CN103367672B - Black box of a kind of battery and preparation method thereof and a kind of lithium ion battery - Google Patents
Black box of a kind of battery and preparation method thereof and a kind of lithium ion battery Download PDFInfo
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- CN103367672B CN103367672B CN201210087023.1A CN201210087023A CN103367672B CN 103367672 B CN103367672 B CN 103367672B CN 201210087023 A CN201210087023 A CN 201210087023A CN 103367672 B CN103367672 B CN 103367672B
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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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Abstract
The present invention relates to a kind of black box of battery, comprise: becket, ceramic ring and stem stem, described metal ring is connected to the outside of described ceramic ring, and the middle part of described ceramic ring is provided with through hole, described stem stem is arranged in described through hole, forms linkage interface between described stem stem and described ceramic ring; The black box of described battery also comprises separator, and described separator seals the inner side of described linkage interface.The invention still further relates to the manufacture method of the black box of above-mentioned battery, and adopt the lithium ion battery of this black box.Separator is comprised at the black box of battery of the present invention; the inner side of the linkage interface of described separator sealing stem stem and ceramic ring; described separator has preferably electrochemical corrosion resistant performance; the linkage interface of protection stem stem and ceramic ring can be played not by the protective effect of electrolytic corrosion, effectively extend the life-span of lithium ion battery.
Description
Technical field
The present invention relates to the technical field of sealing technology of battery; Specifically, black box that the present invention relates to a kind of battery and preparation method thereof and a kind of lithium ion battery.
Background technology
At present, in the packaging technology of conventional battery, Plastic Package, glass packaging and ceramic packaging three major types can be divided into according to encapsulating material; Wherein, plastics sealing-in is considered from angle in useful life, the more difficult instructions for use meeting long-life (more than 20 years) energy-storage battery and reliability electrokinetic cell.In the sealing of existing lithium ion battery, the cover plate of black box and stem stem are mainly by vitreum sealing-in.Such as: CN2419690 discloses a kind of lid of lithium ion battery, battery case cover plate and electrode draw core vitreum sealing; Battery case cover plate has liquid injection hole, the safe valve block sealing of liquid injection hole.The temperature coefficient that battery case, vitreum and electrode draw core is answered identical or close.The sealing of battery and the release of dangerous pressure can be guaranteed, thus improve efficiency and the security performance of lithium ion battery.
But at lithium ion battery Long-Time Service with after storing, the vitreum lower floor directly contacted with the electrolyte of lithium ion battery can be corroded.Such as: French Saft Groupe Sa carries out anticorrosive test by accelerated aging test method to vitreum, after black box and lithium ion battery body are assembled into lithium ion battery, place 7 days at 150 DEG C, found that vitreous surface is corroded, the air-tightness of black box reduces, and is less than 1.0 × 10
-7m
3pa/s.Producing this existing main cause is: lithium metal can go back the silicon dioxide in bare glass, and can constantly penetrate in vitreum, not only reduces the insulation property of glass, more can cause the leakage of lithium battery.At present, the external problems that solves is mainly through the not silica containing corrosion resistance insulating glass of exploitation, and the sealing temperature of this glass is higher, all very harsh to the requirement of instrument and supplies condition.
Thus, ceramic seal becomes the direction of those skilled in the art's primary study, those skilled in the art will appreciate that existing battery adopts aluminium and copper material as the material of the positive and negative electrode stem stem of battery mostly.Because both have low resistivity, the actual resistance of stem stem significantly can be reduced; And adopt aluminum or aluminum alloy shell to reach the object of loss of weight and raising heat dispersion.But, the fusing point of aluminium and copper is on the low side, be respectively 660 DEG C and 1083 DEG C, general Vitrea sealing temperature is then at about 1000 DEG C, thus, when adopting vitreum sealing-in aluminium stem stem, owing to needing to carry out sealing-in below the fusing point of aluminium, Vitrea sealing-in requirement cannot be met, be difficult to realize the sealing-in to aluminium stem stem; And when adopting vitreum sealing-in copper stem stem, also because of the fusing point close to copper, be difficult to ensure sealing-in quality; Meanwhile, also there is the feature of mechanical property deficiency in glass sealing process, is not suitable for electrokinetic cell and uses.
Thus, ceramic seal becomes the direction of those skilled in the art's primary study, but, there is following problems in current ceramic seal technique: pottery exists greatest differences with the thermal coefficient of expansion of aluminium, copper, in product preparation and follow-up use procedure (cold cycling), pottery and the linkage interface place of aluminium, copper exist because thermal mismatching causes the risk of seal failure, in addition, pottery adopts solder to weld with the linkage interface of aluminium, copper usually, there is the problem that resistance to chemical corrosion is not good, thus cause electrolyte leakage, affect the life-span of battery.
Summary of the invention
The present invention is that the black box solving battery in prior art adopts pottery to carry out sealing-in, and the sealing property of black box is poor, causes the technical problem of electrolyte leakage.
In order to solve the problems of the technologies described above, the invention provides a kind of black box of battery, comprise: becket, ceramic ring and stem stem, described metal ring is connected to the outside of described ceramic ring, the middle part of described ceramic ring is provided with through hole, described stem stem is arranged in described through hole, forms linkage interface between described stem stem and described ceramic ring; The black box of described battery also comprises separator, and described separator seals the inner side of described linkage interface.
In the black box of described battery, preferably, the radial dimension of described separator is greater than the radial dimension of described stem stem.
In the black box of described battery, preferably, described separator is the sealing block be made up of rubber type of material or plastic materials or the seal coating formed after being solidified by adhesive.
In the black box of described battery, preferably, described stem stem comprises stem stem external piece and fitting in the stem stem that is connected with described stem stem external piece, and described separator to be fixed in stem stem external piece and described stem stem between fitting.
In the black box of described battery, preferably, the inner side of described stem stem external piece is provided with installing hole; In described stem stem, fitting comprises link for connecting pole piece and stiff end, and described stiff end is fixed in the installing hole of stem stem external piece through separator.
In the black box of described battery, preferably, the black box of described battery is the black box of anode, and described stem stem external piece is made up of the one in the composite material of the composite material of aluminum or aluminum alloy, aluminum or aluminum alloy and ceramic material, aluminum or aluminum alloy and metal material; In described stem stem, fitting is made up of aluminum or aluminum alloy;
Or the black box of described battery is the black box of battery cathode, described stem stem external piece is made up of the one in the composite material of the composite material of copper or copper alloy, copper or copper alloy and ceramic material, copper or copper alloy and metal material; In described stem stem, fitting is made up of copper or copper alloy.
In the black box of described battery, preferably, described stem stem external piece is complex; Described complex comprises porous body and metal material, and described metal material is filled in the hole of described porous body.
In the black box of described battery, preferably, the black box of described battery is the black box of anode, and described metal material is aluminum or aluminum alloy; Described porous body is by one or more porous bodies made in aluminium oxide, aluminium nitride, boron nitride.
In the black box of described battery, preferably, the black box of described battery is the black box of battery cathode, described metal material is copper or copper alloy, and described porous body is by one or more porous bodies made in molybdenum, tungsten, chromium, titanium carbide, carborundum, boron carbide, tungsten carbide.
In the black box of described battery, preferably, described ceramic ring is the one in aluminium oxide ceramics ring, zirconia ceramics ring or aluminium oxide and zirconic composite ceramics ring;
Described becket is aluminium ring or aluminum alloy ring.
Present invention also offers the manufacture method of the black box of above-mentioned battery, comprise the steps:
Step 1, stem stem is arranged in the through hole of ceramic ring, between stem stem and described ceramic ring, forms linkage interface; And metal ring is connected to the outside of ceramic ring;
Step 2, separator to be fixed on stem stem, and to seal the inner side of described linkage interface.
In described manufacture method, preferably, in step 2, described separator is the sealing block adopting at least one in fluorubber, silicon rubber, polytetrafluoroethylene, polyurethane material to be made into; Described stem stem comprises stem stem external piece and fitting in the stem stem that is connected with stem stem external piece, the inner side of described stem stem external piece is provided with installing hole, in described stem stem, fitting comprises link for connecting pole piece and stiff end, by the stiff end of fitting in stem stem is fixed in the installing hole of stem stem external piece through described sealing block, described sealing block to be fixed in stem stem external piece and stem stem between fitting.
In described manufacture method, preferably, in step 2, adopt the adhesive of at least one comprised in epoxy resin, acrylate to be coated on the inner side of the linkage interface of stem stem and described ceramic ring, after solidification, form described separator.
Invention further provides a kind of lithium ion battery, comprise: the housing of at least one end opening, be sealed in the black box of the openend of described housing, seal cavity is formed between described housing and black box, contain pole piece and electrolyte in described seal cavity, described black box adopts the black box of battery as above.
The black box of battery of the present invention comprises separator; the inner side of the linkage interface of described separator sealing stem stem and ceramic ring; described separator has preferably electrochemical corrosion resistant performance; the linkage interface of protection stem stem and ceramic ring can be played not by the protective effect of electrolytic corrosion; make the connection of whole black box reliable; good sealing effect, effectively can improve the useful life of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the battery of the preferred embodiment of the present invention.
Fig. 2 is the schematic diagram of the black box of the battery of the preferred embodiment of the present invention.
Fig. 3-5 is scheme of installations of the black box of the battery of the preferred embodiment of the present invention.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
With reference to the accompanying drawings the specific embodiment of the present invention is described in detail.Herein, same reference numerals represents same composition part.Further, should be appreciated that in describing the invention, " inner side " is near the pole piece of lithium ion battery and the side of electrolyte, the downside namely shown in Fig. 1-5; " outside " side for being connected with external component, the upside namely shown in Fig. 1-5.
The black box of battery of the present invention is used for the sealing of battery, more for the sealing of lithium ion battery, especially high-power lithium ion battery, such as: the sealing of lithium-ion-power cell, lithium-ion energy storage battery.Skilled in the art will recognize that lithium ion battery mainly comprises: housing 11, the electrolyte 13 being positioned over the pole piece 12 in housing 11 and being contained in housing 11.Wherein, described housing 11 is generally aluminum hull or box hat, for placing pole piece 12 and holding electrolyte 13, it is at least provided with opening in one end, in order to avoid spilling of electrolyte, positive and negative electrode black box 2,2 ' is adopted to seal the opening part of housing 11, and external power supply or power consumption equipment.Described pole piece 12 is formed by positive plate, barrier film, negative plate successively stacked or winding, and the structure of pole piece 12 and manufacture method, by existing techniques in realizing, do not repeat at this.
Improvements of the present invention are mainly black box, consult Fig. 2, the black box 2 of the battery of the preferred embodiment of the present invention, comprise: becket 25, ceramic ring 23 and stem stem 21, described becket 25 is socketed on the outside of described ceramic ring 23, the middle part of described ceramic ring 23 is provided with through hole, and described stem stem 21 is arranged in described through hole, forms linkage interface 22 between described stem stem 21 and described ceramic ring 23; The black box of described battery also comprises separator 24, and described separator 24 seals the inner side of described linkage interface 22.
Specifically, described becket 25 is aluminium ring or aluminum alloy ring, and becket 25 welds mutually with the housing 11 of lithium ion battery, to make the opening of black box seal casinghousing 11; Becket 25 for being connected with the housing 11 of lithium ion battery (general realize being connected by welding), to realize being tightly connected of whole black box of the present invention and lithium-ion electric tank main body.The middle part of described becket 25 forms connecting hole, and the aperture of connecting hole equals or slightly larger than the external diameter of ceramic ring 23, for installing ceramic ring 23.It is worth mentioning that, because stem stem 21 is used as a pole of battery, and becket 25 is connected with housing 11, thus needs to ensure that stem stem 21 insulate with becket 25 phase, by the setting of ceramic ring 23, stem stem 21 is connected with becket 25 and ensures the insulation between them.
Described ceramic ring 23 can be the one in aluminium oxide ceramics ring, zirconia ceramics ring, titanium carbide ceramic ring, aluminium nitride ceramics ring, boron nitride ceramics ring, silicon nitride ceramics ring, aluminium oxide and zirconic composite ceramics ring, be preferably aluminium oxide ceramics ring, zirconia ceramics ring or aluminium oxide and zirconic composite ceramics ring, be conducive to being formed with stem stem 21 applying well and connect, and generating process is ripe, advantage of lower cost.Ceramic ring 23 for connecting stem stem 21 and becket 25, and ensures the insulation between stem stem 21 and becket 25; The decay resistance of ceramic ring 23 is very good, by electrolytic corrosion, can not can ensure the useful life of lithium ion battery; And impact strength, the thermal shock resistance of ceramic ring 23 are better than vitreum, make the structure of black box more stable, sealing effectiveness is better; In the present invention, the through hole formed in the middle part of described ceramic ring 23 can be used for making stem stem 21.
Stem stem 21 of the present invention comprises stem stem external piece 211 and fitting 212 in the stem stem that is connected with described stem stem external piece 211, wherein, when the black box of described battery is the black box of anode, described stem stem external piece 211 can be made up of the composite material of the composite material of aluminum or aluminum alloy, aluminum or aluminum alloy and ceramic material, aluminum or aluminum alloy and metal material; In described stem stem, fitting 212 is made up of aluminum or aluminum alloy; When the black box of described battery is the black box of battery cathode, described stem stem external piece 211 can be made up of the composite material of the composite material of copper or copper alloy, copper or copper alloy and ceramic material, copper or copper alloy and metal material; In described stem stem, fitting is made up of copper or copper alloy.
Preferably, the complex that described stem stem external piece 211 is made for composite material, can be cermet complex or metal-metal complex, this complex structure comprises porous body and metal material, and metal material is filled in the hole of described porous body; Described porous body and ceramic ring form combination structure, and described metal material is filled in the hole of described porous body.Described complex structure not only has good electric conductivity, good electric connection can be formed with the pole piece of lithium ion battery, the more important thing is, because described porous body and ceramic ring can form integrative-structure, then (concrete manufacture method refers to following) in described porous body will be filled in after described metallic material.Metal material can form good soaking with porous body, and whole stem stem external piece 211 and ceramic ring 23 form seamless link, and thermal coefficient of expansion matches, and can form good combination, connects reliable, good sealing effect.
It is worth mentioning that, the preferred following material of selection of described porous body: one and metal material, the one namely in aluminum or aluminum alloy, copper or copper alloy has preferably stability, wetability after combining; Two, because the thermal coefficient of expansion of aluminum or aluminum alloy, copper or copper alloy is greater than the thermal coefficient of expansion of ceramic ring, thus require that the thermal coefficient of expansion of porous body is less than the thermal coefficient of expansion of ceramic ring (such as: aluminium oxide ceramics ring, zirconia ceramics ring), like this, after porous body and metal material (one in aluminum or aluminum alloy, copper or copper alloy) compound, the thermal coefficient of expansion of the composite material stem stem obtained can match with the thermal coefficient of expansion of ceramic ring, has preferably thermal shock resistance.Thus, in the preferred case, when the black box of described battery is the black box of anode, described metal material is aluminium (thermal coefficient of expansion is 23.2ppm/K) or aluminium alloy; Described porous body is by one or more porous bodies made of (thermal coefficient of expansion is 0.1-6ppm/K) in aluminium oxide (thermal coefficient of expansion is 7.5ppm/K), aluminium nitride (thermal coefficient of expansion is 4.5ppm/K), boron nitride.When the black box of described battery is the black box of battery cathode, described metal material is copper (thermal coefficient of expansion is 17.9ppm/K) or copper alloy, and described porous body is by one or more porous bodies made in molybdenum (thermal coefficient of expansion is 5.17ppm/K), tungsten (thermal coefficient of expansion is 4.5ppm/K), chromium (thermal coefficient of expansion is 4.9ppm/K), titanium carbide (thermal coefficient of expansion is 7.4ppm/K), carborundum (thermal coefficient of expansion is 4.7ppm/K), boron carbide (thermal coefficient of expansion is 4.5ppm/K), tungsten carbide (thermal coefficient of expansion is 4.7ppm/K).
As shown in Figures 1 and 2, in the present embodiment, the inner side of described stem stem external piece 211 is also formed with installing hole 213, for installing fitting 212 in stem stem in described installing hole; In described stem stem, fitting 212 comprises link 214 and stiff end 216, and described stiff end 216 is installed in the installing hole 213 of stem stem external piece 211, is fixedly connected with fitting in stem stem 212 to make stem stem external piece 211; Described link 214 is for connecting the pole piece of lithium ion battery; The type of attachment of fitting 212 in described stem stem external piece 211 and stem stem, and the setting of installing hole 213 on stem stem external piece 211, the internal stress that stem stem can be made to be subject in long-term colding and heat succeed each other improves, and improves the unmatched problem of thermal coefficient of expansion of ceramic ring and stem stem from structure.
Consult Fig. 1 and Fig. 2, main improvements of the present invention are, the black box 2(2 ' of described battery) also comprise separator 24, described separator 24 seals the inner side of described linkage interface 22; Described separator 24 only can be arranged on linkage interface 22 place; or be arranged on the inner side of the black box of whole battery; as long as the inner side of described linkage interface 22 can be sealed; the version that electrolyte in guarantee battery can not touch linkage interface 22 all can be used for the present invention; thus can effectively protect ceramic ring 23 not to be subject to the corrosion of the electrolyte of inside battery with the linkage interface 22 of stem stem 2; make whole black box have good sealing property and air-tightness, extend the service time of battery.In addition, described linkage interface can be that the combination interface of stem stem and ceramic ring is (when adopting above-mentioned complex stem stem, because porous body and ceramic ring form good seamless combination, without the need to welding), also can be that weld layer is (when adopting metal mandril, need to form weld layer to connect ceramic ring and stem stem, linkage interface is now weld layer), corrode to enable weld layer electrolyte resistance, just existing, negative pole black box adopts precious metal-based solder (such as: Au parent metal) usually, cause cost higher, thus the stem stem of complex is preferably adopted.
In the preferred case, the radial dimension of described separator 24 is more than or equal to the radial dimension of stem stem 21.As shown in Figure 2, the external diameter of described separator 24 is greater than the external diameter of stem stem external piece 211, corresponding perforation 242 is offered corresponding to the installing hole 213 of stem stem external piece 211 in the middle part of it, be fixedly connected with stem stem external piece 211 through rear with for fitting in stem stem 212, the more important thing is, when separator 24 needs by mechanical connection, in described stem stem, separator 24 can be fixed in stem stem external piece 211 and described stem stem between fitting 212 by fitting 212 and stem stem external piece 211 be fixedly connected with effectively.
It should be noted that, described separator 24 can for the sealing block be made up of rubber type of material or plastic materials; In the preferred case, described separator 24 is the sealing block adopting at least one material in fluorubber, silicon rubber, polytetrafluoroethylene, polyurethane material to be made into, the fixing sealing block of shape is made into by adopting above-mentioned material, then adopt the method for mechanical erection, be sealed in the inner side of described linkage interface 22.The mode that described machinery is fixed as previously mentioned; can be fixed in the installing hole 213 of stem stem external piece 211 through separator 24 for making the stiff end 216 of fitting 212 in stem stem; thus described separator 24 to be fixed in stem stem external piece 211 and described stem stem between fitting 212, make described sealing block play the effect of sealing, protection.
Described separator 24 can also be the seal coating formed after being solidified by adhesive, in the preferred case, described separator 24 is the inner side adopting the adhesive of at least one comprised in epoxy resin, acrylate to be coated on linkage interface, the seal coating formed after solidification; By adopting adhesive directly to apply at the inner side of linkage interface 22 (i.e. the inner face of stem stem external piece 211 and ceramic ring 23), then solidifying, playing the effect of sealing, protection.Be understandable that, as long as sealing stem stem 21 can be played all can be used for the present invention with the form that arranges of the separator 24 of the linkage interface 22 of ceramic ring 23, be not limited to the form of above-mentioned mechanical connection and coating Post RDBMS, be also not limited to above-mentioned material.
In sum, the black box of battery of the present invention is provided with separator, the inner side of the linkage interface of described separator sealing stem stem and ceramic ring, described separator has preferably electrochemical corrosion resistant performance, the linkage interface of protection stem stem and ceramic ring can be played not by the protective effect of electrolytic corrosion, the life-span of effective prolongation lithium ion battery, and, by separator, electrolyte and linkage interface (combination interface or weld layer) are effectively isolated, the kind selected of solder is more, precious metal-based solder can not be adopted, effectively cost-saving; In addition, the type of attachment of fitting in described stem stem external piece and stem stem, and the setting of installing hole on stem stem external piece can make stem stem in long-term colding and heat succeed each other, suffered internal stress is eased, and improves the unmatched problem of thermal coefficient of expansion of ceramic ring and stem stem from structure.Further, the stem stem external piece of described stem stem can be complex, comprise porous body and metal material, described porous body is by inserting in the through hole of described ceramic ring by ceramic material or metal material, formed after sintering, thus can and ceramic ring between form good connection, and then will infiltrate in described porous body after metallic material, described metal material and porous body form good combination, and the thermal coefficient of expansion of described complex and described ceramic ring matches, there is good cold-hot impact, the connection of whole black box is reliable, good sealing effect, effectively can improve the useful life of lithium ion battery.
The invention provides the manufacture method of the black box of the battery of above preferred embodiment, comprise the steps:
Step 1, stem stem is arranged in the through hole of ceramic ring, between stem stem and described ceramic ring, forms linkage interface; And metal ring is connected to the outside of ceramic ring;
The middle part of described ceramic ring 23 is formed with through hole, stem stem 21 is arranged in the through hole of ceramic ring 23, forms linkage interface 22 between stem stem 21 and described ceramic ring 23, as previously mentioned, described linkage interface 22 can be the combination interface of stem stem 21 and ceramic ring 23, also can be weld layer.
In this step, the method of forming ceramic ring 23 can adopt method known in those skilled in the art, such as: adopt dry-pressing formed method that ceramic powder is pressed into ceramic ring 23, described ceramic powder can be selected from one or more in aluminium oxide, zirconia, titanium carbide, aluminium nitride, boron nitride, silicon nitride ceramics powder, after forming ceramic ring 23, form through hole at the middle part of ceramic ring 23.
In the shaping stem stem external piece 211 be made up of aluminum or aluminum alloy, copper or copper alloy and stem stem, the method for fitting 212 can be casting die, and when the black box of described battery is the black box of anode, described stem stem external piece 211 is made up of aluminum or aluminum alloy; When in described stem stem, fitting 212 is made up of aluminum or aluminum alloy; When the black box of described battery is the black box of battery cathode, described stem stem external piece 211 is made up of copper or copper alloy, when fitting 212 is made up of copper or copper alloy in described stem stem, adopts casting die to make; It has been method known in those skilled in the art that casting die makes metalwork, does not repeat at this.Further, when the black box of described battery is the black box of anode, when stem stem external piece 211 adopts aluminum or aluminum alloy material, when the solder that described soldering processes adopt is aluminium base solder, brazing temperature is 580 DEG C-640 DEG C, and the holding time is 1-5min.When the black box of described battery is the black box of battery cathode, when stem stem external piece 211 adopts copper or copper alloy, when the solder that described soldering processes adopt is copper base solder, brazing temperature is brazing temperature is 890 DEG C-1000 DEG C, holding time 1-5min.After brazing, between described ceramic ring 23 and the linkage interface of described stem stem external piece 211, form weld layer, stem stem external piece 211 is connected by described weld layer with ceramic ring 23, and now, described linkage interface 22 is weld layer.
In the present invention, preferred described stem stem external piece 211 is complex; Described complex comprises porous body and metal material (when the black box of described battery is the black box of battery cathode, described metal material is copper or copper alloy, when the black box of described battery is the black box of anode, described metal material is aluminum or aluminum alloy), described metal material is filled in the hole of described porous body.The preferred pressureless infiltration method of manufacture method of described complex stem stem or pressure infiltration method, by the material being used for making porous body is made into porous body, described porous body is infiltrated after metallic material, and be filled in the hole of described porous body after cooling, form good combination with described porous body.
Specifically, described pressureless infiltration method, pressure infiltration method comprise the steps: steps A, take the raw material of formula ratio, described raw material packet is containing porous materials, binding agent, surfactant, adopt dry-pressing, extrude, injection moulding, the forming method such as injection prepare green compact, obtained porous body after binder removal, pre-burning.
Wherein, in the preferred case, when the black box of described battery is the black box of anode, the material for porous body is ceramic material, comprises one or more in aluminium oxide, aluminium nitride, boron nitride.When the black box of described battery is the black box of battery cathode, being ceramic material or metal material for making the material of porous body, comprising one or more in molybdenum, tungsten, chromium, titanium carbide, carborundum, boron carbide, tungsten carbide.The binding agent that described binding agent and surfactant can adopt this area conventional and surfactant, its effect and kind have been conventionally known to one of skill in the art.Described binding agent is preferably the one in heteropolymer constituent element paraffinic base binding agent (PW), polyvinyl acetate (PVA), epoxy resin (EP), polyethylene (PE), ethylene-vinyl acetate copolymer (EVA) etc., there is lower fusing point (such as: the fusing point of PW is only 50-60 DEG C), and be easy to removing in the binder removal stage; Described surfactant is preferably the one in stearic acid (SA), oleic acid, and surfactant is preferred ingredient, its role is to the compatibility improving ceramic powder and binding agent.In the present invention, with the ceramic powder of 100 weight portions for benchmark, the content of described binding agent is 7-30 weight portion, and the content of described surfactant is 0.5-3 weight portion.
Described dry-pressing, extrude, equipment that injection moulding, the forming method such as injection adopt and making step be for conventionally known to one of skill in the art, time actual shaping, can according to the difference of the kind of selected porous materials, binding agent, surfactant and content, its preparation condition of suitable adjustment and parameter.In the present invention, preferably, adopt the shaping green compact of method of injection moulding, above-mentioned expansion coefficient material, binding agent, surfactant are carried out batch mixing in hot injection moulding machine, and mixture temperature is 80-150 DEG C; Then shaping green compact in the die cavity that mates with the shape of through holes of ceramic ring are cast onto at the pressure of 0.6-0.75Mpa.
Described binder removal is also conventionally known to one of skill in the art, its role is to remove the binding agent in green compact, can regulate according to actual conditions, in the present invention, preferably slowly to heat up and the mode of temperature-gradient method carries out binder removal, binder removal effect is better, such as: be warming up to 50 DEG C-60 DEG C with the speed of 5 DEG C/min-10 DEG C/min, then 150 DEG C ± 20 DEG C are warming up to the speed of 0.2-0.5 DEG C/min, 1-3h is incubated at 150 DEG C ± 20 DEG C, be warming up to 300 DEG C ± 30 DEG C with the speed of 0.2-0.5 DEG C/min again, at 300 DEG C ± 30 DEG C, be incubated 1-3h.
Described pre-sinter process is also conventionally known to one of skill in the art, can regulate according to actual conditions.At pre-burning stage control calcined temperature, base substrate can be made to obtain certain intensity, and the hole of porous body can be made to be perforate, burn-in time is 1-3h, obtains the porous body with certain porosity and intensity after pre-burning completes; Described porous body and ceramic ring form good combination, and the linkage interface of described ceramic ring and stem stem is the combination interface of porous body and ceramic ring.
Step B, to process at the temperature of metal material more than the fusing point of metal material, the metal material of melting is infiltrated in the hole of described porous body, after cooling, forms porous body.
Described infiltration can selection pressure infiltration also can be pressureless infiltration, the condition of pressure infiltration is: on the fusing point of metal material, carry out under the fusing point of porous body, the metal material of melting is made to infiltrate in the hole of described porous body under pressure, the pressure of pressure infiltration is selected as the case may be, the mode of preferably segmented boosting carries out pressure infiltration, such as: first time adds 5-20MPa pressure, second time adds 50-100MPa pressure, then pressurize 1-10min, the infiltration effect of metal material can be better.The method of the present invention's more preferably pressureless infiltration; the condition of described pressureless infiltration is in the protective atmosphere of vacuum or inert gas; on the fusing point of metal material; carry out under the fusing point of porous materials, to make metallic material form molten metal, and need ensure at such a temperature; the angle of wetting of molten metal and porous body is less than 90 °; now, molten metal can penetrate in the hole of porous body by the capillarity of hole, namely obtains composite material stem stem after infiltration completes.
Described becket adopts casting die to make, and it has been method known in those skilled in the art that casting die makes metalwork, does not repeat at this.In this step, becket 25 is socketed on the outside of ceramic ring 23, between becket 25 and ceramic ring 23, soldering lug is installed, then the soldering of soldering processes phase is adopted, described soldering processes need to use solder to realize soldering below base material metal fusing point, the solder that soldering processes adopt is aluminium base solder, such as: Al-Si alloy, Al-Mg alloy, Al-Si-Mg alloy etc.; The temperature of soldering processes is 580 DEG C-640 DEG C, and the holding time is 1-5min; Atmosphere is vacuum or inert gas atmosphere, and described inert gas atmosphere is preferably nitrogen atmosphere.After brazing, between described becket 25 and the composition surface of ceramic ring 23, form weld layer, becket 25 is connected by described weld layer with ceramic ring 23.
The preferred embodiments of the present invention are also included in the fabrication and installation hole, below 213 of stem stem external piece 211; Such as: when adopting the method shaping stem stem external piece 211 of injection moulding, by die casting fabrication and installation hole 213.Correspondingly, the preferred embodiments of the present invention are also included in described installing hole 221 and install fitting 212 in stem stem, such as: when the black box of described battery is the black box 2 of battery cathode, in stem stem, fitting 212 can adopt copper or copper alloy part; When the black box of described battery is the black box 2 ' of anode, in stem stem, fitting 212 can adopt aluminum or aluminum alloy part; For connecting the pole piece of battery, pole piece is connected by fitting 212 in above-mentioned stem stem, be convenient to weld with pole piece, and the type of attachment of fitting 212 in described stem stem external piece 211 and stem stem, and the setting of installing hole 213 on stem stem external piece 211, the internal stress that stem stem can be made to be subject in long-term colding and heat succeed each other improves, and improves the unmatched problem of thermal coefficient of expansion of ceramic ring and stem stem from structure.In addition, by arranging separator 24 between fitting 212 in stem stem external piece 211 and stem stem, effectively can avoid the linkage interface of electrolytic corrosion stem stem external piece 211 and ceramic ring, structure is more reliable, longer service life.
Step 2, separator to be fixed on stem stem, and to seal the inner side of described linkage interface.
In this step, described separator 24 can for the sealing block be made up of rubber type of material or plastic materials; In the preferred case, described separator 24 is the sealing block adopting at least one material in fluorubber, silicon rubber, polytetrafluoroethylene, polyurethane material to be made into, described fluorubber, silicon rubber, polytetrafluoroethylene, polyurethane material sealing block can commercially buy, and are made the sealing block of required form by machine work; By adopting above-mentioned material to be made into the fixing sealing block of shape, then adopting the method for mechanical erection, separator 24 being sealed in the inner side of described linkage interface 22.The method of described mechanical erection can for be fixed in the installing hole 213 of stem stem external piece 211 by the stiff end 216 of fitting in stem stem 212 through separator 24, to be fixed on by described sealing block 24 in stem stem external piece 211 and stem stem between fitting 212.
Described separator 24 can also be the seal coating formed after being solidified by adhesive, described adhesive can adopt existing can sealed ceramic and metal any one adhesive in the preferred case, described separator 24 is the adhesive adopting at least one comprised in epoxy resin, acrylate, polyurethane resin, preferably comprise the adhesive of at least one of epoxy resin, acrylate, described adhesive can adopt adhesive known in those skilled in the art.In the preferred case: described adhesive can adopt following formula: the formula of epoxy adhesive: epoxy resin 100 mass parts, flexibilizer (is selected from acrylonitrile-butadiene rubber, polysulfide rubber, dibutyl phthalate, one or more in dioctyl phthalate etc.) 10-15 mass parts, thixotropic agent (such as: nano silicon micronization) 0.5-1.5 mass parts, curing agent, amine curing agent can be selected from, acid anhydride type curing agent, one or more in imidazole curing agent, wherein the content of amine curing agent (such as: triethanolamine) is 25-35 mass parts, the content of acid anhydride type curing agent (such as: methyl tetrahydro phthalic anhydride) is 80-100 part, imidazole curing agent (such as: diethyl tetramethyl imidazoles, 1, 2-methylimidazole) content be 2-7 part.The formula of acrylate adhesive: acrylic acid-2-ethyl ethyl ester 8-10 mass parts, vinyl acetate 10-12 mass parts, butyl acrylate 50-57 mass parts, acrylic acid-second hydroxyl ethyl ester 2-3 mass parts, N hydroxymethyl acrylamide 3-5 mass parts, dibenzoyl peroxide 0.1-0.5 mass parts.Adhesive is obtained after being stirred by the raw material of above-mentioned formula.Described adhesive is coated on the inner side of linkage interface, the seal coating formed after solidification, described curing temperature is preferably 20-130 DEG C, and curing time is preferably 1-24 hour; By adopting adhesive directly to apply on the inner side of linkage interface (i.e. the inner face of stem stem external piece), then solidifying, playing the effect of sealing, protection.
As shown in Figure 1, the lithium ion battery of the preferred embodiment of the present invention, comprise positive pole black box 2 and negative pole black box 2 ', one end of housing 11 is provided with two openings, pole piece 12 is positioned in housing 11, and (or carry out fluid injection subsequently through the liquid injection hole on becket 25 to fluid injection in housing 11, known to those skilled in the art), then described positive pole black box 2 and negative pole black box 2 ' are installed on respectively the opening part of housing 11, in this process, described positive pole black box 2 is welded with housing 11 mutually with the becket 25 of negative pole black box 2 ', and by positive pole black box 2, in the stem stem of negative pole black box 2, fitting and pole piece 12 are just, negative plate is connected, after installation, seal cavity is formed between black box and housing, pole piece 12 and electrolyte 13 is contained in sealing space, the stem stem 21 of described positive pole black box 2 and negative pole black box 2 ', the upper end of 21 ' is respectively as the two poles of the earth of lithium ion battery, can external power consumption equipment, due to stem stem 21,21 ' and linkage interface 22 place of described ceramic ring 23 be sealed with separator 24, described separator 24 has preferably electrochemical corrosion resistant performance, the linkage interface of protection stem stem and ceramic ring can be played not by the protective effect of electrolytic corrosion, effectively extend the life-span of lithium ion battery.
Below with reference to specific embodiment 1-6, the present invention is further elaborated.
embodiment 1
The present embodiment 1 composition graphs 3-Fig. 5, for illustration of the making of the black box of anode of the present invention, comprises the steps:
Step 1.1, shaping stem stem external piece 211, make stem stem external piece 211 be formed in the through hole of ceramic ring 23: to take 100gAl
2o
3powder (particle diameter is 20 μm), 1gSA, 10gPW, in hot injection moulding machine, carry out batch mixing, mixture temperature is 100 DEG C, batch mixing evenly after under the pressure of 0.7MPa in ceramic ring 23 die cast green compact, the lower end of described green compact is formed with installing hole 213; Then the assembly of ceramic ring and green compact is carried out binder removal, preheating in resistance furnace, wherein, binder removal step: be warming up to 50 DEG C with the speed of 5 DEG C/min, then 150 DEG C are warming up to the speed of 0.3 DEG C/min, 2h is incubated at 150 DEG C, be warming up to 300 DEG C with the speed of 0.3 DEG C/min again, at 300 DEG C, be incubated 2h; Pre-burning: be warming up to 950 DEG C of preheatings with the speed of 10 DEG C/min after binder removal completes, burn-in time is 2h, after binder removal, pre-burning, obtain Al
2o
3ceramic porous article; Then at N
2in protective atmosphere, rise to 1000 DEG C to Al with the speed of 10 DEG C/min
2o
3ceramic porous article carries out pressureless infiltration almag, makes the almag of melting infiltrate described Al
2o
3in the hole of ceramic porous article, infiltration completes the Al namely obtained as shown in Figure 3
2o
3the assembly of ceramic ring 23 and stem stem external piece 211, form linkage interface 22 between described stem stem external piece 211 and described ceramic ring 23, the lower end of described stem stem external piece 211 is formed with installing hole 213;
Step 1.2, installation becket 25: use Al-Si solder to be scaling powder, under vacuum atmosphere, becket 25 is welded in the outside of ceramic ring 23 at 620 DEG C, insulation 8min, then cools the assembly obtained as shown in Figure 4 fast;
Step 2.1, in the coating of the inner side of combinations thereof body containing the adhesive of epoxy resin, the formula of described adhesive is: epoxy resin E-51100 mass parts, acrylonitrile-butadiene rubber 10 mass parts, nano silicon micronization 1 mass parts, methyl tetrahydro phthalic anhydride 90 mass parts, methylimidazole 1 mass parts, solidify 1 hour at 120 DEG C after coating, as shown in Figure 5, separator 24 is formed, the linkage interface 22 of described separator 24 sealed ceramic ring 23 and stem stem external piece 211 in the inner side of ceramic ring 23 and stem stem external piece 211;
Step 2.2, in the installing hole 213 of described stem stem external piece 211, fitting 212 in aluminium is installed, in described aluminium, the stiff end 216 of fitting 212 is fixed in the installing hole 213 of stem stem external piece 211 through separator 24, obtains the black box A1 of anode as described in Figure 2.
embodiment 2
The present embodiment 2, for illustration of the making of the black box of anode of the present invention, comprises the steps:
Step 1.1, shaping stem stem external piece, make stem stem external piece be formed in the through hole of ceramic ring: to take 100gZrO
2powder (particle diameter is 15 μm), 0.8g oleic acid, 8g polyethylene, in hot injection moulding machine, carry out batch mixing, mixture temperature is 120 DEG C, batch mixing evenly after under the pressure of 0.75MPa in ceramic ring die cast green compact, the lower end of described green compact is formed with installing hole; Then the assembly of ceramic ring and green compact is carried out binder removal, preheating in resistance furnace, wherein, binder removal step: be warming up to 55 DEG C with the speed of 8 DEG C/min, then 160 DEG C are warming up to the speed of 0.2 DEG C/min, 2h is incubated at 160 DEG C, be warming up to 300 DEG C with the speed of 0.3 DEG C/min again, at 300 DEG C, be incubated 2h; Pre-burning: be warming up to 950 DEG C of preheatings with the speed of 10 DEG C/min after binder removal completes, burn-in time is 2h, after binder removal, pre-burning, obtain ZrO
2ceramic porous article; Then at N
2in protective atmosphere, rise to 1200 DEG C to ZrO with the speed of 10 DEG C/min
2ceramic porous article carries out pressureless infiltration fine aluminium, makes the fine aluminium of melting infiltrate described ZrO
2in the hole of ceramic porous article, infiltration completes and namely obtains ZrO
2the assembly of ceramic ring and stem stem external piece, forms linkage interface between described stem stem external piece and described ceramic ring, and the lower end of described stem stem external piece is formed with installing hole;
Step 1.2, installation becket: use Al-Si solder to be scaling powder, under vacuum atmosphere, by the outside of welding metal rings in ceramic ring at 650 DEG C, insulation 10min, then cooling obtains assembly fast;
Polytetrafluoroethylene is made sealing block by the method for step 2, employing injection mo(u)lding, and form perforation in the middle part of described sealing block, the external diameter of sealing block is greater than the external diameter of stem stem external piece, then in the installing hole of described stem stem external piece, fitting in aluminium is installed, in described aluminium, the stiff end of fitting is fixed in the installing hole of stem stem external piece through the perforation of sealing block, sealing block to be fixed in stem stem external piece and stem stem between fitting, to obtain the black box A2 of anode.
embodiment 3
The present embodiment 3, for illustration of the making of the black box of anode of the present invention, comprises the steps:
Step 1, shaping stem stem external piece, make stem stem external piece be formed in the through hole of ceramic ring: the shaping aluminium external piece of method adopting injection moulding, and be formed with installing hole in the lower end of described aluminium external piece; Then use Al-Si alloy to be scaling powder, under vacuum atmosphere, stem stem external piece is welded in the inner side of ceramic ring at 620 DEG C, by the outside of welding metal rings in ceramic ring, insulation 8min, then cools fast and obtain assembly;
Step 2, fluorubber block is processed into the sealing block of required form, and form perforation in the middle part of described sealing block, the external diameter of sealing block is greater than the external diameter of aluminium external piece, then in the installing hole of described aluminium external piece, fitting in aluminium is installed, in described aluminium, the stiff end of fitting is fixed in the installing hole of aluminium external piece through the perforation of sealing block, sealing block to be fixed in aluminium external piece and aluminium between fitting, to obtain the black box A3 of anode.
embodiment 4
The present embodiment 4, for illustration of the making of the black box of battery cathode of the present invention, comprises the steps:
Step 1, shaping stem stem external piece, make stem stem external piece be formed in the through hole of ceramic ring: taking 100gTiC(particle diameter is 18 μm), 0.5gSA, 10gPW, batch mixing is carried out in hot injection moulding machine, mixture temperature is 140 DEG C, batch mixing evenly after under the pressure of 0.65MPa in ceramic ring die cast green compact, the lower end of described green compact is formed with installing hole; Then the assembly of ceramic ring and green compact is carried out binder removal, preheating in hydrogen reducing furnace, wherein, binder removal step: be warming up to 50 DEG C with the speed of 10 DEG C/min, then 160 DEG C are warming up to the speed of 0.3 DEG C/min, 2h is incubated at 160 DEG C, be warming up to 320 DEG C with the speed of 0.3 DEG C/min again, at 320 DEG C, be incubated 2h; Pre-burning: be warming up to 1350 DEG C of preheatings with the speed of 10 DEG C/min after binder removal completes, burn-in time is 2h, obtains TiC ceramic porous article after binder removal, pre-burning; Then in vacuum furnace, (vacuum degree is 10
-3pa), rise to 1350 DEG C with the speed of 10 DEG C/min and carry out pressureless infiltration fine copper to TiC ceramic porous article, the fine copper of melting is infiltrated in the hole of described TiC ceramic porous article, and infiltration completes and namely obtains Al
2o
3the assembly of ceramic ring and stem stem external piece, the lower end of described stem stem external piece is formed with installing hole;
Step 1.2, installation becket: use Al-Si alloy to be scaling powder, under vacuum atmosphere, by the outside of welding metal rings in ceramic ring at 620 DEG C, insulation 8min, then cooling obtains assembly fast;
Step 2.1, in the coating of the inner side of combinations thereof body containing the adhesive of acrylate, the formula of described adhesive is: acrylic acid-2-ethyl ethyl ester 10 mass parts, vinyl acetate 10 mass parts, butyl acrylate 55 mass parts, acrylic acid-second hydroxyl ethyl ester 2 mass parts, N hydroxymethyl acrylamide 4 mass parts, dibenzoyl peroxide 0.3 mass parts, 24 hours are at room temperature solidified after coating, separator is formed, the linkage interface of described separator sealed ceramic ring and stem stem external piece in the inner side of ceramic ring and stem stem external piece;
Step 2.2, in the installing hole of described stem stem external piece, install fitting in copper, in described copper, the stiff end of fitting is fixed in the installing hole of stem stem external piece through separator, obtains the black box A4 of battery cathode.
embodiment 5
The present embodiment 5, for illustration of the making of the black box of battery cathode of the present invention, comprises the steps:
Step 1.1, shaping stem stem external piece, make stem stem external piece be formed in the through hole of ceramic ring: the shaping copper external piece of method adopting injection moulding, and be formed with installing hole in the lower end of described stem stem external piece; Then use Cu-Ti solder, under vacuum atmosphere, stem stem external piece is welded in the inner side of ceramic ring at 1000 DEG C;
Step 1.2, installation becket: use Al-Si alloy to be scaling powder, under vacuum atmosphere, by the outside of welding metal rings in ceramic ring at 620 DEG C, insulation 8min, then cooling obtains assembly fast;
Step 2, adopt injection molding method that polyurethane material is made into sealing block, and form perforation in the middle part of described sealing block, the external diameter of sealing block is greater than the external diameter of stem stem external piece, then in the installing hole of described stem stem external piece, fitting in copper is installed, in described copper, the stiff end of fitting is fixed in the installing hole of stem stem external piece through the perforation of sealing block, sealing block to be fixed in stem stem external piece and copper between fitting, to obtain the black box A5 of battery cathode.
embodiment 6
The present embodiment 6, for illustration of the making of the black box of battery cathode of the present invention, comprises the steps:
Step 1.1, shaping stem stem external piece, make stem stem external piece be formed in the through hole of ceramic ring: the shaping copper external piece of method adopting injection moulding, and be formed with installing hole in the lower end of described stem stem external piece; Then use Cu-Ti solder, under vacuum atmosphere, stem stem external piece is welded in the inner side of ceramic ring at 1000 DEG C;
Step 1.2, installation becket: use Al-Si alloy to be scaling powder, under vacuum atmosphere, by the outside of welding metal rings in ceramic ring at 620 DEG C, insulation 8min, then cooling obtains assembly fast;
Step 2.1, in the coating of the inner side of combinations thereof body containing the adhesive of epoxy resin, the formula of described adhesive is: epoxy resin E-51 mass parts 100, polysulfide rubber 10 mass parts, Nano-meter SiO_2
21.5 mass parts, triethanolamine 25 mass parts, solidifies 2 hours after coating at 80 DEG C, forms separator, the linkage interface of described separator sealed ceramic ring and stem stem external piece in the inner side of ceramic ring and stem stem external piece;
Step 2.2, in the installing hole of described stem stem external piece, install fitting in copper, in described copper, the stiff end of fitting is fixed in the installing hole of stem stem external piece through separator, obtains the black box A6 of battery cathode.
comparative example 1
Comparative example 1 is for illustration of the making of the black box of existing a kind of battery;
Adopt the method for vitreum sealing-in disclosed in CN201397827, by vitreum, sealing-in is carried out to upper cover and aluminium stem stem, obtain the black box D1 of anode; And by vitreum, sealing-in is carried out to the stem stem that upper cover and metallic copper make, obtain the black box D2 of battery cathode.
comparative example 2
Comparative example 2 is for illustration of the making of the black box of existing alternative battery;
Adopt the method for crunch seal, under vacuum, respectively the stem stem that becket, ceramic ring and metallic aluminium, copper are done is welded together, obtain the black box D3 of anode and the black box D4 of battery cathode.
performance test
1, air tightness test
Black box D1, D2, D3, D4 that the black box A1-6 obtained by embodiment 1-6 and comparative example 1,2 obtain are placed in clips chamber, the connecting portion of black box to be tested is exposed clips chamber, 0.6MPa pressure is filled in cavity, pressurize 3min, drips at connecting portion, if bubbling simultaneously, be considered as gas leakage, if do not have bubbling phenomenon, be then considered as air-tightness and meet the demands, test result is as shown in table 1.
Table 1
| outward appearance | |
| a1 | the connecting portion of black box A1 is without bubbling phenomenon. |
| a2 | the connecting portion of black box A2 is without bubbling phenomenon. |
| a3 | the connecting portion of black box A3 is without bubbling phenomenon. |
| a4 | the connecting portion of black box A4 is without bubbling phenomenon. |
| a5 | the connecting portion of black box A5 is without bubbling phenomenon. |
| a6 | the connecting portion of black box A6 is without bubbling phenomenon. |
| d1 | there is bubble in the connecting portion of black box D1, not by air tightness test. |
| d2 | there is bubble in the connecting portion of black box D1, not by air tightness test. |
| d3 | the connecting portion of black box D3 is without bubbling phenomenon. |
| d4 | the connecting portion of black box D4 is without bubbling phenomenon. |
2, cold shock testing
Black box D3, D4 that the black box A1-A6 obtained by embodiment 1-6 and comparative example 2 obtain, 3min is placed in cold water below 0 DEG C, be transferred to immediately in the boiling water of more than 100 DEG C and be incubated 3min, repeat this process, test black box is after completing how many times circulation, still by air tightness test, test result is as shown in table 2.
Table 2
| performance | |
| a1 | black box A1 completes 400 thermal shock cyclic tests, still by air tightness test. |
| a2 | black box A2 completes 400 thermal shock cyclic tests, still by air tightness test. |
| a3 | black box A3 completes 400 thermal shock cyclic tests, still by air tightness test. |
| a4 | black box A4 completes 400 thermal shock cyclic tests, still by air tightness test. |
| a5 | black box A5 completes 400 thermal shock cyclic tests, still by air tightness test. |
| a6 | black box A6 completes 400 thermal shock cyclic tests, still by air tightness test. |
| d3 | black box D3 after completing 200 thermal shock cyclic tests, not by air tightness test. |
| d4 | black box D4 after completing 200 thermal shock cyclic tests, not by air tightness test. |
As can be seen from table 1 and table 2, embodiments of the invention 1-6 make black box A1-6 after 400 thermal shock cyclic tests still by air tightness test, absolutely prove that the connection of the black box made by embodiments of the invention 1-6 is reliable, good sealing effect.
Those skilled in the art easily know; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (12)
1. the black box of a battery, it is characterized in that, comprise: becket, ceramic ring and stem stem, described metal ring is connected to the outside of described ceramic ring, the middle part of described ceramic ring is provided with through hole, described stem stem is arranged in described through hole, forms linkage interface between described stem stem and described ceramic ring; The black box of described battery also comprises separator, and described separator seals the inner side of described linkage interface;
Described stem stem comprises stem stem external piece and fitting in the stem stem that is connected with described stem stem external piece, and described separator to be fixed in stem stem external piece and described stem stem between fitting;
Described stem stem external piece is complex; Described complex comprises porous body and metal material, and described metal material is filled in the hole of described porous body.
2. the black box of battery according to claim 1, is characterized in that, the radial dimension of described separator is greater than the radial dimension of described stem stem.
3. the black box of battery according to claim 1, is characterized in that, described separator is the sealing block be made up of rubber type of material or plastic materials or the seal coating formed after being solidified by adhesive.
4. the black box of battery according to claim 1, is characterized in that, the inner side of described stem stem external piece is provided with installing hole; In described stem stem, fitting comprises link for connecting pole piece and stiff end, and described stiff end is fixed in the installing hole of stem stem external piece through separator.
5. the black box of battery according to claim 1, it is characterized in that, the black box of described battery is the black box of anode, and described stem stem external piece is made up of the one in the composite material of the composite material of aluminum or aluminum alloy, aluminum or aluminum alloy and ceramic material, aluminum or aluminum alloy and metal material; In described stem stem, fitting is made up of aluminum or aluminum alloy;
Or the black box of described battery is the black box of battery cathode, described stem stem external piece is made up of the one in the composite material of the composite material of copper or copper alloy, copper or copper alloy and ceramic material, copper or copper alloy and metal material; In described stem stem, fitting is made up of copper or copper alloy.
6. the black box of battery according to claim 5, is characterized in that, the black box of described battery is the black box of anode, and described metal material is aluminum or aluminum alloy; Described porous body is by one or more porous bodies made in aluminium oxide, aluminium nitride, boron nitride.
7. the black box of battery according to claim 5, it is characterized in that, the black box of described battery is the black box of battery cathode, described metal material is copper or copper alloy, and described porous body is by one or more porous bodies made in molybdenum, tungsten, chromium, titanium carbide, carborundum, boron carbide, tungsten carbide.
8. the black box of battery according to claim 1, is characterized in that, described ceramic ring is the one in aluminium oxide ceramics ring, zirconia ceramics ring or aluminium oxide and zirconic composite ceramics ring;
Described becket is aluminium ring or aluminum alloy ring.
9. a manufacture method for the black box of the battery as described in claim 1-8 any one, comprises the steps:
Step 1, stem stem is arranged in the through hole of ceramic ring, between stem stem and described ceramic ring, forms linkage interface; And metal ring is connected to the outside of ceramic ring;
Step 2, separator to be fixed on stem stem, and to seal the inner side of described linkage interface.
10. manufacture method according to claim 9, is characterized in that, in step 2, described separator is the sealing block adopting at least one in fluorubber, silicon rubber, polytetrafluoroethylene, polyurethane material to be made into; Described stem stem comprises stem stem external piece and fitting in the stem stem that is connected with stem stem external piece, the inner side of described stem stem external piece is provided with installing hole, in described stem stem, fitting comprises link for connecting pole piece and stiff end, by the stiff end of fitting in stem stem is fixed in the installing hole of stem stem external piece through described sealing block, described sealing block to be fixed in stem stem external piece and stem stem between fitting.
11. manufacture methods according to claim 9, it is characterized in that, in step 2, adopt the adhesive of at least one comprised in epoxy resin, acrylate, polyurethane resin to be coated on the inner side of the linkage interface of stem stem and described ceramic ring, after solidification, form described separator.
12. 1 kinds of lithium ion batteries, comprise: the housing of at least one end opening, be sealed in the black box of the openend of described housing, seal cavity is formed between described housing and black box, pole piece and electrolyte is contained in described seal cavity, it is characterized in that, described black box adopts the black box of the battery as described in claim 1-8 any one.
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| CN201210087023.1A CN103367672B (en) | 2012-03-29 | 2012-03-29 | Black box of a kind of battery and preparation method thereof and a kind of lithium ion battery |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335117B1 (en) * | 1998-08-07 | 2002-01-01 | Japan Storage Battery Co., Ltd. | Nonaqueous electrolyte battery having hermetically sealed terminals |
| CN1345099A (en) * | 2000-09-29 | 2002-04-17 | 三洋电机株式会社 | Secondary battery |
| CN2717032Y (en) * | 2004-03-18 | 2005-08-10 | 武汉力兴电源股份有限公司 | Electrode leading-out device for large-capacity battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6696199B2 (en) * | 2002-01-30 | 2004-02-24 | Japan Storage Battery Co., Ltd. | Battery |
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2012
- 2012-03-29 CN CN201210087023.1A patent/CN103367672B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335117B1 (en) * | 1998-08-07 | 2002-01-01 | Japan Storage Battery Co., Ltd. | Nonaqueous electrolyte battery having hermetically sealed terminals |
| CN1345099A (en) * | 2000-09-29 | 2002-04-17 | 三洋电机株式会社 | Secondary battery |
| CN2717032Y (en) * | 2004-03-18 | 2005-08-10 | 武汉力兴电源股份有限公司 | Electrode leading-out device for large-capacity battery |
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