Structure and ion mobility in glasses in the BiF3–PbF2–ZrF4 systems studied by Raman and NMR spectroscopy

Kavun, V. Ya.; Voĭt, E. I.; Yaroshenko, R. M.; Гончарук, В. К.

doi:10.1016/j.jnoncrysol.2014.01.028

Cited by 14 publications

(7 citation statements)

References 32 publications

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“…Figure e shows a Raman spectrum taken at the position of BiF 3 (dark areas in CCD images shown in Figure g) within 30 min after the cell had been assembled. Two peaks at 79 and 111 cm –1 are assigned to o-BiF 3 . After several days, Raman spectra taken at positions of particles often showed a Raman scattering peak of c-BiF 3 , as shown in Figure f .…”

Section: Resultsmentioning

confidence: 91%

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Reactivity and Mechanisms in Fluoride Shuttle Battery Reactions: Difference between Orthorhombic and Cubic BiF₃ Single Microparticles

Yamanaka

Okazaki

Ogumi

et al. 2019

ACS Appl. Energy Mater.

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BiF3 is a strong candidate for a cathode material in fluoride shuttle batteries (FSBs), which utilize defluorination of metal fluorides and fluorination of metals. Much interest has been shown in FSBs as next-generation batteries with high energy densities. Elucidation and control of reactivity and mechanisms in FSB reactions are crucial for the development of FSBs with high performances. In the present work, structural transformation, reactivities, and mechanisms in FSB reactions of BiF3 microparticles partly embedded in a gold plating film (BiF3/gold, mainly orthorhombic BiF3 (o-BiF3) containing small amounts of cubic BiF3 (c-BiF3)) were studied by in-situ Raman microscopy. Reactivities and mechanisms in defluorination were found to be different for o-BiF3 and c-BiF3. In an ionic-liquid-based electrolyte, gradual transformation of o-BiF3 into cubic c-BiF3 occurred. When the voltage of BiF3/gold (cathode) vs a Pb counter electrode (anode) was decreased from OCV (0.7 V) to 0.05 V step by step, direct defluorination of the surfaces of only o-BiF3 started from their contours at 0.45 V and then extended to their center parts and was mostly completed at 0.2 V. Then defluorination of c-BiF3 started at a voltage below 0.2 V by both direct defluorination and dissolution–deposition mechanisms. In the former mechanism, the nucleus of Bi first appeared near the edge of c-BiF3 microparticles, and the nucleus grew for defluorination to proceed over the whole surface. The rate of direct defluorination of c-BiF3 was much slower than that of o-BiF3. Defluorination of c-BiF3 by the dissolution–deposition mechanism was dominant and fast when the excitation beam was strong, probably due to a thermal effect. Such an observation is important for the development of electrodes and electrolytes with proper solubility to better utilize reactions by the two mechanisms to realize FSBs with high performance.

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Section: Resultsmentioning

confidence: 91%

“…Two peaks at 79 and 111 cm −1 are assigned to o-BiF 3 . 28 After several days, Raman spectra taken at positions of particles often showed a Raman scattering peak of c-BiF 3 , as shown in Figure 1f. 23 This indicates that o-BiF 3 transformed into c-BiF 3 by nonelectrochemical reaction with the electrolyte.…”

Section: Resultsmentioning

confidence: 92%

Reactivity and Mechanisms in Fluoride Shuttle Battery Reactions: Difference between Orthorhombic and Cubic BiF₃ Single Microparticles

Yamanaka

Okazaki

Ogumi

et al. 2019

ACS Appl. Energy Mater.

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“…32 In the latter series, a new band centered at 440 cm −1 appears and increases with increasing BiF 3 content, as typically observed in bismuth-containing fluoride glasses, 33 and it lies within the range of the vibrational modes observed for crystalline BiF 3 . 34…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

BiF₃ Incorporation in Na/Ba Mixed Network Modifier Fluoride–Phosphate Glasses: Structural Studies by Solid-State NMR and Raman Spectroscopies

Galleani¹,

Bradtmüller

Fares

et al. 2020

J. Phys. Chem. C

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Bismuth-containing rare-earth codoped fluoride phosphate glasses are promising materials for superbroadband near-infrared (NIR) emission with potential applications in optical amplification. To elucidate their structural organization, this contribution develops a comprehensive multinuclear solid-state single and 31P/19F double resonance NMR strategy, applied to glasses in the system (BiF3) y (50NaPO3–20Ba(PO3)2–20NaF–10BaF2)100–y (y = 0, 5, 10, 20, 30, 40). To separately assess the influence of bismuth and fluorine constituents on the network structure, an additional set of (NaPO3)50–2x (Ba(PO3)2)20–x (NaF)20+2x (BaF2)10+x (x = 0, 2.5, 5.0, 7.5) glasses was also investigated. Introduction of alkali fluoride ions into phosphate glasses is shown to follow a new network modification scheme involving depolymerization of polyphosphate chains under the formation of F-bonded fluorophosphate units. However, a significant part of the fluoride stays separate, interacting exclusively with metal-ion species. 23Na MAS and 23Na{31P} double resonance NMR results are consistent with a local sodium ion environment dominated by phosphate ions in the Bi-free system, whereas in the BiF3-containing glasses, the successive reduction of the dipolar second moment M 2(Na–P) with increasing BiF3 content reflects the expected dilution effect, accompanied by increasing competition of the fluoride ions for ligation with the Na+ ions.

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“…When the excitation beam was placed at a position of one of the BiF 3 particles, spectra shown in Figures b,f (zoomed) were obtained. The peaks at 60, 76, and 115 cm –1 are assigned to o-BiF 3 . When the beam was placed on another BiF 3 particle, spectra shown in Figure c,g (zoomed) were obtained.…”

Section: Resultsmentioning

confidence: 99%

“…The peaks at 60, 76, and 115 cm −1 are assigned to o-BiF 3 . 35 When the beam was placed on another BiF 3 particle, spectra shown in Figure 1c,g (zoomed) were obtained. The broad peak around 150 cm −1 is assigned to c-BiF 3 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Evolution of Fluoride Shuttle Battery Reactions of BiF₃ Microparticles in a CsF/LiBOB/Tetraglyme Electrolyte: Dependence on Structure, Size, and Shape

Yamanaka

Küçük

Ogumi

et al. 2020

ACS Appl. Energy Mater.

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Fluoride shuttle batteries (FSBs) are possible candidates of next-generation batteries with high energy densities that operate by defluorination of metal fluorides and fluorination of metals. Understanding and control of FSB reactions are important for the development of FSBs with high performance. In the present work, evolution of FSB reactions of orthorhombic and cubic BiF3 (o-BiF3 and c-BiF3, respectively) microparticles partly embedded in a gold plating film (BiF3/gold) in a CsF/LiBOB (lithium bis(oxalato)borate)/tetraglyme electrolyte was studied by in situ Raman microscopy. Three-dimensional morphology of embedded BiF3 microparticles was also studied by laser scanning confocal microscopy (LSCM) to elucidate the detailed shape dependence of defluorination. Evolution of FSB reactions was found to be different from that in an ionic-liquid electrolyte reported previously. When the voltage of BiF3/gold vs a Pb counter electrode was decreased from OCV (about 0.5 V), direct defluorination of o-BiF3 and c-BiF3 started at 0.25 and 0.05 V, respectively, which are lower than those in the ionic-liquid electrolyte. The direct defluorination mechanism was always predominant at all CsF concentrations studied from saturation to zero. The sizes of most of the BiF3 microparticles that were defluorinated were less than 3 μm. However, partial defluorination of large (>10 μm) BiF3 (insulator) microparticles often occurred at protruded positions far from the contours (i.e., far from the gold current collector). The results suggest that defluorination occurred at positions with small radii of curvatures, probably due to stronger electric fields. On the other hand, defluorination of o-BiF3 particles with sizes of less than 3 μm started from their contours and proceeded toward their central positions. The observed phenomena have implications for controlling the rate-determining steps in FSB reactions that depend on electrolytes and the sizes and shapes of particles and for designing electrodes and electrolytes for superior FSBs.

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Structure and ion mobility in glasses in the BiF3–PbF2–ZrF4 systems studied by Raman and NMR spectroscopy

Cited by 14 publications

References 32 publications

Reactivity and Mechanisms in Fluoride Shuttle Battery Reactions: Difference between Orthorhombic and Cubic BiF₃ Single Microparticles

Reactivity and Mechanisms in Fluoride Shuttle Battery Reactions: Difference between Orthorhombic and Cubic BiF₃ Single Microparticles

BiF₃ Incorporation in Na/Ba Mixed Network Modifier Fluoride–Phosphate Glasses: Structural Studies by Solid-State NMR and Raman Spectroscopies

Evolution of Fluoride Shuttle Battery Reactions of BiF₃ Microparticles in a CsF/LiBOB/Tetraglyme Electrolyte: Dependence on Structure, Size, and Shape

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Structure and ion mobility in glasses in the BiF3–PbF2–ZrF4 systems studied by Raman and NMR spectroscopy

Cited by 14 publications

References 32 publications

Reactivity and Mechanisms in Fluoride Shuttle Battery Reactions: Difference between Orthorhombic and Cubic BiF3 Single Microparticles

Reactivity and Mechanisms in Fluoride Shuttle Battery Reactions: Difference between Orthorhombic and Cubic BiF3 Single Microparticles

BiF3 Incorporation in Na/Ba Mixed Network Modifier Fluoride–Phosphate Glasses: Structural Studies by Solid-State NMR and Raman Spectroscopies

Evolution of Fluoride Shuttle Battery Reactions of BiF3 Microparticles in a CsF/LiBOB/Tetraglyme Electrolyte: Dependence on Structure, Size, and Shape

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Reactivity and Mechanisms in Fluoride Shuttle Battery Reactions: Difference between Orthorhombic and Cubic BiF₃ Single Microparticles

Reactivity and Mechanisms in Fluoride Shuttle Battery Reactions: Difference between Orthorhombic and Cubic BiF₃ Single Microparticles

BiF₃ Incorporation in Na/Ba Mixed Network Modifier Fluoride–Phosphate Glasses: Structural Studies by Solid-State NMR and Raman Spectroscopies

Evolution of Fluoride Shuttle Battery Reactions of BiF₃ Microparticles in a CsF/LiBOB/Tetraglyme Electrolyte: Dependence on Structure, Size, and Shape