All solid-state sheet battery using lithium inorganic solid electrolyte, thio-LISICON

Inada, Taro; Kobayashi, Takeshi; Sonoyama, Noriyuki; Yamada, Atsuo; Kondô, Shigeo; Nagao, Masanori; Kanno, Ryoji

doi:10.1016/j.jpowsour.2009.06.100

Cited by 88 publications

(77 citation statements)

References 12 publications

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“…As the 6 Li nucleus has a spin of 1, no quadrupolar sideband pattern is expected in these spectra, even for nuclei in noncubic environments. Owing to the very small quadrupole moment of the 6 Li nuclide, the anisotropic quadrupolar coupling is completely averaged out by MAS. Furthermore, the significantly lower magnetic moment of 6 Li, combined with its low natural abundance, greatly reduces homonuclear dipolar broadening effects in the spectra, resulting in significantly enhanced spectroscopic resolution in comparison with 7 Li MAS NMR spectra.…”

Section: ■ Results and Discussionmentioning

confidence: 95%

“…Owing to the very small quadrupole moment of the 6 Li nuclide, the anisotropic quadrupolar coupling is completely averaged out by MAS. Furthermore, the significantly lower magnetic moment of 6 Li, combined with its low natural abundance, greatly reduces homonuclear dipolar broadening effects in the spectra, resulting in significantly enhanced spectroscopic resolution in comparison with 7 Li MAS NMR spectra. 31 As shown in Figure 5b, two distinct types of lithium sites appear well-resolved at sufficiently low temperature (167 K), at 1.2 and −0.2 ppm.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…7 5 S 4 and Li 3.4 Si 0.4 P 0.6 S 4 have already been tested as ceramic solid electrolytes in a battery. 6,38,39 Although these compounds exhibit a high electrochemical stability, the cycling in a battery resulted in the formation of an SEI. 36 In this case, the formation of a stable SEI turned out to be favorable, as it promoted electrode/electrolyte contact and led to fast charge transfer across the interface.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Relaxation delays ranged between 1 and 100 s, dependent on temperature. 6 Li-MAS NMR spectra were recorded at 58.862 MHz and a rotation frequency of 5 kHz. The 90°pulse lengths ranged from 6.9 to 8.0 μs, and relaxation delays between 5 and 150 s were used.…”

Section: S·cmmentioning

confidence: 99%

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New Lithium Chalcogenidotetrelates, LiChT: Synthesis and Characterization of the Li⁺-Conducting Tetralithium ortho-Sulfidostannate Li₄SnS₄

et al. 2012

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A new lithium chalcogenidotetrelate, denoted as LiChT phase, with the elemental combination Li/Sn/S was synthesized as solvent-free and solvent-containing salts. We present and discuss syntheses, crystal structures, spectroscopic and thermal properties of the phases, as well as the Li + ion conductivity of Li 4 SnS 4 , which is formally related to the thio-LISICON parent system Li 4 GeS 4 , and thus represents the first member of a new thiostannate-LISICON family. The solvent-free title compound shows a very promising Li + ion conductivity of 7 × 10 −5 S·cm −1 at 20°C and 3 × 10S·cm −1 at 100°C, which is exceptionally high for a ternary compound. Activation energies for the lithium ion transport measured via impedance spectroscopy (0.41 eV) correlate reasonably well with the values (0.29 to 0.33 eV) deduced from ionic mobility studies by 7 Li solid-state NMR spectroscopy. NMR two-time correlation functions suggest the occurrence of an additional, geometrically more restricted, ultraslow-motional process down to 121 K.

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Section: ■ Results and Discussionmentioning

confidence: 95%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: S·cmmentioning

confidence: 99%

See 2 more Smart Citations

New Lithium Chalcogenidotetrelates, LiChT: Synthesis and Characterization of the Li⁺-Conducting Tetralithium ortho-Sulfidostannate Li₄SnS₄

et al. 2012

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] As a key component of SSLIBs, the electrolyte should possess a high Li + conductivity (σ) at room temperature and low activation energy (E a ) for use over a broad range of operating temperatures. In the meanwhile, properties such as electrochemical stability over a wide working voltage window and chemical stability against electrodes (layered cathode and Li metal anode) should also be preferred.…”

mentioning

confidence: 99%

Fast Li-Ion Transport in Amorphous Li₂Si₂O₅: An Ab Initio Molecular Dynamics Simulation

Lei

Wang

Huang

2016

J. Electrochem. Soc.

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The present study reports an ab-initio molecular dynamics (AIMD) simulation of ionic diffusion in the amorphous Li 2 Si 2 O 5 in a temperature range of 573-823 K. The results show that the amorphous Li 2 Si 2 O 5 is primarily a Li + conductor with negligible O 2− and Si 4+ contributions. The obtained activation energy of 0.47 eV for Li + diffusion is higher than Na + in the analogue amorphous Na 2 Si 2 O 5 , but close to other types of Li + conductors. The predicted Li + conductivity is on the order of 10 −2 S·cm −1 at 623-823 K. Our simulations also reveal that Li + in the amorphous Li 2 Si 2 O 5 diffuses via a hopping mechanism between the nearest sites in the channels formed by two adjacent SiO 4 layers. © The Author Solid-state lithium-ion batteries (SSLIBs) are envisioned to be the next-generation high-power and high-capacity energy storage devices with far less safety and temperature stability issues experienced by the conventional liquid-based counterparts.1-18 As a key component of SSLIBs, the electrolyte should possess a high Li + conductivity (σ) at room temperature and low activation energy (E a ) for use over a broad range of operating temperatures. In the meanwhile, properties such as electrochemical stability over a wide working voltage window and chemical stability against electrodes (layered cathode and Li metal anode) should also be preferred. So far, a broad range of materials have been investigated as potential solid Li 6-8 and sulfide-based compounds with higher ionic conductivities such as the thio-LISICON group (Li 7 P 3 S 11 , σ = 3.2-17 × 10 −3 Scm −1 at 25 Therefore, the aim of the present study is to investigate the ionic transport property, in particularly Li + conductivity, in the amorphous Li 2 Si 2 O 5 that is a close analogue to the known Na + -conductoramorphous Na 2 Si 2 O 5 via a theoretical ab-initio molecular dynamics (AIMD) approach. We selected 573-823 K as the temperature range for the simulation because we have experimentally observed reasonably high conductivity from the amorphous Li 2 Si 2 O 5 in this temperature range. With the help of this AIMD simulation, we will be able to gain the insights into the nature of the observed conductivity. We believe that the outcome of this work is not only important to the understanding of ionic conduction mechanism in solid-state amorphous Li 2 Si 2 O 5 , but also to the identification of new solid-state electrolytes for future solid-state Li-ion batteries. 2 ) valence electrons with a plane wave cutoff energy of 500 eV. The atomic positions were optimized to the level of the maximum ionic force ≤0.02 eV Å −1 . A Verlet algorithm was integrated with Newton's equations of motion at a time step of 2 fs for a total simulation time of 50 ps, i.e., 25,000 steps performed on an NVT ensemble. The frequency of the temperature oscillations was controlled by the Nosé mass during the simulations. A supercell of 2 × 1 × 2 unit cell containing 144 atoms was chosen for a k-point sampling at the -point.Initial configurations.-The simulations started...

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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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All solid-state sheet battery using lithium inorganic solid electrolyte, thio-LISICON

Cited by 88 publications

References 12 publications

New Lithium Chalcogenidotetrelates, LiChT: Synthesis and Characterization of the Li⁺-Conducting Tetralithium ortho-Sulfidostannate Li₄SnS₄

New Lithium Chalcogenidotetrelates, LiChT: Synthesis and Characterization of the Li⁺-Conducting Tetralithium ortho-Sulfidostannate Li₄SnS₄

Fast Li-Ion Transport in Amorphous Li₂Si₂O₅: An Ab Initio Molecular Dynamics Simulation

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

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All solid-state sheet battery using lithium inorganic solid electrolyte, thio-LISICON

Cited by 88 publications

References 12 publications

New Lithium Chalcogenidotetrelates, LiChT: Synthesis and Characterization of the Li+-Conducting Tetralithium ortho-Sulfidostannate Li4SnS4

New Lithium Chalcogenidotetrelates, LiChT: Synthesis and Characterization of the Li+-Conducting Tetralithium ortho-Sulfidostannate Li4SnS4

Fast Li-Ion Transport in Amorphous Li2Si2O5: An Ab Initio Molecular Dynamics Simulation

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

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Product

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New Lithium Chalcogenidotetrelates, LiChT: Synthesis and Characterization of the Li⁺-Conducting Tetralithium ortho-Sulfidostannate Li₄SnS₄

New Lithium Chalcogenidotetrelates, LiChT: Synthesis and Characterization of the Li⁺-Conducting Tetralithium ortho-Sulfidostannate Li₄SnS₄

Fast Li-Ion Transport in Amorphous Li₂Si₂O₅: An Ab Initio Molecular Dynamics Simulation