纤维素纳米纤维基层层自组装透明柔性导电膜及其电致变色柔性超级电容器

doi:10.7503/cjcu20150146

摘要/Abstract

摘要：

以纤维素纳米纤维(CNFs)膜为基材, 通过层层自组装法设计并制备了CNFs/[Cu²⁺-GO]₅/[PANI-PEDOT∶PSS]₁₀复合膜(CGPP膜), 经过除铜, 将氧化石墨烯(GO)还原为还原氧化石墨烯(RGO), 得到CNFs/RGO₅/[PANI-PEDOT∶PSS]₁₀复合导电膜(CRGPP-10膜), 并以H₂SO₄-PVA凝胶为电解质, 双片CRGPP-10膜为电极, 组装了双电极体系的柔性超级电容器S-RGPP. 对CGPP膜和CRGPP-10膜进行紫外-可见光谱、结晶特性和形态表征, 并对S-RGPP的循环伏安(CV)曲线、恒电流充放电性能(GCD)及电化学阻抗谱(EIS)等电化学性能进行分析. 结果表明, 通过层层自组装法制备的CRGPP-10膜具有均匀和透明度可控的优点. 柔性超级电容器S-RGPP的内阻较小, 同时具有双电层(EDL)电容和赝电容性能, 表现出良好的柔性和一定的电致变色性. RGO的加入使S-RGPP的循环稳定性得到改善.

关键词: 纤维素纳米纤维, 还原氧化石墨烯, 层层自组装, 电致变色性, 柔性超级电容器

Abstract:

The cellulose nanofibers(CNFs) film exhibit high visible light transmittance, high mechanical strength, and excellent flexibility. Therefore, CNFs film may be an excellent substrate material for flexible transparent electronic devices. In this paper, we endeavor to prepare the CNFs-based hybrid multilayer thin film CNFs/[Cu²⁺-GO]₅/[PANI-PEDOT∶PSS]₁₀ by layer-by-layer assembly method using divalent copper ions(Cu²⁺) as the crosslinking agent. Then the conductive thin film of CRGPP-10 was got by removing copper ions with solution and using reduction reaction of graphene oxide(GO) with hydroiodic acid solution for reduction of oxide graphene(RGO) from CNFs/[Cu²⁺-GO]₅/[PANI-PEDOT∶PSS]₁₀ film. After that, the supercapacitor fabricated S-RGPP was fabricated using double CRGPP-10 films as electrode when H₂SO₄-PVA gel was used as the electrolyte. The crystalline characteristic and configuration of CRGPP thin films, along with the absorbency characteristics of CRGPP thin films, were analyzed. Meanwhile, the electrochemical characters of the supercapacitor S-RGPP were tested, such as cyclic vollammetry(CV) curves, galvanostatic charge-discharge(GCD) and electrochemical impedance spectroscopy(EIS). The results indicated that the method of the flexible electrochromic film with layer-by-layer assembly method is practicable. The conducting film CRGPP-10 was uniform with controlled transparency. The supercapacitor S-RGPP exhibits an excellent areal capa-citance of 8.15 mF/cm² at a current density of 0.0043 mA/cm². Owing to the addition of RGO reagent, the cycle stability of supercapacitor S-PGPP improved, which is fabricated by CPRPP-10 electrodes. The device exhibited good electrochemical performance, such as the characters of the low resistance, with the capacitive behavior of the electrical double-layer capacitor(EDL) capacitor and pseudo capacitor at the same time. Meanwhile, it showed so better flexible that there was no difference between normal and bent state. The device shows some electrochromism. This study provides a novel method using CNFs as substrate to prepare hybrid electrodes for future flexible supercapacitors.

Key words: Cellulose nanofibers(CNFs), Reduced graphene oxide(RGO), Layer-by-layer assembly method, Electrochromism, Flexible supercapacitor

中图分类号:

O636

TrendMD:

郝红英, 王茜, 邵自强, 杨荣杰. 纤维素纳米纤维基层层自组装透明柔性导电膜及其电致变色柔性超级电容器. 高等学校化学学报, 2015, 36(9): 1838.

HAO Hongying, WANG Xi, SHAO Ziqiang, YANG Rongjie. Transparent Flexible Conductive Thin Films Based on Cellulose Nanofibers by Layer-by-layer Assembly Method and Its Fabricated Electrochromic Flexible Supercapacitors^†. Chem. J. Chinese Universities, 2015, 36(9): 1838.

图/表 14

Scheme 1 Schematic illustration of preparation process of flexible composite membranes CNFs/RGO5/[PANI-PEDOT∶PSS]10 and the flexible supercapacitors S-RGPP

Fig.1 Flexible(A), transparency(B) and UV-Vis absorbance spectrum(C) of CNFs film

Fig.2 TEM(A) and AFM images(B) of CNFs film

Fig.3 UV-Vis absorbance spectra of CNFs/[Cu2+-GO]5/[PANI-PEDOT∶PSS]n composite films of different layers(A) and the relationship between the absorbance of PANI layer and the number of self-assembled layers(B)(A) a. n=0; b. n=2; c. n=4; d. n=5; e. n=8; f. n=10.

Fig.4 XRD patterns of CNFs film(a) and CRGPP-10 film(b)

Fig.5 SEM images of the surface(A) and cross-section(B) of CRGPP-10 film

Fig.6 Typical CV curves of S-RGPP device at different scan ratesScan rate/(mV·s-1): a. 2; b. 5; c. 10; d. 50; e. 100.

Fig.7 Typical galvanostatic charge-discharge curves of S-RGPPCurrent density/(mA·cm-2): a. 0.03; b. 0.04; c. 0.07; d. 0.14.

Fig.8 Areal capacitance of S-RGPP device at different scan rates

Fig.9 EIS with sweep frequencyThe inset shows the magnified high-frequency and medium-frequency regions.

Fig.10 Comparison of CV curves for S-RGPP device tested under normal(a) and bent state(b)

Fig.11 Transmission of S-RGPP device

Fig.12 Cycling stability of S-RGPP device over 3000 cycles

Fig.13 UV-Vis absorbance spectra of S-RGPP at different voltage levels

参考文献 29

[1]	Thompson B. C., Schottland P., Zong K. W., Chemistry of Materials, 2000, 12(6), 1563—1571
[2]	Dyer A. L., Thompson E. J., Reynolds J. R., ACS Applied Materials & Interfaces, 2011, 3(6), 1787—1795
[3]	Yuan L., Yao B., Hu B., Energy & Environmental Science, 2013, 6(2), 470—476
[4]	Hu L., Zheng G., Yao J., Energy & Environmental Science, 2013, 6(2), 513—518
[5]	Wang K., Wu H., Meng Y., Energy & Environmental Science, 2012, 5(8), 8384—8389
[6]	Zhang J., Yu Y., Liu L., Nanoscale, 2013, 5(7), 3052—3057
[7]	Lee T., Yun T., Park B., Journal of Materials Chemistry, 2012, 22(39), 21092—21099
[8]	Yuan Y. F., Xia X. H., Wu J. B., Journal of Membrane Science, 2010, 364(1/2), 298—303
[9]	Barbero C., Planes G. A., Miras M. C., Electrochemistry Communications, 2001, 3(3), 113—116
[10]	Sveg F., Vuk A. S., Hajzeri M., Solar Energy Materials and Solar Cells, 2012, 99, 14—25
[11]	Silva C. H. B., Galiote N. A., Huguenin F., Journal of Materials Chemistry, 2012, 22(28), 14052—14060
[12]	Wei J., Xiong S., Bai Y., Solar Energy Materials and Solar Cells, 2012, 99, 141—147
[13]	Xu N., Shen X., Cui S., High Performance Polymers, 2011, 23(7), 489—493
[14]	Liu X. R., Gao F. Y., Dong G. B., Wang C., Diao X. G., Acta Polymerica Sinica, 2014, 9, 2244—2250
	(刘煦冉, 高方圆, 董国波, 王超, 刁训刚. 高分子学报, 2014, 9, 2244—2250)
[15]	Weng S. H., Zhou J. Z., Lin Z. H., Lin X. H., Chem. J. Chinese Universities, 2012, 33(11), 2501—2508
	(翁少煌, 周剑章, 林仲华, 林新华. 高等学校化学学报, 2012, 33(11), 2501—2508)
[16]	Alemu D., Wei H. Y., Ho K. C., Energy & Environmental Science, 2012, 5(11), 9662—9671
[17]	Zhu H., Xiao Z., Liu D., Energy & Environmental Science, 2013, 6(7), 2105—2111
[18]	Iwamoto S., Kai W., Isogai T., Polymer Degradation and Stability, 2010, 95(8), 1394—1398
[19]	Saito T., Nishiyama Y., Putaux J. L., Colloids and Surfaces A, 2006, 289, 219—225
[20]	Weng Z., Su Y., Wang D. W., Advanced Energy Materials, 2011, 1(5), 917—922
[21]	Gao K. Z, Shao Z. Q., Wu X., Nanoscale, 2013, 5, 5307—5311
[22]	Wang X., Gao K. Z, Shao Z. Q., Peng X. Q., Wu X., Wang F. J., Journal of Power Sources, 2014, 249(1), 148—156
[23]	Tung V. C., Allen M. J., Yang Y., Nature Nanotechnology, 2009, 4(1), 25—29
[24]	Shao L., Jeon J. W., Lutkenhaus J. L., Chemistry of Materials, 2012, 24(1), 181—189
[25]	Chiang J. C., Macdiarmid A. G., Synthetic Metals, 1986, 13(1—3), 193—205
[26]	Ryu K. S., Moon B. W., Joo J., Polymer, 2001, 42(23), 9355—9360
[27]	Sun D. C., Sun D. S., Progress in Chemistry, 2009, 25(7), 111—117
	(孙东成, 孙德生. 化学进展, 2009, 25(7), 111—117)
[28]	Peng W., Li D. Q., Peng J., Peng L. L., Wu C. Z., Xie Y., Science Bulletin, 2013, 58(28/29), 2886—2894
	(彭旭, 李典奇, 彭晶, 彭乐乐, 吴长征, 谢毅. 科学通报, 2013, 58(28/29), 2886—2894)
[29]	Peng L.L., Peng X., Liu B. R., Nano Lett., 2013, 13, 2151—2157