Cathode overpotential investigation by means of “Built-in” potential electrode

The objective of the present work is the development of a “built-in” potential electrode method for direct measurements of the cathode and anode overpotentials and the corresponding interface resistances of solid oxide fuel cells (SOFC). The studies were performed on a yttria-stabilised zirconia (YSZ) electrolyte-supported SOFC using La_0.8Sr_0.2MnO₃ as cathode, GDC as protecting layer and Ni-ScSZ cermet as anode. The mesh potential electrode was placed inside the YSZ membrane near the cathode side. Using the combination of the I-U and the impedance measurements with the built-in potential electrode technique, the temperature dependencies of the electrodes and electrolyte contributions to the total cell resistance were determined.     

Characterization of solid oxide fuel cells based on solid electrolytes or mixed ionic electronic conductors

The relation between cell voltage (V_cell), applied chemical potential difference (Δμ(O₂)) and cell current (I_t) for solid oxide fuel cells (SOFC) based on mixed ionic electronic conductors is derived by considering also the effect of electrode impedance. Four-probe measurements, combined with current interruption analysis, are considered to yield the relation between ionic current (I_i) and overpotential (η). The theoretical relations are used to analyze experiments on fuel cells with Ce_0.8Sm_0.2O_1.9 and Ce_0.8Gd_0.2O_1.9 electrolytes with La_0.8Sr_0.16CoO₃ or Pt as the cathode and Ni/Ce_0.9Ca_0.1O_1.9−xor Pt as the anode. The electrode overpotentials of these cells, determined by current interruption measurements, are discussed assuming different models including impeded mass transport in the gas phase for molecular and monoatomic oxygen and Butler-Volmer type charge transfer overpotential.     

Co-electrolysis of CO2 and H2O in solid oxide cells: Performance and durability

This study examines the initial performance and durability of a solid oxide cell applied for co-electrolysis of CO₂ and H₂O. Such a cell, when powered by renewable/nuclear energy, could be used to recycle CO₂ into sustainable hydrocarbon fuels. Polarization curves and electrochemical impedance spectroscopy were employed to characterize the initial performance and to break down the cell resistance into the resistance for the specific processes occurring during operation. Transformation of the impedance data to the distribution of relaxation times (DRT) and comparison of measurements taken under systematically varied test conditions enabled clear visual identification of five electrode processes that contribute to the cell resistance. The processes could be assigned to each electrode and to gas concentration effects by examining their dependence on gas composition changes and temperature.This study also introduces the use of the DRT to study cell degradation without relying on a model. The durability was tested at consecutively higher current densities (and corresponding overpotentials). By analyzing the impedance spectra before and after each segment, it was found that at low current density operation (− 0.25 A/cm² segment) degradation at the Ni/YSZ electrode was dominant, whereas at higher current densities (− 0.5 A/cm² and − 1.0 A/cm²), the Ni/YSZ electrode continued to degrade but the serial resistance and degradation at the LSM/YSZ electrode began to also play a major role in the total loss in cell performance. This suggests different degradation mechanisms for high and low current density operation.     

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.     

SOFC characteristics along the flow path

Solid oxide fuel cells (SOFCs) in metallic housings were integrally and locally characterised. The tests were performed in counter flow operation for hydrogen concentrations from 2% to 100%, to identify concentration limitations and to optimise fuel utilisation. Cell characterisations were performed by spatially resolved electrochemical impedance spectroscopy (EIS), current density/voltage (i–V) and temperature measurements as well as gas chromatography measurements at 16 distinct points across the cell. The results show a substantial variation of current density and voltage distribution along the flow path with varying hydrogen content and fuel utilisation. The fuel utilisation was calculated from the local current densities and compared to the values measured by gas chromatography. Both sets of results showed good agreement. At low hydrogen inlet concentrations the voltage at the fuel outlet drops to values that might be harmful for the stability of the anode since reoxidation of nickel can occur. The impedances obtained by local EIS did not show an overall coherent dependency on the hydrogen concentration. EIS under load revealed two distinct domains: in the range of hydrogen concentrations of 2–10% H₂ the impedance decreased significantly with increasing hydrogen content whereas at higher hydrogen contents the impedance was hardly affected. This indicates significant concentration and diffusion overpotential at low hydrogen concentrations. The local data showed differing behaviour in the middle of the cell compared to the fuel outlet. Leakage at the sealing could be identified as a possible reason. As an additional method of investigation, the voltage drop over the contact resistance of the cathode side was measured. Temperature measurements show that local temperatures differ significantly depending on the load applied to the cell. This observation emphasizes the importance of a thermal management adapted to the characteristics on operation conditions of the cells, particularly when the stack itself has only a low mass.     

Reactive sputtering deposition and electrochemical characterisation of thin solid electrolyte membranes for solid oxide fuel cells

Solid oxide fuel cells directly convert the chemical energy of a fuel into electricity. To enhance the efficiency of the fuel cells, the thickness of the gastight solid electrolyte membranes should be as thin as possible. Y₂O₃-stabilised ZrO₂ (YSZ) electrolyte films were prepared by reactive sputtering deposition using Zr/Y targets in Ar/O₂ atmospheres. The films were 5 – 8 μm thin and were deposited onto anode substrates made of a NiO/YSZ composite. After deposition of a cathode with the composition La_0.65Sr_0.35MnO₃ the electrochemical properties of such a fuel cell were tested under operating conditions at temperatures between 600 °C and 850 °C. Current-voltage curves were recorded and impedance measurements were performed to calculate apparent activation energies from the fitted resistance data. The conductivity of the YSZ films varied between 4.6·10⁻⁶ S/cm and 2.2·10⁻⁵ S/cm at 400 °C and the fuel cell gave a reasonable power density of 0.4 W/cm² at 0.7 V and 790 °C using H₂ with 3 % H₂O as fuel gas. The gas compositions were varied to distinguish the electrochemical processes of the anode and cathode in the impedance spectra. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

8YSZ/(La0.8Sr0.2)0.95MnO3-δ cathode performance at 1-3 bar oxygen pressures

Pressurised operation of solid oxide fuel cells (SOFC) has been shown to significantly improve their performance (Singhal, 2000) [1], however little work has been done on the effects of pressure on SOFC cathodes. The effect of pressurised oxygen on the area specific polarisation resistance (ASRp) of (La_0.8Sr_0.2)_0.95MnO_3-δ/8YSZ SOFC cathodes was determined by electrochemical impedance spectroscopy (EIS). Pellets of 8YSZ were pressed and sintered at 1350 °C, and screen printed layers of LSM/8YSZ cathode and LSM current collector were applied and sintered at 1300 °C and 1200 °C respectively. EIS was carried out between 1 and 3 bar oxygen at 800-1000 °C. One process dominated the spectra, and was identified as process C, (Jorgensen and Morgensen, 2001) [2] by comparison of measured and reference frequency maxima, the dependence of polarisation resistance on P_O2, the capacitance, and the activation energy. It is suggested that this represents the physical process of dissociative adsorption of oxygen at the triple phase boundaries of the electrode. A second process, with a magnitude almost independent of P_O2, is observed, which may be process B [2], related to transport of oxygen ions in the YSZ.     

Processing and characterization of ultra-thin yttria-stabilized zirconia (YSZ) electrolytic films for SOFC

Sub-micron yttria-stabilized zirconia (YSZ) electrolyte layer was prepared by a liquid state deposition method and with an average thickness of 0.5 μm to improve the performance of the anode-supported solid oxide fuel cell (SOFC). The YSZ precursors, containing yttrium and zirconium species and an additive, poly-vinyl-pyrrolidone (PVP), were spin-coated on a Ni/YSZ anode substrate. Several properties, including crystalline phases, microstructures, and current–voltage (I–V) characteristics, were investigated. The thin film of 4 mol% Y₂O₃-doped ZrO₂ (4YSZ) consisted of cubic, tetragonal, and a trace of monoclinic phases, and showed a crack-free layer after sintering at 1300 °C. The anode supported SOFC, which consists of the Ni–YSZ anode, 4YSZ electrolyte, and Pt/Pd cathode, showed power densities of 477 mW/cm² at 600 °C, and 684 mW/cm² at 800 °C. Otherwise, the surface cracks of the other YSZ-coated samples (e.g. 8YSZ) can be repaired by a multi-coating method.     

Electrochemical cell with two layers cathode for NO decomposition

An electrochemical cell composed of an yttria-stabilized zirconia disk and two layers cathode was used for nitrogen monoxide decomposition. It was found that covering the Pt cathode by a mixture of oxygen ionic conductor (YSZ) and electronic conductor (NiO) leads to enhancement of the performance of the electrochemical cell for NO_x decomposition in the presence of excess oxygen. The decomposition activity was measured for the one-compartment cell oxide|(cathode)|YSZ|(anode) by applying a DC voltage lower than 3.7 V in the temperature range 550–700 °C. The microstructure of the YSZ-NiO mixed oxide electrodes was investigated in dependence of the cell operating condition and the working electrode sintering temperature. The correlation between the microstructure of the mixed oxide electrode and conversion rate of NO was studied. The phenomenon of self-optimization of the microstructure of the NiO-YSZ working electrode during the cell operation was observed and investigated. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Polarization behavior of Ni-YSZ cermet anodes in YSZ fuel cells running on methane under internal reforming conditions

The polarization characteristics of the Ni-YSZ cermet anode/YSZ interface were studied as a function of gas phase composition, temperature and anodic overpotential in methane fuelled internal reforming YSZ fuel cells. AC impedance measurements carried out under open circuit conditions in the temperature range 800 to 900°C showed the presence of at least two rate-limiting processes that were influenced by temperature and gas phase composition. The apparent polarization resistance, R_app, of the Ni-YSZ cermet anode/YSZ interface was found to increase with increasing methane partial pressure and decreasing H₂O partial pressure. The activation energy related to the apparent polarization conductance R _app ⁻¹ varied between 0.7 and 1.1 eV, mainly due to the variation of P_{H 2 O}. The order of magnitude of the apparent capacitance, C_app, values calculated from AC impedance data under open circuit conditions indicate that the observed capacitance corresponds to the double layer capacitance of the Ni/YSZ interface and/or a pseudo-capacitance related to adsorption of species on the Ni-YSZ cermet electrode accompanied by charge transfer. C_app was found to decrease with increasing methane partial pressure. AC impedance measurements carried out under closed circuit conditions at 900 °C and four different P_{H 2 O} showed the appearance of a low-frequency inductive loop at high anodic over-potentials, in addition to the features observed under open circuit conditions. The effect of gas phase composition on R_app was similar to the one observed under open circuit conditions. In addition an almost exponential decrease of R_app with increasing anodic overpotential was observed. The present results are compared with results presented in literature and discussed in the frame of the mechanism of the electrochemical and catalytic reactions taking place over the anode. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

(La0.75Sr0.25)(Cr0.5Mn0.5)O3/YSZ composite anodes for methane oxidation reaction in solid oxide fuel cells

The synthesis and performance of (La_0.75Sr_0.25)(Cr_0.5Mn_0.5)O₃/Y₂O₃–ZrO₂ (LSCM/YSZ) composites are investigated as alternative anodes for the direct utilization of methane (i.e., natural gas) in solid oxide fuel cells. Addition of YSZ phase greatly improves the adhesion and reduces the electrode polarization resistance of the LSCM/YSZ composite anodes. LSCM/YSZ composite anodes show reasonably good performance for the methane oxidation reaction in wet CH₄ and the best electrode performance was achieved for the composite with LSCM contents of 50–60 wt.% with polarization resistances of 2–3 Ω cm² in 97% CH₄/3% H₂O at 850 °C. The electrode impedance for the methane oxidation in wet CH₄ on the LSCM/YSZ composite anodes was characterized by three separable arcs and the electrode behavior could be explained based on the ALS model for the reaction on the MIEC electrode. The results indicate that electrocatalytic activity of the LSCM/YSZ composite anodes for the methane oxidation is likely limited by the oxygen vacancy diffusion in the substituted lanthanum chromite-based materials.     

Electrical properties of GdBaCo2O5+x for ITSOFC applications

In order to develop a cathode that can be used in intermediate temperature solid oxide fuel cells (ITSOFC), the double perovskite material GdBaCo₂O_5+x has been prepared and its electrode performance investigated at temperatures below 700 °C by AC impedance spectroscopy. Preliminary results show that the ASRs of GdBaCo₂O_5+x cathode materials are as low as 0.53 Ω cm² at 645 °C. This encouraging data identifies GdBaCo₂O_5+x as a potential cathode material for ITSOFCs.     

Reaction mechanisms of the copper-manganese spinel cathode in a solid oxide fuel cell

Cu_1.25Mn_1.75O₄ spinel (CMO) was studied as a potential solid oxide fuel cell (SOFC) cathode material at intermediate temperatures. The reaction mechanism of a composite cathode consisting of Cu_1.25Mn_1.75O₄ and yttria-stabilized zirconia (YSZ) was investigated by impedance spectroscopy. The influence of the CMO/YSZ ratio, time exposed to current passage and temperature on the impedance spectra was examined. Activation energy of the corresponding processes was calculated to be near 1 eV and between 1.32 and 1.96 eV for the high and low frequency arcs in the impedance spectra. Comparison between CMO-YSZ and Sr-doped LaMnO₃ (LSM)-YSZ composite cathodes showed they had similar reaction mechanisms. The transport or transfer of oxygen intermediates or oxide ions between the catalyst and electrolyte was suggested to be the rate determining steps between 700 and 800 °C, whereas dissociative adsorption, mass transfer and surface diffusion were rate controlling between 600 and 700 °C.     

Preparation of YSZ films by magnetron sputtering for anode-supported SOFC

YSZ films for anode-supported SOFCs were prepared by reactive sputtering method. It was found that the surface morphology of anode substrate has a very important effect on the quality of sputtered films. By applying an anode functional layer and making the anode surface smooth, dense and uniform YSZ films of 10 µm in thickness were successfully fabricated. The sintering behaviors of the sputtered YSZ films were also discussed. It is suggested that the optimized densification condition for the deposited YSZ films is sintering at 1250 °C for 4 h. Single cells with sputtered YSZ film as electrolyte and LSM-YSZ as active cathode materials were tested. 1.08 V open circuit voltage and a 700 mW/cm² maximum power density were achieved at 750 °C by using humidified H₂ as fuel and air as oxidant.     

Performance of a tubular solid oxide fuel cell with model kerosene reformate gas

A performance of an anode-supported tubular Ni–8YSZ/Ni–ScSZ/ScSZ/GDC/LSC cell was investigated at 650–750 °C by feeding model kerosene reformate gas (H₂, H₂O, CO, CO₂, and CH₄) to a Ni–8YSZ/Ni–ScSZ anode. Variations of gas composition were observed not only between inlet and outlet of anode to estimate the degree of internal reforming, but also during current input by online quadrupole mass spectrometry and Fourier-transform infrared spectrometry.The electrochemical performance of the cell was independent of reforming temperature of kerosene, i.e. gas composition (in particular CH₄ concentration) at moderate anode gas flow rates. At open-circuit states, 10% or less methane in the kerosene-reformed gas was readily converted by steam or CO₂ over the Ni–8YSZ/Ni–ScSZ electrode so that gas compositions could almost follow the thermodynamic equilibrium at 650–750 °C. This suggests that the internal reforming should proceed almost completely over the Ni anode. Consumption of H₂ and CO and production of CO₂ were observed during current input. I–V characteristics remained constant at 650 °C as long as anodic W/F was more than 0.2 kg mmol^− 1 s. It was demonstrated that a catalytic activity of an anode electrode for hydrocarbons will be important for SOFCs with liquid fuels such as kerosene in order not to deteriorate cell performance.     

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.     

Electrocatalytic activity of a Gd2Ti0.6Mo1.2Sc0.2O7-δ anode towards hydrogen and methane electro-oxidation in a solid oxide fuel cell

Mixed conducting oxide anodes are being considered for the direct utilisation of natural gas in high temperature fuel cells. This work refers to the electrochemical characterization of the pyrochlore Gd₂Ti_0.6Mo_1.2Sc_0.2O_7-δ (GTMS) as anode in a solid oxide fuel cell running in low humidity hydrogen or methane. The electro-oxidation reaction was investigated using impedance spectroscopy, potentiostatic measurements and cyclic voltammetry. Kinetic data were obtained for different fuels in the temperature range 845–932 °C. In a methane-fuelled cell, steam reforming appears to be the rate-limiting step. The overall polarisation resistance of the anode under open circuit conditions at 932 °C was 6.86 Ω·cm² in 97% H₂/3% H₂O, and 43 Ω·cm² in 97% CH₄/3% H₂O. For a 97% fuel-3% H₂O/GTMS//YSZ-Al₂O₃//Pt/air cell, the maximum power output at 932 °C was 9.5 mW/cm² and 1.8 mW/cm² in hydrogen and methane, respectively. First investigations on this type of electrode material show unidentified peaks on XRD spectra after electrochemical test, which indicate GTMS instability under experimental conditions. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Impedance investigation on porous Sr-doped LaMnO<Subscript>3</Subscript> films onto Sr-Mg-doped LaGaO<Subscript>3</Subscript> electrolyte

The use of Sr-Mg-doped LaGaO₃ (LSGM), a highly conducting oxygen ion electrolyte, in intermediate temperature solid oxide fuel cells (IT-SOFC) technology requires suitable electrode materials. Because the Sr-doped LaMnO₃ (LSM) cathode coupled with the YSZ electrolyte had shown relatively good performances, it has been also suggested for LSGM-based cells. As cathode overpotential is the main performance limitation, the optimization of the LSM/LSGM interface might be of fundamental relevance in the technology development of LSGM-based IT-SOFC. LSM films with different porosities were screen printed on both faces of the LSGM pellets; their morphology and electrical properties were investigated by scanning electron microscopy and impedance spectroscopy, respectively. Porosity was induced by the addition of icing sugar (3–5 wt%) to the LSM powder during ink preparation. Homogeneous electrode layers with a thickness of about 30 μm were obtained. The higher the sugar amount, the higher the film porosity and the lower the LSM grain size. The Nyquist plots show two low frequency arcs to which the charge transfer and mass transfer process or oxygen dissociation process were associated, respectively. One can expect that the best electrochemical performances are obtained using highly porous electrode. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Electrochemical characterization of mixed conducting and composite SOFC cathodes

The electrochemical performance of La_0.58Sr_0.4Co_0.2Fe_0.8O_3−δ (L58SCF), La_0.9Sr_1.1FeO_4−δ (LS2F) and LSM (La_0.65Sr_0.3MnO_3−δ)/LSM–YSZ (50 wt.% LSM–50 wt.% ZrO₂ (8 mol% Y₂O₃)) cathode electrodes interfaced to a double layer Ce_0.8Gd_0.2O_2−δ (CGO)/YSZ electrolyte was studied in the temperature range of 600 to 850 °C and under flow of 21% O₂/He mixture, using impedance spectroscopy and current density–overpotential measurements. The L58SCF cathode exhibited the highest electrocatalytic activity for oxygen reduction, according to the order: LS2F/CGO/YSZ ≤ LSM/LSM–YSZ/CGO/YSZ < L58SCF/CGO/YSZ.     

Characterization of CO tolerance of PEMFC by ac impedance spectroscopy

The CO tolerance of a proton exchange membrane fuel cell (PEMFC) was investigated by ac impedance spectroscopy. The impedance of the fuel cell could be obtained by feeding oxygen into the cathode side and simulated gas into anode side. Furthermore, the anode impedance could be obtained by feeding hydrogen into the cathode side and simulated gas into anode side. The CO gas had a greater effect on the charge transfer reaction (high frequency arc) and hydrogen dissociative chemisorption (medium frequency arc) but little effect on the low frequency arc. Although the cathode impedance is a main part at high temperature, irrespective of CO concentration (≤100 ppm), the impedance of the full cell depends on anode impedance at low temperature and high CO concentration. It was found that CO gas has little effect on cathode impedance.