WO2016029715A1 - Graphene composite material and preparation method therefor - Google Patents

Graphene composite material and preparation method therefor Download PDF

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WO2016029715A1
WO2016029715A1 PCT/CN2015/078660 CN2015078660W WO2016029715A1 WO 2016029715 A1 WO2016029715 A1 WO 2016029715A1 CN 2015078660 W CN2015078660 W CN 2015078660W WO 2016029715 A1 WO2016029715 A1 WO 2016029715A1
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graphene composite
graphene
composite material
graphite
mpa
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PCT/CN2015/078660
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French (fr)
Chinese (zh)
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李琦
李召平
康飞宇
杜鸿达
孙占威
蔡庆荣
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鸿纳（东莞）新材料科技有限公司
清华大学深圳研究生院
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    • 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
    • C01B32/20—Graphite
    • C01B32/21—After-treatment

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  • the invention relates to the technical field of materials, in particular to a high performance (high thermal conductivity, high conductivity, high strength) graphene composite material and a preparation method thereof.
  • Carbon-based materials there are diamond films with a thermal conductivity of up to 2400 W/mK, vapor-grown nano-carbon fibers (VGCF: 2000 W/mK), carbon nanotubes (CNT: 3000-6600 W/mK), and currently known up to 5300 W/mK.
  • VGCF vapor-grown nano-carbon fibers
  • CNT carbon nanotubes
  • Graphene Carbon-based materials have the advantages of small specific gravity (1.9 to 2.2 g/cc), small thermal expansion, and high thermal conductivity.
  • thermal conductive paper there are two main techniques for using carbon-based materials as thermal conductive paper: one is to compress expanded graphite into paper having a thickness ranging from 50 ⁇ m to 0.3 mm, and the thermal conductivity is 300-500 W/mK, and the resistivity is only The other is about 10 -4 ⁇ cm; the other is a pyrolytic graphite sheet (PGS), usually formed by a PI (polyimide) film at 1000-1400 ° C to form a carbon film, 2700 ⁇ 3000 ° C graphite It has a thermal conductivity of 700 to 1950 W/mK and an electrical conductivity of 10,000 to 20,000 S/cm. The latter is more flexible than the former.
  • PPS pyrolytic graphite sheet
  • Graphite paper prepared from expanded graphite has low thermal conductivity and poor mechanical properties. PGS obtained by graphitization of carbides of PI and other materials has greatly improved thermal conductivity and mechanics of expanded graphite paper. However, the yield of the raw material is only 30% by weight, so the cost is high.
  • an object of the present invention is to provide a graphene composite material, the complex
  • the composite material not only has high thermal conductivity, high electrical conductivity and high strength and other mechanical properties, but also has high yield and low cost.
  • Another object of the present invention is to provide a method of preparing the graphene composite.
  • a graphene composite material comprising 50 to 100 wt% of graphene and 0.001 to 50 wt% of other nanomaterials, and the nanomaterial is carbon nanotube (CNT) and/or nano carbon fiber (VGCF).
  • CNT carbon nanotube
  • VGCF nano carbon fiber
  • the surface of the graphene composite has laminate and/or pleat features.
  • the graphene composite has a grain size of from 10 ⁇ m to 500 ⁇ m; at least ⁇ 10 ⁇ m, preferably ⁇ 50 ⁇ m, more preferably ⁇ 100 ⁇ m, most preferably ⁇ 500 ⁇ m.
  • the graphene composite has a density of from 1.60 g/cc to 2.20 g/cc. At least ⁇ 1.60 g/cc, preferably ⁇ 1.80 g/cc, more preferably ⁇ 2.00 g/cc, most preferably ⁇ 2.20 g/cc.
  • the graphene composite has a tensile strength of from 20 MPa to 100 MPa; at least ⁇ 20 MPa, preferably ⁇ 30 MPa, more preferably ⁇ 50 MPa, and most preferably ⁇ 100 MPa.
  • the graphene composite has a thermal conductivity of 1000 W/m.K to 3000 W/m.K. At least ⁇ 1000 W/m.K, preferably ⁇ 1500 W/m.K, more preferably ⁇ 2000 W/m.K, most preferably ⁇ 3000 W/m.K.
  • the graphene composite has an electrical conductivity of 10,000 S/cm to 1,000,000 S/cm; an electrical conductivity of at least ⁇ 10,000 S/cm, preferably ⁇ 50,000 S/cm, more preferably ⁇ 100,000 S/cm, most preferably ⁇ 1000000S/cm.
  • the graphene composite has a purity (graphitized carbon content) of ⁇ 99.90 wt%.
  • the graphene is a multilayer graphene having a layer number of layers ⁇ 100 layers ( ⁇ 34 nm), preferably a layer of graphene of ⁇ 10 layers ( ⁇ 3.4 nm), more preferably ⁇ 5 layers ( ⁇ 1.7 nm) a small layer of graphene, most preferably 1 to 2 layers ( ⁇ 0.68 nm) of single layer, double layer graphene;
  • the carbon nanotubes are one or more composites of a multi-wall tube of 10 to 100 nm, a small wall tube of 3 to 10 nm, a double wall tube of 3 to 5 nm, and a single wall tube of 0.3 to 3 nm.
  • the nano carbon fiber refers to a carbon fiber grown in a vapor phase of 100 to 150 nm.
  • a method of preparing the graphene composite material comprising the following preparation steps:
  • the above slurry is added to a general-purpose paper machine, and the nano-material is added according to the ratio, and the wet-graphene composite paper with a certain thickness is obtained by dilution and filtration; however, it is not limited to traditional papermaking, coating, printing, mold casting, etc. .
  • the temperature in the high temperature furnace is 1000 ° C ⁇ 5000 ° C
  • the pressure is 0.001 ⁇ 10 MPa
  • recrystallization is carried out under vacuum, inert gas or oxygen atmosphere protection atmosphere.
  • the reaction temperature is at least 1500 ° C, preferably ⁇ 2000 ° C, more preferably ⁇ 2500 ° C, most preferably ⁇ 3000 ° C;
  • the reaction pressure is at least 0.001 MPa, preferably ⁇ 0.1 MPa, more preferably ⁇ 1 MPa, most preferably ⁇ 10 MPa.
  • the reaction atmosphere can be optionally vacuum, any inert gas (nitrogen, argon, etc.), or any oxygen absorber to protect the environment.
  • the preparation method includes, but is not limited to, nano-recrystallization of graphene and crystal growth, or local graphitization reaction under specific conditions. .
  • High performance graphene composites can be present in any shape and in any size such as film, paper, rod, block, tube, and the like.
  • the invention comprises 50-100 wt% of graphene, 0.001-50 wt% of carbon nanotubes or 0.001-50 wt% of nano carbon fibers; the graphene composite material prepared by the invention from the produced graphene, thermal conductivity and thermal diffusivity , conductivity and toughness, have a great improvement (its conductivity is at least ⁇ 10,000S / cm; thermal conductivity ⁇ 1,000W / mK; tensile strength at least; density of at least ⁇ 1.60g / cc; grain size of at least ⁇ 10 ⁇ m ;), and easy to process.
  • Graphene is a two-dimensional sheet-like carbon nanomaterial, which is the basic building block of graphite and carbon nanotubes. Its excellent physical properties have made graphene a hot material in this century.
  • Single-layer graphene resistivity up to 10 -6 ⁇ cm similar to single-walled carbon nanotubes and silver
  • thermal conductivity up to 5300 W/m ⁇ K (similar to single-walled carbon nanotubes, higher than diamond)
  • 1000GPa similar to multi-walled carbon nanotubes, 200 times that of steel
  • electron mobility up to 200000cm 2 /Vs (similar to single-walled carbon nanotubes, 100 times faster than silicon); also has 97.7% transparency (better than nano Carbon tube and ITO) and up to 2630 m 2 /g specific surface area (twice the number of single-walled carbon nanotubes).
  • graphene, carbon nanotubes or nano-carbon fibers with high thermal conductivity, high electrical conductivity, and excellent mechanical properties graphene, carbon nanotubes or nano-carbon fibers can be self-assembled and rearranged to obtain various practical heat-dissipating and conductive components. .
  • the graphene composite material produced by the present invention based on the high performance of graphene has the following advantages:
  • the high-performance graphene composite material of the invention can be widely used in any shape such as film, paper, rod, block, tube, etc., and can be widely used in 3C, flat panel display, LED, battery module, automobile, medical equipment, aerospace, metallurgy, nuclear reaction and other industries.
  • a graphene composite material comprising 90 wt% of a small layer of graphite and 10 wt% of a carbon nanotube (CNT).
  • the above graphite composite film is placed in a high temperature furnace at 1500 ° C, 2200 ° C, 3000 ° C, and then
  • the resistivity of the diaphragm was measured by a four-point method and the thermal conductivity was measured by a laser method. The lowest resistivity was 0.8 ⁇ 10 -5 ohm.cm, the thermal conductivity was 2100 W/mK, and the strength was 50 MPa.
  • a graphene composite material comprising 90% by weight of a small layer of graphite and 10% by weight of VGCF.
  • the graphite composite film is placed in a high temperature furnace at 1500 ° C, 2200 ° C, and 3000 ° C to perform recrystallization treatment; and the graphene composite material is obtained.
  • the resistivity of the diaphragm was measured by a four-point method and the thermal conductivity was measured by a laser method. The lowest resistivity was 2 ⁇ 10 -5 ohm.cm, the thermal conductivity was 1900 W/mK, and the strength was 45 MPa.
  • a graphene composite material comprising 99 wt% of a small layer of graphite and 1 wt% of a CNT.
  • the graphite composite film is placed in a high-temperature furnace at 1500 ° C, 2200 ° C, and 3000 ° C to perform recrystallization treatment; and the graphene composite material is obtained.
  • the resistivity of the diaphragm was measured by a four-point method and the thermal conductivity was measured by a laser method. Obtain the lowest resistivity
  • a graphene composite material comprising 99 wt% of a small layer of graphite and 1 wt% of VGCF.
  • the above graphite composite film is placed in a high temperature furnace at 1500 ° C, 2200 ° C, 3000 ° C, for recrystallization treatment;
  • the resistivity of the diaphragm was measured by a four-point method and the thermal conductivity was measured by a laser method. Get the lowest resistivity of 2
  • the large single crystal formed by recrystallization of the nanographene in the graphene composite material of the present invention As can be seen from FIG. 1, the large single crystal formed by recrystallization of the nanographene in the graphene composite material of the present invention.
  • the surface of the graphene composite material of the present invention has the characteristics of wrinkles and grain boundaries.

Abstract

Provided are a graphene composite material and a preparation method therefor. The graphene composite material comprises: 50wt% to 100wt% of graphene and 0.001wt% to 50wt% of other nanometer materials, the other nanometer materials being carbon nanotubes and/or carbon nanofibers. The preparation method comprises: preparing graphite slurry, adding the graphite slurry in a general-purpose paper machine, adding nanometer materials in proportion, performing dilution and suction filtration to obtain wet graphene composite paper, drying and compacting the wet graphene composite paper to obtain a graphite composite film, placing the graphite composite film in a high temperature furnace for recrystallization, and finally obtaining the graphene composite material. The graphene composite material of the present invention has high purity and has excellent thermal and electrical conductivity and excellent mechanical properties.

Description

一种石墨烯复合材料及其制备方法Graphene composite material and preparation method thereof 技术领域Technical field
本发明涉及材料技术领域，具体涉及一种高性能(高导热、高导电、高强度)石墨烯复合材料及其制备方法。The invention relates to the technical field of materials, in particular to a high performance (high thermal conductivity, high conductivity, high strength) graphene composite material and a preparation method thereof.
背景技术Background technique
随着工作功率的提高，设备体积越来越小，设备散热显得越发重要。当前导热领域应用的材料可分为金、银、铜等金属，氧化铝，氧化镁等氧化物、BN等氮化物及碳系材料。其中碳系材料家族中有导热率高达2400W/m.K的金刚石薄膜，气相生长的纳米碳纤维(VGCF：2000W/m.K)、碳纳米管(CNT：3000～6600W/m.K)和目前已知高达5300W/m.K的石墨烯。碳系材料具有比重小(1.9～2.2g/cc)，热膨胀小，热导率高的优势。As the working power increases, the size of the device becomes smaller and smaller, and the heat dissipation of the device becomes more and more important. Materials currently used in the field of heat conduction can be classified into metals such as gold, silver, and copper, oxides such as alumina and magnesia, nitrides such as BN, and carbon-based materials. Among the carbon-based materials, there are diamond films with a thermal conductivity of up to 2400 W/mK, vapor-grown nano-carbon fibers (VGCF: 2000 W/mK), carbon nanotubes (CNT: 3000-6600 W/mK), and currently known up to 5300 W/mK. Graphene. Carbon-based materials have the advantages of small specific gravity (1.9 to 2.2 g/cc), small thermal expansion, and high thermal conductivity.
目前，利用碳系材料做导热纸的主要有两种技术：一种是将膨胀石墨压制成厚度从50微米到0.3毫米不等的纸，热导率在300～500W/m.K，而电阻率仅在10-4Ω·cm左右；另一种是人造石墨片(pyrolytic graphite sheet，PGS)，通常用PI(聚酰亚胺)膜在1000～1400℃裂解后成碳膜，2700～3000℃石墨化制得，热导率达到700～1950W/m.K，电导率在10000～20000S/cm。后者较前者柔韧性更高。At present, there are two main techniques for using carbon-based materials as thermal conductive paper: one is to compress expanded graphite into paper having a thickness ranging from 50 μm to 0.3 mm, and the thermal conductivity is 300-500 W/mK, and the resistivity is only The other is about 10 -4 Ω·cm; the other is a pyrolytic graphite sheet (PGS), usually formed by a PI (polyimide) film at 1000-1400 ° C to form a carbon film, 2700 ~ 3000 ° C graphite It has a thermal conductivity of 700 to 1950 W/mK and an electrical conductivity of 10,000 to 20,000 S/cm. The latter is more flexible than the former.
以膨胀石墨为原料制备的石墨纸，热导率不高，力学性能差；而以PI及其他材料的碳化物石墨化得到的PGS虽然相对膨胀石墨纸热导率和力学都有很大提高，但其原材料的产率仅有30wt％，因此成本高昂。Graphite paper prepared from expanded graphite has low thermal conductivity and poor mechanical properties. PGS obtained by graphitization of carbides of PI and other materials has greatly improved thermal conductivity and mechanics of expanded graphite paper. However, the yield of the raw material is only 30% by weight, so the cost is high.
发明内容Summary of the invention
为了解决上述问题，本发明的目的在于，提供一种石墨烯复合材料，该复 合材料不仅具有高导热、高导电的电化性能和高强度等力学性能，而且产率高，成本低廉。In order to solve the above problems, an object of the present invention is to provide a graphene composite material, the complex The composite material not only has high thermal conductivity, high electrical conductivity and high strength and other mechanical properties, but also has high yield and low cost.
本发明的目的之二是提供所述石墨烯复合材料的制备方法。Another object of the present invention is to provide a method of preparing the graphene composite.
本发明是通过以下技术方案来实现的：The present invention is achieved by the following technical solutions:
一种石墨烯复合材料，包括石墨烯50～100wt％和其他纳米材料0.001～50wt％，所述纳米材料为碳纳米管(CNT)和/或纳米碳纤维(VGCF)。A graphene composite material comprising 50 to 100 wt% of graphene and 0.001 to 50 wt% of other nanomaterials, and the nanomaterial is carbon nanotube (CNT) and/or nano carbon fiber (VGCF).
较佳地，所述石墨烯复合材料的表面具有层叠和/或褶皱特征。Preferably, the surface of the graphene composite has laminate and/or pleat features.
较佳地，所述石墨烯复合材料的晶粒尺寸为10μm～500μm；至少≥10μm，优选≥50μm，更优选≥100μm，最优选≥500μm。Preferably, the graphene composite has a grain size of from 10 μm to 500 μm; at least ≥ 10 μm, preferably ≥ 50 μm, more preferably ≥ 100 μm, most preferably ≥ 500 μm.
较佳地，所述石墨烯复合材料的密度为1.60g/cc～2.20g/cc。至少≥1.60g/cc，优选≥1.80g/cc，更优选≥2.00g/cc，最优选≥2.20g/cc。Preferably, the graphene composite has a density of from 1.60 g/cc to 2.20 g/cc. At least ≥ 1.60 g/cc, preferably ≥ 1.80 g/cc, more preferably ≥ 2.00 g/cc, most preferably ≥ 2.20 g/cc.
较佳地，所述石墨烯复合材料拉伸强度为20MPa～100MPa；至少≥20MPa，优选≥30MPa，更优选≥50MPa，最优选≥100MPa。Preferably, the graphene composite has a tensile strength of from 20 MPa to 100 MPa; at least ≥ 20 MPa, preferably ≥ 30 MPa, more preferably ≥ 50 MPa, and most preferably ≥ 100 MPa.
较佳地，所述石墨烯复合材料导热率为1000W/m.K～3000W/m.K。至少≥1000W/m.K、优选≥1500W/m.K，更优选≥2000W/m.K，最优选≥3000W/m.K。Preferably, the graphene composite has a thermal conductivity of 1000 W/m.K to 3000 W/m.K. At least ≥1000 W/m.K, preferably ≥1500 W/m.K, more preferably ≥2000 W/m.K, most preferably ≥3000 W/m.K.
较佳地，所述石墨烯复合材料电导率为10000S/cm～1000000S/cm；电导率至少≥10，000S/cm，优选≥50，000S/cm，更优选≥100，000S/cm，最优选≥1000000S/cm。Preferably, the graphene composite has an electrical conductivity of 10,000 S/cm to 1,000,000 S/cm; an electrical conductivity of at least ≥ 10,000 S/cm, preferably ≥ 50,000 S/cm, more preferably ≥ 100,000 S/cm, most preferably ≥1000000S/cm.
较佳地，所述石墨烯复合材料纯度(石墨化碳含量)≥99.90wt％。Preferably, the graphene composite has a purity (graphitized carbon content) of ≥99.90 wt%.
较佳地，所述石墨烯为层数层数≤100层(≤34nm)的多层石墨烯、优选≤10层(≤3.4nm)的少层石墨烯、更优选≤5层(≤1.7nm)的少层石墨烯、最优选1～2层(≤0.68nm)的单层、双层石墨烯；Preferably, the graphene is a multilayer graphene having a layer number of layers ≤100 layers (≤34 nm), preferably a layer of graphene of ≤10 layers (≤3.4 nm), more preferably ≤5 layers (≤1.7 nm) a small layer of graphene, most preferably 1 to 2 layers (≤ 0.68 nm) of single layer, double layer graphene;
较佳地，所述碳纳米管为10～100nm的多壁管、3～10nm的少壁管、3～5nm双壁管、0.3～3nm单壁管中的一种或多种复合物。Preferably, the carbon nanotubes are one or more composites of a multi-wall tube of 10 to 100 nm, a small wall tube of 3 to 10 nm, a double wall tube of 3 to 5 nm, and a single wall tube of 0.3 to 3 nm.
较佳地，所述纳米碳纤维是指100～150nm的气相生长的碳纤维。Preferably, the nano carbon fiber refers to a carbon fiber grown in a vapor phase of 100 to 150 nm.
制备所述石墨烯复合材料的方法，包括如下制备步骤：A method of preparing the graphene composite material, comprising the following preparation steps:
A.制备高浓度少层石墨浆料，具体的制备参考专利号为201210546111.3的 文献；A. Preparation of high concentration and small layer of graphite slurry, the specific preparation reference patent number is 201210546111.3 literature;
B.取上述浆料加入到通用抄纸机，按所述比例加入纳米材料，稀释抽滤得到厚度一定的湿石墨烯复合纸；但不限于传统抄纸、涂覆、印刷、模具铸造等技术。B. The above slurry is added to a general-purpose paper machine, and the nano-material is added according to the ratio, and the wet-graphene composite paper with a certain thickness is obtained by dilution and filtration; however, it is not limited to traditional papermaking, coating, printing, mold casting, etc. .
C.取上述湿石墨烯复合纸烘干后，在25～35MPa压力下压实，得到石墨复合膜；C. taking the above wet graphene composite paper after drying, compacting at a pressure of 25 to 35 MPa to obtain a graphite composite film;
D.将上述石墨复合膜置于高温炉中进行再结晶处理，最后得到所述石墨烯复合材料。D. The above graphite composite film is placed in a high temperature furnace for recrystallization treatment, and finally the graphene composite material is obtained.
其中，所述高温炉中的温度为1000℃～5000℃，压力为0.001～10MPa；再结晶是在真空、惰性气体或吸氧剂保护的气氛下进行。反应温度至少选1500℃、优选≥2000℃、更优选≥2500℃、最优选≥3000℃；反应压力至少0.001MPa、优选≥0.1MPa、更优选≥1MPa、最优选≥10MPa。反应气氛可选真空、任何惰性气体(氮气、氩气等)、或任何吸氧剂保护环境下。Wherein, the temperature in the high temperature furnace is 1000 ° C ~ 5000 ° C, the pressure is 0.001 ~ 10 MPa; recrystallization is carried out under vacuum, inert gas or oxygen atmosphere protection atmosphere. The reaction temperature is at least 1500 ° C, preferably ≥ 2000 ° C, more preferably ≥ 2500 ° C, most preferably ≥ 3000 ° C; the reaction pressure is at least 0.001 MPa, preferably ≥ 0.1 MPa, more preferably ≥ 1 MPa, most preferably ≥ 10 MPa. The reaction atmosphere can be optionally vacuum, any inert gas (nitrogen, argon, etc.), or any oxygen absorber to protect the environment.
该制备方法包括但不限于在特定条件下发生石墨烯的纳米再结晶及晶体长大、或局部石墨化反应。。The preparation method includes, but is not limited to, nano-recrystallization of graphene and crystal growth, or local graphitization reaction under specific conditions. .
高性能石墨烯复合材料可以膜、纸、棒、块、管等任何形状及任何尺寸存在。High performance graphene composites can be present in any shape and in any size such as film, paper, rod, block, tube, and the like.
本发明包括石墨烯50～100wt％、碳纳米管0.001～50wt％或纳米碳纤维0.001～50wt％；本发明从已量产的石墨烯出发制备得到的石墨烯复合材料，热导率，热扩散系数，电导率和韧性，都有很大提升(其电导率至少≥10,000S/cm；导热率≥1，000W/m.K；拉伸强度至少；密度至少≥1.60g/cc；晶粒尺寸至少≥10μm；)，而且易于加工。The invention comprises 50-100 wt% of graphene, 0.001-50 wt% of carbon nanotubes or 0.001-50 wt% of nano carbon fibers; the graphene composite material prepared by the invention from the produced graphene, thermal conductivity and thermal diffusivity , conductivity and toughness, have a great improvement (its conductivity is at least ≥ 10,000S / cm; thermal conductivity ≥ 1,000W / mK; tensile strength at least; density of at least ≥ 1.60g / cc; grain size of at least ≥ 10μm ;), and easy to process.
石墨烯为二维片状碳纳米材料，是石墨与碳纳米管的基本构成单元，其优异的物理性能，已让石墨烯成为本世纪的热门材料。单层石墨烯电阻率高达10-6Ω·cm(与单壁纳米碳管及银类似)；导热系数达5300W/m·K(与单壁纳米碳管类似、高于金刚石)；强度可达1000GPa(与多壁纳米碳管类似、是钢的200倍)；电子迁移率高达200000cm2/V.s(与单壁纳米碳管类似、比硅快100倍)； 同时拥有97.7％透明度(优于纳米碳管及ITO)和高达2630m2/g比表面积(是单壁碳纳米管的两倍)。Graphene is a two-dimensional sheet-like carbon nanomaterial, which is the basic building block of graphite and carbon nanotubes. Its excellent physical properties have made graphene a hot material in this century. Single-layer graphene resistivity up to 10 -6 Ω·cm (similar to single-walled carbon nanotubes and silver); thermal conductivity up to 5300 W/m·K (similar to single-walled carbon nanotubes, higher than diamond); 1000GPa (similar to multi-walled carbon nanotubes, 200 times that of steel); electron mobility up to 200000cm 2 /Vs (similar to single-walled carbon nanotubes, 100 times faster than silicon); also has 97.7% transparency (better than nano Carbon tube and ITO) and up to 2630 m 2 /g specific surface area (twice the number of single-walled carbon nanotubes).
利用石墨烯、碳纳米管或纳米碳纤维的高热导率、高导电率、及优良力学性能的特点，可将石墨烯、碳纳米管或纳米碳纤维自组装重排得到各种实用的散热和导电元件。Using graphene, carbon nanotubes or nano-carbon fibers with high thermal conductivity, high electrical conductivity, and excellent mechanical properties, graphene, carbon nanotubes or nano-carbon fibers can be self-assembled and rearranged to obtain various practical heat-dissipating and conductive components. .
与现有技术相比，本发明基于石墨烯的高性能制得的石墨烯复合材料具有下列优点：Compared with the prior art, the graphene composite material produced by the present invention based on the high performance of graphene has the following advantages:
1)、各项性能指标均高于PGS技术；1), all performance indicators are higher than PGS technology;
2)、可在厚膜(＞100μm)下，获得高导热率；2), can obtain high thermal conductivity under thick film (>100μm);
3)、高效率与高产率；3), high efficiency and high yield;
4)、再结晶温度(或石墨化)低，而且时间短。4) The recrystallization temperature (or graphitization) is low and the time is short.
本发明高性能石墨烯复合材料可以膜、纸、棒、块、管等任何形状存在可广泛应用于3C、平板显示器、LED、电池模组、汽车、医疗器械、航天航空、冶金、核反应等工业的散热、导电、防辐射领域。The high-performance graphene composite material of the invention can be widely used in any shape such as film, paper, rod, block, tube, etc., and can be widely used in 3C, flat panel display, LED, battery module, automobile, medical equipment, aerospace, metallurgy, nuclear reaction and other industries. The field of heat dissipation, conduction and radiation protection.
附图说明DRAWINGS
图1为本发明石墨烯复合材料的截面扫描电镜图像，1 is a cross-sectional scanning electron microscope image of a graphene composite material of the present invention,
图2为本发明石墨烯复合材料的表面扫描电镜图像。2 is a surface scanning electron microscope image of a graphene composite material of the present invention.
具体的实施方式Specific embodiment
下面结合具体实施方式对本发明作进一步的详细说明，以助于本领域技术人员理解本发明。The present invention will be further described in detail below in conjunction with the specific embodiments to help those skilled in the art to understand the invention.
实施例1Example 1
一种石墨烯复合材料，包括少层石墨90wt％和碳纳米管(CNT)10wt％。A graphene composite material comprising 90 wt% of a small layer of graphite and 10 wt% of a carbon nanotube (CNT).
制备方法：Preparation:
A.制备高浓度少层石墨浆料，具体的制备参考专利号为201210546111.3的文献； A. Preparing a high concentration of a small layer of graphite slurry, and specifically preparing a reference patent number 201210546111.3;
B.取上述浆料加入到通用抄纸机，按石墨烯/CNT＝90/10的比例加入CNT，B. The above slurry is added to a general-purpose paper machine, and CNT is added in a ratio of graphene/CNT=90/10.
适当稀释和抽滤得到厚度一定的湿石墨烯复合纸；Dilution and suction filtration to obtain a wet graphene composite paper having a certain thickness;
C.取上述湿纸烘干后，在25MPa压力下压实；C. After the above wet paper is dried, it is compacted under a pressure of 25 MPa;
D.将上述石墨复合膜分别置于高温炉1500℃、2200℃、3000℃中，进行再D. The above graphite composite film is placed in a high temperature furnace at 1500 ° C, 2200 ° C, 3000 ° C, and then
结晶处理；得到所述石墨烯复合材料。Crystallization treatment; obtaining the graphene composite material.
检测：用四点法测量膜片电阻率和激光法测量导热率。获得最低电阻率为0.8×10-5ohm.cm、导热系数为2100W/m.K、强度为50MPa。Detection: The resistivity of the diaphragm was measured by a four-point method and the thermal conductivity was measured by a laser method. The lowest resistivity was 0.8×10 -5 ohm.cm, the thermal conductivity was 2100 W/mK, and the strength was 50 MPa.
实施例2Example 2
一种石墨烯复合材料，包括少层石墨90wt％和VGCF 10wt％。A graphene composite material comprising 90% by weight of a small layer of graphite and 10% by weight of VGCF.
制备方法：Preparation:
A.高浓度少层石墨浆料，制备参考专利201210546111.3；A. High concentration and small layer of graphite slurry, preparation reference patent 201210546111.3;
B.取上述浆料加入到通用抄纸机，按石墨烯/VGCF＝90/10的比例加入VGCF，适当稀释和抽滤得到厚度一定的湿石墨烯复合纸；B. The above slurry is added to a general paper machine, VGCF is added in a ratio of graphene / VGCF = 90/10, and diluted and suction filtered to obtain a wet graphene composite paper having a certain thickness;
C.取上述湿纸烘干后，在35MPa压力下压实；C. After the above wet paper is dried, it is compacted under a pressure of 35 MPa;
D.将上述石墨复合膜分别置于高温炉1500℃、2200℃、3000℃中，进行再结晶处理；得到所述石墨烯复合材料。D. The graphite composite film is placed in a high temperature furnace at 1500 ° C, 2200 ° C, and 3000 ° C to perform recrystallization treatment; and the graphene composite material is obtained.
检测：用四点法测量膜片电阻率和激光法测量导热率。获得最低电阻率为2×10-5ohm.cm、导热系数为1900W/m.K、强度为45MPa。Detection: The resistivity of the diaphragm was measured by a four-point method and the thermal conductivity was measured by a laser method. The lowest resistivity was 2 × 10 -5 ohm.cm, the thermal conductivity was 1900 W/mK, and the strength was 45 MPa.
实施例3Example 3
一种石墨烯复合材料，包括少层石墨99wt％和CNT 1wt％。A graphene composite material comprising 99 wt% of a small layer of graphite and 1 wt% of a CNT.
制备方法：Preparation:
A.高浓度少层石墨浆料的制备参考专利201210546111.3；A. Preparation of high concentration and small layer graphite slurry reference patent 201210546111.3;
B.取上述浆料加入到通用抄纸机，按石墨烯/CNT＝99/1的比例加入CNT，适当稀释和抽滤得到厚度一定的湿石墨烯复合纸；B. The above slurry is added to a general-purpose paper machine, and the CNT is added in a ratio of graphene/CNT=99/1, and appropriately diluted and suction-filtered to obtain a wet graphene composite paper having a certain thickness;
C.取上述湿纸烘干后，在25MPa压力下压实； C. After the above wet paper is dried, it is compacted under a pressure of 25 MPa;
E.将上述石墨复合膜分别置于高温炉1500℃、2200℃、3000℃中，进行再结晶处理；得到所述石墨烯复合材料。E. The graphite composite film is placed in a high-temperature furnace at 1500 ° C, 2200 ° C, and 3000 ° C to perform recrystallization treatment; and the graphene composite material is obtained.
检测：用四点法测量膜片电阻率和激光法测量导热率。获得最低电阻率为Detection: The resistivity of the diaphragm was measured by a four-point method and the thermal conductivity was measured by a laser method. Obtain the lowest resistivity
0.5×10-5ohm.cm、导热系数为2300W/m.K、强度为25MPa。0.5×10 -5 ohm.cm, thermal conductivity of 2300 W/mK, and strength of 25 MPa.
实施例4Example 4
一种石墨烯复合材料，包括少层石墨99wt％和VGCF 1wt％。A graphene composite material comprising 99 wt% of a small layer of graphite and 1 wt% of VGCF.
制备方法：Preparation:
A.高浓度少层石墨浆料的制备参考专利201210546111.3；A. Preparation of high concentration and small layer graphite slurry reference patent 201210546111.3;
B.取上述浆料加入到通用抄纸机，按石墨烯/VGCF＝99/1的比例加入VGCF，适当稀释和抽滤得到厚度一定的湿石墨烯复合纸；B. The above slurry is added to a general-purpose paper machine, and VGCF is added in a ratio of graphene/VGCF=99/1, and appropriately diluted and suction-filtered to obtain a wet graphene composite paper having a certain thickness;
C.取上述湿纸烘干后，在35MPa压力下压实；C. After the above wet paper is dried, it is compacted under a pressure of 35 MPa;
D.将上述石墨复合膜分别置于高温炉1500℃、2200℃、3000℃中，进行再结晶处理；D. The above graphite composite film is placed in a high temperature furnace at 1500 ° C, 2200 ° C, 3000 ° C, for recrystallization treatment;
检测：用四点法测量膜片电阻率和激光法测量导热率。获得最低电阻率为2Detection: The resistivity of the diaphragm was measured by a four-point method and the thermal conductivity was measured by a laser method. Get the lowest resistivity of 2
×10-5ohm.cm、导热系数为2200W/m.K、强度为25MPa。×10 -5 ohm.cm, thermal conductivity of 2200 W/mK, and strength of 25 MPa.
上述实施例，只是本发明的较佳实施例，并非用来限制本发明实施范围，故凡以本发明权利要求所述的特征及原理所做的等效变化或修饰，均应包括在本发明权利要求范围之内。The above embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and equivalent changes or modifications made by the features and principles of the present invention should be included in the present invention. Within the scope of the claims.
从图1中可以看出，本发明所述的石墨烯复合材料中纳米石墨烯经再结晶形成的大单晶体。As can be seen from FIG. 1, the large single crystal formed by recrystallization of the nanographene in the graphene composite material of the present invention.
从图2中可以看出，本发明所述的石墨烯复合材料的表面具有皱褶、晶粒边界的表征特性。 As can be seen from FIG. 2, the surface of the graphene composite material of the present invention has the characteristics of wrinkles and grain boundaries.

Claims (10)

  1. 一种石墨烯复合材料，其特征在于，包括石墨烯50～100wt％和其他纳米材料0.001～50wt％，所述其他材料纳米材料为碳纳米管和/或纳米碳纤维。A graphene composite material comprising 50 to 100 wt% of graphene and 0.001 to 50 wt% of other nanomaterials, wherein the other material nanomaterials are carbon nanotubes and/or nanocarbon fibers.
  2. 如权利要求1所述的石墨烯复合材料，其特征在于，所述石墨烯复合材料的表面具有层叠和/或褶皱特征。The graphene composite of claim 1 wherein the surface of the graphene composite has laminate and/or pleat features.
  3. 如权利要求2所述的石墨烯复合材料，其特征在于，所述石墨烯复合材料的晶粒尺寸为10μm～500μm，密度为1.60g/cc～2.20g/cc。The graphene composite according to claim 2, wherein the graphene composite has a crystallite size of from 10 μm to 500 μm and a density of from 1.60 g/cc to 2.20 g/cc.
  4. 如权利要求3所述的石墨烯复合材料，其特征在于，所述石墨烯复合材料拉伸强度为20MPa～100MPa，导热率为1000W/m.K～3000W/m.K。The graphene composite according to claim 3, wherein the graphene composite has a tensile strength of 20 MPa to 100 MPa and a thermal conductivity of 1000 W/m.K to 3000 W/m.K.
  5. 如权利要求4所述的石墨烯复合材料，其特征在于，所述石墨烯复合材料电导率为10000S/cm～1000000S/cm，纯度≥99.90wt％。The graphene composite according to claim 4, wherein the graphene composite has an electrical conductivity of 10,000 S/cm to 1,000,000 S/cm and a purity of ≥99.90 wt%.
  6. 如权利要求1所述的石墨烯复合材料，其特征在于，所述石墨烯为层数≤100，厚度≤34nm。The graphene composite according to claim 1, wherein the graphene has a layer number of ≤100 and a thickness of ≤34 nm.
  7. 如权利要求1所述的石墨烯复合材料，其特征在于，所述碳纳米管为10～100nm的多壁管、3～10nm的少壁管、3～5nm双壁管、0.3～3nm单壁管中的一种或多种复合物。The graphene composite according to claim 1, wherein the carbon nanotubes are multi-wall tubes of 10 to 100 nm, small wall tubes of 3 to 10 nm, double wall tubes of 3 to 5 nm, and single walls of 0.3 to 3 nm. One or more complexes in the tube.
  8. 如权利要求1所述的石墨烯复合材料，其特征在于，所述纳米碳纤维是指100～150nm的气相生长的碳纤维。 The graphene composite material according to claim 1, wherein the nanocarbon fiber is a vapor-grown carbon fiber of 100 to 150 nm.
  9. 制备如权利要求1-8中任意一项所述石墨烯复合材料的方法，其特征在于，包括如下制备步骤：A method of preparing a graphene composite according to any of claims 1-8, comprising the steps of:
    A.制备高浓度薄层石墨浆料；A. preparing a high concentration thin layer graphite slurry;
    B.取上述浆料加入到通用抄纸机，按所述比例加入纳米材料，稀释抽滤得到厚度一定的湿石墨烯复合纸；B. taking the above slurry is added to a general paper machine, adding nano materials according to the ratio, and diluting and filtering to obtain a wet graphene composite paper having a certain thickness;
    C.取上述湿石墨烯复合纸烘干后，在25～35MPa压力下压实，得到石墨复合膜；C. taking the above wet graphene composite paper after drying, compacting at a pressure of 25 to 35 MPa to obtain a graphite composite film;
    D.将上述石墨复合膜置于高温炉中进行再结晶处理，最后得到所述石墨烯复合材料。D. The above graphite composite film is placed in a high temperature furnace for recrystallization treatment, and finally the graphene composite material is obtained.
  10. 如权利要求9中所述制备石墨烯复合材料的方法，其特征在于，所述高温炉中的温度为1000℃～5000℃，压力为0.001～10MPa；再结晶是在真空、惰性气体或吸氧剂保护的气氛下进行。 A method for preparing a graphene composite according to claim 9, wherein the temperature in the high temperature furnace is from 1000 ° C to 5000 ° C and the pressure is from 0.001 to 10 MPa; and the recrystallization is in a vacuum, an inert gas or an oxygen absorption. The atmosphere is protected under the atmosphere.
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