Pre-oxidation modulated structure of anthracite-derived hard carbon for enhanced sodium storage performance

TANG Jinhui; WU Fayuan; WANG Zhen; QIAN Zhiyong; LAI Xinhui

doi:10.19799/j.cnki.2095-4239.2025.1048

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Pre-oxidation modulated structure of anthracite-derived hard carbon for enhanced sodium storage performance

Energy Storage Materials and Devices | 更新时间：2026-07-13

- Pre-oxidation modulated structure of anthracite-derived hard carbon for enhanced sodium storage performance
- Energy Storage Science and Technology Vol. 15, Issue 6, Pages: 2104-2117(2026)
- 作者机构：
  
  国网江西省电力有限公司电力科学研究院，江西南昌 330096
- 作者简介：
- 基金信息：
- DOI：10.19799/j.cnki.2095-4239.2025.1048
  CLC： O 646
- Received：19 November 2025，
  
  Revised：2026-01-14，
  
  Published：28 June 2026
- 稿件说明：
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汤锦慧, 伍发元, 王震, 等. 预氧化调控无烟煤衍生硬碳结构及其储钠性能[J]. 储能科学与技术, 2026, 15(6): 2104-2117.

TANG Jinhui, WU Fayuan, WANG Zhen, et al. Pre-oxidation modulated structure of anthra-derived hard carbon for enhanced sodium storage performance[J]. Energy Storage Science and Technology, 2026, 15(6): 2104-2117.
汤锦慧, 伍发元, 王震, 等. 预氧化调控无烟煤衍生硬碳结构及其储钠性能[J]. 储能科学与技术, 2026, 15(6): 2104-2117. DOI： 10.19799/j.cnki.2095-4239.2025.1048.

TANG Jinhui, WU Fayuan, WANG Zhen, et al. Pre-oxidation modulated structure of anthra-derived hard carbon for enhanced sodium storage performance[J]. Energy Storage Science and Technology, 2026, 15(6): 2104-2117. DOI： 10.19799/j.cnki.2095-4239.2025.1048.

摘要

无烟煤作为钠离子电池硬碳负极的前驱体，具有碳含量高和成本低的优势，但其直接碳化易石墨化，层间距过小，限制了储钠能力。为此，本研究系统对比了多种预氧化方法，筛选出最优的混酸（硫酸/硝酸）氧化策略，在预氧化温度70℃反应9 h条件下，实现了对类石墨微区结构的有效调控。硫酸作为磺化剂和插层介质，引入磺酸基团，有效打破无烟煤的致密芳香结构并扩大碳层间距，硝酸则作为强氧化剂，通过引入含氮/氧官能团促进芳香片层间的交联，抑制高温石墨化趋势，并协同构建丰富的超微孔与闭孔结构。改性后的无烟煤衍生硬碳材料在0.02 A/g电流密度下可逆容量达321.15 mAh/g，平台容量提升至210.7 mAh/g，即使在2.0 A/g高倍率下仍可保持207.3 mAh/g的可逆容量。选择最佳硬碳材料研究其储钠机制，通过循环伏安、恒电流间歇滴定（GITT）等测试，可以推测低电位区（0.01~0.1 V）的容量贡献主要源于钠离子在闭孔中的填充和在层间的嵌入行为，验证了“吸附-嵌入/填充”的储钠机制。本研究从分子层面实现了对硬碳前驱体结构的精准调控，为低成本、高性能硬碳负极的开发提供了新思路。

Abstract

Anthracite is considered to be a promising precursor for hard carbon anodes in sodium-ion batteries (SIBs)

primarily due to its naturally high fixed-carbon content

structural stability

and low cost. However

the direct carbonization of anthracite tends to induce excessive graphitization

which results in insufficient interlayer spacing (d002) and consequently leads to limited sodium-storage capacity. In particular

it diminishes the plateau capacity in the low-potential region that is critical for achieving high e

nergy density in SIBs. To overcome these structural limitations

in this work we systematically investigated and compared multiple pre-oxidation strategies—including air oxidation

single-acid treatments

and mixed-acid oxidation—aimed at modifying the microstructure of anthracite before carbonization. We identified a mixed-acid oxidation method using sulfuric acid (H

) and nitric acid (HNO

) as the most effective one. Under optimized conditions of 70℃ for 9 hours

this method successfully modulates the graphite-like microdomains in the carbon precursor. In this process

sulfuric acid acts as a sulfonating and intercalating agent

introducing sulfonic groups (—SO

H) that help break the dense aromatic structure of anthracite and expand the interlayer spacing. Nitric acid serves as a strong oxidant

incorporating nitrogen- and oxygen-containing functional groups that promote cross-linking between aromatic layers

thereby suppressing graphitization during high-temperature treatment. The synergistic effect of both acids also facilitates the formation of abundant ultramicropores and closed pores. The optimized hard carbon material exhibits significantly improved electrochemical performance. It delivers a reversible capacity of 321.15 mAh/g at 0.02 A/g

with a plateau capacity of 210.7 mAh/g. Even at the high current density of 2.0 A/g

it maintains a capacity of 207.3 mAh/g

demonstrating excellent rate capability. To investigate the sodium-storage mechanism of the best-performing sample

we employed cyclic voltammetry and a galvanostatic intermittent-titration technique. The results suggest that the capacity in the low-potential region (0.01-0.1 V) arises mainly from sodium-ion insertion into the expanded interlayers and filling into closed pores

supporting a combined "adsorption-intercalation/filling" mechanism. In summary

this study demonstrates a rational and effective pre-oxidation strategy for achieving molecular-level structural tailoring of anthracite-derived ha

rd carbon. The proposed mixed-acid treatment not only enhances the interlayer spacing and introduces beneficial functional groups but also creates a favorable pore structure for sodium storage. These findings offer valuable new insights into the design of low-cost

high-performance carbon anodes for SIBs and underscore the importance of precursor engineering in regulating sodium-storage behavior for next-generation energy-storage systems.

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