CN114105109B - Preparation method of fig-shaped hollow hexagonal boron nitride nanostructured powder - Google Patents

Preparation method of fig-shaped hollow hexagonal boron nitride nanostructured powder Download PDF

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CN114105109B
CN114105109B CN202111408617.3A CN202111408617A CN114105109B CN 114105109 B CN114105109 B CN 114105109B CN 202111408617 A CN202111408617 A CN 202111408617A CN 114105109 B CN114105109 B CN 114105109B
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boron nitride
powder
shaped hollow
hexagonal boron
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CN114105109A (en
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李艳娇
王鑫峰
刘延飞
刘彬
赵少宁
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Rocket Force University of Engineering of PLA
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions

Abstract

The invention discloses a preparation method of fig-shaped hollow hexagonal boron nitride nano-structure powder, which comprises the following steps: 1. mixing boron oxide and metal magnesium powder, and performing ball milling to obtain precursor powder; 2. spreading the precursor powder in a porcelain boat, covering a metal wire mesh and porcelain tiles, placing the porcelain tiles between the metal wire mesh and the air outlet side of the porcelain boat, and heating to obtain white powder; 3. soaking the white powder in hydrochloric acid solution and then flushing; 4. drying to obtain the fig-shaped hollow hexagonal boron nitride nano-structure powder. The invention controls the positions of the metal wire mesh and the ceramic chip on the porcelain boat, so that the concentration of the reaction gas on the inner wall of the air outlet side of the porcelain boat is lower, the growth speed of boron nitride is regulated and controlled to be slow, an onion-shaped hollow capsule structure is formed, and the fig-shaped hollow hexagonal boron nitride nano-structure powder with uniform shape and size, good crystallization, high purity and high yield is obtained and is applied to the fields of heat conduction composite materials, high-temperature structural components and the like.

Description

Preparation method of fig-shaped hollow hexagonal boron nitride nanostructured powder
Technical Field
The invention belongs to the technical field of inorganic micro-nano materials, and particularly relates to a preparation method of fig-shaped hollow hexagonal boron nitride nano-structure powder.
Background
The molecular formula of the boron nitride is BN, is a graphite-like layered structure material composed of nitrogen (N) atoms and boron (B) atoms, has excellent electrical insulation, high temperature resistance, oxidation resistance, chemical corrosion resistance and high heat conductivity, and is widely applied to the high-tech fields of machinery, metallurgy, electronics, aerospace and the like.
Because of the small-size effect, the BN nano material has the advantages of high specific surface area, good adsorptivity and the like on the basis of having the excellent performance of the bulk BN material. At present, the research on nano-scale BN materials is mainly focused on BN nanotubes, compared with the BN nano materials with other morphologies such as BN nanowires, BN nanosheets, BN nanospheres, BN nano onions, micro-nano composite structures and the like, the research on the BN nano materials is started later, the literature reports are very few, and the reports on the fig-shaped hollow hexagonal boron nitride nano structures are less common.
The hollow hexagonal boron nitride nanometer structure is a new form of boron nitride nanometer material, and is a BN nanometer structure which is spherical in shape, provided with a tip, similar to figs or garlic, has a certain wall thickness and is hollow in the middle. On the basis of having excellent performances of insulation, high temperature resistance, oxidation resistance, chemical corrosion resistance, high thermal conductivity and the like of a block boron nitride material, the material has the characteristics of small nanoscale size, small loose packing density and the like due to the structure of the cavity in the material, and is expected to become a good heat conduction composite material additive, a drug carrier, a small packaged container, a protective cover of a photoluminescent material, a hydrogen storage device, a solid-state light source and an optoelectronic device. So far, no report is made about the fig-shaped hollow hexagonal boron nitride nanostructure.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of the fig-shaped hollow hexagonal boron nitride nano structure aiming at the defects in the prior art. According to the method, boron oxide powder and magnesium powder are ball-milled to prepare precursor powder, the precursor powder is placed in a porcelain boat, a metal wire mesh and porcelain chips are covered for heating treatment, the positions of the metal wire mesh and the porcelain chips on the porcelain boat are controlled, so that the concentration of reaction gas on the inner wall of the air outlet side of the porcelain boat is low, the growth speed of boron nitride is regulated and controlled slowly, an onion-shaped hollow capsule structure is formed, and the fig-shaped hollow hexagonal boron nitride nano-structure powder with uniform shape and size, good crystallization, high purity and high yield is obtained.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized by comprising the following steps of:
step one, mixing boron oxide and metal magnesium powder, and then placing the mixture in a planetary ball mill for ball milling treatment to obtain precursor powder; the particle size of the precursor powder is 2-10 mu m;
uniformly spreading the precursor powder obtained in the first step in a porcelain boat, covering a metal wire mesh and porcelain tiles above the porcelain boat, placing the porcelain tiles between the metal wire mesh and the air outlet side of the porcelain boat, and then placing the porcelain tiles in a tubular atmosphere protection annealing furnace for heating treatment to obtain white powder on the inner wall of the air outlet side of the porcelain boat; the heating treatment process comprises the following steps: under the protection of inert gas with the flow of 20-100 mL/min, heating from room temperature to 300 ℃ at the heating rate of 10 ℃/min, stopping introducing inert gas, introducing ammonia gas at the flow of 20-100 mL/min, continuously heating to 1250-1350 ℃ for heat preservation for 2-8 h, stopping introducing ammonia gas, and naturally cooling to room temperature under the protection atmosphere;
step three, dipping the white powder obtained in the step two by adopting hydrochloric acid solution, and then flushing by adopting deionized water;
and fourthly, placing the white powder washed in the third step into a vacuum drying oven for drying to obtain the fig-shaped hollow hexagonal boron nitride nano-structure powder.
The invention adopts low-cost boron oxide powder as boron source, and is mixed with metal magnesium powder for ball milling to prepare precursor powder, then the precursor powder is placed in a porcelain boat, metal wire mesh and porcelain chips are covered on the porcelain boat in turn, and then ammonia gas is introduced into a tubular atmosphere protection annealing furnace for heating treatment, in the heating treatment process, one air inlet end of the porcelain boat is an air inlet side, one air outlet end is an air outlet side, the metal wire mesh is covered above the porcelain boat, and a space for air inlet and air outlet of the porcelain boat is reserved, and is usually covered above the middle part of the porcelain boat, al 2 O 3 The ceramic chip is placed between the metal wire mesh and the air outlet side of the ceramic boat, and the air inlet and air outlet pore spaces are reserved, so that along with the heating treatment process, the magnesium powder in the precursor powder catalyzes the boron oxide to produce B 2 O 2 Gas, B 2 O 2 The gas diffuses through the wire mesh with voids and the wire mesh acts as a catalyst, and the conversion of the contained metal component into droplets catalyzes the penetration of B through the wire mesh 2 O 2 The gas reacts with the ammonia gas which is introduced from the air inlet side and flows through the wire mesh, and boron nitride nanotubes are generated and attached to the wire mesh, and the wire mesh is positioned above the porcelain boat, so that B generated in the porcelain boat is easy to generate 2 O 2 The gas passes through and diffuses upwards, and the ceramic chip prevents the ammonia gas from flowing out from the gas outlet side and leads to partial reflux of the ammonia gas, both of whichThe combined action ensures that the reaction gas participated in the inner boat wall of the air outlet side of the porcelain boat is thinner, the concentration is lower, the catalytic capability is weaker, the boron nitride grows slowly to form an onion-shaped hollow capsule structure, a large amount of white loose powder is formed on the inner wall of the air outlet side of the porcelain boat, and the fig-shaped hollow hexagonal boron nitride nano-structure powder (Hexagonal boron nitride, abbreviated as h-BN) with uniform appearance and size, good crystallization, high purity and high yield is obtained after dipping, washing and drying.
The BN nano material has high heat conductivity, is a good thermal composite material additive, is easy to agglomerate, is easy to greatly reduce the heat conductivity due to agglomeration sinking when being used as a nano fluid additive, has a hollow structure, has a smaller wall thickness, is much lower than that of a solid BN nano material, is easy to suspend in base liquid, has a fig-like shape, has a tip end, effectively reduces agglomeration, ensures the heat conducting performance, and has wide application prospect in the fields of heat conducting composite materials such as electronic heat radiating elements, nano fluids and the like, high-temperature structural parts and the like. In addition, the material prepared by the fig-shaped hollow hexagonal boron nitride nano-structure powder can be applied to drug carriers, small packaged containers, protective covers of photoluminescent materials, hydrogen storage devices, solid-state light sources and optoelectronic devices.
The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized in that the molar ratio of the boron oxide to the metal magnesium powder in the first step is 1:1.5-1:2.5. The invention ensures the smooth proceeding of the subsequent boron oxide reaction catalyzed by the magnesium powder by limiting the molar ratio of the boron oxide to the metal magnesium powder, and simultaneously avoids the phenomenon of tank sticking in the ball milling process, thereby being more convenient to operate.
The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized in that the ball milling treatment time in the first step is 2-12 h. The optimized ball milling treatment time enables boron oxide and metal powder to be fully activated, further ensures the subsequent magnesium powder catalytic reaction, avoids agglomeration of metal powder into large particles due to thermal welding caused by excessive ball milling, and saves energy and time.
The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized in that the metal wire mesh in the second step contains iron. The preferred wire mesh has a relatively strong catalytic capability and a relatively wide source and is readily available.
The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized in that the inert gas and the protective atmosphere in the second step are helium, neon, argon, krypton, xenon or radon.
The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized in that the gas flow rate of the protective atmosphere in the second step is 20-100 mL/min.
The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized in that the volume concentration of the hydrochloric acid solution in the third step is 20%, the soaking time is 4-8 h, and the flushing times are 5-6 times.
The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized in that the drying temperature in the fourth step is 60-90 ℃ and the drying time is 4-8 h.
The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized in that the ceramic chip in the second step is composed of metal oxide.
The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized in that the ceramic chip is Al 2 O 3 Porcelain piece. Because the porcelain boat is usually made of Al 2 O 3 By selecting Al 2 O 3 The ceramic chip avoids introducing other impurities, and further avoids adverse effects on the preparation of a target product by heating treatment.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, boron oxide powder and magnesium powder are ball-milled to prepare precursor powder, the precursor powder is placed in a porcelain boat, then a metal wire mesh and porcelain chips are covered, heating treatment is carried out under an ammonia gas introducing atmosphere, the concentration of reaction gas on the inner wall of the air outlet side of the porcelain boat is lower by controlling the positions of the metal wire mesh and the porcelain chips on the porcelain boat, and then the growth speed of boron nitride is regulated and controlled, so that the growth speed of boron nitride is slow, an onion-shaped hollow capsule structure is formed, and the fig-shaped hollow hexagonal boron nitride nano-structure powder with uniform shape and size, good crystallization, high purity and high yield is obtained.
2. The prepared fig-shaped hollow hexagonal boron nitride nano-structure powder has a hollow structure, the height of the powder is about 300 nm-600 nm, the outer diameter of the powder is about 300 nm-500 nm, the inner diameter of the powder is about 100 nm-400 nm, and the wall thickness of the powder is about 50nm.
3. The prepared fig-shaped hollow hexagonal boron nitride nano-structure powder has a hollow structure, has small wall thickness, low density and easy suspension in liquid, has a pointed end in the fig-shaped shape, effectively reduces aggregation, ensures the heat conducting performance of the fig-shaped hollow hexagonal boron nitride nano-structure powder, and has wide application prospect in the fields of heat conducting composite materials such as electronic radiating elements and nanofluids, high-temperature structural parts and the like.
4. The preparation method has mild reaction conditions and simple process, and the adopted raw materials of boron oxide, metal magnesium powder, metal wire mesh and ceramic chip are cheap and easy to obtain, are nontoxic and harmless, reduce the preparation cost and are suitable for large-scale industrial production.
5. The method prepares the precursor powder through ball milling activation, then heats the precursor powder through the tube-type atmosphere protection annealing furnace to obtain the product, has low equipment requirement, reduces the heating reaction temperature through ball milling activation, thereby reducing the energy consumption and the production cost of the whole preparation process, and simultaneously can purify through simple acid washing, has simple method, is easy to operate, and is easy to realize large-scale industrial production.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1a is a scanning electron microscope image of the fig-shaped hollow hexagonal boron nitride nanostructure powder prepared in example 1 of the present invention.
Fig. 1b is an enlarged view of the area indicated by the left arrow in fig. 1 a.
Fig. 1c is an enlarged view of the area indicated by the right arrow in fig. 1 a.
Fig. 2a is a low-power TEM image of fig-like hollow hexagonal boron nitride nanostructured powder prepared in example 1 of the present invention.
FIG. 2b is a selective area diffraction pattern corresponding to FIG. 2 a.
Fig. 3a is a TEM image of selected areas of the fig-like hollow hexagonal boron nitride nanostructure powder prepared in example 1 of the present invention.
Fig. 3b is a high magnification TEM image of the area indicated by the arrow in fig. 3 a.
Fig. 3c is a high resolution TEM image of the area indicated by the arrow in fig. 3 b.
FIG. 4 is an EDS energy spectrum of the selected region of FIG. 3 a.
Fig. 5a is a B-element plane scan of the selected region of fig. 3 a.
Fig. 5b is an N-element face scan of the selected region of fig. 3 a.
Fig. 5c is a surface scan of Mg element in the selected region of fig. 3 a.
Fig. 5d is an O-element surface scan of the selected area of fig. 3 a.
Detailed Description
Example 1
The embodiment comprises the following steps:
firstly, mixing boron oxide and metal magnesium powder according to a molar ratio of 1:2, then placing the mixture in a ball milling tank of a planetary ball mill, and performing ball milling treatment for 4 hours in a forward and reverse alternate operation mode to obtain precursor powder which is uniformly mixed; the particle size of the precursor powder is 2-10 mu m;
step two, uniformly spreading 0.2g of the precursor powder obtained in the step one in a porcelain boat, and covering a stainless steel wire mesh with the length multiplied by the width multiplied by 30mm and Al above the porcelain boat 2 O 3 The ceramic chip has one air inlet end as air inlet side and one air outlet end as air outlet side, and has metal wire mesh covering the middle part of the ceramic boat and with air inlet and outlet space to hold Al 2 O 3 Placing the porcelain piece on the metal wire mesh and the porcelainThe position between the air outlet sides of the boat is also provided with air inlet and air outlet pore spaces, the boat is placed in a tubular atmosphere protection annealing furnace, the temperature is raised from room temperature to 300 ℃ at the heating rate of 10 ℃/min under the protection of argon with the flow rate of 50mL/min, then the argon is stopped to be introduced, the ammonia is introduced at the flow rate of 50mL/min, the temperature is continuously raised to 1300 ℃ for 8 hours, then the ammonia is stopped to be introduced, the boat is naturally cooled to room temperature under the protection of argon with the gas flow rate of 50mL/min, and white powder is obtained on the inner wall of the air outlet side of the porcelain boat;
step three, soaking the white powder obtained in the step two in a hydrochloric acid solution with the volume concentration of 20% for 6 hours, and then flushing the white powder with deionized water for 6 times;
step four, placing the white powder washed in the step three in a vacuum drying oven for drying to obtain powder of the fig-shaped hollow hexagonal boron nitride nano structure; the drying temperature is 80 ℃ and the drying time is 6 hours.
Fig. 1a is a scanning electron microscope image of the fig-shaped hollow hexagonal boron nitride nano-structure powder prepared in this example, and it can be seen from fig. 1a that the hexagonal boron nitride nano-structure powder of the product has a large quantity and high purity, wherein white arrows in fig. 1a show two different observation areas of the product.
Fig. 1b is an enlarged view of the area indicated by the left arrow in fig. 1a, and it can be seen from fig. 1b that the tip portion of the product hexagonal boron nitride nanostructured powder has a closed shape and an open shape similar to the tip portion of fig.
Fig. 1c is an enlarged view of the area indicated by the right arrow in fig. 1a, and it can be seen from fig. 1c that the product hexagonal boron nitride nanostructured powder has a typical fig-like structure, a matte surface, and a plurality of facets similar to the diamond surface.
Fig. 2a is a low-power TEM image of the fig-shaped hollow hexagonal boron nitride nano-structure powder prepared in this example, and it can be seen from fig. 2a that the diameter of the product hexagonal boron nitride nano-structure powder is uniform, and the product hexagonal boron nitride nano-structure powder is a hollow structure, and has an outer diameter of about 300nm to 500nm, an inner diameter of about 200nm to 400nm, and a wall thickness of about 50nm.
FIG. 2b is a selective area diffraction pattern corresponding to FIG. 2 a. As can be seen from the diffraction ring in FIG. 2b, the product prepared in this example has a hexagonal boron nitride composition.
Fig. 3a is a TEM image of a selected area of the fig-shaped hollow hexagonal boron nitride nano-structure powder prepared in this example, fig. 3b is a high-power TEM image of an arrow indication area in fig. 3a, fig. 3c is a high-resolution TEM image of an arrow indication area in fig. 3b, and it can be seen from fig. 3a to 3c that the product hexagonal boron nitride nano-structure powder is completely crystallized, and the interplanar spacing is about 0.334nm, which accords with the interplanar spacing of hexagonal boron nitride.
Fig. 4 is an EDS spectrum of the selected region of fig. 3a, and the detection result of fig. 4 shows that the atomic ratio of B, N element in the product is 13.82:13.75, close to 1:1, the composition of the product prepared in this example is BN.
Fig. 5a is a B-element surface scan of the selected region in fig. 3a, fig. 5B is an N-element surface scan of the selected region in fig. 3a, fig. 5c is an Mg-element surface scan of the selected region in fig. 3a, fig. 5d is an O-element surface scan of the selected region in fig. 3a, and it can be seen from fig. 5a to fig. 5d that the product prepared in this embodiment is boron nitride and the intermediate coated particles are magnesium oxide.
As can be seen from the drawings, the product prepared by the embodiment is the fig-shaped hollow hexagonal boron nitride nano-structure powder with high quality and purity, good crystallinity and uniform size.
The inert gas and the protective atmosphere in the second step of the present embodiment may be replaced by helium, neon, krypton, xenon or radon.
Example 2
This embodiment differs from embodiment 1 in that: and in the second step, the temperature is raised to 1250 ℃ in the heating treatment process.
Example 3
This embodiment differs from embodiment 1 in that: and in the second step, the temperature is raised to 1350 ℃ in the heating treatment process.
Example 4
This embodiment differs from embodiment 1 in that: in the first step, the mol ratio of the boron oxide to the metal magnesium powder is 1:1.5.
example 5
This embodiment differs from embodiment 1 in that: in the first step, the mol ratio of the boron oxide to the metal magnesium powder is 1:2.5.
example 6
This embodiment differs from embodiment 1 in that: the ball milling treatment time in the first step is 2 hours.
Example 7
This embodiment differs from embodiment 1 in that: the ball milling treatment time in the first step is 8 hours.
Example 8
This embodiment differs from embodiment 1 in that: the ball milling treatment time in the first step is 10 hours.
Example 9
This embodiment differs from embodiment 1 in that: the ball milling treatment time in the first step is 12 hours.
Example 10
This embodiment differs from embodiment 1 in that: and in the third step, the heat preservation time is 2 hours.
Example 11
This embodiment differs from embodiment 1 in that: and in the third step, the heat preservation time is 4 hours.
Example 12
This embodiment differs from embodiment 1 in that: and in the third step, the heat preservation time is 6 hours.
Example 13
This embodiment differs from embodiment 1 in that: and in the third step, the heat preservation time is 10 hours.
Example 14
This embodiment differs from embodiment 1 in that: and step two, adopting vacuumizing to replace argon protection for heating treatment.
Example 15
The embodiment differs from embodiment 1 in that: and step two, vacuumizing, and then introducing argon to replace argon protection for heating treatment.
Example 16
This embodiment differs from embodiment 1 in that: and in the second step, the flow rate of the protective atmosphere argon is 20mL/min.
Example 17
This embodiment differs from embodiment 1 in that: and in the second step, the flow rate of the protective atmosphere argon is 100mL/min.
Example 18
This embodiment differs from embodiment 1 in that: in the second step, the flow rate of the reaction gas ammonia is 20mL/min.
Example 19
This embodiment differs from embodiment 1 in that: in the second step, the flow rate of the reaction gas ammonia is 100mL/min.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.

Claims (8)

1. The preparation method of the fig-shaped hollow hexagonal boron nitride nano-structure powder is characterized by comprising the following steps of:
step one, mixing boron oxide and metal magnesium powder, and then placing the mixture in a planetary ball mill for ball milling treatment to obtain precursor powder; the particle size of the precursor powder is 2-10 mu m; the molar ratio of the boron oxide to the metal magnesium powder is 1:1.5-1:2.5;
uniformly spreading the precursor powder obtained in the first step in a porcelain boat, covering a metal wire mesh and porcelain tiles above the porcelain boat, placing the porcelain tiles between the metal wire mesh and the air outlet side of the porcelain boat, and then placing the porcelain tiles in a tubular atmosphere protection annealing furnace for heating treatment to obtain white powder on the inner wall of the air outlet side of the porcelain boat; the heating treatment process comprises the following steps: under the protection of inert gas with the flow of 20-100 mL/min, heating from room temperature to 300 ℃ at the heating rate of 10 ℃/min, stopping introducing inert gas, introducing ammonia gas at the flow of 20-100 mL/min, continuously heating to 1250-1350 ℃ for heat preservation for 2-8 h, stopping introducing ammonia gas, and naturally cooling to room temperature under the protective atmosphere with the flow rate of 20-100 mL/min;
step three, dipping the white powder obtained in the step two by adopting hydrochloric acid solution, and then flushing by adopting deionized water;
and fourthly, placing the white powder washed in the third step into a vacuum drying oven for drying to obtain the fig-shaped hollow hexagonal boron nitride nano-structure powder.
2. The method for preparing the fig-shaped hollow hexagonal boron nitride nano-structure powder according to claim 1, wherein the ball milling treatment time in the first step is 2-12 hours.
3. The method for preparing the fig-shaped hollow hexagonal boron nitride nano-structure powder according to claim 1, wherein in the second step, the metal wire mesh contains iron.
4. The method for preparing the fig-shaped hollow hexagonal boron nitride nano-structure powder according to claim 1, wherein in the second step, the inert gas and the protective atmosphere are helium, neon, argon, krypton, xenon or radon.
5. The method for preparing the fig-shaped hollow hexagonal boron nitride nano-structure powder according to claim 1, wherein the volume concentration of the hydrochloric acid solution in the third step is 20%, the soaking time is 4-8 h, and the washing times are 5-6.
6. The method for preparing the fig-shaped hollow hexagonal boron nitride nano-structure powder according to claim 1, wherein the drying temperature in the fourth step is 60-90 ℃ and the drying time is 4-8 hours.
7. The method for preparing the fig-shaped hollow hexagonal boron nitride nano-structure powder according to claim 1, wherein in the second step, the ceramic chip is made of metal oxide.
8. The method for preparing the fig-shaped hollow hexagonal boron nitride nano-structure powder according to claim 7, wherein the ceramic chip is Al 2 O 3 Porcelain piece.
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