Vertically aligned nanocomposite (VAN) thin films have shown strong potential in oxide nanoionics but are yet to be explored in detail in solid-state battery systems. Their 3D architectures are attractive because they may allow enhancements in capacity, current, and power densities. In addition, owing to their large interfacial surface areas, the VAN could serve as models to study interfaces and solid-electrolyte interphase formation. Here, we have deposited highly crystalline and epitaxial vertically aligned nanocomposite films composed of a Li x La 0.32±0.05 (Nb 0.7±0.1 Ti 0.32±0.05 )O 3±δ -Ti 0.8±0.1 Nb 0.17±0.03 O 2±δ -anatase [herein referred to as LL(Nb, Ti)O-(Ti, Nb)O 2 ] electrolyte/anode system, the first anode VAN battery system reported. This system has an order of magnitude increased Li + ionic conductivity over that in bulk Li 3x La 1/3−x NbO 3 and is comparable with the best available Li 3x La 2/3−x TiO 3 pulsed laser deposition films. Furthermore, the ionic conducting/electrically insulating LL(Nb, Ti)O and electrically conducting (Ti, Nb)O 2 phases are a prerequisite for an interdigitated electrolyte/anode system. This work opens up the possibility of incorporating VAN films into an all solid-state battery, either as electrodes or electrolytes, by the pairing of suitable materials.
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High ionic conductivity in fluorite δ-bismuth oxide-based vertically aligned nanocomposite thin films
δ-Bi 2 O 3 has long been touted as a potential material for use in solid oxide fuel cells (SOFC) due to its intrinsically high ionic conductivity. However, its limited operational temperature has led to stabilising the phase from >725 °C to room temperature either by doping, albeit with a compromise in conductivity, or by growing the phase confined within superlattice thin films. Superlattice architectures are challenging to implement in functional μSOFC devices owing to their ionic conducting channels being in the plane of the film. Vertically aligned nanocomposites (VANs) have the potential to overcome these limitations, as their nanocolumnar structures are perpendicular to the plane of the film, hence connecting the electrodes at top and bottom. Here, we demonstrate for the first time the growth of epitaxially stabilised δ-Bi 2 O 3 in VAN films, stabilised independently of substrate strain. The phase is doped with Dy and is formed in a VAN film which incorporates DyMnO 3 as a vertically epitaxially stabilising matrix phase. Our VAN films exhibit very high ionic conductivity, reaching 10 −3 S cm −1 at 500 °C. This work opens up the possibility to incorporate thin film δ-Bi 2 O 3 based VANs into functional μSOFC devices, either as cathodes (by pairing δ-Bi 2 O 3 with a catalytically active electronic conductor) and/or electrolytes (by incorporating δ-Bi 2 O 3 with an insulator).
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- NSF-PAR ID:
- 10329976
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 10
- Issue:
- 7
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 3478 to 3484
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Solid‐oxide fuel/electrolyzer cells are limited by a dearth of electrolyte materials with low ohmic loss and an incomplete understanding of the structure–property relationships that would enable the rational design of better materials. Here, using epitaxial thin‐film growth, synchrotron radiation, impedance spectroscopy, and density‐functional theory, the impact of structural parameters (i.e., unit‐cell volume and octahedral rotations) on ionic conductivity is delineated in La0.9Sr0.1Ga0.95Mg0.05O3–
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1ta07308g
