基于纳米纤维素/多壁碳纳米管气凝胶和泡沫镍构筑的三维复合材料及其电容性能

王韵; 胡少恒; 邓阿申; 刘宇杰; 夏燎原

doi:10.13801/j.cnki.fhclxb.20230104.003

基于纳米纤维素/多壁碳纳米管气凝胶和泡沫镍构筑的三维复合材料及其电容性能

doi: 10.13801/j.cnki.fhclxb.20230104.003

1.
湖南邮电职业技术学院，长沙 410015
2.
中南林业科技大学　材料科学与工程学院，长沙 410018

基金项目: 国家自然科学基金(31530009)；湖南省自然科学基金(2021 JJ30042)；湖南省教育厅科学研究项目(20 A508)

详细信息

通讯作者:
夏燎原，博士，教授，硕士生导师，研究方向为生物质储能材料、电催化、阻燃材料　E-mail: xly1516@126.com

中图分类号: TB333
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出版历程
- 收稿日期: 2022-10-14
- 修回日期: 2022-11-29
- 录用日期: 2022-12-02
- 网络出版日期: 2023-01-04
- 刊出日期: 2023-09-15

Three-dimensional hybrid material constructed by cellulose nanofibers/multiwall carbon nanotubes aerogel and foam nickel and its electrochemical capacitance performance

1.
Hunan Post and Telecommunication College, Changsha 410015, China
2.
College of Material Science and Engineering, Central South University of Forestry and Technology, Changsha 410018, China

Funds: National Natural Science Foundation of China (31530009); Hunan Provincial Natural Science Foundation of China (2021 JJ30042); Scientific Research Fund of Hunan Provincial Education Department (20 A508)

摘要

摘要: 三维(3D)电极材料因其独特的结构和优异的电化学性能而被认为是高性能超级电容器的理想候选者。纳米纤维素(CNF)和多壁碳纳米管(MWCNT)被广泛应用于电极材料的开发与设计，但如何利用它们独特的一维纳米结构和固有的物理特性来构筑高性能3D电极材料依然是一个巨大的挑战。采用“自下而上”的策略，以CNF/MWCNT冷冻干燥过程中自聚集形成的气凝胶薄片为填充物，镍泡沫(NF)的3D网状结构为骨架，巧妙构筑了一种具有独特“薄片填充-骨架支撑”结构的MWCNT/CNF-NF三维杂化材料。受益于NF三维骨架优异的导电性和增强作用及MWCNT/CNF气凝胶薄片高的比表面积，以MWCNT/CNF-NF为负载电活性物质聚吡咯(PPy)的平台，通过优化电沉积时间制备的PPy-MWCNT/CNF-NF自支撑电极具有良好的可弯曲性和优异的电化学特性。与预期一样，在5 mA·cm⁻²的电流密度下该电极的面积比容量高达2217.8 mF·cm⁻²(869.9 F·g⁻¹)，经过3000次循环后依然具有90.2%的高容量保持率。
- 纳米纤维素 /
- 碳纳米管 /
- 电活性平台 /
- 聚吡咯 /
- 自支撑电极
Abstract: Three-dimensional (3D) electrode materials are ideal candidates for use in fabricating high-performance supercapacitors, owing to their unique network structure and excellent electrochemical properties. Although cellulose nanofibers (CNF) and multiwall carbon nanotubes (MWCNT) are widely used in the development and design of electrode materials, how to use their unique one-dimensional nanostructures and inherent physical properties to build high-performance 3D electrode materials remains a huge challenge. Herein, an aerogel film produced by the freeze-drying self-aggregation of MWCNTs and CNFs was used as the “filling,” and an inter-connected 3D network of nickel foam (NF) as the “framework,” for well-design and fabrication of an MWCNT/CNF-NF hybrid materials. Benefiting from the excellent conductivity and high specific surface area of the MWCNT/CNF-NF, it is exceptionally suitable for use as the electroactive material platform in the fabrication of high-performance electrodes. Therefore, in this work, the high-performance polypyrrole (PPy)-MWCNT/CNF-NF freestanding electrodes were successfully prepared by optimizing the time of the electroactive material polypyrrole. As expected, the electrode exhibits a high areal capacity of 2217.8 mF·cm⁻² (869.9 F·g⁻¹) at a current density of 5 mA·cm⁻², with good stability even after 3000 charge-discharge cycles.
- cellulose nanofibers /
- carbon nanotubes /
- electroactive platform /
- polypyrrole /
- freestanding electrode

HTML全文

图 1 基于多壁碳纳米管(MWCNT)/纳米纤维素(CNF)气凝胶薄片和镍泡沫(NF)骨架构筑的三维(3D)杂化电极材料示意图

Figure 1. Three-dimensional (3D) hybrid electrode materials schematic diagram based on multiwall carbon nanotubes (MWCNT)/cellulose nanofibers (CNF) aerogel sheets and nickel foam (NF) skeleton

PPy—Polypyrrole

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图 2 PPy-MWCNT/CNF-NF电极C1s (a) 和N1s (b) 的XPS谱图及选区SEM图像和相应的C、N元素EDS分布图 (c)

Figure 2. XPS spectra of C1s (a) and N1s (b) on PPy-MWCNT/CNF-NF electrode, the selected area SEM image and the corresponding distribution of C and N EDS (c)

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图 3 不同样品的SEM图像：((a), (b)) NF；((c), (d)) MWCNT/CNF-NF平台；((e), (f)) PPy-NF；((g), (h)) PPy-MWCNT/CNF-NF；((i), (j)) MWCNT电沉积PPy后的TEM图像；(k) 大范围制备的MWCNT/CNF-NF照片；(l) 裁成条状的PPy-MWCNT/CNF-NF电极的柔性演示

Figure 3. SEM images of different samples: ((a), (b)) NF; ((c), (d)) MWCNT/CNF-NF platform; ((e), (f)) PPy-NF; ((g), (h)) PPy-MWCNT/CNF-NF; ((i), (j)) TEM images of MWCNT after electrodeposited PPy; (k) Photo of MWCNT/CNF-NF prepared by large scale; (l) Flexibility demonstration of PPy-MWCNT/CNF-NF electrodes

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图 4 MWCNT/CNF-NF在5~100 mV·s⁻¹扫描速度下的CV曲线 (a)、1~40 mA·cm⁻²电流密度下的充放电曲线 (b) 和交流阻抗谱图 (c)

Figure 4. CV curves at 5-100 mV·s⁻¹ scanning speed (a), charge-discharge curves at 1-40 mA·cm⁻² current density (b) and Nyquist plots (c) of MWCNT/CNF-NF

Z'—Real impedance; Z''—Imaginary imdepance; R_s—Charge transfer resistance; R_ct—Electrolyte resistance; CPE₁—Constant phase element

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图 5 不同电沉积时间的PPy-MWCNT/CNF-NF电极在100 mV·s⁻¹扫速下收集的CV曲线 (a)、5 mA·cm⁻²的恒电流充放电CP曲线 (b)、PPy负载量和面积比电容与电沉积时间的函数关系 (c)、面积比容量与电流密度的关系 (d)、质量比容量与电流密度的关系 (e) 和Nyquist阻抗谱图 (f)

Figure 5. CV curves collected at 100 mV·s⁻¹ sweep speed (a), CP curves of 5 mA·cm⁻² constant current charge-discharge (b), functional relationship between PPy load and area specific capacitance and electrodeposition time at different electrodeposition time (c), area specific capacity versus current density (d), mass specific capacity versus current density (e) and Nyquist impedance spectrum (f) of PPy-MWCNT/CNF-NF with different electrodeposition times

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图 6 不同电极在100 mV·s⁻¹扫速下收集的CV曲线 (a)、5 mA·cm⁻²的恒电流充放电计时电位分析(CP)曲线 (b)、面积比电容和容量保持率与电流密度的函数关系 (c)；(d) PPy-MWCNT/CNF-NF电极在10 mA·cm⁻²电流密度下的循环稳定性

Figure 6. CV curves collected at 100 mV·s⁻¹ sweep speed (a), Chronopotentiometry (CP) curves of 5 mA·cm⁻² constant current charge-discharge (b), functional relationship between area specific capacitance and capacity retention and current density (c) of different electrodes; (d) Cyclic stability of PPy-MWCNT/CNF-NF electrode at 10 mA·cm⁻²

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表 1 不同沉积时间PPy- MWCNT/CNF-NF电极的命名

Table 1. Naming of PPy-MWCNT/CNF-NF electrode with different electrodeposition time

Sample	Electrodeposition time/s
PPy-MWCNT/CNF-NF-200	200
PPy-MWCNT/CNF-NF-300	300
PPy-MWCNT/CNF-NF-400	400
PPy-MWCNT/CNF-NF-500	500

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