CN103367663B - 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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- CN103367663B CN103367663B CN201210087016.1A CN201210087016A CN103367663B CN 103367663 B CN103367663 B CN 103367663B CN 201210087016 A CN201210087016 A CN 201210087016A CN 103367663 B CN103367663 B CN 103367663B
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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, the middle part of described becket is provided with installing hole, described metal ring is connected to the outside of described ceramic ring, the middle part of described ceramic ring is provided with accepting hole, and described core cylindrical is formed in described accepting hole, and described stem stem is composite material stem stem, comprise low-expansion material and metal material, the thermal coefficient of expansion of described low-expansion material is less than the thermal coefficient of expansion of ceramic ring.The invention still further relates to the manufacture method of the black box of above-mentioned battery, comprise the steps: to provide low-expansion material and metal material, and make described low-expansion material and metal material moulding composite material stem stem; Described composite material stem stem is welded in the accepting hole of ceramic ring, and by the outside of welding metal rings in ceramic ring.In addition, present invention also offers the lithium ion battery adopting this black box.The black box of battery of the present invention adopts composite material stem stem, matches, has good cold-hot impact property, effectively can improve the useful life of lithium ion battery with the thermal coefficient of expansion of ceramic ring.
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: CN201397827 discloses a kind of sealing insulator for lithium batteries, comprise the upper cover that has through hole and interted at the upper stem stem covered by described through hole, being provided with vitreum in through hole, and by vitreum, sealing-in being carried out to upper cover and stem stem.
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.
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, current ceramic seal technique Problems existing be pottery (such as: Al
2o
3thermal coefficient of expansion be 7.5 ppm/K) with aluminium (thermal coefficient of expansion is 23.2 ppm/K), copper (thermal coefficient of expansion is 17.9 ppm/K) thermal coefficient of expansion there is greatest differences, in product preparation and follow-up use procedure (cold cycling), pottery and the junction of aluminium, copper exist because thermal mismatching causes the risk of seal failure.
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 pottery there are differences with the thermal coefficient of expansion of aluminium, copper, thus there is the technical problem of the risk causing seal failure because of thermal mismatching.
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, the middle part of described becket is provided with installing hole, and described metal ring is connected to the outside of described ceramic ring, and the middle part of described ceramic ring is provided with accepting hole, described core cylindrical is formed in described accepting hole, described stem stem is composite material stem stem, comprises low-expansion material and metal material, and the thermal coefficient of expansion of described low-expansion material is less than the thermal coefficient of expansion of ceramic ring.
In the black box of described battery, preferably, with the cumulative volume of described composite material stem stem for benchmark, the content of described low-expansion material is 40-80vol%.
In the black box of described battery, preferably, described low-expansion material forms porous body, and metal material is filled in the hole of described porous body.
In the black box of described battery, preferably, the fusing point of described low-expansion material is higher than the fusing point of described metal material.
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, and described low-expansion material is selected from Al
2o
3, one or more in AlN, BN.
In the black box of described battery, preferably, the black box of described battery is the black box of battery cathode, and described metal material is copper and copper alloy, and described low-expansion material is selected from Mo, W, Cr, TiC, SiC, B
4one or more in C, WC.
In the black box of described battery, preferably, described ceramic ring is the one in aluminium oxide ceramics ring, zirconia ceramics ring, aluminium oxide and zirconic composite ceramics ring; Described becket is aluminium ring or aluminum alloy ring.
In the black box of described battery, preferably, the first weld layer is provided with between described composite material stem stem and ceramic ring; The second weld layer is provided with between described ceramic ring and becket.
Present invention also offers the manufacture method of the black box of above-mentioned battery, comprise the steps:
Step 1, provide low-expansion material and metal material, and make described low-expansion material and metal material moulding composite material stem stem;
Step 2, described composite material stem stem to be welded in the accepting hole of ceramic ring, and by the outside of welding metal rings in ceramic ring.
In described manufacture method, preferably, the method for described low-expansion material and metal material moulding composite material stem stem is the one in powder metallurgic method, pressureless infiltration method, pressure infiltration method.
In described manufacture method, preferably, described low-expansion material is made porous body, then in pressurization or environment with no pressure, at temperature more than the fusing point of metal material, metal material is heat-treated, infiltrate after making metallic material in described porous body, after cooling, form composite material stem stem.
In described manufacture method, preferably, the black box of described battery is the black box of anode, and described metal material is aluminum or aluminum alloy, and described low-expansion material is selected from Al
2o
3, one or more in AlN, BN; Or the black box of described battery is the black box of battery cathode, and described metal material is copper or copper alloy, and described low-expansion material is selected from Mo, W, Cr, TiC, SiC, B
4one or more in C, WC.
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, pole piece and electrolyte is contained in described seal cavity, described black box adopts the black box of battery as above, wherein, the becket of the black box of described battery is connected with housing, and the stem stem of the black box of described battery is connected with described pole piece.
In the black box of battery of the present invention, being connected by arranging ceramic ring between becket with stem stem, making to keep between housing and stem stem insulating and forming seal, wherein, stem stem is used for being electrically connected with the pole piece of battery as the electrode of battery, described stem stem is composite material stem stem, comprise low-expansion material and metal material, the thermal coefficient of expansion of described low-expansion material is less than the thermal coefficient of expansion of ceramic ring, and described metal material (such as: Cu, Al) thermal coefficient of expansion is greater than the thermal coefficient of expansion of ceramic ring, the thermal coefficient of expansion of composite material stem stem and the thermal coefficient of expansion of ceramic ring can be made to match by regulating their ratio, and between described low-expansion material and metal material, there is good stability and wetability, thus, the connection of whole black box is reliable, good sealing effect, there is good cold-hot impact property, effectively can improve the useful life of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the schematic diagram 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.
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: the housing of at least one end opening, the electrolyte being positioned over the pole piece in housing and being contained in housing.In order to avoid spilling of electrolyte, the openend of black box to housing is adopted to seal.Wherein, described housing is generally aluminum hull or box hat, for placing pole piece and holding electrolyte, its at least one end opening.Described pole piece is formed by positive plate, barrier film, negative plate successively stacked or winding, and the structure of pole piece and manufacture method, by existing techniques in realizing, do not repeat at this.
Improvements of the present invention are mainly black box, as shown in Figure 1, the black box of the battery of the preferred embodiment of the present invention, comprise: becket 5, ceramic ring 3 and stem stem 1, the middle part of described becket 5 is provided with installing hole 51, and described becket 5 is socketed on the outside of described ceramic ring 3, and the middle part of described ceramic ring 3 is provided with accepting hole 31, described stem stem 1 is formed in described accepting hole 31, and described stem stem 1 is composite material stem stem.
Specifically, described becket 5 is aluminium ring or aluminum alloy ring, and becket 5 welds mutually with the housing of lithium ion battery, to make the openend of black box seal casinghousing; Certainly, described becket 5 can also be other becket of material identical with housing, such as: steel loop, becket 5 for being connected with the housing 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 5 forms installing hole 51, the aperture of installing hole 51 slightly larger than or equal the external diameter of ceramic ring 3; For installing ceramic ring 3.Skilled in the art will recognize that, stem stem 1 is used as a pole of battery, and housing can be used as another pole of battery, becket 5 is connected with housing, thus need to ensure that stem stem 1 insulate with becket 5 phase, by the setting of ceramic ring 3, stem stem 1 is connected with becket 5 and ensures the insulation between them.
Described ceramic ring 3 is the one in aluminium oxide ceramics ring, zirconia ceramics ring, aluminium oxide and zirconic composite ceramics ring, is preferably aluminium oxide ceramics ring, zirconia ceramics ring.Ceramic ring 3 for connecting stem stem 1 and becket 5, and ensures the insulation between stem stem 1 and becket 5; The decay resistance of ceramic ring 3 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 3 are better than vitreum, make the structure of black box more stable, sealing effectiveness is better; In the present invention, the accepting hole 31 formed in the middle part of described ceramic ring 3, for welding mutually with stem stem 1, thus requires that ceramic ring 3 has certain thickness, adopt ceramic ring 3 as sealing-in medium, compared to employing ceramic wafer, its thickness is thicker, thermal shock resistance and thermal circulation performance better.
Main improvements of the present invention are, described stem stem 1 is composite material stem stem, described composite material stem stem comprises metal material and low-expansion material, described metal material and described low-expansion material are integrated by methods combining such as powder metallurgic method, pressureless infiltration method, pressure infiltration methods, described powder metallurgic method, pressureless infiltration method, pressure infiltration method have been that preparation method conventionally known to one of skill in the art, follow-up describes in detail.In the present invention, preferred pressureless infiltration method or pressure infiltration legal system make composite material stem stem, thus the structure of composite material stem stem of the present invention is preferably low-expansion material and forms 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.
Described low-expansion material is required to meet: have preferably stability, wetability after the one one, in aluminum or aluminum alloy, copper or copper alloy is combined, thus ensures that composite material stem stem has preferably associativity; 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 low-expansion material is less than the thermal coefficient of expansion of ceramic ring, like this, after low-expansion material 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 is just likely substantially equal with the thermal coefficient of expansion of ceramic ring; The metal material or the nonmetallic materials (such as: ceramic material) that meet above-mentioned requirements all can be used as low-expansion coefficient of the present invention.In addition; it is worth mentioning that; when employing pressureless infiltration method, pressure infiltration legal system make composite material stem stem; usually the fusing point of fusing point higher than metal material of low-expansion material is also required; after low-expansion material is made into porous body by guarantee; infiltrate in the process of porous body after heating makes metallic material, the low-expansion material forming porous body can not be melted.
Preferably, when the black box of described battery is the black box of anode, described metal material is aluminum or aluminum alloy, is preferably pure aluminum metal (thermal coefficient of expansion is 23.2 ppm/K); Low-expansion material is selected from aluminium oxide (Al
2o
3thermal coefficient of expansion be 7.5 ppm/K), one or more in aluminium nitride (thermal coefficient of expansion of AlN is 4.5 ppm/K), boron nitride (thermal coefficient of expansion of BN is 0.1-6 ppm/K), low-expansion material has the thermal coefficient of expansion lower than ceramic ring (such as: aluminium oxide ceramics ring, zirconia ceramics ring), and energy and aluminum or aluminum alloy form good compound, it should be noted that, when adopting aluminium oxide ceramics ring, low-expansion material can not adopt Al separately
2o
3material, because they have identical thermal coefficient of expansion, cannot make composite material stem stem reach the thermal coefficient of expansion matched with aluminium oxide ceramics ring.In the preferred case, low-expansion material is selected from AlN, BN or Al
2o
3, the composite material of two kinds in AlN, BN, better combination can be formed with metal material, and thermal coefficient of expansion easily matches in ceramic ring.
When the black box of described battery is the black box of battery cathode, described metal material is copper or copper alloy, be preferably fine copper metal (thermal coefficient of expansion is 17.9 ppm/K), low-expansion material is selected from molybdenum (thermal coefficient of expansion of Mo is 5.17 ppm/K), tungsten (thermal coefficient of expansion of W is 4.5 ppm/K), chromium (thermal coefficient of expansion of Cr is 4.9ppm/K), titanium carbide (thermal coefficient of expansion of TiC is 7.4 ppm/K), carborundum (thermal coefficient of expansion of SiC is 4.7 ppm/K), boron carbide (B
4the thermal coefficient of expansion of C is 4.5 ppm/K), one or more in tungsten carbide (thermal coefficient of expansion of WC is 3.8 ppm/K), these low-expansion materials have the thermal coefficient of expansion lower than ceramic ring (such as: aluminium oxide ceramics ring, zirconia ceramics ring), and can and copper or copper alloy form good compound.In the preferred case, low-expansion material is selected from Cr or Cr and Mo, W, TiC, SiC, B
4one or both composite material in C, WC, because Cr is (1000 DEG C) when being heated to certain temperature, do not reach in the process of its fusing point, atoms permeating is there is between Cr powder granule, the i.e. crystal grain process of growing up, in this process, mutually bond between particle or dissolve each other completely with other low-expansion material powders (such as: Mo, W), the porous body obtained after pre-burning has some strength, and better combination can be formed with metal material, and thermal coefficient of expansion easily matches in ceramic ring.
It is worth mentioning that, the thermal coefficient of expansion of composite material stem stem is adjusted by the volume ratio regulating low-expansion material shared in composite core column material, thus obtain the thermal coefficient of expansion matched with the thermal coefficient of expansion of ceramic ring, with the cumulative volume of described composite material stem stem for benchmark, the content of described low-expansion material is 40-80vol%.
In addition, the first weld layer 2 is provided with between composite material stem stem 1 of the present invention and ceramic ring 3; Preferably, when the black box of described battery is the black box of anode, described first weld layer 2 is aluminium base solder layer, adopts aluminium base solder to weld between composite material stem stem 1 with ceramic ring 3.When the black box of described battery is the black box of battery cathode, described first solder layer 2 is copper-based solder layer, adopts copper-based solder to weld between composite material stem stem with ceramic ring 3.Be provided with the second weld layer 5 between described ceramic ring 3 and becket 5, described second weld layer 5 is aluminium base solder layer, adopts aluminium base solder to weld between ceramic ring 3 with becket 5; By the setting of described first weld layer 2 and the second weld layer 5, realize the connection of above-mentioned composite material stem stem 1 and ceramic ring 3, ceramic ring 3 and becket 5.
As from the foregoing, composite material stem stem of the present invention not only has good electric conductivity, good electric connection can be formed with the pole piece of lithium ion battery, and can match with the thermal coefficient of expansion of ceramic ring, thus form good combination, make the connection of whole black box reliable, good sealing effect.
The invention provides the manufacture method of the black box of the battery of above preferred embodiment, comprise the steps:
Step 1, provide low-expansion material and metal material, and make described low-expansion material and metal material moulding composite material stem stem.
In this step, the selection of described low-expansion material is required to meet: one and metal material, and 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 low-expansion material is less than the thermal coefficient of expansion of ceramic ring, like this, after low-expansion material 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 just likely matches with the thermal coefficient of expansion of ceramic ring; The metal material or the nonmetallic materials (such as: ceramic material) that meet above-mentioned requirements all can be used as low-expansion coefficient of the present invention.
Preferably, when the black box of described battery is the black box of anode, described metal material is aluminum or aluminum alloy, is preferably pure aluminum metal (thermal coefficient of expansion is 23.2 ppm/K); Low-expansion material is selected from Al
2o
3(thermal coefficient of expansion is 7.5 ppm/K), AlN(thermal coefficient of expansion are 4.5 ppm/K), BN(thermal coefficient of expansion is 0.1-6 ppm/K) in one or more, low-expansion material has the thermal coefficient of expansion lower than ceramic ring (such as: aluminium oxide ceramics ring, zirconia ceramics ring), and energy and aluminum or aluminum alloy form good compound.In the preferred case, low-expansion material is selected from AlN, BN or Al
2o
3, the composite material of two kinds in AlN, BN, better combination can be formed with metal material, and thermal coefficient of expansion easily matches in ceramic ring.
When the black box of described battery is the black box of battery cathode, described metal material is copper or copper alloy, be preferably fine copper metal (thermal coefficient of expansion is 17.9 ppm/K), it is 5.17 ppm/K that low-expansion material is selected from Mo(thermal coefficient of expansion), W(thermal coefficient of expansion is 4.5 ppm/K), Cr(thermal coefficient of expansion is 4.9ppm/K), TiC(thermal coefficient of expansion is 7.4 ppm/K), SiC(thermal coefficient of expansion is 4.7 ppm/K), B
4c(thermal coefficient of expansion is 4.5 ppm/K), WC(thermal coefficient of expansion is 3.8 ppm/K) in one or more, these low-expansion materials have the thermal coefficient of expansion lower than ceramic ring (such as: aluminium oxide ceramics ring, zirconia ceramics ring), and can and copper or copper alloy form good compound.In the preferred case, low-expansion material is selected from Cr or Cr and Mo, W, TiC, SiC, B
4one or both composite material in C, WC, because Cr is (1000 DEG C) when being heated to certain temperature, do not reach in the process of its fusing point, atoms permeating is there is between Cr powder granule, the i.e. crystal grain process of growing up, in this process, mutually bond between particle or dissolve each other completely with other low-expansion material powders (such as: Mo, W), the porous body obtained after pre-burning has some strength, and better combination can be formed with metal material, and thermal coefficient of expansion easily matches in ceramic ring.
It is worth mentioning that, the thermal coefficient of expansion of composite material stem stem is adjusted by the volume ratio regulating low-expansion material shared in composite core column material, thus the thermal coefficient of expansion of acquisition and ceramic ring (such as: Al
2o
3thermal coefficient of expansion be 7.5 ppm/K; ZrO
2thermal coefficient of expansion be 10.5 ppm/K) thermal coefficient of expansion that matches, with the cumulative volume of described composite material stem stem for benchmark, the content of described low-expansion material is 40-80vol%.
Described metal material and described low-expansion material are integrated by methods combining such as powder metallurgic method, pressureless infiltration method, pressure infiltration methods, and described powder metallurgic method, pressureless infiltration method, pressure infiltration method have been conventionally known to one of skill in the art; Such as: powder metallurgic method makes composite material stem stem, that low-expansion material, metal material are first carried out ball milling in ball grinder, obtained mixed-powder is poured in the die cavity with certain pressure compressing pressed compact after ball milling is even, then in inert gas atmosphere, first carry out pre-burning, sinter again after obtain composite material stem stem, the temperature of described force value, pre-burning and sintering can be determined according to the fusing point of adopted low-expansion material, metal material, and these have been conventionally known to one of skill in the art.
In the present invention, preferred pressureless infiltration method or pressure infiltration legal system make composite material stem stem, by low-expansion material is made into porous body, infiltrate described porous body after metallic material, and be filled in the hole of described porous body after cooling, form good combination with described porous body.It is worth mentioning that; when employing pressureless infiltration method, pressure infiltration legal system make composite material stem stem; usually the fusing point of fusing point higher than metal material of low-expansion material is also required; after low-expansion material is made into porous body by guarantee; infiltrate in the process of porous body after heating makes metallic material, the low-expansion material forming porous body can not be melted.
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 low-expansion material, 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, described low-expansion material requires according to the making of positive and negative electrode and required thermal coefficient of expansion is selected, and described low-expansion material selection particle diameter is the powder granule of 1-150 micron; Preferably, the powder granule that described low-expansion material selects particle diameter different, such as, selects particle size range 20-100 μm and particle size range at the powder granule of 2-10 μm, selects the powder granule of different-grain diameter scope, make it disperse evenly.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 low-expansion material, 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 low-expansion material, binding agent, surfactant are carried out batch mixing in hot injection moulding machine, and mixture temperature is 80-150 DEG C; Then cast onto and shaping green compact in the die cavity of the accepting hole form fit of ceramic ring 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, such as: the calcined temperature of AlN material is at 1000-1200 DEG C, BN, Al
2o
3the calcined temperature of material is at 1100-1300 DEG C.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.In the process of binder removal and presintering, pass through control temperature, it is all perforate that binding agent can be made to be removed rear left hole, can ensure that the liquation of metal material is fully filled in the hole of porous body under the effect of capillary force like this, make the follow-up density preparing composite material stem stem higher.
According to the requirement of the performance to composite material stem stem, the porosity of obtained porous body is 20-40%, and above-mentioned hole is perforate, exposes the surface of porous body, for filling metal material.The porosity of described porous body can utilize existing drainage to test, the amount of the metal material then needed for the volume computing of porous body, and the volume of porous body is larger, then the coefficient of expansion is lower, more mates with the thermal coefficient of expansion of described ceramic ring; And the packing volume of metal material is larger, the intensity of then obtained composite material stem stem is high, good toughness, better with the electric conductivity of pole piece, thus can regulate the porosity of porous body according to specific needs, thus regulate low-expansion material and metal material in the volume accounting of composite material stem stem.
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 low-expansion material, 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 low-expansion material, 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.
In the present invention, by the volume ratio regulating low-expansion material shared in composite core column material, thus obtain the thermal coefficient of expansion matched with the thermal coefficient of expansion of ceramic ring, with the cumulative volume of described composite material stem stem for benchmark, the content of described low-expansion material is 40-80vol%.
Step 2, described composite material stem stem to be welded in the accepting hole of ceramic ring, and by the outside of welding metal rings in ceramic ring.
In this step, described ceramic ring can adopt the ceramic rings such as commercially available aluminium oxide, zirconia, also can make, the method made 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, described ceramic powder can be selected from one or more in aluminium oxide, Zirconium powder, after forming ceramic ring, forms accepting hole at the middle part of ceramic ring; Described becket can adopt the aluminum or aluminum alloy ring sold, and also can be made by methods such as die casting, the method for making can adopt method known in those skilled in the art, does not repeat at this.
In this step, stem stem 1 is installed in the accepting hole of ceramic ring 3, between stem stem 1 and ceramic ring 3, soldering lug is installed, then adopts soldering processes by the collecting hole wall phase soldering of the lateral surface of described stem stem 1 with ceramic ring 3, thus stem stem 1 is connected in the accepting hole of ceramic ring 3; Described soldering processes have been conventionally known to one of skill in the art, namely adopt and make solder than the low-melting metal material of mother metal, by weldment and solder heat to higher than solder fusing point, lower than the temperature of mother metal fusing point, utilize liquid solder to soak mother metal, the gap between fill assembly realizes the method connecting weldment.Described soldering can use soldering lug (soldering lug is installed and installed by punch forming curved surface annulus exactly), solder paste (method by coating) carries out soldering, the condition of soldering processes: atmosphere is vacuum or inert gas atmosphere, brazing temperature is higher than the temperature of solder lower than the melt temperature of stem stem 1, and the holding time is 1-10 minute.
When the black box of described battery is the black box of anode, when stem stem 1 is for comprising the composite material stem stem of 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 1 is for comprising the composite material stem stem of copper or Cu alloy material, when the solder that described soldering processes adopt is copper base solder, brazing temperature is 890 DEG C-1000 DEG C, holding time 1-5min.After brazing, form the first weld layer 2 between described ceramic ring 3 and the joint face of described stem stem 1, becket 5 is connected by described first weld layer 2 with ceramic ring 3.
In this step, becket 5 is socketed on the outside of ceramic ring 3, between becket 5 and ceramic ring 3, 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, form the second weld layer 4 between described becket 5 and the composition surface of ceramic ring 3, becket 5 is connected by described second weld layer 4 with ceramic ring 3.It is worth mentioning that, if the copper base solder that the first weld layer uses, then first the brazing temperature of soldering stem stem 1 and ceramic ring 3(Cu base solder at 890-1000 DEG C) form the first weld layer, and then brazing metal ring 5 forms the second weld layer (brazing temperature of Al base solder is at 580-640 DEG C) with ceramic ring 3; If what the first weld layer used is also Al base solder, then can carry out soldering to stem stem 1 and ceramic ring 3, becket 5 and ceramic ring 3 simultaneously.
As from the foregoing, in the black box of battery of the present invention, being connected by arranging ceramic ring between becket with stem stem, making to keep between housing and stem stem insulating and forming seal, wherein, stem stem is used for being electrically connected with the pole piece of battery as the electrode of battery, described stem stem is composite material stem stem, comprise low-expansion material and metal material, the thermal coefficient of expansion of described low-expansion material is less than the thermal coefficient of expansion of ceramic ring, and described metal material (such as: Cu, Al) thermal coefficient of expansion is greater than the thermal coefficient of expansion of ceramic ring, the thermal coefficient of expansion of composite material stem stem and the thermal coefficient of expansion of ceramic ring are matched, and between described low-expansion material and metal material, there is good stability and wetability, thus, the connection of whole black box is reliable, good sealing effect, there is good cold-hot impact property, effectively can improve the useful life of lithium ion battery.
When assembling whole lithium ion battery, cell sealing assemble comprises the black box of battery cathode and the black box of anode, two end openings of housing, pole piece is positioned in housing, then the black box of the black box of battery cathode and anode is installed on respectively two openends of housing, in this process, the becket of black box is welded mutually with housing, and the stem stem of black box is connected (specifically with pole piece, the positive plate of pole piece is connected by the stem stem of anode ear with the black box of anode, the negative plate of pole piece is connected by the stem stem of negative electrode lug with the black box of battery cathode, concrete structure is by existing techniques in realizing), after installation, seal cavity is formed between black box and housing, pole piece and electrolyte is contained in sealing space, the stem stem of the black box of battery cathode and the black box of anode is respectively as the two poles of the earth of lithium ion battery, can external power consumption equipment.
Below with reference to specific embodiment 1-9, the present invention is further elaborated.
embodiment 1
The present embodiment 1, for illustration of the making of the black box of anode of the present invention, comprises the steps:
Step 1, adopt and with no pressurely ooze the standby anode composite material stem stem containing 55vol% AlN of legal system:
A, take 300g AlN powder, 4g stearic acid, 72g paraffin, in hot injection moulding machine, carry out batch mixing, mixture temperature is 140 DEG C, batch mixing evenly after cast onto shaping green compact in the die cavity that mates with the internal via shape of ceramic ring at the pressure of 0.65MPa; Then green compact are 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 1200 DEG C of preheatings with the speed of 10 DEG C/min after binder removal completes, burn-in time is 2h; AlN ceramic porous body is obtained after binder removal, pre-burning;
B, at N
2in protective atmosphere, rise to 1000 DEG C with the speed of 10 DEG C/min and be incubated 1h and pressureless infiltration aluminium is carried out to AlN ceramic porous body, make the aluminium liquid of melting infiltrate in the hole of described AlN ceramic porous body, aluminising completes and obtains the composite material stem stem containing 55vol% AlN after cooling;
Step 2, ceramic ring is installed, becket: stem stem is installed in the accepting hole of zirconia ceramics ring, almag ring set is connected to the outside of zirconia ceramics ring, then Al-Si system soldering lug is installed between stem stem and zirconia ceramics ring, and between zirconia ceramics ring and almag ring, then place in a vacuum furnace, soldering 5 minutes at 615 DEG C, make between the lateral surface of composite material stem stem and the collecting hole wall of zirconia ceramics ring, all compact siro spinning technology is obtained by the formation of weld layer between the lateral surface of zirconia ceramics ring and the installation hole wall of almag ring, obtain the black box A1 of anode.
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, the standby composite material positive pole stem stem containing 60vol% BN of employing pressure infiltration legal system:
A, take 300g BN powder, 8g stearic acid, 80g paraffin, adopt the injection moulding technological forming similar to embodiment 1, binder removal, pre-burning (calcined temperature is 1300 DEG C), obtain BN ceramic porous article;
B, employing pressure infiltration method carry out aluminising, BN ceramic porous article is put into die casting and is preheated to 450-550 DEG C, aluminium is heated to 750-850 DEG C and makes it whole melting, with pouring in die casting by aluminium liquid, first time adds 10MPa pressure, and second time adds 100MPa pressure, pressurize 8min, the aluminium liquid of melting infiltrates in the hole of described BN ceramic porous article under stress, obtains the composite material stem stem containing 60vol% BN after cooling;
Step 2, the employing Al-Si system soldering lug identical with embodiment 1 and welding procedure, complete the soldering between composite material stem stem and aluminium oxide ceramics ring and between aluminium oxide ceramics ring and almag ring, obtain the black box A2 of battery.
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, adopt legal system of oozing with no pressure standby containing 60vol% Al
2o
3with the anode composite material stem stem of AlN:
A, take 150g Al
2o
3powder, 150g AlN powder, mix with high speed dispersion agent, then take 5g stearic acid, 50g paraffin, adopts the injection moulding technological forming similar to embodiment 1, binder removal, pre-burning (calcined temperature is 1300 DEG C), after binder removal, pre-burning, obtain Al
2o
3with AlN ceramic porous body;
B, at N
2in protective atmosphere, rise to 1000 DEG C with the speed of 10 DEG C/min and be incubated 1h and pressureless infiltration aluminium is carried out to AlN ceramic porous body, make the aluminium liquid of melting infiltrate described Al
2o
3with in the hole of AlN ceramic porous body, aluminising completes and obtains after cooling containing 60vol% Al
2o
3with the composite material stem stem of AlN;
Step 2, the employing Al-Si system soldering lug identical with embodiment 1 and welding procedure, complete the soldering between composite material stem stem and zirconia ceramics ring and between zirconia ceramics ring and almag ring, obtain the black box A3 of battery.
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, adopt and with no pressurely ooze the standby anode material stem stem containing 60vol% Cr of legal system:
A, take 300g Cr powder, take 2.2g stearic acid, 22g paraffin again, adopt the injection moulding technological forming similar to embodiment 1, binder removal, (calcined temperature is 1100 DEG C in pre-burning, Cr is when 1100 DEG C of preliminary treatment, atoms permeating is there is between Cr powder granule, it is the process of particle growth, in this process, mutually bond between particle, the porous body obtained after pre-burning has some strength, the situation that porous structure falls apart can not be there is when oozing copper for follow-up 1200 DEG C), after binder removal, pre-burning, obtain Cr metal porous body;
B, H in drying
2in atmosphere, rise to 1200 DEG C with the speed of 10 DEG C/min and be incubated 30min and pressureless infiltration copper is carried out to Cr metal porous body, the copper liquid of melting is infiltrated in the hole of described Cr metal porous body, oozes copper and complete and obtain the composite material stem stem containing 60vol% Cr after cooling;
Step 2, installation ceramic ring, becket: stem stem is installed in the accepting hole of zirconia ceramics ring, Au-Cu system soldering lug is installed between stem stem and zirconia ceramics ring, then place in a vacuum furnace, soldering 5 minutes at 1000 DEG C, makes to obtain compact siro spinning technology by the formation of the first weld layer between the collecting hole wall of the lateral surface of composite material stem stem and zirconia ceramics ring; Then aluminum metal ring set is connected to the outside of zirconia ceramics ring, Al-Si system soldering lug is installed between zirconia ceramics ring and aluminum metal ring, then place in a vacuum furnace, soldering 5 minutes at 630 DEG C, make to obtain compact siro spinning technology by the formation of the second weld layer between the installation hole wall of the lateral surface of zirconia ceramics ring and aluminum metal ring, obtain 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, adopt and with no pressurely ooze the standby anode material stem stem containing 65vol% Cr and Mo of legal system:
A, take 150g Cr powder (particle diameter is 100 microns), 150g Mo powder (particle diameter is 5 microns), mix with high speed dispersor, take 1.8g stearic acid again, 18g paraffin, adopt the injection moulding technological forming similar to embodiment 1, binder removal, (calcined temperature is 1000 DEG C in pre-burning, Cr and Mo two kinds of metal dusts are more than 1000 DEG C, it is complete solid solution, that is, these 1000 DEG C of above pre-burnings of temperature, the counterdiffusion of atom phase can be there is between two kinds of metal dusts, mutually bond between particle, the porous body obtained after pre-burning has some strength, the situation that porous structure falls apart can not be there is) when oozing copper for follow-up 1400 DEG C, through binder removal, Cr-Mo metal porous body is obtained after pre-burning,
B, in an ar atmosphere, rise to 1400 DEG C with the speed of 10 DEG C/min and be incubated 2h and pressureless infiltration copper is carried out to Cr-Mo metal porous body, the copper liquid of melting is infiltrated in the hole of described Cr-Mo metal porous body, oozes copper and complete and obtain the composite material stem stem containing 65vol% Cr-Mo after cooling;
Step 2, installation ceramic ring, becket: stem stem is installed in the accepting hole of aluminium oxide ceramics ring, Au-Cu system soldering lug is installed between stem stem and zirconia ceramics ring, then place in a vacuum furnace, soldering 3 minutes at 1000 DEG C, makes to obtain compact siro spinning technology by the formation of the first weld layer between the collecting hole wall of the lateral surface of composite material stem stem and aluminium oxide ceramics ring; Then aluminum metal ring set is connected to the outside of zirconia ceramics ring, Al-Si system soldering lug is installed between aluminium oxide ceramics ring and aluminum metal ring, then place in a vacuum furnace, soldering 5 minutes at 620 DEG C, make to obtain compact siro spinning technology by the formation of the second weld layer between the installation hole wall of the lateral surface of aluminium oxide ceramics ring and aluminum metal ring, 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, the preparation of employing powder metallurgic method contain the anode material stem stem of 65vol% Cr and W: take 150g Cr powder (particle diameter is 100 microns), 150g W powder (particle diameter is 5 microns), 100g Cu powder, load ball milling 24h in stainless steel jar mill, after ball milling, mixed-powder is poured into compressing cylindrical green compact in the die cavity of 150MPa pressure, then by pressed compact 900 DEG C of pre-burning 1h in hydrogen atmosphere, again at 1450 DEG C of sintering 1h, obtain the composite material stem stem of Cr-W and Cu;
Step 2, installation ceramic ring, becket: stem stem is installed in the accepting hole of zirconia ceramics ring, Au-Cu system soldering lug is installed between stem stem and zirconia ceramics ring, then place in a vacuum furnace, soldering 3 minutes at 1000 DEG C, makes to obtain compact siro spinning technology by the formation of the first weld layer between the collecting hole wall of the lateral surface of composite material stem stem and zirconia ceramics ring; Then aluminum metal ring set is connected to the outside of zirconia ceramics ring, Al-Si system soldering lug is installed between zirconia ceramics ring and aluminum metal ring, then place in a vacuum furnace, soldering 5 minutes at 620 DEG C, make to obtain compact siro spinning technology by the formation of the second weld layer between the installation hole wall of the lateral surface of zirconia ceramics ring and aluminum metal ring, obtain the black box A6 of battery cathode.
embodiment 7
The present embodiment 7, for illustration of the making of the black box of battery cathode of the present invention, comprises the steps:
Step 1, the preparation of employing powder metallurgic method contain the anode material stem stem of W and WC: take 150g WC powder (particle diameter is 20 microns), 150g W powder (particle diameter is 5 microns), 70g Cu powder, load ball milling 24h in stainless steel jar mill, after ball milling, mixed-powder is poured into compressing cylindrical green compact in the die cavity of 200MPa pressure, then by pressed compact 900 DEG C of pre-burning 1h in hydrogen atmosphere, again at 1500 DEG C of sintering 1h, obtain the composite material stem stem of W-WC and Cu;
Step 2, installation ceramic ring, becket: stem stem is installed in the accepting hole of zirconia ceramics ring, Au-Cu system soldering lug is installed between stem stem and zirconia ceramics ring, then place in a vacuum furnace, soldering 3 minutes at 1000 DEG C, makes to obtain compact siro spinning technology by the formation of the first weld layer between the collecting hole wall of the lateral surface of composite material stem stem and zirconia ceramics ring; Then aluminum metal ring set is connected to the outside of zirconia ceramics ring, Al-Si system soldering lug is installed between zirconia ceramics ring and aluminum metal ring, then place in a vacuum furnace, soldering 5 minutes at 620 DEG C, make to obtain compact siro spinning technology by the formation of the second weld layer between the installation hole wall of the lateral surface of zirconia ceramics ring and aluminum metal ring, obtain the black box A7 of battery cathode.
embodiment 8
The present embodiment 8, for illustration of the making of the black box of battery cathode of the present invention, comprises the steps:
Step 1, the preparation of employing powder metallurgic method contain the anode material stem stem of Cr and SiC: take 150g SiC powder (particle diameter is 20 microns), 150g Cr powder (particle diameter is 5 microns), 70g Cu powder, load ball milling 20h in stainless steel jar mill, after ball milling, mixed-powder is poured into compressing cylindrical green compact in the die cavity of 180MPa pressure, then by pressed compact 1000 DEG C of pre-burning 1h in hydrogen atmosphere, again at 1200 DEG C of sintering 1h, obtain the composite material stem stem of Cr-SiC and Cu;
Step 2, installation ceramic ring, becket: above-mentioned composite material stem stem is installed in the accepting hole of zirconia ceramics ring, Au-Cu system soldering lug is installed between stem stem and zirconia ceramics ring, then place in a vacuum furnace, soldering 3 minutes at 1000 DEG C, makes to obtain compact siro spinning technology by the formation of the first weld layer between the collecting hole wall of the lateral surface of composite material stem stem and zirconia ceramics ring; Then aluminum metal ring set is connected to the outside of zirconia ceramics ring, Al-Si system soldering lug is installed between zirconia ceramics ring and aluminum metal ring, then place in a vacuum furnace, soldering 5 minutes at 620 DEG C, make to obtain compact siro spinning technology by the formation of the second weld layer between the installation hole wall of the lateral surface of zirconia ceramics ring and aluminum metal ring, obtain the black box A8 of battery cathode.
embodiment 9
The present embodiment 9, for illustration of the making of the black box of battery cathode of the present invention, comprises the steps:
Step 1, adopt legal system of oozing with no pressure standby containing 70vol% TiC-B
4the anode material stem stem of C:
A, take 150g TiC powder (particle diameter is 100 microns), 150g B
4c powder (particle diameter is 5 microns), mix with high speed dispersor and obtain mixed-powder, press paraffin (PW) again: high density polyethylene (HDPE) (HDPE): ethene-vinyl acetate resin copolymer (EVA): stearic acid (SA)=70:15:11:4(weight ratio) batching, pour 130 DEG C of mixing 1h in mixing roll into, obtain heteropolymer constituent element paraffinic base binding agent; Then by TiC-B
4c mixed-powder and paraffinic base binding agent be 130 DEG C of mixing 2h, wherein TiC-B on mixing roll
4c mixed powder accounts for volume 70vol%, mixing end and granulate after, in injector injection moulding, injection temperature 150 DEG C, injection pressure 120Mpa, obtains preform, then preform is carried out binder removal, preheating, wherein, first binder removal step for dissolve degreasing by preform in trichloroethylene, and solution temperature is 40 DEG C, subsequently preform is warming up in vacuum degreasing stove 200 DEG C of insulation 1h, be warming up to 580 DEG C of insulation 2h again, binding agent can be removed completely; Then continue to be warming up to 1500 DEG C and be incubated 2h and carry out presintering, obtain TiC-B
4c ceramic porous article;
B, in vacuum atmosphere, rise to 1400 DEG C with the speed of 10 DEG C/min and be incubated 2h to TiC-B
4c metal porous body carries out pressureless infiltration copper, makes the copper liquid of melting infiltrate described TiC-B
4in the hole of C metal porous body, ooze copper and complete and obtain after cooling containing TiC-B
4the composite material stem stem of C;
Step 2, installation ceramic ring, becket: stem stem is installed in the accepting hole of aluminium oxide ceramics ring, Au-Cu system soldering lug is installed between stem stem and zirconia ceramics ring, then place in a vacuum furnace, soldering 3 minutes at 1000 DEG C, makes to obtain compact siro spinning technology by the formation of the first weld layer between the collecting hole wall of the lateral surface of composite material stem stem and aluminium oxide ceramics ring; Then aluminum metal ring set is connected to the outside of zirconia ceramics ring, Al-Si system soldering lug is installed between aluminium oxide ceramics ring and aluminum metal ring, then place in a vacuum furnace, soldering 5 minutes at 620 DEG C, make to obtain compact siro spinning technology by the formation of the second weld layer between the installation hole wall of the lateral surface of aluminium oxide ceramics ring and aluminum metal ring, obtain the black box A9 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 the stem stem that upper cover and metallic aluminium, copper are done, obtain the black box D1 of anode and 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, respectively the stem stem that 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-A9 obtained by embodiment 1-9 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. |
| a7 | the connecting portion of black box A7 is without bubbling phenomenon. |
| a8 | the connecting portion of black box A8 is without bubbling phenomenon. |
| a9 | the connecting portion of black box A9 is without bubbling phenomenon. |
| d1 | the connecting portion of black box D1 is without bubbling phenomenon. |
| d2 | the connecting portion of black box D1 is without bubbling phenomenon. |
| 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 D1, D2, D3, D4 that the black box A1-9 obtained by embodiment 1-9 and comparative example 1,2 obtain are placed in clips chamber, 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, be a complete cold shock testing process, 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. |
| a7 | black box A7 completes 400 thermal shock cyclic tests, still by air tightness test. |
| a8 | black box A8 completes 400 thermal shock cyclic tests, still by air tightness test. |
| a9 | black box A9 completes 400 thermal shock cyclic tests, still by air tightness test. |
| d1 | black box D1 after completing 107 thermal shock cyclic tests, not by air tightness test. |
| d2 | black box D2 after completing 108 thermal shock cyclic tests, not by air tightness test. |
| d3 | black box D3 after completing 228 thermal shock cyclic tests, not by air tightness test. |
| d4 | black box D4 after completing 230 thermal shock cyclic tests, not by air tightness test. |
As can be seen from table 1 and table 2, embodiments of the invention 1-9 make black box A1-9 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 1-9 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, comprise: becket, ceramic ring and stem stem, the middle part of described becket is provided with installing hole, described metal ring is connected to the outside of described ceramic ring, and the middle part of described ceramic ring is provided with accepting hole, and described core cylindrical is formed in described accepting hole, it is characterized in that, described stem stem is composite material stem stem, comprises metal material and low-expansion material, and the thermal coefficient of expansion of described low-expansion material is less than the thermal coefficient of expansion of ceramic ring; With the cumulative volume of described composite material stem stem for benchmark, the content of described low-expansion material is 40-80vol%.
2. the black box of battery according to claim 1, is characterized in that, described low-expansion material forms porous body, and metal material is filled in the hole of described porous body.
3. the black box of battery according to claim 1, is characterized in that, the fusing point of described low-expansion material is higher than the fusing point of described metal material.
4. the black box of the battery according to claim 1-3 any one, 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, and described low-expansion material is selected from Al
2o
3, one or more in AlN, BN.
5. the black box of the battery according to claim 1-3 any one, it is characterized in that, the black box of described battery is the black box of battery cathode, and described metal material is copper and copper alloy, and described low-expansion material is selected from Mo, W, Cr, TiC, SiC, B
4one or more in C, WC.
6. 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, aluminium oxide and zirconic composite ceramics ring;
Described becket is aluminium ring or aluminum alloy ring.
7. the black box of battery according to claim 1, is characterized in that, is provided with the first weld layer between described composite material stem stem and ceramic ring; The second weld layer is provided with between described ceramic ring and becket.
8. a manufacture method for the black box of the battery as described in claim 1-7 any one, comprises the steps:
Step 1, provide low-expansion material and metal material, and make described low-expansion material and metal material moulding composite material stem stem;
Step 2, described composite material stem stem to be welded in the accepting hole of ceramic ring, and by the outside of welding metal rings in ceramic ring.
9. manufacture method according to claim 8, is characterized in that, the method for described low-expansion material and metal material moulding composite material stem stem is the one in powder metallurgic method, pressureless infiltration method, pressure infiltration method.
10. manufacture method according to claim 8 or claim 9, it is characterized in that, described low-expansion material is made porous body, then in pressurization or environment with no pressure, at temperature more than the fusing point of metal material, metal material is heat-treated, infiltrate after making metallic material in described porous body, after cooling, form composite material stem stem.
11. manufacture methods according to claim 8, 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, and described low-expansion material is selected from Al
2o
3, one or more in AlN, BN;
Or the black box of described battery is the black box of battery cathode, and described metal material is copper or copper alloy, and described low-expansion material is selected from Mo, W, Cr, TiC, SiC, B
4one or more in C, WC.
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 1-7 any one, wherein, the becket of the black box of described battery is connected with housing, and the stem stem of the black box of described battery is connected with described pole piece.
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| US11387497B2 (en) | 2012-10-18 | 2022-07-12 | Ambri Inc. | Electrochemical energy storage devices |
| US10541451B2 (en) | 2012-10-18 | 2020-01-21 | Ambri Inc. | Electrochemical energy storage devices |
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