一步合成Mn3O4@RGO复合材料及其非对称超级电容器的应用

doi:10.15541/jim20150536

摘要/Abstract

摘要：

在乙醇胺和水组成的混合溶剂中, Mn(Ac)₂与氧化石墨烯一步反应得到还原石墨烯(RGO)与黑锰矿纳米颗粒(Mn₃O₄)组成的复合材料Mn₃O₄@RGO。以Mn₃O₄@RGO为正极, RGO为负极, 组装得到了具有优良储能性能的非对称型超级电容器Mn₃O₄@RGO//RGO。基于活性物质的总质量, 电容器的最大能量密度可达21.7 Wh/kg, 相应的功率密度为0.5 kW/kg; 同时, 最大功率密度为8 kW/kg时, 对应的能量密度为11.1 Wh/kg。Mn₃O₄@RGO//RGO还表现出良好的循环稳定性, 在经历5000次循环后, 比电容依然保持88.4%。电容器的良好储能性能可归因于在RGO表面生长的高密度Mn₃O₄纳米颗粒和RGO的良好导电性能。

关键词: Mn3O4, RGO, 复合材料, 溶剂热, 非对称超级电容器

Abstract:

Supercapacitors have attracted dramatic attentions in recent years for their apparent advantages, such as fast charge/discharge rate, high power density and high stability. However, it is still a challenge to improve their energy density for their practical applications. One of the strategies to overcome this drawback is to broaden the working voltage of the devices through assembling asymmetric supercapacitors. Herein, Mn₃O₄@RGO nanocomposites were successfully synthesized by using one-pot approach with Mn(Ac)₂ and GO in the mixed solvent of ethanolamine and water (3:1) without adding any surfactant. The asymmetric supercapacitors (Mn₃O₄@RGO//RGO) assembled with Mn₃O₄@RGO and RGO exhibit excellent performances in energy storage. The asymmetric supercapacitors can achieve a maximum energy density of 21.7 Wh/kg at power density of 500 W/kg and a maximum power density of 8 kW/kg at energy density of 11.1 Wh/kg, based on the total mass of active materials. The Mn₃O₄@RGO//RGO supercapacitors also demonstrated excellent durability retaining 88.4% of their specific capacitances even after 5000 charge/discharge cycles. The excellent performances of Mn₃O₄@RGO//RGO devices in energy storage can be attributed to high density of Mn₃O₄ nanoparticles grown directly on the surfaces of RGO nanosheets, which can dramatically improve the conductivity of materials.

Key words: Mn3O4, graphene, nanocomposites, solvothermal, asymmetric supercapacitors

中图分类号:

TQ174

王超飞, 鲁双, 陈慧龙, 巩飞龙, 龚玉印, 李峰. 一步合成Mn₃O₄@RGO复合材料及其非对称超级电容器的应用[J]. 无机材料学报, 2016, 31(6): 581-587.

WANG Chao-Fei, LU Shuang, CHEN Hui-Long, GONG Fei-Long, GONG Yu-Yin, LI Feng. One-pot Synthesis and Application in Asymmetric Supercapacitors of Mn₃O₄@RGO Nanocomposites[J]. Journal of Inorganic Materials, 2016, 31(6): 581-587.

图/表 6

图1 (a) GO 和 (b) RGO的XRD 图谱, (c) GO与不同试剂还原的RGO的FT-IR图谱

Fig. 1 XRD patterns of (a) GO and (b) RGO, and (c) their FT-IR spectra

图2 (a) RGO和(b、c)Mn3O4@RGO的FESEM照片, (d)Mn3O4@RGO的XRD图谱

Fig. 2 FESEM and images of (a) RGO and (b-c) Mn3O4@RGO nanocomposites, (d) XRD pattern of Mn3O4@RGO nanocomposites

图3 (a、b) RGO和(c、d) Mn3O4@RGO的TEM 和HRTEM图片, 插图为对应的SAED照片

Fig. 3 TEM and HRTEM images of RGO (a-b) and Mn3O4@RGO nanocomposites (c,d), with inset in (d) showing the corresponding SAED pattern

图4 (a、b) Mn3O4@RGO电极和(c、d) RGO电极的CV曲线和恒流充放电曲线

Fig. 4 CV curves of Mn3O4@RGO nanocomposites (a) and RGO (c) measured in a three-electrode cell in 1 mol/L Na2SO4 electrolytes at different scan rates, and charge-discharge curves of supercapacitors constructed with Mn3O4@RGO nanocomposites (b) and RGO (d) in 1 mol/L Na2SO4 electrolytes measured at different current densities

图5 Mn3O4@RGO//RGO非对称两电极超级电容器的CV曲线(a), 恒流充放电曲线(b), 不同充放电电流密度下的质量比电容(c), 以及循环稳定性测试(d), 插图为前20次的循环测试曲线

Fig. 5 (a) Cyclic voltammograms at different scan rates, (b) charge/discharge curves and (c) specific capacitances at different current densities for Mn3O4@RGO//RGO asymmetric supercapacitor in 1 mol/L Na2SO4 electrolytes, and (d) charge-discharge cycling test of Mn3O4@RGO//RGO asymmetric supercapacitor at current density of 4 A/g. Inset shows the galvanostatic charge-discharge cyclic curves of the first twenty cycles at 4 A/g

图6 Mn3O4@RGO//RGO非对称超级电容器的比能量与比功率密度图

Fig. 6 Ragone plots of Mn3O4@RGO//RGO asymmetric supercapacitors

参考文献 38

[1]	YANG F, ZHAO M, SUN Q, et al.A novel hydrothermal synthesis and characterisation of porous Mn3O4 for supercapacitors with high rate capability.RSC Adv., 2015, 5(13): 9843-9847.
[2]	RAJ B G S, RAMPRASAD R N R, ASIRI A M, et al. Ultrasound assisted synthesis of Mn3O4 nanoparticles anchored graphene nanosheets for supercapacitor applications. Electrochimica Acta, 2015, 156(1): 127-137.
[3]	SIMON P, GOGOTSI Y.Materials for electrochemical capacitors .Nat.Mater., 2008, 7(11): 845-854.
[4]	ZHAO X, S NCHEZ B M, DOBSON P J, et al. The role of nanomaterials in redox-based supercapacitors for next generation energy storage devices.Nanoscale, 2011, 3(3): 839-855.
[5]	EL-KADY M F, STRONG V, DUBIN S, et al. Laser scribing of high-performance and flexible graphene-based electrochemical capacitors. Science, 2012, 335(6074): 1326-1330.
[6]	JING M, WANG J, HOU H,et al. Carbon quantum dot coated Mn3O4 with enhanced performances for lithium-ion batteries. J. Mater. Chem. A, 2015, 3(32): 16824-16830.
[7]	XIAO Y, CAO Y, GONG Y, et al.Electrolyte and composition effects on the performances of asymmetric supercapacitors constructed with Mn3O4 nanoparticles-graphene nanocomposites . Journal of Power Sources, 2014, 246(8): 926-933.
[8]	MEI J, ZHANG L.Novel MnOOH-graphene nanocomposites: Preparation, characterization and electrochemical properties for supercapacitors.Journal of Solid State Chemistry, 2015, 221: 178-183.
[9]	CAO Y, XIAO Y, GONG Y, et al.One-pot synthesis of MnOOH nanorods on graphenefor asymmetric supercapacitors. Electrochem. Acta, 2014, 127: 200-207.
[10]	FAN Z, YAN J, WEI T, et al.Asymmetric supercapacitors based on graphene/MnO2 and activated carbon nanofiber electrodes with high power and energy density. Adv. Funct. Mater., 2011, 21(12): 2366-2375.
[11]	QU Q, SHI Y, TIAN S, et al.A new cheap asymmetric aqueous supercapacitor: Activated carbon//NaMnO2. J. Power Sources, 2009, 194(2): 1222-1225.
[12]	GONG Y, GONG F, WANG C, et al.Porous and single crystalline Co3O4 nanospheres for pseudocapacitors with enhanced performance.RSC Adv., 2015, 5: 27266-27272.
[13]	KHOMENKO V, RAYMUNDO-PINERO E, FRACKOWIAK E, et al.High-voltage asymmetric supercapacitors operating in aqueous electrolyte. Appl.Phys.A, 2006, 82(4): 567-573.
[14]	YU C, MASARAPU C, RONG J, et al.Stretchable supercapacitors based on buckled single-walled carbon‐nanotube macrofilms.Adv.Mater., 2009, 21(47): 4793-4797.
[15]	LEI Z, ZHANG J, ZHAO X.Ultrathin MnO2 nanofibers grown on graphitic carbon spheres as high-performance asymmetric supercapacitor electrodes. J. Mater. Chem., 2012, 22(1): 153-160.
[16]	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.
[17]	CHEN B, RAO G, WANG S, et al.Facile synthesis and characterization of Mn3O4 nanoparticles by auto-combustion method.Materials Letters, 2015, 154: 160-162.
[18]	LIU Y, WANG W, WANG Y, et al.Binder-free three-dimensional porous Mn3O4 nanorods/reduced graphene oxide paper-like electrodes for electrochemical energy storage. RSC.Advances, 2014, 4(31): 16374.
[19]	QIAN W, CHEN Z, COTTINGHAM S, et al.Surfactant-free hybridization of transition metal oxide nanoparticles with conductive graphene for high-performance supercapacitor. Green Chem., 2012, 14(2): 371-377.
[20]	XIA H, MENG Y S, LI X, et al.Porous manganese oxide generated from lithiation/delithiation with improved electrochemical oxidation for supercapacitors.J. Mater. Chem., 2011, 21(39): 15521-15526.
[21]	WANG D, LI Y, WANG Q, et al.Facile synthesis of porous Mn3O4 nanocrystal-graphene nanocomposites for electrochemical supercapacitors.Eur. J. Inorg. Chem., 2012, 2012(4): 628-635.
[22]	SHE X, ZHANG X, LIU J, et al.Microwave-assisted synthesis of Mn3O4 nanoparticles@reduced graphene oxide nanocomposites for high performance supercapacitors .Materials Research Bulletin, 2015, 70(2): 945-950.
[23]	WANG H, CUI L F, YANG Y, et al.Mn3O4-graphene hybrid as a high-capacity anode material for lithium ion batteries.J. Am. Chem. Soc., 2010, 132(40): 13978-13980.
[24]	HUMMERS W S, OFFEMAN R E.Preparation of graphitic oxide.J. Am. Chem. Soc., 1958, 80: 1339-1340.
[25]	XIAO Y, LIU S, LI F, et al.3D Hierarchical Co3O4 twin‐spheres with an urchin‐like structure: large‐scale synthesis, multistep‐splitting growth, and electrochemical pseudocapacitors. Adv. Funct. Mater., 2012, 22(19): 4052-4059.
[26]	PARK S, AN J, JUNG I, et al.Colloidal suspensions of highly reduced graphene oxide in a wide variety of organic solvents.Nano Lett., 2009, 9(4): 1593-1597.
[27]	PHAM V H, CUONG T V, HUR S H, et al.Chemical functionalization of graphene sheets by solvothermal reduction of a graphene oxide suspension in N-methyl-2-pyrrolidone.J. Mater. Chem., 2011, 21(10): 3371-3377.
[28]	BOSE V C, BIJU V.Structure, cation valence states and electrochemical properties of nanostructured Mn3O4.Materials Science in Semiconductor Processing, 2015, 35(7): 1-9.
[29]	LI Y, LI X M.Facile treatment of wastewater produced in Hummer's method to prepare Mn3O4 nanoparticles and study their electrochemical performance in an asymmetric supercapacitor. RSC Adv., 2013, 3(7): 2398-2403.
[30]	RAKHI R B, CHEN W, CHA D, et al.High performance supercapacitors using metal oxide anchored graphene nanosheet electrodes. J. Mater. Chem., 2011, 21(40): 16197-16204.
[31]	HU C C, TSOU T W.Ideal capacitive behavior of hydrous manganese oxide prepared by anodic deposition.Electrochem. Commun., 2002, 4(2): 105-109.
[32]	KHOMENKO V, RAYMUNDO-PI ERO E, B GUIN F. A new type of high energy asymmetric capacitor with nanoporous carbon electrodes in aqueous electrolyte. J. Power Sources, 2010, 195(13): 4234-4241.
[33]	XIAO Y, ZHANG A, LIUA S, et al.Free-standing and porous hierarchical nanoarchitectures constructed with cobalt cobaltite nanowalls for supercapacitors with high specific capacitances. J. Power Sources, 2012, 219(12): 140-146.
[34]	YAN J, FAN Z, SUN W, et al.Advanced asymmetric supercapacitors based on Ni(OH)2/graphene and porous graphene electrodes with high energy density . Adv. Funct. Mater., 2012, 22(12): 2632-2641.
[35]	LIU C L, CHANG K H, HU C C, et al.Microwave-assisted hydrothermal synthesis of Mn3O4 reduced graphene oxide composites for high power supercapacitors .J. Power Sources, 2012, 217(11): 184-192.
[36]	ZHU Y, MURALI S, STOLLER M D, et al.Carbon-based supercapacitors produced by activation of graphene.Science, 2011, 332(6037): 1537-1541.
[37]	DELL R.Batteries: fifty years of materials development.Solid State Ionics, 2000, 134(1): 139-158.
[38]	WANG H, DAI H.Strongly coupled inorganic-nano-carbon hybrid materials for energy storage. Chem. Soc. Rev., 2013, 42(7): 3088-3113.

一步合成Mn₃O₄@RGO复合材料及其非对称超级电容器的应用

One-pot Synthesis and Application in Asymmetric Supercapacitors of Mn₃O₄@RGO Nanocomposites

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