CN112194819B - Preparation method of graphene nanosheet/cellulose aerogel composite material - Google Patents
Preparation method of graphene nanosheet/cellulose aerogel composite material Download PDFInfo
- Publication number
- CN112194819B CN112194819B CN202011010794.1A CN202011010794A CN112194819B CN 112194819 B CN112194819 B CN 112194819B CN 202011010794 A CN202011010794 A CN 202011010794A CN 112194819 B CN112194819 B CN 112194819B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- graphene
- cellulose aerogel
- solution
- composite material
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- 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
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—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 at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a graphene nanosheet/cellulose aerogel composite material, which comprises the following steps: firstly, adding graphene nanosheets into deionized water, and performing ultrasonic dispersion to form a graphene nanosheet solution; then soaking the cellulose aerogel into the graphene nanosheet solution, ultrasonically dispersing and drying to obtain graphene nanosheets/cellulose aerogel; and finally, soaking the graphene nanosheet/cellulose aerogel in a polyvinylidene fluoride/N' N dimethylformamide solution, curing and hot-pressing to obtain the graphene nanosheet/cellulose aerogel composite material. The cellulose aerogel with a porous structure is combined with the graphene with a layered structure to obtain a three-dimensional multilayer structure containing a conductive network, and the composite material with low filler content, low thickness and high electromagnetic shielding performance is obtained. Meanwhile, the preparation method is simple, convenient and feasible, has lower production cost and is easy for batch production.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a graphene nanosheet/cellulose aerogel composite material.
Background
The explosive development and widespread adoption of wireless networks, portable digital hardware and communication facilities has greatly facilitated the improvement of people's living standards, but the inevitable electromagnetic interference radiation has increased to an unprecedented level, not only interfering with the normal functions of nearby electronic equipment, but also causing immeasurable damage to human health. Therefore, there is a strong need for efficient electromagnetic interference shielding materials for electronic devices and human beings to avoid these undesirable interference signals. Electromagnetic interference shielding conductive polymer composite materials as a substitute for conventional metals are receiving increasing attention due to their characteristics of easy processing, corrosion resistance, low cost, adjustability, and the like. However, the achievement of excellent electromagnetic interference shielding effects, generally by obtaining high nanofiller loadings and thicknesses, inevitably results in poor processability, poor economic applicability, and severe agglomeration of fillers, thereby greatly hindering the development and applicability of conductive polymer composites.
Studies have demonstrated that the dispersion state of the conductive filler is a determining factor in the shielding performance of high performance conductive polymer composites. In order to solve the problem of filler aggregation, the design of preformed three-dimensional interconnected porous structures for the preparation of functional composites has been intensively studied. As energy and environmental issues become more severe, biomass polymer materials are expected to be investigated for future emi shielding materials due to their biodegradability, non-toxicity and renewable properties. Cellulose aerogel with 3D porous structure, which is the most abundant natural polymer on earth and one of the important cellulose products, is also used as a carrier for constructing functional composite materials. Cellulose aerogels have the characteristics of large specific surface area, low density, high porosity, abundant surface hydroxyls and the like, which provides convenience for integration with well-dispersed organic and inorganic guest substances to develop novel functional composite materials. Although much effort has been put into developing electromagnetic interference shielding materials based on porous materials, composite materials having an open cell structure cannot meet the strict requirements of practical applications because conductive fillers are generally wrapped on cell walls. Most frameworks are not wrapped, have limited space for scattering and reflecting electromagnetic waves, and are also susceptible to electromagnetic wave leakage, resulting in poor electromagnetic interference shielding performance.
Bringing conductive fillers into contact with each other and into alignment as much as possible is one of the most promising methods recognized for manufacturing high performance conductive composites in terms of improving the electromagnetic interference shielding performance of the composite. Recently, it has been confirmed that the orientation distribution of the conductive filler of the multilayer film can greatly improve efficiency to construct a superior electron transport path, thereby enhancing conductivity and electromagnetic interference shielding performance. The multilayer conductive polymers are mainly manufactured by layer-by-layer casting methods, with the intention of adjusting the dispersion of the filler or simply laminating uniform materials with a fixed impedance match. Although these materials have excellent electromagnetic interference shielding properties, there are some disadvantages such as complicated manufacturing processes and poor interfacial adhesion, which greatly hinder their mass production and greatly sacrifice their applicability. Therefore, it is extremely challenging to overcome these drawbacks simultaneously by existing material design strategies.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene nanosheet/cellulose aerogel composite material, and solves the problems of poor interface adhesion and low electromagnetic shielding performance of the existing composite material.
The technical scheme adopted by the invention is that the preparation method of the graphene nanosheet/cellulose aerogel composite material is implemented according to the following steps:
step 1, adding graphene nanosheets into deionized water, and performing ultrasonic dispersion for 1-1.5 hours to form a graphene nanosheet solution with the mass concentration of 1 wt%;
step 2, soaking the cellulose aerogel into the graphene nanosheet solution, ultrasonically dispersing for 5-45min, and then drying in an oven to obtain graphene nanosheets/cellulose aerogel;
and 3, soaking the graphene nanosheet/cellulose aerogel in a polyvinylidene fluoride/N' N dimethylformamide solution, curing, and hot-pressing to obtain the graphene nanosheet/cellulose aerogel composite material.
The present invention is also characterized in that,
in the step 2, the drying temperature is 60-80 ℃, and the drying time is 30-50 min.
In the step 2, the preparation method of the cellulose aerogel specifically comprises the following steps:
step a, placing cellulose in an oven, and drying for 24 hours at the temperature of 60 ℃ to obtain dried cellulose;
step b, uniformly mixing NaOH, urea and deionized water, and stirring for 12 hours at-12 ℃ to obtain a mixed solution; adding the dried cellulose into the mixed solution, and continuously and violently stirring for 2 hours to obtain a uniform and transparent cellulose solution;
the mass ratio of NaOH to urea to deionized water is 7: 12: 81;
the mass ratio of the mixed solution to the dried cellulose is 3: 100, respectively;
step c, adding N' N methylene bisacrylamide powder into the cellulose solution, uniformly stirring, pouring the mixture into a plastic mould, and standing at room temperature for 12 hours to obtain cellulose hydrogel;
d, washing the cellulose hydrogel with deionized water for several times until the washing liquid is neutral, and then carrying out freeze drying for 72 hours at the temperature of minus 60 ℃ to obtain cellulose aerogel; the pressure during freeze-drying was 20 Pa.
In the step 3, the soaking time is 20 min; the curing temperature is 120-150 ℃, and the curing time is 1-1.5 h.
In the step 3, the hot pressing temperature is 180-200 ℃, and the hot pressing time is 5-10 min.
In the step 3, the preparation method of the polyvinylidene fluoride/N' N dimethylformamide solution comprises the following steps: firstly, dispersing polyvinylidene fluoride serving as a solute into N, N-dimethylformamide, stirring in a water bath at the speed of 500rpm for 90min at the temperature of 85 ℃, and uniformly mixing to obtain a polyvinylidene fluoride/N, N-dimethylformamide solution; the mass ratio of the polyvinylidene fluoride to the N, N-dimethylformamide is 15: 85.
the beneficial effects of the invention are:
the graphene nanosheets are used for decorating the porous cellulose aerogel through ultrasonic treatment, and then the efficient electromagnetic interference shielding material with the directional multilayer structure is manufactured through an efficient hot-pressing technology. A polyvinylidene fluoride layer is further integrated to stabilize the graphene nanoplatelet network. Realizes the advantages of unique structure and highly arranged filler, and obtains the composite material with low thickness, excellent physical and chemical stability and high electromagnetic shielding performance. Meanwhile, the preparation method is simple, convenient and feasible, has lower production cost and is easy for batch production.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a graphene nanoplate/cellulose aerogel composite prepared by the method of the present invention;
fig. 2 is an electromagnetic shielding diagram of the graphene nanosheet/cellulose aerogel composite material prepared by the method of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the following detailed description and the accompanying drawings.
The invention relates to a preparation method of a graphene nanosheet/cellulose aerogel composite material, which is implemented according to the following steps:
step 1, adding graphene nanosheets into deionized water, and performing ultrasonic dispersion for 1-1.5 hours to form a graphene nanosheet solution with the mass concentration of 1 wt%;
the average thickness of the graphene nanosheets is less than 30nm, and the production manufacturer of the graphene nanosheets is Xiamen Kanna graphene Co., Ltd;
step 2, soaking the cellulose aerogel into the graphene nanosheet solution, ultrasonically dispersing for 5-45min, then drying in an oven to completely evaporate the solvent and stabilize the conductive network to obtain graphene nanosheets/cellulose aerogel;
the preparation method of the cellulose aerogel comprises the following steps:
step a, placing cellulose in an oven, and drying for 24 hours at the temperature of 60 ℃ to obtain dried cellulose;
in the cellulose, the content of alpha-cellulose exceeds 95 wt%, the average polymerization degree of the cellulose is 500, and a manufacturer is Hubei chemical fiber group company Limited;
step b, uniformly mixing NaOH, urea and deionized water, and stirring for 12 hours at-12 ℃ to obtain a mixed solution; then adding the dried cellulose into the mixed solution, and violently stirring for 2 hours at the temperature of-12 ℃ to obtain a uniform and transparent cellulose solution;
the mass ratio of NaOH to urea to deionized water is 7: 12: 81;
the mass ratio of the mixed solution to the dried cellulose is 3: 100;
step c, adding MBA (N' N methylene bisacrylamide) powder into the cellulose solution, uniformly stirring, pouring the mixture into a plastic mold, and standing at room temperature for 12 hours to form gel, thereby obtaining the cellulose hydrogel;
the molar mass ratio of the N' N dimethyl bisacrylamide to the cellulose is 1: 1;
d, washing the cellulose hydrogel with deionized water for several times until the washing liquid is neutral to remove NaOH, urea and free MBA, and then freeze-drying for 72 hours at-60 ℃ to obtain cellulose aerogel; during freeze drying, the pressure is 20 Pa;
the drying temperature is 60-80 ℃, and the drying time is 30-50 min;
and 3, soaking the graphene nanosheet/cellulose aerogel in a polyvinylidene fluoride/N' N dimethylformamide solution, curing and hot-pressing to obtain the graphene nanosheet/cellulose aerogel composite material.
Soaking for 20 min; the curing temperature is 120-150 ℃, and the curing time is 1-1.5 h;
the hot pressing temperature is 180-200 ℃, and the hot pressing time is 5-10 min;
the preparation method of the polyvinylidene fluoride/N' N dimethylformamide solution comprises the following steps: firstly, dispersing polyvinylidene fluoride serving as a solute into N, N-dimethylformamide, stirring in a water bath at the speed of 500rpm for 90min at the temperature of 85 ℃, and uniformly mixing to obtain a polyvinylidene fluoride/N, N-dimethylformamide solution; the mass ratio of the polyvinylidene fluoride to the N, N-dimethylformamide is 15: 85 parts by weight;
example 1
The invention relates to a preparation method of a graphene nanosheet/cellulose aerogel composite material, which is implemented according to the following steps:
step 1, adding graphene nanosheets into deionized water, and ultrasonically dispersing for 1h to form a graphene nanosheet solution with a mass concentration of 1 wt%;
step 2, soaking the cellulose aerogel into the graphene nanosheet solution, ultrasonically dispersing for 10min, then placing the solution into an oven for drying to completely evaporate the solvent and stabilize the conductive network to obtain the graphene nanosheet/cellulose aerogel;
the drying temperature is 60 ℃, and the drying time is 30 min;
the preparation method of the cellulose aerogel specifically comprises the following steps:
step a, placing cellulose in an oven, and drying for 24 hours at the temperature of 60 ℃ to obtain dried cellulose;
step b, uniformly mixing NaOH, urea and deionized water, and stirring for 12 hours at-12 ℃ to obtain a mixed solution; then adding the dried cellulose into the mixed solution, and violently stirring for 2 hours at the temperature of-12 ℃ to obtain a uniform and transparent cellulose solution;
the mass ratio of NaOH to urea to deionized water is 7: 12: 81;
the mass ratio of the mixed solution to the dried cellulose is 3: 100;
step c, adding MBA (N' N methylene bisacrylamide) powder into the cellulose solution, uniformly stirring, pouring the mixture into a plastic mold, and standing at room temperature for 12 hours to form gel, thereby obtaining the cellulose hydrogel;
the molar mass ratio of the N' N dimethyl bisacrylamide to the cellulose is 1: 1;
d, washing the cellulose hydrogel with deionized water for several times until the washing liquid is neutral to remove NaOH, urea and free MBA, and then freeze-drying for 72 hours at-60 ℃ to obtain cellulose aerogel; during freeze drying, the pressure is 20 Pa;
and 3, soaking the graphene nanosheet/cellulose aerogel in a polyvinylidene fluoride/N' N dimethylformamide solution, curing, and hot-pressing to obtain the graphene nanosheet/cellulose aerogel composite material.
Soaking for 20 min; the curing temperature is 120 ℃, and the curing time is 1 h;
the hot pressing temperature is 180 ℃, and the hot pressing time is 5 min;
the preparation method of the polyvinylidene fluoride/N' N dimethylformamide solution comprises the following steps: firstly, dispersing polyvinylidene fluoride serving as a solute into N, N-dimethylformamide, stirring in a water bath at the speed of 500rpm for 90min at the temperature of 85 ℃, and uniformly mixing to obtain a polyvinylidene fluoride/N, N-dimethylformamide solution; the mass ratio of the polyvinylidene fluoride to the N, N-dimethylformamide is 15: 85.
example 2
The invention relates to a preparation method of a graphene nanosheet/cellulose aerogel composite material, which is implemented according to the following steps:
step 1, adding graphene nanosheets into deionized water, and performing ultrasonic dispersion for 1.2 hours to form a graphene nanosheet solution with a mass concentration of 1 wt%;
step 2, immersing cellulose aerogel into a graphene nanosheet solution, ultrasonically dispersing for 5min, then placing into an oven for drying so as to completely evaporate the solvent and stabilize the conductive network, and obtaining graphene nanosheets/cellulose aerogel;
the drying temperature is 70 ℃, and the drying time is 40 min;
the preparation method of the cellulose aerogel comprises the following steps:
step a, placing cellulose in an oven, and drying for 24 hours at the temperature of 60 ℃ to obtain dried cellulose;
in the cellulose, the content of alpha-cellulose exceeds 95 wt%, the average polymerization degree of the cellulose is 500, and a manufacturer is Hubei chemical fiber group company Limited;
step b, uniformly mixing NaOH, urea and deionized water, and stirring for 12 hours at-12 ℃ to obtain a mixed solution; then adding the dried cellulose into the mixed solution, and violently stirring for 2 hours at the temperature of-12 ℃ to obtain a uniform and transparent cellulose solution;
the mass ratio of NaOH to urea to deionized water is 7: 12: 81;
the mass ratio of the mixed solution to the dried cellulose is 3: 100, respectively;
step c, adding MBA (N' N methylene bisacrylamide) powder into the cellulose solution, uniformly stirring, pouring the mixture into a plastic mold, and standing at room temperature for 12 hours to form gel, thereby obtaining the cellulose hydrogel;
the molar mass ratio of the N' N dimethyl bisacrylamide to the cellulose is 1: 1;
d, washing the cellulose hydrogel with deionized water for several times until the washing liquid is neutral to remove NaOH, urea and free MBA, and then freezing and drying for 72 hours at-60 ℃ to obtain cellulose aerogel; during freeze drying, the pressure is 20 Pa;
and 3, soaking the graphene nanosheet/cellulose aerogel in a polyvinylidene fluoride/N' N dimethylformamide solution, curing, and hot-pressing to obtain the graphene nanosheet/cellulose aerogel composite material.
Soaking for 20 min; the curing temperature is 130 ℃, and the curing time is 1.2 h;
the hot pressing temperature is 190 ℃, and the hot pressing time is 7 min;
the preparation method of the polyvinylidene fluoride/N' N dimethylformamide solution comprises the following steps: firstly, dispersing polyvinylidene fluoride serving as a solute into N, N-dimethylformamide, stirring in a water bath at the speed of 500rpm for 90min at the temperature of 85 ℃, and uniformly mixing to obtain a polyvinylidene fluoride/N, N-dimethylformamide solution; the mass ratio of the polyvinylidene fluoride to the N, N-dimethylformamide is 15: 85.
example 3
The invention relates to a preparation method of a graphene nanosheet/cellulose aerogel composite material, which is implemented according to the following steps:
step 1, adding graphene nanosheets into deionized water, and performing ultrasonic dispersion for 1.5 hours to form a graphene nanosheet solution with a mass concentration of 1 wt%;
step 2, immersing cellulose aerogel into a graphene nanosheet solution, ultrasonically dispersing for 30min, then placing into an oven for drying so as to completely evaporate the solvent and stabilize the conductive network, and obtaining graphene nanosheets/cellulose aerogel;
the drying temperature is 80 ℃, and the drying time is 50 min;
the preparation method of the cellulose aerogel specifically comprises the following steps:
step a, placing cellulose in an oven, and drying for 24 hours at the temperature of 60 ℃ to obtain dried cellulose;
step b, uniformly mixing NaOH, urea and deionized water, and stirring for 12 hours at-12 ℃ to obtain a mixed solution; then adding the dried cellulose into the mixed solution, and violently stirring for 2 hours at the temperature of-12 ℃ to obtain a uniform and transparent cellulose solution;
the mass ratio of NaOH to urea to deionized water is 7: 12: 81;
the mass ratio of the mixed solution to the dried cellulose is 3: 100;
step c, adding MBA (N' N methylene bisacrylamide) powder into the cellulose solution, uniformly stirring, pouring the mixture into a plastic mould, and standing at room temperature for 12 hours to form gel, thereby obtaining the cellulose hydrogel;
the molar mass ratio of the N' N dimethyl bisacrylamide to the cellulose is 1: 1;
d, washing the cellulose hydrogel with deionized water for several times until the washing liquid is neutral to remove NaOH, urea and free MBA, and then freezing and drying for 72 hours at-60 ℃ to obtain cellulose aerogel; during freeze drying, the pressure is 20 Pa;
and 3, soaking the graphene nanosheet/cellulose aerogel in a polyvinylidene fluoride/N' N dimethylformamide solution, curing and hot-pressing to obtain the graphene nanosheet/cellulose aerogel composite material.
Soaking for 20 min; the curing temperature is 150 ℃, and the curing time is 1.5 h;
the hot pressing temperature is 200 ℃, and the hot pressing time is 10 min;
the preparation method of the polyvinylidene fluoride/N' N dimethylformamide solution comprises the following steps: firstly, dispersing polyvinylidene fluoride serving as a solute into N, N-dimethylformamide, stirring in a water bath at the speed of 500rpm for 90min at the temperature of 85 ℃, and uniformly mixing to obtain a polyvinylidene fluoride/N, N-dimethylformamide solution; the mass ratio of the polyvinylidene fluoride to the N, N-dimethylformamide is 15: 85.
example 4
The invention relates to a preparation method of a graphene nanosheet/cellulose aerogel composite material, which is implemented according to the following steps:
step 1, adding graphene nanosheets into deionized water, and performing ultrasonic dispersion for 1 hour to form a graphene nanosheet solution with the mass concentration of 1 wt%;
step 2, soaking the cellulose aerogel into a graphene nanosheet solution, ultrasonically dispersing for 45min, then placing the solution into an oven for drying to completely evaporate the solvent and stabilize the conductive network to obtain graphene nanosheets/cellulose aerogel;
the drying temperature is 60 ℃, and the drying time is 30 min;
the preparation method of the cellulose aerogel comprises the following steps:
step a, placing cellulose in an oven, and drying for 24 hours at the temperature of 60 ℃ to obtain dried cellulose;
step b, uniformly mixing NaOH, urea and deionized water, and stirring for 12 hours at-12 ℃ to obtain a mixed solution; then adding the dried cellulose into the mixed solution, and violently stirring for 2 hours at the temperature of-12 ℃ to obtain a uniform and transparent cellulose solution;
the mass ratio of NaOH to urea to deionized water is 7: 12: 81;
the mass ratio of the mixed solution to the dried cellulose is 3: 100, respectively;
step c, adding MBA (N' N methylene bisacrylamide) powder into the cellulose solution, uniformly stirring, pouring the mixture into a plastic mold, and standing at room temperature for 12 hours to form gel, thereby obtaining the cellulose hydrogel;
the molar mass ratio of the N' N dimethyl bisacrylamide to the cellulose is 1: 1;
d, washing the cellulose hydrogel with deionized water for several times until the washing liquid is neutral to remove NaOH, urea and free MBA, and then freezing and drying for 72 hours at-60 ℃ to obtain cellulose aerogel; during freeze drying, the pressure is 20 Pa;
and 3, soaking the graphene nanosheet/cellulose aerogel in a polyvinylidene fluoride/N' N dimethylformamide solution, curing and hot-pressing to obtain the graphene nanosheet/cellulose aerogel composite material.
Soaking for 20 min; the curing temperature is 145 ℃, and the curing time is 1.5 h;
the hot pressing temperature is 200 ℃, and the hot pressing time is 5 min;
the preparation method of the polyvinylidene fluoride/N' N dimethylformamide solution comprises the following steps: firstly, dispersing polyvinylidene fluoride serving as a solute into N, N-dimethylformamide, stirring in a water bath at the speed of 500rpm for 90min at the temperature of 85 ℃, and uniformly mixing to obtain a polyvinylidene fluoride/N, N-dimethylformamide solution; the mass ratio of the polyvinylidene fluoride to the N, N-dimethylformamide is 15: 85.
fig. 1 is an SEM image of graphene/cellulose aerogel prepared by the method of the present invention. It can be seen from the figure that the prepared composite material has a layered orientation structure, and the three-dimensional framework of the aerogel remains. The special structure enables electromagnetic waves to undergo an absorption-reflection-reabsorption process in the composite material, so that the prepared composite material achieves excellent electromagnetic shielding performance.
Fig. 2 shows electromagnetic shielding effectiveness of cellulose aerogel in 1 wt% graphene aqueous solution for different ultrasonic time, that is, the cellulose aerogel is subjected to ultrasonic treatment in the graphene nanosheet aqueous solution for 5, 15, 30, and 45min to obtain graphene/cellulose aerogel. As can be seen from the figure, pure Cellulose Aerogel (CAF) has little electromagnetic shielding properties due to its non-electrical conductivity. With the increase of the ultrasonic time, the electromagnetic shielding performance is improved, and the optimal electromagnetic shielding performance is 49.5dB, which is mainly caused by the fact that the graphene content is increased due to the increase of the ultrasonic time, so that a more compact conductive network is established.
According to the preparation method of the graphene nanosheet/cellulose aerogel composite material, the graphene nanosheets are adopted to decorate the porous cellulose aerogel through convenient ultrasonic treatment and an efficient hot pressing technology, the preparation process is safe and environment-friendly, the preparation process is simple and low in cost, and the preparation method has wide practicability and popularization value; graphene nanoplate decorated multilayer three-dimensional cellulose aerogel composite composites exhibit exceptional electromagnetic interference shielding durability even after being subjected to intense physical and chemical damage. The composite material with a unique structure innovatively designed in the preparation method has excellent electromagnetic shielding performance, can meet the application requirements in the fields of flexible electronics, aerospace, electronic packaging and the like, and opens up a new way for preparing high-grade electromagnetic interference shielding composite materials.
Claims (6)
1. A preparation method of a graphene nanosheet/cellulose aerogel composite material is characterized by comprising the following steps:
step 1, adding graphene nanosheets into deionized water, and performing ultrasonic dispersion for 1-1.5 hours to form a graphene nanosheet solution with the mass concentration of 1 wt%;
step 2, immersing cellulose aerogel into the graphene nanosheet solution, ultrasonically dispersing for 5-45min, and then drying in an oven to obtain graphene nanosheets/cellulose aerogel;
and 3, soaking the graphene nanosheet/cellulose aerogel in a polyvinylidene fluoride/N' N dimethylformamide solution, curing, and hot-pressing to obtain the graphene nanosheet/cellulose aerogel composite material.
2. The preparation method of the graphene nanosheet/cellulose aerogel composite material as claimed in claim 1, wherein in step 2, the drying temperature is 60-80 ℃ and the drying time is 30-50 min.
3. The method for preparing a graphene nanosheet/cellulose aerogel composite material according to claim 1, wherein in the step 2, the method for preparing the cellulose aerogel specifically comprises:
step a, placing cellulose in an oven, and drying for 24 hours at the temperature of 60 ℃ to obtain dried cellulose;
step b, uniformly mixing NaOH, urea and deionized water, and stirring for 12 hours at-12 ℃ to obtain a mixed solution; adding the dried cellulose into the mixed solution, and continuously and violently stirring for 2 hours to obtain a uniform and transparent cellulose solution;
the mass ratio of NaOH to urea to deionized water is 7: 12: 81;
the mass ratio of the mixed solution to the dried cellulose is 3: 100, respectively;
step c, adding N' N methylene bisacrylamide powder into the cellulose solution, uniformly stirring, pouring the mixture into a plastic mould, and standing at room temperature for 12 hours to obtain cellulose hydrogel;
d, washing the cellulose hydrogel with deionized water for several times until the washing liquid is neutral, and then freeze-drying for 72 hours at the temperature of-60 ℃ to obtain cellulose aerogel; the pressure during freeze drying was 20 Pa.
4. The preparation method of graphene nanoplatelets/cellulose aerogel composite according to claim 1, wherein in the step 3, the soaking time is 20 min; the curing temperature is 120-150 ℃, and the curing time is 1-1.5 h.
5. The preparation method of graphene nanoplatelets/cellulose aerogel composite material as claimed in claim 1, wherein in the step 3, the hot pressing temperature is 180-200 ℃, and the hot pressing time is 5-10 min.
6. The preparation method of graphene nanoplatelets/cellulose aerogel composite material as claimed in claim 1, wherein in the step 3, the preparation method of polyvinylidene fluoride/N' N dimethylformamide solution is as follows: firstly, dispersing polyvinylidene fluoride serving as a solute into N, N-dimethylformamide, stirring in a water bath at the speed of 500rpm for 90min at the temperature of 85 ℃, and uniformly mixing to obtain a polyvinylidene fluoride/N, N-dimethylformamide solution; the mass ratio of the polyvinylidene fluoride to the N, N-dimethylformamide is 15: 85.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011010794.1A CN112194819B (en) | 2020-09-23 | 2020-09-23 | Preparation method of graphene nanosheet/cellulose aerogel composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011010794.1A CN112194819B (en) | 2020-09-23 | 2020-09-23 | Preparation method of graphene nanosheet/cellulose aerogel composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112194819A CN112194819A (en) | 2021-01-08 |
| CN112194819B true CN112194819B (en) | 2022-07-22 |
Family
ID=74014486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011010794.1A Active CN112194819B (en) | 2020-09-23 | 2020-09-23 | Preparation method of graphene nanosheet/cellulose aerogel composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112194819B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112969356A (en) * | 2021-01-19 | 2021-06-15 | 西安理工大学 | Preparation method of polyurethane/graphene nanosheet/sponge composite material |
| CN112911920B (en) * | 2021-02-08 | 2022-09-02 | 浙江环龙新材料科技有限公司 | Preparation method of MXene-carbon aerogel/TPU composite material |
| CN113372609B (en) * | 2021-06-24 | 2022-11-08 | 中南大学 | Porous flexible GNP/PDMS composite material, preparation method thereof and application thereof in strain sensor |
| CN113480781B (en) * | 2021-07-27 | 2022-06-10 | 东北林业大学 | Graphene/nanocellulose/polyvinyl alcohol ternary composite aerogel and preparation method thereof |
| CN113912886A (en) * | 2021-12-08 | 2022-01-11 | 武汉理工大学 | Preparation method of cellulose/polyvinylidene fluoride high-dielectric composite film |
| CN114931907B (en) * | 2022-04-11 | 2024-06-07 | 武汉工程大学 | MXene, conductive polymer and plant cellulose composite aerogel and preparation method and application thereof |
| CN114957991B (en) * | 2022-07-05 | 2023-09-29 | 扬州工业职业技术学院 | Biomass-derived cellulose aerogel material for fireproof door |
| CN115490910B (en) * | 2022-09-30 | 2023-06-30 | 湖北工业大学 | Plant polysaccharide-based multilayer heat insulation aerogel group and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108585919A (en) * | 2018-06-07 | 2018-09-28 | 江苏理工学院 | A kind of preparation method of graphene/luffa hybrid aerogel |
| CN110354766A (en) * | 2019-07-18 | 2019-10-22 | 青岛黑猫炭黑科技有限责任公司 | A kind of cellulose/graphene nano composite aerogel preparation method and application |
| KR20190137377A (en) * | 2018-06-01 | 2019-12-11 | 이성균 | A. (hydrophobic) nano cellulose aerogels for water and air purification and hydrogen production. outside |
-
2020
- 2020-09-23 CN CN202011010794.1A patent/CN112194819B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190137377A (en) * | 2018-06-01 | 2019-12-11 | 이성균 | A. (hydrophobic) nano cellulose aerogels for water and air purification and hydrogen production. outside |
| CN108585919A (en) * | 2018-06-07 | 2018-09-28 | 江苏理工学院 | A kind of preparation method of graphene/luffa hybrid aerogel |
| CN110354766A (en) * | 2019-07-18 | 2019-10-22 | 青岛黑猫炭黑科技有限责任公司 | A kind of cellulose/graphene nano composite aerogel preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Incorporation of graphene nanosheets into cellulose aerogels: enhanced mechanical, thermal, and oil adsorption properties：;Wan, Caichao et al.;《Applied Physics A: Materials Science & Processing》;20161231;第1-7页 * |
| 废弃物基纤维素气凝胶的研究进展;狄莹莹等;《合成材料老化与应用》;20181231;第114-121页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112194819A (en) | 2021-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112194819B (en) | Preparation method of graphene nanosheet/cellulose aerogel composite material | |
| Zhang et al. | Cellulose-chitosan framework/polyailine hybrid aerogel toward thermal insulation and microwave absorbing application | |
| Jia et al. | Construction of compressible Polymer/MXene composite foams for high-performance absorption-dominated electromagnetic shielding with ultra-low reflectivity | |
| CN108811478B (en) | A kind of three-layer laminated MXene electromagnetic shielding foam and preparation method | |
| CN109705313A (en) | A kind of hot adaptive shape-memory polymer and its application method | |
| CN109206961B (en) | Graphene electric-conduction heat-conduction coating and preparation method thereof | |
| CN110951109B (en) | Bacterial cellulose/polypyrrole/polyurethane flexible multifunctional conductive composite material and preparation method thereof | |
| CN106832364A (en) | The preparation method of flexible crosslinked polyimide aerogel | |
| CN111592684B (en) | Preparation method of isolated thermoplastic elastomer composite microporous electromagnetic shielding material | |
| CN111218112A (en) | rGO/polyimide composite aerogel and preparation method and application thereof | |
| CN111424341B (en) | Waste leather superfine fiber, high electromagnetic shielding material compounded by waste leather superfine fiber and polyvinyl alcohol, and preparation methods of waste leather superfine fiber and high electromagnetic shielding material | |
| CN108084484B (en) | Lightweight conductive heat-insulation composite material and preparation method and system thereof | |
| CN109942848A (en) | The preparation method of surface texture hydrophobic type polyimide aerogels film | |
| CN111944273A (en) | Preparation method of epoxy resin impregnated three-dimensional graphene network composite material | |
| CN113185762A (en) | Expanded graphite thermal interface material and preparation method thereof | |
| CN113831724B (en) | Electromagnetic gradient asymmetric conductive composite material and preparation method thereof | |
| CN109134943A (en) | A kind of preparation method of pressure-sensitive cellulose/MWCNTs/TPU composite foam material | |
| CN114479079A (en) | Polyimide aerogel and preparation method thereof | |
| CN101942179B (en) | Polypyrrole-graphite nanosheet-epoxy resin conductive composite material and preparation thereof | |
| CN113861549A (en) | EVA/polypyrrole/MXene composite material and preparation method and application thereof | |
| CN115109292B (en) | Preparation method of graphene foam conductive composite material | |
| CN104943267A (en) | Polytetrafluoroethylene base plate and preparation method thereof | |
| CN111393693A (en) | Preparation method of nano silicon dioxide/polyvinyl alcohol/carapace liquefied product preservative film material | |
| CN115197570B (en) | Soft polyimide foam material with improved cell structure and preparation method thereof | |
| CN112812236B (en) | SMC antenna housing for 5G communication and preparation method thereof |
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 |