Microstructure and performance of novel Ni anode for hollow fibre solid oxide fuel cells

Nickel anodes were deposited on hollow fibre yttria-stabilised zirconia (YSZ) electrolyte substrates for use in solid oxide fuel cells (SOFCs). The hollow fibres are characterised by porous external and internal surfaces supported by a central gas-tight layer (300 μm total wall thickness and 1.6 mm external diameter). The YSZ hollow fibres were prepared by a phase inversion technique followed by high temperature sintering in the range 1200 to 1400 °C. Ni anodes were deposited on the internal surface by electroless plating involving an initial catalyst deposition step with PdCl₂ followed by Ni plating (with a NiSO₄, NaH₂PO₂ and sodium succinate based solution at 70 °C). Fabrication and nickel deposition parameters (nature of solvents, air gap, temperature, electroless bath composition) and heat treatments in oxidising/reducing environments were investigated in order to improve anode and electrolyte microstructure and fuel cell performance. A parallel study of the effect of YSZ sintering temperature, which influences electrolyte porosity, on electrolyte/anode microstructure was performed on mainly dense discs (2.3 mm thick and 15 mm diameter). Complete cells were tested with both disc and hollow fibre design after a La_0.2Sr_0.8Co_0.8Fe_0.2O_3?δ (LSCF) cathode was deposited by slurry coating and co-fired at 1200 °C. Anodes prepared by Ni electroless plating on YSZ electrolytes (discs and hollow fibres) sintered at lower temperature (1000–1200 °C) benefited from a greater Ni penetration compared to electrolytes sintered at 1400 °C. Further increases in anode porosity and performance were achieved by anode oxidation in air at 1200–1400 °C, followed by reduction in H₂ at 800 °C.     

Fabrication of porous Ni–YSZ anodes by PSH-PIM

This paper has investigated the fabrication process of porous Ni–YSZ anodes by the powder injection molding method, in which a powder space holder (PSH) is used. Polymethyl methacrylate (PMMA) has been used as a PSH for mixing with NiO–YSZ powders. For this study, five kinds of feedstock containing 0%, 10%, 20%, 30%, and 40% PMMA by volume were prepared. The thermoplastic binder used for the process had a fixed 35 vol.%, and the powder loads formed the remaining 65, 55, 45, 35, and 25 vol.% of the feedstock. After molding and debinding, the parts were sintered at 1,500 °C. The obtained results showed that increasing the PMMA portion of the feedstock and reducing its powder load causes the viscosity of the feedstock to decrease. The amount of shrinkage of the samples containing 0–30% PMMA showed an almost linear increase with the increase of the PMMA content, and for the samples with 40% PMMA, this increase of shrinkage was higher. The amount of porosity in the samples having 0–30% PMMA increased with the rise in the PMMA content, but in the samples containing 40% PMMA, the amount of porosity decreased, such that it was less than that of the samples with 30% PMMA. The electrical conductivity and flexural strength of all the samples were also studied in this work.     

Characterization of NiO–yttria stabilised zirconia (YSZ) hollow fibres for use as SOFC anodes

NiO–yttria stabilised zirconia (YSZ) hollow fibres with varying NiO content and a desired microstructure were prepared using a phase inversion technique and sintering. By controlling the fabrication parameters, microstructures with predominately finger-like pores near the inner and outer surfaces and a denser central layer with sponge-like pores were produced, for use as substrates for anode-supported hollow fibre solid oxide fuel cells (HF-SOFC). The NiO–YSZ fibres were reduced to Ni–YSZ at 250–700 °C in hydrogen flowing at 20 cm³ min^? 1 to produce Ni–YSZ hollow fibres, the mechanical and electrical properties of which were determined subsequently, reduction to Ni being verified by X-ray diffraction. The effects of NiO concentration and sintering temperature of the fibre precursors on the conductivity, strength and porosity of the reduced hollow fibres were investigated to assess their suitability for use as anode substrates. As expected, increasing Ni concentration increased electrical conductivities and decreased mechanical strength. Sintering temperature had a critical effect in producing axially conductive hollow fibres of sufficient mechanical strength for use as SOFC anodes. The hollow fibres retained their initial microstructure through the reduction process, though ca. 41% volume contraction is predicted on reduction of NiO to Ni, producing increased porosity in the reduced fibres. The mean porosity of the Ni–YSZ hollow fibres was ca. 60% and ca. 40% after sintered at 1250 °C and 1400 °C, respectively. The mean pore sizes for all the fibres after reduction varied between ca. 0.3 and 1 µm. The hollow fibres produced with 60% NiO, of length ca. 300 mm, electrical conductivities of ca. (1–2.25) × 10⁵ S m^? 1 and a porosity of ca. 43% are being used currently to construct and test the electrical behaviour of an anode-supported HF-SOFC.     

Porous electrolyte-supported tubular micro-SOFC design

Due to the poor redox cycling resistance of the second generation of μ-SOFCs, a new generation of SOFC has been recently developed using a porous electrolyte-supported structure to overcome this problem. In this research, the porous structure was successfully fabricated with slip casting using calcined YSZ (ZrO₂ + 8 mol% Y₂O₃) with or without graphite as a pore former. Calcination of YSZ powder at 1300-1500 °C prior to making the slip leads to growth of YSZ crystals and particle size which results in a decrease in surface area and powder sinterability. This was found to be an important criterion in developing the porous structure as, due to the high sinterability of non-calcined YSZ, even the addition of graphite is inadequate to generate sufficient open porosity. A dense YSZ electrolyte layer was immediately coated on the porous structure using YSZ calcined at 1300 °C with a sequential slip casting method. Sample thickness was found to be a function of both graphite content as well as YSZ calcination temperature. Physical properties of the porous YSZ supports and SEM analysis of the support and coated electrolyte are presented.     

Effects of powder sizes and reduction parameters on the strength of Ni–YSZ anodes

In order for solid oxide fuel cells to survive the mechanical loading associated with residual manufacturing stresses, assembly, thermal mismatches, ion activity gradients, or operational loading, one or more components of the cell must provide sufficient mechanical strength. In anode-supported electrolyte designs, the anode layer is called upon to provide the necessary mechanical strength, in addition to fulfilling its electrical and electrochemical roles. To investigate how the starting powder sizes and how the reduction process parameters influenced the strength of NiO(Ni)–YSZ anode laminates, concentric ring-on-ring, biaxial flexure experiments were performed. Two composite microstructures and two reduction processes were examined. One specimen was obtained from powders with only fine (≈ 2 μm) NiO and YSZ particles, while the other had a bi-modal distribution of coarse and fine particles of NiO (11 μm and 5 μm) and YSZ (4 μm and 1 μm). One reduction process introduces forming gas at room temperature, while the other process introduced forming gas only after the specimen reached its reduction temperature (600 or 800 °C). The anodes containing coarse and fine particles had slower reduction rates, poorly connected microstructures, and had 35–40% lower biaxial flexure strengths than anodes with only fine starting powders. The temperature at which forming gas was introduced had a significant impact on the microstructural evolution and thus also on the mechanical properties. Although introducing forming gas at room temperature led to more complete and faster reductions, the resulting microstructures were poorly connected, and the reduced laminates had almost 30% less strength than laminates that were reduced at constant temperature.     

Influence of sintering temperature and aging on properties of cermet Ni/8YSZ materials obtained by citric method

The anode supported cell for solid oxide fuel cell, as a modification of the traditional Ni-YSZ anode supported on electrolyte, is examined in this work. The materials obtained on the base of citric method are presented and investigated in this work. The materials consisted of 40 wt.% Ni/YSZ, 50 wt.% Ni/YSZ and 60 wt.% Ni/YSZ were obtained. The base Ni/YSZ materials are tested on the two ways: (a) aging tests and (b) sintering tests. All the materials after aging and sintering are tested by the impedance spectroscopy. The results of electrical conductivity for samples before and after aging show that only in the case of 40 wt.% Ni/YSZ, sample loses of metallic conductivity after 500 h of heating. The other samples reveal metallic conductivity even after long period of aging. The tests of sintering temperature show that this process does not affect significantly on electrical conductivity of the materials.     

Kinetics of oxidation and reduction of Ni/YSZ cermets

A cyclic reduction and oxidation of Ni/YSZ-cermet anodes for Solid Oxide Fuel Cells (SOFC) resulted in an increase of the polarization resistance. Therefore, investigations concerning kinetics of oxidation/reduction and the impact of redox cycles on the mi-crostructure of Ni/YSZ bulk ceramics were made. The reaction process of the basic system Ni/NiO was compared with cermet bulk samples and the influence of NiO and YSZ particle sizes and sintering temperatures on kinetics and microstructure was studied using thermo-gravimetry and dilatometry. The investigations on bulk ceramics indicated that no length change occurred during reduction, whereas reoxidation led to an increase in the length of the samples which strongly depended on the microstructure. It was shown that bulk samples sintered at temperatures below 1300 °C can withstand redox cycles much better than those sintered at higher temperatures. Furthermore, it was found that by decreasing the NiO particle size and using a NiO/YSZ particle size ratio of aproximately 3:2, a smaller length increase after reoxidation was achieved. An increase of the polarization resistance could be ascribed to the formation of cracks within the bulk sample which interrupt current paths and therefore reduce the amount of the active triple phase boundary. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

The electromagnetic shielding of Ni films deposited on cenosphere particles by magnetron sputtering method

Ni-coated cenosphere particles were successfully fabricated by an ultrasonic-assisted magnetron sputtering equipment. Their surface morphology and microstructure were analyzed using field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). FE-SEM results indicate that the Ni films coated by magnetron sputtering are uniform and compact. Ni film uniformity was related with the sputtering power and a large uniform film could be achieved at lower sputtering power. XRD results imply that the Ni film coated on cenospheres was a face-centered cubic (fcc) structure and the crystallization of film sample increases with increasing the sputtering power. The electromagnetic interference (EMI) shielding effectiveness (SE) of Ni-coated cenosphere particles were measured to be 4-27 dB over a frequency range 80-100 GHz, higher than those of uncoated cenosphere particles. The higher sputtering power and Ni film thickness are the higher EMI SE of the specimens. Ni-coated cenosphere particles are most promising alternative candidates for millimeter wave EMI shielding due to their lightweight, low cost, ease of processing, high floating time, good dispersion and tunable conductivities as compared with typical electromagnetic wave countermeasure materials.     

A Ni/YSZ composite containing Ce0.9Ca0.1O2−δ particles as an anode for SOFCs

A composite material (hereafter referred to as NYC) containing Ni, Y₂O₃-stabilized ZrO₂ (YSZ) and Ce_0.9Ca_0.1O_2−δ (CC10) particles was prepared and used as the anode of solid oxide fuel cells (SOFCs). The performance of NYC was better than that of conventional Ni/YSZ anodes in terms of anodic overpotential and interface impedance. The additional CC10 particles improved the anode properties. XRD results suggest that a solid solution of YSZ and CC10 was produced. From impedance measurements, it is concluded that the solid solution exhibits substantial electronic conduction. Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ anodes exhibited the best properties over the experimental temperature range. A SOFC with an anode of Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ provided the maximum power density and current density. Addition of CC10 with an average particle size of 0.3 μm was more advantageous than that with an average size of 3 μm.     

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.     

Porosity effect on the electrical conductivity of sintered powder compacts

A new equation for calculating the electrical conductivity of sintered powder compacts is proposed. In this equation, the effective resistivity of porous compacts is a function of the fully dense material conductivity, the porosity of the compact and the tap porosity of the starting powder. The new equation is applicable to powder sintered compacts from zero porosity to tap porosity. A connection between this equation and the percolation conduction theory is stated. The proposed equation has been experimentally validated with sintered compacts of six different metallic powders. Results confirm very good agreement with theoretical predictions. PACS  72.15.Eb; 72.90.+y; 81.05.Rm; 81.20.Ev     

Electrical conductivity of thick film YSZ

When yttria-stabilized zirconia (YSZ) electrolyte is coated and co-sintered on top of Ni–YSZ anode support, the measured conductivities of YSZ thick films (10–30 μm thick) are often lower than that of bulk YSZ. In this study, we found the observation by fabricating free-standing YSZ thick films and measuring and comparing in-plain and across-plain conductivities. The in-plane conductivity of free-standing YSZ film matched very well with the conductivity of mm-thick bulk sample. It was further shown that the conductivity decrease can be minimized by using better electrode morphology.Another factor that decreases the film conductivity was identified when the thick film was reduced. The conductivity decrease, ∼26% after reduction for 1h in humidified hydrogen gas, was due to Ni-doping into YSZ during sintering process.In order to minimize the conductivity drop of thick film YSZ during SOFC (solid oxide fuel cell) operation, an intermediate layer may be used between YSZ and anode support to prevent Ni-doping during co-sintering process in addition to the well-designed electrode morphology.     

Highly dispersed anodes for solid oxide fuel cells using NiO/YSZ/BZY triple-phase composite powders prepared by spray pyrolysis

NiO/Y₂O₃-stabilized ZrO₂ (YSZ)/Y-doped BaZrO₃ (BZY) triple-phase composite powders were prepared by spray pyrolysis and evaluated for Ni/YSZ/BZY cermet anodes, which are considered effective for dry CH₄ operation in solid oxide fuel cells. The structure of the particles in these powders was fine crystal fragments, and the individual material phases were clearly separated and highly dispersed within the particles. The Ni/YSZ/BZY cermet anodes fabricated with these composite powders maintained a fine electrode microstructure equivalent to that in a simple Ni/YSZ cermet anode manufactured using a composite powder prepared by spray pyrolysis. Furthermore, the addition of BZY improved the anode performance in humidified H₂ and dry CH₄ operation.     

Materials and reaction mechanisms at anode/electrolyte interfaces for SOFCs

The present paper reviews anodic reaction mechanisms of porous cermet and model anodes at metal/oxide interfaces in solid oxide fuel cells (SOFCs). Some analytical results, electrochemical methods, and reaction models were presented at Ni–YSZ cermets and well defined model anodes. Isotope labeling/secondary ion mass spectrometry (SIMS) analysis techniques were applied to determine the oxygen surface reactivity of oxide electrolytes in reducing atmospheres. The technique was also applied to determine the catalytic activity of metal/oxide interfaces for CH₄ decomposition and reactivity with the reformed gases at the mesh or stripe shaped anodes on different oxides. Observed SIMS images and the electrochemical analyses were compared at the model anode/electrolyte interfaces.     

Synthesis and characterization of a Ni/Ba2In0.6Ti1.4O5.7□0.3 cermet for SOFC application

Ni-based cermets were prepared and reduced from mixtures of NiO and Ba₂In_0.6Ti_1.4O_5.7□_0.3. A cermet containing 18.7 vol.% of Ni exhibits promising characteristics: 40% of open porosity and a lower DC resistivity than a Ni/YSZ cermet with a larger Ni content (30 vol.%). Its thermal expansion coefficient is 11.4 × 10^− 6 K^− 1 whereas that measured for Ba₂In_0.6Ti_1.4O_5.7□_0.3 is 9.9 × 10^− 6 K^− 1. Electrical measurements vs. the Ni content have shown that the percolation threshold corresponds to 15.7 vol.% of Ni. By using saccharose as a pore former, the porosity of the electrode can be tuned. It is shown that the pore size is controlled by the particle size distribution of the pore former.     

A wet-chemical route for the preparation of Ni–BaCe0.9Y0.1O3 − δ cermet anodes for IT-SOFCs

Nano-sized BaCe_0.9Y_0.1O_3 ? δ (BCY10) protonic conductor powders were used to prepare Ni-BCY10 cermets for anode-supported intermediate temperature solid oxide fuel cells. A new wet-chemical route was developed starting from Ni nitrates as precursors for NiO. BCY10 powders were suspended in a Ni nitrate aqueous solution that was evaporated to allow NiO precipitation on the BCY grains, obtaining NiO-BCY10 cermets. To obtain the final Ni-BCY10 anodes, pellets were reduced in dry H₂ at 700 °C. The structural and microstructural properties of the pellets were investigated using X-ray diffraction analysis and field emission scanning electron microscopy. A homogeneous dispersion of perovskite and nickel phases was observed. The chemical stability of the anodes was evaluated under wet H₂ and CO₂ atmosphere at 700 °C. The electrical properties of the Ni-BCY10 pellets were evaluated using electrochemical impedance spectroscopy measurements. The Ni-BCY10 cermet electrodes showed large electronic conductivity, demonstrating percolation through the Ni particles, and low area specific resistance at the BCY10 interface. These characteristics make the cermet suitable for application in BCY-based protonic fuel cells. The developed chemical route offers a simple and low-cost procedure to obtain promising high performance anodes.     

Study of the magnetic microstructure of Ni/NiO nanogranular samples above the electric percolation threshold by magnetoresistance measurements

Magnetoresistance measurements have been exploited to gain information on the magnetic microstructure of two Ni/NiO nanogranular materials consisting of Ni nanocrystallites (mean size of the order of 10 nm) embedded in a NiO matrix and differing in the amount of metallic Ni, ~33 and ~61 vol%. The overall conductance of both samples is metallic in character, indicating that the Ni content is above the percolation threshold for electric conductivity; the electric resistivity is two orders of magnitude smaller in the sample with higher Ni fraction (10(-5) Ωm against 10(-3) Ωm). An isotropic, spin-dependent magnetoresistance has been measured in the sample with lower Ni content, whereas both isotropic and anisotropic magnetoresistance phenomena coexist in the other material. This study, associated with magnetization loop measurements and the comparison with the exchange bias effect, allows one to conclude that in the sample with lower Ni content neither the physical percolation of the Ni nanocrystallites nor the magnetic percolation (i.e., formation of a homogeneous ferromagnetic network) are achieved; in the other sample physical percolation is reached while magnetic percolation is still absent. In both behaviors, a key role is played by the NiO matrix, which brings about a magnetic nanocrystallite/matrix interface exchange energy term and rules both the direct exchange interaction among Ni nanocrystallites and the magnetotransport properties of these nanogranular materials.     

Electrical conductivity of yttria-stabilized zirconia with cobalt addition

Yttria-stabilized zirconia is the most developed solid electrolyte for use in high-temperature solid oxide fuel cells. Commercial yttria-stabilized zirconia powders reach high densification at temperatures higher than that of the usual anode materials. Reduction of the sintering temperature of the solid electrolyte could allow for co-firing of both ceramic components, thereby reducing production costs. The main purpose of this work was to study the effect of small cobalt additions on densification and on electrical conductivity of 8 mol% yttria-stabilized zirconia. Linear shrinkage results show that the onset temperature for shrinkage decreases with increasing cobalt content. Impedance spectroscopy measurements reveal that the electrical conductivity depends on the sintering profile. For specimens sintered at 1400 °C for 0.1 h the electrical conductivity of grains and grain boundaries are almost unchanged with that of 8YSZ. In contrast, for specimens sintered at the same temperature but for 0.5 h of soaking time, the electrical conductivity is higher in 0.025 mol% samples and is lower for 1 mol% Co doped 8YSZ. Degradation of the microstructure by increased porosity was obtained for high additive contents.     

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.