Solid-state supercapacitor based on breath figured polymethyl methacrylate deposited by graphene: the effect of electrode surface

Solid-state supercapacitors are fabricated using transparent polymethyl methacrylate (PMMA) films decorated by breath figures BF, as an electrode and polyvinyl alcohol (PVA)-H₂SO₄ as an electrolyte. The holes on the surface of the transparent PMMA created by BF method have diameters of 0.5–10 μm. Graphene is deposited by spray coating using a dispersion mixture of graphene layers. The fabricated electrodes were characterized by cyclic voltammetry (CV), galvanostatic charge–discharge, electrochemical impedance spectroscopy, charge stability and life time for evaluating their supercapacitance performance. From CV data at 5 mV/s scan rate, high specific capacitance equal to 344 for BFPMMA/G F/g and, 45 F/g for PMMA/G has been measured. By the same way, energy densities have been measured as 430 and 56.25 Wh/kg for the mentioned electrodes, respectively.     

Flexible pillared graphene-paper electrodes for high-performance electrochemical supercapacitors

Flexible graphene paper (GP) pillared by carbon black (CB) nanoparticles using a simple vacuum filtration method is developed as a high-performance electrode material for supercapacitors. Through the introduction of CB nanoparticles as spacers, the self-restacking of graphene sheets during the filtration process is mitigated to a great extent. The pillared GP-based supercapacitors exhibit excellent electrochemical performances and cyclic stabilities compared with GP without the addition of CB nanoparticles. At a scan rate of 10 mV s(-1) , the specific capacitance of the pillared GP is 138 F g(-1) and 83.2 F g(-1) with negligible 3.85% and 4.35% capacitance degradation after 2000 cycles in aqueous and organic electrolytes, respectively. At an extremely fast scan rate of 500 mV s (-1) , the specific capacitance can reach 80 F g(-1) in aqueous electrolyte. No binder is needed for assembling the supercapacitor cells and the pillared GP itself may serve as a current collector due to its intrinsic high electrical conductivity. The pillared GP has great potential in the development of promising flexible and ultralight-weight supercapacitors for electrochemical energy storage.     

Spray pyrolyzed Ni incorporated cobalt oxide thin film electrodes and their electrochemical study

Present work reports on improvements in supercapacitive performance of cobalt oxide by nickel incorporation. Nickel incorporated cobalt oxide get deposited on stainless steel at 573 K via aqueous route. The deposited samples were characterized structurally, morphologically and electrochemically by means of XRD, SEM, CV, CP and impedance. Deposited materials of all samples exhibits face centered cubic crystal structure having revolutionary morphologies. In electrochemical study all electrodes revealed mixed capacitive behavior, giving maximum specific capacitance 385.7 F/g at the scan rate 2 mV/s in 1 M KOH. Charge–discharge study depicts specific energy, specific power and columbic efficiency 9.98 Wh/kg, 2.28 kW/kg and 99.1% respectively. Electrochemical impedance study was scanned in the frequency range 1 mHz–1 MHz to search the internal resistance and capacitive behaviour of the samples.     

Electrochemical performance of conducting polymer and its nanocomposites prepared by chemical vapor phase polymerization method

In this work, conducting polymers poly(3,4-ethylenedioxythiophene) (PEDOT), PEDOT/carbon nanotubes (CNTs), and PEDOT/reduced graphene oxide (RGO) were prepared via an in situ chemical vapor phase polymerization (VPP) process. Experiment results showed that PEDOT and PEDOT nanocomposites were uniformly constructed in oxidant and oxidant nanocomposite films through a modifying template effect. The VPP PEDOT and its nanocomposites were built on aluminium film as supercapaitor electrode materials and electrochemical capacitive properties were investigated by using cycle voltammetry and charge/discharge techniques. The VPP PEDOT exhibited a specific capacitance of 92 F/g at a current density of 0.2 A/g. The VPP PEDOT composites consisting of CNTs and RGO displayed specific capacitances of 137 and 156 F/g, respectively, at the same current density. For VPP nanocomposites, more than 80 % of initial capacitance was retained after 1,000 charge/discharge cycles, suggesting a good cycling stability for electrochemical electrode materials. The good capacitive performance of the conducting polymer nanocomposites are contributed to the synergic effect of the two components.     

SnO2-reduced graphene oxide nanoribbons as anodes for lithium ion batteries with enhanced cycling stability

A nanocomposite material of SnO2-reduced graphene oxide nanoribbons has been developed. In this composite, the reduced graphene oxide nanoribbons are uniformly coated by nanosized SnO2 that formed a thin layer of SnO2 on the surface. When used as anodes in lithium ion batteries, the composite shows outstanding electrochemical performance with the high reversible discharge capacity of 1,027 mAh/g at 0.1 A/g after 165 cycles and 640 mAh/g at 3.0 A/g after 160 cycles with current rates varying from 0.1 to 3.0 A/g and no capacity decay after 600 cycles compared to the second cycle at a current density of 1.0 A/g. The high reversible capacity, good rate performance and excellent cycling stability of the composite are due to the synergistic combination of electrically conductive reduced graphene oxide nanoribbons and SnO2, The method developed here is practical for the large-scale development of anode materials for lithium ion batteries.     

Fabrication of a low defect density graphene-nickel hydroxide nanosheet hybrid with enhanced electrochemical performance

The development of efficient energy storage devices with high capacity and excellent stability is a demanding necessary to satisfy future societal and environmental needs. A hybrid material composed of low defect density graphene-supported Ni(OH)₂ sheets has been fabricated via a soft chemistry route and investigated as an advanced electrochemical pseudocapacitor material. The low defect density graphene effectively prevents the restacking of Ni(OH)₂ nanosheets as well as boosting the conductivity of the hybrid electrodes, giving a dramatic rise in capacity performance of the overall system. Moreover, graphene simultaneously acts as both nucleation center and template for the in situ growth of smooth and large scale Ni(OH)₂ nanosheets. By virtue of the unique two-dimensional nanostructure of graphene, the as-obtained Ni(OH)₂ sheets are closely protected by graphene, effectively suppressing their microstructural degradation during the charge and discharge processes, enabling an enhancement in cycling capability. Electrochemical measurements demonstrated that the specific capacitance of the as-obtained composite is high as 1162.7 F/g at a scan rate of 5 mV/s and 1087.9 F/g at a current density of 1.5 A/g. In addition, there was no marked decrease in capacitance at a current density of 10·A/g after 2000 cycles, suggesting excellent long-term cycling stability.      

Three-dimensional heterostructured MnO2/graphene/carbon nanotube composite on Ni foam for binder-free supercapacitor electrode

In this article, three-dimensional (3D) heterostructured of MnO₂/graphene/carbon nanotube (CNT) composites were synthesized by electrochemical deposition (ELD)-electrophoretic deposition (EPD) and subsequently chemical vapour deposition (CVD) methods. MnO₂/graphene/CNT composites were directly used as binder-free electrodes to investigate the electrochemical performance. To design a novel electrode material with high specific area and excellent electrochemical property, the Ni foam was chosen as the substrate, which could provide a 3D skeleton extremely enhancing the specific surface area and limiting the huge volume change of the active materials. The experimental results indicated that the specific capacitance of MnO₂/graphene/CNT composite was up to 377.1 F g^?1 at the scan speed of 200 mV s^?1 with a measured energy density of 75.4 Wh kg^?1. The 3D hybrid structures also exhibited superior long cycling life with close to 90% specific capacitance retained after 500 cycles.     

Graphene sheets decorated with ZnO nanoparticles as anode materials for lithium ion batteries

ZnO/graphene composites were synthesized using a facile solution-based method. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, thermogravimetric analysis, and Raman spectra revealed that ZnO nanoparticles with a particle size of around 4 nm were densely and homogeneously deposited on graphene sheets. As the anode material for the lithium ion batteries, the ZnO/graphene composites delivered a stable capacity of 404 mAh/g after 100 cycles at a current rate of 0.5 C, which is much superior to bare ZnO nanoparticles. The battery performance result indicates the presence of graphene sheets in the composites effectively enhance the conductivity and accommodate the volume change.     

石墨烯负载花球状二氧化锰复合材料制备及其电容性能研究

利用高锰酸钾与乙醇之间的氧化还原反应,在多孔石墨烯表面沉积纳米二氧化锰花球,获得了一种新型的复合电极材料。通过XRD,TG,SEM,TEM等分析手段确定了材料的晶体结构、化学成分、微观形貌特征。电化学性能测试表明:纳米二氧化锰花球具有优异的比电容,但是倍率性能和循环性能不足。通过在石墨烯表面负载纳米二氧化锰花球,能够显著增加石墨烯的比电容,同时改善纳米二氧化锰花球的倍率性能和循环性能。采用0.5mol/L K_2SO_4电解液,进行三电极循环伏安测试,复合电极材料在2mV·s^-1扫速下的比电容高达295F·g^-1,在1000mV·s^-1扫速下,比电容仍然可达102F·g^-1,同时100mV·s^-1,1000次循环后,电容循环保持率可达96.3%。这表明石墨烯负载花球状二氧化锰材料是一种极具潜力的超级电容器电极材料。     

Preparation of mesoporous carbon materials used in electrochemical capacitor electrode by using natural zeolite template/maltose system

Mesoporous carbons (NZMC) were synthesized by using single-step nanocasting in which maltose was used as carbon precursors and natural zeolite as template. Physical property characterization methods such as field emission scanning electron microscopy, transmission electron microscopy, N₂ absorption/desorption, and X-ray diffraction were employed to determine the structure and crystallinity of NZMC. The results show that the materials possess a disordered lamellar structure and numerous nanopores. The specific surface area and pore volume reach up to 1076.9 m²/g and 1.46 cm³/g, respectively. Typical electrochemical measurements such as constant current charge/discharge test, cyclic voltammetry (CV), and electrochemical impedance spectra revealed that NZMC has excellent charge storage capability. Specific capacitance is 176 F/g in the alkaline media when the current density is 600 mA/g. The CV curve maintains a typical CV quasi-rectangular feature at a scan rate of 5–100 mV/s, which indicates that the materials perform well rate capability. The combination resistance of the carbon materials is 0.78 Ω. After 750 cycles, the specific capacitance retention value is 94.5 %, which proves that NZMC is a promising electrode material for electrochemical capacitors because of its long-term cycle stability.     

MnO nanorods on graphene as an anode material for high capacity lithium ion batteries

The MnO/graphene hybrid nanocomposites were prepared by an in situ reduction method. The MnO₂ nanorods were attached on the graphene oxides (GOs) to form the MnO₂/GO nanocomposites, which were reduced to the MnO/graphene hybrid under argon atmosphere. As the anode material for the lithium ion batteries, the MnO/graphene electrodes delivered a high initial charge capacity up to 747 mAh g^?1 and a stable capacity of 705.8 mAh g^?1 after 100 cycles, which is much superior to pure MnO with initial charge capacity of 456 mAh g^?1 and the stable capacity of 95.6 mAh g^?1 after 100 cycles. The scanning electron microscope images of the MnO/graphene hybrid nanocomposites after cycling demonstrated that the graphene could prevent the MnO from aggregating during the charge/discharge process.     

Enhanced electrochemical capacitance of polyaniline/graphene hybrid nanosheets with graphene as templates

Polyaniline/graphene nanocomposites (PANi/GR) were prepared via PANi covalent grafting from the surface of GR. The unique structure of hybrid nanosheets was formed with uniform PANi layer coating GR without phase separation appearing when the weight ratio of aniline-to-graphene was 1:1. The unique PANi/GR hybrid nanosheets as electrode material for supercapacitors have a specific capacitance as high as 922 F/g at 10 mV/s and still retain a specific capacitance of 106 F/g at a high scan rate of 1 V/s due to synergistic effect between PANi and GR. The capacitance retention was ∼90% after 1000 cycles, which is much better than that of pure PANi or other PANi nanocomposites. The enhanced capacitive performance of PANi/GR hybrid nanosheets makes them have potential application in developing high performance energy storage devices.     

聚吡咯/氧化石墨烯复合电极的制备及性能研究

采用直流电电化学制备了聚吡咯和聚吡咯/石墨烯薄膜电极,研究发现聚吡咯/石墨烯复合电极表面产生了很多小孔和一些羊角状的结构,这可能是由于在聚合过程中,聚合围绕石墨烯吸附对甲基苯磺酸根离子形成的球状体所致。而这些小孔和羊角状的结构在电极的充放电过程中为内层聚吡咯提供了离子交换的通道。在循环伏安的测试中,当扫描速率达到1000mV/S时,聚吡咯/石墨烯复合电极的容量依然保持在229F/g,而纯的PPy电极的容量仅保持在112F/g。     

3D composites of ZnSnO<Subscript>3</Subscript> nanoplates/reduced graphene oxide aerogels as an advanced lithium-ion battery anode

Zinc-based bimetal oxides have received considerable attention as anode for lithium-ion batteries (LIBs). A one-pot self-assembly hydrothermal method is developed for the fabrication of 3D hierarchical structure aerogels from zinc stannate (ZnSnO₃) and reduced graphene oxide (rGO). 3D interconnected porous structure with ZnSnO₃ hexagon nanoplates uniformly dispersed on graphene sheets has been constructed successfully, in which the crystalline hexagon nanoplates ZnSnO₃ are firstly used to prepare ZnSnO₃-based anode materials for LIBs. The as-prepared ZnSnO₃ nanoplates/reduced graphene oxide aerogels (ZnSnO₃–rGAs) electrode demonstrates an excellent reversible capacity (780 mAh g^?1) after 200 cycles at a certain current density (100 mA g^?1) and still delivers a specific capacity of 460 mAh g^?1 even at 1000 mA g^?1. The superior performance of lithium storage is attributed to the 3D porous hierarchical structure and the synergistic effects of uniform hexagon nanoplates ZnSnO₃ and rGO sheets.     

钠离子电池TiO_2/还原氧化石墨烯负极材料的制备及储钠性能

由于钠离子半径比锂离子半径大70%,使得钠离子在石墨电极材料中脱嵌较困难,需要对石墨负极材料进行改性。以天然石墨为原料,采用Hummers法制备氧化石墨烯;在此基础上以钛酸丁酯为原料,采用溶胶-凝胶法制备了TiO_2前驱体/氧化石墨烯(TiO_2/GO)复合材料,通过热处理获得锐钛矿型TiO_2/还原氧化石墨烯(TiO_2/RGO)复合材料。电化学测试结果表明:TiO_2含量为15wt%的TiO_2/RGO复合材料在电流密度为20mA·g~(-1)下的首次放电比容量为74.08mAh·g~(-1),随着循环次数的增加,放电比容量逐渐增大,循环50次后达109.10mAh·g~(-1);充放电效率也呈现出逐渐增大的趋势,循环50次后达65.59%。而纯还原氧化石墨烯首次放电比容量为41.43mAh·g~(-1),循环50次后仅为20.47mAh·g~(-1)。     

One-pot hydrothermal synthesis of rod-like FeOOH/reduced graphene oxide composites for supercapacitor

FeOOH/reduced graphene oxide (rGO) composites have been synthesized by a facile hydrothermal method. The morphology and structure of the obtained products were examined by scanning electron microscope, Raman, X-ray diffraction, thermo gravimetric analysis, and BET. The results show that the FeOOH nanorods were formed on graphene sheets by oxidation of graphene oxide rather than the O₂ in air, and CH₃COONa benefited the growth of FeOOH rods but is not necessary. The products were about 150 nm long obtained with the existence of CH₃COONa, while 50 nm long without CH₃COONa. The FeOOH/rGO generated with CH₃COONa showed capacitance of 501.71 F/g at current density of 2 A/g in 1 mol/L NaOH, while that generated without CH₃COONa showed higher specific capacitance of 537.14 F/g. The difference may be related to the amount of rGO, for the former one contained 82.61 wt% FeOOH while the later one contained 66.13 wt% FeOOH, which indicates the quantity of rGO and the their combination played an important role in the performance of the electrode materials.     

One-step strategy to graphene/Ni(OH)2 composite hydrogels as advanced three-dimensional supercapacitor electrode materials

Graphene-based three-dimensional (3D) macroscopic materials have recently attracted increasing interest by virtue of their exciting potential in electrochemical energy conversion and storage. Here we report a facile one-step strategy to prepare mechanically strong and electrically conductive graphene/Ni(OH)₂ composite hydrogels with an interconnected porous network. The composite hydrogels were directly used as 3D supercapacitor electrode materials without adding any other binder or conductive additives. An optimized composite hydrogel containing ～82 wt.% Ni(OH)₂ exhibited a specific capacitance of ～1,247 F/g at a scan rate of 5 mV/s and ～785 F/g at 40 mV/s (～63% capacitance retention) with excellent cycling stability. The capacity of the 3D hydrogels greatly surpasses that of a physical mixture of graphene sheets and Ni(OH)₂ nanoplates (～309 F/g at 40 mV/s). The same strategy was also applied to fabricate graphene-carbon nanotube/Ni(OH)₂ ternary composite hydrogels with further improved specific capacitances (～1,352 F/g at 5 mV/s) and rate capability (～66% capacitance retention at 40 mV/s). Both composite hydrogels obtained here can deliver high energy densities (～43 and ～47 Wh/kg, respectively) and power densities (～8 and ～9 kW/kg, respectively), making them attractive electrode materials for supercapacitor applications. This study opens a new pathway to the design and fabrication of functional 3D graphene composite materials, and can significantly impact broad areas including energy storage and beyond.      

Chemical adsorption of NiO nanostructures on nickel foam-graphene for supercapacitor applications

Few-layer graphene was synthesized on a nickel foam template by chemical vapor deposition. The resulting three-dimensional (3D) graphene was loaded with nickel oxide nanostructures using the successive ionic layer adsorption and reaction technique. The composites were characterized and investigated as electrode material for supercapacitors. Raman spectroscopy measurements on the sample revealed that the 3D graphene consisted of mostly few layers, while X-ray diffractometry and scanning electron microscopy revealed the presence of nickel oxide. The electrochemical properties were investigated using cyclic voltammetry, electrochemical impedance spectroscopy, and potentiostatic charge–discharge in aqueous KOH electrolyte. The novelty of this study is the use of the 3D porous cell structure of the nickel foam which allows for the growth of highly conductive graphene and subsequently provides support for uniform adsorption of the NiO onto the graphene. The NF-G/NiO electrode material showed excellent properties as a pseudocapacitive device with a high-specific capacitance value of 783 F g^?1 at a scan rate of 2 mV s^?1. The device also exhibited excellent cycle stability, with 84 % retention of the initial capacitance after 1000 cycles. The results demonstrate that composites made using 3D graphene are versatile and show considerable promise as electrode materials for supercapacitor applications.     

Fe_3O_4-ODA/GO/PANI复合材料的制备及其电容性能

在当今能源紧缺的情况下,超级电容器由于具有功率密度高、充放电时间短、循环寿命长等优点而被广泛应用于工业自动化控制、电力、国防以及新能源汽车等众多领域。本文以十八胺修饰的四氧化三铁纳米粒子(Fe_3O_4-ODA),氧化石墨烯(GO)以及苯胺单体为原料,通过原位聚合成功制备了Fe_3O_4-ODA/GO/PANI三元复合电极材料,其比电容高达516F/g,远高于二元复合材料GO/PANI和Fe_3O_4-ODA/PANI的比电容(分别为224F/g和345F/g)。并且,在1000次循环充放电之后,其容量仍可维持86.5%。此外,利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线粉末衍射(XRD)和傅立叶变换红外光谱仪(FT-IR)等手段对该复合材料的形貌和结构进行了表征。     

对苯二酚增强纤维素/石墨烯电极的制备

目的 以纳米纤维素气凝胶为骨架,对苯二酚为增强相,并加入还原氧化石墨烯,制备纳米纤维素/还原氧化石墨烯复合电极薄膜,将其应用于超级电容器。方法 采用超声处理制备纳米纤维素/氧化石墨烯混合溶液;在高温高压的环境下,加入对苯二酚,采用水热合成法和冷冻干燥法制备纳米纤维素/还原氧化石墨烯气凝胶,并最终制成电极膜。结果 在纳米纤维素/还原氧化石墨烯复合气凝胶中,石墨烯可将纳米纤维素均匀包裹,形成三维多孔网络结构;纳米纤维素/还原氧化石墨烯复合电极具有良好的电化学性能,在1 mol/L的H2SO4溶液中,当电流扫描速率为1 mA/cm2时,超级电容器比面积电容高达1.621 F/cm2,且在2000次循环测试后,电容保留率为88.3％。结论 以纳米纤维素为基体制备的纳米纤维素/还原氧化石墨复合电极具有良好的电化学性能,可以用作超级电容器电极。