CN101892530B - Preparation of polyaniline/polypyrrole composite nano fiber electrode materials with core-shell structure - Google Patents
Preparation of polyaniline/polypyrrole composite nano fiber electrode materials with core-shell structure Download PDFInfo
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- CN101892530B CN101892530B CN201010228217XA CN201010228217A CN101892530B CN 101892530 B CN101892530 B CN 101892530B CN 201010228217X A CN201010228217X A CN 201010228217XA CN 201010228217 A CN201010228217 A CN 201010228217A CN 101892530 B CN101892530 B CN 101892530B
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 93
- 239000002121 nanofiber Substances 0.000 title claims abstract description 80
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000007772 electrode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011258 core-shell material Substances 0.000 title abstract 2
- 239000000243 solution Substances 0.000 claims abstract description 66
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 62
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 62
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 28
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 17
- 239000006260 foam Substances 0.000 claims description 17
- 238000007731 hot pressing Methods 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- CUYTYLVEYFUAAX-UHFFFAOYSA-N 4-methylbenzenesulfonic acid;sodium Chemical compound [Na].CC1=CC=C(S(O)(=O)=O)C=C1 CUYTYLVEYFUAAX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 235000014786 phosphorus Nutrition 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002019 doping agent Substances 0.000 abstract 3
- 239000003999 initiator Substances 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 30
- 125000004122 cyclic group Chemical group 0.000 description 30
- 238000000703 high-speed centrifugation Methods 0.000 description 30
- 238000000465 moulding Methods 0.000 description 15
- 230000035484 reaction time Effects 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 229920001940 conductive polymer Polymers 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 5
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 5
- 239000002322 conducting polymer Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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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- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明涉及一种核壳结构的聚苯胺/聚吡咯复合纳米纤维电极材料的制备，包括：(1)取苯胺和苯胺单体引发剂分别溶解在聚苯胺掺杂剂中，然后合并混合液；摇晃，室温下反应；离心和洗涤，得纤维；(2)取纤维加入聚吡咯掺杂剂中，超声分散，并在超声作用下加入吡咯单体，然后滴加吡咯单体引发剂的聚吡咯掺杂剂溶液；保持体系温度在0～5℃，反应；离心和洗涤，干燥，即得。本发明的方法简单，成本低，适合于工业化生产；所得材料用于超级电容器中，表现出较高的比电容值和良好的化学性能稳定性。
The invention relates to the preparation of a polyaniline/polypyrrole composite nanofiber electrode material with a core-shell structure, comprising: (1) dissolving aniline and aniline monomer initiators in polyaniline dopants respectively, and then combining the mixed solutions; Shake, react at room temperature; centrifuge and wash to obtain fibers; (2) take fibers and add them to polypyrrole dopant, ultrasonically disperse, add pyrrole monomers under the action of ultrasound, and then dropwise add pyrrole monomer initiator polypyrrole Dopant solution; keep the system temperature at 0-5°C, react; centrifuge, wash, and dry to obtain. The method of the invention is simple and low in cost, and is suitable for industrialized production; the obtained material is used in supercapacitors, and exhibits high specific capacitance value and good stability of chemical properties.
Description
Technical field
The invention belongs to the preparation field of composite nano fiber electrode materials, particularly relate to a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure.
Background technology
Ultracapacitor is a kind of novel energy-storing device, and it has characteristics such as charging interval weak point, long service life, good temp characteristic, energy savings and environmental protection.Ultracapacitor has huge using value and market potential in various fields such as electric automobile, fuel combination automobile, exceptional load automobile, electric power, railway, communication, national defence, consumption electronic products.Conducting polymer is because of the dynamic process of its charge discharge fast (promptly mix and go doping process rapid), and electric charge can store in whole material volume, and cost is low than metal oxide containing precious metals, has caused people's great attention.Wherein polyaniline (being suitable for acidic electrolysis bath) and polypyrrole (being suitable for neutral electrolyte and alkaline electrolyte) have excellent chemical property, environmental friendliness, characteristics such as synthetic simple and the material that is considered to have most using value.
Research shows that the electric capacity behavior of the conducting polymer that low dimension is orderly obviously is superior to unordered conducting polymer, and its reason can ascribe its aggregated structure high-sequential to, thereby has improved its carrier mobility greatly.The common method of synthesized polyaniline and polypyrrole nano-fiber material has interfacial polymerization, template, emulsion polymerization and electrochemical polymerization method etc.; Bad prolonging like Central South University waited the preparation method who has invented a kind of polyaniline nano fiber clearly; With aniline monomer and oxidant ammonium persulfate is raw material; Utilize the polymerisation that oil/water two-phase interface takes place to prepare polyaniline material; Through optimization and control to interfacial polymerization technology, prepare diameter between 30～120nm, length is that 500nm is to several microns polyaniline nano fiber materials that do not wait (publication number is CN101016660A); Yellow border is bravely waited and is adopted template that a kind of polypyrrole nano structure electrode is provided, and on electrode base material, only covers equally distributed polypyrrole nano line array, and this array proper alignment (publication number is CN101635201A) on described base material; As compound emulsifying agent, n-butanol is an assistant for emulsifying agent to Ma Li etc. with neopelex and hydrochloric acid, and ammonium persulfate is an oxidant, and through the micro-emulsion polymerization reaction, through breakdown of emulsion, washing, drying have been synthesized nano polyaniline powder (publication number is CN1709941A); Wang Jixiao etc. are mixed with electrolyte with pyrroles, polyanion adulterant or anion doped dose of high price and supporting electrolyte; Adopt combination electrode, directly generate the polypyrrole nano line (publication number is CN1465748A) of different length and diameter with potentiostatic method or cyclic voltammetry at electrode surface.Though yet existing these methods are obtaining success aspect the preparation conductive polymer nanometer fiber; But more or less exist the some shortcomings part; Like needs in the interfacial polymerization with an organic solvent, synthetic output is lower, and need reclaim organic solvent in order to avoid cause environmental pollution; The general cost of manufacture of template is higher, when the preparation electrode, need remove template; The a large amount of emulsifying agent of normal employing in the emulsion polymerization course of reaction, last handling process is more loaded down with trivial details; And electrochemical polymerization method needs conductive base, and synthetic product is limited by electrode area.What deserves to be mentioned is the time as electrode material for super capacitor; The conducting polymer of one-component often can only just can show excellent chemical property in acidity or alkaline electrolyte; As being applicable to acidic electrolysis bath owing to polyaniline; Polypyrrole is applicable to alkaline electrolyte, though polypyrrole also can be used for neutral electrolyte, in free from corrosion neutral electrolyte, often shows relatively poor.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure, and this method is simple, and cost is low, is suitable for suitability for industrialized production; The gained material is used for ultracapacitor, shows higher specific capacitance and good stable chemical performance property.
A kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure of the present invention comprises:
(1) gets aniline and aniline monomer initator and be dissolved in respectively in the Polyaniline Doped agent, merge mixed liquor then; Rock, react 5～90min under the room temperature; Product through centrifugal with the washing until neutrality, prepare polyaniline nano fiber;
(2) get above-mentioned polyaniline nano fiber and add in the doped polypyrrole agent, ultrasonic dispersion, and under ultrasonication, add pyrrole monomer, at the uniform velocity drip the doped polypyrrole agent solution of pyrrole monomer initator then; Keep system temperature at 0～5 ℃ in the ultrasonic procedure, reaction 10～60min; Product through centrifugal with the washing after being neutrality, drying promptly gets the polyaniline/polypyrrole composite nano fiber electrode materials with nucleocapsid structure;
The mol ratio of said aniline and initator is 1～6: 1; The mol ratio of aniline and Polyaniline Doped agent is 1: 5～20; The mol ratio of aniline and pyrrole monomer is 1～10: 1; The mol ratio of pyrrole monomer and initator is 1～6: 1; The mol ratio of pyrrole monomer and doped polypyrrole agent is 1: 5～20.
Polyaniline Doped agent in the said step (1) is a kind of in hydrochloric acid, sulfuric acid, phosphoric acid, sulfosalicylic acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, the DBSA.
Aniline monomer initator in the said step (1) is a kind of in ammonium persulfate, ferric trichloride, hydrogen peroxide, bichromate, the benzoyl peroxide.
The speed that said step (1) is rocked is per second 1～5 time.
Doped polypyrrole agent in the said step (2) is a kind of in hydrochloric acid, potassium chloride, sodium chloride, ammonium chloride, sodium nitrate, sodium sulphate, sodium phosphate, DBSA, neopelex, p-methyl benzenesulfonic acid, the p-methyl benzenesulfonic acid sodium etc.
Pyrrole monomer initator in the said step (2) is ammonium sulfate or ferric trichloride.
The doped polypyrrole agent solution of the pyrrole monomer initator in the said step (2) is dissolved in the solution that obtains in the doped polypyrrole agent for the pyrrole monomer initator.
Rate of addition in the said step (2) is 1～5ml/min.
Drying condition in the said step (2) is dry 24h-48h in the 60-80 ℃ of vacuum.
Electrode material in the said step (2) hot pressing 30min under 60 ℃, the pressure of 5MPa is pressed into electrode on nickel foam; With the Pt electrode for being that reference electrode is formed three-electrode system to electrode, Ag/AgCl; Electrolyte is the aqueous solution of potassium chloride, sodium chloride, lithium sulfate, sodium sulphate, potassium sulfate, phosphorus hexafluoride acid lithium, lithium perchlorate, potassium hyperchlorate or their mixture.
As electrode material for super capacitor the time, the strong interaction power height-oriented and that exist between the two of polyaniline and polypyrrole has improved electric charge transfer rate and the charge storage capacity in the charge and discharge process, greatly particularly in neutral electrolyte; Its chemical property and cyclical stability can be regulated and control through the polypyrrole thickness of polyaniline fiber size and polyaniline superficial deposit.
The present invention earlier in the aqueous solution under oscillating condition in-situ polymerization prepare polyaniline nano fiber, again with polyaniline nano fiber be " seed " at the aqueous polymerization polypyrrole, be formed with the polyaniline/polypyrrole composite nano fiber of nucleocapsid structure.
Beneficial effect
(1) preparation method of the present invention is simple and easy to operate, and is with low cost, is suitable for suitability for industrialized production;
(2) the present invention compares with existing conductive polymer nanometer fiber production method and has distinguishing feature; Whole polymerisation is carried out at aqueous phase; Need not template and surfactant; What prepare is the polyaniline/polypyrrole composite nano fiber that nucleocapsid structure is arranged, and the structure of nanofiber can be regulated and control through the monomer concentration of polyaniline and polypyrrole.
(3) polyaniline/polypyrrole composite nano fiber electrode materials with nucleocapsid structure that the present invention makes combines polyaniline and the excellent performance of polypyrrole effectively, and brings into play its cooperative effect; This material is specially adapted to neutral electrolyte, has avoided acidity or alkaline electrolyte to leak corrosion and the pollution that is brought; This composite nano fiber electrode materials shows good electrochemical behavior in neutral potassium sulfate electrolyte, its high specific capacitance can reach 430F/g, after circulation 1000 times, is no more than 20% than the decay of capacitance.
Description of drawings
Fig. 1 has the sem photograph of the polyaniline/polypyrrole composite nano fiber of nucleocapsid structure;
Fig. 2 has the cyclic voltammetry curve of polyaniline/polypyrrole composite nano fiber electrode materials in potassium sulfate solution of nucleocapsid structure.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 1 time under the room temperature is rocked, and the reaction time is controlled at 5min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, sodium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 254F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 25% after 1000 times.
Accurately take by weighing 0.005mol aniline and 0.005mol ferric trichloride and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 3 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 263F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 25% after 1000 times.
Embodiment 3
Accurately take by weighing 0.02mol aniline and 0.02mol potassium bichromate and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 20min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 5 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, lithium perchlorate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 333F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 21% after 1000 times.
Accurately take by weighing 0.02mol aniline and 0.01mol Ammonium Persulfate 98.5 and be dissolved in respectively in the 1M p-methyl benzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 1 time under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 5 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, sodium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 298F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 24% after 1000 times.
Embodiment 5
Accurately take by weighing 0.02mol aniline and 0.005mol ammonium persulfate and be dissolved in respectively in the 1M dodecylbenzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 287F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 22% after 1000 times.
Embodiment 6
Accurately take by weighing 0.01mol aniline and 0.01mol ferric trichloride and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M sodium chloride solution of 100ml; Ultrasonic 30min; Then the 0.005mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 5 ℃, the 0.0025mol ferric trichloride in the 1M sodium chloride solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium sulfate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 345F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 20% after 1000 times.
Embodiment 7
Accurately take by weighing 0.02mol aniline and 0.02mol Ammonium Persulfate 98.5 and be dissolved in respectively in the 1M camphorsulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 3 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M sodium chloride solution of 100ml; Ultrasonic 30min; Then the 0.01mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.0025mol ferric trichloride in the 1M sodium chloride solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium hyperchlorate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 377F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 22% after 1000 times.
Embodiment 8
Accurately take by weighing 0.02mol aniline and 0.02mol ferric trichloride and be dissolved in respectively in the 1M camphorsulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 1 time under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M dodecylbenzenesulfonic acid solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.0025mol ferric trichloride in the 1M sodium chloride solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 288F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 25% after 1000 times.
Embodiment 9
Accurately take by weighing 0.02mol aniline and 0.02mol ferric trichloride and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M sodium chloride solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.005mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, sodium sulphate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 403F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 20% after 1000 times.
Embodiment 10
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 3 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.01mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium hyperchlorate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 399F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 21% after 1000 times.
Embodiment 11
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M dodecylbenzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M p-methyl benzenesulfonic acid sodium solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ammonium persulfate in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 30min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium sulfate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 419F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 20% after 1000 times.
Embodiment 12
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M dodecylbenzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 1 time under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M sodium chloride solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ammonium persulfate in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 50min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 60 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, sodium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 366F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 21% after 1000 times.
Embodiment 13
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M dodecylbenzenesulfonic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M p-methyl benzenesulfonic acid sodium solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ammonium persulfate in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 60min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 80 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, potassium hyperchlorate is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 299F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 22% after 1000 times.
Embodiment 14
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M hydrochloric acid solution of 100ml, two kinds of solution are mixed, the speed with per second 3 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M p-methyl benzenesulfonic acid sodium solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ammonium persulfate in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 48h in 80 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.For being reference electrode to electrode, Ag/AgCl, the mixed liquor of potassium hyperchlorate and potassium chloride is that electrolyte is formed three-electrode system with the Pt electrode, and under the sweep speed of 1mV/s, the ratio capacitance that records is about 347F/g; Under the sweep speed of 5mV/s, circulating, the decay than capacitance is no more than 22% after 1000 times.
Embodiment 15
Accurately take by weighing 0.02mol aniline and 0.02mol ammonium persulfate and be dissolved in respectively in the 1M sulfosalicylic acid solution of 100ml, two kinds of solution are mixed, the speed with per second 5 times under the room temperature is rocked, and the reaction time is controlled at 10min; Product is prepared polyaniline nano fiber through high speed centrifugation and cyclic washing.
Prepared polyaniline nano fiber is joined in the 1M hydrochloric acid solution of 100ml; Ultrasonic 30min; Then the 0.02mol pyrrole monomer is added ultrasonic 30min in the above-mentioned mixed liquor; In ultrasonic, add ice cube, keep system temperature to be stabilized in 0 ℃, the 0.02mol ferric trichloride in the 1M hydrochloric acid solution that is dissolved in 100ml at the uniform velocity slowly is added drop-wise to 5ml/min reacts 40min in the mixed liquor.Product is through high speed centrifugation and cyclic washing, dry 24h in 80 ℃ of vacuum, and the black powder of preparing is the polyaniline/polypyrrole composite nano fiber with nucleocapsid structure.
Above-mentioned black powder is fully levigate in ball mill, join then that ultrasonic 30min fully disperses in the dimethyl sulfoxide solvent, evenly spread upon on the nickel foam collector again, and hot pressing 30min moulding is made into electrode under 60 ℃, the pressure of 5MPa.With the Pt electrode for being reference electrode to electrode, Ag/AgCl; The mixed liquor of potassium sulfate and potassium chloride is that electrolyte is formed three-electrode system; Under the sweep speed of 1mV/s, the ratio capacitance that records is about 357F/g, and circulating, the decay than capacitance is no more than 24% after 1000 times.
Claims (10)
1. preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure comprises:
(1) gets aniline and aniline monomer initator and be dissolved in respectively in the Polyaniline Doped agent, merge mixed liquor then; Rock, react 5～90min under the room temperature; Product through centrifugal with the washing until neutrality, prepare polyaniline nano fiber;
(2) get above-mentioned polyaniline nano fiber and add in the doped polypyrrole agent, ultrasonic dispersion, and under ultrasonication, add pyrrole monomer, at the uniform velocity drip the doped polypyrrole agent solution of pyrrole monomer initator then; Keep system temperature at 0～5 ℃ in the ultrasonic procedure, reaction 10～60min; Product through centrifugal with the washing after being neutrality, drying promptly gets the polyaniline/polypyrrole composite nano fiber electrode materials with nucleocapsid structure;
The mol ratio of said aniline and initator is 1～6: 1; The mol ratio of aniline and Polyaniline Doped agent is 1: 5～20; The mol ratio of aniline and pyrrole monomer is 1～10: 1; The mol ratio of pyrrole monomer and initator is 1～6: 1; The mol ratio of pyrrole monomer and doped polypyrrole agent is 1: 5～20.
2. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the Polyaniline Doped agent in the said step (1) is a kind of in hydrochloric acid, sulfuric acid, phosphoric acid, sulfosalicylic acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, the DBSA.
3. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the aniline monomer initator in the said step (1) is a kind of in ammonium persulfate, ferric trichloride, hydrogen peroxide, bichromate, the benzoyl peroxide.
4. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the speed that said step (1) is rocked is per second 1～5 time.
5. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the doped polypyrrole agent in the said step (2) is a kind of in hydrochloric acid, potassium chloride, sodium chloride, ammonium chloride, sodium nitrate, sodium sulphate, sodium phosphate, DBSA, neopelex, p-methyl benzenesulfonic acid, the p-methyl benzenesulfonic acid sodium.
6. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the pyrrole monomer initator in the said step (2) is ammonium persulfate or ferric trichloride.
7. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the rate of addition in the said step (2) is 1～5ml/min.
8. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the drying condition in the said step (2) is dry 24h-48h in the 60-80 ℃ of vacuum.
9. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the electrode material that makes in the said step (2) hot pressing 30min under 60 ℃, the pressure of 5MPa is pressed into electrode on nickel foam; With the Pt electrode for being that reference electrode is formed three-electrode system to electrode, Ag/AgCl; Electrolyte is the aqueous solution of potassium chloride, sodium chloride, lithium sulfate, sodium sulphate, potassium sulfate, phosphorus hexafluoride acid lithium, lithium perchlorate, potassium hyperchlorate or their mixture.
10. a kind of preparation method with polyaniline/polypyrrole composite nano fiber electrode materials of nucleocapsid structure according to claim 1 is characterized in that: the electrode material that said step (2) makes is used for ultracapacitor.
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