硅酸盐学报

圆形截面、高性能单壁碳纳米管纤维的可控制备

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柳钰可 ¹^,² , 张有权 ¹^,² , 石超 ¹ , 侯鹏翔 ¹^,² , 刘畅 ¹^,²

硅酸盐学报 | 国家自然科学基金重点项目中期成果专题—研究论文 2026,54(2): 373-380

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硅酸盐学报 |国家自然科学基金重点项目中期成果专题—研究论文 2026 , 54 (2) : 373 -380

圆形截面、高性能单壁碳纳米管纤维的可控制备

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柳钰可¹^,², 张有权¹^,², 石超¹, 侯鹏翔¹^,², 刘畅¹^,²

作者信息

^1．中国科学院金属研究所，沈阳材料科学国家研究中心，沈阳 110016

^2．中国科学技术大学材料科学与工程学院，合肥 230026

通讯作者:

刘畅（1973—），男，博士，研究员

侯鹏翔（1975—），女，博士，研究员。

作者简介:

柳钰可（2003—），女，硕士研究生。

Fabrication of Single-wall Carbon Nanotube Fiber with Circular Cross-section and High Performance

Yuke LIU¹^,², Youquan ZHANG¹^,², Chao SHI¹, Pengxiang HOU¹^,², Chang LIU¹^,²

Affiliations

^1.Shenyang National Laboratory for Material Science, Institute of Metal Research, Chinese Academy of Science, Shenyang 110016, China

^2.School of Material Science and Engineering, University of Science and Technology of China, Hefei 230026, China

Corresponding Author:

LIU Chang (1973-), male, Ph.D., Professor; E-mail: cliu@imr.ac.cn

HOU Pengxiang (1975-), female, Ph.D., Professor. E-mail: pxhou@imr.ac.cn

LIU Yuke (2003-), female, Master candidate. E-mail: ykliu23s@imr.ac.cn

出版时间: 2026-02-20 doi: 10.14062/j.issn.0454-5648.20250506

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摘要

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单壁碳纳米管纤维（SWCNTF）具有低密度、高电导率、高强度、高韧性等优点，被认为是高频交流传输线、电磁屏蔽、天线、轻量化增强用理想候选材料。然而，传统湿法纺丝制备的SWCNTF易形成皮芯结构导致其径向结构不均匀、多褶皱，限制了其性能提升和实际应用。针对以上问题，本研究选择N-甲基吡咯烷酮作为凝固浴，降低氯磺酸和凝固浴之间的双扩散速率，显著抑制皮芯结构形成，获得了圆形截面SWCNTF；通过调节凝固浴的成分，提高纤维的最大拉伸比，进一步提高了纤维的电学性能和力学性能。与以丙酮为凝固浴制备的SWCNTF相比，本研究所得纤维的截面圆形度提高了135%，其拉伸强度和弹性模量分别提高了41%和133%。

关键词

单壁碳纳米管纤维 / 圆形度 / 凝固浴 / 双扩散速率

Abstract

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Introduction

Carbon nanotube fibers (CNTFs) are regarded as a promising candidate material for use in high frequency AC transmission line, electromagnetic shielding cable, antenna, lightweight high-strength composites due to their advantages in low-density, high conductivity and high-strength. Recent advances are made in the fabrication of CNTFs, especially those spun by a wet-spinning technology. However, CNTFs fabricated by a conventional wet spinning method generally have irregular cross-section and non-uniform radial structure, resulting in a rapid double diffusion between chlorosulfonic acid (CSA) in the spinning solution and acetone coagulation bath and a significant radial stiffness gradient in the fiber, thus easily leading to core-shell and wrinkled structures. In this work, we selected N-Methylpyrrolidone (NMP) as a coagulation bath to decrease the diffusion rate between CSA and coagulation bath. Single-wall carbon nanotube fibers (SWCNTFs) with a circular cross section could be continuously spun in NMP. We further introduced ethanol into NMP coagulation bath to control the double diffusion rate and viscosity to improve the draw ratio of SWCNTFs. As a result, SWCNTFs with circular cross-section, high orientation, and desirable electrical and mechanical properties were fabricated.

Methods

Single-wall carbon nanotubes (SWCNTFs) with a high crystallinity and a high purity were synthesized by a floating catalyst chemical vapor deposition method. The SWCNTs were put into a beaker, and transferred to a glove box in Ar atmosphere. CSA was then added to the glass bottle, and agitated for 30 min to obtain a liquid crystal (LC) phase. The LC spinning solution was transferred into a stainless steel syringe in Ar atmosphere and extruded through a spinneret into coagulation bath by an injection pump to form macroscopic fibers. An appropriate draw ratio was applied to the SWCNTFs through a drawing device, and fibers were then wound on a PTFE roll and dried under 30 ℃ for 12 h. In this work, all the fibers were spun at a maximum draw ratio that they could endure.

Results and discussion

The SWCNTFs spun from NMP coagulation bath have a higher circularity of 0.80, while their alignment and packing density is relatively low due to the smaller draw ratio. We therefore introduces ethanol into the NMP coagulation bath to tune the double diffusion rate to increase the applied draw ratio. The results show that the maximum draw ratio applied to SWCNTFs increases with the increase of ethanol content and reaches to the maximum value of 169% at the ethanol content of 75%. The obtained SWCNTFs have a high circularity of 0.87 and a high orientation Herman factor of 0.987. We analyzes the mechanical behavior of the nascent fiber in the coagulation bath, clarifying how the coagulation bath affects the formation of wet-spun fibers. The results show that optimizing the coagulation bath viscosity effectively reduces a frictional resistance during fiber formation, while an optimized double diffusion rate promotes a denser packing within the surface solidification layer. These synergistic effects collectively enable higher fiber draw ratios and facilitate the development of a highly oriented microstructure with a circular cross-section.

Conclusion

This study investigated the radial structural heterogeneity and surface wrinkling in conventional wet-spun CNTFs via developing a novel NMP-based coagulation bath. The NMP coagulation bath significantly reduced the double-diffusion rate of CSA, enabling the fabrication of SWCNTFs without a core-shell structure, while improving radial structural uniformity. Ethanol was then introduced into the NMP coagulation bath to improve the draw ratio and orientation of the fibers. The optimized SWCNTFs showed a high circular cross-section of 0.87, which was twice more than that of previously reported SWCNTFs (i.e., 0.37). The fibers simultaneously had high orientation Herman factor of 0.987, high mechanical properties with tensile strength of (1047±44) MPa and Young's modulus of (24.0±3.26) GPa, as well as high electrical characteristics with conductivity of (5.74±0.28)×10⁶ S/m and ampacity of (3.99±0.07)×10⁸ A/m². The developed SWCNTFs with a homogeneous structure and a regular morphology could have a promising potential for applications in high-frequency transmission wires and fiber reinforced composite materials.

Key words

single-wall carbon nanotube fiber / circularity / coagulation bath / double diffusion rate

引用本文

柳钰可, 张有权, 石超, 侯鹏翔, 刘畅. 圆形截面、高性能单壁碳纳米管纤维的可控制备. 硅酸盐学报, 2026 , 54 (2) : 373 -380 . DOI: 10.14062/j.issn.0454-5648.20250506

Yuke LIU, Youquan ZHANG, Chao SHI, Pengxiang HOU, Chang LIU. Fabrication of Single-wall Carbon Nanotube Fiber with Circular Cross-section and High Performance[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (2) : 373 -380 . DOI: 10.14062/j.issn.0454-5648.20250506

基金

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国家自然科学基金重点项目(52130209)

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2026年第54卷第2期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250506

接收时间：2025-06-27
首发时间：2026-10-27
出版时间：2026-02-20

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收稿日期：2025-06-27
修回日期：2025-07-29

基金

国家自然科学基金重点项目(52130209)

作者信息

^1．中国科学院金属研究所，沈阳材料科学国家研究中心，沈阳 110016

^2．中国科学技术大学材料科学与工程学院，合肥 230026

通讯作者:

刘畅（1973—），男，博士，研究员

侯鹏翔（1975—），女，博士，研究员。

参考文献

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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