JP2008261008A - Aluminum alloy sheet for battery cover and its production method - Google Patents
Aluminum alloy sheet for battery cover and its production method Download PDFInfo
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 238000000137 annealing Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 238000005096 rolling process Methods 0.000 claims description 17
- 238000005097 cold rolling Methods 0.000 claims description 9
- 238000000265 homogenisation Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 238000004880 explosion Methods 0.000 abstract 1
- 230000003449 preventive effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 238000000465 moulding Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005098 hot rolling Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910018191 Al—Fe—Si Inorganic materials 0.000 description 1
- 229910018575 Al—Ti Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/02—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
- B21B2001/221—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length by cold-rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
- B21B2001/225—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length by hot-rolling
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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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
本発明は、電池の蓋に用いられるアルミニウム合金板であって、当該蓋をプレス加工で成形したまま焼鈍処理を施さなくても所要の耐圧強度を発揮する電池蓋が得られるアルミニウム合金板及びその製造方法に関する。 The present invention relates to an aluminum alloy plate used for a battery lid, and an aluminum alloy plate capable of obtaining a battery lid that exhibits a required pressure strength without being subjected to an annealing process while the lid is molded by press working, and the aluminum alloy plate It relates to a manufacturing method.
携帯電話等の移動機器に使用される電池には、軽量化の観点から、アルミニウム又はアルミニウム合金製のケース内に電解物質を収容した充放電可能な密閉型電池が多用されている。
しかし、このような充放電可能な密閉型電池は、従来、過充電された場合や過日射された場合等に、電池内部の温度が上昇し、電池ケース壁や電池ケースと蓋との溶接部等が破壊し、内部の液が漏れたりする虞がある等の問題点があった。
As a battery used for a mobile device such as a mobile phone, a chargeable / dischargeable sealed battery in which an electrolytic substance is housed in an aluminum or aluminum alloy case is frequently used from the viewpoint of weight reduction.
However, such a chargeable / dischargeable sealed battery has hitherto been a case where the temperature inside the battery rises when it is overcharged or exposed to excessive sunlight, and the battery case wall or the welded portion between the battery case and the lid. There is a problem that the internal liquid may break down and the liquid inside may leak.
ところで、例えば、携帯電話用のリチウムイオン２次電池のケースは断面が矩形で、厚さが薄く、幅が広く、深さの深い形状をしている。具体的な寸法を示せば内法で厚さ４〜７ｍｍ×幅２０〜３０×深さ４０〜６０ｍｍの形状となっている。このため、このような電池ケース用の板材は、絞り加工やしごき加工（ＤＩ加工ともいう）による加工性の良さを必須条件としている。
また、将来の自動車等の大型移動機器に使用される電池は、上記寸法の各辺を２〜１０倍程度としたものを幾つか積層させた使用形態が考えられている。
By the way, for example, a case of a lithium ion secondary battery for a cellular phone has a rectangular cross section, a thin thickness, a wide width, and a deep shape. If a specific dimension is shown, it will become the shape of thickness 4-7mm x width 20-30x depth 40-60mm by the internal method. For this reason, such a plate material for a battery case is required to have good workability by drawing or ironing (also referred to as DI processing).
Moreover, the battery used for large-sized mobile devices, such as a motor vehicle of the future, is considered to have a usage pattern in which several batteries each having a side of about 2 to 10 times the above dimensions are stacked.
このように、電池ケース用の材料には、ＤＩ加工容易で、かつ、軽量性，高強度性，加工性が要求されている。そして、このような性質を満たすものとして、例えば特許文献１には、Ｍｎ：０.８〜２.０質量％，Ｆｅ：０.６質量％以下，Ｓｉ：０.３質量％以下、残部がＡｌからなるＡ３００３系アルミニウム合金板が提案されており、また特許文献２には、Ｍｎ：０．３〜１.５質量％，Ｆｅ：１.６超〜１.８質量％、残部がＡｌからなるアルミニウム合金板が提案されている。 As described above, the material for the battery case is required to be easily DI processed and to have lightness, high strength, and workability. And as what satisfy | fills such a property, for example, in patent document 1, Mn: 0.8-2.0 mass%, Fe: 0.6 mass% or less, Si: 0.3 mass% or less, remainder is An A3003-based aluminum alloy plate made of Al has been proposed, and in Patent Document 2, Mn: 0.3 to 1.5% by mass, Fe: more than 1.6 to 1.8% by mass, and the balance from Al An aluminum alloy plate has been proposed.
近年においては、素材のみならず、電池ケースの形状・構造を工夫し、上記破壊事故が生じる前に、一定の内圧がかかった場合に電池蓋の特定箇所が破壊し、自己が未然に防がれるような防爆機能を備えたものが提案されている（特許文献３参照）。防爆部は規格的には種々あるとしても、厚さ２０μｍ程度で通常３ＭＰａ程度を目安に防爆部の耐圧強度を定め、その近傍の圧力で防爆部が破壊するように形作られている。
より具体的には、電池蓋に一定の開口部を設け、かつ、この開口部に電池ケースよりも破断圧力の低いアルミニウム箔を張ることにより、電池ケースに防爆機能を備えたものが提案されている。そして、上記特許文献３によれば、電池蓋の開口部に防爆部として金属薄板を張る方法を採用しているので、この金属薄板の板厚チェックを行う必要がなく、検査にかかるコストも大幅に削減できるという優れた効果があるとしている。
In recent years, not only the materials but also the shape and structure of the battery case have been devised, and if a certain internal pressure is applied before the above-mentioned destruction accident occurs, a specific part of the battery lid is destroyed, preventing self-prevention. A device having an explosion-proof function is proposed (see Patent Document 3). Even if there are various types of explosion-proof parts, the pressure-proof strength of the explosion-proof part is determined with a thickness of about 20 μm and usually about 3 MPa as a guide, and the explosion-proof part is destroyed by the pressure in the vicinity.
More specifically, a battery case with an explosion-proof function has been proposed by providing a certain opening in the battery lid and stretching an aluminum foil having a lower rupture pressure than the battery case in the opening. Yes. And according to the above-mentioned
しかしながら、特許文献３で提案された手法では、防爆部としての金属薄板を張る工程が別途必要となるため、製造工程が増すとともに、当該金属薄板の板厚チェックを行う必要がないとはいえ適度に密着しているかどうかを別途検査しなければならないといった問題点も生じてくる。すなわち、電池全体を製造する上で、製造工程が増えるため、作業性が悪いという問題がある。
そこで、本発明者等は、アルミニウム合金板を素材としてプレス加工により、防爆部を備えた電池用蓋を一体成形することとした。
Accordingly, the present inventors have integrally formed a battery lid provided with an explosion-proof portion by press working using an aluminum alloy plate as a raw material.
しかしながら、電池ケースに被せる蓋に、プレス加工により肉薄の防爆部を一体的に形成しようとするとき、当該防爆部は均一の厚さで成形され、所要の耐圧強度を有することが望まれる。しかも、電池ケース蓋のように細かい部品を冷間でのプレス加工で製造しようとするとき、各部位の成形精度を高める必要があるばかりでなく、全体的に均質な製品とするべく品質管理が必要となる。さらに加工後に焼鈍工程を付加しようとすると、手間がかかるのみならず品質にバラツキが生じやすくなる。
本発明は、このような問題を解消すべく案出されたものであり、アルミニウム合金板を素材として電池ケース用の蓋を製造する際、焼鈍工程を採用することなしに、薄肉の防爆部をも一体的にプレス加工で得ることができる電池蓋用アルミニウム合金板を提供することを目的とする。
However, when a thin explosion-proof part is integrally formed on the lid that covers the battery case by pressing, it is desired that the explosion-proof part is formed with a uniform thickness and has a required pressure resistance. In addition, when trying to manufacture small parts such as battery case lids by cold pressing, it is not only necessary to improve the molding accuracy of each part, but also quality control is performed to make the product homogeneous throughout. Necessary. Further, if an annealing process is to be added after processing, not only labor is required, but also the quality tends to vary.
The present invention has been devised to solve such problems, and when manufacturing a lid for a battery case using an aluminum alloy plate as a raw material, a thin-walled explosion-proof portion is formed without employing an annealing process. Another object of the present invention is to provide an aluminum alloy plate for a battery lid that can be obtained integrally by pressing.
本発明の電池蓋用アルミニウム合金板は、その目的を達成するため、Ｆｅ：１.１５〜１.３５質量％，Ｍｎ：０.４０〜０.６０質量％，残部Ａｌと不純物とからなり、不純物としてのＳｉが０.０５質量％以下，Ｃｕが０.０５質量％以下，Ｍｇが０.０５質量％以下に規制された組成と、圧延面において、圧延方向に直角な方向における結晶粒の最大幅が１００μｍ以下，結晶粒の幅の平均が２５μｍ以下の組織を有することを特徴とする。
本発明の電池蓋用アルミニウム合金板は、さらに、Ｔｉ：０.００５〜０.１５質量％、又はＴｉ：０.００５〜０.１５質量％とＢ：０．０００５〜０.０５質量％を含有するものであっても良い。
In order to achieve the object, the aluminum alloy plate for a battery lid of the present invention comprises Fe: 1.15 to 1.35% by mass, Mn: 0.40 to 0.60% by mass, the balance Al and impurities. The composition in which Si as an impurity is controlled to 0.05 mass% or less, Cu is 0.05 mass% or less, and Mg is 0.05 mass% or less, and the crystal grains in a direction perpendicular to the rolling direction on the rolling surface It has a structure having a maximum width of 100 μm or less and an average crystal grain width of 25 μm or less.
The aluminum alloy plate for a battery lid of the present invention further includes Ti: 0.005-0.15 mass%, or Ti: 0.005-0.15 mass% and B: 0.0005-0.05 mass%. It may be contained.
このような微細構造を有するアルミニウム合金板は、上記成分組成を有するアルミニウム合金鋳塊に５３０〜６２０℃×１時間以上の条件で均質化処理を施した後、熱延し、さらに、４０％以上の圧延率で冷延した後に、１℃／秒以上の平均昇温速度で３５０〜５５０℃の範囲内の温度に加熱して保持無し若しくは１０分以下の保持を行って、１℃／秒以上の平均冷却速度となる条件で焼鈍を施すことにより製造される。
焼鈍後、さらに冷延を施してもよい。
The aluminum alloy plate having such a fine structure is subjected to homogenization treatment at 530 to 620 ° C. for 1 hour or more on the aluminum alloy ingot having the above component composition, and then hot rolled, and further 40% or more. After cold rolling at a rolling rate of 1 ° C./second or more, heating to a temperature in the range of 350 to 550 ° C. at an average temperature increase rate of 1 ° C./second or more and holding for 10 minutes or less It is manufactured by performing annealing under conditions that provide an average cooling rate.
After annealing, cold rolling may be further performed.
本発明により提供される電池蓋用アルミニウム合金板は、成分組成が規定されているとともに、粗大結晶粒がなく、微細な結晶粒で構成されているために、所望の耐圧強度を呈するとともに、耐圧強度のバラツキが小さくなっている。このため、プレス成形性に優れ、一体成形しても薄肉の防爆部を精度よく成形することができる。しかも、冷間でのプレス成形後に焼鈍工程を付加しなくてもよいので、安定した品質の電池用蓋を低コストで大量生産することが可能になる。 The aluminum alloy plate for a battery lid provided by the present invention has a specified composition and is composed of fine crystal grains without coarse crystal grains. The intensity variation is small. For this reason, it is excellent in press formability, and a thin-walled explosion-proof part can be accurately formed even if it is integrally formed. In addition, since it is not necessary to add an annealing process after cold press forming, it is possible to mass-produce stable quality battery covers at low cost.
まず、本発明で提供されるアルミニウム合金板が用いられる電池ケース及びその蓋について説明する。
図１は蓋を備えた電池の断面を模式的に表した概略図であり、図２は電池の蓋上面を模式的に表した概略図である。図中、１は密閉型電池、２は電池ケース、３は本発明アルミニウム合金板で形作られた蓋である。４は、電池ケース内に収容されている電解物質で、例えばリチウムイオンが媒体となっている電解物質、５は電池の＋端子、６は＋端子５の周囲を取巻いている絶縁体、７は＋端子へ通じるリード線、８は−端子へ通じるリード線で、これにより電池蓋３が−端子とされる。また、９電解物質４の注入口で注入後は閉止される。１０は＋端子５の取付孔、１１は本明細書中で問題とされている防爆部、１２は電池蓋３と電池ケース２とを周囲密閉接合した溶接部である。
First, a battery case in which the aluminum alloy plate provided by the present invention is used and its lid will be described.
FIG. 1 is a schematic diagram schematically showing a cross section of a battery provided with a lid, and FIG. 2 is a schematic diagram schematically showing a top surface of the battery lid. In the figure, 1 is a sealed battery, 2 is a battery case, and 3 is a lid formed of the aluminum alloy plate of the present invention. 4 is an electrolytic substance accommodated in the battery case, for example, an electrolytic substance in which lithium ions are used as a medium, 5 is a positive terminal of the battery, 6 is an insulator surrounding the
ところで、最初に記載したような厚さ４〜７ｍｍ×幅２０〜３０×深さ４０〜６０ｍｍの形状の電池ケースでは、約１ｍｍ厚のアルミニウム合金板を素材としてプレス加工し、厚さ１０〜３０μｍの防爆部を形成した蓋を一体成形することになる。
そこで、本発明者等は、厚さ１０〜３０μｍの防爆部を有する蓋であっても成形精度良くプレス加工でき、かつ冷間での加工の後にあっても焼鈍することなく所要の耐圧強度を発揮するアルミニウム合金板について鋭意検討した。その結果、成分組成と結晶粒の幅サイズを特定のものとすることにより、上記課題を解決できることを見出した。
以下にその詳細を説明する。
By the way, in a battery case having a shape of 4 to 7 mm thickness x 20 to 30 width x 40 to 60 mm depth as described at the beginning, an aluminum alloy plate having a thickness of about 1 mm is pressed as a material, and the thickness is 10 to 30 μm. The lid on which the explosion-proof portion is formed is integrally formed.
Therefore, the present inventors can perform press processing with high molding accuracy even with a lid having an explosion-proof portion having a thickness of 10 to 30 μm, and provide the required pressure strength without annealing even after cold processing. We have intensively studied about the aluminum alloy plate to be exhibited. As a result, it has been found that the above-mentioned problems can be solved by setting the component composition and the crystal grain width size to be specific.
Details will be described below.
まず、素材のアルミニウム合金として、Ｆｅ：１.１５〜１.３５質量％，Ｍｎ：０.４０〜０.６０質量％を含有し、残部Ａｌと不純物とからなり、不純物としてのＳｉが０.０５質量％以下，Ｃｕが０.０５質量％以下，Ｍｇが０.０５質量％以下に規制された組成を有するものを用いる。
さらに，Ｔｉ：０.００５〜０.１５質量％を、又はＴｉ：０.００５〜０.１５質量％とＢ：０．０００５〜０.０５質量％をともに含有させたものでもよい。
First, the raw material aluminum alloy contains Fe: 1.15 to 1.35% by mass, Mn: 0.40 to 0.60% by mass, the balance is Al and impurities, and Si as an impurity is 0.5. A material having a composition regulated to be 05% by mass or less, Cu is 0.05% by mass or less, and Mg is 0.05% by mass or less is used.
Further, Ti: 0.005 to 0.15% by mass, or Ti: 0.005 to 0.15% by mass and B: 0.0005 to 0.05% by mass may be contained.
Ｆｅ：１.１５〜１.３５質量％
Ｍｎ：０.４０〜０.６０質量％
これらの元素は、アルミニウム合金板に強度を付与すると共に、Ａｌ−（Ｆｅ−Ｍｎ）系の金属間化合物を微細に分散形成して再結晶組織の微細化並びに、ＤＩ成形性を付与する。Ｆｅ及びＭｎの含有量が下限値に満たないと所望の耐圧強度が得られない。しかし、上限値を超えると耐圧強度が高くなりすぎて強度調整のために焼戻処理が必要になる。また、Ａｌ‐（Ｆｅ‐Ｍｎ）系間化合物が粗大かつ多くなってプレス成形性を低下させ、安定した厚さの防爆部が得られ難くなる。
Fe: 1.15 to 1.35% by mass
Mn: 0.40 to 0.60% by mass
These elements impart strength to the aluminum alloy plate and finely disperse and form an Al- (Fe-Mn) -based intermetallic compound to impart a refined recrystallized structure and DI formability. If the content of Fe and Mn is less than the lower limit, the desired pressure strength cannot be obtained. However, if the upper limit is exceeded, the pressure resistance becomes too high, and a tempering treatment is required for strength adjustment. In addition, the Al- (Fe-Mn) intercalation compound is coarse and increases, reducing the press formability and making it difficult to obtain an explosion-proof portion having a stable thickness.
Ｔｉ：０.００５〜０.１５質量％
Ｂ：０.０００５〜０.０５質量％
Ｔｉ又はＢは、鋳造時の鋳造割れ防止のためのものであって、溶湯中にＡｌ−Ｔｉ又はＡｌ−Ｔｉ−Ｂの化合物を形成し、鋳造時の鋳造割れ防止効果がある。鋳造時に鋳造割れを防ぐ対応がなされていれば、必ずしも積極的に添加する必要はない。なお、添加に際してはＴｉ単独でも良いが、Ｔｉ及びＢを共存させると鋳造割れ防止の効果が高い。
Ti: 0.005 to 0.15% by mass
B: 0.0005-0.05 mass%
Ti or B is for preventing casting cracks at the time of casting, and has an effect of preventing casting cracks at the time of casting by forming a compound of Al-Ti or Al-Ti-B in the molten metal. If measures are taken to prevent casting cracks at the time of casting, it is not always necessary to positively add them. In addition, Ti alone may be used at the time of addition, but when Ti and B coexist, the effect of preventing casting cracks is high.
残部はＡｌ及び不純物である。
不純物としてのＳｉが０.１５質量％を超え、Ｃｕが０.０５質量％を超え、あるいはＭｇが０.０５質量％を超えると、プレス加工による加工硬化のバラツキが大きくなって安定した耐圧強度を有する防爆部が得られ難くなる。
特に、ＳｉはＡｌ−Ｆｅ−Ｓｉ系の化合物を形成してプレス成形性を劣化させ、安定した厚さを有する防爆部が得られなくなるので、少ない方が好ましく０.１２質量％以下、さらには０.１０質量％以下にすることが望ましい。
他の不純物含有量は通常の範囲でかまわない。例えばＺｎは０.２５質量％以下好ましくは０.２０質量％以下である。またＣｒは０.１０質量％以下好ましくは０.０５質量％以下である。
The balance is Al and impurities.
When Si as an impurity exceeds 0.15% by mass, Cu exceeds 0.05% by mass, or Mg exceeds 0.05% by mass, variation in work hardening due to press working becomes large and stable pressure resistance It is difficult to obtain an explosion-proof part having
In particular, Si forms an Al-Fe-Si-based compound and deteriorates press formability, and an explosion-proof part having a stable thickness cannot be obtained. Therefore, the smaller one is preferably 0.12% by mass or less, It is desirable to make it 0.10 mass% or less.
The other impurity content may be within a normal range. For example, Zn is 0.25 mass% or less, preferably 0.20 mass% or less. Cr is 0.10% by mass or less, preferably 0.05% by mass or less.
次に結晶粒のサイズについて説明する。
強度を安定して向上させ、プレス成形性を高め、かつ成形精度の優れたプレス成形品を得るには、粗大な結晶粒が存在せず、結晶粒が細かく整ったものが好ましい。
このため、本発明では、結晶粒の幅を、圧延面において、圧延方向に直角な方向における結晶粒の最大幅が１００μｍ以下，結晶粒の幅の平均が２５μｍ以下となったものと規定する。なお、本発明で言う結晶粒の最大幅サイズ及び幅の平均は、圧延面を研磨し、アルマイト処理を施して偏光顕微鏡で観察し、圧延方向に直角な方向をクロスカット法を用いて測定した。図３は、本発明における結晶粒幅の測定部を模式的に示した説明部である。２１は再結晶粒、２２は結晶粒幅の測定面で圧延面、２３は結晶粒の最大幅である。図４は図３と同様な説明図である。２４は焼鈍板を圧延した圧延板で、再結晶粒２１が圧延方向にわずかに伸びている状態で結晶粒の幅を測定する態様を説明している。２５は圧延方向に垂直な方向を示す。
Next, the crystal grain size will be described.
In order to stably improve the strength, improve the press moldability, and obtain a press-molded product with excellent molding accuracy, coarse crystal grains are not present, and crystal grains are finely arranged.
For this reason, in the present invention, the width of the crystal grain is defined as that the maximum width of the crystal grain in a direction perpendicular to the rolling direction is 100 μm or less and the average width of the crystal grain is 25 μm or less on the rolling surface. In addition, the average of the maximum width size and the width of the crystal grains referred to in the present invention was measured by polishing the rolled surface, performing anodized treatment and observing with a polarizing microscope, and using a cross-cut method in a direction perpendicular to the rolling direction. . FIG. 3 is an explanatory view schematically showing a crystal grain width measuring portion in the present invention. 21 is a recrystallized grain, 22 is a measurement surface of a crystal grain width and a rolling surface, and 23 is a maximum width of the crystal grain. FIG. 4 is an explanatory view similar to FIG.
結晶粒の幅が微細なものほど、粗大なものと比べて１結晶粒のメタルフローが板全体に対する影響が小さいために、プレス成形性が高まり、成形精度の優れたプレス成形品を得ることができる。結晶粒の幅の平均が２５μｍ以下であれば、所望の精度の電池用蓋が容易にプレス成形できる。結晶粒の幅の平均が２５μｍを超えると、プレス成形性が劣化し、成形精度も落ちる。
特に幅が１００μｍを超えるような粗大な結晶粒が存在すると、結晶粒の幅の平均が２５μｍを超える場合が多くなるが、２５μｍを超えなくても粗大結晶粒の存在により、粗大粒のメタルフローが板全体のメタルフローに大きく影響し、均等性を失って成形性を低下させることになる。また、幅の大きい粗大結晶粒の存在により薄肉防爆部の材質が不均一となり、粗大な結晶粒を起点として破断しやすく、防爆部の安定性を欠くことになる。
The finer the crystal grain width, the smaller the influence of the metal flow of one crystal grain on the whole plate compared to the coarser one, so that the press formability is improved and a press molded product with excellent molding accuracy can be obtained. it can. If the average width of crystal grains is 25 μm or less, a battery lid with desired accuracy can be easily press-formed. If the average crystal grain width exceeds 25 μm, the press formability deteriorates and the forming accuracy also decreases.
In particular, when there are coarse crystal grains having a width exceeding 100 μm, the average crystal grain width often exceeds 25 μm, but even if it does not exceed 25 μm, the presence of the coarse crystal grains causes the coarse metal flow. Greatly affects the metal flow of the entire plate, and loses uniformity and lowers formability. In addition, the presence of coarse crystal grains having a large width makes the material of the thin-walled explosion-proof part non-uniform, and it tends to break starting from the coarse crystal grains, resulting in lack of stability of the explosion-proof part.
このような粗大結晶粒が存在せず結晶粒の幅の平均が２５μｍ以下となったアルミニウム合金板の製造方法について説明する。
所定の成分組成を有するアルミニウム合金溶湯を通常の手段で鋳造し、鋳塊を得る。連続鋳造法を採用しても良いし、半連続鋳造法を採用しても良い。この際、鋳造割れの発生を抑制すべく、ＴｉやＢを添加しても良い。
得られた鋳塊に均質化処理を施す。この際、予め面削して表面の不均一層を除去することが好ましい。
A method for producing an aluminum alloy plate in which such coarse crystal grains do not exist and the average crystal grain width is 25 μm or less will be described.
A molten aluminum alloy having a predetermined component composition is cast by ordinary means to obtain an ingot. A continuous casting method may be employed, or a semi-continuous casting method may be employed. At this time, Ti or B may be added to suppress the occurrence of casting cracks.
The obtained ingot is homogenized. At this time, it is preferable to remove the uneven layer on the surface by chamfering in advance.
均質化処理；５３０〜６２０℃×１時間以上
粗大な幅を有する結晶粒をなくして微細な幅の結晶粒に整えるには、均質化処理の工程が重要となる。鋳塊中の晶出物を十分に固溶させるためには高めの温度で十分に均質化する必要がある。５３０℃に満たなかったり、１時間に満たない処理では晶出物が残ってしまう。６２０℃を超えると部分溶解の虞がある。また２４時間以上保持しても効果が飽和し、経済的に不利になるだけである。
Homogenization treatment: In order to eliminate crystal grains having a coarse width of 530 to 620 ° C. × 1 hour or more and to prepare crystal grains having a fine width, the step of homogenization treatment is important. In order to sufficiently dissolve the crystallized substance in the ingot, it is necessary to homogenize sufficiently at a higher temperature. Crystallized matter remains in a treatment that is less than 530 ° C. or less than 1 hour. If it exceeds 620 ° C, partial dissolution may occur. Moreover, even if it is kept for 24 hours or more, the effect is saturated, and it is only economically disadvantageous.
均質化処理後、熱延を施す。
熱延は、比較的高温で開始し、高温で仕上げて巻き取る。熱延中に不均一に析出物が出ないように、均一化処理の範囲の温度で開始し３９０℃以上で終了する熱延を行うことが好ましい。熱延終了温度が３９０℃に満たないと、析出物が後工程で悪影響を及ぼすこともある。好ましくは４００℃以上である。
均質化処理及び熱延の過程で晶出物が残存し、あるいは析出物が不均一に析出していると、冷延時に晶出物や析出物の存在する周囲とこれらの存在しない箇所において不均一な歪みが生じ、その結果、最終焼鈍時の再結晶時に歪みの少ない箇所においては粗大な幅を有する再結晶粒が、歪みの大きい箇所においては幅の小さい微細な再結晶粒を生じ、プレス成形性を劣化させることになる。
After homogenization, hot rolling is performed.
Hot rolling starts at a relatively high temperature, finishes and winds at a high temperature. It is preferable to perform hot rolling that starts at a temperature in the range of the homogenization treatment and ends at 390 ° C. or higher so that precipitates do not appear non-uniformly during hot rolling. If the hot rolling end temperature is less than 390 ° C., the precipitate may adversely affect the subsequent process. Preferably it is 400 degreeC or more.
If crystallized material remains in the process of homogenization and hot rolling, or precipitates are deposited non-uniformly, they will not be present in the surroundings where crystallized products or precipitates exist during cold rolling. As a result, uniform strain occurs, and as a result, recrystallized grains having a coarse width are generated at a portion with little strain at the time of recrystallization during final annealing, and fine recrystallized grains having a small width are formed at a portion where strain is large. Formability will be deteriorated.
焼鈍前の冷延；圧延率４０％以上
最終の焼鈍時に幅の小さい再結晶粒を均一微細にするには圧延率を高くして歪みを多く与えておくことが好ましい。４０％に満たないと幅の小さい再結晶粒が微細に均一化しない。
Cold rolling before annealing; rolling rate of 40% or more In order to make the recrystallized grains having a small width at the time of final annealing uniform, it is preferable to increase the rolling rate and give a lot of distortion. If it is less than 40%, the recrystallized grains having a small width are not made uniform finely.
最終焼鈍；１℃／秒以上の平均昇温速度で３５０〜５５０℃の範囲内の温度に加熱して保持無し若しくは１０分以内の保持を行って、１℃／秒以上の平均冷却速度で冷却
再結晶粒を均一微細に整えるには、この焼鈍工程の条件設定も重要な因子になる。温度が３５０℃に満たないと再結晶粒が微細に均一化しない。５５０℃を超えたり、１０分を超えるほどの長時間の焼鈍を行うと、再結晶粒が成長して均一微細な再結晶粒は得られない。
また、焼鈍時の昇温速度及び冷却速度も重要である。冷延時に導入された歪みの不均一な解消を抑制するためには１℃／秒以上の平均速度で急速加熱することが有効であり、再結晶粒の成長を防ぐためには１℃／秒以上の平均速度で急冷することが有効である。なお、冷却速度の制御は２００℃まででよく、冷却下限温度は同様に２００℃程度としておけばよい。
最終の焼鈍後、蓋本体の強度を向上させて傷等が付き難くするために、９０％以下、好ましくは６０％以下の圧延率で最終的な冷延を施しても良い。
Final annealing: Heat to a temperature in the range of 350 to 550 ° C. at an average temperature increase rate of 1 ° C./second or higher and hold for 10 minutes or less and cool at an average cooling rate of 1 ° C./second or higher In order to prepare recrystallized grains uniformly and finely, the setting of conditions for this annealing process is also an important factor. If the temperature is less than 350 ° C., the recrystallized grains are not made uniform finely. When annealing is performed for a long time exceeding 550 ° C. or exceeding 10 minutes, recrystallized grains grow and uniform fine recrystallized grains cannot be obtained.
In addition, the heating rate and cooling rate during annealing are also important. Rapid heating at an average rate of 1 ° C./second or more is effective to suppress non-uniform elimination of strain introduced during cold rolling, and 1 ° C./second or more to prevent the growth of recrystallized grains. It is effective to rapidly cool at an average speed. The cooling rate may be controlled up to 200 ° C., and the cooling lower limit temperature may be set to about 200 ° C. in the same manner.
After the final annealing, the final cold rolling may be performed at a rolling rate of 90% or less, preferably 60% or less, in order to improve the strength of the lid body and make it difficult to be damaged.
実施例１；
次に具体的な実施例について説明する。
表１に示す成分組成のアルミニウム合金溶湯を溶製し、半連続鋳造法で厚さ５３０ｍｍ、幅１１００ｍｍ、金型からの冷却水３.０リットル／ｃｍ分、鋳塊の引出速度５０ｍｍ／分で鋳塊を鋳造した。
Example 1;
Next, specific examples will be described.
The molten aluminum alloy having the composition shown in Table 1 was melted, and the thickness was 530 mm, the width was 1100 mm, the cooling water from the mold was 3.0 liters / cm, and the ingot drawing speed was 50 mm / min. The ingot was cast.
次に該鋳塊を面削後、６００℃×２時間の条件で均質化処理し，保持後熱延を開始し、終了温度４００℃で厚さ６ｍｍの熱延板とした。次いで冷間圧延４パスで１．４ｍｍ厚の冷延板とした。
その後、合金Ｎｏ．１，２，３，５の冷延板については２００℃／秒の平均速度で５００℃まで昇温し、その温度で１０秒保持した後、２００℃まで平均速度２００℃／秒の速さで急冷する焼鈍を行った。次いで室温まで冷却した前記焼鈍板を再度冷延し、厚さ１ｍｍの板とした。合金Ｎｏ．４については焼鈍温度を４５０℃とし、他の条件は同じ処理を施した。
得られた前記厚さ１ｍｍの冷延板について、研磨し、アルマイト処理後の圧延面において圧延方向に直角な方向における結晶粒の最大幅を偏光顕微鏡で観察し、幅の平均は最大幅を含みクロスカット法で測定した。平均幅は、カット長さ／カット線を横断する結晶粒数、で表す。
その結果を表２に示す。
Next, the ingot was subjected to homogenization treatment under conditions of 600 ° C. × 2 hours, hot rolling was started after holding, and a hot rolled sheet having a finishing temperature of 400 ° C. and a thickness of 6 mm was obtained. Subsequently, a cold-rolled sheet having a thickness of 1.4 mm was obtained by 4 passes of cold rolling.
Thereafter, Alloy No. For 1, 2, 3 and 5 cold-rolled plates, the temperature was raised to 500 ° C. at an average speed of 200 ° C./second, held at that temperature for 10 seconds, and then up to 200 ° C. at an average speed of 200 ° C./second. Rapid annealing was performed. Next, the annealed plate cooled to room temperature was cold-rolled again to obtain a plate having a thickness of 1 mm. Alloy No. For No. 4, the annealing temperature was 450 ° C., and other conditions were the same.
The obtained cold-rolled sheet having a thickness of 1 mm is polished, and the maximum width of the crystal grains in the direction perpendicular to the rolling direction is observed with a polarizing microscope on the rolled surface after the alumite treatment, and the average width includes the maximum width. It was measured by the cross cut method. The average width is expressed by the cut length / the number of crystal grains crossing the cut line.
The results are shown in Table 2.
上記で得られた各冷延焼鈍板を供試材とし、電池蓋の防爆部を想定してプレス成形で厚さ２０μｍ（プレス加工率９８％、ｎ数１０個）に加工してその箇所の耐圧強度を測定した。なお、プレス加工率は、｛（基板厚さ−プレス成形後の厚さ）／基板厚さ｝×１００％とした。また、耐圧強度は、所定厚さの試料に所定面積を有する密閉部を形成し、この密閉部に油圧を負荷し、試料を破壊させた時点での圧力とした。
参考とするために、表１のＮｏ.５に示すアルミニウム合金の冷延板を同じく２０μｍ厚にプレス成形した後、昇温バラツキが４０℃である焼鈍炉で３００℃×１時間保持で焼鈍したものについて耐圧強度を測定した。測定面積は２ｍｍ×３ｍｍとした。
耐圧強度の測定値を表２に併せて示す。
Using each cold-rolled annealed plate obtained above as a test material, assuming the explosion-proof part of the battery lid, it was processed into a thickness of 20 μm (press processing rate 98%, n number of 10) by press molding. The pressure strength was measured. The pressing rate was {(substrate thickness-thickness after press molding) / substrate thickness} × 100%. The pressure strength was a pressure at the time when a sealed portion having a predetermined area was formed on a sample having a predetermined thickness, and a hydraulic pressure was applied to the sealed portion to break the sample.
For reference, the aluminum alloy cold-rolled sheet shown in No. 5 in Table 1 was also press-formed to a thickness of 20 μm, and then annealed at 300 ° C. for 1 hour in an annealing furnace having a temperature rise variation of 40 ° C. The compressive strength was measured for the thing. The measurement area was 2 mm × 3 mm.
The measured values of the pressure strength are also shown in Table 2.
表２の結果から、本発明に係る試験Ｎｏ．１，２，３によるものは粗大な幅を有する結晶粒がなく、しかも平均幅も小さく、さらに耐圧強度も適当である。
一方、Ａ１０５０やＡ３００３に相当する試験Ｎｏ．４，５によるものも、粗大な幅を有する結晶粒はなく、しかも平均幅も小さかった。しかしながら、試験Ｎｏ．４によるものはプレス成形で薄く成形した防爆部相当箇所の耐圧強度が低く、電池蓋には適さないことがわかる。また試験Ｎｏ．５によるものはプレス成形で薄く成形した防爆部相当箇所の耐圧強度が高く、適正な防爆作用を期待できない。Ｎｏ．５の合金板を電池蓋に用いるには、試験Ｎｏ．６のように焼鈍を行う必要があるが、通常の工業炉においてはバラツキが大きくなって、安定性に欠ける。
From the results in Table 2, the test No. 1 according to the present invention. The ones according to 1, 2, and 3 do not have crystal grains having a coarse width, have a small average width, and have an appropriate pressure strength.
On the other hand, test numbers corresponding to A1050 and A3003. In the case of Nos. 4 and 5, there were no crystal grains having a coarse width, and the average width was small. However, test no. According to No. 4, the pressure-resistant strength of the portion corresponding to the explosion-proof portion formed thin by press molding is low, and it can be seen that it is not suitable for the battery lid. In addition, Test No. In the case of No. 5, the pressure-resistant strength of the portion corresponding to the explosion-proof portion formed thin by press molding is high, and an appropriate explosion-proof action cannot be expected. No. In order to use the alloy plate of No. 5 for the battery lid, test no. Although it is necessary to carry out the annealing as shown in FIG. 6, in a normal industrial furnace, the variation becomes large and the stability is lacking.
実施例２；
前記表１中のＮｏ．２の成分組成を有するアルミニウム合金を供試材とし、均質化処理、最終焼鈍前の冷延率及び最終焼鈍条件を表３に示すように種々変更して、板厚１ｍｍの焼鈍板を得た。
得られた各焼鈍板について、実施例１と同様に圧延面の結晶粒幅をクロスカット法で測定するとともに、２０μｍ厚にプレス成形して耐圧強度（ｎ数１０個）を測定した。測定面積は２ｍｍ×３ｍｍとした。
その測定結果を表４に示す。
Example 2;
No. in Table 1 above. An aluminum alloy having a component composition of 2 was used as a test material, and an annealing plate having a thickness of 1 mm was obtained by variously changing the homogenization treatment, the cold rolling ratio before final annealing, and the final annealing conditions as shown in Table 3. .
About each obtained annealing board, while measuring the crystal grain width of a rolling surface by the crosscut method similarly to Example 1, it press-molded to 20 micrometers thickness, and measured the pressure strength (several tens of pieces). The measurement area was 2 mm × 3 mm.
The measurement results are shown in Table 4.
表４の結果から、本発明に係る試験Ｎｏ．７〜１０によるものは粗大な幅を有する結晶粒がなく、しかも平均幅も小さく、さらにプレス成形で薄くした防爆部相当箇所の耐圧強度もバラツキが小さく、安定性があった。
一方、本発明の条件から外れている試験Ｎｏ．１１〜１３によるものは、粗大な幅を有する結晶粒があるとともに平均幅が大きく、プレス成形で薄くした防爆部相当箇所の耐圧強度もバラツキが大きく、安定性がなく好ましくないことがわかる。
From the results of Table 4, the test No. 1 according to the present invention is shown. No. 7 to 10 had no crystal grains having a coarse width, had a small average width, and had a small variation in the pressure-resistant strength of the portion corresponding to the explosion-proof portion made thin by press molding, and was stable.
On the other hand, Test No. deviating from the conditions of the present invention. 11 to 13 have crystal grains having a coarse width and a large average width, and the pressure-resistant strength of the portion corresponding to the explosion-proof portion thinned by press molding is greatly varied, which is not preferable because of no stability.
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| JP2007104653A JP5004007B2 (en) | 2007-04-12 | 2007-04-12 | Aluminum alloy plate for battery lid and manufacturing method thereof |
| KR1020070139735A KR101310517B1 (en) | 2007-04-12 | 2007-12-28 | Aluminum alloy plate for battery case and manufacturing method thereof |
| CN201010573300.0A CN102136554B (en) | 2007-04-12 | 2007-12-29 | Aluminum alloy sheet for battery cover and its production method |
| CN2007103008467A CN101469386B (en) | 2007-04-12 | 2007-12-29 | Aluminum alloy sheet for battery cover and its production method |
| KR1020110081467A KR101381028B1 (en) | 2007-04-12 | 2011-08-17 | Battery case made of aluminum alloy and manufacturing method thereof |
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Also Published As
| Publication number | Publication date |
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| KR101381028B1 (en) | 2014-04-04 |
| CN102136554B (en) | 2014-10-01 |
| KR20080092831A (en) | 2008-10-16 |
| CN101469386B (en) | 2011-01-26 |
| KR101310517B1 (en) | 2013-09-25 |
| JP5004007B2 (en) | 2012-08-22 |
| CN101469386A (en) | 2009-07-01 |
| KR20110099204A (en) | 2011-09-07 |
| CN102136554A (en) | 2011-07-27 |
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