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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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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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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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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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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Tetrahedral Complexes
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Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques
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Regulating Sodium Vacancy and Local Coordination Structure Enabled Stable Mn-Based NASICON Cathodes.

Nan Zhang1,2, Han Zhang1,2, Jiaxuan Liu1,2

  • 1State Key Laboratory of Space Power-Sources, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, China.

Angewandte Chemie (International Ed. in English)
|November 26, 2025
PubMed
Summary

Iron doping stabilizes the Na3MnTi(PO4)3 cathode for sodium-ion batteries by reducing defects and mitigating structural distortion. This enhances performance, offering a promising path for high-energy, long-lasting batteries.

Keywords:
Jahn–Teller effectLocal coordinationNa3MnTi(PO4)3Sodium vacancyVoltage hysteresis

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Fabrication of Spatially Confined Complex Oxides
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Fabrication of Spatially Confined Complex Oxides
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Fabrication of Spatially Confined Complex Oxides

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Energy Storage

Background:

  • NASICON-type Na3MnTi(PO4)3 (NMTP) cathodes offer low cost and high capacity for sodium-ion batteries.
  • Voltage hysteresis and structural degradation limit NMTP cathode performance.

Purpose of the Study:

  • To enhance NMTP cathode stability and electrochemical performance through a sodium vacancy and local coordination coupling strategy.
  • To suppress intrinsic antisite defects (IASDs) and Jahn-Teller distortion via low-valent ion doping.

Main Methods:

  • Introduced Fe2+ doping into the NMTP lattice, creating Na3+2xMnTi1-xFex(PO4)3.
  • Employed DFT calculations, ex situ XANES, and ssNMR analyses to investigate the synergistic mechanism.
  • Evaluated electrochemical performance, including specific capacity, rate capability, and cycling stability.

Main Results:

  • Fe2+ doping reduced Na vacancy concentration and activated Na2 sites, suppressing IASDs.
  • Reconstructed Mn-O coordination enhanced MnO6 symmetry, mitigating Jahn-Teller distortion.
  • Optimized Na3.2MnTi0.9Fe0.1(PO4)3 exhibited high capacity (174.2 mAh g-1 at 0.1 C), excellent rate capability (125.5 mAh g-1 at 20 C), and stable cycling (85% retention after 2000 cycles).

Conclusions:

  • The synergistic mechanism of reduced vacancy concentration and stabilized MnO6 symmetry effectively suppresses voltage hysteresis and Jahn-Teller distortion.
  • Fe2+ doping provides a viable strategy for designing high energy density, long-lifespan sodium-ion batteries.
  • This work offers insights into vacancy and coordination engineering for advanced battery materials.