CN113840529A - NiCo2O4@ agaric carbon aerogel composite material and preparation method and application thereof - Google Patents
NiCo2O4@ agaric carbon aerogel composite material and preparation method and application thereof Download PDFInfo
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910005949 NiCo2O4 Inorganic materials 0.000 title claims description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 70
- 238000010521 absorption reaction Methods 0.000 claims abstract description 30
- 239000004964 aerogel Substances 0.000 claims abstract description 30
- 241000233866 Fungi Species 0.000 claims abstract description 25
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000002028 Biomass Substances 0.000 claims abstract description 8
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- 238000013329 compounding Methods 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 235000000023 Auricularia auricula Nutrition 0.000 claims description 7
- 241001149430 Auricularia auricula-judae Species 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
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- 239000006096 absorbing agent Substances 0.000 description 5
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- 229910052596 spinel Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 241000221377 Auricularia Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 241000245665 Taraxacum Species 0.000 description 1
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 description 1
- 241001506047 Tremella Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
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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
- C01P2004/60—Particles characterised by their size
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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
Abstract
The invention provides NiCo for the field of electromagnetic wave absorption2O4The @ black fungus carbon aerogel composite material is prepared by taking black fungus aerogel as a raw material, obtaining biomass-derived porous carbon through a pyrolysis carbonization method, and then compounding NiCo uniformly distributed on the carbon aerogel in situ through two-step experiments of hydrothermal treatment and air heat treatment2O4A nanostructure. Through the regulation and control of the synthesis reagent, NiCo with different nano-morphologies is reasonably constructed2O4The @ edible fungus aerogel derived carbon composite material (C @ NCO) has high-efficiency low-frequency electromagnetic wave absorption performance. Experiments prove that the preparation method of the composite material has the characteristics of stability, controllability, simplicity and easiness in operation, and the prepared composite material has strong absorption at low frequencyThe wide effective absorption frequency band and the thin absorption thickness meet the requirements of the society prevailing in the current wireless communication technology on the low-frequency efficient absorption of the electromagnetic wave absorption material and the requirements of the society prevailing in the current wireless communication technology on the low-frequency efficient absorption of the electromagnetic wave absorption material.
Description
Technical Field
The present invention relates to a functional materialAn electromagnetic absorbing material in the field, in particular to NiCo2O4The @ black fungus carbon aerogel composite material can be obtained through simple heat treatment and in-situ chemical synthesis, and has stable and excellent low-frequency electromagnetic wave absorption performance.
Background
At present, the rapid development of wireless communication and the constant popularization of intelligent driving of automobiles bring convenience to the fast-paced society. While enjoying these conveniences, the large number of electronic devices greatly increase electromagnetic radiation, causing serious electromagnetic pollution problems. With the consequent harm to human health and the natural environment, as well as interference with other equipment, even affecting national safety or causing major accidents. In view of effective purification of harmful electromagnetic waves, researchers have succeeded in developing a series of electromagnetic wave absorbing materials, and current research is mainly focused on high-frequency electromagnetic wave absorption, such as X and Ku bands (8-18 GHz). However, the development of 4G and 5G communication technologies means that the development of efficient electromagnetic wave absorbers for low frequency bands (2-8 GHz) has become a key research direction in the field of electromagnetic pollution protection. In addition, the operating frequency band of various military radars has gradually expanded to the low frequency range. Therefore, it is very necessary to develop a novel electromagnetic wave absorber capable of obtaining high-efficiency absorption at a low frequency.
Due to the stability, lightweight property and good electrical conductivity of carbonaceous materials, research into the carbonaceous materials as electromagnetic wave absorbers has been receiving increasing attention. In addition to the usual one-dimensional carbon materials (carbon fibers and carbon nanotubes) and two-dimensional carbon materials (graphene oxide and MXene), three-dimensional porous carbon materials are also potential candidates, such as expandable graphite and carbon aerogels. In addition, many biomass materials have also been developed as excellent templates for preparing novel porous carbon materials. In particular, the biomass contains a large amount of organic matters, has various unique structural forms, and can be used as an effective matrix of the electromagnetic wave absorbent after high-temperature pyrolysis treatment. More importantly, the practical value of the biological organic fertilizer is greatly improved by a series of advantages of availability, abundant sources, environment friendliness, renewability and the like. To date, most research on biomass-derived carbon absorbents has focused on the control of carbonization temperature and composition, while the geometry of the composite material has been rarely studied. Researches find that the morphology adjustment is an effective way to obtain the optimal wave absorbing performance, so that the adjustment of the morphology of the biomass-derived carbon-based composite material can provide inspiration for further improving the wave absorbing performance.
Furthermore, the wave absorbing properties of single component material systems are limited by impedance mismatches. In order to obtain outstanding wave absorbing properties, carbon materials need to be combined with magnetically lossy materials to optimize impedance matching. Spinel ferrites are expanded to various fields due to their high conductivity, abundant resources, environmental friendliness and low cost. In addition, their low snooker limit, moderate saturation magnetization, appropriate low-frequency natural resonance and double loss mechanism make them well developed in the microwave absorption field, especially in the low-frequency field. Nickel cobalt ore (NiCo)2O4) Is a typical spinel ferrite, and is a popular absorption material due to the advantages of designable morphology, large magnetic anisotropy, strong polarization capacity and the like. The above theory and experiments predict that NiCo2O4 can be used to improve the pure carbon absorber limitations.
Here, we prepared four different forms of Ni-Co precursor (dandelion, echinoid, tremella and rose) on Auricularia carbon aerogel and annealed to obtain C @ NiCo with the same form as expected2O4Hybrid (C @ NCO). By adjusting the form, the electromagnetic parameters, the attenuation capability and the impedance matching characteristic are successfully controlled, and brilliant wave absorbing performance is achieved: at 4.88GHz, the minimum Reflection Loss (RL) is-54.6 dB, the thickness is 4.09mm, and the Effective Absorption Bandwidth (EAB) covers 5.7GHz at 1.85 mm. The wave absorber realizes strong electromagnetic wave absorption in S and C wave bands and also meets the requirement of effective absorption in X and Ku wave bands. Outstanding microwave absorption properties benefit from the combined effects of dipole polarization, interfacial polarization, magnetic losses, conduction losses and antenna structure. This work has provided inspiration for the development of high performance electromagnetic wave absorbing materials with tunable effective frequencies, particularly at low frequencies such as the C and S bands.
In conclusion, a NiCo with high wave absorption performance is developed by simple preparation2O4The @ black fungus carbon aerogel composite material has important significance for development and production of wave-absorbing materials.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a NiCo2O4@ agaric carbon aerogel composite material and a preparation method and application thereof.
The technical scheme adopted by the invention is NiCo2O4The @ black fungus carbon aerogel composite material takes black fungus carbon aerogel of biomass-derived porous carbon as a raw material, and NiCo is uniformly distributed on the black fungus carbon aerogel in an in-situ compounding manner2O4A nanostructure.
The invention also provides NiCo2O4The preparation method of the @ black fungus carbon aerogel composite material comprises the following steps:
step A1: 1mmol nickel nitrate hexahydrate, 2mmol cobalt nitrate hexahydrate and 12mmol additive are dissolved in 30ml deionized water and stirred for 10 minutes to form uniform NiCo2O4A solution;
step A2, adding agaric carbon aerogel into the uniform solution obtained in the step A1, continuously stirring for 6 hours, pouring into 50ml of polytetrafluoroethylene as an inner liner, putting into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 6 hours, and then cooling to room temperature;
step A3, the product prepared in step A2 is filtered and washed 3 times by deionized water and absolute ethyl alcohol respectively, placed in a 60 ℃ oven and dried for 24 hours.
Step A4: and D, carrying out heat treatment on the product obtained in the step A3 in air, wherein the heat treatment temperature is 350 ℃, the heating rate is 1 ℃/min, the heat preservation time is 120 minutes, and cooling to the room temperature along with the furnace.
Preferably, the additive is one of urea and urotropin.
Preferably, 6mmol ammonium fluoride can be further added in the step A1.
The preparation method of the agaric carbon aerogel comprises the following steps:
step B1: ultrasonically cleaning Auricularia auricula with deionized water and anhydrous ethanol for 3 times, each time for 10min, placing in a 60 deg.C oven, and drying for 24 hr;
step B2: soaking the agaric obtained in the step B1 in 60ml of deionized water for 1 hour, transferring the agaric into a polytetrafluoroethylene lining, putting the agaric into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 10 hours, and then cooling to room temperature to obtain an agaric gel solution;
step B3: b2, carrying out ultrasonic treatment on the agaric gel solution obtained in the step B2 for 2 hours, freezing the obtained uniform gel at-85 ℃ overnight, and carrying out vacuum freeze-drying for 72 hours to obtain agaric aerogel;
step B4: and D, carrying out heat treatment on the agaric aerogel obtained in the step B3 in an inert gas atmosphere, wherein the heat treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 120min, and cooling to room temperature along with a furnace to obtain the agaric carbon aerogel.
Preferably, the agaric carbon aerogel is mixed with NiCo2O4The mass ratio of the solution is 1: 1.
preferably, the inert gas in step B4 is one of argon and nitrogen.
Meanwhile, the invention provides NiCo2O4The application of the @ Auricularia carbon aerogel composite material in low-frequency electromagnetic wave absorption.
The invention has the following advantages: the method comprises the steps of obtaining biomass-derived porous carbon by using agaric aerogel as a raw material through a pyrolysis carbonization method, and then compounding NiCo uniformly distributed on carbon aerogel in situ through two-step experiments of hydrothermal treatment and air heat treatment2O4A nanostructure. Through the regulation and control of the synthesis reagent, NiCo with different nano-morphologies is reasonably constructed2O4The @ edible fungus aerogel derived carbon composite material (C @ NCO) has high-efficiency low-frequency electromagnetic wave absorption performance. Experiments prove that the preparation method of the composite material has the characteristics of stability, controllability, simplicity and easiness in operation, and the prepared composite material has strong low-frequency absorption, wide effective absorption frequency band and thin absorption thickness, so that the low-frequency absorption material meets the requirements of the society prevailing in the current wireless communication technology on the electromagnetic wave absorption materialHigh absorption efficiency.
Drawings
FIG. 1 XRD patterns of examples 1-4 and comparative examples.
Detailed Description
The invention will be described in further detail below with reference to the embodiments of the drawing, which are intended to facilitate the understanding of the invention and are not intended to limit the invention in any way.
The invention provides the following specific embodiments, discloses the performance of various combination examples, and analyzes the effect of each experimental parameter in the system. Therefore, this patent specification should be considered to disclose all possible combinations of the described technical solutions.
Example 1:
in this example, the product obtained was NiCo2O4@ Auricularia aerogel composite.
The above NiCo2O4The preparation method of the @ edible fungus aerogel composite material comprises the following steps:
(1) ultrasonically cleaning Auricularia auricula with deionized water and anhydrous ethanol for 3 times, each time for 10min, placing in a 60 deg.C oven, and drying for 24 hr;
(2) soaking the agaric obtained in the step (1) in 60ml of deionized water for 1 hour, transferring the agaric into 100ml of polytetrafluoroethylene serving as a lining, putting the agaric into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 10 hours, and then cooling to room temperature to obtain an agaric gel solution;
(3) carrying out ultrasonic treatment on the agaric gel solution obtained in the step (2) for 2 hours, freezing the obtained uniform gel at-85 ℃ overnight, and carrying out vacuum freeze-drying for 72 hours to obtain agaric aerogel;
(4) carrying out heat treatment on the agaric aerogel obtained in the step (3) in an argon atmosphere, wherein the heat treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 120min, and cooling to room temperature along with a furnace to obtain agaric carbon aerogel;
(5) dissolving 1mmol nickel nitrate hexahydrate, 2mmol cobalt nitrate hexahydrate and 12mmol urea in 30ml deionized water, stirring for 10min to form uniform NiCo2O4A solution;
(6) adding the agaric carbon aerogel obtained in the step (4) into the uniform solution obtained in the step (5), and mixing the agaric carbon aerogel with NiCo2O4The mass ratio of the solution is 1: 1; continuously stirring for 6h, pouring into 50ml of polytetrafluoroethylene as a lining, putting into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 6h, and then cooling to room temperature;
(7) respectively filtering and washing the product prepared in the step (6) by deionized water and absolute ethyl alcohol for 3 times, placing the product in a 60 ℃ oven, and drying the product for 24 hours;
(8) and (4) carrying out heat treatment on the product obtained in the step (7) in air, wherein the heat treatment temperature is 350 ℃, the heat preservation time is 120min, the heating rate is 1 ℃/min, and the product is cooled to room temperature along with the furnace.
The product obtained above was tested as follows:
(A) respectively adopts an irradiation source of Cu-Ka ()λ=1.54 a) (abbreviated as XRD, the same below) to determine the crystal structure of the sample.
(B) And measuring the electromagnetic parameters of the complex dielectric constant and the complex permeability of the electromagnetic parameters by a Siamese 3672B-S vector network analyzer in a frequency range of 2-18GHz by using a coaxial line method. Preparation of a test sample: the product was prepared by uniformly dispersing it in paraffin wax, which was 50% by weight, and then pressing into a ring-shaped article (outer diameter: 7.0 mm, inner diameter: 3.04 mm).
Example 2:
in this example, the product obtained was NiCo2O4@ Auricularia aerogel composite.
Above is NiCo2O4The preparation method of the @ edible fungus aerogel composite material comprises the following steps:
(1) ultrasonically cleaning Auricularia auricula with deionized water and anhydrous ethanol for 3 times, each time for 10min, placing in a 60 deg.C oven, and drying for 24 hr;
(2) soaking the agaric obtained in the step (1) in 60ml of deionized water for 1 hour, transferring the agaric into 100ml of polytetrafluoroethylene serving as a lining, putting the agaric into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 10 hours, and then cooling to room temperature to obtain an agaric gel solution;
(3) carrying out ultrasonic treatment on the agaric gel solution obtained in the step (2) for 2 hours, freezing the obtained uniform gel at-85 ℃ overnight, and carrying out vacuum freeze-drying for 72 hours to obtain agaric aerogel;
(4) carrying out heat treatment on the agaric aerogel obtained in the step (3) in an argon atmosphere, wherein the heat treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 120min, and cooling to room temperature along with a furnace to obtain agaric carbon aerogel;
(5) 1mmol of nickel nitrate hexahydrate, 2mmol of cobalt nitrate hexahydrate, 12mmol of urea and 6mmol of ammonium fluoride are dissolved in 30ml of deionized water and stirred for 10min to form uniform NiCo2O4A solution;
(6) adding the agaric carbon aerogel obtained in the step (4) into the uniform solution obtained in the step (5), and mixing the agaric carbon aerogel with NiCo2O4The mass ratio of the solution is 1: 1, continuously stirring for 6 hours, pouring the mixture into 50ml of polytetrafluoroethylene as a lining, putting the mixture into a stainless steel autoclave, heating the mixture to 120 ℃ in a hydrothermal heating mode, preserving the heat for 6 hours, and then cooling the mixture to room temperature;
(7) respectively filtering and washing the product prepared in the step (6) by deionized water and absolute ethyl alcohol for 3 times, placing the product in a 60 ℃ oven, and drying the product for 24 hours;
(8) and (4) carrying out heat treatment on the product obtained in the step (7) in air, wherein the heat treatment temperature is 350 ℃, the heat preservation time is 120min, the heating rate is 1 ℃/min, and the product is cooled to room temperature along with the furnace.
The product prepared in the above way is tested, and the testing method and the testing content are completely the same as those in the embodiment 1.
Example 3:
in this example, the product obtained was NiCo2O4@ Auricularia aerogel composite.
Above is NiCo2O4The preparation method of the @ edible fungus aerogel composite material comprises the following steps:
(1) ultrasonically cleaning Auricularia auricula with deionized water and anhydrous ethanol for 3 times, each time for 10min, placing in a 60 deg.C oven, and drying for 24 hr;
(2) soaking the agaric obtained in the step (1) in 60ml of deionized water for 1 hour, transferring the agaric into 100ml of polytetrafluoroethylene serving as a lining, putting the agaric into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 10 hours, and then cooling to room temperature to obtain an agaric gel solution;
(3) carrying out ultrasonic treatment on the agaric gel solution obtained in the step (2) for 2 hours, freezing the obtained uniform gel at-85 ℃ overnight, and carrying out vacuum freeze-drying for 72 hours to obtain agaric aerogel;
(4) carrying out heat treatment on the agaric aerogel obtained in the step (3) in an argon atmosphere, wherein the heat treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 120min, and cooling to room temperature along with a furnace to obtain agaric carbon aerogel;
(5) dissolving 1mmol nickel nitrate hexahydrate, 2mmol cobalt nitrate hexahydrate and 12mmol urotropine in 30ml deionized water, stirring for 10min to form uniform NiCo2O4A solution;
(6) adding the agaric carbon aerogel obtained in the step (4) into the uniform solution obtained in the step (5), and mixing the agaric carbon aerogel with NiCo2O4The mass ratio of the solution is 1: 1, continuously stirring for 6 hours, pouring the mixture into 50ml of polytetrafluoroethylene as a lining, putting the mixture into a stainless steel autoclave, heating the mixture to 120 ℃ in a hydrothermal heating mode, preserving the heat for 6 hours, and then cooling the mixture to room temperature;
(7) respectively filtering and washing the product prepared in the step (6) by deionized water and absolute ethyl alcohol for 3 times, placing the product in a 60 ℃ oven, and drying the product for 24 hours;
(8) and (4) carrying out heat treatment on the product obtained in the step (7) in air, wherein the heat treatment temperature is 350 ℃, the heat preservation time is 120min, the heating rate is 1 ℃/min, and the product is cooled to room temperature along with the furnace.
The product prepared in the above way is tested, and the testing method and the testing content are completely the same as those in the embodiment 1.
Example 4:
in this example, the product obtained was NiCo2O4@ Auricularia aerogel composite.
Above is NiCo2O4The preparation method of the @ edible fungus aerogel composite material comprises the following steps:
(1) ultrasonically cleaning Auricularia auricula with deionized water and anhydrous ethanol for 3 times, each time for 10min, placing in a 60 deg.C oven, and drying for 24 hr;
(2) soaking 4g of the agaric obtained in the step (1) in 60ml of deionized water for 1 hour, transferring the agaric into a 100ml of polytetrafluoroethylene lining, putting the agaric into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 10 hours, and then cooling to room temperature to obtain an agaric gel solution;
(3) carrying out ultrasonic treatment on the agaric gel solution obtained in the step (2) for 2 hours, freezing the obtained uniform gel at-85 ℃ overnight, and carrying out vacuum freeze-drying for 72 hours to obtain agaric aerogel;
(4) carrying out heat treatment on the agaric aerogel obtained in the step (3) in an argon atmosphere, wherein the heat treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 120min, and cooling to room temperature along with a furnace to obtain agaric carbon aerogel;
(5) 1mmol of nickel nitrate hexahydrate, 2mmol of cobalt nitrate hexahydrate, 12mmol of urotropine and 6mmol of ammonium fluoride are dissolved in 30ml of deionized water and stirred for 10min to form uniform NiCo2O4A solution;
(6) adding the agaric carbon aerogel obtained in the step (4) into the uniform solution obtained in the step (5), and mixing the agaric carbon aerogel with NiCo2O4The mass ratio of the solution is 1: 1, continuously stirring for 6 hours, pouring the mixture into 50ml of polytetrafluoroethylene as a lining, putting the mixture into a stainless steel autoclave, heating the mixture to 120 ℃ in a hydrothermal heating mode, preserving the heat for 6 hours, and then cooling the mixture to room temperature;
(7) respectively filtering and washing the product prepared in the step (6) by deionized water and absolute ethyl alcohol for 3 times, placing the product in a 60 ℃ oven, and drying the product for 24 hours;
(8) and (4) carrying out heat treatment on the product obtained in the step (7) in air, wherein the heat treatment temperature is 350 ℃, the heat preservation time is 120min, the heating rate is 1 ℃/min, and the product is cooled to room temperature along with the furnace.
The product prepared in the above way is tested, and the testing method and the testing content are completely the same as those in the embodiment 1.
Comparative example:
in this embodiment, the prepared product is an agaric aerogel composite material.
The preparation method of the agaric aerogel composite material comprises the following steps:
(1) ultrasonically cleaning Auricularia auricula with deionized water and anhydrous ethanol for 3 times, each time for 10min, placing in a 60 deg.C oven, and drying for 24 hr;
(2) soaking 4g of the agaric obtained in the step (1) in 60ml of deionized water for 1 hour, transferring the agaric into a 100ml of polytetrafluoroethylene lining, putting the agaric into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 10 hours, and then cooling to room temperature to obtain an agaric gel solution;
(3) carrying out ultrasonic treatment on the agaric gel solution obtained in the step (2) for 2 hours, freezing the obtained uniform gel at-85 ℃ overnight, and carrying out vacuum freeze-drying for 72 hours to obtain agaric aerogel;
(4) and (4) carrying out heat treatment on the agaric aerogel obtained in the step (3) in an argon atmosphere, wherein the heat treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 120min, and cooling to room temperature along with a furnace to obtain the agaric carbon aerogel.
XRD was performed on the product obtained as described above, as shown in FIG. 1.
Table 1 the phase compositions of the materials prepared in examples 1 to 4, and the wave-absorbing properties of the prepared materials are shown below.
The symbols in table 1 have the following meanings:
RL-reflection losses;RL minminimum reflection losses.
Phase analysis: as shown in FIG. 1, examples 1-4 and comparative examples each contained typical amorphous carbon diffraction peaks after heat treatment. Synthesizing NiCo through chemical in-situ reaction2O4After nano-structuring, the composites prepared in examples 1-4 were made from carbon, NiCo2O4Two phasesAnd (4) forming.
Wave-absorbing performance analysis: as can be seen from Table 1, the product C @ NCO-S obtained in example 1 had a minimum RL value of-54.6 dB and a maximum effective absorption bandwidth (RL < -10 dB) of 5.7 GHz. The RL value of the sample C @ NCO-S obtained in example 2 was-46.3 dB, corresponding to an EAB value of 3.1 GHz. The product obtained in example 3 also showed an effective absorption with an RL of-16.5 dB. The maximum RL of the product obtained in the embodiment 4 is-53.8 dB, and the wave-absorbing performance is good. Therefore, the product obtained in example 1 shows excellent wave absorbing performance and has great application potential.
In conclusion, NiCo with excellent wave-absorbing performance can be prepared through simple heat treatment and chemical in-situ synthesis reaction2O4@ Auricularia aerogel composite. Especially, the technological parameters can stably and efficiently prepare NiCo2O4The @ edible fungus aerogel composite material effectively adjusts the wave absorbing performance, thereby greatly promoting the industrial production and having important significance for the wide application and development of the wave absorbing material.
The above embodiments are provided to explain the technical solutions of the present invention in a detailed manner, and it should be understood that the above examples are only specific embodiments of the present invention, and are not intended to limit the present invention. Any modification, addition or equivalent substitution made within the scope of the present invention shall be included within the protection scope of the present invention.
Claims (8)
1. NiCo2O4The @ black fungus carbon aerogel composite material is characterized in that the composite material takes black fungus carbon aerogel of biomass-derived porous carbon as a raw material, and NiCo is uniformly distributed on the black fungus carbon aerogel in an in-situ compounding manner2O4A nanostructure.
2. A NiCo product according to claim 12O4The preparation method of the @ black fungus carbon aerogel composite material is characterized by comprising the following steps of:
step A1: dissolving 1mmol nickel nitrate hexahydrate, 2mmol cobalt nitrate hexahydrate and 12mmol additive in 30ml deionized water, stirring for 10minClock, forming uniform NiCo2O4A solution;
step A2, adding agaric carbon aerogel into the uniform solution obtained in the step A1, continuously stirring for 6 hours, pouring into 50ml of polytetrafluoroethylene as an inner liner, putting into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 6 hours, and then cooling to room temperature;
step A3, respectively filtering and washing the product prepared in the step A2 with deionized water and absolute ethyl alcohol for 3 times, placing the product in a 60 ℃ oven, and drying the product for 24 hours;
step A4: and D, carrying out heat treatment on the product obtained in the step A3 in air, wherein the heat treatment temperature is 350 ℃, the heating rate is 1 ℃/min, the heat preservation time is 120 minutes, and cooling to the room temperature along with the furnace.
3. A NiCo product according to claim 22O4The preparation method of the @ black fungus carbon aerogel composite material is characterized in that the additive is one of urea and urotropine.
4. A NiCo product according to claim 22O4The preparation method of the @ black fungus carbon aerogel composite material is characterized in that 6mmol of ammonium fluoride can be added in the step A1.
5. A NiCo product according to claim 22O4The preparation method of the @ black fungus carbon aerogel composite material is characterized by comprising the following steps of:
step B1: ultrasonically cleaning Auricularia auricula with deionized water and anhydrous ethanol for 3 times, each time for 10min, placing in a 60 deg.C oven, and drying for 24 hr;
step B2: soaking the agaric obtained in the step B1 in 60ml of deionized water for 1 hour, transferring the agaric into a polytetrafluoroethylene lining, putting the agaric into a stainless steel autoclave, heating to 120 ℃ in a hydrothermal heating mode, preserving heat for 10 hours, and then cooling to room temperature to obtain an agaric gel solution;
step B3: b2, carrying out ultrasonic treatment on the agaric gel solution obtained in the step B2 for 2 hours, freezing the obtained uniform gel at-85 ℃ overnight, and carrying out vacuum freeze-drying for 72 hours to obtain agaric aerogel;
step B4: and D, carrying out heat treatment on the agaric aerogel obtained in the step B3 in an inert gas atmosphere, wherein the heat treatment temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 120min, and cooling to room temperature along with a furnace to obtain the agaric carbon aerogel.
6. A NiCo according to claim 52O4The preparation method of the @ black fungus carbon aerogel composite material is characterized in that the black fungus carbon aerogel and NiCo2O4The mass ratio of the solution is 1: 1.
7. a NiCo according to claim 52O4The preparation method of the @ black fungus carbon aerogel composite material is characterized in that the inert gas in the step B4 is one of argon and nitrogen.
8. The NiCo of any of claims 1 to 72O4The application of the @ Auricularia carbon aerogel composite material in low-frequency electromagnetic wave absorption.
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