Solid electrolytes preparation

Rabinovich L, Lev O, Tsirlina GA (1999) Electrochemical characterization of Pd modified ceramic vertical bar carbon electrodes partially flooded versus wetted channel hydrophobic gas electrodes. J Llectroanal Chem 466(l) 45-59 Rog G, Kielski A, Kozlowska-Rog A, Bucko M (1998) Composite (CaFj-AljOj) solid electrolytes-preparation, properties and application to the solid oxide galvanic cells. Ceram Int 24 91-98 Roh S-W, Stetter JR (2003) Amperometric sensing of NOx with cyclic voltammetry. J Electrochem Soc 150(11) H266-H272... 

Tamura S, Imanaka N, Adachi G (2002) Trivalent ion conduction in NASICON type solid electrolyte prepared by ball milling. Solid State Ionics 154-155 767-771... 

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... 

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. 

The dendritic growth of lithium was suppressed on a lithium electrode surface modified by an ultrathin solid polymer electrolyte prepared from 1,1—difluoro-ethane by plasma polymerization [114]. 

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. 

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. 

Direct-current sputtering is not generally applicable for the preparation of thin-film solid electrolytes since these compounds are electronic insulators. The target surface would be charged with the same polarity as that of the ions in the plasma, and the sputtering plasma would rapidly break down. 

In spray pyrolysis, very fine droplets are sprayed onto a heated substrate. The limitations of this process are the same as for spin-on coating. The same is often the case for preparing solid electrolytes by chemical vapor deposition (CVD) processes, which in addition are more expensive, and the precursors are often very toxic. 

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... 

As discussed below, the porosity and surface area of the catalyst film is controllable to a large extent by the sintering temperature during catalyst preparation. This, however, affects not only the catalytically active surface area AG but also the length, t, of the three-phase-boundaries between the solid electrolyte, the catalyst film and the gas phase (Fig. 4.7). 

The sol-gel technique was also used to prepare solid electrolytes containing MEEP, triethoxysilane (TEOS) and lithium triflate. Homogeneous, transparent and mechanicaUy stable materials have been obtained by Gughelmi [611] from a partially hydroxylated MEEP and TEOS, which after doping with LiSOjCFj exhibited a conductivity in the range 3x10 S cm at 60 °C. 

Ion exchangers are polymer electrolytes prepared a priori as insoluble solids (salts, acids, bases hydrated, possibly gel-Uke). Their polymer backbone is three-dimensional. Many are polyvinyl compounds (substituted polyethylenes) having the general formula [-CH2-CXH-] , where different substituents X lead to rather different products ... 

Materials similar to Nation containing immobilized —COO- or —NR3+ groups on a perfluorinated skeleton were also synthesized. These are available in the form of solid membranes or solutions in organic solvents the former can readily be used as solid electrolytes in the so called solid polymer electrolyte (SPE) cells, the latter are suitable for preparing ion-exchange polymeric films on electrodes simply by evaporating the polymer solution in a suitable solvent. 

Two earlier reviews were published on high temperature cells and batteries based on molten salt and solid electrolytes. The first one (69) describes the Li/Cl2 cells, particularly the LiA.l/LiCl-KCl/Cl2 cell with gaseous CI2. Li cells with chalcogenides as cathode materials are mentioned, as well as some details of construction. This review, and the 26 references attached to it, reflects the state of the Li molten salt batteries to the end of 1970 (69). The second review (70), prepared two years later is more comprehensive. It discusses in detail some theoretical problems, the thermodynamics and rate processes in electrochemical cells, and presents tables and... 

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