Improvement of ionic conductivity in A-site lithium doped sodium bismuth titanate

• Published in: Solid state ionics Vol. 317; pp. 32 - 38
• Main Authors: Shih, Duke P.C., Aguadero, Ainara, Skinner, Stephen J.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.04.2018; Elsevier BV
• Subjects: Atmospheres; Bismuth titanate; Bonding strength; Conductivity; Conductors; Current carriers; Data acquisition; Diffusion barriers; Doping; Electric properties; Electrical properties; Electrical resistivity; Ion currents; Lithium; Mass spectrometry; Non-stoichiometry; Oxide-ion conductors; Oxygen diffusion; Oxygen ions; Self diffusion; Sodium bismuth titanate; Solid oxide fuel cells; Vacancies; Oxide-ion conductors; Non-stoichiometry; Oxygen diffusion; Sodium bismuth titanate; Doping
• ISSN: 0167-2738; 1872-7689
• DOI: 10.1016/j.ssi.2018.01.003

Oxide-ion conductors play a significant role in various applications such as solid oxide fuel cells (SOFCs), oxygen separation membranes and sensors. Recently, high ionic conductivity (~1×10−4Scm−1 at 600°C) was found in sodium bismuth titanate (NBT), which originates from oxygen vacancies compensating the introduced Bi-deficiency. By providing pathways with low diffusion barriers, the highly polarizable Bi3+ ions with 6s2 lone pair electrons and weak BiO bonds are also beneficial for the migration of oxygen ions. Here we report the influence of lithium doping on the electrical properties of NBT. The optimal doping level of 4at% Li on the Bi-site improves the ionic conductivity by one order of magnitude to ~7×10−3Scm−1 at 600°C without changing the conduction mechanism, which could be attributed to an increase in the oxygen vacancy concentration based on an acceptor doping mechanism. A further increase in Li content does not improve the total conductivity. Oxygen diffusion data were acquired by the Isotope Exchange Depth Profile (IEDP) method in combination with Secondary Ion-Mass Spectrometry (SIMS). The oxygen self-diffusion coefficients (e.g. 7.04×10−9cm2s−1 at 600°C) are in excellent agreement with the values derived from impedance spectroscopy data, suggesting that the oxygen ions are the main charge carriers in the system. Furthermore, a degradation test was performed for 100h under a variety of atmospheres, showing only a slight decrease in conductivity in both air and oxygen atmospheres attributed to the loss of material from the A-site. Comparison with other oxide-ion conductors indicates that Li-doped NBT materials are promising candidates for intermediate temperature SOFC applications. •Replacement of Bi3+ with Li+ on (Na,Bi)TiO3 A-site enhances total conductivity without changing the conduction mechanism.•The improved conductivity is mainly attributed to an increase in the oxygen vacancy concentration.•Optimal doping level of 4 at% improves electrical conductivity and oxygen self-diffusion by over one order of magnitude.•Li-doped NBT exhibits ionic conductivity comparable to other oxide-ion conductors at temperatures above 600°C.