Solid Oxide Research Articles

Development and investigation of a porous metal-ceramic substrate for solid oxide fuel cells

The process of creating a porous metal-ceramic material based on Ni-Al alloy and gadolinium-doped cerium oxide (CGO) using the thermal explosion method has been investigated. This study aims to analyze the effect of CGO on the thermal explosion parameters and the architecture of the resulting Ni-Al-CGO materials. In this regard, the influence of adding CGO powder to the Ni-Al system on the synthesis process and structure formation during controlled heat loss thermal explosion has been studied. Dependencies of temperature and time characteristics of the thermal explosion on initial parameters have been measured. It has been demonstrated that the concentration of CGO in the initial mixture and heat dissipation from the sample significantly affect the rate of the exothermic reaction. The phase composition of the obtained porous materials, depending on the CGO content and the temperature of subsequent vacuum annealing, was analyzed using X-ray diffraction. The chemical composition and microstructure of the synthesis products were examined through electron microscopy and energy-dispersive X-ray spectroscopy. The possibility of forming metal-ceramic composites with a porosity of 60–65 % for use as supporting substrates for solid oxide fuel cells with a NiO/CGO anode has been shown. An anodic layer of NiO/CGO was applied to a metal-ceramic base of the composition (Ni+25 %Al)+5 %CGO using screen printing, which was then annealed in an air atmosphere at 1300 °C and reduced at 900 °C in a hydrogen atmosphere. The dilatometric method determined that adding 40 wt.% Cr to a mixture of Ni-Al powders reduces the average coefficient of thermal expansion of the new material.

A High-Performance and Durable Direct-Ammonia Symmetrical Solid Oxide Fuel Cell with Nano La0.6Sr0.4Fe0.7Ni0.2Mo0.1O3-δ-Decorated Doped Ceria Electrode.

Solid oxide fuel cells (SOFCs) offer a significant advantage over other fuel cells in terms of flexibility in the choice of fuel. Ammonia stands out as an excellent fuel choice for SOFCs due to its easy transportation and storage, carbon-free nature and mature synthesis technology. For direct-ammonia SOFCs (DA-SOFCs), the development of anode catalysts that have efficient catalytic activity for both NH3 decomposition and H2 oxidation reactions is of great significance. Herein, we develop a Mo-doped La0.6Sr0.4Fe0.8Ni0.2O3-δ (La0.6Sr0.4Fe0.7Ni0.2Mo0.1O3-δ, LSFNM) material, and explore its potential as a symmetrical electrode for DA-SOFCs. After reduction, the main cubic perovskite phase of LSFNM remained unchanged, but some FeNi3 alloy nanoparticles and a small amount of SrLaFeO4 oxide phase were generated. Such reduced LSFNM exhibits excellent catalytic activity for ammonia decomposition due to the presence of FeNi3 alloy nanoparticles, ensuring that it can be used as an anode for DA-SOFCs. In addition, LSFNM shows high oxygen reduction reactivity, indicating that it can also be a cathode for DA-SOFCs. Consequently, a direct-ammonia symmetrical SOFC (DA-SSOFC) with the LSFNM-infiltrated doped ceria (LSFNM-SDCi) electrode delivers a superior peak power density (PPD) of 487 mW cm-2 at 800 °C when NH3 fuel is utilised. More importantly, because Mo doping greatly enhances the reduction stability of the material, the DA-SSOFC with the LSFN-MSDCi electrode exhibits strong operational stability without significant degradation for over 400 h at 700 °C.

Synergetic effect of spontaneous Fe diffusion for enabling immediately switchable operations in NiFe-supported solid oxide cells

Solid oxide cells (SOCs) are highly efficient energy conversion systems, offering switchable capabilities for power and fuel production. NiFe metal-supported structures in SOCs show promising advantages in structural stability and scalability. This study explores the synergistic effect of spontaneous Fe diffusion in NiFe-supported SOCs, enhancing alloy catalyst formation in the electrode and improving the sinterability of the zirconia-based electrolyte. This results in increased activity for carbon fuel reactions, resistance to coking, and a remarkably low ohmic resistance of 0.06 Ω cm2 at 800 °C. The NiFe support also enhances structural stability, enabling reversible and multifuel operation. The single cell achieves exceptional maximum power densities of 2.6 and 2.0 W cm−2 in fuel cell mode (3 % H2O/H2 and dry CO) and current densities of − 1.51 and − 1.38 A cm−2 in electrolysis cell mode (1.3 V, 20 % H2O/H2 and 20 % CO2/CO) at 800 °C, respectively.

Solid oxide fuel cells and electrolysis cells: selected aspects, novel materials and challenges

Solid oxide fuel cells and electrolysis cells: selected aspects, novel materials and challenges

High-Performance Reversible Solid Oxide Cells for Powering Electric Vehicles, Long-Term Energy Storage, and CO2 Conversion.

The rapid population growth coupled with rising global energy demand underscores the crucial importance of advancing intermittent renewable energy technologies and low-emission vehicles, which will be pivotal toward carbon neutralization. Reversible solid oxide cells (RSOCs) hold significant promise as a technology for high-efficiency power generation, long-term chemical energy storage, and CO2 conversion. Herein, RSOCs were, for the first time, studied to power electric vehicles. Based on our experimental results, an ideal RSOC stack was established with reasonable assumptions. Subsequently, through analysis and comparison of important merits, such as power densities, energy densities, charging/refueling time, and fuel economy of RSOC-based electric vehicles (RSOCEVs), conventional internal combustor vehicles (ICEVs), and battery-based electric vehicles (BEVs), the advantages and prospects of RSOCEVs were highlighted. Our H2-H2O RSOCs exhibit high electrochemical performances in both fuel cell (peak power density = 1.6 W cm-2 at 750 °C) and electrolysis modes (current density = 2.0 A cm-2 at 1.3 V and 750 °C), along with durable reversible operation under a wide range of conditions. In CO-CO2, our RSOCs achieved excellent performance in fuel cell mode (peak power density = 0.68 cm-2 at 700 °C). Furthermore, a world record current density of 3.4 A cm-2 at 1.5 V and 750 °C was achieved in the CO2 electrolysis mode. Moreover, an assessment of the CO2 electrolysis efficiency was conducted, offering insights for establishing energy storage strategies and mitigating CO2 emissions. Therefore, the RSOC technology has the potential to assume a central role in a future energy system with abundant renewable power generation while mitigating the CO2 released from fossil fuels.

From Electrolyte and Electrode Materials to Large‐Area Protonic Ceramic Fuel Cells: A Review

AbstractFuel cells can efficiently convert the chemical energy in fuels like hydrogen and methane into electricity and are an important component for the forthcoming hydrogen society. Compared with conventional solid oxide fuel cells (SOFCs) and proton exchange membrane fuel cells (PEMFCs), protonic ceramic fuel cells (PCFCs) using proton conducting solid oxides as the electrolyte operate at intermediate temperature (400–700 °C), enabling the reduction in cost by using inexpensive catalysts and structural materials. In the last couple of decades, the development of electrolyte and electrode materials for PCFCs has seen significant advances, including fabrication of large‐size cells, promoting PCFCs to step out of the lab toward real applications. This review provides a historic overview of the development of proton conducting oxides, summarizes recent progress on the development of electrolyte and electrode materials and large‐size cells, and discusses present problems and challenges ahead.

Correction to: Preparation of Plasma Sprayed GDC Electrolytes for Metal-Supported Solid Oxide Fuel Cells

Correction to: Preparation of Plasma Sprayed GDC Electrolytes for Metal-Supported Solid Oxide Fuel Cells

Optimizing Bilayer Electrolyte Thickness Ratios for High-Performing Low-Temperature Solid Oxide Fuel Cells

Abstract Bilayer electrolytes for low-temperature solid oxide fuel cells (LT-SOFCs) offer the potential for higher power density by lowering the ohmic area specific resistance (ASR) and increasing the open circuit voltage (OCV) of mixed ionic/electronic conducting (MIEC) type electrolyte (e.g., GDC). However, optimizing the bilayer electrolyte thickness ratio is essential to achieve high power densities at low-temperatures (650-500℃). Herein we provide a systematic study of GDC/YCSB bilayer thickness ratios on anode-supported LT-SOFCs. In all cases the bilayer maximum power density (MPD) is higher than single-layer GDC based cells with reduced ohmic ASR values. Specifically, a high MPD of ~1 W/cm2 at 650℃ was achieved on a GDC(20 μm)/YCSB(12 μm) bilayer electrolyte based SOFC, which is 62% higher than single-layer GDC based SOFC (0.64 W/cm2) operating on humidified H2 as fuel. Such enhancement is due to the 9.3% improvement in OCV and 36% reduction in ohmic ASR values with the addition of the YCSB layer. The reduction in ohmic ASR of the bilayer electrolyte SOFCs is due to an increase of GDC electrical conductivity caused by the lower pO2 at the YCSB/GDC interface which must be considered in optimizing the thickness ratio of the bilayer electrolyte for achieving higher power density LT-SOFCs.

Novel sr-doped NdMn0.5Cr0.5O3-δ electrodes for symmetrical solid oxide fuel cell

Solid oxide fuel cells (SOFCs) have emerged as promising energy conversion devices, offering high efficiency and environmental sustainability. Efficient electrode materials are crucial for the overall cell performance of SOFCs. Perovskite type Nd1-xSrxMn0.5Cr0.5O3-δ (x = 0.25, 0.5) (NSCM25, NSCM50) was synthesized via conventional solid-state reaction technique. Structural, thermal and electrochemical characterizations were performed using X-ray diffraction, thermogravimetric analysis, conductivity measurements, scanning electron microscope, thermal expansion coefficient analysis and impedance spectroscopy. Structural analysis revealed that both compositions exhibit orthorhombic symmetry in the Pbnm space group. Thermogravimetric analysis (TGA) indicated minimal weight changes in both pre-reduced and as-prepared samples. The electrical conductivities in air at 600 ℃ were found to be 1.69 S/cm for NSCM25 and 4.91 S/cm for NSCM50, with a decrease observed under reduced oxygen partial pressure. Polarization resistance (Rp) analysis was conducted on symmetrical cells composed of NSCM25|GDC|NSCM25, NSCM50|GDC|NSCM50, NSCM25|YSZ|NSCM25, and NSCM50|YSZ|NSCM50. At 900 ℃, the polarization resistances were 0.12 Ωcm2, 0.21 Ωcm2, 0.11 Ωcm2, and 0.67 Ωcm2, respectively. The results suggest that NSCM25 and NSCM50 hold promise as electrode materials for symmetrical solid oxide fuel cells (SSOFC) employing YSZ or GDC electrolyte.

Oxygen permeability and electrochemical performance of Ca-doped NdBaCo2O5+δ in IT-SOFC

The layered perovskites NdBa1−xCaxCo2O5+δ (NBCax, where x = 0.0, 0.1, 0.2, 0.3, and 0.4) have been synthesized through a conventional solid-state reaction and examined as potential cathode candidates for intermediate-temperature solid oxide fuel cells (IT-SOFC; 600°C–800°C). The Ca-substituted oxides exhibit a P4/mmm tetragonal structure and a phase transition to simple perovskite at x ≥ 0.3. The electrical conductivity in air at 300°C–800°C and oxygen permeation flux of NBCax oxides are influenced by Ca doping content. The activation energy for the oxygen migration process indicates that bulk diffusion is predominant at temperatures below 800°C. X-ray photoelectron spectroscopy indicates the coexistence of Co3+ and Co4+ and oxygen-active sites on the surface of the NBCax oxides. Variations in Co4+ and adsorbed oxygen contents are related to the number of oxygen vacancies and are influenced by Ca content. Among the oxides examined, NdBa0.9Ca0.1Co2O5+δ exhibits good electrical conductivity, high amounts of Co4+ and adsorbed oxygen, high maximum power density of 1286 mW·cm−2 at 800°C in H2 fuel in the La0.9Sr0.1Ga0.8Mg0.2O3 electrolyte–supported cell, and low polarization resistance of the cell, as determined using AC impedance spectroscopy. These findings suggest that Ca incorporation can improve the electrochemical performance of NdBaCo2O5+δ, rendering it a promising candidate for use as a cathode material in IT-SOFCs.

An Active and Stable Cobalt‐Free Ruddlesden–Popper Nd0.8Sr1.2Ni1‐xFexO4±δ Air Electrode for Reversible Proton‐Conducting Solid Oxide Cells

AbstractReversible proton‐conducting solid oxide cells (R‐PSOCs) are considered to be one of the most promising devices for efficient power generation and hydrogen production. However, the requirement of high catalytic activity for fast oxygen reduction/evolution reaction (ORR/OER) and durability under high steam concentration of air electrode materials remains the major challenge for the practical application of R‐PSOCs. Here, a series of cobalt‐free Ruddlesden–Popper perovskite of Nd0.8Sr1.2Ni1‐xFexO4±δ are reported with mixed conductivity for enhanced ORR/OER kinetics. The R‐PSOCs with an optimal Nd0.8Sr1.2Ni0.7Fe0.3O4±δ air electrode show a high peak power density of 1.28 W cm−2 in the fuel cell mode and a promising current density of 3.24 A cm−2 at 1.3 V in the electrolysis cell mode at 700 °C. In addition, the R‐PSOCs show favorable stability under the fuel cell, electrolysis, and reversible modes for hundreds of hours. This work demonstrates that the Ruddlesden–Popper materials can be utilized as suitable air electrodes for R‐PSOCs.

High Conductivity and Diffusion Mechanism of Oxide Ions in Triple Fluorite-Like Layers of Oxyhalides.

Oxide ion conductors are attractive materials because of their wide range of applications, such as solid oxide fuel cells. Oxide ion conduction in oxyhalides (compounds containing both oxide ions and halide ions) is rare. In the present work, we found that Sillén oxychlorides, Bi2-xTexLuO4+x/2Cl (x = 0, 0.1, and 0.2), show high oxide ion conductivity. The bulk conductivity of Bi1.9Te0.1LuO4.05Cl reaches 10-2 S cm-1 at 431 °C, which is much lower than 644 °C of yttria-stabilized zirconia (YSZ) and 534 °C of La0.8Sr0.2Ga0.83Mg0.17O2.815 (LSGM). Thanks to the low activation energy, Bi1.9Te0.1LuO4.05Cl exhibits a high bulk conductivity of 1.5 × 10-3 S cm-1 even at a low temperature of 310 °C, which is 204 times higher than that of YSZ. The low activation energy is attributed to the interstitialcy oxide ion diffusion in the triple fluorite-like layer, as evidenced by neutron diffraction experiments (Rietveld and neutron scattering length density analyses), bond valence-based energy calculations, static DFT calculations, and ab initio molecular dynamics simulations. The electrical conductivity of Bi1.9Te0.1LuO4.05Cl is almost independent of the oxygen partial pressure from 10-18 to 10-4 atm at 431 °C, indicating the electrolyte domain. Bi1.9Te0.1LuO4.05Cl also exhibits high chemical stability under a CO2 flow and ambient air at 400 °C. The oxide ion conduction due to the two-dimensional interstitialcy diffusion is considered to be common in Sillén oxyhalides with triple fluorite-like layers, such as Bi1.9Te0.1RO4.05Cl (R = La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu) and Bi6-2xTe2xO8+xBr2 (x = 0.1, 0.5). The present study opens a new field of materials chemistry: oxide ion-conducting Sillén oxyhalides with triple fluorite-like layers.

High efficiency electricity and gas cogeneration through direct carbon solid oxide fuel cell with cotton stalk biochar

For the first time, biochar derived from a renewable resource, cotton stalk, is used as the feedstock of direct carbon solid oxides fuel cells (DC-SOFCs) for electricity and gas cogeneration. It turns out that the cotton stalk biochar has plenty of naturally grown K and Ca, which are active catalysts for the reverse Boudouard reaction in DC-SOFCs. This natural advantage of the cotton stalk biochar enables an extremely high power density of an anode-supported DC-SOFC at 850 °C, 0.9 W cm−2, which is the highest among those of the reported DC-SOFCs. Meanwhile, high concentration of CO gas, which is an important feedstock for chemical industry, is obtained from the DC-SOFCs. The energy conversion efficiency of the electricity-gas cogeneration of DC-SOFCs reaches over 70%. A novel method, using compressed char, is proposed and carried out for continuous supply of cotton stalk char to a DC-SOFC. The present work has demonstrated the feasibility and advantages of cogenerating electricity and gas through DC-SOFCs with biochar derived from cotton stalk as the feedstock.

Catalytic effect of aluminum on the structural, optical, and electrical properties of LaSrCrO3-δ anode

Solid oxide fuel cell is promising conversion technology due to fuel flexibility, higher efficiency, and environment friendly compared to traditional technology. To enhance the efficiency of the device, selection of anode material is important because it affects the electrochemical performance and operating temperature of the cell. In this work, La0.5Sr0.5AlxCr1-xO3-δ (x = 0, 0.1, 0.2, 0.3, 0.4) anode has been developed using sol-gel method. XRD analysis exhibited a two-phase structure of the prepared anode, one orthorhombic and second rhombohedral phase with crystalline size in the range 15–18 nm. The surface morphology of the prepared anode material shows nano-spheres, dumbbells, and platelets. The elemental analysis confirms the presence of Sr, Cr, La, Al, and O in the prepared material. The metal-oxide formation has been confirmed with Fourier Transform Infrared Spectroscopy. The absorption spectra revealed red shift in bandgap 3.65–2.85 eV by increasing the Al concentration. The maximum dc electrical conductivity of the composition anode La0.5Sr0.5Al0.4Cr0.6O3-δ is found to be 8.01 Scm−1 at 600 °C. The achieved power density of the anode La0.5Sr0.5Al0.4Cr0.6O3-δ is 69 mWcm−2 using hydrogen fuel at 600 °C.

Thermodynamic analysis of a CCHP system with hydrogen production process by methane reforming enhanced by solar-assisted chemical looping adsorption

Combined cooling, heating and power (CCHP) systems integrated with renewable energy can greatly alleviate the fossil energy crisis and greenhouse effect. This work proposes a novel CCHP system, which consists of a solar-assisted sorption enhanced chemical looping steam methane reforming (SE-CL-SMR) hydrogen generation subsystem, a solid oxide fuel cell-gas turbine (SOFC-GT) subsystem, a dual-effect Li-Br absorption chiller/heat pump (DAC/H) subsystem, and a domestic hot water (DHW) subsystem. The impacts of the reformer temperature, pressure, the ratios of steam to carbon, calcium oxide to carbon, and nickel oxide to calcium oxide on the system’s methane conversion rate, hydrogen yield, hydrogen purity, and CO2 capture efficiency are also explored. While ensuring the hydrogen production effect and considering the lowest energy consumption, the optimal reforming temperature, reforming pressure, ratios of S/C, CaO/CH4 and NiO/CaO of the CCHP system are 560 °C, 1 atm, 3, 1 and 0.5, respectively. The system’s energy and exergy analysis is performed under the optimized operating condition. In comparison with the data of reference, the findings demonstrate that the system’s overall power generation efficiency is 53.23 %, the total energy utilization rate is 74.32 %, and the exergy efficiency is 52.87 %.

Numerical simulation of the residual stress of solid oxide fuel cells with a three-dimensional nonplanar cathode–electrolyte interface

The longevity of solid oxide fuel cells is influenced by internal residual stresses, which may induce deformation or fracturing of components. This study investigates the residual stress distribution at the nonplanar cathode–electrolyte interface by approximating the actual interface with trigonometric functions and developing a three-dimensional (3D) model. The model reveals that the stress patterns at nonplanar interfaces can elucidate the genesis of interfacial cracks. During fabrication, anode contraction results in compressive stress within the electrolyte and tensile stress within the anode, with thermal discrepancies between layers being the primary cause of residual stresses. The reduction process diminishes these stresses, thus enhancing the mechanical integrity of the cell. Mitigating interface nonplanarity is beneficial for minimizing residual stress. At each interface crest, the electrolyte exhibits a local minimum in compressive stress, and a local maximum in shear stress occurs between each crest and trough. Furthermore, decreasing the initial porosity and NiO volume fraction can slightly lessen interlayer thermal discrepancies, with little effect on residual stresses.

Evaluation of selected Fe–Cr steels under single- and dual-atmosphere conditions for intermediate-temperature solid oxide fuel cell interconnect applications

For Intermediate-Temperature SOFC, the lower operating temperature allows for a broader range of steel grades to be used as interconnects. This work compares the oxidation performances of six Cr2O3-forming steels and one Al2O3-forming steel, under single- and dual-atmosphere conditions.Single-atmosphere exposures in combination with Cr(VI) evaporation measurements were carried out at 600 °C. Except for AISI 430 all the Cr2O3-forming steels showed protective behaviour with similar Cr(VI) evaporation values and low area specific resistance (ASR) values. Kanthal EF101 showed the lowest level of Cr(VI) vaporisation but substantially higher ASR values.Dual-atmosphere exposures were carried out at 600 °C in Ar-5%H2–3%H2O//air-3%H2O. All Cr2O3-forming steels suffered various degrees of breakaway corrosion. Therefore, operation under dual-atmosphere conditions is likely the life-time-limiting failure mode.

Effects of lanthanide doping on the electrode properties and exsolution behavior of A-site deficient Sr1.9Fe1.3Ni0.2Mo0.5O6-δ double perovskites

Double perovskite oxides of the Sr2Fe1.5Mo0.5O6-δ class are promising electrodes for Solid Oxide Fuel Cells (SOFCs) and Electrolyzers (SOECs) due to their outstanding electrochemical properties and durability. Additionally, their physicochemical properties can be tuned by B-site cation doping, namely, by partially substituting Fe cations with other transition metals such as Ni, Co, Mn, or Cu. This also allows the grain-surface functionalization with metallic alloyed nanocatalysts upon reduction driven by the exsolution phenomena, leading to higher electrocatalytic activity and resistance against sintering and coking. Traditionally, A-site deficiency has been employed to improve the amount of exsolved nanoparticles and, thereby, increase the number of Triple Phase Boundaries in the electrode. However, in Ni-doped non-stoichiometric double perovskite materials (e.g., Sr1.9Fe1.3Ni0.2Mo0.5O6-δ), A-site deficiency results in undesired NiO phase segregations. This, in turn, lowers the number of exsolvable cations, decreasing the number of metallic nanocatalysts compared to the stoichiometric compound. In this work, the impact of A-site doping with lanthanides (viz. Gd, La, Nd, and Pr) on the exsolution ability and electrochemical properties of non-stoichiometric Sr1.9Fe1.3Ni0.2Mo0.5O6-δ was evaluated. The results indicate that lanthanide doping enhances the conductivity of the double perovskites both in oxidizing and reducing atmospheres. In addition, lanthanide dopants that slightly destabilize the cubic structure also improve the exsolution dispersion, which decreases with increasing the double perovskite cell volume. These results illustrate how to design more efficient and durable electrocatalysts by modifying the double perovskite structure with A-site dopants.

A Review on Critical Metals Used in Solid Oxide Cells for Power ↔ X Applications and Materials Recyclability

A Review on Critical Metals Used in Solid Oxide Cells for Power ↔ X Applications and Materials Recyclability

Efficient statistical approach for thermo-electrical properties of gadolinia-doped ceria thin films

The thermo-electrical properties of gadolinia-doped ceria (GDC) thin films play a vital role in solid oxide fuel cell (SOFC) applications. Nonetheless, the effects of temperature, dopant concentration, and thickness on thermal expansion, and ionic conduction remain ambiguous. In the present study, we propose an efficient theoretical approach to emphasize the roles of surface layers and surface vicinity (called next-surface layers) on the thermo-electrical properties of GDC thin films. Using statistical moment method, thermal expansion coefficient, and ionic conductivity are calculated as functions of temperature, dopant concentration, and thickness. The lattice strain and ionic disorder in the surface and next-surface layers cause an increase in thermal expansion coefficient and ionic conductivity of thin films. Compared with bulk GDC, the thermal expansion coefficient is slightly larger while the ionic conductivity is more than one to two orders of magnitude enhancement and exhibits the maximum value at the higher concentration. The ionic conductivity depends non-linearly on the dopant concentration and the maximum conductivity is shifted toward a higher value as the temperature increases. The enhancement in thermal expansion coefficient and ionic conductivity offers new opportunities for SOFC electrolytes whose efficiency can be effectively controlled by tailoring the thickness. The theoretical calculations are compared to measured results from experiments.