Ionic conductivity in LiAlSiO4

Johnson, R. T.; Morosin, B.; Knotek, M. L.; Biefeld, R. M.

doi:10.1016/0375-9601(75)90788-4

Cited by 40 publications

(25 citation statements)

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“…Lithium ion diffusion coefficients at different temperatures were calculated and used to calculate the activation energy of lithium ions in a series of lithium aluminosilicate glasses. The calculated activation energy of lithium ions at the [Al]/ [Li] ratio, R, equal to 0.00 was 0.75 eV, in good agreement with Beier and Frischat's experimental result of 0.78 eV [10]; with R = 1.00, the simulated value was 0.66 eV, in good agreement with the experimental value of 0.68 eV obtained by Johnson et al [14]. The minimum in the activation energy for lithium diffusion is exhibited at R = 1.00 in the simulated glasses, similar to experimentally observed behavior in sodium aluminosilicate glasses.…”

Section: Discussionsupporting

confidence: 90%

“…9, the activation energy for lithium diffusion in these glasses decreases to 0.66 eV by altering the concentration of Al. This value of 0.66 eV at R = 1.00 is similar to the value obtained experimentally in lithium aluminosilicate glasses with an R-value equal to 1.00 (0.68 eV) [14]. Since the preexponential (D 0 ) is quite close for the R = 0.00 and R = 1.00 systems (0.0019 cm 2 /s versus 0.0014 cm 2 /s, respectively, see Table 4), the lower activation energy implies more rapid diffusion in these glasses with R = 1.00.…”

Section: R-valuesupporting

confidence: 86%

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Molecular dynamics simulation of lithium diffusion in Li2O–Al2O3–SiO2 glasses

Garofalini

2004

Solid State Ionics

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Section: Discussionsupporting

confidence: 90%

Section: R-valuesupporting

confidence: 86%

Molecular dynamics simulation of lithium diffusion in Li2O–Al2O3–SiO2 glasses

Garofalini

2004

Solid State Ionics

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“…13 T g values for the aluminosilicate glasses are listed in Table 2. Derived values for glasses of group 1 agree with literature data within AE5 K for EUC, 8,14 SPO, FSP and PET. 8 …”

Section: Determination Of T Gsupporting

confidence: 85%

“…Johnson et al 21 for the eucryptite glass (67.1 kJ mol À1 ) when plotting their data as log sT vs. 1/T. The activation E a for the depolymerized glasses is distinctly higher, with values from 76.5 to 78.1 kJ mol À1 .…”

Section: View Article Onlinementioning

confidence: 99%

Lithium conductivity in glasses of the Li₂O–Al₂O₃–SiO₂system

Ross

Welsch

Behrens

2015

Phys. Chem. Chem. Phys.

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To improve the understanding of Li-dynamics in oxide glasses, i.e. the effect of [AlO 4 ] À tetrahedra and non-bridging oxygens on the potential landscape, electrical conductivity of seven fully polymerized and partly depolymerized lithium aluminosilicate glasses was investigated using impedance spectroscopy (IS).Lithium is the only mobile particle in these materials. Data derived from IS, i.e. activation energies, preexponential factors and diffusivities for lithium, are interpreted in light of Raman spectroscopic analyses of local structures in order to identify building units, which are crucial for lithium dynamics and migration. In polymerized glasses (compositional join LiAlSiO 4 -LiAlSi 4 O 10 ) the direct current (DC) electrical conductivity continuously increases with increasing lithium content while lithium diffusivity is not affected by the Al/Si ratio in the glasses. Hence, the increase in electrical conductivity can be solely assigned to lithium concentration in the glasses. An excess of Li with respect to Al, i.e. the introduction of non-bridging oxygen into the network, causes a decrease in lithium mobility in the glasses. Activation energies in polymerized glasses (66 to 70 kJ mol À1 ) are significantly lower than those in depolymerized networks (76 to 78 kJ mol À1 ) while pre-exponential factors are nearly constant across all compositions. Comparison of the data with results for lithium silicates from the literature indicates a minimum in lithium diffusivity for glasses containing both aluminium tetrahedra and non-bridging oxygens. The findings allow a prediction of DC conductivity for a large variety of lithium aluminosilicate glass compositions.

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“…Ionic conductivity measurements were made by using a two-terminaltechnique (6,9) over the frequency range from 5 to 5 • l0 s Hz. Ionically blocking silver foil electrodes were used and were pressed onto the sample in a BN holder.…”

Section: Experimental Methodsmentioning

confidence: 99%

Ionic Conductivity of Li2 O ‐ Based Mixed Oxides and the Effects of Moisture and LiOH on Their Electrical and Structural Properties

Biefeld¹,

Johnson²

1979

J. Electrochem. Soc.

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Thermal, structural, and electrical measurements on polycrystalline Li20 and certain Li20-based mixed oxides [LisMO4 (M ----A1, Fe, and Ga), Li20 -tZnO, LiYO2, and Li20 Jr Y203 mixtures] indicate that LiOH is produced within these materials on exposure to a moist environment. The presence of LiOH produces an endothermic reaction at ~400°C and a large increase in ionic conductivity above ~400°C [~ = 0.1 (12-cm)-1 at 500°C]. These features are absent under dry conditions (no LiOH). In the dry state, the ionic conductivity varies nearly exponentially with temperature (activation energies of ,~0.5-1.0 eV) and has values ranging from 10 -4 to 10 -~ (~%-cm) -1 at 500-C. All of these materials, except possibly for the Y-containing compounds, appear to have common ionic conductivity characteristics. The electrical and structural properties of the LisMO4 compounds are reproducible on cycling between wet (containing LiOH) and dry (no LiOH) conditions. This does not appear to be the case for the other materials. There is a significant (1-50%) electronic contribution to the conductivity in these materials.There is considerable interest in developing solid lithium ion conductors for potential use in a variety of applications including high energy batteries (1-3). This has lead to a search for new solid electrolytes exhibiting lithium ion conductivity and has stimulated interest in developing a fundamental understanding of ionic transport in solids. Several recent papers have discussed the conduction properties of potential lithium ion solid electrolytes (1-5). Two among the most promising are Li3N [¢(25 °) ~ 1 × 10 -a, ~(300 °) 7 × 10 -2 (~-cm) -1] (4) and Li-~-alumina [q(25 °) 1.3 × 10 -4 ,~(300 °) ~ 9 × 10 -3 (E~-cm)-l] (5). This paper gives thermal, structural, and electrical results obtained on several mixed metal-oxide systems based on Li20. The ionic conductivity of several well-known oxide ion conductors which have the fluorite structure (e.g., CaO stabilized ZrO2) can be explained by an anion vacancy conduction mechanism (6). By analogy, it might be possible to prepare cation conductors by introducing cation vacancies into the inverse-fluorite structure of Li20. Based on this premise the ionic conductivity of several materials in which aliovalent cations were substituted for lithium was investigated in this study. Specifically, the materials examined are polycrystalline Li20, LisMO4 (M : A1, Fe, and Ga), 75 mole percent (m/o) Li20 -t-25 m/o ZnO, LiYO2, and two mixtures of Li20 ~-Y203.An earlier investigation of LisA104, LisGaO4, and LisZnO4 by Raistrick et al. (7) had revealed an anomalous increase in the ionic conductivity of these materials at ,~ 400°C. Values up to 0.5 (~-cm)-i were reported at 500°C which made these materials of interest for thermal battery applications. Our initial studies of * Electrochemical Society Active Member. Key words: electrolyte, ceramics, conductance, DTA.Li~A104 (8) showed that the large conductivity increase was not an intrinsic property of Li~A104 but was due to the presenc...

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Ionic conductivity in LiAlSiO4

Cited by 40 publications

References 3 publications

Molecular dynamics simulation of lithium diffusion in Li2O–Al2O3–SiO2 glasses

Molecular dynamics simulation of lithium diffusion in Li2O–Al2O3–SiO2 glasses

Lithium conductivity in glasses of the Li₂O–Al₂O₃–SiO₂system

Ionic Conductivity of Li2 O ‐ Based Mixed Oxides and the Effects of Moisture and LiOH on Their Electrical and Structural Properties

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Ionic conductivity in LiAlSiO4

Cited by 40 publications

References 3 publications

Molecular dynamics simulation of lithium diffusion in Li2O–Al2O3–SiO2 glasses

Molecular dynamics simulation of lithium diffusion in Li2O–Al2O3–SiO2 glasses

Lithium conductivity in glasses of the Li2O–Al2O3–SiO2system

Ionic Conductivity of Li2 O ‐ Based Mixed Oxides and the Effects of Moisture and LiOH on Their Electrical and Structural Properties

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Lithium conductivity in glasses of the Li₂O–Al₂O₃–SiO₂system