CN113896188A - Preparation method of boron-doped graphene heat-conducting film - Google Patents
Preparation method of boron-doped graphene heat-conducting film Download PDFInfo
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Abstract
The invention relates to a preparation method of a boron-doped graphene heat-conducting film, which comprises the following steps: mixing DBU and alkyl alcohol, and introducing CO into mixed liquid2The white gelatinous solid formed after the gas is the DBUH reversible ionic liquid; adding graphite powder into DBUH reversible ionic liquid serving as a stripping agent and water serving as a solvent, and uniformly stirring to obtain a graphite pre-stripping dispersion liquid; carrying out stripping dispersion on the graphite pre-stripping dispersion liquid under a hydrothermal condition to obtain a graphene mixed dispersion system; fourthly, centrifuging and filtering the graphene mixed system to obtain a pure graphene product; fifthly, dispersing the graphene product in the surfactant aqueous solution, adding the boron salt, fully stirring to obtain a graphene dispersion solution, and performing vacuum filtration to form a film, drying and calcining on the graphene dispersion solution to obtain the graphene heat-conducting film. The invention is simple,The method has the advantages of effectively stripping the graphite sheet layer, preventing the agglomeration of the graphene and causing less damage to the intrinsic structure of the graphene.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a preparation method of a boron-doped graphene heat-conducting film.
Background
Graphene (Graphene) is oneFrom carbon atoms in sp2The hybrid tracks form a hexagonal honeycomb-lattice planar two-dimensional layered material, the material has excellent physical and chemical properties, the thermal conductivity coefficient of the material is as high as 5300W/m.K, which is higher than that of a carbon nano tube and diamond, but the thermal conductivity coefficient of graphene can be reduced due to defects and edge disorder of graphene, and the characteristics of graphene can be further regulated and controlled and the application of the graphene can be expanded by changing the size or the structure of the graphene. The heterogeneous atom doping can effectively regulate and control the performances of the graphene such as an energy band structure and the like, and the application field of the graphene is expanded. Therefore, a controllable preparation method for doping graphene and a performance regulation and control means become research hotspots in the field of material science.
Wang et al successfully prepared single-layer boron-doped graphene (Small 2013, 9, 1316-. Jung et al used a modified Woltz reaction to convert CCl4And BBr3Boron-doped graphene is generated under the action of elemental potassium and is used as a metal-free cathode material of a solar cell (chem.mater. 2014, 26, 3586-. Li et al use a hydrothermal reaction, and implement boron doping of graphene by a chemical reduction method and apply it to a photocatalyst (rsc.adv., 2014, 4, 37992), but these methods have high requirements on equipment and are complex to operate. In view of this, the development of a simple and efficient preparation method is one of the major research points at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a boron-doped graphene heat-conducting film, which is simple, low in cost and capable of realizing industrial production.
In order to solve the above problems, the preparation method of the boron-doped graphene thermal conductive film provided by the invention comprises the following steps:
firstly, 1, 8-diazabicyclo [5.4.0 ] is adopted]Mixing undec-7-ene (DBU) and alkyl alcohol according to the ratio of 0.5-10: 1, introducing CO into the mixed solution at 25 DEG C2Gas, and a white gelatinous solid formed after 60min is the DBUH reversible ionic liquid;
secondly, adding graphite powder into the DBUH reversible ionic liquid serving as a stripping agent and water serving as a solvent, and uniformly stirring to obtain a graphite pre-stripping dispersion liquid;
thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle for stripping dispersion to obtain a graphene mixed dispersion system;
fourthly, centrifuging and filtering the graphene mixed system to obtain a pure graphene product;
fifthly, dispersing the graphene product into a surfactant aqueous solution with the concentration of 3-30 wt%, adding 0.5-10% of boron salt of the mass of the graphene product, fully stirring to obtain a graphene dispersion liquid with the concentration of 0.5-10 mg/mL, and carrying out vacuum filtration to form a film, drying and calcining on the graphene dispersion liquid to obtain the graphene heat conduction film.
The alkyl alcohol in the step is one of methanol, ethanol, hexanol, isopropanol, diethylene glycol, glycerol, 1, 4-butanediol, 1-propanol, tert-butyl alcohol, 1, 3-propanediol, cyclohexanol and glucose.
CO in the step2The gas flow rate is 0.1-50 mL/min.
The graphite powder in the step II is one of scale graphite powder, expanded graphite powder, oxidized graphite powder and natural graphite powder.
The method comprises the step of pre-stripping graphite powder in the dispersion liquid by graphite, wherein the concentration of the graphite powder in the dispersion liquid is 0.5-10 mg/mL.
The stripping and dispersing conditions in the step three mean that the atmosphere is carbon dioxide, the pressure is 1-10 MPa, the hydrothermal temperature is 80-160 ℃, and the time is 3-12 h.
The centrifugal condition in the step four is that the rotating speed is 100-3000 r/min, and the time is 1-10 min.
The surfactant in the surfactant aqueous solution obtained in the step fifthly is one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), polyvinylpyrrolidone (PVP), Sodium Dodecyl Sulfate (SDS), sodium poly (styrene sulfonate), sodium naphthalene sulfonate, anionic polyacrylamide, carboxylate and sulfate.
The boron salt in the step fifthly is aryl borate, and the structural general formula of the boron salt is as follows:
(ii) a In the formula R1Is aryl, R2、R3、R4Are all one of H, alkyl, aryl, halogen or acyl; y is+Is metal Na or K.
The aryl borate is one or more of phenylborate, naphthalene borate, pyrene borate, 2-boric acid anthracene salt, 3-methylbenzylborate, 4-methylbenzylborate, 2- (bromomethyl) phenylborate, 4-hydroxybenzylborate, 2-methoxy-1-naphthyl borate, 4-butoxyphenylborate, 4-carbamylborate, 2-carboxyphenylborate, 4-fluorobenzylborate, 4-biphenylborate and 4-tert-butylbenzoborate.
Compared with the prior art, the invention has the following advantages:
1. the invention takes graphite powder without any pretreatment as a raw material and utilizes DBU + alcohol/CO with a heterocyclic structure2The reversible ionic liquid is a stripping agent for stripping graphite and stabilizing the graphene layer; and then modifying the graphene by utilizing the interaction of the aromatic borate and the graphene and the synergistic effect of high hydrophilicity of the surfactant. Due to the existence of pi-pi bonds, boron is adsorbed on the surface of graphene, and the boron-doped graphene film with high thermal conductivity is obtained after high-temperature reduction.
2. The repeatedly-usable DBUH reversible ionic liquid is used as the stripping agent to replace the traditional DMF and NMP organic solvents, so that the problem of environmental pollution is effectively solved, the method has the advantages of greenness, low toxicity, safety, environmental protection, recyclability and the like, and has the potential of batch production of the high-thermal-conductivity graphene film.
3. The method is simple, low in cost and capable of realizing industrial production, and the graphite sheet can be effectively stripped by the method, so that the graphene is prevented from being agglomerated, and the damage to the intrinsic structure of the graphene is small.
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The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a flow chart of the preparation of the present invention.
Fig. 2 is a raman spectrum of graphene in example 1 of the present invention.
Fig. 3 is an appearance (a) and an SEM image (B) of the graphene thin film in example 1 of the present invention.
Detailed Description
As shown in fig. 1, a method for preparing a boron-doped graphene thermal conductive film includes the following steps:
firstly, 1, 8-diazabicyclo [5.4.0 ] is adopted]Mixing undec-7-ene (DBU) and alkyl alcohol according to the ratio of 0.5-10: 1, introducing CO with the flow rate of 0.1-50 mL/min into the mixed solution of DBU and alcohol at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
Wherein: the alkyl alcohol is one of methanol, ethanol, hexanol, isopropanol, diethylene glycol, glycerol, 1, 4-butanediol, 1-propanol, tert-butanol, 1, 3-propanediol, cyclohexanol, and glucose.
And adding graphite powder into the DBUH reversible ionic liquid serving as a stripping agent and water serving as a solvent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 0.5-10 mg/mL.
Wherein: the stripping agent is DBU/alkyl alcohol + CO2The combination pattern of (1).
The graphite powder is one of scale graphite powder, expanded graphite powder, graphite oxide powder and natural graphite powder.
The solvent may also be other polar solvents.
And thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 1-10 MPa, the hydrothermal temperature is 80-160 ℃ and the time is 3-12 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at a rotating speed of 100-3000 r/min for 1-10 min, then taking the upper-layer solution to filter, and removing impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product into a surfactant aqueous solution with the concentration of 3-30 wt%, adding boron salt with the mass of 0.5-10% of that of the graphene product, fully stirring to obtain a graphene dispersion liquid with the concentration of 0.5-10 mg/mL, and carrying out vacuum filtration to form a film, drying and calcining at 800-1200 ℃ on the graphene dispersion liquid to obtain the graphene heat-conducting film.
Wherein: the surfactant in the surfactant aqueous solution is one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), polyvinylpyrrolidone (PVP), Sodium Dodecyl Sulfate (SDS), sodium poly (styrene sulfonate), sodium naphthalene sulfonate, anionic polyacrylamide, carboxylate and sulfate salt.
The boron salt refers to aryl borate, and the structural general formula of the boron salt is as follows:
(ii) a In the formula R1Is aryl, R2、R3、R4Are all one of H, alkyl, aryl, halogen or acyl; y is+Is metal Na or K.
The aryl borate refers to one or more of phenylborate, naphthalene borate, pyrene borate, 2-boranoanthrylborate, 3-methylbenzylborate, 4-methylbenzylborate, 2- (bromomethyl) phenylborate, 4-hydroxybenzylborate, 2-methoxy-1-naphthyl borate, 4-butoxyphenylborate, 4-carbamylborate, 2-carboxyphenylborate, 4-fluorobenzylborate, 4-biphenylborate and 4-tert-butylbenzoborate.
Embodiment 1 is a method for preparing a boron-doped graphene thermal conductive film, including the steps of:
mixing 15mmol of ethanol and 15mmol of DBU, and introducing CO with the flow rate of 1mL/min into the mixed solution at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
And adding 50mg of graphite powder and 50mL of water into DBUH reversible ionic liquid serving as a stripping agent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1 mg/mL.
And thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 4MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at a rotating speed of 500r/min for 5min, then taking the upper solution to filter, and removing impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product into PVP (polyvinyl pyrrolidone) aqueous solution with the concentration of 30wt%, adding sodium phenylborate with the mass of 10% of that of the graphene product, fully stirring to obtain graphene dispersion liquid with the concentration of 1mg/mL, carrying out vacuum filtration to form a film, drying at 60 ℃ for 12 hours, and then carrying out N-type furnace N drying2Calcining for 3 hours at the temperature of 800 ℃ to obtain the graphene heat-conducting film with high heat-conducting performance.
And performing a raman spectrum test on the obtained graphene product, as shown in fig. 2, finding a characteristic peak of graphene from the graph, and proving that the prepared product is graphene.
SEM tests are carried out on the obtained graphene product, as shown in figure 3, the surface of the graphene film under macroscopical conditions is smooth, flat and free of defects, the surface of the graphene is in a folded structure under microcosmic conditions, and the sheet diameter of the stacked graphene is large.
mixing 15mmol of ethylene glycol and 30mmol of DBU, and introducing CO with the flow rate of 1mL/min into the mixed solution at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
And adding 25mg of graphite powder and 50mL of water into DBUH reversible ionic liquid serving as a stripping agent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 0.5 mg/mL.
And transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 10MPa, the hydrothermal temperature is 140 ℃ and the time is 6 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at the rotating speed of 1000r/min for 5min, then taking the upper solution to filter, and removing impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product into the SDBS aqueous solution with the concentration of 30wt%, adding sodium naphthalene borate with the mass of 10% of that of the graphene product, fully stirring to obtain graphene dispersion liquid with the concentration of 0.5mg/mL, carrying out vacuum filtration to form a film, drying at 60 ℃ for 12 hours, and then carrying out N-type in a tubular furnace2Calcining for 3 hours at the temperature of 900 ℃ to obtain the high heat conductivityGraphene thermal conductive films.
Embodiment 3 is a method for preparing a boron-doped graphene thermal conductive film, including the steps of:
mixing 15mmol of glycerol and 45mmol of DBU, and introducing CO with the flow rate of 1mL/min into the mixed solution at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
And adding 50mg of graphite powder and 50mL of water into DBUH reversible ionic liquid serving as a stripping agent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1 mg/mL.
And thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 6MPa, the hydrothermal temperature is 100 ℃ and the time is 6 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at a rotating speed of 3000r/min for 5min, then taking the upper solution to filter, and removing impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product into PVP (polyvinyl pyrrolidone) aqueous solution with the concentration of 30wt%, adding sodium anthracene borate with the mass of 10% of that of the graphene product, fully stirring to obtain graphene dispersion liquid with the concentration of 1mg/mL, carrying out vacuum filtration to form a film, drying at 60 ℃ for 12 hours, and then carrying out N-type furnace N drying2Calcining for 3 hours at the temperature of 1000 ℃ to obtain the graphene heat-conducting film with high heat-conducting performance.
The results of the thermal conductivity test on the graphene thermal conductive films obtained in examples 1 to 3 are shown in table 1. As can be seen from table 1, the graphene thermal conductive film obtained in the present invention has excellent in-plane thermal conductivity and high thermal conductivity.
TABLE 1 Performance parameters of graphene thermal conductive films of inventive examples 1-3
Embodiment 4 is a method for preparing a boron-doped graphene thermal conductive film, including the steps of:
mixing 15mmol of diethylene glycol and 30mmol of DBU,introducing CO at a flow rate of 1mL/min to the mixed solution at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
And adding 500mg of graphite powder and 50mL of water into DBUH reversible ionic liquid serving as a stripping agent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 10 mg/mL.
And thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 1MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at a rotating speed of 2000r/min for 5min, then taking the upper solution to filter, and removing impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product in SDS (sodium dodecyl sulfate) aqueous solution with the concentration of 30wt%, adding 10% by mass of 3-methyl potassium phenylborate into the graphene product, fully stirring to obtain graphene dispersion liquid with the concentration of 10mg/mL, carrying out vacuum filtration to form a film, drying at 60 ℃ for 12 hours, and then carrying out N-ray filtration in a tubular furnace2Calcining for 5 hours at the temperature of 800 ℃ to obtain the graphene heat-conducting film with high heat-conducting performance.
Embodiment 5 a method for preparing a boron-doped graphene thermal conductive film, includes the following steps:
mixing 15mmol of ethanol and 15mmol of DBU, and introducing CO with the flow rate of 1mL/min into the mixed solution at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
And adding 50mg of graphite powder and 50mL of water into DBUH reversible ionic liquid serving as a stripping agent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1 mg/mL.
And thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 4MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at a rotating speed of 3000r/min for 5min, then taking the upper solution to filter, and removing impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product into the SDBS aqueous solution with the concentration of 30wt%, adding potassium naphthalene borate with the mass of 10% of that of the graphene product, fully stirring to obtain graphene dispersion liquid with the concentration of 0.5mg/mL, carrying out vacuum filtration to form a film, drying at 60 ℃ for 12 hours, and then carrying out N-type furnace N drying2Calcining for 7 hours at the temperature of 800 ℃ to obtain the graphene heat-conducting film with high heat-conducting performance.
Embodiment 6 is a method for preparing a boron-doped graphene thermal conductive film, including the steps of:
mixing 15mmol of hexanol and 15mmol of DBU, and introducing CO with the flow rate of 1mL/min into the mixed liquid at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
And adding 50mg of graphite powder and 50mL of water into DBUH reversible ionic liquid serving as a stripping agent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1 mg/mL.
And thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 6MPa, the hydrothermal temperature is 80 ℃ and the time is 6 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at a rotating speed of 2000r/min for 5min, then taking the upper solution to filter, and removing impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product into an anionic polyacrylamide aqueous solution with the concentration of 30wt%, adding potassium phenylboronate with the mass of 10% of that of the graphene product, fully stirring to obtain a graphene dispersion liquid with the concentration of 1mg/mL, carrying out vacuum filtration to form a film, drying at 60 ℃ for 12 hours, and then carrying out N-type furnace N drying2Calcining for 3 hours at the temperature of 900 ℃ to obtain the graphene heat-conducting film with high heat-conducting performance.
Embodiment 7 is a method for preparing a boron-doped graphene thermal conductive film, including the steps of:
mixing 15mmol of ethylene glycol and 30mmol of DBU, and introducing CO with the flow rate of 1mL/min into the mixed solution at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
And adding 50mg of graphite powder and 100mL of water into DBUH reversible ionic liquid serving as a stripping agent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 0.5 mg/mL.
And thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 5MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at the rotating speed of 5000r/min for 5min, then taking the upper solution to filter, and removing impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product into PVP (polyvinyl pyrrolidone) aqueous solution with the concentration of 30wt%, adding 4-hydroxybenzene potassium borate with the mass of 10% of that of the graphene product, fully stirring to obtain graphene dispersion liquid with the concentration of 0.5mg/mL, performing vacuum filtration to form a film, drying at 60 ℃ for 12 hours, and then performing N-shaped filtration in a tubular furnace2Calcining for 1h at the temperature of 1000 ℃ to obtain the graphene heat-conducting film with high heat-conducting performance.
Embodiment 8 is a method for preparing a boron-doped graphene thermal conductive film, including the steps of:
mixing 15mmol of benzyl alcohol and 15mmol of DBU, and introducing CO with the flow rate of 1mL/min into the mixed solution at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
And adding 150mg of graphite powder and 100mL of water into DBUH reversible ionic liquid serving as a stripping agent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1.5 mg/mL.
And thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 4MPa, the hydrothermal temperature is 150 ℃ and the time is 6 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at the rotating speed of 5000r/min for 5min, then taking the upper solution to filter, and removing impurities to obtain a pure graphene product.
Step of dispersing the graphene product into PVP (polyvinyl pyrrolidone) aqueous solution with concentration of 30wt%Adding sodium 4-methoxybenzoate with the mass of 10% of that of a graphene product, fully stirring to obtain a graphene dispersion liquid with the concentration of 1.5mg/mL, performing vacuum filtration to form a film, drying at 60 ℃ for 12 hours, and then performing N in a tube furnace2Calcining for 1h at 1500 ℃ to obtain the graphene heat-conducting film with high heat-conducting performance.
Embodiment 9 is a method for preparing a boron-doped graphene thermal conductive film, including the steps of:
mixing 15mmol of isopropanol and 15mmol of DBU, and introducing CO with the flow rate of 1mL/min into the mixed solution at 25 DEG C2And (3) gas, and forming a white gelatinous solid after 60min, namely the DBUH reversible ionic liquid.
And adding 50mg of graphite powder and 100mL of water into DBUH reversible ionic liquid serving as a stripping agent, uniformly stirring to obtain the graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 0.5 mg/mL.
And thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle, and stripping and dispersing under the conditions that the atmosphere is carbon dioxide, the pressure is 4MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours to obtain the graphene mixed dispersion system.
And fourthly, centrifuging the graphene mixed system at the rotating speed of 5000r/min for 5min, then taking the upper solution to filter, and removing impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product into PVP (polyvinyl pyrrolidone) aqueous solution with the concentration of 30wt%, adding 2-carboxyl potassium phenylborate salt with the mass of 10% of the graphene product, fully stirring to obtain graphene dispersion liquid with the concentration of 0.5mg/mL, performing vacuum filtration to form a film, drying at 60 ℃ for 12 hours, and then performing N-shaped filtration in a tubular furnace2Calcining for 1h at 1200 ℃ to obtain the graphene heat-conducting film with high heat-conducting performance.
Claims (10)
1. A preparation method of a boron-doped graphene heat conduction film comprises the following steps:
firstly, 1, 8-diazabicyclo [5.4.0 ] is adopted]Mixing 0.5-10% of undec-7-ene and alkyl alcohol: 1, introducing CO into the mixed solution at 25 DEG C2Gas, and a white gelatinous solid formed after 60min is the DBUH reversible ionic liquid;
secondly, adding graphite powder into the DBUH reversible ionic liquid serving as a stripping agent and water serving as a solvent, and uniformly stirring to obtain a graphite pre-stripping dispersion liquid;
thirdly, transferring the graphite pre-stripping dispersion liquid into a high-pressure hydrothermal reaction kettle for stripping dispersion to obtain a graphene mixed dispersion system;
fourthly, centrifuging and filtering the graphene mixed system to obtain a pure graphene product;
fifthly, dispersing the graphene product into a surfactant aqueous solution with the concentration of 3-30 wt%, adding boron salt with the mass of 0.5-10% of the graphene product, fully stirring to obtain a graphene dispersion liquid with the concentration of 0.5-10 mg/mL, and carrying out vacuum filtration, film forming, drying and calcining on the graphene dispersion liquid to obtain the graphene heat conduction film.
2. The method of claim 1, wherein the method comprises: the alkyl alcohol in the step is one of methanol, ethanol, hexanol, isopropanol, diethylene glycol, glycerol, 1, 4-butanediol, 1-propanol, tert-butyl alcohol, 1, 3-propanediol, cyclohexanol and glucose.
3. The method of claim 1, wherein the method comprises: CO in the step2The gas flow rate is 0.1-50 mL/min.
4. The method of claim 1, wherein the method comprises: the graphite powder in the step II is one of scale graphite powder, expanded graphite powder, oxidized graphite powder and natural graphite powder.
5. The method of claim 1, wherein the method comprises: the method comprises the step of pre-stripping graphite powder in the dispersion liquid by graphite, wherein the concentration of the graphite powder in the dispersion liquid is 0.5-10 mg/mL.
6. The method of claim 1, wherein the method comprises: the stripping and dispersing conditions in the step three mean that the atmosphere is carbon dioxide, the pressure is 1-10 MPa, the hydrothermal temperature is 80-160 ℃, and the time is 3-12 h.
7. The method of claim 1, wherein the method comprises: the centrifugal condition in the step four is that the rotating speed is 100-3000 r/min, and the time is 1-10 min.
8. The method of claim 1, wherein the method comprises: the surfactant in the surfactant aqueous solution obtained in the step fifthly is one or more of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium dodecyl sulfate, sodium poly (propylene benzene sulfonate), sodium naphthalene sulfonate, anionic polyacrylamide, carboxylate and sulfate.
9. The method of claim 1, wherein the method comprises: the boron salt in the step fifthly is aryl borate, and the structural general formula of the boron salt is as follows:
(ii) a In the formula R1Is aryl, R2、R3、R4Are all one of H, alkyl, aryl, halogen or acyl; y is+Is metal Na or K.
10. The method of claim 9, wherein the method comprises: the aryl borate is one or more of phenylborate, naphthalene borate, pyrene borate, 2-boric acid anthracene salt, 3-methylbenzylborate, 4-methylbenzylborate, 2- (bromomethyl) phenylborate, 4-hydroxybenzylborate, 2-methoxy-1-naphthyl borate, 4-butoxyphenylborate, 4-carbamylborate, 2-carboxyphenylborate, 4-fluorobenzylborate, 4-biphenylborate and 4-tert-butylbenzoborate.
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