Ni1−x−yMgxAlyO–ScSZ anodes for solid oxide fuel cells

Three types of cermets based on NiO–ScSZ (A), Ni_0.9Mg_0.1O–ScSZ (AMg) and Ni_0.9Mg_0.095Al_0.005O–ScSZ (AMgAl) were applied as SOFC anodes. Humidified H₂ and simulated biogas (CH₄:CO₂ = 6:4) were directly supplied to the anode side of SOFC single cell. Catalytic activities for the reforming and the electrochemical reactions were tested in a typical electrochemical measurement setup. When hydrogen (3% H₂O) was supplied as a fuel, the three anodes showed almost the same voltage losses (anodic overvoltages) of ca. 40 mV at 400 mA cm^− 2 at 1000 °C. However, supplying the simulated biogas, AMg and AMgAl showed smaller losses of 25 and 29 mV, respectively, than those in supplying hydrogen, whereas A showed the loss of more than 40 mV. Through this study, it was revealed that when the biogas is selected as a fuel, the electrochemical efficiency of the internal reforming SOFC is enhanced by using AMg or AMgAl as anode materials instead of A. Although the higher performances of AMg and AMgAl mainly result from the stability of small Ni particles against sintering, in addition to this effect, basic (Ni,Mg)O solid solution or MgO existing in the electrocatalysts contributes to further activity enhancement.     

Synthesis of nickel nanoparticles supported on hollow samaria-doped ceria particles via the solution-spray plasma technique: Anode catalysts for SOFCs

Aiming at SOFC anode applications, we have synthesized nanometer-sized nickel catalysts supported on hollow spherical particles of samaria-doped ceria (Ni/SDC) by spraying a mixed solution of nickel, samarium, and cerium nitrates into an atmospheric pressure plasma. The as-prepared particles consisted of SDC (average diameter d_SDC = ca. 0.8 µm) and uniformly dispersed nanometer-sized NiO particles. When reduced in H₂ at 800 °C or 1000 °C, Ni nanoparticles (average diameter d_Ni = 34 nm) were found to be embedded uniformly into the SDC surface.     

High oxide ion conductivity in Fe and Mg doped LaGaO3 as the electrolyte of solid oxide fuel cells

La(Sr)Ga(Fe,Mg)O₃ exhibited the high oxide ion conductivity and the electrical power generating property of SOFC single cell using La_0.7Sr_0.3Ga_0.7Fe_0.2Mg_0.1O_3-δ (LSGFM) electrolyte was investigated in this study. The transport number of oxide ion is almost 0.8 in LSGFM and so open circuit potential (OCV) is as low as 0.8 V. OCV was strongly affected by anode materials and the highest OCV was achieved on Ni–Fe bimetallic anode. The extremely high power density was achieved by using LSGFM for electrolyte of SOFC. The maximum power densities of the cells can be elevated by coating with oxide ion conductor film at anode side. The maximum power density increased in the following order for coating film: LSGM > SDC > YSZ. The maximum power density of 197 and 100 mW/cm² can be achieved at 873 and 773 K, respectively, when LSGM film deposited on the anode side of LSGFM. Therefore, LSGFM can be used as electrolyte of SOFC operating at intermediate temperature.     

Characteristic stability of bare Au-water nanofluids fabricated by pulsed laser ablation in liquids

Gold nanoparticles (Au-NPs) suspended in water where the suspension is a kind of nanofluid, were produced by pulsed laser ablation in liquids. Under the laser irradiation conditions up to 18 h, the average size of the Au-NPs ranged from 7.1 to 12.1 nm while their size-distribution tended to become narrower with effects of laser-induced fragmentation. Interestingly, the nanofluid showed an outstanding colloidal stability even after 1 month although no dispersants were used. The characteristic stability of bare Au-NPs suspension in water was found to be due to a large negative zeta potential of Au-NPs in water. The thermal conductivity of the Au-NPs (0.018 vol%)/water suspension increased by 9.3±5.4% compared to that of pure water.     

Effect of oxide on carbon deposition behavior of CH4 fuel on Ni/ScSZ cermet anode in high temperature SOFCs

This work investigated the effect of oxide in Ni-zirconia cermets on the carbon deposition behavior in internal reforming SOFCs. Within 800–1000 °C, carbon deposition was found to decrease with increasing temperature on Ni/ScSZ cermet anodes at a low oxygen / carbon ratio (O / C = 0.03) during anodic oxidation of methane. On the contrary, an opposite trend was observed on Ni/YSZ under the same conditions, consisting with the temperature dependence of carbon deposition predicted by a thermodynamic equilibrium calculation. Results of temperature-programmed-reduction (TPR) of NiO mixed with YSZ or ScSZ indicated that interaction of Ni with ScSZ is stronger than that with YSZ. The stronger interaction was corroborated by observed tendency of inhibiting Ni agglomeration by both BET specific surface area analysis and SEM observation. It was also found that the dependence of CO₂ production rate monitored by GC on current density showed a similar dependence trend of the equilibrium CO₂ content on O / C ratio. A model in which H₂O_ad enrichment effects on Ni surface by anodic current depend on the interaction between Ni and the oxide in Ni cermet was proposed to explain the different carbon deposition behaviors between Ni/YSZ and Ni/ScSZ cermets.     

Performance of La-doped strontium titanate (LST) anode on LaGaO3-based SOFC

Ni-containing anode is currently used with many electrolytes of solid oxide fuel cells (SOFCs). However, Ni is easily oxidized and deteriorates the LaGaO₃-based electrolyte. A La-doped SrTiO₃ (LST, La_0.2Sr_0.8TiO₃) is a candidate as an anode material to solve the Ni poisoning problem in LaGaO₃-based SOFC. In this study, a single-phase LST and an LST-Gd_0.2Ce_0.8O_2 ? δ (GDC) composite were tested as the possible anodes on La_0.9Sr_0.1Ga_0.8Mg_0.2O_3 ? δ (LSGM) electrolyte. In order to further improve the anodic performance, Ni was impregnated into the LST-GDC composite anode. The performance was examined from 600 °C to 800 °C by measuring impedance of the electrolyte-supported, symmetric (anode/electrolyte/anode) cells. A polarization resistance (R_p) of LST-GDC anode was much reduced from that of LST anode. When Ni was impregnated into LST-GDC composite, the R_p value was further reduced to ~ 10% of the single-phase LST anode, and it was 1 Ωcm² at 800 °C in 97% H₂ + 3% H₂O atmosphere. A single cell with Ni-impregnated LST-GDC as an anode, Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ (BSCF) as a cathode and LSGM as an electrolyte exhibited the maximum power density of 275 mW/cm² at 800 °C, increased from ~ 60 mW/cm² for the cell using the LST-GDC as an anode. Thus, LST-GDC composite is promising as a component of anode.     

Fe alloying effect on the performance of the Ni anode in hydrogen fuel

Composite materials of YSZ (yttria-stabilized zirconia) with various Ni–Fe alloys were synthesized and evaluated as the solid oxide fuel cell (SOFC) anode using a 200-µm thick YSZ electrolyte as support and YSZ +La_0.8Sr_0.2MnO₃ (LSM) as cathode. The single cell with the YSZ + Ni_0.75Fe_0.25 anode exhibited the highest performance among all the investigated cells, e.g. a peak power density of 403, 337, 218 and 112 mW/cm² was achieved with H₂ fuel at 900, 850, 800 and 750 °C, respectively. The composite anode with the Ni_0.75Fe_0.25 alloy also had the lowest polarization resistance of 0.55 Ω·cm² at 800 °C among all the alloy compositions, indicating that this specific alloy offered a better anode composition than pure Ni. The possible mechanism for the improved performance of Ni with the Fe alloying addition towards H₂ oxidation was discussed.     

Structure and conductivity investigations of alkaline earth substituted uranium oxide,U1 − xMxO2 ± δ (M = Mg,Ca, Sr) for solid oxide fuel cell applications

Alkaline earth substituted UO₂ (U_1 − xM_xO_2 ± δ; M = Mg, Ca, Sr; 0.1 ≤ x ≤ 0.525) with fluorite structure was synthesized in reducing atmosphere. Structure and conductivity properties of U_1 − xM_xO_2 ± δ fluorites were investigated for possible application in solid oxide fuel cells (SOFC). At room temperature and ambient atmosphere the materials are stable; however they decompose at an oxygen partial pressure p_O2 > 10^− 4 atm and temperatures higher than 600 °C. The total conductivity measured for the best conducting U_1 − xM_xO_2 ± δ material with M = Ca and x = 0.177 is as high as 3 S/cm at p_O2 < 10^− 4 atm at 600 °C. The relatively low ionic transference number (t_i∼0.02) is disadvantageous for potential use as electrolyte material for SOFC applications. The high conductivity and possible depolarization effects suggest potential use as anode materials in SOFC.     

Fabrication and characterization of Ni-supported solid oxide fuel cell

Metal-supported solid oxide fuel cells (SOFCs) are promising due to their good mechanical and thermal properties. Stainless steels are often used as a supporting metal. In this study, the possible use of Ni as a supporting metal was tested. Ni is also a good model of supporting metal due to its lack of Cr which poisons Ni anode.YSZ electrolyte and Ni-YSZ anode were coated on a porous Ni support to fabricate Ni-supported SOFC. A porous Ni support in thick-film form (t ~ 150 µm) was prepared by the mold casting of Ni powders. An anode and an electrolyte layer were sequentially coated on the Ni support using screen printing and tape casting methods, respectively. The Ni-supported cell (t ~ 200 µm) was sintered at 1400 °C in a reducing atmosphere and the performance was evaluated at 800 °C with a La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) cathode. The unit cell showed an open circuit voltage (OCV) of 0.96 V and a peak power density of 470 mW/cm² at 800 °C.     

Fabrication of Gd0.5Sr0.5CoO3 film for SOFC cathode by pulsed laser deposition

Gd_0.5Sr_0.5CoO₃ (GSCO) film has been fabricated by pulsed laser deposition (PLD) to be used as the cathode of the solid oxide fuel cell (SOFC). The GSCO thin film obtained has a columnar crystalline structure so that it will have a high permeation property. The PLD technique has been found suitable for growing a film of complex composition because of its good control of stoichiometry and thus for fabricating a GSCO film used as the cathode of the SOFC. The GSCO film has been studied for porosity electrical conductivity and power density. The GSCO film grown at a substrate temperature of 1100 K and oxygen gas pressure of 100 Pa has high electrical conductivity which is 820 S cm^− 1 at 973 K with post annealing at a rather low temperature (1000 K). This value is higher than that of the GSCO film prepared by RF-sputtering with post annealing at a higher temperature (1273 K).     

Micro-solid oxide fuel cell using thick-film ceria

A fabrication method that does not use lithography or etching processes for thick-film based micro-SOFCs (Solid Oxide Fuel Cells) was described and discussed. In this study, a new type of micro-SOFC was fabricated using a free-standing thick-film electrolyte with ~ 20 μm thickness. This structure has the advantages of both electrolyte-support and electrode-support type SOFCs. Generally, the electrolyte should be thicker than e.g., ~ 150 μm since a thinner electrolyte easily cracks in a self-supporting mode during the fabrication procedure. Thus, a new mounting method was developed in order to use a thin-electrolyte film. In this study, a ~ 20 μm-thick GDC (Gd-doped ceria) electrolyte film was successfully mounted on a ~ 400 μm-thick GDC ring by sintering these two pieces together. Ni-GDC and Sm_0.5Sr_0.5CoO₃ were brush painted as an anode and a cathode, respectively. With this new configuration, it was possible to construct an electrolyte-supported SOFC using a thick-film ceria-based electrolyte and measure the power density. The open-circuit voltage (OCV) of the cell in 97%H₂ + 3%H₂O/air was ~ 0.87 V and the maximum power density was ~ 270 mW/cm² at 600 °C. The result shows that the high performance is achievable for the micro-SOFCs using a thick-film ceria-electrolyte operating at 600 °C.     

La0.75Sr0.25Cr0.5Mn0.5O3−δ + Cu composite anode running on H2 and CH4 fuels

La_1−xSr_xCr_1−xM_xO_3−δ (M = Cr, Fe, V) system has been studied as anode materials for solid oxide fuel cells (SOFCs). The perovskite La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCM) is stable in both H₂ and CH₄ atmospheres at temperatures up to 1000°C. However, in the reducing atmospheres of H₂ and CH₄, its electronic conductivity is greatly reduced from its value in air. We have characterized LSCM as the anode of a SOFC having 250 μm-thick La_0.8Sr_0.2Ga_0.83Mg_0.17O_2.815 (LSGM) as the electrolyte and SrCo_0.8Fe_0.2O_3−δ (SCF) as the cathode. We report a comparison of the overpotentials at the following anodes: (1) La_0.4Ce_0.6O_1.8 (LDC) + NiO composite in H₂, (2) porous LSCM in H₂ and CH₄, (3) porous LSCM impregnated with CuO in H₂ and CH₄ and (4) porous LSCM impregnated with CuO and sputtered with Pt in H₂ and CH₄. An LSCM + CuO + Pt anode gave a maximum power output at 850 °C of 850 mW/cm² and 520 mW/cm², respectively, with H₂ and CH₄ as fuel whereas anode (1) gave 1.4 W/cm² at 800 °C in H₂. There was no noticeable coke formation in CH₄ with anodes (2), (3) and (4), which demonstrates that the perovskite oxide is a plausible option for the anode of a SOFC operating with hydrocarbon fuels. We also report the moisture effect in the H₂ and CH₄ fuel-oxidation process.     

Nanostructured Cu-CGO anodes fabricated using a microwave-assisted glycine–nitrate process

This work reports a study of nanostructured copper-doped gadolinium cermet (Cu-CGO) composite anodes prepared via conventional synthesis (CS) and microwave-synthesis (MS) involving the glycine–nitrate process (GNP). A detailed investigation on the mechanical properties, electrical conductivity and electrochemical performance of prepared Cu_0.5(Ce_0.9Gd_0.1)_0.5O_2−δ anodes is included. The prepared samples were characterized by techniques, such as XRD, EDX, SEM and electrical characterizations. After reduction in 10% H₂ and 90% N₂, the DC conductivities of the Cu-CGO anodes prepared via CS-GNP and MS-GNP are found to be 5.43×10³ and 1.09×10⁴ S cm⁻¹ at 700 °C, respectively. The electrochemical performances of the spin-coated anode symmetrical cells sintered at 700 °C are evaluated at cell operating temperatures of 600, 700 and 800 °C. The lowest area specific resistance (ASR) values for the Cu-CGO/CGO/Cu-CGO symmetrical cells prepared via the MS-GNP route at operating temperatures of 600, 700 and 800 °C are found to be 0.34, 0.71 and 1.10 Ω cm², respectively. The as-prepared (via MS-GNP) Cu-CGO anode exhibits excellent electrical and electrochemical performance consistent with the uniform nanostructured morphology compared with the anode prepared via CS-GNP.     

Superiority of sonochemical processing method for the synthesis of barium titanate nanocrystals in contrast to the mechanochemical approach

The results indicated that the ultrasonic sonochemistry which brings into play the acoustic cavitation phenomenon is more powerful and feasible in synthesizing the mixed oxides in contrast to the conventional solid-state approaches. The obtained results demonstrated that the sonochemical approach is able to obtain highly pure powder product at a much lower processing temperature of about 323 K (50 °C) in contrast to 1173 K (900 °C) which is essential for the synthesis by the mechanochemical approach. Sonochemical synthesis benefits from homogenous ordering the reactant ions (which have been dissolved in the solution mixture) into perovskite structure using ultrasonication. This indicates that the acoustic cavitation phenomenon is much more powerful and cost-effective than high energy ball milling in synthesizing nanopowders of the mixed oxide materials. Moreover, the sonochemical processing method is able to prepare the final powder products in a much shorter time by a one-step synthesis approach without the need for the successive calcination in contrast to the solid-state approach.     

Characterization of Sr2.7Ln0.3Fe1.4Co0.6O7 (Ln = La,Nd, Sm,Gd) intergrowth oxides as cathodes for solid oxide fuel cells

Perovskite-related intergrowth oxides Sr_2.7Ln_0.3Fe_1.4Co_0.6O_7 ? δ (Ln = La, Nd, Sm, and Gd) have been investigated as cathode materials for solid oxide fuel cells (SOFC). With decreasing size of the Ln³⁺ ions, the unit cell volume, oxygen content, thermal expansion coefficient (TEC), and total electrical conductivity decrease from Ln = La to Gd. The decreasing unit cell volume and oxygen content is attributed to the decreasing size of Ln³⁺ ions from Ln = La to Gd and a consequent preference for lower coordination numbers. While the decrease in the ionicity of the Ln–O bonds from Ln = La to Gd causes a decrease in the TEC, the increasing amount of oxygen vacancies leads to a decrease in electrical conductivity arising from a thermally activated semiconducting behavior. The cathode polarization conductance (R_p^? 1) measured using the ac-impedance spectroscopy and the catalytic activity for the oxygen reduction reaction in SOFC decrease from Ln = La to Gd partly due to the decrease in electrical conductivity.     

Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid

Porous (Ce_0.5Zr_0.5)O₂ solid solutions were prepared by thermolysis (T = 285 °C) or sonolysis (20 kHz, I = 32 W cm⁻², P_ac = 0.46 W mL⁻¹, T = 200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4–6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce_0.5Zr_0.5)O₂ solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m² g⁻¹ depending on synthesis conditions. The use of Barrett–Joyner–Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce_0.5Zr_0.5)O₂ mixed oxides loaded with 1.5 %wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C.     

Performance and durability of Ni-coated YSZ anodes for intermediate temperature solid oxide fuel cells

NiO-coated YSZ composite powders were synthesized through the Pechini process in order to improve the performance and durability of SOFC anodes. Their microstructures and electrical properties have been investigated with thermal and redox cycling tests. The coverage of NiO crystals on the YSZ surface could be modulated by controlling the composition of the reaction mixture and the ratio of NiO and YSZ. Ni–YSZ electrodes were manufactured by sintering the die-pressed NiO–YSZ pellet at 1400 °C for 3 h, followed by reducing it to 800 °C under hydrogen atmosphere. The anode made from NiO/YSZ composite powder, which has a high homogeneity and plenty of contact sites between Ni and YSZ, has an excellent tolerance against thermal and redox cycling. The maximum power density of a single cell made from NiO/YSZ composite powder was 0.56 W cm^− 2 at 800 °C in reactive gases of humidified hydrogen and air. It can be concluded that the functional NiO/YSZ composite powder will suppress the degradation of anodes and enhance the long-term and redox stability of the unit cell at elevated temperatures.     

Evaluation of Sr- and Mn-substituted LaAlO3 as potential SOFC anode materials

Lanthanum–aluminate-based oxides, (La_0.8Sr_0.2)_1−yAl_1−xMn_xO_3−δ (x = 0, 0.3, 0.5; y = 0 or 0.06) (LSAM), were synthesized and evaluated in detail as potential anode materials for solid oxide fuel cells (SOFCs). The electrical conductivity of LSAM (Mn ≥ 30 mol%) is dominated by p-type electronic conduction and can be treated as a diluted system of lanthanum manganites, (La,Sr)MnO₃. At 810 °C, the electrical conductivity of (La_0.8Sr_0.2)_0.94Al_0.5Mn_0.5O_3−δ (LSAM8255b) reaches 12 S/cm in air and 2.7 S/cm in humidified Ar/4% H₂ (p(O₂) ≈ 10^− 18 bar). The thermal expansion coefficients of LSAM8255a and LSAM8255b match YSZ very well and no chemical reaction was observed between these two perovskite materials and YSZ up to at least 1400 °C. Fairly good electrochemical performance was observed for an LSAM8255b–YSZ composite anode. At 850 °C, the polarization resistances are only 0.34 and 0.50 Ω cm² in wet (∼3% H₂O) Ar/20% H₂ and wet Ar/20% CH₄, respectively. In addition, an exposure to Ar/20% CH₄/3% H₂O for 35 h did not cause any apparent carbon deposition on the electrode. However, the chemical stability of LSAM8255a and LSAM8255b in a typical anode environment under open circuit conditions does not seem sufficient, leading to performance degradation with time in wet Ar/20% H₂ or wet Ar/20% CH₄. Furthermore, relatively large chemical expansion (0.3–0.5%) was observed when the atmosphere was switched from air to wet Ar/4% H₂, which might cause intolerable stress on the thin film electrolyte layer for a large-area anode-supported planar SOFC, but which might be tolerable for small geometries or electrolyte-supported SOFCs.     

Fabrication and characterization of hermetic solid oxide fuel cells without sealant

A simplified solid oxide fuel cell (SOFC) design has been developed that would eliminate the need for external sealants yet maintains the hermetic requirements necessary for separation of fuel from oxidant. This hermetic seal is based on the formation of a solid-state interface, between the electrolyte and the interconnect. The novel SOFC design eliminates unnecessary interface formation and material addition, thus greatly simplifying fuel cell stacks. Overcasting and co-casting techniques were used to fabricate symmetric cell and lateral geometries in order to examine the interfacial characteristics of the hermetic structure and particularly the solid-state seal. Leakage rates determined from mass spectrometry were about 4.57 * 10^− 7 L/s at 750 °C.     

Ni-GDC microtubular cermets

Ni-GDC cermet tubes (~ 3 mm inside diameter, 0.3–0.4 mm wall thickness and ～ 100 mm in length) with different amounts of porosity have been prepared by sintering of NiO-Ce_0.9Gd_0.1O_1.95 (NiO-GDC) nanopowders and further reduction. The NiO-GDC nanopowders were synthesized by chemical route and the different pore density was obtained by modifying the processing conditions (calcining and adjustment of carbonous remains).Ni-GDC cermets were obtained from the sintered NiO-GDC composites using reduction treatment at 700 °C for 3 h in reducing atmosphere (5 vol.% H₂–95 vol.% Ar). After the reduction process, tubes with 25–32% porosity were obtained. Gas permeability and Hg porosimetry studies were used to evaluate permeability, pore distribution and pore density. Electrical conductivity studies of the cermets were also performed.