CN102674326A - Preparation method of tubular graphene with high electrochemical and capacitive property - Google Patents
Preparation method of tubular graphene with high electrochemical and capacitive property Download PDFInfo
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- CN102674326A CN102674326A CN2012101511005A CN201210151100A CN102674326A CN 102674326 A CN102674326 A CN 102674326A CN 2012101511005 A CN2012101511005 A CN 2012101511005A CN 201210151100 A CN201210151100 A CN 201210151100A CN 102674326 A CN102674326 A CN 102674326A
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Abstract
The invention relates to a preparation method of tubular graphene with high electrochemical and capacitive property. According to the invention, a Hummers method is used for simultaneously cutting a multi-wall carbon nano tube along a vertical direction and a transverse direction, so as to form a tubular graphene sheet. The tubular graphene is in a hybrid structure of a one-dimensional carbon nano tube and two-dimensional graphene. The result of an electrochemical property test shows that compared with the multi-wall carbon nano tube, the tubular graphene has the advantage of higher electrochemical and capacitive property.
Description
Technical field
The invention belongs to the electrochemical energy storage field, be specifically related to a kind of preparation method with tubular graphene alkene of high electrochemical capacitive property.
Background technology
Ultracapacitor is a kind of novel energy-storing device that occurs in recent years, and it is compared with present widely used various energy storage devices, and its charge storage discharges and recharges the excellent again secondary cell of speed and efficient far above physical capacitor.In addition; Characteristics such as ultracapacitor also has environmentally safe, has extended cycle life, use temperature wide ranges, safety performance height; Thereby in new energy technology, occupy the critical role that manifests day by day (Chinese SciBull, 2011,56:2092 2097).Carbon nanotube and Graphene are the new carbon that receives much concern in recent years, because of its particular structure performance is obtaining application aspect the electrode material for super capacitor.
Yet in actual procedure, these two kinds of materials all have limitation separately.Graphene causes its capacitive property to be difficult to show because reuniting usually appears in the effect of Van der Waals force or the phenomenon of stacking again; Carbon nanotube since electrolyte ion be difficult to infiltrate into the inboard and lower wetting ability of tube wall and usually show lower electric capacity, particularly serious for multi-walled carbon nano-tubes.Therefore, how modifying and optimize the structure of the two and then improve its capacitive property, is the focus and the difficult point of research at present.Patent (101559940B; 2009) a kind of processing method for electrochemically modifying of carbon nanotube is disclosed, in electrolyte solution, with carbon nanotube as electrode materials; And, adopt various electrochemical methods that carbon nanotube electrode is applied voltage or current processing modification through electrochemical apparatus.Through carbon nanotube being carried out after modification handles, the specific surface area of carbon nanotube enlarges markedly, and wetting ability obviously strengthens, charge capacity, and charging and discharging currents density, capacitive propertieses such as cycle index are also improved significantly.
The present invention attempts through chemical process, is raw material with the multi-walled carbon nano-tubes, prepares the midbody between one dimension carbon nanotube and two-dimentional graphene-structured, and proves the raising of its capacitive property.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with tubular graphene alkene of high electrochemical capacitive property; The tubular graphene alkene of preparing has formed the structure of Graphene on the one hand; On the other hand; Herided the structure of original carbon nanotube again partially, had good electrochemical, experimental implementation is easy.
The preparation method of the tubular graphene alkene that the present invention proposes with high electrochemical capacitive property, concrete steps are following:
(1) Hummers method oxidation:
2～4g multi-walled carbon nano-tubes and 1～2g SODIUMNITRATE are dispersed in 46～92 mL vitriol oils; In ice-water bath, stirred 50-60 minute, 6～12 g potassium permanganate slowly join in the above-mentioned solution, and controlled temperature is no more than 20 ℃; Remove ice-water bath, stirred 50-70 minute down at 32-36 ℃; Then, in above-mentioned solution, slowly add 92 mL water; Add 20～50 mL H at last
2O
2(30%) and 200～400 mL water; Centrifuge washing, vacuum-drying;
(2) NaBH
4Reduction:
The material ultra-sonic dispersion that obtains in 50～100 mL water, is added 500 mg NaBH again
4, stirred 18-26 hour; Centrifuge washing, vacuum-drying promptly obtains tubular graphene alkene.
The capacitive property test:
With gained sample, acetylene black and tetrafluoroethylene by 75%: 20%: 5% quality than mixing manufacture electrode materials; The emulsion that adds tetrafluoroethylene after earlier former three fully being ground again mixes it, and it is online to be coated in 1 cm * 1 cm nickel foam then equably.Adopt three-electrode system in 1 M KOH solution, to carry out electro-chemical test.The foam nickel screen that scribbles electrode materials is as working electrode, and platinum guaze and SCE are respectively as supporting electrode and reference electrode.
Beneficial effect of the present invention is: the chemical process of utilizing a kind of simple and suitable scale operation not only from cut off transversely, and is longitudinally opened business-like multi-walled carbon nano-tubes, has formed the tubular graphene alkene with ad hoc structure and performance.When being applied to electrochemical energy storage materials,, thereby show the energy density higher than multi-walled carbon nano-tubes because this Graphene has bigger specific surface area and reactive behavior point.
Description of drawings
Fig. 1For the present invention prepares the process synoptic diagram.
Fig. 2Field emission scanning electron microscope figure for multi-walled carbon nano-tubes.
Fig. 3Field emission scanning electron microscope figure for tubular graphene alkene.
Fig. 4Projection Electronic Speculum figure for multi-walled carbon nano-tubes.
Fig. 5Projection Electronic Speculum figure for tubular graphene alkene.
Fig. 6Nitrogen adsorption desorption curve for multi-walled carbon nano-tubes and tubular graphene alkene.
Fig. 7For multi-walled carbon nano-tubes and tubular graphene alkene at 50 mV s
-1Cyclic voltammetry curve..
Fig. 8For multi-walled carbon nano-tubes and tubular graphene alkene at 1 A g
-1Charging and discharging curve.
Fig. 9Be multi-walled carbon nano-tubes and the ratio capacitance of tubular graphene alkene under the different electric flow density.
Figure 10For tubular graphene alkene at 5 A g
-1Cycle life figure.
Embodiment
Further specify the present invention through embodiment below.:
Embodiment 1: through the oxidation of strong oxidizer, graphitized material is peeled off.The Hummers method can be carried out oxidation with graphite, again through ultra-sonic dispersion and reduction, can prepare the Graphene of two dimension.Shown in Figure 1, the present invention utilizes same procedure oxidation multi-walled carbon nano-tubes, and through NaBH
4Reduction not only makes carbon nanotube along cut off transversely, like Fig. 2, shown in 3, and can longitudinally open, and like Fig. 4, shown in 5, forms tubular graphene alkene sheet.
With above-mentioned multi-walled carbon nano-tubes and tubular graphene alkene sheet, carry out nitrogen adsorption desorption experiment test.As shown in Figure 6, the specific surface area of multi-walled carbon nano-tubes and tubular graphene alkene sheet is respectively 47 cm
2g
-1With 89 cm
2g
-1. the increase of specific surface area shows that multi-walled carbon nano-tubes is successfully cut off and opens.
With multi-walled carbon nano-tubes and tubular graphene alkene sheet, carry out the cyclic voltammetric test.As shown in Figure 7, the integral area of the cyclic voltammetry curve of tubular graphene alkene sheet shows that obviously greater than the integral area of multi-walled carbon nano-tubes tubular graphene alkene sheet has better capacitive property.
With multi-walled carbon nano-tubes and tubular graphene alkene sheet, carry out the constant current charge test.Like Fig. 8, shown in 9, tubular graphene alkene sheet is at 1 A g
-1The time, than electric capacity up to 196 F g
-1, be higher than ratio electric capacity (the 25 F g of multi-walled carbon nano-tubes far away
-1).
The cycle performance of tubular graphene alkene sheet is shown in figure 10, and after 5000 circulations, capacitance still keeps 99% of initial value.
Embodiment 2:Hummers method oxidation multi-walled carbon nano-tubes keeps multi-walled carbon nano-tubes, SODIUMNITRATE, and the amount of the vitriol oil is constant, and the amount of oxidant potassium permanganate is doubled centrifuge washing, vacuum-drying; By the time the result identical like Fig. 5, promptly from cut off transversely, and longitudinally open.Electro-chemical test shows that capacitive property does not change.Show that the method that this patent adopts is simple, and suitable scale operation.
Claims (1)
1. preparation method with tubular graphene alkene of high electrochemical capacitive property is characterized in that concrete steps are following:
(1) Hummers method oxidation:
2～4g multi-walled carbon nano-tubes and 1～2g SODIUMNITRATE are dispersed in 46～92 mL vitriol oils; In ice-water bath, stirred 50-60 minute, 6～12 g potassium permanganate slowly join in the above-mentioned solution, and controlled temperature is no more than 20 ℃; Remove ice-water bath, stirred 50-70 minute down at 32-36 ℃; Then, in above-mentioned solution, slowly add 92 mL water; Add 20～50 mL 30%H at last
2O
2With 200～400 mL water; Centrifuge washing, vacuum-drying;
(2) NaBH
4Reduction:
The material ultra-sonic dispersion that obtains in 50～100 mL water, is added 500 mg NaBH again
4, stirred 18-26 hour; Centrifuge washing, vacuum-drying promptly obtains tubular graphene alkene.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105122406A (en) * | 2013-03-15 | 2015-12-02 | I·杜 | Electrodes for capacitors from mixed carbon compositions |
| CN105668544A (en) * | 2016-01-19 | 2016-06-15 | 南京信息工程大学 | Oxidized multi-walled carbon nanotube preparation method |
| CN108147392A (en) * | 2018-01-16 | 2018-06-12 | 西南大学 | For the preparation method of carbon nanotube/metal mixed solution of 3D printing |
| CN109553090A (en) * | 2019-01-31 | 2019-04-02 | 中国科学院山西煤炭化学研究所 | A method of cutting carbon nanotube |
| CN110165168A (en) * | 2019-05-15 | 2019-08-23 | 中国科学院上海硅酸盐研究所 | A kind of composite positive pole and its preparation method and application |
| CN111017908A (en) * | 2019-11-05 | 2020-04-17 | 北华大学 | Method for preparing biomass-based membrane by using strip-shaped graphene oxide as binder |
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| CN101575095A (en) * | 2009-05-26 | 2009-11-11 | 北京大学 | Method for preparing graphene |
| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| JP2012006817A (en) * | 2010-06-28 | 2012-01-12 | Toyota Central R&D Labs Inc | Carbon/nitrogen-containing fibrous aggregate and method for producing the same |
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2012
- 2012-05-16 CN CN2012101511005A patent/CN102674326B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575095A (en) * | 2009-05-26 | 2009-11-11 | 北京大学 | Method for preparing graphene |
| JP2012006817A (en) * | 2010-06-28 | 2012-01-12 | Toyota Central R&D Labs Inc | Carbon/nitrogen-containing fibrous aggregate and method for producing the same |
| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105122406A (en) * | 2013-03-15 | 2015-12-02 | I·杜 | Electrodes for capacitors from mixed carbon compositions |
| CN105668544A (en) * | 2016-01-19 | 2016-06-15 | 南京信息工程大学 | Oxidized multi-walled carbon nanotube preparation method |
| CN105668544B (en) * | 2016-01-19 | 2017-11-24 | 南京信息工程大学 | A kind of preparation method of oxidation multi-wall carbon nano-tube tube |
| CN108147392A (en) * | 2018-01-16 | 2018-06-12 | 西南大学 | For the preparation method of carbon nanotube/metal mixed solution of 3D printing |
| CN108147392B (en) * | 2018-01-16 | 2020-10-30 | 西南大学 | Preparation method of carbon nanotube/metal mixed solution for 3D printing |
| CN109553090A (en) * | 2019-01-31 | 2019-04-02 | 中国科学院山西煤炭化学研究所 | A method of cutting carbon nanotube |
| CN110165168A (en) * | 2019-05-15 | 2019-08-23 | 中国科学院上海硅酸盐研究所 | A kind of composite positive pole and its preparation method and application |
| CN110165168B (en) * | 2019-05-15 | 2020-08-14 | 中国科学院上海硅酸盐研究所 | Composite cathode material and preparation method and application thereof |
| CN111017908A (en) * | 2019-11-05 | 2020-04-17 | 北华大学 | Method for preparing biomass-based membrane by using strip-shaped graphene oxide as binder |
| CN111017908B (en) * | 2019-11-05 | 2022-10-04 | 北华大学 | Method for preparing biomass base membrane by using strip-shaped graphene oxide as binder |
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| CN102674326B (en) | 2013-10-16 |
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