CN115094621A - Skin-core type MXene fiber aerogel and preparation method thereof - Google Patents
Skin-core type MXene fiber aerogel and preparation method thereof Download PDFInfo
- Publication number
- CN115094621A CN115094621A CN202210780931.2A CN202210780931A CN115094621A CN 115094621 A CN115094621 A CN 115094621A CN 202210780931 A CN202210780931 A CN 202210780931A CN 115094621 A CN115094621 A CN 115094621A
- Authority
- CN
- China
- Prior art keywords
- mxene
- core
- skin
- fiber
- aerogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
-
- 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
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a skin-core MXene fiber aerogel and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a sheath-core MXene composite fiber; preparing MXene composite fiber aerogel; reducing to prepare graphene/MXene composite fiber aerogel; establishing fusion anchor nodes among MXene-based composite fibers by a wet-laid process to enhance the overall consistency and structural strength of the fiber felt and form a skin-core graphene oxide/MXene colloidal fiber felt; and then preparing the high-conductivity graphene/MXene fiber aerogel through freeze drying and reduction processes, wherein the surface of the MXene fiber is coated by the high-conductivity graphene, and a hydrophobic protective layer is formed on the surface of the MXene, so that the contact area of the MXene and the air can be greatly reduced, the environmental stability and durability of the MXene and the electromagnetic shielding durability can be improved, and the application of the flexible, efficient and durable electromagnetic shielding material is realized.
Description
Technical Field
The invention relates to the technical field of electromagnetic shielding aerogel, in particular to skin-core MXene fiber aerogel and a preparation method thereof.
Background
In recent years, with the rapid development and application of 5G information technology and electronic products, the electromagnetic waves brought by the technology not only affect the precision of precision electronic equipment, but also bring great threats to the leakage of electromagnetic information and even human living environment, for example, the long-term electromagnetic radiation environment increases the risk of cardiovascular and cerebrovascular diseases and the like. In addition, the rapid development of flexible smart wearable electronics also puts new goals and requirements on flexible electromagnetic shielding materials. Therefore, the development of the light-weight, flexible, durable and stable electromagnetic shielding material with high electromagnetic shielding effectiveness is a basic guarantee for meeting the development requirements of the flexible intelligent wearable electronic device.
At present, a flexible conductive electromagnetic shielding material is generally obtained by coating, chemical plating, electroplating and the like on a film or a flexible fabric substrate, however, poor conductivity of the fabric substrate can cause low electromagnetic shielding effectiveness of the prepared electromagnetic shielding material, low coating fastness of the electromagnetic shielding active material, poor air permeability and moisture permeability and the like. Aerogel materials are considered to be an ideal electromagnetic shielding material due to the characteristics of small density, developed pore structure, low specific surface area and the like. MXene, a novel two-dimensional layered nanomaterial, has better dispersibility, processability, conductivity and electromagnetic shielding effectiveness than carbon materials (116dB, Iqbal et al, Science, 2020, 369, 446-. Therefore, the MXene prepared into the aerogel is expected to obtain a material with high electromagnetic shielding effectiveness.
However, MXene is very susceptible to moisture absorption in a humid environment due to its abundant functional groups and surface termination nodes, resulting in oxidation and disintegration of the lamellar structure to form titanium dioxide, ultimately resulting in material performance degradation and loss of function. At present, methods such as antioxidant treatment, surfactant modification, heat treatment and polymer wrapping are generally adopted to inhibit the oxidation of MXene, but the preparation process is complex, and the application performance of the MXene material is influenced by the reduction of the conductivity of the modified MXene material. Therefore, developing an efficient durable electromagnetic shielding MXene aerogel is always a great challenge on the premise of not deteriorating the conductivity of the MXene material; therefore, a skin-core type MXene fiber aerogel and a preparation method thereof are provided for solving the problems.
Disclosure of Invention
In order to make up for the defects of the prior art and solve at least one problem, the invention provides a skin-core MXene fiber aerogel and a preparation method thereof.
A preparation method of a skin-core type MXene fiber aerogel comprises the following steps:
step S1: preparing a sheath-core MXene composite fiber;
step S2: preparing MXene composite fiber aerogel;
step S3: and reducing to prepare the graphene/MXene composite fiber aerogel.
Preferably, in step S1, the core-sheath MXene composite fiber is prepared as follows: MXene dispersion liquid is used as core layer spinning liquid, graphene oxide is used as cortex spinning liquid, a coaxial needle with the inner diameter of 0.16-2.27 mm and the outer diameter of 0.31-2.77 mm is used as a spinneret orifice, the cortex spinning liquid and the core layer spinning liquid are injected into a coagulating bath at the speed of 0.5-600 mL/h to prepare primary spinning colloidal fiber, and the primary spinning colloidal fiber is coagulated in the coagulating bath for 0.5-10 minutes and then transferred into an ethanol water solution.
Preferably, in the step S1, the concentration of the MXene dispersion is selected to be 0.01 to 20 wt%; the concentration of the graphene oxide is selected to be 0.01-20 wt%; wherein the coagulating bath is 0.5-10 wt% of CaCl 2 、0.5～10wt％ZnCl 2 、0.5～10wt％MgCl 2 One or more of 0.5-10 wt% NaCl, absolute ethyl alcohol, 0.1-5% chitosan and 20-99% acetic acid solution.
Preferably, in the step S2, 5 to 200g of the colloidal fibers prepared in the step S1 are prepared into a colloidal fiber mat with a thickness of 0.2 to 20mm by a wet-laying method, and then the colloidal fiber mat is washed with water for 1 to 3 times to sufficiently remove the residual coagulant in the colloidal fiber mat; the gel fiber felt is firstly dried at the temperature of 30-70 ℃ for 0.5-10 minutes and then is prepared into MXene composite fiber aerogel by a freeze drying or supercritical carbon dioxide drying method.
Preferably, in the step S2, in the method of freeze drying or supercritical carbon dioxide drying, the freeze drying temperature is controlled to be-30 ℃ to-100 ℃, and the freeze drying time is controlled to be 5-24 hours; the flow rate of the carbon dioxide fluid used for supercritical carbon dioxide drying is 500-3000L/h, the pressure is 1-20MPa, and the supercritical drying time is 1-20 minutes.
Preferably, in the step S3, the MXene composite fiber aerogel prepared in the step S2 is subjected to chemical reduction or heat treatment to obtain the highly conductive graphene/MXene composite fiber aerogel, wherein the chemical reduction adopts 10 to 55 wt% of hydroiodic acid, 1 to 80 wt% of hydrazine hydrate, 1 to 40 wt% of vitamin C, and 1 to 40 wt% of sodium bisulfite, the chemical reduction temperature is 50 to 95 ℃, and the time is 0.1 to 8 hours; the heat treatment temperature is 220 ℃ and 1500 ℃, and the heat treatment time is 0.1-5 h.
The skin-core MXene fiber aerogel prepared by the preparation method of any one of claims 1 to 6 is applied to the fields of heat preservation and insulation, pressure sensing and oil-water separation.
The invention has the advantages that:
the method comprises the steps of preparing the skin-core graphene oxide/MXene composite fibers by a coaxial spinning method, and establishing fusion anchor nodes among the MXene-based composite fibers by means of better fusion characteristics and easy adhesion characteristics of the skin graphene oxide, so as to enhance the overall consistency and structural strength of a fiber felt and form the skin-core graphene oxide/MXene colloidal fiber felt; and then preparing the highly-conductive graphene/MXene fiber aerogel through freeze drying and reduction processes, wherein the surface of the MXene fiber is coated by the highly-conductive graphene, and a hydrophobic protective layer is formed on the surface of the MXene, so that the water absorption of the MXene composite fiber can be reduced, the contact area of the MXene and air can be greatly reduced, the environmental stability and durability of the MXene and the electromagnetic shielding durability can be improved, and the application of the flexible, efficient and durable electromagnetic shielding material can be realized.
The invention develops an efficient durable MXene-based fiber aerogel material based on a coaxial spinning technology and a wet-laid technology, and the efficient durable MXene-based fiber aerogel material has the following advantages:
1. the popularization is strong. The composite fiber skin layer adopted by the invention can be PEDOT: PSS, carbon nanotubes, PDMS, carboxymethyl cellulose, polyvinyl alcohol, and the like.
2. By utilizing the fusion riveting effect of the cortical graphene oxide, the overall consistency of the MXene-based fiber aerogel structure is improved, the stress dispersion transfer in the stress process is facilitated, and the prepared MXene-based fiber aerogel has excellent compression performance and compression recovery performance.
3. The method has the advantages of simple process, easy realization, low production cost and suitability for batch production.
4. The skin-core MXene-based fiber aerogel prepared by the method is small in density, developed in pores, strong in hydrophobicity and high in conductivity; the skin-core MXene-based fiber aerogel prepared by the method has excellent electromagnetic shielding performance, the electromagnetic shielding efficiency can reach 90dB, an electromagnetic shielding mechanism mainly absorbing waves is shown, and the secondary pollution of electromagnetic waves can be fully reduced; the performance of the core-sheath MXene-based fiber aerogel prepared by the method is adjustable and controllable, and the performance of the core-sheath MXene-based fiber aerogel can be adjusted by adjusting the thickness, the diameter of a spinneret orifice, the area density and the volume density of the fiber aerogel; due to the protection effect of the skin graphene, moisture absorption, oxidation and degradation of MXene are inhibited, the prepared skin-core type MXene-based fiber aerogel has excellent electromagnetic shielding durability, and the retention rate of the electromagnetic shielding effectiveness can reach 85% after 6 months.
5. The application range is wide. The skin-core MXene-based fiber aerogel prepared by the method can be used in the fields of heat preservation and insulation, pressure sensing, oil-water separation and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a schematic diagram of example 1 and comparative example 1 of the present invention;
FIG. 2 is a pictorial view of example 7;
FIG. 3 is a microscopic view of examples 1 and 7 and comparative example 1;
FIG. 4 is the water contact angle for example 7 and comparative example 1;
FIG. 5 is a diagram of a compressed and restored real object in example 7;
FIG. 6 is a scanning electron micrograph, a power spectrum and an aerogel thereof of the fibers prepared in example 7;
FIG. 7 shows the electromagnetic shielding performance of examples 1 to 7;
FIG. 8 shows electromagnetic shielding properties of example 5 and comparative examples 2 to 4;
fig. 9 is electromagnetic shielding durability of example 7 and comparative example 5;
FIG. 10 illustrates the electromagnetic shielding mechanism of examples 1 to 7;
FIG. 11 is a schematic diagram of oil-water separation in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of a skin-core MXene fiber aerogel comprises the following steps:
step S1: preparing a sheath-core MXene composite fiber;
step S2: preparing MXene composite fiber aerogel;
step S3: and reducing to prepare the graphene/MXene composite fiber aerogel.
As an embodiment of the present invention, in step S1, the core-sheath MXene composite fiber is prepared as follows: the method comprises the steps of taking MXene dispersion liquid as core layer spinning liquid, taking graphene oxide as skin layer spinning liquid, taking a coaxial needle with the inner diameter of 0.16-2.27 mm and the outer diameter of 0.31-2.77 mm as a spinneret orifice, injecting the skin layer spinning liquid and the core layer spinning liquid into a coagulating bath at the speed of 0.5-600 mL/h to prepare primary spinning colloidal fibers, coagulating the primary spinning colloidal fibers in the coagulating bath for 0.5-10 minutes, and transferring the primary spinning colloidal fibers into an ethanol water solution.
In one embodiment of the present invention, in step S1, the concentration of the MXene dispersion is selected to be 0.01 to 20 wt%; the concentration of the graphene oxide is selected to be 0.01-20 wt%; wherein the coagulating bath is 0.5-10 wt% of CaCl 2 、0.5～10wt％ZnCl 2 、0.5～10wt％MgCl 2 One or more of 0.5-10 wt% NaCl, absolute ethyl alcohol, 0.1-5% chitosan and 20-99% acetic acid solution.
In step S2, 5 to 200g of the colloidal fibers prepared in step S1 are prepared into a colloidal fiber mat with a thickness of 0.2 to 20mm by a wet-laying method, and then the colloidal fiber mat is washed 1 to 3 times to sufficiently remove the residual coagulant in the colloidal fiber mat; the gel fiber felt is firstly dried at the temperature of 30-70 ℃ for 0.5-10 minutes and then is prepared into MXene composite fiber aerogel by a freeze drying or supercritical carbon dioxide drying method.
In one embodiment of the present invention, in the step S2, the freeze-drying or supercritical carbon dioxide drying method includes controlling the freeze-drying temperature to be-30 ℃ to-100 ℃ and the freeze-drying time to be 5-24 hours; the flow rate of the carbon dioxide fluid used for supercritical carbon dioxide drying is 500-3000L/h, the pressure is 1-20MPa, and the supercritical drying time is 1-20 minutes.
As an embodiment of the invention, in the step S3, the MXene composite fiber aerogel prepared in the step S2 is subjected to chemical reduction or heat treatment to obtain the highly conductive graphene/MXene composite fiber aerogel, wherein the chemical reduction is performed by using 10 to 55 wt% of hydroiodic acid, 1 to 80 wt% of hydrazine hydrate, 1 to 40 wt% of vitamin C, and 1 to 40 wt% of sodium bisulfite, the chemical reduction temperature is 50 to 95 ℃, and the chemical reduction time is 0.1 to 8 hours; the heat treatment temperature is 220 ℃ and 1500 ℃, and the heat treatment time is 0.1-5 h.
The skin-core MXene fiber aerogel prepared by the preparation method of any one of claims 1 to 6 is applied to the fields of heat preservation and insulation, pressure sensing and oil-water separation.
Specific examples are given below:
example 1
A preparation method of a skin-core MXene fiber aerogel comprises the following steps:
1. preparing the core-sheath MXene composite fiber: MXene dispersion liquid with the concentration of 20 wt% is used as core layer spinning liquid, graphene oxide with the concentration of 1 wt% is used as skin layer spinning liquid, a coaxial needle with the inner diameter of 0.23mm and the outer diameter of 0.7mm is used as a spinneret orifice, and the core layer spinning liquid and the outer layer spinning liquid are injected into 5 wt% MgCl at the speed of 1mL/h and 0.5mL/h respectively 2 In the coagulating bath, the as-spun colloidal fibers were coagulated in the coagulating bath for 10 minutes and then transferred to an aqueous ethanol solution.
2. Preparing a skin-core MXene composite fiber aerogel: preparing the colloidal fiber prepared in the step 1 into a colloidal fiber felt with the thickness of 1mm by a wet-laying method, then washing for 3 times to fully remove residual coagulants in the colloidal fiber felt, firstly drying the colloidal fiber felt at 50 ℃ for 5 minutes, and then freeze-drying at-50 ℃ for 24 hours to prepare the skin-core MXene composite fiber aerogel.
3. Reducing to prepare the graphene/MXene composite fiber aerogel: and (3) reducing the skin-core MXene composite fiber aerogel prepared in the step (2) by 45 wt% of hydroiodic acid at 90 ℃ for 4 hours.
As can be seen from fig. 11, the embodiment can almost completely absorb the pump oil, exhibiting good oil-water separation performance.
Example 2
A preparation method of a skin-core type MXene fiber aerogel comprises the following steps:
1. preparing the core-sheath MXene composite fiber: MXene dispersion liquid with the concentration of 20 wt% is used as core layer spinning liquid, graphene oxide with the concentration of 1 wt% is used as skin layer spinning liquid, a coaxial needle with the inner diameter of 0.23mm and the outer diameter of 0.7mm is used as a spinneret orifice, and the core layer spinning liquid and the outer layer spinning liquid are injected into 5 wt% MgCl at the speed of 1mL/h and 0.5mL/h respectively 2 In the coagulation bath, the as-spun colloidal fibers were coagulated in the coagulation bath for 10 minutes and then transferred to an aqueous ethanol solution.
2. Preparing a skin-core MXene composite fiber aerogel: preparing the colloidal fiber prepared in the step 1 into a colloidal fiber felt with the thickness of 2mm by a wet-laying method, then washing for 3 times to fully remove residual coagulants in the colloidal fiber felt, firstly drying the colloidal fiber felt at 50 ℃ for 5 minutes, and then freeze-drying at-50 ℃ for 24 hours to prepare the skin-core MXene composite fiber aerogel.
3. Reducing to prepare the graphene/MXene composite fiber aerogel: and (3) reducing the core-skin MXene composite fiber aerogel prepared in the step (2) by 45 wt% of hydroiodic acid at 90 ℃ for 4 hours.
Example 3
A preparation method of a skin-core MXene fiber aerogel comprises the following steps:
1. preparing the sheath-core MXene composite fiber: MXene dispersion liquid with the concentration of 20 wt% is used as core layer spinning liquid, graphene oxide with the concentration of 1 wt% is used as skin layer spinning liquid, a coaxial needle with the inner diameter of 0.23mm and the outer diameter of 0.7mm is used as a spinneret orifice, and the core layer spinning liquid and the outer layer spinning liquid are injected into 5 wt% MgCl at the speed of 1mL/h and 0.5mL/h respectively 2 In the coagulating bath, the as-spun colloidal fibers were coagulated in the coagulating bath for 10 minutes and then transferred to an aqueous ethanol solution.
2. Preparing a skin-core MXene composite fiber aerogel: preparing the colloidal fiber prepared in the step 1 into a colloidal fiber felt with the thickness of 3mm by a wet-laying method, then washing for 3 times to fully remove residual coagulants in the colloidal fiber felt, drying the colloidal fiber felt at 50 ℃ for 5 minutes, and then freeze-drying at-50 ℃ for 24 hours to prepare the skin-core MXene composite fiber aerogel.
3. Reducing to prepare the graphene/MXene composite fiber aerogel: and (3) reducing the core-skin MXene composite fiber aerogel prepared in the step (2) by 45 wt% of hydroiodic acid at 90 ℃ for 4 hours.
Example 4
A preparation method of a skin-core type MXene fiber aerogel comprises the following steps:
1. preparing the core-sheath MXene composite fiber: MXene dispersion liquid with the concentration of 20 wt% is used as core layer spinning liquid, graphene oxide with the concentration of 1 wt% is used as skin layer spinning liquid, a coaxial needle with the inner diameter of 0.23mm and the outer diameter of 0.7mm is used as a spinneret orifice, and the core layer spinning liquid and the outer layer spinning liquid are injected into 5 wt% MgCl at the speed of 1mL/h and 0.5mL/h respectively 2 In the coagulation bath, the as-spun colloidal fibers were coagulated in the coagulation bath for 10 minutes and then transferred to an aqueous ethanol solution.
2. Preparing a skin-core MXene composite fiber aerogel: preparing the colloidal fiber prepared in the step 1 into a colloidal fiber felt with the thickness of 4mm by a wet-laying method, then washing for 3 times to fully remove residual coagulants in the colloidal fiber felt, firstly drying the colloidal fiber felt at 50 ℃ for 5 minutes, and then freeze-drying at-50 ℃ for 24 hours to prepare the skin-core MXene composite fiber aerogel.
3. Reducing to prepare the graphene/MXene composite fiber aerogel: and (3) reducing the skin-core MXene composite fiber aerogel prepared in the step (2) by 45 wt% of hydroiodic acid at 90 ℃ for 4 hours.
Example 5
A preparation method of a skin-core MXene fiber aerogel comprises the following steps:
1. preparing the core-sheath MXene composite fiber: MXene dispersion with concentration of 20 wt% was used as core layer spinning solution with concentration of 1 wt%The graphene oxide is a skin layer spinning solution, a coaxial needle with the inner diameter of 0.23mm and the outer diameter of 0.7mm is used as a spinneret orifice, and the core layer spinning solution and the outer layer spinning solution are injected into 5 wt% MgCl at the speed of 1mL/h and 0.5mL/h respectively 2 In the coagulation bath, the as-spun colloidal fibers were coagulated in the coagulation bath for 10 minutes and then transferred to an aqueous ethanol solution.
2. Preparing a skin-core MXene composite fiber aerogel: preparing the colloidal fiber prepared in the step 1 into a colloidal fiber felt with the thickness of 5mm by a wet-laying method, then washing for 3 times to fully remove residual coagulants in the colloidal fiber felt, firstly drying the colloidal fiber felt at 50 ℃ for 5 minutes, and then freeze-drying at-50 ℃ for 24 hours to prepare the skin-core MXene composite fiber aerogel.
3. Reducing to prepare the graphene/MXene composite fiber aerogel: and (3) reducing the core-skin MXene composite fiber aerogel prepared in the step (2) by 45 wt% of hydroiodic acid at 90 ℃ for 4 hours.
Example 6
A preparation method of a skin-core type MXene fiber aerogel comprises the following steps:
1. preparing the sheath-core MXene composite fiber: MXene dispersion liquid with the concentration of 20 wt% is used as core layer spinning liquid, graphene oxide with the concentration of 1 wt% is used as skin layer spinning liquid, a coaxial needle with the inner diameter of 0.23mm and the outer diameter of 0.7mm is used as a spinneret orifice, and the core layer spinning liquid and the outer layer spinning liquid are injected into 5 wt% MgCl at the speed of 1mL/h and 0.5mL/h respectively 2 In the coagulation bath, the as-spun colloidal fibers were coagulated in the coagulation bath for 10 minutes and then transferred to an aqueous ethanol solution.
2. Preparing a skin-core MXene composite fiber aerogel: preparing the colloidal fiber prepared in the step 1 into a colloidal fiber felt with the thickness of 6mm by a wet-laying method, then washing for 3 times to fully remove residual coagulants in the colloidal fiber felt, firstly drying the colloidal fiber felt at 50 ℃ for 5 minutes, and then freeze-drying at-50 ℃ for 24 hours to prepare the skin-core MXene composite fiber aerogel.
3. Reducing to prepare the graphene/MXene composite fiber aerogel: and (3) reducing the core-skin MXene composite fiber aerogel prepared in the step (2) by 45 wt% of hydroiodic acid at 90 ℃ for 4 hours.
Example 7
A preparation method of a skin-core type MXene fiber aerogel comprises the following steps:
1. preparing the sheath-core MXene composite fiber: MXene dispersion liquid with the concentration of 20 wt% is used as core layer spinning liquid, graphene oxide with the concentration of 1 wt% is used as skin layer spinning liquid, a coaxial needle with the inner diameter of 0.23mm and the outer diameter of 0.7mm is used as a spinneret orifice, and the core layer spinning liquid and the outer layer spinning liquid are injected into 5 wt% MgCl at the speed of 1mL/h and 0.5mL/h respectively 2 In the coagulation bath, the as-spun colloidal fibers were coagulated in the coagulation bath for 10 minutes and then transferred to an aqueous ethanol solution.
2. Preparing a skin-core MXene composite fiber aerogel: preparing the colloidal fiber prepared in the step 1 into a colloidal fiber felt with the thickness of 7mm by a wet-laying method, then washing for 3 times to fully remove residual coagulants in the colloidal fiber felt, firstly drying the colloidal fiber felt at 50 ℃ for 5 minutes, and then freeze-drying at-50 ℃ for 24 hours to prepare the skin-core MXene composite fiber aerogel.
3. Reducing to prepare the graphene/MXene composite fiber aerogel: and (3) reducing the core-skin MXene composite fiber aerogel prepared in the step (2) by 45 wt% of hydroiodic acid at 90 ℃ for 4 hours.
As can be seen from fig. 2, example 7 is low in density and light in weight, can be suspended on pistil and dandelion without causing deformation of pistil and dandelion, and exhibits light weight characteristics;
as can be seen from fig. 5, the thickness of example 7 after compression with a 100g weight was 4mm, and the thickness of the fibrous aerogel after compression was still 7mm, exhibiting excellent compression resilience. The excellent compression performance and compression recovery performance of the skin-core MXene fiber-based aerogel prepared by the method are mainly attributed to the Y-shaped connection of the fiber aerogel, so that the fiber aerogel has better overall consistency, and the stress is effectively transferred in the compression stress process to disperse the stress;
as can be seen from fig. 6, the MXene fiber prepared in example 7 has a zigzag interface structure and an obvious skin-core structure, the core layer is the MXene fiber, and the skin layer is fully wrapped by graphene; in addition, the MXene-based fiber aerogel prepared in example 7 is formed by bonding fibers to each other to form a Y-shaped bond, and the inside of the aerogel has a large number of hole structures;
as can be seen from fig. 7, in the X-band, the average electromagnetic shielding effectiveness of example 1 is the lowest, and is only 16.53dB, and the average electromagnetic shielding effectiveness of example 7 is the highest, and is up to 83dB, and some frequency bands may exceed 90dB, which is mainly due to the smallest thickness (1mm) of example 1 and the highest thickness (7mm) of example 7, and the higher material thickness will result in more electromagnetic waves being absorbed. Furthermore, it can be seen from the figure that the absorption Shielding Effectiveness (SE) of examples 1 to 7 A ) Much higher than reflective Shielding Effectiveness (SE) R ) The skin-core MXene-based fiber aerogel prepared by the method disclosed by the invention is mainly characterized in that the skin-core MXene-based fiber aerogel has a good impedance matching effect, a small amount of electromagnetic waves are reflected, most of the electromagnetic waves enter the fiber aerogel, and the absorbed electromagnetic waves are converted into heat through the interface polarization effect, the dielectric loss and the ohmic loss effect in the fiber aerogel. The electromagnetic shielding mechanism of the core-skin MXene-based fiber aerogel prepared by the method, which is mainly used for absorption, is favorable for reducing the secondary pollution of electromagnetic radiation;
as can be seen from fig. 10, the electromagnetic shielding mechanism in examples 1 to 7 is absorption of electromagnetic waves, which mainly results from the better impedance matching effect of the fiber aerogel and the medium, resulting in that a small amount of electromagnetic waves are reflected, most of the electromagnetic waves enter the inside of the aerogel, and the energy of the entering electromagnetic waves is converted into heat after multiple reflection attenuation, conductive loss and polarization loss effects inside the fiber aerogel.
Comparative example 1
As shown in fig. 1, fig. 3 and fig. 4, a method for preparing a core-skin MXene fiber aerogel comprises the following steps:
preparation of MXene fiber: same as example 1 except that no coaxial spinning method was used, only MXene dope was prepared by wet spinning.
Preparation of MXene fiber aerogel: same as in example 1.
As can be seen from FIG. 1, the fibers in the embodiment 1 are bonded with each other to form a whole, the structure is uniform and compact, and the whole aerogel has good consistency; comparative example 1 the fibers were loose and did not form an integral aerogel. The graphene oxide introduced by the coaxial wet spinning adopted by the invention has a good fusion effect, and the fibers are mutually bonded to form a net structure so as to improve the structural integrity and consistency of the fiber aerogel;
as can be seen from FIG. 3, the fibers in the fibrous aerogels of example 1 and example 7 are bonded with each other to form a "Y" shaped bond, which gives the fibrous aerogel better structural integrity, while the fibers in comparative example 1 do not have any riveting function, and the inside of the aerogel presents a single fiber state;
as can be seen from fig. 4, example 7 has a water contact angle of 144.7 ° and has excellent hydrophobic characteristics; the water contact angle of comparative example 1 was 81.0 °, exhibiting hydrophilicity. The excellent hydrophobicity of example 7 is primarily due to the hydrophobicity of the cortical graphene.
Comparative example 2
As shown in fig. 8, a method for preparing a skin-core MXene fiber aerogel comprises the following steps:
1. preparing the sheath-core MXene composite fiber: same as in example 1.
2. Preparing a skin-core MXene composite fiber aerogel: same as example 1, except that the area density of the fibrous aerogel was increased to 13.3mg/cm 2 。
Wherein, the graphene/MXene composite fiber aerogel is prepared by reduction: same as in example 1.
Comparative example 3
As shown in fig. 8, a method for preparing a skin-core MXene fiber aerogel comprises the following steps:
1. preparing the sheath-core MXene composite fiber: same as in example 1.
2. Preparing a skin-core MXene composite fiber aerogel: same as example 1, except that the area density of the fibrous aerogel was increased to 15.7mg/cm 2 。
Wherein, the graphene/MXene composite fiber aerogel is prepared by reduction: same as in example 1.
Comparative example 4
As shown in fig. 8, a method for preparing a skin-core MXene fiber aerogel comprises the following steps:
1. preparing the core-sheath MXene composite fiber: same as in example 1.
2. Preparing a skin-core MXene composite fiber aerogel: same as example 1, except that the area density of the fibrous aerogel was increased to 18.9mg/cm 2 。
Wherein, the graphene/MXene composite fiber aerogel is prepared by reduction: same as in example 1.
As can be seen from fig. 8, under the same thickness of the fiber aerogel (5mm), the total electromagnetic shielding effectiveness of example 5 is the lowest, and the electromagnetic shielding effectiveness of comparative example 4 is the highest, that is, the electromagnetic shielding performance of the fiber aerogel increases with the increase of the area density thereof, mainly because at the same thickness, the higher area density means the higher volume density, and the higher content percentage of the conductive filler in the fiber aerogel causes more electromagnetic wave absorption.
Comparative example 5
As shown in fig. 9, a method for preparing a skin-core MXene fiber aerogel comprises the following steps:
1. 31.1mL of 1 wt% MXene dispersion is filtered by vacuum filtration for 1 hour;
wherein the membrane prepared in step 1 is dried for 5 minutes at 60 ℃ to obtain the membrane with the area density of 24.7mg/cm 2 A film of (2).
As can be seen from fig. 9, in example 7, after 6 months, the electromagnetic shielding effectiveness retention rate is as high as 85%, while in comparative example 5, the electromagnetic shielding effectiveness retention rate is only 48.4%, and example 7 exhibits excellent electromagnetic shielding durability, which is mainly due to the better hydrophobicity and protection effect of the skin layer MXene, the contact area of the core layer MXene can be reduced, and the oxidation resistance of the core layer MXene can be improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (7)
1. A preparation method of a skin-core type MXene fiber aerogel is characterized by comprising the following steps: the preparation method comprises the following steps:
step S1: preparing a sheath-core MXene composite fiber;
step S2: preparing MXene composite fiber aerogel;
step S3: and reducing to prepare the graphene/MXene composite fiber aerogel.
2. The method for preparing the skin-core MXene fiber aerogel according to claim 1, wherein the method comprises the following steps: therefore, in step S1, the core-sheath MXene composite fiber is prepared as follows: the method comprises the steps of taking MXene dispersion liquid as core layer spinning liquid, taking graphene oxide as skin layer spinning liquid, taking a coaxial needle with the inner diameter of 0.16-2.27 mm and the outer diameter of 0.31-2.77 mm as a spinneret orifice, injecting the skin layer spinning liquid and the core layer spinning liquid into a coagulating bath at the speed of 0.5-600 mL/h to prepare primary spinning colloidal fibers, coagulating the primary spinning colloidal fibers in the coagulating bath for 0.5-10 minutes, and transferring the primary spinning colloidal fibers into an ethanol water solution.
3. The method for preparing the skin-core MXene fiber aerogel according to claim 2, wherein the method comprises the following steps: in the step S1, the concentration of MXene dispersion liquid is selected to be 0.01-20 wt%; the concentration of the graphene oxide is selected to be 0.01-20 wt%; wherein the coagulating bath is 0.5-10 wt% of CaCl 2 、0.5～10wt％ZnCl 2 、0.5～10wt％MgCl 2 0.5-10 wt% of NaCl, absolute ethyl alcohol, 0.1-5% of chitosan and 20-99% of acetic acid solution.
4. The method for preparing the skin-core MXene fiber aerogel according to claim 3, wherein the method comprises the following steps: in the step S2, 5-200 g of the colloidal fibers prepared in the step S1 are prepared into a colloidal fiber mat with the thickness of 0.2-20 mm by a wet-laid method, and then the colloidal fiber mat is washed for 1-3 times to fully remove the residual coagulant in the colloidal fiber mat; the gel fiber felt is firstly dried at the temperature of 30-70 ℃ for 0.5-10 minutes and then is prepared into MXene composite fiber aerogel by a freeze drying or supercritical carbon dioxide drying method.
5. The method for preparing the skin-core MXene fiber aerogel according to claim 4, wherein the method comprises the following steps: in the step S2, in the freeze drying or supercritical carbon dioxide drying method, the freeze drying temperature is controlled to be-30 ℃ to-100 ℃, and the freeze drying time is controlled to be 5-24 hours; the flow rate of the carbon dioxide fluid used for supercritical carbon dioxide drying is 500-3000L/h, the pressure is 1-20MPa, and the supercritical drying time is 1-20 minutes.
6. The method for preparing the skin-core MXene fiber aerogel according to claim 5, wherein the method comprises the following steps: in the step S3, the MXene composite fiber aerogel prepared in the step S2 is subjected to chemical reduction or heat treatment to obtain the high-conductivity graphene/MXene composite fiber aerogel, wherein the chemical reduction adopts 10-55 wt% of hydroiodic acid, 1-80 wt% of hydrazine hydrate, 1-40 wt% of vitamin C and 1-40 wt% of sodium bisulfite, the chemical reduction temperature is 50-95 ℃, and the chemical reduction time is 0.1-8 hours; the heat treatment temperature is 220 ℃ and 1500 ℃, and the heat treatment time is 0.1-5 h.
7. A skin-core MXene fiber aerogel prepared by the preparation method of any one of claims 1 to 6, wherein the preparation method comprises the following steps: the MXene fiber aerogel is applied to the fields of heat preservation and insulation, pressure sensing and oil-water separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210780931.2A CN115094621B (en) | 2022-07-04 | 2022-07-04 | Sheath-core type MXene fiber aerogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210780931.2A CN115094621B (en) | 2022-07-04 | 2022-07-04 | Sheath-core type MXene fiber aerogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115094621A true CN115094621A (en) | 2022-09-23 |
| CN115094621B CN115094621B (en) | 2023-06-02 |
Family
ID=83296124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210780931.2A Active CN115094621B (en) | 2022-07-04 | 2022-07-04 | Sheath-core type MXene fiber aerogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115094621B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115467082A (en) * | 2022-10-08 | 2022-12-13 | 哈尔滨工业大学 | Preparation method of light and efficient MXene fiber non-woven fabric for electromagnetic shielding |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107680824A (en) * | 2017-11-17 | 2018-02-09 | 浙江大学 | A kind of MXene based composite fibres ultracapacitor |
| CN108620003A (en) * | 2018-05-25 | 2018-10-09 | 哈尔滨工业大学 | The telescopic preparation method with the high MXene/ graphene composite aerogels for being electromagnetically shielded effect |
| CN111799464A (en) * | 2020-07-08 | 2020-10-20 | 中国科学院电工研究所 | MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof |
| CN113692211A (en) * | 2021-08-09 | 2021-11-23 | 中国人民解放军陆军工程大学 | Preparation method of composite film electromagnetic protection material based on MXene-rGO |
| CN114454573A (en) * | 2021-12-28 | 2022-05-10 | 成都大学 | Ti3C2TxMXene/GO heterogeneous membrane and preparation method and application thereof |
-
2022
- 2022-07-04 CN CN202210780931.2A patent/CN115094621B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107680824A (en) * | 2017-11-17 | 2018-02-09 | 浙江大学 | A kind of MXene based composite fibres ultracapacitor |
| CN108620003A (en) * | 2018-05-25 | 2018-10-09 | 哈尔滨工业大学 | The telescopic preparation method with the high MXene/ graphene composite aerogels for being electromagnetically shielded effect |
| CN111799464A (en) * | 2020-07-08 | 2020-10-20 | 中国科学院电工研究所 | MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof |
| CN113692211A (en) * | 2021-08-09 | 2021-11-23 | 中国人民解放军陆军工程大学 | Preparation method of composite film electromagnetic protection material based on MXene-rGO |
| CN114454573A (en) * | 2021-12-28 | 2022-05-10 | 成都大学 | Ti3C2TxMXene/GO heterogeneous membrane and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| JIANQIAO WANG等: "A novel 1D/2D interpenetrating network architecture of MXene/cellulose composite microfiber and graphene for broadband microwave absorption" * |
| QIUYAN YANG等: "MXene/graphene hybridfibers for high performanceflexible supercapacitors" * |
| XIANHONG ZHENG等: "Interfused core-shell heterogeneous graphene/MXene fiber aerogel for high-performance and durable electromagnetic interference shielding" * |
| 郑贤宏 等: "纤维状柔性超级电容器的研究进展" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115467082A (en) * | 2022-10-08 | 2022-12-13 | 哈尔滨工业大学 | Preparation method of light and efficient MXene fiber non-woven fabric for electromagnetic shielding |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115094621B (en) | 2023-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107556495B (en) | A kind of preparation method of functional nano cellulose composite aerogel | |
| US20180282917A1 (en) | Non-woven graphene fiber fabric and preparing method thereof | |
| CN103285920B (en) | Three-dimensional fiber-based aerogel catalyst carrier and preparation method thereof | |
| Zhou et al. | Cellulose for sustainable triboelectric nanogenerators | |
| CN106496639A (en) | A kind of nano-cellulose polypyrrole polyvinyl alcohol composite conducting hydrogel and its preparation method and application | |
| CN107097492B (en) | Ultralight aeroge heat insulating material with waterproof and moisture-permeable function and preparation method thereof | |
| US11897162B2 (en) | Piezoresistive sensor material and preparation method and use thereof | |
| CN115094621B (en) | Sheath-core type MXene fiber aerogel and preparation method thereof | |
| CN113463375B (en) | In-situ hydrophobic modified aramid nano aerogel fiber as well as preparation method and application thereof | |
| CN103265010A (en) | Three-dimensional carbon fiber based aerogel material and preparation method thereof | |
| CN107254056A (en) | A kind of self-healing polyvinyl alcohol alginate dual network gel and preparation method thereof | |
| CN112195647B (en) | High-strength alginate/nano-zinc oxide composite fiber and preparation method thereof | |
| CN113233466A (en) | 3D super-elastic electrospun carbon nanofiber/MXene composite aerogel and synergistic assembly preparation method thereof | |
| CN109281224A (en) | A kind of porous graphene fabric nonwoven cloth and preparation method thereof | |
| CN108642604A (en) | The strontium titanates polypyrrole nano-composite fiber and preparation method of one-dimensional nucleocapsid structure | |
| CN106498712A (en) | Electro-magnetic wave absorption grid material and preparation method thereof | |
| CN113089126B (en) | Conductive network remodeling method based on SBS conductive fiber, conductive composite fiber prepared by using method and preparation method thereof | |
| CN114225088A (en) | Composite multilayer dressing and preparation method and application thereof | |
| CN114316375A (en) | Hierarchical pore structure composite aerogel and preparation method thereof | |
| CN109260502A (en) | A kind of fibroin hyaluronic acid mandruka and its preparation method and application | |
| CN115159500B (en) | Carbon nanofiber aerogel microsphere and preparation method thereof | |
| CN114656680B (en) | Super-elastic silk fibroin micro-nano hybrid fiber aerogel and preparation method and application thereof | |
| CN108611705A (en) | A kind of preparation method of polyacrylonitrile-radical high-performance carbon fibre | |
| CN114989550A (en) | GO/AgNPs conductive hydrogel, preparation method and application thereof | |
| CN109295615B (en) | Preparation method of durable graphene conductive silk fibroin nanofiber membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |