JP2011038122A - Aluminum alloy sheet for secondary battery case and method for producing the same - Google Patents
Aluminum alloy sheet for secondary battery case and method for producing the same Download PDFInfo
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- JP2011038122A JP2011038122A JP2009183488A JP2009183488A JP2011038122A JP 2011038122 A JP2011038122 A JP 2011038122A JP 2009183488 A JP2009183488 A JP 2009183488A JP 2009183488 A JP2009183488 A JP 2009183488A JP 2011038122 A JP2011038122 A JP 2011038122A
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000137 annealing Methods 0.000 claims abstract description 51
- 238000003466 welding Methods 0.000 claims abstract description 36
- 238000005097 cold rolling Methods 0.000 claims abstract description 28
- 230000006641 stabilisation Effects 0.000 claims abstract description 16
- 238000011105 stabilization Methods 0.000 claims abstract description 16
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 238000005096 rolling process Methods 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 238000005098 hot rolling Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000000630 rising effect Effects 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 14
- 230000007423 decrease Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 8
- 238000011282 treatment Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000265 homogenisation Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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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- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
本発明は、二次電池ケース用アルミニウム合金板に関し、特にリチウムイオン二次電池ケース用アルミニウム合金板に関する。 The present invention relates to an aluminum alloy plate for a secondary battery case, and more particularly to an aluminum alloy plate for a lithium ion secondary battery case.
リチウムイオン二次電池（以下二次電池と略称）は、ノート型パーソナルコンピュータや携帯電話などの携帯機器の電源として広く使用されているが、その優れた特性により、電気自動車やハイブリッド車の電源としても採用し始めている。
二次電池は通常、角型または円筒型金属ケースに電極体と電解質液を入れた後に、金属製蓋を付けてレーザ溶接により密封することで製造される。携帯電話等のモバイル電子機器の場合、前記の金属ケースには、アルミニウム合金板を多段プレスして製造したアルミニウム合金角型ケースが採用されていることが多い。従って、アルミニウム合金板には良好なプレス成形性が求められる。また、前述のように、蓋とケースはレーザ溶接によって接合するので、良好なレーザ溶接性も求められる。さらにモバイル電子機器に装着して使用しているときに、再充電により温度と内部圧力が上昇し、電池が膨らんで充電効率が著しく落ちる問題があるために、この内部圧力に耐える高強度アルミニウム合金板材が好ましくなる。
一方、車載二次電池の場合、モバイル電子機器よりはるかに大容量が必須のために、数十個の大型電池を組んだモジュール電池が使用される。安全性を重視する観点から、単体電池のケースには強度の高いステンレス鋼板を多段プレスして製造した角型ケースが採用されていることが多い。
近年、車体の軽量化やコストダウンのニーズが高まり、車載二次電池でもアルミニウム合金ケースを採用するニーズは高くなってきている。
Lithium ion secondary batteries (hereinafter abbreviated as secondary batteries) are widely used as power sources for portable devices such as notebook personal computers and mobile phones, but due to their superior characteristics, they can be used as power sources for electric and hybrid vehicles. Is also beginning to adopt.
A secondary battery is usually manufactured by putting an electrode body and an electrolyte solution in a square or cylindrical metal case, and then attaching a metal lid and sealing it by laser welding. In the case of a mobile electronic device such as a cellular phone, an aluminum alloy square case manufactured by multi-stage pressing of an aluminum alloy plate is often adopted as the metal case. Therefore, the aluminum alloy sheet is required to have good press formability. As described above, since the lid and the case are joined by laser welding, good laser weldability is also required. In addition, when mounted on a mobile electronic device, the temperature and internal pressure rise due to recharging, and the battery swells, causing a problem that the charging efficiency drops significantly. Therefore, a high-strength aluminum alloy that can withstand this internal pressure. A plate material is preferred.
On the other hand, in the case of an in-vehicle secondary battery, a much larger capacity is essential than a mobile electronic device, so a module battery in which several tens of large batteries are assembled is used. From the viewpoint of emphasizing safety, the case of the unit cell is often a square case manufactured by multi-stage pressing of a high-strength stainless steel plate.
In recent years, there has been a growing need for weight reduction and cost reduction of the vehicle body, and the need for adopting an aluminum alloy case for an in-vehicle secondary battery is increasing.
車載用モジュール電池の場合、モバイル電子機器と同様に単体電池ケースの材料にはプレス成形性とレーザ溶接性が求められるが、各々単体電池が外部より強力に拘束されるために、ケース自身には耐膨れへの要求はそれほど厳しくない。
ところが、蓋側では各種制御部品を装着する必要があるために外部より拘束することが難しい。一方、モバイル電子機器用二次電池よりも単体電池が大型化となり、電池内部の圧力が非常に大きくなるために、蓋とケースとの溶接部に対する高強度の要求ははるかに厳しくなる。一般には、ケース用アルミニウム合金板材は、加工硬化により高強度化されている。この場合、アルミニウム合金板自身の強度が高くても、蓋とのレーザ溶接時の入熱により局部的に軟化され、溶接後の溶接部または入熱の影響を受けたその近辺の熱影響部の強度が大幅に低下する。その結果、レーザ溶接部とその熱影響部は電池内部の高い圧力に耐えない恐れがある。
また、電池内部の圧力が大きく増大するために、レーザ溶接時の溶け込み深さを大きくし、接合強度を、モバイル電子機器用二次電池より高める必要がある。このためにレーザ溶接時の速度を下げざるを得ずに生産性が落ちる問題がある。
In the case of an in-vehicle module battery, the material of a single battery case is required to have press formability and laser weldability as in mobile electronic devices. However, since each single battery is strongly restrained from the outside, the case itself has The demand for blistering resistance is not so strict.
However, since it is necessary to mount various control components on the lid side, it is difficult to restrain from the outside. On the other hand, the unit battery becomes larger than the secondary battery for mobile electronic devices, and the pressure inside the battery becomes very large, so the demand for high strength for the welded portion between the lid and the case becomes much stricter. In general, the strength of case aluminum alloy sheets is increased by work hardening. In this case, even if the strength of the aluminum alloy plate itself is high, it is locally softened by heat input during laser welding to the lid, and the welded part after welding or the heat affected part in the vicinity affected by the heat input. The strength is greatly reduced. As a result, the laser weld and the heat affected zone may not withstand the high pressure inside the battery.
Further, since the pressure inside the battery greatly increases, it is necessary to increase the penetration depth during laser welding and to increase the bonding strength as compared with the secondary battery for mobile electronic devices. For this reason, there is a problem that productivity is reduced because the speed at the time of laser welding has to be reduced.
本発明者は、特許文献１において、高強度でプレス成形性、レーザ溶接性、耐膨れ性に優れた二次電池ケース用アルミニウム合金板を提案している。
この合金板は、Ｃｕ：１．０超〜１．８％、Ｍｎ：１．０超〜１．７％、Ｍｇ：０．１〜０．６％を含有し、残部がＡｌと不可避的不純物からなる組成を有し、引張強度２６０〜３５０ＭＰａ、導電率ＩＡＣＳ３９％以上、円相当直径０．５μｍ〜１０μｍの金属間化合物粒子が平均で１１０００〜３００００個／ｍｍ２分散する、というものである。
The present inventor has proposed an aluminum alloy plate for a secondary battery case having high strength and excellent press formability, laser weldability, and swelling resistance in Patent Document 1.
This alloy plate contains Cu: more than 1.0 to 1.8%, Mn: more than 1.0 to 1.7%, Mg: 0.1 to 0.6%, the balance being Al and inevitable impurities The intermetallic compound particles having a tensile strength of 260 to 350 MPa, an electrical conductivity of IACS of 39% or more, and an equivalent circle diameter of 0.5 μm to 10 μm are dispersed in an average of 11000 to 30000 particles / mm 2 .
ところが、特許文献１で言うところのレーザ溶接性とは、レーザによって溶接ができるかどうかを判定しているに過ぎず、レーザ溶接の熱影響による強度低下までは考慮がなされていないという問題点が見出された。
本発明は、上記の問題点に鑑みて成し遂げられたものであり、その目的は、プレス成形性、レーザ溶接性が優れ、かつレーザ溶接による強度低下を回復できるアルミニウム合金板を提供することにある。
However, the laser weldability referred to in Patent Document 1 merely determines whether or not welding can be performed by a laser, and there is a problem that no consideration has been given to a reduction in strength due to the thermal effect of laser welding. It was found.
The present invention has been accomplished in view of the above problems, and an object of the present invention is to provide an aluminum alloy plate that is excellent in press formability and laser weldability and that can recover strength reduction due to laser welding. .
本発明者等は、合金組成、製造条件、特に焼鈍条件について検討を加えたところ、レーザ溶接による強度低下を、自然に又は低温熱処理を施すことにより、回復できることを知見した。
すなわち本発明の二次電池ケース用アルミニウム合金板は、Ｍｎを０．７〜１．４質量％、Ｃｕを０．６〜１．３質量％、Ｍｇを０．２〜０．６質量％、Ｆｅを０．４超〜１．０質量％それぞれ含有し、残部が不可避的不純物及びＡｌからなる組成を有する。そして本発明の二次電池ケース用アルミニウム合金板は、引張強さσｓが２２０〜３１０ＭＰａ、引張強さσｓと耐力ｙｓとの差｜σｓ−ｙｓ｜が２０ＭＰａ以下であり、レーザ溶接部の溶接直後の引張強さをσｉ（ＭＰａ）、回復後の引張強さをσｒ（ＭＰａ）とすると、σｒ／σｉ≧１．２を満足することを特徴とする。なお、本願発明における引張強さσｓ及び耐力ｙｓは、レーザ溶接部を除く素材としての引張強さ及び耐力を意味する。また、本願発明におけるσｉ、σｒは、後述する実施例に記載のレーザ溶接条件、引張強さの測定条件に基づいて特定される値である。また、回復後とは、レーザ溶接後に、格別な処理を行うことなく放置することを意味する。ただし、現実に本発明の二次電池ケース用アルミニウム合金板を製造する場合に、熱処理を加えることを否定するものではない。
The inventors of the present invention have studied the alloy composition, manufacturing conditions, particularly annealing conditions, and have found that the strength reduction due to laser welding can be recovered naturally or by performing low-temperature heat treatment.
That is, the aluminum alloy plate for a secondary battery case of the present invention has a Mn of 0.7 to 1.4% by mass, a Cu of 0.6 to 1.3% by mass, a Mg of 0.2 to 0.6% by mass, Fe is contained in excess of 0.4 to 1.0% by mass, and the balance is composed of inevitable impurities and Al. The aluminum alloy plate for a secondary battery case of the present invention has a tensile strength σs of 220 to 310 MPa, a difference between the tensile strength σs and the yield strength ys | σs−ys | of 20 MPa or less, and immediately after welding of the laser welded portion. When the tensile strength of σi (MPa) and the recovered tensile strength is σr (MPa), σr / σi ≧ 1.2 is satisfied. In addition, tensile strength (sigma) s and yield strength ys in this invention mean the tensile strength and yield strength as a raw material except a laser welding part. Further, σi and σr in the present invention are values specified based on laser welding conditions and tensile strength measurement conditions described in Examples described later. Further, “after recovery” means leaving after laser welding without performing any special treatment. However, when actually manufacturing the aluminum alloy plate for secondary battery cases of this invention, it does not deny adding heat processing.
本発明のアルミニウム合金板は、引張強さが２２０〜３１０ＭＰａ、引張強さと耐力との差（｜σｓ−ｙｓ｜）が２０ＭＰａ以下であることが好ましい。二次電池ケースに要求される機械的強度とプレス成形性を確保するためである。 The aluminum alloy plate of the present invention preferably has a tensile strength of 220 to 310 MPa and a difference between tensile strength and proof stress (| σs−ys |) of 20 MPa or less. This is to ensure the mechanical strength and press formability required for the secondary battery case.
以上の本発明による二次電池ケース用アルミニウム合金板は、以下の製造方法により製造される。すなわち本発明による二次電池ケース用アルミニウム合金板は、Ｍｎを０．７〜１．４質量％、Ｃｕを０．６〜１．３質量％、Ｍｇを０．２〜０．６質量％、Ｆｅを０．４超〜１．０質量％それぞれ含有し、残部が不可避的不純物及びＡｌからなる合金を鋳造し、熱間圧延、冷間圧延、中間焼鈍、安定化焼鈍及び最終冷間圧延の各工程を経て製造される。本発明の製造方法は、中間焼鈍の昇温速度を１０〜２５０℃／秒、保持温度を４５０〜５６０℃、保持時間を５〜６０秒、冷却速度を２０〜２５０℃／秒とし、安定化焼鈍の保持温度を６０〜２２０℃、保持時間を２〜８時間とし、さらに最終冷間圧延の圧下率を１０〜５０％になるように制御することを特徴とする。
上記組成を有し、かつ以上の中間焼鈍、安定化焼鈍及び最終冷間圧延の条件を満足することにより、プレス成形性、レーザ溶接性が優れ、かつレーザ溶接による強度低下が回復できる二次電池ケース用アルミニウム合金板が提供される。
The aluminum alloy plate for a secondary battery case according to the present invention described above is manufactured by the following manufacturing method. That is, the aluminum alloy plate for a secondary battery case according to the present invention has a Mn content of 0.7 to 1.4 mass%, a Cu content of 0.6 to 1.3 mass%, a Mg content of 0.2 to 0.6 mass%, Casting an alloy containing Fe in excess of 0.4 to 1.0% by mass, the balance being inevitable impurities and Al, hot rolling, cold rolling, intermediate annealing, stabilization annealing, and final cold rolling It is manufactured through each process. In the production method of the present invention, the temperature increase rate of the intermediate annealing is 10 to 250 ° C./second, the holding temperature is 450 to 560 ° C., the holding time is 5 to 60 seconds, and the cooling rate is 20 to 250 ° C./second. The annealing holding temperature is 60 to 220 ° C., the holding time is 2 to 8 hours, and the rolling reduction of the final cold rolling is controlled to be 10 to 50%.
A secondary battery having the above composition and satisfying the above conditions of intermediate annealing, stabilization annealing and final cold rolling, which is excellent in press formability and laser weldability and can recover the strength reduction due to laser welding. An aluminum alloy plate for a case is provided.
本発明によれば、プレス成形性、レーザ溶接性が優れ、かつレーザ溶接による強度低下が回復できる二次電池ケース用アルミニウム合金板が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the aluminum alloy plate for secondary battery cases which is excellent in press moldability and laser weldability, and can recover | recover the intensity | strength fall by laser welding is provided.
以下、実施の形態に基づいてこの発明を詳細に説明する。
＜合金組成＞
まず、二次電池ケース用アルミニウム合金板の合金組成について説明する。
＜Ｍｎ：０．７〜１．４質量％＞
Ｍｎは、Ａｌと結合して、鋳造時に晶出物粒子を形成する。この粒子らはプレス成形時の金型への焼きつきを防止し、成形性を高める効果がある。また、Ｍｎは、アルミニウム合金板の強度を高める効果がある。さらに、中間焼鈍時の再結晶粒の成長を抑制し、結晶粒微細化に寄与することによってプレス成形時の成形性を高める効果がある。
Ｍｎ含有量が０．７質量％未満では、上記効果が不十分となり、また、Ｍｎ含有量が１．４質量％を超えると、鋳造時に粗大な晶出物が生成しやすくなり、マトリックス中に分散してプレス成形性が低下する。そこで、本発明は、Ｍｎ含有量を０．７〜１．４質量％とする。好ましいＭｎ含有量は、０．８〜１．３質量％、より好ましいＭｎ含有量は、０．９〜１．２質量％である。
Hereinafter, the present invention will be described in detail based on embodiments.
<Alloy composition>
First, the alloy composition of the aluminum alloy plate for a secondary battery case will be described.
<Mn: 0.7 to 1.4% by mass>
Mn combines with Al to form crystallized particles during casting. These particles have the effect of preventing seizure on the mold during press molding and improving moldability. Further, Mn has an effect of increasing the strength of the aluminum alloy plate. Furthermore, it has the effect of suppressing the growth of recrystallized grains during intermediate annealing and improving the formability during press molding by contributing to refinement of crystal grains.
When the Mn content is less than 0.7% by mass, the above effects are insufficient, and when the Mn content exceeds 1.4% by mass, a coarse crystallized product is easily generated during casting, Disperse to reduce press formability. Then, this invention makes Mn content 0.7-1.4 mass%. A preferable Mn content is 0.8 to 1.3% by mass, and a more preferable Mn content is 0.9 to 1.2% by mass.
＜Ｃｕ：０．６〜１．３質量％＞
Ｃｕは、レーザ溶接後の溶接部強度の自然回復または低温熱処理による強度回復に寄与する主要元素であり、合金板の強度を高める効果がある。また、Ｃｕは高温クリープ特性を高め、耐膨れ性の向上に寄与する効果もある。
Ｃｕ含有量が０．６質量％未満では、それらの効果は不十分となり、Ｃｕ含有量が１．３質量％を超えると、プレス成形性が顕著に低下し、レーザ溶接時の熱間割れ感受性が増加する。そこで、本発明は、Ｃｕ含有量を０．６〜１．３質量％とする。好ましいＣｕ含有量は、０．８〜１．３質量％、より好ましいＣｕ含有量は、１．０〜１．２質量％である。
<Cu: 0.6 to 1.3% by mass>
Cu is a main element contributing to natural recovery of weld strength after laser welding or strength recovery by low-temperature heat treatment, and has an effect of increasing the strength of the alloy plate. Cu also has the effect of enhancing the high temperature creep characteristics and contributing to the improvement of blistering resistance.
If the Cu content is less than 0.6% by mass, these effects are insufficient, and if the Cu content exceeds 1.3% by mass, the press formability is remarkably lowered and the hot cracking susceptibility during laser welding is reduced. Will increase. Then, this invention makes Cu content 0.6-1.3 mass%. A preferable Cu content is 0.8 to 1.3% by mass, and a more preferable Cu content is 1.0 to 1.2% by mass.
＜Ｍｇ：０．２〜０．６質量％＞
Ｍｇは、Ｃｕと一緒に複合添加すると、レーザ溶接後の溶接部強度の自然回復または低温熱処理による強度回復を高める効果がある。また、アルミニウム合金板自身の強度とクリープ性を高め、耐膨れ性の向上に寄与する効果もある。
Ｍｇ含有量が０．２質量％未満では、それらの効果は不十分となり、Ｍｇ含有量が０．６質量％を超えると、レーザ溶接性とプレス成形性が低下する。好ましいＭｇ含有量は、０．２〜０．５質量％、より好ましいＭｇ含有量は、０．３〜０．５質量％である。
<Mg: 0.2-0.6% by mass>
When Mg is added together with Cu, it has the effect of increasing the strength recovery by low-temperature heat treatment or natural recovery of weld strength after laser welding. In addition, there is an effect that the strength and creep property of the aluminum alloy plate itself is increased and the bulging resistance is improved.
If the Mg content is less than 0.2% by mass, these effects are insufficient, and if the Mg content exceeds 0.6% by mass, the laser weldability and the press formability deteriorate. A preferable Mg content is 0.2 to 0.5% by mass, and a more preferable Mg content is 0.3 to 0.5% by mass.
＜Ｆｅ：０．４超〜１．０質量％＞
Ｆｅは、レーザ溶接時のレーザ吸収率を上げる効果があるために、同じ溶接速度でもより大きな溶け込み深さが得られる。
Ｆｅ含有量は０．４質量％以下では、この効果は不十分となり、１．０質量％を超えると、鋳造時に粗大なＦｅ系化合物粒子が発生しやすくなり、プレス成形性が劣化する恐れがある。好ましいＦｅ含有量は、０．５〜０．８質量％、より好ましいＦｅ含有量は、０．５５〜０．７５質量％である。
<Fe: more than 0.4 to 1.0 mass%>
Fe has the effect of increasing the laser absorptance during laser welding, so that a greater penetration depth can be obtained even at the same welding speed.
When the Fe content is 0.4% by mass or less, this effect is insufficient. When the Fe content exceeds 1.0% by mass, coarse Fe-based compound particles are likely to be generated during casting, and press moldability may be deteriorated. is there. A preferable Fe content is 0.5 to 0.8% by mass, and a more preferable Fe content is 0.55 to 0.75% by mass.
＜Ｓｉ：０．１質量％以下＞
Ｓｉは、不可避不純物として存在し、強度を若干高める効果がある。一方、Ｓｉは、レーザ溶接性を若干劣化させる。レーザ溶接性を満足できるのであれば、Ｓｉ含有量を制限する必要はないが、高いレーザ溶接性を要求される場合には、Ｓｉ含有量を０．１％以下に制限することが好ましい。
<Si: 0.1 mass% or less>
Si exists as an unavoidable impurity and has an effect of slightly increasing the strength. On the other hand, Si slightly degrades laser weldability. If the laser weldability can be satisfied, it is not necessary to limit the Si content. However, when high laser weldability is required, it is preferable to limit the Si content to 0.1% or less.
引張強さが２２０〜３１０ＭＰａという制限理由は、引張強さが２２０ＭＰａより低いと、ケース自体の耐圧能力が低下し、３１０ＭＰａを超えると、プレス成形性が落ちるためである。
引張強さと耐力との差が２０ＭＰａ以下という制限理由は、この差が２０ＭＰａを超えると、加工硬化が高くなりすぎて、多段プレス時の成形性が劣るためである。
The reason for limiting the tensile strength to 220 to 310 MPa is that if the tensile strength is lower than 220 MPa, the pressure resistance of the case itself decreases, and if it exceeds 310 MPa, the press formability decreases.
The reason why the difference between the tensile strength and the proof stress is 20 MPa or less is that when this difference exceeds 20 MPa, work hardening becomes too high and the formability during multi-stage pressing is poor.
次に、本発明の製造方法について説明する。
本発明のアルミニウム合金板は、鋳造、均質化処理、熱間圧延、冷間圧延、中間焼鈍、安定化焼鈍、及び最終冷間圧延の各工程を経て製造される。
中間焼鈍は、昇温速度が１０〜２５０℃／秒、保持（焼鈍）温度が４５０〜５６０℃、保持時間が５〜６０秒、冷却速度が２０〜２５０℃／秒になるように制御される。また、安定化焼鈍は、保持（焼鈍）温度が６０〜２２０℃、保持時間が２〜８時間になるように制御される。また、最終冷間圧延工程は、圧下率が１０〜５０％になるように制御される。
Next, the manufacturing method of this invention is demonstrated.
The aluminum alloy sheet of the present invention is manufactured through each process of casting, homogenization treatment, hot rolling, cold rolling, intermediate annealing, stabilization annealing, and final cold rolling.
The intermediate annealing is controlled such that the heating rate is 10 to 250 ° C./second, the holding (annealing) temperature is 450 to 560 ° C., the holding time is 5 to 60 seconds, and the cooling rate is 20 to 250 ° C./second. . Further, the stabilization annealing is controlled so that the holding (annealing) temperature is 60 to 220 ° C. and the holding time is 2 to 8 hours. Further, the final cold rolling process is controlled so that the rolling reduction is 10 to 50%.
＜中間焼鈍＞
中間焼鈍の昇温速度が１０℃／秒より遅いと、その前の冷間圧延時に導入された蓄積エネルギーが解放されるために、再結晶核生成率が低下して、焼鈍後の結晶粒径が大きくなり、プレス成形性が劣る恐れがある。工業的生産規模で昇温速度が２５０℃／秒を超えるためには、高価な設備投入が必要となり、生産コストが増加する。したがって、中間焼鈍の昇温速度は１０〜２５０℃／秒とし、好ましくは５０〜２００℃／秒とし、より好ましくは７０〜１５０℃／秒とする。
中間焼鈍における保持温度が４５０℃より低いと、ＣｕやＭｇの固溶量が減り、アルミニウム合金板自身の引張強さが低下する。また、レーザ溶接部の引張強さの回復度合いも低下し、σｒ／σｉ≧１．２を満足できなくなる恐れがある。保持温度が５６０℃より高くなると、アルミニウム合金板に局部溶融が発生し、プレス成形性が大幅に劣化する可能性がある。したがって、中間焼鈍の保持温度は４５０〜５６０℃とし、好ましくは４８０〜５５０℃とし、より好ましくは５００〜５５０℃とする。
<Intermediate annealing>
If the temperature increase rate of the intermediate annealing is slower than 10 ° C./second, the stored energy introduced during the previous cold rolling is released, so the recrystallization nucleation rate decreases, and the crystal grain size after annealing May increase and press formability may be inferior. In order to increase the rate of temperature increase over 250 ° C./second on an industrial production scale, it is necessary to input expensive equipment and increase the production cost. Therefore, the temperature increase rate of the intermediate annealing is 10 to 250 ° C./second, preferably 50 to 200 ° C./second, more preferably 70 to 150 ° C./second.
When the holding temperature in intermediate annealing is lower than 450 ° C., the amount of Cu and Mg dissolved decreases, and the tensile strength of the aluminum alloy plate itself decreases. In addition, the degree of recovery of the tensile strength of the laser welded portion also decreases, and there is a possibility that σr / σi ≧ 1.2 cannot be satisfied. When the holding temperature is higher than 560 ° C., local melting occurs in the aluminum alloy plate, and press formability may be significantly deteriorated. Therefore, the holding temperature of the intermediate annealing is 450 to 560 ° C, preferably 480 to 550 ° C, more preferably 500 to 550 ° C.
中間焼鈍の保持時間が５秒より短くなると、ＣｕやＭｇの固溶が不十分となり、アルミニウム合金板自身の引張強さの低下、および蓋とのレーザ溶接部の引張強さの回復度合いの低下が生じる。保持時間が６０秒より長くなると、結晶粒が大きくなりすぎで、プレス成形性が劣化する恐れがある。したがって、中間焼鈍の保持時間は５〜６０秒とし、好ましくは１０〜５０秒とし、より好ましくは１５〜３５秒とする。
中間焼鈍時の冷却速度が２０℃／秒より遅いと、冷却中にＣｕとＭｇが析出してしまい、アルミニウム合金板自身の引張強さの低下、および蓋とのレーザ溶接部の引張強さの回復度合いの低下をもたらすために好ましくない。冷却速度が２５０℃／秒を超えると、冷却用の設備投資が増し、生産コストが増加する。したがって、中間焼鈍の降温速度は２０〜２５０℃／秒とし、好ましくは５０〜２００℃／秒とし、より好ましくは７０〜１５０℃／秒とする。
If the holding time of the intermediate annealing is shorter than 5 seconds, the solid solution of Cu and Mg becomes insufficient, the tensile strength of the aluminum alloy plate itself decreases, and the recovery degree of the tensile strength of the laser welded portion with the lid decreases. Occurs. If the holding time is longer than 60 seconds, the crystal grains become too large, and the press formability may deteriorate. Therefore, the holding time of the intermediate annealing is 5 to 60 seconds, preferably 10 to 50 seconds, and more preferably 15 to 35 seconds.
If the cooling rate during the intermediate annealing is slower than 20 ° C./second, Cu and Mg are precipitated during cooling, and the tensile strength of the laser welded portion with the lid is lowered due to the decrease in the tensile strength of the aluminum alloy plate itself. This is not preferable because it causes a reduction in the degree of recovery. When the cooling rate exceeds 250 ° C./second, the capital investment for cooling increases and the production cost increases. Therefore, the temperature decrease rate of the intermediate annealing is 20 to 250 ° C./second, preferably 50 to 200 ° C./second, more preferably 70 to 150 ° C./second.
＜安定化焼鈍＞
中間焼鈍に続いて安定化焼鈍を行う。安定化焼鈍は、保持温度を６０〜２２０℃、保持時間を２〜８時間とする。この安定化焼鈍を施さないと、最終圧延後の室温保管時に板の引張強さが緩やかに上昇し、プレス成形時の生産管理が難しくなる恐れがある。さらに、最終圧延後の室温保管時の時間が長くなると、引張強さが上昇すると同時に耐力の低下も生じて、プレス成形性が顕著に劣化することがある。安定化焼鈍は、一般には最終冷間圧延後に実施することになるが、本発明の場合、中間焼鈍後、最終冷間圧延前に行うことにする。これは、最終冷間圧延後に行うと、引張強さが高すぎるか又は耐力が低すぎてしまい、引張強さと耐力との差が大きくなりすぎてプレス成形性が劣化するためである。
保持温度が６０℃未満、保持時間が２時間未満では、緩やかな引張強さの上昇と耐力の低下を充分に抑制できない恐れがある。一方、保持温度が２２０℃超、保持時間が８時間超では、引張強さの低下幅が大きすぎる。安定化焼鈍の保持温度、保持時間は、保持温度を１００〜２００℃、保持時間を３〜５時間に制御することが好ましく、保持温度を１２０〜１８０℃、保持時間を３．５〜４．５時間に制御することがより好ましい。
<Stabilized annealing>
Stabilization annealing is performed following the intermediate annealing. In the stabilization annealing, the holding temperature is 60 to 220 ° C. and the holding time is 2 to 8 hours. If this stabilization annealing is not performed, the tensile strength of the plate gradually increases during storage at room temperature after final rolling, and production management during press forming may be difficult. Furthermore, if the time at room temperature storage after the final rolling becomes longer, the tensile strength increases and at the same time the proof stress decreases, and the press formability may deteriorate significantly. Stabilization annealing is generally performed after the final cold rolling, but in the case of the present invention, it is performed after the intermediate annealing and before the final cold rolling. This is because, if performed after the final cold rolling, the tensile strength is too high or the proof stress is too low, and the difference between the tensile strength and the proof strength becomes too large and press formability deteriorates.
When the holding temperature is less than 60 ° C. and the holding time is less than 2 hours, there is a possibility that a moderate increase in tensile strength and a decrease in yield strength cannot be sufficiently suppressed. On the other hand, if the holding temperature exceeds 220 ° C. and the holding time exceeds 8 hours, the range of decrease in tensile strength is too large. With respect to the holding temperature and holding time of the stabilization annealing, it is preferable to control the holding temperature to 100 to 200 ° C. and the holding time to 3 to 5 hours, the holding temperature to 120 to 180 ° C., and the holding time to 3.5 to 4. It is more preferable to control to 5 hours.
＜最終冷間圧延＞
最終冷間圧延工程の圧下率は１０〜５０％になるように制御することが好ましい。圧下率が１０％未満では、引張強さと耐力との差が大きくなりすぎるために、多段絞りするプレス成形性が劣る。圧下率が５０％を超えると、引張強さが高くなりすぎて、プレス成形ができない恐れがある。最終冷間圧延における圧下率は、１５〜４０％に制御することが好ましく、２０〜３０％に制御することがより好ましい。
<Final cold rolling>
It is preferable to control the rolling reduction in the final cold rolling step to be 10 to 50%. If the rolling reduction is less than 10%, the difference between the tensile strength and the proof stress becomes too large, so that the press formability for multistage drawing is inferior. If the rolling reduction exceeds 50%, the tensile strength becomes too high and press molding may not be possible. The rolling reduction in the final cold rolling is preferably controlled to 15 to 40%, more preferably 20 to 30%.
以下に実施例及び比較例によって本発明を説明する。
（第１実施例）
表１の試料Ｎｏ.１〜５に示す成分（質量％）のアルミニウム合金を、鋳造、均質化処理、熱間圧延、冷間圧延の各工程によって０．６６ｍｍの板材にした後に、以下の条件の中間焼鈍、安定化焼鈍を行い、その後、厚さ０．５５ｍｍまで最終冷間圧延した。最終冷間圧延の際の圧下率は１６．６％である。
中間焼鈍
昇温速度：１００℃／秒、保持温度：５２０℃、保持時間：２５秒、冷却速度：１５０℃／秒
安定化焼鈍
保持温度：１６０℃、保持時間：４時間
The present invention will be described below with reference to examples and comparative examples.
(First embodiment)
After making the aluminum alloy of the component (mass%) shown in sample Nos. 1 to 5 in Table 1 into a plate material of 0.66 mm by each step of casting, homogenization treatment, hot rolling, and cold rolling, the following conditions are satisfied. Were subjected to intermediate annealing and stabilization annealing, and then the final cold rolling to a thickness of 0.55 mm. The rolling reduction during the final cold rolling is 16.6%.
Intermediate annealing Temperature rising rate: 100 ° C./second, Holding temperature: 520 ° C., Holding time: 25 seconds, Cooling rate: 150 ° C./second Stabilized annealing Holding temperature: 160 ° C., Holding time: 4 hours
（第１比較例）
表１の試料Ｎｏ.１〜５に示す成分組成となるようにした他は、上記第１実施例と同様の方法により、アルミニウム合金板を製造した。最終冷間圧延の際の圧下率は１６．６％であった。
(First comparative example)
An aluminum alloy plate was produced by the same method as in the first example except that the component compositions shown in Sample Nos. 1 to 5 in Table 1 were used. The rolling reduction during the final cold rolling was 16.6%.
以上のアルミニウム合金板（試料）について、下記の評価方法により特性評価を行った。その結果を表２に示す。
＜各特性の評価方法＞
引張強さ，耐力：ＪＩＳ５号試験片を採取し、ＪＩＳ Ｚ ２２４１に定めた方法による引張試験を行って測定し、引張強さσｓと耐力ｙｓとの差（｜σｓ−ｙｓ｜）を求めた。
σｒ／σｉ（レーザ溶接部の溶接直後と回復後の引張強さ）：アルミニウム合金板（試料）上に直線状溶接ビードを作り出した後に、長手方向がこの溶接ビードに垂直、且つ溶接ビードが平行部の長手方向の中央になるようにＪＩＳ５号試験片を作製して引張試験を行って測定した。また、溶接部の強度回復は、レーザ溶接後の約１０日間でほぼ飽和状態になるために、引張試験はレーザ溶接直後と溶接後の１２日目で行うようにした。このレーザ溶接にはＬＤ励起のベースレーザにランプ励起パルスレーザを付加したハイブリッド形の溶接機を用いた。ＬＤ励起レーザの最大平均出力が約２５Ｗ、ランプ励起レーザの最大平均出力が約２５０Ｗである。溶接速度が２５ｍｍ／ｓｅｃ、パルスＨｚが１４０ｐｐｓ、パルス波形が（１．０＋２．０５＋２．００＋１．９５＋１．９０＋１．８５＋１．８０＋１．７５＋１．７０＋１．６５＋１．６０＋１．５０＋１．４０＋１．３０＋１．２０＋１．１０＋１．０５＋１．００＋０．９５＋０．９０）ｋｗ×０．０５ｍｓという溶接条件を用いた。
プレス成形性：径６９．３ｍｍのブランク、径４０ｍｍ、３３ｍｍの２種類のポンチを使用して２段絞りを行って、割れの発生がなく成形できたものを○、割れが発生したものを×として評価した。
レーザ溶接性：上記と同様なレーザ溶接機と溶接条件を用いて、突合せ法によって本発明のアルミニウム合金板を溶接して、割れ、ポロシティ、溶け込み不良などの溶接欠陥がないものを○、あるものを×として評価した。
About the above aluminum alloy plate (sample), the characteristic evaluation was performed with the following evaluation method. The results are shown in Table 2.
<Evaluation method of each characteristic>
Tensile strength, yield strength: JIS No. 5 test piece was sampled and measured by conducting a tensile test according to the method defined in JIS Z 2241 to obtain the difference (| σs−ys |) between the tensile strength σs and the yield strength ys. .
σr / σi (Tensile strength immediately after welding and recovery after laser welding): After creating a linear weld bead on an aluminum alloy plate (sample), the longitudinal direction is perpendicular to the weld bead and the weld bead is parallel A JIS No. 5 test piece was prepared so as to be in the center in the longitudinal direction of the part, and a tensile test was performed for measurement. In addition, since the strength recovery of the welded portion is almost saturated in about 10 days after laser welding, the tensile test was performed immediately after laser welding and on the 12th day after welding. For this laser welding, a hybrid welding machine in which a lamp excitation pulse laser was added to an LD excitation base laser was used. The maximum average power of the LD pump laser is about 25 W, and the maximum average power of the lamp pump laser is about 250 W. The welding speed is 25 mm / sec, the pulse Hz is 140 pps, and the pulse waveform is (1.0 + 2.05 + 2.00 + 1.95 + 1.90 + 1.85 + 1.80 + 1.75 + 1.70 + 1.65 + 1.60 + 1.50 + 1.40 + 1.30 + 1.20 + 1.10 + 1.10). 05 + 1.00 + 0.95 + 0.90) kw × 0.05 ms welding conditions were used.
Press formability: Two-stage drawing using a blank with a diameter of 69.3 mm and two types of punches with a diameter of 40 mm and 33 mm. As evaluated.
Laser weldability: Using the same laser welding machine and welding conditions as described above, the aluminum alloy plate of the present invention is welded by the butt method, and there are no weld defects such as cracks, porosity, penetration defects, etc. Was evaluated as x.
（第２実施例）
表１の第１実施例の試料Ｎｏ．２と同じ成分、同じ鋳造、均質化処理、熱間圧延、冷間圧延の工程で、厚さ０．６６ｍｍ（試料ａ）と厚さ０．７８ｍｍ（試料ｂ）の２種類のアルミニウム合金板を作製した。
試料ａについては、表３の試料Ｎｏ.６〜９に示す条件で中間焼鈍、および安定化焼鈍を行い、その後、厚さ０．４５ｍｍまで最終圧延した。また、試料ｂについては、表３の試料Ｎｏ.１０に示す条件で中間焼鈍、および安定化焼鈍を行い、その後、厚さ０．４５ｍｍまで最終圧延した。この時の最終冷間圧延の圧下率は、試料Ｎｏ.６〜９が３１．８％、試料Ｎｏ.１０が４２．３％である。
(Second embodiment)
Sample No. 1 of the first embodiment in Table 1 was used. 2 kinds of aluminum alloy plates having a thickness of 0.66 mm (sample a) and a thickness of 0.78 mm (sample b) in the same components, the same casting, homogenization treatment, hot rolling and cold rolling processes. Produced.
Sample a was subjected to intermediate annealing and stabilization annealing under the conditions shown in Sample Nos. 6 to 9 in Table 3, and then final rolled to a thickness of 0.45 mm. Moreover, about the sample b, the intermediate annealing and the stabilization annealing were performed on the conditions shown in sample No. 10 of Table 3, and the final rolling was carried out to thickness 0.45mm after that. The reduction ratio of the final cold rolling at this time is 31.8% for sample Nos. 6 to 9, and 42.3% for sample No. 10.
（第２比較例）
また、表１に示した比較例１と同じ成分、同じ鋳造、均質化処理、熱間圧延、冷間圧延の工程で０．６５ｍｍ板を作製した後に、表３の試料Ｎｏ．６，７に示す条件で中間焼鈍を行い、厚さ０．４５ｍｍまで最終圧延してアルミニウム合金板を作製した。この時の最終冷間圧延の際の圧下率は３０．８％であった。
(Second comparative example)
Further, after producing a 0.65 mm plate by the same components, the same casting, homogenization treatment, hot rolling, and cold rolling steps as those in Comparative Example 1 shown in Table 1, Sample No. Intermediate annealing was performed under the conditions shown in 6 and 7, and final rolling was performed to a thickness of 0.45 mm to produce an aluminum alloy plate. At this time, the rolling reduction during the final cold rolling was 30.8%.
第２実施例、第２比較例についても、第１実施例等と同様にアルミニウム合金板の各特性評価を行った。その結果を表４に示す。 For the second example and the second comparative example, each characteristic evaluation of the aluminum alloy plate was performed in the same manner as in the first example. The results are shown in Table 4.
以上の表１〜４で示すように、本発明に従って製造したアルミニウム合金板（第１実施例 試料Ｎｏ．１〜５，第２実施例 試料Ｎｏ．６〜１０）は全て、適切な引張強さを有しており、良好なプレス成形性およびレーザ溶接性を示し、溶接後の溶接部強度の回復が大きくなっている。これにより、第１実施例 試料Ｎｏ．１〜５，第２実施例 試料Ｎｏ．６〜１０は、二次電池ケース用アルミニウム合金板として適切なものと判断される。
一方、本発明の合金組成範囲、または製造条件範囲からはずれた第１比較例 試料Ｎｏ．１〜５，第２比較例 試料Ｎｏ６、７のアルミニウム合金板では、引張強さが低すぎるか、成形性またはレーザ溶接性が劣って、溶接部の強度回復が不十分となっている。これより、第１比較例 試料Ｎｏ．１〜５，第２比較例 試料Ｎｏ６、７のアルミニウム合金板は、二次電池ケース用アルミニウム合金板としては、本発明に比べ、劣ったものと判断される。
As shown in the above Tables 1 to 4, all the aluminum alloy plates (first example sample No. 1 to 5, second example sample No. 6 to 10) manufactured according to the present invention have appropriate tensile strength. It has good press formability and laser weldability, and the recovery of the weld strength after welding is large. As a result, sample No. 1 to 5, Second Example Sample No. 6-10 are judged to be suitable as the aluminum alloy plate for the secondary battery case.
On the other hand, the first comparative example sample No. 1 deviated from the alloy composition range or manufacturing condition range of the present invention. 1-5, 2nd comparative example In the aluminum alloy plate of sample Nos. 6 and 7, tensile strength is too low, or formability or laser weldability is inferior, and strength recovery of a welded part is insufficient. Thus, the first comparative example Sample No. 1-5, 2nd Comparative Example It is judged that the aluminum alloy plate of sample No. 6 and 7 was inferior to this invention as an aluminum alloy plate for secondary battery cases.
（第３比較例）
さらに比較例８として、一般的な製造工程のように安定化焼鈍を最終冷間圧延後に行ってアルミニウム合金板を作製した。具体的には、表１の第１実施例の試料Ｎｏ．２と同じ成分、同じ鋳造、均質化処理、熱間圧延、冷間圧延の工程で、厚さ０．６６ｍｍのアルミニウム合金板を作製した後に、昇温速度１００℃／秒、保持温度５００℃、保持時間２５秒、冷却速度１５０℃／秒の条件で中間焼鈍を行い、０．４５ｍｍまで最終冷間圧延して焼鈍温度１６０℃、保持時間４時間の条件で安定化焼鈍を施した。
第３比較例についても、第１実施例等と同様にアルミニウム合金板の各特性評価を行った。その結果を表５に示す。
(Third comparative example)
Further, as Comparative Example 8, the stabilized annealing was performed after the final cold rolling as in a general manufacturing process to produce an aluminum alloy plate. Specifically, the sample No. 1 of the first embodiment in Table 1 is used. After producing an aluminum alloy plate having a thickness of 0.66 mm in the same components, the same casting, homogenization treatment, hot rolling, and cold rolling, the heating rate is 100 ° C./second, the holding temperature is 500 ° C., Intermediate annealing was performed under the conditions of a holding time of 25 seconds and a cooling rate of 150 ° C./second, and finally cold-rolled to 0.45 mm and subjected to stabilization annealing under the conditions of an annealing temperature of 160 ° C. and a holding time of 4 hours.
For the third comparative example, each characteristic evaluation of the aluminum alloy plate was performed in the same manner as in the first example. The results are shown in Table 5.
Claims (2)
引張強さσｓが２２０〜３１０ＭＰａ、前記引張強さσｓと耐力ｙｓとの差｜σｓ−ｙｓ｜が２０ＭＰａ以下であり、
レーザ溶接部の溶接直後の引張強さをσｉ（ＭＰａ）、回復後の引張強さをσｒ（ＭＰａ）とすると、σｒ／σｉ≧１．２を満足することを特徴とする二次電池ケース用アルミニウム合金板。 Containing 0.7 to 1.4 mass% Mn, 0.6 to 1.3 mass% Cu, 0.2 to 0.6 mass% Mg, and more than 0.4 to 1.0 mass% Fe And the balance consists of an aluminum alloy plate made of inevitable impurities and Al,
The tensile strength σs is 220 to 310 MPa, the difference | σs−ys | between the tensile strength σs and the yield strength ys is 20 MPa or less,
For a secondary battery case characterized in that σr / σi ≧ 1.2 is satisfied, where σi (MPa) is the tensile strength immediately after welding of the laser weld and σr (MPa) is the tensile strength after recovery. Aluminum alloy plate.
中間焼鈍の昇温速度を１０〜２５０℃／秒、保持温度を４５０〜５６０℃、保持時間を５〜６０秒、冷却速度を２０〜２５０℃／秒とし、
安定化焼鈍の保持温度を６０〜２２０℃、保持時間を２〜８時間とし、
最終冷間圧延の圧下率を１０〜５０％とすることを特徴とする二次電池ケース用アルミニウム合金板の製造方法。 Containing 0.7 to 1.4 mass% Mn, 0.6 to 1.3 mass% Cu, 0.2 to 0.6 mass% Mg, and more than 0.4 to 1.0 mass% Fe In the method of producing an aluminum alloy sheet for a secondary battery case by casting an alloy consisting of the inevitable impurities and Al, the remainder being subjected to hot rolling, cold rolling, intermediate annealing, stabilization annealing and final cold rolling. There,
The temperature increase rate of the intermediate annealing is 10 to 250 ° C./second, the holding temperature is 450 to 560 ° C., the holding time is 5 to 60 seconds, the cooling rate is 20 to 250 ° C./second,
The holding temperature of stabilization annealing is 60 to 220 ° C., the holding time is 2 to 8 hours,
A method for producing an aluminum alloy plate for a secondary battery case, wherein the rolling reduction of the final cold rolling is 10 to 50%.
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