原位构建稳定的氮掺杂石墨烯/碳纳米管三维宿主实现无枝晶和长寿命锂金属负极

In situ Construction of a Stable N-doped Graphene/Carbon Nanotubes Three-dimensional Host for Dendrite-free and Long-life Lithium Metal Anodes

摘要

采用化学气相沉积和热解法制备N掺杂石墨烯/碳纳米管(N-G/CNTs), 再经机械辊压到Li片获得N-G/CNTs-Li. 通过表征发现, 细长弯曲的CNTs原位接枝于石墨烯基体. 根据第一性原理, 锂更倾向于在吡咯N和吡啶N上形核沉积. N-G/CNTs半电池展示出仅为21.3 mV的形核过电位. N-G/CNTs-Li对称电池在1 mA/cm²的电流密度下能稳定循环长达1000 h, 在循环过程中始终保持最小的电压极化, 循环100 h后极片呈现光滑紧密的形貌, 无明显锂枝晶形成. 全电池在1C倍率下展现出129.3 mA·h/g的容量和91.5%的容量保持率. 结果表明, N-G/CNTs能够缓解循环过程中电极的体积变化, 有效抑制锂枝晶生长. N-G/CNTs良好的性能可归因于G/CNTs三维框架结构稳定性和高含量氮亲锂物种的协同效应. 因此, N-G/CNTs-Li电极在锂金属电池中具有广阔的应用前景.

Abstract

To suppress the growth of lithium dendrites on lithium metal anodes, this study constructs a stable three-dimensional (3D) host structure of N-doped graphene/carbon nanotubes (N-G/CNTs) designed to suppress dendrite growth and facilitate long cycle life in lithium metal batteries. The N-G/CNTs composite was prepared via chemical vapor deposition (CVD) and pyrolysis, and subsequently mechanically calendered onto a lithium foil to obtain the N-G/CNTs-Li anode. Morphological characterization reveals that slender, curved CNTs are in situ grafted onto the graphene substrate. First-principles calculations indicate that lithium preferentially nucleates and deposits on pyrrolic and pyridinic nitrogen sites. The N-G/CNTs half-cell exhibits a low nucleation overpotential of merely 21.3 mV. Furthermore, the N-G/CNTs-Li symmetric cell demonstrates stable cycling for up to 1000 h at a current density of 1 mA/cm², maintaining minimal voltage polarization throughout. Post-cycling morphology after 100 h shows a smooth and compact electrode surface, completely free of lithium dendrites. The full cell delivers a high capacity of 129.3 mA·h/g and a capacity retention of 91.5% at a 1C rate. These results collectively demonstrate that the N-G/CNTs host effectively mitigates electrode volume fluctuations and suppresses lithium dendrite growth during cycling. The excellent performance of the N-G/CNTs is attributed to the synergistic effect of the stability of the G/CNTs three-dimensional framework structure and the high content of the lithiophilic nitrogen species. Consequently, the N-G/CNTs-Li electrode holds great promise for applications in high-performance lithium metal batteries.

关键词

石墨烯 / 碳纳米管 / 氮掺杂 / 锂枝晶 / 长循环寿命 / 锂金属负极

Key words

Graphene / Carbon nanotubes / N doping / Lithium dendrites / Long cycle life / Lithium metal anodes

参考文献

[1] Liang Y., Huang D. Q., Yin G. D., Wen G., Qin W. X., Yao Y., Wei T., Chem. J. Chinese Universities, 2025, 46(7), 20250024

[2] (梁毅, 黄德权, 殷广达, 闻港, 覃维献, 姚远, 韦韬. 高等学校化学学报, 2025, 46(7), 20250024)

[3] Yu B., Fei L., Li M., Ma Z., Guo B., Chen J., Wang X., Xue Z., Zhou L., Wang J., Energy Storage Mater., 2025, 82, 104579

[4] Song Z., Wei C., Jiang J., Wang D., Wang X., Deng Q., Zhao Q., Zhou A., Li H., Li J., Chem. Eng. J., 2024, 501, 157755

[5] Vishweswariah K., Ningappa N. G., Bouguern M. D., Kumar M. R. A., Armand M. B., Zaghib K., Adv. Energy Mater., 2025, 15(39), 2501883

[6] Liu J., Zhang Y., Zhou J., Wang Z., Zhu P., Cao Y., Zheng Y., Zhou X., Yan C., Qian T., Adv. Funct. Mater., 2023, 33(34), 2302055

[7] Wang S., Sun Y. H., Gao X., Song R., Zhao M. Q., Lu Y., Bao X. B., Luo Q. M., Gou L., Fan X. Y., Chem. J. Chinese Universities, 2024, 45(6), 20240122

[8] (王帅, 孙雨涵, 高欣, 宋瑞, 赵铭钦, 卢垚, 鲍晓冰, 罗巧梅, 苟蕾, 樊小勇. 高等学校化学学报, 2024, 45(6), 20240122)

[9] Tian B., Huang Z., Xu X., Cao X., Wang H., Xu T., Kong D., Zhang Z., Xu J., Zang J., Li X., Wang Y., J. Mater. Sci. Technol., 2023, 132, 50-58

[10] Song M., Li Y., Gao L., Zhao R., Xu Y., Han S., Zhu J., Wang L., Zhao Y., Small, 2024, 20(9), 202306187

[11] Chen A., Gao M., Mo L., Wang J., Xu Z., Miao Y., Liu T., J. Colloid Interf. Sci., 2022, 614, 138-146

[12] Kim Y. B., Seo H. Y., Senthamaraikannan T. G., Cho J. S., Kang Y. C., Lim D., Park G., J. Mater. Sci. Technol., 2024, 192, 95-107

[13] Kim S., Choi J. H., Choi J. C., Jung D. S., Kang Y. C., Carbon, 2025, 243, 120497

[14] He X., Zhang K., Zhu Z., Tong Z., Liang X., Chem. Soc. Rev., 2024, 53, 9-24

[15] Geng D., Yang S., Zhang Y., Yang J., Liu J., Li R., Sham T., Sun X., Ye S., Knights S., Appl. Surf. Sci., 2011, 257(21), 9193-9198

[16] Tasdemir A., Kopuklu B. B., Kirlioglu A. C., Gursel S. A., Yurum A., Int. J. Hydrog. Energy., 2021, 46(21), 11865-11877

[17] Fang Y., Zhang S. L., Wu Z., Luan D., Lou X. W., Sci. Adv., 2021, 7(21), eabg3626

[18] Feng X., Wu H., Gao B., Swietoslawski M., He X., Zhang Q., Nano Res., 2021, 15(1), 352-360

[19] Li X., Chu Z., Jiang H., Dai Y., Zheng W., Liu A., Jiang X., He G., Energy Storage Mater., 2021, 37, 233-241

[20] Zhao C., Xiong S., Li H., Li Z., Qi C., Yang H., Wang L., Zhao Y., Liu T., J. Power Sources, 2021, 483, 229188

[21] Illa M. P., Pathak A. D., Sharma C. S., Khandelwal M., ACS Appl. Energy Mater., 2020, 3(9), 8676-8687

[22] Zhang Z., Wang J., Yan X., Zhang S., Yang W., Zhuang Z., Han W., Energy Storage Mater., 2020, 29, 332-340

[23] Li X., Huang S., Yan D., Zhang J., Fang D., Lim V. Y., Wang Y., Li T., Li Y., Guo L., Yang H., Energy Environ. Mater., 2022, 6(1), 12274

[24] Han S., Hou F., Yuan X., Liu J., Yan X., Chen S., Electrochim. Acta, 2017, 225, 566-573

[25] Niu S., Zhang S., Li D., Wang X., Chen X., Shi R., Shen N., Jin M., Zhang X., Lian Q., Huan R., Amini A., Zhao Y., Cheng C., Chem. Eng. J., 2022, 429, 132156

[26] Yu W., Wang J., Liu F., Cao Y., Deng B., Li J., Xie H., Zhang J., Tong H., Liang C., Carbon, 2025, 236, 120106

[27] Zhang X., Zhao Z., Xu J., Ouyang Q., Zhu C., Zhang X., Zhang X., Chen Y., Carbon, 2021, 177, 216-225

[28] Xu J., Zhang X., Yuan H., Zhang S., Zhu C., Zhang X., Chen Y., Carbon, 2020, 159, 357-365

[29] Luo W., Liu Q., Zhang B., Li J., Li R., Li T., Sun Z., Ma Y., Chem. Eng. J., 2023, 474, 145553

[30] Wang X., Zhang Y., Zheng J., Jiang H., Dong X., Liu X., Meng C., J. Colloid Interface Sci., 2020, 574, 312-323

[31] Li Y., Liu L., Yu Y., Shang X., Meng F., Carbon, 2022, 129, 503-518

[32] Zhang X., Jin S., Seo M. H., Shang C., Zhou G., Wang X., Lia G., Nano Energy, 2022, 93, 106905

[33] Ouyang W., Tan H., Liu X., Wang G., Cao Y., Xun W., Wang X., Yang L., Xu G., Huang J., Su J., ACS Appl. Energy Mater., 2025, 8(13), 9101-9109

[34] Wang G., Hu G., Lan J., Miao F., Zhang P., Shao G., J. Colloid. Interface Sci., 2024, 653, 148-158

[35] Lan Q., Ye D., Zhu X., Yang Y., Chen R., Wang S., Zhang T., Liao Q., Carbon, 2023, 207, 95-104

[36] Liu X., Zhao M., Liu D., Yang J., Han Y., Sultana R., Mohamed Y. M., Nazer H. A., Elnazer A. A., Zhang X., Surf. Interfaces, 2025, 68, 106672

[37] Gu H., Gao M., Shen K., Zhang T., Zhang J., Zheng X., Guo X., Liu Y., Cao F., Gu H., Kong Q., Xiong S., Chin. Chem. Lett., 2024, 35, 109273

[38] Xu S., Lu R., Sun K., Tang J., Cen Y., Luo L., Wang Z., Tian S., Sun X., Adv. Sci., 2022, 9, 2201421

[39] Yang L., Du C., Tian J., Yao X., Zhang Q., Ma X., Zhu Y., Zou M., Cao C., Appl. Catal. B: Environ., 2024, 355, 124190

[40] Xie H., Hou C., Qu Y., Tian H., Lu H., Wu J., Yang S., Ma Y., J. Energy Storage, 2023, 72, 108452

[41] He M., Zong M., Zhang P., Huo S., Zhang X., Song X., Li K., Sep. Purif. Technol., 2022, 297, 121558

[42] Luo K., Wu K., Hou Q., Zhang W., Jiang T., Wang X., Liu X., Liu W., Carbohyd. Polym., 2022, 277, 118833

[43] Han L., Li K., Liu H., Jiao Y., Yin X., Li H., Song Q., Qi L., Chem. Eng. J., 2023, 465, 142839

[44] Chen S., Chen P., Wang Y., Nanoscale, 2011, 3(10), 4323-4329

[45] Sheng J., Han Z., Jia G., Zhu S., Xu Y., Zhang X., Yao Y., Li Y., Adv. Funct. Mater., 2023, 33, 2306785

[46] Peng Z., Song J., Huai L., Jia H., Xiao B., Zou L., Zhu G., Martinez A., Roy S., Murugesan V., Lee H., Ren X., Li Q., Liu B., Li X., Wang D., Xu W., Zhang J., Adv. Energy Mater., 2019, 9(42), 1901764

[47] Liang Y., Liu F., Wang R., Ren J., Wang X., Wang H., Song J., Feng L., Wang R., J. Energy Chem., 2025, 111, 316-327

[48] Feng Y., Li Y., Wang P., Guo Z., Cao F., Ye H., Angew. Chem. Int. Ed., 2023, 62, 202310132

[49] Lee J., Choi S. H., Qutaish H., Hyeon Y., Han S., Heo Y., Whang D., Lee J., Moon J., Park M., Kim J. H., Dou S. X., Energy Storage Mater., 2021, 37, 315-324

[50] Li T., Jiang J., Zhou H., Shang H., Huang M., Gao J., Qu M., Liu W., Zhang H., Peng G., Diam. Relat. Mater., 2022, 130, 109391

[51] Fan Y., Kim D., Chen Y., Bi D., Han Q., Cai Q., Hu X., Mateti S. M., Yu B., Chen Y., Adv. Energy Mater., 2024, 14(26), 2400933

[52] Shu N., Xie J., Wang X., He X., Xiao L., Pan F., Yuan H., Ye J., Chen C., Zhu Y., Energy Storage Mater., 2020, 24, 689-693

[53] Yue L., Wang X., Chen L., Shen D., Shao Z., Wu H., Xiao S., Liang W., Yu Y., Li Y., Energy Environ. Sci., 2024, 17(3), 1117-1131

[54] Liang S. S., Kang S. S., Yang D., Hu J. H., Acta Chim. Sinica, 2022, 80, 1264-1268

[55] (梁世硕, 康树森, 杨东, 胡建华. 化学学报, 2022, 80, 1264-1268)

[56] Liu P., Su H., Liu Y., Zhong Y., Xian C., Zhang Y., Wang X., Xia X., Tu J., Small Struct., 2022, 3, 2200010

基金资助

国家自然科学基金(52362035, 22462023)

内蒙古自治区直属高校基本科研业务费项目(2023QNJS018)

内蒙古自治区科技突围项目(2024KJTW0007)

内蒙古自治区教育厅科研基金(NMGWDRW2025-05)

内蒙古自治区高校创新科研团队项目(NMGIRT2215)

内蒙古自治区教育厅重点项目(YLXKZX-NKD-003)

内蒙古自治区科技计划项目(2024SKYPT0035, 2025KYPT0164, 2025YFDZ0104)

内蒙古自治区“青年科技人才支持计划”项目(NJYT24005)