Solid electrolyte properties of LaF3

Schoonman, J.; Oversluizen, G.; Wapenaar, Kees

doi:10.1016/0167-2738(80)90005-3

Cited by 77 publications

(61 citation statements)

References 17 publications

(11 reference statements)

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“…Fig. 1 presents the bulk electrolyte conductivity of pure LaF, as reported in the literature [2]. Up to about 420 K the conductivity of single crystals is slightly anisotropic (a(]]) > g(1)).…”

Section: Experimental Aspectsmentioning

confidence: 91%

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The small-signal ac response of La1−xBaxF3−x solid solutions

1984

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The small-signal ac response of single crystals of La,_,Ba,F,_, (0 s x G 0.104) with ionically blocking electrodes has been measured in the frequency range lo-* to 10' Hz, and for temperatures from 293 to 1300 K. At low and moderate temperatures the ac bulk response can be modeled with a Debye circuit. The circuit parameters do not have the temperature dependence associated with dipolar reorientation but rather the opposite, as is characteristic of the behavior of free charge carriers. We have developed a model, in which the theoretically expected dependence of the circuit parameters is concordant to the behavior found experimentally. Thermally stimulated depolarization current (TSDC) spectra exhibit five dielectric relaxation peaks, in addition to a space-charge peak. Two peaks have been analyzed in detail. The reorientation enthalpies are concordant with the conduction activation enthalpies.La rtponse signal-faible par courant altematif de monocrystaux du type La,_,Ba,F,_, (0 G x s 0.104) avec des electrodes de blocage des ions a tti mesuree dans le domaine de frequence lo-' a lo5 Hz, et pour des temperatures entre 293 et 1300 K. A des temperatures basses et modtrees la reponse du volume par courant alternatif put &re represent6 a l'aide du circuit Debye. Les parambtres du circuit ne montrent pas la dtpendance de temperature associee a la reorientation dipolaire mais plut& l'oppost, ce qui est caracttristique du comportement des porteurs de charge libre. Nous avons dtvelopp6 un modtle oh la dependance attendu theoriquement des parametres du circuit s'accorde avec le comportement trouvt en experiment. Thermally stimulated depolarization current (TSDC) spectres montrent cinq pits de relaxation dielectrique et en plus un pit de charge d'espace. Deux pits ont BtC analysts en detail. Les enthalpies de reorientation s'accordent avec les enthalpies de l'activation de la conduction.

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Section: Experimental Aspectsmentioning

confidence: 91%

“…Anisotropic fluoride ion $ On leave from Physics Department, Memphis State University, Memphis, Tennessee, USA. conductivity has been observed for undoped LaF3, with a(/c axis) > c+(lc axis) [2].…”

Section: Introductionmentioning

confidence: 96%

The small-signal ac response of La1−xBaxF3−x solid solutions

1984

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“…The electrical properties of LaF 3 are still the subject of some disagreement [14]. This is at least partly due to the tendency of LaF 3 crystals to form oxygen-rich surface layers, which interfere with the determination of the bulk electrical properties.…”

Section: + Pe/p1mentioning

confidence: 99%

“…This is at least partly due to the tendency of LaF 3 crystals to form oxygen-rich surface layers, which interfere with the determination of the bulk electrical properties. Experimental plots [ 14,15] of log oT against 1/T show a change in slope at about 100°C for the pure single crystal and dilute solid solutions Lal_xBaxF3_ x. Sher et al [15] interpret the change in slope as due to the dissociation of impurity-vacancy pairs, with the impurity being either oxygen or a divalent cation. Schoonman et al [ 14], however, discount this interpretation on the basis of their measurements on the solid solution up to x = 0.05.…”

Section: + Pe/p1mentioning

confidence: 99%

“…Experimental plots [ 14,15] of log oT against 1/T show a change in slope at about 100°C for the pure single crystal and dilute solid solutions Lal_xBaxF3_ x. Sher et al [15] interpret the change in slope as due to the dissociation of impurity-vacancy pairs, with the impurity being either oxygen or a divalent cation. Schoonman et al [ 14], however, discount this interpretation on the basis of their measurements on the solid solution up to x = 0.05. As we shall see, a comparable log oT versus 1/T plot can be obtained from the present model, without invoking the dissociation of impurity-vacancy pairs.…”

Section: + Pe/p1mentioning

confidence: 99%

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Bulk conductivity and polarization of ionic crystals exhibiting defect exchange between inequivalent sites

Franceschetti

Shipe

1984

Solid State Ionics

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The bulk conductivity of ionically conducting crystals in which Schottky or Frenkel defects jump between inequivalent sites can be appreciably more complex than that of simpler materials. An equivalent electrical circuit is derived to describe the bulk ac response of crystals of the tysonite type. The circuit has the form of a two-component Maxwell-Wagner capacitor and includes a capacitative element which represents a frequency-dependent bulk polarization not associated with dipolar complexes. The application of the model to LaF3 is discussed.

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CuF₂ as Reversible Cathode for Fluoride Ion Batteries

Thieu

Fawey

Bhatia

et al. 2017

Adv Funct Materials

130

141

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In the search for novel battery systems with high energy density and low cost, fluoride ion batteries have recently emerged as a further option to store electricity with very high volumetric energy densities. Among metal fluorides, CuF 2 is an intriguing candidate for cathode materials due to its high specific capacity and high theoretical conversion potential. Here, the reversibility of CuF 2 as a cathode material in the fluoride ion battery system employing a high F − conducting tysonite-type La 0.9 Ba 0.1 F 2.9 as an electrolyte and a metallic La as an anode is investigated. For the first time, the reversible conversion mechanism of CuF 2 with the corresponding variation in fluorine content is reported on the basis of X-ray photoelectron spectroscopy measurements and cathode/electrolyte interfacial studies by transmission electron microscopy. Investigation of the anode/electrolyte interface reveals structural variation upon cycling with the formation of intermediate layers consisting of i) hexagonal LaF 3 and monoclinic La 2 O 3 phases in the pristine interface;ii) two main phases of distorted orthorhombic LaF 3 and monoclinic La 2 O 3 after discharging; and iii) a tetragonal lanthanum oxyfluoride (LaOF) phase after charging. The fading mechanism of the cell capacity upon cycling can be explained by Cu diffusion into the electrolyte and side reactions due to the formation of the LaOF compound.

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Solid electrolyte properties of LaF3

Cited by 77 publications

References 17 publications

The small-signal ac response of La1−xBaxF3−x solid solutions

The small-signal ac response of La1−xBaxF3−x solid solutions

Bulk conductivity and polarization of ionic crystals exhibiting defect exchange between inequivalent sites

CuF₂ as Reversible Cathode for Fluoride Ion Batteries

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Solid electrolyte properties of LaF3

Cited by 77 publications

References 17 publications

The small-signal ac response of La1−xBaxF3−x solid solutions

The small-signal ac response of La1−xBaxF3−x solid solutions

Bulk conductivity and polarization of ionic crystals exhibiting defect exchange between inequivalent sites

CuF2 as Reversible Cathode for Fluoride Ion Batteries

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CuF₂ as Reversible Cathode for Fluoride Ion Batteries