表面改性对活性炭孔结构及热电转换性能的影响

为探究表面改性对活性炭孔结构及热电转换性能的影响,使用HNO_3和KOH在不同条件下对活性炭进行表面改性,用N2吸附法和XRD图谱表征活性炭改性前后孔结构和石墨化程度的变化。结果表明,改性后活性炭的比表面积和孔容提高,平均孔径减小,并存在石墨晶体结构。干法改性活性炭的比表面积和总孔容由1 077.880m~2/g和0.763cm~3/g分别增加到1 635.268m~2/g和1.128cm~3/g,并且微孔的孔容增加。改性处理可以去除活性炭中的杂质。分别以改性前后活性炭为材料制备固体电极,KCl为电解液,测试活性炭电极的热电转换性能,发现改性后活性炭具有更高的热电转换性能。     

Improvement of supercapacitor parameters by nickel ion intercalation into activated carbon

The relation between the porous structure and the electron structure in carbon materials was investigated in order to optimize the efficiency of the physical-chemical processes in an electric double layer (EDL) formed at the boundary between the carbon material and the electrolyte (KOH 30 % aqueous solution). In particular, an Ni²⁺ intercalative modification of nanoporous carbon resulted in more than a triple increase in the specific capacitance and a significant improvement of the charge-discharge kinetics in the EDL.     

活性炭的孔结构与其电容特性的关系研究

采用传统工艺制备了超级电容器用高比表面积微孔炭,利于氮气吸附、循环伏安和恒流充放电研究了样品的孔结构和电容特性.结果表明,试验研制的微孔炭的比表面积达到2496m2/g,大孔径微孔含量很高,在5mA/cm2的电流密度下,活性炭的比容达到307F/g,而且具有良好的功率特性.超级电容器用活性炭的比容主要来自微孔比表面积的贡献,中孔对比容的贡献很小,其作用主要是改善功率特性.为了获得高比容和高功率密度,活性炭应该具有尽可能多的大孔径微孔和适量的小孔径中孔.     

炭前驱体对活性炭孔结构和电化学性能的影响

分别以毛竹和石油焦为炭前驱体,采用KOH活化法制备超级电容器用高比表面积活性炭材料,考察了碱/炭比对不同炭前驱体所制得的活性炭的孔结构、吸附性能和电容性能的影响。结果表明,在相同的碱/炭比下,竹基活性炭孔径2nm的微孔较发达,而石油焦基活性炭孔径在2～50nm的中孔率较高。在适宜的工艺条件下,以毛竹为炭前驱体可制得比表面积为2610.7m2/g,比电容为206F/g的活性炭材料;以石油焦为炭前驱体可制得比表面积为2597.9m2/g,比电容为213F/g的活性炭材料。     

利用铈盐改性修饰活性炭纤维结构

利用硝酸铈铵对活性炭纤维进行了化学改性。研究了铈盐改性前后活性炭纤维的微观结构和表面化学结构的变化。结果表明，活性炭纤维经铈盐处理后，比表面积降低10％～20％左右，微孔孔径分布没有发生明显的变化，表面氧含量从原子分数11％提高至25％，使活性炭纤维表面形成更多的高价态含氧基团。并通过X射线光电子能谱和热重-红外联用的分析结果相结合，较为详细地、定量地分析了活性炭纤维表面的含氧基团。结果表明，利用热重一红外联用技术对活性炭纤维表面含氧基团的种类及其相对量分析结果与基于X射线光电子能谱的C1s分峰结果定量分析基本一致，两种结果可互为验证。     

多孔聚苯胺/乙炔炭黑复合物的制备及其超级电容特性

采用乙炔炭黑吸附原位聚合方法制备了聚苯胺/炭黑复合材料.利用红外光谱仪、扫描电镜(SEM)及电化学工作站对其结构、形貌及电容特性进行了表征.研究结果表明,聚苯胺/炭黑(PAn/CB)和聚苯胺/氧化炭黑(PAn/CBO)复合物均呈现多孔结构.由于PAn/CBO复合物为纤维状形貌,显示出了更好的超级电容特性,在5mA/cm2放电电流下其放电比电容高达424 F/g.     

Inflating strategy to fabricate highly dispersed Fe,N co-doped hierarchically porous carbon for ORR and supercapacitor

Doped-carbon nanomaterials as effective electrocatalysts have been received widespread attention in oxygen reduction reaction (ORR) and supercapacitors system. Herein, the high-active Fe atoms dispersed on hierarchically porous N-doped carbon (FeNC-X) is synthesized via inflating the Fe-ion-denatured egg-white, followed by activation and pyrolysis. Among them, the as-prepared FeNC-900 for ORR that has an inner-connecting hierarchically porous structure shows a superior performance with a limiting current density of 5.28 mA cm^?2 and half-wave potential (E_1/2) of 0.839 V (vs RHE), and exhibits a 4 e^? ORR pathway in the alkaline medium. FeNC-900 also shows better durability and good methanol tolerance than those of commercial Pt/C. Besides, FeNC-900 exhibits an outstanding specific capacity of 258 F g^?1 at 1 A g^?1 for supercapacitor. The method presented here may provide a cost-efficient approach to fabricate carbon-based materials for ORR and supercapacitors.

     

Composite supercapacitor electrodes made of activated carbon/PEDOT:PSS and activated carbon/doped PEDOT

In this paper, we report on the high electrical storage capacity of composite electrodes made from nanoscale activated carbon combined with either poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) or PEDOT doped with multiple dopants such as ammonium persulfate (APS) and dimethyl sulfoxide (DMSO). The composites were fabricated by electropolymerization of the conducting polymers (PEDOT:PSS, doped PEDOT) onto the nanoscale activated carbon backbone, wherein the nanoscale activated carbon was produced by ball-milling followed by chemical and thermal treatments. Activated carbon/PEDOT:PSS yielded capacitance values of 640 F g^?1 and 26 mF cm^?2, while activated carbon/doped PEDOT yielded capacitances of 1183 F g^?1 and 42 mF cm^?2 at 10 mV s^?1. This is more than five times the storage capacity previously reported for activated carbon–PEDOT composites. Further, use of multiple dopants in PEDOT improved the storage performance of the composite electrode well over that of PEDOT:PSS. The composite electrodes were characterized for their electrochemical behaviour, structural and morphological details and electronic conductivity and showed promise as high-performance energy storage systems.     

A structural supercapacitor based on activated carbon fabric and a solid electrolyte

ABSTRACT

This paper presents investigations to create a structural supercapacitor with activated carbon fabric electrodes and a solid composite electrolyte, consisting of organic liquid electrolyte 1?M TEABF₄ in propylene carbonate and an epoxy matrix where different compositions were considered of 1:2, 1:1 and 2:1 w/w epoxy:liquid electrolyte. Vacuum-assisted resin transfer moulding was used for the impregnation of the electrolyte mixture into the electrochemical double layer capacitor (EDLC) assembly. The best electrochemical performance was exhibited by the 1:2 w/w epoxy: liquid electrolyte ratio, with a cell equivalent-in-series resistance of 160?Ω?cm² and a maximum electrode-specific capacitance of 101.6?mF?g^?1 while the flexural modulus and strength were 0.3?GPa and 29.1?MPa, respectively, indicating a solid EDLC device.     

Preparation of polyaniline coated activated carbon and their electrode performance for supercapacitor

Polyaniline coated mesoporous and microporous activated carbons were prepared by chemical oxidation polymerization of aniline adsorbed on activated carbons. BET and mesopore specific surface areas of the obtained activated carbons decreased by coating with polyaniline. The electrode performance of the polyaniline coated activated carbons for supercapacitor was investigated. The electrochemical pseudo-capacitances increased with increasing polyaniline content in activated carbons. The capacitances due to polyaniline in the mesoporous activated carbon are much higher than those in the microporous activated carbon. The uniform coating of polyaniline on mesopores of activated carbon plays an important role in pseudo-capacitance due to polyaniline.     

氯化铜/活性炭复合电极的制备及性能的研究

以酚醛树脂为活性炭基体,采用化学掺杂法掺杂氯化铜,制备氯化铜／活性炭复合电极材料。通过物理吸附考察了金属氯化铜的存在下不同活化时间对金属复合活性炭孔径分布的影响,实验表明活化时间越长,比表面积越大,中孔含量越高。通过透射电镜和X射线衍射对复合电极的微观结构进行了研究,表明金属铜以纳米级均匀分散在活性炭中。通过比较活性炭电极和复合电极的电化学性能,说明掺杂金属铜可以有效提高比电容,并对充放电机理进行了探讨。     

过渡金属/活性炭电极的电容性能研究

选用微孔和中孔活性炭采用浸渍法负载金属离子,考察在水性电解质中用于超级电容器的活性炭复合电极的电化学性能,探讨活性炭在负载前后的放电容量变化情况.采用低温氮吸附和直流恒流循环实验考察活性炭复合电极的孔结构及电容性能.研究表明:金属Cu、Mn具有比较明显的准电容效应,Co、Ni可提高中孔活性炭的放电容量,而金属Mo、Fe和Y的准电容效应不显著;中孔活性炭负载金属的作用明显强于微孔活性炭;中孔活性炭负载金属Cu时,放电容量随负载量的增加而上升.     

Structural modification and enhanced electron emission from multiwalled carbon nanotubes grown on Ag/Fe catalysts coated Si-substrates

Multiwalled carbon nanotubes and carbon nano-filaments were grown using Fe as the main catalyst and Ag as a co-catalyst by microwave plasma enhanced chemical vapour deposition. In this work we demonstrate the growth behaviour of carbon nanotubes (CNTs) grown on pure Fe-film and Ag–Fe films. We find that using Ag film beneath Fe film significantly abate the catalyst–substrate interactions by acting as a barrier layer as well as enhances the nucleation sites for the growth of CNTs due to the limited solubility with Fe and silicon. Scanning electron microscopy and transmission electron microscopy studies were carried out to image the microstructures of the samples. It was observed that the length of Fe catalyzed CNTs was ∼500 nm and Ag–Fe catalyzed CNTs varied from ∼600 nm to 1.7 μm. Micro Raman spectroscopy confirmed the improved crystalline nature of Ag–Fe CNTs. It was found that I_D/I_G ratio for Fe catalyzed CNTs was ∼1.08 and for Ag–Fe catalyzed CNTs was ∼0.7. The Ag–Fe catalyzed CNTs were found to be less defective as compared to Fe catalyzed CNTs. Field emission measurements using diode configuration, showed that electron emission from Ag–Fe catalyzed CNTs was much stronger as compared to Fe catalyzed CNTs. The threshold field for Ag–Fe catalyzed CNTs was (2.6 V μm⁻¹) smaller as compared to Fe catalyzed CNTs (3.8 V μm⁻¹) and thus shows better emission properties. This enhancement in electron emission mechanism as a result of introduction of Ag underlayer is attributed to the increased emitter sites and improved crystallinity.     

碳纳米管的表面修饰及其对碳纳米管/氟橡胶复合材料导电性能的影响

分别采用混酸和四氟化碳(CF4 ) 等离子体处理技术对碳纳米管(MWCNTs) 进行了表面修饰, 将处理前后的碳纳米管进行了XPS 和SEM 测试, 获得了处理后前的表面形貌和结构, 并采用溶液浇注的方式制备了MWCNTs/氟橡胶(FE) 复合材料, 探讨了不同碳纳米管状态(未处理、混酸处理、CF4等离子体处理) 的导电性能, 结果表明两种表面处理方式可以使MWCNTs 表面接上极性官能团。而且在相同的碳纳米管添加量下(质量分数分别为0. 1 %、0. 5 %、1. 0 %、2. 0 %) , 酸处理MWCNTs/ FE 的渗流阈值最小, 达0. 5 %。      

微孔-介孔高比表面积佛手渣基活性炭的制备

在催化和吸附分离等领域,微孔-介孔结构活性炭有广阔的应用前景。以废弃的佛手渣为原料,运用氢氧化钾活化法制备微孔-介孔高比表面积活性炭。考察了炭化和活化等工艺条件对活性炭结构的影响。结果表明,较佳工艺条件下制备的活性炭碘值为1544mg·g-1,BET比表面积1676m2·g-1,微孔BET比表面积350m2·g-1,孔径集中分布在2～5nm之间。     

椰壳活性炭复合改性及其对模拟烟气中CO_2的吸附性能

以椰壳活性炭为载体,进行HNO3+TEPA复合改性和KOH+TEPA复合改性,并考察活性炭复合改性前后对模拟烟气中CO2的吸附性能,结果表明,KOH+TEPA复合改性后吸附性能提高,HNO3+TEPA复合改性后吸附性能降低。KOH+TEPA复合改性后的活性炭(OH-TEPA-AC)在303K条件下,对模拟烟气(10%(体积分数)CO2,90%(体积分数)N2)中CO2的静态吸附量从改性前的0.670mmol/g提高到1.182mmol/g。在303K条件下,活性炭OH-TEPAAC对模拟烟气中CO2的动态吸附量稳定在0.970~1.152mmol/g间,对引入水分的烟气中CO2的吸附量稳定在1.192~1.215mmol/g间,表现出良好的循环吸附性能及对水分的稳定性。动力学分析表明,OH-TEPA-AC对模拟烟气中CO2的平均吸附热值为-52.0kJ/mol,保证了工业实际应用的经济性。     

Hydrothermal synthesis of porous Co(OH)2 nanoflake array film and its supercapacitor application

Porous α-Co(OH)₂ nanoflake array film is prepared by a facile hydrothermal synthesis method. The α-Co(OH)₂ nanoflake array film exhibits a highly porous net-like structure composed of interconnected nanoflakes with a thickness of 15 nm. The pseudo-capacitive behaviour of the Co(OH)₂ nanoflake array film is investigated by cyclic voltammograms (CV) and galvanostatic charge–discharge tests in 2 M KOH. The α-Co(OH)₂ nanoflake array film exhibits high capacitances of 1017 F g^???1 at 2 A g^???1 and 890 F g^???1 at 40 A g^???1 as well as rather good cycling stability for supercapacitor application. The porous architecture is responsible for the enhancement of the electrochemical properties because it provides fast ion and electron transfer, large reaction surface area and good strain accommodation.