Na-ion conducting solid electrolytes can enable both the enhanced safety profile of all-solid-state-batteries and the transition to an earth-abundant charge-carrier for large-scale stationary storage. In this work, we developed new perovskite-structured Na-ion conductors from the analogous fast Li-ion conducting Li 3 x La 2/3− x TiO 3 (LLTO), testing strategies of chemo-mechanical and defect engineering. Na x La 2/3−1/3 x ZrO 3 (NLZ) and Na x La 1/3−1/3 x Ba 0.5 ZrO 3 (NLBZ) were prepared using a modified Pechini method with varying initial stoichiometries and sintering temperatures. With the substitution of larger framework cations Zr 4+ and Ba 2+ on B- and A-sites respectively, NLZ and NLBZ both had larger lattice parameters compared to LLTO, in order to accommodate and potentially enhance the transport of larger Na ions. Additionally, we sought to introduce Na vacancies through (a) sub-stoichiometric Na : La ratios, (b) Na loss during sintering, and (c) donor doping with Nb. AC impedance spectroscopy and DC polarization experiments were performed on both Na 0.5 La 0.5 ZrO 3 and Na 0.25 La 0.25 Ba 0.5 ZrO 3 in controlled gas environments (variable oxygen partial pressure, humidity) at elevated temperatures to quantify the contributions of various possible charge carriers (sodiummore »
An overview of oxygen vacancy dynamics in (1 − x )(Bi 1/2 Na 1/2 )TiO 3 – x BaTiO 3 solid solution
(Bi 1/2 Na 1/2 )TiO 3 (BNT) based ceramics have been the hot topic for a few years because of their multiple functions, from the piezoelectric properties to more recently the electrostatic energy storage performance. However, some basic issues are still unclear, preventing their wide application in real devices. One of them is the underlying conduction mechanism, the interplay of electronic and ionic carriers as a mixed ionic case and the subsequent quantification. This paper deals with the most basic compositions, which are the typical ones from the (1 − x )(Bi 1/2 Na 1/2 )TiO 3 – x BaTiO 3 (BNT– x BT) phase diagram. The conductivity is primarily investigated by impedance spectroscopy, while different equivalent circuits are applied to different conduction mechanisms. A transition from predominantly ionic to predominantly electronic conduction is revealed to occur with the increase in BaTiO 3 concentration. The mixed ionic–electronic conduction in the composition near the morphotropic phase boundary, namely BNT–7%BT, is identified and then quantified. To verify our interpretation of impedance results, dc degradation is, for the first time, conducted in this family of materials, from which the electronic and ionic conductions can be easily separated by accessing the mean time to more »
- Publication Date:
- NSF-PAR ID:
- 10287708
- Journal Name:
- Journal of Materials Chemistry C
- ISSN:
- 2050-7526
- Sponsoring Org:
- National Science Foundation
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