NaCl辅助构筑高性能沥青基硬炭负极材料

doi:10.11949/0438-1157.20240928

摘要/Abstract

摘要：

石油沥青具有价格低廉、芳香性高、易缩聚等优点，是制备高附加性硬炭负极材料的理想前体。然而，直接碳化沥青的过程中芳香烃和烷烃易发生缩聚和重排，使其石墨化程度高、层间距小、缺陷位点少，导致储钠性能差。因此，提出在沥青预氧化过程中引入NaCl助氧剂，促进沥青的氧化交联反应，抑制沥青分子结构重排，降低硬炭的石墨化度，增大层间距，引入丰富的CO基团和闭孔结构，进而提升沥青基硬炭负极的储钠性能。在30 和300 mA·g^-1下沥青基硬炭负极的比容量高达285.0和145.0 mAh·g^-1，首次库仑效率为96.3%。同时，在30 mA·g^-1下的平台容量为173.2 mAh·g^-1，占总容量的61.4%。此外，该负极在0.1 A·g^-1下循环200圈的容量保持率高达93.94%，表现出优异的循环稳定性能。

关键词: NaCl辅助预氧化, 石油沥青, 硬炭负极, 钠离子电池, 电化学性能

Abstract:

Petroleum asphalt has the advantages of low price, high aromaticity and easy polycondensation, and is an ideal precursor for the preparation of high-additive hard carbon anode materials. However, the aromatic hydrocarbons and alkane in petroleum asphalt are prone to condensation and rearrangement during its direct carbonization, and resulting in high graphitization, small layer spacing coupled with few defect sites, which lead to a poor sodium-ion storage performance. Therefore, this work proposes to introduce NaCl pro-oxygenic agent into the asphalt pre-oxidation process for promoting oxidative cross-linking reaction, inhibiting the rearrangement of the asphalt molecular structure, which can reduce the graphitization degree of hard carbon, expand the layer spacing, and introduce abundant CO groups and closed-pore structures, thereby enhancing the sodium-ion storage performance of the pitch-based hard carbon anode. This asphalt-based hard carbon anode delivers high specific capacities of 285.0 and 145.0 mAh·g^-1 at 30 and 300 mA·g^-1, respectively, coupled with 96.3% initial coulombic efficiency. Meanwhile, it has a high plateau capacity of 173.2 mAh·g^-1 at 30 mA·g^-1, corresponding to 61.4% of the total specific capacity. In addition, the capacity retention rate of this anode is as high as 93.94% for 200 cycles at 0.1 A·g^-1, demonstrating an excellent cycling stability performance.

Key words: NaCl-assisted pre-oxidation, petroleum asphalt, hard carbon anode, sodium-ion battery, electrochemical performance

中图分类号:

TQ 028.8

肖志华, 房浩楠, 郑方植, 孙冬, 陶丽达, 李永峰, 徐春明, 马新龙. NaCl辅助构筑高性能沥青基硬炭负极材料[J]. 化工学报, 2025, 76(2): 846-857.

Zhihua XIAO, Haonan FANG, Fangzhi ZHENG, Dong SUN, Lida TAO, Yongfeng LI, Chunming XU, Xinlong MA. NaCl assisted constructing high-performance pitch-based hard carbon anode material[J]. CIESC Journal, 2025, 76(2): 846-857.

图/表 6

图1 OHC-NaCl的制备示意图（a）；HC，OHC和OHC-NaCl三种硬炭材料前体的FTIR谱图（b）和XPS总图（c）；OHC-NaCl硬炭前体的C 1s分峰谱图（d）；HC，OHC和OHC-NaCl的XRD谱图（e）

Fig.1 Preparation diagram of OHC-NaCl (a); FTIR (b) and XPS (c) patterns of HC, OHC and OHC-NaCl precursors; C 1s spectra of OHC-NaCl precursor (d); XRD patterns of HC, OHC and OHC-NaCl (e)

图2 HC [(a), (b)]，OHC[(c), (d)]和OHC-NaCl[(e), (f)]的SEM和TEM图

Fig.2 The corresponding SEM and TEM images of HC [(a), (b)], OHC [(c), (d)] and OHC-NaCl [(e), (f)]

图3 HC，OHC和OHC-NaCl的拉曼图（a）；OHC（b）和OHC-NaCl（c）的拉曼分峰图；N2吸脱附曲线（d）及孔径分布（e）；XPS总图（f）；OHC（g）和OHC-NaCl（h）的O 1s XPS分峰图及其CO，C—O和O—CO含量占比（i）

Fig.3 Raman patterns of HC, OHC and OHC-NaCl (a); The peak fitting of Raman spectra for OHC (b) and OHC-NaCl (c); N2 adsorption/desorption curves (d) and the corresponding pore-size distribution curves (e); Total XPS survey (f)； O 1s spectra of OHC (g) and OHC-NaCl (h), and the corresponding CO, C—O and O—CO percentage (i)

图4 HC、OHC和OHC-NaCl三种硬炭负极在不同电流密度下的倍率性能（a），在30 mA·g-1下的充放电曲线（b）及其对应的平台容量和斜坡容量（c）；HC（d），OHC（e）和OHC-NaCl（f）在0.1 mV·s-1下的CV曲线；三种电极在100 mA·g-1下循环100圈的容量保持性能和库仑效率曲线（g），OHC-NaCl在70 mA·g-1下循环200圈的容量保持性能和库仑效率曲线（h）；三种电极的电化学阻抗谱图（i）

Fig.4 Rate performance at different current densities (a), charge and discharge profiles at 30 mA·g-1 (b)，and the corresponding plateau capacity and slopping capacity (c) of HC, OHC and OHC-NaCl electrodes; CV curves of HC (d), OHC (e) and OHC-NaCl(f) at 0.1 mV·s-1; Cycling performance and CE at 100 mA·g-1 (g) and 70 mA·g-1(h), respectively; (i) Impedance patterns of HC, OHC and OHC-NaCl

图5 OHC-NaCl负极的比容量和首次库仑效率值与文献对比

Fig.5 Comparison of OHC-NaCl with these reported HC anodes in the specific capacity and coulombic efficiency

图6 NVP//OHC-NaCl全电池的电化学性能：（a）不同电流密度下的倍率性能；（b）充放电曲线；（c）0.4 C下的循环性能(插图为循环100圈后点亮的LEDs灯图)；（d）循环不同圈数的充放电曲线

Fig.6 The electrochemical performance of NVP//OHC-NaCl full cell: (a) Rate performance at various current densities; (b) Charge and discharge profiles within 0.1—2.0 C; (c) Cycling performance for 100 cycles (the inset is the lighted LEDs); (d) Charge and discharge profiles at different cycles at 1st, 20th, 50th, 80th and 100th

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