Study of the oxygen electrode reaction using mixed conducting oxide surface layers. Part II: Small signal analysis

The oxygen gas electrode has been studied for a number of mixed conducting oxide surface layers on top of Gd₂Zr₂O₇ (TGZO) solid electrolytes. In part II of this paper we present the results of frequency dispersion measurements for the electrode reaction, supplying additional information to the results of current-overvoltage experiments presented in part I. For both kinds of experiments the same trends were observed for the electrode polarization. Best results are obtained for a surface layer of TGZO, while p-type mixed conducting oxides give less decreased values of the electrode polarization. High electrode capacitances were found in the case of mixed conducting surface layers (about 700 F/m²). The electrode reactions follow a Butler-Volmer type of equation. Most probably a diffusion process is rate controlling the overall charge transfer process.     

Microstructure and electrochemical properties of porous La2NiO4+δ electrodes spin-coated on Ce0.8Sm0.2O1.9 electrolyte

Porous La₂NiO_4+?? electrodes were prepared from superfine starting powder on dense substrates of Ce_0.8Sm_0.2O_1.9 electrolyte by a spin coating technique. The microstructure and electrochemical properties of the electrodes were investigated within the sintering temperature range of 1,000?C1,100?°C. An obvious effect of sintering temperature on the microstructure and electrochemical properties was detected. The variation of the electrochemical properties with sintering temperature was explained in relation to the microstructural evolution of the porous electrodes. It was detected that the electrode processes greatly depended on the microstructure of the electrodes. The polarization of surface oxygen exchange process was found to be the major contribution to the total electrode polarization. The electrode sintered at 1,050?°C showed the optimum electrocatalytic activity among the investigated electrodes. At 800?°C, the electrode exhibited a polarization resistance of 0.42????cm², an overpotential of 48?mV at a current density of 200?mA?cm^?2 and an exchange current density of 121?mA?cm^?2.     

Electrochemical synthesis of Ag nanoparticles supported on glassy carbon electrode by means of p-isopropyl calix[6]arene matrix and its application for electrocatalytic reduction of H2O2

The silver nanoparticles were prepared on the glassy carbon (GC) electrode, modified with p-iso propyl calix[6]arene, by preconcentration of silver ions in open circuit potential and followed by electrochemical reduction of silver ions. The stepwise fabrication process of Ag nanoparticles was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. The prepared Ag nanoparticles were deposited with an average size of 70 nm and a homogeneous distribution on the surface of electrode. The observed results indicated that the presence of calixarene layer on the electrode surface can control the particle size and prevent the agglomeratione and electrochemical deposition is a promising technique for preparation of nanoparticles due to its easy-to-use procedure and low cost of implementation. Cyclic voltammetry experiments showed that Ag nanoparticles had a good catalytic ability for the reduction of hydrogen peroxide (H₂O₂). The effects of p-isopropyl calix[6]arene concentration, applied potential for reduction of Ag⁺, number of calixarene layers and pH value on the electrocatalytic ability of Ag nanoparticles were investigated. The present modified electrode exhibited a linear range from 5.0 × 10⁻⁵ to 6.5 × 10⁻³ M and a detection limit 2.7 × 10⁻⁵ M of H₂O₂ (S/N = 3) using amperometric method.     

Impedance study of SrTi1−xFexO3−δ (x = 0.05 to 0.80) mixed ionic-electronic conducting model cathode

SrTi_1?xFe_xO_3?δ (STF) model cathodes, with compositions of x = 0.05 to 0.80 were deposited onto single crystal yttria stabilized zirconia by pulsed layer deposition as dense films with well defined area and thickness and studied by electrochemical impedance spectroscopy as a function of electrode geometry, temperature and pO₂. The STF cathode was observed to exhibit typical mixed ionic-electronic behavior with the electrode reaction occurring over the full electrode surface area rather than being limited to the triple phase boundary. The electrode impedance was observed to be independent of electrode thickness and to the introduction of CGO interlayers and inversely proportional to the square of the electrode diameter, pointing to surface exchange limited kinetics. Values for the surface exchange coefficient, k, were calculated and found to be comparable in magnitude to those exhibited by other popular mixed ionic-electronic conductors such as (La,Sr)(Co,Fe)O₃, thereby, confirming the suitability of STF as a model mixed conducting cathode material. The surface exchange coefficient, k, was also found to be insensitive to orders of magnitude change in both bulk electronic and ionic conductivities.     

Optimized annealing conditions to enhance stability of polarization in sputtered HfZrOx layers for non-volatile memory applications

In this paper, we report stable polarization switching in metal-HfZrO_x (HZO)-metal capacitors when pulses are repeatedly applied from the initial state. By examining various process parameters including annealing method, annealing temperature, and annealing time, we investigated the optimal conditions for realizing ferroelectricity in HZO layers deposited by sputtering systems. More specifically, we examined how polarization behaviors evolved as a function of annealing temperatures. Our results showed that annealing HZO capped by a top electrode, when annealing temperature was higher than 850 °C, drives the transformation to large quantities of orthorhombic phases, and enables constant remnant polarization without the fluctuations caused by wake-up and fatigue. We continued to observe stable polarization up to 10⁸ cycles with a pulse width of 5 μs.     

Template synthesis of M/M2S (M = Ag,Cu) hetero-nanowires by electrochemical technique

Metal chalcogenide-based mixed ionic–electronic conductors such as Ag₂S and Cu₂S can be specifically architected for application in nanoelectronic devices. We present a template-confined synthesis of metal chalcogenide (e.g., Ag₂S, Cu₂S) nanowires for mixed conductor-based nanoelectronics. First, the metal nanowire array was electroplated into pores of a porous alumina membrane. Anodic polarization was then used to transform the metal into the metal sulfide in aqueous hydrosulfide (HS⁻) solutions. The as-synthesized mixed conductors' hetero-nanowire array was characterized by X-ray diffraction and electron microscopy. Electronic transport measurements show non-linear and reproducible electrical switching characteristics. The high and low resistance states can be reversibly changed by altering the polarity of the applied voltage between the bottom and top electrodes. The electrical-switching behavior is attributed to electric-field-induced accumulation and dissolution of metallic conducting pathways inside the mixed conductors' nanowires.     

The effect of different concentrations of Na2SnO3 on the electrochemical behaviors of the Mg-8Li electrode

In this research, the effect of the different concentrations of NaSnO₃ as the electrolyte additive in 0.7 mol L^?1 NaCl solution on the electrochemical performances of the magnesium-8lithium (Mg-8Li) electrode are investigated by methods of potentiodynamic polarization, potentiostatic current-time, electrochemical impedance technique, and scanning electron microscopy (SEM). The corrosion resistance of the Mg-8Li electrode is improved when Na₂SnO₃ is added into the electrolyte solution. The potentiostatic current-time curves show that the electrochemical behaviors of the Mg-8Li electrode in the electrolyte solution containing 0.20 mmol L^?1 Na₂SnO₃ is the best. The electrochemical impedance spectroscopy results indicate that the polarization resistance of the Mg-8Li electrode decreases in the following order with the concentrations of Na₂SnO₃: 0.05 mmol L^?1?>?0.00 mmol L^?1?>?0.30 mmol L^?1?>?0.10 mmol L^?1?>?0.20 mmol L^?1. The scanning electron microscopy studies indicate that the electrolyte additive prevents the formation of the dense oxide film on the alloy surface and facilitates the peeling off of the oxidation products.     

Measurements of chemical diffusion coefficients of mixed conducting solids using point electrodes-investigations on Cu2S

The use of point electrodes for measuring chemical diffusion coefficients of mixed conducting solids with prevailing electronic conductivity is described and applied to low temperature Cu₂S. The electrochemical cell consist of the sequence of phases Pt/mixed conductor/Pt-point electrode. Applying small dc voltages to the cell leads to a steady state composition gradient within characteristic times that depend on the radius of the point electrode and on the chemical diffusion coefficient. The composition change after changing electrical voltage or current is followed by measuring the ohmic resistance change as a function of time, using ac nethods in the case of switching off. The method requires that the electronic conductivity depends on the usually small, but variable deviations of the composition of the solids from a definite stoichiometric composition. The measurements on the low temperature phase of Cu₂S give chemical diffusion coefficients ranging between 6.10^-6 cm²/s and 1.10^-7 cm²/s at 60°C.     

Comparison of the effect of PLT and PZT buffer layers on PZT thin films for ferroelectric materials applications

In order to study the effect of different buffer layers on the Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films, 10-nm thick (Pb_0.72La_0.28)Ti_0.93O₃ (PLT) and Pb(Zr_0.52Ti_0.48)O₃ buffer layers have been deposited on the Pt(1 1 1)/Ti/SiO₂/Si substrates by pulsed laser deposition, respectively. The top buffer layers were also deposited on PZT thin films with the same thickness of the seed layers in order to enhance the fatigue characteristics of PZT thin films. We compared the results of dielectric constant, hysteresis loops and fatigue resistance characteristics. It was found that the dielectric properties of PZT thin films with PLT buffer layers were improved by comparing with PZT thin films with PZT buffer layers. The polarization characteristics of PZT thin films with PLT buffer layers were observed to be superior to those of PZT thin films using PZT buffer layers. The remanent polarization of PZT thin films showed 36.3 μC/cm² and 2.6 μC/cm² each in the case of use PLT and PZT buffer layers. For the switching polarization endurance analysis, PZT thin films with PLT buffer layers showed more excellent result than that of PZT thin films with PZT buffer layers.     

An electrochemical and structural investigation of porous composite anode materials for LIB

A porous composite anode for lithium ion battery (LIB) was investigated. The composite anode was prepared by electrodepositing Sn?CSb alloy on a template-like electrode and then annealing it in the atmosphere of N₂, whereas the porous template-like electrode was obtained by forming a sponge-like porous membrane on a copper foil via a mixed phase inversion process, followed by pre-plating Cu through membrane pores in it. SEM and XRD results showed that composite structure of the anode consisted of electrodeposited Sn?CSb alloy dispersed in a PAN-pyrolyzed conjugated conducting polymer gridding, which was tightly connected with the Cu foil through transition alloy layer formed by heat treatment. Due to its relatively reasonable microcosmic structure, the composite anode presented better cycling performance and specific capacity retention during charging and discharging at diverse rates. When cycled between 0 and 2.0?V (vs Li/Li⁺) at 0.5?C rate, the reversible charge/discharge capacity of the composite material remained 415 and 414.8?mAh?g^?1, respectively, after 30 cycles, corresponding to 82.9% of the capacity retention. When charging and discharging at 2?C rate, the composite material electrode showed 71.7% capacity retention at the 30th cycle.     

Direct growth of single crystalline ReO3 nanorods on a tungsten (W) microwire for enhanced electron-transfer reaction kinetics

We report the direct growth of highly single crystalline rhenium trioxide (ReO₃) nanorods on a tungsten (W) microwire electrode via the physical vapor transport process without any catalyst. In our growth mode, ReO₃ nanocubes were initially formed on the surface of a tungsten (W) microwire electrode and further they were anisotropically grown along the [001] crystallographic direction. Furthermore, we performed the fundamental electrochemical experiments so that from cyclic voltammetric measurements, ReO₃ nanorods on a W microwire exhibit a good capacitance and Nernstian behavior for a Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ redox couple in 1 M KNO₃ aqueous solution, indicating a promising electrode material for electrochemical applications.     

Evaluation of a cobalt-free Ba0.5Sr0.5Fe0.9Nb0.1O3?δ cathode material for intermediate-temperature solid oxide fuel cells

A cobalt-free Ba_0.5Sr_0.5Fe_0.9Nb_0.1O_3??? (BSFNb) perovskite-type oxide was investigated as the cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs) with Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte. XRD results showed that BSFNb cathode was chemically compatible with the electrolyte SDC up to 1,000?°C. The maximum output of anode-supported thin-film SOFC reached 503?mW?cm^?2 at 650?°C when employing humidified H₂ as fuel and static air as oxidizer. The electrode polarization resistance was low as 0.078????cm² at 650?°C, and the activation energy of the electrode polarization resistance was 129.72?kJ?mol^?1. The experimental results indicated that the cobalt-free BSFNb was a promising cathode candidate for IT-SOFCs.     

Photoinduced transition of [Fe(CN)5NO] nitroprusside anions to metastable states and electron localization in the (BEDT-TTF)4K[Fe(CN)5NO]2 molecular metal

The crystals of (BEDT-TTF)₄K[Fe(CN)₅NO]₂, representing a quasi-two-dimensional organic metal with conducting layers of bis(ethylenedithio)tetrathiofulvalene (BEDT-TTF) and nonconducting layers containing pho-tochromic nitroprusside anions [Fe(CN)₅NO]^2?, were studied by the method of electron spin resonance. Illuminated by light with a wavelength of 514.5 nm, the organic metal crystals feature the formation of localized paramagnetic centers in the conducting cation layers of BEDT-TTF. The phenomenon of electron localization in the BEDT-TTF layers is related to the light-induced formation of long-lived metastable states of nitroprusside anions.     

Microstructure and electrode properties of La0.6Sr0.4Co0.2Fe0.8O3-δ spin-coated on Ce0.8Sm0.2O2?δ electrolyte

Fine and uniform La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ powder was synthesized by a glycine–nitrate combustion process. La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ electrodes were prepared on dense Ce_0.8Sm_0.2O_2−δ electrolyte substrates using a spin-coating technique by sintering at 900–1,000 °C. The electrode properties of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ were investigated by electrochemical impedance spectroscopy and chronopotentiometry techniques with respect to preparation conditions and the resulting microstructures. The results indicate a significant effect of the microstructure on the electrode processes and polarization characteristics. The oxygen adsorption and dissociation process acted as a larger contribution to the overall electrode polarization R _p in magnitude compared with the charge transfer process due to relatively low porosity levels of the electrodes. It was detected that the grain size of the electrodes exhibited a crucial role on the electrocatalytic reactivity. At 800 °C, the electrode sintered at 950 °C attained a polarization resistance of 0.18 Ω cm², an overpotential of 27 mV at a current density of 200 mA cm⁻², and an exchange current density of 308 mA cm⁻².     

锐钛矿相TiO2纳米管的制备及其染料敏化太阳电池

以商用金红石相TiO₂粉末为原料,通过在碱性溶液中150℃水热48h的方法合成TiO₂纳米管.采用SEM,TEM,XRD分析手段对TiO₂纳米管的形貌和结构演变进行了表征.制成的TiO₂纳米管与TritonX-100,乙酰丙酮混合后,通过丝网印刷的方法涂敷到ITO导电玻璃衬底上,并且在450℃下烧结30min后得到可应用于染料敏化太阳电池的多孔光阳极.将此光阳极浸泡于N719染料敏化后,与镀铂对电极组装电池,两者之间灌 关键词： 2纳米管')" href="#">TiO₂纳米管 染料敏化太阳电池 水热法     

Hidden reentrant superconducting phase in a magnetic field in (TMTSF)<Subscript>2</Subscript>ClO<Subscript>4</Subscript>

We suggest explanation of the high upper critical magnetic field, perpendicular to conducting chains and parallel to conducting layers H _c2 ^b′ ≃ 6 T, experimentally observed in the organic superconductor (TMTSF)₂ClO₄. In particular, we show that H _c2 ^b′ can be higher than both the quasiclassical upper critical field and Clogston-Chandrasekhar paramagnetic limit in a singlet quasi-one-dimensional superconductor. We predict the coexistence of the hidden Reentrant and Larkin-Ovchinnikov-Fulde-Ferrell phases in a magnetic field. Our results are compared to the recent experimental data and shown to be in a good agreement with the experiments.     

Electrode reaction and microstructure of La0.6Sr0.4CoO3−δ thin films

Dense La_0.6Sr_0.4CoO_3−δ film electrodes were deposited by pulsed laser deposition (PLD) on Ce_0.9Gd_0.1O_1.95 electrolytes. The grain size of one film was 300–500 nm, and the other was 30–50 nm. DC polarization and AC impedance measurements were performed at 873 K–1073 K in O₂–Ar gas mixtures. From investigations of the electrochemical capacitances, the rate determining process for both electrodes were confirmed to be the surface reaction. The analyses in the electrochemical resistance revealed that the oxygen adsorption/desorption rate was faster on the electrode with smaller grain size. DC responses agreed with AC results, so the current density on the nano-grain electrode was larger by half an order than those of the sub-micron-grain electrode. Under a dilute oxygen atmosphere, the rate determining step transferred from a surface reaction to a gas phase diffusion.     

Synthesis and electrochemical performance of mixed phase α/β nickel hydroxide by codoping with Ca<Superscript>2+</Superscript> and PO<Subscript>4</Subscript><Superscript>3−</Superscript>

Nickel hydroxide with a unique mixed phase α/β-Ni(OH)₂ was prepared by partially substituting Ca²⁺ for Ni²⁺ with supersonic co-precipitating method firstly. The crystal structure and morphology of the samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The results show that the Ca-substituted Ni(OH)₂ by adding PO₄ ^3? is α/β mixed phase, while the undoped Ni(OH)₂ and the Ca-substituted Ni(OH)₂ without adding PO₄ ^3? are pure β phase. Furthermore, the Ca-substituted Ni(OH)₂ by adding PO₄ ^3? exhibits irregular shape and contains many intercalated water molecules and anions as proven by SEM and FT-IR. Meanwhile, the prepared samples were added into micro-sized beta nickel hydroxide to form biphase electrode materials for Ni-MH battery. The electrochemical performances of the biphase electrodes were characterized by cyclic voltammetry (CV) and charge/discharge tests. The results demonstrate that the biphase electrode with mixed phase α/β-Ni(OH)₂ exhibits higher electrochemical activity, better electrochemical reversibility and charge efficient, higher discharge potential, and better cyclic stability. The specific discharge capacity of Ca-substituted α/β-Ni(OH)₂ electrode can retain 271.7 and 238 mAh/g after 80 cycles at 0.2 and 0.5 C, respectively. This indicates that it may be a promising positive active material for alkaline secondary batteries. The results reported in this work may be useful for the designing and synthesizing of nickel hydroxide materials with superior performance.     

(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.