聚苯胺/介孔碳纳米线复合电极材料的制备和性能

以介孔碳纳米线为基体, 通过电化学方法制备了新型聚苯胺/介孔碳纳米线(PANI/MCFs)复合材料, 采用SEM和TEM等手段对样品的结构和形貌进行了表征. 结果表明, 聚苯胺均匀附在介孔碳纳米线表面, 并填充到纳米线介孔孔道中. 将复合材料组装成三电极体系超级电容器, 用循环伏安、 恒流充放电和交流阻抗等方法对材料的电化学性能进行了测试. 结果显示, 在1 mol/L H₂SO₄溶液中, 复合材料的比电容达到391 F/g, 其循环稳定性也得到显著提高.     

水性聚苯胺纳米线超级电容器电极材料

使用"假高稀"方法,分别以过硫酸铵、硝酸铁和三氯化铁为氧化剂,含有1个乙氧基基团的酸性磷酸酯为质子酸,经过原位聚合制备了直径分别为78～90 nm、18～30 nm和16～25 nm水分散性聚苯胺纳米线.聚苯胺膜的电导率分别为18,32和35 S cm-1,比表面积为65,70和82 m2g-1.该聚苯胺纳米线能够很好地分散在水中,是一种环境友好型超级电容器电极材料.该电极材料在1 mol L-1四乙基氟硼酸/碳酸丙烯酯非水性电解液中,在-1～1 V扫描范围内,以0.4 A g-1的放电速率下,分别得到了110,140和152 F g-1的比容,比电容与材料的比表面积和电导率有关,随着比表面积以及电导率的增大而增大.聚苯胺纳米线电极材料有较高的充放电效率(大于98%),表明了它们有很好的电化学可逆性.     

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.     

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.     

一维有序聚苯胺纳米阵列的制备及电化学储能性能

以导电玻璃FTO为基底电极, 在硫酸溶液中, 分别研究了苯胺单体浓度和恒定电流大小对聚苯胺(PANI)形貌的影响; 同时恒定苯胺单体的浓度和工作电流, 探究了不同类型的质子酸对PANI阵列形貌的影响. 结果表明, 采用恒电流方法可以制备出一维有序PANI纳米线阵列, 而且当苯胺的浓度为0.1 mol/L, 恒电流法的工作电流密度为0.03 mA/cm²时, 所制备的PANI纳米线阵列形貌最佳; 当用HCl, HNO₃和对甲苯磺酸(p-TSA)作为合成PANI的支持液时, 得到树桩状的PANI 纳米结构, 不能得到均一的纳米线阵列结构. 电化学性能测试结果表明, 制备的最佳形貌PANI纳米线阵列的比电容值可达560 F/g; 循环1000周后电容损失率为11%.     

用于超级电容器的锰钴氧化物/碳纤维材料

The development of high-performance supercapacitor electrode materials is imperative to alleviate the ongoing energy crisis. Numerous transition metals (oxides) have been studied as electrode materials for supercapacitors owing to their low cost, environmental-friendliness, and excellent electrochemical performance. Among the developed binary transition metal oxides, manganese cobalt oxides typically show high theoretical capacitance and stable electrochemical performance, and are widely used in the electrode materials of supercapacitors. However, the poor conductivity and active material utilization of manganese cobalt oxide-based electrode materials limit their potential capacitance application. Cotton is mainly composed of organic carbon-containing materials, which can be transformed to carbon fibers after calcination. The resultant carbonaceous material exhibits a large specific surface area and good conductivity. Such advantages could potentially suppress the negative effects caused by the poor conductivity and small specific surface area of manganese cobalt oxides, thereby improving the electrochemical performance. Herein, we firstly deposited manganese cobalt oxides on cotton by a simple hydrothermal method, yielding a composite of manganese cobalt oxides and carbon fibers via subsequent calcination, to improve the electrochemical performance of the electrode material. X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), and electrochemical characterizations were used to investigate the physical, chemical, and electrochemical properties of the prepared samples. The fabricated manganese cobalt oxides in the composite were uniformly dispersed on the carbon fiber surface, which increased the contact between the interface of the electrode material and electrolyte, and enhanced electrode material utilization. The electrode material was confirmed to have well contacted with the electrolyte during a contact angle test. Hence, a pseudo-capacitance reaction completely occurred on the manganese cobalt oxide material. Moreover, the addition of carbon fibers reduced the resistance of the material, resulting in excellent capacitive performance. The capacitance of the prepared composite was 854 F∙g^-1 at a current density of 2 A∙g^-1. The capacitance was maintained at 72.3% after 2000 cycles at a current density of 2 A∙g^-1. These results indicate that the manganese cobalt oxide and carbon fiber composite is a promising electrode material for high-performance supercapacitors. The findings presented herein provide a strategy for coupling with carbon materials to enhance the performance of supercapacitor electrode materials based on manganese cobalt oxides. Thus, novel insights into the design of high-performance supercapacitors for energy management are provided.     

石墨烯-聚苯胺杂化超级电容器电极材料

聚苯胺是一类具有超高比电容的导电高分子材料, 利用其与石墨烯的协同效应, 改善各自的固有缺点, 可以制得高性能的超级电容器. 本文综述了石墨烯-聚苯胺杂化电极材料的制备方法和石墨烯表面性质对电极材料电化学性能的影响, 讨论了优化杂化电极的结构与性能.     

自支撑三维功能化石墨烯/聚苯胺电极材料的制备及超级电容性能

采用水热法制备了三维石墨烯(3D-G),并以十八胺(ODA)为接枝剂对部分还原的氧化石墨烯进行氨基化处理,再利用原位聚合法在氨基化石墨烯表面生长聚苯胺,制备了十八胺功能化石墨烯/聚苯胺(G-ODA/PANI).对材料进行了结构表征、电化学性能分析和材料结构的比电容贡献分析.结果显示,电极材料的电容贡献大部分体现为材料的表面电容,G-ODA/PANI电极片在1 A/g电流密度时的比电容最高可达1080 F/g,是未功能化石墨烯/聚苯胺电极材料(G/PANI)的2.57倍,且循环稳定性也有很大的提高,循环10000周后的比容量保持率为90.8%,比G/PANI高9.6%.     

石墨烯-聚苯胺类超级电容器复合电极材料

聚苯胺理论比容量高、易合成,是一种理想的电极材料,但其循环寿命差,而石墨烯具有高的理论比表面积,将二者复合,充分利用两者之间的协同效应,能够使复合材料具有优异的电化学电容性能。本文回顾了近几年石墨烯-聚苯胺纳米复合材料在超级电容器中的最新研究结果及其制备方法,并对如何优化电极的结构与性能进行讨论,同时介绍了石墨烯-聚苯胺类电极材料在有机超级电容器中的应用进展,最后对石墨烯-聚苯胺复合材料的前景进行了展望。超级电容器用石墨烯-聚苯胺纳米复合材料的发展取决于其合理的微观结构设计,构建理想的三维多孔结构以避免聚苯胺的膨胀与收缩现象是研究的方向之一,此外,在改善石墨烯和聚苯胺间弱的界面相互作用的同时寻求石墨烯性能与功能化的平衡仍是难点,机械性能优异的聚苯胺纳米复合材料对于柔性全固态超级电容器的研究也会起到关键作用。     

原位电化学合成铁基电极材料及其超级电容器性能

采用胶体纳米粒子为模型进行研究。假设活性阳离子均匀分布在导电碳与粘结剂中,电解液离子的渗入可以原位形成活性胶体团簇。通过原位电化学方法合成了不同组成的铁基超级电容器电极材料。在不同的阳离子电解液中,铁胶体离子电极的电容不同,其中在KOH、NaOH、LiOH电解液中分别为1 113、927、755 F·g^-1。通过胶体的介尺度结构构筑,实现离子到材料性能的跨尺度可控调节。通过对胶体模型的拓展,提供了原位组成调节到材料性能跨尺度调控的新方法。     

掺Fe3+MnO2超级电容器电极材料的制备

化学掺杂;掺Fe3+MnO2超级电容器电极材料的制备     

Manganese Oxide/Graphene Aerogel Composites as an Outstanding Supercapacitor Electrode Material

Graphene aerogels (GA), prepared with an organic sol–gel process, possessing a high specific surface area of 793 m² g^?1, a high pore volume of 3 cm³ g^?1, and a large average pore size of 17 nm, were applied as a support for manganese oxide for supercapacitor applications. The manganese oxide was electrochemically deposited into the highly porous GA to form MnO₂/GA composites. The composites, at a high manganese oxide loading of 61 wt. %, exhibited a high specific capacitance of 410 F g^?1 at 2 mV s^?1. More importantly, the high rate specific capacitances measured at 1000 mV s^?1 for these composites were two‐fold higher than those obtained with samples prepared in the absence of the GA support. The specific capacitance retention ratio, based on the specific capacitance obtained at 25 mV s^?1, was maintained high, at 85 %, even at the high scan rate of 1000 mV s^?1, in contrast with the significantly lower value of 67 % for the plain manganese oxide sample. For the cycling stability, the specific capacitance of the composite electrode decayed by only 5 % after 50,000 cycles at 1000 mV s^?1. The success of this MnO₂/GA composite may be attributed to the structural advantages of high specific surface areas, high pore volumes, large pore sizes, and three‐dimensionally well‐connected network of the GA support. These structural advantages made possible the high mass loading of the active material, manganese oxide, large amounts of electroactive surfaces for the superficial redox events, fast mass‐transfer within the porous structure, and well‐connected conductive paths for the involved charge transport.     

多孔氧化镍薄膜的制备及其超级电容器性能

以氟掺杂的SnO₂导电玻璃(FTO)为基底,通过水热法与高温煅烧法相结合成功制备出多孔氧化镍薄膜。 通过场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)、晶体粉末衍射仪(XRD)、X射线光电子能谱(XPS)等技术手段对所制备NiO进行了物相组成、表面形貌及元素价态的表征。 在6 mol/L KOH电解液中,采用循环伏安法、恒电流充放电对NiO薄膜电化学性能进行了研究。 结果表明,在电流密度为2 A/g时,NiO薄膜的比电容可达651.6 F/g,循环1000圈后其电容保留值可达71.6%,是理想的超级电容器电极材料。     

氧化锰表面改性活性炭电极材料的电化学特性

用Mn(NO3)2溶液浸渍-高温热解法对普通活性炭进行表面改性处理以改善其电化学性能. 采用氮气吸附、SEM、XRD等方法研究改性活性炭的比表面积、孔结构、形貌和氧化锰的晶体结构; 用循环伏安、恒流充放电、交流阻抗等电化学方法研究了改性活性炭电极构成的电化学电容器的性能. 结果表明, Mn(NO3)2热解产生的多价态氧化锰有法拉第赝电容效应, 尤其是立方晶形结构的α-Mn2O3, 与活性炭的双电层电容构成了复合电容, 因而改性炭材料的比电容有明显的提高, 其质量比电容达到254 F·g-1, 比未改性炭的165 F·g-1提高了54%. 改性炭电极电化学电容器具有优异的充放电可逆性和稳定性, 而且等效串联电阻较小, 只有0.40 Ω; 经2000次循环的长期测试, 容量保持率几乎达到100%.     

二氧化锰/石墨烯纸电极的制备及其电化学性能

通过电化学法使溶液中的Mn²⁺电解氧化为MnO₂,沉积复合在石墨烯片膜上,形成由MnO₂/石墨烯复合材料构成的纸电极。 采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)、循环伏安(CV)和恒流放电等技术手段对纸电极材料的结构、形貌以及电化学性能进行了研究。 结果表明,MnO₂球形颗粒均匀地沉积在石墨烯片膜上,形成了厚度45 μm的纸电极,经过380 ℃煅烧后,纸电极中的MnO₂晶型由γ-MnO₂转化为β/γ-MnO₂混合晶型,是良好的柔性Li/MnO₂电池的电极材料。 MnO₂/石墨烯纸电极在室温下0.1C放电容量达269 mA·h/g,而且电化学阻抗低、柔韧性好。     

Preparation and Electrochemical Characteristics of Three-dimensional Manganese Oxide Micro-supercapacitor Electrode

In order to increase the electrode surface area and enhance the charge storage capacity, we study the micro electro mechanical system technology to fabricate three-dimensional high aspect ratio micro-electrode structure based on glass. The anodic constant potential method is employed to deposit manganese oxide as electroactive substances on the micro-electrode surface. Cyclic voltammetry and constant current charge-discharge method are both used to prepare electrode electrochemical performance testing, with a two-dimensional electrode without structure for comparison. Experimental results show that three-dimensional elec-trode structure can effectively enhance the charge storage capacity. At 1.0 mA/cm² charge-discharge density, the three-dimensional electrode shows a capacitance of 17.88 mF/cm², seven times higher than the two-dimensional electrode.     

铁氰化锰修饰玻碳电极的制备及其电化学性能

A thin film of manganese hexacyanoferrate （MnHCF） was electrochemically formed on a glassy carbon （GC） electrode to prepare a chemically modified electrode （CME）. The mechanism of film formation of MnHCF and its growth process were investigated in detail by cyclic voltammetry. The results show that the stoichiometric composition of MnHCF is Mn^ⅢFe^Ⅲ（CN）6, an analogue of prussian yellow. There exist three clear-cut stages in the whole modification process and the last stage is indispensable to the fabrication of homogenized, stable MnHCF film and must last for an appropriate time. The surface morphology of MnHCF/GC electrode was characterized by scanning electron microscopy （SEM）, which further verified the effective deposition of MnHCF film on GC. The kinetic constants of MnHCF/GC electrode process were also evaluated. The resulting MnHCF film modified electrode presented good stability and high electrocatalytic activity toward the oxidation of H2O2, indicating that MnHCF film possesses function of catalase and can be expected for analytical purposes.     

Nanocrystalline Manganese Iron Oxide as a Charge Storage Electrode

Phase pure nanocrystalline manganese iron oxide [(Mn_0.37Fe_0.63)₂O₃] was synthesized by combustion technique based on propellant chemistry principle employing citric acid as fuel. The synthesized powder was characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), BET, BJH analysis and electrochemical studies for possible application as a charge storage electrode. The average crystallite size was found to be 18.6 nm from XRD analysis. BET analysis yielded the surface area and specific pore volume of the powder to be 22.96 m² g^?1 and 0.0098 cm³ g^?1 respectively. The specific capacitance from cyclic voltammetric studies at scan rate 5 mV s^?1 was found to be about 30 F g^?1 cm^?2 while from charge discharge studies was found to be 27±1 F g^?1 cm^?2. In addition, the material showed appreciable stability during charge‐discharge cycling.     

炭载二氧化锰的制备和锂离子超级电容器性能的研究

制备了炭气凝胶载二氧化锰(AG-MnO₂)复合材料, 材料物理化学表征表明, 在炭气凝胶表面和微孔内沉积二氧化锰, 改善了炭气凝胶的电化学性能. 以炭二氧化锰复合材料为负极, LiMn₂O₄为正极, 设计出一种新型的高能量密度混合电容器, 并研究了负极工作电位范围对电容器性能的影响. 研究结果表明, 引入高容量的AG-MnO₂复合材料, 并通过扩大负极工作电位区间, 可设计出能量密度高达92 Wh•kg^－1(基于正负极活性质量)的混合电容器, 为炭对称电容器的5倍. 这种混合电容器经过1000次循环, 容量仍然保持在80%以上.     

Mesoporous Manganese Oxide/Lignin-Derived Carbon for High Performance of Supercapacitor Electrodes

This study explores the modification of lignin with surfactants, which can be used as a template to make mesoporous structures, and can also be used in combination with manganese oxide to produce manganese oxide/lignin-derived carbon. Organosolv extraction, using ethanol (70%) at 150 °C, was carried out to extract lignin from oil palm wood. Lignin was then mixed with Pluronic F-127, with and without Mn(NO₃)₂, and then crosslinked with acidic formaldehyde, resulting in a carbon precursor-based modified lignin. Carbonization was carried out at 900 °C to produce lignin-derived carbon and manganese oxide/lignin-derived carbon. The characterization materials included Fourier transform infrared (FTIR) spectroscopy, scanning electron microscope-energy dispersive X-ray (SEM-EDX) mapping, X-ray diffraction (XRD), and N₂-sorption analysis. FTIR curves displayed the vibration bands of lignin and manganese oxide. SEM images exhibited the different morphological characteristics of carbon from LS120% (lignin with a Pluronic surfactant of 120%) and LS120%Mn20% (lignin with a Pluronic of 120% and Mn oxide of 20%). Carbon LS120% (C-LS120%) showed the highest specific surface area of 1425 m²/g with a mean pore size of 3.14 nm. The largest mean pore size of 5.23 nm with a specific surface area of 922 m²/g was exhibited by carbon LS120%-Mn20% (C-LS120%-Mn20%). C-LS120%Mn20% features two phases of Mn oxide crystals. The highest specific capacitance of 345 F/g was exhibited by C-LS120%-Mn20%.