CN114454573A - Ti3C2TxMXene/GO heterogeneous membrane and preparation method and application thereof - Google Patents

Ti3C2TxMXene/GO heterogeneous membrane and preparation method and application thereof Download PDF

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CN114454573A
CN114454573A CN202111626487.0A CN202111626487A CN114454573A CN 114454573 A CN114454573 A CN 114454573A CN 202111626487 A CN202111626487 A CN 202111626487A CN 114454573 A CN114454573 A CN 114454573A
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mxene
heterogeneous
film
membrane
graphene oxide
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李颖
吴开友
杨旭林
李逵
王盼
冯威
雷一鸣
张敏
蒲昀
谈博一
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Chengdu University
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Chengdu University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding

Abstract

The invention discloses a Ti3C2TXMXene/GO heterogeneous membrane and a preparation method and application thereof, belonging to the field of electromagnetic shielding materials and preparation methods and application thereof; the heterogeneous film is composed of GO layer and Ti3C2TXMXene layers are sequentially stacked in a staggered manner to form a three-layer structure film with a micro heterogeneous interface, and the Ti is3C2TXThe MXene/GO heterogeneous film not only has better electromagnetic shielding performance, but also can protect Ti3C2TXMXene is not oxidized to make it haveLong-term effect, can be applied to the field of electromagnetic shielding. Ti of the invention3C2TXThe MXene/GO heterogeneous membrane material belongs to a novel material and can effectively prolong Ti3C2TXThe MXene-based electromagnetic shielding material has a wide application prospect in use and validity period; meanwhile, the preparation method is simple and easy to implement, does not use toxic and harmful solvents, does not cause secondary pollution, and can be used for large-scale industrial production.

Description

Ti3C2TxMXene/GO heterogeneous membrane and preparation method and application thereof
Technical Field
The invention belongs to the field of electromagnetic shielding materials and preparation methods and application thereof, and particularly relates to Ti3C2TXMXene/GO heterogeneous membrane and preparation method and application thereof.
Background
With the rapid development of modern electronic technology, electronic devices and wireless communication devices are widely used, and more electromagnetic radiation and interference are generated, so that the space electromagnetic environment is increasingly complex. Electromagnetic radiation becomes a new type of pollution following noise, water and air pollution, and not only does electromagnetic radiation affect the information security of communication equipment and the normal operation of electronic equipment, but also can harm human health. Therefore, research into a new electromagnetic shielding material has become an indispensable part for protecting electronic components and humans from electromagnetic interference.
MXenes is a novel two-dimensional (2D) transition metal carbide and/or nitride nano material with the molecular formula of Mn+1XnTxWherein M is a transition metal element, X is carbon and/or nitrogen, and Tx is a functional surface terminal group (e.g., -O, -F, and-OH). MXenes is widely used for energy storage, strain sensing, electrical addition due to its excellent metal conductivity, hydrophilicity and good interfacial interaction with polymersHeat, wave absorbing (MA) and electromagnetic shielding. Ti3C2TXMXene is a novel graphene-like two-dimensional material, has a large specific surface area, good conductivity, a large number of surface active sites and a unique layered structure, has wide application in the direction of nano-functional materials, and particularly shows excellent performance and huge application potential in the field of electromagnetic wave absorbing materials. However, Ti3C2TXThe inherent characteristic of easy oxidative deterioration of MXene causes the structure and performance of MXene to change and decrease rapidly in air or humid environment, severely limits the electromagnetic shielding performance and the long-term effect thereof, and cannot be popularized and applied practically.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide Ti3C2TXMXene/GO heterogeneous film capable of preparing Ti by simple method3C2TXMXene/GO heterogeneous films, of Ti3C2TXThe MXene/GO heterogeneous film has good electromagnetic shielding performance and long performance retention.
The purpose of the invention is realized by the following technical scheme: ti3C2TXAn MXene/GO heterogeneous membrane consisting of a graphene oxide layer and Ti3C2TXThe three-layer structure film with a microscopic heterogeneous interface is formed by alternately stacking MXene layers, wherein the top film and the bottom film are graphene oxide layers, and Ti3C2TXThe MXene layer is arranged between the top film and the bottom film.
Further, the Ti3C2TXWherein T is O, OH or F.
Further, the Ti3C2TXTi in MXene/GO heterogeneous film3C2TXThe content of MXene and the content of graphene oxide are both 5-95 wt%. Ti3C2TXMXene tends to be coated by GO, so that the oxidation is delayed, and the graphene has practical use value.
Further, the Ti3C2TX MXene/GTi in O heterogeneous film3C2TXThe thickness of the MXene and the graphene oxide is 2-5 nm.
Further, the Ti3C2TXThe radial dimension of the sheet layer of the graphene oxide in the MXene/GO heterogeneous film is more than 100 nm.
Further, Ti3C2TXThe MXene layer also contains a functional material, and the functional material is ferrite, a nickel-containing compound, a magnetic material, graphene, a carbon-containing nano material or a dielectric material.
Ti3C2TXThe preparation method of the MXene/GO heterogeneous membrane comprises the following steps:
s1, forming a base film: carrying out vacuum filtration on the graphene oxide aqueous solution to form a base film;
s2, forming a functional film: mixing Ti3C2TXPouring MXene dispersion liquid on the formed basement membrane, and performing vacuum filtration to form a functional membrane;
s3, forming a top film: then carrying out vacuum filtration on the graphene oxide aqueous solution to form a top film;
s4, drying: mixing the graphene oxide layer obtained in the step S3 with Ti3C2TXDrying the heterogeneous film with staggered MXene layers to obtain Ti3C2TXMXene/GO heterogeneous membranes.
Further, the Ti3C2TXThe concentration of the MXene dispersion liquid is 5 mg/mL, and the concentration of the graphene oxide is 4 mg/mL. Graphene oxide aqueous solution and Ti with the above concentrations3C2TXMXene nanosheet dispersion liquid is beneficial to improving Ti obtained by preparation3C2TXTi in MXene/GO heterogeneous film3C2TXAbsolute efficiency of MXene.
Further, the suction filtration time of the bottom membrane is 30-60 min, the suction filtration time of the functional membrane is 180-240 min, and the suction filtration time of the top membrane is 300-360 min.
Because of Ti3C2TXMXene is easily oxidized and deteriorated by oxygen in air and is too longThe suction filtration time results in Ti3C2TXMXene is seriously oxidized, EMI performance is reduced, and Ti can be caused by too short pumping filtration time3C2TXThe MXene/GO heterogeneous membrane forms the effect of layered distribution.
Further, the drying temperature is room temperature, and the drying time is 45-52 hours.
The above Ti3C2TXThe application of MXene/GO heterogeneous film in electromagnetic shielding.
The invention introduces a large-size Graphene Oxide (GO) sheet as a protective layer to cover Ti3C2TXMXene layer surface, not only protecting Ti3C2TXMXene is not oxidized by air and can be mixed with Ti3C2TXMXene forms a heterogeneous interface to increase loss; the water solubility of GO also makes the processing very simple and safe; the hydrophilic surface of GO can be bonded with Ti3C2TXMXene forms interaction, and a tight interface ensures the mechanical property of a film material; GO and Ti3C2TXThe heterogeneous interface formed by MXene can also be damaged to electromagnetic waves, and the electromagnetic shielding performance is improved; defects and dielectric properties of GO itself can also improve electromagnetic shielding performance. Thus, Ti of the present invention3C2TXThe MXene/GO heterogeneous film has better electromagnetic shielding performance and can be applied to the field of electromagnetic shielding.
Compared with the prior art, the invention has the following advantages: the invention discloses a long-acting and high-efficiency electromagnetic shielding heterogeneous film Ti3C2TXThe MXene/GO heterogeneous film is formed by a GO layer and Ti3C2TXMXene layers are sequentially and alternately stacked to form the film with the microscopic heterogeneous interface. The Ti3C2TXThe MXene/GO heterogeneous film not only has better electromagnetic shielding performance, but also can protect Ti3C2TXMXene is not oxidized, so that the MXene has long-acting property and can be applied to the field of electromagnetic shielding. Ti of the invention3C2TXThe MXene/GO heterogeneous membrane material belongs to a novel material and can effectively prolong Ti3C2TXThe MXene-based electromagnetic shielding material has a wide application prospect in use and validity period; meanwhile, the preparation method is simple and easy to implement, does not use toxic and harmful solvents, does not cause secondary pollution, and can be used for large-scale industrial production.
Drawings
FIG. 1 is a process for preparing Ti according to the present invention3C2TXFlow diagram of MXene/GO heterogeneous membranes.
FIG. 2 shows Ti prepared in example 4, example 7 and example 83C2TXScanning electron microscope images of MXene/GO heterogeneous films; wherein, the a region is 1G1M1G obtained in example 4, the b region is 2G2M2G obtained in example 7, and the c region is 3G3M3G obtained in example 8, wherein, a ', b ' and c ' are respectively the scanning electron microscope images of a, b and c.
FIG. 3 is a GO membrane of comparative example 1, Ti of comparative example 73C2TXMXene films and Ti from example 73C2TXXRD monitoring of MXene/GO heterogeneous films.
FIG. 4 is a GO membrane of comparative example 1, Ti of comparative example 73C2TXMXene films and Ti from example 73C2TXXRD monitoring results of MXene/GO heterogeneous films after being placed for several days; wherein 2, 3, 5, 9 and 16 in the figure represent days of standing.
FIG. 5 shows Ti prepared in examples 4 to 6 and comparative example 63C2TXEMI performance test results of MXene/GO heterogeneous films.
FIG. 6 shows Ti prepared in examples 5 and 63C2TXMXene/GO heterogeneous films, Ti prepared in comparative example 33C2TXThe MXene film is placed in a room temperature environment to keep the change test result of the EMI value for one week; wherein a is one week before and b is one week after.
FIG. 7 shows Ti prepared in example 13C2TXEMI performance variation for different shelf life of MXene/GO heterogeneous films.
FIG. 8 shows Ti prepared in example 23C2TXEMI performance variation for different shelf life of MXene/GO heterogeneous films.
FIG. 9 shows Ti prepared in example 33C2TXEMI performance variation for different shelf life of MXene/GO heterogeneous films.
FIG. 10 shows Ti prepared in example 53C2TXEMI performance variation for different shelf life of MXene/GO heterogeneous films.
Figure 11 is the EMI performance variation for different shelf times for the GO film prepared in comparative example 2.
FIG. 12 shows Ti prepared in comparative example 43C2TXEMI performance variations for different shelf life of MXene films.
FIG. 13 shows Ti prepared in comparative example 53C2TXEMI performance variation for different shelf life of MXene/GO hybrid films.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
The scope of protection of the invention is not limited to the following:
ti3C2TXAn MXene/GO heterogeneous membrane consisting of a graphene oxide layer and Ti3C2TXThe three-layer structure film with a microscopic heterogeneous interface is formed by alternately stacking MXene layers, wherein the top film and the bottom film are graphene oxide layers, and Ti3C2TXThe MXene layer is arranged between the top film and the bottom film. The Ti3C2TXWherein T is O, OH or F; the Ti3C2TXTi in MXene/GO heterogeneous film3C2TXThe content of MXene and graphene oxide is 5-95 wt%; the Ti3C2TXTi in MXene/GO heterogeneous film3C2TXThe thickness of the MXene and graphene oxide layers is 2-5 nm; the Ti3C2TXThe radial dimension of the sheet layer of the graphene oxide in the MXene/GO heterogeneous film is more than 100 nm.
Example 1: ti3C2TXMXene/GO heterogeneous membrane and preparation method thereof
Buy 4 m separatelyGO solution at g/mL and Ti at 5 mg/mL3C2TXMXene solution;
diluting the GO solution by three times with water to obtain a GO aqueous solution;
slowly dripping 1.5 mL of GO aqueous solution on filter paper with a pore diameter of 0.45 mu m, filtering for about 0.5 h, and slowly dripping 3mL of Ti3C2TXPumping and filtering MXene nanosheet dispersion liquid for about 3 hours, slowly dropwise adding 1.5 mL of GO aqueous solution, pumping and filtering for about 5 hours, taking down the heterogeneous membrane after pumping and filtering, drying for 45 hours at room temperature, and drying for about 24 hours to obtain Ti3C2TXMXene/GO heterogeneous membrane, the preparation flow is shown in figure 1.
Example 2: ti3C2TXMXene/GO heterogeneous membrane and preparation method thereof
Preparation of aqueous GO solution:
0.8 mL of GO (4 mg/mL) was added dropwise to the flask, and 1.6 mL of deionized water was added to dilute three times, and stirred for 15 seconds to prepare an aqueous GO solution.
Preparation of Ti3C2TXMXene/GO heterogeneous membranes:
slowly dripping 2.4 mL of GO aqueous solution on filter paper with a pore diameter of 0.45 mu m, performing suction filtration for about 0.5 h, and slowly dripping 3mL of Ti3C2TXPumping and filtering MXene nanosheet dispersion liquid for about 3h, slowly dropwise adding 2.4 mL of GO aqueous solution, pumping and filtering for about 5 h, taking down the heterogeneous membrane after pumping and filtering, drying at room temperature for 52 h, and drying for about 24h to obtain Ti3C2TXMXene/GO heterogeneous membranes.
Example 3: ti3C2TXMXene/GO heterogeneous membrane and preparation method thereof
Separately purchase 4 mg/mL GO solution and 5 mg/mL Ti3C2TXMXene solution, and the GO solution is diluted three times to obtain a GO aqueous solution.
Slowly dropping 3.6 mL of aqueous solution of LGO onto filter paper with pore diameter of 0.45 μm, filtering for about 0.5 h, and slowly dropping 3mL of Ti3C2TXPumping and filtering the MXene nanosheet dispersion liquid for about 3h, slowly dripping 3.6 mLGO aqueous solution for about 5 h, taking down the heterogeneous membrane after the pumping and filtering are finished, and keeping the room temperature of the heterogeneous membrane at room temperatureDrying for 48 h, and drying for 24h to obtain Ti3C2TXMXene/GO heterogeneous membranes.
Example 4: ti3C2TXMXene/GO heterogeneous membrane and preparation method thereof
Separately purchase 4 mg/mL GO solution and 5 mg/mL Ti3C2TXMXene solution;
the GO solution was diluted three times to obtain a GO aqueous solution.
Slowly dripping 3mL of GO aqueous solution onto filter paper with pore diameter of 0.45 mu m, performing suction filtration for about 0.5 h, and slowly dripping 1 mL of Ti3C2TXPumping and filtering MXene nanosheet dispersion liquid for about 3 hours, slowly dropwise adding 3mL of GO aqueous solution, pumping and filtering for about 5 hours, taking off the heterogeneous membrane after pumping and filtering, drying for 50 hours at room temperature, and drying for about 24 hours to obtain Ti3C2TXMXene/GO heterogeneous membranes.
Example 5: ti3C2TXMXene/GO heterogeneous membrane and preparation method thereof
Separately purchase 4 mg/mL GO solution and 5 mg/mL Ti3C2TXMXene solution;
the GO solution was diluted three times to obtain a GO aqueous solution.
Slowly dripping 3mL of GO aqueous solution onto filter paper with pore diameter of 0.45 mu m, performing suction filtration for about 0.5 h, and slowly dripping 2 mL of Ti3C2TXPumping and filtering MXene nanosheet dispersion liquid for about 3 hours, slowly dropwise adding 3mL of GO aqueous solution, pumping and filtering for about 5 hours, taking off the heterogeneous membrane after pumping and filtering, drying at room temperature for 48 hours, and drying for about 24 hours to obtain Ti3C2TXMXene/GO heterogeneous membranes.
Example 6: ti3C2TXMXene/GO heterogeneous membrane and preparation method thereof
Separately purchase 4 mg/mL GO solution and 5 mg/mL Ti3C2TXMXene solution;
the GO solution was diluted three times to obtain a GO aqueous solution.
Slowly dripping 3mL of GO aqueous solution onto filter paper with pore diameter of 0.45 mu m, and performing suction filtration for about 0.5 hSlowly dropwise adding 3mL of Ti3C2TXPumping and filtering MXene nanosheet dispersion liquid for about 3 hours, slowly dropwise adding 3mL of GO aqueous solution, pumping and filtering for about 5 hours, taking off the heterogeneous membrane after pumping and filtering, drying for 50 hours at room temperature, and drying for about 24 hours to obtain Ti3C2TXMXene/GO heterogeneous membranes.
Example 7: ti3C2TXMXene/GO heterogeneous membrane and preparation method thereof
Separately purchase 4 mg/mL GO solution and 5 mg/mL Ti3C2TXMXene solution;
the GO solution was diluted three times to obtain a GO aqueous solution.
Slowly dripping 3mL of GO aqueous solution onto filter paper with pore diameter of 0.45 mu m, performing suction filtration for about 0.5 h, and slowly dripping 2 mL of Ti3C2TXPumping and filtering the MXene nanosheet dispersion liquid for about 3 hours, slowly dropwise adding 3mL of GO aqueous solution, pumping and filtering for about 5 hours, taking down the heterogeneous membrane after the pumping and filtering are finished, drying at room temperature for 52 hours, and drying for about 24 hours to obtain Ti3C2TXMXene/GO heterogeneous membranes.
Example 8: ti3C2TXMXene/GO heterogeneous membrane and preparation method thereof
Separately purchase 4 mg/mL GO solution and 5 mg/mL Ti3C2TXMXene solution;
the GO solution was diluted three times to give an aqueous GO solution.
Slowly dripping 3mL of GO aqueous solution onto filter paper with pore diameter of 0.45 mu m, performing suction filtration for about 0.5 h, and slowly dripping 3mL of Ti3C2TXPumping and filtering MXene nanosheet dispersion liquid for about 3 hours, slowly dropwise adding 3mL of GO aqueous solution, pumping and filtering for about 5 hours, taking off the heterogeneous membrane after pumping and filtering, drying at room temperature for 48 hours, and drying for about 24 hours to obtain Ti3C2TXMXene/GO heterogeneous membranes.
Example 9: ti added with ferrite3C2TXMXene/GO heterogeneous membrane and preparation method thereof
S1, forming a base film: carrying out vacuum filtration on the graphene oxide aqueous solution, wherein the concentration of the graphene oxide is 4 mg/mL, and the filtration time is 30 min, so as to form a base membrane;
s2, forming a functional film: mixing Ti3C2TXAdding ferrite to MXene dispersion, pouring onto the formed base film, vacuum filtering, and adding Ti3C2TXThe concentration of MXene dispersion liquid is 5 mg/mL, and the suction filtration time is 180 min to form a functional film;
s3, forming a top film: carrying out vacuum filtration on the graphene oxide aqueous solution for 300 min to form a top film;
s4, drying: mixing the graphene oxide layer obtained in the step S3 with Ti3C2TXDrying the heterogeneous film with staggered MXene layers at room temperature for 45 h to obtain the Ti with the added ferrite3C2TXMXene/GO heterogeneous membranes.
Example 10: ti added with magnetic material3C2TXMXene/GO heterogeneous membrane and preparation method thereof
S1, forming a base film: carrying out vacuum filtration on the graphene oxide aqueous solution, wherein the concentration of the graphene oxide is 4 mg/mL, and the filtration time is 60 min, so as to form a base membrane;
s2, forming a functional film: mixing Ti3C2TXAdding magnetic material into MXene dispersion, pouring onto the formed basement membrane, vacuum filtering, and adding Ti3C2TXThe concentration of MXene dispersion liquid is 5 mg/mL, and the suction filtration time is 240 min to form a functional film;
s3, forming a top film: carrying out vacuum filtration on the graphene oxide aqueous solution for 360 min to form a top film;
s4, drying: mixing the graphene oxide layer obtained in the step S3 with Ti3C2TXDrying the MXene layers in staggered heterogeneous films at room temperature for 48 hours to obtain the Ti added with the magnetic material3C2TXMXene/GO heterogeneous membranes.
Example 11: ti added with dielectric material3C2TXMXene/GO heterogeneous membrane and preparation method thereof
S1, forming a base film: carrying out vacuum filtration on the graphene oxide aqueous solution, wherein the concentration of the graphene oxide is 4 mg/mL, and the filtration time is 50 min, so as to form a basement membrane;
s2, forming a functional film: mixing Ti3C2TXAdding dielectric material into MXene dispersion, pouring onto the formed base film, vacuum filtering, and adding Ti3C2TXThe concentration of MXene dispersion liquid is 5 mg/mL, and the suction filtration time is 220 min to form a functional membrane;
s3, forming a top film: carrying out vacuum filtration on the graphene oxide aqueous solution for 340 min to form a top film;
s4, drying: mixing the graphene oxide layer obtained in the step S3 with Ti3C2TXDrying the MXene layer staggered heterogeneous film at room temperature for 52 h to obtain the Ti added with the dielectric material3C2TXMXene/GO heterogeneous membranes.
Comparative example 1: GO membrane and preparation method thereof
The aqueous GO solution prepared in example 1 was taken.
Slowly dripping 3mL of GO aqueous solution on filter paper with the pore diameter of 0.45 mu m, carrying out suction filtration for about 0.5 h, and drying for about 24h to obtain the GO membrane.
Comparative example 2: GO membrane and preparation method thereof
The aqueous GO solution prepared in example 1 was taken.
And slowly dripping 6mL of GO aqueous solution onto filter paper with the pore diameter of 0.45 mu m, carrying out suction filtration for about 0.5 h, and drying for about 24h to obtain the GO membrane.
Comparative example 3: ti3C2TXMXene film and preparation method thereof
2 mL of Ti3C2TXSlowly dripping MXene nanosheet dispersion liquid onto filter paper with the aperture of 0.45 mu m, performing suction filtration for about 3 hours, and drying for about 24 hours to obtain Ti3C2TXMXene films.
Comparative example 4: ti3C2TXMXene film and preparation method thereof
3mL of Ti3C2TXSlowly dripping MXene nanosheet dispersion liquid onto filter paper with the aperture of 0.45 mu m, performing suction filtration for about 3 hours, and drying for about 24 hours to obtain Ti3C2TXMXene films.
Comparative example 5: ti3C2TXMXene/GO mixed film and preparation method thereof
The aqueous GO solution prepared in example 1 was taken.
6mL of the aqueous GO solution was slowly added dropwise to a volume containing 3mL of Ti3C2TXMXene in a beaker, magnetically stir for about 5 min, then add Ti3C2TXSlowly dripping MXene/GO mixed solution on filter paper with the pore diameter of 0.45 mu m, performing suction filtration for about 3h, and drying for about 24h to obtain Ti3C2TXMXene/GO hybrid films.
Comparative example 6: ti3C2TXMXene/GO heterogeneous membrane and preparation method thereof
Separately purchase 4 mg/mL GO solution and 5 mg/mL Ti3C2TXMXene solution.
The GO solution was diluted three times to obtain a GO aqueous solution.
Slowly dripping 3mL of GO aqueous solution onto filter paper with pore diameter of 0.45 mu m, filtering, and slowly dripping 2 mL of Ti3C2TXPumping and filtering MXene nanosheet dispersion, slowly dripping 3mL of GO aqueous solution, and slowly dripping 2 mL of Ti3C2TXCarrying out suction filtration on MXene nanosheet dispersion, slowly dropwise adding 3mL of GO aqueous solution, carrying out suction filtration, taking down the heterogeneous membrane after the suction filtration is finished, and drying for about 24 hours to obtain Ti3C2TXMXene/GO heterogeneous membranes.
Comparative example 7: ti3C2TXMXene films and methods of making the same
Adding 1 mL of Ti3C2TXSlowly dripping MXene nanosheet dispersion liquid onto filter paper with the aperture of 0.45 mu m, performing suction filtration for about 3 hours, and drying for about 24 hours to obtain Ti3C2TXMXene films.
Test example 1:
ti obtained in example 4, example 7 and example 8 was used3C2TXMXene/GO heterogeneous membranes (note in particular that the samples are GO and Ti3C2TXMXene amounts and sequence named, example 1G1M1G, representing samples from 1 mL GO to 1 mL Ti3C2TXMXene-1 mL GO) were prepared by suction filtration in order) and analyzed by scanning electron microscopy, the heterogeneous membrane macrostructure and scanning electron microscopy images are shown in FIG. 2.
Wherein region a in FIG. 2 is 1G1M1G obtained in example 4, region b in FIG. 2 is 2G2M2G obtained in example 7, and region c in FIG. 2 is 3G3M3G obtained in example 8, wherein a ', b ', and c ' are SEM images of a, b, and c, respectively. It can be seen that all the obtained membrane materials are flexible, besides macroscopic color difference, the interlayer structure also has obvious difference, and the membrane is obviously divided into three layers. As can be seen from the areas a ', b ' and c ' in FIG. 2, the heterogeneous membrane prepared by the vacuum filtration method has a regular shape, a flaky shape and a thickness of 2-3 μm.
Test example 2:
ti obtained in examples 1 to 8 was used3C2TXMXene/GO heterogeneous membranes, GO membranes from comparative examples 1 and 2, and Ti from comparative examples 3 and 43C2TXMXene film and Ti from comparative example 53C2TXX-ray diffraction test is carried out on the MXene/GO mixed film, and GO and Ti are shown in figure 33C2TXXRD monitoring results of MXene and 1G1M1G heterogeneous films, and FIG. 4 shows GO and Ti3C2TXXRD monitoring of MXene and heterogeneous films after several days of standing. It can be seen that both GO and Ti are present in the heterogeneous film3C2TXMXene two characteristic diffraction peaks, namely a characteristic diffraction peak belonging to GO (002) at about 10.5 degrees and a characteristic diffraction peak belonging to Ti at about 6.0 degrees3C2TXCharacteristic diffraction peak of MXene (002). With increasing standing time, Ti3C2TXThe MXene (002) peak was gradually shifted toward a high angle, indicating Ti3C2TXMXene layerThe pitch decreases and oxidation of the lamellae occurs.
Test example 3:
ti obtained in examples 4 to 6 and comparative example 6 was used3C2TXEMI performance of the MXene/GO heterogeneous film is tested, the test result is shown in figure 5, and Ti is improved3C2TXThe EMI performance is slightly improved after the MXene content, the average EMI value of 1G2M1G reaches 25 dB, and the average EMI value of 1G3M1G reaches 27 dB. The dosage and EMI values are converted into Absolute efficiency (SSE/t), and the SSE/t of 1G1M1G, 1G2M1G and 1G3M1G are 5425, 2826 and 2035 dB cm2(ii) in terms of/g. Thus, it can be judged that3C2TXAddition of MXene in amounts that increase EMI but for Ti3C2TXThe absolute efficiency of MXene is not beneficial. Probably due to the limitation of experimental conditions, the suction filtration time is multiplied when preparing the multilayer film 1G2M1G2M1G, which leads to Ti3C2TXSevere MXene oxidation and reduced EMI properties, visible as Ti3C2TXAn increase in MXene film thickness did not significantly increase the EMI value.
Test example 4:
ti obtained in examples 5 and 6 was used3C2TXMXene/GO heterogeneous films, Ti from comparative example 33C2TXMXene film test the heterogeneous film was placed in room temperature environment for one week to maintain EMI value change, and the test result is shown in FIG. 6, where Ti can be seen3C2TXThe EMI value of the MXene film is obviously reduced from 37dB to about 25 dB, and the EMI value of the MXene film is reduced by Ti3C2TXThe EMI properties of MXene/GO heterogeneous films were not significantly compromised, confirming GO versus Ti3C2TXProtection of MXene and persistence of heterogeneous films.
Test example 5:
ti obtained in examples 1, 2, 3 and 5 was used3C2TXMXene/GO heterogeneous membranes, GO membranes from comparative example 2, Ti from comparative example 43C2TXMXene film, Ti obtained in comparative example 53C2TXMXene/GO mixed film testing its different lay-upsChanges in EMI properties over time are shown in FIGS. 7, 8, 9, 10, 11, 12 and 13, respectively, and the best combination of EMI properties and EMI property retention is seen for Ti prepared in example 23C2TXMXene/GO heterogeneous membranes.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept within the technical scope of the present invention.

Claims (10)

1. Ti3C2TXAn MXene/GO heterogeneous membrane, characterized in that the heterogeneous membrane is composed of a graphene oxide layer and Ti3C2TXThe three-layer structure film with a microscopic heterogeneous interface is formed by alternately stacking MXene layers, wherein the top film and the bottom film are graphene oxide layers, and Ti3C2TXThe MXene layer is arranged between the top film and the bottom film.
2. A Ti according to claim 13C2TXMXene/GO heterogeneous membrane, characterized in that said Ti is3C2TXTi in MXene/GO heterogeneous film3C2TXThe content of MXene and the content of graphene oxide are both 5-95 wt%.
3. A Ti according to claim 13C2TXAn MXene/GO heterogeneous membrane, wherein the Ti is3C2TXTi in MXene/GO heterogeneous film3C2TXThe thickness of the MXene and the graphene oxide is 2-5 nm.
4. A Ti according to claim 13C2TXMXene/GO heterogeneous membrane, characterized in that said Ti is3C2TXGraphene oxide in MXene/GO heterogeneous filmThe radial dimension of the lamellae is greater than 100 nm.
5. A Ti according to claim 13C2TXMXene/GO heterogeneous films characterized by Ti3C2TXThe MXene layer also contains a functional material, and the functional material is ferrite, a nickel-containing compound, a magnetic material, graphene, a carbon-containing nano material or a dielectric material.
6. A Ti according to claim 13C2TXThe preparation method of the MXene/GO heterogeneous membrane is characterized by comprising the following steps:
s1, forming a base film: carrying out vacuum filtration on the graphene oxide aqueous solution to form a base film;
s2, forming a functional film: mixing Ti3C2TXPouring the MXene dispersion liquid on the formed base membrane, and performing vacuum filtration to form a functional membrane;
s3, forming a top film: then carrying out vacuum filtration on the graphene oxide aqueous solution to form a top film;
s4, drying: mixing the graphene oxide layer obtained in the step S3 with Ti3C2TXDrying the heterogeneous film with staggered MXene layers to obtain Ti3C2TXMXene/GO heterogeneous membranes.
7. A Ti according to claim 63C2TXThe preparation method of the MXene/GO heterogeneous membrane is characterized in that the Ti is prepared3C2TXThe concentration of MXene dispersion was 5 mg/mL, and the concentration of graphene oxide was 4 mg/mL.
8. A Ti according to claim 63C2TXThe preparation method of the MXene/GO heterogeneous membrane is characterized in that the suction filtration time of the bottom membrane is 30-60 min, the suction filtration time of the functional membrane is 180-240 min, and the suction filtration time of the top membrane is 300-360 min.
9. A Ti according to claim 63C2TXThe preparation method of the MXene/GO heterogeneous membrane is characterized in that the drying temperature is room temperature, and the drying time is 45-52 hours.
10. The Ti of any of claims 1-53C2TXThe application of MXene/GO heterogeneous film in electromagnetic shielding.
CN202111626487.0A 2021-12-28 2021-12-28 Ti3C2TxMXene/GO heterogeneous membrane and preparation method and application thereof Pending CN114454573A (en)

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