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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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Impact of volatility, non‐stoichiometry, and atmospheres in perovskite piezoelectric and dielectric materials
Abstract Defect chemistry that results in the thermal processing of dielectric and piezoelectric films, crystals and ceramics ultimately controls the properties and long‐term performance of materials and devices. This paper reviews several thermochemical defect reactions using important perovskite base composition dielectrics including Pb(Zr,Ti)O3, (Na,K)NbO3, (Bi0.5Na0.5)TiO3‒BaTiO3, and Ca(Hf,Ti,Mn)O3. Within this group of perovskite‐based functional materials, we note ways the point defects can be formed to create non‐stoichiometric compositions changing the overall cation‐to‐anion ratios during the synthesis process. These reactions can be developed with the loss of volatile species such as metal and oxygen ions. The relative concentrations of these can impact the over conductions in terms of the mixed contributions of ionic conductivity from the oxygen vacancies and the electronic conductivity, along with microstructure and properties in some cases.
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- Award ID(s):
- 1841453
- PAR ID:
- 10535218
- Publisher / Repository:
- Wiley-Blackwell
- Date Published:
- Journal Name:
- Journal of the American Ceramic Society
- Volume:
- 107
- Issue:
- 12
- ISSN:
- 0002-7820
- Format(s):
- Medium: X Size: p. 7921-7938
- Size(s):
- p. 7921-7938
- Sponsoring Org:
- National Science Foundation
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