CN103366969A - Carbon-coated graphene, preparation method and application thereof - Google Patents
Carbon-coated graphene, preparation method and application thereof Download PDFInfo
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- CN103366969A CN103366969A CN2013102919923A CN201310291992A CN103366969A CN 103366969 A CN103366969 A CN 103366969A CN 2013102919923 A CN2013102919923 A CN 2013102919923A CN 201310291992 A CN201310291992 A CN 201310291992A CN 103366969 A CN103366969 A CN 103366969A
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- graphite alkene
- coated graphite
- graphene oxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 54
- 239000010439 graphite Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- -1 graphite alkene Chemical class 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 13
- 239000012190 activator Substances 0.000 claims description 11
- 238000002203 pretreatment Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 230000037452 priming Effects 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229930091371 Fructose Natural products 0.000 claims description 6
- 239000005715 Fructose Substances 0.000 claims description 6
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000012958 reprocessing Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229940072033 potash Drugs 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 2
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 2
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 14
- 230000003213 activating effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000001720 carbohydrates Chemical class 0.000 abstract 1
- 235000014633 carbohydrates Nutrition 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000004087 circulation Effects 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000003556 assay Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method for carbon-coated graphene. The preparation method includes the steps that after carbohydrates are fully mixed with oxidized graphene, an activating agent is added, the mixture is activated after being dried, and then the carbon-coated graphene is acquired. The sum of height specific surface areas of graphene materials is guaranteed, the density of the graphene is improved, then volume specific capacitance of the graphene is improved, and the technical problems that the graphene can not be used as an electrode material and applied to a super-capacitor due to small volume specific capacitance are solved. The carbon-coated graphene, the preparation method of the carbon-coated graphene and application of the carbon-coated graphene are simple in operation, low in cost, safe, reliable, small in pollution, high in production efficiency, low in cost, high in market competitiveness, wide in application prospect, and capable of being massively produced.
Description
Technical field
The invention belongs to preparation and the application of grapheme material, relate to a kind of carbon coated graphite alkene, preparation method and application thereof, the preparation method of described carbon coated graphite alkene is the dissolving of a kind of glucide and evenly is coated on the preparation of Graphene surface and has high-specific surface area, high-quality than the method for the Graphene of electric capacity and high volumetric capacitance.
Background technology
Graphene (Graphene) is that carbon atom is arranged the Colloidal particles that forms according to hexagonal.After 2004 were found by the scientist of University of Manchester, it just became the focus that scientific circles and industrial quarters are paid close attention to, particularly at the study hotspot that is energy field at the excellent properties of the aspects such as mechanics, calorifics, electricity, optics.Graphene has the specific area of super large, excellent conduction and higher electron mobility, and low thermal coefficient of expansion, and good chemical stability are considered to the optimal electrode material of ultracapacitor.
Ultracapacitor is a kind of Novel energy storage apparatus, and it has the characteristics such as charging interval weak point, long service life, good temp characteristic, energy savings and environmental protection, is widely used in various energy fields.Ultracapacitor is stored energy in isolated electric charge, and larger, the isolated electric charge of area that is used for stored charge is more intensive, and its capacitance is larger.Graphene has high specific area and high conductivity, so that Graphene has the more excellent character of other porous carbon materials as electrode material for super capacitor.But single Graphene is subject to the restriction of factors as electrode material, as reuniting easily between the lamella, causes the raising of the loss of irreversible capacity, and has reduced its conductance as electrode material.On the other hand because nano material generally has 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, Graphene for high-specific surface area, the size of bulk density has important impact to aspect performances such as the electricity of Graphene ultracapacitor, chemistry, it is lower how to develop a kind of cost, volumetric capacitance and energy density are high, the preparation method of the Graphene of good cycle 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 chemistry redox method or CVD method, the unit volume quality (bulk density) 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 that improves the Graphene volumetric capacitance is provided.Little for the Graphene volumetric capacitance, can't be applied to the problem of the 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 is to provide carbon coated graphite alkene and preparation method thereof, and the density of described carbon coated graphite alkene is larger, and volumetric capacitance is high, and cycle performance is better simultaneously.
The first aspect of one of purpose of the present invention is achieved by the following technical solution:
The preparation method of carbon coated graphite alkene of the present invention is: glucide with after graphene oxide fully mixes, is added activator, activate after drying, obtain carbon coated graphite alkene.
Described Graphene evenly coats by the glucide dissolving and on its surface, under the prerequisite that does not change Graphene character, effectively increases the density of Graphene.
The present invention is dissolved in the Graphene surface by glucide and evenly coats, and can effectively increase the density of Graphene, 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 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, the characteristics of stable cycle performance.
Preferably, described glucide is selected from the combination of any a kind or at least 2 kinds in sucrose, glucose, fructose, ribose or the shitosan, is preferably sucrose; The combination of the combination of described combination such as sucrose/glucose, the combination of fructose/shitosan, sucrose/glucose/shitosan etc., preferably sucrose.
The present invention is to by glucide dissolving and in the Graphene coated with uniform, and activating and reducing under the condition at high temperature, obtain the Graphene of the carbon coating of high-specific surface area, thereby so that the volumetric capacitance of prepared grapheme material measures large increase, so that relevant energy density also significantly improves.
The addition of glucide of the present invention is 0.01～1 times of graphene oxide quality, such as 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 coating layer is thicker, so that Graphene can not fully reduce, affects the quality of high volumetric capacitance Graphene than electric capacity and specific area; And the addition of glucide is too small, and the density of Graphene can not Effective Raise.
Activator of the present invention is selected from the combination of any a kind or at least 2 kinds in potassium hydroxide, NaOH, potash or the sodium carbonate, be preferably potassium hydroxide, the combination of the combination of described combination such as potassium hydroxide/NaOH, the combination of potash/NaOH, NaOH/potassium hydroxide/sodium carbonate etc.
The effect of activator of the present invention is to obtain the hole in the graphene sheet layer reaction, increases the specific area of Graphene.
Preferably, the interpolation quality of described activator is 1～12 times of graphene oxide quality, such as 2 times, 4 times, 7 times, 10 times, 11 times, 12 times etc., and preferred 1～10 times, further preferred 1～6 times.
The addition of activator of the present invention is too much, causes easily the excessive erosion of Graphene, lamella well damage, conductivity variation; Addition is very few, and the number in hole is less on the Graphene, affects the specific area of Graphene.
Graphene oxide of the present invention is that graphite is peeled off the product that obtains through oxidation.The step that the present invention peels off after to the method for graphite oxidation and oxidation is concrete the restriction not.
Preferably, preferred any a kind in Hummers method, Brodie method or Staudenmaier method of the mode of described graphite oxidation.
The Brodie method is at first with the HNO of being fuming
3Process 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 concentrated sulfuric acid and fuming nitric aicd mixed acid graphite powder to be processed, and equally also is with KClO
4Be oxidant.
The Hummers method is with graphite powder and anhydrous nitric acid sodium (NaNO
3) join the concentrated sulfuric acid that places in the ice bath, add KMnO under the strong stirring
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, then vacuum dehydration obtains.Resulting oxidized graphite flake layer has pleat beryllium type structure, and oxygen content is larger, and functional group is than horn of plenty, but in pure water fine dispersion.
Preferably, the described mode of peeling off 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, described combination such as microwave is peeled off the combination of peeling off with pyrolysis expansion, combination of peeling off with pyrolysis expansion etc. is peeled off in ultrasonic dispersion, the combination of any a kind or at least 2 kinds in preferred microwave stripping method, thermal reduction stripping method or the ball milling stripping method, further preferred microwave stripping method.
Preferably, described activation temperature is 600～1500 ℃, such as 602 ℃, 750 ℃, 880 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1450 ℃, 1500 ℃ etc., and preferred 600～1200 ℃, more preferably 800 ℃.
Preferably, described soak time is 0.5～5h, preferred 1～3h, such as 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 be not with other of the reaction such as graphene oxide, activator, glucide, 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, particularly 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, 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: mix with the glucide dissolving and with graphene oxide, add activator and fully mix drying;
(2) priming reaction: the mixture that step (1) obtains is put into vacuum tube furnace, take out furnace air after, in vacuum tube furnace, pass into protective gas protection, be warming up to activation temperature, carry out priming reaction;
(3) reprocessing: at the protective atmosphere borehole cooling, washing, drying obtains carbon coated graphite alkene.
As optional technical scheme, carbon coated graphite alkene preparation method of the present invention comprises the steps:
(1) pre-treatment: mix with the glucide dissolving and with graphene oxide, add potassium hydroxide and fully mix drying;
(2) priming reaction: the mixture that step (1) obtains is put into vacuum tube furnace, take out furnace air after, in vacuum tube furnace, pass into protective gas protection, be warming up to 600～1200 ℃, constant temperature 0.5～3h carries out priming reaction; The flow that passes into of described protective atmosphere is preferably 20～200sccm, further preferred 40～120sccm, particularly preferably 100sccm;
(3) reprocessing:, wash to room temperature at the protective atmosphere borehole cooling, drying obtains carbon coated graphite alkene.
The second aspect of one of purpose of the present invention provides a kind of carbon coated graphite alkene, and described carbon coated graphite alkene is prepared by the described method of first aspect.
The present invention is by the glucide dissolving and after the Graphene coated with uniform, activating and reducing under the high temperature, obtain the Graphene of the carbon coating of high-specific surface area, thereby so that the volumetric capacitance of prepared grapheme material measures large increase, so that relevant energy density also significantly improves.
Preferably, the specific area 〉=1200m of carbon coated graphite alkene of the present invention
2/ g, for example 1200m
2/ g, 1310m
2/ g, 1450m
2/ g, 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 1200～3000m
2/ g.
Preferably, with 1M TEABF
4/ PC is electrolyte, and the quality of described grapheme material is 100～200F/g than electric capacity, such as 104F/g, 120F/g, 130F/g, 150F/g, 180F/g, 190F/g, 197F/g etc., and volumetric capacitance is 50～130F/cm
3, 52F/cm for example
3, 90F/cm
3, 102F/cm
3, 107F/cm
3, 110F/cm
3, 130F/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 ultracapacitor, and the electrode material of described ultracapacitor is the described carbon coated graphite of one of purpose alkene.
Capacitance still can reach more than 95% of initial capacitance after described ultracapacitor circulated through 2000 times.
Ultracapacitor of the present invention is this area method of testings commonly used through the process of 2000 circulations, be typically: with the grapheme material for preparing and the PTFE(polytetrafluoroethylene of 60wt%) emulsion, be that the ratio of 95:5 is fully mixed according to mass ratio, then repeatedly roll-in is even through roll squeezer, and making diameter is the Graphene electrodes sheet of 13mm; Be dried to constant weight, assembling obtains testing behind the super capacitor.
The preparation technology of described Graphene electrodes, those skilled in the art can select according to the professional knowledge of oneself grasping, 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):
In the formula, C
pBe condenser capacity; C is capacitance; M is the quality of Activated Graphite alkene.
(unit is F/cm to volumetric capacitance of the present invention
3) computing formula as shown in the formula (II):
In the formula, C
vBe condenser capacity; C is capacitance; V is the quality of Activated Graphite alkene.
Three of purpose of the present invention provides a kind of lithium ion battery, and the negative material of described lithium ion battery is the described carbon coated graphite of one of purpose alkene;
Three of purpose of the present invention provides a kind of purposes that is used for ultracapacitor, lithium ion battery or fuel cell aspect such as carbon coated graphite alkene 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 large to utilize Graphene provided by the invention to develop capacitance, the super capacitor that volume is little.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention guarantee the 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 and be applied to the technical barrier of ultracapacitor for electrode material;
(2) the present invention is simple to operate, cost is low, and is safe and reliable, pollutes fewly, and production efficiency is high, and cost is low, can large-scale production, have the very strong market competitiveness and application prospect widely.
Description of drawings
Fig. 1 is the SEM figure of the described carbon coated graphite of one embodiment of the present invention alkene;
Fig. 2 is the cyclic voltammetry curve of Graphene electrodes in 1M TEABF4/PC electrolyte that embodiment 1 makes;
Fig. 3 is the constant current charge-discharge time graph of the super capacitor that makes of embodiment 1;
Fig. 4 is the cyclic voltammetry curve of Graphene electrodes in 1M TEABF4/PC electrolyte that embodiment 2 makes;
Fig. 5 is the constant current charge-discharge time graph of the super capacitor that makes of embodiment 2;
Fig. 6 is the cyclic voltammetry curve of Graphene electrodes in 1M TEABF4/PC electrolyte that embodiment 3 makes;
Fig. 7 is the constant current charge-discharge time graph of the super capacitor that makes of 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 preparation method of carbon coated graphite alkene comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Hummers legal system, after microwave is peeled off, obtain the graphene oxide powder, for subsequent use; Weighing 1g sucrose is dissolved in fully dissolving in the 100mL deionized water, adds 3g graphene oxide powder and stirs 5h, then adds the KOH of 15g, fully mixing, stirring, drying;
(2) mixture that step (1) is obtained places in the vacuum tube furnace, take out furnace air after, passing into purity in the vacuum tube furnace with the flow of 100sccm is 99.99% argon gas, at 800 ℃ of lower reaction 2h;
(3) naturally be cooled to room temperature after reaction is finished, washing, drying obtain the carbon coated graphite alkene material that volumetric capacitance increases.Fig. 1 is the SEM figure processed of embodiment 1 described carbon coated graphite alkene;
The specific area of the grapheme material for preparing is 1250m
2/ g(adopts U.S.'s health tower specific area and pore analysis instrument NOVA2000e to carry out specific area measuring).
Performance test:
Preparation Graphene electrodes sheet: with the grapheme material for preparing and the PTFE(polytetrafluoroethylene of 60wt%) emulsion is that the ratio of 95:5 is fully mixed according to mass ratio; Then repeatedly roll-in is even through roll squeezer, and making diameter is the Graphene electrodes sheet of 13mm;
The Graphene electrodes sheet for preparing is put into the vacuum drying chamber inner drying to constant weight, and then assembling obtains super capacitor;
With 1M TEABF
4/ PC utilizes electrochemical workstation to carry out electrochemical property test as electrolyte, and Fig. 2 is that the Graphene electrodes that makes of embodiment 1 is at 1M TEABF
4Cyclic voltammetry curve in the/PC electrolyte; Fig. 3 is the constant current charge-discharge time graph of the super capacitor that makes of embodiment 1; The quality of the grapheme material that makes after tested is 189F/g than electric capacity, and volumetric capacitance is 120F/cm
3, energy density is 375Wh/cm
3, still can reach 98% of initial capacitance through capacitance after 2000 circulations.
Embodiment 2:
A kind of preparation method of carbon coated graphite alkene comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Hummers legal system, after microwave is peeled off, obtain the graphene oxide powder, for subsequent use; Weighing 2g glucose is dissolved in fully dissolving in the 100mL deionized water, adds 3g graphene oxide powder and stirs 10h, then adds the KOH of 18g, fully mixing, stirring, drying;
(2) mixture that step (1) is obtained places in the vacuum tube furnace, take out furnace air after, passing into purity in the vacuum tube furnace with the flow of 100sccm is 99.99% argon gas, at 900 ℃ of lower reaction 1h;
(3) naturally be cooled to room temperature after reaction is finished, washing, drying obtain the carbon coated graphite alkene material that volumetric capacitance increases.
The specific area of the grapheme material for preparing is 2590m
2/ 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 1MTEABF
4Cyclic voltammetry curve in the/PC electrolyte; Fig. 5 is the constant current charge-discharge time graph of the super capacitor that makes of embodiment 2; The quality of the grapheme material that makes after tested is 150F/g than electric capacity, and volumetric capacitance is 92F/cm
3, energy density is 288Wh/cm
3, still can reach 95% of initial capacitance through capacitance after 2000 circulations.
Embodiment 3:
A kind of preparation method of carbon coated graphite alkene comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Hummers legal system, after microwave is peeled off, obtain the graphene oxide powder, for subsequent use; Weighing 0.5g fructose is dissolved in fully dissolving in the 100mL deionized water, adds 3g graphene oxide powder and stirs 15h, then adds the KOH of 12g, fully mixing, stirring, drying;
(2) mixture that step (1) is obtained places in the vacuum tube furnace, take out furnace air after, passing into purity in the vacuum tube furnace with the flow of 100sccm is 99.99% argon gas, at 1000 ℃ of lower reaction 1.5h;
(3) naturally be cooled to room temperature after reaction is finished, washing, drying obtain the carbon coated graphite alkene material that volumetric capacitance increases.
The specific area of the grapheme material for preparing is 2995m
2/ 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 1MTEABF
4Cyclic voltammetry curve in the/PC electrolyte; Fig. 7 is the constant current charge-discharge time graph of the super capacitor that makes of embodiment 3; The quality of the grapheme material that makes after tested is 120F/g than electric capacity, and volumetric capacitance is 65F/cm
3, energy density is 203Wh/cm
3, still can reach 96% of initial capacitance through capacitance after 2000 circulations.
Embodiment 4:
A kind of preparation method of carbon coated graphite alkene comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Brodie legal system, after microwave is peeled off, obtain the graphene oxide powder, for subsequent use; Weighing 3g shitosan is dissolved in fully dissolving in the 100mL deionized water, adds 3g graphene oxide powder and stirs 10h, then adds the KOH of 9g and the mixture of 6gNaOH, fully mixing, stirring, drying;
(2) mixture that step (1) is obtained places in the vacuum tube furnace, take out furnace air after, passing into purity in the vacuum tube furnace with the flow of 20sccm is 99.99% argon gas, at 1500 ℃ of lower reaction 0.5h;
(3) naturally be cooled to room temperature after reaction is finished, washing, drying obtain the carbon coated graphite alkene material that volumetric capacitance increases.
The specific area of the grapheme material for preparing is 2820m
2/ 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 that makes after tested is 199F/g than electric capacity, and volumetric capacitance is 129/cm
3, energy density is 403Wh/cm
3, still can reach 97% of initial capacitance through capacitance after 2000 circulations.
Embodiment 5:
A kind of preparation method of carbon coated graphite alkene comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Staudenmaier legal system, after microwave is peeled off, obtain the graphene oxide powder, for subsequent use; Weighing 0.1g fructose is dissolved in fully dissolving in the 100mL deionized water, adds 3g graphene oxide powder and stirs 2h, then adds the NaOH of 18g, fully mixing, stirring, drying;
(2) mixture that step (1) is obtained places in the vacuum tube furnace, take out furnace air after, passing into purity in the vacuum tube furnace with the flow of 20sccm is 99.99% argon gas, at 600 ℃ of lower reaction 5h;
(3) naturally be cooled to room temperature after reaction is finished, washing, drying obtain the high-ratio surface grapheme material that volumetric capacitance increases.
The specific area of the grapheme material for preparing is 1512m
2/ 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 that makes after tested is 100F/g than electric capacity, and volumetric capacitance is 51F/cm
3, energy density is 159Wh/cm
3, still can reach 95% of initial capacitance through capacitance after 2000 circulations.
Embodiment 6:
A kind of preparation method of carbon coated graphite alkene comprises the steps:
(1) pre-treatment: get the standby graphite oxide of Staudenmaier legal system, after microwave is peeled off, obtain the graphene oxide powder, for subsequent use; Weighing 0.1g fructose is dissolved in fully dissolving in the 100mL deionized water, adds 10g graphene oxide powder and stirs 2h, then adds the NaOH of 120g, fully mixing, stirring, drying;
(2) mixture that step (1) is obtained places in the vacuum tube furnace, take out furnace air after, passing into purity in the vacuum tube furnace with the flow of 20sccm is 99.99% argon gas, at 700 ℃ of lower reaction 1h;
(3) naturally be cooled to room temperature after reaction is finished, washing, drying obtain the high-ratio surface grapheme material that volumetric capacitance increases.
The specific area of the grapheme material for preparing is 2290m
2/ 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 that makes after tested is 120F/g than electric capacity, and volumetric capacitance is 55F/cm
3, energy density is 172Wh/cm
3, still can reach 95% of initial capacitance through capacitance after 2000 circulations.
Can be found out by embodiment 1～6, the grapheme material that the present invention prepares is guaranteeing in high-specific surface area and the high-quality situation than electric capacity, greatly improved the volumetric capacitance of grapheme material, 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 and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.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 auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the preparation method of a carbon coated graphite alkene is characterized in that, described method for glucide with after graphene oxide fully mixes, the adding activator activates after drying, obtains carbon coated graphite alkene.
2. the method for claim 1 is characterized in that, described glucide is selected from the combination of any a kind or at least 2 kinds in sucrose, glucose, fructose, ribose or the shitosan, is preferably sucrose;
Preferably, the addition of described glucide is 0.01～1 times of graphene oxide quality.
3. method as claimed in claim 1 or 2 is characterized in that, described activator is selected from the combination of any a kind or at least 2 kinds in potassium hydroxide, NaOH, potash or the sodium carbonate, is preferably potassium hydroxide;
Preferably, the interpolation quality of described activator is 1～12 times of graphene oxide quality, preferred 1～10 times, and further preferred 1～6 times.
4. such as the described method of one of claim 1～3, it is characterized in that described graphene oxide is that graphite is peeled off the product that obtains through oxidation;
Preferably, preferred any a kind in Hummers method, Brodie method or Staudenmaier method of the mode of described graphite oxidation;
Preferably, the described mode of peeling off 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, the combination of any a kind or at least 2 kinds in preferred microwave stripping method, thermal reduction stripping method or the ball milling stripping method, further preferred microwave stripping method.
5. such as the described method of one of claim 1～4, it is characterized in that described activation temperature is 600～1500 ℃, preferred 600～1200 ℃, more preferably 800 ℃;
Preferably, described soak time is 0.5～5h, preferred 1～3h;
Preferably, described activation is carried out in protective atmosphere, and 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, particularly preferably nitrogen;
Preferably, described activation is carried out in vacuum tube furnace.
6. such as the described method of one of claim 1～5, it is characterized in that described method comprises the steps:
(1) pre-treatment: mix with the glucide dissolving and with graphene oxide, add activator and fully mix drying;
(2) priming reaction: the mixture that step (1) obtains is put into vacuum tube furnace, take out furnace air after, in vacuum tube furnace, pass into protective gas protection, be warming up to activation temperature, carry out priming reaction;
(3) reprocessing: at the protective atmosphere borehole cooling, washing, drying obtains carbon coated graphite alkene;
Preferably, described method comprises the steps:
(1) pre-treatment: mix with the glucide dissolving and with graphene oxide, add potassium hydroxide and fully mix drying;
(2) priming reaction: the mixture that step (1) obtains is put into vacuum tube furnace, take out furnace air after, in vacuum tube furnace, pass into protective gas protection, be warming up to 600～1200 ℃, constant temperature 0.5～3h carries out priming reaction; The flow that passes into of described protective atmosphere is preferably 20～200sccm, further preferred 40～120sccm, particularly preferably 100sccm;
(3) reprocessing:, wash to room temperature at the protective atmosphere borehole cooling, drying obtains carbon coated graphite alkene.
7. a carbon coated graphite alkene is characterized in that, described carbon coated graphite alkene is by preparing such as the described method of one of claim 1～6.
8. carbon coated graphite alkene as claimed in claim 7 is characterized in that the specific area 〉=1200m of described Graphene
2/ g is preferably 1200～3000m
2/ g;
Preferably, with 1M TEABF
4/ PC is electrolyte, and the quality of described grapheme material is 100～200F/g than electric capacity, and volumetric capacitance is 50～130F/cm
3
9. a ultracapacitor is characterized in that, the electrode material of described ultracapacitor is claim 7 or 8 described carbon coated graphite alkene;
Preferably, capacitance still can reach more than 95% of initial capacitance after described ultracapacitor circulated through 2000 times.
10. purposes that is used for ultracapacitor, lithium ion battery or fuel cell aspect such as carbon coated graphite alkene as described in claim 7 or 8.
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