高性能超级电容器有序中孔炭材料的研制

采用微湿含浸法制备了一系列具有不同比表面积和孔径分布的超级电容器有序中孔炭材料。采用液氮吸附脱附等温线、小角XRD以及TEM表征了有序中孔炭的孔结构,在1MEt4NBF4|PC电解液中测试了其电化学性能。结果表明,所制得的有序中孔炭的BET比表面积随糠醇加入量的增加先增加后减小,糠醇加入量少制得具有CMK-5结构的有序中孔炭,加入量多制得的CMK-3结构。电化学性能测试结果表明,在1mA·cm-2的充放电电流密度下各有序中孔炭材料比电容的大小顺序与其BET比表面积的大小顺序基本一致,具有CMK-3结构的有序中孔炭的倍率性能最好,并且也好于无序中孔炭的。     

Microwave-irradiated novel mesoporous nickel oxide carbon nanocomposite electrodes for supercapacitor application

Journal of Materials Science: Materials in Electronics - The present work accentuates the aspects of electrochemical analysis determined by cyclic voltammeter (CV), especially enhancement in...     

Direct template synthesis of mesoporous carbon and its application to supercapacitor electrodes

A direct templating method which is facile, inexpensive and suitable for the large scale production of mesoporous carbon is reported herein. A meso-structure surfactant/silicate template was made in a solution phase and resorcinol-formaldehyde as a carbon precursor was incorporated into the template solution. After aging, carbonization and hydrofluoric acid (HF) etching, mesoporous carbon was obtained. Using X-ray diffraction, scanning and transmission electron microscopy and nitrogen sorption, the synthesis mechanism of the mesoporous carbon was elucidated. According to the small angle X-ray scattering measurements, the surface became smoother after the removal of the silica, indicating that the silica was mostly located at the pore surface of the carbon. Also, the calculation of the pore volume demonstrated that the silica was transferred into the pores of the carbon without structural collapse during HF etching. When the prepared mesoporous carbon was applied to a supercapacitor electrode, the rectangular shape of the cyclic voltammogram was less collapsed, even at a high scan rate, which is indicative of its high rate capability. This was due to the low resistance of the electrolyte in the pores (3.8 Ω cm²), which was smaller than that of conventional activated carbon electrodes and even comparable to that of ordered mesoporous carbon electrodes. This improved performance was probably due to the well developed mesoporosity and high pore connectivity of the prepared mesoporous carbon.     

Hierarchical micro- and mesoporous carbide-derived carbon as a high-performance electrode material in supercapacitors

Ordered mesoporous carbide-derived carbon (OM-CDC) materials produced by nanocasting of ordered mesoporous silica templates are characterized by a bimodal pore size distribution with a high ratio of micropores. The micropores result in outstanding adsorption capacities and the well-defined mesopores facilitate enhanced kinetics in adsorption processes. Here, for the first time, a systematic study is presented, in which the effects of synthesis temperature on the electrochemical performance of these materials in supercapacitors based on a 1 M aqueous solution of sulfuric acid and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid are reported. Cyclic voltammetry shows the specific capacitance of the OM-CDC materials exceeds 200 F g(-1) in the aqueous electrolyte and 185 F g(-1) in the ionic liquid, when measured in a symmetric configuration in voltage ranges of up to 0.6 and 2 V, respectively. The ordered mesoporous channels in the produced OM-CDC materials serve as ion-highways and allow for very fast ionic transport into the bulk of the OM-CDC particles. At room temperature the enhanced ion transport leads to 75% and 90% of the capacitance retention at current densities in excess of ～10 A g(-1) in ionic liquid and aqueous electrolytes, respectively. The supercapacitors based on 250-300 μm OM-CDC electrodes demonstrate an operating frequency of up to 7 Hz in aqueous electrolyte. The combination of high specific capacitance and outstanding rate capabilities of the OM-CDC materials is unmatched by state-of-the art activated carbons and strictly microporous CDC materials.     

Mesoporous carbon spheres with uniformly penetrating channels and their use as a supercapacitor electrode material

An optimized nanostructure design for electrode materials of supercapacitors was realized by introducing furfuryl alcohol into as-prepared surfactant-containing spherical host and generating a robust mesoporous structure. The structural characterization shows that the carbon spheres inherit the regular mesopore structure and high surface area of the template and possess a uniform particle size containing well-ordered channels throughout the spheres. By adjusting the initial molar ratio of H₂O to tetraethyl orthosilicate (TEOS), the pore volumes of the templated carbons vary from 0.4 to 0.6 cm³·g^-1 and surface areas are in the range of 610 and 944 m²·g^-1. Furthermore, NiO nanoparticles were incorporated into the carbon spheres by air oxidation of the Ni-containing samples. The use of these spheres in electrode materials for electric double layer capacitors was investigated. The electrochemical measurements show that the specific capacitance of the ordered mesoporous carbon spheres (OMCs-2) can increase by 40% to 205.3 F·g^-1 by the addition of 3 wt% NiO.     

无定型氧化锰超级电容器电极材料

采用化学共沉淀法制备超级电容器用氧化锰电极材料,借助X射线衍射(XRD)、扫描电子显微镜(SEM)、红外光谱(FT-IR)和BET比表面积分析手段对样品进行表征。结果表明,产物为无定型结构,粒径分布较均匀,约在40～50nm,BET比表面积达到160．5m^2／g。在0．5mol／LK2SO4水溶液中,电位窗口为0～0．8V(vs.SCE)内,通过循环伏安和恒流充放电测试,显示该材料制备的电极具有良好的电容行为和功率特性。在扫描速度为4mV／s时,单电极的比容量达到140F／g。     

双模板结构导向剂制备有序介孔炭

以间苯二酚/甲醛制备的酚醛树脂为碳前躯体,三嵌段共聚物F127和P123作为主辅结构导向剂,采用有机-有机自组装的方法制备有序介孔炭(Ordered mesoporous carbons,简称OMCs)。采用X射线衍射仪、透射电镜和N2吸/脱附手段对所制OMCs进行表征,研究了反应时间以及主辅模板剂的比例对介孔孔道结构的影响。结果表明,随着反应时间从24h延长至72 h,介孔炭有序性先增后减;当主辅模板剂F127/P123摩尔比为0.002 7∶0.002 7时,所得介孔炭有序性较好,为P6mm型孔道结构,介孔孔容和比表面积分别为0.59 cm3/g和640.34 m2/g,平均孔径为3.68 nm.     

N-doped ordered mesoporous carbon spheres derived by confined pyrolysis for high supercapacitor performance

Herein, we report a confined pyrolysis strategy to prepare mesoporous carbon nanospheres by which surface area of carbon spheres is increased, pore size is enlarged and effective N-doping is achieved. In this method, the mesoporous polymer sphere as carbon precursor and 2-methylimidazole as nitrogen precursor are encapsulated in a compact silica shell which provides a confined nano-space for the pyrolysis treatment. The in situ generated gases from mesoporous polymer sphere and 2-methylimidazole under pyrolysis diffuse into the pores of mesoporous polymer sphere in the confined compact silica shell, resulting in increased surface area, larger pore size and N-doping due to self-activation effect. As electrodes in supercapacitor, the N-doped mesoporous carbon nanospheres exhibit a significantly enhanced specific capacitance of 326 F g⁻¹ at 0.5 A g⁻¹, which is 2 times higher than that of mesoporous carbon spheres under unconfined pyrolysis condition, exhibiting its potential for electrode materials with high performance.     

Amorphous Mn oxide-ordered mesoporous carbon hybrids as a high performance electrode material for supercapacitors

A supercapacitor has the advantages of both the conventional capacitors and the rechargeable batteries. Mn oxide is generally recognized one of the potential materials that can be used for a supercapacitor, but its low conductivity is a limiting factor for electrode materials. In this study, a hybrid of amorphous Mn oxide (AMO) and ordered mesoporous carbon (OMC) was prepared and characterized using X-ray diffraction, transmission electron microscopy, N2/77 K sorption techniques, and electrochemical analyses. The findings indicate that the electrochemical activities of Mn oxide were facilitated when it was in the hybrid state because OMC acted as a pathway for both the electrolyte ions and the electrons due to the characteristics of the ordered mesoporous structure. The ordered mesoporous structure of OMC was well maintained even after hybridization with amorphous Mn oxide. The electrochemical-activity tests revealed that the AMO/OMC hybrid had a higher specific capacitance and conductivity than pure Mn oxide. In the case where the Mn/C weight ratio was 0.75, the composite showed a high capacitance of 153 F/g, which was much higher than that for pure Mn oxide, due to the structural effects of OMC.     

MnO2/carbon nanotube free-standing electrode recycled from spent manganese-oxygen battery as high-performance supercapacitor material

Journal of Materials Science - Metal–oxygen batteries have been growing rapidly as an energy storage technology in light of their high specific energy density. However, waste...     

Solution blown aligned carbon nanofiber yarn as supercapacitor electrode

Carbon materials with various microtextures and wide availabilities represent very attractive electrode materials for supercapacitors. In this paper, a modified solution blowing process, using a pair of parallel rods as collector, was reported to fabricate carbon nanofiber yarn (CNFY) with polyacrylonitrile (PAN) as precursor polymer. The morphology and structure of the nanofibers were investigated. The PAN precursor and carbon nanofibers were well-aligned and their average diameter was 280 nm and 187 nm, respectively. The performance of CNFY as supercapacitor electrode was evaluated. The CNFY possessed high conductivity of 608.7 Scm^?1 and mass specific capacitance of 70 Fg^?1 at the current density of 500 mAg^?1, and the reduction of capacitance is 29.14 % of the initial value at the current density range from 0.5 to 8 Ag^?1. The superior performance of the CNFY electrode was attributed to the well-aligned structure and high electrical conductivity which afforded the potential application as a novel electrode for supercapacitors.     

The effect of activation methods on the electrochemical performance of ordered mesoporous carbon for supercapacitor applications

Ordered mesoporous carbon (CMK-3) was fabricated by a simple nanocasting method using SBA-15 as a hard template. The CMK-3 had a two-dimensional hexagonal mesoporous structure and a specific surface area of approximately 975.9 m² g^?1. The CMK-3 was modified by HNO₃ solutions with magnetic stirring and ultrasonic activation, respectively, to explore the influence of various activation methods on pore structure, surface state, morphology, and electrochemical performance. The CMK-3 modified by ultrasonic activation (CMK-3-US) reached the optimal specific capacitance of 233.4 A g^?1 at 0.5 A g^?1 and retained 94.2% after 500 cycles in 3 M KOH electrolyte. Furthermore, a symmetric supercapacitor was successfully assembled using CMK-3-US electrodes, which delivered an excellent energy density of 21.5 Wh kg^?1 at a power density of 225 W kg^?1 and exhibited great long-term stability with 97.5% retention after 4000 cycles. Compared to magnetic stirring activation, ultrasonic cavitation could better increase the efficiency of the HNO₃ activation for mesoporous carbon particles. The results indicate ultrasonic activation is an efficient way to modify carbon-based electrode materials for supercapacitors.     

新型超级电容器电极材料

超级电容器以其高功率、长周期使用寿命、环保等独特性能受到人们的广泛关注。决定超级电容器电荷存储的最关键因素是电极材料的特性。首先简要介绍了电容器的电荷储存机理。其次详细介绍了金属有机骨架材料(MOFs)、共价有机骨架材料(COFs)、二维过渡金属碳(氮)化物(MXenes)、金属氮化物(MN)、黑磷(BP)和有机分子电极材料等有望获得高能量密度和功率密度的新兴电极材料,以及最新制作的对称/非对称超级电容器的能量、电容、功率、循环性能和倍率性等参数。研究表明,COFs有望成为新一代廉价、绿色、可持续、多功能的储能装置的有机电极候选材料,其电化学性能仍有很大的提高空间。重点介绍了MOFs、COFs、MN、BP及近年来新型有机电极材料在超级电容器中的应用。最后,对超级电容器未来的发展和关键技术的挑战进行了展望。     

介孔碳材料的制备及对胆红素的优越吸附特性

以MCM-48为模板,利用模板碳化法制备了有序介孔碳材料.运用小角X射线衍射(XRD)、透射电镜(TEM)、紫外可见光谱(UV-vis)等测试方法对介孔碳材料的孔结构参数及对胆红素的吸附特性进行了表征.研究结果表明,介孔碳材料结构高度有序,为立方相Ia3d型,具有高比表面积(1438m2 g-1)、大的孔容(0.98c...     

Preparation and electrochemical properties of nickel oxide as a supercapacitor electrode material

Hydrothermal synthesis has been introduced to fabricate NiO precursor at different temperatures, then nanostructured NiO with a distinct flake-like morphology was obtained via heating at low temperature. The NiO nanoflakes are 50-80 nm in width and 20 nm in thickness. The electrochemical capacitive characterization of the as-prepared NiO was studied in 2 M KOH electrolyte solution. The as-prepared NiO exhibits excellent cycle performance and keeps 91.6% initial capacity over 1000 charge-discharge cycles. Electrochemical impedance spectroscopy study reveals that the NiO electrode is controlled by the mass transfer limitation, and its internal resistance is 0.2 Ω. A specific capacitance approximate to 137.7 F g⁻¹ could be achieved at the current density of 0.2 A g⁻¹ in the potential window of 0-0.46 V in 2 M KOH electrolyte solution, due to higher surface area of NiO nanoflakes, which facilitates transport of electrolyte ions during rapid charge/discharge process. Due to higher surface area of NiO nanoflakes, which facilitates transport of electrolyte ions during rapid charge/discharge process.     

超级电容器用活性炭的制备与电化学表征

以煤焦油沥青为前驱体,采用化学活化法制备了超级电容器用高比表面活性炭和活性炭电极.考察了活化温度对活性炭电极比电容量的影响,研究了活性炭材料的比表面积和孔结构与活性炭电极的充放电性能之间的关系,并对活性碳电极进行了电化学表征.结果表明,在500～700℃,随着活化温度的提高,活性炭电极的比电容量显著增大,当活化温度超过700℃时,活性炭电极材料的比电容量变化不明显.700℃活化温度下所制备的活性炭材料呈现明显的多孔结构,孔容为1.038cm3/g,比表面积为1959m2/g;所制成的活性炭电极比电容量为210F/g,等效内阻为0.9Ω/cm2,10mA/cm2充放电500次后保持90%以上电容量,交流阻抗谱在频率低于转化点时表现出纯粹的电容行为,循环伏安曲线显示出良好的可逆特性.     

Nitrogen-doped graphene/carbon nanohorns composite as a high-performance supercapacitor electrode

Nitrogen-doped graphene/carbon nanohorns composite(NGLC) was prepared by one-step co-pyrolysis of graphene oxide, carbon nanohorns(CNHs), urea, and lignosulfonate. CNHs as spacers were inserted into graphene nanosheets. The introduction of CNHs and the loosened nano-structure of NGLC make it achieve a high specific capacitance of 363 Fg~(-1) at a discharge current density of 1 A g~(-1), and NGLC exhibits an ultrahigh stability of 93.5% capacitance retention ratio after 5000 cycles. The outstanding comprehensive electrochemical performance of NGLC could meet the need of the future acted as an efficient supercapacitor electrode material.     

Metal catalyst adsorption effects in the growth of carbon nanostructures on mesoporous material

Mesoporous silica films were used as host for metal-based (Me = Fe, Co, Ni) nanoparticles via wet impregnation at pH = 5. A hydrogen ion beam was used to reduce the metallic oxide and hydroxides, previously detected by X-ray photoelectron spectroscopy, in metals. Chemical vapor deposition processes at three different conditions varying the acetylene-nitrogen proportion were performed on the mesoporous films decorated by different metal-based nanoparticles. The grown carbon nanostructures were characterized by high-resolution transmission electron microscopy and scanning electron microscopy. The ability to grow carbon nanostructures decreases in the following order: Fe > Co > Ni. When pure acetylene is used, iron allows to form graphene sheets around the metal catalyst like carbon nanocapsules, whereas cobalt allows to form structures that seem to be carbon nanotubes. Nitrogen leads to control the size and shape of carbon nanocapsules for iron catalyst and avoid the growth of such carbon nanotube-like structures for cobalt catalyst.