Multilayer tape casting of large-scale anode-supported thin-film electrolyte solid oxide fuel cells

Tape casting is conventionally used to prepare individual, relatively thick components (i.e., the anode or electrolyte supporting layer) for solid oxide fuel cells (SOFCs). In this research, a multilayer ceramic structure is prepared by sequentially tape casting ceramic slurries of different compositions onto a Mylar carrier followed by co-sintering at 1400 °C. The resulting half-cells contains a 300 μm thick NiO–yttria-stabilized zirconia (YSZ) anode support, a 20 μm NiO–YSZ anode functional layer, and an 8 μm YSZ electrolyte membrane. Complete SOFCs are obtained after applying a Gd_0.1Ce_0.9O₂ (GDC) barrier layer and a Sm_0.5Sr_0.5CoO₃ (SSC) -GDC cathode by using a wet-slurry spray method. The 50 mm × 50 mm SOFCs produce peak power densities of 337, 554, 772, and 923 mW/cm² at 600, 650, 700, and 750 °C, respectively, on hydrogen fuel. A short stack including four 100 mm × 150 mm cells is assembled and tested. Each stack repeat unit (one cell and one interconnect) generates around 28.5 W of electrical power at a 300 mA/cm² current density and 700 °C.     

High-performance NdSrCo2O5+δ–Ce0.8Gd0.2O2-δ composite cathodes for electrolyte-supported microtubular solid oxide fuel cells

NdSrCo₂O_5+δ (NSCO) is a perovskite with an electrical conductivity of 1551.3 S cm⁻¹ at 500 °C and 921.7 S cm⁻¹ at 800 °C and has a metal-like temperature dependence. This perovskite is used as the cathode material for Ce_0.8Gd_0.2O_2-δ (GDC)-supported microtubular solid oxide fuel cells (MT-SOFCs). The MT-SOFCs fabricated in this study consist of a bilayer anode, comprising a NiO–GDC composite layer and a NiO layer, and a NSCO–GDC composite cathode. Three cell designs with different outer tube diameters, GDC thicknesses, and NSCO/GDC ratios are designed. The MT-SOFC with an outer tube diameter of 1.86 mm, an electrolyte thickness of 180 μm, and a 5NSCO–5GDC composite cathode presents the best performance. The flexural strength of the aforementioned cell is 177 MPa, which is sufficient to confer mechanical integrity to the cell. Moreover, the ohmic and polarization resistance values of the cell are 0.22 and 0.09 Ω cm² at 700 °C, respectively, and 0.15 and 0.03 Ω cm² at 800 °C, respectively. These results indicate that the NSCO-GDC composite exhibits high electrochemical activity. The maximum power densities of the cell at 700 and 800 °C are 0.46 and 0.67 W cm⁻², respectively, exceeding those of existing electrolyte-supported MT-SOFCs with similar electrolyte thicknesses.     

Fabrication of electrolyte supported micro-tubular SOFCs using extrusion and dip-coating

Dense electrolyte supported micro tubular solid oxide fuel cells (T-SOFCs) were prepared in this study. Green Zr_0.8Sc_0.2O_2 − δ (ScSZ) electrolyte micro-tubes with a thickness of 300 μm were successfully prepared by extrusion at room temperature. After firing at 1400 °C, the bare electrolyte micro-tube with a thickness of 210 μm, a diameter of 3.8 mm, and a length of 40 mm reached a relative density of 96.84% and a flexural strength of 202 MPa. To achieve a better sintering shrinkage match, the electrolyte micro-tubes were pre-sintered at 1100 °C, coated with NiO/ScSZ (60 vol.%:40 vol.%) in the inner surface of the micro-tubes by dip-coating method, and then co-fired at 1400 °C. After co-sintering, the interface of the porous anode layer and the dense electrolyte layer demonstrated good adhesion and mechanical integrity. Subsequently, a La_0.8Sr_0.2MnO_3 − δ (LSM)/Ce_0.8Gd_0.2O_2 − δ (GDC) (80 vol.%:20 vol.%) cathode layer was coated on the outer surface of the micro-tubes by dip-coating method and post-sintered at 1100 °C. The thicknesses of the anode and cathode layers read approximately 28 and 34 μm respectively. After thermal cycling between 30 °C and 800 °C under 97% N₂–3%H₂ on the anode and air on the cathode, the micro T-SOFCs showed no delamination and retained good adhesion based on the SEM results. The maximum power densities (MPD) of the single cell read 0.26 and 0.23 W cm⁻² respectively at 920 and 900 °C, and the open circuit voltage (OCV) reported the same 1.08 V.     

Achieving high mechanical-strength CH4-based SOFCs by low-temperature sintering (1100 °C)

Despite much progress achieved in the past decades in the process of advancing the low-temperature sintering technologies for Solid oxide fuel cells (SOFCs), such as via the structure design of the electrode materials, the practical application of low-temperature sintered SOFCs (with disqualified mechanical strength) remains challenging. In this work, first, we demonstrate that the appropriate amount of CuO as sintering aids can successfully reduce the co-firing temperature of conventional micron size NiO-YSZ (yttrium-stabilized zirconia (Y₂O₃)_0.08–(ZrO₂)_0.92) anode from about 1400 °C to only 1100 °C. Second, the quantitative structure-activity relationship among the mechanical strength (low-temperature sintering ability) of anode cermets with the inclusion of CuO contents and the densification of YSZ electrolyte was synthetically evaluated, and the optimal Cu–NiO-YSZ anode composition demonstrates almost the equal mechanical strength when compared with the traditional NiO-YSZ anode (sintering at 1400 °C). At last, by comprehensive assessment, 8%Cu–52NiO-40YSZ (8%CuO–NiO-YSZ) shows excellent low-temperature sintering ability, high mechanical strength, optimal power output, and anti-carbon deposition when using as hydrocarbon-based anode for SOFCs.     

Comparison of electrolyte fabrication techniques on the performance of anode supported solid oxide fuel cells

A comparison of three solid oxide electrolyte fabrication processes, namely dip coating, screen printing and tape casting, for planar anode supported solid oxide fuel cells (SOFCs) is presented in this study. The effect of sintering temperature (1325–1400 °C) is also examined. The anode and cathode layers of the anode-supported cells, on the other hand, are fabricated by tape casting and screen printing, respectively. The quality of the electrolytes is evaluated via performance measurements, impedance analyses and microstructural investigations of the cells. It is found that the density of the electrolyte increases with the sintering temperatures for all fabrication methods studied. The results also show that with the process and fabrication parameters considered in this study, both dip coating and screen printing do not yield a desired dense electrolyte structure as proven by open circuit potentials measured and SEM photos. The cells with tape cast electrolytes, on the other hand, provide the highest performances regardless of the electrolyte sintering and cell operating temperatures. The best peak performance of 0.924 W/cm² is obtained from the cell with tape cast electrolyte sintered at 1400 °C. SEM investigations and measured open circuit potentials reveal that almost fully dense electrolyte layer can be obtained with a tape cast electrolyte particularly sintered at temperatures higher than 1350 °C. Impedance analyses indicate that the main reason behind the significantly higher performances is due to not only increased electrolyte density but a decrease in the interface resistance of the anode functional and electrolyte layer is also responsible. This can be explained by the load applied during the lamination step in the fabrication of the tape cast electrolyte, providing better powder compaction and adhesion.     

Experimental optimization of the fabrication parameters for anode-supported micro-tubular solid oxide fuel cells

A systematic optimization of several parameters significant in the fabrication of anode-supported micro-tubular solid oxide fuel cell via extrusion and dip coating is presented in this study. Co-sintering temperature of anode-support and electrolyte, the vehicle type and solid powder content used in electrolyte dip-coating slurry, electrolyte submersion time, cathode sintering temperature, powder ratio in the cathode functional layer, submersion time for the cathode functional layer and, submersion time and coating number of the anode functional layer are studied in this respect and optimized in the given order according to the performance tests and microstructural analyses. The performance of the micro-tubular cell is significantly improved to 0.49 Wcm⁻² at 800 °C after the optimizations, while that of the base cell is only 0.136 Wcm⁻². 12-cell micro-tubular stack is also constructed with the optimized cells and the stack is tested. Each cell in the stack is found to show very close performance to the single-cell performance and the stack with a maximum power of ~26 W at an operating temperature of 800 °C is therefore evaluated to be successful.     

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.     

Thin layer electrolyte impregnation into porous anode-supported fuel cell by ultrasonic spray pyrolysis

An ultrasonic spray pyrolyzed thin layer electrolyte impregnates into a porous anode and extends the depth of triple phase boundaries (TPBs) to several times that of the dense thin-layer thickness. This process, without an anode functional layer, improves the conventional repeated impregnation that results in anode porosity blocking and difficult extending to the anode/electrolyte interface. A (La_0.75Sr_0.2Ba_0.05)_0.175Ce_0.825O_1.981 (LSBC) electrolyte thin layer (iLSBC) is deposited on a porous La_0.3Sr_0.7TiO₃ (LST) anode by ultrasonic spray pyrolysis using 0.1 M LSBC precursor at a substrate temperature of 450 °C, while controlling the solution flow rate and spray volume. The spray pyrolyzed iLSBC/LST half-cells co-fired at 1350 °C/6 h exhibit no evident second phase in the X-ray diffraction analysis. The depth profile of iLSBC/LST indicates an approximately 2.75 μm-thick layer with the Ce element line scanning showing a significantly higher impregnation depth. Slight lattice distortion among the impregnated region may be due to the iLSBC diffusion, resulting in the extension of the TPB area and length. The half-cell reaches a low impedance and achieves a power density of 377 mW/cm² at 750 °C.     

Fabrication and characterization of planar-type SOFC unit cells using the tape-casting/lamination/co-firing method

In this study, solid oxide fuel cells (SOFCs) consisting of a NiO-YSZ anode, a NiO/YSZ-YSZ functional layer, YSZ electrolyte and a (La_0.8Sr_0.2)MnO₃ + yttria-stabilized zirconia (LSM-YSZ) cathode were fabricated by tape-casting, lamination, and a co-firing process. NiO/YSZ-YSZ nano-composite powder was synthesized for the anode functional layer via the Pechini process in order to improve cell performance. After optimization of the slurries for the anode functional anode, electrolyte and cathode, all components were casted so as to fabricate the monolithic laminate. The co-firing temperature was optimized to minimize second phase formation between the (La_0.8Sr_0.2)MnO₃ (LSM) and yttria-stabilized zirconia (YSZ) and to increase the sinterability of the YSZ electrolyte. The YSZ electrolyte was fully sintered with the addition of 0.5 wt% CuO, and the second phases of La₂Zr₂O₇ and SrZrO₃ did not form at 1350 °C. Ni-YSZ anode-supported unit cells were fabricated by co-firing at 1250-1400 °C. The unit cells co-fired at 1250 °C, 1300 °C, 1325 °C, 1350 °C and 1400 °C had maximum power densities of 0.18, 0.18, 0.30, 0.46 and 0.036 W/cm², respectively, in humidified hydrogen (∼3% H₂O) and air at 800 °C.     

Screen-printed thin YSZ films used as electrolytes for solid oxide fuel cells

A thin yttria-stabilized zirconia (8 mol% YSZ) film was successfully fabricated on a NiO-YSZ anode substrate by a screen-printing technique. The scanning electron microscope (SEM) results suggested that the YSZ film thickness was about 31 μm after sintering at 1400 °C for 4 h in air. A 60 wt% La_0.7Sr_0.3MnO₃ + 40 wt% YSZ was screen-printed onto the YSZ film surface as cathode. A single cell was tested from 650 to 850 °C using hydrogen as fuel and ambient air as oxidant, which showed an open circuit voltage (OCV) of 1.02 V and a maximum power density of 1.30 W cm⁻² at 850 °C. The OCV was higher than 1.0 V, which suggested that the YSZ film was quite dense and that the fuel gas leakage through the YSZ film was negligible. Screen-printing can be a promising method for manufacturing YSZ films for solid oxide fuel cells (SOFCs).     

Carbon-resistant Ni-YSZ/Cu–CeO2-YSZ dual-layer hollow fiber anode for micro tubular solid oxide fuel cell

A NiO-YSZ/porous YSZ dual-layer hollow fiber with an asymmetric structure was fabricated by a co-spinning-sintering method. A dense YSZ electrolyte film was prepared on NiO-YSZ layer by dip-coating method and calcined at 1450 °C; subsequently a porous cathode was dip-coated on the dense YSZ electrolyte film using LSM-YSZ (in the weight ratio 4:1) ink to fabricate a micro tubular solid oxide fuel cell (MT-SOFC). Cu–CeO₂ catalyst was impregnated into the porous YSZ layer to form the second anode composition. The power output of the MT-SOFC with Ni-YSZ/Cu–CeO₂-YSZ graded anode was up to 242 mW cm⁻² operated at 850 °C using CH₄ as fuel and air as oxidant. Little carbon deposition was observed on the double anode using methane as the fuel after 60 h' stable operation.     

Zirconia-based materials in alternative energy devices - A strategy for improving material properties by optimizing the characteristics of initial powders

This work is devoted to the demonstration of a real multifunctional material – zirconia based nanopowders, which can be used in the manufacture of various types of devices that convert natural energy sources into electricity (electrolyte and anode for SOFC, moisture-to-electricity converter). It was shown that such characteristics of nanopowders as particle size, specific surface area, and type of surface centers, which depend on the temperature of nanopowder synthesis, could play both a positive and a negative role in the formation of the functional properties of a device. It was found that the synthesis of 8YSZ nanopowders at 700 °C is optimal for the manufacture of a dense electrolyte material and a porous SOFC anode material during sintering at 1400–1450 °C. The addition of a small amount of Al₂O₃ at the synthesis stage accelerates the sintering of the SOFC electrolyte material by 120 °C and leads to increasing the density to 97% of the theoretical value. The strength of the sintered anode material practically does not change after reduction in an atmosphere of N₂–10% H₂–5% CO₂ and the value is 100 MPa.The synthesis temperature of 8YSZ nanopowder at 700 °C is also optimal for the manufacture of porous converters of ambient humidity into electricity. The formation of particles with a given size and type of surface centers allows generating an electric potential (100–200 mV) for hundreds of hours, which is 2–3 times higher than that of larger and smaller powders. The result of the work show that there are optimal conditions for the synthesis of powders (synthesis method, additives, synthesis temperature), as a result of which nanopowders are formed with characteristics (particle size, specific surface area, morphology) necessary and sufficient for the manufacture of several types of materials for devices of alternative energy.     

A composite carbon anode for use in a polymer electrolyte battery

A composite carbon anode has been developed for a room temperature polymer electrolyte cell using poly(ethylene oxide) (PEO). By means of half-cells the charge/discharge process has been studied and the specific capacity of the Li_xC₆ electrode as a function of cycle number determined. This has been supported by impedance analysis which has been carried out at various electrode compositions. Data on the effect of carbon content on performance and the influence of elevated temperature (40°C) are reported. Good cycleability of a polymer electrolyte cell comprising a carbon anode, PEO-based electrolyte and a high voltage intercalating cathode LiMn₂O₄ has been demonstrated.     

Characterization of a circular 80 mm anode supported solid oxide fuel cell (AS-SOFC) with anode support produced using high-pressure injection molding (HPIM)

The current study was oriented at analyzing the performance of an anode-supported solid oxide fuel cell produced using high-pressure injection molding. The cell with a total thickness of 550 μm was produced in the Ceramic Department (CEREL) of the Institute of Power Engineering in Poland and experimentally analyzed in the Energy Department (DENERG) of Politecnico di Torino in Italy. The high-pressure injection molding technique was applied to produce a 500 μm thick anode support NiO/8YSZ 66/34 wt% with porosity of 25 vol%. The screen printing method was used to print a 3 μm thick NiO anode contact layer, 7 μm thick NiO/8YSZ 50/50 wt% anode functional layer, 4 μm thick 8YSZ dense electrolyte, 1.5 μm thick Gd_0,1Ce_0,9O₂ barrier layer and a 30 μm thick La_0,6Sr_0,4Fe_0,8Co_0,2O_3–δ cathode with porosity 25 vol%.The experimental characterization was done at two temperature levels: 750 and 800 °C under fixed anodic and cathodic flow and compositions. The preliminary studies on the application of high-pressure injection molding are discussed together with the advantages of the technology. The performance of two generations of anode-supported cells is compared with data of reference cells with supports obtained using tape casting.     

High performance intermediate temperature micro-tubular SOFCs with Ba0.9Co0.7Fe0.2Nb0.1O3−δ as cathode

In this study, anode supported intermediate temperature micro-tubular solid oxide fuel cells (MT-SOFCs) have been fabricated by combination of phase-inversion, dip-coating, co-sintering and printing method. The MT-SOFC consists of a ∼300 μm wall-thickness Ni–Sc₂O₃ stabilized ZrO₂ (ScSZ) anode tube, ∼10 μm ScSZ dense electrolyte layer, ∼10 μm Ce_0.9Gd_0.1O_2−δ (GDC) membrane buffer layer and ∼50 μm Ba_0.9Co_0.7Fe_0.2Nb_0.1O_3−δ (BCFN) cathode layer. SEM and electrochemical impedance spectroscopy (EIS) analysis suggested that the novel structured anode can remarkably diminish the porous anode geometrical tortuosity and improve the fuel gas diffusivity. High peak power densities of 0.34, 0.51 and 0.72 W cm⁻² have been achieved with humidified hydrogen as the fuel and ambient air as oxidant at 550, 600 and 650 °C, respectively. Further, the cell has demonstrated a very stable performance with no significant cell voltage degradation under a constant current of 0.6 A cm⁻² for over 213 h test at 650 °C.     

Microwave sintering of high-performance BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) electrolytes for intermediate-temperature solid oxide fuel cells

As a promising electrolyte material for solid oxide fuel cells (SOFCs), BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ (BZCYYb) often surfers from its high sintering temperature, which causes Ba evaporation and sluggish grain growth, thus reducing the electrical conductivity. In this work, densified BZCYYb electrolytes were fabricated at temperatures as low as 1400 °C using the microwave sintering technique. Comparing with the conventional sintered ones, a temperature decrease of 150 °C is achieved. The Ba evaporation is effectively suppressed, and large grain sizes of ～4 μm are obtained. The total conductivity for microwave sintered symmetric cell measured in wet air at 700 °C is 3.8 × 10^?2 S cm^?1, benefiting from both enhanced bulk conductivities by 1–2 times and grain boundary conductivities by 50 times. With the microwave sintered BZCYYb as electrolyte, an anode-supported cell reaches a maximum power density of 0.64 W cm^?2 at 700 °C.     

Anode performance control of micro-tubular SOFC via wet coating method

A cathode-supported micro SOFC was prepared via co-sintering technique of a scandia-stabilized zirconia (ScSZ) electrolyte layer and a micro-tubular (La,Sr)_xMnO_3−δ (LSM) support, and subsequent deposition of various anode layers by dip-coating method. The micro-tubular SOFCs were electrochemically evaluated in a humidified H₂ (3% H₂O) atmosphere. An LSM-Ce_0.9Gd_0.1O_1.95 activation layer was also introduced between the cathode tube and the electrolyte layer in order to improve the catalytic activation at the cathode side. The micro SOFCs exhibited a stable open circuit voltage above 1.05 V at 650 °C, and the cells with the anode film thicknesses of 8, 30 and 50 μm generated a maximum power density of 36, 49 and 126 mW/cm², respectively. And, the cell with 50 μm thick anode layer showed about 10 times higher exchange current density than the others, which indicates that the anode performance on the cathode-supported micro SOFC was greatly affected by the thickness of the anode coating layer.     

Microstructure and electrochemical characterization of solid oxide fuel cells fabricated by co-tape casting

A co-tape casting technique was applied to fabricate electrolyte/anode for solid oxide fuel cells. YSZ and NiO-YSZ powders are raw materials for electrolyte and anode, respectively. Through adjusting the Polyvinyl Butyral (PVB) amount in slurry, the co-sintering temperature for electrolyte/anode could be dropped. After being co-sintered at 1400 °C for 5 h, the half-cells with dense electrolytes and large three phase boundaries were obtained. The improved unit cell exhibited a maximum power density of 589 mW cm⁻² at 800 °C. At the voltage of 0.7 V, the current densities of the cell reached 667 mA cm⁻². When the electrolyte and the anode were cast within one step and sintered together at 1250 °C for 5 h and the thickness of electrolyte was controlled exactly at 20 μm, the open-circuit voltage (OCV) of the cell could reach 1.11 V at 800 °C and the maximum power densities were 739, 950 and 1222 mW cm⁻² at 750, 800 and 850 °C, respectively, with H₂ as the fuel under a flow rate of 50 sccm and the cathode exposed to the stationary air. Under the voltage of 0.7 V, the current densities of cell were 875, 1126 and 1501 mA cm⁻², respectively. These are attributed to the large anode three phase boundaries and uniform electrolyte obtained under the lower sintering temperature. The electrochemical characteristics of the cells were investigated and discussed.     

High-performance solid oxide fuel cells with fiber-based cathodes for low-temperature operation

Low-temperature operation of solid oxide fuel cells (SOFCs) results in deterioration in electrochemical performance due to sluggish oxygen reduction reaction (ORR) at the cathode. To enhance the reaction pathway for ORR, La_0.8Sr_0.2MnO₃ (LSM) nanofibers were fabricated by electrospinning and used for low-temperature solid oxide fuel cells operated at 600–700 °C. The morphological and structural characteristics show that the electrospun LSM nanofiber has a highly crystallized perovskite structure with a uniform elemental distribution. The average diameter of the LSM nanofiber after sintering is 380 nm. A symmetric cell of nanofiber-based LSM cathode on scandia-stabilized zirconia (SSZ) electrolyte pellet exhibits much lower area specific resistances compared to commercial LSM powder-based cathode. A single cell based on the nanofiber LSM cathode on yttrium-doped barium cerate-zirconia (BCZY) electrolyte exhibits a power density of 0.35 Wcm⁻² at 600 °C, which increases to 0.85 Wcm⁻² at 700 °C. The cell has an area specific resistance (ASR) of 0.46 Ωcm² at 600 °C, which decreases to 0.07 Ωcm² at 700 °C. The results indicate that the LSM electrode fabricated by the electrospinning process produces a nanostructured porous electrode which optimizes the microstructure and significantly enhances the ORR at the cathode of SOFCs.     

Tape casting fabrication,co-sintering and optimisation of anode/electrolyte assemblies for SOFC based on BIT07-Ni/BIT07

BaIn_0.3Ti_0.7O_2.85 (BIT07) is an electrolyte material for SOFC due to its high ionic conductivity level and its compatibility with mixed ionic and electronic conductor (MIEC) cathode materials, such as LSCF and Nd₂NiO_4+δ. BIT07 is also compatible with NiO to form a cermet as anode material. In this study, the electrolyte material has been prepared by tape casting and characterised. The coupled influences of the powder grain size and the firing temperature have been investigated and optimised to yield a dense electrolyte at 1300 °C. Then anode-supported half-cells (electrolyte/anode), based on BIT07/BIT07-Ni have been prepared by tape casting and co-sintered. The composition and the microstructure of the cermet anode (BIT07 grain size, amount and nature of pore-forming agent) have been optimised to achieve an area surface resistance (ASR) value of about 0.15 Ω cm² at 700 °C under wet reducing atmosphere. The stability of the most performing anode has been followed during 500 h and the observed degradation seems to be due a loss of nickel percolation.