Solid-state electrochemistry electrochemical

D. Tsiplakides, and C.G. Vayenas, Electrode work function and absolute potential scale in solid state electrochemistry. /. Electrochem. Soc. 148(5), E189-E202 (2001). 

Paasch G (2000) The transmission line equivalent eircuit model in solid-state electrochemistry. Electrochem Common 2 371-375. doi 10.1016/S1388-2481(00)00040-0... 

The implications of Equation (4.30) for solid state electrochemistry and electrochemical promotion in particular can hardly be overemphasized It shows that solid electrolyte cells are both work function probes and work function controllers for their gas-exposed electrode surfaces. 

Work function, a quantity of great importance in surface science and catalysis, plays a key role in solid state electrochemistry and in electrochemical promotion. As will be shown in Chapter 7 the work function of the gas-exposed surface of an electrode in a solid electrolyte cell can be used to define an absolute potential scale in solid state electrochemistry. 

It must be emphasized that Equations (5.24) and (5.25) stem from the definitions of Fermi level, work function and Volta potential and are generally valid for any electrochemical cell, solid state or aqueous. We can now compare these equations with the corresponding experimental equations (5.18) and (5.19) found to hold, under rather broad temperature, gaseous composition and overpotential conditions (Figs. 5.8 to 5.16), in solid state electrochemistry ... 

Figure 5.22 reveals the ability of solid state electrochemistry to create new types of adsorption on metal catalyst electrodes. Here oxygen has been supplied not from the gas phase but electrochemically, as 02 via current application for a time, denoted tj, of 1=15 pA at 673 K, i.e. at the same temperature used for gaseous O2 adsorption (Fig. 5.21). Figure 5.23 shows the effect of mixed gaseous-electrochemical adsorption. The Pt surface has been initially exposed to po2 =4x1 O 6 Torr for 1800 s (7.2 kL) followed by electrochemical O2 supply (1=15 pA) for various time periods ti shown on the figure, in order to simulate NEMCA conditions. 

The presence of this backspillover formed effective double layer is important not only for interpreting the effect of electrochemical promotion, but also for understanding the similarity of solid state electrochemistry depicted in Fig. 7.3 with the case of emersed electrodes in aqueous electrochemistry (Fig. 7.2) and with the gedanken experiment of Trasatti (Fig. 7.1) where one may consider that H2O spillovers on the metal surface. This conceptual similarity also becomes apparent from the experimental results. 

Thus the key experimental observation Equation (7.11), is satisfied in presence of spillover. When an external overpotential AUWR is applied, with a concomitant current, I, and O2 flux I/2F, although UWR is not fixed anymore by the Nemst equation but by the extremally applied potential, still the work function Ow will be modified and Equations (7.11) and (7.12), will remain valid as long as ion spillover is fast relative to the electrochemical charge transfer rate I/2F.21 This is the usual case in solid state electrochemistry (Figs. 7.3b, 7.3d) as experimentally observed (Figs. 5.35, 5.23, 7.4, 7.6-7.9). 

Figure 7.12 shows the relationship between the standard oxygen electrode (soe) scale of solid state electrochemistry, the corresponding standard hydrogen electrode (she) scale of solid state electrochemistry, the standard hydrogen electrode (she) scale of aqueous electrochemistry, and the physical absolute electrode scale. The first two scales refer to a standard temperature of 673.15 K, the third to 298.15 K. In constructing Figure 7.12 we have used the she aqueous electrochemical scale as presented by Trasatti.14... 

Bulletin of Electrochemistry, Central Electrochemical Research Institute, Karaikudi, India. Electrochemical and Solid State Letters, Electrochemical Society, Pennington, N.J. Electrochemical Communications. Elsevier, Amsterdam. 

This contribution reviews recent results on [Si(Pc)0]n (Pc = phthalocyaninato) solid state electrochemistry and the structural interconversions that accompany electrochemical doping/undoping processes. In aceto-nitrile/(a-Bu)4N+BF4, it is found that a significant overpotential accompanies initial oxidation of as-polymerized [Si(Pc)0]n. This can be associated with an ortho rhomb ic- te tr agonal structural transformation. 

Royce W. Murray is Kenan Professor of Chemistry at the University of North Carolina at Chapel Hill. He received his B.S. from Birmingham Southern College in 1957 and his Ph.D. from Northwestern University in 1960. His research areas are analytical chemistry and materials science with specialized interests in electrochemical techniques and reactions, chemically derivatized surfaces in electrochemistry and analytical chemistry, electrocatalysis, polymer films and membranes, solid state electrochemistry and transport phenomena, and molecular electronics. He is a member of the National Academy of Sciences. 

These reactions are solid-state insertion electrochemical processes with coupled electron and ion transfers. Figure 4 includes the standard potential of hex-acyanoferrate in aqueous solution. It is rather surprising that the data for the solid-state insertion electrochemistry and... 

We summarize what is special with these prototype fast ion conductors with respect to transport and application. With their quasi-molten, partially filled cation sublattice, they can function similar to ion membranes in that they filter the mobile component ions in an applied electric field. In combination with an electron source (electrode), they can serve as component reservoirs. Considering the accuracy with which one can determine the electrical charge (10 s-10 6 A = 10 7 C 10-12mol (Zj = 1)), fast ionic conductors (solid electrolytes) can serve as very precise analytical tools. Solid state electrochemistry can be performed near room temperature, which is a great experimental advantage (e.g., for the study of the Hall-effect [J. Sohege, K. Funke (1984)] or the electrochemical Knudsen cell [N. Birks, H. Rickert (1963)]). The early volumes of the journal Solid State Ionics offer many pertinent applications. 

There is an extended special literature3,10-16 on applications of solid state electrochemistry and even more on electrochemical devices. According to our objective, in this section applications will be emphasized in which migration and diffusion in the solid state are decisive processes (as discussed in Part I2). We intend to subsume such applications under the headlines composition sensors, composition actors, and energy storage or conversion devices. 

This volume contains four chapters. The topics covered are solid state electrochemistry devices and techniques nanoporous carbon and its electrochemical application to electrode materials for supercapacitors the analysis of variance and covariance in electrochemical science and engineering and the last chapter presents the use of graphs in electrochemical reaction networks. 

Chapter 1 by Joachim Maier continues the solid state electrochemistry discussion that he began in Volume 39 of the Modem Aspects of Electrochemistry. He begins by introducing the reader to the major electrochemical parameters needed for the treatment of electrochemical cells. In section 2 he discusses various sensors electrochemical (composition), bulk conductivity, surface conductivity, galvanic. He also discusses electrochemical energy storage and conversion devices such as fuel cells. 

Claye AS, Fischer JE, Huffman CB, Rinzler AG, Smalley RE. Solid-state electrochemistry of the Li single wall carbon nanotube system. J Electrochem Soc 2000 147 2845-2852. 

These examples and the general subjects mentioned above illustrate that ion conduction and the electrochemical properties of solids are particularly relevant in solid state ionics. Hence, the scope of this area considerably overlaps with the field of solid state electrochemistry, and the themes treated, for example, in textbooks on solid state electrochemistry [27-31] and books or journals on solid state ionics [1, 32] are very similar indeed. Regrettably, for many years solid state electrochemistry/solid state ionics on the one hand, and liquid electrochemistry on the other, developed separately. Although developments in the area of polymer electrolytes or the use of experimental techniques such as impedance spectroscopy have provided links between the two fields, researchers in both solid and liquid electrochemistry are frequently not acquainted with the research activities of the sister discipline. Similarities and differences between (inorganic) solid state electrochemistry and liquid electrochemistry are therefore emphasized in this review. In Sec. 2, for example, several aspects (non-stoichiometry, mixed ionic and electronic conduction, internal interfaces) are discussed that lead to an extraordinary complexity of electrolytes in solid state electrochemistry. 

The doping of a solid is similar to the enhancement of the H30+ or OH- concentration in water by adding a strong acid or base. However, while in water mobilities of dopant ions are frequently similar to those of the native defects H30+ and OH-[69, 70], dopant ions in solids (e.g. CdXg in AgCl) are almost immobile. This is also why supporting electrolytes (i.e. electrolytes with dissolved dopants that enhance the ionic conductivity, but do not influence electrochemical electrode reactions [71, 72], are unknown in solid state electrochemistry. 

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