CN103903877B - A kind of preparation method of graphene/graphene oxide composite current collector - Google Patents
A kind of preparation method of graphene/graphene oxide composite current collector Download PDFInfo
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- CN103903877B CN103903877B CN201210574052.0A CN201210574052A CN103903877B CN 103903877 B CN103903877 B CN 103903877B CN 201210574052 A CN201210574052 A CN 201210574052A CN 103903877 B CN103903877 B CN 103903877B
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Abstract
The preparation method that the invention discloses a kind of graphene/graphene oxide composite current collector, comprises the steps: to prepare graphene oxide film；Prepare graphene suspension；Prepare graphene/graphene oxide film current collector.The preparation method of graphene/graphene oxide composite current collector provided by the invention, by being easier to the graphene oxide preparing integrity and uniformity using graphene oxide suspension as substrate, and add macromolecule, it is made to interact with graphene oxide, the graphene oxide paper of stronger mechanical performance can be obtained, then pass through graphite spraying alkene, its electric conductivity can be strengthened, the mechanical performance of graphene/graphene oxide composite current collector prepared and electrical conductivity can be made all higher, ensure that it has the higher life-span as collector when using, this graphene/graphene oxide composite current collector, with traditional Copper Foil, aluminium foil is compared, the weight of collector can be substantially reduced, and then improve the energy density of ultracapacitor.
Description
Technical field
The present invention relates to field of composite material preparation, the preparation method particularly relating to a kind of graphene/graphene oxide composite current collector.
Background technology
Ultracapacitor is a kind of novel energy storage device, there is the advantages such as high power density (more than 10 times for common batteries), high cycle life (cycle-index is up to more than 100,000 times), fast charging and discharging performance be good, be widely used in the AC-battery power source etc. of military field, device for mobile communication, computer and electric automobile.Usual ultracapacitor main is by electrode active material layer, electrolyte, assemble every thin film, collector, shell etc..The energy density of existing ultracapacitor is generally relatively low, the influence factor of the energy density of ultracapacitor mainly has the electric capacity of electrode material, the voltage of system, electrode material accounts for the proportion of the gross weight of electrode active material layer, collector, sheathing material composition, therefore, the energy-storage property increasing electrode material and the weight reducing each composition material of device can be effectively improved the performance of device.Wherein, the quality reducing collector is the method for an effective raising energy density.
Collector is a kind of structure collecting electric current or part, and major function is to be collected by the electric current that cell active materials produces, it is provided that electron channel, accelerates electric charge transfer, improves discharge and recharge coulombic efficiency.Need to meet the feature such as electrical conductivity height, good mechanical property, light weight, internal resistance be little as collector.
At present, in most document or in industry, general collector positive pole adopts aluminium foil, negative pole to adopt Copper Foil, owing to the density of metal collector is bigger, heavier mass, the weight of general collector accounts for the 20% ~ 25% of whole battery, then electrode material accounts for the proportion of whole battery and greatly reduces, and the energy density ultimately resulting in ultracapacitor is relatively low.
Summary of the invention
Based on the problems referred to above, to be solved by this invention it has a problem in that the preparation method that a kind of graphene/graphene oxide composite current collector is provided.
Technical scheme is as follows:
The preparation method of a kind of graphene/graphene oxide composite current collector, comprises the steps:
The graphene oxide suspension that concentration is 0.25 ~ 1mg/ml is filtered by microporous filter membrane vacuum, macromolecular solution is added subsequently on the forerunner's filter cake being filtrated to get, obtain mixed solution, then continue to filter mixed solution, until filtering completely, the first filter cake obtained, the first filter cake is placed in baking oven in 40 DEG C of drying together with microporous filter membrane, then described first filter cake is taken off from described microporous filter membrane, obtain graphene oxide film；
Being joined by Graphene in solvent, forming concentration after ultrasonic disperse is the graphene suspension of 1 ~ 5mg/ml；
Described graphene suspension is painted on described graphene oxide film surface, after drying at room temperature, then is immersed in alcoholic solution, remove impurity, then dry in the vacuum drying oven of 40 ~ 60 DEG C, obtain described graphene/graphene oxide film current collector.
The preparation method of described graphene/graphene oxide composite current collector, wherein, the concentration of described macromolecular solution is 1% ~ 10%；Described macromolecular solution is PVA(polyvinyl alcohol), PVP(polyvinylpyrrolidone) or PEO(polyethylene glycol oxide) solution, PVA, PVP or PEO account for the 0.1% ~ 10% of whole mixed solution gross mass.
The preparation method of described graphene/graphene oxide composite current collector, wherein, the solvent in described macromolecular solution and graphene oxide suspension is deionized water, ethanol, methanol or isopropanol.
The preparation method of described graphene/graphene oxide composite current collector, wherein, the thickness of described graphene oxide film is 3 ~ 10 μm.
The preparation method of described graphene/graphene oxide composite current collector, wherein, configuration graphene suspension solvent be NMP(N-methyl pyrrolidone), DMF(N, dinethylformamide) or DMAc(N, N-dimethyl acetylamide).
The preparation method of described graphene/graphene oxide composite current collector, wherein, it is 0.2 ~ 5h that described graphene suspension sprays to the drying at room temperature time on described graphene oxide film surface.
The preparation method of graphene/graphene oxide composite current collector provided by the invention, by being easier to the graphene oxide preparing integrity and uniformity using graphene oxide suspension as substrate, and add macromolecule, it is that it interacts with graphene oxide, the graphene oxide paper of stronger mechanical performance can be obtained, then pass through graphite spraying alkene, its electric conductivity can be strengthened, the mechanical performance of graphene/graphene oxide composite current collector prepared and electrical conductivity can be made all higher, ensure that it has the higher life-span as collector when using, this graphene/graphene oxide composite current collector, with traditional Copper Foil, aluminium foil is compared, the weight of collector can be substantially reduced, and then improve the energy density of ultracapacitor.
Detailed description of the invention
Below presently preferred embodiments of the present invention is described in further detail.
Embodiment 1
(1) preparation of graphene oxide film:
The graphene oxide suspension that the concentration configured is 0.25mg/ml is filtered by microporous filter membrane vacuum, when see do not have obvious filtrate on forerunner's filter cake time, crossing, microporous filter membrane adding PVA(polyvinyl alcohol) aqueous solution is (when adding PVA, graphene oxide paper still wets), continue to filter forerunner's filter cake, until filtering completely, obtain the first filter cake, first filter cake is placed in baking oven in 40 DEG C of drying together with microporous filter membrane, then the first filter cake is taken off from from described microporous filter membrane, obtaining graphene oxide film, THICKNESS CONTROL is at 10 μm；Wherein the concentration of PVA is 1%, and it is 0.1% that PVA accounts for whole mass ratio；The solvent of graphene oxide suspension is deionized water.
(2) preparation of graphene suspension: joined by Graphene and carry out ultrasonic disperse 1h in nmp solvent, forms the graphene suspension that concentration is 1mg/ml.
(3) prepared by graphene/graphene oxide composite current collector: by the graphene suspension in above-mentioned (2), it is painted on graphene oxide film, drying at room temperature 0.5h, then it is immersed in alcoholic solution, remove impurity, then dry in the vacuum drying oven of 40 DEG C, obtain graphene/graphene oxide composite current collector.
Embodiment 2
(1) preparation of graphene oxide film:
The graphene oxide suspension that the concentration configured is 0.5mg/ml is filtered by microporous filter membrane vacuum, when see do not have obvious filtrate on forerunner's filter cake time, crossing, microporous filter membrane adds PVP(polyvinylpyrrolidone) alcoholic solution (when adding PVA, graphene oxide paper still wets), continue to filter forerunner's filter cake, until filtering completely, obtain the first filter cake, first filter cake is placed in baking oven in 40 DEG C of drying together with microporous filter membrane, then the first filter cake is taken off from from described microporous filter membrane, obtaining graphene oxide film, THICKNESS CONTROL is at 8 μm；Wherein, the concentration of PVA is 5%, and it is 5% that PVA accounts for whole mass ratio；The solvent of graphene oxide suspension is ethanol.
(2) preparation of graphene suspension: joined by Graphene and carry out ultrasonic disperse 1h in DMF solvent, forms the graphene suspension that concentration is 3mg/ml.
(3) prepared by graphene/graphene oxide composite current collector: by the graphene suspension in above-mentioned (2), it is painted on graphene oxide film, drying at room temperature 1h, then it is immersed in alcoholic solution, remove impurity, then dry in the vacuum drying oven of 50 DEG C, obtain graphene/graphene oxide composite current collector.
Embodiment 3
(1) preparation of graphene oxide film:
The graphite oxide suspension that the concentration configured is 1mg/ml is filtered by microporous filter membrane vacuum, when see do not have obvious filtrate on forerunner's filter cake time, crossing, microporous filter membrane adding PEO(polyethylene glycol oxide) aqueous solution is (when adding PEO, graphene oxide paper still wets), continue to filter forerunner's filter cake, until filtering completely, obtain the first filter cake, first filter cake is placed in baking oven in 40 DEG C of drying together with microporous filter membrane, then the first filter cake is taken off from from described microporous filter membrane, obtaining graphene oxide film, THICKNESS CONTROL is at 10 μm；Wherein, the concentration of PEO is 50%, and it is 10% that PEO accounts for whole mass ratio；The solvent of graphene oxide suspension is isopropanol.
(2) preparation of graphene suspension: joined by Graphene and carry out ultrasonic disperse 2h in DMAc solvent, forms the graphene suspension that concentration is 5mg/ml.
(3) prepared by graphene/graphene oxide composite current collector: by the graphene suspension in above-mentioned (2), it is painted on graphene oxide film, drying at room temperature 2h, then it is immersed in alcoholic solution, remove impurity, then dry in the vacuum drying oven of 60 DEG C, obtain graphene/graphene oxide composite current collector.
Graphene/graphene oxide composite current collector hot strength is tested, and extension test carries out on dynamic mechanical analyzer (DMAQ800/TA), and sample is cut into 3 × 15mm2Rectangular sheet carry out tension test test.
Sample is the graphene/graphene oxide composite current collector of embodiment 1 system, and its hot strength is 327MPa, and intensity is higher.
It should be appreciated that the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, therefore can not thinking the restriction to scope of patent protection of the present invention, the scope of patent protection of the present invention should be as the criterion with claims.
Claims (6)
1. the preparation method of a graphene/graphene oxide composite current collector, it is characterised in that comprise the steps:
The graphene oxide suspension that concentration is 0.25～1mg/ml is filtered by microporous filter membrane vacuum, macromolecular solution is added subsequently on the forerunner's filter cake being filtrated to get, obtain mixed solution, then continue to filter mixed solution, until filtering completely, obtain the first filter cake, first filter cake is placed in baking oven in 40 DEG C of drying together with microporous filter membrane, then described first filter cake is taken off from described microporous filter membrane, obtain graphene oxide film, wherein, described macromolecular solution is poly-vinyl alcohol solution, polyvinylpyrrolidonesolution solution or polyethylene oxide solutions；
Being joined by Graphene in solvent, forming concentration after ultrasonic disperse is the graphene suspension of 1～5mg/ml；
Described graphene suspension is painted on described graphene oxide film surface, after drying at room temperature, then it is immersed in alcoholic solution, removes impurity, then dry in the vacuum drying oven of 40～60 DEG C, obtain described graphene/graphene oxide film current collector.
2. the preparation method of graphene/graphene oxide composite current collector according to claim 1, it is characterised in that the concentration of described macromolecular solution is 1%～10%；Described macromolecular solution is poly-vinyl alcohol solution, polyvinylpyrrolidonesolution solution or polyethylene oxide solutions, and described vinyl alcohol, polyvinylpyrrolidone or polyethylene glycol oxide account for the c of whole mixed solution gross mass, wherein, and 0.1%≤c < 10%.
3. the preparation method of graphene/graphene oxide composite current collector according to claim 1 and 2, it is characterised in that the solvent in described macromolecular solution and graphene oxide suspension is deionized water, ethanol, methanol or isopropanol.
4. the preparation method of graphene/graphene oxide composite current collector according to claim 1, it is characterised in that the thickness of described graphene oxide film is 3～10 μm.
5. the preparation method of graphene/graphene oxide composite current collector according to claim 1, it is characterised in that the solvent of configuration graphene suspension is N-Methyl pyrrolidone, DMF or N,N-dimethylacetamide.
6. the preparation method of graphene/graphene oxide composite current collector according to claim 1, it is characterised in that it is 0.2～5h that described graphene suspension sprays to the drying at room temperature time on described graphene oxide film surface.
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| CN107649348B (en) * | 2017-09-29 | 2021-03-26 | 固力发电气有限公司 | Electric power panel that continues based on graphite alkene surface recombination |
| CN111816459A (en) * | 2020-07-03 | 2020-10-23 | 肇庆理士电源技术有限公司 | Preparation method of graphene current collector |
| CN114540812A (en) * | 2022-01-26 | 2022-05-27 | 山东大学 | Method for preparing reduced graphene film on metal surface |
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| CN101894679A (en) * | 2009-05-20 | 2010-11-24 | 中国科学院金属研究所 | Method for preparing graphene-based flexible super capacitor and electrode material thereof |
| CN102066245A (en) * | 2007-10-19 | 2011-05-18 | 卧龙岗大学 | Process for the preparation of graphene |
| CN102403050A (en) * | 2010-09-08 | 2012-04-04 | 中国科学院金属研究所 | Composite material based on nanometer, preparation method of composite material and application in flexible energy storage device |
| CN102815043A (en) * | 2012-08-02 | 2012-12-12 | 中国科学技术大学 | Preparation method of grapheme and polyaniline composite paper, and products thereof |
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| TW201012749A (en) * | 2008-08-19 | 2010-04-01 | Univ Rice William M | Methods for preparation of graphene nanoribbons from carbon nanotubes and compositions, thin films and devices derived therefrom |
| WO2012135499A1 (en) * | 2011-03-31 | 2012-10-04 | Ganeden Biotech, Inc. | Probiotic sports nutrition compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102066245A (en) * | 2007-10-19 | 2011-05-18 | 卧龙岗大学 | Process for the preparation of graphene |
| CN101894679A (en) * | 2009-05-20 | 2010-11-24 | 中国科学院金属研究所 | Method for preparing graphene-based flexible super capacitor and electrode material thereof |
| CN102403050A (en) * | 2010-09-08 | 2012-04-04 | 中国科学院金属研究所 | Composite material based on nanometer, preparation method of composite material and application in flexible energy storage device |
| CN102815043A (en) * | 2012-08-02 | 2012-12-12 | 中国科学技术大学 | Preparation method of grapheme and polyaniline composite paper, and products thereof |
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