Development of solid oxide fuel cells (SOFCs) by tape-casting and single-step co-firing of monolithic laminates

We developed a cost-effective method to manufacture high performance-monolithic solid oxide fuel cells using nano-composite electrodes, tape-casting and single-step co-firing.     

Synthesis and characterization of NiO/GDC–GDC dual nano-composite powders for high-performance methane fueled solid oxide fuel cells

GDC (gadolinium-doped ceria) is well known as a high oxygen ionic conductor and is a catalyst for the electrochemical reaction with methane fuel leading to the oxidation of deposited carbon that can clog the pores of the anode and break the microstructure of the anode. NiO/GDC–GDC dual nano-composite powders were synthesized by the Pechini process, which were used as an AFL (anode functional layer) or anode substrates along with a GDC electrolyte and LSCF–GDC cathode. The anodes, AFL, and electrolyte were fabricated by a tape-casting/lamination/co-firing. NiO–GDC anode and NiO/GDC–GDC anode-supported unit cells were evaluated in terms of their power density and durability. As a result, the NiO/GDC–GDC dual nano-composite demonstrated an improved power density from 0.4 W/cm² to 0.56 W/cm² with H₂ fuel/air and from 0.3 W/cm² to 0.56 W/cm² with CH₄ fuel/air at 650 °C. In addition, it could be operated for over 500 h without any degradation with CH₄ fuel.     

Performance improvement of anode-supported electrolytes for planar solid oxide fuel cells via a tape-casting/lamination/co-firing technique

Recently, solid oxide fuel cells (SOFCs) have attracted considerable attention because of their low emissions, high-energy conversion efficiency, and flexible usage of various fuels. One of the key problems of applying flat-type SOFCs to large-scale power generation is that unit cells of large area and with a high degree of flatness cannot be manufactured satisfactorily.In this study, the effects of tape-casting, laminating, and co-firing conditions on the flatness of anode-supported electrolyte unit cells have been investigated to improve the cell performance of unit cells. The cells are composed of a Ni-yttria-stabilized zirconia (YSZ) anode, a Ni-YSZ anode functional layer (AFL), a YSZ electrolyte, and a lanthanum strontium manganate (LSM)-YSZ cathode. The flatness of the anode-supported electrolyte is optimized by controlling the firing schedule, the lamination method, and the applied load during firing. A 5 cm × 5 cm (active area 4 cm × 4 cm) unit cell having a reasonable flatness of 55 μm/5 cm shows a higher power output of 11.4 W as compared with 7.7 W a unit cell with a flatness of 200 μm/5 cm, when operating at 800 °C with humidified hydrogen fuel.     

Stress and camber analysis of anode-supported electrolytes by tape-casting and co-firing techniques

Solid oxide fuel cells (SOFCs) have begun to attract attention because of their low emissions, high-energy conversion efficiencies, and flexibility with various fuels. However, it is very difficult to produce large area unit cells with a high degree of flatness using tape-casting and co-firing. Therefore, the understanding of unit cell behavior during co-firing is very important in the manufacturing field of SOFCs.The densification-based finite element method (DFEM) was selected for modeling and analysis of the co-firing behavior of a SOFC unit cell. The DFEM corroborated the experimental results. The anode support thickness mainly affected the camber among the SOFC components.When applying compressive force during co-firing, the camber was minimized when the loading density was near 12 g cm⁻², and the deformation rate increased rapidly as the compressive loading density increased. Additionally, the application of the compressive force affected the internal stress distribution. The co-fired cell with an applied optimal compressive force showed homogeneous stress distribution.     

Applications of nano-composite materials for improving the performance of anode-supported electrolytes of SOFCs

In order to improve the performance of the anode-supported electrolyte of solid oxide fuel cells (SOFCs), the anode electrode is modified by inserting an anode functional layer of nano-composite powders between a Ni–YSZ electrode and YSZ electrolyte. The NiO–YSZ nano-composite powders are fabricated by coating nano-sized Ni and YSZ particles on the YSZ core particle by the Pechini process. The reduction of the polarization resistance of a single cell that is applied to the anode functional layer is attributed to the increasing reaction of three-phase boundaries (TPBs) within the layer and the micro-structured uniformity in the electrode. Two methods were used, namely tape-casting/dip-coating and tape-casting/co-firing, for studying the performance. It can be concluded that the cell with an anode functional layer thickness (15–20 μm) and a microstructure of NiO–YSZ nano-composite materials which was fabricated by the tape-casting/dip-coating method improved the output power (to 1.3 W cm⁻²) at 800 °C using hydrogen as fuel and air as an oxidant.     

Characteristics of SOFC single cells with anode active layer via tape casting and co-firing

SOFC (solid oxide fuel cell) single cells with anode active layers of various thicknesses were fabricated successfully via tape casting and co-firing in order to improve their electrochemical performance and long-term stability. The mercury porosimeter and the gas permeability were measured so as to examine the effects of the anode active layer while under a gaseous flow. It was found that the anode active layers affected the microstructural characteristics as a result of the pore distribution and the gas permeation behavior. The anode active layers improved the cell performance by increasing the number of active sites in the anode. The thickness of the anode active layer was optimized at 20 μm in this work through a combination of the power density, the ohmic ASR (area specific resistance), and the cell ASR. SOFCs with the optimized active layer showed good electrochemical performance at 600–700 °C in hydrogen or hydrocarbon fuel (methane) and excellent long-term stability for 500 h.     

Fabrication and evaluation of anode and thin Y2O3-stabilized ZrO2 film by co-tape casting and co-firing technique

Co-tape casting and co-firing of supporting electrode and electrolyte layers could drastically increase productivity and reduce fabrication cost. In this study, Ni-YSZ anode supporting electrode and the YSZ electrolyte with the size of 6.5 cm × 6.5 cm have been successfully fabricated by co-tape casting and co-firing technique. The cell with 1.5 mm anode and 10 μm electrolyte is flat without warping, cracks or delaminations. The power density reaches 661, 856, 1085 mW cm⁻² at 0.7 V and 750, 800 and 850 °C, respectively. The EIS results demonstrate that the cathodic electrochemical resistance is 0.0680 Ω cm², about twice of the anode's which is 0.0359 Ω cm². SEM images show the dense YSZ film had a crack free of surface morphology. The anode and cathode layers are well-adhered to the YSZ electrolyte layer. The La_0.8 Sr_0.2 MnO_3−δ particles do not form a continuous network. Optimization of finer cathodic microstructure and anodic porosity are underway.     

Fabrication of planar-type SOFC single cells by a novel vacuum dip-coating method and co-firing/infiltration techniques

A novel vacuum dip-coating method has been adopted to form a dense thin yttrium stabilized zirconia (YSZ) layer on the pre-fired Ni/YSZ anode substrate. Scandia-stabilized Zirconia (ScSZ) was screen-printed onto the YSZ layer as the cathode backbone material and co-fired in a single step. Sm_0.5Sr_0.5CoO_3−δ (SSC) nanoparticles were infiltrated into the ScSZ porous layer with a loading of 29.17wt% to gain the composite cathode. Without any optimization, the cell reached a maximum power density of 0.85 W cm⁻² with an area-specific resistance of 0.914 Ω cm² at 750 °C.     

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.     

Fabrication and characterization of an anode-supported hollow fiber SOFC

In this study, an anode-supported hollow-fiber solid oxide fuel cell (SOFC) of diameter 1.7 mm has been successfully fabricated using the phase inversion and vacuum assisted coating techniques. The cell has a special structure consisting of a 12-μm-thick yttria-stabilized zirconia (YSZ) electrolyte film and a Ni-YSZ anode layer which has large finger-like pores on both sides of the hollow-fiber membrane. The hollow-fiber SOFC has an active electrode area of 0.63 cm² and generates maximum power densities of 124, 287 and 377 mW cm⁻² at 600, 700 and 800 °C, respectively, indicating that its use in applications requiring high power density is promising.     

Fabrication and characterization of Cu–Ni–YSZ SOFC anodes for direct use of methane via Cu-electroplating

The Cu–Ni–YSZ cermet anodes for direct use of methane in solid oxide fuel cells have been fabricated by electroplating Cu into a porous Ni–YSZ cermet anode. The uniform distribution of Cu in the Ni–YSZ anode was obtained by electroplating in an aqueous solution mixture of CuSO₄·5H₂O and H₂SO₄ for 30 min with 0.1 A of applied current. When the Cu–Ni–YSZ anode was exposed to methane at 700 °C, the amount of carbon deposited on the anode decreased as the amount of Cu in the Cu–Ni solid solution increased. The power density (0.24 W/cm²) of a single cell with a Cu–Ni–YSZ anode was slightly lower in methane at 700 °C than the power density (0.28 W/cm²) of a single cell with a Ni–YSZ anode. However, the performance of the Ni–YSZ anode-supported single cell degraded steeply over 21 h because of carbon deposition, whereas the Cu–Ni–YSZ anode-supported single cell showed enhanced durability up to 200 h.     

Porous Ni/8YSZ anode of SOFC fabricated by the plasma sprayed method

In the present study, porous electrode coating of Ni/8YSZ on the interconnector material was made by the plasma-spraying. By introducing the pore former into the composite powder, the porous structure of SOFC anode will be obtained. By using the plasma spraying technique for SOFC fabrication, we can avoid the thermal failure between the components of SOFC which made from the traditional sintering method at high temperature. In this study, two kinds of composite powders in the granulate form were prepared, one with the nano carbon as a pore former and the other without the carbon. The results showed that the porous structure of SOFC anode could be achieved by the plasma spraying technique. The porosity of the anode made from the composite powder with pore former was 40%. Without pore former the porosity in the anode coating after hydrogen reduction was almost 30%. These results suggest that this method exhibits the potential to manufacture the porous ceramic/metal composite anode of SOFC to achieve the larger triple phase boundary for fuel oxidation.     

Fabrication of integrated BZY electrolyte matrices for protonic ceramic membrane fuel cells by tape-casting and solid-state reactive sintering

Integrated porous/dense/porous tri-layer BaZr_0.8Y_0.2O_3-δ (BZY) electrolyte asymmetrical matrices were designed for protonic ceramic membrane fuel cells (PCMFCs) and fabricated by multilayer tape-casting and solid-state reactive sintering. The effects of pore-former, sintering aid and sintering program on the microstructure of integrated electrolyte matrices (IEMs) were studied. Graphite and NiO were appropriate pore-former and sintering aid, respectively, and an accelerated heating program was more desirable. The conductivities of the IEM with designed microstructure in different atmospheres were measured by AC impedance spectroscopy at 400–600 °C. The highest conductivity of 6.9 × 10^?3 S cm^?1 at 600 °C was obtained in wet air atmosphere, and the corresponding activation energy was 0.602 eV. Gas-tightness of the IEM was confirmed by a stable open circuit voltage (OCV) of 0.97 V at 600 °C from a button fuel cell with impregnated NiO anode and BaCo_0.4Fe_0.4Zr_0.1Y_0.1O_3-δ (BCFZY) cathode. These indicate that the fabricated BZY-based IEM has great potential for PCMFC application.     

Fabrication of bilayered YSZ/SDC electrolyte film by electrophoretic deposition for reduced-temperature operating anode-supported SOFC

Bilayered Y₂O₃-stabilized ZrO₂ (YSZ)/Sm₂O₃-doped CeO₂ (SDC) electrolyte films were successfully fabricated on porous NiO–YSZ composite substrates by electrophoretic deposition (EPD) based on electrophoretic filtration followed by co-firing with the substrates. In EPD, positively charged YSZ and SDC powders were deposited directly on the substrates, layer by layer from ethanol-based suspensions. Delamination between YSZ and SDC films was avoided by reducing the SDC films’ thickness to ca. 1 μm. A single cell was constructed on the bilayered electrolyte films composed of ca. 4 μm-thick YSZ and ca. 1 μm-thick SDC films. As a cathode in the cell, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−x (LSCF) was used. Maximum output power densities greater than 0.6 W cm⁻² were obtained at 700 °C for the bilayered YSZ/SDC electrolyte cells thus constructed.     

Performance enhancement of biodiesel fueled SOFC using paper-structured catalyst

In this study, performance of solid oxide fuel cell (SOFC) connected with paper-structured catalyst (PSC) was evaluated in the direct feed of wet oleic fatty acid methyl ester (oleic-FAME, C₁₉H₃₆O₂), which is a mono-unsaturated component of practical biodiesel fuels (BDFs), in the steam to carbon ratio (S/C) range between 2.0 and 3.5, and high current density of 1 A cm⁻² (at 0.7 V) was recorded at 800 °C. Long term stability of oleic-FAME fueled SOFC was achieved by the incorporation of PSC into SOFC even under severe operating condition prone to coking (direct feed of unsaturated hydrocarbon with carbon number 19 and low S/C ratio of 2.0). After 100 h test, coking was not observed in both SOFC anode and PSC.     

A cost-effective process for fabrication of metal-supported solid oxide fuel cells

Metal-supported SOFC cells with Y₂O₃ stabilized ZrO₂ as the electrolyte were prepared by a low cost and simple process involving tape casting, screen printing and co-firing. The interfaces were well bonded after the reduction of NiO to Ni in the support and the anode. AC impedance was employed to estimate the cell polarizations under open circuit conditions. It was found that the electrode polarization resistance was high at low temperatures and became equivalent to the ohmic resistance at higher temperatures near 800°°C. The cell performance was evaluated with H₂ as the fuel and air as the oxidant, and maximum power density between 0.23 and 0.80  W/cm² was achieved in the temperature range of 650–800°C, which confirms the applicability of the cost-effective process in fabrication of metal-supported SOFC cells.     

Redox-stable Sr0.9La0.1TiO3-supported SOFC single cells

The stable conductive oxide Sr_0.9La_0.1TiO₃ (SLT), instead of the conventional Ni-zirconia, is applied as supporting porous substrate for an SOFC single cell. Four different composite anode materials: Ni-SSZ (SSZ: (ZrO₂)_0.89(Sc₂O₃)_0.1(CeO₂)_0.01), Ni-GDC (GDC: Ce_0.9Gd_0.1O₂), Ni-GDC-SLT, and GDC-SLT were prepared. The porous thick Sr_0.9La_0.1TiO₃ substrate was stable enough during 50 redox cycles so that OCV showed no decrease during the cycling test. Moreover, the electrochemical performance, redox stability, and performance degradation during the cycling tests were mainly determined by the different electrical and catalytic properties of the composite anode materials.     

Evaluation of Nb- or Mo-alloyed ferritic stainless steel as SOFC interconnect by using button cells

The Fe–22Cr–0.5Mn ferritic stainless steel alloyed with Nb or with Mo is evaluated in the button cell configuration at 750 °C in terms of degradation in ohmic resistance and cathodic polarization resistance. STS444 and Crofer22 APU are also evaluated for comparison. Each polarization element is separated by equivalent circuit analysis on the electrochemical impedance spectroscopy data. Cr deposition on the button cell cathode is also analyzed both qualitatively by transmission electron microscope and quantitatively by inductively coupled plasma. The Nb- or Mo-alloyed ferritic stainless steel shows comparable performance with Crofer22 APU in terms of the increase rate in ohmic resistance and Cr evaporation rate, even without the addition of reactive element such as La. When the same amount of Cr is deposited on the cathode, the cathode performance deteriorates more at the high Cr evaporation rate than at the low Cr evaporation rate.