Materials Solid electrolytes

By far the most important practical use of this sensor is for automotive applications, namely for the control of the air to fuel ratio. It compares favorably with the surface conductivity or high temperature potentiometric sensor (Logothetis, 1987). Other gases could be detected on the same principle provided that the right materials for the electrochemical pump were used. The electrode materials/solid electrolytes used for the construction of potentiometric high temperature sensors (see Table 6.7) could serve as guidance. 

It includes additional information on insertion materials, solid electrolytes, semiconducting electrodes, photoelectrochemistry and the thermoelectric effect. 

In the ceramics field many of the new advanced ceramic oxides have a specially prepared mixture of cations which determines the crystal structure, through the relative sizes of the cations and oxygen ions, and the physical properties through the choice of cations and tlreh oxidation states. These include, for example, solid electrolytes and electrodes for sensors and fuel cells, fenites and garnets for magnetic systems, zirconates and titanates for piezoelectric materials, as well as ceramic superconductors and a number of other substances... 

The addition of MgO leads to the formation of a naiTow range of solid solutions at high temperamre, which decompose to precipitate inclusions of tetragonal Zr02 dispersed in cubic zirconia. The material, which functions as a solid electrolyte, has the added advantage that the inclusions stop the propagation of any cracks which may arise from rapid temperature change. 

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. 

An instructive use has been made of the solid electrolyte, Agl, which conducts by the migration of silver ions. If this material is used as an electrolyte in the cell... 

A signihcant problem in tire combination of solid electrolytes with oxide electrodes arises from the difference in thermal expansion coefficients of the materials, leading to rupture of tire electrode/electrolyte interface when the fuel cell is, inevitably, subject to temperature cycles. Insufficient experimental data are available for most of tire elecuolytes and the perovskites as a function of temperature and oxygen partial pressure, which determines the stoichiometty of the perovskites, to make a quantitative assessment at the present time, and mostly decisions must be made from direct experiment. However, Steele (loc. cit.) observes that tire electrode Lao.eSro.rCoo.aFeo.sOs-j functions well in combination widr a ceria-gadolinia electrolyte since botlr have closely similar thermal expansion coefficients. 

Sodium-Sulfur Batteries. The sodium-sulfur battery consists of molten sodium at the anode, molten sulfur at the cathode, and a solid electrolyte of a material that allows for the passage of sodium only. For the solid electrolyte to be sufficiently conductive and to keep the sodium and sulfur in a liquid state, sodium-sulfur cells must operate at 300°C to 350°C (570°F to 660°F). There has been great interest in this technology because sodium and sulfur are widely available and inexpensive, and each cell can deliver up to 2.3 volts. 

Lyon, S. B. and Fray, D. J., Detection of Hydrogen Generated by Corrosion Reactions using a Solid Electrolyte Probe , Materials Performance, 24, 4, 23-25, April (1984)... 

Fabrication techniques, especially the preparation of thin films of functional materials, have made major progress in recent years. Thin-film solid electrolytes in the range of several nanometers up to several micrometers have been prepared successfully. The most important reason for the development of thin-film electrolytes is the reduction in the ionic resistance, but there is also the advantage of the formation of amorphous materials with stoichiometries which cannot be achieved by conventional techniques of forming crystalline compounds. It has often been observed that thin-film electrolytes produced by vacuum evaporation or sputtering provide a struc-... 

A commonly inexpensive way to prepare solid electrolytes is the formation of monolithic samples. Depending on the required phases and final compounds, a large variety of preparation methods are known. These methods usually provide polycrystalline materials. 

In solid-state batteries, it is extremely favorable to use the solid electrolyte for mechanical support. Despite the larger thickness, which lowers the relative amount for active material in the battery, the advantages are the absence of pinholes of the solid electrolyte, high electronic resistance, and simple multistack fabrication, since the individual cells may be contacted by their electronically conducting current collectors. 

Thin-film solid electrolytes in the range of lpm have the advantage that the material which is inactive for energy storage is minimized and the resistance of the solid electrolyte film is drastically decreased for geometrical reasons. This allows the application of a large variety of solid electrolytes which exhibit quite poor ionic conductivity but high thermodynamic stability. The most important thin-film preparation methods for solid electrolytes are briefly summarized below. 

For the application of solid electrolytes in batteries it is essential to characterize the materials carefully. These measurements may be easily misleading and are often incorrectly interpreted. It is therefore vital that the correct arrangements and procedures are applied. 

In the Na/S system the sulfur can react with sodium yielding various reaction products, i.e. sodium polysulfides with a composition ranging from Na2S to Na2S5. Because of the violent chemical reaction between sodium and sulfur, the two reactants have to be separated by a solid electrolyte which must be a sodium-ion conductor. / " -Alumina is used at present as the electrolyte material because of its high sodium-ion conductivity. 

There is a wide variety of solid electrolytes and, depending on their composition, these anionic, cationic or mixed conducting materials exhibit substantial ionic conductivity at temperatures between 25 and 1000°C. Within this very broad temperature range, which covers practically all heterogeneous catalytic reactions, solid electrolytes can be used to induce the NEMCA effect and thus activate heterogeneous catalytic reactions. As will become apparent throughout this book they behave, under the influence of the applied potential, as active catalyst supports by becoming reversible in situ promoter donors or poison acceptors for the catalytically active metal surface. 

Chapter 3 discusses solid electrolytes and some of their early applications in fuel cells and catalysis. This material is quite familiar to the solid state ionics community but may be helpful to surface scientists, aqueous electrochemists and chemical reaction engineers. 

Today, the term solid electrolyte or fast ionic conductor or, sometimes, superionic conductor is used to describe solid materials whose conductivity is wholly due to ionic displacement. Mixed conductors exhibit both ionic and electronic conductivity. Solid electrolytes range from hard, refractory materials, such as 8 mol% Y2C>3-stabilized Zr02(YSZ) or sodium fT-AbCb (NaAluOn), to soft proton-exchange polymeric membranes such as Du Pont s Nafion and include compounds that are stoichiometric (Agl), non-stoichiometric (sodium J3"-A12C>3) or doped (YSZ). The preparation, properties, and some applications of solid electrolytes have been discussed in a number of books2 5 and reviews.6,7 The main commercial application of solid electrolytes is in gas sensors.8,9 Another emerging application is in solid oxide fuel cells.4,5,1, n... 

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