无模板剂合成用于超级电容器的二氧化锰/石墨烯复合材料(英文)

以尿素、四水合氯化锰和氧化石墨烯为原料,采用水热法并通过热分解制备了一种具有石墨烯包覆结构的石墨烯-二氧化锰复合材料,利用扫描电子显微镜、X射线衍射、比表面积(BET)、拉曼光谱和热失重等技术对其形貌、晶体结构及表面结构进行了表征;在三电极条件下利用循环伏安法、恒流充放电法和交流阻抗法测试了材料的电化学性能,并考察了不同石墨烯含量对材料比电容的影响.结果表明,在不添加模板剂的条件下制备的复合材料中二氧化锰是具有介孔结构的α-MnO2,当复合15%(质量分数)的石墨烯后材料的比表面积从109 m2·g-1提高到168 m2·g-1.复合材料具有更好的电化学性能,在0.2 A·g-1电流密度下复合材料的比电容达到最大值(454 F·g-1),远高于纯二氧化锰的值(294 F·g-1).在2 A·g-1的电流密度下恒流充放电2000次后复合材料的比电容保持率为92%.     

聚吡咯/海藻酸钠纳米球的制备及其应用于高性能超级电容器

用海藻酸钠作为结构导向剂,通过原位氧化聚合吡咯法制备了聚吡咯/海藻酸钠(PPy/SA)纳米球.聚吡咯/海藻酸钠纳米球的形貌和结构通过扫描电镜(SEM)、X射线衍射(XRD)和傅里叶变换红外(FTIR)光谱进行表征.材料的电化学性能通过循环伏安法和恒电流充放电方法进行测试.电化学测试表明,聚吡咯/海藻酸钠纳米球在1 mol L-1KCl电解液中,电流密度为1 A g-1时其比电容高达347 F g-1.与纯聚吡咯相比较,聚吡咯/海藻酸钠纳米球具有更优异的循环稳定性能.     

表面官能团化增强碳纳米笼超级电容器性能

以具有多级孔结构、高比表面积、良好导电性等特征的碳纳米笼(CNCs)为前体,采用硝酸氧化法在CNCs表面引入含氧官能团。以CNCs为超级电容器电极材料,在相同电流密度下,官能团化样品的比电容显著高于纯CNCs;在1 A·g-1下比电容最高可达到255 F·g-1,比纯CNCs的188 F·g-1增加了34%,这表明表面含氧官能团化能够显著提高CNCs的超级电容器比电容。在100 A·g-1的大电流密度下,硝酸氧化后CNCs的比电容保持在111~167 F·g-1,表明具有良好的耐大电流充放电性能。在10 A·g-1的电流密度下循环10 000圈后,CNC-6M样品的比电容由196 F·g-1下降到176 F·g-1,样品的比电容仍保留90%,具有良好的循环稳定性。表面含氧官能团化CNCs所表现出的这种优异的超级电容器性能归因于CNCs的多尺度分级孔结构、高比表面积、良好的导电性、表面亲水性含氧官能团化带来的浸润性提高和引入的赝电容。     

无模板法合成具有分级结构的多孔氧化镍及其电容性能研究(英文)

应用无模板水热法制备了由超薄氧化镍纳米片组装而成的具有分级结构的多孔氧化镍,SEM观察表明经煅烧氧化镍仍保持花状球形结构.电化学测试结果表明,扫速为20 mV.s-1时,其比电容值435 F.g-1,循环1000周期之后,电容值基本没有衰减;电流密度为10 A.g-1时,其比电容值为367 F.g-1.该材料是一种有应用价值的超级电容器材料.     

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.     

空心六边形镍钴硫化物/RGO复合物的合成及其超级电容性能

通过两步法制备了一种空心六边形镍钴硫化物(HHNCS)与还原氧化石墨烯(RGO)的纳米复合材料HHNCS/RGO。利用XRD,SEM,TEM和Raman光谱等对复合物进行表征,发现镍钴硫化物为空心六边形结构,并且均匀地附着在RGO的表面。该纳米复合物用作超级电容器电极表现出优异的电化学性能。在电流密度为1 A·g-1时比电容为927 F·g-1;当电流密度增大到20 A·g-1时,比电容仍高达724 F·g-1,表明材料拥有较好的倍率性能。此外,在电流密度5 A·g-1下循环2 000次后比电容保留有初始值的93%,显示出优异的循环稳定性。HHNCS/RGO优异的电容性能主要是由于RGO的存在不仅增强了材料的导电性,而且作为理想的载体分散HHNCS纳米片。HHNCS/RGO纳米复合物优异的电化学性能使其在超级电容器电极材料领域具有应用前景。     

有序介孔碳负载NiCo2O4电极的制备及其超电容性能

以有序介孔碳(OMC)为载体,采用共沉淀法制备了OMC/NiCo2O4复合物.用X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱和透射电镜(TEM)研究其结构与形貌,发现NiCo2O4纳米颗粒均匀地负载在有序介孔碳上.循环伏安和恒流充放电测试表明,NiCo2O4质量分数为40%时,在1A·g-1的电流密度下,复合物电极的比电容可以达到577.0F·g-1,电流密度为8A·g-1时,比电容可以达到470.8F·g-1,并具有良好的循环稳定性.在2A·g-1的电流密度下,经过2000次循环后,比电容还可达到508.4F·g-1,电容保持率为92.7%.     

具有高效电化学储能的中空网状笼还原氧化石墨烯（英文）

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.     

介孔碳/石墨烯复合材料的制备及其醌类改性电容性能

首先利用硬模板法制备出介孔碳/石墨烯复合材料,然后向复合材料中引入具有赝电容活性的醌类分子进一步增大材料的电容性能。研究结果表明,负载30%(w/w)叔丁基氢醌的介孔碳/石墨烯复合材料具有最佳的电容性能,在电流密度为0.5 A·g~(-1)时,比电容值为355 F·g~(-1);当电流密度高达30 A·g~(-1)时,其比电容值高达226 F·g~(-1),比电容保持率为64%,表现出良好的速率特性。     

石墨烯/钴镍双金属氢氧化物复合材料的制备及电化学性能研究

采用微波辐射与高温裂解相结合的二步还原法制备石墨烯。二步还原使氧化石墨被充分还原和剥离,所得到的石墨烯有较好的传导性,其比表面达675.4 m2.g-1。以此石墨烯为原料,水热法合成出石墨烯/钴镍双金属氢氧化物复合材料,并考察了复合材料作为超级电容电极材料的电化学性能。研究发现,褶皱的石墨烯纳米片均匀分散在钴镍双金属氢氧化物中,这改善了钴镍双金属氢氧化物的传导性和结构稳定性。在0.25 A.g-1电流密度下,复合材料的比电容量是800.2 F.g-1。当电流密度增加至10 A.g-1,比电容量为386.5 F.g-1,恒电流充-放电500次后比电容量仍能保持99%以上,这些呈示该复合材料具有优良的电化学性能。     

Non‐Covalent Functionalization of Graphene with Bisphenol A for High‐Performance Supercapacitors

The reduced graphene oxide (RGO)/bisphenol A (BPA) composites were prepared by an adsorption‐reduction method. The composites are characterized by X‐ray diffraction (XRD), UV‐vis, thermogravimetric (TG) analysis, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM). The results confirm that BPA is adsorbed on the basal plane of RGO by π‐π stacking interaction. Furthermore, the electrochemical behaviors were evaluated by cyclic voltammetry, galvanostatic charge/discharge techniques and electrochemical impedance spectroscopy (EIS). The results show that the RGO/BPA nanocomposites exhibit ultrahigh specific capacitance of 466 F·g^?1 at a current density of 1 A·g^?1, excellent rate capability (more than 81% retention at 10 A·g^?1 relative to 1 A·g^?1) and superior cycling stability (90% capacitance decay after 4000 cycles). Consequently, the RGO/BPA nanocomposites can be regarded as promising electrode materials for supercapacitor applications.     

Hydrothermal Self-assembly Synthesis of Mn3O4Reduced Graphene Oxide Hydrogel and Its High Electrochemical Performance for Supercapacitors

In the present work Mn3O4/reduced graphene oxide hydrogel （Mn3O4-rGOH） with three dimensional （3D） networks was fabricated by a hydrothermal self-assembly route. The morphology, composition, and microstructure of the as-obtained samples were characterized using powder X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, thermogravimetry analysis （TG）, atomic absorption spectrometry （AAS）, field emission scanning electron microscopy （FESEM） and transmission electron microscope （TEM）. Moreover, the electrochemical behaviors were evaluated by cyclic voltammogram （CV）, galvanostatic charge-discharge and electrochemical impedance spectroscopy （EIS）. The test results indicated that the hydrogel with 6.9% Mn3O4 achieved specific capacitance of 148 F.g^-1 at a specific current of 1 A.g^-1, and showed excellent cycling stabilily with no decay after 1200 cycles. In addition, its specific capacitance could retain 70% even at 20 A.g^- 1 in comparison with that at 1 A.g ^-1 and the operating window was up to 1.8 V in a neutral electrolyte.     

石墨烯-氧化钌纳米复合材料的水热法合成及电化学电容性能

通过水热法制备了石墨烯-氧化钌(G-RuO₂)纳米复合材料。对样品进行了X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM)和能量色散谱(EDS)表征。SEM结果表明氧化钌粒子均匀地分散在石墨烯层片上。TEM结果显示氧化钌纳米粒子的平均粒径约为3 nm。对样品进行了循环伏安和充放电性能测试,结果表明在1 A·g^-1的电流密度下,样品在H₂SO₄(1 mol·L^-1)溶液中具有219.7 F·g^-1的比电容。     

Electrochemical capacitance performance of polypyrrole–titania nanotube hybrid

In this study, the polypyrrole–titania nanotube hybrid has been synthesized for an electrochemical supercapacitor application. The highly ordered and independent titania nanotube array is fabricated by an electro-oxidation of titanium sheet through an electrochemical anodization process in an aqueous solution containing ammonium fluoride, phosphoric acid and ethylene glycol. The polypyrrole–titania nanotube hybrid is then prepared by electrodepositing the conducting polypyrrole into well-aligned titania nanotubes through a normal pulse voltammetry deposition process in an organic acetonitrile solution containing pyrrole monomer and lithium perchlorate. The morphology and microstructure of polypyrrole–titania nanotube hybrid are characterized by scanning electron microscopy, infrared spectroscopy and Raman spectroscopy. The electrochemical capacitance performance is determined by cyclic voltammetry and charge/discharge measurement. It indicates that the polypyrrole film can been uniformly deposited on both surfaces of titania nanotube walls, demonstrating a heterogeneous coaxial nanotube structure. The specific capacitance of polypyrrole–titania nanotube hybrid is determined to be 179?F?g^?1 based on the polypyrrole mass. The specific energy and specific power are 7.8?Wh?kg^?1 and 2.8?kW?kg^?1 at a constant charge/discharge current of 1.85?mA?cm^?2, respectively. The retained specific capacitance still keeps 85% of the initial capacity even after 200 cycle numbers. This result demonstrates the satisfying stability and durability of PPy–TiO₂ nanotube hybrid electrode in a cyclic charge/discharge process. Such a composite electrode material with highly ordered and coaxial nanotube hybrid structure can contribute high energy storage for supercapacitor applications.     

KOH-activated nitrogen-doped graphene by means of thermal annealing for supercapacitor

KOH-activated nitrogen-doped graphene nanosheets (aNG) have been synthesized using thermal annealing method and applied in supercapacitor. The samples are characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and electrochemical techniques. Electrochemical results show that a capacitance of 132.4 F g^?1 at a charge/discharge current density of 0.1 A g^?1 is obtained for KOH-activated nitrogen-doped graphene which is nearly five times larger than that without KOH treatment. The present work demonstrates that KOH activation of thermally annealed nitrogen-doped graphene is a promising method for enhancing its application in energy storage system.     

Layered Al‐substituted Cobalt Hydroxides/GO Composites for Electrode Materials of Supercapacitors

In this work, Al‐substituted α‐Co(OH)₂/GO composites with supercapacitive properties were prepared by chemical co‐precipitated method in which cobalt nitrate and aluminum nitrate were used as the raw material, and graphite oxide was employed as carrier. The as‐prepared materials were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and fourier transform infrared spectroscopy (FT‐IR). Cyclic voltammetry (CV) and galvanostatic charge/discharge measurements showed that the Al‐substituted α‐Co(OH)₂/GO electrode material had excellent electrochemical capacitance. The specific capacitance of 1137 F·g⁻¹ was achieved in 6 mol/L KOH solution at a current density of 1 A·g⁻¹ within a potential range of 0–0.5 V. Moreover, only 12% losses of the initial specific capacitance were found after 500 cycles at a current density of 1 A·g⁻¹.     

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%)。     

Thiourea aldehyde resin-based carbon/graphene composites for high-performance supercapacitors

Thiourea aldehyde resin-based heteroatom doping carbon and graphene composites (RHDC/GN) were prepared by an in situ polymerization and carbonization. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that thiourea aldehyde resin deposited on lamellar GO flakes during the polymerization and RHDC/GN composites had a hierarchical structure. The specific capacitance of the RHDC/GN composites was high up to 355 F g^?1, much higher than that of the pure thiourea aldehyde resin-based heteroatom doping carbon (RHDC) with specific capacitance of 135 F g^?1 at a current density of 1.0 A g^?1 in 6-M KOH electrolyte. And the hetroatoms in RHDC/GN composites increase the specific capacitance, and GN enhances the conductivity of the electrodes which is beneficial to improving electrochemical cycling stability of the electrode significantly. The specific capacitance retains 90.97% after 5000 charge-discharge processes at 10 A g^?1, which provides potential as supercapacitors.     

Preparation of polybenzidine submicrorods with controllable morphology using poly (ethylene oxide)-b-polystyrene as a template and its electrochemical properties

Polybenzidine (PBz) particles were formed by the chemical polymerization in micelles of block copolymer by using Poly (ethylene oxide)-b-Polystyrene [PEO₁₁₃-b-PS_x (x = 50, 58 and 100)] as templates. The samples were characterized by IR, UV-vis absorption spectroscopy, transmission electron microscopy, cyclic voltammetry, constant current charge-discharge and electrochemical impedance to determine their morphologies and electrochemical properties. The results show that the prepared PBz is submicron to nanometer rod-like conducting particles with uniform sizes. Removing the templates did not affect the morphology but slightly reduced the size of the PBz particles. The size and morphology of PBz particles can be tuned by adjusting the amount of monomer. The PBz submicrorods showed 412 F·g^?1 specific capacitance in 0.3 mol·L^?1HClO₄ at the current density of 1 A·g^?1, indicating its better electrochemical activity. The specific capacitance of the PBz particles reduced less than 10% after 500 charge-discharge cycles at the current density of 3 A·g^?1, indicating its good cycling stability.