Crystal structure and phase transitions of the lithium ionic conductor Li3PS4

Homma, Kazuaki; Yonemura, Masao; Kobayashi, Takeshi; Nagao, Miki; Hirayama, Masaaki; Kanno, Ryoji

doi:10.1016/j.ssi.2010.10.001

Cited by 320 publications

(430 citation statements)

References 17 publications

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“…The temperature dependence of Figure 3.) This activation energy value, although higher than that reported in a crystalline phase of sulfide solid electrolytes, 24 is still reasonable if compared with values obtained for other amorphous phases. 26 The lithium ion conductivity of our Li 3 PS 4 sample was found to be on the order of 10 −4 Scm −1 .…”

Section: Resultssupporting

confidence: 85%

“…23 In fact, different activation energy values have been reported for this type of electrolyte materials. 24,25 Lithium ion conductivity.-Li 3 PS 4 is a single ion solid conductor and, as such, its mechanism of ionic transport is quite different from that occurring in liquid electrolytes. The temperature dependence of Figure 3.)…”

Section: Resultsmentioning

confidence: 99%

“…The density of the solid electrolyte pellet was 1.64 g · cm −3 at room temperature (24 • C). The pellet was used for determining the ionic conductivity and charge transfer resistance of the electrolyte layer.…”

Section: Synthesis Of LI 3 Psmentioning

confidence: 99%

See 2 more Smart Citations

All Solid-State Lithium–Sulfur Battery Using a Glass-Type P₂S₅–Li₂S Electrolyte: Benefits on Anode Kinetics

Yamada

Ito

Omoda

et al. 2015

J. Electrochem. Soc.

201

132

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Lithium-sulfur (Li-S) batteries are promising candidates for next generation electrical energy storage devices due to their high specific energy. Despite intense research, there are still a number of technical challenges in developing a high performance Li-S battery. To elucidate the issues, an all solid-state Li-S battery was fabricated using Li 3 PS 4 solid electrolyte. Most of the theoretical capacity of sulfur, 1600 mAhg −1 was attained in the initial discharge-charge cycles with a high coulombic efficiency approaching 99%. To verify the benefit of the solid state electrolyte, galvanostatic stripping-deposition tests were also carried out on a symmetrical Li/Li cell and compared with those of a liquid electrolyte (1 M-lithium bis(trifluoromethane sulfonyl) imide (LiTFSI) in a mixture of 1,3-dioxolane (DOL)-diethoxyethane (DEE)). The kinetics and thermodynamics of the solid-state cell are discussed from the viewpoint of the charge transfer processes. This study demonstrates both the merits and drawbacks of using the solid sulfide electrolyte in a Li-S battery and facilitates the further improvement of this important high energy storage device. Lithium-sulfur (Li-S) batteries are attracting growing interest owing to their high specific energy above 3000 Whkg −1 (active material). However, before this technology can be used in practice, there are some significant challenges to overcome, including red-ox shuttle of polysulfides as well as poor lithium cycle performance.The polysulfide redox shuttle originates from the dissolution of the cathode material into the organic electrolyte. So far, various approaches have been suggested to solve the red-ox shuttle issue. LiNO 3 is a well-known additive for optimizing the solid electrolyte interphase (SEI) on lithium metal electrode, such as to block the deposition of polysulfides.1,2 An ionommer (e.g., Nafion) has also been proposed for preventing the polysulfide migration 3 and a buffer solution containing polysulfides can facilitate a good cycle ability as well. 4 The poor lithium cycle performance is due to the consumption of lithium metal during the charge-discharge process. It is well known that the lithium cycling response is primarily determined by the type of electrolyte to which it is in contact. 5,6 In the development of lithiummetal secondary batteries the Figure of Merit (FOM) is the parameter used to evaluate the lithium cycling ability. 5,6 Although lithium metal has a high specific capacity of 3862 mAhg −1 , its effective degree of utilization (i.e., the lithium loss relative to the amount of total input lithium metal) has to be taken into account. Generally, a valid parameter to determine the cycle ability of the lithium anode is the efficiency. For instance, it is difficult to achieve an efficiency higher than 99% for lithium cycling in a typical liquid electrolyte cell due to losses during its dissolution-deposition reaction. Therefore, the improvement of the FOM of a liquid electrolyte Li-S battery has been a major challenge to enhance the charge-disc...

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Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

All Solid-State Lithium–Sulfur Battery Using a Glass-Type P₂S₅–Li₂S Electrolyte: Benefits on Anode Kinetics

Yamada

Ito

Omoda

et al. 2015

J. Electrochem. Soc.

201

132

View full text Add to dashboard Cite

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“…We tested various synthesis conditions and found that although the optimized mixing procedures and cooling rates are important for obtaining monophasic LSiPSO (see Figure S1 and Table S1 in Supplementary Material), the composition is more relevant with respect to the phase that appears in the samples. In the case of the compositions on the Li4SiS2O2-Li3PS4 tie line, the LSiPSO phase was not obtained as a pure phase; the main phases were a β-Li3PS4-derived phase in samples #2 and #3, a LSiPSO phase along with the Li7PS6 phase with an argyroditelike structure in sample #4, and a Si-based LGPS-type phase in sample #5 (Kong et al, 2010;Homma et al, 2011). For compositions derived from the Li4SiS2O2-Li3PS4 tie line, the phases that appeared changed with the amount of SiO2 in the composition; for the samples with smaller amounts of SiO2 compared to the case for sample #4, the Li7PS6 phase and a β-Li3PS4 modification were observed as the main primary phases in the samples #6 and #7, respectively.…”

Section: Electrochemical Measurementsmentioning

confidence: 96%

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

et al. 2016

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“…Experimental densities for amorphous structures have not been measured, to the best of our knowledge. Thus, Figure 3B provides a comparison of the calculated densities of amorphous structures and the experimental densities of the crystals (Yamane et al, 2007;Onodera et al, 2010;Homma et al, 2011). In addition, Figure 3B shows comparisons with the density of crystal obtained by geometrical optimization of the usual DFT calculation.…”

Section: Amorphous Structuresmentioning

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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Crystal structure and phase transitions of the lithium ionic conductor Li3PS4

Cited by 320 publications

References 17 publications

All Solid-State Lithium–Sulfur Battery Using a Glass-Type P₂S₅–Li₂S Electrolyte: Benefits on Anode Kinetics

All Solid-State Lithium–Sulfur Battery Using a Glass-Type P₂S₅–Li₂S Electrolyte: Benefits on Anode Kinetics

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

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

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Crystal structure and phase transitions of the lithium ionic conductor Li3PS4

Cited by 320 publications

References 17 publications

All Solid-State Lithium–Sulfur Battery Using a Glass-Type P2S5–Li2S Electrolyte: Benefits on Anode Kinetics

All Solid-State Lithium–Sulfur Battery Using a Glass-Type P2S5–Li2S Electrolyte: Benefits on Anode Kinetics

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

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

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All Solid-State Lithium–Sulfur Battery Using a Glass-Type P₂S₅–Li₂S Electrolyte: Benefits on Anode Kinetics

All Solid-State Lithium–Sulfur Battery Using a Glass-Type P₂S₅–Li₂S Electrolyte: Benefits on Anode Kinetics