新型高价阳离子导电固体电解质的制备及应用

发布时间：2019-04-22 11:34

【摘要】：高价离子导电固体电解质由于与周围离子的静电引力大,电导率普遍偏低,对具有NASICON型结构的高价离子导体材料进行异种离子掺杂,改善晶体结构和扩展离子传导通道,提高其烧结性能,是增加其离子电导率的有效途径。将具有三维NASICON型结构的三价Al3+离子导电固体电解质中的P位分别用V、Mo、B三种元素进行部分取代,利用高温固相反应法合成了固体电解质(Al0.15Zr0.85)4/3.85Nb P3-x Vx O12(0.0≤x≤0.2)、(Al0.2Zr0.8)(4-x)/3.8Nb P3-x Mox O12(0.0≤x≤0.2)和(Al0.2Zr0.8)(4+2x)/3.8Nb P3-x Bx O12(0.0≤x≤0.2),利用X射线衍射技术(XRD)和扫描电子显微镜技术(SEM)对样品的相组成及微观形貌进行表征,结果表明,制备的固体电解质材料具有三维NASICON型结构,与未掺杂的固体电解质相比,其晶粒连接紧密,致密性明显增强。通过直流极化法测试表明Al3+是主要传导离子,电子传导可忽略不计。利用掺杂制得的固体电解质电性能也得到了极大改善,固体电解质(Al0.15Zr0.85)4/3.85Nb P3-x Vx O12(x=0.1)的电导率600℃下为2.32×10-3 S·cm-1,比未掺杂的(Al0.15Zr0.85)4/3.85Nb(PO4)3提高了将近一个数量级。与未掺杂的铝离子导电固体电解质(Al0.2Zr0.8)4/3.8Nb(PO4)3相比,(Al0.2Zr0.8)(4-x)/3.8Nb P3-x Mox O12(x=0.15)和(Al0.2Zr0.8)(4+2x)/3.8Nb P3-x Bx O12(x=0.1)导电活化能降低,提高了其反应活性,600℃下的电导率分别提高了2.38和1.09倍。以(Al0.15Zr0.85)4/3.85Nb P2.9V0.1O12为固体电解质,Na NO3为敏感材料制备了NO2传感器,150℃为最佳工作温度,且响应稳定性高,抗干扰性能良好。另外,分别以(Al0.2Zr0.8)3.85/3.8Nb P2.85Mo0.15O12和(Al0.2Zr0.8)4.2/3.8Nb P2.9B0.1O12为固体电解质,铝含量为2 wt%的锌铝合金为参比电极制备的铝传感器在500℃下的响应信号较稳定,且响应迅速,其电位响应值与Al含量的对数有良好的线性关系,符合能斯特方程。
[Abstract]:Due to the large electrostatic attraction between the high valence ion conductive solid electrolyte and the surrounding ions, the conductivity is generally low. The high valence ion conductor materials with NASICON structure are doped with different ions to improve the crystal structure and expand the ion conduction channel. Improving its sintering performance is an effective way to increase its ionic conductivity. The P sites in trivalent Al3 ionic conductive solid electrolytes with 3-D NASICON structure were partially replaced by V, Mo and B elements, respectively. Solid electrolyte (Al0.15Zr0.85) 4/3.85Nb P _ 3x Vx O _ 12 (0.0 鈮，

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