CN107665775A - Ultracapacitor based on porous carbon nanosheet and preparation method thereof - Google Patents
Ultracapacitor based on porous carbon nanosheet and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 104
- 239000002135 nanosheet Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 230000004888 barrier function Effects 0.000 claims abstract description 20
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 230000004913 activation Effects 0.000 claims abstract description 15
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 11
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 3
- 239000007772 electrode material Substances 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 33
- 238000001994 activation Methods 0.000 claims description 29
- 235000007164 Oryza sativa Nutrition 0.000 claims description 27
- 235000009566 rice Nutrition 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 16
- 238000003825 pressing Methods 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 10
- 240000008042 Zea mays Species 0.000 claims description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 9
- 235000005822 corn Nutrition 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 240000005979 Hordeum vulgare Species 0.000 claims description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 240000006394 Sorghum bicolor Species 0.000 claims description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 2
- 244000062793 Sorghum vulgare Species 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000019713 millet Nutrition 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 239000005486 organic electrolyte Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000002608 ionic liquid Substances 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims 1
- 235000019796 monopotassium phosphate Nutrition 0.000 claims 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 241000209094 Oryza Species 0.000 description 23
- -1 conductive black Substances 0.000 description 13
- 239000011149 active material Substances 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 241001466460 Alveolata Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention discloses ultracapacitor based on porous carbon nanosheet and preparation method thereof.Capacitor includes setting septate porous carbon nano-electrode piece among at least two layers.Its preparation method includes:(10) microwave bulking carbonization, the activation of (20) ammonia atmosphere, the purification of the porous carbon nanosheet of (30) functionalization, the preparation of (40) electrode slice, the assembling of (50) ultracapacitor:It is all provided with one layer of barrier film between adjacent two layers porous carbon nano-electrode piece, after assembled formation, is infiltrated with electrolyte, obtain ultracapacitor.The ultracapacitor based on porous carbon nanosheet of the present invention, energy density is high, power density is high.
Description
Technical field
The invention belongs to energy storage device technical field, particularly a kind of ultracapacitor based on porous carbon nanosheet and its
Preparation method.
Background technology
Double layer capacitor (EDLCs) or ultracapacitor, it is considered to be a kind of new energy storage devices, because it is super
High specific power density, good stability and long circulation life, cause people greatly pay close attention to (Science 2015,
350,1508-1513).However, compared to commercialized lithium ion battery, (energy density is about 180Wh kg-1), super capacitor
Device is still limited by relatively low energy density (generally below 8Wh kg at present-1), this significantly limit it as major impetus
The application prospect of power supply.
At present, nano material derived from numerous carbon for example porous charcoal, graphene, CNT, carbon fiber, carbon aerogels with
And mesoporous carbon etc., the extensive use in ultracapacitor as electrode material.There are some researches show the ratio surface of carbon material
Product, surface microstructure, chemical composition etc. are vital (J.Am. to ultracapacitor chemical property
Chem.Soc.2015,137,219-225).Particularly, the controlled dimensions of nano-pore and geometry have become people's concern
Focus because nano-pore structure has a great impact to the power density and energy density of carbon-based material.Up to the present,
Substantial amounts of research, including high-temp chlorination carbonaceous material (ACS Nano 2015,9,2556- have been carried out to optimization micro-structural
2564), various template method and the application (ACS Nano 2015,9,11225-11233) the methods of KOH activation methods.It is actual
On, mesoporous carbon template and KOH activation methods are considered as synthesis bigger serface, high porosity, and are used as high-speed ion
Passage is to obtain the common method of high-energy and quality electric capacity.However, there is no doubt that a large amount of pore-creating may result in micro- knot
Structure caves in and brings high pore volume.When specific surface area is higher than 2400m2g-1When, pore volume would generally exceed 1.9cm3g-1, high hole
Gap rate can cause the decline of volume capacity and energy density (Energy Environ.Sci.2016,9,2249-2256) again.Separately
Outside, template and high-temperature chlorination are very time-consuming in most cases because of its complicated processing method.Recently, some are studied
As a result show, particular kind of micropore in carbon material, especially less than 1nm duct, because " micropore effect " to ion go it is molten
Agent and the energy density (Nat.Commun.2015,6,7221-7230) for greatly improving ultracapacitor.However, micropore
In slowly sheath desolvation and Particles Moving so that high rate performance is relatively low.
Therefore, the problem of prior art is present be:The energy density of ultracapacitor is not high, power density is low.
The content of the invention
It is an object of the invention to provide a kind of ultracapacitor based on porous carbon nanosheet, and energy density is high, power
Density is high.Another object is to provide a kind of preparation method of the ultracapacitor based on porous carbon nanosheet.
The technical solution for realizing the object of the invention is:
A kind of ultracapacitor based on porous carbon nanosheet, including at least two layers of porous carbon nano-electrode piece, adjacent
Barrier film is provided between porous carbon nano-electrode piece.
Preferably, the porous carbon nano-electrode piece is by rich amyloid graininess presoma heated by microwave, by swollen
Change the porous carbon nanosheet of functionalization (N is adulterated at high proportion) that carbonization obtains, ammonia atmosphere activates to obtain to be made.
The technical scheme for realizing another object of the present invention is:
A kind of preparation method based on porous carbon nanosheet ultracapacitor, comprises the following steps:
(10) microwave bulking is carbonized:By the rich amyloid graininess presoma microwave heating 10-17 minutes of drying, pass through
Expanded carbonization can obtain porous carbon nanometer sheet;
(20) ammonia atmosphere activates:By porous carbon nanosheet under ammonia atmosphere carbonization-activation, obtain the porous of functionalization
Carbon nanosheet (N is adulterated at high proportion);Activator ground and mixed and carbonization-activation can be added simultaneously, are increased porous carbon nanosheet and are compared table
Area;
(30) purification of the porous carbon nanosheet of functionalization:By the porous carbon nanosheet grinding of above-mentioned functionalization, wash, dry,
Obtain the porous carbon nanosheet of functionalization with superhigh specific surface area;
(40) prepared by electrode slice:Distilled water is added to be sufficiently mixed stirring above-mentioned porous carbon nanosheet, conductive black, binding agent
Slurry is made, rubs grouting material repeatedly to obtain sheet electrode material;Then above-mentioned sheet electrode material is placed on corresponding big
It is placed at 120 DEG C and dries on small collector, after cold pressing, obtains super capacitor electrode slice;
(50) ultracapacitor assembles:One layer of barrier film, assembled formation are all provided between adjacent two layers porous carbon nano-electrode piece
Afterwards, infiltrated with electrolyte, obtain ultracapacitor.
Preferably, the graininess presoma is corn, rice, millet, highland barley, glutinous rice, sorghum rice, one kind of rice cake.
Preferably, in described (20) carbonization-activation step, carbonization-activation temperature is 750-900 DEG C, time 2h.
Preferably, in described (20) carbonization-activation step, selectable activator includes alkali activator, acidic activated
Agent, neutral activator etc..
Preferably, in described (40) electrode slice preparation process, porous carbon nanosheet, conductive black, the mass ratio of binding agent
For 85:10:5.
Preferably, in described (40) electrode slice preparation process, cold pressing pressure is 10~15 MPas, is cold-pressed time 20-60
Second.
Preferably, in described (40) electrode slice preparation process, the electrode slice of gained ultracapacitor smears density and is more than 12
mg/cm2。
Preferably, in described (50) ultracapacitor number of assembling steps, barrier film can be nylon cloth, all-glass paper, PE micropores
One kind in film, polyvinyl alcohol film, asbestos paper.
Preferably, in described (50) ultracapacitor number of assembling steps, electrolyte include aqueous electrolyte, organic electrolyte and
Il electrolyte.
The present invention makes its " blast " process by the heating of simple microwave, you can will be enriched in the graininess presoma of starch
Become crispy and delicious puffed rice (by taking corn as an example), it is caused by fuel factor " bulking effect " that it, which produces mechanism,.Due to outside
The lasting supply of energy, the liquid gasification inside particle, the internal pressure of material increase sharply, and after pressure is released, rice turns
It is melted into puffed rice.It is interesting that the volume ratio iblet of puffed rice expands more than 20 times, this mainly expands instant of detonation and formed
Honeycomb laminated structure (accompanying drawing 1)." bulking effect " is a kind of pure physical-chemical reaction, and it possesses quick and environmentally friendly excellent
Point.Corn continues the porous carbon nanosheet of microwave heating carbonization acquisition after expanded.By combining physical chemistry " bulking effect " and ammonia
The activation of gas atmosphere obtains the porous carbon nanosheet of high-specific surface area functionalization derived from puffed rice, and as the electricity of ultracapacitor
Pole material.This material has the specific surface area (3301m of superelevation2/ g, wherein micropore area reach 95%, particularly 0.69nm
Preferred hole), and show relatively low pore volume (especially particle passage type hole because it has substantial amounts of micropore
Road), and high content N element, thus superior performance of the supercapacitor is shown, it is 0.2A g in current density-1, 6M KOH
To reach 348F g during electrolyte-1, even in 90A g-1High current density under can also reach 286F g-1.Most of all,
Energy density of this material in il electrolyte has reached 103Wh kg-1(53Wh L-1), this is all reported
Biomass derived carbon in one of highest.The invention provides a kind of new synthesis strategy, using it is ready-made, reproducible,
Cheap raw material, by method quick, green and capable of being industrialized, prepare for the optimal of high-performance super capacitor
Electrode material.
Compared with prior art, its remarkable advantage is the present invention:
1st, the invention provides a kind of microwave bulking carbonizatin method to prepare porous carbon nanosheet (PCF), and as high power, height
The method of energy density electrode material for super capacitor;
2nd, PCF provided by the invention has the advantages that high-specific surface area and aperture are adjustable, is a kind of preferable electrode material,
It can be not only used for the electrochemical energy storing devices such as ultracapacitor, lithium ion battery, lithium-sulfur cell, additionally it is possible to for hydrogen storage, catch
Obtain carbon dioxide, the absorption of environmental contaminants, catalyst carrier, biology and optical sensor and wait multiple fields;
3rd, PCF provided by the invention is activated under ammonia atmosphere, has a high proportion of N doping, it is abundant to be advantageous to electrolyte
Into and infiltrate duct, so as to greatly improve the capacity of ultracapacitor;
4th, when PCF provided by the invention is used as electrode material for super capacitor, not only shown in aqueous electrolyte excellent
Different performance (is 0.2A g in current density using 6M KOH as electrolyte-1Capacity is up to 348F g under low current density-1;
90A g-1High current density be high current density under capacity remain to reach 286F g-1), in il electrolyte
Energy density has reached 103Wh kg-1(53Wh L-1)。
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the invention based on porous carbon nanosheet ultracapacitor.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of PCF prepared by embodiment 1.
Fig. 3 is the transmission electron microscope picture (TEM) of PCF prepared by embodiment 1.
Fig. 4 is PCF XRD prepared by embodiment 1-4 and Raman figure.
Fig. 5 is the ammonia gas absorption-desorption curve figure and pore size distribution curve figure of PCF prepared by embodiment 1-4.
Table 1 is PCF specific surface area prepared by embodiment 1-4 and its pore volume tables of data.
Fig. 6 is that PCF prepared by embodiment 1-4 is applied to ultracapacitor device, in aqueous electrolyte (6M KOH)
Performance map.
Fig. 7 is that PCF prepared by embodiment 3-4 is applied to ultracapacitor device, in il electrolyte
(EMIMBF4) in performance of the supercapacitor figure.
Fig. 8 is the scanning electron microscope (SEM) photograph (SEM) of PCF prepared by embodiment 5-8.
Fig. 9 is the transmission electron microscope picture (TEM) of PCF prepared by embodiment 8.
The XPS that Figure 10 is PCF prepared by embodiment 8 schemes.
Figure 11 is that PCF prepared by embodiment 9-12 is applied to ultracapacitor device, in il electrolyte
(EMIMBF4) in cyclic voltammetric performance map.
Embodiment
The present invention is elaborated with reference to the accompanying drawings and examples.
Embodiment 1
Step 1:The rich amyloid corn particle presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with NaOH after mixing, under protection of ammonia in tube furnace
Carbonization-activation 30 minutes, temperature are 750 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and infiltrated with 6M KOH, you can
It is assembled into ultracapacitor device.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of PCF prepared by embodiment 1.It is corn particle presoma after " bulking effect "
The puffed rice (Fig. 2 a-b) with alveolate texture is formd, this cellular structure is made up of 400-900nm thin slice, hole
Footpath is about 10 μm, and original skeleton structure does not change (Fig. 2 c) in pre- carbonisation.After KOH is activated (Fig. 2 d),
Above-mentioned PCF is provided with substantial amounts of micropore and multi-layer thin layer structure.
Fig. 3 is the transmission electron microscope picture (TEM) of PCF prepared by embodiment 1.From the graph, it is apparent that lived by NaOH
PCF after change produces substantial amounts of micropore and Multilayer ultrathin structure, this structure are advantageous to increasing specific surface area, enable electrolyte
Well into duct, so as to improve performance of the supercapacitor.
Embodiment 2
Step 1:The rich amyloid corn particle presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with NaOH after mixing, under protection of ammonia in tube furnace
Carbonization-activation 30 minutes, temperature are 800 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and infiltrated with 6M KOH, you can
It is assembled into ultracapacitor device.
Embodiment 3
Step 1:The rich amyloid corn particle presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with NaOH after mixing, under protection of ammonia in tube furnace
Carbonization-activation 30 minutes, temperature are 850 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and infiltrated with 6M KOH, you can
It is assembled into ultracapacitor device.
Embodiment 4
Step 1:The rich amyloid corn particle presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with NaOH after mixing, under protection of ammonia in tube furnace
Carbonization-activation 30 minutes, temperature are 900 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and infiltrated with 6M KOH, you can
It is assembled into ultracapacitor device.
Fig. 4 is PCF-X prepared by embodiment 1-4 (X is activation temperature) XRD and Raman figure.From XRD it can be seen that
(Fig. 4 a), PCF-X have two wide diffraction maximums at 25.2 and 43.6 °, corresponding to (002) and (101) face, show prepared
Material is typical agraphitic carbon, and the peak width of (002) is significantly increased due to loose structure.In addition, low angle diffracted intensity
To be remarkably reinforced be caused by the presence of a large amount of micropores.In PCF-X Raman spectrum (Fig. 4 b), high IG/ID peak intensities ratio
Imply the generation of a large amount of defects and the presence of a large amount of micropores.Numerous studies show that the fault of construction of carbon can increase avtive spot
Quantity or active surface, and increase the capacity of ultracapacitor.
Fig. 5 is the ammonia gas absorption-desorption curve figure and pore size distribution curve figure of PCF prepared by embodiment 1-4.Inhaled from ammonia
Attached-desorption curve figure (Fig. 5 a) is as can be seen that PCF-X is typical poromerics.Can be with from pore size distribution curve figure (Fig. 5 b)
To find out, PCF-X nano aperture is less than 3nm, most of micropores for less than 2nm, and occurs peak value at 0.69nm, this
It is consistent with the accessible nano aperture of optimal ion.Such microcellular structure is advantageous to the abundant infiltrating material of electrolyte, so as to carry
High capacity of super capacitor.Table 1 is corresponding PCF specific surface area and its pore volume tables of data.As can be seen from the table, with
The raising of KOH activation temperatures, ascendant trend is presented in PCF-X specific surface area, and specific surface area is commercial activated carbon (YP-17D)
1.5-2 times.The specific surface area of superelevation can provide more avtive spots for contact of the electrolyte with PCF-X, hold to improving
Measure significant.
Fig. 6 is that PCF prepared by embodiment 1-4 is applied to ultracapacitor device, in aqueous electrolyte (6M KOH)
Performance map.Fig. 6 a are PCF cyclic voltammetry curve (CV curves), and wherein PCF-900 CV curve shapes are in 500mV s-1Sweep
Speed is lower close to symmetrical rectangle, shows its preferable double electric layers supercapacitor performance.Fig. 6 b are PCF crossing current charging and discharging curve
Figure, wherein PCF-900 and PCF-850 are in 10A g-1High current density under show more symmetrical charging and discharging curve.From how
Qwest curve (Fig. 6 c) is visible, and PCF-X shows almost vertical curve in low frequency region, shows fabulous electric capacity row
For.Warburg diffusion profiles (slope at 45 ° of curve) indicate more preferable ion diffuser efficiency.Corresponding timeconstantτ0(figure
6d) reduce with the rise of activation temperature, PCF-900 τ0Only 1.0s.It is 0.2A g in current density-1When, PCF ratio
Capacity is YP-17D 2 times (Fig. 6 e), and PCF-900 has reached highest 348F g-1.Shown from the visible PCF-900 of Fig. 6 f
High stability, capability retention is up to 95% after 10000 cycle periods.
Fig. 7 is that PCF prepared by embodiment 3-4 is applied to ultracapacitor device, in il electrolyte
(EMIMBF4) performance map in, voltage window are 3.5 times of aqueous electrolyte.Fig. 7 a are PCF-900 cyclic voltammetry curve
(CV curves), wherein PCF-900 CV curves keep symmetrical rectangular structure in 0-3.5V, and are 100mV s sweeping speed-1When throw away
Nearly rectangular shape is kept, shows its preferable double electric layers supercapacitor performance.Fig. 7 b are PCF-900 in different current densities
Under charging and discharging curve figure, show symmetrical charging and discharging curve.Can be seen that PCF-900 from Fig. 7 c has than PCF-850
Higher electric capacity and more preferable conservation rate.Fig. 7 d can be seen that PCF-900 and PCF-850 is shown almost in low frequency region
Vertical curve, show its good capacitance behavior.But in high-frequency region, PCF-900 shows relatively low ESR and shorter
Warburg curves.Fig. 7 e are PCF-900 and PCF-850 energy comparison figure, and wherein PCF-900 energy density is about 103W
h kg-1(53Wh L-1), and in 8A g-1Current density under still keep 66Wh kg-1(34W h L-1) energy density;In 5A
g-1After lower 5000 circulations of current density (Fig. 7 f), capacity is 193F g-1, conservation rate 88%, show good performance.
Embodiment 5
Step 1:The rich amyloid rice pellets presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with NaCl after mixing, under protection of ammonia in tube furnace
Carbonization-activation 30 minutes, temperature are 750 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and infiltrated with 6M KOH, you can
It is assembled into ultracapacitor device.
Embodiment 6
Step 1:The rich amyloid rice pellets presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with NaCl after mixing, under protection of ammonia in tube furnace
Carbonization-activation 30 minutes, temperature are 800 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and infiltrated with 6M KOH, you can
It is assembled into ultracapacitor device.
Embodiment 7
Step 1:The rich amyloid rice pellets presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with NaCl after mixing, under protection of ammonia in tube furnace
Carbonization-activation 30 minutes, temperature are 850 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and infiltrated with 6M KOH, you can
It is assembled into ultracapacitor device.
Embodiment 8
Step 1:The rich amyloid rice pellets presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with NaCl after mixing, under protection of ammonia in tube furnace
Carbonization-activation 30 minutes, temperature are 900 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and infiltrated with 6M KOH, you can
It is assembled into ultracapacitor device.
Fig. 8 PCF derived from the rice prepared by embodiment 5-8 scanning electron microscope (SEM) photograph (SEM).Rice pellets presoma exists
Puffed rice (Fig. 8 a with alveolate texture are also form after " bulking effect "1-c1), this cellular structure is by 500-
1000nm thin slice composition, aperture is about 5-10 μm, and inherits raw skeleton structure (Fig. 8 a in follow-up pre- carbonisation2-
c3)。
Fig. 9 PCF derived from the rice prepared by embodiment 8 transmission electron microscope picture (TEM).It is it can be seen that big
PCF derived from rice has porous porous, Multilayer ultrathin laminated structure, and is rich in N element.Abundant N element can make electrolyte
Quickly enter and infiltrate nano pore, so as to greatly improve performance of the supercapacitor.
The XPS that Figure 10 is PCF prepared by embodiment 8 schemes.It was found from XPS composes (Figure 10 a) entirely, prepared PCF is except C
With O elements, also containing a small amount of N element.The doping of N element, PCF is set to be easier to be infiltrated by electrolyte, so as to improve material double
Performance in electric layer ultracapacitor.
Embodiment 9
Step 1:The rich amyloid rice pellets presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with KOH after mixing, under protection of ammonia in tube furnace carbon
Change activation 30 minutes, temperature is 750 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and uses EMIMBF4Infiltration, i.e.,
It can be assembled into ultracapacitor device.
Embodiment 10
Step 1:The rich amyloid rice pellets presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with KOH after mixing, under protection of ammonia in tube furnace carbon
Change activation 30 minutes, temperature is 800 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and uses EMIMBF4Infiltration, i.e.,
It can be assembled into ultracapacitor device.
Embodiment 11
Step 1:The rich amyloid rice pellets presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with KOH after mixing, under protection of ammonia in tube furnace carbon
Change activation 30 minutes, temperature is 850 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and uses EMIMBF4Infiltration, i.e.,
It can be assembled into ultracapacitor device.
Embodiment 12
Step 1:The rich amyloid rice pellets presoma microwave of drying is heated 12 minutes, is by expanded carbonization
It can obtain porous carbon nanosheet;
Step 2:The porous carbon nanosheet of gained is fully ground with KOH after mixing, under protection of ammonia in tube furnace carbon
Change activation 30 minutes, temperature is 900 DEG C, obtained black solid;
Step 3:By the black solid grind into powder in step 2, with hydrochloric acid and distillation water washing and filter to neutrality
After dry, you can obtain the porous carbon nanosheet (PCF) with superhigh specific surface area;
Step 4:By above-mentioned porous carbon nanosheet (active material), conductive black, binding agent in mass ratio 85:10:5, add
Distilled water is sufficiently mixed stirring and slurry is made, and rubs grouting material repeatedly to obtain sheet electrode material;Then by above-mentioned electrode material
Material is placed on correspondingly sized collector, and 10 MPas of cold pressings were placed at 105 DEG C and dried after 30 seconds, obtained the pole of ultracapacitor
Piece, and the smearing density of electrode material is more than 12mg/cm2;
Step 5:Electrode slice/barrier film/electrode slice is assembled with " sandwich " structure, and uses EMIMBF4Infiltration, i.e.,
It can be assembled into ultracapacitor device.
Figure 11 is that PCF prepared by embodiment 9-12 is applied to ultracapacitor device, in il electrolyte
(EMIMBF4) in cyclic voltammetric performance map.Sweep speed for 20,50,100,200mV/s when, PCF-X cyclic voltammetry curve
Quasi- symmetrical rectangular shape is presented in (Figure 11 a), shows good capacitance behavior.
Claims (13)
- A kind of 1. ultracapacitor based on porous carbon nanosheet, it is characterised in that:Including at least two layers of porous carbon nano-electrode piece, barrier film is provided between adjacent porous carbon nano-electrode piece.
- 2. ultracapacitor according to claim 1, it is characterised in that:The porous carbon nano-electrode piece is obtained more by rich amyloid graininess presoma heated by microwave by expanded carbonization Hole carbon nanosheet, activated to obtain the porous carbon nanosheet of functionalization of high-specific surface area and N doping again with ammonia atmosphere.
- 3. ultracapacitor according to claim 2, it is characterised in that:In the ammonia atmosphere activation process, add activator ground and mixed and mixed with increasing porous carbon nanosheet specific surface area and N It is miscellaneous.
- 4. a kind of preparation method of ultracapacitor as claimed in claim 1, it is characterised in that comprise the following steps:(10) microwave bulking is carbonized:The rich amyloid graininess presoma microwave of drying is heated 5~40 minutes, expanded carbonization Obtain porous carbon nanosheet;(20) ammonia atmosphere activates:By porous carbon nanosheet under ammonia atmosphere carbonization-activation, obtain the function of the doping of N at high proportion Change porous carbon nanosheet;(30) purification of the porous carbon nanosheet of functionalization:By the porous carbon nanosheet grinding of above-mentioned functionalization, wash, dry, obtain High-quality has the porous carbon nanosheet of superhigh specific surface area functionalization;(40) prepared by electrode slice:Distilled water is added to be sufficiently mixed stirring system above-mentioned porous carbon nanosheet and conductive black, binding agent Into slurry, grouting material is rubbed repeatedly to obtain sheet electrode material;Then above-mentioned sheet electrode material is placed on correspondingly sized Collector on, be placed at 120 DEG C and dry after cold pressing, obtain super capacitor electrode slice;(50) ultracapacitor assembles:It is all provided with one layer of barrier film between adjacent two layers porous carbon nano-electrode piece, after assembled formation, uses Electrolyte infiltrates, and obtains ultracapacitor.
- 5. the preparation method of ultracapacitor according to claim 4, it is characterised in that:The graininess presoma is corn, rice, millet, highland barley, glutinous rice, sorghum rice, one kind of rice cake.
- 6. the preparation method of ultracapacitor according to claim 4, it is characterised in that:In (20) the ammonia atmosphere activation step, activation temperature is 450~900 DEG C, and the time is 1-6 hours.
- 7. the preparation method of ultracapacitor according to claim 4, it is characterised in that:In (20) the ammonia atmosphere activation step, selectable alkali activator activator includes potassium carbonate, sodium hydroxide, carbon Sour sodium, ammonia spirit;Acidic activator includes phosphoric acid, phosphoric acid hydrogen ammonia, ammonium di-hydrogen phosphate, potassium dihydrogen phosphate;Neutral activator bag Include zinc chloride, sodium chloride, magnesium chloride, aluminium chloride.
- 8. the preparation method of ultracapacitor according to claim 4, it is characterised in that:In (40) the electrode slice preparation process, porous carbon nanosheet, conductive black, the mass ratio of binding agent are 85:10:5.
- 9. the preparation method of ultracapacitor according to claim 4, it is characterised in that:In (40) the electrode slice preparation process, cold pressing pressure is 1~30 MPa, is cold-pressed 20~60 seconds time.
- 10. the preparation method of ultracapacitor according to claim 4, it is characterised in that:In (40) the electrode slice preparation process, the electrode slice of gained ultracapacitor smears density and is more than 12mg/cm2。
- 11. the preparation method of ultracapacitor according to claim 4, it is characterised in that:In (50) the ultracapacitor number of assembling steps, barrier film be nylon cloth, all-glass paper, PE microporous barriers, polyvinyl alcohol film, One kind in asbestos paper.
- 12. the preparation method of ultracapacitor according to claim 4, it is characterised in that:In (50) the ultracapacitor number of assembling steps, electrolyte includes aqueous electrolyte, organic electrolyte or ionic liquid electricity Solve liquid.
- 13. the preparation method of ultracapacitor according to claim 4, it is characterised in that:In (20) the ammonia atmosphere activation step, activator ground and mixed is added to increase porous carbon nanosheet specific surface area.
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