阅读说明：本技术 一种硼化石墨烯高导热浆料及其制备方法 (Boronized graphene high-thermal-conductivity slurry and preparation method thereof ) 是由 陈大波 冯于界 林勇 徐佳伟 于 2020-04-24 设计创作，主要内容包括：本发明提供了一种硼化石墨烯高导热浆料及其制备方法,该硼化石墨烯高导热浆料由以下步骤制得：首先先制得硼化石墨烯,并利用硅烷偶联剂对硼化石墨烯进行改性,以获得功能性硼化石墨烯分散液；在搅拌状态下,向功能性硼化石墨烯分散液中加入纳米二氧化硅粒子,混合30-120分钟按质量份计,将3-5份含有1.5％-3.5％的硼化石墨烯的功能性硼化石墨烯分散液,与20-30份有机溶剂,4-8份的助剂和补足至80份的纳米二氧化硅粒子采用三维混合技术,充分混合均匀,得到硼化石墨烯高导热浆料。从而提高了浆料与基板的结合力,表现出良好的附着力,提高导热材料的品质性。(The invention provides boronized graphene high-thermal-conductivity slurry and a preparation method thereof, wherein the boronized graphene high-thermal-conductivity slurry is prepared by the following steps: firstly, preparing boronized graphene, and modifying the boronized graphene by using a silane coupling agent to obtain a functional boronized graphene dispersion liquid; under the stirring state, adding nano silicon dioxide particles into the functional boronized graphene dispersion liquid, mixing for 30-120 minutes, and fully and uniformly mixing 3-5 parts of the functional boronized graphene dispersion liquid containing 1.5% -3.5% of boronized graphene, 20-30 parts of organic solvent, 4-8 parts of auxiliary agent and nano silicon dioxide particles which are complemented to 80 parts by mass by adopting a three-dimensional mixing technology to obtain the boronized graphene high-thermal-conductivity slurry. Thereby improving the binding force between the slurry and the substrate, showing good adhesive force and improving the quality of the heat conduction material.)

1. The high-thermal-conductivity boronized graphene slurry is characterized by being prepared by the following steps:

a) adding redox graphene and boric acid into absolute ethyl alcohol, carrying out ultrasonic stirring and uniform dispersion to obtain a mixed material, drying the mixed material at 40 ℃, and pyrolyzing the mixed material at 900 ℃ for 4 hours in an argon environment to obtain boronized graphene;

b) modifying boronized graphene by using a silane coupling agent, reacting the silane coupling agent with the boronized graphene to obtain functional boronized graphene, and dispersing the functional expanded graphene in an N-methylpyrrolidone solution through ultrasonic treatment to form a functional boronized graphene dispersion solution;

c) adding nano silicon dioxide particles into the functional boronized graphene dispersion liquid under the stirring state, and mixing for 30-120 minutes;

d) according to the mass parts, 3-5 parts of functional boronized graphene dispersion liquid containing 1.5% -3.5% of boronized graphene, 20-30 parts of organic solvent, 4-8 parts of auxiliary agent and nano silicon dioxide particles which are complemented to 80 parts are fully and uniformly mixed by adopting a three-dimensional mixing technology through shearing force generated by revolution and autorotation, and the boronized graphene high-thermal-conductivity slurry is obtained.

2. The high thermal conductivity slurry of boronized graphene according to claim 1, wherein the preparation method of boronized graphene comprises the following steps:

a1) and (2) mixing the redox graphene and boric acid according to the mass ratio of 5: 1, adding the mixture into absolute ethyl alcohol, and carrying out ultrasonic stirring for 2-4 hours to obtain a mixed material;

a2) drying the mixed material at 40 ℃, and then putting the mixed material into an argon pyrolysis box;

a3) and pyrolyzing the mixed material for 4 hours at the temperature of 900 ℃ in an argon atmosphere, and naturally cooling to obtain the boronized graphene.

3. The boronized graphene high thermal conductivity paste according to claim 1, characterized in that,

the silane coupling agent is one of A171, A172 and A151.

4. The boronized graphene high thermal conductivity slurry according to claim 1, wherein the preparation method of the nano-silica particles comprises the following steps:

by volume 4: 4: 7, continuously mixing and stirring isopropanol, ammonia water and distilled water for 1 hour;

in the stirring process, adding an ethyl orthosilicate solution uniformly, and stirring to react for 6 hours;

centrifuging to obtain white silicon dioxide, washing with anhydrous ethanol and distilled water for 3 times, and drying at 50 deg.C to obtain nanometer silicon dioxide particles.

5. The boronized graphene high thermal conductivity paste according to claim 1, characterized in that,

the organic solvent is one or more of ethanol, glycol and carbitol.

6. The preparation method of the boronized graphene high-thermal-conductivity slurry is characterized by comprising the following steps of:

a) adding redox graphene and boric acid into absolute ethyl alcohol, carrying out ultrasonic stirring and uniform dispersion to obtain a mixed material, drying the mixed material at 40 ℃, and pyrolyzing the mixed material at 900 ℃ for 4 hours in an argon environment to obtain boronized graphene;

b) modifying boronized graphene by using a silane coupling agent, reacting the silane coupling agent with the boronized graphene to obtain functional boronized graphene, and dispersing the functional expanded graphene in an N-methylpyrrolidone solution through ultrasonic treatment to form a functional boronized graphene dispersion solution;

c) adding nano silicon dioxide particles into the functional boronized graphene dispersion liquid under the stirring state, and mixing for 30-120 minutes;

d) according to the mass parts, 3-5 parts of functional boronized graphene dispersion liquid containing 1.5% -3.5% of boronized graphene, 20-30 parts of organic solvent, 4-8 parts of auxiliary agent and nano silicon dioxide particles which are complemented to 80 parts are fully and uniformly mixed by adopting a three-dimensional mixing technology through shearing force generated by revolution and autorotation, and the boronized graphene high-thermal-conductivity slurry is obtained.

7. The method for preparing the boronized graphene high thermal conductivity paste according to claim 6, wherein in the step a), the method further comprises the steps of:

a1) and (2) mixing the redox graphene and boric acid according to the mass ratio of 5: 1, adding the mixture into absolute ethyl alcohol, and carrying out ultrasonic stirring for 2-4 hours to obtain a mixed material;

a2) drying the mixed material in the step a1) at 40 ℃, and then putting the mixed material into an argon pyrolysis box;

a3) and pyrolyzing the mixed material for 4 hours at the temperature of 900 ℃ in an argon atmosphere, and naturally cooling to obtain the boronized graphene.

8. The method for preparing boronized graphene high thermal conductivity paste according to claim 6, wherein,

the silane coupling agent is one of A171, A172 and A151.

9. The method for preparing boronized graphene high thermal conductivity slurry according to claim 6, wherein in step c), the method for preparing the nano silica particles comprises:

by volume 4: 4: 7, continuously mixing and stirring isopropanol, ammonia water and distilled water for 1 hour;

in the stirring process, adding an ethyl orthosilicate solution uniformly, and stirring to react for 6 hours;

centrifuging to obtain white silicon dioxide, washing with anhydrous ethanol and distilled water for 3 times, and drying at 50 deg.C to obtain nanometer silicon dioxide particles.

10. The preparation method of the boronized graphene high thermal conductivity paste according to claim 6, characterized in that,

the organic solvent in the step d) is one or more of ethanol, glycol and carbitol.

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of new material preparation, in particular to boronized graphene high-thermal-conductivity slurry and a preparation method thereof.

[ background of the invention ]

The graphene is a two-dimensional crystal material formed by tightly stacking carbon atoms, and has good electric conduction and heat conduction properties. With the continuous development of the performance of graphene materials, the excellent mechanical properties, heat conductivity and electrical conductivity of the graphene materials play a role in many aspects, and particularly, in recent years, graphene heating materials, graphene anticorrosive coatings and graphene battery materials are greatly developed.

However, due to the large van der waals force between sheets of graphene, an agglomeration phenomenon easily occurs, so that graphene is difficult to dissolve in water and other common organic solvents. In addition, graphene has poor solubility in many polymers, and the dispersibility of graphene in a matrix needs to be improved, so that the graphene needs to be modified to adjust the performance and structure of graphene in order to improve the application range of graphene in various situations.

[ summary of the invention ]

The invention aims to overcome the defects of the prior art and provides the boronized graphene high-thermal-conductivity slurry and the preparation method thereof so as to further improve the performance of the thermal conductive material.

In order to solve the problems, the invention provides boronized graphene high thermal conductivity slurry which is characterized by being prepared by the following steps:

adding redox graphene and boric acid into absolute ethyl alcohol, carrying out ultrasonic stirring and uniform dispersion to obtain a mixed material, drying the mixed material at 40 ℃, and pyrolyzing the mixed material at 900 ℃ for 4 hours in an argon environment to obtain boronized graphene;

modifying boronized graphene by using a silane coupling agent, reacting the silane coupling agent with the boronized graphene to obtain functional boronized graphene, and dispersing the functional expanded graphene in an N-methylpyrrolidone solution through ultrasonic treatment to form a functional boronized graphene dispersion solution;

adding nano silicon dioxide particles into the functional boronized graphene dispersion liquid under the stirring state, and mixing for 30-120 minutes;

according to the mass parts, 3-5 parts of functional boronized graphene dispersion liquid containing 1.5% -3.5% of boronized graphene, 20-30 parts of organic solvent, 4-8 parts of auxiliary agent and nano silicon dioxide particles which are complemented to 80 parts are fully and uniformly mixed by adopting a three-dimensional mixing technology through shearing force generated by revolution and autorotation, and the boronized graphene high-thermal-conductivity slurry is obtained.

In an embodiment of the present invention, a preparation method of the boronized graphene includes:

and (2) mixing the redox graphene and boric acid according to the mass ratio of 5: 1, adding the mixture into absolute ethyl alcohol, and carrying out ultrasonic stirring for 2-4 hours to obtain a mixed material;

drying the mixed material at 40 ℃, and then putting the mixed material into an argon pyrolysis box;

and pyrolyzing the mixed material for 4 hours at the temperature of 900 ℃ in an argon atmosphere, and naturally cooling to obtain the boronized graphene.

In an embodiment of the present invention, the silane coupling agent is one of a171, a172, and a 151.

In an embodiment of the present invention, a method for preparing the nano silica particles includes:

by volume 4: 4: 7, continuously mixing and stirring isopropanol, ammonia water and distilled water for 1 hour;

in the stirring process, adding an ethyl orthosilicate solution uniformly, and stirring to react for 6 hours;

centrifuging to obtain white silicon dioxide, washing with anhydrous ethanol and distilled water for 3 times, and drying at 50 deg.C to obtain nanometer silicon dioxide particles.

In an embodiment of the present invention, the organic solvent is one or more of ethanol, ethylene glycol, and carbitol.

In one embodiment of the present invention, the method comprises the following steps:

a) adding redox graphene and boric acid into absolute ethyl alcohol, carrying out ultrasonic stirring and uniform dispersion to obtain a mixed material, drying the mixed material at 40 ℃, and pyrolyzing the mixed material at 900 ℃ for 4 hours in an argon environment to obtain boronized graphene;

b) modifying boronized graphene by using a silane coupling agent, reacting the silane coupling agent with the boronized graphene to obtain functional boronized graphene, and dispersing the functional expanded graphene in an N-methylpyrrolidone solution through ultrasonic treatment to form a functional boronized graphene dispersion solution;

c) adding nano silicon dioxide particles into the functional boronized graphene dispersion liquid under the stirring state, and mixing for 30-120 minutes;

d) according to the mass parts, 3-5 parts of functional boronized graphene dispersion liquid containing 1.5% -3.5% of boronized graphene, 20-30 parts of organic solvent, 4-8 parts of auxiliary agent and nano silicon dioxide particles which are complemented to 80 parts are fully and uniformly mixed by adopting a three-dimensional mixing technology through shearing force generated by revolution and autorotation, and the boronized graphene high-thermal-conductivity slurry is obtained.

In an embodiment of the present invention, in the step a), the method further includes the steps of:

a1) and (2) mixing the redox graphene and boric acid according to the mass ratio of 5: 1, adding the mixture into absolute ethyl alcohol, and carrying out ultrasonic stirring for 2-4 hours to obtain a mixed material;

a2) drying the mixed material in the step a1) at 40 ℃, and then putting the mixed material into an argon pyrolysis box;

a3) and pyrolyzing the mixed material for 4 hours at the temperature of 900 ℃ in an argon atmosphere, and naturally cooling to obtain the boronized graphene.

In an embodiment of the present invention, the silane coupling agent is one of a171, a172, and a 151.

In an embodiment of the present invention, in step c), the preparation method of the nano silica particles comprises:

by volume 4: 4: 7, continuously mixing and stirring isopropanol, ammonia water and distilled water for 1 hour;

in the stirring process, adding an ethyl orthosilicate solution uniformly, and stirring to react for 6 hours;

centrifuging to obtain white silicon dioxide, washing with anhydrous ethanol and distilled water for 3 times, and drying at 50 deg.C to obtain nanometer silicon dioxide particles.

In an embodiment of the present invention, the organic solvent in step d) is one or more of ethanol, ethylene glycol, and carbitol.

Compared with the prior art, the invention has the advantages that:

according to the invention, boron is doped into the graphene material to prepare the boronized graphene and the boronized graphene composite slurry, so that the dispersibility of the graphene material is improved, the agglomeration phenomenon is not easy to occur, the compatibility of the graphene material in the heating slurry with the conductive agent and the adhesive is enhanced, the binding force of the slurry and the substrate is improved, good adhesion is shown, and the quality of the heat conduction material is improved.

[ detailed description ] embodiments

The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.

In order to modify graphene to improve the performance of graphene, researches show that the unique two-dimensional hexagonal honeycomb structure of boron alkene endows the graphene with the energy band structure of a Dirac cone and a novel quantum effect. Boron atoms have strong electron deficiency characteristics, part of carbon atoms can be replaced in the compounding process of combining graphene materials, the graphene structure cannot be changed, and boron can be a very suitable doping substance for graphene. The radius of boron atoms is very close to that of carbon atoms, the boronized graphene cannot have great structural distortion, but the boron atoms have one electron less than that of the carbon atoms, the boronized graphene material is fluffy, more folds occur, a porous structure is easily formed among the graphene particles, and due to the electron deficiency of the boron electrons, the charge of the boronized graphene is increased, so that the combination of the graphene and an organic-inorganic material can be greatly improved, and the performance of the composite material is improved. Therefore, the invention provides boronized graphene high-thermal-conductivity slurry and a preparation method thereof.

The invention provides a preparation method of boronized graphene high-thermal-conductivity slurry, which comprises the following steps:

a) adding redox graphene and boric acid into absolute ethyl alcohol, carrying out ultrasonic stirring and uniform dispersion to obtain a mixed material, drying the mixed material at 40 ℃, and carrying out pyrolysis on the mixed material for 4 hours at 900 ℃ in an argon environment to obtain boronized graphene.

b) Modifying boronized graphene by using a silane coupling agent, reacting the silane coupling agent with the boronized graphene to obtain functional boronized graphene, and dispersing the functional expanded graphene in an N-methylpyrrolidone solution through ultrasonic treatment to form a functional boronized graphene dispersion solution.

c) And adding the nano silicon dioxide particles into the functional boronized graphene dispersion liquid under the stirring state, and mixing for 30-120 minutes.

d) According to the mass parts, 3-5 parts of functional boronized graphene dispersion liquid containing 1.5% -3.5% of boronized graphene, 20-30 parts of organic solvent, 4-8 parts of auxiliary agent and nano silicon dioxide particles which are complemented to 80 parts are fully and uniformly mixed by adopting a three-dimensional mixing technology through shearing force generated by revolution and autorotation, and the boronized graphene high-thermal-conductivity slurry is obtained.

In the step a), obtaining the bulked graphene may further include the steps of:

a1) and (2) mixing the redox graphene and boric acid according to the mass ratio of 5: 1, adding the mixture into absolute ethyl alcohol, and carrying out ultrasonic stirring for 2-4 hours to obtain a mixed material;

a2) drying the mixed material in the step a1) at 40 ℃, and then putting the mixed material into an argon pyrolysis box;

a3) and pyrolyzing the mixed material for 4 hours at the temperature of 900 ℃ in an argon atmosphere, and naturally cooling to obtain the boronized graphene.

In one embodiment of the present invention, the silane coupling agent may be one of A171, A172 and A151, wherein A171 is vinyltrimethoxysilane, A172 is vinyltris (β -methoxyethoxy) silane, and A151 is vinyltriethoxysilane.

In step c), the preparation method of the nano silica particles may be:

by volume 4: 4: 7, continuously mixing and stirring isopropanol, ammonia water and distilled water for 1 hour;

in the stirring process, adding an ethyl orthosilicate solution uniformly, and stirring to react for 6 hours;

centrifuging to obtain white silicon dioxide, washing with anhydrous ethanol and distilled water for 3 times, and drying at 50 deg.C to obtain nanometer silicon dioxide particles.

In an embodiment of the present invention, the organic solvent in step d) is one or more of ethanol, ethylene glycol, and carbitol.

The invention will now be described with reference to specific embodiments: