CN106683895A - Anthraquinone-based modified composite electrode material, preparation method and application thereof, and electronic component containing anthraquinone-based modified composite electrode material - Google Patents
Anthraquinone-based modified composite electrode material, preparation method and application thereof, and electronic component containing anthraquinone-based modified composite electrode material Download PDFInfo
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- CN106683895A CN106683895A CN201710040337.9A CN201710040337A CN106683895A CN 106683895 A CN106683895 A CN 106683895A CN 201710040337 A CN201710040337 A CN 201710040337A CN 106683895 A CN106683895 A CN 106683895A
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- Prior art keywords
- anthraquinone
- electrode material
- anthraquinonyl
- combination electrode
- solution
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 73
- 239000007772 electrode material Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- -1 anthraquinonyl Chemical group 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000012986 modification Methods 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 238000013461 design Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 241001597008 Nomeidae Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000003990 capacitor Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000000499 gel Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 229920001940 conductive polymer Polymers 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000004058 9,10-anthraquinones Chemical class 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 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
- H01G11/26—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
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides an anthraquinone-based modified composite electrode material, a preparation method and application thereof, and an electronic component containing the material. According to the method, the anthraquinone precursor is added into the graphene oxide gel and subjected to ultrasonic dispersion to obtain the anthraquinone-modified graphene oxide dispersion liquid. The target composite electrode material is prepared by taking graphene oxide as an oxidant and adopting a hydrothermal method under the conditions of high temperature and high pressure, and the preparation method has the advantages of simplicity, high yield, easiness in batch production and the like; meanwhile, the prepared composite electrode material has good mechanical property and electrochemical activity, and can be used for preparing electronic components such as super capacitors and the like. Furthermore, the prepared electronic component has excellent electrical properties and can be applied to various environments.
Description
Technical field
The present invention relates to novel energy-storing Material Field, modifies combination electrode material and its system in particular to anthraquinonyl
Preparation Method and application, and the electronic devices and components comprising the material.
Background technology
Ultracapacitor, also referred to as electrochemical capacitor, are a kind of new storages between rechargeable battery and capacitor
Energy device, proposes so far from first patent about ultracapacitor, the time of existing over half a century.With traditional capacitor
Compare, ultracapacitor has the features such as energy is high, density is high, its capacitance 1-2 order of magnitude higher than conventional capacitor；
Meanwhile, compared with secondary cell, ultracapacitor also has very big advantage on power and cycle life.Therefore, super electricity
Container has a wide range of applications in fields such as electric power, traffic, space flight, in particular with the promotion and application of green energy resource,
As also can increasingly receiving more extensive concern with ultracapacitor associated with power-type lithium ion battery.
In recent years, it is relatively more with regard to the research work of ultracapacitor, as decision performance of the supercapacitor key factor
Electrode material also become naturally the most important thing of research.Existing electrode material mainly has following several：
(1) using single Graphene or conducting polymer (such as by polythiophene, polyaniline, polypyrrole, poly- anthraquinone etc.)
Material, for preparing ultracapacitor；
(2) after will be the conducting polymers such as polythiophene, polyaniline, polypyrrole and Graphene compound, for preparing super capacitor
Device；
(3) electrochemical process chemical method or chemical copolymerization method prepare anthraquinonyl and graphene composite material, and are used for super electricity
In prepared by container.
However, existing electrode material and/or its preparation method still have more deficiency, for example：Although adopting electrochemistry
The composite property that method reaction is generated is preferable, but electrochemical reaction is less efficient, and product is few, when reacting film layer and being thicker,
It is easy to fall off, cause reaction to terminate in advance；Product is easily come off with colelctor electrode, loses electro-chemical activity, it is difficult to large-scale application；
Meanwhile, then reactions steps are complicated to prepare electrode material using chemical reaction method, chemical copolymerization method or hot melt, instead
During answering, waste is more, and product purity is relatively low, and environmental pollution is more serious.Further, using chemistry
Electrode material prepared by method is generally solid material (caking), reunites very serious, generally requires the methods such as ball milling by which from bulk
Thing wears into powder.And the post-processing approach of this grinding is on the one hand more serious to the damage of conducting polymer, can significantly
The electrochemical properties of conducting polymer are reduced, on the other hand is also difficult to prepare the graphene-based composite wood with nanoscale
Material.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide the preparation method that a kind of anthraquinonyl modifies combination electrode material, present invention side
In method, by graphene oxide is mixed with poly- anthraquinone presoma, and target combination electrode material is prepared with hydro-thermal method, had
Have that preparation method is simple, yield is high, it is easy to the advantages of mass production；Meanwhile, obtained combination electrode material also has good
Good mechanical performance and electro-chemical activity.
The second object of the present invention is to provide one kind anthraquinonyl modification combination electrode by obtained in the method for the invention
Material.Combination electrode material provided by the present invention has the macroscopic three dimensional stereochemical structure formed by redox graphene；Together
When, in microstructure, as redox graphene nanoscale twins surface has also generated poly- anthraquinone, thus also obtain poly- anthracene
The sandwich structure (sandwich structure) of quinone-redox graphene-poly- anthraquinone.Further, due to combination electrode of the present invention
Interaction and the 3-D solid structure bigger serface characteristic having in material between composite, also so that the present invention is compound
Electrode material has good chemical property；Likewise, as 3-D solid structure causes combination electrode material tool of the present invention
There is preferable mechanical performance, and this also causes combination electrode material of the present invention to have excellent mechanical stability.
Third object of the present invention is to provide the application that a kind of anthraquinonyl of the present invention modifies combination electrode material.This
Bright combination electrode material has good chemical property and mechanical performance, it is thus possible to for preparing such as ultracapacitor etc.
Electronic devices and components in.
Fourth object of the present invention is to provide a kind of electronics that combination electrode material is modified comprising anthraquinonyl of the present invention
Components and parts, as the feature combination electrode material for being included has good chemical property and mechanical performance, so that
Electronic devices and components provided by the present invention have excellent electric property, while can also apply in various environment.
In order to realize the above-mentioned purpose of the present invention, spy employs the following technical solutions：
A kind of anthraquinonyl modifies the preparation method of combination electrode material, and methods described comprises the steps：
Graphene oxide gel is taken, supersound process after adding water obtains graphene oxide dispersion；
Poly- anthraquinone presoma, and supersound process after being dissolved are taken, anthraquinone solution is obtained；
After graphene oxide dispersion is mixed with anthraquinone solution, supersound process obtains mixed solution；Then, in mixing
Catalyst is added in solution, and continues stirring mixing, obtain composite solution；
Composite solution is reacted under hydrothermal conditions, anthraquinonyl modification combination electrode material is obtained.
Optionally, in the present invention, the poly- anthraquinone presoma is anthraquinone and/or anthraquinone derivative.
Optionally, the present invention in, the catalyst be nitrite tert-butyl, nitrous acid straight butyl, phosphorus heteropoly tungstic acid, or
The mixed catalyst of one or more in the acid of silica-alumina solid catalysis.
Optionally, in the present invention, the catalyst is 2 with the quality grams ratio of poly- anthraquinone presoma in mixed solution：1~
5：1.
Optionally, in the present invention, in the step of mixing graphene oxide dispersion with anthraquinone solution, graphene oxide
In dispersion liquid, the quality of graphene oxide and the mass ratio of poly- anthraquinone presoma in anthraquinone solution are 1：20~20：1.
Optionally, it is in the present invention, described that composite solution is reacted under hydrothermal conditions, it is the method using heating up stage by stage
Carry out hydro-thermal reaction；Specifically, it is first to be warming up to 80~120 DEG C with the heating rate of 1~5 DEG C/min；Then again with 5~10
DEG C/heating rate of min is warming up to reaction design temperature, last 8~24h of isothermal reaction under reaction design temperature again.
Meanwhile, present invention also offers the anthraquinonyl modification combination electrode material by obtained in the method for the invention.
Optionally, in the present invention, the anthraquinonyl modification combination electrode material is 3-D solid structure；Meanwhile, the material
Sandwich layered microstructure of the material with poly- anthraquinone-redox graphene-poly- anthraquinone.
Likewise, present invention also offers the anthraquinonyl modifies combination electrode material answering in electronic devices and components are prepared
With.
Further, present invention provides the electronic devices and components of combination electrode material are modified comprising the anthraquinonyl.
Compared with prior art, beneficial effects of the present invention are：
(1) preparation method of the present invention is simple, easily prepare, and yield is high, can industrial mass production, meanwhile, product is followed
Ring stability and high temperature stability performance are good；
(2) anthraquinonyl of the present invention modifies combination electrode material excellent combination property, with 3-D solid structure and compares table
Area is big, so as to facilitate ion to carry out adsorption desorption in active material/electrolyte interface, it is possible to increase double electric capacity of active material are special
Property；Simultaneously because ion can carry out the contact of rapid large-area with conductive polymer poly anthraquinone, poly- anthraquinone is also enabled to discharge
Go out higher fake capacitance characteristic, and cause combination electrode material of the present invention that there is higher specific capacity.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described.
Fig. 1 is the composite solution gel provided in one embodiment of the invention；
Fig. 2 be provided in one embodiment of the invention add reactor in treat the composite solution of hydro-thermal reaction；
Fig. 3 is the anthraquinonyl modification combination electrode material product provided in one embodiment of the invention；
Fig. 4 is that the mechanical performance of the anthraquinonyl modification combination electrode material product provided in one embodiment of the invention is drilled
Diagram；
Fig. 5 is the anthraquinonyl modification combination electrode material product SEM figures provided in one embodiment of the invention.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted concrete in embodiment
Condition person, the condition advised according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products that commercially available purchase is obtained can be passed through.
In the inventive method, (using improved Hummer methods, the method is by the industry to prepare graphene oxide gel first
Widely use) and anthraquinone solution；Then, a certain amount of anthraquinone solution, catalyst and a certain amount of graphene oxide gel are filled
It is point uniform, it is ensured that many kinds of substance is fully contacted.Again under hydrothermal conditions (High Temperature High Pressure), graphene oxide (GO) is reduced into
Redox graphene with 3-D solid structure (RGO), while RGO nanometer sheet surface aggregate generates poly- anthraquinone material, and
Form microcosmic and there is the poly- anthraquinone sandwich structures of poly- anthraquinone-RGO-, macroscopic view has the anthraquinone base composite electric of stereoscopic three-dimensional structure
Pole, concrete steps flow process are as follows：
1) graphene oxide gel is taken, supersound process after adding water obtains graphene oxide dispersion；
In this step, deionized water is preferably added in graphene oxide gel；Meanwhile, supersound process is preferably in ice
Carry out under the conditions of bath, it is furthermore preferred that the temperature control of ice bath is at 0~5 DEG C, the time control of supersound process is in 0.5~3h and excellent
That what is selected obtains the dispersion liquid that graphene oxide concentration is 0.5~6mg/ml；
2) poly- anthraquinone presoma, and supersound process after being dissolved are taken, anthraquinone solution is obtained；
In this step, the poly- anthraquinone presoma is anthraquinone and/or anthraquinone derivative, for example, can be 9,10- anthraquinones,
- 9.10 anthraquinone of 1- amino, -9.10 anthraquinone of 2- amino, -9.10 anthraquinone of 1.2- diaminourea, -9.10 anthracene of 1.4- diaminourea
Anthraquinone compounds or the anthraquinone derivatives such as -9.10 anthraquinone of quinone or 2.6- diaminourea；Meanwhile, solution used by anthraquinone dissolving is excellent
Choosing for organic solution, the more preferably mixed solution of acetonitrile/n-butyl alcohol and ethyl acetate/chloroform, wherein, acetonitrile/
The ratio of the volume milliliter number of n-butyl alcohol and ethyl acetate/chloroform is 1：1~50：1；
Further, in this step, the supersound process is carried out under 0~5 DEG C of condition of ice bath, and controls ultrasonic place
The time of reason is 0.5~3h, then obtains the anthraquinone solution that poly- anthraquinone precursor concentration is 0.5~10mg/ml；
3), after mixed graphene oxide dispersion with anthraquinone solution, supersound process obtains mixed solution；
In this step, first have to measure appropriate graphene dispersing solution and anthraquinone solution, and in causing measured solution,
Raw graphite alkene is 20 with the mass ratio of the poly- anthraquinone presoma of raw material：1~1：20；
Meanwhile, in this step, supersound process is carried out under 0~5 DEG C of condition of ice bath, and controls the time of supersound process
For 2~5h；
4) catalyst is added in mixed solution, and continues stirring mixing, obtain composite solution；
In this step, used catalyst is preferably nitrite tert-butyl, nitrous acid straight butyl, phosphorus heteropoly tungstic acid, or
The mixed catalyst of one or more in the acid of silica-alumina solid catalysis；It is furthermore preferred that institute in this step
It is that nitrite tert-butyl, nitrous acid straight butyl, phosphorus heteropoly tungstic acid, or silica-alumina solid are urged with catalyst
Change the one kind in acid；
Meanwhile, catalyst is preferably controlled 2 with the mass ratio of contained poly- anthraquinone presoma in composite solution：1~5：
1；
In order to avoid catalyst photodissociation, so this step is preferably operated in darkroom, while in stirring at low speed bar
Under part, mix 0.5~1h；
5) composite solution is reacted under hydrothermal conditions, obtains anthraquinonyl modification combination electrode material；
In this step, first have to by composite solution add reactor in, and control composite solution amount be reactor capacity
30~70%；
Then reactor is put in high temperature oven, and the method using temperature-gradient method carries out hydro-thermal reaction, specifically, can
With elder generation according to the programming rate of 1~5 DEG C/min, oven temperature is risen to into 80~120 DEG C, for example, can be warming up to 100 DEG C；So
Afterwards, according to 5~10 DEG C of heating rate, oven temperature is risen to into design temperature, can for example arrange design temperature for 150~
200℃；Finally, 8~24h of isothermal reaction at a set temperature, finally gives product；
Further, through above-mentioned reaction, the reaction result of each raw material is as follows：
(1), under High Temperature High Pressure, graphene oxide (GO) is reduced into redox graphene (RGO)；
(2) simultaneously as the Oxidation of GO, under high-temperature and high-pressure conditions, anthraquinone is gone back with GO as organic centre in GO
While former, being attached to GO nanometer sheet surface carries out polyreaction, generates with obvious sandwich structure microstructure, that is, gathers
The structure of the poly- anthraquinones of anthraquinone-RGO-；
(3) composite prepared by hydro-thermal method has obvious 3-D solid structure, can be referred to as hydrogel (diameter
The weight of the cylinder product of 20mm, height 50mm is only 60mg), with preferable three-dimensional mechanical characteristic, can bear larger outer
Power is acted on.
As can be seen here, the inventive method operating procedure is relatively simple, easily prepared, and yield is very high, is suitable to extensive
Industrialized production.
Simultaneously, although the inventive method is also to be combined poly- anthraquinone and Graphene, but prepared yield is far longer than
Electrochemical process, for example：Using the inventive method, the yield of combination electrode material can reach a gram level；At the same time it can also basis
It is sized using the size of reactor, to obtain the product with any thickness.If however, using traditional electrochemistry
Method simultaneously adopts with identical raw material in the application to prepare similar complex, and its yield is only milligram rank, and product is thick
Degree easily comes off once reaching more than 50 microns.
Further, relative to chemical method and electrochemistry, the product prepared by the present invention has 3-D solid structure, can fill
The characteristic of the high-specific surface area of composite is waved in distribution, facilitates ion to carry out adsorption desorption in active material/electrolyte interface, is improved
Double capacitance characteristics of active material, the rapid large-area for being also advantageous for ion with conductive polymer poly anthraquinone are contacted, the poly- anthracene for making
Quinone can discharge higher fake capacitance characteristic.
Further, the inventive method step specifically may be referred to as follows：
(1) graphene oxide (GO) gel is taken, and adds deionized water；Then, under 0~5 DEG C of condition of ice bath, at ultrasound
0.5~3h of reason, obtains the GO dispersion liquid A of 0.5~6mg/ml；
(2) take poly- anthraquinone presoma (for example：9,10- anthraquinones, -9.10 anthraquinone of 1- amino, -9.10 anthracene of 2- amino
Quinone, -9.10 anthraquinone of 1.2- diaminourea, -9.10 anthraquinone of 1.4- diaminourea, -9.10 anthraquinone of 2.6- diaminourea), which is molten
Enter in mixed organic solvents that (acetonitrile/n-butyl alcohol and ethyl acetate, chloroform are according to 1：1~50：1 ratio mixing gained),
And under 0~5 DEG C of condition of ice bath, 0.5~3h of supersound process obtains the anthraquinone solution B of 0.5~10mg/ml；
(3) by GO dispersion liquids A and anthraquinone solution B, according to 20：1~1：20 ratio (the quality of GO and poly- anthraquinone presoma
Than) mixing, and under 0~5 DEG C of condition of ice bath, 2~5h of supersound process obtains mixed solution C；
(4) catalyst nitrite tert-butyl is added in mixed solution C, catalyst with the mass ratio of poly- anthraquinone presoma is
2：1~5：1,0.5~1h of low speed magnetic agitation in dark room, obtain mixed solution D；
(5) by mixed solution D import pyroreaction kettle in, control mixed solution D amount be reactor capacity 30~
70%；
(6) reactor is put in high temperature oven, is reacted using temperature-gradient method method：Leading portion：Room temperature is to 100
DEG C, heating rate is 1~5 DEG C/min；Back segment：100 DEG C are warmed up to setting reaction temperature, (set reaction temperature as 150~200
DEG C), heating rate is 5~10 DEG C/min；The high temperature constant temperature response time is 8~24h.
Anthraquinonyl by obtained by said method of the present invention modifies combination electrode material in macrostructure, with by RGO
The 3-D solid structure for being constituted；And in microstructure, the sandwich structure with the poly- anthraquinones of poly- anthraquinone-RGO-；Meanwhile,
As combination electrode material has larger specific surface area (＞ 1000m2/ g) with higher specific capacity (＞ 200F/g), thus
With good hot properties and cyclical stability, after 4000 circulations, its Capacitance Shift Rate less than 5% (poly- anthraquinone and
Graphene itself is stablized, and adds sandwich structure, can further improve the electrochemical stability of composite), and energy
More than 400 DEG C of high temperature is tolerated enough.
Further, anthraquinonyl modification combination electrode material provided by the present invention as functional material, and can also be used
In preparing the electronic devices and components such as ultracapacitor.
Embodiment 1
(1) appropriate graphene oxide (GO) gel is taken, and adds deionized water；Then, under 0 DEG C of condition of ice bath, ultrasound
2h is processed, the GO dispersion liquid A of 6mg/ml are obtained；
(2) appropriate 9,10- anthraquinones are taken, acetonitrile and ethyl acetate (volume ratio 1 in mixed organic solvents is dissolved in：1)
In mixed solution, and under 0 DEG C of condition of ice bath, supersound process 2h obtains the anthraquinone solution B of 6mg/ml；
(3) according to volume ratio 1：1 ratio, measures appropriate GO dispersion liquids A and anthraquinone solution B respectively, and mixes, Ran Hou
Under 0~5 DEG C of condition of ice bath, 2~5h of supersound process obtains mixed solution C；
(4) the addition catalyst nitrite tert-butyl in mixed solution C, and cause the matter of catalyst and poly- anthraquinone presoma
Amount is than being 2：1, and 0.5~1h of low speed magnetic agitation in dark room, obtain mixed solution D as shown in Figure 1；
(5) mixed solution D is imported in pyroreaction kettle, as shown in Fig. 2 the amount for controlling mixed solution D is held for reactor
The 60% of amount；
(6) reactor is put in high temperature oven, is reacted using temperature-gradient method method：First with the liter of 1~5 DEG C/min
Warm ramp is to 100 DEG C；Then 200 DEG C, and isothermal reaction 24h are warming up to the heating rate of 10 DEG C/min again, obtain as
Anthraquinonyl modification combination electrode material shown in Fig. 3；Further, anthraquinonyl modifies the scanning electron microscope structure of combination electrode material
As shown in Figure 5.
The specific capacity of the anthraquinonyl modification combination electrode material of embodiment 1 is 247F/g, the permanent electricity under 1A/g electric current densities
Stream discharge and recharge 4000 times, its capacity attenuation rate is less than 4%.
Measuring mechanical property, test side are carried out to the anthraquinonyl modification combination electrode material obtained by embodiment 1 further
Method is as follows：
First, randomly select 4 pieces to repeat to test obtained anthraquinonyl modification combination electrode material by 1 method of embodiment；
Then, as shown in Fig. 4 (a), 4 pieces of combination electrode materials are placed on flat glass plate, and rectangular distribution；
Then, the glass plate by one piece of thickness for 5mm is placed on 4 pieces of combination electrode materials, and causes combination electrode material
The corner of material difference supporting glass plate, and each piece of combination electrode material deformation situation is observed after 30min；As a result such as Fig. 4 (b) institutes
Show, 4 pieces of combination electrode materials under the pressure effect of one piece of glass plate, only slightly compress, and obvious deformation does not occur by volume；
Then, then respectively two pieces of identical glass plates are overlapped successively and is positioned on 4 pieces of combination electrode materials, and
Observe each piece of combination electrode material deformation situation after 30min again；As a result as shown in Fig. 4 (b), 4 pieces of combination electrode materials are three
Under the pressure effect of block glass plate, only body is more previous slightly compresses, but does not occur obvious deformation yet；
Finally, again four pieces of glass plates are overlapped and is positioned on 4 pieces of combination electrode materials, and seen after 30min again
Examine each piece of combination electrode material deformation situation；As a result as shown in Fig. 4 (d), pressure of 4 pieces of combination electrode materials in seven pieces of glass plates
Under effect, only body is more previous has compressed, but does not occur obvious deformation yet.
From above-mentioned pressure test, the anthraquinonyl modification combination electrode material by obtained by the inventive method has good
Resistance to compression and mechanical performance.
Embodiment 2
(1) appropriate graphene oxide (GO) gel is taken, and adds deionized water；Then, under 0~5 DEG C of condition of ice bath, surpass
Sonication 1h, obtains the GO dispersion liquid A of 1mg/ml.
(2) appropriate -9.10 anthraquinone of 1.2- diaminourea is taken, n-butyl alcohol and chloroform (volume ratio 10 is dissolved in：1)
In mixed solution, and under 0 DEG C of condition of ice bath, supersound process 2.5h obtains the anthraquinone solution B of 10mg/ml；
(3) according to volume ratio 30：1 ratio, is measured appropriate GO dispersion liquids A respectively and is mixed with anthraquinone solution B, and at 5 DEG C
Under condition of ice bath, supersound process 5h obtains mixed solution C；
(4) catalyst nitrite tert-butyl is added in mixed solution C, catalyst with the mass ratio of poly- anthraquinone presoma is
2：1, low speed magnetic agitation 1h in dark room obtains mixed solution D；
(5) mixed solution D is imported in pyroreaction kettle, the amount for controlling mixed solution D is the 30% of reactor capacity；
(6) reactor is put in high temperature oven, is reacted using temperature-gradient method method：First with the liter of 1~5 DEG C/min
Warm ramp is to 100 DEG C；Then 180 DEG C, and isothermal reaction 24h are warming up to the heating rate of 5 DEG C/min again, are obtained such as figure
Anthraquinonyl modification combination electrode material shown in 3.
The specific capacity of the anthraquinonyl modification combination electrode material of embodiment 2 is 193F/g, the permanent electricity under 1A/g electric current densities
Stream discharge and recharge 4000 times, its capacity attenuation rate is less than 1.5%.
Further, by obtained by embodiment 2 anthraquinonyl modification combination electrode material with 1 combination electrode of embodiment
The suitable compressive property of material and mechanical performance.
The inventive method raw material is cheap and easy to get, and operating procedure simple and fast, and yield is high, it is easy to which industrialization is given birth on a large scale
Produce；Meanwhile, the anthraquinonyl modification combination electrode material chemical property and mechanical performance by obtained by the inventive method is excellent, energy
Enough it is further used as functional material and prepares the electronic devices and components such as ultracapacitor.
Although with specific embodiment illustrate and describing the present invention, but it will be appreciated that without departing substantially from the present invention's
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including all such changes and modifications belonged in the scope of the invention.
Claims (10)
1. a kind of anthraquinonyl modifies the preparation method of combination electrode material, it is characterised in that methods described comprises the steps：
Graphene oxide gel is taken, supersound process after adding water obtains graphene oxide dispersion；
Poly- anthraquinone presoma, and supersound process after being dissolved are taken, anthraquinone solution is obtained；
After graphene oxide dispersion is mixed with anthraquinone solution, supersound process obtains mixed solution；Then, in mixed solution
Middle addition catalyst, and continue stirring mixing, obtain composite solution；
Composite solution is reacted under hydrothermal conditions, anthraquinonyl modification combination electrode material is obtained.
2. preparation method according to claim 1, it is characterised in that the poly- anthraquinone presoma is anthraquinone and/or anthraquinone
Derivant.
3. preparation method according to claim 1, it is characterised in that the catalyst is nitrite tert-butyl, nitrous acid
N-butyl, the mixed catalytic of one or more in phosphorus heteropoly tungstic acid, or the acid of silica-alumina solid catalysis
Agent.
4. preparation method according to claim 3, it is characterised in that the catalyst and poly- anthraquinone forerunner in mixed solution
The quality grams ratio of body is 2：1~5：1.
5. preparation method according to claim 1, it is characterised in that graphene oxide dispersion is being mixed with anthraquinone solution
In the step of conjunction, in graphene oxide dispersion in the quality of graphene oxide and anthraquinone solution poly- anthraquinone presoma mass ratio
Example is 1：20~20：1.
6. preparation method according to claim 1, it is characterised in that described that composite solution is reacted under hydrothermal conditions,
It is that hydro-thermal reaction is carried out using the method for heating up stage by stage；
Specifically, it is first to be warming up to 80~120 DEG C with the heating rate of 1~5 DEG C/min；Then again with the liter of 5~10 DEG C/min
Warm ramp to design temperature is reacted, finally again reaction design temperature under 8~24h of isothermal reaction.
7. anthraquinonyl obtained in the method by any one of claim 1-6 modifies combination electrode material.
8. anthraquinonyl according to claim 7 modifies combination electrode material, it is characterised in that the anthraquinonyl modification is compound
Electrode material is 3-D solid structure；Meanwhile, the material has Sanming City of poly- anthraquinone-redox graphene-poly- anthraquinone
Control layered microstructure.
9. anthraquinonyl modification application of the combination electrode material in electronic devices and components are prepared described in claim 7 or 8.
10. it is a kind of comprising described in claim 7 or 8 anthraquinonyl modify combination electrode material electronic devices and components.
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| CN110783113A (en) * | 2019-11-06 | 2020-02-11 | 西北师范大学 | Preparation and application of indanthrene functionalized graphene three-dimensional network structure composite material |
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