CN101174510A - Conductive dope used for producing super capacitor and its producing method - Google Patents
Conductive dope used for producing super capacitor and its producing method Download PDFInfo
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- CN101174510A CN101174510A CNA2007101656380A CN200710165638A CN101174510A CN 101174510 A CN101174510 A CN 101174510A CN A2007101656380 A CNA2007101656380 A CN A2007101656380A CN 200710165638 A CN200710165638 A CN 200710165638A CN 101174510 A CN101174510 A CN 101174510A
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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 discloses conductive coating used for preparing super capacitor and the preparation method thereof, which comprises porous carbon material, conductive agent, cementing agent and solvent. The components have the weight percentage that the porous carbon material is 18 to 30 percent, the conductive agent is 0.1 to 10 percent, the cementing agent is 1 to 5 percent, and the solvent is 30 to 80 percent, and the total weight is 100; the pH value of the prepared conductive coating is 6-12, the solid content range is 10-55 percent, and the viscosity range is 10-1000 cps. The coating of the invention has excellent binding property with current collector, and has good compatibility with conductive basement film. After secondary solidification, the conductive coating has excellent thermal stability and electrical inertia; and is not influenced by electrolyte; thereby providing a capacitor electrode with low internal resistance, and long service life.
Description
One, technical field
The present invention relates to a kind of electrically-conducting paint and preparation method thereof, more particularly relate to a kind of electrically-conducting paint of preparing ultracapacitor and preparation method thereof that is used to.
Two, technical background
The research and development novel energy is implemented to save energy and reduce the cost, and improving environmental quality is the important content of global energy development strategy.Ultracapacitor is that occur in recent years a kind of has high power, quick charge, the superpower energy storage device of long circulation life.It has the dual-use function of electric capacity and battery concurrently, and its functional density is far above common batteries, and it is a lot of soon to discharge and recharge speed than common batteries, and energy density is far above the common electrical electrolysis condenser, and its energy storage capacity is greater than ordinary capacitor.Compare with ordinary capacitor and battery, ultracapacitor has that volume is little, and capacity is big, and charging rate is fast, has extended cycle life discharge power height, working temperature wide (40 ℃-85 ℃), good reliability and advantage such as with low cost.Ultracapacitor is developing into a kind of novel, efficient, practical energy storage and fast charging and discharging equipment.Thereby, very application prospects is all arranged in fields such as the energy, communication, number, electronics, medical treatment, health, network, automobiles.
A complete ultracapacitor comprises bipolar electrode, electrolyte, collector, four parts of spacer.At present the electrode material of the ultracapacitor of research is mainly aspect four: carbon electrode material, metal oxide and hydrate electrode material thereof, conductive polymer electrodes material, and combination electrode material.The carbon electrode material specific surface is very big, and raw material is cheap, helps realizing industrialized production, but specific capacity is relatively low.The specific capacity of metal oxide and hydrate electrode material thereof is higher, but its expensive cost and the potential safety hazard that environment exists limited their industrially scalable.The operating voltage height of conductive polymer electrodes material, thus the ability of energy storage can be improved.But this class material expands after soaking in organic bath easily, causes poor stability.Combination electrode material adopts different material systems to form to electrode, can improve the energy density of its storage, but its cycle stability is poor.Collector is then normally selected for use electric conductivity good metal and graphite to wait to serve as.
The electrode material of ultracapacitor is the key factor of decision capacitor performance.The technology of preparing of electrode material directly influences the performance of electrode material.Therefore, research and development specific capacity electrode material big, that resistivity is little is the task of top priority.At present, aspects such as the bonding strength of most of electrode materials, thermal stability, corrosion resistance, electric inertia are all not really desirable, and adopt one-shot forming to make, and its internal resistance reaches littler than electric capacity greatly, and can not satisfy the large-scale production requirement.
For the large-scale production that makes electrode material for super capacitor becomes a reality, the preparation of electrode material and technology should break through and innovate to some extent.The electrode material for super capacitor manufacturing technology should be towards Heat stability is good, bonding strength height, corrosion resistance is strong, technology is simple and the direction that is suitable for large-scale production develops.
People such as Mitchell have introduced the electrode design method of two voltage capacitors in United States Patent (USP) 7227737.Electrode is by collector and layers of active electrodes, and promptly active carbon layer is formed.Between two electrodes barrier film is arranged, this structure is immersed in forms ultracapacitor in the electrolyte.The thickness difference of layers of active electrodes, thus cause dissymmetrical structure that different capacitances is arranged.When applied voltage during in this super capacitor, voltage just is distributed on the secondary single capacitor unevenly.Suitably select electrode layers thickness can allow voltage on secondary single capacitor, evenly distribute, thereby improve the limiting voltage of ultracapacitor.People such as clock have introduced impregnation process porous electrode and preparation method thereof in United States Patent (USP) 7147674.The porous electrode material comprises the sealed liquid impregnation process of active carbon, polymer and conductive carbon, and after the active electrode drying, gasket coating has just been sealed the micropore in active carbon and other porous materials, thereby has stoped hydrone and other impurity molecules to shift out.But the hole that gasket coating blow-by aperture is bigger.This pretreated active electrode material can be used for producing the electrode of super capacitor, and the hydrone that is sealed can not react with electrolyte, therefore can improve the limiting voltage of super capacitor.People such as Mitchell have introduced electrode dipping and bonding method in United States Patent (USP) 7102877.Two sides of porous basement membrane, are combined with collector then and are prepared into electrode by the support membrane double side support by conducting liquid dipping back, and this electrode can be used for store energy equipment.People such as Mitchell have introduced combination electrode and preparation method thereof in United States Patent (USP) 7090946.This combination electrode is made by the pressure compacting, is not in conjunction with preparation with binder.Collector is the aluminium foil preparation through surface active or the processing of other surface adhesion.By active carbon as the active electrode material film forming after, plasticate through two rollers, under heating, be pressed on the collector, thereby form electrode material, cut into electrode shape then.This electrode can be used to prepare energy storage devices such as double layer capacitor.People such as Mitchell have introduced a kind of electrode preparation method in United States Patent (USP) 6955684.On collector, be coated with electrically-conducting paint, solidify the ground floor electrically-conducting paint earlier, and then be coated with second layer coating and solidify it, thereby form electrode material.Used electrically-conducting paint is an active carbon, adds PVDF, and is polyamide-based, is dissolved in acetone, butanone, the N-methyl pyrrolidone equal solvent.People such as Bendale have introduced a kind of super capacitor preparation method in the U.S. 6813139.Earlier aluminium shell is swollen through heating, add electrode and two lids up and down.Fasten lid because of contraction when aluminum hull cools off, the aperture on lid adds electrolyte and makes super capacitor to sealing.People such as Nanjundiam are at United States Patent (USP) 6804108; 6643119; 6631074; With 6627252 in introduced electrode preparation method.All be coated with ground floor conductive adhesive (conductive adhesive) coating on the two sides of aluminium foil, after drying, at two-sided active electrode material (the active electrode material) coating of coating, be prepared into electrode material after drying again.Used electrically-conducting paint is water-soluble by active carbon, PVDF, acetone, methylcellulose, own propyl group diene fourth monomer etc.
People such as Zuckerbrod disclose a kind of electrode by utilizing adhesive that active carbon is mixed with powder of stainless steel to prepare in No. the 4448856th, United States Patent (USP).The density of each powder is limited to 25～450 μ m, with these powder coated on nickel wire line or sheet metal as current-collector, thereby make electrode.
The method of above-mentioned manufacturing active carbon or activated fibre electrode has been represented the various technologies that reduce the resistance between active carbon electrode material and the current-collector.
People such as Niu [" High Power Electrochemical Capacitors Based on CarbonNanotube Electrodes ", Applied Physics Letter, 70, pp.1480-1482 (1997)] preparation of carbon nanotube electrode has been proposed, wherein utilize the oxidation processes of nitric acid and replace the functional group of about 10% on the carbon nano tube surface.Compare with the electrode that does not have to handle, surface treated electrode shows more performance.Particularly, they do not use adhesive to improve resistance between the carbon nano-tube by exerting pressure simply, and can prepare this electrode simply.
People such as Ma [" Study of Electrochemical Capacitors Utilizing CarbonNanotube Electrodes ", Journal of Power Sources 84, pp.126-129 (1999)] utilize phenolic resins (PF) powder to prepare carbon nanotube electrode as adhesive.They have proposed to make the following technology of carbon nanotube electrode: the molded mixture of carbon nano-tube and PF powder prepares electrode (A); Heat treatment makes this molded mixture carbonization prepare electrode (B); Electrode is immersed in the hot mixt of the concentrated sulfuric acid and nitric acid, then washing and dry preparation electrode (C).According to results of comparative experiment, electrode (A) shows the highest internal resistance, and this is because adhesive makes the performance degradation of electrode.Therefore, must carry out carbonization technique.It is the highest utilizing the performance of the electrode (C) of carbonization and nitric acid treatment, and is second high with the performance of the electrode (B) of carbonization treatment only.
People such as An [" Supercapacitors Using Single-Walled Carbon NanotubeElectrodes; Advanced Materials; 13; pp.479-500 (2001)] are by exerting pressure to carbon nano-tube and the mixture as the poly-inclined to one side fluorine divinyl (PVDF) of adhesive, then carbonization and prepare carbon nanotube electrode.
Disclose the employing polytetrafluoroethylene in Chinese patent CN-1905100A number, vinylidene is an adhesive, uses the curtain coating coating process and prepares active carbon electrode material.This method has certain exploration to the preparation of electrode material.People such as Li Yongxi disclose the employing polytetrafluoroethylene in Chinese patent CN1317809A number, vinylidene, and phenolic resins, polyvinyl alcohol, carboxymethyl cellulose are the CNT (carbon nano-tube) electrode of adhesive.Tan Qiang waits the people to disclose in Chinese patent CN-1770344A number by force and adopts the electrode material of the composition of polytetrafluoroethylene or poly-inclined to one side tetrafluoroethene and N-methyl pyrrolidone as adhesive.Natural minerals and CNT (carbon nano-tube) compound super capacitor electrode material and preparation method have invented and with the preparation method of Ru/C nanometer combined electrode material in Zhejiang University; Chengdu Organic Chemistry Inst., Chinese Academy of Sciences has invented carbon nano-tube and has been used for electrode material for super capacitor; A kind of preparation method of layered cobalt aluminium bihydroxy composite metal oxide electrode material has invented in Beijing University of Chemical Technology; Ultra-capacitor conductivity titania lithium electrode material with carbon and preparation method thereof has been invented by Fudan University.The application number of the relevant capacitor patent of Shenzhen Graduate School of Tsinghua University is: disclosing polyacrylic acid lipid and polytetrafluoroethylene among the CN-200510033986 is the electrode of adhesive.But because polytetrafluoroethylene and vinylidene bonding strength are not enough, and generally use higher boiling point and toxic solvent.The many companies of the U.S. attempt using this type of adhesive, but the result is all undesirable.Therefore, all can not satisfy the needs of practical application with the electrode material of current method preparation.
Three, summary of the invention
One of purpose of the present invention provides a kind of electrically-conducting paint that is used to prepare ultracapacitor.
Two of purpose of the present invention provides a kind of preparation method who is used to prepare the electrically-conducting paint of ultracapacitor.
These and other objects of the present invention will further embody and set forth by following detailed description and explanation.
The electrically-conducting paint that is used to prepare ultracapacitor of the present invention, comprise porous carbon materials, conductive agent, binding agent and solvent, its weight percentage is: porous carbon materials 18%～30%, conductive agent 0.1%～10%, binding agent 1%～5%, solvent 30%～80%, total weight are 100; The pH value of prepared electrically-conducting paint is 6-12, and the percent solids scope is 10-55%, and range of viscosities is 10-1000cps.
Further, the electrically-conducting paint that is used to prepare ultracapacitor of the present invention, comprise porous carbon materials, conductive agent, binding agent and solvent, its weight percentage is: porous carbon materials 20%～28%, conductive agent 0.5%～8%, binding agent 1.5%～4%, solvent 40%～70%, total weight are 100.
What can select is, the electrically-conducting paint that is used to prepare ultracapacitor of the present invention, comprise porous carbon materials, conductive agent, binding agent and solvent, its weight percentage is: porous carbon materials 20%～28%, conductive agent 2%～6%, binding agent 2.5%～4%, solvent 50%～70%, total weight are 100.
At the electrically-conducting paint that is used for preparing ultracapacitor of the present invention, the pH value of electrically-conducting paint is 8～9, and the percent solids scope is 25～35%, and range of viscosities is 50～300cps.
At the electrically-conducting paint that is used for preparing ultracapacitor of the present invention, described porous carbon materials is the combination of a kind of or two kinds of arbitrary proportions in porous activated carbon and the activated carbon fiber, and its density is 0.5g/cm
3～1.6g/cm
3, further preferable range is 0.7g/cm
3～1.2g/cm
3, specific area is 100m
2/ g～4000m
2/ g; Micro content＜5%, the molal quantity of the active group on surface and the ratio of its carbon molal quantity are 0.1%～2.5%; Described conductive agent is the combination of one or more arbitrary proportions in acetylene black, graphite and the carbon nano-fiber; Described binding agent is the combination of soluble epoxide resin and resinoid one or both arbitrary proportions of modified polyacrylic acid, and solvent is a water.Described binding agent is XZ92598, XZ92546 and XZ92533 soluble epoxide resin and Aqumlam 444A or Robond C-330 modified polypropene acid resin, can be used alone, and also can use the mixture of two or more arbitrary proportion.Used conductive carbon is Vulcon XC-72 or GH-3892; Used electrically conductive graphite specification is Timrex KS6 or Ab-065M.
The electrically-conducting paint that is used to prepare ultracapacitor of the present invention, the surfactant (being preferably 0.1～1 weight %) that also comprises 0.05～5 weight %, as: Surfynol 104S, Surfynol FS-80, Surfynol 104A, Surfynol 420, Surfynol FS-85, Surfynol 104BC, Surfynol 440, Surfynol OP-340, Surfynol 104DPM is preferably SurfynolOP-340; The defrother (being preferably 0.1～1 weight %) that also comprises 0.05～5 weight %, as: Surfynol DF-58, Surfynol DF-40, Surfynol DF-37, Surfynol DF-60, Surfynol DF-70, Surfynol DF-110D, Surfynol DF-62, Surfynol DF-75, Surfynol, defoamer Surfynol DF-66, Surfynol DF-210 is preferably DF-110D; The Dispersion of Particles auxiliary agent (being preferably 0.1～1 weight %) that also comprises 0.05～5 weight %, as: SURFYNOL 2502, and SURFYNOL 5021/5, SURFYNOL CT-111, and SURFYNOL CT-131 is preferably CT-136.
In the present invention, acrylic resin modified is anionic, selects an amount of unsaturated carboxylic acid such as acrylic acid in the monomer of copolymer resins for use, methacrylic acid, maleic anhydride, methylene-succinic acid, make to have carboxyl on the side chain, become ammoniacal liquor to be neutralized into salt with organic amine again and obtain water-soluble.In addition also can be on the resin side chain by selecting for use suitable monomer with introducing-OH hydroxyl ,-CONH
2Acylamino-or-hydrophilic radical such as O-ehter bond and increase the water-soluble of resin.Therefore, the composition of acrylic resin can comprise: monomer, and as methacrylic acid, metering system methyl esters, styrene, ethyl acrylate, butyl acrylate, Hexyl 2-propenoate etc.The hardness of base resin, physical properties such as pliability and resistance to water can achieve the goal by adjusting monomer and combination thereof; In addition the functional monomer as: hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, methacrylic acid, acrylic acid, maleic anhydride etc. can provide hydrophilic radical and water-soluble and provide the cross-linking reaction group for resin; And nertralizer such as ammoniacal liquor, dimethylethanolamine, N-ethylmorpholine, 2-dimethyl propyl alcohol, 2-amino-2-methyl propyl alcohol etc. then can in and resin on carboxyl, salify provides resin water-soluble.The present invention uses the composition of one or more arbitrary proportions of modified polypropene acid resin and soluble epoxide resin, with collector good adhesiveness is arranged, and with the conduction basement membrane good compatibility is arranged.Through having outstanding thermal stability, electric inertia after the secondary curing, be not subjected to electrolytical the influence, thereby low internal resistance, long-life capacitance electrode are provided.
The preparation method who is used to prepare the electrically-conducting paint of ultracapacitor of the present invention, be earlier with binding agent and part surface activating agent, defrother and Dispersion of Particles auxiliary agent are dissolved in the partial solvent, then with the binding agent for preparing, porous carbon materials, conductive agent and remaining surfactant, defrother, the solvent of Dispersion of Particles auxiliary agent and surplus drops in the mixing container, start the speed change mixer, raising speed is to 800-1200 rev/min (being preferably 1000 rev/mins) gradually, after the continuous stirring 2 to 3 hours (being preferably 2.5 to 3 hours), through filtration treatment, be prepared into uniform and stable electrically-conducting paint.Described in the present invention speed change mixer can also be used high shear dispersion machine, sand mill, ball mill, replacements such as three-roller.The speed change stirring dispersion machine that the present invention uses uses the sawtooth pattern impeller, the alternately curved flute profile of bending on the edge of impeller, and the inclination angle is for tangentially becoming 20 °～40 ° angles, and the outer edge surface of each tooth can produce powerful percussion.The tooth outer edge surface promotes object and outwards flows, and forms circulation and shearing force, and rotating speed is generally 1000～1500N/ branch.
The all raw material of Shi Yonging comprises that additive all is conventional uses as surfactant, defrother etc., can buy from market in the present invention.
In the present invention, refer in particular to as non-, all amounts, part, percentage are unit of weight.
Below further specify the present invention by specific embodiment, but embodiment only be used for the explanation, can not limit the scope of the invention.
Four, embodiment
Embodiment 1
(the Ashland ChemicalCompany of company product is learned in A Shilan Dehua with acrylic resin modified Aqualam 444A, 3 parts (solids content) down together), epoxy resin XZ 92598 (Dow Chemical DowChemicals company product, 1 part (solids content) down together), Surfynol OP-340 (U.S. aerification chemical product company product, 0.15 part down together), DF-110D (U.S. aerification chemical product company product, 0.05 part down together), CT-136 (U.S. aerification chemical product company product, down with) 0.3 part be dissolved in respectively in 66.5 parts of water, the content that is used for the electrically-conducting paint adhesive is percent 4 of total weight.
High surface area carbon (porous carbon materials) is used XC-72 (Cobont Corporation product, down together), and content is 25.5 parts in electrically-conducting paint.Select the graphite material, with KS6 (Timcal Graphite and Carbon company product, the down together) electrically conductive graphite of Timrex, content is 3.5 parts in electrically-conducting paint.
With 4kg (solids content) adhesive, 25.5kg carbon, 3.5kg graphite, Surfynol OP-3400.15kg, DF-110D, 0.05kg, CT-136,0.3kg and 66.5kg water (deionized water or distilled water etc.) add in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000 rev/mins gradually, and continuous stirring 2～3h is in stirring, fluid temperature is elevated to 30～40 ℃, and creating pockets of air, stops then stirring, after the filter bag filtration, obtain the electrically-conducting paint product.The adhesiveness of electrically-conducting paint is 4 grades, resistance value≤30, and PH8～9, percent solids is 25～35%, range of viscosities is 50～300cps.
Embodiment 2
With acrylic resin modified Aqualam 444A, 3 parts (solids content), 92546,1 parts of epoxy resin XZ (solids content), Surfynol OP-340,0.15 part, DF-110D, 0.05 part, CT-136,0.3 part, being dissolved in respectively in 66.5 parts of water, the content that is used for the electrically-conducting paint adhesive is percent 4 of total weight.
High surface area carbon is used XC-72 (porous carbon materials), and content is 25.5 parts in electrically-conducting paint.Select the graphite material, with the KS6 electrically conductive graphite of Timrex, content is 3.5 parts in electrically-conducting paint.
With 4kg (solids content) adhesive, 25.5kg activated carbon, 3.5kg graphite, Surfynol OP-340,0.15kg, DF-110D, 0.05kg, CT-136,0.3kg and water 66.5kg add in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000 rev/mins gradually, continuous stirring 2～3 hours, in stirring, fluid temperature is elevated to 30～40 ℃, and creating pockets of air, stop then stirring, after filtering with filter bag, static stand-by.The adhesiveness of electrically-conducting paint is 4 grades, resistance value≤30, and PH8～9, percent solids 25～35%, range of viscosities is 50～300cps.
Embodiment 3
With acrylic resin modified Aqualam 444A, 3 parts (solids content), 92533,1 parts of epoxy resin XZ (solids content), Surfynol OP-340,0.15 part, DF-110D, 0.05 part, CT-136,0.3 part, being dissolved in respectively in 66.5 parts of water, the content that is used for the electrically-conducting paint adhesive is percent 4 of total weight.
High surface area carbon is used XC-72 (porous carbon materials), and content is 25.5 parts in electrically-conducting paint.Select the graphite material, with the KS6 electrically conductive graphite of Timrex, content is 3.5 parts in electrically-conducting paint.
With 4kg (solids content) adhesive, 25.5kg activated carbon, 3.5kg graphite, Surfynol OP-3400.15kg, DF-110D, 0.05kg, CT-136,0.3kg and water 66.5kg add in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000 rev/mins gradually, and continuous stirring 2～3 hours is in stirring, fluid temperature is elevated to 30～40 ℃, and creating pockets of air, stops then stirring, after the filter bag filtration, static stand-by.The adhesiveness of electrically-conducting paint is 4 grades, resistance value≤30, and PH8-9, percent solids 25～35%, range of viscosities is 50～300cps.
Embodiment 4
Robond C-330 is acrylic resin modified, 3 parts (solids content), 92546,1 parts of epoxy resin XZ (solids content), Surfynol OP-340,0.15 part, DF-110D, 0.05 part, CT-136,0.3 part, being dissolved in respectively in 66.5 parts of water, the content that is used for the electrically-conducting paint adhesive is percent 4 of total weight.
High surface area carbon (porous carbon materials) is used XC-72, and content is 25.5 parts in electrically-conducting paint.Select the graphite material, with the KS6 electrically conductive graphite of Timrex, content is 3.5 parts in electrically-conducting paint.
With 4kg (solids content) adhesive, 25.5kg activated carbon, 3.5kg graphite, Surfynol OP-3400.15kg, DF-110D, 0.05kg, CT-136,0.3kg and water 66.5kg add in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000 rev/mins gradually, and continuous stirring 2～3 hours is in stirring, fluid temperature is elevated to 30～40 ℃, and creating pockets of air, stops then stirring, after the filter bag filtration, static stand-by.The adhesiveness of electrically-conducting paint is 4 grades, resistance value≤30, and PH8-9, percent solids 25～35%, range of viscosities is 50～300cps.
Embodiment 5
(the Ashland ChemicalCompany of company product is learned in A Shilan Dehua with acrylic resin modified Aqualam 444A, 3.5 parts (solids content) down together), epoxy resin XZ 92598 (Dow Chemical DowChemicals company product, 1 part (solids content) down together), Surfynol OP-340 (U.S. aerification chemical product company product, 0.25 part down together), DF-110D (U.S. aerification chemical product company product, 0.1 part down together), CT-136 (U.S. aerification chemical product company product, down with) 0.6 part be dissolved in respectively in 65.55 parts of water, the content that is used for the electrically-conducting paint adhesive is percent 4.5 of total weight.
High surface area carbon (porous carbon materials) is used XC-72 (Cobont Corporation product, down together), and content is 28.5 parts in electrically-conducting paint.Select the graphite material, with KS6 (Timcal Graphite and Carbon company product, the down together) electrically conductive graphite of Timrex, content is 0.5 part in electrically-conducting paint.
With 4.5kg (solids content) adhesive, 28.5kg activated carbon, 0.5kg graphite, SurfynolOP-340 0.25kg, DF-110D, 0.1kg, CT-136,0.6kg and 65.55kg water (deionized water or distilled water etc.) add in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000 rev/mins gradually, and continuous stirring 2.8 hours is in stirring, fluid temperature is elevated to 30～40 ℃, and creating pockets of air, stops then stirring, after the filter bag filtration, obtain the electrically-conducting paint product.The adhesiveness of electrically-conducting paint is 4 grades, resistance value≤30, and PH8.5, percent solids is 30～35%, range of viscosities is 200～300cps.
Embodiment 6
With acrylic resin modified Aqualam 444A, 1 part (solids content), 92546,1 parts of epoxy resin XZ (solids content), Surfynol OP-340,0.5 part, DF-110D, 0.5 part, CT-136,0.5 part, being dissolved in respectively in 67.5 parts of water, the content that is used for the electrically-conducting paint adhesive is 2 percent of total weight.
High surface area carbon (porous carbon materials) is used XC-72, and content is 20 parts in electrically-conducting paint.Select the graphite material, with the KS6 electrically conductive graphite of Timrex, content is 9 parts in electrically-conducting paint.
With 2kg (solids content) adhesive, 20kg activated carbon, 9kg graphite, Surfynol OP-3400.5kg, DF-110D, 0.5kg, CT-136,0.5kg and water 67.5kg add in the feed chute, start the high speed shear mixer, rotating speed accelerates to the 1000n/ branch gradually, and continuous stirring 2～3 hours is in stirring, fluid temperature is elevated to 30～40 ℃, and creating pockets of air, stops then stirring, after the filter bag filtration, static stand-by.The adhesiveness of electrically-conducting paint is 4 grades, resistance value≤30, and PH8～9, percent solids 25～35%, range of viscosities is 50～300cps.
Embodiment 7
With acrylic resin modified Aqualam 444A, 2 parts (solids content), 92533,2 parts of epoxy resin XZ (solids content), Surfynol OP-340,0.35 part, DF-110D, 0.15 part, CT-136,0.7 part, being dissolved in respectively in 71.8 parts of water, the content that is used for the electrically-conducting paint adhesive is percent 4 of total weight.
High surface area carbon (porous carbon materials) is used XC-72, and content is 18 parts in electrically-conducting paint.Select the graphite material, with the KS6 electrically conductive graphite of Timrex, content is 5 parts in electrically-conducting paint.
With 4kg (solids content) adhesive, 18kg activated carbon, 5kg graphite, Surfynol OP-3400.35kg, DF-110D, 0.15kg, CT-136,0.7kg and water 71.8kg add in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000 rev/mins gradually, and continuous stirring 2～3 hours is in stirring, fluid temperature is elevated to 30～40 ℃, and creating pockets of air, stops then stirring, after the filter bag filtration, static stand-by.The adhesiveness of electrically-conducting paint is 4 grades, resistance value≤30, and PH8-9, percent solids 25～35%, range of viscosities is 50～300cps.
Embodiment 8
Robond C-330 is acrylic resin modified, part 0.5 (solids content), 92546,0.5 parts of epoxy resin XZ (solids content), Surfynol OP-340,0.05 part, DF-110D, 0.03 part, CT-136,0.03 part, being dissolved in respectively in 80.39 parts of water, the content that is used for the electrically-conducting paint adhesive is 4 percent of total weight.
High surface area carbon (porous carbon materials) is used XC-72, and content is 18 parts in electrically-conducting paint.Select the graphite material, with the KS6 electrically conductive graphite of Timrex, content is 0.5 part in electrically-conducting paint.
With 1kg (solids content) adhesive, 18kg activated carbon, 0.5kg graphite, Surfynol OP-3400.05kg, DF-110D, 0.03kg, CT-136,0.03kg and water 80.39kg add in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000 rev/mins gradually, and continuous stirring 2.5 hours is in stirring, fluid temperature is elevated to 30～40 ℃, and creating pockets of air, stops then stirring, after the filter bag filtration, static stand-by.The adhesiveness of electrically-conducting paint is 3 grades, resistance value≤30, and PH8.5, percent solids 25%, viscosity are 100cps.
Claims (10)
1. electrically-conducting paint that is used to prepare ultracapacitor, it is characterized in that comprising porous carbon materials, conductive agent, binding agent and solvent, its weight percentage is: porous carbon materials 18%～30%, conductive agent 0.1%～10%, binding agent 1%～5%, solvent 30%～80%, total weight are 100; The pH value of prepared electrically-conducting paint is 6-12, and percent solids is 10-55%, and viscosity is 10-1000cps.
2. the electrically-conducting paint that is used to prepare ultracapacitor according to claim 1, it is characterized in that comprising porous carbon materials, conductive agent, binding agent and solvent, its weight percentage is: porous carbon materials 20%～28%, conductive agent 0.5%～8%, binding agent 1.5%～4%, solvent 40%～70%, total weight are 100.
3. the electrically-conducting paint that is used to prepare ultracapacitor according to claim 1, it is characterized in that comprising porous carbon materials, conductive agent, binding agent and solvent, its weight percentage is: porous carbon materials 20%～28%, conductive agent 2%～6%, binding agent 2.5%～4%, solvent 50%～70%, total weight are 100.
4. according to the described electrically-conducting paint that is used to prepare ultracapacitor of one of claim 1-3, the pH value that it is characterized in that electrically-conducting paint is 8～9, and percent solids is 25～35%, and viscosity is 50～300cps.
5. according to the described electrically-conducting paint that is used to prepare ultracapacitor of one of claim 1-4, it is characterized in that described porous carbon materials is the combination of a kind of or two kinds of arbitrary proportions in porous activated carbon and the activated carbon fiber; Described conductive agent is the combination of one or more arbitrary proportions in acetylene black, graphite and the carbon nano-fiber; Described binding agent is the combination of one or both arbitrary proportions of water-soluble epoxy resin and modified polypropene acids, and solvent is a water.
6. according to the described electrically-conducting paint that is used to prepare ultracapacitor of one of claim 1-4, it is characterized in that also comprising the surfactant of 0.05～5 weight %, be preferably OP-340.
7. according to the described electrically-conducting paint that is used to prepare ultracapacitor of one of claim 1-4, it is characterized in that also comprising the defrother of 0.05～5 weight %, be preferably DF-110D.
8. according to the described electrically-conducting paint that is used to prepare ultracapacitor of one of claim 1-4, it is characterized in that also comprising the Dispersion of Particles auxiliary agent of 0.05～5 weight %, be preferably CT-136.
9. the electrically-conducting paint that is used to prepare ultracapacitor according to claim 5, it is characterized in that described binding agent is XZ92598, XZ92546 and XZ92533 water-soluble epoxy resin and Aqumlam444A or Robond C-330 modified polypropene acid resin, can be used alone, also can use the mixture of two or more arbitrary proportion.
10. according to the described preparation method who is used to prepare the electrically-conducting paint of ultracapacitor of one of claim 1-9, it is characterized in that earlier binding agent and part surface activating agent, defrother and Dispersion of Particles auxiliary agent being dissolved in the partial solvent, then binding agent, porous carbon materials, conductive agent and remaining surfactant, defrother, Dispersion of Particles auxiliary agent and the solvent for preparing dropped in the mixing container, start the speed change mixer, raising speed to 1000 rev/min gradually, after the continuous stirring 2 to 3 hours, through filtration treatment, be prepared into uniform and stable electrically-conducting paint.
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| CN101899233A (en) * | 2010-07-29 | 2010-12-01 | 上海翰博实业有限公司 | Supercapacitor electrode corrosion-resistant conductive coating |
| CN102295898A (en) * | 2011-06-08 | 2011-12-28 | 丁建民 | Configuration and coating method of aluminium foil precoat nano conductive carbon primary coat liquid |
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| CN109422260A (en) * | 2017-08-30 | 2019-03-05 | 北京大学 | Method based on active Carbon composites preparation ultra-clean graphene |
| CN109422260B (en) * | 2017-08-30 | 2020-09-04 | 北京大学 | Method for preparing ultra-clean graphene based on activated carbon compound |
| CN109215844A (en) * | 2018-10-25 | 2019-01-15 | 天津普兰能源科技有限公司 | A kind of in-situ corrosion electrocondution slurry and electrode piece preparation method |
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