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。     

Synthesis of NiCo2S4 nanospheres/reduced graphene oxide composite as electrode material for supercapacitor

The NiCo₂S₄ nanospheres arrayed on the surface of reduced graphene oxide (rGO) was fabricated via one-step hydrothermal method. The effect of initial feeding mass of Ni(NO₃)₂·6H₂O and Co(NO₃)₂·6H₂O to rGO on the microstructure and electrochemical performance of the as-prepared composites was studied. The results indicated that the specific capacitances of the composites were first increased and then reduced due to the aggregation of NiCo₂S₄ nanospheres. NiCo₂S₄ nanospheres/rGO composites exhibited a remarkable specific capacitance of 1406 F/g and excellent cyclic stability of 82.36% at the current density of 1 A/g, which were better than those of individual NiCo₂S₄ (792 F/g and 64.77%) counterpart. These results showed that the as-prepared NiCo₂S₄ nanospheres/rGO composites were outstanding candidate for electrode material of supercapacitors.     

Synthesis and electrochemical properties of three-dimensional graphene/polyaniline composites for supercapacitor electrode materials

To improve the specific capacitance and rate capability of electrode material for supercapacitors, a three-dimensional graphene/polyaniline(3DGN/PANI) composite is prepared via in situ polymerization on GN hydrogel. PANI grows on the GN surface as a thin film, and its content in the composite is controlled by the concentration of the reaction monomer. The specific capacitance of the 3DGN/PANI composite containing 10 wt% PANI reaches 322.8 F·g-1at a current density of1 A·g-1, nearly twice as large as that of the pure 3DGN(162.8 F·g-1). The capacitance of the composite is 307.9 F·g-1at 30 A·g-1(maintaining 95.4%), and 89% retention after 500 cycles. This study demonstrates the exciting potential of3DGN/PANI with high capacitance, excellent rate capability and long cycling life for supercapacitors.     

三维多孔复合碳层对电极的制备及其光伏性能研究

基于TiO_2光阳极、Pt对电极的染料敏化太阳能电池(DSSC)因其优异的光电转换特性受到了广泛的关注,然而Pt昂贵的价格制约了其发展与应用.针对这一问题,本文设计、制备了一种由相对致密且高导电的石墨膜(PC层,底层)及多孔碳纳米颗粒膜(CC层,顶层)构成的低成本、高性能三维多孔复合碳层对电极.基于该CC/PC对电极的DSSC具有优异的光伏性能:在1.5标准太阳光照射下,其填充因子高达65.28%(较Pt对电极高4.1%)、光电转换效率高达5.9%(为Pt对电极的94.2%). CC/PC对电极的优异光伏性能主要归因于其独特的三维多孔导电结构,该结构有极高的比表面积和丰富的催化反应活性位,有利于电子的快速传输及离子的快速转移,在这些因素的协同作用下,其光电转换性能大大改善.     

Enhanced electrochemical performance of porous activated carbon by forming composite with graphene as high-performance supercapacitor electrode material

In this work, a novel activated carbon containing graphene composite was developed using a fast, simple, and green ultrasonic-assisted method. Graphene is more likely a framework which provides support for activated carbon (AC) particles to form hierarchical microstructure of carbon composite. Scanning electron microscope (SEM), transmission electron microscope (TEM), Brunauer–Emmett–Teller (BET) surface area measurement, thermogravimetric analysis (TGA), Raman spectra analysis, XRD, and XPS were used to analyze the morphology and surface structure of the composite. The electrochemical properties of the supercapacitor electrode based on the as-prepared carbon composite were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), charge/discharge, and cycling performance measurements. It exhibited better electrochemical performance including higher specific capacitance (284 F g^?1 at a current density of 0.5 A g^?1), better rate behavior (70.7% retention), and more stable cycling performance (no capacitance fading even after 2000 cycles). It is easier for us to find that the composite produced by our method was superior to pristine AC in terms of electrochemical performance due to the unique conductive network between graphene and AC.     

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.     

Ultrasonic-microwave assisted synthesis of three-dimensional polyvinyl alcohol carbonate/graphene oxide sponge and studies of surface resistivity and thermal stability

In the article, graphene oxide (GO) was prepared by flake graphite, nitric acid and peroxyacetic acid via the sonochemical method and characterized, and polyvinyl alcohol carbonate/GO composite (PVAC/GO composite) was synthesized by polyvinyl alcohol (PVA), dimethyl carbonate (DMC) and GO via the approach of transesterification in the case of ultrasonic-microwave synergistic effects and characterized, and three-dimensional PVAC/GO sponge (3D PVAC/GO sponge) was manufactured by PVAC/GO composite via the foaming approach and characterized, and the thermal stability and surface resistivity of 3D PVAC/GO sponge were investigated. Based on those, it had been attested that PVAC polymer was structured by DMC and PVA and had the six-membered lactone rings and the ether bonds, and PVAC/GO composite was constituted by 2D GO lattice and PVAC polymer, and 3D PVAC/GO sponge was constructed by PVAC/GO composite, and the surface resistivity of 3D PVAC/GO sponge with 0.00, 0.60, 1.20, 1.80 and 2.40 g of GO were 9.07 × 10⁷, 6.02 × 10⁷, 4.65 × 10⁷, 2.47 × 10⁷ and 1.06 × 107 O/sq, and the thermal stability of 3D PVAC/GO sponge had improved.     

Preparation and characteristics of Li4Ti5O12 with various dopants as anode electrode for hybrid supercapacitor

Spinel-Li₄Ti₅O₁₂ is successfully synthesized by a solid phase synthesis. The Li₄Ti₅O₁₂ powders with various dopants (Al³⁺, Cr³⁺, Mg²⁺) synthesized at 800 °C are in accordance with the Li₄Ti₅O₁₂ cubic spinel phase structure. The dopants are inserted into the lattice structure of Li₄Ti₅O₁₂ without causing any changes in structural characteristics. In order to study the effect on various dopants, the hybrid supercapacitor is prepared by using un-doped Li₄Ti₅O₁₂ and doped Li₄Ti₅O₁₂ in this work. The electrochemical performance of the hybrid supercapacitor is characterized by impedance spectroscopy and cycle performance. The results show Cr³⁺ and Mg²⁺ dopants enhance the conductivity of Li₄Ti₅O₁₂. Also, Al³⁺ substitution improves the reversible capacity and cycling stability of Li₄Ti₅O₁₂. It is found that effect of dopant on the electrochemical performance of Li₄Ti₅O₁₂ as electrode material for hybrid supercapacitor where the EDLC and the Li ion secondary battery coexist in one cell system.     

基于镍泡沫支撑的Co_3O_4纳米多孔结构的高性能超级电容器电极

在众多能量存储和转化器件中,超级电容器由于具有功率密度高、充放电迅速和优异的循环性能的优点而被广泛研究.然而,较低的比容量和能量密度,限制了超级电容作为大尺度能量存储和转化器件的广泛应用.为了提高超级电容器的比容量,需要增大电极材料和电解质的接触面积,进而促进电极材料俘获/释放电解质中的粒子(例如电子、离子或者小分子).在此,我们通过简单的水热法联合高温退火实验方案能够大规模制备出镍泡沫支撑的Co_3O_4多孔纳米结构.无需借助导电胶和粘合剂,在集流器镍泡沫上"生长"Co_3O_4多孔纳米结构直接作为超级电容的电极材料.这种多孔纳米结构和一体化设计思路不仅能够有效提高电极的导电性,而且能够有效缩短离子和电子的迁移路径.由于多孔的结构特征和优异的导电性能,Co_3O_4电极表现出超高比容量(在电流密度为2.5 m A·cm~(-2)和5.5 m A·cm~(-2)时,比容量分别为1.87 F·cm(-2)(936 F·g-1)和1.80 F·cm~(-2)(907 F·g-1))、较好的倍率性能(电流密度从2.5 m A·cm~(-2)增大到100 m A·cm~(-2)时,保留其48.37%的初始电容)和超高的循环稳定性(经历4000次电流密度为10 m A·cm~(-2)的循环充放电过程,保留其92.3%的比容量).这种多孔纳米结构和一体化设计思路对设计其他高性能储能器件具有重要的指导意义.     

Improvement of the adhesion between polyaniline and commercial carbon paper by acid treatment and its application in supercapacitor electrodes

Commercial carbon paper was coated with polyaniline (PANI) using in situ polymerization of aniline. Prior to the PANI coating, acid treatment was performed to carboxylate the surface of the carbon paper for enhancing PANI adhesion by sonication of the carbon paper in a mixture of concentrated sulfuric and nitric acids. The loading mass density of PANI on the acid-treated carbon paper increased more than three times compared to that on the carbon paper without acid treatment. The specific capacitance also increased from 112 to 174 F/g in a two-electrode system (calculated using a total mass of carbon paper and PANI) due to better PANI coating on the acid-treated carbon paper. The simple acid treatment provides good adhesion of PANI to the commercial carbon paper and can be applied to prepare supercapacitor electrodes.     

Investigation of electrochemical performance of sol-gel derived MgFe2O4 nanospheres as aqueous supercapacitor electrode and bi-functional water splitting electrocatalyst in alkaline medium

Herein this work, we have used the sol-gel chemical synthesis method to prepare spherical shaped MgFe₂O₄ nanoparticles having size 45–50 nm. Using 1 mol L⁻¹ Sodium Perchlorate (NaClO₄) electrolyte, a capacitance of 61 F/g, a capacitance retention of 82.91% (after undergoing 1000 cycles), and an energy density of 41 Wh/kg have been achieved. Using 1 mol L⁻¹ Magnesium Perchlorate (Mg(ClO₄)₂) as electrolyte, a capacitance of 43 F/g, a capacitance retention of 82.15%, and an energy density of 29 Wh/kg have been realized. Furthermore, MgFe₂O₄ nanospheres exhibited an overpotential (η) = 1.09 V, a Tafel slope (b) = 317 mV/dec in regard to alkaline Oxygen Evolution Reaction (OER) electrocatalyst. It also achieved η = 402 mV and b = 241 mV/dec in regard towards alkaline Hydrogen Evolution Reaction (HER) electrocatalyst. These results signify the suitability of MgFe₂O₄ nanoparticles for high energy density aqueous supercapacitor and water splitting electrocatalyst applications.     

Converting of the 2D graphene to its 3D by chicken red blood cells as sheets separator for construction supercapacitor electrode

Here, we report on a facile green and scalable method for the fabrication of porous 3D graphene as a well-known carbon-based material used in many energy storage devices. Chicken red blood cells were used as sheets spacer and heteroatom sources in the construction of 3D graphene. First, the red blood cells were separated from the blood and mixed with graphene oxide. Then, the mixture was freeze-dried and carbonized at 700 °C. The resulted 3D graphene containing heteroatoms was used as a supercapacitor electrode modifier on a glassy carbon electrode and tested with various electrochemical techniques. The supercapacitor electrode showed a specific capacitance of 330 F g⁻¹ at a current density of 1 A g⁻¹, maximum power density of 1958 W kg⁻¹, and maximum energy density of 85 Wh kg⁻¹. Furthermore, the supercapacitive performances were tested in a two-electrode symmetrical system which exhibited a specific capacitance of 238 F g⁻¹ for 1 A g⁻¹. It also showed a power density of 2200 W kg⁻¹ and an appreciable energy density of 160 Wh kg⁻¹. The excellent electrochemical behavior of 3D graphene indicates the promising abilities of the composite for other applications such as biosensors, batteries, electrocatalysts, etc.     

Application of polyaniline nanowires electrodeposited on the FTO glass substrate as a counter electrode for low-cost dye-sensitized solar cells

Polyaniline nanowires (PANI NWs) were deposited onto fluorine-doped tin oxide (FTO) glass substrate using the cyclic voltammetric method with aniline monomer precursor in HCl aqueous solution. The secondary oxidation peak plays an important role in polymerization of aniline monomer and the optimization of catalytic activity of PANI-based counter electrodes was achieved by controlling the number of cycles. The photovoltaic performance of the dye-sensitized solar cells (DSSCs) with PANI NWs counter electrodes (CEs) was optimized at 4th cycles, and then following parameters were obtained: J_sc = 17.2 mA cm⁻², V_oc = 0.71 V, FF = 59.3%, and efficiency (η) = 7.24%. While, J_sc = 14.7 mA cm⁻², V_oc = 0.77 V, FF = 70.6%, and efficiency (η) = 7.98% in cells with Pt CEs. The PANI NWs were attractive as an alternative CEs for the low-cost DSSCs instead of Pt.     

二硒化铁/还原氧化石墨烯的制备及其在染料敏化太阳能电池中的应用

通过水热反应合成出二硒化铁/还原氧化石墨烯(FeSe₂/rGO)复合材料, 并将其作为对电极材料应用于染料敏化太阳能电池(DSSC). 利用X射线衍射、拉曼光谱、场发射扫描电子显微镜和高分辨透射电子显微镜对FeSe₂/rGO的结构和形貌进行了表征. 利用循环伏安法、电化学阻抗谱和Tafel曲线测试分析了FeSe₂/rGO对电极的电催化活性. 结果表明: FeSe₂呈纳米棒结构, 长度在100-200 nm之间, 且紧密地附着在rGO 的表面, FeSe₂/rGO对电极对I₃^-的还原具有很好的催化活性. 电池的J-V曲线测试显示: 基于FeSe₂/rGO对电极的DSSC的转换效率达到了8.90%, 相比基于单纯的FeSe₂对电极的DSSC(7.91%)和rGO对电极的DSSC(5.24%)都有了显著提高, 甚至优于铂对电极的DSSC(8.52%).     

Low platinum loading PtNPs/graphene composite catalyst with high electrocatalytic activity for dye-sensitized solar cells

Platinum nanoparticles(PtNPs)/graphene composite materials are synthesized by a controlled chemical reduction of H2PtCl6 on graphene sheets.The electrocatalytic activity of a PtNPs/graphene composite counter electrode for a dye-sensitized solar cell(DSSC) is investigated.The results demonstrate that the PtNPs/graphene composite has high electrocatalytic activity for the dye-sensitized solar cell.The cell employing PtNPs(1.6 wt%)/graphene counter electrode reaches an conversion efficiency(η)of 3.89% upon the excitation of 100 mW/cm2 AM 1.5 white light,which is comparable to that of the cell with a Pt-film counter electrode(η=3.76%).It suggests that one can use only 14% Pt content of the conventional Pt-film counter electrode to obtain a comparable conversion efficiency.It may be possible to obtain a high performance DSSC using the PtNPs/graphene composite with a very low Pt content as a counter electrode due to its simplicity,low cost,and large scalability.     

还原石墨烯与片状氧化镍复合材料的隐身性能

采用一锅法制备还原石墨烯与片状氧化镍复合材料。复合材料的结构形貌、晶型和电磁参数分别通过扫描电镜、透射电镜、X射线衍射仪以及HP8722ES型矢量网络分析仪进行表征、测试与分析。结果表明,还原石墨烯与片状氧化镍复合材料同纯还原石墨烯相比在低频段(2.0~6.6 GHz)有更佳的吸收宽度和微波吸收能力,还原石墨烯与氧化镍片复合材料的介电损耗显著增加。大尺寸氧化镍片与还原石墨烯紧密复合提高了材料的载流子迁移率,从而提高了材料的吸波特性。     

Synthesis and electrical characteristics of polyaniline nanoparticles and their polymeric composite

Monodisperse polyaniline nanoparticles (PAPSSA) were synthesized from an oxidative dispersion polymerization using poly(sodium 4-styrenesulfonate) (PSSA) as both a polymeric stabilizer and a dopant agent due to its acidity. The nanoparticles were being stabilized with two different molecular weight of PSSA. Size effect of PAPSSA particles were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and dynamic light scattering (DLS). The d.c. electrical conductivity of composite films on the glass substrate was measured by a four-probe method. It was found that the electrical properties of the composite films are affected by the content of nano-sized polyaniline and different molecular weights of stabilizer in the poly(vinyl alcohol) (PVA) matrix.     

One-step synthesis of TiC/multilayer graphene composite by thermal plasma

Graphene hybrid materials have been attracting a great deal of attention due to their superior properties. Nevertheless, problems such as expensive and complicated production processes have limited their application to industrial fields. Here, we introduce a one-step synthesis of titanium carbide (TiC) nanoparticles on multilayer graphene nanosheet (TiC/multilayer graphene) composites using thermal plasma. Although there are three types of titanium alkoxides (titanium ethoxide, titanium isopropoxide and titanium n-butoxide), the TiC/multilayer graphene was synthesized from only titanium isopropoxide. The injection temperature of the precursor was varied to investigate the effects of the precursor concentration in the plasma region. A TiC/multilayer graphene hybrid material with crystalline TiC nanoparticles below 50 nm on graphene nanosheets was observed. The number of graphene nanosheet layers varied from one to over 10 according to the injection temperature. When titanium ethoxide and titanium butoxide were injected, TiC with amorphous carbon and graphite were synthesized. The formation of graphene is considered to be affected by the structure of the carbon chain in the precursors and the concentration in the plasma region.     

石墨烯/氧化铜纳米粒子/铜修饰电极对亚叶酸钙的电催化氧化及其分析应用

采用阳极极化的方法在铜电极表面形成氧化铜纳米粒子,然后采用循环伏安法将羧基化石墨烯电沉积到上述电极表面,成功制备了石墨烯/氧化铜纳米粒子/铜电极,用于碱性溶液中亚叶酸钙的检测.采用循环伏安法对亚叶酸钙在修饰电极上的催化氧化行为进行了研究,阳极扫描极化反向催化伏安法应用于亚叶酸钙的检测.在2.0×10^-7~2.0×10^-5 mol/L范围内,该电极显示出良好的线性关系,灵敏度为22.0 μA·μL/（μmol/cm²）,检测限达到7.6×10^-8 mol/L（S/N=3）,成功应用于实际样品的检测.