CN103274394A - Method for preparing graphene by thermal decomposition - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005979 thermal decomposition reaction Methods 0.000 title abstract description 3
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 239000005715 Fructose Substances 0.000 claims description 3
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- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
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- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
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- 239000002243 precursor Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种利用热分解前驱体直接制备石墨烯粉体的方法。该制备方法以糖类碳氢化合物为石墨烯的碳源，三聚氰胺等为模板剂，将碳源和模板剂混合均匀后，在一定的反应温度和反应时间下进行反应，得到石墨烯。碳源与模板剂质量比优选在1：1-1：100之间；反应温度优选在400-1200°C之间；反应时间优选在0.1-24小时之间；碳源选择较为广泛。本发明用于制备石墨烯，其优势在于：步骤简单，易于操作，适合大规模工业化生产；原料来源广泛，产物纯度高，无副产物，无需分离提纯工艺，工艺环保且产率高。
The invention discloses a method for directly preparing graphene powder by utilizing a thermal decomposition precursor. In the preparation method, sugar hydrocarbons are used as the carbon source of the graphene, melamine and the like are used as the template agent, the carbon source and the template agent are uniformly mixed, and the reaction is carried out at a certain reaction temperature and reaction time to obtain the graphene. The mass ratio of carbon source to templating agent is preferably between 1:1-1:100; the reaction temperature is preferably between 400-1200°C; the reaction time is preferably between 0.1-24 hours; the choice of carbon source is relatively wide. The invention is used to prepare graphene, and its advantages are: simple steps, easy operation, suitable for large-scale industrial production; wide source of raw materials, high product purity, no by-products, no separation and purification process, environmentally friendly process and high yield.
Description
技术领域 technical field
本发明属于碳材料制备技术领域，涉及一种碳氢化合物热分解制备石墨烯的方法。 The invention belongs to the technical field of carbon material preparation, and relates to a method for preparing graphene by thermal decomposition of hydrocarbons.
背景技术 Background technique
石墨烯（Graphene）是一种新型两维结构的碳材料，由sp2碳原子紧密排列形成蜂巢状结构，是一种最新发现的碳的单质材料。石墨烯是目前所知的最薄、机械强度最大的材料，具有优良的导电、导热能力和光学性能。石墨烯的这些优良性能使其在众多领域都有潜在的应用前景，成为近期材料研究的热点。 Graphene (Graphene) is a new type of two-dimensional carbon material, which is closely arranged by sp 2 carbon atoms to form a honeycomb structure. It is a newly discovered elemental material of carbon. Graphene is the thinnest material with the greatest mechanical strength known so far, and has excellent electrical and thermal conductivity and optical properties. These excellent properties of graphene make it have potential application prospects in many fields, and become a hot spot in recent materials research.
石墨烯的研究和应用对其制备方法提出了迫切要求。目前石墨烯的制备方法主要有微机械剥离法、热膨胀石墨法、氧化石墨还原法和气相化学沉积法等方法。其中，微机械剥离法和热膨胀石墨法效率低、产量小，只能限于实验室小规模实验；氧化石墨还原法虽然可大批量制备，但氧化还原过程引入大量缺陷，严重影响其物理及化学性能，特别是导电性能；气相化学沉积法工艺复杂，制备条件苛刻，不适于大批量低成本生产。因此，目前低成本获得大批量的石墨烯产品还存在一定困难。 The research and application of graphene put forward urgent requirements for its preparation method. At present, the preparation methods of graphene mainly include micromechanical exfoliation method, thermal expansion graphite method, graphite oxide reduction method and vapor phase chemical deposition method. Among them, the micromechanical exfoliation method and the thermal expansion graphite method have low efficiency and small output, which can only be limited to small-scale experiments in the laboratory; although the graphite oxide reduction method can be prepared in large quantities, the oxidation-reduction process introduces a large number of defects, which seriously affects its physical and chemical properties. , especially the electrical conductivity; the vapor phase chemical deposition process is complicated, the preparation conditions are harsh, and it is not suitable for mass production at low cost. Therefore, it is still difficult to obtain large quantities of graphene products at low cost.
发明内容 Contents of the invention
本发明的目的是提供一种操作简单、环境友好、转化率高的可用于大规模工业生产制备石墨烯的方法。 The object of the present invention is to provide a method for preparing graphene that is simple to operate, environmentally friendly and has a high conversion rate and can be used in large-scale industrial production.
本发明所提供的石墨烯制备方法是将碳源与模板剂加热分解直接制备石墨烯粉体，包括以下步骤： The graphene preparation method provided by the present invention is to directly prepare graphene powder by thermally decomposing a carbon source and a template agent, comprising the following steps:
（1）将碳源和模板剂按照质量比1：1至1：100研磨混合均匀； (1) Grind and mix the carbon source and template evenly according to the mass ratio of 1:1 to 1:100;
（2）碳源可选择葡萄糖、果糖、麦芽糖等化学式为Cn(H2O)m的糖类化合物； (2) The carbon source can be glucose, fructose, maltose and other sugar compounds with the chemical formula Cn(H 2 O)m;
（3）模板剂可选择三聚氰胺、二聚氰胺、尿素、碳酸氢铵等加热后可完全分解的固体化合物； (3) The templating agent can choose melamine, dicyandiamide, urea, ammonium bicarbonate and other solid compounds that can be completely decomposed after heating;
（4）将碳源和模板剂混合均匀后，加热至400-1200°C，反应0.1-24小时后，冷却至室温得到石墨烯产物。 (4) After mixing the carbon source and template evenly, heat to 400-1200°C, react for 0.1-24 hours, and cool to room temperature to obtain a graphene product.
本发明使用糖类化合物为碳源制备石墨烯，通过拉曼、XRD、比表面测量、透射电镜等分析方法，对产物进行了表征，证明了通过本方法可以制备石墨烯粉体。 The present invention uses sugar compounds as carbon sources to prepare graphene, and characterizes the product through analysis methods such as Raman, XRD, specific surface measurement, and transmission electron microscopy, and proves that graphene powder can be prepared by this method.
本发明提供了一种制备石墨烯的方法，与常规方法相比，此制备方法具有以下优点： The invention provides a kind of method for preparing graphene, compared with conventional method, this preparation method has the following advantages:
（1）步骤简单，易于操作，适合大规模工业化生产； (1) The steps are simple, easy to operate, and suitable for large-scale industrial production;
（2）原料来源广泛，可选择种类多； (2) The source of raw materials is wide, and there are many types to choose from;
（3）产率较高，无副产物，无分离提纯步骤； (3) High yield, no by-products, no separation and purification steps;
（4）反应条件相对温和，常压反应，能耗低。 (4) The reaction conditions are relatively mild, the reaction is under normal pressure, and the energy consumption is low.
附图说明 Description of drawings
图1为本发明实施例1制备的石墨烯产物的拉曼光谱图。 Fig. 1 is the Raman spectrogram of the graphene product prepared in Example 1 of the present invention.
图2为本发明实施例1制备的石墨烯产物的XRD谱图。 Figure 2 is the XRD spectrum of the graphene product prepared in Example 1 of the present invention.
图3为本发明实施例1制备的石墨烯产物的透射电镜照片。 3 is a transmission electron micrograph of the graphene product prepared in Example 1 of the present invention.
图4为本发明实施例2制备的石墨烯产物的拉曼光谱图。 Fig. 4 is the Raman spectrogram of the graphene product prepared in Example 2 of the present invention.
图5为本发明实施例2制备的石墨烯产物的XRD谱图。 Figure 5 is the XRD spectrum of the graphene product prepared in Example 2 of the present invention.
图6为本发明实施例2制备的石墨烯产物的透射电镜照片。 6 is a transmission electron micrograph of the graphene product prepared in Example 2 of the present invention.
图7为本发明实施例3制备的石墨烯产物的拉曼光谱图。 Fig. 7 is the Raman spectrogram of the graphene product prepared in Example 3 of the present invention.
图8为本发明实施例3制备的石墨烯产物的XRD谱图。 Figure 8 is the XRD spectrum of the graphene product prepared in Example 3 of the present invention.
图9为本发明实施例4制备的石墨烯产物的拉曼光谱图。 Fig. 9 is a Raman spectrogram of the graphene product prepared in Example 4 of the present invention.
图10为本发明实施例4制备的石墨烯产物的XRD谱图。 Figure 10 is the XRD spectrum of the graphene product prepared in Example 4 of the present invention.
具体实施方式 Detailed ways
下面通过具体实施例对本发明做进一步说明。 The present invention will be further described below through specific examples.
实施例1： Example 1:
将1.0克葡萄糖和6.0克三聚氰胺研磨混合均匀后，装入坩埚并放入马弗炉中，程序升温至800°C反应2小时，反应结束后自然降温至室温，坩埚中收集产物。在上述条件下，石墨烯的产量为0.4克；拉曼光谱（见图1）显示该样品具有石墨烯材料所具有的G峰、D峰和2D峰；氮气吸附分析显示其比表面积为580m2/g，说明石墨烯产物具有较大的比表面积；从产物的XRD图（见图2）可知，产物具有石墨烯所特有的宽化的衍射峰；图3显示为产物的透射电镜照片，可以清楚看到石墨烯产物为薄纱状。 After 1.0 g of glucose and 6.0 g of melamine were ground and mixed evenly, they were loaded into a crucible and placed in a muffle furnace, and the temperature was programmed to rise to 800° C. for 2 hours. After the reaction, the temperature was naturally cooled to room temperature, and the product was collected in the crucible. Under the above conditions, the output of graphene is 0.4 grams; Raman spectrum (see Figure 1) shows that the sample has G peak, D peak and 2D peak that graphene materials have; nitrogen adsorption analysis shows that its specific surface area is 580m2 /g, indicating that the graphene product has a larger specific surface area; from the XRD pattern (see Figure 2) of the product, it can be seen that the product has a broadened diffraction peak unique to graphene; Figure 3 shows a transmission electron microscope photo of the product, which can be The graphene product is clearly seen as a gauze.
实施例2： Example 2:
将1.0克葡萄糖和40.0克三聚氰胺研磨混合均匀后，装入坩埚并放入马弗炉中，程序升温至800°C反应2小时，反应结束后自然降温至室温，坩埚中收集产物。在上述条件下，石墨烯的产量为0.2克；拉曼光谱（见图4）显示该样品具有石墨烯材料所具有的G峰、D峰和2D峰；氮气吸附分析显示其比表面积为980m2/g，说明石墨烯产物具有较大的比表面积；从产物的XRD图（见图5）可知，产物具有石墨烯所特有的宽化的衍射峰。图6显示为产物的透射电镜照片，可以清楚看到石墨烯产物为薄纱状。 After 1.0 g of glucose and 40.0 g of melamine were ground and mixed evenly, they were loaded into a crucible and placed in a muffle furnace, and the temperature was programmed to rise to 800° C. for 2 hours. After the reaction, the temperature was naturally cooled to room temperature, and the product was collected in the crucible. Under the above conditions, the output of graphene is 0.2 grams; Raman spectrum (see Figure 4) shows that the sample has G peak, D peak and 2D peak that graphene materials have; nitrogen adsorption analysis shows that its specific surface area is 980m2 /g, indicating that the graphene product has a larger specific surface area; from the XRD pattern of the product (see Figure 5), it can be seen that the product has a broadened diffraction peak unique to graphene. Figure 6 shows a transmission electron micrograph of the product, and it can be clearly seen that the graphene product is gauze-like.
实施例3： Example 3:
将1.0克果糖和6.0克三聚氰胺研磨混合均匀后，装入坩埚并放入马弗炉中，程序升温至800°C反应2小时，反应结束后自然降温至室温，坩埚中收集产物。在上述条件下，石墨烯的产量为0.4克；拉曼光谱（见图7）显示该样品具有石墨烯材料所具有特征峰；其比表面积为592m2/g，说明石墨烯产物具有较大的比表面积；产物的XRD图（见图8）显示石墨烯所特有的宽化的衍射峰。 After 1.0 g of fructose and 6.0 g of melamine were ground and mixed evenly, they were loaded into a crucible and placed in a muffle furnace, and the temperature was programmed to rise to 800° C. for 2 hours. After the reaction, the temperature was naturally cooled to room temperature, and the product was collected in the crucible. Under the above conditions, the output of graphene is 0.4 grams; Raman spectrum (see Figure 7) shows that the sample has the characteristic peaks of graphene materials; its specific surface area is 592m 2 /g, indicating that graphene products have larger Specific surface area; the XRD pattern of the product (see Figure 8) shows a broadened diffraction peak unique to graphene.
实施例4： Example 4:
将1.0克葡萄糖和10.0克尿素研磨混合均匀后，装入坩埚并放入马弗炉中，程序升温至800°C反应2小时，反应结束后自然降温至室温，坩埚中收集产物。在上述条件下，石墨烯的产量为0.3克；拉曼光谱（见图9）显示该样品具有石墨烯材料所具有的G峰、D峰和2D峰；其比表面积为520m2/g； XRD图（见图10）显示产物具有石墨烯所特有的宽化的衍射峰。 After 1.0 g of glucose and 10.0 g of urea were ground and mixed evenly, they were loaded into a crucible and placed in a muffle furnace, and the temperature was programmed to rise to 800° C. for 2 hours. After the reaction, the temperature was naturally cooled to room temperature, and the product was collected in the crucible. Under the above conditions, the output of graphene is 0.3 grams; Raman spectrum (see Figure 9) shows that the sample has the G peak, D peak and 2D peak that graphene materials have; its specific surface area is 520m 2 /g; XRD The figure (see Figure 10) shows that the product has broadened diffraction peaks characteristic of graphene.
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| CN105621393A (en) * | 2014-11-28 | 2016-06-01 | 中国科学院大连化学物理研究所 | Functionalized graphene material, and preparation method and application thereof |
| CN108117064A (en) * | 2018-03-01 | 2018-06-05 | 上海理工大学 | A kind of preparation method of fold graphene |
| CN108117064B (en) * | 2018-03-01 | 2021-07-09 | 上海理工大学 | A kind of preparation method of wrinkled graphene |
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