CN110256732A - A kind of ferroso-ferric oxide-graphene-cellulose conduction composite aerogel and preparation method thereof applied to electromagnetic shielding field - Google Patents
A kind of ferroso-ferric oxide-graphene-cellulose conduction composite aerogel and preparation method thereof applied to electromagnetic shielding field Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 77
- 239000001913 cellulose Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000004964 aerogel Substances 0.000 title claims abstract description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 123
- 239000007864 aqueous solution Substances 0.000 claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004202 carbamide Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 34
- 239000000017 hydrogel Substances 0.000 claims abstract description 33
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 13
- 230000001112 coagulating effect Effects 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims 1
- 229930003268 Vitamin C Natural products 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 235000019154 vitamin C Nutrition 0.000 claims 1
- 239000011718 vitamin C Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 239000008367 deionised water Substances 0.000 abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 abstract description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 229940056319 ferrosoferric oxide Drugs 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 235000010980 cellulose Nutrition 0.000 description 23
- 238000002791 soaking Methods 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011782 vitamin Substances 0.000 description 4
- 229940088594 vitamin Drugs 0.000 description 4
- 229930003231 vitamin Natural products 0.000 description 4
- 235000013343 vitamin Nutrition 0.000 description 4
- 150000003722 vitamin derivatives Chemical class 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 206010000269 abscess Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
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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
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
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- 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
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
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Abstract
The invention discloses a kind of ferroso-ferric oxide-graphene-cellulose conduction composite aerogels and preparation method thereof applied to electromagnetic shielding field.The preparation method include: by cellulose dissolution in sodium hydroxide/urea aqueous solution, then casting film-forming obtains hydrogel after graphene oxide water solution being mixed with cellulose solution, after reducing agent in-situ reducing, hydrogel is successively impregnated in the aqueous solution and aqueous slkali of iron chloride and frerrous chloride to in-situ preparation ferroso-ferric oxide again, after deionized water is repeatedly rinsed, up to the ferroso-ferric oxide-graphene-cellulose conduction composite aerogel for being applied to electromagnetic shielding field after freeze-drying.The effectiveness of aeroge provided by the invention is fine.Preparation method provided by the invention has many advantages, such as that technical process is simple and convenient to operate and no pollution to the environment.Composite aerogel provided by the invention can be applied in the fields such as electromagnetic shielding material.
Description
Technical field
The invention belongs to be electromagnetically shielded field, and in particular to a kind of ferroso-ferric oxide-stone applied to electromagnetic shielding field
Black alkene-cellulose conduction composite aerogel and preparation method thereof.
With the development of Modern communication devices, electronic equipment and radio communication are made extensively in our daily life
With.Simultaneously.The harm of electromagnetic radiation is also on the rise, and can not only interfere the normal operation of electronic equipment, can also be to people
The health of class causes damages.Therefore, the harm that this electromagnetic radiation is eliminated using electromagnetic shielding material is urgent need
's.Currently, electromagnetic shielding is widely used in military project and civil field, such as wireless device, aircraft manufacturing, electronic equipment etc..
Therefore, our requirements and performance for electromagnetic shielding material now is also higher and higher.However, traditional electromagnetic shielding material base
It originally is to have based on metal and be unfavorable for processing, easily corrode, therefore the defects of shielding material density is high explores matter
Gently, stable and high electromagnetic shielding performance electromagnetic shielding material is problem in the urgent need to address.Simultaneously with white pollution and
Plastics recovery problem is increasingly severe, recoverable and biodegradable natural polymer more and more attention has been paid to.Fiber
Element has wide application prospects as a kind of the most abundant natural high polymer.Since it is cheap and biodegradable, can be used for
Packaging film and functional material are prepared, to solve problem of environmental pollution.In addition, adding well since cellulose aerogels material has
Work, can electromagnetic shielding material matrix and ferroso-ferric oxide and graphene play a role jointly, to improve the electricity of this material
Magnetic shield performance.The existing good magnetic property of this aerogel material and the advantages such as electric conductivity and light weight, then have
Excellent electromagnetic shielding performance also has the workability and mechanical property of high molecular material, can be widely used in electromagnetic shielding
Etc. multiple fields.
Summary of the invention
In order to overcome the shortcomings of the prior art, the object of the present invention is to provide a kind of applied to electromagnetic shielding field
Ferroso-ferric oxide-graphene-cellulose conduction composite aerogel and preparation method thereof.
The purpose of the present invention is realized at least through one of following technical solution.
A kind of ferroso-ferric oxide-graphene-cellulose conduction applied to electromagnetic shielding field provided by the invention is compound
The preparation method of aeroge, comprising: using cellulose as substrate, combined oxidation graphene, the oxidation of in-situ preparation four three again after reduction
The aerogel composite for being electromagnetically shielded field is prepared in iron;The technique for preparing composite aerogel has process letter
The advantages that single, easy to operate and no pollution to the environment.Composite conducting aeroge provided by the invention can be applied to be electromagnetically shielded
The fields such as material.
A kind of ferroso-ferric oxide-graphene-cellulose conduction applied to electromagnetic shielding field provided by the invention is compound
The preparation method of aeroge, includes the following steps:
(1) sodium hydroxide and urea are added to the water, are uniformly mixed and obtain sodium hydroxide/urea mixed aqueous solution,
Graphene oxide is dispersed in water, and obtains the aqueous solution of graphene oxide;
(2) mixed aqueous solution of step (1) sodium hydroxide/urea is subjected to precooling treatment, cellulose is then added,
It is uniformly mixing to obtain cellulose solution;The aqueous solution of step (1) described graphene oxide is added in cellulose solution, mixing is equal
It is even to obtain mixed liquor;By mixed liquor casting film-forming, coagulating bath processing is then carried out in dilution heat of sulfuric acid, solidification forming obtains water
Gel, repeatedly washing in deionized water after taking-up;
(3) hydrogel after step (2) washing is immersed in progress reduction treatment (in-situ reducing) in reducing agent solution,
Graphene-cellulose composite hydrogel is obtained, repeatedly washing in deionized water after taking-up;
(4) iron chloride and frerrous chloride are added to the water, are uniformly mixed and obtain iron chloride and the mixing of frerrous chloride is water-soluble
Graphene-cellulose composite hydrogel after step (3) washing is successively immersed in the mixed of the iron chloride and frerrous chloride by liquid
In Heshui solution and alkaline solution, ferroso-ferric oxide-graphene-cellulose composite hydrogel is obtained, deionized water is repeatedly washed,
Freeze-drying obtains the ferroso-ferric oxide-graphene-cellulose conduction composite aerogel for being applied to electromagnetic shielding field.
Further, the mass ratio of step (1) sodium hydroxide and urea is 6:14~8:10;The urea and water
Mass ratio is 10:82~14:80;The mass percent concentration of the aqueous solution of the graphene oxide is 0.2~2%.
Preferably, step (2) precooling temperature is -12~-20 DEG C, and pre-coo time is 1-2 hours;Preferably, step
(2) mixing time (mixing time of dissolution cellulose) stirred evenly is 5~10 minutes.
Further, the quality of step (2) described cellulose be sodium hydroxide/urea mixed aqueous solution quality 2~
8%;The mass ratio of step (1) graphene oxide and step (2) described cellulose is 2:98-8:92.
Further, the volume of the aqueous solution of step (2) described graphene oxide is the 10%- of cellulose solution volume
30%.
Further, the mass percent concentration of step (2) described dilution heat of sulfuric acid is 4%-6%, at the coagulating bath
The time of reason is 5-10 minutes.
Further, step (3) described reducing agent solution includes ascorbic aqueous solution, the ascorbic aqueous solution
Concentration be 30-50g/L;The temperature of the reduction treatment is 90-95 degrees Celsius, and the time of the reduction treatment is 1-2 hours.
Further, the molar ratio of step (4) iron chloride and frerrous chloride is 1.6:1.4-2.4:0.6;The chlorine
The mass volume ratio for changing iron and water is 5-10:1g/L.
Further, graphene-cellulose composite hydrogel after step (4) described washing is immersed in iron chloride and chlorination
The time of ferrous mixed aqueous solution is 30-60 minutes;Step (4) described alkaline solution includes sodium hydroxide solution, quality hundred
Point specific concentration is 5%-10%, and graphene-cellulose composite hydrogel after the washing is immersed in the time in aqueous slkali and is
5-10 minutes.
Preferably, the time of freeze-drying described in step (3) is 20-24 hours.
The present invention provides a kind of ferroso-ferric oxide-stone for being applied to electromagnetic shielding field as made from above-mentioned preparation method
Black alkene-cellulose conduction composite aerogel.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
(1) preparation method provided by the invention, used raw cellulose are most extensive volume natural polymers in nature
Sub- material, it is from a wealth of sources, it is cheap, belong to environment-friendly material;The preparation method have simple process, to equipment requirement not
Height is conducive to the advantages that being mass produced and is simple to operate.
(2) the cellulose base aeroge that the present invention is prepared, abscess is uniform, while graphene and ferroso-ferric oxide play
Synergistic effect, can improve the effectiveness of this aerogel material jointly.
Specific embodiment
Specific implementation of the invention is described further below in conjunction with example, but implementation and protection of the invention is not limited to
This.If being that those skilled in the art can refer to prior art reality it is noted that there is the process of not special detailed description below
It is existing or understanding.Reagents or instruments used without specified manufacturer, being considered as can be by the commercially available conventional products being commercially available.
Embodiment 1
The conductive compound airsetting of ferroso-ferric oxide-graphene applied to electromagnetic shielding field that embodiment 1 provides-cellulose
The preparation method of glue, includes the following steps:
(1) 20g sodium hydroxide is added to the water with urea, is uniformly mixed and obtains sodium hydroxide/urea mixed aqueous solution,
In the mixed aqueous solution of the sodium hydroxide/urea, the mass percent concentration of sodium hydroxide is 7wt%, the quality of urea
Percent concentration is 12wt%;0.08 gram of graphene oxide is dispersed in 20 milliliters of water, the aqueous solution of graphene oxide is obtained;
(2) mixed aqueous solution of step (1) sodium hydroxide/urea is subjected to precooling treatment, the temperature of precooling treatment
It is -12 degrees Celsius, the time of precooling treatment is 1 hour;3.92 grams of celluloses are added to 96 grams of sodium hydroxide/urea mixing
It in aqueous solution, stirs 5 minutes, is uniformly mixing to obtain cellulose solution, 100 millis are added in the aqueous solution of 20 milliliters of graphene oxides
It rises in cellulose solution, is uniformly mixed and obtains mixed liquor;By mixed liquor casting film-forming on a glass, then in dilution heat of sulfuric acid
Coagulating bath processing is carried out in (dilution heat of sulfuric acid concentration is 4wt%), the time of coagulating bath processing is 5 minutes, obtains hydrogel, uses
Deionized water washing;
(3) hydrogel after washing step (2) is immersed in 500 milliliters of reducing agent solutions, and (concentration is the vitamin of 30g/L
The aqueous solution of C) in carry out reduction treatment, the temperature of reduction treatment is 95 degrees Celsius, and the time of reduction treatment is 1 hour, is obtained
Graphene-cellulose composite hydrogel, is washed with deionized;
(4) 8mmol iron chloride and 4mmol frerrous chloride are added in 200 milliliters of water, are uniformly mixed and obtain iron chloride and chlorine
Change ferrous mixed aqueous solution;By step (3) washing after graphene-cellulose composite hydrogel be immersed in the iron chloride with
In the mixed aqueous solution of frerrous chloride, soaking time is 30 minutes;Then 100 milliliters of alkaline solution (concentration 5wt% are immersed in
Sodium hydroxide solution) in, soaking time be 5 minutes, obtain ferroso-ferric oxide-graphene-cellulose composite hydrogel, use
Deionized water is repeatedly washed, and freeze-drying obtains the ferroso-ferric oxide-graphene-cellulose for being applied to electromagnetic shielding field
Conductive composite aerogel, the time of freeze-drying are 1 hour.It counts by weight, step (1) graphene oxide and fiber
The ratio of element is 2:98.
(5) pass through above-mentioned steps, ferroso-ferric oxide-graphene-cellulose conduction composite aerogel of preparation is with a thickness of 2 millis
Rice, electromagnetic shielding performance 44dB.This light aerogel material only joined a small amount of graphene, and electromagnetic shielding performance is just
More than the application requirement (20dB) of electromagnetic shielding material.
Embodiment 2
The conductive compound airsetting of ferroso-ferric oxide-graphene applied to electromagnetic shielding field that embodiment 2 provides-cellulose
The preparation method of glue, includes the following steps:
(1) 20g sodium hydroxide is added to the water with urea, is uniformly mixed and obtains sodium hydroxide/urea mixed aqueous solution,
In the mixed aqueous solution of the sodium hydroxide/urea, the mass percent concentration of sodium hydroxide is 6wt%, the quality of urea
Percent concentration is 14wt%;0.16 gram of graphene oxide is dispersed in 20 milliliters of water, the aqueous solution of graphene oxide is obtained;
(2) mixed aqueous solution of step (1) sodium hydroxide/urea is subjected to precooling treatment, the temperature of precooling treatment
It is -18 degrees Celsius, the time of precooling treatment is 1.5 hours;It is mixed that 3.84 grams of celluloses are added to 96 grams of sodium hydroxide/urea
It in Heshui solution, stirs 5 minutes, is uniformly mixing to obtain cellulose solution, the aqueous solution of 10 milliliters of graphene oxides is added 100
In milliliter cellulose solution, it is uniformly mixed and obtains mixed liquor;It is then molten in dilute sulfuric acid by mixed liquor casting film-forming on a glass
Coagulating bath processing is carried out in liquid (dilution heat of sulfuric acid concentration is 4wt%), the time of coagulating bath processing is 7 minutes, obtains water-setting
Glue is washed with deionized;
(3) hydrogel after washing step (2) is immersed in 500 milliliters of reducing agent solutions, and (concentration is the vitamin of 40g/L
The aqueous solution of C) in carry out reduction treatment, the temperature of reduction treatment is 95 degrees Celsius, and the time of reduction treatment is 1.5 hours, is obtained
To graphene-cellulose composite hydrogel, it is washed with deionized;
(4) 8mmol iron chloride and 4mmol frerrous chloride are added in 200 milliliters of water, are uniformly mixed and obtain iron chloride and chlorine
Change ferrous mixed aqueous solution;By step (3) washing after graphene-cellulose composite hydrogel be immersed in the iron chloride with
In the mixed aqueous solution of frerrous chloride, soaking time is 1 hour;Then 100 milliliters of alkaline solution (concentration 5wt% are immersed in
Sodium hydroxide solution) in, soaking time be 5 minutes, obtain ferroso-ferric oxide-graphene-cellulose composite hydrogel, use
Deionized water is repeatedly washed, and freeze-drying obtains the ferroso-ferric oxide-graphene-cellulose for being applied to electromagnetic shielding field
Conductive composite aerogel, the time of freeze-drying are 22 hours.It counts by weight, step (1) graphene oxide and fine
The ratio of dimension element is 4:96.
(5) pass through above-mentioned steps, ferroso-ferric oxide-graphene-cellulose conduction composite aerogel of preparation is with a thickness of 2 millis
Rice, electromagnetic shielding performance 50dB.This light aerogel material only joined a small amount of graphene, and electromagnetic shielding performance is just
More than the application requirement (20dB) of electromagnetic shielding material.Meanwhile with the raising of graphene content, electromagnetic wave is caused in airsetting
Route of transmission in glue material increases, to obtain higher electromagnetic shielding performance.
Embodiment 3
The conductive compound airsetting of ferroso-ferric oxide-graphene applied to electromagnetic shielding field that embodiment 3 provides-cellulose
The preparation method of glue, includes the following steps:
(1) 20g sodium hydroxide is added to the water with urea, is uniformly mixed and obtains sodium hydroxide/urea mixed aqueous solution,
In the mixed aqueous solution of the sodium hydroxide/urea, the mass percent concentration of sodium hydroxide is 8wt%, the quality of urea
Percent concentration is 10wt%;0.24 gram of graphene oxide is dispersed in 20 milliliters of water, the aqueous solution of graphene oxide is obtained;
(2) mixed aqueous solution of step (1) sodium hydroxide/urea is subjected to precooling treatment, the temperature of precooling treatment
It is -20 degrees Celsius, the time of precooling treatment is 1 hour;3.76 grams of celluloses are added to 96 grams of sodium hydroxide/urea mixing
It in aqueous solution, stirs 5 minutes, is uniformly mixing to obtain cellulose solution, 100 millis are added in the aqueous solution of 30 milliliters of graphene oxides
It rises in cellulose solution, is uniformly mixed and obtains mixed liquor;By mixed liquor casting film-forming on a glass, then in dilution heat of sulfuric acid
Coagulating bath processing is carried out in (dilution heat of sulfuric acid concentration is 6wt%), the time of coagulating bath processing is 5 minutes, obtains hydrogel, uses
Deionized water washing;
(3) hydrogel after washing step (2) is immersed in 500 milliliters of reducing agent solutions, and (concentration is the vitamin of 50g/L
The aqueous solution of C) in carry out reduction treatment, the temperature of reduction treatment is 90 degrees Celsius, and the time of reduction treatment is 2 hours, is obtained
Graphene-cellulose composite hydrogel, is washed with deionized;
(4) 8mmol iron chloride and 4mmol frerrous chloride are added in 200 milliliters of water, are uniformly mixed and obtain iron chloride and chlorine
Change ferrous mixed aqueous solution;By step (3) washing after graphene-cellulose composite hydrogel be immersed in the iron chloride with
In the mixed aqueous solution of frerrous chloride, soaking time is 1 hour;Then 100 milliliters of alkaline solution (concentration 10wt% are immersed in
Sodium hydroxide solution), soaking time be 5 minutes, obtain ferroso-ferric oxide-graphene-cellulose composite hydrogel, spend from
Sub- water repeatedly washs, and freeze-drying obtains the ferroso-ferric oxide-graphene-cellulose applied to electromagnetic shielding field and leads
Electric composite aerogel, the time of freeze-drying are 24 hours.It counts by weight, step (1) graphene oxide and fiber
The ratio of element is 6:94.
(5) pass through above-mentioned steps, ferroso-ferric oxide-graphene-cellulose conduction composite aerogel of preparation is with a thickness of 2 millis
Rice, electromagnetic shielding performance 62dB.This light aerogel material only joined a small amount of graphene, and electromagnetic shielding performance is just
Considerably beyond the application requirement (20dB) of electromagnetic shielding material.Meanwhile with the raising of graphene content, causes electromagnetic wave and exist
Route of transmission in aerogel material increases, to obtain higher electromagnetic shielding performance.
Embodiment 4
The conductive compound airsetting of ferroso-ferric oxide-graphene applied to electromagnetic shielding field that embodiment 4 provides-cellulose
The preparation method of glue, includes the following steps:
(1) 20g sodium hydroxide is added to the water with urea, is uniformly mixed and obtains sodium hydroxide/urea mixed aqueous solution,
In the mixed aqueous solution of the sodium hydroxide/urea, the mass percent concentration of sodium hydroxide is 7wt%, the quality of urea
Percent concentration is 12wt%;0.32 gram of graphene oxide is dispersed in 20 milliliters of water, the aqueous solution of graphene oxide is obtained;
(2) mixed aqueous solution of step (1) sodium hydroxide/urea is subjected to precooling treatment, the temperature of precooling treatment
It is -12 degrees Celsius, the time of precooling treatment is 1 hour;3.68 grams of celluloses are added to 96 grams of sodium hydroxide/urea mixing
It in aqueous solution, stirs 5 minutes, is uniformly mixing to obtain cellulose solution, 100 millis are added in the aqueous solution of 20 milliliters of graphene oxides
It rises in cellulose solution, is uniformly mixed and obtains mixed liquor;By mixed liquor casting film-forming on a glass, then in dilution heat of sulfuric acid
Coagulating bath processing is carried out in (dilution heat of sulfuric acid concentration is 5wt%), the time of coagulating bath processing is 5 minutes, obtains hydrogel, uses
Deionized water washing;
(3) hydrogel after washing step (2) is immersed in 500 milliliters of reducing agent solutions, and (concentration is the vitamin of 30g/L
The aqueous solution of C) in carry out reduction treatment, the temperature of reduction treatment is 95 degrees Celsius, and the time of reduction treatment is 1 hour, is obtained
Graphene-cellulose composite hydrogel, is washed with deionized;
(4) 8mmol iron chloride and 4mmol frerrous chloride are added in 200 milliliters of water, are uniformly mixed and obtain iron chloride and chlorine
Change ferrous mixed aqueous solution;By step (3) washing after graphene-cellulose composite hydrogel be immersed in the iron chloride with
In the mixed aqueous solution of frerrous chloride, soaking time is 1 hour;Then 100 milliliters of alkaline solution (concentration 5wt% are immersed in
Sodium hydroxide solution) in, soaking time be 5 minutes, obtain ferroso-ferric oxide-graphene-cellulose composite hydrogel, use
Deionized water is repeatedly washed, and freeze-drying obtains the ferroso-ferric oxide-graphene-cellulose for being applied to electromagnetic shielding field
Conductive composite aerogel, the time of freeze-drying are 1 hour.It counts by weight, step (1) graphene oxide and fiber
The ratio of element is 8:92.
(5) pass through above-mentioned steps, ferroso-ferric oxide-graphene-cellulose conduction composite aerogel of preparation is with a thickness of 2 millis
Rice, electromagnetic shielding performance 74dB.This light aerogel material only joined a small amount of graphene, and electromagnetic shielding performance is just
More than the application requirement (20dB) of electromagnetic shielding material.Meanwhile with the raising of graphene content, electromagnetic wave is caused in airsetting
Route of transmission in glue material increases, to obtain higher electromagnetic shielding performance.
Above embodiments are only preferrred embodiment of the present invention, for explaining only the invention, are not intended to limit the present invention, this
Field technical staff should belong to guarantor of the invention without departing from change made under spirit of the invention, replacement, modification etc.
Protect range.
Claims (10)
1. a kind of ferroso-ferric oxide-graphene-cellulose conduction composite aerogel preparation side applied to electromagnetic shielding field
Method, which comprises the steps of:
(1) sodium hydroxide and urea are added to the water, are uniformly mixed and obtain sodium hydroxide/urea mixed aqueous solution, oxidation
Graphene dispersion in water, obtains the aqueous solution of graphene oxide;
(2) mixed aqueous solution of step (1) sodium hydroxide/urea is subjected to precooling treatment, cellulose is then added, stirred
Uniformly obtain cellulose solution;The aqueous solution of step (1) described graphene oxide is added in cellulose solution, is uniformly mixed
To mixed liquor;By mixed liquor casting film-forming, coagulating bath processing is then carried out in dilution heat of sulfuric acid, obtains hydrogel, wash;
(3) hydrogel after step (2) washing is immersed in reducing agent solution and carries out reduction treatment, obtain graphene-fiber
Plain composite hydrogel, washing;
(4) iron chloride and frerrous chloride are added to the water, are uniformly mixed and obtain the mixed aqueous solution of iron chloride and frerrous chloride, it will
Graphene-cellulose composite hydrogel after step (3) washing is successively immersed in the mixing water of the iron chloride and frerrous chloride
In solution and alkaline solution, ferroso-ferric oxide-graphene-cellulose composite hydrogel is obtained, is washed, freeze-drying obtains described
Ferroso-ferric oxide-graphene-cellulose conduction composite aerogel applied to electromagnetic shielding field.
2. preparation method according to claim 1, which is characterized in that the quality of step (1) sodium hydroxide and urea
Than for 6:14-8:10;The mass ratio of the urea and water is 10:82-14:80;The quality of the aqueous solution of the graphene oxide
Percent concentration is 0.2-2%.
3. preparation method according to claim 1, which is characterized in that step (2) precooling temperature is -20 DEG C ~ -12
DEG C, pre-coo time is 1-2 hours;The quality of step (2) described cellulose is sodium hydroxide/urea mixed aqueous solution quality
2~8%;The mass ratio of step (1) graphene oxide and step (2) described cellulose is 2:98-8:92.
4. preparation method according to claim 1, which is characterized in that the aqueous solution of step (2) described graphene oxide
Volume is the 10%-30% of cellulose solution volume.
5. preparation method according to claim 1, which is characterized in that the quality percentage of step (2) described dilution heat of sulfuric acid
Specific concentration is 4%-6%, and the time of the coagulating bath processing is 5-10 minutes.
6. preparation method according to claim 1, which is characterized in that step (3) described reducing agent solution includes vitamin C
Aqueous solution, the concentration of the ascorbic aqueous solution is 30-50g/L;The temperature of the reduction treatment is 90-95 degrees Celsius,
The time of the reduction treatment is 1-2 hours.
7. preparation method according to claim 1, which is characterized in that step (4) iron chloride and frerrous chloride rub
You are than being 1.6:1.4-2.4:0.6;The mass volume ratio of the iron chloride and water is 5-10:1g/L.
8. preparation method according to claim 1, which is characterized in that step (4) graphene-cellulose compound water congealing
The time that glue is immersed in the mixed aqueous solution of iron chloride and frerrous chloride is 30-60 minutes;Step (4) described alkaline solution includes
Sodium hydroxide solution, the mass percent concentration of the alkaline solution are 5%-10%, the graphene-cellulose composite hydrogel
The time being immersed in alkaline solution is 5-10 minutes.
9. preparation method according to claim 1, which is characterized in that the time of step (4) described freeze-drying is 20-24
Hour.
10. a kind of four oxidations for being applied to electromagnetic shielding field as made from the described in any item preparation methods of claim 1-9
Three-iron-graphene-cellulose conduction composite aerogel.
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