Corrosion lithiated carbons

The excess charge consumed in the first cycle is generally ascribed to SEI formation and corrosion-like reactions of Li C6[19, 66, 118-120]. Like metallic lithium and Li-rich Li alloys, lithiated graphites, and more generally lithiated carbons are thermodynamically unstable in all known electrolytes, and therefore the surfaces which are exposed to the electrolyte have to be kinetically protected by SEI films (see Chapter III, Sec.6). Neverthe-... 

Electrodes The electrocatalytic material of an MCFC is nickel. The cathode becomes oxidized and lithiated during the first hours of the operation. Nickel oxide is soluble in molten carbonates thus in the course of the operation two undesirable effects may occur (1) metallic nickel particles are formed in the electrolyte which can lead to an electronic short circuit of the electrodes, (2) the size of the cathode diminishes. Two approaches have been proposed for solving these problems the use of less corrosive molten carbonate mixtures and more stable cathodes containing iron and cobalt. The nickel anodes usually contain chromium, which promotes the sintering process. 

The two types of high temperature fuel cell are quite different from each other (Table 6). The molten carbonate fuel cell, which operates at 650°C, has a metal anode (nickel), a conducting oxide cathode (e.g. lithiated NiO) and a mixed Li2C03/K2C03 fused salt electrolyte. Sulphur attack of the anode, to form liquid nickel sulphide, is a severe problem and it is necessary to remove H2S from the fuel gas to <1 ppm or better. However, CO is not a poison. Other materials science problems include anode sintering and degradation, corrosion of cell components and evaporation of the electrolyte. Work continues on this fuel cell in U.S.A. and there is some optimism that the problem will be solved within 10 years. 

The search for effective electrocatalysts led to investigations of the corrosive resistance and of the reactivity for the O2 reduction of compounds of metals with other elements like boron, carbon, nitrogen, oxygen, etc. The cathode [78] of the Bacon cell represents the classical example. The porous cathodes were made by pressing and sintering mixtures of carbonyl nickel and ammonium bicarbonate. Subsequently, they were coated with a layer of lithiated nickel oxide. 

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