDROGEN↗

Leak test for solid oxide fuel cells and solid oxide electrolysis cells

A simple, fast, and economical alcohol penetration method for assessing the solid oxide cell to metal window frame seal in a typical planar design is presented. An alcohol such as ethanol or isopropanol is placed into the cavity of a cell sealed to the window frame. Within 3–5 min, one can determine if the glass seal is hermetic by visual observation along the seal edges on the side of the sealed frame. Cross bubbling and open circuit voltage methods for determining whether the seal failed or cracked at high temperature after final stack firing are also discussed.

25 ENERGY STORAGE↗

Development of High Performance Intermediate Temperature Proton-conducting Solid Oxide Electrolysis Cells

Steam electrolysis by solid oxide fuel cell technology, known as SOEC, is considered the most efficient and cost effective option for hydrogen production from renewable sources. By using proton-conducting electrolyte, the SOEC operating temperature can be reduced from over 800oC to below 600oC. Technical barriers associated with the conventional oxygen-ion conducting SOECs, such as hydrogen separation from water, oxidation of steam electrode, and instability of oxygen electrode, can be largely mitigated. In this report, an intermediate temperature (400-600°C) electrolysis technology was developed where a novel proton-conductor and a triple-conducting oxide were used as the electrolyte and anode, respectively. The electrolysis cell demonstrated excellent performance and durability at intermediate temperatures, promising a new prospective for next-generation steam electrolysis.

08 HYDROGEN↗

Progress in metal-supported solid oxide electrolysis cells: A review

There is increasing global interest in using solid oxide electrochemical cells to perform electrolysis. Metal-supported solid oxide electrolysis cells (MS-SOEC) are being developed with stainless steel and Ni-based supports. Additionally, the use of porous metal to support the electrochemically-active layers is anticipated to improve mechanical strength, decrease cost, and increase tolerance to aggressive operating conditions, including rapid thermal excursions. This review summarizes and analyzes the previous decade of progress in MS-SOEC development, and identifies critical needs for future work.

08 HYDROGEN↗

High performing triple-conductive Pr 2 NiO 4+δ anode for proton-conducting steam solid oxide electrolysis cell

The development of proton-conducting solid oxide electrolysis cells for the intermediate-temperature range application is largely hindered by the limited choice of adequate anode materials. In this study, the popular solid oxide fuel cell cathode material Pr 2 NiO 4+δ (PNO) is investigated as the anode for the electrolysis cell, considering its proton-conducting ability. The introduction of protons into the PNO lattice is confirmed through insertion-induced conductivity variation measurements. Good chemical compatibility is verified between PNO and BaZr 0.2 Ce 0.6 Y 0.2 O 3–δ (BZCY) proton-conducting electrolyte. Excellent catalytic activity towards water splitting is observed for the PNO–BZCY composite anode, 0.52 Ω cm 2 for 550 °C, 0.057 Ω cm 2 for 700 °C. The water-splitting process is disclosed by impedance spectroscopy measured under different conditions. Due to proton conduction in PNO, the PNO surface is activated for electrochemical reactions. The non-charge transfer processes account little to the electrode resistance. The performance of the PNO–BZCY anode is determined by two charge transfer processes whose kinetics are governed the electrolyzing potential. This charge transfer-limiting nature is relatively benign since the electrode resistance has been found to exponentially reduce with increasing overpotential. Cathode-supported Ni–BZCY//BZCY//PNO–BZCY thin film electrolyte single cells are fabricated and characterized. ~95% current efficiency is confirmed. At 700 °C, a current density of 977 mA cm –2 is achieved at a 1.3 V electrolyzing potential, e.g. 0.37 V overpotential, which is one of the best performances of proton-conducting steam electrolysis cells so far. The PNO–BZCY anode accounts only for 16% of the overall polarization resistance at 700 °C. Furthermore, these findings prove that the triple-conductive PNO is a promising anode material for proton-based steam electrolysis cells.

25 ENERGY STORAGE↗

Assessment of Protective Coatings for Metal-Supported Solid Oxide Electrolysis Cells

Green hydrogen is essential to achieving carbon neutrality, and solid oxide electrolysis cells can produce hydrogen using renewable power and waste heat. Insufficient long-term durability of solid oxide electrolysis cells has impeded their commercialization. Here, coatings in the porous stainless steel support of metal-supported solid oxide electrolysis cells (MS-SOECs) are used to dramatically improve their performance and durability. The long-term degradation rate of uncoated MS-SOECs is highly dependent on the current density, with the fastest degradation occurring at the highest current density tested, 0.5 A cm -2 . At this current density, coatings are quite effective. Three protective coatings, Co 3 O 4 deposited by atomic layer deposition (ALD), Co 3 O 4 deposited by electroplating deposition (ED), and CuMn 1.8 O 4 (CMO) deposited by electrophoretic deposition (EPD), are explored to enhance the performance of MS-SOECs with La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 -Sm 0.2 Ce 0.8 O 3 (LSCF-SDC) as the oxygen catalyst and SDC-Ni as the fuel catalyst. The initial average current density at 1.4 V is increased with coatings. It is 0.83 mA cm -2 for the ALD cells, 1.05 mA cm -2 for the ED cells, and 1.13 mA cm -2 for the EPD cells, compared to 0.65 mA cm -2 for the bare cells at 700 °C with 50% H 2 -50% H 2 O. The degradation rate over 1000 h of continuous operation is reduced from 36% to 26%, 27%, and 19% kh -1 with the three coatings, respectively. Furthermore, these improvements are ascribed to reduced Cr poisoning on the oxygen catalyst, which is one of the primary degradation modes for this type of MS-SOEC.

25 ENERGY STORAGE↗

Crack Growth Rate at Oxygen Electrode/Electrolyte Interface in Solid Oxide Electrolysis Cells Predicted by Experiment Coupled Multiphysics Modeling

Solid oxide electrolysis cell (SOEC) is a very efficient hydrogen production technology, but the cell degradation is a serious limiting factor for its long-term implementation. Oxygen electrode (OE) delamination is reported to be the critical degradation mechanism. In this study, we present a methodology to understand the delamination failure of the OE due to chemical stress in a better perspective. Several OE configurations were tested: baseline strontium-doped lanthanum cobalt iron oxide (LSCF) single layer design and tantalum-doped strontium cobalt oxide (SCT) - LSCF bilayer designs with different SCT loadings. An electro-chemo-mechanical model is developed to associate the electrochemical behavior of the cell with solid mechanics for calculating crack growth of the cell during long term test. The bilayer configuration with SCT 20 wt% has better performance as it survived in the long-term life test with the least crack length. This study implies that an additional nano-coating of SCT over the OE have improved the species transport and oxygen evolution with reduced chemical stress. As the operating current density decreases, it takes longer time for the cell to reach the delamination with the same critical crack length of 6.5 μ m (∼93% of the electrode/electrolyte interface length). Finally, it was concluded that chemical stress plays a significant role in interface delamination failure, however it may not be the only source of stresses at the interface.

08 HYDROGEN↗

A real-time multiphysics model of a pressurized solid oxide electrolysis cell (SOEC) for cyber-physical simulation

Solid oxide electrolysis cells (SOEC) can play important roles in integrated energy systems (IES) as the hydrogen production hub and the resilience energy hub. When tied to a microgrid with high renewable penetration, the SOEC is subjected to rapid load transitions in response to the intermittent renewable generations that occur not only in diurnal cycles but also in short timeframes (e.g., sub-minute). The cyber-physical simulation approach can derisk operability research but requires a real-time dynamic SOEC model. In the present work, a real-time multiphysics model for pressurized SOEC is developed and validated in the pressure range from 1.4 to 8bar. Further, the accuracy of the single repeating unit (SRU) assumption in SOEC stack simulation is quantified. A guidance of more than 45 cells in one SOEC stack is recommended to safely apply the SRU assumption. Modeling results suggest that at a given current density, more power is consumed by SOEC at elevated operating pressures. The anode air and cathode stream have major impacts on thermal management, highlighting the potential benefit of integrating SOEC with other thermal processes in IES. To achieve high hydrogen production efficiency, the SOEC could operate at the maximum endothermic point to maximize the use of thermal energy. The real-time execution of the developed SOEC model is also demonstrated, which only takes 0.1% of the fixed time step of 5ms. The developed model establishes the basis for cyber-physical simulation of SOEC hybrid systems.

25 ENERGY STORAGE↗

Dynamic operation of metal-supported solid oxide electrolysis cells

Symmetric-structure metal-supported solid oxide fuel cells and electrolysis cells (MS-SOFCs, MS-SOECs) offer several advantages over conventional solid oxide cells, including the use of inexpensive materials, high mechanical strength, and rapid ramp-up ability. Aggressive operation of MS-SOCs in fuel cell mode is well-established, including extremely fast start-up, redox tolerance, and imbalanced pressure. Here, we extend dynamic operation to MS-SOCs in SOEC mode with high steam content for both small button cells and a large rectangular cell, including: steam cycling, thermal cycling, redox cycling and power cycling. Steam cycling entailed switching between 3:97 and 50:50 steam:hydrogen ratio. For thermal cycling, the temperature was rapidly varied between 150°C and 700°C for 50 cycles. Redox cycling involved switching the steam side gas between 50 % humidified H 2 and 50 % humidified N 2 for 5 cycles. Power cycling was performed by operating the cell under variable current density, resulting in cell voltage between 1.3V and 2.8V. Degradation rates for each testing strategy were compared to a baseline cell, and found to be similar. In conclusion, the excellent tolerance to dynamic operation increases confidence that MS-SOECs will be compatible with dynamic or intermittent renewable resources.

08 HYDROGEN↗

Infiltrated electrodes for metal supported solid oxide electrolysis cells

Metal-supported solid oxide cells (MSOCs) are an alternative to conventional solid oxide cells (SOCs) based on ceramic cermets, offering lower material costs and higher operational flexibility. In this study symmetric MSOCs with infiltrated electrodes are explored for steam electrolysis operation to understand the underlying operation and degradation principles and suggest a direction for future MSOCs development. Two different fuel electrode backbones are used: an electronically-conductive lanthanum strontium co-doped iron nickel titanate (LSFNT) infiltrated with cerium-gadolinium oxide (CGO), or an ionic conductive zirconia based backbone (10ScYSZ) infiltrated with Ni:CGO. At the oxygen side, the backbone is 10ScYSZ, which is infiltrated with lanthanum-strontium co-doped cobalt oxide (LSC), or praseodymium oxide as cobalt-free alternative for comparison. This study suggests that the backbone electronic conductivity is key for good electrochemical performance as well as for boosting cell durability. Highly electronically conductive nanoparticles, especially nickel, were observed to irreversibly agglomerate driven by thermal conditions, whereas CGO proved to be a very stable electrocatalyst. At the fuel side, CGO (LSFNT) electrode showed lower ASR and degradation rate than Ni:CGO(ScYSZ) configuration with measured values of 0.50 Ω cm2 and 11 %/1000 h (at 0.60 A/cm2), and 0.70 Ω cm2 and 26 %/1000 h (at 0.50 A/cm2) at 1.30 V, respectively (700 °C, 50 % steam in hydrogen at the fuel side and air at the oxygen electrode side, LSC(ScYSZ) oxygen electrode).

25 ENERGY STORAGE↗