CN115231564A - Graphene thermal interface material and preparation method and application thereof - Google Patents
Graphene thermal interface material and preparation method and application thereof Download PDFInfo
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- CN115231564A CN115231564A CN202110436511.8A CN202110436511A CN115231564A CN 115231564 A CN115231564 A CN 115231564A CN 202110436511 A CN202110436511 A CN 202110436511A CN 115231564 A CN115231564 A CN 115231564A
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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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The application discloses a graphene thermal interface material and a preparation method and application thereof, wherein the thermal interface material comprises a three-dimensional graphene skeleton; the three-dimensional graphene skeleton comprises graphene lamellae, and vertically-oriented micropores are formed among the graphene lamellae. The graphene thermal interface material has continuous uniform vertical orientation micropores, has continuously arranged graphene in the horizontal direction, does not damage the excellent thermal characteristics of the graphene, and can be widely applied to the fields of heat-conducting composite materials and thermal interface materials. The application firstly provides a method for preparing the thermal interface material by a mild foaming method, and the fluffy graphene three-dimensional framework is prepared and has a porous structure with high orientation layer by layer. The method is simple and quick to operate and low in cost.
Description
Technical Field
The application relates to a graphene thermal interface material and a preparation method and application thereof, and belongs to the technical field of heat conduction materials.
Background
Polymers are widely used as electronic packaging materials in semiconductor manufacturing technology due to their low cost, superior mechanical properties, and high thermal and chemical stability. However, the development of the microelectronics industry over the last several decades has led to an increase in the integration level and power density of semiconductor devices. Due to the low thermal conductivity (0.2W/mK), the attendant thermal management requirements push the processing power of conventional polymers beyond their processing power. The special structure of the graphene enables the graphene to have excellent thermal properties (theoretical value: 5300W/mK). However, conventional mixing methods generally enable graphene to aggregate due to strong pi-pi interactions between graphene sheets, and thus graphene is difficult to form a continuous structure. Therefore, graphene is made into a three-dimensional porous macroscopic body, and a heat conduction channel is prefabricated, so that the mainstream method for preparing the high-heat-conduction graphene polymer composite material is provided. So far, methods for preparing graphene three-dimensional porous materials mainly include a suction filtration method, a template assembly method, an ice crystal guiding assembly method and the like. Liu et al (Rsc Advances,2016,6 (27): 22364-22369) use a template assembly method to soak the graphene dispersion on the polyurethane sponge, heat to remove the polyurethane sponge, and finally pour in a polymer to obtain a composite material with a vertical thermal conductivity of 1.52W/mK. However, the method cannot fully exert the high heat conduction characteristic of the graphene, and is complex in steps and difficult to apply. Wong et al (Chemistry of Materials 28.17,2016,28 (17): 6096-6104) use ice crystal orientation to obtain vertically aligned three-dimensional graphene macrostructures by formation of oriented ice crystals, which have a thermal conductivity of 2.13W/mK after being made into a composite material. But the upper limit of the thermal conductivity is limited due to the extremely low content of graphene in the composite material. Liu et al (Chemistry of Materials,2014, 26). However, due to the self-assembly effect of graphene in the suction filtration process, the vertical thermal conductivity of the composite material is 5.43W/mK, and the requirement of high thermal conductivity cannot be met.
In conclusion, a method for preparing a graphene-based thermal interface material with simple preparation, low cost and high thermal conductivity is still lacking in the art.
Disclosure of Invention
According to one aspect of the application, a graphene thermal interface material, a preparation method and an application thereof are provided, wherein the graphene thermal interface material is a three-dimensional graphene material with vertically-arranged graphene continuously and uniformly in the structure and has excellent heat conduction performance.
The thermal interface material comprises a three-dimensional graphene skeleton;
the three-dimensional graphene skeleton comprises graphene lamellae, and vertically-oriented micropores are formed among the graphene lamellae.
Optionally, the thermal interface material has a thickness of 0.1 to 5mm.
Optionally, the density of graphene in the thermal interface material is 0.01-0.5 g/cm 3 ；
The size of the micropores is 10-300 mu m.
Optionally, the thermal interface material may also include a filler;
the filler is filled in the micropores.
Optionally, the filler is selected from at least one of an elastic polymer, a non-elastic polymer;
the elastic polymer is selected from at least one of silicon rubber and rubber;
the non-elastic polymer is selected from at least one of polyimide, epoxy resin, polypropylene, polyethylene, polyphenylene sulfide, polyamide, polycarbonate and polyvinyl chloride.
According to yet another aspect of the present application, there is provided a method of making the above-described thermal interface material, the method comprising at least the steps of:
and (3) soaking the graphene paper in a mixture containing an expanding agent, and expanding and foaming to obtain a three-dimensional graphene framework, namely the thermal interface material.
In the present application, unless otherwise specified, "dipping" means that an object to be dipped is immersed in an excess amount of a dipping solution.
Alternatively, the graphene paper includes graphene paper prepared from graphene oxide, graphene paper directly prepared from graphene sheets, artificial graphite paper carbonized from polyimide, and the like having in-plane horizontal graphene arrangement.
Optionally, the swelling agent is an oxidizing substance;
the oxidizing substance is at least one selected from sulfuric acid, nitric acid, sulfate, nitrate, hydrogen peroxide and potassium permanganate;
preferably, the mixture also comprises solvent water;
preferably, the sulfate may be selected from at least one of iron sulfate, sodium sulfate, potassium sulfate, and copper sulfate.
The nitrate is selected from at least one of ferric nitrate, sodium nitrate, potassium nitrate, and cupric nitrate.
Optionally, the concentration of the swelling agent in the mixture is from 30 to 95wt%.
Specifically, the lower limit of the concentration of the swelling agent in the mixture may be independently selected from 30wt%, 35wt%, 40wt%, 50wt%, 60wt%; the upper concentration limit of the swelling agent may be independently selected from 66wt%, 70wt%, 80wt%, 90wt%, 95wt%.
Optionally, the expansion foaming time is 4-24 h.
Preferably, the expansion foaming time is 12 to 18 hours.
Specifically, the lower limit of the expansion foaming time can be independently selected from 4h, 5h, 8h, 10h, 12h; the upper limit of the expansion foaming time can be independently selected from 14h, 16h, 18h, 20h and 24h.
Optionally, the method further comprises: washing and drying the three-dimensional graphene framework;
the drying mode is not particularly limited, and those skilled in the art can select a freeze-drying or drying mode according to requirements to remove the redundant liquid on the three-dimensional graphene skeleton.
Preferably, the drying conditions include:
the drying temperature is 50-80 ℃, and the drying time is 2-5 h.
More preferably, the drying temperature is 60-70 ℃ and the drying time is 2-3 h.
Optionally, the washing agent used for washing is at least one selected from water and organic solvent.
Preferably, the organic solvent is selected from at least one of methanol, ethanol, acetone, and DMF.
Optionally, the method further comprises:
and carrying out high-temperature annealing treatment on the three-dimensional graphene framework to obtain the thermal interface material.
Optionally, the conditions of the high-temperature annealing treatment are as follows:
the high-temperature annealing temperature is 200-3000 ℃, and the high-temperature annealing time is 2-5 h.
Preferably, the high-temperature annealing temperature is 2000-2800 ℃, and the high-temperature annealing time is 2-3 h.
Specifically, the lower limit of the high temperature annealing temperature can be independently selected from 200 ℃, 500 ℃, 1000 ℃, 1500 ℃ and 2000 ℃; the upper limit of the high temperature annealing temperature may be independently selected from 2200 deg.C, 2400 deg.C, 2600 deg.C, 2800 deg.C, 3000 deg.C.
Specifically, the high temperature annealing time may be independently selected from 2h, 3h, 4h, 5h, or any value therebetween.
Optionally, the method further comprises: and filling a filler in the three-dimensional graphene skeleton.
Optionally, the method further comprises: and filling fillers in the three-dimensional graphene skeleton after high-temperature annealing treatment.
Optionally, the filling method includes:
dipping the three-dimensional graphene skeleton in a mixture containing a polymer monomer, and curing;
preferably, the curing conditions are:
the curing temperature is 50-100 ℃, and the curing time is 0.5-2 h.
Specifically, the lower limit of the curing temperature can be independently selected from 50 ℃, 55 ℃, 60 ℃, 65 ℃ and 70 ℃; the upper limit of the curing temperature may be independently selected from 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 100 deg.C.
Specifically, the curing time may be independently selected from 0.5h, 1h, 1.5h, 2h, or any value therebetween.
According to yet another aspect of the present application, there is provided an electronic packaging material comprising a thermal interface material;
the thermal interface material is selected from at least one of any one of the graphene thermal interface materials and the graphene thermal interface material prepared by any one of the methods.
In the present application, "silica gel" means a rubber in which the main chain is composed of silicon and oxygen atoms alternately, and two organic groups are usually bonded to the silicon atom; "rubber" refers to a high-elasticity polymer material with reversible deformation, which is elastic at room temperature, can generate large deformation under the action of small external force, can recover the original shape after the external force is removed, and does not contain silica gel.
The beneficial effect that this application can produce includes:
1) The graphene thermal interface material has continuous uniform vertical orientation micropores, has continuously arranged graphene in the horizontal direction, is not damaged in graphene sheets, can keep the excellent thermal characteristics of the graphene (the horizontal thermal conductivity is 30W/mK and the vertical thermal conductivity is 7.9W/mK after thermal reduction), and can be widely applied to the fields of heat-conducting composite materials and thermal interface materials. And because of its expanded cellular structure, enables the material to be used longitudinally.
2) The application firstly provides a method for preparing the thermal interface material by a mild foaming method, and the fluffy graphene three-dimensional framework is prepared and has a porous structure with high orientation layer by layer.
3) The preparation method of the graphene thermal interface material is simple and quick to operate and low in cost
Drawings
Fig. 1 is a raman spectrum of the three-dimensional fluffy graphene foam obtained in examples 1 and 7 of the present application;
fig. 2 is a scanning electron micrograph of the three-dimensional fluffy graphene foam obtained in example 1 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
the analysis of the molecular structure of the material was performed using a raman spectrometer (model Renishaw inVia Reflex).
And analyzing the surface structure of the material by using a scanning electron microscope (model Verios G4 UC).
The density of the material was analyzed using an electronic balance.
Analysis of the thermal conductivity of the material was performed using LFA 467 laser scintillator (Netzsch, germany).
According to one embodiment of the application, the graphene paper is placed in the expanding agent solution, the expanded graphene foam is washed, and then the redundant liquid is removed through drying, so that the three-dimensional fluffy graphene foam, namely the thermal interface material, is obtained.
The graphene paper may be graphene paper prepared from graphene oxide, graphene paper directly prepared from graphene sheets, or artificial graphite paper carbonized by polyimide, but is not limited to the above-described method, and any method may be used as long as graphene paper having in-plane-horizontal graphene arrangement can be obtained.
The expanding agent can adopt aqueous solution of sulfuric acid, nitric acid, sulfate, nitrate, hydrogen peroxide, potassium permanganate and other substances with high oxidizing property. Specifically, the expander solution may be a) a conventional solution of the above substances, such as concentrated sulfuric acid, concentrated nitric acid, hydrogen peroxide; or b) preparing an aqueous solution from a solid substance with oxidability, such as a solution obtained by adding potassium permanganate, ferric sulfate, ferric nitrate and the like into water; it is also possible c) to add the solid substance having oxidizing properties directly to the solution of a).
The drying method can be freeze drying or oven drying, such as freeze drying at-40 deg.C to-20 deg.C, or oven drying at 50-80 deg.C.
Another embodiment of the present application includes the steps of:
step a1, placing graphene paper in an expanding agent solution, washing the foamed graphene foam, and then drying to remove redundant liquid to obtain the three-dimensional fluffy graphene foam.
Step a2, soaking the three-dimensional fluffy graphene foam in a mixture containing a polymer prepolymer, and then curing to obtain a graphene/polymer composite material, namely a thermal interface material.
In this step, the mixture contains a prepolymer necessary for forming a polymer and a diluting solvent.
The curing conditions are adjusted according to the physical properties of the filled polymer.
Another embodiment of the present application comprises the following steps:
and step b1, placing the graphene paper in an expanding agent solution, washing the foamed graphene foam, and then drying to remove redundant liquid to obtain the three-dimensional fluffy graphene foam.
And b2, carrying out high-temperature annealing treatment on the three-dimensional fluffy graphene foam to obtain the thermal interface material.
In the step, the density defect of the three-dimensional fluffy graphene foam, namely the three-dimensional graphene skeleton, can be reduced by high-temperature annealing treatment.
Another embodiment of the present application includes the steps of:
and step c1, placing the graphene paper in an expanding agent solution, washing the foamed graphene foam, and then drying to remove redundant liquid to obtain the three-dimensional fluffy graphene foam.
And c2, carrying out high-temperature annealing treatment on the three-dimensional fluffy graphene foam.
And c3, soaking the annealed three-dimensional fluffy graphene foam in a mixture containing a polymer prepolymer, and then curing to obtain the graphene/polymer composite material, namely the thermal interface material.
Example 1
Graphene paper (obtained by graphitizing after graphene oxide is formed by blade coating) with the thickness of 25 μm, wherein the graphene paper is obtained by the graphitizing treatment after the graphene oxide is formed, and the graphene paper is purchased from Fuchen technologies, inc. of Changzhou, 0.1g of the graphene paper is soaked in a mixed solution of concentrated sulfuric acid with the mass fraction of 98% and hydrogen peroxide with the mass fraction of 10% (the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 1.
Example 2
The preparation procedure and procedure in this example were substantially the same as in example 1 above, except that: the graphene paper is an artificial graphite film carbonized by polyimide (purchased from carbon element science and technology, ltd.).
Example 3
The preparation procedure and procedure in this example were substantially the same as in example 1 above, except that: the expanding agent solution is a mixed aqueous solution of concentrated sulfuric acid and sodium nitrate with the mass fraction of 98%, wherein the ratio of the sodium nitrate to the concentrated sulfuric acid to the water is 10g.
Example 4
The preparation procedure and procedure in this example were substantially the same as in example 1 above, except that: the immersion time was 6 hours.
Example 5
The preparation procedure and procedure in this example are substantially the same as in example 1 above, except that: the detergent is a mixed solution consisting of water and absolute ethyl alcohol in a volume ratio of 1.
Example 6
The preparation procedure and procedure in this example are substantially the same as in example 1 above, except that: the drying mode is drying for 10h at 60 ℃.
Example 7
The preparation procedure and procedure in this example were substantially the same as in example 1 above, except that: and (3) annealing the dried three-dimensional graphene foam at 2800 ℃ for 2 hours.
Example 8
The preparation procedure and procedure in this example are substantially the same as in example 1 above, except that: and filling the obtained three-dimensional fluffy graphene foam with PDMS (polydimethylsiloxane) to prepare the PDMS-based composite thermal interface material. The specific operation is as follows:
and (2) soaking the dried three-dimensional fluffy graphene foam in a mixed solution (the ratio is 10.
Raman scattering analysis was performed on the materials obtained in example 1 and example 7
As shown in fig. 1, no obvious D peak appears after expansion treatment, which indicates that the expansion process does not generate great damage to graphene, effectively ensures the lattice structure of graphene itself, ensures that the thermal conductivity loss of graphene is less, and repairs the partially damaged graphene structure at high temperature as the half-peak width of the G peak becomes narrow with the increase of the treatment temperature, thereby further ensuring the improvement of the thermal conductivity of graphene. Wherein RT represents normal temperature, namely the material obtained without annealing treatment in the embodiment; the annealing treatment of the material obtained in example 1 at the corresponding temperature for 2 hours is respectively shown at 1000 ℃ and 2000 ℃;2800 deg.C represents the material obtained under the annealing conditions of example 7.
Scanning Electron microscopy analysis of the Material obtained in example 1
As shown in fig. 2, the material has a three-dimensional framework structure, and the expansion between the original parallel distributed graphene sheets in the framework forms a continuous distributed micropore structure, and micropores have high vertical orientation.
The thermal properties of the materials obtained in examples 1 to 8 were tested:
first, 10 × 1mm sheet samples were prepared from the materials prepared in examples 1 to 8, respectively;
the samples were then tested for vertical thermal conductivity using an LFA 467 laser scintillator (Netzsch, germany) with the results shown in table 1.
TABLE 1 data sheet of graphene macroscopical body sample performance parameters
As can be seen from the above table, the thermal conductivity of the thermal interface material is mainly affected by the framework material, and the addition of the filler has little influence on the thermal conductivity of the material (as in examples 1 and 8); the impregnation expansion time, the drying treatment and the annealing treatment have obvious influence on the thermal conductivity of the material, because the impregnation time prolongs the expansion degree, the shorter the time is, the smaller the expansion proportion is, the higher the density of the graphene skeleton is, the higher the thermal conductivity is, the drying can enable the graphene skeleton to retract, the density of the graphene skeleton is increased, the annealing can repair the defects generated by the graphene in the expansion process, and the thermal conductivity of the graphene skeleton is improved.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A thermal interface material, comprising a three-dimensional graphene backbone;
the three-dimensional graphene skeleton comprises graphene lamellae, and vertically-oriented micropores are formed among the graphene lamellae.
2. A thermal interface material as defined in claim 1, wherein said thermal interface material has a thickness of 0.1-5 mm;
the size of the micropores is 10-300 mu m;
preferably, the density of the graphene in the thermal interface material is 0.01-0.5 g/cm 3 。
3. A thermal interface material as defined in claim 1, wherein said thermal interface material further comprises a filler;
the filler is filled in the micropores;
preferably, the filler is selected from at least one of an elastic polymer, a non-elastic polymer;
the elastic polymer is selected from at least one of silicon rubber and rubber;
the non-elastic polymer is selected from at least one of polyimide, epoxy resin, polypropylene, polyethylene, polyphenylene sulfide, polyamide, polycarbonate and polyvinyl chloride.
4. A method for preparing a thermal interface material according to any one of claims 1 to 3, characterized in that it comprises at least the following steps:
and (3) soaking the graphene paper in a mixture containing an expanding agent, and expanding and foaming to obtain a three-dimensional graphene framework, namely the thermal interface material.
5. The method according to claim 4, wherein the swelling agent is an oxidizing substance;
the substance with oxidability is selected from at least one of sulfuric acid, nitric acid, sulfate, nitrate, hydrogen peroxide and potassium permanganate;
preferably, the mixture also comprises solvent water;
preferably, the concentration of the expanding agent in the mixture is 30 to 95wt%;
preferably, the expansion foaming time is 4 to 24 hours.
6. The method of manufacturing according to claim 4, further comprising: washing and drying the three-dimensional graphene framework;
preferably, the method further comprises:
carrying out high-temperature annealing treatment on the three-dimensional graphene framework to obtain the thermal interface material;
further preferably, the conditions of the high-temperature annealing treatment are as follows:
the high-temperature annealing temperature is 200-3000 ℃, and the high-temperature annealing time is 2-5 h.
7. The method of manufacturing according to claim 4, further comprising: and filling a filler in the three-dimensional graphene skeleton.
8. The method of manufacturing according to claim 6, further comprising: and filling fillers in the three-dimensional graphene framework subjected to high-temperature annealing treatment.
9. The production method according to claim 7 or 8, characterized in that the filling method comprises:
dipping the three-dimensional graphene skeleton in a mixture containing a polymer monomer, and curing;
preferably, the curing conditions are:
the curing temperature is 50-100 ℃, and the curing time is 0.5-2 h.
10. An electronic packaging material, wherein the electronic packaging material comprises a thermal interface material;
the thermal interface material is at least one selected from the group consisting of the graphene thermal interface material according to any one of claims 1 to 3 and the graphene thermal interface material prepared by the method according to any one of claims 4 to 9.
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Citations (4)
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| CN103700513A (en) * | 2013-12-30 | 2014-04-02 | 中山大学 | Graphene paper and preparation method and application thereof |
| CN104261387A (en) * | 2014-09-16 | 2015-01-07 | 中山大学 | Method for large-area preparation of graphene based carbon paper and graphene based carbon paper prepared thereby |
| CN105542728A (en) * | 2016-01-24 | 2016-05-04 | 北京大学 | Method for preparing vertical orientation graphene sheet/high polymer thermal interface material |
| CN112408371A (en) * | 2020-10-30 | 2021-02-26 | 宁波石墨烯创新中心有限公司 | Graphene heat-conducting film, preparation method thereof and electronic equipment |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700513A (en) * | 2013-12-30 | 2014-04-02 | 中山大学 | Graphene paper and preparation method and application thereof |
| CN104261387A (en) * | 2014-09-16 | 2015-01-07 | 中山大学 | Method for large-area preparation of graphene based carbon paper and graphene based carbon paper prepared thereby |
| CN105542728A (en) * | 2016-01-24 | 2016-05-04 | 北京大学 | Method for preparing vertical orientation graphene sheet/high polymer thermal interface material |
| CN112408371A (en) * | 2020-10-30 | 2021-02-26 | 宁波石墨烯创新中心有限公司 | Graphene heat-conducting film, preparation method thereof and electronic equipment |
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