CN101851715A - Aluminium alloy plate for battery case and battery case - Google Patents
Aluminium alloy plate for battery case and battery case Download PDFInfo
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- CN101851715A CN101851715A CN201010127655A CN201010127655A CN101851715A CN 101851715 A CN101851715 A CN 101851715A CN 201010127655 A CN201010127655 A CN 201010127655A CN 201010127655 A CN201010127655 A CN 201010127655A CN 101851715 A CN101851715 A CN 101851715A
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 155
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 75
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 83
- 230000008569 process Effects 0.000 claims description 61
- 238000000137 annealing Methods 0.000 claims description 44
- 238000005097 cold rolling Methods 0.000 claims description 32
- 230000004927 fusion Effects 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003466 welding Methods 0.000 description 69
- 230000002159 abnormal effect Effects 0.000 description 33
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- 238000011156 evaluation Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000007812 deficiency Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910018643 Mn—Si Inorganic materials 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
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- 239000000243 solution Substances 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 229910017082 Fe-Si Inorganic materials 0.000 description 4
- 229910017133 Fe—Si Inorganic materials 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910002551 Fe-Mn Inorganic materials 0.000 description 3
- 229910019752 Mg2Si Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019064 Mg-Si Inorganic materials 0.000 description 2
- 229910019406 Mg—Si Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/12—Alloys based on aluminium with copper as the next major constituent
- C22C21/14—Alloys based on aluminium with copper as the next major constituent with silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
- B22D21/04—Casting aluminium or magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/12—Alloys based on aluminium with copper as the next major constituent
- C22C21/16—Alloys based on aluminium with copper as the next major constituent with magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/12—Alloys based on aluminium with copper as the next major constituent
- C22C21/18—Alloys based on aluminium with copper as the next major constituent with zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/147—Lids or covers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
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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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- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention provides a kind of aluminium alloy plate, contain Mn:0.4～1.5 quality %, Cu:0.7～4.0 quality %, Mg:0.2～1.5 quality %, Si:0.05～1.0 quality %, Fe:0.05～1.0 quality %, surplus is made of Al and unavoidable impurities, in the described unavoidable impurities, below the restriction Zn:0.3 quality %, Ti: be lower than 0.02 quality %, below the B:20 quality ppm, thickness of slab direction central part in the cross section of aluminium alloy plate, maximum length is that the area occupation ratio of the above intermetallic compound of 1 μ m surpasses 0.3% and be lower than 2.1%, and maximum length is that the number of the above intermetallic compound of 11 μ m is 140/mm
2Below.According to this formation, plasticity, pulsed laser weldability, intensity and resistance to pressure (expansibility resistance) excellence are suitable for battery case.
Description
Technical field
The present invention relates to a kind of aluminium alloy plate and manufacture method thereof of lithium-ion secondary cell shell etc. and battery case that uses this aluminium alloy plate of being applicable to.
Background technology
As the power supply of mobile phone and notebook personal computer layer, lithium-ion secondary cell is widely used.The outer dress of this secondary cell is the material of shell (the following battery case that suitably is called), at present for the miniaturization of satisfying battery and lightweight and be used for processed-type (plasticity) that battery case is shaped etc., is using aluminium alloys such as JISA3003 alloy.In this battery, when discharging and recharging, the internal pressure of battery case rises.In addition, in the automobile in summer under such hot environment, prevent to be equipped with the occasion of the electronics of battery, the temperature of battery case self also reaches 60 ℃～90 ℃, because temperature rises, not only internal pressure rises significantly, and battery case is also relaxed with the internal stress of material self.Consequently, the battery case dilatational strain is difficult to when changing battery take out, even has battery case damaged and damage the performance of electronics, causes disruptive danger.
So, even this battery case be required since described battery discharge and recharge and hot environment under use, press in the battery case under the situation about rising, also can keep the resistance to pressure (expansibility resistance) and the proof stress retentivity of the excellence of the desired shape of battery case.On the other hand, for further miniaturization, lightweight and the cost degradation of battery, strong request realizes the thin-walled property of battery case.But, when the existing aluminium alloy plate that is made of JISA3003 alloy etc. is made thin-walled, act on smaller internal pressure even can be easy to generate the resistance to pressure reduction of distortion, battery case, also be easy to generate the problem of expansion and so on.
So, in recent years, developing by in by the aluminium alloy of JIS3000 system (JISA3000 system), adding Cu etc., making the intensity raising of aluminium alloy plate, even make the aluminium alloy plate for battery case that thin-walled property also possesses the resistance to pressure of user mode that can corresponding battery.For example, Japan speciallys permit in No. 3867989 and discloses a kind of aluminium alloy plate for battery case and manufacture method thereof, that is: by Mn, Cu, Mg, the Si that adds specified amount intensity is improved,, possess high resistance to pressure thus even thin-walled property also has sufficient proof stress retentivity.
In addition, in recent years, except that desired strength, resistance to pressure, also require the anti-crackle in the pulsed laser welding also excellent.So, a kind of aluminium alloy plate is disclosed in TOHKEMY 2006-104580 number, by Si, Fe, Cu, Mn, the Mg that adds specified amount intensity is improved, the aggregate value of Si, Fe, Cu and Mg is set at below the 1.5 quality %, prevent the generation of the crackle in the pulsed laser welding thus.
But,, require the intensity of property material for battery shell and resistance to pressure further to improve in order to improve the security of secondary cell more.In addition, in recent years, also proposed to satisfy the requirement that is used for miniaturization, lightweight and cost degradation, so, the requirement of thin-walled property that possesses intensity and resistance to pressure is from needless to say, in addition, the welding speed of studying the pulsed laser welding that makes when making battery case is from present 20～30mm/ high speed to 30 in second～40mm/ technology in second.Thus, the output of input pulsed laser is brought up to present more than 1.1～1.3 times, so, produced new problem.That is, under the situation of carrying out the welding of this high speed,, can see abnormal portion is arranged (irregular weld seam) formation, the discontinuity of weld part takes place easily though do not produce welding crack.This abnormal portion becomes the fusion at the back side that penetrates soldered material, produces performances such as electroconductibility and operating voltage are brought dysgenic problem.Requirement can also be eliminated the property material for battery shell of the problem of relevant this weldability, but the aluminium alloy that can eliminate the JIS3000 system of this weldability problem does not also have.
For example, Japan speciallys permit the aluminium alloy plate for battery case of record in No. 3867989, the content of having put down in writing Zn is that 0.10 quality % is when following, because it is limited in below the specified amount, used thickness is that the pulsed laser weldability of the corresponding aluminium alloy of 1mm when making battery case is also excellent, and records the technology that welding crack in the time of can preventing to use pulsed laser to weld in battery case is made and Zn disperse.But, when making battery case, in welding speed is to carry out under 30～40mm/ high speed condition in second under the situation of pulsed laser welding, though the inhibition effect of welding crack is arranged to a certain extent, but, because not to the restriction of other composition ranges, be used for the pulsed laser output of under high-speed condition, welding, under high condition, can not suppress the generation of above-mentioned abnormal portion.
In addition, the aluminium alloy plate of record in TOHKEMY 2006-104580 number, the aggregate value of Si, Fe, Cu and Mg is set at below the 1.5 quality %,, takes place so can prevent the crackle in the pulsed laser welding because of the aggregate value to Si, Fe, Cu and Mg limits.But, when making battery case, in welding speed is to carry out under 30～40mm/ high speed condition in second under the situation of pulsed laser welding, though the inhibition effect of welding crack is arranged to a certain extent, but, because not to the restriction of other composition ranges, be used for the pulsed laser output of under high-speed condition, welding, under high condition, can not suppress the generation of above-mentioned abnormal portion.In addition, the record of Ti, B is arranged in this special permission communique, but only put down in writing the situation of initiatively adding and initiatively added the effect that obtains by this, promptly, coarse purpose when preventing to be shaped by the crystal grain miniaturization, not touching the high speed of the welding speed of pulsed laser welding, is not the technology of the new problem of corresponding above-mentioned record naturally.
Promptly, can solve in the aluminium alloy plate that has JIS3000 system now, but can not get when turning to the realization of goal thin-walled property the resistance to pressure (expansibility resistance) with the desired light weight of battery case, the thin-walled property of aluminium alloy plate and resistance to pressure are in the problem of the relation of antinomy, but except that these problems, can not solve under the degree of the generation that can not suppress above-mentioned abnormal portion, after welding speed improved, the thin-walled property of aluminium alloy plate, resistance to pressure and weldability were in the problem of the anti-relation of the three rule back ofs the body.Therefore, for battery case, except that thin-walled property that satisfies aluminium alloy plate and resistance to pressure, also take into account and satisfy relatively difficulty of weldability.
In addition, in existing aluminium alloy plate for battery case, there is following problem.
In the aluminium alloy plate for battery case, increased the requirement of raising processibility (plasticity), but, in the processing that is shaped, produced aluminium alloy sometimes and split, process crackle etc. because of the one-tenth difference that is grouped into and creates conditions.
In addition, in order to improve the security of secondary cell more, require the intensity of property material for battery shell and resistance to pressure further to improve.
In addition, in existing aluminium alloy plate for battery case, as mentioned above, realized the raising of the anti-crackle in the pulsed laser welding.But, in recent years, form abnormal portion (irregular weld seam), easily the problem of the discontinuity and so on of weld part take place because the welding speed of the pulsed laser welding when making battery case just at high speed, therefore has at weld part.Therefore, can prevent that crackle in the pulsed laser welding from taking place and can to suppress the requirement of aluminium alloy plate for battery case of generation of abnormal portion also more and more higher.
Summary of the invention
The present invention puts in view of the above problems and develops, purpose is to provide a kind of pulsed laser weldability battery case, that have excellent formability, also have excellence that is used to make, and aluminium alloy plate and manufacture method thereof that intensity and resistance to pressure (expansibility resistance) are improved, and the battery case that uses this aluminium alloy plate.
The inventor etc. study following item at the aluminium alloy plate that is applicable to battery case.
Abnormal portion in the pulsed laser welding be fusing department situation about changing abruptly and self-pulsing laser welding the time (660～750 ℃) generation degree of carrying out remaining in during the resolidification (660～640 ℃) gas hole defect in the weld seam be associated.
During welding, pulsed laser irradiation portion becomes molten state, the bubble that exists hydrogen, shielding gas, metallic vapor etc. to form in its fusion pool.Answer bubble very light, so directly run away from the surface of fusion pool.On the other hand, after round-robin laser illumination finishes, the process of setting of dividing a word with a hyphen at the end of a line, but under the situation that bubble is difficult for running away, remaining untouched easily forms gas hole defect and residual.At this, during the pulsed laser welding, the weld seam that solidifies end is shone next round-robin pulse laser, with stacked new weld seam.Then, again after the fusion, residual pore becomes by the position of pulsed laser irradiation the weld seam that solidifies end by the irradiation of pulse laser, pore expands, usually, by the Charpy key hole specimen hypertrophyization that pulsed laser irradiation forms, laser enters very dark easily.Consequently, fuse into to form more deeply to form and be the improper portion of fusing into.The abnormal portion that the back forms weld part is solidified in this improper portion of fusing into.
So the inventor etc. have carried out investigation with keen determination to the influence of the trace ingredients that relates to of the pore of the generation of above-mentioned abnormal portion (irregular weld seam) and weld seam inside, found that, it is subjected to the situation of Mg, B, Ti content influence, find that also wherein, the influence of B, Ti content is big especially.That is, find by the scope of B, Ti content is suitably changed,, also can prevent the generation of abnormal portion even in the existing alloy be the welding speed of problem fast under the situation.
In addition, investigation has with keen determination been carried out in the influence that welding crack is taken place related trace ingredients, and the result finds that also it is subjected to the situation of Mg, Cu content influence.That is, find, can prevent that in the existing alloy be the generation of the welding crack of problem by the scope of Mg, Cu content is suitably changed.
Starting material of using as the lithium-ion secondary cell shell like this, it is the advantage of aluminium that the inventor etc. not only apply flexibly excellent JIS3000, and, various experimental studies have been carried out in order to develop the starting material that to eliminate the shortcoming when utilizing pulsed laser that it is welded.Its result also finds, the irregular weld seam that contains the welding of paired pulses laser apparatus of Ti and B is the very big influence of bringing of abnormal portion in the starting material, and, be limited in the suitable scope by content Ti contained in this JIS3000 line aluminium alloy material and B, can suppress bubble residual in weld seam, so, can prevent that irregular weld seam from being the generation of abnormal portion.In addition, the excessive interpolation that can reduce the Mg of fusing point can promote because of containing the bubble in weld seam that Ti and B cause residual, so, it must be limited to specified amount.
In order to solve above-mentioned problem, aluminium alloy plate of the present invention, contain Mn:0.4～1.5 quality %, Cu:0.7～4.0 quality %, Mg:0.2～1.5 quality %, Si:0.05～1.0 quality %, Fe:0.05～1.0 quality %, surplus is made of Al and unavoidable impurities, in the described unavoidable impurities, following, the Ti of restriction Zn:0.3 quality %: be lower than 0.02 quality %, below the B:20 quality ppm.
According to this formation, by Mn, Cu, Mg, the Si that contains specified amount, the solid solution in mother metal of various elements, the intensity of aluminium alloy plate improves.
In addition, Mn, Si, Fe by containing specified amount utilize the formation of intermetallic compound, and plasticity improves, and Cu, Mg, Si by containing specified amount separate out Mg
2Si and fine S ' (Al
2CuMg) phase, anti-stress relaxation properties improves.In addition, by the Zn concentration limits is fixed on below the specified amount, when carrying out the laser welding of aluminium alloy plate, the Zn that steam forces down just can not disperse, and can not pollute surrounding environment.In addition, by Ti, B are limited to below the specified amount, when pulsed laser welding irradiation made the starting material fusion, bubble was difficult for remaining in and solidifies in the weld seam, can prevent to produce abnormal portion at weld part.
In the aluminium alloy plate of above-mentioned formation, can also contain that Zr:0.15 quality % is following, Cr:0.40 quality % more than one in following.
According to this formation, the Zr by containing specified amount, among the Cr more than one can make and be organized as refinement, homogenize.
In addition, in the aluminium alloy plate of above-mentioned formation, thickness of slab direction central part in the cross section of described aluminium alloy plate for battery case, maximum length is that the area occupation ratio of the above intermetallic compound of 1 μ m surpasses 0.3% and be lower than 2.1%, and maximum length is that the number of the above intermetallic compound of 11 μ m is 140/mm
2Below.
According to this formation, by Mn, Cu, Mg, the Si that contains specified amount, make the solid solution in parent phase of various elements, the intensity of aluminium alloy plate (compressive strength) improves.In addition, by Mn, Si, the Fe that contains specified amount, plasticity improves because of the formation of intermetallic compound; By Cu, Mg, the Si that contains specified amount, the occasion that the battery that is assembled into is exposed on the occasion in the hot environment and then exposes repeatedly in this hot environment and normal temperature environment, in processed aluminium alloy plate for battery case, Mg
2Si and fine S ' (Al
2CuMg) separate out, the carrying capacity relaxation properties improves.In addition, by with the Zn concentration limit below specified amount, when the laser welding of aluminium alloy plate, the Zn that steam is forced down does not disperse, around can not polluting.In addition, by Ti, B are limited in below the specified amount, when the starting material fusion of pulsed laser welding irradiation, bubble is difficult for solidifying in the weld seam, can prevent the generation of the abnormal portion of weld part.
In addition, by limiting the area occupation ratio that maximum length is the intermetallic compound more than the 1 μ m according to the rules, the oilness that adds man-hour improves, and prevents freezing of aluminium alloy plate, and the crackle can prevent to be shaped the time; By limiting the number that maximum length is the intermetallic compound more than the 11 μ m, the crackle when preventing to be shaped according to the rules.
To maximum length is the manufacture method that the area occupation ratio of the intermetallic compound more than the 1 μ m and number have been carried out the aluminium alloy plate of the above-mentioned formation that limits, comprising: the aluminium alloy that will have described composition fuses, casts and makes the casting process of ingot bar; More than 420 ℃ and be lower than under the temperature of fusing point of described aluminium alloy, described ingot bar is implemented to homogenize the heat treated heat treatment step that homogenizes; The described heat treated ingot bar that homogenizes is carried out the hot rolled hot-rolled process; Behind described hot-rolled process, carry out cold rolling and the cold rolling process making milled sheet; Described milled sheet is implemented the process annealing operation of process annealing; Milled sheet after the described process annealing is implemented final cold rolling final cold rolling process with draft 20～50%, described process annealing is the temperature range that is heated to 420 ℃ or more with the rate of heating more than 100 ℃/minute described milled sheet and is lower than the fusing point of described aluminium alloy, after this temperature range kept for 0～180 second, cool off with the speed of cooling more than 300 ℃/minute.
According to this making method, by implementing to homogenize thermal treatment, the intermetallic compound solid solution diffusion, tissue is homogenized, in addition, by implementing process annealing, final cold rolling in, thickness of slab with aluminium alloy plate is adjusted to desired thickness of slab easily, and produces the intensity raising that aluminium alloy plate is solidified and makes in processing.In addition, the S ' (Al of Mg2Si and miniaturization
2CuMg) phase solid solution.Utilize this solution strengthening, the intensity of aluminium alloy plate improves.In addition, when exposing repeatedly when assembled battery is exposed in the hot environment even in this hot environment and normal temperature environment, in processed aluminium alloy plate for battery case, Mg
2Si and fine S ' (Al
2CuMg) separate out generation constraint effect, the carrying capacity relaxation properties is suppressed, and the resistance to pressure of aluminium alloy plate improves.In addition, by implementing process annealing, because the solution strengthening of various elements, the intensity of aluminium alloy plate improves.In addition, be controlled at specialized range by the draft in will be final cold rolling, stress relaxes phenomenon and is suppressed, and resistance to pressure improves.
Battery case of the present invention is to use the battery case of the aluminium alloy plate of above-mentioned formation.
This battery case has adopted described aluminium alloy plate, so intensity, resistance to pressure (expansibility resistance) are improved.
According to aluminium alloy plate of the present invention, when battery case is formed, has excellent plasticity (attenuate pull and stretch processibility), in addition, the pulsed laser welding property excellent in the pulsed laser welding, has excellent anti-welding crack, weld part intensity, and can suppress the generation of abnormal portion.And then, even with the thickness of slab thin-walled property, also can provide to have excellent intensity, the battery case of resistance to pressure (expansibility resistance).
According to the manufacture method of aluminium alloy plate of the present invention, can make aluminium alloy plate efficiently with described effect.
According to battery case of the present invention, owing to have excellent intensity, resistance to pressure (expansibility resistance), even in lithium-ion secondary cell etc., carry out charge and discharge repeatedly or under hot environment, use, the battery case temperature inside rises, when internal pressure rises thereupon, the dilatational strain amount that also can suppress this battery case is suppressed at suitably lower degree with it.Consequently, can prevent the battery case dilatational strain, the situation that is difficult to take out when changing battery, even battery case is damaged and damage the performance or the disruptive situation of electronics.
Description of drawings
Fig. 1 is the stereographic map of weld part of pulsed laser welding of the evaluation method of the expression pulsed laser weldability that is used for illustrating embodiment;
Fig. 2 is the sectional view that the X-X line of Fig. 1 dissects, and (a) is the sectional view of the situation of the good weld part of expression; (b) be the orthographic plan that expression has produced the situation after the abnormal portion;
Fig. 3 is the synoptic diagram of measuring method that is used to illustrate the bubble generation degree of embodiment.
Embodiment
Below, realize that to being used to the food of aluminium alloy plate of the present invention describes.
(formation of aluminium alloy plate)
Aluminium alloy plate of the present invention is Mn, Cu, Mg, Si, the Fe that contains specified amount, and the aluminium alloy plate that surplus is made of Al and unavoidable impurities is limited in the Zn in the described unavoidable impurities, Ti, B below the specified amount.In addition, limit the area occupation ratio and the number of intermetallic compound of regulation of the thickness of slab direction central part in aluminium alloy plate cross section according to the rules.Below, the reason of the distribution regulation of the qualification reason of each composition and intermetallic compound is described.
(Mn:0.4～1.5 quality %)
Mn is solid solution in parent phase, has the effect of the intensity that improves aluminium alloy plate.Along with the increase of Mn content, its effect increases, the compressive strength in the time of can improving as battery case.In addition, Mn and Al, Fe, Si form intermetallic compound (Al-Fe-Mn series intermetallic compound, Al-Fe-Mn-Si series intermetallic compound), by increasing the number of fine described intermetallic compound, therefore lubricant effect when helping the battery case forming process makes the plasticity of aluminium alloy plate improve.When the content of Mn is lower than 0.4 quality %, can not bring into play solution strengthening, and 1 μ m is above, the number of the fine described intermetallic compound that is lower than 11 μ m is not enough easily, so these effects are insufficient.And when the content of Mn surpassed 1.5 quality %, the number of the thick described intermetallic compound that 11 μ m are above increased, and became the starting point of the crackle when being shaped easily, and the plasticity of aluminium alloy plate reduces.Thereby the content of Mn is set at 0.4～1.5 quality %.
(Cu:0.7～4.0 quality %)
Cu is solid solution in parent phase, has the effect of the intensity that improves aluminium alloy plate.Its effect increases the compressive strength in the time of can improving as battery case along with the increase of Cu content.In addition, Cu has the effect of the intensity raising of the weld part when making the pulsed laser welding.In addition, Cu and Al, Mg strike up partnership and form fine S ' (Al
2CuMg) separate out mutually.This S ' (Al
2CuMg) suppress moving of displacement mutually, make stress relax phenomenon thus and be inhibited, the proof stress retentivity of aluminium alloy plate is improved.When the content of Cu was lower than 0.7 quality %, these effects were insufficient.And when the content of Cu surpasses 4.0 quality %, the moving of displacement by fine S ' (Al
2CuMg) suppress excessively mutually, plasticity is reduced.In addition, because fusing point reduces, produce welding crack in the pulsed laser welding.Thereby the content of Cu is set at 0.7～4.0 quality %.
(Mg:0.2～1.5 quality %)
Mg is solid solution in parent phase, has the effect of the intensity that improves aluminium alloy plate.Its effect increases the compressive strength in the time of can improving as battery case along with the increase of Mg content.In addition, Mg and Si are combined as a whole and separate out Mg
2Si perhaps is combined as a whole and separates out fine S ' (Al with Al, Cu
2CuMg) phase.This Mg
2Si and S ' (Al
2CuMg) suppress moving of displacement mutually, thus, suppress stress and relax phenomenon, the proof stress retentivity of aluminium alloy plate is improved.When the content of Mg was lower than 0.2 quality %, these effects were insufficient.In addition, when the content of Mg was lower than 0.2 quality %, intensity (yield strength) reduced.And the content of Mg is when surpassing 1.5 quality %, and the processing solidified nature of aluminium alloy plate uprises, and plasticity reduces.In addition, because fusing point reduces, in the pulsed laser welding, produce welding crack.
In addition, Mg content surpasses 1.5 quality % and contains sometimes, and fusing point reduces and the Mg atom is vaporized abruptly and ratio that disperse increases, and in the pulsed laser welding abnormal portion takes place.Thereby in order to append the characteristic of the generation that prevents the abnormal portion in the pulsed laser welding, the upper limit of Mg is set at 1.5 quality %.Therefore the content with Mg is set at 0.2～1.5 quality %.
(Si:0.05～1.0 quality %)
Si is solid solution in parent phase, has the effect of the intensity that improves aluminium alloy plate.Its effect increases the compressive strength in the time of can improving as battery case along with the increase of Si content.In addition, Si and Al, Mn, Fe form the Al-Fe-Mn-Si series intermetallic compound, and the number of fine described intermetallic compound is increased, and thus, help battery case to be shaped and add the lubricant effect in man-hour, and the plasticity of aluminium alloy plate is improved.In addition, Si and Mg are combined as a whole and separate out Mg2Si, so, the proof stress retentivity of aluminium alloy plate is improved.When the content of Si was lower than 0.05 quality %, these effects were insufficient.And the content of Si is when surpassing 1.0 quality %, and it is thick that described intermetallic compound becomes easily, becomes the starting point of the crackle when being shaped easily, thereby the plasticity circulation of aluminium alloy plate is to reduce.In addition, thickization of Mg2Si and yield strength is reduced sometimes.In addition, form the Al-Cu-Fe-Si series intermetallic compound sometimes, the solid solution capacity of Cu is reduced.In addition, because fusing point reduces, in the pulsed laser welding, produce welding crack.Thereby the content of Si is set at 0.05～1.0 quality %.
(Fe:0.05～1.0 quality %)
Fe is the same with Mn, Si, form Al-Fe-Mn system, Al-Fe-Mn-Si series intermetallic compound, make the number of fine described intermetallic compound increase, thus, help battery case to be shaped and add the lubricant effect in man-hour, so have the effect of the plasticity raising that makes aluminium alloy plate.When the content of Fe was lower than 0.05 quality %, 1 μ m was above and to be lower than the number of fine intermetallic compound of 11 μ m not enough, and above-mentioned effect is little.And when Fe content surpassed 1.0 quality %, the number of the thick intermetallic compound that 11 μ m are above increased, and became the starting point of the crackle when being shaped easily, so the plasticity of aluminium alloy plate reduces.In addition, the formation quantitative change of Al-Fe-Mn system, Al-Fe-Mn-Si series intermetallic compound is many, therefore, and Mg
2Si separates out minimizing, and the proof stress retentivity reduces sometimes.In addition, form the Al-Cu-Fe-Si series intermetallic compound sometimes, the solid solution capacity of Cu is reduced.Thereby the content of Fe is set at 0.05～1.0 quality %.
(surplus: Al and unavoidable impurities)
The composition of aluminium alloy plate except above-mentioned points, surplus is made of Al and unavoidable impurities.In addition, as unavoidable impurities, for example Ga, the V of contained common known scope, Ni etc. do not hinder effect of the present invention in metal block or the master alloy, so allow to contain this unavoidable impurities.In addition, among the present invention, in the unavoidable impurities, Zn, Ti, B are limited in below the specified amount.
(Zn:0.3 quality % is following)
Zn forces down because of its steam, when pulsed laser welds, disperse easily and to around pollute, and then weld metal crack also takes place easily, make the pulsed laser weldability variation of aluminium alloy plate.Thereby the content of Zn is limited in below the 0.3 quality %.In addition, in order to make above-mentioned contaminative good, Zn content is preferably below the 0.10 quality %.
(Ti: be lower than 0.02 quality %)
Ti has makes that aluminium alloy casting is organized miniaturization, the effect of homogenize (stabilization), casting crack when preventing the plate slab ingot bar of rolling usefulness is purpose, usually add more than the 0.02 quality %, but when excessively adding, thick intermetallic compound is separated out easily and is become the starting point of crackle when being shaped, so Ti is the element that is limited in the following scope of 0.15 quality %.But, as mentioned above, when the 0.02 quality % that interpolation is used always is above, when pulsed laser welds the starting material fusion of shining (660～750 ℃), solidify easy residual gas bubble in the weld seam, so, by the irradiation of pulsed laser welding next time, when solidifying weld seam before one and fusing once more, bubble is difficult to run away in fusion pool.Thus, residual in the weld seam have a gas hole defect, forms darker fusing into and abnormal portion takes place.Thereby Ti content is limited in and is lower than 0.02 quality %.
(B:20 quality ppm is following)
As mentioned above, the casting crack when preventing the plate slab ingot bar of aluminium alloy is purpose, and as the Ti-B mother alloy, B is and Ti element commonly used in actively adding together.But, when B content surpasses 20ppm, with above-mentioned Ti add the same, pulsed laser irradiation portion solidify in the weld seam residual gas bubble easily, shine by pulsed laser welding next time, preceding when solidifying weld seam and fusing once more, bubble is difficult to run away in fusion pool.Thus, residual in the weld seam have a gas hole defect, forms darker fusing into and abnormal portion takes place.Thereby B content is limited in below the 20ppm.
Aluminium alloy plate of the present invention can also contain that Zr:0.15 quality % is following, Cr:0.40 quality % more than one in following.
(below the Zr:0.15 quality %, below the Cr:0.40 quality %)
Zr, Cr have the effect that makes aluminum alloy organization's miniaturization, homogenizes (stabilization).In addition, the recrystallize grain miniaturization in the time of can making resolidification during welding can be avoided welding crack.But when surpassing regulation content separately, the turnover and become the starting point of crackle when being shaped easily of thick intermetallic compound is so the plasticity of aluminium alloy plate reduces.Thereby when adding Zr, Cr, Zr content is set at below the 0.15 quality %, and Cr content is set at below the 0.40 quality %.In addition, lower value is not done special stipulation, but in order to obtain above-mentioned effect, Zr, Cr preferably contain respectively more than the 0.05 quality %.In addition, Zr, Cr also can be used as unavoidable impurities and contain below the described regulation content.
(maximum length is the area occupation ratio of the above intermetallic compound of 1 μ m: surpass 0.3% and be lower than 2.1%)
The maximum length of the thickness of slab direction central part in aluminium alloy plate cross section is that the area occupation ratio of the above intermetallic compound of 1 μ m is set at and surpasses 0.3% and be lower than 2.1%.In addition, the thickness of slab direction central part in so-called cross section specifically is meant with thickness of slab direction center to be 30～50% zone of the thickness of slab at center.
Area occupation ratio is 0.3% when following, when diameter reducing extrusion, removes the lubricant effect deficiency on the female ground of aluminium that is set on drift and the punch die, because of aluminium alloy plate freezes etc., and the plasticity reduction of aluminium alloy plate.And area occupation ratio is 2.1% when above, and thick intermetallic compound is many, becomes the starting point of shaping crackle easily, so the aluminium alloy plasticity reduces.
In addition, in above-mentioned scope, even contain the compound that is lower than 1 μ m, their area occupation ratio can not impact plasticity yet, can contain their intermetallic compound in above-mentioned scope yet.In addition, do not stipulate that also including maximum length in the area occupation ratio is the above intermetallic compounds of 11 μ m about the upper limit of maximum length.
(maximum length is the number of the above intermetallic compound of 11 μ m: 140/mm
2Below)
The maximum length of the thickness of slab direction central part in aluminium alloy plate cross section is that the number of the above intermetallic compound of 11 μ m is set at 140/mm
2Below.
Number surpasses 140/mm
2The time, the number of thick described intermetallic compound is many, becomes the starting point of the crackle when being shaped easily, and therefore, the plasticity of aluminium alloy plate reduces.
Even contain the intermetallic compound that is lower than 11 μ m in above-mentioned scope, their number can not impact plasticity yet, can contain their intermetallic compound in above-mentioned scope yet.In addition, do not stipulate about the upper limit of maximum length.
And the distribution of these intermetallic compounds is controlled by content and described later the creating conditions (heat-treat condition that homogenizes, process annealing condition) of Mn, Mg, Si, Fe.
The detecting unit of intermetallic compound can be enumerated use scanning electron microscope (SEM) as an example.Maximum length is the above intermetallic compound of 1 μ m, the composition (COMPO) of SEM as in, by discerning with the contrast of parent phase, Al-Mn-Fe system, Al-Mn-Fe-Si series intermetallic compound are broken forth whiter than Al parent phase, and the Mg-Si series intermetallic compound comes out more black than Al parent phase.In the intermetallic compound of the thickness of slab direction central part in aluminium alloy plate cross section, cut off aluminium alloy plate and the cut surface that comprises rolling direction and thickness of slab direction is ground, be finish-machined to minute surface as sightingpiston, what observe aluminium alloy plate is 30～50% zone of the thickness of slab at center with thickness of slab direction center.Add up to 1mm from this zone preferred view, shooting
2More than look several the visual field, with area occupation ratio and the number density of image processing apparatus mensuration about the intermetallic compound of specified size.
[manufacture method of aluminium alloy plate]
Example to the manufacture method of aluminium alloy plate of the present invention describes.
At first, will have above-mentioned composition aluminium alloy fusion, cast and make ingot bar, this ingot bar is implemented surfacing cut after, more than 480 ℃ and be lower than under the temperature of fusing point of described aluminium alloy and implement to homogenize thermal treatment.Secondly, it is cold rolling that this heat treated ingot bar that homogenizes is carried out hot rolls, make milled sheet, then, with this milled sheet with the rate of heating more than 100 ℃/minute more than 420 ℃ and the temperature range that is lower than the fusing point of described aluminium alloy heat, after this temperature range kept for 0～180 second, cool off with the speed of cooling more than 300 ℃/minute, implement process annealing thus.Thereafter, finally cold rolling to the milled sheet of having passed through process annealing with draft 20～50% enforcements, make aluminium alloy plate.Need to prove, also can implement 80～200 ℃, 0.5～8 hour final annealing as required having implemented final cold rolling milled sheet.By final annealing, material softening, ductility improves, and therefore, final annealing is the suitable operation that is used to make the plasticity raising.
Then, to describing about the manufacture method that particularly satisfies in the aluminium alloy of the present invention about the aluminium alloy plate of the condition of the area occupation ratio of described intermetallic compound and number.The manufacture method of aluminium alloy plate of the present invention comprises: casting process, the heat treatment step that homogenizes, hot-rolled process, cold rolling process, the centre pushes away or operation, final cold rolling process.Below each operation is described.
＜casting process 〉
Manufacturing process is that the aluminium alloy that will have above-mentioned composition fuses, casts and the operation of making ingot bar.
The method that alloy is fused, casts is not particularly limited, and uses existing known method to get final product.For example, can use vacuum induction furnace to fuse, use Continuous casting process or semicontinuous casting method to cast.
＜heat treatment step homogenizes 〉
The heat treatment step that homogenizes is more than 420 ℃ and be lower than under the temperature of fusing point of described aluminium alloy and implement to homogenize heat treated operation.In addition, in this operation, the most described ingot bar has been implemented to implement to homogenize thermal treatment after the surfacing.
[treatment temp: more than 420 ℃ and be lower than the fusing point of aluminium alloy]
Before ingot bar is rolled, the thermal treatment that need under specified temperature, homogenize (all thermal treatment).By implementing equal thermal treatment, the intermetallic compound solid solution diffusion that crystalline substance goes out when making casting homogenizes tissue.All thermal treatment temp is lower than under 420 ℃ the situation, and homogenizing of the ingot bar that is made of aluminium alloy of the present invention is insufficient.That is, can not get reducing the be shaped effect of number of the thick intermetallic compounds such as Al-Fe-Mn-Si system that add the starting point that becomes crackle man-hour of battery case.And when equal thermal treatment temp arrives the fusing point of aluminium alloy, the ingot bar fusion.Thereby equal thermal treatment temp is set at more than 420 ℃ and is lower than the fusing point of aluminium alloy.In addition, the fusing point of aluminium alloy of the present invention is organized the range that does not coexist about 500～610 ℃ according to it, particularly Cu content fusing point step-down for a long time.In addition, all under 1 hour the situation of heat treatment time less than, homogenizing of ingot bar can not be finished sometimes, so preferred more than 1 hour.
＜hot-rolled process and cold rolling process 〉
Hot-rolled process is that the described heat treated ingot bar that homogenizes is carried out the hot rolled operation.
Cold rolling process is to carry out cold rolling behind described hot-rolled process and operation that make milled sheet.
Hot rolling and cold rolling method are not particularly limited, and use existing known method to get final product.
＜process annealing operation 〉
The process annealing operation is described milled sheet to be implemented the operation of process annealing.
Described process annealing be to described milled sheet with the rate of heating more than 100 ℃/minute more than 420 ℃ and the temperature range that is lower than the fusing point of described aluminium alloy heat, after this temperature range kept for 0～180 second, cool off with the speed of cooling more than 300 ℃/minute.
(rate of heating: more than 100 ℃/minute; Keep: more than 420 ℃, be lower than 0～180 second under the temperature of fusing point of aluminium alloy; Speed of cooling: more than 300 ℃/minute)
By process annealing is implemented in last cold rolling (finally cold rolling) preceding milled sheet, final cold rolling in, just easily the thickness of slab of aluminium alloy plate is adjusted to desired thickness of slab, and produces processing and solidify, thereby the intensity of aluminium alloy plate improves.In addition, by carrying out process annealing, Mg
2Si and fine S ' (Al
2CuMg) solid solution in milled sheet.By this solution strengthening, the intensity of aluminium alloy plate improves.In addition, the battery that is assembled into is exposed on situation in the hot environment, and further is exposed to repeatedly under the situation in this hot environment and the normal temperature environment, in the aluminium alloy plate for battery case that is processed into, and Mg
2Si or S ' (Al
2CuMg) suppress move (the constraint effect) of displacement mutually, and suppress stress and relax phenomenon, make the resistance to pressure of aluminium alloy plate improve.In addition,, make solute element solid solutions in parent phase such as Cu, so by the solution strengthening of these elements, the intensity of aluminium alloy plate improves by carrying out process annealing.
The treatment temp of process annealing is lower than under 420 ℃ the situation, and crystal grain can not recrystallize, so, in final cold rolling process, become the plate that the recrystallized structure in the centre annealing and worked structure are mixed in and be rolled, be shaped to add crackle and uneven surface take place man-hour, plasticity reduces.And the treatment temp of process annealing is when reaching the fusing point of aluminium alloy, the milled sheet fusion.Thereby the process annealing temperature is set at more than 420 ℃ and is lower than the fusing point of aluminium alloy.Need to prove that the fusing point of aluminium alloy of the present invention is the temperature identical with the ceiling temperature of above-mentioned equal thermal treatment, so omit its explanation.In addition, surpassed for 180 seconds in the temperature range hold-time of this process annealing, above-mentioned effect can not increase yet, and productivity is low, so the hold-time was set in below 180 seconds.
In addition, when the rate of heating that the annealed temperature province heats milled sheet between senior middle school is lower than 100 ℃/minute, in the temperature province that heats up midway, solute element becomes thick precipitate, even this precipitate can not solid solution in the treatment temp zone of process annealing.In addition, when the speed of cooling after the process annealing (maintenance) was lower than 300 ℃/minute, the solute element of solid solution was separated out in cooling temperature province midway.In addition, when rate of heating and speed of cooling are slow, overgrowth of crystals sometimes, plasticity reduces.Thereby, the rate of heating that heats in the treatment temp zone of process annealing is set at more than 100 ℃/minute, from the beginning of the treatment temp of process annealing zone, speed of cooling is set at more than 300 ℃/minute, until be cooled to that solute element do not separate out below 100 ℃.
＜final cold rolling process 〉
Final cold rolling process is that the milled sheet of having passed through process annealing is implemented final cold rolling operation with draft 20～50%.
(draft: 20～50%)
Be adjusted to 20～50% by the draft in will be final cold rolling, can suppress stress and relax phenomenon, the resistance to pressure of aluminium alloy plate improves.Draft is lower than under 20% the situation, can not get full intensity sometimes, as the rigidity deficiency of battery case.And draft surpasses at 50% o'clock, and how and easily the accumulation change of distortion advances and recover, the reduction of proof stress retentivity, and the while resistance to pressure reduces.In addition, be shaped to add crackle or uneven surface take place man-hour, so plasticity reduces.Thereby final cold rolling draft is set at 20～50%.
Need to prove,, can not cause in the dysgenic scope, between above-mentioned each operation or front and back, also can comprise other operations such as for example straightening treatment process etc. and clean operation above-mentioned each operation when carrying out the time of the present invention.
[battery case]
Then, battery case of the present invention is described.The shell that battery case of the present invention is to use above-mentioned aluminium alloy plate to make.
The following describes an example of making the method for battery case and secondary cell of aluminium alloy plate of the present invention.
The manufacture method of＜battery case and secondary cell 〉
As the aluminium alloy plate of the present invention of housing main body portion, by the thickness of slab about final cold rolling formation 0.3～0.8mm.This aluminium alloy plate shape is according to the rules cut off, shaped to bottomless drum shape is arranged by extrusion processing or attenuate pull and stretch.And then repeatedly carry out this processing repeatedly side wall surface is uprised gradually, implement processing such as deburring as required, bottom shape according to the rules and sidewall height form thus, as housing main body portion.The shape of battery case is not particularly limited, according to the style of secondary cells such as round shape, pancake rectangular parallelepiped make housing main body portion open above the bottomless drum shape shape arranged.
The thickness of slab decrement (attenuate pull and stretch working modulus) of the sidewall of the housing main body portion of attenuate pull and stretch processing etc. is preferably 30～80%.The thickness of slab decrement is beyond this scope the time, and the sidewall that is difficult to the housing main body portion that will be shaped is adjusted to desired thickness of slab.
In addition, the aluminium alloy plate of the present invention that uses the aluminium alloy identical with housing main body portion to make the thickness of slab about 0.7～1.5mm is made cap.This aluminium alloy plate is cut into top corresponding shape with housing main body portion, forms inlet etc. as cap.Secondary battery material (positive electrode material, negative material, dividing plate etc.) is accommodated in above-mentioned housing main body portion, welds above-mentioned cap in the above.The welding of the pulsed laser of Waveform Control that the welding of housing main body portion and cap is common carrying out.To battery case, inject electrolytic solution from inlet then,, thereby make secondary cell the inlet sealing.
As mentioned above, aluminium alloy plate of the present invention is suitable for utilizing the perfect transfer press of implementing a series of forming process successively, is configured as the molding of the shape that requires, and is particularly suitable for the shell of lithium-ion secondary cell.That is, aluminium alloy plate of the present invention is for the so strict especially processing of the included multistage extruding of perfect transfer press-attenuate pull and stretch processing, has the excellent intensity and the aluminium alloy plate of plasticity (processibility).In addition, aluminium alloy plate of the present invention is can be with pulsed laser with for example housing main body portion when battery case is made and cap aluminium alloy plate that seal reliably, that have the pulsed laser weldability.In addition, be limited to by the content with the Ti in the unavoidable impurities, B and stipulate, the generation of the abnormal portion in can the welding of suppressor pulse laser apparatus can further improve the pulsed laser weldability.
In addition, as mentioned above, battery case with aluminium alloy plate making of the present invention, make the battery case temperature inside rise even in lithium-ion secondary cell etc., discharge and recharge repeatedly or under hot environment, use, thereupon under the situation that internal pressure rises, also the dilatational strain amount of this battery case suitably can be suppressed, make this dilatational strain amount lower.Like this, aluminium alloy plate of the present invention has excellent formability, and can satisfy intensity, resistance to pressure (expansibility resistance).And then, have excellent pulsed laser weldability, anti-welding crack, weld part excellent strength, and the generation of the abnormal portion in can the welding of suppressor pulse laser apparatus.
[embodiment]
More than narrate being used to implement mode of the present invention, confirmed the embodiment of effect of the present invention below and compared particularly to describe less than the comparative example of the underlying condition of unabridged version invention.In addition, the present invention is not limited in this embodiment.
[making] for the examination material
(embodiment No.1～17, comparative example No.18～35)
The aluminium alloy of the composition shown in the table 1 is fused, casts, make ingot bar, after this ingot bar enforcement surfacing, 500 ℃ of thermal treatments that homogenize of implementing 4 hours down.The ingot bar that this equalization was handled is implemented hot rolling, implements cold rollingly again, makes the milled sheet about thickness of slab 0.7mm.Then, this milled sheet is heated to 500 ℃ with 500 ℃/minute rate of heating, after keeping for 30 seconds under this temperature, cools off, carry out process annealing with 500 ℃/minute speed of cooling.At last, carry out finally cold rollingly with rolling rate 30%, make the aluminium alloy plate of thickness of slab 0.5mm.
(embodiment No.36～44, comparative example No.45～53)
The aluminium alloy (is identical composition with embodiment No.5) of the composition shown in the table 2 is fused, casts, make ingot bar, after this ingot bar enforcement surfacing, under the temperature shown in the table 2, implement 4 hours equal thermal treatment.The ingot bar that this equalization was handled is implemented hot rolling, implement again cold rolling, the milled sheet of making the regulation thickness of slab.Then, this milled sheet is carried out process annealing with the rate of heating shown in the table 2, annealing temperature (keeping for 30 seconds) and speed of cooling.At last, carry out finally cold rollingly with the rolling rate stress shown in the table 2, make the aluminium alloy plate of thickness of slab 0.5mm.
Table 1,2 is expressed as being grouped into.In addition, in the table, represent at the numerical value underscore that the composition that does not contain is represented with "-" less than the composition of unabridged version scope of invention.No.34 is the JISA3003 alloy, and No.35 is the alloy based on No. 3867989 record of Japanese Patent.
[table 1]
*: comprise unavoidable impurities
[distribution of intermetallic compound]
Then, the sharp distribution of measuring intermetallic compound in the following method.
At first, downcut aluminium alloy plate and imbed resin, to comprise that the face that rolling direction contains the thickness of slab direction grinds the formation minute surface, with as sightingpiston, (add up to 1mm at the composition (COMPO) of 500 times of acceleration voltage 20KV, multiplying power as middle observation 20 visuals field with scanning electron microscope (SEM)
2).Field of view is to be the center in the scope of the consistent 0.19mm of being in the both sides of thickness of slab direction and thickness of slab direction (go up direction and direction) down with the thickness of slab direction.The part of the demonstration whiter than parent phase is thought Al-Mn-Fe series intermetallic compound or Al-Mn-Fe-Si series intermetallic compound, the part of the demonstration more black than parent phase is thought the Mg-Si series intermetallic compound, obtain the total that maximum length is the area of the intermetallic compound more than the 1 μ m by picture processing, calculate area occupation ratio.In addition, calculating maximum length is the number of the above intermetallic compound of 11 μ m, calculates the number (individual number density) that does not have unit surface.The area occupation ratio of the intermetallic compound of the thickness of slab central part in the cross section of table 3,4 expression aluminium alloy plates and a number density.
[evaluation]
Resulting aluminium alloy plate is carried out following evaluation, the results are shown in table 4,5.
(intensity)
From aluminium alloy plate, downcut JIS5 number tension test sheet in the draw direction mode parallel with rolling direction.With the tension test of this test film enforcement JISZ2241, measure tensile strength, yield strength (0.2% yield strength) and extensible extent.The qualified benchmark of intensity is that yield strength is more than the 220MPa.
(plasticity)
The applying pressure processing machine also is set at 50% with the attenuate pull and stretch working modulus of sidewall, is the rectangular cell housing main body of the casing of 50mm with aluminium alloy plate shaping bottom surface for the height of vertical 5mm * horizontal 30mm, sidewall.At this moment, can be shaped and moulding after do not have shaggy style to be evaluated as have excellent formability " ◎ "; Can be shaped and take place shaggy style seldom and be evaluated as plasticity good " zero "; The sample of crackle taking place during shaping or tangible shaggy sample has taken place is evaluated as plasticity bad " * ".
(pulsed laser weldability)
As shown in Figure 1, be that the aluminium alloy plate 10,10 of 0.5mm faces each other its end face to dispose, by the pulsed laser welding this matching part is welded together with thickness of slab.In pulsed laser welding, utilize a pulsed laser to form the weld part 20 of fusion pool and solidified circle shape, while be moving to overlap along welding line continuously and form by laser apparatus.Welding machine uses the YAG laser apparatus of impulse hunting, welding speed be set at 25mm/ second and 35mm/ second two levels, shielding gas is supplied with nitrogen with 20 liters/minute setting.In addition, the depth of fusion of weld seam is about the condition of 200 μ m during with the aluminium alloy plate shown in the welding No.5, according to selected frequency shown in the table 3 and pulsed laser output.
[table 3]
About estimating, with the naked eye reach having or not of observation by light microscope welding crack, the sample that has obtained sound weld seam is judged to be " zero "; The sample that has produced crackle is judged to be " * ".
In addition, the cross section of dissecing as the X-X line of Fig. 1 cuts out section of weld joint, utilizes opticmicroscope to observe, and measures the depth of fusion of weld seam, and the degree of depth is that the above average evaluation of 180 μ m is the sample " zero " that has obtained sufficient strength of joint; The situation that the degree of depth is lower than 180 μ m is evaluated as the sample " * " (being designated as " fusing into " in the table) that does not obtain sufficient strength of joint because of fusing into deficiency.In addition, shown in Fig. 2 (a), the average evaluation that will not produce abnormal portion 21 (with reference to Fig. 2 (b)) is bead shape good " zero "; Shown in Fig. 2 (b), be bead shape bad " * " (being designated as " generation abnormal portion " in the table) with the average evaluation that produces abnormal portion 21.
On the other hand, about the generation of the paroxysmal weld seam abnormal portion in the pulsed laser welding, the situation occurred of envisioning its related gas hole defect is observed.The measuring method of pore is because therefore pore, utilizes microscopic examination to carry out directly for testing the size that can not judge by the radioactive rays transmission.Promptly, as shown in Figure 3, to comprise the mode of weld seam 20, it is the test film (part that the cubic frame table of the usefulness of the last figure of Fig. 3 shows) of Ls that materials to be welded 10,10 after the pulsed laser welding is taked along welding line direction length, this test film is bought in the resin, central part until the weld part width is ground in the cross section of weld part.Then, carry out microscopic examination for 400～1000 times, measure size, quantity and the position of pore 22 with multiplying power.The size of this pore 22 utilizes microscopical scale to classify by range estimation, is divided into being spaced apart four sections of 1.25 μ m and surpassing 1 section of 7.5 μ m from path 2.5 μ m to 7.5 μ m, adds up to and is divided into 5 sections.In addition, situation occurred about pore 22, it according to the length of welding line direction the diameter of the pore 22 that takes place in the sightingpiston of Ls, calculate its area, this area is multiplied by the number of the pore 22 that is comprised in the scope of its area, the number of this pore 22 of all areal extents is amounted to, obtain total sectional area, remove this total sectional area with viewing distance Ls, calculate pore generation degree.That is, pore generation degree is calculated with following formula.
Pore generation degree (μ m
2/ mm)={ the pore total sectional area (area * number) in the cross section of taking }/Ls
Its result: at pore generation degree is 3.0 μ m
2Under the situation below the/mm, it is good to be evaluated as weld shape; Pore generation degree surpasses 3.0 μ m
2Under the situation of/mm, it is not whole to be evaluated as weld shape.Therefore, pore generation degree is 3.0 μ m
2The situation that/mm is following is evaluated as weld seam and forms well (no abnormal) " zero "; Pore generation degree surpasses 3.0 μ m
2The average evaluation of/mm is that weld seam forms bad " * ".
(resistance to pressure)
Use the square shell of making in the evaluation of above-mentioned plasticity, 294kPa (3kg/cm is arranged in effect
2) the state of interior pressure under, will be heated to 100 ℃ and kept 2 hours by the rectangular cell shell that coincidence impulse laser apparatus welded seal covers material well.After returning to room temperature, measure the expansion addendum modification of the side (face of horizontal wide 30mm * height 50mm) of battery case.The shell of addendum modification below 0.8mm is evaluated as the excellent ◎ of resistance to pressure; Addendum modification surpasses 0.8mm and is that the following shell of 1.0mm is evaluated as resistance to pressure good " zero "; The shell that addendum modification surpasses 1.0mm is evaluated as resistance to pressure bad " * ".
Need to prove that in the table, yield strength does not satisfy the sample of qualified benchmark, represent that ingot bar or milled sheet fusion and the sample that can not estimate are with "-" expression at its numerical value underscore.In addition, during resistance to pressure was estimated, crackle or abnormal portion had taken place and the sample estimated in the sample of estimating because of plasticity is bad, because of in the pulsed laser welding in the weld seam, represent with "-".
(evaluation that aluminium alloy is formed)
As shown in table 4, as No.1～17 of embodiment, owing to satisfy scope of the present invention, so all excellent at intensity, plasticity, pulsed laser weldability, resistance to pressure aspects.
On the other hand, No.18 as a comparative example～35 because of less than the unabridged version scope of invention, become following result.
No.18: because Mn content is lower than lower value, resistance to pressure is poor.On the other hand, about plasticity, suppress the result that yield strength reduces by Cu content, plasticity can be guaranteed reluctantly.In addition, though the number of fine intermetallic compound reduces, maximum length is that the area occupation ratio of the above intermetallic compound of 1 μ m has surpassed 0.3%.
No.19: because Mn content surpasses higher limit, multiple and thickization of intermetallic compound, plasticity is poor.No.20: because Cu content is lower than lower value, weld seam fuses into deficiency, and the pulsed laser weldability is poor.And resistance to pressure is poor.No.21: because Cu content surpasses higher limit, plasticity is poor.And crackle takes place in the weld seam, and the pulsed laser weldability is poor.
No.22: because Mg content is lower than lower value, intensity, resistance to pressure are poor.No.23: because Mg content surpasses higher limit, plasticity is poor.And, crackle, abnormal portion take place in the weld seam, pore generation degree height, the pulsed laser weldability is poor.
No.24: because Si content is lower than lower value, resistance to pressure is poor.On the other hand, about plasticity, suppress the result that yield strength reduces by Cu content, plasticity can be guaranteed reluctantly.In addition, though the number of fine intermetallic compound reduces, maximum length is that the area occupation ratio of the above intermetallic compound of 1 μ m has surpassed 0.3%.No.25: because Si content surpasses higher limit, crackle takes place in the weld seam, the pulsed laser weldability is poor.On the other hand, about plasticity, suppress the result that yield strength reduces by Cu content, plasticity can be guaranteed reluctantly.In addition, though generated thick intermetallic compound, maximum length is that the individual number density of the above intermetallic compound of 11 μ m is below 140.
No.26: because Fe content is lower than lower value, the intermetallic compound deficiency, plasticity is poor.No.27: because Fe content surpasses higher limit, multiple and thickization of intermetallic compound, plasticity is poor.No.28: because Zn content surpasses higher limit, crackle takes place in the weld seam, the pulsed laser weldability is poor.
No.29: because Zr content surpasses higher limit, plasticity is poor.No.30: because Cr content surpasses higher limit, plasticity is poor.In addition, in No.29,30, though generated thick intermetallic compound, maximum length is that the individual number density of the above intermetallic compound of 11 μ m is below 140.No.31 and No.35: because Ti content surpasses higher limit, abnormal portion takes place in the weld seam, pore generation degree height, the pulsed laser weldability is poor.
No.32: because B content surpasses higher limit, abnormal portion takes place in the weld seam, pore generation degree height, the pulsed laser weldability is poor.No.33: owing to Ti content, B content all surpass higher limit, abnormal portion takes place in the weld seam, pore generation degree height, the pulsed laser weldability is poor.No.34: because Cu content, Mg content all are lower than lower value, intensity, resistance to pressure are poor.In addition, weld seam fuses into deficiency, and the pulsed laser weldability is poor.
(evaluation of manufacture method)
As shown in table 5, as No.36～44 of embodiment, owing to satisfy scope of the present invention, so all excellent at intensity, plasticity, pulsed laser weldability, resistance to pressure aspects.
On the other hand, No.45 as a comparative example～53 because of less than the unabridged version scope of invention, become following result.
No.45: because all thermal treatment temp is lower than lower value, the intermetallic compound pilosity, plasticity is poor.No.46: because all thermal treatment temp surpasses higher limit, ingot bar fusion.
No.47: because the rate of heating in the process annealing is lower than lower value, the intermetallic compound pilosity, plasticity is poor.No.48: because the annealing temperature in the process annealing is lower than lower value, plasticity is poor.No.49: because all thermal treatment temp is lower than lower value, homogenizing of ingot bar is insufficient, and the annealing temperature in the process annealing surpasses higher limit, milled sheet fusion.
No.50: because the cooling temperature in the process annealing is lower than lower value, the intermetallic compound pilosity, plasticity is poor.No.51: because rate of heating, annealing temperature and speed of cooling in the process annealing all are lower than lower value, the intermetallic compound pilosity, plasticity is poor.No.52: because final cold rolling draft is lower than lower value, intensity and resistance to pressure are poor.No.53: because final cold rolling draft surpasses higher limit, plasticity is poor.
Claims (7)
1. an aluminium alloy plate is characterized in that, contains Mn:0.4～1.5 quality %, Cu:0.7～4.0 quality %, Mg:0.2～1.5 quality %, Si:0.05～1.0 quality %, Fe:0.05～1.0 quality %, and surplus is Al and unavoidable impurities,
In the described unavoidable impurities, restriction Zn is that 0.3 quality % is following, to be lower than 0.02 quality %, B be below the 20 quality ppm to Ti.
2. aluminium alloy plate as claimed in claim 1 is characterized in that, also contains below the Zr:0.15 quality %.
3. aluminium alloy plate as claimed in claim 1 is characterized in that, also contains below the Cr:0.40 quality %.
4. aluminium alloy plate as claimed in claim 1, it is characterized in that, thickness of slab direction central part in the cross section of described aluminium alloy plate, maximum length is that the area occupation ratio of the above intermetallic compound of 1 μ m surpasses 0.3% and be lower than 2.1%, and maximum length is that the number of the above intermetallic compound of 11 μ m is 140/mm
2Below.
5. the manufacture method of the described aluminium alloy plate of claim 4 is characterized in that, comprising:
Fusion, casting have the aluminium alloy of described composition to make the casting process of ingot bar;
More than 420 ℃ and be lower than the temperature of the fusing point of described aluminium alloy, described ingot bar is implemented to homogenize the heat treated heat treatment step that homogenizes;
Carry out the hot rolled hot-rolled process to having carried out the described heat treated ingot bar that homogenizes;
Behind described hot-rolled process, carry out the cold rolling process that cold rolling is done milled sheet;
Described milled sheet is implemented the process annealing operation of process annealing;
The milled sheet of having carried out described process annealing is implemented final cold rolling final cold rolling process with draft 20～50%,
Described process annealing is the temperature province that is heated to 420 ℃ or more with the rate of heating more than 100 ℃/minute described milled sheet and is lower than the fusing point of described aluminium alloy, after this temperature province kept for 0～180 second, cool off with the speed of cooling more than 300 ℃/minute.
6. as the described aluminium alloy plate of claim 1～4, it is characterized in that, be used for battery case.
7. a battery case is characterized in that, uses the described aluminium alloy plate of claim 1～4.
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| JP2009086072A JP5798710B2 (en) | 2009-03-31 | 2009-03-31 | Aluminum alloy plate and battery case with excellent irregular and bead prevention properties |
| JP2009-086072 | 2009-03-31 | ||
| JP2009-219777 | 2009-09-24 | ||
| JP2009219777A JP5599588B2 (en) | 2009-09-24 | 2009-09-24 | Aluminum alloy plate for battery case, method for producing the same, and battery case |
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| KR20100109504A (en) | 2010-10-08 |
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