WO2014117434A1 - Method for preparing graphene through rapid thermal treatment in air atmosphere - Google Patents

Method for preparing graphene through rapid thermal treatment in air atmosphere Download PDF

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WO2014117434A1
WO2014117434A1 PCT/CN2013/073776 CN2013073776W WO2014117434A1 WO 2014117434 A1 WO2014117434 A1 WO 2014117434A1 CN 2013073776 W CN2013073776 W CN 2013073776W WO 2014117434 A1 WO2014117434 A1 WO 2014117434A1
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graphene
heat treatment
nitrogen
air atmosphere
powder
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PCT/CN2013/073776
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French (fr)
Chinese (zh)
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丁古巧
李修兵
孙静
谢晓明
***
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中国科学院上海微***与信息技术研究所
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Publication of WO2014117434A1 publication Critical patent/WO2014117434A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01B32/184—Preparation

Definitions

  • the invention relates to a method for preparing graphene by rapid heat treatment in an air atmosphere, and belongs to the field of graphene preparation. Background technique
  • Graphene has received extensive attention due to its unique two-dimensional stable structure and photoelectric properties.
  • Single-layer graphene has excellent properties such as good electrical conductivity, large specific surface area and high mechanical stability. Because of these extraordinary properties, their use in nanoelectronics, nanocomposites, lithium-ion batteries, supercapacitors, hydrogen storage, and biomaterials is being studied.
  • methods for preparing graphene mainly include mechanical stripping method, graphene oxide reduction method, ultrasonic dispersion method, chemical synthesis method and the like.
  • CN 102765716 A discloses a method of preparing a graphene powder by ultrasonic dispersion mixing of graphite oxide with a pyridine and an alcohol-based organic solvent, but the ultrasonic stripping yield is low, and it is difficult to control the layer number distribution of graphene.
  • Mechanical stripping can achieve high quality graphene, but dimensional control and yield improvement are difficult and cannot be mass produced.
  • Nanographene sheets can be obtained by directly stripping graphite after weak intercalation, and can be prepared on a large scale, but a conventional redox method is required to realize uniform 1-10 layer graphene preparation.
  • the redox method refers to the Hummer method, the Standenmair method, and the Brodie method.
  • This graphene precursor is reduced and converted to graphene by two means.
  • One is a liquid phase reduction method in which a graphene precursor is first dispersed in a solution by ultrasonication to form a graphene oxide solution, and then graphene is obtained by reduction with a reducing agent such as hydrazine hydrate or hydrogen iodide.
  • Another method is to directly heat the graphene precursor directly, that is, the graphene precursor is heated rapidly in a short period of time, and the oxygen-containing groups and water molecules intercalated between the layers are reacted to form a gas or vaporized to cause graphene.
  • the sheet of the precursor is separated, and the oxygen-containing group removal of the graphene precursor is reduced to graphene.
  • Rapid heat treatment is a method for preparing graphene powder on a large scale, but the prior art needs to be carried out under the protection of inert (argon or nitrogen) or reducing (hydrogen) atmosphere, such as Functionalized Single Graphene Sheets Derived from Splitting Graphite Oxide. The Journal of Physical B Letters.
  • the nitrogen-containing compound further controls the atmosphere and doping in the crucible, and obtains a graphene powder having a high degree of reduction, a large specific surface area, and excellent electrical properties.
  • the present invention is achieved by the following technical solutions: a method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere, in which a precursor of graphene is first placed in a non-sealed covered crucible, and then heat-treated in an air atmosphere.
  • a powder of graphene is obtained.
  • the oxygen inside the crucible is quickly consumed by the reaction of carbon, and at the same time, since the graphene precursor releases a large amount of gas during the heat treatment, the gas escapes from the gap between the crucible and the crucible.
  • the oxygen outside the crucible cannot enter the crucible, thereby achieving control of the atmosphere inside the crucible.
  • the graphene precursor and the nitrogen-containing compound are uniformly mixed and placed in a non-sealed lid crucible, and then heat-treated to obtain a nitrogen-doped graphene powder; during the heat treatment, the ammonia generated in the decomposition of the ammonium salt contains ammonia.
  • the gas can not only further control the atmosphere inside the crucible but also achieve nitrogen doping of the graphene powder.
  • the nitrogen-containing compound is urea or an ammonium salt; the ammonium salt is selected from the group consisting of ammonium carbonate and ammonium hydrogencarbonate.
  • the graphene precursor is intercalated graphite, that is, an oxygen-containing functional group is intercalated between the graphite layers, and the distance between the graphite layers is increased. Common methods for preparing intercalated graphite include the Hummer method, the Standenmair method, and the Brodie method. It can also be obtained using other methods with interpolated effects.
  • the oxygen-containing functional group mainly includes a hydroxyl group, a carboxyl group, an epoxy group and the like, and the intercalated graphite prepared by each of the above methods contains an oxygen-containing functional group such as the above-mentioned hydroxyl group, carboxyl group and epoxy group.
  • the non-sealed cover ⁇ includes but is not limited to quartz, silicon carbide, graphite and stainless steel; the size of the crucible is related to the size of the heat treatment equipment, the typical size is the length X width X height is 50mm x 50mm x 20mm to 400mm x 400mm x 200mm; the thickness of the crucible is related to the material, the typical thickness It is 0.5-2mm ; there is a lid on the raft, just covering the raft, but there is no seal.
  • the gas generated by the decomposition of the precursor forms a positive pressure in the crucible, and the lid is opened to form a gap, so that the gas escapes.
  • the gas is always in the crucible. Out, ⁇
  • the outside gas does not enter the helium, or the gas entering the helium can be ignored.
  • the cockroach is only inaccessible to gas.
  • the manner in which the graphene precursor is uniformly mixed with the nitrogen-containing compound is dry mixing or wet mixing; the dry mixing is to thoroughly stir and mix the dried graphene precursor and the nitrogen-containing compound powder; The wet mixing is carried out by adding a nitrogen-containing compound to an aqueous solution of a graphene precursor, stirring and mixing well, followed by drying to obtain a uniformly mixed powder of a graphene precursor and a nitrogen-containing compound.
  • the ratio of the mass ratio of the graphene precursor to the nitrogen-containing compound is 100: 1 to 100 : 30; by adjusting the mixing ratio, doping with different nitrogen contents can be achieved.
  • the heat treatment temperature is 250 to 850 ° C, and the time is 10 to 120 seconds; the number of layers of graphene obtained is 1-5 layers, the specific surface area (BET) is 500 to 918 m 2 /g, and the specific resistance is 0.02. ⁇ 0.04 ⁇ .
  • the nitrogen doping amount of the graphene product obtained that is, the ratio of the nitrogen atom in the graphene product to the total atomic weight of the graphene product, is controlled at 0.62 to 8.96 at.%.
  • FIG. 1 is a FESEM chart of a graphene powder obtained by heat-treating at 550 ° C for 30 seconds in Example 1.
  • FIG. 2 is a TEM image of a graphene powder obtained by heat-treating at 550 ° C for 30 seconds in Example 1.
  • FIG. 4 is a graph showing changes in BET of graphene powder obtained by different heat treatment times at 550 ° C in Example 2 with heat treatment time.
  • FIG. 5 is Example 2 Heat treatment at different temperatures for 30 seconds to obtain the relationship between BET value and temperature of graphene powder 6 is an XPS chart obtained by using the graphene powder obtained in Example 2 at different temperatures.
  • FIG. 1 is a FESEM chart of a graphene powder obtained by heat-treating at 550 ° C for 30 seconds in Example 1.
  • FIG. 2 is a TEM image of a graphene powder obtained by heat-treating at 550
  • FIG. 7 is a relationship between different urea contents in Example 3 and the obtained graphene powder BET.
  • FIG. 8 is a third embodiment. XPS spectrum of graphene powder obtained by heat treatment of different urea addition amounts
  • FIG. 9 is an XPS spectrum of graphene powder obtained by heat treatment of different urea addition amounts in Example 3.
  • FIG. 10 is a heat treatment at 550 ° C in Example 4.
  • FIG. 11 is an HRTEM image of graphene prepared by heat treatment at 550 ° C for 30 s in Example 4.
  • the numbering of the method steps is merely a convenient means of identifying the various method steps, and is not intended to limit the order of the various method steps or to limit the scope of the invention, the relative In the case where the technical content is not substantially changed, it is also considered to be an area in which the present invention can be implemented.
  • BET Specific surface area Test: The Beijing Jine spectrum F-Sorb 2400 specific surface area tester was used to test the multi-point BET by nitrogen adsorption method. The sample was heated at 100 °C and pre-treated with vacuum for 1 h.
  • FESEM test description Sample testing was performed using Hitachi S4700. The graphene powder is directly pressed onto the conductive adhesive tape, tested after nitrogen purge, or the sample is ultrasonically dispersed in ethanol, and a small amount of droplets are dried on the surface of the conductive tape to test.
  • TEM Transmission electron microscopy
  • HRTEM high-resolution transmission electron microscopy
  • the Model 250 was tested by X-ray photoelectron spectroscopy.
  • the beam used was a monochromatic aluminum wire.
  • the sample was etched with Ar ions for 10 s before testing.
  • a graphene precursor was prepared by the Stamdenmair method. The specific process is as follows: 100 g of 325 mesh natural flake graphite is added to a mixed solution of 950 ml of HN0 3 and 1783.3 ml of H 2 S0 4 , stirred for 30 min, then added with 1100 g of sodium chlorate, reacted at 25 ° C for 12 h, filtered, washed The vacuum green drying was carried out at 90 ° C to obtain a dark green graphene precursor.
  • the dark green graphene precursor was expanded by heat treatment and converted into a black powder.
  • XPS results showed that the main component was SP 2 carbon, and the atomic percentage of oxygen atoms in the product was 7.2 at%.
  • the FESEM test scan of the graphene powder of this example is shown in Fig. 1, and the results show that many thin graphene sheets have a wrinkled morphology.
  • the BET obtained at different temperatures and different heat treatment times is greater than 500 m 2 /g, between 560 and 918 m 2 /g.
  • Heat treatment at 250 and 350 °C for 10 seconds was not tested because the precursor did not swell significantly or undergo a color change. This indicates that the heat treatment time needs to be slightly longer at a low temperature.
  • Figure 4 shows the change in BET of graphene powder obtained at different heat treatment times at 550 °C with heat treatment time.
  • Figure 5 shows the relationship between the BET value and the temperature of the graphene powder obtained by heat treatment at different temperatures for 30 seconds.
  • Figures 4 and 5 show that the BET of the graphene powder is related to the heat treatment temperature and time.
  • Figure 6 is an XPS diagram of the obtained graphene powder obtained at different temperatures.
  • the XPS results show that the oxygen content of the graphene powder obtained at different temperatures is about 7.2 wt%.
  • Example 3 Dry mixing, different urea addition amounts of the same heat treatment temperature to prepare doped graphene powder
  • Example 4 Wet mixing, the same amount of ammonium bicarbonate added to different heat treatment temperatures to prepare graphene powder
  • Figures 10 and 11 show TEM and HRTEM photographs of graphene prepared by heat treatment at 550 ° C for 30 s, respectively.
  • the heat treatment after the ammonium hydrogencarbonate and the graphene precursor are combined does not affect the microscopic morphology of the graphene, and the thickness of the graphene is also 1-5 atomic layers as in the examples 1 and 2.
  • the heat treatment after urea and graphene precursor compounding can not only be carried out in air, but also can achieve controlled nitrogen doping of graphene.
  • Table 3 shows the conductivity of graphene powder obtained by heat treatment at different temperatures for the same content of ammonium bicarbonate. It can be seen from Table 3 that the prepared graphene powder has excellent electrical properties, a specific resistance of 0.02 to 0.04 ⁇ , and a BET of 500 m 2 /g or more.

Abstract

A method for preparing graphene powder through rapid thermal treatment in an air atmosphere. The method comprises: placing a precursor of graphene in an unsealed covered crucible, and performing thermal treatment in an air atmosphere, to obtain graphene powder; alternatively, uniformly mixing the precursor of graphene with a nitrogen-containing compound, then placing the mixture in the unsealed covered crucible, and performing thermal treatment, to obtain nitrogen-doped graphene powder. The method requires no protection from an inert gas or a reducing gas, so that the requirement on equipment is lowered; the thermal treatment temperature of graphene is reduced to 250 to 850°C, which greatly expands the thermal treatment temperature range of graphene, and reduces power consumption; and nitrogen controllable doping of graphene is realized, and the controllable doping facilitates applications of the graphene powder.

Description

一种空气气氛中快速热处理制备石墨烯的方法 技术领域  Method for preparing graphene by rapid heat treatment in air atmosphere
本发明涉及一种空气气氛中快速热处理制备石墨烯的方法， 属于石墨烯制备领域。 背景技术  The invention relates to a method for preparing graphene by rapid heat treatment in an air atmosphere, and belongs to the field of graphene preparation. Background technique
石墨烯由于其独特的二维稳定结构和光电性质受到广泛重视， 单层石墨烯具有良好的导 电性、 较大的比表面积、 高机械稳定性等优越的性能。 由于这些非凡的性能， 人们正在研究 其在纳米电子学、 纳米复合物、 锂离子电池、 超级电容器、 氢储藏以及生物材料中的用途。 目前， 制备石墨烯的方法主要有机械剥离法， 氧化石墨烯还原法、 超声分散法、 化学合成法 等。 中国发明专利公布号 CN 102765716 A公开了一种将氧化石墨与吡啶和醇类有机溶剂混 合超声分散制备石墨烯粉体的方法， 但超声剥离产率低， 并且难以控制石墨烯的层数分布。 机械剥离可以获得高质量的石墨烯， 但尺寸控制和产量提高都很困难， 无法量产。 通过较弱 的插层后直接剥离石墨可以得到纳米石墨烯片， 并且可以规模化制备， 但要实现均匀的 1-10 层石墨烯的制备还是需要传统的氧化还原法。 氧化还原法是指 Hummer法、 Standenmair法和 Brodie法等， 这些方法都是使用强氧化 剂氧化石墨碳原子， 在石墨层间生成含氧官能团， 石墨层间距增加， 获得氧化石墨或称插层 石墨。 这种石墨烯前驱体通过两种方式还原并转化为石墨烯。 一种为液相还原法， 利用超声 的手段先在溶液中分散石墨烯前驱体， 形成氧化石墨烯溶液， 之后再通过水合肼和碘化氢等 还原剂还原获得石墨烯。 另一种方法是直接将石墨烯前驱体进行快速热处理， 即在较短的时 间内使石墨烯前驱体急剧升温， ***层间的含氧基团和水分子等反应生成气体或汽化使石墨 烯前驱体的片层发生分离， 同时石墨烯前驱体含氧基团去除被还原为石墨烯。 快速热处理是一种可以规模化制备石墨烯粉体的方法， 但现有技术需要在惰性 （氩气或 氮气） 或还原性 （氢气） 气氛保护下进行， 如 Functionalized Single Graphene Sheets Derived from Splitting Graphite Oxide. The Journal of Physical B Letters. 110 (2006) 8535-8539, 文献研 究并报道了在 1050 °C快速剥离获得石墨烯的方法。 综述性论文 The Reductin of Graphene Oxide, Carbon, 50 (2012) 3210-3228 , 详细列举了热还原氧化石墨烯的方法， 包括真空高温处 理， 惰性气体热处理和超高真空热处理等。 Graphene has received extensive attention due to its unique two-dimensional stable structure and photoelectric properties. Single-layer graphene has excellent properties such as good electrical conductivity, large specific surface area and high mechanical stability. Because of these extraordinary properties, their use in nanoelectronics, nanocomposites, lithium-ion batteries, supercapacitors, hydrogen storage, and biomaterials is being studied. At present, methods for preparing graphene mainly include mechanical stripping method, graphene oxide reduction method, ultrasonic dispersion method, chemical synthesis method and the like. Chinese Patent Publication No. CN 102765716 A discloses a method of preparing a graphene powder by ultrasonic dispersion mixing of graphite oxide with a pyridine and an alcohol-based organic solvent, but the ultrasonic stripping yield is low, and it is difficult to control the layer number distribution of graphene. Mechanical stripping can achieve high quality graphene, but dimensional control and yield improvement are difficult and cannot be mass produced. Nanographene sheets can be obtained by directly stripping graphite after weak intercalation, and can be prepared on a large scale, but a conventional redox method is required to realize uniform 1-10 layer graphene preparation. The redox method refers to the Hummer method, the Standenmair method, and the Brodie method. These methods use a strong oxidizing agent to oxidize graphite carbon atoms to form an oxygen-containing functional group between the graphite layers, and the graphite layer spacing is increased to obtain graphite oxide or intercalated graphite. This graphene precursor is reduced and converted to graphene by two means. One is a liquid phase reduction method in which a graphene precursor is first dispersed in a solution by ultrasonication to form a graphene oxide solution, and then graphene is obtained by reduction with a reducing agent such as hydrazine hydrate or hydrogen iodide. Another method is to directly heat the graphene precursor directly, that is, the graphene precursor is heated rapidly in a short period of time, and the oxygen-containing groups and water molecules intercalated between the layers are reacted to form a gas or vaporized to cause graphene. The sheet of the precursor is separated, and the oxygen-containing group removal of the graphene precursor is reduced to graphene. Rapid heat treatment is a method for preparing graphene powder on a large scale, but the prior art needs to be carried out under the protection of inert (argon or nitrogen) or reducing (hydrogen) atmosphere, such as Functionalized Single Graphene Sheets Derived from Splitting Graphite Oxide. The Journal of Physical B Letters. 110 (2006) 8535-8539, Literature Research A method for rapidly stripping graphene at 1050 °C was reported. The review of the paper The Reductin of Graphene Oxide, Carbon, 50 (2012) 3210-3228, details the thermal reduction of graphene oxide, including vacuum high temperature treatment, inert gas heat treatment and ultra high vacuum heat treatment.
发明内容 Summary of the invention
本发明的目的在于提供一种在空气气氛中快速热处理制备石墨烯粉体方法， 通过非密封 有盖坩埚实现石墨烯前驱体在快速热处理过程中的气氛控制， 并且通过在石墨烯前驱体中加 入含氮化合物进一步控制坩埚内的气氛和掺杂， 获得还原程度高、 比表面积大且电学性能优 异的石墨烯粉体。 本发明是通过以下技术方案实现的： 一种在空气气氛中快速热处理制备石墨烯粉体方法， 为先将石墨烯的前驱体置于非密封 有盖坩埚中， 然后在空气气氛中进行热处理， 即得到石墨烯的粉体。 采用非密封有盖坩埚， 在热处理过程中， 坩埚内部的氧很快与碳反应消耗掉， 同时由于 石墨烯前驱体在热处理过程中放出大量气体， 气体从坩埚与坩埚盖的缝隙中逸出， 坩埚外的 氧无法进入坩埚内， 从而实现对坩埚内的气氛控制。 将石墨烯前驱体与含氮化合物均匀混合后置于非密封有盖坩埚中， 然后进行热处理， 可 得到氮掺杂的石墨烯粉体； 热处理过程中， 铵盐分解时产生的气体中含有氨气， 不仅能够进 一步控制坩埚内的气氛而且能够实现对石墨烯粉体的氮掺杂。 所述含氮化合物为尿素或铵盐； 所述铵盐选自碳酸铵和碳酸氢铵等。 所述石墨烯前驱体为插层石墨， 即石墨层间***含氧官能团， 石墨层间距离增加。 通用 的制备插层石墨的方法包括 Hummer法、 Standenmair法和 Brodie法等。 也可以使用具有插 层效果的其他方法获得。 所述含氧官能团主要包括羟基、 羧基和环氧基等， 且前述各方法制 备的插层石墨均含有前述羟基、 羧基和环氧基等含氧官能团。  It is an object of the present invention to provide a method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere, and controlling the atmosphere of the graphene precursor in a rapid heat treatment process by using a non-sealed lid crucible, and adding it to the graphene precursor The nitrogen-containing compound further controls the atmosphere and doping in the crucible, and obtains a graphene powder having a high degree of reduction, a large specific surface area, and excellent electrical properties. The present invention is achieved by the following technical solutions: a method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere, in which a precursor of graphene is first placed in a non-sealed covered crucible, and then heat-treated in an air atmosphere. That is, a powder of graphene is obtained. With a non-sealed lid, during the heat treatment, the oxygen inside the crucible is quickly consumed by the reaction of carbon, and at the same time, since the graphene precursor releases a large amount of gas during the heat treatment, the gas escapes from the gap between the crucible and the crucible. The oxygen outside the crucible cannot enter the crucible, thereby achieving control of the atmosphere inside the crucible. The graphene precursor and the nitrogen-containing compound are uniformly mixed and placed in a non-sealed lid crucible, and then heat-treated to obtain a nitrogen-doped graphene powder; during the heat treatment, the ammonia generated in the decomposition of the ammonium salt contains ammonia. The gas can not only further control the atmosphere inside the crucible but also achieve nitrogen doping of the graphene powder. The nitrogen-containing compound is urea or an ammonium salt; the ammonium salt is selected from the group consisting of ammonium carbonate and ammonium hydrogencarbonate. The graphene precursor is intercalated graphite, that is, an oxygen-containing functional group is intercalated between the graphite layers, and the distance between the graphite layers is increased. Common methods for preparing intercalated graphite include the Hummer method, the Standenmair method, and the Brodie method. It can also be obtained using other methods with interpolated effects. The oxygen-containing functional group mainly includes a hydroxyl group, a carboxyl group, an epoxy group and the like, and the intercalated graphite prepared by each of the above methods contains an oxygen-containing functional group such as the above-mentioned hydroxyl group, carboxyl group and epoxy group.
所述非密封有盖坩埚， 材质包括但不限于石英、 碳化硅、 石墨和不锈钢； 坩埚尺寸与热 处理设备尺寸相关， 典型尺寸长 X宽 X高为 50mmx50mmx20mm到 400mmx400mmx200mm; 坩埚厚度与材料相关， 典型厚度为 0.5-2mm; 坩埚上有坩埚盖， 正好盖住坩埚， 但没有密 封。 这种坩埚在热处理石墨烯前驱体的过程中， 前驱体分解产生的气体在坩埚内形成正压 力， 顶开坩埚盖形成缝隙， 使气体逸出， 在热处理过程中， 始终是坩埚内的气体逸出， 坩埚 外的气体并不能进入坩埚， 或者进入坩埚的气体可以忽略。 总体而言， 该坩埚对于气体只进 不出。 所述石墨烯前驱体与含氮化合物均匀混合的方式为干法混合或湿法混合； 所述干法混 合， 是将干燥的石墨烯前驱体和含氮化合物粉体充分搅拌混合； 所述的湿法混合是在石墨烯 前驱体水溶液中加入含氮化合物充分搅拌混合， 再烘干获得石墨烯前驱体和含氮化合物的均 匀混合粉体。 所述的石墨烯前驱体与含氮化合物混合质量之比为 100: 1〜100:30； 通过调节混合比 例， 可实现不同含氮量的掺杂。 所述热处理的温度为 250〜850°C， 时间为 10〜120秒； 所获得石墨烯的层数为 1-5层， 比表面积 （BET) 为 500〜918 m2/g， 电阻率为 0.02〜0.04Ω· η。 对于氮掺杂的石墨烯， 所获得的石墨烯产品氮掺杂量， 即石墨烯产品中氮原子占石墨烯 产品总原子量的比例， 控制在 0.62〜8.96 at.%。 本发明的技术效果及优点在于： The non-sealed cover 坩埚, the material includes but is not limited to quartz, silicon carbide, graphite and stainless steel; the size of the crucible is related to the size of the heat treatment equipment, the typical size is the length X width X height is 50mm x 50mm x 20mm to 400mm x 400mm x 200mm; the thickness of the crucible is related to the material, the typical thickness It is 0.5-2mm ; there is a lid on the raft, just covering the raft, but there is no seal. In the process of heat-treating the graphene precursor, the gas generated by the decomposition of the precursor forms a positive pressure in the crucible, and the lid is opened to form a gap, so that the gas escapes. During the heat treatment, the gas is always in the crucible. Out, 坩埚 The outside gas does not enter the helium, or the gas entering the helium can be ignored. In general, the cockroach is only inaccessible to gas. The manner in which the graphene precursor is uniformly mixed with the nitrogen-containing compound is dry mixing or wet mixing; the dry mixing is to thoroughly stir and mix the dried graphene precursor and the nitrogen-containing compound powder; The wet mixing is carried out by adding a nitrogen-containing compound to an aqueous solution of a graphene precursor, stirring and mixing well, followed by drying to obtain a uniformly mixed powder of a graphene precursor and a nitrogen-containing compound. The ratio of the mass ratio of the graphene precursor to the nitrogen-containing compound is 100: 1 to 100 : 30; by adjusting the mixing ratio, doping with different nitrogen contents can be achieved. The heat treatment temperature is 250 to 850 ° C, and the time is 10 to 120 seconds; the number of layers of graphene obtained is 1-5 layers, the specific surface area (BET) is 500 to 918 m 2 /g, and the specific resistance is 0.02. ~0.04Ω·η. For nitrogen-doped graphene, the nitrogen doping amount of the graphene product obtained, that is, the ratio of the nitrogen atom in the graphene product to the total atomic weight of the graphene product, is controlled at 0.62 to 8.96 at.%. The technical effects and advantages of the present invention are as follows:
不需要惰性气体或还原性气体保护， 因而对于设备的要求降低； 将石墨烯的热处理温度 降低到 250-850°C， 极大地扩展了石墨烯的热处理温度区间， 并且降低了能耗； 实现石墨烯 的可控氮掺杂， 可控掺杂有利于拓展石墨烯粉体的应用。 尿素和铵盐均易溶于水， 因此除了 可以与石墨烯前驱体进行干法混合之外， 还可以在洗涤石墨烯前驱体工艺过程中进行湿法混 合； 尿素或铵盐热分解之后没有任何固体残留， 同时掺杂效果显著， 与利用氨气进行高温掺 杂相比， 具有明显优势。  No need for inert gas or reducing gas protection, so the requirements for equipment are reduced; reducing the heat treatment temperature of graphene to 250-850 °C greatly expands the heat treatment temperature range of graphene and reduces energy consumption; Controllable nitrogen doping of olefins, controlled doping is beneficial to expand the application of graphene powder. Both urea and ammonium salts are easily soluble in water, so in addition to dry mixing with graphene precursors, wet mixing can also be carried out during the washing of graphene precursors; no decomposition of urea or ammonium salts after thermal decomposition The solid residue and the doping effect are remarkable, which has obvious advantages compared with the high temperature doping by ammonia gas.
附图说明 DRAWINGS
图 1是实施例 1在 550°C， 30秒热处理得到的石墨烯粉体的 FESEM图 图 2是实施例 1在 550°C， 30秒热处理得到的石墨烯粉体的 TEM图 图 3是实施例 1在 550°C， 30秒热处理得到的石墨烯粉体的 HRTEM图 图 4是实施例 2中 550°C不同热处理时间得到的石墨烯粉体 BET随热处理时间的变化 图 5是实施例 2中不同温度热处理 30秒得到石墨烯粉体的 BET值和温度的关系 图 6是实施例 2所制得的石墨烯粉体在不同温度下得到的 XPS图 图 7是实施例 3中不同尿素含量与所获得石墨烯粉体 BET的关系图 图 8是实施例 3中不同尿素添加量热处理所获得的石墨烯粉体的 XPS谱图 图 9是实施例 3中不同尿素添加量热处理所获得的石墨烯粉体的 XPS谱图 图 10是实施例 4中 550°C热处理 30s所制备石墨烯的 TEM图 图 11是实施例 4中 550°C热处理 30s所制备石墨烯的 HRTEM图 1 is a FESEM chart of a graphene powder obtained by heat-treating at 550 ° C for 30 seconds in Example 1. FIG. 2 is a TEM image of a graphene powder obtained by heat-treating at 550 ° C for 30 seconds in Example 1. FIG. Example 1 HRTEM image of graphene powder obtained by heat treatment at 550 ° C for 30 seconds FIG. 4 is a graph showing changes in BET of graphene powder obtained by different heat treatment times at 550 ° C in Example 2 with heat treatment time. FIG. 5 is Example 2 Heat treatment at different temperatures for 30 seconds to obtain the relationship between BET value and temperature of graphene powder 6 is an XPS chart obtained by using the graphene powder obtained in Example 2 at different temperatures. FIG. 7 is a relationship between different urea contents in Example 3 and the obtained graphene powder BET. FIG. 8 is a third embodiment. XPS spectrum of graphene powder obtained by heat treatment of different urea addition amounts FIG. 9 is an XPS spectrum of graphene powder obtained by heat treatment of different urea addition amounts in Example 3. FIG. 10 is a heat treatment at 550 ° C in Example 4. TEM image of graphene prepared in 30s FIG. 11 is an HRTEM image of graphene prepared by heat treatment at 550 ° C for 30 s in Example 4.
具体实施方式 以下通过特定的具体实例说明本发明的技术方案。 应理解， 本发明提到的一个或多个方 法步骤并不排斥在所述组合步骤前后还存在其他方法步骤或在这些明确提到的步骤之间还可 以***其他方法步骤； 还应理解， 这些实施例仅用于说明本发明而不用于限制本发明的范 围。 而且， 除非另有说明， 各方法步骤的编号仅为鉴别各方法步骤的便利工具， 而非为限制 各方法步骤的排列次序或限定本发明可实施的范围， 其相对关系的改变或调整， 在无实质变 更技术内容的情况下， 当亦视为本发明可实施的范畴。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the technical solution of the present invention will be described by way of specific specific examples. It should be understood that one or more of the method steps referred to in the present invention does not exclude that other method steps exist before or after the combination step or that other method steps can be inserted between the steps explicitly mentioned; it should also be understood that these The examples are only intended to illustrate the invention and are not intended to limit the scope of the invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient means of identifying the various method steps, and is not intended to limit the order of the various method steps or to limit the scope of the invention, the relative In the case where the technical content is not substantially changed, it is also considered to be an area in which the present invention can be implemented.
测试方法说明：  Test method description:
1. 比表面积 （BET) 测试： 采用北京金埃谱 F-Sorb 2400型比表面积测试仪， 利用氮气 吸附法多点 BET进行测试， 测试前样品进行 100°C加热， 抽真空 lh的预处理。 1. Specific surface area (BET) Test: The Beijing Jine spectrum F-Sorb 2400 specific surface area tester was used to test the multi-point BET by nitrogen adsorption method. The sample was heated at 100 °C and pre-treated with vacuum for 1 h.
2. 电导和电阻率测试说明： 采用 HL5500PC 霍尔测试仪， 具体步骤如下： 称取石墨烯 粉体 15-25mg， 将粉体进行压片， 片子厚度为 0.3〜0.7mm， 然后将四探针轻轻压在片子上， 进行测试。 2. Conductance and resistivity test description: The HL5500PC Hall tester is used. The specific steps are as follows: Weigh 15-25mg of graphene powder, compress the powder, the thickness of the film is 0.3~0.7mm, then the four probes Gently press on the slide and test.
3. FESEM测试说明： 采用 Hitachi S4700进行样品测试。 将石墨烯粉体直接压在导电胶 带上， 氮气吹扫后测试， 或将样品超声分散在乙醇容易中， 取少量滴在导电胶带表面烘干测 试。 3. FESEM test description: Sample testing was performed using Hitachi S4700. The graphene powder is directly pressed onto the conductive adhesive tape, tested after nitrogen purge, or the sample is ultrasonically dispersed in ethanol, and a small amount of droplets are dried on the surface of the conductive tape to test.
4. 透射电镜 （TEM) 和高分辨透射电镜 （HRTEM) 测试： 采用日本 JEOL JEM 2100型 透射电子显微镜进行样品测试。 样品制备方法： 取适量样品置于乙醇溶液中， 超声 10 分 钟， 取均匀悬浮液一滴到微栅支撑膜上， 自然晾干。 4. Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) tests: Samples were tested using a Japanese JEOL JEM 2100 transmission electron microscope. Sample preparation method: Take appropriate amount of sample in ethanol solution, ultrasonic 10 points Clock, take a uniform suspension onto the microgrid support film and let it dry naturally.
5. X射线光电子能谱 （XPS) 测试说明： 采用美国 Thermo Fisher Scientific ESCALAB 5. X-ray photoelectron spectroscopy (XPS) Test description: US Thermo Fisher Scientific ESCALAB
250型 X射线光电子能谱进行样品测试， 所采用的光束是单色铝^线， 样品测试前用 Ar离 子进行 10s刻蚀。 The Model 250 was tested by X-ray photoelectron spectroscopy. The beam used was a monochromatic aluminum wire. The sample was etched with Ar ions for 10 s before testing.
实施例 1 : 空气中快速热处理制备石墨烯粉体： Example 1: Preparation of graphene powder by rapid heat treatment in air:
( 1 ) 采用 Stamdenmair法制备石墨烯前驱体。 具体工艺如下： 将 100克 325 目天然鳞片石 墨加入到 950 mlHN03和 1783.3mlH2S04的混合溶液中， 搅拌 30min, 再加入 1100克氯酸 钠， 25°C反应 12h， 经抽滤、 洗涤、 90°C真空干燥获得墨绿色石墨烯前驱体。 (1) A graphene precursor was prepared by the Stamdenmair method. The specific process is as follows: 100 g of 325 mesh natural flake graphite is added to a mixed solution of 950 ml of HN0 3 and 1783.3 ml of H 2 S0 4 , stirred for 30 min, then added with 1100 g of sodium chlorate, reacted at 25 ° C for 12 h, filtered, washed The vacuum green drying was carried out at 90 ° C to obtain a dark green graphene precursor.
( 2 ) 空气中快速热处理制备石墨烯粉体： 取 200mg 石墨烯前驱体， 置于长 X宽 X高为 50mmx50mmx20mm的材质为碳化硅、 厚度为 0.5-2mm的非密封有盖坩埚中， 快速放入 550 。C的热处理炉中， 保温 30秒取出。  (2) Rapid heat treatment in air to prepare graphene powder: Take 200mg graphene precursor, placed in a non-sealed lid with a length X width X height of 50mmx50mmx20mm and a thickness of 0.5-2mm. Into 550. In the heat treatment furnace of C, it was taken out for 30 seconds.
墨绿色石墨烯前驱体经热处理体积膨胀， 转变为黑色粉末， XPS 结果表明主要成分为 SP2结构的碳， 氧原子在产物中的原子百分含量为 7.2 at%。 The dark green graphene precursor was expanded by heat treatment and converted into a black powder. XPS results showed that the main component was SP 2 carbon, and the atomic percentage of oxygen atoms in the product was 7.2 at%.
本实施例石墨烯粉体 FESEM测试扫描图如图 1所述， 结果显示为许多薄的石墨烯片形 成褶皱的形貌。  The FESEM test scan of the graphene powder of this example is shown in Fig. 1, and the results show that many thin graphene sheets have a wrinkled morphology.
本实施例石墨烯粉体的 TEM和 HRTEM测试的结果分别如图 2和 3所示， 从图中可以 看出所获得的石墨烯粉体的层数为 1-5层。 实施例 2: 不同热处理温度和不同热处理时间制备石墨烯粉体  The results of the TEM and HRTEM tests of the graphene powder of this example are shown in Figs. 2 and 3, respectively, and it can be seen from the figure that the number of layers of the graphene powder obtained is 1-5 layers. Example 2: Preparation of graphene powders at different heat treatment temperatures and different heat treatment times
( 1 ) 石墨烯前驱体的制备同实施例 1 ;  (1) The preparation of the graphene precursor is the same as in the first embodiment;
(2) 制备石墨烯粉体： 分别取 lg 石墨烯前驱体， 置于长宽高为 150mmxl50mmxl00mm 的材质为不锈钢、 厚度为 0.5-2mm 的非密封有盖坩埚中， 分别快速放入 250°C、 350 °C、 450°C、 550°C、 650°C、 750°C、 850°C的热处理炉中， 保温 10， 30， 60， 120 秒 取出。 (2) Preparation of graphene powder: Take lg graphene precursor separately, placed in a non-sealed lid with a length, width and height of 150mmxl50mmxl00mm and a thickness of 0.5-2mm, respectively, and quickly put into 250 °C, In the heat treatment furnace at 350 °C, 450 °C, 550 °C, 650 °C, 750 °C, 850 °C, keep warm for 10, 30, 60, 120 seconds take out.
前述共 28个样品， 这些样品的外观和实施例 1所获得石墨烯相同， SEM和 TEM测试 结果也相似。 BET测试结果如表 1所示。  A total of 28 samples were prepared as described above, and the appearance of these samples was the same as that of the graphene obtained in Example 1, and the SEM and TEM results were similar. The BET test results are shown in Table 1.
表 1 实施例 2石墨烯粉体 BET测试结果  Table 1 Example 2 Graphene powder BET test results
Figure imgf000008_0001
Figure imgf000008_0001
结果表明， 在 250°C热处理 120秒， BET高达 918.38 m2/g。 在不同温度和不同热处理时 间所获得的 BET都大于 500 m2/g， 在 560到 918 m2/g之间。 在 250和 350 °C热处理 10秒 并未测试， 是因为前躯体没有明显膨胀或发生颜色变化。 这表明在低温下热处理时间需要稍 长。 The results showed that the BET was as high as 918.38 m 2 /g after heat treatment at 250 ° C for 120 seconds. The BET obtained at different temperatures and different heat treatment times is greater than 500 m 2 /g, between 560 and 918 m 2 /g. Heat treatment at 250 and 350 °C for 10 seconds was not tested because the precursor did not swell significantly or undergo a color change. This indicates that the heat treatment time needs to be slightly longer at a low temperature.
图 4给出了在 550°C不同热处理时间得到的石墨烯粉体 BET随热处理时间的变化。 图 5 给出了不同温度热处理 30秒得到石墨烯粉体的 BET值和温度的关系。 图 4和图 5表明石墨 烯粉体的 BET和热处理温度和时间这两个因素相关。  Figure 4 shows the change in BET of graphene powder obtained at different heat treatment times at 550 °C with heat treatment time. Figure 5 shows the relationship between the BET value and the temperature of the graphene powder obtained by heat treatment at different temperatures for 30 seconds. Figures 4 and 5 show that the BET of the graphene powder is related to the heat treatment temperature and time.
图 6是所制得的石墨烯粉体在不同温度下得到的 XPS 图。 XPS结果表明， 不同温度下 所获得石墨烯粉体的含氧量均约为 7.2wt%。  Figure 6 is an XPS diagram of the obtained graphene powder obtained at different temperatures. The XPS results show that the oxygen content of the graphene powder obtained at different temperatures is about 7.2 wt%.
实施例 3 : 干法混合， 不同尿素添加量相同热处理温度制备掺杂石墨烯粉体 Example 3: Dry mixing, different urea addition amounts of the same heat treatment temperature to prepare doped graphene powder
( 1 ) 石墨烯前驱体的制备同实施例 1 ;  (1) The preparation of the graphene precursor is the same as in the first embodiment;
(2) 制备石墨烯粉体： 取 10g 石墨烯前驱体和不同质量尿素， 尿素质量分别为 0.1g、 0.3g、 0.5g、 0.7g、 lg、 2g 和 3g， 石墨烯前驱体和尿素的质量比为 100:1， 100:3， 100:5， 100:7， 100:10, 100:20 和 100:30。 在研钵中混合均匀， 然后置于长宽高为 400x400mmx200mm、 材质为不锈钢、 厚度为 0.5-2mm的非密封有盖坩埚中， 快速放 入 550°C的热处理炉中， 保温 30秒取出。 图 7显示的是不同尿素含量与所获得石墨烯粉体 BET 的关系图， 从图中可以看出， 随 着尿素含量升高， 所制备的石墨烯粉体 BET 值逐渐降低。 在石墨烯前驱体和尿素的质量比 为 100:10 时， BET为 609.3 m2/g， 在石墨烯前驱体和尿素的质量比为 100:20 时， BET为 524.2 m2/g。 图 8和 9显示的是实施例 3中不同尿素含量所获得的石墨烯粉体的 XPS图。 XPS结果 表明， 随着尿素含量增加， 掺入到石墨烯晶格中的氮含量也增加， 表 2列出了在热处理过程 中混入不同尿素后所获得石墨烯的掺氮量， 氮掺杂量可控制在 0.62 ％到 8.96 at.%。 当尿素 加入量增加时， 氮掺杂量也随之增加。 表 2 实施例 2不同尿素混合比下石墨烯氮掺杂量 (2) Preparation of graphene powder: 10 g of graphene precursor and different mass of urea, the urea mass is 0.1 g, respectively 0.3g, 0.5g, 0.7g, lg, 2g and 3g, the mass ratio of graphene precursor to urea is 100:1, 100:3, 100:5, 100:7, 100:10, 100:20 and 100 :30. It is evenly mixed in a mortar and then placed in a non-sealed lid with a length and width of 400x400mmx200mm, made of stainless steel and 0.5-2mm thick. It is quickly placed in a heat treatment furnace at 550 °C and taken out for 30 seconds. Figure 7 shows the relationship between the different urea contents and the BET of the graphene powder obtained. It can be seen from the figure that as the urea content increases, the BET value of the prepared graphene powder gradually decreases. When the mass ratio of the graphene precursor to urea is 100:10, the BET is 609.3 m 2 /g, and when the mass ratio of the graphene precursor to urea is 100:20, the BET is 524.2 m 2 /g. Figures 8 and 9 show XPS plots of graphene powders obtained for different urea contents in Example 3. XPS results show that as the urea content increases, the nitrogen content incorporated into the graphene crystal lattice also increases. Table 2 lists the nitrogen doping amount of the graphene obtained after mixing different ureas in the heat treatment process, and the nitrogen doping amount. It can be controlled from 0.62% to 8.96 at.%. As the amount of urea added increases, the amount of nitrogen doping also increases. Table 2 Example 2 graphene nitrogen doping amount under different urea mixing ratio
Figure imgf000009_0001
实施例 4: 湿法混合， 相同碳酸氢铵添加量不同热处理温度制备石墨烯粉体
Figure imgf000009_0001
Example 4: Wet mixing, the same amount of ammonium bicarbonate added to different heat treatment temperatures to prepare graphene powder
( 1 ) 石墨烯前驱体的制备过程同实施例 1 ;  (1) The preparation process of the graphene precursor is the same as in the first embodiment;
(2) 制备石墨烯粉体： 取 0.2g碳酸氢铵， 溶解在 1ml去离子水中， 将配置好的尿素溶液 加入到 2g石墨烯前驱体中， 搅拌混合均匀， 90°C真空干燥， 研磨得到尿素与石墨烯 前驱体复合粉体， 然后置于长宽高为 400x400mmx200mm、 材质为石墨、 厚度为 0.5- 2mm 的非密封有盖坩埚中， 之后快速放入 350°C、 450°C、 550°C、 650°C、 750°C、 850°C的热处理炉中热处理 30s。 图 10和 11分别给出 550°C热处理 30s所制备石墨烯的 TEM和 HRTEM照片， 结果表明 碳酸氢铵和石墨烯前驱体复合之后热处理并不影响石墨烯的微观形貌， 石墨烯的厚度也和实 施例 1和 2—样， 为 1-5个原子层。 结合 BET和 XPS的结果分析， 在尿素和石墨烯前驱体 复合之后热处理不仅能够在空气中进行， 而且能够实现石墨烯的可控氮掺杂。 表 3显示的是相同含量碳酸氢铵， 不同温度热处理所获得石墨烯粉体电导率。 从表 3可 以看出所制备的石墨烯粉体的电学性能优异， 电阻率在 0.02到 0.04 Ω·εηι， 同时 BET保持在 500 m2/g以上。 表 3 实施例 4石墨烯粉体性能表 (2) Preparation of graphene powder: Take 0.2g of ammonium bicarbonate, dissolve in 1ml of deionized water, add the prepared urea solution to 2g of graphene precursor, stir and mix evenly, vacuum dry at 90 °C, and grind The composite powder of urea and graphene precursor is placed in a non-sealed covered crucible with a length, width and height of 400x400mmx200mm, graphite and thickness of 0.5-2mm, and then quickly placed in 350°C, 450°C, 550°. C, heat treatment in 650 ° C, 750 ° C, 850 ° C heat treatment furnace for 30s. Figures 10 and 11 show TEM and HRTEM photographs of graphene prepared by heat treatment at 550 ° C for 30 s, respectively. The heat treatment after the ammonium hydrogencarbonate and the graphene precursor are combined does not affect the microscopic morphology of the graphene, and the thickness of the graphene is also 1-5 atomic layers as in the examples 1 and 2. Combined with the results of BET and XPS analysis, the heat treatment after urea and graphene precursor compounding can not only be carried out in air, but also can achieve controlled nitrogen doping of graphene. Table 3 shows the conductivity of graphene powder obtained by heat treatment at different temperatures for the same content of ammonium bicarbonate. It can be seen from Table 3 that the prepared graphene powder has excellent electrical properties, a specific resistance of 0.02 to 0.04 Ω·εηι, and a BET of 500 m 2 /g or more. Table 3 Example 4 graphene powder performance table
Figure imgf000010_0001
Figure imgf000010_0001

Claims

权利要求书 Claim
1. 一种在空气气氛中快速热处理制备石墨烯粉体方法， 为先将石墨烯的前驱体置于非密封 有盖坩埚中， 然后在空气气氛中进行热处理， 即得到石墨烯的粉体。 A method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere, wherein a graphene precursor is first placed in a non-sealed lid crucible, and then heat-treated in an air atmosphere to obtain a graphene powder.
2. 如权利要求 1 所述的一种在空气气氛中快速热处理制备石墨烯粉体方法， 其特征在于， 先将石墨烯前驱体与含氮化合物均匀混合后置于非密封有盖坩埚中， 然后进行热处理， 即得到氮掺杂的石墨烯粉体； 所述含氮化合物为尿素或铵盐。  2. The method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere according to claim 1, wherein the graphene precursor and the nitrogen-containing compound are uniformly mixed and then placed in a non-sealed lid. Then, heat treatment is performed to obtain a nitrogen-doped graphene powder; the nitrogen-containing compound is urea or an ammonium salt.
3. 如权利要求 1-2 任一所述的一种在空气气氛中快速热处理制备石墨烯粉体方法， 其特征 在于， 所述石墨烯前驱体为插层石墨， 即石墨层间***含氧官能团， 石墨层间距离增 力口； 所述含氧官能团为羟基、 羧基和环氧基。  3. The method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere according to any one of claims 1-2, wherein the graphene precursor is intercalated graphite, that is, intercalated between graphite layers. a functional group, a graphite interlayer distance increasing port; the oxygen-containing functional group is a hydroxyl group, a carboxyl group, and an epoxy group.
4. 如权利要求 1-2 任一所述的一种在空气气氛中快速热处理制备石墨烯粉体方法， 其特征 在于， 所述非密封有盖坩埚的材质选自石英、 碳化硅、 石墨和不锈钢， 坩埚的长 X宽 X高 尺寸为 50mmx50mmx20mm至 lj 400mmx400mmx200mm, 厚度为 0.5-2mm; 坩埚上有坩 埚盖， 正好盖住坩埚， 但没有密封。  The method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere according to any one of claims 1 to 2, wherein the non-sealed lid-shaped material is selected from the group consisting of quartz, silicon carbide, graphite, and Stainless steel, 长 long X width X high size is 50mmx50mmx20mm to lj 400mmx400mmx200mm, thickness is 0.5-2mm; 坩埚 has a 坩埚 cover, just cover the 坩埚, but no seal.
5. 如权利要求 2所述的一种在空气气氛中快速热处理制备石墨烯粉体方法， 其特征在于， 所述石墨烯前驱体与含氮化合物均匀混合的方式为干法混合或湿法混合； 所述干法混 合， 是将干燥的石墨烯前驱体和含氮化合物粉体充分搅拌混合； 所述的湿法混合是在石 墨烯前驱体水溶液中加入含氮化合物充分搅拌混合， 再烘干获得石墨烯前驱体和含氮化 合物的均匀混合粉体。  5. The method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere according to claim 2, wherein the graphene precursor and the nitrogen-containing compound are uniformly mixed by dry mixing or wet mixing. The dry mixing is to thoroughly mix and mix the dried graphene precursor and the nitrogen-containing compound powder; the wet mixing is to add a nitrogen-containing compound to the graphene precursor aqueous solution, stir and mix well, and then dry. A uniformly mixed powder of a graphene precursor and a nitrogen-containing compound is obtained.
6. 如权利要求 2所述的一种在空气气氛中快速热处理制备石墨烯粉体方法， 其特征在于， 所述铵盐选自碳酸铵和碳酸氢铵。  6. The method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere according to claim 2, wherein the ammonium salt is selected from the group consisting of ammonium carbonate and ammonium hydrogencarbonate.
7. 如权利要求 2所述的一种在空气气氛中快速热处理制备石墨烯粉体方法， 其特征在于， 所述石墨烯前驱体与含氮化合物质量之比为 100:1〜100:30。  7. The method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere according to claim 2, wherein a ratio of the mass of the graphene precursor to the nitrogen-containing compound is from 100:1 to 100:30.
8. 如权利要求 1-2 任一所述的一种在空气气氛中快速热处理制备石墨烯粉体方法， 其特征 在于， 所述热处理的温度为 250〜850°C， 时间为 10〜120秒； 所获得石墨烯的层数为 1_ 5层， 比表面积为 500〜918 m7g, 电阻率为 0. 02〜0. 04 Ω · cm。 The method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere according to any one of claims 1 to 2, wherein the heat treatment temperature is 250 to 850 ° C, and the time is 10 to 120 seconds. ; graphene layers is obtained 1_ layer 5, a specific surface area of 500~918 m7g, the resistivity of 0. 02~0 04 Ω · cm..
9. 如权利要求 2 所述的一种在空气气氛中快速热处理制备石墨烯粉体方法， 其特征在于， 所获得的石墨烯产品氮掺杂量， 即石墨烯产品中氮原子占石墨烯产品总原子量的比例， 控制在 0. 62〜8. 96 at. %。  9. The method for rapidly preparing a graphene powder by rapid heat treatment in an air atmosphere according to claim 2, wherein the obtained graphene product has a nitrogen doping amount, that is, a nitrogen atom in the graphene product accounts for a graphene product. The ratio of the total atomic weight is controlled at 0. 62~8. 96 at. %.
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