Three-dimensional hybrid material constructed by cellulose nanofibers/ multiwall carbon nanotubes aerogel and foam nickel and its electrochemical capacitance performance
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摘要:
纳米纤维素(CNF)和多壁碳纳米管(MWCNT)因其独特的一维纳米结构和物理特性而广泛应用于柔性电极材料的开发与设计。然而，CNF虽具有高的比表面积以及良好的柔性，却不具备导电性；MWCNT虽具有良好的导电性，却容易团聚、且容量偏低。因而，如何合理设计并利用CNF和MWCNT的固有特性和优势来构筑高性能的电极依然是一个巨大的挑战。本文采用“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”结构的三维杂化材料(命名为MCN)。受益于NF三维骨架优异的导电性和增强作用以及CNF/ MWCNT气凝胶薄片高的比表面积，以MCN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-MCN自支撑电极具有优异的电化学特性。与设想的一样，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。 基于气凝胶片填充和泡沫镍骨架支撑“自下而上”构筑的三维杂化电极材料 Abstract: Three-dimensional (3-D) 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 3-D 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 3-D network of nickel foam (NF) as the “framework,” for well-design and fabrication of an MWCNT/CNF-NF hybrid materials (named as MCN). Benefiting from the excellent conductivity and high specific surface area of the MCN, 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 PPy-MCN 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.-
Key words:
- cellulose nanofibers /
- carbon nanotubes /
- electroactive platform /
- polypyrrole /
- freestanding electrode
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图 1 基于MWCNT/CNF气凝胶薄片和NF骨架构筑的3-D杂化电极材料示意图
Figure 1. 3-D hybrid electrode materials schematic diagram based on MWCNT/CNF aerogel sheets and NF skeleton
CNF—cellulose nanofibers; MWCNT—multiwall carbon nanotubes; NF—nickel foam
图 2 PPy-MCN电极C 1s (a)和N 1s (b)的XPS谱图以及选区SEM和相应的C、N元素EDS分布图(c)
Figure 2. The XPS spectra of C 1s (a) and N 1s (b) on PPy-MCN electrode, the selected area SEM and the corresponding distribution of C and N EDS (c)
图 3 不同样品的SEM图片：(a, b) NF, (c, d) MCN平台, (e, f) PPy-NF和(g, h) PPy-MCN；(i, j) MWCNT电沉积PPy后的TEM图片；(k) 大范围制备的MCN；(l) 裁成条状的PPy-MCN电极的柔性演示
Figure 3. SEM images of different samples: (a, b) NF, (c, d) MCN platform, (e, f) PPy-NF and (g, h) PPy-MCN; (i, j) TEM images of MWCNT after electrodeposited PPy; (k) Photo of MCN prepared by large scale; (l) Flexibility demonstration of PPy-MCN electrodes
图 4 MCN在(a)5~100 mV·s−1扫描速度下的CV曲线图,(b)1~40 mA·cm−2电流密度下的充放电曲线图,(c)交流阻抗谱图
Figure 4. (a) CV curve of MCN at 5~100 mV·s−1 scanning speed, (b) charge-discharge curve at 1~40 mA·cm−2 current density, (c) Nyquist plots of MCN
图 5 不同电沉积时间的PPy-MCN电极在(a)100 mV·s−1扫速下收集的CV曲线, (b) 5 mA·cm−2的恒电流充放电CP曲线, (c) PPy负载量和面积比电容与电沉积时间的函数关系，(d) 面积比容量与电流密度的关系，(e) 质量比容量与电流密度的关系和(f) Nyquist阻抗谱图
Figure 5. CV curve collected at (a)100 mV·s−1 sweep speed, CP curve of (b)5 mA·cm−2 constant current charge-discharge, (c) functional relationship between PPy load and area specific capacitance and electrodeposition time at different electrodeposition time, (d) area specific capacity versus current density, (e) mass specific capacity versus current density, and (f) Nyquist impedance spectrum
图 6 不同电极在(a)100 mV·s−1扫速下收集的CV曲线, (b) 5 mA·cm−2的恒电流充放电CP曲线, (c)面积比电容和容量保持率与电流密度的函数关系，(d) PPy-MCN电极在10 mA·cm−2电流密度下的循环稳定性
Figure 6. CV curves collected at (a)100 mV·s−1 sweep speed, CP curves of (b) 5 mA·cm−2 constant current charge-discharge, (c) the functional relationship between area specific capacitance and capacity retention and current density, and (d) the cyclic stability of PPy-MCN electrode at 10 mA·cm−2
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