电解液对超级电容器Mn_3O_4电极材料性能的影响

以应用于超级电容电极的锰氧化物材料为主要研究对象,用溶剂热法制备四氧化三锰(Mn3O4)电极材料,以X线衍射(XRD)和扫描电子显微镜(SEM)对材料性能进行了表征,采用循环伏安法、恒电流充放电法和电化学阻抗法对材料电性能进行了测试,分别以1 mol/L硫酸钠(Na2SO4)和6 mol/L氢氧化钾(KOH)为电解液研究了不同电解液对Mn3O4电极材料性能的影响.结果表明,当电流密度为0.5 A/g时,Mn3O4在KOH电解液中的比电容为48 F/g,相比在Na2SO4电解液中所得的比电容22 F/g要大.     

氨解改性煤基活性炭电极材料的电化学性能

以印尼褐煤为原料、KOH活化法制备的煤基活性炭,采用氨水在高压条件下对其进行改性,应用N2吸附仪、傅里叶变换红外光谱(FTIR)表征了活性炭的孔结构和表面化学性质,测定了活性炭制作的电极在3mol/L KOH电解液中的电化学性能.结果表明,经过氨水高压改性处理的活性炭的比表面积和孔结构变化不大,但改性后活性炭表面的N原子含量增多,活性炭表面负载上一定量的C-N,N-H和-NO2等含氮官能团;改性后活性炭的比电容可达348F/g,比改性前提高27%;改性后活性炭电极的导电性增强,循环充放电性能更好,在42.5mA/g的电流密度下经1 000次循环充放电,比电容的保持率可达98.9%.     

物理化学两步活化法制备煤基活性炭电极材料

为提高超级电容器用的活性炭电化学性能,通过物理化学两步活化法制备煤基活性炭.以太西无烟煤为原料,通过成型和炭化后,用CO_2物理活化制得柱状活性炭(AC-1).将AC-1酸洗脱灰,并用KOH水溶液浸渍,进行第2步化学活化,制得超级电容器用的煤基活性炭(AC-2),两步活化后总收率为45.18%.将活性炭制备成电极材料,并在三电极和双层电容器体系下进行电化学性能测试.结果表明:在KOH电解液浓度为6mol/L,电流密度为0.5A/g时,三电极体系下,比电容由68.5F/g(AC-1)提高到122.5F/g(AC-2),在纽扣式超级电容器体系下,比电容由75F/g(AC-1)提高到165.5F/g(AC-2),且AC-2具有良好的长循环稳定性,经过5 000次的循环后电容量几乎无衰减.与物理活化所得活性炭相比,物理化学两步活化所得活性炭的总孔容和中孔率明显增加,其作为电极材料的电化学性能显著提高.     

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.     

煤基活性炭孔结构对电化学性能的影响

以太西无烟煤和灵武烟煤的配合煤为原料在硝酸锰存在下经水蒸气活化制备了活性炭,利用气体吸附仪和电化学工作站表征其孔结构及循环伏安、交流阻抗和恒流充放电等电化学性能.结果表明,比表面积SBET小于900m2/g时,比电容与比表面积成正比,SBET大于900m2/g时,比电容与比表面积成反比;活性炭的总孔容和微孔孔容对比电容的影响与比表面积存在相似的规律;中孔对比电容的影响最为显著,比电容随中孔孔容的增加迅速增加,在0.11～0.14cm3/g区间增幅明显减小,大于0.14cm3/g后迅速减小;制备的煤基活性炭电极的电化学行为表现为双电层电容与准电容协同作用;活性炭电极接触电阻很小,最大约为0.8Ω.     

中孔Co_3O_4材料的电容特性

采用"原位合成模板法"以硅酸为模板、硝酸钴为钴源,制备了中孔Co3O4材料,研究了模板和硝酸钴的质量比对所制得的中孔Co3O4材料的微观结构和电化学性能的影响.用N2等温吸附—脱附和X线衍射测试了其微观结构.结果表明,随着模板质量比的增加,制备得到的Co3O4材料的比表面积增加,中孔结构越明显,结晶性逐渐降低.在6 mol/L氢氧化钾电解液中测试了其电化学性能,最优质量比制得的样品在5 mV/s扫描速率下的比电容达329 F/g.即使在较高扫描速率下,该质量比的中孔Co3O4比电容依然具有很好的保持性.     

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.     

多孔生物质碳/NiCo_2S_4复合材料的制备及电化学性能研究

以萝藦(Metaplexis japonica,一种草本缠绕植物)种子顶端的白色长绢毛为生物质碳的前驱体,氢氧化钾为活化剂,制备了管状的多孔生物质碳材料(AMJ).再通过水热法和硫化过程在多孔生物质碳材料上原位生长Ni Co2S4纳米颗粒.通过X射线衍射(XRD)、扫描电子显微镜(SEM)和N2吸附-脱附分析表征了其微观形貌和结构.呈管状结构的多孔生物质碳材料的比表面积为2 831 m2/g,这有利于电解液/电极界面电荷的积累,同时促进电解液离子的扩散和传输.将AMJ/Ni Co2S4复合材料用作超级电容器电极材料,在三电极体系中进行电化学性能测试.在扫描速度为5 m V/s时,AMJ/Ni Co2S4电极材料的最高比电容可达1 041.6 F/g.同时,与纯Ni Co2S4电极材料相比具有良好的倍率性能和循环稳定性.     

活性石墨烯的制备及其电化学电容特性的研究

将超声分散处理的氧化石墨直接与氢氧化钾按一定比例混合,经过高温活化处理,制备得到活性石墨烯。采用XRD、TEM以及氮气吸脱附对活性石墨烯的微观结构、表面形貌以及比表面积进行表征分析,并考察材料的电化学电容特性。结果表明:经过直接活化制备得到的活性石墨烯具有很高的比表面积(高达1220m~2/g)和较大的孔容积(0.995cm~3/g)。电化学性能测试结果表明:在1A/g电流密度下,6mol/L KOH溶液中活性石墨烯电极材料的质量比电容能达到111F/g,经过5000次充放电循环后,电容保持率仍为99.2%。     

金属有机框架在超级电容器中的应用

成功制备了金属有机框架M3(BTC)2·12H2O(M=Ni和Co),并将其应用于超级电容器电极材料中,通过X线衍射(XRD)表征发现,这些化合物具有同类型的结构,在6 mol/L电解液中,采用循环伏安法和1 000次充放电循环测试其电化学性能.实验表明:Ni3 (BTC)2·12H2O电极材料在扫描速率5 mV/s下,比电容达到了430 F/g;在高扫描速率200 mV/s下,比电容为154 F/g;在扫描速率5 mV/s下1 000次充放电测试其循环寿命后发现,比电容保持率为86％.     

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.     

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.     

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.     

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.     

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。     

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.     

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