Superionic Diffusion through Frustrated Energy Landscape

Stefano, Davide Di; Miglio, Anna; Robeyns, Koen; Filinchuk, Yaroslav; Lechartier, Marine; Senyshyn, Anatoliy; Ishida, Hiroyuki; Spannenberger, Stefan; Prutsch, Denise; Lunghammer, Sarah; Rettenwander, Daniel; Wilkening, Martin; Roling, Bernhard; Kato, Yoshifumi; Hautier, Geoffroy

doi:10.1016/j.chempr.2019.07.001

Cited by 130 publications

(164 citation statements)

References 63 publications

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“…Moreover, we suggest that the local geometrical structure sensitivity of Li‐ion mobility can be correlated to the tetrahedricity (octahedricity) of LiS 4− x O x (LiS 6− x O x ) polyhedral. The standard of tetrahedricity (octahedricity) is consistent with previous study, from 100 (perfect tetrahedron (octahedron)) to 0 for a completely distorted one, using the continuous symmetry measures (CSMs) implemented in pymatgen 46,47. Figure 6b shows a measure of the distortion of Li tetrahedral configuration in LPGSO (red) and LPGS (blue).…”

Section: Resultssupporting

confidence: 83%

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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Section: Resultssupporting

confidence: 83%

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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“…In this sense, the double salt Na 9 (AlS 4 )(SiS 4 ) thus shows similarities to the well-known tetragonal LGPS-phase which shows exceptionally high ionic conductivity that is in part attributable to the low energy barrier for lithium diffusion between face-sharing [LiS 4 ]-tetrahedra (Hori et al, 2015a;Wang et al, 2015). Additionally, the BVEL analysis of Na 9 (AlS 4 )(SiS 4 ) indicates a similar situation to the frustrated energy landscape leading to superionic diffusion in LiTi 2 (PS 4 ) 3 (Di Stefano et al, 2019): The sodium coordination environments are more diverse and the coordination polyhedra more distorted in the double salt Na 9 (AlS 4 )(SiS 4 ) compared to the border phases of the substitution series Na 5-x Al 1-x Si x S 4 . This low local coordination symmetry of sodium and connection of its coordination polyhedra lead to a flat energy landscape for sodium cations in Na 9 (AlS 4 )(SiS 4 ), which is beneficial for ion transport.…”

Section: Discussionmentioning

confidence: 70%

“…Accordingly, in cases where this rule applies, possible conductivity improvements via lattice softness engineering are inherently limited. However, Di Stefano et al (2019) showed for LiTi 2 (PS 4 ) 3 that the highly distorted coordination polyhedra of lithium lead to a frustrated energy landscape, lowering the energy barrier, but increasing the pre-factor due to longer jump distances and a higher entropy for the transition state. In Na 8.5 (AlS 4 ) 0.5 (SiS 4 ) 1.5 a similar influence on the pre-factor as in LiTi 2 (PS 4 ) 3 can be inferred due to the flattening of the energy landscape by the highly distorted sodium coordination polyhedra.…”

Section: Discussionmentioning

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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“…As a general phenomenon, frustrated systems for a wide range of physical phenomena are featured with correlated transition between states. [27][28][29]58,59] As reported in previous studies, the dominant diffusion mechanism in SICs is the concerted migration of multiple Li ions, [24][25][26]28] which can be understood as a correlated transition between two Li + configurations. Such correlated transition has a low migration barrier in a disordered sublattice (Figure 1).…”

Section: Discussionmentioning

confidence: 76%

“…[28] In addition, the significantly increased flexibility of Li-ion positions in large sites leads to an energy degeneracy of the Li sublattice, i.e., a large number of configurations exhibits similar energies, which induces geometrical frustration of the Li sublattice. [27][28][29]58,59] The strong Coulombic interactions among Li ions further complicate the energetics of the Li sublattice. For example, in garnet LLZO (Figure 1), the Li-ion configuration has a known pattern where an occupied 24d site leads to unoccupied nearest-neighbor 96h sites, but occupied next nearest-neighbor 96h sites, as a rearrangement within an enlarged site (i.e., two 96h).…”

Section: Discussionmentioning

confidence: 99%

Crystal Structural Framework of Lithium Super‐Ionic Conductors

Bai

Liu

et al. 2019

Advanced Energy Materials

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replacement of liquid electrolyte and has the potential to achieve improved safety, higher energy density, and longer cycle life than current commercial lithiumion batteries with liquid electrolytes. [17] Despite significant research efforts, only a few Li SIC materials exhibit an ionic conductivity of >10 −3 S cm −1 at room temperature, and some Li SICs suffer from limited stability, poor interfacial compatibility, or high cost in processing and manufacturing. [6,7,18] A strong need exists for fundamental understanding of these SIC materials in order to design and discover new Li SIC materials.A Li-ion conductor material is comprised of a mobile Li-ion sublattice hosted in a crystal structural framework of immobile polyanion groups. The empty space in between these polyanion groups hosts Li ions as Li sites and forms interconnected channels. Li ions migrate among the sites through these channels, contributing to overall ionic transport. Well-known crystal structural frameworks of SICs include NASICON structure of LiM 2 (PO 4 ) 3 (M = Ge, Ti, Sn, Hf, Zr) compositions, [19] garnet structure of Li x La 3 M 2 O 12 (5 ≤ x ≤ 7, M = Nb, Ta, Sb, Zr, Sn) compositions, [20] and LGPS-type structure of Li 10+x M 1+x P 2−x S 12 (0 ≤ x ≤ 1, M = Si, Ge, Sn) compositions. [21] Recent studies have demonstrated that the crystal structural framework determines Li sites, migration pathways, and the energy landscape, and particular crystal structural frameworks are optimal for low energy barrier Li ion migration. [10,22,23] For example, the crystal structural framework with a body-centered cubic (bcc) anion sublattice, such as found in LGPS and Li 7 P 3 S 11 , has been shown to have an energy landscape with the lowest barrier compared to other anion sublattices, such as in facecentered cubic and hexagonal close packed sublattices. [10] However, some SICs with crystal structural frameworks of non-bcc anion sublattices, such as lithium garnet (e.g., LLZO) and lithium NASICON (e.g., LATP), also exhibit high Li + conductivities as high as ≈10 −3 S cm −1 at RT. It remains an open question as to what features of these crystal structure frameworks enable super-ionic conduction.Due to their unique crystal structural frameworks, SIC materials have highly mobile Li-ion sublattices, which are drastically different from those in typical solids (Figure 1). The disordered Li sublattice of SICs facilitates the transport of a large number of Li ions and yields high ionic conductivity. In the disordered Li sublattice, the Li-ion diffusion mechanism is also distinctive As technologically important materials for solid-state batteries, Li superionic conductors are a class of materials exhibiting exceptionally high ionic conductivity at room temperature. These materials have unique crystal structural frameworks hosting a highly conductive Li sublattice. However, it is not understood why certain crystal structures of the super-ionic conductors lead to high conductivity in the Li sublattice. In this study, using topological analysis and ab initio molecula...

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Superionic Diffusion through Frustrated Energy Landscape

Cited by 130 publications

References 63 publications

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

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

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

Crystal Structural Framework of Lithium Super‐Ionic Conductors

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Superionic Diffusion through Frustrated Energy Landscape

Cited by 130 publications

References 63 publications

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

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

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

Crystal Structural Framework of Lithium Super‐Ionic Conductors

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

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