CN109348694A - High-strength flexible self-supporting electromagnetic wave shield film and preparation method thereof - Google Patents
High-strength flexible self-supporting electromagnetic wave shield film and preparation method thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 claims abstract description 63
- 229920001690 polydopamine Polymers 0.000 claims abstract description 43
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 39
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- 238000002156 mixing Methods 0.000 claims description 28
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
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- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 3
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- 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
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Textile Engineering (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention discloses a kind of high-strength flexible self-supporting electromagnetic wave shield films and preparation method thereof, silver nanowires is supported on nano-cellulose by the adhesive attraction of poly-dopamine, high conductivity poly-dopamine modified lithium nano-cellulose conductive fiber is obtained, first passage conductive fiber assists special adsorption to realize to two-dimentional Ti3C2Limellar stripping, improve intercalation rate and interlamellar spacing, obtain single layer or 2-10 layers of few layer of Ti3C2MXene nanometer sheet, while one-dimensional electric fiber and two-dimensional nano piece are self-assembled into three-dimensional " brick-mud " structural conductive network by the electrostatic interaction and hydrogen bond action of positive and negative charge, finally by high pressure filter press technique one-step synthesis flexible electromagnetic shielding film.Flexible self-supporting film prepared by the present invention is significant to electromagnetic shielding effect, and has the characteristics that high mechanical strength, bending flexibility is good, synthesis technology is simple, can meet the specific requirement of flexible electronic in practical application.
Description
Technical field
The present invention relates to a kind of electromagnetic wave shield films and preparation method thereof, more particularly to a kind of flexible electromagnetic shielding film
And preparation method thereof, it is applied to technical field of electromagnetic shielding.
Background technique
Electromagnetic interference and electromagnetic radiation cause to seriously endanger to portable electronic, space flight and national defense safety and human health.
Using metal as traditional electromagnetic shielding material of representative, due to the disadvantages of density is big, flexibility is poor, perishable, it is difficult to meet lightweight just
Take the demand of electronic product development.In recent years, MXene has as a kind of novel two-dimensional layer transition metal carbon/nitride
Excellent metallic conductivity (conductivity is up to 65000S/m) and ferromagnetism become a kind of ideal electromagnetic shielding material, however
Existing MXene electromagnetic wave shield film limits practical application due to the disadvantages of mechanical strength is low, bending is poor.
Forming composite material by addition unclassified stores is an excellent method for solving material defect itself.Section of South Korea
It learns Institute for Research and Technology Shahzad etc. and utilizes sodium alginate intercalation Ti3C2The method of MXene prepares high conductivity, high electromagnetic shielding
The thin-film material of efficiency (about 92dB), but the mechanical performance of film is not provided regrettably, and the tensile strength of ultra-thin materials
It is that can film put into the very important data of practical application with compression strength.The Gogotsi et al. of Univ Drexel of the U.S.
Enhance Ti using polyvinyl alcohol3C2MXene, tensile break strength is enhanced by 22MPa to 91MPa, however conductivity reduces 10
Times.Beijing University of Chemical Technology Zhang Haobin etc. induces Ti using hydrazine hydrate3C2Tx MXene film foams are prepared for hydrophobic, flexible for the first time
With the MXene foam film of lightweight, electromagnet shield effect by it is unexpanded when 53dB be increased to 70dB (X-band, 8.2-
12.4GHz), tensile strength falls to 4MPa by 16.5MPa.
Therefore, it chooses suitable reinforcing material, rationally design process conditions, high-intensitive, flexible, the efficient MXene of exploitation
Electromagnetic wave shield film is of great significance with meeting the performance requirement under flexible device bending deformation, this becomes skill urgently to be resolved
Art problem.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
High-strength flexible self-supporting electromagnetic wave shield film and preparation method thereof, film of the present invention is significant to electromagnetic shielding effect, and has
Have the characteristics that high mechanical strength, bending flexibility are good, the specific requirement of flexible electronic in practical application can be met.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of high-strength flexible self-supporting electromagnetic wave shield film, using the adhesive attraction of poly-dopamine PDA by silver nanowires
AgNWs is supported on nano-cellulose NFC, obtains the poly-dopamine modified lithium conductive fiber that form is AgNWs@PDA-NFC；And lead to
Conductive fiber collaboration special adsorption is crossed, blocky Ti is made3C2In lamella removed, increase Ti3C2Intercalation rate and thin layer between
Away from acquisition single layer or 2-10 layers of few layer of Ti3C2MXene nanometer sheet；Make finally by the electrostatic interaction and hydrogen bond of positive and negative charge
With by one-dimensional AgNWs@PDA-NFC conductive cellulose and two-dimensional Ti3C2MXene nanometer sheet constructs to form having for three-dimensional
" brick-mud " structure type conductive network carries out one-step method assembling by high pressure filter press technique, forms flexible electromagnetic shielding film, mentions
The mechanical strength of high electromagnetic wave shield film.
A kind of preparation method of high-strength flexible self-supporting electromagnetic wave shield film of the present invention, includes the following steps:
A. poly-dopamine (PDA) modified nanometer cellulose (NFC) is dispersed at least 50mL solvent, ultrasonic disperse obtains
Poly-dopamine-nano-cellulose (PDA-NFC) suspension wherein contains poly- DOPA in poly-dopamine-nano-cellulose suspension
The ratio of amine-nano-cellulose (PDA-NFC) is 0.01~0.1w/v%；Above-mentioned nano-cellulose (NFC) preferably uses nanometer
At least one of cellulose fibre, nano-cellulose whisker, regeneration nano-cellulose one-dimensional material；Above-mentioned solvent preferably uses
At least one of water, ethyl alcohol, isopropanol and dimethyl sulfoxide (DMSO) solvent；
B. by Ti3C2Powder is added in the poly-dopamine-nano-cellulose suspension prepared in the step a, and ultrasound is extremely
Few 60min, obtains the single layer of stably dispersing or 2-10 layers of few layer of Ti3C2MXene nanometer sheet and poly-dopamine-nanofiber
The mixing suspension of element, wherein contains Ti in mixing suspension3C2Ratio be 0.01~0.2w/v%；
C. silver nanowires (AgNWs) is added in the mixing suspension prepared in the step b, carries out magnetic agitation extremely
Few 30min obtains being uniformly mixed Ti3C2The high conductivity poly-dopamine that MXene nanometer sheet and form are AgNWs@PDA-NFC changes
Property conductive fiber final mixing suspension, wherein ratio in final mixing suspension containing AgNWs is 0.001~0.01w/
V%；
D. the final suspension prepared in the step c is poured into high-pressure pressure filter, adjusts pressure, filters pressing is to no longer
There is filtrate outflow, takes out filter cake vacuum drying, obtain flexible self-supporting electromagnetic wave shield film.Pass through filter press technique, preferably control pressure
By force it is 0.2~2.0MPa, carries out one-step method assembling, forms flexible electromagnetic shielding film.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the present invention method modified by the pre- intercalation of nano-cellulose and surface, increases Ti3C2Intercalation rate and thin layer between
Away from realization is to blocky Ti3C2Release effect, obtain the Ti of single layer or few layer3C2MXene nanometer sheet；
2. the present invention is acted on using the metal bonding of poly-dopamine surface catechol and AgNWs, AgNWs is adhered to
The surface PDA-NFC obtains AgNWs@PDA-NFC conductive cellulose；The present invention chooses suitable reinforcing material, rationally designs technique
Condition, high-intensitive, flexible, the efficient MXene electromagnetic wave shield film of exploitation are wanted with meeting the performance under flexible device bending deformation
It asks and is of great significance；
3. the present invention is using one-dimensional AgNWs@PDA-NFC conductive fiber and two dimension Ti3C2Intert between nanoscale twins and constructs three
" brick-mud " formula structure of dimension, both strengthens Ti3C2The electron-transport of nanoscale twins interlayer, but the machinery for enhancing fexible film is strong
Degree improves film and reflect, absorbs and the ability of multiple internal reflection electromagnetic wave under complex deformation state, with widely actually answering
Use prospect.
Detailed description of the invention
Fig. 1 is one flexible electromagnetic shielding film material object digital photograph of the embodiment of the present invention.
Fig. 2 is stretching-broken curve figure of one flexible electromagnetic shielding film of the embodiment of the present invention.
Fig. 3 is the electromagnetic shielding performance figure of one flexible electromagnetic shielding film of the embodiment of the present invention.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
Embodiment one
In the present embodiment, referring to Fig. 1, a kind of high-strength flexible self-supporting electromagnetic wave shield film utilizes poly-dopamine PDA
Adhesive attraction silver nanowires AgNWs is supported on nano-cellulose NFC, obtain form be AgNWs@PDA-NFC it is poly- more
Bar amine denatured conductive fiber；And special adsorption is cooperateed with by conductive fiber, make blocky Ti3C2In lamella removed, increase
Ti3C2Intercalation rate and thin layer spacing, obtain include single layer and 2-10 layers of few layer of Ti3C2MXene nanometer sheet；Finally by
The electrostatic interaction and hydrogen bond action of positive and negative charge, by one-dimensional AgNWs@PDA-NFC conductive cellulose and two-dimensional Ti3C2MXene
Nanometer sheet construct to be formed it is three-dimensional there is " brick-mud " structure type conductive network, pass through filter press technique, carry out one-step method assembling, shape
At flexible electromagnetic shielding film.The present embodiment utilizes the metal bonding of poly-dopamine surface catechol and silver nanowires AgNWs
Silver nanowires AgNWs is adhered to the surface PDA-NFC by effect, obtains the poly- DOPA of high conductivity that form is AgNWs@PDA-NFC
Amine denatured conductive fiber.For the present embodiment by filter press technique, control pressure is 2.0MPa, carries out one-step method assembling, forms flexible electrical
Magnetic screen film, referring to Fig. 1.20mg poly-dopamine-nano-cellulose PDA-NFC, 40mg Ti is used in the present embodiment3C2With
10g silver nanowires AgNWs forms flexible electromagnetic shielding film composite material according to component ratio.Silver nanowires is by poly- more
The bonding action of bar amine surface catechol, interacts to form conductive fiber with nano-cellulose.
In the present embodiment, referring to Fig. 1, a kind of preparation side of the present embodiment high-strength flexible self-supporting electromagnetic wave shield film
Method includes the following steps:
A. the nano-cellulose (NFC) uses nano-cellulose fiber, using poly-dopamine (PDA) modified nano fiber
The poly-dopamine of 20mg-nano-cellulose PDA-NFC, i.e., be dispersed in 50mL deionized water, ultrasonic disperse obtains by plain (NFC)
Poly-dopamine-nano-cellulose (PDA-NFC) suspension wherein contains poly- DOPA in poly-dopamine-nano-cellulose suspension
The ratio of amine-nano-cellulose (PDA-NFC) is 0.04w/v%；
B. by the Ti of 40mg3C2Powder is added in the poly-dopamine-nano-cellulose suspension prepared in the step a,
Ultrasonic 60min, that obtain stably dispersing includes single layer and 2-10 layers of few layer of Ti3C2MXene nanometer sheet and poly-dopamine-are received
The mixing suspension of rice cellulose, wherein contains Ti in mixing suspension3C2Ratio be 0.08w/v%；
C. 10g silver nanowires (AgNWs) is added in the mixing suspension prepared in the step b, carries out magnetic force and stirs
30min is mixed, obtains being uniformly mixed Ti3C2The high conductivity poly-dopamine that MXene nanometer sheet and form are AgNWs@PDA-NFC changes
Property conductive fiber final mixing suspension, wherein ratio in final mixing suspension containing AgNWs is 0.002w/v%；
D. the final suspension prepared in the step c is poured into high-pressure pressure filter, adjusting pressure is 2.0MPa, pressure
Filter takes out filter cake vacuum drying, obtains flexible self-supporting electromagnetic wave shield film to there is no filtrate outflows.
Experimental test analysis:
Flexible self-supporting electromagnetic wave shield film manufactured in the present embodiment is subjected to mechanical stretch test and is electromagnetically shielded elegant energy
Test, referring to figs. 2 and 3, the breaking strength of flexible self-supporting electromagnetic wave shield film manufactured in the present embodiment are 63.8MPa,
X-band within the scope of 8-12.5GHz, electromagnetic shielding reach as high as 21.1dB.The present embodiment high-strength flexible self-supporting electromagnetic screen
It covers film and preparation method thereof silver nanowires is supported on nano-cellulose by the adhesive attraction of poly-dopamine, obtains height and lead
Electrical poly-dopamine modified lithium nano-cellulose conductive fiber assists special adsorption to realize to two-dimentional Ti by conductive fiber3C2Piece
Layer removing, improves intercalation rate and interlamellar spacing, obtains the Ti of single layer and few layer mixing3C2MXene nanometer sheet, while one-dimensional electric is fine
Dimension is self-assembled into three-dimensional " brick-mud " structural conductive net by the electrostatic interaction and hydrogen bond action of positive and negative charge with two-dimensional nano piece
Network, finally by high pressure filter press technique one-step synthesis flexible electromagnetic shielding film.Flexible self-supporting film pair manufactured in the present embodiment
Electromagnetic shielding effect is significant, and has the characteristics that high mechanical strength, bending flexibility is good, synthesis technology is simple, can meet reality
The specific requirement of flexible electronic in the application of border.
Embodiment two
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of high-strength flexible self-supporting electromagnetic wave shield film is made using the adherency of poly-dopamine PDA
It is supported on nano-cellulose NFC with by silver nanowires AgNWs, obtains the poly-dopamine modified lithium that form is AgNWs@PDA-NFC
Conductive fiber；And special adsorption is cooperateed with by conductive fiber, make blocky Ti3C2In lamella removed, increase Ti3C2Insert
Layer rate and thin layer spacing, obtaining includes single layer and 2-10 layers of few layer of Ti3C2MXene nanometer sheet；Finally by positive and negative charge
Electrostatic interaction and hydrogen bond action, by one-dimensional AgNWs@PDA-NFC conductive cellulose and two-dimensional Ti3C2MXene nanometer sheet is constructed
Form three-dimensional has " brick-mud " structure type conductive network, passes through filter press technique, carries out one-step method assembling, forms flexible electromagnetism
Shielded film.The present embodiment is acted on using the metal bonding of poly-dopamine surface catechol and silver nanowires AgNWs, and silver is received
Rice noodles AgNWs is adhered to the surface PDA-NFC, and it is conductive to obtain the high conductivity poly-dopamine modified lithium that form is AgNWs@PDA-NFC
Fiber.For the present embodiment by filter press technique, control pressure is 2.0MPa, carries out one-step method assembling, forms flexible electromagnetic shielding film.
6.67mg poly-dopamine-nano-cellulose PDA-NFC, 40mg Ti is used in the present embodiment3C2With 10g silver nanowires AgNWs,
Flexible electromagnetic shielding film composite material is formed according to component ratio.
In the present embodiment, a kind of preparation method of the present embodiment high-strength flexible self-supporting electromagnetic wave shield film, including
Following steps:
A. the nano-cellulose (NFC) uses nano-cellulose fiber, using poly-dopamine (PDA) modified nano fiber
The poly-dopamine of 6.67mg-nano-cellulose PDA-NFC, i.e., be dispersed in 50mL deionized water, ultrasonic disperse obtains by plain (NFC)
To poly-dopamine-nano-cellulose (PDA-NFC) suspension, wherein containing poly- more in poly-dopamine-nano-cellulose suspension
The ratio of bar amine-nano-cellulose (PDA-NFC) is 0.013w/v%；
B. by the Ti of 40mg3C2Powder is added in the poly-dopamine-nano-cellulose suspension prepared in the step a,
Ultrasonic 60min, that obtain stably dispersing includes single layer and 2-10 layers of few layer of Ti3C2MXene nanometer sheet and poly-dopamine-are received
The mixing suspension of rice cellulose, wherein contains Ti in mixing suspension3C2Ratio be 0.08w/v%；
C. 10g silver nanowires (AgNWs) is added in the mixing suspension prepared in the step b, carries out magnetic force and stirs
30min is mixed, obtains being uniformly mixed Ti3C2The high conductivity poly-dopamine that MXene nanometer sheet and form are AgNWs@PDA-NFC changes
Property conductive fiber final mixing suspension, wherein ratio in final mixing suspension containing AgNWs is 0.002w/v%；
D. the final suspension prepared in the step c is poured into high-pressure pressure filter, adjusting pressure is 2.0MPa, pressure
Filter takes out filter cake vacuum drying, obtains flexible self-supporting electromagnetic wave shield film to there is no filtrate outflows.
Experimental test analysis:
Flexible self-supporting electromagnetic wave shield film manufactured in the present embodiment is subjected to mechanical stretch test and is electromagnetically shielded elegant energy
The breaking strength of test, flexible self-supporting electromagnetic wave shield film manufactured in the present embodiment is 39.8MPa, in 8-12.5GHz range
Interior X-band, electromagnetic shielding reach as high as 42.7dB.The present embodiment high-strength flexible self-supporting electromagnetic wave shield film and its preparation
Silver nanowires is supported on nano-cellulose by method by the adhesive attraction of poly-dopamine, is obtained high conductivity poly-dopamine and is changed
Property nano-cellulose conductive fiber, by conductive fiber assist special adsorption realize to two-dimentional Ti3C2Limellar stripping, improve insert
Layer rate and interlamellar spacing obtain the Ti of single layer and few layer mixing3C2MXene nanometer sheet, while one-dimensional electric fiber and two-dimensional nano piece
It is self-assembled into three-dimensional " brick-mud " structural conductive network by the electrostatic interaction and hydrogen bond action of positive and negative charge, finally by high pressure
Filter press technique one-step synthesis flexible electromagnetic shielding film.Flexible self-supporting film manufactured in the present embodiment is aobvious to electromagnetic shielding effect
It writes, and has the characteristics that high mechanical strength, bending flexibility is good, synthesis technology is simple, flexible electronic in practical application can be met
Specific requirement.
Embodiment three
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of high-strength flexible self-supporting electromagnetic wave shield film is made using the adherency of poly-dopamine PDA
It is supported on nano-cellulose NFC with by silver nanowires AgNWs, obtains the poly-dopamine modified lithium that form is AgNWs@PDA-NFC
Conductive fiber；And special adsorption is cooperateed with by conductive fiber, make blocky Ti3C2In lamella removed, increase Ti3C2Insert
Layer rate and thin layer spacing, obtaining includes single layer and 2-10 layers of few layer of Ti3C2MXene nanometer sheet；Finally by positive and negative charge
Electrostatic interaction and hydrogen bond action, by one-dimensional AgNWs@PDA-NFC conductive cellulose and two-dimensional Ti3C2MXene nanometer sheet is constructed
Form three-dimensional has " brick-mud " structure type conductive network, passes through filter press technique, carries out one-step method assembling, forms flexible electromagnetism
Shielded film.The present embodiment is acted on using the metal bonding of poly-dopamine surface catechol and silver nanowires AgNWs, and silver is received
Rice noodles AgNWs is adhered to the surface PDA-NFC, and it is conductive to obtain the high conductivity poly-dopamine modified lithium that form is AgNWs@PDA-NFC
Fiber.For the present embodiment by filter press technique, control pressure is 0.2MPa, carries out one-step method assembling, forms flexible electromagnetic shielding film.
10mg poly-dopamine-nano-cellulose PDA-NFC, 5mg Ti is used in the present embodiment3C2With 10g silver nanowires AgNWs, according to
Component ratio forms flexible electromagnetic shielding film composite material.
In the present embodiment, a kind of preparation method of the present embodiment high-strength flexible self-supporting electromagnetic wave shield film, including
Following steps:
A. the nano-cellulose (NFC) uses nano-cellulose whisker, using poly-dopamine (PDA) modified nano fiber
The poly-dopamine of 10mg-nano-cellulose PDA-NFC, i.e., be dispersed in 50mL ethyl alcohol by plain (NFC), and ultrasonic disperse obtains poly- more
Bar amine-nano-cellulose (PDA-NFC) suspension is wherein received in poly-dopamine-nano-cellulose suspension containing poly-dopamine-
The ratio of rice cellulose (PDA-NFC) is 0.02w/v%；
B. by the Ti of 5mg3C2Powder is added in the poly-dopamine-nano-cellulose suspension prepared in the step a,
Ultrasonic 60min, that obtain stably dispersing includes single layer and 2-10 layers of few layer of Ti3C2MXene nanometer sheet and poly-dopamine-are received
The mixing suspension of rice cellulose, wherein contains Ti in mixing suspension3C2Ratio be 0.01w/v%；
C. 10g silver nanowires (AgNWs) is added in the mixing suspension prepared in the step b, carries out magnetic force and stirs
30min is mixed, obtains being uniformly mixed Ti3C2The high conductivity poly-dopamine that MXene nanometer sheet and form are AgNWs@PDA-NFC changes
Property conductive fiber final mixing suspension, wherein ratio in final mixing suspension containing AgNWs is 0.002w/v%；
D. the final suspension prepared in the step c is poured into high-pressure pressure filter, adjusting pressure is 2.0MPa, pressure
Filter takes out filter cake vacuum drying, obtains flexible self-supporting electromagnetic wave shield film to there is no filtrate outflows.
Experimental test analysis:
Flexible self-supporting electromagnetic wave shield film manufactured in the present embodiment is subjected to mechanical stretch test and is electromagnetically shielded elegant energy
The breaking strength of test, flexible self-supporting electromagnetic wave shield film manufactured in the present embodiment is 34.6MPa, in 8-12.5GHz range
Interior X-band, electromagnetic shielding reach as high as 20.7dB.The present embodiment high-strength flexible self-supporting electromagnetic wave shield film and its preparation
Silver nanowires is supported on nano-cellulose by method by the adhesive attraction of poly-dopamine, is obtained high conductivity poly-dopamine and is changed
Property nano-cellulose conductive fiber, by conductive fiber assist special adsorption realize to two-dimentional Ti3C2Limellar stripping, improve insert
Layer rate and interlamellar spacing obtain the Ti of single layer and few layer mixing3C2MXene nanometer sheet, while one-dimensional electric fiber and two-dimensional nano piece
It is self-assembled into three-dimensional " brick-mud " structural conductive network by the electrostatic interaction and hydrogen bond action of positive and negative charge, finally by high pressure
Filter press technique one-step synthesis flexible electromagnetic shielding film.Flexible self-supporting film manufactured in the present embodiment is aobvious to electromagnetic shielding effect
It writes, and has the characteristics that high mechanical strength, bending flexibility is good, synthesis technology is simple, flexible electronic in practical application can be met
Specific requirement.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
Without departing from the technical principle and inventive concept of high-strength flexible self-supporting electromagnetic wave shield film of the present invention and preparation method thereof,
Belong to protection scope of the present invention.
Claims (7)
1. a kind of high-strength flexible self-supporting electromagnetic wave shield film, it is characterised in that: will using the adhesive attraction of poly-dopamine PDA
Silver nanowires AgNWs is supported on nano-cellulose NFC, and it is conductive to obtain the poly-dopamine modified lithium that form is AgNWs@PDA-NFC
Fiber；And special adsorption is cooperateed with by conductive fiber, make blocky Ti3C2In lamella removed, increase Ti3C2Intercalation rate
With thin layer spacing, single layer or 2-10 layers of few layer of Ti are obtained3C2MXene nanometer sheet；Finally by the electrostatic interaction of positive and negative charge
And hydrogen bond action, by one-dimensional AgNWs@PDA-NFC conductive cellulose and two-dimensional Ti3C2MXene nanometer sheet constructs to form three-dimensional
Have " brick-mud " structure type conductive network, pass through filter press technique, carry out one-step method assembling, formed flexible electromagnetic shielding film.
2. high-strength flexible self-supporting electromagnetic wave shield film according to claim 1, it is characterised in that: utilize poly-dopamine table
The metal bonding of face catechol and silver nanowires AgNWs act on, and silver nanowires AgNWs is adhered to the surface PDA-NFC, obtain
Form is the high conductivity poly-dopamine modified lithium conductive fiber of AgNWs@PDA-NFC.
3. high-strength flexible self-supporting electromagnetic wave shield film according to claim 1, it is characterised in that: pass through filter press technique, control
Pressure processed is 0.2~2.0MPa, carries out one-step method assembling, forms flexible electromagnetic shielding film.
4. the preparation method of high-strength flexible self-supporting electromagnetic wave shield film described in a kind of claim 1, which is characterized in that including
Following steps:
A. poly-dopamine (PDA) modified nanometer cellulose (NFC) is dispersed at least 50mL solvent, ultrasonic disperse obtains poly- more
Bar amine-nano-cellulose (PDA-NFC) suspension is wherein received in poly-dopamine-nano-cellulose suspension containing poly-dopamine-
The ratio of rice cellulose (PDA-NFC) is 0.01~0.1w/v%；
B. by Ti3C2Powder is added in the poly-dopamine-nano-cellulose suspension prepared in the step a, and ultrasound is at least
60min obtains the single layer of stably dispersing or 2-10 layers of few layer of Ti3C2MXene nanometer sheet and poly-dopamine-nano-cellulose
Mixing suspension, wherein contain Ti in mixing suspension3C2Ratio be 0.01~0.2w/v%；
C. silver nanowires (AgNWs) is added in the mixing suspension prepared in the step b, carries out magnetic agitation at least
30min obtains being uniformly mixed Ti3C2The high conductivity poly-dopamine modified lithium that MXene nanometer sheet and form are AgNWs@PDA-NFC
The final mixing suspension of conductive fiber, wherein the ratio in final mixing suspension containing AgNWs is 0.001~0.01w/
V%；
D. the final suspension prepared in the step c is poured into high-pressure pressure filter, adjusts pressure, filters pressing is to there is no filters
Liquid stream goes out, and takes out filter cake vacuum drying, obtains flexible self-supporting electromagnetic wave shield film.
5. the preparation method of high-strength flexible self-supporting electromagnetic wave shield film according to claim 4, it is characterised in that: in institute
It states in a, the nano-cellulose (NFC) is using in nano-cellulose fiber, nano-cellulose whisker, regeneration nano-cellulose
At least one one-dimensional material.
6. the preparation method of high-strength flexible self-supporting electromagnetic wave shield film according to claim 4, it is characterised in that: in institute
It states in a, the solvent is using at least one of water, ethyl alcohol, isopropanol and dimethyl sulfoxide (DMSO) solvent.
7. the preparation method of high-strength flexible self-supporting electromagnetic wave shield film according to claim 4, it is characterised in that: in institute
It states in d, by filter press technique, control pressure is 0.2~2.0MPa, carries out one-step method assembling, forms flexible electromagnetic shielding film.
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Cited By (12)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219066A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Flexible conductive thin film compositing two-dimensional graphene and one-dimensional nanowire and preparation method thereof |
| US20170088429A1 (en) * | 2015-09-24 | 2017-03-30 | Samsung Electronics Co., Ltd. | Mxene nanosheet and manufacturing method thereof |
| CN107099054A (en) * | 2017-05-12 | 2017-08-29 | 深圳大学 | Ti3C2The preparation method of MXene/ polymer composite wave-suction materials |
| CN108264885A (en) * | 2018-01-18 | 2018-07-10 | 北京林业大学 | A kind of electromagnetic shielding film of mechanics enhancing and preparation method thereof |
| CN108409286A (en) * | 2018-03-14 | 2018-08-17 | 南开大学 | Composite colloid material based on inorganic nanowires and preparation method thereof and 3D printing application |
-
2018
- 2018-09-13 CN CN201811064886.0A patent/CN109348694B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219066A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Flexible conductive thin film compositing two-dimensional graphene and one-dimensional nanowire and preparation method thereof |
| US20170088429A1 (en) * | 2015-09-24 | 2017-03-30 | Samsung Electronics Co., Ltd. | Mxene nanosheet and manufacturing method thereof |
| CN107099054A (en) * | 2017-05-12 | 2017-08-29 | 深圳大学 | Ti3C2The preparation method of MXene/ polymer composite wave-suction materials |
| CN108264885A (en) * | 2018-01-18 | 2018-07-10 | 北京林业大学 | A kind of electromagnetic shielding film of mechanics enhancing and preparation method thereof |
| CN108409286A (en) * | 2018-03-14 | 2018-08-17 | 南开大学 | Composite colloid material based on inorganic nanowires and preparation method thereof and 3D printing application |
Cited By (17)
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| CN110090603A (en) * | 2019-04-12 | 2019-08-06 | 湖北大学 | A kind of MXene and graphene oxide composite aerogel and its preparation method and application |
| CN110223800A (en) * | 2019-06-25 | 2019-09-10 | 武汉工程大学 | A kind of preparation method of biodegradable flexible transparent conductive film |
| CN111132533A (en) * | 2019-12-31 | 2020-05-08 | 浙江工业大学 | MXene/silver nanowire composite electromagnetic shielding film |
| CN111132533B (en) * | 2019-12-31 | 2021-07-13 | 浙江工业大学 | MXene/silver nanowire composite electromagnetic shielding film |
| CN112930100A (en) * | 2021-01-20 | 2021-06-08 | 中国电子科技集团公司第三十三研究所 | Metal transparentized electromagnetic shielding material and preparation method thereof |
| CN113004556A (en) * | 2021-02-22 | 2021-06-22 | 西安理工大学 | Preparation method of CNF/MXene-silver nanowire composite film |
| CN113004556B (en) * | 2021-02-22 | 2023-06-27 | 深圳市群智科技有限公司 | Preparation method of CNF/MXene-silver nanowire composite film |
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