CN112499697A - Accordion-shaped NiCo2O4Wave-absorbing material and preparation method thereof - Google Patents

Accordion-shaped NiCo2O4Wave-absorbing material and preparation method thereof Download PDF

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CN112499697A
CN112499697A CN202011435216.2A CN202011435216A CN112499697A CN 112499697 A CN112499697 A CN 112499697A CN 202011435216 A CN202011435216 A CN 202011435216A CN 112499697 A CN112499697 A CN 112499697A
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wave
absorbing material
accordion
nico
metal salt
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CN112499697B (en
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吴宏景
师宾
常卿
张利民
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Northwestern Polytechnical University
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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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • 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
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention belongs to the technical field of inorganic wave-absorbing materials, and discloses a novel accordion-shaped NiCo2O4The wave-absorbing material has a special accordion shape and regular appearance. The preparation method comprises the following steps: s1, dissolving divalent nickel ion metal salt, divalent cobalt ion metal salt and a complexing agent in water to obtain a nickel-cobalt ion complexing solution; s2, adding a template agent and a precipitator into the nickel-cobalt ion complex solution, carrying out hydrothermal reaction, cooling, and then sequentially filtering, washing and drying to obtain a precursor; and S3, calcining the precursor to obtain the catalyst. The accordion-shaped NiCo prepared by the invention2O4The wave-absorbing material has excellent wave-absorbing performance and good application prospect in the field of wave-absorbing materials; and the preparation process is simple, the raw materials are cheap and easy to obtain, the requirement on production equipment is low, and the industrial production is easy to realize.

Description

Accordion-shaped NiCo2O4Wave-absorbing material and preparation method thereof
Technical Field
The invention relates to a method for preparing accordion-shaped NiCo by adding complexing agent2O4A wave-absorbing material and a preparation method thereof, belonging to the technical field of inorganic wave-absorbing materials.
Background
With the development of scientific technology, particularly, rapid development of wireless devices and electronic devices used in industrial and commercial fields, the electronic devices tend to be miniaturized and miniaturized, and the operating band tends to be high frequency. The equipment working in high frequency band is easy to be interfered by electromagnetic wave generated by other electronic devices, which will result in the performance reduction and even paralysis of the equipment. In addition, high frequency electromagnetic waves are harmful to human health. Therefore, with the rapid development of modern high and new electronic technologies and the improvement of the attention degree of people to health care, the requirements on various performances of the wave-absorbing material, such as absorption frequency range, wave-absorbing performance, heat resistance, corrosion resistance, density and the like, are higher and higher, and the research and development of novel wave-absorbing materials become the focus of wide attention of researchers.
Spinel type NiCo2O4Has the advantages of porous structure, high polarization, high loss, large shape anisotropy and the like, and is the most promising electromagnetic wave absorbing material. Recent studies have shown that NiCo2O4The morphology of the NiCo has a profound influence on the microwave absorption performance of the NiCo, the morphology of the NiCo is closely related to a synthesis method, and a hydrothermal method has become a method for preparing NiCo due to the advantages of simple operation, adjustable product morphology and the like2O4The main method of (1). CN110272719A, CN107177053A, CN107244877A, CN107177053B, CN107244877B and the like respectively disclose preparation methods of nickel cobaltate composite wave-absorbing materials, but the preparation methods are complex and have high cost.
Disclosure of Invention
The invention prepares a novel accordion-shaped NiCo quickly and simply by a complexing agent method2O4The wave-absorbing material has the advantages of small thickness and good wave-absorbing performance; and the preparation process is simple, has low requirements on production equipment, and is easy for industrial production.
The invention provides a preparation method of an accordion-shaped wave-absorbing material, which comprises the following specific steps:
s1, dissolving divalent nickel ion metal salt, divalent cobalt ion metal salt and a complexing agent in water to obtain a nickel-cobalt ion complexing solution;
the complexing agent is one or more of ethylenediamine, sodium sulfosalicylate, sodium citrate, oxalic acid, sodium oxalate and disodium ethylene diamine tetraacetate;
s2, adding a template agent and a precipitator into the nickel-cobalt ion complexing solution, carrying out hydrothermal reaction on the obtained mixed solution, cooling, sequentially filtering, washing and drying to obtain a precursor;
s3, calcining the precursor to obtain the accordion-shaped NiCo2O4And (3) a wave-absorbing material.
Preferably, the molar ratio of the divalent nickel ion metal salt to the divalent cobalt ion metal salt is 1: 2;
the molar ratio of the complexing agent to the mixture of the divalent nickel ion metal salt and the divalent cobalt ion metal salt is 0.1-2.5: 1.
further preferably, the anion of the divalent nickel ion metal salt and the divalent cobalt ion metal salt is one of chloride, nitrate, acetate and sulfate.
Preferably, the template agent is cetyl trimethyl ammonium bromide or anhydrous glucose, or a mixture of the two.
Further preferably, the precipitant is one or more of sodium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate and urea.
More preferably, the molar ratio of the templating agent to nickel ions is 0.5-2: 1;
the molar ratio of the precipitant to the mixture of the divalent nickel ion metal salt and the divalent cobalt ion metal salt is 1-3: 1.
preferably, the hydrothermal reaction is carried out at 40-220 ℃ for 10min-24 h.
Preferably, the calcination is at 60-600 ℃ for 0.5-3 h.
The accordion-shaped NiCo prepared by the method2O4The wave-absorbing material is in a regular accordion shape, and is 0.5-1.5 microns wide and 3-5 microns long.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the preparation process, a complexing agent is added, so that the nucleation and growth rate of crystals can be reduced, the growth rates of different crystal faces are adjusted, the morphology of the material is controlled, and the novel accordion-shaped wave-absorbing material is prepared;
(2) the preparation process is simple and has strong controllability;
(3) the effective absorption bandwidth of the prepared wave-absorbing material exceeds 7GHz, the matching thickness is about 2mm, and the requirements of small thickness and wide absorption of the wave-absorbing material are met;
(4) the adopted raw materials are cheap and easy to obtain, and the method has industrialization potential.
Drawings
FIG. 1 is an X-ray diffraction pattern of the wave-absorbing material prepared in each example; wherein, S1, S2 and S3 represent examples 1, 2 and 3, respectively;
FIG. 2 is a scanning electron microscope image of the wave-absorbing material prepared in example 1;
FIG. 3 is a wave-absorbing property diagram of the wave-absorbing material prepared in example 1;
FIG. 4 is a scanning electron microscope image of the wave-absorbing material prepared in example 2;
FIG. 5 is a scanning electron microscope image of the wave-absorbing material prepared in example 3.
Detailed Description
The present invention is further described below by way of examples, but the present invention is not limited by these examples. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
0.1426g of NiCl were accurately weighed in stoichiometric ratio2·6H2O and 0.2855g CoCl2·6H2O, adding into 60mL of deionized water; 0.3528g of sodium oxalate is accurately weighed and added into the solution, and the solution is quickly stirred for 10min to become uniform liquid; 0.1621g of anhydrous glucose and 0.1462g of urea are added in sequence, and high-speed stirring is carried out for 30 min; transferring the solution into a stainless steel reaction kettle, and heating to 220 ℃ for reaction for 10 hours; naturally cooling to room temperature after the reaction is finished, performing suction filtration, washing and drying to obtain a wave-absorbing material precursor; finally calcining for 2h at 400 ℃ to obtain the accordion-shaped NiCo2O4And (3) a wave-absorbing material.
S1 in FIG. 1 is X-ray diffraction of the prepared sampleAnd (4) mapping. All diffraction peak shapes are sharp and are similar to spinel structure NiCo2O4(JCPDS No.20-0718) shows that NiCo is identical2O4The crystal form is complete and has good crystallinity.
Fig. 2 is a scanning electron microscope image of the synthetic wave-absorbing material of the embodiment. From this figure, NiCo can be seen2O4In the shape of a regular accordion.
Example 2
0.1426g of NiCl were accurately weighed in stoichiometric ratio2·6H2O and 0.2855g CoCl2·6H2O, adding into 60mL of deionized water; 1.1790g of sodium sulfosalicylate is accurately weighed and added into the solution, and the solution is rapidly stirred for 10min to become uniform liquid; 0.9720g of anhydrous glucose and 0.38mL of ammonia water are added in sequence, and the mixture is stirred at high speed for 30 min; transferring the solution into a stainless steel reaction kettle, and heating to 40 ℃ for reaction for 24 hours; naturally cooling to room temperature after the reaction is finished, performing suction filtration, washing and drying to obtain a wave-absorbing material precursor; finally calcining for 0.5h at 600 ℃ to obtain the accordion-shaped NiCo2O4And (3) a wave-absorbing material.
In FIG. 1, S2 is the X-ray diffraction pattern of the prepared sample.
FIG. 4 is a scanning electron microscope image of the synthetic wave-absorbing material of this embodiment, from which NiCo can be seen2O4In the shape of a regular accordion.
Example 3
0.1426g of NiCl were accurately weighed in stoichiometric ratio2·6H2O and 0.2855g CoCl2·6H2O, adding into 60mL of deionized water; accurately measuring 12 μ L of ethylenediamine, adding into the above solution, and rapidly stirring for 10min to obtain uniform liquid; 0.6552g of hexadecyl trimethyl ammonium bromide and 0.0711g of ammonium bicarbonate are sequentially added, and the mixture is stirred at a high speed for 30 min; transferring the solution into a stainless steel reaction kettle, heating to 220 ℃ and reacting for 10 min; naturally cooling to room temperature after the reaction is finished, performing suction filtration, washing and drying to obtain a wave-absorbing material precursor; finally calcining for 3h at 60 ℃ to obtain accordion-shaped NiCo2O4And (3) a wave-absorbing material.
In FIG. 1, S3 is the X-ray diffraction pattern of the prepared sample.
FIG. 5 is a scanning electron microscope image of the synthetic wave-absorbing material of this embodiment, from which NiCo can be seen2O4In the shape of a regular accordion.
In the embodiment, the complexing agent is added in the preparation process, so that the nucleation and growth rate of crystals can be reduced, the growth rates of different crystal faces are adjusted, the morphology of the material is controlled, the novel accordion-shaped wave-absorbing material is prepared, and NiCo is added in the calcination temperature range of 60-600 DEG C2O4The appearance of the wave-absorbing material is basically not influenced.
NiCo prepared as a result of examples 1-32O4The properties of the absorbing material are basically the same, so only NiCo prepared in example 1 is used2O4Taking the wave-absorbing material as an example, a vector network analyzer (VNA, agilent n5230A, USA) was used to test the wave-absorbing performance of the accordion-like wave-absorbing material, and the result is shown in fig. 3.
As can be seen from FIG. 3, in the test range of 2-18GHz, the absorption peak of the reflection loss moves to a low frequency with the increase of the thickness of the test sample, and at 9.8GHz, the peak value of the reflection loss of the composite material sample with the thickness of 2.8mm is-49.73 dB, the effective bandwidth of RL < -10dB is 7.08GHz (10.92-18GHz), and the electromagnetic wave in the frequency band can be effectively absorbed.
Comparative example 1
Reference to "NiCo2O4A preparation method of constrained by differential dimensions of building blocks with super electronic wave absorption performance, Wu Hongjing, Qin Ming adn Zhang Limin, Composites Part B,2020,182: 10762' by using sodium citrate as a template agent to hydrothermally synthesize NiCo2O4The prepared wave-absorbing material has an effective absorption bandwidth of 6.08GHz (11.92-18GHz) and a reflection loss peak value of-42.8 dB.
Comparative example 2
Reference is made to "Synthesis and Electromagnetic wave absorption Performance of NiCo2O4nanomaterials with different nanostructures，Zhu Qinghai,Zhang Zilong,Lv Yangyang,Chen Xiqiao,Wu Zhuang,Wang The preparation method of Shuai and Zou Yanhong, CrystEngComm,2019,21: 4568-2O4The prepared wave-absorbing material with the nanoneedle can effectively absorb 4GHz (14-18 GHz) bandwidth and has a reflection loss peak value of-40 dB.
Comparative example 3
With reference to the preparation method in "Sodium citrate associated hydrothermally synthesized with structured morphology and complex dielectric parameters heated electromagnetic wave adsorption, Qin Ming, Lan Di, Wu Guinaglei, Qiao Xiiaoguang and Wu hong jin, Applied Surface Science,2020,504: 144480", NiCo is hydrothermally synthesized2O4The prepared wave-absorbing material has an effective absorption bandwidth of 4.28GHz (13.72-18 GHz) and a reflection loss peak value of-47.9 dB.
Compared with the shapes of microspheres, nano needles, nano sheets and the like prepared in comparative examples 1-3, the special accordion-shaped wave-absorbing material prepared in the embodiment 1 (the wave-absorbing material prepared in the embodiment 1 is taken as an example for effect explanation because the properties of the wave-absorbing material prepared in the embodiments 1-3 are basically the same) has the advantages of small thickness and wider wave-absorbing frequency band, and has good application prospect.
The above disclosure is only for the specific embodiment of the present invention, but the embodiment of the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.

Claims (9)

1. Accordion-shaped NiCo2O4The preparation method of the wave-absorbing material is characterized by comprising the following steps:
s1, dissolving divalent nickel ion metal salt, divalent cobalt ion metal salt and a complexing agent in water to obtain a nickel-cobalt ion complexing solution;
the complexing agent is one or more of ethylenediamine, sodium sulfosalicylate, sodium citrate, oxalic acid, sodium oxalate and disodium ethylene diamine tetraacetate;
s2, adding a template agent and a precipitator into the nickel-cobalt ion complexing solution, carrying out hydrothermal reaction on the obtained mixed solution, cooling, and sequentially filtering, washing and drying to obtain a precursor;
s3, calcining the precursor to obtain the accordion-shaped NiCo2O4And (3) a wave-absorbing material.
2. The accordion-like NiCo of claim 12O4The preparation method of the wave-absorbing material is characterized in that the molar ratio of the divalent nickel ion metal salt to the divalent cobalt ion metal salt is 1: 2;
the molar ratio of the complexing agent to the mixture of the divalent nickel ion metal salt and the divalent cobalt ion metal salt is 0.1-2.5: 1.
3. the accordion-like NiCo of claim 22O4The preparation method of the wave-absorbing material is characterized in that the anion of the divalent nickel ion metal salt and the divalent cobalt ion metal salt is one of chloride ion, nitrate radical, acetate radical and sulfate radical.
4. The accordion-like NiCo of claim 12O4The preparation method of the wave-absorbing material is characterized in that the template agent is cetyl trimethyl ammonium bromide or anhydrous glucose or a mixture of the cetyl trimethyl ammonium bromide and the anhydrous glucose.
5. The accordion-like NiCo of claim 42O4The preparation method of the wave-absorbing material is characterized in that the precipitator is one or more of sodium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate and urea.
6. The accordion-like NiCo of claim 52O4The preparation method of the wave-absorbing material is characterized in that the molar ratio of the template agent to nickel ions is 0.5-2: 1;
the molar ratio of the precipitant to the mixture of the divalent nickel ion metal salt and the divalent cobalt ion metal salt is 1-3: 1.
7. the accordion-like NiCo of claim 12O4The preparation method of the wave-absorbing material is characterized in that the hydrothermal reaction is carried out for 10min-24h at the temperature of 40-220 ℃.
8. The accordion-like NiCo of claim 12O4The preparation method of the wave-absorbing material is characterized in that the calcination is carried out for 0.5-3h at the temperature of 60-600 ℃.
9. An accordion-like NiCo prepared by the method of any of claims 1 to 82O4Wave-absorbing material, said NiCo2O4The wave-absorbing material is in a regular accordion shape, and has a width of 0.5-1.5 μm and a length of 3-5 μm.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109705808A (en) * 2019-02-02 2019-05-03 南京航空航天大学 A kind of cobalt-nickel alloy with MOF structure-porous carbon composite wave-suction material and preparation method thereof
CN110668505A (en) * 2019-09-24 2020-01-10 烟台大学 Cobalt-containing two-dimensional accordion-shaped nanosheet material and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109705808A (en) * 2019-02-02 2019-05-03 南京航空航天大学 A kind of cobalt-nickel alloy with MOF structure-porous carbon composite wave-suction material and preparation method thereof
CN110668505A (en) * 2019-09-24 2020-01-10 烟台大学 Cobalt-containing two-dimensional accordion-shaped nanosheet material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MING QIN等: ""Sodium citrate assisted hydrothermal synthesis of nickel cobaltate absorbers with tunable morphology and complex dielectric parameters toward efficient electromagnetic wave absorption"" *

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