硬碳负极材料的掺杂改性及其储钠性能

金磊; 王欣茹; 李文倩; 王春婷; 张维民; 杨乃涛

doi:10.19799/j.cnki.2095-4239.2026.0437

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硬碳负极材料的掺杂改性及其储钠性能

储能测试与评价 | 更新时间：2026-08-26

- 硬碳负极材料的掺杂改性及其储钠性能
- Doping modification of hard carbon anode materials and sodium storage performance
- 储能科学与技术 2026年15卷第8期页码：3344-3355
- 作者机构：
  
  山东理工大学化学化工学院，山东淄博 255000
- 作者简介：
  
  金磊（1999—），男，硕士研究生，研究方向为能源化工与资源利用，E-mail：15615538093@163.com；
  张维民，副教授，研究方向为能源化工，E-mail：wmzhang@sdut.edu.cn。
- 基金信息：
  
  研究生教育优质课程建设项目：电化学工程(SDUTYKC202425)
- DOI：10.19799/j.cnki.2095-4239.2026.0437
  中图分类号： TM 912
- 收稿：2026-05-19，
  
  修回：2026-05-22，
  
  网络首发：2026-08-26，
  
  纸质出版：2026-08-28
- 稿件说明：
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金磊, 王欣茹, 李文倩, 等. 硬碳负极材料的掺杂改性及其储钠性能[J]. 储能科学与技术, 2026, 15(8): 3344-3355.

JIN Lei, WANG Xinru, LI Wenqian, et al. Doping modification of hard carbon anode materials and sodium storage performance[J]. Energy Storage Science and Technology, 2026, 15(8): 3344-3355.
金磊, 王欣茹, 李文倩, 等. 硬碳负极材料的掺杂改性及其储钠性能[J]. 储能科学与技术, 2026, 15(8): 3344-3355. DOI： 10.19799/j.cnki.2095-4239.2026.0437.

JIN Lei, WANG Xinru, LI Wenqian, et al. Doping modification of hard carbon anode materials and sodium storage performance[J]. Energy Storage Science and Technology, 2026, 15(8): 3344-3355. DOI： 10.19799/j.cnki.2095-4239.2026.0437.

摘要

受锂资源储量有限及储能市场需求快速扩张的双重驱动，钠离子电池（SIB）凭借低成本、高安全性等突出优势为新型储能本体技术多元化发展提供了重要解决方案。硬碳（HC）是目前SIB负极的最优候选材料，且已实现初步商业化应用。然而，其普遍存在首次库仑效率低、可逆比容量较低（约300 mAh/g）、离子迁移动力学缓慢等关键瓶颈。针对上述问题，本研究采用高电负性氟元素掺杂改性策略，以四氟对苯二甲酸（TFA）为氟源，通过简单的高温碳化与复烧工艺制备了一系列酚醛树脂衍生的氟掺杂硬碳负极材料（FHC），系统探究氟掺杂对硬碳微观结构及储钠性能的影响。研究表明，氟掺杂可有效调整碳基质的层间距、缺陷及闭孔结构，增加材料表面及体相储钠活性位点，加快迁移动力学，从而优化电化学储钠性能。电化学测试结果显示，当HC与TFA质量比为1∶2、二次煅烧温度为600℃时，电极在20 mA/g的电流密度下所获得的首次库仑效率高达92.61%，可逆比容量为354.64 mAh/g，在500 mA/g的大电流密度下仍可稳定循环800次以上。

Abstract

Driven by limitation in lithium supply and the rapidly growing demand for large-scale energy storage

sodium-ion batteries have emerged as promising alternatives because of their low cost and high safety. Hard carbon (HC) is currently regarded as one of the most promising anode materials for sodium-ion batteri

es and has already entered preliminary commercial use. However

its practical application remains restricted by several intrinsic issues

including relatively low initial Coulombic efficiency

limited reversible capacity (300 mAh/g)

and slow Na

diffusion kinetics. To address these challenges

this study proposes a fluorine-doping strategy that takes advantage of the strong electronegativity of fluorine. Using tetrafluoroterephthalic acid (TFA) as the fluorine source

a series of phenolic resin-derived fluorine-doped HC materials were successfully prepared through a simple high-temperature carbonization and secondary calcination process. The effects of fluorine doping on the microstructure and sodium storage behavior of HC were systematically investigated. The results demonstrate that fluorine doping effectively regulates the interlayer spacing

defect structure

and closed-pore characteristics of the carbon matrix. It also increases the availability of active sites for sodium storage and accelerates Na

transport kinetics

thereby improving overall electrochemical performance. Electrochemical measurements show that the optimal sample was obtained at an HC/TFA mass ratio of 1∶2 and a secondary calcination temperature of 600 ℃. This material exhibited a high initial Coulombic efficiency (92.61%) and delivered a reversible specific capacity of 354.64 mAh/g at 20 mA/g. In addition

the electrode maintained stable cycling performance over 800 cycles at a high current density (500 mA/g).

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references

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