Functionally-graded composite cathodes for durable and high performance solid oxide fuel cells

A double-layer dual-composite cathode is fabricated and has an ideal cathode microstructure with large electrochemical active sites and enhanced the durability in solid oxide fuel cells (SOFCs). The insertion of a yttria-stabilized zirconia (YSZ)-rich functional layer between the electrolyte and the electrode allows for a graded transition of the YSZ phase, which enhances ionic percolation and minimizes the thermal expansion coefficient mismatch. Electrochemical measurements reveal that the double-layer composite cathode exhibits improved cathodic performance and long-term stability compared with a single-layer composite cathode. A cell with a well-controlled cathode maintains nearly constant interfacial polarization resistance during an 80 h accelerated lifetime test.     

Synthesis of matrix-type NiO–SDC composite particles by spray pyrolysis with acid addition for development of SOFC cermet anode

Matrix-type NiO–SDC composite particles were synthesized by spray pyrolysis from the starting solution containing citric acid without pre-heat treatment. Matrix-type composite particles synthesized in this study were spherical shape with high-dispersed state of NiO and SDC. The calcined matrix-type NiO–SDC composite particles at 500 and 1000 °C showed the high performance of SOFC anode. From the electrochemical characterization, the matrix-type structure was effective to reduce the ohmic loss, and the calcination treatment for the matrix-type composite particles would reduce the anodic polarization. It was found that the addition of citric acid into the starting solution for spray pyrolysis led to the high-dispersed matrix-type NiO–SDC composite particles with spherical shape, which showed the high performance anode, without any pre-heat treatment of the starting solution.     

Compositional influence of LSM-YSZ composite cathodes on improved performance and durability of solid oxide fuel cells

The use of a dual-composite approach, in which both LSM and YSZ nanoparticles are placed on YSZ core particles, allows for the development of an ideal cathode microstructure with improved phase contiguity and durability for use in solid oxide fuel cells. The volume fraction of the conjugated YSZ phase plays a critical role in the optimization of the cathode microstructure for achieving good durability because it acts as an interconnecting bridge between YSZ core particles. However, the presence of excess conjugated YSZ phase interrupts the formation of sufficient triple phase boundary sites by disturbing the contacts between the LSM and YSZ phases. Impedance spectroscopy analysis and microstructural observations provide a better understanding of the influence of the composition on the electrochemical performance and durability of these dual composite cathodes.     

A facial and effective way to prepare high-performance hetero-structured composite cathode for intermediate temperature solid oxide fuel cells

A hetero-structured composite porous cathode has been prepared by mixing 90 wt% single-phase perovskite (SP¹) La_0·6Sr_0·4Co_0·2Fe_0·8O_3-δ (LSCF113²) and 10 wt% Ruddlesden-Popper layered perovskite (RP³) LaSrCo_0·2Fe_0·8O_4-δ (LSCF214⁴) nano-powders. The powders were separately synthesized by wet chemical coprecipitation (CP⁵) method, and subsequently mixed by ball-milling to obtain the composite CP-LSCF214-113 cathode with RP/SP hetero-interface. The hetero-interface has been confirmed by XRD and TEM. The polarization impedance (R_p) of symmetrical cell with the composite cathode achieved 0.024 and 0.147 Ω cm² at 800 and 700 °C, decreasing 65% and 72% of the cathode impedance of CP-LSCF113, respectively. An anode supported SOFC with the CP-LSCF214-113 composite cathode achieved maximum power density of 1.02 W cm^?2 at 800 °C. The CP-LSCF214-113 based single cell also showed acceptable stability similar to CP-LSCF113 based cell over 100 h at 700 °C. Moreover, the CP-LSCF214-113 effectively inhibits the coarsening of grains and the growth of RP phase. The solid state reaction (SSR⁶) method was used for comparison. Our results revealed that the CP method combined with ball-milling and subsequent calcining is an effective way to construct RP/SP hetero-interface in porous cathodes for intermediate temperature solid oxide fuel cells (IT-SOFCs).     

An oxygen reduction reaction active and durable SOFC cathode/electrolyte interface achieved via a cost-effective spray-coating

One of the critical obstacles for commercialization of solid oxide fuel cells (SOFCs) technology is to develop efficient interfaces between cathode and electrolyte that enable high activity toward oxygen reduction reaction (ORR) while maintain long-term durability. Here, we report a cost-effective spray-coating process that applied in the building of an ORR active and durable cathode/electrolyte interface. When tested at 750 °C, such spray-coated cathodes show a typical interfacial polarization resistance of ~0.059 Ωcm², much lower than that of ~0.10 Ωcm² for screen-printed cathodes. Detailed distribution of relaxation time analyses of the impedance spectra over time indicates that the capability of mass transfer and surface exchange process in the spray-coated cathode/electrolyte interface has been enhanced and maintained in the testing periods of ~100 h. As a result, a Ni-based anode supported cell with thin electrolyte and spray-coated cathodes shows an excellent peak power density of 1.012 Wcm⁻², much higher than that of 0.712 Wcm⁻² for cells with screen-printed cathodes, when tested at 750 °C using wet H₂ as fuel and ambient air as oxidant. It is demonstrated that ORR activity and durability of the SOFC cathodes can be dramatically enhanced via a cost-effective spray-coating process.     

A novel water-based cathode ink formulation

A new cathode ink for a solid oxide fuel cell has been developed (patent pending: UK Patent Application Number 1107672.6). A novel, water-based formulation was created and tested against the standard, in-house, acetone-based ink recipe. Poly(N-VinylPyrrolidone) (PVP) was selected as a suitable dispersant and Poly(Vinyl Alcohol) (PVA) as the binder and a range of chain lengths and quantities was tested. The PVA content was adjusted to optimise adhesion of the two layers, as some delamination was observed with the first attempt. Various PVP chain lengths and quantities were tested to determine the effect on ink dispersion, and hence cathode structure and porosity. The electrical performance was tested and found to be favourably comparable with the in-house recipe, giving a marginally higher peak power density of 0.48 W/cm².     

A short review of cathode poisoning and corrosion in solid oxide fuel cell

Solid oxide fuel cell (SOFC) has been recognized as a promising energy conversion device that is expected to play a critical role in solving the global energy and environmental challenges, however, the durability of SOFC under practical working conditions has limited its wide spread deployment and commercialization. Specifically, SOFC cathode often suffers from various contaminations such as Cr and Si arising from the interconnect and sealing materials, respectively, as well as humidity and CO₂ which are inherent in ambient air, resulting in serious issues in long-term performance degradation. In this review, the impacts of certain poisoning and corrosions on SOFC cathode are introduced, and the latest results of durability research on the corrosion resistant properties of cathode under CO₂, humidity, Cr and Si-containing conditions are reviewed. The poisoning and corrosion mechanism and durability of these aspects are systematically assessed and discussed.     

Performance of a novel La(Sr)MnO3-Pd composite current collector for solid oxide fuel cell cathode

The electrochemical performance of LSM-Pd composite material as current collector of SOFC cathode is studied on (La_0.8Sr_0.2)_0.9MnO₃ (LSM90) cathode. The influence of Pd content on contact resistance is investigated. The investigation shows that the contact resistance of LSM-Pd is about 20 mΩ cm² at 750 °C when the composite contains 8 wt% Pd, and it could be comparable to pure Pt. The ohmic resistance of a single cell using LSM-Pd composite is about 255 mΩ cm² that contains 4 wt% Pd as current collector, this value is close to that of a cell using expensive Pt paste as current collector.     

Nanocrystalline doped lanthanum cobalt ferrite and lanthanum iron cobaltite-based composite cathode for significant augmentation of electrochemical performance in solid oxide fuel cell

Sr-doped lanthanum cobalt ferrite (La_0.54Sr_0.40Co_0.20Fe_0.80O_3−δ) and lanthanum iron cobaltite (La_0.54Sr_0.40Fe_0.20Co_0.80O_3−δ)-based mixed ionic and electronic conducting solid oxide fuel cell cathodes are synthesized by autocombustion technique. In order to examine the electrochemical activity including thermal matching with the adjacent cell components, a composite cathode comprising of both the ferritic and cobaltite system is prepared using mechanical mixing. Powder characterizations for cobaltite and ferritic-based perovskite revealed nanocrystallinity (15–30 nm) with particulate size ranging 50–100 nm. Anode-supported half cell with suitable doped ceria based interlayer on the top of the electrolyte and developed composite cathode augments the current density to 3.98 Acm⁻² at 0.7 V at 800 °C. The oxygen reduction reaction kinetics of such composite cathode shows high exchange current density of 1.16 Acm⁻² with relatively low electrode polarization of 0.02 Ωcm² at 800 °C. The electrochemical performance is clinically correlated with the cell microstructure exhibiting minimum SrO diffusion at the electrode-electrolyte interface.     

Degradation behavior of anode-supported solid oxide fuel cell using LNF cathode as function of current load

We investigated the effect of current loading on the degradation behavior of an anode-supported solid oxide fuel cell (SOFC). The cell consisted of LaNi_0.6Fe_0.4O₃ (LNF), alumina-doped scandia stabilized zirconia (SASZ), and a Ni-SASZ cermet as the cathode, electrolyte, and anode, respectively. The test was carried out at 1073 K with constant loads of 0.3, 1.0, 1.5, and 2.3 A cm⁻². The degradation rate, defined by the voltage loss during a fixed period (about 1000 h), was faster at higher current densities. From an impedance analysis, the degradation depended mainly on increases in the cathodic resistance, while the anodic and ohmic resistances contributed very little. The cathode microstructures were observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM).     

Novel perovskite-spinel composite conductive ceramics for SOFC cathode contact layer

Perovskite-spinel composite conductive ceramics are developed for solid oxide fuel cell (SOFC) cathode contact layer. The precursor of the composite materials includes micron-sized La_0.6Sr_0.4Co_0.2Fe_0.8O₃(LSCF) perovskite particles coated by the reduced nano-sized Mn_0.9Y_0.1Co₂O₄ (MYC) spinel material, and then it is sintered in-situ to obtain perovskite-spinel composites. The sintering activity of the composites is enhanced by using the reduced spinel powders. The conductive performance of the composite materials is effectively improved due to the high conductivity of perovskite LSCF particles utilized. Measured at 750^οC under constant current density of 400 mA/cm², after running 200 h, the area specific resistance (ASR) value of cathode contact layer remains relatively stable at around 5.4 mΩ cm². The developed LSCF-MYC composite as cathode contact layer presents good bonding strength with both cathode and interconnection, and shows obviously low contact resistance and high stability.     

Highly efficient and durable anode-supported SOFC stack with internal manifold structure

We have developed a solid oxide fuel cell (SOFC) stack with an internal manifold structure. The stack, which is composed of 25 anode-supported 100-mm-diameter SOFCs, provided an electrical conversion efficiency of 56% (based on the lower heating value of methane, which was used as a fuel) and an output of 350 W when the fuel utilization, current density, and operating temperature were 75%, 0.3 A cm⁻², and 1073 K, respectively. The electrical efficiency and the output were maintained for 1100 h. The cell voltage fluctuation was ±2% for 25 cells. The relationship between average cell voltage and current density in the 25-cell stack was as almost the same as that in the 1- and 10-cell stacks, which suggests that our stack provides almost the same cell performance regardless the number of the cells.     

Ni–Fe + SDC composite as anode material for intermediate temperature solid oxide fuel cell

Composite materials of Sm_0.2Ce_0.8O_1.9 (SDC) with various Ni–Fe alloys were synthesized and evaluated as the anode for intermediate temperature solid oxide fuel cell. The performance of single cells consisting of the Ni–Fe + SDC anode, SDC buffer layer, La_0.8Sr_0.2Ga_0.83Mg_0.17O_2.815 (LSGM) electrolyte, and SrCo_0.8Fe_0.2O_3 − δ (SCF) cathode were measured in the temperature range of 600–800 °C with wet H₂ as fuel. It was found that the anodic overpotentials of the different Fe–Ni compositions at 800 °C were in the following order: Ni_0.8Fe_0.2 < Ni_0.75Fe_0.25 < Ni < Ni_0.7Fe_0.3 < Ni_0.9Fe_0.1 < Ni_0.95Fe_0.05 < Ni_0.33Fe_0.67. The single cell with the Ni_0.8Fe_0.2 + SDC anode exhibited a maximum power density of 1.43 W cm⁻² at 800 °C and 0.62 W cm⁻² at 700 °C. The polarization resistance of the Ni_0.8Fe_0.2 + SDC anode was as low as 0.105 Ω cm² at 800 °C under open circuit condition. A stable performance with essentially negligible increase in anode overpotential was observed during about 160 h operation of the cell with the Ni_0.8Fe_0.2 + SDC anode at 800 °C with a fixed current density of 1875 mA cm⁻². The possible mechanism responsible for the improved electrochemical properties of the composite anodes with the Ni_0.8Fe_0.2 and Ni₀₇₅Fe_0.25 alloys was discussed.     

LaNi0.6Fe0.4O3-Ce0.8Sm0.2O1.9-Ag composite cathode for intermediate temperature solid oxide fuel cells

LaNi_0.6Fe_0.4O₃ (LNF), LNF-Sm_0.2Ce_0.8O_1.9 (SDC), and LNF-SDC-Ag cathodes on SDC electrolytes were investigated at intermediate temperatures using AC impedance spectroscopy. Results show that adding 50 wt.% SDC into LNF yields a significant low area specific resistance (ASR) which was found to be 0.92 Ω cm² at 700 °C. Infiltrating 0.3 mg/cm² Ag into LNF-50 wt.% SDC can improve the electronic conductivity and oxygen exchange reaction activity, and thereby remarkably decrease the ASRs. The ASR value of the LNF-SDC-Ag cathode is as low as 0.18 Ω cm² at 700 °C, and 0.46 Ω cm² at 650 °C. The long-term test shows that the LNF-SDC-Ag cathode may be a promising candidate for solid oxide fuel cells operating at temperatures lower than 650 °C.     

Synthesis and characterization of aluminum-doped perovskites as cathode materials for intermediate temperature solid oxide fuel cells

(Ba_0.5Sr_0.5)(Fe_1-xAl_x)O_3-δ (BSFAx, x = 0–0.2) oxides have been synthesized as novel cobalt-free cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs) using a sol-gel method. The BSFAx (x = 0–0.2) materials have been characterized by X-ray diffraction and scanning electron microscopy. The electrical conductivities and electrochemical properties of the prepared samples have also been measured. At 800 °C, the conductivity drops from 15 S cm⁻¹ to 5 S cm⁻¹ when the doping level of aluminum is increased to 20%. The aluminum-doping concentration has important impacts on the electrochemical properties of BSFAx materials. The BSFA0.09 cathode shows a significantly lower polarization resistance (0.26 Ω cm²) and cathodic overpotential value (55 mV at the current density of 0.1 A cm⁻²) at 800 °C. Furthermore, an anode-supported single cell with BSFA0.09 cathode has been fabricated and operated at a temperature range from 650 to 800 °C with humidified hydrogen (∼3vol% H₂O) as the fuel and the static air as the oxidant. A maximum power density of 676 mWcm⁻² has been achieved at 800 °C for the single cell. We believe that BSFA0.09 is a promising cathode material for future IT-SOFCs application.     

Fabrication of cathode supported solid oxide fuel cell by multi-layer tape casting and co-firing method

La_0.3Sr_0.7FeO_3-δ (LSF)/CeO₂ cathode supported Ce_0.8Sm_0.2O_2-δ (SDC) electrolyte was prepared by a simple multilayer tape casting and co-firing method. SDC electrolyte slurry and LSF/CeO₂ cathode slurry were optimized and the green bi-layer tapes were co-fired at different temperature. Phase characterizations and microstructures of electrolyte and cathode were studied by X-ray diffraction (XRD) and Scan Electronic Microscopy (SEM). No additional phase peak line was observed in electrolyte and cathode support when the sintering temperature lower was than 1400 °C. The electrolytes were extremely dense with the thickness of about 20 μm. The cathode support was porous with electrical conductivity of about 4.21 S/cm at 750 °C. With Ni/SDC as anode, Open Current Voltage and maximum power density reached 0.61 V and 233 mW cm⁻² at 750 °C, respectively.     

Fundamental mechanisms limiting solid oxide fuel cell durability

The fundamental issues associated with solid oxide fuel cell (SOFC) durability have been reviewed with an emphasis on general features in SOFCs and respective anode and cathode related phenomena. As general features, physicochemical properties and cell performance degradation/failure are correlated and bridged by the electrode reaction mechanisms. Particular emphasis is placed on the elemental behaviour of gaseous impurities and the possible role of liquids formed from gaseous substances. The lifetime of a state-of-the-art Ni cermet anodes is limited by a variety of microstructural changes, which mainly result from material transport-, deactivation- and thermomechanical mechanisms. Anode degradation can mainly be influenced by processing, conceptual and operating parameters. Designing a redox stable anode is currently one of the biggest challenges for small scale SOFC systems. Degradation mechanisms of different cathode materials are reviewed with a focus on the intrinsic degradation of doped lanthanum manganites (e.g. LSM) and doped lanthanum ferro-cobaltites (LSCF). Manganese-based perovskites can be regarded to be sufficiently stable, while for the better performing LSCF cathodes some intrinsic degradation was detected. New materials that are supposed to combine a better stability and high performance are also shortly mentioned.     

Monte-Carlo simulation and performance optimization for the cathode microstructure in a solid oxide fuel cell

A 3D micro-scale model is developed to simulate the transport and electrochemical reaction in a composite cathode. This model takes into account the details of the specific cathode microstructure such as random pore structure, active TPB (three phase boundary) site distribution, particle size and composition and their interrelationship to the charge transfer and mass transport processes. Especially, the pore structure and mass diffusion were incorporated into this model. Influence of the microsturcture parameters on the performance was investigated by numerical simulations.     

A high-performance direct carbon solid oxide fuel cell powered by barium-based catalyst-loaded biochar derived from sunflower seed shell

Direct carbon solid oxide fuel cell (DC-SOFC) is one of the most attractive thesises for clean and efficient utilization of solid carbon to produce electricity. According to the operating principle, DC-SOFC performance is closely associated with the carbon sources and catalysts of the reverse Boudouard reaction. Here, we report a high-performance DC-SOFC powered by the biochar derived from sunflower seed shell (SSS) with barium-based catalyst loaded. The physicochemical properties of the SSS biochar are characterized and analyzed detailly. The electrolyte-supported symmetrical SOFC fueled with the SSS biochar gives an output of 216 mW cm^?2 at 850 °C, indicating a great potential of the SSS biochar for DC-SOFCs. More importantly, the best output of 265 mW cm^?2 and open circuit voltage of 1.03 V are obtained from DC-SOFC operated on 5 wt% barium-loaded SSS biochar, which is comparable to the output of 273 mW cm^?2 from the hydrogen-fueled SOFC at 850 °C with the identical configuration. The superiorities of the SSS biochar and barium-based catalyst are also reflected in the operation stability and fuel utilization of DC-SOFCs. The discharge platforms are stable and the longest lifetime is up to 28.0 h under 50 mA with the fuel utilization of 31.3%, which is very excellent and competitive. This work provides a new idea for the effective utilization of the SSS biochar and other biomass for DC-SOFCs.     

Effect of reduced graphene oxide addition on cathode functional layer performance in solid oxide fuel cells

Solid oxide fuel cells (SOFCs) operating at high temperatures are highly efficient electrochemical devices since they convert the chemical energy of a fuel directly into heat and electrical energy. The electrochemical performance of an SOFC is significantly influenced by the materials and microstructure of the electrodes since the electrochemical reactions in SOFCs take place at three/triple phase boundaries (TPBs) within the electrodes. In this study, graphene in the form of reduced graphene oxide (rGO) is added to cathode functional layer (CFL) to improve the cell performance by utilizing the high electrical properties of graphene. Various cells are prepared by varying the rGO content in CFL slurry (1–5 wt %), the number of screen printing (1–3) and the cathode sintering temperature (900–1100 °C). The electrochemical behavior of the cells is evaluated by electrochemical performance and impedance tests. It is observed that there is a ∼26% increase in the peak performance of the cell coated with single layer CFL having 1 wt % graphene and 1050 °C sintering temperature, compared to that of the reference cell.