CN115109288A - MXene film with high conductivity and high mechanical property as well as preparation method and application thereof - Google Patents

MXene film with high conductivity and high mechanical property as well as preparation method and application thereof Download PDF

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CN115109288A
CN115109288A CN202210877139.9A CN202210877139A CN115109288A CN 115109288 A CN115109288 A CN 115109288A CN 202210877139 A CN202210877139 A CN 202210877139A CN 115109288 A CN115109288 A CN 115109288A
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mxene
mechanical property
film
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high conductivity
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杜玉章
孔杰
陆文轩
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Northwestern Polytechnical University
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
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Abstract

The invention relates to the technical field of flexible electronic sensing devices, in particular to an MXene film with high conductivity and high mechanical property, and a preparation method and application thereof. The MXene is used as a matrix, a substance with a large amount of hydroxyl on the surface is used as a crosslinking material, and the substance is intercalated in MXene gaps to obtain an MXene conductive film; the result shows that the MXene conductive film prepared by the method has high conductivity, high mechanical property and good durability, can meet the monitoring requirement on human body movement in medicine, and simultaneously shows great application prospect in the electronic fields of nano generators, human skin and the like.

Description

MXene film with high conductivity and high mechanical property as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of flexible electronic sensing devices, in particular to an MXene film with high conductivity and high mechanical property, and a preparation method and application thereof.
Background
Flexible electronics such as flexible displays, flexible sensors, electronic skins, and 3D flexible printing, etc. need to have not only good electrical conductivity, but also good mechanical properties (such as tensile strength, elongation at break, etc.), which are the prerequisite for the flexible electronics to function properly (Oyawale adetsunji mobiles, Libo Gao, Haitao Zhao, Zhuo Wang, Mukhtar Lawan Adam, zhahao Sun, kalli Liu, jiang, Yang Lu, Zongyou Yin, Xuefeng Yu,2D Materials in heated smart flex electronics, Materials Today, volumeme 50,2021,116-148), therefore, the flexible electronics must have both good electrical conductivity and mechanical properties to ensure the normal use of the product.
In recent years, materials based on high conductivity and high capacitance, such as graphene and MXene, have attracted much attention and studied deeply in the fields of sensors, electrical energy storage, electronic skin, etc., wherein MXene exhibits great application potential in sensor applications due to its characteristics of good conductivity, high capacitance, high sensitivity, etc. (Ying Guo, Mengjuan Zhong, Zhiwei Fang, Pengbo Wan, and Guihua Yu, Nano Letters 201919(2), 1143-. Therefore, many MXene-based thin films with high sensitivity and good conductivity are used to make body sensors.
However, in recent years, MXene-based films still have certain drawbacks, specifically the following problems: firstly, MXene is powder with fine particle size, and does not have film-forming property due to the fact that strong interaction force does not exist among powder MXene particles; secondly, as MXene is not easy to disperse uniformly in the process of combining with other substances, agglomeration is often formed to cause poor film forming property; thirdly, MXene contains active metal Ti, so that the MXene is easily oxidized in the preparation process, and the conductivity of the MXene after film forming is poor; fourthly, the MXene film has poor mechanical property after film formation due to the limited surface groups of the MXene and poor bonding force with other substances, so that the MXene film with high conductivity and high mechanical property, which can overcome the technical defects, is needed.
Disclosure of Invention
Aiming at the defects of the prior art, the MXene film with high conductivity and high mechanical property and the preparation method and the application thereof are provided, the MXene is used as a matrix, a substance with a large amount of hydroxyl groups on the surface is used as a crosslinking material and is intercalated in MXene gaps to obtain the MXene conductive film, and the result shows that the MXene conductive film prepared by the method has high conductivity and high mechanical property and good durability, can meet the monitoring requirement on human body movement in medicine, and simultaneously shows great application prospect in the electronic fields of nano-generators, human skin and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of MXene film with high conductivity and high mechanical property comprises the following steps:
(1) preparation of MXene colloidal solution:
s1, etching the MAX material in an inert atmosphere to obtain etched MXene;
s2, dispersing the etched MXene obtained in the step S1 in a benign solvent to form a stable MXene colloidal solution;
(2) preparing a flexible matrix solution: dissolving a material with the surface containing electronegative groups in a benign solvent, adding a cross-linking agent, and uniformly stirring and mixing to obtain a flexible matrix solution;
(3) preparation of MXene film: and (3) adding the MXene colloidal solution obtained in the step (1) into the flexible matrix solution obtained in the step (2), uniformly mixing, and then heating for crosslinking and forming to obtain the MXene film.
Preferably, the MAX material of step S1 comprises Ti 3 AlC 2 、Nb 2 AlC，Mo 2 Ga 2 C，Ti 2 AlC。
Preferably, the etching method in step S1 includes:
adding lithium fluoride and MAX materials into a hydrochloric acid solution in an inert atmosphere, reacting for 24-48 h at 35-45 ℃, centrifuging, washing, adding an intercalator, vibrating for layering, and vacuum drying to obtain etched MXene;
wherein the concentration of the hydrochloric acid is 9-12 mol/L, and the mass ratio of the lithium fluoride to the MAX material is 1-2: 1; the intercalation agent is selected from deionized water, absolute ethyl alcohol, DMSO or acetone.
Preferably, the benign solvent in step S2 and step (2) is selected from deionized water, absolute ethyl alcohol or DMSO, and the ratio of the mass of etched MXene to the volume of the benign solvent is 0.1-4 g: 5-10 mL.
Preferably, the material of which the surface contains electronegative groups in the step (2) is selected from one or more of acrylamide, sodium alginate, polyvinyl alcohol, polyethylene glycol, chitosan and polymethacrylamide;
the cross-linking agent in the step (2) is selected from tetramethylethylenediamine and FeCl 3 Or formaldehyde, wherein the ratio of the mass of the cross-linking agent, the mass of the material with electronegative groups on the surface and the volume of the benign solvent is 0.01-0.05 g: 1 g: 5-10 mL.
Preferably, when acrylamide or methacrylamide is used as the material with the surface containing electronegative groups in the step (2), an initiator ammonium persulfate is also added.
Preferably, the conditions of the crosslinking reaction in step (3) are as follows: crosslinking for 2-8 h at 30-80 ℃.
Preferably, the volume ratio of the MXene colloidal solution to the flexible matrix solution in the step (3) is 1-4: 1.
The invention also protects the MXene film with high conductivity and high mechanical property prepared by the preparation method.
The invention also protects the application of the MXene film with high conductivity and high mechanical property in preparing the conductive material.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides an MXene conductive film with high mechanical property and high conductivity and a preparation method thereof aiming at the defects of large brittleness, low conductivity, poor mechanical property and the like of the existing film conductive material.
The preparation method of the invention comprises the following steps: hydrochloric acid and lithium fluoride are used as etching agents to treat MXene precursor MAX material Ti 3 AlC 2 Etching is carried out, the Al is removed to obtain accordion-shaped etched MXene, the etching process is the Al removing process, and the MXene forms a layer-by-layer stacked structure after the Al is removed, so that the electronic transmission is facilitated, and the conductivity of the material is improved; ultrasonically dispersing the etched MXene powder in water to obtain MXene colloidal solution; taking acrylamide as a material with the surface containing electronegative groups, adding ammonium persulfate as an initiator, and adding tetramethylethylenediamine as a cross-linking agent to obtain a colloidal solution of the acrylamide; and finally mixing the MXene colloidal solution with the polymethacrylamide colloidal solution, and placing the mixture in a mold to dry to obtain the MXene conductive film.
The preparation method is simple, the adopted hydrochloric acid and the adopted lithium fluoride are safer and more environment-friendly than hydrogen fluoride of the traditional method, the adopted polymethacrylamide matrix is simple to prepare, and the synthesis method is simpler and is easy to operate. The experimental results prove that: the MXene conductive film prepared by the method has high conductivity, high mechanical property and good durability, can meet the requirement of monitoring human body movement in medicine, and simultaneously shows great application prospect in the electronic fields of nano-generators, human skin and the like.
2. The method takes the etched MXene and the material with electronegative groups on the surface as raw materials to prepare the MXene film with high conductivity and high mechanical property, so that the preparation of powdery MXene particles into a film is realized; meanwhile, the MXene surface contains a large number of O, F groups, the bonding force with most substances is poor, the surface of the connecting material selected by the invention contains a large number of hydroxyl groups, and a large number of hydrogen bonds can be formed between the connecting material and O, F groups on the MXene surface, so that effective connection is carried out, and the problem that the bonding force with other substances is poor due to limited MXene surface groups, and the mechanical property after film forming is influenced is solved; according to the invention, by using the colloidal solution with a large number of hydroxyl groups on the surface, the colloidal solution can be effectively combined with the surface electronegative groups of MXene, the MXene is uniformly dispersed, the agglomeration of MXene particles is avoided, and the film forming property of the MXene film is improved; the preparation conditions are vacuum conditions, and the film is treated and stored in an inert atmosphere after the preparation is finished, so that the oxidation of active metal Ti is effectively avoided, the conductivity of the MXene film is improved, and the common problems of the conventional MXene-based film are solved.
3. The invention also has the following advantages:
(1) the acrylamide used by the invention can be prepared in a large amount by a mature process at present, is safe and environment-friendly, is a substance with good toughness and good film forming property, and is cheap and easy to obtain; the surface of PAM contains a large number of electronegative groups which can form a large number of hydrogen bonds with groups O, F on the surface of MXene, thus being beneficial to the combination of MXene and PAM;
(2) the MXene is etched by the aid of the hydrochloric acid and the lithium fluoride instead of the traditional hydrogen fluoride etching, so that safety risks in an etching process are greatly reduced, and operability is improved.
(3) The MXene film prepared by the method is a novel conductive material, has a sheet structure similar to graphene, has high conductivity and high capacitance, and is superior to the traditional conductive material.
Drawings
FIG. 1 is a schematic view of a scanning electron microscope before and after etching of a MAX material in embodiment 1 of the present invention; wherein, FIG. 1(a) is the SEM image before etching the MAX material, and FIG. 1(b) is the SEM image after etching the MAX material;
fig. 2 is a TEM and its energy spectrum of an MXene film prepared in example 2 of the present invention, wherein (a) is a TEM image of an original MAX material, (b) is a TEM image of the MXene film, (C) is a TEM energy spectrum C element distribution diagram of the MXene film, (d) is a TEM energy spectrum O element distribution diagram of the MXene film, (e) is a TEM energy spectrum F element distribution diagram of the MXene film, and (F) is a TEM energy spectrum Ti element distribution diagram of the MXene film;
FIG. 3 is an XRD comparison of MXene film and MAX material in example 2;
FIG. 4 is a schematic diagram of mechanical properties of MXene films prepared in examples 1, 3, 5 and 7 of the present invention;
fig. 5 is a schematic diagram of the conductivity of the MXene conductive film prepared in examples 1, 3, 5 and 7 of the present invention.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental methods described in the examples of the present invention are all conventional methods unless otherwise specified.
Example 1
The preparation method of the MXene film with high conductivity and high mechanical property comprises the following steps:
(1) preparation of etched MXene: adding 40mL of hydrochloric acid and 2g of lithium fluoride into a polytetrafluoroethylene container, and stirring for 30min at 35 ℃ to fully mix the hydrochloric acid and the lithium fluoride; weighing 2g of MAX material, slowly adding into a polytetrafluoroethylene container, and preventing the solution from boiling due to too fast addition; reacting for 24 hours at the constant temperature of 35 ℃ in a nitrogen atmosphere, wherein the whole process needs to be carried out in a fume hood, a reaction product is washed for multiple times by deionized water until the pH of a supernatant after centrifugation is more than 6, acetone is added into the centrifuged product to serve as an intercalation agent, ultrasonic oscillation is carried out for 15min, and vacuum drying is carried out for 24 hours at the temperature of 60 ℃ after suction filtration to obtain etched MXene;
(2) preparation of MXene colloidal solution: weighing 0.27g of etched MXene obtained in the step (1), adding 5mL of deionized water, performing ultrasonic treatment for 2 hours, and uniformly dispersing the mixture in water to obtain a light green MXene colloidal solution;
(3) preparation of a PAM matrix: weighing 0.5g of acrylamide, adding 5mL of deionized water, and ultrasonically dispersing for 5min to dissolve the acrylamide in water; under the ice bath condition, 5mg of ammonium persulfate is added as an initiator, ultrasonic dispersion is carried out for 5min, 30 mu L of tetramethylethylenediamine is added as a catalyst, and ultrasonic oscillation is carried out for 10min to form a stable PAM matrix solution;
(4) preparing an MXene conductive film: adding the MXene colloidal solution obtained in the step (2) into the PAM matrix solution obtained in the step (3), wherein the volume ratio of the MXene colloidal solution to the PAM matrix solution is 1: 1, stirring for 15min until the two are uniformly mixed, slowly pouring the uniformly mixed solution into a mold, putting the mold into a vacuum oven, and performing crosslinking drying for 2h at 45 ℃ to obtain the MXene conductive film (35 MXene).
Example 2
The preparation method of the MXene film with high conductivity and high mechanical property comprises the following steps:
(1) preparation of etched MXene: adding 40mL of hydrochloric acid and 2g of lithium fluoride into a polytetrafluoroethylene container, and stirring for 30min at 40 ℃ to fully mix the hydrochloric acid and the lithium fluoride; weighing 2g of MAX material, slowly adding into a polytetrafluoroethylene container, and preventing the solution from boiling due to too fast addition; reacting for 24 hours at the constant temperature of 40 ℃ in a nitrogen atmosphere, wherein the whole process needs to be carried out in a fume hood, a reaction product is washed for multiple times by deionized water until the pH of a supernatant after centrifugation is more than 6, DMSO (dimethyl sulfoxide) is added as an intercalation agent into the centrifuged product, ultrasonic oscillation is carried out for 15min, and vacuum drying is carried out for 24 hours at the temperature of 50 ℃ after suction filtration to obtain etched MXene;
(2) preparation of MXene colloidal solution: weighing 0.1g of etched MXene obtained in the step (1), adding 5mL of deionized water, performing ultrasonic treatment for 3 hours, and uniformly dispersing the mixture in water to obtain a light green MXene colloidal solution;
(3) preparing a PVA-sodium alginate matrix solution: adding 0.4g of PVA and 5mL of deionized water into a three-necked flask at 95 ℃, condensing and refluxing for 1.5h until the solution is clear and transparent, adding 0.1g of sodium alginate after the solution is cooled, fully stirring, adding 30 mu L of FeCl after the solution is uniformly stirred 3 Continuously stirring the solution for 1h to obtain PVA-sodium alginate matrix solution;
(4) preparing an MXene conductive film: adding the MXene colloidal solution obtained in the step (2) into the PVA-sodium alginate matrix solution obtained in the step (3), wherein the volume ratio of the MXene colloidal solution to the PVA-sodium alginate matrix solution is 1: and 3, stirring for 3 hours until the two are uniformly mixed, putting the uniformly mixed solution into a mold, standing and foaming the sodium alginate, putting the solution into a vacuum oven, and crosslinking and drying for 4 hours at the temperature of 60 ℃ to obtain the MXene conductive film.
Example 3
The preparation method of the MXene film with high conductivity and high mechanical property comprises the following steps:
(1) preparation of etched MXene: adding 40mL of hydrochloric acid and 2g of lithium fluoride into a polytetrafluoroethylene container, and stirring for 30min at 45 ℃ to fully mix the hydrochloric acid and the lithium fluoride; weighing 2g of MAX material, slowly adding into a polytetrafluoroethylene container, and preventing the solution from boiling due to too fast addition; the reaction is carried out for 36 hours at the constant temperature of 45 ℃ in a nitrogen atmosphere, and the whole process needs to be carried out in a fume hood. Washing the reaction product with deionized water for multiple times until the pH of the centrifuged supernatant is greater than 6, adding acetone into the centrifuged product as an intercalating agent, ultrasonically oscillating for 15min, and performing vacuum drying for 36h after suction filtration to obtain etched MXene;
(2) preparation of MXene colloidal solution: weighing 0.5g of etched MXene obtained in the step (1), adding 5mL of absolute ethyl alcohol, performing ultrasonic treatment for 2 hours, and uniformly dispersing the MXene in the absolute ethyl alcohol to obtain a light green MXene colloidal solution;
(3) preparation of polymethacrylamide (PMAm) matrix solution: weighing 0.5g of methacrylamide, adding 5mL of absolute ethyl alcohol, and carrying out ultrasonic dispersion for 5min to dissolve the acrylamide in the absolute ethyl alcohol; under the ice bath condition, 8mg of ammonium persulfate is added as an initiator, ultrasonic dispersion is carried out for 5min, then 40 mu L of tetramethylethylenediamine is added as a catalyst, and ultrasonic oscillation is carried out for 10min to form stable polymethacrylamide matrix solution;
(4) preparing an MXene conductive film: adding the MXene colloidal solution obtained in the step (2) into the polymethacrylamide matrix solution obtained in the step (3), wherein the volume ratio of the MXene colloidal solution to the polymethacrylamide matrix solution is 1: 1, stirring for 15min until the two are uniformly mixed, slowly pouring the uniformly mixed solution into a mold, putting the mold into a vacuum oven, and performing crosslinking drying for 6h at 45 ℃ to obtain the MXene conductive film (67 MXene).
Example 4
The preparation method of the MXene film with high conductivity and high mechanical property comprises the following steps:
(1) preparation of etched MXene: adding 40mL of hydrochloric acid and 2g of lithium fluoride into a polytetrafluoroethylene container, and stirring for 30min at 40 ℃ to fully mix the hydrochloric acid and the lithium fluoride; weighing 2g of MAX material, slowly adding into a polytetrafluoroethylene container, and preventing the solution from boiling due to too fast addition; reacting for 48 hours at the constant temperature of 40 ℃ in a nitrogen atmosphere, wherein the whole process needs to be carried out in a fume hood, a reaction product is washed for multiple times by deionized water until the pH of a supernatant after centrifugation is more than 6, DMSO (dimethyl sulfoxide) is added into the centrifuged product as an intercalator, ultrasonic oscillation is carried out for 15min, and the MXene is obtained after vacuum drying for 36 hours after suction filtration;
(2) preparation of MXene colloidal solution: weighing 4g of etched MXene, adding 5mL of deionized water, performing ultrasonic treatment for 4 hours, and uniformly dispersing the MXene in water to obtain a light green MXene colloidal solution;
(3) preparation of chitosan matrix solution: weighing 0.5g of chitosan, adding 5mL of deionized water, dripping two drops of acetic acid, performing ultrasonic dispersion for 5min to dissolve the chitosan in a dilute solution of the acetic acid, adding 8mg of formaldehyde as a cross-linking agent under the condition of normal temperature, and performing ultrasonic oscillation for 15min to form a stable chitosan matrix solution;
(4) preparing an MXene conductive film: adding the MXene colloidal solution obtained in the step (2) into the chitosan matrix solution obtained in the step (3), wherein the volume ratio of the MXene colloidal solution to the chitosan matrix solution is 1: and 2, stirring for 1h until the two are uniformly mixed, slowly pouring the uniformly mixed solution into a mold, putting the mold into a vacuum oven, and performing crosslinking drying at 45 ℃ for 4h to obtain the MXene conductive film.
Example 5
The preparation method of the MXene film with high conductivity and high mechanical property comprises the following steps:
(1) preparation of etched MXene: adding 30mL of hydrochloric acid, 10mL of deionized water and 2g of lithium fluoride into a polytetrafluoroethylene container, and stirring for 30min at 40 ℃ to fully mix the hydrochloric acid and the deionized water; weighing 2g of MAX material, slowly adding into a polytetrafluoroethylene container, and preventing the solution from boiling due to too fast addition; reacting for 24 hours at the constant temperature of 40 ℃ in an argon atmosphere, wherein the whole process needs to be carried out in a fume hood, washing a reaction product for multiple times by using deionized water until the pH of a supernatant after centrifugation is more than 6, adding the deionized water into the centrifuged product as an intercalation agent, carrying out ultrasonic oscillation for 15min, carrying out suction filtration, and carrying out vacuum drying for 48 hours to obtain etched MXene;
(2) preparation of MXene colloidal solution: weighing 1g of etched MXene, adding 5mL of deionized water, performing ultrasonic treatment for 2h, and uniformly dispersing the MXene in water to obtain a light green MXene colloidal solution;
(3) preparation of polyethylene glycol (PEG) matrix solution: weighing 0.5g of polyethylene glycol, adding 5mL of deionized water, and ultrasonically dispersing at 30 ℃ for 30min to dissolve the polyethylene glycol in the deionized water to form a stable polyethylene glycol (PEG) matrix solution;
(4) preparing an MXene conductive film: adding the MXene colloidal solution obtained in the step (2) into the polyethylene glycol matrix solution obtained in the step (3), wherein the volume ratio of the MXene colloidal solution to the polyethylene glycol matrix solution is 1: 1, stirring for 1h until the two are uniformly mixed, slowly pouring the uniformly mixed solution into a mould, putting the mould into a vacuum oven, and crosslinking and drying at 45 ℃ for 8h to obtain the MXene conductive film (50 MXene).
Example 6
The preparation method of the MXene film with high conductivity and high mechanical property comprises the following steps:
(1) preparation of etched MXene: adding 30mL of hydrochloric acid, 10mL of deionized water and 2g of lithium fluoride into a polytetrafluoroethylene container, and stirring at 45 ℃ for 30min to fully mix the hydrochloric acid and the deionized water; weighing 2g of MAX material, slowly adding into a polytetrafluoroethylene container, and preventing the solution from boiling due to too fast addition; reacting for 36 hours at the constant temperature of 45 ℃ in an argon atmosphere, wherein the whole process needs to be carried out in a fume hood, washing a reaction product for multiple times by using deionized water until the pH of a supernatant after centrifugation is more than 6, adding absolute ethyl alcohol into the centrifuged product as an intercalation agent, carrying out ultrasonic oscillation for 15min, carrying out suction filtration, and carrying out vacuum drying for 48 hours to obtain etched MXene;
(2) preparation of MXene colloidal solution: weighing 0.5g of etched MXene, adding 10mL of deionized water, performing ultrasonic treatment for 2 hours, and uniformly dispersing the MXene in water to obtain a light green MXene colloidal solution;
(3) preparation of polyvinyl alcohol (PVA) matrix solution: weighing 0.5g of polyethylene glycol, adding 5mL of deionized water, and magnetically stirring and dispersing at 95 ℃ for 3h to dissolve polyvinyl alcohol in the deionized water to form a stable polyvinyl alcohol matrix solution;
(4) preparing an MXene conductive film: adding the MXene colloidal solution obtained in the step (2) into the polyvinyl alcohol matrix solution obtained in the step (3), wherein the volume ratio of the MXene colloidal solution to the polyethylene glycol matrix solution is 1: and 2, stirring for 2 hours until the two are uniformly mixed, slowly pouring the uniformly mixed solution into a mold, putting the mold into a vacuum oven, and performing crosslinking drying at 45 ℃ for 4 hours to obtain the MXene conductive film.
Example 7
The preparation method of the MXene film with high conductivity and high mechanical property comprises the following steps:
(1) preparation of etched MXene: adding 30mL of hydrochloric acid, 10mL of deionized water and 2g of lithium fluoride into a polytetrafluoroethylene container, and stirring at 45 ℃ for 30min to fully mix the hydrochloric acid and the deionized water; weighing 2g of MAX material, slowly adding into a polytetrafluoroethylene container, and preventing the solution from boiling due to too fast addition; reacting for 48 hours at the constant temperature of 45 ℃ in an argon atmosphere, wherein the whole process needs to be carried out in a fume hood, the reaction product is washed for multiple times by deionized water until the pH of the supernatant after centrifugation is more than 6, DMSO (dimethyl sulfoxide) is added into the centrifuged product as an intercalator, ultrasonic oscillation is carried out for 15min, and the MXene is obtained after vacuum drying for 36 hours after suction filtration;
(2) preparation of MXene colloidal solution: weighing 2.8g of etched MXene, adding 5mL of deionized water, performing ultrasonic treatment for 3h, and uniformly dispersing the MXene in water to obtain a light green MXene colloidal solution;
(3) preparation of polyvinyl alcohol (PVA) -polyethylene glycol (PEG) matrix solution: weighing 0.3g of polyethylene glycol and 0.2g of polyvinyl alcohol, adding 5mL of deionized water, and ultrasonically dispersing for 30min at 30 ℃ to dissolve the polyethylene glycol and the polyvinyl alcohol in the deionized water to form a stable polyvinyl alcohol-polyethylene glycol matrix solution;
(4) preparing an MXene conductive film: adding the MXene colloidal solution obtained in the step (2) into the polyvinyl alcohol-polyethylene glycol matrix solution obtained in the step (3), wherein the volume ratio of the MXene colloidal solution to the polyvinyl alcohol-polyethylene glycol matrix solution is 1: 1, stirring for 1h until the two are uniformly mixed, slowly pouring the uniformly mixed solution into a mould, putting the mould into a vacuum oven, and crosslinking and drying for 6h at the temperature of 60 ℃ to obtain the MXene conductive film (85 MXene).
Example 8
The preparation method of the MXene film with high conductivity and high mechanical property comprises the following steps:
(1) preparation of etched MXene: adding 30mL of hydrochloric acid, 10mL of deionized water and 2g of lithium fluoride into a polytetrafluoroethylene container, and stirring for 30min at 40 ℃ to fully mix the hydrochloric acid and the deionized water; weighing 2g of MAX material, slowly adding into a polytetrafluoroethylene container, and preventing the solution from boiling due to too fast addition; reacting for 36 hours at the constant temperature of 40 ℃ in an argon atmosphere, wherein the whole process needs to be carried out in a fume hood, washing a reaction product for multiple times by using deionized water until the pH of a supernatant after centrifugation is more than 6, adding absolute ethyl alcohol into the centrifuged product as an intercalation agent, carrying out ultrasonic oscillation for 15min, carrying out suction filtration, and carrying out vacuum drying for 36 hours to obtain etched MXene;
(2) preparation of MXene colloidal solution: weighing 1g of etched MXene, adding 5mL of deionized water, performing ultrasonic treatment for 2h, and uniformly dispersing the MXene in water to obtain a light green MXene colloidal solution;
(3) preparing a polymethacrylamide-polyethylene glycol matrix solution: weighing 0.3g of acrylamide and 0.2g of polyethylene glycol, adding 5mL of deionized water, performing ultrasonic dispersion at 30 ℃ for 30min to dissolve the polyethylene glycol and the acrylamide in the deionized water, adding 5mg of ammonium persulfate serving as an initiator and 60 mu L of tetramethylethylenediamine serving as a catalyst to form a stable polymethacrylamide-polyethylene glycol matrix solution;
(4) preparing an MXene conductive film: adding the MXene colloidal solution obtained in the step (2) into the polymethacrylamide-polyethylene glycol matrix solution obtained in the step (3), wherein the volume ratio of the MXene colloidal solution to the polymethacrylamide-polyethylene glycol matrix solution is 1: and 4, stirring for 1h until the two are uniformly mixed, slowly pouring the uniformly mixed solution into a mold, putting the mold into a vacuum oven, and performing crosslinking drying for 8h at the temperature of 45 ℃ to obtain the MXene conductive film.
Example 9
The preparation method of the MXene thin film with high conductivity and high mechanical property is the same as the preparation steps of the embodiment 1, except that the amount of the lithium fluoride in the step (1) is 3g, and the MXene thin film is obtained by crosslinking at 30 ℃ for 8h in the step (4).
Example 10
The preparation method of the MXene thin film with high conductivity and high mechanical property is the same as the preparation steps of the embodiment 1, except that the amount of the lithium fluoride in the step (1) is 4g, and the MXene thin film is obtained by crosslinking at 80 ℃ for 2h in the step (4).
MXene films with high conductivity and high mechanical property are prepared in the embodiments 1-10 of the invention, and the effects are parallel, and the following conductive film materials prepared in the embodiments 1, 3, 5 and 7 are taken as examples for research, and the specific research methods and results are as follows:
comparing fig. 1(a) to fig. 1(b), fig. 1(b) shows an accordion-like lamellar structure, indicating that MXene has been successfully etched.
In comparison, FIG. 2(a) is a TEM image of the MAX raw material and FIG. (b) is a TEM image of MXene, the MXene lamella after etching is thinner, which proves that Al is removed during etching. The TEM energy spectrum of MXene shows that the etched MXene material contains C, O, F, Ti four elements, which proves that Al element is removed and is consistent with TEM result.
From the XRD of fig. 3, it is shown that after etching MAX, a distinct 002 peak appears around 7 °, which is a characteristic peak of MXene, indicating that MXene has been successfully prepared.
FIG. 4 is a drawing of a conductive film cut to a size of 1X 4cm using a die and subjected to a tensile test using a universal tensile tester; the results show that the mechanical properties of the film gradually decrease with increasing MXene content, and the film has the best mechanical properties at an MXene content of 35%.
FIG. 5 is a graph of the resistance of a thin film material connected across a digital source meter, calculated from voltage and current, and further calculated from the conductivity of the thin film according to the equation σ L/RS; the results show that the film conductivity increases with increasing MXene content;
in the formula, sigma is the conductivity of the sample, L is the length (m) of the sample, R is the resistance (omega) of the sample, S is the cross-sectional area (square meter), and the samples tested are examples 1, 3, 5 and 7.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. The preparation method of the MXene film with high conductivity and high mechanical property is characterized by comprising the following steps:
(1) preparation of MXene colloidal solution:
s1, etching the MAX material in an inert atmosphere to obtain etched MXene;
s2, dispersing the etched MXene obtained in the step S1 in a benign solvent to form a stable MXene colloidal solution;
(2) preparing a flexible matrix solution: dissolving a material with the surface containing electronegative groups in a benign solvent, adding a cross-linking agent, and uniformly stirring and mixing to obtain a flexible matrix solution;
(3) preparation of MXene film: and (3) adding the MXene colloidal solution obtained in the step (1) into the flexible matrix solution obtained in the step (2), uniformly mixing, and then heating for crosslinking and forming to obtain the MXene film.
2. The method for preparing MXene film with high conductivity and high mechanical property as claimed in claim 1, wherein the MAX material of step S1 comprises Ti 3 AlC 2 、Nb 2 AlC，Mo 2 Ga 2 C，Ti 2 AlC。
3. The method for preparing the MXene film with high conductivity and high mechanical property according to claim 1, wherein the etching method in step S1 is as follows:
adding lithium fluoride and MAX materials into a hydrochloric acid solution in an inert atmosphere, reacting for 24-48 h at 35-45 ℃, centrifuging, washing, adding an intercalator, vibrating for layering, and vacuum drying to obtain etched MXene;
wherein the concentration of the hydrochloric acid is 9-12 mol/L, and the mass ratio of the lithium fluoride to the MAX material is 1-2: 1; the intercalation agent is selected from deionized water, absolute ethyl alcohol, DMSO or acetone.
4. The method for preparing the MXene film with high conductivity and high mechanical property according to claim 1, wherein the benign solvent in the step S2 and the step (2) is selected from deionized water, absolute ethyl alcohol or DMSO, and the volume ratio of the etched MXene to the benign solvent is 0.1-4 g: 5-10 mL.
5. The method for preparing the MXene film with high conductivity and high mechanical property according to claim 1, wherein the material with electronegative groups on the surface in the step (2) is selected from one or more of acrylamide, sodium alginate, polyvinyl alcohol, polyethylene glycol, chitosan and polymethacrylamide;
the crosslinking agent is selected from tetramethylethylenediamine, FeCl 3 Or formaldehyde, wherein the volume ratio of the mass of the cross-linking agent, the mass of the material with the surface containing the electronegative groups and the benign solvent is 0.01-0.05 g: 1 g: 5-10 mL.
6. The method for preparing MXene film with high conductivity and high mechanical property as claimed in claim 5, wherein in step (2), when acrylamide or methacrylamide is used as the material with electronegative groups on the surface, initiator ammonium persulfate is also added.
7. The method for preparing MXene film with high conductivity and high mechanical property as claimed in claim 1, wherein the crosslinking reaction conditions in step (3) are as follows: crosslinking for 2-8 h at 30-80 ℃.
8. The method for preparing the MXene film with high conductivity and high mechanical property as claimed in claim 1, wherein the volume ratio of MXene colloid solution to flexible matrix solution in the step (3) is 1-4: 1.
9. An MXene film with high conductivity and high mechanical property prepared by the preparation method of any one of claims 1 to 8.
10. Use of the high conductivity high mechanical property MXene film of claim 9 in the preparation of conductive material.
CN202210877139.9A 2022-07-25 2022-07-25 MXene film with high conductivity and high mechanical property as well as preparation method and application thereof Pending CN115109288A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112876712A (en) * 2021-01-21 2021-06-01 北京理工大学 MXene-based flexible polyvinyl alcohol electromagnetic shielding composite film and preparation method thereof
CN113087972A (en) * 2021-03-25 2021-07-09 北京林业大学 MXene/silver nanowire/nanocellulose composite film and preparation method thereof
WO2022080321A1 (en) * 2020-10-15 2022-04-21 株式会社村田製作所 Electroconductive two-dimensional particles, method for producing same, electroconductive film, electroconductive composite material and electroconductive paste

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022080321A1 (en) * 2020-10-15 2022-04-21 株式会社村田製作所 Electroconductive two-dimensional particles, method for producing same, electroconductive film, electroconductive composite material and electroconductive paste
CN112876712A (en) * 2021-01-21 2021-06-01 北京理工大学 MXene-based flexible polyvinyl alcohol electromagnetic shielding composite film and preparation method thereof
CN113087972A (en) * 2021-03-25 2021-07-09 北京林业大学 MXene/silver nanowire/nanocellulose composite film and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘梅 等: ""PVA 诱导 Ti3C2TxMXene 交联构筑三维结构电极及其储锂性能研究"", 《吉林师范大学学报（自然科学版）》, vol. 43, no. 1, pages 1 - 2 *

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