CN104817076B - Preparation method of high-density multilayer graphene gel material - Google Patents
Preparation method of high-density multilayer graphene gel material Download PDFInfo
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Abstract
The invention belongs to the field of high-performance materials and relates to a preparation method of a high-density multilayer graphene gel material. The preparation method includes following steps: filling a beaker with graphite oxide, adding water, ultrasonic-dispersing the graphite oxide uniformly, adding a reduction agent according to a certain proportion, heating the mixture for a certain time to obtain hydrogel, soaking the hydrogel in the water to remove small molecules in the hydrogel, freeze-drying the hydrogel to obtain single-layer graphene gel, puncturing pores on the single-layer graphene gel, and pouring the mixture of the graphite oxide and the reduction agent in the same proportion onto the graphene gel, wherein the steps hereinabove are carried out for several times to obtain the high-density multilayer graphene gel material. In the invention, by puncturing pores for growing the sol for several times, a problem of producing the high-density gel is solved. The gel material not only is greatly increased in density but also is excellent in mechanical strength, electric conductivity and elasticity.
Description
Technical field
The invention belongs to high performance material field, is related to a kind of preparation method of the multiple Graphene gel of high density.
Background technology
In terms of graphene conductive compound, Stankvoich et al. reported hydrazine hydrate reduction polystyrene in 2006
Compound graphene oxide, composite material exhibits have gone out the percolation threshold of 0.1% (volume fraction), and this is the two-dimensional nano of report
Minimum numerical value in composite.In volume fraction 1%, electrical conductivity reaches 0.1S m-1(S.Stankovich,
D.A.Dikin,G.H.B.Dommett,K.M.Kohlhaas,E.J.Zimney,E.A.Stach,R.D.Piner,
S.T.Nguyen,R.S.Ruoff,Graphene based composite materials,Nature,2006,442,7100,
282)。
The form of Graphene it is various, the controllability of synthetic technology is more limited to.Traditional Graphene synthetic technology is made a general survey of,
It is peeled off or growth course has randomness, and the Graphene shape for preparing, size is different, and the number of plies is also difficult to control to.Graphite
The manufacture major part of alkene device is randomly deposited graphene film acquisition, and the specific Graphene sample of only only a few can
To reach close preferable electric conductivity and can without loss transmit electric current, this limitation greatly hinders Graphene
Basic research and practical application.However, Graphene gel is more light, the range of application of Graphene is allowed to become more extensively,
Gel possesses low-density, big open bore and the characteristic of big specific surface area so that gel electric energy storage (R.P.Maloney,
H.J.Kim, J.S.Sakamoto, ACS Appl.Mater.Interface 2012,4,2318) and heat-insulated field (J.Cai,
S.Liu, J.Feng, S.Kimura, M.Wada, S.Kuga, L.Zhang, Angew.Chem.2012,124,2118) suffer from extensively
General application prospect.
Graphene is in recent years because its excellent heat conduction, conductive and mechanical performance have caused extensive concern.However,
After Graphene becomes polymer, its these properties can only retain (Y.Gu, Y.Xu, Y.Wang, Graphene- by part
wrapped CoS nanoparticles for high-capacity lithium-ion storage,ACS Appl
Mater Interfaces 2013,5,801).These are all attributed to the effect of the strong pi-pi bond between graphene film and piece so as to
Poor dispersion on polymer, even if there is solvent action, graphene film also can be polymerized in solvent volatilization process, and pliable
Song forms bad graphene nano structure (M.Chen, T.Tao, L.Zhang, W.Gao, C.Li, Highly
conductive and stretchable polymer composites based on graphene/MWCNT
network,Chem.Commun.2013,49,1612).This is to directly affects the property that Graphene has very bigger serface,
And then the property of impact grapheme material.In order to overcome above-mentioned defect, can attempt that graphene film is made the structure of 3D, than
Such as piece (H.P.Cong, X.C.Ren, P.Wang, S.H.Yu, the Macroscopic of hydrogel, aeroge and macropore
multifunctional graphene-based hydrogels and aerogels by a metal ion induced
self-assembly process,ACS Nano 2012,6,2693).Graphene aerogel is first by Kistlerll in 1931
Secondary proposition, it is the nanoporous solid-state material of a kind of extremely-low density, macropore volume, high-specific surface area.The all attributions of these features
Connected the constituted tridimensional network of its nano particle.In general, aeroge is obtained first wet by sol-gel process
Gel, then Jing solvent exchange procedures remove the larger solvent of surface tension in network space, finally using special seasoning come
Prepared aeroge.Because aeroge has above specific characteristic so that it has application, such as Cherenkov detections in many fields
Device, catalyst and its carrier, absorption, energy storage, capacitor etc..
The content of the invention
Goal of the invention：It is an object of the invention to provide a kind of preparation method of the multiple Graphene gel of high density, its preparation
Simply, easily operation, can produce in batches.The invention improve the low-density of existing Graphene gel, bad mechanical strength and
The not high problem of electric conductivity, through the improvement of the multiple Graphene gel of the high density, can make Graphene gel in density, machinery
Intensity, electric conductivity aspect are greatly improved.
Technical scheme：In order to solve above-mentioned technical problem, the invention provides a kind of multiple Graphene gel of high density
Preparation method, the preparation method comprises the steps:
1. the method that prepared by a kind of multiple Graphene gel material of high density, is characterized in that step is：1) by graphite oxide
The aqueous solution is made into, ultrasonic disperse is uniform, adds reducing agent, heating a period of time, freeze-drying obtains single-layer graphene gel；2)
Single-layer graphene gel is put in mould, syringe needle acanthopore is used on single-layer graphene gel, pour graphite oxide and reducing agent into
Mixed solution, then by step 1) method regeneration gel obtain two-layer Graphene gel；3) circulation step 1) and 2)
To the multiple Graphene gel of high density；4) by step 3) the multiple Graphene of high density that obtains is made into the aqueous solution, adds adhesive
Ultrasonic disperse is uniform after solution, and then drop coating tests its electrochemistry in electrode surface natural air drying on electrochemical workstation
Energy.
2. step 1) described in graphite oxide be that arbitrary oxidation stripping means system is improved based on Hummers methods principle
.
3. step 1) described in the concentration of graphite oxide be 0.1～100mg/mL.
4. step 1) described in reducing agent include ascorbic acid, sodium borohydride, vulcanized sodium, hydrazine hydrate etc. with reproducibility
One kind in organic or inorganic thing or their arbitrary mixtures.
5. step 1) described in graphite oxide and reducing agent ratio 1:1～1:10
6. step 1) described in reaction time at 1～100 hour.
7. step 1) described in reaction temperature at 40～100 DEG C.
8. step 2) on single-layer graphene gel acanthopore, the acanthopore is carried out in one direction.
9. step 2) in mould used be the arbitrary utensil for just accommodating single-layer graphene gel.
10. step 2) in syringe needle used by acanthopore internal diameter in 0.001～1mm.
11. steps 2) in institute's acanthopore quantity in 1～10000/m2。
12. steps 3) described in cycle-index be more than or equal to 2.
13. steps 4) in adhesive used can be shitosan, polyvinyl acetate.
The present invention has the advantage that compared with prior art：
(1) reducing agent is employed, greatly reduces the temperature needed for reaction, operating process is simple, and easy control of temperature is kept away
The utilization of traditional autoclave is exempted from, so as to greatly save the energy.
(2) method for employing mould, the gel of formation is compared with other gels, there is the advantage that its is unique, and Graphene has
Very strong hydrophobicity, if making the multiple Graphene gel of high density without mould, will be due to the hydrophobicity of itself, in individual layer
Graphene gel periphery grows up to irregular shape, and can not be really in its internal continued growth highdensity so as to not reach
Effect.The introducing of size just suitable mould, also solves a difficult problem of the Graphene gel in periphery growth.
(3) using the method for acanthopore, when the top acanthopore in simple gel, the graphite oxide of addition and the mixing of reducing agent
Liquid will directly be introduced into the inside of simple gel, so as to the gel for regrowing will be inside original gel.In addition, this
The acanthopore means used in invention, it is also possible to open the blind hole inside single-layer graphene gel, so that more mixed
Close liquid to enter.The gel of new growth is just more tight, and density is bigger, and mechanical strength also can be bigger, and electric conductivity also obtains bigger
Improve.
Specific embodiment
Further illustrate the present invention with example below, but the present invention is not intended to be limited thereto.
The experimental technique of unreceipted actual conditions in following embodiment, generally according to normal condition, or according to manufacture
The condition that manufacturer will advise.Heretofore described " room temperature ", " normal pressure " refers to the temperature and air pressure between regular job, generally
25 DEG C, a standard atmospheric pressure.
In the present invention, graphite powder used is native graphite, and using improved Hummers methods graphite oxide is prepared, and
Ultrasound peels off the graphite oxide dispersion for obtaining individual layer or minority layer in deionized water.
Embodiment 1
400mg graphite oxides are put in 100mL (4mg/mL) secondary water, and ultrasonic disperse is uniformly dispersed for 10 hours, are added
The ascorbic acid (1 of 1.2g:3) vigorous agitation, in being put into 40 DEG C of thermostat water bath, heating response 16 hours obtains Graphene
Hydrogel, hydrogel is put in secondary water and is soaked one day, then freeze-drying, obtains Graphene gel, solidifying in original Graphene
Acanthopore on the basis of glue, then pour 1 into:3 graphite oxide and Vitamin C aqueous acid, then with 40 DEG C of heating responses 16 hours,
Freeze-drying again, circulates 10 times, obtains the multiple Graphene gel of high density.The multiple Graphene gel of the high density is used to change
Sensor is learned, test limit can be made to reach 1 × 10-7M。
Embodiment 2
500mg graphite oxides are put in 100mL (5mg/mL) secondary water, and ultrasonic disperse is uniformly dispersed for 10 hours, are added
The ascorbic acid (1 of 1.2g:3) vigorous agitation, in being put into 40 DEG C of thermostat water bath, heating response 16 hours obtains Graphene
Hydrogel, hydrogel is put in secondary water and is soaked one day, then freeze-drying, obtains Graphene gel, solidifying in original Graphene
Acanthopore on the basis of glue, then pour 1 into:3 graphite oxide and Vitamin C aqueous acid, then with 40 DEG C of heating responses 16 hours,
Freeze-drying again, circulates 10 times, obtains the multiple Graphene gel of high density.The multiple Graphene gel of the high density is used to change
Sensor is learned, test limit can be made to reach 1.3 × 10-7M。
Embodiment 3
400mg graphite oxides are put in 100mL (4mg/mL) secondary water, and ultrasonic disperse is uniformly dispersed for 10 hours, add 2g
Ascorbic acid (1:5) vigorous agitation, in being put into 40 DEG C of thermostat water bath, heating response 16 hours obtains Graphene water-setting
Glue, hydrogel is put in secondary water and is soaked one day, then freeze-drying, Graphene gel is obtained, in original Graphene gel
On the basis of acanthopore, then pour 1 into:3 graphite oxide and Vitamin C aqueous acid, then with 40 DEG C of heating responses 16 hours, again
Freeze-drying, circulates 10 times, obtains the multiple Graphene gel of high density.The multiple Graphene gel of the high density is used for into chemistry biography
Sensor, can make test limit reach 2 × 10-7M。
Embodiment 4
400mg graphite oxides are put in 100mL (4mg/mL) secondary water, and ultrasonic disperse is uniformly dispersed for 10 hours, are added
The hydrazine hydrate (1 of 1.2g:3) vigorous agitation, in being put into 40 DEG C of thermostat water bath, heating response 16 hours obtains Graphene water
Gel, hydrogel is put in secondary water and is soaked one day, then freeze-drying, Graphene gel is obtained, in original Graphene gel
On the basis of acanthopore, then pour 1 into:3 graphite oxide and Vitamin C aqueous acid, then with 40 DEG C of heating responses 16 hours, then
Secondary freeze-drying, circulates 10 times, obtains the multiple Graphene gel of high density.The multiple Graphene gel of the high density is used for into chemistry
Sensor, can make test limit reach 2.9 × 10-7M。
Embodiment 5
400mg graphite oxides are put in 100mL (4mg/mL) secondary water, and ultrasonic disperse is uniformly dispersed for 10 hours, are added
The ascorbic acid (1 of 1.2g:3) vigorous agitation, in being put into 70 DEG C of thermostat water bath, heating response 16 hours obtains Graphene
Hydrogel, hydrogel is put in secondary water and is soaked one day, then freeze-drying, obtains Graphene gel, solidifying in original Graphene
Acanthopore on the basis of glue, then pour 1 into:3 graphite oxide and Vitamin C aqueous acid, then with 40 DEG C of heating responses 16 hours,
Freeze-drying again, circulates 10 times, obtains the multiple Graphene gel of high density.The multiple Graphene gel of the high density is used to change
Sensor is learned, test limit can be made to reach 4 × 10-7M。
Embodiment 6
400mg graphite oxides are put in 100mL (4mg/mL) secondary water, and ultrasonic disperse is uniformly dispersed for 10 hours, are added
The ascorbic acid (1 of 1.2g:3) vigorous agitation, in being put into 40 DEG C of thermostat water bath, heating response 18 hours obtains Graphene
Hydrogel, hydrogel is put in secondary water and is soaked one day, then freeze-drying, obtains Graphene gel, solidifying in original Graphene
Acanthopore on the basis of glue, then pour 1 into:3 graphite oxide and Vitamin C aqueous acid, then with 40 DEG C of heating responses 16 hours,
Freeze-drying again, circulates 10 times, obtains the multiple Graphene gel of high density.The multiple Graphene gel of the high density is used to change
Sensor is learned, test limit can be made to reach 4.5 × 10-7M。
Embodiment 7
400mg graphite oxides are put in 100mL (4mg/mL) secondary water, and ultrasonic disperse is uniformly dispersed for 10 hours, are added
The ascorbic acid (1 of 1.2g:3) vigorous agitation, in being put into 65 DEG C of thermostat water bath, heating response 22 hours obtains Graphene
Hydrogel, hydrogel is put in secondary water and is soaked one day, then freeze-drying, obtains Graphene gel, solidifying in original Graphene
Acanthopore on the basis of glue, then pour 1 into:3 graphite oxide and Vitamin C aqueous acid, then with 40 DEG C of heating responses 16 hours,
Freeze-drying again, circulates 10 times, obtains the multiple Graphene gel of high density.The multiple Graphene gel of the high density is used to change
Sensor is learned, test limit can be made to reach 6 × 10-7M。
Embodiment 8
400mg graphite oxides are put in 100mL (4mg/mL) secondary water, and ultrasonic disperse is uniformly dispersed for 10 hours, are added
The ascorbic acid (1 of 1.2g:3) vigorous agitation, in being put into 40 DEG C of thermostat water bath, heating response 16 hours obtains Graphene
Hydrogel, hydrogel is put in secondary water and is soaked one day, then CO 2 supercritical is dried, and Graphene gel is obtained, in original
There is an acanthopore on the basis of Graphene gel, then pour 1 into:3 graphite oxide and Vitamin C aqueous acid, then it is anti-with 40 DEG C of heating
Answer 16 hours, CO 2 supercritical drying again is circulated 30 times, obtains the multiple Graphene gel of high density.By the high density
Multiple Graphene gel is used for chemical sensor, and test limit can be made to reach 2 × 10-8M。
Embodiment 9
400mg graphite oxides are put in 100mL (4mg/mL) secondary water, and ultrasonic disperse is uniformly dispersed for 20 hours, are added
The ascorbic acid (1 of 1.2g:3) vigorous agitation, in being put into 40 DEG C of thermostat water bath, heating response 16 hours obtains Graphene
Hydrogel, hydrogel is put in secondary water and is soaked one day, then freeze-drying, obtains Graphene gel, solidifying in original Graphene
Acanthopore on the basis of glue, then pour 1 into:3 graphite oxide and Vitamin C aqueous acid, then with 40 DEG C of heating responses 16 hours,
Freeze-drying again, circulates 10 times, obtains the multiple Graphene gel of high density.The multiple Graphene gel of the high density is used to change
Sensor is learned, test limit can be made to reach 3.3 × 10-7M。
Claims (8)
1. the method that prepared by a kind of multiple Graphene gel material of high density, is characterized in that step is：1) graphite oxide is made into
The aqueous solution, ultrasonic disperse is uniform, adds reducing agent, and heating a period of time, freeze-drying obtains single-layer graphene gel；2) will be single
Layer graphene gel is put in mould, and syringe needle acanthopore is used on single-layer graphene gel, pours the mixed of graphite oxide and reducing agent into
Close solution, then by step 1) method regeneration gel obtain two-layer Graphene gel；3) circulation step 1) and 2) obtain height
The multiple Graphene gel of density；4) by step 3) the multiple Graphene of high density that obtains is made into the aqueous solution, adds adhesive solvent
Afterwards ultrasonic disperse is uniform, and then drop coating tests its chemical property in electrode surface natural air drying on electrochemical workstation.
2. such as the method described in right 1, it is characterised in that step 1) in reducing agent be to include ascorbic acid, sodium borohydride, sulphur
Change one kind in sodium or hydrazine hydrate or their arbitrary mixtures ".
3. such as the method described in right 1, it is characterised in that step 1) described in graphite oxide and reducing agent ratio 1:1-
1:10。
4. such as the method described in right 1, it is characterised in that step 2) on single-layer graphene gel acanthopore, the acanthopore
It is to carry out in one direction.
5. such as the method described in right 1, it is characterised in that step 2) in mould used coagulate just to accommodate single-layer graphene
Arbitrary utensil of glue.
6. such as the method described in right 1, it is characterised in that step 2) in syringe needle used by acanthopore internal diameter in 0.001～1mm.
7. such as the method described in right 1, it is characterised in that step 2) on single-layer graphene gel acanthopore, acanthopore
Quantity is in 1～10000/m2。
8. such as the method described in right 1, it is characterised in that step 3) described in cycle-index be more than or equal to 2.
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| CN105675182A (en) * | 2015-11-30 | 2016-06-15 | 重庆大学 | Preparation method of cellulose-based flexible stress-strain sensitive material |
| CN106409533B (en) * | 2016-11-16 | 2018-06-22 | 江南大学 | A kind of preparation method of ultracapacitor 3D iron oxide/graphene combination electrode material |
| CN110117003A (en) * | 2018-02-05 | 2019-08-13 | 庄鹏宇 | A kind of preparation method of redox graphene film |
| CN115414874B (en) * | 2022-08-31 | 2023-07-14 | 安普瑞斯（无锡）有限公司 | Multiple polyatomic co-doped carbon aerogel and preparation method and application thereof |
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