WO2015096317A1 - Method for preparing single-layered graphene - Google Patents

Method for preparing single-layered graphene Download PDF

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Publication number
WO2015096317A1
WO2015096317A1 PCT/CN2014/075917 CN2014075917W WO2015096317A1 WO 2015096317 A1 WO2015096317 A1 WO 2015096317A1 CN 2014075917 W CN2014075917 W CN 2014075917W WO 2015096317 A1 WO2015096317 A1 WO 2015096317A1
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autoclave
graphene
gas
graphite powder
preparation
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PCT/CN2014/075917
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French (fr)
Chinese (zh)
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李永峰
李磊
贾希来
杨帆
高金森
徐春明
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中国石油大学(北京)
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Publication of WO2015096317A1 publication Critical patent/WO2015096317A1/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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to a preparation method of graphene, in particular to a preparation method of oligo-layer graphene, and belongs to the field of preparation of chemical materials. Background technique
  • Graphene Since the discovery of graphene in 2004, it has been widely favored by researchers in the field of physics and materials. Graphene is a two-dimensional honeycomb lattice structure carbonaceous material which is closely packed by a single layer of carbon atoms. Although graphene has only one carbon atom layer thickness and is the thinnest of the known materials, it is very strong and hard. Graphene is also the most conductive material known to date. In addition, graphene has many excellent properties: high Young's modulus, thermal conductivity, large specific surface area, and so on. Due to its special properties, graphene has a wide range of applications in electronics, optics, magnetism, biomedicine, sensors, and energy storage. How to prepare high-quality, high-yield graphene has become a hot research topic in the field.
  • the methods for preparing graphene mainly include the following: redox method, chemical vapor deposition method, mechanical stripping method, epitaxial growth method, solvent stripping method, and the like.
  • the above methods have drawbacks in use in specific applications, and most of them belong to the preparation method of multilayer graphene.
  • an object of the present invention is to provide a method for preparing an oligo-layer graphene, which has a simple preparation process and can prepare a small amount of graphene in a large amount and high efficiency.
  • the present invention first provides a method for preparing an oligo-layer graphene, which comprises the following steps:
  • Step 1 Purifying the graphite powder
  • Step 2 directly adding the purified graphite powder into the autoclave or dispersing in a solvent, adding to the autoclave, heating, and after the temperature in the autoclave reaches 35-60, pumping the supercritical fluid into the autoclave;
  • Step 3 After pumping the supercritical fluid to raise the pressure in the autoclave to 75atm-300atm, stir for 30min-20h, then reduce the pressure to lapm within 5s-20s (preferably 10s).
  • the specific pressure reduction method can be carried out according to the conventional method. get on;
  • Step 4 Sampling from the autoclave to obtain the oligo-layer graphene.
  • the supercritical fluid employed is a co 2 supercritical fluid.
  • the graphite powder employed comprises flake graphite powder and/or expanded graphite powder or the like.
  • the solvent employed comprises sodium decyl sulfate and/or sodium dodecylbenzene sulfonate and the like.
  • the rate of agitation in step three is from 1000 to 10000 r/min.
  • the gas obtained by the supercritical fluid after the pressure reduction may be placed in a gas tank for recovery and storage to be recycled.
  • the purification process of the specific graphite powder comprises the following steps: Step 1: ultrasonically cleaning the graphite powder to remove impurities;
  • Step 2 Chemical treatment or other means to remove the heterogeneous substances and impurity elements.
  • the present invention also provides an oligo-layer graphene which is prepared by the above preparation method.
  • the ratio of the oligo-layer graphene having a number of layers of 10 or less prepared by the above method is 60% or more, and preferably, the number of layers of the oligo-graphene is 1-10.
  • the present invention also provides an apparatus for producing the above oligo-layer graphene, which can be used in the above-described method for producing oligo-layer graphene.
  • the device includes a stirring motor, a heating jacket, an autoclave, a gas circulation system, a stirring rod, a stirring head, wherein
  • the stirring rod is vertically located in the middle of the top of the autoclave, and the stirring rod is connected to the stirring motor at one end of the outer portion of the autoclave, and the other end of the bottom of the autoclave is connected to the stirring head;
  • An inlet and a gas inlet are disposed at a top of the autoclave; the inlet and the gas inlet are disposed on both sides of the stirring motor;
  • the heating jacket is wrapped on the outside of the autoclave
  • the bottom of the autoclave is provided with a sample outlet
  • the gas circulation system includes a gas tank, a first wide door, a second wide door, a flow meter, a condensing device, and a third wide door, and the line leading from the gas inlet sequentially connects the first wide door, the gas tank, and the second wide door , the flow meter, the condensing device and the third wide door, the end of the pipeline is connected with the pipeline leading from the gas inlet to form a gas circulation system; wherein the first wide gate, the second wide gate and the third wide gate are used for controlling the opening of the pipeline And closed, the flow meter is used for metering the amount of gas, the gas tank is used for storing the required gas and the recovered gas, the condensing device condenses the gas, and acts together with the external pressure pump to make the gas supercritical, any of which can be used a device capable of implementing this function; The gas circulation system is in communication with the gas inlet.
  • the oligo-graphene is prepared by the above device, first, the first wide gate, the second wide gate, and the third wide gate are in a closed state, and the purified graphite powder is directly added into the autoclave or dispersed in a solvent and then added to a high pressure. In the kettle, heating is performed by a heating jacket.
  • the second wide door and the third wide door are opened, and the gas in the gas tank is condensed by the condensing device, and acts together with the external pressure pump to make the gas Conversion into a supercritical fluid, pumping the supercritical fluid into the autoclave; then, after pumping the supercritical fluid to raise the pressure in the autoclave to 75atm-300atm, the second wide door and the third wide door are closed, and the stirring motor is turned on.
  • the preparation method of the oligo-layer graphene provided by the invention is a method for efficiently preparing the oligo-layer graphene, and can prepare a high-quality oligo-layer graphene in a large amount, and the number of graphene layers prepared by the method is small.
  • the preparation method of the oligo-layer graphene provided by the invention is environmentally friendly, has low production cost, can recycle C0 2 , and reduces co 2 emission and cost. At the same time, it has the advantages of short reaction cycle, simple process, and good integrity of the prepared oligo-graphene.
  • FIG. 1 is a flow chart of a method for preparing an oligo-layer graphene provided by the present invention
  • FIG. 2 is a schematic structural view of an apparatus for preparing an oligo-layer graphene provided by the present invention
  • Example 3 is a transmission electron microscope (TEM) image of the oligo-layer graphene prepared in Example 1;
  • Example 4 is another transmission electron microscope (TEM) image of the oligo-layer graphene prepared in Example 1.
  • Example 5 is a transmission electron microscope (TEM) image of the oligo-layer graphene prepared in Example 2;
  • Figure 6 is another transmission electron microscope (TEM) image of the oligo-layer graphene prepared in Example 2.
  • This embodiment provides an apparatus for preparing an oligo-layer graphene, the structure of which is shown in FIG.
  • the device includes: a stirring motor 3, a heating jacket 2, an autoclave 1, a gas circulation system, a stirring rod 4, and a stirring head 5, wherein the stirring rod 4 is vertically located in the middle of the top of the autoclave 1, and the stirring rod 4 is connected at one end of the outside of the autoclave 1 Mixing motor 3, extending to the other end of the bottom of the autoclave 1 is connected to the stirring head 5;
  • An inlet 6 and a gas inlet 7 are provided at the top of the autoclave 1; the inlet 6 and the gas inlet 7 are placed on both sides of the stirring motor 3;
  • the heating jacket 2 is wrapped outside the autoclave 1;
  • the bottom of the autoclave 1 is provided with a sample outlet 8;
  • the gas circulation system includes a gas tank 12, a first wide door 9, a second wide door 10, a flow meter 11, a condensing device 13 and a third wide door 14, and the line leading from the gas inlet 7 sequentially connects the first wide door 9, gas a tank 12, a second wide door 10, a flow meter 11, a condensing device 13 and a third wide door 14, the end of the line is in communication with a line leading from the gas inlet 7, forming a gas circulation system; wherein, the first wide door 9 and the second The wide door 10 is used for controlling the opening and closing of the pipeline, the flow meter 11 is for metering the amount of gas, the gas tank 12 is for storing the required gas and the recovered gas, the condensing device 13 is condensing the gas, and the external pressure pump As soon as the function is made to make the gas supercritical, any device capable of performing this function can be employed; the gas circulation system is in communication with the gas inlet 7.
  • the oligo-graphene is prepared by the above device, and the preparation flow chart is as shown in FIG. 1.
  • the preparation process may specifically include the following steps:
  • Step 1 Prepare graphite powder: Ultrasonic cleaning (10 times of water washing and 2 times of ethanol washing) to remove impurities and impurity elements;
  • Step 2 Supercritical C0 2 intercalation: the first wide door 9, the second wide door 10, and the third wide door 14 are in a closed state, and the purified flake graphite powder is directly added into the autoclave 1 and heated. After the temperature in the autoclave 1 reaches 35 ° C, the second wide door 10 and the third wide door 14 are opened, and the C0 2 gas in the gas tank 12 is condensed by the condensing device 13, and together with the external pressure pump, C0 2 The gas is converted into a C0 2 supercritical fluid, and the C0 2 supercritical fluid is pumped into the autoclave 1, and the amount of the C0 2 supercritical fluid is metered by the flow meter 11;
  • Step 3 Supercritical C0 2 shearing: After pumping the C0 2 supercritical fluid to raise the pressure in the autoclave 1 to 300 atm, the second wide door 10 and the third wide door 14 are closed, and the stirring motor 3 is turned on for stirring. For 10000r/min, the graphite is peeled off by the shear force generated by the high-speed flowing C0 2 supercritical fluid. After stirring for 30 minutes, the pressure is reduced to lapm within 10s, and the first wide door 9 is opened to recover the gas and then the first wide is closed. Door 9;
  • Step 4 Obtaining graphene: Sampling from the autoclave 1 to obtain the oligo-layer graphene.
  • the obtained oligo-graphene was photographed by a transmission electron microscope (TEM) as shown in Figs. 3 and 4.
  • TEM transmission electron microscope
  • the number of layers of the oligo-layer graphene prepared in this example can be clearly seen from FIG. 3 and FIG. 4, and the lack of graphene can be observed.
  • the trapping was small, and by counting the number of layers thereof, it was found that the ratio of the number of layers of graphene obtained in Example 1 to 10 or less was about 60%.
  • the present embodiment provides a method for preparing an oligo-graphene, which is prepared by using the apparatus described in Embodiment 1, and the method specifically includes the following steps:
  • Step 1 Prepare graphite powder: Ultrasonic cleaning of lg expanded graphite powder (washing once, washing twice with ethanol) to remove impurities and impurity elements;
  • Step 2 Supercritical C0 2 intercalation: The first wide door 9, the second wide door 10, and the third wide door 14 are in a closed state, and the purified expanded graphite powder is dispersed in 200 mL of a 12 wt% twelfth base. After sodium sulfate (SDS), it is added to the autoclave 1 and heated. After the temperature in the autoclave 1 reaches 60 ° C, the second wide door 10 and the third wide door 14 are opened, and the gas can 12 is opened.
  • SDS sodium sulfate
  • the C0 2 gas is condensed by the condensing device 13, and together with the external pressure pump, the C0 2 gas is converted into the C0 2 supercritical fluid, and the C0 2 supercritical fluid is pumped into the autoclave 1, and the amount of the C0 2 supercritical fluid is passed through the flow.
  • Step 3 Supercritical C0 2 shearing: After pumping the C0 2 supercritical fluid to raise the pressure in the autoclave 1 to 75 atm, the second wide door 10 and the third wide door 14 are closed, and the stirring motor 3 is turned on for stirring. For lOOOr/min, the graphite is peeled off by the shear force generated by the high-speed flowing C0 2 supercritical fluid, stirred for 20h, then the pressure is reduced to lapm within 10s, and the first wide door 9 is opened to recover the gas and then closed first. Wide door 9;
  • Step 4 Obtaining graphene: Sampling from the autoclave 1 to obtain the oligo-layer graphene.
  • the obtained oligo-ply graphene was photographed by a transmission electron microscope (TEM) as shown in Figs. 5 and 6. It can be clearly seen from FIG. 5 and FIG. 6 that the number of layers of the oligo-layer graphene prepared in the present embodiment is small, and at the same time, the defects of the graphene are less observed, and the number of layers is counted, and the results obtained in the embodiment 2 are found.
  • the ratio of the number of layers of graphene to 10 or less is about 80%.

Abstract

Provided is a method for preparing single-layered graphene. The method comprises: performing purification treatment on graphite powder; adding the purified graphite powder into a high-pressure kettle, or dispersing the purified graphite powder into a solvent and then adding into the high-pressure kettle; performing heating, and after the temperature in the high-pressure kettle reaches to a pre-set temperature, pumping a supercritical fluid into the high-pressure kettle; after the pressure in the high-pressure kettle is raised to a preset value, stirring for 30 minutes to 20 hours, and rapidly reducing the pressure; and sampling from the high-pressure kettle to obtain the single-layered graphene. Also provided is an apparatus for manufacturing the single-layered graphene. The manufacturing method is green and environmentally-friendly, and needs low production cost, a short period and a simple process; and the integrity of the manufactured graphene sheet layer is good.

Description

一种寡层石墨烯的制备方法 技术领域  Method for preparing oligo-layer graphene
本发明涉及一种石墨烯的制备方法， 特别涉及一种寡层石墨烯的制备方法， 属于化 工材料制备领域。 背景技术  The invention relates to a preparation method of graphene, in particular to a preparation method of oligo-layer graphene, and belongs to the field of preparation of chemical materials. Background technique
从 2004年石墨烯被发现以来， 一直倍受物理和材料领域研究者的普遍青睐。 石墨 烯是一种由单层碳原子紧密堆积而成的二维蜂窝状晶格结构碳质材料。尽管石墨烯只有 一个碳原子层厚度， 并且是已知材料中最薄的一种， 但却非常牢固坚硬。 石墨烯也是目 前已知导电性最出色的材料。 此外， 石墨烯还有许多优异的性能： 如较高的杨氏模量、 热导率、 巨大的比表面积等等。 由于石墨烯的特殊性能， 它在电子学、 光学、 磁学、 生 物医学、 传感器、 储能等方面均有广泛的应用。 而如何制备出高质量、 高产率的石墨烯 已成为本领域热门的研究课题。  Since the discovery of graphene in 2004, it has been widely favored by researchers in the field of physics and materials. Graphene is a two-dimensional honeycomb lattice structure carbonaceous material which is closely packed by a single layer of carbon atoms. Although graphene has only one carbon atom layer thickness and is the thinnest of the known materials, it is very strong and hard. Graphene is also the most conductive material known to date. In addition, graphene has many excellent properties: high Young's modulus, thermal conductivity, large specific surface area, and so on. Due to its special properties, graphene has a wide range of applications in electronics, optics, magnetism, biomedicine, sensors, and energy storage. How to prepare high-quality, high-yield graphene has become a hot research topic in the field.
目前， 制备石墨烯的方法主要包括以下几种： 氧化还原法、 化学气相沉积法、 机械 剥离法、 外延生长法、 溶剂剥离法等。 但是， 上述方法在具体应用时都存在使用缺陷， 而且大多属于多层石墨烯的制备方法。  At present, the methods for preparing graphene mainly include the following: redox method, chemical vapor deposition method, mechanical stripping method, epitaxial growth method, solvent stripping method, and the like. However, the above methods have drawbacks in use in specific applications, and most of them belong to the preparation method of multilayer graphene.
由此可见， 研发出一种寡层石墨烯的制备装置及方法， 是本领域亟待解决的问题之  It can be seen that the development of an apparatus and method for preparing oligo-layer graphene is an urgent problem to be solved in the field.
发明内容 Summary of the invention
为了解决上述问题， 本发明的目的在于提供一种寡层石墨烯的制备方法， 该方法的 制备工艺简单， 可以大量、 高效的制备少层的石墨烯。  In order to solve the above problems, an object of the present invention is to provide a method for preparing an oligo-layer graphene, which has a simple preparation process and can prepare a small amount of graphene in a large amount and high efficiency.
本发明的目的还在于提供一种寡层石墨烯以及用于制备上述寡层石墨烯的装置。 为了达到上述目的， 本发明首先提供了一种寡层石墨烯的制备方法， 其包括以下步 骤：  It is also an object of the present invention to provide an oligo-layer graphene and an apparatus for preparing the above-described oligo-layer graphene. In order to achieve the above object, the present invention first provides a method for preparing an oligo-layer graphene, which comprises the following steps:
步骤一： 对石墨粉进行纯化处理；  Step 1: Purifying the graphite powder;
步骤二： 将纯化后的石墨粉直接加入高压釜内或分散在溶剂中后加入高压釜内， 进 行加热， 待高压釜内的温度达到 35-60 后， 将超临界流体泵入高压釜内；  Step 2: directly adding the purified graphite powder into the autoclave or dispersing in a solvent, adding to the autoclave, heating, and after the temperature in the autoclave reaches 35-60, pumping the supercritical fluid into the autoclave;
步骤三： 通过泵入超临界流体使高压釜内压力升到 75atm-300atm 后， 搅拌 30min-20h, 然后将压力在 5s-20s (优选 10s) 内降为 latm， 具体降压方式可以按照常规 方法进行； 步骤四： 从高压釜内取样， 得到所述寡层石墨烯。 Step 3: After pumping the supercritical fluid to raise the pressure in the autoclave to 75atm-300atm, stir for 30min-20h, then reduce the pressure to lapm within 5s-20s (preferably 10s). The specific pressure reduction method can be carried out according to the conventional method. get on; Step 4: Sampling from the autoclave to obtain the oligo-layer graphene.
根据本发明的具体实施方案， 优选地， 所采用的超临界流体为 co2超临界流体。 根据本发明的具体实施方案，优选地，所采用的石墨粉包括鳞片石墨粉和 /或膨胀石 墨粉等。 According to a particular embodiment of the invention, preferably, the supercritical fluid employed is a co 2 supercritical fluid. According to a particular embodiment of the invention, preferably, the graphite powder employed comprises flake graphite powder and/or expanded graphite powder or the like.
根据本发明的具体实施方案，优选地，所采用的溶剂包括十二垸基硫酸钠和 /或十二 垸基苯磺酸钠等。  According to a particular embodiment of the invention, preferably, the solvent employed comprises sodium decyl sulfate and/or sodium dodecylbenzene sulfonate and the like.
根据本发明的具体实施方案，优选地，所述步骤三中搅拌的速度为 1000-10000r/min。 在上述寡层石墨烯的制备方法中， 可以将所述超临界流体在降压后得到的气体放入 气体罐中回收储存待循环使用。  According to a particular embodiment of the invention, preferably, the rate of agitation in step three is from 1000 to 10000 r/min. In the above preparation method of the oligo-layer graphene, the gas obtained by the supercritical fluid after the pressure reduction may be placed in a gas tank for recovery and storage to be recycled.
根据本发明的具体实施方案， 优选地， 具体石墨粉的纯化处理包括以下步骤： 步骤一： 将石墨粉超声清洗， 去除杂质；  According to a specific embodiment of the present invention, preferably, the purification process of the specific graphite powder comprises the following steps: Step 1: ultrasonically cleaning the graphite powder to remove impurities;
步骤二： 经过化学处理或其它方式去除杂相物质和杂质元素。  Step 2: Chemical treatment or other means to remove the heterogeneous substances and impurity elements.
本发明还提供了一种寡层石墨烯， 其是由上述制备方法制备得到的。  The present invention also provides an oligo-layer graphene which is prepared by the above preparation method.
根据本发明的具体实施方案， 通过上述方法制备的层数在 10层以下的寡层石墨烯 的比率在 60%以上， 优选地， 所述寡层石墨烯的层数为 1-10层。  According to a specific embodiment of the present invention, the ratio of the oligo-layer graphene having a number of layers of 10 or less prepared by the above method is 60% or more, and preferably, the number of layers of the oligo-graphene is 1-10.
本发明还提供了一种用于制备上述寡层石墨烯的装置，其可以用于上述寡层石墨烯 的制备方法。 该装置包括搅拌电机、 加热套、 高压釜、 气体循环***、 搅拌杆、 搅拌头， 其中，  The present invention also provides an apparatus for producing the above oligo-layer graphene, which can be used in the above-described method for producing oligo-layer graphene. The device includes a stirring motor, a heating jacket, an autoclave, a gas circulation system, a stirring rod, a stirring head, wherein
所述搅拌杆竖直位于高压釜顶部的中间，所述搅拌杆在高压釜外面的一端连接搅拌 电机， 延伸至所述高压釜底部的另一端连接搅拌头；  The stirring rod is vertically located in the middle of the top of the autoclave, and the stirring rod is connected to the stirring motor at one end of the outer portion of the autoclave, and the other end of the bottom of the autoclave is connected to the stirring head;
在所述高压釜的顶部设置有进样口和气体入口； 所述进样口与所述气体入口分置于 搅拌电机的两侧；  An inlet and a gas inlet are disposed at a top of the autoclave; the inlet and the gas inlet are disposed on both sides of the stirring motor;
所述加热套包裹在所述高压釜的外部；  The heating jacket is wrapped on the outside of the autoclave;
所述高压釜的底部设置有出样口；  The bottom of the autoclave is provided with a sample outlet;
所述气体循环***包括气体罐、 第一阔门、 第二阔门、 流量计、 冷凝设备和第三阔 门， 从气体入口引出的管线依次连通第一阔门、 气体罐、 第二阔门、 流量计、 冷凝设备 和第三阔门， 管线末端与气体入口引出的管线连通， 构成气体循环***； 其中， 第一阔 门、 第二阔门和第三阔门用于控制管路的开通与闭合， 流量计用于计量气体的量， 气体 罐用于储存所需要的气体和回收的气体， 冷凝设备对气体进行冷凝， 与外界压力泵一起 作用， 使气体成为超临界状态， 可以采用任何能够实现该功能的设备； 所述气体循环***与所述气体入口连通。 The gas circulation system includes a gas tank, a first wide door, a second wide door, a flow meter, a condensing device, and a third wide door, and the line leading from the gas inlet sequentially connects the first wide door, the gas tank, and the second wide door , the flow meter, the condensing device and the third wide door, the end of the pipeline is connected with the pipeline leading from the gas inlet to form a gas circulation system; wherein the first wide gate, the second wide gate and the third wide gate are used for controlling the opening of the pipeline And closed, the flow meter is used for metering the amount of gas, the gas tank is used for storing the required gas and the recovered gas, the condensing device condenses the gas, and acts together with the external pressure pump to make the gas supercritical, any of which can be used a device capable of implementing this function; The gas circulation system is in communication with the gas inlet.
采用上述装置制备寡层石墨烯时， 首先， 第一阔门、 第二阔门、 第三阔门处于闭合 状态， 将纯化后的石墨粉直接加入到高压釜内或分散在溶剂中后加入高压釜内， 通过加 热套进行加热， 待高压釜内的温度达到 35-60 后， 打开第二阔门、 第三阔门， 气体罐 中的气体通过冷凝设备冷凝， 与外界压力泵一起作用使气体转化为超临界流体， 将超临 界流体泵入高压釜内； 然后， 通过泵入超临界流体使高压釜内压力升到 75atm-300atm 后， 关闭第二阔门和第三阔门， 开启搅拌电机进行搅拌， 利用高速流动的超临界流体产 生的剪切力将石墨剥离开， 搅拌 30min-20h后， 将压力在 5s-20s内降为 latm， 打开第一 阔门回收气体后再关闭第一阔门； 最后， 从高压釜内取样， 即制得寡层石墨烯。  When the oligo-graphene is prepared by the above device, first, the first wide gate, the second wide gate, and the third wide gate are in a closed state, and the purified graphite powder is directly added into the autoclave or dispersed in a solvent and then added to a high pressure. In the kettle, heating is performed by a heating jacket. After the temperature in the autoclave reaches 35-60, the second wide door and the third wide door are opened, and the gas in the gas tank is condensed by the condensing device, and acts together with the external pressure pump to make the gas Conversion into a supercritical fluid, pumping the supercritical fluid into the autoclave; then, after pumping the supercritical fluid to raise the pressure in the autoclave to 75atm-300atm, the second wide door and the third wide door are closed, and the stirring motor is turned on. Stirring, using the shear force generated by the high-speed flow of supercritical fluid to separate the graphite, stirring for 30min-20h, the pressure is reduced to lapm within 5s-20s, open the first wide door and then close the first wide Finally, the oligo-graphene is produced by sampling from the autoclave.
本发明所提供的寡层石墨烯的制备方法是高效制备寡层石墨烯的方法， 能大量制备 高质量的寡层石墨烯， 并且该方法制备的石墨烯层数少。  The preparation method of the oligo-layer graphene provided by the invention is a method for efficiently preparing the oligo-layer graphene, and can prepare a high-quality oligo-layer graphene in a large amount, and the number of graphene layers prepared by the method is small.
本发明所提供的寡层石墨烯的制备方法绿色环保，生产成本低，能够循环利用 C02， 降低 co2排放及成本。 同时， 还具有反应周期短， 工艺简单， 制备得到的寡层石墨烯的 片层完整性好等优点。 附图说明 The preparation method of the oligo-layer graphene provided by the invention is environmentally friendly, has low production cost, can recycle C0 2 , and reduces co 2 emission and cost. At the same time, it has the advantages of short reaction cycle, simple process, and good integrity of the prepared oligo-graphene. DRAWINGS
图 1为本发明所提供的寡层石墨烯的制备方法的流程图；  1 is a flow chart of a method for preparing an oligo-layer graphene provided by the present invention;
图 2为本发明所提供的制备寡层石墨烯装置的结构示意图；  2 is a schematic structural view of an apparatus for preparing an oligo-layer graphene provided by the present invention;
图 3为实施例 1制备的寡层石墨烯的透射电镜 （TEM) 图；  3 is a transmission electron microscope (TEM) image of the oligo-layer graphene prepared in Example 1;
图 4为实施例 1制备的寡层石墨烯的另一透射电镜 （TEM) 图；  4 is another transmission electron microscope (TEM) image of the oligo-layer graphene prepared in Example 1.
图 5为实施例 2制备的寡层石墨烯的透射电镜 （TEM) 图；  5 is a transmission electron microscope (TEM) image of the oligo-layer graphene prepared in Example 2;
图 6为实施例 2制备的寡层石墨烯的另一透射电镜 （TEM) 图。  Figure 6 is another transmission electron microscope (TEM) image of the oligo-layer graphene prepared in Example 2.
主要组件符号说明：  Main component symbol description:
1 高压釜 2 加热套 3 搅拌电机 4 搅拌杆 5 搅拌头 6 进样口 7 气体入口 8 出样口 9 第一阔门 10 第二阔门 11 流量计 12 气体罐 13 冷凝设备 14 第三阔门 具体实施方式  1 Autoclave 2 Heating jacket 3 Mixing motor 4 Mixing rod 5 Mixing head 6 Inlet 7 Gas inlet 8 Outlet 9 First wide door 10 Second wide door 11 Flow meter 12 Gas tank 13 Condensing equipment 14 Third wide door detailed description
为了对本发明的技术特征、 目的和有益效果有更加清楚的理解， 现参照说明书附图 对本发明的技术方案进行以下详细说明， 但不能理解为对本发明的可实施范围的限定。  The detailed description of the technical features of the present invention will be understood by the following detailed description of the invention.
实施例 1  Example 1
本实施例提供了一种用于制备寡层石墨烯的装置，其结构如图 2所示。该装置包括： 搅拌电机 3、 加热套 2、 高压釜 1、 气体循环***、 搅拌杆 4、 搅拌头 5， 其中， 搅拌杆 4竖直位于高压釜 1顶部的中间，搅拌杆 4在高压釜 1外面的一端连接搅拌 电机 3， 延伸至高压釜 1底部的另一端连接搅拌头 5; This embodiment provides an apparatus for preparing an oligo-layer graphene, the structure of which is shown in FIG. The device includes: a stirring motor 3, a heating jacket 2, an autoclave 1, a gas circulation system, a stirring rod 4, and a stirring head 5, wherein the stirring rod 4 is vertically located in the middle of the top of the autoclave 1, and the stirring rod 4 is connected at one end of the outside of the autoclave 1 Mixing motor 3, extending to the other end of the bottom of the autoclave 1 is connected to the stirring head 5;
在高压釜 1的顶部设置有进样口 6和气体入口 7; 进样口 6与气体入口 7分置于搅 拌电机 3的两侧；  An inlet 6 and a gas inlet 7 are provided at the top of the autoclave 1; the inlet 6 and the gas inlet 7 are placed on both sides of the stirring motor 3;
加热套 2包裹在高压釜 1的外部；  The heating jacket 2 is wrapped outside the autoclave 1;
高压釜 1的底部设置有出样口 8;  The bottom of the autoclave 1 is provided with a sample outlet 8;
气体循环***包括气体罐 12、 第一阔门 9、 第二阔门 10、 流量计 11、 冷凝设备 13 和第三阔门 14， 从气体入口 7引出的管线依次连通第一阔门 9、 气体罐 12、 第二阔门 10、流量计 11、冷凝设备 13和第三阔门 14，管线末端与从气体入口 7引出的管线连通， 构成气体循环***； 其中， 第一阔门 9和第二阔门 10用于控制管路的开通与闭合， 流 量计 11用于计量气体的量， 气体罐 12用于储存所需要的气体和回收的气体， 冷凝设备 13对气体进行冷凝， 与外界压力泵一起作用， 使气体成为超临界状态， 可以采用任何能 够实现该功能的设备； 气体循环***与气体入口 7连通。  The gas circulation system includes a gas tank 12, a first wide door 9, a second wide door 10, a flow meter 11, a condensing device 13 and a third wide door 14, and the line leading from the gas inlet 7 sequentially connects the first wide door 9, gas a tank 12, a second wide door 10, a flow meter 11, a condensing device 13 and a third wide door 14, the end of the line is in communication with a line leading from the gas inlet 7, forming a gas circulation system; wherein, the first wide door 9 and the second The wide door 10 is used for controlling the opening and closing of the pipeline, the flow meter 11 is for metering the amount of gas, the gas tank 12 is for storing the required gas and the recovered gas, the condensing device 13 is condensing the gas, and the external pressure pump As soon as the function is made to make the gas supercritical, any device capable of performing this function can be employed; the gas circulation system is in communication with the gas inlet 7.
利用上述装置制备寡层石墨烯， 制备流程图如图 1所示， 该制备过程具体可以包括 以下步骤：  The oligo-graphene is prepared by the above device, and the preparation flow chart is as shown in FIG. 1. The preparation process may specifically include the following steps:
步骤一、 准备石墨粉： 将 10g鳞片石墨粉超声清洗 （水洗 1次， 乙醇洗 2次） 以去 除杂相物质和杂质元素；  Step 1. Prepare graphite powder: Ultrasonic cleaning (10 times of water washing and 2 times of ethanol washing) to remove impurities and impurity elements;
步骤二、 超临界 C02插层： 第一阔门 9、 第二阔门 10、 第三阔门 14处于闭合状态， 将纯化后的鳞片石墨粉直接加入到高压釜 1内并进行加热，待高压釜 1内的温度达到 35 °C后， 打开第二阔门 10、 第三阔门 14， 将气体罐 12中的 C02气体通过冷凝设备 13冷 凝， 与外界压力泵的一起作用将 C02气体转化为 C02超临界流体， 将 C02超临界流体 泵入高压釜 1内， C02超临界流体的用量通过流量计 11计量； Step 2: Supercritical C0 2 intercalation: the first wide door 9, the second wide door 10, and the third wide door 14 are in a closed state, and the purified flake graphite powder is directly added into the autoclave 1 and heated. After the temperature in the autoclave 1 reaches 35 ° C, the second wide door 10 and the third wide door 14 are opened, and the C0 2 gas in the gas tank 12 is condensed by the condensing device 13, and together with the external pressure pump, C0 2 The gas is converted into a C0 2 supercritical fluid, and the C0 2 supercritical fluid is pumped into the autoclave 1, and the amount of the C0 2 supercritical fluid is metered by the flow meter 11;
步骤三、超临界 C02剪切：通过泵入 C02超临界流体使高压釜 1内压力升到 300atm 后， 关闭第二阔门 10和第三阔门 14， 开启搅拌电机 3进行搅拌， 转速为 10000r/min， 利用高速流动的 C02超临界流体产生的剪切力将石墨剥离开， 搅拌 30min后将压力在 10s内降为 latm， 打开第一阔门 9回收气体后再关闭第一阔门 9; Step 3: Supercritical C0 2 shearing: After pumping the C0 2 supercritical fluid to raise the pressure in the autoclave 1 to 300 atm, the second wide door 10 and the third wide door 14 are closed, and the stirring motor 3 is turned on for stirring. For 10000r/min, the graphite is peeled off by the shear force generated by the high-speed flowing C0 2 supercritical fluid. After stirring for 30 minutes, the pressure is reduced to lapm within 10s, and the first wide door 9 is opened to recover the gas and then the first wide is closed. Door 9;
步骤四、 得到石墨烯： 从高压釜 1内取样， 得到所述寡层石墨烯。  Step 4: Obtaining graphene: Sampling from the autoclave 1 to obtain the oligo-layer graphene.
对制得的寡层石墨烯通过透射电镜 （TEM) 进行拍照， 如图 3和图 4所示。 从图 3 和图 4可以清楚的看到本实施例制备的寡层石墨烯的层数， 同时可以观察到石墨烯的缺 陷较少， 通过对其层数进行统计， 发现实施例 1制得的石墨烯的层数在 10层以下的比 率约为 60%。 The obtained oligo-graphene was photographed by a transmission electron microscope (TEM) as shown in Figs. 3 and 4. The number of layers of the oligo-layer graphene prepared in this example can be clearly seen from FIG. 3 and FIG. 4, and the lack of graphene can be observed. The trapping was small, and by counting the number of layers thereof, it was found that the ratio of the number of layers of graphene obtained in Example 1 to 10 or less was about 60%.
实施例 2  Example 2
本实施例提供一种寡层石墨烯的制备方法， 其是利用实施例 1所述的装置制备的， 该方法具体包括以下步骤：  The present embodiment provides a method for preparing an oligo-graphene, which is prepared by using the apparatus described in Embodiment 1, and the method specifically includes the following steps:
步骤一、 准备石墨粉： 将 lg膨胀石墨粉超声清洗 （水洗 1次， 乙醇洗 2次） 以去 除杂相物质和杂质元素；  Step 1. Prepare graphite powder: Ultrasonic cleaning of lg expanded graphite powder (washing once, washing twice with ethanol) to remove impurities and impurity elements;
步骤二、 超临界 C02插层： 第一阔门 9、 第二阔门 10、 第三阔门 14处于闭合状态， 将纯化后的膨胀石墨粉分散在 200mL浓度为 lwt%的十二垸基硫酸钠 （SDS) 中后， 加 入到高压釜 1 内并进行加热， 待高压釜 1 内的温度达到 60°C后， 打开第二阔门 10、 第 三阔门 14， 将气体罐 12中的 C02气体通过冷凝设备 13冷凝， 与外界压力泵的一起作 用将 C02气体转化为 C02超临界流体， 将 C02超临界流体泵入高压釜 1 内， C02超临 界流体的用量通过流量计 11计量； Step 2: Supercritical C0 2 intercalation: The first wide door 9, the second wide door 10, and the third wide door 14 are in a closed state, and the purified expanded graphite powder is dispersed in 200 mL of a 12 wt% twelfth base. After sodium sulfate (SDS), it is added to the autoclave 1 and heated. After the temperature in the autoclave 1 reaches 60 ° C, the second wide door 10 and the third wide door 14 are opened, and the gas can 12 is opened. The C0 2 gas is condensed by the condensing device 13, and together with the external pressure pump, the C0 2 gas is converted into the C0 2 supercritical fluid, and the C0 2 supercritical fluid is pumped into the autoclave 1, and the amount of the C0 2 supercritical fluid is passed through the flow. Meter 11 metering;
步骤三、 超临界 C02剪切： 通过泵入 C02超临界流体使高压釜 1内压力升到 75atm 后， 关闭第二阔门 10和第三阔门 14， 开启搅拌电机 3进行搅拌， 转速为 lOOOr/min, 利 用高速流动的 C02超临界流体产生的剪切力将石墨剥离开，搅拌 20h，然后将压力在 10s 内降为 latm， 打开第一阔门 9回收气体后再关闭第一阔门 9; Step 3: Supercritical C0 2 shearing: After pumping the C0 2 supercritical fluid to raise the pressure in the autoclave 1 to 75 atm, the second wide door 10 and the third wide door 14 are closed, and the stirring motor 3 is turned on for stirring. For lOOOr/min, the graphite is peeled off by the shear force generated by the high-speed flowing C0 2 supercritical fluid, stirred for 20h, then the pressure is reduced to lapm within 10s, and the first wide door 9 is opened to recover the gas and then closed first. Wide door 9;
步骤四、 得到石墨烯： 从高压釜 1内取样， 得到所述寡层石墨烯。  Step 4: Obtaining graphene: Sampling from the autoclave 1 to obtain the oligo-layer graphene.
对制得的寡层石墨烯用透射电镜（TEM)进行拍照， 如图 5和图 6所示。 从图 5和 图 6可以清楚的看到本实施例制备的寡层石墨烯的层数， 同时可以观察到石墨烯的缺陷 较少， 通过对其层数进行统计， 发现实施例 2制得的石墨烯的层数在 10层以下的比率 约为 80%。  The obtained oligo-ply graphene was photographed by a transmission electron microscope (TEM) as shown in Figs. 5 and 6. It can be clearly seen from FIG. 5 and FIG. 6 that the number of layers of the oligo-layer graphene prepared in the present embodiment is small, and at the same time, the defects of the graphene are less observed, and the number of layers is counted, and the results obtained in the embodiment 2 are found. The ratio of the number of layers of graphene to 10 or less is about 80%.

Claims

权利要求书 claims
1、 一种寡层石墨烯的制备方法， 其包括以下步骤： 1. A method for preparing oligolayer graphene, which includes the following steps:
步骤一： 对石墨粉进行纯化处理； Step 1: Purify the graphite powder;
步骤二： 将纯化后的石墨粉直接加入高压釜内或分散在溶剂中后加入高压釜内， 进 行加热， 待高压釜内的温度达到 35-60 后， 将超临界流体泵入高压釜内； Step 2: Add the purified graphite powder directly into the autoclave or disperse it in a solvent and then add it into the autoclave and heat it. After the temperature in the autoclave reaches 35-60°C, pump the supercritical fluid into the autoclave;
步骤三： 通过泵入超临界流体使高压釜内压力升到 75atm-300atm 后， 搅拌 30min-20h, 然后将压力在 5s-20s内降为 lata; Step 3: Pump the supercritical fluid into the autoclave to raise the pressure to 75atm-300atm, stir for 30min-20h, and then reduce the pressure to lata within 5s-20s;
步骤四： 从高压釜内取样， 得到所述寡层石墨烯。 Step 4: Take a sample from the autoclave to obtain the oligolayer graphene.
2、 根据权利要求 1所述的制备方法， 其中， 所述超临界流体为 C02超临界流体。 2. The preparation method according to claim 1, wherein the supercritical fluid is C0 2 supercritical fluid.
3、 根据权利要求 1所述的制备方法， 其中， 所述石墨粉包括鳞片石墨粉和 /或膨胀 石墨粉。 3. The preparation method according to claim 1, wherein the graphite powder includes flake graphite powder and/or expanded graphite powder.
4、 根据权利要求 1所述的制备方法， 其中， 所述溶剂包括十二垸基硫酸钠和 /或十 二垸基苯磺酸钠。 4. The preparation method according to claim 1, wherein the solvent includes sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
5、 根据权利要求 1 所述的制备方法， 其中， 所述步骤三中搅拌的速度为 1000-10000r/min。 5. The preparation method according to claim 1, wherein the stirring speed in step three is 1000-10000r/min.
6、根据权利要求 1所述的制备方法，其中，所述步骤三中将压力在 10s内降为 latm。 6. The preparation method according to claim 1, wherein in step three, the pressure is reduced to latm within 10s.
7、 根据权利要求 1所述的制备方法， 其中， 将所述超临界流体降压后得到的气体 放入气体罐中储存待循环使用。 7. The preparation method according to claim 1, wherein the gas obtained after decompressing the supercritical fluid is placed in a gas tank and stored for recycling.
8、 根据权利要求 1所述的制备方法， 其中， 所述石墨粉的纯化处理包括以下步骤: 步骤一： 将石墨粉超声清洗， 去除杂质； 8. The preparation method according to claim 1, wherein the purification treatment of the graphite powder includes the following steps: Step 1: Ultrasonic cleaning of the graphite powder to remove impurities;
步骤二： 经过化学处理或其它方式去除杂相物质和杂质元素。 Step 2: Remove impurities and impurity elements through chemical treatment or other methods.
9、 一种寡层石墨烯， 其是由权利要求 1所述的制备方法制得的。 9. An oligolayer graphene prepared by the preparation method of claim 1.
10、 根据权利要求 9所述的寡层石墨烯， 其中， 所述寡层石墨烯的层数为 1-10层。 10. The oligolayer graphene according to claim 9, wherein the number of layers of the oligolayer graphene is 1-10 layers.
11、 一种用于制备权利要求 9所述的寡层石墨烯的装置， 其包括， 搅拌电机、 加热 套、 高压釜、 气体循环***、 搅拌杆、 搅拌头， 其中， 11. A device for preparing the oligolayer graphene according to claim 9, which includes a stirring motor, a heating jacket, an autoclave, a gas circulation system, a stirring rod, and a stirring head, wherein,
所述搅拌杆竖直位于高压釜顶部的中间，所述搅拌杆在高压釜外面的一端连接搅拌 电机， 延伸至所述高压釜底部的另一端连接搅拌头； The stirring rod is located vertically in the middle of the top of the autoclave, one end of the stirring rod outside the autoclave is connected to the stirring motor, and the other end extending to the bottom of the autoclave is connected to the stirring head;
在所述高压釜的顶部设置有进样口和气体入口； 所述进样口与所述气体入口分置于 搅拌电机的两侧； A sample inlet and a gas inlet are provided on the top of the autoclave; the sample inlet and the gas inlet are located on both sides of the stirring motor;
所述加热套包裹在所述高压釜的外部； 所述高压釜的底部设置有出样口； The heating jacket is wrapped around the outside of the autoclave; The bottom of the autoclave is provided with a sample outlet;
所述气体循环***包括气体罐、 第一阔门、 第二阔门、 流量计、 冷凝设备和第三阔 门， 从气体入口引出的管线依次连通第一阔门、 气体罐、 第二阔门、 流量计、 冷凝设备 和第三阔门， 管线末端与气体入口引出的管线连通， 构成气体循环***； The gas circulation system includes a gas tank, a first wide door, a second wide door, a flow meter, a condensation device and a third wide door. The pipeline leading from the gas inlet connects the first wide door, the gas tank and the second wide door in sequence. , flow meter, condensation equipment and the third wide door, the end of the pipeline is connected with the pipeline leading from the gas inlet to form a gas circulation system;
所述气体循环***与所述气体入口连通。 The gas circulation system is connected with the gas inlet.
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