WO2016197516A1 - Method of industrially preparing graphene-coated nano aluminum powder or nano magnesium powder - Google Patents

Method of industrially preparing graphene-coated nano aluminum powder or nano magnesium powder Download PDF

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WO2016197516A1
WO2016197516A1 PCT/CN2015/092417 CN2015092417W WO2016197516A1 WO 2016197516 A1 WO2016197516 A1 WO 2016197516A1 CN 2015092417 W CN2015092417 W CN 2015092417W WO 2016197516 A1 WO2016197516 A1 WO 2016197516A1
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nano
graphene
powder
rate
aluminum powder
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PCT/CN2015/092417
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French (fr)
Chinese (zh)
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张利强
李永峰
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中国石油大学(北京)
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions

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  • the invention relates to a method for improving the oxidation resistance of graphene coated nano aluminum powder or nano magnesium powder, and belongs to the technical field of corrosion resistance.
  • nano aluminum powder has been widely used in aerospace, chemical, metallurgy (aluminum metallurgy, steelmaking deoxidizer), shipbuilding (conductive coating), refractory materials (magnesium carbon brick for steelmaking furnace), new building materials, anti-corrosion materials, etc. .
  • nano-magnesium powder can be widely used to prepare reducing agent, make flash powder, light alloy raw material, metallurgical desulfurizer, deoxidizer, optical mirror, manufacture magnesium salt, manufacture Grignard reagent, spectrum analysis, etc. Manufacturing raw materials for automobiles, airplanes and rockets.
  • the surface of the nano aluminum powder or the nano magnesium powder easily forms an aluminum oxide or magnesium oxide passivation film in the air, the performance in the composite material is greatly reduced. Therefore, how to effectively inhibit the formation of aluminum oxide or magnesium oxide passivation film on the surface of nano aluminum powder is the key to the large-scale application research of nano aluminum powder and magnesium powder.
  • an object of the present invention is to provide a method for industrially preparing graphene-coated nano aluminum powder or nano magnesium powder to improve its oxidation resistance, and the graphene protective film in the method can effectively suppress nano aluminum
  • the formation of passivation film on the surface of powder or nano-magnesium powder can effectively solve the surface oxidation problem of nano-aluminum powder or nano-magnesium powder.
  • the present invention provides a method for industrially preparing graphene-coated nano-aluminum powder or nano-magnesium powder, the method comprising the following steps:
  • the graphene is dissolved in an organic solvent to prepare a graphene dispersion, and the graphene dispersion is subjected to vacuum treatment to a degree of vacuum higher than 10 ⁇ 2 Pa, wherein the graphene accounts for the total graphene dispersion 1%-99% of weight;
  • nano-aluminum powder or nano-magnesium powder to the vacuum-treated graphene dispersion in an inert atmosphere, stirring for 30min-100min, vacuuming, to a vacuum of more than 10 -2 Pa, to remove the solution a bubble to obtain a crude product, wherein the nano aluminum powder or nano magnesium powder accounts for 1% to 99% of the total weight of the crude product, and the stirring speed is 600 rpm to 3000 rpm;
  • the graphene accounts for 1% to 20% by weight based on the total weight of the graphene dispersion.
  • the nano aluminum powder or the nano magnesium powder is added to the vacuum-treated graphene dispersion at a rate of 0.1 mg/min to 100 mg/min.
  • the nano aluminum powder or the nano magnesium powder accounts for 1% to 20% of the total weight of the crude product.
  • the organic solvent to be used includes an organic solvent containing an unsaturated bond.
  • the organic solvent containing an unsaturated bond is used, including an aqueous solution of polyvinyl alcohol, an aqueous solution of polyacrylic acid or an aqueous solution of N-methylpyrrolidone; more preferably, a concentration of an aqueous solution of polyvinyl alcohol used. More than 90% by weight; the concentration of the aqueous solution of polyacrylic acid used is higher than 90% by weight; the concentration of the aqueous solution of N-methylpyrrolidone (Sinopharm Chemical Co., Ltd.) is higher than 90% by weight.
  • the nano aluminum powder or the nano magnesium powder used is subjected to a concentration of 0.01 mol/L to 1 mol/L of hydrochloric acid or a concentration of 0.01 mol/L to 1 mol/L before use. Treated with sodium hydroxide solution.
  • the nano aluminum powder or the nano magnesium powder used is produced by Beijing Deke Island Gold Technology Co., Ltd., and is kept sealed before being used.
  • the vacuum-treated graphene dispersion is kept in a stirring state.
  • the vacuum-treated graphene dispersion is maintained in a high-speed stirring state to avoid agglomeration of graphene.
  • the high temperature heat treatment comprises the following steps:
  • the container containing the crude product is vacuumed until the vacuum is higher than 10 -2 Pa, then hydrogen is introduced at a rate of 50 mL / min, while nitrogen is introduced at a rate of 300 mL / min, and the aeration time is 15 min;
  • Argon is introduced at a rate of from 100 mL/min to 500 mL/min (more preferably, at 300 mL/min) while hydrogen is introduced at a rate of 10 mL/min to 50 mL/min, more preferably at 35 mL/min.
  • the high temperature heat treatment is completed until cooling to room temperature.
  • the heating rate of the heating is 5 ° C / min - 20 ° C / min, More preferably, the rate of temperature increase is 12 ° C / min.
  • the cooling rate of the cooling is 5 ° C / min - 20 ° C / min, and more preferably, the cooling rate is 10 ° C / min.
  • the hydrothermal treatment comprises the following steps:
  • the crude product is incubated at 90 ° C - 120 ° C for 8 hours to 24 hours, and subjected to a drying treatment to complete the hydrothermal treatment.
  • the graphene used in the present invention is prepared by the conventional Hummers method, and specifically includes the following steps:
  • the solid was dried under vacuum to obtain graphene.
  • the graphene protective film formed by the method for industrially preparing graphene coated nano aluminum powder or nano magnesium powder provided by the method of the invention can effectively inhibit the formation of surface passivation film of nano aluminum powder or nano magnesium powder, and effectively solve the nano aluminum powder. Or surface oxidation problems when the nano-magnesium powder is exposed to air.
  • the method provided by the invention has low raw material price and simple modification method, especially in the process of coating graphene, a series of avoiding contact with air and uniformly coating graphene onto the surface of nano aluminum powder or nano magnesium powder. Process steps such as:
  • Vacuuming the graphene dispersion before incorporation of nano-aluminum powder or nano-magnesium powder can effectively remove the dissolved air in the solution and prevent the nano-aluminum powder or nano-magnesium powder from being oxidized;
  • the surface of the surface is treated with dilute hydrochloric acid or sodium hydroxide solution before using nano aluminum powder or nano magnesium powder to completely remove the oxide layer on the surface;
  • 1a is a schematic view showing the structure of the graphene-coated nano-aluminum powder of Example 1.
  • 1b is a schematic view showing the structure of the graphene-coated nano-magnesium powder of Example 1.
  • Example 2 is a transmission electron micrograph of the graphene-coated nano-aluminum powder of Example 1.
  • Example 3 is an X-ray diffraction curve of the graphene-coated nano aluminum powder of Example 1 and the uncoated nano aluminum powder.
  • 4b is an impedance test curve of the graphene-coated nano-magnesium powder and the graphene-free coated nano-magnesium powder sample of Example 3.
  • This embodiment provides a method for coating graphene-coated nano aluminum powder, the method comprising the following steps:
  • Graphene is prepared by the traditional Hummers method, and includes the following steps:
  • the round bottom reaction bottle is installed in an ice water bath, an appropriate amount of concentrated sulfuric acid is added, and a mixture of 4 g of graphite powder and 2 g of sodium nitrate is added under stirring;
  • the prepared graphene (10 mg) was then rapidly stirred (1000 r/min) in an aqueous polyvinyl alcohol solution (100 mL) to prepare a graphene dispersion, which was evacuated to remove dissolved air in the liquid.
  • nano aluminum powder was added to the prepared 200 mL graphene dispersion at a rate of 1 mg/min and rapidly stirred (1000 r/min) to form a crude product, and the dissolved air in the liquid was removed by vacuuming, wherein the nano aluminum
  • the powder should be treated with dilute hydrochloric acid or sodium hydroxide before adding the graphene mixture to ensure complete removal of the surface trioxide.
  • Aluminum passivation film
  • the crude product was placed in a quartz reactor, and the reactor was pushed to the center of the reaction chamber, the vacuum pump was turned on, and then hydrogen gas was introduced at a rate of 50 mL/min, and nitrogen gas was introduced at a rate of 300 mL/min;
  • the quartz reactor is heated to 400-700 ° C during the graphene growth process and maintained for 30 min, and hydrogen gas is introduced thereto at a rate of 35 mL / min for 20-60 min, wherein the heating rate of heating is 12 ° C / min;
  • the graphene-coated nano-aluminum powder and the graphene-free coated nano-aluminum powder sample prepared in this example were respectively heated at 100 ° C for 30 min in an air atmosphere, and the results showed that the nano-aluminum of the present example was obtained.
  • the powder has almost no change, and the surface of the nano-aluminum powder coated with graphene is whitened, and it is aluminum oxide measured by XRD.
  • the graphene-coated nano-aluminum powder of this embodiment and the X-coated aluminum powder are not coated.
  • the ray diffraction curve is shown in Fig. 3.
  • the content shown in Fig. 3 indicates that the graphene coating layer can effectively improve the oxidation resistance of the nano aluminum powder.
  • This embodiment provides a method for coating graphene-coated nano aluminum powder, the method comprising the following steps:
  • Graphene is prepared by the traditional Hummers method, the specific method is the same as the embodiment 1;
  • nano aluminum powder was added to the prepared 100 mL graphene dispersion at a rate of 2 mg/min, and rapidly stirred (2000 r/min) to form a crude product, which was evacuated to remove dissolved air in the liquid.
  • the nano aluminum powder is treated with dilute hydrochloric acid or sodium hydroxide before adding the graphene mixture to ensure complete removal of the surface aluminum oxide passivation film.
  • the crude product was placed in a hydrothermal reaction vessel, and incubated in an oven at 90 ° C for 12 hours, and dried to obtain a nano-aluminum powder coated with graphene.
  • the graphene-coated nano aluminum powder prepared in this example and the graphene-free coated nano aluminum powder sample were respectively placed in 0.1 mol/L diluted hydrochloric acid for 1 hour, and the nanometer of the present example was found. Almost no change in aluminum powder, The graphene-free nano-aluminum powder produced a large number of bubbles and eventually disappeared completely, indicating that the graphene coating layer can effectively improve the antioxidant capacity of the nano-aluminum powder.
  • This embodiment provides a method for coating graphene-coated nano-magnesium powder, the method comprising the following steps:
  • Graphene is prepared by the traditional Hummers method, and includes the following steps:
  • the round bottom reaction bottle is installed in an ice water bath, an appropriate amount of concentrated sulfuric acid is added, and a mixture of 4 g of graphite powder and 2 g of sodium nitrate is added under stirring;
  • the prepared graphene (10 mg) was then rapidly stirred (1000 r/min) in an aqueous polyvinyl alcohol solution (100 mL) to prepare a graphene dispersion, which was evacuated to remove dissolved air in the liquid.
  • nano aluminum powder was added to the prepared 200 mL graphene dispersion at a rate of 1 mg/min and rapidly stirred (1000 r/min) to form a crude product, and vacuum was used to remove dissolved air in the liquid, wherein, nano magnesium
  • the powder is treated with dilute hydrochloric acid or sodium hydroxide before adding the graphene mixture to ensure complete removal of the surface magnesium oxide passivation film.
  • the crude product was placed in a quartz reactor, and the reactor was pushed to the center of the reaction chamber, the vacuum pump was turned on, and then hydrogen gas was introduced at a rate of 50 mL/min, and nitrogen gas was introduced at a rate of 300 mL/min;
  • the quartz reactor is heated to 400-700 ° C during the graphene growth process and maintained for 30 mins, and hydrogen gas is introduced thereto at a rate of 35 mL / min for 20-60 min, wherein the heating rate of heating is 12 ° C / min;
  • argon gas was introduced at a rate of 300 mL/min, and hydrogen gas was introduced at a rate of 35 mL/min until cooling to room temperature, and the rate of cooling was 10 ° C/min, to obtain a surface-coated graphene-containing nano-magnesium powder.
  • the structure is shown in Figure 1b.
  • the graphene-coated nano-magnesium powder prepared in this example and the graphene-free coated nano-magnesium powder sample were respectively polarized and impedance tested. The results are shown in Fig. 4a and Fig. 4b, and the results are shown.
  • the nano-magnesium powder of the present embodiment has stronger corrosion resistance than the graphene-free nano-magnesium powder.

Abstract

Disclosed is a method of preparing graphene-coated nano aluminum powder or nano magnesium powder, comprising: dissolving a graphene in an organic solvent to prepare a graphene dispersion, applying vacuum to the graphene dispersion until the vacuum level is greater than 10-2 Pa, wherein the graphene accounts for 1-99% by weight of the total weight of the graphene dispersion; adding the vacuumed graphene dispersion into nano aluminum powder or nano magnesium powder in an inert atmosphere, stirring for 30-100 minutes, and applying vacuum to the mixture until the vacuum level is greater than 10-2 Pa to obtain a raw product, wherein the nano aluminum powder or the nano magnesium powder accounts for 1-99% by weight of the total weight of the raw product, and the stirring speed is 600-3000 revolution per minute; performing a high-temperature heat treatment or hydrothermal treatment on the raw product to complete coating of the graphene onto the nano aluminum powder or nano magnesium powder. The present manufacturing method can inhibit the formation of a passivation film on the surface of the nano aluminum powder or nano magnesium powder effectively, thus solving the problem in which the surface of the nano aluminum powder or nano magnesium powder is oxidized easily.

Description

一种工业化制备石墨烯包覆纳米铝粉或纳米镁粉的方法Method for industrially preparing graphene coated nano aluminum powder or nano magnesium powder 技术领域Technical field
本发明涉及一种应用石墨烯包覆纳米铝粉或者纳米镁粉提高其抗氧化能力的方法，属于抗腐蚀技术领域。The invention relates to a method for improving the oxidation resistance of graphene coated nano aluminum powder or nano magnesium powder, and belongs to the technical field of corrosion resistance.
背景技术Background technique
如今，纳米铝粉已经广泛应用于航天、化工、冶金(铝热法冶金、炼钢脱氧剂)、造船(导电涂料)、耐火材料(炼钢炉镁碳砖)、新型建材、防腐材料等领域。而纳米镁粉由于其高活性，可广泛应用制备还原剂，制造闪光粉，轻质合金原料，冶金脱硫剂、脱氧剂、光学镜，制造镁盐，制造格氏试剂，光谱分析等，并可为汽车、飞机、火箭制造原料。然而，由于纳米铝粉或者纳米镁粉表面在空气中极易形成三氧化二铝或者氧化镁钝化膜，大大降低了其在复合材料里的性能。因此，如何有效抑制纳米铝粉表面三氧化二铝或者氧化镁钝化膜的形成是当今纳米铝粉及镁粉大规模应用研究的关键。Nowadays, nano aluminum powder has been widely used in aerospace, chemical, metallurgy (aluminum metallurgy, steelmaking deoxidizer), shipbuilding (conductive coating), refractory materials (magnesium carbon brick for steelmaking furnace), new building materials, anti-corrosion materials, etc. . Due to its high activity, nano-magnesium powder can be widely used to prepare reducing agent, make flash powder, light alloy raw material, metallurgical desulfurizer, deoxidizer, optical mirror, manufacture magnesium salt, manufacture Grignard reagent, spectrum analysis, etc. Manufacturing raw materials for automobiles, airplanes and rockets. However, since the surface of the nano aluminum powder or the nano magnesium powder easily forms an aluminum oxide or magnesium oxide passivation film in the air, the performance in the composite material is greatly reduced. Therefore, how to effectively inhibit the formation of aluminum oxide or magnesium oxide passivation film on the surface of nano aluminum powder is the key to the large-scale application research of nano aluminum powder and magnesium powder.
但是，针对上述问题，目前还未有比较理想的解决办法。因此，探索一种制备工艺简单，成本低廉，解决纳米铝粉或者纳米镁粉表面氧化问题的方法显得尤为重要。However, there is currently no ideal solution to the above problems. Therefore, it is particularly important to explore a method that is simple in preparation process and low in cost, and solves the problem of surface oxidation of nano aluminum powder or nano magnesium powder.
发明内容Summary of the invention
为了解决上述技术问题，本发明的目的在于提供一种工业化制备石墨烯包覆纳米铝粉或者纳米镁粉以提高其抗氧化能力的方法，该方法中的石墨烯保护膜可以有效地抑制纳米铝粉或者纳米镁粉表面钝化膜的形成，有效解决纳米铝粉或者纳米镁粉的表面氧化问题。In order to solve the above technical problems, an object of the present invention is to provide a method for industrially preparing graphene-coated nano aluminum powder or nano magnesium powder to improve its oxidation resistance, and the graphene protective film in the method can effectively suppress nano aluminum The formation of passivation film on the surface of powder or nano-magnesium powder can effectively solve the surface oxidation problem of nano-aluminum powder or nano-magnesium powder.
为了达到上述目的，本发明提供了一种工业化制备石墨烯包覆纳米铝粉或纳米镁粉的方法，该方法包括以下步骤：In order to achieve the above object, the present invention provides a method for industrially preparing graphene-coated nano-aluminum powder or nano-magnesium powder, the method comprising the following steps:
将石墨烯溶于有机溶剂中，制成石墨烯分散液，对石墨烯分散液进行抽真空处理，至真空度高于10-2Pa，其中，所述石墨烯占所述石墨烯分散液总重量的1％-99％；The graphene is dissolved in an organic solvent to prepare a graphene dispersion, and the graphene dispersion is subjected to vacuum treatment to a degree of vacuum higher than 10 −2 Pa, wherein the graphene accounts for the total graphene dispersion 1%-99% of weight;
在惰性气氛中，向经过抽真空处理的石墨烯分散液中加入纳米铝粉或者纳米镁粉，搅拌30min-100min后，进行抽真空处理，至真空度高于10-2Pa，以去除溶液里气泡，得到粗产品，其中，所述纳米铝粉或者纳米镁粉占所述粗产品总重量的1％-99％，所述搅拌的速度为600转/分-3000转/分；Adding nano-aluminum powder or nano-magnesium powder to the vacuum-treated graphene dispersion in an inert atmosphere, stirring for 30min-100min, vacuuming, to a vacuum of more than 10 -2 Pa, to remove the solution a bubble to obtain a crude product, wherein the nano aluminum powder or nano magnesium powder accounts for 1% to 99% of the total weight of the crude product, and the stirring speed is 600 rpm to 3000 rpm;
对所述粗产品进行高温热处理或水热处理，完成石墨烯对纳米铝粉或纳米镁粉的包 覆。Performing high temperature heat treatment or hydrothermal treatment on the crude product to complete the package of graphene to nano aluminum powder or nano magnesium powder cover.
在本发明提供的上述方法中，优选地，所述石墨烯占所述石墨烯分散液总重量的1％-20％。In the above method provided by the present invention, preferably, the graphene accounts for 1% to 20% by weight based on the total weight of the graphene dispersion.
在本发明提供的上述方法中，优选地，以0.1mg/min-100mg/min的速度向经过抽真空处理的石墨烯分散液中加入所述纳米铝粉或者纳米镁粉。In the above method provided by the present invention, preferably, the nano aluminum powder or the nano magnesium powder is added to the vacuum-treated graphene dispersion at a rate of 0.1 mg/min to 100 mg/min.
在本发明提供的上述方法中，优选地，所述纳米铝粉或者纳米镁粉占所述粗产品总重量的1％-20％。In the above method provided by the present invention, preferably, the nano aluminum powder or the nano magnesium powder accounts for 1% to 20% of the total weight of the crude product.
在本发明提供的上述方法中，优选地，采用的有机溶剂包括含有不饱和键的有机溶剂。In the above method provided by the present invention, preferably, the organic solvent to be used includes an organic solvent containing an unsaturated bond.
在本发明提供的上述方法中，优选地，采用的含有不饱和键的有机溶剂包括聚乙烯醇水溶液、聚丙烯酸水溶液或N-甲基吡咯烷酮水溶液；更优选地，采用的聚乙烯醇水溶液的浓度高于90wt％；采用的聚丙烯酸水溶液的浓度高于90wt％；采用的N-甲基吡咯烷酮水溶液(国药集团化学试剂有限公司)的浓度高于90wt％。In the above method provided by the present invention, preferably, the organic solvent containing an unsaturated bond is used, including an aqueous solution of polyvinyl alcohol, an aqueous solution of polyacrylic acid or an aqueous solution of N-methylpyrrolidone; more preferably, a concentration of an aqueous solution of polyvinyl alcohol used. More than 90% by weight; the concentration of the aqueous solution of polyacrylic acid used is higher than 90% by weight; the concentration of the aqueous solution of N-methylpyrrolidone (Sinopharm Chemical Co., Ltd.) is higher than 90% by weight.
在本发明提供的上述方法中，优选地，采用的纳米铝粉或者纳米镁粉在使用前先经浓度为0.01mol/L-1mol/L的盐酸或浓度为0.01mol/L-1mol/L的氢氧化钠溶液处理。In the above method provided by the present invention, preferably, the nano aluminum powder or the nano magnesium powder used is subjected to a concentration of 0.01 mol/L to 1 mol/L of hydrochloric acid or a concentration of 0.01 mol/L to 1 mol/L before use. Treated with sodium hydroxide solution.
在本发明中，采用的纳米铝粉或者纳米镁粉为北京德科岛金科技有限公司生产的，未使用前保持密封状态。In the present invention, the nano aluminum powder or the nano magnesium powder used is produced by Beijing Deke Island Gold Technology Co., Ltd., and is kept sealed before being used.
在本发明提供的上述方法中，优选地，向经过抽真空处理的石墨烯分散液中加入纳米铝粉或者纳米镁粉时，保持经过抽真空处理的石墨烯分散液处于搅拌状态。In the above method provided by the present invention, preferably, when the nano-aluminum powder or the nano-magnesium powder is added to the vacuum-treated graphene dispersion, the vacuum-treated graphene dispersion is kept in a stirring state.
根据本发明的具体实施方式，保持经过抽真空处理的石墨烯分散液处于高速搅拌状态，以避免石墨烯发生团聚。According to a specific embodiment of the present invention, the vacuum-treated graphene dispersion is maintained in a high-speed stirring state to avoid agglomeration of graphene.
在本发明提供的上述方法中，优选地，高温热处理包括以下步骤：In the above method provided by the present invention, preferably, the high temperature heat treatment comprises the following steps:
对装有粗产品的容器进行抽真空处理，至真空度高于10-2Pa，然后以50mL/min的速率通入氢气，同时以300mL/min的速率通入氮气，通气时间为15min；The container containing the crude product is vacuumed until the vacuum is higher than 10 -2 Pa, then hydrogen is introduced at a rate of 50 mL / min, while nitrogen is introduced at a rate of 300 mL / min, and the aeration time is 15 min;
加热至400℃-700℃，维持10min-30min，并且在达到加热温度时以10mL/min-50mL/min(更优选地，以35mL/min)的速率通入氢气20min-60min；Heating to 400 ° C -700 ° C, maintaining 10min-30min, and reaching the heating temperature at a rate of 10mL / min -50mL / min (more preferably, at 35mL / min) into the hydrogen for 20min-60min;
以100mL/min-500mL/min(更优选地，以300mL/min)的速率通入氩气，同时以10mL/min-50mL/min(更优选地，以35mL/min)的速率通入氢气，直到冷却到室温，完成所述高温热处理。Argon is introduced at a rate of from 100 mL/min to 500 mL/min (more preferably, at 300 mL/min) while hydrogen is introduced at a rate of 10 mL/min to 50 mL/min, more preferably at 35 mL/min. The high temperature heat treatment is completed until cooling to room temperature.
在本发明提供的上述方法中，优选地，所述加热的升温速率为5℃/min-20℃/min， 更优选地，升温速率为12℃/min。In the above method provided by the present invention, preferably, the heating rate of the heating is 5 ° C / min - 20 ° C / min, More preferably, the rate of temperature increase is 12 ° C / min.
在本发明提供的上述方法中，优选地，所述冷却的降温速率为5℃/min-20℃/min，更优选地，降温速率为10℃/min。In the above method provided by the present invention, preferably, the cooling rate of the cooling is 5 ° C / min - 20 ° C / min, and more preferably, the cooling rate is 10 ° C / min.
在本发明提供的上述方法中，优选地，所述水热处理包括以下步骤：In the above method provided by the present invention, preferably, the hydrothermal treatment comprises the following steps:
在90℃-120℃下对所述粗产品保温8小时-24小时，经过干燥处理，完成所述水热处理。The crude product is incubated at 90 ° C - 120 ° C for 8 hours to 24 hours, and subjected to a drying treatment to complete the hydrothermal treatment.
本发明中采用的石墨烯是通过传统Hummers方法制备得到的，具体包括以下步骤：The graphene used in the present invention is prepared by the conventional Hummers method, and specifically includes the following steps:
搅拌状态下，向适量的浓硫酸中加入4g石墨粉和2g硝酸钠的混合物；Agitating a mixture of 4 g of graphite powder and 2 g of sodium nitrate in an appropriate amount of concentrated sulfuric acid;
分次加入15g高锰酸钾，快速搅拌并控制反应温度不超过20℃，然后升温到35℃左右，继续搅拌30min，缓慢加入适量的水，搅拌20min后，加入适量双氧水还原残留的氧化剂，使溶液变为亮黄色；Add 15g potassium permanganate in portions, stir rapidly and control the reaction temperature not to exceed 20 °C, then raise the temperature to about 35 °C, continue stirring for 30min, slowly add appropriate amount of water, stir for 20min, add appropriate amount of hydrogen peroxide to reduce residual oxidant, so that The solution turned bright yellow;
趁热过滤，并用质量浓度为5wt％的HCl溶液和去离子水洗涤直到滤液中无硫酸根为止；Filtered hot, and washed with 5% by weight HCl solution and deionized water until there is no sulfate in the filtrate;
将固体真空干燥，即得到石墨烯。The solid was dried under vacuum to obtain graphene.
本发明方法提供的工业化制备石墨烯包覆纳米铝粉或纳米镁粉的方法所形成的石墨烯保护膜可以有效地抑制纳米铝粉或者纳米镁粉表面钝化膜的形成，有效解决纳米铝粉或者纳米镁粉暴露在空气时的表面氧化问题。另外，本发明提供的方法采用的原料价格低廉，改性方法简便，尤其在包覆石墨烯的过程中设计了一系列避免接触空气及使石墨烯均匀包覆到纳米铝粉或者纳米镁粉表面的工艺步骤，如：The graphene protective film formed by the method for industrially preparing graphene coated nano aluminum powder or nano magnesium powder provided by the method of the invention can effectively inhibit the formation of surface passivation film of nano aluminum powder or nano magnesium powder, and effectively solve the nano aluminum powder. Or surface oxidation problems when the nano-magnesium powder is exposed to air. In addition, the method provided by the invention has low raw material price and simple modification method, especially in the process of coating graphene, a series of avoiding contact with air and uniformly coating graphene onto the surface of nano aluminum powder or nano magnesium powder. Process steps such as:
1、掺入纳米铝粉或者纳米镁粉前对石墨烯分散液进行抽真空处理，可有效去除溶液里面溶解的空气，防止纳米铝粉或者纳米镁粉被氧化；1. Vacuuming the graphene dispersion before incorporation of nano-aluminum powder or nano-magnesium powder can effectively remove the dissolved air in the solution and prevent the nano-aluminum powder or nano-magnesium powder from being oxidized;
2、在使用纳米铝粉或者纳米镁粉前利用稀盐酸或氢氧化钠溶液对其表面进行处理，完全去除表面的氧化层；2. The surface of the surface is treated with dilute hydrochloric acid or sodium hydroxide solution before using nano aluminum powder or nano magnesium powder to completely remove the oxide layer on the surface;
3、在惰性气体保护氛围下加入纳米铝粉或者纳米镁粉，可有效防止纳米铝粉或者纳米镁粉被氧化；3. Adding nano aluminum powder or nano magnesium powder under inert gas protection atmosphere can effectively prevent nano aluminum powder or nano magnesium powder from being oxidized;
4、加入纳米铝粉或者纳米镁粉过程中进行高速搅拌，使石墨烯与纳米铝粉或者纳米镁粉充分接触，并且在高速搅拌过程中可使石墨烯褶皱将纳米铝粉或者纳米镁粉完全包覆。4. High-speed stirring during the process of adding nano-aluminum powder or nano-magnesium powder, making graphene fully contact with nano-aluminum powder or nano-magnesium powder, and making graphene wrinkles complete nano-aluminum powder or nano-magnesium powder during high-speed stirring. Coated.
附图说明DRAWINGS
图1a为实施例1的石墨烯包覆纳米铝粉的结构示意图。 1a is a schematic view showing the structure of the graphene-coated nano-aluminum powder of Example 1.
图1b为实施例1的石墨烯包覆纳米镁粉的结构示意图。1b is a schematic view showing the structure of the graphene-coated nano-magnesium powder of Example 1.
图2为实施例1的石墨烯包覆纳米铝粉的透射电子显微图。2 is a transmission electron micrograph of the graphene-coated nano-aluminum powder of Example 1.
图3为实施例1的石墨烯包覆纳米铝粉与未包覆纳米铝粉的X射线衍射曲线。3 is an X-ray diffraction curve of the graphene-coated nano aluminum powder of Example 1 and the uncoated nano aluminum powder.
图4a为实施例3的石墨烯包覆的纳米镁粉与无石墨烯包覆纳米镁粉样品的极化曲线。4a is a polarization curve of the graphene-coated nano-magnesium powder and the graphene-free coated nano-magnesium powder sample of Example 3.
图4b为实施例3的石墨烯包覆的纳米镁粉与无石墨烯包覆纳米镁粉样品的阻抗测试曲线。4b is an impedance test curve of the graphene-coated nano-magnesium powder and the graphene-free coated nano-magnesium powder sample of Example 3.
具体实施方式detailed description
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。The detailed description of the technical features, the advantages and the advantages of the present invention will be understood by the following detailed description of the invention.
实施例1Example 1
本实施例提供了一种石墨烯包覆纳米铝粉的方法，该方法包括以下步骤：This embodiment provides a method for coating graphene-coated nano aluminum powder, the method comprising the following steps:
(1)石墨烯的制备及溶解(1) Preparation and dissolution of graphene
石墨烯采用传统Hummers方法制备，具体包括以下步骤：Graphene is prepared by the traditional Hummers method, and includes the following steps:
在冰水浴中安装好圆底反应瓶，加入适量的浓硫酸，搅拌状态下加入4g石墨粉和2g硝酸钠的混合物；The round bottom reaction bottle is installed in an ice water bath, an appropriate amount of concentrated sulfuric acid is added, and a mixture of 4 g of graphite powder and 2 g of sodium nitrate is added under stirring;
分次加入15g高锰酸钾，快速搅拌并控制反应温度不超过20℃，升温到35℃左右，继续搅拌30min，再缓慢加入适量去离子水，搅拌20min后，加入适量双氧水还原残留的氧化剂，使溶液变为亮黄色；Add 15g potassium permanganate in several portions, stir rapidly and control the reaction temperature not to exceed 20 °C, heat up to about 35 °C, continue stirring for 30min, then slowly add appropriate amount of deionized water, stir for 20min, add appropriate amount of hydrogen peroxide to reduce residual oxidant, Make the solution bright yellow;
趁热过滤，并用质量浓度为5wt％的HCl溶液和去离子水洗涤直到滤液中无硫酸根为止；Filtered hot, and washed with 5% by weight HCl solution and deionized water until there is no sulfate in the filtrate;
将滤饼置于真空干燥箱中充分干燥，得到氧化石墨烯，再加入适量还原剂使其还原成石墨烯；Drying the filter cake in a vacuum drying oven to obtain graphene oxide, and then adding an appropriate amount of reducing agent to reduce it to graphene;
然后将制备好的石墨烯(10mg)加入聚乙烯醇水溶液(100mL)中快速搅拌(1000r/min)，制备成石墨烯分散液，并将其抽真空去除液体中溶解的空气。The prepared graphene (10 mg) was then rapidly stirred (1000 r/min) in an aqueous polyvinyl alcohol solution (100 mL) to prepare a graphene dispersion, which was evacuated to remove dissolved air in the liquid.
(2)石墨烯包覆纳米铝粉(2) Graphene coated nano aluminum powder
在手套箱内，向制备好的200mL石墨烯分散液中以1mg/min速度加入10mg纳米铝粉并快速搅拌(1000r/min)形成粗产品，抽真空去除液体中溶解的空气，其中，纳米铝粉在加入石墨烯混合液之前需经稀盐酸或氢氧化钠处理，以保证完全去除表面三氧化二 铝钝化膜。In the glove box, 10 mg of nano aluminum powder was added to the prepared 200 mL graphene dispersion at a rate of 1 mg/min and rapidly stirred (1000 r/min) to form a crude product, and the dissolved air in the liquid was removed by vacuuming, wherein the nano aluminum The powder should be treated with dilute hydrochloric acid or sodium hydroxide before adding the graphene mixture to ensure complete removal of the surface trioxide. Aluminum passivation film.
(3)高温热处理(3) High temperature heat treatment
将粗产品放入石英反应器中，并将反应器推送到反应室中央，打开真空泵，然后同时以50mL/min的速率通入氢气，以300mL/min的速率通入氮气；The crude product was placed in a quartz reactor, and the reactor was pushed to the center of the reaction chamber, the vacuum pump was turned on, and then hydrogen gas was introduced at a rate of 50 mL/min, and nitrogen gas was introduced at a rate of 300 mL/min;
石英反应器在石墨烯生长过程中加热到400-700℃并维持30min，并且以35mL/min的速率向其中通入氢气20-60min，其中，加热的升温速率为12℃/min；The quartz reactor is heated to 400-700 ° C during the graphene growth process and maintained for 30 min, and hydrogen gas is introduced thereto at a rate of 35 mL / min for 20-60 min, wherein the heating rate of heating is 12 ° C / min;
结束时，以300mL/min的速率通入氩气，以35mL/min的速率通入氢气，直到冷却到室温，冷却的速率为10℃/min，得到表面包覆石墨烯的纳米铝粉，其结构如图1a所示。通过透射电镜观察发现石墨烯通过此方法可均匀包覆到纳米铝粉表面，如图2所示。At the end, argon gas was introduced at a rate of 300 mL/min, and hydrogen gas was introduced at a rate of 35 mL/min until cooling to room temperature, and the cooling rate was 10 ° C/min, to obtain a surface-coated graphene-containing nano aluminum powder. The structure is shown in Figure 1a. It was found by transmission electron microscopy that graphene can be uniformly coated onto the surface of the nano-aluminum powder by this method, as shown in FIG.
在相同的测试条件下，本实施例制得的石墨烯包覆的纳米铝粉与无石墨烯包覆纳米铝粉样品分别在100℃、空气气氛下加热30min，结果显示本实施例的纳米铝粉几乎没有变化，而无石墨烯包覆的纳米铝粉表面则变白，通过XRD测量其为三氧化二铝，本实施例的石墨烯包覆纳米铝粉与未包覆纳米铝粉的X射线衍射曲线如图3所示，图3中所显示的内容表明石墨烯包覆层确实可有效提高纳米铝粉抗氧化能力。Under the same test conditions, the graphene-coated nano-aluminum powder and the graphene-free coated nano-aluminum powder sample prepared in this example were respectively heated at 100 ° C for 30 min in an air atmosphere, and the results showed that the nano-aluminum of the present example was obtained. The powder has almost no change, and the surface of the nano-aluminum powder coated with graphene is whitened, and it is aluminum oxide measured by XRD. The graphene-coated nano-aluminum powder of this embodiment and the X-coated aluminum powder are not coated. The ray diffraction curve is shown in Fig. 3. The content shown in Fig. 3 indicates that the graphene coating layer can effectively improve the oxidation resistance of the nano aluminum powder.
实施例2Example 2
本实施例提供了一种石墨烯包覆纳米铝粉的方法，该方法包括以下步骤：This embodiment provides a method for coating graphene-coated nano aluminum powder, the method comprising the following steps:
(1)石墨烯的制备及溶解(1) Preparation and dissolution of graphene
石墨烯采用传统Hummers方法制备，具体方法同实施例1；Graphene is prepared by the traditional Hummers method, the specific method is the same as the embodiment 1;
然后将5mg石墨烯加入聚丙烯酸水溶液(200mL)中快速搅拌(500r/min)，制备成石墨烯分散液，并将其抽真空去除液体中溶解的空气。Then, 5 mg of graphene was added to a polyacrylic acid aqueous solution (200 mL) and rapidly stirred (500 r/min) to prepare a graphene dispersion, which was evacuated to remove dissolved air in the liquid.
(2)石墨烯包覆纳米铝粉(2) Graphene coated nano aluminum powder
在手套箱内，向制备好的100mL石墨烯分散液中以2mg/min的速度加入20mg纳米铝粉，并快速搅拌(2000r/min)形成粗产品，并将其抽真空去除液体中溶解的空气，其中，纳米铝粉在加入石墨烯混合液之前需经稀盐酸或氢氧化钠处理，以保证完全去除表面三氧化二铝钝化膜。In the glove box, 20 mg of nano aluminum powder was added to the prepared 100 mL graphene dispersion at a rate of 2 mg/min, and rapidly stirred (2000 r/min) to form a crude product, which was evacuated to remove dissolved air in the liquid. Among them, the nano aluminum powder is treated with dilute hydrochloric acid or sodium hydroxide before adding the graphene mixture to ensure complete removal of the surface aluminum oxide passivation film.
(3)水热处理(3) Hydrothermal treatment
将粗产品放入水热反应釜中，在90℃烘箱中保温12小时，经过干燥处理，得到表面包覆石墨烯的纳米铝粉。The crude product was placed in a hydrothermal reaction vessel, and incubated in an oven at 90 ° C for 12 hours, and dried to obtain a nano-aluminum powder coated with graphene.
在相同的测试条件下，本实施例制得的石墨烯包覆的纳米铝粉与无石墨烯包覆纳米铝粉样品分别放入0.1mol/L稀盐酸中1小时，发现本实施例的纳米铝粉几乎没有变化， 而无石墨烯包覆的纳米铝粉则产生大量气泡并最终完全消失，表明石墨烯包覆层确实可有效提高纳米铝粉抗氧化能力。Under the same test conditions, the graphene-coated nano aluminum powder prepared in this example and the graphene-free coated nano aluminum powder sample were respectively placed in 0.1 mol/L diluted hydrochloric acid for 1 hour, and the nanometer of the present example was found. Almost no change in aluminum powder, The graphene-free nano-aluminum powder produced a large number of bubbles and eventually disappeared completely, indicating that the graphene coating layer can effectively improve the antioxidant capacity of the nano-aluminum powder.
实施例3Example 3
本实施例提供了一种石墨烯包覆纳米镁粉的方法，该方法包括以下步骤：This embodiment provides a method for coating graphene-coated nano-magnesium powder, the method comprising the following steps:
(1)石墨烯的制备及溶解(1) Preparation and dissolution of graphene
石墨烯采用传统Hummers方法制备，具体包括以下步骤：Graphene is prepared by the traditional Hummers method, and includes the following steps:
在冰水浴中安装好圆底反应瓶，加入适量的浓硫酸，搅拌状态下加入4g石墨粉和2g硝酸钠的混合物；The round bottom reaction bottle is installed in an ice water bath, an appropriate amount of concentrated sulfuric acid is added, and a mixture of 4 g of graphite powder and 2 g of sodium nitrate is added under stirring;
分次加入15g高锰酸钾，快速搅拌并控制反应温度不超过20℃，升温到35℃左右，继续搅拌30min，再缓慢加入适量去离子水，搅拌20min后，加入适量双氧水还原残留的氧化剂，使溶液变为亮黄色；Add 15g potassium permanganate in several portions, stir rapidly and control the reaction temperature not to exceed 20 °C, heat up to about 35 °C, continue stirring for 30min, then slowly add appropriate amount of deionized water, stir for 20min, add appropriate amount of hydrogen peroxide to reduce residual oxidant, Make the solution bright yellow;
趁热过滤，并用质量浓度为5wt％的HCl溶液和去离子水洗涤直到滤液中无硫酸根为止；Filtered hot, and washed with 5% by weight HCl solution and deionized water until there is no sulfate in the filtrate;
将滤饼置于真空干燥箱中充分干燥，得到氧化石墨烯，再加入适量还原剂使其还原成石墨烯；Drying the filter cake in a vacuum drying oven to obtain graphene oxide, and then adding an appropriate amount of reducing agent to reduce it to graphene;
然后将制备好的石墨烯(10mg)加入聚乙烯醇水溶液(100mL)中快速搅拌(1000r/min)，制备成石墨烯分散液，并将其抽真空去除液体中溶解的空气。The prepared graphene (10 mg) was then rapidly stirred (1000 r/min) in an aqueous polyvinyl alcohol solution (100 mL) to prepare a graphene dispersion, which was evacuated to remove dissolved air in the liquid.
(2)石墨烯包覆纳米镁粉(2) Graphene coated nanometer magnesium powder
在手套箱内，向制备好的200mL石墨烯分散液中以1mg/min速度加入10mg纳米铝粉并快速搅拌(1000r/min)形成粗产品，抽真空去除液体中溶解的空气，其中，纳米镁粉在加入石墨烯混合液之前需经稀盐酸或氢氧化钠处理，以保证完全去除表面氧化镁钝化膜。In the glove box, 10 mg of nano aluminum powder was added to the prepared 200 mL graphene dispersion at a rate of 1 mg/min and rapidly stirred (1000 r/min) to form a crude product, and vacuum was used to remove dissolved air in the liquid, wherein, nano magnesium The powder is treated with dilute hydrochloric acid or sodium hydroxide before adding the graphene mixture to ensure complete removal of the surface magnesium oxide passivation film.
(3)高温热处理(3) High temperature heat treatment
将粗产品放入石英反应器中，并将反应器推送到反应室中央，打开真空泵，然后同时以50mL/min的速率通入氢气，以300mL/min的速率通入氮气；The crude product was placed in a quartz reactor, and the reactor was pushed to the center of the reaction chamber, the vacuum pump was turned on, and then hydrogen gas was introduced at a rate of 50 mL/min, and nitrogen gas was introduced at a rate of 300 mL/min;
石英反应器在石墨烯生长过程中加热到400-700℃并维持30mins，并且以35mL/min的速率向其中通入氢气20-60min，其中，加热的升温速率为12℃/min；The quartz reactor is heated to 400-700 ° C during the graphene growth process and maintained for 30 mins, and hydrogen gas is introduced thereto at a rate of 35 mL / min for 20-60 min, wherein the heating rate of heating is 12 ° C / min;
结束时，以300mL/min的速率通入氩气，以35mL/min的速率通入氢气，直到冷却到室温，冷却的速率为10℃/min，得到表面包覆石墨烯的纳米镁粉，其结构如图1b所示。 At the end, argon gas was introduced at a rate of 300 mL/min, and hydrogen gas was introduced at a rate of 35 mL/min until cooling to room temperature, and the rate of cooling was 10 ° C/min, to obtain a surface-coated graphene-containing nano-magnesium powder. The structure is shown in Figure 1b.
在相同的测试条件下，本实施例制得的石墨烯包覆的纳米镁粉与无石墨烯包覆纳米镁粉样品分别极化及阻抗测试，结果如图4a和图4b所示，结果显示本实施例的纳米镁粉比无石墨烯包覆的纳米镁粉具有更强的抗腐蚀能力。 Under the same test conditions, the graphene-coated nano-magnesium powder prepared in this example and the graphene-free coated nano-magnesium powder sample were respectively polarized and impedance tested. The results are shown in Fig. 4a and Fig. 4b, and the results are shown. The nano-magnesium powder of the present embodiment has stronger corrosion resistance than the graphene-free nano-magnesium powder.

Claims (16)

  1. 一种工业化制备石墨烯包覆纳米铝粉或纳米镁粉的方法，该方法包括以下步骤：A method for industrially preparing graphene coated nano aluminum powder or nano magnesium powder, the method comprising the following steps:
    将石墨烯溶于有机溶剂中，制成石墨烯分散液，对石墨烯分散液进行抽真空处理，至真空度高于10-2Pa，其中，所述石墨烯占所述石墨烯分散液总重量的1％-99％；The graphene is dissolved in an organic solvent to prepare a graphene dispersion, and the graphene dispersion is subjected to vacuum treatment to a degree of vacuum higher than 10 −2 Pa, wherein the graphene accounts for the total graphene dispersion 1%-99% of weight;
    在惰性气氛中，向经过抽真空处理的石墨烯分散液中加入纳米铝粉或者纳米镁粉，搅拌30min-100min后，进行抽真空处理，至真空度高于10-2Pa，得到粗产品，其中，所述纳米铝粉或者纳米镁粉占所述粗产品总重量的1％-99％，所述搅拌的速度为600转/分-3000转/分；Adding nano-aluminum powder or nano-magnesium powder to the vacuum-treated graphene dispersion in an inert atmosphere, stirring for 30 min-100 min, and then vacuuming to a vacuum of more than 10 -2 Pa to obtain a crude product. Wherein the nano aluminum powder or nano magnesium powder accounts for 1%-99% of the total weight of the crude product, and the stirring speed is 600 rpm/3000 rpm;
    对所述粗产品进行高温热处理或水热处理，完成石墨烯对纳米铝粉或纳米镁粉的包覆。The crude product is subjected to high-temperature heat treatment or hydrothermal treatment to complete coating of the nano-aluminum powder or the nano-magnesium powder by graphene.
  2. 根据权利要求1所述的方法，其中，所述石墨烯占所述石墨烯分散液总重量的1％-20％。The method of claim 1 wherein said graphene comprises from 1% to 20% by weight based on the total weight of said graphene dispersion.
  3. 根据权利要求1所述的方法，其中，以0.1mg/min-100mg/min的速度向经过抽真空处理的石墨烯分散液中加入所述纳米铝粉或者纳米镁粉。The method according to claim 1, wherein the nano aluminum powder or the nano magnesium powder is added to the vacuum-treated graphene dispersion at a rate of from 0.1 mg/min to 100 mg/min.
  4. 根据权利要求1所述的方法，其中，所述纳米铝粉或者纳米镁粉占所述粗产品总重量的1％-20％。The method of claim 1 wherein the nano aluminum powder or nano magnesium powder comprises from 1% to 20% by weight of the total weight of the crude product.
  5. 根据权利要求1所述的方法，其中，所述有机溶剂包括含有不饱和键的有机溶剂；所述含有不饱和键的有机溶剂包括聚乙烯醇水溶液、聚丙烯酸水溶液或N-甲基吡咯烷酮水溶液；优选地，所述聚乙烯醇水溶液的浓度高于90wt％；所述聚丙烯酸水溶液的浓度高于90wt％；所述N-甲基吡咯烷酮水溶液的浓度高于90wt％。The method according to claim 1, wherein the organic solvent comprises an organic solvent containing an unsaturated bond; and the organic solvent containing an unsaturated bond comprises an aqueous solution of polyvinyl alcohol, an aqueous solution of polyacrylic acid or an aqueous solution of N-methylpyrrolidone; Preferably, the concentration of the aqueous solution of polyvinyl alcohol is higher than 90% by weight; the concentration of the aqueous solution of polyacrylic acid is higher than 90% by weight; and the concentration of the aqueous solution of N-methylpyrrolidone is higher than 90% by weight.
  6. 根据权利要求1所述的方法，其中，所述纳米铝粉或者纳米镁粉在使用前先经浓度为0.01mol/L-1mol/L的盐酸或浓度为0.01mol/L-1mol/L的氢氧化钠溶液处理。The method according to claim 1, wherein the nano aluminum powder or the nano magnesium powder is subjected to a concentration of 0.01 mol/L to 1 mol/L of hydrochloric acid or a concentration of 0.01 mol/L to 1 mol/L of hydrogen before use. Treatment with sodium oxide solution.
  7. 根据权利要求1所述的方法，其中，向经过抽真空处理的石墨烯分散液中加入纳米铝粉或者纳米镁粉时，保持经过抽真空处理的石墨烯分散液处于搅拌状态。The method according to claim 1, wherein the addition of the nano-aluminum powder or the nano-magnesium powder to the vacuum-treated graphene dispersion maintains the vacuum-treated graphene dispersion in a stirred state.
  8. 根据权利要求1所述的方法，其中，所述高温热处理包括以下步骤：The method of claim 1 wherein said high temperature heat treatment comprises the steps of:
    对装有粗产品的容器进行抽真空处理，至真空度高于10-2Pa，以50mL/min的速率通入氢气，同时以300mL/min的速率通入氮气，通气时间为15min；The vessel containing the crude product is evacuated to a vacuum of more than 10 -2 Pa, and hydrogen gas is introduced at a rate of 50 mL/min, while nitrogen gas is introduced at a rate of 300 mL/min, and the aeration time is 15 min;
    加热至400℃-700℃，维持10min-30min，并且在达到加热温度时以10mL/min-50mL/min的速率通入氢气20min-60min；Heating to 400 ° C -700 ° C, maintaining 10min-30min, and reaching the heating temperature at a rate of 10mL / min -50mL / min into the hydrogen for 20min-60min;
    以100mL/min-500mL/min的速率通入氩气，同时以10mL/min-50mL/min的速率通 入氢气，直到冷却到室温，完成所述高温热处理。Argon gas was introduced at a rate of 100 mL/min to 500 mL/min while passing at a rate of 10 mL/min to 50 mL/min. The hydrogen gas was introduced until the temperature was cooled to room temperature, and the high temperature heat treatment was completed.
  9. 根据权利要求8所述的方法，其中，所述加热的升温速率为5℃/min-20℃/min。The method according to claim 8, wherein the heating has a heating rate of 5 ° C / min to 20 ° C / min.
  10. 根据权利要求9所述的方法，其中，所述加热的升温速率为12℃/min。The method according to claim 9, wherein the heating has a heating rate of 12 ° C / min.
  11. 根据权利要求8所述的方法，其中，所述冷却的降温速率为5℃/min-20℃/min。The method of claim 8 wherein said cooling has a rate of cooling of between 5 ° C/min and 20 ° C/min.
  12. 根据权利要求11所述的方法，其中，所述冷却的降温速率为10℃/min。The method of claim 11 wherein said cooling has a rate of temperature drop of 10 ° C/min.
  13. 根据权利要求8所述的方法，其中，加热至400℃-700℃，维持10min-30min，并且在达到加热温度时以35mL/min速率通入氢气。The method according to claim 8, wherein the heating is carried out to a temperature of from 400 ° C to 700 ° C for 10 min to 30 min, and hydrogen gas is supplied at a rate of 35 mL / min when the heating temperature is reached.
  14. 根据权利要求8所述的方法，其中，以300mL/min的速率通入氩气。The method according to claim 8, wherein argon gas is introduced at a rate of 300 mL/min.
  15. 根据权利要求8所述的方法，其中，以100mL/min-500mL/min的速率通入氩气，同时以35mL/min的速率通入氢气。The method according to claim 8, wherein argon gas is introduced at a rate of from 100 mL/min to 500 mL/min while hydrogen gas is introduced at a rate of 35 mL/min.
  16. 根据权利要求1所述的方法，其中，所述水热处理包括以下步骤：The method of claim 1 wherein said hydrothermal treatment comprises the steps of:
    在90℃-120℃下对所述粗产品保温8小时-24小时，经过干燥处理，完成所述水热处理。 The crude product is incubated at 90 ° C - 120 ° C for 8 hours to 24 hours, and subjected to a drying treatment to complete the hydrothermal treatment.
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