氧化石墨烯的酸性还原及其超级电容性能

doi:10.11949/0438-1157.20190722

摘要/Abstract

摘要：

采用改进的Hummers法制备氧化石墨烯(GO)，在酸性条件(pH=5)下以180°C进行水热还原，通过调节水热反应时间来制备不同还原程度的还原氧化石墨烯(RGO)。研究了不同的水热反应时间对RGO结构及超级电容性能的影响。结果表明：控制水热反应时间可以制备出还原程度不同的RGO，在电化学测试中，随着水热反应时间的延长，RGO电极的比电容呈先上升后下降的趋势。当水热反应时间为6 h时，RGO电极表现出最佳的超级电容性能，其在1 A/g电流密度下比电容达到251 F/g，相对于GO电极提高了225%。经过500次充放电循环后，RGO-6电极比电容保持率达到92%，具有优异的循环稳定性。

关键词: 纳米材料, 浆料, 氧化石墨烯, 酸性还原, 电容性能

Abstract:

Graphene oxide(GO) was prepared by improved Hummers method. Hydrothermal reduction was performed at 180℃ under acidic conditions (pH=5). Reduced graphene oxide (RGO) with different reduction degrees was prepared by adjusting hydrothermal reduction time. The effects of different hydrothermal reduction time on RGO structure and supercapacitive performance were studied. The results showed that RGO with different degree of reduction could be prepared by controlling the time of hydrothermal reduction. With the increase of hydrothermal reduction time, the specific capacitance of the RGO electrode increases at the beginning and then decreases through electrochemical testing. When the hydrothermal reduction time was 6 h, the RGO electrode showed the best supercapacitive performance, and its specific capacitance reached 251 F/g at 1 A/g current density, which was 225% higher than the GO electrode. After 500 charge and discharge cycles, the RGO-6 electrode has a specific capacitance retention rate of 92%, which has excellent cycle stability.

Key words: nanomaterials, slurry, graphene oxide, acid reduction, capacitance performance

中图分类号:

O 646

严正琦, 高江姗, 张鑫韬, 南非, 何燕. 氧化石墨烯的酸性还原及其超级电容性能[J]. 化工学报, 2019, 70(12): 4881-4888.

Zhengqi YAN, Jiangshan GAO, Xintao ZHANG, Fei NAN, Yan HE. Acid reduction of graphene oxide and performance of supercapacitor[J]. CIESC Journal, 2019, 70(12): 4881-4888.

图/表 7

图1 样品的整体形貌(a)和SEM图((b)~(f))和GO的TEM图(g)

Fig.1 Morphology photographs(a) and SEM images of samples((b)—(f)) and TEM of GO(g)

图2 GO和RGO-X的N2吸附-脱附等温线(a)XRD谱图(b)以及红外谱图(c)

Fig.2 N2 adsorption-desorption isotherms(a), XRD patterns(b) and infrared spectra(c) of GO and RGO-X

图3 GO和RGO-X的拉曼光谱图(a)和I D/I G变化趋势(b)

Fig.3 Raman spectra of GO and RGO-X(a) and change trend of I D/I G (b)

图4 GO和RGO-X电极在5 mV/s扫速下的CV曲线(a)和RGO-6电极在不同扫速下的CV曲线(b)

Fig.4 CV curves of GO and RGO-X electrodes at sweep rate of 5 mV/s (a) and CV curves of RGO-6 electrode with different sweep rates(b)

图5 GO和RGO-X电极的交流阻抗谱图(a)及样品的水接触角测试图(b)

Fig.5 Nyquist plots of GO and RGO-X electrodes(a) and water contact angle test chart of samples(b)

图6 GO和RGO-X电极在1 A/g电流密度下的CP曲线(a)和比电容变化趋势(b)

Fig.6 CP curves(a) and specific capacitance trend chart (b) of GO and RGO-X electrodes at 1 A/g current density

图7 GO和RGO-X电极在不同电流密度下的比电容曲线(a)和RGO-6电极在1A/g下的循环寿命(b)

Fig.7 Specific capacitance curves of GO and RGO-X electrodes at different current densities(a) and cycle life diagram of RGO-6 electrode at 1 A/g current density (b)

参考文献 30

1	陈丽娜, 王德禧, 谈述战, 等 . 石墨烯超级电容器的研究进展及其应用[J]. 中国塑料, 2014, 28(6): 8-18.
	Chen L N , Wang D X , Tan S Z , et al . Research progress and application of graphene supercapacitors[J]. China Plastics, 2014, 28(6): 8-18.
2	胡毅, 陈轩恕, 杜砚, 等 . 超级电容器的应用与发展[J]. 电力设备, 2008, 9(1): 19-22.
	Hu Y , Chen X S , Du Y , et al . Application and development of supercapacitors[J]. Electrical Equipment, 2008, 9(1): 19-22.
3	赵雪, 邱平达, 姜海静, 等 . 超级电容器电极材料研究最新进展[J]. 电子元件与材料, 2015, (1): 44-48.
	Zhao X , Qiu P D , Jiang H J , et al . Research progress of electrode materials for supercapacitors [J]. Electronic Components and Materials, 2015, (1): 44-48.
4	Simon P , Gogotsi Y . Materials for electrochemical capacitors[J]. Nature Materials, 2008, 7(11): 845-854.
5	Liu C , Yu Z , Neff D , et al . Graphene-based supercapacitor with an ultrahigh energy density[J]. Nano Letters, 2010, 10(12): 4863-4868.
6	Pan H , Li J , Feng Y P . Carbon nanotubes for supercapacitor[J]. Nanoscale Research Letters, 2010, 5(3): 654-668.
7	Zhi M , Yang F , Meng F , et al . Effects of pore structure on performance of an activated-carbon supercapacitor electrode recycled from scrap waste tires[J]. ACS Sustainable Chemistry & Engineering, 2014, 2(7): 1592-1598.
8	Liu D , Shen J , Li Y J , et al . Pore structures of carbon aerogels and their effects on electrochemical supercapacitor performance[J]. Acta Physico-Chimica Sinica, 2012, 28(28): 843-849.
9	Huang H P , Zhu J J . Preparation of novel carbon-based nanomaterial of graphene and its applications electrochemistry[J]. Chinese Journal of Analytical Chemistry, 2011, 39(7): 963-971.
10	Xu Y , Lin Z , Huang X , et al . Functionalized graphene hydrogel-based high-performance supercapacitors[J]. Advanced Materials, 2013, 25(40): 5779-5784.
11	汪建德, 彭同江, 孙红娟, 等 . 水热反应温度对三维还原氧化石墨烯的形貌、结构和超级电容性能的影响[J]. 物理化学学报, 2014, 30(11): 2077-2084.
	Wang J D , Peng T J , Sun H J , et al . Effect of hydrothermal reaction temperature on morphology, structure and ultracapactance of three-dimensional reduced graphene oxide [J]. Chinese Journal of Physical Chemistry, 2014, 30(11): 2077-2084.
12	Bai Y , Rakhi R B , Chen W , et al . Effect of pH-induced chemical modification of hydrothermally reduced graphene oxide on supercapacitor performance[J]. Journal of Power Sources, 2013, 233(7): 313-319.
13	汪建德, 彭同江, 孙红娟, 等 . 三维还原氧化石墨烯的制备及超级电容性能[J]. 人工晶体学报, 2015, 44(1): 78-84.
	Wang J D , Peng T J , Sun H J , et al . Preparation and ultracapacitor properties of 3D reduced grapheme oxide[J]. Journal of Synthetic Crystals, 2015, 44(1): 78-84.
14	Yan J , Fan Z , Wei S , et al . Advanced asymmetric supercapacitors based on Ni(OH)₂/graphene and porous graphene electrodes with high energy density[J]. Advanced Functional Materials, 2012, 22(12): 2632-2641.
15	牛玉莲, 金鑫, 郑佳, 等 . 石墨烯/钴镍双金属氢氧化物复合材料的制备及电化学性能研究[J]. 无机化学学报, 2012, 28(9): 1878-1884.
	Niu Y L , Jin X , Zheng J , et al . Preparation and electrochemical properties of graphene/cobalt-nickel bimetallic hydroxide composites [J]. Chinese Journal of Inorganic Chemistry, 2012, 28(9): 1878-1884.
16	Yu D , Dai L . Self-assembled graphene/carbon nanotube hybrid films for supercapacitors[J]. Journal of Physical Chemistry Letters, 2009, 1(2): 467-470.
17	Li Y , Zijll M V , Chiang S , et al . KOH modified graphene nanosheets for supercapacitor electrodes[J]. Journal of Power Sources, 2011, 196(14): 6003-6006.
18	Zhang K , Mao L , Zhang L L , et al . Surfactant-intercalated, chemically reduced graphene oxide for high performance supercapacitor electrodes[J]. Journal of Materials Chemistry, 2011, 21(20): 7302-7307.
19	Stobinski L , Lesiak B , Malolepszy A , et al . Graphene oxide and reduced graphene oxide studied by the XRD, TEM and electron spectroscopy methods[J]. Journal of Electron Spectroscopy & Related Phenomena, 2014, 195(15): 145-154.
20	Deng W , Ji X , Gómezmingot M , et al . Graphene electrochemical supercapacitors: the influence of oxygen functional groups[J]. Chemical Communications, 2012, 48(22): 2770-2772.
21	周敏 . 氧化石墨烯的制备与表征[J]. 化工技术与开发, 2017, 46(7): 21-24.
	Zhou M . Preparation and characterization of grapheme oxide[J]. Chemical Technology and Development, 2017, 46(7): 21-24.
22	Ferrari A C , Meyer J C , Scardaci V , et al . Raman spectrum of graphene and graphene layers[J]. Physical Review Letters, 2006, 97(18): 187-190.
23	曲若萌, 李延平, 王玫 . 酸化处理多壁碳纳米管的IR和Raman分析[J]. 化学工程师, 2013, 27(11): 61-63.
	Qu R M , Li Y P , Wang M . IR and Raman analysis of acidizing multiwalled carbon nanotubes [J]. Chemical Engineer, 2013, 27(11): 61-63.
24	杨勇辉, 孙红娟, 彭同江 . 石墨烯薄膜的制备和结构表征[J]. 物理化学学报, 2011, 27(3): 736-742.
	Yang Y H , Sun H J , Peng T J . Preparation and structural characterization of graphene films [J]. Acta Physico-Chimica Sinica, 2011, 27(3): 736-742.
25	Zhao J , Jiang Y , Fan H , et al . Porous 3D few-layer graphene-like carbon for ultrahigh-power supercapacitors with well-defined structure-performance relationship[J]. Advanced Materials, 2017, 29(11): 160-165.
26	朱国银 . 基于碳纳米管-石墨烯-泡沫镍三维复合结构的超级电容器电极制备与性能[D]. 南京: 南京邮电大学, 2014.
	Zhu G Y . Preparation and properties of supercapacitor electrode based on carbon nanotube graphene-nickel foam three-dimensional composite structure [D]. Nanjing: Nanjing University of Posts and Telecommunications, 2014.
27	Mosa I M , Pattammattel A , Kadimisetty K . et al . Ultrathin graphene-protein supercapacitors for miniaturized bioelectronics[J]. Advanced Energy Materials, 2017, 7(17): 251-255.
28	Cao J , Wang Y , Chen C , et al . A Comparison of graphene hydrogels modified with single-walled/multi-walled carbon nanotubes as electrode materials for capacitive deionization[J]. Journal of Colloid and Interface Science, 2018, 5(18): 69-75.
29	Chen Y , Zhang X , Zhang D , et al . High performance supercapacitors based on reduced graphene oxide in aqueous and ionic liquid electrolytes[J]. Carbon, 2011, 49(2): 573-580.
30	Boschnavarro C , Coronado E , Martígastaldo C . Influence of the pH on the synthesis of reduced graphene oxide under hydrothermal conditions[J]. Nanoscale, 2012, 4(13): 3977-3982.

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