Electrochemical capacitors based on highly porous carbons prepared by KOH activation

Various coal and pitch-derived carbonaceous materials were activated for 5 h at 800 °C using potassium hydroxide and 1:4 component ratio. Porosity development of the resultant activated carbons (ACs) was assessed by N₂ sorption at 77 K and their capability of the charge accumulation in electric double layer was determined using galvanostatic, voltammetric and impedance spectroscopy techniques. ACs produced from different precursors are all microporous in character but differ in terms of the total pore volume (from 1.05 to 1.61 cm³ g⁻¹), BET surface area (from 1900 to 3200 m² g⁻¹) and pore size distribution. Very promising capacitance values, ranging from 200 to 320 F g⁻¹, have been found for these materials operating in acidic 1 mol l⁻¹ H₂SO₄ electrolytic solution. The variations in the electrochemical behavior (charge propagation, self-discharge, frequency response) are considered in relation to the porous texture characteristics, elemental composition but also possible effect of structural ordering due to various precursor materials used. Cycling investigation of all the capacitors has been also performed to compare ability of the charge accumulation for different carbon materials during subsequent cycles.     

Synthesis of nanoporous carbons from mixtures of coal tar pitch and furfural and their application as electrode materials

Synthetic nanoporous carbons are prepared by polymerization of mixtures containing coal tar pitch and furfural in different proportions, followed by carbonization of obtained solid product and steam activation of the carbonizate. The chemical composition of the initial mixture significantly affects the physicochemical properties (surface area, pore structure, electro resistance and amount of oxygen-containing groups on the surface) of the obtained materials. The incorporation of oxygen in the precursor mixture by means of furfural, has a strong influence in the synthetic step; increasing the furfural content facilitates the formation of a solid product characterized by a large oxygen content. Moreover, the solid product is more reactive towards activation as the furfural content increases, giving rise to nanoporous carbons with large surface areas and unique chemical features (high density of oxygen functionalities of basic nature). These nanoporous carbons have been investigated as electrodes in electrochemical applications.     

Influence of granular carbons on pitch properties

This paper deals with the study of the variation of properties of four pitches (a commercial impregnating coal tar pitch, an air-blown and two thermally treated pitches) when mixed with four granular carbons (anthracite, graphite, green petroleum coke and foundry coke). As a first step, optical microscopy was used to determine the distribution of the pitch among the granular carbons. The anthracite seems to attract the primary quinoline insolubles present in the commercial and thermally treated pitches. This allows the mesophase spheres to coalesce at unusually low temperatures during the mixing process. In general, the toluene insoluble content of the pitch showed a significant increase after mixing with the granular carbons. This is an indication of the interactions between the different granular carbons and some compounds present in the pitches. Analytical techniques like size exclusion chromatography and differential scanning calorimetric analysis were used in order to obtain information about the characteristics of the components of the pitches that interact with the different granular carbons and their effect on pitch properties. Graphite seems to interact preferentially with the larger molecules whereas the green petroleum coke acts on a wider molecular range.     

Improving the performance of carbon/graphite composites through the synergistic effect of electrostatic self-assembled carbon nanotubes and nano carbon black

Superior performance fillers are considered as an effective means to enhance the performance of carbon/graphite composites. However, poor interfacial properties and incomplete filler networks limit the performance enhancement of the composites. In this study, a new method was proposed to weaken this impact through the synergistic effect of the electrostatic self-assembly of nano carbon black (NCB) onto carbon nanotubes (CNTs). The results showed that the synergistic effect between NCB and the CNTs significantly improved the mechanical and electrical properties of the composites. NCB reduces the porosity of the composites and increases the interaction between the CNTs and matrix. The compressive strength of the composite was 143.2 Mpa, and the flexural strength was 46.3 MPa, which is 210% higher than that of the pristine carbon/graphite composites. Moreover, NCB and CNTs form a globally connected synergistic network in the carbon skeleton. Composites filled with CNTs/NCB exhibited the lowest resistivity and highest thermal conductivity, with a resistance that was 42% lower than that of pristine carbon/graphite composites at 44.8 μΩ m. All of these results suggest that the synergistic effect of CNTs/NCB show great potential to improve the performance of carbon/graphite composites.     

煤沥青的最新研究进展

综述了最近几十年国内外对煤沥青的主要分析方法和以它为原料在制备沥青基中间相、中间相炭微球、针状焦、活性炭、泡沫炭和高性能炭/炭复合材料基体方面的研究和进展,展望了其在材料领域潜在的应用前景和未来发展的趋势.     

Performance evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical capacitors

A ternary composite of CNT/polypyrrole/hydrous MnO₂ is prepared by in situ chemical method and its electrochemical performance is evaluated by using cyclic voltammetry (CV), impedance measurement and constant-current charge/discharge cycling techniques. For comparative purpose, binary composites such as CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ are prepared and also investigated for their physical and electrochemical performances. The specific capacitance (SC) values of the ternary composite, CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ binary composites estimated by CV technique in 1.0 M Na₂SO₄ electrolyte are 281, 150 and 35 F g⁻¹ at 20 mV s⁻¹ and 209, 75 and 7 F g⁻¹ at 200 mV s⁻¹, respectively. The electrochemical stability of ternary composite electrode is investigated by switching the electrode back and forth for 10,000 times between 0.1 and 0.9 V versus Ag/AgCl at 100 mV s⁻¹. The electrode exhibits good cycling stability, retaining up to 88% of its initial charge at 10,000th cycle. A full cell assembled with the ternary composite electrodes shows a SC value of 149 F g⁻¹ at a current loading of 1.0 mA cm⁻² during initial cycling, which decreased drastically to a value of 35 F g⁻¹ at 2000th cycle. Analytical techniques such as scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), Brunauer-Emmet-Teller (BET) surface area measurement and inductively coupled plasma-atomic emission spectrometry (ICP-AES) are also used to characterize the composite materials.     

Characterization of pistachio shell-derived carbons activated by a combination of KOH and CO2 for electric double-layer capacitors

The micropores and surface oxygen functional groups of KOH-activated carbons were respectively extended and desorbed by the gasification of CO₂ during the activation process of chars derived from pistachio shells. These activated carbons (ACs) were found to exhibit ideal capacitive performances (i.e., a rectangular shape of CVs at a wide range of scan rates, high power property, and excellent reversibility) in aqueous electrolytes for electric double-layer capacitors. Although the specific capacitance of these ACs measured at a low scan rate (25 mV s⁻¹) is decreased with reducing the density of surface functional groups, the ideal capacitive characteristics can be maintained at a much higher scan rate (300 mV s⁻¹) when the CO₂ gasification time is equal to or longer than 30 min because of the relatively high proportion of mesopores.     

Coating of graphite anode with coal tar pitch as an effective precursor for enhancing the rate performance in Li-ion batteries: Effects of composition and softening points of coal tar pitch

Effects of compositions and softening points of coal tar pitches (CTPs) on the electrochemical performances especially for first cycle Coulombic efficiency and rate performance, of the amorphous carbon coating on the graphite surface were closely examined. CTPs with higher softening points could afford the better homogeneous amorphous carbon coating on the graphite surface, resulting in the better enhancing rate performance of graphite anode without decreasing the first cycle Coulombic efficiency. CTP with almost complete absence of hexane soluble (HS) fraction always showed the good enhancing effect of the rate performance. HS fraction of CTP, which is a reason for inducing surface defects on the coated carbon, hindered the enhancing effect of electrochemical performances. CTP derived amorphous carbon coating could effectively decrease charge transfer resistance on the graphite electrode–electrolyte interface.     

Preparation and electrochemistry of NiO/SiNW nanocomposite electrodes for electrochemical capacitors

This paper studies nickel oxide/silicon nanowires (NiO/SiNWs) as composite thin films in electrodes for electrochemical capacitors. The SiNWs as backbones were first prepared by chemical etching, and then the Ni/SiNW composite structure was obtained by electroless plating of nickel onto the surface of the SiNWs. Next, the NiO/SiNW nanocomposites were fabricated by annealing Ni/SiNW composites at different temperatures in an oxygen atmosphere. Once the electrodes were constructed, the electrochemical behavior of these electrodes was investigated with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In 2 M KOH solution, the electrode material was found to have novel capacitive characteristics. Finally, when the NiO/SiNW composites were annealed at 400 °C, the maximum specific capacitance value was found to be as high as 681 F g⁻¹ (or 183 F cm⁻³), and the probing of the cycling life indicated that only about 3% of the capacity was lost after 1000 charge/discharge cycles. This study demonstrated that NiO/SiNW composites were the optimal electrode choice for electrochemical capacitors.     

循环伏安法制备聚苯胺/活性炭超级电容器膜电极

采用电化学循环伏安法,在柔性石墨纸基底材料上合成了聚苯胺/活性炭(PANI/AC)复合薄膜。 通过SEM观察了不同扫描圈数下复合薄膜的表面形貌,通过循环伏安(CV)、交流阻抗(EIS)、恒流充放电等电化学测试方法,研究了聚苯胺/活性炭复合电极的电性能。由SEM图谱可知,不同扫描圈数下,聚苯胺/活性炭的形态也有所不同,电化学测试结果表明,以柔性石墨纸为基底材料,扫描圈数在3圈时,不仅比容量较高,达504 F·g^-1,而且循环稳定性较好,经2000次循环后,容量衰减仅为初始容量的14%。     

Intensification of low-grade methane enrichment in nitrogen mixture by CH4/CO2 displacement

To solve the problem of CO₂ uncompleted desorption in the process of CO₂ displacement enhancing the adsorption separation of CH₄/N₂, a small amount of product gas CH₄ was used as purge gas to improve the CO₂ desorption. CH₄/CO₂ mixture gas obtained from desorption step was recycled as the displacement gas to enhance the enrichment of low-grade methane in nitrogen mixture. In this work, the research conducted the experiments for CH₄/N₂ separation using CH₄/CO₂ displacement intensification adsorption and the laboratory-made coconut shell activated carbon as sorbent. The mathematical models were built in gPROMS and the accuracy of models was verified by comparison of simulations and CH₄/N₂/CO₂ breakthrough experiments. The performance of enrichment of low-grade methane with displacement intensification using different displacer was compared. The result showed that the process with CH₄/CO₂ displacement had higher purity product than CO₂ displacement. The CH₄/ CO₂ mixed gas replacement enhanced vacuum pressure swing adsorption cycle experiment was carried out, which can jointly enrich 14% CH₄/ N₂ and 53% CH₄/CO₂ to 98.8%, and at the same time obtain a recovery rate of 77.8%.     

CH4/CO2混合气置换强化含氮低品质甲烷的浓缩

针对CO₂置换吸附分离CH₄/N₂过程中CO₂再生困难的问题,采用少量产品气CH₄真空吹扫以提高CO₂的解吸效果,并以解吸得到的CH₄/CO₂混合气为置换步骤的置换气,通过置换来强化含氮低品质甲烷的浓缩过程。以自制椰壳活性炭为吸附剂,对CH₄/CO₂混合气置换强化吸附回收含氮低品质甲烷工艺过程进行了实验与模拟研究。在gPROMS软件中建立并求解固定床吸附分离模型方程,预测了CH₄、N₂ 和CO₂在自制椰壳活性炭上的竞争吸附穿透曲线,通过预测结果和实验的对比,验证了数学模型方程的准确性。对比了不同置换气强化吸附分离低品质甲烷的效果,结果表明CH₄/CO₂混合气置换强化相对于CO₂置换强化可获得更高纯度产品。进行了CH₄/CO₂混合气置换强化真空变压吸附循环实验,可以将14%的CH₄/N₂和53%的CH₄/CO₂联合富集到98.8%,同时获得77.8%的回收率。     

Synthesis and enhanced supercapacitor performance of carbon self-doping graphitic carbon nitride/NiS electrode material

The thermal oxidation carbon self-doped graphitic carbon nitride/NiS (TC-g-C₃N₄/NiS) composites with high electrochemical performance were synthesized by combining nickel sulfide with carbon self-doping carbon nitride through a hydrothermal method. The graphitic carbon nitride (g-C₃N₄) could improve charge fluidity by carbon self-doping process, and be etched by further heat treatment, which provides conditions for the introduction of NiS particles. NiS particles uniformly adhered to the layers of g-C₃N₄, thus avoiding particle aggregation. The as-prepared active composite maintains high specific capacitance (1162 F/g at the current density of 1 A·g⁻¹) and shows great cycle stability (capacitance retention rate of 82.0% after 8000 cycles). The conductivity of active composite has also been improved. Moreover, the assembled TC-g-C₃N₄/NiS//AC exhibit a relatively high-energy density of 27 Wh/kg and exhibits excellent cycling performance with a capacity retention rate of 87.9% after 8000 cycles. Hence one can see that TC-g-C₃N₄/NiS composites have broad application prospects in the field of supercapacitors.     

Electrochemical properties of MnO2/CNT nanocomposite in neutral aqueous electrolyte as cathode material for asymmetric supercapacitors

A MnO₂/carbon nanotube (CNT) nanocomposite was synthesised using a simple hydrothermal treatment. The nanocomposite exhibits a CNT core/MnO₂ porous sheath hierarchy architecture, which makes it promising as an electrode material for supercapacitors. An asymmetric supercapacitor based on activated carbon (AC) as anode, MnO₂/CNT nanocomposite as cathode and 1M Na₂SO₄ solution as electrolyte was assembled in a Swagelok cell. The full cell exhibits excellent power capability, cycling stability and a high energy density of 23 W h/kg at a power density of 330 W/kg based on the total mass of the active electrode materials. This AC//MnO₂/CNT asymmetric supercapacitor is promising for high-power applications due to its high energy density and power density.     

炭/炭复合材料用浸渍剂煤沥青研究进展

本文介绍了炭/炭复合材料用浸渍剂煤沥青的结构组成与性能特点,分析了影响煤沥青浸渍性能的关键因素,总结对比了近几年浸溃用煤沥青改性方法的优缺点.指出煤沥青的开发和生产应该兼顾残炭率、流动性、黏度和软化点等因素,从而减少浸渍次数,降低炭/炭复合材料的生产成本.     

缺氧/好氧膜-生物反应器处理高浓度含碳和氮工业废水

采用缺氧 /好氧膜 生物反应器 (MBR)处理高浓度含碳和氮工业废水 ,在缺氧反应器的水力停留时间 (HRT)为 5h ,好氧MBR的HRT分别为 1 5、1 0、6h时 ,考察了系统的同时除碳脱氮性能。结果表明 ,好氧MBR的HRT在试验范围内对系统的处理效果没有明显影响 ,即使MBR的HRT降低到 6h,系统对化学需氧量 (COD)、氨氮和总氮的去除率仍可达到 94%、90 %和 73 %以上 ,出水水质达到国家一级排放标准 ;系统中的生物反应对有机物和氮的去除起主要作用 ,但膜对混合液上清液COD有一定去除 ,主要对相对分子质量大于 1 0万的有机物有截留 ;由于膜的高效截留作用 ,MBR中可保持高浓度的污泥量和高硝化活性 ,确保了硝化反应的高效进行     

Li2MnSiO4/C复合材料的制备与性能表征

本文分别以柠檬酸(C6H8O7·H2O)和蔗糖(C12 H22 O11)为碳源,采用溶胶凝胶法合成了Li2 MnSiO4/C材料.X射线衍射(XRD)结果显示合成出的Li2 MnSiO4/C材料均属于正交晶系Pmn21空间群.扫描电子显微镜(SEM)结果表明合成出的Li2 MnSiO4/C1(以C6H8O7·H2O为碳源)材料粒径均在500 nm左右,Li2MnSiO4/C2(以C12 H22O11为碳源)材料粒径在1μn左右.充放电测试结果显示,Li2MnSiO4/C2较Li2 MnSiO4/C1有较高的首次不可逆容量;两种电极材料经几周循环后均具有稳定的循环性能,所制得的Li2 MnSiO4/C1较Li2 MnSiO4/C2具有高的循环容量.     

Synthesis and electrochemical properties of two types of highly ordered mesoporous MnO2

Mesoporous MnO₂ with uniform nanorod morphology and mesoporous β-MnO₂ were prepared using SBA-15 and KIT-6 as the templates, respectively. XRD, nitrogen adsorption analysis, SEM, TEM and EDX techniques were used for the structural characterization. The electrochemical properties of the MnO₂ samples were studied using alkaline Zn/MnO₂ batteries in a 9 M KOH electrolyte solution. Compared to the commercial electrolytic manganese dioxide (EMD), the discharge capacity of the mesoporous MnO₂ nanorods increased by 74.98%, 119.74% and 146.19% at constant currents of 50, 250 and 500 mA g⁻¹, respectively, while the discharge capacity of the mesoporous β-MnO₂ increased by 63.58%, 95.14% and 100.23%.     

在超细催化剂CuO/ZnO/SiO_2上CO_2加氢合成甲醇的优化研究

本文考察了焙烧温度、还原温度、反应温度、反应压力和体积空速对用于ＣＯ２加氢反应的超细ＣｕＯ／ＺｎＯ／ＳｉＯ２催化剂性能和产物分布的影响，确定了催化剂的合适焙烧温度、还原温度，并对ＣＯ２加氢反应条件进行了优化