CN106504910A - A kind of anthraquinone molecular cograft carbon/conducting polymer composite material and preparation method thereof - Google Patents
A kind of anthraquinone molecular cograft carbon/conducting polymer composite material and preparation method thereof Download PDFInfo
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- CN106504910A CN106504910A CN201610939181.3A CN201610939181A CN106504910A CN 106504910 A CN106504910 A CN 106504910A CN 201610939181 A CN201610939181 A CN 201610939181A CN 106504910 A CN106504910 A CN 106504910A
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- China
- Prior art keywords
- carbon
- conducting polymer
- cograft
- anthraquinone
- molecular
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002322 conducting polymer Substances 0.000 title claims abstract description 53
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 43
- 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 42
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002019 doping agent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 claims description 8
- 238000006735 epoxidation reaction Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 claims description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 3
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical class NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 claims description 3
- QXYRRCOJHNZVDJ-UHFFFAOYSA-N 4-pyren-1-ylbutanoic acid Chemical compound C1=C2C(CCCC(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 QXYRRCOJHNZVDJ-UHFFFAOYSA-N 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 229940059939 kayexalate Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- RGHILYZRVFRRNK-UHFFFAOYSA-N anthracene-1,2-dione Chemical compound C1=CC=C2C=C(C(C(=O)C=C3)=O)C3=CC2=C1 RGHILYZRVFRRNK-UHFFFAOYSA-N 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 abstract description 5
- 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 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- -1 oxy radical Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- BUSZLIXFVJAMHW-UHFFFAOYSA-N 3-aminoanthracene-1,2-dione Chemical class C1=CC=C2C=C(C(=O)C(C(N)=C3)=O)C3=CC2=C1 BUSZLIXFVJAMHW-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
Abstract
The present invention relates to a kind of anthraquinone molecular cograft carbon/conducting polymer composite material and preparation method thereof, is to add graphene oxide, epoxy carbon nano tube in the ethanol solution of amino anthraquinones, prepares anthraquinone molecular cograft carbon after being heated to reflux;Then conducting polymer monomer, dopant, oxidant are added in anthraquinone molecular cograft carbon dispersion liquid, under stirring condition, after 0 30 DEG C of 12 24h of reaction, obtains anthraquinone molecular cograft carbon/conducting polymer composite material.The present invention improves Graphene dispersibility in the composite, and widens its potential window by the use of amino anthraquinones molecule as the common grafted graphene oxide of electroactive medium and CNT;Compound Grafting Structure of the two-dimensional graphene piece with one-dimensional CNT is combined with conducting polymer, is obtained the composite of three-dimensional net structure, higher energy density and cyclical stability is shown as electrode material for super capacitor.
Description
Technical field
The present invention relates to a kind of conducting polymer combination electrode material preparation method, belongs to electrode of super capacitor material
Field.
Background technology
Ultracapacitor is a kind of novel energy-storing element between electrostatic condenser and electrochmical power source, its with traditional
Capacitor is compared with accumulator, have the advantages that height ratio capacity, high power density, the service life of length and environmental protection, how should
For various fields such as industry, communication, military and electric automobiles.At present, the conventional electrode material of ultracapacitor mainly has three
Kind:Material with carbon element (with high-specific surface area), conducting polymer materials and metal oxide materials.
Material with carbon element (such as Graphene, CNT, activated carbon etc.) can obtain high following as the representative of electric double layer capacitance
The ring life-span, but its energy density is low.Conducting polymer can be obtained compared with material with carbon element as a kind of Faraday pseudo-capacitance electrode material
Higher energy density is obtained, but which still suffers from the shortcomings of cycle life is not high, ion transmission is slower after multiple discharge and recharge.Closely
Conducting polymer and material with carbon element are carried out compound preparing Faraday pseudo-capacitance/electric double layer capacitance combination electrode material and becoming by Nian Lai
Study hotspot.
Conducting polymer/graphene combination electrode material is showed in terms of ultracapacitor with its excellent chemical property
Go out good application prospect.At present, the research of conducting polymer/graphene combination electrode material has possessed good Research foundation
(Kashani H,Chen LY,Ito Y,Han JH,Hirata A,Chen MW.Bicontinuous nanotubular
graphene–polypyrrole hybrid for high performance flexible
supercapacitors.Nano Energy 2016;19:391-400.Lia Y,Louarnb G,Aubertc P,Alain-
Rizzoa V,Galmichea L,Audeberta P,et al.Polypyrrole-modified graphene sheet
nanocomposites as new efficient materials for supercapacitors.Carbon 2016;
105:510-20.WuZS,Parvez K,Li S,Yang S,Liu ZY,Liu SH,et al.Alternating stacked
graphene-conducting polymer compact films with ultrahigh areal and volumetric
capacitances for high-energy micro-supercapacitors.Adv Mater 2015;27:4054-
61.) in but due to recombination process in Graphene and conducting polymer, the fault of construction problem of Graphene itself, the group of Graphene
Poly- problem etc. is still the principal element for restricting its energy density.Therefore, the redox active of Graphene how is improved, which is made up
Fault of construction, and solve its scattering problem in the composite and still need to further study.
Content of the invention
In order to solve problem above, it is an object of the invention to provide a kind of anthraquinone molecular cograft carbon/conducting polymer is multiple
The preparation method of condensation material, by amino anthracene quinones electric active molecule cograft in two-dimensional graphene and one-dimensional carbon nano tube surface,
While giving Graphene good oxidation reducing activity, its dispersibility in the composite is improved.Secondly, by two-dimensional graphene
Piece is combined with conducting polymer with the compound Grafting Structure of one-dimensional CNT, is obtained and is had the three of excellent electrochemical activity
The composite of dimension network, there is not been reported both at home and abroad for this kind of method.
In order to realize above-mentioned goal of the invention, the technical solution used in the present invention is as follows:
Anthraquinone molecular cograft carbon/conducting polymer composite material, is three constructed by graphene sheet layer and CNT
Dimension network structure, conducting polymer are grown in the surface of graphene film and CNT in the form of granules, the composite table
Reveal good electrochemical capacitance characteristic.Wherein, the size of CNT is 20-40nm, and graphene sheet layer size is 1-2 μm.
A kind of preparation method of anthraquinone molecular cograft carbon/conducting polymer composite material, step are as follows:
During step (1) adds diamino-anthraquinone to ethanol, solution after dissolving, is formed;
Described diamino-anthraquinone be Isosorbide-5-Nitrae-diamino-anthraquinone, 2,6- diamino-anthraquinones, 1,5- diamino-anthraquinone, 1,2- bis-
One kind in amino anthraquinones;
The concentration of diamino-anthraquinone is 1-20g/L.
Step (2) adds graphene oxide, epoxy carbon nano tube in ethanol, and simultaneously ultrasonic disperse is uniform for stirring, is formed
Graphene oxide-epoxidation carbon nano tube dispersion liquid;
The concentration of dispersion liquid is 0.5-10g/L;
Graphene oxide is 4 with the mass ratio of epoxy carbon nano tube:1-1:4.
Step (3), the graphene oxide for forming step (2)-epoxidation carbon nano tube dispersion liquid adds the molten of step (1)
In liquid, in the 70-90 DEG C of 24-48h that flows back, after being cleaned with second alcohol and water repeatedly, centrifugation obtains anthraquinone molecular cograft carbon.
Step (4), the anthraquinone molecular cograft carbon obtained by step (3) is dispersed in water forms dispersion liquid;Dispersion liquid
Concentration be 0.5-3g/L.
Step (5), conducting polymer monomer, dopant, oxidant are sequentially added in step (4) gained dispersion liquid, mixed
Close uniformly, 12-24h is reacted in stirring condition in 0-30 DEG C, product deionized water is cleaned repeatedly, and do in vacuum drying oven
Dry, obtain anthraquinone molecular cograft carbon/conducting polymer composite material.
It is aniline, m-diaminobenzene., pyrroles, the one kind in 3,4- ethylenedioxy thiophenes that described conducting polymer monomer is;
Described dopant be kayexalate, dodecylbenzene sodium sulfonate, p-phthalic acid, 1- pyrene butanoic acid, 1,
One kind in 5- naphthalenedisulfonic acids;
Described oxidant is ferric chloride, Ammonium persulfate., potassium peroxydisulfate or 1- butyl -3- Methylimidazole. titanium tetrachlorides
Salt.
Anthraquinone molecular cograft carbon is 1 with the mass ratio of conducting polymer monomer:20-1:1, conducting polymer monomer with mix
Miscellaneous dose of mol ratio is 4:1-1:2, conducting polymer monomer is 1 with the mol ratio of oxidant:1.
The problem that the present invention reunites for the Graphene that current conducting polymer/graphene combination electrode material is present, will
One-dimensional CNT by the use of Anthraquinones electric active molecule as medium cograft on graphene nanometer sheet, with conducting polymer
The anthraquinone molecular cograft carbon/conducting polymer composite material of three-dimensional net structure is prepared after In-situ reaction, can be used as surpassing
Level capacitor electrode material.
The positive effect of the present invention is as follows:
1st, graphene nanometer sheet is connected with CNT by the use of anthraquinone electric active molecule as medium, cograft structure
The inducible conducting polymer polymer of abundant oxy radical is polymerized in its vicinity, and acquisition three-dimensional net structure can provide excellent
Ion transport capability, the introducing of conducting polymer and anthraquinone electric active molecule are conducive to combination electrode material chemical property
Improve.
2nd, the present invention prepare anthraquinone molecular cograft carbon/conducting polymer combination electrode material can obtain higher-wattage and
Energy density, and good cyclical stability is kept, have a good application prospect as electrode material for super capacitor.
3rd, preparation method of the present invention and equipment is simple, processing ease, easily expands large-scale production.
Description of the drawings
Fig. 1 is the SEM photograph of anthraquinone molecular cograft carbon/conducting polymer composite material prepared by the embodiment of the present invention 1,
Tested using JSM-5610 type scanning electron microscopies (Japanese JEOL companies), sample gold,platinized before testing.Can by SEM image
See, composite presents the three-dimensional net structure that graphene sheet layer is constructed with CNT, and conducting polymer is then with granule
Form is grown in the surface of graphene film and CNT, and the size of CNT is 20-40nm, and graphene sheet layer size is 1-
2μm.
Fig. 2. the circulation volt of the anthraquinone molecular cograft carbon/conducting polymer composite material prepared for the embodiment of the present invention 1
Peace curve (electrolyte:1M H2SO4, sweep speed=10mV/s).From Figure 2 it can be seen that composite material exhibits go out good electrochemical capacitance characteristic,
Its potential window can be widened to 1.7V.
Fig. 3. the discharge and recharge of the anthraquinone molecular cograft carbon/conducting polymer composite material prepared for the embodiment of the present invention 1
Curve (electrolyte:1M H2SO4, electric current density=2A/g).As can be seen from Figure 3, the specific capacitance of composite prepared by embodiment 1 can
According to:Calculate, wherein CmFor specific capacitance, I is discharge current, and △ t are discharge time, and m is active substance
Quality, △ v are the voltage drop in discharge process, are calculated the specific capacitance of composite of the preparation of embodiment 1 then up to 440F/
g.
Specific embodiment
The above of the present invention is described in further detail below by way of specific embodiment.But this should not be understood
Following examples are only limitted to for present disclosure.
Embodiment 1
A kind of preparation method of anthraquinone molecular cograft carbon/conducting polymer composite material, it is characterised in that step is as follows:
(1) 1g 1,4- diamino-anthraquinones ((purchased from Shanghai Industrial Co., Ltd. in future)) are added to 100mL (10g/L)
In ethanol, solution after dissolving, is formed, standby;
(2) by 0.8g graphene oxides, 0.2g epoxidation preparation method of carbon nano-tube referring to Ogrin, D.,
Chattopadhyay,J,Sadana,A.K,Billups,W.E,Barron,A.R.Epoxidation and
deoxygenation of single-walled carbon nanotubes:Quantification of epoxide
Defects.J Am Chem Soc, 2006,128,11322-11323) add in 100mL ethanol, simultaneously ultrasonic disperse is equal for stirring
Even, graphene oxide-epoxidation carbon nano tube dispersion liquid is formed, standby;
(3), the graphene oxide for forming step (2)-epoxidation carbon nano tube dispersion liquid is added in step (1), in 90
DEG C backflow 24h, after being cleaned with second alcohol and water repeatedly, centrifugation obtain anthraquinone molecular cograft carbon.
(4), take the anthraquinone molecular cograft carbon that 0.465g prepares by (3) to be dispersed in 155mL water (concentration 3g/L)
Form dispersion liquid standby.
(5), by 0.465g (5mmol) aniline (purchased from Chemical Reagent Co., Ltd., Sinopharm Group), 0.2575g
(1.25mmol) kayexalate (purchased from Aldrich), 0.81g (5mmol) ferric chloride are (purchased from close europeanized of Tianjin section
Reagent company limited) sequentially add in above-mentioned dispersion liquid, mix homogeneously;Stirring condition reacts 24h, product deionization in 0 DEG C
Water is cleaned repeatedly, and is dried in vacuum drying oven, obtains anthraquinone molecular cograft carbon/conducting polymer composite material.
Embodiment 2
A kind of preparation method of anthraquinone molecular cograft carbon/conducting polymer composite material, its ground different from embodiment 1
Side is:
In step (1), 1g Isosorbide-5-Nitraes-diamino-anthraquinone is changed into 2g 2,6- diamino-anthraquinones;
In step (2), the quality of graphene oxide is changed into 0.01g, and the quality of epoxy carbon nano tube is changed into 0.04g;
In step (4), 0.465g anthraquinone molecular cograft carbon is dispersed in 155mL water and is changed into 0.0134g anthraquinone moleculars altogether
Grafting carbon is dispersed to (concentration 0.5g/L) in 26.8mL water;
In step (5), 0.465g (5mmol) aniline is changed into 0.268g (4mmol) pyrroles, 0.2575g polystyrolsulfon acids
Sodium (1.25mmol) is changed into 2.7878g (8mmol) dodecylbenzene sodium sulfonate, and 0.81g (5mmol) ferric chloride is changed into
0.9128g (4mmol) Ammonium persulfate.;0 DEG C of reaction 24h is changed into 30 DEG C of reaction 12h;
In step (3), 90 DEG C of backflow 24h are changed into 80 DEG C of backflow 36h.
Embodiment 3
A kind of preparation method of anthraquinone molecular cograft carbon/conducting polymer composite material, its ground different from embodiment 1
Side is:
In step (1), 1g Isosorbide-5-Nitraes-diamino-anthraquinone is changed into 0.1g 1,5- diamino-anthraquinones;
In step (2), the quality of graphene oxide is changed into 0.1g, and the quality of epoxy carbon nano tube is changed into 0.1g;
In step (4), 0.465g anthraquinone molecular cograft carbon is dispersed in 155mL water and is changed into 0.108g anthraquinone moleculars and connects altogether
Branch carbon is dispersed to (concentration 1g/L) in 108mL water,;
In step (5), 0.465g (5mmol) aniline is changed into 1.08g (10mmol) m-diaminobenzene., 0.2575g polystyrene
Sodium sulfonate (1.25mmol) is changed into 0.83g (5mmol) p-phthalic acid, and 0.81g (5mmol) ferric chloride is changed into 2.7032g
(10mmol) potassium peroxydisulfate;0 DEG C of reaction 24h is changed into 15 DEG C of reaction 18h.
Embodiment 4
A kind of preparation method of anthraquinone molecular cograft carbon/conducting polymer composite material, its ground different from embodiment 1
Side is:
In step (1), 1g Isosorbide-5-Nitraes-diamino-anthraquinone is changed into 1.5g 1,2- diamino-anthraquinones;
In step (2), the quality of graphene oxide is changed into 0.3g, and the quality of epoxy carbon nano tube is changed into 0.2g;
In step (4), 0.465g anthraquinone molecular cograft carbon is dispersed in 155mL water and is changed into 0.142g anthraquinone moleculars and connects altogether
Branch carbon is dispersed to (concentration 2g/L) in 284mL water;
In step (5), 0.465g (5mmol) aniline is changed into 3,4 ethylenedioxy thiophenes of 0.71g (5mmol), and 0.2575g gathers
Sodium styrene sulfonate (1.25mmol) is changed into 1.4415g (5mmol) 1- pyrene butanoic acid, and 0 DEG C of reaction 24h is changed into 25 DEG C of reaction 16h.
Embodiment 5
A kind of preparation method of anthraquinone molecular cograft carbon/conducting polymer composite material, its ground different from embodiment 1
Side is:
In step (2), the quality of graphene oxide is changed into 0.3g, and the quality of epoxy carbon nano tube is changed into 0.5g;
In step (5), 0.465g (5mmol) aniline is changed into 0.71g (5mmol), 0.2575g kayexalates
(1.25mmol) it is changed into 0.4507g (1.25mmol) 1,5- naphthalenedisulfonic acids, 0.81g (5mmol) ferric chloride is changed into 1.6844g
(5mmol) 1- butyl tri-methylimidazolium titanium tetrachloride salt;
In step (3), 90 DEG C of backflow 24h are changed into 70 DEG C of backflow 48h.
Embodiment 1-5 prepares the performance parameter of composite and is shown in Table 1.
Table 1
Claims (5)
1. anthraquinone molecular cograft carbon/conducting polymer composite material, it is characterised in that be by graphene sheet layer and CNT
The three-dimensional net structure that constructs, conducting polymer are grown in the surface of graphene film and CNT in the form of granules, and this is multiple
Condensation material shows good electrochemical capacitance characteristic;Wherein, the size of CNT is 20-40nm, and graphene sheet layer size is 1-2
μm.
2. the preparation method of the anthraquinone molecular cograft carbon/conducting polymer composite material described in claim 1, its feature exist
In step is as follows:
(1), during, add diamino-anthraquinone to ethanol, solution is formed after dissolving;
(2), graphene oxide, epoxy carbon nano tube are added in ethanol, simultaneously ultrasonic disperse is uniform for stirring, forms graphite oxide
Alkene-epoxidation carbon nano tube dispersion liquid;
(3), the graphene oxide for forming step (2)-epoxidation carbon nano tube dispersion liquid is added in the solution of step (1), in
70-90 DEG C of backflow 24-48h, after being cleaned with second alcohol and water repeatedly, centrifugation obtains anthraquinone molecular cograft carbon;
(4), the anthraquinone molecular cograft carbon obtained by step (3) is dispersed in water and forms dispersion liquid;The concentration of dispersion liquid is
0.5-3g/L;
(5), conducting polymer monomer, dopant, oxidant are sequentially added in step (4) gained dispersion liquid, mix homogeneously,
Stirring condition reacts 12-24h in 0-30 DEG C, and product deionized water is cleaned repeatedly, and dries in vacuum drying oven, obtains anthracene
Quinone molecule cograft carbon/conducting polymer composite material.
3. the preparation method of the anthraquinone molecular cograft carbon/conducting polymer composite material described in claim 2, it is characterised in that
In step (1), described diamino-anthraquinone is Isosorbide-5-Nitrae-diamino-anthraquinone, 2,6- diamino-anthraquinones, 1,5- diamino-anthraquinone, 1,2-
One kind in diamino-anthraquinone;The concentration of diamino-anthraquinone is 1-20g/L.
4. the preparation method of the anthraquinone molecular cograft carbon/conducting polymer composite material described in claim 2, it is characterised in that
In step (2), the concentration of dispersion liquid is 0.5-10g/L;Graphene oxide is 4 with the mass ratio of epoxy carbon nano tube:1-1:
4.
5. the preparation method of the anthraquinone molecular cograft carbon/conducting polymer composite material described in claim 2, it is characterised in that
It is aniline, m-diaminobenzene., pyrroles, the one kind in 3,4- ethylenedioxy thiophenes that conducting polymer monomer described in step (5) is;
Described dopant is kayexalate, dodecylbenzene sodium sulfonate, p-phthalic acid, 1- pyrene butanoic acid, 1,5- naphthalenes
One kind in disulfonic acid;
Described oxidant is ferric chloride, Ammonium persulfate., potassium peroxydisulfate or 1- butyl -3- Methylimidazole. titanium tetrachloride salt;
Anthraquinone molecular cograft carbon is 1 with the mass ratio of conducting polymer monomer:20-1:1, conducting polymer monomer and dopant
Mol ratio be 4:1-1:2, conducting polymer monomer is 1 with the mol ratio of oxidant:1.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103801395A (en) * | 2014-02-26 | 2014-05-21 | 大连理工大学 | Graphene material modified by water-soluble anthraquinone compound and preparation method of graphene material |
CN104466134A (en) * | 2014-12-16 | 2015-03-25 | 华东理工大学 | Preparation method of self-supported graphene/carbon nano tube hybrid foam-loaded amino-anthraquinone polymer |
CN104934236A (en) * | 2015-04-30 | 2015-09-23 | 河海大学 | Method of preparing electroactive molecule grafted graphene doped conductive polymer electrode materials |
CN105551820A (en) * | 2016-03-01 | 2016-05-04 | 聊城大学 | Supercapacitor electrode material and preparation method thereof |
-
2016
- 2016-10-25 CN CN201610939181.3A patent/CN106504910B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103801395A (en) * | 2014-02-26 | 2014-05-21 | 大连理工大学 | Graphene material modified by water-soluble anthraquinone compound and preparation method of graphene material |
CN104466134A (en) * | 2014-12-16 | 2015-03-25 | 华东理工大学 | Preparation method of self-supported graphene/carbon nano tube hybrid foam-loaded amino-anthraquinone polymer |
CN104934236A (en) * | 2015-04-30 | 2015-09-23 | 河海大学 | Method of preparing electroactive molecule grafted graphene doped conductive polymer electrode materials |
CN105551820A (en) * | 2016-03-01 | 2016-05-04 | 聊城大学 | Supercapacitor electrode material and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
BING DING ET AL: "One-step electrochemical composite polymerization of polypyrrole integrated with functionalized graphene/carbon nanotubes nanostructured composite film for electrochemical capacitors", 《ELECTROCHIMICA ACTA》 * |
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