Structure and ionic transport of PbSnF4 superionic conductor

Dénès, Georges; Milova, Galina; Madamba, M. Cecilia; Perfiliev, M.V.

doi:10.1016/0167-2738(96)00094-x

Cited by 42 publications

(13 citation statements)

References 9 publications

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“…At lower temperatures a number of different phases are formed, depending on the cooling rate [17,20,21]. Investigations of the crystal structure of PbSnF 4 at ambient temperature are made difficult by the formation of a number of closely related phases with monoclinic [15,21], orthorhombic [17,[22][23][24] and tetragonal [16,20,23,[25][26][27][28][29] symmetries, depending on the preparation method [30]. However, their structures are all fluorite-related and generally contain long-range ordering of the cations with PbPbSnSnPbPb• • • layers perpendicular to one of the pseudo-cubic axes.…”

Section: Introductionmentioning

confidence: 99%

The crystal structure of α-PbSnF₄ and its anion diffusion mechanism

Castiglione

Madden

Berastegui

et al. 2005

J. Phys.: Condens. Matter

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The crystal structure of PbSnF4 and the nature of the anion diffusion mechanism which characterizes its high ionic conductivity have been investigated by impedance spectroscopy, powder neutron diffraction and computer simulation methods. The ionic conductivity of PbSnF4 undergoes small, but abrupt, increases at 608(4) and 672(3) K characteristic of the and phase transitions. The ambient temperature α-PbSnF4 phase possesses a tetragonal crystal structure (space group P4/nmm), derived from the cubic fluorite arrangement by ordering of the cations in the scheme PbPbSnSnPbPb along the [001] direction. However, the Sn2+–Sn2+ layers contain essentially no F−, with the displaced anions residing in the Pb2+–Sn2+ layers and showing significant disorder, particularly at temperatures close to the upper limit of stability of the α phase. Computer simulations, using interionic potentials derived from first-principles calculations and containing realistic representations of polarization effects, are in good agreement with the measured ionic conductivity and successfully reproduce the experimentally determined ionic distribution. Analysis of the simulated ionic motions demonstrate that the impressive ionic conductivity of α-PbSnF4 at temperatures close to ambient is a consequence of anion diffusion within the Pb2+–Sn2+ layers, whilst those F− within the Pb2+–Pb2+ layers are immobile. At temperatures close to the melting point of the simulated system, increased transfer of anions between the various Pb2+–Pb2+, Pb2+–Sn2+, Sn2+–Sn2+ layers is observed, as the system tends towards a more isotropic anion diffusion process.

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Section: Introductionmentioning

confidence: 99%

The crystal structure of α-PbSnF₄ and its anion diffusion mechanism

Castiglione

Madden

Berastegui

et al. 2005

J. Phys.: Condens. Matter

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“…Consequently, we restricted our focus to the composition–conductivity data set in this study. Note that this data set includes polymorph data, e.g., orthorhombic and tetragonal PbSnF 4 have conductivities of 5 × 10 –5 and 3 × 10 –2 S cm –1 , respectively. , When the same compositions exhibit varied conductivities, the random forest, being an ensemble learning method, predicts the average conductivity of such polymorph data. Even though the omission of these processing, morphological, and structural features, our prediction model still achieved an MAE of logσ less than 1.…”

Section: Resultsmentioning

confidence: 99%

Accelerated Exploration of Fast Fluoride-Ion Conductors Based on Compositional Descriptors

Matsui,

Seki,

Suzuki

et al. 2023

ACS Appl. Energy Mater.

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The exploration of fast fluoride-ion conductors, which can be applied as solid electrolytes of all-solid-state fluoride-ion batteries, requires generalized material design principles. Herein, we used regression learning based on compositional descriptors to predict fluoride-ion conductivity, revealing that random forest regression, mainly considering cation polarizability, enables conductivity prediction in unexplored compositional spaces. Composition-based material exploration aided in identifying compounds with high fluoride-ion conductivity, as exemplified by a tysonite-type species (Ba 0.2 Sn 0.8 F 2 ; 9.0 × 10 −5 S cm −1 at 298 K), and substitution with La resulted in a further increase in conductivity to 1.4 × 10 −4 S cm −1 at 298 K (Ba 0.175 Sn 0.775 La 0.05 F 2.05 ). Thus, we established design principles and accelerated the exploration of fast fluoride-ion conductors using compositional information.

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“…Fluorite-type, tysonite-type, and SnF 2 -based fluoride solid-state electrolytes are mainly studied in FIB systems as fluoride-ion conductors. − Among them, fluorite-type and tysonite-type fluorides represent poor ionic conductivity at room temperature, which is far from meeting the most basic requirements for battery operation. However, two-dimensional (2D) layered SnF 2 -based fluorides (especially PbSnF 4 ) present high ionic conductivity (>10 –3 S cm –1 at RT) , at room temperature, which could meet the requirements of FIBs. Usually, the vacancy and disorder at the F site caused by the stereoactivity of the Sn(II) lone pairs are responsible for satisfactory ionic conductivity.…”

Section: Introductionmentioning

confidence: 99%

Construction and Interfacial Modification of a β-PbSnF₄ Electrolyte with High Intrinsic Ionic Conductivity for a Room-Temperature Fluoride-Ion Battery

Liu

Chen

et al. 2023

ACS Appl. Mater. Interfaces

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Solid-state fluoride-ion batteries (FIBs) attract significant attention worldwide because of their high theoretical volume, energy density, and high safety. However, the large interfacial resistance caused by the point−point contact between the electrolyte and the electrode seriously impedes their further development. Using liquid-phase therapy to construct a conformal interface is a good choice to eliminate the influence of inadequate contact between the electrode and the electrolyte. In this study, a β-PbSnF 4 solid-state electrolyte with high room-temperature ionic conductivity is prepared, and a trace amount of the liquid electrolyte (LE) between the electrode and the electrolyte is introduced in order to minimize the interfacial resistance and enhance the cycle life. The Allen-Hickling simulations show that the introduction of an interfacial wetting agent (LE) can significantly reduce the energy barrier of charge transfer and mass transfer processes at the interface and reciprocate FIBs an enhanced interfacial reaction kinetics. As a result, the initial discharge capacity of the fabricated FIBs is 210.5 mAh g −1 and the capacity retention rate is 82.6% after 50 cycles at room temperature, while the initial discharge capacity of the unmodified battery is only 170.9 mAh g −1 and the capacity retention rate is 22.1% after 50 cycles. Therefore, interfacial modification with a trace amount of LE provides a significant exploration for the improvement of FIB performances.

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Structure and ionic transport of PbSnF4 superionic conductor

Cited by 42 publications

References 9 publications

The crystal structure of α-PbSnF₄ and its anion diffusion mechanism

The crystal structure of α-PbSnF₄ and its anion diffusion mechanism

Accelerated Exploration of Fast Fluoride-Ion Conductors Based on Compositional Descriptors

Construction and Interfacial Modification of a β-PbSnF₄ Electrolyte with High Intrinsic Ionic Conductivity for a Room-Temperature Fluoride-Ion Battery

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Structure and ionic transport of PbSnF4 superionic conductor

Cited by 42 publications

References 9 publications

The crystal structure of α-PbSnF4 and its anion diffusion mechanism

The crystal structure of α-PbSnF4 and its anion diffusion mechanism

Accelerated Exploration of Fast Fluoride-Ion Conductors Based on Compositional Descriptors

Construction and Interfacial Modification of a β-PbSnF4 Electrolyte with High Intrinsic Ionic Conductivity for a Room-Temperature Fluoride-Ion Battery

Contact Info

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The crystal structure of α-PbSnF₄ and its anion diffusion mechanism

The crystal structure of α-PbSnF₄ and its anion diffusion mechanism

Construction and Interfacial Modification of a β-PbSnF₄ Electrolyte with High Intrinsic Ionic Conductivity for a Room-Temperature Fluoride-Ion Battery