Alkaline electrolytes, electrodes

Flartinger S, Pettinger B and Dobihofer K 1995 Cathodic formation of a hydroxyl adsorbate on copper (111) electrodes in alkaline electrolyte J. Electroanal. Chem. 397 335-8... 

It is so universally applied that it may be found in combination with metal oxide cathodes (e.g., HgO, AgO, NiOOH, Mn02), with catalytically active oxygen electrodes, and with inert cathodes using aqueous halide or ferricyanide solutions as active materials ("zinc-flow" or "redox" batteries). The cell (battery) sizes vary from small button cells for hearing aids or watches up to kilowatt-hour modules for electric vehicles (electrotraction). Primary and storage batteries exist in all categories except that of flow-batteries, where only storage types are found. Acidic, neutral, and alkaline electrolytes are used as well. The (simplified) half-cell reaction for the zinc electrode is the same in all electrolytes ... 

Despite the fact that the zinc/ ferricyanide system employs an alkaline electrolyte, the electrode reactions are quite similar to those in zinc/halogen batteries and battery constructions are usually bipolar too. 

Several significant electrode potentials of interest in aqueous batteries are listed in Table 2 these include the oxidation of carbon, and oxygen evolution/reduction reactions in acid and alkaline electrolytes. For example, for the oxidation of carbon in alkaline electrolyte, E° at 25 °C is -0.780 V vs. SHE or -0.682 V (vs. Hg/HgO reference electrode) in 0.1 molL IC0 2 at pH [14]. Based on the standard potentials for carbon in aqueous electrolytes, it is thermodynamically stable in water and other aqueous solutions at a pH less than about 13, provided no oxidizing agents are present. 

In acid electrolytes, carbon is a poor electrocatalyst for oxygen evolution at potentials where carbon corrosion occurs. However, in alkaline electrolytes carbon is sufficiently electrocatalytically active for oxygen evolution to occur simultaneously with carbon corrosion at potentials corresponding to charge conditions for a bifunctional air electrode in metal/air batteries. In this situation, oxygen evolution is the dominant anodic reaction, thus complicating the measurement of carbon corrosion. Ross and co-workers [30] developed experimental techniques to overcome this difficulty. Their results with acetylene black in 30 wt% KOH showed that substantial amounts of CO in addition to C02 (carbonate species) and 02, are... 

The reason for this limited cycle life is the high solubility of the zinc electrode in alkaline electrolyte the zincate ions formed are deposited again during the subsequent charging in the form of dendrites, i.e., of fernlike crystals. They grow in the direction of the counterelectrode and finally cause shorts. 

Figure 17. PMC behavior in the accumulation region, (a) PMC potential curve and photocurrent-potential curve (dashed line) for silicon (dotted with Pt particles) in contact with propylene carbonate electrolyte containing ferrocene.21 (b) PMC potential curve and photocurrent-potential curve (dashed line) for a sputtered ZnO layer [resistivity 1,5 x 103 ft cm, on conducting glass (ITO)] in contact with an alkaline electrolyte (NaOH, pH = 12), measured against a saturated calomel electrode.22...

Metallic zinc was used as a material for the negative electrode in the earliest electrical cell, Volta s pile, and is still employed in a variety of batteries, including batteries with alkaline electrolytes. 

In topochemical reactions all steps, including that of nucleation of the new phase, occur exclusively at the interface between two solid phases, one being the reactant and the other the product. As the reaction proceeds, this interface gradually advances in the direction of the reactant. In electrochemical systems, topochemical reactions are possible only when the reactant or product is porous enough to enable access of reacting species from the solution to each reaction site. The number of examples electrochemical reactions known to follow a truly topochemical mechanism is very limited. One of these examples are the reactions occurring at the silver (positive) electrode of silver-zinc storage batteries (with alkaline electrolyte) ... 

Gold is generally considered a poor electro-catalyst for oxidation of small alcohols, particularly in acid media. In alkaline media, however, the reactivity increases, which is related to that fact that no poisoning CO-hke species can be formed or adsorbed on the surface [Nishimura et al., 1989 Tremihosi-Filho et al., 1998]. Similar to Pt electrodes, the oxidation of ethanol starts at potentials corresponding to the onset of surface oxidation, emphasizing the key role of surface oxides and hydroxides in the oxidation process. The only product observed upon the electrooxidation of ethanol on Au in an alkaline electrolyte is acetate, the deprotonated form of acetic acid. The lack of carbon dioxide as a reaction product again suggests that adsorbed CO-like species are an essential intermediate in CO2 formation. 

OHads formation has a clear voltammetric signature on a number of surfaces, including the (lll)-oriented surfaces of platinum group metals, Pt(lll) in alkaline and acid electrolytes of non-adsorbing anions [Markovic and Ross, 2002], and Au(lll), Au(lOO), and Ag(lll) in neutral and alkaline electrolytes [Savinova et al., 2002]. On these surfaces, the reaction has a reversible character. Anderson and co-workers calculated the reversible potential of Reaction (9.1) on Pt to be 0.62 V with respect to a reversible hydrogen electrode (RHE) [Anderson, 2002]. The Pt(lll)-OH bond energy has been estimated to be about 1.4 eV in an alkaline electrolyte [Markovic and Ross, 2002]. 

In 1899, the nickel-cadmium battery, the first alkaline battery, was invented by a Swedish scientist named Waldmar Jungner. The special feature of this battery was its potential to be recharged. In construction, nickel and cadmium electrodes in a potassium hydroxide solution, it was the first battery to use an alkaline electrolyte. This battery was commercialized in Sweden in 1910 and reached the Unites States in 1946. The first models were robust and had significantly better energy density than lead-acid batteries, but nevertheless, their wide use was limited because of the high costs. 

Aqueous, alkaline fuel cells, as used by NASA for supplemental power in spacecraft, are intolerant to C02 in the oxidant. The strongly alkaline electrolyte acts as an efficient scrubber for any C02, even down to the ppm level, but the resultant carbonate alters the performance unacceptably. This behavior was recognized as early as the mid 1960 s as a way to control space cabin C02 levels and recover and recycle the chemically bound oxygen. While these devices had been built and operated at bench scale before 1970, the first comprehensive analysis of their electrochemistry was put forth in a series of papers in 1974 [27]. The system comprises a bipolar array of fuel cells through whose cathode chamber COz-containing air is passed. The electrolyte, aqueous Cs2C03, is immobilized in a thin (0.25 0.75 mm) membrane. The electrodes are nickel-based fuel cell electrodes, designed to be hydrophobic with PTFE. 

Gamburzev S., Iliev I., Kaisheva A., Steinberg G., Mokrousov L., Behaviour of carbon wetproofed electrodes during long-term operation in alkaline electrolyte, Elektrokhilija, 1980 16 1069-72. 

Sucessful application of the air electrode requires solving some key problems the air electrode catalyst, the alkaline electrolyte carbonization, the oxygen reaction with anode materials, an influence of an air humidity on an electrode behavior. 

C02 is produced as the primary product and this precludes the use of alkaline electrolytes due to the precipitation of CO - in the pores of the anode and consequent electrode fouling. Acid electrolytes lead to problems of corrosion and slow kinetics for the reduction of 02 at the air cathode. 

If aluminum is present on the electrode (for example if used for interconnects), an ammonium fluoride-based electrolyte is more desirable than HF, because A1 is only stable in the pH range of about 4 to 8.5 [Oh4]. Note that PS formation is observed in ammonium fluoride-based electrolytes [Ku5], as well as in water-free mixtures of acetonitrile and HF [Ril, Pr7], but not in alkaline electrolytes. 

Fig. 3.1 The I—V characteristic of (a) a p-type and (b) an n-type silicon electrode under the assumption that the current is dominated by the properties of the semiconductor and is not limited by interface reactions or by diffusion in the electrolyte, (c) The characteristic I—V curve in an alkaline electrolyte under the...

In the next section the charge states of the electrode and the electrochemical reactions are discussed for acidic, especially fluoride-containing electrolytes followed by a section dealing with alkaline electrolytes. 

There are fewer studies devoted to the electrochemistry of silicon in alkaline electrolytes than is the case for HF. This can partly be ascribed to the fact that pore formation is not observed in alkaline electrolytes, which limits the field of applications. This section gives a brief overview of the characteristic features of I-V curves of silicon electrodes in alkaline electrolytes. 

In contrast to acidic electrolytes, chemical dissolution of a silicon electrode proceeds already at OCP in alkaline electrolytes. For cathodic potentials chemical dissolution competes with cathodic reactions, this commonly leads to a reduced dissolution rate and the formation of a slush layer under certain conditions [Pa2]. For potentials slightly anodic of OCP, electrochemical dissolution accompanies the chemical one and the dissolution rate is thereby enhanced [Pa6]. For anodic potentials above the passivation potential (PP), the formation of an anodic oxide, as in the case of acidic electrolytes, is observed. Such oxides show a much lower dissolution rate in alkaline solutions than the silicon substrate. As a result the electrode surface becomes passivated and the current density decreases to small values that correspond to the oxide etch rate. That the current density peaks at PP in Fig. 3.4 are in fact connected with the growth of a passivating oxide is proved using in situ ellipsometry [Pa2]. Passivation is independent of the type of cation. Organic compounds like hydrazin [Sul], for example, show a behavior similar to inorganic ones, like KOH [Pa8]. Because of the presence of a passivating oxide the current peak at PP is not observed for a reverse potential scan. 

The charge states of the silicon electrode in alkaline electrolytes have not been investigated in detail. It can be assumed that the electrode represents an MIS structure above PP, while it behaves similarly to a Schottky junction for potentials below PP. 

At higher anodic potentials an anodic oxide is formed on silicon electrode surfaces. This leads to a tetravalent electrochemical dissolution scheme in HF and to passivation in alkaline electrolytes. The hydroxyl ion is assumed to be the active species in the oxidation reaction [Drl]. The applied potential enables OH to diffuse through the oxide film to the interface and to establish an Si-O-Si bridge under consumption of two holes, according to Fig. 4.4, steps 1 and 2. Details of anodic oxide formation processes are discussed in Chapter 5. This oxide film passivates the Si electrode in aqueous solutions that are free of HF. 

In alkaline electrolytes, in contrast, silicon is readily dissolved at OCP. Under cathodic conditions the dissolution becomes reduced, while under low anodic potentials the dissolution rate is enhanced compared to the OCP rate. If, however, the anodic potential becomes larger than the PP, the silicon electrode is passivated due to a thin anodic oxide film and the dissolution rate becomes negligible. The current density needed to keep the electrode in the passive state corresponds to the dissolution rate of the anodic oxide in the alkaline electrolyte used and is usually very low. 

If a silicon electrode is anodically oxidized in an acidic electrolyte free of HF, the oxide thickness increases monotonically with anodization time. This is also true for alkaline electrolytes if the oxide formation rate exceeds the slow chemical dissolution of the anodic Si02. This monotonic behavior, however, is not necessarily associated with monotonic current-time or potential-time curves. 

The cells shown in Figs. 28 and 29 all operate according to the same principles, which have been developed by Arup. The interior of the cell acts as the anode chamber, and a metal oxide cathode placed inside the cell in an alkaline electrolyte acts as the counter electrode. The hydrogen flux across the integrated membrane (coated with palladium on the internal surface) can be measured as the potential drop across a resistor placed between the membrane and the counter electrode. 

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