CN101140828B - Technique for large-scale producing super capacitor - Google Patents
Technique for large-scale producing super capacitor Download PDFInfo
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- CN101140828B CN101140828B CN2007100713070A CN200710071307A CN101140828B CN 101140828 B CN101140828 B CN 101140828B CN 2007100713070 A CN2007100713070 A CN 2007100713070A CN 200710071307 A CN200710071307 A CN 200710071307A CN 101140828 B CN101140828 B CN 101140828B
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Abstract
The invention discloses a super-capacitors storage producing on scale, which is characterized in its manufacturing method comprising: first, spread coating membrane A, which is to spread the prepared conducting paint onto the current collectors after superficial treatment by coating machine; second, to prepare membrane B, which contains active carbon of 40% to 90%, conductive graphite of 2% to 5%and the bond of 2% to 25% in weight ratio; third, preparing the electrode material by dry process and heat pressing, which is formed by heat pressing of the membranes A and B, after which stripping it into the stripping electrode membrane by adhesive tape splitting machine; fourth, preparing the electrode by dry process, which is to clip two strips of electrode membrane in same size with isolating film by winder; fifth, putting the electrode into the aluminum super-capacitors shell, covered and keying on the positive and negative poles of the electrode by laser welding, and then infusing the electrolyte and sealed, by which the super-capacitors storage is produced.
Description
Technical field
The present invention relates to ultracapacitor, the ultracapacitor technology of a kind of large-scale production specifically.
Background technology
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 a kind of energy quick charge that occurs in recent years, superpower energy storage device.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 promptly 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.Therefore, ultracapacitor is developing into a kind of novel, efficient, practical energy storage and fast charging and discharging equipment.Very application prospects is all arranged in fields such as the energy, communication, number, electronics, medical treatment, health, network, automobiles.
A complete ultracapacitor comprises electrode, electrolyte, collector, four parts of barrier film.The electrode material of the ultracapacitor of research mainly contains four aspects at present: 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.
Electrolyte need have very high conductivity and enough electrochemical stabilities, so that ultracapacitor can be worked under high as far as possible voltage.Existing electrolyte is mainly by solid electrolyte, organic substance electrolyte and aqueous electrolyte.The electrolytical decomposition voltage height of organic substance generally all be higher than 2.5V, but conductivity is poor; Aqueous electrolyte mainly is KOH and H
2SO
4[H2SO4], their decomposition voltage is subjected to the restriction of the decomposition electric potential of water, has only 1.23V, but its conductivity is more than 4 times of organic bath.
The suitable use of barrier film also is very crucial.Organic bath uses polymer (particularly PP) or paper as barrier film usually, and aqueous electrolyte can adopt glass fibre or ceramic diaphragm.
Collector is then normally selected for use electric conductivity good metal and graphite to wait to serve as.
A well behaved ultracapacitor needs four above parts to reach optimum optimization.The ionic conductance height of electrolyte and barrier film, barrier film have high electrical isolation resistance, and electrode electronic conductance height, specific area are big, and barrier film and electrode are thin as far as possible.Wherein, electrode material and electrolytical selection have the greatest impact to capacitance.
The electrode material of ultracapacitor is the key factor of decision capacitor performance, and 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.
Relating to electrode material for super capacitor, to make external partial monopoly as follows:
People such as Mitchell have introduced the electrode design method of two voltage capacitors in United States Patent (USP) the 7227737th patent publication No..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 the super capacitor applied voltage, 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 zhong have introduced impregnation process porous electrode and preparation method thereof in United States Patent (USP) the 7147674th patent publication No..Many property 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) the 7102877th patent publication No..Two sides of porous basement membrane, are combined with collector then and prepare electrode by the support membrane double side support by conducting liquid dipping back.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) the 7090946th patent publication No..This combination electrode is prepared by the pressure compacting, is not in conjunction with preparation with adhesive.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.Through cutting into electrode shape, this electrode can be used to prepare energy storage devices such as double layer capacitor.
People such as Bendale have introduced a kind of electrode preparation method in United States Patent (USP) the 6955694th patent publication No..On collector, be coated with electrically-conducting paint, and solidify the ground floor electrically-conducting paint, and then be coated with second layer coating and solidify it, and 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 United States Patent (USP) the 6813139th patent publication No..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 Nanjundiah have introduced electrode preparation method in United States Patent (USP) the 6804108th patent publication No., the 6643119th patent publication No., the 6631074th patent publication No. and the 6627252nd patent publication No..Two sided coatings ground floor coating on aluminium foil after drying, at the two-sided second layer coating of coating, is prepared into electrode material more after drying.Used electrically-conducting paint is water-soluble by active carbon, PVDF, acetone, methylcellulose, own propyl group diene fourth monomer etc.
People such as Kurabayashi disclose the method for making double electric layer capacitor in United States Patent (USP) the 5099398th patent publication No..In this patent, electrode comprises the porous sintered body of the small activated carbon particles of connection, and current-collector is the form by the conducting film of making such as the mixture of powders of the electric conducting material of carbon and synthetic resin or rubber.For current-collector is adhered to electrode,, electrode is pressed to the dissolved surface of current-collector by the surface dissolution of organic solvent with current-collector.When solvent evaporation, electrode is glued fast to current-collector, has therefore made the electrode that has low contact resistance between electrode and the current-collector.
People such as Kurabayashi disclose the another kind of method of making double electric layer capacitor in United States Patent (USP) the 5072336th patent publication No..In this patent, in order to reduce contact resistance between electrode and the current-collector, by from forming conductive metal film on each surface of each electrode or current-collector, electrode is contacted with current-collector such as the evaporation of metal of gold (Au), silver (Ag), nickel (Ni), platinum (Pt) or copper (Cu).In addition, they disclose in United States Patent (USP) the 5142451st patent publication No. and the 5121301st patent publication No. and have utilized various adhesives to carry out bonding method in the mode that is similar to said method between electrode and current-collector.
People such as Nishino disclose a kind of method of the lip-deep metal level of carbon fiber or activated carbon electrodes as current-collector that be formed on of utilizing in United States Patent (USP) the 4562511st patent publication No..This patent has considered to form on the surface of electrode the whole bag of tricks of metal level, as the use of plasma spraying, arc spraying, vacuum moulding machine, sputter, non-electrolyte plating and electrically-conducting paint.
In United States Patent (USP) the 5102745th, 5304330 and 5080963 patent publication No., people such as Tatarchuk disclose by being heated to the fusing point of metallic fiber, carry out bonding method between electrode that metallic fiber forms and current-collector.Adhesion technique between the carbon fiber that uses in metallic fiber that uses in the following execution current-collector and the electrode.The stainless steel fibre of the about 2um of diameter and diameter are that carbon fiber and the length of 1um～5um is that cellulose and the water of 5mm mixes equably by stirring, filtration then, thereby be formed for the composite fibre synthetic of electrode.This fiber synthetic is pressed into thin slice in mould.Zhi Bei thin slice stands high temperature and pressure then like this, with at its place, crosspoint binder fibre, makes the electrode of the internal resistance with improvement like this.These patents have also been described the additional fibers as adhesive, to help bonding between the above-mentioned fiber.This additional fibers comprises metal, pottery, carbon or its any combination.
People such as Farahmandi disclose the electrode that comprises the active carbon that is woven into fabric in United States Patent (USP) the 5777428th patent publication No. and the 6059847th patent publication No. [the 5777428th and No. 6059847].Use aluminium foil as current-collector, make electrode by the impregnated activated carbon felt of aluminium that utilizes fusing.In this patent, carry out the diffusion-bonded technology by the temperature below 600 ℃ (corresponding to fusing points of aluminium) aluminium foil is attached to aluminium/carbon synthetic electrode, to avoid forming the aluminium carbide that meeting significantly reduces electrode performance by the reaction between carbon and the aluminium.
People such as Zuckerbrod disclose in United States Patent (USP) the 4448856th patent publication No. by utilizing adhesive active carbon to be mixed a kind of electrode for preparing with powder of stainless steel.The density of each powder is limited to 25～450um, 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.Because active carbon can be made into the form of fiber, thereby can consider charcoal treatment is become the whole bag of tricks of electrode.But, can not make fibers form to carbon nano-tube or carbon nano-fiber, this has produced restriction to making carbon nanotube electrode or carbon nano-fiber electrode.Method in common is by the mixture of carbon nano-tube or carbon nano-fiber and adhesive being exerted pressure, making the carbon nanotube electrode or the carbon nano-fiber electrode of dish type.
The domestic partial monopoly that relates to the electrode material for super capacitor making is as follows:
People such as Fu Xutao disclose a kind of automobile-used ultracapacitor in Chinese patent publication number CN1420507A, comprise first electrode, second electrode, electrolyte, collector, barrier film and shell.The absolute capacitance amount of first electrode is greater than the absolute capacitance amount of second electrode, and electrode material is to be made by the material that stores faraday's process or secondary capacitance principle storage power by electric double layer principle or capacitance principle in second electrode.
Shanghai prestige difficult to understand is at Chinese patent publication number CN1431669; CN1431670; CN2541938; With a kind of automobile-used startup ultracapacitor is disclosed among the CN2574196, its fuse by the parcel barrier film around forming the zinc oxide positive plate, serialization activated carbon fiber cloth negative pole becomes with the diaphragm structure that afflux supports.The ultracapacitor of Chinese patent publication number CN1317809 use new material is the preparation method extremely.A kind of capacitor that uses the electrode of new material formation is provided.It includes opposed facing two electrodes, and these electrodes are made up of carbon nano-tube, is arranged on the electrolyte between this two electrode, and is used to separate the electrolytical parting liquid between this two electrode.Chinese patent CN1354482A: the object of extremely making based on the composite powder of electric conductor and fluoropolymer with this powder.The present invention designs a kind of microcomposite powder, and it is coated with the fluoropolymer particles (PVDF) of 0.1～0.5um.According to a preferred form of the present invention, microcomposite powder comprises composition (A, polyethylene glycol), and it is a kind of polymer or oligomer that can be used in the dissolution with solvents of fluoropolymer or conductive compositions non-solvent.Chinese patent publication number CN1483212A patented invention relates to a kind of double layer capacitor, comprise that at least one pair of is connected to the polarizable electrode of current collector, be inserted in the electrode of every pair of electrode by ion-permeable but dividing layer that the electronic isolation material is made and liquid electrolyte.Has the wherein carbon granule layer of nanoaperture pipe distribution according to electrode of the present invention, the size of nanoaperture and electrolytical ionic size coupling.The present invention relates to make a kind of method of this ultracapacitor.
People such as Li Wensheng disclose the employing polytetrafluoroethylene in Chinese patent CN1905100A patent publication No., vinylidene is an adhesive, use the curtain coating coating process and prepare active carbon electrode material.
People such as Li Yongxi disclose the employing polytetrafluoroethylene in Chinese patent CN1317809A patent publication No., vinylidene, and phenolic resins, polyvinyl alcohol, shuttle methylcellulose are the CNT (carbon nano-tube) electrode of adhesive.
It is the electrode material of adhesive that Tan Qiang wait the people to disclose in Chinese patent CN1770344A patent publication No. by force to adopt the composition of polytetrafluoroethylene or poly-inclined to one side tetrafluoroethene and N-methyl pyrrolidone.
The natural minerals of Zhejiang University invention and CNT (carbon nano-tube) compound super capacitor electrode material and preparation method and with the preparation method of Ru/C nanometer combined electrode material;
The carbon nano-tube of Chengdu Organic Chemistry Inst., Chinese Academy of Sciences's invention is used for electrode material for super capacitor;
The preparation method of a kind of layered cobalt aluminium bihydroxy composite metal oxide electrode material of Beijing University of Chemical Technology's invention;
Ultra-capacitor conductivity titania lithium electrode material with carbon and preparation method thereof of Fudan University's invention.But because the vinylidene bonding strength is 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.
The problem of existing super capacitor:
1, the limiting voltage of existing super capacitor is not high, generally at 2.0～2.5 volts, theoretically, the limiting voltage of electric double layer super capacitor can reach 4.0 volts, but remaining impurities among the preparation method of existing electrode, solvent and additive etc. has limited the limiting voltage of super capacitor.
2, useful life is not long.The electrode of existing super capacitor, no matter be with coating processing, still with extruding processing, in prescription, all to add many additives, as: solvent, lubricant, stabilizer, plasticizer, levelling agent etc., various reactions may take place with electrolyte in these additives, thereby reduce the limiting voltage and the useful life of super capacitor.
3, with the electrode of coating process preparation except additive and impurity effect the quality, its coating thickness is restricted, thickness can not be too thick, simultaneously, the uniformity of thickness is also undesirable.If be coated with at twice or repeatedly, equally also have problems such as inhomogeneities, impurity.
Summary of the invention
It is low to the objective of the invention is to overcome prior art super capacitor electrode adhesion intensity, shortcomings such as the not high and production cost height of energy density, the ultracapacitor technology of a kind of fast charging and discharging, a kind of large-scale production is provided, and it will improve active carbon and conductive carbon distributing homogeneity and consistency in electrode; Improve the intensity of electrode film; Reduce the internal resistance of electrode; Increase surface area; Use non-additive dry process method.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
A kind of ultracapacitor technology of large-scale production, this preparation technology comprises:
(1) coating conduction basement membrane, i.e. A film:
The electrically-conducting paint for preparing is coated on the surface treated collector with coating machine, described coating machine is a notch board reticulate pattern dispense tip, and the coating machine oven temperature is 40～110 ℃, according to Gradient distribution at each section baking oven, the coating speed of coating machine is 5～80m/min, and coating weight is 2～10g/m
2, coating thickness is 4～12um, and the A film is the strip coating, and the line thickness error range of coating is 0～1.5mm, and the A film is a double spread, and the line thickness error range of double spread is 0～1.5mm, and the resistance value of A film is less than 30m Ω;
(2) preparation composite conducting basement membrane, i.e. B film:
It is 40～99% that described B film contains the active carbon weight ratio, and containing the electrically conductive graphite weight ratio is 2～50%, and containing the binder wt ratio is 2～25%;
Active carbon is that among XC-72 and the GH-3892 one or both mix by arbitrary proportion, from Cabont company; Electrically conductive graphite is that among K56 and the AB-065M one or both mix by arbitrary proportion, from Timcal Graphite andCarbon company; Adhesive is a thermoplastics, can extrude the processing film forming, and adhesive is an ethylene-tetrafluoroethylene copolymer;
The B film is the mixed-powder that active carbon, electrically conductive graphite and three kinds of powder material of adhesive evenly form through dry powder blend, and dry powder blend is finished in high-speed mixer;
The B film is prepared by three roller plasticators, and the temperature range of the plasticating temperature of three roller plasticators is 300～500 ℃, and the time of plasticating is 10～120 minutes, and the length of prepared B film is 1～2000 meter, and thickness is 50～500um;
(3) dry method hot pressing power backup utmost point material:
Form through adding hot pressing by A film and B film, make the itemize electrode film by adhesive tape cutting machine itemize then;
(4) dry process electrode:
On the up-coiler with the itemize electrode film of two same sizes folder on barrier film be prepared from electrode, the fuse diameter of up-coiler is 5～200mm, the fuse height of coiling is 5～200mm;
(5) electrode is put into aluminum super capacitor shell, cover lid through the both positive and negative polarity of laser welding connection electrode, annotates electrolyte, seals and just makes ultracapacitor.
The best coating speed of described coating machine is 25～55m/min.
The preferred plan of described A film is: coating weight is 2.8～5.2g/m
2, coating thickness is 6～10um, and the A film is the strip coating, and the line thickness error range of coating is 0～0.5mm, and the A film is a double spread, the line thickness error range of double spread is 0～0.5mm.
The preferred plan of described B film is: containing the active carbon weight ratio is 60～80%, and the electrically conductive graphite weight ratio is 10～20%, and the binder wt ratio is 10～20%.
Described B film is prepared by three roller plasticators, its optimised process is: the temperature range of the plasticating temperature of three roller plasticators is 320～380 ℃, the time of plasticating is 30～40 minutes, and the length of prepared B film is 1000～2000 meters, and thickness is 100～250um.
The preparation technology of ultracapacitor of the present invention comprises: the dry process method of conduction coating basement membrane-A membrane preparation method, composite conducting basement membrane-B film dry process technology, dry method hot pressing power backup utmost point material, electrode.
1, conduction coating basement membrane-A membrane preparation method: with spraying coating machine, notch board reticulate pattern coating machine, steel wire blade coating machine or other similar coating machines all can.With steam flow formula, active or passive type deflector roll, with electric heating, oil heating or vapour heating all can, oven temperature does not wait from 40～120 ℃, Gradient distribution is in different baking oven sections, coating speed does not wait to 80 meter per seconds with 10 meter per seconds, according to baking oven length, temperature and coating layer thickness decision.Electrically-conducting paint is added feed well, and aluminium foil is placed on one and puts on the deflector roll, starts coating machine, when treating that aluminium foil moves steady nothing and crumples, begins coating.Design determines according to electrode size for the temperature of coating and thickness.But thickness deviation is at ± 2um, and width tolerance is at ± 0.5mm, and the tolerance of two-sided alignment is at ± 0.5mm.
2, composite conducting basement membrane-B film dry process technology:
The optimum formula design of a, conduction basement membrane-B film; Porous carbon 50%～99%, conductive agent 0%～25%, fluoropolymer binder 1%～25%. further optimum formula are: porous carbon 80%～95%, conductive agent 0%～15%, fluoropolymer binder 3%～15%.
The preparation method of b, conduction basement membrane-B film: the preparation of conduction basement membrane prepares moulding through the method that three roller plasticators add heat plasticization.With after the full and uniform mixing of powder material process, behind the three-roller scrub, the front and back roller is loosened slightly earlier, add material between roller and the central roll backward, start motor, 3 rollers begin to rotate with friction speed.Adjust the spacing of preliminary roller and central roll simultaneously, three center lines of three rollers of make suring are parallel, prevent roller tiltedly.A pair of baffle plate is housed between back roller and the central roll, prevents that slip is excessive, when two rollers inwardly rotated, slip was pulled reinforced seam, and this road gap space is narrow gradually, and most of slip can not pass through, and because of two rollers rotate slip is circulated in reinforced ditch.Bulky grain is scolded feed back slurry top, and granule is by slit in the roller and separated into two parts, and a part is attached on the roller of back, and a part is attached on the central roll.That part of on the back roller gets back to reinforced ditch, that part of being delivered between central roll and the preliminary roller on the central roll.So repeatedly circulation just obtains even mixed material, makes the conduction basement membrane through cooling off in flakes again, and film thickness is 100-250um, minimum 1 meter of length.
3, electrode material dry process method: will conduct electricity basement membrane-B film with scribble the collector-A film of electrically-conducting paint, electrode base film is made in compression moulding under heating and pressurizing.
4, super capacitor electrode preparation method: the electrode film of making is installed on the up-coiler, the insulation barrier film is installed simultaneously, to prepare diameter be 25-50mm and highly be the fuse of 30-80mm to start up-coiler, 100～150 ℃ of [100-150C] vacuumizes 8-12 hour, make the electrode of super capacitor.
5, electrode is put into aluminum super capacitor shell, cover lid through the both positive and negative polarity of laser welding connection electrode, annotates electrolyte, seals and just makes ultracapacitor.
Because the present invention has taked above-mentioned technical measures, it compared with prior art has following advantage:
1, has good temperature tolerance, corrosion resistance and electrode and make desired mechanical and physical property;
2, owing to not adding lubricant, stabilizer, plasticizer, levelling agent etc. in conduction basic mode A mould, the molded work of B, therefore, strengthened stable electrochemical property, thereby prolonged the useful life of ultracapacitor;
3, owing to adopt electrode material dry process physical method to prepare electrode material, production technology is simple, be adapted to the scale preparation ultracapacitor, and environmentally friendly.
Description of drawings
Fig. 1 is the electrode base film structural representation of the embodiment of the invention;
Fig. 2 is the Facad structure schematic diagram of the ultracapacitor monomer of the embodiment of the invention;
Fig. 3 is the longitudinal cross-section structural representation of the ultracapacitor monomer of the embodiment of the invention.
Among the figure: 1 is positive terminal, and 2 is negative terminal, and 3 is positive plate, and 4 is negative plate, and 5 is the porous insulation barrier film, and 6 is electrolyte, and 7 is collector body, and 8 is package casing, and 9 are the conduction basement membrane, and 10 is the collector electrode aluminium foil.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1:
With reference to accompanying drawing, electrically-conducting paint is added feed well, collector electrode aluminium foil 10 is through after the surface treatment, and thickness is 20 ± 2um, and width is 500 ± 2mm, and length is 2000～3000m.Be placed on coating machine one and put on the deflector roll, start coating machine, coating machine is coated with the notch board reticulate pattern, and oven temperature is 40～110 ℃, and coating speed is 35 meters/minute, and coating weight is 4.0 ± 1.2g/m
2, coating thickness is 8 ± 2um, coating density is 0.5 ± 0.25g/cm
3, star strip double spread, line thickness are 85 ± 0.5mm, and two-sided alignment accuracy is ± 0.5mm, and outward appearance needs free from admixture, no white point, no wrinkle, no crimping, defectives such as no bubble prepare that to conduct electricity basement membrane 9 be the A film.
Electrically-conducting paint is made by following method:
Adhesive formula:
Water-soluble ethylene-acrylate copolymer emulsion UCAR Latex 300:15 weight portion, Surfynol OP-340:0.5 weight portion, DF-110D:0.1 weight portion, CT-136:1 weight portion.
Above-mentioned raw materials is dissolved in the water of 83.4 weight portions and makes adhesive.
Adhesive weight ratio in electrically-conducting paint is 20%; The high surface active carbon uses XC-72, and the weight ratio in electrically-conducting paint is 60%; Graphite electrode material is selected the K56 electrically conductive graphite of Timrex for use, and weight ratio is 20% in electrically-conducting paint.
Adhesive, active carbon, graphite and water are added in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000n/min 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.Electrically-conducting paint resistance value≤30m Ω, pH 8-9, solid content 25～35%, bonding scope: 50～300cps.
Conduction is done compound basement membrane B film by active carbon, and the XC-72/GH-3892 weight ratio is 70%, and graphite is 15% for the K56/AB-065M weight ratio, and adhesive comes from Du Pont for the ethylene-tetrafluoroethylene copolymer weight ratio is 15%.Three kinds of powder are even in high-speed mixer for dry mixing, about 30 minutes, then three roller plasticators are heated to 300 ℃, material is slowly added plasticated on the three roller plasticators about 30 minutes, be prepared into the composite conducting B film more than a meter then.Thickness is 100～250um.To conduct electricity basement membrane A and B then is pressed into electrode base film through pressing the stone roller machine when being heated to 300 ℃ of temperature.
Electrode base film is cut slivering by the super capacitor dimensional requirement and be wound into a volume for the use of preparation super capacitor.
With two volume electrode materials, 80um porous insulation barrier film 5 is placed on the up-coiler respectively, be wound into the fuse that diameter is the high 80mm of 50mm, and under 150 ℃, vacuumize put it in the aluminum shell after 8 hours, and upper and lower two lids after will heating cover, after treating the lid cooling, promptly be stuck on the aluminum hull firmly, and then be welded in respectively on positive terminal 1 and the negative terminal 2 with the positive plate 3 and the negative plate 4 of method for laser welding with electrode.Then by the aperture on the lid, in hothouse, add electrolyte 6, and seal and make 3000 farads super capacitor.
Embodiment 2:
With reference to accompanying drawing, electrically-conducting paint is added feed well, collector electrode aluminium foil 10 is through after the surface treatment, and thickness is 20 ± 2um, and width is 500 ± 2mm, and length is 2000～3000m.Be placed on coating machine one and put on the deflector roll, start coating machine, coating machine is coated with the notch board reticulate pattern, and oven temperature is 40～110 ℃, and coating speed is 35 meters/minute, and coating weight is 4.0 ± 1.2g/m
2, coating thickness is 8 ± 2um, coating density is 0.5 ± 0.25g/cm
3, star strip double spread, line thickness are 85 ± 0.5mm, and two-sided alignment accuracy is ± 0.5mm, and outward appearance needs free from admixture, no white point, no wrinkle, no crimping, defectives such as no bubble prepare that to conduct electricity basement membrane 9 be the A film.
Electrically-conducting paint is made by following method:
Adhesive formula:
Water-soluble ethylene-acrylate copolymer emulsion UCAR Latex 357:10 weight portion, Surfynol OP-340:0.5 weight portion, DF-110D:0.1 weight portion, CT-136:1 weight portion.
Above-mentioned raw materials is dissolved in the water of 88.4 weight portions and makes adhesive.
Paint adhesive weight ratio in electrically-conducting paint is 15%; The high surface active carbon uses XC-72, and weight ratio is 70% in electrically-conducting paint; Graphite electrode material is selected the K56 electrically conductive graphite of Timrex for use, and weight ratio is 15% in electrically-conducting paint.
With adhesive, active carbon, graphite and water add in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000n/min 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.Electrically-conducting paint resistance value≤30m Ω, pH value are 8-9, solid content 25～35%, adhesiveness: 50～300cps.
Conduction is done compound basement membrane B film by active carbon, and the XC-72/GH-3892 weight ratio is 70%, and graphite is 15% for the K56/AB-065M weight ratio, and adhesive comes from Du Pont for the ethylene-tetrafluoroethylene copolymer weight ratio is 15%.Three kinds of powder are even in high-speed mixer for dry mixing, about 30 minutes, then three roller plasticators are heated to 300 ℃, material is slowly added plasticated on the three roller plasticators about 30 minutes, be prepared into the composite conducting B film more than a meter then.Thickness is 100～250um.To conduct electricity basement membrane A and B then is pressed into electrode base film through pressing the stone roller machine when being heated to 300 ℃ of temperature.
Electrode base film is cut slivering by the super capacitor dimensional requirement and be wound into a volume for the use of preparation super capacitor.
With two volume electrode materials, 80um porous insulation barrier film is placed on the up-coiler respectively, be wound into the fuse that diameter is the high 80mm of 50mm, and under 150 ℃, vacuumize put it in the aluminum shell after 8 hours, and upper and lower two lids after will heating cover, after treating the lid cooling, promptly be stuck on the aluminum hull firmly, and then be welded in respectively on positive terminal 1 and the negative terminal 2 with the positive plate 3 and the negative plate 4 of method for laser welding with electrode.Then by the aperture on the lid, in hothouse, add electrolyte 6, and seal and make 3000 farads super capacitor.
Embodiment 3:
With reference to accompanying drawing, electrically-conducting paint is added feed well, collector electrode aluminium foil 10 is through after the surface treatment, and thickness is 20 ± 2um, and width is 500 ± 2mm, and length is 2000～3000m.Be placed on coating machine one and put on the deflector roll, start coating machine, coating machine is coated with the notch board reticulate pattern, and oven temperature is 40～110 ℃, and coating speed is 35 meters/minute, and coating weight is 4.0 ± 1.2g/m
2, coating thickness is 8 ± 2um, coating density is 0.5 ± 0.25g/cm
3, star strip double spread, line thickness are 85 ± 0.5mm, and two-sided alignment accuracy is ± 0.5mm, and outward appearance needs free from admixture, no white point, no wrinkle, no crimping, defectives such as no bubble prepare that to conduct electricity basement membrane 9 be the A film.
Electrically-conducting paint is made by following method:
Adhesive formula:
Water-soluble ethylene-acrylate copolymer emulsion UCAR Latex 300:5 weight portion, Surfynol OP-340:0.5 weight portion, DF-110D:0.1 weight portion, CT-136:1 weight portion.
Above-mentioned raw materials is dissolved in the water of 93.4 weight portions and makes adhesive.
Adhesive weight ratio in electrically-conducting paint is 10%; The high surface active carbon uses XC-72, and weight ratio is 80% in electrically-conducting paint; Graphite electrode material is selected the K56 electrically conductive graphite of Timrex for use, and weight ratio is 10% in electrically-conducting paint.
With adhesive, active carbon, graphite and water add in the feed chute, start the high speed shear mixer, rotating speed accelerates to 1000n/min 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.Electrically-conducting paint resistance value≤30m Ω, pH value are 8-9, solid content 25～35%, adhesiveness: 50～300cps.
Conduction is done compound basement membrane B film by active carbon, and the XC-72/GM-3892 weight ratio is 70%, and graphite is 15% for the K56/AB-065M weight ratio, and adhesive comes from Du Pont for the ethylene-tetrafluoroethylene copolymer weight ratio is 15%.Three kinds of powder are even in high-speed mixer for dry mixing, about 30 minutes, then three roller plasticators are heated to 300 ℃, material is slowly added plasticated on the three roller plasticators about 30 minutes, be prepared into the composite conducting B film more than a meter then.Thickness is 100～250um.To conduct electricity basement membrane A and B then is pressed into electrode base film through pressing the stone roller machine when being heated to 300 ℃ of temperature.
Electrode base film is cut slivering by the super capacitor dimensional requirement and be wound into a volume for the use of preparation super capacitor.
With two volume electrode materials, 80um porous insulation barrier film is placed on the up-coiler respectively, be wound into the fuse that diameter is the high 80mm of 50mm, and under 150 ℃, vacuumize put it in the aluminum shell after 8 hours, and upper and lower two lids after will heating cover, after treating the lid cooling, promptly be stuck on the aluminum hull firmly, and then be welded in respectively on positive terminal 1 and the negative terminal 2 with the positive plate 3 and the negative plate 4 of method for laser welding with electrode.Then by the aperture on the lid, in hothouse, add electrolyte 6, and seal and make 3000 farads super capacitor.
Claims (5)
1. the ultracapacitor technology of a large-scale production, it is characterized in that: this preparation technology comprises:
(1) coating conduction basement membrane, i.e. A film:
The electrically-conducting paint for preparing is coated on the surface treated collector with coating machine, described coating machine is a notch board reticulate pattern dispense tip, and the coating machine oven temperature is 40～110 ℃, according to Gradient distribution at each section baking oven, the coating speed of coating machine is 5～80m/min, and coating weight is 2～10g/m
2, coating thickness is 4～12um, and the A film is the strip coating, and the line thickness error range of this coating is 0～1.5mm, and the A film is a double spread, and the line thickness error range of double spread is 0～1.5mm, and the resistance value of A film is less than 30m Ω;
(2) preparation composite conducting basement membrane, i.e. B film:
It is 40～90% that described B film contains the active carbon weight ratio, and containing the electrically conductive graphite weight ratio is 2～50%, and containing the binder wt ratio is 2～25%;
Active carbon is that among XC-72 and the GH-3892 one or both mix by arbitrary proportion, from Cabont company; Electrically conductive graphite is that among K56 and the AB-065M one or both mix by arbitrary proportion, from Timcal Graphite andCarbon company; Adhesive is a thermoplastics, can extrude the processing film forming, and adhesive is an ethylene-tetrafluoroethylene copolymer;
The B film is the mixed-powder that active carbon, electrically conductive graphite and three kinds of powder material of adhesive evenly form through dry powder blend, and dry powder blend is finished in high-speed mixer;
The B film is prepared by three roller plasticators, and the temperature range of the plasticating temperature of three roller plasticators is 300～500 ℃, and the time of plasticating is 10～120 minutes, and the length of prepared B film is 1～2000 meter, and thickness is 50～500um;
(3) dry method hot pressing power backup utmost point material:
Form through adding hot pressing by A film and B film, make the itemize electrode film by adhesive tape cutting machine itemize then;
(4) dry process electrode:
On the up-coiler with the itemize electrode film of two same sizes folder on barrier film be prepared from electrode, the fuse diameter of up-coiler is 5～200mm, the fuse height of coiling is 5～200mm;
(5) electrode is put into aluminum super capacitor shell, cover lid through the both positive and negative polarity of laser welding connection electrode, annotates electrolyte, seals and just makes ultracapacitor.
2. the ultracapacitor technology of a kind of large-scale production according to claim 1, it is characterized in that: the coating speed of described coating machine is 25～55m/min.
3. the ultracapacitor technology of a kind of large-scale production according to claim 1 and 2, it is characterized in that: the coating weight of described A film is 2.8～5.2g/m
2, coating thickness is 6～10um, and the A film is the strip coating, and the line thickness error range of coating is 0～0.5mm, and the A film is a double spread, the line thickness error range of double spread is 0.5mm.
4. the ultracapacitor technology of a kind of large-scale production according to claim 1, it is characterized in that: described B film contains active carbon weight ratio 60～80%, electrically conductive graphite weight ratio 10～20%, binder wt is than 10～20%.
5. according to the ultracapacitor technology of claim 1 or 4 described a kind of large-scale productions; it is characterized in that: described B film is prepared by three roller plasticators; the temperature range of the plasticating temperature of three roller plasticators is 320～380 ℃; the time of plasticating is 30～40 minutes; the length of prepared B film is 1000～2000 meters, and thickness is 100～250um.
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| CN102832052A (en) * | 2012-08-17 | 2012-12-19 | 常州华威电子有限公司 | Production line device and manufacture method of wound type supercapacitor |
| CN102846246A (en) * | 2012-08-31 | 2013-01-02 | 潘志刚 | Automatic liquid dropper of super capacitor |
| CN105609703B (en) * | 2015-12-25 | 2018-04-03 | 超威电源有限公司 | Integrated electrode and manufacture method |
| CN109076786B (en) * | 2018-10-26 | 2023-08-18 | 西安航空学院 | Simple semi-automatic fruit picking device |
| CN114613605A (en) * | 2020-12-04 | 2022-06-10 | 山东圣泉新能源科技有限公司 | Capacitor pole piece, preparation method thereof and super capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1317809A (en) * | 2000-04-12 | 2001-10-17 | 李永熙 | Super-grade capacitor for electrode of using new material and its mfg. method |
| US6804108B2 (en) * | 2000-05-12 | 2004-10-12 | Maxwell Electronics, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1317809A (en) * | 2000-04-12 | 2001-10-17 | 李永熙 | Super-grade capacitor for electrode of using new material and its mfg. method |
| US6804108B2 (en) * | 2000-05-12 | 2004-10-12 | Maxwell Electronics, Inc. | Electrochemical double layer capacitor having carbon powder electrodes |
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