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Universal Bulk Pre-Oxidation Strategy for Programming High-Performance Pitch-Derived Hard Carbon Anodes.

Shuaipeng Liu1, Xiang Wang1, Yangyang Chu1

  • 1State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China.

Small (Weinheim an Der Bergstrasse, Germany)
|November 7, 2025
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Summary

Uniform bulk pre-oxidation of pitch precursors using ammonium-based promoters enhances hard carbons (HCs) for sodium-ion batteries. This strategy improves structural homogeneity and sodium storage performance, enabling high reversible capacity and rate capabilities.

Keywords:
bulk pre‐oxidizationclosed porositygeneral strategypitch‐derived hard carbonsmall‐molecule promotors

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Energy Storage

Background:

  • Pre-oxidation is crucial for hard carbons (HCs) in sodium-ion batteries to prevent graphitization during carbonization.
  • Conventional pre-oxidation methods lead to non-uniform crosslinking, hindering oxygen diffusion and structural homogeneity in pitch precursors.

Purpose of the Study:

  • To develop a chemical bulk-crosslinking strategy for uniform pre-oxidation of pitch precursors.
  • To improve the structural properties and sodium storage performance of pitch-derived hard carbons.

Main Methods:

  • Utilized ammonium-based small molecules (e.g., NH4H2PO4, (NH4)2SO4) as molecular promoters for uniform bulk crosslinking.
  • Investigated the effect of this strategy on oxygen penetration, porosity, and interlayer spacing.
  • Conducted in situ characterization analyses to elucidate the sodium storage mechanism.

Main Results:

  • Achieved uniform oxygen penetration and eliminated gradient crosslinking in pitch precursors.
  • Generated favorable closed porosity and expanded interlayer spacing (0.389 nm).
  • The resulting HC anode exhibited a high reversible capacity (340 mAh g⁻¹ at 30 mA g⁻¹) and excellent rate performance (191.2 mAh g⁻¹ at 300 mA g⁻¹).

Conclusions:

  • The chemical bulk-crosslinking strategy provides a universal platform for uniform pre-oxidation of carbon precursors.
  • This approach offers fundamental insights and scalable material design principles for high-performance sodium-ion batteries.
  • A sequential 'adsorption-intercalation-pore filling' sodium storage mechanism was elucidated.