Non-metallic Electrode Materials

The form in which these materials are used for electrochemistry ranges from a pressed or sintered disc of the powdered material to the technique developed by Tseung in which the catalyst, which may be prepared by freeze drying, or other materials, is mixed with PTFE dispersion and coated onto a metal mesh which acts both as support and electrical conductor to the material. 

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Polymers have served roles in PEM fuel cell cathodes such as modifiers to macrocycle-based electrodes to improve conductivity and stability,165 composite materials with heteropolyacids,166 and as precursors to pyrolyzed catalysts.38,112,132,133 However, as discussed in the previous section, the activity of nitrogen-containing carbon raises the possibility of non-metal electrodes functioning in a cathode environment. Likewise, researchers have noted ORR activity for various conducting polymers containing nitrogen, and recently studies on their potential use in PEM fuel cell cathodes have been reported. 

The insulation around the central electrode is an example of a non-metallic material - in this case, alumina, a ceramic. This is chosen because of its electrical insulating properties and because it also has good thermal fatigue resistance and resistance to corrosion and oxidation (it is an oxide already). 

The semi-consumable electrodes, as the name implies, suffer rather less dissolution than Faraday s law would predict and substantially more than the non-consumable electrodes. This is because the anodic reaction is shared between oxidising the anode material (causing consumption) and oxidising the environment (with no concomitant loss of metal). Electrodes made from silicon-iron, chromium-silicon-iron and graphite fall into this category. 

In electroluminescence devices (LEDs) ionized traps form space charges, which govern the charge carrier injection from metal electrodes into the active material [21]. The same states that trap charge carriers may also act as a recombination center for the non-radiative decay of excitons. Therefore, the luminescence efficiency as well as charge earner transport in LEDs are influenced by traps. Both factors determine the quantum efficiency of LEDs. 

Kohei Uosaki received his B.Eng. and M.Eng. degrees from Osaka University and his Ph.D. in Physical Chemistry from flinders University of South Australia. He vas a Research Chemist at Mitsubishi Petrochemical Co. Ltd. from 1971 to 1978 and a Research Officer at Inorganic Chemistry Laboratory, Oxford University, U.K. bet veen 1978 and 1980 before joining Hokkaido University in 1980 as Assistant Professor in the Department of Chemistry. He vas promoted to Associate Professor in 1981 and Professor in 1990. He is also a Principal Investigator of International Center for Materials Nanoarchitectonics (MANA) Satellite, National Institute for Materials Science (NIMS) since 2008. His scientific interests include photoelectrochemistry of semiconductor electrodes, surface electrochemistry of single crystalline metal electrodes, electrocatalysis, modification of solid surfaces by molecular layers, and non-linear optical spectroscopy at interfaces. 

Initial development of ambient secondary lithium batteries was based on the primary lithium systems described in Chapter 4, consisting of a lithium metal negative, a non-aqueous lithium ion conducting electrolyte and a positive electrode material which could undergo a reversible electrochemical reaction with lithium ions ... 

In certain cases and together with the electrode reaction, in particular that of oxygen reduction at metal surfaces, a non-electrochemical regeneration mechanism operates which is heterogeneous in nature and involves the adsorbed product [165] obviously, it is very dependent on the electrode material and the available surface states. The reaction scheme is thus of the type... 

What can we do for reversible (non polarizable) electrodes In this case we use the fact that different processes occur at different timescales. Instead of the relatively slow change of the voltage in cyclic voltametry, AC potentials with varying frequencies are applied and the current is detected. The method is called impedance spectroscopy. Using impedance spectroscopy, even semiconducting [100] or insulating materials can be analysed by coating them onto metallic electrodes. 

Thus, to perform a reduction of a difficultly reducible substrate in a water-containing system one would normally prefer a metal like Pb, Zn, or Hg, whereas for difficult oxidations Au or Pt would be the anode material of choice. In non-aqueous SSE s the choice of electrode material is not critical from this point of view. 

Fig. 6.18 illustrates the apparatus used. A metal cell (cylindrical tube) was placed in the centrifugal bed (1). A metal electrode (3) was put into the metal cell through a lid (2) made of non-conducting material. The surface of the metal cell served as a second electrode. 

Variation in the metal surface composition is, then, generally expected to yield large variations in the observed rate constant for inner-sphere pathways since the reaction energetics will be sensitive to the chemical nature of the metal surface. For outer-sphere reactions, on the other hand, the rate constants are anticipated to be independent of the electrode material after correction for electrostatic work terms provided that adiabatic (or equally non-adiabatic) pathways are followed. Although a number of studies of the dependence of the rate constants for supposed outer-sphere reactions on the nature of the electrode material have been reported, relatively few refer to sufficiently well-defined conditions where double-layer corrections are small or can be applied with confidence [111-115]. Several of these studies indeed... 

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