CN117737689A - Preparation method of large-size high-quality three-dimensional hexagonal boron nitride network - Google Patents
Preparation method of large-size high-quality three-dimensional hexagonal boron nitride network Download PDFInfo
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- 229910052582 BN Inorganic materials 0.000 title claims abstract description 34
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052796 boron Inorganic materials 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 25
- 239000012298 atmosphere Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 230000001276 controlling effect Effects 0.000 claims abstract description 5
- 239000006260 foam Substances 0.000 claims description 121
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 116
- 229910052759 nickel Inorganic materials 0.000 claims description 58
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 50
- 229910052786 argon Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 238000005530 etching Methods 0.000 claims description 18
- 229910052810 boron oxide Inorganic materials 0.000 claims description 15
- 239000012159 carrier gas Substances 0.000 claims description 15
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000001307 helium Substances 0.000 claims description 10
- 229910052734 helium Inorganic materials 0.000 claims description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000004146 energy storage Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
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- 238000009792 diffusion process Methods 0.000 abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 9
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001338 self-assembly Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- Chemical Vapour Deposition (AREA)
Abstract
The invention relates to the field of new materials and application thereof, in particular to a preparation method of a large-size high-quality three-dimensional hexagonal boron nitride (h-BN) network. The method comprises the steps of taking porous metal as a template, uniformly fixing a boron source on the surface of the pore wall of the template through pretreatment, then using a Chemical Vapor Deposition (CVD) process, taking nitrogen-containing gas as a nitrogen source under proper temperature and atmosphere conditions, catalytically growing h-BN on the surface of a porous metal framework, removing a metal substrate to obtain a high-quality three-dimensional h-BN network, and accurately regulating and controlling the pore diameter, morphology, layer number and the like of the three-dimensional h-BN network through regulating and controlling a substrate template and other reaction parameters. Compared with the existing three-dimensional h-BN network preparation process, the method can avoid uneven growth of the h-BN network due to difficulty in bulk diffusion of a boron source in the preparation of the h-BN network by the CVD process, and has the advantages of adjustable h-BN layer number, network morphology and pore, simple process, low production cost and easiness in mass production. The prepared h-BN has high crystallization quality and can be applied to various fields.
Description
Technical Field
The invention relates to the field of new materials and application thereof, in particular to a preparation method of a large-size high-quality three-dimensional hexagonal boron nitride network.
Background
Hexagonal boron nitride (h-BN) exhibits many excellent physicochemical properties such as: the material has excellent mechanical properties, and the in-plane mechanical strength can reach 500N/m; the h-BN also has excellent high temperature resistance, the oxidation resistance temperature in the air is 1000 ℃, and the temperature resistance can reach 2000 ℃ under the vacuum condition; more importantly, the h-BN also has excellent heat conduction performance, and the theoretical heat conduction can reach 1700-2000W/mK, which is 5 times of that of metallic silver and copper; meanwhile, the h-BN has excellent insulating property, the forbidden bandwidth is 5.26eV, the breakdown strength is as high as 35kV/mm, and the dielectric constant is 2.9. Therefore, the h-BN is an ideal heat conduction, insulation and wave transmission material, and the porous network structure has excellent performances of high porosity, low density, high specific surface area, damping, noise reduction and the like. The porous material constructed by the two-dimensional h-BN can have the intrinsic excellent physical properties of the porous structure and the h-BN, and has great potential application advantages in the fields of heat conduction, energy storage, catalysis, adsorption, aerospace and the like.
The preparation method of the h-BN network material mainly comprises two major types of self-assembly and direct growth, wherein the self-assembly method comprises an ice template method, a salt template method, a bubble template method and the like, and the h-BN sheet is lapped by virtue of Van der Waals force and hydrogen bonds to construct a three-dimensional structure, so that the prepared h-BN porous material is unstable and has poor mechanical property. More importantly, because the h-BN sheets are in a lap joint state, a plurality of microcosmic interfaces exist, and the performances such as heat conduction and the like are not ideal; the direct growth method is mainly a Chemical Vapor Deposition (CVD) method, and uses a porous material such as a metal or a polymer as a skeleton to deposit boron nitride on the skeleton. Compared with the self-assembly method, the h-BN is connected with each other through a covalent bond, and the self-assembly method has more excellent performance. However, the precursors used in CVD are still mainly ammonia borane and borazine, which are expensive and toxic and are not suitable for large-scale preparation. Meanwhile, CVD processes commonly utilize volatilization of gaseous nitrogen and boron sources to the substrate surface for growth. However, gaseous boron sources including ammonia borane are ubiquitous and have large molecular weights, are difficult to uniformly diffuse in the bulk phase, and cannot achieve uniform growth of large-size, especially large-thickness, dense Kong Tixiang h-BN networks. Therefore, the development of the large-size high-quality three-dimensional h-BN network large-scale preparation technology which is economical, environment-friendly, simple and efficient has important significance.
Disclosure of Invention
The invention aims to provide a preparation method of a large-size high-quality three-dimensional hexagonal boron nitride network, which solves the problem that a boron source is difficult to uniformly diffuse in a bulk phase commonly faced by the prior preparation of a large-size and dense-pore boron nitride network by using a CVD (chemical vapor deposition) process, and realizes the uniform and controllable preparation of a large-size, especially large-thickness three-dimensional h-BN network.
The technical scheme of the invention is as follows:
the preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network comprises the following steps:
(1) Adding a solid boron source into pores of a foam metal substrate template in a dry powder or dispersion liquid form through shaking, vibrating, repeatedly lifting, ultrasonic or vacuum impregnation mode, and then putting the foam metal loaded with the boron source into an oven for full drying;
(2) Heating the reaction furnace chamber to a preset pretreatment temperature in a carrier gas protective atmosphere;
(3) Putting foam metal with a solid boron source on the surface into a constant temperature area of a reaction furnace chamber, introducing pretreatment atmosphere, and pretreating for 10-120 min;
(4) Cooling the foam metal pretreated in the step (3) in a carrier gas protective atmosphere, and taking out to obtain foam metal with uniformly distributed boron sources on the surface;
(5) Heating the reaction furnace chamber to a set reduction temperature in a carrier gas protective atmosphere;
(6) Placing pretreated foam metal into a constant temperature area of a reaction furnace chamber, and introducing reducing gas for 10-60 min;
(7) Introducing a mixed atmosphere of nitrogen source gas, reducing gas and carrier gas into a reaction furnace chamber, and converting the solid boron source gas and the nitrogen source gas into h-BN on the surface of the foam metal substrate; in the mixed atmosphere, the flow ratio of the nitrogen source gas to the reducing gas to the carrier gas is 1 (0.5-80) (0-100), and the reaction time is 1-500 min;
(8) And (3) cooling the foam metal obtained in the step (7) in the carrier gas protective atmosphere, and taking out to obtain the three-dimensionally communicated high-quality h-BN network structure growing on the foam metal substrate.
According to the preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network, the foam metal substrate is selectively reserved or removed by adopting metal etching liquid according to specific application requirements, and the h-BN from which the foam metal substrate is removed is sufficiently cleaned and dried to obtain the high-quality three-dimensional h-BN network.
In the preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network, in the step (1), solid boron sources comprise one or more than two of boron oxide, boron powder and boric acid.
In the step (1), a foam metal substrate template is foam metal with a three-dimensional communicated open-cell structure, and the foam metal has a certain boron-solid solubility or can form an intermediate product with boron, including but not limited to an alloy formed by one or more than two metals of foam nickel, foam copper, foam iron and foam cobalt; the porosity of the foam metal substrate template is distributed between 50 and 1000PPI, and the density is between 0.1 and 1.5g/cm 3 The thickness is 0.1 mm-50 mm, and the length and width are 0.5 cm-2 m.
In the preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network, in the step (2), the pretreatment temperature is 300-1050 ℃, preferably 600-1000 ℃.
In the preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network, in the step (3), the pretreatment atmosphere is one or more than two of oxygen, argon, nitrogen, helium or hydrogen, the oxygen and the hydrogen cannot be used at the same time, and the flow is 10-5000 sccm.
In the preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network, in the steps (2), (4), (5), (7) and (8), carrier gas is one or two of argon and helium.
In the preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network, in the step (7), nitrogen source gas is ammonia gas or nitrogen gas, and the flow is 10-2000 sccm; in the steps (6) and (7), the reducing gas is hydrogen, and the flow rate of the reducing gas in the step (6) is 10-5000 sccm; in the steps (5), (6) and (7), the temperature of the reaction furnace chamber is 900-1300 ℃.
According to the preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network, the morphology, the porosity and the layer number index of the prepared three-dimensional h-BN network can be accurately regulated and controlled by selecting different foam metal substrates and/or regulating and controlling the temperature, the boron source type, the nitrogen source type and the reaction atmosphere in the preparation process.
The preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network is applied to the fields of heat conduction, energy storage, catalysis, adsorption or aerospace.
The design mechanism of the invention is as follows:
according to the invention, solid boron source particles are firstly loaded in pores of a foam metal template, and the foam metal is treated under specific atmosphere and temperature, so that the boron source is uniformly distributed and fixed on the surface of the foam metal template. Under the catalysis of the foam metal template and at proper temperature, the solid boron source and the gaseous nitrogen source react on the surface of the foam metal template to produce high quality boron nitride layer.
The invention has the following advantages and beneficial effects:
1. compared with an ice template method, a salt template method, a bubble template method and the like, the invention adopts a CVD technology and utilizes h-BN assembly lap joint of micron/nano-scale sheet diameters to form a network with a large number of interfaces in microcosmic. The h-BN network prepared by the CVD process has the characteristics of controllable layer number and natural long-range communication, thereby having more excellent thermal and mechanical properties.
2. The invention adopts foam metal with high catalytic activity as a substrate template, so that the prepared h-BN has excellent crystallization quality.
3. According to the invention, solid boron source particles are loaded in the pores of the foam metal substrate in advance, and the foam metal is treated under specific atmosphere and temperature, so that the boron source is uniformly distributed and fixed on the surface of the foam metal substrate. The method solves the problem that the boron source is difficult to uniformly diffuse in the bulk phase, which is commonly faced by the prior CVD process for preparing the large-size and dense-pore boron nitride network, and realizes the uniform and controllable preparation of the three-dimensional h-BN network with large size, especially large thickness.
4. According to the invention, by selecting different foam metal substrates and/or regulating and controlling parameters such as temperature, boron source type, nitrogen source type, reaction atmosphere and the like in the preparation process, the indexes such as morphology, porosity, aperture, morphology, layer number and the like of the prepared three-dimensional h-BN network can be accurately regulated and controlled. In the invention, the technical index range reached by the three-dimensional h-BN network structure is as follows: average pore diameter of 25-500 μm, porosity of 50-1000 PPI, number of layers of 1-30 and area of 0.25cm 2 ～4m 2 。
5. Compared with precursor materials such as ammonia borane, borazine and the like which are commonly used in conventional CVD, the boron oxide, boron powder or boric acid is used as a solid boron source, the boron oxide/boron powder composite material has the characteristics of low price, safety and innocuity, and lays a foundation for preparing a large-size high-quality three-dimensional h-BN network in a more economic and environment-friendly scale.
6. The invention has simple process, low production cost and easy mass production. Various characterization means show that the prepared boron nitride has high crystallization quality and can be applied to the fields of heat conduction, energy storage, catalysis, adsorption, aerospace and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a nickel foam surface loaded with boron oxide. Wherein fig. 1b is an enlarged view of a portion of fig. 1a, and the box in fig. 1b is marked with boron oxide powder.
FIG. 2 is a representation of the boron distribution energy spectrum of the surface of nickel foam. Wherein, FIG. 2a is foam nickel, and FIG. 2b is nickel foam surface supported boron oxide.
FIG. 3 is a macroscopic photograph of a three-dimensional h-BN network.
FIG. 4 is a three-dimensional h-BN network scanning electron microscope photograph.
FIG. 5 is a Raman spectrum analysis of a three-dimensional h-BN network. In the figure, the abscissa Raman Shift represents the Raman Shift (cm -1 ) The ordinate Intensity represents the relative Intensity (a.u.).
FIG. 6 is an X-ray diffraction (XRD) analysis of a three-dimensional h-BN network, in which: the abscissa 2Theta represents the diffraction angle (degree), and the ordinate Intensity represents the relative Intensity (a.u.).
FIG. 7 is a macroscopic photograph of a three-dimensional h-BN network.
Fig. 8 is a macroscopic photograph of comparative example 1.
FIG. 9 is a scanning electron micrograph of comparative example 1.
FIG. 10 is a macroscopic photograph of comparative example 2.
Detailed Description
In the specific implementation process, the porous metal is taken as a template, the boron source is uniformly fixed on the surface of the pore wall of the template through pretreatment, then the chemical vapor deposition process is utilized, the nitrogen-containing gas is taken as a nitrogen source under the proper temperature and atmosphere conditions, the h-BN is catalytically grown on the surface of the porous metal framework, and the metal substrate is removed, so that the high-quality three-dimensional h-BN network can be obtained.
The present invention will be further described in detail with reference to the drawings and examples.
Example 1:
foamed nickel with dimensions of 5cm by 7cm by 2mm (porosity 110PPI, density 0.2 g/cm) 3 ) Put into a container containing 10g of boron oxide powder, shake and shake for 10min, and take out to obtain foam nickel loaded with certain boron oxide (figure 1). The pretreatment (solidification and uniform diffusion of boron source) is carried out by adopting a CVD horizontal tube furnace, firstly, the central area is heated to 850 ℃ under the protection of argon, 500sccm of hydrogen is introduced, and after the heat preservation is carried out for 30min, the hydrogen is pushed out of the high temperature area and cooled to room temperature. As can be seen from the spectroscopic analysis of the pretreated nickel foam surface, the boron source is uniformly distributed (fig. 2 b) on the nickel foam substrate surface (fig. 2 a). Heating the central area to 1050 ℃ under the protection of argon, putting pretreated foam nickel into a constant temperature area of a reaction furnace chamber, and introducing 500sccm hydrogen for 20min; continuously introducing 500sccm ammonia gas and 500sccm hydrogen gas into the reaction furnace chamberAnd (3) carrying out reaction by using 1000sccm argon, and growing for 1h to obtain a three-dimensional h-BN network growing on the foam nickel. And cooling to room temperature along with the furnace under the protection of argon, and taking out the foam nickel. And (3) etching the foam nickel by adopting hydrochloric acid etching liquid according to the requirements, and cleaning and drying to obtain the three-dimensional h-BN network. In this embodiment, the technical indexes of the three-dimensional h-BN network structure are as follows: an average pore diameter of 230 μm, a porosity of 110PPI, an average number of layers of 5 layers, and an area of 35cm 2 。
The macroscopic state and the microscopic morphology of the three-dimensional h-BN network are respectively shown in the figures 3 and 4, and the h-BN network has a uniform layer number and a natural long-range communicated open pore structure. As shown in FIG. 5, from the Raman spectrum characterization of the obtained sample, the h-BN characteristic peak appears clearly and sharply without defects due to the higher reaction temperature and the catalytic activity of the metal matrix. As shown in FIG. 6, XRD results can show that the characteristic diffraction peak of the three-dimensional h-BN network is obvious, the peak position is 26.5 degrees, the half-width is 0.102 degrees, and no peak position deviation and no impurity peak exist. The results show that the h-BN prepared by the method has high crystallization quality.
As the boron distribution energy spectrum analysis, the three-dimensional h-BN network microcosmic morphology, the Raman spectrum and the XRD result of the foam metal surface in the embodiment are basically consistent with those of the embodiment 1, the description is omitted.
Example 2:
placing foam nickel with size of 2cm×2cm×5mm into container containing 10g boron oxide powder, shaking for 20min, and taking out to obtain foam nickel loaded with certain boron oxide (porosity of 300PPI, density of 0.5 g/cm) 3 ). The preparation method comprises the steps of adopting a CVD horizontal tube furnace to perform pretreatment, firstly heating a central area to 800 ℃ under the protection of argon, introducing 150sccm of hydrogen, keeping the temperature for 1h, pushing out foam nickel from a high-temperature area, and cooling to room temperature to obtain the foam nickel with the surface uniformly loaded with a solid boron source. Heating the central area to 1000 ℃ under the protection of argon, putting pretreated foam nickel into a constant temperature area of a reaction furnace chamber, and introducing 100sccm hydrogen for 30min; continuously introducing 150sccm ammonia gas and 300sccm hydrogen gas into the reaction furnace chamber to react, and growing for 30min to obtain three-dimensional product growing on the foam nickelh-BN network. And cooling to room temperature along with the furnace under the protection of argon, and taking out the foam nickel. After etching the foam nickel by using hydrochloric acid etching solution according to requirements, cleaning and drying to obtain the three-dimensional h-BN network (figure 7). In this embodiment, the technical indexes of the three-dimensional h-BN network structure are as follows: an average pore diameter of 85 μm, a porosity of 300PPI, an average number of layers of 10 layers, and an area of 4cm 2 。
Example 3:
dissolving 3g boron powder in 30ml ethanol, ultrasonic treating for 30min to obtain boron powder uniform dispersion, and mixing foamed nickel with size of 3cm×3cm×5mm (porosity of 160PPI, density of 0.3 g/cm) 3 ) Repeatedly lifting and drying in the boron powder dispersion liquid to obtain the foam nickel loaded with a certain amount of boron powder. The preparation method comprises the steps of adopting a CVD horizontal tube furnace to perform pretreatment, firstly heating a central region to 900 ℃ under the protection of helium, introducing 150sccm of mixed gas of nitrogen and argon according to the volume ratio of 1:1, keeping the temperature for 1h, pushing out foam nickel from a high-temperature region, and cooling to room temperature to obtain the foam nickel with the surface uniformly loaded with a solid boron source. Heating the central area to 1020 ℃ under the protection of helium, putting pretreated foam nickel into a constant temperature area of a reaction furnace chamber, and introducing 800sccm hydrogen for 50min; and continuously introducing 150sccm ammonia gas and 500sccm hydrogen gas into the reaction furnace cavity to react, and growing for 30min to obtain the three-dimensional h-BN network growing on the foam nickel. And cooling to room temperature along with the furnace under the protection of argon, and taking out the foam nickel. And (3) etching the foam nickel by adopting nitric acid etching liquid according to the requirements, and cleaning and drying to obtain the three-dimensional h-BN network. In this embodiment, the technical indexes of the three-dimensional h-BN network structure are as follows: an average pore diameter of 160 μm, a porosity of 160PPI, an average number of layers of 3 and an area of 9cm 2 。
Example 4:
dissolving 10g boric acid in 200ml pure water, ultrasonic treating for 30min to obtain boric acid solution, and separating foamed nickel with size of 5cm×10cm×1cm (porosity 200PPI, density 0.35 g/cm) 3 ) Repeatedly pulling and drying in boric acid solution to obtain foam nickel loaded with a certain amount of boric acid. Pretreating by adopting a CVD horizontal tube furnace, firstly heating the central area to 600 ℃ under the protection of argon, introducing 100sccm of hydrogen for reaction, and preserving the temperature for 1hPushing out the foam nickel from the high temperature area and cooling to room temperature to obtain the foam nickel with the surface uniformly loaded with the solid boron source. Heating the central area to 1050 ℃ under the protection of argon, putting pretreated foam nickel into a constant temperature area of a reaction furnace chamber, and introducing 120sccm hydrogen for 30min; and continuously introducing 150sccm of nitrogen and 300sccm of hydrogen into the reaction furnace cavity to react, and growing for 2 hours to obtain the three-dimensional h-BN network growing on the foam nickel. And cooling to room temperature along with the furnace under the protection of argon, and taking out the foam nickel. And (3) etching the foam nickel by adopting hydrochloric acid etching liquid according to the requirements, and cleaning and drying to obtain the three-dimensional h-BN network. In this embodiment, the technical indexes of the three-dimensional h-BN network structure are as follows: an average pore diameter of 130 μm, a porosity of 200PPI, an average number of layers of 12 layers, and an area of 50cm 2 。
Example 5:
dissolving 50g boric acid in 2000ml pure water, ultrasonic treating for 30min to obtain boric acid solution, and separating foamed nickel with size of 20cm×40cm×1mm (porosity 400PPI, density 0.5 g/cm) 3 ) Repeatedly pulling and drying in boric acid solution to obtain foam nickel loaded with a certain amount of boric acid. The preparation method comprises the steps of adopting a CVD horizontal tube furnace to perform pretreatment, firstly heating a central area to 700 ℃ under the protection of argon, introducing 2000sccm of hydrogen to perform reaction, after heat preservation for 1h, pushing out the foam nickel from a high-temperature area, and cooling to room temperature to obtain the foam nickel with the surface uniformly loaded with a solid boron source. Heating the central area to 1020 ℃ under the protection of argon, putting pretreated foam nickel into a constant temperature area of a reaction furnace chamber, and introducing 2000sccm hydrogen for 40min; and continuously introducing 1000sccm ammonia gas, 3000sccm hydrogen gas and 2000sccm argon gas into the reaction furnace cavity to react, and growing for 3 hours to obtain the three-dimensional h-BN network growing on the foam nickel. And cooling to room temperature along with the furnace under the protection of argon, and taking out the foam nickel. And (3) etching the foam nickel by adopting hydrochloric acid etching liquid according to the requirements, and cleaning and drying to obtain the three-dimensional h-BN network. In this embodiment, the technical indexes of the three-dimensional h-BN network structure are as follows: an average pore diameter of 64 μm, a porosity of 400PPI, an average number of layers of 20 layers, an area of 800cm 2 。
Example 6:
will be of a sizeCopper foam 3cm X2 cm X3 mm (porosity 90PPI, density 0.15 g/cm) 3 ) Putting the copper foam into a container filled with 10g of boron oxide powder, shaking and oscillating for 20min, and taking out to obtain the foam copper loaded with a certain amount of boron oxide. The preparation method comprises the steps of adopting a CVD horizontal tube furnace to perform pretreatment, firstly heating a central area to 800 ℃ under the protection of helium, introducing 150sccm of hydrogen, keeping the temperature for 1h, pushing out the copper foam from a high-temperature area, and cooling to room temperature to obtain the copper foam with the surface uniformly loaded with a solid boron source. Heating the central area to 1000 ℃ under the protection of helium, putting pretreated foamy copper into a constant temperature area of a reaction furnace chamber, and introducing 70sccm hydrogen for 20min; and continuously introducing 100sccm ammonia gas and 200sccm hydrogen gas into the reaction furnace cavity to react, and obtaining the three-dimensional h-BN network growing on the foam copper after the growth for 4 hours. And cooling to room temperature along with the furnace under the protection of argon, and taking out the foam copper. And (3) according to the requirements, etching the copper foam by using sulfuric acid etching solution, and then cleaning and drying to obtain the three-dimensional h-BN network. In this embodiment, the technical indexes of the three-dimensional h-BN network structure are as follows: an average pore diameter of 282 μm, a porosity of 90PPI, an average number of layers of 4 layers, and an area of 6cm 2 。
Example 7:
foam iron (porosity 110PPI, density 0.26 g/cm) with dimensions of 2cm×2cm×1mm 3 ) Putting into a container filled with 10g of boron oxide powder, shaking for 20min, and taking out to obtain foam iron loaded with a certain amount of boron oxide. The preparation method comprises the steps of adopting a CVD horizontal tube furnace to perform pretreatment, firstly heating a central region to 850 ℃ under the protection of helium, introducing 150sccm of hydrogen, keeping the temperature for 1h, pushing foam iron out of a high-temperature region, and cooling to room temperature to obtain the foam iron with the surface uniformly loaded with a solid boron source. Heating the central area to 1150 ℃ under the protection of helium, putting pretreated foam iron into a constant temperature area of a reaction furnace chamber, and introducing 90sccm hydrogen for 20min; continuously introducing 150sccm ammonia gas and 300sccm hydrogen gas into the reaction furnace cavity for reaction, and growing for 30min to obtain the three-dimensional h-BN network growing on the foam iron. And cooling to room temperature along with the furnace under the protection of argon, and taking out the foam iron. And (3) etching the foam iron by adopting hydrochloric acid etching liquid according to the requirements, and cleaning and drying to obtain the three-dimensional h-BN network.In this embodiment, the technical indexes of the three-dimensional h-BN network structure are as follows: an average pore diameter of 230 μm, a porosity of 110PPI, an average number of layers of 6 and an area of 4cm 2 。
Comparative example 1:
2cm 5mm foam Nickel (porosity 110PPI, density 0.2 g/cm) 3 ) Ultrasonic treatment is carried out for 30min in 10%wt BN nano-sheet isopropanol dispersion liquid, the mixture is taken out and dried for 30min on a heat table at 70 ℃, and the process is repeated for three times, thus realizing the foam nickel with the surface loaded with BN nano-sheets. And (3) adopting a CVD horizontal tube furnace to grow, pushing the foam nickel into a central temperature zone, heating to 1050 ℃ under the protection of argon atmosphere, and preserving heat for 2 hours. And cooling the foam nickel to room temperature along with a furnace under the protection of argon, taking out the foam nickel, etching the foam nickel in hydrochloric acid, and fully cleaning and drying to obtain the high-temperature sintered h-BN network. As shown in fig. 8 and 9, the material is fragile and can not form a complete and communicated three-dimensional network structure in microcosmic because the material only depends on weak interaction force between molecules during sintering, the material is obviously collapsed, the lap joint between the sheet layers is loose, and the layer number is not controllable.
Comparative example 2:
the growth was carried out using a CVD horizontal tube furnace. First, 1 cm. Times.1 cm. Times.5 mm nickel foam (porosity 110PPI, density 0.2 g/cm) 3 ) Placing the powder in a central temperature area of a tube furnace, weighing 0.3g of ammonia borane powder, placing the powder into a quartz boat, pushing the powder into a position of the tube furnace close to an air inlet end, and heating the ammonia borane powder through an external heating table. Heating the central temperature zone to 800 ℃ under the protection of inert atmosphere, and introducing 200sccm of hydrogen for 1h, thereby removing impurities adsorbed on the surface of the foam nickel. The central temperature zone is heated to 1050 ℃, the heat table is heated to 130 ℃, 200sccm argon is introduced as carrier gas, and the growth is carried out for 2 hours. And cooling the nickel foam along with a furnace to room temperature under the protection of argon, taking out the nickel foam, etching the nickel foam in hydrochloric acid, and fully cleaning and drying to obtain the boron nitride network grown by ammonia borane. Due to the steric hindrance of the porous metal structure to the gas flow, the volatilized macromolecular ammonia borane cannot penetrate the nickel foam sufficiently uniformly, resulting in incomplete boron nitride growth in most of the bulk phase of the nickel foam, and thus, there are significant voids in the center of the finally prepared boron nitride foam (fig. 10).
In conclusion, compared with the existing three-dimensional h-BN network preparation process, the method can avoid the problems of uneven growth and limited size caused by difficult bulk diffusion of the boron source, and has the advantages of controllable h-BN layer number and network morphology, simple process, low production cost and easy mass production amplification. The prepared boron nitride has high crystallization quality and can be applied to various fields.
The above examples are provided by way of illustration only and should not be construed as limiting the scope of the invention, and any equivalent or modified method according to the technical solution of the present invention and its inventive concept should be covered in the scope of the invention.
Claims (10)
1. The preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network is characterized by comprising the following steps of:
(1) Adding a solid boron source into pores of a foam metal substrate template in a dry powder or dispersion liquid form through shaking, vibrating, repeatedly lifting, ultrasonic or vacuum impregnation mode, and then putting the foam metal loaded with the boron source into an oven for full drying;
(2) Heating the reaction furnace chamber to a preset pretreatment temperature in a carrier gas protective atmosphere;
(3) Putting foam metal with a solid boron source on the surface into a constant temperature area of a reaction furnace chamber, introducing pretreatment atmosphere, and pretreating for 10-120 min;
(4) Cooling the foam metal pretreated in the step (3) in a carrier gas protective atmosphere, and taking out to obtain foam metal with uniformly distributed boron sources on the surface;
(5) Heating the reaction furnace chamber to a set reduction temperature in a carrier gas protective atmosphere;
(6) Placing pretreated foam metal into a constant temperature area of a reaction furnace chamber, and introducing reducing gas for 10-60 min;
(7) Introducing a mixed atmosphere of nitrogen source gas, reducing gas and carrier gas into a reaction furnace chamber, and converting the solid boron source gas and the nitrogen source gas into h-BN on the surface of the foam metal substrate; in the mixed atmosphere, the flow ratio of the nitrogen source gas to the reducing gas to the carrier gas is 1 (0.5-80) (0-100), and the reaction time is 1-500 min;
(8) And (3) cooling the foam metal obtained in the step (7) in the carrier gas protective atmosphere, and taking out to obtain the three-dimensionally communicated high-quality h-BN network structure growing on the foam metal substrate.
2. The method for preparing the large-size high-quality three-dimensional hexagonal boron nitride network according to claim 1, wherein the foam metal substrate is selected to be reserved or removed by adopting a metal etching solution according to specific application requirements, and the h-BN from which the foam metal substrate is removed is sufficiently cleaned and dried to obtain the high-quality three-dimensional h-BN network.
3. The method for preparing a large-size high-quality three-dimensional hexagonal boron nitride network according to claim 1, wherein in step (1), the solid boron source includes, but is not limited to, one or more of boron oxide, boron powder, and boric acid.
4. The method for preparing the large-size high-quality three-dimensional hexagonal boron nitride network according to claim 1, wherein in the step (1), a foam metal base template is adopted as foam metal with a three-dimensional communicated open-cell structure, and the foam metal has a certain boron-solid solubility or can form an intermediate product with boron, and comprises, but is not limited to, an alloy formed by one or more than two metals selected from foam nickel, foam copper, foam iron and foam cobalt; the porosity of the foam metal substrate template is distributed between 50 and 1000PPI, and the density is between 0.1 and 1.5g/cm 3 The thickness is 0.1 mm-50 mm, and the length and width are 0.5 cm-2 m.
5. The method for preparing a large-size high-quality three-dimensional hexagonal boron nitride network according to claim 1, wherein the pretreatment temperature in step (2) is 300-1050 ℃, preferably 600-1000 ℃.
6. The method for preparing a large-size high-quality three-dimensional hexagonal boron nitride network according to claim 1, wherein in the step (3), the pretreatment atmosphere is one or a mixture of more than two of oxygen, argon, nitrogen, helium or hydrogen, and the oxygen and the hydrogen cannot be used simultaneously, and the flow is 10-5000 sccm.
7. The method for preparing a large-size high-quality three-dimensional hexagonal boron nitride network according to claim 1, wherein in the steps (2), (4), (5), (7) and (8), the carrier gas is one or two of argon and helium.
8. The method for preparing a large-size high-quality three-dimensional hexagonal boron nitride network according to claim 1, wherein in the step (7), the nitrogen source gas is ammonia gas or nitrogen gas, and the flow is 10-2000 sccm; in the steps (6) and (7), the reducing gas is hydrogen, and the flow rate of the reducing gas in the step (6) is 10-5000 sccm; in the steps (5), (6) and (7), the temperature of the reaction furnace chamber is 900-1300 ℃.
9. The preparation method of the large-size high-quality three-dimensional hexagonal boron nitride network according to claim 1, which is characterized in that the morphology, the porosity and the layer number index of the prepared three-dimensional h-BN network can be accurately regulated and controlled by selecting different foam metal substrates and/or regulating and controlling the temperature, the boron source type, the nitrogen source type and the reaction atmosphere in the preparation process.
10. The method for preparing a large-size high-quality three-dimensional hexagonal boron nitride network according to claim 1, wherein the prepared high-quality three-dimensional h-BN network is applied to the fields of heat conduction, energy storage, catalysis, adsorption or aerospace.
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