A kind of high-energy tantalum mixed capacitor shell and manufacture method thereof
Technical field
The present invention relates to capacitor area, particularly relate to a kind of tantalum mixed capacitor shell, and its manufacturing process.
Background technology
The quality of tantalum is very hard, and tantalum is rich in ductility, can pull into filament formula thin foil.Its thermal coefficient of expansion is very little.Tantalum has very outstanding chemical property, has high corrosion resistance.No matter be under the condition of cold-peace heat, hydrochloric acid, red fuming nitric acid (RFNA) and " chloroazotic acid " are not reacted.Can be used to manufacture evaporator boat etc., also can do the electrode of electron tube, rectifier, electrolysis, electric capacity.
Tantalum forms stable anode oxide film in acidic electrolysis bath, the electrolytic capacitor made with tantalum, has that capacity is large, volume is little and the advantage such as good reliability, manufactures the most important purposes that capacitor is tantalum.
As everyone knows, tantalum electrolytic capacitor has the features such as Large Copacity, high voltage and high reliability because of it, is widely used in the electronic device.Along with the electronic electric equipment in the fields such as communication, medical treatment, traffic is to small size, high-power, high-frequency, high working voltage future development, the requirement of electronic equipment to the rated operational voltage of capacitor, high frequency characteristics and volume and capacity ratio is more and more higher, especially in aerospace equipment, significantly improves capacitor energy density and improves payload capability.Therefore, the sealing property of shell and reliability ensure capacitor basis and prerequisite reliably, is also one of problem of numerous scholar's research.
The material that shell uses is tantalum, this material has the premium properties such as fusing point is high, good processability, corrosion-resistant, steam forces down, the coefficient of expansion is little, but tantalum plate hardening phenomenon in drawing and punching course is more serious, easily produce cracking when tantalum shell is extended in deep-draw, draw trace, distortion, affect product size, outward appearance, homogeneity of product etc.
Compared with the CAK whole tantalum capacitor (below Ф 10mm) that volume is little, the internal volume of high energy tantalum capacitor is larger, and isolate and buffering without the employing fluorine glue that CAK series whole tantalum capacitor is such, therefore require higher to the sealing property of tantalum insulated electronic, mechanical strength is better, and impact resistance is stronger.Simultaneously structurally, directly and glass contact, this just requires that the acid resistance of glass is stronger to the sulfuric acid solution of capacitor internal.
The performance and reliability of high energy mixing tantalum capacitor shell directly affects the reliability of capacitor; not only to provide seal protection for high energy mixing tantalum capacitor electrolyte inside; prevent the outside seepage of the electrolyte of capacitor internal, but also be required to be the input and output of capacitor providing current voltage signal and external environment condition is protected.
By patent retrieval, there is following known prior art:
Patent 1:
Application number 201120251913.2, applying date 2011-07-18, authorized announcement date 2012-05-23, a kind of square solid state capacitor, it is characterized in that described square solid state capacitor comprises a cavernous tantalum agglomerate, this tantalum agglomerate is coated in the conducting polymer composite layer of a plasticizing, arranges a carbon paste and elargol layer outside this conducting polymer composite layer, and a negative electrode connects carbon paste and elargol layer.This square solid state capacitor is reasonable in design, and have excellent Low dark curient disposal ability and strengthening puncture voltage, its leakage current (LC) characteristic having stronger puncture voltage (BDV) and improve, can not produce moment punch-through after aging.Its preparation method is simple, easily realizes industrial-scale production.
Patent 2:
Application number: 200610134467.0, the applying date: 2006-11-29, publication date 2007-05-16, the invention belongs to high-power electronic device technical field, relates to a kind of hybrid super capacitor.It is characterized in that the anode making capacitor of tantalum, make the negative electrode of capacitor of ruthenic oxide electrode, fill with electrolyte.Tantalum anode and electrolyte form electrolytic capacitor, and ruthenic oxide electrode forms electrochemical capacitor in the electrolytic solution, and the two forms the ultracapacitor with electrolytic capacitor and electrochemical capacitor Common advantages by electrolyte equivalent series.The tantalum anode of this capacitor is suppressed by tantalum powder and is formed, and ruthenic oxide is coated on substrate collector and forms negative electrode, and electrolyte is sulfuric acid solution.Effect of the present invention and benefit improve the operating voltage of ultracapacitor, and keep the feature of high energy storage density.Eliminate the deficiency that typical ultracapacitor operating voltage is low, plural serial stage can reduce energy storage density and power density, solve the problem that general ultracapacitor can not be used for pulse power system.This capacitor arrangement is simple, and industrial realization is convenient.
Patent 3:
Application number: 200420035723.7, the applying date: 2004-04-28, publication date 2005-06-01, a kind of high-energy tantalum mixed capacitor combined with electrochemical capacitor and tantalum electrolytic capacitor, it comprises one or more anode tantalum core of being suppressed by high specific capacitance tantalum powder, the negative electrode of electrochemical capacitor is formed, multiple separator between one or more electrolyte scribbling amorphous oxide and injection; A tantalum shell, described negative electrode, separator and anode tantalum core overlay in this tantalum shell in accordance with the order from top to bottom successively one by one, a tantalum-glass insulator be made up of tantalum lid and vitreum 7, and described positive wire is drawn through vitreum; Described negative wire is welded on described tantalum and covers; A technique aperture sealed again is after injection of the electrolyte covered at tantalum; A cushion pad; A ring liner be placed in around anode tantalum core.Its small volume, energy density is high.
Patent 4:
Application number: 201010147967.4, the applying date: 2010-04-16, authorized announcement date 2012.05.02, a kind of lead-out mode of full tantalum shell tantalum electrolytic capacitor lead-out wire and capacitor, for monolithic capacitor, the lead-out mode of capacitor is: both positive and negative polarity is drawn and is nickel sheet or the extraction of nickel plating copper sheet, be respectively positive pole nickel sheet or nickel plating copper sheet lead-out tablet and cathode nickel sheet or nickel plating copper sheet lead-out tablet, and have wiring hole for the termination of positive pole nickel sheet or nickel plating copper sheet lead-out tablet and cathode nickel sheet or nickel plating copper sheet lead-out tablet, positive pole nickel sheet or nickel plating copper sheet lead-out tablet are connected with other electron component device with wire with the lead-out tablet that cathode nickel sheet or nickel plating copper sheet lead-out tablet are made, and be positive pole nickel sheet or nickel plating copper sheet lead-out tablet and cathode nickel sheet or nickel plating copper sheet lead-out tablet by laser welding respectively as the welding of capacitor lead-out tablet on the capacitor, as the ejector of condenser capacity.
Found by above retrieval, above technical scheme can not affect novelty of the present invention; And the mutual combination of above patent document can not destroy creativeness of the present invention.
Summary of the invention
The object of this invention is to provide a kind of high-energy tantalum mixed capacitor shell and manufacture method thereof, make high-energy tantalum mixed capacitor shell have good seal performance, be convenient to welding of electrode and external circuit, meet after high-energy tantalum mixed capacitor encapsulation without leakage requirement.
For realizing above object, the present invention adopts following technical scheme.
According to a scheme of the present invention, a kind of high-energy tantalum mixed capacitor shell, described shell includes a tantalum shell (1) and a tantalum insulator cover, and tantalum shell (1) is straight tube hat-shaped structure; Tantalum insulator cover is made up of tantalum lid (6), vitreum (3), tantalum wire (4), steel loop (2), metal tube (5), wherein tantalum lid (6) and tantalum wire (4) are sealed by the vitreum (3) formed after high temperature sintering molten glass, and metal tube (5) is enclosed within the tantalum wire (4) of vitreum of emerging (3) top by mechanical crimp; Described tantalum lid (6) surrounding is provided with crimping, and tantalum lid (6) is welded together by crimping and tantalum shell (1); Described tantalum lid (6) is provided with liquid injection hole (601).
According to another aspect of the present invention, a kind of manufacture method of high-energy tantalum mixed capacitor shell, comprises the steps:
(1) punching press: tantalum plate is struck out tantalum shell and tantalum lid, then carry out polishing, polishing, punching, cleaning etc., obtain tantalum shell and tantalum lid;
(2) cut: tantalum wire, metal tube are cut into required size by drawing, and then carry out deoiling, deburring process, obtain tantalum lead-in wire, steel loop, metal tube;
(3) gob punch forming: glass dust is dry-pressing formed on forcing press, then binder removal, pre-burning are shaping, obtain gob.
(4) crimp steel loop: steel loop and tantalum are covered and carry out Automatic manual transmission under special mould, form tight fit;
(5) assembling sintering: by go up the tantalum lid of steel loop, tantalum goes between, gob on request with assembled in sequence in graphite jig, be pushed in sintering furnace and sintered;
(6) upper metal tube: metal tube is nested on lead-in wire, then crimps, by metal tube and tantalum wire strong bonded.
Further: the polishing described in step (1) carries out polishing grinding by being placed on High Rotation Speed particular manufacturing craft by the tantalum shell after mould punching and tantalum lid, sand paper used of polishing is waterproof abrasive paper, with 200#, 600#, 800#, 1200# waterproof abrasive paper, polished in the surface that need polish successively, remove the defects such as surface indentation (cut), pit, make surface reach bright luster.
Further: the polishing described in step (1) be by polishing after tantalum lid (tantalum shell) effects on surface in vibratory finishing machine or magnetic force polisher carry out light decorations process, Ф 5mm ~ Ф 7mm stainless steel the spherical abrasive material adopted, surface conditioning agent need be added during polishing, surface conditioning agent is 5g ~ 20g, the amount of water is about about 1L ~ 5L, the quantity putting into polished part is 5 ~ 15, and the time is 5 ~ 15 minutes.
Further: the punching described in step (1) is that tantalum lid after polishing is carried out punching by forcing press and Special punching punch die, and punching includes rushes glass sealing hole and liquid injection hole, often rush a hole and all will smear lubricant on drift.
Further: the cutting described in step (2) is that tantalum wire, metal tube are cut into required size by drawing, tantalum wire adopts chopping heading machine to cut, and metal tube adopts high-speed cut-off machine to cut.
Further: the gob drawing described in step (3) is on glass base punch press, utilize mould to suppress medium and small cylinder green compact with holes, then binder removal in box type furnace, pre-burning is shaping, binder removal and pre-sintering temperature are respectively 430 DEG C and 680 DEG C, temperature retention time is respectively 1 hour and 20 minutes, and total time is 5 hours.
Further: the crimping steel loop described in step (4) is on arm pressure machine, utilize mould steel loop and tantalum lid to be crimped together, and makes steel loop and tantalum lid form tight fit, this be engaged in vibration or ultrasonic under can not be separated.
Further: the assembling sintering described in step (5) carries out in graphite jig; first by certain step and requirement, each part and accessory are assembled; utilize argon gas for protective atmosphere; put into tube furnace to sinter; sintering step is: first heat up with the rapid-result degree being less than 40 DEG C/minute, keeps 20 ~ 30 minutes, then cool to 540 DEG C ~ 560 DEG C with the speed of 50 DEG C ~ 100 DEG C/minute when temperature reaches 1050 DEG C; keep 10 minutes, now cool to room temperature with the speed being less than 50 DEG C/min.
Further: the upper metal tube described in step (6) is nested into by metal tube on tantalum lead-in wire, arm pressure machine utilize mould metal tube and tantalum wire are crimped together, make steel loop and tantalum lid form tight fit, this be engaged in vibration or ultrasonic under can not be separated.
Beneficial effect of the present invention: make high-energy tantalum mixed capacitor shell have good seal performance, is convenient to welding of electrode and external circuit, meets after high-energy tantalum mixed capacitor encapsulation without leakage requirement.
Accompanying drawing explanation
Fig. 1 is the structural representation of high-energy tantalum mixed capacitor shell of the present invention.
Fig. 2 is the process curve of sintering.
Fig. 3 is the three-dimensional structure schematic diagram of knot of high-energy tantalum mixed capacitor circular housing of the present invention.
Fig. 4 is the perspective view of high-energy tantalum mixed capacitor square shell of the present invention.
Described in figure, numerical reference is expressed as: 1, tantalum shell; 2, steel loop; 3, vitreum; 4, tantalum wire; 5, metal tube; 6, tantalum lid; 601, liquid injection hole.
Embodiment
In order to make those skilled in the art understand technical scheme of the present invention better, describe the present invention below in conjunction with accompanying drawing, the description of this part is only exemplary and explanatory, should not have any restriction to protection scope of the present invention.
As the structural representation that Fig. 1 is high-energy tantalum mixed capacitor shell of the present invention.Its structural relation is: high-energy tantalum mixed capacitor shell includes a tantalum shell 1 and a tantalum insulator cover, and tantalum shell 1 is straight tube hat-shaped structure; Tantalum insulator cover is made up of tantalum lid 6, vitreum 3, tantalum wire 4, steel loop 2, metal tube 5, wherein tantalum lid 6 and tantalum wire 4 are sealed by the vitreum 3 formed after high temperature sintering molten glass, metal tube 5 is enclosed within the tantalum wire 4 above vitreum 3 of emerging by mechanical crimp; Described tantalum lid 6 surrounding is provided with crimping, and tantalum lid 6 is welded together by crimping and tantalum shell 1; Described tantalum lid 6 is provided with liquid injection hole 601.
Fig. 3, Fig. 4 be respectively high-energy tantalum mixed capacitor shell circular housing of the present invention, square shell structural representation.It embodies two kinds of different concrete structure schemes.Also there are other possible organization plans in theory, do not list one by one at this, but all should work as and belong to protection scope of the present invention.
For can for the purpose of concise description problem, below to the manufacture method of a kind of high-energy tantalum mixed capacitor shell of the present invention hereinafter referred to as this manufacture method.
In this manufacture method, polishing described in step (1) carries out polishing grinding by being placed on High Rotation Speed particular manufacturing craft by the tantalum shell after mould punching and tantalum lid, sand paper used of polishing is waterproof abrasive paper, with 200#, 600#, 800#, 1200# waterproof abrasive paper, polished in the surface that need polish successively, remove the defects such as surface indentation (cut), pit, make surface reach bright luster.
As the optimization of this manufacture method, polishing described in step (1) be by polishing after tantalum lid (tantalum shell) effects on surface in vibratory finishing machine or magnetic force polisher carry out light decorations process, Ф 5mm ~ Ф 7mm stainless steel the spherical abrasive material adopted, surface conditioning agent need be added during polishing, surface conditioning agent is 5g ~ 20g, the amount of water is about about 1L ~ 5L, the quantity putting into polished part is 5 ~ 15, and the time is 5 ~ 15 minutes.
Punching described in step (1) is that tantalum lid after polishing is carried out punching by forcing press and Special punching punch die, and punching includes rushes glass sealing hole and liquid injection hole, often rushes a hole and all will smear lubricant on drift.
Cutting described in step (2) is that tantalum wire, metal tube are cut into required size by drawing, and tantalum wire adopts chopping heading machine to cut, and metal tube adopts high-speed cut-off machine to cut.
The rotating speed of high-speed cut-off machine is 2800 ~ 3800rmp, and the tubing termination after cutting is smooth, and the burr after cutting adopts to add has the cleaning mill of wheel angle abrasive material to carry out tumbling, fully removes the burr after cutting.
Gob drawing described in step (3) is on glass base punch press, utilize mould to suppress medium and small cylinder green compact with holes, then binder removal in box type furnace, pre-burning is shaping, binder removal and pre-sintering temperature are respectively 430 DEG C and 680 DEG C, temperature retention time is respectively 1 hour and 20 minutes, and total time is 5 hours.
Gob described in this manufacture method adopts borosilicate glass material, and in its glass, Main Ingredients and Appearance is Si02, B2O3, Na2O, Al2O3 etc., and first the coefficient of expansion of glass expansion coefficient and tantalum is close, forms matched seal with tantalum; Secondly glass has stronger acid resistance, ensures that glass can stand the corrosion of strong acid; Micro amount of oxygen in last at high temperature tantalum heat absorbing glass forms oxide and is fused to glass, forms good congruent melting layer like this, ensure that the sealing property of tantalum insulator sealing-in between glass and tantalum material.
Crimping steel loop described in step (4) is on arm pressure machine, utilize mould steel loop and tantalum lid to be crimped together, and steel loop and tantalum lid will form tight fit, this be engaged in vibration or ultrasonic under can not be separated.
Assembling sintering described in step (5) carries out in graphite jig; first by certain step and requirement, each part and accessory are assembled; utilize argon gas for protective atmosphere; put into tube furnace to sinter; sintering step is: first heat up with the rapid-result degree being less than 40 DEG C ~ 80 DEG C/minute, keeps 20 ~ 30 minutes, then cool to 540 DEG C ~ 560 DEG C with the speed of 50 DEG C ~ 100 DEG C/minute when temperature reaches 1050 DEG C; keep 10 minutes, now cool to room temperature with the speed of 20 DEG C ~ 50 DEG C/min.
The process curve of described sintering is shown in accompanying drawing 2, wherein:
The programming rate of intensification section 40 DEG C ~ 80 DEG C/min, makes glass reach fusing point in this stage;
T1 is 1000 ~ 1050 DEG C, 20 ~ 30 minutes time, and glass and tantalum material are fully reacted, ensure tantalum lead-in wire and tantalum lid and glass can fully sintered together with;
First paragraph cooling rate is 40 ~ 80 DEG C/min, can lower the temperature as early as possible;
T2 section temperature is 540 DEG C ~ 560 DEG C, is incubated 10 minutes, and the Main Function of T2 section is the internal stress of the glass after eliminating sintering, improves the environmental adaptability such as the cold-and-heat resistent alternation of sintered products;
After T2 section completes, then drop to room temperature with the speed of 20 DEG C ~ 50 DEG C/min.
Extremely stable in tantalum air at normal temperatures, but can chemical combination direct with various nonmetalloid after heating, as hydrogen, oxygen, nitrogen etc., now its mechanical performance also changes, and the SINTERING TECHNOLOGY of the insulator that therefore insulate is the Chief technology of this manufacture method.First just can not select the atmosphere containing above-mentioned several gas when selecting sintering atmosphere, can only inert protective atmosphere be selected, and taking cost into account, select argon gas to be the sintering atmosphere of product;
Upper metal tube described in step (6) be metal tube is nested into tantalum lead-in wire on, arm pressure machine utilizes mould metal tube and tantalum wire are crimped together, steel loop and tantalum lid will form tight fit, this be engaged in vibrate or ultrasonic under can not be separated.
In sum, a kind of high-energy tantalum mixed capacitor shell utilizing this manufacture method to process has good airproof performance, tantalum metal surface non-oxidation or variable color, meets the requirement without the sour leakage of leakage of capacitor.And there is corrosion-resistant, resistance to temperature shock, compression resistance, good environmental adaptability, reliability high.
The disposable battery load electrode glass integration block that buries processed according to this manufacture method can meet following index:
1, solderability: the aging 8h of steam, 245 ± 5 DEG C, time 5 ± 0.5s, tin sticky face >=95%;
2, (predetermined pulse): 5000m is impacted
2/ s;
3, sealing leak rate≤1 × 10
-3pacm
3/ s;
4, temperature cycles :-65 DEG C ~+150 DEG C, 300 times;
5, insulation resistance >=10000M Ω.
High-energy tantalum mixed capacitor shell of the present invention has good seal performance, is convenient to welding of electrode and external circuit, meets after high-energy tantalum mixed capacitor encapsulation without leakage requirement.
It should be noted that, in this article, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thus make to comprise the process of a series of key element, method, article or equipment and not only comprise which key element, but also comprise other key elements clearly do not listed, or also comprise by the intrinsic key element of this process, method, article or equipment.
Apply specific case herein to set forth principle of the present invention and execution mode, the explanation of above example just understands method of the present invention and core concept thereof for helping.The above is only the preferred embodiment of the present invention, should be understood that, due to the finiteness of literal expression, and objectively there is unlimited concrete structure, for those skilled in the art, under the premise without departing from the principles of the invention, some improvement, retouching or change can also be made, also above-mentioned technical characteristic can be combined by rights; These improve retouching, change or combination, or the design of invention and technical scheme are directly applied to other occasion without improving, and all should be considered as protection scope of the present invention.