CN1127771C - Energy storage device and methods of manueacture - Google Patents

Energy storage device and methods of manueacture Download PDF

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Publication number
CN1127771C
CN1127771C CN93119348A CN93119348A CN1127771C CN 1127771 C CN1127771 C CN 1127771C CN 93119348 A CN93119348 A CN 93119348A CN 93119348 A CN93119348 A CN 93119348A CN 1127771 C CN1127771 C CN 1127771C
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Prior art keywords
electrode
coating
precast segment
dry type
capacitor
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CN93119348A
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CN1096611A (en
Inventor
罗伯特·R·唐
詹姆斯·M·鲍普莱特
阿兰·B·迈克伊沃
格雷·E·马森
马克·L·古德温
K·C·萨尔
罗纳德·L·安德森
詹姆斯·P·尼尔森
道格拉斯·克罗迈克
大卫·吴
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Polytron Technologies Inc
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PACIFIC XINFU SCIENCE AND TECHNOLOGY Co Ltd
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Priority claimed from US07/947,414 external-priority patent/US5384685A/en
Priority claimed from US07/947,294 external-priority patent/US5464453A/en
Application filed by PACIFIC XINFU SCIENCE AND TECHNOLOGY Co Ltd filed Critical PACIFIC XINFU SCIENCE AND TECHNOLOGY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • H01M10/0418—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes with bipolar electrodes
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    • H01M4/0421—Methods of deposition of the material involving vapour deposition
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/184—Sealing members characterised by their shape or structure
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/552—Terminals characterised by their shape
    • H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
    • H01M50/557—Plate-shaped terminals
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
    • H01M50/627—Filling ports
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    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/42—Grouping of primary cells into batteries
    • H01M6/46—Grouping of primary cells into batteries of flat cells
    • H01M6/48—Grouping of primary cells into batteries of flat cells with bipolar electrodes
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
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  • Engineering & Computer Science (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Hybrid Cells (AREA)
  • Press-Shaping Or Shaping Using Conveyers (AREA)
  • Secondary Cells (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

A dry preunit (10), includes a plurality of cells (110, 112, 114) in a true bipolar configuration, which are stacked and bonded together, to impart to the device an integral and unitary construction. Each cell (114) includes two electrically conductive electrodes (111A, 111B) that are spaced apart by a predetermined distance. The cell (114) also includes two identical dielectric gaskets (121, 123) that are interposed, in registration with each other, between the electrodes (111A, 11B), for separating and electrically insulating these electrodes. When the electrodes (111A, 111B), and the gaskets (121, 123) are bonded together, at least one fill gap (130) is formed for each cell.

Description

Energy storing device and manufacture method thereof
Technical field
The present invention generally relates to energy storing device, and more specifically he says the method that relates to ambipolar double layer capacity type energy storing device and make this device.
Background technology
Energy storage dress---in recent years,,, done sufficient research as capacitance or battery for the reliable electrical storage device of practicality.Battery has very high energy storage capability usually; But, battery also presents low power density.In contrast, electrolytic capacitor has the high power density of root and a limited energy density.And, have high energy density based on the double layer capacitor of carbon, but because its high equivalent series resistance (ESR.), carbon electrode has low power capacity.Gu this wishes to be had simultaneously the electrical storage device of high energy density and high power density very much.
B.E.Conway has the article of the 1539th page of (in June, 1991) newly release of J.Eletrochem.SOC. (ECS's magazine) 138 (#6) volume to discuss when electrochemical energy is stored from " super capacitor " conversion to " battery ", and has determined the operating characteristic of various capacitive means.
The Canadian Patent 1,196,683 in the November, 1985 of D.Craig has been discussed the use and the pseudo-capacitance of the electrical storage device of the electrode that applies based on oxide ceramics.Yet the capacitor that adopts this invention to obtain has inconsistent electrical characteristics, and insecure often.These devices can not be charged to 1.0 volts of every electric capacity chips, and have big to unsafty leakage current.In addition, these devices have low cycle life.In addition, disclosed encapsulation is a poor efficiency.
United States Patent (USP) 5,121,288 on M.Matroks and the R.Hackbart has been discussed a kind of capacitive power supply of the patent based on Craig, and this power supply can not be used for the present invention.Capacitor arrangement as wireless telephonic power supply is described in this patent; But, capacitor is not described.
The United States Patent (USP) of J.KalenoWsky, 5,063,340 have discussed a kind of capacitive power supply with charge balancing circuit.This circuit is allowed a plurality of single capacitor chip chargings, and each single electric capacity chip is overcharged.The present invention does not need the charge balancing circuit to realize charging fully to a plurality of single electric capacity chip stepped constructions, and the intermediate capacitance chip is overcharged.
People such as H.Lee roll up people such as the 324th page (in January, 1989) and G.Bullard and at IEEE Transaction on Magnetics25 (#1) volume the 102nd page (in January, 1989) the Pulse Electric power characteristic of high energy oxide ceramics for the double layer capacitor of base have been discussed at IEEE Transactions on Magnetics (IEEE, magnetics journal) 25 (#1).Various operating characteristic have been discussed in this list of references, but manufacturing process has not been discussed.The invention provides the device more reliably that has more effective encapsulation.
On the basis of the early stage work of the British patent 3,288,641 of Rightmhe, many-sided improvement has been arranged based on the double layer capacitor of carbon electrode.People such as A.Yoshida are at IEEE Transactions on Components, Hybrids and ManufacturingTechnology (IEEE, element, hybrid circuit and manufacturing technology journal) CHMH-10 volume #1 100-103 page or leaf (in March, 1987) has been discussed a kind of double layer capacitor that is made of active carbon fiber electrode and no water electrolyte.In addition, also showed the encapsulation of this double layer capacitor.The volume of this device is in the 0.4-1cc magnitude, and energy storage capability is approximately 1-10J/cc.
People such as J.Suzuki have discussed the self-discharge characteristics of improvement of the carbon double layer capacitor of the porous isolated material that adopts 0.004 o'clock thickness magnitude (in July, 1986) at No. 82 118-123 pages or leaves of NEC Research and Devolopment (Nippon Electric Company, Ltd.'s research and development periodical).An intrinsic problem based on the electrode of carbon is that it is little that the low conductivity of material makes these devices produce low current density.Second difficult problem is that the stacked structure that adds of a plurality of capacitor chips is not to form by real bipolar electrode configurations.These difficult problems cause poor efficiency encapsulation and lower energy and power density.
Other valuable reference document comprises, for example:
" commentary of the little shape power supply of solid " that S.Sekido delivers at Solid State lonics (solid ionic) 9,10 volume 777-782 (1983).
People such as M.Pham-Thi have discussed percolation threshold and interface optimization problem based on the solid electrolyte double layer capacitor of carbon at Journal of Materials Science Letters (material science journal) 5 volume the 415th page (1986).
Multiple publication has been discussed the manufacturing and the application of these electrodes in the chloro-alkali industry of electrochemical length of schooling chlorine of oxide-coated electrode.Can be referring to for example: the people's such as V.Hook of promulgation on October 8th, 1991 United States Patent (USP) 5,055,169; Praised the United States Patent (USP) 4,052,271 of the H.Beer of cloth on October 4th, 1977; With the United States Patent (USP) 3,562,008 of praising the people such as A.Martinsons of cloth on February 9th, 1971.But, these electrodes do not possess the desired big surface area of high-efficiency double-layer electrode for capacitors usually.
Manufacture method after having reliable long-life electrical storage device and improving is useful.Also wish to have a kind of improved energy storing device, its energy density is at least 20-90J/cc.
The sealing of energy storing device---as mentioned above, in recent years, the electrical storage device of high-energy and high power density having been done sufficient research, for reaching these purposes, is important with the minimum effective encapsulation that expends the realization active material.In capacitor or battery, the space that two electrodes are separated must make this two electrode electric insulations, yet for effective encapsulation, this space or gap should be as far as possible little.Therefore to wish very that a kind of method that can form a spatial separation device or gap, described isolator or gap are arranged be uniformly basically and have little size (less than 5 mils (0.0127cm)).
In having electrolytical electrical storage device (as battery or capacitor), a kind of universal method of keeping interelectrode isolation is to adopt an electric insulation porous interlayer that can see through ion.This interlayer is usually located between the electrode and keeps the required space interval of two electric inter-stages.The porous isolated material, as paper or glass, to this application is useful, and be used in aluminium electrolytic capacitor and the double electric layer capacitor, yet, for the isolation size below 1 or 2 mils (0.00254-0.00508Cm), materials processing is difficult, and the strength of materials of capacitor is very low usually.In addition, the sectional area in the hole of these porous interlayer type isolators is generally the 50-70% magnitude.
The ion of polymer porous division board thoroughly has been used to the carbon double layer capacitor, exists people such as IEEE 224-230 page or leaf (nineteen eighty-two) and Suzuki as people such as Sannada NEC Research and DeaelopmentDiscussed in No. 82 118-123 pages or leaves (in July, 1986).There is the little problem of hole area in these type of isolation plates, thereby cause resistance to increase.
People such as United States Patent (USP) 4764181 Haruyama in promulgation on August 16th, 1988 disclose a kind of method that adopts the photosensitive polymer resin solution to form the electrolytic capacitor of band leptophragmata layer.In the porous electrode of electric double layer capacitor, adopt described solution using method can cause undesirable filling of porous electrode.
General other relevant list of references comprises United States Patent (USP) 3,718,551,4,052,271; With 5055169.All applications of quoting in this application, patent, article, list of references, standard, or the like full content be hereby incorporated by reference.
In view of the foregoing, it is useful having a kind of method that forms reliable little spatial separation between with the electrode in the electrical storage device of big hole sectional area.
Summary of the invention
The present invention relates to a kind ofly both had high energy density, and have the novel electrical storage device of high power density.
The purpose of this invention is to provide the new method that is used to make this electrical storage device.
Another object of the present invention provide a kind of reliable long-life electrical storage device with and improved manufacture method.
A further object of the present invention is to provide effective encapsulation of electrical storage device by reducing gap between anode and the negative electrode, reduces the resistance value that described gap can reduce ionic conducting electrolyte.
Briefly he says, above-mentioned purpose and other purpose realize that by an energy storing device such as capacitor this device comprises the electric capacity chip of a plurality of bipolar structures.These electric capacity chips are stacked and be sticked together, so that this device becomes as a whole and single structure.
Each electric capacity chip comprises two conductive electrodes that separate by preset distance.This electric capacity chip also comprises at least one dielectric spacer, and it is inserted between the electrode, is used to isolate these electrodes and makes their electric insulations.
When electrode and pad stick together, form one at least for each electric capacity chip and fill the gap.Each electric capacity chip also is included in high surface area (porous) conductive coating that forms on (or more) surface of each electrode.This coating preferably includes one group of peripheral dimpling head that closely separates and one group of center dimpling head that separates at a distance.These dimpling heads can be formed by new silk screen printing or photomechanical printing method.These dimpling heads provide the support structure of capacitor chip, and supplementary insulation is provided between electrode.
Ionic conducting medium is filled the hole of capacitor chip gap and high surface area coating.
Description of drawings
By with reference to following explanation and accompanying drawing, above-mentioned and further feature of the present invention and realize that the method for these features will become more clear, invention itself also will be understood better.
Fig. 1 is the perspective view of the assembly 10 of a kind of dry type energy storing device of formation according to the present invention;
Figure 1A is the perspective view of the electrolytical energy storing device 10A of filling of the present invention;
Fig. 2 is the profile of 2-2 along the line of the storage device of Fig. 1, and it illustrates a detachable conductive strips 1117A in storage device.
Fig. 2 A is the profile of 2A-2A along the line of the storage device of Fig. 1;
Fig. 3 is the decomposing schematic representation of the assembly of Fig. 1, wherein depicts three electric capacity chips;
Fig. 4 is the block diagram of the manufacturing process of storage device 10A;
Fig. 5 is the top view of the porous coating of band dimpling head, the part of the storage device of this coating pie graph 1-4;
Fig. 6 is the schematic diagram of the capacitive character equivalent electric circuit of device 10A.
Fig. 7 is the block diagram that is used for making the method for printing screen of dimpling head on the coating of energy storing device of the present invention;
Fig. 8 is the perspective view of the electrode suppor that uses in the manufacture method of Fig. 7;
Fig. 9 is a block diagram of making the method for dimpling head of the present invention in the photomechanical process mode;
Figure 10 is the isometric view that caused a pair of hot-rolling of resist before photomechanical process to the electrode layer press polish;
Figure 11 is the isometric view of mask that places the photoresist top of Figure 10;
Figure 12 is an isometric view, and it illustrates the not protection exposure status partly of the photoresist of Figure 10 and 11;
Figure 13 is the cutaway view along the electrode of the part of the formation energy storing device of the line 13-13 intercepting of Fig. 3;
Figure 14 is two the bipolar electrode profiles with high surface area porous coating that form a capacitor chip on conductive substrates:
Figure 15 is the schematic diagram that is used for fixing the framework of thin backing material in immersion coating technology;
Figure 15 A is the schematic diagram of the line that uses in the framework of Figure 15.
Embodiment
Definition
The definition of following term is not special-purpose:
" band " is meant used thin material strip in the method for making the dry type assembly.After initial heating, remove the filling part that this band forms the hole.
" conductive supporting material " is meant any conducting metal or metal alloy, conducting polymer, conductivity ceramics, electro-conductive glass or their combination.Metal and metal alloy are preferably used in the manufacturing matrix part, and backing material should have greater than about 10 -4The conductivity of S/cm (Siemens/cm).
" second electric conducting material " (having big surface area) is meant the porous electrode coating, in each side of backing material they can be identical also can be different compositions, preferred metal oxide of the present invention comprises the oxide of optional those metals from following material: tin, lead, vanadium, titanium, ruthenium, tantalum, rhodium, osmium, iridium, iron, cobalt, nickel, copper, molybdenum, niobium, chromium, manganese, lanthanum or lanthanide series metal or its alloy or its composition, and be that the raising conductivity may contain the additive resemble calcium.
" electrolyte " is meant the moisture or anhydrous solution or the material of ionic conduction, and it can make the dry type assembly be recharged.
" Cab-O-Sil " be meant the silica filled thing that the CabotCorporation of Tuscola that can the illinois state obtains.There is multiple size selective.
" epoxy resin " is meant the routine definition of the epoxy resin product that is mixed with specific curing agent, is generally the epoxy resin that is mixed with the polyepoxide curing agent polyamine curing agent or that be mixed with polyamine.
" MYLAR " being meant the Dupont of Wilmington Delaware, the polyester material of the polyethylene terephthalate that Inc produces, polyester usually can be with the large quantities of supplies of form of very thin thickness.
" metal oxide " is meant any conducting metal oxide.
" mixed-metal oxides " is meant the conductive oxide mixture of being made up of two or more metal oxides.
" photoresist " is any photo-curing material, normally epoxides or acrylate or their composition.
" ConforMASK " is a kind of poly-platform thing of negativity light that can buy from the Dynachem of the Tustin in California state.This polymer should 50% or lower relative humidity under use. The dry type precast segment of energy storing device
With reference to accompanying drawing, Fig. 1 especially, 2 and 3, show the dry type precast segment 10 of the energy storing device that constitutes according to the present invention here, this energy storing device at first is assembled into dry type precast segment 10.After each capacitor chip set with the electrolyte filling, the surface is heated to close and is fused to outer surface, and to form device 10A, this device is recharged thereafter.
This device precast segment 10 generally comprises a plurality of capacitor chips, and as capacitor chip 110,112 and 114, their instructions according to the present invention form, preparation and stacked.Figure 1A shows the schematic diagram after the assembling of the electrical storage device precast segment 10A that is formed by 12 stacked capacitor chips, but, should be appreciated that for a person skilled in the art, after having read this specification, can adopt the capacitor chip of any different numbers.
For describing for simplicity, Fig. 3 is the decomposing schematic representation of precast segment 10, and it only illustrates 3 capacitor chips 110,112 and 114.These capacitor chips have identical substantially design and structure, therefore only with reference to Fig. 2,2A, 3 and 13. Capacitor chip 114 and 112 is described in detail.
Capacitor chip 114 comprises conduction bipolar electrode 111B in the first conduction external electrode or end plates 111A and second.Electrode 111A and 111B edge by two dielectrics or electrically insulating substrate's bed course 121 and 123 separate.
When the first and second electrode 111A and 111B, insulation liner layer 121 and 123.And conductive porous material (oxide) layer 119 and 120 is sticked together when forming capacitor chip 114, forms a center air filling gap 130 (Fig. 2 A) by these elements.When assembly 10 can use, fill gap 130 with the electrolyte (not shown), to make device 10A.
For this reason, exemplary recess or fill mouthfuls 122 and be shown among Fig. 2 A only is convenient to the usefulness described, and this filling degree of lip-rounding is formed between laying 121 and 123, to allow electrolyte filling gap 130.Fill mouth 122 by the thin slice or the band 117A that are inserted between packed layer 121 and 123, before fusion and bonding laying 121 and 123, form.When laying 121 and 123 was heated, the laying material that band 117A becomes by backflow centered on, and this is formed with regard to making the profile of filling mouth 122.These two layings become the polymer sheet of molten state, and it covers an as far as possible little zone of active conductive coating 119 and 120.
Study electrode 111A and 111B now in more detail, the method for making these electrodes will be described later.A difference between electrode 111A and the 111B is that electrode 111A selectively comprises a tab 160A, so that be connected to the power supply (not shown).
The selectable difference of between electrode 111A and the 111B another is, electrode 111A comprises a porous conductive coating 119, it is deposited on backing material or the structure 116, and bipolar electrode 111B comprises two porous coatings 120 and 131, and they are deposited on either side or the both sides of backing material or structure 111B.Therefore, electrode 111B is a real bipolar electrode.The both sides that should be appreciated that electrode 111A all can apply the porous, electrically conductive layer.
Another selectivity difference between electrode 111A and the 111B is the rigidity of supporting construction 111A and 111B.Electrode 111A as the outer end panel preferably has a more structure of rigidity, and the overall structure of storage device 10A is with enough rigidity so that it can be energized.The electrode 111B interior electrode similar with other needn't have the rigidity that resembles the external electrode 111A, however, and when device 10A is big, need auxiliary supporting construction, therefore electrode is that 111B is used as auxiliary support structure in, and in this case, electrode is the 111B rigidization in wishing.
As a result, backing material 116 is thicker than backing material 118.In this preferred embodiment, backing material 116 has the thickness of about 10 mils (0.0254cm), and backing material 118 has the thickness of about 1 mil (0.00254cm), and other value also can be selected.
Without departing from the scope of the invention, the size of the remaining electrode of electrode 111A, 111B and storage device 10A is determined according to desirable application.For example, in one application, device 10A is small-sized, for example is used for cardiac pacemaker.And in another kind was used, the whole volume of device was 1 cubic metre or bigger, for example is used for motor vehicle.The total capacitance of the size decision storage device 10A of electrode.
In this preferred embodiment, electrode is that 111A and 111B are rectangles, and but, these electrodes and corresponding precast segment 10 also can be various other shapes, and be for example circular, square etc.The adaptation domestic animal that a key character of assembly 10 is its designs, this makes it can be used for various application.
Study coating 119 and 120 now in more detail, the method that forms these coatings will be described afterwards.In this preferred embodiment, coating 119 comprises a plurality of dimpling heads, and coating 120 does not comprise this dimpling head.But, should be appreciated that without departing from the scope of the invention that coating 120 can be selected the design similar to coating 119.
Fig. 5 is the top plan view of coating 119, and it comprises the real array of a dimpling, and is inner face or the flattened side that is deposited on backing material 116, and coating 119 is have high surface area loose structures, conduction and thin.Array comprises two groups of dimpling heads.First group comprises that 125, the second groups on a plurality of circumferential dimpling heads comprise a plurality of dimpling heads 127 that are positioned at central authorities.
In this preferred embodiment, garden week shape plush copper 125 has similar project organization with central plush copper 127, and roughly is hemisphere, but, other shape, for example rectangle also belongs to scope of the present invention.Each plush copper 125 or 127 diameter are about 6 mils (0.01524cm), and the different application of device 10 may require dimpling head 125 and 127 to have the different designs structure.Center-the Center Gap of garden all shape dimplings head 125 is about 20 mils (0.0508cm), and the center-Center Gap of central dimpling head 127 is about 40 mils (0.1016cm).
The reason that garden all shape dimplings head 125 has higher density is to prevent edge shorting.It is to form to isolate between electrode 111A and 111B that central authorities' dimpling head 127 has a more low-density reason, and electrode surface has minimum mask simultaneously.For this reason, allow that laying 121 covers at least a portion of dimpling head 125, but preferably do not cover dimpling head 127.
Garden all shape dimplings head 125 is along the adjacent setting of outer rim of coating 119.Although only draw four row's dimpling heads, it will be understood by those of skill in the art that according to the size and the application of device 10, can increase row's number.Central authorities' dimpling head 127 is with in the similarly adjacent core 132 that is arranged at coating 119 of array layout.As shown in Figure 5, central dimpling head 127 is centered on by garden all shape dimplings head 125.
Dimpling head 125 and 127 is formed on the coating 119, provides additional structural support to give the first and second electrode 111A and 111B.For example, sagging or crooked if the second electrode 111B begins to the first electrode 111A, dimpling head 127 will prevent the contact between these electrodes 111A and the 111B.
Fig. 5 further illustrates, and coating 119 comprises that also a plurality of openings are 133A-133G, band, and promptly 1117A is arranged in this opening, fills mouth 122 with final formation.As what drawn at the large electrode size, recess (being opening) only part extends to core 132.For the small electrode size, recess is across electrode surface, and stretch out to opposite side at its two ends, fills mouthful 133C and 133D thereby form simultaneously, in this case, the width of band is less than or equal to the center-Center Gap of 127 on central dimpling head, but, band (width) is greater than the center-Center Gap of garden week 125 on shape dimpling head, pushes this band to prevent garden week shape dimpling head, and prevent that it from shifting out, in all shape dimplings head of garden, increase opening.In addition, the width of band can be similar to garden week shape dimpling head interval, and needn't adjust in dimpling head figure.
Present research coating 120, it plays the function similar to coating 119, and is deposited on the side in the face of the inboard of the first electrode 111A of electrode 111B.In this preferred embodiment, coating 120 does not comprise plush copper.In another embodiment of precast segment 10, coating 119 and 120 has analog structure, and comprises dimpling head layer.
Study laying 121 and 123 now, the method for making these layings will be described later.Laying 121 is normally identical with 123, and arranges in the mode that overlaps (adjacent and stacked) each other.For for simplicity, only laying 121 is described in detail laying 121 and comprises a continuous garden circumferential portion 143 and a hollow center part 144.
In this preferred embodiment, band 117A or its part are between laying 121 and 123, and the hollow parts that passes through laying promptly 144, and extend peripheral part promptly outside 143.In another embodiment, the integral width that band does not pass through laying has only the part of band to be folded between these layings, and extends through the two edges of laying one side.
Now get back to Fig. 1, next neighboring capacitors chip 112 is simply described.Capacitor chip 112 is roughly the same with capacitor chip 114 aspect design and structure.Capacitor chip 112 comprises as the bipolar electrode 111B of first electrode and the second bipolar electrode 111C.Electrode 111B and 111C are basic identical, and separate each other by the mode of aligning mutually.
The porous coating 131 identical with coating 119 be deposited on backing material 118 in the face of on the surface of electrode 111C, the coating 133 similar to coating 120 is deposited on backing material or the structure 140, it constitutes the part of electrode 111C.
Capacitor chip 112 also comprises two layings 135 and 137, and the laying 121 and 123 of they and capacitor chip 114 is mutually the same.Band 117B forms between laying 135 and 137 and fills mouth 142.
Capacitor chip 110 is basic identical with capacitor chip 114, and comprises the first bipolar electrode 111Y, second electrode 1112, two layings 157 and 159, band 117C, tabs 160 and fill mouthfuls 162.Should note the not shown interior electrode 111Y of Fig. 3.
Now forward Fig. 6 to, draw a capacitive character equivalent electric circuit 200 of representing device 10A here.This circuit 200 is expressed as two capacitor C with capacitor chip 114 1And C 2, capacitor chip 112 is expressed as two capacitor C 3And C 4Capacitor chip 110 is expressed as two capacitor C 5And C 6As a result, install 10 roughly equivs in one group of polyphone capacitor.
Ionic conducting medium (not shown) in porous conductive coating 119 and the capacitor chip 114 combines and constitutes capacitor C 1This ionic conducting medium and coating 120 constitute capacitor C 2Ionic conducting medium in coating 131 and the capacitor chip 112 constitutes capacitor C 3Ionic conducting medium in the capacitor chip 112 and coating 133 constitute capacitor C 4Similarly, capacitor chip 110 is by two container c 5And C 6Expression.
A bipolar structure that importance is an energy storing device of the present invention.Adopt single electrode,, form two series capacitors, as capacitor C as electrode 111B 2And C 3Thereby, form a bipolar electrode B.This design has reduced the overall dimension of device 10A significantly.
Although do not want to be subjected to theory constraint, can help to understand the immense value of charged bilayer for the explanation of the working condition of the capacitive energy storage apparatus of molecular level.For for simplicity, for referencial use for describing Figure 14 with Fig. 3, wherein adopted same reference numbers (and porous material is a mixed-metal oxides).
Figure 14 is the generalized section at edge of the amplification of supporting construction 118,148A and conductive coating (120,131,133,133B).
The central support structure of being described 118 is a metal, but it can be the material that also provides support for coating of any conduction.Coating with high surface area provides structure and the geometry that is used for the energy storage.As what seen from Figure 14, layer 120 grade have the discontinuous surface with many cracks, micropore and mesopore, and they have formed high surface area.
Therefore, porous coating 120 and 131 is applied to and forms bipolar electrode 111B on the supporting construction 118, and coating 133 and 133B then are applied to supporting construction 148A and go up and formation bipolar electrode 111c.After precast segment 10 assembling, drawstring is removed, and form to fill mouthful, and precast segment 10 is filled by electrolyte 190, and filling thereafter mouthful is that 177D is sealed, thereby has formed device 10A.
Install 10A subsequently and be recharged, produce following result simultaneously:
Coating 120 becomes electronegative.Support structure 118 is transmission electronic correspondingly.Therefore, porous coating 131 becomes positively charged.The correspondingly ionization of electrolyte of ion domestic animal conduction.Separate at electrode-electric and just to form an electric double layer on the matter interface, the single electric capacity of each in its forming circuit 200.Therefore, the surface of coating 133 becomes electronegative, and the surface of coating 133B becomes positively charged.Because porous high surface area oxide allows that the effective surface area of electrode becomes very big, so the corresponding electric storage capacity of this device sharply strengthens. Make the method for energy storing device
With reference to Fig. 1-5, do following explanation generally for the method for optimizing of the precast segment 10 of making energy storing device 10A:
(A) backing material preparation
Backing material can carry out selective etch or cleaning by the corrosion or the cleaning of various routines.
In some experiments, if not etching of metal surface, it is very level and smooth.Level and smooth surface causes insufficient adhesion of porous coating sometimes.Etching can form suitably coarse surface.
1. wet etching: a kind of selection process is that metallic support is contacted with moisture inorganic acid, for example, and sulfuric acid, hydrochloric acid.Hydrofluoric acid, nitric acid, perchloric acid or their composition.About 0.1 to 5 hour (being preferably 0.5 hour) carried out in etching usually under the high temperature of 50 to 95 ℃ (being preferably 75 ℃), then use water rinse.The room temperature acid etching is possible.Also can adopt alkaline etching or oxalic acid etching.
2. dry etching: coarse stayed surface can be by sputter, and plasma treatment and/or ion grind and obtain.A kind of selection process is ArRF (argon gas radio frequency) sputter etching, and etching condition is the frequency of energy and the 13.5MHz of the pressure of 0.001-1torr, about 1Kev.Usually, adopt 0.1-10watts/cm 2Power density in 1-60 minute time, clean and make rough surface, another kind of technology is the plasma etching that with reacting gas backing material was carried out under the pressure of 0.1-30torr 1-60 minute, reacting gas is, for example, and oxygen, carbon tetrafluoride and/or sulphur hexafluoride.
3. chemical etching: rough surface can be handled by the electrochemical oxidation in chloride or fluoride aqueous solution and obtain.
(B) coating of backing material
This coating (for example oxide) be porous and mainly by micropore (diameter＜17A) form.Have the wide big crack of 0.1-1 μ m from the teeth outwards, their degree of depth and coating layer thickness are suitable.But, the surface area more than 99% is formed by these micropores, and the average diameter of these micropores is in the 6-12A scope.
After various reprocessings, pore structure can change, to increase average cell size.For example, the steam reprocessing forms bimodal pore distribution.Except that micropore, (the narrow district of diameter＜17-1000A) distributes to have formed the mesopore of the diameter with about 35A.The 85-95% of the surface area of the electrode coating after these are handled is formed by microcellular structure.
Adopt other electrode structure method, this pore size distribution can change, and adopts matted crystal or other institutional framework in the surfactant increase coating solution, can make average cell size be increased to 100-200A, and have only the surface area of 5-10% to come from micropore.Therefore the effective high surface area of coating is long-pending bigger 1000 to 100,000 times than the design surface of electrode.
As shown in figure 13, electrode 111A comprises porous conductive coating 119, and it is formed at least one surface of backing material 116, and backing material 116 conducts electricity, and has enough rigidity, to support coating 119 and to give device 10 with enough strong structural rigidity.
Optimum capacity density and power density that a target of the present invention is a choice device 10.This target is to maximize with the surface area that makes coating 119 by the thickness that reduces fid 116 to realize.The functional density of device 10 further makes it optimization by keeping low resistance.
The surface area of coating 119 is determined with BET method well known in the art.The surperficial optimized surperficial increment rate of expression coating 119 is determined according to following formula:
Surface increment rate=(BET surface area/design surface is long-pending)
In the present invention, surperficial Magnification can reach 10,000 to 100,000.
Coating 119 is porous, and its porosity is in about scope of 5% to 95%, and for effective energy storage, typical porosity ranges is about 20% to 25%.
In the double electric layer capacitor of routine, main device resistance comes from carbon coating.In the present invention, device resistance mainly comes from electrolyte, and electrolyte has the resistance higher than porous conductive coating.
After precast segment 10 was filled electrolyte, it just can be recharged and become device 10A.For electrolyte, main standard be it be ionic conduction and have a bipolar performance.Border between electrode and the electrolyte or boundary zone are known as " electric double layer " in this area, and are used to describe this regional electric charge arrangement.The more detailed description of electric double layer theory is recorded in people's such as Bokrls " modern electrochemistry " the 2nd and rolls up the 6th printed book the 7th chapter (1977).
The capacitance of the surface area effect device 10A of coating, if (for example) surperficial enhancement coefficient is 1000 to 20000, and the electric double layer capacitance metric density is every centimetre 2About 10 to 500 microfarads of interfacial surface area (being the BET surface area), can obtain so to be approximately every centimetre 2The surface that electrode is 0.1 to 10 farad increases capacitance density.
Although the electric double layer theory has been described at this, should be appreciated that other theory or pattern, as the protonation pattern, also can select for use.
High surface area (porous) conductive coating material is applied to backing material.
1. solution methods: porous coating material can be formed by the various reaction raw materials compounds in solution or the sol-gel composition.The multiple application process of these starting compound compositions all is feasible, and is not limited to following method, and curing, hydrolysis and/or pyrolytic process are often used in forming on the backing material coating.The pyrolysis of slaine is undertaken by stove and accessory or infrared radiation source under controlled atmosphere (nitrogen, oxygen, water and/or other inertia and oxidation domestic animal gas) usually.
(a) immersion coating: electrode or supporting construction are impregnated in solution or sol-gel, cover supporting construction with the starting compound coating, and then solidify with pyrolysismethod or other method.This technology can repeat, to increase coating layer thickness.Preferably, backing material be impregnated in metal chloride/alcoholic solution, and then in the oxygen atmosphere of 5-100% under about 250 to 500 ℃ temperature pyrolysis processing 5-20 minute.
Repeat this technology, until obtaining desirable coating weight.Final pyrolysis processing is to carry out 1-10 hour under 250 to 450 ℃, and representative value is about 1-30mg/cm 2Coating be deposited on the backing material, to obtain the capacitance density of the long-pending about 1-10F of every square centimeter of electrode sections.Another kind method is, prepares sol-gel solution with the oxide of nail, silicon, titanium and/or other metal, and applies backing material as stated above.By adjusting the content of the such additive of pH value, water concentration, solvent and/or oxalic acid, formamide and/or surfactant, the discharge frequency characteristic of adjustable coating.
In pyrolysis step, can adopt higher relative humidity, so that realize the transformation of raw material at a lower temperature to oxide.Method for optimizing is, carries out in the process of pyrolysis under being lower than 400 ℃ temperature, keeps about relative humidity more than 50%.
A kind of method for optimizing of (for example 1 mil) supporting construction that immersion coating is thin is to adopt a wire frame structure 300 to keep backing material 118 in tensioned state (Figure 15 and 15A).
Wire frame structure 300 comprises at least two lines 301 and 301A, and their length is greater than the width of backing material 118.Every line 301 and 301A comprise an independent line segment, and this line segment is closely reeled about 360 ° and form two circles 302 and 303 at its each end.These two circles are so reeled, that is, the about 1cm place of its termination on this line plane, the hole 304 and 305 that circle 302 and 303 passes respectively in the backing material is provided with.Hole 304 and 305 is positioned on two angles of adjacent side of backing material.
Other two line 301B and 301C are loaded on all the other two sides of backing material in a similar manner, so that additional support to be provided.
(b) spraying: coating solution is coated on the backing material by spraying method, and solidifies and optionally repetition, is used to increase coating layer thickness.Method for optimizing is, under 0-150 ℃ temperature coating solution is sprayed into substrate, and ultrasonic nozzle or other nozzle are adopted in spraying, with the flow velocity of about 0.1-5ml/min, carry out in the carrier gas of being made up of nitrogen, oxygen and/or other reaction and inert gas.Applying characteristic can control by the partial pressure of oxygen and other reacting gas.
(c) roller coating: adopt the roller coating method to apply the starting compound coating, solidify then and optionally repetition, be used to increase coating layer thickness.Here the available above-described coating that is used for immersion coating.
(d) spin coating: apply starting compound with spin coating method of the prior art, and selectivity repeats.
(e) scraper applies: apply starting compound with the scraper painting method, and selectivity repeats.
2. electrophoretic deposition: on backing material, form porous coating or starting compound coating with the electrophoresis deposition technology, and selectivity repeats.
3. chemical vapor deposition: form porous coating or starting compound coating with known chemical vapor deposition technology.
(c) electrode preliminary treatment
Have found that multiple preliminary treatment (conditioning) or its combination are useful to the electrical characteristics (for example, the lazy domestic animal of electrochemistry, conductivity, operating characteristic etc.) of improving coating.These processing for example comprise:
1. steam treatment: in a closed container, between 150 to 320 ℃, under self-generated pressure, coated electrode contacts 1-6 hour with water saturation steam.
2. reacting gas is handled: between room temperature to 300 ℃, under decompression or low pressure, coated electrode carries out one or many with reacting gas and contacts, reacting gas such as oxygen, ozone, hydrogen, peroxidating gas, carbon monoxide, nitrous oxide, nitrogen dioxide or nitric oxide, method for optimizing is, between room temperature to 100 ℃, under 0.1-2000torr pressure, allow coated electrode contact 0.1-3 hour with the moving air of 5-20wt% ozoniferous.
3. overcritical liquid stream is handled: electrode and overcritical liquid such as carbon dioxide, organic solvent and/or water are flowed contact.Method for optimizing is, by at first raise pressure thereafter elevated temperature reach super critical condition, with supercritical water or carbon dioxide treatment 0.1-5 hour.
4. electrochemical treatments: coated electrode places sulfuric acid electrolyte, and passes to and be enough to anode current that oxygen is emitted, then passes to cathode current.In one embodiment, electrode logical 10mA/cm in 0.5M sulfuric acid 2About 5 minutes of electric current is to produce oxygen.Electrode is relayed to cathode current subsequently, and orders about Open Circuit Potential and fall the hydrogen that has that is back to 0.5V (relatively normal hydrogen electrode) and disengage current potential.
5. reaction liquid is handled: make coated electrode contact 0.1-6 hour with oxidizing liquid being about under the temperature of room temperature to 100 ℃, such as the aqueous solution of hydrogen peroxide, ozone, sulfoxide, potassium permanganate, sodium perchlorate, chromium (VI) isotope and/or their composition.Preferable methods is, with the ozone water solution of 10-100mg/l, handles about 0.5-2 hour at 20-50 ℃, then carries out the water flushing, and another kind of method is the coated electrode of processing in chromate or bichromate solution.
(D) interelectrode isolation
Be the interval that obtains electric insulation and suitably limit between electrode, several different methods is feasible.These methods comprise, for example:
1. dimpling head: the separator 125 and 127 between the coating 119 and 120 is included in the array of little (aspect area and height) plush copper at least one side surface of electrode, promptly 125 and 127, these dimpling heads can be made of thermosets, thermoplastic, elastomeric material, ceramic material or other electrical insulating material.
The method that forms these dimpling heads has following several, but is not limited to this several method:
(a) silk screen print method: the dimpling head is set on the electrode surface by the silk screen print method of routine, exists as the back: silk screen printing " under the title described in detail, in this method, can adopt various elastomeric materials.Photocuring plastics and thermoplastic.Method for optimizing is to adopt acidproof epoxy or VITON Solution.
(b) chemical vapor deposition method: the dimpling head also can be set on the electrode surface by seeing through a mask deposition silicon dioxide, titanium dioxide and/or other insulation oxide or material.
(c) photoetching process: the dimpling head also can be made by photoetching process, as the back under " photolithographic fabrication of dimpling head " title described in detail.
2. the thin spacer of physical property: interelectrode division board be approach, be essentially open architecture material, for example glass.(0.00254-0.01270cm) thick porous glass sheet when preferred material is the 0.001-0.005 that can buy from the WhatmanPaper Ltd of the Clifiton that is positioned at the NJ state.
3. injection moulding division board: the division board between the porous material also can obtain by injection moulding one deck film thin, that be essentially open architecture, for example NAFION , polysulfones, or all gases and sol-gel.
4. air insulated: the slider between the electrode is an air-gap, and it is filled by anhydrous or aqueous electrolyte thereafter.
(E) add the cushions
Be used as the laying of the edge of active electrode surface, for example laying 121,123,135.137,157 and 159 material comprises any organic polymer stable under electricity/chemical environment and processing conditions, and suitable polymers comprises, for example, and polyimides, imines, TEFZEL , polyethylene (height and low-density), polypropylene, other polyolefin, polysulfones, KRATON , other polymer that fluoridize or partially fluorinated or their combination.Laying can form by method for printing screen or other method, as preforming material.
(F) band that is used to fill mouthful
Be used to form and fill mouth, the band (117A, 117B and 117C) of for example filling mouth 122 and 142 is any suitable material with some property, for example, it is different from the laying material, it has the fusion temperature higher than laying material (Tm), and under heating condition described herein, it can not melt, flow or be attached to the laying material.Usually adopt glass, metal, pottery and organic polymer or their combination.
(G) stacked
Stacked structure is by constituting like this, beginning to put end plates, is alternately to arrange laying material, band, electrode thereafter, until forming desirable capacitor chip number, finish to place second end plates at last, and can select a cushioning material layer to be positioned at the top outer of stacked structure.
(H) assembling (heating and cooling)
Under low pressure heat stacked structure, make the laying material reflow, with the perimeter bond and the adjacent electrode that is sealed in the stacked structure of electrode material; Form capacitor chip and an overlapped assembly that assembles of mutually insulated thus.
(a) with radio frequency induction heating (RFIH) heating stacked structure, make the laying material reflow.
(b) evenly heat stacked structure with radiation heating (RH) method, make the laying material reflow, method for optimizing is with (0.5-10Watts/cm 21-100 μ m radiation heating 1-20 minute.
(c) adopt in stove optionally conduction in inert atmosphere and/or Convective Heating method to heat stacked structure, make the laying material reflow.
(I) form the filling mouth
Band is pulled out from the assembly that assembles, have the dry type precast segment that at least one fills mouth to form each capacitor chip.
(J) reprocessing
Multiple follow-up reacting gas being carried out in stacked structure or the stacked structure that assembles or their combination handle, is useful to the whole and long-term electrical characteristics of improving electrode and formed device.These processing be included in step (H) before and/or step (I) afterwards, with hydrogen, nitrogen oxide, carbon monoxide, ammonia and other reducing gas or its combination, in room temperature between the fusion temperature Tm of laying material, the processing carried out under decompression or low pressure.
(K) filling of dry type precast segment
The dry type precast segment will be filled with the moisture or no water electrolyte of ionic conduction.
Preferred electrolyte is the aqueous solution that contains 30% sulfuric acid approximately, because it has high conductivity.Also can be used to obtain current potential based on the no water electrolyte of polypropylene and ethylene carbonate greater than the 1.2V/ capacitor chip.
The method for optimizing of filling the dry type precast segment with liquid electrolyte is, precast segment is put in the operating room, operating room is evacuated to be lower than 1torr, and injects electrolyte; Make electrolyte by filling a mouthful gap that is filled to capacitor chip thus.Another kind method is, precast segment can be placed electrolyte and vacuumizes.Thereby remove in the gap of capacitor chip gas and with electrolyte for it.
In addition, also can adopt non liquid state electrolyte (for example, solid-state and polymer).Electrode is under the situation of coated electrolyte before backflow, do not need to fill mouthful.
(L) sealing of filling mouth
Filling mouth is to form the identical or different polymer supporting film of one deck by refluxing to seal on opening, thereby forms the device of sealing.This carries out with induction heater usually, and the heater localized heating covers the film of filling mouth.
(M) aging
By pressing about 4mA/cm 2Charging current begin with device charge to 0.1V, capacitor chip impels device to charge fully.
(N) test
Terminating method: have several methods to can be used for realizing the electrical connection of capacitor top extraction electrode plate, these methods are described below.
1. end face extraction electrode tab (160 and 160A): end face extraction electrode plate (111A and 111Z) itself has been cut into the shape that extends beyond normal laying periphery.These extensions are allowed the installation line or belt.In typical case, extension is a conducting strip, and all oxides on it is removed the backing material that obtains exposing; The thick nickel strap spot welding of 5 mils (0.0127cm) is so far on the conducting strip,
2. mix silver epoxy
Remove on the exposure of end plates oxide coating or only at a side coated end panel.Bond by the silver epoxy of mixing, make clean nickel foil or copper coin be electrically connected to exposed surface with conduction.Oxide coating exists also can be selected.
3. connector lug: threaded titanium nut is welded to before coating on the thick titanium plate.By realizing with bolt and being electrically connected of titanium nut.
4. pressure contact: before being assembled into the stacked structure of device, remove the oxide of end plates exposed sides, or only at a side coated end panel.The reverse exposed backing material of sputter, titanium for example, with the clean surface, should be prudent during sputter, do not make substrate overheated.Clean Surface is used the titanium sputter thereafter, to lay the tack coat of a cleaning, then uses golden sputter.Gold can be by pressurization or the bonding realization of line electrically contacting of surface therewith as the low contact resistance surface.
Suitable media of being undertaken by CVD or other method such as aluminium, gold, silver, etc. outside deposit.
Device resistance is measured under the 1KHz condition.The device capacitance is to determine that by the coulomb number that measurement makes device charge required fully charging current is about every square centimeter of electrode area 4mA.Leakage current is to measure for keeping the required electric current that charges fully after 30 minutes by charging.
According to desirable application, these devices can be made into various configurations, and the relation by between adjusting device voltage, capacitor chip voltage, electrode area and/or the coating layer thickness can construct the apparatus structure that is suitable for particular requirement.
For the thick coating of per 10 μ m, and the electrode capacitance metric density (C ', unit is F/cm 2) be about 1F/cm 2Therefore, to use thicker coating for obtaining big capacitance.Device capacitance (C) equals the electrode capacitance metric density and multiply by electrode area (A, the cm of unit 2) again divided by 2 times capacitor chip number (n) (equation 1).
Leakage current (i ") is directly proportional with electrode area, and equivalent series resistance (ESR) and electrode area be inversely proportional to (equation 2).The representative value of leakage conductance electric current (1 ") is less than 20 μ A/cm 2
The total quantity of capacitor chip (n) equals overall apparatus voltage (V) divided by capacitor chip voltage (V ') (equation 3) in the device.Capacitor chip voltage up to about 1.2V can adopt aqueous electrolyte to obtain.
Device highly depends on capacitor chip gap (h ') and supporting construction thickness (h "), by the capacitance density (unit: F/cm of capacitor chip quantity and electrode 2) determine, see equation 4.
The equivalent series resistance (ESR) of device is capacitor chip quantity, capacitor chip gap (h '), electrolytical resistivity (r) and be about the function (equation 5) of the product of 2 constant divided by area.
Equation 1 C=C ' A/2n
Equation 2 i " α A α 1/ESR
Equation 3 n=v/v '
Equation 4 h/cm=n (0.002C '+h '+h ")
Equation 5 ESR=2nh ' r/A
By requirements such as research voltage, energy and resistance, device is configured to satisfy the needs of various application.Following example does not also mean that and is subjected to any restriction:
For electric vehicle applications, adopt the device of 100KJ to 3MJ.Employing has about 100 to 10000cm 2High voltage (about 100 to the 1000V) macro-energy (1-5F/cm of electrode area 2) storage device.
For being used to reduce for electrically heated catalytic converter that automobile cold start starts uses, adopt 10 to 80KJ device.This device is approximately 12 to 50V, and to have area be 100 to 1000cm 21-5F/cm 2Electrode.Also can select like this, constitute a device by the several means of parallel connection, to satisfy electric requirement.
For defibrillator is used, adopt that to have area be 0.5 to 10cm 21-3F/cm 2About device of 200 to 400V of electrode.
For uninterrupted power supply is used, can adopt various series/parallel apparatus structures.
Silk screen printing
Study method for printing screen 250 now, with reference to Fig. 7 and 8, method 250 is mainly used in preparation a series of dimpling heads 125 and 127 on coating surface, with in common electrical storage device, and especially be to be used as the gap separator in the formula precast segment energy storing device 10 as capacitor or battery and so on.
The metal that substrate is normally thin, as titanium, zirconium or its alloy, substrate is generally the metal sheet shape, uses always in existing capacitor.
The one or both sides of substrate are coated with the carbon compound of porous or the oxide coating of porous.This step is finished by this area method commonly used.Oxide coating is as the charge storage area of this device.
In addition, can make one group of stacked battery electrode (for example plumbic acid use lead) and electrolytic capacitor (for example aluminium oxide and tantalum).
Importantly, the adjacent coated substrate or the flat surfaces of electrode can not be in contact with one another, and are evenly to isolate.Realize desirable even isolation with epoxy resin dimpling head.
Sample support: coated thin flat substrate will be fixed (or support), and on the plane surface of substrate, the formation of dimpling head is accurate with accurately like this.For foil (0.1 to 5 mil) (0.000254 to 0.0127cm); especially about 1 mil (0.00254cm)); electrode suppor 275 is particularly important; if to the thin slice pumping high vacuum; regular meeting forms harmful indenture in sheet, and it can make the physics of resulting device and electric property produce significant undesirable variation.
Electrode suppor 275 comprises a porous ceramic support 276, and it is useful, because hole dimension is little of being enough to when being evacuated to medium or higher vacuum indenture not to be occurred.Do not make flow of metal or do not destroying under the condition of coating, the smooth ceramic surface of ceramics bracket 276 must closely contact with the surface of electrode 111A.To porous ceramic vacuum degree at least 25 inches of mercury preferably.Vacuum degree is preferably between about 25 to 30 inches of mercury, especially 26 to 29 inches of mercury.
In addition, ceramic substrate should with the flush of arbitrary machinery mount, to guarantee that epoxy resin passes the silk screen hole and produces evenly outstanding, here flush and be meant, rack surface and be used for not having significant difference between the coating surface of electricity storage, the difference between two per 6 inches long surfaces is ± 6 Mills (0.0127cm).
Electrode suppor 275 also comprises metal framework 277, and it also should be smooth as much as possible, so that form the plush copper of uniform-dimension from electrode one side direction opposite side.
Electrode suppor 275 can be bought from many commercial undertakings, for example the Ceramicon Designs in Coloradl state.In addition, sample holder 276 can adopt commercial available metal, alloy or pottery to make.
Usually, form the coated pellet electrode of 5 inches (12.7cm) * 7 inch (17.78cm).
Metallic support 277 has a plurality of alignment pins that are in key position, and as three alignment pins 278,279 and 280, they cooperate with corresponding hole 281,282 and 283 respectively, with electrode 111A calibration and location.The periphery of hole 281,282 and 283 common as close as possible electrode 111A, saving useful electrode surface, another kind of mode is, do not adopt calibration hole, alignment pin is aimed at electrode edge.
Matrix (not shown) with predetermined open figure is laid and is fixed in the conventional silk screen printing frame (not shown), and silk screen is removed.
The epoxy composition and the fluid ring epoxy resins of having mixed are placed on the surface of masterplate, spread out subsequently, to obtain the smooth layer suddenly that is coated with.This can adopt pressure bar, scraper or squeegee to finish.
In general, stationary temperature and humidity are important to obtaining smooth coating.
Take out masterplate subsequently carefully, on the surface of oxide, stay fluid ring epoxy resins plush copper.Then adopt under the atmosphere 100 to 150 ℃ Fast Heating or illumination that the epoxides plush copper is solidified.
Electrode and other combination of electrodes that will have the dimpling head then, and by wet method or dry method assembling.If the employing dry method, before will charging, dry type assembly 10 will be filled electrolyte.
The epoxy resin that solidifies is not important with the liquid electrolyte reaction that is used to make the capacitor with multi-layered electrode at last.
The dimpling head that solidifies plays the evenly spaced effect between electrode that keeps.
As what can see from Fig. 6, the edge of electrode flat surfaces has plush copper 125, and they are more more intensive than those plush coppers 127 of the live part of electrode or middle body.These plush coppers 125 strengthen the support of edge, thereby keep even isolation.In addition, also can adopt rod.
From these instructions, can know clearly that following situation is possible:
Because support stiffness can change, increase or reduce underlayer electrode thickness and will allow the increase of dimpling head insulating space or reduce.
Can adopt other thermosets, thermoelastic material, photo-curing epoxy resin or epoxy resin derivant commonly used in this area.
Can adopt other dimpling head graphic elements, for example square, wire, cross, or the like.Especially, the rod of edge can increase mechanical support.
Make the epoxy resin that to flow reach the temperature that its viscosity is suitable for printing in short-term if desired, also can select the heater strip net.
And then this heating steps of silk screen printing of epoxy resin of carrying out flowing must carry out fast, because the operating time of epoxy resin obviously reduces.
The electrical storage device with dimpling head 125 and 127 of manufacturing is useful as battery, capacitor or similar device.
The photolithographic fabrication of dimpling head
This method mainly is to adopt photoetching technique, electrode substrate or alloy surface on make a series of dimpling heads, with reference to Figure 10,11 and 12.Substrate is generally and resembles metal sheet shape commonly used in the existing capacitor.
Photoresist film 381 is coated on the surface of electrode 111A, described coating is that 724/30 Dynachem vacuum covering device vacuum is laid by adopting commercial available Dynachem ConforMASK thin film coated device and model, or realizes by the roller 384 and 385 that allows photoresist film 381 and electrode 111A pass a pair of heating.
Exposure is that the 1-7KW high voltage exposure light source of employing standard is implemented, and for example mercury vapor light 389.
Adopt reference condition, for example the sodium carbonate of 0.5-1.0% or potash list hyrate in developing tank or the moisture developer solution of conveyor type, show ConforMask thin film coated device and develop.After the development, the electrode of band dimpling head can be carried out neutralisation treatment in 10% dilution heat of sulfuric acid.This can remove all undesired unreacted films, and stays the reacted dimpling head that sticks to electrode surface.
For obtaining best physics and electrical installation characteristic, resulting material is carried out final curing process handle, this curing process comprises that the high voltage curing apparatus of employing routine and the high voltage that carries out of convection current air furnace shine and heat treatment.
A plurality of electrodes are assembled up make (for example) capacitor, as mentioned above.The dimpling head is realized desirable even isolation. The commercial application
As main or auxiliary power supply, and/or as capacitor, energy storing device 10A has multiple application.Its specification is 0.1V to 100000V or 0.1cm 3To 10 5Cm 3The exemplary voltages scope is included in the combination of the scope of application in automobile and other application.
These application comprise following application:The automobile applicationExemplary voltages scope typical sizes (cm3) inner tube of a tyre and the seat damper 1-100 1-1000 seat heater 1-100 1-100 electrons heat catalyst converter 1-1000 1-1000000 electric car engine 100-1000 100-1000000 mixed type electric 1 of automobile engine-1000 10-100000 internal combustion engine/electronic commutator 1-1000 of electrochemical capacitance engine 1-100 100-100000 1-100 regeneration brake/impact absorption 1-1000 5-100 lights a lamp and with battery igniting 1-1000 2-100, light a lamp and only keep the 1-100 1-100 that lights a fireMedical applicationthe heart defibrillator, 10-500, 0.1-100, pacemaker, 1-300, 0.1-300, neural activation device or similar device, 0.1-300, 0.1-300, implantable and device external application, 0.1-300, 0.1-300, the surgery electric tool, 10-700, 1-10, custodial care facility flows, 1-100, 1-100, the automated fluid chromatography, 1-100, 1-20, automatically clinical trial analysis, 1-100, 1-20, computer chromatographical X-ray (CT) scanner, 1-1000, 1-100, dental equipment, 1-200, 1-10, digital radiography equipment, 1-500, 1-1000, electrosurgical equipment, 1-100, 1-10, optical fiber, 1-100, 1-100, check, 1-10, 1-10, hearing aid, 1-10, 0.1-1.0, infusion device, 1-100, 0.1-10, magnetic resonance imaging (MRI), 1-1000, 1-1000, nuclear medical diagnostic equipment, 1-1000, 1-100, the electric patient monitoring system, 1-200, 1-100, respiratory therapy, 1-500, 1-100, the surgery laser instrument, 1-1000, 1-1000, electric surgery support system, 1-100, 1-1000, ultrasonic diagnostic equipment, 1-100, 1-100Automobile engine systemGear shift 1-1000 100-10000 Caddy 1-1000 100-10000 farm implements, subway 1-1000 100-100000 regeneration brake 1-1000 1-100Office/commercial electronic applicationOOTA, Yasuhiko <120> with the disease-associated nucleic acid detection <130> 01S1691P <150> JP 2001-90053 <151> 2001-3-27 <150> JP 2001-284112 <151> 2001-9-18 <160> 72 <210> 1 <211> 21 <212> DNA <213> Hepatitis C virus (Hepatitis C Virus) <400> 1 ccctgtgagg aactwctgtc t <210> 2 <211> 21 <212> DNA <213> Hepatitis C Virus <400> 2 ggtgcacggt ctacgagacc t 21 <210> 3 <211> 26 <212> DNA <213> Hepatitis C Virus <400> 3 tctagccatg gcgttagtry gagtgt 26 <210> 4 <211> 26 <212> DNA <213> Hepatitis C Virus <400> 4 cactcgcaag caccctatca ggcagt 26 <210> 5 <211> 18 <212> DNA <213> Hepatitis C Virus <400> 5 cgctcaatgc ctggagat 18 <210> 6 <211> 18 <212> DNA <213> Hepatitis C Virus <400> 6 cactctatgc ccggccat 18 <210> 7 <211> 18 <212> PNA <213> Hepatitis C Virus <400> 7 cgctcaatac ccagaaat 18 <210> 8 <211> 20 <212> DNA <213> Hepatitis C Virus <400> 8 cgcgcgacta ggaagacttc 20 <210> 9 <211> 20 <212> DNA <213> Hepatitis C Virus <400> 9 cgcgcgacgc gcaaaacttc 20 <210> 10 <211> 20 <212> DNA <213> Hepatitis C Virus <400> 10 tgccttgggg ataggctgac 20 <210> 11 <211> 20 <212> DNA <213> Hepatitis C Virus <400> 11 gagccatcct gcccacccca 20 <210> 12 <211> 20 <212> DNA <213> Hepatitis C Virus <400> 12 gccccatgaa gggcgagaac 20 <210> 13 <211> 20 <212> DNA <213> Hepatitis C Virus <400> 13 accctcgttt ccgtacagag 20 <210> 14 <211> 20 <212> DNA <213> Hepatitis C Virus <400> 14 gctgagccca ggaccggtct 20 <210> 15 <211> 20 <212> DNA <213> Hepatitis C Virus <400> 15 aggaagactt ccgagcggtc 20 <210> 16 <211> 581 <212> DNA <213> Human (Homo sapiens) <400> 16 atgagccaga ctccagggag gcctagaagt gggcaagggg aaacgggaaa ggaggaagat 60 ggtatgggtg tgcctggtta ggggtgggag tgctggacgg agttcgggac aagaggggct 120 ctgcagccat tggcacacaa tgcctgggag tccctgctgg tgctgggatc atcccagtga 180 gccctgggag ggaactgaag acccccaatt accaatgcat ctgttttcaa aaccgacggg 240 gggaaggaca tgcctaggtt caaggatacg tgcaggcttg gatgactccg ggccattagg 300 gagcctccgg agcaccttga tcctcagacg ggcctgatga aacgagcatc tgattcagca 360 ggcctgggtt cgggcccgag aacctgcgtc tcccgcgagt tcccgcgagg caagtgctgn 420 aggtgcgggg ccaggagcta ggtttcgttt ctgctcccgg agccgccctc agcacagggt 480 ctgtgagttt catttcttcg ccggcgcggg gcggggctgg gcgcggggtg aaagaggcga 540 accgagagcg gaggccgcac tccagcactg cgcagggacc g 581 <210> 17 <211> 581 <212> DNA <213> People <400> 17 atgagccaga ctccagggag gcctagaagt gggcaagggg aaacgggaaa ggaggaagat 60 ggtatgggtg tgcctggtta ggggtgggag tgctggacgg agttcgggac aagaggggct 120 ctgcagccat tggcacacaa tgcctgggag tccctgctgg tgctgggatc atcccagtga 180 gccctgggag ggaactgaag acccccaatt accaatgcat ctgttttcaa aaccgacggg 240 gggaaggaca tgcctaggtt caaggatacg tgcaggcttg gatgactccg ggccattagg 300 gagcctccgg agcaccttga tcctcagacg ggcctgatga aacgagcatc tgattcagca 360 ggcctgggtt cgggcccgag aacctgcgtc tcccgcgagt tcccgcgagg caagtgctgn 420 aggtgcgggg ccaggagcta ggtttcgttt ctgcgcccgg agccgccctc agcacagggt 480 ctgtgagttt catttcttcg ccggcgcggg gcggggctgg gcgcggggtg aaagaggcga 540 accgagagcg gaggccgcac tccagcactg cgcagggacc g 581 <210> 18 <211> 581 <212> DNA <213> People <400> 18 atgagccaga ctccagggag gcctagaagt gggcaagggg aaacgggaaa ggaggaagat 60 ggtatgggtg tgcctggtta ggggtgggag tgctggacgg agttcgggac aagaggggct 120 ctgcagccat tggcacacaa tgcctgggag tccctgctgg tgctgggatc atcccagtga 180 gccctgggag ggaactgaag acccccaatt accaatgcat ctgttttcaa aaccgacggg 240 gggaaggaca tgcctaggtt caaggatacg tgcaggcttg gatgactccg ggccattagg 300 gagcctccgg agcaccttga tcctcagacg ggcctgatga aacgagcatc tgattcagca 360 ggcctgggtt cgggcccgag aacctgcgtc tcccgcgagt tcccgcgagg caagtgctgn 420 aggtgcgggg ccaggagcta ggtttcgttt ctgcacccgg agccgccctc agcacagggt 480 ctgtgagttt catttcttcg ccggcgcggg gcggggctgg gcgcggggtg aaagaggcga 540 accgagagcg gaggccgcac tccagcactg cgcagggacc g 581 <210> 19 <211> 581 <212> DNA <213> People <400> 19 atgagccaga ctccagggag gcctagaagt gggcaagggg aaacgggaaa ggaggaagat 60 ggtatgggtg tgcctggtta ggggtgggag tgctggacgg agttcgggac aagaggggct 120 ctgcagccat tggcacacaa tgcctgggag tccctgctgg tgctgggatc atcccagtga 180 gccctgggag ggaactgaag acccccaatt accaatgcat ctgttttcaa aaccgacggg 240 gggaaggaca tgcctaggtt caaggatacg tgcaggcttg gatgactccg ggccattagg 300 gagcctccgg agcaccttga tcctcagacg ggcctgatga aacgagcatc tgattcagca 360 ggcctgggtt cgggcccgag aacctgcgtc tcccgcgagt tcccgcgagg caagtgctgn 420 aggtgcgggg ccaggagcta ggtttcgttt ctgcccccgg agccgccctc agcacagggt 480 ctgtgagttt catttcttcg ccggcgcggg gcggggctgg gcgcggggtg aaagaggcga 640 accgagagcg gaggccgcac tccagcactg cgcagggacc g 581 <210> 20 <211> 22 <212> DNA <213> People <400> 20 aggtgcgggg ccaggagcta gg 22 <210> 21 <211> 22 <212> DNA <213> People <400> 21 ggcctccgct ctcgcttcgc ct 22 <210> 22 <211> 19 <212> DNA <213> People <400> 22 tcgtttctgc tcccggagc 19 <210> 23 <211> 19 <212> DNA <213> People <400> 23 tcgtttctgc gcccggagc 19 <210> 24 <211> 19 <212> DNA <213> People <400> 24 tcgtttctgc ccccggagc 19 <210> 25 <211> 19 <212> DNA <213> People <400> 25 tcgtttctgc acccggagc 19 <210> 26 <211> 20 <212> DNA <213> People <400> 26 cttgtctcgt agctgcagcc 20 <210> 27 <211> 15 <212> PNA <213> People <400> 27 gtttctgctc ccgga 15 <210> 28 <211> 15 <212> PNA <213> People <400> 28 gtttctgcgc ccgga 15 <210> 29 <211> 15 <212> PNA <213> People <400> 29 gtttctgccc ccgga 15 <210> 30 <211> 15 <212> PNA <213> People <400> 30 gtttctgcac ccgga 15 <210> 31 <211> 15 <212> PNA <213> People <400> 31 tgctgtcgat cgcac 15 <210> 32 <211> 15 <212> PNA <213> Hepatitis C Virus <400> 32 cttggggata ggctg 15 <210> 33 <211> 15 <212> PNA <213> Hepatitis C Virus <400> 33 ccatcctgcc caccc 15 <210> 34 <211> 15 <212> PNA <213> Hepatitis C Virus <400> 34 ccatgaaggg cgaga 15 <210> 35 <211> 15 <212> PNA <213> Hepatitis C Virus <400> 35 ctcgtttccg tacag 15 <210> 36 <211> 15 <212> PNA <213> Hepatitis C Virus <400> 36 gagcccagga ccggt 15 <210> 37 <211> 581 <212> DNA <213> People <400> 37 atgagccaga ctccagggag gcctagaagt gggcaagggg aaacgggaaa ggaggaagat 60 ggtatgggtg tgcctggtta ggggtgggag tgctggacgg agttcgggac aagaggggct 120 ctgcagccat tggcacacaa tgcctgggag tccctgctgg tgctgggatc atcccagtga 180 gccctgggag ggaactgaag acccccaatt accaatgcat ctgttttcaa aaccgacggg 240 gggaaggaca tgcctaggtt caaggatacg tgcaggcttg gatgactccg ggccattagg 300 gagcctccgg agcaccttga tcctcagacg ggcctgatga aacgagcatc tgattcagca 360 ggcctgggtt cgggcccgag aacctgcgtc tcccgcgagt tcccgcgagg caagtgctgt 420 aggtgcgggg ccaggagcta ggtttcgttt ctgcncccgg agccgccctc agcacagggt 480 ctgtgagttt catttcttcg ccggcgcggg gcggggctgg gcgcggggtg aaagaggcga 540 accgagagcg gaggccgcac tccagcactg cgcagggacc g 581 <210> 38 <211> 581 <212> DNA <213> People <400> 38 atgagccaga ctccagggag gcctagaagt gggcaagggg aaacgggaaa ggaggaagat 60 ggtatgggtg tgcctggtta ggggtgggag tgctggacgg agttcgggac aagaggggct 120 ctgcagccat tggcacacaa tgcctgggag tccctgctgg tgctgggatc atcccagtga 180 gccctgggag ggaactgaag acccccaatt accaatgcat ctgttttcaa aaccgacggg 240 gggaaggaca tgcctaggtt caaggatacg tgcaggcttg gatgactccg ggccattagg 300 gagcctccgg agcaccttga tcctcagacg ggcctgatga aacgagcatc tgattcagca 360 ggcctgggtt cgggcccgag aacctgcgtc tcccgcgagt tcccgcgagg caagtgctgg 420 aggtgcgggg ccaggagcta ggtttcgttt ctgcncccgg agccgccctc agcacagggt 480 ctgtgagttt catttcttcg ccggcgcggg gcggggctgg gcgcggggtg aaagaggcga 540 accgagagcg gaggccgcac tccagcactg cgcagggacc g 581 <210> 39 <211> 581 <212> DNA <213> People <400> 39 atgagccaga ctccagggag gcctagaagt gggcaagggg aaacgggaaa ggaggaagat 60 ggtatgggtg tgcctggtta ggggtgggag tgctggacgg agttcgggac aagaggggct 120 ctgcagccat tggcacacaa tgcctgggag tccctgctgg tgctgggatc atcccagtga 180 gccctgggag ggaactgaag acccccaatt accaatgcat ctgttttcaa aaccgacggg 240 gggaaggaca tgcctaggtt caaggatacg tgcaggcttg gatgactccg ggccattagg 300 gagcctccgg agcaccttga tcctcagacg ggcctgatga aacgagcatc tgattcagca 360 ggcctgggtt cgggcccgag aacctgcgtc tcccgcgagt tcccgcgagg caagtgctga 420 aggtgcgggg ccaggagcta ggtttcgttt ctgcncccgg agccgccctc agcacagggt 480 ctgtgagttt catttcttcg ccggcgcggg gcggggctgg gcgcggggtg aaagaggcga 540 accgagagcg gaggccgcac tccagcactg cgcagggacc g 581 <210> 40 <211> 581 <212> DNA <213> People <400> 39 atgagccaga ctccagggag gcctagaagt gggcaagggg aaacgggaaa ggaggaagat 60 ggtatgggtg tgcctggtta ggggtgggag tgctggacgg agttcgggac aagaggggct 120 ctgcagccat tggcacacaa tgcctgggag tccctgctgg tgctgggatc atcccagtga 180 gccctgggag ggaactgaag acccccaatt accaatgcat ctgttttcaa aaccgacggg 240 gggaaggaca tgcctaggtt caaggatacg tgcaggcttg gatgactccg ggccattagg 300 gagcctccgg agcaccttga tcctcagacg ggcctgatga aacgagcatc tgattcagca 360 ggcctgggtt cgggcccgag aacctgcgtc tcccgcgagt tcccgcgagg caagtgctgc 420 aggtgcgggg ccaggagcta ggtttcgttt ctgcncccgg agccgccctc agcacagggt 480 ctgtgagttt catttcttcg ccggcgcggg gcggggctgg gcgcggggtg aaagaggcga 540 accgagagcg gaggccgcac tccagcactg cgcagggacc g 581 <210> 41 <211> 1802 <212> DNA <213> People <400> 41 gaattcctgc cagaaagtag agaggtattt agcactctgc cagggccaac gtagtaagaa 60 atttccagag aaaatgctta cccaggcaag cctgtntaaa acaccaaggg gaagcaaact 120 ccagttaatt ctgggctggg ttggtgacta aggttgaggt tgatctgagg ttgagacctt 180 cctctttgga tcaccagctt tcagctcagg gcctgccaat gagtaaatga tagttaacag 240 gtcctggagg ggaatcagct gcccagatac aaagatggga ttcaggtggc agatggaccc 300 gaagaggaca tggagagaaa gaggaagctc ctacagacac ctgggtttcc actcattctc 360 attccctaag ctaacaggca taagccagct ggcaatgcac ggtcccattt gttctcactg 420 ccacggaaag catgtttata gtcttccagc agcaacgcca ggtgtctagg cacagatgaa 480 cccctcctta ggatccccac tgctcatcat agtgcctacc tttgttaaag tactagtcac 540 gcagtgtcac aaggaatgtt tacttttcca aatccccagc tagaggccag ggatgggtca 600 tctatttcta tatagcctgc acccagattg taggacagag ggcatgctng gtaaatatgt 660 gttcattaac tgagattaac cttccctgag ttttctcaca ccaaggtgag gaccatgtcc 720 ctgtttccat cactccctct ccttctcctg agtatggtgg cagcgtctta ctcagaaact 780 gtgacctgtg aggatgccca aaagacctgc cctgcagtga ttgcctgtag ctctccaggc 840 atcaacggct tcccaggcaa agatgggngt gatgncacca aggnagaaaa gggggaacca 900 ggtacgtgtt gggctgttct gtctctgcaa ttctttacct tccagaggaa actgcctggg 960 gatatgagga gactgatgtc ctatttgagt atatttttct caactatact gtaactcaaa 1020 acagagattc agctcgaatt ccacacagca gtttgtgact aatagttgtc ttgccagccc 1080 aggaaagtgg cccacaggtc aggccatccc gtgggacaca ggatgaattt ttcttctctg 1140 ggtcattgtc atgtcagacc cctattcact tcagtaggga tggcaccagg ttcaagaggc 1200 caaagaagag atggagtcag caaacaaaca taggttttac tgggggaatc tgtttacagg 1260 gagatccagc agcagtgggc tggacaggag aacaacaact actggtaaaa acaaatgcag 1320 ttaattttca ctttgcaccc tccctgcagc aacctccacg tggcaacttt atttcttaag 1380 ttattgctct caggtgcaca ccatacagtt attgagagca gtgctcagaa aggtcagtcc 1440 tgggtcaagg tctcccttct cctgagaagg gattgggcat caaactcttg aagagagaga 1500 gcaagaacat agatattaag tcacatttcc tttgtcttcc aacaggccaa gggctcagag 1560 gcttacaggg cccccctgga aagttggggc ctccaggaaa tccagggcct tctgggtcac 1620 caggaccaaa gggccaaaaa ggagaccctg gaaaaagtcc gggtaaggac cccagcaagg 1680 tctgagctga cttcacccag ggttctgaga ccttgagtat ctggtaagag gtgccccttc 1740 tcctgttcct tcaaaggaag atacccaaat ttgctttctg acccagtgcc ctcagccctc 1800 tc 1802 <210> 42 <211> 1802 <212> DNA <213> People <400> 42 gaattcctgc cagaaagtag agaggtattt agcactctgc cagggccaac gtagtaagaa 60 atttccagag aaaatgctta cccaggcaag cctgtntaaa acaccaaggg gaagcaaact 120 ccagttaatt ctgggctggg ttggtgacta aggttgaggt tgatctgagg ttgagacctt 180 cctctttgga tcaccagctt tcagctcagg gcctgccaat gagtaaatga tagttaacag 240 gtcctggagg ggaatcagct gcccagatac aaagatggga ttcaggtggc agatggaccc 300 gaagaggaca tggagagaaa gaggaagctc ctacagacac ctgggtttcc actcattctc 360 attccctaag ctaacaggca taagccagct ggcaatgcac ggtcccattt gttctcactg 420 ccaccgaaag catgtttata gtcttccagc agcaacgcca ggtgtctagg cacagatgaa 480 cccctcctta ggatccccac tgctcatcat agtgcctacc tttgttaaag tactagtcac 540 gcagtgtcac aaggaatgtt tacttttcca aatccccagc tagaggccag ggatgggtca 600 tctatttcta tatagcctgc acccagattg taggacagag ggcatgctng gtaaatatgt 660 gttcattaac tgagattaac cttccctgag ttttctcaca ccaaggtgag gaccatgtcc 720 ctgtttccat cactccctct ccttctcctg agtatggtgg cagcgtctta ctcagaaact 780 gtgacctgtg aggatgccca aaagacctgc cctgcagtga ttgcctgtag ctctccaggc 840 atcaacggct tcccaggcaa agatgggngt gatgncacca aggnagaaaa gggggaacca 900 ggtacgtgtt gggctgttct gtctctgcaa ttctttacct tccagaggaa actgcctggg 960 gatatgagga gactgatgtc ctatttgagt atatttttct caactatact gtaactcaaa 1020 acagagattc agctcgaatt ccacacagca gtttgtgact aatagttgtc ttgccagccc 1080 aggaaagtgg cccacaggtc aggccatccc gtgggacaca ggatgaattt ttcttctctg 1140 ggtcattgtc atgtcagacc cctattcact tcagtaggga tggcaccagg ttcaagaggc 1200 caaagaagag atggagtcag caaacaaaca taggttttac tgggggaatc tgtttacagg 1260 gagatccagc agcagtgggc tggacaggag aacaacaact actggtaaaa acaaatgcag 1320 ttaattttca ctttgcaccc tccctgcagc aacctccacg tggcaacttt atttcttaag 1380 ttattgctct caggtgcaca ccatacagtt attgagagca gtgctcagaa aggtcagtcc 1440 tgggtcaagg tctcccttct cctgagaagg gattgggcat caaactcttg aagagagaga 1500 gcaagaacat agatattaag tcacatttcc tttgtcttcc aacaggccaa gggctcagag 1560 gcttacaggg cccccctgga aagttggggc ctccaggaaa tccagggcct tctgggtcac 1620 caggaccaaa gggccaaaaa ggagaccctg gaaaaagtcc gggtaaggac cccagcaagg 1680 tctgagctga cttcacccag ggttctgaga ccttgagtat ctggtaagag gtgccccttc 1740 tcctgttcct tcaaaggaag atacccaaat ttgctttctg acccagtgcc ctcagccctc 1800 tc 1802 <210> 43 <211> 1802 <212> DNA <213> People <400> 43 gaattcctgc cagaaagtag agaggtattt agcactctgc cagggccaac gtagtaagaa 60 atttccagag aaaatgctta cccaggcaag cctgtntaaa acaccaaggg gaagcaaact 120 ccagttaatt ctgggctggg ttggtgacta aggttgaggt tgatctgagg ttgagacctt 180 cctctttgga tcaccagctt tcagctcagg gcctgccaat gagtaaatga tagttaacag 240 gtcctggagg ggaatcagct gcccagatac aaagatggga ttcaggtggc agatggaccc 300 gaagaggaca tggagagaaa gaggaagctc ctacagacac ctgggtttcc actcattctc 360 attccctaag ctaacaggca taagccagct ggcaatgcac ggtcccattt gttctcactg 420 ccacagaaag catgtttata gtcttccagc agcaacgcca ggtgtctagg cacagatgaa 480 cccctcctta ggatccccac tgctcatcat agtgcctacc tttgttaaag tactagtcac 540 gcagtgtcac aaggaatgtt tacttttcca aatccccagc tagaggccag ggatgggtca 600 tctatttcta tatagcctgc acccagattg taggacagag ggcatgctng gtaaatatgt 660 gttcattaac tgagattaac cttccctgag ttttctcaca ccaaggtgag gaccatgtcc 720 ctgtttccat cactccctct ccttctcctg agtatggtgg cagcgtctta ctcagaaact 780 gtgacctgtg aggatgccca aaagacctgc cctgcagtga ttgcctgtag ctctccaggc 840 atcaacggct tcccaggcaa agatgggngt gatgncacca aggnagaaaa gggggaacca 900 ggtacgtgtt gggctgttct gtctctgcaa ttctttacct tccagaggaa actgcctggg 960 gatatgagga gactgatgtc ctatttgagt atatttttct caactatact gtaactcaaa 1020 acagagattc agctcgaatt ccacacagca gtttgtgact aatagttgtc ttgccagccc 1080 aggaaagtgg cccacaggtc aggccatccc gtgggacaca ggatgaattt ttcttctctg 1140 ggtcattgtc atgtcagacc cctattcact tcagtaggga tggcaccagg ttcaagaggc 1200 caaagaagag atggagtcag caaacaaaca taggttttac tgggggaatc tgtttacagg 1260 gagatccagc agcagtgggc tggacaggag aacaacaact actggtaaaa acaaatgcag 1320 ttaattttca ctttgcaccc tccctgcagc aacctccacg tggcaacttt atttcttaag 1380 ttattgctct caggtgcaca ccatacagtt attgagagca gtgctcagaa aggtcagtcc 1440 tgggtcaagg tctcccttct cctgagaagg gattgggcat caaactcttg aagagagaga 1500 gcaagaacat agatattaag tcacatttcc tttgtcttcc aacaggccaa gggctcagag 1560 gcttacaggg cccccctgga aagttggggc ctccaggaaa tccagggcct tctgggtcac 1620 caggaccaaa gggccaaaaa ggagaccctg gaaaaagtcc gggtaaggac cccagcaagg 1680 tctgagctga cttcacccag ggttctgaga ccttgagtat ctggtaagag gtgccccttc 1740 tcctgttcct tcaaaggaag atacccaaat ttgctttctg acccagtgcc ctcagccctc 1800 tc 1802 <210> 44 <211> 1802 <212> DNA <213> People <400> 44 gaattcctgc cagaaagtag agaggtattt agcactctgc cagggccaac gtagtaagaa 60 atttccagag aaaatgctta cccaggcaag cctgtntaaa acaccaaggg gaagcaaact 120 ccagttaatt ctgggctggg ttggtgacta aggttgaggt tgatctgagg ttgagacctt 180 cctctttgga tcaccagctt tcagctcagg gcctgccaat gagtaaatga tagttaacag 240 gtcctggagg ggaatcagct gcccagatac aaagatggga ttcaggtggc agatggaccc 300 gaagaggaca tggagagaaa gaggaagctc ctacagacac ctgggtttcc actcattctc 360 attccctaag ctaacaggca taagccagct ggcaatgcac ggtcccattt gttctcactg 420 ccactgaaag catgtttata gtcttccagc agcaacgcca ggtgtctagg cacagatgaa 480 cccctcctta ggatccccac tgctcatcat agtgcctacc tttgttaaag tactagtcac 540 gcagtgtcac aaggaatgtt tacttttcca aatccccagc tagaggccag ggatgggtca 600 tctatttcta tatagcctgc acccagattg taggacagag ggcatgctng gtaaatatgt 660 gttcattaac tgagattaac cttccctgag ttttctcaca ccaaggtgag gaccatgtcc 720 ctgtttccat cactccctct ccttctcctg agtatggtgg cagcgtctta ctcagaaact 780 gtgacctgtg aggatgccca aaagacctgc cctgcagtga ttgcctgtag ctctccaggc 840 atcaacggct tcccaggcaa agatgggngt gatgncacca aggnagaaaa gggggaacca 900 ggtacgtgtt gggctgttct gtctctgcaa ttctttacct tccagaggaa actgcctggg 960 gatatgagga gactgatgtc ctatttgagt atatttttct caactatact gtaactcaaa 1020 acagagattc agctcgaatt ccacacagca gtttgtgact aatagttgtc ttgccagccc 1080 aggaaagtgg cccacaggtc aggccatccc gtgggacaca ggatgaattt ttcttctctg 1140 ggtcattgtc atgtcagacc cctattcact tcagtaggga tggcaccagg ttcaagaggc 1200 caaagaagag atggagtcag caaacaaaca taggttttac tgggggaatc tgtttacagg 1260 gagatccagc agcagtgggc tggacaggag aacaacaact actggtaaaa acaaatgcag 1320 ttaattttca ctttgcaccc tccctgcagc aacctccacg tggcaacttt atttcttaag 1380 ttattgctct caggtgcaca ccatacagtt attgagagca gtgctcagaa aggtcagtcc 1440 tgggtcaagg tctcccttct cctgagaagg gattgggcat caaactcttg aagagagaga 1500 gcaagaacat agatattaag tcacatttcc tttgtcttcc aacaggccaa gggctcagag 1560 gcttacaggg cccccctgga aagttggggc ctccaggaaa tccagggcct tctgggtcac 1620 caggaccaaa gggccaaaaa ggagaccctg gaaaaagtcc gggtaaggac cccagcaagg 1680 tctgagctga cttcacccag ggttctgaga ccttgagtat ctggtaagag gtgccccttc 1740 tcctgttcct tcaaaggaag atacccaaat ttgctttctg acccagtgcc ctcagccctc 1800 tc 1802 <210> 45 <211> 1802 <212> DNA <213> People <400> 45 gaattcctgc cagaaagtag agaggtattt agcactctgc cagggccaac gtagtaagaa 60 atttccagag aaaatgctta cccaggcaag cctgtntaaa acaccaaggg gaagcaaact 120 ccagttaatt ctgggctggg ttggtgacta aggttgaggt tgatctgagg ttgagacctt 180 cctctttgga tcaccagctt tcagctcagg gcctgccaat gagtaaatga tagttaacag 240 gtcctggagg ggaatcagct gcccagatac aaagatggga ttcaggtggc agatggaccc 300 gaagaggaca tggagagaaa gaggaagctc ctacagacac ctgggtttcc actcattctc 360 attccctaag ctaacaggca taagccagct ggcaatgcac ggtcccattt gttctcactg 420 ccacngaaag catgtttata gtcttccagc agcaacgcca ggtgtctagg cacagatgaa 480 cccctcctta ggatccccac tgctcatcat agtgcctacc tttgttaaag tactagtcac 540 gcagtgtcac aaggaatgtt tacttttcca aatccccagc tagaggccag ggatgggtca 600 tctatttcta tatagcctgc acccagattg taggacagag ggcatgctng gtaaatatgt 660 gttcattaac tgagattaac cttccctgag ttttctcaca ccaaggtgag gaccatgtcc 720 ctgtttccat cactccctct ccttctcctg agtatggtgg cagcgtctta ctcagaaact 780 gtgacctgtg aggatgccca aaagacctgc cctgcagtga ttgcctgtag ctctccaggc 840 atcaacggct tcccaggcaa agatgggngt gatggcacca aggnagaaaa gggggaacca 900 ggtacgtgtt gggctgttct gtctctgcaa ttctttacct tccagaggaa actgcctggg 960 gatatgagga gactgatgtc ctatttgagt atatttttct caactatact gtaactcaaa 1020 acagagattc agctcgaatt ccacacagca gtttgtgact aatagttgtc ttgccagccc 1080 aggaaagtgg cccacaggtc aggccatccc gtgggacaca ggatgaattt ttcttctctg 1140 ggtcattgtc atgtcagacc cctattcact tcagtaggga tggcaccagg ttcaagaggc 1200 caaagaagag atggagtcag caaacaaaca taggttttac tgggggaatc tgtttacagg 1260 gagatccagc agcagtgggc tggacaggag aacaacaact actggtaaaa acaaatgcag 1320 ttaattttca ctttgcaccc tccctgcagc aacctccacg tggcaacttt atttcttaag 1380 ttattgctct caggtgcaca ccatacagtt attgagagca gtgctcagaa aggtcagtcc 1440 tgggtcaagg tctcccttct cctgagaagg gattgggcat caaactcttg aagagagaga 1500 gcaagaacat agatattaag tcacatttcc tttgtcttcc aacaggccaa gggctcagag 1560 gcttacaggg cccccctgga aagttggggc ctccaggaaa tccagggcct tctgggtcac 1620 caggaccaaa gggccaaaaa ggagaccctg gaaaaagtcc gggtaaggac cccagcaagg 1680 tctgagctga cttcacccag ggttctgaga ccttgagtat ctggtaagag gtgccccttc 1740 tcctgttcct tcaaaggaag atacccaaat ttgctttctg acccagtgcc ctcagccctc 1800 tc 1802 <210> 46 <211> 1802 <212> DNA <213> People <400> 46 gaattcctgc cagaaagtag agaggtattt agcactctgc cagggccaac gtagtaagaa 60 atttccagag aaaatgctta cccaggcaag cctgtntaaa acaccaaggg gaagcaaact 120 ccagttaatt ctgggctggg ttggtgacta aggttgaggt tgatctgagg ttgagacctt 180 cctctttgga tcaccagctt tcagctcagg gcctgccaat gagtaaatga tagttaacag 240 gtcctggagg ggaatcagct gcccagatac aaagatggga ttcaggtggc agatggaccc 300 gaagaggaca tggagagaaa gaggaagctc ctacagacac ctgggtttcc actcattctc 360 attccctaag ctaacaggca taagccagct ggcaatgcac ggtcccattt gttctcactg 420 ccacngaaag catgtttata gtcttccagc agcaacgcca ggtgtctagg cacagatgaa 480 cccctcctta ggatccccac tgctcatcat agtgcctacc tttgttaaag tactagtcac 540 gcagtgtcac aaggaatgtt tacttttcca aatccccagc tagaggccag ggatgggtca 600 tctatttcta tatagcctgc acccagattg taggacagag ggcatgctng gtaaatatgt 660 gttcattaac tgagattaac cttccctgag ttttctcaca ccaaggtgag gaccatgtcc 720 ctgtttccat cactccctct ccttctcctg agtatggtgg cagcgtctta ctcagaaact 780 gtgacctgtg aggatgccca aaagacctgc cctgcagtga ttgcctgtag ctctccaggc 840 atcaacggct tcccaggcaa agatgggngt gatgacacca aggnagaaaa gggggaacca 900 ggtacgtgtt gggctgttct gtctctgcaa ttctttacct tccagaggaa actgcctggg 960 gatatgagga gactgatgtc ctatttgagt atatttttct caactatact gtaactcaaa 1020 acagagattc agctcgaatt ccacacagca gtttgtgact aatagttgtc ttgccagccc 1080 aggaaagtgg cccacaggtc aggccatccc gtgggacaca ggatgaattt ttcttctctg 1140 ggtcattgtc atgtcagacc cctattcact tcagtaggga tggcaccagg ttcaagaggc 1200 caaagaagag atggagtcag caaacaaaca taggttttac tgggggaatc tgtttacagg 1260 gagatccagc agcagtgggc tggacaggag aacaacaact actggtaaaa acaaatgcag 1320 ttaattttca ctttgcaccc tccctgcagc aacctccacg tggcaacttt atttcttaag 1380 ttattgctct caggtgcaca ccatacagtt attgagagca gtgctcagaa aggtcagtcc 1440 tgggtcaagg tctcccttct cctgagaagg gattgggcat caaactcttg aagagagaga 1500 gcaagaacat agatattaag tcacatttcc tttgtcttcc aacaggccaa gggctcagag 1560 gcttacaggg cccccctgga aagttggggc ctccaggaaa tccagggcct tctgggtcac 1620 caggaccaaa gggccaaaaa ggagaccctg gaaaaagtcc gggtaaggac cccagcaagg 1680 tctgagctga cttcacccag ggttctgaga ccttgagtat ctggtaagag gtgccccttc 1740 tcctgttcct tcaaaggaag atacccaaat ttgctttctg acccagtgcc ctcagccctc 1800 tc 1802 <210> 47 <211> 1802 <212> DNA <213> People <400> 47 gaattcctgc cagaaagtag agaggtattt agcactctgc cagggccaac gtagtaagaa 60 atttccagag aaaatgctta cccaggcaag cctgtntaaa acaccaaggg gaagcaaact 120 ccagttaatt ctgggctggg ttggtgacta aggttgaggt tgatctgagg ttgagacctt 180 cctctttgga tcaccagctt tcagctcagg gcctgccaat gagtaaatga tagttaacag 240 gtcctggagg ggaatcagct gcccagatac aaagatggga ttcaggtggc agatggaccc 300 gaagaggaca tggagagaaa gaggaagctc ctacagacac ctgggtttcc actcattctc 360 attccctaag ctaacaggca taagccagct ggcaatgcac ggtcccattt gttctcactg 420 ccacngaaag catgtttata gtcttccagc agcaacgcca ggtgtctagg cacagatgaa 480 cccctcctta ggatccccac tgctcatcat agtgcctacc tttgttaaag tactagtcac 540 gcagtgtcac aaggaatgtt tacttttcca aatccccagc tagaggccag ggatgggtca 600 tctatttcta tatagcctgc acccagattg taggacagag ggcatgctng gtaaatatgt 660 gttcattaac tgagattaac cttccctgag ttttctcaca ccaaggtgag gaccatgtcc 720 ctgtttccat cactccctct ccttctcctg agtatggtgg cagcgtctta ctcagaaact 780 gtgacctgtg aggatgccca aaagacctgc cctgcagtga ttgcctgtag ctctccaggc 840 atcaacggct tcccaggcaa agatgggngt gatgccacca aggnagaaaa gggggaacca 900 ggtacgtgtt gggctgttct gtctctgcaa ttctttacct tccagaggaa actgcctggg 960 gatatgagga gactgatgtc ctatttgagt atatttttct caactatact gtaactcaaa 1020 acagagattc agctcgaatt ccacacagca gtttgtgact aatagttgtc ttgccagccc 1080 aggaaagtgg cccacaggtc aggccatccc gtgggacaca ggatgaattt ttcttctctg 1140 ggtcattgtc atgtcagacc cctattcact tcagtaggga tggcaccagg ttcaagaggc 1200 caaagaagag atggagtcag caaacaaaca taggttttac tgggggaatc tgtttacagg 1260 gagatccagc agcagtgggc tggacaggag aacaacaact actggtaaaa acaaatgcag 1320 ttaattttca ctttgcaccc tccctgcagc aacctccacg tggcaacttt atttcttaag 1380 ttattgctct caggtgcaca ccatacagtt attgagagca gtgctcagaa aggtcagtcc 1440 tgggtcaagg tctcccttct cctgagaagg gattgggcat caaactcttg aagagagaga 1500 gcaagaacat agatattaag tcacatttcc tttgtcttcc aacaggccaa gggctcagag 1560 gcttacaggg cccccctgga aagttggggc ctccaggaaa tccagggcct tctgggtcac 1620 caggaccaaa gggccaaaaa ggagaccctg gaaaaagtcc gggtaaggac cccagcaagg 1680 tctgagctga cttcacccag ggttctgaga ccttgagtat ctggtaagag gtgccccttc 1740 tcctgttcct tcaaaggaag atacccaaat ttgctttctg acccagtgcc ctcagccctc 1800 tc 1802 <210> 48 <211> 1802 <212> DNA <213> People <400> 48 gaattcctgc cagaaagtag agaggtattt agcactctgc cagggccaac gtagtaagaa 60 atttccagag aaaatgctta cccaggcaag cctgtntaaa acaccaaggg gaagcaaact 120 ccagttaatt ctgggctggg ttggtgacta aggttgaggt tgatctgagg ttgagacctt 180 cctctttgga tcaccagctt tcagctcagg gcctgccaat gagtaaatga tagttaacag 240 gtcctggagg ggaatcagct gcccagatac aaagatggga ttcaggtggc agatggaccc 300 gaagaggaca tggagagaaa gaggaagctc ctacagacac ctgggtttcc actcattctc 360 attccctaag ctaacaggca taagccagct ggcaatgcac ggtcccattt gttctcactg 420 ccacngaaag catgtttata gtcttccagc agcaacgcca ggtgtctagg cacagatgaa 480 cccctcctta ggatccccac tgctcatcat agtgcctacc tttgttaaag tactagtcac 540 gcagtgtcac aaggaatgtt tacttttcca aatccccagc tagaggccag ggatgggtca 600 tctatttcta tatagcctgc acccagattg taggacagag ggcatgctng gtaaatatgt 660 gttcattaac tgagattaac cttccctgag ttttctcaca ccaaggtgag gaccatgtcc 720 ctgtttccat cactccctct ccttctcctg agtatggtgg cagcgtctta ctcagaaact 780 gtgacctgtg aggatgccca aaagacctgc cctgcagtga ttgcctgtag ctctccaggc 840 atcaacggct tcccaggcaa agatgggngt gatgtcacca aggnagaaaa gggggaacca 900 ggtacgtgtt gggctgttct gtctctgcaa ttctttacct tccagaggaa actgcctggg 960 gatatgagga gactgatgtc ctatttgagt atatttttct caactatact gtaactcaaa 1020 acagagattc agctcgaatt ccacacagca gtttgtgact aatagttgtc ttgccagccc 1080 aggaaagtgg cccacaggtc aggccatccc gtgggacaca ggatgaattt ttcttctctg 1140 ggtcattgtc atgtcagacc cctattcact tcagtaggga tggcaccagg ttcaagaggc 1200 caaagaagag atggagtcag caaacaaaca taggttttac tgggggaatc tgtttacagg 1260 gagatccagc agcagtgggc tggacaggag aacaacaact actggtaaaa acaaatgcag 1320 ttaattttca ctttgcaccc tccctgcagc aacctccacg tggcaacttt atttcttaag 1380 ttattgctct caggtgcaca ccatacagtt attgagagca gtgctcagaa aggtcagtcc 1440 tgggtcaagg tctcccttct cctgagaagg gattgggcat caaactcttg aagagagaga 1500 gcaagaacat agatattaag tcacatttcc tttgtcttcc aacaggccaa gggctcagag 1560 gcttacaggg cccccctgga aagttggggc ctccaggaaa tccagggcct tctgggtcac 1620 caggaccaaa gggccaaaaa ggagaccctg gaaaaagtcc gggtaaggac cccagcaagg 1680 tctgagctga cttcacccag ggttctgaga ccttgagtat ctggtaagag gtgccccttc 1740 tcctgttcct tcaaaggaag atacccaaat ttgctttctg acccagtgcc ctcagccctc 1800 tc 1802 <210> 49 <211> 1802 <212> DNA <213> People <400> 49 gaattcctgc cagaaagtag agaggtattt agcactctgc cagggccaac gtagtaagaa 60 atttccagag aaaatgctta cccaggcaag cctgtntaaa acaccaaggg gaagcaaact 120 ccagttaatt ctgggctggg ttggtgacta aggttgaggt tgatctgagg ttgagacctt 180 cctctttgga tcaccagctt tcagctcagg gcctgccaat gagtaaatga tagttaacag 240 gtcctggagg ggaatcagct gcccagatac aaagatggga ttcaggtggc agatggaccc 300 gaagaggaca tggagagaaa gaggaagctc ctacagacac ctgggtttcc actcattctc 360 attccctaag ctaacaggca taagccagct ggcaatgcac ggtcccattt gttctcactg 420 <210> 50 <212> DNA <213> People <400> 50 <210> 51 <212> DNA <213> People <400> 51 <210> 52 <212> DNA <213> People <400> 52 <210> 53 <212> DNA <213> People <400> 53 <210> 54 <212> DNA <213> People <400> 54 <210> 55 <212> DNA <213> People <400> 55 <210> 56 <212> DNA <213> People <400> 56 <210> 57 <211> 18 <212> DNA <213> People <400> 57 <210> 58 <211> 18 <212> DNA <213> People <400> 58 <210> 59 <211> 18 <212> DNA <213> People <400> 59 <210> 60 <211> 18 <212> DNA <213> People <400> 60 <210> 61 <211> 18 <212> DNA <213> People <400> 61 <210> 62 <211> 18 <212> DNA <213> People <400> 62 <210> 63 <211> 18 <212> DNA <213> People <400> 63 <210> 64 <211> 18 <212> DNA <213> People <400> 64 <210> 65 <211> 18 <212> DNA <213> People <400> 65 <210> 66 <211> 18 <212> DNA <213> People <400> 66 <210> 67 <211> 18 <212> DNA <213> People <400> 67 <210> 68 <211> 18 <212> DNA <213> People <400> 68 <210> 69 <211> 30 <212> DNA <213> People <400> 69 <210> 70 <211> 30 <212> DNA <213> People <400> 70 <210> 71 <211> 19 <212> DNA <213> People <400> 71 <210> 72 <211> 20 <212> DNA <213> People <400> 72 ...Consumer-electronics applicationsSound System Pocket / household type 1-1201-10 case portable recorder / CD 1-120 1-5 Walkman / Pocket Stereo Machine 1-120 1-5 CB radios 1-1201-10 amateur radio transceivers apparatus used 1-1201-100 cam tape loop automatic recorder 1-1201-10 home satellite antenna reflector 1-1201-10 1-1201-3 microphone monitors and cathode ray tube 1-10001 -100 flash 1-10001-3 receivers, transceivers 1-10001-10 telephone answering device 1-1201-5 network, wireless phone 1-1201-3 1-1201-10 TV Toys and games household equipment 1-10001-10 1-10001-10 1-10001-10 portable cassette recorders (VCRs) 1-120 1-10 disc player 1-1201-10 video game 1-120 1-10 table / bell 1-1201-100Consumer household electrical appliances applicationair purifier, 1-120, 1-100, the sack sealer, 1-150, 1-100, agitator, 1-120, 1-10, full-time clock (Clocks-Total), 1-120, 1-100, alarm and console, 1-120, 1-10, electric coffee grinder, 1-120, 1-10, the coffee processing machine, 1-120, 1-10, convection furnace, 1-1000, 1-1000, quick-fried corn machine, 1-120, 1-10, curly hair ferrochrome/brush, 1-120, 1-5, deep fryer, 1-230, 1-100, electrical blanket, 1-120, 1-10, flashlight, 1-100, 1-10, electric floor polisher, 1-220, 1-100, food processor, 1-120, 1-10, hair dryer, 1-120, 1-5, heating cushion, 1-120, 1-5, home security system, 1-120, 1-100, flatiron, 1-120, 1-5, cutting machine, 1-120, 1-3, beauty care device, 1-120, 1-5, blender, 1-120, 1-5, micro-wave oven, 1-230, 1-10, electric tool, 1-230, 1-100, security system, 1-230, 1-100, shave, 1-120, 1-3, smoke detector, 1-120, 1-5, timer, 1-120, 1-3, toaster/oven, 1-120, 1-5, toothbrush (electronic), 1-120, 1-3, vaporizer, 1-120, 1-10, the water contact maker, 1-120, 1-10, swirler (just carrying formula), 1-120, 1-100Main domestic consumer apparatusCompacting machine 1-120 1-10 dish-washing machine 1-220 1-100 baker 1-120 1-100 refrigerator-freezer 1-220 1-100 utilizes multifunctional range 1-220 1-1000 (Ranges) the refrigerator 1-120 1-100 washing machine 1-220 1-100 water heater 1-220 1-100 of waste heatOutdoor apparatusThe outdoor fence 1-120 of disinsector 1-120 1-10 1-100 power-operated mower 1-220 1-100 riding type hay mover 1-1000 1-1000 riding type tractor 1-1000 1-10000 rotary cultivator 1-1000 1-10000 snowplough/air blast 1-220 1-1000 lawn trimmer 1-220 1-100Other applicationThe electrical deicing machine 1-1000 1-100 electronic fuse 1-1000 1-10 laser instrument 1-1000 1-100 long-range sprinkler 1-1000 of row radar 1-1000 1-1000 1-10000 mutually is used for the i.e. storage of power plant homogenizing load alternately memory (solar energy, fuel cell, the wind-force whirlpool 1-1000 1-10 of the energy of generation, 000,000 take turns/etc.)
Military Application defence 1-10,000 0.1-10.000.000
For application-specific, multiple arrangement series connection and/or parallel connection are reached desirable performance.
The manufacturing of dry type precast segment
Following example only is used for describing and demonstration, and they can not be considered to the restriction to inventing by any way.
Example 1
The manufacturing of dry type precast segment
(A) painting method
Use 35%HNO 3/ 1.5%HF carries out etching in 5 minutes at 60 ℃ of titanium sheets to 1mil (0.00254cm), makes supporting construction thus.The end pole plate is the titanium of 5mil (0.0127cm).
Oxide coating solution is to contain the ruthenium trichloride trihydrate of 0.2M and the columbium pentachloride of 0.2M in the tert-butyl alcohol (SILVER REAGENT).
By under environmental condition, in solution, flooding, the Ti sheet after the etching is carried out dip-coating.Sheet after the coating is invaded solution and is kept taking out then in about 1 second.
After each the coating, 70 ℃ to dry 10 minutes of oxide, 350 ℃ of thermal decompositions of carrying out 10 minutes, take out then and be cooled to room temperature, all these all carry out in ambiance.
Repeat the dip-coating step and reach 10 layers of coating (or any desired quantity), rotation Ti sheet is so that alternately immerse each face.Thickness reaches about 10 microns.
Titanium sheet after applying fully in ambiance in 350 ℃ of final annealings that carry out 3 hours.
(B) electrode gives processing
Under self pressure, the electrode after the coating contacts 3 hours with saturated steam down at 280 ℃ in airtight container.
(C) at interval
Silk screen printing becomes the dimpling head on the one side of electrode, as being described in detail by " silk screen printing " with lower banner.Epoxy compounds is EP21AR, takes from Masterbond of Hackensack, the New Jersey.
In air, the epoxy plush copper was solidified 4 hours at 150 ℃.Then the electrode after applying is molded into the shape of expectation.
(D) add the cushions
Have a side of dimpling head at electrode, the modification high-density polyethylene (HDPE, modification aspect anti-perforation and bonding force) of thick 1.5mil (0.00381cm), wide 30mil (0.0762cm) is set, its peripheral boundary is identical with electrode, then the PULSE HEATING lamination.HDPE Be the PJX2242 grade, take from Phillips-Joannaof Ladd, the Illinois.
(E) band
The band that a thick 0.9mil (0.00229cm), wide 10mil (0.0254cm) are set is at the Dupont of machine direction rip cutting T 2TEFZEL Film 90ZM is across the narrow dimension of liner and electrode surface and aim between the dimpling head.Band can be positioned one of center, the survey of a left side, center or these three kinds of positions, right side, center.
Be provided with on first liner the 2nd HDPE strap clamp between two-layer liner.
Second liner is carried out PULSE HEATING make itself and first liner bonding, and make the band fix in position.
(F) stacked
Begin at the end pole plate of nonmetal (pottery) last line-up jig by 5mil (0.0127cm), stacked electrode/dimpling head/liner/band/spacer assembly, make assembly reach the capacitor chip quantity of expectation, last and stacked with the level and smooth end pole plate termination assembly of 5mil (0.0127cm), it is the position (end perspective) of repetition period by staggered location, left, center, right with Unit three that band is arranged on one, optical pressure is applied to the top of overlapped assembly by a ceramic platen piece, so that optical pressure can keep uniform adjusting to a line and contact on whole overlapped assembly.
(C) reflux
Use radio-frequency induction heater (2.5KW) that overlapped assembly is heated.In three times are rotated, overlapped assembly is arranged on the hub of a spool that diameter is 3 inches (7.62cm), and heated 90 seconds with 32% of setting power.Make the assembly of fusion be cooled to room temperature.
(H) remove tape
The end that exposes to the open air of backguy band is removed tape carefully, stays unlimited filler opening.
Embodiment 2
The another kind of method for making of dry type precast segment
(A) painting method
Carry out 30 minutes etching with 50%HCl at 75 ℃ of titanium sheets, be prepared into supporting construction thus 1mil (0.00254cm).The end pole plate is the titanium of 2mil (0.00508cm).
Oxide coating solution is to contain the ruthenium trichloride trihydrate of 0.3M and the tantalic chloride of 0.2M in isopropyl alcohol (SILVER REAGENT).
By under environmental condition, in solution, flooding, the Ti sheet after the etching is carried out dip-coating.Sheet after the coating immerses solution and keeps taking out then in about 1 second.
After each the coating, in ambiance under 70 ℃ to dry 10 minutes of oxide, in the air-flow of per hour 3 cubic feet 50 volume % oxygen and 50 volume % nitrogen, under 330 ℃, carry out 15 minutes thermal decomposition, take out then and in ambiance, be cooled to room temperature.
Repeat the dip-coating step and reach 30 layers of coating (or any desired quantity), rotation Ti sheet is so that alternately immerse each face.
Titanium sheet after applying fully carries out 3 hours final annealing under these conditions.
(C) at interval
Silk screen printing becomes VITON on the one side of electrode The dimpling head is as being described in detail with lower banner " VII, silk screen printing ".
In air, VITON The dimpling head solidified 30 minutes at 150 ℃.Then the electrode after applying is molded into the shape of expectation.
(D) add the cushions
Modification high-density polyethylene (the HDPE of thick 1.0mil (0.00254cm), wide 20mil (0.0508cm) is set in the electrode both sides, modification aspect anti-perforation and bonding force), its peripheral boundary is identical with electrode, PULSE HEATING lamination then, HDPE is the PJX2242 grade, take from Phillips-Joanna of Ladd, the Illinois.
(E) band
It is that 1mil (0.00254cm) applies TEFLON that a diameter is set The band of tungsten line, cross the narrow dimension of liner and electrode surface and between the dimpling head, aim at, band can be positioned one of center, center left or these three kinds of positions, right side, center.
(F) stacked
Stacked electrode/dimpling head/liner/band/spacer assembly, assembly is begun by the end pole plate of 2mil (0.00508cm), reach desired capacitor chip quantity, smooth end pole plate by 2mil (0.00508cm) stops, and it is the position of repetition period by staggered location, left, center, right (end perspective) with three unit that tape is arranged on one.
(C) reflux
The HDPE liner in nitrogen under 125 ℃ through 120 minutes, thermoplastics is refluxed.Assembly is cooled to room temperature in nitrogen.
(H) tape is removed
Pull out exposed ends and remove tape, stay unlimited filler opening.
Embodiment 3
Another method for making of dry type precast segment
(A) painting method
Carry out 30 minutes etching with 50%HCl at 75 ℃ of titanium sheets, be prepared into supporting construction thus 1mil (0.00254cm).The end pole plate is the titanium of 10mil (0.0254cm).
Oxide coating solution is to close the ruthenium trichloride trihydrate of 0.2M and the tantalic chloride of 0.2M in isopropyl alcohol (SILVER REAGENT).
By under environmental condition, in solution, flood, the Ti sheet after the etching is carried out dip-coating.Sheet after the coating immerses solution and keeps taking out then in about 1 second.
After each the coating, 70 ℃ to dry 10 minutes of oxide, 300 ℃ of thermal decompositions of carrying out 5 minutes, take out then and be cooled to room temperature, institute all carries out in ambiance in steps.
Repeat the dip-coating step and reach 10 layers of coating (or any desired quantity), rotation Ti sheet is so that alternately immerse each face.
Sheet after applying fully in ambiance in 300 ℃ of final annealings that carry out 3 hours.
(B) electrode gives processing
Under self pressure, the electrode after the coating in airtight container 260 ℃ contact 2 hours with saturated steam down.
(C) at interval
Lateral filament reticulated printing at electrode becomes the dimpling head, and subscript is entitled as that " VII, silk screen printing " described in detail in addition.Epoxy compounds is the EP21AR grade, takes from Masterboud, Hackensack, New Jersey.
In air, the epoxy plush copper was solidified 4 hours at 150 ℃.Then the electrode after applying is molded into the shape of expectation.
(D) add the cushions
Have a side of dimpling head at electrode, the modification high-density polyethylene (HDPE, modification aspect anti-perforation and bonding force) of thick 1.5mil (0.00381cm), wide 30mil (0.0762cm) is set, its peripheral boundary is identical with electrode, then the PULSE HEATING lamination.HDPE Be the PJX2242 grade, take from Phillips-Joanna of Ladd, the Illinois.
(E) band
Band (the TEFZEL of a thick 1mil (0.00254cm), wide 10mil (0.0254cm) is set ), across the narrow dimension of liner and electrode surface and between the dimpling head, aim at.Band can be positioned one of center, center left or these three kinds of positions, right side, center.
Second layer HDPE is set on first liner Liner strap clamp between two-layer liner.
Second liner is carried out PULSE HEATING make itself and first liner bonding, and make the band fix in position.
(F) stacked
Stacked electrode/dimpling head/liner/band/spacer assembly, assembly is begun by the end pole plate of 10mil (0.0254cm), reaches desired capacitor chip quantity.End pole plate by 10mil (0.0254cm) begins, reach desired capacitor chip quantity, smooth end pole plate termination by 10mil (0.0254cm) is stacked, and it is that the repetition period is by staggered location, left, center, right (end perspective) with Unit three that band is arranged on one.
(G) reflux
Liner in nitrogen under 160 ℃ through 45 minutes, thermoplastic domestic animal plastics are refluxed.Assembly is cooled to room temperature in nitrogen.
(H) remove band
Carefully draw and expose end removal band to the open air, stay unlimited filler opening.
Embodiment 4
Another method for making of dry type precast segment
(A) painting method
Carry out 30 minutes etching with 50%HCl at 75 ℃ of titanium sheets, make supporting construction thus 1mil (0.00254cm).The end pole plate is the titanium of 5mil (0.0127cm).
Oxide coating solution contains 0.2M (ruthenium trichloride trihydrate and 0.2M (two-isopropoxide (di-isopropxide)) two (2,4-glutaric acid (Pent-anedinate)) titanium in ethanol (SILVER REAGENT).
By under environmental condition, in solution, flooding, the Ti sheet after the etching is carried out dip-coating, the titanium sheet after the coating immerses solution and keeps taking out then in about 1 second.
After each the coating, 70 ℃ to dry 10 minutes of oxide, in oxygen,, take out then and be cooled to room temperature in 350 ℃ of thermal decompositions of carrying out 5 minutes, institute all carries out in ambiance in steps.
Repeat the dip-coating step and reach 30 layers of coating (perhaps any desired quantity), rotation Ti sheet is so that alternately invade each face.
Titanium sheet after applying fully in oxygen atmosphere in 350 ℃ of final annealings that carry out 3 hours.
(C) at interval
On a side of electrode, form the dimpling head by the mask thermal spraying.Thermal spraying material is TEFLON , take from E.I.Du Pont de Nemoure ﹠amp; Co,, Wilmington, Delaware.
TEFLON in air The dimpling head then is molded into the electrode after applying the shape of expectation in 300 ℃ of curing 0.5 hour.
(D) add the cushions
Have a side of dimpling head at electrode, the modification high-density polyethylene (HDPE, modification aspect anti-perforation and bonding force) of thick 1.5mil (0.00381cm), wide 30mil (0.0762cm) is set, its peripheral boundary is identical with electrode, then the PULSE HEATING lamination.HDPE is the PJX2242 grade, takes from Phillips-Joanna of Ladd, the Illinois.
(E) band
Be provided with a thick 1mil (0.00254cm), wide 10mil (0, band (TEFZEL 0254cm) ), across the narrow dimension of liner and electrode surface and between the dimpling head, aim at.Band can be positioned the center.One of center left or these three kinds of positions, right side, center.
The 2nd HDPE is set on first liner Liner is clipped in tape between the two-layer liner.
Second liner is carried out PULSE HEATING, make itself and first liner bonding and make the band fix in position.
(F) stacked
Stacked electrode/dimpling head/liner/tape/spacer assembly, end pole plate element by 5mil (0.0127cm) begins, reach the capacitor chip quantity of expectation, and stopping assembly by the smooth end pole plate of 5mil (0.0217cm), it is the position of repetition period by staggered location, left, center, right (end perspective) with Unit three that band is arranged on one.
(G) reflux
In nitrogen in 190 ℃ of liners through 30 minutes, thermoplastics is refluxed, assembly is chilled to room temperature in nitrogen.
(H) tape is removed
Carefully draw and expose end removal tape to the open air, stay unlimited filler opening.
Embodiment 5
Another method for making of dry type precast segment
(A) painting method
Use 1%HF/20%HNO 3Carry out 1 minute etching at 20 ℃ of zirconium sheets, make supporting construction thus 0.8mil (0.002032cm).The end pole plate is the zirconium of 2mil (0.00508cm).
Oxide coating solution is to contain the ruthenium trichloride trihydrate of 0.2M and the tantalic chloride of 0.1M in isopropyl alcohol (reagent is sewed).
By under environmental condition, in solution, flooding, the Ti sheet after the etching is carried out dip-coating.Ti sheet after the coating immerses solution and keeps taking out then in about 1 second.
After each the coating, 85 ℃ to dry 10 minutes of oxide, in 301 ℃ of thermal decompositions of carrying out 7 minutes, take out then and be chilled to room temperature, institute all carries out in ambiance in steps.
Repeat to soak deposited step and reach 10 layers of coating (or any desired quantity), rotation Ti sheet is so that alternately immerse each face.
In ambiance, under 310 ℃ the Ti sheet that applies fully carried out 2 hours final annealing.
(C) at interval
Side at electrode forms the dimpling head by the mask thermal spraying.Thermal spraying material is TEFLON , take from E.I.DuPont de Nemours ﹠amp; Co., Wilmington, Delaware.
In air under 310 ℃ with TEFLON The dimpling head solidified 1 hour.Then the electrode after applying is molded into the shape of expectation.
(D) add the cushions
A side that has the dimpling head at electrode is provided with thick 1.5mil (0.00381cm), the polypropylene-made liner of wide 30mil (0.0762cm), and its peripheral boundary is identical with electrode, then the PULSE HEATING lamination.
(E) band
Be provided with one and apply TEFLON Diameter be the tungsten band of 1mil (0.00254cm), across the narrow dimension of liner and electrode surface, and between the dimpling head, aim at.Band can be positioned one of center, center left or these three kinds of positions, right side, center.
Second polypropylene-made liner is set on first liner, tape is clipped between the two-layer liner.
Second liner is carried out PULSE HEATING make itself and first liner bonding, and make the tape fix in position.
(F) stacked
Stacked electrode/dimpling head/liner/tape/spacer assembly, by 2mil (0, end pole plate element 00508cm) begins, reach the capacitor chip quantity of expectation, and stopping assembly by the smooth end pole plate of 2mil (0.00508cm), it is the position of repetition period by staggered location, left, center, right (end perspective) with Unit three that band is arranged on one.
(G) reflux
In nitrogen 195 ℃ to liner 60 minutes, thermoplastics is refluxed.Assembly is chilled to room temperature in nitrogen.
(H) tape is removed
Pull out exposed ends and remove to be coated with tape, stay the unlimited hole of filling.
Embodiment 6
The filling of capacitor chip air gap separation
Follow these steps to charge into dry type precast segment 10 with electrolyte.Can adopt in many possible dry type precast segment configurations any.
(H) backfill
Artificial removal's tape opens wide filler opening, and stacked assembly is put into vacuum chamber, is evacuated to 35 milli torrs to assign 5 to 60 minutes.Removing air, with the H of 3.8M by nitrogen 2SO 4Liquid electrolyte introduce vacuum chamber and be packed between the electrode vacuum space every.
(I) sealing filler opening opening
From vacuum chamber, take out the assembly that has charged into electrolyte, use rinsed with deionized water, remove unnecessary electrolyte and dry.HDPE film ((thick 1.5mil (0.00381cm)), and seal whole hole by PULSE HEATING is set on whole filling aperture.
(J) adjust
This device charging up to charging fully, is begun by the 0.1V/ capacitor chip, press the 0.1V/ capacitor chip and increase, until the 1V/ capacitor chip.
(K) test
Test this device by traditional approach, the leakage current of 1V/ capacitor chip is less than 25 μ A/cm 2, the capacitance density of each capacitor chip is greater than 0.1F/cm 2A 10V height of devices is not more than 0.05 inch, and it highly is not more than 0.13 inch 40V device, and it highly is not more than 0.27 inch 100V device.
Performance based on the various geometries of sulfuric acid electrolyte and configuration is as shown in table 1
Table 1
The performance of supercapacitor device
Area/cm 2 ?2 ?2 ?2 ?2 ?25 ?25
Voltage ?10 ?40 ?100 ?100 ?100 ?100
C/MF ?26 ?6.7 ?2.6 ?10 ?150 ?753
The ESR/ milliohm ?100 ?330 ?780 ?780 ?62 ?70
Volume/cc ?0.29 ?0.73 ?1.6 ?1.6 ?11 ?32
Joule (J)/cc ?4.5 ?7.4 ?8.1 ?31 ?69 ?111A
Watt/cc ?860 ?1660 ?2000 ?2000 ?3670 ?1100
Embodiment 7
The another kind of fill method of dry type precast segment
Charge into dry type precast segment 10 with electrolyte according to the following steps.Can adopt in many possible dry type precast segment configurations any.
(H) backfill
Remove line and open wide filler opening.Stacked assembly is put into vacuum chamber and be evacuated to 35 milli torrs to assign 5 to 60 minutes, remove air by nitrogen, the liquid anhydrous electrolyte that contains 0.5MKPF6 in the propene carbonate (propylenecarbonate) is introduced vacuum chamber and charge between the electrode vacuum space every.
(I) sealing filler opening opening
Take out the assembly that has filled electrolyte from vacuum chamber, remove unnecessary electrolyte.HDPE film (thick 1.5mil (0.00381)) and PULSE HEATING are set on whole filler opening opening seal whole hole.
(J) adjust
This device is filled by up to charging fully, begin to increase by the 0.1V/ capacitor chip, until the 1.5V/ capacitor chip.
(K) test
Test this device by conventional method, the leakage current of 1.5V/ capacitor chip is about 100 μ A/cm 2, for the device that 10 capacitor chips are arranged, capacitance density is about 4mf/cm 2
Embodiment 8
The post-treatment condition of device
Below be to utilize adjustment technology behind all gases to regulate the electrical property table (table 3) of the device of electrode rest potential, can make a plurality of capacitor chip devices that are filled with the 4.6M sulfuric acid electrolyte charge to the 1V/ capacitor chip at least thus, and can be observed the leakage current reduction.This processing be before the backflow of gasket material, among and/or carry out afterwards.The gas treatment temperature is lower than the liner used temperature that refluxes, and atmosphere changes inert gas such as nitrogen or argon gas in the backflow.For the processing after the gasket material backflow, before processing, remove joint, in processing procedure, vacuumize and charge into reacting gas periodically.
Table 3
Device performance corresponding to the adjustment of various backs
Gas ?T/℃ The t/ branch ?1”/μA/cm 2 The V/ capacitor chip
?H 2 ?50 ?20 ?8 ?1.0
?CO ?100 ?170 ?40 ?1.0
?CO ?90 ?103 ?12 ?1.0
?CO ?90 ?165 ?20 ?1.0
?CO ?80 ?120 ?25 ?1.1
?NO ?75 ?20 ?27 ?1.0
?NO ?95 ?140 ?21 ?1.1
?NH 3 ?85 ?30 ?26 ?1.0
Utilize silk screen printing to form the dimpling head
Embodiment 9
Utilize silk screen printing on thin on-chip porous coating, to make epoxy resin dimpling head
(A) silk screen prepare-is laid on one 325 purpose stainless steel cloth on the standard silk screen printing framework.This silk screen edge bonding (Dexer epoxy 608 is expected only) is on the latten(-tin) of a less thick 1-1.5mil (0.00254-0.00381cm), and this latten(-tin) has hole (diameter 6.3mil (0.016cm)) that is drilled to or the figure that is etched into expectation.Remove by latten(-tin) overlay area sieve aperture, the remaining latten(-tin) edge that is adhered on the mesh is installed on the framework.
(B) sample clamping-vacuumize on a porous aluminum grip block, the average pore diameter in the hole on this grip block is 10 μ m, uses this plate holder to hold the porous oxide coating of thick 1mil (0.00254cm) in printing process.
(C) epoxy resin-interpolation silica filler, bi-component epoxide-resin MasterBond EP21AR modification to required viscosity (variability: 300000～400000cps).From Master Bond, Inc.of Haokensack, the available epoxy resin in New Jersey with filling of required viscosity.By this epoxy resin of explanation preparation, be about 30 minutes as time of effectively staying of flowable fluid.
(D) silk screen printing parameter
Speed is rolled in rolling: the 1-2 inch per second
Be coated with point (snap off): 20-30mil (0.0508-0.0762cm)
For guaranteeing even coating, the constant temperature and constant humidity of epoxy resin is important.Typical condition is the temperature of about 40～70% relative humidity and about 20-25 ℃.
(E) printing epoxy resin figure-make is the epoxy resin array of protrusions that 1mil (0.00254cm), diameter are about 7.5mil (0.019cm) highly basically, and the typical graphics on the electrode is by press 40mil (0.1016cm) the centre-to-centre spacing dimpling head array formation of deposit at interval.In addition, by center one center distance is decreased to 20mil (0.508cm), the dimpling head density at the peripheral place of electrode is increased, the epoxy resin configuration of silk screen printing was 150 ℃ of minimum curing 4 hours.
Embodiment 10
Silk screen printing forms epoxy resin dimpling head
(A) silk screen preparation---the 230 or 325 order silk screens (8 * 10 inches stainless steels) of no latex on the surface are installed on the standard print frame, as matrix.With the clean material of the Dexter epoxy resin 608 of taking from Dexter etching, the bonding rear side that is positioned silk screen in masterplate (6.0 * 8.5 molybdenums) edge that is drilled to or is washed into.On whole horizontal version mesh members, MYLAR is set , and exert pressure and make epoxy resin smoothly form conforming layer.
Then the tip-tap silk screen, apply epoxy resin, MYLAR be set at the silk screen end face in whole zone Sheet makes epoxy resin level and smooth.Remove the MYLRAR on the silk screen end face then Sheet.Then silk screen matrix version sub-assembly is positioned over 120 ℃ baking oven, cured epoxy resin is 5 minutes in ambiance.Also can be ambient temperature curing epoxy resin 30-60 minute.
Behind baking oven taking-up screen stencil, immediately the MYLAR of silk screen rear side Careful stripping shape.Cut the mesh screen of end face subsequently with sharp cutting edge, must carefully avoid going out cruelly of masterplate.Owing to remove mesh screen from the masterplate figure, any heat-staple resinoid such as epoxy resin can put on the mesh screen masterplate periphery after cutting, and use MYLAR Topped, make epoxy resin level and smooth, guarantee that the silk screen edge is fixed in masterplate.In baking oven, made epoxy resin cure 5 minutes.The gained member is the masterplate of being tightened by the silk screen expansion, prepares printing.
(B) sample clamping---using porosity is 36.5% (porosity of 30-60% is acceptable), bore dia porous ceramic clamping (as Fig. 8) plate (CeramiconDesigns as 4.5-6 μ, Golden, the Colorado, the P-6-C material), the thick 1mil of clamping in printing process) porous oxide coating 0.00254cm) vacuumizes through porous ceramic plate.Ceramic wafer is cut into appropriate size (size and dimension of substrate to be printed).This ceramic wafer inserts aluminium (steel etc.) frame 277 and epoxy resin or other adhesive that can be installed on screen process press then.Grind the polishing ceramic wafer then carefully to flushing as much as possible with metal frame.Add alignment pin 278,279 and 280, utilize hole 281,282 and 283 in position substrate 111A clamping.
(C) epoxy resin-Master Bond EP21ART (a kind of bi-component epoxide-resin (the polyamine curing agent of 33wt% and the liquid-state epoxy resin of 67wt%) viscosity is about 150000～600000cps).By this epoxy resin of explanation preparation.Effective RT as flowable fluid is about 30 minutes.
(D) silk screen printing parameter
Speed is rolled in rolling: 1-2 inch per second (viscosity that depends on epoxy resin)
Be coated with point (snap off): 20-30mil (0.0050-0.0076cm) (relevant, and can suitably regulate) with silk screen tension force
(E) Yin Shua epoxy resin figure---make be highly substantially 1～1.25mil (0.00254～0.00316cm), diameter is the epoxy resin plush copper array of 7.5mil (0.019cm).A typical graphics on the electrode is made of the dimpling head array by center-Center Gap 40mil (0.1cm) deposit.In addition, by center-center distance being decreased to 20mil (0.0508cm), make around the density increase of the dimpling head of electrode periphery.Epoxy resin configuration after the silk screen printing was solidified 4～12 hours in 150 ℃ in ambiance.
Embodiment 11
The parameter of another kind of silk screen printing
(A) isolate altitude range that plush copper isolates plush copper one by one 0.001～0.004 inch (0.00254～0.01016cm), wide 0.006～0.012 inch (0.01524～0.03038cm).Isolate plush copper and can be the combination of round dot, square, rectangle or these shapes.The width of plush copper increases and increases with the plush copper height.
(B) isolation pattern adopts two kinds of figures one by one on electrode base sheet, effective coverage and adhesion side boundary region, and the isolation of effective coverage is protruding presses 0.040 * 0.040 inch (0.1016 * 0.1016cm) center-Center Gap location and round dot normally.The adhesion side boundary region has the plush copper density of increase, and its center-Center Gap is 0.020 * 0.020 inch (0.0508 * 0.0508cm).The row of rectangle is alternately between the row of round dot.
(C) design of isolation configuration is finished in the silk screen preparation one by one in a CAD (computer-aided design) system.This CAD electronic data is converted into the Gerber pattern file, uses this pattern file to produce former figure in the silk screen manufacturing, makes the masterplate of expectation thickness for screen process press.This silk screen prepares to adopt SMT (California, the silk screen manufacturing technology of Santa Clara).
(D) electrode evacuated panel (work piece holder)---porous ceramic plate (GeramlconDesigns, Goden, Colorado, the P-G-C material) be trimmed to peripheral littler by 0.050 than electrode, and fit in the aluminium sheet that designs, and use epoxy resin bonding, aluminium sheet is installed in the screen process press.Top surface is ground polishing and makes it parallel with basal surface, insert around electrode edge placed in the middle, thereby the angle that is formed for electrode base sheet fixed output quota position keeps off with a plurality of pins.
(E) epoxy resin---by adding silica-filled thing, viscosity (300000～400000CPS) of the thixotroping of bi-component epoxide-resin Master Bond EP21AR modification to expectation.By the Master Bond that newly translates the west, the epoxy resin behind the inserts of adding that Inc.of Hackeusack is available to have desired viscosity.By explanation preparation epoxy resin, but be about 30 minutes as effective remaining time of streaming flow.
(F) silk screen printing parameter
The thick film screen process press
Hardometer 40～100 type A are rolled in rolling
Speed 1～2 inch per second is rolled in rolling
Roll over 10～15 pounds of roll extrusion power
Downward braking 0.010～maximum is rolled in rolling, inch
Be coated with 0.010～0.030 inch (0.0254～0.0762cm) of point (snap off)
Embodiment 12
The hot-rolling photolithographic fabrication of dimpling head
(A) the high consistency solder mask ConforMASK of thick 1.5mil (0.0038cm) 2000 are cut into the size identical with electrode.
(B) remove after the separating sheet 382 between photoresist film 381 and the electrode 111A, Confor MASK is set on electrode material surface 111A Film applies photoresist film 381 thus, makes this lamination by warm-up mill (384 and 385) at 150 °F, makes photoresist film 381 and electrode surface 111A bonding.Remove the polyester cover sheet 382A on the photoresist film outside then.
(C) containing the capable dark space mask 387 of transparent apertures (opening 388) is arranged on the photoresist 381.Typical figure is that 6mil (0.0212cm), center-Center Gap are that the hole array of 40mil (0.1cm) constitutes by diameter, and this figure has three behavior high density at the boundary of electrode, and (center-center distance is 20mil (0.0508cm).
(D) film 381 is about 20 seconds of 389 times exposures of mercury vapor lamp by hole 388 and mask 387 at the traditional UV light source.Remove mask then.
(E), through 1.5 minutes the unexposed zone of photoresist developed or peel off by inserting in the liquid tank that contains 1% potash.
(F) with deionized water the electrode surface with dimpling head (discrete point) is carried out feelings then and wash, in 10% sulfuric acid liquid bath, placed 1.5 minutes, use rinsed with deionized water at last.
(G) at first dimpling head 13 is exposed under ultraviolet light, in traditional air-oven, under 300 °F dimpling head (discrete point) is carried out 1 hour final curing.
Electrode 111A after making can directly use or by above-mentioned such processing.
Embodiment 13
The vacuum stack of photoresist
(A) the high-performance solder mask Confor MASK of thick 2.3mil (0.0058cm) 2000 are cut into and are a bit larger tham electrode.
(B) use 724 or 730 type Dynachem vacuum pack system machines, adopt standard operation condition (160 ℃, 0.3 millibar) photoresist film 381 vacuum stacks in electrode 111A, and place on the supporting backboard.Remove polyester cover layer 382A.
(C) the dark space mask 387 that contains multirow transparent apertures 388 is set on photoresist film 831.Typical figure comprise diameter be 6mil (0.0015cm), center-in be spaced apart the array in the hole of 40mil (0.102cm), this figure has the hole of three behavior high density (center-center distance is 20mil (0.0054cm)) at the boundary electrode place.
(D) be to this film exposure 20～40 seconds under the non-parallel ultraviolet source of 3～7KW at power.
(E) in a conveyor type spraying developing apparatus, the potash of use 0.5% develops to the photoresist unexposed area and peels off, then with rinsed with deionized water and turbine drying.
(F) carry out the final curing that the dimpling head guy is followed closely by two step process, at first in Dynachem UVCS933 device, the dimpling head is exposed to ultraviolet light, place it forced air supply baking oven dry then, continue 75 minutes at 300～310 °F.
The electrode of making can directly use, perhaps by above-mentioned such further processing.
Embodiment 14
Be used to control the surfactant of porosity
In stirring and mild heat, in 1 liter isopropyl alcohol, add 32 gram softex kws.After about 1 hour, in this clear solution, add 73 gram TaCl 5With 47 gram RuCl 3H 2O.Finish the coating processes of standard by 300 ℃ of middle pyrolysis of following 5 minutes and 300 ℃ of final pyrolysis of following 3 hours.The average pore diameter of coating increases to about 45A.At 260 ℃, 680 pounds/inch 2Steam in after 2 hours reprocessing, average pore size increases to 120A.
Also can improve the aperture of the coating made from the aqueous solution of 25wt% hexadecyltrimethylammonium chloride.
Embodiment 15
The thermoelastic material liner
The manufacturing process of another kind of structure is (as KRATON the thermoelastic material liner ) be clipped between the two-layer HDPE liner.Device property as hereinbefore.
Embodiment 16
Comprising second material regulates electrolyte its volume is increased
Increase the porous hydrophobic material at each capacitor chip, electrolytical any volume that the Yin Wendu rising is caused increases to be regulated.
This material is arranged in the capacitor chip, or as the gasket material in the HDPE liner of border, or replaces part as the garden sheet of spacer material.
Normally used material is to take from W.L.Gore ﹠amp; Associates, the PTFE material of Inc., thick 1-3mil.The water of PTFE material enters preferably 20～100 pounds/inch of pressures 2
Embodiment 17
Another kind of electrode gives processing
Have dimpling head, liner and backguy band (after the step e) afterwards at electrode, electrode is placed 1M sulfuric acid, the cathode current that utilizes no hydrogen to produce transfers to about 0.5V (with respect to the normal hydrogen electrode) to open circuit potential, the electrode that is immersed in the deionized water is transported in the inert atmosphere (as argon), carries out drying and assembling there.
Although only several embodiments of the present invention are showed here and illustrate, but should understand, for the person skilled in art, can make various improvement and variation by improved method, make electrical storage device such as battery or capacitor, improving to some extent aspect life-span, charging/recyclability and the low-leakage current, and do not breaking away from the spirit and scope of the present invention.All these classes are improved and are changed and all belong in the scope of accompanying Claim.

Claims (42)

1, a kind of dry type precast segment that is used for energy storing device comprises:
At least one is used for first capacitor chip of stored energy, and described first capacitor chip comprises in combination:
A. first conductive electrode;
B. second conductive electrode, described first and second electrodes separate first preset distance: and
C. the first dielectric liner device that is provided with between described first and second electrodes is used for described first electrode and second electrode are separated and electric insulation;
Thus, when described first electrode, described second electrode and described first liner with opening placed in the middle are bonded together, form described first capacitor chip, be formed with the inflation crack that charges into air therebetween.
2, according to the dry type precast segment of claim 1, wherein said first capacitor chip further comprises:
A. the first surface area conductive coating that on a surface of described first electrode, forms, described first coating is arranged between described first electrode and the described cushion device; With
B. the second largest surface area conductive coating that on a surface of described second porous electrode, forms, described second coating is arranged between described second electrode and described first cushion device;
C. first coating, second coating or its in conjunction with on the coating that comprises a plurality of plush coppers, wherein said plush copper gives described first capacitor chip with support structure, and provides supplementary insulation between described first and second electrodes.
3, according to the dry type precast segment of claim 2, wherein said first capacitor chip further comprises first filler opening that is formed by described cushion device, so that allow electrolyte to flow into described filling pore.
4, according to the dry type precast segment of claim 3, wherein said first capacitor chip further comprises first tape that is inserted in described first filler opening; With
Wherein when removing described first tape, described first filler opening opens wide and described filling air gap becomes enterable.
5, according to the dry type precast segment of claim 1 or 4, further comprise at least one second capacitor chip, wherein said first capacitor chip is stacked with described second capacitor chip and be connected, so that make the dry type precast segment constitute an overall structure.
6, according to the dry type precast segment of claim 5, wherein said second conductive electrode is a bipolar electrode, and it is shared by described first and second capacitor chips:
Wherein said second capacitor chip further comprises one the 3rd conductive electrode, and it and described second conductive electrode are provided with Face to face;
Wherein said first and second conductive electrodes separate second and give set a distance.
7, according to the dry type precast segment of claim 6, wherein on second flat surfaces of described second electrode, form one the 3rd coating, so that described second coating is arranged between described second electrode and described second cushion device; With
Wherein said second capacitor chip comprises a plurality of discrete plush copper that is positioned on each electrode surface.
8, according to the dry type precast segment of claim 7, wherein said second capacitor chip further comprises a lip-deep high surface area and coating conduction that is formed on described third electrode; With
Wherein said the 4th coating is arranged between described third electrode and described second cushion device.
9, dry type precast segment according to Claim 8, wherein said second capacitor chip further comprises second filler opening that is formed in described second cushion device.
10, according to the dry type precast segment of claim 9, further comprise the external lug that is used to connect power supply.
11, dry type precast segment according to Claim 8, each in the wherein said first and the 3rd coating include the extra play that one deck has the discrete plush copper of one group of peripheral plush copper and one group of central authorities, and these plush coppers are by arranged in arrays.
12, according to the dry type precast segment of claim 11, wherein the diameter of each plush copper is 6mil (0.015cm);
Center-the Center Gap of described peripheral plush copper is 20mil (0.0508cm);
Center-the Center Gap of described central plush copper is 40mil (0.102cm);
Described periphery and central plush copper have dielectric component.
13, according to the dry type precast segment of claim 6, wherein said first and second give set a distance equates.
14, according to the dry type precast segment of claim 1 or 5, each in wherein said first and second cushion devices includes two dielectric liner, and they aim at setting mutually; With
Wherein said first band is arranged between the described liner, forms described first filler opening with this.
15, according to the dry type assembly of claim 6, wherein said first, second is identical with third electrode and be rectangle.
16, in the formation of claim 1, in the filling gap of each, also contain the porous hydrophobic polymeric material, alleviate the static pressure that increases water with the temperature rising with this.
17, the porous hydrophobic polymeric material of claim 44, wherein this material comprises polytetrafluoroethylene, its water enters and is pressed between 760～7600 torrs.
18, a kind of capacitor precast segment comprises one first capacitor chip at least, and this capacitor comprises:
A. first conductive electrode;
B. second conductive electrode, described first and second electrodes separate first and give set a distance; With
C. the peripheral liner of first dielectric that is provided with between described first and second electrodes separates described first electrode and second electrode and electric insulation;
Thus, when described first electrode, described second electrode and described first cushion device are bonded together formation first capacitor chip, form one therebetween and fill air gap.
19, according to the capacitor precast segment of claim 18, wherein first capacitor chip further comprises:
A. first coating that on a surface of described first electrode, forms, described first coating is arranged between described first electrode and the described cushion device; With
B. second coating that on a surface of described second electrode, forms, described second coating must be arranged between described second electrode and described first cushion device;
C. the one deck that has a plurality of discrete plush coppers; With
Wherein said plush copper gives first capacitor chip with structure support, and provides supplementary insulation between described first and second electrodes.
20,, further comprise at least one second capacitor chip according to the capacitor precast segment of claim 19;
Wherein first and second capacitor chips are stacked and be bonded together, so that the structure that constitutes one is provided for capacitor;
Described second conductive electrode is a bipolar electrode, and is shared by described first and second capacitor chips;
Described second capacitor chip also comprises the 3rd conductive electrode, is provided with Face to face with described second conductive electrode; With
Described first and second conductive electrodes separate second preset distance.
21, the employed conductive coating of dry type precast segment that is used for energy storing device comprises a high surface area porous layer that is coated on the supporter.
22, according to the coating of claim 21, wherein porous layer comprises metal oxide or mixed-metal oxides, and has the big effective surface area that is made of little pore and medium pore basically.
23, a kind of method of using any precast segment among the claim 1-20 to come stored energy, wherein said precast segment charges into ionic conduction electrolyte, sealing and charging.
24, a kind of method of making the dry type precast segment comprises the step that forms at least one first capacitor chip:
A. first conductive electrode and second conductive electrode are separated first preset distance;
B. between described first and second electrodes, first dielectric liner is set, described first and second electrodes are separated and electric insulation;
Thus, when described first electrode, described second electrode and described first cushion device are bonded together when forming described first capacitor chip, form one therebetween and fill air gap.
25, a kind of method of making the capacitor precast segment comprises the step that forms at least one first capacitor chip:
A. first conductive electrode and second conductive electrode are separated first and give set a distance;
B., the first dielectric liner device is set between described first and second electrodes, described first and second electrodes are separated and electric insulation;
Thus, when described first electrode, described second electrode and described first cushion device are bonded together when forming described first capacitor chip, form therebetween and fill air gap.
26, a kind of method of making the capacitor precast segment comprises the step that forms at least one first capacitor chip:
A. the first conductive layer device and the second conductive layer device are separated first and give set a distance;
B. between the described first and second conductive layer devices, the first dielectric liner seal apparatus is set, the described first and second conductive layer devices are separated and electric insulation;
Thus, when described first conductive layer that is used for stored charge, be used for the second conductive layer device of stored charge and described first cushion device that is used to electrode surface is separated is bonded together when forming described first capacitor chip, form therebetween and fill air gap.
27, according to the dry type precast segment manufacture method of claim 24, further comprising the steps of:
A. form first porous conductive coating on a surface of described first electrode, described first coating is arranged between described first electrode and the described cushion device;
B. form second porous conductive coating on a surface of described second electrode, described second coating is arranged between described second electrode and described first cushion device;
C. form a plurality of discrete dimpling heads under described first coating, described plush copper provides support structure for described first capacitor chip; And between described first and second electrodes, provide supplementary insulation.
28, a kind of method of making the dry type precast segment of electrical storage device, this device is used for charge storage, can have and anhydrous or aqueous electrolyte electrodes in contact surface, and this method comprises:
(a) thin slice of the substantially flat of preparation conductive supporting material, on its each flattened side, scribble the thin layer of second electric conducting material identical or different, that have high surface area, two flattened side of conductive supporting can respectively be chosen as a thin slice, and its outer fringe surface is following any one structure:
(i) have the thin layer of second electric conducting material,
(ii) part does not have second electric conducting material, or
(iii) there is not second electric conducting material;
(b) following these steps to be made in moisture or the non-aqueous eletrolyte is stable ion-permeable or semi permeable gap separator:
(i) on the surface of at least one side of the second electric conducting material thin layer, the basic electric insulation dimpling head group uniformly of deposition height,
(ii) on a surface of second electric conducting material, be provided with an ion-permeable of giving cutting earlier or semi-permeable leptophragmata from, perhaps
(iii) on the surface of at least one side of electric conducting material, make ion-permeable or semi-permeable thin layer, perhaps
(iv) make a thin air gap as separator;
(c) with one or more synthetic organic polymer thin layers as gasket material, contact with the outer fringe surface of the one or both sides of step (b) gained thin slice, this polymer is selected from thermoplasticity, thermoelasticity and thermosetting polymer;
(d) on the gasket material or among the thin tape of at least one different materials is set and selectively across thin slice, this tape has the high-melting-point greater than the liner polymeric material, and under treatment conditions, can not melt, flow or permanent and liner is bonding:
(e) make sheet the thin flat finished product repeat stacked, this sheet scribbles the separator that high surface area coating and step (d) are made, this sheet selectively has the end pole plate that is made of thicker support:
(f) stacked the heating that step (e) is made, and exert pressure and make synthetic gasket material mobile, bonding and seal stacked edge effectively, make stacked integral body of solid of the layer that alternately constitutes by conducting strip that scribbles second electric conducting material and ion-permeable separator, optionally make gasket material constitute the poly-platform thing that constitutes one continuously and encapsulate;
(g) stacked whole cooling of solid that step (f) is made;
(h) remove the thin tape of a different materials between every layer at least, between the layer of the conducting strip that scribbles second electric conducting material, form at least one little opening.
29, according to the method for claim 27 or 28, wherein said dimpling head can be pottery, organic elastomer, thermoplastics, or thermosets or its combination.
30, according to the method for claim 29, wherein, step (e) afterwards and step (f) before or step (h) afterwards, the member of stacked integral body is followed these steps to handle:
(j) the dry type precast segment is vacuumized, fully remove residual gas;
(k) near under the ambient pressure, contact the dry type precast segment with one or more reducing gass;
(l) at 20～150 ℃ assembly and reducing gas were heated 0.1～5 hour:
(m) the dry type precast segment is vacuumized;
(n) use the inert gas replacement reducing atmosphere; With
(o) at least optionally repeat a step (j), (k), (l), (m) and (n).
31, according to the method for claim 28, wherein, step (e) afterwards and step (f) before or step (h) afterwards, follow these steps to handle to being stacked to whole member:
(j) the dry type precast segment is vacuumized, fully remove residual gas;
(k) near under the ambient pressure, contact the dry type precast segment with one or more reducing gass;
(l) at 20～150 ℃ assembly and reducing gas were heated 0.1～5 hour;
(m) the dry type precast segment is vacuumized;
(n) replace reducing atmosphere with inert gas: and
(o) at least optionally repeat a step (j), (k), (l), (m) and (n).
32, according to the method for claim 30 or 31, wherein step (j), (m) and (o) in vacuum degree be about 250 milli torrs or lower.
33, according to the method for claim 31 or 32, wherein reducing gas is selected from hydrogen, carbon monoxide, hydrogen oxide, ammonia or its combination;
Inert gas is selected from helium, neon, nitrogen, helium or its combination;
One or more reducing gass contact with assembly in order with one or more inert gases.
34, according to the method for claim 28, wherein:
Be arranged on the top side of device at step (b) gasket material, gasket material between the electrode is sufficiently excessive on volume, so that when when step (f) heats, excessive gasket material is extruded around the outer rim of supporter, makes the integral surface of seamless sealing thus at the edge of overlapped assembly.
35, according to the method for claim 28, wherein:
At step (a), supporter has second electric conducting material on outer fringe surface,
At step (b), the dimpling head is positioned on the surface of second electric conducting material,
At step (c), gasket material is thermoplastic,
At step (e), dististyle is a thicker support,
At step (f), gasket material is excessive, so that make the encapsulation of continuous integral sealing,
At step (g), overlapped assembly is chilled to room temperature,
At step (h), tape can be metal, pottery, organic polymer or its combination.
36, a kind of manufacturing is used for the improving one's methods of electrical storage device of charge storage, comprising:
Dry type precast segment to the either party's manufactured in the foundation claim 28 to 35 vacuumizes,
With aqueous inorganic acid or anhydrous organic electrolyte with vacuumize after the dry type precast segment contact certain hour, being enough to making space backfill between the support chip with filler opening,
Remove all outer surfaces electrolyte and
Close and seal the filler opening opening.
37, according to the dry type precast segment of claim 1 or 5, wherein said first electrode comprises one first conductive porous coating, this coating is formed on the surface of first electrode, and described first coating is between described first electrode and the described cushion device; With
Wherein said second electrode is ambipolar.
38, according to the dry type precast segment of claim 37, wherein said second electrode comprises the first conductive porous coating that is formed on the one surface, makes the described first conductive porous coating between described second electrode and described first cushion device.
39, according to the dry type precast segment of claim 38, wherein said first electrode also comprises the spacer assembly that is formed on described first coating, is spaced to keep described first electrode and second electrode.
40, according to the dry type precast segment of claim 39, wherein said second electrode also comprises and is formed on its another lip-deep second conductive porous coating.
41, according to the dry type precast segment of claim 39, described first and second of described first coating of wherein said first electrode and described second electrode is coated with stacking from metal oxide, mixed-metal oxides, metal nitride and poly-platform thing.
42, according to the dry type precast segment of claim 39, wherein said escapement comprises a plurality of plush coppers; With
Described plush copper gives described first capacitor chip with structure support, and provides supplementary insulation between described first and second electrodes.
CN93119348A 1992-09-18 1993-09-18 Energy storage device and methods of manueacture Expired - Fee Related CN1127771C (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US07/947,414 1992-09-18
US07/947,294 1992-09-18
US07/947,414 US5384685A (en) 1992-09-18 1992-09-18 Screen printing of microprotrusions for use as a space separator in an electrical storage device
US07/947,294 US5464453A (en) 1992-09-18 1992-09-18 Method to fabricate a reliable electrical storage device and the device thereof
US95850692A 1992-10-07 1992-10-07
US07/958,506 1992-10-07

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AU681351B2 (en) 1997-08-28
JPH08501660A (en) 1996-02-20
CN1096611A (en) 1994-12-21
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NO951045L (en) 1995-05-16
WO1994007272A1 (en) 1994-03-31

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