Characterization of the Ni-ScSZ anode with a LSCM-CeO2 catalyst layer in thin film solid oxide fuel cell running on ethanol fuel

Solid oxide fuel cell (SOFC) running directly on hydrocarbon fuels has attracted much attention in recent years. In this paper, a dual-layer structure anode running on ethanol is fabricated by tape casting and screen-printing method, the addition of a LSCM-CeO₂ catalyst layer to the supported anode surface yields better performance in ethanol fuel. The effect that the synthesis conditions of the catalyst layer have on the performances of the composite anodes is investigated. Single cells with this anode are also fabricated, of which the maximum power density reaches 669 mW cm⁻² at 850 °C running on ethanol steam. No significant degradation in performance has been observed after 216 h of cell testing when the Ni-ScSZ13 anode is exposed to ethanol steam at 700 °C. Very little carbon is detected on the anode, suggesting that carbon deposition is limited during cell operation. Consequently, the LSCM-CeO₂ catalyst layer on the surface of the supported anode makes it possible to have good stability for long-term operation in ethanol fuel due to low carbon deposition.     

Preparation and performance characterization of the Fe–Ni/ScSZ cermet anode for oxidation of ethanol fuel in SOFCs

An anodic cermet of Fe–Ni alloy and scandia stabilized zirconia (ScSZ) has been investigated for a solid oxide fuel cell (SOFC) running on ethanol fuel. Composite anodes having alloy compositions of 0, 12.5, 25, 37.5, 50 and 100 wt.% Ni were exposed to ethanol stream at 700 °C for 12 h to demonstrate that carbon formation is greatly suppressed on the Fe–Ni alloys compared to that of pure Ni. Then the short-term stability for the cells with the Ni/ScSZ and Fe_0.5Ni_0.5/ScSZ anodes in ethanol stream at 700 °C was checked over a relative long period of operation. Open circuit voltages (OCVs) increased from 1.03 to 1.1 V, and power densities increased from 120 to 460 mW cm² as the operating temperature of a SOFC with Fe_0.5Ni_0.5/ScSZ anode was increased from 700 to 850 °C in ethanol stream. Electrochemical impedance spectra (EIS) illustrated that the cell with Ni/ScSZ anode exhibits slightly less total impedance than that observed for the cell with Fe_0.5Ni_0.5/ScSZ anode. The performance of a fuel cell made with the Ni/ScSZ and Fe_0.5Ni_0.5/ScSZ anodes was tested in ethanol stream for 48 h and showed a significant decrease in polarization resistance with time. Impedance spectra of similar fuel cells suggest that small carbon deposits are formed with time and that the decrease in polarization resistance is due to enhanced electronic conductivity in the anode.     

High performance direct ethanol fuel cell with double-layered anode catalyst layer

Double-layered anode catalyst layers with two reverse configurations, which consist of 45 wt.% Pt₃Sn/C and PtRu black catalyst layers, were fabricated to improve the performance of a direct ethanol fuel cell (DEFC). The in-house 45 wt.% Pt₃Sn/C catalyst was characterized by XRD and TEM. The cross-sectional double-layered anode catalyst layer was observed by SEM. In DEFC performance test and anode linear sweep voltammetry measurement, the anode with double-layered catalyst layer exhibited better catalytic activity for ethanol electro-oxidation than those with single-layered 45 wt.% Pt₃Sn/C and PtRu black catalyst layers. In terms of anode product distribution, the DEFC with double-layered anode catalyst layer showed a higher yield of acetic acid than that with single-layered PtRu black catalyst layer and a higher yield of CO₂ than that with single-layered 45 wt.% Pt₃Sn/C catalyst layer, respectively. These results suggest that the double-layered anode catalyst layer possessed the advantages of both Pt₃Sn/C and PtRu black catalysts for ethanol electro-oxidation, and thus showed a higher ethanol electro-oxidation efficiency and DEFC performance in the practical polarization potential region.     

Three-dimensional anode engineering for the direct methanol fuel cell

Catalyzed graphite felt three-dimensional anodes were investigated in direct methanol fuel cells (DMFCs) operated with sulfuric acid supporting electrolyte. With a conventional serpentine channel flow field the preferred anode thickness was 100 μm, while a novel flow-by anode showed the best performance with a thickness of 200-300 μm. The effects of altering the methanol concentration, anolyte flow rate and operating temperature on the fuel cell superficial power density were studied by full (2³ + 1) factorial experiments on a cell with anode area of 5 cm² and excess oxidant O₂ at 200 kPa(abs). For operation in the flow-by mode with 2 M methanol at 2 cm³ min⁻¹ and 353 K the peak power density was 2380 W m⁻² with a PtRuMo anode catalyst, while a PtRu catalyst yielded 2240 W m⁻² under the same conditions.     

A comprehensive evaluation of a Ni-Al2O3 catalyst as a functional layer of solid-oxide fuel cell anode

An inexpensive 7 wt.% Ni-Al₂O₃ composite is synthesized by a glycine-nitrate process and systematically investigated as anode catalyst layer of solid-oxide fuel cells operating on methane fuel by examining its catalytic activity towards methane partial oxidation, steam and CO₂ reforming at 600-850 °C, cell performance, mechanical performance, and carbon deposition properties. Ni-Al₂O₃ shows comparable catalytic activities to Ru-CeO₂ for the above three reactions. The cell with a Ni-Al₂O₃ catalyst layer delivers maximum peak power densities of 494 and 532 mW cm⁻² at 850 °C, operating on methane-H₂O and methane-CO₂ mixture gases, respectively, which are comparable to those operating on hydrogen. Ni-Al₂O₃ is found to have better mechanical performance than Ru-CeO₂. O₂-TPO demonstrates that Ni-Al₂O₃ does not inhibit the carbon formation under pure methane atmosphere, while the introduction of steam or CO₂ can effectively suppress coke formation. However, due to the low nickel content in the catalyst layer, the coke formation over the catalyst layer is actually not serious under real cell operation conditions. More importantly, Ni-Al₂O₃ effectively protects the anode layer by greatly suppressing carbon formation over the anode layer, especially near the anode-electrolyte interface. Ni-Al₂O₃ is highly promising as an anode functional layer for solid-oxide fuel cells.     

Direct borohydride fuel cell using Ni-based composite anodes

In this study, nickel-based composite anode catalysts consisting of Ni with either Pd on carbon or Pt on carbon (the ratio of Ni:Pd or Ni:Pt being 25:1) were prepared for use in direct borohydride fuel cells (DBFCs). Cathode catalysts used were 1 mg cm⁻² Pt/C or Pd electrodeposited on activated carbon cloth. The oxidants were oxygen, oxygen in air, or acidified hydrogen peroxide. Alkaline solution of sodium borohydride was used as fuel in the cell. High power performance has been achieved by DBFC using non-precious metal, Ni-based composite anodes with relatively low anodic loading (e.g., 270 mW cm⁻² for NaBH₄/O₂ fuel cell at 60 °C, 665 mW cm⁻² for NaBH₄/H₂O₂ fuel cell at 60 °C). Effects of temperature, oxidant, and anode catalyst loading on the DBFC performance were investigated. The cell was operated for about 100 h and its performance stability was recorded.     

Measurement of oxygen chemical potential in Gd2O3-doped ceria-Y2O3-stabilized zirconia bi-layer electrolyte, anode-supported solid oxide fuel cells

Solid oxide fuel cells (SOFC) were fabricated with gadolinia-doped ceria (GDC)-yttria stabilized zirconia (YSZ), thin bi-layer electrolytes supported on Ni + YSZ anodes. The GDC and YSZ layer thicknesses were 45 μm, and ∼5 μm, respectively. Two types of cells were made; YSZ layer between anode and GDC (GDC/YSZ) and YSZ layer between cathode and GDC (YSZ/GDC). Two platinum reference electrodes were embedded within the GDC layer. Cells were tested at 650 °C with hydrogen as fuel and air as oxidant. Electric potentials between embedded reference electrodes and anode and between cathode and anode were measured at open circuit, short circuit and under load. The electric potential was nearly constant through GDC in the cathode/YSZ/GDC/anode cells. By contrast, it varied monotonically through GDC in the cathode/GDC/YSZ/anode cells. Estimates of oxygen chemical potential, μO₂, variation through GDC were made. μO₂ within the GDC layer in the cathode/GDC/YSZ/anode cell decreased as the current was increased. By contrast, μO₂ within the GDC layer in the cathode/YSZ/GDC/anode cell increased as the current was increased. The cathode/YSZ/GDC/anode cell exhibited maximum power density of ∼0.52 W cm⁻² at 650 °C while the cathode/GDC/YSZ/anode cell exhibited maximum power density of ∼0.14 W cm⁻² for the same total electrolyte thickness.     

Experimental study of commercial size proton exchange membrane fuel cell performance

Commercial sized (16 × 16 cm² active surface area) proton exchange membrane (PEM) fuel cells with serpentine flow chambers are fabricated. The GORE-TEX® PRIMEA 5621 was used with a 35-μm-thick PEM with an anode catalyst layer with 0.45 mg cm⁻² Pt and cathode catalyst layer with 0.6 mg cm⁻² Pt and Ru or GORE-TEX® PRIMEA 57 was used with an 18-μm-thick PEM with an anode catalyst layer at 0.2 mg cm⁻² Pt and cathode catalyst layer at 0.4 mg cm⁻² of Pt and Ru. At the specified cell and humidification temperatures, the thin PRIMEA 57 membrane yields better cell performance than the thick PRIMEA 5621 membrane, since hydration of the former is more easily maintained with the limited amount of produced water. Sufficient humidification at both the cathode and anode sides is essential to achieve high cell performance with a thick membrane, like the PRIMEA 5621. The optimal cell temperature to produce the best cell performance with PRIMEA 5621 is close to the humidification temperature. For PRIMEA 57, however, optimal cell temperature exceeds the humidification temperature.     

Effect of impregnation phases on the performance of Ni-based anodes for low temperature solid oxide fuel cells

Impregnated nanoparticles are very effective in improving the electrochemical performance of solid oxide fuel cell (SOFC) anodes possibly due to the extension of reaction sites and/or the enhancement of catalytic activity. In this work, samaria-doped ceria (SDC), pure ceria, samaria, and alumina oxides impregnated Ni-based anodes are fabricated to compare the site extending and the catalytic effects. Except for alumina, the impregnation of the other three nano-sized oxides could substantially enhance the performance of the anodes for the hydrogen oxidation reactions. Moreover, single cells with CeO₂ and Sm₂O₃ impregnated anodes could exhibit as great performance as those with SDC impregnated anodes. When the impregnation loading reached the optimal value, 1.7 mmol cm⁻³, these cells exhibit very high performance, with peak power densities around 750 mW cm⁻². The high performance of CeO₂ and Sm₂O₃ impregnated anodes demonstrates that the improved performance are mainly attributed to the significantly improved electrochemical activities of the anodes, but not to the extension of triple-phase-boundary, and wet impregnation is indeed an alternative and effective technique to introduce these nano-sized catalytic active oxides into the anode configuration of SOFCs to enhance cell performance, stability and reliability.     

Improved fuel use efficiency in microchannel direct methanol fuel cells using a hydrophilic macroporous layer

We demonstrate state-of-the-art room temperature operation of silicon microchannel-based micro-direct methanol fuel cells (μDMFC) having a very high fuel use efficiency of 75.4% operating at an output power density of 9.25 mW cm⁻² for an input fuel (3 M aqueous methanol solution) flow rate as low as 0.55 μL min⁻¹. In addition, an output power density of 12.7 mW cm⁻² has been observed for a fuel flow rate of 2.76 μL min⁻¹. These results were obtained via the insertion of novel hydrophilic macroporous layer between the standard hydrophobic carbon gas diffusion layer (GDL) and the anode catalyst layer of a μDMFC; the hydrophilic macroporous layer acts to improve mass transport, as a wicking layer for the fuel, enhancing fuel supply to the anode at low flow rates. The results were obtained with the fuel being supplied to the anode catalyst layer via a network of microscopic microchannels etched in a silicon wafer.     

Development of a Ni-Ce0.8Zr0.2O2 catalyst for solid oxide fuel cells operating on ethanol through internal reforming

Inexpensive 20 wt.% Ni-Ce_0.8Zr_0.2O₂ catalysts are synthesized by a glycine nitrate process (GNP) and an impregnation process (IMP). The catalytic activity for ethanol steam reforming (ESR) at 400-650 °C, catalytic stability and carbon deposition properties are investigated. Ni-Ce_0.8Zr_0.2O₂ (GNP) shows a higher catalytic performance than Ni-Ce_0.8Zr_0.2O₂ (IMP), especially at lower temperatures. It also presents a better coking resistance and a lower graphitization degree of the deposited carbon. The superior catalytic activity and coke resistance of Ni-Ce_0.8Zr_0.2O₂ (GNP) is attributed to the small particle size of the active metallic nickel phase and the strong interaction between the nickel and the Ce_0.8Zr_0.2O₂ support, as evidenced by the XRD and H₂-TPR. The Ni-Ce_0.8Zr_0.2O₂ (GNP) is further applied as an anode functional layer in solid oxide fuel cells operating on ethanol steam. The cell yields a peak power density of 536 mW cm⁻² at 700 °C when operating on EtOH-H₂O gas mixtures, which is only slightly lower than that of hydrogen fuel, whereas the cell without the functional layer failed for short-term operations. Ni-Ce_0.8Zr_0.2O₂ (GNP) is promising as an active and highly coking-resistant catalyst layer for solid-oxide fuel cells operating on ethanol steam fuel.     

Use of La0.75Sr0.25Cr0.5Mn0.5O3 materials in composite anodes for direct ethanol solid oxide fuel cells

The perovskite system La_1−xSr_xCr_1−yM_yO_3−δ (M, Mn, Fe and V) has recently attracted much attention as a candidate material for the fabrication of solid oxide fuel cells (SOFCs) due to its stability in both H₂ and CH₄ atmospheres at temperatures up to 1000 °C. In this paper, we report the synthesis of La_0.75Sr_0.25Cr_0.5Mn_0.5O₃ (LSCM) by solid-state reaction and its employment as an alternative anode material for anode-supported SOFCs. Because LSCM shows a greatly decreased electronic conductivity in a reducing atmosphere compared to that in air, we have fabricated Cu-LSCM-ScSZ (scandia-stabilized zirconia) composite anodes by tape-casting and a wet-impregnation method. Additionally, a composite structure (support anode, functional anode and electrolyte) structure with a layer of Cu-LSCM-YSZ (yttria-stabilized zirconia) on the supported anode surface has been manufactured by tape-casting and screen-printing. Single cells with these two kinds of anodes have been fabricated, and their performance characteristics using hydrogen and ethanol have been measured. In the operation period, no obvious carbon deposition was observed when these cells were operated on ethanol. These results demonstrate the stability of LSCM in an ethanol atmosphere and its potential utilization in anode-supported SOFCs.     

A high-performance no-chamber fuel cell operated on ethanol flame

A no-chamber solid-oxide fuel cell operated on a fuel-rich ethanol flame was reported. Heat produced from the combustion of ethanol thermally sustained the fuel cell at a temperature of 500–830 °C. Considerable amounts of hydrogen and carbon monoxide were also produced during the fuel-rich combustion which provided the direct fuels for the fuel cell. The location of the fuel cell with respect to the flame was found to have a significant effect on the fuel cell temperature and performance. The highest power density was achieved when the anode was exposed to the inner flame. By modifying the Ni + Sm_0.2Ce_0.8O_1.9 (SDC) anode with a thin Ru/SDC catalytic layer, the fuel cell envisaged not only an increase of the peak power density to ∼200 mW cm⁻² but also a significant improvement of the anodic coking resistance.     

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.     

Fabrication and impedance studies of DMFC anode incorporated with CNT-supported high-metal-content electrocatalyst

In this study, the fabrication of a direct methanol fuel cell (DMFC) anode with the incorporation of a multiwalled carbon nanotube (CNT)-supported high-metal-content Pt/Ru electrocatalyst, i.e., 40 wt%Pt-20 wt%Ru/CNT, using a novel approach and the resultant DMFC performances were investigated. Employing a vacuum filtration method, we were able to successfully fabricate the DMFC anode with a good electrode structure using an in-house prepared Pt-Ru/CNT electrocatalyst. The catalyst layer was formed directly on a Teflon-treated carbon cloth having a buckypaper texture with a catalyst loading of 4.0 mg cm⁻². From single-cell tests, excellent cell performances were obtained. At 80 °C, the power density was found to be as high as >100 mW cm⁻². This can be attributed to a thinner catalyst layer formed with a more efficient utilization of the catalyst than that using a low-metal-content counterpart, i.e., 20 wt%Pt-10 wt%Ru/CNT, as reported in an earlier study. However, the Nafion^® ionomer content in the catalyst layer played a key role in the anode fabrication to obtain a good cell performance. In addition, the electrochemical impedance spectroscopy (EIS) with a constant phase element (CPE)-based equivalent-circuit model was employed to analyze the fabricated anode. It distinctively revealed some specific characteristics in the resistances and the interface properties. Overall, the obtained impedance results are somewhat different from those of a conventional DMFC anode with the catalyst layer coated onto a porous gas diffusion layer (GDL) on a carbon backing material. Based on the experimental results and the impedance analyses, the high-metal-content Pt-Ru/CNT catalyst was found to be much more favorable and suitable for use as a DMFC anode catalyst.     

In situ Van der Pauw measurements of the Ni/YSZ anode during exposure to syngas with phosphine contaminant

Solid oxide fuel cells (SOFCs) represent an option to provide a bridging technology for energy conversion (coal syngas) as well as a long-term technology (hydrogen from biomass). Whether the fuel is coal syngas or hydrogen from biomass, the effect of impurities on the performance of the anode is a vital question. The anode resistivity during SOFC operation with phosphine-contaminated syngas was studied using the in situ Van der Pauw method. Commercial anode-supported solid oxide fuel cells (Ni/YSZ composite anodes, YSZ electrolytes) were exposed to a synthetic coal syngas mixture (H₂, H₂O, CO, and CO₂) at a constant current and their performance evaluated periodically with electrochemical methods (cyclic voltammetry, impedance spectroscopy, and polarization curves). In one test, after 170 h of phosphine exposure, a significant degradation of cell performance (loss of cell voltage, increase of series resistance and increase of polarization resistance) was evident. The rate of voltage loss was 1.4 mV h⁻¹. The resistivity measurements on Ni/YSZ anode by the in situ Van der Pauw method showed that there were no significant changes in anode resistivity both under clean syngas and syngas with 10 ppm PH₃. XRD analysis suggested that Ni₅P₂ and P₂O₅ are two compounds accumulated on the anode. XPS studies provided support for the presence of two phosphorus phases with different oxidation states on the external anode surface. Phosphorus, in a positive oxidation state, was observed in the anode active layer. Based on these observations, the effect of 10 ppm phosphine impurity (or its reaction products with coal syngas) is assigned to the loss of performance of the Ni/YSZ active layer next to the electrolyte, and not to any changes in the thick Ni/YSZ support layer.     

Effect of platinum amount in carbon supported platinum catalyst on performance of polymer electrolyte membrane fuel cell

The performance of polymer electrolyte membrane fuel cells fabricated with different catalyst loadings (20, 40 and 60 wt.% on a carbon support) was examined. The membrane electrode assembly (MEA) of the catalyst coated membrane (CCM) type was fabricated without a hot-pressing process using a spray coating method with a Pt loading of 0.2 mg cm⁻². The surface was examined using scanning electron microscopy. The catalysts with different loadings were characterized by X-ray diffraction and cyclic voltammetry. The single cell performance with the fabricated MEAs was evaluated and electrochemical impedance spectroscopy was used to characterize the fuel cell. The best performance of 742 mA cm⁻² at a cell voltage of 0.6 V was obtained using 40 wt.% Pt/C in both the anode and cathode.     

Electrochemical performances of solid oxide fuel cells based on Y-substituted SrTiO3 ceramic anode materials

Yttrium-substituted SrTiO₃ has been considered as anode material of solid oxide fuel cells (SOFCs) substituting of the state-of-the-art Ni cermet anodes. Sr_0.895Y_0.07TiO_3−δ (SYT) shows good electrical conductivity, compatible thermal expansion with yttria-stabilized ZrO₂ (YSZ) electrolyte and reliable stability during reduction and oxidation (redox) cycles. Single cells based on SYT anode substrates were fabricated in the dimension of 50 mm × 50 mm. The cell performances were over 1.0 A cm⁻² at 0.7 V and 800 °C, which already reached the practical application level. Although Ti diffusion from SYT substrates to YSZ electrolytes was observed, it did not show apparent disadvantage to the cell performance. The cells survived 200 redox cycles without obvious OCV decrease and macroscopic damage, but performance decreased due to the electronic properties of the SYT material. The influence of water partial pressure on cell performance and coking tolerance of the cells are also discussed in this study.     

Influence of anode thickness on the power output of solid oxide fuel cells with (La,Sr)(Co,Fe)-type cathode

The influence of the thickness of the anode (functional layer) on the power output of anode-supported solid oxide fuel cells with a lanthanum-strontium-cobalt-ferrite cathode was investigated. The anode was applied by vacuum slip casting and the thickness varied between 1 and 22 μm. All other material and microstructural parameters were kept constant. Single cells with dimensions of 50 mm × 50 mm and with an active cathode area of 40 mm × 40 mm were manufactured and tested in an alumina housing with air as oxidant and hydrogen with 3% water vapour as the fuel gas.Results have shown that SOFCs with anodes between 1 and 13 μm have slightly better performance than those with thicker anodes (∼1.7 A cm⁻² versus 1.5 A cm⁻² at 800 °C and 0.7 V). The current densities were discussed with respect to cell area specific resistance, helium leak rate of the half-cell, and microstructure.     

A more efficient anode microstructure for SOFCs based on proton conductors

While the desired microstructure of the state-of-the-art Ni-YSZ anode for a solid oxide fuel cell (SOFC) based on YSZ is well known, the anode microstructure for a SOFC based on a proton conductor is yet to be optimized. In this study, we examined the effect of anode porosity on the performance of a SOFC based on BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb), a mixed ion (proton and oxygen anion) conductor with high ionic conductivity at intermediate temperatures. Three cells with Ni-BZCYYb cermet anodes of different porosities (37%, 42%, and 50%) and identical electrolytes and cathode components were fabricated and tested. Under typical fuel cell operating conditions, the cell with anode of the lowest porosity (37%), prepared without pore former, achieved the highest performance, demonstrating a peak power density of 1.2 W/cm² at 750 °C. This is radically different from the results of Ni-YSZ anodes for YSZ based cells, where high anode porosity (∼55%) is necessary to achieve high performance. The observed increase in performance (or electrocatalytic activity for anode reactions) is attributed primarily to the unique microstructure of the anode fabricated without the use of pore forming precursors.