Li+ and divalent ion conductivity in beta and beta″ alumina

Farrington, G. C.; Dunn, Bruce; Briant, J.L.

doi:10.1016/0167-2738(81)90122-3

Cited by 33 publications

(13 citation statements)

References 5 publications

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“…As an additional benefit, the Li cations usually represent the only mobile species within an immobile anionic framework. Apart from the long known "classic" crystalline Li ion conductors such as Li-β-alumina, LiX·H 2 O (X = Cl, Br, I) [55,56], Li 3y La (2/3)−y TiO 3 (0.04 < y < 0.14), [57][58][59] [80]. The field of Li ion conducting glasses and glass ceramics will not be covered here [81].…”

Section: Crystalline Electrolytesmentioning

confidence: 99%

Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Wüllen¹,

Echelmeyer

Voigt

et al. 2010

Zeitschrift Für Physikalische Chemie

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Ionic TransportResearch on solid ionic conductors for use as electrolytes in all solid state batteries still constitutes a rather vivid branch of today's materials science. Despite enormous efforts, neither the development of a solid electrolyte fulfilling the key requirements such as mechanical stability and high ionic conductivity at ambient temperature has been successful nor has an extended understanding of the local Li coordination motifs in the often amorphous systems been obtained. In this contribution, recent progress both in the development of novel solid state electrolytes with high ionic conductivity and mechanical stability and in the characterization of the local Li coordination motifs in these electrolytes from our laboratory is presented. The work was performed as a project within the framework of the Collaborative Research Centre SFB 458 "Ionic Motion in Materials with Disordered Structures -From Elementary Steps to Macroscopic Transport". Results will be given for polymer electrolytes based on polyethylene oxide (PEO), polyphosphazene (PPZ) and polyacrylonitrile (PAN) with various Li salts, nano-composites of these polymer electrolytes and Al 2 O 3 as a ceramic filler, novel inorganic/organic hybrid electrolytes, in which a mixture of an ionic liquid and Li salt is confined within the pore system of a SiO 2 glass, and a crystalline electrolyte, Li 5 La 3 Nb 2 O 12 . Employing a range of advanced solid state NMR methodologies including dipolar based NMR techniques and pulsed field gradient (PFG) NMR and impedance spectroscopy we were able to obtain a detailed knowledge about the local Li cation coordination motifs and the mechanism of Li transport in these electrolytes. Especially the hybrid electrolytes and the salt rich PAN based polymer electrolytes were identified as rather promising materials which combine a high ionic conductivity and mechanical stability.

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Section: Crystalline Electrolytesmentioning

confidence: 99%

Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Wüllen¹,

Echelmeyer

Voigt

et al. 2010

Zeitschrift Für Physikalische Chemie

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“…The room temperature diffusion coefficient D σ estimated using Eq. (3) 6 Li in pure Li β-alumina has been previously measured by the tracer diffusion technique in the temperature range 200-400…”

Section: A Diffusion Measurementmentioning

confidence: 99%

“…5,6 The molecular formula of β-alumina is (M 2 O) x · 11Al 2 O 3 , where M represents a monovalent cation. For stoichiometric β-alumina, x = 1; however, the material is generally nonstoichiometric and x ranges between 1.2 and 1.3. β-alumina is a layered structure material with monovalent ion containing mirror planes situated between alumina spinel blocks.…”

Section: Introductionmentioning

confidence: 99%

Lithium ion diffusion in Li β-alumina single crystals measured by pulsed field gradient NMR spectroscopy

Chowdhury

Takekawa

Iwai

et al. 2014

The Journal of Chemical Physics

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Lithium ion micrometer diffusion in a garnet-type cubic Li 7 La 3 Zr 2 O 12 (LLZO) studied using 7 Li NMR spectroscopy The Journal of Chemical Physics 146, 024701 (2017) The lithium ion diffusion coefficient of a 93% Li β-alumina single crystal was measured for the first time using pulsed field gradient (PFG) NMR spectroscopy with two different crystal orientations. The diffusion coefficient was found to be 1.2 × 10 −11 m 2 /s in the direction perpendicular to the c axis at room temperature. The Li ion diffusion coefficient along the c axis direction was found to be very small (6.4 × 10 −13 m 2 /s at 333 K), which suggests that the macroscopic diffusion of the Li ion in the β-alumina crystal is mainly two-dimensional. The diffusion coefficient for the same sample was also estimated using NMR line narrowing data and impedance measurements. The impedance data show reasonable agreement with PFG-NMR data, while the line narrowing measurements provided a lower value for the diffusion coefficient. Line narrowing measurements also provided a relatively low value for the activation energy and pre-exponential factor. The temperature dependent diffusion coefficient was obtained in the temperature range 297-333 K by PFG-NMR, from which the activation energy for diffusion of the Li ion was estimated. The activation energy obtained by PFG-NMR was smaller than that obtained by impedance measurements, which suggests that thermally activated defect formation energy exists for 93% Li β-alumina single crystals. The diffusion time dependence of the diffusion coefficient was observed for the Li ion in the 93% Li β-alumina single crystal by means of PFG-NMR experiments. Motion of Li ion in fractal dimension might be a possible explanation for the observed diffusion time dependence of the diffusion coefficient in the 93% Li β-alumina system.

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“…11 Substitutions at various sites in the garnet framework have been reported. 4 For example, partial substitution of Ba for La resulted in the garnet-type Li 6 18 There have been no reports in the literature with regard to the effect of Sm substitution at the Nb-sites in Li 5 La 3 M 2 O 12 . 4 In this paper, the garnet-like metal oxide Li 5+2x La 3 Nb 2-x Sm x O 12 (0 ≤ x ≤ 0.7) is investigated to understand the role of Sm-doping for Nb on Li ion conductivity, chemical stability, and microstructure.…”

mentioning

confidence: 99%

“…These solid electrolytes have also shown to have high Li-ion conductivity with Li ion transference number close to unity. 4 Various types of solid electrolytes, including Li 3 N (σ 25 • C = ∼10 −3 S cm −1 , E a (25 -200 • C) = 0.25 eV), 5 Li-β-alumina (σ 25 • C = ∼10 −3 S cm −1 , E a (-80 -500 • C) = 0.24 eV), 6 Li silicates, (e.g., Li 4 SiO 4, σ 300 • C = ∼10 −5 S cm −1 , E a (91 -324 • C) = 0.87 eV), 7 Li phosphorous oxynitrides (e.g., Li 2.88 PO 3.73 N 0.14 , σ 25 • C = ∼10 −13 S cm −1 , E a (150 -300 • C) = 0.97 eV), 8 A-site deficient perovskite-type oxides (e.g., Li 0.34 La 0.51 TiO 2.94 , σ 25 • C = ∼10 −3 S cm −1 , E a (-50 -100 • C) = 0.4 eV) 9 and garnet-type metal oxides (e.g., Li 6 BaLa 2 Ta 2 O 12 , σ 22 • C = 4 × 10 −5 S cm −1 , E a (22 -300 • C) = 0.4 eV) 10 are being investigated as electrolytes for LIBs. Recent research has shown that garnet-type Li-ion conductors have high total (bulk + grain-boundary) lithium ion conductivity and are chemically stable when in contact with common Li anodes and cathodes at elevated temperatures.…”

mentioning

confidence: 99%

Synthesis, Structure and Li Ion Conductivity of Garnet-like Li_5+2xLa₃Nb_2-xSm_xO₁₂(0 ≤ x ≤ 0.7)

Pinzaru

Thangadurai

2014

J. Electrochem. Soc.

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Here, we report the synthesis, structure and Li ion conductivity of new Sm-doped garnet-type Li 5+2x La 3 Nb 2-x Sm x O 12 (0 ≤ x ≤ 0.7). Powder X-ray diffraction showed the formation of cubic garnet structure up to x = 0.3. Above x = 0.3 impurity phases were observed, due to LiNbO 3 (the joint committee on powder diffraction standards (JCPDS) card No. 01-074-2239), LiSmO 2 (JCPDS Card No. 01-073-1061) and Sm 2 O 3 . The cubic cell constant increased from 12.774(2) Å (x = 0) to 12.851(2) Å (x = 0.3). Scanning electron microscopy showed that Sm-doping results in an increase in density of the samples, as a result of improved particle-to-particle contact. Among the samples investigated, Li 5.6 La 3 Nb 1.7 Sm 0.3 O 12 , showed the highest conductivity of ∼10 −5 S cm −1 at 24 • C which is an order of magnitude higher than that of the parent compound, Li 2 This organic electrolyte is highly flammable, thus, the development of alternative electrolytes that are stable at high temperatures is an important issue. 3,4 To this end, inorganic solid electrolytes are being considered as a possible replacement for the currently used electrolyte since they have been proven to be chemically stable over a wide range of temperatures, low in cost and non-flammable. These solid electrolytes have also shown to have high Li-ion conductivity with Li ion transference number close to unity. Lithium metal oxides with the nominal formula of Li 5 La 3 M 2 O 12 (M = Nb, Ta) have been reported to crystallize in a garnet-type framework (space group Ia-3d). The total Li-ion conductivity of these garnets has been determined by Thangadurai et al. in 13-17 Recently, our group investigated the effect of Y substitution at the M (Nb) sites, in order to increase the Li + conductivity. The compound with the nominal formula Li 6.5 La 3 Nb 1.25 Y 0.75 O 12 showed a total conductivity of about 10 −4 S cm −1 at 25 • C. 18 There have been no reports in the literature with regard to the effect of Sm substitution at the Nb-sites in Li 5 La 3 M 2 O 12 . 4 In this paper, the garnet-like metal oxide Li 5+2x La 3 Nb 2-x Sm x O 12 (0 ≤ x ≤ 0.7) is investigated to understand the role of Sm-doping for Nb on Li ion conductivity, chemical stability, and microstructure. The samples were prepared by conventional solid-state synthesis. Powder X-ray diffraction studies are presented to prove the formation of the garnet-type crystal structure, followed by scanning electron microscopy to show the microstructure of the samples. Electrochemical impedance spectroscopy was used to determine the Li + conductivity of the samples at different temperatures. Thermogravimetric analysis and Fourier transform infrared spectroscopy were used to study the effect of aging on the garnet samples. • C in air for 8 h. LiNO 3 was added in 10% wt excess to compensate for Li 2 O volatization during heating at high temperatures. The mixtures of precursors were ball milled (Pulverisette, Fritsch, Germany), before and after annealing at 700 Experimental Synthesis of Li• C for 6 h, at 200 min −1...

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Li+ and divalent ion conductivity in beta and beta″ alumina

Cited by 33 publications

References 5 publications

Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Lithium ion diffusion in Li β-alumina single crystals measured by pulsed field gradient NMR spectroscopy

Synthesis, Structure and Li Ion Conductivity of Garnet-like Li_5+2xLa₃Nb_2-xSm_xO₁₂(0 ≤ x ≤ 0.7)

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Li+ and divalent ion conductivity in beta and beta″ alumina

Cited by 33 publications

References 5 publications

Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Local Li Cation Coordination and Dynamics in Novel Solid Electrolytes

Lithium ion diffusion in Li β-alumina single crystals measured by pulsed field gradient NMR spectroscopy

Synthesis, Structure and Li Ion Conductivity of Garnet-like Li5+2xLa3Nb2-xSmxO12(0 ≤ x ≤ 0.7)

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Synthesis, Structure and Li Ion Conductivity of Garnet-like Li_5+2xLa₃Nb_2-xSm_xO₁₂(0 ≤ x ≤ 0.7)