CN1965018A - composition comprising colloidal conductive polymer and carbon - Google Patents
composition comprising colloidal conductive polymer and carbon Download PDFInfo
- Publication number
- CN1965018A CN1965018A CNA2005800083802A CN200580008380A CN1965018A CN 1965018 A CN1965018 A CN 1965018A CN A2005800083802 A CNA2005800083802 A CN A2005800083802A CN 200580008380 A CN200580008380 A CN 200580008380A CN 1965018 A CN1965018 A CN 1965018A
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- composition
- carbon
- conductive polymers
- electrode
- electrical condenser
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 130
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
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- 239000000463 material Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 41
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- 239000000126 substance Substances 0.000 claims description 17
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- 238000001246 colloidal dispersion Methods 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
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- 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 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention relates to a composition capable of forming a coating layer and containing a mixture of a colloidal conductive polymer and carbon, a method for producing the same, and use of the composition in a large-capacity electric double layer capacitor used in various electronic devices, power sources, and the like.
Description
Technical field
The present invention relates to comprise the electro-conductive material of (intrinsic) conductive polymers and carbon material, their manufacture method and the purposes in the large vol double-layer capacitor that various electronicss, power supply etc. use.
Background technology
Electro-conductive material is known and with many different forms with use to use.Electro-conductive material based on carbon can use with many different physics and chemical form, form and composition.Pure or pure substantially carbon can be with form utilizations such as carbon black (it mainly also comprises the impurity based on oxygen), graphite (pure C), carbon nanotube and soccerballenes.Another group electro-conductive material is (intrinsic) conductive polymers, has been found that some Preliminary Applications.
These two groups of electro-conductive materials have at least a general character, electroconductibility.For one group or another group material, other character can be proprietary, or can change widely in the group separately.For example, to tens microns scope, and the granularity of soccerballene is in the scope of dust several for the granularity of graphite.The specific surface area of carbon black and carbon nanotube shows paramount about 1000m that reaches
2The high value of/g, and graphite at several m
2In the scope of/g.Polyaniline is as one of representative of conductive polymers, its characteristics are rich redox chemistry, PEDOT (polyethylene dioxythiophene) also claims PEDT, have the redox chemistry of appropriateness or bad reproducibility, and graphite or carbon black does not present the reversible redox chemistry.
In the past, tested the combination of conductive polymers such as polyaniline, polyethylene dioxythiophene, polypyrrole or their derivative and carbonaceous material (carbon black, graphite, carbon nanotube and soccerballene).Though the simple mixtures of described material does not present any significant or reproducible advantage, therefore do not find any commerce or The Application of Technology, but the chemical process that is used for conductive polymers and carbon black or conductive polymers and carbon nanotube combination studied widely.For example, the carbon black that Eeonyx company provides polymerization from the teeth outwards that polyaniline is arranged is as development product on the market (" Eeonomer "), referring to G.Du, A.Epstein, K.Reimer is in American Physical Society's meeting in March, 1996, the M23 of branch, the report among the report M 23.09.Supplier of laboratory chemicals Aldrich has announced the mixture that this chemical mode is produced in their catalogue.Yet this product does not present attracting advantage.
Carbon black/polyaniline mixture can present the zone that one of zone of attracting technological merit can be so-called ' ultracapacitor ', also so-called ' bilayer ' or ' redox electrical condenser '.This zone provides the publication of maximum quantity, has mixed carbon and conductive polymers or the carbon and the conductive polymers of the form of mixture are provided in these publications.
For this reason, mainly used two kinds of combination processes:
-by one day the simple mixed carbon black of ball milling and the powder (U.S. Patent Application Publication NO.2002/0114128) of polyaniline, or otherwise as at Journal of Power Sourees 11,2003,185-190 and Journal of the Electrochemical Society, 148,10,2001, the A1130-A1134 disclosed method is wherein mixed polyaniline or polythiofuran derivative with carbon black powder.Yet the blended concrete grammar is not open.
-the chemistry or the electrochemical polymerization of different conductive polymerss on carbon blacksurface.
Back one method was studied in patent and scientific literature widely.European patent application EP 1 329 918 has been reported the cathode composite of carbon and polyaniline or polypyrrole, wherein electrochemical polymerization conductive polymers.Anode is made by lead.Content the best of finding conductive polymers is 10-15 weight %.Comprise combination of electrodes by the electrical condenser that uses this material manufacturing, described combination of electrodes comprises non-polarizable anode and polarizable negative electrode, and wherein non-polarizable anode is made by lead.
U.S. Patent application 2002/0089807 discloses the intrinsic conducting polymer by chemistry or electrochemical method direct polymerization on the carbon black materials of high hole.Journal of Applied Electrochemistry 33,465-473,2003 disclose the electrochemical polymerization of the polyaniline on the carbon aerogels that is generated by polyacrylonitrile.The sort of method and Journal of Power Sources 117,273-282,2003 and lit.10, Carbon 41,2865-2871, the electrochemical polymerization of 2003 disclosed polyanilines on active porous carbon is similar.At Conference Proceedings ofANTEC ' 98, VoL 2,1197ff, and in 1998, the author has reported the polymerization of polyethylene dioxythiophene on the high surface area film of the carbon of platinum collector electrode carrier.In same publication, reported on congener carbon film by hexafluoro-aqueous isopropanol casting polyaniline.
Electrochimica Acta Vol.41, No.1,21-26,1996 disclose the various redox ultracapacitors of symmetry or asymmetric electrode structure, wherein use and on base material polymerization as the various conductive polymerss of polypyrrole or polythiofuran derivative, be similar at United States Patent (USP) 5,527, the method of using in 640,1996 is wherein passed through electrochemical method polymerization polythiofuran derivative on based on the material of carbon.
As explained above, the mixture for preparing carbon black/conductive polymers usually is used for so-called " ultracapacitor ".This electrical condenser also is commonly referred to " double layer capacitor ", " electrochemistry " or " double-layer capacitor " or " redox electrical condenser " and is called " pseudo-capacity electrical condenser (pseudo-capacity capacitor) " sometimes.
Usually, double layer capacitor is a kind of energy device, wherein two electrodes are arranged opposite to each other, between described two electrodes, arrange spacer, described two electrodes are one of at least by using porous carbonaceous material coating collecting board to obtain, and described porous carbonaceous material has about 100 and 1000m collecting board
2Between/the g and above high-specific surface area.Existing under the electrolyte solution situation, on electrode, apply voltage, at least one electrode, to generate electrical double layer and therefrom to obtain energy.As U.S. Patent No. 5,150, disclosed in 283 specification sheetss and the accompanying drawing, a kind ofly use porous carbonaceous material to reel for electrical double layer electrode pair (each electrode all comprises the polarizable electrode that is connected to collecting board) wherein and be included in type and the laminated button-type of electrical double layer electrode pair in the container as the textural classification of the double layer capacitor of electrode materials.
Convoluted have certain structure, is used to release energy in this structure to the spongy lead of outside be connected to the collecting board of for example being made up of the etching aluminium foil of 20 to 50 μ m thickness.The paste coating aluminium foil that use is made up of powdered mixture to be forming conductive layer, and described paste prepares by mixed active carbon powder and required tackiness agent and required conductive agent.The polarizable electrode of being made up of the active carbon layer that mainly is made of gac is formed on the conductive layer, to obtain the electrical double layer electrode, this electrical double layer electrode pair is arranged opposite to each other, and arranges spacer and coiling therein.
Scheme as an alternative under vacuum, is used to comprise the electrolytical electrolytic solution that is dissolved in wherein and flood the polarizable electrode of being made up of active carbon layer and spacer fully, assembles the electrical double layer electrode by this method.Electrode and spacer are inserted in the housing of being made by aluminium etc. and by using the opening portion of package encapsulation aluminum enclosure.Usually, this is assembled into round tube type.
On the other hand, button-type has a fixed structure, and the polarizable electrode of being made up of active carbon layer in this structure is formed on the discoidal valve metal sheet, to obtain the electrical double layer electrode.This electrical double layer electrode pair is arranged opposite to each other, and arranges insulating spacer therein, this assembling is placed in the metal vessel of being made up of two members.These two electrical double layer electrodes have the discoidal matrix band (or paper tinsel) of valve metal, be connected respectively to the bottom of metal vessel and the inboard of top cover portion, bottom and top cover portion are interconnected, circumference edge portion at them uses the insulation lip ring to seal simultaneously, and in container, fill nonaqueous electrolytic solution, this electrolytic solution offers electrical double layer electrode and spacer fully.As nonaqueous electrolytic solution, for example, use by adding the solution that the Tetrafluoroboric acid Tetrylammonium prepares to the propylene carbonate.
The double layer capacitor of several other structures or redox electrical condenser (so-called " ultracapacitor ") are arranged using, do not do detailed description at this.
The large vol electrochemical capacitor has been proposed, wherein use the combination of electrochemical activity inorganic substance or organic (intrinsic) conductive polymers and above-mentioned porous carbonaceous materials or replace above-mentioned porous carbonaceous materials as electrode materials, and wherein with the common electrical double layer capacitor that uses above-mentioned porous carbonaceous material in the same method use current condenser based on electrical double layer formation, and, use simultaneously based on the current condenser of following the Eo+ of oxidation-reduction reaction on two electrodes, thereby realize large vol.
For example, use electrochemical capacitor (the Physics Letters of ruthenium oxide as electrode active material, 26A, p.209 (1968)) be evaluated as the peak performance electrochemical capacitor of present known use inorganic oxide, and confirmed to have the energy density of 8.3Wh/kg and the output density of 30kW/kg.
In recent years, studied and used the electrical condenser (J.Power Sources, vol.29, p.355 (1990)) of other inorganic oxide mixture system as electrode materials.
And, studied the electrochemical capacitor of (intrinsic) conductive polymers of the redox characteristic that utilizes the Pi-conjugated systems organic substance that is different from above inorganic, metal oxide in recent years energetically as electrode materials.
The electrochemical capacitor that uses conductive polymers has been studied by many institutes, as for characteristic, report is for example arranged, use polypyrrole to produce the capacity of 86C/g and the energy density of 11Wh/kg as electrode materials, use the mixture of polypyrrole and Polythiophene to produce the capacity of 120C/g and the energy density of 27Wh/kg, and use poly--3-(4-fluorophenyl) thiophene to produce the capacity of 52C/g and the energy density (J.Power Sources, vol.47, p.89 (1994)) of 39Wh/kg.
Except the above, be used for the type of large value capacitor interlayer in utilization, usually, laminate structure material (TiS
2, MoS
2, CoO
2, V
6O
13) as electrode materials.In this case, most cases uses asymmetric electrode to come assembling device (day translation No.2002-525864, the 2002-542582 of PCT patent).
In addition, compare as the traditional capacitor of electrode materials with only using porous carbonaceous material, the matrix material that is prepared by above various electrode materialss has been be evaluated as the capacity that reaches much higher in some cases.
[the problem to be solved in the present invention]
Although further investigate, the mixture of carbonaceous material and (intrinsic) conductive polymers also is not used in industrial use.Find that its reason mainly is that uniformity of mixture difference and the performance reproducibility that causes owing to employed manufacture method (as mentioned above) are poor on the nano level yardstick.
On the other hand, it is restricted that above-mentioned use porous carbonaceous material is used for the capacity of conventional double-layer capacitor of polarizable electrode, though they have good rapid charge discharge characteristic.For example, open No.2003-338437 describes as Japanese Patent, uses the gac (surface-area: 650m that obtains by the porous carbonaceous material activation
2/ electrical condenser g) has the electrostatic capacity of 18.3F/g, and this is lower than electrochemical capacitor.
As for the relation between the specific surface area of electrostatic capacity and porous carbonaceous material, when specific surface area arrives 2600m 1500
2In the time of in the scope of/g, obtain the electrostatic capacity of about 22F/cc, but, when specific surface area during greater than this scope, capacity no longer increases, but is tending towards reducing (" Electrical Double Layer Capacitors and Electric PowerStorage Systems ", The Nikkan Kogyo Shimbun, Ltd., p.9).
Except the above, Japanese Patent open Nos.2003-217982,2003-81624,2002-373835 etc. disclose the more examples that use the electrode materials of porous carbonaceous material, but compare with electrochemical capacitor, every kind of example all has lower capacity, and this especially becomes problem in application such as automobile.
In addition, when only using porous carbonaceous material to be used for electrode, need to add acetylene black etc. to the tackiness agent to improve specific conductivity, still, even so add, interface resistance is also very high, this constitutes serious problem.
On the other hand, the electrochemical capacitor of conducting metal oxide is as mentioned above used in existence.Compare with the situation of using above porous carbonaceous material, though this electrochemical capacitor has very high capacity, be based on production cost, this electrochemical capacitor is disadvantageous, because the metal of metal oxide belongs to precious metal usually.For example, in nineteen ninety-five the 5th international symposium holding of Florida, US about double layer capacitor and similar energy storage device, reported and used ruthenium oxide or indium oxide film, in water-based system, had the electrostatic capacity of 160F/cc as the pseudo-capacity electrical condenser of electrode materials.
In addition, compare, use conducting polymer materials to demonstrate much higher capacity usually, but their characteristic can change according to the method that forms electrode as the electrochemical capacitor of electrode materials with the electrical condenser that uses above porous carbonaceous material.For example, described in the flat 6-104141 peace of the open No. of Japanese Patent 6-104142, wherein conductive polymers is deposited on the collecting board by the electrolytic polymerization method, electrical condenser has the internal resistance of capacity and 13.9 Ω of 3.7F, forms the serious problems that electrode generally includes relevant its productive rate by the electrolytic polymerization method.
Therefore, many suggestions have been proposed to use the combination of carbonaceous material (mainly being carbon black) and intrinsic conducting polymer.As mentioned above, only two kinds of methods have been used to prepare this mixture--the dried blend method (by ball milling etc.) of powder and polymerization conductive polymers in the presence of sooty.
By chemical oxidising polymerisation compositing conducting polymkeric substance and the method for preparing matrix material by conductive polymers and other electroconductibility inorganic materials is the obviously relative simple technology that is used to form electrode, discloses many examples of this technology in recent years.Yet its reproducibility is poor, and therefore, this mixture does not have practical use.Equally, when attempting to enlarge in proportion and developing reproducible method, the problem that need overcome is huge.
For example, the open No.2002-265598 of Japanese Patent discloses and has used the matrix material of organic conductive oligopolymer and inorganic materials as electrode materials.Yet in this case, expectability organic conductive oligopolymer does not have high conductivity, so inorganic materials requires to have very high specific conductivity so that reduce internal resistance.
In addition, as the similar situation of using conducting polymer materials, a kind of in porous carbonaceous material the method (Japanese Patent open No.2001-210557) of polymerization conductive polymers can not produce conductive polymers with high conductivity, but caused the increase of electrical condenser internal resistance.
As mentioned above, the example of the electrical condenser of known so far a large amount of use electrochemical activity conductive polymers or inorganic oxide.Yet the use of inorganic materials causes the problem relevant for production cost, and the use of conductive polymers comprises that specific conductivity control, granularity are controlled and the difficulty of reproducibility, causes electrical condenser can not show enough performances.
Therefore the objective of the invention is to create a kind of carbon material/conductive polymers mixture, it can make and show good performance number with reproducible mode, during in particular for the manufacturing of ultracapacitor.
Summary of the invention
The most surprisingly, if conductive polymers is provided and conductive polymer in colloidal form is mixed with carbon material, reproducibly make (intrinsic) conductive polymers and mixture such as the carbon material of carbon black, graphite, carbon nanotube or soccerballene with colloidal state.
Thereby first aspect the present invention relates to a kind ofly can form coating and comprise conductive polymer in colloidal form and the composition of the mixture of carbon.
Second aspect, the present invention relates to a kind of method for compositions that is used to make according to first aspect, described method comprises conductive polymers and carbon and optional additive is dispersed in the liquid dispersion medium and drying liquid dispersion randomly after the coating on base material.
The third aspect the present invention relates to a kind of matrix material, comprises the composition for coating form on the base material that obtains according to the composition of first aspect or the method by second aspect.
Fourth aspect the present invention relates to a kind of electric or electronic products, and it comprises according to the composition of first aspect or according to the matrix material of the third aspect.
The preferred embodiments of the invention openly in the dependent claims.
Preferably, carbon material of the present invention is selected from graphite, carbon black, nanotube and soccerballene.Carbon material of the present invention is also referred to as ' based on the material of carbon ' because they needn't only be made up of chemical element carbon, but also can comprise other element such as hydrogen, oxygen, nitrogen and sulphur.For example, carbon black can comprise the N of H, 0.1-0.7% of 0.3-1.3% and the S of 0-0.7%.According to the mode of making, for oven process or thermal black, the sooty oxygen level can reach 0-1.5%, can paramountly reach 5% for gas phase and thermally oxidized black, can paramountly reach 15% for the carbon black with the oxygen aftertreatment.In addition, can there be fused aromatic compounds on the surface of material.
Term " (intrinsic) conductive polymers " (ICP) is meant and has (many)-conjugated pi electron system the organic polymer of (for example two keys, aromatic series or hetero-aromatic ring or triple bond).They can exist with various states, describe by different empirical formula for every kind, and by () chemical reaction such as oxidation, reduction, acid/alkali reaction or complexing, reversibly conversion mutually basically usually.These reactions are also referred to as " doping " or " compensation " in the literature sometimes, maybe can think to be similar to " charging " and " discharge " of electrochemical method in the battery.At least a may situation be the very good electric conductor of electricity, for example has the specific conductivity greater than 1S/cm (pure state), so just can speak of intrinsic conducting polymer.The ICP of these forms is commonly referred to be radical cation or negatively charged ion polysalt.Up to now, good summary with chemical structure synthetic (intrinsic) conductive polymers that is suitable for the object of the invention can be at SyntheticMetals, Issues17,18and19 (1987) and Synthetic Metals (in the printing) find among the Proceedings of theICSM ' 88 (Santa F é).
The chemical property of conductive polymers of the present invention is not particularly limited, their example comprises polyaniline, polyaniline derivative, Polythiophene, polythiofuran derivative, polypyrrole, the polypyrrole derivative, poly-benzo-thiophene, poly-benzo-thiophene derivative, p-poly-phenyl, the p-poly-phenyl derivative, polyacetylene, the polyacetylene derivative, polydiacetylene, the polydiacetylene derivative, p-phenylene vinylene (polyparaphenylenevinylene), poly (p phenylene vinylene) derivatives, poly-naphthalene and poly-naphthalene derivatives, polyisothianaphthene (PITN), poly-heteroarylidene vinylidene (polyheteroarylenvinylene, ParV) (wherein heteroarylidene can be a thiophene for example, furans or pyrroles), polyphenylene sulfide (PPS), poly-perinaphthene (PPN), poly-phthalocyanine (PPhc) etc. and their derivative (for example the monomer that is replaced by side chain or side group forms), their multipolymer and their physical mixture.The method that is used for the polymerization conductive polymers is not particularly limited, and the available method comprises electrolytic oxidation polymerization, chemical oxidising polymerisation and catalyzed polymerization.The polymkeric substance itself that obtains by the polymerization process of mentioning is a neutral, and itself is non-conductive.Therefore, polymkeric substance is carried out p-doping or n-doping, thereby be transformed into conductive polymers.Be used for adulterated material and be not particularly limited, use can be accepted the material of electron pair usually, such as Lewis acid.Example comprises hydrochloric acid, sulfuric acid, organic sulfonic acid derivative such as p-sulfonic acid, polystyrolsulfon acid, alkyl benzene sulphonate (ABS), camphorsulfonic acid, alkylsulphonic acid, sulphosalicylic acid (sulfosalycilic acid) etc., iron(ic) chloride, cupric chloride and ferric sulfate.
Being provided at which kind of form based on the material of carbon is not critical in the enforcement of the present invention.Conductive polymer in colloidal form can with the form of (do or wet) powdered form, porous-film or matrix material or the material mixing that also provides based on carbon with the form of colloid preparation.Carbon can carry out pre-treatment (for example passing through ball milling), is pre-dispersed in water, organic solvent or the other medium, perhaps forms fiber, nanofiber, film or porous shape or membranous form.Can add conductive polymer in colloidal form to the material based on carbon, vice versa.
For example, carbon dust can be added in the colloidal dispersion of conductive polymers, scheme can apply the carbon back material by the colloidal dispersion that uses conductive polymers, thereby add the conductive polymers dispersion to carbon as an alternative.
Can make the colloidal conductive polymers in various mode, it is known and prior art substantially.For example referring to EP-A-0 329 768 and German patent application No.10 2,004 003 784.According to the present invention, think that the polymer particle that has less than the 500mm size is a colloid.Can be by scanning or transmission electron microscope, perhaps by using laser doppler technique to measure the size of particle.The another kind of method of making polymkeric substance is to carry out its polymerization under the surfactant situation existing, and makes resulting polymers be retained in the reaction medium with colloidal state.In order to be used as colloidal dispersion subsequently, will be by ion-exchange and/or membrane filtration purifying dispersion.
As an alternative the method for scheme be by the polymerization conductive polymers, then neutralization (compensation) thus non-conductive form and obtain the method for meticulous colloidal dispersion (being commonly referred to be " solution ") extremely with solvent.Can the colloidal dispersion of the non-conductive form of this conductive polymers with based on the material mixing of carbon, and can by add suitable material (" doping agent ") as Broenstedt acid, Lewis acid or oxygenant (as iodine, FeCl
3Or other) make the mixture that the obtains conduction that becomes.
Another optimal way is the polymerization conductive polymers, makes it precipitate from reaction medium, can filter, wash then and disperse.EP-B-0 329 768 has described this polymerization methods.Can be by the polymkeric substance that this method obtains from Ormecon GmbH, Germany buys.Specifically capable referring to the embodiment 1 of EP-B-0 329 768 and specification sheets the 8th page, 7-22.
Most preferred mode is to use the conductive polymers dispersion of German patent application No.10 2,004 003 784 descriptions of submitting to as on January 23rd, 2004.Specifically referring to wherein claim 6 and embodiment 1 to 8.The method of German patent application No.10 2,004 003 784 makes can prepare the colloid conductive polymers that has greater than the 100S/cm specific conductivity, and described electric conductivity is favourable for many application.In this method,, make primary particle have diameter, and the powder that obtains is dispersible less than 500nm usually at first according to the polymerization process polymerization conductive polymers of EP-B-0 329 768.According to an embodiment, disperse this powder in first dispersion steps then, succeeded by the regulating step and second dispersion steps.At last, the preparation dispersion is so that colloidal dispersion satisfies following various processing and application demand (viscosity, stability, time of drying and temperature etc.).German patent application No.10 2,004 003 784 has described the dispersion technology that is fit to, and comprises the use of for example using general milling machine, planetary ball mill, homogenizer or ultra-sonic dispersion equipment.
Can be after second dispersion steps (it causes the high viscosity pasty state usually) or after final preparation steps (it causes less viscous liquid usually) with conductive polymers and material mixing based on carbon.
Being preferred for the material based on carbon of the present invention is carbon nanotube, nanofiber, soccerballene, carbon black etc.These materials are easy to reunite and be not easy steeping liq or colloidal dispersion usually.
Because help the use of back carbon/conductive polymers mixture, the colloid conductive polymers should arrive the surface based on the material of carbon.Therefore, preferably provide material based on carbon with the form of highly porous structure, fine powder or colloidal dispersion.If the use dried powder, these powder of preferred pretreatment for example pass through ball milling.Can in planetary-type grinding machine or satellite-type ball mill, carry out ball milling.
Also can in the presence of the conductive polymer in colloidal form dispersion, disperse material, for example in ball mill based on carbon.
Also preferably in water or organic solvent (be with or without and use tensio-active agent (surface active agents), tensio-active agent (tenside) and other material), make dispersion based on the material of carbon.Can in the dispersion machinery of ball mill, ball mill, ultra-sonic dispersion equipment, 2 or 3 roller mills or other the state of the art, make this dispersion.
In order to obtain the high dispersing state, can carry out dispersion process by using general milling machine, planetary ball mill, homogenizer or ultra-sonic dispersion equipment.Wherein use planetary ball mill, preferably stirred at least 30 minutes.Long-time stirring is relevant with technological problems, such as the rising of solvent temperature.Therefore, under stirring, need cooling greater than 1 hour situation.
The preferred paste of producing based on the material of carbon, its can mix with the conductive polymers colloid and need not further dilute and prepare or can be before further diluting and preparing, among or mix with the conductive polymers colloid afterwards.
Can change the relation between carbon and the conductive polymers widely.For example, conductive polymers can be the scope of 1: 50～50: 1 or 1: 50～50: 2 to the weight ratio of carbon.
The final mixture of carbon and conductive polymers can comprise additive image surface promoting agent or stablizer and other material.
Only be subjected to the restriction of validity, price and the final suitability of using based on the selection of the material of carbon with colloid conductive polymers phase blended.Different materials based on carbon can be favourable in application-specific as the mixture of active black and graphitized carbon black.
The situation of conductive polymers is also like this.Though it is not critical that methods and applications of the present invention are required, validity and price can limit the selection of conductive polymers.Usually, all conductive polymerss described above all are available in practice of the present invention.The preferably multipolymer and the derivative of polyaniline and Polythiophene and their derivative, particularly polyaniline and it.
Carbon/conductive polymers according to the present invention can be used for conductor, energy accumulator, transmitter, switch, electrical condenser (condenser), electrical condenser (capacitor) and ultracapacitor, double layer capacitor and redox electrical condenser.
For carbon/conductive polymer applications according to the present invention is stored in () energy, for example be used in the electrical condenser preferred active black and polyaniline or Polythiophene and their derivative.Graphitized carbon black also can be used as annexing ingredient.
Advantageous applications according to composition of the present invention is the electrode materials that is used as large value capacitor.This type of electrical condenser so-called " ultracapacitor " or " double layer capacitor " (" DLC "), (with reference to some the concrete mechanism in this type of electrical condenser particular form) are also referred to as " redox electrical condenser " sometimes.Below, this application is meant " DLC ".
A preferred embodiment of the present invention is to make the material that is used for the large value capacitor electrode, comprises porous carbonaceous material or valve metal, has at least an electrode to be formed by the composition that comprises electroactive substance.Surprisingly, by carbonaceous material is combined with conductive polymer in colloidal form, can bonding consumingly porous carbonaceous material and form stable electrode.And in the prior art, nonconducting organic binder bond is with the tackiness agent that acts on bonding porous carbonaceous material, and electro-conductive material according to the present invention uses tackiness agent to form electrode becomes possibility.In addition, can fully guarantee to be used for the bounding force of bonding collecting board by the control particle diameter.In addition, performance data shows the good structure of electrical double layer, and material according to the invention can easily be flooded electrolyte solution.
Though for scope of the present invention is not critical, usually, in order to be used as electrode materials, mixture comprises (activity) carbon than conductive polymers higher amount.
The specific conductivity of conductive polymers helps the minimizing of electrical condenser equivalent series resistance especially.Though electrode with regard to the electrical condenser that is used to use porous carbonaceous material, it is conventional operation that interpolation acetylene black etc. gives material as specific conductivity, but material according to the invention is characterised in that, by the conductive polymers with 100S/cm or bigger specific conductivity is provided, conductive polymers self has the effect that gives material as specific conductivity, makes that not needing to add especially specific conductivity gives material.Do not give material because do not need to add specific conductivity, so can enlarge the capacity of actual product.In this case, the specific conductivity of conductive polymers is 100S/cm at least, preferred 200S/cm or more than, more preferably 500S/cm or more than.Preferred specific conductivity is high as far as possible, because it has a significant impact the internal resistance of the electrical condenser that will make.
In another embodiment of the invention, conductive polymers is dispersed in water or the organic solvent.Especially, have ready conditions that can be respectively applied for ionogen in the electrical condenser be the situation of water and be used for the situation that ionogen is an organic solvent for the composition of regulation.Especially when electrolyte is water, use the conductive polymers that is dispersed in the organic solvent to help the stability of electrode.
In another embodiment of the present invention, be provided for the electrod composition of electrical condenser, wherein the conductive polymers dispersed elements comprise the solid ingredient that is no more than 20wt% concentration.Particularly when forming electrode, the concentration of solid ingredient influences productivity and cost greatly.Yet the solid ingredient in the conductive polymers dispersed elements also influences the stability of dispersion.Therefore, when considering production cost, the concentration of solid ingredient is no more than 20wt%, and when considering dispersion stable simultaneously, the concentration of solid ingredient is not more than 10wt%, preferably is not more than 5wt%.
In another embodiment of the present invention, preferably concentrate on the specific surface area of porous carbonaceous material.Has the 100m of being not less than by use
2/ g, preferred 500m
2/ g, more preferably 1000m
2The carbonaceous material of/g specific surface area can obtain the DLC of enough capacity.This porous carbonaceous material is dispersed in the dispersed elements of conductive polymers.
Can change the amount of the porous carbonaceous material of use widely.With respect to the weight of solid polyaniline, need add the porous carbonaceous material of 5wt% amount at least.
The charging and discharging speed of addition and electrical condenser is closely related.Under the situation of rapid charge electric discharge device, wish to add porous carbonaceous material relatively largely, under the situation of charging and discharging at a slow speed, wish to add conductive polymers relatively largely.Thereby, according to the present invention, be enough to control addition according to the device demand.In order to obtain to have at least electrical condenser, with regard to the amount of solid ingredient, need to add the conductive polymers that is not less than 5wt% greater than the condenser capacity of only using porous carbonaceous material.In order to obtain enough redox properties, with regard to the amount of solid ingredient, need to add the conductive polymers that preferably is not less than 10wt%.
In another embodiment of the present invention, material is used to the electrode of DLC, and described electrode is arranged opposite to each other, and arranges spacer between electrode, and wherein two electrodes are all by forming with a kind of conductive polymers.Consider their productivity, this structure has the advantage that very cheap device is provided.
In another embodiment of the present invention, material is used to the electrode of DLC, and the composition that wherein is used for forming two electrodes comprises various different conductive polymerss, and described two electrodes are arranged opposite to each other, and arrange spacer between electrode.This is based on following consideration: many organic conductive polymkeric substance show different activities under positive voltage and under negative voltage.In other words, have a kind of method of using conducting polymer materials to obtain the large vol device, when sweep voltage, conducting polymer materials shows the highest electroactive.
In another embodiment of the present invention, described material is used for the electrode of DLC, and wherein one of two electrodes comprise porous carbonaceous material, and another comprises according to porous carbonaceous material/conducting polymer composite material of the present invention.This structure has shown astonishing large vol.
In another embodiment of the present invention, described material is used for the electrode of DLC, and wherein one of two electrodes comprise metal oxide, and another comprises according to porous carbonaceous material of the present invention/conductive polymers mixture.This being configured in obtains under the jumbo situation effective especially by the redox characteristic that utilizes metal oxide electrode.The example of special metal oxide electrode material of wishing is ruthenium oxide and Indium sesquioxide.
In addition, when the inorganic materials among the present invention/conducting polymer composite material bodily form film forming or other layered product, as required, can add stablizer, photostabilizer, filler, tackiness agent, specific conductivity and give agent etc.
Using carbon/colloid conductive polymers mixture in DLC is quite wonderful as the effect of electrode materials.With by being used in the presence of (activity) sooty of DLC or this electrical condenser of polymerization conductive polymers manufacturing on this carbon blacksurface is compared, use electrical condenser to show better character significantly according to mixture manufacturing of the present invention.Yet, it should be noted that scope of the present invention is not subjected to the restriction of the specific nature of DLC constructed in accordance.In other words, can show that the DLC of lower-performance is also in limit of consideration of the present invention.
For example, capacity can be from greater than 50 to being far longer than 200F/g, and for example, power density can be from about 1,000 to several 1,000W/kg, for example, energy density from about 10 to being far longer than 100WH/kg.
Shown in Fig. 6 and Figure 11 (Ragon figure), this feature is arranged so that DLC according to the present invention has exceeded present power and the accessible scope of energy density, is higher than DLC (ultracapacitor) significantly and even is higher than the lithium ion battery of present prior art.
Some reasons of this surprised effect may be that (a) no longer needs tackiness agent or film for additive (in order to form the bonded-electrode material layer on the metal collector surface), (b) lower internal resistance and (c) the additional possibility of redox reaction, all these have increased electrolytical wetting and energy density (electric charge/weight) on accessible surface (can be used for electric charge carrier and their exchange), the electrode materials together, but do not plan to explain by these and limit.
Embodiment
Embodiment
Embodiment 1: the preparation of porous carbonaceous material/conducting polymer composite material electrode
The cocoanut active charcoal (end activation still) that 18g is ground is dispersed in (ORMECON 7301-026-002 in the conductive polymers dispersion of 90.9g, the dimethylbenzene dispersion of conductive polyaniline, solid ingredient: 2.2%), stirred the mixture 60 minutes by planetary ball mill.Further the dimethylbenzene that adds 57.3g stirred the mixture 30 minutes by stirring motor to porous carbonaceous material/conductive polymers slurry, with preparation porous carbonaceous material/conductive polymers dispersion.
The electrode that is used for electrical condenser need be fit to the collecting board of the electrolytic solution that electrical condenser uses.In this embodiment, when using aqueous sulfuric acid (1 mol) as electrolytic solution, the platinum plate is used for electrode, and when using propylene carbonate as electrolytic solution, aluminium is used for electrode.When platinum is used for the collecting board of true capacitor electrode, at first use the surface of file blade coating platinum plate, use the quantitative porous carbonaceous material/conductive polymers dispersion of preparation as mentioned above to apply then.Then, make the platinum plate of coating be in 100 ℃ the high-temperature cabinet 1 hour, fully to remove organic solvent.The electrode that forms is thus carried out the balance (weighing) of electrode active material, directly be used as the electrode of electrical condenser.
When the propylene carbonate solution that uses 1mol/l Tetrafluoroboric acid Tetrylammonium as based on the electrolytic solution of organic solvent the time, aluminium sheet is as collecting board.With use the platinum plate as the situation of collecting board under the same method, scrape the aluminising collecting board and use quantitative porous carbonaceous material/conductive polymers dispersion to apply by file.Afterwards, carried out drying 24 hours at 100 ℃, fully to remove moisture.
The component of dispersion that is used to form porous carbonaceous material/conducting polymer composite material electrode is shown in following table 1.
Table 1
| Conductive polymers | Dispersion medium | Specific surface area (the m of gac 2/g) | Solid ingredient ratio C: | |
| Experiment | ||||
| 1 | Polyaniline | Dimethylbenzene | 1100 | 9∶1 |
| |
Polyaniline | Dimethylbenzene | 1100 | 8∶2 |
| Experiment 3 | Polyaniline | Dimethylbenzene | 1100 | 1∶9 |
| Experiment 4 | Polyaniline | Dimethylbenzene | 1600 | 9∶1 |
| |
Polyaniline | Dimethylbenzene | 1600 | 8∶2 |
| Experiment 6 | Polyaniline | Dimethylbenzene | 1600 | 1∶9 |
| Experiment 7 | Polyaniline | Water | 1600 | 8∶2 |
| Experiment 8 | PEDOT | Water | 1600 | 8∶2 |
Embodiment 2: the production of capacitor unit
The disk that becomes to have the 1cm diameter with each battery lead plate blank of its tight electrodes in contact active substance that has, to prepare two electrodes as preparation among the embodiment 1.Glass fibre filter is cut into the circle with 1.5cm diameter, and as spacer.In addition, under the aqueous systems situation, the aqueous sulfuric acid of 1M is used as electrolytic solution.Under the situation of organic solvent system, the Tetrafluoroboric acid Tetrylammonium propylene carbonate solution of 1M is used as electrolytic solution.
The evaluation of capacitor specific characteristics
Surveying instrument: use can be from Hewlett-Packard Development Company, the internal resistance that the YHP4192A electric impedance analyzer that L.P. obtains is measured each capacitor unit.Use can be from TOYO SYSTEM, and the TOYO system TOSCAT-3100U that Co.LTD obtains carries out the measurement of charging and discharging test.
The charging and discharging test-results of using the electrical condenser of electrode active material shown in the EXPERIMENTAL EXAMPLE 1 is shown in the embodiment in the following table 2.
Table 2
| Test number | Electrode active material | Dispersion | Charge rate (mA/cm 2) | Charging capacity (F/g) | Discharge rate (mA/cm 2) | Loading capacity (F/g) |
| 1 | |
|
10 | 250 | 10 | 250 |
| 2 | |
|
5 | 240 | 5 | 240 |
| 3 | |
|
1 | 220 | 1 | 220 |
| 4 | |
|
10 | 250 | 10 | 250 |
| 5 | |
|
5 | 220 | 5 | 220 |
| 6 | |
|
1 | 170 | 1 | 170 |
| 7 | |
|
10 | 90 | 10 | 90 |
| 8 | |
|
5 | 100 | 5 | 100 |
| 9 | |
|
1 | 150 | 1 | 150 |
| 10 | Experiment 4 | |
10 | 40 | 10 | 40 |
| 11 | Experiment 4 | |
5 | 170 | 5 | 170 |
| 12 | Experiment 4 | |
1 | 170 | 1 | 170 |
| 13 | |
|
10 | 140 | 10 | 140 |
| 14 | |
|
1 | 200 | 1 | 200 |
The result that internal resistance is estimated as depicted in figs. 1 and 2.
Use capacitor unit to measure, this capacitor unit is by using electrode and using the sulphuric acid soln of 1M to form as electrolytic solution, and wherein said electrode uses the dispersed elements of experiment 2 and experiment 5.
Fig. 1 has shown to use to have 1600m
2The internal resistance of the electrical condenser of the porous carbonaceous material of/g specific surface area (impedance characteristic).
Fig. 2 has shown to use to have 1100m
2The internal resistance of the electrical condenser of the porous carbonaceous material of/g specific surface area (impedance characteristic).
The comparative example
Preparation comprises 60wt% activated carbon (about 1600cm
2The specific surface area of/g), 30wt% carbon black and 10wt% are as the mixture of the electrode materials of the tetrafluoroethylene of tackiness agent.Add methyl alcohol in this mixture, be used to form film.Use the roll-in method to prepare electrode slice (wide 10mm, long 10mm, thick 3mm).Dry this sheet under 250 ℃ overwise envrionment conditions.
Use then with the foregoing description 2 in identical method carry out charging and discharging and test.In the case, charging capacity only is about 4.7F/g.
Embodiment 3
1) reagent and equipment:
BELLFINE AP is produced by KABEBO LTD, as absorbent charcoal material.
D1005W (water dispersion of polyaniline) and 7201-026-001 (the dimethylbenzene dispersion of polyaniline) can be from Ormecon GmbH, Ammersbek, and Germany obtains, as conductive polymer in colloidal form.
(TOYO SYSTEM, CO. LTD) carry out the charging and discharging test by using the TOCAT-3100U battery tester.Use 4192A LF electric impedance analyzer (HEWLETTPACKARD) to measure impedance behavior.
2) preparation of conductive polymers and Mixture of Activated Carbon:
By using following step to prepare mixture.Use the satellite-type ball mill with the gac of 8.0g and the ORMECON 7201-026-001 of 90.9g (solid: 2.20%) mixed 60 minutes.This mixture is as electrode materials.This material coating by coating 200 μ m on aluminium sheet is made electrode film.Dry this wet film under 100 ℃ envrionment conditions.
The result:
1: from the composition of organic (dimethylbenzene) polyaniline dispersion (7201-026-001) acquisition
The film that use contains 7201-026-001 and BELLFINE AP mixture carries out the charging and discharging test.At 0.5mA/cm
2, 1mA/cm
2And 5mA/cm
2Measure the charging and discharging performance.Initial capacity under these conditions is listed in the table 3.
Table 3: based on the initial capacity of the electrical condenser of ICP.
| Current density (mA/cm 2) | Capacity (F/g) | Power density (W/kg) | Energy density (Wh/kg) |
| 0.5 | 254.9 | 1090 | 141.6 |
| 1.0 | 237.4 | 1805 | 131.9 |
| 5.0 | 211.3 | 5076 | 117.4 |
Power density and energy density are all good.This capacity is greater than the capacitor volume of only being made by BELLFINE carbon.For ' electrical condenser that BELLFINE ' is only arranged, capacity only are about 30F/g.The result of round-robin test is presented among Fig. 3, Fig. 4 and Fig. 5.
Fig. 3 has shown that use comprises the propylene carbonate ionogen of 0.01M Tetrafluoroboric acid Tetrylammonium, the result of capacitor cycle test under the voltage of 0.5mA current density and 2.0V.
Fig. 4 has shown that use comprises the propylene carbonate ionogen of 0.01M Tetrafluoroboric acid Tetrylammonium, the result of capacitor cycle test under the voltage of 1.0mA current density and 2.0V.
Fig. 5 has shown that use comprises the propylene carbonate ionogen of 0.01M Tetrafluoroboric acid Tetrylammonium, the result of capacitor cycle test under the voltage of 5.0mA current density and 2.0V.
After 4000 round-robin tests, electric capacity reduces to about 1/3 of initial value.Electric capacity after 4000 circulations is listed in the table 4.
Table 4: based on the capacitor volume of ICP, after 4000 circulations
| Current density (mA/cm2) | Capacity (F/g) | Power density (W/kg) | Energy density (Wh/kg) |
| 0.5 | 74 | 1099 | 41.2 |
| 1.0 | 50 | 2051 | 27.9 |
| 5.0 | 73 | 5188 | 41.0 |
The Ragon figure of these round-robin test data as shown in Figure 6.As can be seen, the common height of the capacity ratio of the electrical condenser of evaluation.Specifically, energy density reduces along with the increase of cycle number.Yet, apparent, to compare with initial value, power density changes hardly.At 5mA/cm
2Under the situation of condition, after about 4500 circulations, the rapid variation of characteristic.
In order to understand resistive component, measured impedance characteristic.From 5Hz in the 13MHz scope, carry out the measurement of impedance.Yet, can not find out the interface interaction of ionic species in this frequency zones.At first, check resistance i component (icomponent) by Cole-Cole figure.Then, by the Cole-Cole figure of resistive component after relatively initial resistance component and 4000 circulates, make the change unanimity of each resistance.Under the situation of this electrical condenser, equivalent circuit description is as follows:
With regard to electrical condenser, R1 is a solution resistance, and it is connected with the electrode interface impedance, and R2 is the induced current resistance in reversible potential lower electrode process.This value is subjected to the influence of conductive polymers resistance.Cole-Cole figure as shown in Figure 7.
The value of R1 and R2 is listed in the table 5.
Table 5: use conductive polymers and Mixture of Activated Carbon resistance as the electrical condenser of electrode
| Resistance | 0.5mA/cm2 R1(Ω) | 0.5mA/cm2 R2(Ω) | 5.0mA/cm2 R1(Ω) | 5.0mA/cm2 R2(Ω) |
| Initially | 27 | 18 | 18 | 18 |
| 4000 circulations | 18 | 430 | 18 | 200 |
Above data show that though R1 does not change with two kinds of current densities, R2 is along with 4000 circulations change intensely.Can think that this change depends on the change of conductive polymers resistance, such as the elimination of doping agent, the oxidation of conductive polymers, the decomposition of polymkeric substance etc.
2. the polyaniline of water-dispersion (D1005W)
By utilizing the film on the A1 plate to carry out the charging and discharging test, this film is made by the mixture of D1005W and BELLFINE AP.At 0.5mA/cm
2, 1mA/cm
2And 5mA/cm
2Carry out the charging and discharging test.Initial capacity under these conditions is listed in the table 6.
Table 6: based on the initial capacity of the electrical condenser of ICP
| Current density (mA/cm 2) | Capacity (F/g) | Power density (W/kg) | Energy density (Wh/kg) |
| 0.5 | 185.1 | 1225 | 102.8 |
| 1.0 | 66.07 | 1549 | 36.7 |
| 5.0 | 106.7 | 12769 | 59.3 |
The energy density of using the D1005W electrical condenser is less than the energy density of using the 7201-026-001 electrical condenser.The result of round-robin test such as Fig. 8, Fig. 9 and shown in Figure 10.
Fig. 8 has shown that use comprises the propylene carbonate ionogen of 0.01M Tetrafluoroboric acid Tetrylammonium, the result of capacitor cycle test under the voltage of 0.5mA current density and 2.0V.
Fig. 9 has shown that use comprises the propylene carbonate ionogen of 0.01M Tetrafluoroboric acid Tetrylammonium, the result of capacitor cycle test under the voltage of 1.0mA current density and 2.0V.
Figure 10 has shown that use comprises the propylene carbonate ionogen of 0.01M Tetrafluoroboric acid Tetrylammonium, the result of capacitor cycle test under the voltage of 5.0mA current density and 2.0V.
At 1.0mA/cm
2Situation under, in round-robin test, do not observe changes in capacitance.Yet, at 5.0mA/cm
2Situation under, observe the quick minimizing of electric capacity at 1000 circulation times.Capacity data after 4000 circulations is listed in the table 7.
Capacitor volume after the table 7:4000 circulation based on ICP
| Current density (mA/cm 2) | Capacity (F/g) | Power density (W/kg) | Energy density (Wh/kg) |
| 0.5 | 55.1 | 1233 | 30.6 |
| 1.0 | 63.1 | 1311 | 35.1 |
| 5.0 | 19.4 | 10621 | 10.7 |
The Ragon figure of round-robin test data as shown in figure 11.
Find out clearly that from data energy density reduces along with the increase of cycle number.Yet, to compare with initial value, power density changes hardly.At 1.0mA/cm
2Current density under, power density and energy density are very stable for about 4000 circulations.At 5.0mA/cm
2Down, after about 1000 circulations, the rapid variation of power density.
In order to analyze resistive component, use electric impedance analyzer to carry out impedance measurement.The result of impedance measurement as shown in figure 12, it is to use electric conductive polymer and the Mixture of Activated Carbon Cole-Cole figure as the electrical condenser of electrode.
R1 and R2 value according to Cole-Cole figure are listed in the table 8.
Table 8: use conductive polymers and Mixture of Activated Carbon resistance as the electrical condenser of electrode.
| Resistance | 0.5mA/cm2 R1(Ω) | 0.5mA/cm2 R2(Ω) | 1.0mA/cm2 R1(Ω) | 1.0mA/cm2 R2(Ω) | 5.0mA/cm2 R1(Ω) | 5.0mA/cm2 R2(Ω) |
| Initially | 27 | 150 | 7.4 | 7.8 | 27 | 37 |
| 4000 circulations | 130 | 700 | 65 | 150 | 130 | 520 |
This R2 resistive component is greater than the R2 resistive component based on the electrical condenser of 7201-026-001.Without being limited by theory, think based on the electrical condenser of D1005W and can be owing to the difference of specific conductivity between D1005W and the 7201-026-001 based on the difference of R2 resistance between the electrical condenser of 7201-026-001.After 4000 circulations, the resistance of R1 and R2 all increases intensely.
[invention effect]
As mentioned above, the invention provides a kind of double-layer capacitor, wherein with the mutual positioned opposite of a pair of polarizable electrode, and arrange spacer between electrode, wherein each electrode comprises the solid electrolyte that is included in the conducting polymer in the active carbon layer separately. Especially, by increasing particle diameter and the electrical conductivity of conducting polymer, can obtain to have low internal resistance and jumbo double-layer capacitor.
Claims (25)
1, a kind ofly can form coating and comprise conductive polymer in colloidal form and the composition of the mixture of carbon.
2, according to the composition of claim 1, wherein conductive polymers is selected from the polymkeric substance of aniline, thiophene, pyrroles and substitutive derivative thereof.
3,, wherein there are two or more different conductive polymerss according to the composition of claim 1 or claim 2.
4, according to the composition of aforementioned arbitrary claim, wherein carbon has according to the measurement of BET method greater than 100m
2The specific surface area of/g.
5, according to the composition of aforementioned arbitrary claim, wherein carbon is selected from graphite, carbon black, nanotube and soccerballene.
6, according to the composition of claim 5, wherein carbon is active black.
7, according to the composition of claim 6, wherein active black has greater than 750m
2The specific surface area of/g.
8, according to the composition of aforementioned arbitrary claim, wherein the mean particle size of conductive polymers (number average) is less than 500nm.
9, according to the composition of aforementioned arbitrary claim, wherein the specific conductivity of conductive polymers is greater than 10
-5S/cm.
10, according to the composition of claim 9, wherein specific conductivity is greater than 10S/cm.
11, according to the composition of claim 10, wherein specific conductivity is greater than 100S/cm.
12, according to the composition of aforementioned arbitrary claim, wherein the weight ratio of conductive polymers and carbon is 1: 50～50: 1.
13, according to the composition of aforementioned arbitrary claim, the additive that further comprises other non-vaporising of the liquid dispersion medium of 40～99.5wt% concentration and 0～10wt% concentration, wherein dispersion medium liquid can evaporate under envrionment conditions, the conductive polymers and the carbon component concentrations that exist are 0.5～60wt%, and all weight percent number averages are based on Overall Group's compound.
14, according to the composition of claim 13, wherein liquid dispersion medium comprises water and/or organic solvent.
15, a kind of method for compositions that is used to make according to aforementioned arbitrary claim comprises conductive polymers and carbon and optional additive are dispersed in randomly drying liquid dispersion after being coated on the base material of liquid dispersion medium neutralization.
16, the method for claim 15, wherein conductive polymers is dispersed in first liquid and carbon is dispersed in separately in second liquid, described liquid is identical or different, subsequently each dispersion is mixed, before dispersive step respectively, among or add optional additive afterwards.
17, the method for claim 15, wherein conductive polymers is dispersed in the liquid and is not having to grind carbon under the situation of liquid separately, subsequently this dry grinding carbon is added in the liquid colloidal dispersion of conductive polymers and disperses therein.
18, a kind of matrix material, comprise according to claim 1～14 each composition or the composition that obtains by each method of claim 15～17 for coating form on the base material.
19, the matrix material of claim 18, wherein base material is selected from metal, semi-conductor, plastics, pottery and woodwork.
20, a kind of electric or electronic products, comprise according to claim 1～14 each composition or according to the matrix material of claim 18 or claim 19.
21, the goods of claim 20, wherein said goods are selected from conductor, energy accumulator, transmitter, switch, electrical condenser (condenser), electrical condenser (capacitor) and ultracapacitor, double layer capacitor and redox electrical condenser.
22, the goods of claim 21, described goods are electrical condensers, this electrical condenser comprises ionogen and electrode pair, described electrode pair has the spacer that places therebetween, wherein have at least an electrode comprise according to claim 1～14 each composition or according to the matrix material of claim 18 or claim 19.
23, the electrical condenser of claim 22, wherein two electrodes all comprise according to claim 1～14 each composition or according to the matrix material of claim 18 or claim 19.
24, the electrical condenser of claim 22, one of them electrode comprise according to claim 1～14 each composition or according to the matrix material of claim 17 or claim 18, another electrode is conventional electrode for capacitors.
25, the electrical condenser of claim 24, wherein another electrode comprises using and comprises intrinsic conducting polymer but the current collector of carbon-free composition coating.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004013634A DE102004013634A1 (en) | 2004-03-18 | 2004-03-18 | Composition useful for forming a coating useful in electrical double layer capacitors to form electronic apparatus and power supplies comprises a mixture of a conductive polymer in colloidal form and carbon |
| DE102004013634.3 | 2004-03-18 | ||
| DE102004014021.9 | 2004-03-19 | ||
| DE102004014021 | 2004-03-19 | ||
| US56695404P | 2004-04-29 | 2004-04-29 | |
| US60/566,954 | 2004-04-29 | ||
| PCT/EP2005/002889 WO2005090446A1 (en) | 2004-03-18 | 2005-03-17 | A composition comprising a conductive polymer in colloidal form and carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1965018A true CN1965018A (en) | 2007-05-16 |
| CN1965018B CN1965018B (en) | 2011-03-16 |
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| CN2005800083802A Active CN1965018B (en) | 2004-03-18 | 2005-03-17 | composition comprising colloidal conductive polymer and carbon |
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|---|---|
| CN (1) | CN1965018B (en) |
| DE (1) | DE102004013634A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101874274A (en) * | 2007-11-27 | 2010-10-27 | 玛丽亚·斯特罗姆 | Composite materials including an intrinsically conducting polymer, and methods and devices |
| CN101894680A (en) * | 2010-06-23 | 2010-11-24 | 万裕三信电子(东莞)有限公司 | Electrode plate for electric double layer capacitor and preparation method of electric double layer capacitor |
| CN104387957A (en) * | 2014-11-13 | 2015-03-04 | 山东华亚环保科技有限公司 | Antistatic coating and preparation method thereof |
| TWI611445B (en) * | 2015-09-01 | 2018-01-11 | Hua Qing Xiu | Graphene applied to the contact surface of keyboard keys and its structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007018540A1 (en) * | 2007-04-19 | 2008-10-30 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Electrically conductive composition for use as transparent or non-transparent conductive coating for resistance heating elements e.g. for heating disks, comprises electrically conductive polymer, carbon nanotubes and baytron |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3733404B2 (en) * | 2001-05-22 | 2006-01-11 | 富士重工業株式会社 | Positive electrode for lithium secondary battery and lithium secondary battery |
-
2004
- 2004-03-18 DE DE102004013634A patent/DE102004013634A1/en not_active Withdrawn
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101874274A (en) * | 2007-11-27 | 2010-10-27 | 玛丽亚·斯特罗姆 | Composite materials including an intrinsically conducting polymer, and methods and devices |
| US8920971B2 (en) | 2007-11-27 | 2014-12-30 | Maria Strömme | Composite materials including an intrinsically conducting polymer, and methods and devices |
| CN101894680A (en) * | 2010-06-23 | 2010-11-24 | 万裕三信电子(东莞)有限公司 | Electrode plate for electric double layer capacitor and preparation method of electric double layer capacitor |
| CN104387957A (en) * | 2014-11-13 | 2015-03-04 | 山东华亚环保科技有限公司 | Antistatic coating and preparation method thereof |
| TWI611445B (en) * | 2015-09-01 | 2018-01-11 | Hua Qing Xiu | Graphene applied to the contact surface of keyboard keys and its structure |
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| DE102004013634A1 (en) | 2005-10-06 |
| CN1965018B (en) | 2011-03-16 |
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