Synthesis, structure and lithium ionic conductivity of solid solutions of Li10(Ge1−M )P2S12 (M = Si, Sn)

Kato, Yoshifumi; Saito, Ryoko; Sakano, Mitsuru; Mitsui, Akira; Hirayama, Masaaki; Kanno, Ryoji

doi:10.1016/j.jpowsour.2014.07.159

Cited by 105 publications

(131 citation statements)

References 16 publications

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“…In addition to isovalent substitution, aliovalent substitution can be used to not only alter the polarizability of the lattice and influence the size of diffusion pathways, but also to tune the charge carrier concentration. Similar to the LGPS system (Kamaya et al, 2011;Bron et al, 2013Bron et al, , 2016Kuhn et al, 2013aKuhn et al, ,b, 2014Kato et al, 2014Kato et al, , 2016Hori et al, 2015a,b;Harm et al, 2019), tetrel elements were employed in the Na 3+x T x P 1-x S 4 (T = Si, Sn) system to increase the charge carrier density and increase the overall ionic conductivity. The Sn-containing compounds are structurally very similar to the LGPS-like Li 10 SnP 2 S 12 and show conductivities of 4 · 10 −5 S cm −1 for Na 10 SnP 2 S 12 and the highest measured sodium ionic conductivity at room temperature for sulfides of 4 · 10 −3 S cm −1 for Na 11 Sn 2 PS 12 (Bron et al, 2013;Richards et al, 2016;Duchardt et al, 2018).…”

Section: Introductionmentioning

confidence: 99%

Finding the Right Blend: Interplay Between Structure and Sodium Ion Conductivity in the System Na5AlS4–Na4SiS4

et al. 2020

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The rational design of high performance sodium solid electrolytes is one of the key challenges in modern battery research. In this work, we identify new sodium ion conductors in the substitution series Na 5-x Al 1-x Si x S 4 (0 ≤ x ≤ 1), which are entirely based on earth-abundant elements. These compounds exhibit conductivities ranging from 1.64 · 10 −7 for Na 4 SiS 4 to 2.04 · 10 −5 for Na 8.5 (AlS 4 ) 0.5 (SiS 4 ) 1.5 (x = 0.75). We determined the crystal structures of the Na + -ion conductors Na 4 SiS 4 as well as hitherto unknown Na 5 AlS 4 and Na 9 (AlS 4 )(SiS 4 ). Na + -ion conduction pathways were calculated by bond valence energy landscape (BVEL) calculations for all new structures highlighting the influence of the local coordination symmetry of sodium ions on the energy landscape within this family. Our findings show that the interplay of charge carrier concentration and low site symmetry of sodium ions can enhance the conductivity by several orders of magnitude.

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Section: Introductionmentioning

confidence: 99%

Finding the Right Blend: Interplay Between Structure and Sodium Ion Conductivity in the System Na5AlS4–Na4SiS4

et al. 2020

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“…Li 10 GeP 2 S 12 exhibits extremely high conductivity values on the order of 10 −2 S/cm, equal to or even exceeding those of the liquid electrolytes, in addition to a wide electrochemical window of up to 5 V. Moreover, all‐solid‐state cells using LGPS exhibit excellent performance comparable to that of liquid systems . In addition to the above characteristics that show promise with respect to practical applications in all‐solid‐state batteries, the study of the ionic conduction behavior of LGPS is attractive as a means of examining the conduction mechanism in such materials, and theoretical calculations, crystal structure analysis, and the synthesis of iso‐structural materials have been applied to the modification of LGPS compositions. At present, however, there is no information concerning the phase stability, the LGPS formation region in the Li 4 GeS 4 –Li 3 PS 4 pseudo‐binary system, or the structural relationship between the LGPS phase and the end‐members in the system, γ‐Li 3 PS 4 and Li 4 GeS 4 .…”

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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“…22-0.25 eV (refs 14,15). Replacing Ge in Li 10 GeP 2 S 12 by Sn or Si has been shown to also give a high conductivity with similar activation energy [16][17][18][19][20] . These materials have superior ionic conductivities, comparable to those of liquid electrolytes, making the commercialization of high-performance solid-state Li-ion batteries very promising.…”

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confidence: 99%

Design principles for solid-state lithium superionic conductors

et al. 2015

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Lithium solid electrolytes can potentially address two key limitations of the organic electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochemical stability. However, achieving a Li(+) conductivity in the solid state comparable to existing liquid electrolytes (>1 mS cm(-1)) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centred cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic conductivity, and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.

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Synthesis, structure and lithium ionic conductivity of solid solutions of Li10(Ge1−M )P2S12 (M = Si, Sn)

Cited by 105 publications

References 16 publications

Finding the Right Blend: Interplay Between Structure and Sodium Ion Conductivity in the System Na5AlS4–Na4SiS4

Finding the Right Blend: Interplay Between Structure and Sodium Ion Conductivity in the System Na5AlS4–Na4SiS4

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

Design principles for solid-state lithium superionic conductors

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Synthesis, structure and lithium ionic conductivity of solid solutions of Li10(Ge1−M )P2S12 (M = Si, Sn)

Cited by 105 publications

References 16 publications

Finding the Right Blend: Interplay Between Structure and Sodium Ion Conductivity in the System Na5AlS4–Na4SiS4

Finding the Right Blend: Interplay Between Structure and Sodium Ion Conductivity in the System Na5AlS4–Na4SiS4

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

Design principles for solid-state lithium superionic conductors

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