Acid electrolytes

Alkaline Fuel Cell. The electrolyte ia the alkaline fuel cell is concentrated (85 wt %) KOH ia fuel cells that operate at high (- 250° C) temperature, or less concentrated (35—50 wt %) KOH for lower (<120° C) temperature operation. The electrolyte is retained ia a matrix of asbestos (qv) or other metal oxide, and a wide range of electrocatalysts can be used, eg, Ni, Ag, metal oxides, spiaels, and noble metals. Oxygen reduction kinetics are more rapid ia alkaline electrolytes than ia acid electrolytes, and the use of non-noble metal electrocatalysts ia AFCs is feasible. However, a significant disadvantage of AFCs is that alkaline electrolytes, ie, NaOH, KOH, do not reject CO2. Consequentiy, as of this writing, AFCs are restricted to specialized apphcations where C02-free H2 and O2 are utilized. 

Specifications for sulfuric acid vary rather widely. Exceptions include the federal specifications for "Sulfuric Acid, Technical" and "Sulfuric Acid, Electrolyte (for storage batteries)" and the Food Chemicals Codex specification for sulfuric acid, frequentiy called food-grade acid (although industrywide, "food-grade" is nonspecific). Very Httie has been done to estabUsh industry-wide analytical standards in the United States, except for development of the ASTM analytical methods, designated as E223-88 and summarized in Table 12. 

An electrorefining plant may operate with either an acid or an alkaline bath. The acid bath contains stannous sulfate, cresolsulfonic or phenolsulfonic acids (to retard the oxidation of the stannous tin in the solution), and free sulfuric acid with P-naphthol and glue as addition agents to prevent tree-like deposits on the cathode which may short-circuit the cells. The concentration of these addition agents must be carefliUy controlled. The acid electrolyte operates at room temperature with a current density of ca 86—108 A/m, cell voltage of 0.3 V, and an efficiency of 85%. Anodes (95 wt % tin) have a life of 21 d, whereas the cathode sheets have a life of 7 d. Anode slimes may be a problem if the lead content of the anodes is high the anodes are removed at frequent intervals and scmbbed with revolving bmshes to remove the slime (7). 

As the reduction of the cathode proceeds through equation 1 and the potential decreases, the reduction equation 2 becomes more favorable. First the divalent Mn(OH)2 is solubili2ed to some extent in the mildly acidic electrolyte. 

In both cases, the hydride ion approaches the double bond from the sterically more accessible side of the molecule. Reduction of imines by metals and acids, electrolytically or by formic acid gives saturated secondary amines (38,255). 

Secondly, absorbent particles such as charcoal and soot are intrinsically inert but have surfaces or infrastructures that adsorb SO, and by either coadsorption of water vapour or condensation of water within the structure, catalyse the formation of a corrosive acid electrolyte solution. Dirt with soot assists the formation of patinae on copper and its alloys by retaining soluble corrosion products long enough for them to be converted to protective, insoluble basic salts. 

Masing, G. and Roth, C., Behaviour of Molybdenum and Nickel and Some Molybdenum-nickel Alloys in Acid Electrolytes , Werkstqffe and Korrosion, 3, 176-186, 253-263 (1952)... 

It is somewhat less corrosion resistant than tantalum, and like tantalum suffers from hydrogen embrittlement if it is made cathodic by a galvanic couple or an external e.m.f., or is exposed to hot hydrogen gas. The metal anodises in acid electrolytes to form an anodic oxide film which has a high dielectric constant, and a high anodic breakdown potential. This latter property coupled with good electrical conductivity has led to the use of niobium as a substrate for platinum-group metals in impressed-current cathodic-protection anodes. 

Hard anodic films, 50-100/rm thick, for resistance to abrasion and wear under conditions of slow-speed sliding, can be produced in sulphuric acid electrolytes at high current density and low temperature. Current densities range from 250 to 1 000 Am , with or without superposed alternating current in 20-100g/1 sulphuric acid at —4—I- 10°C. Under these conditions, special attention must be paid to the contact points to the article under treatment, in order to avoid local overheating. 

Prolonged action of the acid electrolyte on thick films may cause the pores to become conical in section, widening towards the upper surface of the film. This will impose an upper limit on film thickness in solvent electrolytes, as found in practice. 

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... 

Carbon shows reasonable electrocatalytic activity for oxygen reduction in alkaline electrolytes, but it is a relatively poor oxygen electrocatalyst in acid electrolytes. A detailed discussion on the mechanism of... 

In acidic electrolytes only lead, because it forms passive layers on the active surfaces, has proven sufficiently chemically stable to produce durable storage batteries. In contrast, in alkaline medium there are several substances basically suitable as electrode materials nickel hydroxide, silver oxide, and manganese dioxide as positive active materials may be combined with zinc, cadmium, iron, or metal hydrides. In each case potassium hydroxide is the electrolyte, at a concentration — depending on battery systems and application — in the range of 1.15 - 1,45 gem"3. Several elec-... 

Even though zinc-bromine batteries operate with a slightly acidic electrolyte (pH 3), they are discussed here briefly, because... 

If an acid electrolyte is used, water is produced only at the cathode. An example is the phosphoric acid fuel cell ... 

Aluminum has a low density it is a strong metal and an excellent electrical conductor. Although it is strongly reducing and therefore easily oxidized, aluminum is resistant to corrosion because its surface is passivated in air by a stable oxide film. The thickness of the oxide layer can be increased by making aluminum the anode of an electrolytic cell the result is called anodized aluminum. Dyes may be added to the dilute sulfuric acid electrolyte used in the anodizing process to produce surface layers with different colors. 

Ishizaki T, Saito N, Takai O, Asakura S, Goto K, Euwa A (2005) An investigation into the effect of ionic species on the formation of ZnTe from a citric acid electrolyte. Electrochim Acta 50 3509-3516... 

A similar procedure has been used to cathodically deposit lead telluride, PbTe, onto n-Si(lOO) wafers from an acidic electrolyte containing Pb(ll) and Te(IV) species at ambient conditions [106], Rock salt PbTe particles with size from 80 to 180 nm were obtained, distributed randomly on the Si substrate. The mechanism of PbTe nucleation was considered to involve OPD of 3D islands of tellurium followed by lead UPD. The barrier for anodic current formed at the n-Si/PbTe interface rendered the deposition of PbTe irreversible, although high-efficiency photooxidation... 

The energetics of the pyrite interface/electrolyte as given by Ennaoui et al. [159] for indifferent acid electrolyte as well as with redox couples in solution is shown in Fig. 5.10. 

The electrocatalytic oxidation of methanol has been widely investigated for exploitation in the so-called direct methanol fuel cell (DMFC). The most likely type of DMFC to be commercialized in the near future seems to be the polymer electrolyte membrane DMFC using proton exchange membrane, a special form of low-temperature fuel cell based on PEM technology. In this cell, methanol (a liquid fuel available at low cost, easily handled, stored, and transported) is dissolved in an acid electrolyte and burned directly by air to carbon dioxide. The prominence of the DMFCs with respect to safety, simple device fabrication, and low cost has rendered them promising candidates for applications ranging from portable power sources to secondary cells for prospective electric vehicles. Notwithstanding, DMFCs were... 

Recently, rhodium and ruthenium-based carbon-supported sulfide electrocatalysts were synthesized by different established methods and evaluated as ODP cathodic catalysts in a chlorine-saturated hydrochloric acid environment with respect to both economic and industrial considerations [46]. In particular, patented E-TEK methods as well as a non-aqueous method were used to produce binary RhjcSy and Ru Sy in addition, some of the more popular Mo, Co, Rh, and Redoped RuxSy catalysts for acid electrolyte fuel cell ORR applications were also prepared. The roles of both crystallinity and morphology of the electrocatalysts were investigated. Their activity for ORR was compared to state-of-the-art Pt/C and Rh/C systems. The Rh Sy/C, CojcRuyS /C, and Ru Sy/C materials synthesized by the E-TEK methods exhibited appreciable stability and activity for ORR under these conditions. The Ru-based materials showed good depolarizing behavior. Considering that ruthenium is about seven times less expensive than rhodium, these Ru-based electrocatalysts may prove to be a viable low-cost alternative to Rh Sy systems for the ODC HCl electrolysis industry. 

Fhosphoric acid does not have all the properties of an ideal fuel cell electrolyte. Because it is chemically stable, relatively nonvolatile at temperatures above 200 C, and rejects carbon dioxide, it is useful in electric utility fuel cell power plants that use fuel cell waste heat to raise steam for reforming natural gas and liquid fuels. Although phosphoric acid is the only common acid combining the above properties, it does exhibit a deleterious effect on air electrode kinetics when compared with other electrolytes ( ) including such materials as sulfuric and perchloric acids, whose chemical instability at T > 120 C render them unsuitable for utility fuel cell use. In the second part of this paper, we will review progress towards the development of new acid electrolytes for fuel cells. 

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