WO2011066811A1 - Method for preparing few-layer graphene and few-layer graphene film - Google Patents

Method for preparing few-layer graphene and few-layer graphene film Download PDF

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WO2011066811A1
WO2011066811A1 PCT/CN2010/079477 CN2010079477W WO2011066811A1 WO 2011066811 A1 WO2011066811 A1 WO 2011066811A1 CN 2010079477 W CN2010079477 W CN 2010079477W WO 2011066811 A1 WO2011066811 A1 WO 2011066811A1
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graphite
anode
oligo
mpa
gas
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PCT/CN2010/079477
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French (fr)
Chinese (zh)
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陈永胜
吴英鹏
张龙
黄毅
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南开大学
天津普兰纳米科技有限公司
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Priority to CN201080062867.XA priority Critical patent/CN102781831B/en
Publication of WO2011066811A1 publication Critical patent/WO2011066811A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/04—Specific amount of layers or specific thickness

Definitions

  • the present application relates to carbon materials and methods for their preparation, and in particular to a process for the preparation of graphene containing different layers and solutions and films thereof.
  • Carbon has many forms of existence, including common graphite, diamond, amorphous carbon, and carbon 60 found in recent years, carbon nanotubes, and graphene. Although these materials are composed of carbon, the structure and properties vary greatly. Among them, graphene is a single-layer graphite or a multi-layer graphite material composed of a single piece of graphite. Graphene materials have many excellent properties, such as extremely high electrical conductivity and mechanical properties. Therefore, the film obtained from the graphene material has a wide application prospect. However, there is currently no good large-scale preparation method. Therefore, there is an urgent need for a large-scale preparation method that is feasible from both research and industrial applications. Overview
  • An aspect of the present application provides a method of preparing an oligo-pigment graphite, the method comprising:
  • Another aspect of the present application provides a method of producing an oligolithic graphite film, the method comprising: mixing an oligolithic graphite solid obtained in the foregoing method with a solvent to prepare a solution, coating the solution, and forming a film Heat in an inert gas.
  • Fig. 1 is an electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of H 2 and He.
  • Fig. 3 is an atomic force micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (30% partial pressure) and He.
  • Figure 4 is an XRD pattern of oligo-ply graphite.
  • Figure 5 is a thermograviogram of oligo-ply graphite.
  • Fig. 6 is an electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He.
  • Fig. 7 is a high-resolution electron transmission micrograph of the oligo-ply graphite synthesized by the arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He.
  • Fig. 8 is a high-resolution electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He.
  • Fig. 9 is an atomic force micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (40% partial pressure) and He.
  • Fig. 10 is a high-resolution electron transmission micrograph of an oligographite synthesized by an arc method in a mixed gas atmosphere of CO 2 (40% partial pressure) and He.
  • Figure 11 is a graph showing the conductivity of a film made of an oligo graphite solution.
  • oligolayer graphite (FG) as used in the present invention means that its molecular constituent unit is
  • single-layer graphite refers to a two-dimensional planar molecular skeleton consisting of a single layer of carbon atoms with a single-chip area between 10 nm 2 and 1000 ⁇ m 2 and a single-sheet thickness between about 0.34 nm and 2 nm.
  • the carbon atoms of the edge portion of the layer in "oligolayer graphite” and “single layer graphite” may be bonded to different organic functional groups such as a hydroxyl group, an amino group, a carboxyl group, an epoxy group or the like depending on the specific preparation method and preparation conditions.
  • An aspect of the present application provides a method of preparing an oligo-pigment graphite, the method comprising:
  • Exemplary inert gases that can be used in the present application include N 2 , He, Ne, Ar, Kr, and Xe.
  • the inert gas is He or Ar or a mixture thereof.
  • Exemplary gases that are reactive with carbon in the present application include, but are not limited to, ammonia, hydrogen, carbon dioxide, air, oxygen, and the like.
  • the volume ratio of the inert gas to the gas which is reactive with carbon in the mixed gas is from 9:95 to 95:5. In certain embodiments of the present application, the volume of the inert gas and the gas reactive with carbon in the mixed gas is from 80:20 to 20:80. In certain embodiments of the present application, the volume of the inert gas and the gas reactive with carbon in the mixed gas is from 75:25 to 25:75.
  • the total pressure of the mixed gas is from 0.02 MPa to 0.4 MPa. In certain embodiments, the total pressure of the mixed gas is from 0.05 MPa to 0.3 MPa. In some embodiments, the total pressure of the mixed gas is from 0.07 MPa to 0.2 MPa.
  • both electrodes are electrodes of carbon material. In some embodiments, both electrodes are electrodes of graphite.
  • the arc discharge process may employ an alternating arc discharge or a direct current arc discharge, and the discharge voltage is 10-200 V, and the current is 10-250A. In certain embodiments, in the method of preparing oligo-pigmented graphite, the arc discharge process may employ an alternating arc discharge or a direct current arc discharge with a discharge voltage of 10-80 V and a current of 50-200 A.
  • the arc discharge process employs a DC arc discharge with a discharge voltage of 15-50 V and a current of 80-180 A. In some embodiments, the arc discharge process employs a direct current arc discharge with a discharge voltage of 15-40 V and a current of 100-150 A.
  • the current during discharge is controlled by the power supply and the voltage between the two electrodes is adjusted by adjusting the distance between the two electrodes.
  • the anode is a consumable electrode.
  • the discharge between the cathode and the anode is exhausted to the anode.
  • a method of making oligo-pigment graphite comprising:
  • Two carbon electrodes are provided as a cathode and an anode, wherein the larger diameter is the cathode and the smaller diameter is the anode;
  • the cathode has a diameter of from 3 mm to 10 cm. In some embodiments, the cathode has a diameter of 1 cm. In certain embodiments, the anode has a diameter of from 2 mm to 8 cm. In certain embodiments, the anode has a diameter of 5 mm.
  • the mixed gas is comprised of an inert gas and a gas that is reactive toward carbon.
  • the method is carried out in an electric furnace.
  • the oligo-pigment graphite obtained by the method may contain graphene sheets of different layers.
  • Another aspect of the present application provides a method of preparing an oligolithic graphite film, the method comprising: directly applying the oligo-pigment graphite solid to a film, or mixing with a solvent to prepare a solution, coating the solution, and The formed film is heated in an inert gas to controllably remove functional groups on the graphene sheets and repair defects to restore the intrinsic conductivity of the graphene to obtain a highly conductive film.
  • a graphene conductive film can be obtained by reducing with a reducing agent, including a gas reducing agent.
  • the solvent used in the preparation of the oligo graphite solution may be any volatile solvent, and exemplary solvents include, but are not limited to: water; hydrazine, hydrazine-dimethylformamide (DMF), hydrazine, hydrazine-dimethyl ethene Amides such as amides; alcohols such as ethanol, methanol, isopropanol; dimethyl sulfoxide (DMSO); Chlorinated solvents such as chlorobenzene, dichlorobenzene, and dichloromethane; esters such as ethyl acetate, methyl acetate, and dimethyl phthalate (DMP).
  • exemplary solvents include, but are not limited to: water; hydrazine, hydrazine-dimethylformamide (DMF), hydrazine, hydrazine-dimethyl ethene Amides such as amides; alcohols such as ethanol, methanol, isopropanol;
  • a coating film method well known in the art may be employed, including but not limited to spin coating, spray coating, dipping, and the like.
  • an oligo-graphite film of the present application may optionally include adding a dispersing agent, a thickener, etc. to the solution prepared by mixing the above oligo-pigment graphite solution or the above-mentioned oligo-pigment graphite solid and a solvent before performing the coating film.
  • a dispersing agent e.g., sodium bicarbonate
  • a thickener e.g., sodium bicarbonate
  • a step of reducing the conductivity of the film by using a reducing agent after the coating film may be optionally included.
  • the reducing vapor is hydrazine hydrate vapor.
  • a pure carbon rod was used as the anode.
  • a mixture of H 2 and He (pressure ratio 1:1) was introduced into the electric arc furnace to a pressure of 0.07 MPa in the furnace. Set the output current to 100 A.
  • the voltage was maintained at about 30 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa.
  • the anode is consumed and the reaction is completed.
  • the product collected in the electric arc furnace is oligo graphite.
  • a pure carbon rod was used as the anode.
  • a mixture of H 2 and He is introduced into the electric arc furnace (pressure ratio)
  • the pressure in the furnace is 0.07 MPa. Set the output current to 150 A. After the discharge started, the voltage was maintained at about 37 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite.
  • Fig. 1 is an electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of H 2 and He.
  • the product is in the form of an oligo-graphite structure, and some of the sheet-like structures are bent to form wrinkles, and a layered structure can be seen.
  • Example 3
  • a pure carbon rod was used as the anode.
  • a mixture of C0 2 and He (C0 2 5% partial pressure) was introduced into the electric arc furnace to a pressure of 0.07 MPa in the furnace. Set the output current to 150 A.
  • the voltage was maintained at about 32 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa.
  • the anode is consumed and the reaction is completed.
  • the product collected in the electric arc furnace is oligo graphite.
  • a pure carbon rod was used as the anode.
  • a mixture of C0 2 and He (C0 2 accounted for 30% partial pressure) was introduced into the electric arc furnace to a pressure of 0.07 MPa in the furnace. Set the output current to 150 A. After the discharge started, the voltage was maintained at about 22 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite.
  • a pure carbon rod was used as the anode.
  • a mixture of C0 2 and He (C0 2 accounted for 30% partial pressure) was introduced into the electric arc furnace to a pressure of 0.07 MPa in the furnace. Set the output current to 200 A. After the discharge started, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite.
  • a pure carbon rod was used as the anode.
  • a mixture of C0 2 and He (C0 2 accounted for 30% partial pressure) was introduced into the electric arc furnace to a pressure of 0.17 MPa in the furnace. Set the output current to 150 A.
  • the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.17 MPa.
  • the anode is consumed and the reaction is completed.
  • the product collected in the electric arc furnace is oligo graphite.
  • FIG. 2 is a Raman spectrum of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (30% partial pressure) and He. From the half-width and peak shape of its 2D peak, it can be estimated that the product is mainly 4 layers of oligo-pigment graphite.
  • Figure 3 is an atomic force micrograph of the oligo-ply graphite synthesized by arc method in a mixed gas atmosphere of CO 2 (30% partial pressure) and He. As can be seen from the figure, the partial thickness of the product graphite sheet is about 2.62 nm, indicating that the product is Oligomerized graphite sheet structure.
  • Example 7
  • a pure carbon rod was used as the anode.
  • a mixture of C0 2 and He (C0 2 accounted for 30% partial pressure) was introduced into the electric arc furnace to a pressure of 0.10 MPa in the furnace. Set the output current to 150 A. After the start of the discharge, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.10 MPa. The anode is consumed and the reaction is completed.
  • the flocculent product collected in the electric arc furnace is oligo graphite.
  • a pure carbon rod was used as the anode.
  • a mixture of C0 2 and He (C 2 2 is divided by 25%) is introduced into the electric arc furnace to a pressure of 0.20 MPa in the furnace. Set the output current to 150 A. After the discharge started, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.20 MPa. The anode is consumed and the reaction is completed.
  • the product collected in the electric arc furnace is oligo graphite.
  • Figure 4 is an XRD pattern of the obtained oligo-ply graphite. It can be seen from the figure that the two peaks indicate that the distance between the product sheets is 3.4 nm and 4.2 nm, respectively, and the peak at 3.4 nm is sharper, indicating that there is a relatively complete ordinary graphite sheet structure in the product, and 4.2 nm The peak is wider, indicating that the product has a layer spacing larger than that of the ordinary graphite sheet, and is in an amorphous state, which conforms to the structure of the oligo graphite.
  • Figure 5 is a thermograviogram of the obtained oligo-ply graphite. As can be seen from the figure, the product has little thermal weight loss throughout the temperature zone, indicating that the product contains less functional groups, much smaller than the single layer graphite and oligo-pigment graphite produced by the conventional solution method.
  • Fig. 6 is an electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He. It can be seen from the figure that the product is a flaky structure of oligo-pigmented graphite, and part of the graphite sheet layer forms wrinkles.
  • Fig. 7 is a high-resolution electron transmission micrograph of the oligo-ply graphite synthesized by the arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He. It can be seen from the figure that the product is a flaky structure of oligo-ply graphite, and the edge indicated by the arrow is a three-layer graphite sheet structure.
  • Fig. 8 is a high-resolution electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He. The flaky graphene formed can be seen from the electron micrograph, and the number of layers of the graphene sheet pleats indicated by the arrows is two, four, and five layers, respectively.
  • Example 9
  • a pure carbon rod was used as the anode.
  • a mixture of C0 2 and He (C 2 2 is divided by 25%) is introduced into the electric arc furnace to a pressure of 0.17 MPa in the furnace. Set the output current to 150 A.
  • the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.17 MPa.
  • the anode is consumed and the reaction is completed.
  • the flocculent product collected in the electric arc furnace is oligo graphite.
  • a pure carbon rod was used as the anode.
  • a mixture of C0 2 and He (C0 2 accounted for 40% partial pressure) was introduced into the electric arc furnace to a pressure of 0.17 MPa in the furnace. Set the output current to 150 A. After the discharge started, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.17 MPa. The anode is consumed and the reaction is completed.
  • the product collected in the electric arc furnace is oligo graphite.
  • Fig. 9 is an atomic force micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (40% partial pressure) and He.
  • the partial thickness of the product graphite sheet was 2.80 nm, indicating that the product was an oligo-graphite sheet structure.
  • Fig. 10 is a high-resolution electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (40% partial pressure) and He. It can be seen from the figure that the product is a flaky structure of oligo-pigment graphite, and the edge indicated by the arrow is a six-layer graphite sheet structure.
  • Example 11
  • the pure carbon rod is machined and used as an anode.
  • a mixture of C0 2 and Ar is introduced (( 0 2 is 33% partial pressure) to a furnace pressure of 0.17 MPa.
  • the output current is set to 150 A.
  • the voltage is maintained by adjusting the distance between the cathode and the anode.
  • the pressure in the furnace was maintained at about 0.17 MPa.
  • the anode was consumed and the reaction was completed.
  • the product in the collection arc furnace was oligo graphite.
  • the pure carbon rod is machined and used as an anode.
  • a mixture of air and He air 50% partial pressure
  • the voltage was maintained at about 30 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at 0.17-0.20 MPa.
  • the anode is consumed and the reaction is completed.
  • the product in the collection arc furnace is oligo graphite. Oligo-layer graphite solution preparation
  • the oligo graphite solution prepared in Example 13 or 14 was obtained by spin coating on a cleaned quartz sheet, and dried by heating to obtain an oligo graphite conductive film.
  • Figure 11 is a graph showing the conductivity of a film made of an oligo graphite solution. Conductivity is ⁇ 10 3

Abstract

Provided is a method for preparing few-layer graphene, which comprises the following steps: (1) providing two carbon electrodes as cathode and anode; and (2) applying a voltage between the two electrodes under a mixed gas atmosphere containing inert gas and gas which is reactive to carbon. Also provided is a method for preparing few-layer graphene film, which comprises the following steps: (1) coating with the solid of few-layer graphene, or mixing the solid of few-layer graphene with solvent to give a solution and then coating with the solution; and (2) heating and reducing the formed film under an atmosphere of inert gas or reducing gas.

Description

寡层石墨及寡层石墨薄膜的制备方法 领域  Preparation method of oligo-layer graphite and oligo-graphite film
本申请涉及碳材料及其制备方法， 具体地涉及含有不同层数的石 墨烯及其溶液和薄膜的制备方法。 背景  The present application relates to carbon materials and methods for their preparation, and in particular to a process for the preparation of graphene containing different layers and solutions and films thereof. Background
碳有多种存在形式， 包括常见的石墨、 金刚石、 无定型碳和近年 发现的碳 60、 碳纳米管和石墨烯。 这些材料虽然都由碳元素构成， 但 结构和性质差别极大。 其中石墨烯为由单片石墨构成的单层石墨或多 层石墨材料。 石墨烯材料具有许多优良的性质， 比如具有极高的导电 能力和机械性能。 因此， 由石墨烯材料获得的薄膜具有广泛的应用前 景。 但目前还没有较好的大规模制备方法。 因此无论从研究和工业应 用方面都急需一种筒单可行的大规模制备方法。 概述  Carbon has many forms of existence, including common graphite, diamond, amorphous carbon, and carbon 60 found in recent years, carbon nanotubes, and graphene. Although these materials are composed of carbon, the structure and properties vary greatly. Among them, graphene is a single-layer graphite or a multi-layer graphite material composed of a single piece of graphite. Graphene materials have many excellent properties, such as extremely high electrical conductivity and mechanical properties. Therefore, the film obtained from the graphene material has a wide application prospect. However, there is currently no good large-scale preparation method. Therefore, there is an urgent need for a large-scale preparation method that is feasible from both research and industrial applications. Overview
本申请的一方面提供了制备寡层石墨的方法， 所述方法包括： An aspect of the present application provides a method of preparing an oligo-pigment graphite, the method comprising:
(1) 将两个碳电极设置为阴极和阳极； 以及 (1) setting two carbon electrodes as a cathode and an anode;
(2) 在包含惰性气体和对碳具有一定反应性的气体的混合气体气 氛下， 对两极施加合适的电压一段时间。  (2) Apply a suitable voltage to the electrodes for a period of time in a mixed gas atmosphere containing an inert gas and a gas reactive with carbon.
本申请的另一方面提供制备寡层石墨薄膜的方法，所述方法包括： 将前述方法中获得的寡层石墨固体与溶剂混合制备成溶液， 将所述溶 液进行涂膜， 以及将形成的膜在惰性气体中加热。 附图说明  Another aspect of the present application provides a method of producing an oligolithic graphite film, the method comprising: mixing an oligolithic graphite solid obtained in the foregoing method with a solvent to prepare a solution, coating the solution, and forming a film Heat in an inert gas. DRAWINGS
图 1为 H2和 He的混合气气氛下电弧法合成的寡层石墨的电子透 射显微镜图。 Fig. 1 is an electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of H 2 and He.
图 2为 CO2(30%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的拉曼光谱图。 2 is a Raman spectrum of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (30% partial pressure) and He.
图 3为 CO2(30%分压）和 He的混合气气氛下电弧法合成的寡层石 墨的原子力显微镜图。 图 4为寡层石墨的 XRD图。 Fig. 3 is an atomic force micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (30% partial pressure) and He. Figure 4 is an XRD pattern of oligo-ply graphite.
图 5为寡层石墨的热重图。  Figure 5 is a thermograviogram of oligo-ply graphite.
图 6为 C02(25%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的电子透射显微镜图。 Fig. 6 is an electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He.
图 7为 C02(25%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的高分辨电子透射显微镜图。 Fig. 7 is a high-resolution electron transmission micrograph of the oligo-ply graphite synthesized by the arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He.
图 8为 C02(25%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的高分辨电子透射显微镜图。 Fig. 8 is a high-resolution electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He.
图 9为 CO2(40%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的原子力显微镜图。 Fig. 9 is an atomic force micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (40% partial pressure) and He.
图 10为 CO2(40%分压）和 He的混合气气氛下电弧法合成的寡 石墨的高分辨电子透射显微镜图。 Fig. 10 is a high-resolution electron transmission micrograph of an oligographite synthesized by an arc method in a mixed gas atmosphere of CO 2 (40% partial pressure) and He.
图 11为由寡层石墨溶液制成的薄膜的导电性曲线。 详述  Figure 11 is a graph showing the conductivity of a film made of an oligo graphite solution. Detailed
在以下的说明中， 包括某些具体的细节以对各个公开的实施方案 提供全面的理解。 然而， 相关领域的技术人员会认识到， 不采用一个 或多个这些具体的细节， 而采用其它方法、 部件、 材料等的情况下可 实现实施方案。  In the following description, certain specific details are included in the description of the various embodiments. However, one skilled in the relevant art will recognize that the embodiments may be practiced without the use of one or more of these specific details and other methods, components, materials, and the like.
除非本申请中另外要求， 在整个说明书和其后的权利要求书中， 词语 "包括 (comprise)" 及其英文变体例如 "包括 (comprises)" 和 "包 括 (comprising)" 应解释为开放式的、 含括式的意义， 即 "包括但不限 于，， 。  The word "comprise" and its English variants such as "comprises" and "comprising" should be interpreted as open-ended throughout the specification and subsequent claims, unless otherwise required by the application. Inclusive meaning, ie "including but not limited to,".
在整个本说明书中提到的 "一实施方案" 或 "实施方案" 或 "在 另一实施方案中" 或 "在某些实施方案中" 意指在至少一实施方案中 包括与该实施方案所述的相关的具体参考要素、 结构或特征。 因此， 在整个说明书中不同位置出现的短语 "在一实施方案中" 或 "在实施 方案中" 或 "在另一实施方案中" 或 "在某些实施方案中" 不必全部 指同一实施方案。 此外， 具体要素、 结构或特征可以任何适当的方式 在一个或多个实施方案中结合。  The word "one embodiment" or "an embodiment" or "in another embodiment" or "in some embodiments" as referred to throughout the specification is meant to include in at least one embodiment with the embodiment. Relevant specific reference elements, structures or features described. Thus, appearances of the phrases "in an embodiment" or "in an embodiment" or "in another embodiment" or "in some embodiments" are not necessarily referring to the same embodiment. Furthermore, the specific elements, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
应当理解， 在本申请说明书和附加的权利要求书中用到的单数形 式的冠词 "一" （对应于英文 "a"、 "an"和" the")包括复数的对象， 除非 文中另外明确地规定。 因此， 例如提到的包括 "惰性气体" 的反应包 括一种惰性气体， 或两种或多种惰性气体。 还应当理解， 术语 "或" 通常以其包括 "和 /或" 的含义而使用， 除非文中另外明确地规定。 It should be understood that the singular forms used in the specification and the appended claims The article "a" (corresponding to the English "a", "an" and "the" is intended to include the plural, unless the context clearly dictates otherwise. Thus, for example, reactions involving "inert gases" include an inert gas, or two or more inert gases. It is also to be understood that the term "or" is generally used in its meaning including "and/or" unless it is specifically defined otherwise.
本发明中所用的术语 "寡层石墨 (FG)" 是指其分子构成单元为由 The term "oligolayer graphite (FG)" as used in the present invention means that its molecular constituent unit is
"单层石墨"构成的多层 (通常为 2-30层)石墨材料。 术语 "单层石墨" 是指由单层碳原子组成的二维平面分子骨架， 其单片面积大小在 10 nm2到 1000 μιη2之间， 单片厚度约在 0.34 nm到 2 nm之间。 A multi-layer (usually 2-30 layers) graphite material consisting of "single layer graphite". The term "single-layer graphite" refers to a two-dimensional planar molecular skeleton consisting of a single layer of carbon atoms with a single-chip area between 10 nm 2 and 1000 μm 2 and a single-sheet thickness between about 0.34 nm and 2 nm.
"寡层石墨" 和 "单层石墨" 中的层边缘部分的碳原子根据具体 的制备方法和制备条件的不同可连接不同的有机官能团， 如羟基、 氨 基、 羧基、 环氧基团等。  The carbon atoms of the edge portion of the layer in "oligolayer graphite" and "single layer graphite" may be bonded to different organic functional groups such as a hydroxyl group, an amino group, a carboxyl group, an epoxy group or the like depending on the specific preparation method and preparation conditions.
本申请的一方面提供了制备寡层石墨的方法， 所述方法包括： An aspect of the present application provides a method of preparing an oligo-pigment graphite, the method comprising:
(1) 将两个碳电极设置为阴极和阳极； 以及 (1) setting two carbon electrodes as a cathode and an anode;
(2) 在包含惰性气体和对碳具有一定反应性的气体的混合气体气 氛下， 对两极施加合适的电压一段时间。  (2) Apply a suitable voltage to the electrodes for a period of time in a mixed gas atmosphere containing an inert gas and a gas reactive with carbon.
可用于本申请中的示例性的惰性气体包括 N2、 He、 Ne、 Ar、 Kr 和 Xe。 在某些实施方案中， 惰性气体为 He或 Ar或其混合物。 Exemplary inert gases that can be used in the present application include N 2 , He, Ne, Ar, Kr, and Xe. In certain embodiments, the inert gas is He or Ar or a mixture thereof.
可用于本申请中的示例性的对碳具有一定反应性的气体包括但不 限于氨气、 氢气、 二氧化碳、 空气、 氧气等。  Exemplary gases that are reactive with carbon in the present application include, but are not limited to, ammonia, hydrogen, carbon dioxide, air, oxygen, and the like.
在某些实施方案中， 混合气体中， 惰性气体与对碳具有一定反应 性的气体的体积比为 9: 95至 95: 5。 在本申请的某些实施方案中， 混合气体中， 惰性气体与对碳具有一定反应性的气体的体积为 80: 20 至 20: 80。 在本申请的某些实施方案中， 混合气体中， 惰性气体与对 碳具有一定反应性的气体的体积为 75 : 25至 25: 75。  In certain embodiments, the volume ratio of the inert gas to the gas which is reactive with carbon in the mixed gas is from 9:95 to 95:5. In certain embodiments of the present application, the volume of the inert gas and the gas reactive with carbon in the mixed gas is from 80:20 to 20:80. In certain embodiments of the present application, the volume of the inert gas and the gas reactive with carbon in the mixed gas is from 75:25 to 25:75.
在某些实施方案中， 混合气体的总压强为 0.02 MPa至 0.4 MPa。 在某些实施方案中， 混合气体的总压强为 0.05 MPa至 0.3 MPa。 在某 些实施方案中， 混合气体的总压强为 0.07 MPa至 0.2 MPa。  In certain embodiments, the total pressure of the mixed gas is from 0.02 MPa to 0.4 MPa. In certain embodiments, the total pressure of the mixed gas is from 0.05 MPa to 0.3 MPa. In some embodiments, the total pressure of the mixed gas is from 0.07 MPa to 0.2 MPa.
在某些实施方案中， 两个电极均为碳材料构成的电极。 在某些实 施方案中， 两个电极均为石墨构成的电极。  In certain embodiments, both electrodes are electrodes of carbon material. In some embodiments, both electrodes are electrodes of graphite.
在某些实施方案中， 在制备寡层石墨的方法中， 电弧放电过程可 采用交流电弧放电或直流电弧放电， 放电电压为 10-200 V, 电流为 10-250A。 在某些实施方案中， 在制备寡层石墨的方法中， 电弧放电过 程可采用交流电弧放电或直流电弧放电， 放电电压为 10-80 V, 电流 50-200 A。 In some embodiments, in the method of preparing oligolithic graphite, the arc discharge process may employ an alternating arc discharge or a direct current arc discharge, and the discharge voltage is 10-200 V, and the current is 10-250A. In certain embodiments, in the method of preparing oligo-pigmented graphite, the arc discharge process may employ an alternating arc discharge or a direct current arc discharge with a discharge voltage of 10-80 V and a current of 50-200 A.
在某些实施方案中， 电弧放电过程采用直流电弧放电， 放电电压 为 15-50 V, 电流为 80-180 A。 在某些实施方案中， 电弧放电过程采 用直流电弧放电， 放电电压为 15-40 V, 电流为 100-150 A。  In some embodiments, the arc discharge process employs a DC arc discharge with a discharge voltage of 15-50 V and a current of 80-180 A. In some embodiments, the arc discharge process employs a direct current arc discharge with a discharge voltage of 15-40 V and a current of 100-150 A.
放电过程中的电流通过电源控制， 并通过调节两电极之间的距离 来调节两电极之间的电压。  The current during discharge is controlled by the power supply and the voltage between the two electrodes is adjusted by adjusting the distance between the two electrodes.
在某些实施方案中， 阳极为消耗电极。  In certain embodiments, the anode is a consumable electrode.
在某些实施方案中， 阴极和阳极间的放电至阳极消耗完毕。  In certain embodiments, the discharge between the cathode and the anode is exhausted to the anode.
在某些实施方案中， 制备寡层石墨的方法， 所述方法包括： In certain embodiments, a method of making oligo-pigment graphite, the method comprising:
(1) 将两个碳电极设置为阴极和阳极， 其中直径较大的为阴极， 直径较小的为阳极； 以及 (1) Two carbon electrodes are provided as a cathode and an anode, wherein the larger diameter is the cathode and the smaller diameter is the anode;
(2) 在包含惰性气体和对碳具有一定反应性的气体的混合气体气 氛下， 对两极施加合适的电压一段时间。  (2) Apply a suitable voltage to the electrodes for a period of time in a mixed gas atmosphere containing an inert gas and a gas reactive with carbon.
在某些实施方案中， 阴极的直径为 3mm至 10cm。 在某些实施方 案中， 阴极的直径为 lcm。 在某些实施方案中， 阳极的直径为 2mm至 8cm。 在某些实施方案中， 阳极的直径为 5mm。  In certain embodiments, the cathode has a diameter of from 3 mm to 10 cm. In some embodiments, the cathode has a diameter of 1 cm. In certain embodiments, the anode has a diameter of from 2 mm to 8 cm. In certain embodiments, the anode has a diameter of 5 mm.
在某些实施方案中， 混合气体由惰性气体和对碳具有一定反应性 的气体构成。  In certain embodiments, the mixed gas is comprised of an inert gas and a gas that is reactive toward carbon.
在某些实施方案中， 所述方法在电炉中进行。  In certain embodiments, the method is carried out in an electric furnace.
该方法获得的寡层石墨可含不同层数的石墨烯片。  The oligo-pigment graphite obtained by the method may contain graphene sheets of different layers.
本申请的另一方面提供了制备寡层石墨薄膜的方法， 所述方法包 括： 将上述寡层石墨固体直接涂抹成膜， 或与溶剂混合制备成溶液， 将所述溶液进行涂膜， 以及将形成的膜在惰性气体中加热， 控制性地 除去石墨烯片上的官能团和修复缺陷， 以恢复石墨烯的本征导电性， 获得高导电性薄膜。 类似地， 可利用还原剂， 包括气体还原剂来还原， 获得石墨烯导电薄膜。  Another aspect of the present application provides a method of preparing an oligolithic graphite film, the method comprising: directly applying the oligo-pigment graphite solid to a film, or mixing with a solvent to prepare a solution, coating the solution, and The formed film is heated in an inert gas to controllably remove functional groups on the graphene sheets and repair defects to restore the intrinsic conductivity of the graphene to obtain a highly conductive film. Similarly, a graphene conductive film can be obtained by reducing with a reducing agent, including a gas reducing agent.
配制寡层石墨溶液时所使用的溶剂可以是任何可挥发的溶剂， 示 例性的溶剂包括但不限于： 水； Ν,Ν-二甲基甲酰胺 (DMF)、 Ν,Ν-二甲 基乙酰胺等酰胺类； 乙醇、 甲醇、 异丙醇等醇类； 二甲亚砜 (DMSO); 氯苯、 二氯苯、 二氯甲烷等氯代溶剂类； 乙酸乙酯、 乙酸甲酯、 邻苯 二甲酸二甲酯 (DMP)等酯类。 The solvent used in the preparation of the oligo graphite solution may be any volatile solvent, and exemplary solvents include, but are not limited to: water; hydrazine, hydrazine-dimethylformamide (DMF), hydrazine, hydrazine-dimethyl ethene Amides such as amides; alcohols such as ethanol, methanol, isopropanol; dimethyl sulfoxide (DMSO); Chlorinated solvents such as chlorobenzene, dichlorobenzene, and dichloromethane; esters such as ethyl acetate, methyl acetate, and dimethyl phthalate (DMP).
在本申请的制备寡层石墨薄膜的方法中， 可以采用本领域公知的 涂膜方法， 包括但不限于旋涂、 喷涂、 浸渍等。  In the method of producing an oligolithic graphite film of the present application, a coating film method well known in the art may be employed, including but not limited to spin coating, spray coating, dipping, and the like.
在本申请的制备寡层石墨薄膜的方法中， 可任选地包括在进行涂 膜之前向上述寡层石墨溶液或者上述寡层石墨固体与溶剂混合制备的 溶液中加入分散剂、 增稠剂等助剂的步骤。  In the method for producing an oligo-graphite film of the present application, it may optionally include adding a dispersing agent, a thickener, etc. to the solution prepared by mixing the above oligo-pigment graphite solution or the above-mentioned oligo-pigment graphite solid and a solvent before performing the coating film. The step of the auxiliary.
在本申请的制备寡层石墨薄膜的方法中， 可任选地包括在涂膜之 后再利用还原剂来还原提高薄膜导电性性的步骤。  In the method of producing an oligolithic graphite film of the present application, a step of reducing the conductivity of the film by using a reducing agent after the coating film may be optionally included.
在某些实施方案中， 所述还原性蒸汽为水合肼蒸汽。  In certain embodiments, the reducing vapor is hydrazine hydrate vapor.
下面通过实施例对本申请进行具体描述， 本实施例只用于对本申 请进行进一步的说明， 不能理解为对本申请保护范围的限制， 本领域 的技术人员根据上述本申请的内容做出一些非本质的改进和调整， 均 属本申请保护范围。  The present application is specifically described by the following examples, which are only used to further illustrate the present application, and are not to be construed as limiting the scope of the present application. Those skilled in the art may make some non-essential according to the content of the above application. Improvements and adjustments are within the scope of this application.
实施例 Example
寡层石墨的合成 Synthesis of oligo-pigmented graphite
实施例 1 Example 1
将纯的碳棒作为阳极。在电弧炉中通入 H2和 He的混合气 (压力比 1 : 1)至炉内压强为 0.07 MPa。 设置输出电流为 100 A。 放电开始后通 过调节阴极阳极间距离将电压维持在约 30 V, 维持炉内压强为约 0.07 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内的产物为寡层石墨。 实施例 2 A pure carbon rod was used as the anode. A mixture of H 2 and He (pressure ratio 1:1) was introduced into the electric arc furnace to a pressure of 0.07 MPa in the furnace. Set the output current to 100 A. After the start of the discharge, the voltage was maintained at about 30 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite. Example 2
将纯的碳棒作为阳极。在电弧炉中通入 H2和 He的混合气 (压力比A pure carbon rod was used as the anode. A mixture of H 2 and He is introduced into the electric arc furnace (pressure ratio)
1 : 1)至炉内压强 0.07 MPa。 设置输出电流为 150 A。 放电开始后通过 调节阴极阳极间距离将电压维持在约 37 V, 维持炉内压强为约 0.07 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内的产物为寡层石墨。 1 : 1) The pressure in the furnace is 0.07 MPa. Set the output current to 150 A. After the discharge started, the voltage was maintained at about 37 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite.
图 1为 H2和 He的混合气气氛下电弧法合成的寡层石墨的电子透 射显微镜图。 由图可以看到， 产物为片状为寡层石墨结构， 部分片状 结构弯折形成褶皱， 可看出层状结构。 实施例 3 Fig. 1 is an electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of H 2 and He. As can be seen from the figure, the product is in the form of an oligo-graphite structure, and some of the sheet-like structures are bent to form wrinkles, and a layered structure can be seen. Example 3
将纯的碳棒作为阳极。 在电弧炉中通入 C02和 He的混合气 (C02 占 5%分压）至炉内压强为 0.07 MPa。 设置输出电流为 150 A。 放电开 始后通过调节阴极阳极间距离将电压维持在约 32 V, 维持炉内压强为 约 0.07 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内的产物为寡层 石墨。 实施例 4 A pure carbon rod was used as the anode. A mixture of C0 2 and He (C0 2 5% partial pressure) was introduced into the electric arc furnace to a pressure of 0.07 MPa in the furnace. Set the output current to 150 A. After the start of the discharge, the voltage was maintained at about 32 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite. Example 4
将纯的碳棒作为阳极。 在电弧炉中通入 C02和 He的混合气 (C02 占 30%分压）至炉内压强为 0.07 MPa。 设置输出电流为 150 A。 放电开 始后通过调节阴极阳极间距离将电压维持在约 22 V , 维持炉内压强为 约 0.07 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内的产物为寡层 石墨。 实施例 5 A pure carbon rod was used as the anode. A mixture of C0 2 and He (C0 2 accounted for 30% partial pressure) was introduced into the electric arc furnace to a pressure of 0.07 MPa in the furnace. Set the output current to 150 A. After the discharge started, the voltage was maintained at about 22 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite. Example 5
将纯的碳棒作为阳极。 在电弧炉中通入 C02和 He的混合气 (C02 占 30%分压）至炉内压强为 0.07 MPa。 设置输出电流为 200 A。 放电开 始后通过调节阴极阳极间距离将电压维持在约 20 V , 维持炉内压强为 约 0.07 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内的产物为寡层 石墨。 实施例 6 A pure carbon rod was used as the anode. A mixture of C0 2 and He (C0 2 accounted for 30% partial pressure) was introduced into the electric arc furnace to a pressure of 0.07 MPa in the furnace. Set the output current to 200 A. After the discharge started, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.07 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite. Example 6
将纯的碳棒作为阳极。 在电弧炉中通入 C02和 He的混合气 (C02 占 30%分压）至炉内压强为 0.17 MPa。 设置输出电流为 150 A。 放电开 始后通过调节阴极阳极间距离将电压维持在约 20 V , 维持炉内压强为 约 0.17 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内的产物为寡层 石墨。 A pure carbon rod was used as the anode. A mixture of C0 2 and He (C0 2 accounted for 30% partial pressure) was introduced into the electric arc furnace to a pressure of 0.17 MPa in the furnace. Set the output current to 150 A. After the start of the discharge, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.17 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite.
图 2为 CO2(30%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的拉曼光谱图。 从其 2D峰的半峰宽和峰型可估计产物主要为 4层 的寡层石墨。 图 3为 CO2(30%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的原子力显微镜图，由图可以看到，产物石墨片的局部厚度为约 2.62 nm, 说明产物为寡层石墨片状结构。 实施例 7 2 is a Raman spectrum of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (30% partial pressure) and He. From the half-width and peak shape of its 2D peak, it can be estimated that the product is mainly 4 layers of oligo-pigment graphite. Figure 3 is an atomic force micrograph of the oligo-ply graphite synthesized by arc method in a mixed gas atmosphere of CO 2 (30% partial pressure) and He. As can be seen from the figure, the partial thickness of the product graphite sheet is about 2.62 nm, indicating that the product is Oligomerized graphite sheet structure. Example 7
将纯的碳棒作为阳极。 在电弧炉中通入 C02和 He的混合气 (C02 占 30%分压）至炉内压强为 0.10 MPa。 设置输出电流为 150 A。 放电开 始后通过调节阴极阳极间距离将电压维持在约 20 V , 维持炉内压强为 约 0.10 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内絮状的产物为 寡层石墨。 实施例 8 A pure carbon rod was used as the anode. A mixture of C0 2 and He (C0 2 accounted for 30% partial pressure) was introduced into the electric arc furnace to a pressure of 0.10 MPa in the furnace. Set the output current to 150 A. After the start of the discharge, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.10 MPa. The anode is consumed and the reaction is completed. The flocculent product collected in the electric arc furnace is oligo graphite. Example 8
将纯的碳棒作为阳极。 在电弧炉中通入 C02和 He的混合气 (C02 占 25%分压）至炉内压强为 0.20 MPa。 设置输出电流为 150 A。 放电开 始后通过调节阴极阳极间距离将电压维持在约 20 V, 维持炉内压强为 约 0.20 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内的产物为寡层 石墨。 A pure carbon rod was used as the anode. A mixture of C0 2 and He (C 2 2 is divided by 25%) is introduced into the electric arc furnace to a pressure of 0.20 MPa in the furnace. Set the output current to 150 A. After the discharge started, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.20 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite.
图 4为所得寡层石墨的 XRD图。 由图可以看到， 两个峰表示产物 片层之间的距离分别为 3.4 nm和 4.2 nm, 其中 3.4 nm处峰较为尖锐， 说明产物中存在较为完整的普通石墨片层结构， 而 4.2 nm处峰较宽， 说明产物中还有层间距大于普通石墨片的结构， 且呈无定形状态， 符 合为寡层石墨的结构。  Figure 4 is an XRD pattern of the obtained oligo-ply graphite. It can be seen from the figure that the two peaks indicate that the distance between the product sheets is 3.4 nm and 4.2 nm, respectively, and the peak at 3.4 nm is sharper, indicating that there is a relatively complete ordinary graphite sheet structure in the product, and 4.2 nm The peak is wider, indicating that the product has a layer spacing larger than that of the ordinary graphite sheet, and is in an amorphous state, which conforms to the structure of the oligo graphite.
图 5为所得寡层石墨的热重图。 由图可以看到， 产物在整个温区 的热失重很少， 说明产物所含有的官能团较少， 远小于普通溶液法制 得的单层石墨和寡层石墨。  Figure 5 is a thermograviogram of the obtained oligo-ply graphite. As can be seen from the figure, the product has little thermal weight loss throughout the temperature zone, indicating that the product contains less functional groups, much smaller than the single layer graphite and oligo-pigment graphite produced by the conventional solution method.
图 6为 C02(25%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的电子透射显微镜图。由图可以看到产物为薄片状结构的寡层石墨， 部分石墨片层形成褶皱。 Fig. 6 is an electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He. It can be seen from the figure that the product is a flaky structure of oligo-pigmented graphite, and part of the graphite sheet layer forms wrinkles.
图 7为 C02(25%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的高分辨电子透射显微镜图。 由图可以看到产物为薄片状结构的寡 层石墨， 箭头所示边缘为三层的石墨片层结构。 图 8为 C02(25%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的高分辨电子透射显微镜图。从电镜图中可看出形成的片状石墨烯， 箭头所示石墨烯片层褶皱处的层数分别为两层、 四层、 五层。 实施例 9 Fig. 7 is a high-resolution electron transmission micrograph of the oligo-ply graphite synthesized by the arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He. It can be seen from the figure that the product is a flaky structure of oligo-ply graphite, and the edge indicated by the arrow is a three-layer graphite sheet structure. Fig. 8 is a high-resolution electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of C0 2 (25% partial pressure) and He. The flaky graphene formed can be seen from the electron micrograph, and the number of layers of the graphene sheet pleats indicated by the arrows is two, four, and five layers, respectively. Example 9
将纯的碳棒作为阳极。 在电弧炉中通入 C02和 He的混合气 (C02 占 25%分压）至炉内压强为 0.17 MPa。 设置输出电流为 150 A。 放电开 始后通过调节阴极阳极间距离将电压维持在约 20 V , 维持炉内压强为 约 0.17 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内絮状的产物为 寡层石墨。 实施例 10 A pure carbon rod was used as the anode. A mixture of C0 2 and He (C 2 2 is divided by 25%) is introduced into the electric arc furnace to a pressure of 0.17 MPa in the furnace. Set the output current to 150 A. After the start of the discharge, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.17 MPa. The anode is consumed and the reaction is completed. The flocculent product collected in the electric arc furnace is oligo graphite. Example 10
将纯的碳棒作为阳极。 在电弧炉中通入 C02和 He的混合气 (C02 占 40%分压）至炉内压强为 0.17 MPa。 设置输出电流为 150 A。 放电开 始后通过调节阴极阳极间距离将电压维持在约 20 V, 维持炉内压强为 约 0.17 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内的产物为寡层 石墨。 A pure carbon rod was used as the anode. A mixture of C0 2 and He (C0 2 accounted for 40% partial pressure) was introduced into the electric arc furnace to a pressure of 0.17 MPa in the furnace. Set the output current to 150 A. After the discharge started, the voltage was maintained at about 20 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at about 0.17 MPa. The anode is consumed and the reaction is completed. The product collected in the electric arc furnace is oligo graphite.
图 9为 CO2(40%分压)和 He的混合气气氛下电弧法合成的寡层石 墨的原子力显微镜图。 由图可以看到， 产物石墨片的局部厚度为 2.80 nm, 说明产物为寡层石墨片状构。 Fig. 9 is an atomic force micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (40% partial pressure) and He. As can be seen from the figure, the partial thickness of the product graphite sheet was 2.80 nm, indicating that the product was an oligo-graphite sheet structure.
图 10为 CO2(40%分压)和 He的混合气气氛下电弧法合成的寡层 石墨的高分辨电子透射显微镜图。 由图可以看到产物为薄片状结构的 寡层石墨， 箭头所示边缘为六层的石墨片层结构。 实施例 11 Fig. 10 is a high-resolution electron transmission micrograph of an oligo-ply graphite synthesized by an arc method in a mixed gas atmosphere of CO 2 (40% partial pressure) and He. It can be seen from the figure that the product is a flaky structure of oligo-pigment graphite, and the edge indicated by the arrow is a six-layer graphite sheet structure. Example 11
将纯的碳棒机械加工后作为阳极。 在电弧炉中通入 C02和 Ar的 混合气 (( 02占 33%分压）至炉内压强为 0.17 MPa。设置输出电流为 150 A。 放电开始后通过调节阴极阳极间距离将电压维持在约 30 V, 维持 炉内压强为约 0.17 MPa。 阳极消耗完毕， 反应结束。 收集电弧炉内的 产物为寡层石墨。 实施例 12 The pure carbon rod is machined and used as an anode. In the electric arc furnace, a mixture of C0 2 and Ar is introduced (( 0 2 is 33% partial pressure) to a furnace pressure of 0.17 MPa. The output current is set to 150 A. After the discharge starts, the voltage is maintained by adjusting the distance between the cathode and the anode. At about 30 V, the pressure in the furnace was maintained at about 0.17 MPa. The anode was consumed and the reaction was completed. The product in the collection arc furnace was oligo graphite. Example 12
将纯的碳棒机械加工后作为阳极。 在电弧炉中通入空气和 He 的 混合气（空气占 50%分压）至炉内压强为 0.17-0.20 MPa。 设置输出电流 为 150 A。放电开始后通过调节阴极阳极间距离将电压维持在约 30 V, 维持炉内压强为 0.17-0.20 MPa。 阳极消耗完毕， 反应结束。 收集电弧 炉内的产物为寡层石墨。 寡层石墨溶液制备  The pure carbon rod is machined and used as an anode. A mixture of air and He (air 50% partial pressure) is introduced into the electric arc furnace to a pressure of 0.17-0.20 MPa. Set the output current to 150 A. After the discharge started, the voltage was maintained at about 30 V by adjusting the distance between the cathode and the anode, and the pressure in the furnace was maintained at 0.17-0.20 MPa. The anode is consumed and the reaction is completed. The product in the collection arc furnace is oligo graphite. Oligo-layer graphite solution preparation
实施例 13 Example 13
将实例 1-12中生成的寡层石墨 1 mg和 1 ml DMF超声混合均匀， 即获得寡层石墨的 DMF溶液。 实施例 14  The oligographite graphite 1 mg and 1 ml of DMF formed in Examples 1-12 were ultrasonically mixed uniformly to obtain a DMF solution of oligo-ply graphite. Example 14
将实例 1—12中生成的寡层石墨 1.7 mg和 1 ml二氯苯混合均匀， 即获得寡层石墨的二氯苯溶液。 导电寡层石墨薄膜的制备  The oligo-pigmented graphite 1.7 mg and the 1 ml of dichlorobenzene produced in Example 1-12 were uniformly mixed to obtain a dichlorobenzene solution of the oligo-ply graphite. Preparation of conductive oligo graphite film
将实例 13或 14中生成的寡层石墨溶液， 通过在清洗干净的石英 片上旋涂， 加热干燥后即获得寡层石墨导电薄膜。  The oligo graphite solution prepared in Example 13 or 14 was obtained by spin coating on a cleaned quartz sheet, and dried by heating to obtain an oligo graphite conductive film.
图 11为由寡层石墨溶液制成的薄膜的导电性曲线。 电导率为~103 Figure 11 is a graph showing the conductivity of a film made of an oligo graphite solution. Conductivity is ~10 3
S/m, 优于其他方法获得的寡层石墨薄膜的导电性。 S/m, superior to the conductivity of the oligolithic graphite film obtained by other methods.

Claims

权利要求书 Claim
1. 制备寡层石墨的方法， 所述方法包括：  A method of preparing an oligo-pigment graphite, the method comprising:
(1) 将两个碳电极设置为阴极和阳极； 以及  (1) setting two carbon electrodes as a cathode and an anode;
(2) 在包含惰性气体和对碳具有一定反应性的气体的混合气体气 氛下， 对两极施加合适的电压一段时间。  (2) Apply a suitable voltage to the electrodes for a period of time in a mixed gas atmosphere containing an inert gas and a gas reactive with carbon.
2. 如权利要求 1所述的方法， 其中所述惰性气体选自 N2、 He、 Ne、 Ar、 Kr或 Xe, 优选为 He或 Ar或其混合物。 2. The method according to claim 1, wherein said inert gas is selected from N 2, He, Ne, Ar , Kr , or Xe, He or Ar is preferably a mixture thereof.
3. 如权利要求 1或 2所述的方法， 其中所述对碳具有一定反应性 的气体选自氨气、 氢气、 二氧化碳、 空气以及氧气， 优选为二氧化碳。 3. Process according to claim 1 or 2, wherein the gas which is reactive towards carbon is selected from the group consisting of ammonia, hydrogen, carbon dioxide, air and oxygen, preferably carbon dioxide.
4. 如权利要求 1至 3中任一权利要求所述的方法， 其中所述惰性 气体与所述对碳具有一定反应性的气体的体积比为 5: 95至 95: 5 , 优选为 80: 20至 20: 80, 更优选为 75: 25至 25: 75。 The method according to any one of claims 1 to 3, wherein a volume ratio of the inert gas to the gas having a certain reactivity with carbon is 5: 95 to 95: 5 , preferably 80: 20 to 20: 80, more preferably 75: 25 to 25: 75.
5. 如权利要求 1至 4中任一权利要求所述的方法， 其中所述混合 气体的总气压为 0.02 MPa至 0.4 MPa, 优选为 0.05 MPa至 0.3 MPa, 更优选为 0.07 MPa至 0.2 MPa。 The method according to any one of claims 1 to 4, wherein the total gas pressure of the mixed gas is from 0.02 MPa to 0.4 MPa, preferably from 0.05 MPa to 0.3 MPa, more preferably from 0.07 MPa to 0.2 MPa.
6. 如权利要求 1至 5中任一权利要求所述的方法， 其中所述放电 电压为 10-200 V, 电流为 10-250 A, 优选的为电压 10-80 V, 电流 50-200A。 The method according to any one of claims 1 to 5, wherein the discharge voltage is 10-200 V, the current is 10-250 A, preferably the voltage is 10-80 V, and the current is 50-200 A.
7. 如权利要求 1至 6中任一权利要求所述的方法， 其中所述放电 过程采用直流电弧放电。 The method according to any one of claims 1 to 6, wherein the discharging process employs a direct current arc discharge.
8. 如权利要求 7所述的方法， 其中所述放电电压为 15-50 V, 电 流为 80-180 A, 更优选电压为 15-40 V, 电流为 100-150 A。 8. The method of claim 7, wherein the discharge voltage is 15-50 V, the current is 80-180 A, more preferably the voltage is 15-40 V, and the current is 100-150 A.
9. 如权利要求 1至 8中任一权利要求所述的方法， 其中阴极和阳 极间的放电至阳极消耗完毕。 9. A method according to any one of claims 1 to 8 wherein the cathode and the anode The discharge between the poles is completed until the anode is consumed.
10. 如权利要求 1至 9中任一权利要求所述的方法， 其中所述阴 极的直径大于所述阳极的直径，优选所述阴极的直径为 3mm至 10cm, 更优选 lcm; 并且优选所述阳极的直径为 2mm至 8cm, 优选 5mm。 10. The method according to any one of claims 1 to 9, wherein the diameter of the cathode is larger than the diameter of the anode, preferably the diameter of the cathode is from 3 mm to 10 cm, more preferably 1 cm; and preferably The diameter of the anode is from 2 mm to 8 cm, preferably 5 mm.
11. 制备寡层石墨薄膜的方法， 所述方法包括： 将权利要求 1-10 中任一权利要求所述的方法中获得的寡层石墨固体直接涂抹成膜， 或 与溶剂混合制备成溶液， 将所述溶液进行涂膜， 以及将形成的膜在惰 性或还原性气体中加热还原。 11. A method of preparing an oligolithic graphite film, the method comprising: directly applying the oligolithic graphite solid obtained in the method of any one of claims 1-10 to a film, or mixing with a solvent to prepare a solution, The solution is coated, and the formed film is heated and reduced in an inert or reducing gas.
12. 如权利要求 11所述的方法， 其中所述溶剂选自水； Ν,Ν-二甲 基甲酰胺 (DMF)、 Ν,Ν-二甲基乙酰胺等酰胺类； 乙醇、 甲醇、 异丙醇 等醇类； 二甲亚砜 (DMSO); 氯苯、 二氯苯、 二氯甲烷等氯代溶剂类； 乙酸乙酯、 乙酸甲酯、 邻苯二甲酸二甲酯 (DMP)等酯类。 12. The method according to claim 11, wherein the solvent is selected from the group consisting of: amides such as hydrazine, hydrazine-dimethylformamide (DMF), hydrazine, hydrazine-dimethylacetamide; ethanol, methanol, and Alcohols such as propanol; dimethyl sulfoxide (DMSO); chlorinated solvents such as chlorobenzene, dichlorobenzene, dichloromethane; esters such as ethyl acetate, methyl acetate, dimethyl phthalate (DMP) class.
13. 如权利要求 11或 12所述的方法， 其还包括在进行涂膜之前 向向权利要求 1至 10中任一权利要求所述的方法中获得的寡层石墨溶 液或者权利要求 11 所述的方法中获得的寡层石墨固体与不同溶剂混 合制备的溶液中加入分散剂、 增稠剂等助剂的步骤。 The method according to claim 11 or 12, further comprising the oligolithite graphite solution obtained by the method according to any one of claims 1 to 10 or the method of claim 11 before the coating film is applied The step of adding an auxiliary agent such as a dispersing agent or a thickener to the solution prepared by mixing the oligo-pigmented graphite solid and the different solvent obtained in the method.
14. 如权利要求 11至 13 中任一权利要求所述的方法， 其还包括 在涂膜之后在还原性蒸汽中还原的步骤。 14. A method according to any one of claims 11 to 13 further comprising the step of reducing in a reducing vapor after coating.
15. 如权利要求 14中所述的方法， 其中所述还原性蒸汽选自水合 肼、 氨气、 肼以及氢气蒸汽或气体。 15. The method of claim 14 wherein the reducing vapor is selected from the group consisting of hydrazine hydrate, ammonia, hydrazine, and hydrogen vapor or gas.
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