Oxygen substitution effects in Li10GeP2S12 solid electrolyte

Sun, Yuhui; Suzuki, Kota; Hara, Kosuke O.; Hori, Shingo; Yano, Taka-aki; Hara, Masahiko; Hirayama, Masaaki; Kanno, Ryoji

doi:10.1016/j.jpowsour.2016.05.100

Cited by 159 publications

(142 citation statements)

References 31 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%

“…using Li 2 O as an oxygen source in synthesis. [ 38 ] The substitution range (0 ≤ x ≤ 0.6) in Li 10 GeP 2 S 12− x O x was determined by observation of the continuous lattice parameter change. When the oxygen‐substituted LGPS was used in the solid‐state cell with Li–In anode and LiCoO 2 , the cell exhibited improved cycle performance compared to that using the non‐doped counterpart, without compromising the ionic conductivity (on the order of ≈10 −2 S cm −1 ).…”

Section: Synthesismentioning

confidence: 99%

See 2 more Smart Citations

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

Kato

Hori

Kanno

2020

Advanced Energy Materials

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137

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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: Synthesismentioning

confidence: 99%

See 1 more Smart Citation

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

Kato

Hori

Kanno

2020

Advanced Energy Materials

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137

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“…Therefore the assembled ASSLIBs with 70Li 2 S−29P 2 S 5 −1P 2 O 5 exhibited better electrochemical performances than those with the pristine electrolyte. Sun et al . reported the oxygen substitution effects in Li 10 GeP 2 S 12 electrolytes.…”

Section: Development Of All‐solid‐state Batteriesmentioning

confidence: 99%

Recent Developments of All‐Solid‐State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes

Zhang

Wang

et al. 2018

Chemistry A European J

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Due to the increasing demand of security and energy density, all-solid-state lithium ion batteries have become the promising next-generation energy storage devices to replace the traditional liquid batteries with flammable organic electrolytes. In this Minireview, we focus on the recent developments of sulfide inorganic electrolytes for all-solid-state batteries. The challenges of assembling bulk-type all-solid-state batteries for industrialization are discussed, including low ionic conductivity of the present sulfide electrolytes, high interfacial resistance and poor compatibility between electrolytes and electrodes. Many efforts have been focused on the solutions for these issues. Although some progresses have been achieved, it is still far away from practical application. The perspectives for future research on all-solid-state lithium ion batteries are presented.

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“…On the other hand, oxides, for example, have good stability and reasonably ionic conductivity 21,25–29. Therefore, it is conceivable that an oxy‐sulfide structure contained not one but at least two or three cation/anion, such as PO 4 or GeS 4 units, that blends the best of both the sulfides and oxides into a whole 26,30. Recent Kato et al have published a patent about the manufacturing method of crystal oxygen‐sulfide solid electrolyte material (Li (4− x ) Si (1− x ) P (x) S (4−2a) O (2a) (LSiPSO), a=1 − x , 0.65 ≤ x ≤ 0.75) 31.…”

Section: Introductionmentioning

confidence: 99%

Li‐Ion Cooperative Migration and Oxy‐Sulfide Synergistic Effect in Li₁₄P₂Ge₂S₁₆₋₆_xO_x Solid‐State‐Electrolyte Enables Extraordinary Conductivity and High Stability

Zhang

Weng

Lin

et al. 2020

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Critical to the development of all‐solid‐state lithium‐ion batteries technology are novel solid‐state electrolytes with high ionic conductivity and robust stability under inorganic solid‐electrolyte operating conditions. Herein, by using density functional theory and molecular dynamics, a mixed oxygen‐sulfur‐based Li‐superionic conductor is screened out from the local chemical structure of β‐Li3PS4 to discover novel Li14P2Ge2S8O8 (LPGSO) with high ionic conductivity and high stability under thermal, moist, and electrochemical conditions, which causes oxygenation at specific sites to improve the stability and selective sulfuration to provide an O‐S mixed path by Li‐S/O structure units with coordination number between 3 and 4 for fast Li‐cooperative conduction. Furthermore, LPGSO exhibits a quasi‐isotropic 3D Li‐ion cooperative diffusion with a lesser migration barrier (≈0.19 eV) compared to its sulfide‐analog Li14P2Ge2S16. The theoretical ionic conductivity of this conductor at room temperature is as high as ≈30.0 mS cm−1, which is among the best in current solid‐state electrolytes. Such an oxy‐sulfide synergistic effect and Li‐ion cooperative migration mechanism would enable the engineering of next‐generation electrolyte materials with desirable safety and high ionic conductivity, for possible application in the near future.

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Oxygen substitution effects in Li10GeP2S12 solid electrolyte

Cited by 159 publications

References 31 publications

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

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

Recent Developments of All‐Solid‐State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes

Li‐Ion Cooperative Migration and Oxy‐Sulfide Synergistic Effect in Li₁₄P₂Ge₂S₁₆₋₆_xO_x Solid‐State‐Electrolyte Enables Extraordinary Conductivity and High Stability

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Oxygen substitution effects in Li10GeP2S12 solid electrolyte

Cited by 159 publications

References 31 publications

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

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

Recent Developments of All‐Solid‐State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes

Li‐Ion Cooperative Migration and Oxy‐Sulfide Synergistic Effect in Li14P2Ge2S16−6xOx Solid‐State‐Electrolyte Enables Extraordinary Conductivity and High Stability

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Product

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

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

Li‐Ion Cooperative Migration and Oxy‐Sulfide Synergistic Effect in Li₁₄P₂Ge₂S₁₆₋₆_xO_x Solid‐State‐Electrolyte Enables Extraordinary Conductivity and High Stability