Electrode reactions at oxygen,noble metal / stabilized zirconia interfaces

The polarization behaviour of electrodes of the type “oxygen, noble metal / stabilized zirconia”, comprising different zirconia-based materials as electrolyte, platinum or gold as metal component and an oxygen containing gas atmosphere, was investigated at elevated temperatures under equilibrium and non-equilibrium conditions by means of impedance spectroscopy. Massive metal contacts were used as part of the working electrodes. Under non-polarized conditions, the experimental results for platinum indicate a basically uniform reaction mechanism in a vast range of temperature and oxygen partial pressure, involving the surface diffusion of dissociatively adsorbed oxygen on platinum towards the electrochemical reaction sites on the electrolyte surface as rate-determining step. The experimental findings for gold are consistent with the occurrence of two competing reaction mechanisms, namely a charge transfer controlled process and a surface diffusion controlled process, each of them prevailing in different regimes of temperature and oxygen partial pressure. Under polarized conditions, a significant decrease of the polarization resistance takes place, followed by the onset of low frequency loops in the impedance spectra. In the case of cathodic polarization, the onset voltage can be correlated with the partial electron conductivity of the electrolyte, thus confirming the hypothesis of direct participation of electronic species of the electrolyte in the electrode reaction under biased conditions. At moderate temperatures, the polarization induced changes in the electrode properties exhibit a slow relaxation behaviour. This can be attributed to the successive annihilation of additional metastable electrochemical reaction sites having been created during the preceding polarization treatment. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy     

Electrical properties of calcia-doped ceria with oxygen ion conduction

The electrical conductivity of sintered specimens of (CeO₂)_1−x(CaO)_x was investigated by employing a standard four-probe dc technique as a function of temperature between 400°C and 900°C, composition from 0.10x0.80, and oxygen partial pressure from 10⁻¹⁸ to 1 atm. The temperature and composition dependence of the emf have been carried out with a concentration cell. X-ray diffraction studies indicated that a cubic fluorite crystal remained in all specimens studied, although the solubility limit of CaO in CeO₂ was assumed to lie close to 23 mol% from the change of the lattice constant. The magnitude of the conductivity decreased slightly with increase of the dopant concentrations up to x=0.50. The conductivity of these specimens was about 100 times larger than that of calcia-stabilized zirconia at 600°C with a smaller activation energies of 0.83–0.89 eV. With further increasing dopant concentrations, the magnitude of the conductivity was found to decrease remarkably. With an increase in the dopant concentration, the domain of primarily ionic conduction extended to a lower partial pressure. The conductivity of (CeO₂)_0.50(CaO)_0.50 was found to be primarily ionic down to 10⁻¹² atm even at 900°C. These results indicate that CaO-doped CeO₂ may be more an attractive candidate for fuel cells and other applications.     

On the behavior of a dense indium oxide/yttria-stabilized zirconia electrode

The electrical, structural and electrochemical properties of a dense In₂O₃ layer in contact with a single crystal YSZ electrolyte were studied. As a result of dc and ac investigations, it was found that under anodic polarization the rate of Faraday reaction at the surface of the In₂O₃ electrode is as low as in an ionically blocked electrode. Under cathodic polarization, however, the electrochemical activity of the electrode improves depending on the magnitude of the polarization voltage. Likewise, the electrode polarization resistance decreases after platinum or praseodymium oxide having been deposited on the surface of the In₂O₃ layer. The possible mechanism responsible for such a peculiar behaviour and the limiting step of the electrode reactions are discussed.     

Reaction kinetics of the Pt, O2(g)|c-ZrO2 system: precursor-mediated adsorption

A micro kinetic model of the Pt, O₂(g)|c-zirconia electrode/electrolyte system was developed in state space form (model M3). The oxygen adsorption/desorption process was modeled as a precursor-mediated surface reaction. The surface diffusion of atomic oxygen and the electrochemical reduction of atomic oxygen near the three-phase boundary (tpb) were considered. It was shown that the simulated charge-transfer behavior of M3 is significantly different from models with ordinary Langmuir kinetics (model M2). The electrochemical rate constant was estimated from selected experimental data as k₁₀=(6.05±0.25)·10⁶ m³/(mol·s). From experimental results it was concluded that only one adsorbed oxygen species is relevant for the dynamic behavior. In porous Pt electrodes binary gas phase diffusion of oxygen in O₂/N₂ gas mixtures becomes relevant at oxygen partial pressures below 10⁻³ atm. The general procedure for state and parameter estimation can be well adopted for the investigation of further reaction mechanisms.     

Oxygen nonstoichiometry and electrical conductivity of the solid solutions La2−xSrxNiOy (0≤x≤0.5)

Oxygen nonstoichiometry and electrical resistance of a series La_2−xSr_xNiO_y solid solutions, where x=0.0, 0.2 and 0.5 in argon flows at oxygen partial pressures 1.5, 10.2, 49.2, 100 and 286 Pa within the temperature range of 20–1050°C were studied. Nickelate oxygen desorption/sorption spectra when heating–cooling at constant rate demonstrated strong dependence of cation composition of the samples. Unlike La_1.5Sr_0.5NiO_y compounds those of La₂NiO_y and La_1.8Sr_0.2NiO_y have weakly bonded oxygen, capable to exchange reversibly with the gas phase at the temperatures higher than 250°C. The equilibrium values of oxygen nonstoichiometry and specific resistance for the these nickelates were determined at 300–1050°C and p_O2=1.5–286 Pa as a functions of temperature versus oxygen partial pressure. All nickelate studied appear to be p-type conductors with metal electric conductivity at equilibrium states.     

Electrical conducting properties of proton-conducting terbium-doped strontium cerate membrane

The electrical conduction behavior of SrCe_0.95Tb_0.05O_3−δ (SCTb) was investigated in different gases at high temperatures. In air, oxygen or nitrogen SCTb shows small electronic-hole conduction below 800°C and oxygen ionic conduction over 800°C with activation energy about 30 kJ/mol and 164–181 kJ/mol respectively. SCTb becomes a protonic conductor in hydrogen or methane in 500–900°C, with the proton conductivity in the range of 10⁻³–10⁻² S/cm, two to three orders of magnitude higher than electronic or oxygen ionic conductivity of SCTb in air or oxygen. The activation energy for protonic conduction in SCTb is 49 kJ/mol in methane and 54 kJ/mol in hydrogen. The electrical conductivity of SCTb in water vapor-saturated nitrogen, air or oxygen is higher than in corresponding gas without water vapor. Presence of water vapor does not affect the electrical conduction of SCTb in hydrogen or methane. Gas permeation measurements show that SCTb membrane is impermeable to hydrogen when the membrane is exposed to hydrogen or methane upstream and nitrogen or oxygen downstream. These results confirm that SCTb is a pure protonic conductor with very low electronic and oxygen ionic conductivity. SCTb will find applications as a high temperature electrolyte in fuel cells or hydrogen sensors.     

Sr-doped LaInO3 and its possible application in a single layer SOFC

The effects of dopants on the electrical conductivity of the perovskite-type oxide LaInO₃ have been investigated. Replacement of La by Sr is the most effective way to enhance the conductivity of LaInO₃, whereas Ca substitution for In is rather difficult due to the large difference in the ion radii. The optimum composition is La_0.9Sr_0.1InO_3−δ whose maximum conductivity is 7.6×10⁻³ S cm⁻¹ at 900°C. The electrical conductivity of La_0.9Sr_0.1InO_3−δ has been measured over a wide range of oxygen partial pressure from pO₂=1 to 10⁻²⁵ atm. P-type and n-type behavior at high and low oxygen partial pressure have been observed, respectively, while at intermediate oxygen partial pressures, the electrical conductivity changes only slightly with the oxygen partial pressure. The concept of a single layer solid oxide fuel cell based on a La_0.9Sr_0.1InO_3−δ ceramic pellet has been tested. A maximum power density of 3 mW cm⁻² at 800°C was achieved when dilute H₂ and air were used as fuel and oxidizing agent, respectively.     

Oxygen transfer processes in (La,Sr)MnO3/Y2O3-stabilized ZrO2 cathodes: an impedance spectroscopy study

Impedance spectroscopy was used to study the oxygen reaction kinetics of La_0.8Sr_0.2MnO₃ (LSM)-based electrodes on Y₂O₃-stabilized ZrO₂ (YSZ) electrolytes. Three types of electrodes were studied: pure LSM, LSM–YSZ composites, and LSM/LSM–YSZ bilayers. The electrodes were formed by spin coating and sintering on single-crystal YSZ substrates. Measurements were taken at temperatures ranging from 550 to 850°C and oxygen partial pressures from 1×10⁻³ to 1 atm. An arc whose resistance R_el had a high activation energy, E_a=1.61±0.05 eV, and a weak oxygen partial pressure dependence, (P_O2)^−1/6, was observed for the LSM electrodes. A similar arc was observed for LSM–YSZ electrodes, where R_el(P_O2)^−0.29 and the activation energy was 1.49±0.02 eV. The combination of a high activation energy and a weak P_O2 dependence was attributed to oxygen dissociation and adsorption rate-limiting steps for both types of electrodes. LSM–YSZ composite cathodes showed substantially lower overall interfacial resistance values than LSM, but exhibited an additional arc attributed to the resistance of YSZ grain boundaries within the LSM–YSZ. At 850°C and low P_O2, an additional arc was observed with size varying as (P_O2)^−0.80 for LSM and (P_O2)^−0.57 for LSM–YSZ, suggesting that diffusion had become an additional rate limiting step. Bilayer LSM/LSM–YSZ electrodes yielded results intermediate between LSM and LSM–YSZ. The results showed that most of the improvement in electrode performance was achieved for a LSM–YSZ layer only ≈2 μm thick. However, a decrease in the grain-boundary resistance would produce much better performance in thicker LSM–YSZ electrodes.     

Solid-state electrochemical CO2 sensor by coupling lithium ion conductor (Li2CO3-Li3PO4-Asl2O3) with oxide ion-electron mixed conductor (La0.9Sr0.1MnO3)

A solid-state electrochemical cell of the type O₂(air), PtLa_0.9Sr_0.1MnO₃/Li₂CO₃(+5 mol% Li₃PO₄ + 6 mol% Al₂O₃)/Au, CO₂, O₂ was composed to determine CO₂ concentration, where Li₂CO₃, a lithium ion conductor, was used as an electrolyte, and the perovskite-type oxide (La_0.9Sr_0.1MnO₃)/O₂-electrode as a reference electrode. The electromotive force (EMF) of the cell was found to be proportional to the logarithm of CO/₂ partial pressure in CO₂/O₂/N₂ gas mixtures at temperatures between 300 and 400 °C. The EMF responded to changes of CO₂ partial pressure within 1 min at 400 °C. The sensitivity to CO₂ of this cell was not affected by coexistence of O₂, and the EMF remained constant after the first 15 days. The mechanism for sensing CO₂ is discussed.     

Oxygen tracer diffusion in La1 − xSrxCoO3

Tracer diffusion of ¹⁸O in dense, polycrystalline La_1−xSr_xCoO₃ for x = 0.1 has been measured in the temperature range 400 to 600 °C and at 500 °C for x = 0.2 at an oxygen partial pressure of 1 × 10⁵ Pa. Depth profiles were obtained by secondary ion mass spectrometry. The diffusion coefficient for La_0.9Sr_0.1CoO₃ is given by D = (17–247) exp[(−232 ± 8 kJ/mole)/RT] cm²/s. This value is several orders of magnitude lower than D extrapolated from the results for x = 0.2 measured in the 700–900 °C temperature range. One possible explanation for the discrepancy is that the two measurements reflect different diffusion paths. As expected, La_0.8Sr_0.2CoO₃ exhibits a higher diffusivity at 500 °C than does La_0.9Sr_0.1CoO₃.     

High temperature transport processes in lithium niobate

The electrical conductivity of single crystal lithium niobate (LiNbO₃) was determined as a function of temperature for various oxygen partial pressures. The electrical conductivity is proportional to P_o2^−1/4 which can be explained by a defect equilibrium involving singly ionized oxygen vacancies and electrons.

Measurements of electrical transport numbers at 1000°K show the electrical conductivity of LiNbO₃ to be ionic at one atmosphere of oxygen and electronic at low oxygen partial pressures.

Thermoelectric measurements indicate that LiNbO₃ at low oxygen partial pressures is n-type and that the concentration of electrons at 1000°K and in an atmosphere of 50% C0/50% CO₂a is 4 × 10¹⁷cm³ with a mobility of 1.7 cm²V sec.

The diffusion of oxygen in LiNbO₃ was determined as a function of temperature at an oxygen partial pressure of 70 Torr. by measuring O¹⁸/O¹⁶ isotope exchange with the gas phase as a function of time. The diffusion data may be represented by D = 3.03 × 10⁻⁶ exp (−29.4 kcal mole⁻¹/RT)cm²sec. Consideration of the Nernst-Einstein relation for oxygen and the variation in conductivity with Li₂O activity indicate that the ionic conduction is caused by transport of lithium ions.     

Ln1−xSrxCoO3(Ln = Sm, Dy) for the electrode of solid oxide fuel cells

The perovskite-type oxides were synthesized in the series of Ln_1−xSr_xCoO₃(Ln = Sm, Dy). The formation of solid solutions in Dy_{1 − x}Sr_xCoO₃ was limited, compared with that in Sm_{1 − x}Sr_xCoO₃. The electrical conductivities of the sintered samples were measured as a function of x in the temperature range 30 to 1000 °C. The highest conductivity of around 500 S/cm at 1000 °C was found in Sm_0.7Sr_0.3CoO₃. The reactivity of all the samples with YSZ was examined at 800–1000 °C for 96 h. The Sr-doped perovskite oxides were more reactive with YSZ and produced SrZrO₃ at 900 °C after 96 h. However, no reaction product between SmCoO₃ and YSZ was observed at 1000 °C for 96 h. The cathodic polarization of the oxide electrodes, sputtered on yttria stabilized zirconia (YSZ), was studied at 800–1000 °C in air. SmCoO₃ shows no degradation of the electrode performance at higher temperatures. The thermal expansion measurements on the sintered samples were carried out from room temperature to 1000 °C. Large thermal expansion coefficients were found in these samples.     

Effect of branching in base polymer on ionic conductivity in hyperbranched polymer electrolytes

Novel hyperbranched polymer, poly[bis(diethylene glycol)benzoate] capped with a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group (poly-Bz1a), was prepared, and its polymer electrolyte with LiN(CF₃SO₂)₂, poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte, was all evaluated in thermal properties, ionic conductivity, and electrochemical stability window. The poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte exhibited higher ionic conductivity compared with a polymer electrolyte based on poly[bis(diethylene glycol)benzoate] capped with an acetyl group (poly-Ac1a), and the ionic conductivity of poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte was to be 7×10⁻⁴ S cm⁻¹ at 80 °C and 1×10⁻⁶ S cm⁻¹ at 30 °C, respectively. The existence of a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group as a branching unit present at ends in the base polymer improved significantly ionic conductivity of the hyperbranched polymer electrolytes. The polymer electrolyte exhibited the electrochemical stability window of 4.2 V at 70 °C and was stable until 300 °C.     

Surface morphology and electrical properties of Bi---Sr---Ca---Cu---O thin films deposited by reactive sputtering from multiple targets

Smooth, superconducting films of Bi₂Sr₂CaCu₂O_8+° have been prepared by reactive sputtering from elemental targets in the presence of ozone. The influence of substrate temperature, deposition rate, and ozone pressure on the resulting films are discussed. Films deposited on SrTiO₃ substrates are c-axis oriented and featureless for substrate temperatures below 710°C. Above this temperature, small inclusions of CuO appear. Films on MgO exhibit mixed a-axis and c-axis orientation below about 710°C, and inclusions of CuO above this temperature. The temperature at which this transition occurs increases with increasing deposition rate. T_c increases and then decreases sharply with decreasing oxygen content. The oxygen partial pressure corresponding to the maximum T_c of 77 K is well above the thermodynamic stability limit for Bi₂Sr₂CaCu₂O_8+°, suggesting that an optimum carrier concentration has been achieved for these films.     

Ionic and electronic conductivity in lead–zirconate–titanate (PZT)

Accurate impedance measurements on differently sized samples of lead–zirconate–titanate (PbZr_0.53Ti_0.47O₃, PZT) have been analyzed with a CNLS procedure, resulting in the separation of the ionic and electronic conductivities over a temperature range from 150 to 630 °C. At 603 °C the electronic conductivity shows approximately a (P_O2)^1/4 dependence, while the ionic conductivity remains constant. Below the Curie transition temperature the oxygen non-stoichiometry becomes frozen-in and the conductivities are strongly dependent on the sample history with respect to temperature sequence and ambient P_O2. A tentative interpretation assumes defect association, i.e. formation of neutral [V_Pb–V_O^··]^× complexes, and electron-hole transfer between lead sites and lead vacancies to control the oxygen ion conductivity in the tetragonal phase.

Annealing PZT-based devices at about 600 °C under low oxygen pressure (1 Pa oxygen) effectively decreases the low temperature electronic conductivity by a factor of 100 and the ionic conductivity by a factor of 10–15 with respect to normal air processing.     

In situ surface analytical investigation of the thermal oxidation of Ti–Al intermetallics up to 1000 °C

The low pressure high temperature oxidation behavior of Ti–Al intermetallics are of interest to power technology aiming to synthesize this material by sintering of powders. This paper presents in situ surface analytical studies of the composition of a two-phase TiAl/Ti₃Al bulk microcrystalline system after oxidizing the same (sputtered) reference surface for 30 min at various oxygen partial pressures and temperatures varying between room temperature (RT) and 1000 °C. The results show that oxidation already begins at very low (<5×10⁻¹⁰ mbar) oxygen pressure, producing Al₂O₃ and the lower oxidation states of Ti. As the oxygen pressure and oxidation temperature increases, TiO₂ becomes dominant up to 900 °C. No phase transition of Al₂O₃ has been observed in this range. No sign of a blocking behavior of the oxide layer is seen. At 1000 °C a new oxide phase, Al₂TiO₅ appears, changing the composition and behavior of the surface drastically. The observed results can be explained by qualitative thermodynamic arguments. The thickness and composition of the oxide overlayer is, however, primarily determined by the oxygen supply.     

Sensors measuring oxygen activity in melts: Development of impedance method for“in-situ” diagnostics and control electrolyte/liquid-metal electrode interface

An impedance method for periodic“in-situ” diagnostics of the solid electrolyte/liquid-metal electrode interface during the lifespan of yttria-stabilized zirconia (YSZ)-based sensors measuring oxygen partial pressure in melts was developed. It was found that the impact of polarization effects on YSZ, stipulated by corrosive measuring environments (molten alkaline metals), is increasing with increase of the working temperature, which may lead to the appearance blocking reaction layers at the electrolyte/liquid-metal electrode interface. The proposed impedance method allows obtaining necessary information about the electrolyte/liquid-metal electrode interface and about the character and the level of polarization of the liquid-metal electrode.     

Determination of different oxygen transport mechanisms and measurement of the oxygen ion conductivity of Y1Ba2Cu3O7−x

By undertaking AC electrochemical impedance experiments on yttria stabilised zirconia electrolytes with polished Y₁Ba₂Cu₃O_7−x electrodes, the activation energy for oxygen ion transport within the bulk of Y₁Ba₂Cu₃O_7−x, in air, over the temperature range 823 K–1043 K, was determined to be 1.50 ± 0.05 eV. At 1000 K the oxygen ionic conductivity was calculated to be around one order of magnitude lower than that in yttria stabilised zirconia. Typical calculated values were σ=5×10⁻⁵ (ω cm)⁻¹ and 6×10⁻³ (ω cm)⁻¹ at the respective temperatures 823 K and 1043 K. By employing a similar cell but with Y₁Ba₂Cu₃O_7−x paste electrodes, oxygen transfer between the Y₁Ba₂Cu₃O_7−x and the electrolyte was found to occur via a surface diffusional processes. Over the temperature range 873 K–1098 K, in air, the activation energy for in-diffusion at the surface was found to be 1.4±0.1 eV and that for out-diffusion at the surface to be 1.76±0.05 eV.     

Crystallization kinetics in ferroelectric thin films: Viability of atomic force microscopy

The pyrochlore to perovskite phase transformation was studied in lead zirconate titanate (PZT) thin films. The films were fabricated on platinum electrodes and annealed by rapid thermal processing (RTP). The phases which formed and their location in the film were analyzed using glancing angle XRD and depth profiling was demonstrated. Grain size and structure, nucleation sites and surface morphology were determined with transmission electron microscop (TEM) and atomic force microscopy (AFM). The role of AFM in this type of transformation study was assessed.

The PZT films crystallized with a (100) orientation which was preferentially nucleated at the platinum/film interface. RTP at 650°C for 15 s was sufficient to complete the transformation. However, columnar grain growth and improvements in the ferroelectric properties were obtained with increased RTP time. A PZT film with RTP at 650°C for 1 min possessed a remanent polarization of 25 μC/cm² and a dielectric constant of ε = 650.     

Study of adsorption of oxygen on β-Al2O3 + Au and β-Al2O3 + Pt: Work function measurements—proposition of a model

To improve the understanding of the electrochemical effects observed on an original potentiometric gas sensor, interactions of oxygen with the device were investigated. This gas sensor is made of a solid electrolyte (treated Na-β-alumina) associated with two metallic electrodes (gold and platinum) located in the same gas mixture. Adsorption of charged oxygen species, considered responsible for the electrical response developed by the sensor, was investigated by work function measurements. Results showed that charged oxygen species only form on partially gold or platinum covered solid electrolyte. Comparison of these results with those obtained in a previous calorimetric study of interactions between oxygen and the same materials suggests the existence of at least two different oxygen species adsorbed on the surface of the sensitive element. The first one, located on the solid electrolyte surface, is neutral and characterized by an endothermal reaction of formation. The second one is charged and probably produced at the gas/solid electrolyte/metallic electrode interface. A mechanism based on the concept of “three phase boundary” and similar to the “reverse spillover” phenomenon is proposed to account for the adsorption of these oxygen species.