Investigating the Li+substructure and ionic transport in Li10GeP2−xSbxS12(0 ≤x≤ 0.25)

Helm, Bianca; Gronych, Lara; Banik, Ananya; Lange, Martin; Li, Cheng; Zeier, Wolfgang G.

doi:10.1039/d2cp04710a

Cited by 2 publications

(2 citation statements)

References 46 publications

(107 reference statements)

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“…To develop solid electrolytes with high ionic conductivities, it is necessary to understand how the chemistry of the host framework modulates the structure and dynamics of the mobile-ion species. ,,, In many families of solid electrolytes, introducing compositional or structural disorder within the host framework is an effective strategy for increasing ionic conductivity. ,,− (M,Sn)F 2 fluorites have previously been proposed to exhibit two distinct forms of host-framework disorder: ,− cation–site-occupation disorder, where the two cationic species are distributed randomly over the available sites, and Sn–lone-pair orientational disorder, where Sn exhibits stereoactive lone pairs with random orientations. This proposed coexistence of two distinct forms of host-framework disorder makes (M,Sn)F 2 fluorites a particular focus of study in the context of understanding the possible interplay between disorder types and how, together, they modulate ion transport.…”

Section: Discussionmentioning

confidence: 99%

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄

Mercadier,

Coles,

Duttine

et al. 2023

J. Am. Chem. Soc.

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Introducing compositional or structural disorder within crystalline solid electrolytes is a common strategy for increasing their ionic conductivity. (M,Sn)F2 fluorites have previously been proposed to exhibit two forms of disorder within their cationic host frameworks: occupational disorder from randomly distributed M and Sn cations and orientational disorder from Sn(II) stereoactive lone pairs. Here, we characterize the structure and fluoride-ion dynamics of cubic BaSnF4, using a combination of experimental and computational techniques. Rietveld refinement of the X-ray diffraction (XRD) data confirms an average fluorite structure with {Ba,Sn} cation disorder, and the 119Sn Mössbauer spectrum demonstrates the presence of stereoactive Sn(II) lone pairs. X-ray total-scattering PDF analysis and ab initio molecular dynamics simulations reveal a complex local structure with a high degree of intrinsic fluoride-ion disorder, where 1/3 of fluoride ions occupy octahedral “interstitial” sites: this fluoride-ion disorder is a consequence of repulsion between Sn lone pairs and fluoride ions that destabilizes Sn-coordinated tetrahedral fluoride-ion sites. Variable-temperature 19F NMR experiments and analysis of our molecular dynamics simulations reveal highly inhomogeneous fluoride-ion dynamics, with fluoride ions in Sn-rich local environments significantly more mobile than those in Ba-rich environments. Our simulations also reveal dynamical reorientation of the Sn lone pairs that is biased by the local cation configuration and coupled to the local fluoride-ion dynamics. We end by discussing the effect of host-framework disorder on long-range diffusion pathways in cubic BaSnF4.

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Section: Discussionmentioning

confidence: 99%

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄

Mercadier,

Coles,

Duttine

et al. 2023

J. Am. Chem. Soc.

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“…Various types of solid electrolytes have been investigated to improve the electrochemical performance of ASSBs. [5][6][7][8][9][10][11][12][13][14] In particular, sulfide-based thiophosphate solid electrolytes (thio-SEs), such as argyrodite-type Li 6 PS 5 Cl (LPSCl), have attracted much attention because of their high ionic conductivity and good mechanical flexibility. [15,16] However, thio-SEs still have challenges of translating research into practical applications, such as poor interfacial stability, although recent efforts showed promise in improving the electrochemical performance of thio-SEs.…”

Section: Introductionmentioning

confidence: 99%

Trimethylsilyl Compounds for the Interfacial Stabilization of Thiophosphate‐Based Solid Electrolytes in All‐Solid‐State Batteries

Kim,

Song

et al. 2023

Advanced Science

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Argyrodite‐type Li6PS5Cl (LPSCl) has attracted much attention as a solid electrolyte for all‐solid‐state batteries (ASSBs) because of its high ionic conductivity and good mechanical flexibility. LPSCl, however, has challenges of translating research into practical applications, such as irreversible electrochemical degradation at the interface between LPSCl and cathode materials. Even for Li‐ion batteries (LIBs), liquid electrolytes have the same issue as electrolyte decomposition due to interfacial instability. Nonetheless, current LIBs are successfully commercialized because functional electrolyte additives give rise to the formation of stable cathode‐electrolyte interphase (CEI) and solid‐electrolyte interphase (SEI) layers, leading to supplementing the interfacial stability between electrolyte and electrode. Herein, inspired by the role of electrolyte additives for LIBs, trimethylsilyl compounds are introduced as solid electrolyte additives for improving the interfacial stability between sulfide‐based solid electrolytes and cathode materials. 2‐(Trimethylsilyl)ethanethiol (TMS‐SH), a solid electrolyte additive, is oxidatively decomposed during charge, forming a stable CEI layer. As a result, the CEI layer derived from TMS‐SH suppresses the interfacial degradation between LPSCl and LiCoO2, thereby leading to the excellent electrochemical performance of Li | LPSCl | LiCoO2, such as superior cycle life over 2000 cycles (85.0% of capacity retention after 2000 cycles).

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Investigating the Li⁺substructure and ionic transport in Li₁₀GeP_2−xSb_xS₁₂(0 ≤x≤ 0.25)

Abstract: Understanding the correlation between ionic motion and crystal structure is crucial for improving solid electrolyte conductivities. Several substitutions in the Li10GeP2S12 structure have been shown favorable impact on the ionic...

Cited by 2 publications

References 46 publications

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄

Trimethylsilyl Compounds for the Interfacial Stabilization of Thiophosphate‐Based Solid Electrolytes in All‐Solid‐State Batteries

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Investigating the Li+substructure and ionic transport in Li10GeP2−xSbxS12(0 ≤x≤ 0.25)

Abstract: Understanding the correlation between ionic motion and crystal structure is crucial for improving solid electrolyte conductivities. Several substitutions in the Li10GeP2S12 structure have been shown favorable impact on the ionic...

Cited by 2 publications

References 46 publications

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF4

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF4

Trimethylsilyl Compounds for the Interfacial Stabilization of Thiophosphate‐Based Solid Electrolytes in All‐Solid‐State Batteries

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Investigating the Li⁺substructure and ionic transport in Li₁₀GeP_2−xSb_xS₁₂(0 ≤x≤ 0.25)

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄