CN103253658B - A kind of high volumetric capacitance Graphene and preparation method thereof - Google Patents
A kind of high volumetric capacitance Graphene and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of Graphene, doped with activated carbon in described graphene sheet layer；The preparation method that the invention also discloses described Graphene: graphene oxide and activator, carbon source material are sufficiently mixed, activates under protective atmosphere is protected, then cooling, washing, the dry Graphene obtaining high volumetric capacitance.The present invention, while ensureing that grapheme material high-specific surface area and high-quality are than electric capacity, improves the volumetric capacitance of Graphene, overcome Graphene due to volumetric capacitance little, it is impossible to be applied to the technical barrier of super capacitor as electrode material；Present invention, avoiding and use chemical reagent in a large number, reduce the consumption that makes of activator, equipment is simple, cost is low, safe and reliable, pollutes few, and production efficiency is high, and cost is low, it is possible to large-scale production, has the very strong market competitiveness and is widely applied prospect.
Description
Technical field
The present invention relates to a kind of high volumetric capacitance Graphene and preparation method thereof, be specifically related to a kind of chemical doping legal system and get everything ready the Graphene and preparation method thereof of high-specific surface area, high volumetric capacitance, belong to preparation and the application of grapheme material.
Background technology
Graphene (Graphene) is the new material of a kind of monolayer laminated structure being made up of carbon atom, it is a kind of formed, with sp2 hybrid orbital, the flat film that hexangle type is honeycomb lattice by carbon atom, it it is the two-dimensional material of only one of which carbon atom thickness, there is the specific surface area of super large, excellent conduction and heat conductivility and good chemical stability.These good character make to become a kind of desirably energy storage material based on the material of Graphene, including super capacitance electrode material, lithium ion battery electrode material, hydrogen storage material, materials in MCFC material etc..
Ultracapacitor is an efficient storage and the system of transmission energy, and it has, and power density is big, capacity big, long service life, the advantage such as economic and environment-friendly, is widely used in various energy field.Material with carbon element, the particularly material with carbon element of sp2 hydridization, become the electrode material of important energy storage device due to its special layer structure, the specific surface area of super large.Material with carbon element such as amorphous carbon, porous carbon, graphite etc. have been widely used in lithium ion battery.
Graphene has high specific surface area and high electrical conductivity, Graphene is made to have, as capacitor material, the character that other porous carbon materials are more excellent, making it be expected to become the ideal electrode material of ultracapacitor, its performance is directly related with the quality of Graphene, the number of plies and specific surface area.There are some researches show that the Graphene obtained by hydrazine redox graphene ratio electric capacity in electrolyte solution with water may be up to 205F/g, after the test of 1200 times, it also still reaches original 90% than electric capacity.Generally there is big specific surface area, little dimensional effect due to nano material, thus the quality of capacitor can be improved than capacity ratio capacity, but its relative volumetric capacitance is relatively low, for energy storage material, reach certain amount of storage and be accomplished by very big volume, limit its development.
Thus, Graphene for high-specific surface area, the aspect performances such as the electricity of Graphene ultracapacitor, chemistry are had important impact by the mass per volume of Graphene, how to develop a kind of less costly, volumetric capacitance is high, the preparation method of the High specific surface area graphene of good cycle and applicable electrolyte, is a problem demanding prompt solution of this area
Summary of the invention
In prior art, owing to the character of Graphene self determines, no matter chemistry redox method or CVD, the mass per volume of prepared Graphene is all only small, the technical problem to be solved in the present invention is to overcome existing defect, it is provided that a kind of method putting forward Graphene volumetric capacitance.Little for Graphene volumetric capacitance, it is impossible to the problem being applied to the electricity devices such as jumbo ultracapacitor, the present invention proposes the Graphene of a kind of high volumetric capacitance, to can effectively solve the problem that this problem.
An object of the present invention is to provide a kind of Graphene, doped with activated carbon in described graphene sheet layer.
The present invention is dopped activated carbon in Graphene, it is possible to effectively increase the density of Graphene, improves the volumetric capacitance of Graphene.The present invention is that the volumetric capacitance improving Graphene proposes a kind of new resolving ideas, and the electric capacity for improving the electric elements such as super capacitor further provides condition.Graphene provided by the invention has that specific surface area is big, quality is higher than electric capacity, and the feature that volumetric capacitance is high.
Preferably, described activated carbon obtains after being activated by carbon source material, the combination of described carbon source material preferably be selected from starch, wood flour, Linesless charcoal, coconut husk, coal, shell or petroleum coke any a kind or at least 2 kinds, the combination of described combination such as starch/Linesless charcoal, the combination of coconut husk/coal, wood flour/shell/Linesless charcoal combination etc., it is preferred that Linesless charcoal and/or petroleum coke, it is particularly preferred to Linesless charcoal.
The present invention is in graphene oxide activation process, additional carbon material, at high temperature carbon source material decomposes and is entrained in Graphene, obtain the Graphene doped with activated carbon, so that the volumetric capacitance amount of prepared grapheme material is greatly improved so that relevant energy density is greatly improved.
Preferably, described activation is high-temperature activation, described high-temperature activation temperature is 500～1500 DEG C, such as 510 DEG C, 620 DEG C, 650 DEG C, 730 DEG C, 790 DEG C, 854 DEG C, 885 DEG C, 906 DEG C, 948 DEG C, 980 DEG C, 1050 DEG C, 1100 DEG C, 1350 DEG C, 1480 DEG C, 1500 DEG C etc., preferred soak time is 0.5～5h, for instance 0.6h, 0.9h, 1.3h, 1.7h, 2.5h, 2.9h, 3.4h, 3.8h, 4.5h, 4.7h etc..
Preferably, the specific surface area >=1500m of described Graphene2/ g, for instance 1530m2/g、1580m2/g、1600m2/g、1630m2/g、1680m2/g、1700m2/g、1900m2/g、2300m2/g、2800m2/g、2900m2/ g etc., it is preferred to 1500～3000m2/g。
Preferably, with 1MTEABF4/PC for electrolyte, the quality of described grapheme material is 100～200F/g than electric capacity, for instance 100F/g, 120F/g, 130F/g, 150F/g, 180F/g, 190F/g, 200F/g etc., and volumetric capacitance is 50～120F/cm3, for instance 52F/cm3、90F/cm3、102F/cm3、107F/cm3、110F/cm3、118F/cm3Deng.
High volumetric capacitance Graphene of the present invention is volumetric capacitance >=50F/cm3Graphene.
The preparation method that the two of the purpose of the present invention are to provide a kind of Graphene as described in one of purpose; described method is for being sufficiently mixed graphene oxide and activator, carbon source material; high-temperature activation is carried out, then cooling, washing, the dry Graphene obtaining high volumetric capacitance under protective atmosphere is protected.
The carbon source material of graphene oxide with activator, addition is sufficiently mixed by the present invention; in high-temperature activation process under protective atmosphere; the carbon source material added is decomposed and is fully doped in the lamella of Graphene; reach the purpose of dopped activated carbon in Graphene; thus ensureing Graphene high-specific surface area; high-quality ratio is under the premise of electric capacity; increase the volumetric capacitance of grapheme material; and the preparation method of Graphene provided by the invention; process is simple; easily operated, environmental protection and yield are high.
Preferably, the combination of in starch, wood flour, Linesless charcoal, coconut husk, coal, shell or petroleum coke any a kind or at least 2 kinds of described carbon source material, the combination of described combination such as starch/coconut husk, the combination of wood flour/petroleum coke, the combination of coal/Linesless charcoal, starch/shell/coal combination etc., preferred Linesless charcoal and/or petroleum coke, it is preferred that Linesless charcoal.
Preferably, the addition of described carbon source material is 0.01～1 times of graphene oxide quality, for instance 0.01 times, 0.02 times, 0.03 times, 0.2 times, 0.5 times, 0.6 times, 0.7 times, 0.8 times, 1 times etc..
The addition of carbon source material of the present invention is too much, affects the quality of high volumetric capacitance Graphene than electric capacity and specific surface area；And the addition of carbon source material is too small, do not reach desirable volumetric capacitance.
Preferably, described activator is the combination of any a kind or at least 2 kinds in potassium hydroxide, sodium hydroxide, phosphoric acid, potassium carbonate or zinc chloride, the combination of described combination such as potassium hydroxide/sodium hydroxide, the combination of phosphoric acid/zinc chloride, the combination of potassium hydroxide/zinc chloride, potassium hydroxide/sodium hydroxide/zinc chloride combination etc.；Those skilled in the art are not it will be clearly understood that described combination includes alkali and the combination of acid, for instance do not include the combination of potassium hydroxide and/or Lithium hydrate and phosphoric acid.
The effect of activator of the present invention is to be obtained by reacting hole on graphene sheet layer, increases the specific surface area of Graphene.Those skilled in the art are it will be clearly understood that in listed activator, phosphoric acid is acid, can with alkali substance reaction, causing that itself or the material reacted lose activity, therefore in the present invention, phosphoric acid cannot be used along with alkaline matters such as potassium hydroxide, sodium hydroxide, potassium carbonate.
Preferably, interpolation quality is graphene oxide quality 1～15 times of described activator, for instance 2 times, 4 times, 7 times, 10 times, 14 times, 14.6 times etc., it is preferable that 1～12 times, it is preferred that 1～6 times.
Concrete addition those skilled in the art of described activator can be selected by By consulting literatures, typical but non-limiting: when individually interpolation hydrogen-oxygen agent, sodium hydroxide are activator, the addition of described activator is 1～15 times of graphene oxide quality；When individually adding potassium carbonate and being activator, the addition of described activator is 1～5 times of graphene oxide quality；When individually adding phosphoric acid or zinc chloride is activator, the addition of described activator is 1～3 times of graphene oxide quality.
The addition of activator of the present invention is too much, it is easy to causing the excessive erosion of Graphene, lamella well damage, electric conductivity is deteriorated；Addition is very few, and on Graphene, the number in hole is less, affects the specific surface area of Graphene.
Preferably, described graphene oxide be graphite oxidized after carry out the product peeled off.The step peeled off after the method for graphite oxidation and oxidation is not particularly limited by the present invention.
Preferably, the mode of described graphite oxidation adopts any a kind in Hummers method, Staudenmaier method or Brodie method.
Brodie method is first with HNO of being fuming3Processing natural micro powder graphite, when graphite is oxidized, nitrate ion is invaded between people's graphite flake layer, then puts into KClO again4Oxidation, throws reactant in a large amount of water of people subsequently, is filtered, be washed to filtrate after neutrality further, dry, obtains graphite oxide.
Staudemaier method is with concentrated sulphuric acid and fuming nitric aicd mixed acid, graphite powder to be processed, also with KClO4For oxidant.
Hummers method is by graphite powder and anhydrous nitric acid sodium (NaNO3) join in the concentrated sulphuric acid being placed in ice bath, add KMnO under strong stirring4, and use volume fraction 3%H2O2Reduce remaining potassium permanganate and MnO2So that it is become colorless solvable MnSO4.Under the process of hydrogen peroxide, suspension becomes glassy yellow.Filtering, wash 3 times, then vacuum dehydration obtains.Obtained oxidized graphite flake layer has pleat beryllium type structure, and oxygen content is relatively big, and functional group is horn of plenty relatively, can fine dispersion in pure water.
Preferably, the combination of in microwave stripping method, pyrolysis expansion stripping method, ultrasonic disperse stripping method, electrostatic repulsion stripping method or thermal reduction stripping method any a kind or at least 2 kinds of the mode of described stripping, the combination etc. that combination, ultrasonic disperse stripping and the pyrolysis expansion that described combination such as microwave is peeled off and pyrolysis expansion is peeled off is peeled off, the combination of any a kind or at least 2 kinds in preferred microwave stripping method, thermal reduction stripping method or ball milling stripping method, it is preferred that microwave stripping method.
Preferably, described high-temperature activation temperature is 500～1500 DEG C, such as 502 DEG C, 625 DEG C, 750 DEG C, 880 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C, 1300 DEG C, 1450 DEG C, 1500 DEG C etc., preferred soak time is 0.5～5h, for instance 0.6h, 0.9h, 1.3h, 1.7h, 2.5h, 2.9h, 3.4h, 3.8h, 4.5h, 4.7h etc..
Reaction of the present invention carries out in inert gas environment, and described noble gas is other that do not react with graphene oxide, activator, carbon source material etc., typical but non-limiting for nitrogen, helium, neon, argon etc..Preferably, the combination of described protective atmosphere preferably be selected from nitrogen, helium or argon any a kind or at least 2 kinds, it is preferred that nitrogen and/or argon, it is most preferred that nitrogen.It is the nitrogen of 99.999% that nitrogen of the present invention is preferably purity, and it is the argon of 99.99% that argon is preferably purity.
Preferably; the flow that passes into of described protective atmosphere is 20-200sccm; such as 20sccm, 50sccm, 62sccm, 69sccm, 76sccm, 84sccm, 97sccm, 103sccm, 115sccm, 123sccm, 138sccm, 145sccm, 155sccm, 167sccm, 179sccm, 185sccm, 190sccm, 200sccm etc.; preferred 40-120sccm, it is preferred that 100sccm；
Preferably, described activation carries out in vacuum tube furnace.
As optimal technical scheme, the preparation method of high volumetric capacitance of the present invention comprises the steps:
(1) pre-treatment: by graphene oxide, carbon source material and activator according to mass ratio 1:(0.01～1): (1～15) is sufficiently mixed, dries；
(2) redox graphene activating: the mixture of the graphene oxide, carbon source material and the activator that step (1) are obtained is put in vacuum tube furnace; after pumping furnace air; in vacuum tube furnace, pass into noble gas protect; it is warming up to 600-1200 DEG C, isothermal reaction 0.5-3h；
(3) post processing: after reaction terminates, drops to room temperature in inert gas shielding, washs, dries, obtains the Graphene of high volumetric capacitance.
The three of the purpose of the present invention are to provide a kind of Graphene electrodes, and described electrode material is the Graphene that one of the object of the invention is described.
Preferably, in described Graphene electrodes material, the content of Graphene is 80～98wt%, for instance 82wt%, 84wt%, 87wt%, 89wt%, 93wt%, 95wt%, 97wt%, 98wt% etc..
The preparation technology of described Graphene electrodes, those skilled in the art can select according to the Professional knowledge that oneself is grasped, and the present invention is not specifically limited.
When the Graphene electrodes prepared with the PTFE emulsion that mass ratio is one of 95:5 mixing purpose described grapheme material and 60wt% is in organic electrolyte, after 2000 circulations, capacitance remains to reach more than the 95% of initial capacitance.
Quality of the present invention than electric capacity (unit is F/g) computing formula as shown in the formula (I):
In formula, CpFor condenser capacity；C is capacitance；M is the quality of Activated Graphite alkene.
(unit is F/cm to volumetric capacitance of the present invention3) computing formula as shown in the formula (II):
In formula, CvFor condenser capacity；C is capacitance；V is the quality of Activated Graphite alkene.
The four of the purpose of the present invention are to provide Graphene as described in one of a kind of purpose for the purposes in ultracapacitor, lithium ion battery or fuel cell.
Owing to Graphene provided by the invention has high-specific surface area, high-quality ratio under the premise of electric capacity, also there is higher volumetric capacitance, utilize Graphene provided by the invention can develop capacitance big, the super capacitor that volume is little.
Compared with prior art, there is advantages that
(1) present invention is while ensureing that grapheme material high-specific surface area and high-quality are than electric capacity, improves the volumetric capacitance of Graphene, overcome Graphene due to volumetric capacitance little, it is impossible to be applied to the technical barrier of super capacitor as electrode material；
(2) present invention, avoiding and use chemical reagent in a large number, reduce the consumption that makes of activator, equipment is simple, cost is low, safe and reliable, pollutes few, and production efficiency is high, and cost is low, it is possible to large-scale production, has the very strong market competitiveness and is widely applied prospect.
Accompanying drawing explanation
Fig. 1 is the preparation technology flow diagram of high volumetric capacitance Graphene described in one embodiment of the present invention；
Fig. 2 is the Graphene electrodes for preparing of embodiment 1 cyclic voltammetry curve in 1MTEABF4/PC electrolyte；
Fig. 3 is the constant current charge-discharge time graph of the super capacitor that embodiment 1 prepares；
Fig. 4 is the Graphene electrodes for preparing of embodiment 2 cyclic voltammetry curve in 1MTEABF4/PC electrolyte；
Fig. 5 is the constant current charge-discharge time graph of the super capacitor that embodiment 2 prepares；
Fig. 6 is the Graphene electrodes for preparing of embodiment 3 cyclic voltammetry curve in 1MTEABF4/PC electrolyte；
Fig. 7 is the constant current charge-discharge time graph of the super capacitor that embodiment 3 prepares.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art understand the present invention it will be clearly understood that described embodiment is only help, are not construed as the concrete restriction to the present invention.
Embodiment 1:
The preparation method of a kind of high volumetric capacitance Graphene, comprises the steps:
(1) take graphite oxide prepared by Hummers method, after microwave is peeled off, obtain graphene oxide powder；
(2) weigh graphene oxide powder and 0.5g Linesless charcoal, the KOH of 15g that 3g step (1) obtains, be sufficiently mixed, stir, dry；
(3) mixture that step (2) obtains is placed in vacuum tube furnace, after pumping furnace air, is the argon of 99.99% with the flow of 100sccm to vacuum tube furnace passes into purity, at 800 DEG C, reacts 1.5h；
(4) it is naturally cooling to room temperature after having reacted, washs, dry, obtain the High specific surface area graphene material that volumetric capacitance increases.Fig. 1 is the preparation technology flow diagram of high volumetric capacitance Graphene described in embodiment 1；
The specific surface area of the grapheme material prepared is 1605.3m2/ g(adopts U.S.'s health tower specific surface area and Porosimetry NOVA2000e to carry out specific area measuring).
Performance test:
Preparation Graphene electrodes sheet: by the PTFE(politef of the grapheme material prepared and 60wt%) emulsion, it is sufficiently mixed according to the ratio that mass ratio is 95:5；Then uniform through roll squeezer repeatedly roll-in, make the Graphene electrodes sheet that diameter is 13mm；
The Graphene electrodes sheet prepared is put into vacuum drying oven inner drying to constant weight, then assembles and obtain super capacitor；
Using 1MTEABF4/PC as electrolyte, utilizing electrochemical workstation to carry out electrochemical property test, Fig. 2 is the Graphene electrodes for preparing of embodiment 1 cyclic voltammetry curve in 1MTEABF4/PC electrolyte；Fig. 3 is the constant current charge-discharge time graph of the super capacitor that embodiment 1 prepares；The quality of the grapheme material prepared after tested is 185.1F/g than electric capacity, and volumetric capacitance is 110.3F/cm3, energy density is 333.7Wh/cm3, after 2000 times circulate, capacitance remains to reach the 97.9% of initial capacitance.
Embodiment 2:
The preparation method of a kind of high volumetric capacitance Graphene, comprises the steps:
(1) take graphite oxide prepared by Hummers method, after microwave is peeled off, obtain graphene oxide powder；
(2) weigh graphene oxide powder and 1g wood flour, the KOH of 18g that 3g step (1) obtains, be sufficiently mixed, stir, dry；
(3) mixture that step (2) obtains is placed in vacuum tube furnace, after pumping furnace air, is the argon of 99.99% with the flow of 120sccm to vacuum tube furnace passes into purity, at 900 DEG C, reacts 1h；
(4) it is naturally cooling to room temperature after having reacted, washs, dry, obtain the High specific surface area graphene material that volumetric capacitance increases.
The specific surface area of the grapheme material prepared is 1996.9m2/ g(assay method is identical with embodiment 1).
Performance test:
Method of testing and embodiment 1 are identical, and Fig. 4 is the Graphene electrodes for preparing of embodiment 2 cyclic voltammetry curve in 1MTEABF4/PC electrolyte；Fig. 5 is the constant current charge-discharge time graph of the super capacitor that embodiment 2 prepares；The quality of the grapheme material prepared after tested is 161.3F/g than electric capacity, and volumetric capacitance is 90.3F/cm3, energy density is 282.2Wh/cm3, after 2000 times circulate, capacitance remains to reach the 95.2% of initial capacitance.
Embodiment 3:
The preparation method of a kind of high volumetric capacitance Graphene, comprises the steps:
(1) take graphite oxide prepared by Hummers method, after microwave is peeled off, obtain graphene oxide powder；
(2) weigh graphene oxide powder and 1g petroleum coke, the KOH of 15g that 3g step (1) obtains, be sufficiently mixed, stir, dry；
(3) mixture that step (2) obtains is placed in vacuum tube furnace, after pumping furnace air, is the argon of 99.99% with the flow of 60sccm to vacuum tube furnace passes into purity, at 1200 DEG C, reacts 0.5h；
(4) it is naturally cooling to room temperature after having reacted, washs, dry, obtain the High specific surface area graphene material that volumetric capacitance increases.
The specific surface area of the grapheme material prepared is 2150.2m2/ g(assay method is identical with embodiment 1).
Performance test:
Method of testing and embodiment 1 are identical, and Fig. 6 is the Graphene electrodes for preparing of embodiment 3 cyclic voltammetry curve in 1MTEABF4/PC electrolyte；Fig. 7 is the constant current charge-discharge time graph of the super capacitor that embodiment 3 prepares；The quality of the grapheme material prepared after tested is 142.2F/g than electric capacity, and volumetric capacitance is 71.1F/cm3, energy density is 222.1Wh/cm3, after 2000 times circulate, capacitance remains to reach the 96.5% of initial capacitance.
Embodiment 4:
The preparation method of a kind of high volumetric capacitance Graphene, comprises the steps:
(1) take graphite oxide prepared by Brodie method, after microwave is peeled off, obtain graphene oxide powder；
(2) weigh graphene oxide powder and 3g petroleum coke, NaOH and the 3gKOH of 15g that 3g step (1) obtains, be sufficiently mixed, stir, dry；
(3) mixture that step (2) obtains is placed in vacuum tube furnace, after pumping furnace air, is the argon of 99.99% with the flow of 20sccm to vacuum tube furnace passes into purity, at 1500 DEG C, reacts 0.8h；
(4) it is naturally cooling to room temperature after having reacted, washs, dry, obtain the High specific surface area graphene material that volumetric capacitance increases.
The specific surface area of the grapheme material prepared is 2731.5m2/ g(assay method is identical with embodiment 1).
Performance test:
Method of testing is identical with embodiment 1, and the quality of the grapheme material prepared after tested is 199.6F/g than electric capacity, and volumetric capacitance is 119.7/cm3, energy density is 374.1Wh/cm3, after 2000 times circulate, capacitance remains to reach the 96.1% of initial capacitance.
Embodiment 5:
The preparation method of a kind of high volumetric capacitance Graphene, comprises the steps:
(1) take graphite oxide prepared by Staudenmaier method, after microwave is peeled off, obtain graphene oxide powder；
(2) weigh graphene oxide powder and 0.03g petroleum coke, 10g phosphoric acid that 3g step (1) obtains, be sufficiently mixed, stir, dry；
(3) mixture that step (2) obtains is placed in vacuum tube furnace, after pumping furnace air, is the argon of 99.99% with the flow of 20sccm to vacuum tube furnace passes into purity, at 500 DEG C, reacts 5h；
(4) it is naturally cooling to room temperature after having reacted, washs, dry, obtain the High specific surface area graphene material that volumetric capacitance increases.
The specific surface area of the grapheme material prepared is 1587.3m2/ g(assay method is identical with embodiment 1).
Performance test:
Method of testing is identical with embodiment 1, and the quality of the grapheme material prepared after tested is 101.2F/g than electric capacity, and volumetric capacitance is 50.1F/cm3, energy density is 156.6Wh/cm3, after 2000 times circulate, capacitance remains to reach the 95.8% of initial capacitance.
Comparative example
The preparation method of a kind of Graphene, comprises the steps:
(1) take graphite oxide prepared by Staudenmaier method, after microwave is peeled off, obtain graphene oxide powder；
(2) weigh graphene oxide powder and the KOH of 15g that 3g step (1) obtains, be sufficiently mixed, stir, dry；
(3) mixture that step (2) obtains is placed in vacuum tube furnace, after pumping furnace air, is the argon of 99.99% with the flow of 20sccm to vacuum tube furnace passes into purity, at 1200 DEG C, reacts 5h；
(4) it is naturally cooling to room temperature after having reacted, washs, dry, obtain the High specific surface area graphene material that volumetric capacitance increases.
The specific surface area of the grapheme material prepared is 2307.5m2/ g(assay method is identical with embodiment 1).
Performance test:
Method of testing is identical with embodiment 1, and the quality of the grapheme material prepared after tested is 113F/g than electric capacity, and volumetric capacitance is 68.2F/cm3, energy density is 213.1Wh/cm3, after 2000 times circulate, capacitance remains to reach the 95.5% of initial capacitance.
Be can be seen that by embodiment 1～5 and comparative example, the grapheme material that the present invention prepares is when ensure that high-specific surface area and high-quality than electric capacity, substantially increase the volumetric capacitance of grapheme material, efficiently solve the technical problem that the Graphene caused owing to volume is excessive cannot be applied on a large scale in super capacitor.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the invention is not limited in above-mentioned detailed process equipment and technological process, namely do not mean that the present invention has to rely on above-mentioned detailed process equipment and technological process could be implemented.The equivalence of each raw material of product of the present invention, it will be clearly understood that any improvement in the present invention, is replaced and the interpolation of auxiliary element, concrete way choice etc. by person of ordinary skill in the field, all falls within protection scope of the present invention and open scope.
Claims (1)
1. a preparation method for high volumetric capacitance Graphene, for following steps:
(1) take graphite oxide prepared by Brodie method, after microwave is peeled off, obtain graphene oxide powder；
(2) weigh graphene oxide powder and 3g petroleum coke, NaOH and the 3gKOH of 15g that 3g step (1) obtains, be sufficiently mixed, stir, dry；
(3) mixture that step (2) obtains is placed in vacuum tube furnace, after pumping furnace air, is the argon of 99.99% with the flow of 20sccm to vacuum tube furnace passes into purity, at 1500 DEG C, reacts 0.8h；
(4) it is naturally cooling to room temperature after having reacted, washs, dry, obtain the High specific surface area graphene material that volumetric capacitance increases；
Described than electric capacity using 1MTEABF4/PC as electrolyte measure, the specific surface area 2731.5m of described Graphene2/ g, the quality of grapheme material is 199.6F/g than electric capacity, and volumetric capacitance is 119.7F/cm3, energy density is 374.1Wh/cm3, after 2000 times circulate, capacitance remains to reach the 96.1% of initial capacitance.
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| CN103723721B (en) * | 2013-11-22 | 2016-02-10 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene oxide modification activated carbon for super capacitors |
| CN103723722B (en) * | 2013-11-22 | 2015-11-18 | 山东欧铂新材料有限公司 | A kind of preparation method of Graphene modification activated carbon for super capacitors |
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