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 (sodium ions, holes, electrons, oxygen ions, protons). Our results showed that the lattice-enlarged NLZ and NLBZ exhibited ∼19× (conventional sintering)/49× (spark plasma sintering) and ∼7× higher Na-ion conductivities, respectively, compared to unexpanded Na 0.42 La 0.525 TiO 3 . Moreover, the Na-ion conductivity of Na 0.5 La 0.5 ZrO 3 is comparable with that of NaNbO 3 , despite having half the carrier concentration. Additionally, more than 96% of the total conductivity in dry conditions was contributed by sodium ions for both compositions, with negligible electronic conductivity and little oxygen ion conductivity. We also identified factors that limited Na-ion transport: NLZ and NLBZ were both challenging to densify using conventional sintering without the loss of Na because of its volatility. With spark plasma sintering, higher density can be achieved. In addition, the NLZ perovskite phase appeared unable to accommodate significant Na deficiency, whereas NLBZ allowed some. Density functional theory calculations supported a thermodynamic limitation to creation of Na-deficient NLZ in favor of a pyrochlore-type phase. Humid environments generated different behavior: in Na 0.25 La 0.25 Ba 0.5 ZrO 3 , incorporated protons raised total conductivity, whereas in Na 0.5 La 0.5 ZrO 3 , they lowered total conductivity. Ultimately, this systematic approach revealed both effective approaches and limitations to achieving super-ionic Na-ion conductivity, which may eventually be overcome through alternative processing routes.
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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 failure. The successful combination of the two methods enables us to have an overview of how the oxygen vacancy dynamics in the BNT– x BT system depends upon the phase nature or the domain structure.
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- PAR ID:
- 10287708
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- ISSN:
- 2050-7526
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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