Construction of nanocellulose-carboxylated carbon nanotube-graphite/polypyrrole flexible electrode composite based on interface interaction
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摘要: 以纳米纤维素(CNF)、羧基化碳纳米管(CNTs—COOH)、铅笔石墨(PGr)、聚吡咯(PPy)为原料，通过真空抽滤、涂覆、氧化聚合等方法，同时基于氢键界面相互作用的原理，制备出具有石墨层结构的CNF-CNTs—COOH-PGr/PPy柔性电极复合材料。结果表明，CNF-CNTs—COOH-PGr/PPy柔性电极复合材料在平直、折叠和拉伸时不会断裂，展现出较强的力学性能，其拉伸强度达到28.90 MPa。亲水性CNF与CNTs—COOH构筑的多孔结构增强了离子和电子的扩散路径。PGr的加入有效增加了CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的导电路径，赋予其优良的导电性能。氧化聚合后得到的CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的电导率达到5.403 S·cm−1。在1 mol·L−1 H2SO4溶液中，0.5 A·g−1电流密度下，CNF-CNTs—COOH-PGr/PPy柔性电极复合材料具有521 F·g−1的高比电容量，且经过1 500次充放电循环后，其电容保持率高达68%。基于柔性电极优良的力学性能、电化学性能和导电性能，CNF-CNTs—COOH-PGr/PPy柔性电极复合材料具备成为柔性储能器件电极材料的基本特性。Abstract: Using nanocellulose(CNF), carboxylated carbon nanotubes(CNTs—COOH), pencil graphite(PGr) and polypyrrole(PPy) as raw materials, the CNF-CNTs—COOH-PGr/PPy flexible electrode composite with graphite layer structure was prepared by vacuum filtration, coating, oxidative polymerization and based on the principle of hydrogen bonding interface interaction. The results show that the CNF-CNTs—COOH-PGr/PPy flexible electrode composite does not break when it is flatted, folded and stretched, and exhibits strong mechanical properties, and its tensile strength reaches 28.90 MPa. The porous structure of hydrophilic CNF and CNTs—COOH enhances the diffusion path of ions and electrons. The addition of PGr effectively improves the conductive path of CNF-CNTs—COOH-PGr/PPy flexible electrode composite and gives it excellent conductive properties. The conductivity of CNF-CNTs—COOH-PGr/PPy flexible electrode composite obtained after the oxidative polymerization reaches 5.403 S·cm−1. In the 1 mol·L−1 H2SO4 solution, the CNF-CNTs—COOH-PGr/PPy flexible electrode composite has a high specific capacitance of 521 F·g−1 at the current density of 0.5 A·g−1. And its capacitance retention rate is as high as 68% after 1 500 charge and discharge cycles. Based on the excellent mechanical properties, the electrochemical properties and electrical conductivity of the flexible electrodes, the CNF-CNTs—COOH-PGr/PPy flexible electrode composite has the basis characteristics for becoming the electrode material for flexible energy storage devices.
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图 1 纳米纤维素(CNF)-羧基化碳纳米管(CNTs—COOH)-铅笔石墨(PGr)/聚吡咯(PPy)柔性电极复合材料的制备过程
Figure 1. Preparation process of nanocellulose(CNF)-carboxylated carbon nanotubes(CNTs—COOH)-pencil graphite(PGr)/polypyrrole (PPy) flexible electrode composite
图 3 CNF、CNTs、CNTs—COOH的TEM图像和CNF-CNTs—COOH复合物的SEM图像
Figure 3. TEM images of CNF, CNTs, CNTs—COOH and SEM image of CNF-CNTs—COOH complex
图 4 超声30 min、静置6 h后CNTs和CNTs—COOH的水分散性对比
Figure 4. Comparison of water dispersibility of CNTs and CNTs—COOH after ultrasonic for 30 min standing for 6 h
图 5 PPy包覆CNF-CNTs—COOH-PGr复合物过程机制
Figure 5. Process mechanism of PPy coated CNF-CNTs—COOH-PGr complex
图 6 CNF-CNTs—COOH-PGr/PPy柔性电复合材料的数码照片
Figure 6. Digital photos of CNF-CNTs—COOH-PGr/PPy flexible electrode composite
图 7 CNF-CNTs—COOH-PGr复合物和CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的应力-应变曲线
Figure 7. Stress-strain curves of CNF-CNTs—COOH-PGr complex and CNF-CNTs—COOH-PGr/PPy flexible electrode composite
图 8 CNF-CNTs—COOH-PGr复合物(a)和PPy聚合不同时间的CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的SEM图像((b)~(e))及CNF-CNTs—COOH-PGr/PPy柔性电极复合材料断面的SEM图像(f)(内置图为断面的放大SEM图像)
Figure 8. SEM images of CNF-CNTs—COOH-PGr complex(a) and CNF-CNTs—COOH-PGr/PPy flexible electrode composites with different PPy polymerization times((b)–(e)), SEM image of cross section of CNF-CNTs—COOH-PGr/PPy flexible electrode composite(f) (Inset is a magnified SEM image of the section)
图 9 CNF-CNTs—COOH、CNF-CNTs—COOH-PGr复合物和CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的FTIR光谱
Figure 9. FTIR spectra of CNF-CNTs—COOH, CNF-CNTs—COOH-PGr complex and CNF-CNTs—COOH-PGr/PPy flexible electrode composite
图 10 CNF-CNTs—COOH、CNF-CNTs—COOH-PGr复合物和CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的电导率
Figure 10. Conductivity of CNF-CNTs—COOH, CNF-CNTs—COOH-PGr complex and CNF-CNTs—COOH-PGr/PPy flexible electrode composites
图 11 CNF-CNTs—COOH-PGr/PPy柔性电极复合材料充当导线点亮发光二极管(LED)的照片
Figure 11. Photograph of CNF-CNTs—COOH-PGr/PPy flexible electrode composite acting as a wire to illuminate light emitting diode (LED)
图 12 CNF-CNTs—COOH-PGr复合物、CNF-CNTs—COOH/PPy和CNF-CNTs—COOH-PGr/PPy柔性电极复合材料在电流密度1 A·g−1的恒电流充放电(GCD)曲线
Figure 12. Galvanostatic charge-discharge(GCD) curves of CNF-CNTs—COOH-PGr complex, CNF-CNTs—COOH/PPy and CNF-CNTs—COOH-PGr/PPy flexible electrode composites at 1 A·g−1 current density
图 13 电流密度0.5 A·g−1下不同聚合时间的CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的GCD曲线
Figure 13. GCD curves of CNF-CNTs—COOH-PGr/PPy flexible electrode composites at different polymerization times and 0.5 A·g−1 current density
图 14 CNF-CNTs—COOH-PGr/PPy1柔性电极复合材料在电流密度为0.5~5 A·g−1下的GCD曲线
Figure 14. GCD curves of CNF-CNTs—COOH-PGr/PPy1 flexible electrode composite at current density of 0.5–5 A·g−1
图 15 不同扫描速率下CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的循环伏安(CV)曲线
Figure 15. Cyclic voltammetry(CV) curves of CNF-CNTs—COOH-PGr/PPy flexible electrode composite at different scan rates
图 16 CNF-CNTs—COOH-PGr复合物、CNF-CNTs—COOH/PPy和CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的Nyquist曲线
Figure 16. Nyquist curves of CNF-CNTs—COOH-PGr complex，CNF-CNTs—COOH/PPy and CNF-CNTs—COOH-PGr/PPy flexible electrode composite
图 17 不同电流密度下CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的比电容量
Figure 17. Specific capacitance of CNF-CNTs—COOH-PGr/PPy flexible electrode composite at different current densities
图 18 CNF-CNTs—COOH-PGr/PPy柔性电极复合材料循环稳定性曲线(内置图为1 485~1 500次循环的GCD曲线)
Figure 18. Cycle stability curve of CNF-CNTs—COOH-PGr/PPy flexible electrode composite (Inset is 1 485–1 500 circles GCD curve)
表 1 不同聚合时间下CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的样品标记
Table 1. Sample labeling of CNF-CNTs—COOH-PGr/PPy flexible electrode composites at different polymerization times
Sample t/min CNF-CNTs—COOH 0 CNF-CNTs—COOH-PGr 0 CNF-CNTs—COOH/PPy0.5 30 CNF-CNTs—COOH-PGr/PPy0.5 30 CNF-CNTs—COOH-PGr/PPy1 60 CNF-CNTs—COOH-PGr/PPy2 120 CNF-CNTs—COOH-PGr/PPy3 240 Note: t—Reaction time of PPy. 
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