CN107804839A - A kind of high resiliency graphene aerogel and preparation method thereof - Google Patents
A kind of high resiliency graphene aerogel and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 134
- 239000004964 aerogel Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000499 gel Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000000017 hydrogel Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005728 strengthening Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- 239000003638 chemical reducing agent Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 238000006722 reduction reaction Methods 0.000 claims description 21
- -1 polypropylene Polymers 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 9
- 238000000352 supercritical drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 229940012017 ethylenediamine Drugs 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 238000004132 cross linking Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229920002521 macromolecule Polymers 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 235000010344 sodium nitrate Nutrition 0.000 description 8
- 239000004317 sodium nitrate Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012286 potassium permanganate Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 4
- 229910001626 barium chloride Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 150000002171 ethylene diamines Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008876 conformational transition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
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Landscapes
- Carbon And Carbon Compounds (AREA)
- Colloid Chemistry (AREA)
Abstract
The present invention relates to a kind of high resiliency aeroge and preparation method thereof, the preparation method comprises the following steps：(1) the step of preparing graphene oxide colloidal sol；(2) the step of preparing graphene hydrogel；(3) drying steps, it is characterised in that also include between step (2) and step (3)：(i) the step of strengthening skeleton；The step (i) is carried out as follows：(a) high-molecular compound is dissolved in good solvent, is configured to Polymer Solution；(b) graphene hydrogel made from step (2) is soaked in the Polymer Solution, obtains Graphene gel；(c) Graphene gel is soaked in poor solvent.The present invention carries out parcel connection using macromolecular chain to graphene sheet layer, so as to improve skeleton crosslinking points and frame strength, can effectively improve the elasticity of graphene aerogel, prepare the high resiliency graphene aerogel material of excellent in mechanical performance.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of high resiliency graphene aerogel and its preparation side
Method.
Background technology
Aerogel material is also referred to as " solid cigarette ", is the minimum solid material of known density in the world at present, its microstructure
On formed by nano particle accumulation, form nano-porous structure, there is the characteristics of density is low, specific surface area is high, thermal conductivity is low, make
Have wide practical use for heat-barrier material, sorbing material etc..
Research at present the most extensively, the most ripe aerogel material of technology be aerosil, it is by colloidal sol-coagulate
Glue method is prepared through supercritical drying again, possess high porosity (>=85%), great specific surface area (250~
800m2/ g), relatively low density (0.03~0.50g/cm3) and relatively low thermal conductivity factor (0.01~0.03W/ (mK)).But
Most aeroges including aerosil form by particle packing, and contact area is small between particle, phase
Interreaction force is weak, thus macroscopically shows easy dry linting, the characteristics of fragility is big, limit its in Elastic heat insulation Material Field should
With.
The laminated structure carbon material that graphene is made up of single carbon atomic layer, with excellent mechanical property and electrically
Energy.Due to its special lamellar structure, graphene has certain bendable folding endurance and flexibility so that it is very suitable for as elastic gas
The component units of gel rubber material.It can be interacted and be connected by π-π between graphene film Rotating fields, form adjustable interaction
Power, advantageously form with integrally-built three dimensional gel.Application publication number be CN101941693A, CN102910625A,
The preparation of graphite oxide aerogel material has been all referred in CN102887508A patent application document, but to its elastic performance
Regulation and control and characterize not yet refer to.Under stress condition, easily it is subjected to displacement between graphene sheet layer, so as to be moved to new balance
New steady s tate is formed on position, does not have the characteristics of elasticity or weaker elasticity after showing graphene stress.
In terms of the elasticity of graphene oxide composite material is improved, current existing method includes：From weak reductant oxygen reduction
Graphite alkene, increase aerogel structure unit wall thickness and addition crosslinking agent.Li Hui seminars of Harbin Institute of Technology select second two
Amine is reducing agent, sodium tetraborate be crosslinking agent be prepared for elastic graphite alkene aeroge (Xiang Xu, Qiangqiang Zhang,
Yikang Yu,Wenli Chen,Han Hu and Hui Li.Naturally Dried Graphene Aerogels with
Superelasticityand Tunable Poisson's Ratio.Adv.Mater.28,9223-9230(2016).)；Greatly
Even Qiu Jieshan seminar of Polytechnics is prepared for elastic graphite alkene aeroge (Han Hu, Zongbin from microwave reduction mode
Zhao,Wubo Wan,Yury Gogotsi,and Jieshan Qiu.Ultralight and Highly Compressible
Graphene Aerogels.Adv.Mater.25,2219-2223(2013).).Application publication number is the special of CN105692607A
Sharp application documents are that adhesive is prepared for a kind of compressible aeroge of graphene from γ-oxo -1- pyrenes butyric acid.
Mode described above has certain requirement to reducing agent system, cross-linking system, by graphene aerogel body
System is modified, and develops a kind of universal method of the high resiliency graphene aerogel material suitable for a variety of systems and does not report temporarily
Road.
The content of the invention
(1) technical problems to be solved
For the elastic poor and existing improvement of existing graphene aerogel material, its elastic preparation method is present
General applicability difference the problem of, the invention provides a kind of high resiliency graphene aerogel and preparation method thereof, the preparation side
Graphene hydrogel is placed in the solution of the good solvent of high-molecular compound by method, treats that macromolecular chain is diffused into inside gel
Afterwards, then with the poor solvent of high-molecular compound line replacement is entered, so that macromolecule switchs to roll up conformation from conformation is unfolded, from
And raising crosslinking points number on graphene sheet layer is attached to, increase system frame strength.Graphene aerogel after drying again
Elasticity been significantly enhanced.
(2) technical scheme
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
A kind of preparation method of high resiliency graphene aerogel, the preparation method include：(1) it is molten to prepare graphene oxide
The step of glue；(2) the step of preparing graphene hydrogel；(3) drying steps, also include between step (2) and step (3)：
(i) the step of strengthening skeleton；The step (i) is carried out as follows：
(a) high-molecular compound is dissolved in good solvent, is configured to Polymer Solution；
(b) graphene hydrogel made from step (2) is soaked in the Polymer Solution, obtains Graphene gel；
(c) Graphene gel is soaked in the poor solvent of high-molecular compound.
Preferably, the high-molecular compound is selected from polypropylene nitrile compounds, polyacrylamide compound, polyamide
Any of class compound, polyesters compound, polysulfones compound；With
The molecular weight of the high-molecular compound is 5000-200000.
It is further preferred that the concentration of the Polymer Solution is 0.5~5wt%.
It is further preferred that the good solvent is selected from DMF, DMA, N- methyl pyrroles
Any of pyrrolidone, dimethyl sulfoxide (DMSO), tetrahydrofuran.
It is highly preferred that immersion number of the graphene hydrogel in the Polymer Solution is not less than 2 times, it is preferably
2~4 times, and single soak time is not less than 3 days, preferably 3~6 days.
Preferably, the poor solvent is selected from liquid alcohol compound or liquid ketone compounds, is preferably selected from ethanol, different
The group of propyl alcohol and acetone composition.
It is further preferred that immersion number of the Graphene gel after step (b) processing in the poor solvent is not
Less than 2 times, preferably 2~4 times, and the time of single immersion was not less than 3 days, preferably 3~5 days.
Preferably, graphene hydrogel is prepared by chemical reduction method, its process conditions is：
Reducing agent used is that the oxidation product after itself having water solubility and being oxidized also is water miscible reducing agent, excellent
Choosing is selected from any of hydrazine hydrate, sodium hydrogensulfite, ascorbic acid, ethylenediamine；
The mass ratio of graphene oxide and reducing agent is 1：(0.5~5)；
The temperature that reduction reaction occurs is 40~200 DEG C, and the reaction time is not less than 12h, preferably 12~20 hours.
Preferably, the concentration of the graphene oxide colloidal sol is 2~15mg/mL, preferably described graphene oxide colloidal sol
PH is 5-7, and potassium content is in below 0.04wt%, and manganese ion content is in below 0.07wt%, and sodium ion number is in 0.05wt%
Hereinafter, graphene oxide layer number is 1-3 layers, lamellar spacing 1-3nm, 1-30 μm of piece footpath；And/or
The drying is using supercritical drying.
Present invention also offers a kind of high resiliency graphene aerogel, it is made of above-mentioned preparation method.
(3) beneficial effect
The above-mentioned technical proposal of the present invention has the following advantages that：
(1) present invention carries out skeleton enhancing using macromolecule to graphene aerogel, and macromolecule passes through in poor solvent
Conformation transition so as to wrap up and be connected to graphene sheet layer between, improve structure crosslinking points number, significantly improve graphene
The elasticity of aeroge, obtained graphene aerogel have high resiliency and three-dimensional structure, can be used as Elastic heat insulation material, electrochemistry
Materials'use.
(2) present invention use skeleton enhancing method by soak high molecular good-solvent solution with it is high molecular bad molten
Agent realizes that process is simple to operation, and the graphene aerogel prepared to different reducing agent systems is applicable, and is had pervasive
Property.
Brief description of the drawings
Fig. 1 is the flow chart of preparation method used in the present invention.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical scheme is clearly and completely described.Obviously, described embodiment is the part of the embodiment of the present invention, and
The embodiment being not all of.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creative work
On the premise of the every other embodiment that is obtained, belong to the scope of protection of the invention.
As shown in figure 1, the preparation method of high resiliency graphene aerogel provided by the invention comprises the following steps：
(1) the step of preparing graphene oxide colloidal sol.
The step can prepare graphene oxide using Hummers methods.Preparing raw material used includes graphite powder, and (granularity is small
In 30 μm of particle, content is more than 95%, carbon content be more than 99%), the concentrated sulfuric acid (95%~98%), potassium permanganate, sodium nitrate,
Hydrogen peroxide (30%), hydrochloric acid, barium chloride, hydrazine hydrate (80%).Specifically comprise the following steps：250mL is assembled in ice-water bath
Reaction bulb, add the appropriate concentrated sulfuric acid, stir the lower solid mixture for adding 2g graphite powders and 1g sodium nitrate, then add by several times
6g potassium permanganate, controlling reaction temperature are no more than 20 DEG C, and stirring reaction for a period of time, is then warming up to 35 DEG C or so, continues to stir
30min is mixed, is slow added into a certain amount of deionized water, is continued after mixing 20min, and adds the oxidation of appropriate hydrogen peroxide reduction residual
Agent, solution is set to be changed into glassy yellow.Filter, and washed with 5%HCl solution and deionized water until sulfate radical-free quilt in filtrate while hot
Untill detecting.Finally filter cake is placed in 60 DEG C of vacuum drying chamber and fully dried, graphite oxide is obtained, saves backup.Will
100mg graphite oxides are scattered in the 100g aqueous solution, obtain the suspension of brown color, then disperse 1h under ultrasound condition, are obtained
Stable dispersion liquid.Then move into four-hole boiling flask, be warming up to 80 DEG C, 2mL hydrazine hydrate is added dropwise, reacts 24h on this condition
After filter, obtained product is rinsed with first alcohol and water successively multiple, then fully dries, obtain in 60 DEG C of vacuum drying chamber
The piece number of plies is 1~3 layer, 1~3nm of lamellar spacing, the graphene oxide that 1~30 μm of piece footpath, is saved backup.
Water is added to be configured to the graphene oxide hydrosol that concentration is 2~15mg/mL above-mentioned graphene oxide, for follow-up
Step.
(2) the step of preparing graphene hydrogel.
The present invention can prepare graphene hydrogel by chemical reduction method, be added in the graphene oxide hydrosol certain
The reducing agent of content, reduction reaction and gel occurs after well mixed at a certain temperature, form graphene hydrogel.Reducing agent
Reducible graphene oxide, the oxy radical (such as epoxy radicals, hydroxyl, carboxyl) of surface of graphene oxide is removed, makes graphite oxide
Alkene is reduced to graphene, occurs to stack so as to gel because π-π interact between graphene sheet layer.Reducing agent used can
To be this as water-soluble and be oxidized product also for water miscible reducing agent, as hydrazine hydrate, sodium hydrogensulfite, ascorbic acid,
Any of ethylenediamine.The mass ratio of graphene oxide and reducing agent can be 1：(0.5~5), for example, 1:0.5、1:1、
1:2、1:3、1:4、1:5.The temperature that reduction reaction occurs is 40~200 DEG C, and the reaction time is not less than 12h, preferably 12~20
Hour.
Except chemical reduction method, graphene hydrogel can be prepared with other self-assembling methods.Such as ultrasonic dispersion.Tool
Body comprises the following steps：By the graphene oxide hydrosol in ultrasonic cleaner ultrasonic disperse more than 12 hours, then, by it
It is sealed in container, is transferred in baking oven, is kept for 72 hours at 85 DEG C, obtain graphene hydrogel.
Different existing graphite oxide aerogel preparation processes, the present invention add step (i) after step (2)：
The step of strengthening skeleton.
The step includes：
(a) high-molecular compound is dissolved in good solvent, is configured to Polymer Solution；
(b) graphene hydrogel made from step (2) is soaked in the Polymer Solution, obtains Graphene gel；
(c) resulting Graphene gel after step (b) processing is soaked in the poor solvent of high-molecular compound.
High-molecular compound is dissolved in good solvent and is configured to solution, high-molecular compound is in unfold conformation wherein.
Wherein, macromolecule is diffused into inside gel skeleton, in gel duct for the graphene hydrogel immersion that above-mentioned steps are obtained
Arranged in conformation is unfolded.The high-molecular compound refers to polypropylene nitrile compounds, polyacrylamide compound, polyamide-based
Any of compound, polyesters compound, polysulfones compound, molecular weight is between 5000-200000.The good solvent
Including water such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), tetrahydrofurans
Soluble solvent, there is good solvability to macromolecule, macromolecular chain is unfolded wherein.The quality of the Polymer Solution
Concentration is 0.5~10% (for example, can be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%).Stone
Black alkene hydrogel repeatedly soaks in Polymer Solution, so that macromolecule soaks number >=2 completely into gel skeleton inside
It is secondary, can be 2~~4 times, single soak time >=3 day, preferably 3~6 days, the quality of Graphene gel reclaimed water point after immersion
Number≤1%.
Resulting Graphene gel after step (b) processing is placed in poor solvent and soaked, carries out solvent displacement.Will
The high molecular Graphene gel of diffusion inside is placed on progress solvent displacement in high molecular poor solvent, when poor solvent expands
When being dissipated to inside gel, the transformation of macromolecule occurred conformation, switch to roll up conformation from conformation is unfolded, so as to be attached to Graphene gel
On skeleton, skeleton crosslinking points and frame strength are added so that the energy barrier under the conditions of external force needed for graphene aerogel deformation
Rise, is easier to return to initial position after deformation.The poor solvent is water miscible solvent, and macromolecule dissolves wherein
Property is poor, including alcohols, ketones solvent, such as ethanol, isopropanol, acetone.Graphene gel is more in high molecular poor solvent
Secondary immersion, so that macromolecule, which is completely transformed into, rolls up conformation, number >=2 time are soaked, such as can be 2~4 times, when single soaks
Between >=3 days, such as can be 3~5 days.
(3) Graphene gel is dried, the step of obtaining graphene aerogel.Drying means in the step can select
Supercritical drying, specifically comprise the following steps：Using carbon dioxide as dried medium, wet gel (was namely soaked bad
The Graphene gel of solvent) it is put into drying kettle, carbon dioxide is passed through, after being forced into 2~4MPa, is to slowly warm up to 50
DEG C, it is further continued for being forced into 10~15MPa, carbon dioxide is entered supercriticality.With carbon dioxide by Graphene gel
Alcohol or ketone solvent are brought separating still into and separated, and after solvent is taken out of completely, are depressured with 1~6MPa/h speed, until recovering
Untill normal pressure, that is, obtain high resiliency graphene aerogel.
Present invention also offers a kind of high resiliency graphene aerogel, it is made of above-mentioned preparation method.The graphene gas
The density of gel is in 0.032~0.081g/cm3, specific surface area is 156~317m2/ g, maximum resiliently compressible amount is 20-
60%, rebound degree.
It is the embodiment that the present invention enumerates below.
Embodiment 1
S11, prepare graphene oxide colloidal sol.
Graphene oxide is prepared using Hummers methods.Preparing raw material used includes graphite powder, and (granularity is less than 30 μm of grain
Son, content be more than 95%, carbon content be more than 99%), the concentrated sulfuric acid (95%~98%), potassium permanganate, sodium nitrate, hydrogen peroxide
(30%), hydrochloric acid, barium chloride, hydrazine hydrate (80%).Specifically comprise the following steps：250mL reaction is assembled in ice-water bath
Bottle, the appropriate concentrated sulfuric acid is added, stir the lower solid mixture for adding 2g graphite powders and 1g sodium nitrate, then gradation adds 6g Gao Meng
Sour potassium, controlling reaction temperature are no more than 20 DEG C, and stirring reaction for a period of time, is then warming up to 35 DEG C or so, continues to stir
30min, a certain amount of deionized water is slow added into, continued after mixing 20min, and add the oxidation of appropriate hydrogen peroxide reduction residual
Agent, solution is set to be changed into glassy yellow.Filter, and washed with 5%HCl solution and deionized water until sulfate radical-free quilt in filtrate while hot
Untill detecting.Finally filter cake is placed in 60 DEG C of vacuum drying chamber and fully dried, graphite oxide is obtained, saves backup.Will
100mg graphite oxides are scattered in the 100g aqueous solution, obtain the suspension of brown color, then disperse 1h under ultrasound condition, are obtained
Stable dispersion liquid.Then move into four-hole boiling flask, be warming up to 80 DEG C, 2mL hydrazine hydrate is added dropwise, reacts 24h on this condition
After filter, obtained product is rinsed with first alcohol and water successively multiple, then fully dries, obtain in 60 DEG C of vacuum drying chamber
The piece number of plies is 1~3 layer, 1~3nm of lamellar spacing, the graphene oxide that 1~30 μm of piece footpath, is saved backup.
Water is added to be configured to the graphene oxide hydrosol that concentration is 10mg/mL above-mentioned graphene oxide, for subsequently walking
Suddenly.
S12, graphene hydrogel is prepared by chemical reduction method.
100mg ethylenediamines are added in the graphene oxide hydrosol that 10mL concentration is 10mg/mL, are stirred.Will be upper
State the hydrosol to be sealed in water heating kettle, heat 14h at 120 DEG C, reduction reaction is fully occurred, and produce gel.
S13, enhancing skeleton.
The number-average molecular weight for weighing certain mass is 30000 polyacrylonitrile, is dissolved in DMF, matches somebody with somebody
The Polymer Solution that mass concentration is 1% is made.Graphene hydrogel is soaked in the Polymer Solution of its 10 times of volumes,
Change a Polymer Solution within every 3 days, change 3 times altogether.Then, Graphene gel is soaked in the ethanol of 10 times of volumes
In, change an ethanol within every 3 days, change 3 times altogether.
S14, Graphene gel dried, obtain graphene aerogel.
Graphene gel after S13 is handled is put into supercritical drying equipment, carbon dioxide to pressure is filled with and reaches
To 3MPa, then equipment is warming up to 50 DEG C, continue to be forced into 15MPa, taken out of alcohol solvent using supercritical carbon dioxide.Extremely
After ethanol removes completely, normal pressure is depressurized to 2MPa/h speed, sample is taken out, obtains graphene aerogel material.
After testing, high resiliency graphite oxide aerogel density manufactured in the present embodiment is 0.05g/cm3, specific surface area is
188m2/ g, maximum resiliently compressible amount are 50%, rebound degree >=90%.
Embodiment 2
S21, prepare graphene oxide colloidal sol.
Graphene oxide is prepared using Hummers methods.Preparing raw material used includes graphite powder, and (granularity is less than 30 μm of grain
Son, content be more than 95%, carbon content be more than 99%), the concentrated sulfuric acid (95%~98%), potassium permanganate, sodium nitrate, hydrogen peroxide
(30%), hydrochloric acid, barium chloride, hydrazine hydrate (80%).Specifically comprise the following steps：250mL reaction is assembled in ice-water bath
Bottle, the appropriate concentrated sulfuric acid is added, stir the lower solid mixture for adding 2g graphite powders and 1g sodium nitrate, then gradation adds 6g Gao Meng
Sour potassium, controlling reaction temperature are no more than 20 DEG C, and stirring reaction for a period of time, is then warming up to 35 DEG C or so, continues to stir
30min, a certain amount of deionized water is slow added into, continued after mixing 20min, and add the oxidation of appropriate hydrogen peroxide reduction residual
Agent, solution is set to be changed into glassy yellow.Filter, and washed with 5%HCl solution and deionized water until sulfate radical-free quilt in filtrate while hot
Untill detecting.Finally filter cake is placed in 60 DEG C of vacuum drying chamber and fully dried, graphite oxide is obtained, saves backup.Will
100mg graphite oxides are scattered in the 100g aqueous solution, obtain the suspension of brown color, then disperse 1h under ultrasound condition, are obtained
Stable dispersion liquid.Then move into four-hole boiling flask, be warming up to 80 DEG C, 2mL hydrazine hydrate is added dropwise, reacts 24h on this condition
After filter, obtained product is rinsed with first alcohol and water successively multiple, then fully dries, obtain in 60 DEG C of vacuum drying chamber
The piece number of plies is 1~3 layer, 1~3nm of lamellar spacing, the graphene oxide that 1~30 μm of piece footpath, is saved backup.
Water is added to be configured to the graphene oxide hydrosol that concentration is 10mg/mL above-mentioned graphene oxide, for subsequently walking
Suddenly.
S22, graphene hydrogel is prepared by chemical reduction method.
100mg ethylenediamines are added in the graphene oxide hydrosol that 10mL concentration is 10mg/mL, are stirred.Will be upper
State the hydrosol to be sealed in water heating kettle, heat 14h at 120 DEG C, reduction reaction is fully occurred, and produce gel.
S23, enhancing skeleton.
The number-average molecular weight for weighing certain mass is 50000 polysulfones, is dissolved in DMF, is configured to
Mass concentration is 0.5% Polymer Solution.Graphene hydrogel is soaked in the Polymer Solution of its 10 times of volumes, often
Change a Polymer Solution within 3 days, change 3 times altogether.Then, Graphene gel is soaked in the ethanol of 10 times of volumes,
Change an ethanol within every 3 days, change 3 times altogether.
S24, Graphene gel dried, obtain graphene aerogel.
Graphene gel after S13 is handled is put into supercritical drying equipment, carbon dioxide to pressure is filled with and reaches
To 3MPa, then equipment is warming up to 50 DEG C, continue to be forced into 15MPa, taken out of alcohol solvent using supercritical carbon dioxide.Extremely
After ethanol removes completely, normal pressure is depressurized to 2MPa/h speed, sample is taken out, obtains graphene aerogel material.
After testing, high resiliency graphite oxide aerogel density manufactured in the present embodiment is 0.035g/cm3, specific surface area
For 195m2/ g, maximum resiliently compressible amount are 55%, springback capacity >=90%.
Embodiment 3
S31, prepare graphene oxide colloidal sol.
Graphene oxide is prepared using Hummers methods.Preparing raw material used includes graphite powder, and (granularity is less than 30 μm of grain
Son, content be more than 95%, carbon content be more than 99%), the concentrated sulfuric acid (95%~98%), potassium permanganate, sodium nitrate, hydrogen peroxide
(30%), hydrochloric acid, barium chloride, hydrazine hydrate (80%).Specifically comprise the following steps：250mL reaction is assembled in ice-water bath
Bottle, the appropriate concentrated sulfuric acid is added, stir the lower solid mixture for adding 2g graphite powders and 1g sodium nitrate, then gradation adds 6g Gao Meng
Sour potassium, controlling reaction temperature are no more than 20 DEG C, and stirring reaction for a period of time, is then warming up to 35 DEG C or so, continues to stir
30min, a certain amount of deionized water is slow added into, continued after mixing 20min, and add the oxidation of appropriate hydrogen peroxide reduction residual
Agent, solution is set to be changed into glassy yellow.Filter, and washed with 5%HCl solution and deionized water until sulfate radical-free quilt in filtrate while hot
Untill detecting.Finally filter cake is placed in 60 DEG C of vacuum drying chamber and fully dried, graphite oxide is obtained, saves backup.Will
100mg graphite oxides are scattered in the 100g aqueous solution, obtain the suspension of brown color, then disperse 1h under ultrasound condition, are obtained
Stable dispersion liquid.Then move into four-hole boiling flask, be warming up to 80 DEG C, 2mL hydrazine hydrate is added dropwise, reacts 24h on this condition
After filter, obtained product is rinsed with first alcohol and water successively multiple, then fully dries, obtain in 60 DEG C of vacuum drying chamber
The piece number of plies is 1~3 layer, 1~3nm of lamellar spacing, the graphene oxide that 1~30 μm of piece footpath, is saved backup.
Water is added to be configured to the graphene oxide hydrosol that concentration is 6mg/mL above-mentioned graphene oxide, for subsequently walking
Suddenly.
S32, graphene hydrogel is prepared by chemical reduction method.
0.18 ascorbic acid is added in the graphene oxide hydrosol that 10mL concentration is 6mg/mL, is stirred.Will be upper
State the hydrosol to be sealed in water heating kettle, heat 18h at 40 DEG C, reduction reaction is fully occurred, and produce gel.
S33, enhancing skeleton.
The number-average molecular weight for weighing certain mass is 60000 polyacrylamide, is dissolved in DMF,
It is configured to the Polymer Solution that mass concentration is 0.5%.The macromolecule that graphene hydrogel is soaked in its 10 times of volumes is molten
In liquid, change a Polymer Solution within every 3 days, change 3 times altogether.Then, Graphene gel is soaked in 10 times of volumes
In ethanol, change an ethanol within every 3 days, change 3 times altogether.
S34, Graphene gel dried, obtain graphene aerogel.
Graphene gel after S13 is handled is put into supercritical drying equipment, carbon dioxide to pressure is filled with and reaches
To 3MPa, then equipment is warming up to 50 DEG C, continue to be forced into 15MPa, taken out of alcohol solvent using supercritical carbon dioxide.Extremely
After ethanol removes completely, normal pressure is depressurized to 2MPa/h speed, sample is taken out, obtains graphene aerogel material.
After testing, high resiliency graphite oxide aerogel density manufactured in the present embodiment is 0.052g/cm3, specific surface area
For 156m2/ g, maximum resiliently compressible amount are 40%, springback capacity >=90%.
The preparation method of embodiment 4 to embodiment 8 is substantially the same with embodiment 1, and difference is shown in Table 1.
Embodiment 9
S91, same to S11.
S92, graphene hydrogel is prepared by ultrasonic dispersion.By the graphene oxide hydrosol in ultrasonic cleaner
Ultrasonic disperse 15 hours, then, it is sealed against, in container, being transferred in baking oven, is kept for 72 hours at 85 DEG C, obtain graphite
Alkene hydrogel.
S93, same to S13.
S94, same to S14.
Except above-described embodiment, the present invention is also prepared for several groups of contrast products.
Embodiment 10
Substantially the same with embodiment 1, difference is：The step of not comprising enhancing skeleton.
Embodiment 11
Substantially the same with embodiment 1, difference is：In the step of strengthening skeleton, do not entered using poor solvent
Row solvent is replaced.
Embodiment 12
Using dimethyl silicone polymer as high polymer material, it is dissolved in curing agent in n-hexane molten as macromolecule
Liquid.Preparation method comprises the following steps：
Aerogel material made from embodiment 10 is impregnated into half an hour in Polymer Solution, then, by aerogel material
It is placed in vacuum drying chamber, is placed 12 hours at 120 DEG C.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (10)
1. a kind of preparation method of high resiliency graphene aerogel, the preparation method include：(1) graphene oxide colloidal sol is prepared
The step of；(2) the step of preparing graphene hydrogel；(3) drying steps, it is characterised in that step (2) and step (3) it
Between also include：(i) the step of strengthening skeleton；The step (i) is carried out as follows：
(a) high-molecular compound is dissolved in good solvent, is configured to Polymer Solution；
(b) graphene hydrogel made from step (2) is soaked in the Polymer Solution, obtains Graphene gel；
(c) Graphene gel is soaked in the poor solvent of high-molecular compound.
2. preparation method according to claim 1, it is characterised in that the high-molecular compound is selected from polypropylene nitrile
Any of compound, polyacrylamide compound, polyamide-based compound, polyesters compound, polysulfones compound；With
The molecular weight of the high-molecular compound is 5000-200000.
3. preparation method according to claim 2, it is characterised in that the concentration of the Polymer Solution be 0.5~
5wt%.
4. preparation method according to claim 2, it is characterised in that the good solvent be selected from DMF,
Any of DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), tetrahydrofuran.
5. preparation method according to claim 4, it is characterised in that the graphene hydrogel is in the Polymer Solution
In immersion number be not less than 2 times, preferably 2~4 times, and single soak time be not less than 3 days, preferably 3~6 days.
6. preparation method according to claim 2, it is characterised in that the poor solvent be selected from liquid alcohol compound or
Liquid ketone compounds, it is preferably selected from the group of ethanol, isopropanol and acetone composition.
7. preparation method according to claim 6, it is characterised in that the Graphene gel after step (b) processing is in institute
State immersion number in poor solvent and be not less than 2 times, preferably 2~4 times, and the time of single immersion be not less than 3 days, preferably
For 3~5 days.
8. according to the preparation method described in any one of claim 1~7, it is characterised in that prepare graphite by chemical reduction method
Alkene hydrogel；
The process conditions of chemical reduction method are：Reducing agent used is the oxidation product after itself having water solubility and being oxidized
For water miscible reducing agent, any of hydrazine hydrate, sodium hydrogensulfite, ascorbic acid, ethylenediamine are preferably selected from；
The mass ratio of graphene oxide and reducing agent is 1：(0.5~5)；
The temperature that reduction reaction occurs is 40~200 DEG C, and the reaction time is not less than 12h, preferably 12~20 hours.
9. according to the preparation method described in any one of claim 1~7, it is characterised in that：
The concentration of the graphene oxide colloidal sol is 2~15mg/mL, and the pH of preferably described graphene oxide colloidal sol is 5-7, potassium from
Sub- content is in below 0.04wt%, and manganese ion content is in below 0.07wt%, and sodium ion number is in below 0.05wt%, graphite oxide
The alkene piece number of plies is 1-3 layers, lamellar spacing 1-3nm, 1-30 μm of piece footpath；And/or
The drying is using supercritical drying.
10. a kind of high resiliency graphene aerogel, it is characterised in that using the preparation method described in any one of claim 1~9
It is made.
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