CN101302341A - Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode - Google Patents
Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode Download PDFInfo
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- CN101302341A CN101302341A CNA2007100543652A CN200710054365A CN101302341A CN 101302341 A CN101302341 A CN 101302341A CN A2007100543652 A CNA2007100543652 A CN A2007100543652A CN 200710054365 A CN200710054365 A CN 200710054365A CN 101302341 A CN101302341 A CN 101302341A
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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
- Y02E60/10—Energy storage using batteries
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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
Abstract
The invention provides a conducting composite material which comprises polypyrrole, polythiophene, polyaniline, polyacetaldehyde, poly1,2-ethenylene thiophene, polyvinylcarbazole and copolymers of the compounds, nano-carbon materials and unsaturated compounds. The conducting composite material improves clinging property among materials, filming property and has low specific resistance, and can maintain the low specific resistance in a high temperature environment. The invention provides a composite electrode, which is made into a certain shape by the conducting composite material which is pressed and spread on a graphite flake, an aluminium flake, a copper sheet, a steel sheet, or alloy of the metals, or foam materials. The composite electrode has reduced specific resistance, and can maintain the specific resistance in a high temperature environment. An ultra-capacitor and a lithium battery which use the composite electrode have excellent properties of low specific resistance and high capacity.
Description
Technical field
The invention belongs to field of functional materials, the present invention relates to the preparation method of conductive composite material and conductive composite material, combined electrode also relates to super large capacitor and lithium cell.
Background technology
The conductive polymer material that comprises electric conductive polymer is expected to be applied to: the purposes that the needs electricity is led, electrically conducting coating, antistatic agent, electromagnetic shielding material, the electro-conductive material of the transparency, battery material, capacitor material, transmitter, electronic material, semiconductive material, solar cell, Organic Light Emitting Diode, field emission type display (FED), touch-screen, EL sheet (Electroluminance), OTFT (Organic thin-film transistor), electrostatic duplicating parts, transfer member, Electronic Paper (epaper), electrofax material etc.
Usually, so-called electric conductive polymer is the polypyrrole class, polythiophene class, and the polyacetylene class, poly-inferior benzene class, polyphenylene 1, the inferior vinyl of 2-, polyaniline compound, the metaldehyde class, poly-vinylene thiophene-based, and these multipolymer etc.These electric conductive polymers can be by chemical oxidative polymerization and the preparation of solid electrolytic polymerization.
In the solid electrolytic polymerization, but in the solid electrolyte mixing solutions that monomer and doping agent by electric conductive polymer constitute, add preformed electrode materials, on electrode, electric conductive polymer is formed film like.Therefore, be difficult to preparation in large quantities.
In contrast to this, in chemical oxidative polymerization, do not have such restriction, the monomer of electric conductive polymer, suitable oxygenant and catalyzer, can be in solution a large amount of electric conductive polymer of polymerization.But, in chemical oxidative polymerization, along with the growth of electric conductive polymer main chain, for the solvability reduction of organic solvent.Therefore, what obtain mostly is insoluble solid shape powder, therefore, is difficult to use with this state.
For addressing this is that, such scheme has been proposed: by importing suitable substituting group or using the polyanion based compound to carry out solubilize to organic solvent.As the example of soluble conductive polymkeric substance, the Baytron-P of H.C.Starck-V TECH Ltd. production etc. is arranged on market.Yet, this polymkeric substance have high resistance and under high-temperature resistance enlarge markedly.
Capacitor with super capacity is a kind of novel energy-storing device, dielectric capacitor is to come store charge by polarization of dielectric, comes store charge and capacitor with super capacity is interaction by electrolyte ion and electrode, so have heavy body, high charge-discharge efficient, advantages such as long lifetime.Can be used for electric vehicle, circuit card, household electrical appliances, the aspect of the recovery energy.
Originally, with the super large capacitor and the lithium cell of activated carbon or fiber activated carbon, loading capacity was low, and the long term maintenance loading capacity is difficulty relatively.
For addressing this problem, use the conductive polymer electrodes of electrolytic polymerization method preparation, compare with the activated carbon electrode and can improve loading capacity (referring to patent documentation 1, for example Japanese Unexamined Patent Application publication spy opens flat 06-104141).
Also have, use after by porous carbon material and chemical oxidative polymerization polymerization electric conductive polymer and the conductive composite material mfg. electrode formed, high discharge capacity and electroconductibility all have rising (referring to patent documentation 2, for example Japanese Unexamined Patent Application publication spy opens 2002-25865).
Summary of the invention
When using the method for patent documentation 1, loading capacity still is insufficient, and internal resistance is also than higher.Adding that productivity is low because of being to use the solid electrolytic polymerization, also must use specific equipment.And the thickness of control electric conductive polymer is also relatively more difficult.
When using the method for patent documentation 1, the mass ratio of electric conductive polymer and porous carbon material is received restriction, and the ratio that increases electric conductive polymer is difficult.
The present invention provides a kind of conductive composite material, be the high resistance problem of solution electric conductive polymer and conductive composite material, and resistance enlarges markedly problem under high-temperature.This conductive composite material has the close property of enhancing to storeroom, the system film, and low-resistivity, and under hot environment, also can keep low-resistivity.This conductive composite material is by pyroles and derivative thereof, thiophene-based and derivative thereof, aniline and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, and the electric conductive polymer that constitutes such as the multipolymer of these compounds, nano-sized carbon material and unsaturated compound and form.
The present invention also provides a kind of combined electrode, and this combined electrode is to have the resistivity that reduces, and also can keep low-resistivity under hot environment.Use the super large capacitor and the lithium cell of this combined electrode, have the excellent properties of low-resistivity and heavy body.
Conductive composite material of the present invention is by pyroles and derivative thereof, thiophene-based and derivative thereof, aniline and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, and the electric conductive polymer that constitutes such as the multipolymer of these compounds, the nano-sized carbon material, and by replacing or unsubstituted vinyl and derivative thereof, replace or unsubstituted ethene ethers and derivative thereof, replace or unsubstituted acrylic amide and derivative thereof, replace or unsubstituted acrylic acid or the like and derivative thereof, replace or unsubstituted vinyl alcohol and derivative thereof, replace or unsubstituted fluoride class, replace or unsubstituted siliceous compounds, and these copolymerization, at least a unsaturated compound in the reactive polymer and forming.
Conductive composite material of the present invention contains conductive composite body at least, can also contain polyanion, doping agent, and electroconductibility is adjusted wedding agent, resinous principle, conductive particle etc.
Conductive composite material of the present invention has the close property of enhancing to storeroom, the system film, and low-resistivity, and under hot environment, also can keep low-resistivity.
Combined electrode of the present invention has the resistivity that reduces, and also can keep low-resistivity under hot environment.Use the super large capacitor and the lithium cell of this combined electrode, have the excellent properties of low-resistivity and heavy body.
Embodiment
Below, preference of the present invention is described.But the present invention is not limited to following each example.For example, the integrant of these examples and mode correspondence or appropriate combination mutually to each other.
Conductive composite material of the present invention is by pyroles and derivative thereof, thiophene-based and derivative thereof, aniline and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, and the electric conductive polymer that constitutes such as the multipolymer of these compounds, the nano-sized carbon material, and by replacing or unsubstituted vinyl and derivative thereof, replace or unsubstituted ethene ethers and derivative thereof, replace or unsubstituted acrylic amide and derivative thereof, replace or unsubstituted acrylic acid or the like and derivative thereof, replace or unsubstituted vinyl alcohol and derivative thereof, replace or unsubstituted fluoride class, replace or unsubstituted siliceous compounds, and these copolymerization, at least a unsaturated compound in the reactive polymer and forming.Also can be by electric conductive polymer, the nano-sized carbon material, solvent, in the solution that oxygenant or catalyzer are formed, the polyreaction by unsaturated compound forms.
Conductive composite material of the present invention contains conductive composite body at least, can also contain polyanion, doping agent, and electroconductibility is adjusted wedding agent, resinous principle, conductive particle etc.
Combined electrode of the present invention is that the combination electrode material made by conductive composite material is repressed or be coated on graphite flake, aluminium flake, and copper sheet, the nickel sheet, the alloy of steel disc or these metal, foam materials is made definite shape and is formed.
(conductive composite material)
Conductive composite material of the present invention is to be used in the nano-sized carbon material and polymerisable electric conductive polymer is monomeric disperses or dissolves in the liquid, use chemical oxidative polymerization, after by oxygenant or catalyzer polymerisable electric conductive polymer free oxygen being changed into electric conductive polymer, in the presence of oxygenant or catalyzer, obtain with the polymer reaction of unsaturated compound or reactive unsaturated compound.When the growth step of reaction of electric conductive polymer is added the polymkeric substance of unsaturated compound or reactive unsaturated compound, generation association reaction between the polymkeric substance of electric conductive polymer and unsaturated compound or reactive unsaturated compound and the conductive composite material that forms.Second preparation method of conductive composite material of the present invention is for using chemical oxidative polymerization, after by oxygenant or catalyzer polymerisable electric conductive polymer free oxygen being changed into electric conductive polymer, in the presence of oxygenant or catalyzer, obtain conductive composite body with the polymer reaction of unsaturated compound or reactive unsaturated compound, also can obtain by mixing the nano-sized carbon material.
(electric conductive polymer)
In conductive composite material of the present invention, so long as main chain is got final product by the organic polymer that common rail system constitutes, there is not particular restriction as electric conductive polymer.For example can enumerate: polypyrrole class and derivative thereof, polythiophene class and derivative thereof, polyacetylene class and derivative thereof, poly-inferior benzene class and derivative thereof, polyphenylene 1, inferior vinyl of 2-and derivative thereof, polyaniline compound and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, and these multipolymer etc.Especially from chemical stabilization under air atmosphere, the good aspect of operability is considered, preferably uses the polypyrrole class,, polythiophene class, polyphenylene 1, the inferior vinyl of 2-, polyaniline compound.
Object lesson as the electric conductive polymer of preferred use can be enumerated: polypyrrole, poly-(3-methyl) pyrroles, poly-(3-ethyl) pyrroles, poly-(3-carboxyl) pyrroles, poly-(3-methyl-4-carboxyl) pyrroles, poly-(3-methyl-4-propyloic) pyrroles, poly-(3-hydroxyl) pyrroles, poly-(3-methoxyl group) pyrroles, poly-(3-oxyethyl group) pyrroles, poly-(3-butoxy) pyrroles, poly-(3-hexyloxy) pyrroles, poly-(3-methyl-4-hexyloxy) pyrroles waits the polypyrrole class; Polythiophene, poly-(3-methyl) thiophene, poly-(3-hexyl) thiophene, poly-(3-decyl) thiophene, poly-(3-phenyl) thiophene, poly-(3-dodecyl) thiophene, poly-(3, the 4-dimethyl) thiophene, poly-(3-hydroxyl) thiophene, poly-(3-methoxyl group) thiophene, poly-(3-oxyethyl group) thiophene, poly-(3-butoxy) thiophene, poly-(3-hexyloxy) thiophene, poly-(3-octyloxy) thiophene, poly-(3-oxygen in last of the ten Heavenly stems base) thiophene, poly-(3-dodecyloxy) thiophene, poly-(3, the 4-dihydroxyl) thiophene, poly-(3, the 4-dimethoxy) thiophene, poly-(3, the 4-diethoxy) thiophene, poly-(3,4-two hexyloxy) thiophene, poly-(3,4-oxygen base in two heptan) thiophene, poly-(3,4-two octyloxies) thiophene, poly-(3,4-didecyl oxygen base) thiophene, poly-(3,4-docosane oxygen base) thiophene, poly-(3, the 4-ethylenedioxy) thiophene, poly-(3, the inferior third dioxy base of 4-) thiophene, poly-(3,4-butylene dihydroxyl) thiophene, poly-(3-methyl-4-methoxyl group) thiophene, poly-(3,4-ethylene dioxy base) thiophene, poly-(3,4-butylene dioxy base) polythiophene class such as thiophene, and polyaniline, poly-(2-aniline sulfonic acid), poly-polyaniline compounds such as (3-aniline sulfonic acid) etc.
These electric conductive polymers can prepare by chemical oxidative polymerization.Under the condition that has oxygenant or catalyzer, change into electric conductive polymer from polymerisable electric conductive polymer free oxygen.As long as having more than 2, the polymeric unit of electric conductive polymer can obtain good electrical conductivity.
The monomeric object lesson of polymerisable electric conductive polymer as preferred use can be enumerated: pyrroles, 3-methylpyrrole, 3-N-ethyl pyrrole N-, the 3-carboxy pyrrole, 3-methyl-4-carboxy pyrrole, 3-methyl-4-propyloic pyrroles, 3-hydroxyl pyrroles, 3-methoxyl group pyrroles, 3-oxyethyl group pyrroles, 3-butoxy pyrroles 3-hexyloxy pyrroles, 3-methyl-4-hexyloxy pyrroles, thiophene, 3 methyl thiophene, 3-hexyl thiophene, 3-decylthiophene, 3-phenyl thiophene, 3-dodecyl thiophene, 3, the 4-thioxene, 3-hydroxyl thiophene, 3-methoxythiophene, 3-oxyethyl group thiophene, 3-butoxy thiophene, 3-hexyloxy thiophene, 3-octyloxy thiophene, 3-oxygen in last of the ten Heavenly stems base thiophene, 3-dodecyloxy thiophene, 3,4-dihydroxyl thiophene, 3, the 4-dimethoxy-thiophene, 3,4-diethoxy thiophene, 3,4-two hexyloxy thiophene, 3,4-oxygen base in two heptan thiophene, 3,4-two octyloxy thiophene, 3,4-didecyl oxygen base thiophene, 3,4-docosane oxygen base thiophene, 3, the 4-Ethylenedioxy Thiophene, 3, the inferior third dioxy base thiophene of 4-, 3,4-butylene dihydroxyl thiophene, 3-methyl-4-methoxythiophene, 3, the 4-ethylene dioxythiophene, 3,4-butylene dioxy base thiophene, aniline, 2-aniline sulfonic acid, 3-aniline sulfonic acid etc.
Can use peroxydisulfate such as ammonium peroxydisulfate, Sodium persulfate, Potassium Persulfate as oxygenant, iron(ic) chloride, ferric sulfate, cupric chloride, transistion metal compounds such as tosic acid iron, silver suboxide, Cs2O metal oxides such as (Se), hydrogen peroxide, superoxide such as ozone, organo-peroxides such as peroxidation benzene first phthalein, oxygen etc.
As the solvent of chemical oxidising polymerisation,, for example can enumerate: water, N-Methyl pyrrolidone (NMP) so long as the solvent of solubilized or dispersion oxygenant or oxypolymerization catalyzer gets final product, N, N '-dimethyl methyl phthalein amine (DMF), N, N '-dimethyl second phthalein amine (DMAc), dimethyl sulfoxide (DMSO) (DMSO), methylphenol, phenol, xylenol, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, methyl ethyl ketone, hexane, benzene, toluene, formic acid, acetate, ethylene carbonate vinegar, propylene carbonate vinegar, dioxane, diethyl ether, dialkyl ether ethylene glycol vinegar, dialkyl ether propylene glycol vinegar, poly-dialkyl ether ethylene glycol vinegar, poly-dialkyl ether propylene glycol vinegar, second eyeball, methoxyl group second eyeball, propionitrile, benzene eyeball, glycol, glycerine, triethylene glycol butyl ether triethylene glycol butyl ether, triethylene glycol butyl ether, the triethylene glycol monobutyl ether, triglycol butyl ether, butoxy triethylene glycol ether etc.As required, these solvents can be independent, two or more mixing, or mix use with other organic solvents.
As polymerization temperature, as long as, be preferable over 0-130 ℃-30-200 ℃ scope.
Conductive composite material of the present invention is in the presence of nano-sized carbon material and oxygenant or catalyzer, after changing into electric conductive polymer by polymerisable electric conductive polymer free oxygen, in the presence of oxygenant or catalyzer, obtain with the polymer reaction of unsaturated compound or reactive unsaturated compound.As required, can oxypolymerization in the presence of doping agent and polyanion.
After conductive composite material of the present invention can also obtain the conductive composite body of electric conductive polymer and unsaturated compound, also can obtain by mixing the nano-sized carbon material.
(nano-sized carbon material)
As the nano-sized carbon material, its principal constituent is a carbon element, and particle diameter is below the 1000nm, and shape etc. all do not have particular restriction.For example can enumerate: particle diameter is the carbon particles of 5-5000nm, porous carbon particle, hydroxylation carbon particles, carboxylated carbon particles, sulfonic group carbon particles, sulfation carbon particles, gac, graphite particle, porous graphite, graphite flake (comprising hand chair form armchair and prionodont zigzag), needle-like graphite, graphite carbon dust, graphite oxide, hydroxylation graphite, carboxylated graphite, sulfonic group fossil China ink, sulfation graphite, staple length are that 10-10000nm and line directly are the carbon fiber of 1-1000nm, graphite fibre, activated carbon fiber, Single Walled Carbon Nanotube, double-wall carbon nano-tube, multiple-wall carbon nanotube, the hydroxylation CNT (carbon nano-tube), carboxylated CNT (carbon nano-tube) etc.
In this conductive composite material, the mass ratio of electric conductive polymer and nano-sized carbon material (electric conductive polymer: the nano-sized carbon material) preferred 99: 1-1: 99, more preferably 80: 20-5: 95.As long as in this scope, good electrical conductivity and loading capacity are then arranged, but when the nano-sized carbon material is lower than this scope, the inadequate tendency of capacity is arranged then.When being higher than this scope, the inadequate tendency of electroconductibility is arranged then.
(unsaturated compound)
In conductive composite material of the present invention, as unsaturated compound so long as can and electric conductive polymer be reacted into complex body and get final product, do not have particular restriction.For example can enumerate: replace or unsubstituted vinyl and derivative (alkylene) thereof, replace or unsubstituted ethene ethers and derivative thereof, replace or unsubstituted acrylic amide and derivative (Acrylamide) thereof, replace or unsubstituted acrylic acid or the like and derivative (Acryl) thereof, replace or unsubstituted vinyl alcohol and derivative thereof, replace or unsubstituted fluoride class, replace or unsubstituted siliceous compounds, and these copolymerization, reactive polymer etc.Be preferably: vinyl and derivative thereof, ethene ethers and derivative thereof, acrylic amide and derivative thereof (Acrylamide), acrylic acid or the like and derivative thereof (Acryl), vinyl alcohol and derivative thereof, vinegar class and derivative thereof, glycols and derivative thereof, glycerols and derivative thereof, fluorochemical class and derivative thereof, and these copolymerization etc.
There is not particular restriction as substituting group.Be preferably: alkyl, carboxyl (COOR), amino (NH), and-oxyl (HO), carbonyl (CO), sulfonic group (SO3H), amide group (CONRR), fat-oxyl (alkoxyl), ester group (ester), ether (ether), epoxy group(ing), silica-based, fluorine-based, aryl etc.
For example can enumerate as preferred unsaturated compound: ethene, propylene, divinyl, vinylbenzene (SM), 2, the 3-dichloropropylene, 1, the 3-dichloropropylene, vinylcarbinol, acrylate chloride, the ethene imidazoles, V-Pyrol RC, the ethene dimethyl sulfoxide (DMSO), divinylsulfone, iso-butylene, diallyl amine, the N-vinyl carbazole, the ethene triazole, vinylpyridine, the ethene pyrazoles, vinyl cyanide (AN), vinyl acetate between to for plastic (VAM), acrylamide (AM), Methacrylamide (MAM), N-alkyl acrylamide, N hydroxymethyl acrylamide (N-MAM), acrylic acid amides, vinylformic acid hydroxyl phthalein amine (HEAA), vinylformic acid (AA), methacrylic acid (MAA), methyl acrylate (MA), methyl methacrylate (MMA), ethyl propenoate (EA), Jia Jibingxisuanyizhi (EMA), butyl acrylate (BA), butyl methacrylate, Isooctyl acrylate monomer (2-EHA), propylene phthalein amine, N, N-dimethyl second phthalein amine (DMA), N,N-DMAA, N, N '-methylene-bisacrylamide (DMAM), ethene methyl first phthalein amine, n-methylolacrylamide, the hydroxyethyl acrylamide, N, N-dioctyl acrylamide, methene base bisacrylamide, Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410, Rocryl 410 (HPMA), vinylformic acid hydroxy butyl ester (HBA), n-BMA (nBMA), Propenoic acid, 2-methyl, isobutyl ester (IBMA), Isooctyl methacrylate (EHMA), isobornyl methacrylate (IBOMA), glycidyl methacrylate (GMA), methacrylic acid cyclohexyl ester (CHMA), tri (propylene glycol) diacrylate (TPGDA), 1,4 butanediol diacrylate (BDDA), Ethylene glycol dimethacrylate (EGDMA), neopentylglycol diacrylate (NPGDA), Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), methylmaleic acid, lauryl methacrylate(LMA) (LMA), vinyl sulfonic acid and vinyl sulfonate, styrene sulfonic acid and styrene sulfonate, vinylformic acid vinyl sulfonic acid and vinylformic acid vinyl sulfonate, first for allyl sulfonic acid and first for allyl sulfonate, methyl allyloxy Phenylsulfonic acid and methyl allyloxy benzene sulfonate, vinylidenefluoride, R 1216 etc.
As oxygenant, catalyzer can use oxygenant recited above and catalyzer, also can use the photopolymerization catalyzer.
As the temperature of reaction of unsaturated compound, so long as-scope of 30-200 ℃ gets final product, and preferred 0-130 ℃, more preferably 20-90 ℃.
In this conductive composite material, the mass ratio of electric conductive polymer and unsaturated compound (electric conductive polymer: compd B) preferred 95: 5-1: 99, more preferably 80: 20-5: 95.As long as in this scope, then electroconductibility and solvent solubility are all high, but when unsaturated compound is lower than this scope, the inadequate tendency of solvent solubility and close property are arranged then.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(polyanion)
In conductive composite material of the present invention, remove unsaturated compound, can also contain polyanion beyond nano-sized carbon material and the electric conductive polymer, when containing polyanion, conductive composite material can obtain good dispersiveness and electroconductibility.
So long as side chain has the carboxylic acid group, sulfonic polymer can use as polyanion.For example can enumerate as main chain: the polyalkylene compound that main chain is made of repeatedly methylene radical, main chain contain the poly-alkenylene compound of the component unit formation of vinyl, poly-vinegar resin, poly-phthalein polyimide resin, poly-phthalimide resin, fluoro-resin, ethenoid resin, Resins, epoxy, xylene resin, the aramid resin, polyurethane is a resin, melmac, phenolic resin, polyethers, acrylic resin and these compositions such as copolymer resins.Polyanion can be that polymerizable monomer and carboxylic acid are that polymerizable monomer obtains with polymerization by sulfonic acid, also can get multipolymer with other polymerizable monomers as required.Can enumerate as concrete example: replace or unsubstituted vinyl sulfonic acid compound, replace or unsubstituted styrene sulfonic acid compound, replace or unsubstituted heterocycle sulfoacid compound, replace or unsubstituted propylene phthalein amine sulfoacid compound, replace or the inferior vinyl sulfonic acid compound of unsubstituted ring, replace or unsubstituted vinyl aromatic sulfoacid compound replacement or unsubstituted vinylformic acid etc.Can enumerate as other polymerizable monomers: replace or unsubstituted vinyl compound, the substitutional crylic acid compound, replace or unsubstituted vinylbenzene, replace or unsubstituted vinyl-amine, the heterogeneous ring compound that contains unsaturated group, replace or unsubstituted propylene phthalein amine compound, replace or unsubstituted ring vinylidene compound, replace or unsubstituted adiene cpd, replace or unsubstituted vinyl aromatic compound, replace or unsubstituted divinyl benzene compound substituted ethylene base oxybenzene compound, replace silyl vinylbenzene arbitrarily, arbitrarily 5-substituted phenol compounds etc.
Can use peroxydisulfate such as ammonium peroxydisulfate, Sodium persulfate, Potassium Persulfate as polymerizing catalyst and oxygenant, iron(ic) chloride, ferric sulfate, cupric chloride, transistion metal compounds such as tosic acid iron, silver suboxide, metal oxides such as Cs2O, hydrogen peroxide, superoxide such as ozone, organo-peroxides such as peroxidation benzene first phthalein, oxygen, photopolymerization catalyzer etc.
The object lesson of poly-sulfonic acid can be enumerated: polyvinyl sulfonic acid with and salt, polystyrolsulfon acid with and salt, the polyacrylic acid vinyl sulfonic acid with and salt, poly-first for allyl sulfonic acid with and salt, poly-methyl allyloxy Phenylsulfonic acid with and salt, poly-sulfonic acid vinegar resin with and salt, poly-sulfonic acid phthalimide resin with and salt etc.
The molecular-weight average of poly-sulfonic acid is so long as 1,000-1, and 000,000 scope gets final product, and preferable range is 5,000-500,000.
As the positively charged ion of polysulfonate for example: tetramethyl ammonium, tetraethyl-ammonium salt, tetrapropyl ammonium salt, 4-butyl ammonium, tetrahexyl ammonium salt, trimethylammonium ethyl ammonium salt, trimethylphenyl ammonium salt, triethyl phenyl ammonium salt, Three methyl Benzene idol phthalein ammonium salt, 4 grades of ammonium salts such as trimethylammonium octyl group ammonium salt, metal cation salt, imidazole-like ionic salt, pyridines ion salt etc.
In this conducing composite material, the mass ratio of poly-sulfonic acid and electric conductive polymer (poly-sulfonic acid: electric conductive polymer) preferred 99: 1-1: 99, more preferably 95: 5-10: 90, most preferably 80: 20-30: 70.As long as in this scope, then electroconductibility and solvent solubility are all high, but when poly-sulfonic acid is lower than this scope, the inadequate tendency of solvent solubility are arranged then.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(doping agent and electroconductibility are adjusted wedding agent)
Can mixing and doping agent and electroconductibility adjustment wedding agent in order to improve its electroconductibility of described electric conductive polymer.Electroconductibility is adjusted the performance that wedding agent is adjusted film-forming properties in addition.
As long as can produce redox reaction with electric conductive polymer, do not limit electron acceptor or electronics and supply and body as doping agent.For example: halogen compound, Lewis acid, protonic acid etc.Can enumerate chlorine, iodine, iodine chloride, fuorine iodine etc. as halogen compound.In addition, can enumerate phosphorus pentafluoride (PF5), arsenic pentafluoride (AsF5), boron trifluoride (BF3), boron trichloride (BC13) etc. as Lewis acid.In addition, can enumerate as protonic acid: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluoroboric acid, mineral acids such as hydrofluoric acid, organic carboxyl acid, organic acids such as organic sulfonic acid, organic cyanogen compound etc.
Can use in aliphatics as organic carboxyl acid, aromatic series contains one or more carboxylic acid groups' material on the annular aliphatic etc.For example can enumerate: formic acid, acetate, oxalic acid, M-nitro benzoic acid, phthalic acid, toxilic acid, fumaric acid, propanedioic acid, tartrate, citric acid, lactic acid, Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, nitroacetic acid, triphenylacetic acid etc.Also can use these amine salt, metal-salt.
Can use in aliphatics as organic sulfonic acid, aromatic series, annular aliphatics etc. are gone up in conjunction with one or more sulfonic materials.Can enumerate as organic sulfonic acid: methylsulphonic acid, ethylsulfonic acid, trifluoromethane sulfonic acid, Phenylsulfonic acid, tosic acid, xylene monosulfonic acid, ethyl phenenyl azochlorosulfonate acid, 2, the 4-acid dimethyl, the dipropyl Phenylsulfonic acid, 4-aniline sulfonic acid, p-chlorobenzenesulfonic acid, naphthene sulfonic acid, methyl naphthalene sulfonic acid, naphthalene sulfonic acid formaldehyde condensation polymer, the green onion disulfonic acid, butyl green onion disulfonic acid, 1-second phthalein oxygen base-3,6,8-trisulfonic acid, 7-amino-1,3,6-naphthalene trisulfonic acid, o-sulfobenzoic acid, 3,5-disulfonic acid phenylformic acid, sulfophthalic acid, sulfo group pure terephthalic acid, cysteic acid, 5-sulphosalicylic acid etc.Also can use these ammonium salt, metal-salt.
In this conducing composite material, be the mol ratio (doping agent: electric conductive polymer) preferred 0.1: 1-10: 1, more preferably 0.5: 1-7: 1 of electric conductive polymer as the content of doping agent.When the content of doping agent is lower than this scope, then can not obtain sufficient electroconductibility sometimes.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
Adjust wedding agent as electroconductibility and can use at hydroxy-containing compounds, carboxylated compound (organic acid) (COOH) contains aminocompound, the amino-contained aromatics contains carbonyl (CO) compound, contains the acetify compound, contain ammonia vinegar based compound, contain ether compound, amide compound contains imide compound, contain acrylic compound, contain epoxy compounds, silicon-containing compound, fluorochemicals etc.For example can enumerate: N-N-methyl-2-2-pyrrolidone N-, N, N '-dimethyl methyl phthalein amine, N, N '-dimethyl second phthalein amine, dimethyl sulfoxide (DMSO), triethylene glycol butyl ether triethylene glycol butyl ether, triethylene glycol butyl ether, the triethylene glycol monobutyl ether, triglycol butyl ether, butoxy triethylene glycol ether, oxeye alcohol, arabitol, 3-amino-1, the 2-propylene glycol, N.F,USP MANNITOL, glycol, glycol ether, triethylene glycol, poly-glycol, glycerine, Glycerol dimer, Polyglycerine, sorbyl alcohol, tetramethylolmethane, dipentaerythritol, 3-methoxyl group-1,2-propylene glycol, allitol, Xylitol, melampyrum, semi-lactosi, pectinose, glucose, monose, disaccharides, polysaccharide, galacturonic acid, glyconic acid, DL-hydroxy-butanedioic acid, glutinous acid, gulonic acid, different VC acid, oxalic acid, oxysuccinic acid, diacid ammonium, vitamin c class, tartrate, D-dibenzoyl tartaric acid, heptonic acid and these hydrochlorate, glucosamine, dioxane, diethyl ether, dialkyl ether ethylene glycol vinegar, dialkyl ether propylene glycol vinegar, poly-dialkyl ether ethylene glycol vinegar, poly-dialkyl ether propylene glycol vinegar, imidazoles, m-phthalic acid, SO 3 sulfonated m-phthalic acid, sour methyl esters, aforementioned unsaturated compound etc.
Can use stiffening agent in order to improve higher film-forming properties.Can use known method and known stiffening agent as curing condition and stiffening agent, not have particular restriction.For example: photochemical reaction, ionic reaction etc.Stiffening agent can be enumerated: aromatic ketone, methyl phenyl ketone, benzophenone, Octabenzone, platinum, ammonium peroxydisulfate, Sodium persulfate, peroxydisulfate such as Potassium Persulfate, iron(ic) chloride, ferric sulfate, cupric chloride, transistion metal compounds such as tosic acid iron, silver suboxide, metal oxides such as Cs2O, hydrogen peroxide, superoxide such as ozone, organo-peroxides such as peroxidation benzene first phthalein, oxygen etc.
In this conducing composite material, electroconductibility is adjusted the mass ratio of wedding agent and conducing composite material, and (electroconductibility is adjusted wedding agent: conducing composite material) preferred 1: 99-99: 1, more preferably 10: 90-95: 5, most preferably 20: 80-90: 10.As long as in this scope, then electroconductibility and solvent solubility are all high, but when electroconductibility adjustment wedding agent is lower than this scope, then can not obtain the tendency of sufficient electroconductibility and film-forming properties sometimes.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(resinous principle)
Conducing composite material of the present invention also can contain other compositions as required.
For example to adjust film-forming properties, film toughness etc. are purpose, can use other organic resins and other additives simultaneously.As organic resin, as long as conducing composite material is held concurrently molten or blending dispersion can be used any thermosetting resin, thermoplastic resin, photo-curable resin relatively.
Resin can be used as its object lesson, for example can enumerate: poly-vinegar resin, poly-phthalimide resin, poly-phthalein polyimide resin, poly-fluoro-resin, polyvinyl resin, Resins, epoxy, xylene resin, polyoxyethylene glycol, aramid resin, polyurethane is a resin, poly-vein system resin, melmac, phenolic resin, polyethers, the copolymer resins of acrylic resin and these materials, siliceous copolymer resins, aforesaid unsaturated compound, aforesaid electroconductibility is adjusted the part of wedding agent etc.
Can add resinous principle arbitrarily in the conducing composite material of the present invention as required, add content and also be not particularly limited.
As other additives so long as can and conducing composite material is held concurrently molten or blending dispersion can be used any defoamer, neutralizing agent, oxidation inhibitor, tensio-active agent, coupling agent, conductive fillers etc. do not have particular restriction.
For example can enumerate as conductive filler: particle diameter is the copper of 5-5000nm, nickel, silver, gold, tin, metallicss such as iron etc.
In this conducing composite material, the mass ratio of conductive filler and conducing composite material (conductive filler: conducing composite material) preferred 1: 99-90: 10, more preferably 20: 80-80: 20.
Conducing composite material of the present invention is by electric conductive polymer, nano-sized carbon material, unsaturated compound and forming.So as mentioned above, can obtain having the close property of enhancing to base material, the system film, and have favorable conductive matrix materials such as high conductance, permanent stability.
Another object of the present invention is by using above-mentioned conducing composite material, a kind of combined electrode with excellent properties is provided, reaching the super large capacitor and the lithium cell that use this combined electrode.
Below to combined electrode of the present invention and use the super large capacitor of this combined electrode to describe as example.
Combined electrode of the present invention is by graphite flake, aluminium flake, and copper sheet, nickel sheet (Ni), the alloy of steel disc or these metal, electro-conductive material and conductive composite materials such as foam materials are made definite shape and are formed.
Combined electrode of the present invention can be used in super large capacitor and lithium cell.The structure of this super large capacitor and lithium cell constitutes, and does not have particular restriction.For example: super large capacitor needs only combined electrode, ionogen, and electrolytic paper gets final product.Lithium cell needs only combined electrode, ionogen, and electrolytic paper, lithium electrode gets final product.
Combined electrode of the present invention is by graphite flake, aluminium flake, and copper sheet, nickel sheet (Ni), the alloy of steel disc or these metal, electro-conductive material such as foam materials and conductive composite material constitute.The preparation method does not have particular restriction.For example: with compacting, coating, spraying, printing, impregnating method.
As conducing composite material, can use aforesaid electric conductive polymer, nano-sized carbon material, unsaturated compound and the conducing composite material that forms.
As long as ionic conductivity is arranged, there is not particular restriction as ionogen.Known ionogen and polymer electrolyte all can use.For example: carboxylic compound, sulfonic group compound, ionic liquid, LiBF
4, LiClO
4, LiPF
6, LiAsF
6, Li (CF
3O
2)
2N, LiC
4F
9SO
3, perchlorate, a tetrafluoro borate, phosphoric acid salt, poly-glycol, poly-phthalein amine, poly-carboxylic compound, poly-sulfoacid compound, polyvinyl alcohol, polyvinyl ether etc.
As electrolytic paper, can use known electric capacity electrolytic paper, and lithium cell electrolysis paper, there is not particular restriction.
Another object of the present invention is to be electrical conductor by using above-mentioned conducing composite material, provides a kind of heavy body that has, the combined electrode of excellent properties such as low-resistivity.And provide a kind of super large capacitor and lithium cell that uses this combined electrode.
Beneficial effect
So conducing composite material in the present invention as mentioned above, can obtain having the close property of enhancing to base material, the system film, and have favorable conductive matrix materials such as high conductance, permanent stability, and have higher intensity.The condensation material of replying by cable of the present invention uses when the electrode of super large capacitor and lithium cell, and this super large capacitor and this lithium cell have heavy body, excellent properties such as low-resistivity.
Embodiment
To conducing composite material of the present invention, the preparation object lesson of combined electrode and super large capacitor describes below.The present invention is not only limited to this object lesson.
(synthetic polystyrene sulfonic acid)
The Sodium styrene sulfonate of 50g is dissolved in the 500ml water, adds the Sodium Persulfate of 0.25g, heated and stirred 3 hours.
Put cold after, spent ion exchange resin cationic exchange after, be modulated to the polystyrolsulfon acid aqueous solution of 3wt% with ion exchanged water.
(preparation conducing composite material 1)
With 3 of 5g, the 4-ethylene dioxythiophene, (line directly is 10nm to the activated carbon fiber of 5g, and surface-area is 1200m
2/ g), and the polystyrolsulfon acid aqueous solution of the 3wt% of 150g, the ammonium persulphate of 10g, the ferric sulfate of 1g, the hydroxyethyl acrylamide of 6g and the pure water of 300ml stirred 4 hours after mixing.After adding 5g Hydroxyethyl acrylate (HEA) in this reaction solution, heated and stirred 3 hours.
Put cold after, throw out is filtered, behind pure water and alcohol flushing, throw out is distributed in the ethanol through mixing to stir, the black-and-blue conducing composite material alcohol dispersion liquid that obtains 5wt% is (to call in the following text: conducing composite material 1).
(preparation conducing composite material 2)
With the pyrroles of 3g, the polystyrolsulfon acid aqueous solution of the 3wt% of 100g, the Sodium Persulfate of 10g, the ferric sulfate of 1g and the pure water of 300ml stirred 30 minutes after mixing.After adding 3g Hydroxyethyl acrylate (HEA) in this reaction solution, heated and stirred 3 hours.Then, the particle diameter of 6g is the carbon material powder of 15nm, stirs 10 minutes.
Put cold after, throw out is filtered, behind pure water and alcohol flushing, throw out is distributed in the ethanol through mixing to stir, the black-and-blue conducing composite material alcohol dispersion liquid that obtains 5wt% is (to call in the following text: conducing composite material 2).
(preparation conducing composite material 3)
With the pyrroles of 5g, (line directly is 10nm to the activated carbon fiber of 5g, and surface-area is 1200m
2/ g), and the ammonium persulphate of 6g, the ferric sulfate of 1g, the hydroxyethyl acrylamide of 6g and the pure water of 400ml stirred 2 hours after mixing.After adding the vinylformic acid (AA) and 5g Hydroxyethyl acrylate (HEA) of 2g in this reaction solution, heated and stirred 3 hours.
Put cold after, throw out is filtered, behind pure water and alcohol flushing, throw out is distributed in the ethanol through mixing to stir, the black-and-blue conducing composite material alcohol dispersion liquid that obtains 6wt% is (to call in the following text: conducing composite material 3).
(preparation conducing composite material 1,2,3)
With the conducing composite material 1 that obtains, conducing composite material 2, conducing composite material 3 separate application are to the aluminium flake that corroded, after dry 30 minutes, the aluminium flake with conductive composite material film that obtains is respectively as combined electrode 1 in 120 ℃ of baking ovens, combined electrode 2, combined electrode 3.
(embodiment 1,2,3)
With the combined electrode 1 that obtains, combined electrode 2 is after combined electrode 3 is processed as diameter 15mm respectively, as two electrodes.Between two electrodes, establish the aqueous sulfuric acid ionogen of polypropylene electrolytic paper and 2 mol, obtain super-capacitor 1 (embodiment 7) super-capacitor 2 (embodiment 8), super-capacitor 3 (embodiment 9).
Calculate with electrode materials weight, press the condition test of the current density of 15mA/1g, calculate the dc static capacity from discharge curve, calculate the capacity of electrode materials unit weight, its result is as shown in table 1.
(comparative example 1)
With the pyrroles of 3g, the polystyrolsulfon acid aqueous solution of the 3wt% of 100g, the Sodium Persulfate of 1Og, the ferric sulfate of 1g and the pure water of 300ml stirred 30 minutes after mixing.Then, surface-area is 1200m
2The activated carbon fiber of/g stirred 10 minutes.
Put cold after, throw out is filtered, behind pure water and alcohol flushing, throw out is distributed in the ethanol through mixing to stir, obtain the black-and-blue conducing composite material alcohol dispersion liquid of 4wt%.
Method similarly to Example 5 prepares combined electrode, and method similarly to Example 8 prepares super-capacitor, test performance, and its result is as shown in table 1.
Table 1
| Electrostatic capacity (F/g) | |
| Embodiment 1 | 83 |
| Embodiment 2 | 62 |
| Embodiment 3 | 76 |
| Comparative example 1 | 56 |
Claims (10)
1. conductive composite material, it is characterized in that by electric conductive polymer, nano-sized carbon material and unsaturated compound form, said electric conductive polymer is by polypyrrole class and derivative thereof, polythiophene class and derivative thereof, polyaniline and derivative thereof, metaldehyde class and derivative thereof, poly-vinylene thiophene-based and derivative thereof, at least a in the multipolymer of polyethylene click and derivative thereof and these compounds.
2. conductive composite material according to claim 1 is characterized in that by electric conductive polymer, the nano-sized carbon material, and solvent, in the solution that oxygenant or catalyzer are formed, the polyreaction by unsaturated compound forms.
3. conductive composite material according to claim 1 is characterized in that in the solution that is formed by electric conductive polymer and unsaturated compound, forms by dispersing nanometer carbon element material.
4. conductive composite material according to claim 1 is characterized in that by electric conductive polymer, the nano-sized carbon material, and solvent, in the solution that oxygenant or catalyzer are formed, the polyreaction by unsaturated compound forms.
5. conductive composite material according to claim 1, it is characterized in that described unsaturated compound is by replacing or unsubstituted vinyl and derivative thereof, replace or unsubstituted ethene ethers and derivative thereof, replace or unsubstituted acrylic amide and derivative thereof, replace or unsubstituted acrylic acid or the like and derivative thereof, replace or unsubstituted vinyl alcohol and derivative thereof, replace or unsubstituted fluoride class, replace or unsubstituted siliceous compounds, and these copolymerization, at least a in the reactive polymer.
6. conductive composite material according to claim 1 is characterized in that wherein containing polyanion.
7. conductive composite material according to claim 1 is characterized in that also containing doping agent, and electroconductibility is adjusted wedding agent, resinous principle, at least a in the conductive particle.
8. a combined electrode is characterized in that containing conductive composite material according to claim 1.
9. combined electrode according to claim 8 is characterized in that conductive composite material is repressed or is coated on graphite flake, aluminium flake, and copper sheet, the nickel sheet, the alloy of steel disc or these metal, foam materials is made definite shape.
10. use the super large capacitor and the lithium cell of combined electrode according to claim 8.
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