CN107658149A - A kind of composite electrode material for super capacitor and preparation method thereof - Google Patents
A kind of composite electrode material for super capacitor and preparation method thereof Download PDFInfo
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- CN107658149A CN107658149A CN201710770517.2A CN201710770517A CN107658149A CN 107658149 A CN107658149 A CN 107658149A CN 201710770517 A CN201710770517 A CN 201710770517A CN 107658149 A CN107658149 A CN 107658149A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003990 capacitor Substances 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 title abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 102
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 49
- -1 Schiff base transition metal Chemical class 0.000 claims abstract description 37
- 239000002262 Schiff base Substances 0.000 claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 31
- 238000011065 in-situ storage Methods 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000002848 electrochemical method Methods 0.000 claims abstract description 8
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000002322 conducting polymer Substances 0.000 claims description 13
- 229920001940 conductive polymer Polymers 0.000 claims description 13
- JBEGXWSLDJCTQZ-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol nickel Chemical group [Ni].Oc1ccccc1C=NCCN=Cc1ccccc1O JBEGXWSLDJCTQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002484 cyclic voltammetry Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 244000137852 Petrea volubilis Species 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 238000002474 experimental method Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 14
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000002242 deionisation method Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- PNNCWTXUWKENPE-UHFFFAOYSA-N [N].NC(N)=O Chemical compound [N].NC(N)=O PNNCWTXUWKENPE-UHFFFAOYSA-N 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical group CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 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
- H01G11/84—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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The present invention principally falls into electrochemical energy storage electrode material for super capacitor field, and in particular to a kind of composite electrode material for super capacitor and preparation method thereof.Methods described prepares the electrode slice for having nitrogen-doped graphene in surface using nitrogen-doped graphene；Electrode slice of the surface with nitrogen-doped graphene is placed in the organic electrolyte containing Schiff base transition metal polymerization thing monomer, in-situ polymerization is carried out by electrochemical method, obtains the hybrid supercapacitor electrode material.Methods described carries out N doping by adding urea to graphene, there is fake capacitance and excellent electrical conductance by the graphene of N doping, it is high by 10% 20% when the pure graphene of its capacity ratio is as substrate, and nitrogen-doped graphene electrode material still keeps stable after multiple discharge and recharge.
Description
Technical field
The present invention principally falls into electrochemical energy storage electrode material for super capacitor field, and in particular to a kind of ultracapacitor
Combination electrode material and preparation method thereof, the specific capacity of conducting polymer ultracapacitor can be improved in organic system, fitted
For ultracapacitor organic electrolyte system.
Background technology
The modern civilization on fossil fuel basis is established because of environmental problem and increasingly by the clean energy resource of sustainable development
Instead of.At present, find and study the clean energy resource of environment-friendly high-efficiency has turned into the only way of human civilization sustainable development.
Ultracapacitor is novel energy storage and the reforming unit between traditional capacitor and secondary cell.It is super
For capacitor because high with power density, energy density is high, the advantages that having extended cycle life and be widely used in such as mobile communication, hand over
The fields such as logical instrument, Aero-Space and information technology, and attracted extensive concern and the research of whole world scholar.Common is super
Capacitor electrode material mainly has carbon material, metal oxide and conducting polymer, and wherein conducting polymer is with its uniqueness
Redox property, cause the broad interest of researcher.Reversible redox reaction, specific volume can occur for conducting polymer
Amount is high, good conductivity, has good application prospect.
In order to strengthen the specific capacity of ultracapacitor and cycle performance, researcher is directed to carrying out height to existing electrode material
The modified exploration of effect.
The content of the invention
For above-mentioned technical problem, the present invention provides a kind of composite electrode material for super capacitor and preparation method thereof, institute
Method is stated in the set-up procedure of electrode material, it is golden using the graphene of N doping as the transition of matrix in-situ polymerization Schiff base
Belong to conducting polymer.N doping is carried out to graphene by adding urea, urea discharges ammonia under high temperature action, can be to stone
Black alkene is nitrogenized, and the high temperature heat radiation of microwave chemical reactor enhances the homogeneity of reaction, by the graphene of N doping
With fake capacitance and excellent electrical conductance, high 10%-20% when the pure graphene of its capacity ratio is as substrate, and N doping graphite
Alkene electrode material still keeps stable after multiple discharge and recharge.
The present invention is achieved by the following technical solutions：
A kind of preparation side of nitrogen-doped graphene and Schiff base transition metal polymerization thing hybrid supercapacitor electrode material
Method, methods described prepare the electrode slice for having nitrogen-doped graphene in surface using nitrogen-doped graphene；The surface is attached
The electrode slice for having nitrogen-doped graphene is placed in the organic electrolyte containing Schiff base transition metal polymerization thing monomer, is passed through
Electrochemical method carries out in-situ polymerization, obtains the hybrid supercapacitor electrode material.
Further, the preparation method of electrode slice of the surface with nitrogen-doped graphene is specially：
Prepare nitrogen-doped graphene：A certain amount of graphene is dissolved in ethanol, stirred, urea is added, continues to stir, is turned after dissolving
Enter reactor, reactor is placed in high temperature microwave chemical reactor and reacted, reaction is taken out after terminating, and is cooled down, is used ethanol
And deionized water cleaning, dry, obtain dried nitrogen-doped graphene；
The preparation of collector titanium sheet：Titanium sheet is cut into the sheet of certain specification, is cleaned and deoiled with sodium carbonate liquor, then go from
Sub- water is put into after rinsing in the hydrochloric acid solution that mass concentration is 30wt%, is washed with deionized water only after soaking 2 h, will finally be washed again
Net titanium sheet is polished smooth with the sand paper of different model, obtains the collector titanium sheet；
The preparation of electrode slice：The dried nitrogen-doped graphene is weighed, is dissolved in dispersant N- methyl-pyrrolidons, is surpassed
Sound crushes, and obtains nitrogen-doped graphene uniform sizing material；The nitrogen-doped graphene uniform sizing material is coated in the collector titanium
The surface of piece, is then placed in baking oven, in 80 DEG C of vacuum drying 12h, naturally cools to room temperature, obtains the surface and is mixed with nitrogen
The electrode slice of miscellaneous graphene.
Further, in described the step of preparing nitrogen-doped graphene：Control consolidating for the graphene and the ethanol
Liquor ratio is 20mg：30-60ml, in the range of this solid-to-liquid ratio, graphene can be fully dissolved in ethanol and not over reaction
Kettle capacity limit；It is 1 to control the mass ratio of graphene and urea:（10-300）；It is anti-that reactor is placed in high temperature microwave chemistry
Answer in device, controlling reaction temperature is 160 DEG C -220 DEG C, reaction time 6h-15h, and the high temperature microwave radiation of suitable duration ensures
Reaction can uniformly occur.
Further, by the preparation process of the collector titanium sheet, the collector titanium sheet prepared will meet afflux
The requirement of body（The specific requirement of collector is that collector titanium sheet should be safe, stable, and is not sent out in electrochemical process with electrolyte
Biochemical reaction）, ensure the repeatability tested.
Further, in the preparation process of the electrode slice, the surface prepared is controlled to have N doping graphite
On the electrode slice of alkene, the carrying capacity of nitrogen-doped graphene is 0.1-0.5mg/cm2, with micropipette rifle to titanium in this load ranges
Piece is coated, and is dried in vacuum environment, 0.1-0.5 mg/cm2Coated weight can ensure that electrode material is equal to electrode slice
Even covering and will not because amount formed greatly it is hardened be unfavorable for the subsequent growth of polymer.
Further, electrode slice of the surface with nitrogen-doped graphene is placed in containing Schiff base transition metal
In the organic electrolyte of polymer monomer, the method for carrying out in-situ polymerization is specially：
Build organic three-electrode system：Using electrode slice of the surface with nitrogen-doped graphene as working electrode, reference electricity
Extremely Ag/AgCl, auxiliary electrode are the active carbon cloth of large area；
In-situ polymerization：Schiff base transition metal polymerization thing monomer is dissolved in organic electrolyte, in organic three electrode
In system, by electrochemical method, the in situ Polymerization growth of the electrode slice with nitrogen-doped graphene on the surface
Schiff base transition metal conducting polymer, obtains the hybrid supercapacitor electrode material.
Further, the Schiff base transition metal polymerization thing monomer is Ni（salen）；It is molten in the organic electrolysis
In liquid, the concentration of the Schiff base transition metal polymerization thing monomer is 1mmol/L-10mmol/L.
Further, the organic electrolyte includes organic solvent and can be dissolved in the organic solvent and the electrolyte ionized；
The organic solvent is the low nonionic organic solvent of electron number, and the low nonionic organic solvent of the electron number is
Any one in propene carbonate, ethylene carbonate, acetonitrile, benzonitrile；In the low organic solvent of electron number, such as acetonitrile
(AN, DN=14.1), vinyl carbonate (EC, DN=16.4), propylene carbonate (PC, DN=15.1) etc., because solvent molecule is given
Electronic capability is weaker, can not be stabilized the coordination compound monomer molecule of oxidation state, therefore Schiff transient metal complex
Irreversible anode electric polymerization reaction can occur in this kind of solvent；The nonionic organic solvent be propene carbonate,
Any one in ethylene carbonate, acetonitrile, benzonitrile；The electrolyte is ionizable organic salt, and the electrolyte is
Tetraethyl ammonium, tetrabutylammonium, triethyl methyl tetrafluoroborate（Such as：Triethyl methyl tetrafluoro boron ammonium（TBAP））In it is any one
Kind.
Further, the electrochemical method is specially cyclic voltammetry, controls the electrochemical process condition to be：Potential window
0V-1.2V, cycle-index 15 times -20 times, the fast scope of sweeping of cyclic voltammetry in situ test is 10 mV/s-700 mV/s, constant current
The current density of charge-discharge test is 0.5A/g.Schiff base transition metal polymerization thing is carried out using cyclic voltammetry in situ
Polymerization, compound are intended to chain type growth, composite is remained the double electric of graphene using above-mentioned electrochemical method
Layer capacitance is provided simultaneously with the redox pseudo-capacitance of conducting polymer, and nitrogenize graphene-based bottom reduce electric charge enter be located at
The resistance of combination electrode polymer film electrode surface hole, so as to enhance storage and releasability of the electric charge in electrode, enter
And obtained combination electrode material has preferable chemical property.
A kind of nitrogen-doped graphene and Schiff base transition metal polymerization thing hybrid supercapacitor electrode material, it is described
Hybrid supercapacitor electrode material includes the electrode slice that surface has nitrogen-doped graphene, and the surface has N doping graphite
In-situ polymerization growth has Schiff base transition metal conducting polymer on the electrode slice of alkene.
The advantageous effects of the present invention：
1）The method of the invention prepares nitrogen-doped graphene using urea, and urea discharges ammonia, ammonia pair under high temperature action
Graphene is nitrogenized, and nitrogen-atoms is embedded in the graphene atomic layer of quasi- two-dimensional structure and is evenly dispersed therein, and increases
The surface utilisation of graphene, promote the growth in situ of Schiff base transition metal conducting polymer monomer in subsequent step,
Therefore, there is fake capacitance and excellent electrical conductance by the graphene of N doping, by the graphene of N doping as conductive base
The specific capacitance of bottom in-situ polymerization conducting polymer is compared than pure graphene and improves 10%-20%, and nitrogen-doped graphene is with leading
Electric polymer combination electrode material still keeps stable after multiple discharge and recharge.
2）The method of the invention is former using nitrogen-doped graphene as Schiff base transition metal conducting polymer monomer
The conductive substrates of position growth, compared with the graphene-based bottom without N doping, because nitrogen-atoms is in standard in nitrogen-doped graphene
Insertion in two-dimensional structure graphene atomic layer, make the graphene layer structure after doping more notable uniform.As conductive base
Bottom growth in situ Schiff base transition metal polymerization thing, under the function of current effectively be grown on nitridation graphene inside and
Surface, the incorporation of nitrogen-atoms reduce electric charge and enter the resistance for being located at combination electrode polymer film electrode surface hole, so as to
Strengthen storage and releasability of the electric charge in electrode, further, the combination electrode material prepared has preferable electrochemistry
Performance.
Brief description of the drawings
Fig. 1 is graphene（Graphene）As conductive substrates in-situ polymerization Ni（salen）With using urea nitrogen in embodiment 1
Change ratio is 1:10（Urea-10）As conductive substrates in-situ polymerization Ni（salen）Cyclic voltammetry curve；
Fig. 2 is graphene（Graphene）As conductive substrates in-situ polymerization Ni（salen）With embodiment 2 ratio is nitrogenized with urea
Example is 1:20（Urea-10）As conductive substrates in-situ polymerization Ni（salen）Cyclic voltammetry curve；
Fig. 3 is that graphene does not nitrogenize（Graphene）As conductive substrates in-situ polymerization Ni（salen）Urea is used with embodiment 3
Nitridation ratio is 1:30（Urea-10）As conductive substrates in-situ polymerization Ni（salen）Cyclic voltammetry curve；
Fig. 4 is graphene（Graphene）As conductive substrates in-situ polymerization Ni（salen）With embodiment 4 ratio is nitrogenized with urea
Example is 1:40（Urea-40）As conductive substrates in-situ polymerization Ni（salen）Cyclic voltammetry curve；
Fig. 5 is graphene（Graphene,GN）As conductive substrates in-situ polymerization Ni（salen）With using nitridation in embodiment 1-4
Graphene is as conductive substrates in-situ polymerization Ni（salen）Constant current charge-discharge curve.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
On the contrary, the present invention covers any replacement done in the spirit and scope of the present invention being defined by the claims, repaiied
Change, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, below to the thin of the present invention
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
Description can also understand the present invention completely.
Embodiment 1
Step 1：Weigh 20mg graphenes to be dissolved in 30ml ethanol, stirring and dissolving, then add 200mg urea and be put into ultrasound
In cell disruptor, ultrasonic 30min, urea is set all to dissolve.
Step 2：Solution obtained by step 1 is transferred into polytetrafluoroethylene (PTFE) to do in the reactor of liner, reactor is placed in
Natural cooling is taken out in 180 DEG C of high temperature microwave chemical reactors, after 12h and is filtered 12h is dried at cleaning 5-6 times, 80 DEG C.
Step 3：Titanium sheet is cut into the sheet that specification is 1cm × 3cm；Cleaned and deoiled with sodium carbonate liquor, deionization
Water is put into 30wt% hydrochloric acid solution after rinsing, and is washed with deionized water again only after soaking 2 h；Finally by clean titanium sheet with not
With model sand paper polish smooth it is stand-by.
Step 4：Weigh dried nitrogen-doped graphene 6mg in step 2 and be dissolved in dispersant N- methyl-pyrrolidons
In, Ultrasonic Pulverization forms uniform slurry, and finely dispersed slurry liquid-transfering gun is added drop-wise to titanium standby in step 3 by several times
Piece surface (adjustment carrying capacity is 0.1mg), is put into baking oven, in 80 DEG C of vacuum drying 12h.
Step 5：The electrode slice that step 4 is obtained carries out cyclic voltammetry and constant current charge-discharge test, organic electrolysis
Liquid is 1mol/L triethyl methyl tetrafluoro boron ammonium（TBAP）Acetonitrile solution, test voltage is 0V-1.2 V, and cyclic voltammetric is surveyed
Examination sweep speed is 40mV/s, and the test current density of constant current charge-discharge is 0.5 A/g.
Embodiment 2
Step 1：Weigh 20 mg graphenes to be dissolved in 30ml ethanol, stirring and dissolving, then add 400mg urea and be put into ultrasound
In cell disruptor, ultrasonic 30min, urea is set all to dissolve.
Step 2：With the step two in embodiment 1.
Step 3：With the step three in embodiment 1.
Step 4：With the step four in embodiment 1.
Step 5：With the step five in embodiment 1.
Embodiment 3
Step 1：Weigh 20 mg graphenes to be dissolved in 30ml ethanol, stirring and dissolving, then add 600mg urea and be put into ultrasound
In cell disruptor, ultrasonic 30min, urea is set all to dissolve.
Step 2：With the step two in embodiment 1.
Step 3：With the step three in embodiment 1.
Step 4：With the step four in embodiment 1.
Step 5：With the step five in embodiment 1.
Embodiment 4
Step 1：Weigh 20 mg graphenes to be dissolved in 30ml ethanol, stirring and dissolving, then add 800mg urea and be put into ultrasound
In cell disruptor, ultrasonic 30min, urea is set all to dissolve.
Step 2：With the step two in embodiment 1.
Step 3：With the step three in embodiment 1.
Step 4：With the step four in embodiment 1.
Step 5：With the step five in embodiment 1.
Embodiment 5
Step 1：With the step one in embodiment 4.
Step 2：With the step two in embodiment 1.
Step 3：Titanium sheet is cut into the sheet that specification is 1cm × 3cm；Cleaned and deoiled with sodium carbonate liquor, deionization
Water is put into 30wt% hydrochloric acid solution after rinsing, and is washed with deionized water again only after soaking 2 h；Finally by clean titanium sheet with not
With model sand paper polish smooth it is stand-by.
Step 4：Weigh dried nitrogen-doped graphene 6mg in step 2 and be dissolved in dispersant N- methyl-pyrrolidons
In, Ultrasonic Pulverization forms uniform slurry, and finely dispersed slurry liquid-transfering gun is added drop-wise to titanium standby in step 3 by several times
Piece surface (adjustment carrying capacity is 0.2mg), is put into baking oven, in 80 DEG C of vacuum drying 12h.
Step 5：With the step five in embodiment 1.
Embodiment 6
Step 1：With the step one in embodiment 4.
Step 2：With the step two in embodiment 1.
Step 3：Titanium sheet is cut into the sheet that specification is 1cm × 3cm；Cleaned and deoiled with sodium carbonate liquor, deionization
Water is put into 30wt% hydrochloric acid solution after rinsing, and is washed with deionized water again only after soaking 2 h；Finally by clean titanium sheet with not
With model sand paper polish smooth it is stand-by.
Step 4：Weigh dried nitrogen-doped graphene 6mg in step 2 and be dissolved in dispersant N- methyl-pyrrolidons
In, Ultrasonic Pulverization forms uniform slurry, and finely dispersed slurry liquid-transfering gun is added drop-wise to titanium standby in step 3 by several times
Piece surface (adjustment carrying capacity is 0.3mg), is put into baking oven, in 80 DEG C of vacuum drying 12h.
Step 5：With the step five in embodiment 1.
Embodiment 7
Step 1：With the step one in embodiment 4.
Step 2：With the step two in embodiment 1.
Step 3：Titanium sheet is cut into the sheet that specification is 1cm × 3cm；Cleaned and deoiled with sodium carbonate liquor, deionization
Water is put into 30wt% hydrochloric acid solution after rinsing, and is washed with deionized water again only after soaking 2 h；Finally by clean titanium sheet with not
With model sand paper polish smooth it is stand-by.
Step 4：Weigh dried nitrogen-doped graphene 6mg in step 2 and be dissolved in dispersant N- methyl-pyrrolidons
In, Ultrasonic Pulverization forms uniform slurry, and finely dispersed slurry liquid-transfering gun is added drop-wise to titanium standby in step 3 by several times
Piece surface (adjustment carrying capacity is 0.4mg), is put into baking oven, in 80 DEG C of vacuum drying 12h.
Step 5：With the step five in embodiment 1.
Embodiment 8
Step 1：With the step one in embodiment 4.
Step 2：With the step two in embodiment 1.
Step 3：Titanium sheet is cut into the sheet that specification is 1cm × 3cm；Cleaned and deoiled with sodium carbonate liquor, deionization
Water is put into 30wt% hydrochloric acid solution after rinsing, and is washed with deionized water again only after soaking 2 h；Finally by clean titanium sheet with not
With model sand paper polish smooth it is stand-by.
Step 4：Weigh dried nitrogen-doped graphene 6mg in step 2 and be dissolved in dispersant N- methyl-pyrrolidons
In, Ultrasonic Pulverization forms uniform slurry, and finely dispersed slurry liquid-transfering gun is added drop-wise to titanium standby in step 3 by several times
Piece surface (adjustment carrying capacity is 0.5mg), is put into baking oven, in 80 DEG C of vacuum drying 12h.
Step 5：With the step five in example 1.
Analyzed from above example and Fig. 1-5：As depicted in figs. 1 and 2, when graphene and the ratio of nitridizing agent urea
Example is 1:10 and 1:When 20, compared with the combination electrode not nitrogenized, there are redox peaks in the former；And from Fig. 3, Fig. 4
Combination electrode cyclic voltammetry curve by nitridation also has an appearance of redox peaks, and in Fig. 3 oxidation peak peak current most
Greatly, illustrate that nitrogenize graphene has rush to the specific capacity for improving Schiff base transition metal polymerization thing electrode material for super capacitor
Enter effect, and it is 1 to nitrogenize ratio:Effect is the most obvious when 30.In addition, from figure 5 it can be seen that pass through the combination electrode of nitridation
The discharge and recharge time of material is all higher than the composite without nitridation, further, multiple with the gradual increase of nitridation ratio
The discharge and recharge time of composite electrode material gradually increases, high 10%-20% when the pure graphene of its capacity ratio is as substrate.
Claims (9)
- A kind of 1. preparation of nitrogen-doped graphene and Schiff base transition metal polymerization thing hybrid supercapacitor electrode material Method, it is characterised in that methods described prepares the electrode slice for having nitrogen-doped graphene in surface using nitrogen-doped graphene； Electrode slice of the surface with nitrogen-doped graphene is placed in containing the organic of Schiff base transition metal polymerization thing monomer In electrolyte, in-situ polymerization is carried out by electrochemical method, obtains the hybrid supercapacitor electrode material.
- 2. a kind of nitrogen-doped graphene and Schiff base transition metal polymerization thing compound super electric capacity according to claim 1 The preparation method of device electrode material, it is characterised in that the preparation method tool of electrode slice of the surface with nitrogen-doped graphene Body is：Prepare nitrogen-doped graphene：A certain amount of graphene is dissolved in ethanol, stirred, urea is added, continues to stir, is turned after dissolving Enter reactor, reactor is placed in high temperature microwave chemical reactor and reacted, reaction is taken out after terminating, and is cooled down, is used ethanol And deionized water cleaning, dry, obtain dried nitrogen-doped graphene；The preparation of collector titanium sheet：Titanium sheet is cut into the sheet of certain specification, is cleaned and deoiled with sodium carbonate liquor, then go from Sub- water is put into after rinsing in the hydrochloric acid solution that mass concentration is 30wt%, is washed with deionized water only after soaking 2 h, will finally be washed again Net titanium sheet is polished smooth with the sand paper of different model, obtains the collector titanium sheet；The preparation of electrode slice：The dried nitrogen-doped graphene is weighed, is dissolved in dispersant N- methyl-pyrrolidons, is surpassed Sound crushes, and obtains nitrogen-doped graphene uniform sizing material；The nitrogen-doped graphene uniform sizing material is coated in the collector titanium The surface of piece, is then placed in baking oven, in 80 DEG C of vacuum drying 12h, naturally cools to room temperature, obtains the surface and is mixed with nitrogen The electrode slice of miscellaneous graphene.
- 3. a kind of nitrogen-doped graphene and Schiff base transition metal polymerization thing compound super electric capacity according to claim 2 The preparation method of device electrode material, it is characterised in that in described the step of preparing nitrogen-doped graphene：Control the graphene Solid-to-liquid ratio with the ethanol is 20mg：30-60ml；It is 1 to control the mass ratio of graphene and urea:（10-300）；Will be anti- Kettle is answered to be placed in high temperature microwave chemical reactor, controlling reaction temperature is 160 DEG C -220 DEG C, reaction time 6h-15h.
- 4. a kind of nitrogen-doped graphene and Schiff base transition metal polymerization thing compound super electric capacity according to claim 2 The preparation method of device electrode material, it is characterised in that the preparation process Jing Guo the collector titanium sheet, the collector prepared Titanium sheet will meet the requirement of collector, ensure the repeatability of experiment.
- 5. a kind of nitrogen-doped graphene and Schiff base transition metal polymerization thing compound super electric capacity according to claim 2 The preparation method of device electrode material, it is characterised in that in the preparation process of the electrode slice, control the surface prepared On electrode slice with nitrogen-doped graphene, the carrying capacity of nitrogen-doped graphene is 0.1-0.5mg/cm2。
- 6. a kind of nitrogen-doped graphene and Schiff base transition metal polymerization thing compound super electric capacity according to claim 1 The preparation method of device electrode material, it is characterised in that by the surface with nitrogen-doped graphene electrode slice be placed in containing In the organic electrolyte of Schiff base transition metal polymerization thing monomer, the method for carrying out in-situ polymerization is specially：Build organic three-electrode system：Using electrode slice of the surface with nitrogen-doped graphene as working electrode, reference electricity Extremely Ag/AgCl, auxiliary electrode are the active carbon cloth of large area；In-situ polymerization：Schiff base transition metal polymerization thing monomer is dissolved in organic electrolyte, in organic three electrode In system, by electrochemical method, the in situ Polymerization growth of the electrode slice with nitrogen-doped graphene on the surface Schiff base transition metal conducting polymer, obtains the hybrid supercapacitor electrode material.
- 7. a kind of nitrogen-doped graphene and Schiff base transition metal polymerization thing compound super electric capacity according to claim 6 The preparation method of device electrode material, it is characterised in that the Schiff base transition metal polymerization thing monomer is Ni（salen）； In the excellent electrolytic solution, the concentration of the Schiff base transition metal polymerization thing monomer is 1mmol/L-10mmol/ L。
- 8. according to a kind of nitrogen-doped graphene of claim 1 or 6 and Schiff base transition metal polymerization thing compound super The preparation method of capacitor electrode material, it is characterised in that the electrochemical method is specially cyclic voltammetry, controls electrochemistry Process condition is：Potential window 0V-1.2V, cycle-index 15 times -20 times, cyclic voltammetry test in situ sweep fast scope as 10 MV/s-700 mV/s, the current density of constant current charge-discharge test is 0.5A/g.
- 9. a kind of nitrogen-doped graphene and Schiff base transition metal polymerization thing hybrid supercapacitor electrode material, its feature It is, the hybrid supercapacitor electrode material includes the electrode slice that surface has nitrogen-doped graphene, and the surface has In-situ polymerization growth has Schiff base transition metal conducting polymer on the electrode slice of nitrogen-doped graphene.
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