CN116947111B - Method for preparing wave-absorbing material by in-situ vulcanization reaction of graphite nano-sheet composite cobalt particles - Google Patents
Method for preparing wave-absorbing material by in-situ vulcanization reaction of graphite nano-sheet composite cobalt particles Download PDFInfo
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- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 131
- 239000010439 graphite Substances 0.000 title claims abstract description 131
- 239000002131 composite material Substances 0.000 title claims abstract description 113
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000002135 nanosheet Substances 0.000 title claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 40
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 20
- 239000011358 absorbing material Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000010941 cobalt Substances 0.000 title claims description 65
- 229910017052 cobalt Inorganic materials 0.000 title claims description 65
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 65
- 239000002245 particle Substances 0.000 title claims description 40
- 238000004073 vulcanization Methods 0.000 title claims description 15
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 37
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000002055 nanoplate Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 125000005498 phthalate group Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000006249 magnetic particle Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 229910021389 graphene Inorganic materials 0.000 description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
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Abstract
The invention relates to the technical field of preparation of graphite nano-sheet composite magnetic particles, in particular to a method for preparing composite powder which is suitable for a wave-absorbing material and has a sheet-core-shell microstructure of graphite nano-sheet-cobalt sulfide. The method has the remarkable advantages of simple preparation process, in-situ reaction generation, easy operation, large-scale mass production and the like.
Description
Technical Field
The invention relates to the technical field of preparation of graphite nano-sheet composite magnetic particles, in particular to a preparation method of a composite material which is suitable for a wave-absorbing material and has a sheet-core-shell microstructure of cobalt sulfide-cobalt-graphite nano-sheets.
Background
Along with the accelerated innovation of the world military technology, the remote precision, intelligence, stealth and unmanned trend of weaponry are more remarkable. Stealth performance has become a typical feature and important capability of new generation weaponry. In recent years, a wave absorbing material technology represented by a novel carbon-based radar wave absorbing composite material such as graphene becomes a key hot spot for stealth technology development. In the electromagnetic wave field, the graphene surface loaded with magnetic particles can form comprehensive performances such as electric loss, magnetic loss, dielectric loss and the like, and the comprehensive performances are improved. The magnetic metal sulfide composite graphite nano-sheet can be well applied to the field of electromagnetic wave absorption.
In the prior art, graphene oxide prepared by a chemical method is mostly used as a carrier for the magnetic metal sulfide composite graphite nano-sheet, and chemical reduction is performed to realize the composite of graphene nano-sheet layers and magnetic oxide, for example, in the preparation method of cobalt metal particles and cobalt oxide composite graphite nano-sheet powder of the Chinese patent, ZL201911250054.2, an oxidizing solution is used for in-situ chemical reaction to precipitate cobalt oxide coated on the surface of cobalt metal, so that a multi-phase composite wave absorber of cobalt oxide-cobalt-graphite nano-sheet is obtained, and a microstructure composite powder of core-shell-sheet is formed, wherein the microstructure composite powder is used for improving the wave absorbing characteristic of the magnetic particle composite graphite nano-sheet, but the magnetic loss of the cobalt oxide composite graphite nano-sheet powder is very high, but the dielectric loss is weaker, and the requirements of the application in the electromagnetic wave absorbing field are still not met.
Therefore, there is a need for a method for preparing graphite nano-sheet composite cobalt metal particles and wave-absorbing materials for in-situ vulcanization reaction, which is easy to operate, has no loop pressure and can be mass-produced.
Disclosure of Invention
The method is simple in preparation process, easy to operate, free of pressure maintaining, capable of realizing large-scale mass production of graphite nano-sheet composite cobalt metal particles and in-situ vulcanization reaction, and capable of obtaining the cobalt sulfur compound.
The embodiment of the application can be realized through the following technical scheme:
the method for preparing the wave-absorbing material by the in-situ vulcanization reaction of the graphite nano-sheet composite cobalt particles is used for preparing the wave-absorbing material in the form of the graphite nano-sheet composite cobalt particles and comprises the following specific steps of:
s1: preparing cobalt-graphite nano-sheet composite powder;
s2: immersing the cobalt-graphite nano-sheet composite powder in an organic solvent ethylene glycol, and fully stirring for more than 2 hours to obtain a cobalt-graphite nano-sheet composite solution;
s3: adding thiourea and a dispersing agent into the solution of the cobalt-graphite nano-sheet composite solution to form an organic solution mixed with cobalt-graphite nano-sheets and a vulcanizing agent;
s4: placing the organic solution mixed with the cobalt-graphite nano-sheets and the vulcanizing agent into a reaction kettle, and reacting for 3-6 hours at 160-180 ℃ to enable the surface of the cobalt-graphite nano-sheet composite to generate a vulcanizing layer, so as to form composite powder with the vulcanizing layer;
s5: taking out the composite powder with the vulcanized layer, and drying the composite powder in a drying box at the temperature of 30-60 ℃ for 2-10 hours to obtain the graphite nano-sheet composite cobalt particles.
Further, the cobalt particles have a particle size in the range of: 0.1-5 microns.
Further, the dispersing agent is silane coupling agent KH-570, wherein the thiourea: the silane coupling agent KH-570: the proportion of the ethylene glycol is 3:0.1 to 1.5:1000.
further, the dispersant is phthalate coupling agent NDZ-401, wherein the thiourea: the phthalate coupling agent NDZ-401: the proportion of the ethylene glycol is 7:0.1 to 1.0:1000.
further, step S1 further comprises the steps of:
s11: immersing the graphite nano-sheets in an oxidizing acid solution for 10-12 hours to obtain graphite micro-sheets;
s12: washing out graphite micro-plates, using a cobalt salt solution containing a reducing agent, adding sodium carboxymethylcellulose with the mass percentage of 0.05-0.5%, and dispersing the acidified graphite micro-plates in the cobalt salt solution under the combined action of mechanical stirring and ultrasonic vibration to obtain a cobalt solution mixed with the graphite micro-plates;
s13: placing the cobalt solution mixed with the graphite micro-plates into a reaction kettle, and reacting for 30-120 minutes at the temperature of 120-180 ℃ to enable cobalt particles to be loaded on the graphite micro-plates, thereby obtaining graphite nano-plate/cobalt composite powder;
s14: and cooling the reaction kettle to room temperature, taking out the graphite nano sheet/cobalt composite powder, and drying in a drying box at 30-60 ℃ to obtain the cobalt-graphite nano sheet composite powder.
The method for preparing the wave-absorbing material by the in-situ vulcanization reaction of the graphite nano-sheet composite cobalt particles has at least the following beneficial effects:
according to the invention, the vulcanizing agent is used for carrying out in-situ chemical reaction, and the cobalt sulfur compound is precipitated and coated on the surface of cobalt metal, so that the cobalt sulfur compound-cobalt-graphite nano sheet multiphase composite wave absorber is obtained, and the core-shell-sheet microstructure composite powder is formed and is used for improving the wave absorbing characteristic of the magnetic particle composite graphite nano sheet.
Drawings
FIG. 1 is a specific preparation step of a method for preparing a wave-absorbing material by in-situ vulcanization reaction of graphite nano-sheet composite cobalt particles;
fig. 2 is an XRD spectrum of the graphite nano-sheet composite cobalt particles obtained in the present invention.
Detailed Description
The present application will be further described below based on preferred embodiments with reference to the accompanying drawings.
In addition, various components on the drawings have been enlarged (thick) or reduced (thin) for ease of understanding, but this is not intended to limit the scope of the present application.
The singular forms also include the plural and vice versa.
In the description of the embodiments of the present application, it should be noted that, if the terms "upper," "lower," "inner," "outer," and the like indicate an azimuth or a positional relationship based on the azimuth or the positional relationship shown in the drawings, or an azimuth or a positional relationship that a product of the embodiments of the present application conventionally puts in use, it is merely for convenience of describing the present application and simplifying the description, and does not indicate or imply that the device or element to be referred to must have a specific azimuth, be configured and operated in a specific azimuth, and therefore should not be construed as limiting the present application. Furthermore, in the description of the present application, the terms first, second, etc. are used herein for distinguishing between different elements, but not necessarily for describing a sequential or chronological order of manufacture, and may not be construed to indicate or imply a relative importance, and their names may be different in the detailed description of the present application and the claims.
The terminology used in this description is for the purpose of describing the embodiments of the present application and is not intended to be limiting of the present application. It should also be noted that unless explicitly stated or limited otherwise, the terms "disposed," "connected," and "connected" should be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; the two components can be connected mechanically, directly or indirectly through an intermediate medium, and can be communicated internally. The specific meaning of the terms in this application will be specifically understood by those skilled in the art.
Fig. 1 is a specific preparation step of a method for preparing a wave-absorbing material by in-situ vulcanization reaction of graphite nano-sheet composite cobalt particles, as shown in fig. 1, and the method for preparing the wave-absorbing material by in-situ vulcanization reaction of graphite nano-sheet composite cobalt particles is used for preparing the wave-absorbing material in the form of graphite nano-sheet composite cobalt particles, and is carried out according to the following specific steps:
s1: preparing cobalt-graphite nano-sheet composite powder;
s2: immersing the cobalt-graphite nano-sheet composite powder in an organic solvent ethylene glycol, and fully stirring for more than 2 hours to obtain a cobalt-graphite nano-sheet composite solution;
s3: adding thiourea and a dispersing agent into the solution of the cobalt-graphite nano-sheet composite solution to form an organic solution mixed with cobalt-graphite nano-sheets and a vulcanizing agent;
s4: placing the organic solution mixed with the cobalt-graphite nano-sheets and the vulcanizing agent into a reaction kettle, and reacting for 3-6 hours at 160-180 ℃ to enable the surface of the cobalt-graphite nano-sheet composite to generate a vulcanizing layer, so as to form composite powder with the vulcanizing layer;
s5: taking out the composite powder with the vulcanized layer, and drying the composite powder in a drying box at the temperature of 30-60 ℃ for 2-10 hours to obtain the graphite nano-sheet composite cobalt particles.
Example 1:
s1: preparing cobalt-graphite nano-sheet composite powder (Co/GNs composite material);
in this embodiment, the cobalt particles have a particle size in the range of: about 0.1 to 5 microns.
S2: immersing the cobalt-graphite nano-sheet composite powder in an organic solvent glycol contained in a beaker, and fully stirring for more than 2 hours to obtain a cobalt-graphite nano-sheet composite solution;
s3: adding thiourea and a silane coupling agent KH-570 into the solution of the cobalt-graphite nano-sheet composite solution, wherein the ratio is thiourea: KH-570: ethylene glycol=3: 0.1:1000 to form an organic solution mixed with cobalt-graphite nanoplatelets and a sulfiding agent;
s4: placing the organic solution mixed with the cobalt-graphite nano-sheets and the vulcanizing agent into a reaction kettle, and reacting for 6 hours at 180 ℃ to enable the surface of the cobalt-graphite nano-sheet composite to generate a vulcanizing layer, so as to ensure that the vulcanizing agent reacts with cobalt particles in situ to generate composite powder with the vulcanizing layer;
s5: and taking out the composite powder with the vulcanized layer, and drying the composite powder in a drying box at the temperature of 60 ℃ for 2 hours to obtain the graphite nano-sheet composite cobalt particles.
In this embodiment, the silane coupling agent KH-570 is used as a dispersing agent, and the silane coupling agent KH-570 has the effect of accelerating the uniform dispersion of the cobalt-graphite nano-sheet composite powder in the aqueous solution with the vulcanizing agent, thereby being beneficial to improving the later vulcanization reaction.
Step S1 further comprises the steps of:
s11: immersing the graphite nano-sheets in an oxidizing acid solution for 10 hours to obtain graphite micro-sheets;
s12: washing out graphite micro-plates, using a cobalt salt solution containing a reducing agent, adding 0.05% by mass of sodium carboxymethyl cellulose, and dispersing the acidified graphite micro-plates in the cobalt salt solution under the combined action of mechanical stirring and ultrasonic vibration to obtain a cobalt solution mixed with the graphite micro-plates;
s13: placing the cobalt solution mixed with the graphite micro-plates into a reaction kettle, and reacting for 45 minutes at 150 ℃ to enable cobalt particles to be loaded on the graphite micro-plates, thereby obtaining graphite nano-plate/cobalt composite powder;
s14: and cooling the reaction kettle to room temperature, taking out the graphite nano sheet/cobalt composite powder, and drying in a drying box at 30 ℃ to obtain the cobalt-graphite nano sheet composite powder.
In this example, concentrated nitric acid is used as the oxidizing acid solution.
In this example, sodium borohydride is used as the reducing agent.
It should be noted that, in the present application, the graphite nano-sheet composite cobalt particles are generated by in-situ reaction of the vulcanizing agent and the cobalt particles, but cannot be generated by reaction of the vulcanizing agent and the cobalt oxide composite graphite nano-sheet powder, because the shell of the cobalt oxide composite graphite nano-sheet powder is a smooth shell, the smooth shell has high magnetic loss and good demagnetization characteristics, but the dielectric loss is lower, and if a composite with higher dielectric loss is desired, the rugged shell is formed on the surface of the cobalt particles, so that the dielectric loss can be increased, and the wave absorbing capability of the composite is further improved. The thin shell of the cobalt oxide composite graphite nano sheet powder is difficult to obtain an uneven shell through nitric acid reaction by carrying out a re-etching reaction outside the shell of the cobalt oxide composite graphite nano sheet powder, so that the method creatively adopts a mode of in-situ reaction of a vulcanizing agent and cobalt particles, and under specific reaction conditions, the surface of the metal cobalt particles generates a cobalt-sulfur compound shell layer which is an uneven shell layer, and the method has the advantage of enhancing dielectric loss and can greatly improve the wave absorbing capacity of the cobalt-sulfur compound shell layer.
FIG. 2 is an XRD spectrum of the graphite nano-sheet composite cobalt particles obtained in the invention, as shown in FIG. 2, in the XRD spectrum, characteristic peak positions of the graphite nano-sheets correspond to 23-26 degrees, which shows that the graphite nano-sheets are taken as a matrix in a composite product, and Co and a compound thereof are composited; a wider "steamed bread peak" appears between 40 and 50 degrees, corresponding to the polycrystalline product of the product metal Co. Co corresponding to standard card at 31 degrees and 52 degrees 9 S 8 Identical, showing that the main product of shell coating in the composite product is Co 9 S 8 . It can be stated that the composite material comprises graphite nano-sheets, metal Co and Co 9 S 8 。
In addition, there are also some applications in which vulcanization reactions are employed, for example, the application number: 201610766152.1, a lithium ion battery cathode, a lithium ion battery, and a preparation method of a cobalt sulfide/graphene nanocomposite, wherein graphene oxide is used in the comparison document, and the surface of the comparison document has a large number of defects, chemical functional groups, carboxyl groups, hydroxyl groups, carbonyl groups and the like, which are not included in the application. And the graphene/cobalt sulfide composite made by the comparison document has the essential difference that the graphene/cobalt composite is coated with the cobalt sulfide shell through in-situ chemical reaction.
Example 2:
the difference between this example and example 1 is that thiourea was used: KH-570: the proportion of ethylene glycol is 3:1.5:1000, in step S5, the composite powder having the vulcanized layer was taken out, and dried in a drying oven at 30 ℃ for 10 hours to obtain graphite nano-sheet composite cobalt particles, and other steps and parameters were the same as in example 1.
Step S1 further comprises the steps of:
s11: immersing the graphite nano-sheets in an oxidizing acid solution for 12 hours to obtain graphite micro-sheets;
s12: washing out graphite micro-plates, using a cobalt salt solution containing a reducing agent, adding 0.5% by mass of sodium carboxymethyl cellulose, and dispersing the acidified graphite micro-plates in the cobalt salt solution under the combined action of mechanical stirring and ultrasonic vibration to obtain a cobalt solution mixed with the graphite micro-plates;
s13: placing the cobalt solution mixed with the graphite micro-plates into a reaction kettle, and reacting for 120 minutes at the temperature of 120 ℃ to enable cobalt particles to be loaded on the graphite micro-plates, thereby obtaining graphite nano-plate/cobalt composite powder;
s14: and cooling the reaction kettle to room temperature, taking out the graphite nano sheet/cobalt composite powder, and drying in a drying box at 60 ℃ to obtain the cobalt-graphite nano sheet composite powder.
In this example, concentrated nitric acid is used as the oxidizing acid solution.
In this example, sodium borohydride is used as the reducing agent.
Example 3:
the method for preparing the wave-absorbing material by the in-situ vulcanization reaction of the graphite nano-sheet composite cobalt particles comprises the following specific steps:
s1: preparing cobalt-graphite nano-sheet composite powder;
s2: immersing the cobalt-graphite nano-sheet composite powder in an organic solvent glycol contained in a beaker, and fully stirring for more than 2 hours to obtain a cobalt-graphite nano-sheet composite solution;
s3: thiourea and phthalate coupling agent NDZ-401 are added into the solution of the cobalt-graphite nano sheet composite solution, and the ratio is thiourea: NDZ-401: ethylene glycol=7: 0.1:1000 to form an organic solution mixed with cobalt-graphite nanoplatelets and a sulfiding agent;
s3: placing the organic solution mixed with the cobalt-graphite nano-sheets and the vulcanizing agent into a reaction kettle, and reacting for 6 hours at 180 ℃ to enable the surface of the cobalt-graphite nano-sheet composite to generate a vulcanizing layer, so as to ensure that the vulcanizing agent reacts with cobalt particles in situ to generate composite powder with the vulcanizing layer;
s4: and taking out the composite powder with the vulcanized layer, and drying the composite powder in a drying box at the temperature of 60 ℃ for 2 hours to obtain the graphite nano-sheet composite cobalt particles.
In this embodiment, the phthalate coupling agent NDZ-401 is used as a dispersing agent, which has the effect of accelerating the uniform dispersion of the cobalt-graphite nano-sheet composite powder in the aqueous solution with the vulcanizing agent, and is helpful for improving the later vulcanization reaction.
Step S1 further comprises the steps of:
s11: immersing the graphite nano-sheets in an oxidizing acid solution for 10 hours to obtain graphite micro-sheets;
s12: washing out graphite micro-plates, using a cobalt salt solution containing a reducing agent, adding a small amount of sodium carboxymethyl cellulose, and dispersing the acidified graphite micro-plates in the cobalt salt solution under the combined action of mechanical stirring and ultrasonic vibration to obtain a cobalt solution mixed with the graphite micro-plates;
s13: placing the cobalt solution mixed with the graphite micro-plates into a reaction kettle, and reacting for 30 minutes at 180 ℃ to enable cobalt particles to be loaded on the graphite micro-plates, thereby obtaining graphite nano-plate/cobalt composite powder;
s14: and cooling the reaction kettle to room temperature, taking out the graphite nano sheet/cobalt composite powder, and drying in a drying box at 60 ℃ to obtain the cobalt-graphite nano sheet composite powder.
Example 4:
the difference between this example and example 3 is that the thiourea used: the phthalate coupling agent NDZ-401: the proportion of the ethylene glycol is 7:1:1000, in step S5, the composite powder having the vulcanized layer was taken out, and dried in a drying oven at 30 ℃ for 10 hours to obtain graphite nano-sheet composite cobalt particles, and other steps and parameters were the same as in example 3.
While the foregoing is directed to embodiments of the present application, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (2)
1. The method for preparing the wave-absorbing material by the in-situ vulcanization reaction of the graphite nano-sheet composite cobalt particles is used for preparing the wave-absorbing material in the form of the graphite nano-sheet composite cobalt particles and is characterized by comprising the following specific steps of:
s1: preparing cobalt-graphite nano-sheet composite powder;
s2: immersing the cobalt-graphite nano-sheet composite powder in an organic solvent ethylene glycol, and fully stirring for more than 2 hours to obtain a cobalt-graphite nano-sheet composite solution;
s3: adding thiourea and a dispersing agent into the solution of the cobalt-graphite nano-sheet composite solution to form an organic solution mixed with cobalt-graphite nano-sheets and a vulcanizing agent;
s4: placing the organic solution mixed with the cobalt-graphite nano-sheets and the vulcanizing agent into a reaction kettle, and reacting for 3-6 hours at 160-180 ℃ to enable the surface of the cobalt-graphite nano-sheet composite to generate a vulcanizing layer, so as to form composite powder with the vulcanizing layer;
s5: taking out the composite powder with the vulcanized layer, and drying the composite powder in a drying box at the temperature of 30-60 ℃ for 2-10 hours to obtain graphite nano-sheet composite cobalt particles;
step S1 further comprises the steps of:
s11: immersing the graphite nano-sheets in an oxidizing acid solution for 10-12 hours to obtain graphite micro-sheets;
s12: washing out graphite micro-plates, using a cobalt salt solution containing a reducing agent, adding sodium carboxymethylcellulose with the mass percentage of 0.05-0.5%, and dispersing the acidified graphite micro-plates in the cobalt salt solution under the combined action of mechanical stirring and ultrasonic vibration to obtain a cobalt solution mixed with the graphite micro-plates;
s13: placing the cobalt solution mixed with the graphite micro-plates into a reaction kettle, and reacting for 30-120 minutes at the temperature of 120-180 ℃ to enable cobalt particles to be loaded on the graphite micro-plates, thereby obtaining graphite nano-plate/cobalt composite powder;
s14: cooling the reaction kettle to room temperature, taking out the graphite nano sheet/cobalt composite powder, and drying in a drying box at 30-60 ℃ to obtain cobalt-graphite nano sheet composite powder;
the dispersing agent is silane coupling agent KH-570, wherein the thiourea is: the silane coupling agent KH-570: the proportion of the ethylene glycol is 3:0.1 to 1.5:1000;
the dispersing agent is phthalate coupling agent NDZ-401, wherein the thiourea is: the phthalate coupling agent NDZ-401: the proportion of the ethylene glycol is 7:0.1 to 1.0:1000.
2. the method for preparing the wave-absorbing material by in-situ vulcanization reaction of graphite nano-sheet composite cobalt particles according to claim 1, which is characterized in that:
the cobalt particles have the particle size range: 0.1-5 microns.
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