Structure and conductivity of perovskite Li0.355La0.35Sr0.3Ti0.995M0.005O3 (M = Al, Co and In) ceramics

Yu, Kun; Jin, Li; Li, Yang; Liu, Gang; Wei, Xiaoyong; Yan, Yan

doi:10.1016/j.ceramint.2019.08.012

Cited by 14 publications

(5 citation statements)

References 49 publications

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“…We speculate that the unintended La-site substitutions at high substitution levels predicted by BVM decreased the bulk conductivity by blocking Li ions pathways because they occupy La-site through which lithium ions hop and via reducing charge carriers concentration, as reported in ref . We also propose that the decrease of bulk conductivity for Ti-site substitutions is due to Ti octahedra distortion induced by the larger and smaller ionic radius elements, thereby decreasing the bottleneck (four oxygen window) for Li diffusion and increasing the lithium transport energy barrier as seen in refs , , . The reduced bulk conductivity in both site substitutions at high substitution levels could be due to decreased charge carrier numbers because the charge was compensated by the Li/La, but it is also undoubtedly related to a decrease in LLTO content .…”

Section: Resultssupporting

confidence: 57%

Benefits and Limitations of 226 Substitutions into Li-La-Ti-O Perovskites

Jonderian,

Peng,

Davies

et al. 2023

Chem. Mater.

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Lithium lanthanum titanate solid electrolyte has high bulk conductivity and stability at high potentials but suffers from low grain boundary conductivity and instability at low potentials. In order to mitigate these two limitations, the effect of single partial substitutions on perovskite (Li-La-Ti-O) materials was studied. The X-ray diffraction patterns showed that numerous substituents enable pure-phase perovskite, a feat that could not previously be accomplished in the unsubstituted materials. Bond valence mismatch is used as a simple predictor of the substitution site and shows that remarkably high mismatches can be tolerated by the perovskite structure. The best substitutions had minimal impact on bulk conductivity but induced minor enhancements in the grain boundary conductivity. Some elements, such as Cr and Mn, increased the electronic conductivity producing good candidates for the electrolyte in the composite cathode for an all-solid-state battery. The electrochemical stability limits were also shifted either to higher or lower potentials by substitutions. Cr substitution resulted in the electrolyte becoming a cathode material with a highly reversible redox peak near 3.43 V (vs Li/Li+). A thorough screening, therefore, yields a combination of materials (unsubstituted as the anode/electrolyte and Cr-substituted as the cathode) that represents a strong candidate for the elusive epitaxial battery, an ideal application of this class of materials given the very high bulk conductivities. Some substitutions also extended the low potential stability limit to below 1.5 V, a shift that would allow the use of Li4Ti5O12 and Nb-based anodes without a buffer layer. Overall, this work shows to what extent the properties of LLTO perovskites can be tuned with substitution in order to meet various application requirements.

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Section: Resultssupporting

confidence: 57%

Benefits and Limitations of 226 Substitutions into Li-La-Ti-O Perovskites

Jonderian,

Peng,

Davies

et al. 2023

Chem. Mater.

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“…To improve stability and conductivity, B‐site substitution has also been widely practiced, including use of trivalent ions Al 3+ , [ 159 ] Co 3+ , [ 159 ] In 3+ , [ 159 ] tetravalent ions Zr 4+ , [ 160 , 161 ] Sn 4+ , [ 162 ] and pentavalent ions Ta 4+ , [ 160 , 161 , 162 ] V 5+ , [ 163 ] and Nb 5+ . [ 163 , 164 ] Partial substitution of Ti 4+ by trivalent ions such as Al 3+ causes increased charge carriers, hence resulting in an enhanced ionic conductivity.…”

Section: Solid‐state Electrolytesmentioning

confidence: 99%

“…The ionic conductivity of the as-deposited Li 0.43 La 0.457 Sr 0.1 TiO 3 thin film at 50 °C was only 1.263 × 10 −6 S cm −1 but increased to with the postannealing temperature and reached a maximum value of 4.631 × 10 −5 S cm −1 after annealing at 300 °C although it still displayed an amorphous structure from XRD characterization, and the conductivity sharply dropped at a higher annealing temperature of 400 °C (Figure 15b). [158] To improve stability and conductivity, B-site substitution has also been widely practiced, including use of trivalent ions Al 3+ , [159] Co 3+ , [159] In 3+ , [159] tetravalent ions Zr 4+ , [160,161] Sn 4+ , [162] and pentavalent ions Ta 4+ , [160,161,162] V 5+ , [163] and Nb 5+ . [163,164] Partial substitution of Ti 4+ by trivalent ions such as Al 3+ causes increased charge carriers, hence resulting in an enhanced ionic conductivity.…”

Section: Perovskite Type Of Electrolytementioning

confidence: 99%

“…[168,170] The systematic investigations of Li 0.5 La 0.5 TiO 4 films that were deposited at various temperatures have demonstrated that the high ionic conductivity comparable to bulk ceramic one can be achieved in an amorphous state. Wide deposition temperature ranges were Influence of dopants on the conductivity: a) changes of lattice parameter as well as ionic conductivity of bulk Li 0.33+x La 0.56−x Sr x TiO 3 after A-site substitution of Sr (data from [159] ), b) changes of ionic conductivity of rf-sputtered Li 0.33+x La 0.56−x Sr x TiO 3 (data from [161] ), c) changes of bulk and grain boundary ionic conductivity at different concentration of Al 3+ , (data from [168] ), d) influence of B-site substitution on the lattice parameters and ionic conductivities of Li 0.24 La 0.587 Ti 1-x Sn x O 3 and Li 0.24-x La 0.587 Ti 1-x Ta x O 3 (data from [162] ), e) conductivity of La (2/3) − x Li 3x ⊡ (1/3) − 2x TiO 3 at different Li + concentration and processing temperatures (data from [169,167,168] ), and f) conductivity of Li 0.5 La 0.5 TiO 4 thin-film electrolytes deposited by PLD at various temperatures (data from [169,171] and [172] where PLD was used, and [176] where melt-quench was used.) studied by Lee [171] and Ahn, [172] showing that with proper control of deposition, the ionic conductivity of the thin film electrolyte deposited at room temperature was about 10 −4 S cm −1 and increased with deposition temperature and was maximized at the deposition temperature between 300 and 400 °C as shown in Figure 15f, [171] while data from Ahn et al showed a continuous decrease, which is consistent with Lee's finding.…”

Section: Perovskite Type Of Electrolytementioning

confidence: 99%

“…Figure15. Influence of dopants on the conductivity: a) changes of lattice parameter as well as ionic conductivity of bulk Li 0.33+x La 0.56−x Sr x TiO 3 after A-site substitution of Sr (data from[159] ), b) changes of ionic conductivity of rf-sputtered Li 0.33+x La 0.56−x Sr x TiO 3 (data from[161] ), c) changes of bulk and grain boundary ionic conductivity at different concentration of Al 3+ , (data from[168] ), d) influence of B-site substitution on the lattice parameters and ionic conductivities of Li 0.24 La 0.587 Ti 1-x Sn x O 3 and Li 0.24-x La 0.587 Ti 1-x Ta x O 3 (data from[162] ), e) conductivity of La (2/3) − x Li 3x ⊡ (1/3) − 2x TiO 3 at different Li + concentration and processing temperatures (data from[169,167,168] ), and f) conductivity of Li 0.5 La 0.5 TiO 4 thin-film electrolytes deposited by PLD at various temperatures (data from[169,171] and[172] where PLD was used, and[176] where melt-quench was used. )…”

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confidence: 99%

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All‐Solid‐State Thin Film μ‐Batteries for Microelectronics

Dai

et al. 2021

Advanced Science

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Continuous advances in microelectronics and micro/nanoelectromechanical systems enable the use of microsized energy storage devices, namely solid-state thin-film -batteries. Different from the current button batteries, the -battery can directly be integrated on microchips forming a very compact "system on chip" since no liquid electrolyte is used in the -battery. The all-solid-state battery (ASSB) that uses solid-state electrolyte has become a research trend because of its high safety and increased capacity. The solid-state thin-film -battery belongs to the family of ASSB but in a small format. However, a lot of scientific and technical issues and challenges are to be resolved before its real application, including the ionic conductivity of the solid-state electrolyte, the electrical conductivity of the electrode, integration technologies, electrochemical-induced strain, etc. To achieve this goal, understanding the processing of thin films and fundamentals of ion transfer in the solid-state electrolytes and hence in the -batteries becomes utmost important. This review therefore focuses on solid-state ionics and provides inside of ion transportation in the solid state and effects of chemistry on electrochemical behaviors and proposes key technology for processing of the -battery.

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