CN108428556A - A kind of graphene/metal anthraquinone complex/carbon/polyaniline super capacitor electrode material and preparation method thereof - Google Patents
A kind of graphene/metal anthraquinone complex/carbon/polyaniline super capacitor electrode material and preparation method thereof Download PDFInfo
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- CN108428556A CN108428556A CN201810225399.1A CN201810225399A CN108428556A CN 108428556 A CN108428556 A CN 108428556A CN 201810225399 A CN201810225399 A CN 201810225399A CN 108428556 A CN108428556 A CN 108428556A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 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 46
- 239000007772 electrode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 28
- 239000003990 capacitor Substances 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- -1 iron ion anthraquinone Chemical class 0.000 claims abstract description 36
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 19
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical class O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of graphene/metal anthraquinone complex/carbon/polyaniline super capacitor electrode materials and preparation method thereof, belong to the synthesis technical field of electrode material for super capacitor, this method mainly includes the following steps that：Graphene oxide is obtained by chemical oxidization method（GO）, graphene oxide and 1,5 diamino-anthraquinones（DAAQ）, green vitriol is in N, N dimethylformamides（DMF）In reduced graphene/iron ion anthraquinone complex prepared by simple one-step method reflux（rGO‑DAAQ/Fe）；Reduced graphene/iron ion anthraquinone complex/carbon/polyaniline super capacitor electrode material is made by in-situ polymerization in dilute hydrochloric acid with aniline in rGO DAAQ/Fe.The present invention is easy to operate, and environmentally protective, specific capacitance is up to 612 F g‑1, cyclical stability is good.
Description
Technical field
The invention belongs to electrode material for super capacitor preparation fields, and in particular to a kind of graphene/metal anthraquinone cooperation
Object/carbon/polyaniline super capacitor electrode material and preparation method thereof.
Background technology
Energy crisis is the unavoidable eternal topic of today's society, with the non-renewable fossil fuel such as oil
Storage capacity is fewer and fewer, and it is the Tough questions that the mankind must face to find regenerative resource.Electric energy is current people's life
A kind of clean energy resource of very big proportion is accounted for, but common battery cannot meet people because power density is low at many aspects
Demand, the fast ultracapacitor of high power density, good cycling stability, charge-discharge velocity comes into being.
The electrode material of ultracapacitor is broadly divided into three classes：Carbon material（Mainly graphene, activated carbon and carbon nanometer
Pipe）；Transition metal oxide or hydroxide（Most common ruthenium-oxide, nickel hydroxide, manganese dioxide etc.）；Conducting polymer
（The polyaniline most represented, polypyrrole, polythiophene）.For carbon material because of its big specific surface area, energy storage mechnism is electric double layer energy storage,
Specific capacitance is smaller.And transition metal oxide or hydroxide and conducting polymer are anti-because possible redox can occur
It answers, their energy storage mechnism is faraday's energy storage, i.e. fake capacitance, although the specific capacitance of the two is larger, cyclical stability
Difference, and most of metal price is expensive, and Environmental compatibility is poor.So recycling suitable super capacitor material to realize height
Specific capacitance, good cyclical stability and Environmental compatibility are the difficult point studied at present and hot spot.
Invention content
In order to overcome the shortcomings of above-mentioned existing electrode material for super capacitor, the present invention provides a kind of graphene/metals
Anthraquinone complex/carbon/polyaniline super capacitor electrode material and preparation method thereof.The method applied in the present invention is simple, logical first
It crosses one-step method to realize the functionalization of graphene and be simultaneously coordinated iron ion, then is aoxidized polyaniline by simple in-situ polymerization
In polymerization.Metal ion used is iron, and relative to other metals, such as copper, nickel etc. is cheap, and Environmental compatibility is good, and can
Big specific capacitance is provided by redox reaction, 1,5- diamino-anthraquinone not only can with covalence graft on graphene and iron from
Son coordination doping, big lamellar structure can also provide certain electric double layer capacitance, and polyaniline conductivity is preferable, can also provide
Larger fake capacitance, graphene can make whole system be in stable state, substantially increase entire material as matrix
Stability.Big specific capacitance and good cyclical stability may be implemented in this ternary composite electrode material use synergistic effect.
The purpose of the present invention is realized especially by following technical scheme.
1,5- diamino-anthraquinones are grafted on graphene by the present invention by one step of high temperature reflux, and realize 1 simultaneously, 5- bis-
The coordination of amino anthraquinones and iron ion is adulterated.The amino not reacted completely on 1,5- diamino-anthraquinones and polyaniline are carried out covalent
Grafting, makes entire graphene/metal anthraquinone complex/polyaniline trielement composite material all in covalent linkage.
A kind of preparation method of graphene/metal anthraquinone complex/carbon/polyaniline super capacitor electrode material, specifically includes
Following steps：
（1）The preparation of reduced graphene/iron ion anthraquinone complex：Graphene oxide is dispersed in N,N-dimethylformamide
In, add 1,5- diamino-anthraquinones, green vitriol, ultrasonic disperse is reacted under reflux state, washed after the completion of reaction
It washs, it is dry, obtain reduced graphene/iron ion anthraquinone complex.
（2）The preparation of reduced graphene/iron ion anthraquinone complex/polyaniline：Reduced graphene/iron ion anthraquinone is matched
Object ultrasonic disperse is closed in dilute hydrochloric acid, adds aniline, then the ammonium persulfate being dissolved in dilute hydrochloric acid is added in ultrasonic disperse,
Low temperature is stirred to react, and is filtered after the completion of reaction, is washed, dry, obtains reduced graphene/iron ion anthraquinone complex/polyaniline three
First electrode material for super capacitor.
Preferably, step（1）The N-N dimethylformamides do not do further dehydration.
Preferably, step（1）The ultrasonic time is 1 h.
Preferably, step（1）The mass ratio of the graphene oxide and 1,5- diamino-anthraquinones is 1:3 -4:1, further
Preferably 1:1.
Preferably, step（1）The mass ratio of the graphene oxide and green vitriol is 5:18 -10:9, into one
Step preferably 5:9.
Preferably, step（1）Dispersion concentration of the graphene oxide in N,N-dimethylformamide is 0.2-8 mg
mL-1, further preferably 1 mg mL-1。
Preferably, step（1）The reaction time is 3-20 h, further preferably 15 h.
Preferably, step（1）The reaction temperature is 100-150 DEG C, further preferably 140 DEG C.
Preferably, step（1）The washing is N-N dimethylformamides, deionized water, absolute ethyl alcohol wash repeatedly.
Preferably, step（1）、（2）The drying temperature is 60 DEG C, and drying time is 8 h.
Preferably, step（2）The first time ultrasonic time is 1 h, and second of ultrasonic time is 0.5 h.
Preferably, step（2）A concentration of 0.5-4 mol L of the dilute hydrochloric acid-1, further preferably 1 mol L-1.Institute
It is 4 to state the ratio between the amount of the substance of the solute of total dilute hydrochloric acid and the amount of substance of aniline monomer:1-16:1, further preferably 8:
1。
Preferably, the amount of dilute hydrochloric acid used respectively accounts for 1/2 twice.
Preferably, step（2）The low temperature is-5-15 DEG C, and further preferably 0 DEG C, the reaction time is 3-24
H, further preferably 10 h.
Preferably, step（2）The mass ratio of the reduced graphene/iron ion anthraquinone complex and aniline monomer is 1:
10-5:1, further preferably 1:2, the ammonium persulfate is 1 with aniline monomer mass ratio:5 -5:1, further preferably 1：
2。
Preferably, step（2）The washing is dilute hydrochloric acid, acetone, deionized water are washed repeatedly.
A kind of graphene/metal anthraquinone complex/carbon/polyaniline super capacitor made from above-described preparation method
Electrode material.
Compared with prior art, the invention has the advantages that and technique effect：
1, the present invention replaces the hydrazine hydrate of severe toxicity to carry out redox graphene with 1,5- diamino-anthraquinones, has the feature of environmental protection, and same
When functionalization graphene, method is simple.
2, the present invention carries out coordination doping using iron ion, cheap environmental protection, and specific capacitance is high.
3, the present invention is realized using polyaniline covalence graft on the big amino of the 1,5- diamino-anthraquinones not reacted completely
High specific capacitance, and aniline monomer is cheap and easy to get.
4, the present invention utilizes the synergistic effect of graphene/metal anthraquinone complex/polyaniline three, makes the electrode obtained material
Specific capacitance be up to 612 F g-1, good cycling stability.
Description of the drawings
Fig. 1 is the low power SEM figures of the electrode material obtained by the embodiment of the present invention 4；
Fig. 2 is the high power SEM figures of the electrode material obtained by the embodiment of the present invention 4；
Fig. 3 is the cyclic voltammogram of the electrode material obtained by the embodiment of the present invention 3；
Fig. 4 is the constant current charge-discharge figure of the electrode material obtained by the embodiment of the present invention 4；
Fig. 5 is the loop test figure of the electrode material obtained by the embodiment of the present invention 4.
Specific implementation mode
The specific implementation of the present invention is described in further detail below in conjunction with example and attached drawing, but the implementation of the present invention
Mode is without being limited thereto.
Embodiment 1
（1）The preparation of reduced graphene/iron ion anthraquinone complex：100 mg graphene oxides are weighed, are dispersed in 500 mL's
In n,N-Dimethylformamide, 300 mg 1,5- diamino-anthraquinones, 360 mg green vitriols, ultrasonic disperse 1 are added
H, 3 h of back flow reaction, filters suspension after the completion of reaction at 100 DEG C, then uses n,N-Dimethylformamide, deionization respectively
Water, absolute ethyl alcohol wash repeatedly, and dry 8 h, obtain reduced graphene/iron ion anthraquinone complex in 60 DEG C of baking oven.
（2）The preparation of reduced graphene/iron ion anthraquinone complex/polyaniline：By 100 mg reduced graphenes/iron ion
Anthraquinone complex is dispersed in 5.4 mL, 4 mol L-1In dilute hydrochloric acid, 1 h of ultrasound adds 1000 mg aniline monomers, ultrasonic disperse
Then the 4 mol L that 5.4 mL have dissolved 200 mg ammonium persulfates are added dropwise in 0.5 h-1Dilute hydrochloric acid, be stirred to react at -5 DEG C
3 h are filtered after the completion of reaction, and are washed repeatedly with dilute hydrochloric acid, acetone, deionized water respectively, dry 8 in 60 DEG C of baking oven
H obtains reduced graphene/iron ion anthraquinone complex/carbon/polyaniline super capacitor electrode material.It is computed, which exists
0.5 A g-1Current density under specific capacitance up to 507 F g-1, specific capacitance also remains with original 72% after cycle 1000 is enclosed.
Embodiment 2
（1）The preparation of reduced graphene/iron ion anthraquinone complex：100 mg graphene oxides are weighed, are dispersed in 12.5 mL's
In n,N-Dimethylformamide, 25 mg 1,5- diamino-anthraquinones, 90 mg green vitriols, ultrasonic disperse 1 are added
H, 20 h of back flow reaction, filters suspension after the completion of reaction at 150 DEG C, then respectively with n,N-Dimethylformamide, go from
Sub- water, absolute ethyl alcohol wash repeatedly, and dry 8 h, obtain reduced graphene/iron ion anthraquinone complex in 60 DEG C of baking oven.
（2）The preparation of reduced graphene/iron ion anthraquinone complex/polyaniline：By 100 mg reduced graphenes/iron ion
Anthraquinone complex is dispersed in 3.4 mL, 0.5 mol L-1In dilute hydrochloric acid, 1 h of ultrasound adds 20 mg aniline monomers, ultrasonic disperse
Then the 0.5 mol L that 3.4 mL have dissolved 100 mg ammonium persulfates are added dropwise in 0.5 h- 1Dilute hydrochloric acid stirs at 15 DEG C anti-
24 h are answered, are filtered after the completion of reaction, and washed repeatedly with dilute hydrochloric acid, acetone, deionized water respectively, it is dry in 60 DEG C of baking oven
8 h obtain reduced graphene/iron ion anthraquinone complex/carbon/polyaniline super capacitor electrode material.It is computed, the electrode material
In 0.5 A g-1Current density under specific capacitance up to 465 F g-1, specific capacitance also remains with original after cycle 1000 is enclosed
79%。
Embodiment 3
（1）The preparation of reduced graphene/iron ion anthraquinone complex：100 mg graphene oxides are weighed, are dispersed in 24.4 mL's
In n,N-Dimethylformamide, 216.6 mg 1,5- diamino-anthraquinones, 144 mg green vitriols, ultrasound point are added
1 h is dissipated, 11.5 h of back flow reaction, filters suspension after the completion of reaction at 125 DEG C, then uses N, N- dimethyl formyls respectively
Amine, deionized water, absolute ethyl alcohol wash repeatedly, and dry 8 h, obtain reduced graphene/iron ion anthraquinone and match in 60 DEG C of baking oven
Close object.
（2）The preparation of reduced graphene/iron ion anthraquinone complex/polyaniline：By 100 mg reduced graphenes/iron ion
Anthraquinone complex is dispersed in 4.9 mL, 2.25 mol L-1In dilute hydrochloric acid, 1 h of ultrasound adds 510 mg aniline monomers, ultrasound point
0.5 h is dissipated, the 2.25 mol L that 4.9 mL have dissolved 1326 mg ammonium persulfates are then added dropwise-1Dilute hydrochloric acid, stir at 5 DEG C
13.5 h of reaction are mixed, are filtered after the completion of reaction, and washed repeatedly with dilute hydrochloric acid, acetone, deionized water respectively, in 60 DEG C of baking oven
8 h of interior drying obtains reduced graphene/iron ion anthraquinone complex/carbon/polyaniline super capacitor electrode material.To obtained production
Object has carried out cyclic voltammetry, as shown in figure 3, the product has two pairs of apparent redox peaks, this is iron ion and gathers
Aniline occurs what redox reaction generated.It is computed, the electrode material is in 0.5 A g-1Current density under specific capacitance it is reachable
526 F g-1, specific capacitance also remains with original 74% after cycle 1000 is enclosed.
Embodiment 4
（1）The preparation of reduced graphene/iron ion anthraquinone complex：100 mg graphene oxides are weighed, are dispersed in 100 mL's
In n,N-Dimethylformamide, 100 mg 1,5- diamino-anthraquinones, 180 mg green vitriols, ultrasonic disperse 1 are added
H, 15 h of back flow reaction, filters suspension after the completion of reaction at 140 DEG C, then respectively with n,N-Dimethylformamide, go from
Sub- water, absolute ethyl alcohol wash repeatedly, and dry 8 h, obtain reduced graphene/iron ion anthraquinone complex in 60 DEG C of baking oven.
（2）The preparation of reduced graphene/iron ion anthraquinone complex/polyaniline：By 100 mg reduced graphenes/iron ion
Anthraquinone complex is dispersed in 8.6 mL, 1 mol L-1In dilute hydrochloric acid, 1 h of ultrasound adds 200 mg aniline monomers, ultrasonic disperse
Then 0.5 h is added dropwise the dilute hydrochloric acid that 8.6 mL have dissolved 400 mg ammonium persulfates, is stirred to react 10 h at 0 DEG C, has reacted
It at rear filtering, and is washed repeatedly with dilute hydrochloric acid, acetone, deionized water respectively, dry 8 h, obtain reduction stone in 60 DEG C of baking oven
Black alkene/iron ion anthraquinone complex/carbon/polyaniline super capacitor electrode material.Scanning electricity is carried out respectively to obtained product
Mirror is tested and constant current charge-discharge test, is respectively the low power and high power scanning electron microscope (SEM) photograph of the product as shown in Figure 1, Figure 2, by can in figure
A strata aniline nano ball is equably grown to find out, on graphene sheet layer, Fig. 4 is in 0.5 A g-1Current density under
Constant current charge-discharge figure, is computed, and the electrode material is in 0.5 A g-1Current density under specific capacitance up to 612 F g-1, Fig. 5
It is the cycle figure that constant current charge-discharge 1000 encloses, as can be seen from Figure, specific capacitance also remains with original after 1000 circle of cycle
83%。
Claims (10)
1. a kind of preparation method of graphene/metal anthraquinone complex/carbon/polyaniline super capacitor electrode material, feature exist
In including the following steps：
（1）The preparation of reduced graphene/iron ion anthraquinone complex：Graphene oxide is dispersed in N,N-dimethylformamide
In, add 1,5- diamino-anthraquinones, green vitriol, ultrasonic disperse is reacted under reflux state, washed after the completion of reaction
It washs, it is dry, obtain reduced graphene/iron ion anthraquinone complex；
（2）The preparation of graphene/metal anthraquinone complex/carbon/polyaniline super capacitor electrode material：By reduced graphene/iron from
Sub- anthraquinone complex ultrasonic disperse adds aniline in dilute hydrochloric acid, then the mistake being dissolved in dilute hydrochloric acid is added in ultrasonic disperse
Ammonium sulfate, low temperature are stirred to react, and are filtered after the completion of reaction, are washed, dry, and it is super to obtain graphene/metal anthraquinone complex/polyaniline
Grade capacitor electrode material.
2. preparation method according to claim 1, which is characterized in that step（1）The graphene oxide and 1,5- diaminos
The mass ratio of base anthraquinone is 1:3-4:1.
3. preparation method according to claim 1, which is characterized in that step（1）The graphene oxide and seven hydration sulphur
Sour ferrous mass ratio is 5:18-10:9.
4. preparation method according to claim 1, which is characterized in that step（1）The graphene oxide is in N, N- diformazans
Dispersion concentration in base formamide is 0.2-8 mg mL-1。
5. preparation method according to claim 1, which is characterized in that step（1）The reaction time is 3-20 h.
6. preparation method according to claim 1, which is characterized in that step（1）The temperature of the reaction is 100-150
℃。
7. preparation method according to claim 1, which is characterized in that step（2）A concentration of 0.5-4 of the dilute hydrochloric acid
mol L-1；Step（2）The ratio between the amount of the substance of the solute of dilute hydrochloric acid in reaction solution and the amount of substance of aniline monomer are 4:1-
16:1。
8. preparation method according to claim 1, which is characterized in that step（2）The low temperature is -5-15 DEG C, described anti-
The time answered is 3-24 h.
9. preparation method according to claim 1, which is characterized in that step（2）The reduced graphene/iron ion anthraquinone
The mass ratio of complex and aniline is 1:10-5:1, the mass ratio of the ammonium persulfate and aniline is 1:5-5:1.
10. a kind of graphene/metal anthraquinone complex/polyphenyl made from claim 1-9 any one of them preparation methods
Amine electrode material for super capacitor.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104332639A (en) * | 2014-11-05 | 2015-02-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of co-doped conductive polymer electrode material |
| CN104934236A (en) * | 2015-04-30 | 2015-09-23 | 河海大学 | Method of preparing electroactive molecule grafted graphene doped conductive polymer electrode materials |
| CN105591152A (en) * | 2016-01-22 | 2016-05-18 | 东北师范大学 | Method for preparing hierarchical porous oxygen-rich carbon nanocones from organic metal complexes |
| CN106504910A (en) * | 2016-10-25 | 2017-03-15 | 河海大学 | A kind of anthraquinone molecular cograft carbon/conducting polymer composite material and preparation method thereof |
-
2018
- 2018-03-19 CN CN201810225399.1A patent/CN108428556B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104332639A (en) * | 2014-11-05 | 2015-02-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of co-doped conductive polymer electrode material |
| CN104934236A (en) * | 2015-04-30 | 2015-09-23 | 河海大学 | Method of preparing electroactive molecule grafted graphene doped conductive polymer electrode materials |
| CN105591152A (en) * | 2016-01-22 | 2016-05-18 | 东北师范大学 | Method for preparing hierarchical porous oxygen-rich carbon nanocones from organic metal complexes |
| CN106504910A (en) * | 2016-10-25 | 2017-03-15 | 河海大学 | A kind of anthraquinone molecular cograft carbon/conducting polymer composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MINQIANG SUN,ET AL.: ""A graphene/carbon nanotube@p-conjugated polymer nanocomposite for high-performance organic supercapacitor electrodes"", 《J. MATER. CHEM. A》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333855A (en) * | 2020-04-03 | 2020-06-26 | 华南师范大学 | 1, 5-dihydroxy anthraquinone copper coordination polymer/graphene compound and preparation and application thereof |
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