M. Advanced Carbon Materials

Organizers：Li Hejun, Cheng Huiming, Jyh-Ming Ting, Kang Feiyu

M-01 Grapheneas a sub-nanospacer in the film–NPs coupling system for strong optical interactions Bingqing Wei Northwestern Polytechnical University/University of Delaware The nanoparticle-film gap (NGF) system has been extensively studied due to its strong local enhancement field. However, there are still some technical limitations in establishing effective and simple ways for reliable and precise control of sub-nanospacer. Here two routes are proposed to solve these issues.First, a novel NGF system is discussed by introducing an ultrathin monolayer graphene as well-defined sub-nanospacer between Ag NPs and Ag film (named G(graphene)-NGF system). The new G–NGF system offers tremendous near-field enhancement with one of the highest enhancement ratios of 1700 reported to date, which is mainly due to multiple couplings including the NP–NP couplings and NP-film couplings.Second, a simple, low-cost, all-copper sandwich system has been obtained by directly depositing Cu NPs onto a graphene sheet, which has been already grown on a Cu foil (Cu-NGF). The new design inherits two key advantages: (1) the NGF coupling system is composed of only cheaper Cu instead of Au and Ag, (2) direct fabrication of the system without transferring graphene will greatly lower the fabrication cost. More importantly, the Cu-NGF system shows a high sensitivity in SERS with the highest enhancement factor (EF is over 1.89×107) reported to date in Cu plasmonic systems. Experimental and theoretical results reveal that the strong EF is mainly because of the strong coupling between Cu NPs and Cu films at the optimal angle of incidence, opening up a new route for Cu materials in SERS applications. M-02 Wearable Electronics Based on Carbon Nanomaterials Yingying Zhang Tsinghua University The development of flexible electronics and equipment attracts significant interests in recent years [1]. Low-dimensional carbon materials are one kind of ideal materials for flexible electronics. It is of great importance to explore low cost and scalable preparation approaches for high performance flexible carbon materials-based wearable electronics. In this,We demonstrated that carbonized silk fabric with a plain-weave structure, based on its unique N-doped graphitic carbon nanostructure and the macroscale woven structure, could be worked as strain sensors with both of high sensitivity (gauge factor of 9.6 in the strain range of 0%-250% and 37.5 in the range of 250%-500%) and high tolerable strain (more than 500%) [2]. Besides, the as-obtained sensors have fast response (<30 ms) and high durability (>10,000 cycles). It was demonstrated that such strain sensors could be used for monitoring both of vigorous human motions (such as jumping, marching, jogging, bending and rotation of joints), subtle human motions (such as pulse, facial expression, respiration and phonation) and even sound, and further demonstrated the capture and reconstruction of human body movements with our sensors, showing their superior performance and tremendous potential applications in wearable electronics and intelligent robots.

The concept could be readily extended to other fabrics, such as cotton, modal, wool fabrics and other artificial or natural fiber fabrics, paving a new way for the low cost and large scale fabrication of wearable strain sensors with superior performance. Our strategy provides new approaches for the low-cost and high performance production of flexible electronics, promising its high potential for practical applications. Besides, we will also present our recent work on the application of carbon nanotubes, graphene and their composites in flexible electronics. M-03 Fullerene Materials: Endohedral and Exohedral Functionalization Shangfeng Yang University of Science and Technology of China The most unique structure of fullerene is its hollow interior, which can encapsulate some species such as atom and molecules. Endohedral functionalization of fullerene generates endohedral fullerenes.[1,2] On the other hand, fullerene can be used as a "module" of organic reactions, and numerous fullerene derivatives have been synthesized via exohedral functionalization of fullerenes. Based on the strong electron-accepting ability, fullerene derivatives have been widely applied as acceptors in organic solar cells. In this talk, we present our recent successful isolation of the long-sought small-bandgap Sc3N@C82,[3] the first V-containing endohedral fullerenes,[4]

and the first monometallic cyanide clusterfullerene— YCN@Cs(6)-C82.[5] Besides, we synthesized an open-cage endohedral fullerene derivative involving a 13-membered ring[6] and an azide addition derivative via exohedral functionalization of endohedral fullerenes.[6] More recently, a nonclassical fullerene derivative C96Cl20 was synthesized via chlorination of C100 fullerene.[8,9] M-04 Ablation of carbon/carbon composites under the nitrogen plasma flame Xuetao Shen School of Materials Science and Engineering, Shaanxi University of Science and Technology Ablation of carbon/carbon composites under a nitrogen plasma flame was studied. The products of the thermal chemical reactions between the combustion gases and carbon were calculated using the principle of free energy minimisation. The results show that Cn(n=1-5), CN(g), C2N, C2N2 are the main ablation products, and that the ablation of carbon/carbon composites is controlled by the sublimation of carbon, thermal chemical reactions and mechanical breakage. The cone-shaped fibers and shell-shaped matrix are attributed to carbon sublimation and thermal chemical reactions, whereas the fractured fibers and fragments result from mechanical breakage. M-05 Raman spectroscopy of pyrocarbon: negative thermal expasion and structunral information Ningkun Liu Northwestern Polytechnical University Pyrocarbon with different textures were analyzed using Raman spectroscopy. The influence of the high temperature to the structure of pyrocarbon was studied. The physical structural information revealed from the full width at half maximum (FWHM) could provide a new method for the discrimination of pyrocarbon with different textures. In addition, the negative thermal expansion of C/C composite was researched using Raman spectroscopy. The competition among different phonon modes, derived from Grüneisen theory, could be used to explain the

mechanism for such negative thermal expansion. The inharmonic vibration of the atoms was considered to contribute to such contraction as the temperature increases. This phenomenon showed that pyrocarbon could behave like crystal while remain its amorphous structure. M-06 Effects of stress and thermal fatigue on the microstructure of carbon/carbon composites Hejun Li, Shouyang Zhang Northwestern Polytechnical University Flexural fatigue and laser radiation tests were conducted to investigate effects of stress and thermal fatigue on the microstructure of carbon fiber reinforced pyrolytic carbon matrix (C/C) composites. For stress fatigue tests, the residual strength anddynamic mechanical behavior of the specimens before and after flexural fatigue tests had been researched. For thermal fatigue tests, the influence of laserintensity, cycle number and fatigue temperature were studied to detect the changes of texture evolution of C/C composites. Results showed that fracture mechanisms, internal friction and dynamic modulus of the specimens with different damage accumulation degrees were changed because of the interfacial damages and cracks produced in stress fatigue tests. On the other hand, cracks, pores on the surface, extinction angle and crystallite size of pyrolytic carbon were affected by the laser experimental parameters. That is, the microstructure changes was the dominant factor leading to the differences of properties of C/C composites between as-prepared specimens and fatigued specimens. M-07 Tailored Carbon Materials for Overcoming Critical Issues in Rechargeable Batteries Arumugam Manthiram University of Texas at Austin Lithium-ion batteries have revolutionized the portable electronics industry, but their widespread application for electric vehicles and grid storage of electricity produced from renewable sources like solar and wind requires optimization of cost, cycle life, safety, energy density, power density, and environmental impact, all of which are directly linked to severe materials challenges. With respect to cost, energy density, and environmental impact, elemental sulfur or oxygen cathodes coupled with lithium-metal or sodium-metal anode have become appealing for rechargeable lithium or sodium batteries. However, both sulfur and oxygen cathodes are hampered by numerous scientific and technological challenges. Carbon plays a major role in overcoming some of the major issues. Accordingly, this presentation will focus on the use of tailored carbon materials for the fabrication of sulfur and air electrodes as well as novel cell configurations. The role of parameters, such as morphology, surface area, type of pores, pore size, and pore volume when coating a variety of carbons (e.g., spherical carbons, carbon nanofibers, carbon nanotubes, and graphene), onto polymer separators in lithium-sulfur batteries will be discussed. In addition, the role of microstructure, pore structure, and surface functional groups of carbons on the oxygen reduction reaction activity in rechargeable hybrid lithium or sodium batteries and aqueous metal-air batteries will be discussed. M-08 Binder-free 3D nanocarbon composites from biomass with tunable meso/micropore ratio for capacitance Yani Zhang, Heng Wu, Tianyan Mao Norwestern Polytechnical University

Recent efforts on designing, controlling and assemblying the architectures of CNT and graphene based electrodes towards taking advantage of their intrisic performace had been widely investigated, while, researchers today give a concern on cost efficiency when used for energy applications with mass production. Natural fibers, such as hemp fibers (including flax, sisal and jute) and cotton fibers, are sustainable and abundant in nature. Their good mechanical resilience, high chemical resistance, low cost, lightweigh t, and disposability make them excellent electrode materials for flexible supercapacitors. They can also be easily weaved into fabric and then readily integrate with wearable electronics. Herein， we present the new application of old materials such as activited natural fibers ultilized as an electrode. A novel one-step synthetic strategy has been developed to simultaneously carbonize and activate low-cost flax fabrics into free-standing and flexible fabrics with hierarchical meso/microporous structures. By simplychanging the heating rateduringrapid heating,the total pore volume, pore sizes, oxygen content, and the mesopore volume/total pore volume (Vmeso/Vtotal) ratio,which are crucial for the electrochemical performance, could be controled and tuned. Notably, the Vmeso/Vtotal ratio is significantly increased from 27.6 % (with heating rate of 5 °C/min) to 67.0 % (with heating rate of 300 °C/min). As a result, the flexible electrodes show excellent electrochemical performance in acqueous electrolyte, including a largespecific capacitance of 205 F/g at current density of 0.1 A/g, a good rate capability (156 F/g at 15 A/g) andan excellent cycling stability (~96.6 % retention after 3000 cycles). These findings demonstrate the huge potential of natural fibers in the applications of high-performance electrochemical capacitors and wearable smart electronics. M-09 A facile route to synthesis three-dimensional graphene with controlled pore size Yong Wang1,2, Yun Yu1, Aihu Feng1,2, Feng Jiang1,2, Yang Yu1, Le Mi1, Lixin Song1 1. Key Laboratory of Inorganic Coating Materials CAS, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, PR China 2. University of Chinese Academy of Sciences, Beijing 100049, PR China

A novel three-dimensional graphene (3D-G) with pore size less than 1 μm was synthesized by sol-gel method. In this method, Nafion was skillfully introduced as modifiers which play important connecting role between graphene oxides (GO). Ethylenediamine was used to produce a chemically linked graphene hydrogel during reducing process, which can then be freeze-dried to remove the absorbed water to form 3D-G. Nafion in GO solution prohibits the re-stacking of individual graphene sheets during reduction and freeze-drying process. By the method mentioned above, the pore size of as-prepared 3D-G could be effectively controlled in 1 μm, which is much less than that of the traditional graphene aerogel material (20-500 μm). The 3D-G with unique structure exhibited excellent properties, such as a high specific surface area, high porosity, low density, high electric conductivity and good mechanical properties. The as-prepared 3D-G has bright application prospect in the field of energy. M-10 Oxidation protection of carbon/carbon composites with an in-situ mullite whisker-toughened silicate glass/SiC coating by molten salt method Jianfeng Huang, Lei Zhou, Liyun Cao, Haibo Ouyang, Cuiyan Li, Jie Fei School of Material Science and Engineering, Shaanxi University of Science and Technology Whisker reinforcement can enhance the thermal shock resistance of coating. Here, a mullite whisker-toughened silicate glass coating for SiC pre-coated carbon/carbon composites (SiC-C/C) was prepared by a novel molten salt

with a later hot dipping method. The phase composition, microstructure, adhesion strength and thermal shock resistance of the coating were investigated. Results show that two-step technique is an effective route to achieve smooth, well-bonded and crack-free mullite whisker-toughened silicate glass coating.Preparing the transition mullite whisker layer and incorporating the mullite whisker can effectively improve the coating interface bonding and baffle the propagation of the microcracks by various toughening mechanisms, including bridging, crack deflection and pull out of mullite whisker. The as-prepared coating has an enhanced thermal shock resistance and the weight loss of the coated samples is only 2.21% after 100 thermal cycles. M-11 Transition Metal Carbides Go 2D Yury Gogotsi Drexel University Two-dimensional (2D) solids-the thinnest materials available to us – offer unique properties and a potential path to device miniaturization. The most famous example is graphene, which is an atomically thin layer of carbon atoms bonded together in-plane with sp2 bonds. In 2011, an entirely new family of 2D solids – transition metal carbides (Ti2C, Ti3C2, Nb4C3, etc.) and carbonitrides – was discovered by Drexel University scientists [1]. Selective etching of the A-group element from a MAX phase results in formation of 2D Mn+1Xn solids, labeled “MXene”. More than different MXenes have been reported to date [2-5]. A new sub-family of multi-element ordered MXenes was discovered recently [2]. Structure and properties of numerous MXenes have been predicted by the density functional theory, showing that MXenes can be metallic or semiconducting, depending on their surface termination. Their elastic constants along the basal plane are expected to be higher than that of the binary carbides. Oxygen or OH terminated MXenes are hydrophilic, but electrically conductive. Hydrazine, urea and other polar organic molecules can intercalate MXenes leading to an increase of their c lattice parameter [3]. When dimethyl sulfoxide or TBAOH was intercalated into Ti3C2, followed by sonication in water, a stable colloidal solution of single- and few-layer flakes was produced. One of the many potential applications for 2D Ti3C2 is in electrical energy storage devices such as batteries, Li-ion capacitors and supercapacitors [3-5]. Cations ranging from Na+ to Mg2+ and Al3+ intercalate MXenes. Ti3C2 paper electrodes, produced by vacuum assisted filtration of an aqueous dispersion of delaminated Ti3C2, show a higher capacity than graphite anodes and also can be charged/discharged at significantly higher rates. They also demonstrate very high intercalation capacitance (up to 1000 F/cm3) in aqueous electrolytes [4]. M-12 Calcium phosphate coating for carbon/carbon composites Leilei Zhang Northwestern Polytechnical University To improve the surface biocompatibility of carbon/carbon composites, calcium phosphate coatings were applied on carbon/carbon composites. The morphology, microstructure and chemical composition of the coating were investigated by scanning electron microscopy, energy dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, raman spectroscopy and X-ray diffraction. The biocompatibility of the coating was investigated by osteoblast-like MG63 cell culture test. M-13

Preparation and thermoelectric properties of graphenenanosheets and polyprrole co-coated cotton fabric Yong Du Shanghai Institute of Technology Graphenenanosheets and polyprrole co-coated cotton fabricwere prepared by using asoaking treatment combining vapour phase polymerization process. The composition, and microstructure of the graphenenanosheets and polyprrole co-coated cotton fabric were characterized by X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FESEM), respectively. The electrical conductivity and Seebeck coefficient of the samples were measured from room temperature to 380 K, and the thermal conductivity were measured at room temperature. Compared to the polyprrole coated cotton fabric, the thermoelectric properties of the co-coated cotton fabric were enhanced. The as-prepared graphene nanosheets and polyprrole co-coated cotton fabrics have great potential to be used in wearable electronics. M-14 Spin-dependent Transport Behaviors in Different Organic Spacers (PVDF, C60, C70, Rubrene) devices Xianmin Zhang, Gaowu Qin I. Introduction The manipulation and utilization of the spin polarization of electrons in organic semiconductors (OSs) has attracted considerable research interest for fundamental material science and potential applications.OSsare expected to possess a large spin-dependent transport (SDT) length due to their weak spin-orbit coupling [1,2]. Nevertheless, a large SDT length inOSshas only been generally observed at low temperatures because the magnetoresistance (MR) effect disappears at room temperature. Understanding spin-dependent transport behaviours in OSs is very important to develop spin-based organic materials and related devices operated at room temperature.In this report, a series of novel organic spin valve devices with a Fe3O4/Al-O/OSs/Co/Al stacking structure were reported. Here, four kinds ofOSs, Poly(vinylidene fluoride) (PVDF), rubrene, C60 and Alq3 were tested in the devices. The spin-dependent transport properties were systemically studied. The PVDF film was fabricated using the Langmuir–Blodgett (LB) technique. Briefly, PVDF and poly(N-dodecylacrylamide) (pDDA) were dissolved in NMP and chloroform with the same solution concentration, respectively. The two resultant solutions of pDDA and PVDF were spread successively at pDDA:PVDF (n:n)=1:50 onto the water surface in a Langmuir trough to obtain PVDF film [6]. The average thickness of each PVDF film layer is 2.3 nm. The other three organic films are deposited using thermal evaporation method. The oxide layers and metallic layers were deposited by magnetron sputtering technique. The devices were prepared by three masks and the area of device was 1.5 ×1.5 mm2. A detailed experimental process can be found in the literature [7]. The LB nanofilms were investigated using atomic force microscopy (AFM) measurements (SPA-400, Seiko Instruments Inc.). The magnetoresistance (MR) curves were measured via the standard four-probe method using a physical property measurement system (Quantum Design). II. Experimental results and discussion Poly(vinylidenefluoride) (PVDF) was also believed as a good spacer candidate to fabricate multifunctional OSVs owing to its ferroelectric property [8]. Moreover, PVDF can form high quality ordered layers, which is beneficial for efficiency electron transport. Velev and Gangineni with their respective colleagues have studied the PVDF based devices with Co/PVDF/O/Co [9] and Fe/PVDF/Fe [10] stacking structures by the first-principle calculations. However, to our knowledge, PVDF based OSVs have not been fabricated in experiment previously. We fabricate OSV devices with an Fe3O4/AlO/PVDF/Co/Al stacking structure.

The magnetoresistance (MR) ratio at room temperature were obtained in these four series of devices. It is noted that the MR ratios at room temperature are over 2% and 0.5% for devices with 3 layers and 13 layers of PVDF, respectively. The device resistances and MR ratios increase with decreasing measurement temperature. Interface spin scattering and crystal defects likely lead to the decrease of electron transport efficiency in the devices with more layer numbers of PVDF. Giant MR ratio over 8% was observed at 300 K in C60-based spin valves, which is one of the highest MR ratios reported to date. Most importantly, a large SDT length of over 100 nm was experimentally observed in the C60

layer at room temperature [11]. Moreover, an interesting dependence of MR ratio on C60 layer thickness has been observed. It was found that the MR ratios sharply increase with the increase of C60 layer thickness from 10 nm to 40 nm, and then slowly increase for the C60 layer increasing till 80 nm. Beyond this range, further increase C60 layer thickness leads to a drastic reduction of MR ratio. It was explained that the competing effects of activation energy and electric field magnitude on the spin diffusion length and carrier mobility in the C60 layer result in a maximum of MR ratio. In addition, the effect of thermal evaporation temperature of C60 layer on MR ratio was also investigated. TunnellingMR ratio was achieved over 6% in rubrene and Alq3 based spin valves at room temperature[7,12]. The MR effect was also systemically investigated by varying the thickness of the OSslayer and measurement temperature to gain insight into the SDT behavior. The MR ratio monotonously decreased with increasing rubrene and Alq3 layer thicknesses, which is differ to the observation in C60 based spin valves. The multiple-step tunneling processes likely resulted in a decrease in the MR ratios with increasing Alq3 layer thickness. By contrast, hopping transport was mainly considered in the thicker C60-based devices. C70 devices were also prepared to perform a compartive study. In summary, organic spin valve devices with a Fe3O4/Al-O/OSs/Co/Al stacking structure were studied. Tunneling MR ratio was achieved at room temperature in rubrene, PVDF and Alq3 based spin valves. Moreover, the tunneling MR ratios decrease with increasing the Oss layer thickness. A giant MR ratio over 8% was observed at 300 K in C60-based spin valves. It is also found that there is a maximum for MR ratios with increasing the C60

layer thickness in the devices. M-15 Flexible Capacitive Energy Storage Devices Based on Graphene Electrodes Under Extreme Conditions Ho Seok Park Sungkyunkwan University With increasing demand for high performance energy storage systems, the feasibility of reliable and functional energy storage devices that well operates under extreme conditions is of prime importance for special applications of electrical vehicle, flexible and wearable electronics, and integrated on-chip systems. The highly bendable and compressible energy storage devices are expected to be adopted in these applicative fields as long as they preserve good performance even under electrochemical and mechanical stresses. Moreover, advanced electrode materials are essential for developing the afore-mentioned functional energy storage devices. In this talk, I will introduce bendable and compressible supercapacitors based on graphene electrodes that can efficiently deliver electrical energy under electrochemical, mechanical and thermal stresses. In order to achieve high performance supercapacitor devices under various stresses, the micro- and macroscopic structures and chemical compositions of graphenes are delicately controlled by chemical modification. The solution chemistry described herein would pave the way to obtain high performances of energy storage materials/devices that are otherwise difficult to realize with current, conventional technologies, leading to breakthroughs for important emerging applications.

M-16 Microstructure and formation mechanism of pyrolytic carbon depositing Shouyang Zhang Northwestern Polytechnical University A single carbon fiber bundle was infiltrated with natural gas under atmospheric pressure and pyrolytic carbon textures of cross-section and surface were studied by polarized light microscopy (PLM) and scanning electronic microscopy (SEM). The infiltration processing parameters, including residence time, surface area / volume (AS/VR) ratio pores and surface flow velocity, resulted in a transformation of gas composition and leading to the transitional textures finally. A systematic analysis about the evolution of various carbon texture was put forwarded on the basis of their surface morphology, that the surface of low textured carbon are covered by coarse big granules, medium texture are smooth spheric grains, and the high textured carbon exhibit approximate smooth plane. Additionally, the formation of pyrolytic carbon was explained as a nucleation-growth mechanism, that vapor-growth carbon nanofiber are formed primarily as the nucleus, pyrolytic carbon were deposited around the nanofiber and converted to stable state periodically. M-17 Room-temperature ferromagnetism in CVD-adamantane films Suppanut Sangphet1, Dulyawat Doonyapisut1, Sumeth Siriroj1, Supree Pinitsoontorn2, Worawat Meevasana1 1. School of Physics, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, Thailand 2. Department of Physics, Faculty of Science, Khon Kaen Uversity, Khon Kaen, Thailand

Objective: Recently there have been reports of room-temperature ferromagnetism induced in carbon compounds, including “Teflon” sheets and “Q-carbon”. In this work, we would like to create room-temperature ferromagnetism from adamantane; this adamantane is the smallest member of the so called “diamondoid” series (nano-diamond structures) which have displayed interesting properties such as negative electron affinity and very low work functions. We would also attempt to study the mechanism of this ferromagnetism. Methods: By using chemical vapor deposition (CVD) technique, we prepared adamantane films on various substrates, e.g. silicon, quartz and sapphire. The magnetic property of these films was studied by vibrating sample magnetometer (VSM). We used x-ray photoemission spectroscopy (XPS) and energy dispersive spectroscopy (EDS) to check element composition on the films. The structures of film surface which may relate to the origin of this ferromagnetism were investigated by Raman and nuclear magnetic resonance (NMR) spectroscopy. Results: We have prepared the CVD-adamantane films with various substrate temperatures. The thin film of decomposed-adamantane molecules, which change their color from white to black, has formed well on the substrates with growth temperature above 1050 C. By using VSM, we found moderately strong ferromagnetism in our CVD-admantane films with saturated magnetization up to 120 emu/cm3 Conclusions: We found ferromagnetisms in CVD-adamantane films at room temperature. By using XPS and EDS, we have confirmed that this ferromagnetism does not arise from magnetic elements. We believe that the origin of this ferromagnetism comes from the non-sp3bondings of carbon atoms (e.g. dangling bond) which were created during the CVD process. While the origin of this magnetic property needs further investigation, the strength of ferromagnetism found here already suggests some applications, e.g. hard drive coating and biocompatible magnetic materials. M-18

A facile method of massively producing three-dimensional silicon nitride nanowire cloth Kebing Guo, Jinhua Lu, Qiang Song, Qian Guo Northwestern Polytechnical University Objective: Silicon nitride (Si3N4) is a kind of superior structural and functional ceramic material, which has widely application as high-strength structural material and wide band gap (5.3eV) semiconductor. However, the brittleness of ceramic restricts its widely application on soft portable devices. In recent years, the emergence of one-dimensional nanostructures provides a possibility to obtain flexible nano-ceramic. Silicon nitride nanowires (Si3N4NWs) inherits the predominant physical and chemical properties of Si3N4 ceramic, meanwhile the special structure of nanowires possesses itself unique properties, such as high aspect ratio, large surface area to volume ratio, good flexibility, interesting optical and electronic properties and superior mechanical performance. However, the synthesized methods that have been reported are complicated and the massive production cannot be achieved.Methods: The uniform solution of polyureasilazane (PSN), acetone, and ferrocene naturally solidified in air firstly. Then, it was ground into homogeneous powder in a quartz mortar. The obtained powder was sifted on a U-like carbon paper with a sieve (140 mash) and was heated in a horizontal tube furnace under the protection of ultra-high purity nitrogen.Results: Two kinds of three-dimensional Si3N4NW cloths were produced via this method. Both of the upper cloth and the lower cloth are composed of ultralong intertwined Si3N4NWs which have the length of more than 2mm. After they were peeled from carbon papers, the lower cloth displayed some strength and roughness due to the composite structure of nanowires and residual ceramics, while the upper cloth showed very light and flexible property. The ultralong length and intertwined structure of nanowires endow the products cloth-like feature. The synthesized Si3N4NWs display perfect signal crystal structure with few structure defects.Conclusion: This method to synthesize Si3N4NWs is facile and easy. If advancing the production equipment, the size and yield of Si3N4NW cloth would be expended largely, which is important in display devices or energy equipment such as flexible batteries and supercapacitors with high power and energy density. M-19 Nano-Carbon Solar Cells Shigeo Maruyama The University of Tokyo A film of single-walled carbon nanotubes (SWNTs) can be a dual-functional layer as electron-blocking-layer and transparent electrode in various solar cells. We have demonstrated efficient SWNT/Si solar cells using dry-deposited high-quality SWNTs and honeycomb-structured SWNTs. Adequately doped mm scale single crystal graphene also exhibited the similar performance. The dual functionality is also demonstrated for organic and perovskite solar cells. For organic solar cells, the SWNT/MoOx/PEDOT:PSS layer was demonstrated as a dual functional layer replacing ITO and organic electron-blocking-layer. By replacing ITO, the flexible device can be easily demonstrated. Similar replacement of ITO was demonstrate for Perovskite type solar cells. On the other hand, It is also possible to replace electron blocking layer and metal electrode for both organic and Perovskite solar cells. This direction is promising for low cost device fabrication and semi-transparent solar cells. M-20 The synthesis and application of fluorinated carbon materials Min-Jung Jung, Young-Seak Lee* Chungnam National University

The fluorination is one of the most effective methods to control the textural and surface properties of carbon materials. I will present the synthesis and application of fluorinated carbon materials such as activated carbons, activated carbon fibers, and carbon nanotubes. So, I will discuss with physical, chemical and electrochemical properties of fluorinated carbon materials to magnify the applications. M-21 The manufacture and prospective application of 3D C/C-SiC in high speed and heavy duty brake systems Peng Xiao, Zhuan Li, Yang Li, Yu-hai Lu, Su-hua Zhu Powder Metallurgy Research Institute, Central south university In order to widely serve for the high speed and heavy duty brake systems, the three-dimensional needle-punched C/C-SiC (C/C-SiC) composites with proper cost, excellent mechanical properties, etc. were developed by combination of chemical vapor infiltration and liquid silicon infiltration. The microstructures, physical properties and bench tests for different high-speed and heavy brake systems had been systematically investigated. The results indicated that the flexural, compressive strength and impact-toughness can reach 182 and 234MPa, 15-24 kJ/m2, respectively. The bench test of C/C-SiC brake disc with diameter of 670 mm and pads for high-speed train, showed that the coefficient of friction (μ) was stable, about 0.32. After four different emergency stops (from maximum 420 km/h-300 km/h to 0 km/h with clamping force 6-24KN), the wear rate of the C/C-SiC pads was 0.21cm3/MJ. The bench test of C/C-SiC for heavy brake systems with inertia and braking pressure were 112.7 kg·m2 and 12 MPa, respectively, showed that the coefficient of static friction was higher than 0.65. At the speed of 1100rpm, 1500rpm and 1850rpm, the deceleration was 4.8m·s-2, 3.7m·s-2 and 3.5m·s-2 respectively. The line wear rate is 1.5 microns per cycle that was less than 1/4 of that of traditional powder materials. Additionally, the bench test for engineering machineries brake system and vehicles showed similarly superior tribological properties. In conclusion, the 3D needle-punched C/C-SiC composites have been demonstrated to be the top choice for the high-speed and heavy-duty brake systems. M-22 Green One Pot Synthesis of Conductive and Magnetic Ni/carbon Aerogel with Enhanced Electromagnetic Absorption Performances Haibo Zhao, Zhibing Fu, Chaoyang Wang Research Center of Laser Fusion, China Academy of Engineering Physics Electromagnetic microwave absorption materials have attracted a great deal of attention because of the growth in utilization of wireless equipment. Aerogel characterized by low density and tunable porosity, is considered as an ideal microwave absorbent, if its inherent electromagnetic property can be improved. However, there have been few reports on the electromagnetic microwaves absorption of electromagnetic functionalized aerogels. In this study, an innovative, easy and green method was presented to synthesize an electromagnetic functionalized Ni/carbon aerogel, in which the formation of Ni nanoparticles and carbon occurred simultaneously from an alginate/Ni2+ hydrogel precursor. The resultant aerogel had a high surface area and porosity and showed a high conductivity and significant magnetism. It exhibited greatly enhanced microwave absorption ability. A minimum RL value of -45 dB was found, with only 10 wt% of functional fillers being used in the test template with a thickness of 2 mm. The detailed absorption mechanism of the aerogel was further investigated.

M-23 Shaddock Peel Derived Hard Carbon as High Performance Anodes for Sodium Ion Batteries Jianfeng Huang, Ruizi Li, Liyun Cao, Zhanwei Xu, Jiayin Li, Haibo Ouyang, Jie Fei School of Material Science and Engineering, Shaanxi University of Science and Technology A shaddock peel derived hard carbon with the dilated intergraphene spacing andhomogeneous dispersion spherical structure is successfully achieved through a hydrothermal followed carbonization process. When used as sodium ion battery anode material, the shaddock peel derived hard carbon exhibits good rate capability and cycling stability, delivering a high initial charge capacity of 263.7 mAh g-1 at 50 mA g-1, retaining a reversible capacity of 81 mA g-1 at 5 A g-1, and showing a capacity retention of 89–92% after 500 cycles. The reason that shaddock peel derived hard carbon works so well is that it uniquely combines uitable graphitization degree, dilated intergraphene spacing (0.381 nm), and homogeneous dispersion spherical structure, which are capable of reversibly accumulating sodium ions through surface adsorption and sodium intercalation. M-24 In-situ reduced graphene oxide-polyvinyl alcohol composite coatings as protective layers on magnesium substrates Xingkai Zhang, Zhou Yan, Zhang Bin, Zhang Junyn Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Graphene is considered an ideal candidate for protective layers owing to its chemical inertia, impermeability and environmental friendliness. It has been demonstrated that graphene films or reduced graphene oxide (rGO) coatings could inhibit the corrosion of copper, nickel, iron, and aluminium. However, graphene films or rGO coatings can hardly be adopted as protective layers on magnesium substrates. It is practically impossible to generate or transfer graphene films grown by chemical vapour deposition on magnesium substrates. Although GO coatings can be prepared on magnesium substrates via spin-coating or dip-coating method, it is hardly to obtain compact GO coatings owing to the poor film-forming ability of GO. Various polymers have been added into the GO suspension and GO-polymer composite coatings were prepared to enhance the compactness of GO coatings, but the GO based composite coatings still cannot provide excellent protective property as the H2O and small ions are easy to permeate through the coatings. Therefore, it is necessary to reduce GO in the coatings to increase the barrier property of GO-polymer composite coatings. So far, there are numerous methods to reduce GO based on chemical or thermal means. GO can be reduced by hydroiodic acid (HI) or ascorbic acid (Vc) solutions, but the HI or Vc solutions will cause severe corrosion of magnesium substrates. Thermal reduction is an effective way to reduce GO, but it requires high temperature and the heating process can make the GO coatings become extremely fragile. In this contribution, in-situ reduced graphene oxide-polyvinyl alcohol composite coatings (rGO-PVA coatings) were developed as protective layers to increase the corrosion resistance of magnesium substrates. GO was dispersed in ultrapure water to form the suspension at a concentration of 5 mg/ml. PVA was added in the GO suspension at a concentration of 1 mg/ml, and the pH value of composite suspension was adjusted to above 10.0 by adding ammonia. Magnesium substrates were immersed in the GO-PVA composite suspension, and then lifted slowly. Afterwards, the samples were blown by hot-blast air to accelerate the evaporation of solvent. The dip-coating procedure was repeated for 10 times to form uniform GO-PVA coatings. Finally, the GO-PVA coatings on magnesium substrates were thermal treated at 120 °C for 2 h to get in-situ reduced GO-PVA coatings

using drying oven. The in-situ reduction method was carried out neither in the solutions containing reductants nor in the reducing or inert atmosphere at high temperature. The morphology, structure and composition of the GO-PVA and in-situ reduced GO-PVA coatings were characterized with Scanning electron microscope, X-ray diffractometer, Raman spectrometer, Fourier transform infrared spectrometer and X-ray photoelectron spectrometer. The corrosion behaviour was evaluated by electrochemical measurements performed in 3.5 wt.% NaCl solution using electrochemical analyser. After the coating process, the magnesium substrates were fully covered by uniform and brown GO-PVA coatings. The coatings changed to black after thermal treated at 120 °C, indicating the reduction of GO. As shown in the SEM photographs, the bright wrinkles, which were the typical phenomenon of GO and rGO coatings, could be seen, and both the coatings were devoid of any cracks or pores. It indicated that the in-situ reduction could not change the morphology and integrity of the GO-PVA coatings. The characteristic X-ray diffraction peak of GO appeared at ~10° was observed in GO-PVA coatings, while, for rGO-PVA coatings, the peak located at ~10° disappeared. The Raman spectrum of rGO-PVA coatings exhibited a notable increase of the intensity ratio of D and G band from 0.64 of GO-PVA coatings to 0.93. The FTIR spectra of GO-PVA and rGO-PVA coatings were compared, and the characteristic absorption peaks of GO-PVA coatings appeared at ~1107 cm-1 (vibration of C-O groups), ~1400 cm-1(bending of O-H groups), ~1622 cm-1 (vibration of C=C groups), ~1731 cm-1 (vibration of C=O groups) and in the region of 3000 to 3600 cm-1 (stretching of O-H groups). After the thermal treatment at 120 °C, the absorption peak located in the region of 3000 to 3600 cm-1 weakened dramatically, and the peaks at ~1107 cm-1, ~1400 cm-1 and ~1731 cm-1 also weakened obviously, demonstrating these oxygen-containing groups were removed significantly. The XRD, Raman and FTIR results confirmed that PVA could effectively reduce GO. The reason for the effective reduction role of PVA might be attributed to the abundant -OH functional groups of PVA. From the XPS results of the GO-PVA and in-situ reduced GO-PVA coatings, it can be obtained that the C/O atomic ratio of rGO-PVA coatings was increased to 5.76 from 2.79 for GO-PVA coatings, suggesting that some oxygen-containing groups were removed. This result could also be conrmed by the C1s spectra of GO-PVA and rGO-PVA coatings. The peaks centered at the binding energy of 284.8 eV, 286.9 eV and 288.8 eV were attributed to C-C/C=C, C-O and C=O groups, respectively. Because of the reducing action of PVA, thermal treatment led to 81% and 61% decrease in the peak area ratio of C-O and C=O groups, respectively. The potentiodynamic polarization tests of the magnesium substrates, and magnesium with GO-PVA and in-situ reduced GO-PVA coatings were carried out in 3.5 wt.% NaCl solutions. Compared with magnesium substrates, the corrosion potential (Ecorr) values of magnesium with GO-PVA and rGO-PVA coatings were about 130 mV and 260 mV more positive, respectively, indicating the magnesium with rGO-PVA coating was harder to corrode. Meanwhile, the corresponding corrosion current density (icorr) values from Tafel fitting were 62.51 μA·cm-2, 12.34 μA·cm-2 and 2.538 μA·cm-2 for magnesium substrates, magnesium with GO-PVA and rGO-PVA coatings, respectively. The rGO-PVA coatings could lower the icorr of magnesium substrates to its 1/25, while GO-PVA coatings could only decrease the icorr to its 1/5. It was confirmed that in-situ reduced GO-PVA coatings had higher corrosion resistance and provided better protective performance. In summary, in-situ reduced GO-PVA coatings prepared by thermal treating GO-PVA coatings at a low temperature (120 °C) have been successfully employed to enhance the corrosion resistance of magnesium. PVA added in GO composite coatings could lead to the in-situreduction of GO in solid state. The reducing effect of PVA was confirmed by XRD, Raman, FTIR and XPS measurements. Since being difference from other reducing process carried out either in solution containing reductants or in the reducing or inert atmosphere at high temperature, the in-situ reduction was a simple and feasible method to prepare reduced graphene oxide composite coatings for a wide range of applications.

M-25 A novel 3D architecture designed for high performance Li-O2 Batteries Rui Mi1,2, zhibing Fu1, Chaoyang Wang1, Hao Liu2, Jun Mei2, Xi Yang1, Haibo Zhao1, Miao Liu1, Minglong Zhong1 1. Research Center of Laser Fusion, Chian Academy of Engineering Physics, Mian Yang, 621900, China 2. Chengdu Green Energy and Green Manufacturing Technology R&D Centre, Southwest Airport Economic Development Zone, Chengdu, 610207, China

Li-O2 batteries are attracting intensive attention due to their large theoretical energy density, comparable with that of gasoline.1 As an excellent carbon material, mainly responsible for the performance of Li-O2 batteries, Nitrogen-doped carbon nanotubes (N-CNTs) have been already used in Li-O2 batteries.2 In this work, N-CNTs and nanosized Co3O4 were successfully composited to catalyze the anion formation in the air electrode of Li-O2

batteries. The N-CNT serves to support the catalyst and provides a surface for the redox reaction to occur. The morphology of the N-CNTs and Co3O4@N-CNTs nanocomposite were characterized by SEM. Fig. 1a and 1b illustrates representative SEM images of the morphology of N-CNTs and Co3O4@N-CNTs nanocomposite. The superior electrochemical performance, as shown in Fig. 1c, could be related to the more nucleation sites and thus a higher dispersion of discharge products which are more easily decomposed in charge process. In general, our results demonstrate that Co3O4@N-CNTs could be further explored as high capacity anode material for Li-O2 application. M-26 Layer-by-layer graphene-like carbon/TiO2 derived from 2D-Ti3C2: towards high photocatalytic activity for hydrogen generation Wenyu Yuan Northwestern Polytechnical University TiO2, as a kind of semiconductor with a band gap of 3.0-3.2 eV, has been widely researched in photocatalytic H2 generation because of its non-toxicity, low cost and high stability. However, TiO2 suffer from low charge transport and low separation ability of electrons-holes, limited the activity in photocatalytic fields. Among various methods, Carbon/TiO2 was be considered as a promising method to improve the photoactivity of TiO2 because the large amount of carbon on the earth, the low-cost and high electrical conductivity. Two-dimensional transition metal carbides, are promising precursors for the synthesis of transition oxides@carbon hybrid materials. Herein, we synthesized layer-by-layer graphene-like carbon/TiO2 (LBL-C@TiO2) via CO2 oxidation of 2D-Ti3C2 at 700 oC. The results indicated that 2D-Ti3C2 have been totally transformed into TiO2 and 3-6 layers of graphene-like carbon after CO2 oxidation. The as prepared LBL-C@TiO2 catalyst delivered fast electron transport, high separation ability of electrons-holes, and high photocatalytic activity for H2 generation. Besides, the structure and architecture also affect the photocatalytic activity of LBL-C@TiO2. The LBL-C@TiO2 materials also possess huge potential in the applications of electrocatalyst, supercapacitor, batteries, sensors and other related fields. M-27 The synergy effect of carbon nanotubes and matrix microstructure for improved flexural properties of carbon/carbon composites Qingliang Shen, Hejun Li, Wei Li, Junjie Ren, Qiang Song, Qiangang Fu Northwestern Polytechnical University

Aims: Carbon/carbon (C/C) composites are excellent ultrahigh temperature thermal-structural materials but with weak fiber-matrix interfaces. Introducing CNTs improves the fiber-matrix bonding strength but cause the degradation of fiber strength and brittle fracture of the composites. Method: For improving the flexural performances of C/C composites, CNTs were electrophoretically deposited on carbon fibers and the compatibility of CNTs with different textured pyrocarbon matrix has been investigated. Results: Mechanical testing results show that after introducing CNTs, the flexural strength increases by 13.9 % to 197 MPa for low-texture-matrix (LT) CNT-C/C composites and increases by 89.6% to 309 MPa in high-texture-matrix (HT) CNT-C/C composites. Transition layer (TL) where CNTs are embedded can be formed neighboring the fibers after a chemical vapor infiltration process. On one hand, improvements in flexural strength are still limited by the overly enhanced interfaces and brittle fracture feature remains for CNT reinforced low texture matrix C/C. On the other hand, fiber/TL/pyrocarbon interfaces in high-texture-matrix composites are enhanced to a moderate degree, where the transition layer in HT-CNT-C/C composites not only ensures the stress transfer efficiency but also shields the cracks from propagating towards the fibers by interface debonding, which significantly improves the utilization of fiber strength and avoids brittle fracture. Additionally, the introducing of CNTs induces protuberance structure of the layered matrix, which improves the cohesion of high texture matrix and reliefs the matrix stress concentration as confirmed by Raman stress analysis. Conclusion: It is clearly demonstrated in this work that the synergy of CNTs with high-texture matrix is a more promising strategy for improving the flexural behaviors of C/C composites. Poster M-P01 Influence of incident angles on ablation behavior and mechanism of ZrB2-SiC modified C/C composites Ying Lu, Kezhi Li, Yue Liu, Maoyan Zhang, Lizhen Xue Northwestern Polytechnical University To investigate the effec of different ablation angles on ablation property of C/C-ZrB2-SiC(ZS) composites prepared via precursor infiltration and pyrolysis (PIP), the samples were tested by oxyacetylene flame at incident angles of 0o and 90o (ZS-0 and ZS-90). Results showed that the latter one had better ablation resistance due to further protection offered byoxidation products on the surface. For ZS-90, the damage was mainly dominated by thermo-chemical ablation. Nevertheless, turbulent flame that formed in the hole made significant contribution to decreace the ablation behavior of ZS-0, its ablation mechanism was mainly mechanical erosion, and thermo-chemical ablation only took the secondary role. It implied that ablation resistance were highly related to the incident angles of the flame, and different mechanisms had been involved for C/C-ZrB2-SiC composites. M-P02 Antistatic property and rub resistance study of polyester fabrics coated with reduced graphene oxide Manqiu Li Shanghai University Graphene slurry was firstly prepared, then pad-roll dyeing method was used to prepare conductive graphene coated polyester fabrics. The coated fabrics were characterized by Martindale test, SEM, FTIR, XPS and square resistance. The smoothness of the fabric is helpful to achieve a high electro-conductivity because it creates

continuity in the coated layer. Different resistance was acquired by varying processing times. After those treatments, the square resistance is up to 896Ω*cm, reaching class-A standard of antistatic property. Moreover, good electro-conductivity is retaining after 10000 times rub by Lissajous routes. It also applied to cotton fabrics. The coated fabric can be used in antistatic overalls and outdoor clothing. M-P03 RGO wrapped urchin-like NiCo2O4 microspheres for a high-performance non-enzymatic glucose sensor Xuemin Yin, Hejun Li, Ruimei Yuan, Leilei Zhang, Qiangang Fu State Key Laboratory of Solidification Processing, Carbon/Carbon Composites Research Center, Northwestern Polytechnical University The detection of glucose is of importance in the field of food, clinical, and biochemical. So it is necessary to find a kind of biosensor to ensure the level of glucose fast, reliably and effectively. In this work,3D hierarchical hollow urchin-shape NiCo2O4 microspheres were fabricated using a simple hydrothermal process and thermal annealing, and the NiCo2O4/rGO nanocomposites were synthesized by the in-situ chemical reduction of GO on the surface of NiCo2O4 microspheres. The structure and morphology of the products were characterized by XRD, XPS, Raman, SEM and TEM. The results shows that the microspheres were assembled by nanowires which is composed of many nanoparticles. rGO was uniformly wrapped on the surface of NiCo2O4 microspheres to improve the electric conductivity. The electrocatalytic behaviors of NiCo2O4/rGO composites towards glucose are investigated by cyclic voltammetry and chronoamperometry, which shows higher electrocatalytic ability than NiCo2O4 and rGO, related to the hierarchical hollow urchin-shape structure and the outstanding conductivity of the rGO. At a potential of +0.5 V, the NiCo2O4/rGO nanocomposite modified glass carbon electrode demonstrates a wide linear range of 1 μM to 0.6 mM and 0.6 to 3.7 mM, with the sensitivities of 0.055 μAμM-1cm-2 and 0.021 μAμM-1cm-2, respectively.Moreover, the electrode also shows a low detection limit of 0.545 μM. It also shows significant electrochemical stability, good reproducibility and excellent selectivity. The results suggest that the NiCo2O4/rGO nanocomposite is a promising electrode material for electrochemical biosensor. M-P04 Structure and Wear behavior of Chopped carbon fiber fabric reinforced carbon-copper composites under Electric Current Jian Yin1, Hongbo Zhang1, Xiang Xiong1, Huijin Tao2, Chaoyong Deng1, Pei Wang1 1. State Key Laboratory of Powder Metallurgy, Central South University, Changsha 2. College of Materials Science and Technology,Central South University,Changsha

Using net-like chopped carbon fiber web integrated needled fabric as the reinforcement, a new type of carbon fiber reinforced carbon and copper matrix (C/C-Cu) composites were prepared by a combination of chemical vapor infiltration and high pressure impregnation technique with Cu alloy. Their wear tests were carried out on a pin-on-disc wear tester (HST-100) under electric current. The microstructures and morphologies of the worn surface were investigated by optical microscopy (OM) and scanning electron microscopy (SEM), respectively. The results show that C/C-Cu composites with chopped carbon fiber fabric have relatively low density, electrical resistivity and wear rates. The corresponding wear mechanisms were identified to be adhesive wear and arc erosion.

M-P05 Morphology Effects on the Supercapacitive Performance of KOH Activated Bacterial Cellulose-based Carbons Chenfeng Ding, Jinle Lan, Yunhua Yu, Xiaoping Yang State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, China Objective: The KOH activated bacterial cellulose-based carbon (a-BC) has been intensively studied, as a cost-effective biomass-based activated carbon for supercapacitor because of its feasible high specific area, flexibility and desirable supercapacitive performance. However, there is no clear evidence that shows the morphology effects on the supercapacitive performance of KOH activated bacterial cellulose-based carbon. Methods: The various dimensional activated bacterial cellulose-based carbons(0D, 1D and 2D) were facilely fabricated through changing the pretreatment of bacterial cellulose before KOH activation and heat treatments. Result: Morphology effects on the supercapacitive performances of the as-prepared a-BCs were studied. For the varied dimensional a-BCs, the micro-morphologies, microscopes, and specific area are quite different, which leads to the differences in their electrochemical properties, such as cycle performance and rate capability. Conclusion: By the aforementioned work, we initially present an interesting relationship between dimensions and electrochemical performance on a-BC, which is greatly beneficial for the fabrication of other activated materials in the field of high-performance electrochemical energy storage in the future. M-P06 Capacitive Deionization of NaCI Solutions with Carbon Aerogel Electrodes Xueping Quan1,2, Zhibing Fu1, Yiong Yi2,2, Chaoyang Wang1 1. Research Center of Laser Fusion, China Academy of Enineering Physics, Mianyang 621900, Sichuan, People,s Republic of China 2. School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621000, Sichuan, People,s Republic of China

The capacitive deionization process has been investigated to develop the technology into a system for desalination. Capacitive deionization (CDI) with carbon aerogel electrodes represents a novel process in desalination of brackish water and has merit due to its low fouling/scaling potential, ambient operational conditions, electrostatic regeneration, and low voltage requirements. The CDI unit system containing a pair of carbon aerogel electrodes showed the maximum ion removal efficiency when the 50 mg/L NaCl solution was recycled at the volume flow rate of 10 mL/min under the applied voltage in the range of 0.8–1.4 V. Under the optimum operating conditions of the CDI unit system ,the test cell made using carbon aerogel electrodes showed fast adsorption and desorption cycle of 30 min and salt removal efficiency of 65% was obtained at 1.2 V. It was evaluated that the CDI process using carbon aerogel electrodes promised to be an effective technology for desalination. M-P07 Synthesis and characterization of Si-substituted hydroxyapatite bioactive coating for SiC coated carbon/carbon composites Qian Guo, Kezhi Li, Leilei Zhang Northwestern Polytechnical University

Objective: To improve the bioactivity of hydroxyapatite (HA), silicon-substituted hydroxyapatite (Si-HA) coating has been prepared on SiC coated carbon/carbon composites. Methods: SiC coating on carbon/carbon composites was prepared by pack cementation technique and Si-HA coating was prepared by electrochemical deposition technology. The surface morphology and element composition of the coatings was tested with a scanning electron microscope (SEM) equipped with energy dispersive spectroscope (EDS). The crystal structure of the coatings was examined using an X-ray diffraction. The structural characteristics of the coatings were analyzed by a Raman spectroscope. The compositions of the coatings were characterized by an Axis Ultra X-ray photoelectron spectroscope (XPS). The functional groups of the coatings were tested using a Fourier transform infrared spectroscope (FTIR).Simulated body fluid (SBF) immersion test was used to investigate the in-vitro bioactivity. Results: SiC inner-layer exhibits a hexagonal prism shape. With the increase of Si substitution, the HA flakes became small, and as the η Si increased to 15%, a porous three-dimensionalnetwork products with the smallest crystal size were synthesized. Si-HA out-layer has a smaller crystal size than HA and covers the SiC inner-layer entirely and uniformly. The SBF test shows that after immersion in SBF for 7 days, Si-HA coatings have been uniformly covered by a layer of apatite, while the apatite layers formed on the pure HA coating exhibits non-homogenous. Conclusion: The presence of silicon in electrolyte played a key role in inhibiting the growth of Si-HA crystals. The Si-HA coating displayed better bioactivity than HA coating, which could induce the formation of apatite layers with less time in SBF. M-P08 The unique feature of curved basal layers for the mesophase pitch based graphite in C/C composites Ju Rong1,3, Zhen Fan2, Zhihai Feng2, Lianlong He1 1. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72# Wenhua Road, Shenyang 110016, China 2. National Key Laboratory of Advanced Functional Composite Materials, Aerospace Research Institute of Materials & Processing Technology, Beijing 100076, China 3. University of Chinese Academy of Sciences, Beijing 100049, China

Objective: In order to fabricate high thermal conductivity composites for aerospace industry, the mesophase pitch is critical raw material due to the preferential graphitization and stable curved basal layers with increasing heat treatment temperature (HTT). Methods: The 2 dimension C/C composites were fabricated by mesophase pitch (MP) based carbon fiber as reinforcement and MP based matrix as filler. The process of heat treatment are consist of stabilization (500℃), carbonization (1000℃) and graphitization (3000℃) to obtain C/C composites. Results: the molten MP based matrix processed much liquid crystals can be easy graphitization with increasing HTT, the relatively perfect graphite will be formed in the matrix according to transmission electron microscopy investigations. It is interesting to note that the basal planes of graphite can be curved with each other to keep stable. This kind of special property can be proved evidently by the microcrystallines in the matrix, which surrounded concentrically by basal planes at the edge of microcrystal. Furthermore, as referred to the MP based carbon fiber, the same curved basal planes have been observed at the edge of fibers, displaying curved basal layers stacking along c axis. For this distinct microstructure of basal planes, the interesting interface between MP based carbon fibers and MP based matrix has been investigated comprehensively which will report in the near future. The reasons for the formation of curved basal layers are attributed to the crystal microstructure of hexagonal

graphite, that is to say, the bonding energy of σ parallel to basal planes is much higher than that of π perpendicular to basal planes. In this case, expanding the basal layers requires strong energy than stacking along c axis, therefore, the state of low energy is stable form for the hexagonal graphite. Accordingly, the microstructure plays a positive role in the transferring thermal in C/C composites, acting as bridge from carbon fiber to the matrix. The measured thermal conductivity of this kind of C/C composites is relatively high in comparison with any other kinds of composites fabricated by different types of carbon fiber and matrix. Conclusion: the basal layers of MP based graphite can curve with each other to keep stable with increasing HTT, this unique feature can be proved evidently not only by the MP based microcrystalline in the matrix but also by the edge of carbon fiber. This microstructure plays an important role in thermal transferring in C/C composites. M-P09 Orientation distribution of high strength polyacrylonitrile-based carbon fibers Xinshuang Guo1,4, Yongxin Cheng1,5, Zhen Fan2, Zhihai Feng2, LianLong He1, Ruigang Liu3, Jian Xu3 1. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72# Wenhua Road, Shenyang 110016, China 2. National Key Laboratory of Advanced Functional Composite Materials, Aerospace Research Institute of Materials and Processing Technology, Beijing 100076, China 3. Laboratory of Polymer Physics and Chemistry, Beijing National Laboratory of Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China 4. University of Chinese Academy of Sciences, Beijing 100049, China 5. University of Science and Technology of China, Hefei 230026, China

Objective: Orientation distribution across the longitudinal sections of high strength polyacrylonitrile (PAN)-based carbon fibers has been studied extensively. However, the common feature of their orientation distribution is still unknown. Methods: We studied five kinds of commercially available high strength PAN-based carbon fibers with circular cross-sections. The orientation angle (OA) was determined from the spread of the (002) arc in selected-area electron-diffraction pattern. The continuous changes of OA across longitudinal sections were used to characterize the orientation distribution. High angle annular dark field scanning TEM imaging was used to investigate the contrast change in the fiber section. Results: The morphologies of fiber cross-sections can be divided into two types according to the presence or absence of the contrast rings. A contrast ring exhibits two contrast zones in the longitudinal section. The OA distribution of carbon fibers without contrast zones approximates a horizontal line. For carbon fibers with contrast zones, the common features of their OA distribution are listed as follows. The OA increases or remains nearly constant in the skin but clearly decreases approaching to the contrast zone. The OA in the contrast zone is usually smaller than that in the skin and core. From the edge of the core to its center, the OA linearly increases quickly over a range of 0.6-1 μm. The OA change is usually nonlinear over greater ranges. Conclusions: Two types of OA distribution features are found in commercially available high strength PAN-based carbon fibers with circular sections. The contrast ring or zone is confirmed as a symbol of the skin-core structure and the boundary between the skin and core. In the longitudinal sections, the basal planes in the contrast zone exhibit highly preferred orientation and the crystallites are less wrinkled compared to the skin and core. Near the center of the core, the basal planes orient randomly. M-P10

Preparation and Characterization of Graphene/Carbon Nanotube Hybrid Thin Films by Drop-Coating Wei Huang, Xi Yang, Chaoyang Wang, Zhibing Fu Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900, China Hybrid thin films were prepared via a drop-coating method through using graphene prepared by chemical vapor deposition(CVD) and carbon nanotubes dispersed in 1, 2-dichlorobenzene as crude materials. The structure and morphology of hybrid thin films were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). It could be seen that the surface density of carbon nanotubes in the hybrid thin film increased linearly with the increase of dispersion concentration. The transmittance and sheet resistance of hybrid thin films with different concentrations of carbon nanotube dispersion were characterized by the UV-visible spectroscopy and four-point probe analyzer. The results indicated that the transmittance and sheet resistance of hybrid thin films decreased with the increase of dispersion concentration. Moreover, it showed that the hybrid thin film had the transmittance (at 550 nm) of 92.18% and sheet resistance of 0.998 kΩ/sq when the concentration of carbon nanotube dispersion was 0.1 mg/ml. The hybrid thin films with different properties could be prepared by adjusting the concentration of carbon nanotube dispersion and they would have the potential applications for transparent electrodes, field effect transistors and the laser mode-locking. M-P11 The Connection Between Pseudographite Domain Dimension of Biomass Carbon and Sodium Ion Battery Storage Jianfeng Huang, Caiwei Wang, Jiayin Li, Liyun Cao, Zhanwei Xu, Yayi Cheng, Ruizi Li School of Material Science and Engineering, Shaanxi University of Science and Technology We prepare a novel hard carbon derived from dandelion as a sodium ion anode by directly pyrolyzing it. The pseudographite domain dimension can be easily changed by means of different temperature controlling. With temperature increasing, the width of graphite layers named La gets larger, but the thickness of layers hardly changes, which causes the average number of layers decreases. After all, the whole volume of pseudigraphite domain are raising. Since La gets larger, more space can be provided for Na+ to storage at lower voltage (below 0.1 V), so the plateau capacity improves significantly. When the current density is 50 mA·g-1, the initial capacity enhances from 53.1% to 59.4% and the plateau capacity obviously increases from 40.1mAh·g-1 to 266.6 mAh·g-1

after 10 cycles, as the temperature is elevated from 800°C to 1200°C. The structure of dandelion can also be well preserved even carbonized at 1200°C, well-protected hollow tube structure is suitable for the transportation of electrolyte and volume expansion during sodium de-intercalation from the material. When the temperature goes up to 1400°C， the tube is destroyed into fragments and the average number of graphite layers increases, which hinder the diffusion path and diffusion rate of Na+, causing only 34 mAh·g-1 capacity storage. Besides, there is no apparent variation to sloping capacity because defects are very little under high temperature condition. As is said above, when the temperature is 1200°C, the length of La (12.6nm) and the structure are both most suitable for sodium ion storage. After 300 cycles , the discharge capacity is still 317.403 mAh·g-1 at 50 mA·g-1 and the Coloumbic efficiency is close to 100 %. When the current density is up to 5 A·g-1, the capacity can keep ~100 mAh·g-1. Excellent cycle performance and rate performance indicate carbonized dandelion is a promising anode material for sodium ion battery storage. M-P12

Preparation of carbon aerogels/carbon nano-onions composites by electron beam irradiation Xi Yang, Zhi-bing Fu, Hai-bo Zhao, Fan Yang, Rui Mi, Chao-yang Wang Research Center of Laser Fusion, China Academy of Engineering Physics Carbon aerogels (CAs) can be used on various applications due to their excellent properties, such as high surface area, special nano-porous structure and controllable density. Carbon nano-onions (CNOs) are the allotrope of fullerenes, which have the unique self-lubricating ability, outstanding chemical stability and mechanical properties. The CAs/CNOs composites may exhibit more excellent features. In this work, a special phase transformation can be observed that the non-crystalline nanospheres of CAs were transformed into CNOs under the action of the electron beam irradiation of HRTEM. For this reason, the CAs were treated with the different energy electron beam irradiation with the larger areas of 10*10 cm2. And the CNOs were formed in the nanoscale carbon framework of CAs. The properties of the resultant composites were investigated in detail. Based on these, many potential applications, such as electrochemical materials and supercapacitor materials, have been proposed. M-P13 Bonding TiO2 Nano-Array Directly on Carbon Fabrics for Outstanding Mechanical and Wet Tribological Properties of Carbon Fabrics/Phenolic Composite Jie Fei, Chao Zhang, Jianfeng Huang, Liyun Cao, Haibo Ouyang, Dan Luo School of Materials Science and Engineering, Shaanxi University of Science and Technology A facile hydrothermal method was developed to graft rutile TiO2 nano array onto carbon fabrics (CFs) by direct covalent bonding to form a TiO2-CFs hierarchical reinforcing structure. The influences of TiO2 nano array on the mechanical and wet tribological properties of thecarbon fabrics reinforced phenolic resin composite (CFRPC) were studied. The grafting without using any coupling agent was evidenced by XRD, RAMAN, FTIR, XPS and SEM spectroscopy. The results showed that the TiO2 array with highly dense, uniform size and preferred orientations was constituted of jagged ends TiO2 nanorods, which were assembled by nanowires with the length about 1 μm, width about 10-20 nm. The composite reinforced by TiO2-CFs (C1) showed the outstanding pore structure with appropriate porosity and permeability compared to the composites reinforced by desized-CFs (C0). Therefore, the tensile strength and interlaminar shear strength of C1 improved by about 85% and 56%, respectively, accompaning with moderate compressibility and high resilience. Further, C1 exhibited increased and more stable friction coefficient with improved wear resistance compared with C0. The polymer matrix composite reinforced by TiO2-CFs is highly promising for extreme mechanical engineering application, especially for high load and long time sliding. M-P14 Hydrothermal synthesis of cobalt oxide anchored with graphene for hydrogen peroxide detection Xinmeng Zhang School of Materials Science and Engineering, Shaanxi University of Science and Technology A new Co3O4-reduced graphene oxide (Co3O4-rGO) nanostructure was successfully prepared by hydrothermal synthesized Co3O4 porous nanoribbons hybridizing with reduced graphene oxide. The Co3O4-rGO modified electrode shows high electrochemical activity for the catalytic reduction and detection of H2O2 in alkaline medium. The non-enzymatic hydrogen peroxide sensor exhibits wide linear range of 1–18.5 mM (R = 0.99439), high adsorption amount about 3.24×10−6 mol/cm2, and a low detection limit of 5.35×10−7 M (S/N = 3). In addition,

the sensor has a fast response (< 5s), good long-term stability, excellent repeatability (3.22 % relative standard deviation), and high selectivity. These outstanding properties of the sensor derive from their particular hybrid structure and synergistic effects between rGO and Co3O4. M-P15 Oxidation resistance and thermal fatigue behavior of the ZrB2-CrSi2-SiC/SiC coated C/C composites Manhong Hu Northwestern Polytechnical University A multiphase ZrB2-CrSi2-SiC coating was prepared on the surface of SiC coated C/C composites by pack cementation. Dynamic oxidation resistance from room temperature to 1500 ºC and thermal fatigue behavior under thermal cycling in air of the specimen was investigated. Thermogravimetry analysis indicates that the ZrB2-CrSi2-SiC coating has a good oxidation protective ability in a wide range of temperature. Thermal fatigue behavior test result shows that with the times of thermal cycle between 1500 ºC and room temperature in air increased, the weight loss of the specimen increased and the fracture mode of the specimen altered. The specimen after 20 thermal cycles exhibited an ideal pseudo-plastic fracture characteristics and relatively high residual flexural strength (83.1 %). Published only Study on Voids of Epoxy Matrix Composites Sandwich Structure Parts Simin He, Youyi Wen, Cailin Li, Wenjun Yu Chengdu Aircraft Industry (Group) Co. Ltd., Chengdu 610091 Void is the most common tiny defect of composite materials. Porosity are closely related to composite structure property. The voids forming in the composites sandwich structural parts with the carbon fiber reinforced epoxy resin skins is researched by adjusting the manufacturing process parameters. The composites laminate different process parameters of difference porosity are prepared. The porosity ultrasonic nondestructive measurement method are developed and verified through microscopic examination. The analysis results show that compaction pressure and compaction time in the manufacturing process have influence on the porosity laminate area. Increase the compaction pressure and compaction time will reduce the porosity of the laminates. The bond-line between honeycomb core and carbon fiber reinforced epoxy resin skins are also analyzed through microscopic examination, the mechanical properties of sandwich structure composites are studied, the less voids, the higher composites mechanical properties. The optimization process parameters and porosity ultrasonic measurement method for composites sandwich structure have been applied to production. Reduction of Nitric Oxide by Mixed Materials of Cement Raw Meal and Biochar Hongxia Guo, Bin Wang, Suping Cui, Xiaoyu Ma, Lu Wei, Yanling Gan School of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China Many studies have indicated that carbon can be reducted to nitric oxide in the temperature above 700°C. Biochar is a kind of renewable carbon material and multiaperture material. Its cost is very low. Many metal oxides have a certain catalytic effect on the reaction that carbon reducted nitric oxide. Cement raw meal contains a lot of metal oxide. The temperature range of cement decomposition kiln is 800~900°C. The temperature can meet the

temperature requirement of carbon reducted NO. Therefore, it is possible that the combination of biochar and cement raw meal directly used to remove NO in the cement decomposition kiln. This paper reports an experimental study of NO reduction by mixed materials of cement raw meal and biochar. The proportion of mixed materials was 95~98 %wt cement raw meal and 2~5 %wt biochar. A detailed parametric study quantifying the effect of various operating parameters on the reduction of nitric oxide in the present of oxygen was carried out. In order to simulate the situation of cement decomposing kiln, the experiment was performed in a fixed bed reactor in the temperature range 800~900°C, O2 concentration range 1~5%, gas flow rate range 450~1350 mL/min. The inlet NO concentration was varied , ranging from 500 to 1500 ppm. The characterization of structure and properties of cement raw meal and biochar was conducted by employing XRD, SEM-EDS, BET, ATR. A kinetic study was also carried out. The result of NO conversation increased with increasing reaction temperature, decreasing O2 concentration, decreasing gas flow rate. The NO conversation can reach more than 60%. Even NO conversation is 90% in the condition of 900°C, 1% O2 concentration, 1000ppm NO concentration, 450ml/min gas flow rate. This method of removing NO is practically feasible. The effect of oxygen plasma etching on graphene over different time studied from mechanical and electrical properties Pengfei Jia, Fengming Pan, Tianhang Chen Nanjing University of Aeronautics and Astronautics In this paper, we report a study of the effect of oxygen plasma etching of chemical vapor deposited (CVD) graphene catalyzed by the Si substrate over different time. Our date from Atomic force microscopy (AFM) and Electronic transport measurements are presented. Experimental investigations verified etching via the oxygen plasma of multilayer graphene introduced new defects to the top graphene layer and this defects play an inducement role in etching of graphene in next etching period. In addition, oxygen plasma bombarding the surface of graphene can change its surface roughness,mechanical behavior and tribological properties.And Electronic transport measurements show a decrease in mobility and minimum conductivity in plasma-etched graphene over different etching-time. The results indicated that after the oxygen plasma etching, the physical properties of grapehe changed regular with increase in etching-time. Our findings are valuable for studying the effects of plasma etching on graphene and changing the physical properties of graphene through artificially generated defects. Enhanced microwave absorption properties of rod-shaped Fe2O3/Fe3O4/MWCNTs nanocomposites Lina Huang Beihang University A novel type of composite absorber, i.e. Fe2O3/Fe3O4/MWCNTs composites, with microwave absorption properties was successfully fabricated by a facile hydrothermal method. After being fabricated, the α-Fe2O3 and Fe3O4 nanoparticles displayed rod-shaped morphology. The complex permittivity and permeability of the Fe2O3/Fe3O4/MWCNTs composites distinctly increased, furthermore, with the introduction of MWCNTs, the Fe2O3/Fe3O4/MWCNTs composites exhibited microwave absorption performance with strong absorption and wide absorption band. In particular, for Fe2O3/Fe3O4/1.7% MWCNTs composite with an absorber thickness of 2.5 mm, the reflection loss (RL) reached a minimum of –44.1 dB at 10.4 GHz and the effective absorption bandwidth (RL<-10dB) covered 3.3 GHz. The enhanced microwave absorption performance of the

Fe2O3/Fe3O4/MWCNTs composites was attributed to the high dielectric loss and improved impedance matching which was closely related to the rod-shaped morphology of Fe2O3, Fe3O4 and the introduction of MWCNTs. A new practical method for homogeneous dispersion of multi-walled carbon nanotubes (MWCNTs) in Mg matrix composites Teng zhang, Shuangming Du, Wanchang Sun, Jumei Zhang, Libin Niu, Xiaohu Hua Xi’an University of Science and Technology It is difficult to disperse multi-walled carbon nanotubes (MWCNTs) in Mg matrix composites homogeneously due to the high specific surface energy between MWCNTs. This would affected the mechanical properties of magnesium matrix composites reinforced by MWCNTs increasing tremendously. It is the key to overcome the MWCNTs themselves aggregate together, and gain homogeneous dispersion of MWCNTs. Moreover, the different density between Mg matrix and MWCNTs is another problem which prevent the MWCNTs disperse homogeneously in Mg matrix composites. In order to solve these problems, a new practical method for homogeneous dispersion of carbon nanotubes in Mg matrix composites was presented in this paper basing on combination the tow-step ball milling and ultrasonication dispersion methods. Firstly, a certain amount of MWCNTs were ball-milled in ethanol solution which contain 5wt% sodium stearate at various rotation speeds (100 rpm–300 rpm) and ball-milling times (0.5h-2h) to break MWCNTs themselves hard aggregate together. Secondly, MWCNTs which were subjected to the ball-milling were dispersed further using ultrasonication method in ethanol solution contain various dispersing agents (SDS, SDBS). Thirdly, the Mg powers were mixed with good dispersion of carbon nanotubes solution and ball-milled for 1h to make MWCNTs coated uniformly on the surface of the magnesium substrate. The results were mainly examined by scanning electron microscopy (SEM). It was found that MWCNTs were dispersed well and some of MWCNTs have directional arrangement. Furthermore, MWCNTs were homogeneously dispersed in Mg matrix composites. The results showed that this method has good application in magnesium matrix composites reinforced by carbon nanotubes. Getting graphite nano-sheets of different sizes by choosing parent graphite: ultrasonication assisted preparation Chunyu Wang, Haiping Liu, Chunlin Qin, Sifu Bi Harbin Institute of Technology at Weihai Objective: In this work, a simple and effective method for preparing graphite nano-sheet (GNS) was investigated. Methods: It is important that the choosing size of parent graphite can obtain smaller size of GNSs diameter or thickness with the ultrasonication treatment. Under the optimal preparing condition, ultrasonication treating parameter is confirmed. The structure was characterized with scanning electron microscopy (SEM), high resolution transmission electron microscopy (HTEM). Results: It is results show that the GNS size decreases sharply at the high power factor stage of ultrasonication and then the decrease slow down with the decrease power factor of ultrasonication treatment. Conclution: It is employed that the choosing smaller size of parent graphite (>200-mesh) can obtain smaller size GNSs with diameter (<10μm) and thickness (~4nm). The influence of chemical admixtures on the dispersion of carbon nanotubes in water and cement pastes Suping Cui, Hui Liu, Jianfeng Wang, Jiachen Wang Department of Materials Science and Engineering, Beijing University of Technology

Carbon nanotubes (CNTs) were found to be able to improve or modify the mechanical property, durability and functional properties of cementitious materials due to their excellent intrinsic properties and composite effects. However, poor dispersion of CNTs leads to the formation of many defect sites in the nano composite and limits the efficiency of the CNTs in the cement matrix.This paper investigates the influence of ultrasonic and three types chemical surfacetants (cationic, anionic and nonionic surfacetants ) on the dispersion of carbon nanotubes. Techniques include UV-vis-NIR spectrophotometer, laser particle size analyzer and scanning electrical microscope (SEM). Results show that: 1) Ultrasonic leads a dispersive effect on CNTs and the best ultrasonic time is 2min; 2) CNTs with more carboxyl groups show better dispersion in water; 3) Three types surfacetants have positive effect on the dispersion of CNTs, among which cationic surfacetants lead to the best dispersibility; 4) the optimum dosage of surfacetants is 5:1 (the mass ratio of dispersant to CNTs); 5) Three types surfacetants can improve the dispersion of CNTs in cement pastes indicated from SEM images. Fabrications and in-situ characteristics of cobalt oxide-reduced graphene oxide composite Rui Wang1,3, Daming Zhu3, Yueliang Gu3, Guangzhi Yin3, Zhenjie Feng2, Xiaolong Li3 1. Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China 2. Department of Physics, College of Sciences, Shanghai University, Shanghai 200444, China 3. Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China

Graphene is a single-atom-thick sheet of carbon atoms packed in two-dimensional (2D) honeycomb lattices, which possesses a large surface area and high electrical/thermal conductivity as well as excellent mechanical properties. However, graphene sheets without functionalization are insoluble and infusible, and the poor processability has limited their large-scale practical applications. For this reason, composites comprised of graphene and inorganic nanoparticles, such as metal, metal oxides and sulphides, have attracted a great deal of attention recently. This functional and interesting nanocomposite exhibits great potential prospects in the fields of energy storage, environmental treatment and so on. In this work, a facile and delicate method was used to fabricate functional graphene-based nanocomposite material, cobalt oxide@reduced graphene oxide (rGO), by drop casing of CoCl2@ graphene oxide water solution. In detail, GO was prepared from graphite power following a modified Hummers method. CoCl2@GO solution dispersions were prepared by physical mixing of CoCl2 in GO solution with sonication. Firstly, CoCl2@GO solution dispersions (15μL) were dropped onto piranha-cleaned Si substrate (1cm×1cm). Secondly, the superlattice structure of Co(OH)2 and GO were synthesized facilely by pre-designed colloid electrostatic self-assembly process on silicon substrate at 300℃, which occurred between the positively charged Co(OH)2 colloid particles and negatively charged GO sheets. The advantage of this method is that Co(OH)2 colloid nanoparticles prepared are positively charged without any surface modifacation, and the Co(OH)2 colloid nanoparticles can be well dispersed in the interlayer of GO. Finally, during the subsequent heat treatment at 500℃, the formation of Cobalt oxide and the reduction of GO to rGO happen simultaneously to obtain the expected composite. Real-time observation of the growth of cobalt oxide@rGO composite was done by in-situ two-dimensional grazing-incident x-ray diffraction (GIXRD) method, which was performed at the 14B beamline of the Shanghai Synchrotron Radiation Facility (SSRF), China. The radiation wavelength of X-ray is 1.24. We found that the intense diffraction peak at 2θ = 22.9°was contributed to plenty water molecules in the CoCl2@GO solution. Then this peak gradually weakened, suggesting that water evaporated overtime. After 20 mins, a diffraction peak of CoCl2@GO@H2O arose and shifted to high angle direction combined with the evaporation of solution water. When the annealing temperature increasing to 300℃, we found that a superlattice structure of Co(OH)2@GO was formed self-assembly, displayed by three ordered diffraction peaks. The formation of the superlattice structure is

contributed to the strong electrostatic attractive interactions between the positively charged Co(OH)2 colloidal nanoparticles and the negatively charged GO nanosheets. In addition, such self-assemble behavior can be further stabilized by the other noncovalent interactions (van der Waals interactions and hydrogen bonding) as well as the chemisorption between the Co(OH)2 colloidal nanoparticles and the groups containing oxygen (carboxylic, hydroxyl, and epoxy groups) presented on the GO surface. At 500 ℃, we found that the ordered diffraction peaks of the superlattice structure weakened and a lot of diffraction rings were produced, indicating the supperlattice structure was destroyed and the cobaltous oxide@reduced graphene oxide material was formed instead. SEM images of cobaltous oxide-rGO showed that the morphology of the composite material are almost consistent with that of the rGO sheets in the range of micrometers, while Co(OH)2 and cobaltous oxide mainly intercalate between the rGO sheets or anchor onto their surface, which indicates that the colloid electrostatic self-assembly process is an effective way to combine the two different components. At the same time, the morphology of the cobaltous oxide nanoparticles anchored onto rGO is irregular spherical with a diameter of about 10–30 nm, which is bigger than that of the Co(OH)2 colloidal precursor. Due to the presence of cobaltous oxide nanoparticles, it would prevent the rGO sheets restacking to increase the activity of rGO’s surface, which is consistent with XRD experiment. Furthermore, Raman spectra of supperlattice Co(OH)2@GO, cobaltous oxide@rGO and GO investigated with Ar+ laser excitation (514.5 nm) were obtained. For all the samples, the G band (1588 cm-1 ) corresponds to the sp2 hybridized carbon and the D band (1341 cm-1) is originating from the disordered carbon. Obviously, G band and D band in the Raman spectrum of Co(OH)2@GO shifted to higher wave numbers, showing that a supperlattice structure of Co(OH)2@GO was obtained. In the Raman spectrum of cobaltous oxide@rGO, the intensity ratio of D over G band is distinctly higher than that of Co(OH)2@GO and GO, which is consistent with the literature. On the other hand, the increased D band intensity of the cobaltous oxide@rGO results from the apparent structure interaction between cobaltous oxide nanoparticles and rGO sheets. In conclusion, we fabricated functional graphene-based nanocomposite material, cobalt oxide@rGO, using a deft method by drop casing of CoCl2@GO solution on silicon substrate. By using in-situ grazing-incident X-ray diffraction, we found that a supperlattice structure of Co(OH)2@GO was formed self-assembly at 300 ℃ induced by the strong electrostatic attractive interactions between the positively charged Co(OH)2 colloidal nanoparticles and the negatively charged GO nanosheets. When the annealing temperature increased to 500 ℃, we observed that the supperlattice structure was destroyed and the cobalt oxide-rGO material was formed instead. Additionally, we obtained that the irregular spherical cobaltous oxide nanoparticles with diameters of 10–30 nm were dispersed and loaded uniformly onto the surfaces of rGO sheets. This material will have significant potentials in energy storage and environmental treatment, etc.