CN113912139A - Efficient electromagnetic wave-absorbing material prepared from biomass carbon and preparation method thereof - Google Patents
Efficient electromagnetic wave-absorbing material prepared from biomass carbon and preparation method thereof Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 49
- 239000011358 absorbing material Substances 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 23
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 241000251468 Actinopterygii Species 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 229910003266 NiCo Inorganic materials 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000000137 annealing Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000010000 carbonizing Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000011324 bead Substances 0.000 description 3
- 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 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 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 description 3
- 239000002994 raw material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis 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
- C01G53/00—Compounds of nickel
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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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
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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Abstract
The invention discloses a high-efficiency electromagnetic wave-absorbing material prepared from biomass carbon and a preparation method thereof, wherein a proper amount of fish scales are firstly decalcified and then subjected to high-temperature pre-carbonization, and then subjected to high-temperature carbonization after activation treatment to obtain a biomass porous carbon material; secondly, dissolving cobalt nitrate, nickel nitrate and glycerol in isopropanol to perform hydrothermal reaction, and then performing annealing treatment to obtain core-shell nickel cobaltate spheres; then carrying out hydrothermal reaction with hydrochloric acid and potassium permanganate to obtain NiCo2O4@MnO2(ii) a Finally, the biomass porous carbon material and NiCo are treated by ultrasonic2O4@MnO2And compounding to obtain the efficient electromagnetic wave-absorbing material prepared from the biomass carbon.The efficient electromagnetic wave-absorbing material prepared by the invention adopts the green and environment-friendly carbon source and is compounded with the magnetic nano material with the core-shell structure, so that biomass waste is well utilized, the wave-absorbing performance of the material is well enhanced, the problems of high density of the magnetic wave-absorbing material and single wave-absorbing mechanism of the nano wave-absorbing material are solved, and the efficient electromagnetic wave-absorbing material has a good application prospect.
Description
Technical Field
The invention relates to the technical field of wave-absorbing material preparation, in particular to a high-efficiency electromagnetic wave-absorbing material prepared from biomass carbon and a preparation method thereof.
Background
In recent years, with the gradual popularization of electronic information technology and wireless communication and the wide application of 5G communication, the electronic technology brings convenience to the life of people, and meanwhile, the problems of electromagnetic interference and electromagnetic pollution are increasingly serious. WHO (world health organization) has listed electromagnetic wave radiation pollution as a fourth environmental pollution source, so overcoming electromagnetic radiation and electromagnetic interference has become a major hotspot problem in the development of the world today.
The electromagnetic wave absorbing material is also called a wave absorbing material, and is an electromagnetic functional material which can convert the energy of incident electromagnetic waves into heat energy and other forms of energy through dielectric loss or can enable the electromagnetic waves to be lost through destructive interference.
The biomass carbon source has the characteristics of rich varieties, low cost, sustainability, cleanness and environmental protection, and is more environment-friendly compared with the traditional carbon source. The traditional carbon material preparation usually needs inorganic or organic chemical reagents and some non-renewable resources as raw materials, and the carbon material is synthesized by complex organic reaction under severe conditions, so that the cost is high and the pollution is serious. With the deepening of the concept of environmental protection, the environment-friendly carbon material is synthesized by using certain low-cost and renewable biomass resources as synthesis raw materials by using a common technical means, and has wide prospect. There are over 1400 million tons of global biomass waste produced by agricultural products per year. The biomass carbon source has the advantages of low cost, abundant varieties, no pollution, renewability and the like, and is considered to be one of the most potential biomass energy sources. Therefore, the conversion of the raw materials into new materials is of great significance for the reasonable utilization of resources and the environmental protection.
Electromagnetic wave absorbing materials have been the focus of current research because they can convert the energy of incident electromagnetic waves into heat energy or other forms of energy loss. The magnetic nano materials such as iron, cobalt, nickel and the like have the advantages of high saturation magnetization, strong magnetic loss capability, low cost and the like, and are regarded as good wave-absorbing materials, but simultaneously, the materials have the defects of large density, low impedance matching level, easy oxidation, narrow absorption frequency band, difficult reduction and the like, and the requirements of the ideal wave-absorbing material on thin thickness, light weight, wide effective absorption frequency band and strong absorption strength are difficult to meet.
The porous carbon material prepared by the biomass carbon source has a porous structure, is easy to regulate and control, is light and large in specific surface area, but the single carbon material has no magnetism, and has poor impedance matching level; the magnetic nano material has high density and low impedance matching level, and further expansion and application of the magnetic nano material are limited. In order to overcome the defects and further optimize the electromagnetic wave absorption performance of the porous carbon material and the magnetic nano material, the invention applies the efficient electromagnetic wave absorbing material prepared from the biomass carbon and the preparation method thereof, the environment-friendly biomass carbon is utilized and is compounded with the magnetic nano material with the core-shell structure, on one hand, the biomass waste is well utilized, on the other hand, the wave absorbing performance of the material is well enhanced, and the invention has good application prospect.
Disclosure of Invention
The invention aims to provide a high-efficiency electromagnetic wave-absorbing material prepared from biomass carbon and a preparation method thereof. The composite wave-absorbing material prepared by the method has stronger reflection loss and wide effective absorption frequency band under the conditions of low filling degree and low matching thickness.
The technical scheme adopted by the invention is that the method for preparing the hierarchical porous carbon material by using the fish scales is characterized by comprising the following specific preparation steps:
1) soaking fish scales in hydrochloric acid for decalcification, washing with deionized water, drying, and pre-carbonizing by high-temperature heating in a vacuum tube furnace under protective atmosphere. Mixing a pre-carbonized sample and an alkaline substance according to the mass ratio of 1: 4, drying after mixing, then placing in a vacuum tube furnace for high-temperature heating carbonization in a protective atmosphere, and cooling to room temperature to obtain the biomass porous carbon material;
2) dissolving cobalt nitrate, nickel nitrate and glycerol in isopropanol, stirring vigorously for a period of time, transferring to a high-pressure reaction kettle for hydrothermal reaction, and then collecting a product through centrifugation;
3) washing the product with deionized water, then vacuum drying, placing the sample after vacuum drying in a tubular furnace, and carrying out high-temperature annealing treatment in the atmosphere of air to obtain the core-shell structure nickel cobaltate spheres;
4) uniformly dispersing nickel cobaltate pellets in deionized water under ultrasound, adding potassium permanganate solid while slowly dropwise adding hydrochloric acid under stirring, fully stirring at room temperature for a period of time, then transferring the mixed solution into a high-pressure reaction kettle for hydrothermal reaction, collecting products through magnetism, respectively cleaning the products with absolute ethyl alcohol and deionized water, and drying to obtain NiCo2O4@MnO2；
5) Mixing NiCo2O4@MnO2Dispersing the biomass carbon into absolute ethyl alcohol through ultrasonic treatment, taking supernatant liquid by using a dropper, dropwise adding the supernatant liquid into a biomass porous carbon material, uniformly mixing the biomass porous carbon material under ultrasonic treatment, and drying the mixture in vacuum to obtain the efficient electromagnetic wave absorbing material prepared from the biomass carbon.
Preferably, in the step 1), the weight of the fish scales is 2-10 g, the concentration of the hydrochloric acid is 0.5-3 mol/L, and the alkaline substances are potassium hydroxide, sodium carbonate and the like.
Preferably, the decalcification time in the step 1) is 12-24 h.
Preferably, the protective atmosphere during high-temperature heating in step 1) is high-purity nitrogen or argon.
Preferably, the temperature rise rate in the high-temperature heating and pre-carbonization step 1) is 1-10 ℃/min, the heating temperature is 200-400 ℃, and the heat preservation time is 1-5 h.
Preferably, the heating rate in the high-temperature heating carbonization in the step 1) is 1-10 ℃/min, the heating temperature is 600-1000 ℃, and the heat preservation time is 0.5-3 h.
Preferably, in the step 2), the mass of the cobalt nitrate is 0.5-1.5 g, the mass of the nickel nitrate is 0.2-0.8 g, the volume of the glycerol is 5-10 mL, and the volume of the isopropanol is 30-50 mL.
Preferably, the temperature of the hydrothermal reaction in the step 2) is 150-200 ℃, and the time is 2-10 h.
Preferably, the temperature of the high-temperature annealing treatment in the step 3) is 300-500 ℃, and the time is 1-5 hours.
Preferably, the volume of the deionized water in the step 4) is 20-80 mL.
Preferably, the mass of the potassium permanganate in the step 4) is 0.5-2 g, the hydrochloric acid is analytically pure, and the volume of the hydrochloric acid is 0.5-2 ml.
Preferably, the stirring time in the step 4) is 20-60 min.
Preferably, the temperature of the hydrothermal reaction in the step 4) is 80-150 ℃, and the time is 30-90 min.
Preferably, the amount of the absolute ethyl alcohol in the step 5) is 10-50 mL.
Preferably, the amount of the supernatant obtained in the step 5) is 3-18 mL.
Preferably, NiCo in the step 5)2O4@MnO2The mass of (A) is 0.05 to 0.1g, and the mass of the porous carbon material is 0.1 to 0.3 g.
Preferably, the temperature in the drying treatment process does not exceed 100 ℃.
The invention synthesizes NiCo by utilizing a biomass carbon source2O4@MnO2The porous carbon composite wave-absorbing material has simple preparation process, the biomass carbon material has high dielectricity, and the NiCo material has high dielectricity2O4@MnO2The nano particles have high saturation magnetization, the composite material has dielectric and magnetic properties, the electromagnetic wave absorption strength can be effectively improved by utilizing the magnetic-electric synergistic effect, the biomass carbon source is cheap and easy to obtain, is green and environment-friendly, and is compounded with the magnetic nano material with the core-shell structure, so that the biomass waste is well utilized, the wave absorption performance of the material is well enhanced, and the application prospect is good.
Drawings
FIG. 1 shows NiCo in example 1 of the present invention2O4@MnO2S of porous carbonAnd (5) EM pictures.
Detailed Description
The invention is further described in detail with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
Example 1
1) Soaking 5.0g of fish scales in 1mol/L hydrochloric acid for 12h, washing with deionized water, drying at 80 ℃, then placing in a vacuum tube furnace, heating and pre-carbonizing at 300 ℃ (the heating rate is 5 ℃/min, and the temperature is kept for 2h) in a nitrogen protective atmosphere, and then mixing with KOH according to the mass ratio of 1: 4, drying after mixing, placing in a vacuum tube furnace, heating and carbonizing at a high temperature of 800 ℃ (the heating rate is 2 ℃/min, and the heat preservation time is 60min) in a nitrogen protective atmosphere, and cooling to room temperature to obtain a porous biomass carbon material;
2) dissolving 0.7g of cobalt nitrate hexahydrate, 0.4g of nickel nitrate hexahydrate and 8mL of glycerol in 40mL of isopropanol, violently stirring for 30min, placing in a high-pressure reaction kettle for hydrothermal reaction (180 ℃, 6h), and collecting a precursor through centrifugation after the hydrothermal reaction;
3) cleaning the precursor with deionized water for 3 times, then drying in vacuum (60 ℃, 12h), placing in a tubular furnace, heating at 450 ℃ (heating rate 5 ℃/min, heat preservation for 2h) in the air atmosphere, and obtaining the core-shell structure nickel cobaltate beads;
4) uniformly dispersing nickel cobaltate pellets in 80mL of deionized water under ultrasound, adding 1.0g of potassium permanganate solid under stirring, then dropwise adding 1.0mL of hydrochloric acid, fully stirring at room temperature for 30min, transferring the mixture into a high-pressure reaction kettle for hydrothermal reaction (100 ℃, 6h), magnetically collecting a product after the hydrothermal reaction, then respectively cleaning with absolute ethyl alcohol and deionized water for three times, and drying at 80 ℃ to obtain NiCo2O4@MnO2；
5) Mixing NiCo2O4@MnO2Dispersing the mixture in 15mL of absolute ethyl alcohol under ultrasonic treatment, taking 9mL of supernatant by using a dropper, adding the supernatant into the porous biomass carbon material, performing ultrasonic treatment for 20min to ensure that the mixture is well and uniformly mixed, and performing vacuum drying (60 ℃, 12h) to obtain the efficient electromagnetic wave absorbing material prepared from the biomass carbon.
Example 2
1) Soaking 2.0g of fish scales in 0.5mol/L hydrochloric acid for decalcification for 18h, washing with deionized water, drying at 85 ℃, placing in a vacuum tube furnace, heating and pre-carbonizing at 200 ℃ (the heating rate is 3 ℃/min, and the temperature is kept for 2h) in a nitrogen protective atmosphere, and then mixing with KOH according to the mass ratio of 1: 3, mixing, drying, placing in a vacuum tube furnace, heating and carbonizing at high temperature of 700 ℃ (the heating rate is 3 ℃/min, and the temperature is kept for 30min) in the nitrogen protective atmosphere, and cooling to room temperature to obtain the porous biomass carbon material;
2) dissolving 0.5g of cobalt nitrate hexahydrate, 0.2g of nickel nitrate hexahydrate and 5mL of glycerol in 30mL of isopropanol, violently stirring for 45min, placing in a high-pressure reaction kettle for hydrothermal reaction (150 ℃, 4h), and collecting a precursor through centrifugation after the hydrothermal reaction;
3) cleaning the precursor with deionized water for 3 times, then drying in vacuum (60 ℃, 12h), placing in a tubular furnace, and heating at 300 ℃ (heating rate of 5 ℃/min, heat preservation for 1h) in the air atmosphere to obtain core-shell structure nickel cobaltate beads;
4) uniformly dispersing nickel cobaltate pellets in 60mL of deionized water under ultrasound, adding 0.5g of potassium permanganate solid under stirring, then dropwise adding 0.5mL of hydrochloric acid, fully stirring at room temperature for 30min, transferring the mixture into a high-pressure reaction kettle for hydrothermal reaction (80 ℃, 6h), magnetically collecting a product after the hydrothermal reaction, then respectively cleaning with absolute ethyl alcohol and deionized water for three times, and drying at 80 ℃ to obtain NiCo2O4@MnO2；
5) Mixing NiCo2O4@MnO2Dispersing in 12mL of absolute ethyl alcohol under ultrasonic treatment, taking 6mL of supernatant by using a dropper, adding into the porous biomass carbon material, carrying out ultrasonic treatment for 30min to well and uniformly mix the materials, and carrying out vacuum drying (60 ℃, 12h) to obtain the efficient electromagnetic wave absorbing material prepared from the biomass carbon.
Example 3
1) Soaking 8.0g of fish scales in 1.5mol/L hydrochloric acid for decalcification for 24h, washing with deionized water, drying at 90 ℃, placing in a vacuum tube furnace, heating and pre-carbonizing at 350 ℃ (the heating rate is 4 ℃/min, and the temperature is kept for 2h) in a nitrogen protective atmosphere, and then mixing with KOH according to the mass ratio of 1: 2, mixing, drying, placing in a vacuum tube furnace, heating and carbonizing at high temperature of 900 ℃ (the heating rate is 5 ℃/min, and the temperature is kept for 180min) in the nitrogen protective atmosphere, and cooling to room temperature to obtain the porous biomass carbon material;
2) dissolving 1.4g of cobalt nitrate hexahydrate, 0.7g of nickel nitrate hexahydrate and 10mL of glycerol in 50mL of isopropanol, violently stirring for 60min, placing in a high-pressure reaction kettle for hydrothermal reaction (160 ℃, 8h), and collecting a precursor through centrifugation after the hydrothermal reaction;
3) cleaning the precursor with deionized water for 3 times, then drying in vacuum (60 ℃, 12h), placing in a tubular furnace, and heating at 500 ℃ (heating rate 3 ℃/min, heat preservation for 1h) in the air atmosphere to obtain the core-shell structure nickel cobaltate beads;
4) uniformly dispersing nickel cobaltate pellets in 70mL of deionized water under ultrasound, adding 2.0g of potassium permanganate solid under stirring, then dropwise adding 2.0mL of hydrochloric acid, fully stirring at room temperature for 30min, transferring the mixture into a high-pressure reaction kettle for hydrothermal reaction (100 ℃, 6h), magnetically collecting a product after the hydrothermal reaction, then respectively cleaning with absolute ethyl alcohol and deionized water for three times, and drying at 80 ℃ to obtain NiCo2O4@MnO2；
5) Mixing NiCo2O4@MnO2Dispersing the mixture in 15mL of absolute ethyl alcohol under ultrasonic treatment, taking 9mL of supernatant by using a dropper, adding the supernatant into the porous biomass carbon material, performing ultrasonic treatment for 20min to ensure that the mixture is well and uniformly mixed, and performing vacuum drying (60 ℃, 12h) to obtain the efficient electromagnetic wave absorbing material prepared from the biomass carbon.
As can be seen from the attached figure 1, the carbon material prepared by the method has the porous characteristic, is favorable for introducing multiple interfacial polarization, and has the surface uniformly loaded with NiCo2O4@MnO2The magnetic nano-particles are beneficial to introducing magnetic loss and effectively improving the absorption strength.
Claims (10)
1. A high-efficiency electromagnetic wave-absorbing material prepared from biomass carbon and a preparation method thereof are characterized by comprising the following steps:
1) soaking fish scales in hydrochloric acid for decalcification, washing with deionized water, drying, placing in a vacuum tube furnace, heating at high temperature in a protective atmosphere for pre-carbonization, mixing with an alkaline substance according to a certain mass ratio, drying, placing in the vacuum tube furnace, heating at high temperature in the protective atmosphere for carbonization, and cooling to room temperature to obtain a porous biomass carbon material;
2) dissolving cobalt nitrate, nickel nitrate and glycerol in isopropanol, violently stirring for a period of time, placing in a high-pressure reaction kettle for hydrothermal reaction, and then collecting a product through centrifugation;
3) washing the product with deionized water, drying the product in vacuum, and then placing the product in a tubular furnace to be heated at high temperature in the air atmosphere to obtain the core-shell structure nickel cobaltate spheres;
4) uniformly dispersing nickel cobaltate pellets in deionized water under ultrasound, adding potassium permanganate solid under stirring, then dropwise adding hydrochloric acid, fully stirring at room temperature, transferring the mixture into a high-pressure reaction kettle, magnetically collecting a product after hydrothermal reaction, then respectively cleaning with absolute ethyl alcohol and deionized water, and drying to obtain NiCo2O4@MnO2；
5) Mixing NiCo2O4@MnO2Dispersing the mixture in absolute ethyl alcohol under ultrasonic treatment, taking supernatant liquid by a dropper, adding the supernatant liquid into a porous biomass carbon material, well and uniformly mixing the mixture under ultrasonic treatment, and drying the mixture in vacuum to obtain the efficient electromagnetic wave absorbing material prepared from the biomass carbon.
2. The efficient electromagnetic wave absorbing material prepared from biomass carbon and the preparation method of the efficient electromagnetic wave absorbing material are characterized in that in the step 1), the weight of fish scales is 2-10 g, the concentration of hydrochloric acid is 0.5-3 mol/L, and the decalcification time is 12-24 h;
3. the efficient electromagnetic wave absorbing material prepared from biomass carbon and the preparation method of the efficient electromagnetic wave absorbing material are characterized in that in the step 1), the alkaline substance is one of potassium hydroxide, sodium carbonate and the like, and the mass ratio is 1: 1-1: 5.
4. The efficient electromagnetic wave absorbing material prepared from biomass carbon and the preparation method of the efficient electromagnetic wave absorbing material are characterized in that the protective atmosphere in the step 1) during high-temperature heating and pre-carbonization is high-purity nitrogen or argon, the temperature during heating and pre-carbonization is 200-400 ℃, the temperature rise rate is 1-10 ℃/min, and the heat preservation time is 1-5 h;
5. the efficient electromagnetic wave absorbing material prepared from biomass carbon and the preparation method of the efficient electromagnetic wave absorbing material are characterized in that the temperature during high-temperature heating and carbonization in the step 1) is 600-1000 ℃, the temperature rise rate is 1-10 ℃/min, and the heat preservation time is 0.5-3 h.
6. The efficient electromagnetic wave absorbing material prepared from biomass carbon and the preparation method of the efficient electromagnetic wave absorbing material are characterized in that in the step 2), the mass of cobalt nitrate is 0.5-1.5 g, the mass of nickel nitrate is 0.2-0.8 g, the volume of glycerol is 5-10 mL, the volume of isopropanol is 30-50 mL, the temperature of hydrothermal reaction is 150-200 ℃, and the time of hydrothermal reaction is 2-10 hours.
7. The efficient electromagnetic wave absorbing material prepared from biomass carbon and the preparation method of the efficient electromagnetic wave absorbing material are characterized in that the temperature of the drying treatment process in the step 3) is not more than 80 ℃, the high-temperature heating temperature is 300-500 ℃, and the time is 1-5 hours.
8. The efficient electromagnetic wave absorbing material prepared from biomass carbon and the preparation method of the efficient electromagnetic wave absorbing material are characterized in that in the step 4), the volume of deionized water is 20-80 mL, the mass of potassium permanganate is 0.5-2 g, the volume of hydrochloric acid is 0.5-2 mL, the stirring time is 20-60 min, the hydrothermal reaction temperature is 80-150 ℃, and the hydrothermal reaction time is 30-90 min.
9. The efficient electromagnetic wave absorbing material prepared from biomass carbon and the preparation method thereof according to claim 1, wherein the temperature of the drying treatment in the step 4) is not more than 100 ℃.
10. The efficient electromagnetic wave absorbing material prepared from biomass carbon and the preparation method of the efficient electromagnetic wave absorbing material are characterized in that the amount of absolute ethyl alcohol in the step 5) is 10-50 mL, and the amount of the supernatant is 3-18 mL.
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