CN113896188B - Preparation method of boron-doped graphene heat conducting film - Google Patents

Preparation method of boron-doped graphene heat conducting film Download PDF

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CN113896188B
CN113896188B CN202111233063.8A CN202111233063A CN113896188B CN 113896188 B CN113896188 B CN 113896188B CN 202111233063 A CN202111233063 A CN 202111233063A CN 113896188 B CN113896188 B CN 113896188B
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graphene
boron
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borate
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CN113896188A (en
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李跃辉
李莹
孙玉霞
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract

The invention relates to a boron dopingThe preparation method of the hybrid graphene heat conducting film comprises the following steps: mixing DBU with alkyl alcohol, and introducing CO into the mixed solution 2 The white gel-like solid formed after the gas is DBUH reversible ionic liquid; secondly, adding graphite powder by taking DBUH reversible ionic liquid as a stripping agent and water as a solvent, and uniformly stirring to obtain graphite pre-stripping dispersion liquid; peeling and dispersing the graphite pre-peeling dispersion liquid under a hydrothermal condition to obtain a graphene mixed dispersion system; centrifuging and filtering the graphene mixed system to obtain a pure graphene product; and fifthly, dispersing the graphene product in a surfactant water solution, adding boron salt, fully stirring to obtain graphene dispersion liquid, and performing vacuum filtration to form a film, drying and calcining on the graphene dispersion liquid to obtain the graphene heat conducting film. The method is simple, low in cost and capable of realizing industrial production, and the graphene sheets can be effectively peeled off by adopting the method, so that the agglomeration of graphene is prevented, and the damage to the intrinsic structure of the graphene is small.

Description

Preparation method of boron-doped graphene heat conducting film
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 a material consisting of carbon atoms in sp 2 The planar two-dimensional layered material with the hexagonal lattice formed by the hybridized orbits has excellent physical and chemical properties, the heat conductivity coefficient is as high as 5300W/m.K, which is higher than that of the carbon nano tube and the diamond, but the defects and the disorder of the edges of the graphene can reduce the heat conductivity coefficient of the graphene, and the characteristics of the 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 energy band structure and other properties of the graphene, and the application field of the graphene is expanded. Therefore, the controllable preparation method and the performance regulation means of graphene doping become research hot spots in the field of material science.
Wang et al successfully prepared monolayer boron-doped graphene by using phenylboronic acid as a precursor by chemical vapor deposition (Small 2013, 9, 1316-1320). Jung et al used an improved Woodface reaction to convert CCl 4 And BBr 3 Boron doped graphene is generated under the action of elemental potassium and is used for a metal-free cathode material of a solar cell (chem. Mater. 2014, 26, 3586-3591). Li et al employ hydrothermal reaction toThe chemical reduction method realizes boron element doping of graphene and is applied to a photocatalyst (rsc.adv., 2014, 4, 37992), but the methods have high requirements on equipment and complex operation. In view of this, development of a simple and efficient preparation method is one of the important points of research at present.
Disclosure of Invention
The invention aims to provide a preparation method of a boron-doped graphene heat conducting film, which is simple and low in cost and can realize industrial production.
In order to solve the problems, the preparation method of the boron-doped graphene heat conducting film comprises the following steps:
1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU) and alkyl alcohol according to the weight ratio of 0.5-10: 1, and introducing CO into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely DBUH reversible ionic liquid;
secondly, adding graphite powder by taking the DBUH reversible ionic liquid as a stripping agent and water as a solvent, and uniformly stirring to obtain a graphite pre-stripping dispersion liquid;
thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle to be stripped and dispersed, so that a graphene mixed dispersion system is obtained;
centrifuging and filtering the graphene mixed system to obtain a pure graphene product;
and fifthly, dispersing the graphene product in 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 graphene dispersion with the concentration of 0.5-10 mg/mL, and performing vacuum filtration to form a film, drying and calcining on the graphene dispersion to obtain the graphene heat conducting film.
The alkyl alcohol in the step (A) refers to one of methanol, ethanol, hexanol, isopropanol, diethylene glycol, glycerol, 1, 4-butanediol, 1-propanol, tertiary butanol, 1, 3-propanediol, cyclohexanol and glucose.
CO in the steps 2 The gas flow rate is 0.1-50 mL/min.
The graphite powder in the steps refers to one of flake graphite powder, expanded graphite powder, graphite oxide powder and natural graphite powder.
And in the step (II), the concentration of graphite powder in the graphite pre-stripping dispersion liquid is 0.5-10 mg/mL.
The stripping and dispersing conditions in the step III are 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 is that the rotating speed is 100-3000 r/min and the time is 1-10 min.
The surfactant in the surfactant aqueous solution in the step II is one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), polyvinylpyrrolidone (PVP), sodium Dodecyl Sulfate (SDS), sodium polyacrylate benzene sulfonate, sodium naphthalene sulfonate, anionic polyacrylamide, carboxylate and sulfate.
The boron salt in the step II is aryl borate, and the structural general formula is as follows:
Figure 959103DEST_PATH_IMAGE001
the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is aryl, R 2 、R 3 、R 4 Are all one of H, alkyl, aryl, halogen or acyl; y is Y + Is metal Na or K.
The aryl borate is one or more of phenylborate, naphthalene borate, pyrene borate, 2-borate anthracene salt, 3-methylbenzene borate, 4-methylbenzene borate, 2- (bromomethyl) phenylborate, 4-hydroxybenzene borate, 2-methoxy-1-naphthyl borate, 4-butoxyphenylborate, 4-carbamoylphenylborate, 2-carboxyphenylborate, 4-fluorobenzeneborate, 4-biphenyl borate and 4-tert-butylphenylborate.
Compared with the prior art, the invention has the following advantages:
1. the invention takes graphite powder without pretreatment as raw material, and uses DBU+alcohol/CO with heterocyclic structure 2 The reversible ionic liquid is taken as a stripping agent to strip graphite and stabilize the graphene layer; the interaction of the aromatic borate and the graphene is then utilized to modify the graphene by the synergistic effect of the high hydrophilicity of the surfactant. Due to piAnd (3) adsorbing boron on the surface of the graphene in the presence of pi bond, and obtaining the boron doped graphene film with high heat conduction performance after high-temperature reduction.
2. The invention uses the reusable DBUH reversible ionic liquid as the stripping agent to replace the traditional DMF and NMP organic solvents, effectively overcomes the problem of environmental pollution, has the advantages of environment friendliness, low toxicity, safety, environmental protection, recycling, and the like, and has the potential of mass production of graphene films with high heat conductivity.
3. The method is simple, low in cost and capable of realizing industrial production, and the graphene sheets can be effectively peeled off by adopting the method, so that the agglomeration of graphene is prevented, and the damage to the intrinsic structure of the graphene is small.
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The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 is a flow chart of the preparation of the present invention.
Fig. 2 is a raman spectrum of graphene of example 1 of the present invention.
Fig. 3 is an appearance (a) and an SEM image (B) of the graphene film according to example 1 of the present invention.
Detailed Description
As shown in fig. 1, a preparation method of a boron-doped graphene heat conducting film comprises the following steps:
1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU) and alkyl alcohol according to the weight ratio of 0.5-10: 1, and introducing CO with the flow rate of 0.1-50 mL/min into the mixed solution of DBU and alcohol at 25 DEG C 2 The gas is formed into a white gel-like 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 (3) taking the DBUH reversible ionic liquid as a stripping agent and water as a solvent, adding graphite powder, uniformly stirring to obtain a 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+CO 2 Is a combination of the modes of (a).
The graphite powder is one of flake graphite powder, expanded graphite powder, graphite oxide powder and natural graphite powder.
The solvent may also be other polar solvents.
And thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, and stripping and dispersing are carried out 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, so that a graphene mixed dispersion system is obtained.
And fourthly, centrifuging the graphene mixed system for 1-10 min at a rotating speed of 100-3000 r/min, and then filtering the upper solution to remove impurities to obtain a pure graphene product.
And fifthly, dispersing the graphene product in 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 with the concentration of 0.5-10 mg/mL, and performing vacuum filtration to form a film, drying and calcining at 800-1200 ℃ on the graphene dispersion 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 polyacrylate benzene sulfonate, sodium naphthalene sulfonate, anionic polyacrylamide, carboxylate and sulfate.
The boron salt refers to aryl borate, and has a structural general formula:
Figure 711158DEST_PATH_IMAGE001
the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is aryl, R 2 、R 3 、R 4 Are all one of H, alkyl, aryl, halogen or acyl; y is Y + Is metal Na or K.
The arylborate is one or more of phenylborate, naphthalene borate, pyrene borate, 2-borate anthracene salt, 3-methylbenzene borate, 4-methylbenzene borate, 2- (bromomethyl) phenylborate, 4-hydroxybenzene borate, 2-methoxy-1-naphthyl borate, 4-butoxyphenylborate, 4-carbamoylphenylborate, 2-carboxyphenylborate, 4-fluorobenzene borate, 4-biphenylborate and 4-tert-butylphenylborate.
Embodiment 1 a method for preparing a boron-doped graphene heat conducting film, comprising the following steps:
mixing 15mmol of ethanol and 15mmol of DBU, and introducing CO with a flow rate of 1mL/min into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely the DBUH reversible ionic liquid.
And (3) taking the DBUH reversible ionic liquid as a stripping agent, adding 50mg of graphite powder and 50mL of water, uniformly stirring to obtain a graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1mg/mL.
Thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, stripping and dispersing are carried out under the conditions that the atmosphere is carbon dioxide, the pressure is 4MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours, and a graphene mixed dispersion system is obtained.
And (3) centrifuging the graphene mixed system at a rotating speed of 500r/min for 5min, and then filtering the upper layer solution to remove impurities to obtain a pure graphene product.
Fifthly, dispersing the graphene product in PVP aqueous solution with the concentration of 30wt%, adding sodium phenylborate with the mass of 10% of the graphene product, fully stirring to obtain graphene dispersion with the concentration of 1mg/mL, vacuum filtering to form a film, and drying at 60 ℃ for 12h, and then adding N in a tube furnace 2 Calcining at 800 ℃ for 3 hours in the atmosphere to obtain the graphene heat conducting film with high heat conducting performance.
And carrying out Raman spectrum test on the obtained graphene product, as shown in fig. 2, finding characteristic peaks of graphene from the graph, and proving that the prepared product is graphene.
SEM test is carried out on the obtained graphene product, as shown in figure 3, the surface of the macroscopic graphene film is smooth and flat without defects, the surface of the microscopic graphene has a fold structure, and the stacked graphene has a larger sheet diameter.
Embodiment 2 a method for preparing a boron doped graphene heat conducting film, comprising the following steps:
mixing 15mmol of ethylene glycol and 30mmol of DBU, and introducing CO with a flow rate of 1mL/min into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely the DBUH reversible ionic liquid.
And (3) taking the DBUH reversible ionic liquid as a stripping agent, adding 25mg of graphite powder and 50mL of water, uniformly stirring to obtain a graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 0.5mg/mL.
Thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, stripping and dispersing are carried out under the conditions that the atmosphere is carbon dioxide, the pressure is 10MPa, the hydrothermal temperature is 140 ℃ and the time is 6 hours, and a graphene mixed dispersion system is obtained.
And (3) centrifuging the graphene mixed system for 5min at a rotating speed of 1000r/min, and then filtering an upper layer solution to remove impurities, thereby obtaining a pure graphene product.
Fifthly, dispersing the graphene product in an SDBS aqueous solution with the concentration of 30wt%, adding sodium naphthalene borate with the mass of 10% of the graphene product, fully stirring to obtain a graphene dispersion with the concentration of 0.5mg/mL, vacuum filtering to form a film, and drying at 60 ℃ for 12h to obtain N in a tubular furnace 2 Calcining at 900 ℃ for 3 hours in the atmosphere to obtain the graphene heat conducting film with high heat conducting performance.
Embodiment 3 a method for preparing a boron-doped graphene heat conducting film, comprising the following steps:
mixing 15mmol of glycerol with 45mmol of DBU, and introducing CO with a flow rate of 1mL/min into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely the DBUH reversible ionic liquid.
And (3) taking the DBUH reversible ionic liquid as a stripping agent, adding 50mg of graphite powder and 50mL of water, uniformly stirring to obtain a graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1mg/mL.
Thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, stripping and dispersing are carried out under the conditions that the atmosphere is carbon dioxide, the pressure is 6MPa, the hydrothermal temperature is 100 ℃ and the time is 6 hours, and a graphene mixed dispersion system is obtained.
And (3) centrifuging the graphene mixed system for 5min at a rotating speed of 3000r/min, and then filtering an upper layer solution to remove impurities, thereby obtaining a pure graphene product.
Fifthly, dispersing the graphene product in PVP aqueous solution with the concentration of 30wt%, adding sodium anthracene borate with the mass of 10% of the graphene product, fully stirring to obtain graphene dispersion with the concentration of 1mg/mL, vacuum filtering to form a film, and drying at 60 ℃ for 12h, and then adding N in a tube furnace 2 Calcining at 1000 ℃ for 3 hours in the atmosphere to obtain the graphene heat conducting film with high heat conducting performance.
The graphene heat conductive films obtained in examples 1 to 3 were subjected to a heat conductivity coefficient test, and the results are shown in table 1. As can be seen from table 1, the graphene heat conducting film obtained by the invention has excellent in-plane thermal conductivity and high heat conductivity.
TABLE 1 graphene thermal conductive film performance parameters of examples 1-3 of the present invention
Figure 533621DEST_PATH_IMAGE002
Embodiment 4 a method for preparing a boron-doped graphene heat conducting film, comprising the following steps:
mixing 15mmol of diethylene glycol and 30mmol of DBU, and introducing CO with a flow rate of 1mL/min into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely the DBUH reversible ionic liquid.
And (3) taking the DBUH reversible ionic liquid as a stripping agent, adding 500mg of graphite powder and 50mL of water, uniformly stirring to obtain a graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 10mg/mL.
Thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, stripping and dispersing are carried out under the conditions that the atmosphere is carbon dioxide, the pressure is 1MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours, and a graphene mixed dispersion system is obtained.
And (3) centrifuging the graphene mixed system at a rotating speed of 2000r/min for 5min, and then filtering an upper layer solution to remove impurities, thereby obtaining a pure graphene product.
Dispersing the graphene product in an SDS water solution with the concentration of 30wt%, adding 10% of 3-methyl phenylpotassium borate by mass of the graphene product, fully stirring to obtain a graphene dispersion with the concentration of 10mg/mL,vacuum filtering to form film, drying at 60deg.C for 12 hr, and adding N into tubular furnace 2 Calcining at 800 ℃ for 5 hours in the atmosphere to obtain the graphene heat conducting film with high heat conducting performance.
Embodiment 5 a method for preparing a boron doped graphene heat conducting film, comprising the following steps:
mixing 15mmol of ethanol and 15mmol of DBU, and introducing CO with a flow rate of 1mL/min into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely the DBUH reversible ionic liquid.
And (3) taking the DBUH reversible ionic liquid as a stripping agent, adding 50mg of graphite powder and 50mL of water, uniformly stirring to obtain a graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1mg/mL.
Thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, stripping and dispersing are carried out under the conditions that the atmosphere is carbon dioxide, the pressure is 4MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours, and a graphene mixed dispersion system is obtained.
And (3) centrifuging the graphene mixed system for 5min at a rotating speed of 3000r/min, and then filtering an upper layer solution to remove impurities, thereby obtaining a pure graphene product.
Fifthly, dispersing the graphene product in an SDBS aqueous solution with the concentration of 30wt%, adding potassium naphthalene borate with the mass of 10% of the graphene product, fully stirring to obtain a graphene dispersion with the concentration of 0.5mg/mL, vacuum filtering to form a film, and drying at 60 ℃ for 12h to obtain N in a tubular furnace 2 Calcining at 800 ℃ for 7 hours in the atmosphere to obtain the graphene heat conducting film with high heat conducting performance.
Embodiment 6 a method for preparing a boron-doped graphene heat conducting film, comprising the following steps:
mixing 15mmol of hexanol and 15mmol of DBU, and introducing CO with a flow rate of 1mL/min into the mixture at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely the DBUH reversible ionic liquid.
And (3) taking the DBUH reversible ionic liquid as a stripping agent, adding 50mg of graphite powder and 50mL of water, uniformly stirring to obtain a graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1mg/mL.
Thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, stripping and dispersing are carried out under the conditions that the atmosphere is carbon dioxide, the pressure is 6MPa, the hydrothermal temperature is 80 ℃ and the time is 6 hours, and a graphene mixed dispersion system is obtained.
And (3) centrifuging the graphene mixed system at a rotating speed of 2000r/min for 5min, and then filtering an upper layer solution to remove impurities, thereby obtaining a pure graphene product.
Dispersing the graphene product in an anionic polyacrylamide aqueous solution with the concentration of 30wt%, adding potassium phenylborate with the mass of 10% of the graphene product, fully stirring to obtain a graphene dispersion with the concentration of 1mg/mL, vacuum filtering to form a film, and drying at 60 ℃ for 12h to obtain N in a tubular furnace 2 Calcining at 900 ℃ for 3 hours in the atmosphere to obtain the graphene heat conducting film with high heat conducting performance.
Embodiment 7 a method for preparing a boron-doped graphene heat conducting film, comprising the following steps:
mixing 15mmol of ethylene glycol and 30mmol of DBU, and introducing CO with a flow rate of 1mL/min into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely the DBUH reversible ionic liquid.
And (3) taking the DBUH reversible ionic liquid as a stripping agent, adding 50mg of graphite powder and 100mL of water, uniformly stirring to obtain a graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 0.5mg/mL.
Thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, stripping and dispersing are carried out under the conditions that the atmosphere is carbon dioxide, the pressure is 5MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours, and a graphene mixed dispersion system is obtained.
And (3) centrifuging the graphene mixed system for 5min at a rotation speed of 5000r/min, and then filtering the upper layer solution to remove impurities to obtain a pure graphene product.
Dispersing the graphene product in PVP aqueous solution with the concentration of 30wt%, adding 4-hydroxyphenylpotassium borate with the mass of 10% of the graphene product, fully stirring to obtain graphene dispersion with the concentration of 0.5mg/mL, vacuum filtering to form a film, and drying at 60 ℃ for 12h, wherein N is in a tube furnace 2 Calcining at 1000 ℃ for 1h in atmosphere to obtain graphene heat conduction with high heat conduction performanceAnd (3) a film.
Embodiment 8 a method for preparing a boron-doped graphene heat conducting film, comprising the following steps:
mixing 15mmol of benzyl alcohol and 15mmol of DBU, and introducing CO with a flow rate of 1mL/min into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely the DBUH reversible ionic liquid.
And (3) taking the DBUH reversible ionic liquid as a stripping agent, adding 150mg of graphite powder and 100mL of water, uniformly stirring to obtain a graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 1.5mg/mL.
Thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, stripping and dispersing are carried out under the conditions that the atmosphere is carbon dioxide, the pressure is 4MPa, the hydrothermal temperature is 150 ℃ and the time is 6 hours, and a graphene mixed dispersion system is obtained.
And (3) centrifuging the graphene mixed system for 5min at a rotation speed of 5000r/min, and then filtering the upper layer solution to remove impurities to obtain a pure graphene product.
Dispersing the graphene product in PVP aqueous solution with the concentration of 30wt%, adding 4-methoxyphenylboric acid sodium salt with the mass of 10% of the graphene product, fully stirring to obtain graphene dispersion with the concentration of 1.5mg/mL, vacuum filtering to form a film, and drying at 60 ℃ for 12h, wherein N is in a tube furnace 2 Calcining at 1500 ℃ for 1h in the atmosphere to obtain the graphene heat conducting film with high heat conducting performance.
Embodiment 9 a method for preparing a boron-doped graphene heat conducting film, comprising the following steps:
mixing 15mmol of isopropanol and 15mmol of DBU, and introducing CO with a flow rate of 1mL/min into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely the DBUH reversible ionic liquid.
And (3) taking the DBUH reversible ionic liquid as a stripping agent, adding 50mg of graphite powder and 100mL of water, uniformly stirring to obtain a graphite pre-stripping dispersion liquid, and enabling the concentration of the graphite powder in the graphite pre-stripping dispersion liquid to be 0.5mg/mL.
Thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle, stripping and dispersing are carried out under the conditions that the atmosphere is carbon dioxide, the pressure is 4MPa, the hydrothermal temperature is 160 ℃ and the time is 6 hours, and a graphene mixed dispersion system is obtained.
And (3) centrifuging the graphene mixed system for 5min at a rotation speed of 5000r/min, and then filtering the upper layer solution to remove impurities to obtain a pure graphene product.
Dispersing the graphene product in PVP aqueous solution with the concentration of 30wt%, adding 2-carboxyphenylpotassium borate with the mass of 10% of the graphene product, fully stirring to obtain graphene dispersion with the concentration of 0.5mg/mL, vacuum filtering to form a film, and drying at 60 ℃ for 12h, and then adding N in a tubular furnace 2 Calcining at 1200 ℃ for 1h in atmosphere to obtain the graphene heat conducting film with high heat conducting performance.

Claims (10)

1. A preparation method of a boron-doped graphene heat conducting film comprises the following steps:
1, 8-diazabicyclo [5.4.0]Undec-7-ene and alkyl alcohol according to the ratio of 0.5-10: 1, and introducing CO into the mixed solution at 25 DEG C 2 The gas is formed into a white gel-like solid after 60min, namely DBUH reversible ionic liquid;
secondly, adding graphite powder by taking the DBUH reversible ionic liquid as a stripping agent and water as a solvent, and uniformly stirring to obtain a graphite pre-stripping dispersion liquid;
thirdly, the graphite pre-stripping dispersion liquid is moved into a high-pressure hydrothermal reaction kettle to be stripped and dispersed, so that a graphene mixed dispersion system is obtained;
centrifuging and filtering the graphene mixed system to obtain a pure graphene product;
and fifthly, dispersing the graphene product in 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 with the concentration of 0.5-10 mg/mL, and performing vacuum filtration to form a film, drying and calcining on the graphene dispersion to obtain the graphene heat conducting film.
2. The method for preparing the boron-doped graphene heat conducting film according to claim 1, wherein the method comprises the following steps: the alkyl alcohol in the step (A) refers to one of methanol, ethanol, hexanol, isopropanol, diethylene glycol, glycerol, 1, 4-butanediol, 1-propanol, tertiary butanol, 1, 3-propanediol and cyclohexanol.
3. The method for preparing the boron-doped graphene heat conducting film according to claim 1, wherein the method comprises the following steps: CO in the steps 2 The gas flow rate is 0.1-50 mL/min.
4. The method for preparing the boron-doped graphene heat conducting film according to claim 1, wherein the method comprises the following steps: the graphite powder in the step (II) refers to one of expanded graphite powder, graphite oxide powder and natural graphite powder.
5. The method for preparing the boron-doped graphene heat conducting film according to claim 1, wherein the method comprises the following steps: and in the step (II), the concentration of graphite powder in the graphite pre-stripping dispersion liquid is 0.5-10 mg/mL.
6. The method for preparing the boron-doped graphene heat conducting film according to claim 1, wherein the method comprises the following steps: the stripping and dispersing conditions in the step III are 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 for preparing the boron-doped graphene heat conducting film according to claim 1, wherein the method comprises the following steps: the centrifugal condition in the step is that the rotating speed is 100-3000 r/min and the time is 1-10 min.
8. The method for preparing the boron-doped graphene heat conducting film according to claim 1, wherein the method comprises the following steps: the surfactant in the surfactant aqueous solution in the step II is one or more of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium dodecyl sulfate, sodium polypropylene benzene sulfonate, sodium naphthalene sulfonate, anionic polyacrylamide, carboxylate and sulfate.
9. A boron as defined in claim 1The preparation method of the doped graphene heat conduction film is characterized by comprising the following steps of: the boron salt in the step II is aryl borate, and the structural general formula is as follows:
Figure DEST_PATH_IMAGE001
the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is aryl, R 2 、R 3 、R 4 Are all one of H, alkyl, aryl, halogen or acyl; y is Y + Is metal Na or K.
10. The method for preparing the boron-doped graphene heat conducting film according to claim 9, wherein the method comprises the following steps: the aryl borate is one or more of phenylborate, naphthalene borate, pyrene borate, 2-borate anthracene salt, 3-methylbenzene borate, 4-methylbenzene borate, 2- (bromomethyl) phenylborate, 4-hydroxybenzene borate, 2-methoxy-1-naphthyl borate, 4-butoxyphenylborate, 4-carbamoylphenylborate, 2-carboxyphenylborate, 4-fluorobenzeneborate, 4-biphenyl borate and 4-tert-butylphenylborate.
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