CN103253658A - Graphene with high volumetric specific capacitance and preparation method thereof - Google Patents
Graphene with high volumetric specific capacitance and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a type of graphene. Active carbon is doped in the graphene sheet. The invention further discloses a preparation method of the graphene. The preparation method comprises the following steps of: adequately mixing oxidized graphene with an activating agent and a carbon-source substance; activating under the protection of a protective atmosphere; and then cooling, washing and drying to obtain the graphene with a high volumetric specific capacitance. According to the graphene and the preparation method disclosed by the invention, the volumetric specific capacitance of the graphene is increased while the high specific surface area and high mass specific capacitance of graphene material are ensured, thus overcoming the technical problem that the graphene cannot be applied to a super-capacitor as an electrode material due to low volumetric specific capacitance. According to the graphene and the preparation method, massive use for chemical reagents is avoided, and the usage amount of the activating agent is reduced; and the graphene is simple in equipment, low in cost, safe and reliable, less in pollution, high in production efficiency, low in cost, capable of being produced on a large scale, very strong in market competitiveness, and wide in application 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 Graphene of high-specific surface area, high volumetric capacitance and preparation method thereof of getting everything ready, belong to preparation and the Application Areas of grapheme material.
Background technology
Graphene (Graphene) is a kind of novel material of the individual layer sheet structure that is made of carbon atom, be a kind ofly to form the flat film that hexangle type is the honeycomb lattice by carbon atom with the sp2 hybridized orbital, it is the two-dimensional material of having only a carbon atom thickness, have the specific surface area of super large, excellent conduction and heat conductivility, and good chemical stability.These good properties make the material based on Graphene become a kind of desirable energy storage material, comprise that super capacitance electrode material, lithium ion battery electrode material, hydrogen storage material, fuel cell are with material etc.
Ultracapacitor is an efficient system that stores and transmit energy, and advantages such as it has, and power density is big, capacity big, long service life, economic environmental protection are widely used in various energy fields.Carbon material, the particularly carbon material of sp2 hydridization are because the specific surface area of its special laminate structure, super large forms the electrode materials into important energy storage device.Carbon material such as decolorizing carbon, porous carbon, graphite etc. are widely used in the lithium ion battery.
Graphene has high specific surface area and high specific conductivity, make Graphene have the more excellent character of other porous carbon materials as capacitor material, make its ideal electrode material that is expected to become ultracapacitor, its performance is directly related with quality, the number of plies and the specific surface area of Graphene.There are some researches show that the ratio electric capacity of Graphene in electrolyte solution with water that obtains by the hydrazine redox graphene can be up to 205F/g, through it also still reaches original 90% than electric capacity after 1200 times the test.Because nano material generally has big specific surface area, little dimensional effect, thereby the quality that can improve electrical condenser is than capacity ratio capacity, but its relative volumetric capacitance is lower, for energy storage material, reaching certain store content just needs very big volume, has limited its development.
Thus, Graphene for high-specific surface area, the unit volume quality of Graphene is to aspect performance important influence such as the electricity of Graphene ultracapacitor, chemistry, it is lower how to develop a kind of cost, the volumetric capacitance height, the high-ratio surface preparation method of graphene of good cycle and suitable electrolyte is a problem demanding prompt solution of this area
Summary of the invention
In the prior art, because the character of Graphene self determines no matter the chemistry redox method still is the CVD method, the unit volume quality of prepared graphene is all very little, the technical problem to be solved in the present invention is to overcome existing defective, and a kind of method of putting forward the Graphene volumetric capacitance is provided.Little at the Graphene volumetric capacitance, can't be applied to the problem of electricity devices such as jumbo ultracapacitor, the present invention proposes a kind of Graphene of high volumetric capacitance, in the hope of can effectively addressing this problem.
One of purpose of the present invention provides a kind of Graphene, is doped with gac in the described Graphene lamella.
The present invention is dopped activated carbon in Graphene, can increase the density of Graphene effectively, improves the volumetric capacitance of Graphene.The present invention has proposed a kind of new solution thinking for the volumetric capacitance that improves Graphene, for the electric capacity that further improves electric elements such as super capacitor provides condition.Graphene provided by the invention has that specific surface area is big, quality is than electric capacity height, and the high characteristics of volumetric capacitance.
Preferably, described gac is obtained by carbon source material activation back, described carbon source material is the combination of any a kind or at least 2 kinds in starch, wood chip, charcoal, coconut husk, coal, shell or refinery coke preferably, described combination is the combination, the combination of coconut husk/coal, the combination of wood chip/shell/charcoal etc. of starch/charcoal for example, further preferred charcoal and/or refinery coke, preferred especially charcoal.
The present invention is in graphene oxide reactivation process, the additional carbon material, at high temperature carbon source material decomposes and is entrained in the Graphene, obtain being doped with the Graphene of gac, thereby make the volumetric capacitance amount of prepared graphene material be greatly improved, make relevant energy density significantly improve.
Preferably, described activation is high-temperature activation, described high-temperature activation temperature is 500～1500 ℃, for example 510 ℃, 620 ℃, 650 ℃, 730 ℃, 790 ℃, 854 ℃, 885 ℃, 906 ℃, 948 ℃, 980 ℃, 1050 ℃, 1100 ℃, 1350 ℃, 1480 ℃, 1500 ℃ etc., preferred soak time is 0.5～5h, for example 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 Graphene
2/ g, for example 1530m
2/ g, 1580m
2/ g, 1600m
2/ g, 1630m
2/ g, 1680m
2/ g, 1700m
2/ g, 1900m
2/ g, 2300m
2/ g, 2800m
2/ g, 2900m
2/ g etc. are preferably 1500～3000m
2/ g.
Preferably, be electrolytic solution with 1M TEABF4/PC, the quality of described grapheme material is 100～200F/g than electric capacity, for example 100F/g, 120F/g, 130F/g, 150F/g, 180F/g, 190F/g, 200F/g etc., volumetric capacitance is 50～120F/cm
3, 52F/cm for example
3, 90F/cm
3, 102F/cm
3, 107F/cm
3, 110F/cm
3, 118F/cm
3Deng.
High volumetric capacitance Graphene of the present invention is volumetric capacitance 〉=50F/cm
3Graphene.
Two of purpose of the present invention provides a kind of as the described preparation method of graphene of one of purpose; described method is for fully to mix graphene oxide with activator, carbon source material; under protective atmosphere protection, carry out high-temperature activation, the Graphene that lower the temperature then, washing, drying obtains high volumetric capacitance.
The present invention fully mixes the carbon source material of graphene oxide with activator, adding; in the high-temperature activation process under protective atmosphere; the carbon source material that adds is decomposed and fully is doped in the lamella of Graphene; reached the purpose of dopped activated carbon in Graphene; thereby guaranteeing the Graphene high-specific surface area; under the prerequisite of high quality than electric capacity; increased the volumetric capacitance of grapheme material; and preparation method of graphene provided by the invention; process is simple; easy handling, environmental protection and output height.
Preferably, described carbon source material is selected from the combination of any a kind or at least 2 kinds in starch, wood chip, charcoal, coconut husk, coal, shell or the refinery coke, described combination is the combination, the combination of wood chip/refinery coke, the combination of coal/charcoal, the combination of starch/shell/coal etc. of starch/coconut husk for example, preferred charcoal and/or refinery coke, further preferred charcoal.
Preferably, the addition of described carbon source material 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 carbon source material of the present invention is too much, influences the quality of high volumetric capacitance Graphene than electric capacity and specific surface area; And the addition of carbon source material is too small, does 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, salt of wormwood or the zinc chloride, and described combination is the combination, the combination of phosphoric acid/zinc chloride, the combination of potassium hydroxide/zinc chloride, the combination of potassium hydroxide/sodium hydroxide/zinc chloride etc. of potassium hydroxide/sodium hydroxide for example; Those skilled in the art should understand that described combination does not comprise the combination of alkali and acid, does not for example comprise the combination of potassium hydroxide and/or lithium hydroxide and phosphoric acid.
The effect of activator of the present invention is to obtain the hole in the reaction of Graphene lamella, increases the specific surface area of Graphene.Those skilled in the art should understand that in listed activator, phosphoric acid is acid, can with alkali substance reaction, cause it or lose activity with the material of its reaction, so among the present invention, phosphoric acid cannot together use with alkaline matters such as potassium hydroxide, sodium hydroxide, salt of wormwood.
Preferably, the interpolation quality of described activator is 1～15 times of graphene oxide quality, for example 2 times, 4 times, 7 times, 10 times, 14 times, 14.6 times etc., and preferred 1～12 times, further preferred 1～6 times.
Concrete addition those skilled in the art of described activator can select by consulting document, typical but non-limiting: when the agent of independent interpolation hydroxide, when sodium hydroxide is activator, the addition of described activator is 1～15 times of graphene oxide quality; When independent interpolation salt of wormwood was activator, the addition of described activator was 1～5 times of graphene oxide quality; When independent interpolation phosphoric acid or zinc chloride were activator, the addition of described activator was 1～3 times of graphene oxide quality.
The addition of activator of the present invention is too much, causes the excessive erosion of Graphene easily, lamella well damage, electroconductibility variation; Addition is very few, and the number in hole is less on the Graphene, influences the specific surface area of Graphene.
Preferably, described graphene oxide is the product that graphite is peeled off after oxidation.The step that the present invention peels off after to the method for graphite oxidation and oxidation is concrete the restriction not.
Preferably, the mode of described graphite oxidation adopts in Hummers method, Staudenmaier method or the Brodie method any a kind.
The Brodie method is at first with the HNO of being fuming
3Handle natural micro powder graphite, when graphite was oxidized, nitrate ion was invaded between people's graphite flake layer, and then dropped into KClO
4Further oxidation is thrown reactant in National People's Congress's water gaging subsequently, filters, be washed to filtrate near neutrality after, drying obtains graphite oxide.
The Staudemaier method is with the vitriol oil and nitrosonitric acid mixing acid Graphite Powder 99 to be handled, and equally also is with KClO
4Be oxygenant.
The Hummers method is with Graphite Powder 99 and anhydrous nitric acid sodium (NaNO
3) joining the vitriol oil that places in the ice bath, the powerful stirring adds KMnO down
4, and use volume fraction 3%H
2O
2Reduce remaining potassium permanganate and MnO
2, make its soluble MnSO that becomes colorless
4Under the processing of hydrogen peroxide, suspension becomes glassy yellow.Filter, wash 3 times, vacuum hydro-extraction obtains then.Resulting oxidized graphite flake layer has pleat beryllium type structure, and oxygen level is bigger, and functional group is than horn of plenty, but in pure water good distribution.
Preferably, the described mode of peeling off is selected from microwave and peels off the expand method of peeling off, ultra-sonic dispersion of method, pyrolysis and peel off method, electrostatic repulsion and peel off the combination that any a kind or at least 2 kinds in the method are peeled off in method or thermal reduction, described combination for example microwave is peeled off with expand combination, the ultra-sonic dispersion peel off of pyrolysis and is peeled off and the pyrolysis combination of peeling off etc. of expanding, preferred microwave is peeled off method, thermal reduction and is peeled off the combination that method or ball milling are peeled off any a kind or at least 2 kinds in the method, and further preferred microwave is peeled off method.
Preferably, described high-temperature activation temperature is 500～1500 ℃, for example 502 ℃, 625 ℃, 750 ℃, 880 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1450 ℃, 1500 ℃ etc., preferred soak time is 0.5～5h, for example 0.6h, 0.9h, 1.3h, 1.7h, 2.5h, 2.9h, 3.4h, 3.8h, 4.5h, 4.7h etc.
Of the present invention being reflected in the inert gas environment carried out, described rare gas element be not with other of reaction such as graphene oxide, activator, carbon source material, typical but non-limiting is nitrogen, helium, neon, argon gas etc.Preferably, described protective atmosphere is the combination of any a kind or at least 2 kinds in nitrogen, helium or argon gas preferably, further preferred nitrogen and/or argon gas, most preferably nitrogen.It is 99.999% nitrogen that nitrogen of the present invention is preferably purity, and it is 99.99% argon gas that argon gas is preferably purity.
Preferably, the feeding flow of described protective atmosphere is 20-200sccm, for example 20sccm, 50sccm, 62sccm, 69sccm, 76sccm, 84sccm, 97sccm, 103sccm, 115sccm, 123sccm, 138sccm, 145sccm, 155sccm, 167sccm, 179sccm, 185sccm, 190sccm, 200sccm etc., preferred 40-120sccm, further preferred 100sccm;
Preferably, described activation is carried 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: with graphene oxide, carbon source material and activator according to mass ratio 1:(0.01～1): fully mix (1～15), drying;
(2) redox graphene and activating: the mixture of graphene oxide, carbon source material and the activator that step (1) is obtained is put into vacuum tube furnace, after taking out furnace air, feeding rare gas element in the vacuum tube furnace protects, be warming up to 600-1200 ℃, isothermal reaction 0.5-3h;
(3) aftertreatment: after reaction finishes, drop to room temperature in protection of inert gas, washing, drying obtain the Graphene of high volumetric capacitance.
Three of purpose of the present invention provides a kind of Graphene electrodes, and described electrode materials is the described Graphene of one of the object of the invention.
Preferably, in the described Graphene electrodes material, the content of Graphene is 80～98wt%, for example 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 expertise of oneself grasping, and the present invention does not do concrete restriction.
When being that 95:5 mixes Graphene electrodes that the PTFE emulsion preparation of one of purpose described grapheme material and 60wt% obtains in organic electrolyte with the mass ratio, still can reach more than 95% of initial capacitance through 2000 circulation back electrical capacitys.
Quality of the present invention than the calculation formula of electric capacity (unit is F/g) suc as formula shown in (I):
In the formula, C
pBe condenser capacity; C is electrical capacity; M is the quality of active Graphene.
(unit is F/cm to volumetric capacitance of the present invention
3) calculation formula suc as formula shown in (II):
In the formula, C
vBe condenser capacity; C is electrical capacity; V is the quality of active Graphene.
Four of purpose of the present invention provides a kind of purposes that is used for ultracapacitor, lithium ion battery or fuel cell aspect as Graphene as described in one of purpose.
Because Graphene provided by the invention has under high-specific surface area, the prerequisite of high quality than electric capacity, also has higher volumetric capacitance, it is big to utilize Graphene provided by the invention to develop electrical capacity, the super capacitor that volume is little.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention has improved the volumetric capacitance of Graphene when guaranteeing that grapheme material high-specific surface area and high quality are than electric capacity, has overcome Graphene because volumetric capacitance is little, can't be applied to the technical barrier of super capacitor as electrode materials;
(2) the present invention has avoided a large amount of use chemical reagent, has reduced the usage quantity of activator, and equipment is simple, cost is low, and is safe and reliable, pollute few, the production efficiency height, cost is low, can scale operation, have the very strong market competitiveness and application prospect widely.
Description of drawings
Fig. 1 is preparation technology's flow diagram of the described high volumetric capacitance Graphene of one embodiment of the present invention;
The cyclic voltammetry curve of the Graphene electrodes that Fig. 2 makes for embodiment 1 in 1M TEABF4/PC electrolytic solution;
The constant current charge-discharge time curve of the super capacitor that Fig. 3 makes for embodiment 1;
The cyclic voltammetry curve of the Graphene electrodes that Fig. 4 makes for embodiment 2 in 1M TEABF4/PC electrolytic solution;
The constant current charge-discharge time curve of the super capacitor that Fig. 5 makes for embodiment 2;
The cyclic voltammetry curve of the Graphene electrodes that Fig. 6 makes for embodiment 3 in 1M TEABF4/PC electrolytic solution;
The constant current charge-discharge time curve of the super capacitor that Fig. 7 makes for embodiment 3.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand that described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1:
A kind of high volumetric capacitance preparation method of graphene comprises the steps:
(1) gets the graphite oxide that the Hummers method prepares, after microwave is peeled off, obtain the graphene oxide powder;
(2) the graphene oxide powder and the 0.5g charcoal that obtain of weighing 3g step (1), the KOH of 15g, fully mixing, stirring, drying;
(3) mixture that step (2) is obtained places in the vacuum tube furnace, take out furnace air after, feeding purity in the vacuum tube furnace with the flow of 100sccm is 99.99% argon gas, at 800 ℃ of reaction 1.5h down;
(4) be cooled to room temperature naturally after reaction is finished, washing, drying obtain the high-ratio surface grapheme material that volumetric capacitance increases.Fig. 1 is preparation technology's flow diagram of embodiment 1 described high volumetric capacitance Graphene;
The specific surface area of the grapheme material for preparing is 1605.3m
2/ g(adopts U.S.'s health tower specific surface area and aperture analyser NOVA2000e to carry out specific area measuring).
Performance test:
Preparation Graphene electrodes sheet: with the grapheme material for preparing and the PTFE(tetrafluoroethylene of 60wt%) emulsion is that the ratio of 95:5 is fully mixed according to mass ratio; Repeatedly roll-in is even through roll squeezer then, and making diameter is the Graphene electrodes sheet of 13mm;
The Graphene electrodes sheet for preparing is put into the vacuum drying oven inner drying to constant weight, and assembling obtains super capacitor then;
As electrolytic solution, utilize electrochemical workstation to carry out electrochemical property test, the cyclic voltammetry curve of the Graphene electrodes that Fig. 2 makes for embodiment 1 in 1M TEABF4/PC electrolytic solution with 1M TEABF4/PC; The constant current charge-discharge time curve of the super capacitor that Fig. 3 makes for embodiment 1; The quality of the grapheme material that makes after tested is 185.1F/g than electric capacity, and volumetric capacitance is 110.3F/cm
3, energy density is 333.7Wh/cm
3, still can reach 97.9% of initial capacitance through 2000 circulation back electrical capacitys.
Embodiment 2:
A kind of high volumetric capacitance preparation method of graphene comprises the steps:
(1) gets the graphite oxide that the Hummers method prepares, after microwave is peeled off, obtain the graphene oxide powder;
(2) the graphene oxide powder and the 1g wood chip that obtain of weighing 3g step (1), the KOH of 18g, fully mixing, stirring, drying;
(3) mixture that step (2) is obtained places in the vacuum tube furnace, take out furnace air after, feeding purity in the vacuum tube furnace with the flow of 120sccm is 99.99% argon gas, at 900 ℃ of reaction 1h down;
(4) be cooled to room temperature naturally after reaction is finished, washing, drying obtain the high-ratio surface grapheme material that volumetric capacitance increases.
The specific surface area of the grapheme material for preparing is 1996.9m
2/ g(measuring method is identical with embodiment 1).
Performance test:
Testing method is identical with embodiment 1, the cyclic voltammetry curve of Graphene electrodes in 1MTEABF4/PC electrolytic solution that Fig. 4 makes for embodiment 2; The constant current charge-discharge time curve of the super capacitor that Fig. 5 makes for embodiment 2; The quality of the grapheme material that makes after tested is 161.3F/g than electric capacity, and volumetric capacitance is 90.3F/cm
3, energy density is 282.2Wh/cm
3, still can reach 95.2% of initial capacitance through 2000 circulation back electrical capacitys.
Embodiment 3:
A kind of high volumetric capacitance preparation method of graphene comprises the steps:
(1) gets the graphite oxide that the Hummers method prepares, after microwave is peeled off, obtain the graphene oxide powder;
(2) the graphene oxide powder and the 1g refinery coke that obtain of weighing 3g step (1), the KOH of 15g, fully mixing, stirring, drying;
(3) mixture that step (2) is obtained places in the vacuum tube furnace, take out furnace air after, feeding purity in the vacuum tube furnace with the flow of 60sccm is 99.99% argon gas, at 1200 ℃ of reaction 0.5h down;
(4) be cooled to room temperature naturally after reaction is finished, washing, drying obtain the high-ratio surface grapheme material that volumetric capacitance increases.
The specific surface area of the grapheme material for preparing is 2150.2m
2/ g(measuring method is identical with embodiment 1).
Performance test:
Testing method is identical with embodiment 1, the cyclic voltammetry curve of Graphene electrodes in 1MTEABF4/PC electrolytic solution that Fig. 6 makes for embodiment 3; The constant current charge-discharge time curve of the super capacitor that Fig. 7 makes for embodiment 3; The quality of the grapheme material that makes after tested is 142.2F/g than electric capacity, and volumetric capacitance is 71.1F/cm
3, energy density is 222.1Wh/cm
3, still can reach 96.5% of initial capacitance through 2000 circulation back electrical capacitys.
Embodiment 4:
A kind of high volumetric capacitance preparation method of graphene comprises the steps:
(1) gets the graphite oxide that the Brodie method prepares, after microwave is peeled off, obtain the graphene oxide powder;
(2) the graphene oxide powder and the 3g refinery coke that obtain of weighing 3g step (1), the NaOH of 15g and 3gKOH, fully mixing, stirring, drying;
(3) mixture that step (2) is obtained places in the vacuum tube furnace, take out furnace air after, feeding purity in the vacuum tube furnace with the flow of 20sccm is 99.99% argon gas, at 1500 ℃ of reaction 0.8h down;
(4) be cooled to room temperature naturally after reaction is finished, washing, drying obtain the high-ratio surface grapheme material that volumetric capacitance increases.
The specific surface area of the grapheme material for preparing is 2731.5m
2/ g(measuring method is identical with embodiment 1).
Performance test:
Testing method is identical with embodiment 1, and the quality of the grapheme material that makes after tested is 199.6F/g than electric capacity, and volumetric capacitance is 119.7/cm
3, energy density is 374.1Wh/cm
3, still can reach 96.1% of initial capacitance through 2000 circulation back electrical capacitys.
Embodiment 5:
A kind of high volumetric capacitance preparation method of graphene comprises the steps:
(1) gets the graphite oxide that the Staudenmaier method prepares, after microwave is peeled off, obtain the graphene oxide powder;
(2) the graphene oxide powder and the 0.03g refinery coke that obtain of weighing 3g step (1), 10g phosphoric acid, fully mixing, stirring, drying;
(3) mixture that step (2) is obtained places in the vacuum tube furnace, take out furnace air after, feeding purity in the vacuum tube furnace with the flow of 20sccm is 99.99% argon gas, at 500 ℃ of reaction 5h down;
(4) be cooled to room temperature naturally after reaction is finished, washing, drying obtain the high-ratio surface grapheme material that volumetric capacitance increases.
The specific surface area of the grapheme material for preparing is 1587.3m
2/ g(measuring method is identical with embodiment 1).
Performance test:
Testing method is identical with embodiment 1, and the quality of the grapheme material that makes after tested is 101.2F/g than electric capacity, and volumetric capacitance is 50.1F/cm
3, energy density is 156.6Wh/cm
3, still can reach 95.8% of initial capacitance through 2000 circulation back electrical capacitys.
Comparative Examples
A kind of preparation method of graphene comprises the steps:
(1) gets the graphite oxide that the Staudenmaier method prepares, after microwave is peeled off, obtain the graphene oxide powder;
(2) the graphene oxide powder that obtains of weighing 3g step (1) and the KOH of 15g, fully mixing, stirring, drying;
(3) mixture that step (2) is obtained places in the vacuum tube furnace, take out furnace air after, feeding purity in the vacuum tube furnace with the flow of 20sccm is 99.99% argon gas, at 1200 ℃ of reaction 5h down;
(4) be cooled to room temperature naturally after reaction is finished, washing, drying obtain the high-ratio surface grapheme material that volumetric capacitance increases.
The specific surface area of the grapheme material for preparing is 2307.5m
2/ g(measuring method is identical with embodiment 1).
Performance test:
Testing method is identical with embodiment 1, and the quality of the grapheme material that makes after tested is 113F/g than electric capacity, and volumetric capacitance is 68.2F/cm
3, energy density is 213.1W h/cm
3, still can reach 95.5% of initial capacitance through 2000 circulation back electrical capacitys.
By embodiment 1～5 and Comparative Examples as can be seen, the grapheme material that the present invention prepares is guaranteeing under high-specific surface area and the high quality situation than electric capacity, improved the volumetric capacitance of grapheme material greatly, efficiently solved because the technical problem that the excessive Graphene that causes of volume can't be used in super capacitor on a large scale.
Applicant's statement, the present invention illustrates detailed process equipment of the present invention and technical process by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a Graphene is characterized in that, is doped with gac in the described Graphene lamella.
2. Graphene as claimed in claim 1, it is characterized in that, described gac is obtained by carbon source material activation back, described carbon source material is the combination of any a kind or at least 2 kinds in starch, wood chip, charcoal, coconut husk, coal, shell or refinery coke preferably, further preferred charcoal and/or refinery coke, preferred especially charcoal;
Preferably, described activation is high-temperature activation, and the temperature of described high-temperature activation is 500～1500 ℃, and preferred soak time is 0.5～5h.
3. Graphene as claimed in claim 1 or 2 is characterized in that, the specific surface area 〉=1500m of described Graphene
2/ g is preferably 1500～3000m
2/ g;
Preferably, be electrolytic solution with 1M TEABF4/PC, the quality of described grapheme material is 100～200F/g than electric capacity, volumetric capacitance is 50～120F/cm
3
4. one kind as the described preparation method of graphene of one of claim 1～3; it is characterized in that; described method is for fully to mix graphene oxide with activator, carbon source material; under protective atmosphere protection, carry out high-temperature activation, the Graphene that lower the temperature then, washing, drying obtains high volumetric capacitance.
5. method as claimed in claim 4 is characterized in that, described carbon source material is selected from the combination of any a kind or at least 2 kinds in starch, wood chip, charcoal, coconut husk, coal, shell or the refinery coke, preferred charcoal and/or refinery coke, further preferred charcoal;
Preferably, the addition of described carbon source material is 0.01～1 times of graphene oxide quality.
6. as claim 4 or 5 described methods, it is characterized in that described activator is the combination of any a kind or at least 2 kinds in potassium hydroxide, sodium hydroxide, phosphoric acid, salt of wormwood or the zinc chloride; Described activator is preferably potassium hydroxide;
Preferably, the interpolation quality of described activator is 1～15 times of graphene oxide quality, preferred 1～12 times, and further preferred 1～6 times;
Preferably, described graphene oxide is the product that graphite is peeled off after oxidation;
Preferably, the mode of described graphite oxidation adopts in Hummers method, Staudenmaier method or the Brodie method any a kind;
Preferably, the described mode of peeling off is selected from microwave and peels off the expand method of peeling off, ultra-sonic dispersion of method, pyrolysis and peel off method, electrostatic repulsion and peel off the combination that any a kind or at least 2 kinds in the method are peeled off in method or thermal reduction, preferred microwave is peeled off method, thermal reduction and is peeled off the combination that method or ball milling are peeled off any a kind or at least 2 kinds in the method, and further preferred microwave is peeled off method.
7. as the described method of one of claim 4～6, it is characterized in that described high-temperature activation temperature is 500-1500 ℃, preferred 600-1200 ℃, more preferably 800 ℃;
Preferably, described soak time is 0.5-5h, preferred 1-3h;
Preferably, described protective atmosphere is the combination of any a kind or at least 2 kinds in nitrogen, helium or argon gas preferably, further preferred nitrogen and/or argon gas, special preferred nitrogen;
Preferably, the feeding flow of described protective atmosphere is 20-200sccm, preferred 40-120sccm, further preferred 100sccm;
Preferably, described activation is carried out in vacuum tube furnace.
8. as the described method of one of claim 4～7, it is characterized in that described method comprises the steps:
(1) pre-treatment: with graphene oxide, carbon source material and activator according to mass ratio 1:(0.01～1): fully mix (1～15), drying;
(2) redox graphene and activating: the mixture of graphene oxide, carbon source material and the activator that step (1) is obtained is put into vacuum tube furnace, after taking out furnace air, feeding rare gas element in the vacuum tube furnace protects, be warming up to 600-1200 ℃, isothermal reaction 0.5-3h;
(3) aftertreatment: after reaction finishes, drop to room temperature in protection of inert gas, washing, drying obtain the Graphene of high volumetric capacitance.
9. a Graphene electrodes is characterized in that, described electrode materials is the described Graphene of one of claim 1-3;
Preferably, in the described Graphene electrodes utmost point material, the content of Graphene is 80～98wt%;
Preferably, the Graphene electrodes material that obtains when the PTFE emulsion preparation that with the mass ratio is one of the claim 1-3 that mixes of 95:5 described grapheme material and 60wt% still can reach more than 95% of initial capacitance through 2000 circulation back electrical capacitys in organic electrolyte.
10. purposes that is used for ultracapacitor, lithium ion battery or fuel cell aspect as Graphene as described in one of claim 1～3.
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