Metal oxide solid electrolytes

Numbers of detectable gases have been increased since Gauthier et al.[3] first proposed the feasibility of solid electrolyte gas sensors for SOj, NOj, CO and so on. Moreover the couple of a metal oxide solid electrolyte and an auxiliary electrode, investigated recently, makes it possible for stable operation and disuse of a reference gas. Electrochemical gas sensors has a strong point of detecting gases selectively because only one kind of ion can permeate through... 

Results of numerous items of research have shown that, in theory, any material can be used in the design of a gas sensor, regardless of its physical, chemical, structural, or electrical properties (Korotcenkov 2010,2011). Prototypes of gas sensors based on covalent semiconductors, semiconducting metal oxides, solid electrolytes, polymers, ionic membranes, organic saniconductors, and ionic salts have already been tested (Sadaoka 1992 Gopel 1996 Haugen and Kvaal 1998 Monkman 2000 Talazac et al. 2001 Eranna et al. 2004 Adhikari and Majumdar 2004). As shown in Table 1.23, these materials may be used... 

Table 2.7 Metal oxide solid electrolytes used in electrochemical Hj gas sensors...

Metal oxide solid electrolytes Temp, of stability (°C) Type of gas sensor... 

Inorganic membranes can be categorized as shown in Table 2.1. The dense inorganic membranes consist of solid layers of metals (Pd, Ag, alloys) or (oxidic) solid electrolytes which allow diffusion of hydrogen (or oxygen). In the case of solid electrolytes transport of ions takes place. Another category of dense membranes consist of a porous support in which a liquid is... 

For example, the electrolyte of alkali fuel cells is a solution of potassium hydroxide (an alkaline, which has a high pH). Solid oxide fuel cells use compoimds of metal oxides as electrolytes. (Fuel cell names are generally... 

Lead and mercury are deposited as micron-sized clusters, predominantly at intercrystallite boundaries [105] so does lithium from the polyethylene oxide solid electrolyte. What is more, Li intercalates into the sp2-carbon [22, 138], Thus, observations on the Li intercalation and deintercalation enable one to detect non-diamond carbon on the diamond film surface. Copper is difficult to plate on diamond [139], There is indirect evidence that Cu electrodeposition, whose early stages proceed as underpotential deposition, also involves the intercrystallite boundaries [140], We note that diamond electrodes seem to be an appropriate tool for use in the well-known electroanalytical method of detection of traces of metal ions in solutions by their cathodic accumulation followed by anodic stripping. The same holds for anodic deposition, e.g. of, Pb as PbCh with subsequent cathodic reduction [141, 142], Figure 30 shows the voltammograms of anodic dissolution of Cd and Pb cathodically predeposited from their salt mixtures on diamond and glassy carbon electrodes. We see that the dissolution peaks are clearly resolved. The detection limit for Zn, Cd, and Pb is as low as a few ppb [143]. 

The calorimetric measurements in metal oxide-aqueous electrolyte solution systems are, beside temperature dependence of the pzc measurements, the method for the determination of the enthalpy of the reaction in this system. Because of the low temperature effects in such systems they demand very high precision. That is why these measurements may be found only in a few papers from the last ten years [89-98]. A predominant number of published measurements were made in the special constricted calorimeters (bath type), stirring the suspension. The flow calorimeters may be used only for sufficiently large particles of the solid. A separate problem is the calculation of the enthalpy of the respective reactions from the total heat recorded in the calorimeter. A total thermal effect consists of the heat of the neutralization in the liquid phase, heat connected with wetting of the solid, heat of the surface reaction and heat effects caused by the ion solvation changes (the ions that adsorb in the edl). Considering the soluble oxides, one should include the effects connected with the transportation of the ions from the solid to the solution... 

The polycrystalline metal film/oxidic solid electrolyte system provides a reasonable approximation to nanocrystalline metal/metal oxide catalysts. 

Vijh, A.K., Acid-base properties of sohd metal oxides in electrolyte solutions in relation to the solid-state properties of metals, Appl. Phys. Commun., 13, 275, 1994. 

Analytical methods applied to estimate oxygen in alkali metals are the fast neutron activation for lithium oxide in lithium, vacuum distillation of excess alkali metal and analysis of the residue by atomic absorption spectrometry to estimate oxygen in sodium, as well as in the heavier alkali metals. Equilibration of oxygen between getters such as vanadium, liquid alkali metals and solid electrolyte oxygen meters, can be applied in several alkali metals. They measure oxygen activities directly in alkali metal circuits or closed containers. 

There have been cases wherein a fluoride ion solid electrolyte, in particular CaF2r has been placed between two different metal oxide electrodes and behaved as if it were an oxide solid electrolyte. That is, the emf was found to be equal to that measured previous with caloia- or yttria-stabilized zirconial No very suitable explanation has been offered yet, but I think that these findings have been published or soon will be. But if my conjectures above are correct, the following explanation could be offered. 

A unique application of the solid oxygen electrolytes is in dre preparation of mixed oxides from metal vapour deposits. For example, the ceramic superconductors described below, have been prepared from mixtures of the metal vapours in the appropriate proporhons which are deposited on the surface of a solid electrolyte. Oxygen is pumped tluough the electrolyte by the application of a polarizing potential across the electrolyte to provide the oxidant for the metallic layer which is formed. 

Another application is in tire oxidation of vapour mixtures in a chemical vapour transport reaction, the attempt being to coat materials with a tlrin layer of solid electrolyte. For example, a gas phase mixture consisting of the iodides of zirconium and yttrium is oxidized to form a thin layer of ytnia-stabilized zirconia on the surface of an electrode such as one of the lanthanum-snontium doped transition metal perovskites Lai j.Srj.M03 7, which can transmit oxygen as ions and electrons from an isolated volume of oxygen gas. 

Solid oxide fuel cells consist of solid electrolytes held between metallic or oxide elecU odes. The most successful fuel cell utilizing an oxide electrolyte to date employs Zr02 containing a few mole per cent of yttrium oxide, which operates in tire temperature range 1100-1300 K. Other electrolytes based... 

The electrical conductivity also increases with increasing metal oxide content, due to the high mobility of the metal ions. For example several glass compositions have been used as solid electrolytes in galvanic cells in which other metal ions apart from the alkaline and alkaline earth ions have been incorporated. The electrochemical cell... 

Dry cells (batteries) and fuel cells are the main chemical electricity sources. Diy cells consist of two electrodes, made of different metals, placed into a solid electrolyte. The latter facilitates an oxidation process and a flow of electrons between electrodes, directly converting chemical energy into electricity. Various metal combinations in electrodes determine different characteristics of the dry cells. For example, nickel-cadmium cells have low output but can work for several years. On the other hand, silver-zinc cells are more powerful but with a much shorter life span. Therefore, the use of a particular type of dry cell is determined by the spacecraft mission profile. Usually these are the short missions with low electricity consumption. Diy cells are simple and reliable, since they lack moving parts. Their major drawbacks are... 

By 19884 it became obvious that the NEMCA effect, this large apparent violation of Faraday s law, is a general phenomenon not limited to a few oxidation reactions on Ag. Of key importance in understanding NEMCA came the observation that NEMCA is accompanied by potential-controlled variation in the catalyst work function.6 Its importance was soon recognized by leading electrochemists, surface scientists and catalysis researchers. Today the NEMCA effect has been studied already for more than 60 catalytic systems and does not seem to be limited to any specific type of catalytic reaction, metal catalyst or solid electrolyte, particularly in view of... 

Nevertheless there are some reactions which never change. Thus NO reduction on noble metals, a very important catalytic reaction, is in the vast majority of cases electrophilic, regardless of the type of solid electrolyte used (YSZ or P"-A1203). And practically all oxidations are electrophobic under fuel lean conditions, regardless of the type of solid electrolyte used (YSZ, p"-Al203, proton conductors, even alkaline aqueous solutions). 

We consider the porous metal catalyst film shown in Figure 11.12 which is interfaced with an O2" conductor. When a positive current, I, is applied between the catalyst and a counter electrode, oxide ions O2 are supplied from the solid electrolyte to the three phase boundaries (tpb) solid electrolyte-metal-gas at a rate I/2F. Some of these O2 will form 02 at the tpb and desorb ... 

State-of-the-art thin film Li" cells comprise carbon-based anodes (non-graphitic or graphite), solid polymer electrolytes (such as those formed by solvent-free membranes, for example, polyethylene oxide, PEO, and a lithium salt like LiPFe or LiCFsSOs), and metal oxide based cathodes, in particular mixed or doped oxides... 

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