Preparation of activated carbons from mesophase pitch and their electrochemical properties

The influences of molar ratio of KOH to C and activated temperature on the pore structure and electrochemical property of porous activated carbon from mesophase pitch activated by KOH were investigated. The surface areas and the pore structures of activated carbons were analyzed by nitrogen adsorption, and the electrochemical properties of the activated carbons were studied using two-electrode capacitors in organic electrolyte. The results indicate that the maximum surface area of 3 190 m2/g is obtained at molar ratio of KOH to C of 5:1, the maximum specific capacitance of 122 F/g is attained at molar ratio of KOH to C of 4:1, and 800 ℃ is the proper temperature to obtain the maximum surface area and capacitance.     

孔结构对煤基活性炭电化学性能的影响

以煤为前驱体,KOH为活化剂制备系列煤基活性炭电极材料.采用N_2吸附法及电化学测试对活性炭的孔结构和电化学性能进行了表征,研究了孔结构对活性炭电极材料的电化学性能的影响.结果表明,采用化学活化法可制备出比表面积1 048～3 581 m~2/g、中孔率7%～91%的活性炭电极材料.在3 mol/L KOH无机电解液体系及1 mol/L(C_2H_5)_4NBF_4/碳酸丙烯酯(PC)有机电解液体系中,活性炭电极材料的比电容分别达到322 F/g,190 F/g.2～3 nm的中孔对电解质离子在电极材料中的扩散有着重要作用,可以有效降低电解液的扩散阻力,提高电极材料比表面积的利用率,从而增强电容器的电化学性能.     

Effect of Adding Microwave Absorber on Structures and Properties of Hypercoal-Based Activated Carbons

Using lignite-based hypercoal as raw material,KOH as activator and CuO as microwave absorber,we prepared hypercoal-based activated carbons by microwave-assisted activation.The pore structure and the electrochemical performance of the activated carbons were tested,and the effects of adding CuO in the activation reaction process were also investigated.The activated carbons prepared were characterized by nitrogen adsorption-desorption,X-ray diffraction (XRD) and scanning electron microscopy (SEM).The specific surface area and mesoporous ratio of the hypercoal-based activated carbon are 1 257 m~2/g and 55.4%,respectively.When the activated carbons are used as the electrode materials,the specific capacitance reaches 309 F/g in 3 M KOH electrolyte.In comparison with those prepared without CuO absorber,the specific capacitance increases by 11.6%.It was proved that the addition of microwave absorber in microwave-assisted activation was a low-cost method for rapidly preparing activated carbon,and it could effectively promote the development of the pore structure and improve its electrochemical performance.     

Comparison of capacitive behavior of activated carbons with different pore structures in aqueous and nonaqueous systems

The pore structures of two activated carbons from sawdust with KOH activation and coconut-shell with steam activation for supercapacitor were analyzed by N2 adsorption method. The electrochemical properties of both activated carbons in 6 mol/L KOH solution and 1 mol/L EtgNPF4/PC were compared, and the effect of pore structure on the capacitance was investigated by cyclic voltammetry, AC impedance and charge-discharge measurements. The results indicate that the capacitance mainly depends on effective surface area, but the power property mainly depends on mesoporosity. At low specific current （1 A/g）, the maximum specific Capacitances of 276.3 F/g in aqueous system and 123.9 F/g in nonaqueous system can be obtained from sawdust activated carbon with a larger surface area of 1 808 m^2/g, butat a high specific current, the specific capacitance of coconut-shell activated carbon with a higher mesoporosity of 75.1% is more excellent. Activated carbon by KOH activation is fitter for aqueous system and that by steam activation is fitter for nonaqueous system.     

应用模板法从煤沥青制备中孔活性炭

以煤沥青为原料,应用纳米二氧化硅模板法制备中孔活性炭,并考察焦模比、碱碳比以及活化温度对活性炭孔结构和收率的影响。结果表明,所得活性炭试样孔径分布最大值与模板剂孔径尺寸相吻合。在焦模比为2∶1、碱碳比为4.5∶1、活化温度为850℃时,所制活性炭总比表面积为1729 m^2/g,其中中孔比表面积为1702 m^2/g,占总比表面积的98.43%。     

Influence of KOH activation techniques on pore structure and electrochemical property of carbon electrode materials

1 INTRODUCTIONSupercapacitor is a kind of newenergy storagedevice , which can fill the gap between the conven-tional capacitor and the battery[1 ,2]. Supercapa-ciors are nowutilizedin many fields ,such as spaceindustry ,national defense ,warindustry ,electricalvehicle , wireless communication, and consume e-lectronics .It is well known that the electrode ma-terial is the key factor to determine the perform-ance of supercapacitor . At present ,the activatedcarbonis the main marketed availa…     

Optimal electrochemical performances of CO2 activated carbon aerogels for supercapacitors

Activated carbon aerogels（ACAs） derived from sol-gel polycondensation of resorcinol （R） and formaldehyde （F） were pyrolyzed under Ar flow and activated in CO2 atmosphere. The morphology of ACAs was characterized by scanning electron microscopy （SEM） and the structural properties were determined by N2 adsorption at 77 K. The results show that ACAs have a typical three-dimensional nanonetwork structure composing of cross-linking of carbon nanoparticles. The specific surface area and the total pore volume remarkably increase with increasing activation time while the previous porous structure still remains. The specific capacitance of the 950-10-ACA electrode can reach up to 212.3 F/g in 6 mol/L KOH electrolyte. The results of constant-current charge-discharge testing indicate that the ACAs electrodes present fast charge- discharge rate and long cycle life （about 98% capacitance retained after 3000 charge-discharge cycles at 1.25 mA/cm2）. Lower internal resistances can be achieved for 950-10-ACA electrode in KOH electrolyte. Our investigations are very important to improve the wettability and electrochemical performance of electrode for supercapacitors.     

Characterization and methanol adsorption of walnut-shell activated carbon prepared by KOH activation

Walnut-shellactivated carbons(WSACs)were prepared by the KOH chemicalactivation.The effects of carbonization temperature,activation temperature,and ratio of KOH to chars on the pore development of WSACs were investigated.Fourier transform infrared spectroscopy(FTIR),X-ray powder diffraction(XRD),and scanning electron microscopy(SEM)were employed to characterize the microstructure and morphology of WSACs.Methanoladsorption performance onto the optimalWSAC and the coal-based AC were also investigated.The results show that the optimalpreparation conditions are a carbonization temperature of 700 ℃,an activation temperature of 700 ℃,and a mass ratio of 3.The BET surface area,the micropore volume,and the micropore volume percentage of the optimalWASC are 1636 m~2/g,0.641 cm~3/g and 81.97%,respectively.There are a lot of micropores and a certain amount of meso-and macropores.The characteristics of the amorphous state are identified.The results show that the optimalWSAC is favorable for methanoladsorption.The equilibrium adsorption capacity of the optimalWSAC is 248.02mg/g.It is shown that the equilibrium adsorption capacity of the optimalWSAC is almost equivalent to that of the common activated carbon.Therefore the optimalWSAC could be a potentialadsorbent for the solar energy adsorption refrigeration cycle.     

纳米门炭结构及超级电容特性

以生石油焦为原料,采用KOH活化法制备纳米门炭。采用氮气吸附法、X射线衍射(XRD)和光电子能谱衍射(XPS)对其孔结构、微晶结构和表面性质进行分析,并以其为电极组装超级电容器,测试了电容特性。结果表明:纳米门炭可在3.5V电压下工作,通过首次充电过程中的电化学活化而获得较大的比电容。样品N900比表面积仅为61m2/g,但比电容确高达136.7F/g,能量密度高达58.1Wh/kg。     

High-performance porous carbon for supercapacitors prepared by one-step pyrolysis of PF/gelatin blends

A high-performance porous carbon material for supercapacitor electrodes was prepared by using a polymer blend method. Phenol-formaldehyde resin and gelatin were used as carbon precursor polymer and pore former polymer, respectively. The blends were carbonized at 800 °C in nitrogen. SEM, BET measurement and BJH method reveal that the obtained carbon possesses a mesoporous characteristic, with the average pore size between 3.0 nm and 5.0 nm. The electrochemical properties of supercapacitor using these carbons as electrode material were investigated by cyclic voltammetry and constant current charge-discharge. The results indicate that the composition of blended polymers has a strong effect on the specific capacitance. When the mass ratio of PF to gelatin is kept at 1:1, the largest surface area of 222 m²/g is obtained, and the specific capacitance reaches 161 F/g.     

Characteristics of activated carbon prepared from Chinese fir sawdust by zinc chloride activation under vacuum condition

The preparation of activated carbon from Chinese fir sawdust by zinc chloride activation under both nitrogen atmosphere and vacuum conditions was carried out in a self-manufactured vacuum pyrolysis reactor. The effects of the system pressure and the activation condition (nitrogen or vacuum) on pore development were investigated. The results show that both high quality activated carbon and high added-value bio-oil can be obtained simultaneously via vacuum chemical activation. The characteristics of the activated carbons produced under vacuum conditions are better than those prepared under nitrogen atmosphere. The performance parameters of the activated carbon obtained under vacuum conditions are as follows: the pore size distribution is mainly microporous, the Brunauer-Emmett-Teller (BET) surface area is 1 070.59 m²/g, the microporous volume is 0.502 4 cm³/g, the average pore size is 2.085 nm, and the iodine adsorption value and the methylene blue adsorption value are 1 142.92 and 131.34 mg/g, respectively. The activated carbon from vacuum chemical activation has developed micropores, and the N₂ adsorption equilibrium constant of the corresponding activated carbon gradually increases with the decrease of reaction system pressure.     

Nanosized Nickel Oxides Derived from the Citrate Gel Process and Performances for Electrochemical Capacitors

Nanosized nickel oxide powders were prepared by thermal decomposition of the nickel citrate gel precursors. The thermal decomposition and powder materials derived from calcination of these gel precursors with various ratios of citric acid （CA） to nickel at different temperatures and times were characterized by thermal analysis （TG/DTA）, scanning electron microscopy （SEM）, x-ray diffraction （XRD）, and measurement of specific surface area （BET） with porosity analyses. The optimized processing conditions of calcination temperature 400℃ for 1 hour with the CA/Ni ratio of 1.2, were determined to produce the nanosized nickel oxide pow- ders with a high specific surface area of 181 m^2/g, nanometer particle sizes of 15-25 nm, micro-pore diameter distribution between 4-10 nm. The capacitance characteristics of the nanosized nickel oxide electrode in various concentrations of KOH solutions were studied by the cyclic voltammetry （CV） exhibiting both a double-layer capacitance and a faradaic pseudocapacitance. The nanosized nickel oxide electrode shows a high cyclic stability and is promising for high performance electrochemical capacitors.     

煤热解沥青炭化程度对KOH活化制备活性炭孔隙结构的影响

以煤热解沥青为原料,采用KOH活化法制备活性炭提高附加值.在不同减压蒸馏终温（VDFT）和不同预炭化温度下得到碳质前驱体,研究碳质前驱体的炭化程度对制备的活性炭孔隙结构的影响.研究表明,碳质前驱体合适的炭化程度,即前驱体中适量的挥发分、H原子、表面官能团以及合适的结构排列,有益于KOH活化.减压蒸馏终温为440℃的多联产煤热解沥青活化得到的活性炭比表面积最大,为2 599 m²/g.减压蒸馏终温为360℃的沥青在400℃下炭化2 h,经KOH活化后可以得到比表面积为2 575 m²/g的高比表面积活性炭,但是需要预炭化处理,工艺相对复杂.     

活性炭比表面积对双电层电容特性的影响

用KOH活化活性炭作为电极材料制作双电层电容器,用接触角测定其润湿性,用恒流充放电、循环伏安等方法研究活性炭的电化学性能。结果显示,炭膜浸润时间最短约为90min,双电层电容器的比电容随比表面积增加而增大。比表面积为1932m^2·g^-1的炭样在1mol·L^-1的H2SO4电解~（677mA·g^-1）中充放电最大比电容为167F·g^-1。     

Electrochemical behavior of diverse vanadium ions at modified graphite felt electrode in sulphuric solution

PAN-based graphite felt (PGF) treated in 98% sulphuric acid for 5 h and then kept at 450 ℃ for 2 h was evaluated for their electrochemical performance as electrodes of vanadium redox battery (VRB). Structure and characteristic of treated PAN-based graphite felt (TPGF) were determined by means of Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Brunauer-Emmett-Teller surface area analysis and VRB test system. The results show that the acid and heat synergistic effect increase the number of —COOH functional groups on the PGF surface, and the PGF is eroded by sulphuric acid oxidation, resulting in the surface area increases from 0.31 m2/g to 0.45 m2/g. The V(Ⅱ)/V(Ⅲ) redox reaction is electrochemically reversible on the TPGF electrode, while the V(Ⅳ)/V(Ⅴ) couple is a quasi reversible process. The diffusion coefficients of the oxidation for V(Ⅳ)/V(Ⅴ) obtained from the scope of peak current Ip vs scan rate v1/2 is 4.4×10-5 cm2/s. The improvement of electrochemical activity for the electrode is mainly ascribed to the increase of the number of —COOH groups on the TPGF, which behaves as active sites catalyzing the vanadium species reactions and accelerating electron transfer reaction and oxygen transfer.     

Microwave-assisted synthesis of 3D flowerlike a-Ni(OH)_2 nanostructures for supercapacitor application

Three-dimensional flowerlike ?-Ni(OH)2 nanostructures were successfully synthesized by the microwave-assisted reflux as short as 30 min. The crystalline structure and morphology of the products were characterized by X-ray diffraction, N2 adsorption-desorption isotherms, field emission scanning electron microscopy, and transmission electron microscopy. The ?-Ni(OH)2 nanostructure shows a large surface area of 173 m2 g?1 and narrow mesopore distribution. The electrochemical properties of the as-prepared ?-Ni(OH)2 as an electrode material for supercapacitor were investigated by cyclic voltammetry and galvanostatic charge-discharge measurements in 6 mol/L KOH electrolyte. The ?-Ni(OH)2 nanostructure shows a maximum specific capacitance of 2030 F g?1 at a current density of 1 A g?1 and exhibits excellent rate capability. These results suggest that it is a promising electrode material for supercapacitor application.     

Influence of nitrogen hetero-substitution on the electrochemical performance of coal-based activated carbons measured in non-aqueous electrolyte

Nitrogen-containing carbons were prepared by modification of activated carbons. The modified carbons were used as electrode materials with improved electrochemical performance. Precursor anthracite was activated by KOH (KOH: anthracite= 1:1), modified by melamine or urea and then treated at 1173 K to obtain the modified carbons. The porous structure, the chemical composition and the electrochemical characteristics of the carbons were investigated by nitrogen sorption, XPS and electrochemical methods respectively. Electrochemical experiments were performed in an organic electrolytic solution of 1 M (C2H5)4NBF4/PC.The samples modified by the different methods showed differences in chemical composition that introduced varying degrees of electrochemical performance enhancement. The presence of nitrogen enhanced the electron donor properties and the surface wettability of the activated carbons: this ensured a sufficient utilization of the exposed surface for charge storage.     

Preparation of Hierarchically Interconnected Porous Banana Peel Activated Carbon for Methylene Blue Adsorption

Hierarchically interconnected porous activated carbon have high specific surface areas, large numbers of dye adsorption sites, and interconnected pores for dye molecule diffusion and transportation. We prepared hierarchically interconnected porous banana peel activated carbons(BPACs) via a green method involving hydrothermal pretreatment and KOH activation, and systematically tested its methylene blue(MB) adsorption capacity. SEM showed that the BPACs had an interconnected porous structure and high-porosity surface. The Brunauer-Emmett-Teller surface area was 601.21 m~2/g, the adsorption average pore diameter was 2.11 nm, and the total pore volume was 0.32 cm~3/g. The MB adsorption capacity increased with increasing temperature, initial MB concentration, and pH value; it decreased with increasing adsorbent dosage. The adsorption isotherms and kinetic results for MB adsorption on BPACs were best described by the Langmuir adsorption and pseudo-second-order kinetic models, respectively. BPACs have a well-developed hierarchically interconnected porous structure, which increase the MB adsorption capacity and removal efficiency. Systematic MB adsorption tests show that BPAC is a highly efficient and easily available adsorbent.     

Synthesis of mesoporous carbon as electrode material for supercapacitor by modified template method

The pore structures and electrochemical performances of mesoporous carbons prepared by silica sol template method as electrode material for supercapacitor were investigated. The mean pore size and mass specific capacitance of the mesoporous carbons increase with the increase of mass ratio of silica sol to carbon source （glucose）. A modified template method, combining silica sol template method and ZnCl2 chemical activation method, was proposed to improve the mass specific capacitance of the mesoporous carbon with an improved BET surface area. The correlation of rate capability and pore structure was studied by constant current discharge and electrochemical impedance spectroscopy. A commercially available microporous carbon was used for comparison. The result shows that mesoporous carbon with a larger pore size displays a higher rate capability. Mesoporous carbon synthesized by modified template method has both high mass specific capacitance and good rate capability.     

Supercapacitors based on high-surface-area graphene

Exfoliated graphite oxide was prepared by an improved Hummers method and was then reduced to graphene with hydrazine in the presence of ammonium hydroxide.N2adsorption–desorption measurement showed that graphene so obtained had a specific surface area as high as 818 m2/g.Galvanostatic charge/discharge curves demonstrated that the as-prepared graphene exhibited a specific capacitance of 186.9 F/g at a current density of 0.1 A/g and that about 96%of the specific capacitance was retained after 2000 cycles at a current density of 5 A/g.