Lithium Superionic Conductor Li9.42Si1.02P2.1S9.96O2.04 with Li10GeP2S12-Type Structure in the Li2S–P2S5–SiO2 Pseudoternary System: Synthesis, Electrochemical Properties, and Structure–Composition Relationships

Hori, Shingo; Suzuki, Kota; Hirayama, Masaaki; Kato, Yoshifumi; Kanno, Ryoji

doi:10.3389/fenrg.2016.00038

Cited by 62 publications

(56 citation statements)

References 33 publications

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“…[ 12 ] Based on this method, which is one of the standard protocols for laboratory‐level research, numerous synthesis methods have been developed, as listed in Table 1 . [ 12,13,28–47 ] A subsequent study reported that synthesis temperatures more than 400 °C are required for the crystallization of the LGPS phase from precursors obtained by mechanochemical treatment. [ 48 ] In‐depth temperature‐composition studies have been performed to obtain high‐purity LGPS phases and comprehend the Li 4 GeS 4 –Li 3 PS 4 pseudo‐binary system.…”

Section: Synthesismentioning

confidence: 99%

“…In contrast to the halogen‐doped system, the oxygen atom noticeably substitutes the sulfide atom in the crystal structure; the existence of solid solutions was confirmed by structural analysis based on synchrotron XRD data. [ 37,38,65 ] Previous studies have systematically investigated oxygen substitution in the LGPS structure, proposing that the oxygen‐substituted LGPS‐type phases show improved electrochemical stability against reduction at low potential, even though they suffer from a tolerable decrease in conductivity. Such properties change depending on the degree of oxygen substitution.…”

Section: Synthesismentioning

confidence: 99%

“…[ 45 ] The latter structure model was also used for LGPS‐type phases in different chemical systems such as Li–Sn–P–S and Li–Si–P–S–O. [ 28,37 ] It is also employed in this review in the following section for a detailed description of Li sites.…”

Section: Structurementioning

confidence: 99%

“…[ 33 ] Deviation from Li– M –P–S was observed when more than 16% of the sulfur was replaced by oxygen; Li 9 P 3 S 9 O 3 and Li 9.42 Si 1.02 P 2.1 S 9.96 O 2.04 exhibit decreased σ 0 compared to Li– M –P–S systems despite possessing comparable activation energies. [ 13,37 ] The lattice dynamics of the LGPS structure may also be influenced by anion substitution. A decrease in the prefactor was also observed in the cation substitution system of Li 9.6 P 3 S 12 .…”

Section: Ionic Transportationmentioning

confidence: 99%

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Li₁₀GeP₂S₁₂‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation

Kato

Hori

Kanno

2020

Advanced Energy Materials

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118

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Ever since the first report on Li10GeP2S12 (LGPS) in 2011, its unique structure and exceptionally high lithium conductivity (>1 × 10−2 S cm−1) have attracted extensive interest, especially for applications in solid‐state ionics and batteries. Herein, studies of LGPS and its modifications are reviewed with a focus on the synthesis, structure, and ionic transportation of LGPS. For material synthesis, the relationships between LGPS and its precursor compounds such as Li3PS4 and Li4GeS4 are discussed. A technique for single‐crystal growth and a family of LGPS‐type materials that are chemically or structurally related to LGPS are then described. The crystal structure of LGPS is analyzed from the viewpoints of tetrahedral framework units, anion sublattice, and Li distributions; furthermore, the conduction mechanism is qualitatively analyzed. Subsequently, ionic transportation in LGPS is studied quantitatively. The origin of the high conductivity is discussed in terms of the activation energy, diffusion coefficient, and its related parameters; and these factors are compared to those of other non‐LGPS‐type conductors. Then, the battery applications are briefly summarized to indicate the potential merits of using LGPS‐type solid electrolytes with high lithium conductivity. Any remaining issues and possible research directions that have emerged from the aforementioned studies are finally highlighted.

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Section: Synthesismentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Section: Structurementioning

confidence: 99%

Section: Ionic Transportationmentioning

confidence: 99%

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Li₁₀GeP₂S₁₂‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation

Kato

Hori

Kanno

2020

Advanced Energy Materials

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118

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“…In principle, more oxygen can be incorporated into a sulfide glass in comparison to a crystalline material owing to the large difference in size between the two chalcogenide anions (ionic radii of 1.4 Å for O 2− and 1.8 Å for S 2− ), and the rigid structural requirements of a crystalline lattice. One of the highest oxygen contents in a crystalline sulfide that has been reported is for Li 9.42 Si 1.02 P 2.1 S 9.96 O 2.04 , that exhibits a conductivity of 0.32 mS cm −1 . In a glass, one is also limited by the solubility of the oxide, but the constraints are fewer.…”

Section: Resultsmentioning

confidence: 99%

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

Kaup

Bazak

Vajargah

et al. 2020

Advanced Energy Materials

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As potential next‐generation energy storage devices, solid‐state lithium batteries require highly functional solid state electrolytes. Recent research is primarily focused on crystalline materials, while amorphous materials offer advantages by eliminating problematic grain boundaries that can limit ion transport and trigger dendritic growth at the Li anode. However, simultaneously achieving high conductivity and stability in glasses is a challenge. New quaternary superionic lithium oxythioborate glasses are reported that exhibit high ion conductivity up to 2 mS cm−1 despite relatively high oxygen: sulfur ratios of more than 1:2, that exhibit greatly reduced H2S evolution upon exposure to air compared to Li7P3S11. These monolithic glasses are prepared from vitreous melts without ball‐milling and exhibit no discernable XRD pattern. Solid‐state NMR studies elucidate the structural entities that comprise the local glass structure which dictates fast ion conduction. Stripping/plating onto lithium metal results in very low polarization at a current density of 0.1 mA cm−2 over repeated cycling. Evaluation of the optimal glass composition as an electrolyte in an all‐solid‐state battery shows it exhibits excellent cycling stability and maintains near theoretical capacity for over 130 cycles at room temperature with Coulombic efficiency close to 99.9%, opening up new avenues of exploration for these quaternary compositions.

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Thio‐/LISICON and LGPS‐Type Solid Electrolytes for All‐Solid‐State Lithium‐Ion Batteries

Tao

Ren²,

et al. 2022

Adv Funct Materials

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As an integral part of all‐solid‐state lithium (Li) batteries (ASSLBs), solid‐state electrolytes (SSEs) must meet requirements in high ionic conductivity, electrochemical/chemical stability toward the electrode. The ionic conductivity of the Li super ionic conductor (LISICON) is limited, and the thio‐LISICON is improved by replacing O2− in the LISICON with S2−. Currently, the ionic conductivity of Li10GeP2S12 (LGPS) has exceeded 10 mS cm−1, which meets the demands of commercial ASSLBs. However, poor stability of SSEs, baneful interfacial reactions, Li dendrite growth, and other factors have impeded the development of ASSLBs. Hence, this review first traces the development progress of thio‐/LISICON and LGPS‐type SSEs, analyzes the complicated ion transport mechanism, and summarizes the effective strategies for improving ionic conductivity. Moreover, exciting methods focusing on electrode interface engineering are outlined separately. As to SSE/anode interface, poor chemical or electrochemical compatibility, poor interfacial contact, and the mechanisms of dendrite formation are discussed. For the SSE/cathode interface, poor interfacial stability and non‐intimate solid–solid contact are daunting challenges. Then, effective methods to improve interface stability and electrochemical performance of ASSLBs with LGPS‐type SSEs are introduced. Finally, combined with the present chances and challenges, the possible future developing directions of LGPS‐based ASSLBs and the perspectives are proposed.

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Lithium Superionic Conductor Li9.42Si1.02P2.1S9.96O2.04 with Li10GeP2S12-Type Structure in the Li2S–P2S5–SiO2 Pseudoternary System: Synthesis, Electrochemical Properties, and Structure–Composition Relationships

Cited by 62 publications

References 33 publications

Li₁₀GeP₂S₁₂‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation

Li₁₀GeP₂S₁₂‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

Thio‐/LISICON and LGPS‐Type Solid Electrolytes for All‐Solid‐State Lithium‐Ion Batteries

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Lithium Superionic Conductor Li9.42Si1.02P2.1S9.96O2.04 with Li10GeP2S12-Type Structure in the Li2S–P2S5–SiO2 Pseudoternary System: Synthesis, Electrochemical Properties, and Structure–Composition Relationships

Cited by 62 publications

References 33 publications

Li10GeP2S12‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation

Li10GeP2S12‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

Thio‐/LISICON and LGPS‐Type Solid Electrolytes for All‐Solid‐State Lithium‐Ion Batteries

Contact Info

Product

Resources

About

Li₁₀GeP₂S₁₂‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation

Li₁₀GeP₂S₁₂‐Type Superionic Conductors: Synthesis, Structure, and Ionic Transportation