CN111302332B - Ultrahigh-thermal-conductivity graphene thick film and preparation method thereof - Google Patents
Ultrahigh-thermal-conductivity graphene thick film and preparation method thereof Download PDFInfo
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Abstract
The invention disclosesA graphene thick film with ultrahigh thermal conductivity along a plane direction and a preparation method thereof are provided. According to the method, firstly, oxidized graphene hydrosol is used for protonating oxidized graphene under an acidic condition, the liquid surface is adjusted to realize orientation arrangement and film formation, and then the ultrahigh heat conduction graphene thick film is obtained through reduction. The method can greatly shorten the preparation period of the graphene thick film material, improve the production efficiency and save the production energy consumption and cost. The ultrahigh heat conduction graphene thick film has the thickness of 50-300 mu m and the density of 1.7-2.1g/cm3The thermal conductivity is more than 1500W/mK.
Description
Technical Field
The invention belongs to the field of heat conduction materials, and particularly relates to a graphene thick film with ultrahigh heat conduction and a preparation method thereof.
Background
The graphene is a single-layer honeycomb crystal structure formed by closely arranging sp2 hybridized carbon atoms, the thermal conductivity of the graphene at room temperature can reach 5000W/mK, is 10 times higher than that of copper at room temperature, is higher than that of diamond and carbon nanotubes, and is a material with the highest thermal conductivity which is currently recognized by human beings.
Currently, in the industrial preparation of the heat-conducting graphene film material, a graphene oxide film is mostly used as a precursor, and the graphene film is obtained through a heat treatment or chemical reduction mode. The final product performance and structure are quite related to the orientation consistency and the arrangement compactness of the graphene oxide in the precursor, and the graphene oxide needs to be dispersed in a dispersion system with low graphene oxide concentration to realize deep stripping of graphene oxide lamella in order to obtain a graphene oxide film with high orientation degree and compact arrangement of an internal structure; in the graphene oxide film forming process, the film needs to be dried at a lower temperature and the dispersing agent needs to be volatilized to form a film so as to ensure that the film structure has a higher compactness; the graphene film is prepared by heat treatment, so that the preparation of the material is long in time consumption and high in cost, and for the preparation of the thick film, a larger amount of dispersing agent needs to be volatilized at a lower temperature, but the dispersing agent is difficult to volatilize due to the hydrophilic characteristic of the graphene oxide, so that the time consumption and the energy consumption are more serious.
At present, the thick film in the industry can be prepared by adopting processes such as multiple film forming or multi-film laminating, for example, a plurality of films with the thickness of about 25 micrometers are laminated on the PI film, but the in-plane thermal conductivity of the final thick film is lower than that of a single PI film due to the thermal resistance of an adhesive layer between the PI film layers. The multiple film forming process of the graphene film also faces the problem that the interface effect between films generates huge thermal resistance, the preparation process is complex, multiple drying can cause structural damage to the cured film, and meanwhile, the energy consumption and the time consumption are high; for the preparation of graphene thick films by lamination, hot pressing treatment is required as described in patent "CN 107140619A", the process is complicated, the production cost is increased, and the assembled graphene oxide film structure is damaged during the compaction process.
In addition, in the process of forming the graphene oxide film, a dispersing agent in one side of the film volatilizes to generate gas and leave a cavity; on the other hand, the concentration of the dispersion system increases along with the increase of the drying degree, so that the surface energy of the system is changed, the graphene oxide lamellar structure in the formed film collapses, defects are left in the film, and the interlayer compactness degree of orientation and arrangement is influenced. And with the increase of the prepared film thickness, the defects in the film correspondingly increase; therefore, the problem that the thermal conductivity of the graphene film in the horizontal direction is reduced along with the increase of the thickness is generally faced in the current graphene film preparation, so that the current preparation method cannot achieve the increase of the graphene film thickness while obtaining higher thermal conductivity of the graphene film in the horizontal direction. Under current process conditions, graphene film products with thicknesses greater than 50 μm typically have in-plane thermal conductivities of less than 800W/mK.
Through researching the properties of the graphene oxide, the ionization of the graphene oxide is inhibited and the graphene oxide is protonated in an acidic environment; the protonated graphene oxide is no longer hydrophilic or alcoholic solution and can be separated from the dispersing agent directly and separated out from the dispersing system. However, due to the fact that the protonated graphene oxide is of a single-layer atomic structure and the surface of the protonated graphene oxide is modified by oxygen-containing functional groups, the two-dimensional plane structure of the protonated graphene oxide becomes extremely unstable after being separated from a dispersion system, the two-dimensional plane structure collapses in water, and the uniform and tight arrangement of graphene sheet layer orientation cannot be guaranteed through direct film forming, so that finally, large graphene films which are well assembled are not arranged between graphene thick film layers, and a large amount of graphene thick films exist between different graphene sheets due to the phonon scattering effect of the interface, and the thermal conductivity of the graphene thick films is extremely poor. The protonated graphene oxide can be stably spread only by a two-dimensional planar structure of the graphene oxide in a solvent with the surface energy equivalent to that of the graphene oxide, and then the film is formed, so that the assembly of a large number of graphene layers in a thick film and a compact structure between layers can be realized, and a graphene thick film product with ultrahigh thermal conductivity can be obtained.
Therefore, a scheme for preparing a graphene film by rapidly obtaining a thick film precursor with a compact structure through one-step forming on the premise of ensuring deep stripping of a graphene oxide sheet layer is urgently needed so as to reduce the production cost and obtain a graphene thick film product with higher thermal conductivity. And based on the characteristic film forming of the oxidized graphene after protonation, the preparation of the graphene thick film of the graphene with ultrahigh heat-conducting property can be realized, and compared with the prior technical scheme, the preparation and film forming process of the precursor does not need to be dried for a long time and can realize one-step forming and high-efficiency preparation.
Disclosure of Invention
The invention aims to overcome the defect of preparing a graphene thick film heat conduction material in the prior art, and provides a graphene oxide thick film material with ultrahigh heat conduction performance and a high-efficiency preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a graphene thick film with ultrahigh heat conductivity comprises the following steps:
(1) washing graphite oxide to be neutral, mixing the graphite oxide with deionized water, and performing ultrasonic stirring to obtain graphene oxide hydrosol; the concentration of the graphene oxide hydrosol is 1-20 mg/mL.
(2) Adding an acidic electrolyte solution into the graphene oxide hydrosol obtained in the step (1) to protonate and separate out graphene oxide sheets to obtain protonated graphene oxide slurry; the acidic electrolyte solution comprises HCl and H2SO4、NH4Cl、NH4HSO4、(NH4)2SO4Preferably HCl and NH4The mass concentration ratio of Cl substance is 1: 23, mixing the solution; and adding an acidic electrolyte solution to reduce the pH value of the graphene oxide dispersion to below 2, preferably 1, so as to protonate and separate out the graphene oxide.
(3) Adding a solvent into the graphene oxide slurry obtained in the step (2) to adjust the surface energy of the liquid, and flattening the protonated graphene oxide sheet; the solvent used comprises one or more of methanol, ethanol, formic acid, acetic acid, glycol and oxalic acid, and preferably absolute ethanol is used according to the volume ratio of the absolute ethanol to the graphene oxide slurry of 1: 4, mixing.
(4) Injecting the graphene oxide slurry obtained in the step (3) into a mold container with a nylon net at the bottom, standing and air-drying to obtain a graphene oxide thick film; the number of the nylon meshes is 1000-1800 meshes, and 1200 meshes is preferred.
(5) And carrying out heat treatment and compaction on the graphene oxide thick film to obtain the ultrahigh heat conduction graphene thick film.
Further, the C/O of the graphite oxide used in the step (1) is 1-5, preferably 1.6; deionized water resistivity greater than 10M Ω cm (25 deg.C); the concentration of the graphene oxide in the graphene oxide hydrosol is 1-20 mg/mL.
Further, the acidic electrolyte solution used in step (2) comprises HCl and H2SO4、NH4Cl、NH4HSO4、(NH4)2SO4Preferably HCl and NH4Cl in a mass concentration ratio of1: 23, mixing the solution; adding an acidic electrolyte solution to reduce the pH value of the graphene oxide dispersion to below 2, preferably 1; so that the graphene oxide in the dispersion system is separated out by protonation, and the separation from the dispersing agent is realized.
Further, the solvent used in step (3) comprises one or more of methanol, ethanol, formic acid, acetic acid, ethylene glycol and oxalic acid; preferably ethanol, and the volume ratio of the ethanol to the graphene oxide slurry is 1: 4, mixing; the solvent maintains the two-dimensional planar structure of the protonated graphene oxide sheets.
Further, the number of the nylon meshes used in the step (4) is 1000-1800 meshes, preferably 1200 meshes; the air drying conditions are as follows: and (3) air-drying at the ambient temperature of 20-50 ℃, preferably 35 ℃, at the air flow rate of 7-12m/s until the water content of the graphene oxide film is less than 5 wt%.
Further, in the step (5), the heat treatment is carried out under the protection of argon, the temperature is raised to 2800-3000 ℃ at the speed of 5-20 ℃/min, and the temperature is kept for 1-2 hours; after cooling, pressing the graphene film to a density of 17-2.1 g/cm at normal temperature3And obtaining the graphene film with ultrahigh heat conductivity.
The graphene thick film with ultrahigh heat conductivity prepared by the preparation method has the thickness of 50-300 mu m and the density of 1.7-2.1g/cm3The prepared film has the heat conductivity of more than 1500W/mK along the plane direction, and when the thickness of the prepared film is more than 300 mu m, the heat conductivity of the prepared film along the plane direction can still be kept above 1000W/mK; and the graphene thick film is an integral homogeneous material, no layering exists, and no bubbling phenomenon exists on the surface.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the preparation process of the graphene thick film, the graphene oxide is protonated and separated from the emulsion, so that the dispersoid in the graphene oxide hydrosol is separated from the dispersing agent, the dispersing agent can be rapidly discharged under the condition of ensuring the stripping quality of graphene oxide lamella, the graphene oxide is rapidly solidified into the thick film, and the concentration and the evaporation of the dispersing agent are not required to be carried out on the graphene oxide dispersoid in the process; the method has the advantages that the high-quality precursor is obtained more efficiently and energy-saving in the preparation process of the graphene thick film, and the energy consumption and the cost for preparing the graphene thick film material are reduced.
(2) According to the preparation process of the precursor graphene oxide thick film, a one-step forming method is adopted, so that on one hand, complicated procedures such as high-temperature hot pressing and the like required in the process of preparing the thick film in a laminated manner or forming the film for multiple times and energy consumption caused by the complicated procedures are avoided, the production efficiency is improved, and the production cost is saved; on the other hand, the thermal resistance caused by the interface effect between the film layers generated by laminating or multiple film forming is avoided, and the heat conducting property of the final product is improved.
(3) According to the invention, the surface energy of the dispersing agent is adjusted, so that the problem of collapse of the oxidized graphene structure after protonation is solved, and the oxidized graphene thick film precursor with high orientation degree and compact arrangement is obtained, so that the problem that the thermal conductivity of the existing graphene thick film material along the plane direction is greatly reduced along with the increase of the thickness of the material is solved, and the thermal conductivity of the final graphene thick film along the plane direction is greatly improved.
Drawings
Fig. 1 is a 2500-fold magnified cross-sectional scanning electron microscope image of the ultra-high thermal conductivity graphene thick film prepared in example 1;
fig. 2 is a scanning electron microscope image of a 25000-fold enlarged cross section of the ultra-high thermal conductive graphene thick film prepared in example 1.
Detailed Description
The invention discloses a graphene thick film with ultrahigh heat conductivity and a preparation method thereof. In order to efficiently obtain a graphene oxide thick film precursor with high orientation degree and compact interlayer arrangement in the process of preparing the ultrahigh heat conduction graphene thick film, the method disclosed by the invention has the advantages that the deeply stripped graphene oxide is subjected to protonation treatment, so that the graphene oxide is separated from a dispersing agent and is separated out from a dispersion system; meanwhile, the adjustment of the solution indicates energy, so that the protonated graphene oxide sheet layer maintains the two-dimensional plane structure. Therefore, under the condition of not needing to be dried for a long time, graphene oxide and a dispersing agent are quickly separated, a high-quality graphene oxide thick film which is highly oriented and has a compact interlayer structure is obtained, and the graphene thick film material with ultrahigh thermal conductivity along the plane direction is further obtained through reduction.
In order to make the technical personnel in the field understand the scheme of the invention better, the following embodiment is combined with the more specific description of the scheme of the invention. The embodiments are only a part of the embodiments of the present invention, but not all of them. The present invention is described in further detail, and the scope of the invention should not be limited by the embodiments, and the insubstantial changes and modifications from the above disclosure, or all other embodiments obtained without inventive step, by those skilled in the art should be considered as falling within the scope of the invention.
Example 1
(1) After graphite oxide with the solid content of 44.6% and the C/O =1.67 was washed to be neutral with deionized water, the graphite oxide was diluted with deionized water to the graphite oxide concentration of 10mg/mL, 200mL of the mixed solution was taken, and water bath ultrasound was performed for 12 hours while stirring at the speed of 300 r/min.
(2) Adding HCl and NH into HCl solution with the mass fraction of 5%4The amount ratio of Cl substance is 1: 23 addition of NH4Cl powder, preparing HCl and NH4Cl mixed solution, and HCl and NH are added into graphene oxide hydrosol4And (4) Cl, reducing the pH value of the graphene oxide hydrosol to 1, and stirring for 30 minutes at the rotating speed of 300 r/min.
(3) Adding the graphene oxide slurry into a slurry, wherein the volume ratio of the slurry to ethanol is 1: 4, adding absolute ethyl alcohol, and stirring for 30 minutes at the rotating speed of 300 r/min.
(4) Sealing the bottom of a mold with a rectangular 1200-mesh nylon net with the bottom of 8cm x 8cm, pouring graphene oxide slurry into the mold along the mold wall, opening a sealing bottom plate to discharge water, standing for 30 minutes, placing the mold in a 35 ℃ blast drying oven, drying for 1 hour, removing the mold, and taking out the graphene oxide thick film.
(5) And (2) placing the graphene oxide film in an argon atmosphere, heating to 3000 ℃ at a heating rate of 10 ℃/min, carrying out thermal reduction and graphitization treatment, applying 20 tons of pressure to the surface of the graphene thick film by using a hydraulic press in a vacuum environment, and keeping for 30 minutes.
The ultrahigh heat conduction graphene thick film obtained by the embodiment has the density of 2.08g/cm3, the thickness of 63 mu m and the thermal conductivity of 1839W/mK at 25 ℃ along the plane direction.
Example 2
(1) After graphite oxide with the solid content of 44.6% and the C/O =1.67 was washed to be neutral with deionized water, the graphite oxide was diluted with deionized water to the graphite oxide concentration of 10mg/mL, 400mL of the mixed solution was taken, and water bath ultrasound was performed for 12 hours while stirring at the speed of 300 r/min.
(2) Adding HCl and NH into HCl solution with the mass fraction of 5%4The amount ratio of Cl substance is 1: 23 addition of NH4Cl powder, preparing HCl and NH4Cl mixed solution, and HCl and NH are added into graphene oxide hydrosol4And (4) Cl, reducing the pH value of the graphene oxide hydrosol to 1, and stirring for 30 minutes at the rotating speed of 300 r/min.
(3) Adding the graphene oxide slurry into a slurry, wherein the volume ratio of the slurry to ethanol is 1: 4, adding absolute ethyl alcohol, and stirring for 30 minutes at the rotating speed of 300 r/min.
(4) Sealing the bottom of a mold with a rectangular 1200-mesh nylon net with the bottom of 5cm by 5cm, pouring graphene oxide slurry into the mold along the mold wall, opening a sealing bottom plate to discharge water, standing for 30 minutes, placing the mold in a 35 ℃ blast drying oven, drying for 1.5 hours, dismantling the mold, and taking out the graphene oxide thick film.
(5) And (2) placing the graphene oxide film in an argon atmosphere, heating to 3000 ℃ at a heating rate of 10 ℃/min, carrying out thermal reduction and graphitization treatment, applying 20 tons of pressure to the surface of the graphene thick film by using a hydraulic press in a vacuum environment, and keeping for 30 minutes.
The ultrahigh heat-conducting graphene thick film obtained in the embodiment has the density of 2.07g/cm3, the thickness of 324 microns and the thermal conductivity of 1537W/mK at 25 ℃ along the plane direction.
Example 3
(1) After graphite oxide with the solid content of 44.6% and the C/O =1.67 was washed to be neutral with deionized water, the graphite oxide was diluted with deionized water to the graphite oxide concentration of 10mg/mL, and 600mL of the mixed solution was subjected to water bath ultrasound for 12 hours while stirring at the speed of 300 r/min.
(2) Adding HCl and NH into HCl solution with the mass fraction of 5%4Cl compoundThe mass ratio of the components is 1: 23 addition of NH4Cl powder, preparing HCl and NH4Cl mixed solution, and HCl and NH are added into graphene oxide hydrosol4And (4) Cl, reducing the pH value of the graphene oxide hydrosol to 1, and stirring for 30 minutes at the rotating speed of 300 r/min.
(3) Adding the graphene oxide slurry into a slurry, wherein the volume ratio of the slurry to ethanol is 1: 4, adding absolute ethyl alcohol, and stirring for 30 minutes at the rotating speed of 300 r/min.
(4) Sealing the bottom of a mold with a rectangular 1200-mesh nylon net with the bottom of 5cm by 5cm, pouring graphene oxide slurry into the mold along the mold wall, opening a sealing bottom plate to discharge water, standing for 30 minutes, placing the mold in a 35 ℃ blast drying oven, drying for 1.5 hours, dismantling the mold, and taking out the graphene oxide thick film.
(5) And (2) placing the graphene oxide film in an argon atmosphere, heating to 3000 ℃ at a heating rate of 10 ℃/min, carrying out thermal reduction and graphitization treatment, applying 20 tons of pressure to the surface of the graphene thick film by using a hydraulic press in a vacuum environment, and keeping for 30 minutes.
The ultrahigh thermal conductivity graphene thick film obtained by the embodiment has the density of 2.07g/cm3, the thickness of 487 mu m and the thermal conductivity of 1374W/mK at 25 ℃ along the plane direction.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. A preparation method of a graphene thick film with ultrahigh heat conductivity is characterized by comprising the following steps:
(1) washing graphite oxide to be neutral, mixing the graphite oxide with deionized water, and stripping the graphite oxide by using an ultrasonic and stirring mode to prepare graphene oxide hydrosol;
(2) adding an acidic electrolyte solution into the graphene oxide hydrosol obtained in the step (1) to protonate and separate out graphene oxide, so as to obtain protonated graphene oxide slurry;
(3) adding a solvent into the graphene oxide slurry obtained in the step (2) to adjust the surface energy of the liquid;
(4) injecting the graphene oxide slurry obtained in the step (3) into a mold container with a nylon net at the bottom, standing to separate water and air-drying to obtain a graphene oxide thick film;
(5) carrying out heat treatment and compaction on the graphene oxide thick film to obtain an ultrahigh heat conduction graphene thick film;
the C/O of the graphite oxide used in the step (1) is 1-5; deionized water resistivity greater than 10M Ω cm; the concentration of the graphene oxide in the graphene oxide hydrosol is 1-20 mg/mL; the acidic electrolyte solution used in the step (2) is HCl and NH4Cl is added according to the mass ratio of 1: 23, mixing the solution; the solvent used in the step (3) is ethanol, and the volume ratio of the ethanol to the graphene oxide slurry is 1: 4, mixing to ensure that the protonated graphene oxide sheet layer maintains the two-dimensional plane structure.
2. The preparation method according to claim 1, wherein the pH value of the graphene oxide dispersion system is reduced to below 2 by adding an acidic electrolyte solution in the step (2); so that the graphene oxide in the dispersion system is separated out by protonation, and the separation from the dispersing agent is realized.
3. The method according to claim 1, wherein the number of the nylon mesh used in the step (4) is 1000 to 1800 mesh; the air drying conditions are as follows: and (3) air-drying at the ambient temperature of 20-50 ℃ and at the air flow rate of 7-12m/s until the water content of the graphene oxide film is less than 5 wt%.
4. The preparation method according to claim 1, wherein the heat treatment in the step (5) is carried out by heating to 2800-3000 ℃ at a rate of 5-20 ℃/min under an argon protective atmosphere, and keeping the temperature for 1-2 hours; and after the temperature is reduced, pressing the graphene film to a density of 17-2.1 g/cm at normal temperature3。
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