Phase transition and conductivity improvement of tetragonal fast lithium ionic electrolyte Li7La3Zr2O12

Wang, X.P.; Hu, Jiulin; Xia, Yonggao; Zhuang, Zhi; Guo, Li; Lü, Hui; Zhang, T.; Fang, Q.F.

doi:10.1016/j.ssi.2013.09.029

Cited by 15 publications

(10 citation statements)

References 23 publications

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“…The polycrystalline ceramic samples of Li 13 Crystalline phases of all the investigated Li 7 La 3 Zr 2 O 12 samples were identified by X-ray diffraction analysis at room temperature using Cu-Ka radiation in the 2y range from 101 to 701 with a step of 0.0331. The whole pattern matching refinement of the XRD patterns was performed using the Fullprof program based on the garnet-like structure, 14 in which a pseudo-Voigt function was used as the profile function in the refinements.…”

Section: Methodsmentioning

confidence: 99%

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li₇La₃Zr₂O₁₂ revealed by an internal friction technique

Wang

Gao

Xia

et al. 2014

Phys. Chem. Chem. Phys.

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The correlation and transport mechanism of lithium ions with the crystal structure of a fast lithium ion conductor Li7La3Zr2O12 are mainly investigated by internal friction (IF) and AC impedance spectroscopy techniques. Compared with the poor conductivity of tetragonal Li7La3Zr2O12, the Al stabilized cubic phase exhibits a good ionic conductivity that can be up to 1.9 × 10(-4) S cm(-1) at room temperature, which can be ascribed to the disordered distribution of lithium ions in the cubic phase. A well-pronounced relaxation IF peak (labeled as peak PC) is observed in the cubic phase while a very weak IF peak (labeled as PT) is observed in the tetragonal phase, further evidencing the difference in lithium ion migration in the two phases. Peak PC can be decomposed into two sub-peaks with the activation energy and the pre-exponential factor of relaxation time being E1 = 0.41 eV and τ01 = 1.2 × 10(-14) s for the lower temperature peak PC1 and E2 = 0.35 eV and τ02 = 1.9 × 10(-15) s for the higher temperature PC2 peak, respectively. Based on the crystalline structure of a cubic garnet-type Li7La3Zr2O12 compound, an atomistic mechanism of lithium ion diffusion via vacancies is suggested, i.e. 48g(96h) ↔ 48g(96h) for peak PC1 and 48g(96h) ↔ 24d for peak PC2, respectively. The weak PT peak in the tetragonal phase is preliminarily interpreted as due to the short jump process among neighboring octahedral sites and vacant tetrahedral sites.

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Section: Methodsmentioning

confidence: 99%

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li₇La₃Zr₂O₁₂ revealed by an internal friction technique

Wang

Gao

Xia

et al. 2014

Phys. Chem. Chem. Phys.

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“…[240][241][242][243] The exchange process may occur preferably in tetrahedral sites over octahedral sites. 259,260 The sensitivity of Li-stuffed garnets to humid air, or more specifically, to H 2 O and CO 2 , could account for several phenomena that are closely related to the conductivity of LLZO-based garnets, including the high measured electrode/electrolyte interfacial impedance, 232,244 the discrepancy on the low temperature tetragonal-cubic phase transition process, [245][246][247][248][249] and the effect of sintering atmosphere. 215 Obviously, much care should be taken for LLZO preparation and storage to warrant repeatable experimental results.…”

Section: Garnet-type Electrolytesmentioning

confidence: 99%

Oxide Electrolytes for Lithium Batteries

et al. 2015

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As the most promising candidate of the solid electrolyte materials for future lithium batteries, oxide electrolytes with highlithium-ion conductivity have experienced a rapid development in the past few decades. Existing oxide electrolytes are divided into two groups, i.e., crystalline group including NASICON, perovskite, garnet, and some newly developing structures, and amorphous/glass group including Li 2 O-MO x (M = Si, B, P, etc.) and LiPON-related materials. After a historical perspective on the general development of oxide electrolytes, we try to give a comprehensive review on the oxide electrolytes with high-lithium-ion conductivity, with special emphasis on the aspect of materials selection and design for applications as solid electrolytes in lithium batteries. Some successful examples and meaningful attempts on the incorporation of oxide electrolytes in lithium batteries are also presented. In the conclusion part, an outlook for the future direction of oxide electrolytes development is given.

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“…The initial materials are high purity La(OH) 3 ). In order to compensate the evaporation loss of lithium at high temperature, an extra of 10 wt.% lithium was added into reaction mixtures, and the detailed synthesis processes had been reported in our previous work [9]. Powder X-ray diffraction (XRD) was used to identify the crystal phase of pure Li 7 La 3 Zr 2 O 12 and cationic stabilized oxides with Cu-Kα radiation (X'pert MPD PRO diffractometer) in the scanning range of 10° to 70° with a step of 0.033°.…”

Section: Methodsmentioning

confidence: 99%

Internal Friction of Li7La3Zr2O12 Based Lithium Ionic Conductors

Wang

Song

et al. 2016

Archives of Metallurgy and Materials

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The diffusion mechanisms of lithium ions in tetragonal phase as well as in Al and Nb stabilized cubic Li7La3Zr2O12 compounds were investigated by low-frequency internal friction technique. In the cubic Li7La3Zr2O12 phase, a remarkable relaxation-type internal friction peak PC with a peak height up to 0.12 was observed in the temperature range from 15°C to 60°C. In the tetragonal phase however, the height of the PT peak dropped to 0.01. The obvious difference of the relaxation strength between the cubic and tetragonal phases is due to the different distribution of lithium ions in lattice, ordered in the tetragonal phase and disordered in the cubic phase. Based on the crystalline structure of the cubic garnet-type Li7La3Zr2O12 compound, it is suggested that the high internal friction peak in the cubic phase may be attributed to two diffusion processes of lithium ions: 96h↔96h and 96h↔24d.

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Phase transition and conductivity improvement of tetragonal fast lithium ionic electrolyte Li7La3Zr2O12

Cited by 15 publications

References 23 publications

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li₇La₃Zr₂O₁₂ revealed by an internal friction technique

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li₇La₃Zr₂O₁₂ revealed by an internal friction technique

Oxide Electrolytes for Lithium Batteries

Internal Friction of Li7La3Zr2O12 Based Lithium Ionic Conductors

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Phase transition and conductivity improvement of tetragonal fast lithium ionic electrolyte Li7La3Zr2O12

Cited by 15 publications

References 23 publications

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li7La3Zr2O12 revealed by an internal friction technique

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li7La3Zr2O12 revealed by an internal friction technique

Oxide Electrolytes for Lithium Batteries

Internal Friction of Li7La3Zr2O12 Based Lithium Ionic Conductors

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Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li₇La₃Zr₂O₁₂ revealed by an internal friction technique

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li₇La₃Zr₂O₁₂ revealed by an internal friction technique