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Related Concept Videos

Metal-Ligand Bonds02:51

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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.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
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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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Complexation Equilibria: The Chelate Effect01:19

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Crystal Field Theory - Octahedral Complexes02:58

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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
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Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
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"Mn-locking" effect by anionic coordination manipulation stabilizing Mn-rich phosphate cathodes.

Wei Zhang1,2,3, Yulun Wu1, Yuhang Dai3

  • 1School of Metallurgy and Environment, Engineering Research Center of the Ministry of Education for Advanced Battery Materials, Hunan Provincial Key Laboratory of Nonferrous Value-Added Metallurgy, Central South University Changsha 410083 P. R. China zhangzhian@csu.edu.cn laiyanqing@csu.edu.cn.

Chemical Science
|August 18, 2023
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Summary
This summary is machine-generated.

Fluorine doping enhances manganese-rich phosphate cathodes for sodium-ion batteries by improving stability and kinetics. This strategy boosts battery performance, enabling high power and stable cycling for advanced energy storage.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Energy Storage

Background:

  • High-voltage cathodes are crucial for high-performance sodium-ion batteries (SIBs).
  • Mn-rich phosphate cathodes face challenges due to low kinetics and structural instability, limiting capacity retention.
  • Developing stable and efficient cathodes is essential for advancing SIB technology.

Purpose of the Study:

  • To investigate the effect of light-weight fluorine (F) doping on Mn-rich phosphate cathodes for SIBs.
  • To enhance the electrochemical performance, specifically power and cyclability, of these cathodes.
  • To understand the mechanism behind F doping's impact on cathode stability and kinetics.

Main Methods:

  • Density Functional Theory (DFT) calculations to analyze electronic structure and bonding.
  • Fluorine (F) doping of Mn-rich phosphate materials.
  • In situ and ex situ characterization techniques to study structural and chemical changes.
  • Electrochemical testing to evaluate rate performance and cycling stability.

Main Results:

  • Fluorine doping significantly reduced the energy gap from 1.52 eV to 0.22 eV.
  • A
  • Mn-locking
  • effect was observed, strengthening Mn-ligand bonding and suppressing Mn dissolution.
  • Improved structural stability and enhanced electronic conductivity were achieved.
  • Electrochemical tests demonstrated outstanding rate performance up to 40C and stable cycling over 1000 cycles at 20C.
  • F doping did not alter the fundamental Na+ storage mechanisms.

Conclusions:

  • Light-weight fluorine doping is an effective strategy to improve the performance of Mn-rich phosphate cathodes.
  • The
  • Mn-locking
  • effect induced by F doping enhances structural integrity and electrochemical kinetics.
  • This anion doping approach offers a viable pathway for developing high-performance polyanionic cathodes for sodium-ion batteries.