Durable SOC stacks for production of hydrogen and synthesis gas by high temperature electrolysis

Electrolysis of steam and co-electrolysis of steam and carbon dioxide was studied in Solid Oxide Electrolysis Cell (SOEC) stacks composed of Ni/YSZ electrode supported SOECs. The results of this study show that long-term electrolysis is feasible without notable degradation in these SOEC stacks. The degradation of the electrolysis cells was found to be influenced by the adsorption of impurities from the applied inlet gases, whereas the application of chromium containing interconnect plates and glass sealings do not seem to influence the durability when operated at 850 °C. Cleaning the inlet gases to the Ni/YSZ electrode resulted in operation without long-term degradation, and may therefore be a solution for operating these Ni/YSZ based SOEC stacks without degradation.     

Improved durability of SOEC stacks for high temperature electrolysis

An experimental study has been conducted at Idaho National Laboratory to demonstrate recent improvements in long-term durability of solid oxide electrolysis cells (SOEC) and stacks. Results of five stack tests are presented. Electrolyte-supported SOEC stacks were provided by Ceramatec Inc. and electrode-supported SOEC stacks were provided by Materials and Systems Research Inc. (MSRI), for these tests. Long-term durability tests were generally operated for durations of 1000 h or more. Stack tests based on technologies developed at Ceramatec and MSRI have shown significant improvement in durability in the electrolysis mode. Long-term degradation rates of 3.2%/khr and 4.6%/khr were observed for MSRI and Ceramatec stacks, respectively. One recent Ceramatec stack even showed negative degradation (performance improvement) over 1900 h of operation. Optimization of electrode and electrolyte materials, interconnect coatings, and electrolyte–electrode interface microstructures contribute to improve the durability of SOEC stacks.     

Steam electrolysis performance of intermediate-temperature solid oxide electrolysis cell and efficiency of hydrogen production system at 300 Nm h

The steam electrolysis performance of an intermediate-temperature solid oxide electrolysis cell (SOEC) was measured at 650 °C at various steam concentrations. The cell voltage decreased with increasing steam concentration, which was attributed to a decrease in the steam electrode polarization. The highest performance of the SOEC was 1.32 V at 0.57 A cm⁻². On the basis of the electrolytic characteristics of this cell, the efficiency of a hydrogen production system operating at a capacity of 300 N m³ h⁻¹ was estimated. The system efficiency reached a higher heating value (HHV standard) of 98% due to the effective recovery of thermal energy from exhaust gas.     

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.     

Enhanced steam electrolysis with exsolved iron nanoparticles in perovskite cathode

The sustainable supply of clean energy may depend on the hydrogen, which usually derives from steam electrolysis for SOEC. However, the current steam electrolysis using SOEC still faces many challenges, such as low catalytic efficiency, poor structural stability. We synthesize a series of La_0.6Sr_0.4Fe_xO_3-δ (LSF_x, x = 0.8–1.2) materials, utilizing in situ exsolved metal (Fe) nanoparticles to construct a metal-oxide interface to enhance the performance of steam electrolysis and coking resistance. The active metal-oxide interface can effectively improve the performance of steam electrolysis. The H₂ production reaches 4.52 mL min^?1 cm^?2 with the current efficiency of 97.81% at 1.6 V and 850 °C for the cell with LSF_1.1-Ce_0.8Sm_0.2O_3-δ cathode and anode. It shows excellent long-term stability and redox cycling capability after dozens of hours of operation. This research is of great significance for efficient hydrogen production.     

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.     

A promising strontium and cobalt-free air electrode Pr1-xCaxFeO3-δ for solid oxide electrolysis cell

A promising strontium and cobalt-free ferrite Pr_1-xCa_xFeO_3-δ (PCF, x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) has been synthesized successfully by glycine-nitrate combustion method and used as the air electrode of solid oxide electrolysis cell (SOEC) for steam electrolysis. The crystal structure and electricity conductivity of PCF are investigated in detail. According to the conductivity test, Pr_0.6Ca_0.4FeO_3-δ (PCF64) with higher conductivity is selected as the air electrode to preparing the single cell with structure of PCF64|GDC|SSZ|YSZ-NiO. Under SOFC mode, the maximum power density of the single cell is 462.93 mW cm⁻² at 800 °C with hydrogen as fuel. Under SOEC mode, the current density reaches 277.14 mA cm⁻² and the corresponding hydrogen production rates is 115.84 mL cm⁻² h⁻¹ at 800 °C at 1.3 V. In the 10 h short-term stability test, the cell shows good electrolysis stability.     

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.     

Solid oxide cells with cermet of silver and gadolinium-doped-ceria symmetrical electrodes for high-performance power generation and water electrolysis

A cermet of silver and gadolinium-doped-ceria (Ag-GDC) is investigated as novel symmetrical electrode material for (ZrO₂)_0.92(Y₂O₃)_0.08 (YSZ) electrolyte-supported solid oxide cells (SOCs) operated in fuel cell (SOFC) and electrolysis (SOEC) modes. The electrochemical performances are evaluated by measuring the current density-voltage characteristics and impedance spectra of the SOCs. The activity of hydrogen and air electrodes is investigated by recording overpotential versus current density in symmetrical electrode cells, respectively in hydrogen and air, using a three-electrode method. Conventional hydrogen electrode, Ni-YSZ, and oxygen electrode, LSCF (La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ)-GDC, are tested as comparison. The results show that, as an oxygen electrode, Ag-GDC is more active than LSCF-GDC in catalyzing both oxygen reduction reaction (ORR) in an SOFC and oxygen evolution reaction (OER) in an SOEC. As a hydrogen electrode, Ag-GDC is more active than Ni-YSZ in catalyzing hydrogen oxidation reaction (HOR) in an SOFC and hydrogen evolution reaction (HER) in an SOEC, especially in high steam concentration. An SOC with symmetrical Ag-GDC electrodes operated in a fuel cell mode, with 3% H₂O humidified H₂ as the fuel, displays a peak power density of 395 mWcm^?2 at 800 °C. Its polarization resistance at open circuit voltage is 0.21 Ω cm². Ag-GDC electrode can be operated even at pure steam. An SOEC operated for electrolyzing 100% H₂O, the current density reaches 720 mA cm^?2 under 1.3 V at 800 °C.     

Assessment of hydrogen production from waste heat using hybrid systems of Rankine cycle with proton exchange membrane/solid oxide electrolyzer

A techno-economic assessment of hydrogen production from waste heat using a proton exchange membrane (PEM) electrolyzer and solid oxide electrolyzer cell (SOEC) integrated separately with the Rankine cycle via two different hybrid systems is investigated. The two systems run via three available cement waste heats of temperatures 360 °C, 432 °C, and 780 °C with the same energy input. The waste heat is used to run the Rankine cycle for the power production required for the PEM electrolyzer system, while in the case of SOEC, a portion of waste heat energy is used to supply the electrolyzer with the necessary steam. Firstly, the best parameters; Rankine working fluid for the two systems and inlet water flow rate and bleeding ratio for the SOEC system are selected. Then, the performance of the two systems (Rankine efficiency, total system efficiency, hydrogen production rate, and economic and CO₂ reduction) is investigated and compared. The results reveal that the two systems' performance is higher in the case of steam Rankine than organic, while a bleeding ratio of 1% is the best condition for the SOEC system. Rankine output power, total system efficiency, and hydrogen production rate rose with increasing waste heat temperature having the same energy. SOEC system produces higher hydrogen production and efficiency than the PEM system for all input waste heat conditions. SOEC can produce 36.9 kg/h of hydrogen with a total system efficiency of 23.8% at 780 °C compared with 27.4 kg/h and 14.45%, respectively, for the PEM system. The minimum hydrogen production cost of SOEC and PEM systems is 0.88 $/kg and 1.55 $/kg, respectively. The introduced systems reduce CO₂ emissions annually by about 3077 tons.     

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.     

A study on solid oxide electrolyzer stack and system performance based on alternative mapping models

In this study, a solid oxide electrolyzer cell (SOEC) stack model is developed based on an alternative mapping concept. The SOEC stack performance in a commercial hot box is systematically studied under different operating currents, flow rates, and flow directions. The results revealed that the SOEC stack operated in a hot box has thoroughly different temperature distributions, resulting in additional efficiency losses and an increase in thermal neutral voltage. The SOEC stack model computation results are summarized into stack performance diagrams and used in the system design. A 6-Nm³/h SOEC system with preheaters and recycling cathode materials is designed, and its performance is studied. The system efficiency is greatly influenced by the steam generator, and an external steam source can help increase the total efficiency of the system to more than 83%. Even the current increase may deteriorate the stack performance. It can increase the SOEC system efficiency by saving energy in the steam generator and preheaters. An increase in the flow rate around anode and cathode can improve the system capacity and efficiency. The system's maximum capacity is limited by the preheater heat balance and the stack output temperature. The feasible maximum system capacity is 33.4 kW electrolysis electric power input and 9.93 Nm³/h hydrogen production rate. At a constant system capacity, decreasing the air flow rate can minimize the heat losses in anode off-gas and achieve more than 87% nonsteam system efficiency.     

Preparation and electrochemical behavior of dense YSZ film for SOEC

High Temperature Electrolysis (HTE) through a solid oxide electrolytic cell (SOEC) had been receiving more and more attentions recently because of its high conversion efficiency (45–59%) and its potential usage for large-scale hydrogen or synthetic fuels production. One of the key technologies associated with SOEC fabrication was to prepare dense yttria-stabilized zirconia (YSZ) electrolyte film on the surface of hydrogen electrode. A novel screen-printing method was developed to fabricate gas-tight YSZ films on porous NiO-YSZ to reduce ohmic resistance of electrolytes and improve electrochemical performance of cells in this paper. The effects of pre-calcining temperature of cathodes, numbers of printing layers and sintering temperature of YSZ films were investigated in detail. SEM and EIS analyses revealed that the selected process parameters had significant influences on the microscopic morphology of YSZ electrolyte film, the OCVs and power density of the prepared cells. After optimization, a 10 μm dense YSZ film was prepared successfully on porous NiO-YSZ support with an OCV of 1.069 V and the electrolysis current density up to 0.681 A/cm² at 1.50 V and 850 °C.     

Comparison of ceria and zirconia based electrolytes for solid oxide electrolysis cells

Steam electrolysis for hydrogen production is investigated in solid oxide electrolysis cell (SOEC). Sc³⁺, Ce⁴⁺, and Gd³⁺ are doped in zirconia (SCGZ) and compared with yttria stabilized zirconia (YSZ) and gadolinium doped ceria (GDC) electrolyte. Electrolyte-supported cells are fabricated. The SCGZ and YSZ electrolytes are dense with >95% relative density while GDC is less densified. The activation energy of conduction of the SCGZ electrolyte is the lowest at 65.58 kJ mol^?1 although phase transformation is detected after electrolyte fabrication process. Cathode-supported cell having SCGZ electrolyte (Ni-SCGZ/SCGZ/BSCF) shows the highest electrochemical performance. Durability test of the cells in electrolysis mode is carried out over 60 h (0.3 A cm^?2, 1073 K, H₂O to H₂ ratio of 70:30). Significant performance degradation of Ni-GDC/YSZ/GDC/BSCF cell is observed (0.0057 V h^?1) whereas the performance of Ni-YSZ/YSZ/BSCF and Ni-SCGZ/SCGZ/BSCF are rather stable under the same operating conditions. The BSCF remains attaching to the SCGZ electrolyte and additional phase transformation is not observed after prolong operation.     

High temperature electrolysis of hydrogen bromide gas for hydrogen production using solid oxide membrane electrolyzer

Using solid oxide membrane, this paper presents the theoretical modeling of the high temperature electrolysis of hydrogen bromide gas for hydrogen production. The electrolysis of hydrogen halides such as hydrogen bromide is an attractive process, which can be coupled to hybrid thermochemical cycles. The high temperature electrolyzer model developed in the present study includes concentration, ohmic, and activation losses. Exergy efficiency, as well as energy efficiency parameters, are used to express the thermodynamic performance of the electrolyzer. Moreover, a detailed parametric study is performed to observe the effects of various parameters such as current density and operating temperature on the overall system behavior. The results show that in order to produce 1 mol of hydrogen, 1.1 V of the applied potential is required, which is approximately 0.8 V less compared to high temperature steam electrolysis under same conditions (current density of 1000 A/m² and temperature of 1073 K). Furthermore, it is found that with the use of the presented electrolyzer, one can achieve energy and exergy efficiencies of about 56.7% and 53.8%, respectively. The results presented in this study suggest that, by employing the proposed electrolyzer, two-step thermochemical cycle for hydrogen production may become more attractive especially for nuclear- and concentrated solar-to-hydrogen conversion applications.     

Sr2Fe1.5+xMo0.5O6-δ cathode with exsolved Fe nanoparticles for enhanced CO2 electrolysis

Solid oxide electrolysis cell (SOEC) can perform CO₂ electrolysis to produce CO feedstock. In this work, we show Sr₂Fe_1.5+xMo_0.5O_6-δ with exsolved Fe nanoparticles to enhance the activity to CO₂ electrolysis. A single SOEC with a configuration of SF_1.5+xM-SDC/LSGM/LSM-SDC shows a current density of 1.16 A cm⁻² at 1.8 V, which presents the CO production rate of 6.85 mL min⁻¹ cm⁻² and the current efficiency of up to 96.3% at 850 °C. We further demonstrate a stable electrolysis performance without obvious degradation being observed even after a long-time operation of 100 h. The exsolved metal-oxide interfaces function as three phase boundary which transports gas molecules, oxygen ions and electrons and therefore accommodate CO₂ splitting in electrochemical process.     

Elementary reaction modeling and experimental characterization of solid oxide fuel-assisted steam electrolysis cells

A one-dimensional elementary reaction kinetic model for solid oxide fuel-assisted steam electrolysis cell (SOFEC) is developed coupling heterogeneous elementary reactions, electrochemical reaction kinetics, electrode microstructure and transport processes of charge and mass. This model is calibrated and validated by experimental data from a button cell with anode gases of H₂, CO and CH₄ at 800 °C. After comparisons with solid oxide electrolysis cell (SOEC), the energy demands, performance and efficiency of CO-assisted SOFEC and CH₄-assisted SOFEC are investigated numerically. One important finding is that over 80% of electricity can be saved by SOFEC at a current density of 3000 A m⁻². SOFEC assisted by CO or CH₄ for steam electrolysis has better performance than SOEC, especially by CH₄. The efficiencies of 12% CO-SOFEC and 12% CH₄-SOFEC are at least, respectively, 7% and 30% higher than that of SOEC at 800 °C with the current density of below 2500 A m⁻². Finally, the effects of type of assisting-fuel, fuel composition and applied voltage are studied. It is found that CO-SOFEC shows higher anode polarization and thus lower performance than CH₄-SOFEC with the same molar fraction of fuel. It is also found that the performance of SOFEC increases with increasing proportion of assisted fuel in anode at high current density.     

Thermodynamic and electrochemical analyses of a solid oxide electrolyzer for hydrogen production

In this paper, a modeling of the Solid Oxide Electrolysis Cell (SOEC), through energetic, exergetic and electrochemical modeling approaches, is conducted, and its performance, particularly through exergy efficiency, is analyzed under various operating conditions and state properties for optimum hydrogen production. In a comprehensively performed parametric study, at a single electrolysis cell scale, the effects of varying some operating conditions, such as temperature, pressure, steam molar fraction and the current density on the cell potential and hence the performance are investigated. In addition, at the electrolyzer system scale, the overall electrolyzer performance is investigated through energy and exergy efficiencies, in addition to the system's power density consumption, hydrogen production rate, heat exchange rates and exergy destruction parameters. The present results show that the overall solid oxide electrolyzer energy efficiency is 53%, while the exergy efficiency is 60%. The exergy destruction at a reduced operating temperature increases significantly. This may be overcome by the integration of this system with a source of steam production.     

High temperature water electrolysis in solid oxide cells

Hydrogen production via high temperature steam electrolysis is a promising technology as it involves less electrical energy consumption compared to conventional low temperature water electrolysis, as consequence of the more favourable thermodynamic and electrochemical kinetic conditions for the reaction. This paper reports on the Solid Oxide Electrolyser Cell (SOEC) performance as function of the operating parameters temperature, humidity and current density. Current–voltage measurements are coupled with impedance spectroscopy, in order to identify the different loss terms in the cell behaviour coming from the electrolyte resistance and the electrode processes. Remarkably high electrical-to-hydrogen energy conversion efficiencies are achieved (e.g., cell voltages of 1.0 and 1.25 V at −1 A cm⁻² and 900 and 800 °C, respectively). Results obtained, moreover, show that an important limitation for the electrolysis reaction, at least at moderate absolute humidity values below about 70 vol.% can be the steam diffusion in the hydrogen/steam electrode.