CN114574169B - Vanadium dioxide-boron nitride phase-change heat-conducting composite material and preparation method and application thereof - Google Patents
Vanadium dioxide-boron nitride phase-change heat-conducting composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a vanadium dioxide-boron nitride phase-change heat-conducting composite material, and a preparation method and application thereof. The preparation method comprises the following steps: carrying out hydrothermal reaction on vanadium salt, a reducing agent, boron nitride and a doping agent in a solvent; wherein the boron nitride is hexagonal boron nitride. According to the invention, a hydrothermal method is adopted to synthesize the vanadium dioxide-boron nitride phase-change heat-conducting composite material, and nano vanadium dioxide is adsorbed on the hexagonal boron nitride nanosheets. On the one hand, the vanadium dioxide is used for endowing the material with phase change heat storage capacity; on the other hand, through the electron-phonon coupling effect between vanadium dioxide and boron nitride, higher heat conductivity is obtained under the condition of lower boron nitride loading, the production cost is reduced, and meanwhile, the protection effect of the boron nitride on the vanadium dioxide is improved, and the heat stability of the vanadium dioxide is improved. Compared with the prior art, the heat-conducting material has the advantages of no oil spilling phenomenon, good heat stability and high heat conductivity coefficient.
Description
Technical Field
The invention relates to the technical field of chemical engineering, in particular to a vanadium dioxide-boron nitride phase-change heat-conducting composite material and a preparation method and application thereof.
Background
The phase change material (Phase Change Material, PCM) is capable of changing state of matter and providing latent heat without changing temperature. Wherein, the traditional organic phase-change material has large phase-change enthalpy value, low cost, mild property, no supercooling, corrosion and the likeThe problems are low in price and easy to obtain, and the method is always a hot spot for research in the field of phase change materials. However, the organic phase change material has two major difficulties in application, namely, the organic phase change material mostly belongs to the category of solid-liquid phase change materials, the material is in a liquid state after absorbing heat, the change of the phase change volume is large, the phenomenon of oil spilling is easy to occur, and the thermal stability is poor; secondly, the heat conductivity coefficient of the organic phase change material is generally smaller and is generally 0.15-0.3W/(m.K), so that the heat storage and release speed of the material are influenced, and the use is influenced. Compared with the organic phase change material, the inorganic phase change material has the characteristics of repeated use, no oil spilling phenomenon generally, high long-term use reliability and environmental protection, and has wide application prospect in the field of heat conduction materials. The vanadium dioxide has the primary reversible phase change at 68 ℃, has the phase change heat storage capacity, has small volume change in the phase change process, and has the intrinsic thermal conductivity of 4-6W.m -1 ·K -1 The vanadium dioxide has better heat conduction capability, but is easy to oxidize after being placed in the air for a long time, and has poorer heat stability.
Hexagonal boron nitride has a lamellar crystal structure resembling graphite and is therefore also referred to as "white graphene". The material has good electrical insulation, thermal conductivity and chemical stability, and is a good refractory and high-temperature-resistant material and a good heat-conducting material. Therefore, the preparation of the vanadium dioxide-boron nitride composite material is expected to obtain the phase change material with better heat conducting property and reliable stability.
Disclosure of Invention
Aiming at the background technology, the invention provides a vanadium dioxide-boron nitride phase-change heat-conducting composite material, a preparation method and application thereof, and the phase-change heat-conducting composite material is innovatively assembled into a composite structure with phase-change heat storage and high heat-conducting capability through organic solvent heat treatment by utilizing the phase-change heat storage capability of vanadium dioxide and the good heat stability and the excellent heat conducting capability of hexagonal boron nitride, so that a novel phase-change heat-conducting material with good heat stability is provided.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the invention provides a preparation method of a vanadium dioxide-boron nitride phase-change heat-conducting composite material, which comprises the following steps:
carrying out organic solvothermal reaction on vanadium salt, a reducing agent, boron nitride and a doping agent in an organic solvent;
wherein the boron nitride is hexagonal boron nitride.
In a preferred embodiment, the vanadium salt is a +5 valent vanadium salt, and specific examples thereof include ammonium metavanadate, ammonium pyrovanadate, ammonium orthovanadate, ammonium polyvanadate, ammonium decavanadate, and the like, and the above vanadium salts may be used singly or in any combination.
As a preferred embodiment, the reducing agent is selected from any one or more of oxalic acid, citric acid, formic acid and acetic acid.
As a preferred embodiment, the dopant is selected from any one or more of (1) salts of tungsten, magnesium, molybdenum, niobium, tantalum, zinc, aluminum, copper, (2) transition metal telluride, and (3) tellurium oxide compound;
preferably, the dopant is selected from any one or a mixture of ammonium tungstate and tellurium dioxide; it is further preferable to use a mixture of ammonium tungstate and tellurium dioxide.
In the technical scheme of the invention, the transition metal telluride can be vanadium telluride, titanium telluride, tungsten telluride, molybdenum telluride, copper telluride, zinc telluride, tin telluride and the like; examples of the tellurium oxide compound include tellurium oxide, tellurium sulfide, and tellurium selenide.
As a preferred embodiment, the organic solvent is any one or more of ethanol, N-Dimethylformamide (DMF), isopropanol and N-methylpyrrolidone (NMP).
In a preferred embodiment, the temperature of the organic solvent thermal reaction is 180 to 260 ℃, for example 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃ or any value therebetween;
preferably, the time of the organic solvent thermal reaction is 12-24 hours;
preferably, the organic solvent thermal reaction is carried out under the stirring condition, and the stirring rotating speed is preferably 100-500 r/min.
In certain specific embodiments, the method of making further comprises post-treatment; the post-treatment comprises centrifugation, washing, drying and annealing; the washing is respectively washing with ethanol and acetone; the drying is carried out for 4-12 hours at the temperature of 40-80 ℃; the annealing is 600-800 ℃ annealing for 2-5 hours, such as 600 ℃ annealing, 620 ℃ annealing, 640 ℃ annealing, 660 ℃ annealing, 680 ℃ annealing, 700 ℃ annealing, 720 ℃ annealing, 740 ℃ annealing, 760 ℃ annealing, 780 ℃ annealing, 800 ℃ annealing.
In the technical scheme of the invention, the VO with the phase change function can be improved by annealing 2 Purity of the phases.
As a preferred embodiment, the preparation method specifically comprises the following steps:
1) Dissolving ammonium metavanadate, oxalic acid, hexagonal boron nitride, ammonium tungstate and/or tellurium dioxide in an organic solvent to obtain a dispersion liquid;
2) Heating the dispersion liquid obtained in the step 1) to 180-260 ℃ under the stirring of 100-500 r/min, and reacting for 12-24 hours;
3) Centrifuging the product obtained in the step 2), discarding clear liquid, washing and washing out residual reactants by using ethanol and acetone respectively, centrifuging, and drying in a vacuum drying oven at 40-80 ℃ for 4-12 h;
4) And (3) annealing the product obtained in the step (3) for 2-5 hours at 600-800 ℃ to obtain pure-phase-change vanadium dioxide.
Preferably, in the step 1), the dosage ratio of the ammonium metavanadate, oxalic acid, hexagonal boron nitride, ammonium tungstate and tellurium dioxide is (100-300 mg): (200-700 mg): (50-150 mg): (2.7-7.5 mg): (0.8-4.0 mg).
In still another aspect, the invention provides the vanadium dioxide-boron nitride phase-change heat-conducting composite material obtained by the preparation method.
In yet another aspect, the present invention provides the use of the vanadium dioxide-boron nitride phase change thermally conductive composite material described above in the preparation of a thermal interface material.
The technical scheme has the following advantages or beneficial effects:
according to the invention, a hydrothermal method is adopted to synthesize the vanadium dioxide-boron nitride phase-change heat-conducting composite material, and nano vanadium dioxide is adsorbed on the hexagonal boron nitride nanosheets. In the organic solvent thermal reaction process, the hexagonal boron nitride powder is thermally stripped by an organic solvent to obtain hexagonal boron nitride nano-sheets, and simultaneously, a pentavalent vanadium source is reduced to tetravalent vanadium, and vanadium dioxide grows in situ on the hexagonal boron nitride nano-sheets. On one hand, the phase change heat storage capacity is endowed to the composite material through vanadium dioxide; on the other hand, through the electron-phonon coupling effect between vanadium dioxide and boron nitride, higher heat conductivity is obtained under the condition of lower boron nitride loading, so that the production cost can be reduced, and meanwhile, the boron nitride plays a role in protecting the vanadium dioxide, and the heat stability of the vanadium dioxide is improved. Compared with the prior art, the heat-conducting material has the advantages of no oil spilling phenomenon, good heat stability and high heat conductivity coefficient. In addition, the phase transition temperature of the vanadium dioxide is reduced by doping metal ions, and the application range of the phase transition material is enlarged.
Drawings
Fig. 1 is an SEM image of the vanadium dioxide-boron nitride composite material prepared in example 1.
FIG. 2 is a graph of the differential calorimetric test results of the vanadium dioxide-boron nitride composites prepared in examples 1-4 and commercial vanadium dioxide.
FIG. 3 is a Differential Scanning Calorimetric (DSC) curve of the vanadium dioxide-boron nitride composite prepared in example 1 and commercial vanadium dioxide and its 300℃heat treatment of 3 h.
Detailed Description
The following examples are only some, but not all, of the examples of the invention. Accordingly, the detailed description of the embodiments of the invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the present invention, all the equipment, raw materials and the like are commercially available or commonly used in the industry unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
In the following examples, hexagonal boron nitride was in the form of powder, which was purchased from national pharmaceutical chemicals Co., ltd.
Example 1:
(1) 200 mg ammonium metavanadate, 461.5 mg oxalic acid, 100mg hexagonal boron nitride and 15 mL isopropanol are added into a glass beaker, 4.36 mg ammonium tungstate and 1.36 mg tellurium dioxide are added, and the mixture is stirred for 30min to obtain a dispersion liquid;
(2) Transferring the dispersion liquid into a hydrothermal reaction kettle, adding polytetrafluoroethylene stirring magneton, and sealing; under the magnetic stirring condition, the reaction kettle is gradually heated to 260 ℃, the stirring speed is set to 400 r/min, and the reaction is carried out for 24 hours;
(3) Cooling to room temperature after the reaction is completed, opening a reaction kettle, transferring the product into a centrifuge tube, centrifuging for 10 minutes at 8000 revolutions per minute, discarding clear liquid, washing for 1 time by using ethanol and acetone respectively, centrifuging again under the same condition, and drying the product in a vacuum drying oven at 40 ℃ for 5 hours;
(4) And (3) placing the obtained product in a tube furnace, annealing at 800 ℃ for 2 hours under nitrogen atmosphere, and cooling to room temperature to obtain the vanadium dioxide-boron nitride phase-change heat-conducting composite material.
The vanadium dioxide-boron nitride phase change heat conduction composite material prepared in the embodiment is a nano sheet material, and as shown in fig. 1, vanadium dioxide is successfully attached to a boron nitride nano sheet.
Example 2:
(1) 200, mg ammonium metavanadate, 461.5 mg oxalic acid, 100mg hexagonal boron nitride and 20, mL ethanol are added into a glass beaker, 4.36, mg ammonium tungstate and 2.72, mg tellurium dioxide are added, and stirring is carried out for 30min to obtain a dispersion liquid;
(2) Transferring the dispersion liquid into a hydrothermal reaction kettle, adding polytetrafluoroethylene stirring magneton, and sealing; under the magnetic stirring condition, the reaction kettle is gradually heated to 260 ℃, the stirring speed is set to 400 r/min, and the reaction is carried out for 24 hours;
(3) Cooling to room temperature after the reaction is completed, opening a reaction kettle, transferring the product into a centrifuge tube, centrifuging for 10 minutes at 8000 revolutions per minute, discarding clear liquid, washing for 1 time by using ethanol and acetone respectively, centrifuging again under the same condition, and drying the product in a vacuum drying oven at 40 ℃ for 5 hours;
(4) And (3) placing the obtained product in a tube furnace, annealing at 800 ℃ for 2 hours under nitrogen atmosphere, and cooling to room temperature to obtain the vanadium dioxide-boron nitride phase-change heat-conducting composite material.
The vanadium dioxide-boron nitride phase-change heat-conducting composite material prepared in the embodiment is a nano sheet material.
Example 3:
(1) 200 mg ammonium metavanadate, 461.5 mg oxalic acid, 100mg hexagonal boron nitride and 20 mg DMF are added into a glass beaker, and 4.36 mg ammonium tungstate is added, and stirred for 30min to obtain a dispersion;
(2) Transferring the dispersion liquid into a hydrothermal reaction kettle, adding polytetrafluoroethylene stirring magneton, and sealing; under the magnetic stirring condition, the reaction kettle is gradually heated to 260 ℃, the stirring speed is set to 400 rpm, and the reaction is carried out for 24 hours;
(3) Cooling to room temperature after the reaction is completed, opening a reaction kettle, transferring the product into a centrifuge tube, centrifuging for 10 minutes at 8000 revolutions per minute, discarding clear liquid, washing for 1 time by using ethanol and acetone respectively, centrifuging again under the same condition, and drying the product in a vacuum drying oven at 40 ℃ for 5 hours;
(4) And (3) placing the obtained product in a tube furnace, annealing at 800 ℃ for 2 hours under nitrogen atmosphere, and cooling to room temperature to obtain the vanadium dioxide-boron nitride phase-change heat-conducting composite material.
The vanadium dioxide-boron nitride phase change heat conduction composite material prepared in the embodiment is a nano sheet material and has a multi-stage structure.
Example 4:
(1) 200 mg ammonium metavanadate, 461.5 mg oxalic acid, 100mg hexagonal boron nitride and 20 mg NMP are added into a glass beaker, 2.72 mg tellurium dioxide is added, and stirring is carried out for 0.5 hour to obtain a dispersion liquid;
(2) Transferring the dispersion liquid into a hydrothermal reaction kettle, adding polytetrafluoroethylene stirring magneton, and sealing; under the magnetic stirring condition, the reaction kettle is gradually heated to 260 ℃, the stirring speed is set to 400 r/min, and the reaction is carried out for 24 hours;
(3) Cooling to room temperature after the reaction is completed, opening a reaction kettle, transferring the product into a centrifuge tube, centrifuging for 10 minutes at 8000 per minute, discarding clear liquid, washing for 1 time respectively by using ethanol and acetone, centrifuging again under the same condition, and drying the product in a vacuum drying oven at 40 ℃ for 5 hours;
(4) And (3) placing the obtained product in a tube furnace, annealing at 800 ℃ for 2 hours under nitrogen atmosphere, and cooling to room temperature to obtain the vanadium dioxide-boron nitride phase-change heat-conducting composite material.
The vanadium dioxide-boron nitride phase-change heat-conducting composite material prepared in the embodiment is a nano sheet material.
Effect examples
(1) Thermal conductivity testing:
the vanadium dioxide-boron nitride phase change heat conductive composite materials prepared in examples 1-4 were added to bisphenol a epoxy resin (containing 40 wt% of curing agent) at 40% wt%, stirred and defoamed in a vacuum mixer at 2000 r/min for 30min, poured into a mold, cured at 165 ℃ for 2 h to obtain test pieces, and tested for heat conductivity on a hot wire transient heat conductivity instrument, and the test results are shown in table 1.
TABLE 1
As can be seen from table 1, the composite material prepared by the invention has good thermal conductivity, wherein the composite material has better thermal conductivity when doped with tungsten and tellurium simultaneously.
(2) Differential scanning calorimeter test:
as can be seen from the results of differential calorimetric test of the composite materials of examples 1-4 and commercial pure vanadium dioxide in FIG. 2, the composite materials of examples 1-4 maintain the primary phase transition characteristics of vanadium dioxide and are lower than the phase transition temperature of commercial pure vanadium dioxide.
(3) Thermal stability:
FIG. 3 shows commercially pure vanadium dioxide (VO 2 ) And vanadium dioxide-boron nitride (VO) prepared in example 1 of the present invention 2 -BN) composite material and differential scanning after being heated at 300 ℃ for 3 hoursA calorimetric (DSC) curve. As can be seen from the figure, pure VO 2 After the heating oxidation treatment, the DSC peak is obviously weakened, namely the heat stability is poor; and VO is 2 The DSC peak of the BN composite material does not change obviously before and after the heating oxidation treatment, which proves that the thermal stability of the BN composite material is obviously improved.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (9)
1. The preparation method of the vanadium dioxide-boron nitride phase-change heat-conducting composite material is characterized by comprising the following steps of:
carrying out organic solvothermal reaction on vanadium salt, a reducing agent, boron nitride and a doping agent in an organic solvent;
wherein the boron nitride is hexagonal boron nitride; the vanadium salt is +5-valent vanadium salt; the doping agent is selected from any one or a mixture of ammonium tungstate and tellurium dioxide;
the vanadium salt is ammonium metavanadate, and the reducing agent is oxalic acid;
the relation of the dosage of the reaction raw materials is as follows:
the dosage ratio of the ammonium metavanadate, oxalic acid, hexagonal boron nitride and ammonium tungstate is (100-300 mg): (200-700 mg): (50-150 mg): (2.7-7.5 mg);
or, the dosage ratio of the ammonium metavanadate, oxalic acid, hexagonal boron nitride and tellurium dioxide is (100-300 mg): (200-700 mg): (50-150 mg): (0.8-4.0 mg);
or, the dosage ratio of the ammonium metavanadate, oxalic acid, hexagonal boron nitride, ammonium tungstate and tellurium dioxide is (100-300 mg): (200-700 mg): (50-150 mg): (2.7-7.5 mg): (0.8-4.0 mg);
the temperature of the organic solvent thermal reaction is 180-260 ℃; the time of the organic solvent thermal reaction is 12-24 hours;
the preparation method also comprises post-treatment; the post-treatment comprises centrifugation, washing, drying and annealing; the annealing is performed for 2-5 hours at 600-800 ℃.
2. The method according to claim 1, wherein the dopant is a mixture of ammonium tungstate and tellurium dioxide.
3. The preparation method according to claim 1, wherein the organic solvent is any one or more of ethanol, N-dimethylformamide, isopropanol and N-methylpyrrolidone.
4. The method of claim 1, wherein the organic solvothermal reaction is performed under stirring.
5. The method according to claim 4, wherein the stirring speed is 100-500 r/min.
6. The method according to claim 1, wherein the washing is ethanol and acetone washing, respectively; and the drying is carried out for 4-12 hours at the temperature of 40-80 ℃.
7. The preparation method according to claim 1, characterized in that it comprises in particular the following steps:
1) Dissolving ammonium metavanadate, oxalic acid, hexagonal boron nitride, ammonium tungstate and/or tellurium dioxide in an organic solvent to obtain a dispersion liquid;
2) Heating the dispersion liquid obtained in the step 1) to 180-260 ℃ under the stirring of 100-500 r/min, and reacting for 12-24 hours;
3) Centrifuging the product obtained in the step 2), discarding clear liquid, washing and washing out residual reactants by using ethanol and acetone respectively, centrifuging, and drying in a vacuum drying oven at 40-80 ℃ for 4-12 h;
4) And (3) annealing the product obtained in the step (3) for 2-5 hours at 600-800 ℃ to obtain the vanadium dioxide-boron nitride phase-change heat-conducting composite material.
8. The vanadium dioxide-boron nitride phase-change heat-conducting composite material obtained by the preparation method of any one of claims 1 to 7.
9. Use of the vanadium dioxide-boron nitride phase change heat conductive composite material of claim 8 in the preparation of a thermal interface material.
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