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…     

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.     

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.     

Preparation and electrochemical characterization of activated carbons by chemical-physical activation

A process was proposed based on the combination of chemical and physical activation for the production of activated carbons used as the electrode material for electric double layer capacitor (EDLC). By material characterization and electrochemical methods, the influences of the activitation process on the specific surface area, pore structure and electrochemical properties of the activated carbons were investigated. The results show that specific surface area, the mesopore volume, and the specific capacitance increase with the increase of the mass ratio of KOH to char (m(KOH)/m(char)) and the activation time, respectively. When m(KOH)/m(char) is 4.0, the specific surface area and the mesopore volume reach the maximum values, i.e. 1 960 m²/g and 0.308 4 cm³/g, and the specific capacitance is 120.7 F/g synchronously. Compared with the chemical activation, the activated carbons prepared by chemical-physical activation show a larger mesopore volume, a higher ratio of mesopore and a larger specific capacitance. Foundation item: Project(2007BAE12B01) supported by the National Key Technology Research and Development Program of China     

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.     

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.     

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.     

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。     

载镍活性炭材料及复合型超级电容器

为提高碳基电化学电容器的比电容和和能量密度,采用化学沉积法将少量镍氧化物沉积在活性炭上,得到沉积镍氧化物的活性炭材料并以此材料做成复合电极用于混合型电化学电容器的正极.研究显示,沉积镍氧化物后,碳材料的比表面积略有减小,但孔径分布没有明显变化.复合电极作为混合型电容器的正极时,比电容达到194.01F/g,比纯活性炭正极的175F/g提高了10.84%;复合电极在6mol/L的电解液中析氧电势为0.296V,比纯活性炭电极的0.220V高出0.076V,因此,具有较高的能量密度.不同放电电流密度下的恒电流测试结果显示,沉积镍氧化物活性炭复合电极的比电容值没有明显变化,与纯活性炭电极一样表现出良好的功率特性.采用沉积镍氧化物活性炭作为正极材料的复合型电容器,在6mol/L的KOH水溶液作为电解液时,单体电容器的工作电压可以达到1.2V,高于纯活性炭制备的双层型电容器0.2V.充放电循环10000次时,复合型电容器的电容仅降低到初始电容的90%.上述结果表明,在活性炭上沉积少量镍氧化物颗粒可以提高碳基电化学电容器的比电容和能量密度.     

Preparation and properties of pitch carbon based supercapacitor

Using the mesophase pitch as precursor, KOH and CO2 as activated agents, the activated carbon electrode material was fabricated by physical-chemical combined activated technique for supercapacitor. The influence of activated process on the pore structure of activated carbon was analyzed and 14 F supercapacitor with working voltage of 2.5 V was prepared. The charge and discharge behaviors, the properties of cyclic voltammetry, specific capacitance, equivalent serials resistance (ESR), cycle properties, and temperature properties of prepared supercapacitor were examined. The cyclic voltammetry curve results indicate that the carbon based supercapacitor using the self-made activated carbon as electrode materials shows the desired capacitance properties. In 1 mol/L Et4NBF4/AN electrolyte, the capacitance and ESR of the supercapacitor are 14.7 F and 60 m?, respectively. The specific capacitance of activated carbon electrode materials is 99.6 F/g; its energy density can reach 2.96 W·h/kg under the large current discharge condition. There is no obvious capacitance decay that can be observed after 5000 cycles. The leakage current is below 0.2 mA after keeping the voltage at 2.5 V for 1 h. Meanwhile, the supercapacitor shows desired temperature property; it can be operated normally in the temperature ranging from -40 ℃ to 70 ℃.     

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%。     

氧化钴/有序中孔炭超级电容器复合材料的制备及其性能

采用微湿含浸-溶剂热法制备了高比表面积和高比电容的氧化钴/有序中孔炭超级电容器复合材料.采用液氮吸附脱附等温线和X线衍射,以及透射电镜表征了复合材料的孔结构,在6 mol/L 氢氧化钾电解液中测试了其电化学性能.测试结果表明:在5 mV/s充放电扫描速率下,复合材料的比电容达到1079.6 F/g,并且具有良好的循环寿命,显示了优异的电化学性能.     

微波活化甘蔗渣合成活性炭及其电化学电容特性

以甘蔗渣为原料,ZnCl2为活化剂,分别采用微波加热活化和管式炉加热活化制备了一系列活性炭材料,并研究了微波活化法制备的活性炭在水或离子液体电解液体系中的电容特性.氮气吸附测试表明:活化剂的浓度与活性炭的孔结构密切相关,加热方式对孔径结构的影响不大,但微波活化法在加热效率和均匀性方面具有明显的优势.当活化剂的浓度从20wt%增大到60wt%时,活性炭的平均孔径从2.5nm逐渐增大到7.0nm.电化学测试表明:在离子液体中炭材料的电容性能与其孔径大小密切相关,孔径尺寸越大,其电容性能越好.离子液体电容器能提供远高于水相电容器的能量密度.AC60在功率密度为2.5kW/kg时,仍能提供9.2Wh/kg的能量密度.     

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。     

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.     

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.     

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.     

纳米氧化镍的制备及其电化学电容

通过金属碳酸盐、硝酸(氧化剂)和柠檬酸(燃料)的凝胶-燃烧方法合成了纳米氧化镍粉体。在柠檬酸与Ni2+的摩尔比为1.3:1,热处理温度为400℃的条件下,以1mol/LKOH水溶液为电解液对纳米NiOx制备的电极进行了循环伏安、充放电及电化学阻抗谱分析。分析结果表明纳米NiOx电极在KOH水溶液电解液中具有良好的赝电容特性,其平均比容量最大为78.8F/g,并具有良好的循环寿命。     

不同活化方式制备碳电极材料的电化学性能

以碳化后的中间相沥青为原料,分别采用化学活化和物理-化学联合活化工艺制备了超级电容器用活性炭电极材料,对不同活化方式制备的活性炭电极材料的微晶结构、孔径分布、比电容量、循环伏安和交流阻抗特性进行了比较。实验结果表明：采用物理-化学联合活化工艺制备的活性炭电极材料具有更理想的微晶结构和中孔含量。活性炭电极材料的结构与孔隙分布对电性能有明显影响,采用联合活化方式制备的电极材料具有较高的面积比容量、较好的功率特性及较理想的电容特性。