Hydrogen and synthetic fuel production using pressurized solid oxide electrolysis cells

Wind and solar power is troubled by large fluctuations in delivery due to changing weather. The surplus electricity can be used in a Solid Oxide Electrolyzer Cell (SOEC) to split CO₂ + H₂O into CO + H₂ (+O₂). The synthesis gas (CO + H₂) can subsequently be catalyzed into various types of synthetic fuels using a suitable catalyst. As the catalyst operates at elevated pressure the fuel production system can be simplified by operating the SOEC at elevated pressure. Here we present the results of a cell test with pressures ranging from 0.4 bar to 10 bar. The cell was tested both as an SOEC and as a Solid Oxide Fuel Cell (SOFC). In agreement with previous reports, the SOFC performance increases with pressure. The SOEC performance, at 750 °C, was found to be weakly affected by the pressure range in this study, however the internal resistance decreased significantly with increasing pressure.     

Electrochemical reduction of CO2 in solid oxide electrolysis cells

This paper describes results on the electrochemical reduction of carbon dioxide using the same device as the typical planar nickel-YSZ cermet electrode supported solid oxide fuel cells (H₂-CO₂, Ni-YSZ|YSZ|LSCF-GDC, LSCF, air). Operation in both the fuel cell and the electrolysis mode indicates that the electrodes could work reversibly for the charge transfer processes. An electrolysis current density of ≈1 A cm⁻² is observed at 800 °C and 1.3 V for an inlet mixtures of 25% H₂-75% CO₂. Mass spectra measurement suggests that the nickel-YSZ cermet electrode is highly effective for reduction of CO₂ to CO. Analysis of the gas transport in the porous electrode and the adsorption/desorption process over the nickel surface indicates that the cathodic reactions are probably dominated by the reduction of steam to hydrogen, whereas carbon monoxide is mainly produced via the reverse water gas shift reaction.     

Integration of solid oxide electrolyser,entrained gasification,and Fischer-Tropsch process for synthetic diesel production: Thermodynamic analysis

A novel integrated renewable-based energy system for production of synthetic diesel is proposed and simulated in this study. This system merges solid oxide electrolyser (SOE), entrained gasification (EG) and Fischer-Tropsch (FT) technologies. Two case scenarios are considered here. In the first case, the electrolyser unite produce syngas through co-electrolysis of steam and carbon dioxide, while in the second case only steam is electrolyzed. The effects of SOEC and EG operating pressure and temperatures on the system performance in each case are investigated and compared. It is shown that the operating condition of electrolyser subsystem has a more considerable effect on the performance of the integrated system as compared to the gasification subsystem. Also waste heat recovery results in about 43 and 2 percentage point increase in energy and exergy efficiency, respectively. It is also shown that internal recovering of oxygen has the best effect on the system performance.     

Hydrogen production performance of 3-cell flat-tubular solid oxide electrolysis stack

Flat-tubular solid oxide electrolysis cells have been manufactured with a ceramic interconnector in a body to minimize the stack volume and eliminate metallic components. The NiO-YSZ supports are prepared by the extrusion method, and the other cell components, which included the electrolyte, air electrode, and ceramic interconnector, are fabricated by slurry coating methods. The active area of a single cell is 30 cm², and the gas tightness of the stack is checked in the range below 2 bars. The effects of the operating conditions on the performance of a solid oxide electrolysis stack are investigated using electrochemical impedance spectroscopy and the I-V test. Consequently, it is confirmed that sufficient steam content stimulates the electrochemical splitting of water and decreases the activation energy for water electrolysis at a high temperature. In our 3-cell stack test, the hydrogen production rate is 4.1 lh⁻¹, and the total hydrogen production was 144.32 l during 37.1 h of operation.     

System level heat integration and efficiency analysis of hydrogen production process based on solid oxide electrolysis cells

The solid oxide electrolysis cells (SOEC) technology is a promising solution for hydrogen production with the highest electrolysis efficiency. Compared with its counterparts, operating at high temperature means that SOEC requires both power and heat. To investigate the possibility of coupling external waste heat with the SOEC system, and the temperature & quantity requirement for the external waste heat, a universal SOEC system operating at atmospheric pressure is proposed, modeled and analyzed, without specific waste heat source assumption such as solar, geothermal or industrial waste heat. The SOEC system flow sheet is designed to create opportunity for external waste heat coupling. The results show that external waste heat is required for feed stock heating, while the recommended coupling location is the water evaporator. The temperature of the external waste heat should be above 130 °C. For an SOEC system with 1 MW electrolysis power input, the required external waste heat is about 200 kW. When the stack operates at thermoneutral state and 800 °C, the specific energy consumption is 3.77 kWh/Nm³-H₂, of which electric power accounts for 84% (3.16 kWh/Nm³-H₂) and external waste heat accounts for 16% (0.61 kWh/Nm³-H₂). The total specific energy consumption remains almost unchanged when operating the SOEC stack around the thermoneutral condition.     

Thermodynamic analysis of an integrated power generation system driven by solid oxide fuel cell

A new integrated power generation system driven by the solid oxide fuel cell (SOFC) is proposed to improve the conversion efficiency of conventional energy by using a Kalina cycle to recover the waste heat of exhaust from the SOFC-GT. The system using methane as main fuel consists an internal reforming SOFC, an after-burner, a gas turbine, preheaters, compressors and a Kalina cycle. The proposed system is simulated based on the developed mathematical models, and the overall system performance has been evaluated by the first and second law of thermodynamics. Exergy analysis is conducted to indicate the thermodynamic losses in each components. A parametric analysis is also carried out to examine the effects of some key thermodynamic parameters on the system performance. Results indicate that as compressor pressure ratio increases, SOFC electrical efficiency increases and there is an optimal compressor pressure ratio to reach the maximum overall electrical efficiency and exergy efficiency. It is also found that SOFC electrical efficiency, overall electrical efficiency and exergy efficiency can be improved by increasing air flow rate. Also, the largest exergy destruction occurs in the SOFC followed by the after-burner, the waste heat boiler, the gas turbine. The compressor pressure ratio and air flow rate have significant effects on the exergy destruction in some main components of system.     

Thermodynamic analysis of interactions between Ni-based solid oxide fuel cells (SOFC) anodes and trace species in a survey of coal syngas

A thermodynamic analysis was conducted to characterize the effects of trace contaminants in syngas derived from coal gasification on solid oxide fuel cell (SOFC) anode material. The effluents from 15 different gasification facilities were considered to assess the impact of fuel composition on anode susceptibility to contamination. For each syngas case, the study considers the magnitude of contaminant exposure resulting from operation of a warm gas cleanup unit at two different temperatures and operation of a nickel-based SOFC at three different temperatures. Contaminant elements arsenic (As), phosphorous (P), and antimony (Sb) are predicted to be present in warm gas cleanup effluent and will interact with the nickel (Ni) components of a SOFC anode. Phosphorous is the trace element found in the largest concentration of the three contaminants and is potentially the most detrimental. Poisoning was found to depend on the composition of the syngas as well as system operating conditions. Results for all trace elements tended to show invariance with cleanup operating temperature, but results were sensitive to syngas bulk composition. Synthesis gas with high steam content tended to resist poisoning.     

Theoretical study on pressurized operation of solid oxide electrolysis cells

In this paper the influence of pressure on the performance of solid oxide electrolysis cells is theoretically analyzed in a pressure range between 0.05 and 2 MPa. A previously validated electrochemical model of a solid oxide fuel cell stack is used to predict electrolysis behavior. The effect of pressure on thermodynamics, kinetics and gas diffusion is discussed. It is shown that thermodynamics are negatively influenced by an increase in pressure whereas kinetics and gas transport are improved. Overall pressure effects are therefore only small. At low current density the electrolysis cell shows better performance at low pressure whereas performance improves with pressure at high current densities.     

Gas transport in hydrogen electrode of solid oxide regenerative fuel cells for power generation and hydrogen production

To further develop solid oxide regenerative fuel cell (SORFC) technology, the effect of gas diffusion in the hydrogen electrode on the performance of solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells (SOECs) is investigated. The hydrogen electrode-supported cells are fabricated and tested under various operating conditions in both the power generation and hydrogen production modes. A transport model based on the dusty-gas model is developed to analyze the multi-component diffusion process in the porous media, and the transport parameters are obtained by applying the experimentally measured limiting current data to the model. The structural parameters of the porous electrode, such as porosity and tortuosity, are derived using the Chapman–Enskogg model and microstructural image analysis. The performance of an SOEC is strongly influenced by the gas diffusion limitation at the hydrogen electrode, and the limiting current density of an SOEC is substantially lower than that of an SOFC for the standard cell structure under normal operating conditions. The pore structure of the hydrogen electrode is optimized by using poly(methyl methacrylate) (PMMA), a pore-forming agent, and consequently, the hydrogen production rate of the SOEC is improved by a factor of greater than two under moderate humidity conditions.     

Long-term tests of a Jülich planar short stack with reversible solid oxide cells in both fuel cell and electrolysis modes

A two-cell planar stack in the Jülich F-design with solid oxide cells has been built and the reversible operation between fuel cell and electrolysis modes has been demonstrated. The cells were anode supported cells (ASC) with yttria-stabilized zirconia (YSZ) electrolytes, Ni/YSZ hydrogen electrodes and perovskite oxygen electrodes with lanthanum strontium cobalt ferrite (LSCF). This paper summarizes and discusses the preliminary experimental results on the long-term aging tests of the reversible solid oxide planar short stack for fuel cell operation (4000 h) at a current density of 0.5 A cm⁻² which shows a degradation of 0.6% per 1000 h and for steam electrolysis operation (3450 h) and co-electrolysis operation of CO₂ and H₂O (640 h) under different current densities from −0.3 to −0.875 A cm⁻² which show different degradation rates depending on current density and on steam or co-electrolysis.     

Thermodynamic modeling of an integrated biomass gasification and solid oxide fuel cell system

An integrated process of biomass gasification and solid oxide fuel cells (SOFC) is investigated using energy and exergy analyses. The performance of the system is assessed by calculating several parameters such as electrical efficiency, combined heat and power efficiency, power to heat ratio, exergy destruction ratio, and exergy efficiency. A performance comparison of power systems for different gasification agents is given by thermodynamic analysis. Exergy analysis is applied to investigate exergy destruction in components in the power systems. When using oxygen-enriched air as gasification agent, the gasifier reactor causes the greatest exergy destruction. About 29% of the chemical energy of the biomass is converted into net electric power, while about 17% of it is used to for producing hot water for district heating purposes. The total exergy efficiency of combined heat and power is 29%. For the case in which steam as the gasification agent, the highest exergy destruction lies in the air preheater due to the great temperature difference between the hot and cold side. The net electrical efficiency is about 40%. The exergy combined heat and power efficiency is above 36%, which is higher than that when air or oxygen-enriched air as gasification agent.     

Analysis of pressurized operation of 10 layer solid oxide electrolysis stacks

High temperature steam electrolysis using solid oxide electrolysis cell (SOEC) technology can provide hydrogen as fuel for transport or as base chemical for chemical or pharmaceutical industry. SOECs offer a great potential for high efficiencies due to low overpotentials and the possibility for waste heat use for water evaporation. For many industrial applications hydrogen has to be pressurized before being used or stored. Pressurized operation of SOECs can provide benefits on both cell and system level, due to enhanced electrode kinetics and downstream process requirements. Experimental results of water electrolysis in a pressurized SOEC stack consisting of 10 electrolyte supported cells are presented in this paper. The pressure ranges from 1.4 to 8 bar. Steady-state and dynamically recorded U(i)-curves as well as electrochemical impedance spectroscopy (EIS) were carried out to evaluate the performance of the stack under pressurized conditions. Furthermore a long-term test over 1000 h at 1.4 bar was performed to evaluate the degradation in exothermic steam electrolysis mode. It was observed that the open circuit voltage increases with higher pressure due to well-known thermodynamic relations. No increase of the limiting current density was observed with elevated pressure for the ESC-stacks (electrolyte supported cell) that were investigated in this study. The overall and the activation impedance were found to decrease slightly with higher pressure. Within the impedance studies, the ohmic resistance was found to be the most dominant part of the entire cell resistance of the studied electrolyte supported cells of the stack. A constant current degradation test over 1000 h at 1.4 bar with a second stack showed a voltage degradation rate of 0.56%/kh.     

Deficiency of hydrogen production in commercialized planar Ni-YSZ/YSZ/LSM-YSZ steam electrolysis cells

Deficient, or non-linear hydrogen production is for the first time experimentally observed in large-scale planar Ni-YSZ/YSZ/LSM-YSZ steam electrolysis cells. The apparent coinciding of the concentration polarization and Faraday efficiency decrease at certain current density (?0.5Acm^?2 or -0.6Acm^?2 for selected steam content) indicates that steam starvation appears to affect the hydrogen production's linearity, which in essence the Ni/NiO redox process is believed to play a role in such normal SOEC operations. The SOEC survives 10h extreme polarization through electric conduction and oxygen vacancy transportation. Rational SOEC working mode is recommended accordingly. The present work is complementary for the general application of the Faraday's Law to estimate hydrogen production, and to further evaluate the SOEC's overall characteristics.     

A vanadium-doped BSCF perovskite for CO2 electrolysis in solid oxide electrolysis cells

CO₂ electrolysis through solid oxide electrolysis cells (SOECs) is a promising strategy for converting CO₂ to useful fuels and chemicals powered by renewable energy. Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) is a widely-investigated anode material of SOEC on account of its high and catalytic activity. However, its poor stability under CO₂ atmosphere limits its application as cathode in CO₂ electrolysis. Herein, we develop a vanadium-doped BSCF material Ba_0.5Sr_0.5(Co_0.8Fe_0.2)_1-xV_xO_3-δ (BSCFV_x) for SOEC cathode. The doping of V into B site of BSCF decreases the basicity of perovskite oxide and increases its stability under CO₂ atmosphere, thus improving the CO₂ electrolysis performance. Compared to BSCF, the cell of BSCFV_0.01 cathode shows a better tolerance to CO₂ and achieves 48.3% increase in current density at 1.6 V and 800 °C.     

Thermodynamic,exergoeconomic and exergoenvironmental analyses and optimization of a solid oxide fuel cell-based trigeneration system

This study proposes a trigeneration system based on solid oxide fuel cell (SOFC) for generating power, cooling and heating simultaneously. The system mainly contains a SOFC, a gas turbine (GT), an organic Rankine cycle (ORC), a steam ejector refrigerator (SER) and a heat exchanger. The thermodynamic, exergoeconomic and exergoenvironmental models of proposed trigeneration system are developed, and the effects of design parameters on system performances are analyzed. The results indicate that the system average product cost and environmental impact per unit of exergy increase with SOFC inlet temperature and working pressure, the pinch point temperature difference and evaporating pressure of Generator, while decrease with the current density of fuel cell. Finally, optimization is performed to achieve the optimal exergy-based performance. It is revealed that though the system exergy efficiency is decreased by 7.64% after optimization, the system average product cost and environmental impact per unit of exergy are significantly reduced.     

Model validation and performance analysis of regenerative solid oxide cells: Electrolytic operation

The use of regenerative, high temperature solid oxide cells (SOCs) as energy storage devices has the potential for round-trip efficiencies that are competitive with other storage technologies. The focus of the current study is to investigate regenerative SOC operation (i.e., working in both fuel cell and electrolysis modes) through a combination of modeling and numerical simulation. As an intermediate step, this paper focuses on the electrolysis mode and presents a dynamic cell model that couples the reversible electrochemistry, reactant chemistry, and the thermo-fluidic phenomena inside a cell channel. The model is calibrated and validated using available experimental and numerical data for button cells, single cells, and multi-cell stacks supplied with either steam or syngas. Parametric studies are also performed to show how the investigated parameters affect model validity. The results show that the present model can accurately simulate the electrolytic cell behavior, especially in the low current range, which is a favored operating point in practical systems. It is observed that improvements in stack-level model precision require further investigation to better represent the contact resistance of the stack components and to improve the estimation of the activation polarization throughout the operating envelope. It is also concluded that the CO₂ electrochemical reaction can be neglected when the concentration of the steam supplied to the cell is high enough to support the water–gas shift reaction.     

Electrochemical performance of solid oxide electrolysis cell electrodes under high-temperature coelectrolysis of steam and carbon dioxide

The SOEC electrodes during steam (H₂O) electrolysis, carbon dioxide (CO₂) electrolysis, and the coelectrolysis of H₂O/CO₂ are investigated. The electrochemical performance of nickel-yttria stabilised zirconia (Ni-YSZ), Ni-Gd_0.1Ce_0.9O_1.95 (Ni-GDC), and Ni/Ruthenium-GDC (Ni/Ru-GDC) hydrogen electrodes and La_0.8Sr_0.2MnO_3−δ-YSZ (LSM-YSZ), La_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ (LSCF), and La_0.8Sr_0.2FeO_3−δ (LSF) oxygen electrodes are studied to assess the losses of each electrode relative to a reference electrode. The study is performed over a range of operating conditions, including varying the ratio of H₂O/H₂ and CO₂/CO (50/50 to 90/10), the operating temperature (550-800 °C), and the applied voltage. The activity of Ni-YSZ electrodes during H₂O electrolysis is significantly lower than that for H₂ oxidation. Comparable activity for operating between the SOEC and solid oxide fuel cell (SOFC) modes is observed for the Ni-GDC and Ni/Ru-GDC. The overpotential of H₂ electrodes during CO₂ reduction increases as the CO₂/CO ratio is increased from 50/50 to 90/10 and further increases when the electrode is exposed to a 100% CO₂ (800 °C), corresponding to the increase in the area specific resistance. The electrodes exhibit comparable performance during H₂O electrolysis and coelectrolysis, while the electrode performance is lower in the CO₂-electrolysis mode. The activity of all the O₂ electrodes as an SOFC cathode is higher than that as SOEC anodes. Among these O₂ electrodes, LSM-YSZ exhibits the nearest to symmetrical behaviour.     

High efficiency process for the production of pure oxygen based on solid oxide fuel cell–solid oxide electrolyzer technology

This paper presents a novel system for production of pure oxygen based on the integration of a solid oxide fuel cell (SOFC) and a solid oxide electrolyzer (SOEC). In the proposed arrangement, the SOFC provides electricity, heat and H₂O in vapour phase to the SOEC which carries out the inverse reactions of the SOFC, that is the separation of H₂O into H₂ (used as a fuel for the SOFC) and O₂ (representing the yield of the system). Simulations carried out in different operating conditions show that when the integrated SOFC–SOEC device runs at low current densities (less than 1000 A m⁻²), pure oxygen can be generated with an electric consumption comparable to mid-size cryogenic air separation units, and significantly lower than small scale systems based on the PSA technology.