Working electrode materials, potential range

Table 4.5. Working potential ranged" of different working electrode materials [.59].

The limited anodic potential range of mercury electrodes has precluded their utility for monitoring oxidizable compounds. Accordingly, solid electrodes with extended anodic potential windows have attracted considerable analytical interest. Of the many different solid materials that can be used as working electrodes, the most often used are carbon, platinum, and gold. Silver, nickel, and copper can also be used for specific applications. A monograph by Adams (17) is highly recommended for a detailed description of solid-electrode electrochemistry. 

The guiding criterion for the choice of a working electrode is that it must be made of a redox-inert material, at least in the potential range of interest. 

The working electrodes found to be useful at room temperature can also be used at low temperature. There are no special constraints. Platinum is probably the most widely used, simply because it is the most common electrode material for room-temperature work. A mercury electrode can also be employed, either as a hanging mercury drop electrode (HMDE) [23], a thin mercury film on a solid support, or an amalgam [26]. The HMDE was reported to extend the range of usable potentials to somewhat more negative values than found with platinum [23]. Of course, below -39°C, the HMDE is actually a solid electrode however, no detectable change in its voltammetric behavior is noted at the phase transition. 

The electrochemical window of pure molten cryolite has not been expressly stated, but a voltammogram of purified cryolite recorded at a graphite working electrode exhibits very little residual current over the range of potentials extending from 0.4 to -1.9 V vs. a nickel wire quasi-reference electrode [7]. Physical property data for molten cryolite and phase equilibria for the AlF3-NaF melt system have been summarized [31,32]. The extremely high temperature of cryolite places severe constraints on the materials that can be used for cells. Platinum and boron nitride are the materials of choice. 

As the capacity of the two electrodes is different, even in a symmetric capacitor, Equation 8.1 indicates that the value of C is determined by the electrode with the smallest capacity value. Moreover, the later electrode operates in a larger potential window than the other one, which consequently reduces the voltage range of the device. This drawback can be circumvented by balancing the respective masses of the electrodes or by using, for each electrode, different materials working in their optimal potential range. 

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