CN114752090B - Co/PEDOT composite flexible self-supporting film and preparation and application thereof - Google Patents
Co/PEDOT composite flexible self-supporting film and preparation and application thereof Download PDFInfo
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- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 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 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 239000013067 intermediate product Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 35
- 235000011187 glycerol Nutrition 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- DZMKCIZPYSTJLZ-UHFFFAOYSA-L cobalt(2+);2,3-dihydroxypropanoate Chemical compound [Co+2].OCC(O)C([O-])=O.OCC(O)C([O-])=O DZMKCIZPYSTJLZ-UHFFFAOYSA-L 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- H05K9/0075—Magnetic shielding materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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Abstract
The invention relates to a Co/PEDOT composite flexible self-supporting film and preparation and application thereof, wherein the preparation method comprises the following steps: (1) Adding cobalt nitrate hexahydrate into glycerol and isopropanol solution, and stirring to completely dissolve the cobalt nitrate hexahydrate to obtain a transparent light pink mixed solution; (2) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction, washing and drying the obtained reaction product to obtain brown precursor powder; (3) Placing the precursor powder in hydrogen-containing argon atmosphere for high-temperature reduction, and then cooling to room temperature to obtain an intermediate product Co ball; (4) Dispersing Co balls in a methanol solution of PEDOT, fully dispersing the Co balls by ultrasonic, and carrying out vacuum suction filtration and drying to obtain a target product. The Co/PEDOT composite flexible self-supporting film has the shielding effectiveness reaching 51.5dB in the frequency range of 8.2-12.4GHz, and shows excellent electromagnetic interference shielding capability.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and relates to a Co/PEDOT composite flexible self-supporting film, and preparation and application thereof.
Background
With the rapid development of modern electronic information technology, electronic equipment is developed towards the directions of intelligence, high frequency, density and multifunctionality, and particularly the arrival of the 5G network era, the rapid popularization of intelligent electronic equipment brings great convenience to daily communication and life of people. People enjoy the convenience brought by the technologies, and meanwhile, because electromagnetic waves with different frequencies are inevitably generated in the operation process, the normal operation of other electronic equipment can be interfered, the information safety of the communication equipment can be threatened, and the human health is greatly endangered. Therefore, in order to reduce or avoid the influence of electromagnetic radiation, it is highly desirable to explore materials having efficient shielding properties. The electromagnetic shielding material is capable of preventing propagation and diffusion of electromagnetic waves, confining radiant energy within a safe range, thereby ensuring stable operation of the microelectronic device and eliminating unnecessary and increasingly severe electromagnetic radiation. Although the traditional metal electromagnetic shielding material has good electromagnetic shielding performance, the shielding mechanism is single, and the metal electromagnetic shielding material has the limitations of high density, easy corrosion, difficult processing and the like, and is difficult to meet the increasing demands of the emerging fields of flexible electronic devices and the like. Therefore, development of a flexible electromagnetic shielding material having ultra-thin and lightweight characteristics has become a research hotspot.
Transition group magnetic metals such as iron, cobalt, nickel and alloys thereof have intrinsic ferromagnetism, and can consume electromagnetic waves in an eddy current mode, however, the transition group magnetic metals have the problems of high density, easy corrosion, difficult processing and the like, and the transition group magnetic metals are limited to be widely applied in the fields of aerospace, communication, medical treatment and the like.
The conductive polymer has good conductivity, can consume electromagnetic waves in an electric form, and has the characteristics of light weight, easy processing, good flexibility, corrosion resistance and the like, so that the conductive polymer is paid more attention.
The preparation method for developing the flexible-base electronic shielding material has important significance for developing flexible electronic devices, electronic skins and the like by combining the electromagnetic shielding principle and the characteristics of the conductive polymer.
Disclosure of Invention
The invention aims to provide a Co/PEDOT composite flexible self-supporting film, and preparation and application thereof.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a Co/PEDOT composite flexible self-supporting film, which comprises the following steps:
(1) Adding cobalt nitrate hexahydrate into glycerol and isopropanol solution, and stirring to completely dissolve the cobalt nitrate hexahydrate to obtain a transparent light pink mixed solution;
(2) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction, washing and drying the obtained reaction product to obtain brown precursor powder;
(3) Placing the precursor powder in hydrogen-containing argon atmosphere for high-temperature reduction, and then cooling to room temperature to obtain an intermediate product Co ball;
(4) Dispersing Co balls in a methanol solution of PEDOT, fully dispersing the Co balls by ultrasonic, and carrying out vacuum suction filtration and drying to obtain a target product.
Further, in the step (1), the concentration of cobalt nitrate hexahydrate in the mixed solution is 0.005-0.02 mol/L;
the volume ratio of glycerol to isopropanol is (5-10): (20-45).
Further, in the step (2), the temperature of the hydrothermal reaction is 120-200 ℃ and the time is 5-12 h.
Further, in the step (2), the washing process is as follows: and adopting deionized water and ethanol to centrifugally wash for a plurality of times at 8000-10000 rpm.
Further, in the step (2), the drying process specifically includes: vacuum drying at 60-80 deg.c.
Further, in the step (3), the volume fraction of hydrogen in the hydrogen argon atmosphere is 4-6%.
Further, in the step (3), the high-temperature reduction process specifically includes: calcining at 550-650 deg.c for 4-6 hr.
Further, in the step (4), the concentration of the methanol solution of PEDOT is 0.3-0.5 g/L, preferably 0.4g/L, and the addition amount of the Co balls is 0.4-10g/L after the addition.
The second technical scheme of the invention provides a Co/PEDOT composite flexible self-supporting film, which is prepared by adopting any one of the preparation methods. Porous nano Co spheres are distributed in the obtained flexible self-supporting film, the porous nano Co spheres are spherical, the size of the porous nano Co spheres is 200 nm-1 mu m, and a nano pore structure is distributed on the surface of the porous nano Co spheres.
The third technical scheme of the invention provides application of the Co/PEDOT composite flexible self-supporting film, and the flexible self-supporting film is used as an electromagnetic shielding material. When the method is applied specifically, the steps are as follows: the self-supporting film prepared was cut to a size of 10.2X12.9 mm 2 Is a rectangular sample of (c). The electromagnetic interference shielding effectiveness in the frequency range of 8.2-12.4GHz is tested by a waveguide method by using a vector network analyzer with the model of Agilent N5230C.
The invention combines the Co magnetic metal material with stronger magnetic loss with the conductive polymer PEDOT to obtain the novel two-dimensional film electromagnetic shielding material with light weight and strong electromagnetic loss capacity.
The micro-nano metal magnetic material has stronger electromagnetic loss capacity and controllability based on small size and surface effect compared with the traditional block material, and can change the magnetic domain topological structure by regulating the shape, size and assembly form. Is beneficial to improving the magnetic conductivity. Based on this, porous Co spheres of nano-size were prepared. By adjusting the temperature and the reaction time of the calcination precursor, the microcosmic result of the porous Co spheres can be changed greatly, and the structural change affects the electromagnetic parameters of the material, thereby affecting the loss capacity of the material on electromagnetic waves. The self-supporting film with stronger flexibility can be prepared by compounding the self-supporting film with the conductive polymer PEDOT, and a conductive network formed between the self-supporting film and the conductive polymer PEDOT is beneficial to enhancing the attenuation capability of electromagnetic waves and improving the electromagnetic shielding performance.
The invention adopts a high-efficiency and simple hydrothermal reaction method to synthesize the precursor cobalt glycerate. After high-temperature reduction in hydrogen argon atmosphere, the product particles have better dispersibility and no obvious agglomeration phenomenon. The organic-inorganic self-supporting film formed by combining with PEDOT shows excellent performance in the field of electromagnetic shielding.
Compared with the prior art, the Co/PEDOT self-supporting film provided by the invention has stronger flexibility and heat dissipation. The porous nano Co balls have rich pore structures, so that multiple scattering and multiple reflection are increased, reflection loss of electromagnetic waves in the material is enhanced, interface polarization is increased at rich interfaces in the composite structure to absorb and attenuate the electromagnetic waves, the Co balls are uniformly dispersed in the PEDOT to form a conductive network, excellent conductivity is endowed to the composite film material, and attenuation of the electromagnetic waves by the electric loss form is enhanced. The flexible self-supporting film material which has good electromagnetic shielding performance and is easy to prepare has good application prospect.
Drawings
FIG. 1 is a scanning electron microscope, a transmission electron microscope and a self-supporting thin film graph of porous nano Co spheres and a flexible self-supporting thin film of example 1, wherein (a 1) the transmission electron microscope graph of the porous nano Co spheres of example 1; (a2) Example 1-transmission electron microscopy of single porous nano Co spheres; (b1) Example 1-scanning electron microscope image of porous nano Co spheres; (b2) Example 1-scanning electron microscope image of porous nano Co spheres with high magnification; (c1) Example 1-Co/PEDOT composite flexible self-supporting film photograph; (c2) Example 1-cross-sectional scanning electron microscope image of Co/PEDOT composite flexible self-supporting film.
FIG. 2 is an X-ray diffraction pattern of the porous nano Co spheres of example 1-2.
Fig. 3 is an electromagnetic shielding effectiveness, including total electromagnetic shielding performance, reflective electromagnetic shielding performance, and absorptive electromagnetic shielding performance, of the composite flexible self-supporting film of example 1-Co/PEDOT.
Fig. 4 is an electromagnetic shielding effectiveness, including total electromagnetic shielding performance, reflective electromagnetic shielding performance, and absorptive electromagnetic shielding performance, of the example 2-Co/PEDOT composite flexible self-supporting film.
Fig. 5 shows the total electromagnetic interference Shielding Effectiveness (SET) of the flexible self-supporting film of examples 1-4 Co/PEDOT.
FIG. 6 is a scanning electron microscope and transmission electron microscope image of the product obtained by calcining the cobalt glycerate precursor in air and continuing high temperature reduction in example 5.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the examples which follow, PEDOT was prepared according to the following references: [ doi.org/10.1016/j.energy.2018.12.124, dan Ni, haijun Song, yuanxun Chen, kefeng Cai, free-standing highly conducting PEDOT films for flexible thermoelectric generator, energy,170 (2019), 53-61 ]. The remainder, unless specifically stated, are all indicated as conventional commercially available materials or conventional processing techniques in the art.
Example 1:
preparation of Co/PEDOT composite flexible self-supporting film:
first, 0.3mmol Co (NO 3 ) 2 ·6H 2 O,5mL glycerol and 25mL isopropanol were added to a 100mL beaker at vigorousIs completely dissolved under the magnetic stirring to obtain a uniform and transparent light pink solution.
Next, the solution was transferred to a teflon lined stainless steel hot-water reactor and heated at 180 ℃ for 5 hours. After cooling to room temperature, centrifugal washing with deionized water and ethanol for several times, vacuum drying at 60 ℃, and collecting to obtain brown cobalt glycerate precursor.
Finally, placing the precursor powder into a porcelain boat, placing into a tube furnace, and reducing at 650 ℃ for 5 hours under hydrogen-argon atmosphere (hydrogen volume fraction is 5%), wherein the heating rate is 2 ℃/min -1 Naturally cooling to room temperature to obtain black powder of porous cobalt balls with the size of about 200-300nm.
8mg of porous Co balls are taken to be dispersed in 20mL of methanol solution of PEDOT with the concentration of 0.4g/L, the solution is fully dispersed by ultrasonic treatment for 30min, suction filtration is carried out under the vacuum condition, and the solution is placed in room temperature for drying, thus obtaining the target flexible self-supporting film product.
Example 2:
compared to example 1, the vast majority are identical, except in this example: the amount of the porous Co pellets weighed was 80mg.
Example 3:
compared to example 1, the vast majority are identical, except in this example: the amount of the porous Co pellets weighed was 40mg.
Example 4:
compared to example 1, the vast majority are identical, except in this example: the amount of the porous Co pellets weighed was 160mg.
The microscopic morphology of the morphology-controllable multi-shaped Co spheres in the above examples was characterized by scanning electron microscopy (SEM, hitachi FE-SEM S-4800) and powder samples were coated on the surface of the conductive paste for testing. The microstructure information of the multi-state Co balls is characterized by a transmission electron microscope (TEM, JEOL JEM-2100F), and powder samples are subjected to ultrasonic dispersion in ethanol and then are dripped on a carbon-supported copper mesh for drying and testing. The X-ray diffraction spectrum was measured by a bruker d8 Advance instrument. Electromagnetic shielding parameters in the range of 8.2 to 12.4GHz were tested using a vector network analyzer model Agilent N5230C.
Fig. 1 is a Transmission Electron Microscope (TEM) image and a Scanning Electron Microscope (SEM) image of the multi-shaped Co spheres synthesized in the above embodiment 1, where the size of the nano Co spheres is about 200-300nm, the surface has a uniformly distributed nano pore structure, the particle size distribution of the sample is relatively uniform, the particle dispersibility is relatively good, and the self-supporting film obtained by vacuum filtration has high integrity and strong flexibility.
FIG. 2 is an X-ray diffraction (XRD) analysis of the porous Co spheres of examples 1-2 described above. In the figure, diffraction peaks at 2θ=44.22°,51.52 ° and 75.85 ° correspond to (111), (200) and (220) crystal planes (JCPDS No. 15-0806) of simple cubic Co. XRD pattern analysis demonstrates the compositional information of the material and no significant impurities and miscibility are present.
Fig. 3-4 show the electromagnetic interference shielding effectiveness of the above-described embodiment 1-2Co/PEDOT composite flexible self-supporting film, including total electromagnetic Shielding Effectiveness (SET), reflected electromagnetic Shielding Effectiveness (SER) and absorbed electromagnetic Shielding Effectiveness (SEA), for revealing the mechanism of excellent electromagnetic shielding effectiveness. Compared with example 1, the content ratio of the Co spheres in example 2 is increased, and then the reflection electromagnetic Shielding Effectiveness (SER) of the composite film is not obviously changed, but the absorption electromagnetic Shielding Effectiveness (SEA) of the composite film is obviously enhanced, so that the absorption electromagnetic shielding effectiveness is increased to a certain extent, and the content ratio of the porous Co spheres has a larger influence on the electromagnetic shielding effectiveness of the flexible film.
Fig. 5 shows the total electromagnetic interference Shielding Effectiveness (SET) of the flexible self-supporting film of examples 1-4 Co/PEDOT. As the Co sphere to PEDOT mass ratio increases from 1:1 to 20:1, the total electromagnetic Shielding Effectiveness (SET) of the composite film was about 30dB,41dB,45dB and 50dB, respectively; and the reflection electromagnetic Shielding Effectiveness (SER) of the composite film is not obviously changed along with the increase of the Co content, but the absorption electromagnetic Shielding Effectiveness (SEA) of the composite film is continuously improved, so that the total electromagnetic shielding effectiveness is further improved, and the content of the porous Co balls in the composite self-supporting film is an important condition for regulating and controlling electromagnetic parameters to influence the electromagnetic shielding effectiveness.
Example 5:
compared to example 1, the vast majority are identical, except in this example: the precursor cobalt glycerate is placed in a muffle furnace before high-temperature reduction, calcined in an air atmosphere, and then placed in a tube furnace for high-temperature reduction.
FIG. 6 is a scanning electron microscope and transmission electron microscope image of the product obtained by calcining the cobalt glycerate precursor in air and continuing high temperature reduction in example 5. The spherical morphology of the final product Co obtained in example 5 was destroyed and a more severe agglomeration occurred compared to example 1.
Example 6:
compared to example 1, the vast majority are identical, except in this example: the molar concentration of cobalt nitrate hexahydrate in the mixed solution is 0.006mol/L, and the volume ratio of glycerin to isopropanol is 1:5.
example 7:
compared to example 1, the vast majority are identical, except in this example: the molar concentration of cobalt nitrate hexahydrate in the mixed solution is 0.02mol/L, and the volume ratio of glycerin to isopropanol is 1:3.
example 8:
compared to example 1, the vast majority are identical, except in this example: the hydrothermal reaction temperature was 120 ℃.
Example 9:
compared to example 1, the vast majority are identical, except in this example: the hydrothermal reaction temperature was 200 ℃.
Example 10:
compared to example 1, the vast majority are identical, except in this example: the hydrothermal reaction time was 7 hours.
Example 11:
the vast majority of the reactions were identical to example 1, except that in this example the hydrothermal reaction time was 10 hours.
Example 12:
the vast majority of the reactions were identical to example 1, except that in this example the hydrothermal reaction time was 12 hours.
Example 13:
most of the same as in example 1 except that in this example, the temperature of the high temperature reduction was adjusted to calcine at 550℃for 4 hours.
Example 14:
most of the same as in example 1 except that in this example, the temperature of the high temperature reduction was adjusted to calcine at 600℃for 5 hours.
Example 15:
most of the same as in example 1 except that in this example, the temperature of the high temperature reduction was adjusted to calcine at 650 ℃ for 4 hours.
Example 16:
most of the same as in example 1 except that in this example, the temperature of the high temperature reduction was adjusted to calcine at 650 ℃ for 6h.
Example 17:
most of them are the same as in example 1 except that in this example, the hydrogen gas in the hydrogen argon atmosphere was used in an amount of 4% by volume.
Example 18:
most of them are the same as in example 1 except that in this example, the volume fraction of hydrogen in the hydrogen argon atmosphere used was 6%.
Example 19:
compared to example 1, the vast majority are identical, except in this example: the molar concentration of cobalt nitrate hexahydrate in the mixed solution is 0.005mol/L, and the volume ratio of glycerin to isopropanol is 1:9.
example 20:
compared to example 1, the vast majority are identical, except in this example: the molar concentration of cobalt nitrate hexahydrate in the mixed solution is 0.01mol/L, and the volume ratio of glycerin to isopropanol is 1:2.
the previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (5)
1. The preparation method of the Co/PEDOT composite flexible self-supporting film is characterized by comprising the following steps of:
(1) Adding cobalt nitrate hexahydrate into glycerol and isopropanol solution, and stirring to completely dissolve the cobalt nitrate hexahydrate to obtain a transparent light pink mixed solution;
(2) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction, washing and drying the obtained reaction product to obtain brown precursor powder;
(3) Placing the precursor powder in hydrogen-containing argon atmosphere for high-temperature reduction, and then cooling to room temperature to obtain an intermediate product Co ball;
(4) Dispersing Co balls in a methanol solution of PEDOT, fully dispersing the Co balls by ultrasonic treatment, and carrying out vacuum suction filtration and drying to obtain a target product;
in the step (1), the concentration of cobalt nitrate hexahydrate in the mixed solution is 0.005-0.02 mol/L;
the volume ratio of glycerol to isopropanol is (5-10): (20-45);
in the step (2), the temperature of the hydrothermal reaction is 120-200 ℃ and the time is 5-12 h;
in the step (3), the volume fraction of hydrogen in the hydrogen-argon atmosphere is 4-6%;
in the step (3), the high-temperature reduction process specifically comprises the following steps: calcining for 4-6 hours at 550-650 ℃;
in the step (4), the concentration of the methanol solution of PEDOT is 0.3-0.5 g/L, and the addition amount of the Co balls is 0.4-10g/L after the addition.
2. The method for preparing the Co/PEDOT composite flexible self-supporting film according to claim 1, wherein in the step (2), the washing process is as follows: and adopting deionized water and ethanol to centrifugally wash for a plurality of times at 8000-10000 rpm.
3. The method for preparing the Co/PEDOT composite flexible self-supporting film according to claim 1, wherein in the step (2), the drying process is specifically as follows: and (5) drying in vacuum at 60-80 ℃.
4. A Co/PEDOT composite flexible self-supporting film prepared by the preparation method according to any one of claims 1 to 3.
5. The use of a Co/PEDOT composite flexible self-supporting film according to claim 4, wherein the flexible self-supporting film is used as an electromagnetic shielding material.
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