CN110491676A - A method of high pressure resistant electrode material is prepared using porous carbon polyaniline - Google Patents
A method of high pressure resistant electrode material is prepared using porous carbon polyaniline Download PDFInfo
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- CN110491676A CN110491676A CN201910686427.4A CN201910686427A CN110491676A CN 110491676 A CN110491676 A CN 110491676A CN 201910686427 A CN201910686427 A CN 201910686427A CN 110491676 A CN110491676 A CN 110491676A
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- porous carbon
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- polyaniline
- mixture
- electrode material
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 90
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000007772 electrode material Substances 0.000 title claims abstract description 25
- 230000000640 hydroxylating effect Effects 0.000 claims abstract description 62
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000003990 capacitor Substances 0.000 claims abstract description 12
- 241000209140 Triticum Species 0.000 claims abstract description 10
- 235000021307 Triticum Nutrition 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 235000013312 flour Nutrition 0.000 claims abstract description 10
- 238000012360 testing method Methods 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000012153 distilled water Substances 0.000 claims description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 238000004090 dissolution Methods 0.000 claims 1
- 235000015110 jellies Nutrition 0.000 claims 1
- 239000008274 jelly Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 4
- 239000012190 activator Substances 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000003575 carbonaceous material Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of methods for preparing high pressure resistant electrode material using porous carbon polyaniline, including prepare hydroxylating porous carbon, preparation hydroxylating porous carbon/polyaniline composite material, are prepared into electrode slice and carry out electrochemical property test.The beneficial effects of the present invention are: using wheat flour as carbon source, potassium hydroxide (KOH), urea is raw material, wherein potassium hydroxide is activator, obtaining the hydroxylating porous carbon of N doping through high temperature cabonization-acid processing method is presoma, then prepares hydroxylating porous carbon/polyaniline composite material by in-situ polymerization；The composite material for the polyaniline-coated hydroxylating porous carbon that the present invention prepares, it is conductive can the stable advantage of excellent, large specific surface area, physicochemical properties, can be used as the electrode material of the aqueous super capacitor with extra-high voltage window.
Description
Technical field
The present invention relates to a kind of methods for preparing high pressure resistant electrode material, specially a kind of to be prepared using porous carbon polyaniline
The method of high pressure resistant electrode material belongs to the manufacturing technology field of supercapacitor.
Background technique
In recent years, the dependence with the increasing living standard of people and industrial development to petroleum, Global Oil storage
The problem of the problem of amount decline is with global warming is more prominent, seek a kind of cleaning and renewable new energy source or technology seem to
It closes important.In order to cope with energy crisis and environmental degradation problem, scientists extensive concern and develop solar energy, tide energy,
The secondary energy sources such as the non-renewable energy such as thermal energy and electrochemical energy.And lithium ion battery, traditional capacitor and supercapacitor are common
Electrochemical storage device, wherein supercapacitor is one of the electrochemical energy storage technology of current great application prospect, as one
A kind of energy storage device of kind bridge joint traditional capacitor and secondary cell, supercapacitor have power density high, and charging rate is fast,
The advantages such as service life cycle is long, and Applicable temperature range is wide, and storage life is long, environmentally protective, and maintenance cost is low.
Currently, the lower energy density of supercapacitor is therefore the disadvantage for limiting its development and applying is not being damaged
Promoting energy density under the premise of losing power density becomes Research Challenges.Again by formula: energy density (E=(CAsc×ΔV2)/
7.2, wh/kg), power density (P=3600E/ △ t, w/kg) is it is found that the method for improving super capacitor energy density has two
Kind: first is that improving the specific capacitance of electrode active material；Second is that widening the electrochemical window of supercapacitor.Polyaniline is common
The electrode material of supercapacitor, polyaniline have the advantages that low in cost, preparation is simple, large specific surface area, but most of
The voltage window of polyaniline is all relatively low, and single-electrode voltage window is generally 0~1V, with the asymmetric voltage after carbon material assembling
Window is general≤1.7V.
Summary of the invention
The object of the invention is that providing to solve the above-mentioned problems and a kind of preparing resistance to height using porous carbon polyaniline
The method for pressing electrode material.
The present invention is through the following technical solutions to achieve the above objectives: a kind of prepare high pressure resistant electricity using porous carbon polyaniline
The method of pole material, comprising the following steps:
Step 1, preparation hydroxylating porous carbon, wheat flour, urea, KOH are mixed according to a certain mass ratio plus distilled water dissolves,
It is uniformly mixed, and obtains porous carbon after high temperature cabonization, and HNO is added into porous carbon sample3Solution, after ultrasonic treatment, with steaming
Distilled water is washed to PH ≈ 7, and hydroxylating porous carbon can be obtained after vacuum drying；
Step 2, preparation hydroxylating porous carbon/polyaniline composite material sequentially add under ice-water bath conditional
1MH2SO4, hydroxylating porous carbon, aniline monomer, ammonium persulfate, wherein using ammonium persulfate as initiator, make aniline monomer in step
In-situ polymerization on hydroxylating porous carbon made from rapid 2, reaction terminates afterwards for 24 hours, PH ≈ 7 is washed with distilled water to, after vacuum drying
Prepare hydroxylating porous carbon/polyaniline composite material；
Step 3 is prepared into electrode slice, and hydroxylating porous carbon/polyaniline, acetylene black, Kynoar are pressed certain matter
Amount ratio is ground, until being coated on steel mesh after micron level, electrode slice is made after vacuum drying；
Step 4 carries out electrochemical property test.
As further scheme of the invention: the step 1 includes:
1.1, wheat flour 5g is taken, then takes urea, KOH.Wheat flour, urea, KOH are mixed according to the mass ratio of 1:1:1, added
Enter 100ml distilled water, uniform to mixture to mixture progress strong stirring using glass bar, it is yellow that mixture, which can be observed,
Cloudy colloidal object；
1.2, mixture is put into baking oven, adjusts the temperature to 100 DEG C, the moisture in mixture is completely removed；
1.3, carbonization pore-creating is carried out, under protection of argon gas, is carried out the mixture after drying at 800 DEG C of heat using tube furnace
2h is managed, heating rate is 2 DEG C/min, and after the completion of heat treatment, cooled to room temperature takes out product；
1.4, product is washed with distilled water to remove its impurity, appropriate 10%HNO is added in backward product3Solution, and
70 DEG C~80 DEG C are heated to, during which ultrasonic 30min need to repeatedly add 10%HNO3Solution guarantees that solution submerges mixture, ultrasound
After be washed with distilled water mixture to pH ≈ 7, for 24 hours, it is more that hydroxylating can be obtained in the oven drying that mixture is placed in 100 DEG C
Hole carbon.
As further scheme of the invention: the step 2 includes:
2.1, three-necked flask is placed in ice-water bath, whole process should ensure that device is in lower temperature (0 DEG C), and need
It keeps being passed through argon gas into device and be protected；
2.2,40ml 1M H is injected into three-necked flask2SO4With 46.65uL aniline monomer, it is put into magneton, magnetic agitation
100mg hydroxylating porous carbon, magnetic agitation 2h is added in 15min after mixing；
2.3,0.1142gAPS is taken to be dissolved in 40ml 1M H2SO4, pour into clean closed constant pressure funnel and instill three mouthfuls dropwise
In flask, magnetic agitation is kept for 24 hours, product is washed with distilled water mixture to pH ≈ 7, and it is dry that place the product in 100 DEG C of baking ovens
It is dry for 24 hours, finally obtain hydroxylating porous carbon/polyaniline composite material.
As further scheme of the invention: the step 3 includes:
3.1,4*1cm is chosen2The steel mesh of 200 mesh is collector, steeps in acetone more than 15min, is washed with distilled water,
It is put into oven drying；
3.2, by the porous carbon of hydroxylating made from step 2/polyaniline (active material), acetylene black, Kynoar
(PVDF) it is put into mortar and grinds for 8:1.5:0.5 in mass ratio, be added suitable N, N-dimethylformamide (DMF) solvent,
So that material is sufficiently mixed into paste, uniformly coated with scraper with collector on, area about 1*1cm2；
3.3, collector is put into 100 DEG C of vacuum ovens, takes out tabletting after dry, pressure 10Mpa, pressure maintaining 20s,
Obtained electrode slice load capacity about 2-3mg.
As further scheme of the invention: the step 4 includes:
4.1, it using electrochemical workstation, successively works in the method for three electrodes and CV, EIS, GCD survey is carried out to electrode material
Examination.Wherein electrolyte is 1M H2SO4, it is platinized platinum (Pt) to electrode that reference electrode, which is saturated calomel electrode (SCE),；
4.2, using electrochemical workstation, CV, EIS, GCD test successively are carried out to electrode material in the method for two electrodes.
Wherein electrolyte is 1M H2SO4, just extremely hydroxylating porous carbon, cathode are hydroxylating porous carbon/polyaniline, and composition hydroxylating is more
Hole carbon // hydroxylating porous carbon/carbon/polyaniline super capacitor.
The beneficial effects of the present invention are: this prepares high pressure water system super capacitor electrode using hydroxylating porous carbon/polyaniline
The method design of pole material is reasonable:
1. acid processing can be such that carbon surface is roughened, thus increased reaction when preparing hydroxylating porous carbon/polyaniline
Active site improves effective contact surface area, and aniline monomer can be better dispersed in porous carbon materials surface, and firm at it
Surface in situ grows polyaniline；
2. acid processing can make porous carbon have more hydrophilic functional groups (such as :-COOH ,-OH), and it is more to obtain hydroxylating
Hole carbon can have better wellability to improve its hydrophily in the electrolytic solution.The largely oxygen-containing function such as-COOH ,-OH
Group easily occurs redox reaction in electrode charge and discharge process and generates pseudo capacitance, thus greatly improves the ratio of sample
Capacitor；
3. compared to electrode material of the metal oxide as supercapacitor is used, the hydroxylating of this method preparation is porous
Carbon/polyaniline composite material has simple process, cost more cheap, also has cycle performance and high rate performance more excellent
Advantage, so that carbon composite is reached high voltage window 2.0V in the aqueous electrolyte of safe green, be a kind of high performance-price ratio
Ideal electrode material.
Detailed description of the invention
Fig. 1 is hydroxylating porous carbon/polyaniline scanning electron microscope sem and the element energy spectrum analysis of preparation of the embodiment of the present invention
Figure；
Fig. 2 is hydroxylating porous carbon/polyaniline charge and discharge electrograph of preparation of the embodiment of the present invention；
Fig. 3 is hydroxylating porous carbon/polyaniline cycle life figure (5A/g) of preparation of the embodiment of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Fig. 1~3 are please referred to, a method of high pressure resistant electrode material, including following step are prepared using porous carbon polyaniline
It is rapid:
Step 1, preparation hydroxylating porous carbon, wheat flour, urea, KOH are mixed according to a certain mass ratio plus distilled water dissolves,
It is uniformly mixed, and obtains porous carbon after high temperature cabonization, and HNO is added into porous carbon sample3Solution, after ultrasonic treatment, with steaming
Distilled water is washed to PH ≈ 7, and hydroxylating porous carbon can be obtained after vacuum drying；
Wherein, step 1 includes:
1.1, wheat flour 5g is taken, then takes urea, KOH.Wheat flour, urea, KOH are mixed according to the mass ratio of 1:1:1, added
Enter 100ml distilled water, uniform to mixture to mixture progress strong stirring using glass bar, it is yellow that mixture, which can be observed,
Cloudy colloidal object；
1.2, mixture is put into baking oven, adjusts the temperature to 100 DEG C, the moisture in mixture is completely removed；
1.3, carbonization pore-creating is carried out, under protection of argon gas, is carried out the mixture after drying at 800 DEG C of heat using tube furnace
2h is managed, heating rate is 2 DEG C/min, and after the completion of heat treatment, cooled to room temperature takes out product；
1.4, product is washed with distilled water to remove its impurity, appropriate 10%HNO is added in backward product3Solution, and
70 DEG C~80 DEG C are heated to, during which ultrasonic 30min need to repeatedly add 10%HNO3Solution guarantees that solution submerges mixture, ultrasound
After be washed with distilled water mixture to pH ≈ 7, for 24 hours, it is more that hydroxylating can be obtained in the oven drying that mixture is placed in 100 DEG C
Hole carbon.
Step 2, preparation hydroxylating porous carbon/polyaniline composite material sequentially add under ice-water bath conditional
1MH2SO4, hydroxylating porous carbon, aniline monomer, ammonium persulfate, wherein using ammonium persulfate as initiator, make aniline monomer in step
In-situ polymerization on hydroxylating porous carbon made from rapid 2, reaction terminates afterwards for 24 hours, PH ≈ 7 is washed with distilled water to, after vacuum drying
Prepare hydroxylating porous carbon/polyaniline composite material；
Wherein, step 2 includes:
2.1, three-necked flask is placed in ice-water bath, whole process should ensure that device is in lower temperature (0 DEG C), and need
It keeps being passed through argon gas into device and be protected；
2.2,40ml 1M H is injected into three-necked flask2SO4With 46.65uL aniline monomer, it is put into magneton, magnetic agitation
100mg hydroxylating porous carbon, magnetic agitation 2h is added in 15min after mixing；
2.3,0.1142gAPS is taken to be dissolved in 40ml 1M H2SO4, pour into clean closed constant pressure funnel and instill three mouthfuls dropwise
In flask, magnetic agitation is kept for 24 hours, product is washed with distilled water mixture to pH ≈ 7, and it is dry that place the product in 100 DEG C of baking ovens
It is dry for 24 hours, finally obtain hydroxylating porous carbon/polyaniline composite material.
Step 3 is prepared into electrode slice, and hydroxylating porous carbon/polyaniline, acetylene black, Kynoar are pressed certain matter
Amount ratio is ground, until being coated on steel mesh after micron level, electrode slice is made after vacuum drying；
Wherein, step 3 includes:
3.1,4*1cm is chosen2The steel mesh of 200 mesh is collector, steeps in acetone more than 15min, is washed with distilled water,
It is put into oven drying；
3.2, by the porous carbon of hydroxylating made from step 2/polyaniline (active material), acetylene black, Kynoar
(PVDF) it is put into mortar and grinds for 8:1.5:0.5 in mass ratio, be added suitable N, N-dimethylformamide (DMF) solvent,
So that material is sufficiently mixed into paste, uniformly coated with scraper with collector on, area about 1*1cm2；
3.3, collector is put into 100 DEG C of vacuum ovens, takes out tabletting after dry, pressure 10Mpa, pressure maintaining 20s,
Obtained electrode slice load capacity about 2-3mg.
Step 4 carries out electrochemical property test.
Wherein, step 4 includes:
4.1, using electrochemical workstation, CV, EIS, GCD test successively are carried out to electrode material in the method for three electrodes.
Wherein electrolyte is 1M H2SO4, it is platinized platinum (Pt) to electrode that reference electrode, which is saturated calomel electrode (SCE),；
4.2, using electrochemical workstation, CV, EIS, GCD test successively are carried out to electrode material in the method for two electrodes.
Wherein electrolyte is 1M H2SO4, just extremely hydroxylating porous carbon, cathode are hydroxylating porous carbon polyaniline, and composition hydroxylating is more
Hole carbon hydroxylating porous carbon/polyaniline capacitor.
As shown in Figure 1, hydroxylating porous carbon/polyaniline uniform pore diameter of preparation can be observed in SEM figure, and more
Hole carbon surface has uniformly coated one layer of fine granularity substance, and composes at element energy spectrum analysis figure N element (polyaniline characteristic element)
Peak is obvious, illustrates that existing material is polyaniline, and homoepitaxial is on the surface of hydroxylating porous carbon.
As shown in Figure 2, hydroxylating porous carbon hydroxylating porous carbon/polyaniline composition supercapacitor can be filled with low current
Electricity, heavy-current discharge, and charging and discharging curve is distributed symmetrically, and has the characteristics that super electric capacitor electric double layer capacitance, and can reach
The high voltage window of 2.0V, and by the charging and discharging curve under 1A/g current density calculate power density 998.5W/kg (in energy
Density is under 29.4Wh/kg).
From the figure 3, it may be seen that hydroxylating porous carbon // hydroxylating porous carbon/polyaniline coulombic efficiency circulation 10,000 circle after still
It can reach 100%, and its wave portion near 100% is since the extraneous factors such as temperature, humidity, noise, vibration cause.
Working principle: in aqueous super capacitor, porous carbon materials can be super electricity due to flourishing pore structure
Container offer electric double layer capacitance, excellent conductivity, electrode material resistance itself are small；Polyaniline, can under the conditions of acid test
Caused by redox reaction occurs, show Faraday's fake capacitance behavior, itself-NH can with porous carbon-
OH ,-COOH form hydrogen bond action, are stabilized.Again due to the hydroxylation of porous carbon materials, between porous carbon/polyaniline
Synergistic effect make composite material have good hydrophily, chemical stability, meanwhile, uniform aperture and three-dimensional porous knot
Structure has high contact area in the electrolytic solution, accelerates the transfer efficiency of ionic mobility and electronics, reduces solution resistance, also subtracts
The polarization of light current pole in the solution, and then improve the potential window of electrode charge and discharge process.The polyphenyl that the present invention prepares
Amine coats the composite material of hydroxylating porous carbon, it is conductive can stable excellent of excellent, large specific surface area, physicochemical properties
Point can be used as the electrode material of the aqueous super capacitor with extra-high voltage window.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (5)
1. a kind of method for preparing high pressure resistant electrode material using porous carbon polyaniline, it is characterised in that: the following steps are included:
Step 1, preparation hydroxylating porous carbon, wheat flour, urea, KOH are mixed according to a certain mass ratio plus distilled water dissolution, mixing
Uniformly, and after high temperature cabonization porous carbon is obtained, and HNO is added into porous carbon sample3Solution after ultrasonic treatment, uses distilled water
Hydroxylating porous carbon can be obtained to PH ≈ 7 in washing after vacuum drying；
Step 2, preparation hydroxylating porous carbon/polyaniline composite material sequentially add 1MH under ice-water bath conditional2SO4, hydroxyl
Base porous carbon, aniline monomer, ammonium persulfate, wherein using ammonium persulfate as initiator, make aniline monomer made from the step 2
In-situ polymerization on hydroxylating porous carbon, reaction terminates afterwards for 24 hours, is washed with distilled water to PH ≈ 7, prepares hydroxyl after vacuum drying
Change porous carbon/polyaniline composite material；
Step 3 is prepared into electrode slice, according to a certain mass ratio by hydroxylating porous carbon/polyaniline, acetylene black, Kynoar
It is ground, until being coated on steel mesh after micron level, electrode slice is made after vacuum drying；
Step 4 carries out electrochemical property test.
2. a kind of method for preparing high pressure resistant electrode material using porous carbon polyaniline according to claim 1, feature
Be: the step 1 includes:
1.1, wheat flour 5g is taken, then takes urea, KOH.Wheat flour, urea, KOH are mixed according to the mass ratio of 1:1:1, are added
100ml distilled water, uniform to mixture to mixture progress strong stirring using glass bar, it is that yellow is muddy that mixture, which can be observed,
Turbid jelly；
1.2, mixture is put into baking oven, adjusts the temperature to 100 DEG C, the moisture in mixture is completely removed；
1.3, carbonization pore-creating is carried out, under protection of argon gas, the mixture after drying is subjected to 800 DEG C of heat treatments using tube furnace
2h, heating rate is 2 DEG C/min, and after the completion of heat treatment, cooled to room temperature takes out product；
1.4, product is washed with distilled water to remove its impurity, appropriate 10%HNO is added in backward product3Solution, and be heated to
70 DEG C~80 DEG C, during which ultrasonic 30min need to repeatedly add 10%HNO3Solution guarantees that solution submerges mixture, after ultrasonic
Mixture is washed with distilled water to pH ≈ 7, for 24 hours, hydroxylating porous carbon can be obtained in the oven drying that mixture is placed in 100 DEG C.
3. a kind of method for preparing high pressure resistant electrode material using porous carbon polyaniline according to claim 1, feature
Be: the step 2 includes:
2.1, three-necked flask is placed in ice-water bath, whole process should ensure that device is in lower temperature (0 DEG C), and need to protect
It holds and is passed through argon gas into device and is protected；
2.2, into three-necked flask inject 40ml1M H2SO4With 46.65uL aniline monomer, it is put into magneton, magnetic agitation 15min,
100mg hydroxylating porous carbon, magnetic agitation 2h are added after mixing；
2.3,0.1142gAPS is taken to be dissolved in 40ml1M H2SO4, pour into clean closed constant pressure funnel and instill three-necked flask dropwise
In, keep magnetic agitation for 24 hours, product is washed with distilled water mixture to pH ≈ 7, and place the product in 100 DEG C of oven dryings
For 24 hours, hydroxylating porous carbon/polyaniline composite material is finally obtained.
4. a kind of method for preparing high pressure resistant electrode material using porous carbon polyaniline according to claim 1, feature
Be: the step 3 includes:
3.1,4*1cm is chosen2The steel mesh of 200 mesh is collector, steeps in acetone more than 15min, is washed with distilled water, is put into baking
Case is dry；
3.2, the porous carbon of hydroxylating made from step 2/polyaniline (active material), acetylene black, Kynoar (PVDF) are pressed
Mass ratio is put into mortar for 8:1.5:0.5 and grinds, and suitable N is added, N-dimethylformamide (DMF) solvent fills material
Point be mixed into paste, uniformly coat with scraper and collector on, area about 1*1cm2；
3.3, collector is put into 100 DEG C of vacuum ovens, takes out tabletting, pressure 10Mpa after dry, pressure maintaining 20s is obtained
Electrode slice load capacity about 2-3mg.
5. a kind of method for preparing high pressure resistant electrode material using porous carbon polyaniline according to claim 1, feature
Be: the step 4 includes:
4.1, using electrochemical workstation, CV, EIS, GCD test successively are carried out to electrode material in the method for three electrodes.Wherein
Electrolyte is 1M H2SO4, it is platinized platinum (Pt) to electrode that reference electrode, which is saturated calomel electrode (SCE),；
4.2, using electrochemical workstation, CV, EIS, GCD test successively are carried out to electrode material in the method for two electrodes.Wherein
Electrolyte is 1M H2SO4, just extremely hydroxylating porous carbon, cathode are hydroxylating porous carbon/polyaniline, and composition hydroxylating is porous
Carbon // hydroxylating porous carbon/carbon/polyaniline super capacitor.
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