CN108329495B - Graphene-cellulose nanocrystalline composite heat-conducting film with bionic structure and preparation thereof - Google Patents
Graphene-cellulose nanocrystalline composite heat-conducting film with bionic structure and preparation thereof Download PDFInfo
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Abstract
The invention relates to a graphene-cellulose nanocrystalline heat-conducting film with a bionic structure and a preparation method thereof, wherein the composite film has a shell-like brick-slurry laminated structure, and the preparation method comprises the following steps: (1) mixing a GO solution and a CNC solution in a certain proportion, stirring, coating, and drying; (2) annealing and reducing the film obtained in the step (1) at a high temperature to obtain the target product graphene composite heat-conducting film. Compared with the prior art, the method has the advantages that CNC is embedded between graphene layers by a self-assembly method, and a graphene layered shell-like structure is constructed, so that the heat conduction and electric conduction performance of the graphene film are improved.
Description
Technical Field
The invention relates to the field of film material preparation, in particular to a graphene-cellulose nanocrystalline composite heat-conducting film with a bionic structure and a preparation method thereof.
Background
The rapid development of modern aerospace, electronic computer and other industries has put more and more stringent requirements on the performance of integrated chips. The heat dissipation performance of the chip has become an important factor for restricting the working efficiency of the electronic device, and therefore, the high thermal conductive material has become a hotspot of the current electronic industry research. Compared with the existing commonly used heat dissipation materials such as metal and the like, the carbon material has the advantages of high heat conductivity coefficient (such as 2000W/mK of graphite, 2300W/mK of diamond and 3500W/mK of carbon nano tube), light density, low thermal expansion coefficient and the like, can replace the traditional heat dissipation material, and meets the requirements of functionalization, miniaturization, lightness, thinness and integration of electronic devices.
Among many carbon materials, graphene is receiving much attention due to its special structure and excellent properties. Graphene is an sp2The single-layer two-dimensional planar carbon material formed by hybridizing carbon atoms has a plurality of excellent performances such as ultrahigh carrier mobility, high strength, high specific surface area and the like. The heat conductivity coefficient of the single-layer graphene measured by the experiment can reach 5300W/mK, and is far higher than that of other common heat conducting materials. The graphene is used as a raw material to prepare the heat-conducting film, so that the heat dissipation performance of the electronic device is expected to be greatly improved.
At present, the application of graphene films in the field of heat conduction has been reported in a plurality of patents, such as chinese patents CN104229783B, CN105523547B, CN105731435B, etc. However, the pure graphene film reported at present still has many defects of low interfacial heat conduction, poor mechanical properties and the like. Therefore, it is necessary to introduce new carbon nano-reinforcement to further improve the thermal conductivity, the electric conductivity and the mechanical properties of the graphene film.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a graphene-cellulose nanocrystalline composite heat and electricity conducting film with a bionic structure and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the invention aims to provide a graphene-cellulose nanocrystalline heat-conducting film with a bionic structure, wherein a brick-slurry structure similar to a shell is constructed by a graphene sheet layer and CNC. The graphene sheets act as matrix "bricks" in the structure, with CNC uniformly dispersed between the stacked graphene sheets acting as a linker "mud" in the structure.
The invention also aims to provide a preparation method of the graphene-cellulose nanocrystalline heat conducting film with the bionic structure, which comprises the following steps:
(1): mixing the GO solution and the CNC solution, stirring, evaporating to prepare a membrane, and drying;
(2): annealing and reducing the film obtained in the step (1) at high temperature to obtain the target product graphene-cellulose nanocrystalline composite heat-conducting film.
Preferably, in the step (1): expanded graphite is used as a raw material, and GO aqueous dispersion is prepared by an improved Hummers method (the specific process is shown in Advanced Materials,2013.25(26): 3583-.
Preferably, in the step (1): extracting CNC solution from plant material by acid hydrolysis. More preferably, the acid used in the acid hydrolysis process is sulfuric acid, which comprises the following steps:
adding plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a mass ratio of 1:1, hydrolyzing at 65 ℃ for 1.5h, adding deionized water for dilution, standing, centrifuging, dialyzing, and performing ultrasound to obtain a CNC solution.
Preferably, in the step (1): the plant material is cotton or hemp.
Preferably, in the step (1): the mixing ratio of the GO water dispersion and the CNC solution meets the following requirements: the mass ratio of GO to CNC solute is 0.01-100: 1.
Preferably, in the step (1): the process conditions for preparing the film by evaporation are as follows: evaporating in a constant temperature far infrared oven for more than 12h at the temperature of 60 ℃.
Preferably, in the step (2): the high-temperature annealing process is to anneal for 0.5-2 h at 600-3000 ℃ under the condition of nitrogen.
The invention limits the addition proportion of each component, the processing temperature and other process parameters. If the CNC addition ratio is too low, the effect of improving the heat-conducting property of the CNC on the graphene film cannot be exerted; if the CNC addition ratio is too high, CNC is easy to agglomerate, so that the heat-conducting property is reduced. If the processing temperature is too low, the graphene cannot be fully reduced and the CNC cannot be fully carbonized, and the heat-conducting property of the graphene film cannot be exerted; if the processing temperature is too high, the required energy consumption and cost are increased.
Compared with the prior art, the invention enlightens the natural layered brick-slurry nano structure of the shell, and the CNC is embedded between graphene layers by using a self-assembly method to construct a graphene layered shell-like structure. The graphene sheet layers act as matrix "bricks" in the structure, providing the basic thermal conductivity. The CNC is uniformly dispersed among the graphene sheet layers and serves as a connecting agent 'slurry' in the structure, so that the CNC can be effectively connected with the graphene sheet layers, and a heat conduction channel among the graphene sheet layers is further increased. The structure is beneficial to the improvement of the thermal conductivity of the graphene film in the in-plane direction and the inter-plane direction.
Drawings
Fig. 1 is a scanning electron microscope photograph of a plane before high-temperature reduction of a graphene-cellulose nanocrystal composite film obtained in example 1 of the present invention;
fig. 2 is a scanning electron microscope photograph of a cross section of the graphene-cellulose nanocrystal composite film obtained in example 1 of the present invention before high temperature reduction;
fig. 3 is a scanning electron microscope photograph of a cross section of the graphene-cellulose nanocrystal composite film obtained in example 1 of the present invention after high temperature reduction;
fig. 4 is a transmission electron microscope photograph of the graphene-cellulose nanocrystal composite film obtained in example 1 of the present invention after high temperature reduction.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
In the following examples, the process conditions for the evaporation film formation were as follows: evaporating in a constant temperature far infrared oven at 60 deg.C for more than 12 hr.
In the following examples, the modified Hummers method is described in detail in the literature advanced materials,2013.25(26):3583-3587. And other reagents or methods and processes are not required or conventional in the art can be adopted if the method is not specially described.
Example 1
Preparing GO aqueous dispersion by using expanded graphite as a raw material and utilizing an improved Hummers method; adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution. Mixing the prepared CNC solution and GO water dispersion according to the solute mass ratio of 1:1, diluting, stirring, coating and drying. Annealing and reducing the obtained film at 1500 ℃ for 2 h.
Fig. 1 is a scanning electron microscope photograph of a plane before high-temperature reduction of a graphene-cellulose nanocrystal composite film obtained in example 1 of the present invention; as can be seen from the figure, the CNC is uniformly dispersed on the surface of GO, which shows that a good self-assembly effect is formed between GO and CNC.
Fig. 2 is a scanning electron microscope photograph of a cross section of the graphene-cellulose nanocrystal composite film obtained in example 1 of the present invention before high temperature reduction; as can be seen from the figure, the CNC is uniformly dispersed between GO layers, which shows that a good self-assembly effect is formed between GO and CNC.
Fig. 3 is a scanning electron microscope photograph of a cross section of the graphene-cellulose nanocrystal composite film obtained in example 1 of the present invention after high temperature reduction; as can be seen from the figure, the carbonized CNC still keeps a rod-shaped structure and is uniformly dispersed among graphene layers, so that an interlayer heat conduction path is formed, and the improvement of heat conduction performance is promoted.
Fig. 4 is a transmission electron microscope photograph of the graphene-cellulose nanocrystal composite film obtained in example 1 of the present invention after high temperature reduction. As can be seen from the figure, the carbonized CNC still keeps a rod-shaped structure and is uniformly dispersed among graphene layers, so that an interlayer heat conduction path is formed, and the improvement of heat conduction performance is promoted.
Comparative example 1
Expanded graphite is used as a raw material, and a GO water dispersion is prepared by utilizing an improved Hummers method. Diluting the prepared GO water dispersion, stirring, coating and drying. Annealing and reducing the obtained film at 1500 ℃ for 2 h.
Example 2
Preparing GO aqueous dispersion by using expanded graphite as a raw material and utilizing an improved Hummers method; adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution. Mixing the prepared CNC solution and GO water dispersion according to the solute mass ratio of 1:4, diluting, stirring, coating and drying. Annealing and reducing the obtained film at 1500 ℃ for 2 h.
Example 3
Preparing GO aqueous dispersion by using expanded graphite as a raw material and utilizing an improved Hummers method; adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution. Mixing the prepared CNC solution and GO water dispersion according to a solute mass ratio of 4:1, diluting, stirring, coating and drying. Annealing and reducing the obtained film at 1500 ℃ for 2 h.
Example 4
Preparing GO aqueous dispersion by using expanded graphite as a raw material and utilizing an improved Hummers method; adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution. Mixing the prepared CNC solution and GO water dispersion according to the solute mass ratio of 1:1, diluting, stirring, coating and drying. Annealing and reducing the obtained film at the high temperature of 800 ℃ for 2 h.
Example 5
Preparing GO aqueous dispersion by using expanded graphite as a raw material and utilizing an improved Hummers method; adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution. Mixing the prepared CNC solution and GO water dispersion according to the solute mass ratio of 1:1, diluting, stirring, coating and drying. Annealing and reducing the obtained film at the high temperature of 1000 ℃ for 2 h.
Example 6
Preparing GO aqueous dispersion by using expanded graphite as a raw material and utilizing an improved Hummers method; adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution. Mixing the prepared CNC solution and GO water dispersion according to the solute mass ratio of 1:1, diluting, stirring, coating and drying. Annealing and reducing the obtained film at the high temperature of 1200 ℃ for 2 h.
The thermal conductivity of the film was determined by laser-flash method according to the standard ASTM E1461-13.
The conductive properties of the films were tested using a four-probe resistance meter according to the standard ASTM F84.
The test results are shown in table 1.
TABLE 1
The performance data for examples 1-6 and comparative example 1 are set forth in table 1. Compared with the thermal conductivity of the pure graphene film in comparative example 1, the graphene-cellulose nanocrystalline film in example 1 exhibits higher in-plane and inter-plane thermal and electrical conductivity coefficients; compared with the embodiments 2 and 3, the parameter of the cellulose nanocrystal content in the embodiment 1 is most optimized, and the performance is improved most obviously; compared with the examples 4-6, the parameter of the processing temperature is the most optimized in the example 1, and the performance is improved most obviously.
Example 7
Preparing GO aqueous dispersion by using expanded graphite as a raw material and utilizing an improved Hummers method; adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution. Mixing the prepared CNC solution and GO water dispersion according to the solute mass ratio of 1:100, diluting, stirring, coating and drying. Annealing and reducing the obtained film at the high temperature of 600 ℃ for 0.5 h.
Example 8
Preparing GO aqueous dispersion by using expanded graphite as a raw material and utilizing an improved Hummers method; adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution. Mixing the prepared CNC solution and GO water dispersion according to a solute mass ratio of 100:1, diluting, stirring, coating and drying. Annealing and reducing the obtained film at the high temperature of 3000 ℃ for 1 h.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A preparation method of a graphene-cellulose nanocrystalline heat conduction film with a bionic structure is characterized in that the heat conduction film is composed of graphene sheet layers and CNC, and a shell-like brick-slurry structure is constructed, wherein the graphene sheet layers serve as base bodies of bricks, and the CNC is uniformly dispersed among the graphene sheet layers and serves as a connecting agent slurry for connecting the graphene sheet layers;
the preparation method comprises the following steps:
(1): mixing the GO solution and the CNC solution, stirring, and evaporating to prepare a membrane;
(2): annealing and reducing the film obtained in the step (1) at a high temperature to obtain a target product graphene heat-conducting film;
in the step (1), mixing a GO solution and a CNC solution according to the mass ratio of solutes of 0.01-100: 1;
the high-temperature annealing process in the step (2) comprises the following steps: annealing at 600-3000 ℃ for 0.5-2 h under the condition of nitrogen.
2. The preparation method of the graphene-cellulose nanocrystalline heat conducting film with the bionic structure according to claim 1, wherein the GO aqueous dispersion in the step (1) is prepared by using expanded graphite as a raw material and utilizing a Hummers method.
3. The method for preparing the graphene-cellulose nanocrystalline heat conducting film with the bionic structure according to claim 1, wherein the CNC solution in the step (2) is extracted from plant raw materials by using an acid hydrolysis method.
4. The method for preparing the graphene-cellulose nanocrystalline heat conducting film with the bionic structure according to claim 3, wherein an acid used in the acid hydrolysis method is sulfuric acid, and the steps are as follows:
adding plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a mass ratio of 1:1, heating for hydrolysis, adding deionized water for dilution, standing, centrifuging, dialyzing, and performing ultrasound to obtain a CNC solution.
5. The method for preparing the graphene-cellulose nanocrystalline heat conducting film with the bionic structure according to claim 4, wherein the plant raw material is cotton or hemp.
6. The preparation method of the graphene-cellulose nanocrystalline heat conducting film with the bionic structure according to claim 4, wherein the technological conditions of heating hydrolysis are as follows: hydrolysis was carried out at 65 ℃ for 1.5 h.
7. The preparation method of the graphene-cellulose nanocrystalline heat conducting film with the bionic structure according to claim 1, wherein the evaporation film-making process conditions in the step (1) are as follows: evaporating for 12h in a constant temperature far infrared oven at 60 ℃.
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| CN110144063A (en) * | 2019-05-13 | 2019-08-20 | 浙江工业大学 | A kind of heat conductive insulating cellulose membrane and preparation method thereof |
| CN110240892A (en) * | 2019-07-03 | 2019-09-17 | 桂林理工大学 | A kind of bionic laminar graphene/imide derivative thermally conductive film and preparation method thereof |
| CN110845752B (en) * | 2019-11-04 | 2022-03-25 | 上海大学 | Composite graphene heat-conducting film with bionic structure and preparation thereof |
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| CN113024281B (en) * | 2021-02-28 | 2022-10-14 | 西北工业大学 | Silicon carbide/graphene bionic laminated coating and preparation method thereof |
| CN114920995B (en) * | 2022-04-01 | 2023-04-28 | 西北工业大学 | Graphene/nanocellulose laminated microstructure, preparation method, device and application |
| CN116553533A (en) * | 2023-05-09 | 2023-08-08 | 浙江道明超导科技有限公司 | Preparation method of graphene sealing material |
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