CN106809822B - A kind of preparation method of super-elasticity graphene aerogel - Google Patents
A kind of preparation method of super-elasticity graphene aerogel Download PDFInfo
- Publication number
- CN106809822B CN106809822B CN201710046029.7A CN201710046029A CN106809822B CN 106809822 B CN106809822 B CN 106809822B CN 201710046029 A CN201710046029 A CN 201710046029A CN 106809822 B CN106809822 B CN 106809822B
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphene aerogel
- shape
- preparation
- aerogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 103
- 239000004964 aerogel Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000006260 foam Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000017 hydrogel Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- -1 formaldehyde, saccharide compound Chemical class 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000006227 byproduct Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 description 14
- 239000004814 polyurethane Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000013138 pruning Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009966 trimming Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 206010000269 abscess Diseases 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention belongs to aeroge preparing technical fields,It is related to a kind of preparation method of super-elasticity graphene aerogel,Appropriate reducing agent is added in graphene oxide dispersion,With block of polymeric foam adsorption and oxidation graphene dispersing solution,And restore graphene oxide foam block oil bath heating,Again by being freeze-dried sample drying,Then foam of polymers is removed by high-temperature heat treatment to obtain graphene aerogel,Regulate and control the shape of final graphene aerogel by designing the shape of foam of polymers,And without as the preparation process of other graphene aerogels,Regulate and control its shape by changing the shape of container,Therefore the manufacturing cost of graphene aerogel is greatly reduced,And the graphene aerogel of complicated shape can be prepared,This method preparation process is simple,Design concept is ingenious,Raw material is prepared to be easy to get,Preparation efficiency is high,And the graphene aerogel prepared has excellent chemical property,Application environment is friendly,Wide market.
Description
Technical field：
The invention belongs to aeroge preparing technical field, it is related to a kind of preparation method of graphene aerogel, particularly one
The preparation method of kind super-elasticity graphene aerogel, regulates and controls the graphene finally prepared by changing the shape of polymer template
The shape of aeroge.
Background technology：
Graphene is a kind of two-dimensional slice material of single layer of carbon atom composition, has excellent mechanical, electricity and hot property.Mesh
The preparation method of preceding graphene mainly has：Mechanical stripping method, chemical vapour deposition technique, plane of crystal epitaxial growth method and oxidation are also
Former method.Wherein, oxidation-reduction method is the method for most possible industrialized production graphene.By cheap graphite Hummers methods
Oxidation stripping is self-assembled into three-dimensional grapheme net into graphene oxide, graphene oxide dispersion by chemistry or thermal reduction
Network, then by being further dried to obtain graphene aerogel.Graphene aerogel can arbitrary adjustable shape, elasticity it is also fine,
It can still be restored to the original state after compression 80%, have ultrafast, superelevation adsorption capacity to organic solvent, be that the oil sucting force being reported is most strong
Material, existing oil suction product can only generally inhale the liquid of 10 times or so of sole mass, and graphene aerogel can absorb 250 times
Left and right, reaches as high as 900 times, and only oil suction does not absorb water；Graphene aerogel also is able to be applied to a lot of other fields, such as pass
Sensor, sound insulating material, ultracapacitor, catalytic electrode material etc. are greatly expanded the application of graphene.Some researchers
Improve the mechanical property of graphene aerogel by improving preparation method, for example, Qiu etc. be prepared for by multistep method it is ultralight
Resilient graphene aerogel, the aeroge have more than 80% resilience [L.Qiu, Z.Liu, L.Y.Chang, Y.Z.Wu,
D.Li,Nature Communications,2012,3,1241].At this stage graphene aerogel mainly have it is several under several preparations
Method, first, graphene aerogel is done via reduced graphene hydrogel is formed after graphene oxide gel using freezing
Dry or supercritical drying drying method is prepared into graphene aerogel；Second is that graphene oxide dispersion directly freezed is dried, then lead to
The method for crossing reduction obtains graphene aerogel.The shape of graphene aerogel prepared by both methods can be with the shape of container
It is similar, because can be shunk when Graphene gel according to container shapes equal proportion [W.F.Chen, L.F.Yan,
L.Y.Chang, Y.Z.Wu, D.Li, Nanoscale, 2011,3,3132], that is to say, that it can only be by changing container shapes ability
Desired aeroge sample is obtained, this undoubtedly increases production cost, also limits production efficiency, therefore, is related to preparing a kind of
The preparation method of super-elasticity graphene aerogel regulates and controls the shape of final aeroge by changing the shape of polymer template,
Preparation process is simple and fast.
Invention content：
It is an object of the invention to overcome shortcoming of the existing technology, seek to design a kind of super-elasticity graphene aerogel
Preparation method, using polymer as template, regulate and control the shape of final aeroge by changing the shape of polymer template, prepare
Aeroge have excellent resilience, higher mechanical strength and excellent chemical property.
To achieve these goals, the preparation method concrete technology of super-elasticity graphene aerogel of the present invention includes
Following steps：
(1) a concentration of 0.5~12mg/ml graphene oxide solutions are first added in reaction utensil, adds reducing agent and stir
It mixes uniformly, makes within 30~120 minutes graphene oxide solution and reducing agent that oxidation fully occur also in 0~30 DEG C of stirred in water bath
Original reaction, the mixed solution that graphene-containing is made are spare；The reducing agent and the mass ratio of graphene oxide solution are 1：1~
10：1, one kind in hydrazine hydrate, sodium borohydride, formaldehyde, saccharide compound, ascorbic acid, amino acid of the reducing agent or
A variety of mixing；
(2) block of polymeric foam is trimmed to and is needed graphene aerogel to be prepared identical with pruning tool at room temperature
Shape, the volume of the block of polymeric foam after processing is 4.8-5.2cm3, which is put into mixed solution
Reaction utensil is placed on heating reduction 8~24 hours in 70~100 DEG C of oil baths again after adsorbing mixed solution 5-60 minutes, be made
To the mixture containing graphene-polymer hydrogel, remaining reducing agent and other by-products, the block of polymeric foam is poly-
It is arbitrary in styrene, polyurethane, polypropylene, polyethylene terephthalate, polyvinyl chloride, poly- melamine, polyethylene
It is a kind of；
(3) mixture prepared in step (2) is dialysed 1~4 day in deionized water, to wash away remaining reducing agent and
Other by-products, the graphene-polymer hydrogel purified；
(4), by the graphene-polymer hydrogel of purifying obtained in step (3) at -40 DEG C -- freeze 20- at 196 DEG C
It 60 minutes, freezes in graphene-polymer hydrogel superfluous water, then in temperature is -15~30 DEG C, vacuum degree 0.1-
It is obtained more the water freezed in graphene-polymer hydrogel to be made directly to distil discharge dry 5-10 hour under the conditions of 165Pa
The graphene-polymer aeroge of pore structure；
(5), by graphene obtained-polyurethane aeroge in 500-1000 DEG C of baking oven, under inert atmosphere be heat-treated 1~
5 hours, block of polymeric foam is made to be carbonized, to remove block of polymeric foam, be made identical with trimming post-consumer polymer foam block
The graphene aerogel of shape, the inert atmosphere are selected from：Nitrogen, argon gas, helium or nitrogen, argon gas, helium and hydrogen
Mixed gas.
The graphene aerogel prepared using the method for the invention is measured, aperture is 10~50 microns, close
It spends for 5~15mg/cm3, conductivity is 0.01~0.2S/cm；And the graphene aerogel has good rebound characteristics, pressure
Original shape can be returned to after contracting 95%；Prepared graphene aerogel has good chemical property, in 0.3A/g
Lower high specific thermoelectricity capacitance is up to 150F/g；Increase current strength to 50A/g, specific capacitance value retains 71%；Undergo 10000 perseverances
Current cycle charge and discharge specific capacitance value can retain more than 86%.
Compared with prior art, the present invention it has the following advantages：Graphene aerogel prepared by the present invention is one kind two
The inorganic conductive aeroge of the three-dimensional network of graphene composition is tieed up, there is uniform foam structure and light, with excellent
Different resilience, higher mechanical strength and good chemical property；It, can be poly- by designing using foam of polymers as template
The shape of object foam is closed to regulate and control the shape of final graphene aerogel, and without as the preparation process of other graphene aerogels
Equally, regulate and control its shape by changing the shape of container, therefore greatly reduce the manufacturing cost of graphene aerogel, and
The graphene aerogel of complicated shape can be prepared, this method preparation process is simple, and design concept is ingenious, prepares raw material and is easy to get,
Preparation efficiency is high, and the graphene aerogel prepared has excellent chemical property, and application environment is friendly, and market prospects are wide
It is wealthy.
Description of the drawings：
Fig. 1 is scanning electron microscope (SEM) figure of graphene aerogel of the present invention.
Fig. 2 is compression stress-compression strain of the graphene aerogel of the present invention in cycle compression performance test
Curve.
Fig. 3 (a) is the cyclic voltammetry curve schematic diagram of graphene aerogel electrode of the present invention；Fig. 3 (b) is this hair
The impulse electricity curve synoptic diagram of the bright graphene aerogel electrode being related to；Fig. 3 (c) is graphene aerogel of the present invention electricity
Specific capacitance value conservation rate figure after 10000 constant current cycle charge-discharges of experience of pole.
Specific embodiment
Below in conjunction with the accompanying drawings and pass through embodiment the present invention is described in further detail.
Embodiment 1：
The preparation method of super-elasticity graphene aerogel that the present embodiment is related to, specific process step include：
(1), 5mg hydrazine hydrates are added in the reaction utensil for filling a concentration of 5mg/ml graphene oxide solutions of 10ml as also
Former agent, stirring in water bath makes graphene oxide solution and hydrazine hydrate that redox reaction fully occur in 20 minutes at 20 DEG C, is made and contains
The mixed solution of graphene is spare；
(2), polyurethane foam is trimmed to and is needed graphene aerogel to be prepared identical with pruning tool at room temperature
Shape, the volumes of the polyurethane foamed blocks after processing is 4.8-5.2cm3, which is put into mixed solution
After adsorbing mixed solution 5-30 minutes, then reaction utensil is placed in 70 DEG C of oil baths and is heated 20 hours, be made containing graphite
The mixture of alkene-polyurethane hydrogel, remaining hydrazine hydrate and other by-products；
(3), the mixture prepared in step (2) is dialysed 2 days in deionized water, to wash away hydrazine hydrate and other pairs
Product, the graphene-polyurethane hydrogel purified；
(4), graphene-polyurethane hydrogel of purifying obtained in step (3) at -196 DEG C is freezed 30 minutes, made
Superfluous water freezes in graphene-polyurethane hydrogel, then in temperature is -15~30 DEG C, vacuum degree be 0.1Pa under the conditions of dry 5
Hour, the water freezed in graphene-polyurethane hydrogel to be made directly to distil discharge, graphene-poly- ammonia of obtained porous structure
Ester aeroge；
(5), it by graphene obtained-polyurethane aeroge in 500 DEG C of baking ovens, is heat-treated 2 hours, makes under nitrogen atmosphere
Polyurethane foamed blocks are carbonized, to remove polyurethane foamed blocks, the stone of polyurethane foamed blocks same shape after being made and trimming
Black alkene aeroge.
Embodiment 2：
The preparation method of super-elasticity graphene aerogel that the present embodiment is related to, specific process step include：
(1), 150mg ascorbic acid is added in the reaction utensil for filling a concentration of 7.5mg/ml graphene oxide solutions of 10ml
As reducing agent, stirring in water bath makes graphene oxide solution and ascorbic acid that redox fully occur for 60 minutes anti-at 10 DEG C
Should, the mixed solution that graphene-containing is made is spare；
(2), polypropylene foam block is trimmed to and needed graphene aerogel phase to be prepared with pruning tool at room temperature
Same shape, the volume of the polypropylene foam block after processing is 4.8-5.2cm3, which is put into mixed solution
In come after adsorbing mixed solution 30 minutes, then reaction utensil is placed in 100 DEG C of oil baths and is heated 8 hours, be made containing graphene-
The mixture of polypropylene hydrogel, remaining ascorbic acid and other by-products；
(3), the mixture prepared in step (2) is dialysed 2 days in deionized water, to wash away ascorbic acid and other
By-product, the graphene purified-polypropylene hydrogel；
(4), the graphene of purifying obtained in step (3)-polypropylene hydrogel at -75 DEG C is freezed 40 minutes, made
Superfluous water freezes in graphene-polypropylene hydrogel, then in temperature is -15~30 DEG C, and dry 5 is small under the conditions of vacuum degree is 20Pa
When, the water freezed in graphene-polypropylene hydrogel to be made directly to distil discharge, graphene-polypropylene of porous structure is made
Aeroge；
(5), it by graphene obtained-polypropylene aeroge in 1000 DEG C of baking ovens, is heat-treated 1 hour under argon atmosphere,
Polypropylene foam block is made to be carbonized, to remove polyurethane foamed blocks, polyurethane foamed blocks same shape after being made and trimming
Graphene aerogel.
Embodiment 3：
The preparation method of super-elasticity graphene aerogel that the present embodiment is related to, specific process step include：
(1), 150mg sodium borohydrides are added in the reaction utensil for filling a concentration of 12mg/ml graphene oxide solutions of 10ml
As reducing agent, stirring in water bath makes graphene oxide solution and sodium borohydride that redox fully occur for 100 minutes anti-at 30 DEG C
Should, the mixed solution that graphene-containing is made is spare；
(2), polyethylene terephthalate foam block is trimmed to and needed with pruning tool at room temperature and is to be prepared
The identical shape of graphene aerogel, the volume of the polyethylene terephthalate foam block after processing is 5cm3, this is gathered
Ethylene glycol terephthalate foam block is put into mixed solution come after adsorbing mixed solution 30 minutes, then reaction utensil is placed on
Heated 24 hours in 60 DEG C of oil baths, be made containing graphene-polyethylene terephthalate hydrogel, remaining sodium borohydride and
The mixture of other by-products；
(3), the mixture prepared in step (2) is dialysed 2 days in deionized water, to wash away sodium borohydride and other
By-product, the graphene purified-polyethylene terephthalate hydrogel；
(4), by the graphene of purifying obtained in step (3)-polyethylene terephthalate hydrogel at -50 DEG C
Freezing 40 minutes freezes in graphene-polyethylene terephthalate hydrogel superfluous water, then in temperature is -15~30
DEG C, vacuum degree is 10 hours dry under the conditions of being 50Pa, to make what is freezed in graphene-polyethylene terephthalate hydrogel
Water directly distils discharge, and graphene-polyethylene terephthalate aeroge of porous structure is made；
(5), by graphene obtained-polyethylene terephthalate aeroge in 600 DEG C of baking ovens, under nitrogen atmosphere
Heat treatment 2 hours, makes polyethylene terephthalate foam block be carbonized, to remove polyethylene terephthalate bubble
Foam block, the graphene aerogel of polyethylene terephthalate foam block same shape after being made and trimming.
The graphene aerogel prepared in embodiment 1 is subjected to SEM tests, as shown in Figure 1, graphene aerogel abscess knot
Structure, abscess-size are 15-50 microns；The graphene aerogel prepared in example 2 is subjected to compression reaction test, compression ratio is maximum
Up to 95%, as shown in Fig. 2, can be returned to original height after the every second compression of the graphene aerogel prepared, illustrate to prepare
Graphene aerogel have good resilience.
The graphene aerogel prepared in embodiment 3 is placed in the electrolyte solution of 6mol/L, tests its electrochemistry
Capacitive property, such as the cyclic voltammetry curve schematic diagram that Fig. 3 (a) is graphene aerogel electrode prepared by embodiment 3, Fig. 3 (b) is
The impulse electricity curve synoptic diagram of graphene aerogel electrode prepared by embodiment 3, Fig. 3 (c) are graphene gas prepared by embodiment 3
Specific capacitance value can retain more than 86% after 10000 constant current cycle charge-discharges of experience of gel electrode, under 0.3A/g most
Big specific heat capacitance is up to 150F/g；Increase current strength to 50A/g, specific capacitance value retains 71%.
Claims (3)
1. a kind of preparation method of super-elasticity graphene aerogel, it is characterised in that preparation method concrete technology includes following step
Suddenly：
(1) a concentration of 0.5~12mg/ml graphene oxide solutions are first added in reaction utensil, add reducing agent and stirred equal
It is even, make within 30~120 minutes graphene oxide solution and reducing agent that redox fully occur in 0~30 DEG C of stirred in water bath anti-
Should, the mixed solution that graphene-containing is made is spare；The reducing agent and the mass ratio of graphene oxide solution are 1：1~10：1,
The reducing agent is one or more mixed in hydrazine hydrate, sodium borohydride, formaldehyde, saccharide compound, ascorbic acid, amino acid
It closes；
(2) block of polymeric foam is trimmed to the shape identical with graphene aerogel to be prepared is needed at room temperature, after processing
Block of polymeric foam volume be 4.8-5.2cm3, which is put into mixed solution to adsorb mixed solution
Reaction utensil is placed in 70~100 DEG C of oil baths heating reduction 8~24 hours again after 5-60 minutes, be made containing graphene-
The mixture of polyalcohol hydrogel, remaining reducing agent and other by-products, the block of polymeric foam is polystyrene, poly- ammonia
Any one in ester, polypropylene, polyethylene terephthalate, polyvinyl chloride, poly- melamine, polyethylene；
(3) mixture prepared in step (2) is dialysed 1~4 day in deionized water, to wash away remaining reducing agent and other
By-product, the graphene-polymer hydrogel purified；
(4), by the graphene-polymer hydrogel of purifying obtained in step (3) at -40 DEG C -- 20-60 points are freezed at 196 DEG C
Clock freezes in graphene-polymer hydrogel superfluous water, then in temperature is -15~30 DEG C, and vacuum degree is 0.1-165Pa items
Dry 5-10 hour under part, the water freezed in graphene-polymer hydrogel to be made directly to distil discharge, obtained porous structure
Graphene-polymer aeroge；
(5), it is small that 1~5 is heat-treated by graphene-polymer aeroge obtained in 500-1000 DEG C of baking oven, under inert atmosphere
When, block of polymeric foam is made to be carbonized, to remove block of polymeric foam, is made and trims post-consumer polymer foam block same shape
Graphene aerogel.
2. the preparation method of super-elasticity graphene aerogel according to claim 1, it is characterised in that the graphite prepared
Alkene aeroge has rebound characteristics, still is able to be returned to original shape after compression 95%.
3. the preparation method of the super-elasticity graphene aerogel according to any claim in claim 1-2, feature
It is that the inert atmosphere is selected from：Nitrogen, argon gas, helium or nitrogen, argon gas, helium and hydrogen mixed gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710046029.7A CN106809822B (en) | 2017-01-22 | 2017-01-22 | A kind of preparation method of super-elasticity graphene aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710046029.7A CN106809822B (en) | 2017-01-22 | 2017-01-22 | A kind of preparation method of super-elasticity graphene aerogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106809822A CN106809822A (en) | 2017-06-09 |
| CN106809822B true CN106809822B (en) | 2018-06-22 |
Family
ID=59111236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710046029.7A Expired - Fee Related CN106809822B (en) | 2017-01-22 | 2017-01-22 | A kind of preparation method of super-elasticity graphene aerogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106809822B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706395A (en) * | 2017-10-30 | 2018-02-16 | 成都格莱飞科技股份有限公司 | A kind of preparation method of polyester/graphite alkene aerogel composite |
| CN107804839B (en) * | 2017-11-28 | 2019-12-10 | 航天特种材料及工艺技术研究所 | High-elasticity graphene aerogel and preparation method thereof |
| CN108275674B (en) * | 2018-02-02 | 2021-05-25 | 东华大学 | Super-elastic graphene aerogel with thermoelectric effect and preparation method thereof |
| CN108250728B (en) * | 2018-03-09 | 2020-11-03 | 四川大学 | Polymer/graphene aerogel composite foam material and preparation method thereof |
| CN109575467B (en) * | 2018-10-24 | 2021-01-15 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Preparation method of graphene-PVC composite material |
| CN111847429B (en) * | 2019-04-28 | 2023-03-21 | 深圳光启岗达创新科技有限公司 | Preparation method and application of three-dimensional graphene wave-absorbing material |
| CN110127670A (en) * | 2019-05-16 | 2019-08-16 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of graphene three-dimensional structure aeroge hydrophobic material |
| CN110451493B (en) * | 2019-09-02 | 2021-10-22 | 内蒙古农业大学 | Graphene aerogel and preparation method and application thereof |
| CN113277864B (en) * | 2020-02-20 | 2022-05-31 | 中国科学院化学研究所 | Preparation method of carbonaceous aerogel and aerogel |
| CN112794705A (en) * | 2021-01-13 | 2021-05-14 | 兰州大学 | Method for preparing hyperelastic silicon oxide nano ceramic aerogel based on graphene serving as template |
| CN115650215A (en) * | 2022-10-27 | 2023-01-31 | 厦门伟然新碳科技有限公司 | Preparation method of high-elasticity waterborne polyurethane/graphene aerogel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626171A (en) * | 2013-11-28 | 2014-03-12 | 中国科学技术大学 | Preparation method of oil-water separation material |
| CN104276565A (en) * | 2014-07-16 | 2015-01-14 | 东华大学 | Preparation method of ultralight graphene elastic aerogel |
| CN104843676A (en) * | 2014-12-03 | 2015-08-19 | 北汽福田汽车股份有限公司 | Preparation method for graphene aerogel |
| CN105694433A (en) * | 2016-03-30 | 2016-06-22 | 天津大学 | Preparation method of polymer foam/graphene composite material integrating high heat conductivity and high flexibility |
-
2017
- 2017-01-22 CN CN201710046029.7A patent/CN106809822B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626171A (en) * | 2013-11-28 | 2014-03-12 | 中国科学技术大学 | Preparation method of oil-water separation material |
| CN104276565A (en) * | 2014-07-16 | 2015-01-14 | 东华大学 | Preparation method of ultralight graphene elastic aerogel |
| CN104843676A (en) * | 2014-12-03 | 2015-08-19 | 北汽福田汽车股份有限公司 | Preparation method for graphene aerogel |
| CN105694433A (en) * | 2016-03-30 | 2016-06-22 | 天津大学 | Preparation method of polymer foam/graphene composite material integrating high heat conductivity and high flexibility |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106809822A (en) | 2017-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106809822B (en) | A kind of preparation method of super-elasticity graphene aerogel | |
| Xiao et al. | N, S-containing polycondensate-derived porous carbon materials for superior CO2 adsorption and supercapacitor | |
| CN106422995B (en) | A kind of graphene aerogel and its hybrid composite material and the preparation method and application thereof | |
| CN104355302B (en) | The preparation method of a kind of Graphene/polyimide-based carbon aerogels | |
| CN112094625A (en) | Boron nitride nanotube aerogel/phase change heat conduction composite material and preparation method thereof | |
| Lei et al. | Highly nitrogen-doped three-dimensional carbon fibers network with superior sodium storage capacity | |
| Zhao et al. | Efficient synthesis of nitrogen and oxygen co-doped hierarchical porous carbons derived from soybean meal for high-performance supercapacitors | |
| Gao et al. | Bifunctional 3D n-doped porous carbon materials derived from paper towel for oxygen reduction reaction and supercapacitor | |
| CN105314629A (en) | Method for directly preparing co-doping three-dimensional graphene electrode material through biomass carbon sources | |
| CN107188171B (en) | Porous carbon materials and preparation method and the porous carbon-based electrode material for supercapacitor prepared using the porous carbon materials | |
| CN103466604A (en) | Preparation method of porous graphene | |
| Teng et al. | Biotemplating preparation of N, O-codoped hierarchically porous carbon for high-performance supercapacitors | |
| CN104071768B (en) | Part graphitization porous carbon electrode material of aperture fractional distribution and preparation method thereof | |
| CN110921721B (en) | Preparation and application of metal organic framework-derived bimetallic hydroxide | |
| CN107017091A (en) | Nitrogenous multistage porous carbon/graphene composite material and its preparation method and application | |
| Hu et al. | Nitrogen-doped hierarchical porous carbons prepared via freeze-drying assisted carbonization for high-performance supercapacitors | |
| CN106910638A (en) | A kind of is carbon material and its preparation method and application of template based on Zr MOFs composites | |
| Lv et al. | One-pot synthesis of nitrogen-doped carbon aerogels derived from sodium lignosulfonate embedded in carrageenan for supercapacitor electrode materials | |
| Chen et al. | Synthesis of nitrogen‐doped porous carbon monolith for binder‐free all‐carbon supercapacitors | |
| Zong et al. | Zeolitic imidazolate framework-8 derived two-dimensional N-doped amorphous mesoporous carbon nanosheets for efficient capacitive deionization | |
| CN110371970A (en) | A kind of preparation method of the rich nitrogen grading porous carbon material of high-specific surface area | |
| CN108831759B (en) | Graphene/chitosan porous carbon composite material and preparation method and application thereof | |
| CN105819440A (en) | Method for preparing block graphene aerogel | |
| CN108039283B (en) | A kind of rich N doping multi-stage porous carbon material and the preparation method and application thereof based on in-situ polymerization | |
| CN107215871A (en) | A kind of preparation method of activated carbon for super capacitors |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180622 |