WO2016011987A1 - 石墨烯薄膜及其制备方法 - Google Patents

石墨烯薄膜及其制备方法 Download PDF

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WO2016011987A1
WO2016011987A1 PCT/CN2015/087825 CN2015087825W WO2016011987A1 WO 2016011987 A1 WO2016011987 A1 WO 2016011987A1 CN 2015087825 W CN2015087825 W CN 2015087825W WO 2016011987 A1 WO2016011987 A1 WO 2016011987A1
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graphene
graphene oxide
substrate
film
mixture
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孙蓉
黄胜云
符显珠
郭慧子
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Shenzhen Institute of Advanced Technology of CAS
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    • C01B32/00—Carbon; Compounds thereof
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  • the invention relates to the technical field of thermal conductive materials, in particular to a method for preparing a graphene film and a graphene film prepared by the method.
  • thermal conductive materials include ceramics, epoxy glass, diamonds, metals, and composite materials. Some of them have been matured in the field of electronic packaging, but there are more or less disadvantages. For example, although W-Cu alloy has excellent thermal conductivity, low thermal expansion coefficient and good package air tightness, its density is too high, resulting in limited application.
  • Graphene is a single layer of atomic thickness graphite with a two-dimensional honeycomb grid structure. Its thermal conductivity is 5300W/m ⁇ K, which is higher than diamond and carbon nanotubes. It is the material with the highest strength. It is harder than diamonds, 100 times higher than the best steel, and its Young's modulus is 1100Gpa. The tensile strength is 130Gpa. At present, Chinese scientists use vacuum filtration to prepare chopped carbon fibers and graphene oxide into composite paper, and then reduce to obtain graphene composite paper with a thermal conductivity of 977 W/m ⁇ K in the horizontal plane.
  • the vacuum filtration method consumes energy, has a long cycle, and has a small product area, is not suitable for industrial production, and is difficult to prepare a large-area graphene film. Therefore, it is necessary to find a simple and easy method, energy saving, short cycle, and mass production.
  • a method for preparing a graphene film comprising the following steps:
  • the heat-treated mixture is coated on a substrate, and dried to obtain a substrate-supported graphene oxide composite film, and then the substrate-loaded graphene oxide composite film is subjected to high-temperature annealing treatment to obtain a substrate-supported graphite.
  • the olefin composite film separates the substrate and the graphene film to obtain the graphene film.
  • the step of formulating the suspension of graphene oxide is to add graphene oxide to water, and to uniformly disperse the graphene oxide by mechanical stirring or ultrasonic dispersion to obtain a suspension of the graphene oxide.
  • the mechanical agitation rate is from 50 r/min to 500 r/min, and the agitation time is from 1 h to 10 h; and the ultrasonic dispersion is dispersed for 0.5 h to 5 h under ultrasonic waves having a power of 100 W to 1000 W.
  • the concentration of graphene oxide in the suspension of graphene oxide is from 0.5 g/L to 5 g/L.
  • the binder is selected from at least one of starch, dextrin, polyvinyl alcohol, and carboxymethyl cellulose.
  • the mass of the binder is from 0.1% to 10% by mass of the graphene oxide.
  • the heat treatment is performed at 40 ° C to 100 ° C for 10 min to 60 min.
  • the operation of applying the heat-treated mixture to a substrate and drying to obtain a substrate-loaded graphene oxide composite film is by a doctor blade method or a thermal evaporation method.
  • the operation of subjecting the substrate-loaded graphene oxide composite film to a high temperature annealing treatment is to load the substrate-loaded graphene oxide composite film at 500 ° C to 1050 ° C in a protective gas atmosphere.
  • the next treatment is 0.5h ⁇ 5h.
  • a graphene film prepared by the above method for preparing a graphene film is prepared.
  • the method for preparing the above graphene film is prepared by preparing graphene oxide into a suspension of graphene oxide, adding a binder to obtain a mixture, and coating the mixture on a substrate to prepare a substrate-loaded graphene oxide composite film, which is subjected to high temperature annealing and After separation, a graphene film is obtained.
  • the method Compared with the vacuum pumping method, the method has the advantages of simple preparation process, short preparation period, and can prepare a large area of graphene film, which is suitable for industrial production.
  • FIG. 1 is a flow chart showing a method of preparing a graphene film according to an embodiment.
  • a method for preparing a graphene film according to an embodiment includes the following steps S110 to S130 .
  • Step S110 preparing a suspension of graphene oxide.
  • the graphene oxide is added to water, and the graphene oxide is uniformly dispersed by mechanical stirring or ultrasonic dispersion to obtain a suspension of graphene oxide.
  • the rate of mechanical agitation is from 50 r/min to 500 r/min, and the agitation time is from 1 h to 10 h. More preferably, the mechanical agitation power is from 100 r/min to 500 r/min, and the agitation time is from 1 h to 5 h.
  • Ultrasonic dispersion is dispersed for 0.5 h to 5 h under ultrasonic waves with a power of 100 W to 1000 W. More preferably, The ultrasonic power is 500W to 1000W, and the dispersion time is 0.5h to 3h.
  • the concentration of graphene oxide in the suspension of graphene oxide is from 0.5 g/L to 5 g/L.
  • the concentration is selected such that the graphene oxide is well dispersed on the one hand, and the thickness uniformity of the graphene film can be ensured; on the other hand, the thickness of the obtained graphene film is prevented from being too small.
  • the concentration of graphene oxide is from 1 g/L to 5 g/L.
  • Step S120 adding a binder to the suspension of graphene oxide to obtain a mixture, and heat-treating the mixture.
  • a binder is added to the suspension of graphene oxide to obtain a mixture, and the heat treatment is performed to dissolve the binder to obtain a mixture having a certain viscosity to facilitate subsequent coating.
  • the binder is at least one selected from the group consisting of starch, dextrin, polyvinyl alcohol, and carboxymethyl cellulose.
  • the quality of the binder is from 0.1% to 10% by mass of the graphene oxide to ensure that the mixture has a suitable viscosity, and in the subsequent high temperature annealing treatment, the binder can be completely removed to obtain properties.
  • the heat treatment is carried out by incubating the mixture at 40 ° C to 100 ° C for 10 min to 60 min to sufficiently dissolve the binder.
  • the temperature of the heat treatment is from 50 ° C to 95 ° C.
  • Step S130 applying the heat-treated mixture to the substrate, and drying to obtain a substrate-loaded graphene oxide composite film, and then subjecting the substrate-loaded graphene oxide composite film to high-temperature annealing treatment to obtain a substrate-loaded graphene.
  • the composite film is separated from the substrate and the graphene film to obtain a graphene film.
  • the substrate may be a copper foil, a titanium foil or the like, preferably a copper foil.
  • the copper foil is used as a carrier to prepare a graphene film, and also has the function of catalytically reducing graphene oxide, which is beneficial to the subsequent reduction of graphene oxide by high temperature annealing treatment.
  • the price of the copper foil is relatively low, and a large area of the graphene film can be prepared by using the copper foil as a substrate, which is advantageous for reducing the manufacturing cost.
  • the shape and size of the graphene film can be adjusted by changing the shape and size of the copper foil.
  • the thickness of the copper foil is preferably 5 ⁇ m to 200 ⁇ m.
  • a thicker copper foil is used to avoid the copper foil being melted at a high temperature.
  • a copper foil having a thickness of 10 ⁇ m or more is selected.
  • the thickness of the copper foil is more preferably from 9 ⁇ m to 150 ⁇ m.
  • the step of washing and drying the substrate is also included.
  • the cleaning step is specifically: the substrate is placed in an ultrasonic cleaner and washed with water, and then washed with ethanol.
  • the drying step is specifically: drying the substrate in a blast drying oven or a vacuum drying oven, and drying at a temperature of 20 ° C to 80 ° C for 1 h to 10 h. The substrate is cleaned and dried before being coated to avoid subsequent contamination of the graphene film by contaminants such as dust.
  • the substrate-supported graphene oxide composite film can be obtained by a doctor blade method, a spray coating method or a thermal evaporation method.
  • the blade coating method is to apply a mixture onto a substrate by a knife coater, and the substrate of the mixture is dried to remove the solvent to obtain a substrate-supported graphene oxide composite film.
  • the spraying method is to spray the mixture onto a substrate, dry the substrate coated with the mixture, and remove the solvent to obtain a substrate-loaded graphene oxide composite film.
  • the operation of drying the substrate coated with the mixture is carried out by placing the substrate coated with the mixture in a blast drying oven or a vacuum drying oven for drying at a temperature of 30 ° C to 100 ° C for a time of 0.5h ⁇ 5h.
  • the thermal evaporation method is to pour the mixture onto the surface of the substrate, and heat the substrate to evaporate the solvent in the mixture.
  • the substrate is heated to 60 ° C to 90 ° C and the heating time is 0.5 h to 2 h.
  • the substrate-loaded graphene oxide composite film is prepared by a doctor blade method, which is favorable for obtaining a graphene film having a good thickness uniformity.
  • the operation of subjecting the substrate-loaded graphene oxide composite film to high-temperature annealing treatment is specifically: treating the substrate-loaded graphene oxide composite film at 500 ° C to 1080 ° C for 0.5 h to 5 h in a protective gas atmosphere.
  • the shielding gas is selected from at least one of nitrogen, argon, helium, and hydrogen.
  • the purpose of high temperature annealing is to reduce graphene oxide.
  • the reduction by high-temperature heat treatment is more complete than the reduction using a chemical reducing agent, and the obtained graphene film has superior thermal conductivity and electrical properties.
  • the high temperature annealing temperature is from 500 ° C to 1050 ° C.
  • a graphene-supported graphene composite film is obtained, the graphene film is peeled off from the substrate, and the graphene film and the substrate are separated to obtain a graphene film.
  • the method for preparing the above graphene film is prepared by preparing graphene oxide into a suspension of graphene oxide, adding a binder to obtain a mixture, and coating the mixture on a substrate to prepare a substrate-loaded graphene oxide composite film, which is subjected to high temperature annealing and After separation, a graphene film is obtained.
  • the method is related to the vacuum suction filtration method Compared with the simple process, short preparation period and low energy consumption, it can prepare a large area of graphene film, which is suitable for industrial production.
  • a graphene film having a thickness of 500 nm to 100 ⁇ m can be prepared by the above method for preparing a graphene film.
  • the experimental results show that the graphene film prepared by the above method for preparing graphene film has a thermal conductivity of 500 W/m ⁇ K to 1000 W/m ⁇ K, a tensile strength of 10 MPa to 500 MPa, and an elastic modulus of 2 GPa to 50 GPa. It shows that the obtained graphene film has excellent thermal conductivity and mechanical properties.
  • the graphene film prepared by the above method for preparing a graphene film can be directly used as a heat sink material, and has great application prospects in electronic packaging.
  • Test of thermal diffusivity coefficient A The in-plane thermal diffusivity of the sample was tested using a laser flash device of the type NETZSCH LFA 447 NanoFlash.
  • 3 g of graphene oxide was weighed and uniformly dispersed in 1 L of deionized water by an ultrasonic processor to obtain a suspension of graphene oxide having a mass solubility of 3 g/L, wherein the ultrasonic power was 500 W and the dispersion time was 2 h.
  • 9 mg of polyvinyl alcohol was added to obtain a mixture, and the mixture was placed in an oven at 85 ° C for 10 minutes to dissolve the polyvinyl alcohol.
  • the copper foil with a thickness of 30 ⁇ m was placed in an ultrasonic cleaner and washed with water, then immersed in ethanol for 30 minutes, taken out and placed in a blast drying oven and blast dried at 80 ° C for 1 h.
  • the heat-treated mixture was applied to the surface of the clean and dry copper foil by a knife coater, and the copper foil coated with the mixture was placed in a blast oven at 80 ° C for 2 hours to obtain a copper foil-loaded graphene oxide composite film. .
  • the copper foil-loaded graphene oxide composite film was taken out and subjected to high-temperature reduction treatment.
  • the high-temperature reduction treatment method is to place a copper foil-loaded graphene oxide composite film in a tube furnace, and a mixed gas of argon gas and hydrogen gas (95% by volume of argon gas and 5% by volume of hydrogen gas) is introduced. Restore The temperature was 900 ° C and the time was 2 h, and a copper foil-loaded graphene composite film was obtained.
  • graphene film is peeled off from the surface of the copper foil to obtain a high-performance graphene film.
  • a 30 ⁇ m thick graphene film having a thermal conductivity of 791.3 W/m ⁇ K, a tensile strength of 30.5 MPa, and an elastic modulus of 3.7 GPa can be prepared by the above method.
  • the heat-treated mixture was applied to the surface of the clean and dry copper foil by a knife coater, and the copper foil coated with the mixture was placed in a blast oven at 80 ° C for 2 hours to obtain a copper foil-loaded graphene oxide composite film. .
  • the copper foil-loaded graphene oxide composite film was taken out and subjected to high-temperature reduction treatment.
  • the high-temperature reduction treatment method is to place a copper foil-loaded graphene oxide composite film in a tube furnace, and argon gas is introduced thereto, and the reduction temperature is 1000 ° C for 2 hours to obtain a copper foil-loaded graphene composite film.
  • the graphene film is peeled off from the surface of the copper foil to obtain a high-performance graphene film.
  • a 50 ⁇ m thick graphene film having a thermal conductivity of up to 759 W/m ⁇ K, a tensile strength of 26.7 MPa, and an elastic modulus of 4.6 GPa can be prepared by the above method.
  • 3 g of graphene oxide was weighed and uniformly dispersed in 1 L of deionized water by an ultrasonic processor to obtain a suspension of graphene oxide having a mass solubility of 3 g/L, wherein the ultrasonic power was 500 W and the dispersion time was 2 h.
  • 3 mg of polyvinyl alcohol was added to obtain a mixture, and the mixture was placed in an oven at 85 ° C for 10 minutes to dissolve the polyvinyl alcohol.
  • a copper foil having a thickness of 30 ⁇ m was placed in an ultrasonic cleaner and washed with water, then immersed in ethanol for 30 minutes, taken out, placed in a blast drying oven, and blast dried at 20 ° C for 10 hours.
  • the heat-treated mixture was applied to the surface of the clean and dry copper foil by a knife coater, and the copper foil coated with the mixture was placed in a blast oven at 80 ° C for 1 hour to obtain a copper foil-loaded graphene oxide composite film. .
  • the copper foil-loaded graphene oxide composite film was taken out and subjected to high-temperature reduction treatment. High temperature reduction The method is to place a copper foil-loaded graphene oxide composite film in a tube furnace, pass nitrogen gas, and the reduction temperature is 900 ° C for 4 hours to obtain a copper foil-loaded graphene composite film. Finally, the graphene film is peeled off from the surface of the copper foil to obtain a high-performance graphene film.
  • a 30 ⁇ m thick graphene film having a thermal conductivity of 821.1 W/m ⁇ K, a tensile strength of 41.1 MPa, and an elastic modulus of 5.2 GPa can be prepared by the above method.
  • 3 g of graphene oxide was weighed and uniformly dispersed in 1 L of deionized water by an ultrasonic processor to obtain a suspension of graphene oxide having a mass solubility of 3 g/L, wherein the ultrasonic power was 800 W and the dispersion time was 1 h.
  • 9 mg of polyvinyl alcohol was added to obtain a mixture, and the mixture was placed in an oven at 85 ° C for 10 minutes to dissolve the polyvinyl alcohol.
  • the copper foil with a thickness of 30 ⁇ m was placed in an ultrasonic cleaner and rinsed with water, then immersed in ethanol for 60 minutes, taken out and placed in a blast drying oven and blast dried at 30 ° C for 8 hours.
  • the heat-treated mixture was poured onto the surface of a clean, dry copper foil, and the copper foil coated with the mixture was placed on a hot plate and heated to 90 ° C for 1 hour to obtain a copper foil-loaded graphene oxide composite film.
  • the copper foil-loaded graphene oxide composite film was taken out and subjected to high-temperature reduction treatment.
  • the high-temperature reduction treatment method is to place a copper foil-loaded graphene oxide composite film in a tube furnace, and a mixed gas of argon gas and hydrogen gas (95% by volume of argon gas and 5% by volume of hydrogen gas) is introduced.
  • the reduction temperature was 900 ° C for 2 h, and a copper foil-supported graphene composite film was obtained.
  • graphene film is peeled off from the surface of the copper foil to obtain a high-performance graphene film.
  • a 10 ⁇ m thick graphene film having a thermal conductivity of 873.5 W/m ⁇ K, a tensile strength of 37.3 MPa, and an elastic modulus of 4.8 GPa can be prepared by the above method.
  • the copper foil coated with the mixture was dried in a blast oven at 80 ° C for 2 h to obtain a copper foil-supported graphene oxide composite film.
  • the copper foil-loaded graphene oxide composite film was taken out and subjected to high-temperature reduction treatment.
  • the high-temperature reduction treatment method comprises placing a copper foil-loaded graphene oxide composite membrane in a tube furnace, and introducing a mixed gas of argon gas and hydrogen gas (the volume percentage of argon gas is 80%, and the volume percentage of hydrogen gas is 20%).
  • the reduction temperature was 500 ° C for 5 h, and a copper foil-supported graphene composite film was obtained.
  • graphene film is peeled off from the surface of the copper foil to obtain a high-performance graphene film.
  • a 50 ⁇ m thick graphene film having a thermal conductivity of 576.5 W/m ⁇ K, a tensile strength of 47.2 MPa, and an elastic modulus of 6.2 GPa can be prepared by the above method.
  • the mixture was applied to the surface of a clean, dry copper foil by thermal evaporation, and the copper foil coated with the mixture was placed in a blast oven at 75 ° C for 3 hours to obtain a copper foil-loaded graphene oxide composite film.
  • the copper foil-loaded graphene oxide composite film was taken out and subjected to high-temperature reduction treatment.
  • the high-temperature reduction treatment method is to place a copper foil-loaded graphene oxide composite film in a tube furnace, pass nitrogen gas, and the reduction temperature is 500 ° C for 5 hours to obtain a copper foil-loaded graphene composite film.
  • the graphene film is peeled off from the surface of the copper foil to obtain a high-performance graphene film.
  • a 500 nm thick graphene film can be prepared by the above method, and has a thermal conductivity of 679.5 W/m ⁇ K, a tensile strength of 41.5 MPa, and an elastic modulus of 5.1 GPa.
  • the mixture was applied to a clean, dry copper foil surface by a knife coater, and the copper foil coated with the mixture was dried in a blast oven at 100 ° C for 0.5 h to obtain a copper foil-supported graphene oxide composite film.
  • the copper foil-loaded graphene oxide composite film was taken out and subjected to high-temperature reduction treatment.
  • the high-temperature reduction treatment method is to place a copper foil-loaded graphene oxide composite film in a tube furnace, pass nitrogen gas, and the reduction temperature is 1050 ° C for 0.5 h to obtain a copper foil-loaded graphene composite film.
  • the graphene film is peeled off from the surface of the copper foil to obtain a high-performance graphene film.
  • a 1 ⁇ m thick graphene film can be prepared by the above method, and has a thermal conductivity of up to 979.2 W/m ⁇ K, a tensile strength of 63.5 MPa, and an elastic modulus of 7.9 GPa.
  • the treated mixture was applied to the surface of a clean, dry copper foil by a knife coater, and the copper foil coated with the mixture was placed in a forced air oven at 30 ° C for 5 hours to obtain a copper foil-loaded graphene oxide composite film. .
  • the copper foil-loaded graphene oxide composite film was taken out and subjected to high-temperature reduction treatment.
  • the high-temperature reduction treatment method is to place a copper foil-loaded graphene oxide composite film in a tube furnace, pass nitrogen gas, and the reduction temperature is 800 ° C for 1 hour to obtain a copper foil-loaded graphene composite film.
  • the graphene film is peeled off from the surface of the copper foil to obtain a high-performance graphene film.
  • a 2 ⁇ m thick graphene film can be prepared by the above method, and has a thermal conductivity of up to 903.1 W/m ⁇ K, a tensile strength of 35.2 MPa, and an elastic modulus of 4.2 GPa.

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Abstract

本发明涉及石墨烯薄膜及其制备方法，该石墨烯薄膜的制备方法包括配制氧化石墨烯的悬浮液；向所述氧化石墨烯的悬浮液中加入粘合剂得到混合物，对所述混合物进行保温处理；以及将经过保温处理的所述混合物涂覆于衬底上，并进行干燥得到衬底负载氧化石墨烯复合膜，然后将所述衬底负载氧化石墨烯复合膜进行高温退火处理，得到衬底负载石墨烯复合膜，分离所述衬底和石墨烯薄膜，得到所述石墨烯薄膜的步骤。该方法与真空抽率的方法相比，制备工艺简单、制备周期短，能够制备大面积的石墨烯薄膜，适合工业化生产。

Description

石墨烯薄膜及其制备方法 技术领域
本发明涉及导热材料技术领域，特别是涉及一种石墨烯薄膜的制备方法及采用该方法制备的石墨烯薄膜。
背景技术
随着电子技术的飞速发展，封装的小型化和组装的高密度化以及各种新型封装技术的不断涌现，导致了芯片发热量急剧上升，芯片寿命降低。研究表明，温度每升高10℃，Si或GaAs半导体因寿命缩短而产生的失效是原来的三倍。这是由于在微电子集成电路或者大功率整流器件中，材料之间的散热差导致热疲劳及热膨胀系数不匹配产生热应力引起的。因此导热系数和热膨胀系数是发展现代电子封装材料所必须考虑的两大基本因素。因此，导热材料对现代电子封装至关重要。
传统的导热材料有陶瓷、环氧玻璃、金刚石、金属及其复合材料等，有些在电子封装领域中应用已经较为成熟，但是或多或少存在一些缺点。如W-Cu合金尽管具有优异的导热性能及低的热膨胀系数和较好的封装气密性，但是其密度过高，导致了其应用受到限制。
石墨烯是单层原子厚度的石墨，具有二维蜂窝状网格结构。其导热系数为5300W/m·K，高于金刚石和碳纳米管，是已知强度最高的物质，比钻石还坚硬，比最好的钢铁高上100倍，其杨氏模量为1100Gpa，拉伸强度为130Gpa。目前，中国科学家利用真空抽滤的方法将短切碳纤维与氧化石墨烯制备成复合纸，再进行还原获得石墨烯复合纸，其水平面内的导热率高达977W/m·K。但是真空抽滤的方法耗能、周期长，且产品面积较小，不适合工业化生产，并且难以制备大面积的石墨烯薄膜。因此，需要寻找一种简单易行的方法，节能、周期短，实现大规模生产。
发明内容
基于此，有必要提供一种工艺简单、能耗较低的石墨烯薄膜的制备方法，并能制备大面积的石墨烯薄膜。
进一步，提供一种由上述石墨烯薄膜的制备方法的制备的石墨烯薄膜。
一种石墨烯薄膜的制备方法，包括如下步骤：
配制氧化石墨烯的悬浮液；
向所述氧化石墨烯的悬浮液中加入粘合剂得到混合物，对所述混合物进行保温处理；及
将经过保温处理的所述混合物涂覆于衬底上，并进行干燥得到衬底负载氧化石墨烯复合膜，然后将所述衬底负载氧化石墨烯复合膜进行高温退火处理，得到衬底负载石墨烯复合膜，分离所述衬底和石墨烯薄膜，得到所述石墨烯薄膜。
在其中一个实施例中，所述配制氧化石墨烯的悬浮液的步骤是将氧化石墨烯加入水中，采用机械搅拌或超声分散使氧化石墨烯分散均匀，得到所述氧化石墨烯的悬浮液。
在其中一个实施例中，所述机械搅拌的速率为50r/min～500r/min，搅拌的时间为1h～10h；所述超声分散是在功率为100W～1000W的超声波下分散0.5h～5h。
在其中一个实施例中，所述氧化石墨烯的悬浮液中，氧化石墨烯的浓度为0.5g/L～5g/L。
在其中一个实施例中，所述粘合剂选自淀粉、糊精、聚乙烯醇及羧甲基纤维素中的至少一种。
在其中一个实施例中，所述粘合剂的质量是所述氧化石墨烯的质量的0.1％～10％。
在其中一个实施例中，所述保温处理的操作是于40℃～100℃下保温10min～60min。
在其中一个实施例中，所述将经过保温处理的所述混合物涂覆于衬底上，并进行干燥得到衬底负载氧化石墨烯复合膜的操作是采用刮涂法或热蒸发法。
在其中一个实施例中，所述将所述衬底负载氧化石墨烯复合膜进行高温退火处理的操作是在保护气体氛围中，将所述衬底负载氧化石墨烯复合膜于500℃～1050℃下处理0.5h～5h。
一种由上述石墨烯薄膜的制备方法制备的石墨烯薄膜。
上述石墨烯薄膜的制备方法将氧化石墨烯配制成氧化石墨烯的悬浮液后，加入粘合剂得到混合物，将混合物涂覆于衬底上制备衬底负载氧化石墨烯复合膜，经过高温退火及分离后，即得到石墨烯薄膜。该方法与真空抽率的方法相比，制备工艺简单、制备周期短，能够制备大面积的石墨烯薄膜，适合工业化生产。
附图说明
图1为一实施方式的石墨烯薄膜的制备方法的流程图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。
请参阅图1，一实施方式的石墨烯薄膜的制备方法，包括如下步骤S110至步骤S130。
步骤S110：配制氧化石墨烯的悬浮液。
将氧化石墨烯加入水中，采用机械搅拌或超声分散的方式将氧化石墨烯分散均匀，得到氧化石墨烯的悬浮液。
优选地，机械搅拌的速率为50r/min～500r/min，搅拌的时间为1h～10h。更优选地，机械搅拌的功率为100r/min～500r/min，搅拌的时间为1h～5h。
超声分散是在功率为100W～1000W的超声波下分散0.5h～5h。更优选地， 超声波的功率为500W～1000W，分散时间为0.5h～3h。
优选地，氧化石墨烯的悬浮液中，氧化石墨烯的浓度为0.5g/L～5g/L。选用该浓度，一方面使氧化石墨烯较好地分散，能够保证石墨烯薄膜的厚度均匀性；另一面避免所得的石墨烯薄膜的厚度过小。更优选地，氧化石墨烯的浓度为1g/L～5g/L。
步骤S120：向氧化石墨烯的悬浮液中加入粘合剂得到混合物，对混合物进行保温处理。
向氧化石墨烯的悬浮液中加入粘合剂得到混合物，保温处理使粘合剂溶解后得到具有一定粘度的混合物，以利于后续涂覆。
粘合剂选自淀粉、糊精、聚乙烯醇及羧甲基纤维素中的至少一种。优选地，粘合剂的质量占氧化石墨烯的质量的0.1％～10％，以保证使混合物具有合适的粘度，并在后续的高温退火处理中，能够较完全将粘合剂除去，得到性能优越的石墨烯薄膜。更优选地，粘合剂的质量占氧化石墨烯的质量的0.5％～10％。
保温处理的操作为将该混合物于40℃～100℃下保温10min～60min，使粘合剂充分溶解。优选地，保温处理的温度为50℃～95℃。
步骤S130：将经过保温处理的混合物涂覆于衬底上，并进行干燥得到衬底负载氧化石墨烯复合膜，然后将衬底负载氧化石墨烯复合膜进行高温退火处理，得到衬底负载石墨烯复合膜，分离衬底和石墨烯薄膜，得到石墨烯薄膜。
衬底可以为铜箔、钛箔等，优选为铜箔。铜箔作为载体制备石墨烯薄膜，同时还具有催化还原氧化石墨烯的作用，有利于后续高温退火处理对氧化石墨烯的还原。并且，铜箔的价格相对较低，采用铜箔作为衬底可以制备大面积的石墨烯的薄膜，有利于降低制备成本。石墨烯薄膜的形状和大小可以通过改变铜箔的形状和大小进行调整。
铜箔的厚度优选为5μm～200μm。当后续高温退火较高时，选用较厚的铜箔，以避免高温下铜箔被熔化。例如，当后续高温退火的温度大于900℃时，选用厚度为10μm以上的铜箔。铜箔的厚度更优选为9μm～150μm。
将混合物涂覆于衬底上的步骤之前，还包括对衬底进行清洗和干燥的步骤。 清洗的步骤具体为：将衬底置于超声清洗器中用清水清洗，然后再用乙醇浸泡清洗。干燥的步骤具体为：将清洗后的衬底置于鼓风干燥箱或真空干燥箱中进行干燥处理，干燥温度为20℃～80℃，时间为1h～10h。对衬底进行清洗和干燥后再进行涂覆，以避免后续得到石墨烯薄膜被灰尘等污染物污染。
可以采用刮涂法、喷涂法或热蒸发法得到衬底负载氧化石墨烯复合膜。
刮涂法是采用刮涂器将混合物涂覆于衬底上，将混合物的衬底进行干燥，除去溶剂，得到衬底负载氧化石墨烯复合膜。
喷涂法是将混合物喷涂于衬底上，将涂覆有混合物的衬底进行干燥，除去溶剂，得到衬底负载氧化石墨烯复合膜。
优选地，将涂覆有混合物的衬底进行干燥的操作是将涂覆有混合物的衬底放入鼓风干燥箱或真空干燥箱中进行干燥处理，干燥温度为30℃～100℃，时间为0.5h～5h。
热蒸发法是将混合物倒入衬底表面，对衬底进行加热，使混合物中的溶剂蒸发。优选地，将衬底加热至60℃～90℃，加热时间为0.5h～2h。
优选采用刮涂法制备衬底负载氧化石墨烯复合膜，有利于得到厚度均匀性较好的石墨烯薄膜。
将衬底负载氧化石墨烯复合膜进行高温退火处理的操作具体为：在保护气体氛围中，将衬底负载氧化石墨烯复合膜于500℃～1080℃下处理0.5h～5h。
保护气体选自氮气、氩气、氦气及氢气中的至少一种。
高温退火的目的是对氧化石墨烯进行还原。采用高温热处理进行还原，相比于使用化学还原剂进行还原，还原较为彻底，所获得的石墨烯薄膜的导热性能及电学性能较优。更优选地，高温退火的温度为500℃～1050℃。
高温退火后，得到衬底负载石墨烯复合膜，将石墨烯薄膜从衬底上撕下来，将石墨烯薄膜和衬底分离，即得到石墨烯薄膜。
上述石墨烯薄膜的制备方法将氧化石墨烯配制成氧化石墨烯的悬浮液后，加入粘合剂得到混合物，将混合物涂覆于衬底上制备衬底负载氧化石墨烯复合膜，经过高温退火及分离后，即得到石墨烯薄膜。该方法与真空抽滤的方法相 比，工艺简单、制备周期短、能耗低，能够制备大面积的石墨烯薄膜，适合工业化生产。
采用上述石墨烯薄膜的制备方法能够制备厚度为500nm～100μm的石墨烯薄膜。
经实验表明，采用上述石墨烯薄膜的制备方法制得的石墨烯薄膜的导热率为500W/m·K～1000W/m·K，拉伸强度为10Mpa～500Mpa，弹性模量为2Gpa～50Gpa，说明制得的石墨烯薄膜的导热性能和力学性能较优。
采用上述石墨烯薄膜的制备方法制备得到的石墨烯薄膜可以直接作为散热器材料，在电子封装方面具有很大的应用前景。
以下通过具体实施例对上述石墨烯薄膜的制备方法进一步阐述。
以下具体实施例的测定方法如下：
(1)热扩散系数A的测试：采用型号为NETZSCH LFA 447 NanoFlash的激光闪光装置，测试样品的面内热扩散系数。
(2)比热容Cp的测试：采用型号为NETZSCH DSC 200 F3的差示扫描量热仪，测试样品的比热容。
(3)热导率K＝AQCp，其中Q为样品的体积密度。
实施例1
称取3g氧化石墨烯，通过超声处理器均匀分散在1L去离子水中，获得质量溶度为3g/L的氧化石墨烯的悬浮液，其中超声功率为500W，分散时间为2h。向氧化石墨烯的悬浮液中加入9mg聚乙烯醇得到混合物，将混合物置于85℃的烘箱中保温处理10min，使得聚乙烯醇溶解。将厚度为30μm的铜箔置于超声波清洗器中用清水清洗，然后用乙醇浸泡30min，取出放置于鼓风干燥箱中于80℃下鼓风干燥1h。利用刮涂器将经过保温处理的混合物涂覆到洁净、干燥的铜箔表面，将涂覆有混合物的铜箔置于80℃的鼓风烘箱中干燥2h，获得铜箔负载氧化石墨烯复合膜。将铜箔负载氧化石墨烯复合膜取出，进行高温还原处理。高温还原处理的方法是将铜箔负载氧化石墨烯复合膜置于管式炉中，通入氩气和氢气的混合气体(氩气的体积百分比为95％，氢气的体积百分比为5％)，还原 温度为900℃，时间为2h，获得铜箔负载石墨烯复合膜。最后将石墨烯膜从铜箔表面揭下，获得高性能的石墨烯膜。通过上述方法可制备30μm厚的石墨烯薄膜，其导热率高达791.3W/m·K，拉伸强度为30.5Mpa，弹性模量在3.7Gpa。
实施例2
称取5g氧化石墨烯，通过超声处理器均匀分散在1L去离子水中，获得质量溶度为5g/L的氧化石墨烯的悬浮液，其中超声功率为1000W，分散时间为5h。向氧化石墨烯的悬浮液中加入9mg聚乙烯醇得到混合物，将混合物置于85℃的烘箱中10min，使得聚乙烯醇溶解。将厚度为60μm的铜箔置于超声波清洗器中用清水清洗，然后用乙醇浸泡30min，取出放置于鼓风干燥箱中于50℃下鼓风干燥4h。利用刮涂器将经保温处理的混合物涂覆到洁净、干燥的铜箔表面，将涂覆有混合物的铜箔置于80℃的鼓风烘箱中干燥2h，获得铜箔负载氧化石墨烯复合膜。将铜箔负载氧化石墨烯复合膜取出，进行高温还原处理。高温还原处理的方法是将铜箔负载氧化石墨烯复合膜置于管式炉中，通入氩气，还原温度为1000℃，时间为2h，获得铜箔负载石墨烯复合膜。最后将石墨烯膜从铜箔表面揭下，获得高性能的石墨烯膜。通过上述方法可制备50μm厚的石墨烯薄膜，其导热率高达759W/m·K，拉伸强度为26.7Mpa，弹性模量在4.6Gpa。
实施例3
称取3g氧化石墨烯，通过超声处理器均匀分散在1L去离子水中，获得质量溶度为3g/L的氧化石墨烯的悬浮液，其中超声功率为500W，分散时间为2h。向氧化石墨烯的悬浮液中加入3mg聚乙烯醇得到混合物，将混合物置于85℃的烘箱中10min，使得聚乙烯醇溶解。将厚度为30μm的铜箔置于超声波清洗器中用清水清洗，然后用乙醇浸泡30min取出放置于鼓风干燥箱中于20℃下鼓风干燥10h。利用刮涂器将经过保温处理的混合物涂覆到洁净、干燥的铜箔表面，将涂覆有混合物的铜箔置于80℃的鼓风烘箱中干燥1h，获得铜箔负载氧化石墨烯复合膜。将铜箔负载氧化石墨烯复合膜取出，进行高温还原处理。高温还原处 理的方法是将铜箔负载氧化石墨烯复合膜置于管式炉中，通入氮气，还原温度为900℃，时间为4h，获得铜箔负载石墨烯复合膜。最后将石墨烯膜从铜箔表面揭下，获得高性能的石墨烯膜。通过上述方法可制备30μm厚的石墨烯薄膜，其导热率高达821.1W/m·K，拉伸强度为41.1Mpa，弹性模量在5.2Gpa。
实施例4
称取3g氧化石墨烯，通过超声处理器均匀分散在1L去离子水中，获得质量溶度为3g/L的氧化石墨烯的悬浮液，其中超声功率为800W，分散时间为1h。向氧化石墨烯的悬浮液中加入9mg聚乙烯醇得到混合物，将混合物置于85℃的烘箱中10min，使得聚乙烯醇溶解。将厚度为30μm的铜箔置于超声波清洗器中用清水清洗，然后用乙醇浸泡60min，取出放置于鼓风干燥箱中于30℃下鼓风干燥8h。将经过保温处理的混合物倒入洁净、干燥的铜箔表面，将涂覆有混合物的铜箔置于加热板上加热到90℃，加热1h，获得铜箔负载氧化石墨烯复合膜。将铜箔负载氧化石墨烯复合膜取出，进行高温还原处理。高温还原处理的方法是将铜箔负载氧化石墨烯复合膜置于管式炉中，通入氩气和氢气的混合气体(氩气的体积百分比为95％，氢气的体积百分比为5％)，还原温度为900℃，时间为2h，获得铜箔负载石墨烯复合膜。最后将石墨烯膜从铜箔表面揭下，获得高性能的石墨烯膜。通过上述方法可制备10μm厚的石墨烯薄膜，其导热率高达873.5W/m·K，拉伸强度为37.3Mpa，弹性模量在4.8Gpa。
实施例5
称取5g氧化石墨烯，通过超声处理器均匀分散在1L去离子水中，获得质量溶度为5g/L的氧化石墨烯的悬浮液，其中超声功率为1000W，分散时间为3h。向氧化石墨烯的悬浮液中加入500mg聚乙烯醇得到混合物，将混合物置于85℃的烘箱中10min，使得聚乙烯醇溶解。将厚度为10μm的铜箔置于超声波清洗器中用清水清洗，然后用乙醇浸泡60min，取出放置于鼓风干燥箱中于40℃下鼓风干燥6h。利用刮涂器将经过保温处理的混合物涂覆到洁净、干燥的铜箔表面， 将涂覆有混合物的铜箔置于80℃的鼓风烘箱中干燥2h，获得铜箔负载氧化石墨烯复合膜。将铜箔负载氧化石墨烯复合膜取出，进行高温还原处理。高温还原处理的方法是将铜箔负载氧化石墨烯复合膜置于管式炉中，通入氩气和氢气的混合气体(氩气的体积百分比为80％，氢气的体积百分比为20％)，还原温度为500℃，时间为5h，获得铜箔负载石墨烯复合膜。最后将石墨烯膜从铜箔表面揭下，获得高性能的石墨烯膜。通过上述方法可制备50μm厚的石墨烯薄膜，其导热率高达576.5W/m·K，拉伸强度为47.2Mpa，弹性模量在6.2Gpa。
实施例6
称取0.5g氧化石墨烯，通过机械搅拌均匀分散在1L去离子水中，获得质量溶度为0.5g/L的氧化石墨烯的悬浮液，其中机械搅拌的速率为100r/min，搅拌时间为10h。向氧化石墨烯的悬浮液中加入20mg淀粉和5mg羧甲基纤维素得到混合物，将混合物置于40℃的烘箱中60min，使得淀粉溶解。将厚度为5μm的铜箔置于超声波清洗器中用清水清洗，然后用乙醇浸泡60min，取出放置于鼓风干燥箱中于75℃下鼓风干燥1.5h。采用热蒸发的方式将混合物涂覆于洁净、干燥的铜箔表面，将涂覆有混合物的铜箔置于75℃的鼓风烘箱中干燥3h，获得铜箔负载氧化石墨烯复合膜。将铜箔负载氧化石墨烯复合膜取出，进行高温还原处理。高温还原处理的方法是将铜箔负载氧化石墨烯复合膜置于管式炉中，通入氮气，还原温度为500℃，时间为5h，获得铜箔负载石墨烯复合膜。最后将石墨烯膜从铜箔表面揭下，获得高性能的石墨烯膜。通过上述方法可制备500nm厚的石墨烯薄膜，其导热率高达679.5W/m·K，拉伸强度为41.5Mpa，弹性模量在5.1Gpa。
实施例7
称取1g氧化石墨烯，通过机械搅拌均匀分散在1L去离子水中，获得质量溶度为1g/L的氧化石墨烯的悬浮液，其中机械搅拌的速率为500r/min，搅拌时间为1h。向氧化石墨烯的悬浮液中加入5mg糊精得到混合物，将混合物置于95℃ 的烘箱中15min，使得糊精溶解。将厚度为200μm的铜箔置于超声波清洗器中用清水清洗，然后用乙醇浸泡30min，取出放置于鼓风干燥箱中于75℃下鼓风干燥1.5h。利用刮涂器将混合物涂覆到洁净、干燥的铜箔表面，将涂覆有混合物的铜箔置于100℃的鼓风烘箱中干燥0.5h，获得铜箔负载氧化石墨烯复合膜。将铜箔负载氧化石墨烯复合膜取出，进行高温还原处理。高温还原处理的方法是将铜箔负载氧化石墨烯复合膜置于管式炉中，通入氮气，还原温度为1050℃，时间为0.5h，获得铜箔负载石墨烯复合膜。最后将石墨烯膜从铜箔表面揭下，获得高性能的石墨烯膜。通过上述方法可制备1μm厚的石墨烯薄膜，其导热率高达979.2W/m·K，拉伸强度为63.5Mpa，弹性模量在7.9Gpa。
实施例8
称取2g氧化石墨烯，通过机械搅拌均匀分散在1L去离子水中，获得质量溶度为2g/L的氧化石墨烯的悬浮液，其中机械搅拌的速率为250r/min，搅拌时间为2.5h。向氧化石墨烯的悬浮液中加入200mg羧甲基纤维素得到混合物，将混合物置于100℃的烘箱中10min，使得羧甲基纤维素溶解。将厚度为150μm的铜箔置于超声波清洗器中用清水清洗，然后用乙醇浸泡60min，取出放置于鼓风干燥箱中于75℃下鼓风干燥1.5h。利用刮涂器将经过保护处理的混合物涂覆到洁净、干燥的铜箔表面，将涂覆有混合物的铜箔置于30℃的鼓风烘箱中干燥5h，获得铜箔负载氧化石墨烯复合膜。将铜箔负载氧化石墨烯复合膜取出，进行高温还原处理。高温还原处理的方法是将铜箔负载氧化石墨烯复合膜置于管式炉中，通入氮气，还原温度为800℃，时间为1h，获得铜箔负载石墨烯复合膜。最后将石墨烯膜从铜箔表面揭下，获得高性能的石墨烯膜。通过上述方法可制备2μm厚的石墨烯薄膜，其导热率高达903.1W/m·K，拉伸强度为35.2Mpa，弹性模量在4.2Gpa。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域 的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种石墨烯薄膜的制备方法，包括如下步骤：
    配制氧化石墨烯的悬浮液；
    向所述氧化石墨烯的悬浮液中加入粘合剂得到混合物，对所述混合物进行保温处理；及
    将经过保温处理的所述混合物涂覆于衬底上，并进行干燥得到衬底负载氧化石墨烯复合膜，然后将所述衬底负载氧化石墨烯复合膜进行高温退火处理，得到衬底负载石墨烯复合膜，分离所述衬底和石墨烯薄膜，得到所述石墨烯薄膜。
  2. 根据权利要求1所述的石墨烯薄膜的制备方法，其特征在于，所述配制氧化石墨烯的悬浮液的步骤是将氧化石墨烯加入水中，采用机械搅拌或超声分散使氧化石墨烯分散均匀，得到所述氧化石墨烯的悬浮液。
  3. 根据权利要求2所述的石墨烯薄膜的制备方法，其特征在于，所述机械搅拌的速率为50r/min～500r/min，搅拌的时间为1h～10h；所述超声分散是在功率为100W～1000W的超声波下分散0.5h～5h。
  4. 根据权利要求1所述的石墨烯薄膜的制备方法，其特征在于，所述氧化石墨烯的悬浮液中，氧化石墨烯的浓度为0.5g/L～5g/L。
  5. 根据权利要求1所述的石墨烯薄膜的制备方法，其特征在于，所述粘合剂选自淀粉、糊精、聚乙烯醇及羧甲基纤维素中的至少一种。
  6. 根据权利要求1所述的石墨烯薄膜的制备方法，其特征在于，所述粘合剂的质量是所述氧化石墨烯的质量的0.1％～10％。
  7. 根据权利要求1所述的石墨烯薄膜的制备方法，其特征在于，所述保温处理的操作是于40℃～100℃下保温10min～60min。
  8. 根据权利要求1所述的石墨烯薄膜的制备方法，其特征在于，所述将经过保温处理的所述混合物涂覆于衬底上，并进行干燥得到衬底负载氧化石墨烯复合膜的操作是采用刮涂法或热蒸发法。
  9. 根据权利要求1所述的石墨烯薄膜的制备方法，其特征在于，所述将所 述衬底负载氧化石墨烯复合膜进行高温退火处理的操作是在保护气体氛围中，将所述衬底负载氧化石墨烯复合膜于500℃～1050℃下处理0.5h～5h。
  10. 一种由权利要求1～9所述的石墨烯薄膜的制备方法制备的石墨烯薄膜。
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