CN117603659B - A method for preparing liquid metal/graphene three-dimensional thermal conductive material and thermal conductive polymer composite material - Google Patents
A method for preparing liquid metal/graphene three-dimensional thermal conductive material and thermal conductive polymer composite material Download PDFInfo
- Publication number
- CN117603659B CN117603659B CN202410073128.4A CN202410073128A CN117603659B CN 117603659 B CN117603659 B CN 117603659B CN 202410073128 A CN202410073128 A CN 202410073128A CN 117603659 B CN117603659 B CN 117603659B
- Authority
- CN
- China
- Prior art keywords
- graphene
- liquid metal
- thermal conductive
- dimensional heat
- heat conduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 169
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 156
- 239000004020 conductor Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 21
- 229920001940 conductive polymer Polymers 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 claims abstract description 34
- 239000004814 polyurethane Substances 0.000 claims abstract description 34
- 239000002135 nanosheet Substances 0.000 claims abstract description 31
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 28
- 229910052738 indium Inorganic materials 0.000 claims abstract description 28
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052718 tin Inorganic materials 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 230000001070 adhesive effect Effects 0.000 claims abstract description 14
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract 5
- 238000001179 sorption measurement Methods 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002322 conducting polymer Substances 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 11
- 238000003763 carbonization Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000000945 filler Substances 0.000 description 18
- 239000004925 Acrylic resin Substances 0.000 description 13
- 229920000178 Acrylic resin Polymers 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 229920005830 Polyurethane Foam Polymers 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000011496 polyurethane foam Substances 0.000 description 11
- 239000006262 metallic foam Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 4
- 238000004227 thermal cracking Methods 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
Description
技术领域Technical Field
本发明涉及一种导热材料及导热高分子复合材料的制备方法，特别是涉及一种液态金属/石墨烯三维导热材料及导热高分子复合材料的制备方法。The invention relates to a method for preparing a heat-conducting material and a heat-conducting polymer composite material, and in particular to a method for preparing a liquid metal/graphene three-dimensional heat-conducting material and a heat-conducting polymer composite material.
背景技术Background technique
导热聚合物材料具有重量轻、成本低、力学性能好、耐腐蚀性能强以及可加工性能好等特点，被广泛应用于热界面材料。由于导热聚合物材料中聚合物基体的本征热导率非常低，引入高导热填料是提高复合材料热导率的常规且可行的方法。然而，虽然导热填料可以有效提高聚合物的导热性能，但是导热网络的形成通常发生在较高填料填充水平下。高负载量以及第二相的存在都会影响复合材料的性能，导致其难以满足热界面材料的设计要求。Thermally conductive polymer materials are widely used in thermal interface materials due to their light weight, low cost, good mechanical properties, strong corrosion resistance and good processability. Since the intrinsic thermal conductivity of the polymer matrix in thermally conductive polymer materials is very low, the introduction of high thermal conductivity fillers is a conventional and feasible method to improve the thermal conductivity of composite materials. However, although thermally conductive fillers can effectively improve the thermal conductivity of polymers, the formation of thermal conductive networks usually occurs at higher filler filling levels. High loading and the presence of a second phase will affect the performance of the composite material, making it difficult to meet the design requirements of thermal interface materials.
石墨烯的二维平面结构与高横纵比使其非常适合作为填料来制备导热聚合物材料，这类材料具有良好的可加工性能、耐腐蚀性能且生产成本低廉等优点。现有技术，石墨烯通常以粉体的形式分散到聚合物基体当中。为了形成连续的导热通道，石墨烯的负载量一般要在20wt%以上，然而这种粉末分散型石墨烯/聚合物复合材料的粘度较高且力学性能较差，给产业化发展带来一定的阻碍。此外，分散在基体中的石墨烯片和聚合物之间存在大量的两相界面，会造成严重的声子散射，而且石墨烯粉体在基体中的分散效果会受到共轭作用的影响，这些因素都会使复合材料的导热性能降低。The two-dimensional planar structure and high aspect ratio of graphene make it very suitable as a filler to prepare thermally conductive polymer materials. Such materials have the advantages of good processability, corrosion resistance and low production cost. In the prior art, graphene is usually dispersed into the polymer matrix in the form of powder. In order to form a continuous heat conduction channel, the loading amount of graphene is generally more than 20wt%. However, the viscosity of this powder-dispersed graphene/polymer composite material is high and the mechanical properties are poor, which brings certain obstacles to industrial development. In addition, there are a large number of two-phase interfaces between the graphene sheets and the polymer dispersed in the matrix, which will cause serious phonon scattering, and the dispersion effect of graphene powder in the matrix will be affected by the conjugation effect. These factors will reduce the thermal conductivity of the composite material.
发明内容Summary of the invention
针对上述现有技术的缺陷，本发明提供了一种液态金属/石墨烯三维导热材料的制备方法，以及使用该液态金属/石墨烯三维导热材料的导热高分子复合材料的制备方法，解决传统胶粘剂必须依赖高导热填料含量（>40%）获得高导热性能但又会导致粘结强度大幅度降低（<10N）的问题，即解决导热性能与粘结性能矛盾的问题。In view of the defects of the above-mentioned prior art, the present invention provides a method for preparing a liquid metal/graphene three-dimensional thermally conductive material, and a method for preparing a thermally conductive polymer composite material using the liquid metal/graphene three-dimensional thermally conductive material, so as to solve the problem that traditional adhesives must rely on a high thermal conductive filler content (>40%) to obtain high thermal conductivity but will cause a significant reduction in bonding strength (<10N), that is, to solve the problem of the contradiction between thermal conductivity and bonding performance.
本发明技术方案如下：一种液态金属/石墨烯三维导热材料的制备方法，将聚氨酯海绵，浸入液态金属/石墨烯混合物中挤压吸附饱和后在保护气氛下加热裂解聚氨酯海绵完全碳化得到独立碳骨架的液态金属/石墨烯三维导热材料，所述液态金属/石墨烯混合物中液态金属由镓、铟和锡组成，所述液态金属/石墨烯混合物中石墨烯为石墨烯纳米片。The technical scheme of the present invention is as follows: a method for preparing a liquid metal/graphene three-dimensional thermal conductive material, comprising: immersing a polyurethane sponge in a liquid metal/graphene mixture, squeezing and adsorbing the mixture until saturated, and then heating and cracking the polyurethane sponge under a protective atmosphere to completely carbonize the polyurethane sponge to obtain a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton, wherein the liquid metal in the liquid metal/graphene mixture is composed of gallium, indium and tin, and the graphene in the liquid metal/graphene mixture is a graphene nanosheet.
本发明的另一技术方案如下：一种液态金属/石墨烯三维导热高分子复合材料的制备方法，将所述液态金属/石墨烯三维导热材料浸润胶粘剂并抽真空混合得到液态金属/石墨烯三维导热高分子复合材料，所述液态金属/石墨烯三维导热材料在所述液态金属/石墨烯三维导热高分子复合材料的体积占比为5%～20%，优选为10%～20%。Another technical solution of the present invention is as follows: a method for preparing a liquid metal/graphene three-dimensional thermally conductive polymer composite material, wherein the liquid metal/graphene three-dimensional thermally conductive material is impregnated with an adhesive and vacuum-mixed to obtain a liquid metal/graphene three-dimensional thermally conductive polymer composite material, wherein the liquid metal/graphene three-dimensional thermally conductive material accounts for 5% to 20% of the volume of the liquid metal/graphene three-dimensional thermally conductive polymer composite material, preferably 10% to 20%.
进一步地，所述聚氨酯海绵的孔径为50～200μm。Furthermore, the pore size of the polyurethane sponge is 50 to 200 μm.
进一步地，所述液态金属/石墨烯混合物中液态金属与石墨烯纳米片的质量比为1:1～1:3。Furthermore, the mass ratio of liquid metal to graphene nanosheets in the liquid metal/graphene mixture is 1:1 to 1:3.
进一步地，所述液态金属中镓、铟、锡的质量百分比分别为20%～40%、40%～50%、20%～40%。Furthermore, the mass percentages of gallium, indium and tin in the liquid metal are 20% to 40%, 40% to 50% and 20% to 40% respectively.
进一步地，所述加热裂解时的加热温度为400～600℃。Furthermore, the heating temperature during the heating cracking is 400-600°C.
与现有技术相比，本发明所提供的技术方案的优点在于：Compared with the prior art, the advantages of the technical solution provided by the present invention are:
石墨烯纳米片骨架配合碳化聚氨酯为复合材料提供了连续的三维热传导路径，大大降低了内部的声子散射，即使在较低的填充含量下，也能有效地提高胶材的导热性能。The graphene nanosheet skeleton combined with carbonized polyurethane provides a continuous three-dimensional heat conduction path for the composite material, greatly reducing the internal phonon scattering, and effectively improving the thermal conductivity of the adhesive even at a lower filling content.
填料间的界面热阻，即填料间的接触热阻，不同于填料与胶粘剂间的界面热阻，在填料分数较低时，影响胶材导热率的主要因素为填料与胶粘剂间的界面热阻，当填料分数增大时，填料间开始相互搭接，填料间的接触热阻就开始体现出来，并常常占据主导作用。填料的搭接涉及导热网络的形成，而此时填料间的接触热阻大小（也即热量从填料传递到相邻填料的难易程度）便成为影响导热网络的关键因素。本发明液态金属在石墨烯片层间形成连接，可以大大降低填料间的界面热阻，大幅提高了网络互联性和热导率。The interfacial thermal resistance between fillers, that is, the contact thermal resistance between fillers, is different from the interfacial thermal resistance between fillers and adhesives. When the filler fraction is low, the main factor affecting the thermal conductivity of the adhesive is the interfacial thermal resistance between fillers and adhesives. When the filler fraction increases, the fillers begin to overlap each other, and the contact thermal resistance between fillers begins to manifest, and often plays a dominant role. The overlap of fillers involves the formation of a thermal conductive network, and at this time, the size of the contact thermal resistance between fillers (that is, the ease of heat transfer from fillers to adjacent fillers) becomes a key factor affecting the thermal conductive network. The liquid metal of the present invention forms a connection between graphene sheets, which can greatly reduce the interfacial thermal resistance between fillers and greatly improve the network connectivity and thermal conductivity.
另外本发明得到的液态金属/石墨烯三维导热材料直接形成导热网络结构，可以在较低的填料含量下提升胶材的导热率，避免高填料含量导致的胶材粘结性能下降的问题。In addition, the liquid metal/graphene three-dimensional thermally conductive material obtained by the present invention directly forms a thermally conductive network structure, which can improve the thermal conductivity of the adhesive material at a lower filler content and avoid the problem of decreased adhesive performance caused by high filler content.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步说明，应理解这些实施例仅用于说明本发明而不用于限制本发明的范围，在阅读了本说明之后，本领域技术人员对本说明的各种等同形式的修改均落于本申请所附权利要求所限定的范围内。The present invention is further described below in conjunction with examples. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of the present invention. After reading this description, various equivalent modifications to this description by those skilled in the art fall within the scope defined by the claims attached to this application.
实施例1，将聚氨酯海绵（孔径100μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为24%，铟的质量占比为40%，锡的质量占比为36%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:2混合。In Example 1, a polyurethane sponge (pore size 100 μm) is cut into an original foam skeleton, and then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption is saturated. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 24%, the mass proportion of indium is 40%, and the mass proportion of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:2.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温500℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数15%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at a high temperature of 500°C under nitrogen protection, and the foam was quickly pyrolyzed and coated to completely carbonize the polymer, thereby obtaining a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to prepare a liquid metal foam/acrylic high thermal conductive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 15%.
实施例2，将聚氨酯海绵（孔径100μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为24%，铟的质量占比为40%，锡的质量占比为36%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:2混合。In Example 2, a polyurethane sponge (pore size 100 μm) is cut into an original foam skeleton, and then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption is saturated. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 24%, the mass proportion of indium is 40%, and the mass proportion of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:2.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温500℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数20%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at a high temperature of 500°C under nitrogen protection, and the polymer was completely carbonized by rapid thermal cracking to obtain a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to make a liquid metal foam/acrylic high thermal conductive tape, in which the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 20%.
实施例3，将聚氨酯海绵（孔径100μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为24%，铟的质量占比为40%，锡的质量占比为36%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:2混合。In Example 3, a polyurethane sponge (pore size 100 μm) is cut into an original foam skeleton, and then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption is saturated. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 24%, the mass proportion of indium is 40%, and the mass proportion of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:2.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温500℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数10%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at a high temperature of 500°C under nitrogen protection, and the foam was quickly pyrolyzed and coated to completely carbonize the polymer, thereby obtaining a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to prepare a liquid metal foam/acrylic high thermal conductive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 10%.
实施例4，将聚氨酯海绵（孔径100μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为24%，铟的质量占比为40%，锡的质量占比为36%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:2混合。In Example 4, a polyurethane sponge (pore size 100 μm) is cut into an original foam skeleton, and then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption is saturated. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 24%, the mass proportion of indium is 40%, and the mass proportion of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:2.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温500℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数5%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at a high temperature of 500°C under nitrogen protection, and the polymer was completely carbonized by rapid thermal cracking to obtain a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to make a liquid metal foam/acrylic high thermal conductive tape, in which the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 5%.
实施例5，将聚氨酯海绵（孔径100μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为24%，铟的质量占比为40%，锡的质量占比为36%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:1混合。In Example 5, a polyurethane sponge (pore size 100 μm) is cut into an original foam skeleton, which is then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption is saturated. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 24%, the mass proportion of indium is 40%, and the mass proportion of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:1.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温500℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数15%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at a high temperature of 500°C under nitrogen protection, and the foam was quickly pyrolyzed and coated to completely carbonize the polymer, thereby obtaining a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to prepare a liquid metal foam/acrylic high thermal conductive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 15%.
实施例6，将聚氨酯海绵（孔径100μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为24%，铟的质量占比为40%，锡的质量占比为36%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:3混合。In Example 6, a polyurethane sponge (pore size 100 μm) is cut into an original foam skeleton, and then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption is saturated. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 24%, the mass proportion of indium is 40%, and the mass proportion of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:3.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温500℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数15%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at a high temperature of 500°C under nitrogen protection, and the foam was quickly pyrolyzed and coated to completely carbonize the polymer, thereby obtaining a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to prepare a liquid metal foam/acrylic high thermal conductive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 15%.
实施例7，将聚氨酯海绵（孔径100μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为30%，铟的质量占比为50%，锡的质量占比为20%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:2混合。In Example 7, a polyurethane sponge (pore size 100 μm) is cut into an original foam skeleton, and then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption is saturated. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 30%, the mass proportion of indium is 50%, and the mass proportion of tin is 20%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:2.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温500℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数15%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at a high temperature of 500°C under nitrogen protection, and the foam was quickly pyrolyzed and coated to completely carbonize the polymer, thereby obtaining a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to prepare a liquid metal foam/acrylic high thermal conductive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 15%.
实施例8，将聚氨酯海绵（孔径100μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为40%，铟的质量占比为40%，锡的质量占比为20%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:2混合。In Example 8, a polyurethane sponge (pore size 100 μm) is cut into an original foam skeleton, and then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption is saturated. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 40%, the mass proportion of indium is 40%, and the mass proportion of tin is 20%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:2.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温500℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数15%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at a high temperature of 500°C under nitrogen protection, and the foam was quickly pyrolyzed and coated to completely carbonize the polymer, thereby obtaining a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to prepare a liquid metal foam/acrylic high thermal conductive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 15%.
实施例9，将聚氨酯海绵（孔径200μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为24%，铟的质量占比为40%，锡的质量占比为36%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:2混合。In Example 9, a polyurethane sponge (pore size 200 μm) is cut into an original foam skeleton, and then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption is saturated. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 24%, the mass proportion of indium is 40%, and the mass proportion of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:2.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温400℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数15%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at 400°C under nitrogen protection, and the foam was quickly pyrolyzed and coated to completely carbonize the polymer, thereby obtaining a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to prepare a liquid metal foam/acrylic high thermal conductive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 15%.
实施例10，将聚氨酯海绵（孔径50μm）切成原始泡沫骨架，随后浸入液态金属/石墨烯混合物中，重复挤压聚氨酯海绵至吸附饱和。液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为24%，铟的质量占比为40%，锡的质量占比为36%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:2混合。In Example 10, a polyurethane sponge (pore size 50 μm) is cut into an original foam skeleton, and then immersed in a liquid metal/graphene mixture, and the polyurethane sponge is repeatedly squeezed until adsorption saturation. The liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 24%, the mass proportion of indium is 40%, and the mass proportion of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5 μm and a thickness of about 40 nm, and the liquid metal and the graphene nanosheet are mixed in a mass ratio of 1:2.
通过上述挤压吸附工艺在聚氨酯泡沫骨架表面组装了液态金属/石墨烯，将组装后的泡沫在氮气保护下高温600℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的液态金属/石墨烯三维导热材料。然后将液态金属/石墨烯三维导热材料浸润丙烯酸树脂并抽真空，制成液态金属泡沫/丙烯酸高导热胶带，其中液态金属/石墨烯三维导热材料的体积分数15%。Liquid metal/graphene was assembled on the surface of the polyurethane foam skeleton by the above-mentioned extrusion adsorption process, and the assembled foam was heated at a high temperature of 600°C under nitrogen protection, and the polymer was completely carbonized by rapid thermal cracking to obtain a liquid metal/graphene three-dimensional thermal conductive material with an independent carbon skeleton. Then, the liquid metal/graphene three-dimensional thermal conductive material was infiltrated with acrylic resin and vacuumed to make a liquid metal foam/acrylic high thermal conductive tape, in which the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 15%.
对比例1为纯丙烯酸制成的胶带。Comparative Example 1 is an adhesive tape made of pure acrylic acid.
对比例2将液态金属/石墨烯按体积分数15%直接以机械搅拌的方式混入丙烯酸树脂中制成导热胶带，其中液态金属/石墨烯混合物中液态金属由金属镓（Ga）、铟（In）和锡（Sn）熔合而成，其中镓的质量占比为24%，铟的质量占比为40%，锡的质量占比为36%。液态金属/石墨烯混合物中石墨烯为大小为5μm、厚度约40nm的石墨烯纳米片，液态金属与石墨烯纳米片按质量比1:2混合。Comparative Example 2: Liquid metal/graphene is directly mixed into acrylic resin by mechanical stirring at a volume fraction of 15% to prepare a thermal conductive tape, wherein the liquid metal in the liquid metal/graphene mixture is fused by metal gallium (Ga), indium (In) and tin (Sn), wherein the mass proportion of gallium is 24%, the mass proportion of indium is 40%, and the mass proportion of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nanosheet with a size of 5μm and a thickness of about 40nm, and the liquid metal and the graphene nanosheet are mixed at a mass ratio of 1:2.
对比例3，将聚氨酯海绵（孔径100μm）切成原始泡沫骨架，随后浸入石墨烯纳米片溶液中重复挤压聚氨酯海绵至吸附饱和，石墨烯纳米大小为5μm、厚度约40nm。在聚氨酯泡沫骨架表面组装石墨烯，将组装后的泡沫在氮气保护下高温500℃加热，快速热裂解包覆泡沫，使聚合物完全碳化，得到独立碳骨架的石墨烯导热材料。然后将石墨烯导热材料浸入丙烯酸树脂中并抽真空，制成丙烯酸导热胶带，其中液态金属/石墨烯三维导热材料的体积分数15%。In comparative example 3, a polyurethane sponge (pore size 100 μm) was cut into a raw foam skeleton, and then immersed in a graphene nanosheet solution and repeatedly squeezed the polyurethane sponge until adsorption saturation, the graphene nanosheet size was 5 μm and the thickness was about 40 nm. Graphene was assembled on the surface of the polyurethane foam skeleton, and the assembled foam was heated at a high temperature of 500 ° C under nitrogen protection, and the polymer was completely carbonized by rapid thermal cracking to obtain a graphene thermal conductive material with an independent carbon skeleton. The graphene thermal conductive material was then immersed in acrylic resin and vacuumed to make an acrylic thermal conductive tape, in which the volume fraction of the liquid metal/graphene three-dimensional thermal conductive material was 15%.
测试上述各实施例和对比例的胶带的导热率，热导率测试方法参照ASTME1461标准执行，结果如表1所示。The thermal conductivity of the adhesive tapes of the above embodiments and comparative examples was tested. The thermal conductivity test method was performed according to ASTM E1461 standard. The results are shown in Table 1.
表1为各实施例及各对比例的导热系数测试结果。Table 1 shows the thermal conductivity test results of various embodiments and comparative examples.
按照GB 2792-2014标准测定的导热胶带的180°剥离力。具体来说，将导热胶带裁剪成25mmx200mm标准胶带,然后将其粘接在经过丙酮擦拭后的不锈钢板上，用2kg重的橡胶辊前后滚压三次后来除去钢板与胶带之间可能存在的气泡。放置15min 后，对其由电子剥离试验机在300mm/min的剥离速度下进行180°剥离力的测试。每个样品所得到的剥离力是测量三次的剥离力平均后的结果，结果如表2所示。The 180° peeling force of the thermal conductive tape was measured according to GB 2792-2014. Specifically, the thermal conductive tape was cut into 25mmx200mm standard tapes, and then bonded to a stainless steel plate wiped with acetone. A 2kg rubber roller was used to roll back and forth three times to remove any bubbles that may exist between the steel plate and the tape. After standing for 15 minutes, the 180° peeling force was tested at a peeling speed of 300mm/min using an electronic peeling tester. The peeling force obtained for each sample is the average result of the three peeling force measurements, as shown in Table 2.
表2为各实施例及各对比例的剥离力测试结果。Table 2 shows the peeling force test results of each embodiment and each comparative example.
由上述测试结果可以看出，相比于直接将液态金属以及石墨烯纳米片作为导热填料混入丙烯酸树脂制作导热胶带，以聚氨酯海绵作泡沫骨架进行碳化后得到的导热材料在胶带中能发挥更好的导热效果，并且对胶带粘结力的影响更小。It can be seen from the above test results that compared with directly mixing liquid metal and graphene nanosheets as thermal conductive fillers into acrylic resin to make thermal conductive tape, the thermal conductive material obtained by carbonizing polyurethane sponge as the foam skeleton can play a better thermal conductive effect in the tape and has less impact on the bonding strength of the tape.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410073128.4A CN117603659B (en) | 2024-01-18 | 2024-01-18 | A method for preparing liquid metal/graphene three-dimensional thermal conductive material and thermal conductive polymer composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410073128.4A CN117603659B (en) | 2024-01-18 | 2024-01-18 | A method for preparing liquid metal/graphene three-dimensional thermal conductive material and thermal conductive polymer composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117603659A CN117603659A (en) | 2024-02-27 |
| CN117603659B true CN117603659B (en) | 2024-04-19 |
Family
ID=89958192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410073128.4A Active CN117603659B (en) | 2024-01-18 | 2024-01-18 | A method for preparing liquid metal/graphene three-dimensional thermal conductive material and thermal conductive polymer composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117603659B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105321724A (en) * | 2015-11-20 | 2016-02-10 | 中国科学技术大学 | Three-dimensional porous graphene, preparation method and application therefor |
| CN110607167A (en) * | 2019-10-14 | 2019-12-24 | 苏州大学 | A three-dimensional composite heat dissipation slurry containing liquid metal and a heat dissipation film prepared therefrom |
| CN112374490A (en) * | 2020-10-31 | 2021-02-19 | 华南理工大学 | Three-dimensional porous graphene/polyurethane flexible stress-strain sensor and preparation method thereof |
| CN112447634A (en) * | 2019-09-02 | 2021-03-05 | 清华大学 | Thermal interface material with low Young modulus and high thermal conductivity as well as preparation method and application thereof |
| CN114369365A (en) * | 2021-12-06 | 2022-04-19 | 华东理工大学 | Preparation method of pre-constructed three-dimensional graphene network and heat-conducting composite material |
| CN114835494A (en) * | 2022-06-08 | 2022-08-02 | 常州二维碳素科技股份有限公司 | Preparation method of high-performance graphene heat-conducting film |
| CN116285909A (en) * | 2023-03-08 | 2023-06-23 | 广东光钛领先新材料有限公司 | Leakage-proof liquid metal-graphene material and preparation method thereof |
| CN117279345A (en) * | 2022-11-24 | 2023-12-22 | 东莞市光钛科技有限公司 | Preparation method and application of high-heat-conductivity flexible electromagnetic shielding material |
-
2024
- 2024-01-18 CN CN202410073128.4A patent/CN117603659B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105321724A (en) * | 2015-11-20 | 2016-02-10 | 中国科学技术大学 | Three-dimensional porous graphene, preparation method and application therefor |
| CN112447634A (en) * | 2019-09-02 | 2021-03-05 | 清华大学 | Thermal interface material with low Young modulus and high thermal conductivity as well as preparation method and application thereof |
| CN110607167A (en) * | 2019-10-14 | 2019-12-24 | 苏州大学 | A three-dimensional composite heat dissipation slurry containing liquid metal and a heat dissipation film prepared therefrom |
| CN112374490A (en) * | 2020-10-31 | 2021-02-19 | 华南理工大学 | Three-dimensional porous graphene/polyurethane flexible stress-strain sensor and preparation method thereof |
| CN114369365A (en) * | 2021-12-06 | 2022-04-19 | 华东理工大学 | Preparation method of pre-constructed three-dimensional graphene network and heat-conducting composite material |
| CN114835494A (en) * | 2022-06-08 | 2022-08-02 | 常州二维碳素科技股份有限公司 | Preparation method of high-performance graphene heat-conducting film |
| CN117279345A (en) * | 2022-11-24 | 2023-12-22 | 东莞市光钛科技有限公司 | Preparation method and application of high-heat-conductivity flexible electromagnetic shielding material |
| CN116285909A (en) * | 2023-03-08 | 2023-06-23 | 广东光钛领先新材料有限公司 | Leakage-proof liquid metal-graphene material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117603659A (en) | 2024-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110951254A (en) | Boron nitride composite high-thermal-conductivity insulating polymer composite material and preparation method thereof | |
| CN110540729B (en) | Light high-conductivity shielding material and preparation method thereof | |
| CN109206961B (en) | A kind of graphene conductive and thermally conductive coating and preparation method thereof | |
| CN111171449B (en) | High-thermal-conductivity polypropylene/graphene composite material and preparation method thereof | |
| CN100514502C (en) | Polymer-based carbon conductivity macromolecule composite material | |
| CN114891485B (en) | Graphene framework heat-conducting composite material based on three-dimensional vertical arrangement and preparation method thereof | |
| CN105330857A (en) | Preparation method of PANI (polyaniline)-GO (graphene oxide)-CNTs (carbon nanotubes) composited electromagnetic shielding material | |
| CN108521683A (en) | Nanocellulose graphene oxide electrothermal material and preparation method thereof | |
| CN107674349A (en) | Low-dielectric-constant fluorine-containing polymer composite material and preparation method thereof | |
| CN104934237A (en) | Preparation method for nitrogen-doped porous carbon/graphene two-dimensional composite electrode material | |
| CN105802016B (en) | PP base stage ear materials and preparation method thereof | |
| CN114725458A (en) | Preparation method of CCM (continuous catalytic cracking) with catalyst coating not easy to crack | |
| CN117603659B (en) | A method for preparing liquid metal/graphene three-dimensional thermal conductive material and thermal conductive polymer composite material | |
| CN107903575B (en) | A kind of preparation method of graphene phenolic resin-based composite fiber membrane for capacitor electrode | |
| CN113044834B (en) | Graphene macroscopic body material, graphene/polymer composite material, preparation method and application thereof | |
| Niu et al. | Corrosion and high temperature resistance effectively EMI shielding PTFE-CNTs nanocomposites | |
| CN115595125A (en) | A kind of graphite insulation heat conduction composite material and preparation method thereof | |
| CN118448665A (en) | Expanded graphite flake graphite composite fuel cell plate and preparation method thereof | |
| CN115000413B (en) | A heat-resistant carbon-coated aluminum foil for power battery current collector and a preparation method thereof | |
| WO2020232773A1 (en) | Polyphenylene sulfide composite material film having high vertical thermal conductivity and preparation method therefor | |
| CN106009517A (en) | Conductive epoxy resin/nickel-plated carbon fiber composite foam and preparation method thereof | |
| CN113150498B (en) | High-strength heat-conducting insulating epoxy resin composite material and preparation method thereof | |
| CN112961450B (en) | A CNTs@r-fGS/PVDF composite material and its preparation method | |
| KR20120006782A (en) | Electrochemical Capacitor Electrode and Manufacturing Method Thereof | |
| KR102709695B1 (en) | Multilayer Film for Electromagnetic Wave Shielding and Manufacturing Method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |