WO2012167700A1

WO2012167700A1 - Method for preparing graphene by using solid carbon source

Info

Publication number: WO2012167700A1
Application number: PCT/CN2012/076190
Authority: WO
Inventors: 瞿研
Original assignee: 无锡第六元素高科技发展有限公司
Priority date: 2011-06-09
Filing date: 2012-05-29
Publication date: 2012-12-13
Also published as: CN102259849A

Abstract

The present invention relates to a method for preparing graphene by using solid carbon source. The method comprises heating a substrate coated by solid carbon source in protection atmosphere, and then obtaining a metal substrate deposited with graphene by cooling down. The solid carbon source is selected from organic polymer, preferably from polymethyl methacrylate and/or polydimethylsiloxane, more preferably from polydimethylsiloxane. The method for preparing graphene provided by present invention does not use explosive gas and the production process is safe and credible. Meanwhile, the size of the graphene provided by present invention can be up to a size more than 1 centimeter; the graphene is superior in quality and has good transparence; and the thickness of the graphene can be controllable from monolayer to multilayer. The monoatomiclayer graphene can be easily obtained by the method.

Description

一种固态碳源制备石墨烯的方法 Method for preparing graphene by solid carbon source

技术领域 Technical field

本发明涉及石墨烯材料的制备技术领域，具体地涉及一种化学气相沉积制备单层和多层石墨烯的方法。 The present invention relates to the technical field of preparation of graphene materials, and in particular to a method for preparing single layer and multilayer graphene by chemical vapor deposition.

背景技术 Background technique

石墨烯，英文名 Graphene, 是碳原子按照六角排列而成的二维晶格结构。作为单层碳原子平面材料，石墨烯可以通过剥离石墨材料而得到。这种石墨晶体薄膜自 2004年被曼彻斯特大学的科学家发现之后，石墨烯就成为科学界和工业界关注的焦点。石墨烯的厚度只有 0.335nm，不仅是己知材料中最薄的一种，还非常牢固坚硬；作为单质，他在室温下传递电子的速度比已知所有的导体和半导体都快（石墨烯中电子的迁移速度达到了光速的 1/300)。由于石墨烯的特殊原子结构，其中载流子（电子和空穴）的行为必须用相对论量子力学 ( Relativistic Quantum Mechanics ) 才能描绘。由于其高电子迁移率以及高透光率，石墨烯可能被应用在各种信息技术领域，例如作为透明导电电极应用在平板显示器上，或者作为沟道层应用在高频 /射频晶体管上。同时，作为单层碳原子结构，石墨烯的理论比表面积高达 2630m²/g。如此高的比表面积使得以基于石墨烯的材料成为极有前途的能量储存活性材料，使得石墨烯材料有可能在储氢、新型锂离子电池、超级电容器或者燃料电池得到应用。 Graphene, the English name Graphene, is a two-dimensional lattice structure in which carbon atoms are arranged in hexagons. As a single-layer carbon atom planar material, graphene can be obtained by peeling off a graphite material. Since the graphite crystal film was discovered by scientists at the University of Manchester in 2004, graphene has become the focus of attention in the scientific and industrial circles. Graphene has a thickness of only 0.335 nm, which is not only the thinnest of the known materials, but also very strong and hard. As a simple substance, it transmits electrons at room temperature faster than all known conductors and semiconductors (graphene The migration speed of electrons reaches 1/300 of the speed of light). Due to the special atomic structure of graphene, the behavior of carriers (electrons and holes) must be characterized by Relativistic Quantum Mechanics. Due to its high electron mobility and high light transmittance, graphene may be used in various information technology fields, for example, as a transparent conductive electrode for flat panel displays, or as a channel layer for high frequency/RF transistors. Meanwhile, as a single layer structure of carbon atoms, the theoretical specific surface area of up graphene 2630m ² / g. Such a high specific surface area makes the graphene-based material a promising energy storage active material, making it possible to use graphene materials in hydrogen storage, new lithium ion batteries, supercapacitors or fuel cells.

目前有以下几种方法制备这种特殊的材料： There are several ways to prepare this special material:

1. 轻微摩擦法或撕胶带法（粘贴 HOPG (高定向热解石墨）） 1. Slight rubbing or tearing tape method (paste HOPG (highly oriented pyrolytic graphite))

这种方法简单易行，容易得到高质量的石墨烯。但是产率极低，在一块 Si 衬底上通常只能得到若干片微米见方的石墨烯。因此这种方法只适用于实验室制备石墨烯，不适用于工业化大规模生产。 This method is simple and easy to obtain high quality graphene. But the yield is extremely low, in a piece of Si Usually only a few micrometers of graphene are obtained on the substrate. Therefore, this method is only suitable for the preparation of graphene in the laboratory, and is not suitable for industrial mass production.

2. 加热 SiC法 2. Heating SiC method

该法是通过加热单晶 6H-SiC脱除 Si，在单晶（0001 )面上分解出石墨烯片层。具体过程是：将经氧气或氢气刻蚀处理得到的样品在高真空下通过电子轰击加热，除去氧化物。用俄歇电子能谱确定表面的氧化物完全被移除后，将样品加热使之温度升高至 1250-1450°C后恒温 1分钟到 20分钟，从而形成极薄的石墨层，经过几年的探索， Berger等人已经能可控地制备出单层或是多层石墨烯。由于其厚度由加热温度决定，制备大面积具有单一厚度的石墨烯比较困难。 In this method, Si is removed by heating single crystal 6H-SiC, and a graphene sheet is decomposed on the single crystal (0001) plane. The specific process is as follows: A sample obtained by etching with oxygen or hydrogen is heated by electron bombardment under high vacuum to remove oxides. After the Auchen electron spectroscopy is used to confirm that the oxide on the surface is completely removed, the sample is heated to raise the temperature to 1250-1450 ° C and then thermostated for 1 minute to 20 minutes to form a very thin graphite layer. Exploration, Berger et al. have been able to controllably prepare single or multi-layer graphene. Since the thickness is determined by the heating temperature, it is difficult to prepare a graphene having a single thickness in a large area.

该方法可以实现大尺寸，高质量石墨烯制备，是一种对实现石墨烯器件的实际应用非常重要的制备方法，缺点是 SiC过于昂贵，并且得到的石墨烯难以转移到其他衬底上。 The method can realize large-size, high-quality graphene preparation, and is a preparation method which is very important for realizing the practical application of the graphene device. The disadvantage is that SiC is too expensive, and the obtained graphene is difficult to transfer to other substrates.

3. 化学分散法 3. Chemical dispersion method

氧化石墨是石墨在 H₂S0₄、 HN0₃、 HC10₄等强氧化剂的作用下，或电化学过氧化作用下，经水解后形成的。氧化石墨同样是一层状共价化合物，层间距离大约为 0.8nm (石墨为 0.335nm)，依制备方法而异。一般认为，氧化石墨中含有 -C-OH、 -C-O-C, 甚至 -COOH等基团。和石墨不同，由于极性基团的存在，氧化石墨片层具有较强的亲水或极性溶剂的特性。因此，氧化石墨在外力，如超声波的作用下在水中或其他极性溶剂中可以发生剥离，形成单层氧化石墨烯 (Graphene Oxide )。制得氧化石墨烯后，再通过化学还原使所制氧化石墨烯脱氧重新石墨化，保持其几何形貌时可恢复部分其导电性。 Graphite oxide is formed by the hydrolysis of graphite under the action of strong oxidants such as H ₂ S0 ₄ , HN0 ₃ , HC10 ₄ or by electrochemical peroxidation. Graphite oxide is also a layered covalent compound with a interlayer distance of about 0.8 nm (graphite is 0.335 nm), which varies depending on the preparation method. It is generally considered that graphite oxide contains a group such as -C-OH, -COC, or even -COOH. Unlike graphite, the graphite oxide sheet has a strong hydrophilic or polar solvent property due to the presence of polar groups. Therefore, the graphite oxide can be peeled off in water or other polar solvent by an external force such as ultrasonic waves to form a single layer of graphene oxide (Graphene Oxide). After the graphene oxide is obtained, the graphene oxide is deoxidized and re-graphitized by chemical reduction, and the conductivity of the portion can be restored when the geometrical morphology is maintained.

该方法在氧化和还原过程中将天然石墨粉解离成单层石墨。虽然在氧化还原过程中只是部分还原其导电性（破坏了石墨烯本身的高电子迁移率），但是其产品具有相当高的粉末比表面积（>700m²/g)，且过程相对简单，因此该方法比较适合工业化大规模生产石墨烯材料。但是在氧化还原过程中只是部分还原其导电性（破坏了石墨烯本身的高电子迁移率）。 The method dissociates natural graphite powder into a single layer of graphite during oxidation and reduction. Although it only partially reduces its conductivity during the redox process (destroying the high electron mobility of graphene itself), The product has a relatively high powder specific surface area (>700 m ² /g) and the process is relatively simple, so the method is more suitable for industrial large-scale production of graphene materials. However, it is only partially reduced in conductivity during the redox process (destroying the high electron mobility of the graphene itself).

4、金属衬底化学气相沉积法（CVD， Chemical Vapor Deposition) 4. Metal substrate chemical vapor deposition (CVD, Chemical Vapor Deposition)

化学气相沉积法是利用衬底的原子结构外延出石墨烯，首先让碳原子在高温（1000°C ) 下溶解到金属衬底中，金属的碳溶解度随着温度降低而降低。当衬底冷却后，碳原子在金属中达到过饱和状态，之前溶解的大量碳原子就会析出到金属表面形成厚度可控的石墨烯。 The chemical vapor deposition method utilizes the atomic structure of the substrate to epitaxially form graphene. First, the carbon atoms are dissolved in the metal substrate at a high temperature (1000 ° C), and the carbon solubility of the metal decreases as the temperature decreases. When the substrate is cooled, the carbon atoms are supersaturated in the metal, and a large amount of carbon atoms dissolved before they are deposited on the metal surface to form a graphene having a controlled thickness.

这种方法可以得到高质量大面积（厘米尺寸）的单层或者多层石墨烯，是目前最为重要的一种石墨烯制备方法。然而，制备石墨烯的过程需要用到可燃性气体，例如氢气和甲烷，具有一定的危险性。 This method can obtain high-quality large-area (cm-size) single-layer or multi-layer graphene, and is currently the most important method for preparing graphene. However, the process of preparing graphene requires the use of flammable gases such as hydrogen and methane, which are dangerous.

现有技术已有报道，选用 SiC作为固体碳源来生长石墨烯（Hofrichter J, Szafranek B N, Otto M, et al. Synthesis of graphene on silicon dioxide by a solid carbon source [J]. Nano Letters, 2010, 10(1): 36-42. )。但是该方法所使用的 SiC价格昂贵，造成石墨烯的成本较高。 It has been reported in the prior art that SiC is used as a solid carbon source to grow graphene (Hofrichter J, Szafranek BN, Otto M, et al. Synthesis of graphene on silicon dioxide by a solid carbon source [J]. Nano Letters, 2010, 10(1): 36-42. ). However, the SiC used in this method is expensive, resulting in a high cost of graphene.

如何开发一种缺陷低、透光性好、尺寸大且厚度单一可控的石墨烯，并且其制备方法简单、易控、安全（如不使用***性气体），是本领域的一个技术问题。 How to develop a graphene with low defect, good light transmittance, large size and single thickness controllable, and its preparation method is simple, easy to control and safe (such as not using explosive gas), which is a technical problem in the art.

发明内容 Summary of the invention

针对现有技术的不足，本发明的目的之一在于克服现有石墨烯制备方法的缺陷，提供了一种制备超大面积单层或者多层石墨烯薄膜的方法。所述方法是利用固体碳源，在保护气氛中完成渗碳-析碳的过程。 In view of the deficiencies of the prior art, one of the objects of the present invention is to overcome the deficiencies of the existing method for preparing graphene, and to provide a method for preparing a super-large area single-layer or multi-layer graphene film. The method utilizes a solid carbon source to complete the carburization-carbonization process in a protective atmosphere.

本发明是通过如下技术方案实现的：所述方法是在保护气氛中，加热涂覆有固体碳源的衬底，降温得沉积有石墨烯的金属衬底。 The invention is achieved by the following technical solutions: The method is to heat a substrate coated with a solid carbon source in a protective atmosphere, and to cool the metal substrate on which graphene is deposited.

所述固体碳源选自有机聚合物，本领域技术人员所能获知的任何一种有机聚合物均可用于本发明，例如聚甲基丙烯酸甲酯（PMMA)、聚二甲基硅氧烷 (PDMS)、酚醛树脂、聚丙烯酰胺（PMA) 等，本发明不做具体限定。在综合考虑了固体碳源的分解温度、熔化温度等条件后，本发明所述的固体碳源优选自聚甲基丙烯酸甲酯和 \或聚二甲基硅氧烷，进一歩优选聚二甲基硅氧烷。 The solid carbon source is selected from the group consisting of organic polymers, and any of the organic polymers known to those skilled in the art can be used in the present invention, such as polymethyl methacrylate (PMMA), polydimethylsiloxane ( PDMS), phenol resin, polyacrylamide (PMA), etc., are not specifically limited in the present invention. The solid carbon source of the present invention is preferably selected from polymethyl methacrylate and/or polydimethylsiloxane, and preferably polydimethylene, after taking into consideration conditions such as decomposition temperature and melting temperature of the solid carbon source. Silicone.

在本发明中，衬底为金属衬底。衬底的选择决定了石墨烯的生长温度、生长机制和使用的保护气类型，同时，金属的晶体类型和晶体取向也会影响石墨烯的生长质量。本发明在考虑了金属的熔点、溶碳量以及是否有稳定的金属碳化物等因素后，本发明所述金属衬底选自镍箔、铜箔、铷箔、钴箔、钯箔、铂箔、铱箔或钌箔中的任意 1种或至少 2种的组合，例如铜箔、镍箔、钯金属箔、钴 -钯合金箔、铜 -铱-钌合金箔等，优选铜箔和 /或镍箔，进一歩优选镍箔。 In the present invention, the substrate is a metal substrate. The choice of substrate determines the growth temperature, growth mechanism and type of shielding gas used. At the same time, the crystal type and crystal orientation of the metal also affect the quality of graphene growth. The metal substrate of the present invention is selected from the group consisting of nickel foil, copper foil, tantalum foil, cobalt foil, palladium foil, platinum foil after considering the melting point of the metal, the amount of carbon dissolved, and whether there is a stable metal carbide or the like. Any one or a combination of at least two of ruthenium foil or ruthenium foil, such as copper foil, nickel foil, palladium metal foil, cobalt-palladium alloy foil, copper-ruthenium-iridium alloy foil, etc., preferably copper foil and/or Nickel foil, a preferred nickel foil.

本发明所述保护气由氢气与惰性气体组成，本发明所述的保护气不具有可燃性、 ***性，能够保证生产过程的安全可靠。保护气中氢气与惰性气体的体积比越大，危险性越大（容易***）；但是体积比越小，石墨烯沉积过程的保护又不彻底，因此，本发明所述保护气优选氢气的体积百分比 3vol%，例如 2·9νο1%、 2·82νο1%、 2·54νο1%、 2·33νο1%、 2· 1νο1%、 1·87νο1%、 1·4νο1%、 1·2νο1%、 1.0vol%、 0.8νο1%等，优选 l-3vol%，进一歩优选 2-3vol%。 The shielding gas of the invention consists of hydrogen and an inert gas. The shielding gas according to the invention is not flammable and explosive, and can ensure the safety and reliability of the production process. The larger the volume ratio of hydrogen to inert gas in the shielding gas, the greater the risk (easy to explode); however, the smaller the volume ratio, the less the protection of the graphene deposition process. Therefore, the shielding gas of the present invention preferably has a volume of hydrogen. Percentage 3vol%, for example, 2·9νο1%, 2·82νο1%, 2·54νο1%, 2·33νο1%, 2·1νο1%, 1·87νο1%, 1·4νο1%, 1·2νο1%, 1.0vol%, 0.8 Οο1%, etc., preferably 1-3 vol%, further 2-3 vol%.

优选地，本发明所述保护气体中的惰性气体为不与石墨烯反应的气体，任何一种本领域技术人员能够获知的，不与石墨烯反应的气体均可用于本发明。优选地，所述惰性气体选自氮气、氦气、氖气、氩气、氪气或氙气中的任意 1 种或至少 2种的组合，所述组合例如氮气 /氦气、氦气 /氖气、氩气 /氖气、氦气 / 氪气 /氖气、氦气 /氖气 /氩气等，进一歩优选氮气、氩气或氦气中的任意 1种或至少 2种的组合；特别优选氮气和 /或氩气。本发明对所述惰性气体的纯度不做具体限定，优选地，本发明所述的惰性气体的纯度为 99.99%。 Preferably, the inert gas in the shielding gas of the present invention is a gas which does not react with graphene, and any gas which is known to those skilled in the art and which does not react with graphene can be used in the present invention. Preferably, the inert gas is selected from any one or a combination of at least two of nitrogen, helium, neon, argon, neon or xenon, such as nitrogen/helium, helium/helium. , argon / helium, helium / Helium/helium, helium/helium/argon, etc., preferably one or a combination of at least two of nitrogen, argon or helium; particularly preferably nitrogen and/or argon. The purity of the inert gas is not specifically limited in the present invention. Preferably, the purity of the inert gas of the present invention is 99.99%.

作为优选技术方案，本发明所述固态碳源制备石墨烯的方法包括如下歩骤： As a preferred technical solution, the method for preparing graphene by the solid carbon source of the present invention comprises the following steps:

( 1 ) 在衬底上涂覆固体碳源； (1) coating a solid carbon source on the substrate;

(2 ) 将衬底置于真空反应炉中； (2) placing the substrate in a vacuum reactor;

(3 ) 除去真空腔内的氧气； (3) removing oxygen from the vacuum chamber;

(4) 向真空腔内注入保护气体； (4) injecting a shielding gas into the vacuum chamber;

( 5 ) 升温、保温、同时保持保护气流量； (5) Heating, keeping warm, and maintaining the flow of protective gas;

( 6) 降温，得沉积石墨烯的金属衬底； (6) cooling, a metal substrate on which graphene is deposited;

(7 ) 取出沉积有石墨烯的金属衬底。 (7) A metal substrate on which graphene is deposited is taken out.

优选地，歩骤（1 ) 所述在衬底上涂覆固体碳源包括如下歩骤： Preferably, the step (1) of coating the solid carbon source on the substrate comprises the following steps:

( la) 在衬底表面喷涂有机聚合物作为固态碳源； (la) spraying an organic polymer on the surface of the substrate as a solid carbon source;

( lb) 将衬底置于甩胶机上匀化； ( lb) placing the substrate on a silicone machine to homogenize;

( lc) 将经匀化的金属衬底加热。 ( lc) The homogenized metal substrate is heated.

其中，歩骤（la) 所述有机聚合物的喷涂量没有具体限定，本领域技术人员可以根据实际的试验情况（例如基体的大小、所需获得的石墨烯片层的大小、有机聚合物的种类等）进行选择，本发明优选有机聚合物的喷涂量为 0.1-10ml，例如 0.11mL、 0.13mL、 0.29mL、 0.84mL、 1.2mL、 2.8mL、 3.3mL、 4.5mL、 6.8mL、 7.5mL、 8.0mL、 8.5mL、 9.5mL、 9.7mL等。 Wherein, the spraying amount of the organic polymer in the step (la) is not specifically limited, and those skilled in the art can according to actual experimental conditions (for example, the size of the substrate, the size of the graphene sheet to be obtained, and the organic polymer). Type, etc.) In the present invention, it is preferred that the organic polymer is sprayed in an amount of 0.1 to 10 ml, for example, 0.11 mL, 0.13 mL, 0.29 mL, 0.84 mL, 1.2 mL, 2.8 mL, 3.3 mL, 4.5 mL, 6.8 mL, 7.5 mL. 8.0 mL, 8.5 mL, 9.5 mL, 9.7 mL, and the like.

歩骤（lb ) 将衬底置于甩胶机上匀化的目的是为了使碳源均匀的涂覆在基体上，从而使得到的石墨烯层厚度更加均一。本领域技术人员能够获知的任何一种能够达到该目的的手段均可用于本发明，本发明不做限定。优选地，本发明通过甩胶机使碳源均匀的涂覆在基体上。甩胶机，是一种利用旋转产生的离心力原理，将胶液均匀甩开，平铺到材料表面的机械装置。 Step (lb) The purpose of homogenizing the substrate on a silicone machine is to uniformly coat the carbon source on the substrate, thereby making the resulting graphene layer more uniform in thickness. Any means that can be achieved by those skilled in the art that can achieve the object can be used in the present invention, and the present invention is not limited thereto. Preferably, the present invention uniformly coats the carbon source on the substrate by means of a silicone machine. The silicone machine is a mechanical device that uses the principle of centrifugal force generated by rotation to evenly pry the glue and lay it on the surface of the material.

优选地，本发明歩骤（lb)所述的甩胶机的转速为 500-10000转 /min，优选 700-10000转 /min，进一歩优选 1200-10000转 /min， Preferably, the speed of the rubberizing machine described in the step (lb) of the present invention is 500-10000 rpm, preferably 700-10000 rpm, and further preferably 1200-10000 rpm.

优选地，本发明歩骤（lb)所述的甩胶机的匀化时间为 10s-30min，例如 10s、 21s、 24s、 39s、 50s、 58s、 1.3min、 1.9min、 3.5min、 12.8min、 7.5min、 15.8min、 16.5min、 17.2min、 18.8min、 19min、 19.8min等，优选 12s-25min，进一歩优选 12s-22min。 Preferably, the homogenizing time of the rubberizing machine described in the step (lb) of the present invention is 10 s-30 min, for example, 10 s, 21 s, 24 s, 39 s, 50 s, 58 s, 1.3 min, 1.9 min, 3.5 min, 12.8 min, 7.5 min, 15.8 min, 16.5 min, 17.2 min, 18.8 min, 19 min, 19.8 min, etc., preferably 12 s-25 min, further preferably 12 s-22 min.

优选地，本发明歩骤（lc) 将经匀化的金属衬底加热，所述的加热温度为 30-200 °C, 例如 31°C、 35.5°C、 48°C、 70°C、 95°C、 116°C、 147°C、 168°C、 170 °C、 185°C、 198°C等;所述加热时间优选 10s-60min,例如 12s, 40s、 59s、 1.3min、 5min、 llmir 27min、 32.5min、 42min、 58min、 59.5min、 59.8min。 Preferably, the step (lc) of the present invention heats the homogenized metal substrate at a heating temperature of 30 to 200 ° C, for example, 31 ° C, 35.5 ° C, 48 ° C, 70 ° C, 95 °C, 116 ° C, 147 ° C, 168 ° C, 170 ° C, 185 ° C, 198 ° C, etc.; the heating time is preferably 10 s - 60 min, such as 12 s, 40 s, 59 s, 1.3 min, 5 min, llmir 27 min, 32.5 min, 42 min, 58 min, 59.5 min, 59.8 min.

优选地，歩骤（3) 所述除去真空腔内的氧气包括如下歩骤： Preferably, the removing the oxygen in the vacuum chamber according to the step (3) comprises the following steps:

(3a) 将真空腔抽真空； (3a) evacuating the vacuum chamber;

(3b) 将惰性气体注入真空腔； (3b) injecting an inert gas into the vacuum chamber;

(3c) 将真空腔再次抽真空； (3c) vacuuming the vacuum chamber again;

(3d)重复歩骤（3b)和歩骤（3c)，直至将真空腔内的氧气分压 lxl0-⁶torr。优选地，歩骤（3a) 抽真空至真空状态为 2-15<10-²torr，例如 2<10·²ίθΓΓ、 2.3<10-²torr、 2.7<10-²torr、 4.2<10-²torr、 4.9<10-²torr、 6.1 <10-²torr、 6.7<10-²torr、 7.5xl0-²torr、 8.7xl0-²torr、 9xl0-²torr、 11.4xl0-²torr、 12.9xl0-²torr、 13.9xl0-²torr、 14.4xl0-²torr、14.7xl0-²torr、15xl0-²torr等，优选 3-10xl0-²torr，最优选 4-8xl0-²torr。 (3d) ho repeating step (3b), and ho step (3c), the vacuum chamber until the oxygen partial pressure lxl0- ⁶ torr. Preferably, ho step (3a) is evacuated to a vacuum state 2-15 <10- ² torr, e.g. ^{2 <10 · 2 ίθΓΓ, 2.3} <10- 2 torr, 2.7 <10- 2 torr, 4.2 <10- 2 Torr, 4.9<10- ² torr, 6.1 <10- ² torr, 6.7<10- ² torr, 7.5xl0- ² torr, 8.7xl0- ² torr, 9xl0- ² torr, 11.4xl0- ² torr, 12.9xl0- ² ^{^{torr, 13.9xl0- 2 torr, 14.4xl0- 2}} torr, 14.7xl0- 2 torr, 15xl0- 2 torr and the like, preferably 3-10xl0- ² torr, and most preferably 4-8xl0- ² torr.

优选地，歩骤（3b) 惰性气体的注入量为使真空腔内的压力为 10torr，例如 lltorr、 22torr、 36torr、 49torr、 51torr、 67torr、 78torr、 80torr、 80.4torr、 85torr、 98torr、 99torr、 100torr、 101torr、 103.1torr、 163torr、 203torr、 255torr、 708torr、 1020torr等，优选 100torr。 Preferably, the inert gas is injected in a step (3b) such that the pressure in the vacuum chamber is 10 torr, for example, lltorr, 22 torr, 36 torr, 49 torr, 51 torr, 67 torr, 78 torr, 80 torr, 80.4 torr, 85 torr, 98torr, 99torr, 100torr, 101torr, 103.1torr, 163torr, 203torr, 255torr, 708torr, 1020torr, etc., preferably 100 torr.

优选地，歩骤（3b) 所述惰性气体与还原气体中的惰性气体相同，选自氮气、氦气、氖气、氩气、氪气、氙气中的任意 1种或至少 2种的组合；本发明对所述惰性气体的纯度不做具体限定，只需要将真空腔中的氧气除去以达到氧气分压 lxl0_⁶torr为标准即可，优选地，本发明所述的惰性气体的纯度为 99.99%。 Preferably, the inert gas in the step (3b) is the same as the inert gas in the reducing gas, and is selected from any one of nitrogen, helium, neon, argon, helium, and neon, or a combination of at least two; the present invention is the purity of the inert gas is not particularly limited, and only need to remove oxygen in the vacuum chamber to achieve a partial pressure of oxygen as the standard lxl0_ ⁶ torr, and preferably, the purity of the inert gas in the present invention is 99.99 %.

优选地，歩骤（3c) 抽真空至真空状态为 2-15<10-²torr，例如 2<10-²torr、 2.1xl0-²torr、 3.7<10-²torr、 4.9<10-²torr、 5.9<10-²torr、 6.2<10-²torr、 7.1 <10-²torr、 8.6xl0-²torr、 10.8xl0-²torr、 llxl0-²torr、 11.8xl0-²torr、 12.7xl0-²torr、 13.5xl0-²torr、 14.9xl0-²torr、 14.3xl0-²torr、 15 l0-²torr,优选 3-10xl0-²torr，最优选 4-8x10-²torr。 Preferably, ho step (3c) was evacuated to a vacuum of 2-15 <10- ² torr, for example, ^{^{2 <10- 2 torr, 2.1xl0- 2}} torr, 3.7 <10- 2 torr, 4.9 <10- 2 torr , 5.9<10- ² torr, 6.2<10- ² torr, 7.1 <10- ² torr, 8.6xl0- ² torr, 10.8xl0- ² torr, llxl0- ² torr, 11.8xl0- ² torr, 12.7xl0- ² torr ^{^{, 13.5xl0- 2 torr, 14.9xl0- 2 torr}} , 14.3xl0- 2 torr, 15 l0- 2 torr, preferably 3-10xl0- ² torr, and most preferably 4-8x10- ² torr.

优选地，歩骤（3d) 所述的歩骤（3b) 和歩骤（3c) 的重复次数为 2-8次，例如 2次、 3次、 4次、 6次、 8次，优选 2-5次，最优选 2-3次。 Preferably, the number of repetitions of the step (3b) and the step (3c) described in the step (3d) is 2-8 times, for example, 2 times, 3 times, 4 times, 6 times, 8 times, preferably 2- 5 times, most preferably 2-3 times.

歩骤（3)所述除去真空腔内的氧气的目的是为了防止经过渗碳 -析碳得到的石墨烯与真空腔中的气体发生反应，尤其是与其中的氧气发生反应。因此，歩骤（3) 需要不断重复 "抽真空-充入惰性气体 -抽真空-充入惰性气体"的歩骤，直至将真空腔内的氧气分压 lxl0_⁶torr，本领域技术人员应该明了，此处所述的氧气分压越低，最后得到的石墨烯的质量越好，例如所述的氧气分压为 lxl0-⁶torr、 0.98xl0-⁶torr、 0.92xl0-⁶torr、 0.82xl0-⁶torr、 0.88xl0-⁶torr等。 The purpose of removing oxygen in the vacuum chamber as described in the step (3) is to prevent the graphene obtained by the carburization-carbonization from reacting with the gas in the vacuum chamber, especially with oxygen therein. Thus, ho step (3) requires repeated "evacuation - filled with an inert gas - vacuum - filled with an inert gas" is ho step, the vacuum chamber until the oxygen partial pressure lxl0_ ⁶ torr, should be apparent to those skilled in the art , the lower the oxygen partial pressure described herein, the better the quality of the resulting graphene, for example, the oxygen partial pressure ^{^{lxl0- 6 torr, 0.98xl0- 6 torr,}} 0.92xl0- 6 torr, 0.82xl0- ⁶ torr, 0.88xl0- ⁶ torr, etc.

优选地，气体的注入流量均独立地选自 l-100sccm，例如 l.lsccm、 1.9sccm、 3.5sccm、 9.7sccm、 15sccm、 29sccm、 44sccm、 69sccm、 87sccm、 98sccm、 99.5sccm 等，优选 4-96sccm，进一歩优选 20-80sccm。所述的气体的注入流量包括歩骤（3) 所述的惰性气体流量、歩骤（4) 所述的保护气气体流量和歩骤（7) 所述的惰性气体流量。 Preferably, the injection flow rate of the gas is independently selected from 1 to 100 sccm, such as 1.1 sccm, 1.9 sccm, 3.5 sccm, 9.7 sccm, 15 sccm, 29 sccm, 44 sccm, 69 sccm, 87 sccm, 98 sccm, 99.5 sccm, etc., preferably 4-96 sccm. Further, it is preferably 20-80 sccm. The injection flow rate of the gas includes the inert gas flow rate described in the step (3), the shielding gas gas flow rate described in the step (4), and the inertness described in the step (7). Sexual gas flow.

优选地，本发明所述惰性气体的纯度 99.99%，例如 99.991%、 99.999%等。歩骤（5 )所述升温的温度为石墨烯的生长温度，取决于衬底的种类和碳源的种类。 Preferably, the inert gas of the present invention has a purity of 99.99%, such as 99.991%, 99.999%, and the like. Step (5) The temperature of the temperature rise is the growth temperature of graphene, depending on the kind of the substrate and the kind of the carbon source.

优选地，本发明歩骤（5 )所述升温的温度为 800-1150°C，例如 800°C、 801 °C、 817°C、 832°C、 897°C、 922 °C、 989 °C、 1020°C、 1090°C、 1106°C、 1130°C、 1170°C、 1200°C等，优选 800-1100 °C，进一歩优选 880-1080 °C，特别优选 900-1000 Preferably, the temperature rising temperature in the step (5) of the present invention is 800-1150 ° C, for example, 800 ° C, 801 ° C, 817 ° C, 832 ° C, 897 ° C, 922 ° C, 989 ° C 1020 ° C, 1090 ° C, 1106 ° C, 1130 ° C, 1170 ° C, 1200 ° C, etc., preferably 800-1100 ° C, further preferably 880-1080 ° C, particularly preferably 900-1000

°C。 °C.

优选地，本发明歩骤（5 )所述升温至最高温度后，维持最高温度进行保温，所述保温时间为 l-100min，例如 l. lmin、 1.5min、 5.0min、 18.2min、 25.5min、 29.8min、 34min、 38.2min、 43min、 63.1min、 78.8min、 85.1min、 94.2min、 97.8min、 99.4min等，优选 4-93min，进一歩优选 4.5-82min。 Preferably, after the temperature is raised to the highest temperature in the step (5) of the present invention, the highest temperature is maintained for the heat retention, and the holding time is 1-100 min, for example, l. lmin, 1.5 min, 5.0 min, 18.2 min, 25.5 min, 29.8 min, 34 min, 38.2 min, 43 min, 63.1 min, 78.8 min, 85.1 min, 94.2 min, 97.8 min, 99.4 min, etc., preferably 4-93 min, further preferably 4.5-82 min.

本发明歩骤（6)所述降温的速率决定了石墨烯沉积的速度和沉积得到的石墨烯的外观形貌，优选地，歩骤（6) 所述降温为降至室温，降温速度为 2-18°C /s，例如 2.1 °C/s、 2.7°C/s、 5.8°C/s、 6.9°C/s、 7.6°C/s、 l l °C/s、 13.5 °C/s、 16°C/s、 17.8°C/s等，优选 3-9°C/s，进一歩优选 8°C/s。 The rate of cooling according to step (6) of the present invention determines the speed of graphene deposition and the appearance of graphene deposited. Preferably, the temperature drop is reduced to room temperature and the temperature drop rate is 2 -18 ° C / s, such as 2.1 ° C / s, 2.7 ° C / s, 5.8 ° C / s, 6.9 ° C / s, 7.6 ° C / s, ll ° C / s, 13.5 ° C / s, 16 ° C / s, 17.8 ° C / s, etc., preferably 3-9 ° C / s, further preferably 8 ° C / s.

固态碳源制备石墨烯的原理推测如下：升温至一定高温（800-1150°C )，碳源中的碳元素分解，衬底的溶碳量随温度升高而升高，碳元素渗入衬底，保持该温度一定时间以使衬体中溶入的碳元素达到平衡，然后以一定速率降温，使石墨烯析出，在衬底表面生长得到石墨烯。由此推测的原理可以看出，歩骤（5 ) 所述的升温的温度与碳源的分解温度、衬体的溶碳量和溶碳温度有关；歩骤（5 ) 所述的保温时间与歩骤（6)所述的降温的速率与所要制得的石墨烯的外观形貌 (例如石墨烯的厚度、均一性、表面光滑度等）有着密切的关系。本发明经过歩骤（1 ) - ( 6) 已经得到沉积于衬底的石墨烯，但是如果瞬间释放压力，大量的空气涌入真空腔，则肯定会造成石墨烯的氧化，如何将制得的石墨烯取出，并保证其不被空气中的氧气氧化，就需要进行歩骤（7)，所述歩骤（7 ) 具体包括如下歩骤： The principle of preparing graphene from solid carbon source is presumed as follows: When the temperature is raised to a certain high temperature (800-1150 °C), the carbon element in the carbon source is decomposed, and the amount of carbon dissolved in the substrate increases with the increase of temperature, and the carbon element penetrates into the substrate. The temperature is maintained for a certain period of time to balance the carbon dissolved in the liner, and then the temperature is lowered at a certain rate to precipitate the graphene, and graphene is grown on the surface of the substrate. From this presumed principle, it can be seen that the temperature of the temperature rise described in the step (5) is related to the decomposition temperature of the carbon source, the carbon dissolved amount of the liner, and the carbonization temperature; the holding time described in the step (5) is The rate of temperature reduction described in step (6) is closely related to the appearance of the graphene to be produced (e.g., thickness, uniformity, surface smoothness, etc. of graphene). The present invention has obtained graphene deposited on a substrate through steps (1) - (6), but if a moment of pressure is released, a large amount of air is poured into the vacuum chamber, which will definitely cause oxidation of graphene, how to make it. The graphene is taken out and ensured that it is not oxidized by oxygen in the air, and the step (7) is required. The step (7) specifically includes the following steps:

(7a) 关闭保护气体进气闽、碳源气体进气闽和真空泵； (7a) closing the shielding gas inlet port, the carbon source gas inlet port, and the vacuum pump;

(7b) 打开惰性气体进气闽，充入惰性气体至真空腔内气压为 1个大气压； (7b) Opening the inert gas inlet port, filling the inert gas into the vacuum chamber at a pressure of 1 atmosphere;

(7c) 取出衬底。 (7c) Remove the substrate.

本发明在化学沉积技术的基础上，发展出更为安全、操作性更好的固态碳源石墨烯制备技术。在金属衬底表面喷涂有机薄膜，在高温环境下及还原性气体保护下，有机薄膜在金属衬底的催化作用下分解出碳原子。碳原子在金属表面结晶形成石墨烯薄膜。该方法不涉及危险性气体，是一种安全的石墨烯制备技术。 The invention develops a safer and more operable solid carbon source graphene preparation technology based on the chemical deposition technology. The organic film is sprayed on the surface of the metal substrate, and under the high temperature environment and the reducing gas, the organic film decomposes carbon atoms under the catalytic action of the metal substrate. The carbon atoms crystallize on the surface of the metal to form a graphene film. This method does not involve hazardous gases and is a safe graphene preparation technique.

能够达到以上发明目的的实验装置均可实现本发明，本领域技术人员可以根据自己掌握的专业知识实现在固态碳源制备石墨烯的过程。本发明的优选技术方案是在真空反应炉中完成。本发明所述的真空反应炉为本领域技术人员所熟知的设备，典型但非限制性的有管式炉或气氛炉。 The present invention can be realized by an experimental apparatus capable of achieving the above object, and a person skilled in the art can realize a process of preparing graphene in a solid carbon source based on his own expertise. The preferred embodiment of the invention is accomplished in a vacuum reactor. The vacuum reactor of the present invention is well known to those skilled in the art, and typically, but not exclusively, a tube furnace or an atmosphere furnace.

作为优选技术方案，本发明所述的固态碳源制备石墨烯的方法在化学固相沉积***中进行，所述的化学固相沉积***由保护气流量计 1、惰性气体流量计 2、石英管 4、管式炉 5、真空计 6和衬底 7组成；其中，石英管 4置于管式炉 5 中，石英管 4的一侧通过保护气流量计 1、惰性气体流量计 2分别与保护气体和惰性气体气瓶相连，石英管 4的另一侧依次与真空计 6和真空泵相连。 As a preferred technical solution, the method for preparing graphene by the solid carbon source of the present invention is carried out in a chemical solid phase deposition system, wherein the chemical solid phase deposition system comprises a protective gas flow meter, an inert gas flow meter 2, and a quartz tube. 4. The tube furnace 5, the vacuum gauge 6 and the substrate 7 are composed; wherein, the quartz tube 4 is placed in the tube furnace 5, and one side of the quartz tube 4 is protected by a protective gas flow meter 1 and an inert gas flow meter 2, respectively. The gas is connected to an inert gas cylinder, and the other side of the quartz tube 4 is sequentially connected to a vacuum gauge 6 and a vacuum pump.

作为另一个可选技术方案，所述的石英管和管式炉可以换成一个具有较大空间的气氛炉，其操作歩骤与上述管式炉相同。作为可选技术方案，本发明所述固态碳源制备石墨烯的的方法包括如下歩骤： As an alternative technical solution, the quartz tube and the tube furnace can be replaced by an atmosphere furnace having a larger space, and the operation step is the same as that of the above tube furnace. As an alternative technical solution, the method for preparing graphene by the solid carbon source of the invention comprises the following steps:

(la) 在衬底表面喷涂有机聚合物作为固态碳源； (la) spraying an organic polymer on the surface of the substrate as a solid carbon source;

(lb) 将衬底置于甩胶机上匀化； (lb) placing the substrate on a silicone machine to homogenize;

(lc) 将经匀化的金属衬底加热； (lc) heating the homogenized metal substrate;

(2) 将衬底置于真空反应炉中； (2) placing the substrate in a vacuum reactor;

(3a) 将真空腔抽真空； (3a) evacuating the vacuum chamber;

(3c) 将真空腔再次抽真空； (3c) vacuuming the vacuum chamber again;

(3d)重复歩骤（3b)和歩骤（3c)，直至将真空腔内的氧气分压≤lxl0-⁶torr;(3d) ho repeating step (3b), and ho step (3c), the vacuum chamber until the oxygen partial pressure ≤lxl0- ⁶ torr;

(5) 升温、保温、同时保持保护气流量； (5) Heating, heat preservation, and maintaining the flow of protective gas;

(6) 降温，得沉积石墨烯的金属衬底； (6) cooling, a metal substrate on which graphene is deposited;

(7a) 关闭还原性气体进气闽、碳源气体进气闽和真空泵； (7a) closing the reducing gas inlet port, the carbon source gas inlet port, and the vacuum pump;

(7b) 打开惰性气体进气闽，充入惰性气体至真空腔内气压为 1个大气压; (7c) 取出衬底。 (7b) Open the inert gas inlet 闽 and fill with inert gas until the pressure in the vacuum chamber is 1 atm; (7c) Remove the substrate.

或，本发明所述固态碳源制备石墨烯的的方法包括如下歩骤： Or, the method for preparing graphene by the solid carbon source of the present invention comprises the following steps:

(la) 在衬底表面喷涂有机聚合物（0.1-lOmLPMMA或 PDMS) 作为固态碳源； (la) spraying an organic polymer (0.1-lOmL PMMA or PDMS) on the surface of the substrate as a solid carbon source;

(lb) 将衬底置于甩胶机上匀化，所述甩胶机转速为 500-10000转 /min，甩胶时间为 10s-30min; (lb) the substrate is placed on a silicone mixer, the speed of the silicone machine is 500-10000 rpm, and the glue time is 10 s-30 min;

(lc) 将经匀化的金属衬底加热，加热温度为 30-200 °C，加热时间为 10s-60min; (2) 将衬底置于真空反应炉中； (lc) heating the homogenized metal substrate, heating temperature is 30-200 ° C, heating time is 10s-60min; (2) placing the substrate in a vacuum reactor;

(3a) 将管式炉或气氛炉的气压抽真空至 4-8xl0_²torr; (3a) evacuating the air pressure of the tube furnace or the atmosphere furnace to 4-8xl0_ ² torr;

(3b) 以气体流量 1-lOOsccm将纯度 99.99%的惰性气体注入到真空腔中； (3c) 关闭惰性气体进气闽门，将管式炉或气氛炉的气压抽至极限 4-8 l0-²torr_; (3b) Injecting 99.99% pure inert gas into the vacuum chamber at a gas flow rate of 1-100 sccm; (3c) Closing the inert gas intake valve and pumping the gas pressure of the tube furnace or the atmosphere furnace to the limit 4-8 l0- ² torr _;

(3d) 重复歩骤（3b) 和歩骤（3c) 2-3次，直至将真空腔内的氧气分压 ^l l0-⁶torr_; (3d) Repeat step (3b) and step (3c) 2-3 times until the oxygen in the vacuum chamber is divided into ^l0- ⁶ torr _;

(5)升温至 800-1100°C，并保持在最高温度 l-100min，同时保持保护气流 (5) Warm up to 800-1100 ° C, and keep at the highest temperature l-100min while maintaining the protective airflow

(7b) 打开惰性气体进气闽，充入惰性气体至真空腔内气压为 1个大气压; (7b) Opening the inert gas inlet port, filling the inert gas into the vacuum chamber at a pressure of 1 atmosphere;

(7c) 取出衬底。 (7c) Remove the substrate.

可选地，本发明通过如下技术方案实现： Optionally, the present invention is implemented by the following technical solutions:

一种固态碳源制备石墨烯的方法，歩骤如下： A method for preparing graphene from a solid carbon source, and the steps are as follows:

(1)在金属衬底表面喷涂有机聚合物作为固态碳源，然后将上述金属衬底置于甩胶机上匀化，再将经匀化的金属衬底加热； (1) spraying an organic polymer on the surface of the metal substrate as a solid carbon source, then homogenizing the metal substrate on a silicone machine, and heating the homogenized metal substrate;

(2)将歩骤（1) 的加热后的喷涂固态碳源的金属衬底置于真空反应炉中，在除去真空腔内氧气的情况下，将保护气注入真空腔中，并升温至 800-1100 °C，保持最高温度 1-lOOmin, 同时保持保护气流量，即得沉积石墨烯的金属衬底。 (2) placing the heated metal substrate of the solid carbon source in step (1) in a vacuum reactor, and injecting the shielding gas into the vacuum chamber while removing oxygen in the vacuum chamber, and heating the temperature to 800 -1100 ° C, maintaining the maximum temperature of 1-100 min while maintaining the flow of shielding gas, that is, a metal substrate on which graphene is deposited.

优选地，所述除去真空腔内氧气的方法是： Preferably, the method for removing oxygen in the vacuum chamber is:

(1) 将管式炉或气氛炉的气压抽至极限真空状态 4-8X 10_²torr_; (2 )以气体流量 1-lOOsccm将纯度高于 99.99%的惰性气体注入到真空腔中；(1) pumping the air pressure of the tube furnace or the atmosphere furnace to the ultimate vacuum state 4-8X 10_ ² torr _; (2) injecting an inert gas having a purity higher than 99.99% into the vacuum chamber at a gas flow rate of 1-100 sccm;

( 3 ) 关闭惰性气体进气闽门，将管式炉或气氛炉的气压抽至极限 4-8 X 10-²torr_; (3) Close the inert gas intake door and pump the air pressure of the tube furnace or the atmosphere furnace to the limit of 4-8 X 10- ² torr _;

(4) 重复操作歩骤（2 ) 和歩骤（3 ) 2-3次，直至将管式炉或气氛炉内的残余氧气除至氧气分压小于 10_⁶torr。 (4) Repeat steps (2) and (3) 2-3 times until the residual oxygen in the tube furnace or atmosphere furnace is removed to a partial pressure of oxygen of less than 10 _ ⁶ torr.

优选地，所述金属衬底为铜箔或镍箔。 Preferably, the metal substrate is a copper foil or a nickel foil.

优选地，所述作为固态碳源的有机聚合物为 PMMA或 PDMS。 Preferably, the organic polymer as a solid carbon source is PMMA or PDMS.

优选地，所述保护气为体积比为 97%氩气与 3%氢气的混合气体。 Preferably, the shielding gas is a mixed gas of a volume ratio of 97% argon gas and 3% hydrogen gas.

优选地，一种固态碳源制备石墨烯的方法，歩骤如下： Preferably, a method for preparing graphene from a solid carbon source is as follows:

( 1 ) 在金属衬底表面喷涂有机聚合物（0.1-lOmL PMMA或 PDMS ) 作为固态碳源，然后将上述金属衬底置于甩胶机上匀化（转速为 500-10000转 /min，时间为 10s-30min)，再将经匀化的金属衬底加热（加热温度 30-200 °C，时间为 10s-60min) _; (2) 将歩骤（1 ) 的加热后的喷涂固态碳源的金属衬底置于真空反应炉中，在除去真空腔内氧气的情况下，将保护气注入真空腔中，并升温至 800-1100 °C , 保持在最高温度 l-100min，同时保持保护气体流量，即得沉积石墨烯的金属衬底。 (1) spraying an organic polymer (0.1-lOmL PMMA or PDMS) on the surface of the metal substrate as a solid carbon source, and then homogenizing the above metal substrate on a silicone machine (rotation speed of 500-10000 rev / min, time is 10s-30min), then heat the homogenized metal substrate (heating temperature 30-200 °C, time is 10s-60min) _; (2) heat the sprayed solid carbon source metal after the step (1) The substrate is placed in a vacuum reactor, and in the case of removing oxygen in the vacuum chamber, the shielding gas is injected into the vacuum chamber, and the temperature is raised to 800-1100 ° C, and maintained at the highest temperature for l-100 min while maintaining the flow rate of the shielding gas. That is, a metal substrate on which graphene is deposited.

本发明的目的之二在于提供一种前述通过固态碳源制备得到的石墨烯，所述石墨烯厚度可控；所述石墨烯的厚度为单原子层石墨烯或者多原子层石墨烯。本发明通过控制保护气体的流速、升温温度、保温时间、降温速率等操作条件，来得到单原子层石墨烯或者多原子层石墨烯。 A second object of the present invention is to provide a graphene prepared by a solid carbon source, wherein the thickness of the graphene is controllable; and the graphene has a thickness of a single atomic layer graphene or a polyatomic layer graphene. The present invention obtains a single atomic layer graphene or a polyatomic layer graphene by controlling operating conditions such as a flow rate of a shielding gas, a temperature rising temperature, a holding time, and a temperature decreasing rate.

优选地，所述石墨烯为多原子层石墨烯； Preferably, the graphene is a polyatomic layer graphene;

优选地，所述石墨烯为单原子层石墨烯。 Preferably, the graphene is a monoatomic layer graphene.

本发明的目的之三在于提供一种通过固态碳源制备得到的石墨烯的用途，所述石墨烯用于能量储存活性材料、微处理器、电池、显示器和柔性电子器件，优选用于储氢、锂离子电池、超级电容器或者燃料电池，以及纳电子器件、高频电路、光子传感器、基因电子测序、减少噪音、高频 /射频晶体管、平板显示和柔性显示器。 A third object of the present invention is to provide a use of graphene prepared by a solid carbon source, The graphene is used for energy storage active materials, microprocessors, batteries, displays, and flexible electronic devices, preferably for hydrogen storage, lithium ion batteries, supercapacitors or fuel cells, and nanoelectronic devices, high frequency circuits, photonic sensors , Gene electronic sequencing, noise reduction, HF/RF transistors, flat panel displays and flexible displays.

与现有技术相比，本发明具有如下有益效果： Compared with the prior art, the present invention has the following beneficial effects:

( 1 )本发明提供固态碳源制备石墨烯不使用***性气体、生产过程安全可罪； (1) The present invention provides a solid carbon source for preparing graphene without using an explosive gas, and the production process is safe and guilty;

(2) 本发明提供的石墨烯的尺寸可以达到厘米以上尺寸； (2) The graphene provided by the present invention may have a size of more than a centimeter;

(3 ) 本发明提供的石墨烯产品具有极高质量、透光性好； (3) The graphene product provided by the invention has high quality and good light transmittance;

(4)本发明提供的石墨烯的厚度从单层到多层可控，容易得到单原子层石墨烯。 (4) The thickness of the graphene provided by the present invention is controllable from a single layer to a plurality of layers, and a monoatomic layer of graphene is easily obtained.

附图说明 DRAWINGS

附图用来提供对本发明的进一歩理解，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。 The drawings are intended to provide a further understanding of the invention, and are intended to be a part of the description of the invention.

图 1是本发明实施例 1-3所述化学固相沉积***的结构示意图； 1 is a schematic structural view of a chemical solid phase deposition system according to Embodiments 1-3 of the present invention;

图 2是本发明实施例 3所制备石墨烯的拉曼光谱图。 Fig. 2 is a Raman spectrum diagram of graphene prepared in Example 3 of the present invention.

附图标记 Reference numeral

1-保护气流量计、 2-惰性气体流量计、 4-石英管、 5-管式炉、 6-真空计和 7- 衬底。 1-protective gas flow meter, 2-inert gas flow meter, 4-quartz tube, 5-tube furnace, 6-vacuum meter and 7-substrate.

具体实施方式 detailed description

为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。 In order to facilitate the understanding of the present invention, the present invention is exemplified by the following. It should be understood by those skilled in the art that the present invention is not to be construed as limited.

实施例 1 采用高温分解固态碳源，在金属衬底上结晶形成石墨烯薄膜，所述方法在化学固相沉积***中进行，包括以下制备歩骤： Example 1 Forming a graphene film on a metal substrate by pyrolysis of a solid carbon source, the method being carried out in a chemical solid phase deposition system, comprising the following preparation steps:

( la) 取 20mm²的平整的金属铜箔，固定于玻璃片上，将玻璃片固定在离心甩胶机上，在金属衬底表面喷滴 0. ImL PMMA (固态碳源聚甲基丙烯酸甲酯）； ( lb) 设定甩胶机转速为 500转 /min，时间为 30min。； (La) takes 20mm flat metal foil ² is fixed to the glass sheet, the glass sheet is fixed to the centrifugal rejection of the melter, the surface of the substrate sprayed metal droplets 0. ImL PMMA (polymethyl methacrylate solid carbon source) ( lb) Set the speed of the silicone machine to 500 rpm and the time is 30 minutes. ;

( lc) 取下玻璃片上的金属衬底，在加热盘上加热至 30°C，时间为 60min_; (2 ) 将喷涂固态碳源的金属衬底 7置于石英管 4中； ( lc) removing the metal substrate on the glass piece, heating to 30 ° C on the heating plate for 60 min _; (2) placing the metal substrate 7 coated with the solid carbon source in the quartz tube 4;

(3a) 将石英管 4的气压抽至极限真空状态 4 X 10-²torr_; (3a) pumping the air pressure of the quartz tube 4 to the ultimate vacuum state 4 X 10- ² torr _;

(3b)设定惰性气体流量计 2的气体流量 5sccm，将惰性气体注入到石英管 (3b) setting the gas flow rate of the inert gas flow meter 2 to 5 sccm, injecting inert gas into the quartz tube

4中； 4;

(3c) lOmin后，关闭惰性气体流量计 2的进气闽门，将石英管 4的气压抽至极限 4 Χ 10·² torr; (3c) After lOmin, close the intake valve of the inert gas flow meter 2, and draw the air pressure of the quartz tube 4 to the limit 4 Χ 10· ² torr;

( 3d) 重复歩骤（3b) 和歩骤（3c) 的操作歩骤 2次；直到将石英管 4内的残余氧气驱赶干净至氧气分压 10_⁶torr_; (3d) Repeat the steps of step (3b) and step (3c) twice; until the residual oxygen in the quartz tube 4 is driven clean to a partial pressure of oxygen 10_ ⁶ torr _;

(4)设定保护气流量计 1的气体流量为 5sccm，将保护气持续注入石英管 4 中； (4) setting the gas flow rate of the protective gas flow meter 1 to 5 sccm, and continuously injecting the shielding gas into the quartz tube 4;

( 5 ) 将管式炉 5的温度升高到 800 °C，保持在最高温度的持续时间为 lOOmin; (5) raising the temperature of the tube furnace 5 to 800 ° C, maintaining the maximum temperature for a duration of lOOmin;

( 6) 将管式炉 5温度降至室温，降温速度为 18°C/s; (6) The temperature of the tube furnace 5 is lowered to room temperature, and the cooling rate is 18 ° C / s;

(7a) 关闭保护气流量计 1进气闽门、真空泵； (7a) Close the protective gas flow meter 1 intake valve, vacuum pump;

(7b)设定惰性气体流量计 2流量为 lOOsccm, 用惰性气体将石英管 4的气压充满到 1个大气压状态； (7b) setting the inert gas flow meter 2 the flow rate is lOOsccm, and the air pressure of the quartz tube 4 is filled with an inert gas to an atmospheric pressure state;

(7c) 打开石英管 4，取出已沉积石墨烯的金属衬底 7。其中，所述保护气体为 97vol%氩气和 3vol%氢气的混合气体。 (7c) The quartz tube 4 is opened, and the metal substrate 7 on which graphene has been deposited is taken out. Wherein, the shielding gas is a mixed gas of 97 vol% argon gas and 3 vol% hydrogen gas.

实施例 2 Example 2

采用高温分解固态碳源，在金属衬底上结晶形成石墨烯薄膜，所述方法在化学固相沉积***中进行，包括以下制备歩骤： The graphene film is crystallized on a metal substrate by pyrolysis of a solid carbon source, and the method is carried out in a chemical solid phase deposition system, including the following preparation steps:

( la) 取 50mm²平整的金属镍箔，固定于玻璃片上，将玻璃片固定在离心甩胶机上，在金属衬底表面喷滴 lOmLPDMS (固态碳源聚二甲基硅氧烷）；(la) taking 50mm ² flat metal nickel foil, fixed on the glass piece, fixing the glass piece on the centrifugal glue machine, spraying lOmLPDMS (solid carbon source polydimethylsiloxane) on the surface of the metal substrate;

( lb) 设定甩胶机转速为 10000转 /min，时间为 30s; ( lb) Set the speed of the silicone machine to 10,000 rpm, and the time is 30 s;

( lc) 取下玻璃片上的金属衬底，在加热盘上加热 200°C，时间为 10s; ( lc) remove the metal substrate on the glass piece, and heat it on the heating plate for 200 ° C for 10 s;

(2 ) 将喷涂固态碳源的金属衬底 7置于石英管 4中； (2) placing a metal substrate 7 coated with a solid carbon source in the quartz tube 4;

(3a) 将石英管 4的气压抽至极限真空状态 8 X 10_²torr_; (3a) pumping the air pressure of the quartz tube 4 to the ultimate vacuum state 8 X 10_ ² torr _;

(3b)设定惰性气体流量计 2的气体流量 lOOsccm.将惰性气体注入到石英管 4中； (3b) setting the gas flow rate of the inert gas flow meter 2 lOOsccm. injecting an inert gas into the quartz tube 4;

(3c) lOmin后，关闭惰性气体流量计 2的进气闽门，将石英管 4的气压抽至极限 8 X 10·² torr; (3c) After lOmin, close the intake valve of the inert gas flow meter 2, and draw the air pressure of the quartz tube 4 to the limit of 8 X 10 · ² torr;

(3d) 重复歩骤（3b) 和歩骤（3c) 的操作歩骤 5〜8次；直到将石英管 4 内的残余氧气驱赶干净至氧气分压小于 10_⁶torr_; (3d) ho repeating step (3b), and ho step (3c) step operation ho 5 ~ 8 times; until the residual oxygen in the quartz tube 4 to a clean driven oxygen partial pressure of less than 10_ ⁶ _torr;

(4) 设定保护气流量计 1的气体流量 lOOsccm, 将保护气持续注入到真空腔中； (4) Set the gas flow rate of the protective gas flow meter 1 to 100 sccm, and continuously inject the shielding gas into the vacuum chamber;

( 5 )将管式炉 5的温度升高到 1100 °C，保持在最高温度的持续时间为 5min; (5) raising the temperature of the tube furnace 5 to 1100 ° C, maintaining the maximum temperature for 5 min;

( 6) 将管式炉 5温度降至室温，降温速度为 2°C/s; (6) The temperature of the tube furnace 5 is lowered to room temperature, and the cooling rate is 2 ° C / s;

(7a) 关闭保护气流量计 1进气闽门、真空泵 8; (7a) Close the protective gas flow meter 1 Intake valve, vacuum pump 8;

( 7b) 设定惰性气体流量计 2流量为 50sccm，用惰性气体将石英管 4的气压充满到 1个大气压状态； (7c) 打开石英管 4，取出己沉积石墨烯的金属衬底 7。 (7b) setting the flow rate of the inert gas flow meter 2 to 50 sccm, and filling the air pressure of the quartz tube 4 with an inert gas to an atmospheric pressure state; (7c) The quartz tube 4 is opened, and the metal substrate 7 on which graphene has been deposited is taken out.

其中，所述保护气体为体积比 99.99%以上的氩气。 The protective gas is argon gas having a volume ratio of 99.99% or more.

实施例 3 Example 3

( la) 取 30mm²平整的金属铜箔，固定于玻璃片上，将玻璃片固定在离心甩胶机上，在金属衬底表面喷滴 5mL PMMA (固态碳源聚甲基丙烯酸甲酯）；(la) take 30mm ² flat metal copper foil, fix it on the glass piece, fix the glass piece on the centrifugal squeegee machine, spray 5mL PMMA (solid carbon source polymethyl methacrylate) on the surface of the metal substrate;

( lb) 设定甩胶机转速为 5000转 /min，时间为 lOmin; ( lb) set the speed of the silicone machine to 5000 rpm, the time is lOmin;

( lc)取下玻璃片上的金属衬底，在加热盘上加热至 100°C，时间为 lOmin; ( lc) remove the metal substrate on the glass piece, heated to 100 ° C on the heating plate, the time is lOmin;

(3a) 将石英管 4的气压抽至极限真空状态 6 X 10-² torr; (3a) pumping the air pressure of the quartz tube 4 to an ultimate vacuum state 6 X 10- ² torr;

( 3b) 设定惰性气体流量计 2的气体流量 50sccm，将惰性气体注入到石英管 4中； (3b) setting the gas flow rate of the inert gas flow meter 2 to 50 sccm, and injecting the inert gas into the quartz tube 4;

(3c) lOmin后，关闭惰性气体流量计 2的进气闽门，将石英管 4的气压抽至极限 6 X 10-²torr_; (3c) After lOmin, close the intake valve of the inert gas flow meter 2, and draw the air pressure of the quartz tube 4 to the limit of 6 X 10- ² torr _;

(3d) 重复歩骤（3b) 和歩骤（3c) 的操作歩骤 3〜5次；直到将石英管 4 内的残余氧气驱赶干净至氧气分压小于 10_⁶torr_; (3d) ho repeating step (3b), and ho step (3c) step operation ho ~ 5 times; until the residual oxygen in the quartz tube 4 to a clean driven oxygen partial pressure of less than 10_ ⁶ _torr;

(4)设定保护气流量计 1的气体流量为 50sccm，将保护气持续注入石英管 (4) Setting the gas flow rate of the protective gas flow meter 1 to 50 sccm, continuously injecting the shielding gas into the quartz tube

4中； 4;

( 5 )将管式炉 5的温度升高到 950°C，保持在最高温度的持续时间为 55分钟； (5) raising the temperature of the tube furnace 5 to 950 ° C, maintaining the maximum temperature for a duration of 55 minutes;

( 6) 将管式炉 5温度降至室温，降温速度为 5°C/s; (7b) 设定惰性气体流量计 2流量为 75sccm，用惰性气体将石英管 4的气压充满到 1个大气压状态； (6) The temperature of the tube furnace 5 is lowered to room temperature, and the cooling rate is 5 ° C / s; (7b) setting the flow rate of the inert gas flow meter 2 to 75 sccm, and filling the air pressure of the quartz tube 4 with an inert gas to an atmospheric pressure state;

(7c) 打开石英管 4，取出己沉积石墨烯的金属衬底 7。 (7c) Open the quartz tube 4 and take out the metal substrate 7 on which graphene has been deposited.

其中，所述保护气体为 97vol%氩气和 3vol%氢气的混合气体。 Wherein, the shielding gas is a mixed gas of 97 vol% argon gas and 3 vol% hydrogen gas.

图 2是实施例 3所得石墨烯的拉曼光谱，从该图可以看出： Figure 2 is a Raman spectrum of graphene obtained in Example 3, from which it can be seen that:

(1) 存在石墨烯的两个本征拉曼峰 -G峰和 2D峰（1580CHV¹和 2680cm-¹);(1) There are two intrinsic Raman-G peaks and 2D peaks of graphene (1580 CHV ¹ and 2680 cm- ¹ );

(2) 2D峰的强度大约为 G峰的两倍，说明所得石墨烯为单原子层；(2) The intensity of the 2D peak is about twice that of the G peak, indicating that the obtained graphene is a monoatomic layer;

(3)缺陷峰 -D峰（1350cm-¹) 几乎不能分辨，说明所得石墨烯具有极高晶体质量。 (3) The defect peak-D peak (1350 cm - ¹ ) is almost indistinguishable, indicating that the obtained graphene has an extremely high crystal quality.

实施例 4 Example 4

(la) 取 30mm²平整的金属钯箔，固定于玻璃片上，将玻璃片固定在离心甩胶机上，在金属衬底表面喷滴 8mLPDMS; (la) Take 30mm ² flat metal palladium foil, fixed on the glass piece, fix the glass piece on the centrifugal glue machine, spray 8mLPDMS on the surface of the metal substrate;

(lb) 设定甩胶机转速为 10000转 /min，时间为 10s; (lb) Set the speed of the silicone machine to 10,000 rpm, and the time is 10 s;

(lc)取下玻璃片上的金属衬底，在加热盘上加热至 120°C，时间为 15min; (2) 将喷涂固态碳源的金属衬底 7置于石英管 4中； (lc) removing the metal substrate on the glass piece and heating to 120 ° C on the heating plate for 15 min; (2) placing the metal substrate 7 coated with the solid carbon source in the quartz tube 4;

(3a) 将石英管 4的气压抽至极限真空状态 15X ΙΟ ΟΓΓ; (3a) Pumping the air pressure of the quartz tube 4 to the ultimate vacuum state 15X ΙΟ ΟΓΓ;

(3b) 设定惰性气体流量计 2的气体流量 50sccm，将惰性气体注入到石英管 4中； (3b) setting the gas flow rate of the inert gas flow meter 2 to 50 sccm, and injecting the inert gas into the quartz tube 4;

(3c) lOmin后，关闭惰性气体流量计 2的进气闽门，将石英管 4的气压抽至极限 2X10-²torr; (3c) After lOmin, close the intake valve of the inert gas flow meter 2, and draw the air pressure of the quartz tube 4 to the limit 2X10-2 ² torr;

(3d) 重复歩骤（3b) 和歩骤（3c) 的操作歩骤 4〜8次；直到将石英管 4 内的残余氧气驱赶干净至氧气分压 10_⁶torr_; (3d) Repeat steps (3b) and (3c) for steps 4 to 8; until quartz tube 4 The residual oxygen in the drive is driven clean to a partial pressure of oxygen of 10_ ⁶ torr _;

(4) 设定保护气流量计 1的气体流量为 lsccm, 将保护气持续注入石英管 (4) Set the gas flow rate of the protective gas flow meter 1 to lsccm, and continuously inject the shielding gas into the quartz tube.

4中； 4;

( 5 )将管式炉 5的温度升高到 1150°C，保持在最高温度的持续时间为 lmin; (5) raising the temperature of the tube furnace 5 to 1150 ° C, maintaining the maximum temperature for a duration of lmin;

( 6) 将管式炉 5温度降至室温，降温速度为 5°C/s; (6) The temperature of the tube furnace 5 is lowered to room temperature, and the cooling rate is 5 ° C / s;

( 7b) 设定惰性气体流量计 2流量为 75sccm，用惰性气体将石英管 4的气压充满到 1个大气压状态； (7b) Setting the inert gas flow meter 2 The flow rate is 75 sccm, and the air pressure of the quartz tube 4 is filled with an inert gas to an atmospheric pressure state;

其中，所述保护气体为 98vol%氦气和 2vol%氢气的混合气体。 Wherein, the shielding gas is a mixed gas of 98 vol% helium and 2 vol% hydrogen.

申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。 The Applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims

1、一种固态碳源制备石墨烯的方法，其特征在于，所述方法是在保护气氛中，加热涂覆有固体碳源的衬底，降温得沉积有石墨烯的金属衬底；所述固体碳源选自有机聚合物，优选聚甲基丙烯酸甲酯和 \或聚二甲基硅氧垸，进一歩优选聚二甲基硅氧垸。 A method for preparing graphene by using a solid carbon source, wherein the method comprises: heating a substrate coated with a solid carbon source in a protective atmosphere, and cooling a metal substrate on which graphene is deposited; The solid carbon source is selected from the group consisting of organic polymers, preferably polymethyl methacrylate and/or polydimethylsiloxane, and further preferably polydimethylsiloxane.

2、如权利要求 1所述的方法，其特征在于，所述衬底选自金属衬底，所述金属衬底选自镍箔、铜箔、铷箔、钴箔、钯箔、铂箔、铱箔或钌箔中的任意 1 种或至少 2种的组合，优选铜箔和 /或镍箔，进一歩优选镍箔； 2. The method according to claim 1, wherein the substrate is selected from the group consisting of a metal substrate selected from the group consisting of nickel foil, copper foil, tantalum foil, cobalt foil, palladium foil, platinum foil, Any one or a combination of at least two of ruthenium foil or ruthenium foil, preferably copper foil and/or nickel foil, further preferred nickel foil;

优选地，所述保护气由氢气与惰性气体组成； Preferably, the shielding gas is composed of hydrogen and an inert gas;

优选地，所述惰性气体为不与石墨烯反应的气体，优选氮气、氦气、氖气、氩气、氪气或氙气中的任意 1种或至少 2种的组合，进一歩优选氮气、氩气或氦气中的任意 1种或至少 2种的组合；特别优选氮气和 /或氩气； Preferably, the inert gas is a gas that does not react with graphene, preferably any one or a combination of at least two of nitrogen, helium, neon, argon, helium or neon. Further, preferably nitrogen or argon. Any one or a combination of at least two of gas or helium; particularly preferably nitrogen and/or argon;

优选地，所述保护气中氢气的体积百分比 3vol%，优选 l-3vol%，进一歩优选 2-3vol%。 Preferably, the volume percentage of hydrogen in the shielding gas is 3 vol%, preferably 1-3 vol%, further preferably 2-3 vol%.

3、如权利要求 1或 2所述的方法，其特征在于，所述方法包括如下歩骤： 3. The method according to claim 1 or 2, wherein the method comprises the following steps:

4、如权利要求 3 所述的方法，其特征在于，歩骤（1 ) 所述在衬底上涂覆固体碳源包括如下歩骤：（la) 在衬底表面喷涂有机聚合物作为固态碳源；（lb) 将衬底置于甩胶机上匀化；（lc) 将经匀化的金属衬底加热。 4. The method according to claim 3, wherein the coating the solid carbon source on the substrate comprises the following steps: (la) spraying an organic polymer on the surface of the substrate as a solid carbon Source; (lb) The substrate is placed on a silicone mixer to homogenize; (lc) the homogenized metal substrate is heated.

5、如权利要求 4所述的方法，其特征在于，歩骤（3) 所述除去真空腔内的氧气包括如下歩骤：（3a)将真空腔抽真空；（3b)将惰性气体注入真空腔； (3c) 将真空腔再次抽真空；（3d) 重复歩骤（3b) 和歩骤（3c)，直至将真空腔内的氧气分压 lxl0-⁶torr_; 5. The method according to claim 4, wherein the removing the oxygen in the vacuum chamber by the step (3) comprises the following steps: (3a) vacuuming the vacuum chamber; (3b) injecting the inert gas into the vacuum chamber; (. 3C) the vacuum chamber was evacuated again; (3D) ho repeating step (3b), and ho step (3c), the vacuum chamber until the oxygen partial pressure lxl0- ⁶ _torr;

优选地，歩骤（3a)抽真空至真空状态为 2-15xl0—²torr，优选 3-10xl0—²torr，最优选 4-8xl0-²torr; Preferably, the step (3a) is evacuated to a vacuum of 2-15 x 10 - ² torr, preferably 3 - 10 x 10 - ² torr, and most preferably 4 - 8 x 10 - ² torr;

优选地，歩骤（3b) 惰性气体的注入量为使真空腔内的压力为 ^lOtorr, 优选 100 11~_; 优选地，歩骤（3b) 所述惰性气体选自氮气、氦气、氖气、氩气、氪气、氙气中的任意 1种或至少 2种的组合； Preferably, the inert gas is injected in the vacuum chamber so that the pressure in the vacuum chamber is 10 Torr, preferably 100 11 〜 _; preferably, the inert gas is selected from the group consisting of nitrogen, helium and neon. Any one or a combination of at least two of argon, helium and neon;

优选地，歩骤（3c)抽真空至真空状态为 2-15xl0—²torr，优选 3-10xl0—²torr，最优选 4-8xl0-²torr; Preferably, the step (3c) is evacuated to a vacuum of 2-15 x 10 - ² torr, preferably 3 - 10 x 10 - ² torr, and most preferably 4 - 8 x 10 - ² torr;

优选地，歩骤（3d) 所述的歩骤（3b) 和歩骤（3c) 的重复次数为 2-8次，优选 2-5次，最优选 2-3次。 Preferably, the number of repetitions of the step (3b) and the step (3c) described in the step (3d) is 2-8 times, preferably 2-5 times, and most preferably 2-3 times.

6、如权利要求 4或 5所述的方法，其特征在于，歩骤（4) 所述的保护气体的注入流量为 l-100sccm，优选 4-96sccm，进一歩优选 20-80sccm; 所述保护气的纯度 99.99%； The method according to claim 4 or 5, wherein the injection flow rate of the shielding gas according to the step (4) is 1-100 sccm, preferably 4-96 sccm, further preferably 20-80 sccm; The purity of the gas is 99.99%;

优选地，歩骤（5)所述升温的温度为 800-1150°C，优选 800-1100°C，进一歩优选 880-1080 °C，特别优选 900-1000°C; Preferably, the temperature of the step (5) is 800-1150 ° C, preferably 800-1100 ° C, further preferably 880-1080 ° C, particularly preferably 900-1000 ° C;

优选地，（5) 所述保温的时间为 l-100min，优选 4-93min，进一歩优选 4.5-82min_; Preferably, (5) the incubation time is 1-100 min, preferably 4-93 min, further preferably 4.5-82 min _;

优选地，歩骤（6) 所述降温为降至室温，降温速度为 2-18°C/s，优选 3-9 °C/s，进一歩优选 8°C/s。 Preferably, the temperature drop is reduced to room temperature, and the temperature drop rate is 2-18 ° C / s, preferably 3-9 ° C / s, further preferably 8 ° C / s.

7、如权利要求 4-6之一所述的方法，其特征在于，歩骤（7 )所述取出沉积有石墨烯的金属衬底包括如下歩骤： 7. The method according to any one of claims 4-6, wherein the extracting the metal substrate deposited with graphene as described in step (7) comprises the following steps:

(7a) 关闭还原性气体进气阀、碳源气体进气阀和真空泵； (7a) closing the reducing gas intake valve, the carbon source gas intake valve, and the vacuum pump;

(7b) 打开惰性气体进气阀，充入惰性气体至真空腔内气压为 1个大气压; (7b) Open the inert gas inlet valve and fill with inert gas until the pressure in the vacuum chamber is 1 atmosphere;

(7c) 取出衬底。 (7c) Remove the substrate.

8、如权利要求 1-7之一所述的方法，其特征在于，所述方法包括如下歩骤: ( la) 在衬底表面喷涂有机聚合物作为固态碳源； The method according to any one of claims 1 to 7, wherein the method comprises the steps of: (la) spraying an organic polymer on the surface of the substrate as a solid carbon source;

( lc) 将经匀化的金属衬底加热； ( lc) heating the homogenized metal substrate;

(3a) 将真空腔抽真空； (3a) evacuating the vacuum chamber;

(3c) 将真空腔再次抽真空； (3c) vacuuming the vacuum chamber again;

(3d)重复歩骤（3b)和歩骤（3c)，直至将真空腔内的氧气分压 1 x 10— ⁶torr;(3d) ho repeating step (3b), and ho step (3c), the vacuum chamber until the oxygen partial pressure 1 x 10- ⁶ torr;

(7c) 取出衬底。 (7c) Remove the substrate.

9、一种如权利要求 1-8之一所述的方法通过固态碳源制备得到的石墨烯，其特征在于，所述石墨烯厚度可控； 9. A graphene prepared by a solid carbon source according to the method of any one of claims 1-8, wherein the graphene has a thickness that is controllable;

优选地，所述石墨烯为多原子层石墨烯；优选地，所述石墨烯为单原子层石墨烯。 Preferably, the graphene is a polyatomic layer graphene; Preferably, the graphene is a monoatomic layer graphene.

10、一种如权利要求 9所述的石墨烯的用途，其特征在于，所述石墨烯用于能量储存活性材料、微处理器、电池、显示器和柔性电子器件，优选用于储氢、锂离子电池、超级电容器或者燃料电池，以及纳电子器件、高频电路、光子传感器、基因电子测序、减少噪音、高频 /射频晶体管、平板显示和柔性显示器。 10. Use of graphene according to claim 9, characterized in that the graphene is used for energy storage active materials, microprocessors, batteries, displays and flexible electronic devices, preferably for hydrogen storage, lithium Ion batteries, supercapacitors or fuel cells, as well as nanoelectronics, high frequency circuits, photonic sensors, gene electronics sequencing, noise reduction, HF/RF transistors, flat panel displays and flexible displays.