CN115159511A - Graphene material, preparation method thereof and heat-conducting gasket - Google Patents
Graphene material, preparation method thereof and heat-conducting gasket Download PDFInfo
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Abstract
The scheme discloses a graphene material, a preparation method thereof and a heat conduction gasket, wherein graphene oxide slurry is coated on the surface of a substrate, and a first layer of template is arranged after the graphene oxide slurry is coated; drying the graphene oxide slurry between the substrate and the first layer of template to form a first layer of graphene oxide coating; coating the graphene oxide slurry on the first layer of template, and then arranging a second layer of template; drying the graphene oxide slurry between the first layer of template and the second layer of template to form a second layer of graphene oxide coating; repeating the steps of coating the graphene oxide slurry, setting the template and drying to a preset thickness to obtain a graphene oxide blank; carrying out heat treatment on the blank to obtain a graphene material which is composed of multiple graphene layers, wherein layered gaps exist between the upper graphene layer and the lower graphene layer, and multiple graphene columns are distributed between the layered gaps; wherein the template is made of foaming material; the template is provided with a through hole penetrating through the template along the thickness direction. The graphene material is used for preparing the reinforced composite material, and is simple and feasible.
Description
Technical Field
The invention relates to the technical field of heat conduction materials, in particular to a graphene material, a preparation method thereof and a heat conduction gasket.
Background
The graphene heat-conducting film is generally a graphene film structure material with high heat conductivity formed by coating, drying and heat treating graphene oxide slurry. The heat-conducting material has good heat-conducting property (the heat-conducting coefficient is more than 1500W/(m.K)), excellent structural strength and excellent flexible and foldable property, and is widely applied to the fields of smart phones, tablet computers, ultrathin notebooks and the like. Meanwhile, the graphene heat-conducting film has a wide application prospect in composite materials, particularly high-heat-conducting composite materials. However, when the graphene thermal conductive film is used for preparing the composite material, the composite material has the problems of poor mechanical property, easy cracking and the like due to insufficient bonding force with matrix materials such as high polymers and the like. The reason for this is that the graphene thermal conductive film has a dense structure, and it is difficult to impregnate a matrix material such as a polymer into the graphene thermal conductive film. In contrast, patent documents CN112852159A, CN113147115A, CN113290958A, and CN113510979A disclose that a composite material is prepared by using a foam structure-filling polymer or the like inside a graphene foam film. However, since the pores inside the graphene foam film are small in size and mostly closed, great difficulty is added to the impregnation of a matrix material such as a polymer, and only a small amount of pores can be filled. Therefore, the obtained composite material is not compact, still has poor mechanical properties and is easy to crack.
Disclosure of Invention
One purpose of the scheme is to provide a preparation method of a graphene material, and the graphene material prepared by the method is simple and feasible and used for preparing various reinforced composite materials.
Another object of the present disclosure is to provide a graphene material prepared by the above method, wherein the graphene material has layered voids and through holes composed of graphene distributed in the layered voids.
The third purpose of this scheme provides a graphite alkene heat conduction gasket.
In order to achieve the purpose, the scheme is as follows:
a preparation method of a graphene material comprises the following steps:
coating graphene oxide slurry on the surface of a base material, and arranging a first layer of template after coating;
drying the graphene oxide slurry between the substrate and the first layer of template to form a first layer of graphene oxide coating; coating the graphene oxide slurry on the first layer of template, and then arranging a second layer of template;
drying the graphene oxide slurry between the first layer of template and the second layer of template to form a second layer of graphene oxide coating;
repeating the steps of coating the graphene oxide slurry, setting the template and drying to a preset thickness to obtain a graphene oxide blank;
carrying out heat treatment on the graphene oxide blank to obtain a graphene material which is composed of multiple graphene layers, wherein layered gaps exist between the upper graphene layer and the lower graphene layer, and a plurality of graphene columns are distributed between the layered gaps;
wherein the template is made of a foaming material; and the template is provided with a through hole penetrating through the template along the thickness direction.
In the above heat treatment process, the graphene oxide is thermally reduced to graphene; the template foams to form a layered gap, and a small amount of carbon layer formed after heat treatment is integrated with the graphene.
Preferably, the layered gap is a layer of gap existing between upper and lower adjacent graphene layers, the size of the gap of the layered gap in the direction parallel to the graphene layers is 50 μm to 1000 μm, and the size of the gap in the direction perpendicular to the graphene layers is 30 μm to 200 μm;
the template is provided with a plurality of through holes.
The size of the layered gap is lower than 50 μm in the direction parallel to the graphene layer, so that the gap is too small to facilitate the subsequent polymer to be immersed; if the thickness is more than 1000 mu m, the gap is too large, which is not beneficial to the stability of the whole body, the gap structure is easy to collapse, and the sample is damaged; in the vertical direction, if the thickness is less than 30 μm, the gap is too small, which is not favorable for the subsequent polymer to be immersed; if the thickness is more than 200 μm, the voids are too large, which is disadvantageous to the stability of the whole, and the void structure is easily collapsed, thus damaging the sample.
Preferably, the temperature for heat treatment of the graphene oxide blank is 2400 ℃ or higher, and preferably 2800 ℃ or higher;
the graphene oxide layer is formed by coating and drying graphene oxide slurry; the drying temperature is 40-150 ℃.
Preferably, the weight percentage of the graphene oxide in the graphene oxide slurry is 0.5wt.% to 10wt.%, and preferably, the weight percentage of the graphene oxide is 2wt.% to 8wt.%.
The content of the graphene oxide in the graphene oxide slurry is lower than 0.5wt.%, the slurry is too thin and cannot be coated, and the content of the graphene oxide in the graphene oxide slurry is higher than 10wt.%, and the slurry is too thick and cannot be coated.
Preferably, the thickness of the graphene oxide layer is 0.1mm to 1mm, and preferably, the thickness of the graphene oxide layer is 0.25mm to 0.8mm. The thickness of the graphene oxide layer is lower than 0.1mm, so that accurate control cannot be carried out; higher than 1mm, too thick coating, easy formation of own pores by graphene oxide, uncontrolled and difficult realization of control of the internal gaps of the whole material
Preferably, the method further comprises peeling off the substrate after obtaining the graphene oxide blank with the preset thickness;
the base material includes polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), copper foil, aluminum film or glass.
Preferably, the thickness of the template layer is 5-50 μm, and the thickness of the template layer is 10-20 μm; the aperture size of the through hole on the template layer is 50-200 mu m, and the aperture size of the through hole is preferably 100-150 mu m; the hole pitch between every two through holes on the template layer is 100-200 μm, and preferably the hole pitch is 120-160 μm.
The thickness of the template layer is less than 5 mu m, the template layer cannot play a role when being too thin, and the formed gap structure is not obvious; the thickness is higher than 50 μm, so that the gap is too large, and the mechanical stability of a sample is influenced; the aperture of the through hole on the template layer is smaller than 50 mu m, which causes poor combination between upper and lower graphene layers, and larger than 200 mu m, which causes unsmooth communication between gaps, thus being not beneficial to the later stage of the immersion of high molecular polymer; the hole pitch between the through holes is less than 100 mu m, so that the gaps are too small, and the later-stage polymer immersion is not facilitated; above 200 μm, the voids are too large and do not contribute to the mechanical stability of the sample.
Preferably, the foaming material is a polymer film, and comprises epoxy resin, phenolic resin, furfural resin, polyimide (PI), polyarylacetylene (PAA), polymethyl methacrylate (PMMA), asphalt, ABS, PC-ABS, polyethylene terephthalate (PET) or Polyurethane (PU).
In a second aspect, a graphene material prepared by any one of the above preparation methods is provided, wherein the graphene material is composed of multiple graphene layers, layered gaps exist between upper and lower adjacent graphene layers, and multiple graphene columns are distributed between the layered gaps.
The third aspect provides a graphene heat conduction gasket, which is prepared from the graphene material, and comprises the steps of immersing the prepared graphene material into a high molecular polymer, taking out the graphene material, curing and molding the graphene material, and cutting the graphene material into sheets along the thickness direction to prepare the graphene heat conduction gasket; in the graphene thermal conductive gasket, the weight percentage of graphene is 30wt.% to 70wt.%, and preferably, the weight percentage of graphene is 40wt.% to 60wt.%.
The content of graphene in the heat-conducting gasket is lower than 30wt.%, so that the heat-conducting performance of the material is obviously reduced due to the excessively low content of graphene; above 70wt.%, the high molecular weight polymer content is too low and the sample is prone to cracking during use.
The beneficial effect of this scheme as follows:
1. the preparation method provided by the application prepares the graphene material with a layered gap and a through hole structure between graphene layers;
2. the prepared graphene material can be used for reinforcing a composite material;
3. the enhancement mode is simple and easy to implement;
4. the prepared graphene material is directly impregnated and reinforced to obtain the graphene heat-conducting gasket with excellent heat-conducting property and mechanical property.
Drawings
In order to illustrate the implementation of the solution more clearly, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the solution, and that other drawings may be derived from these drawings by a person skilled in the art without inventive effort.
Fig. 1 is a schematic structural diagram of a graphene oxide blank prepared in an example.
Detailed Description
Embodiments of the present solution are described in further detail below. It is clear that the described embodiments are only a part of the embodiments of the present solution, and not an exhaustive list of all embodiments. It should be noted that, in the present embodiment, features of the embodiment and the embodiment may be combined with each other without conflict.
The terms first, second and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It will be appreciated that the data so used may be interchanged where appropriate. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The inventor of the present application provides a graphene material, which is composed of multiple graphene layers, wherein layered gaps exist between upper and lower adjacent graphene layers, and multiple graphene columns are distributed between the layered gaps, and the layered gaps exist between the graphene layers, and the graphene columns are distributed between the layered gaps, so that the upper and lower adjacent graphene layers are connected through the graphene columns.
After the graphene material is immersed into the high-molecular polymer, the high-molecular polymer immersed into the layered gap of the same layer forms a whole after being cured, therefore, the graphene of each upper layer and each lower layer in the obtained composite material is mutually continuous, and the high-molecular polymer after being cured distributed between the graphene layers forms a whole.
According to the application, organic silica gel is used as a high molecular polymer and combined with the prepared graphene material, so that the graphene heat conduction gasket with excellent heat conduction performance and good mechanical property is obtained.
The application provides a preparation method of a graphene material, which comprises the following steps:
coating graphene oxide slurry on the surface of a base material, and arranging a first layer of template after coating;
drying the graphene oxide slurry between the substrate and the first layer of template to form a first layer of graphene oxide coating; coating the graphene oxide slurry on the first layer of template, and then arranging a second layer of template;
drying the graphene oxide slurry between the first layer of template and the second layer of template to form a second layer of graphene oxide coating;
repeating the steps of coating the graphene oxide slurry, setting the template and drying to a preset thickness to obtain a graphene oxide blank;
carrying out heat treatment on the graphene oxide blank to obtain a graphene material which is composed of multiple graphene layers, wherein layered gaps exist between upper and lower adjacent graphene layers, and a plurality of graphene columns are distributed between the layered gaps;
wherein the template is made of foaming material; the template is provided with a through hole penetrating through the template along the thickness direction.
The thickness direction in the scheme is the direction vertical to the plane of the template.
In the above heat treatment process, the graphene oxide is thermally reduced to graphene; the template foams to form a layered gap, and a small amount of carbon layer formed after heat treatment is integrated with the graphene.
Due to the through holes in each layer of the template, after the graphene oxide slurry is coated on the template, the graphene oxide slurry flows into the through holes, and when the graphene oxide slurry is subjected to heat treatment, the graphene oxide slurry in the through holes forms graphene columns.
In one embodiment, the weight percent of graphene oxide in the graphene oxide slurry is 0.5 to 10wt.%, preferably the weight percent of graphene oxide is 2 to 8wt.%, such as 0.5wt.%,1wt.%,2wt.%,2.5wt.%,3.5wt.%,4wt.%,4.5wt.%,5wt.%,5.5wt.%,6wt.%,6.5wt.%,7wt.%,7.5wt.%,8wt.%,9wt.% or 10wt.%; the graphene oxide layer has a thickness of 0.1 to 1mm, preferably 0.25 to 0.8mm, such as 0.1mm,0.2mm,0.25mm,0.3mm,0.35mm,0.4mm,0.45mm,0.5mm,0.55mm,0.6mm,0.65mm,0.7mm,0.75mm,0.8mm,0.9mm or 1.0mm.
In one embodiment, the substrate comprises at least one of PET, PP, PE, PVC, PTFE, copper foil, aluminum film and glass.
In one embodiment, the template layer has a thickness of 5 μm to 50 μm, preferably a thickness of 10 μm to 20 μm, such as 5 μm,10 μm,11 μm,12 μm,13 μm,14 μm,15 μm,16 μm,17 μm,18 μm,19 μm,20 μm,25 μm,30 μm,35 μm,40 μm,45 μm or 50 μm; the size of the aperture of the through-hole on the template layer is 50 μm to 200 μm, preferably the size of the aperture of the through-hole is 100 μm to 150 μm, such as 50 μm,55 μm,60 μm,65 μm,70 μm,75 μm,80 μm,85 μm,90 μm,95 μm,100 μm,105 μm,110 μm,115 μm,120 μm,125 μm,130 μm,135 μm,140 μm,145 μm,150 μm,155 μm,160 μm,165 μm,170 μm,175 μm,180 μm,185 μm,190 μm,195 μm, or 200 μm; the hole pitch between each two through holes on the template layer is 100 μm to 200 μm, preferably 120 μm to 160 μm, such as 100 μm,110 μm,120 μm,125 μm,130 μm,135 μm,140 μm,145 μm,150 μm,155 μm,160 μm,170 μm,180 μm,190 μm or 200 μm.
In one embodiment, the layered voids are a layer of voids existing between upper and lower adjacent graphene layers, and the size of the voids of the layered voids in a direction parallel to the graphene layers is 50 μm to 1000 μm, such as 50 μm,100 μm,200 μm,300 μm,400 μm,500 μm,600 μm,700 μm,800 μm,900 μm or 1000 μm; the size of the voids in a direction perpendicular to the graphene layer is from 30 μm to 200 μm, such as 30 μm,40 μm,50 μm,60 μm,70 μm,80 μm,90 μm,100 μm,110 μm,120 μm,130 μm,140 μm,150 μm,160 μm,170 μm,180 μm,190 μm or 200 μm.
In one embodiment, the template has a plurality of through holes.
In one embodiment, the graphene oxide blank is heat treated at a temperature of 2400 ℃ or higher, preferably at a temperature of 2800 ℃ or higher; the graphene oxide layer is formed by coating and drying graphene oxide slurry; the drying temperature is 40-150 deg.C, such as 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C or 150 deg.C.
In one embodiment, the template is a polymer film comprising epoxy, phenolic, furfural, polyimide (PI), polyarylacetylene (PAA), polymethylmethacrylate (PMMA), asphalt, ABS, PC-ABS, polyethylene terephthalate (PET), or Polyurethane (PU).
The graphene material is composed of multiple graphene layers, layered gaps exist between the upper graphene layer and the lower graphene layer, and multiple graphene columns are distributed between the layered gaps.
The application also provides a graphene heat-conducting gasket which is prepared from the graphene material, and the preparation method comprises the steps of immersing the prepared graphene material into a high-molecular polymer, taking out the graphene material, curing and molding the graphene material, and cutting the graphene material into sheets along the thickness direction to prepare the graphene heat-conducting gasket; in the prepared graphene thermal conductive pad, the weight percentage of the graphene is 30wt.% to 70wt.%, and preferably, the weight percentage of the graphene is 40wt.% to 60wt.%, for example, 30wt.%,40wt.%,45wt.%,50wt.%,55wt.%,60wt.% or 70wt.%.
The thickness of the graphene used for preparing the heat conducting gasket is not particularly limited, and is preferably 25 to 100mm in the application.
The present application will be described below with reference to specific examples.
A preparation method of a graphene heat conduction gasket comprises the following steps:
coating graphene oxide slurry on the surface of a base material, and arranging a first layer of template after coating;
drying the graphene oxide slurry between the substrate and the first layer of template to form a first layer of graphene oxide coating; coating the graphene oxide slurry on the first layer of template, and then arranging a second layer of template;
drying the graphene oxide slurry between the first layer of template and the second layer of template to form a second layer of graphene oxide coating;
repeating the steps of coating the graphene oxide slurry, setting a template and drying to a preset thickness to obtain a graphene oxide blank;
carrying out heat treatment on the graphene oxide blank to obtain a graphene material which is composed of multiple graphene layers, wherein layered gaps exist between the upper graphene layer and the lower graphene layer, and multiple graphene columns are distributed between the layered gaps;
immersing a graphene material with layered gaps into a high-molecular polymer;
and after curing and forming, cutting the obtained product into pieces along the thickness direction to obtain the graphene heat-conducting gasket.
The graphene material with the layered voids prepared in each embodiment is subjected to a performance parameter test, and the thermal diffusion coefficient of the graphene material is tested by referring to an ASTME1461 flash method;
testing the specific heat capacity of the graphene material by referring to ASTM E1269-2018 differential scanning calorimetry; testing the density of the graphene material according to GB 4472-1984;
in the present application, the thermal conductivity of the graphene material is calculated by using the following formula:
K＝λ·C p ·ρ
k-thermal conductivity, in W/(m.K);
lambda-thermal diffusion coefficient in mm 2 /s；
C p -specific heat capacity, in units J/(g · K);
rho-density in g/cm 3 ；
Testing the heat conductivity coefficient and the application thermal resistance of the graphene heat conduction gasket made of the graphene material by referring to an ASTMD5470 test method, wherein the application thermal resistance is the sum of intrinsic thermal resistance and thermal contact resistance of the upper surface and the lower surface;
the longitudinal compressibility and compression resilience of the graphene heat-conducting gasket are tested according to the ASTM D395 determination method, and the compression rate of a sample under 40psi pressure and the rebound rate of the sample after being compressed to 50% strain and then being kept for 30min are respectively tested.
For comparison, in the embodiment of the application, the applied thermal resistance, the compressibility, the compression resilience and other performances of the graphene thermal conductive gasket are tested, and a sample with the thickness of 0.5mm is uniformly adopted.
Examples 1 to 5
In each embodiment of the present application, the graphene material and the graphene thermal pad are prepared according to the above steps of preparing the graphene material and the graphene thermal pad, except that the raw materials used for preparing the graphene material, the template material, the thickness of the template, the aperture of the through hole formed in the template, and the distance between every 2 through holes when a plurality of through holes are formed, the drying condition for the graphene oxide slurry and the heat treatment condition for the graphene oxide blank are different as shown in table 1, the characteristics and performance test results of the graphene material prepared in each embodiment are shown in table 2, and the content of graphene in the graphene thermal pad prepared in each embodiment and the performance test results of the thermal pad are shown in table 3. The solid content in the graphene oxide slurry of each example refers to the content of graphene oxide in the graphene oxide slurry. In each embodiment, liquid silica gel is used as an adhesive for bonding a high molecular polymer and a graphene coating, and other types of adhesives are also applicable.
Fig. 1 illustrates a structure of a graphene oxide blank in each embodiment, in which graphene oxide layers 1 and templates 2 are alternately arranged, and after a predetermined thickness is reached, the graphene oxide blank is subjected to a heat treatment to obtain a graphene material with layered voids.
TABLE 1
TABLE 2
TABLE 3
From above embodiment can learn, this application has realized the preparation of the graphite alkene material that has the stratiform space through going on template and the coating interval of oxidation graphite alkene thick liquids when preparing graphite alkene material, and wherein the size in stratiform space can be regulated and control through the template size, and the size in stratiform space makes things convenient for the dipping of high-molecular polymer moreover.
The graphene material prepared by the application keeps an integral continuous structure, and when the graphene material is applied to a composite material, a heat conduction channel is continuous, so that the heat conduction effect is enhanced and maximized; the high molecular polymer immersed in the layered gap of each layer forms a continuous structure, so that the mechanical property of the composite material is improved to the maximum extent; the prepared graphene material is directly impregnated and matched with a cutting and slicing process, and a graphene heat conduction gasket product with good heat conduction performance and stable mechanical property can be obtained.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A preparation method of a graphene material is characterized by comprising the following steps:
coating graphene oxide slurry on the surface of a base material, and arranging a first layer of template after coating;
drying the graphene oxide slurry between the substrate and the first layer of template to form a first layer of graphene oxide coating; coating the graphene oxide slurry on the first layer of template, and then arranging a second layer of template;
drying the graphene oxide slurry between the first layer of template and the second layer of template to form a second layer of graphene oxide coating;
repeating the steps of coating the graphene oxide slurry, setting the template and drying to a preset thickness to obtain a graphene oxide blank;
carrying out heat treatment on the graphene oxide blank to obtain a graphene material which is composed of multiple graphene layers, wherein layered gaps exist between the upper graphene layer and the lower graphene layer, and a plurality of graphene columns are distributed between the layered gaps;
wherein the template is made of a foaming material;
and the template is provided with a through hole penetrating through the template along the thickness direction.
2. The preparation method according to claim 1, wherein the layered voids are a layer of voids existing between upper and lower adjacent graphene layers, the size of the voids in the direction parallel to the graphene layers is 50 to 1000 μm, and the size of the voids in the direction perpendicular to the graphene layers is 30 to 200 μm;
the template is provided with a plurality of through holes.
3. The preparation method according to claim 1, wherein the temperature for heat treatment of the graphene oxide blank is 2400 ℃ or higher, preferably 2800 ℃ or higher;
the graphene oxide layer is formed by coating and drying graphene oxide slurry; the drying temperature is 40-150 ℃.
4. The preparation method according to claim 3, wherein the weight percentage of the graphene oxide in the graphene oxide slurry is 0.5-10 wt.%, preferably 2-8 wt.%.
5. A method of preparation according to claim 1, characterised in that the graphene oxide layer has a thickness of 0.1 to 1mm, preferably a thickness of 0.25 to 0.8mm.
6. The method according to claim 1, further comprising peeling the substrate after obtaining a graphene oxide blank of a predetermined thickness;
the base material comprises polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, copper foil, aluminum film or glass.
7. The method according to claim 2, wherein the template layer has a thickness of 5 to 50 μm, preferably 10 to 20 μm; the aperture size of the through hole on the template layer is 50-200 mu m, and the aperture size of the through hole is preferably 100-150 mu m; the hole pitch between every two through holes on the template layer is 100-200 μm, and preferably, the hole pitch is 120-160 μm.
8. The method according to claim 1, wherein the foaming material is a polymer film comprising epoxy resin, phenolic resin, furfural resin, polyimide, polyarylacetylene, polymethyl methacrylate, asphalt, ABS, PC-ABS, polyethylene terephthalate, or polyurethane.
9. The graphene material prepared by the preparation method according to any one of claims 1 to 8, wherein the graphene material is composed of multiple graphene layers, layered gaps exist between the upper graphene layer and the lower graphene layer, and multiple graphene columns are distributed between the layered gaps.
10. A graphene heat conduction gasket is characterized by being prepared from the graphene material of claim 9, and comprising the steps of immersing the prepared graphene material into a high-molecular polymer, taking out the graphene material, solidifying and molding the graphene material, and cutting the graphene material into sheets along the thickness direction to prepare the graphene heat conduction gasket; in the graphene thermal conductive pad, the weight percentage of graphene is 30-70 wt.%, preferably 40-60 wt.%.
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