WO2016074393A1 - 规模化制备大片石墨烯的方法 - Google Patents

规模化制备大片石墨烯的方法 Download PDF

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WO2016074393A1
WO2016074393A1 PCT/CN2015/074139 CN2015074139W WO2016074393A1 WO 2016074393 A1 WO2016074393 A1 WO 2016074393A1 CN 2015074139 W CN2015074139 W CN 2015074139W WO 2016074393 A1 WO2016074393 A1 WO 2016074393A1
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graphene
graphite powder
scale preparation
acid
graphite
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French (fr)
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拜永孝
胡新军
沙嫣
沙晓林
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上海史墨希新材料料技有限公司
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Priority to EP15859074.5A priority Critical patent/EP3219668B1/en
Priority to US15/525,584 priority patent/US10717652B2/en
Publication of WO2016074393A1 publication Critical patent/WO2016074393A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • 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
    • 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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • 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
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/02—Single layer graphene
    • 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
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area

Definitions

  • the present invention relates to a method for the large scale preparation of large sheets of graphene.
  • Graphene is a monoatomic layer honeycomb two-dimensional grid structure composed of carbon atoms by sp 2 hybridization. Graphene exists in a two-dimensional crystal structure with a thickness of only 0.334 nm. It is the thinnest material known in the world and is the basic unit for constructing other dimensions of carbonaceous materials. It can be wrapped to form zero-dimensional fullerenes. Formed one-dimensional carbon nanotubes, which are stacked to form three-dimensional graphite (Allen MJ, Tung VC, Kaner R B. Honeycomb carbon: A review of graphene [J]. Chemical Reviews, 2010, 110(1): 132- 145.). Thanks to this special two-dimensional structure, graphene has many special properties.
  • graphene has many other characteristics in terms of electrical and magnetic properties, such as room temperature quantum Hall effect, bipolar electric field effect, ferromagnetism, superconductivity and the like. These excellent properties make graphene have broad application prospects in the fields of nanoelectronic devices, gas sensors, energy storage and composite materials (Geim AK, Novoselov K S. The rise of graphene [J]. Nature Materials, 2007, 6 ( 3): 183-191.).
  • the radial scale of the graphene sheets prepared is small, especially in the subsequent process of ultrasonic stripping, which is very serious to the graphene edge structure. Due to the instantaneous large impact energy provided by the ultrasonic waves and the instantaneous high temperature microenvironment of the material and the medium, the graphene sheet is subjected to strong shearing force and impact force to be broken into micron, submicron or even nano-scale lamellar radial. size. Therefore, the chemical oxidation and ultrasonic stripping preparation processes of the existing liquid phase oxidation-reduction method are difficult to obtain graphene having a large-sized sheet structure.
  • the current chemical stripping method is inseparable from the water washing process, and a large cohesive force is generated between the graphite sheets after the water washing, so that the viscosity of the graphite oxide becomes extremely large instantaneously.
  • This not only makes the cleaning process for further removal of ions and impurities extremely difficult but takes longer and consumes more power to complete the washing, filtering and drying of the graphite oxide.
  • the strong cohesive force makes the spacing between the intercalated graphite oxide sheets reversed, that is, the spacing of the graphite oxide sheets is reduced. This result makes the peeling of graphene more difficult, which is very unfavorable for the peeling of the sheets. .
  • the current process of preparing graphene by liquid phase chemical stripping method is generally characterized by harsh preparation conditions, complicated process, low efficiency, and small radial dimension of the sheet.
  • the prepared graphene has many lattice defects, severe destruction of the SP 2 hybrid structure, and large loss of intrinsic properties due to excessive oxidation and intense reaction. Therefore, it is necessary and urgent to develop a method for preparing a graphene which has a mild intercalation, a simple process, a high production efficiency, a large radial dimension of the sheet, and a scale preparation.
  • the sheet size of graphene has a decisive influence on the electrical properties of electronic devices, composite materials, and the mechanical properties, antistatic properties, gas barrier properties, electrical conductivity and thermal conductivity of graphene-polymer nanocomposites ( Lin X, Shen X, Zheng Q, Yousefi N, Ye L, Mai YW, et al. Fabrication of Highly-Aligned, Conductive, and Strong Graphene Papers Using Ultralarge Graphe Oxide Sheets. ACS Nano. 2012;6(12):10708- 19).
  • Graphene with large radial dimension can effectively form a complete network structure in the matrix of the constructed material.
  • the network structure of Unicom and Bridge can significantly improve the antistatic property, gas barrier resistance and conductivity of the material.
  • the object of the present invention is to provide a raw material with low cost, easy availability, simple operation, simple process (high efficiency), high yield, large radial dimension of the sheet and good crystal structure (quality). High) method for the preparation of large sheets of graphene.
  • the method for large-scale preparation of large-sized graphene according to the present invention is composed of three steps of graphite oxidation---diluted hydrochloric acid cleaning--high temperature treatment. Achieve low cost, high efficiency, low energy consumption and ring scale for high-quality large-scale graphene preparation a friendly way.
  • the invention relates to a method for large-scale preparation of large-sized graphene.
  • the graphite powder is intercalated with an acid and an oxidizing agent under mild conditions, and the metal and inorganic ions are washed away with dilute hydrochloric acid, filtered and dried, and obtained by high temperature treatment.
  • the large piece of graphene The current oxidation-reduction method is required to require a high temperature, continuous and multi-step oxidation process, and the conventional method is used to generate a large cohesive force between the graphite sheets after water washing, so that the viscosity of the graphite oxide becomes very large instantaneously. Fatal flaws.
  • the invention effectively solves the strong van der Waals force and cohesion between the sheets produced by the post-treatment of graphite oxide in the current oxidation-reduction method, and the reverse spacing of the intercalated graphite oxide sheets is the graphite oxide sheet.
  • the problem that the spacing is rapidly reduced is effectively solved. Since the adhesion between the layers of the graphite oxide sheet makes the peeling of the graphite after oxidation more difficult, it is very disadvantageous for the peeling of the graphite sheet to obtain a thinner graphene.
  • the acid is selected from a mixture of one or more of concentrated sulfuric acid, concentrated nitric acid, phosphoric acid, and perchloric acid.
  • the oxidizing agent is selected from one or more of potassium permanganate, potassium chlorate, sodium chlorate, potassium persulfate, and potassium dichromate.
  • the graphite powder is selected from one or a combination of natural flake graphite powder, expandable graphite powder, and expanded graphite powder.
  • the graphite powder has a sheet radial dimension of 300 to 500 ⁇ m.
  • the prepared large-sized graphene has a radial dimension of 20 um to 200 um, and the graphene can be controlled by controlling the kinetic conditions such as the ratio of the materials of the reaction, the reaction time, and the stirring rate. Radial scale size and distribution.
  • the amount of acid per gram of graphite powder is 20 to 60 ml; and the amount of oxidizing agent per gram of graphite powder is 5 to 10 g.
  • the amount of dilute hydrochloric acid per gram of graphite powder is 150-350 ml; and the concentration of the diluted hydrochloric acid is 0.5-10%.
  • the temperature of the high temperature treatment is 500 to 1050 °C.
  • sheet peeling is achieved by high temperature processing. Sheet peeling is achieved without the need for ultrasonic peeling and long-term high energy shearing and high speed grinding processes employed in conventional oxidation-reduction methods. The loss of the intrinsic properties of the prepared graphene is avoided by the severe destruction of the crystal structure of the graphite oxide under the action of strong ultrasonic, cavitation and strong energy for a long time.
  • the method specifically includes the following steps:
  • the filter cake is pulverized and treated at a high temperature for 15 to 30 seconds to obtain the large piece of graphene.
  • step A the amount of hydrogen peroxide per gram of graphite powder is 2 to 20 ml; and the amount of water per gram of graphite powder is 150 to 200 ml.
  • the drying temperature is 30 to 85 ° C, and the drying time is 48 to 200 hours.
  • the pulverizing device adopts one of a wheel mill, a vibration mill, a turbo pulverizer, a jet mill, a fan coal mill, a sand mill, a colloid mill, a ball mill, and a household pulverizer. .
  • the present invention has the following beneficial effects:
  • the raw materials used in the invention are cheap, the process is simple, the efficiency is high, no water washing is needed, no ultrasonic peeling is needed, and a small amount of volatile hydrochloric acid molecules are adsorbed between the sheets of graphite oxide, and the oxygen content of the graphite oxide is treated at high temperature.
  • the group decomposes rapidly, generating a large amount of gas to promote separation of the sheets.
  • the graphite oxide sheet adsorbed with hydrochloric acid molecules can also expand and release the gas to be instantaneously peeled off.
  • the above double action realizes efficient stripping of the graphite oxide, and avoids severe damage to the graphene crystal structure and stripping when ultrasonic stripping is used.
  • the disadvantage of continuous smashing of the radial dimension of the layer, thereby obtaining graphene having a large radial size and high quality, is easy to realize industrial mass production.
  • the radial dimension of the graphene prepared by the invention is between 20 um and 200 um, and the radial size and distribution of the graphene can be controlled by controlling the graphite raw materials and the reaction conditions, and the prepared graphene has few defects.
  • Graphene is dispersed in N-methylpyrrolidone, and the conductivity of the membrane is up to 600 S/cm. It can meet the requirements of high quality graphene products in the composite materials and electronics industries.
  • Figure 1 is a process flow diagram for preparing graphene
  • Example 2 is an X-ray diffraction pattern of graphite, graphite oxide, and graphene in Example 1;
  • Figure 3 is a SEM photograph of graphene
  • Figure 4 is a partial TEM photograph of a graphene sheet
  • Example 5 is a Raman spectrum of graphene, graphite oxide, and graphite powder in Example 2.
  • the invention relates to a method for large-scale preparation of large-sized graphene.
  • the large-sized graphite is intercalated and modified by using an acid and an oxidizing agent, and the metal and inorganic ions therein are washed away with dilute hydrochloric acid, filtered and dried, and high-temperature treatment is performed to obtain high quality.
  • the large amount of graphene effectively avoids the problems of the high-efficiency preparation of high-quality graphene which is caused by the conventional method of washing with water to neutral.
  • the invention comprises the following steps:
  • the graphite may be one or a combination of natural flake graphite, expandable graphite or expanded graphite, and the sheet size of the graphite may be selected from 300 to 500 ⁇ m.
  • the acid (recognized as 98% acid) is one or a mixture of concentrated sulfuric acid, concentrated nitric acid, phosphoric acid, perchloric acid.
  • the oxidizing agent is one or more of potassium permanganate, potassium chlorate, sodium chlorate, potassium persulfate, and potassium dichromate.
  • the ratio of graphite to acid is 1 g: 20 to 60 ml
  • the ratio of graphite to oxidizing agent is 1 g: 5 to 10 g
  • the ratio of graphite to 20% (v/v) aqueous hydrogen peroxide solution is 1 g: 2 to 20 ml.
  • the mixed aqueous solution of the graphite oxide obtained above is vacuum-filtered, washed with a 10% hydrochloric acid aqueous solution, and the residual metal ions and inorganic ions are washed and filtered, and then dried at a constant temperature.
  • the ratio of graphite to dilute hydrochloric acid for washing is 1 g: 300 to 500 ml, and the dried temperature of the graphite oxide cake after filtration is 30 to 85 ° C, and the drying temperature of the graphite oxide cake is 48 to 200 hours.
  • the filter cake obtained by washing the diluted hydrochloric acid is mechanically pulverized and treated at a certain high temperature for 15 to 30 seconds to obtain a large piece of graphene, and the graphene yield of the layer having a layer of 10 or less is 90% or more.
  • the pulverizing equipment is one of a wheel mill, a vibration mill, a turbine pulverizer, a jet mill, a fan coal mill, a sand mill, a colloid mill, a ball mill, a household pulverizer, and the like.
  • the high temperature range of the graphite oxide powder treatment is 500 to 1350 °C. See the following examples for details:
  • the embodiment relates to a method for large-scale preparation of large-sized graphene, and the specific preparation process is as shown in FIG. 1:
  • the mixed aqueous solution of graphite oxide was vacuum-filtered, washed with 1 L of 10% (V/V) and 1 L of 0.5% (V/V) hydrochloric acid, and the residual metal ions and inorganic ions were washed clean and dried at 60 ° C for 48 hours.
  • the cake was pulverized into a powder by a household pulverizer, and treated at 1050 ° C for 15 s to obtain a large piece of graphene, and the yield of graphene having a layer number of 10 or less was 90% or more.
  • the large-sized graphene obtained above has a graphene sheet having a radial dimension of 50% between 20 and 100 ⁇ m and a graphene sheet having a radial dimension of more than 100 ⁇ m of 15%.
  • the characteristic peak of the natural graphite powder is 26.4°, which is the (002) crystal plane of the graphite crystal.
  • the layer spacing is 0.34 nm.
  • the (002) peak of the natural graphite powder disappears, and the characteristic peak of the graphite oxide is 10.8°, which is a characteristic peak of the (001) crystal plane, and the corresponding layer spacing is 0.84 nm.
  • Graphene has a characteristic peak (002) at 26.4°.
  • the characteristic peak of graphene at this position is obviously broadened, indicating that the interlamellar spacing of graphene is larger than that of natural graphite powder. That is, the natural graphite powder is peeled off into graphene.
  • Fig. 3 is a SEM photograph of graphene prepared in the present example
  • Fig. 4 is a partial TEM photograph of graphene sheets. 3 and 4, the graphene sheets prepared by the invention have large radial dimensions, flat sheet structure, few crystal defects and high quality.
  • the embodiment relates to a method for large-scale preparation of large-sized graphene, and the specific preparation process is as shown in FIG. 1:
  • the cake was pulverized into a powder by a household pulverizer, and treated at 850 ° C for 30 s to obtain a large piece of graphene, and the yield of graphene having a layer number of 10 or less was 90% or more.
  • the large-sized graphene obtained as described above has a graphene sheet having a radial dimension of 65% between 20 and 100 ⁇ m and a graphene sheet having a radial dimension of more than 100 ⁇ m of 13%.
  • the main characteristic peaks of the graphite-thin Raman spectrum are D peak (at 1340 cm -1 ), G peak (1580 cm -1 ), and 2D peak (2700 cm -1 ).
  • the generation process of the D peak involves the scattering process of the incident on the incident photon and thus reflects the disorder caused by the graphite thinning due to groups, defects and edges. The more defects, the higher the degree of disorder and the stronger the D peak.
  • the graphite powder is oxidized and intercalated, the defects increase and the D peak is high. After the high temperature expansion and reduction, the D peak is obviously weakened, indicating that the graphene prepared by the invention has few defects and high quality.
  • the embodiment relates to a method for large-scale preparation of large-sized graphene, and the specific preparation process is as shown in FIG. 1:
  • the large-sized graphene obtained as described above has a graphene sheet having a radial dimension of 80% between 20 and 100 ⁇ m and a graphene sheet having a radial dimension of more than 100 ⁇ m of 5%.
  • the embodiment relates to a method for large-scale preparation of large-sized graphene, and the specific preparation process is as shown in FIG. 1:
  • the cake was pulverized into a powder by a household pulverizer, and treated at 1050 ° C for 15 s to obtain a large piece of graphene, and the yield of graphene having a layer number of 10 or less was 90% or more.
  • the large-sized graphene obtained above has a graphene sheet having a radial dimension of 70% between 20 and 100 ⁇ m and a graphene sheet having a radial dimension of more than 100 ⁇ m of 8%.
  • the graphite oxide prepared in Example 1 was treated at 1350 ° C for 15 s to obtain a large piece of graphene, and the graphene yield having a layer number of 10 or less was 90% or more.
  • the quality of graphene obtained after treatment at 1350 ° C is higher, and the D peak in the Raman spectrum is substantially disappeared, that is, the defects and structural incompleteness of graphene are greatly reduced and lowered at higher temperatures.
  • the intrinsic properties of the prepared large graphene such as conduction and heat conduction are further improved.
  • the graphite intercalation process adopts a gentle method.
  • the post-treatment process of washing, filtering and drying of the graphite oxide after intercalation treatment is very simple and efficient, and avoids a series of high-quality and high-efficiency graphene constraints caused by washing the graphite oxide to neutral with a large amount of distilled water.
  • the problem of preparation The raw materials used in the invention are cheap, mild in condition, simple in process, low in energy consumption, environmentally friendly, and do not require water washing and ultrasonic stripping, and are easy to realize industrial mass production.
  • the scale distribution of the graphene prepared by the invention is between 20 um and 200 um, and the radial scale and size distribution of the graphene sheet layer can be controlled by selecting the graphite raw material and controlling the reaction conditions.
  • the graphene prepared by the invention has few defects and high quality, and can basically maintain its intrinsic properties, especially electrical properties and thermal conductivity.
  • the graphene dispersion is filtered to a film with a conductivity of 600 S/cm or more, which satisfies the high-quality graphite in the field of functional properties of graphene films, fibers and composite materials using its mechanical properties and electronic materials and functional coatings. Requirements for olefin products.

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Abstract

提供一种规模化制备大片石墨烯的方法：通过用酸和氧化剂在温和的条件下对石墨粉进行插层处理，用稀盐酸洗去其中的金属及无机离子，过滤干燥，高温处理即可。该方法突破了传统方法用大量去离子水将氧化石墨洗至中性时产生的一系列制约石墨烯高效率制备的瓶颈；易实现批量生产。所制备石墨烯的片层径向尺度分布在20 μm～200 μm之间。

Description

规模化制备大片石墨烯的方法 技术领域
本发明涉及一种规模化制备大片石墨烯的方法。
背景技术
石墨烯是由碳原子通过sp2杂化构成的单原子层蜂窝状二维网格结构。石墨烯以二维晶体结构存在,厚度只有0.334nm,是目前世界上已知的最薄的材料，也是构筑其它维度炭质材料的基本单元,它可以包裹起来形成零维的富勒烯,卷起来形成一维的碳纳米管,层层堆积形成三维的石墨(Allen M J,Tung V C,Kaner R B.Honeycomb carbon:A review of graphene[J].Chemical Reviews,2010,110(1):132-145.)。得益于这种特殊的二维结构，石墨烯具有许多特殊的性能。其理论比表面积高达2630m2/g，拥有超高的杨氏模量(～1100GPa)和断裂强度(125GPa)，以及优良的热传导性(～5000W/(m×k))和载流子传导率(2×105cm2/v)，此外，石墨烯在电和磁学性能等方面也有很多其他的特性，如室温量子霍尔效应、双极性电场效应、铁磁性、超导性等。这些优异的性能使得石墨烯在纳米电子器件、气体传感器、能量存储及复合材料等领域有广阔的应用前景(Geim A K,Novoselov K S.The rise of graphene[J].Nature Materials,2007,6(3):183-191.)。
至今虽然世界各国已提出了制备石墨烯的多种方法，但所制备石墨烯片层径向尺度均较小，尤其是后续需要超声剥离的工艺过程对石墨烯边沿结构破坏非常严重。由于超声波提供的瞬时巨大冲击能量以及物料与介质作用部分瞬间的高温微环境，使石墨烯片层受到强剪切力和冲击力而碎裂为微米、亚微米甚至是纳米级别的片层径向尺寸。因而现有的液相氧化-还原方法的化学氧化和超声剥离制备过程很难得到片层结构大尺寸的石墨烯。同时，目前化学剥离法都离不开水洗过程，水洗后的氧化石墨片层之间产生巨大的内聚力，使得氧化石墨的粘度瞬间变得非常大。这样不但使进一步去除离子和杂质的清洗过程变的异常困难而需要更长的时间和消耗更大的动力来完成氧化石墨的洗涤、过滤和干燥。而且强大内聚力使得插层后的氧化石墨片层间的间距逆向发展即氧化石墨片层的间距会有所减小，这一结果使石墨烯的剥离变得愈加困难，非常不利于片层的剥离。若要达到有效的超声剥离和片层分离就需要更大功率和更长时间的超声处理来实 现。可以想见氧化石墨长时间处于强烈超声和空化状态其晶体结构就会发生严重的破坏而导致所制备石墨烯部分性能的损失。这是目前液相氧化-还原的化学剥离法制备石墨烯的又一瓶颈问题。此外，目前液相氧化-还原的化学剥离法需要非常长的时间和十分巨大的动力消耗用来解决氧化石墨的洗涤和过滤过程，这一制约因素使其产品的制备成本大幅提高，生产效率急剧降低。总之，目前液相化学剥离方法制备石墨烯的过程普遍存在制备条件苛刻、工艺复杂、效率较低、片层径向尺度小。所制备石墨烯由于氧化过度和反应剧烈而导致晶格缺陷多、SP2杂化结构破坏严重、本征性能丧失较大。因而，开发一种温和插层、工艺简便、生产高效、片层径向尺寸大及规模制备的石墨烯的制备方法是必要而迫切的。
石墨烯的片层大小对电子器件、复合材料的导电性和石墨烯-聚合物纳米复合材料的机械性能、抗静电性、抗气体阻隔性、导电性和导热性等性能均有着决定性的影响(Lin X,Shen X,Zheng Q,Yousefi N,Ye L,Mai Y-W,et al.Fabrication of Highly-Aligned,Conductive,and Strong Graphene Papers Using UltralargeGraphene Oxide Sheets.ACS Nano.2012；6(12):10708-19)。片层径向尺寸较大的石墨烯，能够有效地在所构筑材料基体内形成较完整的网络结构，联通和搭桥式的网络结构可以显著地提高材料的抗静电性、抗气体阻隔性、导电性和导热性等综合性能，与普通小片石墨烯相比，径向尺度较大的大片石墨烯使用较低的添加量就可以实现和达到所构筑材料的上述功能性。因此大片石墨烯的制备和规模化生产技术是迫切而关键的。目前，已经有以小粒度石墨粉或膨胀石墨为原料，采用改进的Hummers法制备氧化石墨烯的专利报道，然而以小粒径石墨粉为原料时，其氧化效率较高。现有技术以大粒度鳞片状石墨为原料时，其氧化效率及氧化石墨的可剥离度均较差，产品需要进行后续的分级分离，产率低，工艺繁琐。例如闵永刚等[CN 103741264A]先用强酸对石墨进行插层，高温膨胀，再用Hummers法进行氧化，离心、透析后得到大片的氧化石墨烯，所得石墨烯产品的片层径向尺寸较小(20～80μm)，制备工艺复杂，成本较高。
发明内容
本发明的目的在于针对上述现有技术存在的不足，提供一种原料成本低廉、易得、操作简便及工艺简单(效率高)、产率高、片层径向尺寸大且晶体结构完好(质量高)的规模化制备大片石墨烯的方法。
本发明所述的规模化制备大片石墨烯的方法，由石墨氧化---稀盐酸清洗---高温处理三个步骤构成。实现了高质量大片石墨烯规模化制备的低成本、高效率、低能耗及环 境友好的途径。
本发明的目的是通过以下技术方案来实现的：
本发明涉及一种规模化制备大片石墨烯的方法，通过用酸和氧化剂在温和的条件下对石墨粉进行插层处理，用稀盐酸洗去其中的金属及无机离子，过滤干燥，高温处理得到所述大片石墨烯。避免了目前氧化-还原的方法需要高温、持续和多步氧化的处理过程，并且杜绝了传统方法水洗后的氧化石墨片层之间产生巨大的内聚力而使氧化石墨的粘度瞬间变得非常大的致命缺陷。粘度增大可使石墨烯制备过程中去除离子和杂质的清洗过程变的异常困难而需要更长的时间和消耗更大的动力来完成氧化石墨的洗涤、过滤和干燥。同时，本发明有效破解了目前氧化-还原方法中氧化石墨后处理时产生的片层间强大的范德华力和内聚力，而使得插层后的氧化石墨片层间的间距逆向发展即氧化石墨片层的间距会迅速减小的问题得到有效解决。因为氧化石墨片层间作用力的增强会使得氧化后石墨的剥离变得愈加困难，非常不利于氧化石墨片层的剥离而获得片层更薄的石墨烯。
作为优选技术方案，所述酸选自浓硫酸、浓硝酸、磷酸、高氯酸中一种或几种的混合物。
作为优选技术方案，所述氧化剂选自高锰酸钾、氯酸钾、氯酸钠、过硫酸钾以及重铬酸钾中的一种或几种。
作为优选技术方案，所述石墨粉选自天然鳞片石墨粉、可膨胀石墨粉、膨胀石墨粉中的一种或几种的组合。所述石墨粉的片层径向尺寸为300～500μm。
作为优选技术方案，所制备得到的大片石墨烯的片层径向尺度分布在20um～200um之间，并且可以通过对反应的物料配比、反应时间、搅拌速率等动力学条件控制来调控石墨烯的径向尺度大小和分布。
作为优选技术方案，每克石墨粉对应的酸用量为20～60ml；每克石墨粉对应的氧化剂用量为5～10g。
作为优选技术方案，每克石墨粉对应的稀盐酸用量为150～350ml；所述稀盐酸的体积百分比浓度为0.5～10％。
作为优选技术方案，所述高温处理的温度为500～1050℃。本发明中采用高温处理实现片层剥离。片层剥离不需要传统氧化-还原方法采用的超声剥离和长时间高能量剪切与高速研磨处理来实现。避免了氧化石墨长时间处于强烈超声、空化状态及强能量作用下其晶体结构发生严重破坏而导致所制备石墨烯本征性能的丧失。
作为优选技术方案，所述方法具体包括如下步骤：
A、将石墨粉与酸混合，在冰浴中缓慢加入氧化剂，混合均匀后在冰浴中反应2～48小时，升温到35℃，继续氧化36～120小时后，用水稀释，加入过氧化氢，得到含有氧化石墨的混合水溶液；
B、将所述含有氧化石墨的混合水溶液抽滤过滤，先用10％(V/V)稀盐酸清洗，再用0.5～1％(V/V)的稀盐酸将残留的金属离子及无机离子清洗干净，过滤、干燥，得滤饼；
C、将所述滤饼粉碎，高温处理15～30秒，即得所述大片石墨烯。
作为优选技术方案，步骤A中，每克石墨粉对应的过氧化氢用量为2～20ml；每克石墨粉对应的水的用量为150～200ml。
作为优选技术方案，步骤B中，所述干燥温度为30～85℃，干燥时间为48～200小时。
作为优选技术方案，步骤C中，所述粉碎设备采用轮碾机、振动磨、涡轮粉碎机、气流粉碎机、风扇磨煤机、砂磨机、胶体磨、球磨机、家用粉碎机中的一种。
与现有技术相比，本发明具有如下有益效果：
1、本发明所用原料廉价，工艺简便，效率高且不需要水洗，不需要超声剥离，少量可挥发性的盐酸分子吸附在氧化石墨的片层之间，在高温处理时，氧化石墨的含氧基团快速分解，产生大量的气体促使片层分离。同时吸附有盐酸分子的氧化石墨片也能膨胀和释放出气体而使其瞬间剥离，上述双重作用便实现了氧化石墨的高效剥离，并且避免了用超声剥离时对石墨烯晶体结构严重破坏和片层径向尺寸的连续打碎的弊端，从而获得片层径向尺寸大且质量高的石墨烯，易实现工业化大批量生产。
2、本发明制备的石墨烯的片层径向尺度分布在20um～200um之间，可以通过对石墨原料及反应条件控制来调控石墨烯的径向尺度大小和分布，制备的石墨烯缺陷少、质量高、比表面积大，尤其是其机械性能、电学性能和导热性能损失小。石墨烯分散在N-甲基吡咯烷酮中，抽滤成膜的导电率在600S/cm以上，可满足复合材料、电子工业领域对高质量石墨烯产品的要求。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明专利的其它特征、目的和优点将会变得更明显：
图1为制备石墨烯的工艺流程图；
图2为实施例1中石墨、氧化石墨和石墨烯的X射线衍射图谱；
图3为石墨烯的SEM照片；
图4为石墨烯片的局部TEM照片；
图5为实施例2中石墨烯、氧化石墨、石墨粉的拉曼图谱。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明涉及一种规模化制备大片石墨烯的方法，通过用酸和氧化剂对大片石墨进行插层和修饰处理，用稀盐酸洗去其中的金属及无机离子，过滤干燥，高温处理得到高质量的大片石墨烯，有效避免了常规方法用水洗至中性而产生的一系列制约高质量石墨烯高效率制备的问题。本发明包括以下步骤：
(1)将石墨与酸混合，在冰浴中缓慢加入氧化剂，混合均匀后在冰浴中反应2～48小时，升温到35℃，继续氧化36～120小时后，用水稀释，加入一定量的过氧化氢，得到含有氧化石墨的混合水溶液。石墨可为天然鳞片石墨、可膨胀石墨或膨胀石墨的一种或几种的组合，石墨的片层大小可选择300～500μm。酸(公认为是98％的酸)为浓硫酸、浓硝酸、磷酸、高氯酸中一种或几种混合物。氧化剂为高锰酸钾、氯酸钾、氯酸钠、过硫酸钾以及重铬酸钾中的一种或几种。石墨与酸的比例为1g:20～60ml,石墨与氧化剂的比例为1g:5～10g，石墨与20％(V/V)过氧化氢水溶液的比例为1g:2～20ml。
(2)将上述得到的氧化石墨的混合水溶液真空过滤，用10％盐酸水溶液清洗，将残留的金属离子及无机离子清洗干净并过滤后，在一定的温度下干燥。石墨与清洗用稀盐酸的比例为1g:300～500ml，过滤后氧化石墨滤饼的干燥温度为30～85℃，氧化石墨滤饼的干燥温度时间为48～200小时。
(3)将稀盐酸清洗后得到的滤饼用机械粉碎，在一定的高温下处理15～30秒，即可得到大片石墨烯，层数在10层以下的石墨烯产率在90％以上。粉碎设备为轮碾机、振动磨、涡轮粉碎机、气流粉碎机、风扇磨煤机、砂磨机、胶体磨、球磨机、家用粉碎机等的一种。氧化石墨粉处理的高温范围500～1350℃。具体见以下各实施例：
实施例1
本实施例涉及一种规模化制备大片石墨烯的方法，具体制备工艺如图1所示：
将12g 500μm天然鳞片石墨与260ml浓硫酸混合，在冰浴条件下缓慢加入60g高锰酸钾，混合均匀后在冰浴中反应2小时，升温到35℃，继续氧化48小时后，缓慢加入1.8L水，加入30ml20％(V/V)的过氧化氢水溶液，得到含有氧化石墨的混合水溶液。氧化石墨的混合水溶液真空过滤，分别用1L 10％(V/V)和1L 0.5％(V/V)盐酸清洗，将残留的金属离子及无机离子清洗干净，在60℃下干燥48小时。用家用粉碎机将滤饼粉碎成粉末，在1050℃下处理15s得到大片石墨烯，层数在10层以下的石墨烯产率在90％以上。
上述所得的大片石墨烯，石墨烯片层径向尺寸在20～100um之间的有50％，石墨烯片层径向尺寸大于100μm的有15％。
图2为石墨、氧化石墨和石墨烯的X射线衍射图，由图2可知，天然石墨粉的特征峰在26.4°，为石墨晶体的(002)晶面。根据布拉格衍射方程计算，层间距为0.34nm。当天然石墨粉被氧化后，天然石墨粉的(002)峰消失，氧化石墨的特征峰在10.8°，为(001)晶面特征峰，对应层间距为0.84nm。而石墨烯在26.4°的位置出现特征峰(002)，相对于天然石墨粉的特征峰，石墨烯在此位置的特征峰明显宽化，表明石墨烯比天然石墨粉的片层间距增大，即天然石墨粉被剥离成了石墨烯。
图3为本实施例制得的石墨烯的SEM照片，图4为石墨烯片的局部TEM照片。由图3、4可知，本发明所制备的石墨烯片层径向尺寸大、片结构平展、晶体缺陷少、质量高。
实施例2
本实施例涉及一种规模化制备大片石墨烯的方法，具体制备工艺如图1所示：
将12g 500μm可膨胀石墨与720ml浓硫酸混合，在冰浴条件下缓慢加入120g氯酸钾，混合均匀后在冰浴中反应48小时，升温到35℃，继续氧化36小时后，缓慢加入2L水，加入240ml的过氧化氢，得到含有氧化石墨的混合水溶液。氧化石墨的混合水溶液真空过滤，分别用2L 10％(V/V)和1L 0.5％(V/V)的盐酸清洗，将残留的金属离子及无机离子清洗干净，在85℃下干燥100小时。用家用粉碎机将滤饼粉碎成粉末，在850℃下处理30s得到大片石墨烯，层数在10层以下的石墨烯产率在90％以上。
上述所得的大片石墨烯，石墨烯片层径向尺寸在20～100um之间的有65％，石墨烯片层径向尺寸大于100μm的有13％。
图5为本实施例制得的石墨烯、氧化石墨、石墨粉的拉曼图，石墨稀的拉曼光谱的主要特征峰是D峰(位于1340cm-1)、G峰(1580cm-1)和2D峰(2700cm-1)。D峰的产生过程涉及缺陷对入射光子的散射过程因此能反映石墨稀由于基团、缺陷和边缘引起的无序 度。缺陷越多，无序度越高，D峰越强。石墨粉经氧化插层后，缺陷增多，D峰高，经过高温膨胀还原后，D峰明显减弱，说明该发明制备的石墨烯缺陷少、质量高。
实施例3
本实施例涉及一种规模化制备大片石墨烯的方法，具体制备工艺如图1所示：
将12g 300μm石墨粉与480ml高氯酸混合，在冰浴条件下缓慢加入90g过硫酸钾，混合均匀后在冰浴中反应20小时，升温到35℃，继续氧化120小时后，缓慢加入2.4L水，加入24ml的过氧化氢，得到含有氧化石墨的混合水溶液。氧化石墨的混合水溶液真空过滤，分别用1.4L 10％(V/V)和1L 1％(V/V)的盐酸清洗，将残留的金属离子及无机离子清洗干净，在30℃下干燥200小时。用家用粉碎机将滤饼粉碎成粉末，在500℃下处理30s得到大片石墨烯，层数在10层以下的石墨烯产率在85％以上。
上述所得的大片石墨烯，石墨烯片层径向尺寸在20～100um之间的有80％，石墨烯片层径向尺寸大于100μm的有5％。
实施例4
本实施例涉及一种规模化制备大片石墨烯的方法，具体制备工艺如图1所示：
将12g 400μm膨胀石墨与240ml磷酸混合，在冰浴条件下缓慢加入60g重铬酸钾，混合均匀后在冰浴中反应2小时，升温到35℃，继续氧化48小时后，缓慢加入1.8L水，加入30ml的过氧化氢，得到含有氧化石墨的混合水溶液。氧化石墨的混合水溶液真空过滤，分别用1L 10％(V/V)和1L 0.8％(V/V)的盐酸清洗，将残留的金属离子及无机离子清洗干净，在60℃下干燥。用家用粉碎机将滤饼粉碎成粉末，在1050℃下处理15s得到大片石墨烯，层数在10层以下的石墨烯产率在90％以上。
上述所得的大片石墨烯，石墨烯片层径向尺寸在20～100um之间的有70％，石墨烯片层径向尺寸大于100μm的有8％。
实施例5
将实施例1所制备氧化石墨，采用1350℃下处理15s得到大片石墨烯，层数在10层以下的石墨烯产率在90％以上。与实施例1相比1350℃处理后所获得石墨烯的质量更高，拉曼光谱中的D峰基本上消失即石墨烯的缺陷和结构不完整性在更高的温度下极大地减少和降低。说明采用更高温度(譬如1350℃)剥离和还原氧化石墨在1050℃剥离和还原的过程获得更少缺陷和更大还原程度即还原更加彻底的高质量石墨烯。所制备大片石墨烯的诸如导电、导热等本征性能会进一步提升。
综上所述，本发明的规模化制备大片石墨烯的方法中，石墨插层过程采用温和方 式，插层处理后的氧化石墨的洗涤、过滤和干燥等后处理过程非常简便和高效，避免了用大量蒸馏水水将氧化石墨洗至中性时产生的一系列制约石墨烯高质量、高效率制备的问题。本发明所用原料廉价，条件温和、工艺简便，能耗低、环境友好且不需要水洗和超声剥离，易实现工业化大批量生产。本发明所制备的石墨烯的尺度分布在20um～200um之间，可以通过对石墨原料选择及反应条件控制来实现石墨烯片层的径向尺度和尺寸分布的调控。本发明所制备的石墨烯缺陷少、质量高，基本能够保持其本征性能尤其是电学性能和导热性。石墨烯分散液抽滤成膜的导电率在600S/cm以上，可满足石墨烯薄膜、纤维及复合材料等利用其机械性能和电子材料与功能涂层等发挥其功能性特性领域对高质量石墨烯产品的要求。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (11)

  1. 一种规模化制备大片石墨烯的方法，其特征在于，通过用酸和氧化剂在温和的条件下对石墨粉进行插层处理，用稀盐酸洗去其中的金属及无机离子，过滤干燥，高温处理得到所述大片石墨烯。
  2. 根据权利要求1所述的规模化制备大片石墨烯的方法，其特征在于，所述酸选自浓硫酸、浓硝酸、磷酸、高氯酸中一种或几种的混合物。
  3. 根据权利要求1所述的规模化制备大片石墨烯的方法，其特征在于，所述氧化剂选自高锰酸钾、氯酸钾、氯酸钠、过硫酸钾以及重铬酸钾中的一种或几种。
  4. 根据权利要求1所述的规模化制备大片石墨烯的方法，其特征在于，所述石墨粉选自天然鳞片石墨粉、可膨胀石墨粉、膨胀石墨粉中的一种或几种的组合。
  5. 根据权利要求1所述的规模化制备大片石墨烯的方法，其特征在于，每克石墨粉对应的酸用量为20～60ml；每克石墨粉对应的氧化剂用量为5～10g。
  6. 根据权利要求1所述的规模化制备大片石墨烯的方法，其特征在于，每克石墨粉对应的稀盐酸用量为150～350ml；所述稀盐酸的体积百分比浓度为0.5～10％。
  7. 根据权利要求1所述的规模化制备大片石墨烯的方法，其特征在于，所述高温处理的温度为500～1350℃。
  8. 根据权利要求1所述的规模化制备大片石墨烯的方法，其特征在于，所述大片石墨烯的片层径向尺度分布在20μm～200μm。
  9. 根据权利要求1～8中任一项所述的规模化制备大片石墨烯的方法，其特征在于，所述方法包括如下步骤：
    A、将石墨粉与酸混合，在冰浴中缓慢加入氧化剂，混合均匀后在冰浴中反应2～48小时，升温到35℃，继续氧化36～120小时后，用水稀释，加入过氧化氢，得到含有氧化石墨的混合水溶液；
    B、将所述含有氧化石墨的混合水溶液真空过滤，用体积浓度为10％的稀盐酸清洗，再用体积浓度为0.5～1％的稀盐酸将残留的金属离子及无机离子清洗干净，过滤、干燥，得滤饼；
    C、将所述滤饼粉碎，高温处理15～30秒，即得所述大片石墨烯。
  10. 根据权利要求9所述的规模化制备大片石墨烯的方法，其特征在于，步骤A中，每克石墨粉对应的过氧化氢用量为2～20ml；每克石墨粉对应的水的用量为150～200ml。
  11. 根据权利要求9所述的规模化制备大片石墨烯的方法，其特征在于，步骤B中，所述干燥温度为30～85℃，干燥时间为48～200小时；步骤C中，所述粉碎设备采用轮碾机、振动磨、涡轮粉碎机、气流粉碎机、风扇磨煤机、砂磨机、胶体磨、球磨机、家用粉碎机中的一种。
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