一步合成还原氧化石墨烯/MnO2复合材料及其电化学性能

doi:10.15541/jim20150004

摘要/Abstract

摘要：

通过水热法, 利用氧化石墨烯(GO)和二价锰盐, 一步合成了还原氧化石墨烯/MnO₂(RGO/M)复合电极材料。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼光谱(RS)、傅里叶红外光谱(FTIR)和场发射扫描电镜(FESEM)等测试电极材料的物性, 通过循环伏安、交流阻抗和恒流充放电等方法研究电极材料的电化学性能。结果表明, 在一定水热反应条件下, 通过控制GO与二价锰盐配比, 可以调节RGO/M的结构及其电化学性能。在1 A/g电流密度下, 所得RGO/M复合电极的比电容可达277 F/g, 经过500次循环后, 保持率达到98%。

关键词: 还原氧化石墨烯, 二氧化锰, 水热法, 比电容, 超级电容器

Abstract:

Reduced graphene oxide/MnO₂ (RGO/M) composites were successfully prepared via one-step hydrothermal routine, in which graphene oxide serviced as the oxidant and Mn²⁺ as the reducer. The morphology and microstructure of the nanocomposites were characterized by X-ray diffraction (XRD) analysis, X-ray Photoelectron Spectroscope (XPS), Raman spectra (RS), Fourier transform infrared (FTIR) spectroscope and field emission scanning electron microscope (FESEM). In addition, the electrochemical properties of the composite were evaluated by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy techniques for supercapacitor applications. The results indicate that the RGO/M composites displayed controllable specific capacitance in acidic electrolytes by adjusting the molar ratio of GO to manganous chloride at a specific hydrothermal reaction condition. In the optimal case, a specific capacitance of 277 F/g can be obtained in 1 mol/L H₂SO₄ at a scan current density of 1 A/g, with a capacitance retention of 98% after 500 cycles.

Key words: reduced graphene oxide, manganese dioxide, hydrothermal, specific capacitance, supercapacitor

中图分类号:

O646

侯渊, 张邦文, 邢瑞光, 布林朝克. 一步合成还原氧化石墨烯/MnO₂复合材料及其电化学性能[J]. 无机材料学报, 2015, 30(8): 855-860.

HOU Yuan, ZHANG Bang-Wen, XING Rui-Guang, BULIN Chao-Ke. One-step Synthesis and Electrochemical Properties of Reduced Graphene Oxide/MnO₂ Composites[J]. Journal of Inorganic Materials, 2015, 30(8): 855-860.

图/表 11

图1 NG、GO及RGO/M3复合材料的XRD图谱

Fig. 1 XRD patterns of NG, GO and RGO/M3 composite

图2 GO与RGO/M3复合材料的RS谱

Fig. 2 Raman spectra of GO and RGO/M3 composite

图3 RGO/M3复合材料的XPS图谱

Fig. 3 XPS spectra of the RGO/M3 composite

图4 GO与RGO/M3复合材料的FTIR谱

Fig. 4 FTIR spectra of the GO and RGO/M3 composite

图5 RGO/M3的FESEM图(a)、(b)和(c)与EDS面扫图(d)

Fig. 5 FESEM images (a-c), FSEM image and the corresponding EDS elemental mapping images (d)

图6 RGO/M形成机理示意图

Fig. 6 Schematic of the formation mechanism of RGO/M composites

图7 纯RGO与不同比例RGO/M的循环伏安曲线(10 mV/s)

Fig. 7 Cyclic voltammograms of RGO/M and RGO with different molar ratios at a scan rate of 10 mV/s

图8 不同比例RGO/M的放电曲线(1 A/g)

Fig. 8 Discharge curves (at 1 A/g) of RGO/M with different molar ratios

图9 RGO/M3在不同扫描速率下的循环伏安曲线

Fig. 9 Cyclic voltammograms of RGO/M3 at various scan rates

图10 RGO/M3的交流阻抗图

Fig. 10 Nyquist plots of RGO/M3

图11 1 A/g扫描速率下RGO/M3比电容的循环性能

Fig. 11 Cycle performance of RGO/M3 at a scan rate of 1 A/g

参考文献 27

[1]	CONWAY B E.Transition from “supercapacitor” to “battery” behavior in electrochemical energy storage.J. Electrochem. Soc., 1991, 138(6): 1539-1548.
[2]	JIANG Q, QU M Z, ZHANG B L, et al.Progress of research on electrode materials for electrochemical supercapacitors.Journal of Inorganic Materials, 2002, 17(4): 649-656.
[3]	LEE J W, HALL A S, KIM J D, et al.A facile and template-free hydrothermal synthesis of Mn3O4 nanorods on graphene sheets for supercapacitor electrodes with long cycle stability.Chem. Mater., 2012, 24(6): 1158-1164.
[4]	WANG G, ZHANG L, ZHANG J.A review of electrode materials for electrochemical supercapacitors.J. Chem. Soc. Rev., 2012, 41(2): 797-828.
[5]	XIAO X Z, YI Q F.Synthesis and electrochemical capacity of MnO2/SMWCNT/PANI ternary composites.Journal of Inorganic Materials, 2013, 28(8): 825-830.
[6]	YU G, HU L, VOSGUERITCHIAN M, et al.Solution-processed graphene/MnO2 nanostructured textiles for high-performance electrochemical capacitors.Nano Lett., 2011, 11(7): 2905-2911.
[7]	FENG Y Q, TANG F L, LANG J W, et al.Facile approach to preparation of nitrogen-doped graphene and its supercapacitive performance.Journal of Inorganic Materials, 2013, 28(6): 677-682.
[8]	MAO L, ZHANG K, CHAN H S O, et al. Nanostructured MnO2/graphene composites for supercapacitor electrodes: the effect of morphology, crystallinity and composition. J. Mater. Chem., 2012, 22(5): 1845-1851.
[9]	WEI W, CUI X, CHEN W, et al.Manganese oxide-based materials as electrochemical supercapacitor electrodes.Chem. Soc. Rev., 2011, 40(3): 1697-1721.
[10]	ZHANG L L, WEI T, WANG W, et al.Manganese oxide-carbon composite as supercapacitor electrode materials.Microporous Mesoporous Mater., 2009, 123(1): 260-267.
[11]	XIA H, WANG Y, LIN J, et al.Hydrothermal synthesis of MnO2/CNT nanocomposite with a CNT core/porous MnO2 sheath hierarchy architecture for supercapacitors. Nanoscale Res. Lett., 2012, 7(1): 1-10.
[12]	WU Z S, REN W, WANG D W, et al.High-energy MnO2 nanowire/graphene and graphene asymmetric electrochemical capacitors.ACS Nano, 2010, 4(10): 5835-5842.
[13]	QIAN Y, LU S, GAO F.Preparation of MnO2/graphene composite as electrode material for supercapacitors. J. Mater. Sci., 2011, 46(10): 3517-3522.
[14]	LOH K P, BAO Q, ANG P K, et al.The chemistry of graphene. J. Mater. Chem., 2010, 20(12): 2277-2289.
[15]	GEIM A K.Graphene: status and prospects.Science, 2009, 324(5934): 1530-1534.
[16]	YUAN X Y.Progress in preparation of graphene.Journal of Inorganic Materials, 2011, 26(6): 561-570.
[17]	WANG L L, XING R G, ZHANG B W, et al.Preparation and electrochemical properties of functionalized graphene/polyaniline composite electrode materials.Acta Phys-Chim. Sin., 2014, 30(9): 1659-1666.
[18]	ZHAO X, ZHANG L, MURALI S, et al.Incorporation of manganese dioxide within ultraporous activated graphene for high-performance electrochemical capacitors.ACS Nano, 2012, 6(6): 5404-5412.
[19]	LI Z, WANG J, LIU S, et al.Synthesis of hydrothermally reduced graphene/MnO2 composites and their electrochemical properties as supercapacitors.J. Power Pources, 2011, 196(19): 8160-8165.
[20]	LEE J W, HALL A S, Kim J D, et al.A facile and template-free hydrothermal synthesis of Mn3O4 nanorods on graphene sheets for supercapacitor electrodes with long cycle stability. Chem. Mater., 2012, 24(6): 1158-1164.
[21]	LI L, HE Y Q, CHU X F, et al.Hydrothermal synthesis of partially reduced graphene oxide-K2Mn4O8 nanocomposites as supercapacitors.Acta Phys-Chim. Sin., 2013, 29(8): 1681-1690.
[22]	Kovtyukhova N I, Ollivier P J, Martin B R, et al.Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations.Chem. Mater., 1999, 11(3): 771-778.
[23]	MALARD L M, PIMENTA M A, DRESSELHAUS G, et al.Raman spectroscopy in graphene.Physics Reports, 2009, 473(5): 51-87.
[24]	LI Z P, MI Y J, LIU X H, et al.Flexible graphene/MnO2 composite papers for supercapacitor electrodes.J. Mater. Chem., 2011, 21(38): 14706-14711.
[25]	DEVARAJ S, MUNICHANDRAIAH N.Effect of crystallographic structure of MnO2 on its electrochemical capacitance properties. J. Phys. Chem. C, 2008, 112(11): 4406-4417.
[26]	STOLLER M D, RUOFF R S.Best practice methods for determining an electrode material's performance for ultracapacitors.Energy Environ. Sci., 2010, 3(9): 1294-1301.
[27]	ZHANG K, ZHANG L L, ZHAO X, et al.Graphene/polyaniline nanofiber composites as supercapacitor electrodes.Chem. Mater., 2010, 22(4): 1392-1401.

一步合成还原氧化石墨烯/MnO₂复合材料及其电化学性能

One-step Synthesis and Electrochemical Properties of Reduced Graphene Oxide/MnO₂ Composites

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