NaClO4改性煤沥青基硬碳材料及其储钠性能研究
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1.太原理工大学 材料科学与工程学院,山西 太原 030024 ;2.太原理工大学 电气与动力工程学院,山西 太原 030024 ;3.东华理工大学 水资源与环境工程学院,江西 南昌 330013

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常茂林(1996—),硕士研究生,主要从事储能用碳基新材料方面的研究。

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TM912

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山西省基础研究计划(202403021211028)


NaClO4 modified coal tar pitch-based hard carbon material and its sodium storage performance
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1.College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024 , China ;2.College of Electrical and Power Engineering, Taiyuan University of Technology, Taiyuan 030024 , China ;3.School of Water Resources and Environment, East China University of Technology, Nanchang 330013 , China

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    摘要:

    煤沥青(Coal tar pitch, CTP)是煤焦油加工后的产物,富含稠环芳烃,具有碳产率高、孔隙可调、成本低及易加工等特点,是制备钠离子电池硬碳负极材料理想的前驱体。然而,在高温碳化过程中, CTP的稠环芳烃结构易形成致密石墨微晶,阻碍钠离子嵌入/脱出,从而限制其在钠离子电池中的应用。 针对上述问题,本文提出“气固双干扰”调控策略,利用高氯酸钠(NaClO4 )热分解产生的气相与固相产物协同调控煤沥青前驱体的微观结构。具体作用机制为:①气相分解产物(O2 )可促进煤沥青分子链发生交联反应,有效抑制其石墨化进程;②固相分解产物(NaCl)能够阻碍沥青芳香族链间的强 π-π 共轭堆叠,缓解过度堆积,同时优化材料的孔道结构。经优化制备的CTP硬碳(P20-500-1400)表现出胶囊状纳米石墨筹结构,且富含大量孔隙结构,这种结构为钠离子的存储提供了丰富的活性位点,同时为钠离子的传输提供了便捷的通道,显著提升了材料的储钠性能。相较于未改性样品,P20-500-1400的可逆容量提升了1.8倍,达到232.5 mAh·g? 1 ,首效为84%。在1.5 A·g? 1 的大电流密度下,容量为187.4 mAh·g? 1 ;在0.3 A·g? 1 的电流密度下循环 1 000圈后容量仍能保持在 190.5 mAh·g? 1 ,容量保持率为 91%。本工作可为高性能、低成本钠离子电池负极材料的开发提供理论基础和技术参考。

    Abstract:

    Coal tar pitch (CTP), a product derived from coal tar processing, is rich in polycyclic aromatic hydrocarbons (PAHs), and is an ideal precursor for the preparation of hard carbon anode materials for sodium-ion batteries (SIBs) because of its high carbon yield, tunable porosity, low cost, and easy processability. However, during high-temperature carbonization, the polycyclic aromatic structure of CTP is prone to forming dense graphitic microcrystals, which hinder the insertion/extraction of sodium ions and limit its application in SIBs. To address this issue, this paper proposes a “gas-solid dual-interference” strategy, in which the gas-phase and solid-phase products generated during the decomposition of sodium perchlorate (NaClO4 ) synergistically regulate the structure of the coal tar pitch precursor:① the gas-phase decomposition product (O2 ) promotes the cross-linking of coal tar pitch molecules and effectively suppresses the graphitization process;② the solid-phase decomposition product (NaCl) hinders the strong π-π interactions between the aromatic chains of the pitch and alleviates excessive stacking while optimizing the pore structure. The optimally prepared CTP-based hard carbon (P20-500-1400) exhibits a capsule-like nano-graphitic structure and is rich in abundant pore structures, which provide abundant active sites for sodium-ion storage, as well as facilitated pathways for sodium-ion transport. Compared with the unmodified sample, the reversible capacity of P20-500-1400 is increased by 1. 8 times to 232. 5 mAh·g-1 , with an initial coulombic efficiency of 84%. The capacity is 187. 4 mAh·g-1 at a high current density of 1. 5 A·g-1 , and can still be maintained at 190. 5 mAh·g-1 after 1 000 cycles at 0. 3 A·g-1 , with a capacity retention of 91%. This work provides a theoretical basis and technical reference for the development of high-performance and low-cost anode materials for SIBs.

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常茂林,严轶阳,张瑾,等 . NaClO4改性煤沥青基硬碳材料及其储钠性能研究[J]. 中国有色冶金,2026,55(2): 118-127.

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  • 收稿日期:2025-11-28
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  • 在线发布日期: 2026-05-12
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