CN104916459A - Preparation method of highly-oriented graphene film for supercapacitor - Google Patents
Preparation method of highly-oriented graphene film for supercapacitor Download PDFInfo
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- CN104916459A CN104916459A CN201510366344.9A CN201510366344A CN104916459A CN 104916459 A CN104916459 A CN 104916459A CN 201510366344 A CN201510366344 A CN 201510366344A CN 104916459 A CN104916459 A CN 104916459A
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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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- 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 invention relates to a preparation method of a highly-oriented graphene film for a supercapacitor. The preparation method comprises the following steps: washing graphite oxide, then adding deionized water to obtain a suspension liquid, performing ultrasonic and centrifugal washing, then performing rotary evaporation on a supernatant liquor to obtain a graphite oxide slurry; scraping and coating the graphite oxide slurry on the surface of a copper coil to manufacture a graphite oxide film, and then performing radiation reduction treatment to obtain the highly-oriented graphene film. The film is formed by adopting a scraping method, the reduction process adopts photoreduction, the process is simple, and the method is liable to industrial production; and the highly-oriented graphene film for the supercapacitor prepared by the preparation method is better in flexibility and high in specific capacitance, and has a wide application in the fields of flexible energy storage such as flexible supercapacitors and lithium ion batteries.
Description
Technical field
The invention belongs to the preparation field of ultracapacitor thin-film material, particularly a kind of ultracapacitor preparation method of high orientation graphene film.
Background technology
2004, the people such as the Geim of Manchester university of Britain found by carbon atom with Sp
2monoatomic layer two dimensional crystal-Graphene (Graphene) that hydridization is connected to form, Graphene is by the another new carbon structural form that it is found that after fullerene and carbon nano-tube, is one of current optimal two-dimension nano materials.The discovery of Graphene, makes the diversity of people to carbon have more deep understanding, defines the diamond from the Graphene of the carbon nano-tube of the fullerene of zero dimension, one dimension, two dimension to three-dimensional and graphite complete carbon family system.As the two-dimentional quantum regime that a kind of room-temperature stable exists, traditional Condensed Matter Physics theory has been broken in the discovery of Graphene, overthrow the prophesy that strict two dimensional crystal that former people generally believe cannot exist at limited temperature, great impact may have been produced on the development of Condensed Matter Physics theory.Graphene is a kind of strict two dimensional crystal material, because it has unique Structure and Properties, becomes rapidly the focus of international field of new research.
The people such as M.D.Stoller are in Nano Letter 8 (2008) 3498-3452 reported first for the graphene powder of electrode material for super capacitor, and grapheme material ratio capacitance in aqueous electrolyte prepared by this method reaches 135F/g.But the compound that Graphene prepared by this chemical method is still powder needs and binding agent and conductive agent just can make electrode of super capacitor.The people such as X.F.Duan report the graphene film electrode of super capacitor adopting hydro thermal method preparation to have three-dimensional structure on ACS Nano DOI:10.1021/nn4000836, and this Graphene electrodes has shown outstanding volumetric capacitance and quality compares electric capacity.
But the method being commonly used to now prepare graphene film comprises chemical vapour deposition technique, suction filtration membrane formation process and hydro thermal method etc., preparation process is complicated, and equipment requirement is high, yields poorly and is all unfavorable for large-scale production.
The application of this right adopts knife coating film forming, and adopts photoreduction, and preparation process reduction process is all simple.Have not yet to see the report adopting photoreduction legal system for high orientation graphene membrane electrode material.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of ultracapacitor with high orientation graphene film, the method technique is simple, be easy to suitability for industrialized production, prepared ultracapacitor has better pliability with high orientation graphene film, ratio capacitance is high, has wide application in the flexible energy storage such as flexible super capacitor, lithium ion battery field.
A kind of ultracapacitor of the present invention preparation method of high orientation graphene film, comprising:
(1) washed by graphite oxide, then add in deionized water, obtain suspension, ultrasonic, centrifuge washing removes unstripped graphite composite powder, then by supernatant rotary evaporation, obtains graphite oxide slurry;
(2) by graphite oxide slurry blade coating at copper foil surface, obtained graphite oxide film, then carries out irradiation reduction treatment, obtains high orientation graphene film.
In described step (1), washing is deionized water washing 2-4 time.
In described step (1), the concentration of suspension is 0.5 ~ 6mg/mL.
In described step (1), ultrasonic time is 1-3h.
In described step (1), centrifuge washing is: centrifugal 10 ~ 40min under 2500 ~ 3500r/min condition.
In described step (1), rotary evaporation is rotary evaporation under 40 ~ 55 DEG C of conditions.
In described step (2), graphite oxide slurry blade coating is specially at copper foil surface: the Copper Foil that surface clean is good is adsorbed in doctor knife coater surface, by blade coating cutter setting thickness, starts doctor knife coater by graphite oxide slurry blade coating at copper foil surface.
Described blade coating cutter setting thickness is 50 ~ 200 μm.
Irradiating reduction treatment in described step (2) is: under being placed in xenon lamp, reduction 3-12h is irradiated at 10 ~ 20cm place.
Graphite oxide is prepared into by the present invention can the slurry of blade coating, and blade coating, on conductive substrates surface, is prepared into large-area graphite oxide film, and adopts simple photoreduction method, graphite oxide film is reduced into high orientation graphene film.There is height-oriented graphene film interlayer charge transmission resistance low, be extremely conducive to the collection liquid surface that electric charge directly imports to conduction.
Adopt the high orientation graphene film of ultracapacitor prepared by this method, preparation technology is simple, be easy to suitability for industrialized production, prepared ultracapacitor has better pliability with high orientation graphene film, ratio capacitance is high, has wide application in the flexible energy storage such as flexible super capacitor, lithium ion battery field.
beneficial effect
(1) the method preparation technology is simple, and film forming procedure is without the need to conductive agent, binding agent, and reduction process adopts photoreduction, without the need to chemical reagent and heating process;
(2) graphene film for supercapacitor that prepared by the method has better pliability, and ratio capacitance is high, has wide application in the flexible energy storage such as flexible super capacitor, lithium ion battery field.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of high orientation graphene film, graphene powder, graphite oxide powder and original graphite in embodiment 1;
Fig. 2 is the digital photograph of various samples prepared by embodiment 1: (A) graphite oxide film; (B) figure is the high orientation graphene film after reduction; (C) figure is the high orientation graphene film of self-supporting.
Fig. 3 is the impedance spectrum of high orientation graphene film three electrode test prepared by embodiment 1, and illustration is high-frequency region collection of illustrative plates;
Fig. 4 is the cyclic voltammetry curve of high orientation graphene film three electrode test in 1M sodium sulphate electrolyte under different scanning rates prepared by embodiment 1;
Fig. 5 is the graphene film three electrode test structure prepared of embodiment 1 constant current charge-discharge curve first under different current density in 1M sodium sulphate electrolyte.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Be mixed with the deionized water suspension that concentration is 0.5mg/mL after graphite oxide being spent deionized water 2 times, the centrifugal 40min of ultrasonic 1h, 2500r/min washs and removes unstripped graphite composite powder, by supernatant at 40 DEG C of rotary evaporations to forming graphite oxide slurry.The Copper Foil that surface clean is good is adsorbed in doctor knife coater surface, blade coating cutter is set as 50 μm, start doctor knife coater by graphite oxide slurry blade coating at copper foil surface, obtained graphite oxide film, under graphite oxide film being placed in xenon lamp, 10cm place irradiates reduction 3h and get final product.
Fig. 1 is the X ray diffracting spectrum of high orientation graphene film, graphene powder, graphite oxide powder and original graphite.In figure, the position of the diffraction maximum of original graphite is positioned at 2 θ=26.5 °, and be the spike that intensity is very high, interplanar distance is the interplanar distance 0.334nm of typical graphite, the position that the peak position that graphite oxide occurs is set to graphite oxide typical peaks is 2 θ=11 °, graphene powder, because arrange uneven between lamella, is occur steamed bun peak in 2 θ=25.14 °, high orientation graphene film is then because curve appears in the regularly arranged of graphene sheet layer, diffraction maximum also shows as stronger spike, but then obvious broadening compared with original graphite, interplanar distance then changes 0.342nm into.
Fig. 2 is the digital photograph of the various samples of product: (A) graphite oxide film; (B) figure is the high orientation graphene film after reduction; (C) figure is the high orientation graphene film of self-supporting.Can be found out by digital photograph presents typically orange-yellow at graphite oxide film, then change black into after reduction, and film forming evenly and have certain gloss.
Fig. 3 is the impedance spectrum of product three electrode test, and illustration is high-frequency region collection of illustrative plates, carries out to gained impedance curve the contact resistance R that matching obtains graphene film
sbe 3.57 Ω, transferring charge resistance R
ctbe 4.52 Ω.
Fig. 4 is that product is at the cyclic voltammetry curve of two electrode test structures in 1M sodium sulphate electrolyte under different scanning rates, the high specific electric capacity of high orientation graphene film reaches 302F/g as calculated, maximum energy density is 26.8Wh/kg, and maximum power density is 23.4kW/kg.
Fig. 5 is product at two electrode test structures constant current charge-discharge curve first under different current density in 1M sodium sulphate electrolyte.Show that product all has good charge-discharge characteristic under different charging and discharging currents density.
Embodiment 2
Be mixed with the deionized water suspension that concentration is 6mg/mL after graphite oxide being spent deionized water 4 times, the centrifugal 10min of ultrasonic 3h, 3500r/min washs and removes unstripped graphite composite powder, by supernatant at 55 DEG C of rotary evaporations to forming graphite oxide slurry.The Copper Foil that surface clean is good is adsorbed in doctor knife coater surface, blade coating cutter is set as 200 μm, start doctor knife coater by graphite oxide slurry blade coating at copper foil surface, obtained graphite oxide film, under graphite oxide film being placed in xenon lamp, 20cm place irradiates reduction 12h and get final product.
X-ray diffraction analysis is indicated as and prepares high orientation graphene film, impedance analysis shows that contact resistance, transferring charge resistance are lower, cyclic voltammetry curve analysis has higher ratio capacitance, energy density and power density, and constant current charge-discharge analysis has good charge-discharge performance.
Embodiment 3
Be mixed with the deionized water suspension that concentration is 3mg/mL after graphite oxide being spent deionized water 3 times, the centrifugal 20min of ultrasonic 1h, 3000r/min washs and removes unstripped graphite composite powder, by supernatant at 45 DEG C of rotary evaporations to forming graphite oxide slurry.The Copper Foil that surface clean is good is adsorbed in doctor knife coater surface, blade coating cutter is set as 100 μm, start doctor knife coater by graphite oxide slurry blade coating at copper foil surface, obtained graphite oxide film, under graphite oxide film being placed in xenon lamp, 15cm place irradiates reduction 6h and get final product.
X-ray diffraction analysis is indicated as and prepares high orientation graphene film, impedance analysis shows that contact resistance, transferring charge resistance are lower, cyclic voltammetry curve analysis has higher ratio capacitance, energy density and power density, and constant current charge-discharge analysis has good charge-discharge performance.
Embodiment 4
Be mixed with the deionized water suspension that concentration is 2mg/mL after graphite oxide being spent deionized water 2 times, the centrifugal 30min of ultrasonic 1h, 3000r/min washs and removes unstripped graphite composite powder, by supernatant at 45 DEG C of rotary evaporations to forming graphite oxide slurry.The Copper Foil that surface clean is good is adsorbed in doctor knife coater surface, blade coating cutter is set as 100 μm, start doctor knife coater by graphite oxide slurry blade coating at copper foil surface, obtained graphite oxide film, under graphite oxide film being placed in xenon lamp, 15cm place irradiates reduction 9h and get final product.
X-ray diffraction analysis is indicated as and prepares high orientation graphene film, impedance analysis shows that contact resistance, transferring charge resistance are lower, cyclic voltammetry curve analysis has higher ratio capacitance, energy density and power density, and constant current charge-discharge analysis has good charge-discharge performance.
Claims (9)
1. a ultracapacitor preparation method for high orientation graphene film, comprising:
(1) graphite oxide is washed, then add in deionized water, obtain suspension, ultrasonic, centrifugal, then by supernatant rotary evaporation, obtain graphite oxide slurry;
(2) by graphite oxide slurry blade coating at copper foil surface, obtained graphite oxide film, then carries out irradiation reduction treatment, obtains high orientation graphene film.
2. a kind of ultracapacitor according to claim 1 preparation method of high orientation graphene film, is characterized in that: in described step (1), washing is deionized water washing 2-4 time.
3. a kind of ultracapacitor according to claim 1 preparation method of high orientation graphene film, is characterized in that: in described step (1), the concentration of suspension is 0.5 ~ 6mg/mL.
4. a kind of ultracapacitor according to claim 1 preparation method of high orientation graphene film, is characterized in that: in described step (1), ultrasonic time is 1-3h.
5. a kind of ultracapacitor according to claim 1 preparation method of high orientation graphene film, is characterized in that: centrifugally in described step (1) be: centrifugal 10 ~ 40min under 2500 ~ 3500r/min condition.
6. a kind of ultracapacitor according to claim 1 preparation method of high orientation graphene film, is characterized in that: in described step (1), rotary evaporation is rotary evaporation under 40 ~ 55 DEG C of conditions.
7. a kind of ultracapacitor according to claim 1 preparation method of high orientation graphene film, it is characterized in that: in described step (2), graphite oxide slurry blade coating is specially at copper foil surface: the Copper Foil that surface clean is good is adsorbed in doctor knife coater surface, by blade coating cutter setting thickness, start doctor knife coater by graphite oxide slurry blade coating at copper foil surface.
8. a kind of ultracapacitor according to claim 7 preparation method of high orientation graphene film, is characterized in that: described blade coating cutter setting thickness is 50 ~ 200 μm.
9. a kind of ultracapacitor according to claim 1 preparation method of high orientation graphene film, is characterized in that: irradiating reduction treatment in described step (2) is: under being placed in xenon lamp, reduction 3-12h is irradiated at 10 ~ 20cm place.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105742079A (en) * | 2016-03-09 | 2016-07-06 | 东华大学 | Preparation method for graphene/polyaniline composite material taking cotton cloth as substrate |
| CN107195707A (en) * | 2017-06-02 | 2017-09-22 | 东华大学 | A kind of quantum dot based on photoresponse/graphene film optical detection material and its preparation and application |
| CN107331529A (en) * | 2017-05-31 | 2017-11-07 | 中国人民解放军国防科学技术大学 | Graphene oxide slurry, miniature Graphene electrodes and preparation method thereof, miniature graphene ultracapacitor |
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| CN102983012A (en) * | 2012-12-12 | 2013-03-20 | 东华大学 | Preparation method of graphene film for supercapacitor |
| CN103854880A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Graphene electrode sheet and preparation method and application thereof |
| CN104609404A (en) * | 2015-01-08 | 2015-05-13 | 北京理工大学 | Method for preparing graphene and composite material through sunlight reduction or laser reduction |
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Patent Citations (4)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742079A (en) * | 2016-03-09 | 2016-07-06 | 东华大学 | Preparation method for graphene/polyaniline composite material taking cotton cloth as substrate |
| CN105742079B (en) * | 2016-03-09 | 2018-08-03 | 东华大学 | A kind of cotton is the preparation method of the grapheme/polyaniline composite material of substrate |
| CN107331529A (en) * | 2017-05-31 | 2017-11-07 | 中国人民解放军国防科学技术大学 | Graphene oxide slurry, miniature Graphene electrodes and preparation method thereof, miniature graphene ultracapacitor |
| CN107331529B (en) * | 2017-05-31 | 2019-07-16 | 中国人民解放军国防科学技术大学 | Graphene oxide slurry, miniature Graphene electrodes and preparation method thereof |
| CN107195707A (en) * | 2017-06-02 | 2017-09-22 | 东华大学 | A kind of quantum dot based on photoresponse/graphene film optical detection material and its preparation and application |
| CN107195707B (en) * | 2017-06-02 | 2020-01-14 | 东华大学 | Quantum dot/graphene film light detection material based on photoresponse and preparation and application thereof |
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