CN113873859A - Preparation method of CoFe @ MXene/carbon aerogel composite material - Google Patents

Preparation method of CoFe @ MXene/carbon aerogel composite material Download PDF

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CN113873859A
CN113873859A CN202111041252.5A CN202111041252A CN113873859A CN 113873859 A CN113873859 A CN 113873859A CN 202111041252 A CN202111041252 A CN 202111041252A CN 113873859 A CN113873859 A CN 113873859A
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mxene
cofe
powder
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任鹏刚
郭铮铮
宗泽
任芳
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Xian University of Technology
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Xian University of Technology
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    • 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
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels

Abstract

The invention discloses a preparation method of a CoFe @ MXene/carbon aerogel composite material, which comprises the following steps: firstly, etching MAX phase precursor by LiF-HCl to prepare small-layer MXene powder; CoFe by hydrothermal method2O4Growing on MXene in situ; using less layers of MXene powder and CoFe2O4Preparation of CoFe from @ MXene powder2O4@ MXene/cellulose aerogel; finally, CoFe2O4And putting the @ MXene/cellulose aerogel into a tube furnace for carbonization. The CoFe @ MXene/carbon aerogel composite material prepared by the method disclosed by the invention is excellent in electromagnetic shielding performance and strong in absorption capacity, and can meet the application requirements in the fields of aerospace, electronic packaging and the like.

Description

Preparation method of CoFe @ MXene/carbon aerogel composite material
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a CoFe @ MXene/carbon aerogel composite material.
Background
With the wide application of electromagnetic wave technology in human daily life and the development trend of miniaturization and integration of electronic devices, the electromagnetic wave pollution generated along with the wide application brings convenience to human life, and the normal work of precise instruments is seriously influenced, and even certain threat is caused to human health. Although the conventional electromagnetic shielding material based on impedance mismatch has high shielding efficiency, the electromagnetic environment tends to be complicated by serious secondary pollution of electromagnetic waves. Therefore, it is important to design an electromagnetic shielding material having both high-efficiency electromagnetic shielding performance and strong electromagnetic wave absorption capability to solve the problem.
A great deal of research finds that the introduction of magnetic components into the composite material to provide magnetic loss and the construction of a three-dimensional conductive network are key strategies for relieving impedance mismatch between the material and a free space, so that more electromagnetic waves can enter the interior of the composite material, and multiple reflection and scattering in the interior of the material are enhanced. CoFe alloy and Ti3C2Tx(MXene) has been widely used as a typical magnetic material and conductive filler for shielding materials, however MXene has difficulty in forming a strong three-dimensional skeleton due to its weak gelation ability. In recent years, biomass carbon materials for shielding have received attention because of their advantages such as low cost and reproducibility. Cellulose is one of the almost inexhaustible low-cost biomass resources on earth, and is considered as an advanced candidate raw material for building a three-dimensional framework structure due to the fact that the cellulose contains a large number of hydrogen bonds. MXene and CoFe are provided with a platform by cellulose to form a strong three-dimensional skeleton. In addition, researches show that the three-dimensional high-connectivity conductive network of the composite material plays a crucial role in the conductivity and the electromagnetic shielding effect of the composite material. The aerogel formed by cellulose is used as a precursor, and can be converted into a three-dimensional continuous porous conductive framework through a simple pyrolysis process on the premise of not damaging the structure of the aerogel.
Disclosure of Invention
The invention aims to provide a preparation method of a CoFe @ MXene/carbon aerogel composite material, and solves the problems of low electromagnetic shielding performance and poor electromagnetic wave absorption capability of the composite material in the prior art.
The technical scheme adopted by the invention is that the preparation method of the CoFe @ MXene/carbon aerogel composite material is implemented according to the following steps:
step 1, etching Ti by LiF-HCl3AlC2Preparing a precursor into less-layer MXene powder;
step 2, preparation of CoFe by hydrothermal method2O4@ MXene powder;
step 3, using CoFe2O4Preparation of CoFe from @ MXene powder and cellulose2O4@ MXene/cellulose aerogel;
step 4, CoFe obtained in step 32O4And putting the @ MXene/cellulose aerogel into a tubular furnace for carbonization treatment to obtain the CoFe @ MXene/carbon aerogel composite material.
The present invention is also characterized in that,
in step 1, the specific steps are as follows:
step 1.1, fully mixing LiF and HCl, and then slowly adding MAX phase precursor powder under an ice bath condition to obtain a mixture;
the mass ratio of LiF, HCl and MAX phase precursor powder is 1: 20: 1;
step 1.2, the mixture was stirred at 35 ℃ for 24 hours to obtain Ti3C2TxThe suspension is then repeatedly centrifuged and washed with deionized water until the pH of the solution is 7 to obtain Ti3C2TxA precipitate;
step 1.3, adding Ti3C2TxDispersing the precipitate in deionized water, performing ultrasonic treatment for 15min to promote layering of multiple layers of MXene, then continuing to centrifuge at 3500r/min for 15min, circulating for several times, and taking supernatant to obtain a few layers of MXene dispersion liquid;
step 1.4, freezing the obtained small-layer MXene dispersion liquid at-26 ℃ in advance, and freeze-drying the small-layer MXene dispersion liquid by using a freeze dryer to obtain small-layer MXene powder.
In the step 2, the method specifically comprises the following steps: dissolving PVP in deionized water under magnetic stirring, and dissolving Fe (NO) after PVP is completely dissolved3)3·9H2O、Co(NO3)2·6H2Adding O and small-layer MXene powder into the solution, ultrasonically dispersing for 30 min, adding urea, mixing, transferring the mixed solution into a high-pressure reaction kettle, sealing, performing hydrothermal reaction at 180 deg.C for 12 hr, naturally cooling to room temperature, collecting precipitate, washingDrying to obtain CoFe2O4@ MXene powder.
PVP、Fe(NO3)3·9H2O、Co(NO3)2·6H2The mass ratio of O, the less-layer MXene powder, the urea and the deionized water is 0.15: 0.135-0.404: 0.097-0.145: 0.7047-0.548: 0.12: 60.
in step 3, the method specifically comprises the following steps:
step 3.1, adding NaOH and urea into deionized water, stirring for 15min to obtain a mixed solution, and then placing the mixed solution in a refrigerator for refrigeration; adding cellulose powder, stirring, freezing the solution in refrigerator, thawing naturally, adding CoFe2O4@ MXene powder, ultrasonic dispersing, freezing at-26 deg.C for 12 hr, naturally thawing, adding MBA, and stirring;
step 3.2, pouring the mixed solution obtained in the step 3.1 into a mold of a six-hole cell culture plate, and standing for one day to obtain CoFe2O4@ MXene/cellulose hydrogel, washing with deionized water to neutral, freezing at-26 deg.C for 12 hr, and freeze drying for 48 hr to obtain CoFe2O4@ MXene/cellulose aerogel.
In the step 3.1, the refrigeration temperature is-12 ℃, and the refrigeration time is 12 hours; the freezing temperature is-26 deg.C, and the freezing time is 24 h.
In step 3.1, NaOH, Urea, CoFe2O4The mass ratio of the @ MXene powder to the cellulose powder to the MBA to the deionized water is 7: 12: 0.1458: 2.43: 2.34: 81.
in step 4, the carbonization conditions are specifically as follows: introducing nitrogen at the speed of 50-100 mL/s, heating to 300 ℃ at the speed of 3 ℃/min, preserving heat for 1h, then heating to 800-1200 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature.
The invention has the advantages that through the design of the highly interconnected three-dimensional conductive network, the magnetic filler is introduced to provide magnetic loss, and the high-performance electromagnetic shielding composite material which is dominant by an absorption mechanism is prepared; meanwhile, the preparation method is simple and easy to implement, low in production cost and capable of realizing batch production.
Drawings
FIG. 1 shows the total electromagnetic Shielding Effectiveness (SE) of CoFe @ MXene/carbon aerogel at different CoFe contents in the process of the present inventionT) A drawing;
FIG. 2 is SE of CoFe @ MXene/carbon aerogel at different CoFe contents in the process of the present inventionR、SEAA drawing;
FIG. 3 shows the total electromagnetic Shielding Effectiveness (SE) of CoFe @ MXene/carbon aerogel at different carbonization temperatures in the process of the present inventionT) A drawing;
FIG. 4 is SE of CoFe @ MXene/carbon aerogel at different carbonization temperatures in the process of the present inventionR、SEAFigure (a).
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The preparation method of the CoFe @ MXene/carbon aerogel composite material is implemented according to the following steps:
step 1, etching Ti by LiF-HCl3AlC2Preparing a precursor into less-layer MXene powder; the method comprises the following specific steps:
step 1.1, fully mixing LiF and HCl, and then slowly adding MAX phase precursor powder under an ice bath condition to obtain a mixture;
the mass ratio of LiF, HCl and MAX phase precursor powder is 1: 20: 1;
MAX phase precursor powder (Ti)3AlC2Powder) was produced by the beijing forsman technologies company. The purity of the MAX phase precursor powder is 98%, and the particle size of the MAX phase precursor powder is 200 meshes.
Step 1.2, the mixture was stirred at 35 ℃ for 24 hours to obtain Ti3C2TxThe suspension is then repeatedly centrifuged and washed with deionized water until the pH of the solution is 7 to obtain Ti3C2TxA precipitate;
when in centrifugal washing, the centrifugal rate is 3500 r/min;
step 1.3, adding Ti3C2TxDispersing the precipitate in deionized water, ultrasonic treating for 15min,the layering of multiple layers of MXene is promoted, then the centrifugation is continued for 15min at the speed of 3500r/min, the circulation is carried out for a plurality of times, and the supernatant is taken to obtain a small-layer MXene dispersion liquid;
step 1.4, freezing the obtained small-layer MXene dispersion liquid at-26 ℃ in advance, and freeze-drying the small-layer MXene dispersion liquid by using a freeze dryer to obtain small-layer MXene powder;
step 2, preparing CoFe with different magnetic material contents by a hydrothermal method2O4@ MXene powder;
the method specifically comprises the following steps: dissolving polyvinylpyrrolidone (PVP) in deionized water under magnetic stirring, and dissolving Fe (NO) after completely dissolving3)3·9H2O、Co(NO3)2·6H2Adding O and a small layer of MXene powder into the solution, performing ultrasonic dispersion for 30 minutes, adding urea, uniformly mixing, transferring the mixed solution into a high-pressure reaction kettle, sealing, performing hydrothermal reaction at 180 ℃ for 12 hours, naturally cooling to room temperature, collecting precipitate, washing and drying to obtain CoFe2O4@ MXene powder;
PVP、Fe(NO3)3·9H2O、Co(NO3)2·6H2the mass ratio of O, the less-layer MXene powder, the urea and the deionized water is 0.15: 0.135-0.404: 0.097-0.145: 0.7047-0.548: 0.12: 60, adding a solvent to the mixture;
step 3, using CoFe2O4Preparation of CoFe from @ MXene powder and cellulose2O4@ MXene/cellulose aerogel; the method specifically comprises the following steps:
step 3.1, adding NaOH and urea into deionized water, stirring for 15min to obtain a mixed solution, and then placing the mixed solution in a refrigerator for refrigeration; adding cellulose powder, stirring, freezing the solution in refrigerator, thawing naturally, adding CoFe2O4@ MXene powder, ultrasonic dispersing, freezing at-26 deg.C for 12 hr, naturally thawing, adding MBA, and stirring;
the refrigeration temperature is-12 ℃, and the refrigeration time is 12 h. The freezing temperature is-26 ℃, and the freezing time is 24 hours;
NaOH, Urea, CoFe2O4The mass ratio of the @ MXene powder to the cellulose powder to the MBA to the deionized water is 7: 12: 0.1458: 2.43: 2.34: 81;
step 3.2, pouring the mixed solution obtained in the step 3.1 into a mold of a six-hole cell culture plate, and standing for one day to obtain CoFe2O4@ MXene/cellulose hydrogel, washing with deionized water to neutral, freezing at-26 deg.C for 12 hr, and freeze drying for 48 hr to obtain CoFe2O4@ MXene/cellulose aerogel;
step 4, CoFe obtained in step 32O4And putting the @ MXene/cellulose aerogel into a tubular furnace for carbonization treatment to obtain the CoFe @ MXene/carbon aerogel composite material.
The carbonization conditions are specifically as follows: introducing nitrogen at the speed of 50-100 mL/s, heating to 300 ℃ at the speed of 3 ℃/min, preserving heat for 1h, then heating to 800-1200 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature.
Example 1
The preparation method of the CoFe @ MXene/carbon aerogel composite material is implemented according to the following steps:
step 1, etching Ti by LiF-HCl3AlC2Precursor preparation of few-layer Ti3C2TxMXene powder, the concrete steps are as follows:
step 1.1, fully mixing 2g of LiF with 40mL of 9mol/L HCl, and then slowly adding 2g of MAX phase precursor powder under the ice bath condition;
step 1.2, the above mixture is stirred at 35 ℃ for 24 hours to obtain Ti3C2TxRepeatedly washing the suspension with deionized water until the pH is 7, and centrifuging at 3500 r/min;
step 1.3, adding Ti3C2TxDispersing the precipitate in 100ml of deionized water, performing ultrasonic treatment for 15min to promote layering of multiple layers of MXene, then continuing to centrifuge at the speed of 3500r/min for 15min, circulating for multiple times, and taking supernatant to obtain MXene dispersion liquid;
step 1.4, freezing the obtained small-layer MXene dispersion liquid at-26 ℃ for 12 hours in advance, and then freezing and drying for 48 hours to obtain small-layer MXene powder.
Step 2, preparation of CoFe by hydrothermal method2O4@ MXene powder, the specific steps are as follows:
step 2.1, 0.15g of polyvinylpyrrolidone (PVP) was dissolved in 60mL of deionized water with magnetic stirring. After complete dissolution, 0.135g Fe (NO) is added3)3·9H2O、0.097gCo(NO3)2·6H2O and 0.7047g of small-layer MXene powder are added into the solution mixture, ultrasonic dispersion is carried out for 30 minutes, 0.12g of urea is added, and the mixture is uniformly mixed;
PVP、Fe(NO3)3·9H2O、Co(NO3)2·6H2the mass ratio of O, the less-layer MXene powder, the urea and the water is 0.15: 0.135: 0.097: 0.7047: 0.12: 60.
step 2.2, the mixture was transferred to an autoclave, sealed, kept at 180 ℃ for 12h and then cooled naturally to room temperature. Collecting the precipitate, washing and drying to obtain CoFe2O4CoFe with a load of 10 wt% in MXene2O4@ MXene powder.
Step 3, using CoFe2O4Preparation of CoFe from @ MXene powder and cellulose2O4The @ MXene/cellulose aerogel comprises the following specific steps:
step 3.1, adding NaOH and urea powder into deionized water, stirring for 15min to uniformly disperse the NaOH and urea powder, placing the mixed solution in a refrigerator at the temperature of-12 ℃ for 12h, taking out the mixed solution, adding 2.43g of cellulose powder, and uniformly stirring by using a glass rod; freezing the solution in a refrigerator at-26 deg.C for 24 hr, thawing naturally at room temperature, and adding prepared CoFe2O4@ MXene powder, after ultrasonic dispersion, freezing again for 12h, naturally thawing, adding 2.34g N, N-Methylene Bisacrylamide (MBA), and vigorously stirring with a glass rod to uniformly disperse the powder;
NaOH, Urea, CoFe2O4The mass ratio of the @ MXene powder to the cellulose powder to the MBA to the water is 7: 12: 0.1458: 2.43: 2.34: 81;
in the step 3.2, the step of the method,pouring the mixed solution obtained in the step 3.1 into a mould of a six-hole cell culture plate, standing for one day to obtain CoFe2O4@ MXene/cellulose hydrogel, washing with deionized water to neutral, freezing at-26 deg.C for 12 hr, and freeze drying for 48 hr to obtain CoFe2O4@ MXene/cellulose aerogel;
and 4, putting the aerogel obtained in the step 3 into a tubular furnace as a precursor for carbonization treatment to prepare the CoFe @ MXene/carbon aerogel composite material.
The carbonization conditions are specifically as follows: introducing nitrogen at the speed of 50mL/s, raising the temperature to 300 ℃ at the speed of 3 ℃/min, preserving the heat for 1h, raising the temperature to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature.
Compared with a commercial electromagnetic shielding material (20dB), the electromagnetic shielding effectiveness of the CoFe @ MXene/carbon aerogel composite material prepared in example 1 is 38.6dB, and is correspondingly improved by 93%.
Example 2
The preparation method of the CoFe @ MXene/carbon aerogel composite material is implemented according to the following steps:
step 1, etching Ti by LiF-HCl3AlC2Precursor preparation of few-layer Ti3C2TxMXene powder, the concrete steps are as follows:
step 1.1, fully mixing 2g of LiF with 40mL of 9mol/L HCl, and then slowly adding 2g of MAX phase precursor powder under the ice bath condition;
step 1.2, the above mixture is stirred at 35 ℃ for 24 hours to obtain Ti3C2TxRepeatedly washing the suspension with deionized water until the pH is 7, and centrifuging at 3500 r/min;
step 1.3, adding Ti3C2TxDispersing the precipitate in 100ml of deionized water, performing ultrasonic treatment for 15min to promote layering of multiple layers of MXene, then continuing to centrifuge at the speed of 3500r/min for 15min, circulating for multiple times, and taking supernatant to obtain MXene dispersion liquid;
step 1.4, freezing the obtained small-layer MXene dispersion liquid at-26 ℃ for 12 hours in advance, and then freezing and drying for 48 hours to obtain small-layer MXene powder.
Step 2, preparing CoFe with different magnetic material contents by a hydrothermal method2O4@ MXene powder, the specific steps are as follows:
step 2.1, 0.15g of polyvinylpyrrolidone (PVP) was dissolved in 60mL of deionized water with magnetic stirring. After complete dissolution, 0.27g Fe (NO) was added3)3·9H2O、0.194gCo(NO3)2·6H2O and 0.6264g of small-layer MXene powder are added into the solution mixture, ultrasonic dispersion is carried out for 30 minutes, 0.12g of urea is added, and the mixture is uniformly mixed;
PVP、Fe(NO3)3·9H2O、Co(NO3)2·6H2the mass ratio of O, the less-layer MXene powder, the urea and the water is 0.15: 0.27: 0.194: 0.6264: 0.12: 60.
step 2.2, the mixture was transferred to an autoclave, sealed, kept at 180 ℃ for 12h and then cooled naturally to room temperature. Collecting the precipitate, washing and drying to obtain CoFe2O4CoFe with 20 wt% load in MXene2O4@ MXene powder.
Step 3, using CoFe2O4Preparation of CoFe from @ MXene powder and cellulose2O4The @ MXene/cellulose aerogel comprises the following specific steps:
step 3.1, adding NaOH and urea powder into deionized water, stirring for 15min to uniformly disperse the NaOH and urea powder, placing the mixed solution in a refrigerator at the temperature of-12 ℃ for 12h, taking out the mixed solution, adding 2.43g of cellulose powder, and uniformly stirring by using a glass rod; freezing the solution in a refrigerator at-26 deg.C for 24 hr, thawing naturally at room temperature, and adding prepared CoFe2O4@ MXene powder, after ultrasonic dispersion, freezing again for 12h, naturally thawing, adding 2.34g N, N-Methylene Bisacrylamide (MBA), and vigorously stirring with a glass rod to uniformly disperse the powder;
NaOH, Urea, CoFe2O4The mass ratio of the @ MXene powder to the cellulose powder to the MBA to the water is 7: 12: 0.1458: 2.43: 2.34: 81;
step 3.2, mixingPouring the mixed solution obtained in the step 3.1 into a mould of a six-hole cell culture plate, standing for one day to obtain CoFe2O4@ MXene/cellulose hydrogel, washing with deionized water to neutral, freezing at-26 deg.C for 12 hr, and freeze drying for 48 hr to obtain CoFe2O4@ MXene/cellulose aerogel;
and 4, putting the aerogel obtained in the step 3 into a tubular furnace as a precursor for carbonization treatment to prepare the CoFe @ MXene/carbon aerogel composite material.
The carbonization conditions are specifically as follows: introducing nitrogen at the speed of 50-100 mL/s, heating to 300 ℃ at the speed of 3 ℃/min, preserving heat for 1h, then heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature.
Compared with a commercial electromagnetic shielding material (20dB), the electromagnetic shielding effectiveness of the CoFe @ MXene/carbon aerogel composite material prepared in example 2 is 47.2dB, and is correspondingly improved by 136%.
Example 3
The preparation method of the CoFe @ MXene/carbon aerogel composite material is implemented according to the following steps:
step 1, etching Ti by LiF-HCl3AlC2Precursor preparation of few-layer Ti3C2TxMXene powder, the concrete steps are as follows:
step 1.1, fully mixing 2g of LiF with 40mL of 9mol/L HCl, and then slowly adding 2g of MAX phase precursor powder under the ice bath condition;
step 1.2, the above mixture is stirred at 35 ℃ for 24 hours to obtain Ti3C2TxRepeatedly washing the suspension with deionized water until the pH is 7, and centrifuging at 3500 r/min;
step 1.3, adding Ti3C2TxDispersing the precipitate in 100ml of deionized water, performing ultrasonic treatment for 15min to promote layering of multiple layers of MXene, then continuing to centrifuge at the speed of 3500r/min for 15min, circulating for multiple times, and taking supernatant to obtain MXene dispersion liquid;
step 1.4, freezing the obtained small-layer MXene dispersion liquid at-26 ℃ for 12 hours in advance, and then freezing and drying for 48 hours to obtain small-layer MXene powder.
Step 2, preparing CoFe with different magnetic material contents by a hydrothermal method2O4@ MXene powder, the specific steps are as follows:
step 2.1, 0.15g of polyvinylpyrrolidone (PVP) was dissolved in 60mL of deionized water with magnetic stirring. After complete dissolution, 0.27g Fe (NO) was added3)3·9H2O、0.194gCo(NO3)2·6H2O and 0.6264g of small-layer MXene powder are added into the solution mixture, ultrasonic dispersion is carried out for 30 minutes, 0.12g of urea is added, and the mixture is uniformly mixed;
PVP、Fe(NO3)3·9H2O、Co(NO3)2·6H2the mass ratio of O, the less-layer MXene powder, the urea and the water is 0.15: 0.404: 0.145: 0.548: 0.12: 60.
step 2.2, the mixture was transferred to an autoclave, sealed, kept at 180 ℃ for 12h and then cooled naturally to room temperature. Collecting the precipitate, washing and drying to obtain CoFe2O4CoFe with a loading of 30 wt% in MXene2O4@ MXene powder.
Step 3, using CoFe2O4Preparation of CoFe from @ MXene powder and cellulose2O4The @ MXene/cellulose aerogel comprises the following specific steps:
step 3.1, adding NaOH and urea powder into deionized water, stirring for 15min to uniformly disperse the NaOH and urea powder, placing the mixed solution in a refrigerator at the temperature of-12 ℃ for 12h, taking out the mixed solution, adding 2.43g of cellulose powder, and uniformly stirring by using a glass rod; freezing the solution in a refrigerator at-26 deg.C for 24 hr, thawing naturally at room temperature, and adding prepared CoFe2O4@ MXene powder, after ultrasonic dispersion, freezing again for 12h, naturally thawing, adding 2.34g N, N-Methylene Bisacrylamide (MBA), and vigorously stirring with a glass rod to uniformly disperse the powder;
NaOH, Urea, CoFe2O4The mass ratio of the @ MXene powder to the cellulose powder to the MBA to the water is 7: 12: 0.1458: 2.43: 2.34: 81;
in the step 3.2, the step of the method,pouring the mixed solution obtained in the step 3.1 into a mould of a six-hole cell culture plate, standing for one day to obtain CoFe2O4@ MXene/cellulose hydrogel, washing with deionized water to neutral, freezing at-26 deg.C for 12 hr, and freeze drying for 48 hr to obtain CoFe2O4@ MXene/cellulose aerogel;
and 4, putting the aerogel obtained in the step 3 into a tubular furnace as a precursor for carbonization treatment to prepare the CoFe @ MXene/carbon aerogel composite material.
The carbonization conditions are specifically as follows: introducing nitrogen at the speed of 50-100 mL/s, heating to 300 ℃ at the speed of 3 ℃/min, preserving heat for 1h, then heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature.
Compared with a commercial electromagnetic shielding material (20dB), the electromagnetic shielding effectiveness of the CoFe @ MXene/carbon aerogel composite material prepared in example 3 is 51.5dB, and is correspondingly improved by 157.5%.
Example 4
The preparation method of the CoFe @ MXene/carbon aerogel composite material is implemented according to the following steps:
step 1, etching Ti by LiF-HCl3AlC2Precursor preparation of few-layer Ti3C2TxMXene powder, the concrete steps are as follows:
step 1.1, fully mixing 2g of LiF with 40mL of 9mol/L HCl, and then slowly adding 2g of MAX phase precursor powder under the ice bath condition;
step 1.2, the above mixture is stirred at 35 ℃ for 24 hours to obtain Ti3C2TxRepeatedly washing the suspension with deionized water until the pH is 7, and centrifuging at 3500 r/min;
step 1.3, adding Ti3C2TxDispersing the precipitate in 100ml of deionized water, performing ultrasonic treatment for 15min to promote layering of multiple layers of MXene, then continuing to centrifuge at the speed of 3500r/min for 15min, circulating for multiple times, and taking supernatant to obtain MXene dispersion liquid;
step 1.4, freezing the obtained small-layer MXene dispersion liquid at-26 ℃ for 12 hours in advance, and then freezing and drying for 48 hours to obtain small-layer MXene powder.
Step 2, preparing CoFe with different magnetic material contents by a hydrothermal method2O4@ MXene powder, the specific steps are as follows:
step 2.1, 0.15g of polyvinylpyrrolidone (PVP) was dissolved in 60mL of deionized water with magnetic stirring. After complete dissolution, 0.27g Fe (NO) was added3)3·9H2O、0.194gCo(NO3)2·6H2O and 0.6264g of small-layer MXene powder are added into the solution mixture, ultrasonic dispersion is carried out for 30 minutes, 0.12g of urea is added, and the mixture is uniformly mixed;
PVP、Fe(NO3)3·9H2O、Co(NO3)2·6H2the mass ratio of O, the less-layer MXene powder, the urea and the water is 0.15: 0.404: 0.145: 0.548: 0.12: 60.
step 2.2, the mixture was transferred to an autoclave, sealed, kept at 180 ℃ for 12h and then cooled naturally to room temperature. Collecting the precipitate, washing and drying to obtain CoFe2O4CoFe with a loading of 30 wt% in MXene2O4@ MXene powder.
Step 3, using CoFe2O4Preparation of CoFe from @ MXene powder and cellulose2O4The @ MXene/cellulose aerogel comprises the following specific steps:
step 3.1, adding NaOH and urea powder into deionized water, stirring for 15min to uniformly disperse the NaOH and urea powder, placing the mixed solution in a refrigerator at the temperature of-12 ℃ for 12h, taking out the mixed solution, adding 2.43g of cellulose powder, and uniformly stirring by using a glass rod; freezing the solution in a refrigerator at-26 deg.C for 24 hr, thawing naturally at room temperature, and adding prepared CoFe2O4@ MXene powder, after ultrasonic dispersion, freezing again for 12h, naturally thawing, adding 2.34g N, N-Methylene Bisacrylamide (MBA), and vigorously stirring with a glass rod to uniformly disperse the powder;
NaOH, Urea, CoFe2O4The mass ratio of the @ MXene powder to the cellulose powder to the MBA to the water is 7: 12: 0.1458: 2.43: 2.34: 81;
step 3.2, pouring the mixed solution obtained in the step 3.1 into a mould of a six-hole cell culture plate, and standing for one day to obtain CoFe2O4@ MXene/cellulose hydrogel, washing with deionized water to neutral, freezing at-26 deg.C for 12 hr, and freeze drying for 48 hr to obtain CoFe2O4@ MXene/cellulose aerogel;
and 4, putting the aerogel obtained in the step 3 into a tubular furnace as a precursor for carbonization treatment to prepare the CoFe @ MXene/carbon aerogel composite material.
The carbonization conditions are specifically as follows: introducing nitrogen at the speed of 50-100 mL/s, raising the temperature to 300 ℃ at the speed of 3 ℃/min, preserving the heat for 1h, raising the temperature to 1000 ℃ at the speed of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature.
Compared with a commercial electromagnetic shielding material (20dB), the electromagnetic shielding effectiveness of the CoFe @ MXene/carbon aerogel composite material prepared in example 4 is 62.9dB, and is correspondingly improved by 214.5%.
Example 5
The preparation method of the CoFe @ MXene/carbon aerogel composite material is implemented according to the following steps:
step 1, etching Ti by LiF-HCl3AlC2Precursor preparation of few-layer Ti3C2TxMXene powder, the concrete steps are as follows:
step 1.1, fully mixing 2g of LiF with 40mL of 9mol/L HCl, and then slowly adding 2g of MAX phase precursor powder under the ice bath condition;
step 1.2, the above mixture is stirred at 35 ℃ for 24 hours to obtain Ti3C2TxRepeatedly washing the suspension with deionized water until the pH is 7, and centrifuging at 3500 r/min;
step 1.3, adding Ti3C2TxDispersing the precipitate in 100ml of deionized water, performing ultrasonic treatment for 15min to promote layering of multiple layers of MXene, then continuing to centrifuge at the speed of 3500r/min for 15min, circulating for multiple times, and taking supernatant to obtain MXene dispersion liquid;
step 1.4, freezing the obtained small-layer MXene dispersion liquid at-26 ℃ for 12 hours in advance, and then freezing and drying for 48 hours to obtain small-layer MXene powder.
Step 2, preparing CoFe with different magnetic material contents by a hydrothermal method2O4@ MXene powder, the specific steps are as follows:
step 2.1, 0.15g of polyvinylpyrrolidone (PVP) was dissolved in 60mL of deionized water with magnetic stirring. After complete dissolution, 0.27g Fe (NO) was added3)3·9H2O、0.194gCo(NO3)2·6H2O and 0.6264g of small-layer MXene powder are added into the solution mixture, ultrasonic dispersion is carried out for 30 minutes, 0.12g of urea is added, and the mixture is uniformly mixed;
PVP、Fe(NO3)3·9H2O、Co(NO3)2·6H2the mass ratio of O, the less-layer MXene powder, the urea and the water is 0.15: 0.404: 0.145: 0.548: 0.12: 60.
step 2.2, the mixture was transferred to an autoclave, sealed, kept at 180 ℃ for 12h and then cooled naturally to room temperature. Collecting the precipitate, washing and drying to obtain CoFe2O4CoFe with a loading of 30 wt% in MXene2O4@ MXene powder.
Step 3, using CoFe2O4Preparation of CoFe from @ MXene powder and cellulose2O4The @ MXene/cellulose aerogel comprises the following specific steps:
step 3.1, adding NaOH and urea powder into deionized water, stirring for 15min to uniformly disperse the NaOH and urea powder, placing the mixed solution in a refrigerator at the temperature of-12 ℃ for 12h, taking out the mixed solution, adding 2.43g of cellulose powder, and uniformly stirring by using a glass rod; freezing the solution in a refrigerator at-26 deg.C for 24 hr, thawing naturally at room temperature, and adding prepared CoFe2O4@ MXene powder, after ultrasonic dispersion, freezing again for 12h, naturally thawing, adding 2.34g N, N-Methylene Bisacrylamide (MBA), and vigorously stirring with a glass rod to uniformly disperse the powder;
NaOH, Urea, CoFe2O4The mass ratio of the @ MXene powder to the cellulose powder to the MBA to the water is 7: 12: 0.1458: 2.43: 2.34: 81;
step 3.2, pouring the mixed solution obtained in the step 3.1 into a mould of a six-hole cell culture plate, and standing for one day to obtain CoFe2O4@ MXene/cellulose hydrogel, washing with deionized water to neutral, freezing at-26 deg.C for 12 hr, and freeze drying for 48 hr to obtain CoFe2O4@ MXene/cellulose aerogel;
and 4, putting the aerogel obtained in the step 3 into a tubular furnace as a precursor for carbonization treatment to prepare the CoFe @ MXene/carbon aerogel composite material.
The carbonization conditions are specifically as follows: introducing nitrogen at the speed of 50-100 mL/s, raising the temperature to 300 ℃ at the speed of 3 ℃/min, preserving the heat for 1h, then raising the temperature to 1200 ℃ at the speed of 5 ℃/min, preserving the heat for 2h, and cooling to the room temperature.
Compared with a commercial electromagnetic shielding material (20dB), the electromagnetic shielding effectiveness of the CoFe @ MXene/carbon aerogel composite material prepared in example 5 is 75.5dB, and is improved by 277.5%.
SE of CoFe @ MXene/carbon aerogel composite material prepared by the method under different CoFe contentsTFIG. 1 shows that as the content of CoFe in MXene increases, the shielding effectiveness increases; SE of CoFe @ MXene/carbon aerogel at different carbonization temperaturesTAs shown in fig. 3, the shielding effectiveness increases with increasing carbonization temperature. FIGS. 2 and 4 show SE of the composite material at different magnetic filler contents and carbonization temperaturesR、SEAIt is evident from the figure that the shielding mechanism is mainly absorbing and very small reflecting, all<3dB, CoFe @ MXene/carbon aerogel composite material glue shows excellent electromagnetic shielding performance.
The action mechanism of the method is as follows: by using the CoFe @ MXene/carbon aerogel composite material with the magnetic three-dimensional network structure, when electromagnetic waves enter, the incident electromagnetic waves and the surface are easy to enter the material due to the optimization of the magnetic component and the porous structure on impedance matching. And because of the addition of CoFe and MXene in the composite material, a large number of effective interfaces are obtained, interface polarization and dipole polarization are induced, dielectric loss is improved, stronger electromagnetic wave loss capability is further generated, and thus more excellent electromagnetic shielding performance is obtained.
According to the CoFe @ MXene/carbon aerogel composite material prepared by the method, the unique design of the three-dimensional structure of the composite material and the action of the magnetic components improve impedance matching, electromagnetic waves can enter more easily, multiple reflection and scattering occur in a porous structure, incident waves are attenuated through the magnetic loss of CoFe and interface polarization and dipole polarization caused by a large number of effective interfaces, and therefore excellent electromagnetic shielding performance is obtained. The prepared composite material has electromagnetic shielding effectiveness of 75.5dB when the content of CoFe in MXene is 30 wt% and the carbonization temperature is 1200 ℃. This provides a feasible solution for manufacturing the electromagnetic shielding material with excellent electromagnetic shielding performance and electromagnetic wave absorption performance.
According to the preparation method of the CoFe @ MXene/carbon aerogel composite material, the CoFe @ MXene/carbon aerogel composite material with high electromagnetic shielding performance is prepared by using a freeze drying method, an in-situ synthesis method and a high-temperature carbonization process, the preparation process is safe and environment-friendly, the preparation process is simple, the cost is low, and the preparation method has wide practicability and popularization value; the CoFe @ MXene/carbon aerogel composite material prepared by the preparation method disclosed by the invention is excellent in electromagnetic shielding performance and can meet the application requirements in the fields of aerospace, electronic packaging and the like.

Claims (8)

  1. The preparation method of the CoFe @ MXene/carbon aerogel composite material is characterized by comprising the following steps:
    step 1, etching Ti by LiF-HCl3AlC2Preparing a precursor into less-layer MXene powder;
    step 2, preparation of CoFe by hydrothermal method2O4@ MXene powder;
    step 3, using CoFe2O4Preparation of CoFe from @ MXene powder and cellulose2O4@ MXene/cellulose aerogel;
    step 4, CoFe obtained in step 32O4And putting the @ MXene/cellulose aerogel into a tubular furnace for carbonization treatment to obtain the CoFe @ MXene/carbon aerogel composite material.
  2. 2. The preparation method of the CoFe @ MXene/carbon aerogel composite material according to claim 1, wherein in the step 1, the specific steps are as follows:
    step 1.1, fully mixing LiF and HCl, and then slowly adding MAX phase precursor powder under an ice bath condition to obtain a mixture;
    the mass ratio of LiF, HCl and MAX phase precursor powder is 1: 20: 1;
    step 1.2, the mixture was stirred at 35 ℃ for 24 hours to obtain Ti3C2TxThe suspension is then repeatedly centrifuged and washed with deionized water until the pH of the solution is 7 to obtain Ti3C2TxA precipitate;
    step 1.3, adding Ti3C2TxDispersing the precipitate in deionized water, performing ultrasonic treatment for 15min to promote layering of multiple layers of MXene, then continuing to centrifuge at 3500r/min for 15min, circulating for several times, and taking supernatant to obtain a few layers of MXene dispersion liquid;
    step 1.4, freezing the obtained small-layer MXene dispersion liquid at-26 ℃ in advance, and freeze-drying the small-layer MXene dispersion liquid by using a freeze dryer to obtain small-layer MXene powder.
  3. 3. The preparation method of CoFe @ MXene/carbon aerogel composite material according to claim 1, wherein in the step 2, specifically: dissolving PVP in deionized water under magnetic stirring, and dissolving Fe (NO) after PVP is completely dissolved3)3·9H2O、Co(NO3)2·6H2Adding O and a small layer of MXene powder into the solution, performing ultrasonic dispersion for 30 minutes, adding urea, uniformly mixing, transferring the mixed solution into a high-pressure reaction kettle, sealing, performing hydrothermal reaction at 180 ℃ for 12 hours, naturally cooling to room temperature, collecting precipitate, washing and drying to obtain CoFe2O4@ MXene powder.
  4. 4. The method of claim 3, wherein the PVP, Fe (NO) aerogel composite3)3·9H2O、Co(NO3)2·6H2The mass ratio of O, the less-layer MXene powder, the urea and the deionized water is 0.15: 0.135-0.404: 0.097-0.145: 0.7047-0.548: 0.12: 60.
  5. 5. the preparation method of CoFe @ MXene/carbon aerogel composite material according to claim 1, wherein in the step 3, specifically:
    step 3.1, adding NaOH and urea into deionized water, stirring for 15min to obtain a mixed solution, and then placing the mixed solution in a refrigerator for refrigeration; adding cellulose powder, stirring, freezing the solution in refrigerator, thawing naturally, adding CoFe2O4@ MXene powder, ultrasonic dispersing, freezing at-26 deg.C for 12 hr, naturally thawing, adding MBA, and stirring;
    step 3.2, pouring the mixed solution obtained in the step 3.1 into a mold of a six-hole cell culture plate, and standing for one day to obtain CoFe2O4@ MXene/cellulose hydrogel, washing with deionized water to neutral, freezing at-26 deg.C for 12 hr, and freeze drying for 48 hr to obtain CoFe2O4@ MXene/cellulose aerogel.
  6. 6. The preparation method of CoFe @ MXene/carbon aerogel composite material according to claim 5, wherein in the step 3.1, the refrigeration temperature is-12 ℃ and the refrigeration time is 12 h; the freezing temperature is-26 deg.C, and the freezing time is 24 h.
  7. 7. The method for preparing CoFe @ MXene/carbon aerogel composite material according to claim 5, wherein in step 3.1, NaOH, urea, CoFe2O4The mass ratio of the @ MXene powder to the cellulose powder to the MBA to the deionized water is 7: 12: 0.1458: 2.43: 2.34: 81.
  8. 8. the preparation method of the CoFe @ MXene/carbon aerogel composite material according to claim 1, wherein in the step 4, the carbonization conditions are specifically as follows: introducing nitrogen at the speed of 50-100 mL/s, heating to 300 ℃ at the speed of 3 ℃/min, preserving heat for 1h, then heating to 800-1200 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature.
CN202111041252.5A 2021-09-06 2021-09-06 Preparation method of CoFe @ MXene/carbon aerogel composite material Pending CN113873859A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477182A (en) * 2022-02-11 2022-05-13 哈尔滨师范大学 Preparation method of three-dimensional folded titanium carbide xerogel and application of lithium ion battery cathode material thereof
CN114804108A (en) * 2022-02-25 2022-07-29 西安理工大学 N, S preparation method of co-doped MXene/cellulose derived carbon aerogel
CN114874751A (en) * 2022-04-14 2022-08-09 山东大学 Gradient heating folded MXene/TiO 2 Preparation method of paraffin wax and electromagnetic shielding application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477182A (en) * 2022-02-11 2022-05-13 哈尔滨师范大学 Preparation method of three-dimensional folded titanium carbide xerogel and application of lithium ion battery cathode material thereof
CN114477182B (en) * 2022-02-11 2023-10-10 哈尔滨师范大学 Preparation method of three-dimensional wrinkled titanium carbide xerogel and application of three-dimensional wrinkled titanium carbide xerogel in lithium ion battery cathode material
CN114804108A (en) * 2022-02-25 2022-07-29 西安理工大学 N, S preparation method of co-doped MXene/cellulose derived carbon aerogel
CN114804108B (en) * 2022-02-25 2023-09-15 西安理工大学 Preparation method of N, S co-doped MXene/cellulose derived carbon aerogel
CN114874751A (en) * 2022-04-14 2022-08-09 山东大学 Gradient heating folded MXene/TiO 2 Preparation method of paraffin wax and electromagnetic shielding application thereof

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