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Artigo Científico | Termodinâmica | Inglês | 14/01/2004
Autores: Luiz Fernando Brum Malta, Tsuneharu Ogasawara
Palavras-chave: anode reaction, ceria electrolytes, degradation of ceria, sofcs
Resumo: This work is concerned with thermodynamic analysis of the stability of some ceria electrolytes under contact with hydrogen gas nearby anode in fuel cells. It was considered the following types of ceria-electrolytes: pure ceria, strontium-doped ceria, calcium-doped ceria and calcium-bismuth-doped ceria. The equilibrium Log (pH2O/pH2) vs. T diagrams were constructed for x = 0.1 and 0.01, where x is the fraction of initial ceria converted to Ce2O3 (proportional to the ratio between activities of Ce3+ and Ce4+ in the ceria electrolyte, which is proportional to the fraction of electronic conduction in the electrolyte at a given temperature). The predictions of the diagrams are as follows: (a) Ce1.9Ca0.1Bi0.8O5.1 and Ce0.9Sr0.1O1.9 are less stable than pure ceria for the whole temperature range (from 0 to 1000 °C); (b) Ce0.9Ca0.1O1.9 is more stable than pure ceria below about 650 °C for x = 0.1 and below about 400 °C for x = 0.01; (c) at each temperature in the considered range the pressure ratio pH2O(g)/pH2(g) has to be higher than thermodynamically predicted in order to keep CeO2 stable in the electrolyte contacting hydrogen gas. Thermodynamic predictions are entirely capable of explaining experimental data published on the subject (irreversible cell degradation in the case of SrO-doped ceria; weight loss from doped-ceria electrolyte above 700 °C; oxygen gas release during sintering of ceria).
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