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Ionic Crystal Structures02:42

Ionic Crystal Structures

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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
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Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. 
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Ionic Association01:28

Ionic Association

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The ionic association is the association of oppositely charged ions in an electrolyte solution to form ion pairs. Bjerrum defined ion pairs as two oppositely charged ions whose electrostatic attraction exceeds the thermal energy of the system, typically expressed as 2kT. Electrostatic attraction depends on ionic charge, separation distance, and the dielectric constant of the medium. Thermal energy, represented by kT, reflects the tendency of ions to move independently due to molecular motion.
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Theory of Strong Electrolytes01:23

Theory of Strong Electrolytes

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The interionic forces of the strong electrolytes depend on the solvent's dielectric constant, which is the ability of a solvent to store electrical energy, based on its polarizability. and the solution's concentration. In high-dielectric solvents and in dilute solutions, weak electrostatic forces keep ions apart. However, in low-dielectric solvents or concentrated solutions, stronger interionic forces may cause ions to pair up as ionic doublets despite being fully ionized. The theory of strong...
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Electrolyte and Nonelectrolyte Solutions02:21

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Substances that undergo either a physical or a chemical change in solution to yield ions that can conduct electricity are called electrolytes. If a substance yields ions in solution, that is, if the compound undergoes 100% dissociation, then the substance is a strong electrolyte. Complete dissociation is indicated by a single forward arrow. For example, water-soluble ionic compounds like sodium chloride dissociate into sodium cations and chloride anions in aqueous solution.
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Pure substances consist of only one type of matter. A pure substance can be an element or a compound. An element consists of only one type of atom, while a compound consists of two or more types of atoms held together by a chemical bond. Elements are classified as atomic or molecular based on the nature of their basic units.
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Solid electrolytes for fluoride ion batteries: ionic conductivity in polycrystalline tysonite-type fluorides.

Carine Rongeat1, M Anji Reddy, Raiker Witter

  • 1Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT) , Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.

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Fluoride ion batteries offer high energy density but require better solid electrolytes. This study improved ionic conductivity in tysonite-type La(1-y)Ba(y)F(3-y) solid solutions by addressing grain boundary effects through heat treatment.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Solid-State Chemistry

Background:

  • Fluoride ion batteries (FIBs) are promising high-energy-density alternatives to Li-ion batteries.
  • Current FIB performance is limited by the ionic conductivity of solid electrolytes.
  • Tysonite-type rare-earth fluorides, like LaF3, show potential for solid electrolytes.

Purpose of the Study:

  • To investigate the ionic conductivity of polycrystalline La(1-y)Ba(y)F(3-y) solid solutions for FIB applications.
  • To understand the conduction mechanisms and the impact of grain boundaries on ionic conductivity.
  • To explore methods for improving ionic conductivity in these materials.

Main Methods:

  • Synthesis of La(1-y)Ba(y)F(3-y) solid solutions (0 ≤ y ≤ 0.15) using ball milling.
  • Detailed ionic conductivity analysis using DC and AC conductivity measurements.
  • Heat treatment of the synthesized materials to evaluate its effect on conductivity.

Main Results:

  • The study analyzed the ionic conductivity of La(1-y)Ba(y)F(3-y) solid solutions.
  • DC and AC conductivity analyses revealed a conduction mechanism influenced by grain boundary blocking.
  • Heat treatment of the electrolyte material resulted in improved ionic conductivity.

Conclusions:

  • Grain boundaries significantly impede ionic conductivity in tysonite-type fluoride solid electrolytes.
  • Heat treatment is an effective strategy to mitigate the detrimental effects of grain boundaries.
  • This research opens new avenues for developing high-performance solid electrolytes for fluoride ion batteries.