CN106653379A - Lasagna nano graphene and preparation method and application thereof - Google Patents
Lasagna nano graphene and preparation method and application thereof Download PDFInfo
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- CN106653379A CN106653379A CN201610892075.4A CN201610892075A CN106653379A CN 106653379 A CN106653379 A CN 106653379A CN 201610892075 A CN201610892075 A CN 201610892075A CN 106653379 A CN106653379 A CN 106653379A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- 239000007772 electrode material Substances 0.000 claims abstract description 24
- 239000003990 capacitor Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 46
- 235000008429 bread Nutrition 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 26
- 239000012159 carrier gas Substances 0.000 claims description 15
- 230000008961 swelling Effects 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011229 interlayer Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 238000009825 accumulation Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 150000001720 carbohydrates Chemical class 0.000 claims description 7
- 235000014633 carbohydrates Nutrition 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- -1 oxygen hydrocarbon Chemical class 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000003209 petroleum derivative Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 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 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- FRYDSOYOHWGSMD-UHFFFAOYSA-N [C].O Chemical compound [C].O FRYDSOYOHWGSMD-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 5
- 238000007906 compression Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- 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
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- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a lasagna nano graphene and a preparation method and application thereof. The graphene has a diameter of 50 to 300 nm and a thickness of 1/5 to 1/2 of the diameter. Small graphene sheets are vertically supported between slice layers, and the spacing between the slice layers is 0.7 to 1 nm. The preparation method comprises the steps of first, preparing nano slice layered precursor, and then performing high-temperature roasting to generate a porous pie oxide template; and after carbon deposition under a high temperature, removing the oxide template and conducting drying. The preparation method has the characteristics of simple operation, high yield, low cost and easy expansion. The performance advantage lies in that when a large amount of lasagna nano graphenes are stacked, the lasagna nano graphenes are anti-compression and hard to overlap, and the stacked structure is not easy to swell by an electrolyte. The lasagna nano graphene is suitable for use as an electrode material of a super capacitor under high voltage, and has the characteristics of having a high energy density per unit area and being not easy to attenuate.
Description
Technical field
The invention belongs to technical field of graphene, is related to a kind of multi-layer steamed bread shape nano-graphene and preparation method thereof and answers
With.
Background technology
Ultracapacitor is a kind of equipment of the capacitance principle energy storage of utilization electrochemistry, high with power density, using the longevity
The long advantage of life, can serve as the storage (such as wind energy and tide energy) of erratic current, and Large-sized Communication instrument (such as steamer or
Aircraft) standby lighting power supply, it is also possible to the tune peak function for making battery is used.But compared with lithium ion battery, super capacitor
The energy density of device is than relatively low, in terms of some such as small volumes, the vehicles and mobile electronic device of heavyweight application
It is restricted.
Ultracapacitor is mainly made up of parts such as electrode material, electrolyte, barrier film and Collective Flow and packaging shells, wherein
Electrode material is crucial.The electrode material that can be used for the capacitor of 3～4V at present be the CNT or Graphene of pure carbon or
Thin layer graphite etc..The Graphene obtained by chemical vapour deposition technique or thin layer graphite, its oxygen content is low, easy removal, be expected to 3～
Applied in the capacitor of 4V.
But graphite or Graphene are usually the planar materials of two dimension, when a large amount of electrode materials are assembled, easily overlap, lose
Specific surface area and suitable aperture, cause the wettability power of electrolyte low, and performance is difficult to play.Prepare the Graphene of Wrinkled, shell
Shape Graphene solves the problems, such as overlapping when can partly pile up.But these structures yet suffer from the relatively large problem of superposed surfaces,
So yet suffer from losing the shortcoming of part specific surface area and aperture.Also there is the multistage three-dimensional structure of patent report Graphene
(such as fibrous heap collective, cap-like structure heap collective, sheet heap collective), preferably solves the problems, such as overlapping.But due to its structure
Symmetry is poor, when compacting forms electrode slice, can leave hole, causes bulk density to be difficult to improve.It is simultaneously such to pile up knot
Structure is easily swelling by electrolyte so that carbon nanomaterial disperses everywhere in the devices, and having causes lug short circuit.Meanwhile, before template
The yield of the Graphene of method growth is high not enough, causes its cost to remain high.
The content of the invention
Above-mentioned in order to overcome the shortcomings of current technology, the present invention proposes a kind of multi-layer steamed bread shape nano-graphene and its preparation side
Method and application, using new template method multi-layer steamed bread shape nano-graphene is prepared, with meet engineering processing requirement with it is further
The requirement of reduces cost.
The present invention is to be achieved through the following technical solutions：
A kind of multi-layer steamed bread shape nano-graphene, a diameter of 50～300nm, thickness is the 1/5～1/2 of diameter, and piece interlayer has
Little graphene film vertical support, sheet interlayer spacing is 0.7～1nm, and specific surface area is 800～2000m2/g。
Described multi-layer steamed bread shape nano-graphene, be by carbon source at 800～1100 DEG C on porous pie template surface
Graphene is cracked to form, then obtained from porous pie template is dissolved.
Density is compressed into for 300～600kg/m3Accumulation body, it is its 2～20 times that the accumulation body is placed into quality
In ionic liquid, swelling ratio is less than 3% in 3h, and swelling ratio is less than 50% in 20h.
Using multi-layer steamed bread shape nano-graphene as electrode material, in the case where operating voltage is 3.5～4V, using ionic liquid electricity
Solution liquid, is 160～220F/g based on the capacitive property of the electrode material of monodisperse status；
Multi-layer steamed bread shape nano-graphene is encapsulated into capacitor as electrode material, its quality is controlled for device quality
When 20%, the capacitive property based on electrode material is 130～150F/g.
A kind of preparation method of multi-layer steamed bread shape nano-graphene, including following operation：
1) using the one kind in the kaolin of 5～100nm nano-sheets, hydrocarbonate of magnesia, basic magnesium carbonate, alumina silicate or
Various, 0.2～3h in solution of the immersion containing 0.1～1mol/L carbohydrate is compacted sediment after filtration, obtains nanometer sheet
Stratiform presoma；
2) nanometer sheet stratiform presoma is placed in reactor, 0.2～3h of roasting at 200～950 DEG C, while be passed through containing
Carrier of oxygen or carbon dioxide containing gas, form porous pie oxide template；
Then the gas being passed through is switched into inert gas, and is passed through the carbon source carried by carrier gas；Temperature adjustment is to 800～1100
DEG C, carbon source is cracked to form Graphene on porous pie template surface, and logical carbon source is stopped after 0.2～4h of reaction, treats that it is naturally cold
But；
3) there is the porous pie template of Graphene acid or alkaline solution dissolving deposition, multi-layer steamed bread is obtained after separation
Shape nano-graphene, is dried after it is fully washed.
The solution of described carbohydrate is one or more in glucose, starch, cellulose；Described sediment
It is to be compacted under the pressure of 5～40MPa using tablet press machine, measures nanometer sheet stratiform presoma.
Oxygen purity is 0.5～100% in described oxygen-containing gas, and remaining is nitrogen；In carbon dioxide containing gas
Carbon dioxide volume fraction is 1～20%, and remaining is nitrogen.
Described carbon source is C1～C15Petroleum hydrocarbon, halogenated hydrocarbons, oxygen hydrocarbon and nitrogen hydrocarbon in one or more；Carrier gas is hydrogen
One or more in gas, argon gas, nitrogen or helium, carbon source is 1 with the volume ratio of carrier gas:0.1～1:20；Carbon source air speed is:
0.2～1.5g/g/h.
It is described after the completion of carbon source is passed through, the Graphene being deposited in porous pie oxide mould agent be its quality 6～
30%.
Hydrochloric acid or the sulfuric acid will deposit the porous pie template dissolving for having Graphene；
Or will deposit the porous pie template dissolving for having Graphene with NaOH or potassium hydroxide solution.
Application of the described multi-layer steamed bread shape nano-graphene in electrode material is prepared.
Compared with prior art, the present invention has following beneficial technique effect：
The multi-layer steamed bread shape nano-graphene that the present invention is provided, with the big and thin feature of piece, piece interlayer has little graphene film
Vertical support, when electrode slice is pressed into, is better able to solid matter, and space is little between piece and piece, both beneficial to raising bulk density, and
Beneficial to the electrode slice improved after compacting stability (not swelling) in the electrolytic solution.Compared with existing graphene product, make
Obtaining the probability of shorted devices reduces by 90%.
The multi-layer steamed bread shape nano-graphene preparation method that the present invention is provided, prepares first nanometer sheet stratiform presoma, then
High-temperature roasting is carried out, cellular cake oxide template is generated；The carbon distribution under high temperature, after by oxide template remove, be dried and
.Preparation method has the characteristics of simple to operate, high income, easy amplification with low cost.
The multi-layer steamed bread shape nano-graphene preparation method that the present invention is provided, cheap carbohydrate is adsorbed in nanometer sheet
Interlayer, is used as the method for preparing foraminous die plate agent, with inexpensive efficient feature, than existing other alcohols template cost drops
It is low by 20～50%；Carbohydrate portions are extruded out in pressing process, contribute to forming the connection of nanoscale twins, so as to
During growth Graphene, the graphite flake for having part vertical in lamella separates lamella, serves the specific surface area for ensureing that Graphene is big
And the effect do not reunited.Than the method low cost 30～50% of meticulous Control architecture pore structure；Because carbohydrate is for front
The special role of body is driven, the activity of foraminous die plate agent can be increased, the yield of final multi-layer steamed bread nano-graphene is made, than former stone
Black alkene improves 50～100%, and therefore preparation cost reduces by 20～50%.
The multi-layer steamed bread shape nano-graphene that the present invention is provided suitably does the electrode material of ultracapacitor under high voltage, has
Unit area energy storage density is high, is difficult the characteristics of decaying.Its performance advantage is incompressible when being bulk deposition, is difficult to overlap, heap
Product structure is difficult swelling by electrolyte.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The multi-layer steamed bread shape nano-graphene that the present invention is provided, is prepared by following operation：
1) using the one kind in the kaolin of 5～100nm nano-sheets, hydrocarbonate of magnesia, basic magnesium carbonate, alumina silicate or
Various, 0.2～3h in solution of the immersion containing 0.1～1mol/L carbohydrate is compacted sediment after filtration, obtains nanometer sheet
Stratiform presoma；
2) nanometer sheet stratiform presoma is placed in reactor, 0.2～3h of roasting at 200～950 DEG C, while be passed through containing
Carrier of oxygen or carbon dioxide containing gas, form porous pie oxide template；
Then the gas being passed through is switched into inert gas, and is passed through the carbon source carried by carrier gas；Temperature adjustment is to 800～1100
DEG C, carbon source is cracked to form Graphene on porous pie template surface, and logical carbon source is stopped after 0.2～4h of reaction, treats that it is naturally cold
But；
3) there is the porous pie template of Graphene acid or alkaline solution dissolving deposition, multi-layer steamed bread is obtained after separation
Shape nano-graphene, is dried after it is fully washed.
Specific embodiment and the detection of corresponding multi-layer steamed bread shape nano-graphene capacitive property is given below.
Embodiment 1
The preparation of multi-layer steamed bread shape nano-graphene, including following operation：
The use of thickness is the kaolin of 5nm nano-sheets, immerses 3h in 0.1mol/L D/Ws, after filtration, profit
It is compacted under the pressure of 40MPa with tablet press machine.
By above-mentioned product, in being placed in reactor, it is passed through oxygen-containing gas (oxygen purity is 0.5%, and remaining is nitrogen)
The roasting 1h at 550 DEG C.Easily decompose composition effusion in above-mentioned product, surplus materials forms porous pie oxide template；Then
The gas being passed through is switched into argon gas, carbon source (C is passed through8～C15Petroleum hydrocarbon) and carrier gas (mixture of hydrogen and argon gas, volume ratio
For 1:0.6).Carbon source air speed is 1.5g/g/h, and carbon source is 1 with the volume ratio of carrier gas:0.1, carbon source at 1000 DEG C, in porous cake
Shape template surface is cracked to form Graphene；After reaction 0.2h, stop logical carbon source.
There is the porous pie template (mass fraction of Graphene is 6%) of Graphene molten deposition with sodium hydroxide solution
Solution, gained multi-layer steamed bread shape nano-graphene product with deionized water is washed 5 times, through conventional drying, finally gives product.
After testing, the prepared a diameter of 300nm of multi-layer steamed bread shape nano-graphene, thickness is the 1/5 of diameter, and piece interlayer has
Little graphene film vertical support, sheet interlayer spacing is 0.7nm.Specific surface area is 1200m2/g。
It is 300kg/m when density is compressed into the pressure of 5MPa3Accumulation body.It is it that the accumulation body is put to quality
In 2 times of ionic liquid (such as EMIBF4), swelling ratio is less than 3% in 3h, and swelling ratio is less than 50% in 20h.
In the case where operating voltage is 3.5V, using il electrolyte, the electric capacity based on the electrode material of monodisperse status
Performance is 160F/g.Be encapsulated into capacitor, control its quality be device quality 20% when, the electric capacity based on electrode material
Performance is 130F/g.
Embodiment 2
The preparation of multi-layer steamed bread shape nano-graphene, including following operation：
The use of thickness is the hydrocarbonate of magnesia of 100nm nano-sheets, immerses 3h in 1mol/L amidins, after filtration,
It is compacted under the pressure of 5MPa using tablet press machine.
By above-mentioned product, in being placed in reactor, it is passed through oxygen-containing gas (oxygen purity is 100%) and roasts at 200 DEG C
Burn 0.2h.Easily decompose composition effusion in above-mentioned product, surplus materials forms porous pie oxide template；Then gas is switched
For argon gas, carbon source (C is passed through1～C7Petroleum hydrocarbon) (mixture of hydrogen and nitrogen, volume ratio is 1 with carrier gas:4).Carbon source air speed is
0.5g/g/h, carbon source is 1 with the volume ratio of carrier gas:2, carbon source is cracked to form stone at 900 DEG C on porous pie template surface
Black alkene.After reaction 4h, stop logical carbon source.
Porous pie template (mass fraction of Graphene the is 30%) dissolving for having Graphene will be deposited with hydrochloric acid, by institute
Obtain multi-layer steamed bread shape nano-graphene product with deionized water to wash 5 times, through conventional drying, finally give product.
The prepared a diameter of 50nm of multi-layer steamed bread shape nano-graphene, thickness is the 1/2 of diameter, and piece interlayer has little Graphene
Piece vertical support, sheet interlayer spacing is 1nm.Specific surface area is 2000m2/g。
It is 600kg/m when density is compressed into the pressure of 5MPa3Accumulation body.It is it that the accumulation body is put to quality
20 times of ionic liquid is (such as EMIBF4) in, swelling ratio is less than 3% in 3h, and swelling ratio is less than 50% in 20h.
In the case where operating voltage is 4V, using il electrolyte (such as EMIBF4), the electrode material based on monodisperse status
The capacitive property of material is 200F/g.Be encapsulated into capacitor, control its quality be device quality 20% when, based on electrode material
The capacitive property of material is 150F/g.
Embodiment 3
The preparation of multi-layer steamed bread shape nano-graphene, including following operation：
The use of thickness is the basic magnesium carbonate of 20nm nano-sheets, immerses 1h in 0.5mol/L cellulose aqueous solutions, filter
Afterwards, it is compacted under the pressure of 25MPa using tablet press machine.
By above-mentioned product, in being placed in reactor, it is passed through containing CO2Gas (CO2Volume fraction is 20%, and remaining is nitrogen)
Roasting 3h at 950 DEG C.Easily decompose composition effusion in above-mentioned product, surplus materials forms porous pie oxide template.Then will
Gas switches to argon gas, is passed through carbon source (mixture of dichloro-benzenes and expoxy propane, mass ratio 1:1) with carrier gas (helium and nitrogen
Mixture, volume ratio is 1:1).Carbon source air speed is 1g/g/h, and carbon source is 1 with the volume ratio of carrier gas:0.5, carbon source is at 800 DEG C
Under, it is cracked to form Graphene on porous pie template surface.After reaction 1h, stop logical carbon source.
Porous pie template (mass fraction of Graphene the is 25%) dissolving for having Graphene will be deposited with sulfuric acid, by institute
Obtain multi-layer steamed bread shape nano-graphene product with deionized water to wash 5 times, through conventional drying, finally give product.
The prepared a diameter of 200nm of multi-layer steamed bread shape nano-graphene, thickness is the 1/3 of diameter, and piece interlayer has little graphite
Alkene piece vertical support, sheet interlayer spacing is 0.8nm.Specific surface area is 800m2/g。
It is 500kg/m when density is compressed into the pressure of 5MPa3Accumulation body.It is it that the accumulation body is put to quality
In 20 times of ionic liquid (such as EMIBF4), swelling ratio is less than 3% in 3h, and swelling ratio is less than 50% in 20h.
In the case where operating voltage is 4V, using il electrolyte, the capacitive character based on the electrode material of monodisperse status
Can be 180F/g.Be encapsulated into capacitor, control its quality be device quality 20% when, the capacitive character based on electrode material
Can be 140F/g.
Embodiment 4
The preparation of multi-layer steamed bread shape nano-graphene, including following operation：
The use of thickness is the alumina silicate of 60nm nano-sheets, immerses 2h in 0.5mol/L D/Ws, after filtration, profit
It is compacted under the pressure of 20MPa with tablet press machine.
By above-mentioned product, in being placed in reactor, it is passed through containing CO2Gas (oxygen purity is 1%, and remaining is nitrogen) exists
Roasting 1.5h at 750 DEG C.Easily decompose composition effusion in above-mentioned product, surplus materials forms porous pie oxide template.Then
Gas is switched into argon gas, carbon source (mixture of chloroform, isopropanol and dimethylformamide, mass ratio 0.1 is passed through:1：0.5)
(mixture of helium and nitrogen, volume ratio is 1 with carrier gas:5).Carbon source air speed is the volume ratio of 0.2g/g/h, carbon source and carrier gas
For 1:20, carbon source is cracked to form Graphene at 850 DEG C on porous pie template surface.After reaction 2h, stop logical carbon source.
The porous pie template for having Graphene will be deposited with potassium hydroxide solution (mass fraction of Graphene is 20%)
Dissolving, gained multi-layer steamed bread shape nano-graphene product with deionized water is washed 5 times, through conventional drying, finally gives product.
The prepared a diameter of 150nm of multi-layer steamed bread shape nano-graphene, thickness is the 1/4 of diameter, and piece interlayer has little graphite
Alkene piece vertical support, sheet interlayer spacing is 0.9nm.Specific surface area is 1650m2/g。
It is 550kg/m when density is compressed into the pressure of 5MPa3Accumulation body.It is it that the accumulation body is put to quality
10 times of ionic liquid is (such as EMIBF4) in, swelling ratio is less than 3% in 3h, and swelling ratio is less than 40% in 20h.
In the case where operating voltage is 4V, using il electrolyte (such as EMIBF4), the electrode material based on monodisperse status
The capacitive property of material is 165F/g.Be encapsulated into capacitor, control its quality be device quality 20% when, based on electrode material
The capacitive property of material is 135F/g.
Example given above is to realize the present invention preferably example, the invention is not restricted to above-described embodiment.This area
Technical staff any nonessential addition, the replacement made according to the technical characteristic of technical solution of the present invention, belong to this
The protection domain of invention.
Claims (10)
1. a kind of multi-layer steamed bread shape nano-graphene, it is characterised in that its a diameter of 50～300nm, thickness is the 1/5～1/ of diameter
2, sheet interlayer spacing is 0.7～1nm, and piece interlayer has little graphene film vertical support, and specific surface area is 800～2000m2/g。
2. multi-layer steamed bread shape nano-graphene as claimed in claim 1, it is characterised in that be by carbon source at 800～1100 DEG C
Graphene is cracked to form on porous pie template surface, then obtained from porous pie template is dissolved.
3. multi-layer steamed bread shape nano-graphene as claimed in claim 1, it is characterised in that it is compressed into density for 300～
600kg/m3Accumulation body, it is that swelling ratio is less than in 3h in its 2～20 times ionic liquid that the accumulation body is placed into quality
3%, swelling ratio is less than 50% in 20h.
4. multi-layer steamed bread shape nano-graphene as claimed in claim 1, it is characterised in that using multi-layer steamed bread shape nano-graphene as
Electrode material, the electrode material in the case where operating voltage is 3.5～4V, using il electrolyte, based on monodisperse status
Capacitive property is 160～220F/g；
Multi-layer steamed bread shape nano-graphene is encapsulated into capacitor as electrode material, its quality is controlled for the 20% of device quality
When, the capacitive property based on electrode material is 130～150F/g.
5. a kind of preparation method of multi-layer steamed bread shape nano-graphene, it is characterised in that including following operation：
1) using one kind in the kaolin of 5～100nm nano-sheets, hydrocarbonate of magnesia, basic magnesium carbonate, alumina silicate or many
Kind, 0.2～3h in solution of the immersion containing 0.1～1mol/L carbohydrate is compacted sediment after filtration, obtains nanoscale twins
Shape presoma；
2) nanometer sheet stratiform presoma is placed in reactor, 0.2～3h of roasting at 200～950 DEG C, while being passed through oxygenous
Body or carbon dioxide containing gas, form porous pie oxide template；
Then the gas being passed through is switched into inert gas, and is passed through the carbon source carried by carrier gas；Temperature adjustment to 800～1100 DEG C,
Carbon source is cracked to form Graphene on porous pie template surface, and logical carbon source is stopped after 0.2～4h of reaction, treats its natural cooling；
3) there is the porous pie template of Graphene acid or alkaline solution dissolving deposition, multi-layer steamed bread shape is obtained after separation and is received
Rice Graphene, is dried after it is fully washed.
6. the preparation method of multi-layer steamed bread shape nano-graphene as claimed in claim 5, it is characterised in that described carbon hydrate
The solution of thing is one or more in glucose, starch, cellulose；Described sediment is in 5～40MPa using tablet press machine
Pressure under be compacted, measure nanometer sheet stratiform presoma.
7. the preparation method of multi-layer steamed bread shape nano-graphene as claimed in claim 5, it is characterised in that described oxygen-containing gas
Middle oxygen purity is 0.5～100%, and remaining is nitrogen；In carbon dioxide containing gas carbon dioxide volume fraction be 1～
20%, remaining is nitrogen.
8. the preparation method of multi-layer steamed bread shape nano-graphene as claimed in claim 5, it is characterised in that described carbon source is C1
～C15Petroleum hydrocarbon, halogenated hydrocarbons, oxygen hydrocarbon and nitrogen hydrocarbon in one or more；Carrier gas is in hydrogen, argon gas, nitrogen or helium
Plant or various, carbon source is 1 with the volume ratio of carrier gas:0.1～1:20；Carbon source air speed is:0.2～1.5g/g/h.
9. the preparation method of multi-layer steamed bread shape nano-graphene as claimed in claim 5, it is characterised in that be passed through in carbon source and complete
Afterwards, the Graphene being deposited in porous pie oxide mould agent is the 6～30% of its quality；
The porous pie template dissolving for having Graphene will be deposited with hydrochloric acid or sulfuric acid；Or, with NaOH or potassium hydroxide
Solution will deposit the porous pie template dissolving for having Graphene.
10. application of the multi-layer steamed bread shape nano-graphene described in claim 1 in electrode material is prepared.
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