WO2016101208A1 - Single-layer graphene dispersion liquid and preparation method therefor - Google Patents
Single-layer graphene dispersion liquid and preparation method therefor Download PDFInfo
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- the invention relates to the field of nano material processing, in particular to a single layer graphene dispersion and a preparation method thereof.
- Graphene is another important carbon material after fullerenes and carbon nanotubes.
- Graphene is a honeycomb hexagonal planar two-dimensional crystal formed by arranging a single layer of carbon atoms, and the carbon atoms are hybridized in the form of sp 2 .
- the surface area of graphene is as high as 2630 m 2 /g, which is twice that of single-walled carbon nanotubes; the electron mobility at room temperature exceeds 200,000 cm 2 /V ⁇ s, which is higher than that of single crystal silicon; the thermal conductivity is as high as 5300 W/m ⁇ K, high.
- resistivity is only 10 -6 ⁇ cm, similar to silver; single-layer graphene is almost completely transparent, each layer only absorbs 2.3% of light; graphene is currently the thinnest and strongest nano in the world Material, its strength can reach 1000GPa, which is 200 times that of steel.
- graphene sheets are prone to aggregation and affect the performance of graphene. Therefore, graphene is usually dispersed in an organic solvent or an aqueous solution of a surfactant, and solvent molecules or surfactant molecules are adsorbed on the surface of graphene. In this way, monolayer dispersion of graphene is achieved by means of intermolecular forces or electrostatic repulsion forces. Uniform and stable dispersions are important conditions for the application and research of graphene in many fields. However, the concentration of graphene dispersions reported at present is low, which limits the industrialization of graphene.
- the main methods of the graphene dispersion are: directly dispersing the mixture of graphene or graphene and the surface active ultrasonically under ultrasonic water bath conditions.
- Jonathan N. Coleman Umar Khan, Arlene O'Neill, Mustafa Lotya, Sukanta De, Jonathan N. Coleman. High-Concentration Solvent Exfoliation of Graphene, Small, 2010, 6, 864-871.
- NMP nitrogen methylpyrrolidone
- the graphene dispersion obtained by this method has a low concentration and is a multi-layer graphene sheet, and has a long processing time, which severely limits the actual demand of graphene.
- Dan Li Dan Li, Marc B. Müller, Scott Gilje, Richard B. Kaner, Gordon G. Wallace. Processable Aqueous Dispersions of Graphene Nanosheets, Nature Nanotechnology, 2008, 3, 101-105.
- aqueous graphene oxide solution A certain amount of hydrazine hydrate and aqueous ammonia solution were reduced at 95 ° C for 1 h to obtain a graphene dispersion having a concentration of 0.5 mg mL -1 .
- the graphene dispersion obtained by this method has low concentration and poor stability and cannot meet various industrial requirements.
- the existing graphene dispersion has a high preparation cost, which restricts the industrialization process of graphene.
- the graphene sheets in the existing commercial graphene dispersions are all in a plurality of layers, and it is difficult to obtain a single layer of graphene dispersion.
- CN104151582 A method for preparing a graphene-polyimide conductive black film is provided. First, the expanded graphite is subjected to secondary expansion to obtain secondary expanded graphite, and the secondary expanded graphite and the black filler dispersion are mixed and ultrasonically stripped. A dispersion of graphene and a black filler was obtained, and the dispersion was prepared by adding a diamine monomer or the like to a material which can be cast on a glass plate. In this method, graphitic olefin is prepared by using secondary expanded graphite. However, the graphene dispersion produced by ultrasonic stripping has good fluidity, and it can be said that the concentration is low, and it is impossible to prove that graphene exists as a single layer.
- CN102942177 provides a method for preparing graphene sheets, (1) thermally expanding the expandable graphite into worm-like graphite, immersing in an alkaline solution, filtering, washing, and then dispersing in a solvent to obtain micro-nano graphite.
- the micro-nano graphene sheet prepared in the step (1) is dispersed in an inorganic strong protonic acid, soaked, filtered, and then immersed in a H 2 O 2 solution, followed by suction filtration, washing, and drying; (3) transferring the micro-nano graphene sheet treated in the step (2) to a solvent, dispersing at a constant temperature, and then performing secondary expansion after suction filtration or drying; (4) treating the step (3)
- the micro-nano graphene sheet is transferred to a solvent for ultrasonic dispersion, filtered and dried, and then transferred to a furnace having a reducing protective atmosphere, and subjected to high-temperature deoxidation and reduction to obtain a graphene sheet. Scanning electron micrographs show that the graphene prepared by this method has poor dispersibility and produces a build-up phenomenon.
- An object of the present invention is to provide a single-layer graphene dispersion liquid and a preparation method thereof, which solve the problem that single-layer graphene is difficult to disperse.
- One aspect of the present invention provides a method for preparing a single layer graphene dispersion, comprising:
- Step 1 preparing graphite into secondary expanded graphite; step 2, mixing the secondary expanded graphite and dispersant at a mass ratio of 5:1 to 1:5 to obtain a mixed dispersion system; and step 3, the mixed dispersion system Mechanical shear stripping is performed; in step 4, a single layer graphene dispersion is obtained.
- the dispersing agent comprises: sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, sodium cholate, polystyrene, One or more of cetyltrimethylammonium bromide.
- the mixed dispersion system further comprises: water or a solvent; the solvent comprises: cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone , 1,3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoic acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-A Pyrrolidone, dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, N-octylpyrrolidone, dioxolane, ethyl acetate, 1-azonaphthalene, benzoin, ethanolamine, diethyl citrate, N - dodecylpyrrolidone, pyridine, dimethyl decanoate, ethanol, ace
- the apparatus used for the mechanical shearing comprises: one or more of a ball mill, an emulsifier, a disperser, a grinder, a homogenizer, and a fluid collider.
- a ball mill emulsifier
- a disperser emulsifier
- a grinder emulsifier
- a homogenizer emulsifier
- a fluid collider emulsifier
- the mechanical shear rate is from 2000 to 15000 revolutions per minute, and/or the mechanical shear time is from 1 to 30 hours.
- the method for preparing the secondary expanded graphite comprises: step a. oxidizing the graphite; and step b. expanding the graphite treated in step a.
- the graphite treated in step b is further subjected to oxidation treatment; step d.
- the graphite after the step c is subjected to high-temperature reduction expansion to obtain secondary expanded graphite.
- the oxidizing agent used includes: sulfuric acid, nitric acid, potassium permanganate, potassium chlorate One or more of hydrogen peroxide, nitrous acid, and hypochlorous acid.
- the temperature of the high temperature reduction expansion is 600 to 1800 °C.
- Another aspect of the present invention provides a single-layer graphene dispersion prepared by the above method, comprising: 1 to 10 wt% of graphene, 0.01 to 5 wt% of a dispersant; and the graphene dispersion
- concentration is 10 to 60 mg mL -1
- diameter of the graphene is 200 nm to 10 ⁇ m
- the dispersing agent is sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, sodium cholate, One or more of polystyrene, cetyltrimethylammonium bromide.
- the single-layer graphene dispersion further comprises: water or a solvent
- the solvent comprises: cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone, 1,3- Dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoic acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, dimethic acid Amide, cyclohexylpyrrolidone, benzyl ether, isopropanol, N-octylpyrrolidone, dioxolane, ethyl acetate, 1-azonaphthalene, benzoin, ethanolamine, diethyl citrate, N-dodecyl Pyrrolidone, pyridine, dimethyl decanoate, ethanol,
- the single-layer graphene dispersion liquid provided by the embodiment of the invention and the preparation method thereof are compared with the prior art, firstly, the graphite is prepared into secondary expanded graphite, the van der Waals force between the graphite molecules is destroyed, and the secondary expanded graphite exhibits slice separation. Structure; adding dispersant agent to increase dispersibility; mechanically shearing and stripping the mixed dispersion system of secondary expanded graphite and dispersant, separating the sheet of secondary expanded graphite to obtain single-layer graphene
- the dispersing agent disperses to obtain a graphene dispersion which is preferably dispersed in a single layer.
- Example 1 is an optical photograph of a graphene dispersion in Example 1 of the present invention.
- Example 2 is a transmission electron micrograph of a graphene dispersion in Example 1 of the present invention.
- Example 3 is a graphene Raman spectrum in Example 1 of the present invention.
- Fig. 4 is a view showing that the graphene dispersed ultraviolet visible spectrum in Example 1 of the present invention proves that the dispersibility is good.
- the present invention provides a single-layer graphene dispersion and a preparation method thereof.
- the preparation method of the single-layer graphene dispersion comprises:
- Step 1 preparing graphite into secondary expanded graphite
- Step 2 mixing the secondary expanded graphite and the dispersant at a mass ratio of 5:1 to 1:5 to obtain a mixed dispersion system
- Step 3 mechanically shearing the mixed dispersion system
- step 4 a single layer of graphene dispersion is obtained.
- the single-layer graphene dispersion prepared by the above-mentioned single-layer graphene dispersion preparation method comprises: 1 to 10 wt% of graphene, 0.01 to 5 wt% of a dispersant; and the concentration of the graphene dispersion is 10 to 60 mg mL -1
- Graphene has a diameter of 200 nm to 10 ⁇ m; dispersant is sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, sodium cholate, polystyrene, cetyltrimethyl One or more of ammonium bromide.
- graphite is first prepared into secondary expanded graphite to destroy van der Waals force between graphite molecules, and secondary expanded graphite exhibits a sheet separation structure; on the basis of which a dispersant is added to increase dispersibility; Mechanically shearing with a mixed dispersion system of a dispersing agent, separating a sheet of secondary expanded graphite to obtain a single layer of graphene, and dispersing by a dispersing agent, obtaining a dispersing property, and dispersing the graphene in a single layer liquid.
- Mechanical shearing separates the graphite layers of the secondary expanded graphite.
- the mechanical equipment such as a ball mill, an emulsifier, a disperser, a grinder, a homogenizer, and a fluid collider can be peeled off to obtain a small layer.
- Graphene in which a spherical or rod-shaped grinding medium is added to these mechanical devices, the shearing area can be increased, and the peeling effect can be further improved, and a single-layer graphene can be obtained.
- the use of the grinding medium facilitates uniform dispersion of the dispersion and improves the dispersion of the dispersion.
- the oxidized graphite is expanded in a tube furnace for 30 seconds to 5 minutes at a temperature of 1000-1300 ° C to obtain a primary expanded graphite, and the expanded graphite is treated in the same manner as above. - 1500 ° C high temperature reduction expansion to obtain secondary expanded graphite.
- Preparation of single-layer graphene dispersion mixing secondary expanded graphite and polyvinylpyrrolidone to obtain a mixed dispersion system at a mass ratio of 3:2; mechanically shearing the mixed dispersion system by a ball mill at a shear rate of 2000 rpm.
- the mechanical shearing time is 20 hours, and a single layer graphene dispersion is obtained, which comprises: 6 wt% graphene, 4 wt% dispersant; the graphene has a diameter of 200 nm to 8 micrometers;
- the oxidizing agent may be replaced by one or more of potassium permanganate, hydrogen peroxide, hypochlorous acid, and nitrous acid.
- the dispersing agent may also be selected from one or more of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium cholate, polystyrene, cetyltrimethylammonium bromide.
- the graphene dispersion obtained in this example was optically imaged.
- the single-layer graphene dispersion was a black viscous slurry, and the dispersion was inverted, and almost no flow occurred, and the dispersion was good. Good, stable, high concentration characteristics.
- Photographed under a transmission electron microscope, as shown in Fig. 2 the dispersion was almost entirely a single layer of graphene sheets.
- the powder of the preparation dispersion was subjected to Raman characterization, and by the shape of the 2D peak, we judged that a single layer of graphene was obtained, as shown in FIG.
- the absorption spectrum of the ultraviolet-visible light of the different concentration dispersions was measured, and the maximum absorption peak showed a linear relationship indicating that the dispersion of the graphene dispersion was good, as shown in FIG.
- the graphene dispersion solves the problems of poor dispersibility, low stability, and low concentration of graphene in water and various organic solvents.
- This process is stirred for 72h, the treated graphite is washed with a large amount of water to be neutral, and dried to obtain powder;
- the oxidized graphite is expanded in a tube furnace at a temperature of 1300 to 1500 ° C for a period of 30 S to 5 min.
- the expanded graphite is treated by the same method as above, and the expanded graphite is treated at a high temperature of 800 to 1800 ° C. A secondary expanded graphite was obtained.
- Preparation of single-layer graphene dispersion mixing the secondary expanded graphite and polyvinylpyrrolidone by a mass ratio of 1:1 to obtain a mixed dispersion system; mechanically shearing the shear dispersion system by a fluid collider, shear rate The degree of mechanical shearing is 5 hours, and the mechanical shearing time is 5 hours, to obtain a single-layer graphene dispersion, which is 7 wt% of graphene and 7 wt% of dispersant; the graphene has a diameter of 500 nm to 10 Micron
- the oxidizing agent may also be replaced by one or more of potassium permanganate, sulfuric acid, hypochlorous acid, and nitrous acid in the embodiment.
- the dispersing agent may also be selected from one or more of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium cholate, polystyrene, cetyltrimethylammonium bromide.
- the secondary expanded graphite and sodium cholate are mixed at a mass ratio of 3:1 to obtain a mixed dispersion system; the solvent N-octylpyrrolidone is added to the mixed dispersion system, and the mixture is mixed by a fluid emulsifier
- the finally obtained solution was mechanically sheared in a homogenizer (loaded with a spherical grinding medium) at a shear rate of 8000 rpm and a mechanical shearing time of 30 hours to obtain a single layer graphene dispersion, wherein 5 wt % graphene, 1.7 wt% dispersant; the graphene has a diameter of 200 nm to 8 ⁇ m;
- the oxidizing agent may also be one or more of concentrated sulfuric acid, concentrated nitric acid, potassium permanganate, and potassium chlorate.
- the dispersing agent may also be selected from one or more of sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, polystyrene, cetyltrimethylammonium bromide, or bile Sodium is shared with alternative dispersants.
- the solvent can also be replaced by cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone, 1,3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoin Acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, dioxolane, acetic acid Ethyl ester, 1-azinone, benzoic aldehyde, ethanolamine, diethyl decanoate, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl acetate, ethylene glycol, toluene, g One or more of an alkane, a pent
- the oxidizing agent may also be one or more of concentrated nitric acid, concentrated sulfuric acid, hypochlorous acid, and hydrogen peroxide.
- the dispersing agent may also be selected from sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, sodium cholate, one or more polystyrenes, or cetyltrimethyl bromide. Ammonium is shared with alternative dispersants.
- the solvent can also be replaced by cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone, 1,3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoin Acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, N-octylpyrrolidone, Dioxolane, ethyl acetate, 1-azaphthalene, benzoin, ethanolamine, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl acetate, ethylene glycol, toluene, g One or more of an alkane, pentane,
- the graphene dispersion obtained by the method has high concentration and strong stability, and is a single-layer graphene sheet.
- the preparation process is simple, the cost is low, and the advantages of industrial production are favorable.
- the obtained graphene dispersion has potential practical application value in the fields of light and electric materials.
Abstract
The present invention relates to the field of nanomaterial processing, and particularly to a single-layer graphene dispersion liquid and a preparation method therefor. The dispersion liquid comprises 1 to 10 wt% of graphene and 0.01 to 5 wt% of a dispersing agent. The concentration of the graphene dispersion liquid is 10 to 60 mg mL-1, and the diameter of graphene is 200 nm to 10 µm. The preparation method comprises: preparing secondary expanded graphite from graphite; mixing the secondary expanded graphite with a dispersing agent to obtain a mixed dispersion system; and carrying out mechanical shearing and peeling on the mixed dispersion system, so as to obtain a single-layer graphene dispersion liquid. According to the present invention, layers of secondary expanded graphite can be subjected to mechanical separation to obtain single-layer graphene; and by means of the dispersion effect of the dispersing agent, a graphene dispersion liquid that is good in dispersity and exists in a single layer can be obtained.
Description
本发明涉及纳米材料加工领域，具体而言，涉及单层石墨烯分散液及其制备方法。The invention relates to the field of nano material processing, in particular to a single layer graphene dispersion and a preparation method thereof.
2004年，英国曼彻斯特大学物理学家安德烈·海姆和康斯坦丁·诺沃肖洛夫，在实验中成功地从石墨中分离出石墨烯，而证实它可以单独存在，由于两人在“二维石墨烯材料的开创性实验”，共同获得2010年诺贝尔物理学奖，拉开了石墨烯制备的序幕。石墨烯是继富勒烯和碳纳米管后又一重要的碳材料。石墨烯是由单层碳原子排列形成的蜂窝状六角平面二维晶体，碳原子是以sp2形式杂化。石墨烯的表面积高达2630m2/g，是单壁纳米碳管的两倍；常温下电子迁移率超过200000cm2/V·s，比单晶硅都高；导热系数高达5300W/m·K，高于金刚石；电阻率只有10-6Ω·cm，与银类似；单层石墨烯几乎是完全透明的，每层只吸收2.3％的光；石墨烯是目前世界上最薄，而且最强的纳米材料，它的强度可达1000GPa，是钢的200倍。石墨烯这些优异的特性使其在气体传感器、光电子器件、化学能源(太阳能电池、锂离子电池)、催化剂、抗静电等领域具有巨大的潜在应用。In 2004, the physicists of the University of Manchester, André Heim and Konstantin Novoselov, succeeded in separating graphene from graphite in experiments, and confirmed that it can exist alone, because the two "The pioneering experiment of two-dimensional graphene materials", jointly won the 2010 Nobel Prize in Physics, opened the prelude to the preparation of graphene. Graphene is another important carbon material after fullerenes and carbon nanotubes. Graphene is a honeycomb hexagonal planar two-dimensional crystal formed by arranging a single layer of carbon atoms, and the carbon atoms are hybridized in the form of sp 2 . The surface area of graphene is as high as 2630 m 2 /g, which is twice that of single-walled carbon nanotubes; the electron mobility at room temperature exceeds 200,000 cm 2 /V·s, which is higher than that of single crystal silicon; the thermal conductivity is as high as 5300 W/m·K, high. In diamond; resistivity is only 10 -6 Ω·cm, similar to silver; single-layer graphene is almost completely transparent, each layer only absorbs 2.3% of light; graphene is currently the thinnest and strongest nano in the world Material, its strength can reach 1000GPa, which is 200 times that of steel. These excellent properties of graphene make it a huge potential application in the fields of gas sensors, optoelectronic devices, chemical energy sources (solar cells, lithium ion batteries), catalysts, antistatic, and the like.
在实际的应用中，石墨烯片层容易发生聚集，影响石墨烯性能的发挥，因此通常将石墨烯分散在有机溶剂或表面活性剂水溶液中，溶剂分子或表面活性剂分子吸附在石墨烯的表面上，依靠分子间作用力或静电排斥力，实现石墨烯的单层分散。均一、稳定的分散液是石墨烯在众多领域应用和研究的重要条件，但目前报道的石墨烯分散液的浓度都较低，限制了石墨烯的产业化发展。
In practical applications, graphene sheets are prone to aggregation and affect the performance of graphene. Therefore, graphene is usually dispersed in an organic solvent or an aqueous solution of a surfactant, and solvent molecules or surfactant molecules are adsorbed on the surface of graphene. In this way, monolayer dispersion of graphene is achieved by means of intermolecular forces or electrostatic repulsion forces. Uniform and stable dispersions are important conditions for the application and research of graphene in many fields. However, the concentration of graphene dispersions reported at present is low, which limits the industrialization of graphene.
目前，石墨烯分散液的主要方法有：直接将石墨烯或石墨烯与表面活性的混合液在超声波的水浴条件下超声分散。例如，Jonathan N.Coleman(Umar Khan,Arlene O’Neill,Mustafa Lotya,Sukanta De,Jonathan N.Coleman.High-Concentration Solvent Exfoliation of Graphene,Small,2010,6,864-871.)等研究者将片状的石墨分散到溶剂氮甲基吡咯烷酮(NMP)中，利用超声波超声460h，得到石墨烯分散液，其浓度是3.3mg mL-1。这种方法得到的石墨烯分散液浓度低，且为多层石墨烯片、处理时间长，严重限制了石墨烯的实际需求。Dan Li(Dan Li,Marc B.Müller,Scott Gilje,Richard B.Kaner,Gordon G.Wallace.Processable Aqueous Dispersions of Graphene Nanosheets,Nature Nanotechnology,2008,3,101-105.)等研究者将氧化石墨烯水溶液用一定量的水合肼和氨水溶液95℃还原1h，得到浓度是0.5mg mL-1的石墨烯分散液，这种方法得到的石墨烯分散液浓度低、稳定性差，不能满足工业的各种需求。总体来说，现有石墨烯分散液的制备成本较高，制约了石墨烯的产业化进程。此外，由于石墨烯片层的聚集作用，现有商业化的石墨烯分散液中石墨烯片层均为多层存在，难以获得单层的石墨烯分散液。At present, the main methods of the graphene dispersion are: directly dispersing the mixture of graphene or graphene and the surface active ultrasonically under ultrasonic water bath conditions. For example, Jonathan N. Coleman (Umar Khan, Arlene O'Neill, Mustafa Lotya, Sukanta De, Jonathan N. Coleman. High-Concentration Solvent Exfoliation of Graphene, Small, 2010, 6, 864-871.) The graphite was dispersed in a solvent of nitrogen methylpyrrolidone (NMP), and ultrasonically sonicated for 460 hours to obtain a graphene dispersion having a concentration of 3.3 mg mL -1 . The graphene dispersion obtained by this method has a low concentration and is a multi-layer graphene sheet, and has a long processing time, which severely limits the actual demand of graphene. Dan Li (Dan Li, Marc B. Müller, Scott Gilje, Richard B. Kaner, Gordon G. Wallace. Processable Aqueous Dispersions of Graphene Nanosheets, Nature Nanotechnology, 2008, 3, 101-105.) and other researchers use aqueous graphene oxide solution A certain amount of hydrazine hydrate and aqueous ammonia solution were reduced at 95 ° C for 1 h to obtain a graphene dispersion having a concentration of 0.5 mg mL -1 . The graphene dispersion obtained by this method has low concentration and poor stability and cannot meet various industrial requirements. In general, the existing graphene dispersion has a high preparation cost, which restricts the industrialization process of graphene. In addition, due to the aggregation of the graphene sheets, the graphene sheets in the existing commercial graphene dispersions are all in a plurality of layers, and it is difficult to obtain a single layer of graphene dispersion.
CN104151582给出一种石墨烯-聚酰亚胺导电黑膜的制备方法，首先对膨胀石墨进行二次膨胀得到二次膨胀石墨，将二次膨胀石墨和黑色填料分散液混合，对其进行超声剥离得到石墨烯与黑色填料的分散液，该分散液在加入二胺单体等制备可以流延在玻璃板上的物质。在该方法中采用了二次膨胀石墨制备石墨烯，但是，采用超声剥离的方式生产的石墨烯分散液流动性较好，也可以说浓度较低，且无法证明石墨烯为单层存在。CN104151582 A method for preparing a graphene-polyimide conductive black film is provided. First, the expanded graphite is subjected to secondary expansion to obtain secondary expanded graphite, and the secondary expanded graphite and the black filler dispersion are mixed and ultrasonically stripped. A dispersion of graphene and a black filler was obtained, and the dispersion was prepared by adding a diamine monomer or the like to a material which can be cast on a glass plate. In this method, graphitic olefin is prepared by using secondary expanded graphite. However, the graphene dispersion produced by ultrasonic stripping has good fluidity, and it can be said that the concentration is low, and it is impossible to prove that graphene exists as a single layer.
CN102942177给出一种石墨烯片的制备方法，(1)将可膨胀石墨进行热膨胀处理成蠕虫状石墨，再用碱性溶液浸泡、抽滤、洗涤后置于溶剂中进行超声分散得微纳米石墨烯片；(2)将步骤(1)中制备得到的微纳米石墨烯片分散到无机强质子酸中浸泡，抽滤后转入H2O2溶液中浸泡，然后抽滤、洗涤、干燥；(3)将经步骤(2)处理过的微纳米石墨烯片转移到溶剂中分散，恒温静置，
再经抽滤或干燥后进行二次膨胀；(4)将经步骤(3)处理过的微纳米石墨烯片转移到溶剂中进行超声分散，过滤干燥后转移至具有还原保护气氛的炉子中，进行高温脱氧还原后即得石墨烯片。通过扫描电镜图片可以看出该方法制备的石墨烯分散性较差，产生堆积现象。CN102942177 provides a method for preparing graphene sheets, (1) thermally expanding the expandable graphite into worm-like graphite, immersing in an alkaline solution, filtering, washing, and then dispersing in a solvent to obtain micro-nano graphite. (2) The micro-nano graphene sheet prepared in the step (1) is dispersed in an inorganic strong protonic acid, soaked, filtered, and then immersed in a H 2 O 2 solution, followed by suction filtration, washing, and drying; (3) transferring the micro-nano graphene sheet treated in the step (2) to a solvent, dispersing at a constant temperature, and then performing secondary expansion after suction filtration or drying; (4) treating the step (3) The micro-nano graphene sheet is transferred to a solvent for ultrasonic dispersion, filtered and dried, and then transferred to a furnace having a reducing protective atmosphere, and subjected to high-temperature deoxidation and reduction to obtain a graphene sheet. Scanning electron micrographs show that the graphene prepared by this method has poor dispersibility and produces a build-up phenomenon.
发明内容Summary of the invention
本发明的目的在于提供一种单层石墨烯分散液及其制备方法，以解决单层石墨烯难以分散的问题。An object of the present invention is to provide a single-layer graphene dispersion liquid and a preparation method thereof, which solve the problem that single-layer graphene is difficult to disperse.
本发明一个方面提供了一种单层石墨烯分散液的制备方法，包括：One aspect of the present invention provides a method for preparing a single layer graphene dispersion, comprising:
步骤1，将石墨制备成二次膨胀石墨；步骤2，将所述二次膨胀石墨、分散剂按质量比5:1～1:5混合得到混合分散体系；步骤3，将所述混合分散体系进行机械剪切剥离；步骤4，得到单层石墨烯分散液。Step 1: preparing graphite into secondary expanded graphite; step 2, mixing the secondary expanded graphite and dispersant at a mass ratio of 5:1 to 1:5 to obtain a mixed dispersion system; and step 3, the mixed dispersion system Mechanical shear stripping is performed; in step 4, a single layer graphene dispersion is obtained.
在一些实施例中，优选为，所述步骤2中，所述分散剂包括：十二烷基苯磺酸钠、十二烷基磺酸钠、聚乙烯吡咯烷酮、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵一种或多种。In some embodiments, preferably, in the step 2, the dispersing agent comprises: sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, sodium cholate, polystyrene, One or more of cetyltrimethylammonium bromide.
在一些实施例中，优选为，所述步骤2中，所述混合分散体系还包括：水或溶剂；所述溶剂包括：环戊酮、环己酮、哌啶-1-甲醛、乙烯基吡咯烷酮、1，3-二甲基-2-咪唑啉、溴苯、氰苯、苯甲基安息香酸、N，N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、二甲乙酰胺、环己基吡咯烷酮、苄醚、异丙醇、N-辛基吡咯烷酮、二氧戊环、乙酸乙酯、1-氮萘、安息香醛、乙醇胺、酞酸二乙酯、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、甲苯、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜、二氯代苯、氯仿、四氢呋喃的一种或多种。In some embodiments, preferably, in the step 2, the mixed dispersion system further comprises: water or a solvent; the solvent comprises: cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone , 1,3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoic acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-A Pyrrolidone, dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, N-octylpyrrolidone, dioxolane, ethyl acetate, 1-azonaphthalene, benzoin, ethanolamine, diethyl citrate, N - dodecylpyrrolidone, pyridine, dimethyl decanoate, ethanol, acetone, vinyl acetate, ethylene glycol, toluene, heptane, pentane, hexane, formamide, dimethylformamide, dimethyl One or more of sulfoxide, dichlorobenzene, chloroform, and tetrahydrofuran.
在一些实施例中，优选为，所述步骤3中，所述机械剪切采用的设备包括：球磨机、乳化机、分散机、研磨机、匀质机、流体对撞机中的一种或多种。
In some embodiments, preferably, in the step 3, the apparatus used for the mechanical shearing comprises: one or more of a ball mill, an emulsifier, a disperser, a grinder, a homogenizer, and a fluid collider. Kind.
在一些实施例中，优选为，所述机械剪切的速度为2000～15000转/分钟，和/或，所述机械剪切的时间为1～30小时。In some embodiments, preferably, the mechanical shear rate is from 2000 to 15000 revolutions per minute, and/or the mechanical shear time is from 1 to 30 hours.
在一些实施例中，优选为，所述步骤1中，所述二次膨胀石墨的制备方法包括：步骤a.将所述石墨进行氧化处理；步骤b.将步骤a处理后的石墨进行膨胀处理；步骤c.将步骤b处理后的石墨再进行氧化处理；步骤d.将步骤c处理后的石墨进行高温还原膨胀得到二次膨胀石墨。In some embodiments, preferably, in the step 1, the method for preparing the secondary expanded graphite comprises: step a. oxidizing the graphite; and step b. expanding the graphite treated in step a. Step c. The graphite treated in step b is further subjected to oxidation treatment; step d. The graphite after the step c is subjected to high-temperature reduction expansion to obtain secondary expanded graphite.
在一些实施例中，优选为，所述步骤a中，在氧化处理中，其中石墨与氧化剂的质量比25:1～45:1，采用的氧化剂包括：硫酸、硝酸、高锰酸钾、氯酸钾、双氧水、亚硝酸、次氯酸中的一种或多种。In some embodiments, preferably, in the step a, in the oxidation treatment, wherein the mass ratio of graphite to oxidant is 25:1 to 45:1, the oxidizing agent used includes: sulfuric acid, nitric acid, potassium permanganate, potassium chlorate One or more of hydrogen peroxide, nitrous acid, and hypochlorous acid.
在一些实施例中，优选为，所述步骤d中，所述高温还原膨胀的温度为600～1800℃。In some embodiments, preferably, in the step d, the temperature of the high temperature reduction expansion is 600 to 1800 °C.
本发明另一个方面还提供了一种通过上述方法制备的单层石墨烯分散液，其特征在于，包括：1～10wt％的石墨烯、0.01～5wt％分散剂；所述石墨烯分散液的浓度为10～60mg mL-1、石墨烯的直径为200纳米～10微米；所述分散剂为十二烷基苯磺酸钠、十二烷基磺酸钠、聚乙烯吡咯烷酮、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵一种或多种。Another aspect of the present invention provides a single-layer graphene dispersion prepared by the above method, comprising: 1 to 10 wt% of graphene, 0.01 to 5 wt% of a dispersant; and the graphene dispersion The concentration is 10 to 60 mg mL -1 , and the diameter of the graphene is 200 nm to 10 μm; the dispersing agent is sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, sodium cholate, One or more of polystyrene, cetyltrimethylammonium bromide.
在一些实施例中，优选为，单层石墨烯分散液还包括：水或溶剂，所述溶剂包括：环戊酮、环己酮、哌啶-1-甲醛、乙烯基吡咯烷酮、1，3-二甲基-2-咪唑啉、溴苯、氰苯、苯甲基安息香酸、N，N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、二甲乙酰胺、环己基吡咯烷酮、苄醚、异丙醇、N-辛基吡咯烷酮、二氧戊环、乙酸乙酯、1-氮萘、安息香醛、乙醇胺、酞酸二乙酯、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、甲苯、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜、二氯代苯、氯仿、四氢呋喃的一种或多种。
In some embodiments, preferably, the single-layer graphene dispersion further comprises: water or a solvent, and the solvent comprises: cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone, 1,3- Dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoic acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, dimethic acid Amide, cyclohexylpyrrolidone, benzyl ether, isopropanol, N-octylpyrrolidone, dioxolane, ethyl acetate, 1-azonaphthalene, benzoin, ethanolamine, diethyl citrate, N-dodecyl Pyrrolidone, pyridine, dimethyl decanoate, ethanol, acetone, vinyl acetate, ethylene glycol, toluene, heptane, pentane, hexane, formamide, dimethylformamide, dimethyl sulfoxide, dichloro One or more of benzene, chloroform and tetrahydrofuran.
本发明实施例提供的单层石墨烯分散液及其制备方法，与现有技术相比，首先将石墨制备成二次膨胀石墨，破坏石墨分子间的范德华力，二次膨胀石墨呈现片层分离结构；在此基础上加入分散剂剂增加分散性；对二次膨胀石墨和分散剂的混合分散体系进行机械剪切剥离，将二次膨胀石墨的片层分离即可得到单层石墨烯，借助分散剂的分散作用，得到分散性较好，以单层存在的石墨烯分散液。The single-layer graphene dispersion liquid provided by the embodiment of the invention and the preparation method thereof are compared with the prior art, firstly, the graphite is prepared into secondary expanded graphite, the van der Waals force between the graphite molecules is destroyed, and the secondary expanded graphite exhibits slice separation. Structure; adding dispersant agent to increase dispersibility; mechanically shearing and stripping the mixed dispersion system of secondary expanded graphite and dispersant, separating the sheet of secondary expanded graphite to obtain single-layer graphene The dispersing agent disperses to obtain a graphene dispersion which is preferably dispersed in a single layer.
图1为本发明实施例1中石墨烯分散液光学照片；1 is an optical photograph of a graphene dispersion in Example 1 of the present invention;
图2为本发明实施例1中石墨烯分散液透射电镜照片；2 is a transmission electron micrograph of a graphene dispersion in Example 1 of the present invention;
图3为本发明实施例1中石墨烯Raman光谱；3 is a graphene Raman spectrum in Example 1 of the present invention;
图4为本发明实施例1中石墨烯分散紫外可见光谱证明分散性好。Fig. 4 is a view showing that the graphene dispersed ultraviolet visible spectrum in Example 1 of the present invention proves that the dispersibility is good.
下面通过具体的实施例结合附图对本发明做进一步的详细描述。The present invention will be further described in detail below with reference to the accompanying drawings.
考虑到目前单层石墨烯制作困难，且极易聚集的问题，本发明提供了一种单层石墨烯分散液及其制备方法。In view of the current difficulty in making single-layer graphene and the problem of extremely easy aggregation, the present invention provides a single-layer graphene dispersion and a preparation method thereof.
该一种单层石墨烯分散液的制备方法，包括：The preparation method of the single-layer graphene dispersion comprises:
步骤1，将石墨制备成二次膨胀石墨； Step 1, preparing graphite into secondary expanded graphite;
步骤2，将二次膨胀石墨、分散剂按质量比5:1～1:5混合得到混合分散体系； Step 2, mixing the secondary expanded graphite and the dispersant at a mass ratio of 5:1 to 1:5 to obtain a mixed dispersion system;
步骤3，将混合分散体系进行机械剪切剥离； Step 3, mechanically shearing the mixed dispersion system;
步骤4，得到单层石墨烯分散液。In step 4, a single layer of graphene dispersion is obtained.
通过上述单层石墨烯分散液的制备方法制备的单层石墨烯分散液，包括：1～10wt％的石墨烯、0.01～5wt％分散剂；石墨烯分散液的浓度为10～60mg mL-1；石墨烯的直径为200纳米～10微米；分散剂为十二烷基苯磺酸钠、十二烷基磺酸钠、聚乙烯吡咯烷酮、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵一种或多种。
The single-layer graphene dispersion prepared by the above-mentioned single-layer graphene dispersion preparation method comprises: 1 to 10 wt% of graphene, 0.01 to 5 wt% of a dispersant; and the concentration of the graphene dispersion is 10 to 60 mg mL -1 Graphene has a diameter of 200 nm to 10 μm; dispersant is sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, sodium cholate, polystyrene, cetyltrimethyl One or more of ammonium bromide.
在本实施例中，首先将石墨制备成二次膨胀石墨，破坏石墨分子间的范德华力，二次膨胀石墨呈现片层分离结构；在此基础上加入分散剂增加分散性；对二次膨胀石墨和分散剂的混合分散体系进行机械剪切，将二次膨胀石墨的片层分离即可得到单层石墨烯，借助分散剂的分散作用，得到分散性较好，以单层存在的石墨烯分散液。In the present embodiment, graphite is first prepared into secondary expanded graphite to destroy van der Waals force between graphite molecules, and secondary expanded graphite exhibits a sheet separation structure; on the basis of which a dispersant is added to increase dispersibility; Mechanically shearing with a mixed dispersion system of a dispersing agent, separating a sheet of secondary expanded graphite to obtain a single layer of graphene, and dispersing by a dispersing agent, obtaining a dispersing property, and dispersing the graphene in a single layer liquid.
机械剪切将二次膨胀石墨的各层石墨分离，经发明人研究发现，采用机械设备如球磨机、乳化机、分散机、研磨机、匀质机、流体对撞机进行剥离可以得到少层的石墨烯，在这些机械设备中增加球状、棒状研磨介质，可增大剪切面积，进一步改善剥离效果，可得到单层石墨烯。而且研磨介质的使用利于分散液的均匀分散，改善了分散液的分散效果。Mechanical shearing separates the graphite layers of the secondary expanded graphite. According to the research of the inventors, it is found that the mechanical equipment such as a ball mill, an emulsifier, a disperser, a grinder, a homogenizer, and a fluid collider can be peeled off to obtain a small layer. Graphene, in which a spherical or rod-shaped grinding medium is added to these mechanical devices, the shearing area can be increased, and the peeling effect can be further improved, and a single-layer graphene can be obtained. Moreover, the use of the grinding medium facilitates uniform dispersion of the dispersion and improves the dispersion of the dispersion.
接下来，对该单层石墨烯分散液的制备做更为详细的说明：Next, the preparation of the single-layer graphene dispersion is described in more detail:
实施例1Example 1
制备二次膨胀石墨：将5g石墨放500mL的三口烧瓶中，将三口烧瓶浸到冰水混合物里，然后加入45mL的浓硝酸和87.5mL的浓硫酸，将55g的氯酸钾缓慢的加到三口烧瓶中(至少加超过15分钟。注意：在加氯酸钾时会产生二氧化氯，浓度高时会产生***)，这个过程搅拌处理72小时，用大量的水将处理的石墨洗成中性，干燥后获得粉末；然后对氧化后的石墨在管式炉中，膨胀时间30秒-5分钟，温度在1000-1300℃情况下进行高温还原得到一次膨胀石墨，采用上述同样的方法处理一次膨胀石墨后在600-1500℃高温还原膨胀得到二次膨胀石墨。Preparation of secondary expanded graphite: 5 g of graphite was placed in a 500 mL three-necked flask, and the three-necked flask was immersed in an ice-water mixture, then 45 mL of concentrated nitric acid and 87.5 mL of concentrated sulfuric acid were added, and 55 g of potassium chlorate was slowly added to the three-necked flask. (At least 15 minutes added. Note: chlorine dioxide will be produced when potassium chlorate is added, and it will explode when the concentration is high.) This process is stirred for 72 hours. The treated graphite is washed with a large amount of water to be neutral. Powder; then the oxidized graphite is expanded in a tube furnace for 30 seconds to 5 minutes at a temperature of 1000-1300 ° C to obtain a primary expanded graphite, and the expanded graphite is treated in the same manner as above. - 1500 ° C high temperature reduction expansion to obtain secondary expanded graphite.
制备单层石墨烯分散液：将二次膨胀石墨、聚乙烯吡咯烷酮混合得到混合分散体系按质量比3:2；通过球磨机对混合分散体系进行机械剪切，剪切速度为2000转/分钟，所述机械剪切的时间为20小时，得到单层石墨烯分散液，其中含有：6wt％的石墨烯、4wt％分散剂；所述石墨烯的直径为200纳米～8微米；
Preparation of single-layer graphene dispersion: mixing secondary expanded graphite and polyvinylpyrrolidone to obtain a mixed dispersion system at a mass ratio of 3:2; mechanically shearing the mixed dispersion system by a ball mill at a shear rate of 2000 rpm. The mechanical shearing time is 20 hours, and a single layer graphene dispersion is obtained, which comprises: 6 wt% graphene, 4 wt% dispersant; the graphene has a diameter of 200 nm to 8 micrometers;
需要说明的是，在本实施例中，氧化剂还可以替换为高锰酸钾、双氧水、次氯酸、亚硝酸中的一种或多种。It should be noted that, in this embodiment, the oxidizing agent may be replaced by one or more of potassium permanganate, hydrogen peroxide, hypochlorous acid, and nitrous acid.
分散剂还可以选自：十二烷基苯磺酸钠、十二烷基磺酸钠、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵一种或多种。The dispersing agent may also be selected from one or more of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium cholate, polystyrene, cetyltrimethylammonium bromide.
将该实施例得到的石墨烯分散液进行光学成像，如图1所示，该单层石墨烯分散液为黑色粘稠的浆料，将分散液倒置，几乎不发生流动，具有良好的分散性好，稳定性、高的浓度的特征。在透射电镜下拍照，如图2所示，分散液几乎全部为单层石墨烯片。将制备分散液的粉末进行拉曼表征，通过2D峰的形状，我们判断得到了单层石墨烯，如图3所示。将该实施例得到的石墨烯分散液稀释后，测量稀释不同浓度分散液的紫外可见光的吸收光谱，最大的吸收峰呈线性关系表明石墨烯分散液的分散性好，如图4所示。从这四张图可以看到，它涉及石墨烯分散液的高含量、良好的分散性和单层特性。该石墨烯分散液解决了石墨烯在水及其各种有机溶剂中分散性差、稳定性低、浓度较低等问题。The graphene dispersion obtained in this example was optically imaged. As shown in FIG. 1, the single-layer graphene dispersion was a black viscous slurry, and the dispersion was inverted, and almost no flow occurred, and the dispersion was good. Good, stable, high concentration characteristics. Photographed under a transmission electron microscope, as shown in Fig. 2, the dispersion was almost entirely a single layer of graphene sheets. The powder of the preparation dispersion was subjected to Raman characterization, and by the shape of the 2D peak, we judged that a single layer of graphene was obtained, as shown in FIG. After diluting the graphene dispersion obtained in this example, the absorption spectrum of the ultraviolet-visible light of the different concentration dispersions was measured, and the maximum absorption peak showed a linear relationship indicating that the dispersion of the graphene dispersion was good, as shown in FIG. As can be seen from these four figures, it relates to a high content of graphene dispersion, good dispersibility and single layer properties. The graphene dispersion solves the problems of poor dispersibility, low stability, and low concentration of graphene in water and various organic solvents.
实施例2Example 2
制备二次膨胀石墨：将5g石墨放500mL的三口烧瓶中，将三口烧瓶浸到冰水混合物里，然后加入50mL的浓硝酸和98mL的双氧水，将45g的氯酸钾缓慢的加到三口烧瓶中(至少加超过15min。注意：在加氯酸钾时会产生二氧化氯，浓度高时会产生***)，这个过程搅拌处理72h，用大量的水将处理的石墨洗成中性，干燥后获得粉末；然后对氧化后的石墨在管式炉中，膨胀时间30S～5min，温度在1300～1500℃情况下进行高温还原得到一次膨胀石墨，采用上述同样的方法处理一次膨胀石墨后在800～1800℃高温还原膨胀得到二次膨胀石墨。Preparation of secondary expanded graphite: 5 g of graphite was placed in a 500 mL three-necked flask, the three-necked flask was immersed in an ice-water mixture, then 50 mL of concentrated nitric acid and 98 mL of hydrogen peroxide were added, and 45 g of potassium chlorate was slowly added to the three-necked flask (at least Add more than 15min. Note: chlorine dioxide will be produced when potassium chlorate is added, and it will explode when the concentration is high. This process is stirred for 72h, the treated graphite is washed with a large amount of water to be neutral, and dried to obtain powder; The oxidized graphite is expanded in a tube furnace at a temperature of 1300 to 1500 ° C for a period of 30 S to 5 min. The expanded graphite is treated by the same method as above, and the expanded graphite is treated at a high temperature of 800 to 1800 ° C. A secondary expanded graphite was obtained.
制备单层石墨烯分散液：将二次膨胀石墨、聚乙烯吡咯烷酮质量比1:1，混合得到混合分散体系；通过流体对撞机对混合分散体系进行机械剪切，剪切速
度为10500转/分钟，所述机械剪切的时间为5小时，得到单层石墨烯分散液，其，7wt％的石墨烯、7wt％分散剂；所述石墨烯的直径为500纳米～10微米；Preparation of single-layer graphene dispersion: mixing the secondary expanded graphite and polyvinylpyrrolidone by a mass ratio of 1:1 to obtain a mixed dispersion system; mechanically shearing the shear dispersion system by a fluid collider, shear rate
The degree of mechanical shearing is 5 hours, and the mechanical shearing time is 5 hours, to obtain a single-layer graphene dispersion, which is 7 wt% of graphene and 7 wt% of dispersant; the graphene has a diameter of 500 nm to 10 Micron
需要说明的是，在本实施例中，氧化剂还可以在在本实施例中，氧化剂还可以替换为高锰酸钾、硫酸、次氯酸、亚硝酸中的一种或多种。It should be noted that, in this embodiment, the oxidizing agent may also be replaced by one or more of potassium permanganate, sulfuric acid, hypochlorous acid, and nitrous acid in the embodiment.
分散剂还可以选自：十二烷基苯磺酸钠、十二烷基磺酸钠、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵铵一种或多种。The dispersing agent may also be selected from one or more of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium cholate, polystyrene, cetyltrimethylammonium bromide.
实施例3Example 3
制备二次膨胀石墨：将5g石墨放500mL的三口烧瓶中，将三口烧瓶浸到冰水混合物里，然后加入45mL的亚硝酸和87.5mL的双氧水，将55g的次氯酸缓慢的加到三口烧瓶中(至少加超过15min。)，这个过程搅拌处理72h，用大量的水将处理的石墨洗成中性，干燥后获得粉末；然后对氧化后的石墨在管式炉中，膨胀时间30S～5min，温度在1300～1500℃情况下进行高温还原得到一次膨胀石墨，采用上述同样的方法处理一次膨胀石墨后在1300～1500℃高温还原膨胀得到二次膨胀石墨。Preparation of secondary expanded graphite: 5 g of graphite was placed in a 500 mL three-necked flask, the three-necked flask was immersed in an ice-water mixture, then 45 mL of nitrous acid and 87.5 mL of hydrogen peroxide were added, and 55 g of hypochlorous acid was slowly added to the three-necked flask. Medium (at least more than 15min.), this process is stirred for 72h, the treated graphite is washed with a large amount of water to be neutral, dried to obtain a powder; then the oxidized graphite in a tube furnace, the expansion time is 30S ~ 5min The temperature is reduced at 1300 to 1500 ° C to obtain primary expanded graphite, and the expanded graphite is treated in the same manner as above, and then expanded and expanded at a high temperature of 1300 to 1500 ° C to obtain secondary expanded graphite.
制备单层石墨烯分散液：将二次膨胀石墨、胆酸钠按质量比是3:1，混合得到混合分散体系；在混合分散体系中加入溶剂N-辛基吡咯烷酮，通过流体乳化机对混合最后得到的溶液在均质机(内装载球状研磨介质)中进行机械剪切，剪切速度为8000转/分钟，机械剪切的时间为30小时，得到单层石墨烯分散液，其中，5wt％的石墨烯、1.7wt％分散剂；所述石墨烯的直径为200纳米～8微米；Preparation of single-layer graphene dispersion: the secondary expanded graphite and sodium cholate are mixed at a mass ratio of 3:1 to obtain a mixed dispersion system; the solvent N-octylpyrrolidone is added to the mixed dispersion system, and the mixture is mixed by a fluid emulsifier The finally obtained solution was mechanically sheared in a homogenizer (loaded with a spherical grinding medium) at a shear rate of 8000 rpm and a mechanical shearing time of 30 hours to obtain a single layer graphene dispersion, wherein 5 wt % graphene, 1.7 wt% dispersant; the graphene has a diameter of 200 nm to 8 μm;
需要说明的是，在本实施例中，氧化剂还可以在浓硫酸、浓硝酸、高锰酸钾、氯酸钾中的一种或多种。It should be noted that, in this embodiment, the oxidizing agent may also be one or more of concentrated sulfuric acid, concentrated nitric acid, potassium permanganate, and potassium chlorate.
分散剂还可以选自：十二烷基苯磺酸钠、十二烷基磺酸钠、聚乙烯吡咯烷酮、聚苯乙烯、十六烷基三甲基溴化铵一种或多种，或胆酸钠和可替代的其他分散剂共用。
The dispersing agent may also be selected from one or more of sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, polystyrene, cetyltrimethylammonium bromide, or bile Sodium is shared with alternative dispersants.
溶剂还可以由以下物质替代：环戊酮、环己酮、哌啶-1-甲醛、乙烯基吡咯烷酮、1，3-二甲基-2-咪唑啉、溴苯、氰苯、苯甲基安息香酸、N，N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、二甲乙酰胺、环己基吡咯烷酮、苄醚、异丙醇、二氧戊环、乙酸乙酯、1-氮萘、安息香醛、乙醇胺、酞酸二乙酯、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、甲苯、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜、二氯代苯、氯仿、四氢呋喃的一种或多种。The solvent can also be replaced by cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone, 1,3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoin Acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, dioxolane, acetic acid Ethyl ester, 1-azinone, benzoic aldehyde, ethanolamine, diethyl decanoate, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl acetate, ethylene glycol, toluene, g One or more of an alkane, a pentane, a hexane, a formamide, a dimethylformamide, a dimethyl sulfoxide, a dichlorobenzene, a chloroform, and a tetrahydrofuran.
实施例4：Example 4:
制备二次膨胀石墨：将5g石墨放500mL的三口烧瓶中，将三口烧瓶浸到冰水混合物里，然后加入45mL的高锰酸钾和87.5mL的亚硝酸，将55g的氯酸钾缓慢的加到三口烧瓶中(至少加超过15min。注意：在加氯酸钾时会产生二氧化氯，浓度高时会产生***)，这个过程搅拌处理72h，用大量的水将处理的石墨洗成中性，干燥后获得粉末；然后对氧化后的石墨在管式炉中，膨胀时间30S～5min，温度在1300～1500℃情况下进行高温还原得到一次膨胀石墨，采用上述同样的方法处理一次膨胀石墨后高温还原膨胀得到二次膨胀石墨。Preparation of secondary expanded graphite: 5 g of graphite was placed in a 500 mL three-necked flask, and the three-necked flask was immersed in an ice-water mixture, then 45 mL of potassium permanganate and 87.5 mL of nitrous acid were added, and 55 g of potassium chlorate was slowly added to the three-neck. In the flask (at least more than 15min. Note: chlorine dioxide will be produced when potassium chlorate is added, and it will explode when the concentration is high). This process is stirred for 72h, and the treated graphite is washed with a large amount of water to be neutral. Powder; then the oxidized graphite in a tube furnace, the expansion time is 30S ~ 5min, the temperature is 1300 ~ 1500 ° C under high temperature reduction to obtain a primary expanded graphite, the same method is used to treat the expanded graphite after high temperature reduction expansion Secondary expansion of graphite.
制备单层石墨烯分散液：将二次膨胀石墨、十六烷基三甲基溴化铵按质量比5:1混合得到混合分散体系；又加入溶剂酞酸二乙酯；通过分散机(内含棒状研磨介质)对混合分散体系进行机械剪切，剪切速度为13500转/分钟，所述机械剪切的时间为4小时，得到单层石墨烯分散液，其中，1wt％的石墨烯、0.2wt％分散剂；所述石墨烯的直径为800纳米～5微米；Preparation of single-layer graphene dispersion: mixing secondary expanded graphite and cetyltrimethylammonium bromide in a mass ratio of 5:1 to obtain a mixed dispersion system; adding solvent diethyl ruthenate; passing through a dispersing machine The rod-shaped grinding medium was subjected to mechanical shearing at a shear rate of 13,500 rpm, and the mechanical shearing time was 4 hours to obtain a single-layer graphene dispersion, wherein 1 wt% of graphene, 0.2wt% dispersant; the graphene has a diameter of 800 nm to 5 microns;
需要说明的是，在本实施例中，氧化剂还可以在浓硝酸、浓硫酸、次氯酸、双氧水中的一种或多种。It should be noted that, in this embodiment, the oxidizing agent may also be one or more of concentrated nitric acid, concentrated sulfuric acid, hypochlorous acid, and hydrogen peroxide.
分散剂还可以选自：十二烷基苯磺酸钠、十二烷基磺酸钠、聚乙烯吡咯烷酮、胆酸钠、聚苯乙烯一种或多种，或十六烷基三甲基溴化铵和可替代的其他分散剂共用。
The dispersing agent may also be selected from sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, polyvinylpyrrolidone, sodium cholate, one or more polystyrenes, or cetyltrimethyl bromide. Ammonium is shared with alternative dispersants.
溶剂还可以由以下物质替代：环戊酮、环己酮、哌啶-1-甲醛、乙烯基吡咯烷酮、1，3-二甲基-2-咪唑啉、溴苯、氰苯、苯甲基安息香酸、N，N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、二甲乙酰胺、环己基吡咯烷酮、苄醚、异丙醇、N-辛基吡咯烷酮、二氧戊环、乙酸乙酯、1-氮萘、安息香醛、乙醇胺、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、甲苯、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜、二氯代苯、氯仿、四氢呋喃的一种或多种；或酞酸二乙酯和其他可替代的溶剂共用。The solvent can also be replaced by cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone, 1,3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoin Acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, N-octylpyrrolidone, Dioxolane, ethyl acetate, 1-azaphthalene, benzoin, ethanolamine, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl acetate, ethylene glycol, toluene, g One or more of an alkane, pentane, hexane, formamide, dimethylformamide, dimethyl sulfoxide, dichlorobenzene, chloroform, tetrahydrofuran; or diethyl phthalate and other alternative solvents Share.
该方法得到的石墨烯分散液浓度高、稳定性强、且为单层石墨烯片。此外，制备工艺简单、成本低，以及有利于产业化生产等优点。该获得的石墨烯分散液在光、电材料等领域具有潜在的实际应用价值。The graphene dispersion obtained by the method has high concentration and strong stability, and is a single-layer graphene sheet. In addition, the preparation process is simple, the cost is low, and the advantages of industrial production are favorable. The obtained graphene dispersion has potential practical application value in the fields of light and electric materials.
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，对于本领域的技术人员来说，本发明可以有各种更改和变化。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。
The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.
Claims (10)
- 一种单层石墨烯分散液的制备方法，其特征在于，包括：A method for preparing a single-layer graphene dispersion, comprising:步骤1，将石墨制备成二次膨胀石墨；Step 1, preparing graphite into secondary expanded graphite;步骤2，将所述二次膨胀石墨、分散剂按质量比5:1～1:5混合得到混合分散体系；Step 2, mixing the secondary expanded graphite and the dispersant at a mass ratio of 5:1 to 1:5 to obtain a mixed dispersion system;步骤3，将所述混合分散体系进行机械剪切剥离；Step 3, performing mechanical shear stripping on the mixed dispersion system;步骤4，得到单层石墨烯分散液。In step 4, a single layer of graphene dispersion is obtained.
- 如权利要求1所述的单层石墨烯分散液的制备方法，其特征在于，所述步骤2中，所述分散剂包括：十二烷基苯磺酸钠、十二烷基磺酸钠、聚乙烯吡咯烷酮、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵一种或多种。The method for preparing a single-layer graphene dispersion according to claim 1, wherein in the step 2, the dispersing agent comprises: sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, One or more of polyvinylpyrrolidone, sodium cholate, polystyrene, cetyltrimethylammonium bromide.
- 如权利要求1所述的单层石墨烯分散液的制备方法，其特征在于，所述步骤2中，所述混合分散体系还包括：水或溶剂；The method for preparing a single-layer graphene dispersion according to claim 1, wherein in the step 2, the mixed dispersion system further comprises: water or a solvent;所述溶剂包括：环戊酮、环己酮、哌啶-1-甲醛、乙烯基吡咯烷酮、1，3-二甲基-2-咪唑啉、溴苯、氰苯、苯甲基安息香酸、N，N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、二甲乙酰胺、环己基吡咯烷酮、苄醚、异丙醇、N-辛基吡咯烷酮、二氧戊环、乙酸乙酯、1-氮萘、安息香醛、乙醇胺、酞酸二乙酯、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、甲苯、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜、二氯代苯、氯仿、四氢呋喃的一种或多种。The solvent includes: cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinyl pyrrolidone, 1,3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoic acid, N , N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone, dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, N-octylpyrrolidone, dioxane Ring, ethyl acetate, 1-azinone, benzoic aldehyde, ethanolamine, diethyl decanoate, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl acetate, ethylene glycol, One or more of toluene, heptane, pentane, hexane, formamide, dimethylformamide, dimethyl sulfoxide, dichlorobenzene, chloroform, tetrahydrofuran.
- 如权利要求1所述的单层石墨烯分散液的制备方法，其特征在于，所述步骤3中，所述机械剪切采用的设备包括：球磨机、乳化机、分散机、研磨机、匀质机、流体对撞机中的一种或多种。 The method for preparing a single-layer graphene dispersion according to claim 1, wherein in the step 3, the equipment used for the mechanical shearing comprises: a ball mill, an emulsifier, a disperser, a grinder, and a homogenizer. One or more of a machine or a fluid collider.
- 如权利要求4所述的单层石墨烯分散液的制备方法，其特征在于，所述机械剪切的速度为2000～15000转/分钟，和/或，所述机械剪切的时间为1～30小时。The method for preparing a single-layer graphene dispersion according to claim 4, wherein the mechanical shearing speed is 2000 to 15000 rpm, and/or the mechanical shearing time is 1 to 30 hours.
- 如权利要求1-5任一项所述的单层石墨烯分散液的制备方法，其特征在于，所述步骤1中，所述二次膨胀石墨的制备方法包括：The method for preparing a single-layer graphene dispersion according to any one of claims 1 to 5, wherein in the step 1, the method for preparing the secondary expanded graphite comprises:步骤a.将所述石墨进行氧化处理；Step a. oxidizing the graphite;步骤b.将步骤a处理后的石墨进行膨胀处理；Step b. Expanding the graphite treated in step a;步骤c.将步骤b处理后的石墨再进行氧化处理；Step c. The graphite treated in step b is further subjected to oxidation treatment;步骤d.将步骤c处理后的石墨进行高温还原膨胀得到二次膨胀石墨。Step d. The graphite after the step c is subjected to high temperature reduction expansion to obtain secondary expanded graphite.
- 如权利要求6所述的单层石墨烯分散液的制备方法，其特征在于，所述步骤a中，在氧化处理中，其中石墨与氧化剂的质量比25:1～45:1，采用的氧化剂包括：硫酸、硝酸、高锰酸钾、氯酸钾、双氧水、次氯酸、亚硝酸中的一种或多种。The method for preparing a single-layer graphene dispersion according to claim 6, wherein in the step (a), in the oxidation treatment, the mass ratio of graphite to oxidant is 25:1 to 45:1, and the oxidizing agent is used. Including: one or more of sulfuric acid, nitric acid, potassium permanganate, potassium chlorate, hydrogen peroxide, hypochlorous acid, and nitrous acid.
- 如权利要求6所述的单层石墨烯分散液的制备方法，其特征在于，所述步骤d中，所述高温还原膨胀的温度为600～1800℃。The method for preparing a single-layer graphene dispersion according to claim 6, wherein in the step d, the temperature of the high-temperature reduction expansion is 600 to 1800 °C.
- 一种通过权利要求1-8任一项所述单层石墨烯分散液的制备方法制备的单层石墨烯分散液，其特征在于，包括：1～10wt％的石墨烯、0.01～5wt％分散剂；所述石墨烯分散液的浓度为10～60mg mL-1、石墨烯的直径为200纳米～10微米；所述分散剂为十二烷基苯磺酸钠、十二烷基磺酸钠、聚乙烯吡咯烷酮、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵一种或多种。A single-layer graphene dispersion prepared by the method for preparing a single-layer graphene dispersion according to any one of claims 1-8, comprising: 1 to 10 wt% of graphene, 0.01 to 5 wt% of dispersion The graphene dispersion has a concentration of 10 to 60 mg mL -1 , and the graphene has a diameter of 200 nm to 10 μm; the dispersant is sodium dodecylbenzenesulfonate or sodium dodecyl sulfate Or one or more of polyvinylpyrrolidone, sodium cholate, polystyrene, cetyltrimethylammonium bromide.
- 如权利要求9所述的单层石墨烯分散液，其特征在于，还包括：水或溶剂，所述溶剂包括：环戊酮、环己酮、哌啶-1-甲醛、乙烯基吡咯烷酮、1，3-二甲基-2-咪唑啉、溴苯、氰苯、苯甲基安息香酸、N，N-二甲基丙烯基脲酮、N-乙基-2-吡咯烷酮、N-甲基吡咯烷酮、二甲乙酰胺、环己基吡咯烷酮、苄醚、异丙醇、N-辛基吡咯烷酮、二氧戊环、乙酸乙酯、1-氮萘、安息香醛、乙醇胺、 酞酸二乙酯、N-十二烷基吡咯烷酮、吡啶、酞酸二甲酯、乙醇、丙酮、乙酸乙烯酯、乙二醇、甲苯、庚烷、戊烷、己烷、甲酰胺、二甲基甲酰胺、二甲基亚砜、二氯代苯、氯仿、四氢呋喃的一种或多种。 The single-layer graphene dispersion according to claim 9, further comprising: water or a solvent comprising: cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone, 1 ,3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoic acid, N,N-dimethylpropenyl ketone, N-ethyl-2-pyrrolidone, N-methylpyrrolidone , dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, N-octylpyrrolidone, dioxolane, ethyl acetate, 1-azaphthalene, benzoin, ethanolamine, Diethyl citrate, N-dodecylpyrrolidone, pyridine, dimethyl decanoate, ethanol, acetone, vinyl acetate, ethylene glycol, toluene, heptane, pentane, hexane, formamide, dimethyl One or more of carbenamide, dimethyl sulfoxide, dichlorobenzene, chloroform, and tetrahydrofuran.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342026A (en) * | 2018-03-23 | 2018-07-31 | 长春工业大学 | A method of graphene-poly styrene composite material is prepared by graphite and styrene |
| CN108704500A (en) * | 2018-04-04 | 2018-10-26 | 北京石墨烯技术研究院有限公司 | A kind of method that graphene disperses in metal powder |
| CN110015658A (en) * | 2019-03-21 | 2019-07-16 | 安徽工程大学 | A kind of water-based graphite alkene dispersion liquid and preparation method thereof |
| CN113387349A (en) * | 2021-05-12 | 2021-09-14 | 无锡启仁化工科技有限公司 | Method for efficiently preparing graphene sol |
| CN113800505A (en) * | 2021-08-02 | 2021-12-17 | 江苏杉元科技有限公司 | Graphene aqueous slurry and preparation method thereof |
| CN114560461A (en) * | 2022-03-23 | 2022-05-31 | 北京明湖华胜超导新材料技术研究院有限公司 | Preparation method for preparing single-layer graphene by biological agent |
| CN114804922A (en) * | 2021-01-21 | 2022-07-29 | 邓茜丹 | Hole sealing agent for copper plating pretreatment of gouging carbon rod and preparation method thereof |
| CN116375009A (en) * | 2022-12-26 | 2023-07-04 | 中国科学院福建物质结构研究所 | Preparation method of modified graphene |
| CN116462896A (en) * | 2023-04-18 | 2023-07-21 | 江苏馨德高分子材料股份有限公司 | Sheath material for low-smoke halogen-free flame-retardant optical cable and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993061A (en) * | 2009-08-19 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing high-quality graphene with controllable layer number |
| CN102167311A (en) * | 2011-03-09 | 2011-08-31 | 华侨大学 | Method for preparing graphene on large scale |
| CN103935997A (en) * | 2014-05-10 | 2014-07-23 | 由伟 | Method for producing graphene based on sodium dodecylbenzene sulfonate |
| CN104151582A (en) * | 2014-07-17 | 2014-11-19 | 哈尔滨工业大学 | Method for preparing graphene-polyimide conductive black film |
| CN104495826A (en) * | 2014-12-25 | 2015-04-08 | 北京航空航天大学 | Single-layer graphene dispersion liquid and preparation method thereof |
-
2014
- 2014-12-25 WO PCT/CN2014/094949 patent/WO2016101208A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993061A (en) * | 2009-08-19 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing high-quality graphene with controllable layer number |
| CN102167311A (en) * | 2011-03-09 | 2011-08-31 | 华侨大学 | Method for preparing graphene on large scale |
| CN103935997A (en) * | 2014-05-10 | 2014-07-23 | 由伟 | Method for producing graphene based on sodium dodecylbenzene sulfonate |
| CN104151582A (en) * | 2014-07-17 | 2014-11-19 | 哈尔滨工业大学 | Method for preparing graphene-polyimide conductive black film |
| CN104495826A (en) * | 2014-12-25 | 2015-04-08 | 北京航空航天大学 | Single-layer graphene dispersion liquid and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| GUO, XIAOQIN ET AL.: "Few-layer Graphene Nanosheets Produced by Ultrasonic Exfoliation of Secondary Expanded Graphene", JOURNAL OF FUNCTIONAL MATERIALS, vol. 44, no. 12, 31 December 2013 (2013-12-31), pages 1800 - 1803 * |
| GUO, XIAOQIN ET AL.: "Preparation and Characterization of Graphene Nanoplatelets", NEW CHEMICAL MATERIALS, vol. 41, no. 7, 31 July 2013 (2013-07-31), pages 128 - 130 * |
| KNIEKE, C. ET AL.: "Scalable production of graphene sheets by mechanical delamination", CARBON, vol. 48, no. 11, 12 May 2010 (2010-05-12), pages 3196 - 3204 * |
| SHULUN ET AL.: "Research Progress of Preparation of Graphene", ADHESION, 10 December 2013 (2013-12-10), pages 084 - 088 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342026A (en) * | 2018-03-23 | 2018-07-31 | 长春工业大学 | A method of graphene-poly styrene composite material is prepared by graphite and styrene |
| CN108704500A (en) * | 2018-04-04 | 2018-10-26 | 北京石墨烯技术研究院有限公司 | A kind of method that graphene disperses in metal powder |
| CN110015658A (en) * | 2019-03-21 | 2019-07-16 | 安徽工程大学 | A kind of water-based graphite alkene dispersion liquid and preparation method thereof |
| CN114804922A (en) * | 2021-01-21 | 2022-07-29 | 邓茜丹 | Hole sealing agent for copper plating pretreatment of gouging carbon rod and preparation method thereof |
| CN113387349A (en) * | 2021-05-12 | 2021-09-14 | 无锡启仁化工科技有限公司 | Method for efficiently preparing graphene sol |
| CN113800505A (en) * | 2021-08-02 | 2021-12-17 | 江苏杉元科技有限公司 | Graphene aqueous slurry and preparation method thereof |
| CN113800505B (en) * | 2021-08-02 | 2023-07-25 | 江苏杉元科技有限公司 | Graphene aqueous slurry and preparation method thereof |
| CN114560461A (en) * | 2022-03-23 | 2022-05-31 | 北京明湖华胜超导新材料技术研究院有限公司 | Preparation method for preparing single-layer graphene by biological agent |
| CN116375009A (en) * | 2022-12-26 | 2023-07-04 | 中国科学院福建物质结构研究所 | Preparation method of modified graphene |
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