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WO2011066809A1 - 寡层石墨及其薄膜的制备方法 - Google Patents

寡层石墨及其薄膜的制备方法 Download PDF

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Publication number
WO2011066809A1
WO2011066809A1 PCT/CN2010/079473 CN2010079473W WO2011066809A1 WO 2011066809 A1 WO2011066809 A1 WO 2011066809A1 CN 2010079473 W CN2010079473 W CN 2010079473W WO 2011066809 A1 WO2011066809 A1 WO 2011066809A1
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Prior art keywords
graphite
acid
concentrated
oligo
film
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English (en)
French (fr)
Inventor
陈永胜
解敏雨
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Tianjin Pulan Nano Technology Co Ltd
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Tianjin Pulan Nano Technology Co Ltd
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Priority to US13/582,542 priority Critical patent/US20130043436A1/en
Priority to CN2010800627925A priority patent/CN102791627A/zh
Publication of WO2011066809A1 publication Critical patent/WO2011066809A1/zh
Anticipated expiration legal-status Critical
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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
    • 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
    • C01B32/194—After-treatment
    • 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
    • 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
    • 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
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • 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
    • 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
    • C01B2204/06—Graphene nanoribbons

Definitions

  • the present application relates to a carbon material and a method of producing the same, and in particular to a method for preparing an oligo graphite solution and a solid having different layers and a film 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 oligo-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 oligolithite graphite solution, the method comprising: controlling oxidation of graphite with an oxidizing agent in the presence of an acid.
  • Another aspect of the present application provides a method of preparing an oligolithic graphite solid, the method comprising removing a solvent from the above oligo graphite solution.
  • Another aspect of the present application provides a method of preparing an oligolithic graphite film, the method comprising: coating a solution prepared by mixing the above oligolithite graphite solution or the above oligolithite graphite solid with a solvent, and forming the formed film at The reduction is carried out by heating or reduction in an inert gas or by using a reducing agent to remove a functional group on the graphene to obtain a film material having high conductivity.
  • Figure 1 is a graph of X-ray diffraction (XRD) data of an oligolithic graphite solid according to the present application.
  • Fig. 2 is an atomic force microscopy (AFM) chart of the thickness and number of layers of an oligolithic graphite solid according to the present application.
  • AFM atomic force microscopy
  • 3 is a conductivity curve obtained by an oligo-ply graphite according to the present application.
  • oligolayer graphite refers to a multilayer (usually 2-30 layers) graphite material whose molecular building blocks are composed of "single layer graphite".
  • single-layer graphite refers to a two-dimensional planar molecular skeleton consisting of a single layer of carbon atoms with a single-area size between 10 nm 2 and 1,000 ⁇ m 2 and a monolith thickness between 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.
  • intercalation refers to the insertion of a substance (ie, a guest such as sulfuric acid, nitric acid, etc., and inorganic oxides such as Ti0 2 , ZnO, W0 3 , SnO 2 , etc.) into a lamellar junction.
  • a substance ie, a guest such as sulfuric acid, nitric acid, etc., and inorganic oxides such as Ti0 2 , ZnO, W0 3 , SnO 2 , etc.
  • Another substance in the structure ie, the main body, such as graphite, hydrotalcite, etc.).
  • An aspect of the present application provides a method of preparing an oligolithite graphite solution comprising: controlling oxidation of graphite with an oxidizing agent in the presence of an acid.
  • a method of preparing an oligolithite graphite solution comprising: controlling oxidation of graphite with an oxidant in the presence of an acid;
  • the impurities in the reaction mixture are removed with water and/or hydrogen peroxide.
  • a method of making an oligolithite graphite solution comprising: controlling oxidation and a poor layer of graphite with an oxidizing agent in the presence of an acid.
  • a method of preparing an oligolithite graphite solution comprising: controlling oxidation and a poor layer of graphite with an oxidizing agent in the presence of an acid; and removing impurities from the reaction mixture with water and/or hydrogen peroxide.
  • Exemplary oxidizing agents useful in the methods of preparing oligolithite graphite solutions of the present application include, but are not limited to, alkali metal permanganates, hypochlorites, chlorates, perchlorates, chromates, dichromic acid Salt, persulfate, etc.; or peroxide such as hydrogen peroxide or dibenzoyl peroxide (BPO).
  • a preferred oxidizing agent is an alkali metal permanganate or dichromate, more preferably KMn0 4 .
  • the weight ratio of the raw graphite to the oxidant is from 1:1 to 1:5. In certain embodiments, the weight ratio of raw graphite to oxidant is from 1:2 to 1:3.
  • Exemplary acids useful in the process of preparing the oligolithite graphite solution of the present application include, but are not limited to, concentrated acid, concentrated nitric acid, perchloric acid, acetic acid, acetic anhydride, and the like, preferably concentrated acid, concentrated nitric acid, or a mixture thereof.
  • the acid used is from 15 milliliters to 90 milliliters per gram of the raw graphite.
  • the acid used is concentrated sulfuric acid and the concentrated sulfuric acid is used in an amount of from 15 ml to 90 ml per gram of the raw material graphite. In certain embodiments, the acid used is concentrated sulfuric acid, and the concentrated sulfuric acid is used in an amount of from 20 ml to 50 ml per gram of the raw material graphite.
  • the acid used is a mixture of concentrated sulfuric acid and concentrated nitric acid, wherein concentrated nitric acid can be formed in situ by reaction of an alkali metal nitrate with an acid.
  • the alkali metal nitrate 'sodium salt is preferably sodium nirate or potassium nitrate.
  • the acid used is a concentrated acid and a mixture of concentrated nitric acid formed by the reaction of sodium nitrate with concentrated acid, wherein the concentrated sulfuric acid is used per gram of the raw graphite.
  • the amount is 15 ml to 90 ml; and the weight ratio of raw graphite to sodium nitrate is 1: 0.5 to
  • the acid used is a concentrated acid and a mixture of concentrated nitric acid formed by the reaction of sodium nitrate with concentrated gram acid, wherein the concentrated sulfuric acid is used in an amount of 15 ml to 90 ml per gram of the raw material graphite;
  • the weight ratio of raw graphite to sodium nitrate is from 1:0.7 to 1:1.
  • the acid used is a mixture of concentrated acid and concentrated nitric acid formed by the reaction of sodium nitrate with concentrated gram acid, wherein the concentrated sulfuric acid is used in an amount of from 20 ml to 50 ml per gram of the raw material graphite; And the weight ratio of the raw material graphite to the sodium nitrate is 1:0.5 to 1:2.
  • the acid used is a mixture of concentrated acid and concentrated nitric acid formed by the reaction of sodium nitrate with concentrated gram acid, wherein the concentrated sulfuric acid is used in an amount of from 20 ml to 50 ml per gram of the raw material graphite; And the weight ratio of raw graphite to sodium nitrate is 1: 0.7 to 1:1.
  • the oxidation reaction is between 10 and 80.
  • the temperature of C is carried out.
  • the oxidation reaction is between 30 and 50. Under C.
  • the oxidation reaction has a reaction time of from 0.1 to 10 days. In some embodiments, the oxidation reaction has a reaction time of from 2 to 6 days.
  • the oligo graphite obtained by the method for producing an oligo graphite solution according to the present application may contain graphene sheets of different numbers.
  • water and hydrogen peroxide are added to the reaction system to remove impurities in the reaction mixture.
  • the amount of water to be added, the amount and concentration of hydrogen peroxide to be added are not particularly limited as long as impurities in the reaction system can be removed.
  • Another aspect of the present application provides a method of preparing an oligolithic graphite solid, the method comprising removing a solvent from the above oligo graphite solution.
  • Method such as evaporation, evaporation under reduced pressure, and the like.
  • Another aspect of the present application provides a method of preparing an oligolithic graphite film, the method comprising: coating a solution prepared by mixing the above oligolithite graphite solution or the above oligolithite graphite solid with a solvent, and forming the formed film at Heating in an inert gas.
  • An exemplary solvent used in formulating the oligo graphite solution may be any volatile solvent including, but not limited to: water; N,N-dimethylformamide (DMF), N,N-dimethylacetamide Amides; alcohols such as ethanol, methanol, isopropanol; dimethyl sulfoxide (DMSO); chlorobenzene, a chlorinated solvent such as dichlorobenzene or dichloromethane; an ester such as ethyl acetate, methyl acetate or dimethyl phthalate (DMP).
  • DMF N,N-dimethylformamide
  • DMSO dimethyl sulfoxide
  • chlorobenzene a chlorinated solvent such as dichlorobenzene or dichloromethane
  • an ester such as ethyl acetate, methyl acetate or dimethyl phthalate (DMP).
  • 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 in a reducing vapor after the coating film may optionally be included.
  • the functional groups on the graphene sheets and the repair defects are controlled to remove 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 reducing vapor is hydrazine hydrate vapor, hydrogen or ammonia.
  • the present invention is specifically described by the following examples. The present invention is only used to further illustrate the present invention, and is 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. Example
  • Fig. 1 is X-ray diffraction (XRD) data of the obtained oligo-pigment graphite.
  • XRD X-ray diffraction
  • Figure 2 is an atomic force microscopy (AFM) chart showing the thickness and number of layers of the oligo-pigmented graphite material. It can be seen that the thickness is between 0.5 and 10 nm, and most of it is between 2-4 nm. It is indicated that the oligo graphite is composed of a single layer of graphite having several layers to several tens of layers.
  • AFM atomic force microscopy
  • Example 4 The oligographite 0.1 mg and 1 ml of DMF formed in Example 1 or 2 were ultrasonically mixed uniformly to obtain a DMF solution of oligo-ply graphite.
  • Example 4 The oligographite 0.1 mg and 1 ml of DMF formed in Example 1 or 2 were ultrasonically mixed uniformly to obtain a DMF solution of oligo-ply graphite.
  • Example 5 The oligo graphite 6 mg produced in Example 1 or 2 and 1 ml of water were uniformly mixed to obtain an aqueous solution of oligo graphite.
  • Example 5 The oligo graphite 6 mg produced in Example 1 or 2 and 1 ml of water were uniformly mixed to obtain an aqueous solution of oligo graphite.
  • the oligo graphite solution produced in Example 1 or 2, or the oligo graphite solution in Example 4 was spin-coated on the cleaned glass, dried and then reduced (heated in an inert gas, 400 ° C) for 2 h. That is, an oligo graphite conductive film is obtained.
  • Fig. 3 is a graph showing the conductivity obtained by the oligo graphite of the present invention.
  • the conductivity of the electroconductive film was calculated from the graph to be about 100 S/cm, which is superior to the conductivity of the single-layered graphite film obtained under the same conditions.
  • Example 6
  • the oligo graphite solution produced in Example 1 or 2, or the oligo graphite solution in Example 4 was spin-coated on the cleaned glass, first reduced with hydrazine hydrate vapor, and then reduced by heating (heated in an inert gas) , 400 ° C) 2 h, that is, an oligo-pigment graphite conductive film is obtained.
  • Its electrical conductivity is about 110 S/cm, which is superior to the conductivity of a single-layer graphite film obtained under the same conditions.
  • the oligo graphite solution prepared in Example 1 or 2, or the oligo graphite solution in Example 4 was spin-coated on the cleaned glass, and reduced with hydrazine hydrate vapor to obtain an oligo graphite conductive film.
  • the conductivity is 0.03 S/cm.

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Description

寡层石墨及其薄膜的制备方法 领域
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寡 层石墨溶液和固体以及其薄膜的制备方法。 背景
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寡 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
本申请的一方面提供了制备寡层石墨溶液的方法，所述方法包括： 将石墨在酸存在下用氧化剂进行控制性氧化。
本申请的另一方面提供了制备寡层石墨固体的方法， 所述方法包 括从上述寡层石墨溶液中除去溶剂。
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： 将上述寡层石墨溶液或者上述寡层石墨固体与溶剂混合所制备的 溶液进行涂膜， 以及将形成的膜在惰性气体中加热还原或利用还原剂 进行还原， 除去石墨烯上的官能团， 以获得高导电性的薄膜材料。 附图说明
图 1为本申请涉及的一种寡层石墨固体的 X射线衍射 (XRD)数据 图。
图 2为本申请涉及的一种寡层石墨固体的厚度和层数的原子力显 微镜 (AFM)统计图。
图 3为通过本申请涉及的一种寡层石墨获得的导电性曲线。 详述
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。
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" 。
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。
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 "酸" 的反应包括一种 酸， 或两种或多种酸。 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。
本申请中所用的术语 "寡层石墨 (FG)" 是指其分子构成单元为由 "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， 其单片面积大小约在 10 nm2到 1,000 μιη2之间， 单片厚度约在 0.34 nm到 2 nm之间。
"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。
本申请中所用的术语 "插层"是指将一种物质（即客体，例如硫酸、 硝酸等和无机氧化物如 Ti02、 ZnO、 W03、 Sn02等)插入到具有片层结 构的另一种物质（即主体， 例如石墨、 水滑石等）中。
本申请的一方面提供了制备寡层石墨溶液的方法， 其包括： 将石 墨在酸存在下用氧化剂进行控制性氧化。
在某些实施方案中， 制备寡层石墨溶液的方法， 其包括： 将石墨在酸存在下用氧化剂进行控制性氧化； 以及
用水和 /或双氧水除去反应混合物中的杂质。
在某些实施方案中， 制备寡层石墨溶液的方法， 其包括： 将石墨 在酸存在下用氧化剂进行控制性氧化和差层。
在某些实施方案中， 制备寡层石墨溶液的方法， 所述方法包括： 将石墨在酸存在下用氧化剂进行控制性氧化和差层； 以及 用水和 /或双氧水除去反应混合物中的杂质。
可用于本申请的制备寡层石墨溶液的方法的示例性的氧化剂包括 但不限于碱金属的高锰酸盐、 次氯酸盐、 氯酸盐、 高氯酸盐、 铬酸盐、 重铬酸盐、 过硫酸盐等； 或者过氧化氢、 过氧化二苯甲酰 (BPO)等过 氧化物。 优选的氧化剂为碱金属的高锰酸盐或重铬酸盐， 更优选为 KMn04。
在某些实施方案中， 原料石墨与氧化剂的重量比为 1 : 1至 1 : 5。 在某些实施方案中， 原料石墨与氧化剂的重量比为 1 : 2至 1 : 3。
可用于本申请的制备寡层石墨溶液的方法的示例性的酸包括但不 限于浓 酸、 浓硝酸、 高氯酸、 乙酸及乙酸酐等， 优选为浓^ £酸、 浓 硝酸或其混合物。
在某些实施方案中， 所用的酸相对于每克原料石墨， 用量为 15 毫升至 90毫升。
在某些实施方案中， 所用的酸为浓硫酸， 且相对于每克原料石墨， 浓硫酸的用量为 15毫升至 90毫升。 在某些实施方案中， 所用的酸为 浓硫酸， 且相对于每克原料石墨， 浓硫酸的用量为 20毫升至 50毫升。
在某些实施方案中， 所用的酸为浓硫酸与浓硝酸的混合物， 其中 浓硝酸可以通过碱金属硝酸盐与 酸反应而原位形成的。 所述碱金属 硝'酸盐优选硝'酸钠或硝'酸钾。
在某些实施方案中， 所用的酸为浓 酸以及通过硝酸钠与浓^ £酸 反应生成的浓硝酸的混合物， 其中相对于每克原料石墨， 浓硫酸的用 量为 15毫升至 90毫升； 并且原料石墨与硝酸钠的重量比为 1 : 0.5至
1 : 2。 在某些实施方案中， 所用的酸为浓 酸以及通过硝酸钠与浓石克 酸反应生成的浓硝酸的混合物， 其中相对于每克原料石墨， 浓硫酸的 用量为 15毫升至 90毫升； 并且原料石墨与硝酸钠的重量比为 1 : 0.7 至 1 : 1。 某些实施方案中， 所用的酸为浓 ^£酸以及通过硝酸钠与浓石克 酸反应生成的浓硝酸的混合物， 其中相对于每克原料石墨， 浓硫酸的 用量为 20毫升至 50毫升； 并且原料石墨与硝酸钠的重量比为 1 : 0.5 至 1 : 2。 某些实施方案中， 所用的酸为浓 ^£酸以及通过硝酸钠与浓石克 酸反应生成的浓硝酸的混合物， 其中相对于每克原料石墨， 浓硫酸的 用量为 20毫升至 50毫升； 并且原料石墨与硝酸钠的重量比为 1 : 0.7 至 1 : 1。
在某些实施方案中， 氧化反应在 10-80。C的温度下进行。 在某些 实施方案中， 氧化反应在 30-50。C下进行。
在某些实施方案中， 氧化反应的反应时间为 0.1-10天。 在某些实 施方案中， 氧化反应的反应时间为 2-6天。
根据本申请的制备寡层石墨溶液的方法所获得的寡层石墨可含不 同层数的石墨烯片。
在本申请的制备寡层石墨溶液的方法中， 当氧化反应完成后， 需 向反应体系中加入水和双氧水以除去反应混合物中的杂质。 对加入的 水的量、 加入的双氧水的量及浓度均没有特别的限制， 只要能够除去 反应体系中的杂质即可。
本申请的另一方面提供了制备寡层石墨固体的方法， 所述方法包 括从上述寡层石墨溶液中除去溶剂。 法， 例如蒸发、 减压蒸发等。
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： 将上述寡层石墨溶液或者上述寡层石墨固体与溶剂混合所制备的 溶液进行涂膜， 以及将形成的膜在惰性气体中加热。
配制寡层石墨溶液时所使用的示例性的溶剂可以是任何可挥发的 溶剂， 包括但不限于： 水； N,N-二甲基甲酰胺 (DMF)、 N,N-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。
在本发明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。
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。
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 后在还原性蒸汽中还原的步骤。 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。
在某些实施方案中， 所述还原性蒸汽为水合肼蒸汽， 氢气或氨气。 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发 明进行进一步的说明， 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。 实施例
实施例 1 :
将 5.0 g石墨与 3.75 g NaN03加入到 1 L的圓底三口瓶中，然后边 搅拌边緩慢倒入 190 ml浓硫酸。 混合均匀后緩慢加入 11.25 g KMn04 固体， 之后保持冰浴 3 h使之降至室温后。 搅拌 6天后， 緩慢向反应 体系中滴加 500 ml蒸馏水， 并在 95-98。C下恒温反应 3小时， 待反应 液冷却后， 加入 15 ml双氧水 (30wt%水溶液）， 然后在常温下搅拌。 将 反应溶液使用离心机的方法进行除杂后即获得寡层石墨水溶液产品。 再将溶剂水除去即获得寡层石墨产品。
图 1为所获寡层石墨的 X射线衍射 (XRD)数据， 从图中可看出， 获得的寡层石墨和单层石墨相比，在衍射角 26.4。有一衍射峰，其表明 所获得石墨产品为寡层结构。
图 2为获得的寡层石墨材料的厚度和层数的原子力显微镜 (AFM) 统计图， 可以看出其厚度在 0.5-10 nm之间， 大部分在 2-4 nm之间， 表明寡层石墨由具有从几层到数十层单层石墨构成。 实施例 2:
将 10.0 g石墨与 8 g NaN03加入到 1 L的圓底三口瓶中， 然后边 搅拌边緩慢倒 400 ml浓硫酸。混合均匀后緩慢加入 25 g KMn04固体， 之后保持冰浴 3 h使之降至室温后。 搅拌 8天后， 緩慢向反应体系中 滴加 1000 ml蒸馏水， 并在 95-98。C下恒温反应 5小时， 待反应液冷 却后， 加入 30 1111双氧水(3(½1%水溶液）， 然后在常温下搅拌。 将反应 溶液使用离心机的方法进行除杂后即获得寡层石墨水溶液产品， 再将 溶剂水除去即获得寡层石墨产品。 实施例 3:
将实例 1或 2中生成的寡层石墨 0.1 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 4:
将实例 1或 2中生成的寡层石墨 6 mg和 1 ml水混合均匀， 即获 得寡层石墨的水溶液。 实施例 5:
将实例 1或 2中生成的寡层石墨溶液， 或实例 4中的寡层石墨溶 液， 通过在清洗干净的玻璃上旋涂， 干燥后再还原（在惰性气体加热， 400。C)2 h, 即获得寡层石墨导电薄膜。
图 3为通过本发明的寡层石墨获得的导电性曲线。 从图中计算得 到该导电薄膜的电导率为约 100 S/cm, 优于同样条件下获得的单层石 墨薄膜的导电性。 实施例 6:
将实例 1或 2中生成的寡层石墨溶液， 或实例 4中的寡层石墨溶 液， 通过在清洗干净的玻璃上旋涂， 先利用水合肼蒸汽还原， 然后再 利用加热还原（在惰性气体加热， 400°C)2 h ,即获得寡层石墨导电薄膜。 其电导率为约 110 S/cm, 优于同样条件下获得的单层石墨薄膜的导电 性。 实施例 7:
将实例 1或 2中生成的寡层石墨溶液， 或实例 4中的寡层石墨溶 液， 通过在清洗干净的玻璃上旋涂， 利用水合肼蒸汽还原， 即获得寡 层石墨导电薄膜。 电导率为 0.03 S/cm。

Claims

权利要求书
1. 制备寡层石墨溶液的方法， 所述方法包括：
将石墨在酸存在下， 用氧化剂进行控制性氧化。
2. 如权利要求 1所述的方法， 其中所述氧化剂选自碱金属的高锰 酸盐、 次氯酸盐、 氯酸盐、 高氯酸盐、 铬酸盐、 重铬酸盐、 过硫酸盐； 或者过氧化氢、 过氧化二苯甲酰 (BPO)等过氧化物， 优选为碱金属的 高锰酸盐或重铬酸盐， 更优选为 KMn04。
3. 如权利要求 1或 2所述的方法， 其中石墨与所述氧化剂的重量 比为 1 : 1至 1 : 5 , 优选为 1 : 2至 1 : 3。
4. 如权利要求 1至 3中任一权利要求所述的方法， 其中所述酸选 自浓^ £酸、 浓硝酸、 高氯酸、 乙酸及乙酸酐， 优选为浓^ £酸、 浓硝酸 或其混合物。
5. 如权利要求 1至 4中任一权利要求所述的方法， 其中所述酸为 浓硫酸， 且相对于每克原料石墨， 浓硫酸的用量为 15毫升至 90毫升， 优选为 20毫升至 50毫升。
6. 如权利要求 1至 4中任一权利要求所述的方法， 其中所述酸为 浓石克酸与浓硝酸的混合物， 其中浓硝酸可以通过硝酸钠或硝酸钾与石克 酸反应而原位形成的。
7. 如权利要求 6所述的方法， 其中所述酸为浓石充酸以及通过硝酸 钠与浓硫酸反应而原位形成的浓硝酸的混合物， 其中相对于每克原料 石墨， 浓硫酸的用量为 15毫升至 90毫升，优选为 20毫升至 50毫升； 并且原料石墨与硝酸钠的重量比为 1 : 0.5至 1 : 2,优选为 1 : 0.7至 1 : 1。
8 如权利要求 1至 7中任一权利要求所述的方法， 其中氧化反应 在 10-80。C的温度下进行， 优选在 30-50。C下进行。
9. 如权利要求 1至 8中任一权利要求所述的方法， 其中氧化反应 的反应时间为 0.1-10天， 优选为 2-6天。
10. 如权利要求 1至 9中任一权利要求所述的方法， 其还包括用 水和 /或双氧水除去反应混合物中的杂质。
11. 制备寡层石墨固体的方法， 所述方法包括从权利要求 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中除去溶剂。
12. 制备寡层石墨薄膜的方法， 所述方法包括： 将权利要求 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溶剂混合所制备的溶液进行 涂膜， 以及将形成的膜在惰性气体中加热。
13. 如权利要求 12所述的方法， 其中所述溶剂选自水； N,N-二甲 基甲酰胺 (DMF)、 N,N-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。
14. 如权利要求 12或 13所述的方法， 其还包括在进行涂膜之前 向权利要求 1至 8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 9所述的方法中获得的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。
15. 如权利要求 12至 14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。
16. 如权利要求 15中所述的方法， 其中所述还原性蒸汽选自水合 肼蒸汽、 氢气以及氨气。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103224233A (zh) * 2013-04-28 2013-07-31 上海应用技术学院 一种碳材料及其制备方法
CN103833008A (zh) * 2012-11-20 2014-06-04 中国科学院兰州化学物理研究所 一种常温下石墨烯的制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103253662B (zh) * 2013-06-01 2015-04-15 上海轻丰新材料科技有限公司 一种大规模、可操控、低成本的石墨烯制备方法
CN104310386B (zh) * 2014-10-14 2017-01-11 南开大学 一种基于石墨烯的光驱动材料的制备方法及其应用
CN112357909B (zh) * 2020-11-11 2022-02-15 四川恒瑞天成科技有限公司 一种石墨烯多孔膜的制备方法及应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101474898A (zh) * 2009-01-16 2009-07-08 南开大学 基于石墨烯的导电碳膜及制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6596396B2 (en) * 2000-08-09 2003-07-22 Mitsubishi Gas Chemical Company, Inc. Thin-film-like particles having skeleton constructed by carbons and isolated films
DE10256963B4 (de) * 2002-12-05 2006-10-19 Hilti Ag Verfahren zur Steuerung der Expansionseigenschaften von thermisch expandierbaren Schwefelsäure-Graphitpartikeln und deren Verwendung
WO2008048295A2 (en) * 2005-11-18 2008-04-24 Northwestern University Stable dispersions of polymer-coated graphitic nanoplatelets
US20120128570A1 (en) * 2008-10-11 2012-05-24 Vorbeck Materials Corp. Process for the preparation of graphite oxide and graphene sheets
US8821745B2 (en) * 2008-12-23 2014-09-02 The Trustees Of The University Of Pennsylvania High yield preparation of macroscopic graphene oxide membranes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101474898A (zh) * 2009-01-16 2009-07-08 南开大学 基于石墨烯的导电碳膜及制备方法和应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HIGGINBOTHAM, A. L. ET AL.: "Graphite Oxide Flame-Retardant Polymer Nanocomposites", ACS APPLIED MATERIALS & INTERFACES, vol. 1, no. 10, 22 September 2009 (2009-09-22), pages 2256 - 2261 *
HIRATA, M. ET AL.: "Thin-film particles of graphite oxide 1: High-yield synthesis and flexibility of the particles", CARBON, vol. 42, no. 14, 2004, pages 2929 - 2937 *
LERF, A. ET AL.: "Structure of Graphite Oxide Revisited", J. PHYS. CHEM. B, vol. 102, no. 23, 13 May 1998 (1998-05-13), pages 4477 - 4482 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103833008A (zh) * 2012-11-20 2014-06-04 中国科学院兰州化学物理研究所 一种常温下石墨烯的制备方法
CN103224233A (zh) * 2013-04-28 2013-07-31 上海应用技术学院 一种碳材料及其制备方法

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