Sulfide glasses: Glass forming region, structure and ionic conduction of glasses in Na2SXS2 (XSi; Ge), Na2SP2S5 and Li2SGeS2 systems

Ribes, M.; Barrau, B.; Souquet, J.L.

doi:10.1016/0022-3093(80)90430-5

Cited by 167 publications

(109 citation statements)

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“…The difference in microstructure affects the total conductivity (especially conductivity at grain-boundary) of the pellets. Figure 3 shows the electrical conductivities of Na 3 PS 4 glass, glass-ceramic electrolytes, and typical inorganic solid electrolytes [9][10][11][12][13][14][15] that have Na + ion conductivities. All the conductivities in this figure were determined from the total resistance, which includes both bulk-grain and grain-boundary components.…”

Section: Resultsmentioning

confidence: 99%

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Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries

et al. 2012

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Innovative rechargeable batteries that can effectively store renewable energy, such as solar and wind power, urgently need to be developed to reduce greenhouse gas emissions. All-solid-state batteries with inorganic solid electrolytes and electrodes are promising power sources for a wide range of applications because of their safety, long-cycle lives and versatile geometries. Rechargeable sodium batteries are more suitable than lithium-ion batteries, because they use abundant and ubiquitous sodium sources. solid electrolytes are critical for realizing allsolid-state sodium batteries. Here we show that stabilization of a high-temperature phase by crystallization from the glassy state dramatically enhances the na + ion conductivity. An ambient temperature conductivity of over 10 − 4 s cm − 1 was obtained in a glass-ceramic electrolyte, in which a cubic na 3 Ps 4 crystal with superionic conductivity was first realized. All-solid-state sodium batteries, with a powder-compressed na 3 Ps 4 electrolyte, functioned as a rechargeable battery at room temperature.

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Section: Resultsmentioning

confidence: 99%

“…Moreover, a drastic reduction in the interparticle resistance of electrolytes without high-temperature sintering is highly significant, because this is critical for developing large-scale solid-state batteries. However, no highly conductive electrolytes suitable for roomtemperature operation of batteries have been found [9][10][11][12][13][14][15] .…”

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confidence: 99%

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries

et al. 2012

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“…Variation of the ionic conductivity with temperature for 0.5Li2S + 0.5[(1 -x)GeS2 + xGeO2) glasses and compared with that of 0.5Li2S + 0.5GeS2 glass prepared by twin roller quenching 14 and rapid quenching methods. 13 The slopes of the Arrenius plots for 0.5Li2S + 0.5GeS2 glass are very different depending on the quenching rate, which gives different activation energies. 37 (0.41) 37 0.5Li2S + 0.5GeS2 ity must be caused by a structural change to the glass that in turn leads to a decrease in the activation energy.…”

Section: Ionic Conductivities Of 05li 2 Smentioning

confidence: 99%

“…First, we searched and found various GeS 2 -based lithium glasses exhibiting high conductivity of ∼10 -3 to 10 -4 (Ω cm) -1 , 8,[13][14][15][16][17][18][19][20] and these glasses are shown in Table 1. LiI-doped glasses show the highest conductivity as expected, but they have been excluded in our investigations due to the instability of LiI in contact with Li metal.…”

Section: Introductionmentioning

confidence: 99%

Anomalous Ionic Conductivity Increase in Li₂S + GeS₂ + GeO₂ Glasses

2006

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Numerous studies of the ionic conductivities in oxide-doped chalcogenaide glasses have shown the anomalous result that the ionic conductivity actually increases significantly (by more than a factor of 10 in some cases) by the initial addition of an oxide phase to a pure sulfide glass. After this initial sharp increase, the conductivity then monotonically decreases with further oxide addition. While this behavior is important to the application of these glasses for Li batteries, no definitive understanding of this behavior has been elucidated. To examine this effect further and more completely, the ionic conductivities of 0.5Li2S + 0.5[(1 − x)GeS2 + xGeO2] glasses have been measured on disc-type bulk glasses. The ionic conductivity of the 0.5Li2S + 0.5GeS2 (x = 0) glass was observed to increase from 4.3 × 10-5 (Ω cm)-1 to 1.5 × 10-4 (Ω cm)-1 while the activation energy decreased to 0.358 eV from 0.385 eV by the addition of 5 mol % of GeO2. Further addition of GeO2 monotonically decreased the conductivity and increased the activation energy. On the basis of our previous studies of the structure of this glass system, the Anderson and Stuart model was applied to explain the decrease in the activation energy and increase in the conductivity. It is suggested that the "doorway" radius between adjacent cation sites increases slightly (from 0.29(±0.05) Å to 0.40(±0.05) Å) with the addition of oxygen to the glass and is proposed to be the major cause in decreasing the activation energy and thereby increasing the conductivity. Further addition of oxides appears to contract the glass structure (and the doorway radius) leading to an increase in the conductivity activation energy and a decrease in the conductivity. Numerous studies of the ionic conductivities in oxide-doped chalcogenaide glasses have shown the anomalous result that the ionic conductivity actually increases significantly (by more than a factor of 10 in some cases) by the initial addition of an oxide phase to a pure sulfide glass. After this initial sharp increase, the conductivity then monotonically decreases with further oxide addition. While this behavior is important to the application of these glasses for Li batteries, no definitive understanding of this behavior has been elucidated. To examine this effect further and more completely, the ionic conductivities of 0.5Li 2 S + 0.5[(1 -x)GeS 2 + xGeO 2 ] glasses have been measured on disc-type bulk glasses. The ionic conductivity of the 0.5Li 2 S + 0.5GeS 2 (x ) 0) glass was observed to increase from 4.3 × 10 -5 (Ω cm) -1 to 1.5 × 10 -4 (Ω cm) -1 while the activation energy decreased to 0.358 eV from 0.385 eV by the addition of 5 mol % of GeO 2 . Further addition of GeO 2 monotonically decreased the conductivity and increased the activation energy. On the basis of our previous studies of the structure of this glass system, the Anderson and Stuart model was applied to explain the decrease in the activation energy and increase in the conductivity. It is suggested that the "doorway" radius between adjacen...

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“…Many studies have been conducted for enhancing the conductivity of solid electrolytes. 1)3) Sulfide based glassy solid electrolytes in the systems Li 2 SSiS 2 and Li 2 SP 2 S 5 showed lithium ion conductivity higher than 10 ¹4 S cm ¹1 at room temperature. 4), 5) The sulfide glasses were prepared not only by conventional melt quenching but also mechanical milling using a planetary ball mill apparatus.…”

Section: Introductionmentioning

confidence: 98%

Preparation and characterization of superionic conducting Li7P3S11 crystal from glassy liquids

Minami

Hayashi

Tatsumisago

2010

J. Ceram. Soc. Japan

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Superionic Li+ ion conducting Li 7 P 3 S 11 crystal was prepared by crystallization of the 70Li 2 S·30P 2 S 5 (mol %) glass and melt. In the case of crystallization of the 70Li 2 S·30P 2 S 5 glass, the crystallized electrolyte heated at 360°C for 1 h showed a conductivity of 4.1 © 10 ¹3 S cm ¹1 at room temperature. In the case of crystallization from the 70Li 2 S·30P 2 S 5 melt, a single phase of the Li 7 P 3 S 11 crystal was obtained by crystallization of the melt at 700°C for 48 h and then quenching in ice water. The crystallized electrolyte showed the conductivity of 2.9 © 10 ¹3 S cm ¹1 at room temperature. The precipitated crystal depended on the heat treatment temperature, holding time, and cooling rate. In both crystallization processes from the glass and melt, the Li 7 P 3 S 11 crystal was precipitated as a primary phase from supercooled liquids and thus the superionic conducting Li 7 P 3 S 11 crystal is a high temperature phase at the composition 70Li 2 S·30P 2 S 5 .

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Sulfide glasses: Glass forming region, structure and ionic conduction of glasses in Na2SXS2 (XSi; Ge), Na2SP2S5 and Li2SGeS2 systems

Cited by 167 publications

References 5 publications

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries

Anomalous Ionic Conductivity Increase in Li₂S + GeS₂ + GeO₂ Glasses

Preparation and characterization of superionic conducting Li7P3S11 crystal from glassy liquids

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Sulfide glasses: Glass forming region, structure and ionic conduction of glasses in Na2SXS2 (XSi; Ge), Na2SP2S5 and Li2SGeS2 systems

Cited by 167 publications

References 5 publications

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries

Anomalous Ionic Conductivity Increase in Li2S + GeS2 + GeO2 Glasses

Preparation and characterization of superionic conducting Li7P3S11 crystal from glassy liquids

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Product

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Anomalous Ionic Conductivity Increase in Li₂S + GeS₂ + GeO₂ Glasses