CN112538761B - Integrated impedance gradient flexible wave-absorbing material and preparation method thereof - Google Patents
Integrated impedance gradient flexible wave-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an integrated impedance gradient flexible wave-absorbing material and a preparation method thereof. The integrated impedance gradient flexible wave-absorbing material comprises a base material and an MXene/PPy complex which is combined on the surface of the base material and in the pores of the base material; the MXene/PPy composite refers to a composite formed by MXene and PPy particles attached to the pores or edges of the MXene sheets; the concentration of PPy particles in the MXene/PPy composite body is gradually changed along the thickness direction of the base material; the base material is open-pore sponge, non-woven fabric or three-dimensional space fabric with pore structure and thickness. According to the invention, the polymerization rate and diffusion distribution of the PPy are regulated and controlled by a freezing interface polymerization or gas phase polymerization method, so that the concentration of the PPy can be distributed in a gradient manner from top to bottom in the thickness direction of the polymer substrate loaded with MXene in the polymerization process, and further the impedance gradient is realized. The addition of PPy will increase the dipole polarization and increase the heterointerface, and adjust the impedance mismatch caused by too high conductivity of MXene. The wave-absorbing material has good impact resistance, air permeability and environmental stability.
Description
Technical Field
The invention relates to an integrated impedance gradient flexible wave-absorbing material and a preparation method thereof, belonging to the technical field of microwave absorbing materials.
Background
The high absorptivity of the wave-absorbing material depends on the synergistic adjustment effect of the wave-absorbing agent and the material structure on the impedance matching and attenuation performance. The wave-absorbing material is generally composed of a wave-absorbing agent and a base material. The most widely studied and used wave absorbers include the classes of electrical resistance, dielectric and magnetic losses. For example, carbonyl iron powder, metal oxide conductive polymer, etc., have the disadvantages of high density, easy corrosion, poor dispersibility, undesirable electrical conductivity, etc. The graphene which is researched most thermally at present has high conductivity, but is difficult to combine with fabrics, and has the defects of poor adhesion, easy shedding and uneven conductivity.
MXene is a novel two-dimensional material with high conductivity and hydrophilicity, and has a unique accordion-shaped layered structure which is favorable for multiple reflection and absorption of electromagnetic waves, but the impedance mismatch is easily caused by the excessively high conductivity, and the environmental stability is poor. At present, most of researches on MXene and composite wave-absorbing materials thereof are powder, thin film, aerogel and the like, and the requirements of large-area wave-absorbing and shielding bodies cannot be met.
The single wave absorbing agent is difficult to realize broadband and high-efficiency wave absorbing performance. The wave absorbing performance is improved by adopting multi-layer composite wave absorption, and the impedance matching of each layer is considered. The traditional impedance gradual change wave-absorbing material is formed by laminating multiple layers of homogeneous materials, each layer of electromagnetic parameters are constant, air medium interference cannot be avoided between layers, and the problems that the interlayer combination degree is not high, the wave-absorbing material is easy to peel off after being bent for many times or used and the like exist. The patent application (CN 106671514B) discloses a wave-absorbing composite material with a discontinuous impedance gradual change structure, which realizes impedance gradual change by alternative mould pressing of a wave-transmitting layer and an electric loss layer with different concentrations, the composite material has good wave-absorbing capability in a X, Ku wave band, the preparation method of the impedance gradual change wave-absorbing honeycomb body disclosed in the patent application (CN 109774211A) and the wave-absorbing adhesive film disclosed in the patent application (CN 109423008A) and the preparation method thereof and the impedance gradual change wave-absorbing structural member, the honeycomb layer and other functional layers are alternately bonded in the two patents to realize impedance gradual change and effectively change the absorption bandwidth, however, the layers need additional bonding, the preparation method is complex, and an integrated impedance gradient wave-absorbing material and a preparation method for forming the impedance gradient wave-absorbing material at one time are lacked, so that the material resistance is gradually changed in the thickness direction without interference of an interlayer dielectric layer.
Disclosure of Invention
The invention aims to provide an integrated impedance gradient flexible wave-absorbing material and a preparation method thereof.
The invention provides an integrated impedance gradient flexible wave-absorbing material, which comprises a base material, and an MXene/PPy complex which is combined on the surface of the base material and in pores of the base material;
the MXene/PPy composite refers to a composite formed by MXene and PPy particles attached to the pores or edges of the MXene layers;
the concentration of the PPy particles in the MXene/PPy composite body is gradually changed along the thickness direction of the substrate;
the base material is open-pore sponge, non-woven fabric or three-dimensional space fabric with a pore structure and thickness.
The PPy particles are particles obtained by polymerizing pyrrole monomers in the thickness direction of the base material with MXene attached through freezing polymerization or gas phase polymerization;
the thickness direction of the base material is gradually changed, which means that the concentrations of PPy particles attached to the upper surface and the lower surface of the base material are obviously different, so that the upper surface resistance and the lower surface resistance are different, and the difference is larger than 300 omega.
In the invention, the open-cell sponge is made of a high polymer foam material;
the high polymer foaming material can be polyethylene, polystyrene polyethylene, polyurethane polyethylene or rubber-plastic blending material.
The non-woven fabric is prepared from a high polymer fiber material in a needling, hot melt bonding, spunlace or melt blowing mode;
the three-dimensional space fabric is formed by weaving a high polymer fiber material;
the thickness of the three-dimensional spaced fabric is 0.5-30 mm, the longitudinal density is 5-80 transverse rows/5 cm, and the transverse density is 5-65 longitudinal rows/5 cm;
the high polymer fiber material can be cotton fiber, viscose cellulose fiber, polyester fiber, acrylic fiber, nylon fiber, ultra-high molecular weight polyethylene fiber, carbon fiber or polyarylate fiber.
In the flexible wave-absorbing material, MXene is Ti3C2TX、Nb2CTX、Ti2CTX、Mo2CTX、Ti4N3TXAnd V2CTXAny one of, wherein, TXDenotes a surface functional group, e.g. ═O, -OH, -F, etc.
The functional group on the MXene surface is beneficial to forming hydrogen bonds with polar groups on the surfaces of other materials, is an important guarantee for good combination of the MXene and the polar groups on the surfaces of other materials, and can improve the air permeability and the flexibility of the multilayer composite material. Although the MXene has poor environmental stability due to the hydrophilicity, in the invention, the MXene is prevented from being further oxidized by introducing PPy (polypyrrole) between the MXene layers and at the edge of the sheet layer, and the final composite flexible wave-absorbing material is gradually changed in concentration gradient in the thickness direction by controlling the diffusion of PPy, so that the gradient of impedance is gradually changed, the synergistic effect of the gradient of impedance and the specific pore structure of the three-dimensional space fabric or the perforated sponge is further realized, the impedance matching is improved, the multiple reflection of electromagnetic waves is increased, and the wave-absorbing performance can be greatly improved.
The structural schematic diagram of the flexible wave-absorbing material prepared by the invention is shown in figure 1.
The invention further provides a preparation method of the flexible wave-absorbing material, which comprises the following steps:
s1, preparing a few layers or multiple layers of MXene by adopting a liquid phase MAX phase stripping method; generally, 1 to 3 layers of MXene are few layers of MXene, and MXene larger than 3 layers is called multilayer MXene;
s2, soaking the base material in the MXene dispersion liquid, draining until no liquid drops drop or drying to obtain the base material loaded with the MXene, and then obtaining the flexible wave-absorbing material through the following steps (1) or (2):
(1) soaking the base material in a solution containing an oxidant or a mixed solution containing the oxidant and a doping agent, and suspending until no liquid drops or drying; then placing the mixture above pyrrole monomer, pyrrole monomer and organic solvent or communicating with pyrrole steam, carrying out polymerization reaction, and drying to obtain the product;
(2) soaking the base material in a solution containing an oxidant or a mixed solution containing the oxidant and a dopant, and freezing; and then pouring the mixed solution of the pyrrole monomer and the organic solvent onto the frozen base material for polymerization reaction, and drying to obtain the material.
In the above method, in step S1, the MAX phase is Ti3AlC2、Nb2AlC、Ti2AlC、Mo2GaC、Ti4AlN3Or V2AlC；
Preparing MXene by using lithium fluoride and hydrochloric acid as etching agents;
the conditions for preparing the MXene are as follows:
the mass of the lithium fluoride is 1-15 g; the concentration of the hydrochloric acid is 6-12M; the mass of the MAX phase is 1-10 g, and the particle size is larger than 400 meshes;
the concentration of the prepared MXene dispersion liquid is 1-20 mg/ml;
and adding the oxidant and the dopant into the MXene dispersion liquid to obtain the mixed liquid.
In the above method, in steps S2(1) and (2), the oxidizing agent is any one of ammonium persulfate, potassium persulfate, sodium persulfate, calcium persulfate, hydrogen peroxide, copper chloride and ferric chloride hexahydrate;
the dopant is any one of hydrochloric acid, 5-sulfosodium salicylate, p-toluenesulfonic acid, naphthalenesulfonic acid, sodium p-toluenesulfonate, sodium dodecylbenzenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid and camphorsulfonic acid;
in the steps S2(1) and (2), the molar ratio of the pyrrole monomer to the oxidant is 1-9: 1-9, specifically 1: 1. 4: 1. 1: 5. 1: 2 or 2: 3;
the molar ratio of the pyrrole monomer to the dopant is 1-20: 1-9, specifically 1: 1. 1: 2. 2: 1. 7: 9 or 20: 1;
in the steps S2(1) and (2), the drying temperature is 40-80 ℃, and the drying time is 6-24 h;
before the drying, the method further comprises the step of repeatedly washing the product of the polymerization reaction with water and ethanol.
In the above method, in step S2(1), the drying is performed under vacuum;
in the step S2(2), the freezing temperature is-24-0 ℃ and the time is 0.5-72 h.
In the method, in the step S2(1), the temperature of the polymerization reaction is 24-80 ℃ and the time is 1-15 h;
in the step S2(2), the temperature of the polymerization reaction is-24 to 6.5 ℃, and the time is 0.5 to 240 hours.
In the above method, in steps S2(1) and (2), the organic solvent is any one of cyclohexane, carbon tetrachloride and chloroform;
in the mixed liquid of the pyrrole monomer and the organic solvent, the concentration of the pyrrole monomer is 0.1-5M.
The invention has the following beneficial effects:
according to the invention, the polymerization rate and diffusion distribution of PPy (polypyrrole) are regulated and controlled by a frozen interface polymerization or gas phase polymerization method, so that the PPy can be in concentration gradient distribution from top to bottom in the thickness direction of the polymer substrate loaded with MXene in the polymerization process, and further the impedance gradient is realized. The addition of PPy will increase the dipole polarization and increase the heterointerface, and adjust the impedance mismatch caused by too high conductivity of MXene. The invention prepares samples with different concentration distributions by changing the reaction temperature, the concentration of an initiator, the concentration of a monomer, the polymerization time, the fabric structure and the porosity of the open pore sponge, has the characteristic of impedance gradual change in the thickness direction, enables electromagnetic waves to be reflected and absorbed for many times under the synergistic action of the interval fabric with the pore structure and the open pore sponge, improves the wave absorbing efficiency of the material, endows the integrated impedance gradual change wave absorbing material with good impact resistance, air permeability and environmental stability, avoids the defects of layer composite impedance gradual change wave absorbing material, poor interlayer combination degree, complex preparation process, heavy weight and the like, and meets the requirements of the light and high-efficiency wave absorbing material.
Drawings
Fig. 1 is a schematic structural diagram of an MXene-based integrated impedance gradient flexible wave-absorbing material prepared by the method.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation by freezing interfacial polymerization
1g LiF and 20ml 6M HCl are mixed and stirred for 5min, and then 1g Ti is slowly added into the mixed solution3AlC2Stirring for 24h at 35 ℃, centrifuging and washing with deionized water at 3500rpm for 10 times, centrifuging for 5min each time, pouring out the upper layer solution, dispersing the bottom layer precipitate in deionized water, and ultrasonically vibrating for 1h to obtain the upper layer solution which is the few-layer Ti3C2TXDispersion, concentration 5 mg/ml. Soaking 0.8mm thick, 22 mm in length and 35 mm in width in polyester spacer fabric to obtain Ti3C2TXDispersing for 15min, vacuum drying at 60 deg.C, and placing in 0.5M FeCl3·6H2Freezing at-5 deg.C for 12 hr in a mixed solution of O and 0.5M sodium 5-sulfosalicylate, and pouring a cyclohexane solution containing 0.5M pyrrole monomer (wherein pyrrole monomer and FeCl)3·6H2The molar ratio of O is 1: 1, the molar ratio of pyrrole monomer to 5-sodium sulfosalicylate is 1: 1) polymerizing for 4h at 0 ℃, taking out a sample, alternately washing for 10 times by using deionized water and absolute ethyl alcohol, and then placing in a 60 ℃ oven for 12h to obtain Ti3C2TX/PPy(TXO, -OH and-F) impedance gradual change wave-absorbing spacing fabric.
Ti prepared in this example3C2TXThe difference of the upper surface resistance and the lower surface resistance of the/PPy impedance gradual change wave-absorbing spacing fabric is 5.3K omega, the minimum value of the reflection loss is-16 dB in the range of 2-18GHz, and the bandwidth with the reflection loss less than-10 dB is 2.45 GHz. It can be seen that the composite material can realize effective absorption of electromagnetic waves (the absorption of 90% of electromagnetic waves with a reflection loss of-10 dB is called effective absorption).
Example 2 preparation by freezing interfacial polymerization
2g LiF and 40ml 12M HCl are mixed and stirred for 5min, and then 2g Nb is slowly added into the mixed solution2Stirring AlC at 35 deg.C for 24h, centrifuging with deionized water at 3500rpm for 10 times (5 min each time), pouring out the upper layer solution, dispersing the bottom layer precipitate in deionized water, and ultrasonic vibrating for 2.5h to obtain the upper layer solution as the few-layer Nb2CTXDispersion, concentrationIs 5 mg/ml. Soaking a polyurethane open-cell sponge with a thickness of 1.2mm and a porosity of 50% in the obtained Nb2CTXAnd (3) dispersing for 15min, then drying at 60 ℃ in vacuum, and adding into a mixed solution of 0.18M ammonium persulfate and 0.38M HCl, wherein the molar ratio of pyrrole monomer to ammonium persulfate is 1: 1, the molar ratio of pyrrole monomer to HCl is 1: 2) freezing at-10 deg.C for 24 hr, pouring carbon tetrachloride solution containing 0.18M pyrrole monomer onto the frozen sample, polymerizing at 0 deg.C for 72 hr, taking out the sample, washing with deionized water and anhydrous ethanol for 10 times, and oven-drying at 60 deg.C for 12 hr to obtain Nb2CTX/PPy(TXO, -OH and-F) impedance gradient wave-absorbing sponge.
Nb prepared in this example2CTXThe difference between the upper surface resistance and the lower surface resistance of the/PPy impedance gradient sponge is 500 omega, the minimum value of the reflection loss is-36 dB within the range of 2-18GHz, and the bandwidth with the reflection loss less than-10 dB is 3.96 GHz. Therefore, the composite material can realize high-strength absorption of electromagnetic waves.
Example 3 preparation by freezing interfacial polymerization
3g LiF and 90ml 12M HCl are mixed and stirred for 5min, and then 3g Ti is slowly added into the mixed solution2Stirring AlC at 35 ℃ for 24h, centrifuging and washing with deionized water at 3500rpm for 10 times, each time for 5min, pouring out the upper solution, dispersing the bottom precipitate in deionized water, and ultrasonically vibrating for 1h to obtain the upper solution which is Ti with few layers2CTXDispersion, concentration 10 mg/ml. Taking a pure cotton non-woven fabric with the thickness of 2.2mm and the porosity of 60 percent, and soaking the pure cotton non-woven fabric in the obtained Ti2CTXAdding the dispersion into a mixed solution of 0.065M ammonium persulfate and 0.13M HCl after drying at 60 ℃ in vacuum for 15min, freezing for 24h at-20 ℃, pouring a carbon tetrachloride solution containing 0.26M pyrrole monomer onto the frozen sample (wherein the molar ratio of the pyrrole monomer to the ammonium persulfate is 4: 1, and the molar ratio of the pyrrole monomer to the HCl is 2: 1), polymerizing for 100h at-20 ℃, taking out the sample, alternately washing for 10 times by using deionized water and absolute ethyl alcohol, and placing the sample into a 60 ℃ oven for 12h to obtain Ti2CTX/PPy(TXIs O, -OH and-F) and has gradually changed impedanceAnd (6) spinning cloth.
Ti prepared in this example2CTXThe difference between the upper surface resistance and the lower surface resistance of the/PPy impedance gradual change non-woven fabric is 1.2K omega, the minimum value of the reflection loss is-22 dB in the range of 2-18GHz, and the bandwidth with the reflection loss less than-10 dB is 3.61 GHz. Therefore, the composite material can realize the absorption of more than 99 percent of electromagnetic waves
Example 4 gas phase polymerization preparation
2g LiF and 40ml 12M HCl are mixed and stirred for 5min, then 1g Ti is slowly added into the mixed solution3AlC2Stirring for 24h at 35 ℃, centrifuging and washing with deionized water at 3500rpm for 10 times, centrifuging for 5min each time, pouring out the upper layer solution, dispersing the bottom layer precipitate in deionized water, and ultrasonically vibrating for 1h to obtain the upper layer solution which is the few-layer Ti3C2TXDispersion, concentration 2 mg/ml. Soaking dacron spacer fabric with thickness of 1mm, longitudinal density of 28 and transverse density of 30 in the obtained Ti3C2TXTaking out the dispersion after 15min, drying at 80 deg.C under vacuum, and soaking in 0.1M FeCl3·6H2Taking out the solution after 5min in the O solution, and draining until no liquid drops drop. Placing the obtained spacer fabric above 0.5M chloroform solution containing pyrrole monomer, polymerizing for 4h at room temperature, and taking out the sample (wherein, pyrrole monomer and FeCl3·6H2The molar ratio of O is 1: 5) alternately washing with deionized water and anhydrous ethanol for 10 times, and placing in a 60 deg.C oven for 12h to obtain Ti3C2TX/PPy(TXO, -OH and-F) impedance gradual change wave-absorbing spacing fabric.
Ti prepared in this example3C2TXThe difference between the upper surface resistance and the lower surface resistance of the/PPy impedance gradual change wave-absorbing spacing fabric is 2K omega, the minimum value of the reflection loss is-14 dB in the range of 2-18GHz, and the bandwidth with the reflection loss less than-10 dB is 1.68 GHz. It can be seen that the composite material can realize effective absorption of electromagnetic waves (the absorption of 90% of electromagnetic waves with a reflection loss of-10 dB is called effective absorption).
Example 5 preparation by gas phase polymerization
3.2g LiF and 90ml 9M HCl are mixed and stirred for 5min, and then the mixture is addedSlowly adding 2g Ti into the solution3AlC2Stirring at 35 ℃ for 36h, centrifuging and washing with deionized water at 3500rpm for 10 times, each time for 5min, pouring out the upper layer solution, dispersing the bottom layer precipitate in deionized water, and ultrasonically vibrating for 2.5h to obtain the upper layer solution of Ti with few layers3C2TXDispersion, concentration 3 mg/ml. Soaking acrylic non-woven fabric with thickness of 10mm and porosity of 50% in the obtained Ti3C2TXAdding 0.42M FeCl into the dispersion3·6H2O and 0.63M naphthalenesulfonic acid, taking out after 30min, and vacuum drying for 12h at 60 ℃. The resulting spacer fabric was placed over 0.21M cyclohexane containing pyrrole monomers (where pyrrole monomers were combined with FeCl)3·6H2The molar ratio of O is 1: 2, the molar ratio of pyrrole monomer to naphthalene sulfonic acid is 7: 9) polymerizing for 3.5h at room temperature, taking out a sample, alternately washing for 10 times by using deionized water and absolute ethyl alcohol, and then placing in a 60 ℃ drying oven for 12h to obtain Ti3C2TX/PPy(TXO, -OH and-F) impedance gradual change wave-absorbing non-woven fabric.
Ti prepared in this example3C2TXThe difference between the upper surface resistance and the lower surface resistance of the/PPy impedance gradual change wave absorption non-woven fabric is 520 omega, the minimum value of the reflection loss is-21.2 dB in the range of 2-18GHz, and the bandwidth with the reflection loss smaller than-10 dB is 2.3 GHz. Therefore, the composite material has good electromagnetic wave absorption performance.
Example 6 preparation by gas phase polymerization
8g LiF and 160ml 9M HCl are mixed and stirred for 5min, and then 10g Ti is slowly added into the mixed solution2Stirring AlC at 35 deg.C for 36h, centrifuging with deionized water at 3500rpm for 10 times each for 5min, pouring out the upper layer solution, dispersing the bottom layer precipitate in deionized water, and ultrasonic vibrating for 2.5h to obtain the upper layer solution of Ti layer2CTXDispersion, concentration 10 mg/ml. Soaking polyurethane sponge with thickness of 20mm and porosity of 80% in the obtained Ti2CTXTaking out after 10min, vacuum drying at 50 deg.C for 12 hr, soaking in 0.42M FeCl3·6H2Mixing of O and 0.014M sodium dodecylbenzenesulfonateTaking out the solution after 30min, and vacuum drying the solution at 60 ℃ for 12 h. The resulting spacer fabric was placed in a beaker and placed in an ice bath and communicated through a glass tube to a solution containing 0.28M pyrrole monomer (where pyrrole monomer and FeCl3·6H2The molar ratio of O is 2: 3, the molar ratio of the pyrrole monomer to the sodium dodecyl benzene sulfonate is 20: 1) heating the pyrrole solution in a 65 ℃ water bath, carrying out the whole reaction in a closed vacuum environment, taking out a sample after polymerizing for 3h, alternately washing for 10 times by using deionized water and absolute ethyl alcohol, and then placing in a 60 ℃ drying oven for 12h to obtain Ti2CTX/PPy(TXO, -OH and-F) impedance gradient wave-absorbing sponge.
Ti prepared in this example2CTXThe difference between the upper surface resistance and the lower surface resistance of the/PPy impedance gradual change wave-absorbing sponge is 410 omega, the minimum value of the reflection loss is-34.8 dB within the range of 2-18GHz, and the bandwidth with the reflection loss less than-10 dB is 3.5 GHz. Therefore, the composite material can realize high-strength absorption of electromagnetic waves.
Claims (10)
1. An integrated impedance gradient flexible wave-absorbing material comprises a base material and an MXene/PPy complex which is combined on the surface of the base material and in pores of the base material;
the MXene/PPy composite refers to a composite formed by MXene and PPy particles attached to the pores or edges of the MXene layers;
the concentration of the PPy particles in the MXene/PPy composite body is gradually changed along the thickness direction of the substrate;
the base material is open-pore sponge, non-woven fabric or three-dimensional space fabric with a pore structure and thickness.
2. The flexible wave absorbing material of claim 1, wherein: the open-cell sponge is made of a high polymer foam material;
the high polymer foaming material is polyethylene, polystyrene polyethylene, polyurethane polyethylene or rubber-plastic blending material.
3. The flexible wave absorbing material of claim 1, wherein: the non-woven fabric is prepared from a high polymer fiber material in a needling, hot melt bonding, spunlace or melt blowing mode;
the three-dimensional space fabric is formed by weaving a high polymer fiber material;
the thickness of the three-dimensional spaced fabric is 0.5-30 mm, the longitudinal density is 5-80 transverse rows/5 cm, and the transverse density is 5-65 longitudinal rows/5 cm;
the high polymer fiber material is cotton fiber, viscose cellulose fiber, polyester fiber, acrylic fiber, nylon fiber, ultra-high molecular weight polyethylene fiber, carbon fiber or polyarylate fiber.
4. A flexible wave absorbing material according to any one of claims 1 to 3 wherein: the MXene is Ti3C2TX、Nb2CTX、Ti2CTX、Mo2CTX、Ti4N3TXAnd V2CTXAny one of, wherein, TXRepresents a surface functional group.
5. A preparation method of the flexible wave-absorbing material in any one of claims 1 to 4, comprising the following steps:
s1, preparing a few layers or multiple layers of MXene by adopting a liquid phase MAX phase stripping method;
s2, soaking the base material in the MXene dispersion liquid, draining until no liquid drops drop or drying to obtain the base material loaded with the MXene, and then obtaining the flexible wave-absorbing material through the following steps (1) or (2):
(1) soaking the base material in a mixed solution containing an oxidant and a dopant, and suspending until no liquid drops or drying; then placing the mixture above pyrrole monomer, pyrrole monomer and organic solvent or communicating with pyrrole steam, carrying out polymerization reaction, and drying to obtain the product;
(2) soaking the base material in a mixed solution containing an oxidant and a dopant, and freezing; and then pouring the mixed solution of the pyrrole monomer and the organic solvent onto the frozen base material for polymerization reaction, and drying to obtain the material.
6. The method of claim 5, wherein: in step S1, the MAX phase is Ti3AlC2、Nb2AlC、Ti2AlC、Mo2GaC、Ti4AlN3Or V2AlC；
Preparing MXene by using lithium fluoride and hydrochloric acid as etching agents;
the conditions for preparing the MXene are as follows:
the mass of the lithium fluoride is 1-15 g; the concentration of the hydrochloric acid is 6-12M; the mass of the MAX phase is 1-10 g, and the particle size is larger than 400 meshes;
the concentration of the prepared MXene dispersion liquid is 1-20 mg/ml;
and adding the oxidant and the dopant into the MXene dispersion liquid to obtain the mixed liquid.
7. The production method according to claim 5 or 6, characterized in that: in the steps S2(1) and (2), the oxidizing agent is any one of ammonium persulfate, potassium persulfate, sodium persulfate, calcium persulfate, hydrogen peroxide, copper chloride, and ferric chloride hexahydrate;
the dopant is any one of hydrochloric acid, 5-sulfosodium salicylate, p-toluenesulfonic acid, naphthalenesulfonic acid, sodium p-toluenesulfonate, sodium dodecylbenzenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid and camphorsulfonic acid;
in the steps S2(1) and (2), the molar ratio of the pyrrole monomer to the oxidant is 1-9: 1-9; the molar ratio of the pyrrole monomer to the dopant is 1-20: 1-9;
in the steps S2(1) and (2), the drying temperature is 40-80 ℃, and the drying time is 6-24 h;
before the drying, the method further comprises the step of repeatedly washing the product of the polymerization reaction with water and ethanol.
8. The production method according to claim 5 or 6, characterized in that: in step S2(1), the drying is performed under vacuum conditions;
in the step S2(2), the freezing temperature is-24-0 ℃ and the time is 0.5-72 h.
9. The production method according to claim 5 or 6, characterized in that: in the step S2(1), the temperature of the polymerization reaction is 24-80 ℃, and the time is 1-15 h;
in the step S2(2), the temperature of the polymerization reaction is-24 to 6.5 ℃, and the time is 0.5 to 240 hours.
10. The production method according to claim 5 or 6, characterized in that: in the steps S2(1) and (2), the organic solvent is any one of cyclohexane, carbon tetrachloride and chloroform;
in the mixed liquid of the pyrrole monomer and the organic solvent, the concentration of the pyrrole monomer is 0.1-5M.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154832A (en) * | 2010-12-31 | 2011-08-17 | 泉州红瑞兴纺织有限公司 | Fabric coating finishing agent with electromagnetic shielding function and preparation method thereof |
| CN108831760A (en) * | 2018-06-15 | 2018-11-16 | 武汉工程大学 | A kind of N doping MXene material and its preparation method and application |
| CN109003836A (en) * | 2018-08-13 | 2018-12-14 | 湖北汽车工业学院 | A kind of preparation method based on MXene flexible fabric electrode and its application in supercapacitor |
| CN111223687A (en) * | 2020-01-13 | 2020-06-02 | 常州大学 | Preparation method of MXene/PANI-based high-capacity linear supercapacitor electrode |
-
2020
- 2020-11-12 CN CN202011260603.7A patent/CN112538761B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154832A (en) * | 2010-12-31 | 2011-08-17 | 泉州红瑞兴纺织有限公司 | Fabric coating finishing agent with electromagnetic shielding function and preparation method thereof |
| CN108831760A (en) * | 2018-06-15 | 2018-11-16 | 武汉工程大学 | A kind of N doping MXene material and its preparation method and application |
| CN109003836A (en) * | 2018-08-13 | 2018-12-14 | 湖北汽车工业学院 | A kind of preparation method based on MXene flexible fabric electrode and its application in supercapacitor |
| CN111223687A (en) * | 2020-01-13 | 2020-06-02 | 常州大学 | Preparation method of MXene/PANI-based high-capacity linear supercapacitor electrode |
Non-Patent Citations (5)
| Title |
|---|
| Interfacing MXene flakes on fiber fabric as an ultrafast electron transport;Xiaolong Li etc.;《Energy Storage Materials》;20200604(第33期);第2.1-2.2节、第3节 * |
| Pseudocapacitive Electrodes Produced by Oxidant‐Free Polymerization of Pyrrole between the layers of 2D Titanium Carbide(MXene);M.Boota.etc.;《ADVANCED MATERIALS》;20161231(第28期);全文 * |
| Ti3C2Tx MXene polyaniline (PANI) sandwich intercalation structure composites constructed for microwave absorption;Huawei Wei etc.;《Composites Science and Technology》;20181024;全文 * |
| 导电聚合物基复合吸波材料的研究进展;张捷 等;《纳微电子技术》;20180228;第55卷(第2期);引言部分 * |
| 新型MXene复合吸波材料研究进展;淳道勇;《广州化工》;20190831;第47卷(第15期);全文 * |
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