WO2012116594A1 - 加热氧化石墨的有机溶剂悬浮液制备石墨烯的方法，由此方法获得的石墨烯及其用途 - Google Patents

加热氧化石墨的有机溶剂悬浮液制备石墨烯的方法，由此方法获得的石墨烯及其用途 Download PDF

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WO2012116594A1
WO2012116594A1 PCT/CN2012/071069 CN2012071069W WO2012116594A1 WO 2012116594 A1 WO2012116594 A1 WO 2012116594A1 CN 2012071069 W CN2012071069 W CN 2012071069W WO 2012116594 A1 WO2012116594 A1 WO 2012116594A1
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graphene
suspension
organic solvent
heating
graphite oxide
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French (fr)
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瞿研
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无锡第六元素高科技发展有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • 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
    • 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
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/23—Oxidation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to a method for preparing graphene by chemical dispersion method, and belongs to the technical field of graphene preparation.
  • it relates to a method of preparing graphene by heating an organic solvent suspension of graphite oxide.
  • Graphene the English name Graphene, is a two-dimensional lattice structure in which carbon atoms are arranged in hexagons. As a single-layer carbon atom planar material, graphene can be obtained by peeling off a graphite material. Since the graphite crystal film was discovered by scientists at the University of Manchester in 2004, graphene has become the focus of attention in the scientific and industrial circles. Graphene has a thickness of only 0.335 nm, which is not only the thinnest of the known materials, but also very strong and hard; as a simple substance, it transmits electrons at room temperature faster than all known conductors and semiconductors (graphene The migration speed of electrons reaches 1/300 of the speed of light).
  • graphene Due to the special atomic structure of graphene, the behavior of carriers (electrons and holes) must be characterized by relativistic quantum mechanics. Meanwhile, as a single-layer carbon atom structure, the theoretical specific surface area of graphene is as high as 2630 m 2 /g. Such a high specific surface area makes graphene-based materials a promising energy storage active material, and graphene materials may be used in hydrogen storage, new lithium ion batteries, supercapacitors or fuel cells.
  • Graphite oxide is formed by the hydrolysis of graphite under the action of a strong oxidant such as H 2 S0 4 , HN0 3 or HC10 4 or by electrochemical peroxidation.
  • Graphite oxide is also a layered covalent compound with a interlayer distance of about 0.8 nm (graphite is 0.335 nm) depending on the preparation method.
  • the ink contains groups such as -C-OH, -COC and -COOH.
  • electrostatic repulsion exists between the layers of graphite oxide due to the presence of polar groups.
  • the graphite oxide can be peeled off in water or other polar solvent under the action of an external force such as ultrasonic waves to form a single layer of graphene oxide o to obtain graphene oxide, and then to reduce the graphite oxide produced by reduction.
  • the alkene deoxidizes and re-graphitizes to restore partial conductivity while maintaining its geometry.
  • the method cleaves natural graphite powder into a single layer of graphite during oxidation and reduction. Although it only partially reduces its conductivity during the redox process (destroying the high electron mobility of graphene), its product has a relatively high powder specific surface area (>700 m 2 /g), so this method is most suitable for industrial scale. Production of graphene materials. However, due to the presence of oxygen-containing functional groups, graphite oxide and its cleaved monolithic graphene conductance are very low. In order to apply graphene materials to conductive-related applications, researchers have continually explored various reduction methods in order to improve the quality (mainly conductivity) of reduced graphene oxide. At present, there are mainly the following methods: the hydration trap reduction method shown in Fig. 1, the heat treatment reduction method shown in Fig. 2, and the microwave irradiation reduction method shown in Fig. 3.
  • the chemical reduction method can obtain a suspension after reduction of graphene oxide, but the process is cumbersome and is not conducive to mass production.
  • the reducing agents used therein such as hydrazine hydrate, are very toxic, posing a greater threat to human health and environmental protection.
  • the thermal reduction method has the advantages of quickness and complete reduction; however, since heating generally needs to be carried out at a high temperature of 1000 degrees Celsius or more, the energy consumption of the entire process is increased.
  • this method requires relatively expensive equipment such as a high temperature furnace. Microwave irradiation heating has the characteristics of high speed, low cost and simple use.
  • This process can be carried out in a conventional microwave oven, and the black fluffy graphene powder can be obtained within a minute by irradiating the graphite oxide particles.
  • ordinary microwave irradiation is carried out in the air.
  • the graphene obtained by first reduction is easily burned under microwave irradiation and even causes fire, which poses a potential safety threat for large-scale application of this method.
  • the burning of graphene consumes carbon in the product, resulting in a lower final yield.
  • the specific surface of the graphene material obtained by heat reduction and microwave reduction is usually less than 500 square meters per gram, indicating that the graphene material is not a single layer, but has an average of 4 to 5 layers.
  • CN 102259851A discloses a method for preparing graphene by low-temperature chemical reduction method, which comprises using graphene oxide prepared by chemical oxidation as a raw material, comprising a reduction reaction step of reducing graphene oxide to graphene, the reduction reaction.
  • the aluminum oxide is used as a reducing agent to reduce the graphene oxide at a temperature of 60 ° C to 180 ° C by controlling the concentration of the reducing agent and the type of the solvent, and the oxygen-containing functional group on the graphene oxide ( The removal of epoxy, hydroxyl, carboxyl and carbonyl groups completely restores the conductivity of graphene to produce graphene.
  • CN 101941694A discloses a green preparation method of high-dispersion graphene, first preparing graphite oxide, then ultrasonically stripping to obtain graphene oxide, and adding water-soluble high polymer as a dispersing agent, and reducing the surface under ultraviolet irradiation. High polymer modified graphene with high dispersion.
  • the technical problem to be solved by the present invention is to overcome the defects of preparing graphene by the prior chemical dispersion method, and to provide a method for chemically dispersing graphene which is low temperature operation, anhydrous, and suitable for mass production.
  • the basic idea of the invention is to disperse the graphite oxide in an anhydrous polar organic solvent, and then use the high boiling point and lower vapor pressure of the organic solvent to directly heat at a lower temperature (the temperature required for heating and reduction).
  • the organic solvent suspension is such that the monolithic graphene oxide therein is deoxidized to restore its high conductivity.
  • This utilizes the strong interaction between graphene oxide and polar organic solvent molecules, cleavage of graphite oxide to a single layer by intercalation of organic solvent molecules, and then directly transfers energy to the surface of single-layer graphene oxide through organic solvent molecules, thereby removing An oxygen-containing functional group on the surface.
  • the present invention employs the following technical solutions:
  • a method for preparing graphene by heating an organic solvent suspension of graphite oxide comprising the following steps:
  • the obtained solid was directly dried (3) to obtain a graphene material.
  • the graphite oxide used in the present invention is prepared by the Hummers method. This can be done by the following procedure: 10 g of 200 mesh natural flake graphite is slowly added to a 2000 mL large beaker containing 230 mL of concentrated sulfuric acid (precooled to 0 ° C) while stirring, maintaining the temperature at (0 ⁇ 1) °C.
  • the polar organic solvent of the present invention is an anhydrous polar organic solvent, and a person skilled in the art can make a reasonable selection according to actual needs. Preference is given to N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, dimethyl sulfoxide, propylene carbonate, dimethylformamide or a mixture of at least two, for example hydrazine-methyl-2- Pyrrolidone, hydrazine, hydrazine-dimethylacetamide, propylene carbonate, hydrazine, hydrazine-dimethylacetamide/dimethyl sulfoxide/propylene carbonate, propylene carbonate/dimethylformamide, etc.
  • a polar organic solvent having a polar moment greater than 2 Debye particularly preferably propylene carbonate, dimethylformamide, hydrazine-methyl-2-pyrrolidone or a mixture of at least two, such as carbon Acid propylene, dimethylformamide/N-methyl-2-pyrrolidone, propylene carbonate/dimethylformamide/N-methyl-2-pyrrolidone.
  • the ultrasonic mode described in the above (1) is prior art, and can be obtained by a person skilled in the art by common knowledge or experience, and is not particularly limited herein.
  • the reasonable ultrasonic time is l ⁇ 8h, for example, 1.5h, 4h, 5.8h, 7h, 7.8h, etc., preferably 2 ⁇ 5h, and further 3.6h.
  • the concentration of the suspension in the step (1) is 0.01 to 10 g/L, for example, 0.1 g/L, 2 g/L, 4.5 g/L, 6 g/L, 8.4 g/L, 9.7 g/L, etc. can be used for the implementation. In the present invention, it is preferably 1 to 8 g/L, and further preferably 5 g/L.
  • the suspension concentration is a mass to volume ratio of graphite oxide to a polar organic solvent.
  • Step (2) The heating method is water bath heating, oil bath heating, microwave heating or ultrasonic heating, and further heating is preferably performed by an oil bath.
  • Other ways that can be used to heat the suspension to black can be selected by those skilled in the art, and the specific operation mode is prior art, and will not be described again.
  • the suspension according to step (1) is heated to 80 ⁇ 200 ° C for 4 ⁇ 24h; the heating end temperature can be selected from 85 ° C, 93 ° C, 108 ° C, 145 ° C, 180 ° C, 195 ° C, etc., preferably 100 ⁇ 150 ° C, further one 125 ° C, the holding time can be selected 5h, 8h, 13h, 17h, 20h, 23h, etc., preferably 8 ⁇ 15h, further one is preferably 10h. It is apparent that the present invention is a low temperature heating mode.
  • the stirring speed is 100 ⁇ 1000r/min, for example, 230r/min, 380r/min, 520r/min, 625r/min, 800r/min, 983r/min, etc., preferably 200. ⁇ 600r/min, further one is preferably 500r/min.
  • Step (3) The solid-liquid separation method is a prior art, and the solid-liquid separation does not change the physicochemical properties of the obtained solid.
  • the solid-liquid separation does not change the physicochemical properties of the obtained solid.
  • the filtration includes suction filtration, pressure filtration, vacuum filtration, centrifugal filtration, vacuum filtration, membrane filtration, and ultrafiltration.
  • the filtration operation is a commonly used means for solid-liquid separation by those skilled in the art, and the present invention is not particularly limited.
  • the organic electrolyte solution is preferably 1 M TEA-BF 4 /PC; the retention body is an electrode of a supercapacitor or a lithium battery.
  • a method for preparing graphene by heating an organic solvent suspension of graphite oxide preferably comprising the following steps:
  • a graphene prepared by the above method has a conductance greater than lS/m.
  • a graphene obtained by the above method can be directly used in a device highly sensitive to moisture, such as a supercapacitor or a lithium ion battery, and can also be further removed to obtain a graphene powder or paper-like material.
  • the process of the invention comprises ultrasonic dispersion of graphite oxide in a polar organic solvent, heating of the resulting suspension at low temperature, and subsequent steps of solid-liquid separation and drying.
  • the invention is characterized in that the strong interaction between the polarity of the functional group in the graphite oxide and the polar organic solvent molecule is used to realize the cleavage and reduction of the graphite oxide in the same medium, thereby effectively simplifying the production process and preventing other Pollution is especially the entry of water.
  • the completely dry (anhydrous) graphene material thus obtained has a conductivity of more than 5 orders of magnitude higher than that of graphite oxide, is greater than 1 S/m, and has a certain degree of dispersion stability in an organic solvent, and can be directly used for some A device that is highly sensitive to moisture, such as a supercapacitor or a lithium-ion battery. Alternatively, the organic solvent may be removed to obtain a graphene powder or paper material.
  • the steps involved in the present invention The instrument is simple, and the process is easy to mass-produce, resulting in a low-cost, high-conductivity, anhydrous graphene material that does not require any reducing chemicals.
  • Figure 1 shows the hydration trap reduction method
  • Figure 2 shows the heat treatment reduction method
  • FIG. 3 shows the microwave irradiation reduction method
  • FIG. 4 is a flow chart of a method of preparing graphene of the present invention.
  • a method for directly obtaining a graphene material by heating in propylene carbonate includes the following preparation steps:
  • step 2 the graphite oxide suspension obtained in step 1 is placed in an oil bath and stirred and heated to 150 ° C for 4 h, stirring speed 200 r / min;
  • step 3 pour the suspension obtained in step 2 into a vacuum filtration device, open the vacuum door for suction filtration until no droplets are dripped; after washing 1 ml of electrolyte solution (1M TEA-BF 4 /PC), quickly filter Lmin;
  • the slurry material obtained in the step 3 is directly applied to the supercapacitor retaining body as an organic supercapacitor electrode.
  • the conductivity of the graphene material was determined to be 2.6 S/m using a four-probe tester.
  • Example 2 The conductivity of the graphene material was determined to be 2.6 S/m using a four-probe tester.
  • a method for directly obtaining a graphene material by heating in propylene carbonate includes the following preparation steps:
  • step 2 the graphite oxide suspension obtained in step 1 is placed in an oil bath and stirred and heated to 150 ° C, and maintained for 20 h, stirring speed lOOOr / min;
  • step 3 pour the suspension obtained in step 2 into a vacuum filter device, and open the vacuum door for suction filtration until no droplets are dripped;
  • the slurry material obtained in the step 3 is dried to obtain a graphene powder material.
  • the conductance of the graphene powder material was measured by a four-probe tester to be 5.1 S/m.
  • a method for directly obtaining a graphene material by heating in dimethylformamide includes the following preparation steps:
  • step 2 the graphite oxide suspension obtained in step 1 is placed in an oil bath and stirred and heated to 150 ° C, and maintained for 15 h, stirring speed 200 r / min;
  • step 3 pour the suspension obtained in step 2 into a vacuum filtration device, open the vacuum door for suction filtration until no droplets are dripped; after washing 1 ml of electrolyte solution (1M TEA-BF 4 /PC), quickly filter Lmin;
  • the slurry material obtained in the step 3 is directly applied to the electrode of the lithium battery as an organic supercapacitor electrode.
  • the conductance of the graphene powder material was measured by a four-probe tester to be 4.6 S/m.
  • Example 4 A method for directly obtaining a graphene material by heating in N-methyl-2-pyrrolidone comprises the following preparation steps:
  • the graphite oxide suspension obtained in the first step is placed in an oil bath and stirred and heated to 150 ° C for 4 h, and the stirring speed is 200 r / min ;
  • step 3 pour the suspension obtained in step 2 into a vacuum filter device, and open the vacuum door for suction filtration until no droplets are dripped;
  • the slurry material obtained in the step 3 is directly dried to obtain a paper-like and powdery mixed graphene material.
  • the conductance of the graphene material was measured by a four-probe tester to be 6.1 S/m.
  • a method for directly obtaining a graphene material by heating in a mixture of propylene carbonate and N-methyl-2-pyrrolidone comprises the following steps:
  • step 2 the graphite oxide suspension obtained in step 1 is placed in an oil bath and stirred and heated to 80 ° C for 24 h, stirring speed lOOr / min;
  • step 3 pour the suspension obtained in step 2 into a vacuum filtration device, open the vacuum door for suction filtration until no droplets are dripped; after washing 1 ml of electrolyte solution (1M TEA-BF 4 /PC), quickly filter Lmin;
  • the slurry material obtained in the step 3 is directly applied to the supercapacitor retaining body as an organic supercapacitor electrode.
  • the conductance of the graphene material was measured by a four-probe tester to be 3.9 S/m.
  • Example 6 A method for directly obtaining a graphene material by heating in propylene carbonate includes the following preparation steps:
  • step 2 The graphite oxide suspension obtained in step 1 is placed in an oil bath and heated to 200 ° C, and kept for 20 h, stirring speed 800 r / min;
  • step 3 pour the suspension obtained in step 2 into a vacuum filter device, and open the vacuum door for suction filtration until no droplets are dripped;
  • the slurry material obtained in the step 3 is dried to obtain a graphene powder material.
  • the conductance of the graphene powder material was measured by a four-probe tester to be 6.3 S/m.
  • the conductivity of the completely dry (anhydrous) graphene material obtained in Examples 1-6 of the present invention is more than 5 orders of magnitude higher than that of graphite oxide, and both are greater than lS/m, and have a certain degree of dispersion stability in an organic solvent. And does not require any reducing chemicals.

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Description

说 明 书
加热氧化石墨的有机溶剂悬浮液制备石墨烯的方法， 由此方法获得的石墨烯及其用途 技术领域
本发明涉及一种化学分散法制备石墨烯的方法， 属于石墨烯制备技术领域。 具体地说， 涉及一种加热氧化石墨的有机溶剂悬浮液制备石墨烯的方法。
背景技术
石墨烯， 英文名 Graphene, 是碳原子按照六角排列而成的二维晶格结构。 作为单层碳原子平面材料， 石墨烯可以通过剥离石墨材料而得到。 这种石墨晶 体薄膜自 2004年被曼彻斯特大学的科学家发现之后， 石墨烯就成为科学界和工 业界关注的焦点。石墨烯的厚度只有 0.335纳米，不仅是已知材料中最薄的一种， 还非常牢固坚硬； 作为单质， 它在室温下传递电子的速度比已知所有的导体和 半导体都快 (石墨烯中电子的迁移速度达到了光速的 1/300)。 由于石墨烯的特殊 原子结构， 其中载流子 （电子和空穴） 的行为必须用相对论量子力学 (relativistic quantum mechanics)才能描绘。 同时， 作为单层碳原子结构， 石墨烯的理论比表 面积高达 2630m2/g。 如此高的比表面积使得以基于石墨烯的材料成为极有前途 的能量储存活性材料， 石墨烯材料有可能在储氢、 新型锂离子电池、 超级电容 器或者燃料电池得到应用。
目前， 石墨烯的制备方法有多种， 如轻微摩擦法或撕胶带发（粘贴 HOPG)、 加热 SiC法、 金属衬底化学气相沉积法、 化学分散法等； 其中， 化学分散法最 适合工业化大规模生产石墨烯材料， 适用范围较广。
氧化石墨是石墨在 H2S04、 HN03、 HC104等强酸等强氧化剂的作用下， 或 电化学过氧化作用下， 经水解后形成的。 氧化石墨同样是一层状共价化合物， 层间距离大约为 0.8nm (石墨为 0.335nm) 依制备方法而异。 一般认为， 氧化石 墨中含有 -C-OH、 -C-O-C和 -COOH等基团。和石墨不同， 由于极性基团的存在， 氧化石墨片层之间存在静电排斥作用。 因此， 氧化石墨在外力， 如超声波的作 用下在水中或其它极性溶剂中可以发生剥离， 形成单层氧化石墨烯 （graphene oxide ) o 制得氧化石墨烯后， 再通过还原使所制氧化石墨烯脱氧重新石墨化， 保 持其几何形貌时可恢复部分导电性。
该方法在氧化和还原过程中将天然石墨粉解理成单层石墨。 虽然在氧化还 原过程中只是部分还原其导电性 （破坏了石墨烯高电子迁移率性质）， 但是其产 品具有相当高的粉末比表面积 （>700m2/g)， 因此该方法最适合工业化大规模生 产石墨烯材料。 然而， 由于含氧官能团的存在， 氧化石墨及其解理成的单片石 墨烯电导非常低。 为了将石墨烯材料应用于导电相关的用途中， 研究者不断探 索各种还原方法， 以期提高还原氧化石墨烯的质量 （主要是导电性）。 目前， 主 要有下面几种方法： 图 1所示的水合阱还原法， 图 2所示的热处理还原法， 图 3 所示的微波辐照还原法。
以上的几种还原方法具有不同的特点。 其中化学还原法可以得到氧化石墨 烯还原之后的悬浮液， 但是其过程繁琐， 不利于大规模生产。 而且其中所用的 还原剂， 比如水合肼具有非常大的毒性， 对人身健康和环境保护构成了较大的 威胁。 热还原方法具有快速和还原比较彻底的优点； 但是由于加热一般需要在 1000摄氏度以上的高温下进行， 增加了整个过程的能耗。 而且， 这个方法需要 高温加热炉等比较昂贵设备。 微波辐照加热具有速度快， 成本低， 使用简单等 特点。 此过程可在普通微波炉中进行， 辐照氧化石墨颗粒一分钟之内即可得到 黑色的蓬松的石墨烯粉末。 但是普通的微波辐照在空气中进行， 先还原得到的 石墨烯在微波辐照下极易燃烧甚至引起火患， 为这个方法的大规模应用带来了 潜在的安全威胁。 而且， 石墨烯的燃烧消耗了产物里的碳， 使得最终产率较低。 另外， 用加热还原和微波还原得到的石墨烯材料的比表面通常小于 500平方米 每克， 说明其中的石墨烯材料并非单层， 而是有平均 4~5层的堆叠。
CN 102259851A公开了一种低温化学还原法制备石墨烯的方法， 该方法以 化学氧化制备的石墨烯氧化物为原料， 包括将石墨烯氧化物还原成石墨烯的还 原反应歩骤， 所述还原反应歩骤以碘化铝为还原剂， 通过控制还原剂浓度和溶 剂种类， 在 60°C ~180°C的温度下实现对石墨烯氧化物的还原， 将石墨烯氧化物 上面的含氧官能团 (环氧、羟基、羧基及羰基)去除，较彻底恢复石墨烯的导电性， 制得石墨烯。
CN 101941694A公开了一种高分散性石墨烯的绿色制备方法， 首先制备氧 化石墨， 然后超声剥离得到氧化石墨烯， 再加入水溶性的高聚物作为分散剂， 在紫外光辐照下还原得到表面高聚物修饰的高分散性石墨烯。
另夕卜， 很多电化学相关的应用比如有机电解质的超级电容器和锂离子电池， 对水分非常敏感。 微量的水分可能被电化学分解产生氢气和氧气在器件里面积 累， 在一定的条件下就会起火燃烧或者爆炸。
发明内容
本发明要解决的技术问题是克服现有化学分散法制备石墨烯的缺陷， 提供 了一种低温操作、 无水、 适于大规模生产的石墨烯化学分散制备方法。
本发明的基本思路是， 把氧化石墨分散在无水极性有机溶剂中， 然后利用 有机溶剂的高沸点和较低蒸汽压， 直接在较低的温度下 （相于加热还原所需温 度） 加热有机溶剂悬浮液， 从而使其中的单片氧化石墨烯脱氧， 以恢复其高导 电性。 这利用了氧化石墨烯和极性有机溶剂分子的强相互作用， 通过有机溶剂 分子插层解理氧化石墨至单层， 然后通过有机溶剂分子直接把能量传到单层氧 化石墨烯表面， 从而去除表面的含氧官能团。 为达此目的， 本发明采用以下技术方案：
加热氧化石墨的有机溶剂悬浮液制备石墨烯的方法， 包括以下歩骤：
( 1 ) 将氧化石墨加入极性有机溶剂中， 超声制得悬浮液；
(2) 将上述悬浮液加热至黑色， 出现部分或者全部凝聚；
(3 ) 将歩骤 （2) 的黑色悬浮液进行固液分离， 去除极性有机溶剂后得到 固体；
(4) 向歩骤 （3 ) 所得固体中滴入有机电解质溶液并抽滤， 得黑色浆状物 并直接涂布于羁留体使用； 或，
直接干燥歩骤 （3 ) 所得固体， 得到石墨烯材料。
本发明所用氧化石墨通过 Hummers法制备得到。 可通过如下歩骤进行： 将 10g 200目天然鳞片石墨在搅拌下缓慢加入到装有 230mL浓硫酸 (预先冷却至 0 °C)的 2000mL的大烧杯中， 温度维持在 (0± 1)°C， 再先后缓慢连续加入 5g硝酸 钠与 30g高锰酸钾的混合物， 在搅拌下维持 (0± 1)°C， 2h至反应完全， 在 (35士 3)°C恒温水浴中， 搅拌下保温 30min， 缓慢加入 460mL水， 使温度上升至 98°C， 在此温度下维持 15min; 用温水稀释到 1400mL， 倒入 25ml的过氧化氢 (30%)， 趁热过滤， 用 5%HC1充分洗涤滤饼， 直至滤液中无硫酸根离子 (用 BaCl2溶液 检测)， 于 50°C在真空干燥箱干燥 48h， 密封保存待用。
本发明所述极性有机溶剂为无水极性有机溶剂， 本领域技术人员可以根据 实际需要进行合理选择。 优选 N-甲基 -2-吡咯垸酮、 Ν,Ν-二甲基乙酰胺、 二甲亚 砜、 碳酸丙烯、 二甲基甲酰胺或至少两种的混合物， 例如 Ν-甲基 -2-吡咯垸酮、 Ν,Ν-二甲基乙酰胺、 碳酸丙烯、 Ν,Ν-二甲基乙酰胺 /二甲亚砜 /碳酸丙烯、 碳酸丙 烯 /二甲基甲酰胺等， 进一歩优选电偶极矩大于 2德拜的极性有机溶剂， 特别优 选碳酸丙烯、 二甲基甲酰胺、 Ν-甲基 -2-吡咯垸酮或至少两种的混合物， 例如碳 酸丙烯、 二甲基甲酰胺 /N-甲基 -2-吡咯垸酮、 碳酸丙烯 /二甲基甲酰胺 /N-甲基 -2- 吡咯垸酮等。
歩骤 （1 ) 所述的超声方式为现有技术， 所属领域技术人员可以通过公知常 识或经验获得， 此处无特殊限制。 合理的超声时间为 l~8h， 例如可以选择 1.5h、 4h、 5.8h、 7h、 7.8h等， 优选 2~5h， 进一歩优选 3.6h。
歩骤（1 )所述悬浮液浓度为 0.01~10g/L， 例如 0.1g/L、 2g/L、 4.5g/L、 6g/L、 8.4g/L、 9.7g/L等均可用于实施本发明， 优选 l~8g/L， 进一歩优选 5g/L。所述悬 浮液浓度为氧化石墨与极性有机溶剂的质量体积比。
歩骤 （2) 所述加热方式为水浴加热、 油浴加热、 微波加热或超声加热， 进 一歩优选油浴加热方式。 本领域技术人员能够获知的其他可用于加热悬浮液至 黑色的方式均可选用， 具体操作方式为现有技术， 不再赘述。
将歩骤 （1 )所述悬浮液加热至 80~200°C并保持 4~24h; 加热终点温度可选 择 85°C， 93 °C , 108°C， 145°C， 180°C， 195°C等， 优选 100~150°C， 进一歩 125 °C， 保持时间可选择 5h， 8h， 13h， 17h， 20h， 23h等， 优选 8~15h， 进一歩优 选 10h。 很明显， 本发明为低温加热方式。
在上述加热过程中同时进行磁力搅拌或机械搅拌， 搅拌速度为 100~1000r/min,例如 230r/min， 380r/min, 520r/min, 625r/min, 800r/min, 983r/min 等， 优选 200~600r/min， 进一歩优选 500r/min。
歩骤 （3 ) 固液分离方式为现有技术， 所述固液分离以不改变所获得的固体 的物理化学性质为准。 优选过滤、 离心分离、 沉淀、 重力沉降、 离心沉降， 进 一歩优选过滤、 离心分离。
所述过滤包括抽滤、 压滤、 真空过滤、 离心过滤、 真空抽滤、 膜过滤、 超 滤。 过滤操作为本领域技术人员进行固液分离常用手段， 本发明并无特殊限制。 所述有机电解质溶液优选 1M TEA-BF4/PC; 所述羁留体为超级电容器或者 锂电池的电极。
一种加热氧化石墨的有机溶剂悬浮液制备石墨烯的方法， 优选包括以下歩 骤：
( 1 ) 将氧化石墨加入无水极性有机溶剂中， 超声 l~8h 制得浓度为 0.01~10g/L的悬浮液；
(2)将上述悬浮液在 80~200°C加热 4~24h， 至悬浮液变成黑色， 同时有部 分或者全部凝聚；
(3 ) 将歩骤 （2) 的黑色悬浮液过滤， 去除极性有机溶剂后得到滤饼；
(4) 向歩骤 （3 ) 所得滤饼中滴入有机电解质溶液并抽滤， 得黑色浆状物 并直接涂布于羁留体使用； 或直接干燥歩骤 （3 ) 所得滤饼， 得到石墨烯材料。
一种如上所述方法制得的石墨烯， 其电导大于 lS/m。
一种如上所述方法制得的石墨烯， 可直接用于对水分高度敏感的器件， 比 如超级电容器或者锂离子电池中， 也可以进一歩去除有机溶剂， 得到石墨烯粉 状或者纸状材料。
本发明工艺流程包括氧化石墨在极性有机溶剂中的超声分散， 低温加热所 得悬浮液， 以及后续的固液分离和干燥等歩骤。 本发明的特点是利用氧化石墨 中官能团的极性与极性有机溶剂分子之间的强相互作用， 在同一种介质中实现 氧化石墨的解理与还原， 有效地简化了生产歩骤并防止其他污染尤其是水的进 入。 如此得到的完全干燥 （无水） 的石墨烯材料电导比氧化石墨高出 5个量级 以上， 大于 lS/m， 且在有机溶剂中有一定程度的分散性稳定性， 可直接用于某 些对水分高度敏感的器件， 比如超级电容器或者锂离子电池中。 此外， 也可以 进一歩去除有机溶剂， 得到石墨烯粉状或者纸状材料。 本发明所涉及的歩骤和 仪器简单， 流程易于大规模生产， 从而得到价格低廉的， 兼高电导的无水石墨 烯材料， 不需要任何还原性的化学试剂。
附图说明
图 1所示的是水合阱还原法；
图 2所示的是热处理还原法；
图 3所示的是微波辐照还原法；
图 4是本发明制备石墨烯方法的流程图。
下面对本发明进一歩详细说明。 但下述的实例仅仅是本发明的简易例子， 并不代表或限制本发明的权利保护范围， 本发明的权利范围以权利要求书为准。 具体实施方式
以下结合附图对本发明的优选实施例进行说明， 应当理解， 此处所描述的 优选实施例仅用于说明和解释本发明， 并不用于限定本发明。
实施例 1 :
利用在碳酸丙烯中直接加热得到石墨烯材料的方法， 包括以下制备歩骤：
1、 称取 lg氧化石墨颗粒置于玻璃烧杯中， 加入 1L无水碳酸丙烯， 用针状 超声设备超声 2h， 得到 lg/L的氧化石墨悬浮液；
2、 将歩骤 1得到的氧化石墨悬浮液， 置于油浴中搅拌加热至 150°C并保持 4h， 搅拌速度 200r/min;
3、 将歩骤 2得到的悬浮液倒入真空过滤装置， 开启真空闽门进行抽滤， 直 至无液滴滴下；滴 1ml的电解质溶液（1M TEA-BF4/PC)洗涤后，快速抽滤 lmin;
4、 将歩骤 3得到的浆状物质直接涂布于超级电容器羁留体作为有机超级电 容器电极使用。
用四探针测试仪测定石墨烯材料的电导为 2.6S/m。 实施例 2:
利用在碳酸丙烯中直接加热得到石墨烯材料的方法， 包括以下制备歩骤：
1、 称取 10g氧化石墨颗粒置于玻璃烧杯， 加入 2L无水碳酸丙烯， 用针状 超声设备超声 5h， 得到 5g/L的氧化石墨悬浮液；
2、 将歩骤 1得到的氧化石墨悬浮液， 置于油浴中搅拌加热至 150°C， 并保 持 20h， 搅拌速度 lOOOr/min;
3、 将歩骤 2得到的悬浮液倒入真空过滤装置， 开启真空闽门进行抽滤， 直 至无液滴滴下；
4、 将歩骤 3得到的浆状物质烘干得石墨烯粉状材料。
用四探针测试仪测定石墨烯粉状材料的电导为 5.1S/m。
实施例 3:
利用在二甲基甲酰胺中直接加热得到石墨烯材料的方法， 包括以下制备歩 骤：
1、 称取 7g氧化石墨颗粒置于玻璃烧杯， 加入 1L无水二甲基甲酰胺， 用针 状超声设备超声 2h， 得到 7g/L的氧化石墨悬浮液；
2、 将歩骤 1得到的氧化石墨悬浮液， 置于油浴中搅拌加热至 150°C， 并保 持 15h， 搅拌速度 200r/min;
3、 将歩骤 2得到的悬浮液倒入真空过滤装置， 开启真空闽门进行抽滤， 直 至无液滴滴下；滴 1ml的电解质溶液（1M TEA-BF4/PC)洗涤后，快速抽滤 lmin;
4、 将歩骤 3得到的浆状物质直接涂布于锂电池的电极作为有机超级电容器 电极使用。
用四探针测试仪测定石墨烯粉状材料的电导为 4.6S/m。
实施例 4: 利用在 N-甲基 -2-吡咯垸酮中直接加热得到石墨烯材料的方法， 包括以下制 备歩骤：
1、称取 10g氧化石墨颗粒置于玻璃烧杯，加入 1L无水 N-甲基 -2-吡咯垸酮， 用针状超声设备超声 3h， 得到 10g/L的氧化石墨悬浮液；
2、 将歩骤 1得到的氧化石墨悬浮液， 置于油浴中搅拌加热至 150°C， 并保 持 4h， 搅拌速度 200r/min;
3、 将歩骤 2得到的悬浮液倒入真空过滤装置， 开启真空闽门进行抽滤， 直 至无液滴滴下；
4、 将歩骤 3得到的浆状物质直接烘干得纸状与粉末状混合石墨烯材料。 用四探针测试仪测定石墨烯材料的电导为 6.1S/m。
实施例 5:
利用在碳酸丙烯、 N-甲基 -2-吡咯垸酮混合液中直接加热得到石墨烯材料的 方法， 包括以下制备歩骤：
1、 称取 O.Olg氧化石墨颗粒置于玻璃烧杯中， 加入 1L无水碳酸丙烯、 N- 甲基 -2-吡咯垸酮混合液，用针状超声设备超声 lh，得到 lg/L的氧化石墨悬浮液;
2、 将歩骤 1 得到的氧化石墨悬浮液， 置于油浴中搅拌加热至 80°C并保持 24h， 搅拌速度 lOOr/min;
3、 将歩骤 2得到的悬浮液倒入真空过滤装置， 开启真空闽门进行抽滤， 直 至无液滴滴下；滴 1ml的电解质溶液（1M TEA-BF4/PC)洗涤后，快速抽滤 lmin;
4、 将歩骤 3得到的浆状物质直接涂布于超级电容器羁留体作为有机超级电 容器电极使用。
用四探针测试仪测定石墨烯材料的电导为 3.9S/m。
实施例 6: 利用在碳酸丙烯中直接加热得到石墨烯材料的方法， 包括以下制备歩骤：
1、 称取 10g氧化石墨颗粒置于玻璃烧杯， 加入 2L无水碳酸丙烯， 用针状 超声设备超声 8h， 得到 5g/L的氧化石墨悬浮液；
2、 将歩骤 1得到的氧化石墨悬浮液， 置于油浴中搅拌加热至 200°C， 并保 持 20h， 搅拌速度 800r/min;
3、 将歩骤 2得到的悬浮液倒入真空过滤装置， 开启真空闽门进行抽滤， 直 至无液滴滴下；
4、 将歩骤 3得到的浆状物质烘干得石墨烯粉状材料。
用四探针测试仪测定石墨烯粉状材料的电导为 6.3S/m。
本发明实施例 1-6得到的完全干燥（无水）的石墨烯材料电导比氧化石墨高 出 5个量级以上， 均大于 lS/m， 且在有机溶剂中有一定程度的分散性稳定性， 并且不需要任何还原性的化学试剂。
最后应说明的是： 以上所述仅为本发明的优选实施例而已， 并不用于限制 本发明， 尽管参照前述实施例对本发明进行了详细的说明， 对于本领域的技术 人员来说， 其依然可以对前述各实施例所记载的技术方案进行修改， 或者对其 中部分技术特征进行等同替换。 凡在本发明的精神和原则之内， 所作的任何修 改、 等同替换、 改进等， 均应包含在本发明的保护范围之内。

Claims

权 利 要 求 书
1、 加热氧化石墨的有机溶剂悬浮液制备石墨烯的方法， 其特征在于， 包括 以下歩骤：
( 1 ) 将氧化石墨加入极性有机溶剂中， 超声制得悬浮液；
(2) 将上述悬浮液加热至黑色， 出现部分或者全部凝聚；
(3 ) 将歩骤 （2) 的黑色悬浮液进行固液分离， 去除极性有机溶剂后得到 固体；
(4) 向歩骤 （3 ) 所得固体中滴入有机电解质溶液并抽滤， 得黑色浆状物 并直接涂布于羁留体使用； 或，
直接干燥歩骤 （3 ) 所得固体， 得到石墨烯材料。
2、 如权利要求 1 所述的方法， 其特征在于， 所述氧化石墨通过 Hummers 法制备得到。
3、 如权利要求 1或 2所述的方法， 其特征在于， 所述极性有机溶剂为无水 极性有机溶剂， 优选 N-甲基 -2-吡咯垸酮、 Ν,Ν-二甲基乙酰胺、 二甲亚砜、 碳酸 丙烯、 二甲基甲酰胺或至少两种的混合物， 进一歩优选电偶极矩大于 2德拜的 极性有机溶剂， 特别优选碳酸丙烯、 二甲基甲酰胺、 Ν-甲基 -2-吡咯垸酮或至少 两种的混合物。
4、 如权利要求 1-3之一所述的方法， 其特征在于， 歩骤（1 )所述的超声时 间为 l~8h， 优选 2~5h， 进一歩优选 3.6h;
歩骤 （1 ) 所述悬浮液浓度为 0.01~10g/L， 优选 l~8g/L， 进一歩优选 5g/L。
5、 如权利要求 1-4之一所述的方法， 其特征在于， 歩骤（2)所述加热方式 为水浴加热、 油浴加热、 微波加热或超声加热， 进一歩优选油浴加热方式； 将歩骤 （1 )所述悬浮液加热至 80~200°C并保持 4~24h; 加热终点温度优选 100~150°C， 进一歩 125°C， 保持时间优选 8~15h， 进一歩优选 10h;； 加热过程中同时进行磁力搅拌或机械搅拌， 搅拌速度为 100~1000r/min， 优 选 200~600r/min， 进一歩优选 500r/min。
6、 如权利要求 1-5之一所述的方法， 其特征在于， 歩骤（3 ) 固液分离方式 优选过滤、 离心分离、 沉淀、 重力沉降、 离心沉降； 进一歩优选过滤、 离心分 所述过滤包括抽滤、 压滤、 真空过滤、 离心过滤、 真空抽滤、 膜过滤、 超 滤。
7、 如权利要求 1-6之一所述的方法， 其特征在于， 所述有机电解质溶液优 选 1M TEA-BF4/PC; 所述羁留体为超级电容器或者锂电池的电极。
8、 如权利要求 1所述的方法， 其特征在于， 包括以下歩骤：
( 1 ) 将氧化石墨加入无水极性有机溶剂中， 超声 l~8h 制得浓度为 0.01~10g/L的悬浮液；
(2)将上述悬浮液在 80~200°C下加热 4~24h， 至悬浮液变成黑色， 同时有 部分或者全部凝聚；
(3 ) 将歩骤 （2) 的黑色悬浮液过滤， 去除极性有机溶剂后得到滤饼；
(4) 向歩骤 （3 ) 所得滤饼中滴入有机电解质溶液并抽滤， 得黑色浆状物 并直接涂布于羁留体使用； 或直接干燥歩骤 （3 ) 所得滤饼， 得到石墨烯材料。
9、 一种如权利要求 1-8之一所述方法制得的石墨烯， 其特征在于， 其电导 大于 lS/m。
10、 一种如权利要求 9所述石墨烯的用途， 可直接用于对水分高度敏感的 器件， 优选超级电容器或者锂离子电池中， 也可以进一歩去除有机溶剂， 得到 石墨烯粉状或者纸状材料。
PCT/CN2012/071069 2011-02-28 2012-02-13 加热氧化石墨的有机溶剂悬浮液制备石墨烯的方法，由此方法获得的石墨烯及其用途 WO2012116594A1 (zh)

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