Synthesis and electrochemical energy storage performance of biomass-based porous hierarchical activated carbon-polyaniline composites
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摘要: 为制备高性能、低成本的储能器件,本文通过简单的一步原位化学聚合的方法制备了生物质基多级孔活性炭-聚苯胺复合材料(HAC-PANI),并探讨了其在超级电容器(SCs)及锌离子混合超级电容器(ZHSCs)领域的应用。研究结果表明,复合材料中HAC的分级多孔结构和高的比表面积为PANI提供了生长位点,有效减少了PANI的团聚现象,并能促进电化学储能过程中电解质离子的传输,降低界面电荷传递电阻。当HAC与苯胺单体(AN)的质量比为1∶2时,PANI纳米颗粒均匀生长在HAC基底上,所得复合电极材料(HAC-2PANI)的电化学储能性能达到最佳,在三电极体系下质量比电容高达415.6 F·g−1(@1 A·g−1)。二电极体系下,基于HAC-2PANI的全固态超级电容器(s-HAC-PANI-SC)质量比电容为217.4 F·g−1(@1 A·g−1)、能量密度为26.5 W·h·kg−1、功率密度为1875.0 W·kg−1。由于PANI中赝电容的引入,以HAC-2PANI为阴极、Zn箔为阳极所构建的锌离子混合超级电容器(HAC-PANI-ZHSC)在0.2 A·g−1的电流密度下呈现出高的比容量(91.8 mA·h·g−1)、能量密度(64.3 W·h·kg−1)和功率密度(140.0 W·kg−1),并具有良好的倍率性能和循环稳定性,表明了生物质基活性炭复合材料在高性能、低成本电化学储能器件中潜在的应用前景。
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关键词:
- 生物质基活性炭 /
- 聚苯胺 /
- 复合材料 /
- 超级电容器 /
- 金属离子混合超级电容器
Abstract: To fabricate high performance energy storage devices with low cost, this work proposed a facile method to prepare biomass-based hierarchical activated carbon-polyaniline composites (HAC-PANI) via an in-situ chemi-cal polymerization method, and their applications in supercapacitors (SCs) and zinc-ion hybrid supercapacitors (ZHSCs) were investigated. The results show that hierarchical porous structure and high specific area of HAC provide growth sites for PANI and effectively reduce the agglomeration of PANI and meanwhile promote the transport of electrolyte ions, and degrease the charge transfer resistance. When the mass ratio of HAC to aniline monomer (An) is 1∶2, uniform PANI nanoparticles were observed growing on HAC, and the resulting composite (HAC-2PANI) electrode exhibits the optimum performance. Under the three-electrode system, the mass specific capacitance of HAC-2PANI reaches as high as 415.6 F·g−1(@1 A·g−1). The HAC-2PANI based all-solid supercapacitor (s-HAC-PANI-SC) displays a specific capacitance of 217.4 F·g−1(@1 A·g−1), an energy density of 26.5 W·h·kg−1 and a power density of 1875.0 W·kg−1. The zinc-ion hybrid supercapacitor (HAC-PANI-ZHSC) constructed with HAC-2PANI as the cathode and Zn foil as the anode exhibits a high specific capacity of 91.8 mA·h·g−1(@0.2 A·g−1), a remarkable energy density of 64.3 W·h·kg−1, and a power density of 140.0 W·kg−1, indicating promising potentials of biomass-based carbon composites for high performance and low cost electrochemical energy storage devices.-
Key words:
- biomass-based carbon /
- polyaniline /
- composites /
- supercapacitors /
- metal-ion hybrid supercapacitors
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图 2 低倍率及高倍率SEM图像:(a) HAC;(b) PANI;(c) HAC-0.5PANI;(d) HAC-1PANI;(e) HAC-2PANI;(f) HAC-3PANI;HAC-2PANI的低倍率 (g) 及高倍率 (h) TEM图像
Figure 2. Lower and higher-magnification SEM images: (a) HAC; (b) PANI; (c) HAC-0.5PANI; (d) HAC-1PANI; (e) HAC-2PANI; (f) HAC-3PANI; Lower (g) and higher-magnification (h) TEM images of HAC-2PANI
图 3 HAC和HAC-2PANI的氮气吸附-解吸附曲线 (a)、孔径分布图 (b)、XRD图谱 (c)、Raman图谱 (d)、XPS能谱图 (e) 及HAC-2PANI的高分辨率N1s图谱 (f)
Figure 3. Nitrogen adsorption-desorption curves (a), pore size distribution (b), XRD pattern (c), Raman spectra (d), XPS spectra (e) of HAC and HAC-2PANI and high resolution N1s spectrum of HAC-2PANI (f)
图 4 不同质量比HAC-PANI三电极体系电化学性能:(a) CV曲线;(b) GCD曲线; (c) EIS曲线;(d) HAC-2PANI在不同扫描速率下的CV曲线;(e) HAC-2PANI在20 mV·s−1下的电容贡献和扩散控制贡献;(f) HAC-2PANI在不同扫描速率下电容贡献和扩散控制的贡献比;(g) HAC-2PANI在不同电流密度下的GCD曲线;(h) HAC-2PANI的倍率性能;(i) HAC-2PANI的循环稳定性能
Figure 4. Electrochemical performances of different mass ratio HAC-PANI under the three-electrode configuration: (a) CV curves; (b) GCD curves; (c) EIS spectra; (d) CV curves at different scan rates of HAC-2PANI; (e) Separation of capacitance current and diffusion current at 20 mV·s−1 of HAC-2PANI; (f) Ratio of capacitive contribution and diffusion contribution at different scan rates of HAC-2PANI; (g) GCD curves at different current densities of HAC-2PANI; (h) Rate capacity of HAC-2PANI; (i) Cycling stability of HAC-2PANI
图 5 HAC-2PANI 水系超级电容器(HAC-PANI-SC)的电化学性能:(a) CV曲线;(b) GCD曲线;(c)拉贡图;HAC-2PANI 全固态超级电容器(s-HAC-PANI-SC)的电化学性能:(d) CV曲线;(e) GCD曲线;(f) HAC-PANI-SC、s-HAC-PANI-SC和HAC-SC器件在不同电流密度下质量比电容的对比
Figure 5. Electrochemical performance of HAC-2PANI based supercapacitor (HAC-PANI-SC): (a) CV curves; (b) GCD curves; (c) Ragone plot; Electrochemical performance of HAC-2PANI based all-solid supercapacitor (s-HAC-PANI-SC): (d) CV curves; (e) GCD curves; (f) Comparison of specific capacitance of HAC-PANI-SC, s-HAC-PANI-SC and HAC-SC devices at different current densities
图 6 (a) HAC-2PANI 锌离子混合超级电容器(HAC-PANI-ZHSC)的结构示意图;(b) HAC-ZHSC和HAC-PANI-ZHSC的CV曲线;(c) HAC-PANI-ZHSC在不同电流密度下的放电曲线;(d) HAC-ZHSC和HAC-PANI-ZHSC在不同电流密度下比容量的比较;(e) HAC-PANI-ZHSC的循环稳定曲线;(f) HAC-PANI-ZHSC点亮LED灯的数码照片(从左至右依次为0、2、5、12 h)
Figure 6. (a) Schematic structure of HAC-2PANI based zinc-ion hybrid supercapacitor (HAC-PANI-ZHSC); (b) CV curves of HAC-ZHSC and HAC-PANI-ZHSC; (c) Discharge curves of HAC-PANI-ZHSC at different current densities; (d) Comparison of specific capacity at different current densities of HAC-ZHSC and HAC-PANI-ZHSC; (e) Cycling stability of HAC-PANI-ZHSC; (f) Digital photos of HAC-PANI-ZHSC lighting an LED lamp at 0, 2, 5, and 12 h
表 1 不同HAC和苯胺(AN)质量比下HAC-PANI复合材料的命名
Table 1. Scheme of HAC-PANI composites with different mass ratio of HAC and aniline (AN)
Sample Mass ratio of HAC and AN HAC-0.5PANI 1∶0.5 HAC-1PANI 1∶1 HAC-2PANI 1∶2 HAC-3PANI 1∶3 -
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