Electrochemical solid electrolyte gas sensors — hydrocarbon and NOx analysis in exhaust gases

For the in situ measurement of the free oxygen concentration and the equilibrium oxygen partial pressure oxygen sensors based on zirconia solid electrolytes are widely used in order to monitor and control technical high temperature processes. Similarly combustibles (HC, CO) and NO_x can be determined in non equilibrated oxygen containing gas mixtures of exhausts by mixed potential sensors and amperometric solid electrolyte sensors. It is expected that their long-term stability is similar to that of oxygen sensors. In both cases the electrode material with the desired electrochemical and catalytic properties is the key component. Different electrode materials made of perovskites (La_1-xSr_xCr_1-yGa_yO_3-δ) and composites (Au/Metal oxide) were investigated in different combustibles including CO, C₃H_6/8, C₇H₈ and CH₄. The response behaviour of mixed potential sensors is determined by the catalytic activity of the measuring electrode, which is closely connected with the defect structure and depends on the measuring conditions. Furthermore the electrode response can be understood by electrokinetic data. Gas symmetrical mixed potential sensors with electrodes made of Au/Nb₂O₅ composites show maximum sensitivity. By using Ptreference electrodes without equilibrium behaviour the sensors are applicable in lean and rich mixtures as well. In the amperometric sensor mode the consecutive determination of oxygen and NO_x or combustibles at two working electrodes is possible. The catalytic activity of the oxygen pumping electrode should be low in order to avoid the decomposition of NO and HC respectively. Alternatively, the electrochemical reduction of NO can be performed at a single working electrode, made of materials with improved NO selectivity, without the previous reduction of oxygen. Paper presented at th 8th EuroConference on Ionics, Ixia, Rhodos, Greece, Sept. 15–21, 2002.     

NiO+YSZ anode substrate for screen-printing fabrication of YSZ electrolyte film in solid oxide fuel cell

Anode substrate has a great effect on screen-printing fabrication of yttria-stabilized zirconia (YSZ) electrolyte film and cell performance. In this work, NiO+YSZ anode substrate was prepared by a conventional ceramic sintering method, on which dense YSZ electrolyte film was successfully fabricated by screen-printing method. Microstructure of the anode substrate and cell performance were investigated. The optimal amount of addition of starch to the anode substrate was 20 wt%. The optimal temperature for pre-sintering of NiO powder was 800 °C. A single cell with the NiO powder pre-sintered at 800 °C exhibited the highest power density of 0.95 W cm⁻² at 700 °C.     

Performance of a double-layer CGO/YSZ electrolyte for solid oxide fuel cells

The use of a double-layer ceria-gadolinia (CGO) - yttria-stabilized zirconia (YSZ) electrolyte has been suggested as an alternative for efficient intermediate temperature operation of Solid Oxide Fuel Cells (SOFC). CGO offers the advantage of high ionic conductivity and good chemical compatibility with Co-containing cathode perovskite materials, while YSZ serves as an electron blocking layer. The main problem for the applicability of such a composite film still remains the formation of a poorly conductive solid solution phase at the CGO/YSZ interface. The microstructure and the elemental distribution of this solid solution phase were examined with the aid of electronic probe microanalysis. Powders with the same composition were synthesized in order to examine their crystal structure and electrical properties, with the objective to propose a suitable gradation at the interface in order to improve the feasibility of CGO/YSZ two- layer composite electrolyte films. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998     

Investigation of solid sodium reference electrodes for solid-state electrochemical gas sensors

Several types of solid reference electrodes for potentiometric gas sensors based on solid sodium ion conductors (e.g., Na⁺-/-Alumina or NASICON) are described and the observed experimental results are discussed in view of theoretical predictions. Defined sodium activities are established by appropriate equilibria of binary and ternary phases. The binary systems Na-Sb and Na-Bi, and the ternary systems Na-M-O (M is a transition-metal, Co or Ni) were found to show excellent kinetic performance and are capable to fix the chemical potential of sodium well defined over extended periods of time. Some of the sodium reference electrodes are even stable in air. The results are compared with the application of elemental sodium as reference electrode.     

Catalytic and electrocatalytic oxidation of methane on palladium electrodes in a solid electrolyte cell

The catalytic oxidation of methane on polycrystalline palladium films was studied at 550-750°C and atmosheric total pressure. The reaction was studied under both open and closed-circuit. Under open circuit, and when yttria-stabilized zirconia (YSZ) was used as solid electrolyte, the technique of Solid Electrolyte Potentiometry (SEP) was used to monitor the thermodynamic activity of oxygen adsorbed on the Pd electrode during reaction. The main products were those of complete oxidation, i.e. CO₂ and H₂O. Under closed-circuit, the effect of electrochemical oxygen “pumping” to or from the catalyst was studied. Non-faradaic (NEMCA) phenomena were observed but the reaction rate enhancement factors (A) were not as large as with previously studied catalytic systems. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996.     

Reference electrodes for low-temperature gas sensors

The behavior of sodium oxide bronzes in contact with sodium-conducting solid electrolytes in atmospheres of oxygen, carbon dioxide, hydrogen sulfide, and humid air was investigated. The exchange currents at the Na_xCoO_y/NASICON interface was determined. It is shown that among the sodium-cobalt oxide bronzes the β-phase of the composition Na_0.6CoO₂ is the most reversible one (exchange current 236 μA/cm²). Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 Sept. 1994     

Polymer electrolyte based solid state redox supercapacitors with poly (3-methyl thiophene) and polypyrrole conducting polymer electrodes

Types I and II solid state redox supercapacitors have been constructed using polypyrrole (pPy) and poly (3-methyl thiophene) (pMeT) conducting polymer electrodes with lithium ion conducting polymer electrolyte poly(ethylene oxide) (PEO)-LiCF₃SO₃ plasticised with poly (ethylene glycol) (PEG). The performance of the capacitors has been characterised by a.c. impedance, linear sweep voltammetry, galvanostatic charge-discharge methods and long term cycling tests. The asymmetric type II capacitors with p-doped pPy and pMeT electrodes give a capacitance value ∼ 2 mF cm⁻² (equivalent to 18 Fg⁻¹ of the total mass of the electrodes) and can be charged up to the voltage of 1.7 V. The symmetric type 1 capacitors of the configuration pPy | polymer electrolyte | pPy and pMeT | polymer electrolyte | pMeT show comparable values of capacitance but they are limited to the working voltage of <1.0 V. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Electron beam physical vapor deposition of YSZ electrolyte coatings for SOFCs

YSZ electrolyte coatings were prepared by electron beam physical vapor deposition (EB-PVD) at a high deposition rate of up to 1 μm/min. The YSZ coating consisted of a single cubic phase and no phase transformation occurred after annealing treatment at 1000 °C. A typical columnar structure was observed in this coating by SEM and feather-like characteristics appeared in every columnar grain. In columnar grain boundaries there were many micron-sized gaps and pores. In TEM image, many white lines were found, originating from the alignment of nanopores existing within feather-like columnar grains. The element distribution along the cross-section of the coating was homogeneous except Zr with a slight gradient. The coating exhibited a characteristic anisotropic behavior in electrical conductivity. In the direction perpendicular to coating surface the electrical conductivity was remarkably higher than that in the direction parallel to coating surface. This mainly attributed to the typical columnar structure for EB-PVD coating and the existence of many grain boundaries along the direction parallel to coating surface. For as-deposited coating, the gas permeability coefficient of 9.78 × 10⁻⁵ cm⁴ N⁻¹ s⁻¹ was obtained and this value was close to the critical value of YSZ electrolyte layer required for solid oxide fuel cell (SOFC) operation.     

Simulation of resistance switching of memory cells based on solid electrolyte

The electrochemical reaction induced resistance switching of memory cells based on solid electrolyte is simulated by an interface-tracking method using a two-dimensional model. For the switching-on process, the simulating results show that metal dendrites will be formed in the solid electrolyte, switching the device to a low-resistance state. For the switching-off process, the dendrite will be dissolved and the conductive channel eventually breaks down, switching the device to a high-resistance state.     

Recent progress in LaGaO3 based solid electrolyte for intermediate temperature SOFCs

Partial electronic and oxide ionic conduction in LaGaO₃ doped with Sr and Mg, Co for Ga site was studied with the ion blocking method. It was found that doping small amount of Co into Ga site is effective for elevating the oxide ion conductivity. However, it is seen that the partial electronic conduction monotonically increases with increasing Co amount and P_O2 at p–n transition was shifted to lower value. Even at X = 0.1, the oxide ion conductivity in LSGMC is still dominant. Calculation on the theoretical leakage of electrolyte of solid oxide fuel cells suggests that the highest efficiency of the electrolyte was achieved around 100 μm in thickness for La_0.8Sr_0.2Ga_0.8Mg_0.15Co_0.05O₃ (LSGMC). Preparation of LSGMC film on Ni–Sm_0.2Ce_0.8O₂ porous anode was studied with the colloidal spray method. In order to prevent the reaction between substrate and film, La doped CeO₂ was used for the interlayer film. In accordance with the theoretical calculation, open circuit potential of the cell using LSGMC film electrolyte with 40 μm thickness becomes much smaller than the theoretical value. However, fairly large maximum power density (0.21 W/cm²) can be achieved at 873 K and even at 773 K, the maximum power density of the cell as high as 0.12 W/cm² was exhibited on the SOFC using 40 μm thickness LSGMC electrolyte.     

Performance of YSZ oxygen sensors protected by electrochemical filters

The performance of nernstian Yttria Stabilized Zirconia (YSZ) oxygen sensors can be seriously affected when in contact with some aggressive industrial furnace atmospheres. Longer life time can be obtained for sensors protected with electrochemical filters. The most relevant parameters determining the protected sensor performance are the ratio between the sensor and the filter oxygen electrochemical permeabilities, and the volume of the electrode protection chamber. The ratio between materials electrochemical permeabilities determines the sensor oxygen activity applicability domain and the deviation between the effective (steady state) and desirable (theoretical) sensor reading. The protected chamber volume will influence the time response behavior. Theoretical predictions on sensor performance are compared with experimental data obtained for protected YSZ sensors conceived for moderately oxidizing atmospheres (1 Pa<Po₂<21 kPa). Two different cases are studied including one single phase and one composite (ionic + electronic conductor) electrochemical filter. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 Sept. 1994.     

Artificial solid electrolyte interphase based on polyacrylonitrile for homogenous and dendrite-free deposition of lithium metal

High chemical reactivity, large volume changes, and uncontrollable lithium dendrite growth have always been the key problems of lithium metal anodes.Coating has been demonstrated as an effective strategy to protect the lithium metal.In this work, the effects of polyacrylonitrile(PAN)-based coatings on electrodeposited lithium have been studied.Our results show that a PAN coating layer provides uniform and dendrite-free lithium deposition as well as better cycling performance with carbonate electrolyte.Notably, heat treatment of the PAN coating layer promotes the formation of larger deposit particle size and higher coulombic efficiency(85%).The compact coating layer of heat-treated PAN with a large Young modulus(82.7 GPa) may provide stable protection for the active lithium.Improved homogeneity of morphology and mechanical properties of heat-treated PAN contribute to the larger deposit particles.This work provides new feasibility to optimize the polymer coating through rational modification of polymers.     

基于阻抗模型解析的氧化锆固体电解质组织结构演变模型

晶界对多元多晶电解质材料电导率的影响, 已成为制约高温固体电解质材料发展的瓶颈. 传统的晶界观察方法难以将高温下材料的组织结构与电导性能相对应. 鉴于此, 本文研究了部分稳定氧化锆(PSZ) 固体电解质材料的变温交流阻抗特性, 并对交流阻抗谱进行了拟合分析, 发现等效拟合电路随温度的上升而发生变化. 通过对不同等效电路模型的物理解析, 得出PSZ电解质材料显微结构在高温下的演变模型. 经进一步分析, 演绎出一种'短程有序'的'晶界桥接'组织模型, 为改善PSZ电解质材料的晶界电导提供了参考.     

Effect of starting powder on screen-printed YSZ films used as electrolyte in SOFCs

Screen-printing technology was developed to fabricate dense YSZ electrolyte films onto NiO–YSZ porous anode substrates. A single fuel cell of Ni-YSZ/YSZ (31 μm)/LSM-YSZ was successfully prepared by screen-printing technology. Using humidified hydrogen as fuel and ambient air as oxidant, the fuel cell provided the maximum power densities of 0.18, 0.33, 0.58, 0.97 and 1.3 W/cm² at 650, 700, 750, 800 and 850 °C, respectively. The properties of the starting YSZ powder exerted a significant effect on the characteristics of the screen-printed YSZ electrolyte films. The aggregates of the powder could be partially broken by ball milling. The YSZ powder with a small particle size and a narrow particle size distribution helped to obtain dense YSZ films. The films prepared from the YSZ powder with high aggregates were very porous, which resulted in a low open circuit voltage, a high ohmic resistance, a high polarization resistance and thus a poor cell performance.     

Impurities and solid electrolyte failure

A thermodynamically based model is used to assess the effects of the formation of a layer of lowered ionic conductivity and increased electronic conductivity on the applied voltage at which solid electrolyte failure is to be expected. Such a layer can result from electrolyte contamination with electrode impurities. It is found that when a significant electrolyte resistivity increase is produced, electrolyte failure can be initiated by a mechanism that deposits sodium internally in the solid electrolyte. The results stress the necessity of operating solid electrolyte cells, such as Na/S, in a manner that minimizes electrode contamination.     

Influence of YSZ electrolyte thickness on the characteristics of plasma-sprayed cermet supported tubular SOFC

Novel Ni–Al₂O₃ cermet-supported tubular SOFC cell was fabricated by thermal spraying. Flame-sprayed Al₂O₃–Ni cermet coating played dual roles of a support tube and an anode current collector. Y₂O₃-stabilized ZrO₂ (YSZ) electrolyte was deposited by atmospheric plasma spraying (APS) to aim at reducing manufacturing cost. The gas tightness of APS YSZ coating was achieved by post-densification process. The influence of YSZ coating thickness on the performance of SOFC test cell was investigated in order to optimize YSZ thickness in terms of open circuit voltage of the cell and YSZ ohmic loss. It was found that the reduction of YSZ thickness from 100 μm to 40 μm led to the increase of the maximum output power density from 0.47 W/cm² to 0.76 W/cm² at 1000 °C. Using an APS 4.5YSZ coating of about 40 μm as the electrolyte, the test cell presented a maximum power output density of over 0.88 W/cm² at 1030 °C. The results indicate that SOFCs with thin YSZ electrolyte require more effective cathode and anode to improve performance.     

Silicon micropillar electrodes of lithiumion batteries used for characterizing electrolyte additives

The <100> crystal-oriented silicon micropillar array platforms were prepared by microfabrication processes for the purpose of electrolyte additive identification. The silicon micropillar array platform was used for the study of fluorinated vinyl carbonate (FEC), vinyl ethylene carbonate (VEC), ethylene sulfite (ES), and vinyl carbonate (VC) electrolyte additives in the LiPF₆ dissolved in a mixture of ethylene carbonate and diethyl carbonate electrolyte system using charge/discharge cycles, electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, and x-ray photoelectron spectroscopy. The results show that the silicon pillar morphology displays cross-shaped expansion after lithiation/delithiation, the inorganic lithium salt keeps the silicon pillar morphology intact, and the organic lithium salt content promotes a rougher silicon pillar surface. The presence of poly-(VC) components on the surface of FEC and VC electrodes allows the silicon pillar to accommodate greater volume expansion while remaining intact. This work provides a standard, fast, and effective test method for the performance analysis of electrolyte additives and provides guidance for the development of new electrolyte additives.     

Impedance characteristics of three-phase electrodes on solid electrolytes

Previously obtained theoretical expressions for the impedance associated with the diffusion of neutral species through a permeable electrode and along the electrode/electrolyte interface are discussed as they apply to gas electrodes on solid electrolytes. A new result, describing diffusion under circular electrode contacts, is obtained. Representative impedance-plane, admittance-plane and Bode-type plots are given for each theoretical model. The effects of rate-controlling adsorption-desorption exchange with the gas phase are considered, as is the applicability of the idealized theoretical models to irregular electrodes.     

A one-chamber solid electrolyte fuel cell for chemical cogeneration

A one chamber solid oxide fuel cell (SOFC) which works in a flow of a mixture of CH₄ and air has been studied in the present author's laboratory. This new type cell consists of Pt | Solid Electrolyte | Au, in which both electrodes are exposed to the CH₄₊₂ai r mixture with a CH₄/O₂ ratio of 2 at elevated temperatures, and it generates an electric power producing hydrogen and carbon monoxide (synthetic gas) with a H₂/CO ratio of about 2. A large difference in catalytic activity for the partial oxidation of CH₄ between the Pt and Au electrode materials leads to an oxygen concentration cell which can generate an electric power between them. In this paper the author describes such a one-chamber fuel cell with respect to their structural feature, performance as a fuel cell and their component materials citing the experimental results made by his laboratory's group. Paper presented at the 97th Xiangshan Science Conference on New Solid State Fuel Cells, Xiangshan, Beijing, China, June 14–17, 1998.