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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.
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The addition of an inert ionic compound increases the solubility of a sparingly soluble salt. For example, adding potassium nitrate to a saturated solution of calcium sulfate significantly enhances the solubility of calcium sulfate. Le Châtelier's principle cannot predict this shift in the equilibrium. Instead, this could be explained in terms of changes in the effective concentration of the ions in solution in the presence of added inert salt.
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When a substance such as sodium chloride is added to water, it dissolves, forming an aqueous solution. The extent of dissolution is called solubility. The process of dissolution can exist in equilibrium, just like other chemical processes. Solubility equilibria are also called precipitation equilibria because the process of solubility can be reversible. The reverse of the solubility process is called precipitation.
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Ionic Bonding and Electron Transfer02:48

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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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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Simple Methods for the Preparation of Non-noble Metal Bulk-electrodes for Electrocatalytic Applications
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Fluorination-Enhanced Surface Stability of Disordered Rocksalt Cathodes.

Linze Li1, Juhyeon Ahn2, Yuan Yue2

  • 1Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, WA, 99354, USA.

Advanced Materials (Deerfield Beach, Fla.)
|December 15, 2021
PubMed
Summary

Fluorine substitution in cation-disordered rocksalt (DRX) oxides enhances Li-ion battery cathode stability by mitigating oxygen loss and interfacial reactions, improving cycling performance.

Keywords:
cathodescycling stabilitydisordered rocksaltfluorine substitutionlattice stabilityoxygen loss

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Solid-State Chemistry

Background:

  • Cation-disordered rocksalt (DRX) oxides offer high energy density for next-generation Li-ion batteries.
  • Capacity fade remains a significant challenge for DRX cathode materials.
  • Partial fluorine (F) substitution is a potential strategy to improve cycling stability.

Purpose of the Study:

  • To elucidate the atomistic mechanism by which fluorine substitution enhances the cycling stability of Mn-based DRX cathodes.
  • To investigate the structural and chemical evolution of Li-Mn-Nb-O-Fₓ (x = 0, 0.05, 0.2) cathodes during cycling.
  • To reveal the atomic origin of improved surface stability with increasing fluorine content.

Main Methods:

  • Advanced transmission electron microscopy (TEM) based imaging techniques.
  • Spectroscopy techniques for chemical analysis.
  • In-situ/operando analysis of cathode materials during battery cycling.

Main Results:

  • Fluorine substitution reduces oxygen (O) redox activity in the DRX lattice.
  • Increased fluorine concentration mitigates the formation of oxygen-deficient surface layers.
  • Low fluorine substitution leads to amorphous cathode-electrolyte interphase (CEI) formation and voids.
  • High fluorine concentration minimizes oxygen loss and interfacial reactions, enhancing surface stability.

Conclusions:

  • Fluorine substitution is an effective strategy to improve the cycling stability of DRX cathode materials.
  • The beneficial effect of fluorination stems from reduced oxygen activity and suppressed interfacial reactions.
  • Understanding anion substitution mechanisms guides the development of advanced cathode materials for Li-ion batteries.