锂离子电池Si/C/石墨复合负极材料的电化学性能

采用热裂解方法, 热解分散于聚偏二氟乙烯溶液中的硅和石墨, 得到了具有稳定电化学循环性能的Si/C/石墨复合负极材料。透射电子显微镜观察发现, 复合材料形貌为无定型碳包裹硅颗粒的核壳结构。通过系统研究不同Si粒径和石墨含量对电极电化学性能的影响, 发现Si颗粒粒径越小复合材料电化学循环稳定性能越优越, 适当的降低石墨含量有利于电极材料剩余比容量的提高。当Si粒径为50 nm, Si与石墨质量比1:1时, 电极材料具有1741.6 mAh/g的首次放电比容量和72.5%的首次库仑效率, 60次循环后, 可逆比容量保持在820 mAh/g。热解有机物形成碳包覆的结构能有效地改善硅基类负极材料的电化学循环性能。     

高性能锂离子电池SiO/C/G复合负极材料研究

以一氧化硅、蔗糖及天然石墨为原料, 通过高能球磨和热解工艺制备了电化学性能优异的SiO/C/G复合负极材料。采用X射线衍射仪(XRD)和扫描电子显微镜(SEM)对复合材料的物相和形貌进行了表征。所制备的复合材料中, 纳米SiO颗粒(＜50 nm＝被无定形碳粘结并均匀分散在石墨鳞片上。电化学性能测试表明, 该复合材料100次循环后, 可逆容量高达1108.9 mAh/g, 容量保持率为103.8%。优异的电化学性能主要归因于纳米SiO颗粒在无定形碳基体中的均匀分布、无定形碳基体的缓冲作用和石墨相对复合材料导电性能的改善。     

膨胀石墨基炭/炭复合电极的制备及含酚废水的降解

以压缩膨胀石墨为基体、蔗糖为炭源、磷酸为活化剂,经碳化、活化压片制得膨胀石墨基炭/炭复合电极(EGC电极)。采用低温液氮吸附法和扫描电镜(SEM)进行表征,研究了蔗糖浓度对电极表面结构和孔道特征的影响规律,并以苯酚为处理目标物,考察了不同的电解条件。结果表明,EGC电极以膨胀石墨为骨架,包覆炭膜,孔径主要分布在0.5～2.5nm之间,蔗糖浓度为50%制备的EGC电极比表面积最高,电化学氧化苯酚效果最优。电解苯酚试验中,降低苯酚初始浓度、增加电流密度和电解质浓度有利于提高苯酚的降解效率。     

The synergy of a three filler combination in the conductivity of epoxy composites

Epoxy resin filled with carbon materials including graphite nanoplatelets, carbon blacks and carbon nanotubes was synthesized via a liquid mixing method. It was suggested that the conductivity of the composite filled with three fillers was much higher than that filled with only one or two carbon fillers. While the percolation threshold was 1 wt.% and 0.5 wt.% respectively for the composites filled with pure graphite nanopatelets and graphite nanoplatelet/carbon black (mass ratio of 9:1), it was only 0.2 wt.% for the nanocomposites filled with graphite nanoplatelets/carbon black/carbon nanotubes (mass ratio of 7:1:2). The synergistic conductive effect among the three carbon fillers was investigated in detail.     

PRODUCTION OF CARBON NANOTUBES IN AIR

Carbon nanotubes were produced by plasma discharging of graphite electrodes in air at 1 atm. The combined yield of CNTs and carbon nanoparticles is ∼20 wt % relative to the mass of cathode deposits or 14 wt% of graphite electrode consumed. The yields of CNTs and carbon nanoparticles under different inert gas atmospheres, such as He, Ar, N₂, and air were compared.     

Manufacture of a polymer-based carbon nanocomposite as bipolar plate of proton exchange membrane fuel cells

The aim of this paper is to prepare a polymer-based carbon nanocomposite reinforced by carbon fiber cloth (CF) to be utilized as bipolar plate of proton exchange membrane (PEM) fuel cell. For this purpose, some single, double, and triple-filler composites were manufactured by using phenolic resin as polymer (P) and graphite (G), carbon fiber (CF) and expanded graphite (EG) as fillers. The production method was compression-molding technique. The electrical conductivity, flexural strength, toughness, hardness, porosity, and hydrogen permeability tests were then measured to determine the mechanical and physical properties. A triple-filler composite containing 45 wt.% G, 10 wt.% CF, 5 wt.% EG, reinforced by a layer of CF cloth, was selected as composite bipolar plate. The electrical conductivity, thermal conductivity, and flexural strength of this composite were 74 S/cm, 9.6 W/m K, and 74 MPa, respectively, which are higher than the specified value by department of energy in USA (DOE). The composite bipolar plate used in the single fuel cell assembly showed a maximum power density 810 mW/cm². In this paper, a material selection was performed on the different materials of bipolar plates. It can be concluded that the composite bipolar plates are more suitable for high life time stationary applications.     

The effect of mold pressing pressure and composition on properties of nanocomposite bipolar plate for proton exchange membrane fuel cell

This paper is an attempt to introduce a suitable composite to be used in the bipolar plate of proton exchange membrane fuel cell (PEMFC). At first the effect of the mold pressing pressure and graphite content on the through-plane and in-plane electrical conductivities, flexural strength, hardness, density, porosity and water absorption of phenolic resin/graphite composite was investigated. The two mold pressing pressures, 15 and 740 bar were applied in 20, 30, 40, 50, 60, 70 and 80 wt.% graphite contents. The characterization was also conducted by an optical microscope, a stereoscope and the scanning electron microscopy. The results showed that the pressure considerably affects all properties and can dramatically change the porosity percentage of the composite. To improve conductivity and strength, the composite composition was modified by the nanosheet expanded graphite and carbon fiber. In an optimum composition, the in-plane and through-plane electrical conductivity and flexural strength reached 1518, 76 S/cm and 84 MPa, respectively. In this study, the contact resistance between the bipolar plate and carbon paper (as a gas diffusion layer) was also determined by changing the clamping pressure.     

Cf/ZrC-ZrB2-SiC-C超高温陶瓷复合材料的显微结构表征

利用X-射线衍射、扫描电子显微镜和透射电子显微镜对Cf/ZrC-ZrB2-SiC-C超高温陶瓷复合材料的相组成、纤维/热解碳层的界面特征和超高温陶瓷基体的显微结构特征进行了表征。在碳纤维表面有一层厚度为2～3μm石墨化程度较高的热解碳界面层,该界面层可以避免采用PIP工艺制备超高温陶瓷基体时可能对碳纤维造成的损伤。热解碳层与碳纤维之间为弱机械结合,其界面间分布着20～30 nm的ZrC纳米颗粒。Cf/ZrC-ZrB2-SiC-C超高温陶瓷复合材料基体主要由ZrC,ZrB2,SiC和石墨相(Cg)组成。基体中石墨的(002)面沿着ZrC,ZrB2或SiC的表面生长。在石墨与ZrB2和石墨与SiC的界面没有观察到取向关系,界面处既没有反应层也没有非晶相存在。在石墨与ZrC之间存在ZrC(111)∥Cg(002),ZrC[110]∥Cg[010]的取向关系。ZrB2和SiC之间也没有界面反应和非晶层存在。     

Synthesis of silicon monoxide-pyrolytic carbon-carbon nanofiber composites and their hybridization with natural graphite as a means of improving the anodic performance of lithium-ion batteries

Novel composites of silicon monoxide, pyrolytic carbon and carbon nanofiber (SiO/PyC/CNF) were hybridized with natural graphite (NG) as a means of improving the anodic performance of Li-ion batteries. Samples were made with hybridization levels of 10-30?wt% of NG exhibited excellent cyclability with a discharge capacity of 389-522?mAh?g(-1) in a Li-ion battery system. SiO/PyC/CNF composite hybrids showed better cyclability than other carbon composites containing SiO/PyC and SiO/CNF. These hybridization effects were attributed to the lower contact resistance of SiO/PyC/CNF in the electrode. The internal spaces created throughout the SiO/PyC/CNF composite and their effect on material dispersion in the hybridized electrodes may have prevented electrode damage by relieving tensions induced by the expansion of SiO particles in the electrode over the course of repeated charge and discharge processes.     

Effect of the addition of milled carbon fiber as a secondary filler on the electrical conductivity of graphite/epoxy composites for electrical conductive material

In this work, carbon composite bipolar plates consisting of synthetic graphite and milled carbon fibers as a conductive filler and epoxy as a polymer matrix developed using compression molding is described. The highest electrical conductivity obtained from the described material is 69.8 S/cm for the in-plane conductivity and 50.34 S/cm for the through-plane conductivity for the composite containing 2 wt.% carbon fiber (CF) with 80 wt.% filler loading. This value is 30% greater than the electrical conductivity of a typical graphite/epoxy composite with 80 wt.% filler loading, which is 53 S/cm for the in-plane conductivity and 40 S/cm for the through-plane conductivity. The flexural strength is increased to 36.28 MPa compared to a single filler system, which is approximately 25.22 MPa. This study also found that the General Effective Media (GEM) model was able to predict the in-plane and through-plane electrical conductivities for single filler and multiple filler composites.     

PRODUCTION OF CARBON NANOTUBES IN AIR

Carbon nanotubes were produced by plasma discharging of graphite electrodes in air at 1 atm. The combined yield of CNTs and carbon nanoparticles is ～20 wt % relative to the mass of cathode deposits or 14 wt% of graphite electrode consumed. The yields of CNTs and carbon nanoparticles under different inert gas atmospheres, such as He, Ar, N₂, and air were compared.     

基于界面相互作用构建纳米纤维素-羧基化碳纳米管-石墨/聚吡咯柔性电极复合材料

以纳米纤维素(CNF)、羧基化碳纳米管(CNTs—COOH)、铅笔石墨(PGr)、聚吡咯(PPy)为原料,通过真空抽滤、涂覆、氧化聚合等方法,同时基于氢键界面相互作用的原理,制备出具有石墨层结构的CNF-CNTs—COOH-PGr/PPy柔性电极复合材料。结果表明,CNF-CNTs—COOH-PGr/PPy柔性电极复合材料在平直、折叠和拉伸时不会断裂,展现出较强的力学性能,其拉伸强度达到28.90 MPa。亲水性CNF与CNTs—COOH构筑的多孔结构增强了离子和电子的扩散路径。PGr的加入有效增加了CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的导电路径,赋予其优良的导电性能。氧化聚合后得到的CNF-CNTs—COOH-PGr/PPy柔性电极复合材料的电导率达到5.403 S·cm?1。在1 mol·L?1 H₂SO₄溶液中,0.5 A·g?1电流密度下,CNF-CNTs—COOH-PGr/PPy柔性电极复合材料具有521 F·g?1的高比电容量,且经过1 500次充放电循环后,其电容保持率高达68%。基于柔性电极优良的力学性能、电化学性能和导电性能,CNF-CNTs—COOH-PGr/PPy柔性电极复合材料具备成为柔性储能器件电极材料的基本特性。      

Integration of a carbon nanotube based electrode in silicon microtechnology to fabricate electrochemical transducers

An original approach was developed and validated for the fabrication of a carbon nanotube (CNT) electrode synthesized directly onto a carbon buffer thin film deposited on a highly doped monocrystalline silicon surface. The buffer layer of amorphous carbon thin film was deposited by physical vapour deposition on the silicon substrate before CNT synthesis. For this purpose, nickel was deposited on the carbon buffer layer by an electrochemical procedure and used as a catalyst for the CNT growth. The CNT synthesis was achieved by plasma enhanced chemical vapour deposition (PECVD) in an electron cyclotron resonance (ECR) plasma chamber using a C(2)H(2)/NH(3) gas mixture. In order to evaluate the electrochemical behaviour of the CNT-based electrode, the carbon layer and the silicon/carbon interface were studied. The resulting buffer layer enhanced the electronic transport from the doped silicon to the CNTs. The electrode surface was studied by XPS and characterized by both SEM and TEM. The electrochemical response exhibited by the resulting electrodes modified with CNTs was also examined by cyclic voltammetry. The whole process was found to be compatible with silicon microtechnology and could be envisaged for the direct integration of microsensors on silicon chips.     

Construction and performance evaluation of mediator-less microbial fuel cell using carbon nanotubes as an anode material

A microbial fuel cell (MFC) is a device that converts chemical energy to electrical energy using the catalytic reaction of microorganisms. We investigated the performance of mediator-less MFC with carbon nanotubes (CNTs)/graphite felt composite electrodes. The addition of CNTs to a graphite felt electrode increases the specific surface area of the electrode and enhances the charge transfer capability so as to cause considerable improvement of the electrochemical activity for the anode reaction in a MFC. The performance of the MFC using CNTs/graphite felt electrode has been compared against a plain graphite felt electrode based MFC. A CNTs/graphite felt electrode showed as high as 15% increase in the power density (252 mW/m2) compared to graphite felt electrode (214 mW/m2). The CNTs/graphite felt anode therefore offers good prospects for application in MFCs.     

The physical properties of polyurethane/graphite nanosheets/carbon black foaming conducting nanocomposites

Using polyester polyol and diphenylmethane diisocyanate (MDI) as basic component, and using graphite nanosheets (GN) and carbon black (CB) as conductive filler, polyurethane/graphite nanosheets/carbon black foaming conducting nanocomposites have been prepared by filling mold curing reaction. The morphology, electrical properties and mechanical properties of the prepared PU/GN foams have been investigated. It showed that the percolation threshold effect of PU/GN composite occurred at the content around 12 wt.% of the GN, which was lower than that of carbon black (CB) composite. Besides, PU/GN foams showed much better conductive properties and mechanical properties than that of CB system.     

One‐Step Synthesis of Superbright Water‐Soluble Silicon Nanoparticles with Photoluminescence Quantum Yield Exceeding 80%

Fluorescent silicon nanoparticles (SiNPs) have shown potential applications in bioimaging/biolabelling, sensing, and nanomedicine/cancer therapy due to their superior properties such as excellent photostability, low cytotoxicity, and versatile surface modification capability. Here, a simple, high‐yield, and one‐pot method is developed to prepare superbright, water‐soluble, and amine‐functionalized SiNPs with photoluminescence quantum yield (PLQY) comparable to fluorescent II–VI semiconductor quantum dots (QDs) but with much lower cytotoxicity. By introducing a commercially available amine‐containing silane molecule, N‐[3‐(trimethoxysilyl)propyl]ethylenediamine (DAMO), water‐soluble SiNPs are prepared with PLQY of 82.4% via a microwave‐assisted method. To the best of our knowledge, this is the highest PLQY value ever reported for water‐soluble fluorescent SiNPs. The silicon element in our SiNPs is mainly four‐valent silicon and thus these SiNPs may also be termed as oxidized silicon nanospheres or silica nanodots. We have also demonstrated the importance of the silane structure (e.g., a suitable amine content) on the photoluminescence property of the prepared SiNPs. As revealed by the time‐resolved photoluminescence technique, the highest PLQY value of DAMO SiNPs is correlated with their monoexponential decay with a relatively long fluorescence lifetime. In addition, the potential use of these SiNPs has also been demonstrated for fluorescent patterning/printing and ion sensing (including Cu²⁺ and Hg²⁺).     

纳米纤维素/碳纳米管/纳米银线柔性电极的制备

目的以竹粉为原料制备纳米纤维素,并将其作为基底材料制备纳米纤维素/碳纳米管/纳米银线复合电极,应用于柔性超级电容器。方法采用化学机械处理法,将竹粉通过化学处理以及研磨、超声等处理,制备成纳米纤维素悬浮液;分别将多壁碳纳米管和纳米银线超声分散于溶剂中;最后,通过层层自组装制备纳米纤维素/碳纳米管/纳米银线复合电极,同时,作为对照组,制备纳米纤维素/碳纳米管复合电极。结果纳米纤维素纤丝的直径大约为30~100 nm,相互之间缠绕成网状结构,是很好的支撑材料,纳米纤维素/碳纳米管/纳米银线复合电极具有很好的成膜性和电化学性能,在扫描速率为30 m V/s时,面积比电容达到77.95 m F/cm~2。结论以纳米纤维素为基底,通过层层自组装方法制备的纳米纤维素/碳纳米管/纳米银线复合电极具有较好的电化学性能,可作为柔性超级电容器的电极。     

Hardfacing characteristics of S42000 stainless steel powder with added silicon nitride using a CO2 laser

This study examined hardfaced cladding of S42000 stainless steel powder with added silicon nitride Si₃N₄ on a medium carbon steel using a 1200-W CO₂ laser. Experimental results indicated that a well-proportioned cladding layer was obtained with an overlap of 50% at a traverse speed of 5 mm/s and a powder feed rate of 2 g/min. The degree of dilution, depth/width (D/W) ratio and microhardness of the cladding layer was increased by adding up to 5 wt.% silicon nitride. Retained austenite and wear decreased with increasing amounts of silicon nitride addition. The silicon nitride decomposed in the cladding layer during the laser treatment.     

Preparation, Properties and Application of C/C-SiC Composites Fabricated by Warm Compacted-in situ Reaction

Carbon fibre reinforced carbon and SiC dual matrices composites (C/C-SiC) show superior tribological properties, high thermal shock resistance and good abrasive resistance, and they are promising candidates for advanced brake and clutch systems. The microstructure, mechanical properties, friction and wear properties, and application of the C/C-SiC composites fabricated by warm compacted-in situ reaction were introduced. The results indicated that the composites were composed of 50-60 wt pct carbon, 2-10 wt pct residual silicon and 30-40 wt pct silicon carbide. The C/C-SiC brake composites exhibited good mechanical properties. The value of flexural strength and compressive strength could reach 160 and 112 MPa, respectively. The impact strength was about 2.5 kJ·m^-2. The C/C-SiC brake composites showed excellent tribological performance, including high coefficient of friction (0.38), good abrasive resistance (1.10 μm/cycle) and brake steadily on dry condition. The tribological properties on wet condition could be mostly maintained. The silicon carbide matrix in C/C-SiC brake composites improved the wear resistance, and the graphite played the lubrication function, and right volume content of graphite was helpful to forming friction film to reduce the wear rate. These results showed that C/C-SiC composites fabricated by warm compacted-in situ reaction had excellent properties for use as brake materials.     

全钒液流电池用碳纳米管-石墨复合电极的研究

将石墨(GP)和多壁碳纳米管(MWNT)按不同比例压片制成电极,用于全钒氧化还原液流电池电极材料,通过循环伏安、交流阻抗、充放电测试、SEM手段对MWNT-GP复合电极进行表征和分析.研究结果表明,MWNT含量为15wt%的MWNT-GP复合电极性能最佳,对组装成的静态电池在电流密度20~80mA/cm2进行充放电性能比较,电流效率均在93%以上,电压效率随着电流密度的增加而有所下降.