WO2014183243A1

WO2014183243A1 - Method for preparing graphene material and use thereof in chemical energy storage and/or conversion

Info

Publication number: WO2014183243A1
Application number: PCT/CN2013/074275
Authority: WO
Inventors: 王要兵; 洪茂椿
Original assignee: 中国科学院福建物质结构研究所
Priority date: 2013-05-14
Filing date: 2013-05-14
Publication date: 2014-11-20

Abstract

The present invention provides a method for preparing a graphene material and the use thereof in chemical energy storage and/or conversion. The method comprises the following steps: 1) adding graphene oxide into a dispersion medium so as to obtain a graphene oxide suspension; 2) spray-drying the suspension so as to obtain graphene oxide particles; 3) reducing the graphene oxide particles through an atmospheric reduction. Furthermore, the resulting material is applied as the electrode material of super capacitors, the capacity of which is able to reach 120 F/g. The method of the present invention can obtain porous micron-sized graphene particles in a macro amount. The graphene material of the present invention can be used as the electrode material of super capacitors, catalyst carriers or infrared optical materials.

Description

说明书一种制备石墨烯材料的方法及其在化学储能和 /或转化中的用途技术领域 Description Method for preparing graphene material and use thereof in chemical energy storage and/or conversion

本发明涉及石墨烯材料领域，尤其是涉及一种制备石墨烯材料的方法及其在化学储能和 /或转化领域，尤其是在超级电容器中的用途。背景技术 Field of the Invention This invention relates to the field of graphene materials, and more particularly to a method of preparing graphene materials and their use in the field of chemical energy storage and/or conversion, especially in supercapacitors. Background technique

自从英国曼彻斯特大学的安德烈. K.海姆 (Andre K. Geim)等在 2004年制备出石墨烯材料以来，由于其独特的结构和光电性质，石墨烯材料受到了广泛的重视。单层石墨由于其大的比表面积，优良的导电、导热性能和低的热膨胀系数而被认为是理想的材料。其例如具有如下性能：①高强度,杨氏模量 (l，100GPa)，断裂强度 (125GPa); ②高热导率 (5，000W/mK); ③高导电性、高载流子传输率 (200，000cm²/V's); ④高比表面积 (理论计算值： 2，630m²/g)。尤其是由于其高导电性，大的比表面积及其单分子层的二维纳米尺度的结构性质，石墨烯材料可在超级电容器和锂离子电池中用作电极材料。到目前为止，制备石墨烯的方法有许多种，其中氧化-还原法是一种能够大量制备石墨烯且产率较高的方法，整个过程涉及到将石墨氧化成氧化石墨，氧化石墨在进一步在外力作用下剥落产生氧化石墨烯，再化学或热还原为石墨烯。化学还原是一种较为简单的还原石墨烯的方法，其有利于石墨烯与其他物质的复合。但是，还原后的石墨烯很容易团聚，导致一些性能的丧失，同时也难以加工，不利于产业化。发明内容 Since the preparation of graphene materials in 2004 by Andre K. Geim of the University of Manchester in the United Kingdom, graphene materials have received extensive attention due to their unique structural and optoelectronic properties. Single-layer graphite is considered to be an ideal material due to its large specific surface area, excellent electrical conductivity, thermal conductivity, and low coefficient of thermal expansion. It has, for example, the following properties: 1 high strength, Young's modulus (l, 100 GPa), breaking strength (125 GPa); 2 high thermal conductivity (5,000 W/mK); 3 high conductivity, high carrier transport rate ( 200,000 cm ² /V's); 4 high specific surface area (theoretical calculated value: 2,630 m ² /g). Especially due to its high electrical conductivity, large specific surface area and its two-dimensional nanoscale structural properties of monolayers, graphene materials can be used as electrode materials in supercapacitors and lithium ion batteries. So far, there are many methods for preparing graphene, wherein the oxidation-reduction method is a method capable of preparing graphene in a large amount and having a high yield, and the whole process involves oxidizing graphite into graphite oxide, and graphite oxide is further in Exfoliation by external force produces graphene oxide, which is then chemically or thermally reduced to graphene. Chemical reduction is a relatively simple method of reducing graphene, which is beneficial to the composite of graphene and other substances. However, the graphene after reduction is easily agglomerated, resulting in some loss of performance and difficulty in processing, which is not conducive to industrialization. Summary of the invention

本发明的目的在于克服上述现有技术的缺点，提供一种制备石墨烯材料的方法，所述方法基于氧化法制备的氧化石墨烯水溶液，将其喷雾干燥并进行气氛还原而获得具有多孔结构的石墨烯微球。 The object of the present invention is to overcome the above disadvantages of the prior art and to provide a method for preparing a graphene material, which is based on an aqueous solution of graphene oxide prepared by an oxidation method, spray-dried and subjected to atmosphere reduction to obtain a porous structure. Graphene microspheres.

本发明采用如下技术方案： 1)将氧化石墨烯添加至分散介质中以获得氧化石墨烯的悬浮液； The invention adopts the following technical solutions: 1) adding graphene oxide to a dispersion medium to obtain a suspension of graphene oxide;

2)将所述悬浮液喷雾干燥，从而获得氧化石墨烯颗粒； 2) spray drying the suspension to obtain graphene oxide particles;

3)通过气氛还原方法将所述氧化石墨烯颗粒还原。 3) Reduction of the graphene oxide particles by an atmosphere reduction method.

步骤 1)中所用的氧化石墨烯可通过氧化法 (例如 hummers改进法)制备。在所述氧化法中，通常使石墨粉和氧化剂在一定温度下反应，从而制得氧化石墨。所述氧化石墨在进一步在外力作用下剥落产生氧化石墨烯。所用氧化剂例如可为过硫酸钾、酸、高锰酸钾等。氧化法是本领域技术人员所公知的，例如参见 JACS, 1958， 80， 1339。 The graphene oxide used in the step 1) can be produced by an oxidation method such as a hummers modification method. In the oxidation method, graphite powder and an oxidizing agent are usually reacted at a certain temperature to obtain graphite oxide. The graphite oxide is further peeled off by an external force to produce graphene oxide. The oxidizing agent used may be, for example, potassium persulfate, acid, potassium permanganate or the like. Oxidation methods are well known to those skilled in the art, for example, see JACS, 1958, 80, 1339.

在本发明的实施方案中，步骤 1)中所用的分散介质为水、乙醇、丙酮、 NMP、离子液体或其混合物，优选为水。所述离子液体中的阳离子例如为咪唑、季铵、咔唑、吡啶等阳离子；其中的阴离子例如为氟硼酸根、氟磷酸根、二 (三氟甲磺酰)亚氨阴离子、二 (氟磺酰)亚氨阴离子、三氟甲磺酰氟磺酰亚氨阴离子等。 In an embodiment of the invention, the dispersion medium used in step 1) is water, ethanol, acetone, NMP, an ionic liquid or a mixture thereof, preferably water. The cation in the ionic liquid is, for example, a cation such as imidazole, quaternary ammonium, carbazole or pyridine; wherein the anion is, for example, fluoroborate, fluorophosphate, bis(trifluoromethanesulfonyl)imide, and bis(fluorosulfonate) An acyl imino anion, a trifluoromethanesulfonyl fluorosulfonimide anion or the like.

在本发明的优选实施方案中，在步骤 1)中将氧化石墨烯与添加剂一起添加至所述介质中。所用的添加剂为能在步骤 2)的喷雾干燥温度或步骤 3)的还原温度下与氧化石墨烯之间发生物理或者化学反应以例如形成新的化学结构的那些，例如含氨基有机化合物如氨基酸、尿素、硫脲、芳香胺类化合物 (如对苯二胺)等，含羟基的有机化合物如乙二醇、甘油、环糊精、葡萄糖等；以及甲醛等。所述添加剂还可为能在步骤 2)的喷雾干燥温度下发生聚合反应，从而与氧化石墨烯形成混合物或者引发所述聚合反应的化合物，例如聚合物单体如苯乙烯、曱基丙烯酸、苯胺等以及引发剂如自由基聚合引发剂，阳离子聚合引发剂、阴离子聚合引发剂等。所述添加剂还可为能在步骤 3)的还原温度下分解产生气体的那些，如：氨基酸、乙酸铵、碳酸氢铵等。其中，添加剂的用量基于所述分散介质重量为 0.0001-30重量％，优选为 0.001-20重量％，更优选为 0.01-15重量％，更优选为 0.01-10重量％，最优选为 0.01-5重量％。 In a preferred embodiment of the invention, graphene oxide is added to the medium together with an additive in step 1). The additives used are those which can undergo physical or chemical reactions with the graphene oxide at the spray drying temperature of step 2) or the reduction temperature of step 3) to form, for example, new chemical structures, such as amino-containing organic compounds such as amino acids, Urea, thiourea, aromatic amine compounds (such as p-phenylenediamine), hydroxyl group-containing organic compounds such as ethylene glycol, glycerin, cyclodextrin, glucose, etc.; and formaldehyde. The additive may also be a compound which can undergo a polymerization reaction at the spray drying temperature of step 2) to form a mixture with the graphene oxide or initiate the polymerization reaction, such as a polymer monomer such as styrene, mercaptoacrylic acid, aniline. And an initiator such as a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator, and the like. The additives may also be those which are capable of decomposing to produce a gas at the reduction temperature of step 3), such as amino acids, ammonium acetate, ammonium hydrogencarbonate and the like. Wherein the additive is used in an amount of 0.0001 to 30% by weight, based on the weight of the dispersion medium, preferably 0.001 to 20% by weight, more preferably 0.01 to 15% by weight, still more preferably 0.01 to 10% by weight, most preferably 0.01 to 55% by weight. weight%.

申请人经过长期研究出人意料地发现，使用上述能在喷雾干燥或还原温度下与氧化石墨烯之间发生物理或者化学反应的添加剂以及上述能在喷雾干燥温度下发生聚合反应的添加剂有助于在石墨烯微球上形成新的结构如氨基、羟基等，从而获得稳定的石墨烯微球；其次，在氧化石墨烯的喷雾干燥或还原过程中，使用上述能在喷雾干燥或还原温度下分解产生气体的添加剂有助于在石墨烯微球表面上形成多孔结构。在优选实施方案中，步骤 1)中的氧化石墨烯悬浮液中的氧化石墨烯浓度为 0.01mg/ml至 10g/ml，优选为 lmg/ml至 lg/ml。 After long-term research, the Applicant has surprisingly found that the use of the above additives capable of physical or chemical reaction with graphene oxide at spray drying or reduction temperatures and the above-mentioned additives which can be polymerized at spray drying temperatures contribute to the graphite. Forming new structures such as amino groups, hydroxyl groups, etc. on the olefinic microspheres to obtain stable graphene microspheres; secondly, in the spray drying or reduction process of graphene oxide, using the above-mentioned gas which can be decomposed at a spray drying or reduction temperature to generate a gas The additive helps to form a porous structure on the surface of the graphene microspheres. In a preferred embodiment, the graphene oxide suspension in the graphene oxide suspension in step 1) has a concentration of from 0.01 mg/ml to 10 g/ml, preferably from 1 mg/ml to lg/ml.

在优选实施方案中，在步骤 1)中，通过例如搅拌、超声、微波等方式将所述氧化石墨烯于^ t介质中。 In a preferred embodiment, in step 1), the graphene oxide is placed in a medium by, for example, stirring, sonication, microwave or the like.

在本发明的实施方案中，在步骤 2)中，将所述悬浮液喷雾干燥，从而获得氧化石墨烯颗粒。所述喷雾干燥技术可为离心喷雾，超声喷雾、气流喷雾或者压力喷雾技术中的一种或者几种。喷雾干燥设备是本领域技术人员所公知的。优选采用压力喷雾技术。所述氧化石墨烯颗粒的尺寸可受原料的浓度、进风口温度、出风口温度、以及离心速度 (或者压力)等参数的影响。因此，在步骤 2)中，优选对原料的浓度、喷雾压力、进风温度、出风温度、以及离心速度 (或者压力)等参数进行优化，以获得具有所需尺寸、结构和所需电性能的氧化烯石墨颗粒。原料浓度如上文对步骤 1)的悬浮液中的氧化石墨烯浓度所述。本发明人经过长期研究意外地发现，在下述工艺条件下实施喷雾干燥能获得具有所需尺寸、结构和所需电性能的氧化烯石墨颗粒：在压力喷雾技术中，喷雾压力可为 l-10MPa，优选 4-6MPa; 进风温度可为 120-200°C，优选 140-160°C; 出风温度可为 80-120°C, 优选 90-100°C。在离心喷雾技术中，离心速度可为 50-10000转 /分钟，优选 2000-5000转 /分钟。所得氧化烯石墨颗粒的直径为 lOOnm至 ΙΟΟμπι, 优选为 500nm至 5μπι。 In an embodiment of the invention, in step 2), the suspension is spray dried to obtain oxidized graphene particles. The spray drying technique can be one or more of a centrifugal spray, an ultrasonic spray, a jet spray, or a pressure spray technique. Spray drying equipment is well known to those skilled in the art. Pressure spray technology is preferred. The size of the graphene oxide particles may be affected by parameters such as the concentration of the raw material, the temperature of the inlet, the temperature of the outlet, and the centrifugal speed (or pressure). Therefore, in step 2), parameters such as the concentration of the raw material, the spray pressure, the inlet air temperature, the outlet temperature, and the centrifugal speed (or pressure) are preferably optimized to obtain the desired size, structure, and desired electrical properties. Acryl oxide graphite particles. The raw material concentration is as described above for the graphene oxide concentration in the suspension of step 1). The inventors have unexpectedly discovered through long-term research that spray drying can be carried out under the following process conditions to obtain oxyalkylene graphite particles having a desired size, structure and desired electrical properties: In a pressure spray technique, the spray pressure can be from 1 to 10 MPa. Preferably, the inlet air temperature may be from 120 to 200 ° C, preferably from 140 to 160 ° C; and the outlet temperature may be from 80 to 120 ° C, preferably from 90 to 100 ° C. In the centrifugal spray technique, the centrifugal speed may be from 50 to 10,000 rpm, preferably from 2,000 to 5,000 rpm. The obtained oxyalkylene graphite particles have a diameter of from 100 nm to ΙΟΟμm, preferably from 500 nm to 5 μm.

在步骤 3)中，通过气氛还原将获自步骤 2)的氧化石墨烯颗粒还原。所述还原在还原性气氛下进行。所述还原性气氛可为 H₂、 NH₃、 BH₃、 PH₃、 H₂S等中的一种或多种，其中任选添加 N₂。还原温度为 60-1000°C，优选 60-800°C，更优选 60-600°C，更优选 60-400°C, 更优选 60-200°C，仍更优选 60-150°C，仍更优选 80-120°C，最优选 90-100°C。所述还原反应可在高温气氛反应炉，优选管式炉中进行。所述还原可通过将所得氧化石墨烯颗粒置于管式炉中，密封，通入一种或多种 H₂、 NH₃、 BH₃、 PH₃、 H₂S等的气体 (其中任选添加 N₂)，升温至所需还原温度而进行。还原时间为 10分钟至 10小时，优选为 30分钟至 2小时。 In step 3), the graphene oxide particles obtained from step 2) are reduced by atmosphere reduction. The reduction is carried out under a reducing atmosphere. The reducing atmosphere may be one or more of H ₂ , NH ₃ , BH ₃ , PH ₃ , H ₂ S, etc., wherein N _{2 is} optionally added. The reduction temperature is 60-1000 ° C, preferably 60-800 ° C, more preferably 60-600 ° C, more preferably 60-400 ° C, still more preferably 60-200 ° C, still more preferably 60-150 ° C, still More preferably, it is 80-120 ° C, and most preferably 90-100 ° C. The reduction reaction can be carried out in a high temperature atmosphere reactor, preferably a tube furnace. The reduction may be carried out by placing the obtained graphene oxide particles in a tube furnace, sealing, and introducing one or more gases of H ₂ , NH ₃ , BH ₃ , PH ₃ , H ₂ S, etc. (optionally added thereto) N ₂ ) is carried out by raising the temperature to the desired reduction temperature. The reduction time is from 10 minutes to 10 hours, preferably from 30 minutes to 2 hours.

令人惊讶的是，本发明人经过长期研究，发现采用上述本发明的方法可获得稳定的具有微纳米结构的多孔石墨烯颗粒。在本文中， "微纳米结构" 意指所得多孔石墨烯颗粒具有微米级或纳米级初级粒径，且每个颗粒上具有微米级和纳米级孔。 Surprisingly, the inventors have found through long-term studies that the above-described method of the present invention can obtain a stable porous graphene particle having a micro/nano structure. As used herein, "micro-nanostructure" means that the resulting porous graphene particles have a micron- or nano-scale primary particle size with micron- and nano-scale pores on each particle.

更加令人惊讶的是，本发明人经过长期研究，发现如果先对获自步骤 2)的氧化石墨烯颗粒进行低温处理，随后对其进行高温处理，可获得具有更好的性能和微纳米结构的多孔石墨烯颗粒。 Even more surprisingly, the inventors have found through long-term research that if the oxide stone obtained from step 2) is first The urethane particles are subjected to low temperature treatment, followed by high temperature treatment to obtain porous graphene particles having better properties and micro/nanostructures.

上述低温和高温处理通过如下方式进行：将得到的氧化石墨烯颗粒置于管式炉中，密封，通入一种或多种 H₂、 NH₃、 BH₃、 PH₃、 H₂S等的气体 (其中任选添加 N₂)，先在较低温度下进行低温处理，形成多孔的氧化石墨烯微米颗粒，随后在较高温度和一种或多种 H₂、 NH₃、 BH₃、 PH₃、 H₂S的气氛 (其中任选添加 N₂)下进行高温反应处理，冷却，得到稳定的多孔的石墨烯颗粒。 The above low temperature and high temperature treatment is carried out by: placing the obtained graphene oxide particles in a tube furnace, sealing, and introducing one or more kinds of H ₂ , NH ₃ , BH ₃ , PH ₃ , H ₂ S, etc. The gas, optionally with the addition of N ₂ , is first treated at a lower temperature to form porous graphene oxide microparticles, followed by higher temperatures and one or more of H ₂ , NH ₃ , BH ₃ , PH _3. The atmosphere of H ₂ S (where N _{2 is} optionally added) is subjected to a high temperature reaction treatment and cooled to obtain stable porous graphene particles.

因此，在本发明的优选实施方案中，本发明涉及一种制备石墨烯材料的方法，所述方法包括如下步骤： Accordingly, in a preferred embodiment of the invention, the invention relates to a method of preparing a graphene material, the method comprising the steps of:

1)将氧化石墨烯添加至分散介质中以获得氧化石墨烯的悬浮液； 1) adding graphene oxide to a dispersion medium to obtain a suspension of graphene oxide;

3) 首先在低温气氛下还原所述氧化烯石墨颗粒，随后在高温气氛下进行还原，由此获得稳定的多孔石墨烯微球。 3) First, the alkylene oxide graphite particles are reduced under a low temperature atmosphere, followed by reduction under a high temperature atmosphere, whereby stable porous graphene microspheres are obtained.

在上述涉及低温气氛还原和高温气氛还原的优选实施方案中，上文对步骤 1)和 2) 所作的描述及其优选实施方案也同样适用于该优选实施方案。具体地，在上述涉及低温气氛还原和高温气氛还原的优选实施方案中： In the above-described preferred embodiment relating to the reduction of the low temperature atmosphere and the reduction of the high temperature atmosphere, the above description of the steps 1) and 2) and preferred embodiments thereof are equally applicable to the preferred embodiment. Specifically, in the above preferred embodiment involving low temperature atmosphere reduction and high temperature atmosphere reduction:

(1) 步骤 1)中所用的氧化石墨烯可通过氧化法 (例如 hummers改进法)制备。 (1) The graphene oxide used in the step 1) can be produced by an oxidation method (for example, a hummers modification method).

(2) 步骤 1)中所用的分散介质为水、乙醇、丙酮、 NMP、离子液体或其混合物，优选为水。所述离子液体中的阳离子例如为咪唑、季铵、咔唑、吡啶等阳离子；其中的阴离子例如为氟硼酸根、氟磷酸根、二 (三氟曱磺酰)亚氨阴离子、二 (氟磺酰)亚氨阴离子、三氟甲磺酰氟磺酰亚氨阴离子等。 (2) The dispersion medium used in the step 1) is water, ethanol, acetone, NMP, an ionic liquid or a mixture thereof, preferably water. The cation in the ionic liquid is, for example, a cation such as imidazole, quaternary ammonium, carbazole or pyridine; wherein the anion is, for example, fluoroborate, fluorophosphate, bis(trifluorosulfonyl)imide, and bis (fluorosulfonate) An acyl imino anion, a trifluoromethanesulfonyl fluorosulfonimide anion or the like.

(3)在该优选实施方案中，在步骤 1)中将氧化石墨烯与添加剂一起添加至所述分散介质中。所用的添加剂为可在步骤 2)的喷雾干燥温度或步骤 3)的还原温度下与氧化石墨烯之间发生物理或者化学反应以例如形成新的化学结构的那些，例如含氨基有机化合物如氨基酸、尿素、硫脲、芳香胺类化合物 (如对苯二胺)等，含羟基的有机化合物如乙二醇、甘油、环糊精、葡萄糖等；以及曱醛等。所述添加剂还可为可在步骤 2)的喷雾干燥温度下发生聚合反应，从而与氧化石墨烯形成混合物或者引发所述聚合反应的化合物，例如聚合物单体如苯乙烯、曱基丙烯酸、苯胺等以及引发剂如自由基聚合引发剂，阳离子聚合引发剂、阴离子聚合引发剂等。所述添加剂还可为可在步骤 3)的还原温度下分解产生气体的那些，如：氨基酸、乙酸铵、碳酸氢铵等。其中，添加剂的用量基于所述^:介质重量为 0.0001-30重量％，优选为 0.001-20重量％，更优选为 0.01-15重量％，更优选为 0.01-10重量％，最优选为 0.01-5重量％。 (3) In the preferred embodiment, graphene oxide is added to the dispersion medium together with the additive in step 1). The additives used are those which can undergo physical or chemical reactions with the graphene oxide at the spray drying temperature of step 2) or the reduction temperature of step 3) to form, for example, new chemical structures, such as amino-containing organic compounds such as amino acids, Urea, thiourea, aromatic amine compounds (such as p-phenylenediamine), hydroxyl group-containing organic compounds such as ethylene glycol, glycerin, cyclodextrin, glucose, etc.; and furfural. The additive may also be a compound which can be polymerized at the spray drying temperature of step 2) to form a mixture with the graphene oxide or initiate the polymerization, such as a polymer monomer such as styrene, mercaptoacrylic acid, aniline. And an initiator such as a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator, and the like. The additive may also be Those which decompose to generate a gas at the reduction temperature of the step 3), such as: amino acid, ammonium acetate, ammonium hydrogencarbonate or the like. Wherein the amount of the additive is from 0.0001 to 30% by weight, preferably from 0.001 to 20% by weight, more preferably from 0.01 to 15% by weight, still more preferably from 0.01 to 10% by weight, most preferably 0.01-based on the weight of the medium: 5 wt%.

(4) 步骤 1)中的氧化石墨烯悬浮液中的氧化石墨烯浓度为 0.01mg/ml至 10g/ml，优选为 lmg/ml至 lg/ml。 (4) The concentration of graphene oxide in the graphene oxide suspension in step 1) is from 0.01 mg/ml to 10 g/ml, preferably from 1 mg/ml to lg/ml.

(5)在步骤 1)中，通过例如搅拌、超声、微波等方式将所述氧化石墨烯分散于分散介质中。 (5) In the step 1), the graphene oxide is dispersed in a dispersion medium by, for example, stirring, ultrasonication, microwave, or the like.

(6)在步骤 2)中，将所述悬浮液喷雾干燥，从而获得氧化石墨烯颗粒。所述喷雾干燥技术可为离心喷雾，超声喷雾、气流喷雾或者压力喷雾技术中的一种或者几种。喷雾干燥设备是本领域技术人员所公知的。优选采用压力喷雾技术。所述氧化石墨烯颗粒的尺寸可受原料的浓度、进风口温度、出风口温度、以及离心速度 (或者压力）等参数的影响。因此，在步骤 2)中，优选对原料的浓度、喷雾压力、进风温度、出风温度、以及离心速度 (或者压力)等参数进行优化，以获得具有所需尺寸、结构和所需电性能的氧化烯石墨颗粒。原料浓度如上文对所述悬浮液中的氧化石墨烯浓度所述。本发明人经过长期研究意外地发现，在下述工艺条件下实施喷雾干燥能获得具有所需尺寸、结构和所需电性能的氧化烯石墨颗粒：在压力喷雾技术中，喷雾压力可为 l-10MPa, 优选 4-6MPa; 进风温度可为 120-200°C，优选 140-160°C; 出风温度可为 80-120°C, 优选 90-100°C。在离心喷雾技术中，离心速度可为 50-10000转 /分钟，优选 2000-5000转 /分钟。所得氧化烯石墨颗粒的直径为 lOOnm至 ΙΟΟμπι , 优选为 500ϋπι-5μιη。 (6) In the step 2), the suspension is spray-dried to obtain graphene oxide particles. The spray drying technique can be one or more of a centrifugal spray, an ultrasonic spray, a jet spray, or a pressure spray technique. Spray drying equipment is well known to those skilled in the art. Pressure spray techniques are preferred. The size of the graphene oxide particles may be affected by parameters such as the concentration of the raw material, the temperature of the inlet, the temperature of the outlet, and the centrifugal speed (or pressure). Therefore, in step 2), parameters such as the concentration of the raw material, the spray pressure, the inlet air temperature, the outlet temperature, and the centrifugal speed (or pressure) are preferably optimized to obtain the desired size, structure, and desired electrical properties. Acryl oxide graphite particles. The starting material concentration is as described above for the graphene oxide concentration in the suspension. The inventors have unexpectedly discovered through long-term research that spray drying can be carried out under the following process conditions to obtain oxyalkylene graphite particles having a desired size, structure and desired electrical properties: In a pressure spray technique, the spray pressure can be from 1 to 10 MPa. Preferably, the inlet air temperature may be from 120 to 200 ° C, preferably from 140 to 160 ° C; and the outlet temperature may be from 80 to 120 ° C, preferably from 90 to 100 ° C. In the centrifugal spray technique, the centrifugal speed can be from 50 to 10,000 rpm, preferably from 2,000 to 5,000 rpm. The obtained oxyalkylene graphite particles have a diameter of from 100 nm to ΙΟΟμm, preferably from 500 ϋπι to 5 μm.

发明人经过长期深入研究，出人意料地发现所述低温气氛还原有助于进一步除去所述氧化石墨烯颗粒表面上吸附的水分和不稳定的氧原子，由此形成多孔结构；而随后的高温气氛还原能使石墨烯进一步交联，从而形成稳定的多孔石墨烯微球。 After intensive research, the inventors have unexpectedly found that the low temperature atmosphere reduction helps to further remove the adsorbed moisture and unstable oxygen atoms on the surface of the graphene oxide particles, thereby forming a porous structure; and subsequent high temperature atmosphere reduction. The graphene can be further crosslinked to form stable porous graphene microspheres.

所述低温气氛还原通常在 80-200°C的温度下进行，优选在 100-180°C，更优选 150°C下进行。所述高温气氛还原通常在高于 200°C至 1000°C的温度下进行，优选在 400-800°C, 更优选 600°C下进行。低温还原时间为 10分钟至 5小时，优选为 30分钟至 2小时；高温还原时间为 10分钟至 5小时，优选为 30分钟至 2小时。 The low temperature atmosphere reduction is usually carried out at a temperature of from 80 to 200 ° C, preferably from 100 to 180 ° C, more preferably at 150 ° C. The high temperature atmosphere reduction is usually carried out at a temperature higher than 200 ° C to 1000 ° C, preferably at 400 to 800 ° C, more preferably 600 ° C. The low temperature reduction time is from 10 minutes to 5 hours, preferably from 30 minutes to 2 hours; and the high temperature reduction time is from 10 minutes to 5 hours, preferably from 30 minutes to 2 hours.

在上述涉及低温气氛还原和高温气氛还原的该优选实施方案中，步骤 3)中所用的气氛为 H₂、 NH₃、 BH₃、 PH₃、 H₂S等中的一种或多种，其中任选添加 N₂。其中，所述低温气氛还原和高温气氛还原中的还原气氛可相同或不同，优选相同。 In the above preferred embodiment relating to the reduction of the low temperature atmosphere and the reduction of the high temperature atmosphere, the atmosphere used in the step 3) is one or more of H ₂ , NH ₃ , BH ₃ , PH ₃ , H ₂ S, etc., wherein Optionally add N ₂ . Among them, The reducing atmosphere in the low-temperature atmosphere reduction and the high-temperature atmosphere reduction may be the same or different, and preferably the same.

通过本发明方法获得的多孔石墨烯微球具有微米级或纳米级尺寸，所述微球上布满了微米和纳米级孔。 The porous graphene microspheres obtained by the method of the present invention have a micron- or nano-scale size, and the microspheres are covered with micron and nanoscale pores.

因此，在本发明的一个实施方案中，本发明涉及一种多孔石墨烯微球，其具有微米级或纳米级尺寸，其特征在于，所述微球上具有微米和纳米级孔。所述多孔石墨婦微球可通过本发明的方法获得。 Accordingly, in one embodiment of the invention, the invention relates to a porous graphene microsphere having a micron or nanometer size, characterized in that the microspheres have micron and nanoscale pores. The porous graphite microspheres can be obtained by the method of the present invention.

本发明的多孔石墨烯微球非常适于制备超级电容器的电极材料，而且由其制备的电容器具有优异的充放电、循环伏安、寿命等电性能。 The porous graphene microspheres of the present invention are very suitable for preparing electrode materials for supercapacitors, and capacitors prepared therefrom have excellent electrical properties such as charge and discharge, cyclic voltammetry, and lifetime.

由石墨烯微球制备电容器的方法是本领域技术人员所已知的，其例如可包括如下步骤：混料、搅拌、涂布、压片、裁片、组装以形成扣式电容器。由本发明多孔石墨烯微球制备的电容器具有优异的充放电、循环伏安、寿命等电化学性能。特别地，由本发明多孔石墨烯微球制备的电容器的有机电解液体系的容量大于 80F/g，耐压性大于 3.5V, 倍率性能大于 10A/g，长寿命 1000次>80%。 Methods of preparing capacitors from graphene microspheres are known to those skilled in the art and can include, for example, the following steps: compounding, agitating, coating, tableting, cutting, assembling to form a button capacitor. The capacitor prepared from the porous graphene microsphere of the present invention has excellent electrochemical properties such as charge and discharge, cyclic voltammetry, and lifetime. In particular, the organic electrolyte system of the capacitor prepared from the porous graphene microsphere of the present invention has a capacity of more than 80 F/g, a pressure resistance of more than 3.5 V, a rate performance of more than 10 A/g, and a long life of 1000 times > 80%.

本发明的多孔石墨烯微球还可用作催化剂载体，例如用于燃料电池或者锂空气电池中阴极催化氧化还原氧气分子的反应中；以及用作红外光学材料，例如用于电磁屏蔽物体的仪器中。 The porous graphene microspheres of the present invention can also be used as a catalyst support, for example, in the reaction of a cathodically catalyzed redox oxygen molecule in a fuel cell or a lithium air battery; and as an infrared optical material, such as an instrument for electromagnetically shielding an object. in.

因此，在本发明的一个实施方案中，本发明涉及本发明的多孔石墨烯微球的用途，其中将其用作超级电容器的电极材料，用作催化剂载体或红外光学材料。 Accordingly, in one embodiment of the present invention, the present invention relates to the use of the porous graphene microspheres of the present invention, which is used as an electrode material for a supercapacitor, as a catalyst carrier or an infrared optical material.

本发明的多孔石墨烯微球制备方法的优点在于：同时该石墨烯微球具备微纳米级的稳定多孔结构，又不同于纳米结构以及宏观结构的石墨烯材料 (单纯的纳米级石墨烯容易聚集，导致各种性能的丧失)。通过喷雾干燥技术以及气氛还原技术可以宏量的制备，便于工业化生产，本发明的微纳米结构的粉体材料既可以保持性能的稳定，获得石墨烯颗粒的尺寸和单分散性和目前市场上使用的超级电容器活性炭材料的物理性质相似，可以较好的分散在溶剂中，直接代替现有的产品，可以较好的匹配已有的生产工艺，便于工艺衔接。 The method for preparing the porous graphene microsphere of the invention has the advantages that: the graphene microsphere has a stable nano-scale stable porous structure, and is different from the nanostructure and the macrostructure of the graphene material (the simple nano-scale graphene is easy to aggregate , resulting in loss of various properties). The spray drying technique and the atmosphere reduction technique can be prepared in a large amount for industrial production. The powder material of the micro/nano structure of the present invention can maintain the stability of the performance, obtain the size and monodispersity of the graphene particles, and are currently used on the market. The supercapacitor activated carbon material has similar physical properties, can be well dispersed in a solvent, directly replaces the existing product, can better match the existing production process, and facilitates process connection.

因此，本发明涉及如下技术方案： Therefore, the present invention relates to the following technical solutions:

1.一种制备石墨烯材料的方法，其包括如下步骤： A method of preparing a graphene material, comprising the steps of:

2)将所述悬浮液喷雾干燥，从而获得氧化石墨烯颗粒； 3)通过气氛还原将所述氧化石墨烯颗粒还原。 2) spray drying the suspension to obtain graphene oxide particles; 3) Reduction of the graphene oxide particles by atmosphere reduction.

2.根据第 1项的方法，其中在步骤 1)中，还向在所述悬浮液中添加添加剂；其中所述添加剂为能在步骤 2)的喷雾干燥温度或步骤 3)的还原温度下与氧化石墨或者石墨烯之间发生物理或者化学反应以形成新的化学结构的那些，例如含氨基有机化合物如氨基酸、尿素、硫脲、芳香胺化合物如对苯二胺，含羟基的有机化合物如乙二醇、甘油、环糊精、葡萄糖；以及曱趁；能在步骤 2)的喷雾干燥温度下发生聚合反应，从而与氧化石墨烯形成混合物或者引发所述聚合反应的化合物，例如聚合物单体如苯乙烯、甲基丙烯酸、苯胺以及引发剂如自由基聚合引发剂，阳离子聚合引发剂、阴离子聚合引发剂；能在步骤 3)的还原温度下分解产生气体的那些，如氨基酸、乙酸铵、碳酸氢铵。 2. The method according to item 1, wherein in step 1), an additive is further added to the suspension; wherein the additive is capable of being at a spray drying temperature of step 2) or a reduction temperature of step 3) Those in which physical or chemical reactions occur between graphite oxide or graphene to form new chemical structures, such as amino-containing organic compounds such as amino acids, urea, thiourea, aromatic amine compounds such as p-phenylenediamine, hydroxyl-containing organic compounds such as B. a diol, glycerin, cyclodextrin, glucose; and hydrazine; a compound which can be polymerized at a spray drying temperature of step 2) to form a mixture with the graphene oxide or initiate the polymerization, such as a polymer monomer For example, styrene, methacrylic acid, aniline, and an initiator such as a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator; those which can decompose to generate a gas at the reduction temperature of the step 3), such as an amino acid, ammonium acetate, Ammonium bicarbonate.

3.根据第 2项的方法，其中所述添加剂的用量基于所述分散介质重量为 0.0001-30 重量％，优选为 0.001-20重量％，更优选为 0.01-15重量％, 更优选为 0.01-10重量％，最优选为 0.01-5重量％。 3. The method according to item 2, wherein the additive is used in an amount of 0.0001 to 30% by weight, based on the weight of the dispersion medium, preferably 0.001 to 20% by weight, more preferably 0.01 to 15% by weight, still more preferably 0.01- 10% by weight, most preferably 0.01 to 5% by weight.

4.根据第 1-3任一项的方法，其中步骤 2)中的喷雾干燥为离心喷雾，超声喷雾、气流喷雾或者压力喷雾中的一种或者几种；优选为离心喷雾或者压力喷雾。 4. The method according to any one of items 1 to 3, wherein the spray drying in the step 2) is one or more of a centrifugal spray, an ultrasonic spray, a gas spray or a pressure spray; preferably a centrifugal spray or a pressure spray.

5. 根据第 4项的方法，其中在压力喷雾技术中，喷雾压力为 l-10MPa，优选 4-6MPa , 进风温度为 120-200°C , 优选 140-160°C，出风温度为 80-120°C，优选 90-100°C;在离心喷雾技术中，离心速度为 50-10000转 /分钟，优选 2000-5000转 /分钟。 5. The method according to item 4, wherein in the pressure spray technique, the spray pressure is l-10 MPa, preferably 4-6 MPa, the inlet air temperature is 120-200 ° C, preferably 140-160 ° C, and the outlet temperature is 80. -120 ° C, preferably 90-100 ° C; in the centrifugal spray technique, the centrifugation speed is 50-10000 rpm, preferably 2000-5000 rpm.

6.根据第 1-5中任一项的方法，其中步骤 3)中的气氛还原在还原性气氛下进行，所述还原性气氛为 H₂、 NH₃、 BH₃、 PH₃、 H₂S中的一种或多种，其中任选添加 N₂。 6. The method according to any one of items 1 to 5, wherein the reduction of the atmosphere in the step 3) is carried out under a reducing atmosphere of H ₂ , NH ₃ , BH ₃ , PH ₃ , H ₂ S One or more of them, wherein N _{2 is} optionally added.

7. 根据第 1-6中任一项的方法，其中步骤 3)中还原温度为 60-1000°C，优选 60-800°C, 更优选 60-600°C，更优选 60-400°C，更优选 60-200°C，仍更优选 60-150°C，仍更优选 80-120°C，最优选 90-100°C; 还原时间为 10分钟至 10小时，优选为 30分钟至 2小时。 7. The method according to any one of the items 1 to 6, wherein the reduction temperature in the step 3) is 60 to 1000 ° C, preferably 60 to 800 ° C, more preferably 60 to 600 ° C, still more preferably 60 to 400 ° C. More preferably, it is 60-200 ° C, still more preferably 60-150 ° C, still more preferably 80-120 ° C, most preferably 90-100 ° C; the reduction time is 10 minutes to 10 hours, preferably 30 minutes to 2 hour.

8. —种制备石墨烯材料的方法，其包括如下步骤： 8. A method of preparing a graphene material, comprising the steps of:

3) 首先在低温气氛下还原所述氧化烯石墨颗粒，随后在高温气氛下进行还原，由此获得多孔石墨; ί敖球。 9.根据第 8项的方法，其中低温气氛还原的温度为 80-200°C，优选为 100-180°C，更优选为 150°C; 高温气氛还原的温度为高于 200°C至 1000°C, 优选为 400-800°C，更优选为 600°C。 3) First, the oxyalkylene graphite particles are reduced under a low temperature atmosphere, followed by reduction under a high temperature atmosphere, thereby obtaining porous graphite; 9. The method according to item 8, wherein the temperature at which the low temperature atmosphere is reduced is 80 to 200 ° C, preferably 100 to 180 ° C, more preferably 150 ° C; and the temperature at which the high temperature atmosphere is lowered is higher than 200 ° C to 1000 °C, preferably 400-800 ° C, more preferably 600 ° C.

10.根据第 8或 9项的方法，其中低温气氛还原和高温气氛还原的时间为 10分钟至 5小时，优选为 30分钟至 2小时。 10. The method according to item 8 or 9, wherein the reduction in the low temperature atmosphere and the high temperature atmosphere is from 10 minutes to 5 hours, preferably from 30 minutes to 2 hours.

11.根据第 8-10中任一项的方法，其中在步骤 1)中，还向在所述悬浮液中添加添加剂；其中所述添加剂为能在步骤 2)的喷雾干燥温度或步骤 3)的还原温度下与氧化石墨或者石墨烯之间发生物理或者化学反应以形成新的化学结构的那些，例如含氨基有机化合物如氨基酸、尿素、硫脲、芳香胺化合物如对苯二胺，含羟基的有机化合物如乙二醇、甘油、环糊精、葡萄糖；以及甲酪；能在步骤 2)的喷雾干燥温度下发生聚合反应，从而与氧化石墨烯形成混合物或者引发所述聚合反应的化合物，例如聚合物单体如苯乙烯、甲基丙烯酸、苯胺以及引发剂如自由基聚合引发剂，阳离子聚合引发剂、阴离子聚合引发剂；能在步骤 3)的还原温度下分解产生气体的那些，如氨基酸、乙酸铵、碳酸氢铵。 The method according to any one of items 8 to 10, wherein in step 1), an additive is further added to the suspension; wherein the additive is a spray drying temperature which can be at step 2) or step 3) Those which physically or chemically react with graphite oxide or graphene at a reduction temperature to form a new chemical structure, such as amino-containing organic compounds such as amino acids, urea, thiourea, aromatic amine compounds such as p-phenylenediamine, hydroxyl groups Organic compounds such as ethylene glycol, glycerin, cyclodextrin, glucose; and methyl ketone; compounds which can undergo polymerization at the spray drying temperature of step 2) to form a mixture with the graphene oxide or initiate the polymerization, For example, a polymer monomer such as styrene, methacrylic acid, aniline, and an initiator such as a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator; those which can decompose to generate a gas at the reduction temperature of the step 3), such as Amino acid, ammonium acetate, ammonium hydrogencarbonate.

12.根据第 11项的方法，其中添加剂的用量基于所述分散介盾重量为 0.0001-30 重量％，优选为 0.001-20重量％，更优选为 0.01-15重量％, 更优选为 0.01-10重量％，最优选为 0.01-5重量％。 12. The method according to item 11, wherein the additive is used in an amount of 0.0001 to 30% by weight, based on the weight of the dispersion medium shield, preferably 0.001 to 20% by weight, more preferably 0.01 to 15% by weight, still more preferably 0.01 to 10% by weight. The weight % is most preferably from 0.01 to 5% by weight.

13.根据第 8-12中任一项的方法，其中步骤 2)中的喷雾干燥为离心喷雾，超声喷雾、气流喷雾或者压力喷雾中的一种或者几种；优选为离心喷雾或者压力喷雾。 The method according to any one of the items 8-12, wherein the spray drying in the step 2) is one or more of a centrifugal spray, an ultrasonic spray, a gas spray or a pressure spray; preferably a centrifugal spray or a pressure spray.

14. 根据第 13项的方法，其中在压力喷雾技术中，喷雾压力为 l-10MPa，优选 4-6MPa , 进风温度为 120-200°C , 优选 140-160°C，出风温度为 80-120°C，优选 90-100°C;在离心喷雾技术中，离心速度为 50-10000转 /分钟，优选 2000-5000转 /分钟。 14. The method according to item 13, wherein in the pressure spray technique, the spray pressure is l-10 MPa, preferably 4-6 MPa, the inlet air temperature is 120-200 ° C, preferably 140-160 ° C, and the outlet temperature is 80. -120 ° C, preferably 90-100 ° C; in the centrifugal spray technique, the centrifugation speed is 50-10000 rpm, preferably 2000-5000 rpm.

15.根据第 8-14中任一项的方法，其中步骤 3)中的低温和高温气氛还原在还原性气氛下进行，所述还原性气氛为 H₂、 NH₃、 BH₃、 PH₃、 H₂S中的一种或多种，其中任选添力口 N₂。 15. The method according to any one of the items 8-14, wherein the low temperature and high temperature atmosphere reduction in step 3) is carried out under a reducing atmosphere of H ₂ , NH ₃ , BH ₃ , PH ₃ , One or more of H ₂ S, wherein the force port N _{2 is} optionally added.

16. 一种通过第 1-15中任一项的方法获得的石墨烯材料。 16. A graphene material obtained by the method of any of the first to fifteenth.

17.通过第 1-15中任一项的方法获得或者根据第 16项的石墨烯材料的用途，其中将其用作超级电容器的电极材料，用作催化剂载体或红外光学材料。 17. The use of the graphene material obtained according to the method of any one of the items 1-15, or the use of the graphene material according to item 16, wherein it is used as an electrode material of a supercapacitor, as a catalyst carrier or an infrared optical material.

附图说明图 1为根据实施例 1通过喷雾干燥和气氛还原反应获得的多孔石墨烯颗粒的扫描电镜照片。 DRAWINGS 1 is a scanning electron micrograph of porous graphene particles obtained by spray drying and atmosphere reduction reaction according to Example 1.

图 2依次为用实施例 1的多孔石墨烯颗粒制备的超级电容器的充放电曲线 (3.5V, 2.7V)、循环伏安曲线以及循环寿命曲线。其中图 2最后一图中的小图是其中大图的局部放大图。具体实施方式 Fig. 2 is a graph showing the charge and discharge curves (3.5 V, 2.7 V), cyclic voltammetry curves, and cycle life curves of the supercapacitors prepared using the porous graphene particles of Example 1. The small image in the last figure of Figure 2 is a partial enlarged view of the large image. detailed description

下面通过实施例进一步详细阐述本发明但是本领域技术人员了解，本发明的实施例并非是对本发明保护范围的限制，任何在本发明基础上做出的改进和变化，都在本发明的保护范围之内。 The invention is further illustrated by the following examples, but it is understood by those skilled in the art that the embodiments of the present invention are not intended to limit the scope of the present invention. Any modifications and changes made on the basis of the present invention are within the scope of the present invention. within.

在下文实施例中，所述粒径通过 SEM拍照，然后通过对 SEM照片进行测量而获得。实施例 1 In the examples below, the particle size was photographed by SEM and then obtained by measuring SEM photographs. Example 1

1)通过氧化还原法 (hummers改进法)获得氧化石墨烯 (参见 JACS, 1958， 80, 1339)。 1) Graphene oxide is obtained by a redox method (Hummers improvement method) (see JACS, 1958, 80, 1339).

其具体步骤为将 20g 50目石墨粉、 10g过硫酸钟和 10g五氧化二磷加入 80°C的浓硫酸中，搅拌均匀，冷却 6h, 洗涤至中性，干燥。将干燥后的样品加入 0°C、 230mL的浓硫酸中，再加入 60g高锰酸钾，混合物的温度保持在 20°C以下，然后在 35°C的油浴中保持 2h后，緩慢加入 920mL去离子水。 15分钟后，再加入 2.8L去离子水 (其中含有 50mL浓度为 30%的双氧水)，之后混合物颜色变为亮黄色，趁热抽滤，再用 5L浓度为 10%的盐酸进行洗涤，抽滤，在 60°C下真空干燥 48h即得到氧化石墨烯。 The specific steps are as follows: 20 g of 50 mesh graphite powder, 10 g of persulfate clock and 10 g of phosphorus pentoxide are added to concentrated sulfuric acid at 80 ° C, stirred uniformly, cooled for 6 hours, washed to neutrality, and dried. The dried sample was added to 0 ° C, 230 mL of concentrated sulfuric acid, 60 g of potassium permanganate was added, the temperature of the mixture was kept below 20 ° C, and then kept in an oil bath at 35 ° C for 2 h, then slowly added 920 mL. Deionized water. After 15 minutes, add 2.8 L of deionized water (containing 50 mL of 30% hydrogen peroxide), then the color of the mixture turned bright yellow, filtered while hot, and washed with 5 L of 10% hydrochloric acid. The graphene oxide was obtained by vacuum drying at 60 ° C for 48 h.

2)通过喷雾干燥制备氧化石墨烯微球 2) Preparation of graphene oxide microspheres by spray drying

将 10克由步骤 1)获得的氧化石墨烯与 2克添加剂尿素一起添加至 500克的去离子水中，超声分散，从而获得石墨烯的均匀悬浮液。在 IMPa的喷雾压力， 120°C的进风温度， 80°C的出风温度下，借助喷雾干燥机 (型号 SY-600, 上海世远生物有限公司）将所述悬浮液喷雾干燥，由此获得粒径为 2-10μπι的氧化石墨烯微球。 10 g of the graphene oxide obtained in the step 1) was added together with 2 g of the additive urea to 500 g of deionized water, and ultrasonically dispersed to obtain a uniform suspension of graphene. The suspension was spray dried by means of a spray dryer (Model SY-600, Shanghai Shiyuan Biotechnology Co., Ltd.) at a spray pressure of IMPa, an inlet air temperature of 120 ° C, and an outlet temperature of 80 ° C. Graphene oxide microspheres having a particle diameter of 2 to 10 μm were obtained.

3)通过气氛还原制备多孔石墨烯微球 3) Preparation of porous graphene microspheres by atmosphere reduction

将 2克由步骤 2)获得的氧化石墨微球置于管式炉中，密封。首先，将温度升至 150°C，并以 0.5L/分钟的流速通入 H₂/N₂，从而进行低温还原。其中 H₂与 N₂的体积比为 1:9，低温还原的时间为 30分钟。随后，在保持还原气氛 (即，流速、 ¾与的体积比)不变的情况下，将温度升至 600°C，继续反应 2小时，获得多孔石墨烯微球。随后，使温度降至室温，取出所述多孔石墨烯微球。 2 g of the graphite oxide microspheres obtained in the step 2) were placed in a tube furnace and sealed. First, the temperature was raised to 150 ° C, and H ₂ /N _{2 was introduced} at a flow rate of 0.5 L/min to carry out low-temperature reduction. Wherein the volume ratio of H ₂ to N ₂ For 1:9, the low temperature reduction time is 30 minutes. Subsequently, while maintaining the reducing atmosphere (i.e., the flow rate, the volume ratio of 3⁄4), the temperature was raised to 600 ° C, and the reaction was continued for 2 hours to obtain porous graphene microspheres. Subsequently, the temperature was lowered to room temperature, and the porous graphene microspheres were taken out.

使用扫描电子显微镜观察所得的多孔石墨烯微球。图 1显示了所得多孔石墨烯微球的扫描电镜照片。由图 1可以看出，所述多孔石墨烯微球的尺寸为粒径为 5-15μπι，且每个微球表面布满了纳米级的孔结构。 The obtained porous graphene microspheres were observed using a scanning electron microscope. Figure 1 shows a scanning electron micrograph of the obtained porous graphene microspheres. As can be seen from Fig. 1, the size of the porous graphene microspheres is 5-15 μm, and the surface of each microsphere is covered with a nano-scale pore structure.

4) 由多孔石墨烯微球制备超级电容器 4) Preparation of supercapacitors from porous graphene microspheres

将根据上述方法制备的多孔石墨烯微球作为正极材料，按照质量比为 85:5:10的比例，将所述多孔石墨烯^ t球、聚偏氟乙烯粘结剂和导电剂乙块黑均匀混合以得到浆料。随后，将所述浆料刮刀涂覆至铝箔上，干燥、軋膜、切边处理，从而制得超级电容器极片。随后按照电极片、隔膜、电极片的顺序叠片组装成电芯，再用电池壳体密封电芯，随后通过设置在电池壳体上的注液口向电池壳体内注入四乙基铵氟硼酸 /乙腈电解液，密封注液口，得到超级电容器。测试其充放电、循环伏安、寿命等电化学性能。所得结果示于图 2中。所得电容器的容量、耐压性、倍率性能和寿命汇总于表 1中。实施例 2 The porous graphene microspheres prepared according to the above method are used as a positive electrode material, and the porous graphene ball, the polyvinylidene fluoride binder, and the conductive agent are black at a mass ratio of 85:5:10. Mix evenly to obtain a slurry. Subsequently, the slurry blade was applied to an aluminum foil, dried, rolled, and trimmed to obtain a super capacitor pole piece. Then, according to the order of the electrode sheet, the diaphragm and the electrode sheet, the battery is assembled into a battery core, and then the battery core is sealed with the battery case, and then the tetraethylammonium fluoroboric acid is injected into the battery case through the liquid injection port provided on the battery case. / Acetonitrile electrolyte, sealed injection port, get super capacitor. The electrochemical performance of charge and discharge, cyclic voltammetry, and lifetime was tested. The results obtained are shown in Fig. 2. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1. Example 2

1)通过氧化还原法 (hummers改进法)获得氧化石墨烯 (摘自 JACS, 1958， 80, 1339); 1) obtaining graphene oxide by redox method (hummers improvement method) (taken from JACS, 1958, 80, 1339);

按照与实施例 1相同的方法获得氧化石墨烯。 Graphene oxide was obtained in the same manner as in Example 1.

将 100克由步骤 1)获得的氧化石墨烯与 20克添加剂对苯二胺一起添加至 500克的去离子水中，超声，从而获得石墨烯的均匀悬浮液。在 lOMPa的喷雾压力， 200°C 的进风温度， 95°C的出风温度下，借助喷雾干燥机 (型号 SY-600)将所述悬浮液喷雾干燥，由此获得尺寸为粒径为 2-10μπι的氧化石墨烯微球。 100 g of the graphene oxide obtained in the step 1) was added together with 20 g of the additive p-phenylenediamine to 500 g of deionized water, and ultrasonicated to obtain a uniform suspension of graphene. The suspension was spray-dried by means of a spray dryer (model SY-600) at a spray pressure of 10 MPa, an inlet air temperature of 200 ° C, and an outlet temperature of 95 ° C, thereby obtaining a particle size of 2 -10 μm of graphene oxide microspheres.

将 2克由步骤 2)获得的氧化石墨微球置于管式炉中，密封。首先，将温度升至 120°C，并以 0.5L/分钟的流速通入 NH₃/N₂，从而进行低温还原。其中 NH₃与 N₂的体积比为 1:9，低温还原的时间为 30分钟。随后，在保持还原气氛 (即，流速、 NH₃与 N₂的体积比)不变的情况下，将温度升至 1000°C, 继续反应 2小时，获得多孔石墨烯微球。随后，使温度降至室温，取出所述多孔石墨烯微球。 2 g of the graphite oxide microspheres obtained in the step 2) were placed in a tube furnace and sealed. First, the temperature was raised to 120 ° C, and NH ₃ /N _{2 was introduced} at a flow rate of 0.5 L/min to carry out low-temperature reduction. Wherein the volume ratio of NH ₃ to N ₂ is 1:9, and the time of low temperature reduction is 30 minutes. Subsequently, while maintaining the reducing atmosphere (i.e., the flow rate, the volume ratio of NH ₃ to N ₂ ) constant, the temperature was raised to 1000 ° C, and the reaction was continued for 2 hours to obtain porous graphene microspheres. Subsequently, the temperature was lowered to room temperature, and the porous graphene microspheres were taken out.

使用扫描电子显微镜观察所得的多孔石墨烯微球。电镜结果显示，所述多孔石墨烯微球的粒径为 2-8μπι，且每个微球表面布满了纳米级的孔结构。 The obtained porous graphene microspheres were observed using a scanning electron microscope. The results of electron microscopy showed that the porous graphene microspheres had a particle diameter of 2-8 μm, and the surface of each microsphere was covered with a nano-scale pore structure.

根据实施例 1所述的方法，使用由步骤 3)获得的多孔石墨烯微球制备超级电容器。测定所得超级电容器的容量、耐压性、倍率性能和寿命，结果汇总于表 1中。实施例 3 According to the method described in Example 1, a supercapacitor was prepared using the porous graphene microspheres obtained in the step 3). The capacity, pressure resistance, rate performance and life of the obtained supercapacitor were measured, and the results are summarized in Table 1. Example 3

将 1克由步骤 1)获得的氧化石墨烯与 0.2克添加剂甲酪一起添加至 500克的去离子水中，超声^：，从而获得石墨烯的均匀悬浮液。在 2MPa的喷雾压力， 160°C的进风温度， 80°C的出风温度下，借助喷雾干燥机 (型号 SY-600, 上海世远生物有限公司）将所述悬浮液喷雾干燥，由此获得粒径为 2-10μπι的氧化石墨烯微球。 One gram of the graphene oxide obtained in the step 1) was added together with 0.2 g of the additive methyl ketone to 500 g of deionized water, and ultrasonically: to obtain a uniform suspension of graphene. The suspension was spray dried by means of a spray dryer (Model SY-600, Shanghai Shiyuan Bios Co., Ltd.) at a spray pressure of 2 MPa, an inlet air temperature of 160 ° C, and an outlet temperature of 80 ° C. Graphene oxide microspheres having a particle diameter of 2 to 10 μm were obtained.

将 2克由步骤 2)获得的氧化石墨微球置于管式炉中，密封。首先，将温度升至 200°C，并以 0.5L/分钟的流速通入 BH₃/N₂，从而进行低温还原。其中 BH₃与 N₂的体积比为 1:9，低温还原的时间为 30分钟。随后，在保持还原气氛 (即，流速、 BH₃与 N₂的体积比)不变的情况下，将温度升至 400°C，继续反应 2小时，获得多孔石墨烯^ t球。随后，使温度降至室温，取出所述多孔石墨烯微球。 2 g of the graphite oxide microspheres obtained in the step 2) were placed in a tube furnace and sealed. First, the temperature was raised to 200 ° C, and BH ₃ /N _{2 was introduced} at a flow rate of 0.5 L/min to carry out low-temperature reduction. Wherein the volume ratio of BH ₃ to N ₂ is 1:9, and the time of low temperature reduction is 30 minutes. Subsequently, while maintaining the reducing atmosphere (i.e., the flow rate, the volume ratio of BH ₃ to N ₂ ) was changed, the temperature was raised to 400 ° C, and the reaction was continued for 2 hours to obtain a porous graphene ball. Subsequently, the temperature was lowered to room temperature, and the porous graphene microspheres were taken out.

使用扫描电子显微镜观察所得的多孔石墨烯微球。电镜结果显示，所述多孔石墨烯微球的粒径为 1-10μπι，且每个微球表面布满了微米和纳米级的孔结构。 The obtained porous graphene microspheres were observed using a scanning electron microscope. The results of electron microscopy showed that the porous graphene microspheres had a particle diameter of 1-10 μm, and the surface of each microsphere was covered with pore structures of micrometers and nanometers.

根据实施例 1所述的方法，使用由步骤 3)获得的多孔石墨烯微球制备超级电容器。测定所得超级电容器的容量、耐压性、倍率性能和寿命，结果汇总于表 1中。实施例 4 According to the method described in Example 1, a supercapacitor was prepared using the porous graphene microspheres obtained in the step 3). The capacity, pressure resistance, rate performance and life of the obtained supercapacitor were measured, and the results are summarized in Table 1. Example 4

1)通过氧化还原法 (hummers改进法)获得氧化石墨烯 (摘自 JACS, 1958， 80, 1339); 按照与实施例 1相同的方法获得氧化石墨烯。 1) obtaining graphene oxide by redox method (hummers improvement method) (taken from JACS, 1958, 80, 1339); Graphene oxide was obtained in the same manner as in Example 1.

将 10克由步骤 1)获得的氧化石墨烯与 2克添加剂碳酸氢铵一起添加至 500克的去离子水中，超声分散，从而获得石墨烯的均匀悬浮液。在 5MPa的喷雾压力， 120°C 的进风温度， 80°C的出风温度下，借助喷雾干燥机 (型号 SY-600)将所述悬浮液喷雾干燥，由此获得粒径为 2-10μπι的氧化石墨婦微球。 10 g of the graphene oxide obtained in the step 1) was added together with 2 g of the additive ammonium hydrogencarbonate to 500 g of deionized water, and ultrasonically dispersed to obtain a uniform suspension of graphene. The suspension was spray-dried by means of a spray dryer (model SY-600) at a spray pressure of 5 MPa, an inlet air temperature of 120 ° C, and an outlet temperature of 80 ° C, thereby obtaining a particle size of 2-10 μm. The graphite oxide microspheres.

将 2克由步骤 2)获得的氧化石墨微球置于管式炉中，密封。首先，将温度升至 80°C，并以 0.5L/分钟的流速通入 PH₃/N₂，从而进行低温还原。其中 PH₃与 N₂的体积比为 1:9，低温还原的时间为 30分钟。随后，在保持还原气氛 (即，流速、 8¾与的体积比)不变的情况下，将温度升至 250°C，继续反应 1小时，获得多孔石墨烯微球。随后，使温度降至室温，取出所述多孔石墨烯微球。 2 g of the graphite oxide microspheres obtained in the step 2) were placed in a tube furnace and sealed. First, the temperature was raised to 80 ° C, and PH ₃ /N _{2 was introduced} at a flow rate of 0.5 L/min to carry out low-temperature reduction. Wherein the volume ratio of PH ₃ to N ₂ is 1:9, and the time of low temperature reduction is 30 minutes. Subsequently, while maintaining the reducing atmosphere (i.e., the flow rate, the volume ratio of 83⁄4 to the same), the temperature was raised to 250 ° C, and the reaction was continued for 1 hour to obtain porous graphene microspheres. Subsequently, the temperature was lowered to room temperature, and the porous graphene microspheres were taken out.

使用扫描电子显微镜观察所得的多孔石墨烯微球。电镜结果显示，所述石墨烯微球的粒径为 1-15μπι, 且每个微球表面布满了微米和纳米级的孔结构。 The obtained porous graphene microspheres were observed using a scanning electron microscope. The results of electron microscopy showed that the graphene microspheres had a particle size of 1-15 μm, and the surface of each microsphere was covered with pore structures of micrometers and nanometers.

根据实施例 1所述的方法，使用由步骤 3)获得的多孔石墨烯微球制备超级电容器。测定所得超级电容器的容量、耐压性、倍率性能和寿命，结果汇总于表 1中。实施例 5 According to the method described in Example 1, a supercapacitor was prepared using the porous graphene microspheres obtained in the step 3). The capacity, pressure resistance, rate performance and life of the obtained supercapacitor were measured, and the results are summarized in Table 1. Example 5

类似于实施例 1的方法制备石墨烯微球，不同之处在于，将步骤 2)获得的氧化石墨微球在 400°C下还原 2小时。使用扫描电子显微镜观察由此获得的多孔石墨烯微球。电镜结果显示，所述多孔石墨烯微球的粒径为 2-10μπι，且每个微球表面布满了纳米级的孔结构。 Graphene microspheres were prepared in a manner similar to that of Example 1, except that the oxidized stone microspheres obtained in the step 2) were reduced at 400 ° C for 2 hours. The thus obtained porous graphene microspheres were observed using a scanning electron microscope. The results of electron microscopy showed that the porous graphene microspheres had a particle diameter of 2 to 10 μm, and the surface of each microsphere was covered with a nanometer pore structure.

根据实施例 1所述的方法，使用所述多孔石墨烯微球制备超级电容器。测定所得超级电容器的容量、耐压性、倍率性能和寿命，结果汇总于表 1中。实施例 6 According to the method described in Example 1, a supercapacitor was prepared using the porous graphene microspheres. The capacity, pressure resistance, rate performance and life of the obtained supercapacitor were measured, and the results are summarized in Table 1. Example 6

类似于实施例 5的方法制备石墨烯微球，不同之处在于，将步骤 2)获得的氧化石墨微球在 1000°C下还原 2小时。使用扫描电子显微镜观察由此获得的多孔石墨烯微球。电镜结果显示，所述多孔石墨烯微球的粒径为 2-15μπι，且每个微球表面布满了纳米级的孔结构。 Graphene microspheres were prepared in a manner similar to that of Example 5, except that the graphite oxide microspheres obtained in the step 2) were reduced at 1000 ° C for 2 hours. The porous graphene microparticle thus obtained was observed using a scanning electron microscope Ball. The results of electron microscopy showed that the porous graphene microspheres had a particle size of 2-15 μm, and the surface of each microsphere was covered with a nano-scale pore structure.

根据实施例 1所述的方法，使用所述多孔石墨烯微球制备超级电容器。测定所得超级电容器的容量、耐压性、倍率性能和寿命，结果汇总于表 1中。实施例 7 According to the method described in Example 1, a supercapacitor was prepared using the porous graphene microspheres. The capacity, pressure resistance, rate performance and life of the obtained supercapacitor were measured, and the results are summarized in Table 1. Example 7

类似于实施例 1的方法制备石墨烯微球，不同之处在于，所用还原气氛为 Η₂。使用扫描电子显微镜观察由此获得的多孔石墨烯微球。电镜结果显示，所述多孔石墨烯微球的粒径为 2-10μπι，且每个微球表面布满了微米和纳米级的孔结构。 Graphene microspheres were prepared in a manner similar to that of Example 1, except that the reducing atmosphere used was Η ₂ . The thus obtained porous graphene microspheres were observed using a scanning electron microscope. The results of electron microscopy showed that the porous graphene microspheres had a particle diameter of 2-10 μm, and the surface of each microsphere was covered with pore structures of micrometers and nanometers.

根据实施例 1所述的方法，使用所述多孔石墨烯微球制备超级电容器。测定所得超级电容器的容量、耐压性、倍率性能和寿命，结果汇总于表 1中。实施例 8 According to the method described in Example 1, a supercapacitor was prepared using the porous graphene microspheres. The capacity, pressure resistance, rate performance and life of the obtained supercapacitor were measured, and the results are summarized in Table 1. Example 8

类似于实施例 1的方法制备石墨烯微球，不同之处在于，所用还原气氛为 /^ ¾, 其中 ¾与 ΝΗ₃的体积比为 2: 8。使用扫描电子显微镜观察由此获得的多孔石墨烯微球。电镜结果显示，所述多孔石墨烯微球的粒径为 5-15μπι，且每个微球表面布满了微米和纳米级的孔结构。 It prepared similar to Example 1 graphene microspheres embodiment, except that the reducing atmosphere is a / ^ ¾ used, wherein the volume ratio of ₃ ¾ and ΝΗ is 2: 8. The thus obtained porous graphene microspheres were observed using a scanning electron microscope. The results of electron microscopy showed that the porous graphene microspheres had a particle diameter of 5-15 μm, and the surface of each microsphere was covered with pore structures of micrometers and nanometers.

根据实施例 1所述的方法，使用所述多孔石墨烯微球制备超级电容器。测定所得超级电容器的容量、耐压性、倍率性能和寿命，结果汇总于表 1中。对比实施例 1 According to the method described in Example 1, a supercapacitor was prepared using the porous graphene microspheres. The capacity, pressure resistance, rate performance and life of the obtained supercapacitor were measured, and the results are summarized in Table 1. Comparative Example 1

类似于实施例 1的方法制备石墨烯微球，不同之处在于在制备氧化石墨悬浮液的过程中不使用任何添加剂。使用由此获得的石墨烯微球制备电容器，测定所得电容器的容量、耐压性、倍率性能和寿命，结果汇总于表 1中。对比实施例 2 Graphene microspheres were prepared in a manner similar to that of Example 1, except that no additives were used in the preparation of the graphite oxide suspension. A capacitor was prepared using the thus obtained graphene microspheres, and the capacity, pressure resistance, rate performance and life of the obtained capacitor were measured, and the results are summarized in Table 1. Comparative Example 2

类似于实施例 1的方法制备石墨烯微球，不同之处在于在喷雾压力为 20MPa，进风温度为 300°C，出风温度为 200°C。使用由此获得的石墨烯微球制备电容器，测定所得电容器的容量、耐压性、倍率性能和寿命，结果汇总于表 1中。表 1 由石墨烯微球制备的电容器的电性能 Graphene microspheres were prepared in a manner similar to that of Example 1, except that the spray pressure was 20 MPa, the inlet air temperature was 300 ° C, and the outlet air temperature was 200 °C. A capacitor was prepared using the thus obtained graphene microspheres, and the capacity, pressure resistance, rate performance, and life of the obtained capacitor were measured, and the results are summarized in Table 1. Table 1 Electrical properties of capacitors prepared from graphene microspheres

由上表可以看出，与不添加任何添加剂的对比实施例 1相比，采用添加剂的本发明实施例 1-8具有更高的容量；其次，与不采用本发明优选喷雾干燥工艺参数的对比实施例 2相比，采用本发明优选喷雾干燥工艺参数的实施例 1-8能获得更好的电性能；最后，与在单一温度下还原的实施例 5-6相比，采用低温还原与高温还原组合的实施例 1-4和 7-8能获得更好的电性能。 As can be seen from the above table, the inventive examples 1-8 using the additive have a higher capacity than the comparative example 1 in which no additive is added; second, the comparison with the preferred spray drying process parameters without the use of the present invention In comparison with Example 2, Examples 1-8 using the preferred spray drying process parameters of the present invention gave better electrical properties; finally, compared to Examples 5-6 which were reduced at a single temperature, low temperature reduction and high temperature were employed. Examples 1-4 and 7-8 of the reduction combination gave better electrical properties.

由上表还可以看出，由本发明的多孔石墨烯微球制备的超级电容器具有良好的电性能，容量大于 80F/g,耐压性大于 3.5V,倍率性能大于 10A/g，长寿命 1000次>80%。 It can also be seen from the above table that the supercapacitor prepared by the porous graphene microsphere of the invention has good electrical properties, the capacity is greater than 80 F/g, the pressure resistance is greater than 3.5 V, the rate performance is greater than 10 A/g, and the long life is 1000 times. >80%.

通过本发明方法制备的多孔石墨烯微球具有微米级至纳米级的尺寸，且每个微球表面布满了纳米级的孔结构。而且，通过本发明方法制备的多孔石墨烯微球能保持性能的稳定，获得石墨烯颗粒的尺寸和单分散性和目前市场上使用的超级电容器活性炭材料的物理性质相似，可以较好的分散在溶剂中直接代替现有的产品，可以较好的匹配已有的生产工艺，便于工艺衔接。 The porous graphene microspheres prepared by the method of the present invention have a size ranging from micron to nanometer, and each microsphere surface is covered with a nanoscale pore structure. Moreover, the porous graphene microspheres prepared by the method of the invention can maintain the stability of the performance, and the size and monodispersity of the obtained graphene particles are similar to those of the supercapacitor activated carbon materials currently used on the market, and can be preferably dispersed in The solvent directly replaces the existing product, which can better match the existing production process and facilitate the process connection.

应当理解的是，上述针对本发明较佳实施例的表述较为详细，并不能因此而认为是对本发明专利保护范围的 P艮制，本发明的专利保护范围应以所附权利要求为准。 It should be understood that the above description of the preferred embodiments of the present invention is to be considered as a preferred embodiment of the invention.

Claims

权利要求 Rights request

3)通过气氛还原将所述氧化石墨烯颗粒还原。 3) Reduction of the graphene oxide particles by atmosphere reduction.

2.根据权利要求 1的方法，其中在步骤 1)中，还向在所述悬浮液中添加添加剂；其中所述添加剂为能在步骤 2)的喷雾干燥温度或步骤 3)的还原温度下与氧化石墨或者石墨烯之间发生物理或者化学反应以形成新的化学结构的那些，例如含氨基有机化合物如氨基酸、尿素、硫脲、芳香胺化合物如对苯二胺，含羟基的有机化合物如乙二醇、甘油、环糊精、葡萄糖；以及曱酪；能在步骤 2)的喷雾干燥温度下发生聚合反应，从而与氧化石墨烯形成混合物或者引发所述聚合反应的化合物，例如聚合物单体如苯乙烯、曱基丙烯酸、苯胺以及引发剂如自由基聚合引发剂，阳离子聚合引发剂、阴离子聚合引发剂；能在步骤 3)的还原温度下分解产生气体的那些，如酸、乙酸铵、碳酸氢铵。 2. The method according to claim 1, wherein in step 1), an additive is further added to the suspension; wherein the additive is capable of being at a spray drying temperature of step 2) or a reduction temperature of step 3) Those in which physical or chemical reactions occur between graphite oxide or graphene to form new chemical structures, such as amino-containing organic compounds such as amino acids, urea, thiourea, aromatic amine compounds such as p-phenylenediamine, hydroxyl-containing organic compounds such as B. a diol, glycerin, cyclodextrin, glucose; and strontium; a compound which can be polymerized at a spray drying temperature of step 2) to form a mixture with the graphene oxide or initiate the polymerization, such as a polymer monomer For example, styrene, mercaptoacrylic acid, aniline, and an initiator such as a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator; those which can decompose to generate a gas at the reduction temperature of the step 3), such as an acid, ammonium acetate, Ammonium bicarbonate.

3. 根据权利要求 2的方法，其中所述添加剂的用量基于所述分散介质重量为 0.0001-30重量％, 优选为 0.001-20重量％, 更优选为 0.01-15重量％，更优选为 0.01-10 重量％, 最优选为 0.01-5重量％。 3. The method according to claim 2, wherein the additive is used in an amount of 0.0001 to 30% by weight, based on the weight of the dispersion medium, preferably 0.001 to 20% by weight, more preferably 0.01 to 15% by weight, still more preferably 0.01- 10% by weight, most preferably 0.01 to 5% by weight.

4. 根据权利要求 1-3中任一项的方法，其中在压力喷雾技术中，喷雾压力为 l-10MPa , 优选 4-6MPa , 进风温度为 120-200°C , 优选 140-160°C , 出风温度为 80-120°C，优选 90-100°C; 在离心喷雾技术中，离心速度为 50-10000转 /分钟，优选 2000-5000转 /分钟。 The method according to any one of claims 1 to 3, wherein in the pressure spray technique, the spray pressure is from 1 to 10 MPa, preferably from 4 to 6 MPa, and the inlet air temperature is from 120 to 200 ° C, preferably from 140 to 160 ° C. The outlet temperature is 80-120 ° C, preferably 90-100 ° C; in the centrifugal spray technique, the centrifugal speed is 50-10000 rpm, preferably 2000-5000 rpm.

5. —种制备石墨烯材料的方法，其包括如下步骤： 5. A method of preparing a graphene material, comprising the steps of:

3) 首先在低温气氛下还原所述氧化烯石墨颗粒，随后在高温气氛下进行还原，由此获得多孔石墨烯 :球。 3) First, the alkylene oxide graphite particles are reduced under a low temperature atmosphere, followed by reduction under a high temperature atmosphere, thereby obtaining porous graphene: balls.

6. 根据权利要求 5的方法，其中低温气氛还原的温度为 80-200°C，优选为 100-180°C, 更优选为 150°C; 高温气氛还原的温度为高于 200°C至 1000°C, 优选为 400-800°C, 更优选为 600°C。 6. The method according to claim 5, wherein the temperature of the low temperature atmosphere reduction is from 80 to 200 ° C, preferably 100-180 ° C, more preferably 150 ° C; the temperature of the high-temperature atmosphere reduction is higher than 200 ° C to 1000 ° C, preferably 400-800 ° C, more preferably 600 ° C.

7.根据权利要求 5-6中任一项的方法，其中在步骤 1)中，还向在所述悬浮液中添加添加剂；其中所述添加剂为能在步骤 2)的喷雾干燥温度或步骤 3)的还原温度下与氧化石墨或者石墨烯之间发生物理或者化学反应以形成新的化学结构的那些，例如含氨基有机化合物如氨基酸、尿素、硫脲、芳香胺化合物如对苯二胺，含羟基的有机化合物如乙二醇、甘油、环糊精、葡萄糖；以及甲酪；能在步骤 2)的喷雾干燥温度下发生聚合反应，从而与氧化石墨烯形成混合物或者引发所述聚合反应的化合物，例如聚合物单体如苯乙烯、曱基丙烯酸、苯胺以及引发剂如自由基聚合引发剂，阳离子聚合引发剂、阴离子聚合引发剂；能在步骤 3)的还原温度下分解产生气体的那些，如氨基酸、乙酸铵、碳酸氢铵。 The method according to any one of claims 5 to 6, wherein in step 1), an additive is further added to the suspension; wherein the additive is at a spray drying temperature of step 2) or step 3 Those that physically or chemically react with graphite oxide or graphene at a reduction temperature to form a new chemical structure, such as amino-containing organic compounds such as amino acids, urea, thiourea, aromatic amine compounds such as p-phenylenediamine, a hydroxyl group organic compound such as ethylene glycol, glycerin, cyclodextrin, glucose; and methyl ketone; a compound which can be polymerized at a spray drying temperature of the step 2) to form a mixture with the graphene oxide or initiate the polymerization reaction For example, a polymer monomer such as styrene, mercaptoacrylic acid, aniline, and an initiator such as a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator; those which can decompose to generate a gas at the reduction temperature of the step 3), Such as amino acids, ammonium acetate, ammonium bicarbonate.

8.根据权利要求 5-7任一项的方法，其中步骤 3)中的低温和高温气氛还原在还原性气氛下进行，所述还原性气氛为 H₂、 NH₃、 BH₃、 PH₃、 H₂S中的一种或多种，其中任选添力口 N₂。 The method according to any one of claims 5 to 7, wherein the low temperature and high temperature atmosphere reduction in the step 3) is carried out under a reducing atmosphere of H ₂ , NH ₃ , BH ₃ , PH ₃ , One or more of H ₂ S, wherein the force port N _{2 is} optionally added.

9. 一种通过权利要求 1-8任一项的方法获得的石墨烯材料。 9. A graphene material obtained by the method of any one of claims 1-8.

10. 通过权利要求 1-8任一项的方法获得或者根据权利要求 9的石墨烯材料的用途，其中将其用作超级电容器的电极材料，用作催化剂载体或红外光学材料。 10. Use of the graphene material obtained by the method of any one of claims 1-8 or according to claim 9, wherein it is used as an electrode material for a supercapacitor, as a catalyst carrier or an infrared optical material.