石墨烯纳米孔道内受限水介电常数影响因素的分子动力学模拟

受限水的介电特性对于石墨烯电容器的储能效率有着重大的影响.因此本文使用分子动力模方法,研究了不同石墨烯纳米孔道宽度(0.812～10 nm)下内受限水介电常数的分布及其影响因素.结果表明,在石墨烯纳米孔道内部受限水双电层结构可分为空隙层、界面层和体相层三个部分.其整体的介电常数随孔道大小的降低而线性减少.这是由内部体相层的宽度的降低而导致的.此外电极电压大小和石墨烯-水相互作用参数ε_CO的强弱也会显著改变电极表面的双电层(Electric Double Layers, EDLs)结构.其中电压的增大使得介电常数分布的震荡的程度也随之增加,最终导致了整体介电常数的减小.与之类似,亲水态的石墨烯表面(高ε_CO)下受限水分布的震荡程度也显著增加,这导致了整体介电常数的降低.     

不同N掺杂构型石墨烯的量子电容研究

超级电容器是一种利用界面双电层储能或在电极材料表面及近表面发生快速可逆氧化还原反应而储能的装置, 其特点是功率密度高、循环寿命长. 制备出兼有高能量密度的电极材料是当前超级电容器研究的重点. 以提高电容储能为目标, 通过掺杂N原子来调制石墨烯的电子结构, 使用基于密度泛函理论的第一原理计算了不同N掺杂构型石墨烯的态密度和能带结构, 拟合出了石墨烯的量子电容, 分析了量子电容储能提升的原因.     

固体离子双电层电容器主要参数的直流测试方法

快离子导体的一个重要应用领域是固体离子器件[1].双电层电容器就是一个例子.无极性固体离子双电层电容器的物理模型如图1所示.图2的虚线框内是它的等效线路.Cd是两个双电层电容串联的总电容(由于Cd很大,可以忽略体电容的贡献);Rs是等效串联电阻,主要是离子导体的电阻; R1是漏电阻,它表征双电层电容器泄漏电流的能力.Cd,Rs及R1是决定离子电容器性质的三个主要参量.由于Cd大,Rs的值也十分可观,用通常的电容电桥无法测试,因此人们通常进行直流测试.文献[2]报道了恒流充电测试Rs和Cd的方法.我们在研究离子双电层电容器的过程中采用了两种…     

中空笼状多孔结构镍钴层状氢氧化物的制备及其电化学性能

超级电容器以功率密度高、寿命长、环境友好等优点在各种能量存储设备中受到广泛关注.所以,提高电极材料的储能性能对超级电容器的开发与应用具有重要的意义.具有特定纳米结构的功能材料作为超级电容器电极材料时具有优异的电化学性能,原因在于其能提供丰富的电化学活性位点、高的比表面积和增加电解质与材料的接触面积.因此,本文以ZIF-67纳米晶为模板,利用硝酸盐刻蚀的方法制备中空笼状镍钴层状氢氧化物(NiCo-LDH),并研究其作为超级电容器电极材料的储能性能.借助X射线衍射、扫描电镜、透射电镜、低温氮气吸附/脱附和电化学测试等手段分析所得NiCo-LDH的结构、形貌和电化学性能.结果表明:NiCo-LDH由纳米片组装形成中空笼状结构,拥有丰富的介孔和大孔孔道以及较高的比表面积,从而有助于增加电活性位点,促使电解液与电极材料的充分接触,进而显著提高材料的储能性能.当刻蚀用镍、钴盐质量比为1:1时,样品Ni₁Co₁-LDH的比电容可达801 F·g^-1(电流密度为0.5 A·g^-1),且在大电流密度下(10 A·g<...     

电化学制备钛网负载聚吡咯/石墨烯复合膜及其在超级电容器中的应用

通过电化学的方法在钛网上制备了聚吡咯与石墨烯的复合物薄膜,其过程是先在钛网上通过自组装干燥膜法附着上石墨烯氧化物膜,而后采用电化学还原的方法原位还原制备得到石墨烯膜,随后加入吡咯单体,再通过电化学聚合的方法在石墨烯的表面生长聚吡咯,得到的聚吡咯开始以颗粒的形式存在,而后随着聚合的进行得到了链状的聚吡咯.得到的复合膜有高的比表面积和导电性,可以作为电极活性材料用于超级电容器中提供赝电容,结果表明,复合膜作为电极材料的超级电容器拥有高的性能,比电容达400 F/g,并且电极的充放电稳定性高,5000次复合膜充放电循环后比电容还能保留82%,说明该材料适合于超级电容器.     

氮掺杂石墨烯纳米片的制备及其电化学性能

以石墨片为原料,在氮气气氛下,通过机械针磨法制备了氮掺杂石墨烯纳米片.扫描电子显微镜和比表面积分析表明机械针磨过程可以有效地将大尺寸石墨片破碎成石墨烯纳米片.在石墨片的破碎过程中,会引起C—C键的破坏.因此,在破坏的边缘位置能够产生碳活性点.这些碳活性点可以与氮反应实现氮元素的掺杂.X射线光电子能谱分析表明碳活性点与氮反应使氮元素掺入石墨烯结构边缘,形成吡咯型氮和吡啶型氮.电化学阻抗谱分析表明所制备的氮掺杂石墨烯纳米片对I_3~-还原反应具有较高的电催化活性,循环伏安与恒流充放电测试表明氮掺杂石墨烯纳米片具有较好的电容性能.较高的比表面积和边缘氮掺杂结构是氮掺杂石墨烯纳米片具有优异电化学性能的主要原因.因此,氮掺杂石墨烯纳米片可以应用于染料敏化太阳能电池对电极和超级电容器电极.     

静电纺丝法简便合成的碳纳米纤维——二氧化锰超级电容器电极材料的制备及研究

超级电容器是近几年迅速发展起来的一种新型储能元件,决定其性能的最重要因素是电极材料.本文报道以廉价的二氧化锰(MnO2)作为赝电容材料,采用静电纺丝法简便合成碳纳米纤维-MnO2电极材料,并尝试在样品中更高比例地掺杂MnO2以使更多的MnO2纳米颗粒镶嵌在碳纳米纤维中,以提高其电容性能,并系统地研究了所制备的电极材料的结构及其电化学性能.     

基于镍泡沫支撑的Co_3O_4纳米多孔结构的高性能超级电容器电极

在众多能量存储和转化器件中,超级电容器由于具有功率密度高、充放电迅速和优异的循环性能的优点而被广泛研究.然而,较低的比容量和能量密度,限制了超级电容作为大尺度能量存储和转化器件的广泛应用.为了提高超级电容器的比容量,需要增大电极材料和电解质的接触面积,进而促进电极材料俘获/释放电解质中的粒子(例如电子、离子或者小分子).在此,我们通过简单的水热法联合高温退火实验方案能够大规模制备出镍泡沫支撑的Co_3O_4多孔纳米结构.无需借助导电胶和粘合剂,在集流器镍泡沫上"生长"Co_3O_4多孔纳米结构直接作为超级电容的电极材料.这种多孔纳米结构和一体化设计思路不仅能够有效提高电极的导电性,而且能够有效缩短离子和电子的迁移路径.由于多孔的结构特征和优异的导电性能,Co_3O_4电极表现出超高比容量(在电流密度为2.5 m A·cm~(-2)和5.5 m A·cm~(-2)时,比容量分别为1.87 F·cm(-2)(936 F·g-1)和1.80 F·cm~(-2)(907 F·g-1))、较好的倍率性能(电流密度从2.5 m A·cm~(-2)增大到100 m A·cm~(-2)时,保留其48.37%的初始电容)和超高的循环稳定性(经历4000次电流密度为10 m A·cm~(-2)的循环充放电过程,保留其92.3%的比容量).这种多孔纳米结构和一体化设计思路对设计其他高性能储能器件具有重要的指导意义.     

含碳Na-β(β")-Al_2O_3的导电性能

本文研究了含碳(1—10)wt％的Na-β(β″)-Al_2O_3,指出含碳6wt％以下仍是良好的快离子导体,而且由于混入了碳,离子电导率比纯的Na-β(β″)-Al_2O_3提高一到两个数量级。样品的体电阻,晶界电阻,双电层电容及其漏电阻等参量都随含碳量的不同而变化。文中详细地讨论了碳的影响。在-40℃到80℃温度范围测量了纯样品与含碳样品的电导温度特性,指出含碳的Na-β(β″)-Al_2O_3 是做双电层电容器的良好材料。     

退火温度调控多层折叠石墨烯力学性能的分子动力学模拟

退火是石墨烯宏观组装材料常用的制备工艺之一,广泛用于其性能的调控.在石墨烯基材料中,石墨烯片层由于其自身的二维特性通常在微纳米尺度下呈现出多层折叠的结构.然而这种微观结构对材料力学性能退火调控的影响仍未得到充分的了解.为了阐明多层折叠石墨烯力学性能与退火温度间的调控关系,基于分子动力学模拟研究了材料弹性模量、拉伸强度、极限应变以及断裂韧性等关键力学性能参数随退火温度的变化规律,进而结合观察微观结构的演化过程揭示了性能调控现象的物理机制.结果表明:更高的退火温度将增强多层折叠石墨烯的弹性模量与拉伸强度,但同时削弱了其极限应变,并且其断裂韧性能够在一定退火温度范围内实现强化.研究发现,以上力学性能的调控作用归因于更高的退火温度将造成更加密集的层间交联,从而增强了折叠区域层间界面的相互作用,并限制了折叠结构的形态展开,致使结构破坏模式发生转变.     

棱形石墨烯纳米孔道内离子传输性能的分子动力学模拟

纳米通道的尺寸、结构和表面化学对其内部溶液的分布结构和输运性质有着重大影响.本文研究了一种全新的菱形石墨烯纳米通道.这种理想的通道与最近被广泛研究的金属有机框架材料(MOF)的内部结构类似,有着与传统的碳纳米管截然不同的内部结构.本文使用分子动力学模拟的方法研究在不同尺寸的菱形石墨烯纳米通道内的KCl溶液的性质,并将其与同尺寸的单壁碳纳米管进行了比较.研究结果表明在小孔道内(<20?)其内部的溶液结构呈现若干个密度极高的聚集区域,即出现了结晶化的趋势．这一研究结果,将为MOF的结构设计提供思路,从而有望实现类似于生物离子通道的高选择性和高传输能力.     

Capacitance properties of ordered porous carbon materials prepared by a templating procedure

The electrochemical performance of carbon materials with a highly ordered nanoporous structure is investigated in two-electrode supercapacitors. The materials were prepared by a templating procedure using a silica matrix (type MCM-48 or SBA-15) with an organized porosity in which carbon was inserted, either by chemical vapor decomposition of propylene or by impregnation with a sucrose solution followed by carbonisation. After the removal of silica, a micro-mesoporous carbon residue is recovered which displays an uniform pore size distribution. Such a well-defined nanostructure is interesting for a fundamental study of the double layer capacitance behavior. The performance of supercapacitors built with electrodes prepared from the templated carbon was tested in acidic, alkaline and organic electrolyte solutions. High values of capacitance in aqueous and organic media were obtained with a rectangular shape of the voltammograms over a wide range of scan rates indicating a quick charge propagation. Especially, the templated carbons prepared by the impregnation of sucrose in MCM-48 display high capacitance values due to the formation of an adequate micro-mesoporous network during their formation. A marked shift of capacitance drop at higher values of frequency is clearly observed for the materials rich in mesopores; the mesopores make easier the diffusion of the ions to the active surface.     

双尺度疏油结构纳米通道滑移效应的研究

针对双尺度结构表面疏油特性的优异性,采用分子动力学的方法建立油液流体正十六烷烃分子模型,研究双尺度结构壁面润湿性影响下的纳米通道内流体的流动特性,通过对通道壁面亲疏油性下的双尺度结构的构建,与光滑壁面和单尺度壁面进行比较来探究双尺度纳米通道表面结构影响下油液流体在纳米通道内密度分布、速度分布、速度滑移和滑移长度的影响.模拟结果表明:对于亲油通道壁面,双尺度结构壁面亲油性明显加强,主流区域流体密度、流体速度和速度滑移都减小,甚至出现负滑移;而对于疏油通道壁面,双尺度分层结构能加强壁面的疏油性,通道内壁面形成稳定的气层使流体主流区域的密度增大,并且通道内流体的速度、速度滑移和滑移长度明显大于光滑和单尺度结构壁面.因此,纳米通道内双尺度结构能改变通道壁面的润湿性,并且能够加强流体在纳米疏油通道内的滑移减阻效应,为纳米通道内油液运输以及润滑薄膜减阻提供了设计基础.     

Impurity effects on ionic-liquid-based supercapacitors

Small amounts of an impurity may affect the key properties of an ionic liquid and such effects can be dramatically amplified when the electrolyte is under confinement. Here the classical density functional theory is employed to investigate the impurity effects on the microscopic structure and the performance of ionic-liquid-based electrical double-layer capacitors, also known as supercapacitors. Using a primitive model for ionic species, we study the effects of an impurity on the double layer structure and the integral capacitance of a room temperature ionic liquid in model electrode pores and find that an impurity strongly binding to the surface of a porous electrode can significantly alter the electric double layer structure and dampen the oscillatory dependence of the capacitance with the pore size of the electrode. Meanwhile, a strong affinity of the impurity with the ionic species affects the dependence of the integral capacitance on the pore size. Up to 30% increase in the integral capacitance can be achieved even at a very low impurity bulk concentration. By comparing with an ionic liquid mixture containing modified ionic species, we find that the cooperative effect of the bounded impurities is mainly responsible for the significant enhancement of the supercapacitor performance.     

离子凝胶薄膜栅介石墨烯场效应管

在石墨烯场效应晶体管栅介结构中引入具有良好电容特性或极化特性的材料可改善晶体管性能.本文采用化学气相沉积制备的石墨烯并以PVDF-[EMIM]TF2N离子凝胶薄膜(ion-gel film)作为介质层制备底栅型石墨烯场效应管(graphene-based field effect transistor, GFET),研究其电学特性以及真空环境和温度对GFET性能的影响.结果表明离子凝胶薄膜栅介石墨烯场效应晶体管表现出良好的电学特性,室温空气环境中,与SiO_2栅介GFET相比, ion-gel膜栅介GFET开关比(J_(on)/J_(off))和跨导(g_m)分别提高至6.95和3.68×10~(–2) mS,而狄拉克电压(V_(Dirac))低至1.3 V;真空环境下ion-gel膜栅介GFET狄拉克电压最低可降至0.4 V;随着温度的升高, GFET的跨导最高可提升至6.11×10~(–2) mS.     

Quantum capacitance in monolayers of silicene and related buckled materials

Silicene and related buckled materials are distinct from both the conventional two dimensional electron gas and the famous graphene due to strong spin orbit coupling and the buckled structure. These materials have potential to overcome limitations encountered for graphene, in particular the zero band gap and weak spin orbit coupling. We present a theoretical realization of quantum capacitance which has advantages over the scattering problems of traditional transport measurements. We derive and discuss quantum capacitance as a function of the Fermi energy and temperature taking into account electron–hole puddles through a Gaussian broadening distribution. Our predicted results are very exciting and pave the way for future spintronic and valleytronic devices.     

Nitrogen-Doped Porous Graphene Coated with Fe3O4 Nanoparticles for Advanced Supercapacitor Electrode Material with Improved Electrochemical Performance

With the increasing demand for high-performance energy storage devices, single materials of ordinary structures for electrode materials have become increasingly difficult to meet people's needs. Therefore, composites of inimitable structures have drawn considerable attention. In this work, nitrogen-doped porous graphene coated with Fe₃O₄ nanoparticles (NPGF) is prepared by an efficient and green pyrolysis method. Structural and compositional characterizations confirm that the NPGF nanohybrids possess uniformly distributed pore structure and quite pure composition which is free of any impurities. In addition, electrochemical characterization verifies the excellent electrochemical performance, such as high-specific capacitance (713 F g⁻¹ at 1 A g⁻¹), prominent rate capability (capacitance retention of 77.3% and 67.9% when the current density is increased respectively from 1 to 10 and 20 A g⁻¹), and outstanding cycling stability (capacitance retention of 94.3% after 3000 cycles). Such promising results suggest that the NPGF nanohybrids have great application prospects in future high-performance supercapacitors.     

Flexible Graphene‐, Graphene‐Oxide‐, and Carbon‐Nanotube‐Based Supercapacitors and Batteries

Flexible energy‐storage devices increasingly attract attention owing to their advantages of providing lightweight, portable, wearable, or implantable capabilities. Many efforts are made to explore the structures and fabrication processes of flexible energy‐storage devices for commercialization. Here, the most recent advances in flexible energy‐storage devices based on graphene, graphene oxide (GO), and carbon nanotubes (CNTs), are described, including flexible supercapacitors and batteries. First, properties, synthesis methods, and possible applications of those carbon‐based materials are described. Then, the development of carbon‐nanotube‐based flexible supercapacitors, graphene/graphene‐oxide‐based flexible supercapacitors, and graphene‐ and carbon‐nanotube‐based flexible battery electrodes are discussed. Finally, the future trends and perspectives in the development of flexible energy‐storage devices are highlighted.     

非简谐振动对石墨烯量子电容和热稳定性的影响

采用固体物理理论和方法,研究了单层石墨烯的量子电容和它的温度稳定性随温度和电压的变化规律,探讨原子非简谐振动对它的影响.结果表明:(1)当电压一定时,单层石墨烯的量子电容和温度稳定性系数均随温度升高发生非线性变化,电压小于2.3 V时,量子电容随温度升高而增大,温度稳定性系数随温度升高由缓慢变化到很快增大,电压高于2.3 V时,量子电容随温度升高先增大后减小,而其温度稳定性系数随温度升高由缓慢变化到很快减小.温度一定时,量子电容只在电压值为0.4～2.8 V范围内才变化较小,而电压值大于2.8 V时,量子电容迅速减小并趋于0;(2)与简谐近似相比,非简谐项会使石墨烯量子电容有所增大,且温度愈高,两者的差愈大,非简谐效应愈显著,温度为300 K时,非简谐的量子电容要比简谐近似的值大0.33%,而温度为1 000 K时,差值增大到1.47%;(3)电压在1.5～1.8 V之间,而温度低于800 K时,石墨烯量子电容的温度稳定性系数最小且不随温度而变,储能性能的温度稳定性最好;(4)非简谐项会使它的量子电容热稳定性系数比简谐近似的值增大,且增大的情况与温度有关,当温度为400 K时量子电容热...