Stereoactive Electron Lone Pairs Facilitate Fluoride Ion Diffusion in Tetragonal BaSnF4 DOI
Xiliang Lian, Damien Dambournet, Mathieu Salanne

и другие.

Chemistry of Materials, Год журнала: 2024, Номер 37(1), С. 378 - 386

Опубликована: Дек. 16, 2024

Solid-state ionic conductors are of primary importance for the design tomorrow's batteries. In lithium- or sodium-ion-based materials, alkali cations diffuse through three-dimensional channels consisting interconnected tetrahedral octahedral sites with low free energy barriers between them. Fluoride ion stand out in this landscape since materials highest conductivities belong to MSnF4 family (in which M2+ is a divalent cation), whose structure layered and characterized by double-layers Sn2+ along given direction. Importantly, these display stereoactive electron lone pairs (LPs) that seemingly play an important role not only stabilizing Sn–Sn layer but also modulating fluoride diffusive behavior. However, despite previous experimental simulation studies, involvement LPs conduction mechanism remains be quantitatively understood. work, we simulate BaSnF4 tetragonal using machine learning-based molecular dynamics, interaction potential trained on density functional theory data. We investigated Sn–LP–Sn lowering diffusion landscape. particular, show how F– ions jump across occur much more frequently than Ba–F–Ba one, resulting formation vacancies Ba–Sn layers. Concurrently, LP stereochemical activity fluctuates accommodate F jumping. addition, presence enhances flexibility Sn ions, leads increase two-dimensional several orders magnitude. These results contribute our understanding interplay diffusion, helping explain good performance material fluoride-ion

Язык: Английский

Solid-state synthesis and ion transport characteristics of the β-KSbF4 for all-solid-state fluoride-ion batteries DOI
Jiali Liu,

Huahui Zhao,

Jingcheng Xia

и другие.

Journal of Energy Chemistry, Год журнала: 2024, Номер 94, С. 758 - 767

Опубликована: Март 27, 2024

Язык: Английский

Процитировано

26
Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF4 DOI Creative Commons

Briséïs Mercadier,

Samuel W. Coles, Mathieu Duttine

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(43), С. 23739 - 23754

Опубликована: Окт. 16, 2023

Introducing compositional or structural disorder within crystalline solid electrolytes is a common strategy for increasing their ionic conductivity. (M,Sn)F

Язык: Английский

Процитировано

10
Point-defect chemistry for ionic conduction in solid electrolytes with isovalent cation mixing DOI Creative Commons
T. Ogawa, Kazuyuki Sato, Kazuhiro Mori

и другие.

Journal of Materials Chemistry A, Год журнала: 2024, Номер 12(45), С. 31173 - 31184

Опубликована: Янв. 1, 2024

The atomic-scale mechanism of enhanced ionic conductivity in (Ba,Ca)F 2 with isovalent cation mixing is revealed via a first-principles investigation defect formation and migration.

Язык: Английский

Процитировано

4
Polymer Electrolyte Based All‐Solid‐State Rechargeable Fluoride Ion Batteries DOI
Yifan Yu, G. S. Li, Chilin Li

и другие.

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 2, 2024

Abstract Rechargeable fluoride ion batteries (FIBs) are one of the most promising energy storage candidates in view high density and low cost. The development highly F‐conductive, safe, flexible electrolytes is central task for construction high‐performance FIBs. Hereby, this work first proposes a polyvinyl alcohol (PVA)‐borax‐glycerol (PBG) polymer electrolyte. F − transport along PVA chain realized by interaction between ‐OH on motion would facilitate migration . B(OH) 4 dissociated from borax can be used as cross‐linking agent, react with hydroxyl groups dehydration process to form 3D cross‐linked structure. optimized ionic conductivity (as 2.82 × 10 −4 S cm −1 at 30 °C 1.08 −3 60 °C) PBG obtained. flat soft surface significantly reduce activation interfacial process. Benefitting easier transport, electrolyte makes all‐solid‐state FIBs enable reversible cycling current 125 mA g

Язык: Английский

Процитировано

3
Development of All-Solid-State Fluoride Ion Battery with Enhanced Electrochemical Stability DOI

M Meena,

Amrtha Bhide

Journal of Alloys and Compounds, Год журнала: 2025, Номер unknown, С. 178963 - 178963

Опубликована: Фев. 1, 2025

Язык: Английский

Процитировано

0
Lone-Pair Driven Na-Ion Diffusion Leading to Highly Conductive Na2(BH4)(NH2) Phases DOI

Kshitij Srivastava,

César Menéndez Muñiz,

Tapasendra Adhikary

и другие.

ACS Applied Energy Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 3, 2025

Язык: Английский

Процитировано

0
Revealing an Intercalation Nature of High‐Capacity Conversion Cathode Materials for Fluoride‐Ion Batteries by Operando Studies DOI Creative Commons

Hong Chen,

Roland Schoch, Jean‐Noël Chotard

и другие.

Small Methods, Год журнала: 2025, Номер unknown

Опубликована: Июнь 4, 2025

Abstract To improve the performance of high‐energy‐density electrode materials for all‐solid‐state fluoride‐ion batteries (ASSFIBs), it is important to understand structure and phase evolution during operation, which closely correlated capacity fading. In this study, an operando cell designed compatible with laboratory X‐ray diffraction (XRD) monitor real‐time structural changes bismuth trifluoride (BiF 3 ) cathodes degradation ionic conductor BaSnF 4 under negative potentials at 100 °C. Supported by ex‐situ XRD, our results reveal a multi‐step defluorination BiF : from orthorhombic (o‐BiF cubic (c‐BiF ), then distorted (o’‐BiF finally metallic (Bi), indicating partial intercalation‐type character. Formation oxidefluoride (BiOF) beyond 200 mAh g −1 attributed oxygen impurities introduced via solid‐state synthesis. absorption spectroscopy (XAS) confirms continuous reduction Bi 3+ 0 intermediate phases. Rietveld refinement quantifies fractions transitions, enabling model defluorination. Comparison XRD XAS reveals that contributes transport both fluoride impurities, leading BiOF formation. also exhibits broad stability window, occurring below −200 mV, rather than expected −50 mV vs. Sn/SnF 2 .

Язык: Английский

Процитировано

0
Insights into the Micro-Structure-Transport Relationships of the Fluoride-Ion Conductor t-BaSnF4 Synthesized by Spark Plasma Sintering DOI

Briséïs Mercadier,

Christophe Legein, Monique Body

и другие.

Chemistry of Materials, Год журнала: 2024, Номер unknown

Опубликована: Авг. 7, 2024

The tetragonal ordered form of BaSnF4 is particular interest, as its ionic conductivity high enough to enable uses an electrolyte in all-solid-state fluoride-ion batteries. Despite several studies related synthesis, structure, and diffusion mechanism, reported routes often yield impurities well unexplained variation the unit-cell c-axis length. Here, we report on single-phase synthesis t-BaSnF4 via spark plasma sintering, a method that could be used prepare bulk-type inorganic batteries one step. By optimizing different parameters (temperature, setup features, etc.), reached 5 × 10–3 S·cm–1 at 30 °C. In addition, show two main factors affect conductivity. First, microstructural scale, preferential growth crystallites along results decrease resulting powders because two-dimensional (2D) this material. Second, atomic increase length concomitant with A combined neutron diffraction 19F solid-state magic angle spinning (MAS) NMR study reveals observed due partial occupancy octahedral interstitial sites. allows us identify these sites (the F4 site) distinct isotropic chemical shift values. Furthermore, variable-temperature MAS F4-ions do not exchange fluoride-ions (F1 F3) are responsible for transport properties. Hence, tends lower 2D conductivity, can guideline ensure preparation highly conductive samples provided microstructure controlled. Overall, provides novel route pure while establishing better understanding affecting

Язык: Английский

Процитировано

1
Unveiling kinetic characteristics of the interface between solid electrolyte and cathode for all-solid-state fluoride ion batteries towards a wide-temperature application DOI
Jiali Liu,

Huahui Zhao,

Yixuan Chen

и другие.

Journal of Power Sources, Год журнала: 2024, Номер 625, С. 235736 - 235736

Опубликована: Ноя. 1, 2024

Язык: Английский

Процитировано

0
How mechanochemistry affects the composition and properties of disordered fluorite BaSnF4? DOI Creative Commons

Briséïs Mercadier,

Christophe Legein, Mathieu Duttine

и другие.

Comptes Rendus Chimie, Год журнала: 2024, Номер 27(G1), С. 343 - 352

Опубликована: Ноя. 27, 2024

Mechanochemistry has been widely used to enable the formation of homogenous mixed phases, particularly in field fluoride ion conductors. In this work, we have investigated effect applying long duration time high energy ball milling on disordered fluorite BaSnF4. We systematically compared properties two samples, one prepared using a commonly reported protocol and obtained after longer duration. Microstructural analysis by X-ray line refinement Williamson–Hall diagrams showed that increasing resulted decrease particle size from 13 6 nm suppressed occurrence microstrains, which were identified as twinned regions microscopy analysis. Prolongation treatment is also associated with ionic conductivity identical jump activation energy. 119Sn Mössbauer spectroscopy revealed presence new signature assigned Sn(IV) an oxide–fluoride environment. hypothesized environment originates anion-excess fluorite-type phase BaSn 1-x (II) Sn x (IV) F 4 O induced prolonged milling. Such hypothesis supported ions located within octahedral sites, are likely be bound resulting their lower mobility shown 19F solid-state NMR. Overall, work demonstrates interplay between microstructure, composition transport conductors indeed complex, many factors at play, including size, strain, defects or composition. Supplementary Materials: material for article supplied separate file: crchim-361-suppl.pdf La mécanochimie été largement appliquée pour permettre la d'une mixte homogène, en particulier dans le domaine des conducteurs d'ions fluorure. Dans ce travail, nous avons étudié l'effet de l'application longue durée broyage sur fluorine désordonnée Nous systématiquement comparé les propriétés deux échantillons, l'un préparé selon protocole habituel et l'autre obtenu après une plus longue. L'analyse microstructurale obtenue par diffraction rayons X révélé que l'augmentation du à billes entraîne diminution taille particules supprime l'apparition micro-déformations. prolongation traitement est également associée conductivité ionique avec énergie d'activation identique saut l'ion spectroscopie présence nouvelle attribuée un environnement oxyde-fluorure. émis l'hypothèse nouvel provient type excès d'anions induite prolongé. Cette hypothèse étayée fluorure sites octaédriques, qui sont probablement liés mobilité faible, comme montre RMN l'état solide. l'ensemble, travail l'interaction entre micro-structure, fait complexe nombreux facteurs entrent jeu, notamment taille, déformations, défauts ou Compléments : Des compléments fournis cet fichier séparé

Процитировано

0