物理化学学报 >> 2025, Vol. 41 >> Issue (10): 100119.doi: 10.1016/j.actphy.2025.100119

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通过分子内氧化提升沥青衍生硬碳的储钠性能以用于高性能钠离子电池

李文慧1, 唐亚昆1,*(), 周玉生3, 张月1,*(), 张文海1, 马庆涛1, 刘浪1,*(), 董森1, 曹余良1,2,*   

  1. 1 碳基能源资源化学与利用国家重点实验室; 新疆大学化学学院, 新疆 乌鲁木齐 830017
    2 有机硅化合物及材料教育部工程研究中心, 武汉大学化学与分子科学学院, 湖北 武汉 430072
    3 北京钠元素时代新材料科技有限公司, 北京 102600
  • 收稿日期:2025-04-20 修回日期:2025-05-27 录用日期:2025-06-11 发布日期:2025-09-29
  • 通讯作者: Email: yktang@xju.edu.cn (唐亚昆)yuezhang@xju.edu.cn (张月)liulang@xju.edu.cn (刘浪)ylcao@whu.edu.cn (曹余良)
  • 基金资助:
    新疆维吾尔自治区重点研发项目(2024B01009-1); 新疆维吾尔自治区重点研发项目(2024B04008-3); 上海合作组织科技伙伴计划和国际科技合作计划(2023E01004); 国家自然科学基金(22368047); 国家自然科学基金(22468048)

Enhanced sodium storage performance of asphalt-derived hard carbon through intramolecular oxidation for high-performance sodium-ion batteries

Wenhui Li1, Yakun Tang1,*(), Yusheng Zhou3, Yue Zhang1,*(), Wenhai Zhang1, Qingtao Ma1, Lang Liu1,*(), Sen Dong1, Yuliang Cao1,2,*   

  1. 1 State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources; College of Chemistry, Xinjiang University, Urumqi 830017, Xinjiang Uygur Autonomous Region, China
    2 Engineering Research Center of Organosilicon Compounds & Materials of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei Province, China
    3 Beijing Sodium Element Era New Material Technology Co., Ltd., 102600 Beijing, China
  • Received:2025-04-20 Revised:2025-05-27 Accepted:2025-06-11 Published:2025-09-29
  • Contact: Email: yktang@xju.edu.cn (Yakun Tang)yuezhang@xju.edu.cn (Yue Zhang)liulang@xju.edu.cn (Lang Liu)ylcao@whu.edu.cn (Yuliang Cao)
  • Supported by:
    the Key R & D Program of Xinjiang Uygur Autonomous Region(2024B01009-1); the Key R & D Program of Xinjiang Uygur Autonomous Region(2024B04008-3); the Shanghai Cooperation Organization Science and Technology Partnership Program and International Science and Technology Cooperation Program(2023E01004); the National Natural Science Foundation of China(22368047); the National Natural Science Foundation of China(22468048)

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摘要：

高性能、低成本硬碳的发展对钠离子电池的商业化起到了至关重要的作用。由于沥青具有分布广泛，资源丰富，和成本低廉的特点，被认为是适宜的硬碳前驱体。但因其容量小、电化学反应动力学差，进一步限制了其应用。本文通过混酸的协同作用，成功通过分子内氧化合成了沥青基硬碳纳米片。硫酸的引入有效促进了沥青分子层间结构的膨胀与解离，进而显著增强了硝酸对沥青分子的分子内氧化效率。混酸氧化过程有效地引入了含氧官能团(OFGs)，增大了层间距和形成更多纳米多孔结构，从而增加了可逆容量和提高了速率性能。优化后的沥青基硬碳在0.03 A∙g−1的电流密度下，可逆充电容量由115.0 mAh∙g−1提高至304.4 mAh∙g−1，平台容量提高5.5倍。本研究揭示了液相酸氧化对储钠型硬碳结构和组成的影响，揭示了制备低成本、高性能沥青基硬碳的有效方法。

关键词: 钠离子电池, 沥青基硬碳, 碳纳米片, 分子内氧化

Abstract:

The development of high-performance and low-cost hard carbon plays a crucial role in the commercialization of sodium-ion batteries (SIBs). Asphalt is considered a suitable hard carbon precursor due to its wide distribution, abundance, and cost-effectiveness. However, its low capacity and poor electrochemical reaction kinetics limit its further application. Herein, we have successfully synthesized asphalt-based hard carbon nanosheets through a process of intramolecular oxidation, facilitated by the synergistic action of mixed acids. The introduction of sulfuric acid plays a crucial role in expanding the tightly packed asphalt molecules, which in turn allows for the intramolecular oxidation of asphalt molecules by nitric acid. This oxidation process effectively introduces oxygen-containing functional groups (OFGs), leading to an increase in interlayer spacing and the formation of a more nanoporous structure, resulting in both enhanced capacity and improved rate performance. The optimized asphalt-based hard carbon boosts reversible capacity from 115.0 to 304.4 mAh∙g−1 at 0.03 A∙g−1, and the plateau capacity is increased by 5.5 times. This work provides a profound understanding of the impact of liquid-phase acid oxidation on the structure and composition of sodium-storage hard carbon, and further unveils an effective method for obtaining low-cost and high-performance asphalt-based hard carbon.

Key words: Sodium-ion battery, Asphalt-based hard carbon, Nanosheet, Intramolecular oxidation