Crystal Structure of High-Temperature Phase of Lithium Ionic Conductor, Li<sub>3</sub>PS<sub>4</sub>

Homma, Kenji; Yonemura, Masao; Nagao, Masanori; Hirayama, Masaaki; Kanno, Ryoji

doi:10.1143/jpsjs.79sa.90

Cited by 46 publications

(44 citation statements)

References 12 publications

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“…Examples of these impurity phases include Li 3 PS 4 and Li 4 GeS 4 (both are the end members of the phase diagram), as well as Li 4 P 2 S 7 (Li 4 P 2 S 6 ), Li 7 PS 6 , and Li 2 GeS 3 . [ 19,20,53–56 ] Reports have postulated that the samples contained amorphous phases, whose amount influences the ionic conductivity when synthesis temperatures below 550 °C are used. [ 48 ] These reports indicate that secondary phase components in the sample are partially responsible for differences in the reported conductivity and thermal stability.…”

Section: Synthesismentioning

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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122

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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%

“…Such compounds include Li 4 GeS 4 , Li 2 GeS 3 , Li 7 PS 6 , Li 3 PS 4 , and Li 4 P 2 S 7 (Li 4 P 2 S 6 ). [ 19,20,53–56 ]…”

Section: Synthesismentioning

confidence: 99%

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

Kato

Hori

Kanno

2020

Advanced Energy Materials

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122

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“…Fig. 9 shows the PS 4 tetrahedral arrangements of Li 3 PS 4 modifications of the γ and β-phases along with the structure of the α-phase [12], and the materials of other well-known poly-anion systems. Table 5 summarizes crystal systems and cell parameters of γ-, β-, and α-phases of other lithium conducting materials..…”

Section: Tablementioning

confidence: 99%

Crystal structure and phase transitions of the lithium ionic conductor Li3PS4

et al. 2011

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“…An LGPS phase exhibiting extremely high ionic conductivity exists in the Li 4 GeS 4 –Li 3 PS 4 quasi‐binary system, and this system contains various compounds having several structure types: α‐, β‐, and γ‐type Li 3 PS 4 , as well as Li 4 GeS 4 having a β‐Li 3 PS 4 ‐type structure . Among these phases, the β‐type modification, also known as the thio‐LISICON phase, shows particularly high ionic conductivity, on the order of 10 −3 S/cm .…”

Section: Introductionmentioning

confidence: 99%

“…An LGPS phase exhibiting extremely high ionic conductivity exists in the Li 4 GeS 4 -Li 3 PS 4 quasi-binary system, and this system contains various compounds having several structure types: a-, b-, and c-type Li 3 PS 4 , as well as Li 4 GeS 4 having a b-Li 3 PS 4 -type structure. 20,21,23 Among these phases, the btype modification, also known as the thio-LISICON phase, shows particularly high ionic conductivity, on the order of 10 À3 S/cm. 24 Each of these structures is composed of isolated PS 4 tetrahedra that together form a three-dimensional framework structure, similar to those observed for the analogous oxide phases in the Li 3 PO 4 -related systems (LISICON).…”

Section: Introductionmentioning

confidence: 99%

Phase Diagram of the Li₄GeS₄–Li₃PS₄ Quasi‐Binary System Containing the Superionic Conductor Li₁₀GeP₂S₁₂

et al. 2015

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A phase diagram is constructed for the quasi-binary Li 4 GeS 4 -Li 3 PS 4 system containing the lithium superionic conductor Li 10 GeP 2 S 12 (LGPS), having an LGPS-type structure, and the b-Li 3 PS 4 -type phase, having a thio-LISICON structure. The LGPS and thio-LISICON intermediate compounds are found to exhibit solid solution ranges and show incongruent melting at 650°C and 560°C, respectively. The end-member Li 4 GeS 4 has a compositional range of 0 < k < 0.3 in [(1 -k) Li 4 GeS 4 + k Li 3 PS 4 ], while the other end-member cLi 3 PS 4 has no solid solution range. The crystal structures appearing in the binary systems are the a-, b-, and c-type Li 3 PS 4 structures and the LGPS-type structure, and these are formed by PS 4 tetrahedra with different arrangements in each structure. The phase and structural relationships between the compounds appearing in the Li 4 GeS 4 -Li 3 PS 4 system are thus clarified.

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Crystal Structure of High-Temperature Phase of Lithium Ionic Conductor, Li₃PS₄

Cited by 46 publications

References 12 publications

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

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

Crystal structure and phase transitions of the lithium ionic conductor Li3PS4

Phase Diagram of the Li₄GeS₄–Li₃PS₄ Quasi‐Binary System Containing the Superionic Conductor Li₁₀GeP₂S₁₂

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Crystal Structure of High-Temperature Phase of Lithium Ionic Conductor, Li3PS4

Cited by 46 publications

References 12 publications

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

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

Crystal structure and phase transitions of the lithium ionic conductor Li3PS4

Phase Diagram of the Li4GeS4–Li3PS4 Quasi‐Binary System Containing the Superionic Conductor Li10GeP2S12

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Crystal Structure of High-Temperature Phase of Lithium Ionic Conductor, Li₃PS₄

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

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

Phase Diagram of the Li₄GeS₄–Li₃PS₄ Quasi‐Binary System Containing the Superionic Conductor Li₁₀GeP₂S₁₂