WO2017128929A1 - Method for preparing graphene dispersion and article thereof - Google Patents

Method for preparing graphene dispersion and article thereof Download PDF

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WO2017128929A1
WO2017128929A1 PCT/CN2017/000051 CN2017000051W WO2017128929A1 WO 2017128929 A1 WO2017128929 A1 WO 2017128929A1 CN 2017000051 W CN2017000051 W CN 2017000051W WO 2017128929 A1 WO2017128929 A1 WO 2017128929A1
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graphite
graphene
graphene dispersion
acid
cation
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卢红斌
林珊
张佳佳
董雷
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复旦大学
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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
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • the invention belongs to the technical field of graphene preparation, and relates to a method for preparing a high concentration ultra-clean graphene dispersion liquid in a green environment, specifically, using graphite or graphite intercalation compound as a raw material, and expanding in a certain manner, and then performing in an ionic liquid. Peeling to obtain a graphene dispersion having a high concentration and a high conductivity.
  • the former such as chemical vapor deposition and epitaxial growth, can obtain high-quality graphene with complete crystal lattice and few defects, but its preparation cost is high and it cannot meet the commercial needs of large-scale production. Therefore, a "top-down" method for preparing graphene at low cost and high efficiency has attracted attention.
  • the most commonly used methods are redox and liquid phase stripping, but they still have various deficiencies, so that the current graphene scale application is greatly limited.
  • the redox process not only severely destroys the structure and properties of graphene due to the use of strong oxidants, but also introduces too much heavy metals, causing environmental pollution.
  • ionic liquids are a new class of environmentally friendly green solvents, which are composed of organic cations and organic or inorganic anions, which are liquid at room temperature or near room temperature. They have good thermal stability and dissolution energy. Strong strength, low vapor pressure, low melting point, wide electrochemical window, good electrical and thermal conductivity, good light transmission and refractive index, high heat capacity and good stability. Because ionic liquids are similar to the surface energy of graphene, they can be used as a good solvent for stripping graphene to replace traditional organic solvents that are volatile, poor in thermal stability and highly toxic.
  • the object of the present invention is to develop a low-cost, high-efficiency method for preparing a high-concentration high-quality graphene dispersion.
  • the method has the advantages of simple operation flow, environmental protection, high efficiency, low cost, and the like, and is especially suitable for large-scale industrial production, and has broad industrial application prospects.
  • a method for preparing a high concentration and high quality graphene dispersion liquid at a low cost and high efficiency wherein the specific steps are: (1) using a graphite or graphite intercalation compound as a raw material, by thermal expansion or chemical expansion The method expands to weaken the interaction between the graphite layers, and then (2) in the ionic liquid, the interaction between the ⁇ -anion and the cation is used to achieve the peeling under mechanical force, and the high-concentration and high-conductivity super-clean graphene is obtained. Dispersions.
  • the graphite described in the step (1) means any one of flake graphite, artificial graphite or expandable graphite, and has a carbon content of more than 95% and a radial dimension of less than 5 mm.
  • the graphite intercalation compound refers to a product obtained by reacting graphite and an intercalating agent at 0 to 500 ° C (preferably 0-100 ° C) for 5 minutes to 48 hours, wherein graphite and intercalation are obtained.
  • the mass ratio of the agent is 1:0.1-20 (preferably 1:0.1-10).
  • the intercalating agent means ammonium persulfate, ferric chloride, zinc chloride, potassium dichromate, chromium trioxide, potassium permanganate, potassium ferrate, hydrogen peroxide, concentrated sulfuric acid, concentrated hydrochloric acid, One of concentrated nitric acid, perchloric acid, concentrated phosphoric acid or glacial acetic acid or any combination thereof, concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, perchloric acid, concentrated phosphoric acid and ice vinegar The concentration of the acid is 10-20 moles/liter.
  • the chemical expansion method means that a graphite or graphite intercalation compound is introduced into an expansion agent for expansion to weaken the graphene interlayer interaction.
  • the expansion agent is selected from the group consisting of concentrated sulfuric acid, ammonium oxalate, oxalic acid, potassium oxalate, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, sodium carbonate or sodium hydrogencarbonate. Or several, wherein the molar concentration of the aqueous solution is 0.1-18 mol/liter, and the amount of the expansion agent is 0.1-100 times that of the graphite.
  • the ionic liquid described in the step (2) is a salt which is composed of an organic cation and an organic/inorganic anion and which is liquid at room temperature or near room temperature.
  • the organic cation is selected from the group consisting of 1-ethyl-3-methylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1,2-diethyl-3-methylimidazolium cation And one of 1,2-dimethyl-3-ethylimidazolium cation, 1-methyl-2-pyrrolidone cation, N-methylpyrrolidone or 2-hydroxyethyltrimethylammonium cation.
  • the anion is selected from the group consisting of: tetrafluoroborate ion, hexafluoride phosphate ion, hydrogen sulfate ion, nitrate ion, perchlorate ion, hydrogen phosphate ion, halogen anion, mesylate ion, trifluoroacetic acid One of a root ion, a urea or a hydroxyethoxy ion.
  • the molar ratio of the organic cation to the organic/inorganic anion is 1:0.1-10, and the concentration of the graphite or graphite intercalation compound in the ionic liquid is 1-100 mg/ml (preferably 5-100 mg/ml).
  • the mechanical force described in the step (2) refers to one of probe ultrasonic, water bath ultrasonic, high speed shear, ball milling or high pressure homogenization.
  • the ultrasonic or water bath ultrasonic power of the probe is 50-5000 W (preferably 50-3000 W)
  • the ultrasonic time is 5 minutes-5 hours
  • the high-speed shearing speed is 10-28000 rpm. (preferably 500-28000 rpm)
  • the shear time is 10 minutes to 10 hours
  • the pressure of the high pressure homogenization treatment is below 150 MPa
  • the flow rate is below 30,000 liters/hour.
  • the rotation speed is 100-1000 rpm
  • the grinding time is 10 minutes - 10 hours.
  • the concentration of the high concentration graphene dispersion described in the step (2) is from 1 to 100 mg/ml, preferably from 20 to 80 mg/ml, more preferably from 30 to 80 mg/ml.
  • the graphene has an average radial size in the graphene dispersion ranging from 1 to 500 ⁇ m, preferably from 1 to 250 ⁇ m, more preferably from 1 to 100 ⁇ m.
  • an article comprising the graphene dispersion according to the first aspect of the invention.
  • a method for preparing a graphene dispersion comprising the steps of:
  • the graphene dispersion obtained in the step (b) is filtered or coated to form a graphene film.
  • the graphene film has an electric conductivity of from 1,000 to 10 5 S/cm, preferably from 1,100 to 5,000 S/cm, more preferably from 1,500 to 3,000 S/cm.
  • the steps in the preparation method of the first aspect of the invention may all be used in the third aspect of the invention.
  • a method for preparing a graphene dispersion comprising the steps of:
  • step (ii) mixing the stirred reaction product of step (i) with a swelling agent to obtain a graphene aggregate
  • the graphene dispersion obtained in the step (iii) is filtered or smeared to form a graphene film.
  • the graphene film has an electric conductivity of from 1,000 to 10 5 S/cm, preferably from 1,100 to 5,000 S/cm, more preferably from 1,500 to 3,000 S/cm.
  • the steps in the preparation method of the first aspect of the invention may all be used in the fourth aspect of the invention.
  • the invention has the following advantages:
  • the graphene prepared by the technique of the present invention has few defects, high electrical conductivity, high concentration, and a yield of more than 90%.
  • the invention is environmentally friendly and does not cause environmental pollution, and the obtained graphene does not contain any metal impurities, which is advantageous for downstream applications.
  • the ionic liquid used in the present invention can be recycled, recycled, and energy-saving.
  • the graphene dispersion prepared by the invention has high concentration and is not easy to aggregate, and can adjust the viscosity according to the unique characteristics of the ionic liquid, and is beneficial to the storage and transportation of graphene.
  • the invention has mild reaction conditions, simple process, low energy consumption, wide source of graphite, low production cost and high efficiency, and is convenient for large-scale industrial production.
  • Figure 1 is a physical diagram of a high concentration graphene dispersion
  • TEM transmission electron micrograph
  • SAED selected area electron diffraction pattern
  • Figure 3 is a Raman spectrum of graphene.
  • the "radial size”, ie, the “side dimension”, refers to the largest dimension in the XY plane except for the thickness direction (z direction).
  • the graphene in the graphene dispersion of the present invention, has an average radial size ranging from 1 to 500 ⁇ m, preferably from 1 to 250 ⁇ m, more preferably from 1 to 100. Micron.
  • the expanding agent expands the intercalated graphite to release the inter-layer space and weaken the inter-layer interaction force.
  • the expansion of the present invention is carried out by using one or several expansion agents selected from the group consisting of concentrated sulfuric acid, ammonium oxalate, oxalic acid, potassium oxalate, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, sodium carbonate or hydrogencarbonate.
  • one or more of the aqueous sodium solutions, the solvent may be water or other solvents well known to those skilled in the art.
  • the expansion of the present invention is liquid expansion rather than solid expansion, which is simple in operation and lower in cost.
  • the method can effectively realize the stripping of graphene, the obtained graphene is a small layer, the yield is more than 95%, and has a complete lattice structure, and the measured electrical conductivity is 1300 S/cm.
  • the probe of 0.5 g of flake graphite and 20 ml of 1-ethyl-3-methylimidazolium tetrafluoroborate was sonicated for 3 hours to obtain a black viscous liquid, which was then washed and dispersed with NMP, and it was found that most of the graphite was sunk. At the bottom, it means that the graphite does not undergo expansion, and the effect of peeling directly in the ionic liquid is not good, and high concentration of graphene dispersion cannot be achieved.

Abstract

The present invention provides a method for preparing a graphene dispersion and an article thereof. The method uses a graphite or a graphite intercalation compound as a raw material and prepares an ultrapure graphene dispersion having a high concentration and a high electric conductivity by using a method of thermal expansion or chemical expansion to weaken an interaction force between graphite layers, and using π-interactions with an anion and a cation in an ionic liquid for achieving peeling under a mechanical force. The present invention also provides an article comprising the graphene dispersion or manufactured from the graphene dispersion. The method does not introduce impurities and the ionic liquid used can be recycled for reuse, making the method suitable for large-scale industrial production.

Description

[根据细则37.2由ISA制定的发明名称]　一种制备石墨烯分散液的方法及其制品[Invention name established by ISA according to Rule 37.2] Method for preparing graphene dispersion and product thereof 技术领域Technical field
本发明属于石墨烯制备技术领域，涉及一种绿色环保制备高浓度超净石墨烯分散液的方法，具体为以石墨或石墨层间化合物为原料，通过一定的方式膨胀后，在离子液体中进行剥离，得到高浓度、高电导率的石墨烯分散液。The invention belongs to the technical field of graphene preparation, and relates to a method for preparing a high concentration ultra-clean graphene dispersion liquid in a green environment, specifically, using graphite or graphite intercalation compound as a raw material, and expanding in a certain manner, and then performing in an ionic liquid. Peeling to obtain a graphene dispersion having a high concentration and a high conductivity.
背景技术Background technique
自2004年石墨烯通过透明胶带粘贴法成功从石墨上分离出来，因具有优异的性能和广阔的应用前景，引起广泛研究者和产业界的强烈兴趣，已经掀起一阵研究和产业应用热潮。然而，要实现石墨烯的工业化应用，需要解决的首要问题仍是高质量石墨烯的低成本、环境友好的制备问题。此前，石墨烯制备一直被认为会造成大量的环境污染问题，这已经引起人们的高度重视，但如何实现环境友好的低成本制备仍是石墨烯产业亟待解决的关键核心问题。目前，石墨烯的制备方法主要分为两类，即“自下而上”和“自上而下”法。前者如化学气相沉积法和外延生长法，它们虽能得到晶格完整、少缺陷的高质量石墨烯，但其制备成本昂贵，无法满足大规模生产的商业需要。因此，低成本、高效率制备石墨烯的“自上而下”方法备受关注。对于后者，最为常用的为氧化还原法和液相剥离法，但它们仍然存在各种不足，以至于现在的石墨烯规模化应用受到了极大限制。氧化还原法由于采用强氧化剂不仅严重破坏了石墨烯的结构和性能，还引入过多的重金属，造成环境污染。而液相剥离法虽能很好地保护石墨烯晶格的完整性，但其在溶剂中的分散浓度较低，不利于石墨烯的大规模生产、储存和运输，因此也制约了石墨烯在工业上的大规模使用。许多研究者为了提高石墨烯的分散浓度，通过延长超声时间、加入表面活性剂或聚合物等方法加以改善，但是却带来另外的负面影响。例如，长时间的超声，会导致石墨烯的片层尺寸减小、增加能量损耗；表面活性剂或聚合物辅助的剥离，其最终石墨烯产物中残留的表面活性剂或聚合物不易除去，从而影响了石墨烯的应用和性能，制约着石墨烯的应用。因此，如何实现绿色环保、高效率制备高浓度的石墨烯是工业上迫切需要解决的问题，也是制约石墨烯产业化应用的、目前亟待解决的关键核心问题。Since 2004, graphene has been successfully separated from graphite by the transparent tape sticking method. Due to its excellent performance and broad application prospects, it has aroused strong interest from researchers and industry, and has already set off a wave of research and industrial application. However, in order to realize the industrial application of graphene, the primary problem to be solved remains the low-cost, environmentally-friendly preparation of high-quality graphene. Previously, graphene preparation has been considered to cause a large number of environmental pollution problems, which has attracted people's attention, but how to achieve environmentally friendly low-cost preparation is still a key core issue to be solved in the graphene industry. At present, the preparation methods of graphene are mainly divided into two categories, namely, "bottom up" and "top down" methods. The former, such as chemical vapor deposition and epitaxial growth, can obtain high-quality graphene with complete crystal lattice and few defects, but its preparation cost is high and it cannot meet the commercial needs of large-scale production. Therefore, a "top-down" method for preparing graphene at low cost and high efficiency has attracted attention. For the latter, the most commonly used methods are redox and liquid phase stripping, but they still have various deficiencies, so that the current graphene scale application is greatly limited. The redox process not only severely destroys the structure and properties of graphene due to the use of strong oxidants, but also introduces too much heavy metals, causing environmental pollution. While the liquid phase stripping method can well protect the integrity of the graphene lattice, its dispersion concentration in the solvent is low, which is not conducive to the large-scale production, storage and transportation of graphene, thus restricting the graphene in Large-scale use in industry. In order to increase the dispersion concentration of graphene, many researchers have improved by extending the ultrasonic time, adding a surfactant or a polymer, but have other negative effects. For example, prolonged ultrasound can result in reduced sheet size of graphene and increased energy loss; surfactant or polymer-assisted stripping, the residual surfactant or polymer remaining in the final graphene product is not easily removed, thereby It affects the application and performance of graphene and restricts the application of graphene. Therefore, how to achieve high environmental protection and high efficiency in the preparation of high concentration of graphene is an urgent problem to be solved in the industry, and it is also a key core problem that needs to be solved urgently to restrict the application of graphene industrialization.
众所周知，离子液体是一类环境友好的新型绿色溶剂，是由有机阳离子和有机或无机阴离子组成，在室温或近室温条件下呈液态的一类盐。它们具有热稳定性好、溶解能 力强、蒸汽压低不挥发、低熔点、电化学窗口宽、导电与导热性良好、透光性与折光率好、热容高、稳定性良好等优点。由于离子液体与石墨烯的表面能相近，因此可作为剥离石墨烯的良溶剂，以替代那些易挥发、热稳定性差和毒性强的传统有机溶剂。且π-阴阳离子间强烈的相互作用，可有效抵御石墨片层间自身的π-π作用，防止发生剥离石墨烯的再次聚集，使石墨烯稳定地分散在溶剂中，实现高浓度的石墨烯制备。中国专利《一种用离子液体制备高分散性石墨烯的方法》(CN103663442A)虽能实现石墨烯的高分散性，但该专利是以氧化石墨烯作为前驱体，自然不可避免在一定程度上破坏了石墨烯的结构。2015年Nature Chemistry上报道的一篇《借助微波和离子液体快速高效地将石墨剥离成“单层”石墨烯》(Nature Chemistry,2015,7,730-736)，虽可快速高效制备高浓度的石墨烯，但该方法只适合少体积，少量的石墨，无法实现工业上大规模的生产需求，且要求离子液体在微波处理过程必须产生氢氟酸以实现对石墨的插层，以至于提高了离子液体的制备成本，也提升了石墨烯的成本，从而使得该技术在现阶段实现规模化应用是不可能的或不现实的。因此，开发一种绿色环保、高效率制备高浓度高质量的石墨烯分散液是目前石墨烯产业发展的当务之急。It is well known that ionic liquids are a new class of environmentally friendly green solvents, which are composed of organic cations and organic or inorganic anions, which are liquid at room temperature or near room temperature. They have good thermal stability and dissolution energy. Strong strength, low vapor pressure, low melting point, wide electrochemical window, good electrical and thermal conductivity, good light transmission and refractive index, high heat capacity and good stability. Because ionic liquids are similar to the surface energy of graphene, they can be used as a good solvent for stripping graphene to replace traditional organic solvents that are volatile, poor in thermal stability and highly toxic. And the strong interaction between π-anion and cation can effectively resist the π-π interaction between the graphite sheets, prevent the re-aggregation of the exfoliated graphene, and stably disperse the graphene in the solvent to achieve high concentration of graphene. preparation. The Chinese patent "A method for preparing highly dispersible graphene using ionic liquids" (CN103663442A) can achieve high dispersibility of graphene, but the patent uses graphene oxide as a precursor, which naturally inevitably destroys to some extent. The structure of graphene. A report on Nature Chemistry in 2015, "Using microwaves and ionic liquids to quickly and efficiently strip graphite into "single layer" graphene (Nature Chemistry, 2015, 7, 730-736), although it can quickly and efficiently prepare high concentrations of graphene However, this method is only suitable for a small volume, a small amount of graphite, can not achieve industrial large-scale production requirements, and requires that ionic liquid must generate hydrofluoric acid in the microwave treatment process to achieve intercalation of graphite, so as to improve the ionic liquid The cost of preparation also increases the cost of graphene, making it impossible or unrealistic for the technology to achieve scaled application at this stage. Therefore, the development of a green, high-efficiency preparation of high-concentration and high-quality graphene dispersion is an urgent task in the development of the graphene industry.
发明内容Summary of the invention
本发明的目的在于开发一种低成本、高效率制备高浓度高质量的石墨烯分散液方法。该方法具有操作流程简单、环保、高效、成本低等优点，尤其适合大规模工业化生产，具有广泛的工业应用前景。The object of the present invention is to develop a low-cost, high-efficiency method for preparing a high-concentration high-quality graphene dispersion. The method has the advantages of simple operation flow, environmental protection, high efficiency, low cost, and the like, and is especially suitable for large-scale industrial production, and has broad industrial application prospects.
本发明的具体技术方案如下：The specific technical solutions of the present invention are as follows:
本发明第一方面，提供了一种低成本、高效率制备高浓度高质量的石墨烯分散液方法，具体步骤为：(1)以石墨或石墨层间化合物为原料，通过热膨胀法或化学膨胀法进行膨胀，来削弱石墨层间相互作用力，然后(2)在离子液体中，利用π-阴阳离子间的相互作用，在机械力下实现剥离，得到高浓度高电导率的超净石墨烯分散液。According to a first aspect of the present invention, a method for preparing a high concentration and high quality graphene dispersion liquid at a low cost and high efficiency is provided, wherein the specific steps are: (1) using a graphite or graphite intercalation compound as a raw material, by thermal expansion or chemical expansion The method expands to weaken the interaction between the graphite layers, and then (2) in the ionic liquid, the interaction between the π-anion and the cation is used to achieve the peeling under mechanical force, and the high-concentration and high-conductivity super-clean graphene is obtained. Dispersions.
本发明中，步骤(1)所述的石墨是指鳞片石墨、人造石墨或可膨胀石墨中任一种，碳含量大于95％，径向尺寸小于5毫米。In the present invention, the graphite described in the step (1) means any one of flake graphite, artificial graphite or expandable graphite, and has a carbon content of more than 95% and a radial dimension of less than 5 mm.
本发明中，所述的石墨层间化合物是指石墨与插层剂在0-500℃(较佳地为0-100℃)下反应5分钟-48小时得到的产物，其中，石墨与插层剂的质量比为1:0.1-20(较佳地为1:0.1-10)。In the present invention, the graphite intercalation compound refers to a product obtained by reacting graphite and an intercalating agent at 0 to 500 ° C (preferably 0-100 ° C) for 5 minutes to 48 hours, wherein graphite and intercalation are obtained. The mass ratio of the agent is 1:0.1-20 (preferably 1:0.1-10).
本发明中，所述的插层剂是指过硫酸铵、氯化铁、氯化锌、重铬酸钾、三氧化铬、高锰酸钾、高铁酸钾、双氧水、浓硫酸、浓盐酸、浓硝酸、高氯酸、浓磷酸或冰醋酸中的一种或它们之间的任意组合，所用浓硫酸、浓盐酸、浓硝酸、高氯酸、浓磷酸和冰醋 酸的浓度为10-20摩尔/升。In the present invention, the intercalating agent means ammonium persulfate, ferric chloride, zinc chloride, potassium dichromate, chromium trioxide, potassium permanganate, potassium ferrate, hydrogen peroxide, concentrated sulfuric acid, concentrated hydrochloric acid, One of concentrated nitric acid, perchloric acid, concentrated phosphoric acid or glacial acetic acid or any combination thereof, concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, perchloric acid, concentrated phosphoric acid and ice vinegar The concentration of the acid is 10-20 moles/liter.
本发明中，所述的化学膨胀法是指将石墨或石墨层间化合物投入膨胀剂中进行膨胀，以削弱石墨烯层间相互作用。In the present invention, the chemical expansion method means that a graphite or graphite intercalation compound is introduced into an expansion agent for expansion to weaken the graphene interlayer interaction.
本发明中，所述的膨胀剂选自下组：浓硫酸、草酸铵、草酸、草酸钾、双氧水、过硫酸铵、过硫酸钠、过硫酸钾、碳酸钠或碳酸氢钠水溶液中的一种或几种，其中，水溶液的摩尔浓度为0.1-18摩尔/升，膨胀剂用量为石墨的0.1-100倍。In the present invention, the expansion agent is selected from the group consisting of concentrated sulfuric acid, ammonium oxalate, oxalic acid, potassium oxalate, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, sodium carbonate or sodium hydrogencarbonate. Or several, wherein the molar concentration of the aqueous solution is 0.1-18 mol/liter, and the amount of the expansion agent is 0.1-100 times that of the graphite.
本发明中，步骤(2)所述的离子液体是由有机阳离子和有机/无机阴离子组成，在室温或近室温条件下呈液态的盐。其中，有机阳离子选自下组：1-乙基-3-甲基咪唑阳离子、1-乙基-2,3-二甲基咪唑阳离子、1,2-二乙基-3-甲基咪唑阳离子、1,2-二甲基-3-乙基咪唑阳离子、1-甲基-2-吡咯烷酮阳离子、N-甲基吡咯烷酮或2-羟乙基三甲铵阳离子中的一种。阴离子选自下组：四氟化硼酸根离子、六氟化磷酸根离子、硫酸氢根离子、硝酸根离子、高氯酸根离子、磷酸氢根离子、卤素阴离子、甲磺酸根离子、三氟乙酸根离子、脲或羟乙氧根离子中的一种。有机阳离子和有机/无机阴离子摩尔比为1:0.1-10，石墨或石墨层间化合物在离子液体中的浓度为1-100毫克/毫升(较佳地为5-100毫克/毫升)。In the present invention, the ionic liquid described in the step (2) is a salt which is composed of an organic cation and an organic/inorganic anion and which is liquid at room temperature or near room temperature. Wherein the organic cation is selected from the group consisting of 1-ethyl-3-methylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1,2-diethyl-3-methylimidazolium cation And one of 1,2-dimethyl-3-ethylimidazolium cation, 1-methyl-2-pyrrolidone cation, N-methylpyrrolidone or 2-hydroxyethyltrimethylammonium cation. The anion is selected from the group consisting of: tetrafluoroborate ion, hexafluoride phosphate ion, hydrogen sulfate ion, nitrate ion, perchlorate ion, hydrogen phosphate ion, halogen anion, mesylate ion, trifluoroacetic acid One of a root ion, a urea or a hydroxyethoxy ion. The molar ratio of the organic cation to the organic/inorganic anion is 1:0.1-10, and the concentration of the graphite or graphite intercalation compound in the ionic liquid is 1-100 mg/ml (preferably 5-100 mg/ml).
本发明中，步骤(2)所述的机械力是指探头超声、水浴超声、高速剪切、球磨法或高压均质法中的一种。其中，所述的探头超声或水浴超声的功率为50-5000W(较佳地为50-3000W)，超声时间为5分钟-5小时，所述的高速剪切的转速为10-28000转/分钟(较佳地为500-28000转/分钟)，剪切时间为10分钟-10小时，所述的高压均质处理的压力在150兆帕以下，流量在30000升/小时以下，所述的球磨转速为100-1000转/分钟，研磨时间为10分钟-10小时。In the present invention, the mechanical force described in the step (2) refers to one of probe ultrasonic, water bath ultrasonic, high speed shear, ball milling or high pressure homogenization. Wherein, the ultrasonic or water bath ultrasonic power of the probe is 50-5000 W (preferably 50-3000 W), the ultrasonic time is 5 minutes-5 hours, and the high-speed shearing speed is 10-28000 rpm. (preferably 500-28000 rpm), the shear time is 10 minutes to 10 hours, the pressure of the high pressure homogenization treatment is below 150 MPa, and the flow rate is below 30,000 liters/hour. The rotation speed is 100-1000 rpm, and the grinding time is 10 minutes - 10 hours.
本发明中，步骤(2)所述的高浓度石墨烯分散液浓度为：1-100毫克/毫升，较佳地为20-80毫克/毫升，更佳地为30-80毫克/毫升。In the present invention, the concentration of the high concentration graphene dispersion described in the step (2) is from 1 to 100 mg/ml, preferably from 20 to 80 mg/ml, more preferably from 30 to 80 mg/ml.
在另一优选例中，所述的石墨烯分散液中，石墨烯的平均径向尺寸范围为1-500微米，较佳地为1-250微米，更佳地为1-100微米。In another preferred embodiment, the graphene has an average radial size in the graphene dispersion ranging from 1 to 500 μm, preferably from 1 to 250 μm, more preferably from 1 to 100 μm.
本发明第二方面，提供一种制品，所述制品包含如本发明第一方面所述的石墨烯分散液。According to a second aspect of the invention, there is provided an article comprising the graphene dispersion according to the first aspect of the invention.
本发明第三方面，提供一种制备石墨烯分散液的方法，包括步骤：According to a third aspect of the invention, a method for preparing a graphene dispersion is provided, comprising the steps of:
(a)将石墨与膨胀剂在0-100℃下混合，得到膨胀石墨；(a) mixing graphite and a swelling agent at 0-100 ° C to obtain expanded graphite;
(b)将步骤(a)得到的膨胀石墨与离子液体混合，得到石墨烯分散液；(b) mixing the expanded graphite obtained in the step (a) with an ionic liquid to obtain a graphene dispersion;
(c)任选地，将步骤(b)所得的石墨烯分散液过滤或涂抹成膜，得到石墨烯薄膜。 (c) Optionally, the graphene dispersion obtained in the step (b) is filtered or coated to form a graphene film.
在另一优选例中，所述石墨烯薄膜的电导率为1000-105S/cm，较佳地为1100-5000S/cm，更佳地为1500-3000S/cm。In another preferred embodiment, the graphene film has an electric conductivity of from 1,000 to 10 5 S/cm, preferably from 1,100 to 5,000 S/cm, more preferably from 1,500 to 3,000 S/cm.
在另一优选例中，本发明第一方面所述的制备方法中的步骤可全部用于本发明第三方面。In another preferred embodiment, the steps in the preparation method of the first aspect of the invention may all be used in the third aspect of the invention.
本发明第四方面，提供一种制备石墨烯分散液的方法，包括步骤：According to a fourth aspect of the invention, a method for preparing a graphene dispersion is provided, comprising the steps of:
(i)将石墨与插层剂在0-100℃下搅拌反应；(i) stirring the graphite and the intercalation agent at 0-100 ° C;
(ii)将步骤(i)的搅拌反应产物与膨胀剂混合，得到石墨烯聚集体；(ii) mixing the stirred reaction product of step (i) with a swelling agent to obtain a graphene aggregate;
(iii)将步骤(ii)得到的石墨烯聚集体与离子液体混合，得到石墨烯分散液；(iii) mixing the graphene aggregate obtained in the step (ii) with the ionic liquid to obtain a graphene dispersion;
(iv)任选地，将步骤(iii)所得的石墨烯分散液过滤或涂抹成膜，得到石墨烯薄膜。(iv) Optionally, the graphene dispersion obtained in the step (iii) is filtered or smeared to form a graphene film.
在另一优选例中，所述石墨烯薄膜的电导率为1000-105S/cm，较佳地为1100-5000S/cm，更佳地为1500-3000S/cm。In another preferred embodiment, the graphene film has an electric conductivity of from 1,000 to 10 5 S/cm, preferably from 1,100 to 5,000 S/cm, more preferably from 1,500 to 3,000 S/cm.
在另一优选例中，本发明第一方面所述的制备方法中的步骤可全部用于本发明第四方面。In another preferred embodiment, the steps in the preparation method of the first aspect of the invention may all be used in the fourth aspect of the invention.
需注意的是，上述机理性的描述不作为对本发明保护范围的限制，本发明中的制备方法主要由所述步骤进行限定。It should be noted that the above-described mechanistic description is not intended to limit the scope of the present invention, and the preparation method in the present invention is mainly defined by the steps.
本发明与现有技术相比具有以下优势：Compared with the prior art, the invention has the following advantages:
(1)本发明技术制备的石墨烯缺陷少、电导率高、浓度高、产率大于90％。(1) The graphene prepared by the technique of the present invention has few defects, high electrical conductivity, high concentration, and a yield of more than 90%.
(2)本发明绿色环保，不造成环境污染，得到的石墨烯不含任何金属杂质，有利下游应用。(2) The invention is environmentally friendly and does not cause environmental pollution, and the obtained graphene does not contain any metal impurities, which is advantageous for downstream applications.
(3)本发明所使用的离子液体可以回收，循环利用，节能减排。(3) The ionic liquid used in the present invention can be recycled, recycled, and energy-saving.
(4)本发明制备的石墨烯分散液浓度高，不易聚集，可根据离子液体独有的特性，调节其粘稠度，有利石墨烯的储存和运输。(4) The graphene dispersion prepared by the invention has high concentration and is not easy to aggregate, and can adjust the viscosity according to the unique characteristics of the ionic liquid, and is beneficial to the storage and transportation of graphene.
(5)本发明反应条件温和，工序简单，能耗低，石墨来源广泛，生产成本低廉，效率高，便于进行大规模工业化生产。(5) The invention has mild reaction conditions, simple process, low energy consumption, wide source of graphite, low production cost and high efficiency, and is convenient for large-scale industrial production.
附图说明DRAWINGS
图1为高浓度石墨烯分散液实物图；Figure 1 is a physical diagram of a high concentration graphene dispersion;
图2为石墨烯的透射电镜图(TEM)和选区电子衍射图(SAED)；2 is a transmission electron micrograph (TEM) and a selected area electron diffraction pattern (SAED) of graphene;
图3为石墨烯的拉曼光谱图(Raman)。 Figure 3 is a Raman spectrum of graphene.
具体实施方式detailed description
下面结合附图和具体实施例对本发明做进一步阐述。以下实施例旨在对本发明进行说明，对发明内容本身不做任何限定。应该理解，本发明提到的一个或多个步骤不排斥在所述组合步骤前后还存在其它方法和步骤，或者这些明确提及的步骤之间还可以***其它方法和步骤。还应理解，这些实例仅用于说明本发明而不用于限制本发明的范围。除非另有说明，各方法步骤的编号仅为鉴别各方法步骤的目的，而非为限制每个方法的排列次序或限定本发明的实施范围，其相对关系的改变或调整，在无实质技术内容变更的条件下，当亦视为本发明可实施的范畴。The present invention will be further described below in conjunction with the drawings and specific embodiments. The following examples are intended to illustrate the invention, and the invention itself is not limited in any way. It should be understood that one or more of the steps referred to in the present invention does not exclude other methods and steps that exist before or after the combination of steps, or that other methods and steps can be inserted between the steps specifically mentioned. It is also to be understood that the examples are not intended to limit the scope of the invention. Unless otherwise stated, the numbering of each method step is only for the purpose of identifying each method step, and is not intended to limit the order of each method or to limit the scope of implementation of the present invention, and the relative relationship is changed or adjusted without substantial technical content. The terms of the invention are also considered to be within the scope of the invention.
术语说明Terminology
径向尺寸Radial size
如本文所用，所述“径向尺寸”即Lateral Size，也称“侧面尺寸”，是指除厚度方向(z方向)外的XY平面内的最大尺寸。As used herein, the "radial size", ie, the "side dimension", refers to the largest dimension in the XY plane except for the thickness direction (z direction).
在另一优选例中，本发明所述的石墨烯分散液中，所述石墨烯的平均径向尺寸范围为1-500微米，较佳的为1-250微米，更佳地为1-100微米。In another preferred embodiment, in the graphene dispersion of the present invention, the graphene has an average radial size ranging from 1 to 500 μm, preferably from 1 to 250 μm, more preferably from 1 to 100. Micron.
膨胀剂Expansion agent
如本文所用，所述膨胀剂对插层石墨进行膨胀，以释放层间空间、削弱层间相互作用力。As used herein, the expanding agent expands the intercalated graphite to release the inter-layer space and weaken the inter-layer interaction force.
本发明所述膨胀是采用选自下组一种或几种膨胀剂进行：浓硫酸、草酸铵、草酸、草酸钾、双氧水、过硫酸铵、过硫酸钠、过硫酸钾、碳酸钠或碳酸氢钠水溶液中的一种或几种，溶剂可以为水或其它本领域技术人员熟知的溶剂。The expansion of the present invention is carried out by using one or several expansion agents selected from the group consisting of concentrated sulfuric acid, ammonium oxalate, oxalic acid, potassium oxalate, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, sodium carbonate or hydrogencarbonate. One or more of the aqueous sodium solutions, the solvent may be water or other solvents well known to those skilled in the art.
本发明所述膨胀是液态膨胀而非固态膨胀，操作简便，成本更低。The expansion of the present invention is liquid expansion rather than solid expansion, which is simple in operation and lower in cost.
实施例1Example 1
将50毫升浓硫酸，10克过硫酸铵和10毫升去离子水在5℃条件下混合搅拌10分钟，加入1克鳞片石墨，在20℃水浴中连续搅拌24小时后，得到膨胀石墨。水洗过滤后，加入50毫升1-乙基-3-甲基咪唑四氟硼酸盐，超声处理2小时，得到粘稠的高浓度的石墨烯分散液，浓度为16毫克/毫升，如图1所示。50 ml of concentrated sulfuric acid, 10 g of ammonium persulfate and 10 ml of deionized water were mixed and stirred at 5 ° C for 10 minutes, and 1 g of flake graphite was added thereto, and continuously stirred for 24 hours in a water bath at 20 ° C to obtain expanded graphite. After washing with water, 50 ml of 1-ethyl-3-methylimidazolium tetrafluoroborate was added and sonicated for 2 hours to obtain a viscous high concentration graphene dispersion at a concentration of 16 mg/ml, as shown in Fig. 1. Shown.
从图2透射电子显微镜(TEM)结果可看出本方法实现了石墨烯的充分剥离，所得石墨烯为少层，产率90％以上。从图2获得的选区电子衍射图(SAED)和图3拉曼光谱图(Raman)可知所得的石墨烯没有引入缺陷，具有完整的晶格结构，其薄膜电导率为1100 S/cm。From the results of transmission electron microscopy (TEM) in Fig. 2, it can be seen that the method achieves sufficient stripping of graphene, and the obtained graphene is a small layer with a yield of more than 90%. From the selected area electron diffraction pattern (SAED) obtained in Fig. 2 and the Raman spectrum in Fig. 3, it can be seen that the obtained graphene has no defects introduced and has a complete lattice structure, and the film conductivity is 1100. S/cm.
实施例2Example 2
将50毫升浓硫酸，10克过硫酸铵和10毫升去离子水在5℃条件下混合搅拌10分钟，加入1克鳞片石墨，在20℃水浴中连续搅拌24小时后，得到膨胀石墨。水洗过滤后，加入50毫升1-乙基-3-甲基咪唑四氟硼酸盐，高速剪切机以13000转/分钟处理2小时，得到粘稠的高浓度的石墨烯分散液，浓度为16毫克/毫升，如图1所示。所得石墨烯为少层，产率90％以上。并且，所得的石墨烯没有引入缺陷，具有完整的晶格结构，其薄膜电导率为1000S/cm。50 ml of concentrated sulfuric acid, 10 g of ammonium persulfate and 10 ml of deionized water were mixed and stirred at 5 ° C for 10 minutes, and 1 g of flake graphite was added thereto, and continuously stirred for 24 hours in a water bath at 20 ° C to obtain expanded graphite. After washing with water, 50 ml of 1-ethyl-3-methylimidazolium tetrafluoroborate was added, and the mixture was treated at 13,000 rpm for 2 hours at a high speed shear to obtain a viscous high concentration graphene dispersion at a concentration of 16 mg / ml, as shown in Figure 1. The obtained graphene is a small layer, and the yield is 90% or more. Moreover, the obtained graphene has no defects introduced and has a complete lattice structure, and its film conductivity is 1000 S/cm.
实施例3Example 3
将50毫升浓硫酸，10克过硫酸铵和10毫升去离子水在5℃条件下混合搅拌10分钟，加入1克鳞片石墨，在20℃水浴中连续搅拌24小时后，得到膨胀石墨。水洗过滤后，加入50毫升1-乙基-3-甲基咪唑四氟硼酸盐，然后以转速1000转/分钟球磨处理10小时，得到粘稠的高浓度的石墨烯分散液，浓度为16毫克/毫升。所得石墨烯为少层，产率90％以上。并且，所得的石墨烯没有引入缺陷，具有完整的晶格结构，其薄膜电导率为1000S/cm。50 ml of concentrated sulfuric acid, 10 g of ammonium persulfate and 10 ml of deionized water were mixed and stirred at 5 ° C for 10 minutes, and 1 g of flake graphite was added thereto, and continuously stirred for 24 hours in a water bath at 20 ° C to obtain expanded graphite. After washing with water, 50 ml of 1-ethyl-3-methylimidazolium tetrafluoroborate was added, followed by ball milling at 1000 rpm for 10 hours to obtain a viscous high concentration graphene dispersion at a concentration of 16 Mg/ml. The obtained graphene is a small layer, and the yield is 90% or more. Moreover, the obtained graphene has no defects introduced and has a complete lattice structure, and its film conductivity is 1000 S/cm.
实施例4Example 4
将50毫升浓硫酸，10克过硫酸铵和10毫升去离子水在5℃条件下混合搅拌10分钟，加入1克鳞片石墨，在20℃水浴中连续搅拌24小时后，得到膨胀石墨。水洗过滤后，加入50毫升1-乙基-3-甲基咪唑四氟硼酸盐，用高压均质处理机以60MPa、30升/小时流速进行剥离，得到粘稠的高浓度石墨烯分散液，浓度为16克毫克/毫升。所得石墨烯为少层，产率95％以上。并且，所得的石墨烯没有引入缺陷，具有完整的晶格结构，其薄膜电导率为1000S/cm。50 ml of concentrated sulfuric acid, 10 g of ammonium persulfate and 10 ml of deionized water were mixed and stirred at 5 ° C for 10 minutes, and 1 g of flake graphite was added thereto, and continuously stirred for 24 hours in a water bath at 20 ° C to obtain expanded graphite. After washing with water, 50 ml of 1-ethyl-3-methylimidazolium tetrafluoroborate was added, and the mixture was peeled off at a flow rate of 60 MPa and 30 liters/hour using a high-pressure homogenizer to obtain a viscous high-concentration graphene dispersion. The concentration is 16 g mg/ml. The obtained graphene was a few layers, and the yield was 95% or more. Moreover, the obtained graphene has no defects introduced and has a complete lattice structure, and its film conductivity is 1000 S/cm.
实施例5Example 5
将30毫升浓硫酸与10毫升浓硝酸在5℃冰水浴条件下混合搅拌10分钟，加入1克鳞片石墨，在20℃水浴中连续搅拌10小时后，过滤，得到GICs。然后，缓慢投入200毫升0.1摩尔/升草酸溶液中，于室温下反应1d后，过滤水洗，得到膨胀石墨。接着，缓慢投入40毫升1-乙基-3-甲基咪唑六氟磷酸盐，高速剪切机以22000转/分钟转速处理2小时，得到粘稠的高浓度的石墨烯分散液，浓度为21毫克/毫升。该方法可 有效实现石墨烯的剥离，所得石墨烯为少层，产率94％以上，且具有完整的晶格结构，测得的薄膜电导率为1200S/cm。30 ml of concentrated sulfuric acid and 10 ml of concentrated nitric acid were mixed and stirred for 10 minutes in an ice water bath at 5 ° C, 1 g of flake graphite was added, and the mixture was continuously stirred for 10 hours in a water bath at 20 ° C, and then filtered to obtain GICs. Then, it was slowly poured into 200 ml of a 0.1 mol/liter oxalic acid solution, and after reacting for 1 d at room temperature, it was filtered and washed with water to obtain expanded graphite. Next, 40 ml of 1-ethyl-3-methylimidazolium hexafluorophosphate was slowly added, and the mixture was treated at a high speed shear at 22,000 rpm for 2 hours to obtain a viscous high concentration graphene dispersion at a concentration of 21 Mg/ml. The method can Effectively realize the peeling of graphene, the obtained graphene is a small layer, the yield is more than 94%, and has a complete lattice structure, and the measured film conductivity is 1200 S/cm.
实施例6Example 6
将1克鳞片石墨(碳含量>95％)，30毫升双氧水(30％)与70毫升浓硫酸混合搅拌15分钟后，停止搅拌，在室温下静置24小时，得到膨胀石墨。多次水洗过滤后，投入25毫升1-甲基-2吡咯烷酮磷酸氢盐离子液体中，用高速剪切机以30000转/分钟转速处理10分钟，得到粘稠的高浓度的石墨烯分散液，浓度为35毫克/毫升。该方法可有效实现石墨烯的剥离，所得石墨烯为少层，产率达90％以上，且具有完整的晶格结构，测得的薄膜电导率为1500S/cm。1 g of flake graphite (carbon content > 95%), 30 ml of hydrogen peroxide (30%) and 70 ml of concentrated sulfuric acid were mixed and stirred for 15 minutes, the stirring was stopped, and the mixture was allowed to stand at room temperature for 24 hours to obtain expanded graphite. After multiple times of washing with water, it was poured into 25 ml of 1-methyl-2-pyrrolidone hydrogen phosphate ionic liquid, and treated with a high-speed shear at 30,000 rpm for 10 minutes to obtain a viscous high-concentration graphene dispersion. The concentration is 35 mg/ml. The method can effectively realize the exfoliation of graphene, the obtained graphene is a small layer, the yield is more than 90%, and has a complete lattice structure, and the measured film conductivity is 1500 S/cm.
实施例7Example 7
将1克鳞片石墨(碳含量95％以上)与20克三氧化铬混合，加入15毫升浓盐酸(38％)，在25℃水浴条件下搅拌2小时后，过滤，用水和丙酮重复洗多次，得到克ICs。然后，加入200毫升双氧水(30％)，于室温下反应1天后，过滤水洗，得到膨胀石墨。接着，缓慢投入25毫升1-甲基-2吡咯烷酮甲磺酸盐离子液体中，用高速剪切机以15000转/分钟转速处理2小时，得到粘稠的高浓度的石墨烯分散液，浓度为35毫克/毫升。该方法可有效实现石墨烯的剥离，所得石墨烯为少层，产率达95％以上，且具有完整的晶格结构，测得的电导率为1300S/cm。1 gram of flake graphite (carbon content of 95% or more) was mixed with 20 g of chromium trioxide, 15 ml of concentrated hydrochloric acid (38%) was added, and the mixture was stirred under a water bath at 25 ° C for 2 hours, filtered, and repeatedly washed with water and acetone. , get grams of ICs. Then, 200 ml of hydrogen peroxide (30%) was added, and after reacting for 1 day at room temperature, it was filtered and washed with water to obtain expanded graphite. Then, it was slowly poured into 25 ml of 1-methyl-2-pyrrolidone mesylate ionic liquid, and treated with a high speed shear at 15,000 rpm for 2 hours to obtain a viscous high concentration graphene dispersion at a concentration of 35 mg / ml. The method can effectively realize the stripping of graphene, the obtained graphene is a small layer, the yield is more than 95%, and has a complete lattice structure, and the measured electrical conductivity is 1300 S/cm.
实施例8Example 8
将1克鳞片石墨(碳含量>95％)，30毫升双氧水(30％)与70毫升浓硫酸混合搅拌15分钟后，停止搅拌，在室温下静置24小时，得到膨胀石墨。多次水洗过滤后，投入25毫升1-甲基-2吡咯烷酮高氯酸氢盐离子液体中，用高压均质处理机以150兆帕、500升/小时流速进行剥离，得到粘稠的高浓度的石墨烯分散液，浓度为30毫克/毫升。该方法可有效实现石墨烯的剥离，所得石墨烯为少层，产率达92％以上，且具有完整的晶格结构，测得的薄膜电导率为1500S/cm。1 g of flake graphite (carbon content > 95%), 30 ml of hydrogen peroxide (30%) and 70 ml of concentrated sulfuric acid were mixed and stirred for 15 minutes, the stirring was stopped, and the mixture was allowed to stand at room temperature for 24 hours to obtain expanded graphite. After multiple times of washing with water, it was poured into 25 ml of 1-methyl-2-pyrrolidone perchlorate ionic liquid, and stripped at a flow rate of 150 MPa and 500 liter/hour with a high pressure homogenizer to obtain a viscous high concentration. The graphene dispersion has a concentration of 30 mg/ml. The method can effectively realize the exfoliation of graphene, the obtained graphene is a small layer, the yield is over 92%, and has a complete lattice structure, and the measured film conductivity is 1500 S/cm.
实施例9Example 9
将1克人造石墨与30毫升浓硫酸剧烈搅拌24小时后，再加入10毫升发烟硝酸于室温下继续搅拌24小时。继而缓慢向混合物中加入40毫升去离子水，静置1小时 后，水洗多次，过滤干燥。接着在1000℃管式炉中加热30s后得到热膨胀石墨。然后，缓慢投入25毫升1-乙基-3-甲基咪唑六氟磷酸盐，用高速剪切机以28000转/分钟转速处理5小时，得到粘稠的高浓度的石墨烯分散液，浓度为30毫克/毫升。该方法可有效实现石墨烯的剥离，所得石墨烯为少层，产率达93wt％以上，且具有完整的晶格结构，测得的电导率为1200S/cm。After vigorously stirring 1 gram of artificial graphite with 30 ml of concentrated sulfuric acid for 24 hours, further stirring was continued for 24 hours at room temperature by adding 10 ml of fuming nitric acid. Then slowly add 40 ml of deionized water to the mixture and let stand for 1 hour. After that, it was washed several times with water and dried by filtration. The thermally expanded graphite was then obtained by heating in a 1000 ° C tube furnace for 30 s. Then, 25 ml of 1-ethyl-3-methylimidazolium hexafluorophosphate was slowly added and treated with a high speed shear at 28,000 rpm for 5 hours to obtain a viscous high concentration graphene dispersion at a concentration of 30 mg / ml. The method can effectively realize the exfoliation of graphene, the obtained graphene is a small layer, the yield is more than 93 wt%, and has a complete lattice structure, and the measured electrical conductivity is 1200 S/cm.
实施例10Example 10
将500毫升浓硫酸，100克过硫酸铵和100毫升去离子水在5℃条件下混合搅拌10分钟，加入1克鳞片石墨，在20℃水浴中连续搅拌24小时后，得到膨胀石墨。水洗过滤后，加入50毫升1-乙基-3-甲基咪唑六氟硼酸盐，用高速剪切机以28000转/分钟转速处理2小时，得到粘稠的高浓度的石墨烯分散液，浓度为100毫克/毫升。所得石墨烯为少层，产率92％以上，并且，得到的石墨烯没有引入额外缺陷，具有完整的晶格结构，其薄膜电导率为1300S/cm。500 ml of concentrated sulfuric acid, 100 g of ammonium persulfate and 100 ml of deionized water were mixed and stirred at 5 ° C for 10 minutes, and 1 g of flake graphite was added thereto, and continuously stirred for 24 hours in a water bath at 20 ° C to obtain expanded graphite. After washing with water, 50 ml of 1-ethyl-3-methylimidazolium hexafluoroborate was added and treated with a high speed shear at 28,000 rpm for 2 hours to obtain a viscous high concentration graphene dispersion. The concentration is 100 mg/ml. The obtained graphene was a small layer with a yield of 92% or more, and the obtained graphene did not introduce an additional defect, and had a complete lattice structure, and its film conductivity was 1300 S/cm.
实施例11Example 11
将1克可膨胀石墨在1000℃管式炉中加热30s后得到热膨胀石墨后，将其加入50毫升1-乙基-3-甲基咪唑六氟硼酸盐，用高速剪切机以28000转/分钟转速处理2小时，得到粘稠的高浓度的石墨烯分散液，浓度为50毫克/毫升。所得石墨烯为少层，产率90％以上，并且，得到的石墨烯没有额外引入缺陷，具有完整的晶格结构，其薄膜电导率为1200S/cm。After heating 1 gram of expandable graphite in a 1000 ° C tube furnace for 30 s to obtain heat-expanded graphite, it was added to 50 ml of 1-ethyl-3-methylimidazolium hexafluoroborate and used a high-speed shear at 28,000 rpm. Treatment at /min. speed for 2 hours gave a viscous, high concentration graphene dispersion at a concentration of 50 mg/ml. The obtained graphene was a small layer with a yield of 90% or more, and the obtained graphene had no additional introduction defects, and had a complete lattice structure, and its film conductivity was 1200 S/cm.
对比例1Comparative example 1
将0.5克鳞片石墨与20毫升1-乙基-3-甲基咪唑四氟硼酸盐中探头超声3小时，得到黑色的粘稠液，然后用NMP洗涤并分散，发现石墨大部分都沉入底部，即说明石墨不经过膨胀，直接在离子液体中剥离的效果不佳，无法实现高浓度的石墨烯分散。The probe of 0.5 g of flake graphite and 20 ml of 1-ethyl-3-methylimidazolium tetrafluoroborate was sonicated for 3 hours to obtain a black viscous liquid, which was then washed and dispersed with NMP, and it was found that most of the graphite was sunk. At the bottom, it means that the graphite does not undergo expansion, and the effect of peeling directly in the ionic liquid is not good, and high concentration of graphene dispersion cannot be achieved.
对比例2Comparative example 2
将1克鳞片石墨(碳含量>95％)，10克过硫酸铵和10毫升去离子水在5℃条件下混合搅拌10分钟后，在室温下静置24小时，得到膨胀石墨。多次水洗过滤后，投入25毫升NMP中用高速剪切机以18000转/分钟转速处理2小时，得到黑色的悬浮液，静置片刻后，发现有大量石墨沉入底部，说明膨胀石墨在传统的有机溶剂中，剥离效果不佳，片层较厚，产率较低，无法实现高浓度的石墨烯分散。 1 g of flake graphite (carbon content > 95%), 10 g of ammonium persulfate and 10 ml of deionized water were mixed and stirred at 5 ° C for 10 minutes, and then allowed to stand at room temperature for 24 hours to obtain expanded graphite. After multiple washings and filtration, it was poured into 25 ml of NMP and treated with a high-speed shear at 18,000 rpm for 2 hours to obtain a black suspension. After standing for a while, a large amount of graphite was found to sink to the bottom, indicating that expanded graphite was conventional. In the organic solvent, the peeling effect is not good, the sheet layer is thick, the yield is low, and high concentration of graphene dispersion cannot be achieved.

Claims (13)

  1. 一种制备高浓度超净石墨烯分散液的方法，包括步骤：以石墨或石墨层间化合物为原料，通过热膨胀法或化学膨胀法进行膨胀，来削弱石墨层间相互作用力，然后在离子液体中，利用π-阴阳离子间的相互作用，在机械力作用下实现剥离，得到高浓度高电导率的超净石墨烯分散液。A method for preparing a high concentration ultra-clean graphene dispersion, comprising the steps of: using a graphite or graphite intercalation compound as a raw material, expanding by a thermal expansion method or a chemical expansion method to weaken the interaction force between the graphite layers, and then in the ionic liquid In the middle, the interaction between the π-anion and the cation is used to achieve the peeling under the action of mechanical force, and a super-clean graphene dispersion having a high concentration and high conductivity is obtained.
  2. 根据权利要求1所述的方法，其特征在于，所述的石墨是指鳞片石墨、人造石墨或可膨胀石墨中任一种，碳含量大于95％，径向尺寸小于5毫米；所述的石墨层间化合物由石墨与插层剂在0-500℃下反应5分钟-48小时得到，其中：石墨与插层剂的质量比为1:0.1-10。The method according to claim 1, wherein said graphite refers to any one of flake graphite, artificial graphite or expandable graphite, having a carbon content of more than 95% and a radial dimension of less than 5 mm; said graphite The interlayer compound is obtained by reacting graphite with an intercalating agent at 0 to 500 ° C for 5 minutes to 48 hours, wherein the mass ratio of graphite to intercalant is 1:0.1-10.
  3. 根据权利要求2所述的方法，其特征在于，所述的插层剂是指过硫酸铵、氯化铁、氯化锌、双氧水、重铬酸钾、三氧化铬、高锰酸钾、高铁酸钾、浓硫酸、浓盐酸、浓硝酸、高氯酸、浓磷酸或冰醋酸中的一种或它们之间的任意组合，所用浓硫酸、浓盐酸、浓硝酸、高氯酸、浓磷酸和冰醋酸的浓度为10-20摩尔/升。The method according to claim 2, wherein said intercalant means ammonium persulfate, ferric chloride, zinc chloride, hydrogen peroxide, potassium dichromate, chromium trioxide, potassium permanganate, high iron. One of potassium acid, concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, perchloric acid, concentrated phosphoric acid or glacial acetic acid or any combination thereof, concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, perchloric acid, concentrated phosphoric acid and The concentration of glacial acetic acid is 10-20 mol/l.
  4. 根据权利要求1所述的方法，其特征在于，所述化学膨胀法是将石墨或石墨层间化合物投入膨胀剂中，所述膨胀剂为浓硫酸、草酸铵、草酸、草酸钾、双氧水、碳酸钠或碳酸氢钠水溶液中的一种或几种，其摩尔浓度为0.1-18摩尔/升，膨胀剂用量为石墨质量的1-100倍。The method according to claim 1, wherein the chemical expansion method is to introduce a graphite or graphite intercalation compound into a swelling agent, which is concentrated sulfuric acid, ammonium oxalate, oxalic acid, potassium oxalate, hydrogen peroxide, carbonic acid. One or more of sodium or sodium hydrogencarbonate aqueous solution having a molar concentration of 0.1-18 mol/liter and a swelling agent dosage of 1-100 times the mass of the graphite.
  5. 根据权利要求1所述的方法，其特征在于，所述的离子液体是由有机阳离子和有机/无机阴离子组成，为在室温或近室温条件下呈液态的盐，其中：有机阳离子为1-乙基-3-甲基咪唑阳离子、1-乙基-2,3-二甲基咪唑阳离子、1,2-二乙基-3-甲基咪唑阳离子、1,2-二甲基-3-乙基咪唑阳离子、1-甲基-2-吡咯烷酮阳离子、N-甲基吡咯烷酮或2-羟乙基三甲铵阳离子中的一种，阴离子为四氟化硼酸根离子、六氟化磷酸根离子、硫酸氢根离子、硝酸根离子、高氯酸根离子、磷酸氢根离子、卤素阴离子、甲磺酸根离子、三氟乙酸根离子、脲或羟乙氧根离子中的一种，有机阳离子与有机/无机阴离子阳的摩尔比为1:0.1-10，石墨或石墨层间化合物在离子液体中的浓度为5-100mg毫克/毫升。The method according to claim 1, wherein said ionic liquid is composed of an organic cation and an organic/inorganic anion, and is a salt which is liquid at room temperature or near room temperature, wherein: the organic cation is 1-B. 3-methylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1,2-diethyl-3-methylimidazolium cation, 1,2-dimethyl-3-ethyl One of a base imidazolium cation, a 1-methyl-2-pyrrolidone cation, an N-methylpyrrolidone or a 2-hydroxyethyltrimethylammonium cation, the anion being a tetrafluoroborate ion, a hexafluorophosphate ion, a sulfuric acid Hydrogen ion, nitrate ion, perchlorate ion, hydrogen phosphate ion, halogen anion, mesylate ion, trifluoroacetate ion, urea or hydroxyethoxy ion, organic cation and organic/inorganic The molar ratio of anionic to cation is 1:0.1-10, and the concentration of the graphite or graphite intercalation compound in the ionic liquid is 5-100 mg mg/ml.
  6. 根据权利要求1所述的方法，其特征在于，所述的机械力是指探头超声、水浴超声、高速剪切或球磨法或高压均质法中的一种。The method of claim 1 wherein said mechanical force is one of probe ultrasound, water bath ultrasound, high speed shear or ball milling or high pressure homogenization.
  7. 根据权利要求6所述的方法，其特征在于，所述的探头和超声水浴超声的功率为50-5000W，超声时间为5分钟-5小时；所述的高速剪切的转速为500-28,000转/分钟，剪切时间为10分钟-10小时；所述的球磨转速为200-1000转/分钟，研磨时间为10分钟-10小时；所述的高压均质机处理的压力为10-150MPa，物料流速在30-40000升/小时。 The method according to claim 6, wherein said probe and ultrasonic water bath have a power of 50-5000 W and an ultrasonic time of 5 minutes to 5 hours; said high-speed shearing speed is 500-28,000 rpm. /min, the shearing time is 10 minutes - 10 hours; the ball milling speed is 200-1000 rpm, the grinding time is 10 minutes - 10 hours; the high pressure homogenizer processing pressure is 10-150 MPa, The material flow rate is between 30 and 40,000 liters / hour.
  8. 根据权利要求1所述的方法，其特征在于，所述的步骤(2)中，所述的高浓度石墨烯分散液浓度为：1-100毫克/毫升，电导率为1000S/cm以上。The method according to claim 1, wherein in the step (2), the concentration of the high concentration graphene dispersion is from 1 to 100 mg/ml, and the conductivity is above 1000 S/cm.
  9. 根据权利要求1所述的方法，其特征在于，所述的石墨烯分散液中，石墨烯的平均径向尺寸范围为1-500微米。The method of claim 1 wherein in the graphene dispersion, the graphene has an average radial dimension ranging from 1 to 500 microns.
  10. 一种制品，所述制品包含如权利要求1所述的石墨烯分散液或由权利要求1所述的石墨烯分散液制备。An article comprising the graphene dispersion of claim 1 or the graphene dispersion of claim 1.
  11. 一种制备石墨烯分散液的方法，包括步骤：A method for preparing a graphene dispersion, comprising the steps of:
    (a)将石墨与膨胀剂在0-100℃下混合，得到膨胀石墨；(a) mixing graphite and a swelling agent at 0-100 ° C to obtain expanded graphite;
    (b)将步骤(a)得到的膨胀石墨与离子液体混合，得到石墨烯分散液；(b) mixing the expanded graphite obtained in the step (a) with an ionic liquid to obtain a graphene dispersion;
    (c)任选地，将步骤(b)所得的石墨烯分散液过滤或涂抹成膜，得到石墨烯薄膜。(c) Optionally, the graphene dispersion obtained in the step (b) is filtered or coated to form a graphene film.
  12. 如权利要求11所述的方法，其特征在于，所述石墨烯薄膜的电导率为1000-105S/cm，较佳地为1100-5000S/cm，更佳地为1500-3000S/cm。The method according to claim 11, wherein the graphene film has an electric conductivity of from 1,000 to 10 5 S/cm, preferably from 1,100 to 5,000 S/cm, more preferably from 1,500 to 3,000 S/cm.
  13. 一种制备石墨烯分散液的方法，包括步骤：A method for preparing a graphene dispersion, comprising the steps of:
    (i)将石墨与插层剂在0-100℃下搅拌反应；(i) stirring the graphite and the intercalation agent at 0-100 ° C;
    (ii)将步骤(i)的搅拌反应产物与膨胀剂混合，得到石墨烯聚集体；(ii) mixing the stirred reaction product of step (i) with a swelling agent to obtain a graphene aggregate;
    (iii)将步骤(ii)得到的石墨烯聚集体与离子液体混合，得到石墨烯分散液；(iii) mixing the graphene aggregate obtained in the step (ii) with the ionic liquid to obtain a graphene dispersion;
    (iv)任选地，将步骤(iii)所得的石墨烯分散液过滤或涂抹成膜，得到石墨烯薄膜。 (iv) Optionally, the graphene dispersion obtained in the step (iii) is filtered or smeared to form a graphene film.
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