Activation,microstructure, and polarization of solid oxide fuel cell cathodes

Activation effect can be defined as the enhancement of the electrochemical performance or activity of the solid oxide fuel cell cathodes such as Sr-doped LaMnO₃ (LSM) with the polarization/current passage treatment under fuel cell operation conditions. In this paper, the activation effect of the cathodic polarization/current passage on the O₂ reduction reaction of the LSM-based cathodes is reviewed. In addition to the activation effect, cathodic polarization/current passage also has a significant effect on the microstructure of the LSM electrodes and the morphology between the LSM electrode and Y₂O₃-ZrO₂ electrolyte interface. A mechanism involving the incorporation of SrO species into the LSM lattice and the formation of oxygen vacancies is proposed for the activation effect of the polarization.     

Electrochemical dissolution of Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> in acid solutions

The present study deals with the electrochemical reductive dissolution of Mn₃O₄, which was added to carbon-paste electroactive electrodes (CPEEs) in acid solutions. It was found that in the experimental conditions the thermodynamically stable form of manganese was . Kinetic features of the electrochemical reductive dissolution of Mn₃O₄, which was realized under potential cycling conditions (+1.0 V→−0.7 V→+1.0 V), were determined by the electrode polarization direction. It was shown that the cathodic reduction of Mn₃O₄ was accomplished in three stages. Manganese was dissolved in the supporting solution only at the third stage. The first two stages involved solid-phase reactions. The anodic cycling stage included an active dissolution of Mn₃O₄ and the lower manganese oxide (MnO) accumulated on the electrode surface during the cathodic reduction.     

Options for adjustment of microstructure and conductivity of cathodic substrates of La(Sr)MnO<Subscript>3</Subscript>

The electrodes of solid-oxide fuel cells (SOFCs) must be characterized by high conductivity to decrease ohmic losses and sufficient porosity to provide high gas diffusion rate. In the cases, when the SOFC electrodes are substrates, they must be synthesized at the temperature above the temperature of formation of their solid-electrolyte coating. Herewith, manufacturing of supporting electrodes with the required micro-structure is rather complicated. The present paper studies the effect of the method of manufacturing of the initial La_0.6Sr_0.4MnO₃ (LSM) powders, their degree of dispersion, introduction of sintering additives and pore agents on their microstructure, conductivity, and possibility of adjusting the temperature of SOFC cathodic substrate formation at which the required characteristics are reached. It is shown that sintering of cathodic substrates to the relative density of 65–70% can be carried out at the temperatures from 1050 to 1350–1400°C, which would allow obtaining electrolyte films of powders with different sintering ability on such substrates. The average pore size in cathodic substrates can be varied in the range of 0.4 to 2.5 μm by using the initial LSM powder with different dispersion degree and by employing graphite as a pore agent. At 900°C, conductivity of cathodic substrates of LSM grows at an increase in their relative density from 50% to 70% approximately from 50 to 100 S/cm and weakly depends on the dispersion degree of the initial powders.     

Phase-pure nanocrystalline Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> for a lithium-ion battery

Phase-pure nanocrystalline Li₄Ti₅O₁₂ with BET surface areas between 183 and 196 m²/g was prepared via an improved synthetic protocol from lithium ethoxide and titanium(IV) butoxide. The phase purity was proved by X-ray powder diffraction, Raman spectroscopy and cyclic voltammetry. Thin-film electrodes were prepared from two nanocrystalline samples of Li₄Ti₅O₁₂ and one microcrystalline commercial sample. Li-insertion behavior of these electrodes was related to the particle size.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic     

Photoluminescence dependence on imposing bias for ZnGa2O4 and ZnGa2O4 activated with Mn or Cr n-type semiconductor electrodes

Photoluminescence (PL) dependence was investigated by imposing cathodic and anodic bias for ZnGa₂O₄, ZnGa₂O₄:Mn and ZnGa₂O₄:Cr n-type semiconductor electrodes. Under the cathodic bias PL intensity was weak at about 1/3 times compared with imposing no bias, while under the anodic bias the intensity was strong at about 2 times maximally by using the ZnGa₂O₄:Mn and ZnGa₂O₄:Cr electrodes although no change about the intensity was observed by using the ZnGa₂O₄ electrode. These results suggest that the emission attributed to recombination between electrons and holes is decreased by flow of cathodic current under the cathodic bias while the emission is increased to decrease at non-radiative transition rates under the anodic bias when the energy relaxation occurs.     

Electrochemical behavior of composite cathodes in contact with solid electrolyte La<Subscript>10</Subscript>Ge<Subscript>6</Subscript>O<Subscript>27</Subscript>

The cathodic overvoltage of composite cathodes 50 wt % La_0.8Sr_0.2MnO₃ (LSM) + 50 wt % La₁₀Ge₆O₂₇ (LGO) (further on, LSM-LGO), LSM-SSZ (Zr_0.835Sc_0.165O_2?δ), Ag-Pd-LGO, and Ag-Pd-SSZ in contact with the LGO electrolyte is measured. The temperature dependences of the polarization conductivity and the working-current densities of the same composite cathodes are investigated. The study is performed at 700–900°C. A comparison with the SSZ electrolyte is conducted. The chemical interaction in the LSM-LGO composition is studied. It is demonstrated that the interaction of lanthanum-strontium manganite with lanthanum germanate occurs with the dissolution of the initial phases in one another and with the formation of fresh phases at elevated temperatures. Coefficients of linear thermal expansion of the LGO and SSZ electrolytes and the LSM, LSM-LGO, and LSM-SSZ electrode materials are compared at 40–900°C. Most of the studied electrodes in contact with the LGO electrolyte demonstrate thermomechanical stability and high electrochemical activity.     

Electrochemical study of Meldola's blue,methylene blue and toluidine blue immobilized on a SiO<Subscript>2</Subscript>/Sb<Subscript>2</Subscript>O3 binary oxide matrix obtained by the sol-gel processing method

SiO₂/Sb₂O₃ (SiSb), having a specific surface area, S _BET, of 788 m² g⁻¹, an average pore diameter of 1.9 nm and 4.7 wt% of Sb, was prepared by the sol-gel processing method. Meldola's blue (MeB), methylene blue (MB) and toluidine blue (TB) were immobilized on SiSb by an ion exchange reaction. The amounts of the dyes bonded to the substrate surface were 12.49, 14.26 and 22.78 μmol g⁻¹ for MeB, MB and TB, respectively. These materials were used to modify carbon paste electrodes. The midpoint potentials (E _m) of the immobilized dyes were −0.059, −0.17 and −0.18 V vs. SCE for SiSb/MeB, SiSb/MB and SiSb/TB modified carbon paste electrodes, respectively. A solution pH between 3 and 7 practically did not affect the midpoint potential of the immobilized dyes. The electrodes presented reproducible responses and were chemically stable under various oxidation-reduction cycles. Among the immobilized dyes, MeB was the most efficient to mediate the electron transfer for NADH oxidation in aqueous solution at pH 7. In this case, amperometric detection of NADH at an applied potential of 0 mV vs. SCE gives linear responses over the concentration range of 0.1–0.6 mmol L⁻¹, with a detection limit of 7 μmol L⁻¹.     

Multicycle chronoamperometry at rotating ring-disc electrode as a method of current separation into partial currents of silver ionization,Ag<Subscript>2</Subscript>O formation and its chemical dissolution in alkaline medium

A method of multicycle chronoamperometry at rotating ring-disc electrode is suggested for experimental separation of the disc polarization current into its components that correspond to the substrate metal ionization, an oxide formation, and the oxide chemical dissolution. The method was validated by the example of the Ag|Ag₂O|OH^?(H₂O) system. At moderate anodic potentials of Ag-disc (0.48–0.51 V), silver active dissolution from open areas of its surface and through film’s pores dominates; the phase-forming current, hence, the current efficiency of this process drops down rapidly. At the potentials of the maximum at voltammograms (0.52–0.53 V), when the silver active dissolution current is suppressed, the phase-forming currents dominate; they exceed the oxide chemical dissolution rate significantly. The Ag₂O film thickness increases rapidly, the current efficiency of the oxide formation process approaches 100% during the entire disc polarization period. The Ag(I)-oxide chemical dissolution rate constant practically does not depend on the anodic phase-formation potential; however, it somewhat varies depending on the oxide film thickness, thus reflecting changes in the film structure and, possibly, chemical composition (from AgOH to Ag₂O).     

Untersuchungen über die selektive Katalyse der Elektrodenreaktionen im Aasserstoff-Brom-Speichersystem

Summary Considerable rates are obtained for the hydrogen electrode reactions using WC-gas-diffusion electrodes which are not impaired by active Br₂ in the solution. Tafel-lines withb-values of appr. 30 mV for both, anodic and cathodic current density potential curves, can be attributed to the Tafel-reaction as the rate controlling step. High reversibility (very low polarization) of the Br₂/2 Br^– redox couple is observed at activated carbon plastic composite material. The presence of H₂ does not influence the electrode behavior. The use of both substrates in the H₂/Br₂ storage system provides definite advantages of the conceptual design and operation due to their electrocatalytic selectivity.

     

Structure and electrical properties of Pb(Zr<Subscript>0.25</Subscript>Ti<Subscript>0.75</Subscript>)O<Subscript>3</Subscript> thin films on LaNiO<Subscript>3</Subscript>—Coated thermally oxidized Si substrates

Pb(Zr_0.25Ti_0.75)O₃ (PZT25) thin films were prepared on LaNiO₃-coated thermally oxidized silicon substrates by chemical solution deposition method, where LaNiO₃ electrodes were also prepared by a chemical solution deposition technique. The dielectric constant and dielectric loss of the PZT25 thin films were 570 and 0.057, respectively. The remanent polarization and coercive field were 20.11 μC/cm² and 60.7 kV/cm, respectively. The PZT25 thin films on LaNiO₃-coated thermally oxidized silicon substrates showed improved fatigue characteristics compared with their counterparts on plantium-coated silicon substrates.     

Effect of Ta on the corrosion performance of Mo<Subscript>3</Subscript>Si intermetallic in NaCl solutions

The effect of Ta contents on the corrosion performance of Mo₃Si intermetallic in 0.5 M NaCl has been evaluated. Materials included Mo₃Si plus 5, 17, 53, 60, and 74 at% Ta. Techniques included potentiodynamic polarization curves and linear polarization resistance curves. Except for 74 at% Ta, additions of Ta induced a passive region, decreasing the anodic current density, the free corrosion potential, the pitting potential, and the corrosion current density.     

Effects of particle size on the electrochemical performances of a layered double hydroxide, [Ni<Subscript>4</Subscript>Al(OH)<Subscript>10</Subscript>]NO<Subscript>3</Subscript>

In this paper, the electrochemical performances of a layered double hydroxide, [Ni₄Al(OH)₁₀]NO₃, of different particle sizes are studied. The results show that the particle size of the sample has evident effects on its discharge capacity at high current density, although a larger capacity may be observed for the bigger particles when they are discharged at lower current densities, e.g. 0.2 A g⁻¹. However, the capacity decreases more quickly than that of the sample in smaller particle size when the current density increases. For example, the discharge capacity of the smallest particle remains as high as 180 mAh·g⁻¹ even at very high current density, e.g. 4.0 A g⁻¹. The results also show that long time soaked electrodes in 7 mol l⁻¹ KOH have improved performance, especially for the hydrothermal samples. It also seems that there is an optimal size for materials, which can maintain their performance for longer time.     

Polarization Characteristics of Composite Electrodes in Electrochemical Cells with Solid Electrolytes Based on CeO<Subscript>2</Subscript> and LaGaO<Subscript>3</Subscript>

For two types of electrochemical cells with oxygen-conducting solid electrolytes based on lanthanum gallate (LSGM) and cerium oxide (SDC) studied are the temperature dependences of the polarization conductivity of air electrodes prepared from lanthanum-strontium manganite (LSM) and composites LSM-LSGM, LSM-SDC, and LSM-SSZ (SSZ is zirconium dioxide-based electrolyte). Effect of praseodymium oxide, added into these electrodes as a modifier, on their electrochemical properties is examined. Electrochemical systems with an LSM/LSGM interface exhibit low electrochemical activity toward the oxygen reaction, because during the formation of electrodes, LSM interacts with LSGM to form a poorly conducting product.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 602–606.Original Russian Text Copyright © 2005 by Yaroslavtsev, Kuzin, Bronin, Bogdanovich.     

Use of anodized tubular TiO<Subscript>2</Subscript> photoanodes in light-sensitized enzymatic hydrogen production

In this study, an anodized tubular TiO₂ electrode (ATTE) on titanium foil was prepared and used both as a photoanode and a cathode in an enzymatic photoelectrochemical system to split water into oxygen and hydrogen. The effect of applied voltage when anodized, thickness of the foil, electrolytes, annealing temperature, and cathodes was investigated (optimum conditions: 20 V of applied voltage in 0.5 vol.% of hydrofluoric acid, 0.25-mm foil thickness, and 450–650°C annealing temperature). The samples with higher activities had similar X-ray diffraction (XRD) patterns, clearly indicating that the samples showing the highest evolution rate were composed of both anatase and rutile, while those showing a lower evolution rate were made of either anatase or rutile. The ATTE successfully replaced the Pt mesh cathode and the immobilization of the enzyme enhanced the H₂ evolution by 50% (from ca. 66 to 99 μmol/(h × cm²)). Moreover, the use of KOH instead of Tris–HCl buffer in a cathodic compartment further increased the H₂ evolution to 115 μmol/(h × cm²).     

Deposition of chromium species on Sr-doped LaMnO3 cathodes in solid oxide fuel cells

The system of chromia-forming alloy/Sr-doped LaMnO₃ (LSM) electrode/3 mol%Y₂O₃–ZrO₂ (TZ3Y) electrolyte has been investigated at 900°C in air under cathodic polarization conditions. Deposition of chromium species was found to occur preferentially at the TZ3Y electrolyte surface, forming a deposit ring around the edge of the LSM electrode coating. The width of the ring was about 60 μm for an LSM electrode polarized for about 50 h. Overpotential (η) increases with polarization time. In contrast to η, electrode interface resistance (R_E) measured under open circuit conditions decreases initially after passing the current and remains almost constant with polarization. The results indicate that the deposition process of chromium species may not be dominated by electrochemical reduction processes in competition with O₂ reduction at an early stage of polarization.     

Electrochemical properties of perovskite and A<Subscript>2</Subscript>MO<Subscript>4</Subscript>-type oxides used as cathodes in protonic ceramic half cells

Three selected materials have been prepared and shaped as cathode of half cells using the proton-conducting electrolyte BaCe_0.9Y_0.1O_3 − δ (BCY10): two perovskite compounds, Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ (BSCF) and La_0.6Sr_0.4Fe_0.8Co_0.2O_3 − δ (LSFC), and the praseodymium nickelate Pr₂NiO_4 + δ (PRN) having the K₂NiF₄-type structure. The electrochemical properties of these compounds have been studied under zero current conditions (two-electrode cell) and under polarization (three-electrode cell). Their measured area-specific resistances were about 1–2 Ω cm² at 600 °C. Under direct current polarization, it appears that the three compounds show almost similar values of current densities at 625 °C; however, at lower temperatures, BSCF appears to be the most efficient cathode material.     

Photoelectrochemical processes at interfaces of nanostructured TiO<Subscript>2</Subscript>/carbon black composites studied by scanning photoelectrochemical microscopy

The local photoelectrochemical response of TiO₂/carbon black photocatalysts was studied by means of scanning photoelectrochemical microscopy performed under UV illumination and external polarization. Catalysts obtained by sol-gel techniques showed a uniform response that improved under anodic polarization, in contrast to the non-uniform response of mixtures that show enhancement under cathodic polarization. To explain the differences in photoelectrochemical activity, we performed electrochemical and capacitive studies under dark condition, finding a larger positive shift in the rest potential of sol-gel composites plus evidence of Fermi-level pinning. We propose the last is related to the presence of carbon states with a strong acceptor character formed during the sol-gel synthesis. An energy band diagram of the composites were sketched based on the data obtained.     

The electrochemical properties of Ni<Subscript>3</Subscript>C carbide

The electrochemical properties of Ni₃C was studied. In acidic sulfate solutions, the carbide is characterized by high overpotential of its oxidation as compared with nickel. In the case of carbide oxidation, the anodic reaction orders with respect to anions are low, indicating a weak dependence of the rate of the anodic process on the solution composition. Significant differences in the kinetics of the anodic processes indicate different mechanisms of the oxidation of nickel and its carbide. The rate and kinetic parameters of the hydrogen evolution reaction are comparable on Ni and Ni₃C. In neutral and alkaline solutions, the metal and carbide samples were similar in their electrochemical characteristics. The anodically grown oxide film is thinner on nickel carbide than on nickel metal, and the oxide formed on the carbide is more readily reduced under cathodic polarization. This film is also more resistant to the pitting attack than the oxide film on nickel metal.     

Electrocatalytic properties of La0.9Sr0.1MnO3-based electrodes for oxygen reduction

Electrochemical reduction of oxygen at the interface between a La_0.9Sr_0.1MnO₃ (LSM)-based electrode and an electrolyte, either yttria-stabilized-zirconia (YSZ) or La_0.8Sr_0.2Ga_0.9Mg_0.1O₃ (LSGM), has been investigated using DC polarization, impedance spectroscopy, and potential step methods at temperatures from 1053 to 1173 K. Results show that the mechanism of oxygen reduction at an LSM/electrolyte interface changes with the type of electrolyte. At an LSM/YSZ interface, the apparent cathodic charge transfer coefficient is about 1 at high temperatures, implying that the rate-determining step (r.d.s.) is the diffusion of partially reduced oxygen species, while at an LSM/LSGM interface the cathodic charge transfer coefficient is about 0.5, implying that the r.d.s. is the donation of electrons to atomic oxygen. The relaxation behavior of the LSM/electrolyte interfaces displays an even more dramatic dependence on the type of electrolyte. Under cathodic polarization, the current passing through an LSM/YSZ interface increases with time whereas that through an LSM/LSGM interface decreases with time, further confirming that it is the triple phase boundaries (TPBs), rather than the surface of the LSM or the LSM/gas interface, that dominate the electrode kinetics when LSM is used as an electrode. Electronic Publication     

The effects of ultrasound on the direct electrosynthesis of solid K<Subscript>2</Subscript>FeO<Subscript>4</Subscript> and the anodic behaviors of Fe in 14 M KOH solution

The effects of ultrasound on the direct electrosynthesis of solid K₂FeO₄ and the anodic behaviors of pure iron were investigated, and the physical properties of samples were characterized by means of X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The experimental results showed that the existence of ultrasound can decrease the formation potential of ferrate(VI) and the passivation extent of iron anode, and this leads to higher current efficiency for the direct electrosynthesis of solid ferrate(VI) at 65 °C in 14 M KOH solution. It was also found that, in the experimental scope suitable ultrasonic power (14.6 W), shorter electrolysis duration and smaller electrolysis current can improve the apparent current efficiency of the electrosynthesis, and the largest current efficiency under suitable experimental conditions reached 77.2%.