CN102674326B - 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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- CN102674326B CN102674326B CN2012101511005A CN201210151100A CN102674326B CN 102674326 B CN102674326 B CN 102674326B CN 2012101511005 A CN2012101511005 A CN 2012101511005A CN 201210151100 A CN201210151100 A CN 201210151100A CN 102674326 B CN102674326 B CN 102674326B
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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 now widely used various energy storage devices, and its charge storage discharges and recharges again excellent secondary cell of speed and efficient far above physical capacitor.In addition, ultracapacitor also has environmentally safe, has extended cycle life, use temperature wide ranges, safety performance high, thereby in new energy technology, occupy the critical role (Chinese SciBull, 2011,56:2092 2097) that day by day manifests.Carbon nanotube and Graphene are the new carbon that receives much concern in recent years, because its unique structure properties is obtaining application aspect the electrode material for super capacitor.
Yet in actual procedure, this bi-material has 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 focus and the difficult point of at present research.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 by electrochemical apparatus, adopt various electrochemical methods that carbon nanotube electrode is applied voltage or current processing modification.By carbon nanotube being carried out after the modification, the specific surface area of carbon nanotube enlarges markedly, and wetting ability obviously strengthens, charge capacity, and charging and discharging currents density, the capacitive propertieses such as cycle index also are significantly improved.
The present invention attempts by chemical process, take multi-walled carbon nano-tubes as raw material, prepares the intermediate 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 again the structure of original carbon nanotube partially, have good chemical property, experimental implementation is easy.
The preparation method of the tubular graphene alkene with high electrochemical capacitive property that the present invention proposes, concrete steps are as follows:
(1) Hummers method oxidation:
2～4g multi-walled carbon nano-tubes and 1～2g SODIUMNITRATE are dispersed in 46～92 mL vitriol oils, stirred 50-60 minute in ice-water bath, 6～12 g potassium permanganate slowly join in the mentioned solution, and the control temperature is no more than 20 ℃, remove ice-water bath, 32-36 ℃ of lower the stirring 50-70 minute; Then, in mentioned solution, slowly add 92 mL water; Add at last 20～50 mL H
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 namely 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 again tetrafluoroethylene after first former three fully being ground mixes it, and it is online then to be coated in equably 1 cm * 1 cm nickel foam.Adopt three-electrode system in 1 M KOH solution, to carry out electro-chemical test.Scribble the foam nickel screen of electrode materials as working electrode, platinum guaze and saturated calomel electrode 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 transversely cutting, 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, because this Graphene has larger specific surface area and reactive behavior point, thereby show the energy density higher than multi-walled carbon nano-tubes.
Description of drawings
Fig. 1Be preparation process synoptic diagram of the present invention.
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 different current densities.
Figure 10For tubular graphene alkene at 5 A g
-1Cycle life figure.
Embodiment
Further specify the present invention below by embodiment.:
Embodiment 1: by the oxidation of strong oxidizer, graphitized material is peeled off.The Hummers method can be carried out oxidation with graphite, again by 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 transversely cutting, such as Fig. 2, shown in 3, and can longitudinally open, and such as 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 cyclic voltammetry.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.Such as 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 as shown in figure 10, through 5000 times the circulation after, 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 such as Fig. 5, namely from transversely cutting, 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 as follows:
(1) Hummers method oxidation:
2～4g multi-walled carbon nano-tubes and 1～2g SODIUMNITRATE are dispersed in 46～92 mL vitriol oils, stirred 50-60 minute in ice-water bath, 6～12 g potassium permanganate slowly join in the mentioned solution, and the control temperature is no more than 20 ℃, remove ice-water bath, 32-36 ℃ of lower the stirring 50-70 minute; Then, in mentioned solution, slowly add 92 mL water; Add at last 20～50 mL 30%H
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 namely obtains tubular graphene alkene.
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| US9472354B2 (en) * | 2013-03-15 | 2016-10-18 | InHwan Do | Electrodes for capacitors from mixed carbon compositions |
| 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 |
| CN108147392B (en) * | 2018-01-16 | 2020-10-30 | 西南大学 | Preparation method of carbon nanotube/metal mixed solution for 3D printing |
| CN109553090B (en) * | 2019-01-31 | 2020-05-22 | 中国科学院山西煤炭化学研究所 | Method for cutting carbon nano tube |
| 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 |
| 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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| CN101575095B (en) * | 2009-05-26 | 2012-12-12 | 北京大学 | Method for preparing graphene |
| JP5558935B2 (en) * | 2010-06-28 | 2014-07-23 | 株式会社豊田中央研究所 | Carbon nitrogen-containing fibrous aggregate and method for producing the same |
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