Electrochemical historical perspectives

Figure 1.3. Fuel cell types and their advantages and disadvantages [8], (Reproduced by permission of ECS-The Electrochemical Society, from Perry ML, Fuller TF. A historical perspective of fuel cell technology in the twentieth century.)...

A historical perspective on impedance spectroscopy is presented in Table 1. A brief listing of advances in this field cannot be comprehensive, and many important contributions are not mentioned. The reader may wish to explore other historical perspectives, such as that provided by Macdonald. Chapters written by Sluyters-Rehbach and Sluyters and by Lasia provide excellent overviews of the field. Nevertheless, Table 1 provides a useful guide to the trends in areas related to electrochemical impedance spectroscopy. These areas include the types of systems investigated, the instrumentation used to make the measurements, including changes in the accessible frequency range, the methods used to represent the resulting data, and the methods used to interpret the data in terms of quantitative properties of the system. 

Most scanning electrochemical microscopy (SECM) experiments are conducted in the amperometric mode, yet microelectrodes have for many years been used as potentiometric devices. Not surprisingly, several SECM articles have described how the tip operated in the potentiometric mode. In this chapter we aim to present the background necessary to understand the differences between amperometric and potentiometric SECM applications. Since many aspects of SECM are covered elsewhere in this monograph, we have focused on the progress made in the held of potentiometric microelectrodes and presented it in the context of SECM experiments. Starting with an historical perspective, the key discoveries that facilitated the development and applications of micro potentiometric probes are highlighted. Fabrication techniques and recipes are reviewed. Basic theoretical principles are covered as well as properties and technical operational details. In the second half of the chapter, SECM potentiometric applications are discussed. There the differences between the conventional amperometric mode are developed and emphasized. 

W.T. Grubb and L.W. Niedrach, Batteries with solid ion-exchange membrane electrolytes. II. Low-temperature hydrogen-oxygen fuel cells, J. Electrochem. Soc., 1969, 107, 131 M.L. Perry and T.F. Fuller, Historical perspective of fuel cell technology in the 20th century, J. Electrochem. Soc., 2002,149, S59-S67. 

In contrast to aromatic moieties, absence of w-resonance for aliphatic compounds results in very low oxidation rates even though the reactions may be favored thermodynamically. StabiUzation of free-radical products from aliphatic compounds can be achieved alternatively via their adsorption to the surface of noble metal electrodes. Unfortunately, adsorption of organic molecules and free radicals also has the consequence of fouling of the electrode and loss of its activity [57]. The historical perspective of nonreactivity for ahphatic compounds at noble metal electrodes can be attributed to surface fouling as a result of high, but transient, catalytic activity. An alternative approach is to combine electrochemical detection with on-hne cleaning. Hence, in order to maintain uniform and reproducible electrode activity at noble metal electrodes for polar aliphatic compounds. 

Feldberg, S.W. (2004) Simulation of electroanalytical systems 1962-2002. A personal perspective from ad hoc simulations to a generalized simulator, in Historical Perspectives on the Evolution of Electrochemical Tools (eds J. Leddy, R Vanysek and V. Birss), The Electrochemical Society, New Jersey, USA, p. 191. 

Perry ML, Fuller TF. A historical perspective of fuel cell technology in the 20th Century. J Electrochem Soc 2002 149 S59-67. 

Prediction of salt electrochemical stability in the context of Li-ion batteries has mainly involved predicting the Eox of novel lithium salt anions, frequently without any focus on the subsequent decomposition reaction products and mechanisms. However, with recent results on oxidation promoted solvent-anion reactions [57] and the rapid development of solvent-free ionic liquid (IL) electrolytes, investigations of both anion and cation decomposition products are foreseen by us to become more frequent and important - particularly in connection with the passivation phenomena at the negative electrode. As for solvents, we will here follow the historical development of studies and methods, followed by some more recent works that together with our remarks outline our perspective on the future. 

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