Review of composite cathodes for intermediate-temperature solid oxide fuel cell applications

A composite cathode exhibits low activation polarisation by spreading its electrochemically active area within its volume. Composite cathodes enable the development of high-performance electrodes for solid oxide fuel cells (SOFCs) at intermediate temperatures (600 °C – 800 °C) because of their significant role in determining the kinetics of oxygen reduction reaction (ORR). Few anions O²⁻ are transferred through the electrolyte component when the ORR is low, thereby lowering the reaction with cation H⁺ from an anode side to transfer electrons along the outer circuit to the cathode side to participate in ORR. The resistance to the ORR at the cathode is minimised, thereby contributing to performance degradation and efficiency loss in existing SOFCs, especially at intermediate temperatures. The suitability and compatibility of the cathode and electrolyte are crucial in the development of cathodes and electrochemical reactions. The intercomponent compatibility is important to ensure the robustness and durability of SOFCs, especially at an operating temperature around 800 °C, at which the components experience extreme thermal and mechanical stresses. Composite cathodes are used to improve cathode performance. These composite cathodes help enhance the properties of mixed electronic–ionic conductors and the intercomponent compatibility. Herein, we reviewed historical data of composite-cathode development for SOFCs, including its basic principle and criteria. The overall performance of as-synthesised composite cathodes in terms of microstructure, electrochemical reaction and intercomponent compatibility is briefly discussed.     

Boosting the electrocatalytic performance of Fe-based perovskite cathode electrocatalyst for solid oxide fuel cells

The development of cathode materials with excellent electrocatalytic activity and CO₂ tolerance is an important direction for the wide application of solid oxide fuel cells. Herein, the cobalt-free perovskite oxides Bi_0.5Sr_0.5Fe_1-xV_xO_3-δ (BSFVx, x = 0.025, 0.05 and 0.075) are developed as the efficient cathode electrocatalysts for SOFCs. The V-doping strategy is beneficial to improve the thermal stability, CO₂ tolerance and electrochemical performance of undoped Bi_0.5Sr_0.5FeO_3-δ. Among all samples, Bi_0.5Si_0.5Fe_0.95V_0.05O_3-δ (BSFV0.05) cathode presents excellent oxygen reduction reaction activity, achieving a lower polarization resistance of 0.076 Ω cm² and the peak power density of the single cell with the BSFV0.05 cathode reaches to 1.16 W cm⁻² at 700 °C, which can be comparable to those of the representative cobalt-based cathodes. Furthermore, the improved CO₂ tolerance of the BSFV0.05 cathode can be ascribed to the high acidity of the V⁵⁺ and the larger average bonding energy in the oxide.     

Synthesis and characterization of co-doped ceria-based electrolyte material for low temperature solid oxide fuel cell

Co-doped CeO₂ (Ba_0.10Ga_0.10Ce_0.80O_3–δ) was synthesized via a cost-effective co-precipitation technique, and the electrochemical properties of the solid oxide fuel cell were studied. The microstructural and surface morphological properties were investigated by XRD and SEM, respectively. The structure of the prepared material was found to be cubic fluorite with an average crystallite size of 36?nm. The ionic conductivity of the prepared BGC (Ba_0.10Ga_0.10Ce_0.80O_3–δ) electrolyte material was measured as 0.071?S?cm^?1. The activation energy was found to be 0.46?eV using an Arrhenius plot. The maximum power density and current density achieved were 375?mW?cm^?2 and 893?mA?cm^?2, respectively, at 650?°C with hydrogen as a fuel. This study shows that the prepared co-doped electrolyte material could be used as a potential electrolyte to lower the operating temperature of solid oxide fuel cells.     

Electrospun composite nanofibers for intermediate-temperature solid oxide fuel cell electrodes

Considering the dominant loss associated with surface oxygen exchange reactions among other complex electrochemical processes, the design of an electrode structure for the reasonable operation of solid oxide fuel cells is challenging. The surface oxygen exchange reaction can be considerably facilitated using composite nanofibers containing the electrode, electrolyte, and catalyst. The composite nanofiber electrodes containing Pd show the smallest polarization resistance of 0.031 Ωcm² and the maximum power density of 0.7 W/cm² at 650 °C, which are 39.2% and 12.5% improved values compare to the catalyst-free composite nanofiber electrodes, respectively. These results provide an facile fabrication strategy for developing high-performance electrodes for use in solid oxide fuel cells.     

Novel CO2-tolerant Co-based double perovskite cathode for intermediate temperature solid oxide fuel cells

For the commercial application of solid oxide fuel cells (SOFCs), CO₂-tolerant cathode materials with high electrochemical activity are required. Here, we discuss the performance of double perovskite Pr_0.2Sr_1.8CoTiO_6?δ (P02STC) as a potential cathode material for SOFCs. P02STC has a cubic structure and keeps lattice structure stable in the CO₂ atmosphere. The average thermal expansion coefficient is 17.8 × 10^–6 K^–1 at 30–900 °C in air. The P02STC cathode exhibits good electrochemical performance with a low polarization resistance of 0.080 Ωcm² at 700 °C. The P02STC cathode shows good structure stability, electrochemical performance stability, and excellent tolerance to CO₂ poisoning for the symmetrical cells based on the 350 h stability test in air and the 150 h stability test in O₂ containing 5%CO₂ at 700 °C. The electrolyte-supported single cell with a P02STC cathode shows a maximum power density of 677 mW cm^? 2 at 800 °C. The single cell operates stably for 250 h at a constant current of 0.3 A/cm² without obvious degrading performance. According to all of the experimental results, the P02STC sample might be a promising candidate cathode for SOFCs.     

Design of dedicated instrumentation for temperature distribution measurements in solid oxide fuel cells

A thermocouple was designed for temperature distribution measurements in solid oxide fuel cells. A theoretical model, based on mixed convective–radiative heat transfer was used to predict the thermocouple response. The proposed flat type thermocouple was shown to be a high sensitive, low error temperature sensor, capable of satisfying the requirements for solid oxide fuel cell thermal behaviour research. Thereafter, a purpose-built, thin, flat-type thermocouple has been used for temperature distribution measurements at the cathode side of a planar solid oxide fuel cell. High temperature conditions of 1223K have been tested. Beside temperature mapping, local hot spots have been easily located.     

Layered NdBaCo2−xNixO5+δ perovskite oxides as cathodes for intermediate temperature solid oxide fuel cells

The effect of Ni substitution on the crystal chemistry, thermal and electrochemical properties, and catalytic activity for oxygen reduction reaction of the layered NdBaCo_2−xNi_xO_5+δ perovskite oxides has been investigated for 0 ≤ x ≤ 0.6. The oxygen content (5 + δ) and oxidation state of the (Co, Ni) ions in the air-synthesized NdBaCo_2−xNi_xO_5+δ samples decrease with increasing Ni content, accompanied by a structural transition from tetragonal (0 ≤ x ≤ 0.4) to orthorhombic (x = 0.6). Similarly, the thermal expansion coefficient (TEC) and electrical conductivity also decrease with increasing Ni content. The x = 0.2 and 0.4 samples exhibit slightly improved performance as cathodes in single cell solid oxide fuel cell (SOFC) compared to the x = 0 sample, which is in accordance with the ac-impedance data. Among the samples studied, the x = 0.4 sample exhibits a combination of low thermal expansion and high catalytic activity for the oxygen reduction reaction in SOFC.     

The transient operation of a solid oxide fuel cell monolith under forced periodic reversal of the flow

The forced periodic reversal of the flow is proposed for the case of a Solid Oxide Fuel Cell (SOFC) monolith. A one-dimensional non-steady state heterogeneous model is applied to an investigation of H₂ electrochemical oxidation in a co-current flow solid oxide monolithic fuel cell. Results are reported on the transient evolution along the reactor, of the species conversion, temperature distribution, thermodynamic energy conversion efficiency and volumetric power density. This novel transient operation of an SOFC leads to improved and highly efficient performances, thus allowing for a combination of the concepts of a regenerative heat preheater and of an electrocatalytic converter, in a single SOFC monolithic assembly.     

Influence of copper oxide modification of a platinum cathode on the activity of direct methanol fuel cell

To determine whether a copper oxide modified Pt cathode (PtCuO_m) improves a performance of direct methanol fuel cells (DMFC), we performed structural and morphological analysis of the cathode and measured current-potential profile and impedance spectroscopy. Comparing with an unmodified Pt cathode, we found that PtCuO_m prepared by rf sputtering techniques induced higher oxygen reduction reaction rate and suppressed electrocatalytic oxidation of methanol, which is the main reason of the mixed potential occurred at a cathode. Therefore, PtCuO_m increased the power performance of DMFC applying both oxygen and air and electrochemical impedance spectra clearly supported the difference of the performance between unmodified and modified Pt electrodes. These results may play a role in better long-term stability of DMFC systems.     

A high-performance solid oxide fuel cell with a layered electrolyte for reduced temperatures

The application of conventional zirconia-based electrolytes is limited to relatively high temperatures (ie > 750°C) due to their poor conductivities at low temperatures. Doped ceria has much higher conductivities; however, when exposed to fuel, electronic current develops within the material, which impairs cell performance and efficiency. Herein, we report a novel layered electrolyte structure consisting of a 10 µm samaria-doped ceria primary layer and a 2 µm scandia-ceria-stabilized zirconia protection layer on the fuel side. The cell had five layers and was fabricated using a tape casting and ultrasonic spraying technique. By carefully selecting the raw materials, the bilyer electrolyte was sintered to full density at a low temperature of 1250°C. The adverse interdiffusion and undesirable reactions between the two layers were largely avoided. A fuel cell with the layered electrolyte structure, operated on hydrogen fuel, produced a high open circuit voltage 1.07 V and a power density of 321 mW/cm² at 0.8 V and 600°C, 76% improvement compared to the fuel cell with a scandia-stabilized zirconia/samaria-doped ceria bilayer electrolyte reported in literature.     

Synthesis and characterization of Sr2+ and Mg2+ doped LaGaO3 by co-precipitation method followed by hydrothermal treatment for solid oxide fuel cell applications

In the present study, LSGM (La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8) powder has been synthesized using precipitation route followed by hydrothermal treatment. Quantitative phase analyses of different powders, have been done by Rietveld analyses of the XRD data and they reveal formation of single phase orthorhombic LSGM at 1400 °C, 8 h. Morphology of the calcined powder and microstructure of the sintered pellets are observed by transmission electron microscope (TEM) and scanning electron microscope (SEM), respectively. Thermal analysis has been carried out to find out the thermal expansion co-efficient. Successive electrical characterization of the 99% dense sintered pellet has been done by impedance spectroscopic analysis. The diffused semicircles observed in the Nyquist plots have been simulated as (RQ)(RQ) circuit and the total ionic conductivity obtained is found to be the highest for LSGM synthesized by similar routes.     

Nano-stuctured Pt-Fe/C as cathode catalyst in direct methanol fuel cell

Pt-Fe/C catalysts were prepared by a modified polyol synthesis method in an ethylene glycol (EG) solution, and then were heat-treated under H₂/Ar (10 vol.%) at moderate temperature (300 °C, Pt-Fe/C300) or high temperature (900 °C, Pt-Fe/C900). As comparison, Pt-Fe/C alloy catalyst was prepared by a two-step method (Pt-Fe/C900B). X-ray diffraction (XRD) and transmission electron microscopy (TEM) images show that particles size of the catalyst increases with the increase of treatment temperatures. Pt-Fe/C300 catalyst has a mean particle size of 2.8 nm (XRD), 3.6 nm (TEM) and some Pt-Fe alloy was partly formed in this sample. Pt-Fe/C900B catalyst has the biggest particle size of 6.2 nm (XRD) and the best Pt-Fe alloy form. Cyclicvoltammetry (CV) shows that Pt-Fe/C300 has larger electrochemical surface area than other Pt-Fe/C and the highest utilization ratio of 76% among these Pt-based catalysts. Rotating disk electrode (RDE) cathodic curves show that Pt-Fe/C300 has the highest oxygen reduction reaction (ORR) mass activity (MA) and specific activity (SA), as compared with Pt/C catalyst in 1.0 M HClO₄. However, Pt-Fe/C catalyst does not appears to be a more active catalyst than Pt/C for ORR in 1.0 M HClO₄ + 0.1 M CH₃OH. Pt-Fe/C300 exhibits higher ORR activity and better performance than other Pt-Fe/C or Pt/C catalysts when employed for cathode in direct methanol single cell test, the enhancement of the cell performance is logically attributed to its higher ORR activity, which is probably attributed to more Pt⁰ species existing and Fe ion corrosion from the catalyst.     

LaNi0.9Ru0.1O3 as a cathode catalyst for a direct borohydride fuel cell

LaNi_0.9Ru_0.1O₃ as cathode catalyst for a direct borohydride fuel cell (DBFC) was synthesized and investigated for the first time. The electrochemical experiments indicated that perovskite-type oxide LaNi_0.9Ru_0.1O₃ exhibited higher electrochemical performance compared with LaNiO₃, which suggested incorporation of element Ru into LaNiO₃ could further improve the catalytic ability for oxygen reduction reaction (ORR) in alkaline solution. LaNi_0.9Ru_0.1O₃ catalyst was found to have good tolerance of BH₄⁻. Meanwhile the maximum power density of 171 mW cm⁻² was obtained at 65 °C without using any precious ion exchange membrane. A life test indicated that the DBFC displayed no significant degradation for about 70 h testing. The electrochemical data suggested that LaNi_0.9Ru_0.1O₃, which provided a simple way to construct DBFCs without using any ion exchange membrane, might be promising cathode catalyst with high performance and low cost for DBFCs.     

Properties of CuMn1.5Ni0.5O4 spinel as high-performance cathode for solid oxide fuel cells

Spinel oxide cathode has made great progress in solid oxide fuel cells (SOFCs) because of its special characteristics different from perovskite. In this study, a spinel-structured SOFC cathode, CuMn_1.5Ni_0.5O₄ (CMN), is proposed. Rietveld refinement shows that CMN takes the cubic structure of the space group of P4₃32. CMN shows a high conductivity of about 70.0–91.2 S cm⁻¹ at 600–800 ºC in the air and exhibits good catalytic activity for oxygen. A symmetric cell with CMN-GDC composite cathode demonstrates a low Rp of 0.047 Ω cm² at 800 ºC. The charge transfer of oxygen is the rate-limiting process at lower temperatures. The performance test results of the button cell with CMN-GDC composite cathode are excellent, with high power densities of 1342.4 mW cm⁻² at 800 ºC. After a110h long-term test, the cell runs stably, and no microstructure damage is observed.     

Review of perovskite-structure related cathode materials for solid oxide fuel cells

In this article, different perovskite-structure related materials are reviewed, which could be potential candidates for cathode materials in solid oxide fuel cells. Solid oxide fuel cells provide an alternative, environmentally viable and efficient option to conventional electricity-producing devices. Different properties are required for the materials to qualify as a cathode for solid oxide fuel cells. Therefore, the analysis and review are done based on the process parameters and their effect on the electrical conductivity, electrochemical properties, the coefficient of thermal expansion and mechanical properties of different cathode materials. Fracture toughness and hardness have been the focus while analysing the mechanical properties. The selection of the initial composition, dopants and their valence plays a vital role in deciding the properties mentioned above of cathode materials. The prospective cathode materials classified as cobalt-based and cobalt-free are further bifurcated based on the A-site elements of the perovskite (ABO₃) structure. Also given in this article is the summary of the latest development on the cathode materials. As observed from the properties studied, cobalt-based materials tend to have higher conductivity than cobalt-free materials. While cobalt-free compositions are cost-effective and have a comparable coefficient of thermal expansion with other components of solid oxide fuel cells. The last section of the article gives the future scope of the research.     

Enhancing the performance and stability of solid oxide fuel cells by adopting samarium-doped ceria buffer layer

In this work, the Sm_0.2Ce_0.8O_1.9 (SDC) buffer layer was used to replace the Gd_0.1Ce_0.9O_1.95 (GDC) buffer layer to improve the long-term stability and performance of the solid oxide fuel cells (SOFCs) in the intermediate temperature (550–750 °C). The buffer layer was prepared by screen printing method. The micromorphology of the SDC buffer layer and the cell structures was observed by scanning electron microscopy (SEM). The electrochemical impedance spectroscopy (EIS) results showed that the polarization resistance (R_P) of the cell with SDC buffer layer was smaller than that of the cell with GDC buffer layer, reducing the R_P values by 43.52% and 43.33%, respectively (SDC-cell: 0.12 Ω cm² at 650 °C and 0.27 Ω cm² at 600 °C). The maximum power density of the cell with SDC buffer layer is 560 mW cm⁻² at 650 °C, which was 25% higher than that with GDC buffer layer. The long-term durability of the cell with SDC buffer layer was better than that of the cell with GDC buffer layer. These provide an excellent prospect for utilizing SDC buffer layer.     

Electrochemical behaviour of propane-fed solid oxide fuel cells based on low Ni content anode catalysts

Two different low Ni content (10 wt.%) anode catalysts were investigated for intermediate temperature (800 °C) operation in solid oxide fuel cells fed with dry propane. Both catalysts were prepared by the impregnation of a Ni-precursor on different oxide supports, i.e. gadolinia doped ceria (CGO) and La_0.6Sr_0.4Fe_0.8Co_0.2O₃ perovskite, and thermal treated at 1100 °C for 2 h. The Ni-modified perovskite catalyst was mixed with a CGO powder and deposited on a CGO electrolyte to form a composite catalytic layer with a proper triple-phase boundary. Anode reduction was carried out in-situ in H₂ at 800 °C for 2 h during cell conditioning. Electrochemical performance was recorded at different times during 100 h operation in dry propane. The Ni-modified perovskite showed significantly better performance than the Ni/CGO anode. A power density of about 300 mW cm⁻² was obtained for the electrolyte supported SOFC in dry propane at 800 °C. Structural investigation of the composite anode layer after SOFC operation indicated a modification of the perovskite structure and the occurrence of a La₂NiO₄ phase. The occurrence of metallic Ni in the Ni/CGO system caused catalyst deactivation due to the formation of carbon deposits.     

Biodiesel formulations as fuel for internally reforming solid oxide fuel cell

Biodiesel (alkyl ester of rapeseed oil) is prepared using various, methyl, ethyl and butyl alcohols through the transesterification process. Sodium hydroxide and sulfuric acid are used as catalyst for methyl alcohol, ethyl alcohol and butyl alcohol respectively. Biodiesel-water formulations are formulated using water and emulsifiers like sodium lauryl sulphate (SLS) and SPAN 80 in a high shear mixer. The formulations are tested at 800 °C as fuel for internal reforming in solid oxide fuel cells (SOFCs). The formulations based on methyl and butyl esters require the use of emulsifiers to prepare stable emulsions, while ethyl esters are able to form stable emulsions without emulsifiers. The decrease in the biodiesel concentration of formulation does not have any effect on the power density of the ethyl ester formulation. Fuel cells fuelled with 20% formulations lasted longer than 50% formulations in all the formulations tested as result of increase in steam carbon ratio resulting in effective removal of carbon deposited on the anode surface. Butyl ester formulations exhibited the worst performance in both types of formulation tests. The best performance was exhibited by 20% ethyl formulation in terms of life of the cell but 50% methyl ester formulations exhibit the highest power density.     

Electric field-assisted sintering anode-supported single solid oxide fuel cell

Cosintering (La_0.84Sr_0.16MnO₃ thin-film cathode/ZrO₂: 8 mol% Y₂O₃ thin-film solid electrolyte/55 vol.% ZrO₂:8 mol% Y₂O₃ + 45 vol.% NiO anode, ϕ = 12 × 1.5 mm thick pellet) was achieved by applying an electric field for 5 min at 1200°C. Impedance spectroscopy measurements of the anode-supported three-layer cell show an improvement of the electrical conductivity in comparison to that of a conventionally sintered cell. The scanning electron microscopy images of the cross-sections of electric field-assisted pressureless sintered cells show a fairly dense electrolyte and porous anode and cathode. Joule heating, resulting from the electric current due to the application of the AC electric field, is suggested as responsible for sintering. Dilatometric shrinkage curves, electric voltage and current profiles, impedance spectroscopy diagrams, and scanning electron microscopy micrographs show how anode-electrolyte-cathode ceramic cells can be cosintered at temperatures lower than the usually required.