CN111591981B - A kind of preparation method of low-layer tulle-like nitrogen-doped graphene - Google Patents
A kind of preparation method of low-layer tulle-like nitrogen-doped graphene Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于材料制备领域，具体涉及一种低层薄纱状掺氮石墨烯乙醇插层微波嵌入的制备方法及应用。The invention belongs to the field of material preparation, and in particular relates to a preparation method and application of a low-layer gauze-like nitrogen-doped graphene ethanol intercalation microwave embedding.
背景技术Background technique
当下化石能源不断枯竭，由于人口基数大需求也就越来越大，因此新的能源如生物质能、风能、海洋能、核能和太阳能等的发展已迫在眉睫。随着国家对环境问题的越来越重视，研究环保型工艺得到广泛的认可。国家倡导低碳环保，然而发展优异性能的储能器件非常重要，可以应用到太阳能储能板、超级电容器、锂离子电池、燃料电池以及新能源汽车。超级电容器的理想电极材料应具有三个特性：高比电容用于提高能量密度，极好的倍率性能用于维持高功率输出、良好的可逆性满足充放电循环寿命。关于如何高产量获得高质量的石墨烯对未来的开发和应用至关重要。With the continuous depletion of fossil energy and the increasing demand due to the large population base, the development of new energy sources such as biomass energy, wind energy, ocean energy, nuclear energy and solar energy is imminent. As the country pays more and more attention to environmental issues, research on environmentally friendly processes has been widely recognized. The country advocates low carbon and environmental protection, but it is very important to develop energy storage devices with excellent performance, which can be applied to solar energy storage panels, supercapacitors, lithium-ion batteries, fuel cells and new energy vehicles. The ideal electrode material for supercapacitors should have three characteristics: high specific capacitance for improving energy density, excellent rate capability for maintaining high power output, and good reversibility to meet the charge-discharge cycle life. How to obtain high-quality graphene in high yield is crucial for future development and applications.
超级电容器是有潜力发展的高效储能能源，在储能领域由于其优异的电化学性能而吸引广泛的关注。超级电容器设备主要是由工作电极，集电极，电解液，隔膜和包装材料组成。电极材料是影响超级电容器性能最重要的组成部分。碳基材料未来的发展将主要集中在高功率石墨类负极及非石墨类高容量碳负极。这类材料理论容量较大，但在使用的过程中容易出现生产周期长、样品易团聚，制备低层数石墨烯困难的问题，因而制约了它的发展。石墨烯性能的研究实现广泛应用，以可靠、低成本、高品质的方式制备所需要的多孔石墨烯。关于如何改善石墨烯材料性能的工艺条件问题，学术界展开了一系列的研究。Supercapacitors are potential high-efficiency energy storage energy sources, which have attracted extensive attention in the field of energy storage due to their excellent electrochemical properties. Supercapacitor devices are mainly composed of working electrodes, collectors, electrolytes, separators and packaging materials. Electrode material is the most important component that affects the performance of supercapacitors. The future development of carbon-based materials will mainly focus on high-power graphite anodes and non-graphite high-capacity carbon anodes. This kind of material has a large theoretical capacity, but it is prone to problems such as long production cycle, easy agglomeration of samples, and difficulty in preparing low-layer graphene in the process of use, thus restricting its development. The study of graphene properties realizes a wide range of applications to prepare the desired porous graphene in a reliable, low-cost, and high-quality manner. A series of studies have been carried out in the academic community on how to improve the process conditions of graphene material properties.
石墨烯因其极高的导热性和导电性，优异的机械强度和较大的比表面积而在电化学超级电容器中具有巨大的发展潜力。近年来研究中发现石墨烯(Graphene)是一种由碳原子以sp2杂化轨道组成六角型呈蜂巢晶格的二维碳纳米材料。具有硬度高、韧度好、比表面积大、良好的储能材料。但同时也有缺陷，由于π-π强相互作用形成团聚的石墨烯片，不能为电解质离子传导提供足够的通道，从而导致减缓了电容器活性和速率能力。为了解决这个问题，需要对石墨烯的各种功能进行修饰，形成三维掺氮石墨烯气凝胶，多孔且相互连接的三维结构具有较大的比表面积，可促进电解质离子的快速扩散。但实施步骤有待改进及完善，研究反应条件简单易行且能合成的少量产品的工艺。氮掺杂碳材料，将氮原子配合到碳中格子，研究出性能优良的掺杂多孔石墨烯材料对超级电容器的发展至关重要，还可以应用在新能源汽车储能电池。Graphene has great development potential in electrochemical supercapacitors due to its extremely high thermal and electrical conductivity, excellent mechanical strength and large specific surface area. In recent years, it has been found that graphene (Graphene) is a two-dimensional carbon nanomaterial with a hexagonal honeycomb lattice composed of carbon atoms with sp 2 hybrid orbitals. It has high hardness, good toughness, large specific surface area and good energy storage material. However, it also suffers from the drawback that agglomerated graphene sheets due to strong π-π interactions cannot provide sufficient channels for electrolyte ion conduction, resulting in slowed capacitor activity and rate capability. To solve this problem, various functions of graphene need to be modified to form three-dimensional nitrogen-doped graphene aerogels. The porous and interconnected three-dimensional structure has a large specific surface area, which can promote the rapid diffusion of electrolyte ions. However, the implementation steps need to be improved and perfected, and the process of studying the reaction conditions is simple and feasible and can synthesize a small amount of products. Nitrogen-doped carbon materials, which combine nitrogen atoms into carbon lattices, and research on doped porous graphene materials with excellent performance are crucial to the development of supercapacitors, and can also be used in new energy vehicle energy storage batteries.
目前国内外已有不少关于石墨烯材料的制备方法，但不同的制备方法与制备条件对石墨稀的结构性能有很大的影响。当前制备石墨稀的主要方法有微波溶剂热法、化学气相沉积法(CVD)、固相微波辐射法以及热处理法等。尽管CVD法能制备出比表面积大的石墨烯，但其工艺复杂，制备成本高，周期长，并且衬底表面生成的石墨烯转移难度较大。固相微波辐射法直接对石墨的前驱体进行微波加热，将其剥离成单层或多层的石墨烯。由于剥离时间久、前驱体中含氧量高影响剥离效果。而乙醇插层微波嵌入法制备低层多孔氮掺杂石墨烯，成本低、环保、产物能稳定存在于水或有机溶剂当中无需后续的基底转移，为获得少量低层薄纱状掺氮石墨烯材料的开发和工业化应用提供了一种可行的制备方法。At present, there are many preparation methods of graphene materials at home and abroad, but different preparation methods and preparation conditions have a great influence on the structural properties of graphene. At present, the main methods for preparing graphene include microwave solvothermal method, chemical vapor deposition (CVD) method, solid-phase microwave radiation method and thermal treatment method. Although the CVD method can prepare graphene with a large specific surface area, its process is complicated, the preparation cost is high, the cycle is long, and the graphene generated on the surface of the substrate is difficult to transfer. The solid-phase microwave irradiation method directly microwaves the graphite precursor to exfoliate it into single-layer or multi-layer graphene. Due to the long peeling time and the high oxygen content in the precursor, the peeling effect is affected. The ethanol intercalation microwave intercalation method to prepare low-layer porous nitrogen-doped graphene has low cost, environmental protection, and the product can exist stably in water or organic solvents without subsequent substrate transfer. The development and industrial application provides a feasible preparation method.
研究乙醇插层微波嵌入法，通过调节碳-碳平面石墨烯结构内的键。而且石墨烯晶格中的碳被杂原子取代可以防止石墨烯片的重堆并增强法拉第反应的电化学性能。杂原子的掺入还可以改变电子结构和密度。在费米能级上克服了量子纳米碳的电容极限，最终比电容增加。与传统工业方法相比，此方法其生产成本较低，原理简单，操做可行性强，能量产制备低层含氮石墨烯等优点，有着广泛的工业应用前景。目前此方法引起材料的微观结构和性能变化等方面的研究工作开展的还相对较少，对石墨烯改性方面的研究大部分处于探索状态，而在实际的应用方面的研究则相对缓慢。The microwave intercalation method for ethanol intercalation was investigated by tuning the bonds within the carbon-carbon planar graphene structure. Moreover, the replacement of carbon in the graphene lattice by heteroatoms can prevent the recombination of graphene sheets and enhance the electrochemical performance of the Faradaic reaction. The incorporation of heteroatoms can also change the electronic structure and density. The capacitance limit of quantum nanocarbons is overcome at the Fermi level, and finally the specific capacitance increases. Compared with traditional industrial methods, this method has the advantages of low production cost, simple principle, strong operational feasibility, and energy production to prepare low-layer nitrogen-containing graphene, and has broad industrial application prospects. At present, there are relatively few studies on the microstructure and performance changes of materials caused by this method. Most of the research on graphene modification is in the exploratory state, while the research on practical applications is relatively slow.
发明内容SUMMARY OF THE INVENTION
针对现有技术存在的问题，本发明的目的在于提供一种乙醇插层微波嵌入制备低层薄纱状掺氮石墨烯的方法，获得高比容量的多孔掺氮石墨烯材料，将其应用于超级电容器中。In view of the problems existing in the prior art, the purpose of the present invention is to provide a method for preparing low-layer tulle-like nitrogen-doped graphene by ethanol intercalation microwave intercalation, to obtain a porous nitrogen-doped graphene material with high specific capacity, and to apply it to super in the capacitor.
本发明的具体技术方案为：The specific technical scheme of the present invention is:
一种低层薄纱状掺氮石墨烯的制备方法，包括如下步骤：A preparation method of low-layer tulle-like nitrogen-doped graphene, comprising the following steps:
(1)氮掺杂石墨烯的制备：(1) Preparation of nitrogen-doped graphene:
将鳞片石墨与浓硫酸和浓硝酸的混合液按照1:110g/ml混合；并在45℃下搅拌；随后，添加高锰酸钾与石墨质量比为6:1，并且继续搅拌后升温至60℃反应7h后，再继续升温至90℃反应40min；然后将反应后的溶液自然冷却至室温；冷却后的溶液与乙醇插层溶剂按照体积比22:1～1.5混合反应，超声波处理，然后向其中加入二乙醇胺(DEA)与插层后溶液体积比为1～5:100进行掺杂氮，将溶液装进高压反应釜中，加热温度190-220℃，加热8-12h，最后将溶液抽滤，去离子水洗涤重复抽滤至pH＝7为止，冷冻干燥，得到含氮石墨烯；The mixed solution of flake graphite and concentrated sulfuric acid and concentrated nitric acid was mixed according to 1:110g/ml; and stirred at 45 ° C; subsequently, the mass ratio of potassium permanganate and graphite was added to be 6:1, and the temperature was raised to 60 °C after continuing to stir. After 7 hours of reaction at ℃, the temperature was continued to be raised to 90 ℃ for 40 min; then the reacted solution was cooled to room temperature naturally; the cooled solution was mixed with ethanol intercalation solvent according to the volume ratio of 22:1 to 1.5, ultrasonically treated, and then added to the mixture. The volume ratio of the solution after adding diethanolamine (DEA) to the intercalation is 1-5:100 for nitrogen doping, the solution is put into an autoclave, the heating temperature is 190-220 ° C, heating for 8-12 h, and finally the solution is pumped Filter, wash with deionized water and repeat suction filtration until pH=7, freeze-dry to obtain nitrogen-containing graphene;
(2)微波嵌入多孔低层含氮石墨烯的合成：(2) Synthesis of microwave-embedded porous low-layer nitrogen-containing graphene:
将步骤(1)得到的含氮石墨烯放在真空管中，微波炉中嵌入，微波功率为700-800W，反应时间为2-5min，获得多孔含氮石墨烯粉体。The nitrogen-containing graphene obtained in step (1) is placed in a vacuum tube, embedded in a microwave oven, the microwave power is 700-800 W, and the reaction time is 2-5 min to obtain porous nitrogen-containing graphene powder.
其中，所述的石墨是市购的规格为325目石墨粉产品。Wherein, the described graphite is a commercially available graphite powder product with a specification of 325 meshes.
所述的溶液H2SO4质量浓度为98％，硝酸质量浓度为65％，高锰酸钾含量为大于99.5％，二乙醇胺(DEA)含量≥99.0％，乙醇质量分数为99.7％。 The H2SO4 mass concentration of the solution is 98%, the mass concentration of nitric acid is 65%, the content of potassium permanganate is greater than 99.5%, the content of diethanolamine (DEA) is greater than or equal to 99.0%, and the mass fraction of ethanol is 99.7%.
进一步地，所用浓硫酸和浓硝酸按照10:1体积比混合。Further, the used concentrated sulfuric acid and concentrated nitric acid were mixed in a volume ratio of 10:1.
冷却后的溶液与乙醇插层溶剂按照体积比22:1。The cooled solution and the ethanol intercalation solvent are in a volume ratio of 22:1.
二乙醇胺(DEA)与插层后溶液体积比为约1～2:100。The volume ratio of diethanolamine (DEA) to the solution after intercalation is about 1-2:100.
上述方法制得的具有低层薄纱状多孔掺氮石墨烯的应用，将其用于制造纽扣式超级电容器，包括如下步骤：The application of the low-layer tulle-like porous nitrogen-doped graphene obtained by the above method, which is used to manufacture a button-type supercapacitor, comprises the following steps:
(1)电极片的制备：按78:12:10(wt％)称取活性物质含氮石墨烯、导电剂乙炔黑和粘结剂聚四氟乙烯，加入适量去离子水，调成浆状。将浆料均匀涂敷于Φ＝10mm的泡沫镍上(已称重)。真空120℃下干燥1h、压片、称重，备用。(1) Preparation of electrode sheet: Weigh the active material nitrogen-containing graphene, the conductive agent acetylene black and the binder polytetrafluoroethylene according to 78:12:10 (wt%), add an appropriate amount of deionized water, and adjust into a slurry . The slurry was evenly coated on nickel foam with Φ=10mm (weighed). Dry under vacuum at 120 °C for 1 h, press into tablets, weigh, and set aside.
(2)组装纽扣式电容器：在真空手套箱中，将下壳、集流体(泡沫镍)/正电极、隔膜、负电极/集流体(泡沫镍)、垫片、弹簧、适量3mol/L KOH电解液和上壳按此顺序组装成纽扣式超级电容器,以50kg/cm2的压力对超级电容器进行封口。(2) Assemble the button capacitor: in a vacuum glove box, place the lower case, current collector (nickel foam)/positive electrode, diaphragm, negative electrode/current collector (nickel foam), gasket, spring, an appropriate amount of 3mol/L KOH The electrolyte and the upper case were assembled into a button-type supercapacitor in this order, and the supercapacitor was sealed with a pressure of 50kg/ cm2 .
本发明的有益效果为：The beneficial effects of the present invention are:
现有技术中利用微波溶剂热法、化学气相沉积法(CVD)、固相微波辐射法以及热处理法等过程中会出现成本高、生产周期长、样品堆叠，引入杂质多造成导电性差，这本来是一种缺陷，而本发明正好利用生产周期长、石墨烯易堆叠的这种缺陷，利用乙醇插层微波嵌入法在新的反应条件下乙醇插层制备掺氮石墨烯然后微波嵌入合成低层多孔掺氮石墨烯，获得具有高比容量的薄纱状多孔掺氮石墨烯材料。In the prior art, the use of microwave solvothermal method, chemical vapor deposition (CVD), solid-phase microwave radiation method and heat treatment method will cause high cost, long production cycle, sample stacking, and poor conductivity due to the introduction of impurities. It is a defect, and the present invention just takes advantage of the defects of long production cycle and easy stacking of graphene, and uses the ethanol intercalation microwave intercalation method to prepare nitrogen-doped graphene by ethanol intercalation under new reaction conditions, and then microwave intercalation to synthesize low-level porous graphene. Nitrogen-doped graphene, a tulle-like porous nitrogen-doped graphene material with high specific capacity is obtained.
现有技术中，在经过氧化还原法得到的具有掺杂石墨烯只能使其表面多孔容量衰减明显，不能充分保证石墨烯导电性。本发明中通过微波能量使石墨杂化结构中的π电子的移动转化为热能，将前驱体中的含氧官能团以及掺杂的物质快速分解为CO2和H2O气体。当气体产生的压力超过片层间的范德华力时，含氮石墨烯片层之间被剥离获得1-4层多孔掺氮石墨烯。而这种多孔氮掺杂结构的丰富氧化还原活性位点为离子扩散和电子传输提供有效的途径。利用微波嵌入法制得的样品缩短了反应时间，多孔性更明显。低层掺氮石墨烯表现出较纯石墨烯更多优异的性能，呈无序、透明、褶皱的薄纱状，显示出较高的比电容和良好的循环寿命。通过对插层微波嵌入法反应条件的研究，发展了一种简便快捷、低能耗制备高性能石墨烯的方法，在乙醇制备出含氮石墨烯后微波嵌入使其在微波作用下发生雪崩般的脱氧反应。解决制备石墨烯层数高影响导电性能、零带隙影响离子通过速率问题，通过此方法增大了石墨烯片层间距，制备比表面积大的低层多孔高质量掺氮石墨烯薄膜。这种多孔性可以提高物质运输速率而且可以有效的打开石墨烯的能带隙，并将此含氮多孔石墨烯应用于超级电容器电极中，可以提高离子运输速率、电化学性能及稳定性能优良，为新一代储能器件做出一定的贡献。In the prior art, the doped graphene obtained by the redox method can only make the surface porous capacity attenuate significantly, and the electrical conductivity of the graphene cannot be fully guaranteed. In the present invention, the movement of π electrons in the graphite hybrid structure is converted into heat energy by microwave energy, and the oxygen-containing functional groups and doped substances in the precursor are rapidly decomposed into CO 2 and H 2 O gases. When the pressure generated by the gas exceeds the van der Waals force between the sheets, the nitrogen-containing graphene sheets are exfoliated to obtain 1-4 layers of porous nitrogen-doped graphene. The abundant redox active sites of this porous nitrogen-doped structure provide an efficient pathway for ion diffusion and electron transport. The samples prepared by the microwave intercalation method have shortened reaction time and more obvious porosity. Low-layer nitrogen-doped graphene exhibits more excellent properties than pure graphene, in the form of disordered, transparent, wrinkled tulle, showing high specific capacitance and good cycle life. Through the study of the reaction conditions of the intercalation microwave intercalation method, a simple, fast, low-energy-consumption method for preparing high-performance graphene was developed. deoxygenation reaction. To solve the problem that the high number of graphene layers affects the electrical conductivity and the zero band gap affects the ion passage rate, the graphene sheet spacing is increased by this method, and the low-layer porous high-quality nitrogen-doped graphene film with large specific surface area is prepared. This porosity can improve the material transport rate and can effectively open the energy band gap of graphene, and the nitrogen-containing porous graphene can be applied to supercapacitor electrodes, which can improve the ion transport rate, excellent electrochemical performance and stability. Contribute to a new generation of energy storage devices.
整个制备工艺流程简单、材料成本低、易于操作、制得的含氮石墨烯具有多孔且相互连接的三维结构、比表面积大、1-4层薄膜以及较好的导电性，用于超级电容器后，可促进电解质离子的快速扩散，不仅比容量有很大提高，而且稳定性能有所改进。The whole preparation process is simple, the material cost is low, the operation is easy, and the prepared nitrogen-containing graphene has a porous and interconnected three-dimensional structure, a large specific surface area, 1-4 layers of thin films and good conductivity. , which can promote the rapid diffusion of electrolyte ions, not only the specific capacity is greatly improved, but also the stability performance is improved.
附图说明Description of drawings
图1为实施例1的纽扣式电容器组装实物图。FIG. 1 is a physical view of the assembled button capacitor of Example 1. FIG.
图2为材料对比的FE-SEM扫描电镜形貌图。(a)未用乙醇插层的掺氮石墨烯；(b)未掺氮的石墨烯；(c)乙醇插层掺氮石墨烯。Figure 2 is the FE-SEM scanning electron microscope morphology image of the material comparison. (a) N-doped graphene without ethanol intercalation; (b) N-doped graphene; (c) N-doped graphene with ethanol intercalation.
具体实施方式Detailed ways
实施例1Example 1
本实施例的低层薄纱状掺氮石墨烯的制备方法按照以下步骤进行：The preparation method of the low-layer tulle-like nitrogen-doped graphene of the present embodiment is carried out according to the following steps:
(1)掺氮石墨烯的制备：(1) Preparation of nitrogen-doped graphene:
将2.0g的鳞片石墨与220ml的浓硫酸和浓硝酸按照10:1体积比混合，并在45℃下搅拌30min。随后，添加12.0g高锰酸钾与石墨质量比为6:1，并且继续搅拌40min后升温60℃反应7h后再继续升温90℃反应40min。然后将反应后的溶液自然冷却至室温。冷却后的溶液与乙醇插层溶剂按照体积比22:1混合反应，超声波处理20分钟，然后向其中加入二乙醇胺(DEA)与溶液体积比为1:100进行掺杂氮，将溶液装进反应釜中200℃加热12h，最后将溶液抽滤，去离子水洗涤重复抽滤至pH＝7为止，冷冻干燥，得到含氮石墨烯；2.0 g of flake graphite was mixed with 220 ml of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 10:1, and stirred at 45° C. for 30 min. Subsequently, 12.0 g of potassium permanganate and graphite were added in a mass ratio of 6:1, and the temperature was increased for 40 minutes, followed by a reaction at 60 °C for 7 hours, and then continued at a temperature of 90 °C for 40 minutes. Then, the reacted solution was naturally cooled to room temperature. The cooled solution and the ethanol intercalation solvent were mixed and reacted according to the volume ratio of 22:1, ultrasonically treated for 20 minutes, and then diethanolamine (DEA) was added to the solution in a volume ratio of 1:100 to carry out nitrogen doping, and the solution was loaded into the reaction. Heating at 200°C for 12h in the kettle, finally filtering the solution, washing with deionized water and repeating suction filtration until pH=7, freeze-drying to obtain nitrogen-containing graphene;
(2)微波嵌入多孔低层含氮石墨烯的合成：(2) Synthesis of microwave-embedded porous low-layer nitrogen-containing graphene:
将第(1)步得到的含氮石墨烯(NG)放在真空管中，微波炉中所用的微波功率为750W，反应时间为3min，获得多孔含氮石墨烯粉体。The nitrogen-containing graphene (NG) obtained in step (1) was placed in a vacuum tube, the microwave power used in the microwave oven was 750W, and the reaction time was 3 min to obtain porous nitrogen-containing graphene powder.
其中，所述的石墨是市购的规格为325目石墨粉产品。Wherein, the described graphite is a commercially available graphite powder product with a specification of 325 meshes.
所述的溶液H2SO4质量浓度为98％，硝酸质量浓度为65％，高锰酸钾含量为大于99.5％，二乙醇胺(DEA)含量≥99.0％，乙醇质量分数为99.7％。 The H2SO4 mass concentration of the solution is 98%, the mass concentration of nitric acid is 65%, the content of potassium permanganate is greater than 99.5%, the content of diethanolamine (DEA) is greater than or equal to 99.0%, and the mass fraction of ethanol is 99.7%.
在经过步骤(2)后最终得到的薄纱状多孔掺氮石墨烯中具有良好的电子及离子迁移性，可应用于制备电容器电极材料。如图2所示，FE-SEM电镜图分析石墨烯的微观形貌。图a可以看出未使用乙醇插层的掺氮石墨烯团聚现象严重，图b显示未掺氮的石墨烯分层未分开，层片堆叠。图c显示乙醇插层掺氮石墨烯片层呈薄纱状，层片之间的间距变大，表面积展开层片分层效果非常好。而且氮掺入后，观察到与未掺氮石墨烯相同的形态，表明掺杂前后表面微观结构得以保留。The gauze-like porous nitrogen-doped graphene finally obtained after the step (2) has good electron and ion mobility, and can be used for preparing capacitor electrode materials. As shown in Figure 2, the FE-SEM electron microscope image analyzes the microscopic morphology of graphene. Figure a shows that the nitrogen-doped graphene without ethanol intercalation has serious agglomeration, and Figure b shows that the layers of the undoped graphene are not separated and the layers are stacked. Figure c shows that the ethanol-intercalated nitrogen-doped graphene sheets are in the shape of gauze, the spacing between the sheets becomes larger, and the surface area expansion of the sheets has a very good delamination effect. Moreover, after nitrogen doping, the same morphology as that of undoped graphene was observed, indicating that the surface microstructure was preserved before and after doping.
本实施例的薄纱状掺氮多孔石墨烯的应用是将其用于制造纽扣式超级电容器，具体按照以下步骤进行，纽扣式电容器组装实物图如图1所示：The application of the tulle-shaped nitrogen-doped porous graphene in this embodiment is to use it to manufacture a button-type supercapacitor, which is specifically carried out according to the following steps. The physical diagram of the button-type capacitor assembly is shown in Figure 1:
(1)电极片的制备：按78:12:10(wt％)称取活性物质含氮石墨烯、导电剂乙炔黑和粘结剂聚四氟乙烯，加入适量去离子水，调成浆状。将浆料均匀涂敷于Φ＝10mm的泡沫镍上(已称重)。真空120℃下干燥1h、压片、称重，备用。(1) Preparation of electrode sheet: Weigh the active material nitrogen-containing graphene, the conductive agent acetylene black and the binder polytetrafluoroethylene according to 78:12:10 (wt%), add an appropriate amount of deionized water, and adjust into a slurry . The slurry was evenly coated on nickel foam with Φ=10mm (weighed). Dry under vacuum at 120 °C for 1 h, press into tablets, weigh, and set aside.
(2)组装纽扣式电容器：在真空手套箱中，将下壳、集流体(泡沫镍)/正电极、隔膜、负电极/集流体(泡沫镍)、垫片、弹簧、适量3mol/L KOH电解液和上壳按此顺序组装成纽扣式超级电容器,以50kg/cm2的压力对超级电容器进行封口。(2) Assemble the button capacitor: in a vacuum glove box, place the lower case, current collector (nickel foam)/positive electrode, diaphragm, negative electrode/current collector (nickel foam), gasket, spring, an appropriate amount of 3mol/L KOH The electrolyte and the upper case were assembled into a button-type supercapacitor in this order, and the supercapacitor was sealed with a pressure of 50kg/ cm2 .
实施例2Example 2
(1)掺氮石墨烯的制备：(1) Preparation of nitrogen-doped graphene:
将2.0g的鳞片石墨与220ml的浓硫酸和浓硝酸按照10:1体积比混合，并在45℃下搅拌30min。随后，添加12.0g高锰酸钾与石墨质量比为6:1，并且继续搅拌40min后升温60℃反应7h后再继续升温90℃反应40min。然后将反应后的溶液自然冷却至室温。冷却后的溶液与乙醇插层溶剂按照体积比22:1.5混合反应，超声波处理30分钟，然后向其中加入二乙醇胺(DEA)与溶液体积比为2:100进行掺杂氮，将溶液装进反应釜190℃加热10h，最后将溶液抽滤，去离子水洗涤重复抽滤至pH＝7为止，冷冻干燥，得到含氮石墨烯；2.0 g of flake graphite was mixed with 220 ml of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 10:1, and stirred at 45° C. for 30 min. Subsequently, 12.0 g of potassium permanganate and graphite were added in a mass ratio of 6:1, and the temperature was increased for 40 minutes, followed by a reaction at 60 °C for 7 hours, and then continued at a temperature of 90 °C for 40 minutes. Then, the reacted solution was naturally cooled to room temperature. The cooled solution and the ethanol intercalation solvent are mixed and reacted according to the volume ratio of 22:1.5, ultrasonically treated for 30 minutes, and then diethanolamine (DEA) is added to the solution in a volume ratio of 2:100 to carry out nitrogen doping, and the solution is loaded into the reaction. The kettle was heated at 190 °C for 10 h, and finally the solution was suction filtered, washed with deionized water, and repeatedly suction filtered until pH=7, and freeze-dried to obtain nitrogen-containing graphene;
(2)微波嵌入多孔低层含氮石墨烯的合成：(2) Synthesis of microwave-embedded porous low-layer nitrogen-containing graphene:
将第(1)步得到的含氮石墨烯(NG)放在真空管中，微波炉中所用的微波功率为800W，反应时间为2min，获得多孔含氮石墨烯粉体。The nitrogen-containing graphene (NG) obtained in step (1) was placed in a vacuum tube, the microwave power used in the microwave oven was 800W, and the reaction time was 2min to obtain porous nitrogen-containing graphene powder.
其中，所述的石墨是市购的规格为325目石墨粉产品。Wherein, the described graphite is a commercially available graphite powder product with a specification of 325 meshes.
所述的溶液H2SO4质量浓度为98％，硝酸质量浓度为65％，高锰酸钾含量为大于99.5％，二乙醇胺(DEA)含量≥99.0％，乙醇质量分数为99.7％。 The H2SO4 mass concentration of the solution is 98%, the mass concentration of nitric acid is 65%, the content of potassium permanganate is greater than 99.5%, the content of diethanolamine (DEA) is greater than or equal to 99.0%, and the mass fraction of ethanol is 99.7%.
在经过步骤(2)后最终得到的薄纱状多孔掺氮石墨烯中具有良好的电子及离子迁移性，可应用于制备锂离子电池电极材料。The gauze-like porous nitrogen-doped graphene finally obtained after the step (2) has good electron and ion mobility, and can be applied to the preparation of lithium-ion battery electrode materials.
本实施例的薄纱状掺氮多孔石墨烯的应用是将其用于制造扣式锂离子电池，具体按照以下步骤进行：The application of the tulle-shaped nitrogen-doped porous graphene of the present embodiment is to use it to manufacture a button-type lithium ion battery, which is specifically carried out according to the following steps:
(1)制电极片：使用涂浆法进行电极制备，将活性材料氮掺杂石墨烯，乙腈黑，粘结剂PVDF按照质量比8:1:1的比例溶解在NMP中，搅拌约30min，制成浆状，然后用刀片小心地将电极材料浆液平整均匀的涂抹在载流体铜箔上。然后在真空烘干箱中80℃处理8h，烘干后压制成电极片。(1) Electrode preparation: Electrode preparation was carried out by slurry coating method. The active material nitrogen-doped graphene, acetonitrile black, and the binder PVDF were dissolved in NMP according to the mass ratio of 8:1:1, and stirred for about 30 minutes. Make a slurry, and then use a blade to carefully spread the electrode material slurry evenly and evenly on the copper foil of the carrier fluid. Then, it was treated in a vacuum drying box at 80°C for 8 hours, and dried and pressed into electrode sheets.
(2)组装纽扣电池：在真空手套箱中，利用电池壳，用金属锂片作为正电极，将正极壳、电极片、隔膜、弹簧片、锂片、垫片、适量电解液溶液和负极壳按此顺序组装成纽扣电池，使用手动封口机对电池进行封口处理。(2) Assemble the button battery: In the vacuum glove box, use the battery shell, use the metal lithium sheet as the positive electrode, and assemble the positive electrode shell, electrode sheet, separator, spring sheet, lithium sheet, gasket, appropriate amount of electrolyte solution and negative electrode shell. Assemble the button battery in this order, and use the manual sealing machine to seal the battery.
Claims (5)
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