CN112552681A - Functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film and preparation method thereof - Google Patents
Functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of composite materials, and provides a functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film and a preparation method thereofAnd (3) azole to obtain a functionalized boron nitride nanosheet/MXene/polybenzimidazole blending solution, and performing suction filtration on the blending solution to obtain the composite film. The invention utilizes the three-dimensional structure of the polybenzimidazole polymer to lead the modified boron nitride and MXene with electronegativity to generate electrostatic self-assembly so as to form the self-supporting film which takes the polybenzimidazole as a framework and takes the functionalized boron nitride nanosheet and the MXene as mixed filler. Boron nitride nanosheet and Ti3C2The filling network formed by the synergistic effect of Tx bridging effectively reduces the interface thermal resistance and endows the composite film with excellent heat-conducting property. The method is simple and effective, and the prepared high-thermal-conductivity film has wide application prospects in the fields of energy, electronics and the like.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film and a preparation method thereof.
Background
With the rapid development of technology, electronic components and their devices are gradually integrated, miniaturized and lightweight, and the integration degree of these devices is continuously increased, which means that a large amount of heat is generated during use. The concentration of large amounts of heat can have a detrimental effect on the safety and lifetime of electronic components. Therefore, in order to ensure that the heat generated by the electronic components generating heat is discharged in time, the electronic equipment can be operated safely and stably for a long time, and the heat dissipation is a problem which is urgently needed to be solved at present.
Boron nitride becomes a heat-conducting mixed filler with wide application due to the ultrahigh heat-conducting property, good insulating property and mechanical property of the boron nitride. Filling high thermal conductivity mixed filler to prepare polymer-based composite material is the most common method for improving the thermal conductivity of polymer material at present. The improvement of the polymer performance of the mixed filler is mainly caused by the good dispersion of the mixed filler in the polymer and the interaction between the mixed filler and the polymer matrix. Unmodified functionalized boron nitride is easy to agglomerate and cannot be well dispersed in a solution, so that the surface of the boron nitride nanosheet needs to be modified to enhance the interaction between the boron nitride nanosheet and a polymer matrix.
However, most polymer materials have low heat conductivity, and the intrinsic heat conductivity coefficient does not exceed 0.2W/(mK), so that the use requirements of the industry cannot be met. Therefore, a high thermal conductive mixed filler is required to fill the polymer to obtain a composite material with high thermal conductivity.
Disclosure of Invention
The invention aims to solve the problem that the heat conductivity improved by the single mixed filler filled polymer is not obvious enough, and aims to provide a high-heat-conductivity functionalized boron nitride nanosheet/MXene/polybenzimidazole high-heat-conductivity composite film and a preparation method thereof.
The invention provides a preparation method of a functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film, which is characterized by comprising the following steps of: respectively dispersing amino-functionalized boron nitride nanosheets and MXene nanosheets in a dispersing agent, mixing to obtain a mixed solution, then adding polybenzimidazole into the mixed solution to obtain a functionalized boron nitride nanosheet/MXene/polybenzimidazole blended solution, and carrying out suction filtration on the blended solution to obtain a functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film with polybenzimidazole as a framework and boron nitride nanosheets and MXene nanosheets as mixed fillers, wherein the mass ratio of the mixed fillers to the polybenzimidazole is 0.01-0.30.
In the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film provided by the invention, the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film also has the following characteristics: dispersing an amino functionalized boron nitride nanosheet in a dispersing agent to obtain a boron nitride nanosheet dispersion liquid, and specifically operating as follows: step S1-1, calcining boron nitride powder in a nitrogen furnace at 800-1000 ℃ for 1-4 h, carrying out melt reaction on the calcined boron nitride powder and urea for 3-6 h under the nitrogen atmosphere, dispersing the obtained solid in water, carrying out centrifugation after ultrasonic stripping, collecting supernatant, filtering the supernatant and collecting filter cakes, and then washing and drying the filter cakes to obtain amino-functionalized boron nitride nanosheets; and step S1-2, dispersing the amino functionalized boron nitride nanosheets in a dispersing agent to obtain a boron nitride nanosheet dispersion liquid.
In the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film provided by the invention, the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film also has the following characteristics: the method comprises the following steps of (1) dispersing MXene nanosheets in a dispersing agent to obtain MXene nanosheet dispersion liquid, and specifically comprises the following steps: step S2-1, adding titanium aluminum carbide into hydrofluoric acid for etching, centrifugally washing until the pH value of the washing liquid is neutral, and drying to obtain MXene nanosheets; and step S2-2, dispersing the MXene nanosheets in a dispersing agent to obtain an MXene nanosheet dispersion liquid.
In the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film provided by the invention, the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film also has the following characteristics: the preparation method comprises the following steps of ultrasonically mixing a boron nitride nanosheet dispersion liquid and an MXene nanosheet dispersion liquid to obtain a mixed liquid, adding polybenzimidazole into the mixed liquid, and stirring at 80-100 ℃ for 3-8 h.
In the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film provided by the invention, the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film also has the following characteristics: wherein the mass ratio of the boron nitride powder to the urea is 1: 4-1: 7, and the melting reaction temperature is 130-140 ℃.
In the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film provided by the invention, the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film also has the following characteristics: in step S2-1, 1g of titanium aluminum carbide is added into 20ml of 40% hydrofluoric acid and etched for 45-55 h under the stirring condition, and after etching is finished, water is used for centrifugal washing for 3 times, and then ethanol is used for centrifugal washing until the pH value of the washing liquid is neutral.
In the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film provided by the invention, the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film also has the following characteristics: wherein, in the step S1-1, the temperature is raised to 800-1000 ℃ at the speed of 1-5 ℃/min during calcination, the airflow speed of nitrogen is 10-20 cc/min, and the ultrasonic stripping time is 8-12 h; the centrifugation speed is 2500rpm to 4000rpm, the centrifugation time is 5min to 20min, the drying temperature is 60 ℃ to 80 ℃, and the drying time is 12h to 48 h.
In the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film provided by the invention, the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film also has the following characteristics: and then, carrying out vacuum drying on the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film at the temperature of 80-100 ℃ for 12-48 h.
In the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film provided by the invention, the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film also has the following characteristics: wherein the dispersant is any one of dimethyl sulfoxide, dimethylformamide or N-methylpyrrolidone.
The invention also provides a functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film which has the characteristics and is prepared by the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film.
Action and Effect of the invention
According to the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film, firstly, the amino functionalized boron nitride nanosheet and the MXene nanosheet are respectively dispersed in a dispersing agent, mixed liquid is obtained after mixing, then polybenzimidazole is added into the mixed liquid to obtain the functionalized boron nitride nanosheet/MXene/polybenzimidazole blended liquid, and the blended liquid is subjected to suction filtration to obtain the composite film. The invention uses the three-dimensional structure of the polybenzimidazole polymer as a binder, and makes the modified boron nitride containing amino and MXene with electronegativity undergo electrostatic self-assembly to form the self-supporting film which takes the polybenzimidazole as a framework and takes the functionalized boron nitride nanosheet and the MXene as mixed fillers. Functionalized boron nitride nanosheets and Ti in the film3C2Filling network formed by synergistic effect of Tx bridgingThe method can effectively reduce the interface thermal resistance, finally promote the heat transfer, and eliminate the adverse effects that the boron nitride is directly adopted as the mixed filler, the mixed filler is easy to agglomerate, the filling amount is high, the composite material is low in flexibility and the like. Compared with the prior art, the invention utilizes the functionalized boron nitride nanosheet, the stripped MXene and the polybenzimidazole as the assembly, the functionalized boron nitride nanosheet and the Ti3C2The synergistic effect of the ternary composite system of Tx and polybenzimidazole is beneficial to improving the mechanical property of the ternary composite material. Meanwhile, the composite film is endowed with excellent heat-conducting property, the method is simple and effective, and the prepared high-heat-conducting film has wide application prospect in the fields of energy, electronics and the like.
Drawings
FIG. 1 is a photograph of a commercially available boron nitride and a boron nitride nanosheet dispersion prepared in example 1;
FIG. 2 is a photograph of an MXene nanosheet dispersion prepared in example 1;
fig. 3 is an SEM image of functionalized boron nitride nanoplates made in example 1;
fig. 4 is an SEM image of MXene nanoplatelets prepared in example 1;
FIG. 5 is a photograph of a functionalized boron nitride nanosheet/MXene/polybenzimidazole composite film prepared in example 1; and
FIG. 6 is a thermal conductivity diagram of the functionalized boron nitride nanosheet/MXene/polybenzimidazole composite film prepared in examples 1-4.
Detailed Description
In order to make the technical means, creation features, achievement purposes and effects of the present invention easy to understand, the following embodiments and the accompanying drawings are used to specifically describe a functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film and a preparation method thereof.
In the following examples, unless otherwise specified, all the conventional commercially available raw materials or conventional processing techniques in the art are indicated.
The invention provides a preparation method of a functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film (hereinafter referred to as a composite film), which comprises the following specific operations:
respectively dispersing amino-functionalized boron nitride nanosheets and MXene nanosheets in a dispersing agent, mixing to obtain a mixed solution, then adding polybenzimidazole into the mixed solution to obtain a functionalized boron nitride nanosheet/MXene/polybenzimidazole blended solution, carrying out suction filtration on the blended solution to obtain a functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film with polybenzimidazole as a framework and boron nitride nanosheets and MXene nanosheets as mixed fillers, wherein the mass ratio of the mixed fillers to the polybenzimidazole is 0.01-0.30.
Wherein the boron nitride nanosheet dispersion is obtained by:
step S1-1, placing boron nitride powder in a nitrogen furnace, raising the temperature to 800-1000 ℃ at the speed of 1-5 ℃/min, calcining for 1-4 h, and keeping the airflow speed of nitrogen at 10-20 cc/min during calcining. And carrying out melt reaction on the calcined boron nitride powder and urea for 3-6 h in a nitrogen atmosphere, wherein the melt reaction temperature is 130-140 ℃. And after the melting reaction is finished, dispersing the obtained solid in deionized water, ultrasonically stripping for 8-12 h, then centrifuging for 5-20 min at the speed of 2500-4000 rpm, collecting the supernatant in which the boron nitride nanosheet is dispersed, and discarding the underlying thick-layer gathered boron nitride powder. Filtering the supernatant to collect a filter cake, washing the filter cake, and drying at 60-80 ℃ for 12-48 h to obtain the amino functionalized boron nitride nanosheet. In the step, the mass ratio of the boron nitride powder to the urea is 1: 4-1: 7.
And step S1-2, dispersing the amino functionalized boron nitride nanosheets in a dispersing agent to obtain a boron nitride nanosheet dispersion liquid.
The MXene nanosheet dispersion is obtained by the following operations: :
in step S2-1, step S2-1, 1g of titanium aluminum carbide (Ti)3AlC2) Adding the mixed solution into 20ml of 40% hydrofluoric acid, etching for 45-55 h under the stirring condition, after etching is finished, centrifugally washing for 3 times by using water, centrifugally washing by using ethanol until the pH value of a washing solution is neutral, and drying to obtain the MXene nanosheet. In this step, the magnetic stirring speed of the etchingThe degree is 450 r/min-550 r/min, the centrifugation speed of the deionized water is 4800 r/min-5200 r/min, the centrifugation time is 5 min-10 min, the centrifugation is carried out for 3 times, the centrifugation speed of the ethanol is 8000 r/min-10000 r/min, and the centrifugation time is 5 min-10 min.
And step S2-2, dispersing the MXene nanosheets in a dispersing agent to obtain an MXene nanosheet dispersion liquid.
The specific operation of film formation is as follows:
ultrasonically mixing the boron nitride nanosheet dispersion liquid and the MXene nanosheet dispersion liquid to obtain a mixed liquid, then adding polybenzimidazole into the mixed liquid, and stirring for 3-8 h at 80-100 ℃ to obtain a blended liquid. And (3) carrying out vacuum filtration on the blended solution to obtain a functional boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film (namely a composite film), and then carrying out vacuum drying on the composite film for 12-48 h at the temperature of 80-100 ℃.
The dispersant is any one of dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) or N-methylpyrrolidone (NMP). In the following examples, DMSO is used only as an example, and DMF or NMP can achieve the same effect.
< example 1>
A preparation method of a composite film containing 1 wt% of boron nitride nanosheet/MXene mixed filler comprises the following specific steps:
(1) the boron nitride powder was calcined in a 1000 ℃ tube furnace under nitrogen gas for 3 h.
(2) 1g of calcined boron nitride powder and 5g of urea are placed in a round-bottom flask, and are heated to 140 ℃ in an oil bath under nitrogen gas to carry out melting reaction for 6 hours.
(3) After the reaction is finished, dispersing the solid in 500ml of deionized water, carrying out ultrasonic stripping treatment for 10 hours to obtain dispersion liquid, and then centrifuging the dispersion liquid at the rotating speed of 3000rpm for 10min to obtain supernatant; filtering the supernatant, washing the filter cake with deionized water, preferably performing suction filtration by using a filtering method, and drying the collected solid at 60 ℃ for 10 hours to obtain the urea functionalized boron nitride nanosheet.
(4) Mixing 1g of Ti3AlC2Gradually and slowly adding into 20ml40 wt%Stirring the solution in hydrofluoric acid solution at the rotating speed of 500r/min for reacting at room temperature for 48 hours, respectively adopting deionized water and ethanol for centrifugal washing until the pH value of the solution is neutral, and performing vacuum drying; the centrifugation speed of deionized water is 5000r/min, the centrifugation time is 5min, the centrifugation is carried out for 3 times, the centrifugation speed of ethanol is 8000r/min, and the centrifugation time is 5 min.
(5) Taking out the powder, adding the powder into dimethyl sulfoxide, stirring for 24h at 35 ℃, and then centrifuging and washing to remove the dimethyl sulfoxide. Then adding a proper amount of deionized water, and crushing the cells for 10 hours. Centrifuging for 10min, collecting supernatant, and freeze drying to obtain MXene at a centrifuging rate of 3500 r/min.
(6) And (2) respectively ultrasonically dispersing the boron nitride nanosheet and the MXene nanosheet with the same mass of 2.5mg in 5ml of dimethyl sulfoxide solution, ultrasonically blending to prepare a boron nitride nanosheet/MXene mixed solution, then adding 0.5g of polybenzimidazole powder into the mixed solution, magnetically stirring for 5 hours at 100 ℃, and after the reaction is finished, carrying out vacuum filtration to form a film to obtain the composite film. During vacuum filtration, the filter membrane is an organic nylon filter membrane with the diameter of 50mm and the aperture of 0.2 mu m, and the composite membrane is dried for 24 hours in vacuum at the temperature of 80 ℃.
< example 2>
A preparation method of a composite film containing 5 wt% of boron nitride nanosheet/MXene mixed filler comprises the following specific steps:
(1) the boron nitride powder was calcined in a 1000 ℃ tube furnace under nitrogen gas for 3 h.
(2) 1g of calcined boron nitride powder and 5g of urea are placed in a round-bottom flask, and are heated to 140 ℃ in an oil bath under nitrogen gas to carry out melting reaction for 6 hours.
(3) After the reaction is finished, dispersing the solid in 500ml of deionized water, carrying out ultrasonic stripping treatment for 10 hours to obtain dispersion liquid, and then centrifuging the dispersion liquid at the rotating speed of 3000rpm for 10min to obtain supernatant; filtering the supernatant, washing with deionized water, preferably performing suction filtration, and drying the collected solid at 60 ℃ for 10h to obtain the urea functionalized boron nitride nanosheet.
(4) Mixing 1g of Ti3AlC2Gradually slow downSlowly adding into 20ml of 40 wt% hydrofluoric acid solution, stirring at 500r/min for reacting at room temperature for 48h, respectively centrifugally washing with deionized water and ethanol until the pH value of the solution is neutral, and vacuum drying; the centrifugation speed of deionized water is 5000r/min, the centrifugation time is 5min, the centrifugation is carried out for 3 times, the centrifugation speed of ethanol is 8000r/min, and the centrifugation time is 5 min.
(5) Taking out the powder, adding the powder into dimethyl sulfoxide, and stirring the mixture for 24 hours at the temperature of 35 ℃. After the reaction is finished, centrifuging and washing are carried out to remove the dimethyl sulfoxide. Then adding a proper amount of deionized water, and crushing the cells for 10 hours. Centrifuging for 10min, collecting supernatant, and freeze drying to obtain MXene at a centrifuging rate of 3500 r/min.
(6) Respectively ultrasonically dispersing a boron nitride nanosheet and an MXene nanosheet with the same mass of 13.1mg in 5ml of dimethyl sulfoxide solution, ultrasonically blending to prepare a boron nitride nanosheet/MXene mixed solution, then adding 0.5g of polybenzimidazole powder into the mixed solution, magnetically stirring for 5 hours at 100 ℃, and after the reaction is finished, carrying out vacuum filtration to form a film to obtain the composite film. During vacuum filtration, the filter membrane is an organic nylon filter membrane with the diameter of 50mm and the aperture of 0.2 mu m, and the composite membrane is dried for 24 hours in vacuum at the temperature of 80 ℃.
< example 3>
A preparation method of a composite film containing 10 wt% of boron nitride nanosheet/MXene mixed filler comprises the following specific steps:
(1) the boron nitride powder was calcined in a 1000 ℃ tube furnace under nitrogen gas for 3 h.
(2) 1g of calcined boron nitride powder and 5g of urea are placed in a round-bottom flask, and are heated to 140 ℃ in an oil bath under nitrogen gas to carry out melting reaction for 6 hours.
(3) After the reaction is finished, dispersing the solid in 500ml of deionized water, carrying out ultrasonic stripping treatment for 10 hours to obtain dispersion liquid, and then centrifuging the dispersion liquid at the rotating speed of 3000rpm for 10min to obtain supernatant; filtering the supernatant, washing with deionized water, preferably performing suction filtration, and drying the collected solid at 60 ℃ for 10h to obtain the urea functionalized boron nitride nanosheet.
(4) Mixing 1g ofTi3AlC2Gradually and slowly adding the mixture into 20ml of 40 wt% hydrofluoric acid solution, stirring at the rotating speed of 500r/min for reacting at room temperature for 48 hours, respectively carrying out centrifugal washing by using deionized water and ethanol until the pH value of the solution is neutral, and carrying out vacuum drying; the centrifugation speed of deionized water is 5000r/min, the centrifugation time is 5min, the centrifugation is carried out for 3 times, the centrifugation speed of ethanol is 8000r/min, and the centrifugation time is 5 min.
(5) Taking out the powder, adding the powder into dimethyl sulfoxide, and stirring the mixture for 24 hours at the temperature of 35 ℃. After the reaction is finished, centrifuging and washing are carried out to remove the dimethyl sulfoxide. Then adding a proper amount of deionized water, and crushing the cells for 10 hours. Centrifuging for 10min, collecting supernatant, and freeze drying to obtain MXene at a centrifuging rate of 3500 r/min.
(6) Respectively ultrasonically dispersing a boron nitride nanosheet and an MXene nanosheet with the same mass of 27.8mg in 5ml of dimethyl sulfoxide solution, ultrasonically blending to prepare a boron nitride nanosheet/MXene mixed solution, then adding 0.5g of polybenzimidazole powder into the mixed solution, magnetically stirring for 5 hours at 100 ℃, and after the reaction is finished, carrying out vacuum filtration to form a film to obtain the composite film. During vacuum filtration, the filter membrane is an organic nylon filter membrane with the diameter of 50mm and the aperture of 0.2 mu m, and the composite membrane is dried for 24 hours in vacuum at the temperature of 80 ℃.
< example 4>
A preparation method of a composite film containing 20 wt% of boron nitride nanosheet/MXene mixed filler comprises the following specific steps:
(1) the boron nitride powder was calcined in a 1000 ℃ tube furnace under nitrogen gas for 3 h.
(2) 1g of calcined boron nitride powder and 5g of urea are placed in a round-bottom flask, and are heated to 140 ℃ in an oil bath under nitrogen gas to carry out melting reaction for 6 hours.
(3) After the reaction is finished, dispersing the solid in 500ml of deionized water, carrying out ultrasonic stripping treatment for 10 hours to obtain dispersion liquid, and then centrifuging the dispersion liquid at the rotating speed of 3000rpm for 10min to obtain supernatant; filtering the supernatant, washing with deionized water, preferably performing suction filtration, and drying the collected solid at 60 ℃ for 10h to obtain the urea functionalized boron nitride nanosheet.
(4) Mixing 1g of Ti3AlC2Gradually and slowly adding the mixture into 20ml of 40 wt% hydrofluoric acid solution, stirring at the rotating speed of 500r/min for reacting at room temperature for 48 hours, respectively carrying out centrifugal washing by using deionized water and ethanol until the pH value of the solution is neutral, and carrying out vacuum drying; the centrifugation speed of deionized water is 5000r/min, the centrifugation time is 5min, the centrifugation is carried out for 3 times, the centrifugation speed of ethanol is 8000r/min, and the centrifugation time is 5 min.
(5) Taking out the powder, adding the powder into dimethyl sulfoxide, and stirring the mixture for 24 hours at the temperature of 35 ℃. After the reaction is finished, centrifuging and washing are carried out to remove the dimethyl sulfoxide. Then adding a proper amount of deionized water, and crushing the cells for 10 hours. Centrifuging for 10min, collecting supernatant, and freeze drying to obtain MXene at a centrifuging rate of 3500 r/min.
(6) And (2) respectively ultrasonically dispersing a boron nitride nanosheet and an MXene nanosheet with the same mass of 62.5mg in 5ml of dimethyl sulfoxide solution, ultrasonically blending to prepare a boron nitride nanosheet/MXene mixed solution, then adding 0.5g of polybenzimidazole powder into the mixed solution, magnetically stirring for 5 hours at 100 ℃, and after the reaction is finished, carrying out vacuum filtration to form a film to obtain the composite film. During vacuum filtration, the filter membrane is an organic nylon filter membrane with the diameter of 50mm and the aperture of 0.2 mu m, and the composite membrane is dried for 24 hours in vacuum at the temperature of 80 ℃.
< comparative example 1>
A preparation method of a pure polybenzimidazole film comprises the following specific steps:
0.5g of polybenzimidazole powder is added into 10ml of dimethyl sulfoxide, the mixture is stirred by oil bath magnetic force for 5 hours at the temperature of 100 ℃, after the reaction is finished, an organic nylon filter membrane with the diameter of 50mm and the pore diameter of 0.2 mu m is selected as the filter membrane, the vacuum filtration is carried out, the pure polybenzimidazole film is prepared, and the film is dried for 24 hours at the temperature of 80 ℃.
< test example >
The dispersibility of the functionalized boron nitride nanosheets, MXene nanosheets and commercially available boron nitride prepared in examples 1-4 was tested, and SEM detection of the functionalized boron nitride nanosheets and MXene nanosheets prepared in examples 1-4 resulted in similar dispersibility and SEM of the functionalized boron nitride nanosheets and MXene nanosheets in examples 1-4, so only the results of example 1 are shown.
Fig. 1 is a photograph comparing the functionalized boron nitride nanosheets prepared in example 1 with a commercially available boron nitride dispersion, wherein the commercially available boron nitride is stacked and not well dispersed in the solution, and the functionalized boron nitride nanosheet dispersion is well dispersed and does not exhibit agglomeration stacking.
Fig. 2 is a photograph of the MXene/dimethylsulfoxide dispersion obtained in example 1, and it can be seen that MXene is well dispersed in the dimethylsulfoxide solution.
Fig. 3 is an SEM image of the boron nitride nanosheet prepared in example 1, from which it can be seen that boron nitride gave better exfoliation.
Fig. 4 is an SEM image of MXene obtained in example 1, and it can be seen that MXene has a superior peeling effect.
FIG. 5 is a photograph of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film prepared in example 1.
The films prepared in examples 1 to 4 and comparative example 1 were subjected to a thermal conductivity test, specifically:
firstly, cutting into a wafer with the diameter of 25mm and the thickness of less than 0.5mm, and directly measuring the thermal diffusivity (alpha) of the material by a transient method by using a laser method thermal conductivity analyzer (LFA467) of Germany NETZSCH. The specific heat capacity (c) of the composite was characterized by a differential scanning calorimeter (NetzschDSC200F3) based on astm e 1269-2011. Finally, the thermal conductivity (λ) is calculated by the formula λ ═ α ρ c, and the result is shown in fig. 6.
Fig. 6 is a thermal conductivity curve diagram of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film prepared in examples 1-4, and it can be seen from the graph that the thermal conductivity of the composite film is gradually increased along with the mixed filling of the boron nitride nanosheet and the MXene.
Effects and effects of the embodiments
According to the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film provided by the embodiment, firstly, the amino-functionalized boron nitride nanosheet and the MXene nanosheet are respectively dispersed in the dispersing agentAnd mixing to obtain a mixed solution, adding polybenzimidazole into the mixed solution to obtain a functional boron nitride nanosheet/MXene/polybenzimidazole blended solution, and performing suction filtration on the blended solution to obtain the composite film. The invention uses the three-dimensional structure of the polybenzimidazole polymer as a binder, and makes the modified boron nitride containing amino and MXene with electronegativity undergo electrostatic self-assembly to form the self-supporting film which takes the polybenzimidazole as a framework and takes the functionalized boron nitride nanosheet and the MXene as mixed fillers. Functionalized boron nitride nanosheets and Ti in the film3C2The filling network formed by the synergistic effect of Tx bridging can effectively reduce the interface thermal resistance, finally promote the heat transfer, and eliminate the adverse effects that the boron nitride is directly adopted as the mixed filler, the mixed filler is easy to agglomerate, the filling amount is high, the composite material is low in flexibility and the like. Compared with the prior art, the invention utilizes the functionalized boron nitride nanosheet, the stripped MXene and the polybenzimidazole as the assembly, the functionalized boron nitride nanosheet and the Ti3C2The synergistic effect of the ternary composite system of Tx and polybenzimidazole is beneficial to improving the mechanical property of the ternary composite material. Meanwhile, the composite film is endowed with excellent heat-conducting property, the method is simple and effective, and the prepared high-heat-conducting film has wide application prospect in the fields of energy, electronics and the like.
In the embodiment, the amino functionalization of boron nitride is realized through the reaction of boron nitride and urea, and then the functionalized boron nitride nano material is realized through ultrasonic stripping; meanwhile, MXene nanosheets are prepared through ultrasonic stripping, so that MXene is dispersed more uniformly, a good filler-polymer interface can be formed, and interface thermal resistance is reduced.
The mass ratio of the mixed filler to the polybenzimidazole is 0.01-0.30, and the heat conducting property of the composite film is improved due to the filling of the mixed filler.
The mass ratio of the boron nitride powder to the urea is 1: 4-1: 7, the temperature of the melting reaction is 130-140 ℃, so that the boron nitride and the urea are fully reacted, the amino group of the urea is better grafted on the edge of the boron nitride, and the edge of the amino group of the boron nitride is successfully functionalized.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film is characterized by comprising the following steps:
respectively dispersing amino-functionalized boron nitride nanosheets and MXene nanosheets in a dispersing agent, mixing to obtain a mixed solution, then adding polybenzimidazole into the mixed solution to obtain a functionalized boron nitride nanosheet/MXene/polybenzimidazole blended solution, carrying out suction filtration on the blended solution to obtain a functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film with the polybenzimidazole as a framework and the boron nitride nanosheets and the MXene nanosheets as mixed fillers,
wherein the mass ratio of the mixed filler to the polybenzimidazole is 0.01-0.30.
2. The preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film according to claim 1, wherein the preparation method comprises the following steps:
dispersing the amino functionalized boron nitride nanosheet in a dispersing agent to obtain a boron nitride nanosheet dispersion liquid, wherein the specific operations are as follows:
step S1-1, calcining boron nitride powder in a nitrogen furnace at 800-1000 ℃ for 1-4 h, carrying out melt reaction on the calcined boron nitride powder and urea for 3-6 h under the nitrogen atmosphere, dispersing the obtained solid in water, carrying out centrifugation after ultrasonic stripping, collecting supernatant, filtering the supernatant and collecting filter cakes, and then washing and drying the filter cakes to obtain amino-functionalized boron nitride nanosheets;
and S1-2, dispersing the amino functionalized boron nitride nanosheet in a dispersing agent to obtain the boron nitride nanosheet dispersion liquid.
3. The preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film according to claim 2, wherein the preparation method comprises the following steps:
the MXene nanosheet is dispersed in a dispersing agent to obtain MXene nanosheet dispersion liquid, and the specific operation is as follows:
step S2-1, adding titanium aluminum carbide into hydrofluoric acid for etching, centrifugally washing until the pH value of a washing liquid is neutral, and drying to obtain the MXene nanosheets;
and step S2-2, dispersing the MXene nanosheets in a dispersing agent to obtain the MXene nanosheet dispersion liquid.
4. The preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film according to claim 3, wherein the preparation method comprises the following steps:
ultrasonically mixing the boron nitride nanosheet dispersion liquid and the MXene nanosheet dispersion liquid to obtain the mixed liquid, then adding the polybenzimidazole into the mixed liquid, and stirring for 3-8 h at the temperature of 80-100 ℃.
5. The preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film according to claim 3, wherein the preparation method comprises the following steps:
wherein the mass ratio of the boron nitride powder to the urea is 1: 4-1: 7, and the melting reaction temperature is 130-140 ℃.
6. The preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film according to claim 3, wherein the preparation method comprises the following steps:
in step S2-1, 1g of titanium aluminum carbide is added into 20ml of 40% hydrofluoric acid and etched for 45-55 h under the stirring condition, and after etching is finished, water is used for centrifugal washing for 3 times, and then ethanol is used for centrifugal washing until the pH value of a washing liquid is neutral.
7. The preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film according to claim 3, wherein the preparation method comprises the following steps:
wherein in the step S1-1, the temperature is raised to 800-1000 ℃ at the rate of 1-5 ℃/min during calcination, the airflow velocity of nitrogen is 10-20 cc/min,
the ultrasonic stripping time is 8-12 h; the centrifugation speed is 2500rpm to 4000rpm, the centrifugation time is 5min to 20min, the drying temperature is 60 ℃ to 80 ℃, and the drying time is 12h to 48 h.
8. The preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film according to claim 1, wherein the preparation method comprises the following steps:
and carrying out vacuum filtration on the blended solution under reduced pressure to obtain the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film, and then carrying out vacuum drying on the functionalized boron nitride nanosheet/MXene/polybenzimidazole high-thermal-conductivity composite film at the temperature of 80-100 ℃ for 12-48 h.
9. The preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film according to claim 1, wherein the preparation method comprises the following steps:
wherein the dispersant is any one of dimethyl sulfoxide, dimethylformamide or N-methylpyrrolidone.
10. A functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film, which is characterized by being prepared by the preparation method of the functionalized boron nitride nanosheet/MXene/polybenzimidazole high thermal conductivity composite film according to any one of claims 1 to 9.
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