WO2023087135A1 - Method for preparing graphene - Google Patents

Method for preparing graphene Download PDF

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WO2023087135A1
WO2023087135A1 PCT/CN2021/130865 CN2021130865W WO2023087135A1 WO 2023087135 A1 WO2023087135 A1 WO 2023087135A1 CN 2021130865 W CN2021130865 W CN 2021130865W WO 2023087135 A1 WO2023087135 A1 WO 2023087135A1
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graphene
hydrogen peroxide
preparing graphene
expanded graphite
graphite
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PCT/CN2021/130865
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French (fr)
Chinese (zh)
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梁亚涛
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广东聚石化学股份有限公司
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Priority to PCT/CN2021/130865 priority Critical patent/WO2023087135A1/en
Publication of WO2023087135A1 publication Critical patent/WO2023087135A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation

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  • the invention belongs to the technical field of graphene, in particular to a method for preparing graphene.
  • Graphene is a single layer of carbon atoms composed of sp2 hybrid orbitals in a hexagonal honeycomb lattice.
  • Graphene is the basic unit for constructing other dimensional carbon materials. When its existence mode changes, it can form fullerenes, carbon nanotubes, graphite, etc., respectively.
  • Graphene has excellent electrical, optical, mechanical and other properties, in addition to excellent thermal conductivity and high charge carrier mobility. Due to these excellent properties, it is used in composite materials, energy, general health, seawater Desalination and many other fields have become research hotspots. The different demands for graphene in many fields have also derived many methods and processes for preparing graphene.
  • Expandable graphite is a crystalline compound that uses physical or chemical methods to insert non-carbonaceous reactants between graphite layers, combine with the hexagonal network plane of carbon, and maintain the graphite layer structure.
  • the interlayer compound When expandable graphite encounters high temperature, the interlayer compound will decompose, generating a thrust along the C-axis direction between the graphite layers, which is much greater than the interlayer binding force of graphite ions, which can push the graphite layers apart to form Vermicular expanded graphite.
  • the interlayer spacing of expanded graphite is larger, the van der Waals force between layers is smaller, and it is easier to exfoliate and prepare graphene.
  • CN107500279A uses expandable graphite as a raw material, graphene quantum dots as a stripping liquid, utilizes a mechanical stripping method and is equipped with a secondary ultrasonic treatment process, thereby realizing batch production and preparation of graphene.
  • the price of graphene quantum dots is much higher than that of graphene.
  • the exfoliated graphene is at the micro-nano level.
  • Graphene quantum dots are well dispersed in the exfoliated graphene system, and the recycling rate is extremely low. Although this method can obtain graphene products simply and quickly, it cannot be produced on a large scale due to the high cost of preparation.
  • CN103950927A Mix expanded graphite and sodium bicarbonate solution, heat up to 190°C and stir for 1.5 hours, then use sodium bicarbonate to decompose to generate carbon dioxide to generate peeling force between expandable graphite sheets, and after carbon dioxide is dissolved in water, the formed Alkaline conditions cause electrostatic repulsion between graphene sheets, thereby forming graphene.
  • the preparation process requires high temperature and high pressure, high energy consumption, and the introduction of sodium bicarbonate is difficult to remove.
  • the object of the present invention is to provide a method for preparing graphene in an environment-friendly manner.
  • the invention provides a kind of method for preparing graphene, and this preparation method comprises the following steps:
  • the particle size of the expandable graphite is 50 mesh to 100 mesh.
  • the expansion ratio of the expandable graphite is 200-400 times; more preferably, the expansion ratio of the expandable graphite is 250-350 times.
  • the carbon content of the expandable graphite is ⁇ 98wt%.
  • the expansion treatment is one or both of thermal expansion treatment and microwave expansion treatment.
  • the thermal expansion treatment refers to heating and expanding the expandable graphite in a nitrogen or inert gas atmosphere, and the heating temperature is 600°C to 800°C, and the expansion treatment The time is 30s to 90s; more preferably, the thermal expansion treatment refers to heating the expandable graphite in a nitrogen atmosphere to 650°C to 750°C for 50s to 70s.
  • step 1) of the method for preparing graphene pulverization is one or more of ball milling, grinding, jet milling.
  • the particle size D50 of the material is pulverized to no greater than 20 ⁇ m; further preferably, the particle size D50 of the material is pulverized to no greater than 10 ⁇ m.
  • step 2) of the method for preparing graphene the mass ratio of expanded graphite powder to hydrogen peroxide is 1: (10-100).
  • the mass percentage of H 2 O 2 in hydrogen peroxide is 5%-50%; further preferably, the mass percentage of H 2 O 2 in hydrogen peroxide is 10%-40%.
  • the time for mixing and stirring is 3 minutes to 10 minutes; more preferably, the time for mixing and stirring is 4 minutes to 6 minutes.
  • the degassing mode is vacuum degassing.
  • the degassing is specifically vacuum degassing at 1-10 kPa for 3 min-10 min.
  • the temperature of ultrasonic peeling is 50°C to 100°C; more preferably, the temperature of ultrasonic peeling is 50°C to 80°C; still more preferably, the temperature of ultrasonic peeling 50°C to 60°C.
  • the ultrasonic peeling time is 0.5h-2h; more preferably, the ultrasonic peeling time is 1h-2h.
  • the power of the ultrasound is 0.5kW-3kW, and the frequency of the ultrasound is 20kHz-60kHz.
  • the thermal decomposition temperature is 100°C-160°C.
  • the time for thermal decomposition is 0.5h-2h; more preferably, the time for thermal decomposition is 1h-2h.
  • step 2) of the method for preparing graphene after ultrasonic stripping, the hydrogen peroxide is decomposed into water and oxygen by heating and heating; in the process of heating and heating, a titration test can be carried out with potassium permanganate solution to detect whether the hydrogen peroxide is decomposed completely.
  • the drying method is spray drying.
  • the present invention also provides a kind of graphene, which is prepared by the above method.
  • the invention provides a method suitable for large-scale production and preparation of graphene, which is green, pollution-free, safe and environment-friendly.
  • the graphene prepared by the method of the invention has the advantages of uniform size, few defects and the like.
  • the present invention uses expandable graphite as raw material. After puffing treatment, the layer spacing of the product is larger than that of flake graphite, the van der Waals force is smaller, and the energy required for peeling is less. Compared with the traditional use of flake graphite or highly oriented pyrolytic graphite, the time is shorter and the stripping efficiency is higher. However, graphite oxide is used as a raw material, and its preparation process is complicated and the cost is high, which is at least 5 times that of expandable graphite.
  • Hydrogen peroxide is used as the stripping solution. Compared with deionized water, the surface tension of hydrogen peroxide is smaller, and it is easier to wet the expanded graphite. Degassing treatment is also carried out, so that hydrogen peroxide can more easily penetrate into the gaps of the expanded graphite to replace the original air, so that the hydrogen peroxide can fully wet the expanded graphite.
  • the hydrogen peroxide slowly decomposes when the temperature rises, and the generated bubbles completely peel off the expanded graphite.
  • the "cavitation effect" generated by the ultrasound is used to cooperate with the bubbles generated by the hydrogen peroxide to completely strip the expanded graphite into graphene.
  • the temperature is raised to completely decompose the hydrogen peroxide, and the graphene is dried to obtain the product.
  • the entire stripping efficiency is efficient and convenient, and there is no discharge of three wastes in the production process, and the stripping efficiency is far better than that of using water or organic solvents.
  • the peeling time is short, and the defects of the obtained product are small, the particle size is more uniform, and the quality is better.
  • Fig. 1 is the sample scanning electron micrograph that embodiment 1 makes
  • FIG. 2 is a scanning electron micrograph of the sample prepared in Comparative Example 1.
  • the graphene preparation method of this example is as follows:
  • the graphene preparation method of this example is as follows:
  • the graphene preparation method of this example is as follows:
  • the sample preparation method of this example is as follows:

Abstract

A method for preparing graphene: 1) subjecting expandable graphite to expansion treatment, and then pulverizing to obtain expanded graphite powder; 2) mixing the expanded graphite powder with hydrogen peroxide and stirring, degassing, performing ultrasonic peeling, heating to decompose hydrogen peroxide, and drying to obtain graphene. The graphene prepared by the described method has the advantages of uniform size, few defects, and so on.

Description

一种制备石墨烯的方法A kind of method for preparing graphene 技术领域technical field
本发明属于石墨烯技术领域，具体涉及一种制备石墨烯的方法。The invention belongs to the technical field of graphene, in particular to a method for preparing graphene.
背景技术Background technique
石墨烯是一种由sp2杂化轨道组成六角型呈蜂巢品格的碳原子单层。石墨烯是构建其他维数碳材料的基本单元，当它的存在方式改变时，可以分别形成富勒烯、碳纳米管和石墨等等。石墨烯具有优异的电学、光学、力学等性能，此外还有优异的导热性能以及极高的电荷载流子迁移率，由于这些优异的性质，使得它在如复合材料、能源、大健康、海水淡化等众多领域成为了研究的热点。众多领域对石墨烯需求的不同，也衍生了许多制备石墨烯的方法和工艺。Graphene is a single layer of carbon atoms composed of sp2 hybrid orbitals in a hexagonal honeycomb lattice. Graphene is the basic unit for constructing other dimensional carbon materials. When its existence mode changes, it can form fullerenes, carbon nanotubes, graphite, etc., respectively. Graphene has excellent electrical, optical, mechanical and other properties, in addition to excellent thermal conductivity and high charge carrier mobility. Due to these excellent properties, it is used in composite materials, energy, general health, seawater Desalination and many other fields have become research hotspots. The different demands for graphene in many fields have also derived many methods and processes for preparing graphene.
常用制备石墨烯的方法主要包括机械剥离法，气相沉积法，外延生长法和氧化还原法，机械剥离法只适合实验室制备石墨烯样品，气相沉积法和外延生长法对设备要技术的要求较高，生产难度较大，氧化还原法虽然可以大量生产，但制备的产品缺陷多，且生产过程中污染严重。后续也有人开发出湿法研磨工艺制备石墨烯，即以鳞片石墨为原料，将其分散在溶剂中，利用机械力将石墨剥离成石墨烯。虽然整个制备过程绿色环保，且得到的石墨烯产品的品质相对也较高，石墨层间的范德华力较大，要制备成石墨烯需要剥离的时间较久，因此导致湿法剥离制备的石墨烯价格居高不下。Commonly used methods for preparing graphene mainly include mechanical exfoliation, vapor deposition, epitaxial growth, and redox methods. Mechanical exfoliation is only suitable for preparing graphene samples in laboratories. Vapor deposition and epitaxial growth have relatively high technical requirements for equipment. High, the production is difficult, although the redox method can be mass-produced, but the prepared products have many defects, and the pollution in the production process is serious. Later, some people also developed a wet grinding process to prepare graphene, that is, using flake graphite as raw material, dispersing it in a solvent, and using mechanical force to peel graphite into graphene. Although the whole preparation process is green and environmentally friendly, and the quality of the obtained graphene product is relatively high, the van der Waals force between the graphite layers is relatively large, and it takes a long time to peel off to prepare graphene, so the graphene prepared by wet exfoliation Prices remain high.
可膨胀石墨是一种利用物理或化学的方法使得非碳质反应物***石墨层间，与炭素的六角网络平面结合的同时又保持了石墨层状结构的晶体化合物。当可膨胀石墨遇到高温时，层间化合物将分解，产生一种沿石墨层间C轴方向的推力，这个推力远大于石墨离子的层间结合力，可以使得石墨层间被推开，形成蠕虫状的膨胀石墨。相对于鳞片石墨而言，膨胀石墨的层间距更大，层与层之间的范德华力更小，更容易剥离制备成石墨烯。Expandable graphite is a crystalline compound that uses physical or chemical methods to insert non-carbonaceous reactants between graphite layers, combine with the hexagonal network plane of carbon, and maintain the graphite layer structure. When expandable graphite encounters high temperature, the interlayer compound will decompose, generating a thrust along the C-axis direction between the graphite layers, which is much greater than the interlayer binding force of graphite ions, which can push the graphite layers apart to form Vermicular expanded graphite. Compared with flake graphite, the interlayer spacing of expanded graphite is larger, the van der Waals force between layers is smaller, and it is easier to exfoliate and prepare graphene.
现有公开的文献中，CN107500279A以可膨胀石墨为原料，石墨烯量子点为剥离液，利用机械剥离法并配有二次超声处理工艺，从而实现批量化生产制备石墨烯。但石墨烯量子点的售价远高于石墨烯的价格，虽然也可以部分回收再利用，但剥离的石墨烯是微纳米级别的。石墨烯量子点在剥离后的石墨烯体系中分散良好，回收利用率极低。虽然该方法可以简单快速的得到石墨烯产品，但受限于制备成本高昂，无法规模化生产。In the existing published literature, CN107500279A uses expandable graphite as a raw material, graphene quantum dots as a stripping liquid, utilizes a mechanical stripping method and is equipped with a secondary ultrasonic treatment process, thereby realizing batch production and preparation of graphene. However, the price of graphene quantum dots is much higher than that of graphene. Although it can also be partially recycled, the exfoliated graphene is at the micro-nano level. Graphene quantum dots are well dispersed in the exfoliated graphene system, and the recycling rate is extremely low. Although this method can obtain graphene products simply and quickly, it cannot be produced on a large scale due to the high cost of preparation.
CN103950927A将膨胀石墨和碳酸氢钠溶液混合后，升温至190℃条件下搅拌1.5h后，利用碳酸氢钠分解产生二氧化碳在可膨胀石墨片层间产生剥离力，而且二氧化碳溶解在水中后，形成的碱性条件使得石墨烯片层间形成静电斥力，从而形成石墨烯。但制备过程中需要高温高压，能耗高，且引入的碳酸氢钠较难被除干净。CN103950927A Mix expanded graphite and sodium bicarbonate solution, heat up to 190°C and stir for 1.5 hours, then use sodium bicarbonate to decompose to generate carbon dioxide to generate peeling force between expandable graphite sheets, and after carbon dioxide is dissolved in water, the formed Alkaline conditions cause electrostatic repulsion between graphene sheets, thereby forming graphene. However, the preparation process requires high temperature and high pressure, high energy consumption, and the introduction of sodium bicarbonate is difficult to remove.
此外，还有许多关于膨胀石墨制备石墨烯的研究报告，但或多或少存在以下问题：可膨胀石墨膨化处理后，未膨胀的原料分离问题；膨胀石墨剥离阶段的剥离方式问题；剥离时选用的辅助剥离助剂的剥离效率、成本以及后期除去辅助剥离助剂的难易问题等等。In addition, there are many research reports on the preparation of graphene from expanded graphite, but there are more or less the following problems: after the expansion of expandable graphite, the separation of unexpanded raw materials; the problem of the stripping method of the expanded graphite stripping stage; The stripping efficiency and cost of the auxiliary stripping aid and the difficulty of removing the auxiliary stripping aid in the later stage, etc.
发明内容Contents of the invention
为了克服现有技术存在的上述问题，本发明的目的在于提供一种绿色环保制备石墨烯的方法。In order to overcome the above-mentioned problems existing in the prior art, the object of the present invention is to provide a method for preparing graphene in an environment-friendly manner.
为了实现上述的目的，本发明所采取的技术方案是：In order to realize above-mentioned purpose, the technical scheme that the present invention takes is:
本发明提供了一种制备石墨烯的方法，这种制备方法包括以下步骤：The invention provides a kind of method for preparing graphene, and this preparation method comprises the following steps:
1)将可膨胀石墨进行膨胀处理，然后粉碎，得到膨胀石墨粉料；1) expanding the expandable graphite, and then pulverizing it to obtain expanded graphite powder;
2)将膨胀石墨粉料与双氧水混合搅拌，再脱气，然后进行超声剥离，再加热分解双氧水，然后干燥，得到石墨烯。2) Mix and stir the expanded graphite powder with hydrogen peroxide, then degas, then perform ultrasonic peeling, then heat to decompose hydrogen peroxide, and then dry to obtain graphene.
优选的，这种制备石墨烯的方法步骤1)中，可膨胀石墨的粒径为50目～100目。Preferably, in step 1) of the method for preparing graphene, the particle size of the expandable graphite is 50 mesh to 100 mesh.
优选的，这种制备石墨烯的方法步骤1)中，可膨胀石墨的膨胀倍率为200～400倍；进一步优选的，可膨胀石墨的膨胀倍率为250～350倍。Preferably, in step 1) of the method for preparing graphene, the expansion ratio of the expandable graphite is 200-400 times; more preferably, the expansion ratio of the expandable graphite is 250-350 times.
优选的，这种制备石墨烯的方法步骤1)中，可膨胀石墨的碳含量≥98wt％。Preferably, in step 1) of the method for preparing graphene, the carbon content of the expandable graphite is ≥98wt%.
优选的，这种制备石墨烯的方法步骤1)中，膨胀处理为热膨胀处理、微波膨胀处理中的一种或两种。Preferably, in step 1) of the method for preparing graphene, the expansion treatment is one or both of thermal expansion treatment and microwave expansion treatment.
优选的，这种制备石墨烯的方法步骤1)的膨胀处理中，热膨胀处理是指将可膨胀石墨置于氮气或者惰性气体气氛中加热膨胀处理，加热的温度为600℃～800℃，膨胀处理的时间为30s～90s；进一步优选的，热膨胀处理是指将可膨胀石墨置于氮气气氛中加热至650℃～750℃膨胀处理50s～70s。Preferably, in the expansion treatment of step 1) of the method for preparing graphene, the thermal expansion treatment refers to heating and expanding the expandable graphite in a nitrogen or inert gas atmosphere, and the heating temperature is 600°C to 800°C, and the expansion treatment The time is 30s to 90s; more preferably, the thermal expansion treatment refers to heating the expandable graphite in a nitrogen atmosphere to 650°C to 750°C for 50s to 70s.
优选的，这种制备石墨烯的方法步骤1)中，粉碎为球磨、研磨、气流磨中的一种或多种。Preferably, in step 1) of the method for preparing graphene, pulverization is one or more of ball milling, grinding, jet milling.
优选的，这种制备石墨烯的方法步骤1)中，粉碎至物料的粒径D50不大于20μm；进一步优选的，粉碎至物料的粒径D50不大于10μm。Preferably, in step 1) of the method for preparing graphene, the particle size D50 of the material is pulverized to no greater than 20 μm; further preferably, the particle size D50 of the material is pulverized to no greater than 10 μm.
优选的，这种制备石墨烯的方法步骤2)中，膨胀石墨粉料与双氧水的质量比为1∶(10～100)。Preferably, in step 2) of the method for preparing graphene, the mass ratio of expanded graphite powder to hydrogen peroxide is 1: (10-100).
优选的，这种制备石墨烯的方法步骤2)中，双氧水的H 2O 2质量百分比为5％～50％；进一步优选的，双氧水的H 2O 2质量百分比为10％～40％。 Preferably, in step 2) of the method for preparing graphene, the mass percentage of H 2 O 2 in hydrogen peroxide is 5%-50%; further preferably, the mass percentage of H 2 O 2 in hydrogen peroxide is 10%-40%.
优选的，这种制备石墨烯的方法步骤2)中，混合搅拌的时间为3min～10min；进一步优选的，混合搅拌的时间为4min～6min。Preferably, in step 2) of the method for preparing graphene, the time for mixing and stirring is 3 minutes to 10 minutes; more preferably, the time for mixing and stirring is 4 minutes to 6 minutes.
优选的，这种制备石墨烯的方法步骤2)中，脱气的方式为真空脱气。Preferably, in step 2) of the method for preparing graphene, the degassing mode is vacuum degassing.
优选的，这种制备石墨烯的方法步骤2)中，脱气具体为在1～10kPa下真空脱气3min～10min。Preferably, in step 2) of the method for preparing graphene, the degassing is specifically vacuum degassing at 1-10 kPa for 3 min-10 min.
优选的，这种制备石墨烯的方法步骤2)中，超声剥离的温度为50℃～100℃；进一步优选的，超声剥离的温度为50℃～80℃；再进一步优选的，超声剥离的温度为50℃～60℃。Preferably, in step 2) of the method for preparing graphene, the temperature of ultrasonic peeling is 50°C to 100°C; more preferably, the temperature of ultrasonic peeling is 50°C to 80°C; still more preferably, the temperature of ultrasonic peeling 50°C to 60°C.
优选的，这种制备石墨烯的方法步骤2)中，超声剥离的时间为0.5h～2h；进一步优选的，超声剥离的时间为1h～2h。Preferably, in step 2) of the method for preparing graphene, the ultrasonic peeling time is 0.5h-2h; more preferably, the ultrasonic peeling time is 1h-2h.
优选的，这种制备石墨烯的方法步骤2)中，超声的功率为0.5kW～3kW，超声的频率为20kHz～60kHz。Preferably, in step 2) of the method for preparing graphene, the power of the ultrasound is 0.5kW-3kW, and the frequency of the ultrasound is 20kHz-60kHz.
优选的，这种制备石墨烯的方法步骤2)中，加热分解的温度为100℃～160℃。Preferably, in step 2) of the method for preparing graphene, the thermal decomposition temperature is 100°C-160°C.
优选的，这种制备石墨烯的方法步骤2)中，加热分解的时间为0.5h～2h；进一步优选的，加热分解的时间为1h～2h。Preferably, in step 2) of the method for preparing graphene, the time for thermal decomposition is 0.5h-2h; more preferably, the time for thermal decomposition is 1h-2h.
这种制备石墨烯的方法步骤2)中，在超声剥离后，通过升温加热分解双氧水为水和氧气；在升温加热的过程中，可以通过用高锰酸钾溶液进行滴定测试，检测双氧水是否分解完全。In step 2) of the method for preparing graphene, after ultrasonic stripping, the hydrogen peroxide is decomposed into water and oxygen by heating and heating; in the process of heating and heating, a titration test can be carried out with potassium permanganate solution to detect whether the hydrogen peroxide is decomposed completely.
优选的，这种制备石墨烯的方法步骤2)中，干燥的方式为喷雾干燥。Preferably, in step 2) of the method for preparing graphene, the drying method is spray drying.
本发明还提供了一种石墨烯，是由上述的方法制得。The present invention also provides a kind of graphene, which is prepared by the above method.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明提供了一种适合于规模化生产制备石墨烯的方法，该方法绿色无污染，安全环保。通过本发明方法制备得到的石墨烯具有尺寸均匀，缺陷少等优点。The invention provides a method suitable for large-scale production and preparation of graphene, which is green, pollution-free, safe and environment-friendly. The graphene prepared by the method of the invention has the advantages of uniform size, few defects and the like.
与现有技术相比，本发明的优点具体如下：Compared with prior art, advantage of the present invention is specifically as follows:
1、本发明以可膨胀石墨为原材料，膨化处理后，产品的层间距要比鳞片石墨的层间距大，范德华力更小，剥离时需要的能量更少。比传统利用鳞片石墨或高定向热解石墨剥离时用的时间更短，剥离效率更高。而使用氧化石墨为原料，其制备工艺复杂，成本高昂，至少为可膨胀石墨的5倍以上。1. The present invention uses expandable graphite as raw material. After puffing treatment, the layer spacing of the product is larger than that of flake graphite, the van der Waals force is smaller, and the energy required for peeling is less. Compared with the traditional use of flake graphite or highly oriented pyrolytic graphite, the time is shorter and the stripping efficiency is higher. However, graphite oxide is used as a raw material, and its preparation process is complicated and the cost is high, which is at least 5 times that of expandable graphite.
2、对超声剥离前的样品进行粉碎处理，样品越小，超声剥离时作用在样品上的“空穴效应”越明显，从而使得样品更容易被剥离。2. Pulverize the sample before ultrasonic peeling. The smaller the sample, the more obvious the "cavitation effect" on the sample during ultrasonic peeling, which makes the sample easier to peel.
3、以双氧水为剥离溶液，相对于去离子水来说双氧水的表面张力更小，更容易润湿膨胀石墨。还进行脱气处理，使得双氧水更容易渗透到膨胀石墨的空隙间来代替原来的空气，从而使得双氧水充分润湿膨胀石墨。超声剥离阶段，升温时双氧水缓慢分解，产生的气泡将膨胀石墨完全剥离开，而超声剥离时，利用超声产生的“空穴效应”协同双氧水产生的气泡将膨胀石墨完全剥离成石墨烯。待剥离完成后，升温将双氧水完全分解后，将石墨烯干燥即可得到产品。整个剥离效率高效便捷，且生产过程中无三废的排放，剥离效率远胜于利用水或有机溶剂剥离的效率。而且剥离时间短，得到的产品的缺陷小，粒径更均匀，品质更好。3. Hydrogen peroxide is used as the stripping solution. Compared with deionized water, the surface tension of hydrogen peroxide is smaller, and it is easier to wet the expanded graphite. Degassing treatment is also carried out, so that hydrogen peroxide can more easily penetrate into the gaps of the expanded graphite to replace the original air, so that the hydrogen peroxide can fully wet the expanded graphite. In the ultrasonic stripping stage, the hydrogen peroxide slowly decomposes when the temperature rises, and the generated bubbles completely peel off the expanded graphite. During the ultrasonic stripping, the "cavitation effect" generated by the ultrasound is used to cooperate with the bubbles generated by the hydrogen peroxide to completely strip the expanded graphite into graphene. After the peeling is completed, the temperature is raised to completely decompose the hydrogen peroxide, and the graphene is dried to obtain the product. The entire stripping efficiency is efficient and convenient, and there is no discharge of three wastes in the production process, and the stripping efficiency is far better than that of using water or organic solvents. Moreover, the peeling time is short, and the defects of the obtained product are small, the particle size is more uniform, and the quality is better.
4、整个生产过程中，能耗低，安全，高效，且生产过程绿色环保，易于放大和推广。4. During the whole production process, the energy consumption is low, safe and efficient, and the production process is green and environmentally friendly, easy to scale up and popularize.
附图说明Description of drawings
图1是实施例1制得的样品扫描电镜图；Fig. 1 is the sample scanning electron micrograph that embodiment 1 makes;
图2是对比例1制得的样品扫描电镜图。FIG. 2 is a scanning electron micrograph of the sample prepared in Comparative Example 1.
具体实施方式Detailed ways
以下通过具体的实施例对本发明的内容作进一步详细的说明。实施例中所用的原料如无特殊说明，均可从常规商业途径得到。The content of the present invention will be described in further detail below through specific examples. The raw materials used in the examples can be obtained from conventional commercial channels unless otherwise specified.
实施例1Example 1
本例的石墨烯制备方法如下：The graphene preparation method of this example is as follows:
将100g碳含量99wt％、80目、膨胀倍率300倍的膨胀石墨置于高温膨胀炉中，于氮气氛围中700℃膨胀60s后，将膨胀后的样品利用气流粉碎机研磨粒径至D50为10μm。取10g研磨后的样品置于烧瓶中后，加入500mLH 2O 2质量百分比为30％的双氧水后连续搅拌5min， 真空脱气5min后，升温至60℃，利用3kW、30kHz的超声连续剥离1h后，升温至150℃搅拌1h直至无起泡(使用高锰酸钾溶液滴定判断双氧水分解完全)后，喷雾干燥，即可得到石墨烯样品。 Put 100g of expanded graphite with a carbon content of 99wt%, 80 mesh, and an expansion ratio of 300 times in a high-temperature expansion furnace, and expand it at 700°C for 60s in a nitrogen atmosphere, and then grind the expanded graphite with a jet mill until the particle size of D50 is 10 μm . Take 10g of the ground sample and place it in a flask, add 500mL H 2 O 2 30% hydrogen peroxide, stir continuously for 5 minutes, degas in vacuum for 5 minutes, heat up to 60°C, and use 3kW, 30kHz ultrasonic to continuously peel for 1h , heated to 150° C. and stirred for 1 h until no foaming occurred (it was judged that the hydrogen peroxide was completely decomposed by titration with potassium permanganate solution), and then spray-dried to obtain a graphene sample.
实施例2Example 2
本例的石墨烯制备方法如下：The graphene preparation method of this example is as follows:
将100g碳含量99wt％、100目、膨胀倍率300倍的膨胀石墨置于高温膨胀炉中，于氮气氛围中700℃膨胀60s后，将膨胀后的样品利用气流粉碎机研磨粒径至D50为8μm。取10g研磨后的样品置于烧瓶中后，加入800mLH 2O 2质量百分比为20％的双氧水后连续搅拌5min，真空脱气5min后，升温至70℃，利用2kW、30kHz的超声连续剥离1h后，升温至150℃搅拌1h直至无起泡(使用高锰酸钾溶液滴定判断双氧水分解完全)后，喷雾干燥，即可得到石墨烯样品。 Put 100g of expanded graphite with a carbon content of 99wt%, 100 mesh, and an expansion ratio of 300 times in a high-temperature expansion furnace. After expanding for 60 seconds at 700°C in a nitrogen atmosphere, the expanded graphite is ground with a jet mill until the particle size of D50 is 8 μm. . Take 10g of the ground sample and place it in a flask, add 800mL H 2 O 2 hydrogen peroxide with a mass percentage of 20%, stir continuously for 5min, degas in vacuum for 5min, heat up to 70°C, and use 2kW, 30kHz ultrasonic to continuously peel for 1h , heated to 150° C. and stirred for 1 h until no foaming occurred (it was judged that the hydrogen peroxide was completely decomposed by titration with potassium permanganate solution), and then spray-dried to obtain a graphene sample.
实施例3Example 3
本例的石墨烯制备方法如下：The graphene preparation method of this example is as follows:
将80g碳含量99wt％、50目、膨胀倍率300倍的膨胀石墨置于高温膨胀炉中，于氮气氛围中700℃膨胀60s后，将膨胀后的样品利用气流粉碎机研磨粒径至D50为10μm。取10g研磨后的样品置于烧瓶中后，加入1000mLH 2O 2质量百分比为30％的双氧水后连续搅拌5min，真空脱气5min后，升温至60℃，利用1kW、30kHz的超声连续剥离0.5h后，升温至155℃搅拌2h直至无起泡(使用高锰酸钾溶液滴定判断双氧水分解完全)后，喷雾干燥，即可得到石墨烯样品。 Put 80g of expanded graphite with a carbon content of 99wt%, 50 mesh, and an expansion rate of 300 times in a high-temperature expansion furnace. After expanding for 60 seconds at 700°C in a nitrogen atmosphere, the expanded sample is ground by a jet mill until the particle size of D50 is 10 μm. . Take 10g of the ground sample and place it in a flask, add 1000mLH 2 O 2 with 30% hydrogen peroxide, stir continuously for 5min, degas in vacuum for 5min, raise the temperature to 60°C, and use 1kW, 30kHz ultrasonic to continuously peel for 0.5h Afterwards, heat up to 155° C. and stir for 2 hours until there is no foaming (use potassium permanganate solution to titrate to judge that the hydrogen peroxide is completely decomposed), and then spray dry to obtain a graphene sample.
对比例1Comparative example 1
本例样品的制备方法如下：The sample preparation method of this example is as follows:
将100g碳含量99wt％，80目、膨胀倍率300倍的膨胀石墨置于高温膨胀炉中，于氮气氛围中700℃膨胀60s后，将膨胀后的样品利用气流粉碎机研磨粒径至D50为10μm。取10g研磨后的样品置于烧瓶中后，加入500mL去离子水后连续搅拌5min，真空脱气5min后，升温至60℃，利用3kW、30kHz的超声连续剥离1h后，升温至150℃搅拌1h后，喷雾干燥，即可得到石墨烯与膨胀石墨的混合样品。Put 100g of expanded graphite with a carbon content of 99wt%, 80 mesh, and an expansion ratio of 300 times in a high-temperature expansion furnace. After expanding for 60 seconds at 700°C in a nitrogen atmosphere, the expanded sample is ground by a jet mill until the particle size of D50 is 10 μm. . Take 10g of the ground sample and place it in a flask, add 500mL of deionized water, stir continuously for 5min, degas in vacuum for 5min, then raise the temperature to 60°C, use 3kW, 30kHz ultrasonic to continuously peel for 1h, then raise the temperature to 150°C and stir for 1h After spray drying, a mixed sample of graphene and expanded graphite can be obtained.
实施例1制得的样品扫描电镜图见附图1，对比例1的样品扫描电镜图见附图2。通过图1和图2的SEM图对比可知，实施例1制得的样品粒径更均匀，缺陷少，证明剥离效果更好。而对比例1制得的样品中样品尺寸随着超声剥离进一步的膨胀，但同时还有未剥离的膨胀石墨的结构的存在，剥离效果较差。See accompanying drawing 1 for the scanning electron micrograph of the sample prepared in Example 1, and refer to accompanying drawing 2 for the scanning electron microscopic drawing of the sample of comparative example 1. From the comparison of the SEM images in Figure 1 and Figure 2, it can be seen that the sample prepared in Example 1 has a more uniform particle size and fewer defects, which proves that the peeling effect is better. However, in the sample prepared in Comparative Example 1, the size of the sample further expanded with the ultrasonic exfoliation, but at the same time, there was an unexfoliated expanded graphite structure, and the exfoliation effect was poor.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (6)

  1. 一种制备石墨烯的方法，其特征在于：包括以下步骤：A method for preparing graphene, characterized in that: comprises the following steps:
    1)将可膨胀石墨进行膨胀处理，然后粉碎，得到膨胀石墨粉料；1) expanding the expandable graphite, and then pulverizing it to obtain expanded graphite powder;
    2)将膨胀石墨粉料与双氧水混合搅拌，再脱气，然后进行超声剥离，再加热分解双氧水，然后干燥，得到石墨烯；2) mixing and stirring the expanded graphite powder with hydrogen peroxide, then degassing, then performing ultrasonic peeling, reheating to decompose hydrogen peroxide, and then drying to obtain graphene;
    所述步骤1)中，粉碎至物料的粒径D50不大于20μm；In the step 1), pulverize until the particle size D50 of the material is not greater than 20 μm;
    所述步骤2)中，膨胀石墨粉料与双氧水的质量比为1∶(10～100)；超声剥离的温度为50℃～100℃，超声剥离的时间为0.5h～2h；加热分解的温度为100℃～160℃，加热分解的时间为0.5h～2h。In said step 2), the mass ratio of expanded graphite powder to hydrogen peroxide is 1: (10-100); the temperature of ultrasonic peeling is 50°C-100°C, and the time of ultrasonic peeling is 0.5h-2h; the temperature of thermal decomposition The temperature is 100 ℃ ~ 160 ℃, and the time for thermal decomposition is 0.5h ~ 2h.
  2. 根据权利要求1所述的一种制备石墨烯的方法，其特征在于：步骤1)中，膨胀处理为热膨胀处理。A kind of method for preparing graphene according to claim 1, is characterized in that: in step 1), expansion treatment is thermal expansion treatment.
  3. 根据权利要求1所述的一种制备石墨烯的方法，其特征在于：步骤1)中，粉碎为球磨、研磨、气流磨中的一种或多种。A kind of method for preparing graphene according to claim 1, is characterized in that: in step 1), pulverizing is one or more in ball milling, grinding, jet mill.
  4. 根据权利要求1所述的一种制备石墨烯的方法，其特征在于：步骤2)中，双氧水的H 2O 2质量百分比为5％～50％。 A method for preparing graphene according to claim 1, characterized in that: in step 2), the mass percentage of H 2 O 2 in hydrogen peroxide is 5% to 50%.
  5. 根据权利要求1所述的一种制备石墨烯的方法，其特征在于：步骤2)中，脱气的方式为真空脱气。A kind of method for preparing graphene according to claim 1, is characterized in that: in step 2), the mode of degassing is vacuum degassing.
  6. 一种石墨烯，其特征在于：是由权利要求1～5任一项所述的方法制得。A graphene, characterized in that: it is made by the method described in any one of claims 1-5.
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CN109319771A (en) * 2018-12-03 2019-02-12 青岛岩海碳材料有限公司 A kind of preparation method of graphene
CN110203913A (en) * 2019-05-30 2019-09-06 广东聚石化学股份有限公司 A method of preparing graphene
WO2020229881A1 (en) * 2019-05-16 2020-11-19 Arcelormittal A method for the manufacture of graphene oxide from expanded kish graphite

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CN102942177A (en) * 2012-11-15 2013-02-27 中山大学 Method for preparing graphene sheet
CN104071777A (en) * 2014-06-19 2014-10-01 哈尔滨翔科新材料有限公司 Preparation method of graphene
US20180370801A1 (en) * 2016-01-18 2018-12-27 King Abdullah University Of Science And Technology Expansion and exfoliation of graphite to form graphene
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