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.     

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.     

Investigation on Li-ion battery charging polarization characteristics and influence factors

An electrochemical-thermal Li-ion battery model considering electrochemical reactions and heat transfer was established. Firstly, polarization characteristics were analyzed in principle and polarization voltage was calculated. Then, cell voltage V and polarization voltage V _p versus SOC (state of charge) at different CC (constant-current) charging rates were discussed. Thirdly, average polarization P _A and cutoff SOC SOC_c were proposed to quantize the polarization level and its influence on charging under different charging conditions. Finally, influence factors on battery polarization including electrolyte salt concentration, electrolyte conductivity, active material particle radius, positive electrode conductivity, and ambient temperature were studied. In addition, influence of the factors on SOC_c and heat generation was investigated. The results show that polarization voltage has direct effect on cell voltage and is negatively related with charging performance and positively related with heat generation. Higher electrolyte salt concentration, positive electrode conductivity, lower electrode particle radius, and ambient temperature make for lower polarization voltage.     

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     

Study of solid electrolyte polarization by a complex admittance method

The polarization behavior of zirconia-yttria solid electrolyte specimens with platinum electrodes has been studied over a temperature range of 400° to 800°C and a wide range of oxygen partial pressures. The complex admittance of these specimens was determined over a frequency range from d.c. to 100kHz. An analysis of these data in the complex admittance plane indicated the presence of three polarizations: (1) an electrode polarization characterized by a double layer capacity and an effective resistance for the overall electrode reaction, O₂(gas) + 2e(platinum) O²⁻ (electrolyte); (2) a capacitive-resistive electrolyte polarization, probably corresponding to a partial blocking of oxygen ions at the electrolyte grain boundaries by an impurity phase there; and (3) a pure ohmic electrolyte polarization.     

Removal of tarnishing and roughness of copper surface by electropolishing treatment

Tarnishing and roughness of copper surface can be removed by electropolishing treatment (EP) imparting a bright and smooth surface at suitable conditions, e.g. current density, time, temperature, and viscosity. It was carried out by using an electrolytic cell containing phosphoric acid 55% as the electrolytic solution. Both copper working electrode and lead counter electrode, and reference electrode (SCE) were connected to a Potentiostat/Galvanostat to allow an electric current to pass through the solution. Some additives such as soluble starch, ethylene glycol, and methanol were added to reduce defects formed on the copper surface during EP process. The results showed that the highest gloss value was obtained by applying electric potential 1.5 V at the passive region of polarization curve. The surface was investigated after EP treatment, where SEM and EDX showed lower roughness in case of addition of both soluble starch and ethylene glycol more than methanol. Moreover, AFM analysis showed the lowest roughness in case of soluble starch more than other additives.     

Oxygen permeation studies on La0.8Sr0.2Ga0.75Mg0.15Co0.10O3±δ

Oxygen permeation measurements were carried out on La_0.8Sr_0.2Ga_0.75Mg_0.15Co_0.10O_3±δ specimens of different thickness at temperatures between 673 and 1173 K under various gradients of oxygen partial pressure. Simultaneously, the open circuit cell voltage was measured. It was shown that the investigated compositions were characterized by a high oxygen permeation rate, and, consequently, by a high electronic conductivity. The electrode polarization effect was experimentally proved, and the influence of the measurement conditions on the degree of the electrode polarization effect was studied and discussed in detail. In particular, this mentioned influence was found to be sufficiently smaller at higher oxygen partial pressures in the cathode (oxygen-rich) compartment, while the change of p_O2 on the anode (oxygen-lean) side of the permeation cell did not lead to any sufficient electrode polarization. The values of the hole conductivity calculated from the experimental results found to be at least influenced by electrode polarization were used for calculations of the hole conductivity. The comparison of these values with results obtained by other experimental techniques (by p_O2-dependence of the total conductivity measured using impedance spectroscopy and Hebb–Wagner-polarization technique) demonstrated a satisfactory agreement.     

Electrical study of cathodic activation and relaxation of La0,80Sr0,20MnO3

The effect of cathodic activation of sprayed La_0.8Sr_0.2MnO₃ (LSM) films has been studied by electrochemical spectroscopy impedance (EIS). LSM powder was prepared by a citrate route and X-ray diffraction analyses show a complete LSM crystallization without La₂O₃ or La(OH)₃ as side products. Porosity and grain size estimated from scanning electronic microscopy gave values of 33% and 100 nm, respectively. EIS measurement was performed on a Pt/yttria-stabilized zirconia/LSM cell before and after a cathodic current load (300 mA/cm²) on LSM electrode. The relaxation process, which is time-dependent, has been investigated. A drastic decrease of the electrode resistance was noticed just after applying the cathodic current, but after 9 h at optimized valence configuration in air at 850 °C, the recorded polarization resistance gradually enhanced until it almost reached the initial value. The resulting diagrams have been fitted using a Gerischer associated with a resistor and constant phase elements. This simple method has permitted us to observe that only the electrode interfaces are modified by a cathodic activation and the microstructure remains nearly constant.     

电化学方法在染料电致发光器件中的应用

本文用电化学循环伏安法（I－V）,紫外光谱法（UV）和荧光光谱法（PL）,比较了Alq,PBD和BBOT的紫外吸收谱图及I－V曲线上的电化学行为,实验结果指出,Alq,PBD和BBOT的电化学行为均不可逆,均有大的阴极还原峰电流,表明它们是优良的电子传输体,从氧化还原峰的分析所得到的能带隙宽度的定性结果与UV图上的结果相一致,PL结果表明它们均具有良好的光致发光性能。     

Influence of ferric iron on the electrochemical behavior of pyrite

The electrochemical behavior of a pyrite electrode in a sulfuric acid solution with different concentrations of ferric iron (Fe³⁺) was investigated using electrochemical techniques including measurements of open circuit potential, cyclic voltammetry, Tafel polarization curves and electrochemical impedance spectroscopy (EIS). The results show that the pyrite oxidation process takes place via a two-step reaction at the interface of the pyrite electrode and the electrolyte, and that a passivation film composed of elemental sulfur, polysulfides, and metal-deficient sulfide is formed during the process of the first-step reaction. Ferric iron plays an important role in the dissolution of pyrite by enhancing the direct oxidation. The Tafel polarization curves indicate that the polarization current of the pyrite electrode increases with an increase in Fe³⁺ concentration. It has also been shown that the higher concentration of Fe³⁺, the more easily the pyrite can be transformed into the passivation region. Moreover, the EIS response is found to be sensitive to changes in Fe³⁺ concentration.     

热交联型聚氨酯集成双通道电光调制器的制备及其性质的研究

研究了交联型聚氨酯材料集成衰减全反射型双通道聚合物波导电光调制器的制备和性能。这种电光调制器的制备技术非常简单,只要用两个分立的下电极代替单通道调制器中的下电极即可。通过测量器件的调制特性,在832 nm波长下,获得了最大电光系数为24.2 Pm/V,调制带宽约为500 MHz、插入损耗低于1.5 dB。由于器件上下电极的垂直距离为微米级、而通道之间的水平距离为毫米量级的设计,使各通道之间的场不会引起相互交迭,因而未测到各通道间的串扰。另外,热交联型聚合物材料的采用提高了整个器件的热稳定性,在100℃经过800 h后,电光系数仍然保持初值的88%。     

水溶液体系ESR现场测量新型电解池

设计并研制了用于水溶液体系进行电化学激发-电子自旋共振测量的电解池。以亚甲蓝溶液和聚吡咯薄膜修饰电极的现场ESR研究为例,对该电解池的性能进行了考察。实验不仅为上述两个体系的研究提供了新的信息,而且也证明电解池设计合理、控制工作电极电位准确、响应快及灵敏度高,对研究水溶液体系电化学反应中间体、特别是现场制备和研究薄膜化学修饰电极极为有用。     

锂离子电池多尺度数值模型的应用现状及发展前景

锂离子电池是一种较为复杂的电化学系统, 其涵盖质量传递、电荷传递、热量传递以及多种电化学反应等物理化学过程. 其不仅物理尺度跨越大, 从微观活性颗粒、极片、电芯跨越到电池模组, 还面临着成组配对以及均衡性的问题, 这些问题加剧了电池设计和性能综合评估的难度. 通过计算机数值仿真技术, 建立数学模型, 全面和系统地捕捉电池工作过程各物理场的相互作用机理, 分析其演化规律, 能够为优化电池系统设计提供理论支撑. 本文对锂离子电池的数值模型研究进展和发展趋势进行了综述. 同时对主要理论模型进行了分类整理, 总结了它们的特点、适用范围和局限性, 指出了将来进一步研究的方向和难点所在, 这些对锂离子电池多尺度数值模型的理论研究和工程应用都具有指导性的意义.     

Separation of electrode reactions in multi electrode amperometric sensors

Multi electrode amperometric sensors based on stabilized zirconia have been studied with respect to the simultaneous detection of oxygen and NO. Both gases are of particular interest in oxygen rich exhaust gases. With a setup consisting of two subsequent electrodes it was possible to separate the reduction of oxygen and the reduction of NO spatially. Hence the currents of the two electrodes are directly correlated with the oxygen and the NO concentrations. Combustible gases like CO are oxidized at the oxygen electrode, thus lowering the effective oxygen concentration in the cell. H₂O and CO₂ are partly reduced at the NO electrode. This effect strongly depends on the applied potential and may be eliminated by an appropriate selection of the working parameters. The results demonstrate the potential of such multi electrode cells to the simultaneous detection of several gas components. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Study of the superionic system AgI-PbI2-Ag2O-B2O3

The superionic system AgI-PbI₂-Ag₂O-B₂O₃ with two compositions has been prepared. The pelletised samples were investigated with regard to conductivity, modulus and dielectric analysis at various temperatures and frequencies. The activation energy determined for the samples was found to be varying between 0.09 to 0.10 eV. The effect of polarization at the electrode has been analyzed from conductivity spectra. From the impedance and modulus analysis it has been found that the system is non-ideal and there exists a distribution of relaxation times which is independent of temperature.     

基于评价函数的极紫外多层膜反射式起偏器和检偏器设计

 基于三种不同评价函数,利用全局优化算法设计了极紫外波段高性能反射式多层膜偏振元件。通过比对不同评价函数的设计结果,分析了评价函数、工作角度及膜层数对反射式多层膜偏振片性能的影响,确定了极紫外多层膜反射式偏振片设计的角度选择、膜层数选择及评价函数选择标准。为解决传统的单一性能优化造成的偏振度损失的问题,构造了偏振比对数结合反射率的评价函数,该方法设计的偏振元件性能优于传统优化方法设计的结果。     

Electrochemical Studies of Polymeric Carbons. II. Surface Layer Formation on Glassy Carbon Electrodes in Chloride Solutions as Studied by Radiotracer Techniques

The interaction of chloride ions with glassy carbon electrodes is studied by means of ³⁶Cl as radiotracer. Chloride ions are bonded on the electrode in case of anodization depending on electrode potential and duration of the polarization. Strong interaction is observed at electrode potentials more positive than +1.3 V. A significant part of the chloride ions bonded at the glassy carbon can not be displaced neither by cathodic polarization nor by rinsing with water or non-labelled solutions. It is concluded that chloride ions are chemically bonded at the surface and the surface region of glassy carbon.     

Preparation of cathodes for thin film SOFCs

SOFCs are expected to become competitive devices for electrical power generation, but successful application is dependent on decreasing working temperature from 1000 to 800 °C, without detrimental effects on resistance and on electrode processes. This requires a reduction of the stabilized zirconia electrolyte thickness and an optimization of the electrodes, especially the cathode, where losses are higher. Strontium doped lanthanum manganites are the most common materials tested as cathodes for SOFCs working at high temperature (1000 °C). This cathode material presents high electronic and oxygen-ion conductivities, a thermal expansion coefficient compatible with stabilized zirconia and good catalytic activity. For thin film SOFC devices working at intermediate temperatures (less than 800°C), we have studied the optimization of this type of cathode. Strontium doped lanthanum manganite has been deposited on yttria stabilized zirconia electrolyte substrates by spray-pyrolysis and by RF sputtering. The electrode performances depend strongly on cathode microstructure, influenced by processing conditions. With spray-pyrolysis processes, large porosity is expected. This is important for the supply of oxygen, via O₂ molecules through the pores to the triple phase boundaries, where the gas, the cathode and the electrolyte are in contact and where oxygen reduction may occur. However, large porosity can have a nefaste effect on electronic conductivity. With RF sputtering, denser films with higher electronic conductivity are obtained. But, in that case, the supply of oxygen occurs via adsorbed O-atoms in a diffusion process through the cathode to the electrolyte. Spraypyrolysis and RF sputtering have been compared relative to electrode properties. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Evaluation of solid electrolyte cells with a versatile electrochemical technique

Voltage losses in fuel cells and other solid electrolyte systems are due to several mass transport and kinetics processes at the electrode/electrolyte interface as well as to ohmic contributions from the electrolyte, electrodes, current collectors and contact resistances. Electrochemical impedance spectroscopy (EIS) has been in use for several decades in fuel cell research and is quite effective in determining the contribution of individual electrode and electrolyte processes. However, data acquisition and analysis can be time-consuming and the technique has many limitations whilst cell performance and operating conditions are varying rapidly with time especially when the cells are under current load. The galvanostatic current interruption (GCI) technique is fast and can be used under a wide range of operating as well as for rapidly varying loads and cell performance conditions. In this paper a totally new and very simple way of adapting commercially available equipment has been described to perform high quality, reliable and fast GCI measurements over a range of different currents in one sequence without having to use an electronic switch or a solid state relay or a separate fast data logging system. Its versatility has been demonstrated with a number of standard RC circuits simulating slow electrode and fast electrolyte processes and by evaluating a number of solid oxide fuel cell materials. The GCI technique has been shown to be able to determine the composition of all standard test circuits within ±1 % of those determined from the EIS technique and actual values of circuit components. The technique has been applied to investigating solid electrolyte cells and produced excellent results.