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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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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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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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Crystalline solids are divided into four types: molecular, ionic, metallic, and covalent network based on the type of constituent units and their interparticle interactions.
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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid sodium chloride, the lattice energy is the enthalpy change of the process:
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Updated: Dec 21, 2025

Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications
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Dual-Doped Cubic Garnet Solid Electrolytes with Superior Air Stability.

Ljalem Hadush Abrha1, Tesfaye Teka Hagos2, Yosef Nikodimos1

  • 1Nano-electrochemistry Laboratory, Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 106, Taiwan.

ACS Applied Materials & Interfaces
|May 15, 2020
PubMed
Summary

Dual-doped garnets, Li6.05La3Ga0.3Zr1.95Nb0.05O12 ((Ga, Nb)-LLZO), exhibit enhanced air stability and reduced interfacial resistance. This breakthrough improves the potential of garnet solid electrolytes for practical applications in solid-state batteries.

Keywords:
air stabilitydual-doped cubic garnetinterfacial resistanceionic conductivitymorphologystable Li plating/stripping

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Solid-State Chemistry

Background:

  • Lithium7La3Zr2O12 (LLZO) garnets are promising solid electrolytes for lithium-ion batteries due to their high ionic conductivity and safety.
  • However, LLZO's practical application is hindered by instability during synthesis and storage, leading to high interfacial resistance.

Purpose of the Study:

  • To synthesize and characterize air-stable, dual-doped LLZO garnets with improved properties.
  • To investigate the effect of gallium (Ga) and niobium (Nb) doping on LLZO's structural stability and electrochemical performance.

Main Methods:

  • Synthesis of dual-doped Li6.05La3Ga0.3Zr1.95Nb0.05O12 ((Ga, Nb)-LLZO) cubic-phase garnets.
  • Characterization using Raman spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) to analyze impurity formation.
  • Electrochemical testing of Li//Li symmetric cells to evaluate plating/stripping behavior and interfacial resistance.
  • Rietveld refinement of XRD patterns to determine dopant site occupancy.

Main Results:

  • The synthesized (Ga, Nb)-LLZO garnets exhibit an ionic conductivity of 9.28 × 10-3 S cm-1.
  • Compared to undoped or singly doped LLZO, (Ga, Nb)-LLZO shows significantly reduced formation of LiOH and Li2CO3 upon air exposure.
  • Electrochemical tests reveal less polarization and more stable plating/stripping behavior for (Ga, Nb)-LLZO compared to (Ca, Nb)-LLZO.
  • Rietveld refinement indicates Ga preferentially occupies Li sites and Nb occupies Zr sites, contributing to improved stability.

Conclusions:

  • Dual doping with Ga and Nb significantly enhances the air stability of LLZO garnets by minimizing detrimental impurity phases.
  • The specific site occupancy of Ga and Nb in the LLZO structure leads to reduced interfacial resistance and improved electrochemical performance.
  • This work presents a promising strategy for developing highly stable garnet solid electrolytes for advanced solid-state batteries.