Heterogeneous F anion transport, local dynamics and electrochemical stability of nanocrystalline La1−xBaxF3−x

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Abstract

Solid state ion conductors exhibiting fast ion dynamics are of utmost importance for the development of modern energy storage systems or sensors. For the realization of fluoride ion batteries (FIBs), that is, batteries relying on F ions as charge carriers, materials with fast fluorine anion dynamics are needed. Here we used high-energy ball milling to incorporate BaF2 into the tysonite structure of LaF3 and studied ion dynamics by both broadband impedance and 19F nuclear magnetic resonance (NMR) spectroscopy. The nanocrystalline solid solution formed revealed increased ion conductivity compared to pure LaF3. Apart from the formation of F vacancies through aliovalent substitution, the increase in conductivity is also stimulated by the introduction of lattice strain and the high degree of local disorder produced. While long-range ion dynamics has been studied recently, less information is known about local ion hopping processes to which 19F NMR spin-lattice relaxation is sensitive. In this work, we tried to correlate short-range ion diffusion with long-range transport properties measured by conductivity spectroscopy. Additionally, we used electrochemical polarization and cyclic voltammetry to judge whether the ternary fluoride shows a sufficiently high electrochemical stability to work in FIBs.

Original languageEnglish
Pages (from-to)481-490
Number of pages10
JournalEnergy Storage Materials
Volume16
DOIs
Publication statusPublished - 1 Jan 2019
Externally publishedYes

Fingerprint

Anions
Negative ions
Ions
Fluorides
Spin-lattice relaxation
Fluorine
Ball milling
Charge carriers
Transport properties
Energy storage
Nuclear magnetic resonance spectroscopy
Cyclic voltammetry
Vacancies
Solid solutions
Substitution reactions
Nuclear magnetic resonance
Spectroscopy
Polarization
Sensors

Keywords

  • Conductivity
  • Diffusion
  • Electrolytes
  • Fluorides
  • Nanocrystalline ceramics
  • NMR

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)
  • Energy Engineering and Power Technology

Cite this

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title = "Heterogeneous F anion transport, local dynamics and electrochemical stability of nanocrystalline La1−xBaxF3−x",
abstract = "Solid state ion conductors exhibiting fast ion dynamics are of utmost importance for the development of modern energy storage systems or sensors. For the realization of fluoride ion batteries (FIBs), that is, batteries relying on F− ions as charge carriers, materials with fast fluorine anion dynamics are needed. Here we used high-energy ball milling to incorporate BaF2 into the tysonite structure of LaF3 and studied ion dynamics by both broadband impedance and 19F nuclear magnetic resonance (NMR) spectroscopy. The nanocrystalline solid solution formed revealed increased ion conductivity compared to pure LaF3. Apart from the formation of F vacancies through aliovalent substitution, the increase in conductivity is also stimulated by the introduction of lattice strain and the high degree of local disorder produced. While long-range ion dynamics has been studied recently, less information is known about local ion hopping processes to which 19F NMR spin-lattice relaxation is sensitive. In this work, we tried to correlate short-range ion diffusion with long-range transport properties measured by conductivity spectroscopy. Additionally, we used electrochemical polarization and cyclic voltammetry to judge whether the ternary fluoride shows a sufficiently high electrochemical stability to work in FIBs.",
keywords = "Conductivity, Diffusion, Electrolytes, Fluorides, Nanocrystalline ceramics, NMR",
author = "Stefan Breuer and Maria Gombotz and Veronika Pregartner and Ilie Hanzu and Martin Wilkening",
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AU - Breuer, Stefan

AU - Gombotz, Maria

AU - Pregartner, Veronika

AU - Hanzu, Ilie

AU - Wilkening, Martin

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Solid state ion conductors exhibiting fast ion dynamics are of utmost importance for the development of modern energy storage systems or sensors. For the realization of fluoride ion batteries (FIBs), that is, batteries relying on F− ions as charge carriers, materials with fast fluorine anion dynamics are needed. Here we used high-energy ball milling to incorporate BaF2 into the tysonite structure of LaF3 and studied ion dynamics by both broadband impedance and 19F nuclear magnetic resonance (NMR) spectroscopy. The nanocrystalline solid solution formed revealed increased ion conductivity compared to pure LaF3. Apart from the formation of F vacancies through aliovalent substitution, the increase in conductivity is also stimulated by the introduction of lattice strain and the high degree of local disorder produced. While long-range ion dynamics has been studied recently, less information is known about local ion hopping processes to which 19F NMR spin-lattice relaxation is sensitive. In this work, we tried to correlate short-range ion diffusion with long-range transport properties measured by conductivity spectroscopy. Additionally, we used electrochemical polarization and cyclic voltammetry to judge whether the ternary fluoride shows a sufficiently high electrochemical stability to work in FIBs.

AB - Solid state ion conductors exhibiting fast ion dynamics are of utmost importance for the development of modern energy storage systems or sensors. For the realization of fluoride ion batteries (FIBs), that is, batteries relying on F− ions as charge carriers, materials with fast fluorine anion dynamics are needed. Here we used high-energy ball milling to incorporate BaF2 into the tysonite structure of LaF3 and studied ion dynamics by both broadband impedance and 19F nuclear magnetic resonance (NMR) spectroscopy. The nanocrystalline solid solution formed revealed increased ion conductivity compared to pure LaF3. Apart from the formation of F vacancies through aliovalent substitution, the increase in conductivity is also stimulated by the introduction of lattice strain and the high degree of local disorder produced. While long-range ion dynamics has been studied recently, less information is known about local ion hopping processes to which 19F NMR spin-lattice relaxation is sensitive. In this work, we tried to correlate short-range ion diffusion with long-range transport properties measured by conductivity spectroscopy. Additionally, we used electrochemical polarization and cyclic voltammetry to judge whether the ternary fluoride shows a sufficiently high electrochemical stability to work in FIBs.

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KW - Electrolytes

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KW - NMR

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