Li7-xLa3Sn2-xNbxO12 (x=0.25–1) cubic lithium garnet

Saranya, K.; Deviannapoorani, C.; Dhivya, L.; Ramakumar, S.; Janani, N.; Murugan, Ramaswamy

doi:10.1016/j.matlet.2012.03.002

Cited by 15 publications

(13 citation statements)

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“…These values are somewhat lower as compared to those reported earlier: 3.5 × 10 −4 S cm −1 (LLHTO, x = 0.45) 22 and 2.41 × 10 −4 S cm −1 (LLSTO, x = 0.45). 21 Such differences may have various origins. Bulk properties and interfacial ion transport is expected to be influenced by sintering procedures, final Li compositions, the defect chemistry, and the element distribution in the ceramics.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Such investigations are expected to be helpful in refining our understanding of ionic conduction in garnet-type electrolytes. Previous studies have shown that Nb, Ta, and Al stabilize the cubic form of the LLSO phase; 17,19,20 another investigation showed that Ta is also able to stabilize cubic-LLHO 21,22 at ambient temperature. To the best of our knowledge, no study so far is available in literature that systematically looked at the change of bulk ionic conductivities of the two solid solutions of Li In the present study, we took advantage of a ceramic sintering approach and systematically investigated the connections between phases, Li content, microstructure and Li + transport properties by using powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and broadband impedance and conductivity spectroscopy.…”

Section: ■ Introductionmentioning

confidence: 96%

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Anomalies in Bulk Ion Transport in the Solid Solutions of Li₇La₃M₂O₁₂ (M = Hf, Sn) and Li₅La₃Ta₂O₁₂

et al. 2020

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Cubic Li 7 La 3 Zr 2 O 12 (LLZO), stabilized by supervalent cations, is one of the most promising oxide electrolyte to realize inherently safe all-solid-state batteries. It is of great interest to evaluate the strategy of supervalent stabilization in similar compounds and to describe its effect on ionic bulk conductivity σ′ bulk . Here, we synthesized solid solutions of Li 7– x La 3 M 2– x Ta x O 12 with M = Hf, Sn over the full compositional range ( x = 0, 0.25...2). It turned out that Ta contents at x of 0.25 (M = Hf, LLHTO) and 0.5 (M = Sn, LLSTO) are necessary to yield phase pure cubic Li 7– x La 3 M 2– x Ta x O 12 . The maximum in total conductivity for LLHTO (2 × 10 –4 S cm –1 ) is achieved for x = 1.0; the associated activation energy is 0.46 eV. At x = 0.5 and x = 1.0, we observe two conductivity anomalies that are qualitatively in agreement with the rule of Meyer and Neldel. For LLSTO, at x = 0.75 the conductivity σ′ bulk turned out to be 7.94 × 10 –5 S cm –1 (0.46 eV); the almost monotonic decrease of ion bulk conductivity from x = 0.75 to x = 2 in this series is in line with Meyer–Neldel’s compensation behavior showing that a decrease in E a is accompanied by a decrease of the Arrhenius prefactor. Altogether, the system might serve as an attractive alternative to Al-stabilized (or Ga-stabilized) Li 7 La 3 Zr 2 O 12 as LLHTO is also anticipated to be highly stable against Li metal.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 96%

Anomalies in Bulk Ion Transport in the Solid Solutions of Li₇La₃M₂O₁₂ (M = Hf, Sn) and Li₅La₃Ta₂O₁₂

et al. 2020

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“…The PXRD patterns of LLZ and Al-LLZ precursors sintered at various temperatures along with the reported cubic 4 and tetragonal phase 6,24 The PXRD pattern of the LLZ precursor sintered at 800 C in tetragonal phase exposed to humid conditions results in the formation of cubic like garnet phase as shown in Fig. 2(d).…”

Section: Structural Analysismentioning

confidence: 88%

Influence of sintering additives on densification and Li⁺ conductivity of Al doped Li₇La₃Zr₂O₁₂ lithium garnet

et al. 2014

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“…2 Following the initial results of high Li + conduction in the LLZ there has been a significant interest in the synthesis, structural characterisation and electrical conductivity of Ta, Nb, Al, Ga, Si and Y substituted LLZ [4][5][6][7][8][9][10][11][12] and related system Li 7 La 3 M 2 O 12 (M = Sn, Hf). [13][14][15][16] The LLZ in tetragonal phase exhibits lower ionic conductivity by two orders of magnitude compared to the cubic phase. 17 Systematic studies suggest that the unintentional incorporation of Al 3+ ions into LLZ during the high-temperature solid state synthesis using an alumina crucible helps to stabilize the cubic phase against the tetragonal one.…”

Section: Introductionmentioning

confidence: 99%

Structure and Li+ dynamics of Sb-doped Li7La3Zr2O12 fast lithium ion conductors

Ramakumar

Satyanarayana

Manorama

et al. 2013

Phys. Chem. Chem. Phys.

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Antimony-doped lithium stuffed garnets Li(7-x)La3Zr(2-x)Sb(x)O12 (x = 0.2-1.0) prepared using a conventional solid state reaction method are characterized using Powder X-ray Diffraction (PXRD), Scanning Electron Microscopy (SEM), Energy Dispersive Analysis by X-ray (EDAX), AC Impedance spectroscopy, Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Raman spectroscopic techniques. PXRD confirms the formation of a garnet-like structure with cubic symmetry for the entire selected compositional range. Among the investigated compounds, the compound with an Sb content corresponding to x = 0.4, i.e. Li6.6La3Zr1.6Sb0.4O12 exhibits the maximum total (bulk + grain boundary) ionic conductivity of 7.7 × 10(-4) S cm(-1) at 30 °C. The shape of the imaginary part of the modulus spectra suggests that the relaxation processes are non-Debye in nature. The full width at half maximum (FWHM) for the master modulus curve of Li6.6La3Zr1.6Sb0.4O12 is found to be the smallest among the investigated lithium garnets. The full width at half maximum (FWHM) of the (7)Li MAS NMR spectrum for the composition Li6.6La3Zr1.6Sb0.4O12 is the smallest among the investigated compounds. Raman data collected for the compounds in this series indicates an increase of Li(+) occupancy in the tetrahedrally coordinated site with an associated decrease of Li(+) occupancy in the octahedrally coordinated site during an increase of x in Li(7-x)La3Zr(2-x)Sb(x)O12. The present investigation reveals that the optimal Li(+) concentration required to achieve the maximum room-temperature Li(+) conductivity in Li(7-x)La3Zr(2-x)Sb(x)O12 lithium stuffed garnet is around x = 0.4.

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Li7-xLa3Sn2-xNbxO12 (x=0.25–1) cubic lithium garnet

Cited by 15 publications

References 9 publications

Anomalies in Bulk Ion Transport in the Solid Solutions of Li₇La₃M₂O₁₂ (M = Hf, Sn) and Li₅La₃Ta₂O₁₂

Anomalies in Bulk Ion Transport in the Solid Solutions of Li₇La₃M₂O₁₂ (M = Hf, Sn) and Li₅La₃Ta₂O₁₂

Influence of sintering additives on densification and Li⁺ conductivity of Al doped Li₇La₃Zr₂O₁₂ lithium garnet

Structure and Li+ dynamics of Sb-doped Li7La3Zr2O12 fast lithium ion conductors

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Li7-xLa3Sn2-xNbxO12 (x=0.25–1) cubic lithium garnet

Cited by 15 publications

References 9 publications

Anomalies in Bulk Ion Transport in the Solid Solutions of Li7La3M2O12 (M = Hf, Sn) and Li5La3Ta2O12

Anomalies in Bulk Ion Transport in the Solid Solutions of Li7La3M2O12 (M = Hf, Sn) and Li5La3Ta2O12

Influence of sintering additives on densification and Li+ conductivity of Al doped Li7La3Zr2O12 lithium garnet

Structure and Li+ dynamics of Sb-doped Li7La3Zr2O12 fast lithium ion conductors

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Anomalies in Bulk Ion Transport in the Solid Solutions of Li₇La₃M₂O₁₂ (M = Hf, Sn) and Li₅La₃Ta₂O₁₂

Anomalies in Bulk Ion Transport in the Solid Solutions of Li₇La₃M₂O₁₂ (M = Hf, Sn) and Li₅La₃Ta₂O₁₂

Influence of sintering additives on densification and Li⁺ conductivity of Al doped Li₇La₃Zr₂O₁₂ lithium garnet