基于环烷烃/乙醇混合碳源高性能碳纳米管纤维的连续化制备

doi:10.6023/A23040163

摘要/Abstract

利用化学气相沉积和干法纺丝方法可以制备得到碳纳米管纤维, 但受限于反应碳源较为单一, 目前纤维的力学和电学性能还难以有效满足实际应用需求, 如何实现高性能碳纳米管纤维的连续制备, 仍是本领域一个重要挑战. 本研究通过设计十氢萘/乙醇新型二元混合碳源, 重点调控环烷烃/乙醇的组分比例, 实现了高性能碳纳米管纤维的连续化制备, 收集速率达到220 m/h. 相比于已报道的由单一乙醇碳源制备的碳纳米管纤维, 由混合碳源制备的碳纳米管纤维拉伸断裂强度(750 MPa)提升了1倍以上, 力学性能在弯折百万次后仍保持稳定; 电导率(4.8×10³ S/cm)提升4倍以上, 可有效满足纤维储能器件应用需求, 所构建的纤维状锂-二氧化碳电池显示良好电化学性能.

关键词: 碳纳米管纤维, 化学气相沉积, 浮动催化剂, 连续制备, 混合碳源

Due to the excellent physical and chemical properties, carbon nanotubes show broad applications in a variety of fields such as composite materials, catalysis, energy, medicine and sensor. However, at present, the carbon nanotubes are mainly practically used in the form of powders. Carbon nanotube fibers can be prepared by the methods of chemical vapor deposition and/or dry spinning. However, the carbon source used in previous study mainly has single component, making the mechanical and electrical properties of carbon nanotube fibers still difficult to effectively meet the practical application requirements. It remains challenging to realize continuous preparation of high-performance carbon nanotube fibers. In this work, a new cycloalkane/ethanol mixing carbon source was designed to obviously promote the continuous growth process and properties of carbon nanotube fibers. After carefully optimizing the component ratio of decahydronaphthalene/ethanol in the precursor solution, and systematically optimizing reaction conditions such as catalyst content (ferrocene and thiophene), injection rate of the precursor solution, and the flow rate of carrier gas (argon and hydrogen), the continuous preparation of high-performance carbon nanotube fibers was realized. When the mass ratio of decahydronaphthalene to ethanol carbon source in precursor solution is 3∶7, the high-performance carbon nanotube fibers can be continuously produced for a long time with a collection rate of 220 m/h. It shows improved mechanical and electrical properties compared with the carbon nanotube fiber prepared by using single ethanol carbon source. For instance, the tensile strength of carbon nanotube fiber is increased by more than 1 time (750 MPa). The carbon nanotube fiber has good flexibility and can shows stable mechanical properties after millions of bending cycles. The conductivity is increased by more than 4 times (4.8×10³ S/cm), which can effectively meet the application requirements of fiber energy-storing devices. The application of carbon nanotube fibers in a fiber-shaped lithium-carbon dioxide battery is demonstrated with good electrochemical performance.

Key words: carbon nanotube fiber, chemical vapor deposition, floating catalyst, continuous preparation, mixing carbon source

引用此文

赵天成, 蒋鸿宇, 张琨, 徐一帆, 康欣悦, 胥鉴宸, 周旭峰, 陈培宁, 彭慧胜. 基于环烷烃/乙醇混合碳源高性能碳纳米管纤维的连续化制备[J]. 化学学报, 2023, 81(6): 565-571.

Tiancheng Zhao, Hongyu Jiang, Kun Zhang, Yifan Xu, Xinyue Kang, Jiancheng Xu, Xufeng Zhou, Peining Chen, Huisheng Peng. Continuous Preparation of High-performing Carbon Nanotube Fibers Based on Cycloalkane/ethanol Mixing Carbon Source[J]. Acta Chimica Sinica, 2023, 81(6): 565-571.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 6

图1. 利用浮动催化剂化学气相沉积法连续制备碳纳米管纤维示意图

Figure 1. Schematic of continuous preparation of carbon nanotube fibers by floating catalyst chemical vapor deposition method

图2. 碳纳米管纤维的低倍(a)和高倍(b)扫描电子显微镜照片与透射电子显微镜照片(c); (d)由不同十氢萘含量混合碳源制备的碳纳米管纤维在532 nm激发波长下的拉曼光谱

Figure 2. (a) Low- and (b) high-magnification SEM and TEM (c) images of carbon nanotube fibers; (d) Raman spectra of carbon nanotube fibers prepared by mixing carbon sources with different decahydronaphthalene contents at excitation wavelength of 532 nm

图3. (a)混合碳源中不同十氢萘含量条件下碳纳米管纤维拉曼光谱中的IG与ID峰比值; (b)基于不同十氢萘含量混合碳源制备的碳纳米管纤维在785 nm激发波长下的拉曼光谱; (c)混合碳源中不同十氢萘含量条件下碳纳米管纤维拉曼光谱中2D(G')峰位置; (d)由混合碳源制备的碳纳米管纤维的热失重曲线

Figure 3. (a) The ratios of IG to ID peaks in Raman spectra of carbon nanotube fibers under different decahydronaphthalene contents in mixed carbon sources; (b) Raman spectra of carbon nanotube fibers prepared by mixing carbon sources with different decahydronaphthalene contents at 785 nm excitation wavelength; (c) plot of Raman 2D(G') peak position for carbon nanotube fibers with different decahydronaphthalene contents in mixing carbon sources; (d) thermogravimetric curves of carbon nanotube fibers based on mixing carbon sources

图4. (a, b)碳源中环烷烃含量对碳纳米管纤维的拉伸强度(a)和电导率(b)的影响; (c, d)反应液注入速率对碳纳米管纤维的拉伸强度(c)和电导率(d)的影响

Figure 4. (a, b) Effect of decahydronaphthalene content in carbon sources on tensile strength (a) and electrical conductivity (b) of carbon nanotube fibers; (c, d) effect of reaction liquid inject speed on tensile strength (c) and electrical conductivity (d) of carbon nanotube fibers

图5. 基于十氢萘/乙醇二元混合碳源的碳纳米管纤维力学性能. (a)收卷在塑轴上的连续碳纳米管纤维照片; (b)单根碳纳米管纤维悬挂50 g砝码和缠绕在试管上的照片; (c)碳纳米管纤维的应力?应变曲线; (d)碳纳米管纤维在不同弯折次数后的拉伸强度与初始值的比值

Figure 5. Mechanical properties of carbon nanotube fibers based on decahydronaphthalene/ethanol mixing carbon sources. (a) Photograph of reels of carbon nanotube fibers; (b) photograph of carbon nanotube fiber hanging a weight of 50 g (left) and wrapped around a glass tube (right); (c) stress-strain curves of carbon nanotube fibers; (d) comparison of tensile strength of carbon nanotube fibers with original value after increasing bending cycles

图6. 基于碳纳米管纤维制备的锂-二氧化碳电池. (a)锂-二氧化碳纤维电池的结构示意图; (b)锂-二氧化碳纤维电池的首次充放电电压-时间曲线; (c)锂-二氧化碳纤维电池的循环性能; (d)锂-二氧化碳纤维电池点亮宇航员模型中LED灯泡的照片

Figure 6. Fiber-shaped lithium-carbon dioxide battery based on carbon nanotube fiber. (a) Schematic of fiber-shaped lithium-carbon dioxide fiber battery; (b) the voltage-time curve of the first charge and discharge; (c) cycle performance of fiber-shaped lithium-carbon dioxide battery; (d) photograph of LED in astronaut model powered by the lithium-carbon dioxide fiber battery

参考文献 30

[1]	Iijima, S. Nature 1991, 354, 56. doi: 10.1038/354056a0
[2]	Yadav, M. D.; Dasgupta, K.; Patwardhan, A. W.; Joshi, J. B. Ind. Eng. Chem. Res. 2017, 56, 12407. doi: 10.1021/acs.iecr.7b02269
[3]	Li, R.; Jiang, Q.; Zhang, R. Sci. Bull. 2022, 67, 784. doi: 10.1016/j.scib.2022.01.008
[4]	Wu, K.; Zhang, Y.; Yong, Z.; Li, Q. Acta Phys. Chim. Sin. 2022, 38, 2106034.
[5]	Peng, B.; Locascio, M.; Zapol, P.; Li, S.; Mielke, S. L.; Schatz, G. C.; Espinosa, H. D. Nat. Nanotechnol. 2008, 3, 626. doi: 10.1038/nnano.2008.211 pmid: 18839003
[6]	Behabtu, N.; Young, C. C.; Tsentalovich, D. E.; Wang, X.; Ma, A. W. K.; Bengio, A.; Waarbeek, R. F.; Jong, J. J.; Hoogerwerf, R. E.; Fairchild, S. B.; Maruyama, B.; Knon, J.; Talmon, Y.; Otto, M. J.; Pasquali, M. Science 2013, 339, 182. doi: 10.1126/science.1228061
[7]	Vigolo, B.; Penicaud, A.; Coulon, C.; Sauder, C.; Pailler, R.; Journet, C.; Bernier, P.; Poulin, P. Science 2000, 290, 1331. pmid: 11082056
[8]	Liu, T.; Bai, Z.; Huang, X.; Hu, J.; Zhang, K. China Textile Leader 2021, 8, 44. (in Chinese)
	(刘天应, 白志强, 黄璇, 胡建臣, 张克勤, 纺织导报, 2021, 8, 44.)
[9]	Feng, C.; Liu, K.; Wu, J. S.; Liu, L.; Cheng, J. S.; Zhang, Y.; Sun, Y.; Li, Q.; Fan, S.; Jiang, K. Adv. Funct. Mater. 2010, 20, 885. doi: 10.1002/adfm.200901960
[10]	Zhang, M.; Atkinson, K. R.; Baughman, R. H. Science 2004, 306, 1358. pmid: 15550667
[11]	Jiang, K. L.; Li, Q. Q.; Fan, S. S. Nature 2002, 419, 801. doi: 10.1038/419801a
[12]	Sun, L.; Cui, H.; Yu, H. Hi-Tech Fiber and Application 2022, 2, 49. (in Chinese)
	(孙灵鑫, 崔红, 余惠琴, 高科技纤维与应用, 2022, 2, 49.)
[13]	Li, Y. L.; Kinloch, I. A.; Windle, A. H. Science 2004, 304, 276. doi: 10.1126/science.1094982
[14]	Zhu, H. W.; Xu, C. L.; Wu, D. H.; Wei, B. Q.; Vajtai, R.; Ajayan, P. M. Science 2002, 296, 884. pmid: 11988567
[15]	Zhong, X. H.; Li, Y. L.; Liu, Y. K.; Qiao, X. H.; Feng, Y.; Liang, J.; Jin, J.; Zhu, L.; Hou, F.; Li, J. Y. Adv. Mater. 2010, 22, 692. doi: 10.1002/adma.200902943
[16]	Baughman, R. H.; Zakhidov, A. A.; Heer, W. A. Science 2002, 297, 787. doi: 10.1126/science.1060928 pmid: 12161643
[17]	Kimura, H.; Goto, J.; Yasuda, S.; Sakurai, S.; Yumura, M.; Futaba, D. N.; Hata, K. Sci. Rep. 2013, 3, 3334. doi: 10.1038/srep03334 pmid: 24276860
[18]	Chen, P. N.; Xu, Y. F.; He, S. S.; Sun, X.; Pan, S.; Deng, J.; Chen, D.; Peng, H. Nat. Nanotechnol. 2015, 10, 1077. doi: 10.1038/nnano.2015.198
[19]	Qiu, Y.; Song, Y.; Li, Y. Mater. Rep. 2022, 36, 21010059.
[20]	Janas, D.; Koziol K. K. Nanoscale 2016, 8, 19475. doi: 10.1039/C6NR07549E
[21]	Zhao, X. L.; Ando, Y.; Qin, L. C.; Kataura, H.; Maniwa, Y.; Saito, R. Appl. Phys. Lett. 2002, 81, 2550. doi: 10.1063/1.1502196
[22]	Majumder, M.; Chopra, N.; Andrews, R.; Hinds, B. J. Nature 2005, 438, 44. doi: 10.1038/438044a
[23]	Hou, G.; Chauhan, D.; Ng, V.; Xu, C.; Yin, Z.; Paine, M.; Su, R.; Shanov, V.; Mast, D.; Schulz, M.; Liu, Y. Mater. Des. 2017, 132, 112. doi: 10.1016/j.matdes.2017.06.070
[24]	Araujo, P. T.; Maciel, I. O.; Pesce, P. B. C.; Pimenta, M. A.; Doorn, S. K.; Qian, H.; Hartschuh, A.; Steiner, M.; Grigorian, L.; Hata, K.; Jorio, A. Phys. Rev. B 2008, 77, 241403. doi: 10.1103/PhysRevB.77.241403
[25]	Ferrari, A. C.; Meyer, J. C.; Scardaci, V.; Casiraghi, C.; Lazzeri, M.; Mauri, F.; Piscanec, S.; Jiang, D.; Novoselov, K. S.; Roth, S.; Geim, A. K. Phys. Rev. Lett. 2006, 97, 187401. doi: 10.1103/PhysRevLett.97.187401
[26]	Reguero, V.; Alemán, B.; Mas, B.; Vilatela, J. J. Chem. Mater. 2014, 26, 3550. doi: 10.1021/cm501187x
[27]	Gspann, T. S.; Juckes, S. M.; Niven, J. F.; Johnson, M. B.; Elliott, J. A.; White, M. A.; Windle, A. H. Carbon 2017, 114, 160. doi: 10.1016/j.carbon.2016.12.006
[28]	Hou, G.; Su, R.; Wang, A.; Ng, V.; Li, W.; Song, Y.; Zhang, L.; Sundaram, M.; Shanov, V.; Mast, D.; Lashmore, D. Carbon 2016, 102, 513. doi: 10.1016/j.carbon.2016.02.087
[29]	Wasel, W.; Kuwana, K.; Reilly, P. T.; Saito, K. Carbon 2007, 45, 833. doi: 10.1016/j.carbon.2006.11.013
[30]	Zhang, G.; Mann, D.; Zhang, L.; Javey, A.; Li, Y.; Yenilmez, E.; Wang, Q.; Mcvittie, J. P.; Nishi, Y.; Gibbons, J.; Dai, H. Proc. Natl. Acad. Sci. U. S. A. 2005, 102, 16141. doi: 10.1073/pnas.0507064102