WO2016173111A1

WO2016173111A1 - Graphene dispersing agent and preparation method therefor

Info

Publication number: WO2016173111A1
Application number: PCT/CN2015/082577
Authority: WO
Inventors: 朱英; 王建峰; 滕超; 江雷
Original assignee: 北京天恒盛通科技发展有限公司
Priority date: 2015-04-29
Filing date: 2015-06-26
Publication date: 2016-11-03
Also published as: CN104959050A

Abstract

Provided are a graphene dispersing agent and a preparation method therefor. The concentration of the graphene dispersing agent is 1 mg/mL to 60 mg/mL, wherein the content of the dispersing agent is 0 to 6% (by weight), and the length of a graphene sheet is 100 nm to 6000 nm. The method for preparing the graphene dispersing agent comprises: providing a graphene material; adding a dispersing agent into a solvent to form a solution; mixing the graphene material with the solution to form a uniform solution; and adding the mixed solution to a grinding device using balls, bars or sections as mediums, performing grinding for 1 h to 100 h, so as to obtain a graphene dispersing agent. The obtained graphene dispersing agent has good stability and a high dispersion concentration.

Description

说明书一种石墨烯分散液及其制备方法 Graphene dispersion liquid and preparation method thereof

技术领域 Technical field

[0001] 本发明属于纳米材料技术领域，尤其涉及高分散、高稳定、高浓度、高产率的石墨烯分散液，以及以球或棒或段为介质的研磨设备制备石墨烯分散液的方法背景技术 [0001] The present invention belongs to the field of nano material technology, and particularly relates to a high dispersion, high stability, high concentration, high yield graphene dispersion, and a method for preparing a graphene dispersion by using a ball or rod or a segment as a medium grinding device. Technology

[0002] 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"二维石墨烯材料的幵创性实验"，共同获得 2010年诺贝尔物理学奖，拉幵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 sp ²形式杂化。石墨烯的比表面积高达 2630 m 2/g，是单壁纳米碳管的两倍；常温下电子迁移率超过 200000 cm ²/V.s，比单晶硅都高；导热系数高达 5300 W/nvK，高于金刚石；电阻率只有 10 ⁶ [0002] In 2004, Physicist Andrei Heim and Konstantin of the University of Manchester in the United Kingdom, Novoselov, successfully separated graphene from graphite in experiments, and confirmed that it can exist alone, due to The two men won the 2010 Nobel Prize in Physics for the "Invasive Experiment of Two-Dimensional Graphene Materials" and pulled 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 . Graphene has a specific surface area of up to 2630 m 2 /g, which is twice that of single-walled carbon nanotubes; electron mobility at room temperature exceeds 200,000 cm ² /Vs, which is higher than that of single crystal silicon; thermal conductivity is as high as 5300 W/nvK, high In diamond; resistivity is only 10 ⁶

Q 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 1000 GPa，是钢的 2 00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。 Q 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 nanomaterial in the world, and its intensity can reach 1000 GPa. It is 200 times that of steel. These excellent properties of graphene make it a potential application in gas sensors, optoelectronic devices, chemical energy (solar cells, lithium-ion batteries), catalysts, antistatic and other fields.

[0003] 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、稳定的石墨烯分散液在众多研究领域中具有重要的应用，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。 [0003] 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 graphite. On the surface of the olefin, monolayer dispersion of graphene is achieved by means of intermolecular forces or electrostatic repulsion forces. Uniform and stable graphene dispersions have important applications in many fields of research, but the concentration of graphene dispersions reported so far is low, which limits the industrialization of graphene.

[0004] 现有的石墨烯分散液的主要方法有：直接将石墨或石墨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 J. N. Coleman等研究者 (U. Khan, , A. O'Neill, M. Lotya, S. De, J. N. Coleman, Small, 6, 864-871.)将片状的石墨分散到溶剂 NMP 中，利用超声波超声 460 h，得到石墨烯的浓度是 3.3 mg L -i .这种方法得到的石墨烯分散液浓度低，超声吋间长，严重限制了工业生产和需求。分散还原氧化石墨烯， Dan Li等研究者（Dan Li, Marc B. Muller, Scott Gilje, Richard B. Kaner, Gordon G. Wallace. Nature Nanotechnology, 2008, 3, 101-105.) 将氧化石墨 ¾7_ 溶液用一定量的水合肼和氨水溶液 95°C还原 lh，得到浓度是 0.5 mg-L -i的石墨烯分散液，这种方法得到的石墨烯分散液浓度低且稳定性很差，不能满足工业的各种需求。此外，现有石墨烯分散液的制备主要以石墨烯为原料，将石墨烯分散在溶剂中，因此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结构存在，难以获得寡层的石墨烯分散液。 [0004] The main methods of the existing graphene dispersion are: directly dispersing graphite or graphite and a surface active mixture under ultrasonic water bath conditions. For example, researchers such as JN Coleman (U. Khan, , A. O'Neill, M. Lotya, S. De, JN Coleman, Small, 6, 864-871.) Disperse the flake graphite into the solvent NMP and use ultrasonic sonication for 460 h to obtain a graphene concentration of 3.3 mg L -i. The graphene dispersion obtained by the method has a low concentration and a long inter-electron length, which severely limits industrial production and demand. Dispersion-reduced graphene oxide, Dan Li et al. (Dan Li, Marc B. Muller, Scott Gilje, Richard B. Kaner, Gordon G. Wallace. Nature Nanotechnology, 2008, 3, 101-105.) Graphite oxide 3⁄47_ solution It is reduced by a certain amount of hydrazine hydrate and ammonia solution at 95 ° C for 1 h to obtain a graphene dispersion with a concentration of 0.5 mg-L -i. The graphene dispersion obtained by this method has a low concentration and poor stability and cannot meet the industrial requirements. Various needs. In addition, the existing graphene dispersion is mainly prepared by using graphene as a raw material and dispersing graphene in a solvent. Therefore, the preparation cost of the graphene dispersion is high, 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 multilayer structure, and it is difficult to obtain the graphene dispersion of the oligo layer.

技术问题 technical problem

[0005] 因此，针对上述技术问题，本发明的目的在于提供一种高分散、高稳定、高浓度、高产率的寡层石墨烯分散液。所述的石墨烯分散液浓度是： l mg/mL~100 mg/mL, 其中分散剂含量 0~6 % (重量)；石墨烯片的长度是 100-6000 nm。 Accordingly, in view of the above technical problems, an object of the present invention is to provide a highly dispersed, highly stable, high-concentration, high-yield oligo-layer graphene dispersion. The concentration of the graphene dispersion is: l mg/mL to 100 mg/mL, wherein the dispersant content is 0-6 wt%; the length of the graphene sheet is 100-6000 nm.

[0006] 本发明的另一目的在于提出一种制备高分散、高稳定、高浓度、高产率的石墨烯分散液的方法，步骤包括：将石墨原料、分散剂及水或者各种溶剂形成混合溶液后，通过以球或棒或段为介质的研磨设备所形成的机械剪切力将团聚的石墨进行分离，形成大量分散的石墨烯分散液。 Another object of the present invention is to provide a method for preparing a highly dispersed, highly stable, high concentration, high yield graphene dispersion, the steps comprising: mixing a graphite raw material, a dispersing agent, and water or various solvents. After the solution, the agglomerated graphite is separated by mechanical shearing force formed by a grinding device of a ball or a rod or a segment to form a large amount of dispersed graphene dispersion.

问题的解决方案 Problem solution

技术解决方案 Technical solution

[0007] 本发明通过以下技术方案实现。 The present invention is achieved by the following technical solutions.

[0008] 一种石墨烯分散液，包括石墨烯、分散剂和溶剂，其特征在于，所述的石墨烯分散液浓度是： 1 mg/mL〜60 mg/mL，其中分散剂含量 0〜6 <¾ (重量)；石墨烯片的长度是 100〜6000 nm。 [0008] A graphene dispersion comprising graphene, a dispersant and a solvent, wherein the graphene dispersion concentration is: 1 mg/mL to 60 mg/mL, wherein the dispersant content is 0 to 6 <3⁄4 (by weight); The length of the graphene sheet is 100 to 6000 nm.

[0009] 优选地，所述石墨烯为寡层石墨烯。 [0009] Preferably, the graphene is an oligo-layer graphene.

[0010] 优选地，所述的分散剂为：十二烷基苯磺酸钠、十二烷基磺酸钠、对苯乙烯磺酸钠、聚对苯乙烯磺酸钠、木质素磺酸钠、十二烷基硫酸钠、聚乙烯吡咯烷酮、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵、聚乙烯醇、吐温 80中的一种或两种。 [0010] Preferably, the dispersing agent is: sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, sodium p-styrenesulfonate, sodium polypyristate, sodium lignosulfonate , sodium lauryl sulfate, polyvinylpyrrolidone One or two of sodium cholate, polystyrene, cetyltrimethylammonium bromide, polyvinyl alcohol, and Tween 80.

[0011] 优选地，所述的溶剂为水、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、 Ν,Ν-二甲基丙烯基脲酮、 Ν-乙基 -2-吡咯烷酮、 Ν-甲基吡咯烷酮、二甲乙酰胺、环己基吡咯烷酮、苄醚、异丙醇、 Ν-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、 Ν-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、庚院、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。 [0011] Preferably, the solvent is water, cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinyl pyrrolidone, 1,3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene , benzyl benzoic acid, hydrazine, hydrazine-dimethylpropenyl ketone, hydrazine-ethyl-2-pyrrolidone, hydrazine-methylpyrrolidone, dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, hydrazine - octylpyrrolidone, dioxolane, ethyl acetate, 1-nitrogen naphthalene, benzoin, ethanolamine, diethyl phthalate, decyl-dodecylpyrrolidone, pyridine, dimethyl decanoate, ethanol, acetone, One or more of vinyl acetate, ethylene glycol, toluene, gemamine, pentane, hexane, formamide, dimethylformamide, dimethyl sulfoxide, dichlorobenzene, chloroform, tetrahydrofuran.

[0012] 一种制备根据以上技术方案中任一项所述的石墨烯分散液的方法，所述方法的步骤包括： [0012] A method of preparing a graphene dispersion according to any one of the preceding claims, wherein the method comprises the steps of:

[0013] 将石墨原料、分散剂及溶剂形成混合溶液； [0013] forming a graphite raw material, a dispersing agent and a solvent into a mixed solution;

[0014] 将上述混合溶液加入到以球或棒或段为介质的研磨设备中，研磨吋间为 1〜100 h，得到石墨烯分散液。 [0014] The above mixed solution is added to a grinding apparatus using a ball or a rod or a segment as a medium, and the grinding crucible is 1 to 100 hours to obtain a graphene dispersion.

[0015] 通过以球或棒或段为介质的研磨设备所形成的机械剪切力将团聚的石墨进行剥离，形成寡层石墨烯。 [0015] The agglomerated graphite is peeled off by mechanical shearing force formed by a grinding apparatus using a ball or a rod or a segment as a medium to form an oligo-layer graphene.

[0016] 优选地，所述石墨烯为寡层石墨烯。 [0016] Preferably, the graphene is an oligo-layer graphene.

[0017] 优选地，所述的石墨原料为鳞片石墨 [0017] Preferably, the graphite raw material is flake graphite

[0018] 优选地，所述的石墨原料为可膨胀石墨。 [0018] Preferably, the graphite raw material is expandable graphite.

[0019] 优选地，所述的石墨原料为一次膨胀石墨。 [0019] Preferably, the graphite raw material is primary expanded graphite.

[0020] 优选地，所述的以球或棒或段为介质的研磨设备为：球磨机、砾磨机、砂磨机 [0020] Preferably, the grinding device with a ball or a rod or a segment as a medium is: a ball mill, a gravel mill, a sand mill

、棒磨机等中的一种或多种。 One or more of a rod mill, and the like.

[0021] 优选地，所述的球或棒或段的种类为砾石、卵石、瓷球、玛瑙球、合金球、氧化铁球、钢球、钢棒、氧化铜球、氧化锆球、氧化铝球、合金棒、氧化铁棒、氧化铜棒、氧化锆棒、氧化铝棒、钢段、合金段、氧化铜段、氧化铝段、氧化铁段、氧化锆段中的一种或几种。 [0021] Preferably, the type of the ball or rod or segment is gravel, pebbles, porcelain balls, agate balls, alloy balls, iron oxide balls, steel balls, steel rods, copper oxide balls, zirconia balls, alumina One or more of a ball, an alloy rod, an iron oxide rod, a copper oxide rod, a zirconia rod, an alumina rod, a steel segment, an alloy segment, a copper oxide segment, an alumina segment, an iron oxide segment, and a zirconia segment.

[0022] 优选地，所述球的直径为 0.01mm〜100 mm。 [0022] Preferably, the ball has a diameter of 0.01 mm to 100 mm.

[0023] 优选地，所述棒的直径为 0.01 mm— 200 mm,长度为 0.1 mm— 200 mm。 [0024] 优选地，所述的段的直径为 0.01 mm〜100 mm。 [0023] Preferably, the rod has a diameter of 0.01 mm to 200 mm and a length of 0.1 mm to 200 mm. [0024] Preferably, the segment has a diameter of 0.01 mm to 100 mm.

发明的有益效果 Advantageous effects of the invention

有益效果 Beneficial effect

[0025] 该方法得到的石墨烯分散液浓度高、稳定性强、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。 [0025] The graphene dispersion obtained by the method has the advantages of high concentration, strong stability, simple preparation process, low cost, and favorable industrial production. The obtained graphene dispersion has potential practical application value in the fields of light and electric materials.

对附图的简要说明 Brief description of the drawing

附图说明 DRAWINGS

[0026] 图 1为实施例 1中所得到的石墨烯分散液光学照片。 1 is an optical photograph of a graphene dispersion obtained in Example 1.

[0027] 图 2为实施例 1中获得的石墨烯片的透射电镜照片。 2 is a transmission electron micrograph of the graphene sheet obtained in Example 1.

本发明的实施方式 Embodiments of the invention

[0028] 实施例 1 Embodiment 1

[0029] ( 1) 取 10 g制备石墨粉的原料。 [0029] (1) Take 10 g of a raw material for preparing graphite powder.

[0030] (2) 取 0.5 g的对苯乙烯磺酸钠加入到 180 mL的 N-甲基吡咯烷酮里，搅拌 15 min至完全溶解。 [0030] (2) 0.5 g of sodium p-styrenesulfonate was added to 180 mL of N-methylpyrrolidone and stirred for 15 min until completely dissolved.

[0031] (3) 将步骤 1中的石墨粉原料与步骤 2中的溶液混合，形成均匀的混合物。 (3) The graphite powder raw material in the step 1 is mixed with the solution in the step 2 to form a homogeneous mixture.

[0032] (4) 取步骤（3) 的混合液加入到以球或棒或段为介质的研磨设备中，研磨 10 h，即可以得到浓度 50 mg/mL的寡层石墨烯。 [0032] (4) The mixture of the step (3) is added to a grinding apparatus using a ball or a rod or a segment as a medium, and after grinding for 10 hours, an oligo-layer graphene having a concentration of 50 mg/mL can be obtained.

[0033] 所述的原料为：石墨、可膨胀石墨、一次膨胀石墨。 [0033] The raw materials are: graphite, expandable graphite, primary expanded graphite.

[0034] 所述的分散剂为：十二烷基苯磺酸钠、十二烷基磺酸钠、对苯乙烯磺酸钠、聚对苯乙烯磺酸钠、木质素磺酸钠、十二烷基硫酸钠、聚乙烯吡咯烷酮、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵、聚乙烯醇、吐温 80的一种或两种； [0034] The dispersing agent is: sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, sodium p-styrenesulfonate, sodium polypyristate, sodium lignosulfonate, twelve One or both of sodium alkyl sulfate, polyvinylpyrrolidone, sodium cholate, polystyrene, cetyltrimethylammonium bromide, polyvinyl alcohol, Tween 80;

[0035] 所述的溶剂为水、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、 Ν,Ν-二甲基丙烯基脲酮、 Ν-乙基- 2-吡咯烷酮、 Ν-甲基吡咯烷酮、二甲乙酰胺、环己基吡咯烷酮、苄醚、异丙醇、 Ν-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、庚院、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； [0035] The solvent is water, cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinyl pyrrolidone, 1,3-dimethyl- _2- imidazoline, bromobenzene, cyanobenzene, benzo Kean acid, hydrazine, hydrazine-dimethylpropenyl ketone, hydrazine-ethyl-2-pyrrolidone, hydrazine-methylpyrrolidone, dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, oxime-octyl Pyrrolidone, dioxolane, ethyl acetate, 1-nitrogen naphthalene, benzoin, ethanolamine, bismuth citrate Ester, N-dodecylpyrrolidone, pyridine, dimethyl decanoate, ethanol, acetone, vinyl acetate, ethylene glycol, toluene, gamma, pentane, hexane, formamide, dimethylformamide, One or more of dimethyl sulfoxide, dichlorobenzene, chloroform, tetrahydrofuran;

[0036] 所述的以球或棒或段为介质的研磨设备为：球磨机、砾磨机、砂磨机、棒磨机等中的一种或多种。 [0036] The grinding device using a ball or a rod or a segment as a medium is one or more of a ball mill, a gravel mill, a sand mill, a rod mill, and the like.

[0037] 所述的球或棒或段的种类为砾石、卵石、瓷球、玛瑙球、合金球、氧化铁球、钢球、钢棒、氧化铜球、氧化锆球、氧化铝球、合金棒、氧化铁棒、氧化铜棒、氧化锆棒、氧化铝棒、钢段、合金段、氧化铜段、氧化铝段、氧化铁段、氧化锆段中的一种或几种。 [0037] The type of the ball or rod or segment is gravel, pebbles, porcelain balls, agate balls, alloy balls, iron oxide balls, steel balls, steel rods, copper oxide balls, zirconia balls, alumina balls, alloys. One or more of a rod, an iron oxide rod, a copper oxide rod, a zirconia rod, an alumina rod, a steel segment, an alloy segment, a copper oxide segment, an alumina segment, an iron oxide segment, and a zirconia segment.

[0038] 所述球的直径为 0.01mm〜100 mm。 [0038] The diameter of the ball is 0.01 mm to 100 mm.

[0039] 所述棒的直径为 0.01 mm〜200 mm,长度为 0.1 mm〜200 mm。 [0039] The rod has a diameter of 0.01 mm to 200 mm and a length of 0.1 mm to 200 mm.

[0040] 所述的段的直径为 0.01 mm〜100 mm。 [0040] The segment has a diameter of 0.01 mm to 100 mm.

[0041] 所得到的石墨烯分散液光学照片如图 1所示，获得的石墨烯片的透射电镜照片如图 2所示。 [0041] An optical photograph of the obtained graphene dispersion liquid is shown in Fig. 1, and a transmission electron micrograph of the obtained graphene sheet is shown in Fig. 2.

[0042] 以上所述的实施例，只是本发明较优选的具体实施方式的一种，本领域的技术人员在本发明技术方案范围内进行的变化和替换都应包含在本发明的保护范围内。 The above-mentioned embodiments are only one of the more preferred embodiments of the present invention, and variations and substitutions made by those skilled in the art within the scope of the technical solutions of the present invention are included in the protection scope of the present invention. .

Claims

权利要求书 Claim

一种石墨烯分散液，包括石墨烯、分散剂和溶剂，其特征在于，所述的石墨烯分散液浓度是： l mg/mL〜60 mg/mL，其中分散剂含量 0〜6 % (重量)；石墨烯片的长度是 100〜6000 nm。 A graphene dispersion comprising graphene, a dispersant and a solvent, wherein the graphene dispersion has a concentration of: l mg/mL to 60 mg/mL, wherein the dispersant content is 0 to 6 % (weight) The length of the graphene sheet is 100 to 6000 nm.

根据权利要求 1所述的石墨烯分散液，其特征在于，所述石墨烯为寡层石墨烯。 The graphene dispersion according to claim 1, wherein the graphene is an oligo Graphene.

根据权利要求 1或 2所述的石墨烯分散液，其特征在于，所述的分散剂为：十二烷基苯磺酸钠、十二烷基磺酸钠、对苯乙烯磺酸钠、聚对苯乙烯磺酸钠、木质素磺酸钠、十二烷基硫酸钠、聚乙烯吡咯烷酮、胆酸钠、聚苯乙烯、十六烷基三甲基溴化铵、聚乙烯醇、吐温 80中的一种或两种。 The graphene dispersion according to claim 1 or 2, wherein the dispersing agent is: sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, sodium p-styrenesulfonate, poly Sodium p-styrene sulfonate, sodium lignosulfonate, sodium lauryl sulfate, polyvinylpyrrolidone, sodium cholate, polystyrene, cetyltrimethylammonium bromide, polyvinyl alcohol, Tween 80 One or two of them.

根据权利要求 1或 2所述的石墨烯分散液，其特征在于，所述的溶剂为水、环戊酮、环己酮、哌啶 -1-甲醛、乙烯基吡咯烷酮、 1, The graphene dispersion according to claim 1 or 2, wherein the solvent is water, cyclopentanone, cyclohexanone, piperidine-1-carbaldehyde, vinylpyrrolidone, 1,

3-二甲基 -2-咪唑啉、溴苯、氰苯、苯甲基安息香酸、 Ν, Ν-二甲基丙烯基脲酮、 Ν-乙基 -2-吡咯烷酮、 Ν-甲基吡咯烷酮、二甲乙酰胺、环己基吡咯烷酮、苄醚、异丙醇、 Ν-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、 Ν-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、庚院、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。 3-dimethyl-2-imidazoline, bromobenzene, cyanobenzene, benzyl benzoic acid, hydrazine, hydrazine-dimethylpropenyl ketone, hydrazine-ethyl-2-pyrrolidone, hydrazine-methylpyrrolidone, Dimethylacetamide, cyclohexylpyrrolidone, benzyl ether, isopropanol, decyl-octylpyrrolidone, dioxolane, ethyl acetate, 1-nitrogen naphthalene, benzoin, ethanolamine, diethyl citrate, cesium-tweldium Alkyl pyrrolidone, pyridine, dimethyl decanoate, ethanol, acetone, vinyl acetate, ethylene glycol, toluene, gamma, pentane, hexane, formamide, dimethylformamide, dimethyl sulfoxide, One or more of dichlorobenzene, chloroform, and tetrahydrofuran.

一种制备根据权利要求 1-4中任一项所述的石墨烯分散液的方法，所述方法的步骤包括： A method of preparing a graphene dispersion according to any one of claims 1 to 4, the steps of the method comprising:

提供石墨原料； Providing graphite raw materials;

将分散剂加入到溶剂中形成溶液； Adding a dispersing agent to the solvent to form a solution;

将石墨原料与所述溶液混合，形成均匀的混合液； Mixing the graphite raw material with the solution to form a uniform mixed liquid;

将所述混合液加入到以球或棒或段为介质的研磨设备中，研磨吋间为Adding the mixture to a grinding device using a ball or rod or a segment as a medium, grinding the crucible

1-100 h，得到石墨烯分散液。 1-100 h, a graphene dispersion was obtained.

根据权利要求 5所述的方法，其特征在于，所述石墨烯为寡层石墨烯 [权利要求 7] 根据权利要求 5所述的方法，其特征在于，所述的石墨原料为鳞片石墨或可膨胀石墨。 The method according to claim 5, wherein the graphene is an oligo-graphene [Clave 7] The method according to claim 5, wherein the graphite raw material is flake graphite or expandable graphite.

[权利要求 8] 根据权利要求 5所述的方法，其特征在于，所述的石墨原料为一次膨胀石墨。 [Claim 8] The method according to claim 5, wherein the graphite raw material is primary expanded graphite.

[权利要求 9] 根据权利要求 5所述的方法，其特征在于，所述的以球或棒或段为介质的研磨设备为：球磨机、砾磨机、砂磨机、棒磨机中的一种或多种 [Claim 9] The method according to claim 5, wherein the grinding device using a ball or a rod or a segment as a medium is: one of a ball mill, a gravel mill, a sand mill, and a rod mill Kind or more

[权利要求 10] 根据权利要求 5-9任一项所述的方法，其特征在于，所述的球或棒或段的种类为砾石、卵石、瓷球、玛瑙球、合金球、氧化铁球、钢球、钢棒、氧化铜球、氧化锆球、氧化铝球、合金棒、氧化铁棒、氧化铜棒、氧化锆棒、氧化铝棒、钢段、合金段、氧化铜段、氧化铝段、氧化铁段、氧化锆段中的一种或多种。 [Claim 10] The method according to any one of claims 5-9, wherein the type of the ball or the rod or the segment is gravel, pebbles, porcelain balls, agate balls, alloy balls, iron oxide balls , steel ball, steel rod, copper oxide ball, zirconia ball, alumina ball, alloy rod, iron oxide rod, copper oxide rod, zirconia rod, alumina rod, steel segment, alloy segment, copper oxide segment, alumina One or more of a segment, an iron oxide segment, and a zirconia segment.