High lithium ion conducting glass-ceramics in the system Li2S–P2S5

Mizuno, Fuminori; Hayashi, Akitoshi; Tadanaga, Kiyoharu; Tatsumisago, Masahiro

doi:10.1016/j.ssi.2006.04.017

Cited by 309 publications

(253 citation statements)

References 13 publications

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“…, which depend on the degree of crystallinity and the grain boundary of Li7P3S11 (Mizuno et al, 2005(Mizuno et al, , 2006Seino et al, 2014). Cubic Na3PS4 is crystallized from the Na3PS4 glass prepared by mechanical milling.…”

Section: Preparation Processmentioning

confidence: 99%

Development of Sulfide Solid Electrolytes and Interface Formation Processes for Bulk-Type All-Solid-State Li and Na Batteries

2016

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All-solid-state batteries with inorganic solid electrolytes (SEs) are recognized as an ultimate goal of rechargeable batteries because of their high safety, versatile geometry, and good cycle life. Compared with thin-film batteries, increasing the reversible capacity of bulk-type all-solid-state batteries using electrode active material particles is difficult because contact areas at solid-solid interfaces between the electrode and electrolyte particles are limited. Sulfide SEs have several advantages of high conductivity, wide electrochemical window, and appropriate mechanical properties, such as formability, processability, and elastic modulus. Sulfide electrolyte with Li7P3S11 crystal has a high Li + ion conductivity of 1.7 × 10 −2 S cm −1 at 25°C. It is far beyond the Li + ion conductivity of conventional organic liquid electrolytes. The Na + ion conductivity of 7.4 × 10 −4 S cmis achieved for Na3.06P0.94Si0.06S4 with cubic structure. Moreover, formation of favorable solid-solid interfaces between electrode and electrolyte is important for realizing solid-state batteries. Sulfide electrolytes have better formability than oxide electrolytes. Consequently, a dense electrolyte separator and closely attached interfaces with active material particles are achieved via "room-temperature sintering" of sulfides merely by cold pressing without heat treatment. Elastic moduli for sulfide electrolytes are smaller than that of oxide electrolytes, and Na2S-P2S5 glass electrolytes have smaller Young's modulus than Li2S-P2S5 electrolytes. Cross-sectional SEM observations for a positive electrode layer reveal that sulfide electrolyte coating on active material particles increases interface areas even with a minimum volume of electrolyte, indicating that the energy density of bulk-type solid-state batteries is enhanced. Both surface coating of electrode particles and preparation of nanocomposite are effective for increasing the reversible capacity of the batteries. Our approaches to form solid-solid interfaces are demonstrated.

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Section: Preparation Processmentioning

confidence: 99%

Development of Sulfide Solid Electrolytes and Interface Formation Processes for Bulk-Type All-Solid-State Li and Na Batteries

2016

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“…Much research has been conducted since the first report that the glass and glass-ceramic phases are fast ionic conductors (Zhang and Kennedy, 1990). At present, the maximum conductivity occurs at 70-80 mol% Li 2 S (i.e., 30-20 mol% P 2 S 5 ), depending on the conditions during preparation (Minami et al, 2006;Mizuno et al, 2006). In general, it is difficult to prepare sulfide glasses with higher Li concentrations because crystallization occurs easily during the cooling process.…”

Section: Introductionmentioning

confidence: 99%

Structure and Ionic Conductivity of Li2S–P2S5 Glass Electrolytes Simulated with First-Principles Molecular Dynamics

Baba

Kawamura

2016

Front. Energy Res.

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Lithium thiophosphate-based materials are attractive as solid electrolytes in all-solidstate lithium batteries because glass or glass-ceramic structures of these materials are associated with very high conductivity. In this work, we modeled lithium thiophosphates with amorphous structures and investigated Li + mobilities by using molecular dynamics calculations based on density functional theory (DFT-MD). The structures of xLi 2 S-(100 − x)P 2 S 5 (x = 67, 70, 75, and 80) were created by randomly identifying appropriate compositions of Li + , PS The implication is that these amorphous structures are metastable. There was good agreement between calculated and experimental structure factors determined from X-ray scattering. The differences between the structure factors of amorphous structures were small, except for the first sharp diffraction peak, which was affected by the environment between Li and S atoms. Li + diffusion coefficients obtained from DFT-MD calculations at various temperatures for picosecond simulation times were on the order of 10 −3 -10 −5 Å 2 /ps. Ionic conductivities evaluated by the Nernst-Einstein relationship at 298.15 K were on the order of 10 −5 S/cm. The ionic conductivity of the amorphous structure with x = 75 was the highest among the amorphous structures because there was a balance between the number density and diffusibility of Li + . The simulations also suggested that isolated S atoms suppress Li + migration.

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“…2,3 Li 2 S-P 2 S 5 glasses and glass-ceramics exhibited high conductivities of 10 ¹3 S cm ¹1 at room temperature and wide electrochemical windows of 05 V (vs. Li + /Li). 4,5 Li-Ge-P-S system crystals showed very high conductivities of 10…”

Section: Introductionmentioning

confidence: 99%

Glass Electrolytes with High Ion Conductivity and High Chemical Stability in the System LiI-Li2O-Li2S-P2S5

et al. 2013

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The Li 2 O-Li 2 S-P 2 S 5 glasses, which were prepared by a reaction of the Li 2 S-P 2 S 5 glass and Li 2 O, hardly generated H 2 S gas in air. These glasses showed relatively high ion conductivities about 10 −4 S cm −1 at room temperature. However, these conductivities were lower than those of original sulfide glasses. In this study, an addition of LiI to the Li 2 OLi 2 S-P 2 S 5 glasses was examined in order to improve ion conductivities. The 30LiI·70(0.07Li 2 O·0.68Li 2 S·0.25P 2 S 5 ) glass showed high ion conductivity of 1.3 × 10 −3 S cm −1 at room temperature, and hardly generated H 2 S gas in air. On the other hand, the 30LiI·70(0.07Li 2 O·0.68Li 2 S·0.25P 2 S 5 ) glass was electrochemically stable in the potential range of 0-10 V. Moreover, the all-solid-state C/LiCoO 2 cell using the 30LiI·70(0.07Li 2 O·0.68Li 2 S·0.25P 2 S 5 ) glass as solid electrolytes worked as lithium secondary batteries at room temperature, and exhibited a good cycle performance. Therefore, the 30LiI·70(0.07Li 2 O·0.68Li 2 S·0.25P 2 S 5 ) glass was a suitable electrolyte for all-solidstate cells because the glass had high conductivity, wide electrochemical window and high chemical stability to moisture.

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High lithium ion conducting glass-ceramics in the system Li2S–P2S5

Cited by 309 publications

References 13 publications

Development of Sulfide Solid Electrolytes and Interface Formation Processes for Bulk-Type All-Solid-State Li and Na Batteries

Development of Sulfide Solid Electrolytes and Interface Formation Processes for Bulk-Type All-Solid-State Li and Na Batteries

Structure and Ionic Conductivity of Li2S–P2S5 Glass Electrolytes Simulated with First-Principles Molecular Dynamics

Glass Electrolytes with High Ion Conductivity and High Chemical Stability in the System LiI-Li2O-Li2S-P2S5

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