三维筋撑石墨烯负载氧化锰的超级电容器

石墨烯基超级电容器,其功率密度较高,但能量密度受限。开发以三维石墨烯材料为载体的复合型赝电容多孔电极,是解决方案之一。本文采用铵盐辅助化学发泡法,制备了三维筋撑石墨烯泡沫体(SG);以SG为载体,采用水热还原法在其表面生长二氧化锰(MnO₂)纳米棒阵列,从而构建了MnO₂/SG自支撑多孔材料。利用MnO₂/SG复合电极,组装了超级电容器,在0.5 A·g^-1的电流密度下,比电容达343.6 F·g^-1;经5000次循环,其容量保持率为83.8%;在500 W·kg^-1的功率密度下,其能量密度达11.93 W·h·kg^-1。因此,MnO₂/SG复合电极是一种性能优异的赝电容材料,在电化学储能领域有良好的应用前景。     

Spray dryer processed graphene oxide/reduced graphene oxide for high-performance supercapacitor

This study deals with the utility of mini spray dryer process to improve the dispersibility, of graphene oxide(GO) and its application for high-performance supercapacitor. Initially, the neutral solution of GO was obtained using the modified Hummer's method. After this, the prepared GO solution was processed by mini spray dryer to obtain a more purified, lighter, and dispersed form of GO which is named as spray dryer processed GO (SPGO). The SPGO thus obtained showed excellent dispersibility behavior with various solvents, which is not found in case of conventional oven drying. Furthermore, utility of SPGO and its reduced form (r-SPGO) for supercapacitor applications have been investigated. Results obtained from the cyclic voltammetry(CV) analysis, impedance, and charge-discharge behavior of supercapacitor fabricated using r-SPGO shows enhanced features. Therefore, the simple spray dried GO and its reduced form, that is, r-SPGO can be utilized as a potential candidate for the supercapacitor application. Herein, as synthesized SPGO exhibited the specific capacitance of 12.07 and 37.6 F/g with PVA-H₃PO₄ and 1 mol/L H₃PO₄, respectively, at a scan rate of 5 mV/s. On the other hand, reduced form of SPGO, that is, r-SPGO showed the specific capacitance of 27.16 and 230 F/g with PVA-H₃PO₄ and 1 mol/L H₃PO₄, respectively.     

Bifunctional ternary manganese oxide/vanadium oxide/reduced graphene oxide as electrochromic asymmetric supercapacitor

A bifunctional ternary manganese oxide/vanadium oxide/reduced graphene oxide (MnO₂/V₂O₅/rGO) was developed for asymmetric electrochromic supercapacitor (EC-SC) application. The elemental mapping revealed uniformly distributed MnO₂, V₂O₅ and rGO, depicting homogenous synthesis of the hybrid composite. The phase composition, vibration modes and valance state of the ternary composite were analyzed via X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis, respectively. Interestingly, the as-prepared MnO₂/V₂O₅/rGO composite disclosed tremendous C_sp of 1403.5 F/g, which was higher compared to MnO₂/V₂O₅ (801.1 F/g), V₂O₅ (613.1 F/g), MnO₂ (126.7 F/g) and rGO (60.7 F/g). MnO₂/V₂O₅/rGO that appeared in dark green switched its visual color to orange at the charged state, confirming the electrochromic property. The bifunctional manganese oxide/vanadium oxide/reduced graphene oxide//copper-based metal-organic framework/reduced graphene oxide (MnO₂/V₂O₅/rGO//MrGO) asymmetrical EC-SC device revealed outstanding cycling stability (90.3% charge retention over 5000 cycles), tremendous specific capacitance (652.7 F/g) and maximum specific energy (60.4 Wh/kg). MnO₂/V₂O₅/rGO//MrGO asymmetrical EC-SC device demonstrated reversible color changes from dark green to orange at the discharged and charged states, respectively. The significantly great electrochromic and supercapacitive performance revealed that MnO₂/V₂O₅/rGO//MrGO is an outstanding electroactive candidate for the next generation of electrochromic supercapacitors.     

Vertically oriented polyaniline‐graphene nanocomposite based on functionalized graphene for supercapacitor electrode

Polyaniline functionalized reduced graphene oxide (PORGO) is prepared by interfacial polymerization and then vertically oriented polyaniline‐graphene (PANI‐PORGO) nanocomposites based on PORGO are developed successfully by in situ polymerization. The morphology and structure are characterized by field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT‐IR), Raman spectra and X‐ray diffraction (XRD). The electrochemical tests indicate that the specific capacitance of PORGO and PANI‐PORGO is as high as 291 and 369 F/g, respectively, at the current density of 1 A/g. PANI—PORGO nanocomposite exhibits high electrochemical activity and enhanced cycle stability with a capacitance retention of 81.2% after 500 cycles at 10 A/g. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44808.     

Three-dimensional oxygen-doped porous graphene: Sodium chloride-template preparation,structural characterization and supercapacitor performances

Supercapacitor is a new type of energy storage device, which has the advantages of high-power property and long cycle life. In this study, three-dimensional graphene (3D-GN) with oxygen doping and porous structure was prepared from graphene oxide (GO) by an inexpensive sodium chloride (NaCl) template, as a promising electrode material for the supercapacitor. The structure, morphology, specific surface area, pore size, of the sample were characterized by XRD, SEM, TEM and BET techniques. The electrochemical performances of the sample were tested by CV and CDC techniques. The 3D-GE product is a three-dimensional nano material with hierarchical porous structures, its specific surface area is much larger than that of routine stacked graphene (GN), and it contains a large number of mesoporous and macropores, a small amount of micropores. The capacitance characteristics of the 3D-GN electrode material are excellent, showing high specific capacitance (173.5 F·g^-1 at 1 A·g^-1), good rate performance (109.2 F·g^-1 at 8 A·g^-1) and long cycle life (88% capacitance retention after 10,000 cycles at 8 A·g^-1)     

3D石墨烯/导电聚合物气凝胶复合材料在超级电容器中的研究进展

分析了近年来超级电容器电极材料尤其是3D石墨烯/导电聚合物气凝胶复合电极材料在超级电容器方面的研究进展,详细介绍了目前3D石墨烯气凝胶的制备方法,总结了3D石墨烯/导电聚合物气凝胶复合材料的不足和在存储领域的发展方向.     

三维有序结构聚苯胺/石墨烯纳米复合材料的制备及其在超级电容器电极中应用

用硼氢化钠(NaBH_4)还原氧化石墨烯得到还原石墨烯(rGO)分散液,rGO分散液与苯胺在酸性条件下原位聚合得到高比表面积三维有序结构的聚苯胺/石墨烯纳米复合材料。由场发射扫描电镜(FESEM)、透射电镜(TEM)、X射线光电子能谱(XPS)和X射线衍射(XRD)对其表面形貌和结构进行表征。结果表明:复合材料的比表面积高达136.9 m~2/g,高于纯聚苯胺的比表面积(32.71 m~2/g);直径10~20 nm的聚苯胺纳米棒均匀地垂直生长在石墨烯表面。在0.5 A/g的电流密度下,复合材料比电容达到358 F/g,大于石墨烯和聚苯胺的比电容;当充放电电流密度由0.5 A/g增加到10 A/g时,电容保留率达74.3%,表现出增强的倍率性能;在10 A/g高电流密度下,经过500次的充放电循环后容量保持率达到83.7%。     

石墨烯/δ-MnO2复合材料的制备及其超级电容器性能

采用螯合法制备了RGO/δ-MnO₂复合材料,并用X射线粉末衍射（XRD）、低压氮气吸附脱附（BET）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、能谱（EDS）、热重（TGA）对其结构和物相进行表征。采用循环伏安测试（CV）、恒电流充放电（GCD）以及循环测试对所制材料电化学储能进行测试。结果表明RGO/δ-MnO₂复合材料比纯石墨烯和纯δ-MnO₂具有更优异的电化学性能。当电流密度为1 A·g^-1时,RGO/δ-MnO₂复合材料的比电容可达322.6 F·g^-1,比纯δ-MnO₂电极材料高234.2 F·g^-1,比纯石墨烯高212.1 F·g^-1。当电流密度放大10倍后,RGO/δ-MnO₂复合材料的比电容保留率为79.1%。在1000次恒流充放电测试后,比电容为252 F·g^-1（99.6%）,说明该方法制备的RGO/δ-MnO₂复合材料是一种有应用前景的超级电容器电极材料。     

Three-dimensional graphene layers prepared by a gas-foaming method for supercapacitor applications

Inspired by baking bread, our research group demonstrates a novel method for baking three-dimensional (3D) graphene layers with an open porous network, pore size in the range of dozens of nanometers to several hundred nanometers, and a pore wall thickness of about 10 nm. Such continuously cross-linking structures not only effectively overcome the restacking and agglomeration of graphene nanosheets but also possess more channels between nanosheets to lower the resistance for electron access to the inter-space. Compared with reduced graphene oxide (rGO) prepared at the same temperature, the unique 3D porous-structured graphene layers also contain 4.3 at.% nitrogen. When the 3D graphene layers are employed as an active electrode material for a supercapacitor, a high specific capacitance (SC) of 231.2 F g⁻¹ at 1 A g⁻¹ is displayed after electrochemical activation, approximately two times that of rGO. Only <1.0% of the capacitance degrades after 8000 cycles, exhibiting its excellent cycle stability; furthermore, it liberates a high energy density of 32.1 Wh kg⁻¹ at a power density of 500 W kg⁻¹. The attractive performances of 3D graphene layers make them a promising candidate as an electrode material for supercapacitors.     

Silver nanoparticles decorated polypyrrole/graphene nanocomposite: A potential candidate for next‐generation supercapacitor electrode material

In the present study, we report a simple method to synthesize silver (Ag)‐polypyrrole (PPy)/graphene (Gr) nanocomposite as efficient electrode materials for supercapacitor application. The probable interaction between Ag nanoparticles with both PPy and Gr were characterized by FTIR, UV–visible, and Raman spectroscopies. The morphological analysis confirmed that the Gr sheets are uniformly coated by PPy and in the coated Gr sheets there is the presence of Ag nanoparticles. The Ag‐PPy/Gr nanocomposite achieved the highest specific capacitance of 472 F/g at a 0.5 A/g current density. Better energy and power density also obtained for the nanocomposite. The presence of both Ag nanoparticles and Gr is the main reason for the enhancement of the electrochemical properties of the nanocomposite. Based on the superior electrochemical properties, the nanocomposite can be used for next‐generation supercapacitor electrode material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44724.     

石墨烯/聚吡咯复合电极材料超电容性能研究进展

分析了目前石墨烯和聚吡咯(PPy)用作电极材料的不足,详细介绍了近年来超级电容器用石墨烯/PPy复合电极材料的研究进展,指出石墨烯/PPy复合材料在能量转换和存储领域的未来发展方向.     

Nano graphene porous/conductive polymer as a composite material for energy storage in supercapacitors

This research studies the improving effects of graphene porous (GP) on the supercapacitive performance of a polyaniline/graphene porous (PANI/GP) nanocomposite. GP nanosheets were synthesized via chemical vapor deposition, and PANI/GP was electrochemically composited through successive cyclic voltammetry. The samples were characterized by fast Fourier transform infrared (FTIR), x-ray diffraction (XRD), and scanning electron microscopy (SEM), and energy-dispersive x-ray spectrometry (EDS) techniques. Porous GP nanosheets were uniformly dispersed in the composite structure. Furthermore, the electrochemical performances of the synthesized samples were compared using galvanostatic charge/discharge, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). Incorporating GP into the PANI significantly increased specific capacitance from 276 (in PANI) to 577 F/g (in PANI/GP). The electrochemical stability of electrodes was compared during 1000 successive charge/discharge cycles. After 1000 cycles, PANI/GP kept 90% of its initial capacitance, and only 25% of the charge storage capacitance of bare PANI remained.     

纤维素基生物质多孔炭的制备及其超级电容器性能研究

以棉纤维素为原料,采用硝酸盐、尿素、纤维素共混后热裂解的方法制备分级多孔炭HPC样品,通过改变煅烧温度和KOH活化处理对多孔炭比表面积及孔结构进行调控。对比三个不同温度煅烧活化处理后样品的循环伏安曲线、恒电流充放电曲线、比容量等电化学参数,结果表明,4AC@HPC800样品作为超级电容器工作电极具有优良的电化学性能,其比表面积高达2433.8 m²·g^-1,在1 A·g^-1的电流密度下比容量高达234.7 F·g^-1,在大电流密度10 A·g^-1时依然有207.6 F·g^-1的比容量,具有良好的倍率性能;电极在2 A·g^-1的电流密度下循环10000次后依然有196.1 F·g^-1的比容量,表明其具有长时工作的特性。     

氧化石墨烯的酸性还原及其超级电容性能

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。     

纤维素基生物质多孔炭的制备及其超级电容器性能研究

以棉纤维素为原料,采用硝酸盐、尿素、纤维素共混后热裂解的方法制备分级多孔炭HPC样品,通过改变煅烧温度和KOH活化处理对多孔炭比表面积及孔结构进行调控。对比三个不同温度煅烧活化处理后样品的循环伏安曲线、恒电流充放电曲线、比容量等电化学参数,结果表明,4AC@HPC800样品作为超级电容器工作电极具有优良的电化学性能,其比表面积高达2433.8 m²·g^-1,在1 A·g^-1的电流密度下比容量高达234.7 F·g^-1,在大电流密度10 A·g^-1时依然有207.6 F·g^-1的比容量,具有良好的倍率性能;电极在2 A·g^-1的电流密度下循环10000次后依然有196.1 F·g^-1的比容量,表明其具有长时工作的特性。     

MOFs基材料在超级电容器中的应用

金属有机骨架材料（MOFs）多样的组成与结构、高的比表面积和丰富的孔结构等优势,使其逐渐成为高性能电化学储能与转换电极材料研究的热点之一。本文主要介绍了MOFs在超级电容器中的应用研究,阐述了MOFs自身及其复合材料和衍生物（多孔碳、金属硫化物及氧化物）在超级电容器材料应用领域的研究进展,讨论了MOFs基超级电容器的结构特征及其在电化学储能领域中展现出特殊的性质和新颖的功能,提出了MOFs构筑的超级电容器在新能源储存与转换领域发挥的重要作用,最后对MOFs基超级电容器自身结构稳定性差、导电率偏低及其实际应用受限进行了分析。     

Cauliflower-like poly(3,4-ethylenedioxythipohene)/nanocrystalline cellulose/manganese oxide ternary nanocomposite for supercapacitor

A cauliflower-like ternary nanocomposite of poly(3,4-ethylenedioxythipohene)/nanocrystalline cellulose/manganese oxide (PEDOT/NCC/MnO₂) was synthesized using one-step electropolymerization technique. The effect of manganese (Mn) concentration on the supercapacitive performance was investigated. The structural and morphology studies were conducted using field emission scanning electron microscope, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray diffraction. The morphology of ternary nanocomposite at an optimized concentration of Mn resembles the cauliflower-like structure. The two-electrode electrochemical analysis of a ternary nanocomposite PEDOT/NCC/MnO₂ exhibited a higher specific capacitance of 144.69 F/g at 25 mV/s in 1.0 M potassium chloride compared to PEDOT/NCC(63.57 F/g). PEDOT/NCC/MnO₂ ternary nanocomposite was able to deliver a specific power of 494.9 W/kg and 10.3 Wh/kg of specific energy at 1 A g⁻¹ and retained 83% of initial capacitance after 2,000 cycles. These promising results from the incorporation of Mn displayed great prospective in developing PEDOT/NCC/MnO₂ as an electrode material for supercapacitor.     

Reduced graphene oxide–poly(methyl methacrylate) nanocomposite as a supercapacitor

An exhaustive study on a nanocomposite–poly(methyl methacrylate) matrix material as a supercapacitor is presented. The study includes morphological, structural, and electrochemical characterization. Different electrolytes were used, for which both pseudocapacitance (for reduced graphene oxide) and electric double‐layer capacitance (for functionalized graphene) were observed. An optimum nanocomposite weight percentage was found (2%), and the best performance with highest capacitance (30.4 F/g) was seen for the electrolyte including the smallest anions (OH^?), being among the best values for similar systems, that is, a nanocomposite/nonconductive polymer matrix. In addition, a model is presented that explains the underlying electron transport mechanism. The results are promising for the construction of supercapacitors based on novel nanocomposite–poly(methyl methacrylate) matrix materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46685     

离子组成对氧化石墨烯在饱和多孔介质中迁移行为的影响

采用室内饱和石英砂柱一维渗流模拟实验,研究离子强度相同、离子组成(钠吸附比)不同的电解质溶液对氧化石墨烯(GO)在地下环境中迁移行为的影响。通过测定GO穿透过程的沉积动力学曲线,结合数学模型与界面化学理论,对其迁移沉积机理进行分析。结果显示,当钠吸附比从0增加到∞时,砂柱出流最大浓度升高,GO回收率增加,穿透实验沉积速率、去除效率和吸附效率分别从0.356 min^-1、1.04×10^-2、0.054减小到0.039 min^-1、1.1×10^-3、0.003。研究认为布朗扩散是造成GO颗粒与石英砂粒相互接触的主要机制,Ca²⁺浓度变化是造成不同钠吸附比环境下GO不同迁移行为的主要因素,其机理在于Ca²⁺与GO发生电中和与桥接作用,改变了颗粒间的静电斥力与引力平衡,进而影响了GO颗粒粒度与形态,并最终强化了砂柱对GO的截留效应。