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Mn掺杂的NaxCoO2多晶制备与电输运性质研究

Lan YU,Guo-wen YAN,Yu-kun LIU,Tai-ping SHAO,Peng-xiang ZHANG,Jia-lin SUN

Gongneng Cailiao/Journal of Functional Materials（2011）

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Abstract
采用固相反应法制备了沿(00l)面高度择优取向的γ相NaxCoO2(X=0.5+δ,0.7)和Na0.5+δCo0.95Mn0.05O2系列多晶,且微量Mn掺杂阻碍了晶粒的长大.77～300K电阻率-温度曲线表明,NaγCoO2为金属的电输运行为,在相同烧结工艺下,Mn掺杂导致Na0.5+δCo0.95Mn0.05O2电阻率有很大提高且为绝缘体行为,但经920℃/10h进一步烧结后,转变为电阻率大大降低的金属行为.分析认为,Mn4+的3d轨道交叠能带e'g+a1g的电子数比Co3.5+少,使得载流子数量降低;并且Mn4+的t2g轨道的电子最高占据能级比Co3.5+低,使电子在Mn4+和Co3+/Co4+之间跃迁时存在能隙,从而电子跃迁几率降低,载流子局域化.晶界增多导致的晶界散射,也增加了电阻率.
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3d electron orbital,Curve of resistivity vs temperature,Na 0.5+δ Co 0.95Mn 0.05O 2,Na xCoO 2,X-ray diffraction
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