Protective Graphite Coating for Two-Dimensional Carbon/Carbon Composites

Two-dimensional carbon/carbon(2D C/C)composites are a special class of carbon/carbon composites,generally obtained by combining resin-impregnated carbon fiber clothes,which are then cured and carbonized.This study deals with the preparation of a protective coating for these materials.This coating,based on graphite,was prepared by the slurry method.The effect of graphite and phenolic resin powders with different weight ratios was examined.The results have shown that the coating slurry can fill the pores and cracks of the composite surface,thereby densifying the surface layer of the material.With the increase of the graphite powder/phenolic resin weight ratio,the coating density is enhanced while the coating surface flatness decreases;moreover,the protective ability of coating against erosion first increases(from 1:3 to 2:2)and then decreases(from 2:2 to 3:1).When the weight ratio is about 1:1,the coating for 2D C/C composites exhibits the best erosion resistance,which greatly aids these materials during gas quenching.In this case,the erosion rate is decreased by approximately 41.5%at the impact angle of 30°and 52.3%at normal impact,respectively.This can be attributed to the ability of the coating slurry to infiltrate into the substrate,thereby bonding the fibers together and increasing the compactness of the 2D C/C composites.

Anti-oxidation behavior of chemical vapor reaction SiC coatings on different carbon materials at high temperatures

To protect carbon materials from oxidation,SiC coatings were prepared on carbon/carbon(C/C)composites and graphite by chemical vapor reaction.SEM and XRD analyses show that the coatings obtained are composed of SiC grains and micro-crystals. The influence of different carbon substrates on oxidation behavior of coated samples was investigated,and then their oxidation mechanisms were studied.Oxidation test shows that the SiC coated graphite has a better oxidation resistance than SiC coated C/C composites at high temperatures(1 623 K and 1 823 K).In the oxidation process,the oxidation curves of SiC coated C/C composites are linear,while those of SiC coated graphite follow a quasi-parabolic manner.The oxidation mechanism of the former is controlled by chemical reaction while the latter is controlled by oxygen diffusion based on the experimental results.The variation of oxidation behavior and mechanism of SiC coatings on two kinds of carbon substrates are primarily contributed to their structure differences.

Tailoring carbon chains for repairing graphite from spent lithium-ion battery toward closed-circuit recycling

Graphite, as a strategic mineral resource, the recycling from spent lithium-ion batteries(LIBs) has attracted considerable attention for meeting considerable economic value. However, closed-circuit recycling still suffers from the lack of effective repair methods. Considering the existing defects, a series of Cchain length carbons have been successfully introduced to repair spent graphite. Obviously, with the evolution of carbon resources, the thickness and pores of the coating layer were tailored with the functional groups. Benefitting from the increased active sites and created fold structure, their coulombic efficiency is obviously restored from 14% to 86.89%, while the stable capacity is kept at approximately 384.9 mAh gafter 100 cycles. Moreover, their excellent rate properties are kept about approximately 200 mAh gat2 C, meeting the standard of commercial materials. Supported by the detailed kinetic behaviors, the enhanced rate is mainly dominated by pseudocapacitive behaviors, accompanied by deepening redox reactions. Meanwhile, the cost of the proposed approach for recycling spent graphite is 894.87 $ t^(-1),and the recycling profit for regenerating graphite is approximately 7000 $ t^(-1). Given this, this work is anticipated to shed light on the closed-circuit recycling of spent graphite and offer significant strategies to repair graphite.

Catalytic graphitization of polyacrylonitrile(PAN)-based carbon fibers with Fe-Cr_2O_3 composite coating

The process of electrodepositing Fe-Cr2O3 composite coating on polyacrylonitrile （PAN）-based carbon fibers and its catalytic graphitization were studied. Carbon fibers with and without electrodeposited Fe-Cr2O3 composite coating were heat treated at different temperatures and the structural changes were characterized by XRD, Raman spectroscopy and SEM. The results indicate that Fe-Cr2O3 composite coating exhibits a significant catalytic effect on graphitization of carbon fibers at low temperatures. When the Fe-Cr2O3-coated carbon fibers were heat treated at 1 300℃ the interlayer spacing （doo2） and ratio of relative peak area （AD/AG） reach 3.364/k and 0.34, respectively. Whereas, the extent of graphitization of pristine carbon fibers is comparatively low even after heat treatment at 2 800℃ and the values of doo2 and AD/AG are 3.414 A and 0.68, respectively. The extent of graphitization of carbon fibers increases not only with the increase of the catalyst gross but also the Cr2O3 content in Fe-Cr2O3 coating. The catalytic effect of Fe-Cr2O3 composite coating accords with the dissolution-precipitation mechanism.

Ir Protective Coatings for Carbon Structural Materials

Ir coatings were deposited on the heat-treated C/C composites and graphite by double glow plasma. Microstructure and morphology of the coating and substrate were observed by SEM and TEM. The effect of the surface treatment for the carbon structural materials on the microstructure of the coating was investigated. Many large gaps and pores appeared on the surface of the substrates after heat treatment. The Ir coating did not fully covered on the surface of heat-treated C/C composite and graphite substrates because of the large gaps and pores on the surface of substrates. The Ir coating exhibited excellent ablation resistance at super-high temperature. After super-high temperature ablation, the coating kept the integrity, but the coating was weekly bonded to the substrates. Some microcracks and micropores appeared on the surface of as-ablated coating. The Ir coating would need thick enough to cover and fill the large microgaps and micropores on the surface of the heat-treated C/C and graphite substrates.

Catalytic graphitization of polyacrylonitrile-based carbon fibers coated with Prussian blue

Prussian blue(PB) was used as catalyst to improve the extent of graphitization of polyacrylonitrile(PAN)-based carbon fibers.PB was deposited on carbon fibers by anodic electrodeposition and the thickness of PB coating(PB content) was controlled by adjusting the electrodeposition time.PAN-based carbon fibers with PB coating were heat-treated and the extent of graphitization was measured by X-ray diffractometry and Raman spectroscopy.The results indicate that the extent of graphitization of PAN-based carbon fibers is enhanced in the presence of the coating.When the PB-coated carbon fibers were heat-treated at 1 900 ℃,interlayer spacing(d002) and crystallite size(Lc) reach 0.336 8 and 21.2 nm respectively.Contrarily,the values of d002 and Lc are 0.341 4 and 7.4 nm respectively when the bare carbon fibers were heat-treated at 2 800 ℃.Compared with the bare carbon fibers,PB can make the heat treatment temperature(HTT) drop more than 500 ℃ in order to reach the same extent of graphitization.Furthermore,the research results show that PB content also has a certain influence on the extent of graphitization at the same HTT.

Development of a Graphite Coating and Its Transfer from Batch to Coil Process for Application in PEMFC for Hydrogen-Powered Vehicles

In the present paper, coating systems consisting of a metallic corrosion barrier and a conductive graphitic carbon layer were deposited by a DC vacuum arc process. The coatings were developed in a batch process for application in the polymer electrolyte membrane fuel cell (PEMFC), and transferred to a continuous coil process to facilitate industrial mass production. The coating samples in the coil process had to achieve comparable results to the samples produced in the batch process, to meet the requirements of the environment prevailing in the fuel cell.The transfer to roll-to-roll processes is a crucial factor for commercial upscaling of PEMFC production. The experimental results showed that the electrical conductivity and corrosion resistance of the samples in the coil process were significantly improved compared to the uncoated base material and showed comparable performance to batch coated samples. X-ray photoelectron spectroscopy (XPS) was performed to determine the depth profile and the surface composition. Additional measurements were recorded for the contact resistances using the four-wire sensing method as well as corrosion resistance using potentiodynamic methods.

Soft carbon-coated bulk graphite for improved potassium ion storage

Potassium-ion batteries(PIBs) have attracted tremendous attention for large-scale energy storage fields based on abundant potassium resources. Graphite is a promising anode material for PIBs due to its low potassium ion intercalation voltage and mature industrialized preparation technology. However, the inability of graphitic structures to endure large volume change during charge/discharge cycles is a major limitation in their advancement for practical PIBs. Herein, a soft carbon-coated bulk graphite composite is synthesized using PTCDA as a carbon precursor. The PTCDA-derived soft carbon coating layer with large interlayer distance facilities fast potassium ion intercalation/extraction in the BG@C composite and buffers severe volume change during the charge/discharge cycles. When tested as anode for PIBs, the composite realizes enhanced rate capability(131.3 mAh/g at 2 C, 1 C=279 m A/g) and cycling performance(capacity retention of 76.1% after 150 cycles at 0.5 C). In general, the surface modification route to engineer graphite anode could inherently improve the electrochemical performance without any structural alteration.

A Novel Modification Approach for Natural Graphite Anode of Li-ion Batteries

To improve the rate capability and cyclability of natural graphite anode for Li-ion batteries,a novel modification approach was developed.The modification approach included two steps:(a)high-energy ball milling in a rotary autoclave containing alumina balls,H_3PO_4 and ethanol;(b)coating with pyrolytic carbon from phenlic resin.The treated graphite shows obvious improvement compared with the original natural graphite in electrochemical properties such as cyclability and rate capability,especially at high current density.The primary reasons leading to the improvement in rate capability and cyclability are that the diffusion impedance of Li^+ in graphite is reduced due to the fact that P filtered into graphite layers can mildly increase interlayer distances,and the fact that the structural stability of graphite surface is enhanced since the coated pyrolytic carbon can depress the co-intercalation of solvated lithium ion.

Low Temperature Preparation of Carbide Coated Carbon for Refractory Castable Applications

Titanium carbide （ TiC ） coated graphite flakes （GF） and carbon black （CB） powders were prepared at relatively low temperatures （ 750 - 950 ℃ ） using a no- vel molten salt synthesis technique. The in-situ formed TiC coatings were homogeneous and crack-free and their thicknesses could be readily controlled/tailored by simply adjusting the Ti/C ratio. Compared to their uncoated counterparts, as prepared TiC coated GF and CB showed much improved water-wettability/dispersivity and rheological properties, and thus could be potentially used to prepare carbon-containing refractory castables.

Investigation towards scalable processing of silicon/graphite nanocomposite anodes with good cycle stability and specific capacity

Silicon/graphite(Si/Gr)nanocomposites with controlled void spaces and encapsulated by a carbon shell(Si/Gr@void@C)are synthesized by utilizing high-energy ball milling to reduce micron-sized particles to nanoscale,followed by carbonization of polydopamine(PODA)to form a carbon shell,and finally partial etching of the nanostructured Si core by NaOH solution at elevated temperatures.In particular,the effects of ball milling time and NaOH etching temperature on the electrochemical properties of Si/Gr@void@C are investigated.Increasing the ball milling time results in the improved specific capacity of Si-based anodes.Carbon coating further enhances the specific capacity and capacity retention over charge/discharge cycles.The best cycle stability is achieved after partial etching of the Si core inside Si/Gr@void@C particles at either 70 or 80C,leading to little or no capacity decay over 130 cycles.However,it is found that both carbon coating and NaOH etching processes cause some surface oxidation of the nanostructured Si particles derived from high-energy ball milling.The surface oxidation of the nanostructured Si results in decreases in specific capacity and should be minimized in future studies.The mechanistic understanding developed in this study paves the way to further improve the electrochemical performance of Si/Gr@void@C nanocomposites in future.

低温热处理对Graphit-iC类石墨碳膜组织结构及耐磨性的影响

应用拉曼光谱(Raman)等测试方法分析了不同热处理温度对PVD技术制备的Graphit-iC类石墨碳膜涂层的组织结构、显微硬度、结合强度和磨损率的影响规律。结果表明:随温度升高,涂层发生sp3→sp2结构转变,相对强度比I_D/I_G增加,石墨化倾向增大;涂层磨损率在25～250℃温度区间内保持较低的水平,当温度继续上升后表面显微硬度及结合力降低,磨损率显著增大,耐磨性降低。

电极材料对三维电极-电Fenton处理制药废水的影响

目的研究电极材料在三维电极-电Fenton处理制药废水过程中对COD去除率的影响,找寻最佳工艺条件。方法以模拟阿奇霉素制药废水为处理对象,分析在相同控制条件下以阳极材料、活性炭粒子电极类型、浓度对制药废水中COD去除效果的影响,并确定最佳试验条件。结果综合成本考虑,三维电极-电Fenton体系处理制药废水以石墨为阴极材料,以钛涂钌铱作为阳极材料,柱炭粒径为3 mm、投加量为100 g/L时处理效果最好,COD去除率达到77.39%,可生化性由0.072提高至0.353。结论阳极材料、粒子电极的粒径、浓度对于三维电极-电Fenton体系处理制药废水的降解效果具有较大影响;研究结果可以满足后续生物处理要求。

Spontaneous escape behavior of silver from graphite-like carbon coating and its inhibition mechanism

A series of silver-doped graphite-like carbon coatings was prepared on the surface of aluminum alloy using the magnetron sputtering method. The spontaneous escape behavior and inhibition mechanism of silver from graphite-like carbon coating were studied. The results showed that when the sample prepared with a 0.01-A current on the silver target was placed in an atmospheric environment for 0.5 h, an apparent silver escape phenomenon could be observed. However, the silver escape phenomenon was not observed for samples prepared with a 0.05-A current on the silver target if the sample was retained in a 10^（-1） Pa vacuum environment, even after 48 h. Compared with the sample placed in the atmospheric environment immediately after an ion plating process, the silver escape time lagged for 6 h. Nanometer-thick pure carbon coating coverage could effectively suppress silver escape. When the coating thickness reached700 nm, permanent retention of silver could be achieved in the silver-doped graphite-like carbon coating.As the silver residue content in the graphite-like carbon coating increased from 2.27 at.% to 5.35 at.%, the interfacial contact resistance of the coating decreased from 51mΩcm^2 to 6 mΩcm^2.

Performance of activated carbon coated graphite bipolar electrodes on capacitive deionization method for salinity reduction

This research investigates a capacitive deionization method for salinity reduction in a batch reactor as a new approach for desalination.Reductions of cost and energy compared with conventional desalination methods are the significant advantages of this approach.In this research,experiments were performed with a pair of graphite bipolar electrodes that were coated with a one-gram activated carbon solution.After completing preliminary tests,the impacts of four parameters on electrical conductivity reduction,including(1)the initial concentration of feed solution,(2)the duration of the tests,(3)the applied voltage,and(4)the pH of the solution,were examined.The results show that the maximum efficiency of electrical conductivity reduction in this laboratory-scale reactor is about 55%.Furthermore,the effects of the initial concentration of feed solution are more significant than the other parameters.Thus,using the capacitive deionization method for water desalination with low and moderate salt concentrations(i.e.,brackish water)is proposed as an affordable method.Compared with conventional desalination methods,capacitive deionization is not only more efficient but also potentially more environmentally friendly.

In Vitro Biocompatibility of MC3T3-E1 Osteoblast-like Cells on Arg-Gly-Asp Acid Peptides Immobilized Graphite-like Carbon Coating on Carbon/Carbon Composites

Carbon/carbon （C/C） composites were deposited with graphite-like carbon （GLC） coating, and then, Arg-Gly- Asp acid （RGD） peptides were successfully immobilized onto the functionalized GLC coating. GLC coating was utilized to prevent carbon particles releasing and create a uniform surface condition for C/C composites. RGD peptides were utilized to improve biocompatibility of GLC coating. Surface chemical characterizations of functionalized GLC coating were detected by contact angle measurement, X-ray photoelectron spectroscopy and Raman spectra. Optical morphology of GLC coatings was observed by confocal laser scanning microscopy. In vitro biological performance was determined using samples seeded with MC3T3-E1 osteoblast-like cells and cultured for 1 week. Surface characterizations and morphological analysis indicated that C/C composites were covered by a dense and uniform GLC coating. Contact angle of GLC coating was reduced to 27.2° when it was functionalized by H202 oxidation at 40 ℃ for 1 h. In vitro cytological test showed that the RGD peptides immobilized GLC coating had a significant improvement in biocompatibility. It was suggested that RGD peptides provided GLC coating with a bioactive surface to improve cell adhesion and proliferation on C/C composites.

聚醚醚酮与不同硬质涂层配副的摩擦学行为对比

目的对比聚醚醚酮(PEEK)与不锈钢、CrN涂层、Cr/GLC多层涂层3种配副的大气环境摩擦学行为。方法采用多靶磁控溅射镀膜技术在17-4PH不锈钢基底表面制备CrN涂层和Cr/GLC多层涂层。采用摩擦磨损试验机和三维轮廓仪对配副摩擦因数和磨损率进行测试,采用扫描电镜、拉曼光谱仪和显微红外光谱仪等方法,表征不同配副摩擦前后的表面物理化学状态,剖析涂层与PEEK配副的磨损机理。结果CrN涂层和Cr/GLC多层涂层均显著提高了不锈钢基底的摩擦性能,相较于PEEK与17-4PH不锈钢配副,CrN涂层和Cr/GLC多层涂层的摩擦因数都显著降低。此外,涂层的磨损率分别降低了93.1%、97.4%;对应PEEK配副的磨损体积也分别降低了35.1%和65.8%。在3种配副条件下,PEEK摩擦后均发生了芳香环的开放、取代、交联,以及不同程度的结晶度损失,结晶度的顺序为未磨PEEK>PEEK-Cr/GLC>PEEK-CrN>PEEK-17-4。结论CrN涂层的硬度、粗糙度较高,且缺少润滑,黏着磨损更显著,PEEK材料发生了大量转移,转移材料在减轻PEEK磨损的同时也阻止了结晶度的降低。PEEK与Cr/GLC多层涂层配副表现出最佳的耐磨损性能,主要归因于摩擦时PEEK结晶度的维持及GLC中富石墨相赋予涂层的低剪切润滑作用。

微晶石墨改性用作锂离子电池负极材料

微晶石墨存在加工性能差、低首效的缺点,对此采用了高温石墨化、碳化包覆对微晶石墨进行改性,引入了超高分子羧甲基纤维素钠(CMC)作为分散剂。与改性前的微晶石墨对比,加工性能和电化学性能得到大幅度提升。利用激光粒度分布仪等表征了其物理性能,利用SEM等分析了微晶石墨的结构和表面形貌,利用浆料粘度的变化表征其加工性能,并通过扣电测试了其电化学性能。结果表明:高温处理后的微晶石墨扣电首效由64.2%提升至87.1%,克容量发挥275.2 mAh/g提升至343.3 mAh/g;包覆后的微晶石墨浆料稳定性更好,克容量发挥达到394 mAh/g;使用超高分子CMC保证浆料稳定性的同时,也改善电池的倍率性能。

沥青碳包覆量对隐晶质石墨电化学性能的影响

以吉林某地高纯球形化隐晶质石墨为原料,利用石油沥青对其进行包覆-炭化改性处理,制备锂离子电池负极材料,考察了沥青碳包覆量对隐晶质石墨负极材料结构及电化学性能的影响。结果表明,沥青碳包覆层改善了隐晶质石墨的表面形貌,改性后的隐晶质石墨具有更好的循环充放电性能和倍率充放电性能。当包覆量为14%时,经30次循环充放电后试样的放电容量保持率较未改性试样提高8.88%。当包覆量为18%时,在1 C电流密度下,试样放电容量保持率较未改性试样提高69.12%。

长寿命循环的磷酸铁锂电池及材料、工艺

利用预锂化技术以及预锂化材料(也称为补锂剂、预锂化添加剂)的富锂优势,将预锂化材料添加在磷酸铁锂(LFP)电池正极极片中,研制了磷酸铁锂方形铝壳51 Ah全电池,以及软包7 Ah全电池,并进行了循环寿命方面的测试和研究。利用以往经验分析了正极、负极等主材(比如磷酸铁锂、石墨、电解液配比、集流体、隔膜)到辅料(正、负极黏合剂,导电剂等)以及预锂化材料的特性和对电池寿命的影响,以化学反应方程式的形式分析了已经工业化的几种预锂化材料的补锂机理以及补锂容量值。试验结果表明,添加预锂化材料的7 Ah电池循环寿命在9000周,而没有添加预锂化材料的7 Ah电池的循环寿命在5300周,添加预锂化材料的7 Ah电池的循环性能明显优于未添加预锂化材料的电池,循环寿命提高了50%左右;能量效率方面:添加预锂化材料的7 Ah电池的常温25℃,0.2 C能量转化效率为96.74%,0.5 C能量转化效率为94.80%,1 C能量转化效率为92.67%,均高于未添加预锂化材料的7 Ah电池的能量转化效率。本研究有助于推动预锂化技术以及预锂化材料在磷酸铁锂长循环新型储能电池中的应用,为长寿命磷酸铁锂电池的设计研发提供实验依据。