CN108530643B - A kind of preparation method of graphene Polyaniline Grafted composite material - Google Patents
A kind of preparation method of graphene Polyaniline Grafted composite material Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 97
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 230000009435 amidation Effects 0.000 claims abstract description 14
- 238000007112 amidation reaction Methods 0.000 claims abstract description 14
- 238000012983 electrochemical energy storage Methods 0.000 claims abstract description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 4
- 238000001548 drop coating Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 graphene modified Carbon Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
-
- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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 relates to a kind of preparation methods of graphene Polyaniline Grafted composite material that can be used for electrochemical energy storage.The following steps are included: the preparation of carboxyl-functional graphene oxide, the preparation of amidation graphene, the preparation of graphene Polyaniline Grafted.The beneficial effects of the invention are as follows the preparation method novel and uniques of graphene Polyaniline Grafted composite material.
Description
Technical field
The present invention relates to a kind of preparation methods of graphene Polyaniline Grafted composite material that can be used for electrochemical energy storage, belong to
In materials synthesis and electrochemical research field.
Technical background
Electrochemical capacitor is also referred to as supercapacitor, compared with conventional batteries, due to there is high power density, quickly fills
Flash-over characteristic, longer cycle life and environment friendly, cause great concern in the past few decades.According to its energy storage
Mechanism, supercapacitor can be divided into double layer capacitor and pseudocapacitors, the former accumulates electricity at the interface of electrode and electrolyte
Lotus, the latter store energy by the Reversible redox reaction of electrode material.Compared with other energy storage devices, supercapacitor
It can the charge and discharge under very high rate.The performance of this brilliance makes supercapacitor be expected to be applied in a variety of manners in energy
Storage facilities.
Graphene because its good electric conductivity, thermal stability and mechanical property as matrix electrode material in recent years one
It is directly the hot spot of research, but graphene disadvantage easy to reunite limits its capacitive property.Conductive polymer polyanaline has high ratio
Capacitor is easily-synthesized, the advantage that environmental stability is good, inexpensive, can pass through the reunion of prevention graphene after compound with graphene
To increase the specific surface area of electrode material.Some researches show that polyaniline and graphene is connected by covalent effect, can be improved multiple
The chemical property of condensation material.In order to enhance the grafting performance of polyaniline and prevent graphene from reuniting, pass through p-aminophenyl first
The diazotization of acid is upper on the surface of graphene to introduce nucleation site.Pass through conjugation key connection polyaniline and graphene, Ke Yijia
The transmission of fast electronics and reduction interface resistance, while the electric conductivity of composite material can be improved and improve the electricity of corresponding device
Capacitive energy.
Summary of the invention
The purpose of the invention is to provide a kind of graphene Polyaniline Grafted composite materials that can be used for electrochemical energy storage
Preparation method.The present invention provides a kind of preparation methods of novel energy storage material, and amidized graphene is passed through chemistry
Oxidizing process Polyaniline Grafted is to obtain graphene Polyaniline Grafted composite material.
A kind of preparation method packet of graphene Polyaniline Grafted composite material can be used for electrochemical energy storage of the present invention
Include following steps:
A, it the preparation of carboxyl-functional graphene oxide: weighs 0.1g p-aminobenzoic acid and is dissolved in 4mL concentrated hydrochloric acid, obtain
To white suspension, it is cooled to 0 DEG C and stirs, 3mL NaNO is then added dropwise2Ice water solution, obtain p-aminobenzoic acid
And NaNO2Mixed solution and continue stir 30min, graphene oxide ultrasonic disperse into 10mL ice water and is slowly added into
In above-mentioned mixed solution, then at 0 DEG C stir 3h after be warming up to 25 DEG C, continue to stir at 25 DEG C, by product spend from
Sub- water washing, filtering are simultaneously freeze-dried the graphene oxide for obtaining carboxyl-functional for 24 hours at -42 DEG C；
B, the preparation of amidation graphene: the carboxyl-functional graphene oxide in step a is added in ethylene glycol and is surpassed
Sonication 10min, is then added ammonium hydroxide, obtains carboxyl-functional graphene oxide dispersion, and above-mentioned dispersion liquid is transferred to
In 100mL autoclave, cooling after 10h is then reacted at 180 DEG C, product is washed with deionized, is filtered, simultaneously
It is freeze-dried at -42 DEG C for 24 hours, obtains amidation graphene；
C, the amidation graphene in step b the preparation of graphene Polyaniline Grafted: is added to 100mL 1M HCl
In, aniline is added under ice bath stirring, obtains the dispersion liquid of amidation graphene and aniline, weighs 0.12g ammonium persulfate and is dissolved in
It in 100mL 1M HCl and is added in above-mentioned dispersion liquid, continues to stir under ice bath, product is washed with deionized, mistake
It filters and is freeze-dried the polyaniline for obtaining graphene grafting for 24 hours at -42 DEG C.Resulting graphene Polyaniline Grafted is dispersed
Into ultrapure water, the dispersion liquid of 2mg/mL is obtained, the 10 μ L dispersant liquid drops is pipetted with liquid-transfering gun and is applied to the surface of glass-carbon electrode simultaneously
It is dried with infrared lamp, then using the glass-carbon electrode of graphene Polyaniline Grafted modification as working electrode, supplemented by saturated calomel electrode
Electrode is helped, platinum plate electrode is to electrode, the H of 1mol/L2SO4For electrolyte, polyphenyl is grafted to graphene by electrochemical workstation
Amine carries out constant current charge-discharge test.
Further, NaNO in the step a2Molar concentration be 0.2~0.3mol/L, the quality of graphene oxide is
0.05~0.1g, mixing time is 6~8h at 25 DEG C.
Further, the quality of carboxyl-functional graphene oxide is 0.1~0.2g, the volume of ethylene glycol in the step b
For 40~50mL, the volume of ammonium hydroxide is 1~2mL.
Further, the quality of amidation graphene is 80~120mg in the step c, the volume of aniline is 0.15~
0.2mL, mixing time is 9h under ice bath.
The beneficial effects of the present invention are: the preparation method novel and unique of graphene Polyaniline Grafted composite material.
Detailed description of the invention
The following further describes the present invention with reference to the drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphene Polyaniline Grafted composite material prepared in embodiment one；
Fig. 2 be the graphene Polyaniline Grafted prepared in embodiment one, the graphene/polyaniline prepared in comparative example one,
The constant current charge-discharge figure of the polyaniline prepared in the graphene and comparative example three prepared in comparative example two.
Specific embodiment
Presently in connection with specific embodiment, the present invention will be further described, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment one:
A kind of preparation method for the graphene Polyaniline Grafted composite material can be used for electrochemical energy storage, including following step
It is rapid:
(1) it weighs 0.1g p-aminobenzoic acid to be dissolved in 4mL concentrated hydrochloric acid, obtains white suspension, be cooled to 0 DEG C and stir
It mixes, 3mL 0.24mol/L NaNO is then added dropwise2Ice water solution, obtain p-aminobenzoic acid and NaNO2Mixed solution
And continue to stir 30min, 0.1g graphene oxide ultrasonic disperse into 10mL ice water and is slowly added into above-mentioned mixed solution
In, 25 DEG C are warming up to after then stirring 3h at 0 DEG C, continues to stir 6h at 25 DEG C, product is washed with deionized, mistake
It filters and is freeze-dried the graphene oxide for obtaining carboxyl-functional for 24 hours at -42 DEG C.
(2) graphene oxide of the carboxyl-functional in 0.15g step (1) is added in 40mL ethylene glycol and is ultrasonically treated
Then 10min is added 1.5mL ammonium hydroxide, obtains carboxyl-functional graphene oxide dispersion, above-mentioned dispersion liquid is transferred to
In 100mL autoclave, cooling after 10h is then reacted at 180 DEG C, product is washed with deionized, is filtered, simultaneously
It is freeze-dried at -42 DEG C for 24 hours, obtains amidation graphene.
(3) amidation graphene in 100mg step (2) is added in 100mL 1M HCl, is added under ice bath stirring
0.2mL aniline obtains the dispersion liquid of amidation graphene and aniline, weighs 0.12g ammonium persulfate and is dissolved in 100mL 1M HCl
After be added in above-mentioned dispersion liquid, continue under ice bath stir 9h, product is washed with deionized, is filtered and at -42 DEG C
Freeze-drying for 24 hours, obtains the polyaniline of graphene grafting.As shown in Figure 1, graphene Polyaniline Grafted shows the stick of some distortions
The polyaniline folding of shape structure is entangled, is coated on graphene outer layer.Resulting graphene Polyaniline Grafted is distributed to
In ultrapure water, the dispersion liquid of 2mg/mL is obtained, pipette 10 μ L drop coatings in the surface of glass-carbon electrode with liquid-transfering gun and is dried with infrared lamp
Dry, then using the glass-carbon electrode of graphene Polyaniline Grafted modification as working electrode, saturated calomel electrode is auxiliary electrode, platinized platinum
Electrode is to electrode, the H of 1mol/L2SO4For electrolyte, permanent electricity is carried out to graphene Polyaniline Grafted by electrochemical workstation
Flow charge-discharge test.Such as Fig. 2, discharge time can be read from the constant current charge-discharge test chart of graphene Polyaniline Grafted,
And it is 1A/g when ratio that the graphene Polyaniline Grafted modified glassy carbon electrode, which can be calculated, in current density in conjunction with formula (1)
Capacitor is 553F/g.
In formula (1), Cs represents specific capacitance, and I represents electric current, and t is discharge time, and m represents modification on glass-carbon electrode
The quality of graphene Polyaniline Grafted, V represent potential window.
Comparative example one:
A kind of preparation method for the graphene/polyaniline material can be used for electrochemical energy storage, comprising the following steps:
(1) 0.15g graphene oxide is added in 40mL ethylene glycol and is ultrasonically treated 10min, 1.5mL ammonia is then added
Above-mentioned solution is transferred in 100mL autoclave by water, reacts 10h at 180 DEG C, product is washed with deionized,
It filters and is freeze-dried at -42 DEG C for 24 hours, obtain graphene.
(2) graphene in 100mg step (1) is added in 100mL 1M HCl, 0.2mL benzene is added under ice bath stirring
Amine is weighed after 0.12g ammonium persulfate is dissolved in 100mL 1M HCl and is added in said mixture, continues to stir 9h under ice bath,
Product is washed with deionized, is filtered and is freeze-dried for 24 hours at -42 DEG C, graphene/polyaniline is obtained.It will be resulting
Graphene/polyaniline is distributed in ultrapure water, obtains the dispersion liquid of 2mg/mL, pipettes 10 μ L drop coatings in glass-carbon electrode with liquid-transfering gun
Surface and dried with infrared lamp, then using graphene/polyaniline modification glass-carbon electrode as working electrode, saturated calomel electrode
For auxiliary electrode, platinum plate electrode is to electrode, the H of 1mol/L2SO4For electrolyte, by electrochemical workstation to graphene/poly-
Aniline carries out constant current charge-discharge test.Such as Fig. 2, can be read from the constant current charge-discharge test chart of graphene/polyaniline
Discharge time, and it is 1A/g that the graphene/polyaniline modified glassy carbon electrode, which can be calculated, in current density in conjunction with formula (1)
When specific capacitance be 426F/g.
Comparative example two:
A kind of preparation method for the graphene can be used for electrochemical energy storage, comprising the following steps:
0.15g graphene oxide is added in 40mL ethylene glycol and is ultrasonically treated 10min, 1.5mL ammonium hydroxide is then added, it will
Above-mentioned solution is transferred in 100mL autoclave, reacts 10h at 180 DEG C, product is washed with deionized, is filtered,
And be freeze-dried at -42 DEG C for 24 hours, obtain graphene.By resulting graphene dispersion into ultrapure water, point of 2mg/mL is obtained
Dispersion liquid pipettes 10 μ L drop coatings in the surface of glass-carbon electrode with liquid-transfering gun and is dried with infrared lamp, then with the glass of graphene modified
Carbon electrode is working electrode, and saturated calomel electrode is auxiliary electrode, and platinum plate electrode is to electrode, the H of 1mol/L2SO4For electrolysis
Liquid carries out constant current charge-discharge test to graphene by electrochemical workstation.Such as Fig. 2, from constant current charge-discharge test chart
Discharge time can be read, and it is 1A/ that the graphene modified glass-carbon electrode, which can be calculated, in current density in conjunction with formula (1)
Specific capacitance is 156F/g when g.
Comparative example three:
A kind of preparation method for the polyaniline can be used for electrochemical energy storage, comprising the following steps:
0.2mL aniline monomer is added in 100mL 1M HCl, 30min is stirred under ice-water bath, obtains aniline solution.
0.12g ammonium persulfate is dissolved in 100mL 1M HCl and is slowly added into above-mentioned aniline solution, stirs 9h under ice bath.Product is used
Deionized water washing is filtered and is freeze-dried at -42 DEG C for 24 hours, and polyaniline is obtained.By resulting dispersing polyaniline to ultrapure
In water, the dispersion liquid of 2mg/mL is obtained, pipette 10 μ L drop coatings in the surface of glass-carbon electrode with liquid-transfering gun and is dried with infrared lamp, so
Afterwards using the glass-carbon electrode of Polyaniline-modified as working electrode, saturated calomel electrode is auxiliary electrode, platinum plate electrode be to electrode,
The H of 1mol/L2SO4For electrolyte, constant current charge-discharge test is carried out to polyaniline by electrochemical workstation.Such as Fig. 2, from poly-
Discharge time can be read in the constant current charge-discharge test chart of aniline, and the polyaniline can be calculated in conjunction with formula (1)
Modified glassy carbon electrode specific capacitance when current density is 1A/g is 342F/g.
Claims (4)
1. a kind of preparation method for the graphene Polyaniline Grafted composite material that can be used for electrochemical energy storage, it is characterised in that: step
It is rapid as follows:
A, it the preparation of carboxyl-functional graphene oxide: weighs 0.1g p-aminobenzoic acid and is dissolved in 4mL concentrated hydrochloric acid, obtain white
Color suspension is cooled to 0 DEG C and stirs, 3mL NaNO is then added dropwise2Ice water solution, obtain p-aminobenzoic acid and
NaNO2Mixed solution and continue to stir 30min, graphene oxide ultrasonic disperse into 10mL ice water and is slowly added into
It states in mixed solution, is warming up to 25 DEG C after then stirring 3h at 0 DEG C, continues to stir at 25 DEG C, by product deionization
Water washing, filtering are simultaneously freeze-dried for 24 hours at -42 DEG C, obtain carboxyl-functional graphene oxide；
B, the preparation of amidation graphene: the carboxyl-functional graphene oxide in step a is added in ethylene glycol at ultrasound
10min is managed, ammonium hydroxide is then added, obtains carboxyl-functional graphene oxide dispersion, above-mentioned dispersion liquid is transferred to 100mL high
It presses in reaction kettle, cooling after 10h is then reacted at 180 DEG C, product is washed with deionized, is filtered and at -42 DEG C
Freeze-drying for 24 hours, obtains amidation graphene；
C, the preparation of graphene Polyaniline Grafted: the amidation graphene in step b is added in 100mL 1M HCl, ice bath
It is added with stirring aniline, obtains the dispersion liquid of amidation graphene and aniline, 0.12g ammonium persulfate is weighed and is dissolved in 100mL 1M
It in HCl and is added in above-mentioned dispersion liquid, continues to stir under ice bath, product is washed with deionized, is filtered and -42
It is freeze-dried at DEG C for 24 hours, obtains graphene Polyaniline Grafted；Resulting graphene Polyaniline Grafted is distributed in ultrapure water,
The dispersion liquid of 2mg/mL is obtained, the 10 μ L dispersant liquid drops is pipetted with liquid-transfering gun and is applied to the surface of glass-carbon electrode and is dried with infrared lamp
Dry, then using the glass-carbon electrode of graphene Polyaniline Grafted modification as working electrode, saturated calomel electrode is auxiliary electrode, platinized platinum
Electrode is to electrode, the H of 1mol/L2SO4For electrolyte, permanent electricity is carried out to graphene Polyaniline Grafted by electrochemical workstation
Flow charge-discharge test.
2. a kind of preparation side for the graphene Polyaniline Grafted composite material that can be used for electrochemical energy storage according to claim 1
Method, it is characterized in that: NaNO in the step a2Molar concentration be 0.2~0.3mol/L, the quality of graphene oxide is 0.05
~0.1g, mixing time is 6~8h at 25 DEG C.
3. a kind of preparation side for the graphene Polyaniline Grafted composite material that can be used for electrochemical energy storage according to claim 1
Method, it is characterized in that: carboxyl-functional graphene oxide quality is 0.1~0.2g in the step b, the volume of ethylene glycol is 40~
50mL, ammonium hydroxide are 1~2mL.
4. a kind of preparation side for the graphene Polyaniline Grafted composite material that can be used for electrochemical energy storage according to claim 1
Method, it is characterized in that: the quality of amidation graphene is 80~120mg in the step c, the volume of aniline is 0.15~0.2mL,
Mixing time is 9h under ice bath.
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| CN109456478B (en) * | 2018-10-22 | 2021-04-02 | 东华大学 | Preparation method of graphene/polyaniline binary wave-absorbing material |
| CN110734727A (en) * | 2018-10-23 | 2020-01-31 | 嘉兴学院 | Preparation method of conductive adhesive of polyaniline modified flaky carbon powder |
| CN110289176B (en) * | 2019-02-25 | 2021-07-02 | 常州大学 | Preparation method of polyaniline grafted reduced graphene oxide/multi-walled carbon nanotube composite material for electrochemical energy storage |
| CN113593931B (en) * | 2021-06-30 | 2022-04-01 | 燕山大学 | Preparation method of supercapacitor electrode material NiCoMn-LDH/functionalized graphene |
| CN114220670B (en) * | 2021-12-16 | 2023-09-12 | 福州大学 | Preparation method of non-covalent hybridized MOF graphene aerogel/molybdenum capacitor electrode material |
| CN115064666B (en) * | 2022-05-11 | 2023-11-03 | 万向一二三股份公司 | Conductive polymer grafted graphene coated silicon anode material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104064363A (en) * | 2014-05-20 | 2014-09-24 | 东华大学 | 3D petal-shaped graphene-polyaniline super-capacitor electrode material and preparation method thereof |
| CN104445155A (en) * | 2013-09-17 | 2015-03-25 | 中国科学院大连化学物理研究所 | Carboxyl functionalized graphene material and preparation method thereof |
| CN104910378A (en) * | 2015-05-26 | 2015-09-16 | 浙江理工大学 | Preparation method for polyaniline/graphene oxide nanocomposite |
| CN105860064A (en) * | 2016-06-17 | 2016-08-17 | 西北师范大学 | Preparation method of polyaniline/carboxylated graphene composite material |
-
2018
- 2018-04-13 CN CN201810333284.4A patent/CN108530643B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445155A (en) * | 2013-09-17 | 2015-03-25 | 中国科学院大连化学物理研究所 | Carboxyl functionalized graphene material and preparation method thereof |
| CN104064363A (en) * | 2014-05-20 | 2014-09-24 | 东华大学 | 3D petal-shaped graphene-polyaniline super-capacitor electrode material and preparation method thereof |
| CN104910378A (en) * | 2015-05-26 | 2015-09-16 | 浙江理工大学 | Preparation method for polyaniline/graphene oxide nanocomposite |
| CN105860064A (en) * | 2016-06-17 | 2016-08-17 | 西北师范大学 | Preparation method of polyaniline/carboxylated graphene composite material |
Non-Patent Citations (1)
| Title |
|---|
| 羧基化石墨烯基导电聚吡咯复合材料的超电容性能;李娜;《应用化学》;20130331;第30卷(第3期);正文第355页第1.3-1.4节 * |
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