Solid electronic conductivity

A quite different approach was introduced in the early 1980s [44-46], in which a dense solid electrode is fabricated which has a composite microstructure in which particles of the reactant phase are finely dispersed within a solid, electronically conducting matrix in which the electroactive species is also mobile. There is thus a large internal reactant/mixed-conductor matrix interfacial area. The electroactive species is transported through the solid matrix to this interfacial region, where it undergoes the chemical part of the electrode reaction. Since the matrix material is also an electronic conductor, it can also act as the electrode s current collector. The electrochemical part of the reaction takes place on the outer surface of the composite electrode. 

The charged reactant for the sink electrochemical reaction is supplied by the solid electrochemical cell of a PEVD system. The solid phase (E) is an exclusive ionic conductor for (A +) or (A ), and serves as the solid electrolyte. (C) and (W) are solid electronic conducting phases, and contact (E) from both sides as counter and working electrodes, respectively. They coimect with the external electric circuit, which consists of a dc source and other possible measurement devices. Because the conductivity changes in nature from ionic to electronic at the electrode/electrolyte interfaces, the solid electrochemical cell in a PEVD system effectively separates the transport paths of ionic and electronic charged carriers... 

Thermal energy is transported by two mechanisms in solids—electronic conduction and lattice or phonon conduction. An electrical analog for thermal conduction is shown in Fig. 2 [% The total thermal conductivity. A, is the sum of the electronic term and the lattice term. For pure metals and dilute alloys, thermal conduction is dominated by the electronic term, while for heavily alloyed metals, the phonon contribution is appreciable. 

The catalyst is then mixed with a solubilized form of ionomer, which is then used as an ink to print a thin catalyst layer on the order of 10 microns thick. The catalyst layer, then, is comprised of the solid, electronically conducting carbon phase, decorated with platinum, a largely contiguous network of ionomer to provide ionic transport through the thickness of the layer, and the voids that provide a pathway for gas and liquid access. 

Porous-electrode theory has been used to describe a variety of electrochemical devices including fuel cells, batteries, separation devices, and electrochemical capacitors. In many of these systems, the electrode contains a single solid phase and a single fluid phase. Newman and Tiedemann reviewed the behavior of these flooded porous electrodes [23]. Many fuel-cell electrodes, however, contain more than one fluid phase, which introduces additional complications. Typical fuel cell catalyst layers, for example, contain both an electrolytic phase and a gas phase in addition to the solid electronically conducting phase. An earher review of gas-diffusion electrodes for fuel cells is provided by Bockris and Srinivasan [24]. 

The I A membrane may be contacted on the inner side with a solid, electronically conducting material to form an all-solid-state electrode. This is generally regarded to be a sound practice only if the two contacting solid phases can equilibrate, i.e., there is at least one charged species (ion or electron)... 

Electrolyte a substance, liquid or solid, which conducts electrical current by movement of ions (not of electrons). In corrosion science, an electrolyte is usually a liquid solution of salts dissolved in a solvent, or a molten salt. The term also applies to polymers and ceramics which are ionically conductive. 

The proposed model for the so-called sodium-potassium pump should be regarded as a first tentative attempt to stimulate the well-informed specialists in that field to investigate the details, i.e., the exact form of the sodium and potassium current-voltage curves at the inner and outer membrane surfaces to demonstrate the excitability (e.g. N, S or Z shaped) connected with changes in the conductance and ion fluxes with this model. To date, the latter is explained by the theory of Hodgkin and Huxley U1) which does not take into account the possibility of solid-state conduction and the fact that a fraction of Na+ in nerves is complexed as indicated by NMR-studies 124). As shown by Iljuschenko and Mirkin 106), the stationary-state approach also considers electron transfer reactions at semiconductors like those of ionselective membranes. It is hoped that this article may facilitate the translation of concepts from the domain of electrodes in corrosion research to membrane research. 

One leading prototype of a high-temperature fuel cell is the solid oxide fuel cell, or SOFC. The basic principle of the SOFC, like the PEM, is to use an electrolyte layer with high ionic conductivity but very small electronic conductivity. Figure B shows a schematic illustration of a SOFC fuel cell using carbon monoxide as fuel. 

Traditionally, the chemical stability of the electrode/electrolyte interface and its electronic properties have not been given as much consideration as structural aspects of solid electrolytes, in spite of the fact that the proper operation of a battery often depends more on the interface than on the solid electrolyte. Because of the high ionic conductivity in the electrolyte and the high electronic conductivity in the electrode, the voltage falls completely within a very narrow region at the electrolyte/electrode interface. 

Electronic conductivity of thin-film solid electrolytes. Besides having low electronic transference numbers, it is essential for thin films of the order of 1 jim that the magnitude of the electronic resistance is low in order to prevent self-discharge of the battery. For this reason, specific electronic resistances in the range of 1012-1014 Qcm are required for thin-film solid electrolytes. Often the color may be a valuable indication of the electronic conductivity. In this regard, solid electrolytes should preferably be transparent white [20]. 

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. 

Measurements of photoconductivity and of the Hall potential [367] are accurate and unambiguous methods of detecting electronic conduction in ionic solids. Kabanov [351] emphasizes, however, that the absence of such effects is not conclusive proof to the contrary. From measurements of thermal potential [368], it is possible to detect solid-solution formation, to distinguish between electronic and positive hole conductivity in semi-conductors and between interstitial and vacancy conductivity in ionic conductors. 

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... 

When a solid electrolyte component is interfaced with two electronically conducting (e.g. metal) films (electrodes) a solid electrolyte galvanic cell is formed (Fig. 3.3). Cells of this type with YSZ solid electrolyte are used as oxygen sensors.8 The potential difference U R that develops spontaneously between the two electrodes (W and R designate working and reference electrode, respectively) is given by ... 

This study, in conjunction with that discussed in 12.2.1.2, show that when using aqueous electrolytes or Nafion saturated with H20, the induction of NEMCA on finely dispersed noble metal catalysts is rather straightforward. The role of the electronically conducting porous C support is only to conduct electrons and to support the finely dispersed catalyst. The promoting species can reach the active catalyst via the electrolyte or via the aqueous film without having to migrate on the surface of the support, as is the case when using ceramic solid electrolytes. 

There are no specific requirements for the solid electrolytes (pellets or tubes) used in electrochemical promotion experiments. However they should be stable under the conditions of the experimental study. Also one should know the type of ionic conductivity and the possibility of appearance of mixed ionic-electronic conductivity under the conditions of electrochemical promotion. This is quite essential for the correct interpretation of results. Addresses of suppliers of solid electrolytes included in Table B.l are presented below ... 

As outlined in chapter 1 the term electrode is used - contrary to the suggestion of W. Nemst - to designate the electronically conducting phase only, the term electrolyte solution covers all types of ionically conducting phases (solutions, melts, solids) being in contact with the former phase. 

As pure elements, almost all the transition metals are solids that conduct heat and electricity and are malleable and ductile. Although they share these general properties, transition metals display variations in other properties that can be traced to their different numbers of valence electrons. 

In the solid, electrons reside in the valence band but can be excited into the conduction band by absorption of energy. The energy gap of various solids depends upon the nature of the atoms comprising the solid. Semiconductors have a rather narrow energy gap (forbidden zone) whereas that of insulators is wide (metals have little or no gap). Note that energy levels of the atoms "A" are shown in the valence band. These will vary depending upon the nature atoms present. We will not delve further into this aspect here since it is the subject of more advanced studies of electronic and optical materieds. 

Double Substitution In such processes, two substitutions take place simultaneously. For example, in perovskite oxides, La may be replaced by Sr at the same time as Co is replaced by Fe to give solid solutions Lai Sr Coi yFey03 5. These materials exhibit mixed ionic and electronic conduction at high temperatures and have been used in a number of applications, including solid oxide fuel cells and oxygen separation. 

In addition to metals, other substances that are solids and have at least some electronic conductivity can be used as reacting electrodes. During reaction, such a solid is converted to the solid phase of another substance (this is called a solid-state reaction), or soluble reaction products are formed. Reactions involving nomnetaUic solids occur primarily in batteries, where various oxides (MnOj, PbOj, NiOOH, Ag20, and others) and insoluble salts (PbS04, AgCl, and others) are widely used as electrode materials. These compounds are converted in an electrochemical reaction to the metal or to compounds of the metal in a different oxidation state. 

Nonmetal electrodes are most often fabricated by pressing or rolling of the solid in the form of fine powder. For mechanical integrity of the electrodes, binders are added to the active mass. For higher electronic conductivity of the electrode and a better current distribution, conducting fillers are added (carbon black, graphite, metal powders). Electrodes of this type are porous and have a relatively high specific surface area. The porosity facilitates access of dissolved reactants (H+ or OH ions and others) to the inner electrode layers. 

The electronic conductivity of metal oxides varies from values typical for insulators up to those for semiconductors and metals. Simple classification of solid electronic conductors is possible in terms of the band model, i.e. according to the relative positions of the Fermi level and the conduction/valence bands (see Section 2.4.1). 

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