纳米纤维素/还原氧化石墨烯复合材料用于高性能超级电容器

以高浓度氧化石墨烯(GO)溶液作为反应前驱体,纳米纤维素(NC)作为物理间隔物和电解液储存器,通过简单的一步水热法制备了纳米纤维素/还原氧化石墨烯(NC/rGO)复合材料,并探究了其作为超级电容器电极材料的潜力。结果如下：NC添加量为1 mL所制备的NC/rGO-1具有最佳电化学性能。基于NC/rGO-1的无黏合剂对称型超级电容器在0.3 A·g^-1的电流密度下显示出了269.33 F·g^-1和350.13 F·cm^-3的高质量和体积比电容,并在10.0 A·g^-1时仍能达到215.88 F·g^-1和280.62 F·cm^-3(其初始值的80.15%)。组装器件还显示出了较高的质量和体积能量密度(9.3 Wh·kg^-1和12.13 Wh·L^-1)和出色的循环性能(10 A·g^-1下10 000次循环后其初始比电容仅减少6.02%)。     

Ag+掺杂聚苯胺的制备及其电容特性研究

以苯胺为单体,采用界面聚合法合成了不同浓度的Ag⁺掺杂的聚苯胺(PANI/Ag⁺),使用傅里叶变换红外光谱（FT-IR）、X射线衍射（XRD）和场发射扫描电镜（SEM）等手段对其结构和形貌进行了分析和表征. 在0.5 mol•L^-1 Na₂SO₄电解液中,通过循环伏安（CV）、恒流充放电（CP）以及电化学阻抗（EIS）等技术研究了其电化学性能. 结果表明,当电流密度为5 mA•cm^-2时,PANI/0.12mol•L^-1 Ag⁺的比电容达529 F•g^-1,循环1000次后比电容保持51%,相对于无Ag⁺掺杂的PANI,表现出更优良的电化学电容特性.     

功能化石墨烯/聚苯胺复合电极材料的制备和电化学性能

利用水合肼还原十八胺(ODA)接枝的氧化石墨烯(GO),得到了十八胺功能化石墨烯(ODA-G),将ODAG与聚苯胺(PANI)通过溶液共混法,制备了功能化石墨烯和聚苯胺纳米复合材料(ODA-G/PANI).采用傅里叶变换红外(FTIR)光谱、X射线衍射(XRD)、热重分析(TGA)、拉曼(Raman)光谱及透射电镜(TEM),对复合材料的结构和形貌进行了表征;利用循环伏安、恒流充放电及交流阻抗谱等,对复合材料的电化学性能进行了测试.结果显示,少量ODA-G的引入为PANI的电化学氧化还原反应提供了更多的电子通道和活性位置,有利于提高PANI的赝电容.在电流密度1.0 A·g-1下,2%(w)ODA-G/PANI的比电容达到787 F·g-1,而相应的PANI仅有426 F·g-1.此外,ODA-G/PANI的循环稳定性也远高于纯PANI.     

电化学电容器氮化钒负极材料性能研究

利用高温氨解还原氧化钒（V₂O₅）制备了氮化钒（VN）纳米材料. 采用XRD、SEM与TEM观察分析样品的结构和形貌,采用氮气吸附、循环伏安曲线以及恒流充放电曲线测试样品的比表面积、孔径分布和电极电化学性能. 结果表明,VN样品属于立方晶系（Fm3m [225]）,其大小均一,近似球形,氨解时间的加长（12 h）,小颗粒间相互交联可形成一定的介孔. 50 mA?g-1电流密度下VN-c电极的比电容能达到192 F.g-¹,1000周期循环其比电容仍有150 F.g^-1,同时具有双电层电容性能和氧化还原反应的准电容性能.     

BC/CoNi2S4@PPy柔性复合电极材料的制备及电化学性能

本文采用溶剂热、原位聚合和真空抽滤相结合的方法制备了用于超级电容器的细菌纤维素/镍钴硫化物/聚吡咯(BC/CoNi₂S₄@PPy)柔性电极材料,通过X射线衍射、场发射扫描电镜、红外光谱、氮气吸脱附、拉伸强度和接触角表征了材料的形貌结构、组成、机械性能和亲水性,并采用循环伏安法和恒电流充放电测试了复合材料的电化学性能。结果表明,表面含氧官能团丰富的BC纤维网络结构对氧化还原活性物质CoNi₂S₄的生长和导电聚合物PPy的分布具有引导作用,CoNi₂S₄均匀分布在BC网络中,且PPy均匀包覆在BC纤维和CoNi₂S₄纳米球表面构成具有丰富孔隙结构的三维导电网络,使得该复合材料具有较好的机械性(抗拉强度达28.0±0.1 MPa)、亲水性(对6 mol·L^-1 KOH的瞬间接触角为43.6°)及良好的导电性。该电极材料在1 A·g^-1下比电容高达2670 F·g^-1,充放电循环10000次后比电容的保持率为82.73%,且经1000次反复弯曲后电化学性能保持不变。此外,将其与活性炭组成的非对称超级电容器,在1 A·g^-1下比电容为1428 F·g^-1,最高能量密度和功率密度分别达49.8 Wh·kg^-1和741.8 W·kg^-1。     

Mn3O4/石墨烯复合材料的制备与电化学性能研究

本文以氧化石墨烯（GO）溶液为氧化剂,采用水热法使GO直接氧化Mn(Ac)₂制备Mn₃O₄/石墨烯复合材料,并通过在制备过程中加入氨水提高了复合材料中GO的还原程度与Mn₃O₄颗粒的分散性. 制得的Mn₃O₄/石墨烯复合材料表现出优异的电化学性能. 在0.5 A·g^-1的电流密度下复合材料质量比容量可达到850 mAh·g^-1,0.5 A·g^-1时充放电循环测试200周容量保持率为99%.     

硼、氮共掺杂多孔碳的制备及其超电容性能

分别以含氮菲咯啉、四硼酸钾和醋酸锌为碳源、活化剂和模板,制备了B、N共掺杂多孔碳(BN-PC),并探究模板质量对BN-PC结构和储电性能的影响。当醋酸锌质量为5 g时,所得BN-PC₅中B、N杂原子含量分别为20.21%、18.29%。电化学测试结果表明,以6 mol·L^-1KOH为电解液,BN-PC₅电极展现出高的比电容(在0.05 A·g^-1电流密度下为255 F·g^-1)、优异的倍率性能(在20 A·g^-1电流密度下为188 F·g^-1)和卓越的循环稳定性(在5 A·g^-1的电流密度下循环10 000次比电容保持率为97%)。以3mol·L^-1ZnSO₄为电解液,在平均功率密度为56 W·kg^-1时,BN-PC₅电容器的能量密度可达27 Wh·kg^-1。     

三维还原氧化石墨烯/聚苯胺复合材料的制备及其超级电容性能

以制备的氧化石墨凝胶和聚苯胺纳米线为原料, 将二者按一定的质量比进行混合超声分散, 再以混合分散液为前驱体采用一步水热法制备得到三维还原氧化石墨烯(RGO)/聚苯胺(PANI) (RGP)复合材料, 采用扫描电镜(SEM), 透射电镜(TEM), X射线衍射(XRD), 傅里叶变换红外(FT-IR)光谱, X射线光电子能谱(XPS)和电化学测试等分析研究了复合材料的形貌、结构和超级电容性能. 结果表明, 复合材料既保持了还原氧化石墨烯的基本形貌, 又能使聚苯胺较好地镶嵌在还原氧化石墨烯的网状结构中; 且当氧化石墨与聚苯胺的质量比为1:1时复合材料在0.5 A·g^-1电流密度下比电容可高达758 F·g^-1, 即使在大电流密度(30 A·g^-1)下其比容量仍高达400 F·g^-1,在1A·g^-1电流密度下循环1000次后比容量保持率为86%, 表现出了良好的倍率性能和循环稳定性, 其超级电容性能远优于单纯的还原氧化石墨烯和聚苯胺, 其优异的超级电容性能可归咎于二者的相互协同作用.     

具有高效电化学储能的中空网状笼还原氧化石墨烯

通过ZnO模板辅助电沉积法制备了中空网状笼还原氧化石墨烯,具有纳米管、多孔结构、网状结构和3D微米中空笼等多层次架构. 这样的结构能够同时促进电化学活性物种的传输,提高电极材料的利用率,以及提升超级电容器性能. 该类中空网状笼还原氧化石墨烯做超级充电器电极材料时表现出了优良的电化学性能,研究结果显示,在1.0 A•g^-1时比电容达到393 F•g^-1. 而且当电流密度从1.0 A•g^-1增加到20 A•g^-1,电容仅衰减了21.2%,10000周循环后比电容损失小于1%,表明具有优异的电容稳定性.     

碳纳米管/聚苯胺/石墨烯复合纳米碳纸及其电化学电容行为

通过真空抽滤的方法制备碳纳米管纸,并对其进行循环伏安电化学氧化处理.以该电化学氧化处理的碳纳米管(CV-CNT)纸为基体,采用电化学聚合沉积聚苯胺(PANI),随后吸附石墨烯(GR),制备具有三明治夹心结构的碳纳米管/聚苯胺/石墨烯(CV-CNT/PANI/GR)复合纳米碳纸.该结构外层为GR,内层由PANI包裹的CNT形成网络骨架,充分发挥三者各自优势构建柔性电极材料.用场发射扫描电镜(FE-SEM)、透射电子显微镜(TEM)、拉曼光谱对其形貌与结构进行表征,并测试其电化学性能.研究发现:PANI呈纳米晶须状,并均匀包裹在CV-CNT表面;该复合碳纸具有良好的电容特性、大电流充放电特性以及良好的循环稳定性能.电流密度为0.5A·g-1时,比电容可达415F·g-1;20A·g-1时仍能保持106F·g-1的比电容.由于GR的保护作用,1000次循环之后较CV-CNT/PANI保持更高的有效比电容.该CV-CNT/PANI/GR复合碳纸展现出在高性能超级电容器柔性电极材料的潜在应用价值.     

氧化石墨掺杂的电化学活性自支撑聚苯胺膜

以氧化石墨（GO）为掺杂剂和模板,采用化学原位聚合法并通过调节苯胺单体和氧化石墨的质量比,合成了层状结构的聚苯胺/氧化石墨(PANI/GO)层状结构的自支撑膜。SEM和XRD研究表明,当苯胺单体与GO的质量比为67:1时,PANI/GO复合材料具有层间距~1.36 nm的层状结构,证实 GO的模板功能。XPS和FTIR研究表明PANI/GO复合材料中的典型的聚苯胺的掺杂态,进一步证实GO的掺杂功能。此外,电化学和热失重测量表明PANI/GO层状结构的自支撑膜呈现良好的热稳定性和高电化学活性.     

Effect of electrostatic forces control on the structure and properties of polyaniline/graphene oxide nanocomposite

The effects of electrostatic forces (EF), control on the morphology, structure, and electrochemical properties of polyaniline, PANI/graphene oxide (GO), nanocomposites prepared by interfacial electropolymerization (IEP), are studied in this work. FESEM images showed that the IEP method can form the PANI/GO nanocomposites when the EF-control has been found mainly on the PANI nanofibers formation and growth on the GO film surface; and the EF-enhancement can form PANI nanofibers with small nano-diameter, longer length, uniform morphology, high order and well orientation as compared with the EF-reduction-formed sample. The EF-enhancement-formed PANI/GO nanocomposite showed improved electrochemical properties than that of the EF-reduction-formed sample due to the EF-enhancement that enhances the C–N structure for PANI/GO nanocomposite.     

Surfactant-assisted synthesis of polyaniline nanofibres without shaking and stirring: effect of conditions on morphology and conductivity

Polyaniline (PANI) nanofibres were synthesised by the chemical oxidative polymerisation method using ammonium peroxydisulphate (APS) as an oxidant/initiator. In this work, a surfactant-assisted method without shaking and stirring was used for the synthesis of PANI nanofibres. The effect was investigated of various parameters such as monomer/oxidant ratio, polymerisation temperature, and the presence of surfactant (Triton X-100 as a non-ionic surfactant) on the morphology and electrical conductivity of nanofibres. The morphology of PANI nanofibres was characterised by scanning electron microscopy and transmission electron microscopy. The results demonstrate that the morphology of PANI nanofibres was significantly influenced by the aniline/APS mole ratio, polymerisation temperature and presence of the surfactant during synthesis. The results showed that more regular and consistent nanofibres were obtained using a monomer/oxidant ratio of 4 at ambient temperature of polymerisation. PANI nanofibres with diameters in the range of 10?C100 nm and length up to several ??m were obtained. PANI nanofibres were also characterised using FTIR and UV-VIS absorption spectroscopy. The electrochemical behaviour of PANI nanofibres was studied by cyclic voltammetry. It was found that the electrical conductivity of PANI nanofibres increased with the increasing monomer/oxidant ratio and decreasing polymerisation temperature, respectively.     

One‐Step Electrodeposition to Layer‐by‐Layer Graphene–Conducting‐Polymer Hybrid Films

One‐step fabrication of graphene–polyaniline (graphene–PANI) hybrid film was facilely achieved by cyclic voltammetric electrolysis of a bath containing both graphene oxide (GO) and aniline, where graphene is obtained by electrochemical reduction of GO and PANI is simultaneously obtained by aniline electropolymerization. As there is no strong attraction between aniline and GO under the electrodeposition conditions, the independent depositions of PANI and reduced GO nanosheets at their greatly differed potentials led to alternate layered graphene–PANI films, with the topmost layer being PANI particles or graphene sheets just by changing the initial scan directions. The two kinds of graphene–PANI hybrid films present excellent but different electrical and electrochemical behaviors.     

石墨烯-ITO复合电极对聚苯胺薄膜电致变色性质的影响

采用改进的Hummers法制备氧化石墨烯(GO),首先,石墨与浓硫酸、过硫酸钾和五氧化二磷反应制得强氧化产物,随后将其与浓硫酸、硝酸钠、高锰酸钾反应,经双氧水发泡、酸洗、超声等合成氧化石墨烯水溶液,再通过金属箔还原和基底转移过程制备GO-氧化铟锡(ITO)复合电极材料.通过金属箔还原和基底转移过程制备GO-氧化铟锡(ITO)复合电极材料.利用电化学聚合法在GO-ITO复合电极上制备聚苯胺(PANI)薄膜,并对其形貌结构、电化学及电致变色性质进行表征.结果表明,与ITO电极相比,采用GO-ITO复合电极制备的PANI的成膜性得到明显改善,复合电极具有更加均匀细致的颗粒表面,增大了聚合物与电解液之间的接触面积,为电致变色过程中平衡离子的注入/脱出提供了更多的通道,因而PANI薄膜在700nm处的光学对比度提高了约13%,响应速度缩短了约2.6 s,着色效率高达169.6 cm2/C.GO的引入保持了PANI良好的电化学稳定性.GO-ITO复合电极有效改善了聚合物的综合性能,对于聚合物电致变色材料及器件的开发具有潜在的应用前景.     

Efficacy of Polyaniline (PANI) nanofibres for capturing Diclofenac (DC) drug from its aqueous solutions

Pharmaceutical drug contamination in water nowadays is deteriorating the ecological components. A remedial approach is therefore a necessity. This study focuses on the synthesis of PANI nanofibres employing the oxidative polymerization method using ammonium persulphate (APS) as oxidant. The synthesized nanofibres were characterized using HR-TEM, FT-IR and XRD. The HRTEM image exhibited the nano-range structure of PANI with a rough surface. The FT-IR spectra inferred about the role of surface capping groups involved in the uptake mechanism. The crystallinity of PANI was well assessed by the X-Ray Diffraction analysis. The interaction between the studied drug diclofenac (DC) and polyaniline (PANI) showed a rapid equilibrium time 120 min favored at pH 5.0 achieving maximum adsorptive capacity (q_e) of 471.08 mg g ^?1. The uptake process followed the pseudo-second order kinetic model (R² = 1) with intra-particle diffusivity model (R² = 0.9810) as the governing step and best fitting values into Langmuir isotherm model (R² = 0.9822) inferred about the favourable adsorption of DC forming monolayer over PANI having q_m to be 943.83 mg g^?1. The drug DC was easily desorbed up to 85.31% by using 0.1 M aq ethanol and was exhausted after five cycles of reusability. The whole adsorptive mechanism involved electrostatic interactions along with hydrogen bonding.     

Physicochemical interactions between polyaniline and graphene oxide: the reasons for the stability of their chemical structure and thermal properties

Several works are reported in the literature on the use of a conducting polymer such as polyaniline (PANI) and its combination with graphene oxide (GO). Graphene derivatives have an important contribution to improve the electrochemical performance of charge transfer and polarization of the polymer in energy storage cells. To understand the chemical phenomena in PANI–GO interaction, this article presents the relationships of the thermal, chemical, and morphostructural properties of this composite material. This synergistic effect between the materials is responsible for performance enhancing. Therefore, in this work, after PANI electrosynthesis on carbon fiber and further dipping of GO, Field Emission Gun, Raman spectroscopy, X-Ray Excited Electron Photon Spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, Differential Scanning Calorimetry, and thermogravimetric techniques were used to characterize these materials. GO tends to stabilize the molecular structure of PANI in its protonation/deprotonation and redox processes. Through thermal analysis, it was possible to observe that GO increases the stability of PANI at higher temperatures, minimizing mass loss rates and changing the polymer's glass transition temperature. And when observing the structure of the material under the influence of temperature, the GO kept the structures practically unaltered (PANI crystallographic orientation) up to 150 °C. These facts highlight important material stability data to be considered in energy storage system applications.     

Polyaniline micro-/nanostructures: morphology control and formation mechanism exploration

This article provides a brief overview of recent work by the authors’ group as well as related researches reported by others on controlling the morphology and exploring the formation mechanism of typical micro-/nanostructures of polyaniline (PANI) and aniline oligomers through template-free aniline chemical oxidation process. The contents are organised as follows: (i) tuning the morphology of aniline polymerisation products by employing ultrasonic irradiation, mass transfer, and pH profiles; (ii) exploring the formation mechanism of micro-/nanostructures during aniline chemical oxidation through examining the precipitation behaviours of aniline oligomers and polymers in a post-synthetic system; (iii) tailoring PANI micro-/nanostuctures into pre-designed morphology by introducing certain heterogeneous nucleation centres; (iv) application potential of PANI nanofibres in the areas of transparent conductive film, electromagnetic interference-shielding coating and graphene-based electrode materials. This short review concludes with our perspectives on the challenges faced in gaining the exact formation mechanism of PANI micro-/nanostructures and the future research possibility for morphologically precisely controlled PANI micro-/nanostructures.     

Production of Metal‐Free Composites Composed of Graphite Oxide and Oxidized Carbon Nitride Nanodots and Their Enhanced Photocatalytic Performances

A novel metal‐free composite (GN) composed of two types of carbon‐based nanomaterials, graphite oxide (GO) and 2D oxidized carbon nitride (OCN) nanodots was produced. Chemical and morphological characterizations reveal that GN contains a main component of GO with well‐dispersed 2D OCN nanodots. GN shows enhanced photocatalytic performance for degrading an organic pollutant, Rhodamine B, under visible light.     

In Situ Synthesis and Nonvolatile Rewritable‐Memory Effect of Polyaniline‐Functionalized Graphene Oxide

A new polyaniline (PANI)‐functionalized graphene oxide (GO‐PANI) was prepared by using an in situ oxidative graft polymerization of aniline on the surface of GO. Its highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), ionization potential (IP), and electron affinity (EA) values experimentally estimated by the onset of the redox potentials were ?5.33, ?3.57, 5.59, and 3.83 eV, respectively. A bistable electrical‐switching effect was observed in electronic device with the GO‐PANI film sandwiched between the indium tin oxide (ITO) and Al electrodes. This device exhibited two accessible conductivity states, that is, the low‐conductivity (OFF) state and the high‐conductivity (ON) state, and can be switched to the ON state under a negative electrical sweep, and can also be reset to the initial OFF state by a reverse (positive) electrical sweep. The ON state is nonvolatile and can withstand a constant voltage stress of ?1 V for 3 h and 10⁸ read cycles at ?1 V under ambient conditions. The nonvolatile nature of the ON state and the ability to write, read, and erase the electrical states, fulfill the functionality of a rewritable memory. An ON/OFF current ratio of more than 10⁴ at ?1 V achieved in this memory device is high enough to promise a low misreading rate through the precise control of the ON and OFF states. The mechanism associated with the memory effects was elucidated from molecular simulation results.