CN106517160A - Method for preparing isotropic superelastic graphene aerogel - Google Patents
Method for preparing isotropic superelastic graphene aerogel Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 107
- 239000004964 aerogel Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 238000007710 freezing Methods 0.000 claims abstract description 12
- 230000008014 freezing Effects 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000006835 compression Effects 0.000 claims abstract description 9
- 238000007906 compression Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 18
- 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 16
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 8
- 229930003268 Vitamin C Natural products 0.000 claims description 8
- 206010000269 abscess Diseases 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000011718 vitamin C Substances 0.000 claims description 8
- 235000019154 vitamin C Nutrition 0.000 claims description 8
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000499 gel Substances 0.000 claims description 7
- 239000000017 hydrogel Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 4
- 230000006872 improvement Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 210000002421 cell wall Anatomy 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 230000003014 reinforcing effect Effects 0.000 claims 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 241000894007 species Species 0.000 description 12
- 239000004141 Sodium laurylsulphate Substances 0.000 description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001413 cellular effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- 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
- C01B2204/26—Mechanical 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
- C01P2006/16—Pore diameter
-
- 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
- C01P2006/17—Pore diameter distribution
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Abstract
The invention provides a method for preparing isotropic superelastic graphene gasgel. The method comprises the following steps: firstly, stirring and mixing an oxidized graphene aqueous dispersion, a reducing agent and sodium dodecyl sulfate (SDS) at low speed, and then stirring at high speed; heating, freezing, melting at room temperature, washing with ethanol and drying at atmospheric pressure to obtain the isotropic superelastic graphene aerogel. The method provided by the invention has the advantages of simple process and is suitable for industrial production, and the obtained graphene aerogel is isotropic, has uniform cell size, and has excellent compression recovery and good electrochemical performance.
Description
【Technical field】
The present invention relates to a kind of preparation method of isotropism super-elasticity graphene aerogel, belongs to new material technology of preparing
Field, while falling within aeroge preparing technical field.
【Background technology】
Graphene aerogel is obtained through physically or chemically crosslinking by graphene sheet layer.With two kinds of aeroge and Graphene
The double grading of component：Ultralight, porous, conduction, hydrophobic oleophilic oil and with good compression resilience, these properties cause stone
Black alkene aeroge has huge potential using value in terms of catalyst carrier, conductive devices, oily waste treatment and energy snubber.
Graphene aerogel is prepared as raw material with graphene oxide possibility is provided for large-scale production graphene aerogel,
And template is widely used in its preparation process, compared to other Organic substances as template, ice template method with which more
Plus environmental protection, attract the extensive concern of researcher the advantages of succinct.At present ice is removed and is able to completely keep the poroid knot of Graphene
The method of structure is most of to be still dried or lyophilization for supercritical carbon dioxide.The Chinese invention of Application No. CN104925787A
Patent is prepared for pure graphene aerogel using constant pressure and dry first, but the aeroge that the method is obtained forms hole by template of ice
Shape structure, direction orientations of the cavernous structure for being formed along ice-crystal growth, the properties of aeroge show it is each to
Different in nature the characteristics of, and hole wall is thicker, the specific surface area of made graphene aerogel is less.In Application No. CN105600777A
Using dodecyl sodium sulfate as foaming agent, the bubble generated using its stirring is template to state's patent of invention, is prepared for styrene
The grapheme foam of modification, but the invention, first with lyophilization again after liquid nitrogen freezing, preparation process is excessively complicated.Hence with
Simply, effective method prepares that wall is thin, hyperelastic graphene aerogel, to realizing that its large-scale production still has important reality
Border meaning.
【The content of the invention】
[technical problem to be solved]
It is an object of the invention to provide a kind of preparation method of isotropism super-elasticity graphene aerogel.
Another object of the present invention is to provide a kind of method in regulation and control graphene aerogel aperture.
[technical scheme]
Technical scheme provides a kind of preparation method of the hyperelastic graphene aerogel of isotropism, and which is special
Levy and be：The aeroge with lauryl sodium sulfate aqueous solution in stirring the bubble that formed as template, then under heat auxiliary
Graphene oxide is reduced with reducing agent, strong π-π interact and graphene sheet layer is arranged closely in around bubble, most
Post-heating is dried the unnecessary solvent of removing and obtains isotropic super-elasticity graphene aerogel.Its compression ratio is maximum up to 95%
More than., between 100nm 160nm, the size in its aperture is between 100 500 μm for wall thickness.
The present invention is achieved through the following technical solutions：
A kind of preparation method of the hyperelastic graphene aerogel of isotropism, the method is first by graphene oxide moisture
Dispersion liquid, the aqueous solution of sodium lauryl sulphate (SDS) and reducing agent carry out stirring at low speed mixing, then high-speed stirred；Then heat
Reduction, is allowed to form gel；Melt after freezing at room temperature；After cleaning, normal pressure is dried, that is, obtain isotropic super
Elastic graphite alkene aeroge.The aperture of made graphene aerogel can pass through the speed of stirring and the temperature adjusting of freezing, abscess
The thickness of wall can be regulated and controled by changing the concentration of graphene oxide solution.
In accordance with another preferred embodiment of the present invention, it is characterised in that the method is comprised the following steps：
1) graphene oxide aqueous dispersions are prepared.
2) by reducing agent, lauryl sodium sulfate aqueous solution and graphene oxide aqueous dispersions stirring at low speed mix homogeneously；
High-speed stirred is foaming afterwards.
3) by step 2) in mixed liquor heating 30-360min formed gel.
4) by step 3) in gel be cooled to after room temperature again -80 DEG C -10 DEG C freezing 3-12h, with increase Graphene coagulate
The intensity of Jiao Bi.
5) by step 4) in the cleaning of Graphene hydrogel, after removing impurity under normal pressure 30-70 DEG C be dried 12-48h, obtain final product
Isotropic super-elasticity graphene aerogel.
In accordance with another preferred embodiment of the present invention, it is characterised in that：Graphene oxide can using Brodie methods,
Prepared by the methods such as the Hummer of Staudenmaier methods, Hummer, s methods and improvement, s methods, preferably Hummer, s methods, optimum
Select the Hummer for improvement, s methods.
Another kind of preferred implementation of the invention, it is characterised in that：The concentration of Graphene aqueous dispersions used is
2-10mg·ml-1。
In accordance with another preferred embodiment of the present invention, it is characterised in that：The mode of stirring is unrestricted, and preferred magnetic force is stirred
Mix, and the speed of stirring at low speed is 60-300r min-1, the speed of high-speed stirred is 500-2500r min-1, preferred 1000-
2000r·min-1。
In accordance with another preferred embodiment of the present invention, it is characterised in that：The time of stirring at low speed is 3-15min, wherein
It is preferred that 5-10min；The time of high-speed stirred is 1-10min, wherein it is preferred that 2-5min.
In accordance with another preferred embodiment of the present invention, it is characterised in that：Reducing agent used be vitamin C, hydrogen iodide and
One or several in hydrazine hydrate.
In accordance with another preferred embodiment of the present invention, it is characterised in that：The temperature of reduction is 60-95 DEG C, wherein it is preferred that
For 75-85 DEG C.
In accordance with another preferred embodiment of the present invention, it is characterised in that：The big I in the aperture of the graphene aerogel
It is controlled with the temperature by adjusting freezing environment.The temperature of freezing is -10 DEG C -80 DEG C, and preferred temperature is -20 DEG C.
In accordance with another preferred embodiment of the present invention, it is characterised in that：The big I in graphene aerogel aperture passes through
Control stir speed (S.S.), graphene oxide moisture liquid concentration and cryogenic temperature are controlled.
In accordance with another preferred embodiment of the present invention, it is characterised in that：During cleaning solvent used be ethanol, methanol and
One kind in acetone.
Graphene aerogel prepared in accordance with the present invention it is characterized in that：The wall thickness of the graphene aerogel abscess can lead to
The concentration for crossing graphene oxide aqueous dispersions used is controlled.
Graphene aerogel prepared in accordance with the present invention it is characterized in that：The Graphene hydrogel is directly heated at ambient pressure
Graphene aerogel is obtained.
[beneficial effect]
The present invention is as a result of as above technical scheme, thus has the advantage that：
1st, be prepared for isotropism using the method for constant pressure and dry and compression reaction performance reach more than 95% Graphene
Aeroge.
2nd, the graphene aerogel cell wall using the method preparation is thinner, and its thickness is between 100-160nm.
3rd, the graphene aerogel prepared using the method has isotropic structure, and the modulus of vertical and horizontal is basic
It is identical, show isotropism；And Graphene airsetting prepared by existing utilization constant pressure and dry technology is respectively provided with anisotropy.
4th, the aperture of the graphene aerogel prepared using the method is adjustable between 100 500 μm, and its aperture
It is evenly distributed, size can be regulated and controled by the concentration of the temperature of freezing environment, stir speed (S.S.) and graphene oxide moisture liquid.
5th, as the invention has used the atmosphere pressure desiccation of improvement, compared to lyophilization and supercritical drying, technique is more
Plus it is simple, provide possibility for large-scale production graphene aerogel.
【Description of the drawings】
After Fig. 1 is the mixing of graphene oxide aqueous dispersions in embodiment 1, lauryl sodium sulfate aqueous solution and vitamin C
Pictorial diagram before and after stirring.
Fig. 2 is 1,2,3,4 made graphene aerogel cross section scanning electron microscope (SEM) photograph of embodiment.
Fig. 3 is embodiment 4 and 1 made graphene aerogel cross section scanning electron microscope (SEM) photograph of comparative example.
Fig. 4 is embodiment 4 and 1 made graphene aerogel longitudinal section scanning electron microscope (SEM) photograph of comparative example.
Fig. 5 is the photo in embodiment 3 before and after the compression of gained graphene aerogel.
【Specific embodiment】
The present invention is further described with reference to embodiment.But protection scope of the present invention is not limited only to this.
Embodiment 1.
Prepare 3mg ml-1Graphene oxide aqueous dispersions.Take the above-mentioned graphene oxide aqueous dispersions of 6ml and be placed in cylinder
In shape bottle, the 50mg ml of 0.5ml are added thereto to-1The vitamin C of SDS and 36mg, 300r min-1Stirring 3min, then
1000r·min-1Magnetic agitation 2min, reacts 45min in being put into 80 DEG C of air dry ovens, be put into after taking out and being cooled to room temperature-
Freeze 3 hours in 20 DEG C of low temperature environment, melt under room temperature, subsequently with ethanol purge 3 times, the hydrogel after cleaning is put into into 60
DEG C air dry oven in be dried 24h, that is, obtain form and keep good graphene aerogel.Its average pore size is 490 μm, hole
Thin and thick 100nm or so.
Embodiment 2
, with embodiment 1, except for the difference that the concentration of graphene oxide is 4mg ml for the species of material therefor and technological process-1,
Ascorbic consumption is 48mg.Finally give shape and keep good cellular graphene aerogel, its internal holes still it is larger its
Average pore size is 420 μm.
Embodiment 3
, with embodiment 1, except for the difference that the concentration of graphene oxide is 5mg ml for the species of material therefor and technological process-1,
Ascorbic consumption is 60mg.The graphene aerogel that shape keeps good is obtained, its internal holes size is more uniform, averagely
Aperture is 300 μm.Its wall thickness is 120nm.
Embodiment 4
, with embodiment 1, except for the difference that the concentration of graphene oxide is 7mg ml for the species of material therefor and technological process-1,
Ascorbic consumption is 84mg.Obtained shape and kept good graphene aerogel, its pore size distribution it is more uniform and
Average pore size is 250 μm.Its wall thickness is 160nm.
Embodiment 5
, with embodiment 3, the speed stirred after except for the difference that mixing is 500r for the species of material therefor and technological process
min-1, finally given the graphene aerogel that shape keeps good.
Embodiment 6
, with embodiment 3, after except for the difference that mixing, the speed of high-speed stirred is for the species of material therefor and technological process
1500r·min-1, finally given the cellular graphene aerogel that shape keeps good.
Embodiment 7
, with embodiment 3, after except for the difference that mixing, the speed of high-speed stirred is for the species of material therefor and technological process
2000r·min-1, finally given the cellular graphene aerogel that shape keeps good.
Embodiment 8
The species and process flow embodiment 3 of material therefor, after except for the difference that mixing, the speed of high-speed stirred is 2500r
min-1, finally given the cellular graphene aerogel that shape keeps good.
Embodiment 9
, with embodiment 3, after except for the difference that mixing, the speed of high-speed stirred is for the species of material therefor and technological process
3000r·min-1, finally given the cellular graphene aerogel that shape keeps good.
Embodiment 10
The species of material therefor and technological process are -80 DEG C with the temperature of freezing environment unlike embodiment 3, final
The cellular graphene aerogel that shape keeps good is arrived.Its aperture is 100 μm or so, compared with gained Graphene in embodiment 3
The aperture of aeroge is little.
Comparative example 1
Prepare 5mg ml-1Graphene oxide aqueous dispersions.Take the above-mentioned graphene oxide aqueous dispersions of 6ml and be placed in cylinder
In shape bottle, the vitamin C of 60mg, 1000r min-1Magnetic agitation 2min, reacts 45min in being put into 80 DEG C of air dry ovens, takes
It is put into after going out to be cooled to room temperature in -20 DEG C of refrigerator and freezes 3 hours, melts under room temperature after taking-up, afterwards with ethanol purge 3 times,
Afterwards the hydrogel for having cleaned is put in 60 DEG C of air dry oven and is dried 24h, that is, obtain the Graphene that form keeps good
Aeroge.But this graphene aerogel wall is thicker for 240nm, and aperture averaging is 800 μm, presents anisotropy.
Comparative example 2
The species of material therefor and technological process with embodiment 3, except for the difference that by graphene oxide water solution, dodecyl
Direct 2000r min after aqueous sodium persulfate solution and vitamin C mixing-1Stirring 2min.Inside the graphene aerogel for finally giving
Structure heterogeneity, defect are more.
Comparative example 3
The species of material therefor and technological process with embodiment 3, except for the difference that by graphene oxide water solution, dodecyl
200r min after aqueous sodium persulfate solution and vitamin C mixing-1Graphene hydrogel is directly reduced to after stirring at low speed 2min.Most
The substantially no abscess of the material for obtaining eventually.
Comparative example 4
, with embodiment 3, except for the difference that the temperature of freezing environment is -190 DEG C, finally for the species of material therefor and technological process
The graphene aerogel hole for obtaining caves in, it is impossible to keep the original form of hydrogel.
As seen from Figure 1 by graphene oxide, body after lauryl sodium sulfate aqueous solution and vitamin C mixing
Product is increased by about one time, and the increase of its volume is because adding SDS stirrings to define bubble, and these bubbles are subsequent graphite
The formation of alkene aeroge provides template.As can see from Figure 2 with the increase of graphene oxide concentration, the thickness of graphene wall
Degree increases, and hole is more uniform, and presents alveolate texture, so as to the formation for demonstrating cavernous structure has benefited from SDS foaming.Figure
The cross-sectional view of 3 graphene aerogels to be formed in embodiment 4 and comparative example 1, it can be seen that the present invention foams to be formed with SDS
Graphene aerogel of the abscess for template, abscess are circle, and average diameter is 250 μm, and does not add SDS, with ice crystal as template
The abscess of graphene aerogel is ellipse, and its major diameter is 800 μm or so, 200 μm or so of minor axis diameter, and its aperture is bright
It is aobvious larger.This is because SDS foams presents circle, and graphite aeroge cellular structure prepared by existing constant pressure and dry technology
The form and dimension of the ice as template is limited to, and the size foamed with SDS depends on the consumption of SDS and the speed of stirring,
Therefore the abscess-size of made graphene aerogel of the invention is more easy to control.Made Graphene gas of the invention as can be seen from Figure 4
The longitudinal section of gel still presents circular blister, and the longitudinal section of graphene aerogel is in prepared by existing constant pressure and dry technology
Reveal the orderly channel design in longitudinal direction.And can be seen that the cell wall of made graphene aerogel of the invention is thinner by contrast,
Between 100-160nm, slim and graceful transparence is presented.Can see in photo before and after compressing from Fig. 5, made graphite of the invention
Deformation after the compression ratio of alkene aeroge reaches 95% and compression can recover, and illustrate which has good compression resilience.
Claims (10)
1. a kind of preparation method of isotropism super-elasticity graphene aerogel, the method be with graphene oxide as raw material, and
The abscess for producing is stirred with lauryl sodium sulfate aqueous solution to prepare as template；It is characterized in that the method is depositing in reducing agent
Under, after graphene oxide aqueous dispersions are mixed with lauryl sodium sulfate aqueous solution stirring at low speed, then high-speed stirred foaming,
Then graphene oxide layer is reduced to form tridimensional network, then freezes the hole wall formed by reinforcing graphene sheet layer, most
Normal heating is dried afterwards, obtains isotropic graphene aerogel.
2. as claimed in claim 1 a kind of preparation method of graphene aerogel, it is characterised in that the method is comprised the following steps：
1) graphene oxide aqueous dispersions are prepared；
2) by reducing agent, lauryl sodium sulfate aqueous solution and graphene oxide aqueous dispersions stirring at low speed mix homogeneously；Afterwards
High-speed stirred is foaming；
3) by step 2) made mixed liquor heating, form gel；
4) by step 3) freeze after the cooling of made gel；
5) by step 4) in Graphene hydrogel melt after clean, normal heating be dried, that is, obtain isotropic super-elasticity
Graphene aerogel.
3. preparation method according to claim 2, it is characterised in that：The speed and high-speed stirred speed of stirring at low speed is respectively
60-300r·min-1With 500-3000r min-1, mixing time is respectively 3-15min and 1-10min.
4. preparation method according to claim 2, it is characterised in that：Described graphene oxide can using Brodie methods,
It is prepared by the Hummer of Staudenmaier methods, Hummer, s methods and improvement, s methods.
5. preparation method according to claim 2, it is characterised in that：The concentration of Graphene aqueous dispersions used is 2-10mg ml-1。
6. preparation method according to claim 2, it is characterised in that：It is 60-95 DEG C that step 3 is thermally formed the temperature of gel, plus
The hot time is 30-360min, and the time of step 4 freezing is 3-12h, and the temperature of freezing is -80 to -10 DEG C.
7. preparation method according to claim 2, it is characterised in that：During reducing agent used is vitamin C, hydrogen iodide and hydrazine hydrate
One or several.
8. preparation method according to claim 2, it is characterised in that：During during cleaning, solvent used is ethanol, methanol and acetone
One kind；The temperature of constant pressure and dry is 30-70 DEG C, and the dry time is 12-48h.
9. preparation method according to claim 1, it is characterised in that：The compression ratio of made graphene aerogel reach 95% with
On；The size in its aperture is 100-500 μm；Wall thickness is 100nm-160nm.
10. preparation method according to claim 2, it is characterised in that：Made graphene aerogel pore size can be by stirring
Mix the control of speed, graphene oxide moisture liquid concentration and cryogenic temperature；The thickness of cell wall can be by changing graphene oxide water
The concentration of dispersion liquid is regulated and controled.
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659099A (en) * | 2012-05-29 | 2012-09-12 | 上海第二工业大学 | Preparation method of anisotropic graphene foam |
| CN104495820A (en) * | 2014-12-17 | 2015-04-08 | 北京化工大学 | Porous graphene aerogel and preparation method thereof |
| CN105384165A (en) * | 2015-12-18 | 2016-03-09 | 首都师范大学 | Spongy-like lightweight graphene aerogel preparation method |
| CN105600777A (en) * | 2016-01-29 | 2016-05-25 | 北京理工大学 | Preparation method of polystyrene modified three-dimensional graphene foam |
-
2016
- 2016-11-22 CN CN201611025874.8A patent/CN106517160B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659099A (en) * | 2012-05-29 | 2012-09-12 | 上海第二工业大学 | Preparation method of anisotropic graphene foam |
| CN104495820A (en) * | 2014-12-17 | 2015-04-08 | 北京化工大学 | Porous graphene aerogel and preparation method thereof |
| CN105384165A (en) * | 2015-12-18 | 2016-03-09 | 首都师范大学 | Spongy-like lightweight graphene aerogel preparation method |
| CN105600777A (en) * | 2016-01-29 | 2016-05-25 | 北京理工大学 | Preparation method of polystyrene modified three-dimensional graphene foam |
Non-Patent Citations (2)
| Title |
|---|
| LINGXIAO LV ET AL;: "Solution-Processed Ultraelastic and Strong Air-Bubbled Graphene Foams", 《SMALL》 * |
| RUJING ZHANG ET AL;: "Three-dimensional porous graphene sponges assembled with the combination of surfactant and freeze-drying", 《NANO RESEARCH》 * |
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