Electrochemical capacitors based on the composite of graphene and nickel foam

An improved Hummers method was developed for the simple and efficient production of high-quality graphene oxide(GO), and the composite of GO and nickel foam(NF)(GO/NF) was fabricated by ultrasonication-vacuum-assisted deposition of an aqueous solution of GO on NF. After chemical or thermal reduction, the composite of reduced GO and nickel foam(r GO/NF) was obtained. The electrochemical capacitance performance of r GO/NF was investigated using cyclic voltammetry and galvanostatic charge/discharge measurements. The chemically reduced r GO/NF composite(C-r GO/NF) exhibited high specific capacitance of 379 F/g at 1.0 A/g and 266.5 F/g at 10 A/g. We also prepared thermally reduced graphene oxide at 473 K in order to illuminate the difference in effect between the chemical and low-temperature thermal reduction methods on electrochemical properties. The cycling performance of thermally reduced r GO/NF composite(T-r GO/NF) and C-r GO/NF had ~91% and ~95% capacitance retention after 2000 cycles in a 6 mol/L KOH electrolyte, respectively. Electrochemical experiments indicated that the obtained r GO/NF has very good capacitive performance and could be used as a potential application of electrochemical capacitors. Our work revealed high electrochemical capacitor performance of r GO/NF composite and provided a facile method of r GO/NF preparation.     

Facile synthesis of high electrical conductive CoP via solid-state synthetic routes for supercapacitors

Co-P precursor was prepared by a mechanical alloying method and then is controlled to synthesis of Co P phase through an annealing method. The optimal conditions of ball milling and annealing temperature are investigated. The Co P exhibits higher electrical conductivity than graphite and cobalt oxide, showing excellent pseudocapacitive properties due its high electrical conductivity which can result in a fast electron transfer in high rate charge–discharge possess. The as-obtained Co P electrode achieves a high specific capacitance of 447.5 F/g at 1 A/g, and displays an excellent rate capability as well as good cycling stability. Besides, the asymmetric supercapacitor(ASC) based on the Co P as the positive electrode and activated carbon(AC) as the negative electrode was assembled and displayed a high rate capability(60%of the capacitance is retained when the current density increased from 1 A/g to 12 A/g), excellent cycling stability(96.7% of the initial capacitance is retained after 5000 cycles), and a superior specific energy of19 Wh/kg at a power density of 350.8 W/kg. The results suggest that the Co P electrode materials have a great potential for developing high-performance electrochemical energy storage devices.     

Core@shell sulfur@polypyrrole nanoparticles sandwiched in graphene sheets as cathode for lithium–sulfur batteries

A nano sulfur-based composite cathode material featured by uniform core@shell-structured sulfur@polypyrrole nanoparticles sandwiched in three-dimensional graphene sheets conductive network(S@PPy/GS) is fabricated via a facile solution-based method. The S@PPy nanoparticles are synthesized by in situ chemical oxidative polymerization of pyrrole on the surface of sulfur particles,and then graphene sheets are covered outside the S@PPy nanoparticles,forming a three-dimensional conductive network. When evaluating the electrochemical performance of S@PPy/GS in a lithium–sulfur battery,it delivers large discharge capacity,excellent cycle stability,and good rate capability. The initial discharge capacity is up to 1040 m Ah/g at 0.1 C,the capacity can remain 537.8 m Ah/g at 0.2 C after 200 cycles,even at a higher rate of 1 C,the specific capacity still reaches 566.5 m Ah/g. The good electrochemical performance is attributed to the unique structure of S@PPy/GS,which can not only provide an excellent transport of lithium and electron ions within the electrodes,but also retard the shuttle effect of soluble lithium polysulfides effectively,thus plays a positive role in building better lithium-sulfur batteries.     

Synthesis and Electrochemical Performance of Co3O4/Graphene

Co3O4/reduced graphene oxide composites were synthesized via a simple electrochemical method from graphene oxide and Co（NO3）2·6H2O as raw materials.Co3O4 nanoparticles with sizes of around 30-50 nm were distributed on the surface of graphene nanosheets confirmed by scanning electron microscopy and transmission electron microscopy.Electrochemical properties of Co3O4/graphene composite were tested by cyclic voltammetry,galvanostatic charge-discharge,and electrochemical impedance spectroscopy.The Co3O4/reduced graphene oxide composite was used as the pseudocapacitor electrode in the 2 mol/L NaOH aqueous electrolyte solution.The Co3O4/reduced graphene oxide composite electrode exhibited a specific capacitance of 357 F/g at a current density of 0.5 A/g in a three-electrode system.72％ of capacitance was retained when the current density increased to 3 A/g.The Co3O4/reduced graphene oxide composite prepared electrodes show a high rate capability and excellent long-term stability.After 1000 cycles of charge and discharge,the capacitance is still maintained 87％ at a current density of 1 A/g,indicating that the composite is a oromising alternative electrode material used for supercapacitors.     

Secondary Activation of Commercial Activated Carbon and its Application in Electric Double Layer Capacitor

The cheap commercial activated carbon (AC) was improved through the secondary activation under steam in the presence of FeCl2 catalyst in the temperature range of 800-950℃ and its application in electric double layer capacitors(EDLCs) with organic electrolyte was studied. The re-acivation of AC results in the increases in both specific capacitance and high rate capability of DELCs. For AC treated under optimized conditions, its discharge specific capacitance increases up to 55.65F/g, an increase of about 33% as compared to the original AC, and the high rate capability was increased significantly.The good performances of EDLC with improved AC were correlated to the increasing mesoporous ratio.     

Microporous carbon nanofibers prepared by combining electrospinning and phase separation methods for supercapacitor

Microporous carbon nanofibers(MCNFs) derived from polyacrylonitrile nanofibers were fabricated via electrospinning technology and phase separation in the presence of polyvinylpyrrolidone(PVP).PVP together with a mixed solvent of N,N-Dimethylformamide and dimethyl sulfoxide was used as poreforming agent.The influences of PVP content in casting solution on the structure and electrochemical performance of the MCNFs were also investigated.The highest capacitance of 200 F/g was obtained on a three-electrode system at a scan rate of 0.5 A/g.The good performance was owing to the high specific surface area and the large amount of micro-pores,which enhanced the absorption and the transportation efficiency of electrolyte ion during charge/discharge process.This research indicated that the combination of electrospinning and phase separation technology could be used to fabricate microporous carbon nanofibers as electrode materials for supercapacitors with high specific surface area and outstanding electrochemical performance.     

Preparation of nano-PANI@MnO_2 by surface initiated polymerization method using as a nano-tubular electrode material:The amount effect of aniline on the microstructure and electrochemical performance

In this study,nano-polyanline and manganese oxide nanometer tubular composites(nano-PANI@MnO2)were prepared by a surface initiated polymerization method and used as electrochemical capacitor electrode materials; and the effect of aniline amount on the microstructure and electrochemical performance was investigated. The microstructures and surface morphologies of nano-PANI@MnO2 were characterized by X-ray diffraction,scanning electron microscopy and fourier transformation infrared spectroscope. The electrochemical performance of these composite materials was performed with cyclic voltammetry,charge–discharge test and electrochemical impedance spectroscopy,respectively. The results demonstrate that the feed ratio of aniline to MnO2 played a very important role in constructing the hierarchically nano-structure,which would,hence,determine the electrochemical performance of the materials. Using the templateassisted strategy and controlling the feed ratio of aniline to MnO2,the nanometer tubular structure of nanoPANI@MnO2 was obtained. A maximum specific capacitance of 386 F/g was achieved in aqueous 1 mol/L Na NO3 electrolyte with the potential range from 0 to 0.6 V(vs. SCE).     

Facile Synthesis of Bi2MoO6 Nanosheets@Nitrogen and Sulfur Codoped Graphene Composites for Sodium-ion Batteries

Recently,sodium-ion batteries gradually become the promising alternative to lithium-ion batteries because of cost considerations.In this work,a kind of Bi2MoO6 nanosheets@N,S codoped graphene composite is designed and fabricated for sodium storage applications.Detailed characterizations are employed to investigate its morphology,structure and chemical compositions.When evaluated as an anode material for sodium-ion batteries,the as-prepared composite is able to display a specific capacity of 254 mA·h/g after 50 cycles at a current density of 0.2 A/g,and 186 mA·h/g at 1.6 A/g during the rate capability test.As a result,the further morphology and structure optimization is still required for high performance sodium-ion batteries.     

Boosting the Energy Density of Flexible Asymmetric Supercapacitor with Three Dimensional Fe2O3 Composite Brush Anode

Flexible asymmetric supercapacitor is fabricated with three dimensional(3D)Fe2O3/Ni(OH)2 composite brush anode and Ni(OH)2/MoO2 honeycomb cathode.Particularly for 3D composite brush anode,a layer of thin Fe2O3 film is firmly adhered on a 3D Ni brush current collector with the assist of Ni(OH)2,functioning as both adherence layer and pseudocapacitive active material.The unique 3D Ni brush current collector possesses large surface area and stretching architecture,which facilitate to achieve the composite anode with high gravimetric capacitance of 2158 F/g.In terms of cathode,Ni(OH)2 and MoO2 have a synergistic effect to improve the specific capacitance,and the resulting Ni(OH)2/MoO2 honeycomb cathode shows a very high gravimetric capacitance up to 3264 F/g.The asymmetric supercapacitor(ASC)has balanced cathode and anode,and exhibits an ultrahigh gravimetric capacitance of 1427 F/g and an energy density of 476 W·h/kg.The energy density of ASC is 3-4 times higher than those of other reported aqueous electrolyte-based supercapacitors and even comparable to that of commercial lithium ion batteries.The device also shows marginal capacitance degradation after 1000 cycles'bending test,demonstrating its potency in the application of flexible energy storage devices.     

Self-standing rationally functionalized graphene as high-performance electrode materials for supercapacitors

Supercapacitors（SCs） have attracted much attention as one of the alternative energy devices due to their high power performance,long cycle life,and low maintenance cost.Graphene is considered as an innovative and promising material due to its large theoretical specific surface area,high electrical conductivity,good mechanical properties and chemical stability.Herein,we report an effective strategy for elaborately constructing rationally functionalized self-standing graphene（SG） obtained from giant graphene oxide（GGO） paper followed by an ultrarapid thermal-processing.This treatment results in both the exfoliation of graphene sheets and the reduction of GGO by elimination of oxygencontaining groups.The as-prepared SG electrode materials without additive and conducting agent provide an excellent combination of the electrical double layer capacitor（EDLC） and pseudocapacitor（PC） functions and exhibit superior electrochemical performance,including high specific capacitance,good rate capability and excellent cycling stability when investigated in three-electrode electrochemical cells.     

Enhanced Capacitive Characteristics of Activated Carbon by Secondary Activation

The effect of the improvement of commercial activated carbon(AC) on its specific capacitance and high rate capability of double layer(dl) charging/discharging process has been studied. The improvement of AC was carried out via a secondary activation under steam in the presence of catalyst NiCl2, and the suitable condition was found to be a heat treatment at about 875 ℃ for 1 h. Under those conditions, the discharge specific capacitance of the improved AC increases up to 53. 67 F/g, showing an increase of about 25% as compared with that of as-received AC. The good rectangular-shaped voltammograms and A.C. impedance spectra prove that the high rate capability of the capacitor made of the improved AC is enhanced significantly. The capacitance resistance (RC) time constant of the capacitor containing the improved AC is 1.74 s, which is much lower than that of the one containing as-received AC(an RC value of 4. 73 s). It is noted that both kinds of AC samples show a similar specific surface area and pore size distribution, but some changes have taken place in the carbon surface groups, especially a decrease in the concentration of surface carbonyl groups after the improvement, which have been verified by means of X-photoelectron spectroscopy. Accordingly, it is suggested that the decrease in the concentration of surface carbonyl groups for the improved AC is beneficial to the organic electrolyte ion penetrating into the pores, thus leading to the increase in both the specific capacitance and high rate capability of the supercapacitor.     

NiCo_2O_4 decorated PANI–CNTs composites as supercapacitive electrode materials

Hierarchical Ni Co_2O_4/PANI/CNTs hybrid composites were designed and fabricated having a layer of Ni Co_2O_4 on the surface of PANI encapsulated CNTs with different morphologies. Physicochemical attributes of the synthesized composites were examined by FTIR, UV–visible and X-ray diffraction(XRD)techniques. Morphological aspects were evaluated by field-emission scanning microscopy(FESEM),electron diffraction spectroscopy(EDS), high resolution transmission electron microscopy(HRTEM) and selected area electron diffraction(SAED) studies. Electrochemical measurements revealed an improved specific capacitance of 2250 F/g at a scan rate of 5 m V/s and 2000 F/g at a current density of 1 A/g with good rate capability using a three-electrode system. These enhanced features are achieved from the well designed nanostructure and the synergistic contributions of individual components in the electrode material.     

The pseudocapacitance mechanism of graphene/CoAl LDH and its derivatives:Are all the modifications beneficial?

Cobalt-Aluminum layered double hydroxide(CoAl LDH) is a hopeful electrode material due to the advantage of easy modifiability for preparing LDH-based derivatives.However,there is short of modification methods to prepare the Co-based derivatives from CoAl LDH and also short of an intuitive perspective to analyze the pseudocapacitance mechanism of CoAl LDH and its derivatives.Herein,Graphene/CoAl LDH and its derivatives including Graphene/CoS,Graphene/CoS-1,Graphene/CoOOH,Graphene/CoP were prepared by reasonably using alkali etching treatment,sulfofication and phosphorization.The specific capacitance of Graphene/CoAl LDH,Graphene/CoS,Graphene/CoS-1,Graphene/CoOOH,Graphene/CoP at1 A g^-1 are 260.7,371.3,440.8,61.4 and 122.2 F g^-1,especially.The pseudocapacitance mechanism of Graphene/CoAl LDH and its derivatives was analyzed.Due to the positive effect of sulfofication on the electrical conductivity of GO and cobalt sulfide,the Graphene/CoS and Graphene/CoS-1 exhibit the optimal electrochemical performance and superior rate capability.In addition,due to the repulsion effect between Graphene and OH-,the Graphene/CoAl LDH exhibits optimal cycling stability of 224.1% capacitance retention after 20000 cycles.Besides,the reason of terrible specific capacitance of Graphene/CoOOH is that the presence of H bond in interlayer of CoOOH inhibits the interaction between Co3+ and OHspecies.Hence,not all modifications will increase the specific capacitance of the electrode materials.Overall,this work provides us with a detailed analysis of the electrochemical mechanism and correlation of CoAl LDH and its derivatives from the perspective of crystal structure and composition.     

A bird nest-like manganese dioxide and its application as electrode in supercapacitors

A novel bird nest-like nanostructured MnO2(BNNS-MnO2) was prepared by a facile and cost-effective strategy. Their structures and morphologies were characterized by field emission scanning electron microscopy, transmission electron microscopy and powder X-ray diffraction. Capacitive behaviors were investigated by cyclic voltammetry and galvanostatic charge-discharge. The obtained nano-MnO2 possesses a well designed loose-assembled hierarchical nanoarchitecture with an appropriate crystallinity which gives rise to excellent performances as an electrode material for supercapacitors. A maximum specific capacitance of 917 F/g has been obtained at a current density of 5 mA/cm2 in 6 mol/L KOH aqueous solution, and a specific capacitance of 210 F/g has been maintained for 500 cycles. As the low cost of MnSO4 and KCr2O7 and the low reaction temperature, the present method avoids the requirements for complicated operations, time/energy-consuming and expensive reagents, and perhaps is ready for the industrialization of nano-MnO2 production.     

KOH activated carbon derived from biomass-banana fibers as an efficient negative electrode in high performance asymmetric supercapacitor

Here we demonstrate the fabrication, electrochemical performance and application of an asymmetric supercapacitor(AS) device constructed with β–Ni(OH)_2/MWCNTs as positive electrode and KOH activated honeycomb-like porous carbon(K-PC) derived from banana fibers as negative electrode. Initially,the electrochemical performance of hydrothermally synthesized β–Ni(OH)_2/MWCNTs nanocomposite and K-PC was studied in a three-electrode system using 1 M KOH. These materials exhibited a specific capacitance(Cs) of 1327 F/g and 324 F/g respectively at a scan rate of 10 m V/s. Further, the AS device i.e.,β–Ni(OH)_2/MWCNTs//K-PC in 1 M KOH solution, demonstrated a Cs of 156 F/g at scan rate of 10 m V/s in a broad cell voltage of 0–2.2 V. The device demonstrated a good rate capability by maintaining a Cs of 59 F/g even at high current density(25 A/g). The device also offered high energy density of 63 Wh/kg with maximum power density of 5.2 kW/kg. The AS device exhibited excellent cycle life with 100% capacitance retention at 5000 th cycle at a high current density of 25 A/g. Two AS devices connected in series were employed for powering a pair of LEDs of different colors and also a mini fan.     

Optimizing the electrolyte salt of aqueous zinc-ion batteries based on a high-performance calcium vanadate hydrate cathode material

It is urgent to develop high-performance cathode materials for the emerging aqueous zinc-ion batteries with a facile strategy and optimize the related components.Herein,a Ca0.23V2O5·0.95 H2O nanobelt cathode material with a rather large interlayer spacing of 13.0 A is prepared via a one-step hydrothermal approach.The battery with this cathode material and 3 M Zn(CF3SO3)2 electrolyte displays high specific capacity(355.2 mAh g^-1 at 0.2 A g^-1),great rate capability(240.8 mAh g^-1 at 5 A g^-1),and excellent cyclability(97.7% capacity retention over 2000 cycles).Such superior performances are ascribed to fast electrochemical kinetics,outstanding electrode/electrolyte interface stability,and nearly dendrite-free characteristic.Instead,when ZnSO4 or Zn(ClO4)2 is used to replace Zn(CF3SO3)2,the electrochemical performances become much inferior,due to the slow electrochemical kinetics,inhomogeneous Zn stripping/plating process,and the formation of large dendrites and byproducts.This work not only discloses a high-performance cathode material for aqueous zinc-ion batteries but also offers a reference for the choice of electrolyte salt.     

纳米氧化钴－氧化钌复合型超级电容器的研究

A novel type of composite electrode based on sheet like cobalt oxide particles has been used in supercapacitors. Cobalt oxide cathodically deposited from Co（NO3）2 solution with carbon nanotubes as matrix exhibited large pseudo-capacitance of 322 F·g^-1 in 6 mol·L^-1 KOH. A sol-gel process for the preparation of ultrafine RuO2 particles was developed to design electrodes with large surface area. The composite electrodes were developed by the deposition of RuO： on the surface of carbon nanotubes. A specific capacitance of 785 F·g^-1 can be achieved with the 20% carbon nanotubes loaded. To characterize the metal oxide nanocomposite electrode, a cyclic voltammetry and AC impedance test are executed. This study also reports a hybrid capacitor, which consists of cobalt oxide composite as a cathode and ruthenium oxide composite as an anode. The electrochemical performance of the hybrid capacitor is characterized by a dc charge/discharge test and cyclic voltammograms. The hybrid capacitor shows capacitor behavior with an extended operating voltage of 1.4 V. The maximum energy density and specific power density of the cell reach the value of 23.7 and 8.1 kW·g^-1 respectively. The hybrid capacitor exhibits high-energy density and stable power characteristics.     

Liquid phase synthesis of dendritic nickel carbide alloy with high conductivity for advanced energy storage

Alloy materials have attracted increasing attentions because they possess superior electrical conductivity which can contribute to excellent electrochemical performance. Herein a dendritic Ni_3C alloy material has been prepared by the pyrolysis of nickel acetylacetonate employing oleylamine as a reductant and 1-octadecene or octadecane as the solvent. The current–voltage curves indicating that the electrical conductivity of Ni_3C is higher than that of nickel oxide. Electrochemical testing indicates that a high specific capacity of 390 C/g is found in alkaline electrolyte at 0.5 A/g, and deliver excellent rate characteristic as well as cycle life. The excellent electrochemical performance may be attributed to its high electrical conductivity and dendritic nanostructure that can promote diffusion of electrolyte ions. In addition, the AC//Ni_3C asymmetric supercapacitor has been assembled at a cell voltages between 0 and 1.6 V, achieving a maximum energy density of 37 Wh/kg(at a power density of 0.3995 k W/kg), and this manifests that the Ni_3C alloy is a promising electrode material for electrochemical energy storage.     

Zinc tartrate oriented hydrothermal synthesis of microporous carbons for high performance supercapacitor electrodes

A novel zinc tartrate oriented hydrothermal synthesis of microporous carbons was reported. Zinc–organic complex obtained via a simple chelation reaction of zinc ions and tartaric acid is introduced into the networks of resorcinol/formaldehyde polymer under hydrothermal condition. After carbonization process, the resultant microporous carbons achieve high surface area(up to 1255 m~2/g) and large mean pore size(1.99 nm) which guarantee both high specific capacitance(225 F/g at 1.0 A/g) and fast charge/discharge operation(20 A/g) when used as a supercapacitor electrode. Besides, the carbon electrode shows good cycling stability, with 93% capacitance retention at 1.0 A/g after 1000 cycles. The welldesigned and high-performance microporous carbons provide important prospects for supercapacitor applications.     

超声波处理对球形β-Ni(OH)2结构及电化学性能的影响

A method of ultrasonic treatment （UST） was first used to modify the structure and electrochemical performance of nickel hydroxide for the active material of nickel series alkaline batteries. The experimental results showed that UST was an effective method to improve the electrochemical performance of β-Ni（OH）2 such as specific discharge capacity, discharge potential, electrochemical reversibility and oxygen evolution over-potential. The results of electrochemical impedance spectroscopy, powder X-ray diffraction and particle size distribution indicated that the improvement of the performance of β-Ni（OH）2 through UST was attributed to the reduction of the charge-transfer resistance （Rt） and the diffusion impedance （Zw）, which resulted from the decrease of the crystallite and particle size and the increase of interlayer spacing. Diffusion coefficient of proton DH of ultrasonic treated β-Ni（OH）2 gained by CV tests was 1.13 × 10^-11 cm^2/s, and the average discharge specific capacity of ultrasonic treated β-Ni（OH）2 electrode was 301 mAh/g.