Fabrication of high-performance supercapacitors based on transversely oriented carbon nanotubes

High-performance supercapacitors with organic electrolyte 1 M TEABF₄ (tetraethyl ammonium tetrafluoroborate) in PC (propylene carbonate) were fabricated and tested, based on multiwall carbon nanotubes (MWNTs) deposited by electrophoresis on three types of alternative substrates: aluminium foil, ITO (indium tin oxide) coated PET (polyethylene terephthalate) film and PET film. In all cases, SEM (scanning electron microscopy) and STEM (scanning transmission electron microscopy) micrographs demonstrated that protruding, transversely oriented MWNT structures were formed, which should increase the transverse conductivity of these MWNT electrodes. The best supercapacitor cell of MWNT electrodes deposited on aluminium foil displayed good transverse orientation of the MWNT structures as well as an in-plane MWNT network at the feet of the protruding structures, which ensured good in-plane conductivity. Capacitor cells with MWNT electrodes deposited either on ITO-coated PET film or on PET film demonstrated lower but still very good performance due to the high density of transversely oriented MWNT structures (good transverse conductivity) but some in-plane inhomogeneities. Capacitor cells with drop-printed MWNTs on aluminium foil, without any transverse orientation, had 16–30 times lower specific capacitance and 5–40 times lower power density than the capacitor cells with the electrophoretically deposited MWNT electrodes.     

Fast electron energy loss spectrum of an amorphous tungsten trioxide film

The forward scattering energy loss spectrum of 300 KeV electrons transmitted through thin films of WO₃ has been measured in the energy range of 0.8–225 eV with an energy loss resolution of 0.1 eV. Energy losses due to excitation of color centers, inter band transitions and core elestrons in WO₃ have been identified. Measurement of the elastic electron difraction pattern revealed the amorphous nature of the film with structural differences depending upon the preparative methods.     

中能高浓度氦离子注入对钨微观结构的影响

采用15 keV, 剂量1×10¹⁷/cm², 温度为600 ℃氦离子注入钨, 分别以块体钨研究氦离子对钨的表面损伤; 以超薄的钨透射电镜样品直接注入氦离子, 研究该条件下钨的微观结构变化, 以了解氦离子与钨的相互作用过程; 采用扫描电子显微镜、聚焦离子束扫描显微镜、透射电子显微镜、高分辨透射电子显微镜等分析手段研究氦离子注入对钨表面显微结构的影响及氦泡在钨微观结构演化中的作用.     

Defect and electrical properties of nanocrystalline tungsten trioxide

Nanocrystalline tungsten trioxide particles were prepared by a wet-chemical method. Transmission electron microscope (TEM) analysis shows that the average grain size is about 15nm. The oxygen deficiency of nanometre-sized sample is higher than that of ordinary tungsten trioxide. The electric conductivity increases because of high oxygen deficiency. Ironic relaxation polarization and crystallographic shear (CS) planes theory were used to explain the unusual dielectric characteristic of nanocrystalline tungsten trioxide.     

Rod-like polyaniline supported on three-dimensional boron and nitrogen-co-doped graphene frameworks for high-performance supercapacitors

In this work, novel three-dimensional (3D) boron and nitrogen-co-doped three-dimensional (3D) graphene frameworks (BN-GFs) supporting rod-like polyaniline (PANI) are facilely prepared and used as electrodes for high-performance supercapacitors. The results demonstrated that BN-GFs with tuned electronic structure can not only provide a large surface area for rod-like PANI to anchor but also effectively facilitate the ion transfer and charge storage in the electrode. The PANI/BN-GF composite with wrinkled boron and nitrogen-co-doped graphene sheets interconnected by rod-like PANI exhibits excellent capacitive properties with a maximum specific capacitance of 596 F/g at a current density of 0.5 A/g. Notably, they also show excellent cycling stability with more than 81% capacitance retention after 5000 charge-discharge cycles.     

三氧化钨表面氢吸附机理的第一性原理研究

采用基于密度泛函理论的第一性原理平面波超软赝势方法,在广义梯度近似下,研究了立方WO_3,WO_3(001)表面结构及其氢吸附机理.计算结果表明立方晶体WO_3理论带隙宽度为0.587 eV.WO_3(001)表面有WO终止(001)表面和O终止(001)表面两种结构,表面结构优化后W—O键长和W—O—W键角改变,从而实现表面弛豫;WO终止(001)表面和O终止(001)表面分别呈现n型半导体特征和p型半导体特征.分别计算了H原子吸附在WO终止(001)表面和O终止(001)表面的H—O_(2c)—H,H—O_(2c)…H—O_(2c),H—O_(1c)—H和H—O_(1c)…H—O_(1c)四种吸附构型,其中H—O_(1c)—H吸附构型的吸附能最小,H—O键最短,H失去电子数最多,分别为-3.684 eV,0.0968 nm和0.55e,此吸附构型最稳定.分析其吸附前后的态密度,带隙从吸附前的0.624 eV增加到1.004 eV,价带宽度基本不变.H的1s轨道电子与O的2p,2s轨道电子相互作用,在-8和-20 eV附近各形成了一个较强的孤立电子峰,两个H原子分别与一个O_(1c)原子形成化学键,最终吸附反应生成了一个H_2O分子,同时产生了一个表面氧空位.     

High density behaviour of nuclear symmetry energy

There exists profound discrepancy in the high density behaviour of the nuclear symmetry energy obtained in realistic variational many-body (VMB) calculations and in relativistic mean-field (RMF) calculations. While the symmetry energy decreases to negative values in the former approach it increases monotonically in the latter one. The origin of this discrepancy is discussed and it is argued that VMB prediction is more reliable. It is shown that vanishing of the symmetry energy implies proton-neutron separation instability in dense matter.This work was partially supported by KBN grants 2 0204 91 01 and 2 0054 91 01.     

Ab initio study of oxygen point defects on tungsten trioxide surface

The gas response of tungsten trioxide (WO3) based sensors strongly depends on the surface properties. Reconstructed surfaces and oxygen point defects at the surface of the monoclinic WO3 are studied using a self-consistent scheme based on first-principle. The oxygen vacancy is found to be the predominant defect independently of the oxygen partial pressure. Indeed, under rich oxygen atmosphere the formation enthalpies are found to be 1.45 eV in LDA (1.28 eV in GGA) for the oxygen vacancy instead of 2.70 eV (2.42 eV) for the oxygen adatom. When the oxygen partial pressure is lowered, the oxygen vacancy formation enthalpy decreases and becomes exothermic under very O-poor condition (? 1.65 eV in LDA and ? 1.36 eV in GGA). On the other hand, the formation enthalpy of an oxygen adatom rises. Finally, the oxygen vacancy formation acts as a n-doping by introducing negative charge carriers at the bottom of the conduction band. All these results can be very helpful in order to explain the electrical resistivity measurements.     

基于非线性超传导的能流不对称传输现象的研究

研究了非线性传输线电路禁带内能量的不对称传输现象. 传输线电路中的两子电路结构相同,电感参数不同,并且具有低通滤波器的特点. 鉴于驱动频率在通频带的截止频率之上,所以形成不对称能流的载体为 禁带内传播的非线性波.该研究中,产生不对称能量传输的机理与非线性超传导现象密切相关. 通过调整耦合电感的大小,总结出传输能量与耦合强度之间的变化规律. 同时也采用仿真的方式分析了驱动电压幅值与传输能量间的相关性. 最后,通过在实验上改变驱动频率的大小,得到超传导发生时的门限电压与驱动频率间的依赖关系, 该关系与理论计算的结果完全定性一致.     

Synthesis of pyrochlore tungsten trioxide thin film and electrochemical lithium intercalation

The pyrochlore tungstate thin film has been prepared by an autoclave hydrothermal method at a temperature of 200 °C. The film was characterized by X-ray diffractometry, X-ray photoelectron spectroscopy and scanning electron micrograph measurements, showing that pure pyrochlore phase of sodium tungstate containing a small amount of water was formed by heating the film at a temperature of 350 °C. The cyclic voltammetric and galvanostic measurements revealed that a reversible electrochemical lithium intercalation into the crystal lattice of pyrochlore tungstate film takes place with charge-discharge cycling. Furthermore, the thermodynamics and kinetics of electrochemical lithium intercalation into the pyrochlore sodium tungstate film were also studied.     

高能密度物理实验装置FP-1及其应用

 综述了由高能密度物理装置FP-1驱动的固体套筒内爆研究情况。主要内容包括FP-1脉冲功率装置的特性和所进行的主要物理实验：铝套筒内爆、双套筒碰撞和微喷射、套筒的内爆脉冲屈曲等，给出了各类实验的典型结果。     

高能量密度氘、氦的第一原理研究进展

极端条件下氘、氦的研究对于凝聚态物理、等离子体物理、天体物理以及惯性约束聚变的研究具有重要意义.文章综述了近年来温稠密区、热稠密区以及低温高压区的最新研究进展,归纳了尚待解决的科学问题,从而为进一步的研究提供参考.     

高能量密度氘、氦的第一原理研究进展

极端条件下氘、氦的研究对于凝聚态物理、等离子体物理、天体物理以及惯性约束聚变的研究具有重要意义.文章综述了近年来温稠密区、热稠密区以及低温高压区的最新研究进展,归纳了尚待解决的科学问题,从而为进一步的研究提供参考.     

高能密度物理实验装置FP-1及其应用

综述了由高能密度物理装置FP-1驱动的固体套筒内爆研究情况。主要内容包括FP-1脉冲功率装置的特性和所进行的主要物理实验：铝套筒内爆、双套筒碰撞和微喷射、套筒的内爆脉冲屈曲等,给出了各类实验的典型结果。     

Longitudinal unzipping of carbon nanotubes and their electrochemical performance in supercapacitors

The capacitive properties of graphene nanoribbons (GNRs) with different reduction levels were investigated. GNRs have been synthesized through thermal reduction of oxidized GNRs in the temperature range 100–400 °C. Oxidized GNRs were synthesized by longitudinal unzipping of multi-walled carbon nanotubes (MWCNTs) by means of chemical treatments. Scanning electron microscopy and transmission electron microscopy observations showed, that the efficient tube unzipping yielded improved effective surface area without any tube annihilation by the unzipping process of MWCNTs. Electrochemical studies indicated that through unzipping of MWCNTs, specific capacitance increased from 8 to 28 F g⁻¹ at discharge current density of 0.5 A g⁻¹, confirming increased active surface area and increased defect density in the MWCNTs surface. Unzipping of MWCNTs resulted in decreased rate capability of the electrode because of low electrical conductivity due to oxidization during the unzipping process. Thermal reduction of unzipped sample affected both specific capacitance and rate capability of electrodes. The highest specific capacitance of 62 F g⁻¹ at discharge current density of 0.5 A g⁻¹ was obtained for the sample unzipped and thermally annealed at about 150 °C. The amount of oxygen-containing groups was shown to be an important factor influencing the performance of the GNRs. These results make unzipped MWCNTs promising electrode materials for supercapacitor applications.     

应用于脉冲功率系统的高储能密度电容器

介绍了现有技术条件下脉冲电容器的各种性能参数及其测试方法,包括储能密度、寿命、保压性能、绝缘电阻等;同时介绍了元件的主要分析测试手段,如大电测试、保压测试等,并研究了后处理工艺、介质系统优化和绝缘系统优化对电容器性能的影响。在此基础上,面向不同应用条件如大电流放电、长寿命、真空环境等,对高储能密度脉冲电容器进行研究,并给出相应的性能参数、限制条件和发展前景。研究结果表明:50 kV/20 F的电容器,可实现120 kA/80 s的大电流输出,并通过-50~60 ℃的高低温考核;基于绝缘系统优化的浸渍型脉冲电容器,充放电寿命为干式结构的2~3倍,储能密度为2.0 kJ/L时,寿命大于1 000次,储能密度为1.3 kJ/L时,寿命大于10 000次;1.4 kJ/L高储能密度电容器,可以工作在气压小于10-3 Pa的真空条件下,输出电流达100 kA。     

应用于脉冲功率系统的高储能密度电容器

介绍了现有技术条件下脉冲电容器的各种性能参数及其测试方法,包括储能密度、寿命、保压性能、绝缘电阻等;同时介绍了元件的主要分析测试手段,如大电测试、保压测试等,并研究了后处理工艺、介质系统优化和绝缘系统优化对电容器性能的影响。在此基础上,面向不同应用条件如大电流放电、长寿命、真空环境等,对高储能密度脉冲电容器进行研究,并给出相应的性能参数、限制条件和发展前景。研究结果表明：50 kV/20 F的电容器,可实现120 kA/80 s的大电流输出,并通过-50~60 ℃的高低温考核;基于绝缘系统优化的浸渍型脉冲电容器,充放电寿命为干式结构的2~3倍,储能密度为2.0 kJ/L时,寿命大于1 000次,储能密度为1.3 kJ/L时,寿命大于10 000次;1.4 kJ/L高储能密度电容器,可以工作在气压小于10-3 Pa的真空条件下,输出电流达100 kA。     

Binding energy of transition atoms adsorbed on tungsten

We develop a statistical method to estimate the density of states from the knowledge of its first moments. We apply this method to the calculation of the density of states of an s band in a simple cubic lattice. Then we use it to determine the binding energy of a transition atom adsorbed on tungsten in a LCAO approximation. The binding energies obtained agree with the experimental values, but they do not exhibit the experimental peak which may be due to correlation effects.     

Preparation, characterization and photocatalytic activity of multi-walled carbon nanotube-supported tungsten trioxide composites

Multi-walled carbon nanotube (MWCNT)-supported tungsten trioxide (WO₃) composite catalysts were prepared by liquid-phase process. WO₃ nanoparticles grew on the inner and outer surface of MWCNTs. Their photocatalytic activities in the degradation of the Rhodamine B Dye were studied. The effects of mass ratio of MWCNTs to WO₃ were discussed. X-ray diffraction, field emission transmission electron microscopy, thermogravimetric-differential thermal analysis and ultraviolet-visible light absorption spectra were carried out to characterize the composite catalysts. The results indicated that the optimum mass ratio of MWCNTs to WO₃ is 5:100.     

High field microscopy of nickel on tungsten

Field emission and field ion microscopy have been used to study the properties of nickel layers adsorbed on tungsten, and the growth of nickel crystallites. The first monolayer of nickel has a maximum density of 0.97 ± 0.05 × 10¹⁹ atoms m^?2 and results in an increase in the work function which can be attributed to the formation of dipoles of moment μ₀ = 1.70 ± 0.08 × 10^?30Cm at zero coverage and polarizability $\text{α = 7.3 ± 0.05}\text{A}\text{?}{}^3$. Nickel desorbs from the tungsten surface with activation energy 4.22 ± 0.01 eV and second layer atoms desorb with activation energy 3.2 ± 0.02 eV. Surface diffusion of second and higher layers over clean tungsten layer is believed to proceed by the “unrolling carpet” mechanism, with activation energy 0.93 ± 0.03 eV in close agreement with measurements of surface self-diffusion of nickel. Nickel does not dissolve appreciably in single-crystal tungsten and we confirm that atomic disordering at the nickel-tungsten interface is confined within a few angstroms of the interface. Well-ordered crystallites can be grown from a central nuclear structure which develops on (110)W. Combination of field ion and field emission techniques indicate that the crystallites adopt the expected growth form, having surfaces comprising large low-index faces, and also serve to confirm that field emission images alone cannot be relied upon to give an indication of crystallite shape. Crystallites invariably form upon an adsorbed layer which is at least one atom thick but may be thicker depending upon conditions of growth. The growth of crystals in situ offers the possibility of generating well-ordered low-index planes of large area which are suitable for further study, but it has yet to be confirmed that they behave as surface planes of bulk nickel.