CN103366969B - A kind of carbon coated graphite alkene, preparation method and application thereof - Google Patents

A kind of carbon coated graphite alkene, preparation method and application thereof Download PDF

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CN103366969B
CN103366969B CN201310291992.3A CN201310291992A CN103366969B CN 103366969 B CN103366969 B CN 103366969B CN 201310291992 A CN201310291992 A CN 201310291992A CN 103366969 B CN103366969 B CN 103366969B
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carbon coated
graphite alkene
coated graphite
graphene
peeled
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CN103366969A (en
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李璐
徐怀良
刘琼馨
瞿研
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Nantong Sixth Element Material Technology Co ltd
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SIXTH ELEMENT (CHANGZHOU) Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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Abstract

The present invention relates to a kind of preparation method of carbon coated graphite alkene, described method, for after glucide is fully mixed with graphene oxide, adds activator, activates after drying, obtains carbon coated graphite alkene. The present invention ensure grapheme material high-specific surface area and in, improved the density of Graphene, and then improved its volumetric capacitance, overcome Graphene because volumetric capacitance is little, limited it and be applied to the technical barrier of ultracapacitor for electrode material; The present invention is simple to operate, cost is low, safe and reliable, pollutes less, and production efficiency is high, and cost is low, can large-scale production, there is the very strong market competitiveness and application prospect widely.

Description

A kind of carbon coated graphite alkene, preparation method and application thereof
Technical field
The invention belongs to preparation and the application of grapheme material, relate to a kind of carbon coated graphite alkene, preparationMethod and application thereof, the preparation method of described carbon coated graphite alkene is that a kind of glucide dissolves and is evenly coatedThere is high-specific surface area, high-quality than the Graphene of electric capacity and high volumetric capacitance in Graphene surface preparationMethod.
Background technology
Graphene (Graphene) is that carbon atom is arranged the Colloidal particles forming according to hexagonal. From 2004After year being found by the scientist of University of Manchester, it is at aspects such as mechanics, calorifics, electricity, opticsExcellent properties, just becomes the focus that scientific circles and industrial quarters are paid close attention to, particularly in the research heat that is energy fieldPoint. Graphene has the specific area of super large, the conduction of excellence and higher electron mobility, hot swollenly lowSwollen coefficient, and good chemical stability, be considered to the optimal electrode material of ultracapacitor.
Ultracapacitor is a kind of Novel energy storage apparatus, and it has short, long service life of charging interval, temperatureDegree characteristic is good, save the features such as the energy and environmental protection, is widely used in various energy fields. Super capacitorDevice is stored energy in isolated electric charge, closeer for larger, the isolated electric charge of area of stored chargeCollection, its capacitance is larger. Graphene has high specific area and high electrical conductivity, makes Graphene conductElectrode material for super capacitor has the more excellent character of other porous carbon materials. But single Graphene is usedMake electrode material, be subject to the restriction of factors, as easily reunited between lamella, cause irreversible capacityThe raising of loss, and reduced its conductance as electrode material. On the other hand because nano material is generalThere is large specific area, little dimensional effect, although the quality that can improve capacitor than capacitance,Because its bulk density is less, relative volumetric capacitance and energy density are all lower.
Thus, for the Graphene of high-specific surface area, the size of bulk density is to Graphene super capacitorThe aspect such as electricity, the chemistry performance of device has important impact, how to develop a kind of cost lower, volumeHigher than electric capacity and energy density, the preparation method of the Graphene of good cycle, be one of this area urgentlyThe problem solving.
Summary of the invention
In prior art, because the character of Graphene self determines, no matter chemistry redox method or CVDMethod, the unit volume quality (bulk density) of prepared Graphene is all very little, the skill that the present invention will solveArt problem is to overcome existing defect, and a kind of method that improves Graphene volumetric capacitance is provided. For graphiteAlkene volumetric capacitance is little, cannot be applied to the problem of the electricity devices such as jumbo ultracapacitor, the present inventionA kind of Graphene of high volumetric capacitance is proposed, to can effectively addressing this problem.
One of object of the present invention is to provide carbon coated graphite alkene and preparation method thereof, described carbon coated graphiteThe density of alkene is larger, and volumetric capacitance is high, and cycle performance is better simultaneously.
The first aspect of one of object of the present invention is achieved by the following technical solution:
The preparation method of carbon coated graphite alkene of the present invention is: by fully mixed to glucide and graphene oxideAfter closing, add activator, activate after drying, obtain carbon coated graphite alkene.
Described Graphene dissolves by glucide and is evenly coated on its surface, is not changing GrapheneUnder the prerequisite of character, effectively increase the density of Graphene.
The present invention is dissolved in Graphene surface by glucide and is evenly coated, and can effectively increase stoneThe density of China ink alkene, the volumetric capacitance of raising Graphene. The present invention is that the volumetric capacitance that improves Graphene is carriedGo out a kind of new solution thinking, for the electric capacity that further improves the electric elements such as super capacitor provides condition.Graphene provided by the invention has that specific area is large, quality is higher than electric capacity and volumetric capacitance, cycle performanceStable feature.
Preferably, described glucide is selected from any 1 in sucrose, glucose, fructose, ribose or shitosanKind or the combination of at least 2 kinds, be preferably sucrose; Combination, the fructose/shell of for example sucrose/glucose of described combinationThe combination of glycan, the combination of sucrose/glucose/shitosan etc., preferably sucrose.
The present invention is to dissolving by glucide and in Graphene coated with uniform, and at high temperature under conditionActivating and reducing, obtains the coated Graphene of carbon of high-specific surface area, thereby makes prepared grapheme materialVolumetric capacitance amount be greatly improved, make relevant energy density also significantly improve.
The addition of glucide of the present invention is 0.01~1 times of graphene oxide quality, for example 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 glucide of the present invention is too much, and clad is thicker, makes the Graphene can not be abundantReduction, affects the quality of high volumetric capacitance Graphene than electric capacity and specific area; And the interpolation of glucideMeasure too smallly, the density of Graphene can not effectively improve.
Activator of the present invention is selected from any 1 in potassium hydroxide, NaOH, potash or sodium carbonateKind or the combination of at least 2 kinds, be preferably potassium hydroxide, the group of for example potassium hydroxide/NaOH of described combinationClose, combination, the combination of NaOH/potassium hydroxide/sodium carbonate etc. of potash/NaOH.
The effect of activator of the present invention is that reaction obtains hole on graphene sheet layer, increases GrapheneSpecific area.
Preferably, the interpolation quality of described activator is 1~12 times of graphene oxide quality, for example 2 times,4 times, 7 times, 10 times, 11 times, 12 times etc., preferably 1~10 times, further preferably 1~6 times.
The addition of activator of the present invention is too much, easily causes the excessive erosion of Graphene, and lamella damagesSeriously, electric conductivity variation; Addition is very few, and on Graphene, the number in hole is less, affects the ratio table of GrapheneArea.
Graphene oxide of the present invention is that graphite peels off through oxidation the product obtaining. The present invention is to graphite oxidationMethod and oxidation after not concrete restriction of the step peeled off.
Preferably, the mode of described graphite oxidation is preferably from Hummers method, Brodie method or StaudenmaierIn method any a kind.
Brodie method is first with the HNO of being fuming3Process natural micro powder graphite, when graphite is oxidized, nitrate ionInvade between people's graphite flake layer, and then drop into KClO4Further oxidation, throws reactant in National People's Congress's water gaging subsequently,Filter, be washed to filtrate and approach after neutrality, dry, obtain graphite oxide.
Staudemaier method is with the concentrated sulfuric acid and fuming nitric aicd mixed acid, graphite powder to be processed, and is equally alsoWith KClO4For oxidant.
Hummers method is by graphite powder and anhydrous nitric acid sodium (NaNO3) join the dense sulphur being placed in ice bathIn acid, under strong stirring, add KMnO4, and use volume fraction 3%H2O2Reduce remaining potassium permanganate andMnO2, make its soluble MnSO that becomes colorless4. Under the processing of hydrogen peroxide, suspension becomes glassy yellow.Filter, wash 3 times, then vacuum dehydration obtains. The oxidized graphite flake layer obtaining has pleat beryllium type structure,And oxygen content is larger, functional group, can fine dispersion in pure water compared with horn of plenty.
Preferably, the mode of peeling off described in preferably from microwave peel off, pyrolysis expansion is peeled off, ultrasonic dispersion is peeled off,Electrostatic repulsion is peeled off or the combination of any a kind or at least 2 kind of thermal reduction in peeling off, and described combination is for example micro-Ripple is peeled off the combination of peeling off with pyrolysis expansion, ultrasonic dispersion and is peeled off the combination of peeling off with pyrolysis expansion etc., preferablyThe combination of any a kind or at least 2 kinds in microwave stripping method, thermal reduction stripping method or ball milling stripping method, entersThe preferred microwave stripping method of one step.
Preferably, described activation temperature is 600~1500 DEG C, for example 602 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., preferably 600~1200 DEG C, enterOne step is preferably 800 DEG C.
Preferably, described soak time is 0.5~5h, preferably 1~3h, for example 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 is carried out in inert gas environment, described inert gas for not with graphene oxide,Other of the reaction such as activator, glucide, typical but non-limiting is nitrogen, helium, neon, argonGas etc.
Preferably, preferably any a kind or at least 2 in nitrogen, helium or argon gas of described protective atmosphereThe combination of planting, further preferred nitrogen and/or argon gas, particularly preferably nitrogen. Nitrogen of the present invention is preferablyPurity is 99.999% nitrogen, and it is 99.99% argon gas that argon gas is preferably purity.
Preferably, described activation is carried out in vacuum tube furnace.
As optimal technical scheme, carbon coated graphite alkene preparation method of the present invention comprises the steps:
(1) pre-treatment: glucide is dissolved and mixed with graphene oxide, add activator abundantMix, dry;
(2) priming reaction: the mixture that step (1) is obtained is put into vacuum tube furnace, pumps in stoveAfter air, in vacuum tube furnace, pass into protective gas protection, be warming up to activation temperature, liveChange reaction;
(3) post processing: at protective atmosphere borehole cooling, washing, dry, obtain carbon coated graphite alkene.
As optional technical scheme, carbon coated graphite alkene preparation method of the present invention comprises the steps:
(1) pre-treatment: glucide is dissolved and mixed with graphene oxide, add potassium hydroxide to fillDivide and mix, dry;
(2) priming reaction: the mixture that step (1) is obtained is put into vacuum tube furnace, pumps in stoveAfter air, in vacuum tube furnace, pass into protective gas protection, be warming up to 600~1200 DEG C, constant temperature0.5~3h, carries out priming reaction; The flow that passes into of described protective atmosphere is preferably 20~200sccm, enters onePreferably 40~120sccm, particularly preferably 100sccm of step;
(3) post processing: to room temperature, washing, is dried, and obtains carbon coated graphite at protective atmosphere borehole coolingAlkene.
The second aspect of one of object of the present invention is to provide a kind of carbon coated graphite alkene, described carbon coated graphiteAlkene is prepared by the method described in first aspect.
The present invention is dissolved by glucide and after Graphene coated with uniform, activating and reducing under high temperature,Obtain the coated Graphene of carbon of high-specific surface area, thereby make the volume ratio electricity of prepared grapheme materialCapacity is greatly improved, and relevant energy density is also significantly improved.
Preferably, the specific area >=1200m of carbon coated graphite alkene of the present invention2/ g, for example 1200m2/g、1310m2/g、1450m2/g、1530m2/g、1580m2/g、1600m2/g、1630m2/g、1680m2/g、1700m2/g、1900m2/g、2300m2/g、2800m2/g、2900m2/ g etc., are preferably 1200~3000m2/g。
Preferably, with 1MTEABF4/ PC is electrolyte, and the quality of described grapheme material than electric capacity is100~200F/g, for example 104F/g, 120F/g, 130F/g, 150F/g, 180F/g, 190F/g, 197F/gDeng, volumetric capacitance is 50~130F/cm3, for example 52F/cm3、90F/cm3、102F/cm3、107F/cm3、110F/cm3、130F/cm3Deng.
High volumetric capacitance Graphene of the present invention is volumetric capacitance >=50F/cm3Graphene.
Two of object of the present invention is to provide a kind of ultracapacitor, and the electrode material of described ultracapacitor isThe carbon coated graphite alkene that one of object is described.
Described ultracapacitor capacitance after 2000 circulations still can reach the more than 95% of initial capacitance.
Ultracapacitor of the present invention is the conventional method of testings in this area through the process of 2000 circulations,Be typically: by the PTFE(polytetrafluoroethylene (PTFE) of the grapheme material preparing and 60wt%) emulsion, pressThe ratio that is 95:5 according to mass ratio is fully mixed, and then through roll squeezer, repeatedly roll-in is even, makes diameter and isThe Graphene electrodes sheet of 13mm; Be dried to constant weight, assembling obtains testing after super capacitor.
The preparation technology of described Graphene electrodes, the specialty that those skilled in the art can grasp according to oneselfKnowledge is selected, and the present invention is not specifically limited.
Quality of the present invention is than the computing formula of electric capacity (unit is F/g) as shown in the formula (I):
C p = C m · · · · · · · · · · · · · · · · · · · · · · · · · ( 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):
C v = C v · · · · · · · · · · · · · · · · · · · · · · · · · ( II )
In formula, CvFor condenser capacity; C is capacitance; V is the quality of Activated Graphite alkene.
Three of object of the present invention is to provide a kind of lithium ion battery, and the negative material of described lithium ion battery isThe carbon coated graphite alkene that one of object is described;
Three of object of the present invention be to provide a kind of as described in one of object carbon coated graphite alkene for super capacitorThe purposes of device, lithium ion battery or fuel cell aspect.
Because Graphene provided by the invention has high-specific surface area, high-quality than under the prerequisite of electric capacity, also toolHave higher volumetric capacitance, utilize Graphene provided by the invention to develop capacitance large, volume is littleSuper capacitor.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention ensure grapheme material high-specific surface area and in, improved the density of Graphene,And then improved its volumetric capacitance, and overcome Graphene because volumetric capacitance is little, limit it for electrodeMaterial is applied to the technical barrier of ultracapacitor;
(2) the present invention is simple to operate, cost is low, safe and reliable, pollutes less, and production efficiency is high, and cost is low,Can large-scale production, there is the very strong market competitiveness and application prospect widely.
Brief description of the drawings
Fig. 1 is the SEM figure of carbon coated graphite alkene described in one embodiment of the present invention;
Fig. 2 is the cyclic voltammetric of the Graphene electrodes that makes of embodiment 1 in 1MTEABF4/PC electrolyteCurve;
Fig. 3 is the constant current charge-discharge time graph of the super capacitor that makes of embodiment 1;
Fig. 4 is the cyclic voltammetric of the Graphene electrodes that makes of embodiment 2 in 1MTEABF4/PC electrolyteCurve;
Fig. 5 is the constant current charge-discharge time graph of the super capacitor that makes of embodiment 2;
Fig. 6 is the cyclic voltammetric of the Graphene electrodes that makes of embodiment 3 in 1MTEABF4/PC electrolyteCurve;
Fig. 7 is the constant current charge-discharge time graph of the super capacitor that makes of embodiment 3.
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 should understand,Described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1:
A preparation method for carbon coated graphite alkene, comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Hummers legal system, obtain being oxidized stone after microwave is peeled offChina ink alkene powder, for subsequent use; Weigh 1g sucrose and be dissolved in fully dissolving in 100mL deionized water, add 3g oxidationGraphene powder stirs 5h, then adds the KOH of 15g, fully mixes, stirs, is dried;
(2) mixture step (1) being obtained is placed in vacuum tube furnace, pumps after furnace air, withThe flow of 100sccm is 99.99% argon gas to passing into purity in vacuum tube furnace, at 800 DEG C, reacts 2h;
(3) reacted the rear room temperature that is naturally cooled to, washing, dry, obtains the carbon that volumetric capacitance increasesCoated graphite alkene material. Fig. 1 is the SEM figure processed of carbon coated graphite alkene described in embodiment 1;
The specific area of the grapheme material preparing is 1250m2/ g(adopt U.S. health tower specific area withPore analysis instrument NOVA2000e carries out specific area measuring).
Performance test:
Preparation Graphene electrodes sheet: by the PTFE(polytetrafluoroethyl-ne of the grapheme material preparing and 60wt%Alkene) emulsion, the ratio that is 95:5 according to mass ratio is fully mixed; Then through roll squeezer, repeatedly roll-in is even,Making diameter is the Graphene electrodes sheet of 13mm;
The Graphene electrodes sheet preparing is put into vacuum drying chamber inner drying to constant weight, and then assembling obtainsSuper capacitor;
With 1MTEABF4/ PC, as electrolyte, utilizes electrochemical workstation to carry out electrochemical property test,Fig. 2 is that the Graphene electrodes that makes of embodiment 1 is at 1MTEABF4Cyclic voltammetry curve in/PC electrolyte;Fig. 3 is the constant current charge-discharge time graph of the super capacitor that makes of embodiment 1; The Graphene making after testedThe quality of material is 189F/g than electric capacity, and volumetric capacitance is 120F/cm3, energy density is 375Wh/cm3,After 2000 circulations, capacitance still can reach 98% of initial capacitance.
Embodiment 2:
A preparation method for carbon coated graphite alkene, comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Hummers legal system, obtain being oxidized stone after microwave is peeled offChina ink alkene powder, for subsequent use; Weigh 2g glucose and be dissolved in fully dissolving in 100mL deionized water, add 3g oxygenFunctionalized graphene powder stirs 10h, then adds the KOH of 18g, fully mixes, stirs, is dried;
(2) mixture step (1) being obtained is placed in vacuum tube furnace, pumps after furnace air, withThe flow of 100sccm is 99.99% argon gas to passing into purity in vacuum tube furnace, at 900 DEG C, reacts 1h;
(3) reacted the rear room temperature that is naturally cooled to, washing, dry, obtains the carbon that volumetric capacitance increasesCoated graphite alkene material.
The specific area of the grapheme material preparing is 2590m2/ g(assay method is identical with embodiment 1).
Performance test:
Method of testing is identical with embodiment 1, and Fig. 4 is that the Graphene electrodes that makes of embodiment 2 is at 1MTEABF4Cyclic voltammetry curve in/PC electrolyte; Fig. 5 is the constant current of the super capacitor that makes of embodiment 2Discharge and recharge time graph; The quality of the grapheme material making is after tested 150F/g than electric capacity, volume ratio electricityHold for 92F/cm3, energy density is 288Wh/cm3, at the beginning of after 2000 circulations, capacitance still can reach95% of beginning electric capacity.
Embodiment 3:
A preparation method for carbon coated graphite alkene, comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Hummers legal system, obtain being oxidized stone after microwave is peeled offChina ink alkene powder, for subsequent use; Weigh 0.5g fructose and be dissolved in fully dissolving in 100mL deionized water, add 3g oxygenFunctionalized graphene powder stirs 15h, then adds the KOH of 12g, fully mixes, stirs, is dried;
(2) mixture step (1) being obtained is placed in vacuum tube furnace, pumps after furnace air, withThe flow of 100sccm is 99.99% argon gas to passing into purity in vacuum tube furnace, reaction at 1000 DEG C1.5h;
(3) reacted the rear room temperature that is naturally cooled to, washing, dry, obtains the carbon that volumetric capacitance increasesCoated graphite alkene material.
The specific area of the grapheme material preparing is 2995m2/ g(assay method is identical with embodiment 1).
Performance test:
Method of testing is identical with embodiment 1, and Fig. 6 is that the Graphene electrodes that makes of embodiment 3 is at 1MTEABF4Cyclic voltammetry curve in/PC electrolyte; Fig. 7 is the constant current of the super capacitor that makes of embodiment 3Discharge and recharge time graph; The quality of the grapheme material making is after tested 120F/g than electric capacity, volume ratio electricityHold for 65F/cm3, energy density is 203Wh/cm3, at the beginning of after 2000 circulations, capacitance still can reach96% of beginning electric capacity.
Embodiment 4:
A preparation method for carbon coated graphite alkene, comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Brodie legal system, obtain graphene oxide after microwave is peeled offPowder, for subsequent use; Weigh 3g shitosan and be dissolved in fully dissolving in 100mL deionized water, add 3g oxidation stoneChina ink alkene powder stirs 10h, then adds the KOH of 9g and the mixture of 6gNaOH, fully mixes, stirsMix, be dried;
(2) mixture step (1) being obtained is placed in vacuum tube furnace, pumps after furnace air, withThe flow of 20sccm is 99.99% argon gas to passing into purity in vacuum tube furnace, at 1500 DEG C, reacts 0.5h;
(3) reacted the rear room temperature that is naturally cooled to, washing, dry, obtains the carbon that volumetric capacitance increasesCoated graphite alkene material.
The specific area of the grapheme material preparing is 2820m2/ 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 making after tested than electric capacity is199F/g, volumetric capacitance is 129/cm3, energy density is 403Wh/cm3, after 2000 circulationsCapacitance still can reach 97% of initial capacitance.
Embodiment 5:
A preparation method for carbon coated graphite alkene, comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Staudenmaier legal system, be oxidized after microwave is peeled offGraphene powder, for subsequent use; Weigh 0.1g fructose and be dissolved in fully dissolving in 100mL deionized water, add 3gGraphene oxide powder stirs 2h, then adds the NaOH of 18g, fully mixes, stirs, is dried;
(2) mixture step (1) being obtained is placed in vacuum tube furnace, pumps after furnace air, withThe flow of 20sccm is 99.99% argon gas to passing into purity in vacuum tube furnace, at 600 DEG C, reacts 5h;
(3) reacted the rear room temperature that is naturally cooled to, washing, dry, obtains the height that volumetric capacitance increasesSpecific surface grapheme material.
The specific area of the grapheme material preparing is 1512m2/ 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 making after tested than electric capacity is100F/g, volumetric capacitance is 51F/cm3, energy density is 159Wh/cm3, after 2000 circulationsCapacitance still can reach 95% of initial capacitance.
Embodiment 6:
A preparation method for carbon coated graphite alkene, comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Staudenmaier legal system, be oxidized after microwave is peeled offGraphene powder, for subsequent use; Weigh 0.1g fructose and be dissolved in fully dissolving in 100mL deionized water, add 10gGraphene oxide powder stirs 2h, then adds the NaOH of 120g, fully mixes, stirs, is dried;
(2) mixture step (1) being obtained is placed in vacuum tube furnace, pumps after furnace air, withThe flow of 20sccm is 99.99% argon gas to passing into purity in vacuum tube furnace, at 700 DEG C, reacts 1h;
(3) reacted the rear room temperature that is naturally cooled to, washing, dry, obtains the height that volumetric capacitance increasesSpecific surface grapheme material.
The specific area of the grapheme material preparing is 2290m2/ 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 making after tested than electric capacity is120F/g, volumetric capacitance is 55F/cm3, energy density is 172Wh/cm3, after 2000 circulationsCapacitance still can reach 95% of initial capacitance.
Can be found out by embodiment 1~6, the grapheme material that the present invention prepares is ensureing high-ratio surfaceLong-pending and high-quality, than in the situation of electric capacity, has improved the volumetric capacitance of grapheme material greatly, effectively solvesThe technical problem that cannot apply in super capacitor on a large scale of the Graphene that causes because volume is excessive.
Applicant's statement, the present invention illustrates detailed process equipment and process of the present invention by above-described embodimentFlow process, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that the present inventionMust rely on above-mentioned detailed process equipment and process flow process could implement. Person of ordinary skill in the field shouldThis understands, any improvement in the present invention, the equivalence replacement to the each raw material of product of the present invention and auxiliary elementThe selections of interpolation, concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims (29)

1. a preparation method for carbon coated graphite alkene, is characterized in that, described method be by glucide withGraphene oxide adds activator after fully mixing, and activates after drying, obtains carbon coated graphite alkene;
Described glucide is selected from any a kind or extremely in sucrose, glucose, fructose, ribose or shitosanThe combination of few 2 kinds; The addition of described glucide is 0.01~1 times of graphene oxide quality;
Described activator is selected from any a kind or extremely in potassium hydroxide, NaOH, potash or sodium carbonateThe combination of few 2 kinds; The interpolation quality of described activator is 1~12 times of graphene oxide quality;
Described activation temperature is 600~1500 DEG C, and described soak time is 0.5~5h.
2. the method for claim 1, is characterized in that, described glucide is sucrose.
3. the method for claim 1, is characterized in that, described activator is potassium hydroxide.
4. method as claimed in claim 3, is characterized in that, the interpolation quality of described activator is oxidation1~10 times of Graphene quality.
5. method as claimed in claim 3, is characterized in that, the interpolation quality of described activator is oxidation1~6 times of Graphene quality.
6. the method for claim 1, is characterized in that, described graphene oxide is that graphite is through oxidationPeel off the product obtaining.
7. method as claimed in claim 6, is characterized in that, the mode of described graphite oxidation is selected fromIn Hummers method, Brodie method or Staudenmaier method any a kind.
8. method as claimed in claim 6, is characterized in that, described in the mode peeled off be selected from microwave peel off,Pyrolysis expansion is peeled off, ultrasonic dispersion is peeled off, electrostatic repulsion is peeled off, ball milling is peeled off or thermal reduction appointing in peeling offThe anticipate combination of a kind or at least 2 kinds.
9. method as claimed in claim 8, is characterized in that, described in the mode peeled off be selected from microwave peel off,Thermal reduction is peeled off or the combination of any a kind or at least 2 kind of ball milling in peeling off.
10. method as claimed in claim 9, is characterized in that, described in the mode peeled off be that microwave is peeled off.
11. the method for claim 1, is characterized in that, described activation temperature is 600~1200 DEG C.
12. methods as claimed in claim 11, is characterized in that, described activation temperature is 800 DEG C.
13. the method for claim 1, is characterized in that, described soak time is 1~3h.
14. the method for claim 1, is characterized in that, described activation is entered in protective atmosphereOK.
15. methods as claimed in claim 14, is characterized in that, described protective atmosphere be selected from nitrogen,The combination of any a kind or at least 2 kinds in helium or argon gas.
16. methods as claimed in claim 15, is characterized in that, described protective atmosphere be nitrogen and/Or argon gas.
17. methods as claimed in claim 16, is characterized in that, described protective atmosphere is nitrogen.
18. the method for claim 1, is characterized in that, described activation is entered in vacuum tube furnaceOK.
19. the method for claim 1, is characterized in that, described method comprises the steps:
(1) pre-treatment: glucide is dissolved and mixed with graphene oxide, add activator abundantMix, dry;
(2) priming reaction: the mixture that step (1) is obtained is put into vacuum tube furnace, pumps in stoveAfter air, in vacuum tube furnace, pass into protective gas protection, be warming up to activation temperature, liveChange reaction;
(3) post processing: at protective atmosphere borehole cooling, washing, dry, obtain carbon coated graphite alkene.
20. methods as claimed in claim 19, is characterized in that, described method comprises the steps:
(1) pre-treatment: glucide is dissolved and mixed with graphene oxide, add potassium hydroxide to fillDivide and mix, dry;
(2) priming reaction: the mixture that step (1) is obtained is put into vacuum tube furnace, pumps in stoveAfter air, in vacuum tube furnace, pass into protective gas protection, be warming up to 600~1200 DEG C, constant temperature0.5~3h, carries out priming reaction; The flow that passes into of described protective atmosphere is 20~200sccm;
(3) post processing: to room temperature, washing, is dried, and obtains carbon coated graphite at protective atmosphere borehole coolingAlkene.
21. methods as claimed in claim 20, is characterized in that, described protective atmosphere pass into flowBe 40~120sccm.
22. methods as claimed in claim 21, is characterized in that, described protective atmosphere pass into flowFor 100sccm.
23. 1 kinds of carbon coated graphite alkene, is characterized in that, described carbon coated graphite alkene is by as claim 1~22One of described method prepare.
24. carbon coated graphite alkene as claimed in claim 23, is characterized in that, the ratio table of described GrapheneArea >=1200m2/g。
25. carbon coated graphite alkene as claimed in claim 24, is characterized in that, the ratio table of described GrapheneArea is 1200~3000m2/g。
26. carbon coated graphite alkene as claimed in claim 23, is characterized in that, with 1MTEABF4/PCFor electrolyte, the quality of described grapheme material is 100~200F/g than electric capacity, and volumetric capacitance is50~130F/cm3
27. 1 kinds of ultracapacitors, is characterized in that, the electrode material of described ultracapacitor is that right is wantedAsk the carbon coated graphite alkene described in 23-26 any one.
28. ultracapacitors as claimed in claim 27, is characterized in that, described ultracapacitor processAfter 2000 circulations, capacitance still can reach the more than 95% of initial capacitance.
29. 1 kinds as described in claim 23-26 any one carbon coated graphite alkene for ultracapacitor, lithium fromThe purposes of sub-battery or fuel cell aspect.
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