Abstract:High-quality, idiomorphic, single-phase Li5La3Nb2O12 crystals were successfully
grown using
a LiOH flux cooling method at the relatively low temperature of 500
°C at a solute concentration of 5 mol %. The grown Li5La3Nb2O12 crystals had polyhedral
shapes with well-developed, flat {211} and {110} faces. Their shapes
were relatively uniform, and the average crystal size was approximately
59.2 μm. No aggregation was observed in scanning electron microscopy
images. The high crystallinity of the Li5La3Nb2O12 crysta… Show more
“…It indicates that the tilted grain boundary represented by the Σ3 (2–1–1) = (1–21) models is one of the most stable grain boundaries in the Li 5 La 3 Nb 2 O 12 system. This computationally predicted trend is consistent with the thermodynamically stable faces of the Li 5 La 3 Nb 2 O 12 crystals grown from a molten LiOH flux 25 .Figure 6Trajectories of the Li, La, Nb, and O framework atoms obtained for Σ3 (2–1–1) = (1–21) at a temperature of 1300 K.Figure 7RDFs for the Li, La, Nb, and O interactions in the bulk (black) and at the tilted grain boundary Σ3 (2–1–1) = (1–21) model (red): ( a ) Li-Li, ( b ) La-La, ( c ) Nb-Nb, ( d ) O-O, ( e ) La-Li, ( f ) Nb-Li, ( g ) O-Li, (h) Li-O, ( i ) La-O, and ( j ) Nb-O.Figure 8( a ) Arrhenius plots of the Li + conductivity calculated for isotropic 3D Li diffusion path in the bulk garnet Li 5 La 3 Nb 2 O 12 along the a , b , and c axes. ( b ) Fitted Li + conductivity at 300 K derived from the MSD analysis.
…”
Section: Resultssupporting
confidence: 80%
“…The face angle analysis suggests that the crystal surface was dominantly surrounded by larger {211} and smaller {110} faces. Such crystallographic features dovetail with those of Li 5 La 3 Nb 2 O 12 single crystals that were homogeneously grown from LiOH flux (with LiOH·H 2 O, La 2 O 3 , and Nb 2 O 5 powders reacting in a crucible) 25 .Figure 3Time-dependent SEM images of the Nb substrate during reaction in a molten LiOH flux with La 2 O 3 at 500 °C in air: ( a ) as-purchased Nb substrate, after ( b ) 10 min, ( c ) 60 min, and ( d ) 600 min.
…”
Section: Resultsmentioning
confidence: 66%
“…We have reported the Li + conductivity of the sinter bodies prepared from the Li 5 La 3 Nb 2 O 12 crystals of which it was grown from LiOH flux under same recipe described in this paper 25 . The Li + conductivity was of 5 × 10 −6 S·cm −1 at room temperature, as evaluated by conventional electrochemical impedance spectroscopy.…”
Section: Resultsmentioning
confidence: 99%
“…We applied similar recipe of the flux growth of polyhedral shaped Li 5 La 3 Nb 2 O 12 single crystals the crystal layer formation 25 . La 2 O 3 (0.305 g) and LiOH·H 2 O (0.295 g) were mixed in an alumina crucible 30 mL in volume for 30 min.…”
In this work, we demonstrate the direct growth of cubic Li5La3Nb2O12 crystal layer on the LiCoO2 substrate through the conversion of ultra-thin Nb substrate in molten LiOH flux. The initial thickness of the Nb layer determines that of the crystal layer. SEM and TEM observations reveal that the surface is densely covered with well-defined polyhedral crystals. Each crystal is connected to neighboring ones through the formation of tilted grain boundaries with Σ3 (2–1–1) = (1–21) symmetry which show small degradation in lithium ion conductivity comparing to that of bulk. Furthermore, the sub-phase formation at the interface is naturally mitigated during the growth since the formation of Nb2O5 thin film limits the whole reaction kinetics. Using the newly developed stacking approach for stacking solid electrolyte layer on the electrode layer, the grown crystal layer could be an ideal ceramic separator with a dense thin-interface for all-solid-state batteries.
“…It indicates that the tilted grain boundary represented by the Σ3 (2–1–1) = (1–21) models is one of the most stable grain boundaries in the Li 5 La 3 Nb 2 O 12 system. This computationally predicted trend is consistent with the thermodynamically stable faces of the Li 5 La 3 Nb 2 O 12 crystals grown from a molten LiOH flux 25 .Figure 6Trajectories of the Li, La, Nb, and O framework atoms obtained for Σ3 (2–1–1) = (1–21) at a temperature of 1300 K.Figure 7RDFs for the Li, La, Nb, and O interactions in the bulk (black) and at the tilted grain boundary Σ3 (2–1–1) = (1–21) model (red): ( a ) Li-Li, ( b ) La-La, ( c ) Nb-Nb, ( d ) O-O, ( e ) La-Li, ( f ) Nb-Li, ( g ) O-Li, (h) Li-O, ( i ) La-O, and ( j ) Nb-O.Figure 8( a ) Arrhenius plots of the Li + conductivity calculated for isotropic 3D Li diffusion path in the bulk garnet Li 5 La 3 Nb 2 O 12 along the a , b , and c axes. ( b ) Fitted Li + conductivity at 300 K derived from the MSD analysis.
…”
Section: Resultssupporting
confidence: 80%
“…The face angle analysis suggests that the crystal surface was dominantly surrounded by larger {211} and smaller {110} faces. Such crystallographic features dovetail with those of Li 5 La 3 Nb 2 O 12 single crystals that were homogeneously grown from LiOH flux (with LiOH·H 2 O, La 2 O 3 , and Nb 2 O 5 powders reacting in a crucible) 25 .Figure 3Time-dependent SEM images of the Nb substrate during reaction in a molten LiOH flux with La 2 O 3 at 500 °C in air: ( a ) as-purchased Nb substrate, after ( b ) 10 min, ( c ) 60 min, and ( d ) 600 min.
…”
Section: Resultsmentioning
confidence: 66%
“…We have reported the Li + conductivity of the sinter bodies prepared from the Li 5 La 3 Nb 2 O 12 crystals of which it was grown from LiOH flux under same recipe described in this paper 25 . The Li + conductivity was of 5 × 10 −6 S·cm −1 at room temperature, as evaluated by conventional electrochemical impedance spectroscopy.…”
Section: Resultsmentioning
confidence: 99%
“…We applied similar recipe of the flux growth of polyhedral shaped Li 5 La 3 Nb 2 O 12 single crystals the crystal layer formation 25 . La 2 O 3 (0.305 g) and LiOH·H 2 O (0.295 g) were mixed in an alumina crucible 30 mL in volume for 30 min.…”
In this work, we demonstrate the direct growth of cubic Li5La3Nb2O12 crystal layer on the LiCoO2 substrate through the conversion of ultra-thin Nb substrate in molten LiOH flux. The initial thickness of the Nb layer determines that of the crystal layer. SEM and TEM observations reveal that the surface is densely covered with well-defined polyhedral crystals. Each crystal is connected to neighboring ones through the formation of tilted grain boundaries with Σ3 (2–1–1) = (1–21) symmetry which show small degradation in lithium ion conductivity comparing to that of bulk. Furthermore, the sub-phase formation at the interface is naturally mitigated during the growth since the formation of Nb2O5 thin film limits the whole reaction kinetics. Using the newly developed stacking approach for stacking solid electrolyte layer on the electrode layer, the grown crystal layer could be an ideal ceramic separator with a dense thin-interface for all-solid-state batteries.
“…Here, we propose a one-step synthetic route to prepare cubic-phase LLZ using LiOH-based flux growth. The flux method, which is conventionally used for crystal growth from the liquid phase, can possibly provide a growth temperature that is lower than the melting points of the solutes [25][26][27][28][29][30] (ref. 28) has been demonstrated in our previous studies.…”
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