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.     

Novel copper-based anodes for solid oxide fuel cells with samaria-doped ceria electrolyte

A novel copper-based anode for low-temperature solid oxide fuel cells was prepared through the conventional ceramic technology and using CuO and SDC (Ce_0.8Sm_0.2O_1.9) powders with controlled particle size. The new Cu–SDC anode also contained highly dispersed CeO₂ and Ni particles to increase its surface area and fuel cell performance. The specific surface area of the Cu–SDC bare anode, CeO₂ and Ni-dispersed phases were estimated to be 1.53, 39.4 and 86.4 m² g⁻¹, respectively. Solid oxide fuel cells having the new anode were tested for both humid hydrogen and methane. Power densities of ca. 250 mW cm⁻² were achieved in H₂ at 600 °C and in CH₄ 700 °C, even if the SDC–electrolyte supporting membrane was 250-μm thick. Short term stability tests (maximum 64 h) showed an initial impairment, but not dramatic, of the new anode performance and the formation of carbon deposits. The addition of MoO_x to the new anode did not prevent the formation of carbon deposits.     

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.     

23,000 h steam electrolysis with an electrolyte supported solid oxide cell

An electrolyte supported solid oxide cell of 45 cm² area was operated in the steam-electrolysis mode during more than 23,000 h before scheduled shutdown, of which 20,000 h with a current density of j = ?0.9 A cm^?2. The cell consisted of a scandia/ceria doped zirconia electrolyte (6Sc1CeSZ), CGO diffusion-barrier/adhesion layers between electrolyte and electrodes, a lanthanum strontium cobaltite ferrite (LSCF) oxygen electrode, and a nickel/gadolinia-doped ceria (Ni/GDC) steam/hydrogen electrode. Voltage degradation in the operation period with j = ?0.9 A cm^?2 was 7.4 mV/1000 h (0.57%/1000 h) and the increase in the area specific resistance 8 mΩ cm²/1000 h. The final cell voltage was 1.33 V (at 851 °C cell temperature). After dismantling, the cell showed no mechanical damage at electrolyte and H₂/H₂O electrode; a small fraction of the oxygen electrode was delaminated. Impedance spectroscopy applied at the steady state DC current density confirmed a degradation dominated by an increasing ohmic term, mainly due to ionic conductivity decay in the electrolyte. In addition, a small non-ohmic and at least partly reversible O₂ electrode contribution to degradation was identified, affected by a pollution from the (compressor) purge air.     

Comparative study of the nano-composite electrolytes based on samaria-doped ceria for low temperature solid oxide fuel cells (LT-SOFCs)

Ceria-based electrolyte materials have great potential in low and intermediate temperature solid oxide fuel cell applications. In the present study, three types of ceria-based nano-composite electrolytes (LNK-SDC, LN-SDC and NK-SDC) were synthesized. One-step co-precipitation method was adopted and different techniques were applied to characterize the obtained ceria-based nano-composite electrolyte materials. TGA, XRD and SEM were used to analyze the thermal effect, crystal structure and morphology of the materials. Cubic fluorite structures have been observed in all composite electrolytes. Furthermore, the crystallite sizes of the LN-SDC, NK-SDC, LNK-SDC were calculated by Scherrer formula and found to be in the range 20 nm, 21 nm and 19 nm, respectively. These values emphasize a good agreement with the SEM results. The ionic conductivities were measured using EIS (Electrochemical Impedance Spectroscopy) with two-probe method and the activation energies were also calculated using Arrhenius plot. The maximum power density was achieved 484 mW/cm² of LNK-SDC electrolyte at 570 °C using the LiCuZnNi oxide electrodes.     

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.     

Role of initial microstructure on nickel-YSZ cathode degradation in solid oxide electrolysis cells

Electrical performance degradation relating to materials interactions at elevated temperatures is one of the primary technical limitations to the near term successful commercialization of solid oxide electrolysis cells (SOECs). Electrochemical performance and structural degradation of nickel-YSZ fuel electrodes (SOEC cathodes) were studied as functions of materials, preparation techniques, and operating conditions. Significant electrochemical degradation was observed in cells operated at 840 °C with and without voltage bias. Carbon deposition, Ni evaporation, and impurity poisoning were not observed to negatively affect performance. However, the high Ni content and large initial Ni particle size caused rapid Ni migration and agglomeration. The agglomeration reduced Ni electrical interconnectivity as well as contact area with the current collector.     

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.     

Gadolinium doped ceria-impregnated nickel-yttria stabilised zirconia cathode for solid oxide electrolysis cell

Steam electrolysis (H₂O → H₂ + 0.5O₂) was investigated in solid oxide electrolysis cells (SOECs). The electrochemical performance of GDC-impregnated Ni-YSZ and 0.5% wt Rh-GDC-impregnated Ni-YSZ was compared to a composite Ni-YSZ and Ni-GDC electrode using a three-electrode set-up. The electrocatalytic activity in electrolysis mode of the Ni-YSZ electrode was enhanced by GDC impregnation. The Rh-GDC-impregnated Ni-YSZ exhibited significantly improved performance, and the electrode exhibited comparable performance between the SOEC and SOFC modes, close to the performance of the composite Ni-GDC electrode. The performance and durability of a single cell GDC-impregnated Ni-YSZ/YSZ/LSM-YSZ with an H₂ electrode support were investigated. The cell performance increased with increasing temperature (700 °C-800 °C) and exhibited comparable performance with variation of the steam-to-hydrogen ratio (50/50 to 90/10). The durability in the electrolysis mode of the Ni-YSZ/YSZ/LSM-YSZ cell was also significantly improved by the GDC impregnation (200 h, 0.1 A/cm², 800 °C, H₂O/H₂ = 70/30).     

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.     

Performance of anode-supported solid oxide fuel cell using novel ceria electrolyte

The potential of a novel co-doped ceria material Sm_0.075Nd_0.075Ce_0.85O_2−δ as an electrolyte was investigated under fuel cell operating conditions. Conventional colloidal processing was used to deposit a dense layer of Sm_0.075Nd_0.075Ce_0.85O_2−δ (thickness 10 μm) over a porous Ni-gadolinia doped ceria anode. The current-voltage performance of the cell was measured at intermediate temperatures with 90 cm³ min⁻¹ of air and wet hydrogen flowing on cathode and anode sides, respectively. At 650 °C, the maximum power density of the cell reached an exceptionally high value of 1.43 W cm⁻², with an area specific resistance of 0.105 Ω cm². Impedance measurements show that the power density decrease with decrease in temperature is mainly due to the increase in electrode resistance. The results confirm that Sm_0.075Nd_0.075Ce_0.85O_2−δ is a promising alternative electrolyte for intermediate temperature solid oxide fuel cells.     

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.     

The properties of the fuel electrode of solid oxide cells under simulated seawater electrolysis

In this study, electrolysis of seawater in flat-tube nickel-yttria-stabilized zirconia (Ni-YSZ) electrode-supported solid oxide electrolysis cells (SOECs) were modeled and the effects of variations in electrical conductivity and microstructure of Ni-YSZ electrode support were investigated. When the current density was greater than 700 mA·cm⁻², the conductivity of the electrode support decreased slightly with an increase in current density at 800 °C in hydrogen reduction environment; the conductivity of the electrode support decreased with an increase in the current density when the current density was greater than 400 mA·cm⁻² at 800 °C in the seawater electrolysis environment. During long-term durability experiment of seawater electrolysis, the degradation rates in area specific resistance (ASR) were 0.096 mΩ·cm²/100 h and 0.207 mΩ·cm²/100 h with a current density of 300 mA·cm⁻² (i.e., ≤400 mA·cm⁻²) and 1000 mA·cm⁻² (i.e., ≥400 mA·cm⁻²), respectively. Besides, the various ions commonly present in seawater did not contaminate the Ni-YSZ support during the long-term durability test. The degradation mechanism of seawater electrolysis in flat-tube SOECs is discussed and clarified.     

Effect of sintering aids on sintering kinetic behavior of praseodymium doped ceria based electrolyte material for solid oxide cells

The present study investigates the effect of sintering additives (Li, Co, Fe, and Mg) on the sintering kinetic behavior of the praseodymium-doped-ceria (PDC) electrolyte of solid oxide electrolyzer cell. 3Li-PDC, 3Co-PDC, 3Fe-PDC, and 3 Mg-PDC pellets were obtained from the synthesis of PDC nano-powder by microwave-assisted co-precipitation method using isopropyl alcohol as a solvent and followed by sintering additive wetness impregnation method. Linear shrinkage and shrinkage rate data suggest a positive sintering effect for 3Li-PDC and 3Co-PDC pellets and a negative sintering effect for 3 Mg-PDC and 3Fe-PDC pellets than compared to PDC pellets alone. The addition of lithium as a sintering additive (3Li-PDC) had reduced the sintering temperature of PDC from 1100 °C to 850 °C. For PDC, 3Li-PDC, 3Co-PDC, 3Fe-PDC and 3 Mg-PDC pellets sintered at 1100 °C, 850 °C, 1000 °C, 1200 °C, 1100 °C for 2 h resulted in a relative density of 93.6 ± 0.25, 95.8 ± 0.45, 95.0 ± 0.20, 92.7 ± 0.10, and 94.5 ± 0.10%, respectively. The XRD patterns of the sintered PDC pellets suggested a secondary phase formation (PrO₂) in 3Co-PDC, 3Fe-PDC, and 3 Mg-PDC pellets indicating that the addition of these sintering aids results in poor solubility limit of Pr in CeO₂. On the other hand, XRD patterns of PDC and Li-PDC sintered pellets displayed no secondary peak indicating good solid-solution formation. The activation energy of the 3Li-PDC pellet is obtained from CHR and Dorn methods and was found to be 182 kJ/mol and 196 kJ/mol. From the CHR method, for the 3Li-PDC pellet, the initial sintering behavior is by the grain boundary diffusion mechanism (m = ~2).     

Efficient and stable heterostructured air electrode for solid oxide steam electrolysis

High performance and excellent durability are essential for the practical application of solid oxide electrolysis cell (SOEC). Here we have demonstrated efficient and durable solid oxide steam electrolysis by constructing active La_0.8Sr_0.2CoO_3-δ/Gd_0.2Ce_0.8O_2-δ (LSC/GDC) heterointerface in air electrode using a simple co-impregnation method. The heterostructured air electrode exhibits the outstanding activity for oxygen evolution reaction, and its exchange current density (557 mA cm^?2) is 69 times higher than that of the traditional LSM-YSZ. The resulting cell reaches ?1.86 A cm^?2 @1.3 V and ?2.30 A cm^?2 @1.5 V at 800 °C and 50% absolute humidity (A.H), and the polarization resistance from the oxygen electrode only is 0.02 Ω cm². Most importantly, the heterostructured cell presents excellent long-term stability for the 1035 h steam electrolysis operation and excellent durability for 100 times charge-discharge cycles. In the heterostructured air electrode, the problem of electrode delamination is avoided due to the reduced oxygen partial pressure at anode/electrolyte resulting from easy diffusion of O^2? at the interphase, and the coarsening of LSC and GDC nanoparticles is limited because of the LSC/GDC percolative interfaces from phase segregation process. This work proposes a simple and effective strategy to design heterointerface for efficient and durable solid oxide steam electrolysis.     

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.     

Micro modelling of solid oxide electrolysis cell: From performance to durability

An in-house micro model has been built to describe the electrochemical mechanisms governing both H₂ and O₂ electrodes operating in SOEC mode. A special attention has been paid to take into account the microstructure properties of the ionic, electronic and gas phases as well as the processes occurring therein.     

Thermodynamic analysis of synthetic hydrocarbon fuel production in pressurized solid oxide electrolysis cells

A promising way to store wind and solar electricity is by electrolysis of H₂O and CO₂ using solid oxide electrolysis cells (SOECs) to produce synthetic hydrocarbon fuels that can be used in existing fuel infrastructure. Pressurized operation decreases the cell internal resistance and enables improved system efficiency, potentially lowering the fuel production cost significantly. In this paper, we present a thermodynamic analysis of synthetic methane and dimethyl ether (DME) production using pressurized SOECs, in order to determine feasible operating conditions for producing the desired hydrocarbon fuel and avoiding damage to the cells. The main parameters of cell operating temperature, pressure, inlet gas composition and reactant utilization are varied to examine how they influence cell thermoneutral and reversible potentials, in situ formation of methane and carbon at the Ni–YSZ electrode, and outlet gas composition. For methane production, low temperature and high pressure operation could improve the system efficiency, but might lead to a higher capital cost. For DME production, high pressure SOEC operation necessitates higher operating temperature in order to avoid carbon formation at higher reactant utilization. Optimal operating conditions are dependent on the total system design.     

Enhancing the long-term stability of Ag based seals for solid oxide fuel/electrolysis applications by simple interconnect aluminization

Ag-(0–8 mol%) CuO is used to successfully join aluminized ferritic stainless steel interconnect to the ceria-gadolinia (CGO) barrier layer of a solid oxide fuel/electrolysis cell by reactive air brazing at 1000 °C in air. The wetting of AgCuO on CGO is tailored by varying the CuO content. The effects of the CuO content on the joint microstructure are discussed. The long-term stability of brazed joints is evaluated by aging in oxidizing (air) and reducing (4% H₂–50% H₂ON₂) atmospheres at 800 °C for 250 h. An Ag-2mol% CuO braze results in the best joint stability during aging. Aluminization of the steel to create an alumina surface layer provides excellent protection of the steel both during the joining process and aging in the 2 atm. No degradation related to steel corrosion and outward diffusion of elements from the steel can be observed.