CN1737964A - Use of pad printing in the manufacture of capacitors - Google Patents
Use of pad printing in the manufacture of capacitors Download PDFInfo
- Publication number
- CN1737964A CN1737964A CN 200410085570 CN200410085570A CN1737964A CN 1737964 A CN1737964 A CN 1737964A CN 200410085570 CN200410085570 CN 200410085570 CN 200410085570 A CN200410085570 A CN 200410085570A CN 1737964 A CN1737964 A CN 1737964A
- Authority
- CN
- China
- Prior art keywords
- substrate
- ink
- ruthenium
- active material
- capacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- Y02E60/522—
Landscapes
- Manufacture Or Reproduction Of Printing Formes (AREA)
Abstract
Deposition of a metal-containing reagent solution or suspension onto a conductive substrate by various pad-printing techniques is described. This results in a pseudocapacitive oxide coating, nitride coating, carbon nitride coating, or carbide coating having an acceptable surface area for incorporation into an electrolytic capacitor, such as one have a tantalum anode.
Description
Background of invention
1, invention field
The present invention relates generally to produce the equipment that chemical energy is converted to electric energy, relate in particular to the lining seal technology that on conductive substrate, is coated with electrode activity reagent solution or suspension.Preferably, for electrolytic capacitor, reagent solution or suspension are active material of cathode, such as containing ruthenium compound.Provide as printing-ink but contain ruthenium compound, comprise moisture or not aqueous carrier and stick, be preferably polymerized thylene carbonate hydrocarbon ester stick.The invention still further relates in the pressure electron tube metal anode of electrolytic capacitor polymerized thylene carbonate hydrocarbon ester is used as stick.
2, prior art
The electrode of band high-ratio surface area forms hundreds of μ F/cm
2Ratio electric capacity, this class electrode is suitable as anode in the electrochemical capacitor that requires high specific capacitance and/or the negative electrode in negative electrode and the electrolytic capacitor.
Male or female in the electrochemical capacitor or the negative electrode in the electrolytic capacitor generally comprise the substrate of a slice conducting metal such as titanium or tantalum, are furnished with pseudo-capacitance oxide coating, nitride coatings, carbonitride coating or carbide coating.In ruthenium-oxide negative electrode occasion, suspension or solution by coating ruthenium-oxide or its precursor such as ruthenic chloride or nitrosyl ruthenium nitrate on substrate form active material.Then the substrate of such coating is heated to the temperature that is enough to solvent evaporated, and suitable, change this precursor, on substrate, make the pseudo-capacitance film of the ruthenium-oxide of porous, high surface area.
Description of the Prior Art the methods that contact with the pseudo-capacitance reagent solution of various substrates.For example, people's such as people such as Shah and Muffoletto U.S. Patent No. 5,894,403,5,920,455,5,926,362,6,224,985,6,334,879 and 6,468,605 (transfer the assignee of the present invention entirely, and be included in here by reference) have been described and have been utilized supersonic spraying that conductive substrate coating is contained the ruthenium reagent solution.Than other all common technology, comprise infusion process, compressed air atomization and collosol and gel are at on-chip sedimentation, and supersonic spraying is a kind of improvement.Compare with the electrode that supersonic spraying is made, the capacitance of the electrode of these fabrication techniques of front is lower than electric capacity.And in view of the controllability and the reproducibility of infusion process, compressed air atomization and collosol and gel deposition technology, the utmost point is difficult to critically control the coating form, has directly influenced capacitance.Although the coating of ullrasonic spraying deposit generally has good form, there was the spraying problem in this technology, especially when active material is relatively costly, as ruthenium, can influence production cost.
Therefore, compare with other known depositing technics, though it is a kind of improvement that active agent solution is ejected on the substrate, can provide the energy storage ability qualified capacitor, still require further improvement the spray rate that manufactures a finished product of negative effect of very big mistake of being wasted.With lining seal technology active agent solution or suspension are applied on the conductive substrate, can improve the rate of manufacturing a finished product.
Summary of the invention
The present invention describes with various lining seal technology metallic reagent solution or suspension is deposited on the conductive substrate, pseudo-capacitance oxide coating, nitride coatings, carbonitride coating or carbide coating have been drawn thus, it is suitable that surface area that it is qualified and ullrasonic spraying obtain, but because of crossing spraying is not a problem, so improved rate of finished products.Other advantage comprises that coating layer thickness is even, adhesiveness is better, and when being stored in high temperature during accelerated life test, has kept long-term behaviour.
In lining seal technology, printing-ink comprises dissolving or fine being diffused in contains ruthenium reagent in the stable suspension.In either case, system all needs moisture or water-free carrier.Printing ink prints on the conductive substrate, and the latter removes slimicide through heating and solvent evaporated, sometimes reagent is converted to the ruthenium compound of expectation.Stick is the viscosity modifier of a kind of aid in treatment reagent ink and lining seal technology.After being heated to evaporating solvent, suitable, conversion contains ruthenium precursor, and required ruthenium coating is provided, and stays the residual carbon of minute quantity after stick is burnt.Residual carbon is crossed the performance that influences electrolytic capacitor at most.
In the tantalum powder of valve metal powder anode such as compression of dry-pressing, existing polymerized thylene carbonate hydrocarbon ester is also effective as stick.
Those skilled in the art can understand various purpose of the present invention more by reading the detailed description below in conjunction with accompanying drawing.
Brief description
Fig. 1 is the first embodiment schematic diagram that the present invention seals Prink ink cup lining printing apparatus 10, and the preceding seal plug 12 of circulation beginning, substrate 16, base plate 46 and reagent ink cup 54 are shown.
Fig. 2 is the schematic diagram of lining printing apparatus 10, and reagent ink 14 injects the groove 52 of base plate, seal plug contact printing ink.
Fig. 3 is the schematic diagram of lining printing apparatus 10, and the seal plug of last China ink vertically is positioned at substrate 16 tops.
Fig. 4 is the schematic diagram of lining printing apparatus 10, the seal plug contact substrate of last China ink.
Fig. 5 is the schematic diagram of lining printing apparatus 10 before the substrate of last China ink moves on to another processing step.
Fig. 6 goes up black substrate perspective view.
Fig. 6 A is a seal plug perspective view.
Fig. 7 is the schematic diagram that the present invention seals Prink ink cup lining printing apparatus 100 second embodiment, seal plug 12 is shown vertically is positioned at substrate 16 tops, and Prink ink cup 54 injects reagent ink the groove 102 of base plate 104 before the circulation beginning.
Fig. 8 is the schematic diagram of lining printing apparatus 100, and reagent ink 14 has injected bottom plate groove, and the seal plug vertically is positioned at the printing ink top.
Fig. 9 is the schematic diagram of lining printing apparatus 100, and Yin Sai picks up the printing ink in the bottom plate groove.
Figure 10 is the schematic diagram of lining printing apparatus 100, and the seal plug of last China ink vertically is positioned at the substrate top.
Figure 11 is the schematic diagram of lining printing apparatus 100, the seal plug contact substrate of last China ink.
Figure 12 is the schematic diagram of lining printing apparatus 100 before the substrate of last China ink moves to another processing step.
Figure 13 is the schematic diagram that the present invention seals Prink ink cup lining printing apparatus 110 the 3rd embodiment, seal plug 12 is shown vertically is positioned at above base plate 116 grooves 118 before the circulation beginning.
Figure 14 is the schematic diagram of lining printing apparatus 110, and reagent ink 14 has injected bottom plate groove, and the seal plug vertically is positioned at the printing ink top.
Figure 15 is the schematic diagram of lining printing apparatus 110, and Yin Sai is at the printing ink that picks up in the bottom plate groove.
Figure 16 is the schematic diagram of lining printing apparatus 110, and the seal plug of last China ink vertically is positioned at the substrate top.
Figure 17 is the schematic diagram of lining printing apparatus 110, the seal plug contact substrate of last China ink.
Figure 18 is the schematic diagram of lining printing apparatus 110 before the substrate of last China ink moves to another processing step.
Figure 19 is the schematic diagram that the present invention opens wide printing ink pond lining printing apparatus 200, and the preceding seal plug 12 of circulation beginning, substrate 16, base plate 202 and printing ink pond 206 are shown.
Figure 20 is the schematic diagram of lining printing apparatus 200, and reagent ink 14 is inserted 204 li of base plate 202 grooves by scraper plate, and unnecessary printing ink is removed by scraper 212.
Figure 21 is the schematic diagram of lining printing apparatus 200, seal plug 12 contact printing ink.
Figure 22 is the schematic diagram of lining printing apparatus 200, and the seal plug 12 of last China ink vertically is positioned at substrate 16 tops.
Figure 23 is the schematic diagram of lining printing apparatus 200, the seal plug 12 contact substrates 16 of last China ink.
Figure 24 is the schematic diagram of wheel transfer plate lining printing apparatus 300, reagent ink 14 that base plate drum 304 picks up 302 li in pond is shown passing to master rotor 306, and finally passes to the substrate that is positioned on the substrate wheel 308.
Figure 25 is the schematic diagram of wheel transfer plate lining printing apparatus 300, and reagent ink 14 just passes to master rotor 306 from base plate drum 304.
Figure 26 is the schematic diagram of wheel transfer plate lining printing apparatus 300, and reagent ink 14 has touched master rotor 306.
Figure 27 is the schematic diagram of wheel transfer plate lining printing apparatus 300, and reagent ink 14 just passes to substrate on the substrate wheel 308 from master rotor 306.
Figure 28 is the curve chart of drawing by the average energy that tantalum capacitor provides, and the lining seal ruthenium-oxide of capacitor cathode is heated to various final temperatures.
Figure 29 is that the weight of polypropylene carbonic ester stick is lost the relation curve with heating-up temperature.
Figure 30 is that the present invention serves as a contrast the X-ray diffraction scintigram that is heated to the ruthenium-oxide of various final temperatures behind the seal.
Figure 31 is heated to the average specific electric capacity that is coated with ruthenium-oxide titanium substrate of all temps and the curve chart of electrolytic capacitor imagination capacitance calculated value.
Figure 32 and 33 is coated on ruthenium-oxide on the titanium substrate He in the prior art with lining seal technology to be coated on the on-chip ruthenium-oxide backscatter images of titanium with supersonic spraying.
Figure 34 A and 34B are the XRF scintigrams of ruthenic oxide coating, and the former prints the technology deposit with the ullrasonic spraying rubbing method deposit of prior art, the latter with the printing ink pond lining of sealing.
The detailed description of preferred embodiment
With reference to describing the present invention containing the reagent ink deposit of active material or its precursor or being applied to on-chip various lining seal technology.Lining seal technology comprises with sealing Prink ink cup lining seal, opening wide the technology that printing ink pond lining prints and wheel transfer plate lining seal is carried out.
Referring now to accompanying drawing, Fig. 1 ~ 5 illustrate first embodiment of sealing Prink ink cup lining printing apparatus 10, and this example makes reagent solution or suspension printing ink 14 precisions and contacts substrate equably with seal plug 12 (Fig. 6 A).Substrate can be plane institution movement or formed parts, as box portion 16 (Fig. 6).Reagent ink solution or suspension are by moisture or aqueous carrier and organic stick are not formed.Suitable solvent comprises terpinol (boiling point=220 ℃), butyl carbitol (boiling point=230 ℃), cyclohexanone (boiling point=155.6 ℃), n-octanol (boiling point=171 ℃), 1,2-ethylidene glycol (boiling point=197 ℃), glycerine (boiling point=290 ℃) and water, these all are the high relatively solvents in junction point, do not evaporate under the room temperature, keep rheological characteristic or viscosity during printing.
But suitable salt and proliferation compound comprise nitrate, sulfate, halide, acetate and phosphate, can make active material, they are oxide, nitride, carbide or the carbonitride of column element down: ruthenium, cobalt, manganese, molybdenum, tungsten, tantalum, iron, niobium, iridium, titanium, zirconium, hafnium, rhodium, vanadium, osmium, palladium, platinum, nickel and lead.
The preferable reagent precursor of ruthenium oxide coatings is ruthenium halide, nitric acid ruthenium, ruthenium acetate or ruthenium sulfate or organic salt.This respect suitable precursor comprises the soluble salts of ruthenic chloride (III) hydrate, nitrosyl ruthenium (III) nitrate, nitrosyl ruthenium (III) acetate, nitrosyl ruthenium (III) sulfate and ammonium chlordene ruthenium (III).Physical efficiency can not be divided into two-phase with any ratio and above-mentioned solvent before these can mix.And ruthenic oxide and these solvents form dispersion, hinder to use precursor compound.
Reagent solution can comprise second kind or more kinds of metal, and second metal is oxide form or its precursor.Second kind of metal is selected from one or more in the following element and composition thereof: tantalum, titanium, nickel, iridium, platinum, palladium, gold, silver, cobalt, molybdenum, manganese, tungsten, iron, zirconium, hafnium, rhodium, vanadium, osmium, niobium.In a preferred embodiment of the present invention, the reagent solution that constitutes printing ink 14 comprises oxide or its precursor of ruthenium and tantalum.
The concentration of reagent ink 14 is preferably every liter of about 150 ~ 500 gram reagent compound.
No matter the material of substrate 16, the coating integrality mainly depends on the mechanical engagement with contact surface, thereby key is reasonably to prepare substrate 16 to guarantee coating quality.For example, the substrate surface cleannes are all very important in all coating systems, and this respect requires substrate 16 not to be operated the lubricating oil of equipment or people's contaminations such as hand perspiration.Substrate cleans and to comprise chemical method, and such as with conventional ungrease treatment moisture and not aqueous solution, those skilled in the art knows.Also can use the plasma cleaning method.
After the substrate surface cleaning, next the factor of most critical is a surface roughness when coating adheres to.Diapire 18 can be used the chemical method roughening, for example makes substrate and contains hydrofluoric acid and/or the hydrochloric acid of ammonium bromide with methyl alcohol etc. and contact; The utilization plasma etching; And mechanical means, as after scraping, machine work, iron wire brush, thick tapping, sandblast, the thick tapping again in conjunction with sandblast and cleaning, and grind such as the Scotch-Brite sand paper that substrate contact 3M company is made.
Wish, can before coating, improve the conductivity of substrate 16.The exposed surface of metal and metal alloy generally has natural oxide, and this is a kind of resistive layer, if with the substrate of this material as electrode for capacitors, preferably removes this oxide or makes it conduction before the deposit active coating thereon.For improving the conductivity of substrate 16, can use various technology.People's such as Muffoletto U.S. Patent No. 6,740,420 illustrates and has described a kind of this type of technology, and this patent has transferred the assignee of the present invention, is included in here by reference.
Sealing Prink ink cup lining printing apparatus 10 comprises main frame 22, has fixed vertical backbar 26 and cantilever 28 on its platform 24.One roughly c-shaped plate 30 is anchored on platform, vertical beam and cantilever with further supporting main frame.Seal plug 12 hangs from cantilever 28, and this arm is along vertical driving up and down relatively.
Piston rod 36 keeps the tight spacing relation with cylinder 42, critically controls the catenary motion axis and the attached seal plug 12 of plunger 34.Confinement plate 44 is anchored near the piston rod 36 the plunger 34, guarantees that plunger makes progress unlikelyly to shrink too much and impaired by C shape plate 30 and cantilever collision.
As shown in Figure 1, the sealing Prink ink cup printing process of first embodiment of the invention is positioned at piece 58 beginnings with substrate 16, and piece 58 heat conduction are bearing on the workbench 60.Workbench 60 is controlled temperature system preferably, and provides piece 58 motions.Like this, piece is passed to substrate 16 to heat, makes its temperature maintenance being to solidify, and is suitable, reagent ink is converted to the active material of expectation.Piece 58 also can remain on the environment of room temperature treatment.For describing this heating transfer process in more detail, can be with reference to aforesaid U.S. Patent No. 5,894,403,5,920,455,5,926,362,6,224,985,6,334,879 and 6,468,605.
Perhaps, the conductive substrate (not shown) that is not box portion is bearing on the heat-conducting block, at this moment, conductive substrate generally is the plane, touches box portion after being coated with the reagent ink that is converted to the curing activity material, as described in inciting somebody to action with reference to Figure 24 ~ 27 later on.
As shown in Figure 1, the seal circulation of the lining of first embodiment is positioned at retracted position with base plate 46 and begins, its groove 52 with directly aim at encircling 56 Prink ink cups 54 of making magnetic seal.
Among Fig. 2, base plate moves to left, make the reagent ink 14 of inserting groove 52 break away from Prink ink cup 54 fully and with seal plug 12 perpendicular alignmnet critically of withdrawal.Plunger 34 is driven and is moved seal plug 12 along downward direction then, and the lining portion 40 contact printing ink 14 of extension pick up printing ink 14 on its print surface.As previously mentioned, the lining portion 40 of extension has curved surface, prevents printing ink 14 sputters when helping seal plug 12 to move to contact with substrate.In this respect, seal plug 12 drives downwards, and 40 distortion enter groove 52 and pick up the reagent ink 14 that is deposited on the inside up to lining portion.
As shown in Figure 3, then base plate 46 withdrawals leave with substrate 16 vertical alignings in, last black seal plug 12 just contracts to lifting the position.The groove 52 of base plate 46 is aimed at Prink ink cup 54 once more, refills reagent ink inside.At this moment, workbench 60 is driven simultaneously and is moved into a certain position, and the heat-conducting block 58 of bearing substrate 16 is directly aimed at below the seal plug 12 of last China ink.
Among Fig. 4, it is moving to drive seal plug 12 along downward direction, makes substrate 16 diapires 18 touch the lining portion 40 of China ink on it.At this moment, 40 distortion of lining portion contact the zone that substrate diapire 18 is coated with reagent ink fully.The surface tension of reagent ink contact diapire 18 is greater than the surface tension of printing ink contact seal plug lining portion 40.Like this, when seal plug 12 moved into the retracted position of Fig. 5, reagent ink 14 just was deposited on the box portion diapire 18.Workbench 60 is its starting position of retraction also.
When reagent ink 14 deposited on the diapire 18 of substrate 16, heat-conducting block 58 and workbench 60 remain on substrate temperature to be enough to solvent is evaporated or disperses from the reagent mixture of deposition.In addition, can print at ambient temperature, desolvate and remove in the processing afterwards.Will describe in detail as following, the substrate of coating remakes independently heating steps, and precursor is converted to oxide, and the ions diffusion of deposition is gone into substrate, to obtain suitable joint or adhesion strength.This heating steps also wants heated substrate with evaporating solvent.
Like this, after box portion 16 coated reagent ink, the temperature of diapire 18 was enough to begin to disperse or the evaporating solvent material.Need, this can carry out at ambient temperature.Preferably, at the almost moment that contacts with reagent ink 14 evaporating solvent from substrate 16, thus the active material of cathode of deposition relative thin or the rete of its precursor.Under the situation of aqueous solution, substrate is heated to first temperature that is at least 100 ℃, flash evapn falls solvent from the reagent solution of deposition.More preferably, when deposited reagent printing ink, substrate is heated to first temperature up to 220 ℃, and the first higher temperature causes bigger evaporation rate of solvent.Film thickness be decided to be 1 micron or below.
Contain at the goods active material under the situation of compound of ru oxide, nitrate, sulfate, acetate, chloride or the phosphate precursor of deposition are heated to the temperature that is enough to burn stick and reagent ink is converted to porous, high surface pseudo-capacitance film.The typical case is 5 minutes to 6 hours heating time.
For example, in deposition and remove desolvate after, at least 5 minutes in 3 hours, the substrate that is coated with precursor is heated to 300 ~ 500 ℃ or the second preferable 350 ℃ temperature.In order almost completely to decompose and to burn stick in the pseudo-capacitance film, last heating-up temperature is preferable is at least 300 ℃.Remaining stick accessory substance can negative effect electric capacity.
The reagent precursor is converted to contains ru oxide, this is unique heating agreement.Once tried to form and contained ru oxide,, be more preferred from 350 ℃, lasted at least 5 minutes as long as last heating is at least 300 ℃ with stepping heating agreement.
Or after embryo deposit heating, the slow and stably temperature of oblique ascension substrate 16, for example 1 ℃/minute, preferably 6 ℃/minute, reach at least 300 ~ 500 ℃ until temperature, be more preferred from 350 ℃.Then substrate is kept a period of time under maximum temperature, be enough to make precursor to convert its conduct to and contain the last form of ru oxide, and be enough to make active material to diffuse into substrate 16.At 300 ℃, more preferably heated at least 5 minutes or bigger down at 350 ℃.
In another embodiment, for various purposes, the temperature of substrate 16 keeps to such an extent that be enough to that moment converts precursor to porous, high surface goods active coating on substrate.Especially when the precursors to deposit reagent ink, substrate temperature reaches 100 ~ 500 ℃, is preferably at least 200 ℃.Be more preferred from 300 ℃, also wanting good is 350 ℃, so that precursor moment is converted to required goods.For guaranteeing that conversion fully and stick burn, coating is heated a period of time in addition again.
The decomposition temperature of aforesaid poly-(ethylene carbonate) stick is 220 ℃, and poly-(propylene carbonate) stick is 250 ℃.Therefore, minimum last heating-up temperature must surpass these temperature, with the non-toxic by-products that guarantees stick is burnt till main carbonated and water fully.
Precursor deposition and convert the goods active coating to after, no matter whether moment take place, all to be cooled to ambient temperature to substrate 18 gradually and remain in the depositing temperature of heating, strengthening bond strength, or by the specific distribution curvilinear motion.Generally speaking, preferably in substrate and heating when air or oxygen-containing gas contact.
Contain under the situation of ru oxide producing porous, the thickness of the coating that obtains is preferably hundreds of dusts to 0.1 millimeter or bigger.The inner surface area of porous coating is 1 ~ 1500 meter
2/ gram.And the diameter of the most of particle of porous coating is all less than 500 nanometers.
Though not shown, the substrate 16 that will go up China ink takes off from the workbench 60 of heat-conducting block 58 with heating, is reprocessed into the electric energy memory device, as capacitor.Then, second substrate located repetitive cycling on heat-conducting block.
Fig. 7 ~ 12 illustrate second embodiment of sealing Prink ink cup of the present invention lining printing apparatus 100, and this equipment comprises many with the same element of the equipment described with reference to Fig. 1 ~ 5 10, and these parts are with same label.
As shown in Figure 7, sealing Prink ink cup lining printing apparatus 100 comprises main frame 22, and its platform 24 is fixed in the vertical beam 26 of supporting extension arms 28.In this example, seal plug 12 not only drives up and down, and cantilever 28 moves forward and backward relatively, but the base plate that this example need not back and forth drive, but Prink ink cup 54 back and forth drives.Therefore Fig. 7 illustrates the Prink ink cup 54 of aiming at static base plate 104 grooves 102, deposits a reagent ink 14 inside.Seal plug 12 is in retracted position, vertical substrate 16 tops that are bearing on substrate 58 and the workbench 60 that are aligned in.
Among Fig. 8, Prink ink cup 54 leaves its groove 102 along base plate 104 withdrawals, and a reagent ink 14 of deposition has been loaded in the inside.Similarly, seal plug 12 along cantilever 28 move with Prink ink cup 54 along static base plate 104 mobile phases with distance, the vertical top that is positioned at the reagent ink 14 that is deposited on 102 li of bottom plate grooves now.
Figure 13 ~ 18 illustrate the 3rd embodiment that the present invention seals Prink ink cup lining printing apparatus 110, this equipment comprise many with respectively with reference to Fig. 1 ~ 5 and 7 ~ 12 equipment 10 and the 100 same elements of describing, so the same label of same parts employing.
Especially as shown in figure 13, lining printing apparatus 110 comprises the main frame 112 of supporting plunger 34 and piston rod 36 shells 114, and plunger 34 and piston rod 36 can drive up and down along cylinder 42.Confinement plate 44 guarantees that plunger 34 was not upwards withdrawn far and collision shell 114, and seal plug 12 utilizes liner plate 32 to be anchored on plunger 36 ends removably.
As shown in figure 15, bottom plate groove 118 has been filled after reagent ink 14 and Prink ink cup 54 move on to the position that breaks away from seal plug 12, and plunger 34 promptly drives downwards, and this moves down Yin Sai and contacts base plate 116, reagent ink 14 is picked up in the lining portion 40 of its extension.Then, the seal of last China ink is filled in 12 retraction lift units.Then, seal plug 12 drives forwards, and with substrate 16 vertical alignings the on the workbench 60 that is bearing in heat-conducting block 58 and heating, this location is shown in Figure 16.
Figure 17 illustrates the seal plug 12 that drives contact substrate 16 downwards, 40 distortion of lining portion, and contact will be coated with the zone of the box diapire 18 of reagent ink fully.Like this, when seal plug 12 moved into the retracted position of Figure 18, reagent ink 14 was deposited on the box diapire 18.Then, the substrate 16 of last China ink takes off from the workbench 60 of heat-conducting block 58 and heating, is reprocessed into the electric energy memory device.Second substrate is positioned on the heat-conducting block, when Prink ink cup 54 and seal 56 when base plate 116 runs to position shown in Figure 13, the groove 118 that base plate is 116 li critically loads reagent ink 14 again.12 recirculation of seal plug are picked up printing ink as previously mentioned and it are deposited on the aforesaid substrate.
Like this, the circulation of lining printing apparatus 110 does not finish, and passes base plate 116 up to Prink ink cup 54 and moves back and forth, all loads groove 118 at every turn.This helps Prink ink cup 54, and 116 each motions form the upward circulation timei of the substrate of China ink through base plate.
Figure 19 ~ 23 illustrate another embodiment of the present invention, and it has used unlimited printing ink of the present invention pond lining printing apparatus 200.Open wide printing ink pond lining printing apparatus 200 and comprise the base plate 202 of being with groove 204 and the printing ink pond 206 that contains reagent ink 14.It is vertical that what be contained in base plate 202 tops is backbar 208, it for seal plug 12, isolate offset plate 210 and scraper 212 provides vertical translation.Isolate offset plate by connecing backbar with first overarm 214 that can drive pivot member 216.The bar 220 that auxiliary arm 218 can dock pivot member 216 moves axially.Second can drive pivot member 222 is positioned at supplementary wall 218 far-ends and supporting isolation offset plate 210, contacts and does not contact with base plate 202 by rotatablely moving.
Horizontal beam 224 connects down overarm 214, and scraper 212 is bearing in horizontal beam 224 far-ends with the pivot rotation mode.But actuating arm 226 is connected between backbar 208 and the auxiliary arm 218, scraper 212 is critically pivoted and contacts and does not contact with base plate 202.
As shown in figure 19, use the lining seal circulation of opening wide printing ink pond printing equipment 200, from a certain amount of reagent ink 14 being inserted the pond 206 that is positioned at base plate 202.Isolate offset plate 210 and pass printing ink pond 206, a certain amount of reagent ink 14 is moved on on the upper surface of base plate 202, when the isolation offset plate moved to left, reagent ink 14 just flowed into groove 204.After groove was filled with, scraper 212 is travelling backwards to the right on groove, and unnecessary reagent ink 14 is scraped into printing ink pond 206, so just the correct reagent ink of quantity was injected groove 204.
Among Figure 21, isolation offset plate 210 is pivoted into scraper 212 and does not contact base plate 202, this Wear.Among the figure, seal plug 12 also moves down, thereby lining portion 40 contact reagent inks 14 that extend and it is picked up on its print surface, and what the seal plug 12 withdrawal immigrations of going up China ink then were located immediately at substrate 16 tops lifts position (Figure 22).Seal plug 12 shown in Figure 23 drives downwards and contacts substrate diapires 18 together with lining portion black on it 40.Because the distortion of lining portion, it contacts the zone that substrate 16 will be coated with reagent ink thereon fully.As previously mentioned, heat-conducting block 58 and workbench 60 remain on desired temperatures with substrate.Then, the workbench 60 of the substrate 16 of last China ink from heat-conducting block 58 and heating taken off, be reprocessed into the electric energy memory device.Second substrate is contained on the heat-conducting block, repeats this circulation.
Figure 24 ~ 27 illustrate another embodiment of wheel transfer plate lining printing apparatus 300, and this equipment comprises the printing ink pond 302 that contains reagent ink, base plate 304, master rotor 306 and the substrate runner 308 of rotary drum form.Though not shown among the figure, runner 308 supporting polyliths are processed to the substrate of electric energy memory device of the present invention later on.
Among Figure 25, main drum 306 has moved into contact base plate drum 304.Main drum 306 is equipped with the best release contact surface 306A that is made of silicone, and reagent ink 14 is delivered on it, from base plate as shown in figure 26.The substrate runner 308 of rotation moves into the main drum 306 of contact, and reagent ink 14 is deposited on the substrate (not shown) that loads on it.In this example, substrate is a panel-like member, makes Overheating Treatment as previously mentioned, is bearing in then on the diapire 18 of substrate 16, shown in former width of cloth figure.
The anode of electrolytic capacitor generally is made of coccoid valve metal, be selected from tantalum, aluminium, titanium, niobium, zirconium, hafnium, tungsten, molybdenum, vanadium, silicon and germanium and composition thereof are coccoid, its way be Powdered valve metal for example the tantalum powder be pressed into pellet shapes, therefrom stretch out anode tap, under vacuum with the high temperature sintering bead.Preferably, be preferably poly-(alkylene carbonate) promotion and suppress the bonding of powder with aforementioned a kind of stick.Stick has increased not sintering strength to press body, is beneficial to powder and flows before compacting.To tantalum, available electron bundle melting process or sodium reduction prepared powder, this is that those skilled in the art know.
No matter with which kind of PROCESS FOR TREATMENT valve metal powder, the valve metal powder structure of compacting is the tantalum bead particularly, generally generate in the electrolyte at tunicle and arrived required voltage by anodic oxidation, tunicle generates electrolyte and comprises ethylene glycol or polyethylene glycol, deionized water and H
3PO
4, its conductance is 250 ~ 2600 μ S/cm (40 ℃).It is H that another kind of main tunicle generates electrolyte
3PO
4Aqueous solution, its conductance is up to 20000 μ S/cm (40 ℃).Anodic oxidation is inserted electrolyte to the hole of the valve metal body of compacting, forms continuous dielectric oxide film on sintered body.Anodic oxidation produces oxide skin(coating) on terminal lead/anode tap solder joint.
The anode also aluminium or the titanium body of the aluminium of useful etch or titanium foil or sintering constitutes.
The separating layer structure of being made up of an insulating material between anode and the negative electrode prevents internal electric short circuit between electrode.Separating layer material and anode and active material of cathode be chemically reactive not, and these two kinds of active materials and electrolyte be chemically reactive and not dissolving not.In addition, in the electro-chemical reaction process of capacitor, the porosity of separating layer material is enough to allow electrolyte flow through.Exemplary separating layer material comprises: the polyolefine fabric of braiding and nonwoven, contain polypropylene and polyethylene, perhaps fluorine-contained polymerisate fibre comprises poly-PVF, polyethylene-tetrafluoroethene (polyethylenetetrafluovoethylene) and the polyethylene-trifluoro-ethylene (polyethylenechlorotrifluouoethylene) stacking or overlapped polyolefin or fluoropolymer microporous barrier compiled; Non-woven glass cloth, glass fiber material and ceramic material.Suitable microporous barrier comprises the barrier film (C.H.Dexter Div., Dexter company) that brand is the polyethylene barrier film (DMS Solutech) of SOLUPOR, polytetrafluoroethylene (Polytetrafluovoethylene) barrier film (Chemplast company) that brand is ZITEX, brand is CELGARD polypropylene diaphragm (Celanese Plastic company) and brand are DEXIGLAS.Generally be used for being included in the scope of the present invention in the capacitor based on cellulosic separating layer.Electrolyte according to using can deal with to improve its wettability separating layer.
Utilization is by the electrolyte in the electrolyte injection opening injection shell, and anode and negative electrode are interrelated.Any specific anode and the known electrolyte that active material of cathode uses that qualified capacitive property is provided in being chosen in the desired operation scope all is included in the scope of the present invention.Suitable electrolyte is included in the sulfuric acid in the aqueous solution.Specifically, under up to 125 volts voltage, 38% sulfuric acid solution is functional.Known 10 ~ 20% phosphoric acid/aqueous solution can improve equivalent series resistance (ESR) and puncture voltage.People's such as Shah United States Patent (USP) NO.6,219,222 and people's such as Liu NO.6,687,117 have all described other suitable electrolyte, and these patents have transferred the assignee of the present invention, are included in here by reference.
Following case description serves as a contrast the capacitor that seal technology is made with the present invention, and has proposed optimal mode by the present inventor.
Example I
The 150 piece titanium substrates as box portion similar to substrate in the accompanying drawing 16 are coated the ruthenic oxide active material with sealing oil ink reservoir lining seal technology of the present invention.Printing ink is ruthenic oxide and the polyvinyl butyral resin stick suspension in terpinol and the butyl carbitol solvent mixture.Then the substrate of coating is divided into three groups, 50 every group.First group is heated to 200 ℃ of maximum temperatures, and second group is heated to 300 ℃, and the 3rd group is heated to 400 ℃.
Constitute test capacitor by the cathode substrate of handling, each capacitor comprises compacting and the anodised tantalum powder anode that cooperates between the box portion two, and box portion comprises the ruthenium-oxide cathode that is heated to same end temperature.Electrolyte injects seal box and contacts anode and negative electrode, and anode and negative electrode are spaced from each other with separating layer.Form three group capacitors thus, 25 every group.Every 14 days each capacitor is charged to 215 volts and 16.5 ohmic resistors are discharged.During this period, they are deposited in 85 ℃.
Figure 28 is a certain group of curve chart that average energy constituted that each capacitor provides.Particularly, curve 400 is the mean value that negative electrode is heated to 200 ℃ capacitor, and curve 402 is the mean value that negative electrode is heated to 300 ℃ capacitor, and curve 404 is the mean value that negative electrode is heated to 400 ℃ capacitor.Obviously, aspect the energy efficiency of capacitor, the last heating-up temperature of the ruthenium-oxide cathode material of lining seal is very important.Deeply convince that 300 ℃ is the temperature that poly-(propylene carbonate) stick is decomposed into harmless carbon dioxide and water fully.
Example II
The loss in weight of poly-(alkylene carbonate) stick of the curve representation of Figure 29 and the relation of heating-up temperature.Curve 410 is made of the stick that heats in the air, and curve 412 is made of the stick that heats in the hydrogen, and curve 414 is made of the stick of (1 torr) heating in the vacuum, and curve 416 is made of the stick that heats in the nitrogen.As can be seen, the loss in weight nearly all occurs in before 300 ℃ of heating.
Example III
The substrate that the same quadrat method lining that uses with body plan example I three group capacitors prints is heated to 250 ℃, 300 ℃, 350 ℃ and 450 ℃ respectively, does X-ray diffraction (XRD) analysis then, the results are shown in Figure 30.The degree of crystallinity of this XRD curve representation ruthenium-oxide active material, the material of many crystallizations is represented at higher peak.Obviously, be heated to the crystallization of ruthenium-oxide material of 250 ℃ of end temperatures not as being heated to other material of higher temperature.
Example IV
Occasion for the coating substrate being applied to ultra-capacitor (metal oxide such as ruthenic oxide are as the two capacitor of negative electrode and positive plate) importantly makes than electric capacity to reach maximum.But for the coating ruthenium-oxide substrate in the electrolysis mixed capacitor as the occasion of negative electrode, such as the capacitor of the tantalum powder anode with compacting, this point is unimportant, because anode has been arranged systematic function.
Suppose that the tantalum anode of the electrolytic capacitor of formation has the capacitor C a of 1mF, negative electrode contains 2.7178 milligrams of ruthenic oxides, and this quality draws cathode capacitance Cc=1mF under 250 ℃.This electrolytic capacitor can be modeled as the system that anode is connected with the cathodic electricity container, and available formula C=Ca * Cc/ (Ca+Cc) calculates the electric capacity that this electrolytic capacitor draws.The curve 420 of Figure 31 is electric capacity calculated values of this imagination electrolytic capacitor.
The capacitor that constitutes comprises the substrate of implementing the same method lining seal of I capacitor with body plan, and negative electrode is heated to Figure 31 abscissa temperature indicative.It is undisputable fact that electric capacity descends under higher anneal temperature.The curve 422 of Figure 31 is pointed out the temperature dependence of the electric capacity of these electrolytic capacitors based on the negative electrode annealing temperature, and this is the bar horizontal line in essence.Illustration is an amplification diagrammatic sketch, shows that this example replaces 250 ℃ with 350 ℃ of temperature, and total capacitance is reduced to 0.996F by 0.999F, reduces 0.3%.Most of electrolytic capacitors are only used a small amount of cathode material, can compensate the unoptimizable electric capacity that compares with more active material of cathode.
Example V
Substrate with the same method lining seal of the capacitor of body plan example I is heated to 350 ℃, remakes the impact shock test.Vibration test comprises with following grade makes random vibration to capacitor along each of three normal axis: 10Hz:0.03G2/Hz, 40Hz:0.03G2/Hz, 500Hz:0.003G2/Hz, every axle 1 hour.Shock test comprises uses the illusory weight that is equivalent to test unit weight that capacitor is added shock pulse, and this shock pulse is that 250 grams continue 1 millisecond.Capacitor is done three times with the both direction of three normal axis and is impacted (amounting to 18 times impacts).
Figure 32 illustrates the backscatter images of the substrate that takes off from capacitor, it and the backscatter images of the capacitor of similar manufacturing shown in Figure 33 photograph in pairs, and the latter's negative electrode is by according to aforesaid U.S. Patent No. 5,894,403,5,920,455,5,926,362,6,224,985,6,334,879 and 6,468,605 hot sprayings are formed to the on-chip nitrosyl ruthenium nitrate of titanium precursor.The last heating-up temperature of this comparison substrate is 350 ℃.Among Figure 33, the dark space is the titanium substrate, and the light color district is the ruthenium-oxide material.Obviously, most of ruthenium-oxide material can not adhere to substrate and come off.On the contrary, the substrate of the present invention of Figure 32 shows that ruthenium-oxide after the impact shock test, still keeps adhering to fully the titanium substrate.
Example VI
Figure 34 A and 34B illustrate the XRF figure (XRF) of two ruthenium oxide layer.The former is by pressing aforesaid U.S. Patent No.5,894,403,5,920,455,5,926,362,6,224,985,6,334,879 and 6, the nitrosyl ruthenium nitrate of 468,605 ullrasonic spraying deposits is made after heating converts the goods ruthenium-oxide to, and the latter's the scintigram sealing oil ink reservoir method of using by oneself is made the ruthenium oxide layer of lining seal.In each occasion, the XRF signal strength signal intensity all is proportional to the thickness of ruthenic oxide layer.The topographic map (Figure 34 A) of the ruthenic oxide layer thickness that ultrasonic spraying process produces changes to 3.85 of utmost point light gray portion from 1.2 of peripheral utmost point dark space, and reaches 4.88 of dark-grey portion of scanning center.Thickness distribution is a chevron, and range of readings is 1.20 ~ 4.88.
Under the contrast, the signal strength signal intensity of the titanium dioxide of lining seal nail coating is much even, and utmost point light gray shadow region is corresponding to maximum signal 3.90, they signal strength signal intensity be 3.60 a large amount of in the top on grey highland.Some paddy (dark-grey) is 3.30.About 90% lining seal surface has 3.30 ~ 3.90 signal strength signal intensity, differ with the highland average height ± 10%.As can be seen, signal only drops to 2.40 at extremely outlying place, and peak height reaches 4.50.
Therefore, oxide coating, nitride coatings, carbonitride coating or the carbide coating of lining seal technology of the present invention by pseudo-capacitance is provided obviously reached its various purposes.The thickness of this type coating is even, adheres to preferablely, when accelerated aging test, preserve and can keep long-term behaviour in high temperature, qualified surface area and supersonic spraying obtain quite, but rate of finished products has improved.
Those skilled in the art obviously knows, can make various corrections and without prejudice to appended scope of the present invention as the claim defined to innovative idea described herein.
Claims (42)
1, a kind of capacitor is characterized in that comprising:
A) anode
B) comprise the negative electrode of active material of cathode, described active material of cathode is characterized by the reagent ink of transferring to conductive substrate from print pad; With
C) electrolyte of contact anode and negative electrode.
2, capacitor as claimed in claim 1, wherein reagent ink comprises active material of cathode or its precursor that is dissolved or suspended in the solvent.
3, capacitor as claimed in claim 2, wherein solvent is selected from terpinol, butyl carbitol, cyclohexanone, n-octanol, ethylidene glycol, glycerine, water and composition thereof.
4, capacitor as claimed in claim 1, wherein the stick that comprises of reagent ink be selected from ethyl cellulose, acrylic resin, polyvinyl alcohol, polyvinyl butyral resin and general molecular formula be R-O-C (=O)-O, wherein poly-(alkylene carbonate) of R=C1 ~ C5.
5, capacitor as claimed in claim 4, wherein stick is poly-(ethylene carbonate) or poly-(propylene carbonate).
6, capacitor as claimed in claim 1, wherein first metal that comprises of active material of cathode is selected from ruthenium, cobalt, manganese, molybdenum, tungsten, tantalum, iron, niobium, iridium, titanium, zirconium, hafnium, rhodium, vanadium, osmium, palladium, platinum, nickel and lead.
7, capacitor as claimed in claim 1, wherein second metal that comprises of active material of cathode is selected from tantalum, titanium, nickel, iridium, platinum, palladium, gold, silver, cobalt, molybdenum, manganese, tungsten, iron, zirconium, hafnium, rhodium, vanadium, osmium, niobium and composition thereof.
8, capacitor as claimed in claim 1, wherein print pad is selected from sealing Prink ink cup lining printing apparatus, opens wide printing ink pond lining printing apparatus and wheel transfer plate lining printing apparatus.
9, capacitor as claimed in claim 1, wherein negative electrode comprises the active material of cathode that contacts conductive substrate, and conductive substrate is selected from titanium, molybdenum, tantalum, niobium, cobalt, nickel, stainless steel, tungsten, platinum, palladium, gold, silver, copper, chromium, vanadium, aluminium, zirconium, hafnium, zinc, iron and alloy thereof.
10, capacitor as claimed in claim 9, wherein conductive substrate is the plane.
11, capacitor as claimed in claim 9, wherein conductive substrate is a box portion.
12, a kind of reagent ink that contacts substrate with the electrode of formation electric energy memory device is characterized in that described reagent ink comprises:
A) active material;
B) be used for the solvent of this active material; With
C) stick.
13, reagent ink as claimed in claim 12, wherein active material is oxide, nitride, carbide or the carbonitride of first metal, and first metal is selected from ruthenium, cobalt, manganese, molybdenum, tungsten, tantalum, iron, niobium, iridium, titanium, zirconium, hafnium, rhodium, vanadium, osmium, palladium, platinum, nickel and lead.
14, reagent ink as claimed in claim 12, wherein solvent is selected from terpinol, butyl carbitol, cyclohexanone, n-octanol, ethylidene glycol, glycerine, water and composition thereof.
15, reagent ink as claimed in claim 12, wherein stick be selected from ethyl cellulose, acrylic resin, polyvinyl alcohol, polyvinyl butyral resin and general molecular formula be R-O-C (=O)-O, wherein poly-(alkylene carbonate) of R=C1 ~ C5.
16, reagent ink as claimed in claim 15, wherein stick is poly-(ethylene carbonate) or poly-(propylene carbonate).
17, reagent ink as claimed in claim 12, wherein active material is dissolved in the solvent.
18, reagent ink as claimed in claim 12, wherein active material is suspended in the solvent.
19, reagent ink as claimed in claim 12, wherein active material is the ruthenium in the solvent, form is ruthenium-oxide or a kind of precursor, and precursor is selected from ruthenic chloride (III) hydrate, nitrosyl ruthenium (III) nitrate, nitrosyl ruthenium (III) acetate, nitrosyl ruthenium (III) sulfate and ammonium chlordene ruthenium (III).
20, a kind of method that is provided for the electrode of electric energy memory device is characterized in that comprising step:
A) provide substrate;
B) provide and contain active material, the reagent ink of solvent and stick;
C) reagent ink is made electrode by lining seal technology contact substrate; With
D) in the electric energy memory device, use this electrode.
21, method as claimed in claim 21, wherein substrate is selected from titanium, molybdenum, tantalum, niobium, cobalt, nickel, stainless steel, tungsten, platinum, palladium, gold, silver, copper, chromium, vanadium, aluminium, zirconium, hafnium, zinc, iron and alloy thereof.
22, method as claimed in claim 21, wherein active material is oxide, nitride, carbide or the carbonitride of first metal, and first metal is selected from ruthenium, cobalt, manganese, molybdenum, tungsten, tantalum, iron, niobium, iridium, titanium, zirconium, hafnium, rhodium, vanadium, osmium, palladium, platinum, nickel and lead.
23, method as claimed in claim 21, wherein solvent is selected from terpinol, butyl carbitol, cyclohexanone, n-octanol, ethylidene glycol, glycerine, water and composition thereof.
24, method as claimed in claim 21, wherein stick is poly-(alkylene carbonate), general molecular formula is R-O-C)=O)-O, wherein R=C1 ~ C5.
25, method as claimed in claim 24, wherein poly-(alkylene carbonate) is poly-(ethylene carbonate) or poly-(propylene carbonate).
26, method as claimed in claim 21, wherein active material is dissolved in the solvent.
27, method as claimed in claim 21, wherein active material is suspended in the solvent.
28, method as claimed in claim 21, wherein active material is the ruthenium in the solvent, form is ruthenium-oxide or a kind of precursor, and precursor is selected from ruthenic chloride (III) hydrate, nitrosyl ruthenium (III) nitrate, nitrosyl ruthenium (III) acetate, nitrosyl ruthenium (III) sulfate and ammonium chlordene ruthenium (III).
29, method as claimed in claim 21, wherein print pad is selected from sealing Prink ink cup lining printing apparatus, opens wide printing ink pond lining printing apparatus and wheel transfer plate lining printing apparatus.
30, method as claimed in claim 21, wherein substrate is the plane.
31, method as claimed in claim 21, wherein substrate is a box portion.
32, method as claimed in claim 21 is characterized in that, substrate is provided when being included in reagent ink contact substrate at ambient temperature.
33, method as claimed in claim 21 is characterized in that, when being included in reagent ink contact substrate substrate is heated to above ambient temperature.
34, method as claimed in claim 21 is characterized in that, when being included in reagent ink contact substrate substrate is heated to 300 ~ 500 ℃ maximum temperature.
35, method as claimed in claim 21 is characterized in that, is included in behind the substrate contact reagent ink maximum temperature that substrate is heated to 300 ~ 500 ℃.
36, method as claimed in claim 21 is characterized in that, comprise the maximum temperature that substrate is heated to 350 ℃, and reagent ink contacts with it.
37, a kind of for the electric energy memory device provides the method for electrode, it is characterized in that comprising step:
But a) prepare the metal of conduct flowing powder;
B) this granulated metal is mixed with stick;
C) granulated metal and stick are pressed into a formed body; With
D) be heated into body to decompose stick basically.
38, method as claimed in claim 37, it is characterized in that, the oxide that provides as first metal is provided, the active material of nitride, carbide or carbonitride, and first metal is selected from ruthenium, cobalt, manganese, molybdenum, tungsten, tantalum, iron, niobium, iridium, titanium, zirconium, hafnium, rhodium, vanadium, osmium, palladium, platinum, nickel and lead.
39, method as claimed in claim 37, it is characterized in that, comprise the selection stick, described stick be selected from ethyl cellulose, acrylic resin, polyvinyl alcohol, polyvinyl butyral resin and general molecular formula be R-O-C (=O)-O, wherein poly-(alkylene carbonate) of R=C1 ~ C5.
40, method as claimed in claim 37 is characterized in that, comprises that autohemagglutination (ethylene carbonate) or poly-(propylene carbonate) select stick.
41, method as claimed in claim 37 is characterized in that, also comprises the formed body that anodic oxidation is obtained by step d).
42, method as claimed in claim 37 is characterized in that, the electrode that provides as capacitor tantalum body is provided.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/920,942 US7116547B2 (en) | 2003-08-18 | 2004-08-18 | Use of pad printing in the manufacture of capacitors |
| US10/920,942 | 2004-08-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1737964A true CN1737964A (en) | 2006-02-22 |
Family
ID=36080726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410085570 Pending CN1737964A (en) | 2004-08-18 | 2004-10-14 | Use of pad printing in the manufacture of capacitors |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1737964A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101484988B (en) * | 2006-07-05 | 2012-08-08 | 亚利桑那董事会，代理并代表亚利桑那州立大学的法人团体 | Method of temporarily attaching a rigid carrier to a substrate |
| CN102653164A (en) * | 2011-03-04 | 2012-09-05 | 深圳富泰宏精密工业有限公司 | Rubber head structure and pad printing machine thereof |
| CN106965546A (en) * | 2017-04-10 | 2017-07-21 | 益阳阳光电子科技有限公司 | A kind of automatic splicing equipment of aluminum electrolytic capacitor casing inker and its tape splicing method |
| CN107851510A (en) * | 2015-08-12 | 2018-03-27 | 株式会社村田制作所 | Capacitor |
-
2004
- 2004-10-14 CN CN 200410085570 patent/CN1737964A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101484988B (en) * | 2006-07-05 | 2012-08-08 | 亚利桑那董事会，代理并代表亚利桑那州立大学的法人团体 | Method of temporarily attaching a rigid carrier to a substrate |
| CN102653164A (en) * | 2011-03-04 | 2012-09-05 | 深圳富泰宏精密工业有限公司 | Rubber head structure and pad printing machine thereof |
| CN107851510A (en) * | 2015-08-12 | 2018-03-27 | 株式会社村田制作所 | Capacitor |
| CN107851510B (en) * | 2015-08-12 | 2019-06-14 | 株式会社村田制作所 | Capacitor |
| CN106965546A (en) * | 2017-04-10 | 2017-07-21 | 益阳阳光电子科技有限公司 | A kind of automatic splicing equipment of aluminum electrolytic capacitor casing inker and its tape splicing method |
| CN106965546B (en) * | 2017-04-10 | 2023-02-07 | 益阳阳光电子科技有限公司 | Automatic tape splicing device of aluminum electrolytic capacitor sleeve printer and tape splicing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7244279B2 (en) | Use of poly(alkylene) carbonates in the manufacture of valve metal anodes for electrolytic capacitors | |
| US20080013257A1 (en) | Poly(Alkylene) Carbonates As Binders In The Manufacture Of Valve Metal Anodes For Electrolytic Capacitors | |
| CN1210736C (en) | Solid electrolytic condenser and manufacture method thereof | |
| EP1829686A2 (en) | Method of pad printing in the manufacture of capacitors | |
| US20080007894A1 (en) | Poly (Alkylene) Carbonates As Binders In The Manufacture Of Valve Metal Anodes For Electrolytic Capacitors | |
| CN1291420C (en) | Conductive material using carbon nano-tube, and manufacturing method thereof | |
| CN100350651C (en) | Anode compositions having an elastomeric binder and an adhesion promoter | |
| EP2613389A1 (en) | Air electrode for lithium air battery and method of making the same | |
| CN1309513C (en) | Tantalum and tantalum nitride powder mixtures for electrolytic capactitors substrates | |
| CN1875516A (en) | Electrolyte sheet with protruding features having undercut angles and method of separating such sheet from its carrier | |
| US20050090108A1 (en) | High capacitance electrode and methods of producing same | |
| JP2005294832A (en) | Forming method of electrode structure useful for energy storage device | |
| EP1789982A2 (en) | Methods and apparatus for producing carbon cathodes | |
| CN1617954A (en) | Deposition method for nanostructure materials | |
| CN1871378A (en) | Deposition method for nanostructure materials | |
| CN1992110A (en) | Solid electrolytic capacitor element, solid electrolytic capacitor, and manufacturing method thereof | |
| CN1793438A (en) | Anode oxidating electrolysing liquid under inhibiting arc state of magnesium alloy and process for anode oxidating | |
| AU750036B2 (en) | Paste for producing sintered refractory metal layers, notably earth acid metal electrolytic capacitors or anodes | |
| CN1737964A (en) | Use of pad printing in the manufacture of capacitors | |
| EP0032754B1 (en) | Porous nickel coated electrodes, process for making same and a paste composition used in said process | |
| CN101047068A (en) | Solid electrolytic capacitor | |
| CN104025221A (en) | Distortion-free screen-printed anodes on ta/nb sheet | |
| Kandasamy et al. | Facile one-pot synthesis of flower like cobalt oxide nanostructures on nickel plate and its supercapacitance properties | |
| CN1307143A (en) | Method and device for producing film | |
| CN1280852C (en) | Solid electrolytic capacitor making process and apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |