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Dabadghao, V., D.A. Allan, M. Li, J.C. Eslick, J. Ma, S.E. Zitney, D. Bhattacharyya, and L.T. Biegler, “Nonlinear Model Predictive Control for Solid-Oxide Electrolysis Cell Systems,” AIChE 2022 Annual Meeting, Phoenix, AZ, November 13-18 (2022).
Direct CO 2 electrolysis using solid oxide electrolysis cells (CO 2 -SOECs) holds promise to efficiently convert carbon dioxide to carbon monoxide and oxygen. Cathodes with desirable catalytic activity and chemical stability play a critical role in the development of direct CO 2 -SOECs. Although Sr 2 Fe 1.5 Mo 0.5 O 6–δ (SFM) has exhibited promise for direct CO 2 -SOECs due to its redox stability, it suffers from insufficient activity for the CO 2 reduction reaction (CO 2 RR). Here we report interface engineering of nanosized Pr 6 O 11 on the SFM cathode obtained through infiltration to promote the CO 2 RR performance for direct CO 2 -SOECs. The effect of Pr 6 O 11 loading on the performance of the CO 2 RR is systematically investigated. At 800 °C, the current density of the Pr 6 O 11 infiltrated SFM cathode with an optimum Pr 6 O 11 loading of 14.8 wt% reaches 1.61 A cm –2 at 1.5 V, more than double that of the SFM cathode (0.76 A cm –2 ) under the same operating conditions. X-ray photoelectron spectroscopy (XPS) characterization and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis indicate that the adsorption ability of CO 2 on the SFM cathode has been significantly improved by the formation of Pr 6 O 11 . Temperature-programmed desorption (TPD) of CO 2 measurements further manifest that a 14.8 wt% Pr 6 O 11 -SFM cathode has better CO desorption capacity. In addition, polarization resistance of the SFM cathode has significantly decreased with the addition of Pr 6 O 11 . Three-electrode measurement was used to analyze the improved electrode kinetics. Finally, these results demonstrate that the formation of Pr 6 O 11 in the SFM cathode through infiltration is a promising approach for increasing CO 2 RR activity for CO 2 -SOECs.
The objective of this study is to establish a detailed techno-economic analysis to assess the effectiveness of incremental technology improvements needed for solid oxide electrolysis cell (SOEC) technology to achieve the U.S. DOE’s Hydrogen Shot goal of hydrogen production at less than $1 per kilogram. The pathway considers incremental technology improvements to key system parameters, with system performance and cost assessed for each pathway step. Briefly, the steps include cell voltage degradation rate improvements, operational current density increases, operating temperature reduction, improved steam utilization, increased system capacity factor, and reduced cell/stack capital costs. Each step is assessed at both atmospheric and pressurized (8 bar) operating conditions. To supplement assessment at each of these discrete stepwise improvements, sensitivity studies are conducted to understand the relative impact of each parameter and identify avenues for additional cost reductions. System efficiency and levelized costs of hydrogen (LCOH) for each case are presented. For the end-of-pathway case, which includes all the incremental research and development improvements, the cost of hydrogen produced is reduced by 50 percent from the state-of-the-art case.
The Controls and Dynamics Technology Branch at NASA Glenn Research Center are interested in combining a solid oxide fuel cell (SOFC) to operate in conjunction with a gas turbine engine. A detailed engine model currently exists in the Matlab/Simulink environment. The idea is to incorporate a SOFC model within the turbine engine simulation and observe the hybrid system's performance. The fuel cell will be heated to its appropriate operating condition by the engine s combustor. Once the fuel cell is operating at its steady-state temperature, the gas burner will back down slowly until the engine is fully operating on the hot gases exhausted from the SOFC. The SOFC code is based on a steady-state model developed by The U.S. Department of Energy (DOE). In its current form, the DOE SOFC model exists in Microsoft Excel and uses Visual Basics to create an I-V (current-voltage) profile. For the project's application, the main issue with this model is that the gas path flow and fuel flow temperatures are used as input parameters instead of outputs. The objective is to create a SOFC model based on the DOE model that inputs the fuel cells flow rates and outputs temperature of the flow streams; therefore, creating a temperature profile as a function of fuel flow rate. This will be done by applying the First Law of Thermodynamics for a flow system to the fuel cell. Validation of this model will be done in two procedures. First, for a given flow rate the exit stream temperature will be calculated and compared to DOE SOFC temperature as a point comparison. Next, an I-V curve and temperature curve will be generated where the I-V curve will be compared with the DOE SOFC I-V curve. Matching I-V curves will suggest validation of the temperature curve because voltage is a function of temperature. Once the temperature profile is created and validated, the model will then be placed into the turbine engine simulation for system analysis.
Allan, D.A., V. Dabadghao, M. Li, J.C. Eslick, J. Ma, D. Bhattacharyya, S.E. Zitney, and L.T. Biegler, “NMPC for Setpoint Tracking Operation of a Solid Oxide Electrolysis Cell System,” Foundations of Computer Aided Process Operations / Chemical Process Control (FOCAPO/CPC 2023), San Antonio, TX, January 8-12 (2023).
Addressing the challenges posed by inferior electrochemical performance at low temperatures and the uncertain Faradaic efficiency (FE) represents a pivotal undertaking in the development of high performance and efficient proton-conducting solid oxide electrolysis cells (P-SOECs). In this work, a novel oxygen electrode material BaCo0.8Zr0.1Zn0.1O3-d (BCZZ) is first designed and synthesized. At 600 °C, P-SOECs with BCZZ oxygen electrode achieve an electrolysis current density of 1.98 A cm-2 with an ˜90% FE at 1.3 V. Utilizing 1-inch P-SOECs as a reliable platform, the effect of extrinsic operating conditions (i.e., steam concentration, voltage, current density, and temperature) and intrinsic properties of P-SOECs (i.e., electrolyte material and electrolyte thickness) on FE are further systemically investigated, both experimentally and theoretically.
Solid oxide electrochemical cells (SOECs) stand out as a highly promising clean energy technology that offers several benefits, showing significant potential to play a pivotal role in the transition towards a sustainable and low-carbon energy future. SOECs can efficiently convert the chemical energy stored in fuels to electricity in fuel cell mode, and produce various chemicals from abundant feedstocks (e.g., CO 2 , H 2 O) and intermittent solar/wind-based renewable electricity. Despite extensive efforts that have been devoted to designing novel materials and optimizing SOEC manufacturing processes, aiming to achieve enhanced energy efficiency, the current SOECs still suffer from poor performance, which is mainly due to the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics. To address this challenge, in this work, we have successfully designed an in situ formed hybrid oxygen electrode material (Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ ), which significantly improves the surface oxygen exchange coefficient and bulk oxygen-ion diffusion coefficient, enhancing the OER and ORR electrocatalytic activities. Further, the SOECs equipped with this newly developed oxygen electrode achieved exceptional performance for power generation using both hydrogen and propane as the fuels. At 750 °C, a peak power density of 2.4 W cm -2 was obtained with H 2 as the fuel. Additionally, the SOECs attain unprecedented performance in steam electrolysis mode. A current density of 4.4 A cm -2 was achieved at 1.3 V and 750 °C, which represents the highest performance among all yttria-stabilized zirconia (YSZ) electrolyte-based SOECs. The SOECs also deliver remarkable stability during the accelerated stability testing, highlighting the great potential of Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ as a high-performance oxygen electrode for next generation SOECs.
Abstract Porous buffer layers for anode-supported solid oxide fuel cells (SOFCs) have been investigated for many years with different thicknesses of the buffer layer in each study. In this work, micro-tubular SOFCs having samarium-doped ceria (SDC) and gadolinium-doped ceria (GDC) buffer layers are compared using the current–voltage technique, electrochemical impedance spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The thickness of the porous SDC and GDC buffer layer is investigated systematically with the thickness varying between 0.3 and 2.0 μm. The power density varies between 212 and 1004 mW/cm2 for samples having different SDC buffer layer thickness. Comparable changes occur for the SOFCs with a GDC buffer layer, but less variation in polarization losses resulted. Variation in electrochemical performance varies due to changes in ohmic resistance, cathode activation polarization, and interfacial reactions between the cathode and electrolyte materials.
Here, this study reports the catalytic activity of transition metal electrocatalysts (Co, Ni, and Cu) incorporated into Gd 0.1 Ce 0.9 O 1.95 (GDC10) cathodes for the electroreduction of CO 2 in solid oxide electrolyzer cells (SOECs). CO 2 electroreduction performance of cells having porous and non-infiltrated GDC10 cathodes was compared with the performance of cells containing transition metal electrocatalysts infiltrated into porous GDC10 cathodes at 750, 800, and 850°C. Results showed that cells with Co infiltrated cathodes had the best catalytic activity towards CO 2 electroreduction. Furthermore, these cells displayed good stability towards CO electroreduction, having a faradaic efficiency value close to 100% with insignificant voltage increase when tested for 48h at 750 and 850°C under the current densities of 0.2, and 0.4Acm -2 , respectively.
Rapid load transition is an essential requirement for integrated energy systems to maintain grid resilience as more renewable resources are added to the grid. Integrated solid oxide fuel cell - gas turbine (SOFC-GT) systems can provide high efficiency and low carbon emissions over a broad range of turndown. These hybrids also have the potential to enable rapid grid response. The challenge has been to demonstrate effective control strategies to manage load transitions. In the present study, a load transition of ~50% was achieved in 10 s using a novel but simple strategy. Power demand on the SOFC and the GT were ramped down concurrently. During this transition, the SOFC anode fuel was manipulated to maintain SOFC fuel utilization while the cathode inlet air flow and temperature were also manipulated to thermally protect the SOFC. This study was conducted using the Hybrid Performance (Hyper) facility at the National Energy Technology Laboratory (NETL) in a co-simulation environment with the Idaho National Laboratory (INL)'s grid-simulation. The load ramping strategy was tested using a hardware-based cyber-physical simulation methodology. The results demonstrate a high-fidelity representation of SOFC-GT hybrid dynamics and validation of the control strategy. Thermal and electrochemical transients indicated that the SOFC was well protected during rapid load turndown without violating operability constraints. This demonstration revealed the non-linear nature of tightly coupled SOFC-GT system components, especially the non-linear response of SOFC cathode air flow and inlet temperature controls. These results highlight the needs and challenges in developing adaptive automatic controls for autonomous rapid load transitions. This work demonstrates that SOFC-GT hybrids are a viable option to provide the fast-ramping characteristics essential to accommodate high levels of variable renewable power while maintaining grid resilience, reliability, and environmental performance. The results also demonstrate the utility of co-simulation in advancing the tightly-coupled integrated energy systems needed to meet goals for zero-carbon power generation.
As the aviation industry moves towards higher efficiency electrical power generation, all electric aircraft, or zero emissions and more quiet aircraft, fuel cells are sought as the technology that can deliver on these high expectations. The Hybrid Solid Oxide Fuel Cell system combines the fuel cell with a microturbine to obtain up to 70 percent cycle efficiency, and then distributes the electrical power to the loads via a power distribution system. The challenge is to understand the dynamics of this complex multi-discipline system, and design distributed controls that take the system through its operating conditions in a stable and safe manner while maintaining the system performance. This particular system is a power generation and distribution system and the fuel cell and microturbine model fidelity should be compatible with the dynamics of the power distribution system in order to allow proper stability and distributed controls design. A novel modeling approach is proposed for the fuel cell that will allow the fuel cell and the power system to be integrated and designed for stability, distributed controls, and other interface specifications. This investigation shows that for the fuel cell, the voltage characteristic should be modeled, but in addition, conservation equation dynamics, ion diffusion, charge transfer kinetics, and the electron flow inherent impedance should also be included.
As the aviation industry moves toward higher efficiency electrical power generation, all electric aircraft, or zero emissions and more quiet aircraft, fuel cells are sought as the technology that can deliver on these high expectations. The hybrid solid oxide fuel cell system combines the fuel cell with a micro-turbine to obtain up to 70% cycle efficiency, and then distributes the electrical power to the loads via a power distribution system. The challenge is to understand the dynamics of this complex multidiscipline system and the design distributed controls that take the system through its operating conditions in a stable and safe manner while maintaining the system performance. This particular system is a power generation and a distribution system, and the fuel cell and micro-turbine model fidelity should be compatible with the dynamics of the power distribution system in order to allow proper stability and distributed controls design. The novelty in this paper is that, first, the case is made why a high fidelity fuel cell mode is needed for systems control and stability designs. Second, a novel modeling approach is proposed for the fuel cell that will allow the fuel cell and the power system to be integrated and designed for stability, distributed controls, and other interface specifications. This investigation shows that for the fuel cell, the voltage characteristic should be modeled but in addition, conservation equation dynamics, ion diffusion, charge transfer kinetics, and the electron flow inherent impedance should also be included.
A material consisting of a barium calcium aluminosilicate glass reinforced with 4 weight percent of boron nitride nanotubes (BNNTs) has shown promise for use as a sealant in planar solid oxide fuel cells (SOFCs).
The variability of renewable energy sources poses challenges for reliable grid operation. Conventional thermal power sources, though reliable, often lack operational flexibility. Hybrid energy systems that integrate Solid Oxide Fuel cells (SOFC) with Internal Combustion Engines (ICE) offer a promising solution by achieving relatively higher efficiency and grid-following capability. This study investigates performance of a 100-kW pressurized SOFC-ICE hybrid cycle. In this configuration, unutilized SOFC fuel is used to drive the engine, with a turbocharger providing air supply and an external reformer generating syngas. System components were numerically modeled using MATLAB/SIMULINK for the SOFC and reformer, and EBSILON® for the ICE and balance of plant. Parametric studies varied fuel utilization (70-90%), reformer temperature (600 – 1000K), anode off-gas recirculation (0 – 70%), and current density (0.2 – 0.55 A/cm2). Results show that the SOFC and ICE operate as thermally independent topping and bottoming cycles, achieving peak efficiency of 62% under optimized conditions.
Nanopowders of La(0.6)Sr(0.4)CoO(3-x) (LSC) and Sm(0.5)Sr(0.5)CoO(3-x) (SSC) compositions, which are being investigated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFC) with La(Sr)Ga(Mg)O(3-x) (LSGM) as the electrolyte, were synthesized by low-temperature sol-gel method using metal nitrates and citric acid. Thermal decomposition of the citrate gels was followed by simultaneous DSC/TGA methods. Development of phases in the gels, on heat treatments at various temperatures, was monitored by x-ray diffraction. Solgel powders calcined at 550 to 1000 C consisted of a number of phases. Single perovskite phase La(0.6)Sr(0.4)CoO(3-x) or Sm(0.5)Sr(0.5)CoO(3-x) powders were obtained at 1200 and 1300 C, respectively. Morphological analysis of the powders calcined at various temperatures was done by scanning electron microscopy. The average particle size of the powders was approx.15 nm after 700 C calcinations and slowly increased to 70 to 100 nm after heat treatments at 1300 to 1400 C.
This study provides a combined experimental and computational investigation into the structure and impact of the cation interdiffusion layer that appears at the gadolinium doped ceria (GDC)/yttria stabilized zirconia (YSZ) interface in solid oxide electrolysis cells (SOECs). Scanning transmission electron microscopy (STEM) illustrates that a ∼0.4 μm interdiffusion layer (IDL) with an intermixed cation distribution and fine grain size forms upon sintering. STEM identifies that the interdiffusion layer exists in the cubic fluorite structure despite changes in cation composition. The interdiffusion layer microstructure formed during sintering does not change during SOEC testing at either 1.3V or heightened voltage pulse testing. Modeling predicts that ionic conductivity may decrease in the interdiffusion layer due to Coulombic trapping between mobile oxygen vacancies and excess Gd 3+ acceptor dopants. Yet, the density and continuous nature of the layer should benefit cell stability by substantially reducing the formation of SrZrO 3 , which is corroborated by STEM and Synchrotron X-ray diffraction (XRD). We conclude that the interdiffusion layer acts as a beneficial barrier to Sr diffusion, when operating in a regime where electrolyte void formation is not observed.
This work applies a multiscale mechanistic damage model developed for brittle ceramics and implemented in commercial finite element (FE) packages via user subroutines to study progressive damage in solid oxide fuel cells (SOFC) subjected to thermomechanical loading under normal operating and shutdown conditions including redox effects. The damage model captures the micromechanics of stiffness reduction due to material porosity change and microcracking and integrates the as-obtained stiffness reduction law into a continuum damage mechanics (CDM) formulation for the evolution of microcracks up to fracture. The volumetric “swelling” that occurs during redox is treated in constitutive modeling similarly to thermal expansion, but swelling strains are irreversible. Furthermore, this damage model was first validated through predictions of strength and stress-strain response for the SOFC electrode materials. Next, it has been applied to predict the potential for degradation in a generic planar SOFC stack with large active area cells. Multicell stack models were simulated in both co-flow and counter-flow configurations. In addition, a constant temperature redox cycle was also simulated to capture overall cell electrode damage due to volumetric swelling of the nickel (Ni)-based anode in the anode-supported cells.
The report “America’s Strategy to Secure the Supply Chain for a Robust Clean Energy Transition” lays out the challenges and opportunities faced by the United States in the energy supply chain as well as the federal government plans to address these challenges and opportunities. It is accompanied by several issue-specific deep dive assessments, including this one, in response to Executive Order 14017 “America’s Supply Chains,” which directs the Secretary of Energy to submit a report on supply chains for the energy sector industrial base. The Executive Order is helping the federal government to build more secure and diverse U.S. supply chains, including energy supply chains. This report is one of a series that supports the analysis of the energy industrial base called for in Executive Order 14017 on America’s supply chains (Exec. Order No. 14017, 2021). Specifically, it provides a review of the supply chain for water electrolyzers and fuel cells with a focus on polymer electrolyte membrane electrolyzer cells (PEMEC), polymer electrolyte membrane fuel cells (PEMFC), solid oxide electrolyzer cells (SOEC), and solid oxide fuel cells (SOFC). Water electrolysis and fuel cells are a nascent industry with little prior information related to supply chain needs and constraints. This report provides a preliminary assessment; further industry peer review and revisions are expected.