Understanding supercapacitors based on nano-hybrid materials with interfacial conjugation

The recent fast development of supercapacitors,also known scientifically as electrochemical capacitors,has benefited significantly from synthesis,characterisations and electrochemistry of nanomaterials.Herein,the principle of supercapacitors is explained in terms of performance characteristics and charge storage mechanisms,i.e.double layer(or interfacial) capacitance and pseudo-capacitance.The semiconductor band model is applied to qualitatively account for the pseudo-capacitance in association with rectangular cyclic voltammograms(CVs) and linear galvanostatic charging and discharging plots(GCDs),aiming to differentiate supercapacitors from rechargeable batteries.The invalidity of using peak shaped CVs and non-linear GCDs for capacitance measurement is highlighted.A selective review is given to the nano-hybrid materials between carbon nanotubes and redox active materials such as electronically conducting polymers and transition metal oxides.A new concept,"interfacial conjugation",is introduced to reflect the capacitance enhancement resulting from π-π stacking interactions at the interface between two materials with highly conjugated chemical bonds.The prospects of carbon nanotubes and graphenes for supercapacitor applications are briefly compared and discussed.Hopefully,this article can help readers to understand supercapacitors and nano-hybrid materials so that further developments in materials design and synthesis,and device engineering can be more efficient and objective.     

Advanced materials for aqueous supercapacitors in the asymmetric design

Supercapacitors have been recognized as one of the promising energy storage devices in the future energy technology. In this perspective, rapid progress is made in the development of fundamental and applied aspects of supercapacitors. Various techniques have been developed specifically to estimate the specific capacitance. Numerous efforts have been made in the literature to increase the specific capacitance of electrode materials. Recently, researchers pay more attention on designing supercapacitors of asymmetric type with extending cell voltage and dissimilar materials with complementary working potentials. Researchers try to increase the specific energy of asymmetric supercapacitors (ASCs). Conversely, it is still a challenge to find a suitable operation conditions for ASCs in various designs, especially for the one with battery type electrode. In this review, we describe our recent research works and other reports on the preparation of various nanostructured electrode materials and the performances of both symmetric and asymmetric supercapacitors. Finally, we demonstrate effects of charge balance on the capacitive performances of ASCs which consist of one electrode material of the battery type and one capacitive material. We also demonstrate how to evaluate the charge capacities of both positive and negative electrode materials for this ASC application.     

Facile construction of novel CoMoO4 microplates@CoMoO4 microprisms structures for well-stable supercapacitors

A simple and controllable strategy has been developed to fabricate CoMoO_4 microplates/CoMoO_4 microprisms(CMCMs) structures on Ni foam via a facile, cost-effective, two-step hydrothermal route. The as-grown 3D architecture exhibited excellent areal capacitance of 4.33 F cm~(-2)at a galvanostatic chargedischarge current density of 50 mA cm~(-2)(6 Ag~(-1)) and outstanding cycle performance with only 2.8%degradation over 6500 cycles in the 3 M KOH solution. The asymmetric all-solid-state supercapacitors based on activated carbon(AC) and CMCMs exhibited much better electrochemical performance than the symmetric counterpart, showing an areal capacitance of 95.22 mF cm~(-2)at the current density of 12 m A cm~(-2)and excellent cycling stability with 92.27% of the initial capacitance after 5000 cycles. These results may provide useful guidelines for materials selection and configuration designs for the novel energy storage devices based on Co Mo O4 components and substrates.     

用于高性能超级电容器的基于蚕沙的二氧化锰/碳纳米复合材料

MnO₂/biomass carbon nanocomposite was synthesized by a facile hydrothermal reaction. Silkworm excrement acted as a carbon precursor, which was activated by ZnCl₂ and FeCl₃ combining chemical agents under Ar atmosphere. Thin and flower-like MnO₂ nanowires were in-situ anchored on the surface of the biomass carbon. The biomass carbon not only offered high conductivity and good structural stability but also relieved the large volume expansion during the charge/discharge process. The obtained MnO₂/biomass carbon nanocomposite electrode exhibited a high specific capacitance (238 F·g?1 at 0.5 A·g?1) and a superior cycling stability with only 7% degradation after 2000 cycles. The observed good electrochemical performance is accredited to the materials’ high specific surface area, multilevel hierarchical structure, and good conductivity. This study proposes a promising method that utilizes biological waste and broadens MnO₂-based electrode material application for next-generation energy storage and conversion devices.     

铜配合物[Cu(C3N2H3)2(H2NC6H4SO3)2(H2O)2]·2H2O的合成和晶体结构

合成了一种新的铜配合物[Cu(C3N2H3)2(H2NC6H4SO3)2(H2O)2]·2H2O,经元素分析和X-射线衍射得该化合物的分子式为C18H26CuN6O10S2,该晶体属单斜晶系,空间群为P 121／n,晶胞参数为a=7．2928(15) A,b=15．635(3)A,c=11．361(2)A;α=γ=90°,β=104．94(3)°;Z=2;DC=1．629 mg／m3;F(000)= 634;对于可观测衍射点的R1=0．0548,wR2=0．1516,S=1．014;最终差图中最大电子密度峰值和洞值分别为0．968e．A-3和-0．465e．A-3．两个对氨基苯磺酸和两个吡唑各自提供一个N原子、另有两个H2O分别与 Cu2 配位,Cu2 的配位多面体为畸变八面体．     

MnO_2/竹炭超级电容器电极材料的性能

采用机械球磨法将竹炭和MnO2按不同比例复合,得到一系列不同配比的MnO2/竹炭电容器电极复合材料,对其进行扫描电子显微镜(SEM),X射线衍射(XRD)和热重分析(TG-DSC),并进行循环伏安和电化学充放电测试。结果发现,当MnO2在复合材料中的质量分数为1%时,电极比容量可以达到338 F/g,100次循环后维持在260 F/g,显示很好的电化学性能。     

二维开放骨架硫酸镧的水热合成与表征

采用水热合成方法，以氧化镧、硫酸和哌嗪、水为原料得到了具有新颖结构的硫酸镧．单晶衍射结果表明该化合物是有机胺支撑的、通过镧与硫酸根配位形成的层状开放骨架结构，该化合物也用元素分析、差热-热重和红外进行了表征．结果表明结构解析能够同相应的表征较好地吻合．     

酚醛树脂基活性炭微球的制备及其电化学性能

以苯酚和甲醛为原料,盐酸为催化剂,制备醇溶性酚醛树脂前驱体,探讨炭化温度对炭微球性能的影响,并将炭微球在3 mol/L HNO3溶液中活化后得到活性炭微球。利用红外光谱、X线衍射(XRD)、扫描电镜(SEM)、循环伏安、恒流充放电、循环寿命等对该材料进行表征及电化学性能测试。研究结果表明:炭微球的最佳炭化温度为750℃,在该温度下制备的炭微球具有良好的球形形貌,其结构为部分石墨化的无定形炭;活性炭微球作为电容器电极材料具有良好的电化学性能,在1 mV/s扫描速度下比电容达到247.8 F/g;在0.5 A/g电流密度充放电下扣式超级电容器比电容高达60 F/g,且充放电循环5 000次后比电容几乎没有衰减。     

超级电容器电极材料纳米Fe3O4的制备及其性能研究

采用化学共沉淀法制备了纳米Fe3O4,系统考察了n(Fe3+):n(Fe2+)、反应pH值、熟化温度等对纳米Fe3O4生成的影响,从而确定最佳反应条件.将纳米Fe3O4应用到超级电容器上,研究了其作为电容器电极材料的电化学性能.结果表明:在最佳反应条件下,制备出的纳米Fe3O4的晶体结构完整;经电化学性能测定,Fe3O...     

Mn_7C_3@C核壳型纳米粒子制备及其超级电容器电极特性

以甲烷作为碳源气体,块体锰作为原料,采用一种简单的直流电弧等离子体法成功制备了Mn_7C_3@C核壳型纳米粒子,用于高性能超级电容器的电极材料.所制备的Mn_7C_3@C核壳型纳米粒子平均直径为30~35nm.拉曼光谱结果显示石墨碳壳具有良好的导电性.通过循环伏安、恒电流充放电及电化学交流阻抗谱对Mn_7C_3@C核壳型纳米粒子电极材料进行电化学性能分析,结果表明其具有高比电容、快速充放电等优异的电化学性能.在扫描速率为1mV/s时,比电容最高可达185.8F/g.同时具有良好的循环稳定性,在100mV/s扫描速率下1 000次循环伏安测试后,比电容仍保持为最初的88%,与单纯Mn_7C_3(79%)相比,有明显提高.Mn_7C_3@C核壳型纳米粒子电极材料优异的电化学性能归因于其良好的核壳结构,富缺陷碳层具有良好的导电性,有助于离子的传输和结构的稳定,而内核Mn_7C_3主要产生赝电容,在C和Mn_7C_3的协同作用下产生双电层和赝电容双模式储能机制.     

MnO2/碳纳米球电化学超级电容器电极材料的制备与性能研究

利用水热法合成了纳米棒状的MnO_2/碳纳米球(CNPs)作为电化学超级电容器的电极材料.利用场发射扫描电镜(FESEM)、X射线衍射光谱分析(XRD)对样品的微观形貌、物相进行分析;利用循环伏安法和恒电流充放电测试材料的电化学性能.结果表明:纳米棒状MnO_2/CNPs复合材料具有良好的电化学性能.在0.1 A/g的电流密度,1 mol/L Na_2SO_4电解液中,电极材料的比电容高达305.6 F/g,远高于纯碳球的比电容(49.3 F/g),当电流密度增至5 A/g时,材料的比电容为235 F/g,比电容仍能保持76.9%.     

CuO/CeO2/ZSM-5催化剂的合成、表征及催化性能的研究

以ZSM - 5分子筛为载体用浸渍法混合负载Cu、Ce ,研制出一种复氧化物分子筛催化剂MxOy/ZSM - 5(Cu、Ce) .考察了它对液相合成乙酸丁酯反应的催化活性 ,并探讨了催化剂的制备条件对催化活性的影响 ,用IR、DTA、TG、ICP、比表面仪等技术对催化剂进行表征 .结果表明 :在Cu∶Ce =3∶1,T =12 0℃ ,酸∶醇 =1∶2 ,催化剂用量为 3g ,t =6h时 ,乙酸丁酯的产率高达 96 % ,且催化剂制备成本低 ,催化剂热稳定性好 .     

壳聚糖水解技术对超级电容器电极材料性能的影响

壳聚糖是一类具备天然氮元素的海洋生物质,可作为制备超级电容器的前驱体,但溶解性质限制了其反应均匀性。本研究以壳聚糖为原料,利用自主研发的水解法制备壳寡糖均相溶液,作为前驱体制备超级电容器电极材料。实验采用了三电极体系对该电极材料多性能进行表征,包括循环性能、阻抗、元素分析、SEM、TEM、XRD等,探讨了水解工艺对电极材料综合性能的影响,并且与出发原料壳聚糖进行对比。结果表明：壳寡糖电极材料性能有了明显的提升,在电流密度为0.5 A g-1时比电容高达227.5 F g-1,具有优秀的循环稳定性,1000圈循环后比电容仍未有明显下降,且电极的膜阻抗和电荷转移电阻较小,说明该工艺制备的壳寡糖具有很好的超级电容器方面应用前景。     

新型三维无机-有机杂化材料的水热法合成

文中通过溶剂热法合成无机有机杂化材料Co₂(bpp)₄V₄O₁₂·4H₂O(bpp为1,3-联(4-吡啶基)丙烷),对影响溶剂热反应的主要因素如反应物摩尔比、反应温度、pH值等进行系统研究,确定了合成这种新型化合物的最佳条件。同时还比较说明刚性4,4'-联吡啶和柔性1,2-二-(4吡啶基)乙烷和1,3-二(4-吡啶基)丙烷对无机骨架的影响和Co₂(bpp)₄V₄O₁₂·4H₂O晶体结构的新颖之处。     

Influence of thermal-decomposition temperatures on structures and properties of V2O5 as cathode materials for lithium ion battery

Submicron spherical V2O5 particles with a uniform size and a lower crystallinity were successfully synthesized by a chemical precipitationthermal decomposition technique using the commercial V2O5 powders as starting material. The crystal structure and grain morphology of samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM), respectively. Electrochemical testing such as discharge–charge cycling(CD) and cyclic voltammetry(CV) were employed in evaluating their electrochemical properties as cathode materials for lithium ion battery. Results reveal that the crystallinity and crystalline size of V2O5 particles increased when the thermal-decomposition temperature increased from 400 ℃ to 500 ℃, and their adhesiveness was also synchronously increased. This indicate that the thermaldecomposition temperature palyed a significant influence on electrochemical properties of V2O5 cathodes. The V2O5 sample obtained at 400 ℃ delivered not only a high initial discharge capacity of 330 m A h g-1and also the good cycle stability during 50 cycles due to its higher values ofα in crystal structure and better dispersity in grain morphology.     

石墨烯/Cu-MOF锂电池负极材料的制备及电化学性能研究

金属有机骨架化合物是一种由金属离子与有机配体通过配位键或共价键合成的新型的电极材料。然而,其低的电子导电率和严重的不可逆锂存储制约了该材料在锂电池领域的实际应用。石墨烯具有一系列独特属性,如高的导电率、高表面积、化学稳定性,机械强度和柔韧性,多孔结构。通常用来掺杂在电极材料中以提高循环性能和增加电池的容量。在本实验中,我们研究了Cu-MOF掺杂石墨烯(Cu-MOF/RGO)作为锂电负极材料的电化学性能。结果表明,在充放电电流密度为50 mA g-1时,充放电循环50次后,材料的放电比容量可达到520 mAh g-1。同时该材料也显示出较好的倍率性能和较高的库仑效率。由此可以看出Cu-MOF/RGO是一种具有前景的锂离子电池负极材料。     

交流激励电容层析成像(ECT)C／V转换电路的分析

介绍一种基于交流激励型的电容层析成像(ECT)的C／V转换电路．主要分析了电路的工作原理,实际应 用中的反馈模式电路．该电路具有较强抗干扰能力,稳定性好和较小的漂移．     

MnO@CoMn$_{textbf{2}}$O$_{textbf{4}}$/N-C纳米线复合材料的制备及其作为锂离子电池阳极材料的电化学性能

过渡金属氧化物作为锂离子电池(lithium-ion batteries, LIBs)阳极材料时具有较高的理论容量, 但因其电导率低, 以及充放电过程中的体积膨胀效应常会导致容量的快速衰减. 碳包覆是提升金属氧化物导电性的有效方法, 二者之间的协同效应也可以有效提升材料的电化学性能. 以MnO$_{2}$纳米线为模板制备出MnO$_{2}$@ZIF-67有机-无机杂化纳米结构, 再通过退火处理合成了氮掺杂碳包覆的MnO@CoMn$_{2}$O$_{4}$纳米线复合材料(MnO@CoMn$_{2}$O$_{4}$@N-C). ZIF-67的有机配体在高温煅烧过程中发生碳化反应, 产生了氮掺杂碳, 提升了导电性. 当作为锂离子电池阳极材料时, MnO@CoMn$_{2}$O$_{4}$/N-C纳米线复合材料在0.1 A/g电流密度下的首次放电比容量为1 594.6 mA$cdot$h/g, 并且在100次充放电循环后的放电比容量仍保持在 925.8 mA$cdot$h/g, 在0.5 A/g电流密度下经200次充放电循环后的放电比容量仍维持在837.6 mA$cdot$h/g, 同时具有优异的倍率循环性能. 这种优异的电化学储能特性主要来源于复合材料的特殊结构, 以及氮掺杂碳的包覆.     

载体的酸处理条件对整体式钌-堇青石催化剂性能的影响

研究了堇青石经硝酸处理后对整体式钌基氨合成催化剂性能的影响.利用BET、XRD、X射线荧光半定量分析(XRF)和Boehm滴定等测试手段对酸处理前后的堇青石进行表征,并对催化剂的反应性能进行评价.结果表明:堇青石经硝酸处理后,Mg、A l离子溶出,载体表面酸性增强,并且随着酸处理强度的增加,表面酸性进一步增加,与未经酸处理的堇青石相比,总酸量可以增加一个多数量级.同时,酸处理条件对堇青石的表面织构也有较大的影响,如温和的酸处理条件并不能改变堇青石的孔结构以及比表面积,而苛刻的酸处理条件可以有效地提高堇青石的比表面积、比孔容积,改善堇青石的孔径分布.但是,酸处理并没有改变堇青石载体的物相结构.催化剂的活性随着堇青石载体的酸处理强度的增加而降低,即比表面积越大、表面酸性越强催化剂的活性越低,可见,载体的表面酸性是决定催化剂活性的主要因素.