WO2015000152A1 - Method for preparing graphene/nano-carbon particle composite - Google Patents

Method for preparing graphene/nano-carbon particle composite Download PDF

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Publication number
WO2015000152A1
WO2015000152A1 PCT/CN2013/078770 CN2013078770W WO2015000152A1 WO 2015000152 A1 WO2015000152 A1 WO 2015000152A1 CN 2013078770 W CN2013078770 W CN 2013078770W WO 2015000152 A1 WO2015000152 A1 WO 2015000152A1
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graphene
carbon
spray
suspension
nano
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PCT/CN2013/078770
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French (fr)
Chinese (zh)
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王要兵
洪茂椿
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中国科学院福建物质结构研究所
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Priority to PCT/CN2013/078770 priority Critical patent/WO2015000152A1/en
Publication of WO2015000152A1 publication Critical patent/WO2015000152A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to the field of graphene materials, in particular to a method for preparing a graphene/nanocarbon particle composite material, and to the application of a mesene/nanoparticle composite material in a supercapacitor. Background technique
  • graphene materials can be used as electrode materials in supercapacitors and lithium ion batteries. So far, graphite has been prepared.
  • 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 further vaporizing graphite to peel off under external force.
  • Graphene oxide 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.
  • the graphene after reduction is easily agglomerated, resulting in loss of some functions and difficulty in processing, which is not conducive to industrialization.
  • Graphene research has become a hot research topic in current materials.
  • Graphene is also a kind of carbon material. It has the same properties as carbon materials in many aspects, but at the same time it exists in a two-dimensional structure, so it has unique properties, graphene. And the application of nano carbon particles is particularly extensive. Based on the above reasons, in order to take advantage of these two different materials, we have proposed a new method for preparing graphene/nano-particle materials. Summary of the invention
  • the present invention provides a method for preparing a graphene composite material loaded with carbon nanoparticles, comprising the following steps:
  • step 5) The powder obtained in the step 4) is subjected to reduction treatment, and after the reduction is completed, it is cooled to room temperature in a reducing atmosphere, washed and dried to finally obtain a graphene composite material loaded with carbon nanoparticles.
  • the graphite raw material used in the present invention may be a graphite flake such as natural flake graphite, graphite powder, ketjen black or the like.
  • nanocarbon particles in the present invention are not particularly referred to as spherical particles, but refer to other carbon materials having a nanometer size in addition to graphene.
  • the nanocarbon particles used in the present invention may be carbon 60, carbon black, acetylene black, ketjen black, carbon nanotubes, carbon nanofibers or a combination thereof.
  • the nanocarbon particles have a size of 2 to 100 nm, preferably 10 to 80 nm, more preferably 20 to 60 nm, and most preferably 20 to 50 nm; in the case of spherical carbon particles, the size means an average diameter; In the case of carbon, the size refers to the average thickness; in the case of carbon nanofibers, the size refers to the diameter of the fiber; in the case of other shapes, it refers to between any two points on the surface of the material. The longest straight line distance.
  • the method of preparing graphene oxide by graphite oxide is an improved Hummers method, which is well known to those skilled in the art, for example, see JACS, 1958, 80, 1339.
  • the surfactant for dispersing the nano carbon particles may be any surfactant capable of uniformly dispersing carbon nanoparticles and graphene oxide, uniformly mixing, and being water-washed after high temperature, including but not limited to anionic surfactants. , cationic surfactant, zwitterionic surfactant, nonionic surfactant and special surfactant, wherein the anionic surfactants are: sulfate type, carboxylate type, sulfonate type and phosphate
  • the cationic surfactants are: quaternary ammonium salt type, imidazolium salt type and pyridinium salt type; wherein the zwitterionic surfactants are: acid type, betaine type, pyrazoline type, etc.;
  • the ionic surfactants are: polyoxyethylene, phenolyl alcohol amine, sorbitan fatty acid ester, amine oxide, alkyl glycoside and the like.
  • the special surfactant contains a fluorocarbon surfactant (for example, C 2 F 5 (OCF 2 CF(CF 3 )) 2 OC 2 F 4 S0 3 Na), a silicon-containing surfactant, a Gemini surfactant, and the like.
  • the surfactant is usually used in an amount of 0.001 to 30 g/L, preferably 0.01 to 10 g/L, and most preferably 0.1 to 5 g/L.
  • the nanocarbon particles are used in an amount of from 1 to 50%, preferably from 1 to 20%, most preferably from 5 to 15%, based on the mass of the graphene oxide.
  • the spray drying technique used in the present invention may be a centrifugal spray, an ultrasonic spray, a jet spray or a pressure spray technique or a combination thereof.
  • Spray drying equipment is well known to those skilled in the art.
  • Pressure spray techniques are preferred.
  • the size of the carbon nanoparticle-loaded graphene composite 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 the spray drying process, 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.
  • Composite material is preferably optimized to obtain the desired size, structure, and desired electrical properties.
  • the inventors have found through long-term studies that spray drying can be carried out under the following process conditions to obtain an oxyalkylene graphene/carbon nanoparticle composite having the desired size, structure and particularly good electrical properties: under pressure
  • the spray pressure is l-10 MPa, preferably 4-6 MPa
  • the inlet air temperature is 120-200 ° C, preferably 140-160 ° C
  • the outlet temperature is 80-120 ° C, preferably 90-100 ° C
  • the centrifugal speed is from 50 to 10,000 rpm, preferably from 2,000 to 5,000 rpm.
  • the resulting powder was subjected to a reduction treatment under a reducing atmosphere.
  • the reducing agent used in the reduction treatment is preferably a reducing gas including, but not limited to, hydrogen, or a mixed gas of hydrogen and an inert gas.
  • the volume ratio of hydrogen to inert gas is from 1:100 to 30:100, preferably from 5:100 to 20:100, more preferably 10 : 100-20:100, most preferably 10:100-15:100.
  • the inert gas is argon, nitrogen, helium or neon.
  • the reduction treatment time is from 1 to 10 hours, preferably from 2 to 4 hours.
  • the temperature of the reduction treatment is from 600 to 1200 ° C, preferably from 600 to 800 ° C.
  • the reduction treatment is usually carried out in a tube furnace. Specific tube furnaces are well known to those skilled in the art.
  • the inventors have found through long-term intensive studies that the spray-dried powder is first pre-heat treated under an inert atmosphere, and then the powder is cooled to room temperature, followed by reduction under a reducing atmosphere. By reacting, a carbon nanoparticle-loaded graphene composite material having particularly excellent properties can be obtained.
  • low temperature pretreatment is beneficial to the decomposition of reactive groups.
  • the pore structure is formed, and the later reduction treatment is advantageous for improving the conductivity of the graphene material and further stabilizing the structure.
  • the present invention is directed to a method of preparing a graphene composite loaded with carbon nanoparticles, comprising the steps of:
  • step 5) The powder obtained in the step 4) is placed under an inert gas atmosphere, preheated, and then cooled to room temperature, followed by reduction in a reducing atmosphere, and after reduction, cooling to a reducing atmosphere At room temperature, it is washed and dried to finally produce a graphene composite loaded with carbon nanoparticles.
  • the preheat treatment temperature is usually 300 to 500 ° C, preferably 320 to 400 ° C, and most preferably 350 to 400 ° C; the preheat treatment time is usually 1 to 12 hours, preferably 2-4 hours.
  • the inert gas used in the inert atmosphere is argon, nitrogen, helium or neon.
  • the reduction treatment is carried out at a temperature of from 600 to 1200 ° C, preferably from 600 to 800 ° C; and the reduction treatment is usually carried out for from 1 to 10 hours, preferably from 2 to 4 hours.
  • the preheating and reduction treatments of the present invention are generally carried out in a tube furnace, which may be carried out in the same tube furnace or in a different tube furnace, but preferably in the same tube furnace. Specific tube furnaces are well known to those skilled in the art.
  • the present invention relates to an embodiment in which the powder obtained after drying is placed in a tube furnace with an inert gas and slowly heated to a temperature of 300 to 500 ° C for 10 to 12 hours at 10 ° C / mi, and then the powder is further Cooling to room temperature with the furnace; then introducing a mixed gas of hydrogen and an inert gas into the tubular furnace (for example, hydrogen, or a volume ratio of 1:100-30:100), wherein the inert gas is argon gas, nitrogen gas , helium or helium) 5-10m i, control the flow rate of reducing gas to 60mL / min, the air in the tube furnace is discharged to form a reducing atmosphere, and then the temperature is raised to 600-1200 ° C, at this temperature Keep heating for l-10h, after the reduction is completed, cool to room temperature under reducing atmosphere, and repeatedly wash with distilled water and absolute ethanol to remove residual surfactant and its residue after high temperature conversion (such as inorganic salt), the final system A graphene
  • the carbon nanoparticle graphene composite of the present invention can be used as a supercapacitor material, a catalyst carrier or Infrared optical material.
  • the nano carbon particles can be well dispersed between the sheets of graphene, a synergistic effect can be exerted; in the composite material prepared by the method, both of them
  • the composite not only prevents the agglomeration of the graphene sheets, but also prevents the agglomeration between the carbon particles, effectively increasing the specific surface area of the composite, thereby improving the capacitance performance thereof; and the conductivity of the graphene sheets and the carbon nanoparticles are high.
  • the resulting composite material also has a higher conductivity;
  • the composite material prepared by the method has a high specific surface area and has wide application prospects in the field of supercapacitors;
  • Figure 1 is a particle obtained by spray drying in Example 1.
  • Fig. 2 is a graph showing the charge and discharge curves of the supercapacitor prepared in Example 1. detailed description
  • the invention provides a graphene/nano carbon particle composite material and a preparation method thereof, firstly, the natural flake graphite is oxidized into graphene oxide, the surfactant dissolves the nano particles to form a suspension, and the graphene oxide nano carbon particles are obtained by mixing.
  • the suspension is stirred at room temperature, and after mixing uniformly, the mixed suspension is spray-dried, the solvent is removed to obtain a powder, and the powder is placed in a tube furnace protected by an inert gas to be heated and reduced.
  • the invention provides a process for preparing a graphene composite material loaded with carbon nanoparticles as follows: natural flake graphite ⁇ graphene oxide ⁇ graphene oxide suspension ⁇ carbon nanoparticle and graphene mixed suspension ⁇ graphene/nanocarbon Granular composites.
  • the present invention relates to the following aspects:
  • a method for preparing a graphene/nano carbon particle composite material comprising the steps of:
  • nanocarbon particles are selected from the group consisting of carbon 60, carbon black, aceton black, ketjen black, carbon nanotubes, carbon nanofibers, or a combination thereof.
  • nanocarbon particles have a size of from 2 to 100 nm, preferably from 10 to 80 nm, more preferably from 20 to 60 nm, and most preferably from 20 to 50 nm.
  • step 4 employs a centrifugal spray, an ultrasonic spray, a gas spray or a pressure spray technique, or a combination thereof.
  • the spray drying is carried out by a pressure spray technique, wherein 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.
  • the reducing atmosphere is hydrogen or a mixed gas of hydrogen and an inert gas.
  • the method according to any one of 1-8, wherein the reduction treatment in a) and b) of step 5) is from 1 to 10 hours, preferably from 2 to 4 hours.
  • the preheating temperature is 300-500 ° C, preferably 320-400 ° C, most preferably 350 ° C;
  • the preheat treatment time is 1-12 hours, preferably 2-4 hours.
  • a graphene/nanocarbon particle composite obtained by the method of any of 1-11.
  • Example 1 The preparation process of the present invention is further illustrated by the following examples, and the embodiments of the present invention are not intended to limit the scope of the present invention. Any modifications and variations made on the basis of the present invention are within the scope of the present invention.
  • Example 1
  • 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. After drying under vacuum at 60 ° C for 48 hours, graphene oxide was obtained, which was added to deionized water and stirred to obtain a suspension.
  • 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. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • Ketjen black ECP600JD (Switzerland, Temco ECP600JD, particle size 20 nm) was added to 500 mL of deionized water together with 5 g of surfactant dodecyltetraethyl quaternary ammonium salt. The ultrasonic power was dispersed for 100 min for 30 min, thereby obtaining a uniform suspension of Ketchen Black ECP600JD.
  • 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 capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • 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. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • 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, Seal the injection port to get a supercapacitor. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • Example 5 Example 5:
  • 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. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1.
  • 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. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1. Comparative Example 1
  • Example 7 A graphene/nanocarbon particle composite was prepared similarly to the procedure of Example 6, and a supercapacitor was prepared according to the procedure of Example 6 (6), and its capacity, pressure resistance, rate performance and life were measured. The results are summarized in Table 1. in. The difference from Example 6 was that, at the time of spray drying, a spray pressure of 3 MPa, an inlet air temperature of 200 ° C, and an outlet air temperature of 90 ° C were employed.
  • Example 7 A graphene/nanocarbon particle composite was prepared similarly to the procedure of Example 6, and a supercapacitor was prepared according to the procedure of Example 6 (6), and its capacity, pressure resistance, rate performance and life were measured. The results are summarized in Table 1. in. The difference from Example 6 was that, at the time of spray drying, a spray pressure of 3 MPa, an inlet air temperature of 200 ° C, and an outlet air temperature of 90 ° C were employed.
  • Example 7
  • a graphene/nanocarbon particle composite was prepared in a manner similar to that of Example 6, and a supercapacitor was prepared according to the procedure of the procedure (6) of Example 1, and the capacity, pressure resistance, rate performance and life were measured.
  • the results are summarized in Table 1. in.
  • the difference from Example 1 is that after spray drying, 2 g of the obtained powder is slowly heated to 800 ° C at 10 ° C / mi in a tube furnace having a volume ratio of 20:100 hydrogen and an inert gas. After maintaining the temperature for 5 h, after the reduction, the mixture was cooled to room temperature under a hydrogen atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the surfactant and its residue, and finally a graphene/carbon nanoparticle composite material was obtained.
  • the graphene/nanocarbon particle composite prepared by the present invention has better electrical properties.

Abstract

The present invention provides a method for preparing a graphene/nano-carbon particle composite. The method comprises: 1) oxidizing graphite to prepare oxidized graphene, and adding the obtained oxidized graphene into water to prepare a suspension liquid; 2) adding nano-carbon particles into a water solution with a surface active agent to obtain a suspension liquid of the nano-carbon particles; 3) mixing the suspension liquid of the oxidized graphene with the suspension liquid of the nano-carbon particles, so as to obtain a mixed suspension liquid; 4) performing spray drying on the uniformly mixed suspension liquid to obtain powder; and 5) performing reduction treatment on the powder obtained in step 4), or placing the powder obtained in step 4) in an inert gas atmosphere, preheating the powder, and then performing reduction reaction in a reducing atmosphere, so as to finally prepare the graphene composite loaded with the nano-carbon particles. The present invention also relates to the graphene/nano-carbon particle composite obtained by using the method of the present invention, and applications of the graphene/nano-carbon particle composite used as a supercapacitor material, a catalyst carrier or an infrared optical material.

Description

说明书 一种石墨烯纳米碳颗粒复合材料的制备方法 技术领域  Preparation method of graphene nano carbon particle composite material
本发明涉及石墨烯材料领域， 尤其涉及一种石墨烯 /纳米碳颗粒复合材料的制备 方法， 以及所 墨烯 /纳 颗粒复合材料在超级电容器中的应用。 背景技术  The invention relates to the field of graphene materials, in particular to a method for preparing a graphene/nanocarbon particle composite material, and to the application of a mesene/nanoparticle composite material in a supercapacitor. Background technique
自从英国曼彻斯特大学的安德烈 ·Κ·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膚， 石墨婦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、 高栽流子传输率 (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廣， 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， 氣化石 墨再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它物质的复合。 但是， 还原后的石墨烯很容易团聚， 导致一些功能的丧失， 同时也难以加工， 不利于产业 化。 Since the preparation of graphene materials by Andre K. Geim of the University of Manchester in the UK in 2004, due to its unique structure and photoelectricity, graphite materials have received extensive attention. 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 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 planting Stream transfer 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 conductivity, large specific surface area and its two-dimensional nanoscale structure of monolayers, graphene materials can be used as electrode materials in supercapacitors and lithium ion batteries. So far, graphite has been prepared. There are many methods for olefins, 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 further vaporizing graphite to peel off under external force. Graphene oxide, 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 loss of some functions and difficulty in processing, which is not conducive to industrialization.
石墨烯的研究已经成为目前材料的研究热点， 石墨烯也是碳材料的一种， 在很 多方面与碳材料有相同的性质， 但同时它又以二维结构存在， 因此具有独特的性质， 石墨烯和纳米碳颗粒的应用都特别广泛。 基于以上原因， 为了发挥这两种不同材料 的优势， 我们提出了一种新型石墨烯 /纳^^颗粒材料的制备方法。 发明内容  Graphene research has become a hot research topic in current materials. Graphene is also a kind of carbon material. It has the same properties as carbon materials in many aspects, but at the same time it exists in a two-dimensional structure, so it has unique properties, graphene. And the application of nano carbon particles is particularly extensive. Based on the above reasons, in order to take advantage of these two different materials, we have proposed a new method for preparing graphene/nano-particle materials. Summary of the invention
替换页 (细则笫 26条) 基于上述问题， 本发明提供了一种负载有碳纳米颗粒的石墨烯复合材料的制备 方法， 包括如下步骤： Replacement page (Article 26) Based on the above problems, the present invention provides a method for preparing a graphene composite material loaded with carbon nanoparticles, comprising the following steps:
1)将石墨氧化以制备氧化石墨烯， 将所得氧化石墨烯添加至水中制得悬浮液；  1) oxidizing graphite to prepare graphene oxide, adding the obtained graphene oxide to water to prepare a suspension;
2)将纳米碳颗粒添加至表面活性剂的水溶液中以获得纳米碳颗粒的悬浮液；  2) adding nano carbon particles to an aqueous solution of a surfactant to obtain a suspension of nano carbon particles;
3)将氧化石墨烯悬浮液与纳米碳颗粒悬浮液混合， 得到氧化石墨烯 /纳米碳颗粒的均 匀混合悬浮液；  3) mixing the graphene oxide suspension with the nano carbon particle suspension to obtain a uniform mixed suspension of graphene oxide/nano carbon particles;
4)将步骤 3)中所得的混合悬浮液喷雾干燥， 得到粉末；  4) spray-drying the mixed suspension obtained in the step 3) to obtain a powder;
5)对步骤 4)中所得的粉末进行还原处理， 还原完毕后， 在还原气氛下冷却至室温， 清 洗并干燥， 从而最终制得负载有碳纳米颗粒的石墨烯复合材料。  5) The powder obtained in the step 4) is subjected to reduction treatment, and after the reduction is completed, it is cooled to room temperature in a reducing atmosphere, washed and dried to finally obtain a graphene composite material loaded with carbon nanoparticles.
本发明所用的石墨原料可为石墨片如天然鳞片石墨、 石墨粉、 科琴黑等。  The graphite raw material used in the present invention may be a graphite flake such as natural flake graphite, graphite powder, ketjen black or the like.
应理解的是， 本发明中的"纳米碳颗粒"并非特指球状颗粒， 而是指除石墨烯之 外具有纳米尺寸的其他碳材料。 具体而言， 本发明所用的纳米碳颗粒可为碳 60、 碳 黑、 乙炔黑、 科琴黑、 碳纳米管、 碳纳米纤维或其组合。 所述纳米碳颗粒的尺寸为 2-100nm, 优选为 10-80nm， 更优选为 20-60nm， 最优选为 20-50nm; 在球状碳颗粒的 情况下， 所述尺寸是指平均直径； 在片状碳的情况下， 所述尺寸是指平均厚度； 在 碳纳米纤维的情况下， 所述尺寸是指纤维的直径； 在其他形状的情况下， 是指该材 料表面上任意两点之间的最长的直线距离。  It should be understood that the "nanocarbon particles" in the present invention are not particularly referred to as spherical particles, but refer to other carbon materials having a nanometer size in addition to graphene. Specifically, the nanocarbon particles used in the present invention may be carbon 60, carbon black, acetylene black, ketjen black, carbon nanotubes, carbon nanofibers or a combination thereof. The nanocarbon particles have a size of 2 to 100 nm, preferably 10 to 80 nm, more preferably 20 to 60 nm, and most preferably 20 to 50 nm; in the case of spherical carbon particles, the size means an average diameter; In the case of carbon, the size refers to the average thickness; in the case of carbon nanofibers, the size refers to the diameter of the fiber; in the case of other shapes, it refers to between any two points on the surface of the material. The longest straight line distance.
通过氧化石墨而制备氧化石墨烯的方法为改进的 Hummers法， 其是本领域技术 人员所公知的， 例如可参见 JACS， 1958， 80， 1339。  The method of preparing graphene oxide by graphite oxide is an improved Hummers method, which is well known to those skilled in the art, for example, see JACS, 1958, 80, 1339.
用于分散纳米碳颗粒的表面活性剂可为任何能均匀分散碳纳米粒子与氧化石墨 烯， 使其混合均匀， 并且可在高温后水洗除去的表面活性剂， 包括但不限于阴离子 型表面活性剂， 阳离子型表面活性剂， 两性离子型表面活性剂， 非离子型表面活性 剂以及特种表面活性剂， 其中阴离子型表面活性剂为： 硫酸盐型、 羧酸盐型、 磺酸 盐型以及磷酸盐型等； 其中阳离子型表面活性剂为： 季铵盐型、 咪唑盐型以及吡啶 盐型等； 其中两性离子型表面活性剂为： 酸型、 甜菜碱型、 以及吡唑啉型等； 其中非离子型表面活性剂为： 聚氧乙烯、 坑基酰醇胺、 失水山梨醇脂肪酸酯、 氧化 胺、 烷基糖苷等。 特种表面活性剂 包含氟碳类表面活性剂（如： C2F5(OCF2CF(CF3))2OC2F4S03Na)， 含硅的表面活性剂以及 Gemini表面活性剂等。 表面活性剂的用量通常为 0.001-30g/L， 优选为 0.01-10g/L, 最优选为 0.1-5g/L。 所述纳米碳颗粒的用量为 1-50%， 优选为 1-20%， 最优选为 5-15%， 基于氧化石 墨烯的质量。 The surfactant for dispersing the nano carbon particles may be any surfactant capable of uniformly dispersing carbon nanoparticles and graphene oxide, uniformly mixing, and being water-washed after high temperature, including but not limited to anionic surfactants. , cationic surfactant, zwitterionic surfactant, nonionic surfactant and special surfactant, wherein the anionic surfactants are: sulfate type, carboxylate type, sulfonate type and phosphate The cationic surfactants are: quaternary ammonium salt type, imidazolium salt type and pyridinium salt type; wherein the zwitterionic surfactants are: acid type, betaine type, pyrazoline type, etc.; The ionic surfactants are: polyoxyethylene, phenolyl alcohol amine, sorbitan fatty acid ester, amine oxide, alkyl glycoside and the like. The special surfactant contains a fluorocarbon surfactant (for example, C 2 F 5 (OCF 2 CF(CF 3 )) 2 OC 2 F 4 S0 3 Na), a silicon-containing surfactant, a Gemini surfactant, and the like. The surfactant is usually used in an amount of 0.001 to 30 g/L, preferably 0.01 to 10 g/L, and most preferably 0.1 to 5 g/L. The nanocarbon particles are used in an amount of from 1 to 50%, preferably from 1 to 20%, most preferably from 5 to 15%, based on the mass of the graphene oxide.
本发明所用的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 技术或其组合。 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。 所述负载有碳纳米颗粒的石墨烯复合材料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， 在喷雾干燥过程中， 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复合材料。 令人惊讶的是， 本 发明人经过长期研究发现， 在下述工艺条件下实施喷雾干燥能获得具有所需尺寸、 结构和特别好的电性能的氧化烯石墨烯 /碳纳米颗粒复合材料： 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。 在上述工艺条件下， 能获得具有特别好的性能的氧化石墨烯 / 复合材料。  The spray drying technique used in the present invention may be a centrifugal spray, an ultrasonic spray, a jet spray or a pressure spray technique or a combination thereof. Spray drying equipment is well known to those skilled in the art. Pressure spray techniques are preferred. The size of the carbon nanoparticle-loaded graphene composite 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 the spray drying process, 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. Composite material. Surprisingly, the inventors have found through long-term studies that spray drying can be carried out under the following process conditions to obtain an oxyalkylene graphene/carbon nanoparticle composite having the desired size, structure and particularly good electrical properties: under pressure In the 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; the outlet temperature is 80-120 ° C, preferably 90-100 ° C; In the centrifugal spray technique, the centrifugal speed is from 50 to 10,000 rpm, preferably from 2,000 to 5,000 rpm. Under the above process conditions, graphene oxide/composites with particularly good properties can be obtained.
在喷雾干燥后， 在还原气氛下对所得粉末进行还原处理。  After spray drying, the resulting powder was subjected to a reduction treatment under a reducing atmosphere.
还原处理中所用的还原剂优选为还原气体， 包括但不限于氢气， 或者氢气与惰 性气体的混合气体。 在后一情况下， 即， 使用氢气与惰性气体的混合气体的情况下， 氢气与惰性气体的体积比为 1:100-30:100， 优选为 5:100-20:100， 更优选为 10:100-20:100, 最优选为 10:100-15:100。 所述惰性气体为氩气、 氮气、 氦气或氖气。 还原处理的时间为 1-10小时， 优选为 2-4小时。 还原处理的温度为 600-1200 °C， 优选 为 600-800°C。 所述还原处理通常在管式炉中进行。 具体的管式炉是本领域技术人员 所熟知的。  The reducing agent used in the reduction treatment is preferably a reducing gas including, but not limited to, hydrogen, or a mixed gas of hydrogen and an inert gas. In the latter case, that is, in the case of using a mixed gas of hydrogen and an inert gas, the volume ratio of hydrogen to inert gas is from 1:100 to 30:100, preferably from 5:100 to 20:100, more preferably 10 : 100-20:100, most preferably 10:100-15:100. The inert gas is argon, nitrogen, helium or neon. The reduction treatment time is from 1 to 10 hours, preferably from 2 to 4 hours. The temperature of the reduction treatment is from 600 to 1200 ° C, preferably from 600 to 800 ° C. The reduction treatment is usually carried out in a tube furnace. Specific tube furnaces are well known to those skilled in the art.
还原完毕后， 在还原气氛下冷却至室温， 并用蒸馏水和无水乙醇反复清洗以除 去残留的表面活性剂及其经高温转化后所得残余物 (例如无机盐)， 最终制得负载有碳 纳米颗粒的石墨烯复合材料。  After the reduction is completed, it is cooled to room temperature under a reducing atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the residual surfactant and the residue obtained after high-temperature conversion (for example, an inorganic salt), thereby finally preparing carbon nanoparticles loaded. Graphene composite.
另一方面， 令人惊讶的是， 本发明人经过长期深入的研究发现， 在惰性气氛下， 首先对喷雾干燥的粉末进行预热处理， 再将粉末冷却至室温， 接着于还原气氛下进 行还原反应， 可获得具有特别好的性能的负载有碳纳米颗粒的石墨烯复合材料。 不 希望被理论所束缚， 申请人经过长期研究发现低温预处理有利于活性基团的分解， 形成孔洞结构， 而后期的还原处理有利于提高石墨烯材料的导电率， 进一步的稳定 其结构。 On the other hand, surprisingly, the inventors have found through long-term intensive studies that the spray-dried powder is first pre-heat treated under an inert atmosphere, and then the powder is cooled to room temperature, followed by reduction under a reducing atmosphere. By reacting, a carbon nanoparticle-loaded graphene composite material having particularly excellent properties can be obtained. Without wishing to be bound by theory, the applicant has long found that low temperature pretreatment is beneficial to the decomposition of reactive groups. The pore structure is formed, and the later reduction treatment is advantageous for improving the conductivity of the graphene material and further stabilizing the structure.
因此， 在本发明的一个优选实施方案中， 本发明涉及一种负载有碳纳米颗粒的 石墨烯复合材料的制备方法， 包括如下步骤：  Accordingly, in a preferred embodiment of the present invention, the present invention is directed to a method of preparing a graphene composite loaded with carbon nanoparticles, comprising the steps of:
1)将石墨氧化以制备氧化石墨烯， 将所得氧化石墨烯添加至水中制得悬浮液；  1) oxidizing graphite to prepare graphene oxide, adding the obtained graphene oxide to water to prepare a suspension;
2)将纳米碳颗粒添加至表面活性剂的水溶液中以获得纳米碳颗粒的悬浮液；  2) adding nano carbon particles to an aqueous solution of a surfactant to obtain a suspension of nano carbon particles;
3)将氧化石墨烯悬浮液与纳米碳颗粒悬浮液混合， 得到氧化石墨烯 /纳米碳颗粒的均 匀混合悬浮液；  3) mixing the graphene oxide suspension with the nano carbon particle suspension to obtain a uniform mixed suspension of graphene oxide/nano carbon particles;
4)将步骤 3)中所得的混合悬浮液喷雾干燥， 除去溶剂后得到粉末。  4) The mixed suspension obtained in the step 3) is spray-dried, and the solvent is removed to obtain a powder.
5)将步骤 4)中所得的粉末置于惰性气体氛围下， 对其进行预热处理， 再将粉末冷却至 室温，接着于还原气氛下进行还原反应，还原完毕后，在还原气氛下冷却至室温， 清洗并干燥， 最终制得负载有碳纳米颗粒的石墨烯复合材料。  5) The powder obtained in the step 4) is placed under an inert gas atmosphere, preheated, and then cooled to room temperature, followed by reduction in a reducing atmosphere, and after reduction, cooling to a reducing atmosphere At room temperature, it is washed and dried to finally produce a graphene composite loaded with carbon nanoparticles.
在上述实施方案中， 步骤 1)-4)的条件和操作如上文所定义。  In the above embodiment, the conditions and operations of steps 1) to 4) are as defined above.
在上述实施方案中， 预热处理的温度通常为 300-500°C， 优选为 320-400°C， 最优 选为 350-400°C ; 预热处理的时间通常为 1-12小时， 优选为 2-4小时。 惰性气氛所用的 惰性气体为氩气、 氮气、 氦气或氖气。 预热处理之后， 将所得粉末随炉冷却至室温， 然后在还原性气氛下进行还原处理。 还原处理的温度为 600-1200 °C， 优选为 600-800 °C ; 还原处理的时间通常为 1-10小时， 优选为 2-4小时。 本发明的预热处理和 还原处理通常在管式炉中进行， 其可在同一管式炉或不同管式炉中进行， 但优选在 同一管式炉中先后进行。 具体的管式炉是本领域技术人员所熟知的。  In the above embodiment, the preheat treatment temperature is usually 300 to 500 ° C, preferably 320 to 400 ° C, and most preferably 350 to 400 ° C; the preheat treatment time is usually 1 to 12 hours, preferably 2-4 hours. The inert gas used in the inert atmosphere is argon, nitrogen, helium or neon. After the preliminary heat treatment, the obtained powder was cooled to room temperature with a furnace, and then subjected to a reduction treatment under a reducing atmosphere. The reduction treatment is carried out at a temperature of from 600 to 1200 ° C, preferably from 600 to 800 ° C; and the reduction treatment is usually carried out for from 1 to 10 hours, preferably from 2 to 4 hours. The preheating and reduction treatments of the present invention are generally carried out in a tube furnace, which may be carried out in the same tube furnace or in a different tube furnace, but preferably in the same tube furnace. Specific tube furnaces are well known to those skilled in the art.
具体地， 本发明涉及如下实施方案， 其中将干燥后所得的粉末放入通有惰性气 体的管式炉中以 10°C/m i緩慢升温至 300-500°C加热 l-12h， 再将粉末随炉冷却至室 温； 接着向管式炉中通入还原气体 (如： 氢气， 或者体积比为 1:100-30:100)的氢气与 惰性气体的混合气体， 其中惰性气体为氩气、 氮气、 氦气或氖气) 5-10m i， 控制还原 气体的流量为 60mL/min， 将管式炉中的空气排出， 形成还原气氛， 然后将温度升至 600-1200°C , 在此温度下保持加热 l-10h， 还原完毕后， 在还原气氛下冷却至室温， 并用蒸馏水和无水乙醇反复清洗以除去残留的表面活性剂及其经高温转化后所得残 余物 (例如无机盐)， 最终制得负载有碳纳米颗粒的石墨烯复合材料。  Specifically, the present invention relates to an embodiment in which the powder obtained after drying is placed in a tube furnace with an inert gas and slowly heated to a temperature of 300 to 500 ° C for 10 to 12 hours at 10 ° C / mi, and then the powder is further Cooling to room temperature with the furnace; then introducing a mixed gas of hydrogen and an inert gas into the tubular furnace (for example, hydrogen, or a volume ratio of 1:100-30:100), wherein the inert gas is argon gas, nitrogen gas , helium or helium) 5-10m i, control the flow rate of reducing gas to 60mL / min, the air in the tube furnace is discharged to form a reducing atmosphere, and then the temperature is raised to 600-1200 ° C, at this temperature Keep heating for l-10h, after the reduction is completed, cool to room temperature under reducing atmosphere, and repeatedly wash with distilled water and absolute ethanol to remove residual surfactant and its residue after high temperature conversion (such as inorganic salt), the final system A graphene composite loaded with carbon nanoparticles.
本发明的碳纳米颗粒的石墨烯复合材料可用作超级电容器材料、 催化剂载体或 红外光学材料。 The carbon nanoparticle graphene composite of the present invention can be used as a supercapacitor material, a catalyst carrier or Infrared optical material.
本发明具有如下有益效果：  The invention has the following beneficial effects:
(1)在由本发明方法制备的复合材料中， 由于纳米碳颗粒能够很好的分散在石墨 烯的片层之间， 能发挥协同效应； 在通过该方法制备出的复合材料中， 二者的复合 不仅防止石墨烯片的片间团聚， 而且防止碳颗粒之间的团聚， 有效提高了复合材料 的比表面积， 从而提高了其电容性能； 同时石墨烯片与碳纳米颗粒的导电率都较高， 使得所得的复合材料也具有较高的导电性；  (1) In the composite material prepared by the method of the present invention, since the nano carbon particles can be well dispersed between the sheets of graphene, a synergistic effect can be exerted; in the composite material prepared by the method, both of them The composite not only prevents the agglomeration of the graphene sheets, but also prevents the agglomeration between the carbon particles, effectively increasing the specific surface area of the composite, thereby improving the capacitance performance thereof; and the conductivity of the graphene sheets and the carbon nanoparticles are high. , the resulting composite material also has a higher conductivity;
(2)该方法制备的复合材料具有较高的比表面积， 在超级电容器领域具有广泛的 应用前景；  (2) The composite material prepared by the method has a high specific surface area and has wide application prospects in the field of supercapacitors;
(3)碳纳米颗粒成本低廉， 来源广泛， 便于复合材料的大规模化生产。 附图说明  (3) Carbon nanoparticles are low in cost and widely available, facilitating large-scale production of composite materials. DRAWINGS
图 1为实施例 1中的喷雾干燥获得的颗粒。  Figure 1 is a particle obtained by spray drying in Example 1.
图 2为实施例 1制备的超级电容器的充放电曲线。 具体实施方式  Fig. 2 is a graph showing the charge and discharge curves of the supercapacitor prepared in Example 1. detailed description
本发明提供的是一种石墨烯 /纳米碳颗粒复合材料及其制备方法， 先通过将天然 鳞片石墨氧化成氧化石墨烯， 表面活性剂溶解纳米颗粒形成悬浮液， 混合获得氧化 石墨烯纳米碳颗粒的悬浮液， 在室温下搅拌， 混合均匀后， 将混合悬浮液喷雾干燥， 除去溶剂后得到粉末， 将粉末放入通有惰性气体保护的管式炉中加热还原。  The invention provides a graphene/nano carbon particle composite material and a preparation method thereof, firstly, the natural flake graphite is oxidized into graphene oxide, the surfactant dissolves the nano particles to form a suspension, and the graphene oxide nano carbon particles are obtained by mixing. The suspension is stirred at room temperature, and after mixing uniformly, the mixed suspension is spray-dried, the solvent is removed to obtain a powder, and the powder is placed in a tube furnace protected by an inert gas to be heated and reduced.
本发明提供一种负载有碳纳米颗粒的石墨烯复合材料的制备工艺流程如下： 天然鳞片石墨→氧化石墨烯→氧化石墨烯悬浮液→碳纳米颗粒与石墨烯混合悬 浮液→石墨烯 /纳米碳颗粒复合材料。  The invention provides a process for preparing a graphene composite material loaded with carbon nanoparticles as follows: natural flake graphite→ graphene oxide→ graphene oxide suspension→ carbon nanoparticle and graphene mixed suspension→ graphene/nanocarbon Granular composites.
具体地， 本发明涉及如下方面：  Specifically, the present invention relates to the following aspects:
1. 一种石墨烯 /纳米碳颗粒复合材料的制备方法， 其特征在于， 包括如下步骤： A method for preparing a graphene/nano carbon particle composite material, comprising the steps of:
1)将石墨氧化以制备氧化石墨烯， 将所得氧化石墨烯添加至水中制得悬浮液；1) oxidizing graphite to prepare graphene oxide, adding the obtained graphene oxide to water to prepare a suspension;
2)将纳米碳颗粒添加至表面活性剂的水溶液中以获得纳米碳颗粒的悬浮液；2) adding nano carbon particles to an aqueous solution of a surfactant to obtain a suspension of nano carbon particles;
3)将所述氧化石墨烯悬浮液与纳米碳颗粒悬浮液混合， 得到氧化石墨烯 /纳米碳 颗粒的均匀混合悬浮液； 4)将步骤 3)中所得的均匀混合悬浮液喷雾干燥， 得到粉末； 3) mixing the graphene oxide suspension with the nano carbon particle suspension to obtain a uniform mixed suspension of graphene oxide/nano carbon particles; 4) spray-drying the homogeneous mixed suspension obtained in the step 3) to obtain a powder;
5)对步骤 4)中所得的粉末进行如下处理：  5) The powder obtained in the step 4) is treated as follows:
a)在还原气氛下进行还原处理， 还原完毕后， 在还原气氛下冷却至室温， 清洗 并干燥， 最终制得负载有碳纳米颗粒的石墨烯复合材料； 或者  a) performing a reduction treatment under a reducing atmosphere, after the reduction is completed, cooling to room temperature under a reducing atmosphere, washing and drying to finally obtain a graphene composite material loaded with carbon nanoparticles; or
b)将步骤 4)中所得的粉末置于惰性气体氛围下， 对其进行预热处理， 再将粉末 冷却至室温； 接着于还原气氛下进行还原反应， 还原完毕后， 在还原气氛下冷却至 室温， 清洗并干燥， 最终制得负载有碳纳米颗粒的石墨烯复合材料。  b) The powder obtained in the step 4) is placed under an inert gas atmosphere, preheated, and then cooled to room temperature; then the reduction reaction is carried out under a reducing atmosphere, and after the reduction is completed, it is cooled to a reducing atmosphere. At room temperature, it is washed and dried to finally produce a graphene composite loaded with carbon nanoparticles.
2.根据 1的方法， 其中所述纳米碳颗粒选自碳 60、 碳黑、 乙块黑、 科琴黑、 碳纳 米管、 碳纳米纤维或其组合。  2. The method according to 1, wherein the nanocarbon particles are selected from the group consisting of carbon 60, carbon black, aceton black, ketjen black, carbon nanotubes, carbon nanofibers, or a combination thereof.
3.根据 1或 2的方法， 其中所述纳米碳颗粒的尺寸为 2-100nm， 优选为 10-80nm， 更优选为 20-60nm， 最优选为 20-50nm。  3. The method according to 1 or 2, wherein the nanocarbon particles have a size of from 2 to 100 nm, preferably from 10 to 80 nm, more preferably from 20 to 60 nm, and most preferably from 20 to 50 nm.
4. 根据 1-3中任一项所述的方法， 其特征在于， 所述石墨烯 /纳米碳颗粒复合材 料中的纳米碳颗粒的用量为 1-50%， 优选为 1-20%， 最优选为 5-15%， 基于氧化石墨 烯的质量。  4. The method according to any one of claims 1 to 3, wherein the nano carbon particles in the graphene/carbon nanoparticle composite material are used in an amount of 1 to 50%, preferably 1 to 20%, most It is preferably 5-15% based on the mass of graphene oxide.
5.根据 1-4中任一项所述的方法，其特征在于，步骤 4)的喷雾干燥采用离心喷雾， 超声喷雾、 气流喷雾或者压力喷雾技术或其组合。  The method of any of 1-4, wherein the spray drying of step 4) employs a centrifugal spray, an ultrasonic spray, a gas spray or a pressure spray technique, or a combination thereof.
6.根据 5的方法， 喷雾干燥采用压力喷雾技术进行， 其中喷雾压力为 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。  6. According to the method of 5, the spray drying is carried out by a pressure spray technique, wherein 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.
7.根据 5的方法， 其特征在于， 其中喷雾干燥采用离心喷雾技术进行， 其中离心 速度为 50-10000转 /分钟， 优选 2000-5000转 /分钟。  7. The method according to 5, characterized in that the spray drying is carried out by a centrifugal spray technique, wherein the centrifugal speed is from 50 to 10,000 rpm, preferably from 2,000 to 5,000 rpm.
8.根据 1-7中任一项的方法， 其特征在于， 其中还原气氛为氢气， 或者氢气与惰 性气体的混合气体。  The method according to any one of 1 to 7, wherein the reducing atmosphere is hydrogen or a mixed gas of hydrogen and an inert gas.
9.根据 1-8中任一项的方法， 其特征在于， 其中步骤 5)的 a)和 b)中还原处理的时 间为 1-10小时， 优选为 2-4小时。  The method according to any one of 1-8, wherein the reduction treatment in a) and b) of step 5) is from 1 to 10 hours, preferably from 2 to 4 hours.
10.根据 1-9中任一项的方法， 其特征在于， 其中步骤 5)的 a)和 b)中的还原温度为 600-1200°C , 优选为 600-800°C。  10. Process according to any one of 1 to 9, characterized in that the reduction temperature in a) and b) of step 5) is from 600 to 1200 ° C, preferably from 600 to 800 ° C.
11. 根据 1-10中任一项的方法， 其中在步骤 5)的 b)中， 预热处理的温度为 300-500 °C ,优选为 320-400°C， 最优选为 350°C ; 预热处理的时间为 1-12小时，优选为 2-4小时。 11. The method according to any one of 1 to 10, wherein in the step b), the preheating temperature is 300-500 ° C, preferably 320-400 ° C, most preferably 350 ° C; The preheat treatment time is 1-12 hours, preferably 2-4 hours.
12.根据 1-11中任一项的方法获得的石墨烯 /纳米碳颗粒复合材料。  12. A graphene/nanocarbon particle composite obtained by the method of any of 1-11.
13.根据 1-11中任一项的方法获得的石墨烯 /纳米碳颗粒复合材料或权利要求 12 的石墨烯 /纳米碳颗粒复合材料作为超级电容器材料、 催化剂载体或红外光学材料的 用途。  13. Use of a graphene/nanocarbon particle composite obtained by the method of any of 1 to 11 or a graphene/carbon nanoparticle composite of claim 12 as a supercapacitor material, a catalyst carrier or an infrared optical material.
下面通过实施例进一步详细阐述本发明的制备工艺， 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。 实施例 1  The preparation process of the present invention is further illustrated by the following examples, and the embodiments of the present invention are not intended to limit the scope of the present invention. Any modifications and variations made on the basis of the present invention are within the scope of the present invention. Example 1
(1)氧化石墨烯悬浮液的制备：通过氧化还原法 (hummers改进法)获得氧化石墨烯 (参见 JACS, 1958， 80, 1339): 其具体步骤为将 20g的 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高锰酸鉀， 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， 将其添加至去离子水中， 搅拌， 制得悬浮液。  (1) Preparation of Graphene Oxide Suspension: Graphene oxide was obtained by a redox method (Hummers improvement method) (see JACS, 1958, 80, 1339): The specific procedure is 20 g of 50 mesh graphite powder, 10 g of persulfuric acid The bell and 10 g of phosphorus pentoxide were added to concentrated sulfuric acid at 80 ° C, stirred uniformly, cooled for 6 h, washed until neutral, 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. After drying under vacuum at 60 ° C for 48 hours, graphene oxide was obtained, which was added to deionized water and stirred to obtain a suspension.
(2)纳米碳颗粒悬浮液的制备：将 10g乙炔黑 (粒度约 30nm)与 lg表面活性剂十二烷 基磺酸钠一起添加至 500mL去离子水中，超声功率为 100w^L30min,从而获得乙炔 黑的均匀悬浮液。  (2) Preparation of nano carbon particle suspension: 10 g of acetylene black (particle size about 30 nm) was added to 500 mL of deionized water together with lg surfactant sodium dodecyl sulfate, and the ultrasonic power was 100 w L 30 min, thereby obtaining acetylene. A black homogeneous suspension.
(3)混合悬浮液的制备： 将所述氧化石墨烯悬浮液与纳米碳颗粒悬浮液混合， 在 室温下搅拌 lh， 得到均匀分散的混合悬浮液； 其中所述乙炔黑与氧化石墨烯的质量 比为 1 ： 100;  (3) Preparation of the mixed suspension: mixing the graphene oxide suspension with the nano carbon particle suspension, and stirring at room temperature for 1 hour to obtain a uniformly dispersed mixed suspension; wherein the quality of the acetylene black and graphene oxide Ratio is 1: 100;
(4)通过喷雾干燥制备乙块黑颗粒与石墨烯混合物： 在 4MPa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， 获得干燥的粉末。 喷雾干燥颗粒的 SEM示于图 1中。 由图 1可以看出， 形成了夹杂在石墨烯片之间的纳米尺度的球形颗粒。  (4) Preparation of a mixture of black granules and graphene by spray drying: at a spray pressure of 4 MPa, an inlet air temperature of 120 ° C, and an outlet temperature of 80 ° C, by means of a spray dryer (model SY-600, Shanghai) Shiyuan Biological Co., Ltd.) spray-dried the suspension to obtain a dry powder. The SEM of the spray dried granules is shown in Figure 1. As can be seen from Fig. 1, nano-scale spherical particles interposed between the graphene sheets are formed.
(5)通过气氛还原制备石墨烯 /乙炔黑复合材料： 将 2g得到的粉末放入通有惰性气 体的管式炉中以 10°C/min緩慢升温至 500°C， 保持此温度 5h, 再将粉末随炉冷却至室 温。 然后向管式炉中通入氢气 5min, 控制氢气流量为 60mL/min， 将管式炉中的气氛 排出， 然后将温度升至 800°C， 在此温度下保持加热 6h， 还原完毕后， 在氢气气氛下 冷却至室温， 并用蒸馏水和无水乙醇反复清洗以除去表面活性剂及其残留物， 最终 制得石墨烯 /纳米碳颗粒复合材料。 (5) Preparation of graphene/acetylene black composite by atmosphere reduction: 2 g of the obtained powder was placed in an inert gas The tube furnace was slowly heated to 500 ° C at 10 ° C / min, maintained at this temperature for 5 h, and the powder was cooled to room temperature with the furnace. Then, hydrogen gas was introduced into the tube furnace for 5 min, the hydrogen flow rate was controlled to 60 mL/min, the atmosphere in the tube furnace was discharged, and then the temperature was raised to 800 ° C, and the temperature was kept at this temperature for 6 h. After the reduction was completed, The mixture was cooled to room temperature under a hydrogen atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the surfactant and its residue, and finally a graphene/carbon nanoparticle composite material was obtained.
(6)由石墨烯 /乙炔黑复合材料制备超级电容器： 将根据上述方法制备的复合材料 作为正极材料， 按照质量比为 85： 5： 10的比例， 将所述负载有碳纳米颗粒的石墨烯 复合材料、 聚偏氟乙烯粘结剂和导电剂乙炔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、 轧膜、 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 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  (6) Preparation of supercapacitor from graphene/acetylene black composite material: The composite material prepared according to the above method is used as a positive electrode material, and the carbon nanoparticle-loaded graphene is loaded at a mass ratio of 85:5:10. The composite material, the polyvinylidene fluoride binder and the conductive agent acetylene black were uniformly mixed to obtain a slurry. Subsequently, the slurry blade was applied to an aluminum foil, dried, rolled, and trimmed to obtain a supercapacitor 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. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1. Example 2
(1)氧化石墨烯悬浮液的制备： 以与实施例 1相同的方式制备氧化石墨烯悬浮液。  (1) Preparation of graphene oxide suspension: A graphene oxide suspension was prepared in the same manner as in Example 1.
(2)纳米碳颗粒悬浮液的制备： 将 10g科琴黑 ECP600JD (瑞士，特密高 ECP600JD, 粒度 20nm)与 5g表面活性剂十二烷基四乙基季铵盐一起添加至 500mL去离子水中，超 声功率为 lOOw分散 30min, 从而获得科琴黑 ECP600JD的均匀悬浮液。  (2) Preparation of nano carbon particle suspension: 10 g of Ketjen black ECP600JD (Switzerland, Temco ECP600JD, particle size 20 nm) was added to 500 mL of deionized water together with 5 g of surfactant dodecyltetraethyl quaternary ammonium salt. The ultrasonic power was dispersed for 100 min for 30 min, thereby obtaining a uniform suspension of Ketchen Black ECP600JD.
(3)混合悬浮液的制备：将所述氧化石墨烯悬浮液与科琴黑 ECP600JD的悬浮液混 合， 在室温下搅拌 10h， 得到均匀分散的混合悬浮液； 其中所述科琴黑 ECP600JD与 氧化石墨烯的质量比为 1: 20;  (3) Preparation of mixed suspension: mixing the graphene oxide suspension with a suspension of Ketchen Black ECP600JD, and stirring at room temperature for 10 hours to obtain a uniformly dispersed mixed suspension; wherein the Ketjen black ECP600JD and oxidation The mass ratio of graphene is 1:20;
(4)通过喷雾干燥制备科琴黑 ECP600JD颗粒与石墨烯混合物： 在 6MPa的喷雾压 力， 200°C的进风温度， 120°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， 获得干燥的粉末。  (4) Preparation of Ketchen Black ECP600JD particles and graphene mixture by spray drying: at a spray pressure of 6 MPa, an inlet air temperature of 200 ° C, and an outlet temperature of 120 ° C, by means of a spray dryer (model SY-600, Shanghai Shiyuan Biological Co., Ltd. spray-dried the suspension to obtain a dry powder.
(5)通过气氛还原制备石墨烯 /科琴黑 ECP600JD复合材料： 将 2g得到的粉末放入 通有惰性气体的管式炉中以 10°C/m i緩慢升温至 300°C， 保持此温度 5h, 再将粉末随 炉冷却至室温。 然后向管式炉中通入氢气 5min, 控制氢气流量为 60mL/min， 将管式 炉中的空气排出， 然后将温度升至 600°C， 在此温度下保持加热 6h， 还原完毕后， 在 氢气气氛下冷却至室温， 并用蒸餾水和无水乙醇反复清洗以除去表面活性剂及其残 留物， 最终制得石墨烯 /纳米碳颗粒复合材料。 (5) Preparation of graphene/Ketjen black ECP600JD composite by atmosphere reduction: 2 g of the obtained powder was placed in a tube furnace with an inert gas and slowly heated to 300 ° C at 10 ° C / mi, maintaining this temperature for 5 h. Then, the powder was cooled to room temperature with the furnace. Then, hydrogen gas was introduced into the tube furnace for 5 minutes, the hydrogen flow rate was controlled to 60 mL/min, the air in the tube furnace was discharged, and then the temperature was raised to 600 ° C, and the temperature was kept at this temperature for 6 hours. After the reduction was completed, The mixture was cooled to room temperature under a hydrogen atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the surfactant and its residue, and finally a graphene/carbon nanoparticle composite material was obtained.
(6)由石墨烯 /科琴黑 ECP600JD复合材料制备超级电容器： 将根据上述方法制备 的复合材料作为正极材料， 按照质量比为 85： 5： 10的比例， 将所述负载有碳纳米颗 粒的石墨烯复合材料、 聚偏氟乙烯粘结剂和导电剂乙炔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、 轧膜、 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 3  (6) Preparation of supercapacitor from graphene/Ketjen black ECP600JD composite material: The composite material prepared according to the above method is used as a positive electrode material, and the carbon nanoparticle is loaded at a mass ratio of 85:5:10. The graphene composite material, the polyvinylidene fluoride binder, and the conductive agent acetylene black were uniformly mixed to obtain a slurry. Subsequently, the slurry blade was applied to an aluminum foil, dried, rolled, and trimmed to obtain a supercapacitor 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 capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1. Example 3
(1)氧化石墨烯悬浮液的制备： 以与实施例 1相同的方式制备氧化石墨烯悬浮液。  (1) Preparation of graphene oxide suspension: A graphene oxide suspension was prepared in the same manner as in Example 1.
(2)纳米碳颗粒悬浮液的制备： 将 10g碳 60与 2g表面活性剂十二烷基氨基酸一起添 加至 500mL去离子水中， 超声功率为 100w^L30min， 从而获得碳 60的均匀悬浮液。  (2) Preparation of nano carbon particle suspension: 10 g of carbon 60 was added together with 2 g of surfactant dodecyl amino acid to 500 mL of deionized water at an ultrasonic power of 100 W L 30 min to obtain a uniform suspension of carbon 60.
(3)混合悬浮液的制备： 将所述氧化石墨烯悬浮液与碳 60悬浮液混合， 在室温下 搅拌 5h， 得到均匀分散的混合悬浮液； 其中所述碳 60与氧化石墨烯的质量比为 1： 1;  (3) Preparation of mixed suspension: mixing the graphene oxide suspension with a carbon 60 suspension, and stirring at room temperature for 5 hours to obtain a uniformly dispersed mixed suspension; wherein the mass ratio of the carbon 60 to graphene oxide Is 1:1;
(4)通过喷雾干燥制备碳 60颗粒与石墨烯混合物： 在 4MPa的喷雾压力， 150°C的 进风温度， 100°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， 获得干燥的粉末。  (4) Preparation of a mixture of carbon 60 particles and graphene by spray drying: at a spray pressure of 4 MPa, an inlet air temperature of 150 ° C, and an outlet air temperature of 100 ° C, by means of a spray dryer (model SY-600, Shanghai World) Far Bio Co., Ltd.) spray-suspension the suspension to obtain a dry powder.
(5)通过气氛还原制备石墨烯 /碳 60复合材料： 将 2g得到的粉末放入通有惰性气体 的管式炉中以 10°C/m i緩慢升温至 350°C ,保持此温度 5h，再将粉末随炉冷却至室温。 然后向管式炉中通入氢气 5min，控制氢气流量为 60mL/min，将管式炉中的空气排出， 然后将温度升至 1000 °C， 在此温度下保持加热 6h， 还原完毕后， 在氢气气氛下冷却 至室温， 并用蒸馏水和无水乙醇反复清洗以除去表面活性剂及其残留物， 最终制得 石墨婦 /纳米碳颗粒复合材料。  (5) Preparation of graphene/carbon 60 composite by atmosphere reduction: 2 g of the obtained powder was placed in a tube furnace with an inert gas and slowly heated to 350 ° C at 10 ° C / mi, maintaining this temperature for 5 h, and then The powder was cooled to room temperature with the oven. Then, hydrogen gas was introduced into the tube furnace for 5 minutes, the hydrogen flow rate was controlled to 60 mL/min, the air in the tube furnace was discharged, and then the temperature was raised to 1000 ° C, and the temperature was kept at this temperature for 6 hours. After the reduction was completed, The mixture was cooled to room temperature under a hydrogen atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the surfactant and its residue, thereby finally obtaining a graphite/nano carbon particle composite.
(6)由石墨烯 /碳 60复合材料制备超级电容器： 将根据上述方法制备的复合材料作 为正极材料， 按照质量比为 85： 5： 10的比例， 将所述负载有碳纳米颗粒的石墨烯复 合材料、 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 4 (6) Preparation of supercapacitor from graphene/carbon 60 composite material: The composite material prepared according to the above method is used as a positive electrode material, and the carbon nanoparticle-loaded graphene is loaded at a mass ratio of 85:5:10. The composite material, the polyvinylidene fluoride binder, and the conductive agent b black were uniformly mixed to obtain a slurry. Subsequently, the pulp will be The scraper is coated on an aluminum foil, dried, rolled, and trimmed to produce a supercapacitor 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. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1. Example 4
(1)氧化石墨烯悬浮液的制备： 以与实施例 1相同的方式制备氧化石墨烯悬浮液。  (1) Preparation of graphene oxide suspension: A graphene oxide suspension was prepared in the same manner as in Example 1.
(2)纳米碳颗粒悬浮液的制备： 将 10g碳纳米管 (深圳， 德方纳米、 长： 5-20um， 直径： 小于 3nm)与 4g表面活性剂聚氧乙烯一起添加至 500mL去离子水中， 超声功率 为 lOOw分散 30min， 从而获得碳纳米管的均匀悬浮液。  (2) Preparation of nano carbon particle suspension: 10 g of carbon nanotubes (Shenzhen, Defang nanometer, length: 5-20 um, diameter: less than 3 nm) was added to 500 mL of deionized water together with 4 g of surfactant polyoxyethylene. The ultrasonic power was dispersed for 100 min for 30 min, thereby obtaining a uniform suspension of carbon nanotubes.
(3)混合悬浮液的制备： 将所述氧化石墨烯悬浮液与碳纳米管混合， 在室温下搅 拌 4h， 得到均匀分散的混合悬浮液； 其中所述碳纳米管与氧化石墨烯的质量比为 1: 10;  (3) Preparation of mixed suspension: mixing the graphene oxide suspension with carbon nanotubes and stirring at room temperature for 4 hours to obtain a uniformly dispersed mixed suspension; wherein the mass ratio of the carbon nanotubes to graphene oxide Is 1: 10;
(4)通过喷雾干燥制备碳纳米管颗粒与石墨烯混合物：在 4MPa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， 获得干燥的粉末。  (4) Preparation of a mixture of carbon nanotube particles and graphene by spray drying: at a spray pressure of 4 MPa, an inlet air temperature of 120 ° C, and an outlet temperature of 80 ° C, by means of a spray dryer (Model SY-600, Shanghai) Shiyuan Biological Co., Ltd.) spray-dried the suspension to obtain a dry powder.
(5)通过气氛还原制备石墨烯 /碳纳米管复合材料： 将 2g得到的粉末放入通有惰性 气体的管式炉中以 10°C/m i緩慢升温至 400°C， 保持此温度 5h, 再将粉末随炉冷却至 室温。 然后向管式炉中通入氢气 5min， 控制氢气流量为 60mL/min， 将管式炉中的空 气排出， 然后将温度升至 900°C， 在此温度下保持加热 6h， 还原完毕后， 在氢气气氛 下冷却至室温， 并用蒸餾水和无水乙醇反复清洗以除去表面活性剂及其残留物， 最 终制得石墨烯 /纳米碳颗粒复合材料。  (5) Preparation of graphene/carbon nanotube composite material by atmosphere reduction: 2 g of the obtained powder was placed in a tube furnace with an inert gas, and the temperature was slowly raised to 400 ° C at 10 ° C/mi, and the temperature was maintained at 5 h. The powder was then cooled to room temperature with the furnace. Then, hydrogen gas was introduced into the tube furnace for 5 minutes, the hydrogen flow rate was controlled to 60 mL/min, the air in the tube furnace was discharged, and then the temperature was raised to 900 ° C, and the temperature was kept at this temperature for 6 hours. After the reduction was completed, The mixture was cooled to room temperature under a hydrogen atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the surfactant and its residue, and finally a graphene/carbon nanoparticle composite material was obtained.
(6)由石墨烯 /碳纳米管复合材料制备超级电容器： 将根据上述方法制备的复合材 料作为正极材料， 按照质量比为 85： 5： 10的比例， 将所述负载有碳纳米颗粒的石墨 烯复合材料、 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、 轧膜、 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 5: (6) Preparation of supercapacitor from graphene/carbon nanotube composite material: The composite material prepared according to the above method is used as a positive electrode material, and the carbon nanoparticle-loaded graphite is loaded at a mass ratio of 85:5:10. The olefin composite material, the polyvinylidene fluoride binder, and the conductive agent b black are uniformly mixed to obtain a slurry. Subsequently, the slurry blade was applied to an aluminum foil, dried, rolled, and trimmed to obtain a supercapacitor 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, Seal the injection port to get a supercapacitor. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1. Example 5:
(1)氧化石墨烯悬浮液的制备： 以与实施例 1相同的方式制备氧化石墨烯悬浮液。  (1) Preparation of graphene oxide suspension: A graphene oxide suspension was prepared in the same manner as in Example 1.
(2)纳米碳颗粒悬浮液的制备： 将 10g碳纳米纤维（日本东洋纺， 直径： 5-20nm)与 lg表面活性剂十二烷基三乙基硅一起添加至 500mL去离子水中， 超声功率为 lOOw分 散 30min从而获得乙炔黑的均匀悬浮液。  (2) Preparation of nano carbon particle suspension: 10 g of carbon nanofiber (Japan Toyobo, diameter: 5-20 nm) was added to 500 mL of deionized water together with lg surfactant dodecyltriethylsilane, ultrasonic power Disperse for 100 min for lOOw to obtain a homogeneous suspension of acetylene black.
(3)混合悬浮液的制备： 将所述氧化石墨烯悬浮液与碳纳米纤维混合， 在室温下 搅拌 10h， 得到均匀分散的混合悬浮液； 其中所述乙炔黑与氧化石墨烯的质量比为 1: 20；  (3) Preparation of mixed suspension: mixing the graphene oxide suspension with carbon nanofibers and stirring at room temperature for 10 hours to obtain a uniformly dispersed mixed suspension; wherein the mass ratio of the acetylene black to the graphene oxide is 1: 20;
(4)通过喷雾干燥制备碳纳米纤维颗粒与石墨烯混合物： 在 4MPa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， 获得干燥的粉末。  (4) Preparation of a mixture of carbon nanofiber particles and graphene by spray drying: at a spray pressure of 4 MPa, an inlet air temperature of 120 ° C, and an outlet temperature of 80 ° C, by means of a spray dryer (Model SY-600, Shanghai) Shiyuan Biological Co., Ltd.) spray-dried the suspension to obtain a dry powder.
(5)通过气氛还原制备石墨烯 /碳纳米纤维复合材料： 将 2g得到的粉末放入通有惰 性气体的管式炉中以 10°C/m i緩慢升温至 450°C， 保持此温度 5h， 再将粉末随炉冷却 至室温。 然后向管式炉中通入氢气 5min， 控制氢气流量为 60mL/min， 将管式炉中的 空气排出， 然后将温度升至 800°C， 在此温度下保持加热 6h， 还原完毕后， 在氢气气 氛下冷却至室温， 并用蒸馏水和无水乙醇反复清洗以除去表面活性剂及其残留物， 最终制得石墨烯 /纳米碳颗粒复合材料。  (5) Preparation of graphene/carbon nanofiber composite by atmosphere reduction: 2 g of the obtained powder was placed in a tube furnace with an inert gas, and the temperature was slowly raised to 450 ° C at 10 ° C / mi, and the temperature was maintained for 5 h. The powder was then cooled to room temperature with the furnace. Then, hydrogen gas was introduced into the tube furnace for 5 minutes, the hydrogen flow rate was controlled to 60 mL/min, the air in the tube furnace was discharged, and then the temperature was raised to 800 ° C, and the temperature was kept at this temperature for 6 hours. After the reduction was completed, The mixture was cooled to room temperature under a hydrogen atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the surfactant and its residue, and finally a graphene/carbon nanoparticle composite material was obtained.
(6)由石墨烯 /碳纳米纤维复合材料制备超级电容器： 将根据上述方法制备的复合 材料作为正极材料， 按照质量比为 85： 5： 10的比例， 将所述负载有碳纳米颗粒的石 墨烯复合材料、 聚偏氟乙烯粘结剂和导电剂乙炔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、 轧膜、 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 6: (6) Preparation of supercapacitor from graphene/carbon nanofiber composite material: The composite material prepared according to the above method is used as a positive electrode material, and the carbon nanoparticle-loaded graphite is loaded at a mass ratio of 85:5:10. The olefin composite material, the polyvinylidene fluoride binder, and the conductive agent acetylene black are uniformly mixed to obtain a slurry. Subsequently, the slurry blade was applied to an aluminum foil, dried, rolled, and trimmed to obtain a supercapacitor 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. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1. Example 6
(1)氧化石墨烯悬浮液的制备： 以与实施例 1相同的方式制备氧化石墨烯悬浮液。  (1) Preparation of graphene oxide suspension: A graphene oxide suspension was prepared in the same manner as in Example 1.
(2)纳米碳颗粒悬浮液的制备： 将 10g科琴黑 ECP (瑞士、 特密 ECP)与 2g表面活性 剂（C2F5(OCF2CF(CF3))2OC2F4S03Na)—起添加至 500mL去离子水中， 超声功率为 100w^L30min, 从而获得科琴黑 ECP的均匀悬浮液。 (2) Preparation of nano carbon particle suspension: 10 g of Ketjen black ECP (Swiss, Tem ECP) and 2 g of surfactant (C 2 F 5 (OCF 2 CF(CF 3 )) 2 OC 2 F 4 S0 3 Na) - Addition to 500 mL of deionized water, ultrasonic power of 100 w ^ L 30 min, to obtain a uniform suspension of Ketchen Black ECP.
(3)混合悬浮液的制备： 将所述氧化石墨烯悬浮液与科琴黑 ECP混合， 在室温下 搅拌 8h， 得到均匀分散的混合悬浮液； 其中所述科琴黑 ECP与氧化石墨烯的质量比 为 1: 10；  (3) Preparation of mixed suspension: The graphene oxide suspension is mixed with Ketchen Black ECP and stirred at room temperature for 8 hours to obtain a uniformly dispersed mixed suspension; wherein the Ketjen black ECP and graphene oxide are The mass ratio is 1:10;
(4)通过喷雾干燥制备科琴黑 ECP颗粒与石墨烯混合物： 在 4MPa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， 获得干燥的粉末。  (4) Preparation of a mixture of Ketchen black ECP particles and graphene by spray drying: at a spray pressure of 4 MPa, an inlet air temperature of 120 ° C, and an outlet temperature of 80 ° C, by means of a spray dryer (model SY-600, Shanghai Shiyuan Biological Co., Ltd. spray-dried the suspension to obtain a dry powder.
(5)通过气氛还原制备石墨烯 /科琴黑 ECP复合材料： 将 2g得到的粉末放入通有惰 性气体的管式炉中以 10°C/m i緩慢升温至 500°C， 保持此温度 5h， 再将粉末随炉冷却 至室温。 然后向管式炉中通入氢气 5min， 控制氢气流量为 60mL/min， 将管式炉中的 空气排出， 然后将温度升至 700°C， 在此温度下保持加热 6h， 还原完毕后， 在氢气气 氛下冷却至室温， 并用蒸馏水和无水乙醇反复清洗以除去表面活性剂及其残留物， 最终制得石墨烯 /纳米碳颗粒复合材料。  (5) Preparation of graphene/Ketjen black ECP composite by atmosphere reduction: 2 g of the obtained powder was placed in a tube furnace with an inert gas and slowly heated to 500 ° C at 10 ° C / mi, maintaining this temperature for 5 h. Then, the powder was cooled to room temperature with the furnace. Then, hydrogen gas was introduced into the tube furnace for 5 minutes, the hydrogen flow rate was controlled to 60 mL/min, the air in the tube furnace was discharged, and then the temperature was raised to 700 ° C, and the temperature was kept at this temperature for 6 hours. After the reduction was completed, The mixture was cooled to room temperature under a hydrogen atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the surfactant and its residue, and finally a graphene/carbon nanoparticle composite material was obtained.
(6)由石墨烯 /科琴黑 ECP复合材料制备超级电容器： 将根据上述方法制备的复合 材料作为正极材料， 按照质量比为 85： 5： 10的比例， 将所述负载有碳纳米颗粒的石 墨烯复合材料、 聚偏氟乙烯粘结剂和导电剂乙炔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、 轧膜、 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。 所得电容器的容量、 耐压性、 倍率性能和寿命汇总于表 1中。 对比实施例 1  (6) Preparation of supercapacitor from graphene/Ketjen black ECP composite material: The composite material prepared according to the above method is used as a positive electrode material, and the carbon nanoparticle is loaded at a mass ratio of 85:5:10. The graphene composite material, the polyvinylidene fluoride binder, and the conductive agent acetylene black were uniformly mixed to obtain a slurry. Subsequently, the slurry blade was applied to an aluminum foil, dried, rolled, and trimmed to obtain a supercapacitor 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. Test its electrochemical performance such as charge and discharge, cyclic voltammetry, and lifetime. The capacity, pressure resistance, rate performance and life of the obtained capacitor are summarized in Table 1. Comparative Example 1
类似于实施例 6的程序制备石墨烯 /纳米碳颗粒复合材料， 并按照实施例 6步骤 (6) 的程序制备超级电容器， 测定其容量、 耐压性、倍率性能和寿命， 结果汇总于表 1中。 与实施例 6的不同之处在于， 在喷雾干燥时， 采用 3MPa的喷雾压力， 200°C的进风温 度， 90°C的出风温度。 实施例 7 A graphene/nanocarbon particle composite was prepared similarly to the procedure of Example 6, and a supercapacitor was prepared according to the procedure of Example 6 (6), and its capacity, pressure resistance, rate performance and life were measured. The results are summarized in Table 1. in. The difference from Example 6 was that, at the time of spray drying, a spray pressure of 3 MPa, an inlet air temperature of 200 ° C, and an outlet air temperature of 90 ° C were employed. Example 7
类似于实施例 6的程序制备石墨烯 /纳米碳颗粒复合材料， 并按照实施例 1步骤 (6) 的程序制备超级电容器， 测定其容量、 耐压性、倍率性能和寿命， 结果汇总于表 1中。 与实施例 1的不同之处在于，在喷雾干燥后，将 2g得到的粉末^通有体积比为 20:100 氢气与惰性气体的管式炉中以 10°C/m i緩慢升温至 800°C， 保持此温度 5h, 还原完毕 后， 在氢气气氛下冷却至室温， 并用蒸馏水和无水乙醇反复清洗以除去表面活性剂 及其残留物， 终制得石墨烯 /纳米碳颗粒复合材料。  A graphene/nanocarbon particle composite was prepared in a manner similar to that of Example 6, and a supercapacitor was prepared according to the procedure of the procedure (6) of Example 1, and the capacity, pressure resistance, rate performance and life were measured. The results are summarized in Table 1. in. The difference from Example 1 is that after spray drying, 2 g of the obtained powder is slowly heated to 800 ° C at 10 ° C / mi in a tube furnace having a volume ratio of 20:100 hydrogen and an inert gas. After maintaining the temperature for 5 h, after the reduction, the mixture was cooled to room temperature under a hydrogen atmosphere, and repeatedly washed with distilled water and absolute ethanol to remove the surfactant and its residue, and finally a graphene/carbon nanoparticle composite material was obtained.
Figure imgf000015_0001
Figure imgf000015_0001
1的数据可以看出，通过本发明制备的石墨烯 /纳米碳颗粒复合材料均具有较 好的电性能。 首先， 由实施例 1-6与对比实施例 1的对比可以看出， 采用处于本发明范 围之内的干燥条件获得的实施例 1-6的石墨烯 /纳米碳颗粒复合材料的电性能优于对 比实施例 1的电性能。其次， 由使用预热处理和还原处理相结合的实施例 1-6与单独采 用还原处理的实施例 7的纳米复合材料的电性能可以看出， 使用预热处理和还原处理 获得的石墨烯 /纳米碳颗粒复合材料的电性能均高于单独采用还原处理获得的石墨烯 /纳米碳颗粒复合材料的电性能。 由此可见， 与单独采用还原处理相比， 采用预热处 理和还原处理能进一步提高石墨烯 /纳米碳颗粒复合材料的电性能。  As can be seen from the data of 1, the graphene/nanocarbon particle composite prepared by the present invention has better electrical properties. First, it can be seen from the comparison of Examples 1-6 with Comparative Example 1 that the electrical properties of the graphene/nanocarbon particle composites of Examples 1-6 obtained by using the drying conditions within the scope of the present invention are superior. The electrical properties of Example 1 were compared. Secondly, it can be seen from the electrical properties of the nanocomposites of Example 7 using the combination of the preheat treatment and the reduction treatment and the reduction treatment of the nanocomposite of Example 7, using the preheat treatment and the reduction treatment to obtain the graphene/ The electrical properties of the nano-carbon particle composites are higher than those of the graphene/nano carbon particle composites obtained by the reduction treatment alone. It can be seen that the preheating treatment and the reduction treatment can further improve the electrical properties of the graphene/carbon nanoparticle composite material compared with the reduction treatment alone.
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限制， 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 intended to be a

Claims

权利要求 Rights request
1. 一种石墨烯 /纳米碳颗粒复合材料的制备方法， 其特征在于， 包括如下步骤：A method for preparing a graphene/nano carbon particle composite material, comprising the steps of:
1)将石墨氧化以制备氧化石墨烯， 将所得氧化石墨烯添加至水中制得悬浮液； 1) oxidizing graphite to prepare graphene oxide, adding the obtained graphene oxide to water to prepare a suspension;
2)将纳米碳颗粒添加至表面活性剂的水溶液中以获得纳米碳颗粒的悬浮液；  2) adding nano carbon particles to an aqueous solution of a surfactant to obtain a suspension of nano carbon particles;
3)将所述氧化石墨烯悬浮液与纳米碳颗粒悬浮液混合， 得到氧化石墨烯 /纳米碳颗粒 的均匀混合悬浮液；  3) mixing the graphene oxide suspension with the nano carbon particle suspension to obtain a uniform mixed suspension of graphene oxide/nano carbon particles;
4)将步骤 3)中所得的均匀混合悬浮液喷雾干燥， 得到粉末；  4) spray-drying the homogeneous mixed suspension obtained in the step 3) to obtain a powder;
5)对步骤 4)中所得的粉末进行如下处理：  5) The powder obtained in the step 4) is treated as follows:
a)在还原气氛下进行还原处理， 还原完毕后， 在还原气氛下冷却至室温， 清洗 并干燥， 最终制得负载有碳纳米颗粒的石墨烯复合材料； 或者  a) performing a reduction treatment under a reducing atmosphere, after the reduction is completed, cooling to room temperature under a reducing atmosphere, washing and drying to finally obtain a graphene composite material loaded with carbon nanoparticles; or
b)将步骤 4)中所得的粉末置于惰性气体氛围下， 对其进行预热处理， 再将粉末 冷却至室温； 接着于还原气氛下进行还原反应， 还原完毕后， 在还原气氛下 冷却至室温， 清洗并干燥， 最终制得负载有碳纳米颗粒的石墨烯复合材料。  b) The powder obtained in the step 4) is placed under an inert gas atmosphere, preheated, and then cooled to room temperature; then the reduction reaction is carried out under a reducing atmosphere, and after the reduction is completed, it is cooled to a reducing atmosphere. At room temperature, it is washed and dried to finally produce a graphene composite loaded with carbon nanoparticles.
2.根据权利要求 1的方法， 其中所述纳米碳颗粒选自碳 60、 碳黑、 乙炔黑、 科琴 黑、碳纳米管、碳纳米纤维或其组合。优选地，其中所述纳米碳颗粒的尺寸为 2-100nm， 优选为 10-80nm， 更优选为 20-60nm， 最优选为 20-50nm。  The method according to claim 1, wherein the nanocarbon particles are selected from the group consisting of carbon 60, carbon black, acetylene black, ketjen black, carbon nanotubes, carbon nanofibers, or a combination thereof. Preferably, wherein the nanocarbon particles have a size of from 2 to 100 nm, preferably from 10 to 80 nm, more preferably from 20 to 60 nm, and most preferably from 20 to 50 nm.
3. 根据权利要求 1-2中任一项所述的方法， 其特征在于， 所述石墨烯 /纳米碳颗 粒复合材料中的纳米碳颗粒的用量为 1-50%, 优选为 1-20%， 最优选为 5-15%, 基于 氧化石墨烯的质量。  The method according to any one of claims 1 to 2, wherein the amount of nano carbon particles in the graphene/carbon nanoparticle composite material is 1-50%, preferably 1-20%. Most preferably 5-15% based on the mass of graphene oxide.
4. 根据权利要求 1-3中任一项所述的方法， 其特征在于， 步骤 4)的喷雾干燥采用 离心喷雾， 超声喷雾、 气流喷雾或者压力喷雾技术或其组合。 优选地， 喷雾干燥采 用压力喷雾技术进行， 其中喷雾压力为 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。 更优选地， 其中 喷雾干燥采用离心喷雾技术进行， 其中离心速度为 50-10000转 /分钟， 优选 2000-5000 转 /分钟。  The method according to any one of claims 1 to 3, characterized in that the spray drying of step 4) employs a centrifugal spray, an ultrasonic spray, a jet spray or a pressure spray technique or a combination thereof. Preferably, the spray drying is carried out by a pressure spray technique, wherein the spray pressure is from 1 to 10 MPa, preferably from 4 to 6 MPa; the inlet air temperature is from 120 to 200 ° C, preferably from 140 to 160 ° C; and the outlet temperature is from 80 to 120 ° C. , preferably 90-100 ° C. More preferably, wherein the spray drying is carried out by a centrifugal spray technique, wherein the centrifugal speed is from 50 to 10,000 rpm, preferably from 2,000 to 5,000 rpm.
5.根据权利要求 1-4中的方法， 其特征在于， 其中所述还原气体为氢气， 或者氢 气与惰性气体的混合气体。 The method according to any one of claims 1 to 4, wherein the reducing gas is hydrogen or a mixed gas of hydrogen and an inert gas.
6.根据权利要求 1-5中任一项的方法， 其特征在于， 其中步骤 5)的 a)和 b)中还原 处理的时间为 1-10小时， 优选为 2-4小时。 The method according to any one of claims 1 to 5, wherein the time of the reduction treatment in a) and b) of the step 5) is from 1 to 10 hours, preferably from 2 to 4 hours.
7.根据权利要求 1-6中任一项的方法， 其特征在于， 其中步骤 5)的 a)和 b)中的还 原温度为 600-1200°C , 优选为 600-800°C。  The method according to any one of claims 1 to 6, wherein the reduction temperature in a) and b) of step 5) is from 600 to 1200 ° C, preferably from 600 to 800 ° C.
8.根据权利要求 1-7中任一项的方法， 其中在步骤 5)的 b)中， 预热处理的温度为 300-500 °C , 优选为 320-400°C， 最优选为 350°C ; 预热处理的时间通常为 1-12小时， 优 选为 2-4小时。  The method according to any one of claims 1 to 7, wherein in the step b), the preheating temperature is 300-500 ° C, preferably 320-400 ° C, most preferably 350 ° C; The preheat treatment time is usually from 1 to 12 hours, preferably from 2 to 4 hours.
9.根据权利要求 1-8中任一项的方法获得的石墨烯 /纳米碳颗粒复合材料。  The graphene/nanocarbon particle composite obtained by the method according to any one of claims 1-8.
10.根据权利要求 1-8 中任一项的方法获得的石墨烯 /纳米碳颗粒复合材料或权 利要求 9的石墨烯 /纳米碳颗粒复合材料作为超级电容器材料、 催化剂载体或红外光 学材料的用途。  10. Use of a graphene/nanocarbon particle composite obtained by the method according to any one of claims 1-8 or a graphene/carbon nanoparticle composite according to claim 9 as a supercapacitor material, a catalyst carrier or an infrared optical material .
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