CN116815499A - Method for growing carbon nano tube by carbon fiber surface loaded core-shell structure catalyst and application - Google Patents
Method for growing carbon nano tube by carbon fiber surface loaded core-shell structure catalyst and application Download PDFInfo
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- CN116815499A CN116815499A CN202310741022.2A CN202310741022A CN116815499A CN 116815499 A CN116815499 A CN 116815499A CN 202310741022 A CN202310741022 A CN 202310741022A CN 116815499 A CN116815499 A CN 116815499A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 160
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 160
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 121
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 39
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000011258 core-shell material Substances 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 61
- 239000002243 precursor Substances 0.000 claims abstract description 44
- 230000002787 reinforcement Effects 0.000 claims abstract description 44
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000002105 nanoparticle Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 239000006012 monoammonium phosphate Substances 0.000 claims description 6
- 238000006056 electrooxidation reaction Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000009990 desizing Methods 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 4
- 239000000306 component Substances 0.000 abstract 3
- 239000008358 core component Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
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- 235000019441 ethanol Nutrition 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- VENMWZIMYAYKOI-UHFFFAOYSA-N nickel(2+) propan-2-one dinitrate Chemical compound CC(=O)C.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] VENMWZIMYAYKOI-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a method for growing carbon nanotubes by using a catalyst with a core-shell structure on the surface of a carbon fiber, which comprises the following steps ofAnd the carbon nano tube-carbon fiber multi-scale reinforcement prepared based on the method and the application thereof. The implementation method of the invention comprises the following steps: after the carbon fiber is surface activated, the precursor A is firstly prepared 0 Uniformly soaking and drying the solvent in the solution of (2), and then performing thermal reduction isolated from air to lead the precursor A 0 A core component a converted into a catalyst; the carbon fiber loaded with the component A is then fed into the precursor B again 0 The solvent is uniformly immersed in the solution and dried, and the shell component B of the catalyst is formed by adopting the same thermal reduction method. The method can effectively utilize different catalytic properties of different components, so that the carbon nano tube with regular structure and high yield is grown on the surface of the carbon fiber, the accompaniment of amorphous carbon impurities is reduced, and the damage to the carbon fiber in the process is reduced.
Description
Technical Field
The invention relates to the technical field of carbon fiber surface modification, in particular to a method for growing carbon nanotubes by using a catalyst with a core-shell structure supported on the surface of a carbon fiber and application of the catalyst.
Background
The statements in this section merely relate to the background of the present disclosure and may not necessarily constitute prior art.
As one of the emerging high performance materials of great interest, carbon fiber has been used in a large number in the fields of weaponry, aerospace, building reinforcement, geological mining, vehicle ships, sporting goods, and the like. However, the most important form of application, carbon fiber reinforced composites, are limited in terms of various mechanical properties by poor bonding of the fiber/matrix interface. The nano-scale reinforcement of the interface phase with a certain thickness, namely the carbon nano tube-carbon fiber multi-scale reinforcement, is realized by growing a carbon nano tube network on the surface of the carbon fiber in situ, and the nano-scale reinforcement is one of the most potential interface reinforcement methods. The preparation method of the multi-scale reinforcement has realized serialization, and has the advantages of easy operation, low equipment cost and the like.
The catalyst is a core element for preparing the carbon nano tube-carbon fiber. The carbon source molecules are separated into active carbon units under the catalysis of the carbon source molecules, and the carbon units are diffused in the catalyst particles and assembled into a carbon nano tube structure on the surface of the carbon fiber. The carbon nanotube catalyst widely used at present comprises magnetic nano particles such as iron, cobalt, nickel and the like and non-magnetic nano particles such as copper and the like. The catalyst is formed on the surface of the carbon fiber in situ in a precursor conversion mode, and metals with different physical properties can form nano particles with different distributions and sizes on the surface of the carbon fiber and also show different catalytic behaviors. Presently disclosed catalysts include single component catalysts, as well as multi-component catalysts composed of two or more metals in combination. However, from the perspective of individual particles, the constituent structure is a homogeneous metal or alloy, i.e., a catalyst of homogeneous structure.
The carbon nano tube-carbon fiber multi-scale reinforcement prepared at present has the following problems: irregular carbon nanotube structure, uneven carbon nanotube distribution, coating of carbon fiber surface by a large amount of amorphous carbon impurities, strength reduction caused by catalyst etching of carbon fiber surface, and the like. These problems can further lead to the composite materials having internal defects, stress concentrations, poor resin wetting, and other weaknesses. The use of different metals as catalysts can circumvent one or both of these problems, but other problems are correspondingly exacerbated, which is a difficult problem for catalysts of homogeneous structure to cross over.
In summary, various homogeneous structure catalysts adopted in the prior art have difficulty in solving various defects of carbon nanotube structures, distribution, impurities, damage of the catalyst to fiber strength and the like existing in the prepared carbon nanotube-carbon fiber. The homogeneous composition structure makes the catalytic performance of various metals difficult to be synergistically exerted.
Disclosure of Invention
In view of the above, the invention provides a method for growing carbon nanotubes by using a carbon fiber surface supported core-shell catalyst and application thereof, and the formation of the carbon nanotubes mainly depends on the surface layer diffusion due to the difference of the diffusion mechanism of an active carbon unit in the surface layer and the inside of particles of the catalyst.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect, the invention provides a method for growing carbon nanotubes by using a carbon fiber surface supported core-shell catalyst, which is characterized by comprising the following steps:
s1: carrying out surface activation on the carbon fiber;
s2: precursor A 0 Uniformly dipping the solution on the surface of the carbon fiber after surface activation, and then drying the solvent in the solution to lead the precursor A 0 Loading the precursor A on the surface of the carbon fiber 0 Carbon fibers of (2);
s3: loading the precursor A in a heating device which is isolated from air and filled with hydrogen 0 Is subjected to thermal reduction treatment to lead the precursor A 0 Converting into nano particles A to obtain carbon fibers loaded with the nano particles A;
s4: feeding the carbon fiber loaded with the nano particles A into a precursor B 0 Soaking in the solution, and drying the solvent in the solution to obtain the precursor B 0 Loading on the surface of the carbon fiber to obtain the nano-particle A and the precursor B 0 Carbon fibers of (2); loading nanoparticle A and precursor B in a heating device isolated from air and filled with hydrogen 0 Is subjected to thermal reduction treatment to lead the precursor B 0 The outer layer of the nano particle A is reduced into a nano particle B, and the carbon fiber with the A@B core-shell structure catalyst loaded on the surface in situ is obtained;
s5: and (3) delivering the carbon fiber with the A@B core-shell structure catalyst loaded on the surface in situ into a chemical vapor deposition furnace filled with hydrogen and a gaseous carbon source, so that the gaseous carbon source is decomposed under the action of the catalyst to form carbon nanotubes, and thus the carbon nanotube-carbon fiber multi-scale reinforcement is obtained.
In a second aspect, the invention provides a carbon nanotube-carbon fiber multi-scale reinforcement prepared by the method for growing carbon nanotubes by using the carbon fiber surface supported core-shell catalyst.
In a third aspect, the present invention provides a carbon fiber composite comprising the carbon nanotube-carbon fiber multi-scale reinforcement of the second aspect.
In a fourth aspect, the invention provides the use of the carbon fiber composite material in military equipment, aerospace, sporting goods, industrial equipment, infrastructure, marine vehicles, and new energy component energy.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst can effectively combine different catalytic performances of the A, B catalyst components, and can obtain a catalyst with excellent performance by selecting metal with uniform particle size and distribution and lower melting point as an A component (core), such as copper or copper-nickel alloy, and selecting metal with high catalytic efficiency as a B component (shell), such as nickel; meanwhile, the metal with small diffusion coefficient in the carbon fiber is adopted as the A component, such as copper, so that the damage of the fiber strength can be remarkably reduced.
(2) The excellent catalyst prepared by the invention can effectively improve the regularity and yield of the carbon nano tube, and simultaneously reduce the formation of amorphous carbon impurities, thereby obviously improving the mechanical properties of the carbon nano tube-carbon fiber multi-scale reinforcement and the composite material thereof.
(3) The preparation method of the carbon nano tube-carbon fiber multi-scale reinforcement has good suitability with the existing mainstream process operation and process equipment, is simple to operate, has low process requirements, and has continuous preparation conditions, so that the preparation method has potential for large-scale application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic illustration of the mechanism of the process according to the invention, wherein the right-hand insert is a scanned view of the elements of the catalyst obtained in step 4 of example 1;
fig. 2 (a) is a transmission electron microscopic view of the carbon nanotubes in the carbon nanotube-carbon fiber multi-scale reinforcement obtained in example 1, and fig. 2 (b) is a transmission electron microscopic view of the carbon nanotubes in the carbon nanotube-carbon fiber multi-scale reinforcement obtained in comparative example 2;
fig. 3 (a) is a secondary electron scanning electron microscope image of the surface of the carbon nanotube-carbon fiber multi-scale reinforcement obtained in example 1, and fig. 3 (b) is a secondary electron scanning electron microscope image of the surface of the carbon nanotube-carbon fiber multi-scale reinforcement obtained in comparative example 2.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As introduced in the background art, various homogeneous structure catalysts adopted in the prior art have difficulty in solving various defects of carbon nano tube structures, distribution, impurities, damage of the catalyst to fiber strength and the like existing in the prepared carbon nano tube-carbon fiber. Based on the above, the invention provides a method for growing carbon nanotubes by loading a core-shell structure catalyst on the surface of a carbon fiber, which comprises the following steps:
s1: carrying out surface activation on the carbon fiber to enable the surface of the carbon fiber to have polar functional groups and rough grooves, so that the permeation of a precursor solution and the adhesion of reduced nano particles are facilitated;
s2: precursor A 0 The solution is uniformly impregnated on the surface of the activated carbon fiber, and then the solvent is dried to lead the solute precursor A to be 0 Loading onto the surface of the fiber;
s3: loading the precursor A in a heating device which is isolated from air and filled with hydrogen 0 Is subjected to thermal reduction treatment to lead the precursor A 0 Conversion to nanoparticle a;
s4: will be loaded with sodiumCarbon fiber feeding precursor B of rice grain A 0 Soaking in the solution, and drying the solvent to obtain the precursor B 0 Loading onto the surface of the fiber; loading nanoparticle A and precursor B in a heating device isolated from air and filled with hydrogen 0 Is subjected to thermal reduction treatment to lead the precursor B 0 Is reduced to nano particles B outside the nano particles A; collecting the obtained carbon fiber to obtain the carbon fiber with the A@B core-shell structure catalyst loaded on the surface in situ;
s5: the carbon fiber with the A@B core-shell structure catalyst loaded on the surface in situ is sent into a chemical vapor deposition furnace filled with hydrogen and a gaseous carbon source, so that the carbon source is decomposed under the action of the catalyst to form carbon nanotubes; collecting the obtained fiber to obtain the carbon nano tube-carbon fiber multi-scale reinforcement.
In some embodiments, the steps may be performed separately or continuously on a continuous apparatus with a travel speed of the carbon fiber tow of 5-25cm/min, preferably 15-20cm/min.
In some embodiments, the carbon fiber is any one of level T300, level T700, level T800 and level T1000, the number of filaments is any one of 1K, 3K, 6K and 12K, and the form is any one of chopped carbon fiber, continuous carbon fiber, carbon fiber fabric and carbon fiber paper; the carbon fiber is unglued carbon fiber or commercial carbon fiber which is subjected to desizing.
In some embodiments, the method of surface activation in step S1 is electrochemical oxidation treatment or chemical oxidation.
In some embodiments, the surface activation method in step S1 is preferably electrochemical oxidation treatment, and the specific treatment method is: taking carbon fiber as an anode and graphite as a cathode, wherein the charge density in the carbon fiber is 50-150C/g, and the electrolyte is deionized water solution of monoammonium phosphate, diammonium phosphate or ammonium bicarbonate, and the concentration is 2-6wt.%; preferably, the charge density is 80-120C/g, and the electrolyte is 3-5wt.% monoammonium phosphate deionized water solution.
In some embodiments, the precursor a 0 And precursor B 0 Respectively isA. Any one or more of metal chloride, metal nitrate and metallocene corresponding to the two components B, wherein the solvent in the precursor solution is any one of deionized water, ethanol and acetone, and the total concentration of metal ions in the precursor solution is 0.01-0.1mol/L; preferably, the precursor is metal nitrate, the solvent is ethanol, and the total concentration of metal ions in the solution is 0.02-0.05mol/L.
In some embodiments, the component a is a mixture of any one or more of copper, iron, cobalt, nickel, and the component B is a mixture of any one or more of copper, iron, cobalt, nickel that is different from component a. Preferably, the component A is copper, cobalt or copper-nickel alloy with a molar ratio of 1-5:1, and the component B is nickel, iron or copper-nickel alloy which is different from the component A and has a molar ratio of 0.2-1:1.
In some embodiments, the heating device in steps S3 and S4 is a tube furnace, the temperature of the thermal reduction treatment is 350-500 ℃, the flow rate of the hydrogen is 0.2-1.5L/min, and the time of the thermal reduction treatment is 2-15min.
In some embodiments, the gaseous carbon source is any one or more of methane, acetylene, carbon monoxide, gaseous ethanol, and the flow ratio of hydrogen to gaseous carbon source is 0.8-3:1. preferably, the carbon source is acetylene, and the flow ratio of the hydrogen to the gaseous carbon source is 1-1.5:1.
in some embodiments, the furnace temperature of the chemical vapor deposition furnace is 500-750 ℃, and the chemical vapor deposition reaction time is 2-15min; preferably, the furnace temperature of the chemical vapor deposition furnace is 600-650 ℃, and the chemical vapor deposition reaction time is 3-10min.
In another embodiment of the invention, a carbon nanotube-carbon fiber multi-scale reinforcement prepared by the method for growing carbon nanotubes by using the carbon fiber surface supported core-shell catalyst is provided.
In another embodiment of the present invention, there is provided an application of the carbon nanotube-carbon fiber multi-scale reinforcement in preparing a composite material, including but not limited to directly using the continuous fiber obtained by the continuous device of the present invention to prepare a unidirectional composite material, or preparing a fabric from carbon fiber and then preparing the composite material. The obtained carbon nano tube-carbon fiber multi-scale reinforcement is mainly applied to preparing resin matrix composite materials and can also be used for preparing composite materials by compounding with other matrixes.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the present invention will be further described in detail with reference to specific examples.
Example 1
Step 1: commercial T800-grade carbon fiber (12K) is pulped and then is sent into an electrolytic cell, 5wt.% of monoammonium phosphate solution is used as electrolyte in the electrolytic cell, a graphite plate is used as a cathode, continuously advancing carbon fiber tows are used as anodes, the charge density on the carbon fibers is 100C/g, then the electrolyte is washed out in deionized water, and the electrolyte is dried by a 70 ℃ oven;
step 2: soaking the activated carbon fiber obtained in the step 1 in an absolute ethyl alcohol solution containing 0.03mol/L copper nitrate for 10min, and then drying the activated carbon fiber in a 70 ℃ oven;
step 3: delivering the carbon fiber with copper ions obtained in the step 2 into a tubular furnace (A) for treatment for 5min, and introducing hydrogen with the flow of 0.6L/min into the furnace, wherein the furnace temperature is 400 ℃;
step 4: immersing the carbon fiber with the nano copper particles obtained in the step 3 in an absolute ethanol solution containing 0.02mol/L nickel nitrate for 10min, then drying the carbon fiber with the nano copper particles in a 70 ℃ oven, and sending the carbon fiber into a tubular furnace (B) which is arranged in the same way as the tubular furnace (A) for 5min;
step 5: feeding the carbon fiber loaded with the catalyst obtained in the step 4 into a tubular furnace (C) which is isolated from air and filled with mixed gas of hydrogen and acetylene, and treating for 8min, wherein the flow rate of the hydrogen in the furnace is 0.4L/min, the flow rate of the acetylene is 0.2L/min, and the furnace temperature is 650 ℃;
and 5, collecting the obtained carbon fibers after the step 5 to obtain the carbon nanotube-carbon fiber multi-scale reinforcement.
Example 2
The difference from example 1 is that: the absolute ethanol solution in the step 2 contains 0.02mol/L copper nitrate and 0.01mol/L nickel nitrate.
Example 3
The difference from example 1 is that: the absolute ethanol solution in the step 2 contains 0.03mol/L cobalt nitrate.
Example 4
The difference from example 1 is that: the absolute ethanol solution in the step 2 contains 0.01mol/L copper nitrate and 0.02mol/L cobalt nitrate.
Example 5
The difference from example 1 is that: the absolute ethyl alcohol solution in the step 2 contains 0.04mol/L copper nitrate; the absolute ethanol solution in the step 4 contains 0.01mol/L nickel nitrate.
Example 6
The difference from example 1 is that: the absolute ethanol solution in the step 4 contains 0.02mol/L ferric nitrate.
Example 7
The difference from example 1 is that: the absolute ethanol solution in the step 4 contains 0.02mol/L cobalt nitrate.
Example 8
The method for growing the carbon nano tube on the surface of the continuous carbon fiber at ultralow temperature is implemented by adopting a continuous device, and the advancing speed of the carbon fiber tows is set to be 20cm/min in the following continuous steps;
step 1: continuously running non-slurry T300 grade carbon fiber (3K) is subjected to surface activation through an electrolytic cell, is cleaned through a deionized water tank, and is dried through a 70 ℃ oven; wherein the electrolyte is 3wt.% of monoammonium phosphate deionized water solution, the cathode is a graphite plate, and the charge quantity density in the carbon fiber is 80C/g;
step 2: the carbon fiber treated in the step 1 is then soaked in a mixed acetone solution of copper nitrate and cobalt nitrate for 5min, and then is dried in a 70 ℃ oven;
step 3: the carbon fiber treated in the step 2 is then subjected to thermal reduction in a tubular furnace with argon gas seals at two ends and hydrogen gas mixed gas filled in the tubular furnace for 10min; wherein the concentration of copper ions in the solution is 0.02mol/L, the concentration of cobalt ions in the solution is 0.02mol/L, the temperature of the tube furnace is 500 ℃, and the hydrogen flow is 1L/min;
step 4: the carbon fiber treated in the step 3 is then soaked in nickel nitrate acetone solution for 5min, then dried in a 70 ℃ oven, and then subjected to thermal reduction in a tubular furnace filled with hydrogen mixed gas in which argon gas seals are arranged at two ends for 10min; wherein the concentration of nickel ions in the solution is 0.01mol/L, the temperature of the tube furnace is 500 ℃, and the hydrogen flow is 1L/min;
step 5: the carbon fiber treated in the step 4 is then put into a tube furnace with both ends sealed by nitrogen gas and filled with mixed gas of hydrogen and methane for carbon nanotube growth for 15min; the temperature of the tube furnace is 700 ℃, the hydrogen flow is 0.7L/min, and the methane flow is 0.3L/min;
and 5, continuously collecting the product by using a filament collecting machine to obtain the continuous carbon nano tube-carbon fiber multi-scale reinforcement.
Example 9
Step 1: soaking the short-cut T700 carbon fiber in acetone for 24 hours to remove slurry, taking out and drying by a 60 ℃ oven, then soaking in 10wt.% hydrogen peroxide for 30 minutes to activate the surface, taking out and drying by the 60 ℃ oven;
step 2: soaking the carbon fiber obtained in the step 1 in 0.03mol/L cobalt nitrate deionized water solution for 10min, taking out, and drying by using a 60 ℃ oven;
step 3: then the carbon fiber dried in the step 2 is put into a closed furnace, air is discharged and hydrogen with the volume of 1.2L/min is introduced, and the temperature is raised to 450 ℃ and kept for 10min;
step 4: taking out the carbon fiber obtained in the step 3, soaking the carbon fiber in 0.02mol/L ferric nitrate deionized water solution for 10min, taking out the carbon fiber, drying the carbon fiber by using a 60 ℃ oven, then putting the carbon fiber into a closed furnace, discharging air, introducing 1.2L/min of hydrogen, heating the carbon fiber to 450 ℃ and keeping the temperature for 10min, introducing 0.8L/min of acetylene, and heating the carbon fiber to 600 ℃ and keeping the temperature for 10min;
and (3) collecting the carbon fibers obtained in the step (4) to obtain the chopped carbon nanotube-carbon fiber multi-scale reinforcement.
Comparative example 1
The difference from example 1 is that: the absolute ethyl alcohol solution in the step 2 contains 0.05mol/L copper nitrate; step 5 is directly performed without performing step 4 after step 3.
Comparative example 2
The difference from comparative example 1 is that: the absolute ethanol solution in the step 2 contains 0.05mol/L nickel nitrate.
Comparative example 3
The difference from comparative example 1 is that: the absolute ethanol solution in the step 2 contains 0.05mol/L cobalt nitrate.
Comparative example 4
The difference from comparative example 1 is that: the absolute ethanol solution in the step 2 contains 0.02mol/L copper nitrate and 0.03mol/L nickel nitrate.
Comparative example 5
The difference from comparative example 1 is that: the absolute ethanol solution in the step 2 contains 0.03mol/L copper nitrate and 0.02mol/L nickel nitrate.
As can be seen from the combination of the element scanning results in FIG. 1 and the X-ray photoelectron spectroscopy element analysis results in Table 1, the catalyst obtained in step 4 of example 1 has a core-shell structure with an outer layer of nickel and an inner layer of copper.
TABLE 1X-ray photoelectron Spectrometry characterization of the composition of the catalyst obtained in step 4 of example 1 at different etch depths
| Depth of etching | Cu atomic ratio (at%) in metal | Ni atomic ratio (at%) in metals |
| 1nm | 8 | 92 |
| 5nm | 33 | 67 |
| 9nm | 72 | 28 |
| 13nm | 64 | 36 |
| 17nm | 42 | 58 |
Table 2 shows the graphitization degree of the multi-scale reinforcement of the carbon nano tube-carbon fiber prepared in the examples 1-2 and the comparative examples 1-5 according to the present invention.
TABLE 2 comparative table of graphitization degree of carbon nanotube-carbon fiber multiscale reinforcement
As can be seen from table 2, the carbon nanotube-carbon fiber multiscale reinforcement prepared by using the core-shell structure catalyst supported on the carbon fiber surface of the present invention has significantly better graphitization degree (i.e., smaller raman R value) than the carbon nanotube prepared by using the homogeneous catalyst of each comparative example. As can be seen from fig. 2, the carbon nanotubes on the surface of the product obtained in example 1 had a regular hollow tubular structure, while the surface of comparative example 2 using a single nickel component had a nanowire structure. As can be seen from fig. 3, the multi-scale reinforcement of carbon nanotubes-carbon fibers obtained in example 1 has uniform thickness, is very clear, contains almost no nodules and clusters, and the multi-scale reinforcement of carbon nanotubes-carbon fibers prepared in comparative example 2 is more disordered and accompanies a large amount of impurities. As can be seen from the Chemical Vapor Deposition (CVD) products and distribution summarized in Table 2, in the comparative examples, the products were either rare (as in comparative example 1) or too dense with poor structures such as impurities and clusters, whereas the CVD deposition products obtained in the present invention were mainly carbon nanotubes uniformly and densely distributed on the surface of the carbon fibers.
Table 3 shows the physical properties of the multi-scale reinforcement of carbon nanotubes-carbon fibers prepared in examples 1-2 and comparative examples 1-5 of the present invention.
TABLE 3 physical Properties of carbon nanotube-carbon fiber multiscale reinforcement
As can be seen from table 3, the carbon deposition amount of the carbon nanotube-carbon fiber multiscale reinforcement prepared according to the present invention is significantly higher than that of comparative examples 1 and 3 using pure copper and pure cobalt catalysts, comparable to comparative examples 4 and 5 using copper nickel alloy catalysts, and lower than that of comparative example 2 using pure nickel catalysts. Although comparative examples 2, 4, and 5 have higher carbon deposition amounts, it can be seen from table 2 and fig. 3 that more amorphous carbon impurities exist in each of comparative examples 2, 4, and 5. Too little growth of the carbon nanotubes may result in insufficient interfacial bonding of the resin, while too much carbon nanotubes and accompanying impurities may result in the resin being blocked from impregnating. The invention not only avoids the mass production of impurities, but also obtains more high-quality deposition products. These advantages can also be seen from the specific surface area and contact angle data of table 3, the larger specific surface area side reflects less carbon impurities blocking the pores in the product of the invention; lower contact angles indicate better wettability, higher porosity and less amorphous impurity carbon. The data show that the carbon nano tube-carbon fiber multi-scale reinforcement prepared by the invention has obvious structural advantages compared with the prior art.
Table 4 shows the comparison of interface properties of the carbon nanotube-carbon fiber multi-scale reinforcement prepared in the examples and comparative examples.
TABLE 4 carbon nanotube-carbon fiber multiscale reinforcement interfacial properties
The structural advantage in the microcosmic field enables the multi-scale reinforcement of the carbon nano tube-carbon fiber prepared by the invention to be greatly improved in the aspect of interface performance. Table 4 shows that the interfacial shear strength and the interlaminar shear strength of the multi-scale reinforcement of carbon nanotubes-carbon fibers prepared in examples 1 and 2 are significantly better than those of each of the comparative examples. Comparison of interlayer shear modulus shows that the carbon nano tube prepared by the invention has obvious reinforcing effect on the interface of the composite material, so that the modulus of the composite material is greatly improved. The mechanical property of the prepared composite material is greatly improved by firmly combining the interfaces, which proves that the carbon nano tube-carbon fiber multi-scale reinforcement obtained by catalyzing the growth of the carbon nano tube by adopting the carbon fiber in-situ supported core-shell structure catalyst has excellent performance.
Table 5 shows the tensile properties of the fiber monofilaments of the carbon nanotube-carbon fiber multi-scale reinforcement prepared in the examples and comparative examples of the present invention after catalyst loading and carbon nanotube growth.
TABLE 5 tensile Properties of fiber monofilaments after catalyst loading and carbon nanotube growth
The loading of the metal catalyst results in a weakening of the carbon fiber strength, which is restored to some extent by the CVD process. The degree of damage caused by different kinds of metals is different, and compared with cobalt and nickel, copper has less damage to carbon fibers. Copper is less catalytically efficient and therefore less repair is caused during CVD. It can be seen from table 5 that the advantages of the core-shell catalyst with copper as the inner core and nickel as the outer layer are combined in the embodiment 1, so that the damage caused by the loading of the catalyst is reduced, the higher repairing effect is ensured, and finally, the carbon nano tube-carbon fiber multi-scale reinforcement with the highest tensile strength and modulus is obtained, and the tensile performance is even better than that of the carbon fiber serving as the raw material. The strengthening of the tensile property of the reinforcement body also enhances various mechanical properties of the composite material.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for growing the carbon nano tube by using the catalyst with the core-shell structure loaded on the surface of the carbon fiber is characterized by comprising the following steps of:
s1: carrying out surface activation on the carbon fiber;
s2: precursor A 0 Uniformly dipping the solution on the surface of the carbon fiber after surface activation, and then drying the solvent in the solution to lead the precursor A 0 Loading the precursor A on the surface of the carbon fiber 0 Carbon fibers of (2);
s3: loading the precursor A in a heating device which is isolated from air and filled with hydrogen 0 Is subjected to thermal reduction treatment to lead the precursor A 0 Converting into nano particles A to obtain carbon fibers loaded with the nano particles A;
s4: feeding the carbon fiber loaded with the nano particles A into a precursor B 0 Soaking in the solution, and drying the solvent in the solution to obtain the precursor B 0 Loading on the surface of the carbon fiber to obtain the nano-particle A and the precursor B 0 Carbon fibers of (2); loading nanoparticle A and precursor B in a heating device isolated from air and filled with hydrogen 0 Is subjected to thermal reduction treatment to lead the precursor B 0 Coated on the outer layer of the nano particle AReducing the carbon fiber into nano particles B to obtain carbon fiber with A@B core-shell structure catalyst loaded on the surface in situ;
s5: and (3) delivering the carbon fiber with the A@B core-shell structure catalyst loaded on the surface in situ into a chemical vapor deposition furnace filled with hydrogen and a gaseous carbon source, so that the gaseous carbon source is decomposed under the action of the catalyst to form carbon nanotubes, and thus the carbon nanotube-carbon fiber multi-scale reinforcement is obtained.
2. The method for growing carbon nanotubes by using a carbon fiber surface supported core-shell catalyst according to claim 1, wherein the precursor A 0 And precursor B 0 The precursor solution contains one or more of metal chloride, metal nitrate and metallocene corresponding to A, B, wherein the solvent in the precursor solution is any one of deionized water, ethanol and acetone, and the total concentration of metal ions in the precursor solution is 0.01-0.1mol/L; preferably, the precursor is metal nitrate, the solvent is ethanol, and the total concentration of metal ions in the solution is 0.02-0.05mol/L.
3. The method for growing carbon nanotubes by using the carbon fiber surface supported core-shell catalyst according to claim 1, wherein the component A is a mixture of any one or more of copper, iron, cobalt and nickel, and the component B is a mixture of any one or more of copper, iron, cobalt and nickel different from the component A; preferably, the component A is copper, cobalt or copper-nickel alloy with a molar ratio of 1-5:1, and the component B is nickel, iron or copper-nickel alloy which is different from the component A and has a molar ratio of 0.2-1:1.
4. The method for growing carbon nanotubes by using the carbon fiber surface supported core-shell catalyst according to claim 1, wherein the heating equipment in the steps S3 and S4 is a tube furnace, the temperature of the thermal reduction treatment is 350-500 ℃, the flow rate of the hydrogen is 0.2-1.5L/min, and the time of the thermal reduction treatment is 2-15min.
5. The method for growing carbon nanotubes by using the carbon fiber surface supported core-shell catalyst according to claim 1, wherein the gaseous carbon source is any one or more of methane, acetylene, carbon monoxide and gaseous ethanol, and the flow ratio of the hydrogen to the gaseous carbon source is 0.8-3:1, a step of; preferably, the carbon source is acetylene, and the flow ratio of the hydrogen to the gaseous carbon source is 1-1.5:1, a step of;
the furnace temperature of the chemical vapor deposition furnace is 500-750 ℃, and the chemical vapor deposition reaction time is 2-15min; preferably, the furnace temperature of the chemical vapor deposition furnace is 600-650 ℃, and the chemical vapor deposition reaction time is 3-10min.
6. The method for growing carbon nanotubes by using the carbon fiber surface supported core-shell structure catalyst according to claim 1, wherein the carbon fiber is any one of a T300 grade, a T700 grade, a T800 grade and a T1000 grade, the number of the carbon fiber is any one of 1K, 3K, 6K and 12K, and the carbon fiber is any one of a chopped carbon fiber, a continuous carbon fiber, a carbon fiber fabric and a carbon fiber paper;
the carbon fiber is unglued carbon fiber or commercial carbon fiber which is subjected to desizing.
7. The method for growing carbon nanotubes by using the carbon fiber surface supported core-shell catalyst according to claim 1, comprising the steps of: the surface activation method in the step S1 is electrochemical oxidation treatment or chemical oxidation; preferably an electrochemical oxidation treatment method, and the specific treatment mode is as follows: taking carbon fiber as an anode and graphite as a cathode, wherein the charge density in the carbon fiber is 50-150C/g, and the electrolyte is deionized water solution of monoammonium phosphate, diammonium phosphate or ammonium bicarbonate, and the concentration is 2-6wt.%; preferably, the charge density is 80-120C/g, and the electrolyte is 3-5wt.% monoammonium phosphate deionized water solution.
8. A carbon nanotube-carbon fiber multiscale reinforcement prepared by the method for growing carbon nanotubes by supporting a core-shell catalyst on the surface of carbon fiber according to any one of claims 1 to 7.
9. A carbon fiber composite comprising the carbon nanotube-carbon fiber multi-scale reinforcement of claim 8.
10. Use of the carbon fiber composite material of claim 9 in military equipment, aerospace, sporting goods, industrial equipment, infrastructure, marine vehicles, and new energy component energy.
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