不同N掺杂构型石墨烯的量子电容研究

超级电容器是一种利用界面双电层储能或在电极材料表面及近表面发生快速可逆氧化还原反应而储能的装置, 其特点是功率密度高、循环寿命长. 制备出兼有高能量密度的电极材料是当前超级电容器研究的重点. 以提高电容储能为目标, 通过掺杂N原子来调制石墨烯的电子结构, 使用基于密度泛函理论的第一原理计算了不同N掺杂构型石墨烯的态密度和能带结构, 拟合出了石墨烯的量子电容, 分析了量子电容储能提升的原因.     

氮掺杂石墨烯纳米片的制备及其电化学性能

以石墨片为原料,在氮气气氛下,通过机械针磨法制备了氮掺杂石墨烯纳米片.扫描电子显微镜和比表面积分析表明机械针磨过程可以有效地将大尺寸石墨片破碎成石墨烯纳米片.在石墨片的破碎过程中,会引起C—C键的破坏.因此,在破坏的边缘位置能够产生碳活性点.这些碳活性点可以与氮反应实现氮元素的掺杂.X射线光电子能谱分析表明碳活性点与氮反应使氮元素掺入石墨烯结构边缘,形成吡咯型氮和吡啶型氮.电化学阻抗谱分析表明所制备的氮掺杂石墨烯纳米片对I_3~-还原反应具有较高的电催化活性,循环伏安与恒流充放电测试表明氮掺杂石墨烯纳米片具有较好的电容性能.较高的比表面积和边缘氮掺杂结构是氮掺杂石墨烯纳米片具有优异电化学性能的主要原因.因此,氮掺杂石墨烯纳米片可以应用于染料敏化太阳能电池对电极和超级电容器电极.     

电化学阴极沉积制备氧化钴/CNTs复合电极的准电容特性

采用电化学阴极沉积还原Co(NO3)2的方法制备了具有准电容特性的氧化钴电极材料,其比容量达到280 F／g,采用CNTs作为电极基体,在其表面均匀的沉积了纳米钴化镍颗粒并由此制备了氧化钴碳纳米管复合电极材料.采用循环伏安,恒流充放电,交流阻抗及扫描电镜等方法考察了复合电极材料的容量特性、阻抗特性、自放电特性以及电极表观特征．实验表明复合电极具有良好的电化学特性,CNTs基体在明显降低氧化镍材料的阻抗的同时还提高了电极材料的电化学容量并拓宽了电极材料的有效工作电位窗,复合电极在1 mol／L KOH电解液中比容量达到322 F／g且表现了良好的电化学可逆性．并分别采用氧化钴／CNTs复合电极作为正极,活性炭纤维作为负极制备了复合型电化学电容器,其工作电压达到1．4 V,电容器质量比容量达到47 F／g．在0．1 A／cm2放电时,复合型电容器的能量密度达到10 Wh／kg,兼具高能量特性和优良的大电流放电特性．     

电化学超级电容器电极材料的研究进展

超级电容器是一种利用电化学双电层储能或在电极材料表面及近表面发生快速可逆氧化还原反应而储能的装置,具有高的比功率、比能量和长的循环寿命.文章综述了超级电容器电极材料的储能机理、特点及应用,并重点介绍了石墨烯、二氧化锰及其复合电极材料在超级电容器中应用的最新研究进展.     

多孔碳纳米球的制备及其电化学性能

以三嵌段共聚物F108为软模板,通过水热法合成酚醛树脂球并在氮气氛围下碳化、KOH活化处理,最终得到多孔碳纳米球材料.通过扫描电子显微镜、透射电子显微镜和氮气吸附分析仪对样品进行表征,结果表明样品的平均粒径为120 nm,球形度高,比表面积达到1403 m~2/g,孔径分布广.通过X射线衍射研究样品的结晶度,傅里叶红外光谱分析样品表面官能团的情况,结果表明KOH处理和高温处理使得样品的微晶结构有序度提高,表面官能团含量降低.以多孔碳纳米球作为超级电容器电极的活性物质,电化学特性测试结果表明,多孔碳纳米球材料的比电容能够达到132 F/g(0.2 A/g),在10 A/g的电流密度下,经过10000次循环充放电后,电容量保留率为97.5%.本文采用水热法制备的多孔碳纳米球电化学性能良好,适用于超级电容器电极材料,研究结果表明,比表面积大、孔径分布合适(具有一定介孔含量)、结晶度高和含有少量表面官能团的理化特性的电极材料,其电化学性能更加优越.     

石墨烯/聚乙撑二氧噻吩薄膜储能特性（英）

为了有效利用石墨烯和导电聚合物材料,光雕石墨烯/聚3,4-乙撑二氧噻吩(LSG/PEDOT)复合薄膜通过一种灵巧的光雕工艺制备出来。在此复合薄膜中,每种组分对薄膜的电化学性能提升都有独特的贡献。循环伏安、交流阻抗及恒流充放电测试用来检测薄膜的电化学性能。结果显示,在引入PEDOT纳米颗粒后,LSG/PEDOT复合薄膜显示出更好的能量存储能力。复合薄膜的比容量达到64.33 F/cm3,是光雕石墨烯比容量(3.89 F/cm3)的20倍,复合薄膜经过1000次循环后仍能保持初始容量的94.6%。复合薄膜电化学性能的提升主要是由于引入的PEDOT纳米颗粒既阻挡了石墨烯的层层堆叠,又增加了整个薄膜的比表面积。此种灵活的光雕工艺还可以用来大规模制备超级电容器电极。     

石墨烯在超级电容器中的应用

正1.引言超级电容器是一种介于传统电容器和二次电池之间的新型电化学储能元件,它拥有功率密度高、充放电速率快、环境友好、温度特性好及使用寿命长等优点(表1),已在备用电源系统、便携式电子设备和电动汽车领域有广泛的应用。众所周知,电极材料是超级电容器的关键所在,它决定着电容器的主要性能指标,如能量密度、功率密度和循环稳定性等,所以制备合成具有优异性能的电极材料成为超级电容器研究的核心课题。目前,超级电容器的电极材料主要可以分为三类:碳基材料、过渡金属化合物和导电聚合物如图1     

中空笼状多孔结构镍钴层状氢氧化物的制备及其电化学性能

超级电容器以功率密度高、寿命长、环境友好等优点在各种能量存储设备中受到广泛关注.所以,提高电极材料的储能性能对超级电容器的开发与应用具有重要的意义.具有特定纳米结构的功能材料作为超级电容器电极材料时具有优异的电化学性能,原因在于其能提供丰富的电化学活性位点、高的比表面积和增加电解质与材料的接触面积.因此,本文以ZIF-67纳米晶为模板,利用硝酸盐刻蚀的方法制备中空笼状镍钴层状氢氧化物(NiCo-LDH),并研究其作为超级电容器电极材料的储能性能.借助X射线衍射、扫描电镜、透射电镜、低温氮气吸附/脱附和电化学测试等手段分析所得NiCo-LDH的结构、形貌和电化学性能.结果表明:NiCo-LDH由纳米片组装形成中空笼状结构,拥有丰富的介孔和大孔孔道以及较高的比表面积,从而有助于增加电活性位点,促使电解液与电极材料的充分接触,进而显著提高材料的储能性能.当刻蚀用镍、钴盐质量比为1:1时,样品Ni₁Co₁-LDH的比电容可达801 F·g^-1(电流密度为0.5 A·g^-1),且在大电流密度下(10 A·g<...     

电化学阴极沉积制备氧化镍/碳纳米管复合电极的准电容特性

采用催化裂解的方法制备了碳纳米管,其比容量为12F/g.采用碳纳米管作为电极基体,采用阴极电化学还原Ni(NO3)2的方法在碳纳米管基体表面均匀的沉积了纳米氧化镍颗粒并由此制备了氧化镍碳纳米管复合电极材料.采用循环伏安、恒流充放电、交流阻抗及扫描电镜等方法考察了复合电极材料的容量特性、阻抗特性、自放电特性以及电极表观特征.实验表明复合电极具有良好的电化学特性,碳纳米管基体在明显降低氧化镍材料的阻抗的同时还提高了电极材料的电化学容量并拓宽了电极材料的有效工作电位窗,复合电极在6mol/LKOH电解液中比容量达到25F/g且表现了良好的电化学可逆性.与碳纳米管基电容器相比,采用氧化镍复合电极材料组装的电容器具有较低的自放电率.     

MnO_2/石墨烯复合电极材料的制备与储能性能

以葡萄糖为还原剂,天然石墨片为原料,采用Hummer法制备了石墨烯粉末(Graphene);并以该产物、KMnO4和HCl为原料,采用水热法制备了MnO2/Graphene复合材料。用扫描电子显微镜和X射线衍射对所制备的复合材料进行了表征,结果表明,水热法制备的MnO2材料为纯的α-MnO2相,且石墨烯粉末的加入并没有影响MnO2的晶体结构。在1mol/L Na2SO4电解液中进行了循环伏安和计时电位扫描测试,电极材料电化学性能稳定,具有较好的可逆性,在1.27mA/cm2电流密度下进行充放电测试时,电极比电容为147.9F/g;再循环1000次后,电极仍能保持稳定的电容,是一种理想的电化学电极材料。     

In Situ Synthesis and Characterization of Polypyrrole/Graphene Conductive Nanocomposites via Electrochemical Polymerization and Chemical Reduction

Polypyrrole/graphene sheets (PPy/GNs) nanocomposite electrodes were in- situ synthesized via electrochemical polymerization and chemical reduction from pyrrole (Py) and graphene oxide (GO). The surface morphologies of the nanocomposites were observed by scanning electron microscopy (SEM). The SEM results showed graphene sheets (GNs) scattered on the surface of the polypyrrole (PPy), and the morphologies of PPy/GNs nanocomposites manufactured by pulse current (PC-PPy/GNs) or direct current (DC-PPy/GNs) were smoother than that of PC-PPy. The electrochemical capacitance properties of the nanocomposite films were measured by cyclic voltammetry (CV), galvanostatic charge and discharge (GC), and electrochemical impedance spectroscopy (EIS) techniques in 3 mol·L^?1 KCl aqueous solutions. The results indicated that the specific capacitance of the DC-PPy/GNs nanocomposite was 13.5% higher than that of a PC-PPy electrode. Comparison of the electrochemical performance of the nanocomposites indicated that the PC-PPy/GNs nanocomposite had higher specific capacitance and better charging/discharging capability than that of the DC-PPy/GNs nanocomposite. The specific capacitance of the PC-PPy/GNs nanocomposite could reach to 280 F·g^?1 at a scanning rate of 100 mV·s^?1.     

Silver nanoparticles decorated on a three-dimensional graphene scaffold for electrochemical applications

Silver metal nanoparticles were decorated by electron beam evaporation on graphene foam (GF) grown by chemical vapour deposition. X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, and atomic force microscopy were used to investigate the structure and morphology of the graphene foam/silver nanoparticles (GF/Ag). Both samples were tested as electrodes for supercapacitors. The GF/Ag exhibited a significantly higher capacitive performance, including a specific capacitance value of (~110 Fg⁻¹) and excellent cyclability in a three-electrode electrochemical cell. These results demonstrate that graphene foam could be an excellent platform for metal particles for investigating improved electrochemical performance.     

Electrode surface treatment and electrochemical impedance spectroscopy study on carbon/carbon supercapacitors

Power improvement in supercapacitors is mainly related to lowering the internal impedance. The real part of the impedance at a given frequency is called ESR (equivalent series resistance). Several contributions are included in the ESR: the electrolyte resistance (including the separator), the active material resistance (with both ionic and electronic parts) and the active material/current collector interface resistance. The first two contributions have been intensively described and studied by many authors. The first part of this paper is focused on the use of surface treatments as a way to decrease the active material/current collector impedance. Al current collector foils have been treated following a two-step procedure: electrochemical etching and sol-gel coating by a highly-covering, conducting carbonaceous material. It aims to increase the Al foil/active material surface contact leading to lower resistance. In a second part, carbon-carbon supercapacitor impedance is discussed in term of complex capacitance and complex power from electrochemical impedance spectroscopy data. This representation permits extraction of a relaxation time constant that provides important information on supercapacitor behaviour. The influence of carbon nanotubes addition on electrochemical performance of carbon/carbon supercapacitors has also been studied by electrochemical impedance spectroscopy. PACS 82.45.Yz; 81.16.-c     

Hollow polypyrrole nanosphere embedded in nitrogen-doped graphene layers to obtain a three-dimensional nanostructure as electrode material for electrochemical supercapacitor

A novel approach was developed to prepare hollow polypyrrole (PPy) nanospheres and nitrogen-doped graphene/hollow PPy nanospheres (NG/H-PPy) composites. In this process, uniform poly (methyl methacrylate-butyl methacrylate-methacrylic acid) (PMMA-PBMA-PMAA) latex microspheres as sacrificial templates were synthesized by using an emulsion polymerization method. Then, hollow PPy nanospheres were obtained on the surface of PMMA-PBMA-PMAA microspheres by in situ chemical oxidative polymerization. Finally, H-PPy was embedded in NG layers successfully through a simple approach. The nanobeads have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectra, and Fourier transform infrared spectra (FTIR). Different electrochemical methods including cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) have been applied to study the electrochemical properties. The specific capacitance of NG/H-PPy composites based on the three-electrode system is as high as 575 F g^?1 at a current density of 1 A g^?1 and enhanced stability about 90.1 % after 500 cycles, indicating that the composite has an impressive capacitance and excellent cycling performance.     

Rod-like polyaniline supported on three-dimensional boron and nitrogen-co-doped graphene frameworks for high-performance supercapacitors

In this work, novel three-dimensional (3D) boron and nitrogen-co-doped three-dimensional (3D) graphene frameworks (BN-GFs) supporting rod-like polyaniline (PANI) are facilely prepared and used as electrodes for high-performance supercapacitors. The results demonstrated that BN-GFs with tuned electronic structure can not only provide a large surface area for rod-like PANI to anchor but also effectively facilitate the ion transfer and charge storage in the electrode. The PANI/BN-GF composite with wrinkled boron and nitrogen-co-doped graphene sheets interconnected by rod-like PANI exhibits excellent capacitive properties with a maximum specific capacitance of 596 F/g at a current density of 0.5 A/g. Notably, they also show excellent cycling stability with more than 81% capacitance retention after 5000 charge-discharge cycles.     

3D Nanostructured Polypyrrole/Sodium Alginate Conducting Hydrogel from self-assembly with High Supercapacitor Performance

Due to their possible ideal three dimensional (3D) nanostructures and excellent electrochemical properties, conducting hydrogels have attracted much attention in recent years. Herein, pyrrole monomer was directly dissolved in an aqueous solution of sodium alginate (SA), and was allowed to undergo in-situ polymerization to form polypyrrole (Ppy), resulting in formation of Ppy/SA, a conducting hydrogel, via self-assembly between the polymers. Observation by SEM indicated that the microstructure of the Ppy/SA hydrogel was a typical 3D nano-cylinder network, with the cylinders formed by entanglements of the Ppy and SA molecular chains (cylinder diameter was ～100 nm). The electrochemical measurements of cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy indicated that the Ppy/SA hydrogel possessed typical pseudocapacitance, good charging and discharging rate performance, and favorable capacitive behavior; the specific capacity reached up to 249 F/g at the current density of 0.2 A/g. We suggest it has great potential in the field of high-performance electrode materials for supercapacitors.     

Synthesis and characterization of nitrogen-doped graphene hollow spheres as electrode material for supercapacitors

Recently, the rapid development of graphene industry in the world, especially in China, provides more opportunities for the further extension of the application field of graphene-based materials. Graphene has also been considered as a promising candidate for use in supercapacitors. Here, nitrogen-doped graphene hollow spheres (NGHS) have been successfully synthesized by using industrialized and pre-processed graphene oxide (GO) as raw material, SiO₂ spheres as hard templates, and urea as reducing-doping agents. The results demonstrate that the content and pretreatment of GO sheets have important effect on the uniform spherical morphologies of the obtained samples. Industrialized GO and low-cost urea are used to prepare graphene hollow spheres, which can be a promising route to achieve mass production of NGHS. The obtained NGHS have a cavity of about 270 nm, specific surface area of 402.9 m² g^?1, ultrathin porous shells of 2.8 nm, and nitrogen content of 6.9 at.%. As electrode material for supercapacitors, the NGHS exhibit a specific capacitance of 159 F g^?1 at a current density of 1 A g^?1 in 6 M KOH aqueous electrolyte. Moreover, the NGHS exhibit superior cycling stability with 99.24% capacitive retention after 5000 charge/discharge cycles at a current density of 5 A g^?1.     

Performance of C/C electric double layer capacitors with coal-based active carbon electrodes

Coal-based active carbon was prepared and used as electrodes of electric double-layer capacitors (EDLCs). The performance of EDLCs using active carbon electrodes with different pore structure was studied, including cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. With an increase of sodium hydrate/coal ratio, the pore structure of active carbon is greatly improved, resulting in larger double-layer capacitance. The capacitance of asymmetric EDLC is up to 65.98 F/g. Moreover, it is found that different pore structure of active carbon is necessary for positive and negative electrodes. Asymmetric EDLC not only exhibits high capacitance but also shows excellent charge-discharge performance, suggesting that it is very suitable and promising to design electrode materials for supercapacitors.     

Fabrication of functionalized nitrogen-doped graphene for supercapacitor electrodes

A unique and convenient one-step hydrothermal process for synthesizing functionalized nitrogen-doped graphene (FGN) via ethylenediamine, hydroquinone, and graphene oxide (GO) is described. The graphene sheets of FGN provide a large surface area for hydroquinone molecules to be anchored on, which can greatly enhance the contribution of pseudocapacitance. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and electrochemical workstation are used to characterize the materials. The nitrogen content exhibited in FGN can be up to 9.83 at.%, and the as-produced graphene material shows an impressive specific capacitance of 364.6 F g^?1 at a scan rate of 10 mV s^?1, almost triple that of the graphene (GN)-based one (127.5 F g^?1). Furthermore, the FGN electrodes show excellent electrochemical cycle stability with 94.4 % of its initial capacitance retained after 500 charge/discharge cycles at the current density of 3 A g^?1.     

Capacitance properties of poly(3,4-ethylenedioxythiophene)/carbon nanotubes composites

The electrochemical properties of composites prepared from an electrically conducting polymer poly(3,4-ethylenedioxythiophene), i.e. PEDOT and multiwalled carbon nanotubes (CNTs) have been investigated for supercapacitor application. The novel composite material was prepared by chemical or electrochemical polymerization of EDOT directly on the nanotubes or from a homogenous mixture of PEDOT and CNTs. Acetylene black (AB) has been also used as a composite component in order to evaluate whether nanotubes are giving improved properties or not. Electrodes prepared from such composites were used in supercapacitors operating in acidic (1 M H₂SO₄), alkaline (6M KOH) and organic (1 M TEABF₄ in AN) electrolytic solutions. The capacitance values were estimated by galvanostatic, voltammetry and impedance spectroscopy techniques with two- or three-electrode cell configuration. Due to the open mesoporous network of nanotubes, the easily accessible electrode/electrolyte interface allows quick charge propagation in the composite material and an efficient reversible storage of energy in PEDOT during subsequent charging/discharging cycles. The composites with AB supply quite good capacitance results, however, nanotubes as electrode component gave definitively a more homogenous dispersion of PEDOT that should give a better charge propagation. The values of capacitance for PEDOT/carbon composites ranged from 60 to 160 F/g and such material has a good cycling performance with a high stability in all the electrolytes. Organic medium is especially interesting because of higher energy stored. Another quite important advantage of this composite is its significant volumetric energy because of the high density of PEDOT.