CN115259111A - Preparation method of boron nitride nanotube - Google Patents
Preparation method of boron nitride nanotube Download PDFInfo
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- CN115259111A CN115259111A CN202210498314.3A CN202210498314A CN115259111A CN 115259111 A CN115259111 A CN 115259111A CN 202210498314 A CN202210498314 A CN 202210498314A CN 115259111 A CN115259111 A CN 115259111A
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 24
- 239000002071 nanotube Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical group [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002017 high-resolution X-ray diffraction Methods 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- C01B21/0641—Preparation by direct nitridation of elemental boron
-
- 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
- C01B21/0646—Preparation by pyrolysis of boron and nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
Abstract
The invention relates to a preparation method of a boron nitride nanotube, which comprises the steps of ball-milling a boron source and a lithium-containing catalyst in a ball-milling tank of an organic medium under the protection of nitrogen or ammonia gas, and drying in a drying oven in vacuum; and carrying out chemical vapor deposition on the ball-milled boron source and lithium-containing catalyst mixture in a tube furnace containing nitrogen gas to obtain a primary boron nitride nanotube, and carrying out acid washing and heat treatment on the primary boron nitride nanotube to obtain a final boron nitride nanotube. The technical scheme provided by the invention improves the purity and crystallinity of the boron nitride nanotube by utilizing a purification mode combining acid washing and heat treatment while preparing the boron nitride nanotube on a large scale.
Description
Technical Field
The invention relates to preparation of a nano material, in particular to a preparation method of a boron nitride nanotube.
Background
The structure of Boron Nitride Nanotubes (BNNTs) formed by curling graphite-like layered hexagonal boron nitride (hBN) along a specific direction is similar to that of Carbon Nanotubes (CNTs), the mechanical property and the thermophysical property can be compared with those of the Carbon Nanotubes (CNTs), the oxidation resistance and the chemical stability of the BNNTs are more excellent than those of the CNTs, the oxidation resistance temperature of the BNNTs in the air is as high as 700-950 ℃, and the CNTs are generally only 450-500 ℃.
In the aspect of electrical performance, BNNTs is a semiconductor with a wide forbidden band, the forbidden band width is 5.5-6.0 eV, and the BNNTs is not influenced by the pipe diameter and chirality; in addition, BNNTs also has piezoelectricity, super-hydrophobicity, hydrogen storage, neutron absorption and good biocompatibility, and has huge application potential in the fields of composite materials, semiconductor devices, biomedicine and energy.
In recent years, many researchers have been working on the synthesis of BNNTs, and the existing methods for preparing BNNTs mainly include arc discharge method, laser ablation method, template method, chemical vapor deposition method and ball milling annealing method. The arc discharge method and the laser ablation method are generally carried out at a high temperature of more than 2000 ℃, and have the defects of harsh reaction conditions, low yield, high equipment cost and the like. The existing template method for preparing BNNTs adopts an alumina template and a CNTs template, adds a nitrogen source and a boron source to carry out high-temperature processing, and then removes the templates by a chemical method, but the defects are that the templates can be used as impurities to pollute the BNNTs, and the purity of the obtained BNNTs is low.
Although the existing chemical vapor deposition method is a method capable of preparing a large amount of BNNTs, for example, chinese patent No. CN101717077A discloses a technical scheme of mixing B powder and metal oxide, using reduced metal particles as a catalyst, and introducing nitrogen gas for high-temperature heat preservation to generate BNNTs, the method has the disadvantages that the tube diameter of BNNTs is difficult to control, the process stability is poor, the purity is low, and the mass production is difficult.
While chinese patent No. CN107758633A discloses a technical scheme of ball milling B powder and catalyst or ball milling B powder directly with Fe-containing ball milling beads to obtain a precursor with higher activity, and then reacting in a high temperature deposition furnace containing a nitrogen source to generate BNNTs, but the method further improves the activity of B source, and is one of the most promising methods for mass synthesis of BNNTs nanotubes at present, but the prepared BNNTs still have lower quality, and generally have the problems of poor impurities and crystallinity, etc.
Therefore, it is necessary to provide a technical solution that can not only batch-produce BNNTs, but also greatly improve the quality of BNNTs.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a method for preparing BNNTs in high volumes and quality.
The purpose of the invention is realized by adopting the following technical scheme:
a method for preparing boron nitride nanotubes comprises the following steps:
(1) Under the atmosphere of ammonia or nitrogen, after ball milling a boron source and a lithium-containing catalyst in a ball milling tank of an organic medium, drying the mixture in a drying oven in vacuum;
(2) In a tubular furnace under the protective atmosphere of nitrogen-containing gas, carrying out chemical vapor deposition on the mixture in the alumina crucible to obtain a primary boron nitride nanotube;
(3) And (3) purifying and thermally treating the primary boron nitride nanotube obtained in the step (2) to obtain a final boron nitride nanotube.
Preferably, in the step (1),
the molar ratio of the boron source to the lithium-containing catalyst is 1 (0.1-1);
the molar ratio of the mixture to the organic medium is 1 (5-10).
Preferably, the ball milling of step (1) comprises:
ball milling for 12-24 h at the rotating speed of 200-300 r/min by using ceramic beads with the diameter of 0.4-0.6 cm;
the mass ratio of the ceramic beads to the mixture is (7-10): 1.
preferably, in step (1):
the boron source is selected from elemental boron and/or a boron-containing compound;
the lithium-containing catalyst is selected from Li2O、Li2CO3、LiNO3And LiOH.
Preferably, the ball milling tank in the step (1) is a zirconia ball milling tank.
Preferably, the average particle size of the mixture in the step (1) is 80-120 nm.
Preferably, the chemical vapor deposition in step (2) comprises:
introducing inert gas with the purity of 99.99 percent at the speed of 100-300 ml/min, heating to 1200-1350 ℃ at the speed of 5-10 ℃/min, introducing nitrogen-containing gas with the purity of 99.99 percent at the speed of 100-200 ml/min, preserving the heat for 2-4 h, and cooling to room temperature at the speed of 5-10 ℃/min.
Preferably, the protective atmosphere in the step (2) is introduced in an amount of 100-250 ml/min, and the purity is 99.99 percentNH3Or a nitrogen-hydrogen mixed gas.
Preferably, the purification of step (3) comprises acid washing and/or water washing of the acid wash with one or more acids selected from hydrochloric acid, nitric acid and sulfuric acid.
Preferably, the heat treatment in step (3) comprises treatment at 1500-1700 ℃ for 2-4 h.
Compared with the closest prior art, the technical scheme provided by the invention has the following beneficial effects:
1. in the invention, under the protection atmosphere of ammonia gas or nitrogen gas, a boron source and a lithium-containing catalyst are ball-milled in a ball-milling tank of an organic medium, and the obtained mixture is vacuum-dried in a drying oven; carrying out chemical vapor deposition on the obtained mixture in the alumina crucible in a tubular furnace in the protective atmosphere of nitrogen-containing gas to obtain a primary boron nitride nanotube; acid washing and heat treatment are carried out on the obtained primary boron nitride nanotube to obtain the final boron nitride nanotube.
The boron nitride nanotube prepared by deposition is subjected to heat treatment in the scheme provided by the invention, and the heat treatment temperature is controlled to be 1500-1700 ℃, so that the aims of improving the degree of lattice order and the crystallinity are fulfilled; overcomes the defects of low lattice order degree, disordered amorphous structure caused by unclear layered structure and low crystallinity in the prior art when preparing the boron nitride nanotube at the temperature lower than 1500 ℃; and the subsequent acid washing and heat treatment processes which are carried out successively avoid the interference of impurities on the crystallization of the boron nitride nanotube in the heat treatment process, further improve the crystallinity and obtain the boron nitride nanotube with complete shape.
2. According to the technical scheme provided by the invention, the Li-containing compound is used as the catalyst, so that the catalyst has high catalytic activity, and under the process condition of the invention, the solid solution formed by the metal Li at high temperature can simultaneously take account of the solid solubility of the B element and the N element, so that the improvement of the conversion rate is very facilitated.
3. According to the technical scheme provided by the invention, the zirconia ball-milling tank and the ceramic ball-milling beads are used for replacing an iron ball-milling tank and ball-milling beads, so that on one hand, the introduction of metal impurities is avoided, on the other hand, the activity of B elements is improved, the introduction of impurities is fundamentally removed, and the conversion efficiency of the boron nitride nanotube is greatly improved.
Drawings
FIG. 1 is a schematic diagram of a process for preparing BNNTs according to the invention;
FIG. 2 is a photomicrograph of primary BNNTs obtained in example 1 of the present invention;
FIG. 3 is a low magnification SEM photograph of primary BNNTs obtained in example 1 of the present invention;
FIG. 4 is a high magnification SEM photograph of primary BNNTs obtained in example 1 of the present invention;
FIG. 5 is a high magnification SEM photograph of acid-washed primary BNNTs obtained in example 1 of the present invention;
FIG. 6 is a high-power TEM image of the primary BNNTs obtained in example 1 of the present invention after acid washing;
FIG. 7 is a high magnification TEM image of the final BNNTs obtained in example 1 of the present invention;
FIG. 8 is a high resolution XRD pattern of the resulting final BNNTs of example 3 of the present invention;
FIG. 9 is a BNNTs Raman spectrum obtained in example 3 of the present invention before heat treatment;
FIG. 10 is a BNNTs Raman spectrum obtained after heat treatment in example 3 of the present invention.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention as claimed in the appended claims.
Example 1
(1) Mixing of boron source and lithium-containing catalyst: in N2In a ball milling tank under the gas protection atmosphere, rotating speed of 250 r/min is used for mixing amorphous B and Li2O and do notAnd (3) carrying out ball milling on the mixture of water and ethanol for 12 hours, and drying in a vacuum drying oven to obtain a mixture with the average particle size of 120nm.
Wherein, amorphous B and Li2The molar ratio of the O catalyst is 12The diameter of the grinding bead of the ceramic ball is 0.6cm, and the mass ratio of the ball material is 10:1.
(2) Preparing BNNTs: and uniformly spreading the dried mixture in an alumina crucible, and performing chemical vapor deposition in a high-temperature tube furnace.
Wherein, under the protection atmosphere of Ar with the purity of 99.99 percent and the speed of 100ml/min, the temperature is increased to 1200 ℃ at the temperature increasing speed of 10 ℃/min, the temperature is preserved for 2h, NH with the purity of 99.99 percent is introduced at the speed of 150ml/min3And (3) cooling to room temperature at the cooling rate of 10 ℃/min under the atmosphere to obtain the primary BNNTs.
(3) Purification of primary BNNTs: and (3) sequentially washing the primary BNNTs obtained in the step (2) with 36% hydrochloric acid for 6 hours, washing with deionized water, drying, and introducing into a high-temperature tube furnace with the purity of 99.99 percent under the protective atmosphere of Ar gas at the speed of 100ml/min for heat treatment for 2 hours to obtain the BNNTs.
The steps (1) to (3) of example 1 were repeated in the remaining examples, but the parameters corresponding to the steps and the quality parameters of the examples are shown in the following table;
FIG. 1 is a schematic diagram of a process for preparing BNNTs according to the invention;
FIG. 2 is a photomicrograph of the primary BNNTs obtained in example 1 of the present invention, which clearly shows that the primary BNNTs obtained are in the form of clusters, have a mass of 0.21g and an average length of about 40 μm;
FIG. 3 is a low magnification SEM photograph of primary BNNTs obtained in example 1 of the present invention, showing that the primary BNNTs obtained in the present invention have a low amount of impurity particles;
FIG. 4 is a high magnification SEM photograph of primary BNNTs obtained in example 1 of the present invention, with catalyst impurity particles visible on the top of the BNNTs;
FIG. 5 is a high power SEM photograph of acid-washed primary BNNTs obtained in example 1 of the present invention, showing that the acid-washed BNNTs have clean surfaces and no impurity particles;
FIG. 6 is a high-power TEM photograph of the primary BNNTs obtained in example 1 of the present invention after acid washing, wherein the acid-washed BNNTs have clean surfaces, partially disordered amorphous structures in the structures and poor crystallinity;
FIG. 7 is a high magnification TEM image of the final BNNTs obtained in example 1 of the invention, and comparing with FIG. 6, it can be seen that the BNNTs after heat treatment have a clear layered structure, and the crystallinity is higher than that of the BNNTs before heat treatment;
FIG. 8 is a high resolution XRD pattern of terminal BNNTs obtained in example 3 of the present invention, wherein only BNNTs phase is present in the pattern, the half-width peak of XRD is smaller, and the crystallinity of BNNTs is good; wherein intensity represents "intensity"; degree represents "degree"; the abscissa indicates that: 2 θ (degrees);
FIG. 9 is a BNNTs Raman spectrum before heat treatment obtained in example 3 of the present invention; wherein intensity represents "intensity"; wavenumber means "wavenumber".
FIG. 10 is a Raman spectrum of the thermally treated BNNTs obtained in example 3 of the invention, comparing with FIG. 9, the peaks after thermal treatment were narrower than before thermal treatment, and the crystallinity of the BNNTs after thermal treatment was significantly improved. Wherein intensity represents "intensity"; wavenumber indicates "wavenumber".
According to the embodiment, the scheme is suitable for preparing BNNTs by various boron sources and lithium-containing catalysts, and has wide application range; the yield is more than 85 percent; BNNTs has complete shape, high crystallinity and good mechanical property. The process is simple, and can realize high-quality and macro-scale production of BNNTs.
Finally, it should be noted that: although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. A method for preparing boron nitride nanotubes is characterized by comprising the following steps:
(1) Under the atmosphere of nitrogen or ammonia, after a boron source and a lithium-containing catalyst are ball-milled in a ball-milling tank of an organic medium, the mixture is dried in a drying oven in vacuum;
(2) In a tubular furnace under the protective atmosphere of nitrogen-containing gas, carrying out chemical vapor deposition on the mixture in the alumina crucible to obtain a primary boron nitride nanotube;
(3) And (3) purifying and thermally treating the primary boron nitride nanotube obtained in the step (2) to obtain a final boron nitride nanotube.
2. The method of claim 1, wherein in step (1),
the molar ratio of the boron source to the lithium-containing catalyst is 1 (0.1-1);
the molar ratio of the mixture to the organic medium is 1 (5-10).
3. The method of claim 1, wherein the ball milling of step (1) comprises:
ball milling with ceramic beads of 0.4-0.6 cm diameter at 200-300 rpm for 12-24 hr;
the mass ratio of the ceramic beads to the mixture is (7-10): 1.
4. the method of claim 1, wherein in step (1):
the boron source is selected from elemental boron and/or a boron-containing compound;
the lithium-containing catalyst is selected from Li2O、Li2CO3、LiNO3And LiOH.
5. The method of claim 1, wherein the ball mill pot in step (1) is a zirconia ball mill pot.
6. The method of claim 1, wherein the average particle size of the compound in step (1) is 80 to 120nm.
7. The method of claim 1, wherein the chemical vapor deposition in step (2) comprises:
introducing inert gas with the purity of 99.99 percent at the speed of 100-300 ml/min, heating to 1200-1350 ℃ at the speed of 5-10 ℃/min, introducing nitrogen-containing gas with the purity of 99.99 percent at the speed of 100-200 ml/min, preserving the temperature for 2-4 h, and cooling to room temperature at the speed of 5-10 ℃/min.
8. The method of claim 1, wherein the protective atmosphere in step (2) is NH with a purity of 99.99% introduced in an amount of 100-250 ml/min3Or a nitrogen-hydrogen mixed gas.
9. The method of claim 1, wherein the purifying of step (3) comprises acid washing and/or water washing the acid wash with one or more acids selected from hydrochloric acid, nitric acid, and sulfuric acid.
10. The method of claim 1, wherein the heat treatment of step (3) comprises treatment at 1500-1700 ℃ for 2-4 hours.
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