复合导电剂在超细炭微球超级电容器中的应用研究

导电剂能否在电极材料中形成良好的导电网络是影响超级电容器性能的关键因素之一. 以改进St?ber法合成了高比表面积且具有多级孔结构的超细空心炭微球,以其为电极材料,对比研究了碳纳米管/炭黑复合导电剂与单一导电剂对基于超细空心炭微球超级电容器性能的影响. 研究发现,在0.2 A/g的电流密度下,采用复合导电剂时其比电容为205.7 F/g,远高于单一导电剂时的比电容. 尤其在100 A/g的大电流密度下,采用复合导电剂时的比电容高达104.0 F/g,相比炭黑导电剂提高了275%. 分析表明,纤维状的碳纳米管和炭黑可在本身易团聚的超细空心炭微球中形成点-线协同作用的导电网络,这是提升超级电容器性能的主要原因.      

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%.     

Carbon nanotube and conducting polymer composites for supercapacitors

Composites of carbon nanotubes and conducting polymers can be prepared via chemical synthesis, electrochemical deposition on preformed carbon nanotube electrodes, or by electrochemical co-deposition. The composites combine the large pseudocapacitance of the conducting polymers with the fast charging/discharging double-layer capacitance and excellent mechanical properties of the carbon nanotubes. The electrochemically co-deposited composites are the most homogeneous and show an unusual interaction between the polymer and nanotubes, giving rise to a strengthened electron delocalisation and conjugation along the polymer chains. As a result they exhibit excellent electrochemical charge storage properties and fast charge/discharge switching, making them promising electrode materials for high Dower suDercapacitors.     

沸石咪唑骨架衍生空心纳米电极材料可控制备及其电化学性能研究

超级电容器是介于可充电电池和传统电容器之间的一种新型储能器件。它具有高功率密度、快速充放电和环境友好等优点。在众多应用于超级电容器的电极材料中,金属有机骨架材料因具有大的比表面积,可灵活调控的组成和结构,是十分理想的电极材料之一,又由于其易于合成、独特的结构和反应特性,也是制备纳米结构电极材料的理想模板之一。以沸石咪唑骨架（zeolitic lmidazolate framework,ZIF）-67为前驱体,采用二水合钼酸钠盐溶液刻蚀的方法成功制备了空心CoMo 层状双金属氢氧化物（layered double hydroxides, LDH）纳米笼结构,同时还讨论了钼酸钠的用量对最终产物形貌和性能的影响。当用作超级电容器电极材料时,所制备的空心Co₁Mo₅ LDH在1 A/g的时候最多可提供578 F/g的比电容,当电流密度增加到10 A/g时,比电容保持在346 F/g。与活性炭组装成非对称超级电容器后,该储能器件在功率密度750 W/kg时,能量密度最大可达到21.25 W·h/kg。在5 A/g的电流密度下,经过15 000次充放电循环后,仍保持了90%的初始容量。     

基于超级电容器的TiN@CNTF电极制备及性能研究

超级电容器因其独特的性能在便携式、可穿戴电子器件领域有着很大的应用潜力。目前对超级电容器的研究主要集中在对超级电容器电极材料的研究上。碳纳米管纤维具有电导率高、力学性能好、柔韧性高等优点,是超级电容器的理想电极材料。但是,碳纳米管纤维电容量的提升被其较小的比表面积所限制。通过在碳纳米管纤维表面生长三维阵列能够有效提高碳管纤维的比表面积,从而增大电容量。因此,采用水热法,在碳纳米管纤维表面成功生长TiO2纳米阵列,并通过氨气氮化获得了TiN@CNTF电极材料。采用三电极测试TiN@CNTF电极在Na2SO4溶液中的比电容达到215.5mF/cm2,有望作为一种柔性超级电容器的负极材料得到应用。     

Development of N-doped carbons from zeolite-templating route as potential electrode materials for symmetric supercapacitors

N-doped carbons were fabricated from zeolite-templated carbon via modification with melamine and mild KOH activation. The N-doping treatment and KOH activation slightly lowered the surface areas of pristine zeolite-templated carbon; nonetheless, N-doped carbons with a lower surface area exhibited much higher capacitance and cycling stability as fabricated into symmetric supercapacitor. Significantly, N-doped carbon obtained at 700℃ showed a capacitance of 45.7 F/g at 0.1 A/g and 42.0 F/g at 10 A/g for the fabricated supercapacitor with 6 M KOH electrolyte, with 92% retention of initial capacitance as current density increased up to 100-fold. This performance was attributed to the dual contribution of electric double-layer capacitance and pseudo-capacitance. The assembled supercapacitor also exhibited excellent cycling stability, with 91% capacitance retention at 10 A/g after 10000 cycles.     

淀粉基活性炭的制备及在超级电容器中的应用

以淀粉为原料,分别采用H₃PO₄活化法和物理-化学复合活化法制备活性炭,并将制备的活性炭组装成超级电容器。研究了制备工艺对活性炭孔结构及电容特性的影响;通过氮气吸附和SEM方法表征了淀粉基活性炭的孔结构和表面形貌,通过循环伏安曲线、恒流充放电、交流阻抗实验考察了其电化学性能。结果表明,比表面积与比电容并没有线性关系;物理-化学复合活化法在温度为850 ℃、活化时间为2h条件下,制备的淀粉基活性炭比表面积为1438 m²/g,比电容为150 F/g。     

CNTs/TiO2 composites and its elect rochemical properties after UV light irradiation

Due to the unique structure and special physical and chemical properties, carbon nanotubes (CNTs) have potential applications in supercapacitors. Recently, CNTs and their composites as a kind of supercapacitor electrode material have been made many achievements. In this paper, a CNTs/TiO2 composite was prepared successfully with hydrothermal method, and was used as a supercapacitor electrode material. After the tests on surface chemistry and electrochemical property, it was found that: (1) the capacitance of the CNTs/TiO2 composite electrode increased by 56%, compared with pure CNTs electrode, (2) after UV light irradiation pretreatment, due to the special photoelectric effect of TiO2 which improves the interfacial property and electrochemical property of the composite electrode, the capacitance further increased by 53% when compared with the electrode without the pretreatment, and meanwhile, the cycle life also increased significantly, i.e., the capacitance was up to 97%, after 100 cycles of charge and discharge, (3) due to the improvement of the interfacial property, the ion transport in the composite electrode became smoother, and the pore utilization was also effectively enhanced during high-current charge and discharge, and (4) due to the generation of a large amount of oxygen-containing groups on the TiO 2 surface after UV pretreatment, the CNTs/TiO2 composite electrode earned extra large pseudo capacitance, and therefore the capacitance of the composite electrode was further increased. Based on the experimental results in the present study a new process to improve surface character and electrochemicalproperty of the electrode has been developed by using a metal oxide as both pseudo capacitive material and surface modification material of the composites with a UV light irradiation.     

Functionalized graphene oxide based on p-phenylenediamine as spacers and nitrogen dopants for high performance supercapacitors

p-Phenylenediamine （PPD） functionalized graphene oxide （GO） materials （PPDG） were prepared through a one-step solvothermal process and their appli-cation as supercapacitors （SCs） were studied. The PPD is not only as the spacers to prevent aggregating and re-stacking of the graphene sheets in the preparing process but also as nitrogen sources to obtain the nitrogen-doped graphene. The structures of PPDG were characterized by Fourier transformed infrared spectroscopy （FT-IR）, X-ray diffraction spectroscopy （XRD）, Raman spectroscopy and X-ray photoelectron spectroscopy （XPS） and the results show that the nitrogen-doped graphene was achieved with nitrogen content as high as 10.85 at.%. The field emission scanning electron microscopy （FE-SEM） and high resolu-tion transmission electron microscopy （HR-TEM） have confirmed that the morphologies of PPDG were looselayered with less aggregation, indicating that PPD mole-cules, as spacers, effectively prevent the graphene sheets from restacking during the solvothermal reaction. The special loose textures make PPDG materials exhibit excellent electrochemical performance for symmetric SCs with superior specific capacitance （313 F/g at 0.1 A/g）, rate capability and cycling stability. The present synthesis method is convenient and may have potential applications as ultrahigh performance SCs.     

聚合物共混法制备超级电容器用多孔炭材料

以酚醛树脂为前驱体,以聚乙二醇为致孔剂,采用聚合物共混法制备超级电容器用中孔炭电极材料. 采用N2吸附法测试了炭材料的比表面积和孔结构参数. 采用恒流充放电、循环伏安、交流阻抗等评价了其在1mol·L-1Et4NBF4/PC有机电解液中的电化学双电层电容性能. 结果表明,酚醛树脂和聚乙二醇等比例共混炭化制备的多孔炭的比表面积为618m2·g-1,中孔率为59.7%,比电容为32F·g-1,大电流性能和循环性能良好.     

孔道结构对有序介孔炭电化学性能的影响

以三嵌段共聚物（F127）为模板剂,间苯二酚（R）和甲醛（F）为碳前驱体,在外加的酸性条件下通过自组装的方法制得了F127/RF复合材料,然后经碳化处理得到具有高度有序孔道结构的介孔炭材料（OMCs）,通过XRD、TEM、N₂吸/脱附手段(77K低温下)对其进行结构表征。测试结果表明有序介孔炭材料的BET比表面积和总孔体积分别为770m²/g和0.65cm³/g。以有序介孔炭材料为电极制备超级电容器,对其进行直流恒流充放电测试、循环伏安测试和交流阻抗测试,结果显示在电流密度为0.02A/g时OMC-3比容量为130F/g,100次充放电循环后电容量保持率在99%以上。     

超级电容器用新型微晶炭的结构及其电容性能

以热处理后的煤沥青焦为原料,采用KOH活化法制备了具有较小比表面积(＜200m~2/g)的系列微晶炭.采用N_2吸附、X射线衍射(XRD)和X射线光电子能谱(XPS)等手段表征了微晶炭的孔结构、微晶结构以及表面化学性质,研究了微晶炭作为超级电容器电极材料在1 mol/L的四乙基四氟化硼酸铵盐/碳酸丙烯酯电解液体系中的电容性能.结果表明:制得的微晶炭具有大量类石墨微晶和较高的石墨化度,d_(002)(晶面层间距)为0.356～0.666 nm,表面含碳量大于95%;活化6 h后,在4.0 V下微晶炭的质量比电容高达139 F/g.微晶炭的储电行为包括插层电容和双电层电容两部分,其中电活化所造成的插层电容是决定微晶炭最终比电容的主要因素,插层电容主要由电极材料的石墨化度决定.     

Fabrication and Electrochemical Properties of Carbon Nanotube-based Composite Electrodes for Electrochemical Capacitor Applications

1 Results Electrochemical capacitors (ECs) are expected to be used in hybrid electric vehicles in combination with batteries or fuel cells because of their higher power density than batteries. ECs using electrical double layer capacitance of carbon based materials and pseudocapacitance of transition metal oxides are called electrochemical double layer capacitors (EDLC) and supercapacitors (or pseudocapacitor), respectively. Transition metal oxides are considered the best candidates for high energy dens...     

Linear and non-linear pseudocapacitances with or without diffusion control

Pseudocapacitance is an important reversible charge storage mechanism in many electrode materials. Although the concept was first proposed in early 1960s, it has been more widely studied following the observation of rectangular cyclic voltammograms (CVs) when testing some transition metal oxides and electronically conducting polymers, and the association with supercapacitor. However, interpretation of pseudocapacitance is inconsistent in the literature. Although all agree that materials are pseudocapacitive if they undergo Faradaic reactions and exhibit rectangular CVs, some have regarded any surface confined Faradaic reactions which may present non-rectangular or even peak-shaped CVs to be pseudocapacitive. In the case of rectangular CVs, the amount of charge stored in the electrode is a linear function of the electrode potential, whilst for non-rectangular or peak-shaped CVs, the relationship is non-linear. It is shown in this article that only linear pseudocapacitance is of relevance to supercapacitor, but non-linear pseudocapacitance may find applications in rechargeable battery and supercapattery. Further, it is clarified that the equation i ​= ​k₁v ​+ ​k₂v^1/2 is useful in analysis of electrode kinetics in terms of surface confinement and diffusion control. However, this kinetic equation is blind to the thermodynamically determined charge storage mechanisms as shown by experimental evidence, and should not be used to differentiate non-capacitive Faradaic processes from pseudocapacitance, either linear or non-linear.     

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.     

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.     

应用于超级电容器的碳纳米管电极的几个特点

为拓展碳纳米管的实际应用 ,对碳纳米管应用于超级电容器的电极材料的特点作了深入分析。碳纳米管电极具有独特的孔隙结构和高比表面积利用率 ;碳纳米管表面可以形成丰富的官能团 ,具有较好的吸附特性。此外 ,作者提出了采用酸处理或球磨工艺打断碳纳米管、提高其内腔利用率的方法。可以预料 ,碳纳米管在这一领域将得到广泛应用     

Mangosteen peel-derived activated carbon for supercapacitors

This work reports the effects of activation temperatures on the porous development and electrochemical performance of activated carbons. Herein, activated carbons were prepared from the biowaste of mangosteen peel by using KOH activation at temperatures of 400, 600, and 800 ?°C. The results demonstrate that the specific surface area increases with increasing the activation temperatures in which the well-developed porous structure after KOH activation at 800 ?°C provides the highest specific surface area of 1039 ?m² ?g^?1. At 600 ?°C, the activated carbon delivers the highest specific capacitance value of 182 ?F ?g^?1 ?at a current density of 0.5 ?A ?g^?1 in 3 ?M KOH aqueous electrolyte. This is correlated well with its high micropore fractions (99%). Moreover, it was found that the activation temperature changes the major contribution of oxygen-containing functional group on surface of activated carbon, which is beneficial for the enhancement of the specific capacitance value of activated carbon at the temperature of 600 ?°C. This work suggests that the activation temperature is a key to optimizing the electrochemical performance of activated carbons. Overall, our activated carbons can be considered as a strong candidate for use as electrode materials in supercapacitors.     

Mn_2O_3/CRF复合材料的制备及其在超级电容器中的应用

通过采用沉淀法在碳气凝胶表面负载金属氧化物三氧化二锰,制备得到Mn_2O_3/CRF复合材料。采用X射线衍射及电镜扫描等技术对所制备的复合材料进行结构形貌表征。实验结果发现碳气凝胶具有多重片层结构且孔隙发达。通过调节锰盐的含量考察三氧化二锰负载量对复合材料电化学性能的影响作用。采用循环伏安法及充放电测试对材料的电化学性能进行测试,结果表明Mn_2O_3/CRF复合材料具有良好的电容性及较好的可逆性。当Mn_2O_3含量达15%时复合材料的比电容最大,可达118.5 F/g。通过充放电测试1000次后发现该电极的比电容依然能够保持在一稳定值上,具有较好的稳定性。     

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。