CN109627004B - Heat-conducting and electric-conducting graphene film and preparation method thereof - Google Patents
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Abstract
The invention discloses a heat-conducting and electric-conducting graphene film and a preparation method thereof. The preparation method comprises the following steps: mixing the prepared graphene oxide aqueous solution with dopamine hydrochloride-Tris buffer solution, taking the graphene oxide-dopamine aqueous solution, preparing a film through vacuum assistance, reducing the film by using a reducing agent, and heating the reduced film to 800-1000 ℃ in an argon atmosphereoC, preserving heat, and then heating to 2800-3000 DEGoAnd C, preserving heat, naturally cooling to room temperature, and mechanically molding the graphitized graphene film. The heat-conducting and electric-conducting graphene film disclosed by the invention has high mechanical property, high heat conductivity and high electric conductivity.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a high-strength high-heat-conductivity electric-conduction graphene film and a preparation method thereof.
Background
With the rapid development of electronic technology, electronic devices such as mobile phones and notebook computers are continuously miniaturized and portable, and meanwhile, the functions of the electronic devices are increasingly powerful, so that integrated circuits become more fine and complex, the current density is rapidly increased, the electronic devices generate a large amount of heat in the operation process, the heat needs to be rapidly conducted from the electronic devices to the air, otherwise, the normal operation of the electronic devices is seriously affected, and the service life of the electronic devices is shortened, and therefore, the demand for ultra-thin high-thermal-conductivity materials is increasing. Meanwhile, a large amount of electromagnetic waves can be emitted in the operation process of electronic equipment, and the electromagnetic waves can cause electromagnetic interference on one hand, influence the normal operation of other equipment, and secondly cause great threat to human health, so that an ultrathin high-conductivity material is urgently needed for shielding electromagnetic pollution generated by tiny equipment. Therefore, there is an urgent need for new ultra-thin materials with high thermal conductivity and electrical conductivity.
As a material with the best electrical and thermal conductivity, graphene plays an important role in ultrathin thermal and electrical conductive materials. The graphene oxide film formed by stacking graphene sheets can be prepared by a suction filtration method, a film scraping method, a spin coating method and the like, the structural defects of the graphene oxide can be further repaired by reduction and high-temperature calcination, and the heat conduction and electric conductivity of the graphene film are improved, so that the graphene oxide film is applied to electronic equipment such as mobile phones, tablet computers, notebook computers and the like.
However, in the prior art, although high-temperature graphitization treatment, mechanical die pressing and other modes are adopted, it is still difficult to prepare the graphene film with ultrahigh heat and electrical conductivity, the thermal conductivity of the graphene film is limited to 1700W/mK, and the electrical conductivity is limited to 10000S/cm, and meanwhile, the mechanical property of the graphene film is poor and limited within 100MPa due to the damage of volatile gas to the film sheet structure in the graphitization process. The mechanical properties and the heat and electricity conductivity of the graphene film cannot meet the requirements of rapid development of electronic science and technology.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide a heat-conducting and electric-conducting graphene film, which can improve the mechanical property of the material and the heat-conducting and electric-conducting properties of the material. The invention also provides a preparation method of the graphene film.
The technical problem to be solved by the invention is realized through the technical scheme, the heat-conducting and electric-conducting graphene film provided by the invention is prepared by blending a dopamine hydrochloride-Tris buffer solution and a graphene solution to prepare a film, the film is formed by stacking graphene sheet layers, carbon nanoparticles formed by carbonizing polydopamine are uniformly distributed inside the graphene sheet layers and among the sheet layers, and the graphene sheet layers and the carbon nanoparticles are crosslinked together.
The invention provides a preparation method of the heat-conducting and electric-conducting graphene film, which comprises the following steps:
step 1, preparing graphene oxide with the average size of 120-150 mu m into a graphene oxide aqueous solution with the concentration of 0.5-30 mg/ml;
step 3, mixing the graphene oxide aqueous solution with dopamine hydrochloride-Tris buffer solution, stirring and reacting at 0-75 ℃ for at least 0.5h, centrifuging at 500-12000 rpm for at least 5min, and removing precipitate to obtain graphene oxide-poly dopamine aqueous solution;
step 4, preparing a film from the graphene oxide-polydopamine aqueous solution through vacuum assistance, and reducing the film by using a reducing agent;
step 5, heating the reduced film to 800-1000 ℃ at a speed of 1-5 ℃/min under an argon atmosphere, and preserving heat for at least 5 min; then continuously heating to 2800-3000 ℃ at the speed of 5-30 ℃/min, preserving the heat for at least 10min, and naturally cooling to room temperature to obtain a graphitized graphene film;
and 6, mechanically molding the graphitized graphene film.
In the step 1, the preparation of the graphene oxide with the average size of 120-150 μm comprises the following steps:
step 1), mixing flake graphite with the average size of 200-1000 mu m, chromium trioxide and hydrochloric acid according to the ratio of 1g to 1-30 g to 10-100 ml, reacting for at least 0.5h under stirring, washing with deionized water, adding 5-300 ml of hydrogen peroxide, reacting for at least 0.5h, and vacuum drying for at least 1h to obtain expanded graphite;
step 2), mixing the obtained expanded graphite, concentrated sulfuric acid and phosphoric acid according to a ratio of 1g to 50-500 ml, stirring and reacting at a temperature of 0-10 ℃ for at least 5min, then adding 1-90 g of potassium permanganate, and reacting at a temperature of 0-100 ℃ for at least 1 h;
step 3) adding 2500ml of water and 5-500 ml of hydrogen peroxide, and continuing to react for 5-480 min; adding 5-200 ml of hydrochloric acid, reacting for at least 1h, centrifuging to remove acid liquor, washing with deionized water until the pH value is 6-7, and magnetically stirring at room temperature for at least 0.5h to obtain a graphene oxide aqueous solution with the average size of 120-150 mu m.
In the step 3, the graphene oxide aqueous solution and the dopamine hydrochloride-Tris buffer solution are mixed according to the weight ratio of 1: 0.025-2.
In the step 4, the reducing agent is hydroiodic acid or hydrazine hydrate; since hydriodic acid does not cause the film to generate a large number of bubbles during the reduction process, which causes the film to expand, hydriodic acid is preferably used as the reducing agent. The reduction temperature is 50-100 ℃, and the reduction time is 0.5-24 h.
In the step 6, the pressure of the mechanical die pressing is 100-500 Mpa, the pressure maintaining time is at least 0.5h, and the pressurizing temperature is 30-250 ℃.
According to the preparation method, a dopamine hydrochloride-Tris buffer aqueous solution and a graphene oxide solution are blended and then subjected to vacuum assisted membrane preparation, dopamine acts with oxygen-containing groups on graphene oxide lamella through amino groups of the dopamine, and meanwhile dopamine is oxidized and self-polymerized to generate polydopamine to obtain a polydopamine-graphene oxide composite membrane, the polydopamine plays a role in reduction and crosslinking on the graphene oxide, and the polydopamine is carbonized to generate carbon nanoparticles with a graphite crystal structure after further chemical reduction, high-temperature graphitization treatment and mechanical mould pressing, so that on one hand, the structural compactness of the graphene membrane and the orientation of the inner lamella of the graphene membrane are improved, and the defect of the graphene lamella is eliminated; on the other hand, the high-conductivity carbon nano particles are uniformly dispersed and embedded between the graphene sheet layers, so that the effects of crosslinking and reinforcing the filler are achieved, and meanwhile, the mechanical property and the heat conduction and electric conductivity of the graphene film are greatly improved.
The performance indexes of the heat-conducting and electric-conducting graphene film are as follows: the density is 2.12 to 2.33g/cm3The tensile strength is 85-150 Mpa, and the elongation at break is 11-15.4%; the electrical conductivity is 12578-15000S/cm, and the thermal conductivity is 2048-2860W/mK.
The heat-conducting and electric-conducting graphene film disclosed by the invention has high mechanical property, high heat-conducting property and electric-conducting property, and has a wider application prospect in the fields of heat-conducting and electric-conducting devices and electromagnetic shielding devices.
Drawings
The drawings of the invention are illustrated as follows:
FIG. 1 is SEM and TEM photographs of the graphene thin film obtained in example 3 of the present invention
FIG. 1(a) is an SEM photograph at a resolution of 10 μm,
FIG. 1(b) is a TEM photograph with a resolution of 200nm,
FIG. 1(c) is a TEM photograph with a resolution of 10nm,
FIG. 1(d) is a TEM photograph of carbonized polydopamine nanoparticles with a resolution of 2 nm;
fig. 2 is a raman spectrum of the graphene film obtained in example 3 of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
the concentrated sulfuric acid used in the following examples was 98% by mass, the hydrochloric acid was 37% by mass, the hydrogen peroxide was 30% by mass, and the phosphoric acid was 85% by mass.
Examples of preparing graphene oxide with an average size of 120-150 μm include:
example 1
Step 1), taking 3g of crystalline flake graphite with the average size of 200 mu m, adding 3g of chromium trioxide and 30ml of hydrochloric acid, reacting at room temperature for 0.5h, washing, adding 15ml of hydrogen peroxide, reacting for 0.5h, and vacuum-drying for 1h to obtain expanded graphite;
step 2), taking 1g of expanded graphite, adding 50ml of concentrated sulfuric acid and 50ml of phosphoric acid, stirring at the low temperature of 0 ℃ for 5min, then adding 1g of potassium permanganate, and reacting at the temperature of 0 ℃ for 1 h;
and 3) adding 100ml of ice water, adding 5ml of hydrogen peroxide, reacting for 5min, adding 5ml of hydrochloric acid, reacting for 1h, centrifuging to remove acid liquor, washing with deionized water until the pH value is 6-7, and magnetically stirring at room temperature for 0.5h to obtain a graphene oxide aqueous solution with the average size of 120-150 mu m.
Example 2
Step 1), taking 3g of crystalline flake graphite with the average size of 500 mu m, adding 30g of chromium trioxide and 200ml of hydrochloric acid, reacting at room temperature for 1h, washing, adding 500ml of hydrogen peroxide, reacting for 6h, and vacuum drying for 12h to obtain expanded graphite; ,
step 2), taking 1g of expanded graphite, adding 120ml of concentrated sulfuric acid and 60ml of phosphoric acid, stirring at the low temperature of 10 ℃ for 120min, then adding 15g of potassium permanganate, and reacting at the temperature of 50 ℃ for 12 h;
step 3), adding 600ml of ice water, adding 200ml of hydrogen peroxide, reacting for 120min, adding 100ml of hydrochloric acid, reacting for 24h, centrifuging to remove acid liquor, washing with deionized water until the pH value is 6-7, and magnetically stirring at room temperature for 24h to obtain a graphene oxide aqueous solution with the average size of 120-150 mu m.
Example 3
Step 1), taking 3g of crystalline flake graphite with the average size of 1000 mu m, adding 90g of chromium trioxide and 300ml of hydrochloric acid, reacting at room temperature for 5 hours, washing, adding 900ml of hydrogen peroxide, reacting for 96 hours, and vacuum-drying for 96 hours to obtain expanded graphite;
step 2), taking 1g of expanded graphite, adding 500ml of concentrated sulfuric acid and 500ml of phosphoric acid, stirring for 480min at low temperature of 5 ℃, then adding 90g of potassium permanganate, and reacting for 96h at 100 ℃;
and 3), adding 2500ml of ice water, adding 500ml of hydrogen peroxide, reacting for 480min, adding 200ml of hydrochloric acid, reacting for 96h, centrifuging to remove acid liquor, washing with deionized water until the pH value is 6-7, and magnetically stirring for 48h at room temperature to obtain a graphene oxide aqueous solution with the average size of 120-150 mu m.
Examples of preparing the thermally and electrically conductive graphene film include:
example 1
Step 1, preparing graphene oxide with the average size of 120-150 mu m into a graphene oxide aqueous solution with the concentration of 0.5 mg/ml;
step 3, mixing the prepared graphene oxide aqueous solution with dopamine hydrochloride-Tris buffer solution according to the weight ratio of 1: 1, stirring and reacting for 0.5h at 0 ℃, centrifuging for 5min at 500rpm, and removing precipitates to obtain the graphene oxide-poly dopamine aqueous solution;
step 4, preparing a film by taking 20ml of graphene oxide-polydopamine aqueous solution through vacuum assistance, and reducing the film in hydrazine hydrate for 0.5h at 80 ℃;
step 5, heating the reduced film to 1000 ℃ at the speed of 1 ℃/min under the argon atmosphere, and preserving the heat for 5 min; then continuously heating to 2800 ℃ at the speed of 5 ℃/min, preserving the heat for 10min, and naturally cooling to room temperature to obtain a graphitized graphene film;
and 6, pressing the graphitized graphene film for 0.5h at the temperature of 30 ℃ under 100MPa to obtain the high-thermal-conductivity and high-electric-conductivity graphene film.
The prepared graphene film has the tensile strength of 85MPa, the elongation at break of 14.7%, the electric conductivity of 12578S/cm and the thermal conductivity of 2050W/mK.
Example 2
Step 1, preparing graphene oxide with the average size of 120-150 mu m into a graphene oxide aqueous solution with the concentration of 30 mg/ml;
step 3, mixing the prepared graphene oxide aqueous solution and dopamine hydrochloride-Tris buffer solution according to the weight ratio of 1: 2, mixing, stirring and reacting for 6h at 75 ℃, centrifuging for 60min at 12000rpm, and removing precipitates to obtain a graphene oxide-polydopamine aqueous solution;
step 4, preparing a film by taking 1ml of graphene oxide-polydopamine aqueous solution through vacuum assistance, and reducing the film in hydroiodic acid at 50 ℃ for 12 hours;
step 5, heating the reduced film to 800 ℃ at the speed of 2 ℃/min under the argon atmosphere, and preserving the heat for 60 min; then continuously heating to 2900 ℃ at the speed of 10 ℃/min, preserving the heat for 120min, and naturally cooling to room temperature to obtain the graphitized graphene film;
and step 6, pressing the graphitized graphene film for 96 hours at 350MPa and 150 ℃ to obtain the high-thermal-conductivity and electric-conductivity graphene film.
The prepared graphene film can reach 124MPa, the breaking elongation can reach 13.5%, the electric conductivity can reach 13200S/cm, and the thermal conductivity can reach 2370W/mK.
Example 3
Step 1, preparing graphene oxide with the average size of 120-150 mu m into a graphene oxide aqueous solution with the concentration of 10 mg/ml;
step 3, mixing the prepared graphene oxide aqueous solution and dopamine hydrochloride-Tris buffer solution according to the weight ratio of 1: 1, mixing, stirring and reacting for 6 hours at 50 ℃, centrifuging for 30 minutes at 3000rpm, and removing precipitates to obtain a graphene oxide-polydopamine aqueous solution;
step 4, preparing a film by taking 5ml of graphene oxide-polydopamine aqueous solution through vacuum assistance, and reducing the film in hydroiodic acid at 100 ℃ for 24 hours;
step 5, heating the reduced film to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere, and preserving the heat for 30 min; then continuously heating to 3000 ℃ at the speed of 30 ℃/min, preserving the heat for 240min, and naturally cooling to room temperature to obtain a graphitized graphene film;
and 6, pressing the graphitized graphene film for 96 hours at the temperature of 250 ℃ under 500MPa to obtain the high-thermal-conductivity and electric-conductivity graphene film.
The prepared graphene film can reach 150MPa, the elongation at break can reach 11%, the electric conductivity can reach 15000S/cm, and the thermal conductivity can reach 2860W/mK.
Example 4 (comparative example)
The difference from example 3 is: in step 3, mixing the graphene oxide aqueous solution with dopamine hydrochloride-Tris buffer solution according to the dosage proportion listed in Table 1;
TABLE 1
As seen from table 1: with the increase of the dosage of the dopamine-Tris hydrochloride buffer solution, the tensile strength, the electrical conductivity and the thermal conductivity are increased, and the elongation at break is reduced.
Fig. 1 is SEM and TEM photographs of the graphene film obtained in example 3, and it can be seen that the obtained graphene film has a compact lamellar structure, and after the poly-dopamine is carbonized, carbon nanoparticles having a graphite crystal structure are formed, and the carbon nanoparticles are uniformly dispersed in the graphene lamellar layer, and play a role in crosslinking and enhancing in the graphene lamellar layer. Fig. 2 is a raman spectrum of the graphene film obtained in example 3, and it can be seen that the ratio of the D peak to the G peak of the obtained graphene film is 0.0042, which indicates that the graphene film has few defects and has a complete graphene structure.
Claims (9)
1. A heat and electricity conductive graphene film is characterized in that: the method comprises the steps of preparing a membrane by blending dopamine hydrochloride-Tris buffer solution and graphene oxide solution, wherein the membrane is formed by stacking graphene sheet layers, carbon nanoparticles formed by carbonizing polydopamine are uniformly distributed inside the graphene sheet layers and among the sheet layers, and the graphene sheet layers and the carbon nanoparticles are crosslinked together.
2. The preparation method of the heat-conducting and electric-conducting graphene film as claimed in claim 1, which is characterized by comprising the following steps:
step 1, preparing graphene oxide with the average size of 120-150 mu m into a graphene oxide aqueous solution with the concentration of 0.5-30 mg/mL;
step 2, preparing dopamine hydrochloride-Tris buffer solution with the concentration of 0.5-30 mg/mL;
step 3, mixing the graphene oxide aqueous solution with dopamine hydrochloride-Tris buffer solution at the concentration of 0-75%oStirring and reacting for at least 0.5h under the condition of C,centrifuging at 500-12000 rpm for at least 5min, and removing the precipitate to obtain graphene oxide-polydopamine aqueous solution;
step 4, preparing a film from the graphene oxide-polydopamine aqueous solution through vacuum assistance, and reducing the film by using a reducing agent;
step 5, reducing the reduced film by 1-5 times in an argon atmosphereoHeating to 800-1000 ℃ at a rate of C/minoC, preserving the heat for at least 5 min; then continuing to use the method for 5-30 DEG CoHeating to 2800-3000 at C/minoC, preserving the heat for at least 10min, and naturally cooling to room temperature to obtain a graphitized graphene film;
and 6, mechanically molding the graphitized graphene film.
3. The method for preparing the thermally and electrically conductive graphene film according to claim 2, wherein in the step 1, the preparation of the graphene oxide with the average size of 120-150 μm comprises the following steps:
step 1), mixing flake graphite with the average size of 200-1000 mu m, chromium trioxide and hydrochloric acid according to the ratio of 1g to 1-30 g to 10-100 mL, reacting for at least 0.5h under stirring, washing with deionized water, adding 5-300 mL of hydrogen peroxide, reacting for at least 0.5h, and vacuum drying for at least 1h to obtain expanded graphite;
step 2), mixing the obtained expanded graphite, concentrated sulfuric acid and phosphoric acid according to the proportion of 1 g: 50-500 mL, and heating at the temperature of 0-10 DEG CoStirring and reacting for at least 5min under C, then adding 1-90 g of potassium permanganate, and reacting at 0-100 DEGoC, reacting for at least 1 h;
step 3) adding 2500mL of water and 5-500 mL of hydrogen peroxide, and continuing to react for 5-480 min; adding 5-200 mL of hydrochloric acid, reacting for at least 1h, centrifuging to remove acid liquor, washing with deionized water until the pH value is 6-7, and magnetically stirring at room temperature for at least 0.5h to obtain a graphene oxide aqueous solution with the average size of 120-150 mu m.
4. The method for preparing a thermally and electrically conductive graphene film according to claim 2 or 3, wherein in step 3, the aqueous solution of graphene oxide and the dopamine-Tris hydrochloride buffer solution are mixed in a weight ratio of 1: 0.025-2.
5. The method for preparing the thermally and electrically conductive graphene film according to claim 4, wherein in the step 4, the reducing agent is hydroiodic acid or hydrazine hydrate.
6. The method for preparing the thermally and electrically conductive graphene film according to claim 5, wherein in the step 4, the reduction temperature is 50 to 100%oAnd C, the reduction time is 0.5-24 h.
7. The method for preparing the thermally and electrically conductive graphene film according to claim 6, wherein in the step 6, the pressure of the mechanical die pressing is 100 to 500MPa, the pressure-maintaining time is at least 0.5h, and the pressing temperature is 30 to 250%oC。
8. The method for preparing the thermally and electrically conductive graphene film according to claim 7, wherein: in step 3, the graphene oxide aqueous solution and the dopamine hydrochloride-Tris buffer solution are mixed according to the weight ratio of 1: 1.
9. The method for preparing the thermally and electrically conductive graphene film according to claim 8, wherein: in the step 1, the concentration of the graphene oxide aqueous solution is 10 mg/mL; in step 2, the concentration of dopamine hydrochloride-Tris buffer is 10 mg/mL.
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| CN110278702B (en) * | 2019-06-04 | 2021-02-19 | 江南石墨烯研究院 | High-stretch high-elasticity electromagnetic shielding composite material and preparation method thereof |
| CN112280541A (en) * | 2019-07-24 | 2021-01-29 | 天津大学 | Preparation method of high-thermal-conductivity composite material based on graphitized poly-dopamine-coated metal particles |
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