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本文采用吸收-解吸氧的方法测定了CaO-ZrO_2在氧压10~(-8)～1.0大气压范围内的过剩氧浓度,实验研究了影响过剩氧浓度的各种因素:氧压,温度,掺杂氧化物及杂质。结果表明,具有变价的过渡金属氧化物是该材料过剩氧浓度的决定因素。关于电子正孔扑捉模型的假设从实验上得到了证实。在本文条件下电子正孔的扑捉中心是Fe″Z r。过剩氧浓度随温度升高而升高。氧在该陶瓷的溶解热为191 kJ/mole。利用晶体缺陷热力学平衡导出了电子正孔浓度与氧压的依赖关系,在恒温下电子正孔总浓度正比于Po_2~(1/4),理论表达式与实验测量结果一致。本文的发现对于改进固体电解质的响应时间具有重要意义。
In this paper, the excess oxygen concentration of CaO-ZrO 2 in the pressure range of 10-8 (-8) ~ 1.0 was measured by the method of absorption-desorption of oxygen. Various factors influencing the excess oxygen concentration were experimentally studied: oxygen pressure, temperature, Doping oxides and impurities. The results show that the transition metal oxide with a variable price is the determinant of the excess oxygen concentration of the material. Assumptions about the electronic positive hole capture model have been experimentally confirmed. In this paper, the center of electron hole capture is Fe "Z r. The excess oxygen concentration increases with increasing temperature. The heat of dissolution of oxygen in this ceramic is 191 kJ / mole. The thermodynamic equilibrium of crystal defects is used to derive the electron positive The dependence of pore concentration and oxygen pressure on the oxygen concentration is proportional to Po_2 ~ (1/4) at constant temperature, and the theoretical expression is consistent with the experimental results. The findings of this paper are of great significance for improving the response time of solid electrolyte.