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.     

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.     

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.     

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.     

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.     

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.     

Transient operation of a solid oxide electrolysis cell

In order to investigate the transient behaviour of a solid oxide electrolysis cell, tests were carried out on a single SOEC both under steady-state and transient conditions for 600 h. Steady-state operation was performed at the reference current of −20 A, corresponding to the thermoneutral voltage (1.28 V), whereas transient tests consisted in 1800 square waves applied over 140 cumulated hours, with a current of −1 A and −20 A as well as 0 A and −20 A. Independently from the operating conditions, the measured voltage degradation rate of 5% (70 mV)/1000 h was stable for the entire experiment. Consequently, it was concluded that an SOEC can be operated under on–off conditions with no increase of the degradation rate. This result paves the way for modular operation of a high temperature electrolyser fed with intermittent electrical energy.     

Recent anode advances in solid oxide fuel cells

Solid oxide fuel cells (SOFCs) are electrochemical reactors that can directly convert the chemical energy of a fuel gas into electrical energy with high efficiency and in an environment-friendly way. The recent trends in the research of solid oxide fuel cells concern the use of available hydrocarbon fuels, such as natural gas. The most commonly used anode material Ni/YSZ cermet exhibits some disadvantages when hydrocarbons were used as fuels. Thus it is necessary to develop alternative anode materials which display mixed conductivity under fuel conditions. This article reviews the recent developments of anode in SOFCs with principal emphasis on the material aspects. In addition, the mechanism and kinetics of fuel oxidation reactions are also addressed. Various processes used for the cost-effective fabrication of anode have also been summarized. Finally, this review will be concluded with personal perspectives on the future research directions of this area.     

A simple analysis of current collection in tubular solid oxide fuel cells

A transmission line analysis is presented for the axial current collection in tubular solid oxide fuel cells (SOFC). Closed form analytical solutions are obtained for two modes of current collection: (1) Current collection at one end. (2) Current collection across opposite ends. The analysis shows that cell resistance is lower for current collection at one end compared to that at the opposite ends, with the best case scenario being current collection at both ends. In addition, the analysis shows that for the case of tubular cells, performance may not indefinitely increase with increasing temperature. Experimental data are presented on planar and tubular cells that demonstrate significant differences in temperature dependence. It is projected that under certain conditions, performance of tubular cells may actually decrease with increasing temperature. A design of tubular cells with spines which can substantially lower current collection losses is described.     

The effect of gas compositions on the performance and durability of solid oxide electrolysis cells

High-temperature electrolysis with various gas compositions has been performed to investigate the effects of the hydrogen partial pressure and the humidity generated by the steam electrode on the performance and durability of solid oxide electrolysis cells. The power density of the button cell used in this research is 0.48 W cm⁻² at 750 °C, and the flow rates of the air and humidified hydrogen are 100 cc min⁻¹. By changing the flow ratio of H₂:Ar:H₂O(g) from 10:0:4 to 1:9:4, the cell's OCV decreases from 0.973 V to 0.877 V, and the charge transfer resistance increases from 1.126 Ω cm² to 1.645 Ω cm². The close relationship between the conversion efficiency of high-temperature electrolysis and steam composition is evident in the increase in the cell's charge transfer resistance from 0.381 Ω cm² to 1.056 Ω cm² as the steam content changed from 40 vol% to 3 vol%. Although the electrochemical splitting of water is stimulated in the short term by excessive steam flow, the Ni-YSZ electrodes have been damaged by the steam electrode's low H₂ partial pressure. Consequently, the steam electrode's gas composition must be optimized in the long-term because of the trade-off between performance and durability, which depends on the water concentration of the steam electrodes.