CN115197674A - Cobaltosic oxide/nickel oxide/PEDOT wave-absorbing material and preparation method thereof - Google Patents
Cobaltosic oxide/nickel oxide/PEDOT wave-absorbing material and preparation method thereof Download PDFInfo
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 61
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 title claims abstract description 50
- 239000011358 absorbing material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 42
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 22
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000012153 distilled water Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 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 abstract description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 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 10
- 239000012265 solid product Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004471 Glycine Substances 0.000 claims description 7
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000005485 electric heating Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- 238000011049 filling Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 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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- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
Abstract
Adding nickel hydroxide powder and 2-methylimidazole into methanol, stirring and dissolving to obtain a mixed solution, dropwise adding a methanol solution of cobalt nitrate hexahydrate while stirring, uniformly mixing, standing and aging, then carrying out centrifugal separation, filtering, washing and drying to obtain a precursor, calcining the precursor in air, cooling to obtain a cobaltosic oxide/nickel oxide mixture, adding the cobaltosic oxide/nickel oxide mixture, sodium dodecyl sulfate and p-toluenesulfonic acid into distilled water, uniformly mixing, adding an EDOT monomer to obtain a mixed solution, heating to 45-50 ℃, dropwise adding an iron chloride hexahydrate solution into the mixed solution, stirring for reaction, washing, filtering and drying to obtain the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material. Compared with the prior art, the material has the advantages of simple preparation process and low raw material cost, and the prepared wave-absorbing material has the characteristics of strong absorption, low-frequency band absorption and thin matching thickness, and has good application prospect in the field of electromagnetic wave absorption.
Description
Technical Field
The invention relates to a preparation method of cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material, belonging to the technical field of wave-absorbing materials.
Background
As microwave technology is widely applied to the civil and military fields, various problems caused by electromagnetic wave pollution are more and more serious. The electromagnetic wave radiation can not only influence the health of people through electromagnetic wave radiation and cause the probability of cancer of people to increase, but also cause the running of precise instruments to cause problems, thereby shortening the service life of expensive instruments. At present, electromagnetic wave absorbing materials are an important approach to solve this problem.
Generally, electromagnetic waves can be classified into three types, incident electromagnetic waves, reflected electromagnetic waves, and transmitted electromagnetic waves. In order to realize that the material can meet the conditions of practical application, the electromagnetic wave absorption material should meet the characteristics of strong absorption, wide effective absorption frequency band, thin matching thickness, small density and light weight as much as possible. For this reason, researchers have designed and controlled various microstructures for materials.
PEDOT is a polymer of EDOT (3,4-ethylenedioxythiophene monomer), an important conductive polymer material, and has excellent electrochemical activity, a moderate band gap, a low oxidation-reduction potential and excellent environmental adaptability. The conductive polymer-based wave-absorbing material is often characterized by low density and high conductivity, but has the problems of impedance mismatching, strong reflection and the like. At present, there are researchers by mixing magnetic Fe 3 O 4 The particles and PEDOT are chemically oxidized and polymerized in situ to obtain Fe with a core-shell structure 3 O 4 The @ PEDOT composite material has the performance lower than-20 dB in medium and high frequency bands, but is insufficient in S wave band and wave-absorbing strength.
Disclosure of Invention
The invention aims to provide a preparation method of cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material aiming at the defects of the prior art, the prepared composite wave-absorbing material has the characteristics of thin matching thickness, small density and strong absorption, has wave-absorbing performance lower than-10 dB in a low frequency band, and has higher wave-absorbing capacity and effective absorption bandwidth in a medium-high frequency band.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material comprises the following steps:
(1) Adding nickel hydroxide powder and 2-methylimidazole into methanol, stirring and dissolving to obtain a mixed solution, dropwise adding a methanol solution of cobalt nitrate hexahydrate into the mixed solution while stirring, uniformly mixing, standing and aging, then performing centrifugal separation, filtering, washing a solid product with methanol, and finally drying to obtain a precursor;
(2) Calcining the precursor in air, and then cooling to room temperature to obtain a cobaltosic oxide/nickel oxide mixture;
(3) Adding a cobaltosic oxide/nickel oxide mixture, sodium dodecyl sulfate and p-toluenesulfonic acid into distilled water, uniformly stirring, and then adding an EDOT (3,4 ethylenedioxythiophene) monomer to obtain a mixed solution;
(4) And (3) heating the mixed solution obtained in the step (3) to 45-50 ℃, dropwise adding ferric chloride hexahydrate solution into the mixed solution, stirring for reaction after dropwise adding, washing a reaction product after the reaction is finished, filtering, and drying a solid product to obtain the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material.
Further, in the step (1), the molar ratio of the nickel hydroxide to the 2-methylimidazole is 1.
Further, in the step (1), the molar ratio of the nickel hydroxide to the cobalt nitrate hexahydrate is 1:2.
Further, in the step (1), the preparation method of the nickel hydroxide powder comprises the following steps: dissolving nickel nitrate hexahydrate in distilled water, dropwise adding ammonia water into the solution until the solution is dark blue, and then adding glycine, wherein the molar ratio of glycine to nickel nitrate hexahydrate is 1: and 4, transferring the mixed solution to a reaction kettle after uniformly mixing, then placing the reaction kettle in an electric heating forced air drying oven, heating to 100 ℃ for reaction for 6 hours, cooling to room temperature after the reaction is finished, alternately washing the reaction product with absolute ethyl alcohol and distilled water, filtering, and finally drying to obtain the catalyst.
Further, in the step (1), the rotation speed of the centrifugal separation is 8000-10000 r/min, and the time is 5-10 min.
Further, in the step (2), the calcining temperature is 500 ℃, and the calcining time is 3-4 h.
Further, in the step (3), the molar ratio of the sodium dodecyl sulfate to the EDOT is 1:5, the molar ratio of the p-toluenesulfonic acid to the EDOT is 10:1.
further, in the step (3), the usage amount of the cobaltosic oxide/nickel oxide mixture is 50-220 g/mol of the EDOT monomer based on the usage amount of the EDOT monomer.
Further, in the step (4), the molar ratio of the ferric chloride hexahydrate and EDOT is 1:1.
The invention has the beneficial effects that:
firstly, preparing a precursor, then calcining the precursor in the air to obtain a cobaltosic oxide/nickel oxide mixture, and then carrying out chemical oxidation self-polymerization reaction on the cobaltosic oxide/nickel oxide/PEDOT mixture and a conductive polymer monomer EDOT to obtain the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material. The prepared wave-absorbing material not only has wave-absorbing performance lower than-10 dB in a low-frequency band, but also has higher wave-absorbing capacity and effective absorption bandwidth in medium-high frequency. The preparation process is simple, the operation is easy, the production cost is low, the prepared material is a wave-absorbing material with low-frequency band absorption, strong absorption and thin matching thickness, when the matching thickness is 5.0mm, the filling amount is 30 percent, the frequency is 3.77GHz, the maximum reflection loss is-17.93 dB, and the effective bandwidth is 1.04GHz (3.32-4.36 GHz); when the matching thickness is 2.0mm, the filling amount is 30%, and the frequency is 10.33GHz, the maximum reflection loss is-48.41 dB, the effective bandwidth is 2.48GHz (9.21-11.69 GHz), and the wave-absorbing material is small in density, strong in absorption and good in development prospect.
Drawings
FIG. 1 is an XRD pattern of the precursor prepared in example 3;
FIG. 2 is an XRD pattern of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 3;
FIG. 3 is a FT-IR chart of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in examples 1-3;
FIG. 4 is an SEM image of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 3;
FIG. 5 is a reflection loss curve of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 1 at a thickness of 1.0-5.5 mm;
FIG. 6 is a reflection loss curve of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 2 at a thickness of 1.0-5.5 mm;
FIG. 7 is a reflection loss curve of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 3 at a thickness of 1.0-5.5 mm.
Detailed Description
The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments. It is to be understood that the following text is merely illustrative of one or more specific embodiments of the invention and does not strictly limit the scope of the invention as specifically claimed.
Example 1
A preparation method of cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material comprises the following steps:
(1) Adding 3mmol of nickel hydroxide powder and 30mmol of 2-methylimidazole into 60mL of methanol, and magnetically stirring for dissolving to obtain a mixed solution; dropwise adding a methanol solution of hexahydrate cobalt nitrate into the mixed solution while stirring, wherein the molar ratio of nickel hydroxide to hexahydrate cobalt nitrate is 1:2, uniformly mixing, standing and aging for one day, then performing centrifugal separation (9000 r/min,6 min), filtering, washing a solid product for 3 times by using methanol, and finally drying to obtain a precursor;
the preparation method of the nickel hydroxide powder comprises the following steps: dissolving 10mmol of nickel nitrate hexahydrate in 100mL of distilled water, dropwise adding ammonia water into the solution until the solution is dark blue, then adding 2.5mmol of glycine, uniformly mixing, transferring the mixed solution to a reaction kettle, placing the reaction kettle in an electric heating forced air drying box, heating to 100 ℃, reacting for 6 hours, cooling to room temperature after the reaction is finished, alternately washing the reaction product with absolute ethyl alcohol and distilled water, filtering, and finally drying to obtain the nickel nitrate hexahydrate.
(2) Heating the precursor to 500 ℃ at the speed of 5 ℃/min in the air, calcining for 3h, and then cooling to room temperature to obtain a cobaltosic oxide/nickel oxide mixture;
(3) Adding 0.215g of cobaltosic oxide/nickel oxide mixture, 0.8mmol of sodium dodecyl sulfate and 40mmol of p-toluenesulfonic acid into 100mL of distilled water, uniformly stirring, and then adding 4mmol (450 mu L) of EDOT monomer to obtain a mixed solution;
(4) Heating the mixed solution obtained in the step (3) to 50 ℃, dropwise adding ferric chloride hexahydrate into the mixed solution, wherein the molar ratio of ferric chloride hexahydrate to EDOT is 1:1, stirring and reacting for 24 hours after dropwise adding is finished, washing a reaction product by using absolute ethyl alcohol and distilled water alternately after the reaction is finished, filtering and drying a solid product to obtain the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material, wherein the cobaltosic oxide/nickel oxide accounts for 33.3% of the mass of the wave-absorbing material.
Example 2
A preparation method of cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material comprises the following steps:
(1) Adding 3mmol of nickel hydroxide powder and 30mmol of 2-methylimidazole into 60mL of methanol, and magnetically stirring for dissolving to obtain a mixed solution; dropwise adding a methanol solution of hexahydrate cobalt nitrate into the mixed solution while stirring, wherein the molar ratio of nickel hydroxide to hexahydrate cobalt nitrate is 1:2, uniformly mixing, standing and aging for one day, then performing centrifugal separation (9000 r/min,6 min), filtering, washing a solid product for 3 times by using methanol, and finally drying to obtain a precursor;
the preparation method of the nickel hydroxide powder comprises the following steps: dissolving 10mmol of nickel nitrate hexahydrate in 100mL of distilled water, dropwise adding ammonia water into the solution until the solution is dark blue, then adding 2.5mmol of glycine, uniformly mixing, transferring the mixed solution to a reaction kettle, placing the reaction kettle in an electric heating forced air drying box, heating to 100 ℃, reacting for 6 hours, cooling to room temperature after the reaction is finished, alternately washing the reaction product with absolute ethyl alcohol and distilled water, filtering, and finally drying to obtain the nickel nitrate hexahydrate.
(2) Heating the precursor to 500 ℃ at the speed of 5 ℃/min in the air, calcining for 3h, and then cooling to room temperature to obtain a cobaltosic oxide/nickel oxide mixture;
(3) Adding 0.430g of cobaltosic oxide/nickel oxide mixture, 0.8mmol of sodium dodecyl sulfate and 40mmol of p-toluenesulfonic acid into 100mL of distilled water, uniformly stirring, and then adding 4mmol (450 mu L) of EDOT monomer to obtain a mixed solution;
(4) And (3) heating the mixed solution obtained in the step (3) to 50 ℃, dropwise adding an iron chloride hexahydrate solution into the mixed solution, wherein the molar ratio of the iron chloride hexahydrate to the EDOT is 1:1, stirring and reacting for 24 hours after dropwise adding, alternately washing a reaction product by using absolute ethyl alcohol and distilled water after the reaction is finished, filtering, and drying a solid product to obtain the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material.
Example 3
A preparation method of cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material comprises the following steps:
(1) Adding 3mmol of nickel hydroxide powder and 30mmol of 2-methylimidazole into 60mL of methanol, and magnetically stirring for dissolving to obtain a mixed solution; dropwise adding a methanol solution of hexahydrate of cobalt nitrate into the mixed solution while stirring, wherein the molar ratio of nickel hydroxide to hexahydrate of cobalt nitrate is 1:2, uniformly mixing, standing and aging for one day, then performing centrifugal separation (9000 r/min,6 min), filtering, washing a solid product with methanol for 3 times, and finally drying to obtain a precursor;
the preparation method of the nickel hydroxide powder comprises the following steps: dissolving 10mmol of nickel nitrate hexahydrate in 100mL of distilled water, dropwise adding ammonia water into the solution until the solution is dark blue, then adding 2.5mmol of glycine, uniformly mixing, transferring the mixed solution to a reaction kettle, placing the reaction kettle in an electric heating forced air drying box, heating to 100 ℃, reacting for 6 hours, cooling to room temperature after the reaction is finished, alternately washing the reaction product with absolute ethyl alcohol and distilled water, filtering, and finally drying to obtain the nickel nitrate hexahydrate.
(2) Heating the precursor to 500 ℃ at the speed of 5 ℃/min in the air, calcining for 3h, and then cooling to room temperature to obtain a cobaltosic oxide/nickel oxide mixture;
(3) Adding 0.860g of cobaltosic oxide/nickel oxide mixture, 0.8mmol of sodium dodecyl sulfate and 40mmol of p-toluenesulfonic acid into 100mL of distilled water, uniformly stirring, and then adding 4mmol (450 mu L) of EDOT monomer to obtain a mixed solution;
(4) And (3) heating the mixed solution obtained in the step (3) to 50 ℃, dropwise adding an iron chloride hexahydrate solution into the mixed solution, wherein the molar ratio of the iron chloride hexahydrate to the EDOT is 1:1, stirring and reacting for 24 hours after dropwise adding, alternately washing a reaction product by using absolute ethyl alcohol and distilled water after the reaction is finished, filtering, and drying a solid product to obtain the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material.
Fig. 1 is an XRD pattern of the precursor prepared in example 3, and characteristic peaks of nickel hydroxide (JCPDS 14-0117) corresponding to diffraction peaks appearing at 2 θ =19.3 °, 33.1 °, 38.5 °, 52.1 °, 59.1 °, 62.7 °, and 72.7 °, respectively, are shown by the pattern, and have crystal face indices of (001), (100), (101), (102), (110), (111), and (201), respectively. As shown in figure 1, in the XRD pattern of the precursor, the sharp peak of the ZIF-67 shows that the crystal form is complete and the purity is good, and compared with a standard PDF card, the sharp peak has no other impurity peaks, which indicates that the ZIF-67 precursor is successfully synthesized, and the sharp peak has no other impurity peaks except the nickel hydroxide and the ZIF-67, and indicates that the precursor is successfully prepared.
Fig. 2 is an XRD chart of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 3, and it can be shown that diffraction peaks appearing at 2 θ =19.0 °, 31.2 °, 36.8 °, 38.5 °, 44.8 °, 55.6 °, 59.3 ° and 65.2 ° respectively correspond to characteristic peaks (JCPDS 74-2120) of cobaltosic oxide, and their crystal plane indexes are (111), (220), (311), (222), (400), (422), (511) and (440), respectively; diffraction peaks appearing at 2 θ =37.2 °, 43.3 °, 62.8 ° and 75.3 ° respectively correspond to characteristic peaks of nickel oxide (JCPDS 71-1179) having crystal plane indices of (111), (200), (220), and (311), respectively. Compared with a standard PDF card, the material has no impurity peak, and indicates that the cobaltosic oxide/nickel oxide material is successfully prepared. As can be seen from the corresponding graph of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material, a wider polymer diffraction peak is formed at 26.5 degrees and corresponds to the characteristic peak of PEDOT, which shows that the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material is successfully prepared.
Absorption of examples 1-3 using a Fourier Infrared spectrometerPhase structure analysis is carried out on the wave material, and figure 3 is an FT-IR diagram of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in the embodiment 1-3, wherein 1512 cm and 1343cm are shown in the diagram -1 The peak at (A) is due to C = C/C-C elongation of the thiophene ring, 1199, 1142, 1086cm -1 Due to the stretching action of C-O-C, 981 and 839cm -1 Due to the stretching of the ring of the cyclic ethylene at 689cm -1 The peak at position (A) is due to the symmetrical C-S-C elongation in the thiophene ring, at 571cm -1 And 663cm -1 The peak value of (A) is a characteristic peak of Co-O and Ni-O. The infrared characteristic peak of PEDOT can be seen in the wave-absorbing material maps of examples 1-3, which shows that cobaltosic oxide/nickel oxide/PEDOT is successfully prepared.
Fig. 4 is an SEM image of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 3, where fig. 4 (a) corresponds to PEDOT, fig. 4 (b) corresponds to cobaltosic oxide, fig. 4 (c) corresponds to nickel oxide, and fig. 4 (d) corresponds to cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material, it can be seen that the individual PEDOT has a stacked structure, cobaltosic oxide has a special bowl-shaped shape, niO has a petal-shaped layered structure, introduction of cobaltosic oxide increases a magnetic loss mechanism of the composite material, and the layered structure of NiO can increase a transmission path of electromagnetic waves, so that the electromagnetic waves can be reflected and refracted multiple times inside the material, thereby enhancing a loss capability, and PEDOT provides more channels for electron transmission, so that the material has higher conductance loss. The composite material has excellent electromagnetic wave absorption performance through the synergistic effect of magnetism and dielectric.
And analyzing the electromagnetic parameters of the sample by means of a Vector Network Analyzer (VNA) to further calculate the wave absorbing performance of the sample. The test results are shown in FIGS. 5-7.
Fig. 5 is a reflection loss curve of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 1 at a thickness of 1.0-5.5 mm, fig. 6 is a reflection loss curve of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 2 at a thickness of 1.0-5.5 mm, fig. 7 is a reflection loss curve of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material prepared in example 3 at a thickness of 1.0-5.5 mm, as shown in fig. 5, when the matching thickness is 5.0mm, the filling amount is 30%, the frequency is 8.36GHz, the maximum reflection loss is-13.88 dB, and the effective bandwidth is 1.64GHz (7.76-9.45 GHz); as shown in FIG. 6, when the matching thickness is 5.0mm, the filling amount is 30%, the maximum reflection loss is-10.55 dB and the effective bandwidth is 0.88GHz (9.94-10.82 GHz) at a frequency of 10.45 GHz; as shown in FIG. 7, when the matching thickness is 5.0mm, the filling amount is 30%, the maximum reflection loss is-17.93 dB and the effective bandwidth is 1.04GHz (3.32-4.36 GHz) at the frequency of 3.77 GHz; when the matching thickness is 2.0mm, the filling amount is 30%, and the frequency is 10.33GHz, the maximum reflection loss is-48.41 dB, and the effective bandwidth is 2.48GHz (9.21-11.69 GHz).
Claims (10)
1. A preparation method of cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material is characterized by comprising the following steps:
(1) Adding nickel hydroxide powder and 2-methylimidazole into methanol, stirring and dissolving to obtain a mixed solution, dropwise adding a methanol solution of cobalt nitrate hexahydrate into the mixed solution while stirring, uniformly mixing, standing and aging, then performing centrifugal separation, filtering, washing a solid product with methanol, and finally drying to obtain a precursor;
(2) Calcining the precursor in air, and then cooling to room temperature to obtain a cobaltosic oxide/nickel oxide mixture;
(3) Adding a cobaltosic oxide/nickel oxide mixture, sodium dodecyl sulfate and p-toluenesulfonic acid into distilled water, uniformly stirring, and then adding an EDOT monomer to obtain a mixed solution;
(4) And (3) heating the mixed solution obtained in the step (3) to 45-50 ℃, dropwise adding ferric chloride hexahydrate solution into the mixed solution, stirring for reaction after dropwise adding, washing a reaction product after the reaction is finished, filtering, and drying a solid product to obtain the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material.
2. The method for preparing the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material according to claim 1, wherein in the step (1), the molar ratio of the nickel hydroxide to the 2-methylimidazole is 1.
3. The preparation method of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material according to claim 1, wherein in the step (1), the molar ratio of the nickel hydroxide to the cobalt nitrate hexahydrate is 1:2.
4. The preparation method of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material according to claim 1, wherein in the step (1), the preparation method of the nickel hydroxide powder comprises the following steps: dissolving nickel nitrate hexahydrate in distilled water, dropwise adding ammonia water into the solution until the solution is dark blue, and then adding glycine, wherein the molar ratio of glycine to nickel nitrate hexahydrate is 1: and 4, transferring the mixed solution to a reaction kettle after uniformly mixing, then placing the reaction kettle in an electric heating forced air drying oven, heating to 100 ℃ for reaction for 6 hours, cooling to room temperature after the reaction is finished, alternately washing the reaction product with absolute ethyl alcohol and distilled water, filtering, and finally drying to obtain the catalyst.
5. The preparation method of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material as claimed in claim 1, wherein in the step (1), the rotation speed of the centrifugal separation is 8000-10000 r/min, and the time is 5-10 min.
6. The preparation method of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material according to claim 1, wherein in the step (2), the calcination temperature is 500 ℃, and the calcination time is 3-4 h.
7. The preparation method of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material according to claim 1, wherein in the step (3), the molar ratio of the sodium dodecyl sulfate to the EDOT is 1:5.
8. the preparation method of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material according to claim 1, wherein in the step (3), the molar ratio of the p-toluenesulfonic acid to the EDOT is 10:1.
9. the method for preparing the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material according to claim 1, wherein in the step (3), the dosage of the cobaltosic oxide/nickel oxide mixture is 50-220 g/mol of the EDOT monomer based on the dosage of the EDOT monomer.
10. The preparation method of the cobaltosic oxide/nickel oxide/PEDOT composite wave-absorbing material according to any one of claims 1 to 9, wherein in the step (4), the molar ratio of the ferric chloride hexahydrate and the EDOT is 1:1.
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Application publication date: 20221018 Assignee: Jiangsu Chuangqi Testing Technology Co.,Ltd. Assignor: YANCHENG INSTITUTE OF TECHNOLOGY Contract record no.: X2024980001234 Denomination of invention: A cobalt tetroxide/nickel oxide/PEDOT absorbing material and its preparation method Granted publication date: 20231024 License type: Common License Record date: 20240122 |
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