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Related Concept Videos

Properties of Transition Metals02:58

Properties of Transition Metals

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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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Electrodeposition is a technique used to separate an analyte from interferents by electrochemical processes. Here, the analyte is a metal ion that can be deposited on an electrode immersed in the sample solution. The electrochemical setup consists of an anode and a cathode. When an electric current is applied to the setup, oxidation occurs at the anode. At the cathode, which consists of a large metal surface, metal ions undergo reduction and deposit onto the surface.
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Spontaneous redox reactions occur abundantly in nature. The chemical reaction occurring in a disposable AA battery powering our remote controls is one such example of a spontaneous redox reaction. Another example is the immersion of coiled copper wire into an aqueous silver nitrate solution. The reaction shows a gradual, visually impressive color change from colorless to bright blue and the formation of a grey precipitate on the copper wire. In this experiment,...
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The degradation of metals due to natural electrochemical processes is known as corrosion. Rust formation on iron, tarnishing of silver, and the blue-green patina that develops on copper are examples of corrosion. Corrosion involves the oxidation of metals. Sometimes it is protective, such as the oxidation of copper or aluminum, wherein a protective layer of metal oxide or its derivatives forms on the surface, protecting the underlying metal from further oxidation. In other cases, corrosion is...
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In redox reactions, the transfer of electrons occurs between reacting species. Electron transfer is described by a hypothetical number called the oxidation number (or oxidation state). It represents the effective charge of an atom or element, which is assigned using a set of rules.
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Transition Metal Slab Gliding: One Key Process for Activating Anionic Redox Reaction in P2-Type Transition Metal

Dongxiao Wang1, Feihu Zou1, Weiguang Lin2

  • 1Materials Genome Institute, Shanghai University, Shanghai, 200444, China.

Advanced Science (Weinheim, Baden-Wurttemberg, Germany)
|April 3, 2025
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Summary

Anionic redox in sodium-ion batteries is key for cathode performance. This study reveals how Ti4+ substitution in Na-ion battery cathodes activates reversible oxygen redox reactions, enhancing energy density.

Keywords:
P2‐type cathodeanionic redox reactionion migrationsodium‐ion batterytransition metal slab gliding

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Solid-state Chemistry

Background:

  • Anionic redox chemistry significantly impacts layered oxide cathode performance in sodium-ion batteries.
  • The exact mechanisms driving anionic redox, particularly in transition metal-stoichiometric oxides, remain unclear.
  • Existing models focus on Na-O-A configurations, which are not applicable to all systems exhibiting oxygen redox.

Purpose of the Study:

  • To investigate the mechanism of reversible anionic redox in transition metal-stoichiometric P2-type layered oxide cathodes for sodium-ion batteries.
  • To elucidate the role of Ti4+ substitution in activating oxygen redox reactions.
  • To enhance the energy density and stability of sodium-ion battery cathodes.

Main Methods:

  • Synthesis and characterization of P2-type Na2/3Cu1/3Mn2/3O2 and its Ti4+-substituted analogue (Na2/3Cu1/3Mn1/2Ti1/6O2).
  • Electrochemical testing, including galvanostatic cycling to assess capacity and stability.
  • Structural analysis to understand the impact of Ti4+ substitution on transition metal layer arrangements and migration.

Main Results:

  • Ti4+ substitution disrupts ordered transition metal layers, promoting slab gliding and migration.
  • New Na-O-vacancy configurations are formed upon Ti4+ substitution, enabling reversible oxygen redox.
  • The Ti4+-substituted cathode (Na2/3Cu1/3Mn1/2Ti1/6O2) achieved an initial discharge capacity of 153 mAh g-1 and 80% retention after 300 cycles at 2C.

Conclusions:

  • Ti4+ substitution is an effective strategy to activate reversible anionic redox in transition metal-stoichiometric layered oxide cathodes.
  • The study provides insights into the mechanism of oxygen redox beyond Na-O-A configurations.
  • This research offers pathways to improve the energy density and cycle life of sodium-ion batteries.