CN102400015B - Aluminium Alloy Plate For Cell Box And Cell Box - Google Patents
Aluminium Alloy Plate For Cell Box And Cell Box Download PDFInfo
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- CN102400015B CN102400015B CN201110267253.1A CN201110267253A CN102400015B CN 102400015 B CN102400015 B CN 102400015B CN 201110267253 A CN201110267253 A CN 201110267253A CN 102400015 B CN102400015 B CN 102400015B
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 81
- 238000003466 welding Methods 0.000 claims abstract description 100
- 230000035515 penetration Effects 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 230000004927 fusion Effects 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 230000033228 biological regulation Effects 0.000 claims description 5
- 230000001788 irregular Effects 0.000 abstract description 32
- 230000002159 abnormal effect Effects 0.000 abstract description 4
- 239000011324 bead Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 36
- 230000000694 effects Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 238000005266 casting Methods 0.000 description 12
- 239000000956 alloy Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 229910000765 intermetallic Inorganic materials 0.000 description 8
- 208000037656 Respiratory Sounds Diseases 0.000 description 7
- 238000005097 cold rolling Methods 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 230000008602 contraction Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229910018131 Al-Mn Inorganic materials 0.000 description 4
- 229910018461 Al—Mn Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910018643 Mn—Si Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/20—Bonding
- B23K26/32—Bonding taking account of the properties of the material involved
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Plasma & Fusion (AREA)
- Inorganic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Laser Beam Processing (AREA)
Abstract
When carrying out pulse laser welding over JISA3000 aluminium alloy plate for a cell box, the abnormal part (irregular weld pass) can be avoided. The aluminium alloy plate for a cell boxy comprises, by mass, 0.8 to 1.5% of Mn, 0.05 to 0.2% of Cu, 0.05 to 0.6% of Si, and 0.05 to 0.7% of Fe. According to the requirement, by mass, Zn is below 0.05%, Ti below 0.04, and B below 10 ppm. The remains are constituted by A1 and some unavoidable impurity. Even when the penetration depth of the laser is over 0.25mm, the irregular weld pass can still be avoided.
Description
Technical field
The present invention relates to aluminum alloy plate for battery box and cell box that lithium-ion secondary cell case etc. uses.
Background technology
As the battery of mobile telephone and subnotebook PC etc., lithium-ion secondary cell is widely used.In material as the housing (being suitable for below claiming cell box) of the shell of this secondary cell, always in order to miniaturization and the lightweight of battery, also have to be used in the processibility (plasticity) being configured as cell box (mainly cell box main body) good, and use aluminium alloy material.
In the battery of mobile telephone and notebook computer, battery be expanded into problem.Therefore, in order to obtain high strength, with Al-Mn system alloy for base material and the alloy that is added with Cu, Mg in a large number obtains exploitation (with reference to patent documentation 1).But, different from the battery of mobile telephone etc., although lightweight expected by for motor vehicle cell box, but establish due to housing and framework etc. and intensity to a certain degree can be obtained, so there is no the intensity of this degree of battery requiring to reach mobile telephone etc., it would be better to and both require that there is intensity, require again the alloy that processibility/weldability is good.
As the aluminium alloy of such cell box, there will be a known the Al-Mn line aluminium alloy (with reference to patent documentation 2) based on JISA3003.Al-Mn line aluminium alloy laser welding is excellent, compares, easily obtain fusion penetration with the fine aluminium such as JISA1050.In the processing of the aluminium alloy of cell box, use pulse laser together with continuous laser.Pulse laser compares with continuous laser, there is the feature that the welding of applicable thin-walled material is such, but because welding conditions is strict, so aluminium alloy cracking, has, in fine aluminium, the such problem of irregular welding bead (welding bead is irregular) (patent documentation 3) occurs
[patent documentation 1] Japanese Patent No. 3867989 publication
[patent documentation 2] JP 2002-134069 publication
[patent documentation 3] JP 2009-287116 publication
The material thin from the such thickness of slab of battery boxes for portable telephone case aluminium is different, in the cell box of automobile, due to the thickness that thickness of slab acquires a certain degree, in order to obtain the weld part intensity specified, needs to deepen fusion penetration.But in JISA3003 aluminium alloy, if fusion penetration is more than 0.25mm, then the shape stability of welding bead significantly reduces, and the incidence of irregular welding bead sharply increases.This irregular welding bead according to circumstances can become the fusion penetration being penetrated into the welded material back side, produces the problem performance of electroconductibility and operating voltage etc. being caused to disadvantageous effect.The weld part that there occurs irregular welding bead is presented in Fig. 1 (b), Fig. 2 (b).Be be formed as large diameter welding bead in Fig. 1 (b), in Fig. 2 (b), two place's dark fusion penetration welding beads are irregular welding beads.Fig. 1 (a), Fig. 2 (a) represent the weld part that irregular welding bead does not occur.The diameter of welding bead is neat, and the degree of depth of fusion penetration is substantially certain.
Summary of the invention
The present invention in view of such prior art problem points and do, its object is to, a kind of aluminum alloy plate for battery box with processibility (particularly main part) for being made into cell box and pulsed laser welding is provided, and uses the cell box of this aluminum alloy plate for battery box.
The generation of the abnormal portion (irregular welding bead) of pulse laser welding, as described below, to from (660 ~ 750 DEG C) during pulse laser melting to resolidification (660 ~ 640 DEG C) during remain in the generation degree of the gas hole defect in welding bead relevant (with reference to patent documentation 3).
During welding, pulsed laser irradiation portion forms molten state, in this molten bath, there is the bubble formed by hydrogen, shielding gas, metal vapors etc.At the end of the pulsed laser irradiation of 1 pulse, pulsed laser irradiation portion, to process of setting transition, but when bubble is difficult to discharge from molten bath, easily directly to remain as gas hole defect.During pulsed laser welding, overlapping welding bead and by pulsed laser irradiation below again on the welding bead solidifying end.Then, solidify terminate road by the irradiation of pulse laser again melting time, residual pore is by pulsed laser irradiation, air porous expanded, and aperture (the キ mono-ホ mono-Le) hypertrophyization usually formed due to pulsed laser irradiation, the easy depth of laser enters.Consequently fusion penetration is formed very dark, becomes the steady fusion penetration portion of non-perseverance.The steady fusion penetration portion of this non-perseverance solidifies, and becomes the irregular welding bead of weld part.
With the fusion penetration degree of depth of below 0.25mm, when Al-Mn alloy sheets for common JISA3003 aluminium alloy etc. carries out pulse laser welding, even if also can not there is irregular welding bead with Large Heat Input Welding, but in the scope of fusion penetration more than 0.25mm, its incidence will sharply uprise.
Therefore, the present inventors, in order to develop the advantage of the JISA3000 line aluminium alloy plate of the former material excellence both given play to as lithium ion battery case, again when deepening the fusion penetration degree of depth that pulsed laser welding is formed, still can prevent the former material of the generation of irregular welding bead, carry out various experimental study.
Consequently, the present inventors find, as the containing of Ti and B of the trace ingredients of JISA3000 line aluminium alloy, great impact is produced for the irregular welding bead in pulse welding, and by by the rules of content of Ti and B contained in this alloy in suitable scope, the generation of irregular welding bead can be prevented.
Namely, aluminum alloy plate for battery box of the present invention (being suitable for below being called aluminium alloy plate), it is characterized in that, containing Mn:0.8 ~ 1.5 quality %, Cu:0.05 ~ 0.2 quality %, Si:0.05 ~ 0.6 quality %, Fe:0.05 ~ 0.7 quality %, regulation Zn at below 0.05 quality %, Ti lower than 0.04 quality %, B lower than 10 quality ppm, surplus is made up of Al and inevitable impurity.
Above-mentioned aluminium alloy plate, by containing Mn, Cu, Si with specified amount, the solid solution in parent phase of each element, the intensity of aluminium alloy plate improves.In addition, by containing Mn, Si, Fe with specified amount, due to the formation of intermetallic compound, plasticity improves.In addition, by by Zn concentration guidelines below specified amount, when the laser welding of aluminium alloy plate, the Zn that steam forces down can not disperse, and can not pollute around.And, by Ti, B are defined in below specified amount, when pulsed laser welding irradiates the melting of the former material carried out, solidify in welding bead and be difficult to residual bubble, prevent the generation of the irregular welding bead of weld part.
Above-mentioned aluminum alloy plate for battery box, such as automobile cell box use time, use have to a certain degree thick thickness of slab (such as more than 0.5mm).Above-mentioned aluminum alloy plate for battery box, even if when the fusion penetration degree of depth is the degree of depth more than 0.25mm, also can prevent the generation of the irregular welding bead in pulsed laser welding.
Cell box is made up of box main body and lid material, and both carry out pulsed laser welding.Above-mentioned aluminum alloy plate for battery box, as box main body and the use of lid material of cell box.But lid material also can replace with other the aluminium alloy such as JISA1050 aluminium alloy.
Aluminum alloy plate for battery box of the present invention, has excellent pulsed laser welding.Specifically, even in the pulsed laser welding of the very dark fusion penetration degree of depth (more than 0.25mm) that can not prevent irregular welding bead from occurring in current material, the generation of irregular welding bead also can be prevented.Therefore, needs form the automobile use of the dark fusion penetration degree of depth etc. cell box material with pulse laser welding is suitable as.
In addition, aluminum alloy plate for battery box of the present invention, remains the intensity same with current material, and the plasticity (contraction processibility) with when form box main body required excellence the same as current material.
Accompanying drawing explanation
Fig. 1 is the vertical view (optical microscope photograph) of the weld part that pulse laser welding is formed, and (a) represents good weld part, and (b) represents the weld part that there occurs irregular welding bead.
Fig. 2 is the sectional view (optical microscope photograph) of the weld part that pulse laser welding is formed, and (a) represents good weld part, and (b) represents the weld part that there occurs irregular welding bead.In (a), (b), the gauge of bottom right represents 200 μm.
Embodiment
Below, aluminum alloy plate for battery box of the present invention is further illustrated.
[formation of aluminium alloy plate]
Aluminium alloy plate of the present invention, be contain Mn, Cu, Si, Fe with specified amount, Zn, Ti, B are defined in below specified amount, the aluminium alloy plate that surplus is made up of Al and inevitable impurity.
Below, the restriction reason for each composition is described.
(Mn:0.8 ~ 1.5 quality %)
Mn is solid solution in parent phase, improves the intensity of aluminium alloy plate, has the effect that compressive strength is improved, along with the increase of Mn content can improve intensity.In addition, Mn and Al, Fe, Si form intermetallic compound, (Al-Fe-Mn series intermetallic compound, Al-Fe-Mn-Si series intermetallic compound), and it is separated out imperceptibly, contribute to the lubricant effect when formed machining becomes cell box, the plasticity of behaviour's alloy sheets is improved.But when Mn content is lower than 0.8 quality %, these effects are insufficient, if more than 1.5 quality %, then the quantity of thick intermetallic compound increases, and easily becomes the starting point of crackle when being shaped, and the plasticity of aluminium alloy plate reduces.Therefore, Mn content is more than 0.8 quality %, below 1.5 quality %.Be preferably more than 0.9 quality %, below 1.3 quality %.
(Cu:0.05 ~ 0.2 quality %)
Cu solid solution and there is the effect of intensity improving aluminium alloy plate.But when Cu content is lower than 0.05 quality %, this effect is insufficient, if more than 0.2 quality %, then easily there is welding crack, be not therefore preferred.Therefore, Cu content is more than 0.05 quality %, below 0.2 quality %.Be preferably more than 0.1 quality %, below 0.18 quality %.
(Si:0.05 ~ 0.6 quality %)
Si is solid solution in parent phase, improves the intensity of aluminium alloy plate, has the effect that compressive strength is improved.In addition, Si and Al, Mn, Fe form Al-Fe-Mn-Si series intermetallic compound (with reference to about the description before Mn), and the plasticity of aluminium alloy plate is improved.But when Si content is lower than 0.05 quality %, these effects are insufficient, if more than 0.6 quality %, then between aforementioned metal, compound is thick, easily become the starting point of crackle when being shaped, the plasticity of aluminium alloy plate reduces.In addition, if Si content is more than 0.6 quality %, then easily there is welding crack.Therefore, Si content is more than 0.05 quality %, below 0.6 quality %.Be preferably more than 0.05 quality %, below 0.2 quality %.
(Fe:0.05 ~ 0.7 quality %)
Fe and Mn, Si are same, form Al-Fe-Mn system, Al-Fe-Mn-Si series intermetallic compound (with reference to about the description before Mn), have the effect that the plasticity of aluminium alloy plate is improved.But when Fe content is lower than 0.05 quality %, this effect is insufficient, if more than 0.7 quality %, then the quantity of thick described intermetallic compound increases, and easily becomes the starting point of crackle when being shaped, and the plasticity of aluminium alloy plate reduces.In addition, if Fe content is more than 0.7 quality %, then easily there is pore.Therefore, Fe content is more than 0.05 quality %, below 0.7 quality %.Be preferably more than 0.4 quality %, below 0.6 quality %.
As above, its content is substantially according to the composition of JISA3003 for the main component of aluminium alloy plate of the present invention.The surplus of removing Mn, Cu, Fe, Si, except Ti, B described later, is made up of Al and inevitable impurity.Inevitable impurity is included in matrix metal and master alloy.Ti, B and main inevitable impurity are below described.
(Ti is lower than 0.04 quality %)
Ti has makes the miniaturization of aluminium alloy cast structure, the effect of homogenize (stabilization), to prevent for the purpose of the casting crack of rolling slab when casting, conventional in the scope of 0.02 ~ 0.15 quality %.But, when the aluminium alloy of aforementioned component, if containing Ti at more than 0.04 quality %, then the former material under pulsed laser irradiation when melting (660 ~ 750 DEG C) easily solidifying remaining pore in welding bead.Therefore, with pulsed laser irradiation below again melting and solidification welding bead time, as previously described, fusion penetration is formed deeply (the steady fusion penetration portion of non-perseverance), and it solidifies and has abnormal portion (irregular welding bead) to occur at weld part.In aluminium alloy of the present invention, Ti contains as inevitable impurity in matrix metal (containing in waste material), or as required as the element that master alloy is added for the purpose of above effect.In any case, its content all needs to be defined as lower than 0.04 quality % (containing 0%).
(B is lower than 10 quality ppm)
B, as aforementioned, for the purpose of casting crack during to prevent aluminium alloy at slab ingot casting, actively adds together with Ti as Ti-B mother alloy and the element commonly used.But, when the aluminium alloy of aforementioned component, when B content is more than 10 quality ppm, the same with aforesaid Ti, easy remaining pore in welding bead is solidified in pulsed laser irradiation portion, with pulsed laser irradiation below again melting and solidification welding bead time, fusion penetration is formed deeply, and it solidifies and abnormal portion (irregular welding bead) occurs.In aluminium alloy of the present invention, B contains as inevitable impurity in matrix metal (containing in blank), or as required as the element that master alloy is added for the purpose of above effect.In any case, its content all needs to be defined as lower than 10 quality ppm (containing 0ppm).Be preferably below 9 quality ppm.
(inevitable impurity)
As main inevitable impurity, Zn, Zr, Cr, Ga, V, Ni, Mg etc. can be enumerated.
Wherein Zn is because steam forces down, so around easily dispersing when pulsed laser welding and polluting, bead crack easily occurs in addition, makes the pulsed laser welding of aluminium alloy plate be deteriorated.Therefore, Zn content is defined in below 0.05 quality %.Be preferably below 0.04 quality %.
As Zr, Cr, Ga, V, Ni, Mg etc. of other inevitable impurity, if in usually known scope, then effect of the present invention can not be hindered.These inevitable impurity containing being respectively below 0.05 quality %, as the inevitable total impurities comprising Ti, B and Zn, allow in the scope of 0.15 quality %.
[manufacture method of aluminium alloy plate]
Then, the example for the manufacture method of aluminium alloy plate of the present invention is described.
First, fusing, casting have the aluminium alloy of aforementioned component, make ingot casting, after implementing face milling, implement to homogenize thermal treatment with more than 480 DEG C and lower than the temperature of aforementioned aluminium alloy fusing point to this ingot casting.Secondly, hot rolling and cold rolling, making milled sheet are carried out for this process heat treated ingot casting that homogenizes.Then, with more than 100 DEG C/minute rate of heating, this milled sheet is heated to more than 420 DEG C and lower than the temperature province of aforementioned aluminium alloy fusing point, after this temperature province keeps 0 ~ 180 second, cool with the speed of cooling of more than 300 DEG C/minute, implement process annealing thus.Afterwards, the draft with 20 ~ 50% is implemented finally cold rolling for the milled sheet that have passed through process annealing, becomes aluminium alloy plate.Further, also can as required, for the final annealing implementing finally cold rolling milled sheet and implement 80 ~ 200 DEG C, 0.5 ~ 8 hour.By final annealing, material softening, unit elongation improves, and therefore final annealing is the operation being suitable for plasticity is improved.
[cell box]
Then, cell box of the present invention is described.Cell box of the present invention, uses aforementioned aluminium alloy plate to make.
Below, the example being made the method for cell box and secondary cell by aluminium alloy plate of the present invention is described.
[making method of cell box and secondary cell]
As the aluminium alloy plate of the present invention in box main body portion, through finally cold rolling and become the thickness of slab of about 0.7 ~ 2.0mm.This aluminium alloy plate being cut into the shape of regulation, to be processed by drawing or contraction processes shape for there being bottomless drum shape shape.Repeatedly repeat this processing again, slowly increase side wall surface, implement the processing of finishing etc. as required, be configured as the bottom shape of regulation and profile height and become box main body portion.Box main body portion be open above have bottomless drum shape shape.The shape of cell box is not particularly limited, and has the rectangular parallelepiped etc. of round shape, flat, follows the specification of secondary cell.
The thickness reduction (contraction working modulus) of the sidewall in the box main body portion that contraction processing etc. causes amounts to and is preferably 30 ~ 80%.When thickness reduction is beyond this scope, the thickness of slab that the sidewall of the box main body of shaping adjusts to needs is had any problem.
In addition, with the aluminium alloy identical with box main body portion, make cap with the aluminium alloy plate of the present invention of thickness of slab about 0.7 ~ 2.0mm.This aluminium alloy plate is cut into the shape corresponding above with box main body portion, formation inlet etc. and become cap.But cap also can be made by other aluminium alloys such as JISA1050 aluminium alloys.Hold secondary battery material (positive electrode material, negative material, dividing plate etc.) in aforementioned box main body portion, weld described cap above.The welding of box main body portion and cap is undertaken by the pulsed laser welding being subject to Waveform Control.Then, be injected into cell box by electrolytic solution from inlet, sealing inlet, becomes secondary cell.
As more than, aluminium alloy plate of the present invention, by implementing the multiple position press of a series of formed machining in order and being configured as the molding of the shape of expection, it is particularly suitable for the cell box of lithium-ion secondary cell.That is, aluminium alloy plate of the present invention, in the face of multistage drawing-such processing harsh especially of contraction processing that multiple position press comprises, has excellent plasticity (processibility).In addition, aluminium alloy plate of the present invention also has pulsed laser welding, such as, when being made into cell box, and can with pulse laser positively watertight chest main part and cap.
[embodiment]
Below, the embodiment confirming effect of the present invention is compared with the comparative example not meeting important document of the present invention, is described particularly.
[making for examination material]
Melt, the aluminium alloy of composition shown in casting table 1 and become ingot casting, after face milling is implemented to this ingot casting, implement the thermal treatment that homogenizes in 4 hours with 540 DEG C.Hot rolling is implemented for this process heat treated ingot casting that homogenizes, then implements cold rolling.With 500 DEG C/minute, the milled sheet after cold rolling is heated to 520 DEG C, after keeping 30 seconds with this temperature, cools with 500 DEG C/minute and carry out process annealing.Finally, the draft with 30% carries out finally cold rolling, becomes the aluminium alloy plate of thickness of slab 1.0mm.
[table 1]
| Mn | Cu | Mg | Si | Fe | Ti | Zn | B* | Al | |
| Embodiment 1 | 0.97 | 0.15 | 0.01 | 0.11 | 0.64 | 0.003 | 0.01 | 9.6 | Surplus |
| Comparative example 1 | 0.96 | 0.15 | 0.01 | 0.11 | 0.63 | 0.005 | 0.01 | 15.0 | Surplus |
| Comparative example 2 | 0.96 | 0.15 | 0.01 | 0.11 | 0.65 | 0.011 | 0.01 | 22.5 | Surplus |
| Comparative example 3 | 0.96 | 0.15 | 0.01 | 0.12 | 0.64 | 0.024 | 0.01 | 27.2 | Surplus |
| Comparative example 4 | 0.98 | 0.15 | 0.01 | 0.11 | 0.65 | 0.034 | 0.01 | 25.8 | Surplus |
| Comparative example 5 | 0.97 | 0.15 | 0.01 | 0.11 | 0.66 | 0.257 | 0.01 | 57.7 | Surplus |
| Comparative example 6 | 0.98 | 0.15 | 0.01 | 0.11 | 0.66 | 0.06O | 0.01 | 20.1 | Surplus |
| Comparative example 7 | 0.96 | 0.15 | 0.01 | 0.11 | 0.66 | 0.054 | 0.01 | 27.4 | Surplus |
| Embodiment 2 | 0.97 | 0.14 | 0.01 | 0.11 | 0.65 | 0.021 | 0.01 | 6.7 | Surplus |
| Comparative example 8 | 1.15 | 0.16 | 0.01 | 0.28 | 0.51 | 0.030 | 0.01 | 24.7 | Surplus |
| Comparative example 9 | 1.12 | 0.15 | 0.01 | 0.25 | 0.53 | 0.O30 | 0.01 | 18.0 | Surplus |
| Comparative example 10 | 1.10 | 0.76 | 0.42 | 0.26 | 0.10 | 0.010 | 0.O1 | 15.0 | Surplus |
*ppm
[pulsed laser welding test]
Pulse welding test is carried out with the aluminium alloy plate obtained.
As shown in Figure 1, the aluminium alloy plate of configuration two same compositions, makes end face dock each other, by this docking section of pulsed laser welding.Weld length (welding bead length) is 90mm.In pulsed laser welding, form molten bath by 1 pulse laser and the weld part of round shape that solidifies along with the movement of laser, overlap while be formed along welding line continuously.Welding machine uses the YAG laser of impulse hunting; weld with following condition: welding speed is that 20cm/ divides; peak-peak output rating 4.5kW; frequency 10Hz; the energy (heat input) of every 1 pulse is 24J/p (condition 1), 25J/p (condition 2), 26J/p (condition 3); pulse shape control is implemented by descending slope (ダ ウ Application ス ロ mono-プ), and shielding gas is the nitrogen of 20 liters/min.Further, the heat input of every 1 pulse is by the Timing of descending slope.
[weldability evaluation]
In the evaluation of pulse laser welding, first, whether welding crack is there occurs with naked eyes and observation by light microscope, full terms 1 ~ condition 3 times, the judgement that can obtain crossing over all flawless sound welding bead of welding bead total length is "○", even if condition 1 ~ condition 3 a certain in occur place's crackle, be also judged to be "×".
In addition, with observation by light microscope irregular welding bead generation number (the every 90mm of welding bead length).Specifically, as shown in Figure 1, 2, the shooting plane of weld part and the optical microscope photograph of welding bead central part section, add up irregular welding bead generation number.On this basis, the situation of irregular welding bead does not occur at full terms for 1 ~ 3 time, weld bead shape is good and be evaluated as "○", no matter condition 1 ~ 3 which under, even if be also evaluated as weld bead shape bad "×" when there is 1 irregular welding bead.
In addition, the fusion penetration degree of depth (perfecting the fusion penetration degree of depth in portion) is measured from the optical microscope photograph of the section of weld part.
Above result display in table 2.
[table 2]
The degree of depth: mm
As shown in table 2, there is the embodiment No.1,2 that one-tenth given to this invention is grouped into and welding crack does not occur, in in condition 2, condition 3 ~ large-line energy condition time (situation that the fusion penetration degree of depth is dark) also not there is irregular welding bead etc., pulsed laser welding is excellent.
On the other hand, although comparative example No.1 ~ 9 bead crack do not occur, the content of Ti and/or B does not meet regulation of the present invention, and therefore irregular welding bead occurs, particularly in condition 2, condition 3 ~ large-line energy condition under, the frequency of generation significantly increases.In addition, the many comparative example No.10 of Mg, Cu content, at welding bead generation crackle, can not get the weld part perfected.
(embodiment 2)
[making for examination material]
For the aluminium alloy shown in table 3, implement the manufacturing process identical with embodiment 1, become the aluminium alloy plate of thickness of slab 10mm.[table 3]
| Mn | Cu | Mg | Si | Fe | Zn | Ti | B* | Al | |
| Embodiment 3 | 0.82 | 0.15 | - | 0.11 | 0.62 | 0.01 | 0.003 | 9.1 | Surplus |
| Embodiment 4 | 0.97 | 0.15 | - | 0.11 | 0.64 | 0.01 | 0.003 | 9.6 | Surplus |
| Embodiment 5 | 1.42 | 0.15 | - | 0.12 | 0.66 | 0.01 | 0.004 | 9.7 | Surplus |
| Embodiment 6 | 0.96 | 0.07 | - | 0.11 | 0.65 | 0.01 | 0.003 | 9.3 | Surplus |
| Embodiment 7 | 0.98 | 0.14 | - | 0.07 | 0.61 | 0.01 | 0.003 | 9.6 | Surplus |
| Embodiment 8 | 1.00 | 0.15 | - | 0.56 | 0.68 | 0.01 | 0.004 | 9.8 | Surplus |
| Embodiment 9 | 0.98 | 0.16 | - | 0.11 | 0.08 | 0.01 | 0.003 | 9.0 | Surplus |
| Embodiment 10 | 1.00 | 0.15 | - | 0.12 | 0.35 | 0.01 | 0.003 | 9.6 | Surplus |
| Embodiment 11 | 0.98 | 0.15 | 0.04 | 0.12 | 0.65 | - | 0.004 | 9.3 | Surplus |
| Embodiment 12 | 0.97 | 0.15 | - | 0.11 | 0.64 | 0.04 | 0.003 | 9.5 | Surplus |
| Embodiment 13 | 0.98 | 0.15 | - | 0.12 | 0.64 | 0.01 | 0.003 | 6.5 | Surplus |
| Comparative example 11 | 0.75 | 0.15 | - | 0.11 | 0.55 | 0.01 | 0.003 | 9.5 | Surplus |
| Comparative example 12 | 1.61 | 0.16 | - | 0.12 | 0.64 | 0.01 | 0.003 | 9.6 | Surplus |
| Comparative example 13 | 0.97 | 0.03 | - | 0.11 | 0.66 | 0.01 | 0.003 | 9.6 | Surplus |
| Comparative example 14 | 0.98 | 0.23 | - | 0.11 | 0.65 | 0.01 | 0.003 | 9.4 | Surplus |
| Comparative example 15 | 1.00 | 0.14 | - | 0.03 | 0.65 | 0.01 | 0.003 | 9.6 | Surplus |
| Comparative example 16 | 0.99 | 0.15 | - | 0.66 | 0.63 | 0.01 | 0.004 | 9.8 | Surplus |
| Comparative example 17 | 0.96 | 0.16 | - | 0.11 | 0.03 | 0.01 | 0.003 | 9.6 | Surplus |
| Comparative example 18 | 0.99 | 0.15 | - | 0.11 | 0.76 | 0.01 | 0.004 | 9.5 | Surplus |
| Comparative example 19 | 1.00 | 0.15 | - | 0.12 | 0.65 | 0.07 | 0.003 | 9.3 | Surplus |
| Comparative example 20 | 0.98 | 0.14 | - | 0.11 | 0.64 | 0.01 | 0.05 | 9.8 | Surplus |
| Comparative example 21 | 0.97 | 0.15 | - | 0.11 | 0.56 | 0.01 | 0.005 | 12.2 | Surplus |
| Comparative example 22 | 0.98 | 0.15 | - | 0.11 | 0.65 | 0.01 | 0.006 | 15.3 | Surplus |
*ppm
Following test is carried out with the aluminium alloy plate obtained.The display of its result in table 4.
[strength trial]
From aluminium alloy plate, make draw direction parallel with rolling direction and cut the tension test sheet of No. JIS5, implementing the tension test of JISZ2241 with this test film.0.2% yield strength is 130N/mm
2above is evaluated as qualified "○", lower than 130N/mm
2the defective "×" of evaluation.
[formability test]
By aluminium alloy plate, use extrusion processing machine, make the contraction working modulus of sidewall be 40%, shaped bottom indulges 15mm × horizontal 120mm, the rectangular battery box main body of the casing of the height 90mm of sidewall.At this moment, crackle can not had to be shaped, after being shaped, the formative of surface free variable color and vertical stripe apperance is excellent, is evaluated as qualified "○", occur during shaping crackle or have significant variable color or vertical conditional, and plasticity is bad, is evaluated as defective "×".
(pulsed laser welding test)
Test same test method and condition (wherein, the energy (heat input) of every 1 pulse being set as a condition of 25J/p) with the pulsed laser welding of embodiment 1, carry out the pulse laser welding of aluminium alloy plate.
(weldability evaluation)
About whether there is welding crack and irregular welding bead, being observed by observational technique similarly to Example 1, judging qualified "○" and defective "×" with same evaluation method.
With measuring method similarly to Example 1, the optical microscope photograph according to the section of weld part measures the fusion penetration degree of depth (perfecting the fusion penetration degree of depth in portion), and the judgement that can obtain the fusion penetration degree of depth of more than 0.25mm is qualified "○".
[table 4]
As shown in table 4, have embodiment No.3 ~ 13 that one-tenth given to this invention is grouped into, all can obtain the fusion penetration degree of depth of more than 0.25mm, welding crack and irregular welding bead do not occur, pulse welding is excellent.
On the other hand, its Mn of comparative example No.11 is containing quantity not sufficient, and intensity difference, its Mn content of comparative example No.12 is superfluous, and plasticity is poor.Its Cu of comparative example No.13 is containing quantity not sufficient, and plasticity is poor, and its Cu content of comparative example No.14 is superfluous, and welding crack occurs.Its Si of comparative example No.15 containing quantity not sufficient, intensity and plasticity poor, its Si content of comparative example No.16 is superfluous, and plasticity is poor, generation welding crack.Its Fe of comparative example 17 is containing quantity not sufficient, and its Fe content of comparative example No.18 is superfluous, plasticity inequality.Its Zn content of comparative example No.19 is superfluous, and welding crack occurs.
Its Ti content of comparative example No.20 is superfluous, and comparative example No.21,22 its B content are superfluous, and irregular welding bead all occurs.
Claims (4)
1. the aluminum alloy plate for battery box of a pulsed laser welding excellence, it is characterized in that, containing Mn:0.8 ~ 1.5 quality %, Cu:0.05 ~ 0.2 quality %, Si:0.05 ~ 0.6 quality %, Fe:0.05 ~ 0.7 quality %, regulation Zn at below 0.05 quality %, Ti lower than 0.04 quality %, B lower than 10 quality ppm, surplus is made up of Al and inevitable impurity, further, the fusion penetration degree of depth obtained by pulsed laser welding is more than 0.25mm.
2. the aluminum alloy plate for battery box of pulsed laser welding excellence according to claim 1, is characterized in that, thickness of slab is more than 0.5mm.
3. a cell box main body, is characterized in that, is made up of the aluminum alloy plate for battery box described in claim 1 or 2.
4. a cell box, is characterized in that, is the cell box cell box main body be made up of the aluminium alloy plate described in claim 1 or 2 and battery cover material being carried out pulsed laser welding, and wherein, the fusion penetration degree of depth of laser is more than 0.25mm.
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| EP2851154B1 (en) | 2012-05-15 | 2019-08-28 | Toyota Jidosha Kabushiki Kaisha | Welding method, welding device, and battery manufacturing method |
| JP5954099B2 (en) * | 2012-10-12 | 2016-07-20 | 日本軽金属株式会社 | Aluminum alloy sheet for battery cases with excellent formability, heat dissipation and weldability |
| CN103469015B (en) * | 2013-08-12 | 2016-04-06 | 安徽盛达前亮铝业有限公司 | A kind of production technique of battery cover aluminum alloy sheet |
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