纤维素基生物质多孔炭的制备及其超级电容器性能研究

以棉纤维素为原料,采用硝酸盐、尿素、纤维素共混后热裂解的方法制备分级多孔炭HPC样品,通过改变煅烧温度和KOH活化处理对多孔炭比表面积及孔结构进行调控。对比三个不同温度煅烧活化处理后样品的循环伏安曲线、恒电流充放电曲线、比容量等电化学参数,结果表明,4AC@HPC800样品作为超级电容器工作电极具有优良的电化学性能,其比表面积高达2433.8 m²·g^-1,在1 A·g^-1的电流密度下比容量高达234.7 F·g^-1,在大电流密度10 A·g^-1时依然有207.6 F·g^-1的比容量,具有良好的倍率性能;电极在2 A·g^-1的电流密度下循环10000次后依然有196.1 F·g^-1的比容量,表明其具有长时工作的特性。     

纤维素基生物质多孔炭的制备及其超级电容器性能研究

以棉纤维素为原料,采用硝酸盐、尿素、纤维素共混后热裂解的方法制备分级多孔炭HPC样品,通过改变煅烧温度和KOH活化处理对多孔炭比表面积及孔结构进行调控。对比三个不同温度煅烧活化处理后样品的循环伏安曲线、恒电流充放电曲线、比容量等电化学参数,结果表明,4AC@HPC800样品作为超级电容器工作电极具有优良的电化学性能,其比表面积高达2433.8 m²·g^-1,在1 A·g^-1的电流密度下比容量高达234.7 F·g^-1,在大电流密度10 A·g^-1时依然有207.6 F·g^-1的比容量,具有良好的倍率性能;电极在2 A·g^-1的电流密度下循环10000次后依然有196.1 F·g^-1的比容量,表明其具有长时工作的特性。     

Preparation and electrochemical performance of polyaniline-based carbon nanotubes as electrode material for supercapacitor

Nitrogen-containing carbon nanotubes (CNTs) with open end and low specific surface area were prepared via the carbonization of polyaniline (PANI) nanotubes synthesized by a rapidly mixed reaction. On the basis of analyzing the morphologies and structures of the original and carbonized PANI nanotubes, the electrochemical properties of PANI-based CNTs obtained at different temperatures as electrode materials for supercapacitors using 30 wt.% aqueous solution of KOH as electrolyte were investigated by galvanostatic charge/discharge and cyclic voltammetry. It was found that the carbonized PANI nanotubes at 700 °C exhibit high specific capacitance of 163 F g⁻¹ at a current density of 0.1 A g⁻¹ and excellent rate capability in KOH solution. Using X-ray photoelectron spectroscopy measurement the nitrogen state and content in PANI-CNTs were analysed, which could play important roles for the enhancement of electrochemical performance. When the appropriate content of nitrogen is present, the presence of pyrrole or pyridone and quaternary nitrogen is beneficial for the improvement of electron mobility and the wettability of electrode.     

对位芳纶气凝胶粉体的制备与性能研究

以对位芳纶纳米纤维(PANF)水凝胶为原料,将冻凝胶粉碎法与冷冻干燥法相结合,制备出PANF气凝胶粉体。系统研究了对位芳纶气凝胶粉体的微观结构及性能参数,以及制备条件对产物形貌的影响,并初步探究了其应用。结果表明,液氮冷冻制备的PANF气凝胶粉体具有多孔结构,松装密度约为17.0 kg?m^-3,孔隙率约为98.8%,BET比表面积可达126.30 m²?g^-1。PANF气凝胶粉体的耐热性优异,在氮气气氛下500℃前几乎无分解;热导率较低,约为0.03 W?m^-1·K^-1。气凝胶粉体具有吸附罗丹明B等染料的特征,同时可作为纳米填充材料增强聚氨酯乳胶膜等聚合物材料的硬度,其低热导率表明其有望应用于绝热领域。     

A novel high power symmetric ZnO/carbon aerogel composite electrode for electrochemical supercapacitor

We present, for the first time, a new material of symmetric electrochemical supercapacitor in which zinc oxide (ZnO) with carbon aerogel (CA) was used as active material. Physical properties of ZnO/CA composite were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that ZnO has single hexagonal structure and the grain size increases with increase of ZnO compository. The result of cyclic voltammetry indicates that the specific capacitance of ZnO/CA composite in 6 M KOH electrolyte was approximately 25 F/g at 10 mV/s for 2:1 composition. AC impedance analysis reveals that ZnO with carbon aerogel powder enhanced the conductivity by reducing the internal resistance. Galvanostatic charge/discharge measurements were done at various current densities, namely 25, 50, 75, and 100 mA/cm². It was found that the cells have excellent electrochemical reversibility and capacitive characteristics in KOH electrolyte. The maximum capacitance of the ZnO/CA supercapacitor was 500 F/g at 100 mA/cm². It has been observed that the specific capacitance is constant up to 500 cycles at all current densities, which implies that the dendrite formation was controlled.     

Dispersing WO3 in carbon aerogel makes an outstanding supercapacitor electrode material

Tungsten oxide, originally poor in capacitive performance, was made an excellent electrode material for supercapacitors, by dispersing it to carbon aerogels (CA), a conductive and mesoporous hosting template, that drastically improved the utilization of WO₃ for capacitance generation. The WO₃ was introduced to the CA, in a form of well-dispersed single crystalline nanoparticles of 15–40 nm in size, with a simple immersion-calcination process. A one order of magnitude improvement in specific capacitance was achieved with the present composition, from 54 F/g for WO₃ nanoparticles to 700 F/g for WO₃/CA composites (scaned at 25 mV/s in 0.5 M H₂SO₄ over a potential window of −0.3 to 0.5 V). The WO₃/CA composites exhibited an excellent high rate capability with a 60% retention in specific capacitance at 500 mV/s, almost perfect cycle efficiency of 99%, and outstanding cycling stability of only 5% decay in specific capacitance after 4000 cycles.     

Enhanced surface hydrophobisation for improved performance of carbon aerogel electrochemical capacitor

A more efficient surfactant vinyltrimethoxysilane (vtmos) than previously reported one, sodium oleate (OAS), has been employed to enhance surface hydrophobisation of carbon aerogel for electric double layer capacitor (EDLC) application. In comparison with attachment of hydrophobic moiety of OAS species to carbon surface grafting of vinyltrimethoxysilane functional group enhances more efficiently the hydrophobisation of carbon material and the affinity toward propylene carbonate (PC) solvent, and accordingly improves more considerably the wettability of carbon in PC-based electrolyte solution. The enhanced wettability facilitates more rapid electrolyte ions transport within micropores of the vtmos modified carbon aerogel, resulting in lower internal resistance and energy loss than OAS modified carbon capacitor, and also favors more surface area for EDL formation, resulting in higher specific capacitance and energy for vtmos modified carbon aerogel electrochemical capacitor. In addition, vtmos modified carbon material has shown comparable charge-discharge cycling stability to that obtained by the original carbon.     

Preparation and properties of PAN-based carbon fiber-reinforced SiCO aerogel composites

To overcome the brittleness issue of SiCO aerogels, the polyacrylonitrile-based (PAN) carbon fiber was impregnated with SiCO sol to obtain carbon fiber-reinforced SiCO aerogel composites (C/SiCO). SiCO sol was prepared through an acid-alkaline two-step catalysis by using methyltrimethoxysilane (MTMS) and dimethyldiethoxysilane (DMDES) as precursors. C/SiCO-1, C/SiCO-2 and C/SiCO-3 were obtained after repeated impregnation of the SiCO sol and gelating, aging, supercritical drying and pyrolyzing one to three times. SEM images show that the SiCO aerogel fills the pores between the carbon fibers, and the nanoporous structure of the SiCO aerogel can effectively improve the thermal insulation of the composites. As the times of impregnation of the SiCO sol increased, the mechanical properties and oxidation resistance of C/SiCO have been improved significantly. The bending strength of C/SiCO-3 was 32.52 MPa, and the compressive strength (25%ε) was 51.98 MPa. After heating at 1600 °C, the linear shrinkage in the thickness direction of C/SiCO-1 was 20.72%, while that of C/SiCO-3 was only 1.85%. A dense SiO₂ molten oxide film formed on the surface of C/SiCO at high temperature, and its extremely low oxygen permeability effectively protected the inside of the composites.     

活性炭的微结构与超级电容器性能的构效关系

以生物质柞木为原料,采用不同活化法制备具有不同结构特征的柞木基活性炭,利用N₂吸附、FT-IR、XPS、XRD、Raman光谱等表征手段对活性炭的微结构特性进行解析,探究活化方式对活性炭微结构性能的影响;微结构与超级电容器性能的构效关系。研究表明： KOH和H₃PO₄-KOH法制备的活性炭微孔发达,炭结构表面缺陷位与杂原子丰富,在低电流密度下表现出更高的比电容;H₃PO₄-KOH法制备的活性炭具备更宽的微介孔分布与孔道连通性,使其具有更好的电容保持率;CO₂、H₃PO₄和H₃PO₄-CO₂法制备的活性炭介孔发达,微孔体积小,孔道连通性差,炭结构相对完整,裸露于炭结构表面的缺陷与杂原子相对较少,尽管电容保持率较高,但比电容较低。因此,高性能的超级电容器活性炭电极应具有发达的微孔结构、较宽的微介孔分布、通畅的微介孔连通结构,同时含有更多的裸露于炭结构表面的结构缺陷与杂原子基团,从而提高超级电容器的能量密度。     

用于超级电容器的硫化钴/石墨烯气凝胶复合材料的研究

采用一步水热法,在乙二胺的辅助下,制备了硫化钴/石墨烯气凝胶(CoS/GA)复合材料。通过X射线衍射法(XRD)、扫描电镜(SEM)、电化学性能测试对材料进行了表征和测试。结果表明:制备的材料晶型规整,30～100 nm的CoS粒子均匀地分布在石墨烯气凝胶上。用作超级电容器时,在电流密度0.5 A/g时,CoS/GA复合材料比电容值达574 F/g,是纯CoS的1.4倍;充放电循环1 000次后,比电容保持率为94.4%。硫化钴/石墨烯复合材料的电化学性能较好,具有较大的比电容和较好的循环稳定性,是一种可用于超级电容器的较有潜力的电极材料。     

夹心型生物碳电极材料的制备及超级电容器性能

选择板栗壳为碳源(CC),炭化后用KOH活化,制得CC700-OH电极材料.通过SEM、TEM、XRD以及BET等对其形貌和性能进行了表征与测试,发现CC700-OH具有孔/片穿插的夹心结构.在电流密度为1 A/g时,比电容为540 F/g,在电流密度为10 A/g下,循环6000圈后比电容仍可保持初始值的98％.在二...     

超盐环境下含氮碳气凝胶的制备及其在超级电容器中的应用

多孔碳材料因其优异的导电性和稳定性,以及成本低廉等优点而成为当今的研究热点之一。以苯酚、甲醛和三聚氰胺为原料,利用高浓度氯化锌来提供超盐环境,经溶剂热反应后,在氮气中800℃下热解制得了含氮碳气凝胶(NCA)。扫描电子显微镜、拉曼光谱、X射线光电子能谱和氮气吸附等表征结果表明,该含氮碳气凝胶具有分级多孔蜂窝状结构,其比表面积高达729.6 m2/g。采用三电极测试体系测试了含氮碳气凝胶的电化学性能,结果表明,在三电极体系中,以0.5 mol/L H₂SO₄作为电解液,含氮碳气凝胶在电流密度为1 A/g时比电容达到350.7 F/g;在电流密度为20 A/g时,经过10000次充放电后,含氮碳气凝胶的电容保持率仍高达97.8%。在双电极体系中,含氮碳气凝胶在800 W/kg的功率密度下,能量密度可达26.8 (W·h)/kg。上述结果表明,该含氮碳气凝胶是一种非常理想的超级电容器电极材料。     

Preparation and one-step activation of microporous carbon nanofibers for use as supercapacitor electrodes

Microporous carbon nanofibers were prepared by electrospinning from resole-type phenolic resin, followed by one-step activation. KOH was utilized to tune the fiber diameter and improve porous texture. By adjusting KOH content in the spinning solution, the fiber diameter could be controlled in the range of 252–666 nm and the microporous volume and specific surface area could be greatly improved. The electrochemical measurements in 6 M KOH aqueous solution showed that the microporous carbon nanofibers possessed high specific capacitance, considerable rate performance, and superior specific surface capacitance to conventional microporous carbons. The maximal specific capacitance of 256 F g⁻¹ and high specific surface capacitance of 0.51 F m⁻² were achieved at 0.2 A g⁻¹. Furthermore, the specific capacitance could still remain 170 F g⁻¹ at 20 A g⁻¹ with the retention of 67%. Analysis showed that the high specific surface capacitance of the resultant carbons was mainly attributed to optimized pore size (0.7–1.2 nm) and the excellent rate performance should be principally due to the reduced ion transportation distance derived from the nanometer-scaled fibers.     

Preparation of aerogel beryllium borate with supercritical carbon dioxide drying

A supercritical carbon dioxide drying technique was developed to prepare nanometer particulate materials. The technique consists of preparation of an aqueous gel, filtering, washing, replacement of the water in the gel with a mixture solvent of n-butanol and ligroin and supercritical carbon dioxide drying. The product was characterized with TEM, XRD and X-ray small-angle scattering. The results indicated that an amorphous aerogel of the beryllium borate was obtained with this technique. The diameter of the product particles was about 7 nm. Isopropyl alcohol supercritical drying was also used to prepare aerogel beryllium borate, where recrystallization took place due to the high critical temperature of isopropanol.     

活性炭/二氧化锰纳米复合材料的合成及超级电容性能

以商业活性炭为载体,通过硝酸表面改性活性炭,引入含氧官能团,为棒状二氧化锰(MnO2)和活性炭的结合提供桥梁。采用化学沉淀法在炭表面反应生成纳米结构的棒状二氧化锰,制备二氧化锰/改性活性炭(MnO2/OAC)复合电极材料。采用扫描电镜(SEM)、X射线衍射(XRD)对其结构进行表征;采用循环伏安法、恒流充放电对其电化学性能进行研究。结果表明,生成的MnO2均匀地负载在碳的表面,颗粒的直径在20~50nm;在1mol/L的Na2SO4电解液中,MnO2/OAC6复合电极材料体现了极佳的比电容,达到369.7F/g。材料优异的电化学性能归功于活性炭发达的孔隙结构和MnO2提供的法拉第电容。     

活性炭/二氧化锰纳米复合材料的合成及超级电容性能

以商业活性炭为载体,通过硝酸表面改性活性炭,引入含氧官能团,为棒状二氧化锰(MnO2)和活性炭的结合提供桥梁。采用化学沉淀法在炭表面反应生成纳米结构的棒状二氧化锰,制备二氧化锰/改性活性炭(MnO2/OAC)复合电极材料。采用扫描电镜(SEM)、X射线衍射(XRD)对其结构进行表征;采用循环伏安法、恒流充放电对其电化学性能进行研究。结果表明,生成的MnO2均匀地负载在碳的表面,颗粒的直径在20⁵0nm;在1mol/L的Na2SO4电解液中,MnO2/OAC6复合电极材料体现了极佳的比电容,达到369.7F/g。材料优异的电化学性能归功于活性炭发达的孔隙结构和MnO2提供的法拉第电容。     

Preparation and electrochemical investigation of the polyaniline/activated carbon nanocomposite for supercapacitor applications

The polyaniline (PANI)/activated carbon (AC) nanocomposite electrodes were prepared by electropolymerization of aniline monomers on the surface of AC/polyvinyl alcohol (PVA) electrodes for supercapacitor studies. Fourier transforms infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses were performed to characterize the structure and morphology of the nanocomposite electrodes. The electrochemical properties of the prepared nanocomposite electrodes and the supercapacitive behavior of the PANI, AC, and AC/PANI/PVA electrodes were investigated using cyclic voltammetry (CV) and galvanostatic charge/discharge measurements, respectively. Morphological studies showed that a thin film of PANI has been uniformly deposited on the porous surface of AC electrode, and an ordered arrangement of nanostructures with interlinked porous network has been made. Electrochemical measurements showed that AC particles prevent the degradation of PANI chains during charge/discharge cycles. The specific capacitance of the AC/PANI/PVA nanocomposite electrode was 338.15 F/g which is higher than that of the pristine AC electrode (0.08 F/g). This is due to the contribution of PANI chains by their pseudocapacitance (redox reaction) properties. Although the specific capacitance of PANI electrode (378.57 F/g) was greater than that of the nanocomposite electrode, the cyclic stability of the PANI electrode was lower than that of the AC/PANI/PVA nanocomposite electrode.     

Hierarchically Fe-doped porous carbon derived from phenolic resin for high performance supercapacitor

Supercapacitors are promising for high power application in the recent years. In particular, the conversion of simple and available carbon materials into economic and high performance electrical devices receives excellent scientific and technological interest. This paper reports a one-step strategy for synthesizing hierarchical porous carbon derived from phenolic resin (PR), which is then used to configure electric double-layer capacitors (EDLCs). Here, a carbon material with a flexible porous structure, large specific surface area, and high graphitization degree is prepared using potassium ferrate (K₂FeO₄) to catalytically activate PR and to realize synchronous carbonization and graphitization. This method overcomes the disadvantage of time-consuming, high-cost, and environmentally unfriendly. In addition, the as-prepared carbon material has a high specific surface area (1086 m² g^?1) and a large pore size (3.07 nm), which can increase the transfer rate of electrolyte ions. The specific capacitance of the obtained electrode material is 315 F g^?1 at 1.0 A g^?1, and the optimized electrode material has an ultra-long cycle lifetime (capacitance retention rate is 96.3% after 10,000 cycles). Thus, the hierarchically Fe-doped porous carbon material derived from PR material is expected to realize high rate capacitance for supercapacitor applications.     

Preparation and characterization of magnetic carbon aerogel from pyrolysis of sodium carboxymethyl cellulose aerogel crosslinked by iron trichloride

Multifunctional carbon aerogel was prepared by pyrolysis of sodium carboxymethyl cellulose aerogel after sol–gel processing and freeze-drying. Ferric iron and D-(+)-gluconic acid-lactone were used as cross-linker and releasing agent, respectively. The as-prepared carbon aerogel was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffractometry, thermogravimetric analysis, nitrogen adsorption measurements, vibrating sample magnetometry and water contact angle tests. The carbon aerogel had a high specific surface area of 742.34 m²/g and contained mostly mesopores. Its density was as low as 0.062 g/cm³. The carbon aerogel morphology has an uneven three-dimensional structure and presented a type-IV adsorption isotherm. Carbonization resulted in the destruction of the carboxymethyl cellulose crystalline structure, damage to the oxygen-containing functional groups and provided the carbon aerogel with good magnetic properties. The carbon aerogel displayed good hydrophobicity and flame retardance, which has potential application in adsorption, hydrophobic materials and fireproofing.     

Room-temperature synthesis and characterization of cobalt-doped carbon nanofibers

The graphite surfaces were irradiated by Ar⁺ ions with and without a simultaneous Co supply at room temperature. The sputtered surface without Co supply was characterized by densely distributed conical protrusions with aligned carbon nanofibers (CNFs) on the tops, whereas Ar⁺-bombarded surfaces with a simultaneous Co supply were covered with asparagus-like (micrometer order in base diameter) or nanofibrous (10–50 nm in diameter) structures depending on the supply rate of Co atoms. No CNF-tipped cones were observed to form. For the nanofibers containing carbon and cobalt, the hysteresis behavior observed in the magnetization property by applying magnetic fields in directions perpendicular and parallel (in-plain) to the substrate was almost identical, whereas a continuous 1 µm thick-Co film showed the strong in-plane anisotropy. Other materials could be readily incorporated into CNFs by choosing the suitable metal sources. Thus, the ion-irradiation method is expected to open up a new approach to fabricate ferromagnetic 1-D nanomaterials at room temperature.