WO2019184289A1

WO2019184289A1 - Method for preparing high-fluidity graphene conductive paste

Info

Publication number: WO2019184289A1
Application number: PCT/CN2018/109030
Authority: WO
Inventors: 赵永彬; 苏凯民; 吴开付; 马立军; 殷玉强; 张在忠
Original assignee: 山东欧铂新材料有限公司
Priority date: 2018-03-29
Filing date: 2018-09-30
Publication date: 2019-10-03
Also published as: CN110322986A; CN110322986B

Abstract

A method for preparing graphene conductive paste, comprising the following steps: first stripping graphite dispersion liquid under an ultrasonic condition, and then separating to obtain a graphene nanosheet; then mixing the obtained graphene nanosheet, a dispersing agent, and a solvent to obtain a pre-paste; and finally sanding and beating the obtained pre-paste to obtain the graphene conductive paste. A low-temperature and normal-pressure liquid-phase stripping method is selected. A method for graphite-solvent mixing, ultrasonic dispersion, and wet sanding is adopted. The graphene nanosheet is prepared, and then flowing graphene conductive paste is prepared. Graphene can be quickly prepared under mild conditions at a low cost. Moreover, the prepared graphene has a complete laminated structure without surficial decoration, maintains the intrinsic characteristics of a two-dimensional slice layer, has high conductivity and fluidity, and can be applied to the field of lithium batteries, supercapacitors, conductive coatings, etc. as a conductive additive.

Description

一种高流动性石墨烯导电浆料的制备方法Method for preparing high-flow graphene conductive paste

本申请要求于2018年03月29日提交中国专利局、申请号为201810272675.X、发明名称为“一种高流动性石墨烯导电浆料的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。The present application claims priority to Chinese Patent Application No. 201, 810, 272, 675, s, filed on March 29, 2018, and entitled "Preparation of a Highly Flowing Graphene Conductive Paste", all of which are The content is incorporated herein by reference.

技术领域Technical field

本发明属于石墨烯技术领域，涉及一种石墨烯导电浆料的制备方法，尤其涉及一种高流动性石墨烯导电浆料的制备方法。The invention belongs to the technical field of graphene, and relates to a preparation method of a graphene conductive paste, in particular to a method for preparing a high fluidity graphene conductive paste.

背景技术Background technique

石墨烯是由单层碳原子六方紧密堆积而成的二维晶体材料，厚度约为0.335纳米，具有完美的晶体结构，具有超强的导电性能，是目前导电性最好的材料，其理论电子迁移率为200000cm2/V.S，理论热导率为5000W/m.K。石墨烯因其具有导电性、超高的比表面积、独特的二维网状结构、高强度及高电子迁移率等优异的性能，引起了人们的广泛关注，进而也促进了石墨烯制备技术的快速发展。正是由于具有上述诸多的优异物理化学性质，其在储能材料，环境工程，灵敏传感方面被广泛应用，被称为“黑金”或是“新材料之王”，而且潜在的应用前景广大，目前已成为全世界的关注焦点与研究热点。Graphene is a two-dimensional crystal material composed of hexagonal packing of a single layer of carbon atoms. It has a thickness of about 0.335 nm. It has a perfect crystal structure and excellent electrical conductivity. It is the most conductive material and its theoretical electrons. The mobility was 200,000 cm 2 /VS, and the theoretical thermal conductivity was 5000 W/mK. Graphene has attracted much attention due to its excellent properties such as electrical conductivity, ultra-high specific surface area, unique two-dimensional network structure, high strength and high electron mobility, which has also promoted graphene preparation technology. Rapid development. Because of its excellent physical and chemical properties, it is widely used in energy storage materials, environmental engineering, and sensitive sensing. It is called “black gold” or “king of new materials” and has potential applications. At present, it has become the focus of attention and research hotspots around the world.

为实现石墨烯的此类应用，能够制备具有优异性能石墨烯的制备方法就成为必须的任务。然而在实际应用中，石墨烯的制备就是制约石墨烯实际应用和发展的一个主要障碍。虽然至今科研人员已开发出众多的石墨烯制备方法。其中比较主流的方法有氧化石墨还原法、外延生长法和化学气相沉积法(CVD)等。氧化石墨还原法是目前制备石墨烯的最佳方法之一，是将天然石墨与强酸和强氧化性物质反应生成氧化石墨，经过超声分散制备成氧化石墨烯(单层氧化石墨)，加入还原剂去除氧化石墨表面的含氧基团，如羧基、环氧基和羟基，得到石墨烯。该方法操作简单、制备成本低，可以大规模的制备出石墨烯，但因其在制备过程中引入强氧化剂浓硫酸或高锰酸钾等，不可避免地破坏了石墨烯的晶格结构，引入大量缺陷，从而导致石墨烯本征性能的严重缺失。In order to achieve such applications of graphene, it is an essential task to prepare a method for preparing graphene having excellent properties. However, in practical applications, the preparation of graphene is a major obstacle to the practical application and development of graphene. Although researchers have developed a number of graphene preparation methods to date. Among the more mainstream methods are graphite oxide reduction, epitaxial growth and chemical vapor deposition (CVD). The graphite oxide reduction method is one of the best methods for preparing graphene. It is to react natural graphite with strong acid and strong oxidizing substances to form graphite oxide. After ultrasonic dispersion, it is prepared into graphene oxide (single layer of graphite oxide) and added with reducing agent. The oxygen-containing groups on the surface of the graphite oxide, such as a carboxyl group, an epoxy group, and a hydroxyl group, are removed to obtain graphene. The method has the advantages of simple operation, low preparation cost, and can prepare graphene on a large scale, but the introduction of a strong oxidant concentrated sulfuric acid or potassium permanganate in the preparation process inevitably destroys the lattice structure of graphene, and introduces A large number of defects lead to a serious lack of intrinsic properties of graphene.

化学气相沉积法(Chemical Vapor Deposition，CVD)是指反应物质在气态条件下发生化学反应，生成固态物质沉积在加热的固态基体表面，进而制得固体材料的工艺技术。用外延生长法和化学气相沉积法虽然能够得到晶格完整、少缺陷的高品质大面积的石墨烯，但其制备成本昂贵、产率低、制备工艺要求苛刻，无法满足大规模生产的商业需要。因而上述的这些制备方法还不能满足现实中高品质石墨烯产业化的要求。Chemical Vapor Deposition (CVD) refers to a process in which a reaction substance undergoes a chemical reaction under a gaseous condition to form a solid substance deposited on the surface of a heated solid substrate to produce a solid material. Although epitaxial growth method and chemical vapor deposition method can obtain high quality and large area graphene with complete lattice and less defects, the preparation cost is high, the yield is low, the preparation process is demanding, and the commercial needs of large-scale production cannot be satisfied. . Therefore, the above preparation methods cannot meet the requirements of the industrialization of high-quality graphene in reality.

溶剂剥离法是最近两年才提出的，它的原理是将少量的石墨分散于溶剂中，形成低浓度的分散液，在高温高压下进行插层反应，破坏石墨层间的范德华力，此时溶剂可以***石墨层间，进行层层剥离，制备出石墨烯。此方法不会像氧化-还原法那样破坏石墨烯的结构，可以制备高质量的石墨烯。但是存在对设备要求高，反应危险和成本高等问题，而且也存在化学试剂污染的问题。The solvent stripping method was proposed in the last two years. Its principle is to disperse a small amount of graphite in a solvent to form a low concentration dispersion, and intercalate the reaction under high temperature and high pressure to destroy the van der Waals force between the graphite layers. The solvent can be inserted between the graphite layers to carry out layer peeling to prepare graphene. This method does not destroy the structure of graphene like the oxidation-reduction method, and can produce high-quality graphene. However, there are problems such as high equipment requirements, high reaction risks, and high cost, and there are also problems of chemical reagent contamination.

更主要的是，无论上述哪种方法制备的石墨烯均欠缺流动性，无法解决石墨烯易团聚的固有缺陷，使得石墨烯在应用时缺乏流动性。More importantly, the graphene prepared by any of the above methods lacks fluidity, and cannot solve the inherent defects of graphene easy agglomeration, so that graphene lacks fluidity in application.

因此，为了更好的实现石墨烯的商业应用，如何得到一种更环保的制备高品质石墨烯的方法，同时克服石墨烯易团聚的缺陷，提高其流动性，是领域内各研发企业所面临的关键性挑战和亟待解决的问题之一。Therefore, in order to better realize the commercial application of graphene, how to obtain a more environmentally friendly method for preparing high-quality graphene, while overcoming the defects of graphene easy agglomeration and improving its fluidity, is faced by various R&D enterprises in the field. One of the key challenges and issues that need to be addressed.

发明内容Summary of the invention

有鉴于此，本发明要解决的技术问题在于提供一种石墨烯导电浆料的制备方法，特别是一种高流动性石墨烯导电浆料的低温制备方法，本发明提供的常温液相剥离法，能在温和条件下快速、低成本的得到具有更好的导电性能的石墨烯，而且配合助剂，形成高流动性的石墨烯导电浆料，可作为导电添加剂在锂电池、超级电容器等领域。In view of this, the technical problem to be solved by the present invention is to provide a method for preparing a graphene conductive paste, in particular, a low-temperature preparation method for a high-flow graphene conductive paste, and the normal temperature liquid phase stripping method provided by the present invention It can quickly and low-cost obtain graphene with better conductivity under mild conditions, and it can form high-flow graphene conductive paste with additives, which can be used as conductive additive in lithium battery, supercapacitor and other fields. .

本发明提供了一种石墨烯导电浆料的制备方法，包括以下步骤：The invention provides a preparation method of a graphene conductive paste, comprising the following steps:

1)将石墨分散液在超声的条件下进行剥离后，再分离，得到石墨烯纳米片；1) after the graphite dispersion is stripped under ultrasonic conditions, and then separated to obtain graphene nanosheets;

2)将上述步骤得到的石墨烯纳米片、分散剂和溶剂进行混合后，得到预浆料；2) mixing the graphene nanosheets obtained by the above steps, a dispersing agent and a solvent to obtain a pre-slurry;

3)将上述步骤得到的预浆料进行砂磨打浆后，得到石墨烯导电浆料。3) After the pre-slurry obtained in the above step is sanded and beaten, a graphene conductive paste is obtained.

优选的，所述石墨分散液中的石墨包括石墨粉、鳞片石墨、人造石墨、可膨胀石墨和膨胀石墨中的一种或多种；Preferably, the graphite in the graphite dispersion comprises one or more of graphite powder, flake graphite, artificial graphite, expandable graphite, and expanded graphite;

所述石墨分散液中石墨的质量浓度为0.5％～5％；The mass concentration of graphite in the graphite dispersion is 0.5% to 5%;

所述石墨分散液中的溶剂包括水和与水互溶的有机溶剂。The solvent in the graphite dispersion includes water and an organic solvent which is miscible with water.

优选的，所述与水互溶的有机溶剂包括甲醇、乙醇、乙二醇、甘油、丙酮、四氢呋喃、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和二甲基亚砜中的一种或多种；Preferably, the water-miscible organic solvent comprises methanol, ethanol, ethylene glycol, glycerin, acetone, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide. One or more

所述与水互溶的有机溶剂在所述石墨分散液中的质量浓度为30％～70％；The mass concentration of the water-miscible organic solvent in the graphite dispersion is 30% to 70%;

所述超声的功率为600～3000W；所述超声的时间为1～20h；The ultrasonic power is 600-3000 W; the ultrasonic time is 1-20 h;

所述分离后还包括干燥步骤。The separation also includes a drying step.

优选的，所述剥离的方式包括搅拌、剪切、球磨和砂磨中的一种或多种；Preferably, the manner of peeling comprises one or more of stirring, shearing, ball milling and sanding;

所述石墨烯纳米片的含碳量大于等于98％；The graphene nanosheet has a carbon content of 98% or more;

所述石墨烯纳米片的厚度为小于等于5nm；The thickness of the graphene nanosheet is less than or equal to 5 nm;

所述石墨烯纳米片的片径为1～20μm。The graphene nanosheet has a sheet diameter of 1 to 20 μm.

优选的，所述分散剂包括聚乙烯吡咯烷酮、聚偏氯乙烯、聚丙烯、十六烷基三甲基溴化铵和十二烷基苯磺酸钠中的一种或多种；Preferably, the dispersing agent comprises one or more of polyvinylpyrrolidone, polyvinylidene chloride, polypropylene, cetyltrimethylammonium bromide and sodium dodecylbenzenesulfonate;

所述溶剂包括水、乙醇、丙酮、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和二甲基亚砜中的一种或多种；The solvent includes one or more of water, ethanol, acetone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide;

所述预浆料中，所述分散剂的质量浓度为0.2％～10％；In the pre-slurry, the mass concentration of the dispersant is 0.2% to 10%;

所述预浆料中，所述石墨烯纳米片的质量浓度为1％～10％。In the pre-slurry, the graphene nanosheet has a mass concentration of 1% to 10%.

优选的，所述砂磨为湿法砂磨；Preferably, the sanding is wet sanding;

所述砂磨的砂磨介质的尺寸为0.1～2mm；The sanding sanding medium has a size of 0.1 to 2 mm;

所述石墨烯导电浆料的电导率大于等于40000S/m。The electrical conductivity of the graphene conductive paste is greater than or equal to 40,000 S/m.

优选的，所述湿法砂磨为湿法超细砂磨；Preferably, the wet sanding is wet superfine sanding;

所述砂磨介质包括硅酸锆珠、氧化锆珠、玻璃珠和钢珠中的一种或多种；The sanding medium comprises one or more of zirconium silicate beads, zirconia beads, glass beads and steel balls;

所述砂磨的次数为2～50次。The number of sanding is 2 to 50 times.

优选的，所述石墨为经过预处理后的石墨；Preferably, the graphite is pretreated graphite;

所述预处理的步骤为：The steps of the pre-processing are:

A)将石墨和小分子插层剂进行反应后，得到插层石墨；A) after the graphite and the small molecule intercalation agent are reacted, the intercalated graphite is obtained;

B)将上述步骤得到的插层石墨经过高温膨胀后，得到处理后的石墨。B) After the intercalated graphite obtained in the above step is expanded at a high temperature, the treated graphite is obtained.

优选的，所述石墨的粒度为50～10000目；Preferably, the graphite has a particle size of 50 to 10000 mesh;

所述石墨的碳含量大于等于70％；The carbon content of the graphite is greater than or equal to 70%;

所述小分子插层剂包括小分子高温可分解化合物；The small molecule intercalating agent comprises a small molecule high temperature decomposable compound;

所述反应的时间为10～30小时；所述反应的温度为0～40℃。The reaction time is 10 to 30 hours; the temperature of the reaction is 0 to 40 °C.

优选的，所述小分子插层剂包括硫酸、硝酸、尿素、碳酸氢钠、碳酸二氢钠、碳酸氢二钠、草酸、磷酸、高氯酸、高碘酸和三氟甲磺酸中的一种或多种；Preferably, the small molecule intercalating agent comprises sulfuric acid, nitric acid, urea, sodium hydrogencarbonate, sodium dihydrocarbonate, disodium hydrogencarbonate, oxalic acid, phosphoric acid, perchloric acid, periodic acid and trifluoromethanesulfonic acid. One or more;

所述石墨与小分子插层剂的质量比为1：(1～5)；The mass ratio of the graphite to the small molecule intercalant is 1: (1 ~ 5);

所述高温膨胀的温度为500～1200℃；The high temperature expansion temperature is 500 to 1200 ° C;

所述高温膨胀的时间为5～60秒。The high temperature expansion time is 5 to 60 seconds.

本发明提供了一种石墨烯导电浆料的制备方法，包括以下步骤，首先将石墨分散液在超声的条件下进行剥离后，再分离，得到石墨烯纳米片；然后将上述步骤得到的石墨烯纳米片、分散剂和溶剂进行混合后，得到预浆料；最后将上述步骤得到的预浆料进行砂磨打浆后，得到石墨烯导电浆料。与现有技术相比，本发明针对现有的微机械剥离法可以制备出高质量石墨烯，但存在产率低和成本高的不足，不满足工业化和规模化生产要求，目前只能作为实验室小规模制备。化学气相沉积法可以制备出高质量大面积的石墨烯，但是理想的基片材料单晶镍的价格太昂贵，大大限制了石墨烯工业化生产，成本较高，工艺复杂。氧化-还原法会导致石墨烯部分电学性能的损失，使石墨烯的应用受到限制。而常规的溶剂剥离法存在的高温高压缺陷以及产率低的问题。本发明选择了低温常压的液相剥离法，创造性的采用石墨-溶剂混合-超声分散-湿法砂磨的方法，通过先制备石墨烯纳米片，然后再制备流动的石墨烯导电浆料，能够在温和条件下快速、低成本地制备石墨烯。而且本发明制备的石墨烯具有完整的片层结构，没有进行表面修饰，保持二维片层的本征特点。本发明制备的石墨烯导电浆料具有高导电性、高流动性的特点，可作为导电添加剂在锂电池、超级电容器、导电涂层等领域。The present invention provides a method for preparing a graphene conductive paste, comprising the steps of: first separating a graphite dispersion under ultrasonic conditions, and then separating to obtain a graphene nanosheet; and then obtaining the graphene obtained in the above step After the nanosheet, the dispersant and the solvent are mixed, a pre-slurry is obtained; finally, the pre-pulp obtained in the above step is sanded and beaten to obtain a graphene conductive paste. Compared with the prior art, the present invention can produce high-quality graphene for the existing micro-mechanical stripping method, but has the disadvantages of low yield and high cost, does not meet the requirements of industrialization and large-scale production, and can only be used as an experiment at present. Small-scale preparation of the room. Chemical vapor deposition can produce high-quality large-area graphene, but the ideal substrate material single-crystal nickel is too expensive, which greatly limits the industrial production of graphene, high cost and complicated process. The oxidation-reduction method causes a loss of electrical properties of the graphene portion, which limits the application of graphene. The conventional solvent stripping method has the problems of high temperature and high pressure defects and low yield. The invention selects a liquid phase stripping method of low temperature and normal pressure, and creatively adopts a graphite-solvent mixing-ultrasonic dispersion-wet sanding method, by preparing a graphene nanosheet first, and then preparing a flowing graphene conductive paste. Graphene can be produced quickly and at low cost under mild conditions. Moreover, the graphene prepared by the invention has a complete sheet structure without surface modification, and maintains the intrinsic characteristics of the two-dimensional sheet. The graphene conductive paste prepared by the invention has the characteristics of high conductivity and high fluidity, and can be used as a conductive additive in the fields of lithium batteries, super capacitors, conductive coatings and the like.

实验结果表明，本发明制备的高导电石墨烯浆料，碳含量大于等于99.5％，电导率大于50000S/m，能达到70000S/m，10s ^-1时粘度小于1500mPa·s。 The results showed that highly conductive graphene prepared slurry of the present invention, the carbon content of not less than 99.5%, a conductivity greater than 50000S / m, can reach 70000S / m, a viscosity of less than 1500mPa · s 10s ^-1 time.

附图说明DRAWINGS

图1为本发明对比例1制备的高导电石墨烯的流变测试数据曲线；1 is a rheological test data curve of the highly conductive graphene prepared in Comparative Example 1 of the present invention;

图2为本发明实施例1制备的高导电石墨烯的流变测试数据曲线；2 is a rheological test data curve of the highly conductive graphene prepared in Example 1 of the present invention;

图3为本发明实施例2制备的高导电石墨烯的流变测试数据曲线；3 is a rheological test data curve of the highly conductive graphene prepared in Example 2 of the present invention;

图4为本发明实施例3制备的高导电石墨烯的流变测试数据曲线。4 is a rheological test data curve of the highly conductive graphene prepared in Example 3 of the present invention.

具体实施方式detailed description

为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为了进一步说明本发明的特征和优点，而不是对发明权利要求的限制。For a better understanding of the invention, the preferred embodiments of the invention are described in the accompanying claims,

本发明所有原料，对其来源没有特别限制，在市场上购买的或按照本领域技术人员熟知的常规方法制备的即可。All the raw materials of the present invention are not particularly limited in their source, and are commercially available or prepared according to a conventional method well known to those skilled in the art.

本发明所有原料，对其纯度没有特别限制，本发明优选采用分析纯或石墨烯制备领域常规的纯度要求。The purity of all the raw materials of the present invention is not particularly limited, and the present invention preferably employs conventional purity requirements in the field of analytically pure or graphene preparation.

本发明所有原料，其牌号和简称均属于本领域常规牌号和简称，每个牌号和简称在其相关用途的领域内均是清楚明确的，本领域技术人员根据牌号、简称以及相应的用途，能够从市售中购买得到或常规方法制备得到。All the raw materials and the abbreviations of the present invention belong to the conventional brands and abbreviations in the field, and each brand and abbreviation are clear and clear in the field of their related uses, and those skilled in the art can according to the brand name, the abbreviation and the corresponding use. It is commercially available or prepared by conventional methods.

本发明首先将石墨分散液在超声的条件下进行剥离后，再分离，得到石墨烯纳米片。In the present invention, the graphite dispersion is first peeled off under ultrasonic conditions, and then separated to obtain a graphene nanosheet.

本发明对所述石墨分散液中石墨的选择没有特别限制，以本领域技术人员熟知的石墨材料即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述石墨优选包括石墨粉、鳞片石墨、人造石墨、可膨胀石墨和膨胀石墨中的一种或多种，更优选为石墨粉、鳞片石墨、人造石墨、可膨胀石墨或膨胀石墨。The invention has no particular limitation on the selection of the graphite in the graphite dispersion, and the graphite material which is well known to those skilled in the art can be selected, and the person skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention The graphite preferably includes one or more of graphite powder, flake graphite, artificial graphite, expandable graphite, and expanded graphite, more preferably graphite powder, flake graphite, artificial graphite, expandable graphite, or expanded graphite.

本发明对所述石墨分散液中石墨的粒度没有特别限制，以本领域技术人员熟知的石墨粉的粒径即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述石墨分散液优选为石墨粉的分散液，所述石墨的粒度优选为50～10000目，更优选为100～5000目，更优选为 500～3000目，最优选为1000～2000目。The particle size of the graphite in the graphite dispersion is not particularly limited, and the particle size of the graphite powder well known to those skilled in the art may be selected, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements. The graphite dispersion of the present invention is preferably a dispersion of graphite powder, and the graphite preferably has a particle size of 50 to 10,000 mesh, more preferably 100 to 5,000 mesh, more preferably 500 to 3,000 mesh, and most preferably 1000 to 2000. Head.

本发明对所述石墨分散液中石墨的碳含量没有特别限制，以本领域技术人员熟知的石墨粉的碳含量即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述石墨的碳含量优选大于等于70％，更优选大于等于80％，最优选为大于等于90％，具体可以为70％～95％，也可以为75％～90％，或者为78％～93％。The carbon content of the graphite in the graphite dispersion is not particularly limited, and the carbon content of the graphite powder well known to those skilled in the art may be selected, and those skilled in the art may select according to actual production conditions, product requirements, and quality requirements. The carbon content of the graphite of the present invention is preferably 70% or more, more preferably 80% or more, most preferably 90% or more, specifically 70% to 95%, or 75% to 90%, or It is 78% to 93%.

本发明对所述石墨分散液中石墨的浓度没有特别限制，以本领域技术人员熟知的常规浓度即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高后续产品的性能，提高石墨分散液的均匀性，本发明所述石墨分散液中石墨的质量浓度优选为0.5％～5％，更优选为1.5％～4％，更优选为2.5％～3％。The concentration of graphite in the graphite dispersion of the present invention is not particularly limited, and can be selected and adjusted according to actual production conditions, product requirements, and quality requirements by a person skilled in the art, and the present invention can be selected and adjusted according to actual production conditions, product requirements, and quality requirements. In order to improve the performance of the subsequent product and improve the uniformity of the graphite dispersion, the mass concentration of graphite in the graphite dispersion of the present invention is preferably from 0.5% to 5%, more preferably from 1.5% to 4%, still more preferably 2.5%. 3%.

本发明对所述石墨分散液中的溶剂没有特别限制，以本领域技术人员熟知的常规溶剂即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高后续产品的性能，提高石墨分散液的均匀性，所述石墨分散液中的溶剂特别优选包括水和与水互溶的有机溶剂。本发明所述与水互溶的有机溶剂优选包括甲醇、乙醇、乙二醇、甘油、丙酮、四氢呋喃、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和二甲基亚砜中的一种或多种，更优选为甲醇、乙醇、乙二醇、甘油、丙酮、四氢呋喃、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮或二甲基亚砜。The solvent in the graphite dispersion of the present invention is not particularly limited, and can be selected and adjusted according to actual production conditions, product requirements, and quality requirements by those skilled in the art, and the present invention is The performance of the subsequent product is improved to improve the uniformity of the graphite dispersion, and the solvent in the graphite dispersion particularly preferably includes water and a water-miscible organic solvent. The water-miscible organic solvent of the present invention preferably comprises methanol, ethanol, ethylene glycol, glycerin, acetone, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide. One or more of them are more preferably methanol, ethanol, ethylene glycol, glycerin, acetone, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.

本发明对所述石墨分散液中的溶剂的具体组成比例没有特别限制，以本领域技术人员熟知的常规配比即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高后续产品的性能，提高石墨分散液的均匀性，所述与水互溶的有机溶剂在所述石墨分散液中的质量浓度优选为30％～70％，更优选为40％～60％，更优选为45％～55％。The specific composition ratio of the solvent in the graphite dispersion of the present invention is not particularly limited, and can be selected according to the actual production conditions, product requirements, and quality requirements by a person skilled in the art. In order to improve the performance of the subsequent product and improve the uniformity of the graphite dispersion, the mass concentration of the water-miscible organic solvent in the graphite dispersion is preferably 30% to 70%, more preferably 40%. ～60%, more preferably 45% to 55%.

本发明对所述剥离的方式没有特别限制，以本领域技术人员熟知的此类剥离的方式即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高最终产品的性能，所述剥离的方式优选为机械剥离，即采用机械剥离与超声搭配的方式进行剥离，具体优选包括搅拌、剪切、球磨和砂磨中的一种或多种，更优选为搅拌、剪切、球磨和砂磨，并同时进行超声。The manner of the peeling of the present invention is not particularly limited, and may be selected and adjusted according to actual production conditions, product requirements, and quality requirements by those skilled in the art. The present invention is The performance of the final product is improved, and the peeling is preferably mechanical peeling, that is, peeling by means of mechanical peeling and ultrasonic matching, and specifically preferably one or more of stirring, shearing, ball milling and sanding, more preferably For agitation, shearing, ball milling and sanding, and simultaneous ultrasound.

本发明对所述剥离的温度没有特别限制，以本领域技术人员熟知的此类剥离的温度即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高最终产品的性能和液相分离法的优势，所述剥离的温度优选为室温，即优选为0～40℃，更优选为5～35℃，更优选为10～30℃，更优选为15～25℃。The temperature of the peeling is not particularly limited in the present invention, and the temperature of such peeling, which is well known to those skilled in the art, may be selected, and those skilled in the art may select and adjust according to actual production conditions, product requirements, and quality requirements. The performance of the final product and the advantage of the liquid phase separation method are improved, and the temperature of the peeling is preferably room temperature, that is, preferably 0 to 40 ° C, more preferably 5 to 35 ° C, still more preferably 10 to 30 ° C, still more preferably 15 ~25 ° C.

本发明对所述超声的条件没有特别限制，以本领域技术人员熟知的常规条件即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高后续产品的性能，提高石墨分散液的均匀性，所述超声的功率优选为600～3000W，更优选为1100～2500W，更优选为1600～2000W。所述超声的时间，即剥离的时间，优选为1～20h，更优选为5～16h，更优选为9～12h，具体可以为1h、2h、8h或20h。The condition of the ultrasound is not particularly limited, and the conventional conditions well known to those skilled in the art may be used. Those skilled in the art may select and adjust according to actual production conditions, product requirements, and quality requirements, and the present invention is to improve subsequent products. The performance of the graphite dispersion is improved, and the power of the ultrasonic wave is preferably 600 to 3000 W, more preferably 1100 to 2500 W, still more preferably 1600 to 2000 W. The time of the ultrasonication, that is, the time of peeling, is preferably from 1 to 20 h, more preferably from 5 to 16 h, still more preferably from 9 to 12 h, and specifically may be 1 h, 2 h, 8 h or 20 h.

本发明对所述分离的方式没有特别限制，以本领域技术人员熟知的常规分离方式即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述分离优选为过滤分离，更具体优选包括抽滤。本发明所述分离后优选还包括干燥步骤。本发明对所述干燥的具体方式和条件没有特别限制，以本领域技术人员熟知的常规干燥方式和条件即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整。The manner of the separation of the present invention is not particularly limited, and the conventional separation method well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements and quality requirements, and the separation according to the present invention. Preference is given to filtration separation, more particularly preferably to suction filtration. Preferably, after the separation of the present invention, a drying step is also included. The specific manner and conditions of the drying of the present invention are not particularly limited, and the conventional drying methods and conditions well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements, and quality requirements.

本发明为进一步提高后续产品的导电性能，提高石墨分散液的均匀性，所述石墨分散液中的石墨更优选为经过预处理后的石墨。本发明特别优选所述预处理的步骤具体为：In order to further improve the electrical conductivity of the subsequent product and improve the uniformity of the graphite dispersion, the graphite in the graphite dispersion is more preferably pretreated graphite. Particularly preferred steps of the pretreatment of the present invention are:

本发明对上述步骤中石墨的选择和要求，以及相应的优选原则，与前述石墨烯导电浆料的制备方法中所对应原料的选择和要求，以及相应的优选原则可以进行对应，在此不再一一赘述。The selection and requirements of the graphite in the above steps, and the corresponding preferred principles, may correspond to the selection and requirements of the corresponding raw materials in the preparation method of the foregoing graphene conductive paste, and corresponding preferred principles, and no longer One by one.

本发明首先将石墨和小分子插层剂进行反应后，得到插层石墨。The present invention firstly reacts graphite and a small molecule intercalant to obtain intercalated graphite.

本发明对所述小分子插层剂的选择没有特别限制，以本领域技术人员熟知的小分子插层剂即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高最终产品的性能，所述小分子插层剂优选为小分子高温可分解化合物，更优选包括硫酸、硝酸、尿素、碳酸氢钠、碳酸二氢钠、碳酸氢二钠、草酸、磷酸、高氯酸、高碘酸和三氟甲磺酸中的一种或多种，更优选为硫酸、硝酸、尿素、碳酸氢钠、碳酸二氢钠、碳酸氢二钠、草酸、磷酸、高氯酸、高碘酸或三氟甲磺酸。更优选为硫酸、硝酸、尿素、碳酸氢钠、碳酸二氢钠、碳酸氢二钠、草酸或磷酸。The selection of the small molecule intercalating agent in the present invention is not particularly limited, and the small molecule intercalating agent well known to those skilled in the art can be selected, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. In order to improve the performance of the final product, the small molecule intercalating agent is preferably a small molecule high temperature decomposable compound, more preferably including sulfuric acid, nitric acid, urea, sodium hydrogencarbonate, sodium dihydrocarbonate, disodium hydrogencarbonate, oxalic acid. One or more of phosphoric acid, perchloric acid, periodic acid and trifluoromethanesulfonic acid, more preferably sulfuric acid, nitric acid, urea, sodium hydrogencarbonate, sodium dihydrocarbonate, disodium hydrogencarbonate, oxalic acid, phosphoric acid , perchloric acid, periodic acid or trifluoromethanesulfonic acid. More preferred are sulfuric acid, nitric acid, urea, sodium hydrogencarbonate, sodium dihydrocarbonate, disodium hydrogencarbonate, oxalic acid or phosphoric acid.

本发明对所述小分子插层剂的用量没有特别限制，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高最终产品的性能，所述石墨与小分子插层剂的质量比优选为1：(1～5)，更优选为1：(1.5～4.5)，更优选为1：(2～4)，最优选为1：(2.5～3.5)。The amount of the small molecule intercalating agent used in the present invention is not particularly limited, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality requirements. The present invention improves the performance of the final product. The mass ratio of the molecular intercalation agent is preferably 1: (1 to 5), more preferably 1: (1.5 to 4.5), still more preferably 1: (2 to 4), and most preferably 1: (2.5 to 3.5).

本发明对所述反应的温度没有特别限制，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高最终产品的性能和液相分离法的优势，特别的将反应温度维持在室温，即所述反应的温度优选为0～40℃，更优选为5～35℃，更优选为10～30℃，更优选为15～25℃。The temperature of the reaction is not particularly limited in the present invention, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality requirements. The present invention is advantageous for improving the performance of the final product and the advantages of the liquid phase separation method. The reaction temperature is maintained at room temperature, that is, the temperature of the reaction is preferably 0 to 40 ° C, more preferably 5 to 35 ° C, still more preferably 10 to 30 ° C, still more preferably 15 to 25 ° C.

本发明对所述反应的时间没有特别限制，以本领域技术人员熟知的液相分离法的常规插层反应时间即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述反应的时间优选为10～30h，更优选为12～28h，更优选为15～25h，更优选为17～24h，具体可以为10h、15h、20h或30h。The time of the reaction of the present invention is not particularly limited, and the conventional intercalation reaction time of the liquid phase separation method well known to those skilled in the art is sufficient, and those skilled in the art can select and according to actual production conditions, product requirements, and quality requirements. The time of the reaction according to the present invention is preferably 10 to 30 h, more preferably 12 to 28 h, still more preferably 15 to 25 h, still more preferably 17 to 24 h, and specifically 10 h, 15 h, 20 h or 30 h.

本发明采用小分子高温可分解插层剂对石墨进行插层，小分子高温可分解化合物能够实现小分子进入层间，减少石墨反应，保持石墨片层完整的结构；而且还避免了高温高压的反应条件，进一步下调了插层反应的温度，可以在更低温度和普通室温条件下等温和条件实现石墨的有效插层，得到石墨插层化合物，降低了制备过程的损耗和能耗，绿色环保。The invention adopts a small molecule high temperature decomposable intercalating agent to intercalate graphite, and the small molecule high temperature decomposable compound can realize small molecules entering the interlayer, reduce the graphite reaction, maintain the intact structure of the graphite sheet layer, and avoid the high temperature and high pressure. The reaction conditions further reduce the temperature of the intercalation reaction, and the effective intercalation of graphite can be realized under isothermal conditions at a lower temperature and ordinary room temperature conditions, thereby obtaining a graphite intercalation compound, which reduces the loss and energy consumption of the preparation process, and is environmentally friendly. .

本发明为提高制备方法的实用性，完整工艺路线，所述反应后优选还包括后处理步骤。本发明对所述后处理的具体步骤没有特别限制，以本领域技术人员熟知的后处理步骤即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述后处理优选包括水洗和分离，更具体优选为水洗至中性和离心分离。The invention is to improve the practicability of the preparation method, the complete process route, and preferably further comprises a post-treatment step after the reaction. The specific steps of the post-treatment of the present invention are not particularly limited, and the post-processing steps well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements, and quality requirements. The post treatment preferably comprises water washing and separation, more particularly preferably water washing to neutral and centrifugal separation.

本发明然后将上述步骤得到的插层石墨经过高温膨胀后，得到膨胀石墨。The present invention then expands the intercalated graphite obtained in the above step by high temperature to obtain expanded graphite.

本发明对所述高温膨胀的温度没有特别限制，以本领域技术人员熟知的此类膨胀的温度即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高最终产品的性能和液相分离法的优势，所述高温膨胀的温度优选为500～1200℃，更优选为600～1100℃，更优选为700～1000℃，更优选为800～900℃。The temperature of the high temperature expansion of the present invention is not particularly limited, and the temperature of such expansion is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality requirements. In order to improve the performance of the final product and the advantage of the liquid phase separation method, the temperature of the high temperature expansion is preferably 500 to 1200 ° C, more preferably 600 to 1100 ° C, still more preferably 700 to 1000 ° C, still more preferably 800 to 900 ° C. .

本发明对所述高温膨胀的时间没有特别限制，以本领域技术人员熟知的高温膨胀的时间即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述高温膨胀的时间优选为5～60秒，更优选为10～55秒，更优选为15～50秒，更优选为25～40秒，具体可以为5秒、10秒、30秒或60秒。The time for the high temperature expansion of the present invention is not particularly limited, and the time of high temperature expansion which is well known to those skilled in the art can be selected, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements. The time for the high temperature expansion is preferably 5 to 60 seconds, more preferably 10 to 55 seconds, still more preferably 15 to 50 seconds, still more preferably 25 to 40 seconds, and specifically 5 seconds, 10 seconds, 30 seconds or 60 seconds. .

本发明经过上述步骤得到了石墨烯纳米片。本发明对所述石墨烯纳米片的具体性能参数没有特别限制，本领域技术人员参照上述方法即可得到具体该性能的石墨烯纳米片，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述石墨烯纳米片的含碳量优选大于等于98％，更优选大于等于98.5％，更优选大于等于99％。所述石墨烯纳米片的厚度优选为小于等于5nm，更优选为小于等于4nm，更优选为小于等于3nm。所述石墨烯纳米片的片径优选为1～20μm，更优选为5～16μm，更优选为9～12μm。The present invention obtains graphene nanosheets through the above steps. The specific performance parameters of the graphene nanosheets of the present invention are not particularly limited, and those skilled in the art can obtain graphene nanosheets having specific properties according to the above methods, and those skilled in the art can obtain actual production conditions, product requirements, and quality according to actual conditions. The selection and adjustment are required. The carbon content of the graphene nanosheet of the present invention is preferably 98% or more, more preferably 98.5% or more, and still more preferably 99% or more. The thickness of the graphene nanosheet is preferably 5 nm or less, more preferably 4 nm or less, and still more preferably 3 nm or less. The sheet diameter of the graphene nanosheet is preferably from 1 to 20 μm, more preferably from 5 to 16 μm, still more preferably from 9 to 12 μm.

本发明随后将上述步骤得到的石墨烯纳米片、分散剂和溶剂进行混合后，得到预浆料。The present invention then mixes the graphene nanosheets obtained in the above steps, a dispersant, and a solvent to obtain a pre-slurry.

本发明对所述分散剂的具体选择没有特别限制，以本领域技术人员熟知的常规分散剂即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高后续产品的性能，提高预浆料的均匀性，所述分散剂优选包括聚乙烯吡咯烷酮、聚偏氯乙烯、聚丙烯、十六烷基三甲基溴化铵和十二烷基苯磺酸钠中的一种或多种，更优选为聚乙烯吡咯烷酮、聚偏氯乙烯、聚丙烯、十六烷基三甲基溴化铵或十二烷基苯磺酸钠。The specific selection of the dispersing agent in the present invention is not particularly limited, and a conventional dispersing agent well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements, and quality requirements, and the present invention is Improving the performance of the subsequent product and improving the uniformity of the pre-slurry, the dispersing agent preferably comprises polyvinylpyrrolidone, polyvinylidene chloride, polypropylene, cetyltrimethylammonium bromide and dodecylbenzenesulfonic acid One or more of sodium is more preferably polyvinylpyrrolidone, polyvinylidene chloride, polypropylene, cetyltrimethylammonium bromide or sodium dodecylbenzenesulfonate.

本发明对所述分散剂的用量没有特别限制，以本领域技术人员熟知的常规用量即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高后续产品的性能，提高预浆料的均匀性，所述预浆料中，所述分散剂的质量浓度优选为0.2％～10％，更优选为0.7％～9％，更优选为2％～8％，更优选为4％～6％。The amount of the dispersing agent used in the present invention is not particularly limited, and can be selected and adjusted according to actual production conditions, product requirements, and quality requirements by those skilled in the art, and the present invention is to improve the follow-up. The performance of the product improves the uniformity of the pre-slurry. In the pre-slurry, the mass concentration of the dispersant is preferably 0.2% to 10%, more preferably 0.7% to 9%, still more preferably 2% to 8 % is more preferably 4% to 6%.

本发明对所述溶剂的具体选择没有特别限制，以本领域技术人员熟知的常规溶剂即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高后续产品的性能，提高预浆料的均匀性，所述溶剂优选包括水、乙醇、丙酮、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和二甲基亚砜中的一种或多种，更优选为水、乙醇、丙酮、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮或二甲基亚砜。The specific selection of the solvent in the present invention is not particularly limited, and can be selected and adjusted according to actual production conditions, product requirements, and quality requirements by those skilled in the art, and the present invention is to improve the follow-up. The performance of the product, improving the uniformity of the pre-slurry, the solvent preferably comprising one of water, ethanol, acetone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide Or more, more preferably water, ethanol, acetone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.

本发明对所述溶剂的用量没有特别限制，以本领域技术人员熟知的常规溶剂用量即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明为提高后续产品的性能，提高预浆料的均匀性，所述预浆料中，所述石墨烯纳米片的质量浓度优选为1％～10％，更优选为2％～9％，更优选为3％～8％，更优选为4％～7％。The amount of the solvent used in the present invention is not particularly limited, and can be selected and adjusted according to actual production conditions, product requirements, and quality requirements by those skilled in the art, and the present invention is to improve the follow-up. The performance of the product improves the uniformity of the pre-slurry. In the pre-slurry, the mass concentration of the graphene nanosheet is preferably from 1% to 10%, more preferably from 2% to 9%, still more preferably 3%. ～8%, more preferably 4% to 7%.

本发明对所述混合的方式没有特别限制，以本领域技术人员熟知的混合方式即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述混合的方式优选为搅拌混合。The manner of the mixing of the present invention is not particularly limited, and can be selected and adjusted according to actual production conditions, product requirements, and quality requirements by those skilled in the art, and the mixed type of the present invention. The mode is preferably agitation mixing.

本发明最后将上述步骤得到的预浆料进行砂磨打浆后，得到石墨烯导电浆料。In the final invention, after the pre-slurry obtained in the above step is sanded and beaten, a graphene conductive paste is obtained.

本发明为提高最终产品的性能，提供石墨烯导电浆料的流动性和导电性能，特别优选采用砂磨的方式进行打浆。本发明对所述砂磨的具体方式没有特别限制，以本领域技术人员熟知的砂磨方式即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述砂磨的方式优选为湿法砂磨，更优选为湿法超细砂磨，即采用湿法超细砂磨机进行砂磨，具体类型可以为棒销式纳米砂磨机。In order to improve the performance of the final product, the present invention provides the flowability and electrical conductivity of the graphene conductive paste, and it is particularly preferable to perform the beating by sanding. The specific manner of the sanding in the present invention is not particularly limited, and the sanding method well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements, and quality requirements, and the present invention The sanding method is preferably wet sanding, more preferably wet superfine sanding, that is, sanding using a wet superfine sand mill, and the specific type may be a pin-type nano sand mill.

本发明对所述砂磨的砂磨介质没有特别限制，以本领域技术人员熟知的砂磨介质即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述砂磨介质优选包括硅酸锆珠、氧化锆珠、玻璃珠和钢珠中的一种或多种，更优选为硅酸锆珠、氧化锆珠、玻璃珠或钢珠，更优选为硅酸锆珠或氧化锆珠。本发明所述砂磨的砂磨介质的尺寸优选为0.1～2mm，更优选为0.5～1.5mm，更优选为0.8～1.2mm。The sanding medium of the sanding is not particularly limited, and the sanding medium is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements, and the present invention The sanding medium preferably comprises one or more of zirconium silicate beads, zirconia beads, glass beads and steel beads, more preferably zirconium silicate beads, zirconia beads, glass beads or steel beads, more preferably silicic acid. Zirconium beads or zirconia beads. The sanding media of the present invention preferably has a size of from 0.1 to 2 mm, more preferably from 0.5 to 1.5 mm, still more preferably from 0.8 to 1.2 mm.

本发明对所述砂磨的次数没有特别限制，以本领域技术人员熟知的砂磨次数即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述砂磨的次数优选为多次砂磨，具体可以为2～50次，更优选为5～35次，更优选为10～30次，更优选为15～25次。The number of times of the sanding is not particularly limited in the present invention, and the number of sandings well known to those skilled in the art may be selected, and those skilled in the art may select and adjust according to actual production conditions, product requirements, and quality requirements. The number of sanding is preferably a plurality of sanding, specifically 2 to 50 times, more preferably 5 to 35 times, still more preferably 10 to 30 times, still more preferably 15 to 25 times.

本发明对所述砂磨的其他条件没有特别限制，以本领域技术人员熟知的砂磨条件即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整，本发明所述砂磨的功率优选为2～15KW，更优选为5～12KW，更优选为7～10KW。所述砂磨的加工处理量优选为1～100L/h，更优选为10～90L/h，更优选为30～70L/h，更优选为40～60L/h。The other conditions of the sanding in the present invention are not particularly limited, and the sanding conditions well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual production conditions, product requirements, and quality requirements. The power of the sanding is preferably 2 to 15 KW, more preferably 5 to 12 KW, still more preferably 7 to 10 KW. The processing amount of the sanding is preferably from 1 to 100 L/h, more preferably from 10 to 90 L/h, still more preferably from 30 to 70 L/h, still more preferably from 40 to 60 L/h.

本发明经过上述步骤得到的石墨烯导电浆料，是一种高导电石墨烯导电浆料，本发明对所述高导电石墨烯的性能和结构没有特别限制，以本领域技术人员熟知的高导电石墨烯的性能和结构即可，本领域技术人员根据前述制备方法进行制备即可得到高导电石墨烯导电浆料中石墨烯的性能和结构，本发明所述高导电石墨烯导电浆料中的高导电石墨烯呈薄片状，其厚度优选为小于等于5nm，更优选为小于等于4nm，更优选为小于等于3nm。本发明所述石墨烯厚度为通过原子力显微镜测得的随意选取20个片层的平均厚度。The graphene conductive paste obtained by the above steps is a highly conductive graphene conductive paste, and the present invention has no particular limitation on the performance and structure of the highly conductive graphene, and is highly conductive as known to those skilled in the art. The performance and structure of the graphene are sufficient, and those skilled in the art can prepare the properties and structures of the graphene in the highly conductive graphene conductive paste according to the preparation method described above, and the conductive paste in the highly conductive graphene conductive paste of the present invention. The highly conductive graphene has a sheet shape, and its thickness is preferably 5 nm or less, more preferably 4 nm or less, and still more preferably 3 nm or less. The graphene thickness of the present invention is an average thickness of 20 sheets randomly selected by atomic force microscopy.

本发明所述高导电石墨烯，碳含量由元素分析测得，碳含量优选大于等于99.5％。In the highly conductive graphene of the present invention, the carbon content is determined by elemental analysis, and the carbon content is preferably 99.5% or more.

本发明所述高导电石墨烯，电导率由四探针电导率测试法测得，电导率优选大于40000S/m，更优选为大于等于45000S/m，更优选为大于等于50000S/m，更能够达到70000S/m。The high conductivity graphene of the present invention has conductivity measured by a four-probe conductivity test method, and the conductivity is preferably more than 40000 S/m, more preferably 45000 S/m or more, more preferably 50,000 S/m or more, and more capable of It reaches 70,000 S/m.

本发明上述步骤提供了一种含有高导电石墨烯的导电浆料，本发明选择了低温常压的液相剥离法，创造性的采用石墨-溶剂混合-超声分散-超高压均质的方法，更进一步优选采用小分子插层-高温膨胀的石墨预处理方式，通过先制备石墨烯纳米片，然后再制备流动的石墨烯导电浆料，能够在温和条件下快速、低成本地制备石墨烯。而且本发明制备的石墨烯具有完整的片层结构，没有进行表面修饰，保持二维片层的本征特点。本发明制备的石墨烯导电浆料具有高导电性、高流动性的特点，又通过对现有商用导电剂性能不足的研究，利用石墨烯优异的导电特性，采用上述方法，制得石墨烯导电浆料，应用于锂电池正极材料，以显著提高锂电池的倍率性能、循环寿命等。本发明的导电浆料导电性能优异，分散均匀、流动性好，而且工艺简单，容易实现，适合大批量制被石墨烯导电浆料。The above steps of the present invention provide a conductive paste containing highly conductive graphene. The present invention selects a liquid phase stripping method of low temperature and normal pressure, and creatively adopts a graphite-solvent mixing-ultrasonic dispersion-ultrahigh pressure homogenization method. It is further preferred to use a small molecule intercalation-high temperature expansion graphite pretreatment method to prepare graphene rapidly and at low cost under mild conditions by first preparing graphene nanosheets and then preparing a flowing graphene conductive paste. Moreover, the graphene prepared by the invention has a complete sheet structure without surface modification, and maintains the intrinsic characteristics of the two-dimensional sheet. The graphene conductive paste prepared by the invention has the characteristics of high conductivity and high fluidity, and through the study of the insufficient performance of the existing commercial conductive agent, the graphene is electrically conductive by using the excellent electrical conductivity characteristics of the graphene. The slurry is applied to a positive electrode material of a lithium battery to significantly improve the rate performance, cycle life, and the like of the lithium battery. The conductive paste of the invention has excellent electrical conductivity, uniform dispersion, good fluidity, simple process and easy realization, and is suitable for high-precision graphiteene conductive paste.

为了进一步说明本发明，以下结合实施例对本发明提供的一种石墨烯导电浆料的制备方法进行详细描述，但是应当理解，这些实施例是在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制，本发明的保护范围也不限于下述的实施例。In order to further illustrate the present invention, a method for preparing a graphene conductive paste provided by the present invention will be described in detail below with reference to the embodiments, but it should be understood that these embodiments are carried out under the premise of the technical solution of the present invention. The detailed description of the present invention and the specific operation of the present invention are not intended to limit the scope of the present invention, and the scope of the present invention is not limited to the embodiments described below.

对比例1Comparative example 1

原材料为1000目天然石墨(青岛东凯石墨有限公司)。将10g石墨与50g碳酸二氢钠混合分散于100g水中，将混合液机械搅拌，室温下反应20小时，再加入400g水稀释，离心得到插层石墨。将插层石墨置于1000℃的马弗炉中，膨胀30s。5g膨胀后的石墨分散于5mL N-甲基吡咯烷酮中，800W超声剥离8h，300rmp球磨2h，得到高导电石墨烯。The raw material is 1000 mesh natural graphite (Qingdao Dongkai Graphite Co., Ltd.). 10 g of graphite and 50 g of sodium dihydrocarbonate were mixed and dispersed in 100 g of water, and the mixture was mechanically stirred, reacted at room temperature for 20 hours, diluted with 400 g of water, and centrifuged to obtain intercalated graphite. The intercalated graphite was placed in a muffle furnace at 1000 ° C for 30 s. 5 g of the expanded graphite was dispersed in 5 mL of N-methylpyrrolidone, 800 W ultrasonic stripping for 8 h, and 300 rmp ball milling for 2 h to obtain highly conductive graphene.

对本发明对比例1制备的高导电石墨烯进行流变粘度表征。The high conductivity graphene prepared in Comparative Example 1 of the present invention was characterized by rheological viscosity.

测试方法：石墨烯样品的流变粘度测试由安东帕MCR302流变仪进行测试得到。Test method: The rheological viscosity test of the graphene sample was tested by an Anton Paar MCR302 rheometer.

参见图1，图1为本发明对比例1制备的高导电石墨烯的流变测试数据曲线。Referring to Fig. 1, there is shown a rheological test data curve of the highly conductive graphene prepared in Comparative Example 1 of the present invention.

由图1可知，本发明对比例1制备的高导电石墨烯在10s ^-1的剪切速率条件下，粘度为2353mPa·s，表观流动性较差。 As can be seen from Fig. 1, the highly conductive graphene prepared in Comparative Example 1 of the present invention has a viscosity of 2353 mPa·s at a shear rate of 10 s ^-1 and a poor apparent fluidity.

对本发明对比例1制备的高导电石墨烯进行元素分析，本发明对比例1制备的高导电石墨烯的碳含量达到了99.414％。Elemental analysis was carried out on the highly conductive graphene prepared in Comparative Example 1 of the present invention, and the carbon content of the highly conductive graphene prepared in Comparative Example 1 of the present invention reached 99.414%.

对本发明对比例1制备的高导电石墨烯，采用四探针电导率测试法，测量电导率。For the highly conductive graphene prepared in Comparative Example 1 of the present invention, the conductivity was measured by a four-probe conductivity test method.

测试方法：石墨烯样品的电导率通过将样品压制成直径为10mm的圆片，由苏州晶格四探针电导率测试仪进行测试得到。Test method: The conductivity of the graphene sample was obtained by testing the sample into a wafer having a diameter of 10 mm and testing it by a Suzhou four-probe conductivity tester.

本发明对比例1制备的高导电石墨烯的电导率为51000S/m。The conductivity of the highly conductive graphene prepared in Comparative Example 1 of the present invention was 51,000 S/m.

对本发明对比例1制备的高导电石墨烯的稳定性进行测试。The stability of the highly conductive graphene prepared in Comparative Example 1 of the present invention was tested.

测试方法：将石墨烯样品导入密闭透明样品瓶中，置于60℃的烘箱中，24小时候再次进行流变仪测试其粘度。Test method: The graphene sample was introduced into a closed transparent sample bottle, placed in an oven at 60 ° C, and the rheometer was again tested for viscosity at 24 hours.

24小时后，对比例1制备的高导电石墨烯分层明显，流变数据显示约大于3000mPa·s。After 24 hours, the highly conductive graphene prepared in Comparative Example 1 was clearly layered, and the rheological data showed about more than 3000 mPa·s.

实施例1Example 1

将8g石墨粉与1L乙醇配成1.5L的水溶液，将其600r/min机械搅拌30min，1000W超声12h后抽滤烘干得到石墨烯纳米片，将3g纳米片、2g聚乙烯吡咯烷酮与95g乙醇混合，600r/min机械搅拌10min，800W超声20min，得到混合液。再用0.3mm氧化锆珠的砂磨机，循环打浆120min，得到流动性好的石墨烯导电浆料。8g graphite powder and 1L ethanol were mixed into 1.5L aqueous solution, mechanically stirred at 600r/min for 30min, 1000W ultrasonic for 12h, then filtered and dried to obtain graphene nanosheets, and 3g nanosheets, 2g polyvinylpyrrolidone and 95g ethanol were mixed. 600 r / min mechanical stirring for 10 min, 800 W ultrasonic for 20 min, to obtain a mixed solution. Then, using a sand mill of 0.3 mm zirconia beads, the pulp was pulverized for 120 minutes to obtain a graphene conductive paste having good fluidity.

对本发明实施例1制备的高导电石墨烯进行流变粘度表征。The high conductivity graphene prepared in Example 1 of the present invention was characterized by rheological viscosity.

参见图2，图2为本发明实施例1制备的高导电石墨烯的流变测试数据曲线。Referring to FIG. 2, FIG. 2 is a rheological test data curve of the highly conductive graphene prepared in Example 1 of the present invention.

由图2可知，本发明实施例1制备的高导电石墨烯在10s ^-1的剪切速率条件下，粘度为788mPa·s，表观流动性较好。 As can be seen from Fig. 2, the highly conductive graphene prepared in Example 1 of the present invention has a viscosity of 788 mPa·s at a shear rate of 10 s ^-1 and a good apparent fluidity.

对本发明实施例1制备的高导电石墨烯进行元素分析，本发明实施例1制备的高导电石墨烯的碳含量达到了99.621％。Elemental analysis was performed on the highly conductive graphene prepared in Example 1 of the present invention, and the carbon content of the highly conductive graphene prepared in Example 1 of the present invention reached 99.621%.

对本发明实施例1制备的高导电石墨烯，采用四探针电导率测试法，测量电导率。For the highly conductive graphene prepared in Example 1 of the present invention, the conductivity was measured by a four-probe conductivity test method.

本发明实施例1制备的高导电石墨烯的电导率达到了57000S/m。The conductivity of the highly conductive graphene prepared in Example 1 of the present invention reached 57,000 S/m.

对本发明实施例1制备的高导电石墨烯的稳定性进行测试。The stability of the highly conductive graphene prepared in Example 1 of the present invention was tested.

24小时后，实施例1制备的高导电石墨烯无分层，流变数据显示约为810mPa·s，流动性较好。After 24 hours, the highly conductive graphene prepared in Example 1 had no delamination, and the rheological data showed about 810 mPa·s, and the fluidity was good.

实施例2Example 2

将15g石墨粉与1L乙醇配成1.5L的水溶液，将其400r/min机械搅拌30min，2000W超声3h后抽滤烘干得到石墨烯纳米片，将7g纳米片、3g聚偏氯乙烯与90g二甲基乙酰胺混合，700r/min机械搅拌20min，1000W超声30min，得到混合液。再用0.8mm硅酸锆珠的砂磨机，循环打浆20min，得到流动性好的石墨烯导电浆料。15g graphite powder and 1L ethanol were mixed into 1.5L aqueous solution, mechanically stirred at 400r/min for 30min, 2000W ultrasonic for 3h, then filtered and dried to obtain graphene nanosheets, 7g nanosheets, 3g polyvinylidene chloride and 90g two Methylacetamide was mixed, mechanically stirred at 700 r/min for 20 min, and ultrasonicated at 1000 W for 30 min to obtain a mixed solution. Further, using a 0.8 mm zirconia bead mill, the pulp was cyclically beaten for 20 minutes to obtain a graphene conductive paste having good fluidity.

对本发明实施例2制备的高导电石墨烯进行流变粘度表征。The high conductivity graphene prepared in Example 2 of the present invention was characterized by rheological viscosity.

参见图3，图3为本发明实施例2制备的高导电石墨烯的流变测试数据曲线。Referring to FIG. 3, FIG. 3 is a rheological test data curve of the highly conductive graphene prepared in Example 2 of the present invention.

由图3可知，本发明实施例2制备的高导电石墨烯在10s ^-1的剪切速率条件下，粘度为774mPa·s，表观流动性较好。 As can be seen from Fig. 3, the highly conductive graphene prepared in Example 2 of the present invention has a viscosity of 774 mPa·s at a shear rate of 10 s ^-1 and a good apparent fluidity.

对本发明实施例2制备的高导电石墨烯进行元素分析，本发明实施例2制备的高导电石墨烯的碳含量达到了99.58％。The elemental analysis of the highly conductive graphene prepared in Example 2 of the present invention, the carbon content of the highly conductive graphene prepared in Example 2 of the present invention reached 99.58%.

对本发明实施例2制备的高导电石墨烯，采用四探针电导率测试法，测量电导率。For the highly conductive graphene prepared in Example 2 of the present invention, the conductivity was measured by a four-probe conductivity test method.

本发明实施例2制备的高导电石墨烯的电导率达到了59000S/m。The conductivity of the highly conductive graphene prepared in Example 2 of the present invention reached 59000 S/m.

对本发明实施例2制备的高导电石墨烯的稳定性进行测试。The stability of the highly conductive graphene prepared in Example 2 of the present invention was tested.

24小时后，实施例2制备的高导电石墨烯无分层，流变数据显示约为790mPa·s，流动性较好。After 24 hours, the highly conductive graphene prepared in Example 2 had no delamination, and the rheological data showed about 790 mPa·s, and the fluidity was good.

实施例3Example 3

将20g石墨粉与1L乙醇配成1.5L的水溶液，将其600r/min机械搅拌20min，3000W超声6h后抽滤烘干得到石墨烯纳米片，将4g纳米片、4g十二烷基苯磺酸钠与92gN-甲基吡咯烷酮混合，600r/min机械搅拌20min，1000W超声20min，得到混合液。再用1.0mm硅酸锆珠的砂磨机，循环打浆240min得到流动性好的石墨烯导电浆料。20g graphite powder and 1L ethanol were mixed into 1.5L aqueous solution, mechanically stirred at 600r/min for 20min, 3000W ultrasonic for 6h, then filtered and dried to obtain graphene nanosheets, 4g nanosheets, 4g dodecylbenzenesulfonic acid Sodium was mixed with 92 g of N-methylpyrrolidone, mechanically stirred at 600 r/min for 20 min, and ultrasonicated at 1000 W for 20 min to obtain a mixed solution. Then, using a sand mill of 1.0 mm zirconium silicate beads, the slurry was lubricated for 240 minutes to obtain a graphene conductive paste having good fluidity.

对本发明实施例3制备的高导电石墨烯进行流变粘度表征。The high conductivity graphene prepared in Example 3 of the present invention was characterized by rheological viscosity.

参见图4，图4为本发明实施例3制备的高导电石墨烯的流变测试数据曲线。Referring to FIG. 4, FIG. 4 is a rheological test data curve of the highly conductive graphene prepared in Example 3 of the present invention.

由图4可知，本发明实施例3制备的高导电石墨烯在10s ^-1的剪切速率条件下，粘度为872mPa·s，表观流动性较好。 As can be seen from Fig. 4, the highly conductive graphene prepared in Example 3 of the present invention has a viscosity of 872 mPa·s at a shear rate of 10 s ^-1 and a good apparent fluidity.

对本发明实施例3制备的高导电石墨烯进行元素分析，本发明实施例3制备的高导电石墨烯的碳含量达到了99.462％。Elemental analysis was performed on the highly conductive graphene prepared in Example 3 of the present invention, and the carbon content of the highly conductive graphene prepared in Example 3 of the present invention reached 99.462%.

对本发明实施例3制备的高导电石墨烯，采用四探针电导率测试法，测量电导率。For the highly conductive graphene prepared in Example 3 of the present invention, the conductivity was measured by a four-probe conductivity test method.

本发明实施例3制备的高导电石墨烯的电导率达到了62000S/m。The conductivity of the highly conductive graphene prepared in Example 3 of the present invention reached 62000 S/m.

对本发明实施例3制备的高导电石墨烯的稳定性进行测试。The stability of the highly conductive graphene prepared in Example 3 of the present invention was tested.

24小时后，实施例3制备的高导电石墨烯无分层，流变数据显示约为920mPa·s，流动性较好。After 24 hours, the highly conductive graphene prepared in Example 3 had no delamination, and the rheological data showed about 920 mPa·s, and the fluidity was good.

以上对本发明提供的一种高流动性石墨烯导电浆料的制备方法进行了详细的介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想，包括最佳方式，并且也使得本领域的任何技术人员都能够实践本发明，包括制造和使用任何装置或***，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。本发明专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。The method for preparing a high-flow graphene conductive paste provided by the present invention is described in detail above. The principles and embodiments of the present invention are described in detail herein. The description of the above embodiments is only used for The method of the present invention, as well as the core concepts thereof, are included in the best mode of the invention, and are intended to enable any person skilled in the art to practice the invention, including making and using any device or system, and performing any combination. It should be noted that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention. The scope of the invention is defined by the claims, and may include other embodiments that are apparent to those skilled in the art. Such other embodiments are intended to be included within the scope of the appended claims.

Claims

一种石墨烯导电浆料的制备方法，其特征在于，包括以下步骤：A method for preparing a graphene conductive paste, comprising the steps of:

1)将石墨分散液在超声的条件下进行剥离后，再分离，得到石墨烯纳米片；1) after the graphite dispersion is stripped under ultrasonic conditions, and then separated to obtain graphene nanosheets;

2)将上述步骤得到的石墨烯纳米片、分散剂和溶剂进行混合后，得到预浆料；2) mixing the graphene nanosheets obtained by the above steps, a dispersing agent and a solvent to obtain a pre-slurry;

3)将上述步骤得到的预浆料进行砂磨打浆后，得到石墨烯导电浆料。3) After the pre-slurry obtained in the above step is sanded and beaten, a graphene conductive paste is obtained.
根据权利要求1所述的制备方法，其特征在于，所述石墨分散液中的石墨包括石墨粉、鳞片石墨、人造石墨、可膨胀石墨和膨胀石墨中的一种或多种；The preparation method according to claim 1, wherein the graphite in the graphite dispersion comprises one or more of graphite powder, flake graphite, artificial graphite, expandable graphite, and expanded graphite;

所述石墨分散液中石墨的质量浓度为0.5％～5％；The mass concentration of graphite in the graphite dispersion is 0.5% to 5%;

所述石墨分散液中的溶剂包括水和与水互溶的有机溶剂。The solvent in the graphite dispersion includes water and an organic solvent which is miscible with water.
根据权利要求2所述的制备方法，其特征在于，所述与水互溶的有机溶剂包括甲醇、乙醇、乙二醇、甘油、丙酮、四氢呋喃、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和二甲基亚砜中的一种或多种；The preparation method according to claim 2, wherein the water-miscible organic solvent comprises methanol, ethanol, ethylene glycol, glycerin, acetone, tetrahydrofuran, dimethylformamide, dimethylacetamide, N. - one or more of methyl pyrrolidone and dimethyl sulfoxide;

所述与水互溶的有机溶剂在所述石墨分散液中的质量浓度为30％～70％；The mass concentration of the water-miscible organic solvent in the graphite dispersion is 30% to 70%;

所述超声的功率为600～3000W；所述超声的时间为1～20h；The ultrasonic power is 600-3000 W; the ultrasonic time is 1-20 h;

所述分离后还包括干燥步骤。The separation also includes a drying step.
根据权利要求1所述的制备方法，其特征在于，所述剥离的方式包括搅拌、剪切、球磨和砂磨中的一种或多种；The preparation method according to claim 1, wherein the peeling means comprises one or more of stirring, shearing, ball milling, and sanding;

所述石墨烯纳米片的含碳量大于等于98％；The graphene nanosheet has a carbon content of 98% or more;

所述石墨烯纳米片的厚度为小于等于5nm；The thickness of the graphene nanosheet is less than or equal to 5 nm;

所述石墨烯纳米片的片径为1～20μm。The graphene nanosheet has a sheet diameter of 1 to 20 μm.
根据权利要求1所述的制备方法，其特征在于，所述分散剂包括聚乙烯吡咯烷酮、聚偏氯乙烯、聚丙烯、十六烷基三甲基溴化铵和十二烷基苯磺酸钠中的一种或多种；The preparation method according to claim 1, wherein the dispersing agent comprises polyvinylpyrrolidone, polyvinylidene chloride, polypropylene, cetyltrimethylammonium bromide, and sodium dodecylbenzenesulfonate. One or more of

所述溶剂包括水、乙醇、丙酮、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和二甲基亚砜中的一种或多种；The solvent includes one or more of water, ethanol, acetone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide;

所述预浆料中，所述分散剂的质量浓度为0.2％～10％；In the pre-slurry, the mass concentration of the dispersant is 0.2% to 10%;

所述预浆料中，所述石墨烯纳米片的质量浓度为1％～10％。In the pre-slurry, the graphene nanosheet has a mass concentration of 1% to 10%.
根据权利要求1所述的制备方法，其特征在于，所述砂磨为湿法砂磨；The preparation method according to claim 1, wherein the sanding is wet sanding;

所述砂磨的砂磨介质的尺寸为0.1～2mm；The sanding sanding medium has a size of 0.1 to 2 mm;

所述石墨烯导电浆料的电导率大于等于40000S/m。The electrical conductivity of the graphene conductive paste is greater than or equal to 40,000 S/m.
根据权利要求6所述的制备方法，其特征在于，所述湿法砂磨为湿法超细砂磨；The preparation method according to claim 6, wherein the wet sanding is wet superfine sanding;

所述砂磨介质包括硅酸锆珠、氧化锆珠、玻璃珠和钢珠中的一种或多种；The sanding medium comprises one or more of zirconium silicate beads, zirconia beads, glass beads and steel balls;

所述砂磨的次数为2～50次。The number of sanding is 2 to 50 times.
根据权利要求1所述的制备方法，其特征在于，所述石墨为经过预处理后的石墨；The preparation method according to claim 1, wherein the graphite is pretreated graphite;

所述预处理的步骤为：The steps of the pre-processing are:

A)将石墨和小分子插层剂进行反应后，得到插层石墨；A) after the graphite and the small molecule intercalation agent are reacted, the intercalated graphite is obtained;

B)将上述步骤得到的插层石墨经过高温膨胀后，得到处理后的石墨。B) After the intercalated graphite obtained in the above step is expanded at a high temperature, the treated graphite is obtained.
根据权利要求8所述的制备方法，其特征在于，所述石墨的粒度为50～10000目；The preparation method according to claim 8, wherein the graphite has a particle size of 50 to 10,000 mesh;

所述石墨的碳含量大于等于70％；The carbon content of the graphite is greater than or equal to 70%;

所述小分子插层剂包括小分子高温可分解化合物；The small molecule intercalating agent comprises a small molecule high temperature decomposable compound;

所述反应的时间为10～30小时；所述反应的温度为0～40℃。The reaction time is 10 to 30 hours; the temperature of the reaction is 0 to 40 °C.
根据权利要求9所述的制备方法，其特征在于，所述小分子插层剂包括硫酸、硝酸、尿素、碳酸氢钠、碳酸二氢钠、碳酸氢二钠、草酸、磷酸、高氯酸、高碘酸和三氟甲磺酸中的一种或多种；The preparation method according to claim 9, wherein the small molecule intercalating agent comprises sulfuric acid, nitric acid, urea, sodium hydrogencarbonate, sodium dihydrocarbonate, disodium hydrogencarbonate, oxalic acid, phosphoric acid, perchloric acid, One or more of periodic acid and trifluoromethanesulfonic acid;

所述石墨与小分子插层剂的质量比为1：(1～5)；The mass ratio of the graphite to the small molecule intercalant is 1: (1 ~ 5);

所述高温膨胀的温度为500～1200℃；The high temperature expansion temperature is 500 to 1200 ° C;

所述高温膨胀的时间为5～60秒。The high temperature expansion time is 5 to 60 seconds.