CN108198699A - A kind of self-supporting graphene film/polyaniline@polyaniline hierarchical structures combination electrode, preparation method and application - Google Patents
A kind of self-supporting graphene film/polyaniline@polyaniline hierarchical structures combination electrode, preparation method and application Download PDFInfo
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- CN108198699A CN108198699A CN201711294079.3A CN201711294079A CN108198699A CN 108198699 A CN108198699 A CN 108198699A CN 201711294079 A CN201711294079 A CN 201711294079A CN 108198699 A CN108198699 A CN 108198699A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention is a kind of preparation method of the flexible composite electrode material of the graphene/polyaniline@polyanilines of self-supporting, graphene oxide is formed the flexible carrier of self-supporting by this method by vacuum filtration first, polyaniline nano fiber is synthesized on its surface by in-situ polymerization again, finally in the electrolyte containing aniline monomer, pass through constant potential chemical deposition, the polyaniline nano palpus of 40 50nm is grown on polyaniline fiber, obtains the classification composite construction based on graphene film.The preparation method effectively increases the electric conductivity of polyaniline nano fiber network, also improve wellability of the flexible compound electrode to electrolyte simultaneously, the composite material is made to show good chemical property, there is good application prospect in super capacitor material field.
Description
Technical field
The invention belongs to new energy materials fields, relate generally to a kind of self-supporting graphene film/polyaniline@polyanilines classification
The preparation of structure composite electrode, can be as the electrode material of ultracapacitor.
Background technology
Flexible ultracapacitor as a kind of novel energy storage device, have higher volumetric power density and
The advantages that portable, cheap, safe, while there is highly important application value in following wearable electronic devices field.However
The energy density of flexible capacitor is still relatively low at present, seriously constrains its commercial applications.Therefore, it develops with high ratio
The flexible electrode material of capacity is the difficult point studied at present.This requires design more rational combined electrode structure to break through electricity
While making its holding electrode material performance, it is strong to have the machinery that bears to be bent or fold for material original chemical property in pole
Degree, the electrochemistry loss of energy caused by so as to avoid ess-strain.
In numerous electrode materials, the grapheme material of two-dimensional structure has abundant specific surface area, ideal electric conductivity
The characteristics such as matter, high intensity and outstanding flexibility, have become the selection to attract attention in self-supporting flexible substrate.Although stone
The research of black alkene electrode material achieves certain progress, but serious reunion stack-up issue can occurs in it in preparation process,
Actual capacity and theoretical capacity is caused still to have very big gap, also has a certain distance from real commercial applications.At present, mainly
By the structure of reasonable design and the preparation method of modified electrode material, come shorten graphite alkenes electrode material theoretical performance with
Gap between actual performance.
Polyaniline is as a kind of low cost, conductive characteristic (the conductivity 100- of environment friendly and protrusion
10000S/m), while there is the specific capacity of 500-3400F/g；The electric conductivity of different doped polyanilines has very big area
Not, it is three kinds of complete reduction-state, intermediate state, complete oxidation state redox states respectively, wherein complete reduction-state and complete oxygen
Both states of change state are conductive states, can be applied to electrode active material；At present for the polyphenyl of these three different conditions
The Study of synthesis method of amine it is more thorough, mainly with the monomer concentration of building-up process, dopant species and polymerization time etc.
It is related；
Invention content
In order to solve the disadvantage that stability difference and specific capacity of the polyaniline compound conducting polymer composite in electrode material are low,
It is an object of the present invention to propose a kind of graphene self-supported membrane for preparing as substrate, and it is classified and ties in its surface construction three-dimensional
The polyaniline fiber combination electrode material method of structure, performance of the polyaniline in electrode material to be overcome to limit.
The present invention is that the dispersion liquid of graphene is formed a kind of graphene film of self-supporting by the method for vacuum filtration, and
The hierarchical structure of polyaniline is constructed on graphene film by two-stage process.Interconnection between polyaniline nano fiber is built
One conductive network, and the classification composite construction formed effectively increase the contact area of polyaniline and electrolyte, and
Conductive network has been advanced optimized, while has in turn ensured ideal gap structure, has effectively increased ion/electron transfer rate.
Therefore, the specific capacity of polyaniline/graphene combination electrode, energy density and the cyclical stability obtained has larger improvement.
The present invention is realized by following technology path：
The preparation method of a kind of self-supporting graphene film/polyaniline@polyaniline hierarchical structure combination electrodes, including following step
Suddenly：
Graphene oxide obtained is filtered by vacuum using Hummers methods and is formed a film, then under the reduction of hydroiodic acid,
Graphene oxide membrane is reduced into redox graphene film；
After the self-supported membrane of gained is cut into 1 × 2cm, by the method for in-situ polymerization, 0.1mol/L persulfuric acid is used
Ammonium grows polyaniline nano fiber structure as initiator on the surface of gained graphene film；
Using three-electrode system, by above-mentioned gained graphene film/polyaniline array, it is immersed in the electrolysis containing aniline monomer
In liquid, under 0.8V current potentials, constant voltage electrochemical deposition, sedimentation time 5-30min are carried out.
Concentration of aniline in above-mentioned electrolyte is 0.05-0.2mol/L, sulfuric acid concentration 0.05-0.2mol/L.
Above-mentioned self-supporting graphene film/polyaniline@polyaniline hierarchical structures combination electrode is applied to ultracapacitor.
Graphene film/polyaniline nano hierarchical structure that the present invention is prepared using in-situ polymerization and electrodeposition process, have with
Lower outstanding feature：
1. by above preparation route it is found that first the present invention be by graphene oxide solution vacuum filtration film forming after again into
Row reduction, effectively prevents agglomeration traits of the graphene during reduction reaction, and retain its flexibility.
2. on the basis of this support membrane, using in-situ polymerization, polyaniline nano is assembled in graphene membrane surface
Fiber avoids and adds additional binding agent, so as to effectively reduce the internal resistance of electrode material, then recycles constant pressure electro-deposition side
Method grows polyaniline nano palpus on polyaniline nano fiber, further improves layer/polyaniline conductive network, while also remain suitable
Suitable porosity ensures coming into full contact between the electrode material and electrolyte.
3. gained combination electrode of the invention shows excellent performance in electro-chemical test, show it in super capacitor
Device electrode material field is widely used prospect.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture of graphene film.
Fig. 2 is the scanning electron microscopic picture of graphene film/polyaniline composite electrode.
Fig. 3,4 for the scanning electron microscopic picture of graphene film/polyaniline@polyaniline hierarchical structures, (low amplification factor and height are put
Big multiple).
Fig. 5 is the electrochemical property test figure for implementing graphene film/polyaniline in 1.
Fig. 6 is the electrochemical property test figure for implementing graphene film/polyaniline@polyanilines in 2.
Specific implementation method
It is further illustrated the present invention below with case study on implementation, but protection scope of the present invention is not limited in implementation case
Example.The other variations and change that those skilled in the art makes in the case of without departing from the spirit and scope of protection of the present invention
It is dynamic, it is included within protection scope of the present invention.
The illustratively preparation route of graphene film first：Graphene oxide is prepared by the Hummers methods of improvement.It is first
1.0g graphite and 1.0g sodium nitrate are first weighed, is added in 1L beakers after grinding uniformly, it is dense to be slowly added to 60mL under condition of ice bath
Sulfuric acid is sufficiently stirred；6.0g potassium permanganate is weighed again, in adding in beaker in 3h in batches, while maintain condition of ice bath, treats that its is complete
After full addition, it is transferred to and is heated in 35 DEG C of oil bath pans and stir more than 10h, then add the deionization of 150mL 50-60 DEG C
Water, stirs 2h, and centrifugation obtains graphene oxide precipitation, finally washed with 5% hydrochloric acid solution and a large amount of deionized waters
To neutrality, graphene oxide powder is obtained after freeze-drying；
Gained graphene oxide powder is dissolved in deionized water, is made into the solution of 0.5mg/mL, takes the above-mentioned oxygen of 50mL
Graphite alkene solution forms a film through vacuum filtration, at a temperature of 90 DEG C, 20ml hydroiodic acids (57%) reductase 12 h is added in, after taking-up
1 × 2cm sizes are cut into, and are washed with deionized water, ethyl alcohol, drying for standby.
Embodiment 1：
The graphene film cut immerses the 0.1M camphorsulfonic acid solution of 40ml, adds the aniline monomer of 0.6 mmol,
After being sufficiently stirred, add 20mL 0.1M sodium peroxydisulfates solution and cause aniline monomer polymerization, taken out after reacting 6h under room temperature
Sample, and being rinsed well with a large amount of deionized waters and ethyl alcohol, the later drying overnight in vacuum drying oven, obtains sample 1, labeled as stone
Black alkene/polyaniline；
Embodiment 2：
The sulfuric acid of 0.1M and the aniline solution of 0.1M is configured, the wherein ratio of water and ethyl alcohol is 1:1, by above-described embodiment 1
Middle gained sample 1 (graphene film/polyaniline) is immersed in the electrolyte, the constant pressure electro-deposition 10min under the voltage of 0.8V, it
After be washed with deionized and dry, sample 2 is obtained, labeled as graphene/polyaniline@polyanilines.
Above-mentioned graphene/polyaniline, graphene/polyaniline are gathered with field emission scanning electron microscope (JSM-4800)
Aniline combination electrode material carries out morphology characterization；
Directly as working electrode after drying, while the sulfuric acid of 1M is configured in combination electrode material in embodiment 1 and example 2
The solution of sodium is as electrolyte, and using platinized platinum as to electrode, Ag/AgCl electrodes are reference electrode, form three-electrode system, in occasion China
CHI660E electrochemical workstations carry out electro-chemical test, cyclic voltammetry voltage range selection -0.1-0.9V, as a result as schemed
5、6.Under the sweep speed of 5mV/s, the specific capacity of graphene/polyaniline is 568.3F/g and graphene/polyaniline@polyphenyl
The specific capacity of amine is 735.4F/g, and the specific capacity under different scanning rates is as shown in the table：
| Current density | 5mv/s | 10mv/s | 20mv/s | 30mv/s | 50mv/s |
| Embodiment 1 | 568.3F/g | 543.2F/g | 513.3F/g | 488.6F/g | 430.8F/g |
| Embodiment 2 | 735.4F/g | 603.4F/g | 550.0F/g | 525.8F/g | 506.7F/g |
Claims (7)
1. a kind of preparation method of self-supporting graphene film/polyaniline@polyaniline hierarchical structure combination electrodes, which is characterized in that
The preparation method of above-mentioned electrode material includes following several steps：
Using Hummers methods, by the oxidation of nitric acid and potassium permanganate by commercialized graphite flake oxidative exfoliation into individual layer
Graphene, then rinsed with a large amount of hydrochloric acid and deionized water, it is water-soluble to be configured to certain density graphene after freeze-drying
Liquid recycles vacuum filtration method to obtain the graphene film of self-supporting；
Polyaniline nano fiber is grown by situ chemical oxidative polymerization in graphene membrane surface；
Using three-electrode system, using constant potential electrochemical deposition method, load is had to the graphene film of polyaniline nano fiber
It is immersed in the electrolyte containing aniline monomer, realizes that polyaniline nano must be in polyaniline fiber surface vertical-growth.
2. preparation method according to claim 1, which is characterized in that the nanofiber uniform vertical of polyaniline is grown in stone
On the film of black alkene, polyaniline fiber nano array structure is formed, the diameter of the polyaniline fiber is in 100-120nm, the battle array
The height of row is in 40-50nm.
3. preparation method according to claim 1, which is characterized in that the time of the in-situ polymerization is used in 4-10h, aniline
Amount is in 0.3-0.9mmol.
4. preparation method according to claim 1, which is characterized in that a concentration of 0.05- of sulfuric acid in the electrolyte
0.2mol/L, concentration of aniline 0.05-0.2mol/L.
5. preparation method according to claim 1, which is characterized in that the array that the polyaniline fiber is formed equably is given birth to
It grows on the surface of graphene film；The also polyaniline nano palpus of homoepitaxial 40-50nm on polyaniline fiber simultaneously.
6. a kind of self-supporting graphene film/polyaniline@polyaniline hierarchical structure combination electrodes, which is characterized in that by claim 1
Preparation method obtain.
7. a kind of application of self-supporting graphene film/polyaniline@polyaniline hierarchical structure combination electrode materials, which is characterized in that
The graphene film/polyaniline@polyaniline hierarchical structures combination electrode material is applied to ultracapacitor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114121496A (en) * | 2021-10-28 | 2022-03-01 | 中国科学院深圳先进技术研究院 | Flexible composite electrode, preparation method thereof and flexible energy storage device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103137342A (en) * | 2013-02-06 | 2013-06-05 | 燕山大学 | Grapheme-polyaniline super capacitor electrode material and preparation method thereof |
| CN103337377A (en) * | 2013-06-14 | 2013-10-02 | 哈尔滨工业大学 | Preparation method for well-organized high-capacity self-supporting film based on epitaxial growth of polyaniline on graphene surface |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103137342A (en) * | 2013-02-06 | 2013-06-05 | 燕山大学 | Grapheme-polyaniline super capacitor electrode material and preparation method thereof |
| CN103337377A (en) * | 2013-06-14 | 2013-10-02 | 哈尔滨工业大学 | Preparation method for well-organized high-capacity self-supporting film based on epitaxial growth of polyaniline on graphene surface |
Non-Patent Citations (2)
| Title |
|---|
| HASSAN H.K.: "Electropolymerization of Aniline Over Chenmically Converted Graphene Systematic Study and Effect of Dopant", 《INTERNATIONAL JOURNAL OF ELECTROCHEMICAL SCIENCE》 * |
| 王义师: "石墨烯／聚苯胺复合材料的制备、电化学性能及机理研究", 《中国优秀硕士学位论文全文数据库工程科技I辑2013年第6期》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114121496A (en) * | 2021-10-28 | 2022-03-01 | 中国科学院深圳先进技术研究院 | Flexible composite electrode, preparation method thereof and flexible energy storage device |
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