CaZr_(0．9)In_(0．1)O_(3-α)高温质子导体管的制备及性质表征

PREPARATION AND CHARACTERIZATION OF HIGH TEMPERATURE PROTON CONDUCTOR TUBE CaZr_(0.9)In_(0.1)O_(3-α)

采用固相反应法合成了高温质子导体CaZr_(0.9)In_(0.1)O_(3-α).XRD分析表明,混合粉体经1673 K×10 h煅烧后形成了预期的钙钛矿结构的CaZrO_3基固溶体.激光粒度分析表明,煅烧后的粉体粒度呈双峰分布,主峰对应0.389-0.584μm,次峰对应3.409-5.867μm,平均粒径为1.878μm.采用热压铸成型并经1823 K×8 h烧结的质子导体管密度为理论密度的97.44%,SEM断口形貌显示其颗粒尺寸在1—3μm之间,结构致密.EDS和电感耦合等离子发射光谱分析(ICP- AES)表明,烧结后的材料中In含量降低.DSC-TG分析表明这是由于在烧结过程中部分In_2O_3升华和离解造成的.CaZr_(0.9)In_(0.1)O_(3-α)在空气氛中931-1300 K范围内的电导率为9.10×10^(-5)-1.21×10^(-2)S/xm,略低于氢气氛下的测定值,但高于CaZr_(097)In_(0.03)O_(3-α)在空气中的测定值,电导激活能为1.47 eV,符合理论预测.

High temperature proton conductor CaZr0.9In0.1O3-α was prepared by solid state reaction. XRD result showed that the powders consisted of the expected perovskite structural CaZrO3- based solid solution after calcining at 1673 K for 10 h. Laser diffraction particle size analysis indicated that the particle size distribution of the calcined powders displayed a bimodal distribution pattern with a high peak in the range of 0.389---0.584 μm and a low peak in the range of 3.409-5.867μm, and the average particle size is 1.878 μm. The relative density of the proton conductor tubes formed by using hot pressure casting reached 97.44% after sintering at 1823 K for 8 h, SEM also showed that the sintered sample is dense and particle size range is 1--3 μm. EDS and ICP-AES analysis revealed that the content of In element decreased in the material after sintering, DSC-TG analysis displayed it is due to the sublimation and dissociation of In2O3 during the sintering. The conductivity range of CaZr0.9In0.1O3-α is 9.10×10^-5-1.21×10^-2S/cm in air, which is little smaller than that in H2 and larger than that of CaZr0.9In0.1O3-α in air in the temperature range of 931--1300 K, and the activation energy is 1.47 eV which is corresponding to the theoretical prediction.