CN105271204B - A kind of graphene/graphene nanobelt composite aquogel and preparation method thereof - Google Patents
A kind of graphene/graphene nanobelt composite aquogel and preparation method thereof Download PDFInfo
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- CN105271204B CN105271204B CN201510807596.0A CN201510807596A CN105271204B CN 105271204 B CN105271204 B CN 105271204B CN 201510807596 A CN201510807596 A CN 201510807596A CN 105271204 B CN105271204 B CN 105271204B
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Abstract
The invention belongs to technical field of nano material, and in particular to a kind of graphene/graphene nanobelt composite aquogel and preparation method thereof.Graphene nanobelt of the present invention is by radially being cut off and stripping is prepared to multi-walled carbon nanotube.Described graphene/graphene nanobelt composite aquogel is in the presence of reducing agent, and the tridimensional network that primary reconstruction obtains is carried out by graphene nanometer sheet and graphene nanobelt.The graphene sheet layer of two dimension plays a part of skeletal support mainly as physical cross-linked network, and quasi-one-dimensional graphene nanobelt plays a part of connection graphene sheet layer as through bridge.The present invention is a kind of easy new method for synthesizing and regulating and controlling graphene-based composite three dimensional structure, simple to operate, is easily controlled, cost is cheap pollution-free, is easy to mass produce.Graphene provided by the invention/graphene nanobelt composite aquogel can turn into a kind of electrode material of the preferably new energy devices such as carrier material and ultracapacitor.
Description
Technical field
The invention belongs to grapheme material technical field, and in particular to a kind of graphene/graphene nanobelt compound water congealing
Glue and preparation method thereof, it may be used as the electrode material of the new energy devices such as carrier material and ultracapacitor.
Technical background
Graphene is the graphite of monolithic layer, by sp2Carbon atom Hexagonal array forms.Graphene possesses higher inside current-carrying
Transport factor（200000 cm2 V-1 s-1）, good thermal conductivity（~ 5000 W m-1 K-1）, high transmission rate（~ 97.7%）And reason
By specific surface area（2630 m2 g-1）, and excellent mechanical strength.Therefore, graphene has wide application in many aspects
Prospect.But in actual applications, because the π π of graphene film interlayer interact, graphene sheet layer is easy to stack again,
The structure of class graphite is formed, the excellent properties of graphene in itself is not fully used.Therefore, how graphite is effectively suppressed
The stacking of alkene lamella is to realize the wide variety of key of grapheme material.
Graphene nanobelt is a kind of accurate one-dimensional c-based nanomaterial, and it has adhered to the excellent physical chemistry of carbon nanomaterial
Performance, such as higher electric conductivity, excellent mechanical property and good chemical stability.In addition, graphene nanobelt is special
Edge effect cause its have than graphene, CNT more flexibly adjustable property.These special natures make it in energy
The field such as amount conversion and storage, field-effect transistor, electronic sensor, high molecule nano composite material all has extremely wide
Application prospect, turn into the study hotspot in carbon nanomaterial field.
Self assembly is to be tied by interactions such as hydrogen bond, π π stackings and electrostatic attractions come the multistage being physical crosslinking
A kind of effective ways of structure.Self assembling process is a kind of spontaneous process, and by reasonably designing, self assembling process can be by multigroup
Point simultaneously carry out without influence product formation, and the structure of self assembly can assign material some be different from the only of bulk mass
Characteristic energy, so as to widen its application field.This self-assembling technique is applied in graphene-based composite, tool can be formed
There is the three-dimensional porous network structure of high-specific surface area, so as to effectively suppress mutual between graphene sheet layer and graphene nanobelt
Stack, be advantageous to the transmission of electronics and the migration of ion.
The content of the invention
It is an object of the invention to provide graphene/graphene nanobelt that a kind of preparation process is simple, cost is cheap is multiple
Heshui gel rubber material and preparation method thereof.
Graphene provided by the present invention/graphene nanobelt compound hydrogel material, its preparing raw material composition include：Oxygen
Graphite, single wall or multi-walled carbon nanotube, potassium permanganate, the concentrated sulfuric acid, ascorbic acid, sodium ascorbate, hydroiodic acid etc..
Graphene provided by the present invention/graphene nanobelt compound hydrogel material, its preparation process are to use reducing agent
Stannic oxide/graphene nano piece, stannic oxide/graphene nano band are subjected to in-situ reducing and self assembly prepares.Specific steps are such as
Under：
（1）Graphite oxide is scattered in deionized water, through ultrasonic disperse, obtains the oxidation of certain density stable dispersion
Graphene dispersing solution；
（2）Reducing agent is added in graphene oxide water solution in proportion, ultrasound makes it be uniformly dispersed, and is mixed
Liquid；
（3）The aqueous dispersions of a certain amount of stannic oxide/graphene nano band are instilled into step（2）In the mixed liquor of gained, stirring
For a period of time, homogeneous dispersion liquid is formed；
（4）By step（3）The mixed dispersion liquid of gained keeps standing at a certain temperature, oil bath reaction a period of time, i.e.,
It can obtain graphene/graphene nanobelt composite aquogel.
In the present invention, described stannic oxide/graphene nano band is radially to cut off CNT by solution oxide method to be prepared into
Arrive, the method refers to the Al of patent US 2010/0105834.
In the present invention, reducing agent used is selected from：Ascorbic acid（Vitamin C）, sodium ascorbate, hydroiodic acid, to benzene two
Phenol.
In the present invention, step（1）Described graphite oxide is prepared by Hummers methods, graphene oxide dispersion concentration
For 2-5 mg/mL.
In the present invention, step（2）The concentration of described reducing agent is 40-80 mmol/L.
In the present invention, step（3）Concentration of the described stannic oxide/graphene nano with aqueous dispersions is 0.5-1.5 mg/mL.
In the present invention, step（4）The quality of graphene oxide and stannic oxide/graphene nano band in described mixed dispersion liquid
Than for 4:1~1:1.
In the present invention, step（4）Described temperature is 80-100 DEG C, and the reaction time is 0.5-3.5 h.
Use SEM（SEM）, transmission electron microscope（TEM）, X-ray diffractometer（XRD）, electrochemistry work
Make station characterize the structure and morphology of graphene-graphene nanobelt composite aquogel that the present invention is obtained and its be used as it is super
The performance of capacitor electrode material, its result are as follows：
（1）SEM test results show：There is more prepared graphene/graphene nanobelt composite aquogel in the present invention
Level pore space structure, graphene sheet layer are built into the skeleton structure of three-dimensional network, graphene sheet layer bag with graphene nanobelt jointly
Banded graphene nanobelt is wrapped up in, and graphene nanobelt is through between graphene sheet layer simultaneously.It is this three-dimensional multiple
Close network and not only form hierarchical porous structure, and improve the specific surface area of material；
（2）TEM test results further demonstrate that：Prepared graphene/graphene nanobelt compound water congealing in the present invention
Glue is by graphene sheet layer and graphene nanobelt collaboration is scattered and self assembly forms.Graphene nanobelt has high draw ratio
And special band edge, and banded graphene nanobelt is connected with each other by the lamellar structure of graphene, thus
The conductive network structure formed further promotes the special performance of graphene nanobelt to be fully used.And graphene nano
Band is interspersed in graphene sheet layer simultaneously, while is served again and suppressed the effect that graphene sheet layer stacks；
（3）XRD test results show：Prepared stannic oxide/graphene nano band（GONR）Have in 2 θ=10.0 ° one stronger
Diffraction maximum, illustrate that CNT is successfully peeled off into nanometer band structure.Graphene nanobelt after reduction（GNR）
There is a wider diffraction maximum 2 θ=26.0 °, correspond to（002）Crystal face.Similarly, prepared graphene oxide（GO）2
There is a stronger diffraction maximum θ=10.0 °, illustrate graphene（G）Successfully aoxidized.After reduction, have in 2 θ=26.0 °
One wider diffraction maximum, is also corresponded to（002）Crystal face.And graphene/graphene nanobelt（G/GNR）Composite is similar
XRD spectrum again demonstrate compound and successfully reduced in the presence of reducing agent；
（4）Electrochemical workstation test result shows that prepared graphene/graphene nano belt composite is used as super
During level capacitor electrode material, there is excellent specific capacitance performance, can be drawn from constant current charge-discharge curve, it is close in electric current
Spend for 1 A/g when, its specific capacity value can reach 187.5 F/g.
The advantage of the invention is that：
1st, preparation process is simple, environmental protection, easily operated, is a kind of effective efficiently preparation method；
2nd, experimental design is ingenious：
First, it is the graphene of two dimension and the progress of quasi-one-dimensional graphene nanobelt is compound so that high conductivity, Gao Bibiao
The graphene of area is connected with each other with the graphene nanobelt with unique draw ratio and marginal texture to be run through, and increases composite wood
The specific surface area of material, has effectively constructed multilevel hierarchy；
Second, composite is prepared by the method for simple self assembly, reaction condition is gentle, and can be shorter
Realized in time by a variety of reducing agents；
Graphene prepared by the present invention/graphene nanobelt composite aquogel, can be used as it is a kind of preferably carrier material with
And the electrode material of the new energy devices such as ultracapacitor.
Brief description of the drawings
Fig. 1 is the photo of graphene/graphene nanobelt composite aquogel prepared by embodiment 1.
Fig. 2 is the SEM figures after graphene/graphene nanobelt composite aquogel freeze-drying prepared by embodiment 1.
Fig. 3 is the TEM figures of graphene/graphene nano belt composite prepared by embodiment 1.
Fig. 4 is the XRD of graphene/graphene nano belt composite prepared by embodiment 1.
Fig. 5 is graphene/graphene nano belt composite prepared by embodiment 1（A）Cyclic voltammetry curve,（B）It is permanent
Current charge-discharge electricity curve.
Embodiment
With reference to instantiation, the present invention is expanded on further.It should be understood that these embodiments be merely to illustrate the present invention and
It is not used in limitation the scope of the present invention.In addition, after the content of the invention lectured has been read, those skilled in the art can be right
The present invention makes various changes or modification, and these equivalent form of values equally fall within the application appended claims limited range.
Embodiment 1, the present embodiment comprise the following steps：
（1）Graphite oxide is scattered in deionized water, ultrasound obtains the graphene oxide point of 2 mg/mL stable dispersion
Dispersion liquid；
（2）170 mg ascorbic acid are added in 12 mL graphene oxide water solutions, ultrasound makes it be uniformly dispersed；
（3）The mg/mL stannic oxide/graphene nanos of 8 mL 1.5 band aqueous dispersions are instilled into step（2）In the mixed liquor of gained,
Stirring a period of time, form homogeneous dispersion liquid；
（4）By step（3）The mixed liquor of gained kept at 90 DEG C stand, oil bath react 1 h, you can obtain graphene/
Graphene nanobelt composite aquogel.
Shown in SEM figures, TEM figures as Fig. 1-Fig. 3 after the photo of the composite aquogel, freeze-drying.
Embodiment 2, the present embodiment comprise the following steps：
（1）Graphite oxide is scattered in deionized water, ultrasound obtains the graphene oxide point of 2 mg/mL stable dispersion
Dispersion liquid；
（2）170 mg ascorbic acid are added in 9 mL graphene oxide water solutions, ultrasound makes it be uniformly dispersed；
（3）The mg/mL stannic oxide/graphene nanos of 13.3 mL 1.4 band aqueous dispersions are instilled into step（2）The mixed liquor of gained
In, stirring a period of time, form homogeneous dispersion liquid；
（4）By step（3）The mixed liquor of gained kept at 90 DEG C stand, oil bath react 2 h, you can obtain graphene/
Graphene nanobelt composite aquogel.
Embodiment 3, the present embodiment comprise the following steps：
（1）Graphite oxide is scattered in deionized water, ultrasound obtains the graphene oxide point of 2 mg/mL stable dispersion
Dispersion liquid；
（2）170 mg ascorbic acid are added in 14.4 mL graphene oxide water solutions, ultrasound makes it be uniformly dispersed；
（3）The mg/mL stannic oxide/graphene nanos of 5.3 mL 1.4 band aqueous dispersions are instilled into step（2）The mixed liquor of gained
In, stirring a period of time, form homogeneous dispersion liquid；
（4）By step（3）The mixed liquor of gained keeps standing at 90 DEG C, and 0.5 h is reacted in oil bath, you can obtains graphite
Alkene/graphene nanobelt composite aquogel.
Embodiment 4, the present embodiment comprise the following steps：
（1）Graphite oxide is scattered in deionized water, ultrasound obtains the graphene oxide point of 2 mg/mL stable dispersion
Dispersion liquid；
（2）273 mg 45% hydroiodic acid is added in 12 mL graphene oxide water solutions, ultrasound makes it scattered equal
It is even；
（3）The mg/mL stannic oxide/graphene nanos of 8 mL 1.5 band aqueous dispersions are instilled into step（2）In the mixed liquor of gained,
Stirring a period of time, form homogeneous dispersion liquid；
（4）By step（3）The mixed liquor of gained keeps standing at 90 DEG C, and 2.5 h are reacted in oil bath, you can obtain graphite
Alkene/graphene nanobelt composite aquogel.
Embodiment 5, the present embodiment comprise the following steps：
（1）Graphite oxide is scattered in deionized water, ultrasound obtains the graphene oxide point of 2 mg/mL stable dispersion
Dispersion liquid；
（2）72 mg sodium ascorbates are added in 12 mL graphene oxide water solutions, ultrasound makes it be uniformly dispersed；
（3）The mg/mL stannic oxide/graphene nanos of 12 mL 1 band aqueous dispersions are instilled into step（2）In the mixed liquor of gained,
Stirring a period of time, form homogeneous dispersion liquid；
（4）By step（3）The mixed liquor of gained kept at 95 DEG C stand, oil bath react 5 h, you can obtain graphene/
Graphene nanobelt composite aquogel.
Claims (4)
1. the preparation method of a kind of graphene/graphene nanobelt compound hydrogel material, it is characterised in that comprise the following steps that：
（1）Graphite oxide is scattered in deionized water, through ultrasonic disperse, obtains the graphene oxide dispersion of stable dispersion；
（2）Reducing agent is added in graphene oxide water solution, ultrasound makes it be uniformly dispersed, and obtains mixed liquor；
（3）The aqueous dispersions of stannic oxide/graphene nano band are instilled into step（2）In the mixed liquor of gained, stirring a period of time, shape
Into homogeneous dispersion liquid；
（4）By step（3）The mixed dispersion liquid of gained keeps standing at a certain temperature, is reacted through oil bath, that is, obtain graphene/
Graphene nanobelt composite aquogel；
Step（1）Described in graphene oxide dispersion concentration be 2-5 mg/mL；
Step（2）Described in the concentration of reducing agent be 40-80 mmol/L；
Step（3）Described in concentration of the stannic oxide/graphene nano with aqueous dispersions be 0.5-1.5 mg/mL；
Step（4）Described in mixed dispersion liquid in the mass ratio of graphene oxide and stannic oxide/graphene nano band be 4:1~1:1；
The temperature of described oil bath reaction is 80-100 °C, and the reaction time is 0.5-6.5 h.
2. the preparation method of graphene/graphene nanobelt composite aquogel according to claim 1, it is characterised in that step
（2）Described in reducing agent be selected from ascorbic acid, sodium ascorbate, hydroiodic acid, hydroquinones.
A kind of 3. graphene that preparation method as described in claim 1 is prepared/graphene nanobelt composite aquogel.
4. as graphene according to claim 3/graphene nanobelt composite aquogel is used as carrier material and super
The application of the electrode material of capacitor new energy devices.
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| CN106082341B (en) * | 2016-06-07 | 2018-02-23 | 东华大学 | A kind of preparation method of molybdenum sulfide/graphene graphene nanobelt aerogel composite |
| CN106207125B (en) * | 2016-08-23 | 2018-10-26 | 东华大学 | Sulfur doping selenizing molybdenum/graphene-graphene nanobelt aeroge and its preparation |
| CN106970116B (en) * | 2017-03-20 | 2019-09-10 | 中国石油大学(华东) | The sensitive polyhedral cobaltosic oxide of a kind of pair of acetone-three-dimensional porous Graphene gel composite material film |
| CN107731570B (en) * | 2017-11-24 | 2019-10-18 | 南京正森环保科技有限公司 | A kind of method that Supercapacitor carbon surface chemistry group is eliminated |
| CN108101029A (en) * | 2017-12-25 | 2018-06-01 | 信利光电股份有限公司 | A kind of preparation method of graphene-Nano-Zinc water-setting gel electrode |
| CN108132289A (en) * | 2017-12-25 | 2018-06-08 | 信利光电股份有限公司 | A kind of preparation method of graphene-nano-silver water gel electrode |
| CN112265982A (en) * | 2020-10-23 | 2021-01-26 | 哈尔滨工业大学 | Preparation method of N-doped graphene/graphene nanoribbon composite aerogel |
| CN115376836B (en) * | 2022-09-14 | 2023-08-01 | 南通海星电子股份有限公司 | Preparation method and application of caffeic acid modified chemically-cut carbon nano tube self-assembled composite material |
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| CN103449413A (en) * | 2012-05-30 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method of graphene nanoribbons |
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| CN103449413A (en) * | 2012-05-30 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method of graphene nanoribbons |
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