CN116285885A - Cu (copper) alloy 2-x S/Graphene composite wave-absorbing material and preparation method thereof - Google Patents
Cu (copper) alloy 2-x S/Graphene composite wave-absorbing material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
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- 239000004575 stone Substances 0.000 claims 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 29
- 229910052955 covellite Inorganic materials 0.000 description 29
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- 230000005670 electromagnetic radiation Effects 0.000 description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a Cu 2‑x The S/Graphene composite wave-absorbing material and the preparation method thereof comprise the following steps: mixing a sulfur-containing precursor solution and a copper source, and performing centrifugal sample washing to prepare a CuS dispersion liquid; preparing graphene organic stripping liquid by an ultrasonic method; mixing graphene organic stripping solution and CuS dispersion solution according to a certain proportion, and adding guest cation Cu 2+ And reducing agent, centrifugally washing to obtain Cu 2‑ x S/Graphene composite wave-absorbing material, wherein Cu 2‑x S particles are uniformly attached to a single layer of two-dimensional pattern, wherein Cu 2‑x The mass ratio of S to Graphene is 1 (0.01-0.15), and the value range of x is more than or equal to 0 and less than or equal to 1, so as to meet the requirements of 'thin, light, wide and strong' of the wave-absorbing material.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to Cu 2-x S/Graphene composite wave-absorbing material and a preparation method thereof.
Background
With the development of electronic information technology, the wide application of high-frequency equipment brings convenience to society and simultaneously brings harm to electromagnetic radiation. Electromagnetic radiation and electromagnetic interference have an influence on human body, industry, business and the like, so that the application requirements of the wave-absorbing material are sharply increased.
An electromagnetic wave absorbing material is a material capable of attenuating an incident electromagnetic wave by its own absorption, and its principle is that the electromagnetic wave is converted into other forms of energy such as heat energy, electric energy or mechanical energy by dielectric loss to be consumed.
Electromagnetic wave absorbing materials are widely applied in civil, military and aerospace fields, and have become research hot spots in the aspects of electromagnetic shielding, electromagnetic stealth, electromagnetic radiation interference resistance and the like. In addition, the wave absorbing material is applied to microwave communication, microwave darkrooms, computers, medical diagnosis and treatment and household appliances, and can greatly reduce the interference of electromagnetic waves on equipment and the injury to human bodies.
The wave-absorbing materials currently on the market include magnetic loss type wave-absorbing materials, electric loss type wave-absorbing materials, plasma wave-absorbing materials and the like. Among them, the magnetic loss type wave absorbing material represented by ferrite and carbonyl iron powder has the advantages of high magnetic permeability and high impedance matching, but has the disadvantages of high density and poor temperature stability. The electric loss type wave absorbing material represented by the conductive polymer and the carbon wave absorbing agent has the characteristics of high conductivity, low density and high temperature resistance, but has poor impedance matching and narrow wave absorbing band. The plasma wave absorbing material has the advantages of thin coating, wide frequency band and strong wave absorption, but radioactive elements of the material are harmful to human bodies, so that the practical application of the material in the wave absorbing field is limited.
Therefore, a novel wave-absorbing material with good stability, strong compatibility, light weight and high absorption is sought to become a hot spot for current research.
Patent document CN108862366A discloses a sheet Cu developed by the team of the inventors of the present application 2-x Application of S nanocrystalline as microwave absorbent and preparation method thereof, wherein, flaky Cu 2-x When S (x is more than or equal to 0 and less than or equal to 1) nanocrystalline is used as a microwave absorbent, the nanocrystalline has good electromagnetic wave reflection loss performance when the mass filling rate is 20-60%, but Cu 2-x The S nanocrystalline particles are easy to agglomerate, and the dispersibility thereof needs to be further improved.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a Cu 2-x S/Graphene composite wave-absorbing material and preparation method thereof for improving Cu 2-x The dispersibility of the S nano-crystal can meet the requirements of 'thin, light, wide and strong' of the wave absorbing material.
To achieve the above object, embodiments provide a Cu 2-x S/Graphene composite wave-absorbing material, cu 2-x S particles are uniformly attached to a single layer of two-dimensional pattern, wherein Cu 2-x The mass ratio of S to Graphene is 1 (0.01-0.15), and the value range of x is more than or equal to 0 and less than or equal to 1.
The Cu is 2-x In the S/Graphene composite wave-absorbing material, graphene (Graphene) improves Cu 2-x S nanocrystalline dispersibility, and the effect of improving the interface polarization characteristic and dielectric property of the material; cu (Cu) 2-x S is made of Cu 2+ Reaction of CuS with a reducing agent, cu 2-x The change of the content of copper ion vacancies in S can change the dielectric property of the material, thereby affecting the electromagnetic wave reflection loss capacity of the material, so Cu is regulated and controlled 2+ The mol ratio of CuS to Cu can be regulated 2-x Wave absorbing performance of the S/Graphene composite wave absorbing material.
Wherein CuS (covellite) is a P-type (vacancy-type) semiconductor material having a formal oxidation state of (Cu + ) 3 (S 2- )(S 2 - ) The valence of copper ions in CuS is +1. Preferably, in the Cu 2-x In the S/Graphene composite wave-absorbing material, when x=0.7-1, cu 2-x The S/Graphene composite wave-absorbing material has electromagnetic wave reflection loss capacity of-45 to-60 dB in the frequency band of 8-10 GHz.
To achieve the above object, embodiments also provide a Cu 2-x The preparation method of the S/Graphene composite wave-absorbing material comprises the following steps:
(1) Mixing a sulfur-containing precursor solution and a copper source, and performing centrifugal sample washing to prepare a CuS dispersion liquid;
(2) Preparing graphene organic stripping liquid by an ultrasonic method;
(3) Mixing graphene organic stripping solution and CuS dispersion solution according to a certain proportion, and adding guest cation Cu 2+ And reducing agent, centrifugally washing to obtain Cu 2-x S/Graphene composite wave-absorbing material.
Preferably, in step (1), the sulfur-containing precursor solution is obtained by the following preparation method:
dissolving a certain amount of sulfur precursor in an organic solvent, adding an appropriate amount of oil-soluble surfactant, stirring and heating to 120-200 ℃ at a heating rate of 5-15 ℃/min under vacuum, and preserving heat for 30-60 min to form a completely dissolved sulfur-containing precursor solution, wherein the molar ratio of the organic solvent to the oil-soluble surfactant is 1 (0.8-1.2), the concentration of the sulfur-containing precursor solution is controlled to be 2-5 g/L, and the sulfur-containing precursor is selected from at least one of sulfur powder, sodium sulfide and hydrate thereof. Wherein the organic solvent is octadecene organic solvent, and the oil-soluble surfactant is one selected from oleyl dimethyl tertiary amine, oleyl amine (primary oleate) and 1-amino octane.
Preferably, in step (1), the sulfur-containing precursor solution and the copper source are mixed and subjected to centrifugal washing to prepare the CuS dispersion, comprising:
introducing inert gas into a reaction device filled with sulfur-containing precursor solution, adding a certain amount of copper source, wherein the Cu source/S source is less than 0.5 according to the molar ratio, vacuumizing and stirring for reaction for 40-90 min, cooling to room temperature, centrifugally washing samples at 2500-5000 rpm for 3-10 min to obtain a CuS sample, and dissolving the CuS sample in an organic solvent to form CuS dispersion liquid. Wherein the copper source is selected from at least one of copper acetate and its hydrate. The organic solvent is toluene organic solvent.
Preferably, in the step (2), the method for preparing the graphene organic stripping solution by using an ultrasonic method comprises the following steps:
dissolving graphene in an organic solvent, adding a surfactant, stirring for 30-60 min at room temperature, performing ultrasonic treatment for 60-120 min to form graphene suspension, centrifuging the graphene suspension at a rotating speed of 1000-2000 rpm for 10-30 min, and taking supernatant as graphene organic stripping liquid; wherein the organic solvent of the graphene is selected from any one of ethylene glycol, dimethylformamide, methyl pyrrolidone and tetrahydrofuran; the graphene surfactant is selected from any one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and polyethylene oxide-polypropylene oxide-polyethylene oxide.
Preferably, in the step (3), after the graphene organic stripping solution and the CuS dispersion solution are mixed according to a certain proportion, guest cation Cu is added 2+ And reducing agent, centrifugally washing to obtain Cu 2-x The S/Graphene composite wave-absorbing material comprises:
adding graphene suspension into CuS dispersion according to the mass ratio of graphene to CuS of 1 (0.01-0.15), adding reducing agent according to the mol ratio of CuS to reducing agent of 1 (3-10), stirring for 20-60 min, and then mixing according to CuS and Cu 2+ The molar ratio of (1) to (0.2-2) of guest cation Cu 2+ Stirring and reacting for 2-10 min, centrifuging and washing sample at 8000-12000 rpm for 5-10 min, vacuum drying at 150-220 deg.C for 60-120 min to obtain Cu 2-x S/Graphene composite wave-absorbing material. Wherein the reducing agent is at least one selected from hydrazine hydrate, ascorbic acid and ethylene glycol.
To achieve the above object, embodiments also provide a Cu 2-x S/Graphene composite wave-absorbing material, wherein the Cu 2-x The S/Graphene composite wave-absorbing material is prepared according to the preparation method.
Compared with the prior art, the invention has the beneficial effects that at least the following steps are included:
make full use of Cu 2-x The S nano particles have the advantages of high dielectric property, high specific surface area of Graphene, light weight and the like, and Cu with the wave-absorbing property of 'thin, light, wide and strong' is synthesized by a simple chemical conversion preparation method 2-x S/Graphene composite wave-absorbing material, cu 2-x The S/Graphene composite wave-absorbing material can be used as a microwave absorbent alone or as a functional material in combination with a matrix material such as paraffin. Has good application prospect in the technical field of microwave electronics.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a Cu provided in the examples 2-x A flow chart of a preparation method of the S/Graphene composite wave-absorbing material;
FIG. 2 is a diagram showing Cu in example 1 of the present invention 1.125 XRD pattern of S/Graphene composite wave-absorbing material;
FIG. 3 is a diagram showing Cu in example 1 of the present invention 1.125 TEM image of S/Graphene composite wave-absorbing material;
FIG. 4 shows Cu in example 1 of the present invention 1.125 An electromagnetic wave reflection loss diagram of the S/Graphene composite wave absorbing material;
FIG. 5 is a diagram showing Cu in example 2 of the present invention 1.75 XRD pattern of S/Graphene composite wave-absorbing material;
FIG. 6 is a diagram showing Cu in example 2 of the present invention 1.75 Electromagnetic wave reflection loss diagram of S/Graphene composite wave absorbing material.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and the described embodiments are only some, but not all, of the possible embodiments of the present invention, and are intended to provide a basic understanding of the present invention, and are not intended to identify key or critical elements of the present invention or to define the scope of the present invention. It is easy to understand that, according to the technical solution of the present invention, those skilled in the art may propose other implementations that can be replaced with each other without changing the true spirit of the present invention. Accordingly, the following detailed description and drawings are merely illustrative of the invention and are not intended to be exhaustive or to limit the invention to the precise form disclosed.
Compared with the flaky Cu disclosed in CN108862366A 2-x S nanocrystalline for further improving Cu 2-x Dispersibility of S nanocrystals, avoiding Cu 2-x S nano-crystal agglomeration and compactionExample provides a Cu 2-x S/Graphene composite wave-absorbing material, cu by utilizing high specific surface area of Graphene 2-x S nano crystals can be uniformly distributed on the surface of the Graphene, so that Cu is greatly improved 2- x The S nano-crystal has dispersibility and material interface polarization capability, and the prepared composite wave absorber not only has excellent wave absorption reflection loss performance, but also has wider wave absorption band under-10 dB reflection loss.
The Cu is 2-x The S/Graphene composite wave-absorbing material consists of Graphene organic solution, cuS dispersion liquid and guest cation Cu 2+ Obtained by reaction of Cu 2-x S particles are uniformly attached to a single layer of two-dimensional pattern, wherein Cu 2-x The mass ratio of S to Graphene is 1 (0.01-0.15), the value range of x is 0-1, and Cu is regulated and controlled by adjusting 2+ Molar ratio between/CuS to regulate Cu 2-x Wave absorbing performance of the S/Graphene composite wave absorbing material.
As shown in FIG. 1, the embodiment also provides a Cu as described above 2-x The preparation method of the S/Graphene composite wave-absorbing material comprises the following steps:
introducing inert gas into a reaction device filled with sulfur-containing precursor solution, adding a certain amount of copper source, vacuumizing and stirring for reaction for 40-90 min, cooling to room temperature, centrifugally washing samples at 2500-5000 rpm for 3-10 min to obtain CuS samples, and dissolving the CuS samples in an organic solvent to form CuS dispersion liquid. Wherein the copper source is selected from at least one of copper acetate and its hydrate.
The preparation method of the sulfur-containing precursor solution comprises the following steps:
dissolving a certain amount of sulfur precursor in an organic solvent, adding an appropriate amount of oil-soluble surfactant, stirring and heating to 120-200 ℃ at a heating rate of 5-15 ℃/min under vacuum, and preserving heat for 30-60 min to form a completely dissolved sulfur-containing precursor solution, wherein the molar ratio of the organic solvent to the oil-soluble surfactant is 1 (0.8-1.2), and the concentration of the sulfur-containing precursor solution is controlled to be 2-5 g/L. Wherein the sulfur-containing precursor is selected from at least one of sulfur powder, sodium sulfide and hydrate thereof.
dissolving graphene in an organic solvent, adding a surfactant, stirring for 30-60 min at room temperature, performing ultrasonic treatment for 60-120 min to form graphene suspension, centrifuging the graphene suspension at a rotating speed of 1000-2000 rpm for 10-30 min, and taking supernatant as graphene organic stripping liquid; wherein the organic solvent of the graphene is selected from any one of ethylene glycol, dimethylformamide, methyl pyrrolidone and tetrahydrofuran; the graphene surfactant is selected from any one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and polyethylene oxide-polypropylene oxide-polyethylene oxide.
Step 3, mixing the graphene organic stripping solution and the CuS dispersion solution according to a certain proportion, and adding guest cation Cu 2+ And reducing agent, centrifugally washing to obtain Cu 2-x The S/Graphene composite wave-absorbing material comprises:
adding graphene suspension into CuS dispersion according to the mass ratio of graphene to CuS of 1 (0.01-0.15), adding reducing agent according to the mol ratio of CuS to reducing agent of 1 (3-10), stirring for 20-60 min, and then mixing according to CuS and Cu 2+ The molar ratio of (1) to (0.2-2) of guest cation Cu 2+ Stirring and reacting for 2-10 min, centrifuging and washing sample at 8000-12000 rpm for 5-10 min, vacuum drying at 150-220 deg.C for 60-120 min to obtain Cu 2-x S/Graphene composite wave-absorbing material. Wherein the reducing agent is at least one selected from hydrazine hydrate, ascorbic acid and ethylene glycol.
Based on the above preparation method steps, the following is further described and illustrated with reference to the accompanying drawings and specific examples.
Example 1
Adding 0.096g of graphene into a reaction bottle containing 213ml of ethylene glycol organic solvent, magnetically stirring for 30min, adding 0.096g of cetyltrimethylammonium chloride surfactant, continuously stirring for 30min, performing ultrasonic treatment for 80min to form graphene suspension, and centrifuging the graphene suspension at a centrifugation speed of 1000rpm for 10min to obtain a supernatant serving as graphene organic stripping liquid.
A reaction flask with the capacity of 500ml is newly taken, 100ml of octadecene organic solvent and 100ml of oil-based dimethyl tertiary amine surfactant are added, then 0.64g of sulfur powder is weighed and poured into the reaction flask, the reaction flask is placed on a heatable magnetic stirrer, the reaction flask is stirred and heated to 150 ℃ at the heating rate of 5 ℃ per minute under vacuum, ar gas is introduced into the reaction flask after heat preservation for 30min, 1.995g of copper acetate monohydrate is weighed and poured into the reaction flask, stirring reaction is carried out for 50min after vacuumizing, and then the reaction flask is gradually cooled to room temperature.
Adding 40ml of methanol into the reaction solution cooled to room temperature, stirring uniformly, centrifuging at a centrifugal speed of 5000rpm for 3min, dissolving a CuS sample obtained by centrifugation in 29ml of toluene to obtain CuS dispersion, adding the CuS dispersion into graphene organic stripping solution, adding 8.800g of ascorbic acid reducing agent into the graphene stripping solution, stirring until the ascorbic acid reducing agent is completely dissolved, and adding Cu providing guest cations 2+ After stirring for 3min, stopping the reaction, uniformly mixing the obtained reaction solution with 240ml of methanol, centrifuging at 12000rpm for 5min, and drying the obtained sample in an oven at 200 ℃ for 150min to obtain Cu 1.125 S/Graphene composite wave-absorbing material.
FIG. 2 is a diagram showing Cu in example 1 of the present invention 1.125 XRD patterns of the S/Graphene composite wave-absorbing material correspond to the diffraction peak of the (1 0 1) plane of Graphene and the diffraction peak of the copper sulfide ore Cu in figure 2 1.125 The diffraction peak at the S (0 0 22) (1 0 13) (1 1 1) (1 16) (1 1 24) surface is weak because the graphene is in a single-layer or double-layer state after being peeled off, and the crystallinity is low. FIG. 3 is a diagram showing Cu in example 1 of the present invention 1.125 TEM image of S/Graphene composite wave-absorbing material, cu can be seen from FIG. 3 1.125 S particles are very uniformly distributed on the graphene, so that the advantage of large specific surface area of the graphene is utilized well, and Cu is facilitated 1.125 S particles fully reflect and consume electromagnetic waves; FIG. 4 shows Cu in example 1 of the present invention 1.125 The electromagnetic wave reflection loss diagram of the S/Graphene composite wave-absorbing material can be found from FIG. 4 1.125 The electromagnetic wave reflection loss bandwidth of the S/Graphene composite wave absorbing material smaller than-10 dB reaches 10GHz, and the maximum reflection loss capacity is-44.8 dB. The wave absorbing material can be applied to the microwave absorbing field requiring broadband and high electromagnetic wave reflection loss.
Example 2
Adding 0.096g of graphene into a reaction bottle containing 213ml of ethylene glycol organic solvent, magnetically stirring for 30min, adding 0.096g of cetyltrimethylammonium chloride surfactant, continuously stirring for 30min, performing ultrasonic treatment for 80min to form graphene suspension, and centrifuging the graphene suspension at a centrifugation speed of 1000rpm for 10min to obtain a supernatant serving as graphene organic stripping liquid.
A reaction flask with the capacity of 500ml is newly taken, 100ml of octadecene organic solvent and 100ml of oil-based dimethyl tertiary amine surfactant are added, then 0.64g of sulfur powder is weighed and poured into the reaction flask, the reaction flask is placed on a heatable magnetic stirrer, the reaction flask is stirred and heated to 150 ℃ at the heating rate of 5 ℃ per minute under vacuum, ar gas is introduced into the reaction flask after heat preservation for 30min, 1.995g of copper acetate monohydrate is weighed and poured into the reaction flask, stirring reaction is carried out for 50min after vacuumizing, and then the reaction flask is gradually cooled to room temperature.
Adding 40ml of methanol into the reaction solution cooled to room temperature, stirring uniformly, centrifuging at a centrifugal speed of 5000rpm for 3min, dissolving the obtained sample in 29ml of toluene, adding into graphene organic stripping solution, adding 8.800g of ascorbic acid reducing agent into the graphene stripping solution, stirring until the ascorbic acid reducing agent is completely dissolved, and adding Cu providing guest cations 2+ 1.995g of copper acetate monohydrate, stirring for 3min, stopping the reaction, uniformly mixing the obtained reaction solution with 240ml of methanol, centrifuging at 12000rpm for 5min, and drying the centrifuged sample in an oven at 200 ℃ for 150min to obtain Cu 1.75 S/Graphene composite wave-absorbing material.
FIG. 5 is a diagram showing Cu in example 2 of the present invention 1.75 The XRD pattern of the S/Graphene composite wave-absorbing material can be seen from the figure 5, and the diffraction peak of the Graphene (1 0 1) surface and the penthiocopper Cu appear in the X-ray diffraction 1.75 Diffraction peaks of S (16 0) (18 2 1) (12 8 1) (22 0) (0 8) (8 8 6) surfaces are due to graphene strippingAfter separation, the crystal is in a single-layer or double-layer state, and the crystallinity is low, so that the diffraction peak is weak. FIG. 6 is a diagram showing Cu in example 2 of the present invention 1.75 As can be seen from FIG. 6, the electromagnetic wave reflection loss diagram of the S/Graphene composite wave-absorbing material is compared with Cu 1.125 S/Graphene composite wave-absorbing material, cu 1.75 The bandwidth of the S/Graphene composite wave-absorbing material is narrowed, and the maximum reflection loss capacity is-25.2 dB. This is because of Cu 2+ An increase in the amount, resulting in Cu 1.75 The carrier concentration in the S/Graphene composite wave-absorbing material is reduced, and the resonance loss of the carrier to electromagnetic waves is reduced. The wave absorbing material can be independently applied and regulated on chemical components aiming at specific frequency bands and specific electromagnetic wave reflection loss degree.
The foregoing detailed description of the preferred embodiments and advantages of the invention will be appreciated that the foregoing description is merely illustrative of the presently preferred embodiments of the invention, and that no changes, additions, substitutions and equivalents of those embodiments are intended to be included within the scope of the invention.
Claims (10)
1. Cu (copper) alloy 2-x S/Graphene composite wave-absorbing material is characterized by comprising Cu 2-x S particles are uniformly attached to a single layer of two-dimensional pattern, wherein Cu 2-x The mass ratio of S to Graphene is 1 (0.01-0.15), and the value range of x is more than or equal to 0 and less than or equal to 1.
2. Cu (copper) alloy 2-x The preparation method of the S/Graphene composite wave-absorbing material is characterized by comprising the following steps of:
(1) Mixing a sulfur-containing precursor solution and a copper source, and performing centrifugal sample washing to prepare a CuS dispersion liquid;
(2) Preparing graphene organic stripping liquid by an ultrasonic method;
(3) Mixing graphene organic stripping solution and CuS dispersion solution according to a certain proportion, and adding guest cation Cu 2+ And reducing agent, centrifugally washing to obtain Cu 2-x S/Graphene composite wave-absorbing material.
3. Cu according to claim 2 2-x The preparation method of the S/Graphene composite wave-absorbing material is characterized in that in the step (1), the sulfur-containing precursor solution is obtained by the following preparation method:
dissolving a certain amount of sulfur precursor in an organic solvent, adding an appropriate amount of oil-soluble surfactant, stirring and heating to 120-200 ℃ at a heating rate of 5-15 ℃/min under vacuum, and preserving heat for 30-60 min to form a completely dissolved sulfur-containing precursor solution, wherein the molar ratio of the organic solvent to the oil-soluble surfactant is 1 (0.8-1.2), and the concentration of the sulfur-containing precursor solution is controlled to be 2-5 g/L.
4. The Cu of claim 3 2-x The preparation method of the S/Graphene composite wave-absorbing material is characterized in that the sulfur-containing precursor is selected from at least one of sulfur powder, sodium sulfide and hydrate thereof.
5. Cu according to claim 2 2-x The preparation method of the S/Graphene composite wave-absorbing material is characterized in that in the step (1), a sulfur-containing precursor solution and a copper source are mixed, and a centrifugal sample washing is carried out to prepare a CuS dispersion liquid, wherein the preparation method comprises the following steps:
introducing inert gas into a reaction device filled with a sulfur-containing precursor solution, adding a copper source, wherein the Cu source/S source is less than 0.5 according to the molar ratio, vacuumizing and stirring for reaction for 40-90 min, cooling to room temperature, centrifugally washing samples at 2500-5000 rpm for 3-10 min to obtain a CuS sample, and dissolving the CuS sample in an organic solvent to form a CuS dispersion liquid.
6. Cu according to claim 2 or 5 2-x The preparation method of the S/Graphene composite wave-absorbing material is characterized in that the copper source is at least one selected from copper acetate and hydrates thereof.
7. Cu according to claim 2 2-x The preparation method of the S/Graphene composite wave-absorbing material is characterized in that in the step (2), the stone is prepared by an ultrasonic methodAn graphene organic stripping solution comprising:
dissolving graphene in an organic solvent, adding a surfactant, stirring for 30-60 min at room temperature, performing ultrasonic treatment for 60-120 min to form graphene suspension, centrifuging the graphene suspension at a rotating speed of 1000-2000 rpm for 10-30 min, and taking supernatant as graphene organic stripping liquid;
wherein the organic solvent of the graphene is selected from any one of ethylene glycol, dimethylformamide, methyl pyrrolidone and tetrahydrofuran;
the graphene surfactant is selected from any one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and polyethylene oxide-polypropylene oxide-polyethylene oxide.
8. Cu according to claim 2 2-x The preparation method of the S/Graphene composite wave-absorbing material is characterized in that in the step (3), after Graphene organic stripping solution and CuS dispersion solution are mixed according to a certain proportion, guest cation Cu is added 2+ And reducing agent, centrifugally washing to obtain Cu 2-x The S/Graphene composite wave-absorbing material comprises:
adding graphene suspension into CuS dispersion according to the mass ratio of graphene to CuS of 1 (0.01-0.15), wherein the molar ratio of CuS to reducing agent is 1: adding reducing agent in the proportion of (3-10) and stirring for 20-60 min, and then mixing according to CuS and Cu 2+ The molar ratio of (1) to (0.2-2) of guest cation Cu 2+ Stirring and reacting for 2-10 min, centrifuging and washing sample at 8000-12000 rpm for 5-10 min, vacuum drying at 150-220 deg.C for 60-120 min to obtain Cu 2-x S/Graphene composite wave-absorbing material.
9. Cu according to claim 2 or 8 2-x The preparation method of the S/Graphene composite wave-absorbing material is characterized in that the reducing agent is at least one selected from hydrazine hydrate, ascorbic acid and ethylene glycol.
10. Cu (copper) alloy 2-x S/Graphene composite wave-absorbing material is characterized in thatThe Cu is 2-x The S/Graphene composite wave-absorbing material is prepared according to the preparation method of claims 2-9.
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