CN116375475A - Construction method for preparing oriented boron nitride aerogel by low-cost freeze-drying-free method - Google Patents
Construction method for preparing oriented boron nitride aerogel by low-cost freeze-drying-free method Download PDFInfo
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Abstract
The invention discloses a construction method for preparing oriented boron nitride aerogel by a low-cost and freeze-drying-free method, and provides a construction method for preparing oriented boron nitride aerogel by a low-cost and freeze-drying-free method for preparing oriented boron nitride aerogel. In order to realize the interconnection between boron nitride sheets, graphene oxide is introduced into the system to be used as chemical glue for bonding the sheets. In order to improve the energy consumption and time consumption of the traditional freeze drying, the preparation of the boron nitride aerogel is directly realized by adopting air drying in combination with chemical hydrothermal reduction and ice template orientation.
Description
Technical Field
The invention belongs to the field of thermal interface materials, relates to a construction method of a high-performance thermal interface material, and in particular relates to a construction method of a low-cost and non-freeze-drying method oriented boron nitride aerogel.
Background
In the heat transfer process, heat flow is blocked due to the existence of an interface, a certain temperature drop is generated at the interface position, and heat is accumulated at the interface position to form interface thermal resistance. For the reason of the generation of contact thermal resistance, the conventional wisdom is that the actual contact area of the two interfaces is small, less than 0.1% of the total area, due to the unavoidable interface roughness caused by machining, and the contact at the interfaces is not completely even if an elastic thermal interface material is added. The contact area generated by the contact is limited, so that the heat flow line is contracted, and larger contact thermal resistance is generated. In order to improve the larger thermal resistance caused by rough contact, a high-heat-conductivity interface material can be adopted to fill the interface gaps and strengthen the interface heat transfer.
Boron nitride has a high in-plane thermal conductivity and is often used as a heat conducting filler to enhance the thermal properties of the resin, especially in some cases where high thermal conductivity is required for insulation. Because of its graphene-like two-dimensional structure, boron nitride also has anisotropy of thermal conductivity, and in order to fully exploit its advantages in-plane thermal conductivity, it is necessary to orient the boron nitride in order to conduct heat from a heat source to a heat sink material.
Boron nitride has excellent heat conductivity coefficient, but the interaction between the sheet layers is lacking, and when the three-dimensional macroscopic body is prepared, the boron nitride can be bonded to form aerogel only by adopting a mode of blending with a polymer or introducing an adhesive, such as nanocellulose and the like. The nanocellulose binder can be used as a heat conduction path to realize heat transportation between boron nitride sheets in the heat transfer process, but the binder with low heat conductivity can greatly influence the transfer of phonons between the heat conduction sheets, so that other high-conductivity binders are required to realize excellent heat conduction between the sheets.
The graphene oxide is used as an oxidized derivative of graphene and can be used as chemical glue for connecting substances, so that the invention aims to solve the problem of interlayer contact of boron nitride sheets, and the graphene oxide is introduced into a boron nitride system to serve as the chemical glue for realizing the interconnection of boron nitride. In addition, after the graphene oxide is chemically reduced, the thermal conductivity is recovered, and the thermal conductivity between the sheets can be further improved. Secondly, for the three-dimensional communication network structure of the orientation structure, a freeze drying mode is generally adopted for drying samples, the drying process is severe in condition, low temperature and low pressure are needed, and energy and time are consumed.
Disclosure of Invention
In order to realize the preparation of the boron nitride aerogel with the orientation structure, the invention provides a construction method for preparing the oriented boron nitride aerogel by a low-cost method without freeze drying. In order to realize the interconnection between boron nitride sheets, graphene oxide is introduced into the system to be used as chemical glue for bonding the sheets. In order to improve the energy consumption and time consumption of the traditional freeze drying, the preparation of the boron nitride aerogel is directly realized by adopting air drying in combination with chemical hydrothermal reduction and ice template orientation.
The invention aims at realizing the following technical scheme:
a construction method for preparing oriented boron nitride aerogel by a low-cost method without freeze drying comprises the following steps:
step one: boron nitride powder was added to the graphene oxide solution in batches and mixed using a cell pulverizer. The boron nitride is added in small quantity for many times in batches to improve the mixing uniformity of the boron nitride, so that the agglomeration caused by adding the boron nitride once is avoided, and the difficulty of mixing uniformity is increased.
In the step, the concentration of graphene oxide is more than 5-15 mg/ml, so that the serious shrinkage of hydrogel caused by insufficient skeleton concentration in the chemical reduction process is avoided, but the excessive high solution viscosity is avoided, the orientation is influenced, the specific concentration is based on the viscosity of the mixed solution, and the final mixed solution has fluidity.
In the step, the mass ratio of the boron nitride to the graphene is not higher than 1-5: 1, the defect of insufficient content of graphene oxide is avoided, and the bonding effect is reduced.
Step two: and placing the graphene oxide-boron nitride mixed solution in a freezing mold, fully mixing the graphene oxide-boron nitride mixed solution with a reducing agent, and then performing pre-reduction treatment.
In this step, the reducing agent is ascorbic acid, and may be other reducing agents for promoting gel, such as potassium hydroxide, hydroiodic acid, hydrazine hydrate, sodium borohydride, etc.
In the step, the thermal conductivity of the bottom of the freezing mould is 5-400W m -1 K -1 Is metal with side wall heat conductivity of 0.01-2W m -1 K -1 Is composed of a polymer of (a).
In the step, the time of the pre-reduction treatment is controlled within 1-3 h.
In the step, the mass ratio of graphene oxide to reducing agent is 1:1 to 1:5.
step three: and (5) placing the mixed solution after heat balance into a refrigerating device for directional refrigeration.
In this step, the refrigerating apparatus includes a cold source, a refrigerating container, a cold homogenizing liquid, and a refrigerating mold, wherein: a cold homogenizing liquid is arranged between the freezing container and the freezing mould; the cold source can be liquid nitrogen, the solution such as ethanol is used as soaking solution in a stainless steel container, the freezing speed is controlled by controlling the height from the liquid level of the liquid nitrogen, or the freezing speed is regulated by changing the heat conductivity of the bottom material of the freezing mould, and the cold source can also be any refrigerating material or device such as other refrigerating liquids or semiconductor refrigerating plates; the cold source can be a refrigerating device such as liquid nitrogen, a semiconductor refrigerating plate and the like; the cold homogenizing liquid can be organic solvent with low freezing point (-40 deg.C) such as methanol and ethanol; the bottom of the freezing mould can be silver, copper, aluminum, stainless steel and the like with the thermal conductivity of 10-400 Wm -1 K -1 The side wall is made of a material with a thermal conductivity of 0.1-5 Wm -1 K -1 The low thermal conductive polymer can be silica gel, epoxy resin, acrylic plate and the like.
In the step, the orientation freezing is realized by using liquid nitrogen at normal temperature.
Step four: thawing the frozen sample, and heating the sample under the air condition after the frozen sample is completely thawed, so that the sample is converted into hydrogel.
In the step, the thawed sample is heated for 2-4 hours under the air condition of 50-70 ℃ to ensure that an oriented structure is maintained, the preformed degree is that the surface of the sample is pressed and deformed but not sticky, no obvious shrinkage exists, and if the shrinkage phenomenon is serious, the reaction time is shortened or the dosage of graphene oxide is increased.
Step five: the hydrogel is cooled to room temperature, subjected to heat balance, and then placed in a refrigerating device for secondary directional refrigeration, so that the structure is reinforced to be oriented.
In the step, the directional freezing is carried out under the same freezing condition as the third step, so that the directional structure is further enhanced.
In this step, the heat balance is performed under the same heat balance conditions as in the third step.
Step six: after the secondary frozen sample is completely thawed, the secondary frozen sample is heated under air condition to thoroughly mold the hydrogel.
In the step, the thawed sample reacts for 6-8 hours under the air condition of 50-60 ℃ to thoroughly form hydrogel.
Step seven: and cooling the thoroughly formed hydrogel to room temperature, and putting the hydrogel into a refrigerator for freezing to improve the mechanical property of the hydrogel.
In this step, the hydrogel is frozen at-20 to-30℃for about 4 hours, so as to strengthen the skeleton structure.
Step eight: after thawing the frozen hydrogel, heating under air condition to further reduce the graphene oxide hydrogel.
In the step, the unfrozen hydrogel is reduced under the air condition of 50-80 ℃ for 8-12 h.
Step nine: and (3) washing the reduced hydrogel with deionized water for several times, removing the internal solution, and drying at normal temperature or by heating to finally obtain the aerogel with the vertical structure.
In the step, the hydrogel washed by deionized water is dried for about 5 to 10 hours under the air condition of 50 to 70 ℃ to finally obtain the directional structure with parallel bottom and vertical upper part.
Step ten: under vacuum or inert atmosphere, the aerogel is subjected to high-temperature treatment at 1000-3000 ℃, and is preserved for about 2-4 hours (limited to a specific range), so that the crystallinity of the aerogel is further improved, and the thermal conductivity is further improved.
On the basis of an ice template method, the invention prepares the vertically arranged boron nitride sponge macroscopic body by utilizing chemical reduction shaping and combining two directional freezing casting. The key point of the preparation method is that chemical bonding is realized by utilizing interaction between graphene oxide and boron nitride, and the boron nitride aerogel with an orientation structure is prepared by utilizing ice crystal growth driving and chemical hydrothermal reduction.
Compared with the prior art, the invention has the following advantages:
1. the invention realizes the assembly of the two-dimensional nano-sheets without interaction such as boron nitride or graphene sheets by utilizing the chemical bonding effect of the graphene oxide, and reduces the use of organic binders.
2. The invention can dry the hydraulic component under the air condition, avoids conventional freeze drying and simplifies the preparation.
3. According to the invention, samples with different sizes can be prepared by designing the moulds with different sizes, and large-size sample preparation can be realized.
4. According to the invention, an upward temperature gradient (directional arrangement in the Z-axis direction) is provided for the sample through the cold source, the liquid crystal property of the pre-reduced graphene oxide is changed, the fluidity is poor, and the vertical structure can be maintained.
5. After chemical hydrothermal reduction, the interaction between graphene oxide sheets is realized by partial reduction, meanwhile, the interaction between the graphene oxide sheets and boron nitride is maintained, mixed hydrogel is formed, the mechanical strength of an orientation structure is enhanced by repeated freezing, no capillary action is caused in the air drying process, and the complete structure is maintained.
Drawings
FIG. 1 is a flow chart of boron nitride aerogel preparation with vertical structure;
FIG. 2 is a schematic diagram of a boron nitride aerogel production apparatus having a vertical structure;
FIG. 3 is a graphical representation of the boron nitride aerogel prepared in example 1;
fig. 4 is an overall SEM image of the sample in example 1, the upper image being in the vertical direction, the lower image being SEM images in both horizontal directions.
In the figure, 1: cold source, 2: high heat conduction base, 3: low thermal conductivity sidewall, 4: an oriented structure.
Detailed Description
The following embodiments are provided to further illustrate the technical scheme of the present invention, but not to limit the technical scheme, and all modifications and equivalent substitutions are included in the scope of the present invention without departing from the spirit and scope of the technical scheme.
Example 1
The embodiment provides a construction method for preparing oriented boron nitride aerogel by a low-cost method without freeze drying, as shown in fig. 1, the specific steps of the method are as follows:
1) Preparing graphene oxide dispersion liquid: 4g of flake graphite is weighed and placed in a beaker, 450ml of concentrated sulfuric acid and 50ml of phosphoric acid are poured into the beaker to prepare a mixed solution I, and the mixed solution I is stirred for 40 minutes at room temperature. Placing the beaker in a water bath for water bath heating, adding 18g of potassium permanganate into the mixed solution I for 8 times to obtain a mixed solution II, heating the mixed solution II at a constant temperature of 70 ℃, taking out after 16 hours, and cooling at room temperature. After cooling to room temperature, slowly pouring the mixed solution II into 700ml of hydrogen peroxide mixed ice water, standing for 24 hours, filtering out supernatant, taking the lower solution, and centrifugally washing to obtain the high-concentration graphene oxide solution. And finally dispersing the washed high-concentration graphene oxide solution in deionized water to obtain a graphene oxide dispersion liquid with the concentration of 20mg/mL for later use. The prepared graphene oxide dispersion liquid is placed in an environment of 11 ℃ for heat balance. The preparation method of the 700ml hydrogen peroxide mixed ice water comprises the steps of dissolving 6ml of hydrogen peroxide solution with the mass fraction of 30% in water to form 700ml of mixed solution III, and placing the mixed solution III in a refrigerator in a subzero environment for freezing to obtain the hydrogen peroxide mixed ice water.
2) Mixing boron nitride and graphene oxide in a separate solution: 100ml of graphene oxide dispersion liquid with the concentration of 10mg/ml is taken and placed in a beaker, 5g of boron nitride is added into the solution in batches, and the mixture is mixed by shaking for 10min by using a cell pulverizer.
3) Pre-reducing the boron nitride mixed solution: after adding 2g of ascorbic acid into a beaker, manually stirring for 10min, placing the mixed solution in a vacuum device, vacuumizing, maintaining the pressure for 15min under the vacuum degree of-0.1 MPa, repeating for 3 times, placing the mixed solution in a room temperature environment for 2h, and treating until the liquid has no fluidity.
3) The pre-reduced mixed solution was subjected to thermal equilibration at 9 ℃ for 1 h. After removal, ordered assembly is performed on the freezer. The liquid level of liquid nitrogen is 4cm away from the top of the container, and the freezing time is controlled to be 20min. The refrigerating device is shown in figure 2 and comprises a cold source, a refrigerating container and a refrigerating mould, wherein the cold source is an insulated polyethylene container, and liquid nitrogen is filled in the cold source; the freezing container is a stainless steel container, and organic solvents such as ethanol and the like are filled in the freezing container to serve as soaking solution; the bottom of the freezing mould is an aluminum plate with the thickness of 13 x 1cm, the side wall is a square silica gel frame with the width of 1cm and the thickness of 1.5cm, and the external length of the frame is 9cm.
5) Thawing the frozen boron nitride ice crystal mixture at room temperature, placing the frozen boron nitride ice crystal mixture in the air at 60 ℃ for preforming treatment for 1.5 hours after the frozen boron nitride ice crystal mixture is completely thawed, and taking out the sample after the sample forms a jelly shape.
6) After cooling to room temperature, the sample was placed in a 9 ℃ environment for 1h of thermal equilibration, and after equilibration, secondary directional freezing was performed.
7) After thawing the twice frozen sample, placing the sample in an air condition of 60 ℃ for reaction for 4 hours until the sample is molded.
8) And cooling the molded sample to room temperature, and then putting the cooled sample into a refrigerator at the temperature of minus 30 ℃ for freezing, and carrying out skeleton reinforcement treatment for 3 hours.
9) And taking out and thawing the completely frozen sample, transferring the sample into other containers from a mold after the completely frozen sample is thawed, adding 10ml of deionized water, and reacting for 5 hours at 60 ℃ and 6 hours at 80 ℃ under the air condition to obtain the mild boron nitride hydrogel with certain chemical property.
10 Hydrogel washing and drying): cooling the hydrogel, adding 50ml of deionized water, soaking and washing, heating the solution at 65 ℃ for 15min during washing, taking out the hydrogel after washing for 4 times, and heating and drying in a blast drying oven at 60 ℃ to obtain the vertical oriented boron nitride aerogel (figure 3).
Fig. 4 is an overall SEM image of the boron nitride aerogel having a vertical structure prepared in this example. As can be seen from the figure, the embodiment prepares the orientation structure with long range order.
When the thermal conductivity of the thermal interface material prepared by the embodiment is tested, the thermal conductivity in the vertical direction can reach 1W/m.K when the volume fraction of the boron nitride is 2vol.%, and the horizontal thermal conductivity is 0.2W/m.K, so that the anisotropy of the thermal conductivity is shown.
Example 2
The embodiment provides a construction method for preparing oriented boron nitride aerogel by a low-cost method without freeze drying, as shown in fig. 1, the specific steps of the method are as follows:
1) Preparing graphene oxide dispersion liquid: 4g of flake graphite is weighed and placed in a beaker, 450ml of concentrated sulfuric acid and 50ml of phosphoric acid are poured into the beaker to prepare a mixed solution I, and the mixed solution I is stirred for 40 minutes at room temperature. Placing the beaker in a water bath for water bath heating, adding 18g of potassium permanganate into the mixed solution I for 8 times to obtain a mixed solution II, heating the mixed solution II at a constant temperature of 70 ℃, taking out after 16 hours, and cooling at room temperature. After cooling to room temperature, slowly pouring the mixed solution II into 700ml of hydrogen peroxide mixed ice water, standing for 24 hours, filtering out supernatant, taking the lower solution, and centrifugally washing to obtain the high-concentration graphene oxide solution. And finally dispersing the washed high-concentration graphene oxide solution in deionized water to obtain a graphene oxide dispersion liquid with the concentration of 20mg/mL for later use. The prepared graphene oxide dispersion liquid is placed in an environment of 11 ℃ for heat balance. The preparation method of the 700ml hydrogen peroxide mixed ice water comprises the steps of dissolving 6ml of hydrogen peroxide solution with the mass fraction of 30% in water to form 700ml of mixed solution III, and placing the mixed solution III in a refrigerator in a subzero environment for freezing to obtain the hydrogen peroxide mixed ice water.
2) Mixing boron nitride and graphene oxide in a separate solution: 100ml of graphene oxide dispersion liquid with the concentration of 10mg/ml is taken and placed in a beaker, 5g of boron nitride is added into the solution in batches, and the mixture is mixed by shaking for 10min by using a cell pulverizer.
3) Pre-reducing the boron nitride mixed solution: after adding 2g of ascorbic acid into a beaker, manually stirring for 10min, placing the mixed solution in a vacuum device, vacuumizing, maintaining the pressure for 15min under the vacuum degree of-0.1 MPa, repeating for 3 times, placing the mixed solution in a room temperature environment for 2h, and treating until the liquid has no fluidity.
3) The pre-reduced mixed solution was subjected to thermal equilibration at 9 ℃ for 1 h. After removal, ordered assembly is performed on the freezer. The liquid level of liquid nitrogen is 4cm away from the top of the container, and the freezing time is controlled to be 20min. The refrigerating device is shown in figure 2 and comprises a cold source, a refrigerating container and a refrigerating mould, wherein the cold source is an insulated polyethylene container, and liquid nitrogen is filled in the cold source; the freezing container is a stainless steel container, and organic solvents such as ethanol and the like are filled in the freezing container to serve as soaking solution; the bottom of the freezing mould is an aluminum plate with the thickness of 13 x 1cm, the side wall is a square silica gel frame with the width of 1cm and the thickness of 1.5cm, and the external length of the frame is 9cm.
5) Thawing the frozen boron nitride ice crystal mixture at room temperature, placing the frozen boron nitride ice crystal mixture in the air at 60 ℃ for preforming treatment for 1.5 hours after the frozen boron nitride ice crystal mixture is completely thawed, and taking out the sample after the sample forms a jelly shape.
6) After cooling to room temperature, the sample was placed in a 9 ℃ environment for 1h of thermal equilibration, and after equilibration, secondary directional freezing was performed.
7) After thawing the twice frozen sample, placing the sample in an air condition of 60 ℃ for reaction for 4 hours until the sample is molded.
8) And cooling the molded sample to room temperature, and then putting the cooled sample into a refrigerator at the temperature of minus 30 ℃ for freezing, and carrying out skeleton reinforcement treatment for 3 hours.
9) And taking out and thawing the completely frozen sample, transferring the sample into other containers from a mold after the completely frozen sample is thawed, adding 10ml of deionized water, and reacting for 5 hours at 60 ℃ and 6 hours at 80 ℃ under the air condition to obtain the mild boron nitride hydrogel with certain chemical property.
10 Hydrogel washing and drying): cooling the hydrogel, adding 50ml of deionized water, soaking and washing, heating the solution at 65 ℃ for 15min during washing, taking out the hydrogel after washing for 4 times, and heating and drying in a blast drying oven at 60 ℃ to obtain the vertical oriented boron nitride aerogel (figure 3).
11 Under nitrogen protection, the aerogel is treated at 2000 ℃.
When the thermal conductivity of the thermal interface material prepared by the embodiment is tested, the thermal conductivity in the vertical direction can reach 6W/m.K when the volume fraction of the boron nitride is 2vol.%, and the horizontal thermal conductivity is 1W/m.K, so that the anisotropy of the thermal conductivity is shown.
Example 3
The embodiment provides a construction method for preparing oriented boron nitride aerogel by a low-cost method without freeze drying, as shown in fig. 1, the specific steps of the method are as follows:
1) Preparing graphene oxide dispersion liquid: 4g of flake graphite is weighed and placed in a beaker, 450ml of concentrated sulfuric acid and 50ml of phosphoric acid are poured into the beaker to prepare a mixed solution I, and the mixed solution I is stirred for 40 minutes at room temperature. Placing the beaker in a water bath for water bath heating, adding 18g of potassium permanganate into the mixed solution I for 8 times to obtain a mixed solution II, heating the mixed solution II at a constant temperature of 70 ℃, taking out after 16 hours, and cooling at room temperature. After cooling to room temperature, slowly pouring the mixed solution II into 700ml of hydrogen peroxide mixed ice water, standing for 24 hours, filtering out supernatant, taking the lower solution, and centrifugally washing to obtain the high-concentration graphene oxide solution. And finally dispersing the washed high-concentration graphene oxide solution in deionized water to obtain a graphene oxide dispersion liquid with the concentration of 20mg/mL for later use. The prepared graphene oxide dispersion liquid is placed in an environment of 11 ℃ for heat balance. The preparation method of the 700ml hydrogen peroxide mixed ice water comprises the steps of dissolving 6ml of hydrogen peroxide solution with the mass fraction of 30% in water to form 700ml of mixed solution III, and placing the mixed solution III in a refrigerator in a subzero environment for freezing to obtain the hydrogen peroxide mixed ice water.
2) Mixing boron nitride and graphene oxide in a separate solution: 100ml of graphene oxide dispersion liquid with the concentration of 10mg/ml is taken and placed in a beaker, 5g of boron nitride is added into the solution in batches, and the mixture is mixed by shaking for 10min by using a cell pulverizer.
3) Pre-reducing the boron nitride mixed solution: after adding 2g of ascorbic acid into a beaker, manually stirring for 10min, placing the mixed solution in a vacuum device, vacuumizing, maintaining the pressure for 15min under the vacuum degree of-0.1 MPa, repeating for 3 times, placing the mixed solution in a room temperature environment for 2h, and treating until the liquid has no fluidity.
3) The pre-reduced mixed solution was subjected to thermal equilibration at 9 ℃ for 1 h. After removal, ordered assembly is performed on the freezer. The liquid level of liquid nitrogen is 4cm away from the top of the container, and the freezing time is controlled to be 20min. The refrigerating device is shown in figure 2 and comprises a cold source, a refrigerating container and a refrigerating mould, wherein the cold source is an insulated polyethylene container, and liquid nitrogen is filled in the cold source; the freezing container is a stainless steel container, and organic solvents such as ethanol and the like are filled in the freezing container to serve as soaking solution; the bottom of the freezing mould is an aluminum plate with the thickness of 13 x 1cm, the side wall is a square silica gel frame with the width of 1cm and the thickness of 1.5cm, and the external length of the frame is 9cm.
5) Thawing the frozen boron nitride ice crystal mixture at room temperature, placing the frozen boron nitride ice crystal mixture in the air at 60 ℃ for preforming treatment for 1.5 hours after the frozen boron nitride ice crystal mixture is completely thawed, and taking out the sample after the sample forms a jelly shape.
6) After cooling to room temperature, the sample was placed in a 9 ℃ environment for 1h of thermal equilibration, and after equilibration, secondary directional freezing was performed.
7) After thawing the twice frozen sample, placing the sample in an air condition of 60 ℃ for reaction for 4 hours until the sample is molded.
8) And cooling the molded sample to room temperature, and then putting the cooled sample into a refrigerator at the temperature of minus 30 ℃ for freezing, and carrying out skeleton reinforcement treatment for 3 hours.
9) And taking out and thawing the completely frozen sample, transferring the sample into other containers from a mold after the completely frozen sample is thawed, adding 10ml of deionized water, and reacting for 5 hours at 60 ℃ and 6 hours at 80 ℃ under the air condition to obtain the mild boron nitride hydrogel with certain chemical property.
10 Hydrogel washing and drying): cooling the hydrogel, adding 50ml of deionized water, soaking and washing, heating the solution at 65 ℃ for 15min during washing, taking out the hydrogel after washing for 4 times, and heating and drying in a blast drying oven at 60 ℃ to obtain the vertical oriented boron nitride aerogel (figure 3).
11 Under nitrogen protection, the aerogel is subjected to 3000 ℃.
When the thermal conductivity of the thermal interface material prepared by the embodiment is tested, the thermal conductivity in the vertical direction can reach 13W/m.K when the volume fraction of the boron nitride is 2vol.%, and the horizontal thermal conductivity is 1.6W/m.K, so that the anisotropy of the thermal conductivity is shown.
Comparative example 1
This comparative example attempts to prepare boron nitride aerogels without using graphene oxide as a binder, intended to be compared with examples 1-3, the specific steps of the method are as follows:
1) Mixing boron nitride solution: 100ml of deionized water was placed in a beaker, 5g of boron nitride was added to the solution in portions, and the mixture was mixed by shaking for 10min with a cell pulverizer.
3) Pre-reduction of boron nitride solution: after adding 2g of ascorbic acid in a beaker, stirring for 10min manually, placing the mixed solution in a vacuum device, vacuumizing, maintaining the pressure for 15min under the vacuum degree of-0.1 MPa, repeating for 3 times, and standing the mixed solution for 2h at room temperature.
3) The pre-reduced mixed solution was subjected to thermal equilibration at 9 ℃ for 1 h. After removal, ordered assembly is performed on the freezer. The liquid level of liquid nitrogen is 4cm away from the top of the container, and the freezing time is controlled to be 20min. The refrigerating device is shown in figure 2 and comprises a cold source, a refrigerating container and a refrigerating mould, wherein the cold source is an insulated polyethylene container, and liquid nitrogen is filled in the cold source; the freezing container is a stainless steel container, and organic solvents such as ethanol and the like are filled in the freezing container to serve as soaking solution; the bottom of the freezing mould is an aluminum plate with the thickness of 13 x 1cm, the side wall is a square silica gel frame with the width of 1cm and the thickness of 1.5cm, and the external length of the frame is 9cm.
5) Thawing the frozen boron nitride ice crystal mixture at room temperature, and after complete thawing, performing preforming treatment at 60 ℃ for 1.5h, and taking out the sample.
6) After cooling to room temperature, the sample was placed in a 9 ℃ environment for 1h of thermal equilibration, and after equilibration, secondary directional freezing was performed.
7) After thawing the twice frozen sample, placing the sample in an air condition of 60 ℃ for reaction for 4 hours until the sample is molded.
8) Cooling the molded sample to room temperature, and then putting the cooled sample into a refrigerator at the temperature of minus 30 ℃ for freezing for 3 hours.
9) And taking out the completely frozen sample, thawing, adding 10ml of deionized water after complete thawing, and reacting for 5 hours at 60 ℃ and 6 hours at 80 ℃.
10 Solution drying: the sample obtained in step 9 was heated and dried in a blow-drying oven at 60 ℃.
The boron nitride hydrogel and the aerogel cannot be obtained through the comparative example steps, after hydrothermal reduction, the boron nitride is still in a mixed solution state, and after drying by a blast drying oven, the boron nitride powder is obtained.
Claims (10)
1. The method for constructing the oriented boron nitride aerogel by using the low-cost method without freeze drying is characterized by comprising the following steps of:
step one: uniformly dispersing boron nitride in a graphene oxide solution, wherein the mass ratio of the boron nitride to the graphene oxide is not higher than 1-5: 1, a step of;
step two: placing the boron nitride mixed solution in a freezing mold, fully mixing the boron nitride mixed solution with a reducing agent, and then performing pre-reduction treatment, wherein the mass ratio of graphene oxide to the reducing agent is controlled to be 1:1 to 5;
step three: carrying out heat balance on the mixed solution after pre-reduction, and placing the mixed solution after heat balance in a refrigerating device for directional refrigeration;
step four: thawing the frozen sample, and heating the sample under the air condition after the frozen sample is completely thawed, so that the sample is converted into hydrogel;
step five: cooling the hydrogel to room temperature, performing heat balance, and then placing the hydrogel in a refrigerating device for secondary directional refrigeration to strengthen the structure orientation;
step six: after the secondary frozen sample is completely thawed, heating is carried out under the air condition, so that the hydrogel is thoroughly formed;
step seven: cooling the thoroughly formed hydrogel to room temperature, and putting the hydrogel into a refrigerator for freezing to improve the mechanical property of the hydrogel;
step eight: thawing the frozen hydrogel, heating under air condition, and further reducing the obtained hydrogel;
step ten: washing the reduced hydrogel with deionized water to remove the internal solution, and heating and drying to obtain boron nitride aerogel with a vertical structure;
step eleven: and (3) carrying out high-temperature treatment on the boron nitride aerogel at 1000-3000 ℃ under vacuum or inert atmosphere.
2. The method of claim 1, wherein in the first step, the graphene oxide concentration is not less than 5-15 mg/ml.
3. The method for constructing the oriented boron nitride aerogel by the low-cost freeze-drying-free method according to claim 1, wherein in the second step, the reducing agent is one of ascorbic acid, potassium hydroxide, hydroiodic acid, hydrazine hydrate and sodium borohydride; the bottom heat conductivity of the freezing mould is 5-400W m -1 K -1 Has a sidewall thermal conductivity of 0.01 to 2Wm -1 K -1 Is composed of a polymer of (a).
4. The method for constructing the oriented boron nitride aerogel by the low-cost freeze-drying-free method according to claim 1, wherein in the second step, the time of the pre-reduction treatment is controlled within 1-3 h.
5. The method for constructing a low-cost, freeze-drying-free oriented boron nitride aerogel according to claim 1, wherein in the third and sixth steps, a heat balance treatment is performed at 5-15 ℃ for 1-10 hours.
6. The method for constructing a low-cost, freeze-drying-free oriented boron nitride aerogel according to claim 1, wherein in step five, the thawed sample is heated at 50-70 ℃ for 2-4 hours.
7. The method for constructing the oriented boron nitride aerogel by the low-cost freeze-drying-free method according to claim 1, wherein in the step seven, the unfrozen sample is reacted for 3-4 hours under the air condition of 50-60 ℃ to thoroughly form the hydrogel.
8. The method for constructing a low-cost, freeze-drying-free oriented boron nitride aerogel according to claim 1, wherein in step eight, the hydrogel is frozen at-20 to-30 ℃.
9. The method for constructing the oriented boron nitride aerogel by the low-cost freeze-drying-free method according to claim 1, wherein in the step nine, the unfrozen hydrogel is reduced under the air condition of 50-90 ℃ for 8-12 h.
10. The method for constructing the oriented boron nitride aerogel by the low-cost freeze-drying-free method according to claim 1, wherein in the step ten, the hydrogel washed by deionized water is dried for 5-10 hours under the air condition of 50-70 ℃.
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