JPH11156995A - Clad plate, battery case using it, and manufacture thereof - Google Patents
Clad plate, battery case using it, and manufacture thereofInfo
- Publication number
- JPH11156995A JPH11156995A JP10091099A JP9109998A JPH11156995A JP H11156995 A JPH11156995 A JP H11156995A JP 10091099 A JP10091099 A JP 10091099A JP 9109998 A JP9109998 A JP 9109998A JP H11156995 A JPH11156995 A JP H11156995A
- Authority
- JP
- Japan
- Prior art keywords
- plate
- pure
- based alloy
- clad
- thin layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｃｕ(銅)板又はＣ
ｕ基合金板とＡｌ(アルミニウム)板又はＡｌ基合金板と
を一体に接合したクラッド板とこれを用いた電池用ケー
ス並びにこれらの製造方法に関する。TECHNICAL FIELD The present invention relates to a Cu (copper) plate or C
The present invention relates to a clad plate in which a u-based alloy plate and an Al (aluminum) plate or an Al-based alloy plate are integrally joined, a battery case using the same, and a method of manufacturing these.
【０００２】[0002]
【従来の技術】近年、携帯電話に代表される電子機器の
小型化・軽量化が著しく、それらの構成部品であるリチ
ウムイオン電池やニッカド電池等の電気部品、又はＩ
Ｃ、ダイオード、半導体素子その他の各種電子デバイス
用のケース、或いは電子機器用接点部品も同様に小型化
・軽量化が強く求められている。このような小型化・軽
量化に対応していく上で、上記電池等の電気部品や電子
デバイス自体の軽量化を図るため、それら自体のケース
やそれらを収納するのに用いるケースの材質も、従来の
鋼やステンレス鋼等のようなＦｅ系材料からＡｌ又はそ
の合金への移行が試みられている。2. Description of the Related Art In recent years, the size and weight of electronic devices such as mobile phones have been remarkably reduced in size and their components, such as electric components such as lithium ion batteries and nickel cadmium batteries, or I / O batteries.
Similarly, a case for C, a diode, a semiconductor element, and other various electronic devices, or a contact part for electronic equipment is also strongly required to be reduced in size and weight. In order to cope with such miniaturization and weight reduction, in order to reduce the weight of electric components such as the battery and the electronic device itself, the material of the case itself and the case used to store them are also required. Attempts have been made to transition from conventional Fe-based materials such as steel and stainless steel to Al or its alloys.
【０００３】確かに、Ａｌ又はその合金の比重はＦｅ系
材料の約３分の１であるため、大幅な軽量化が可能とな
る。しかし、ＡｌやＡｌ合金の強度は、Ｆｅ系材料より
もかなり低いため、Ｆｅ系材料と同等の強度にするに
は、上記ケース等の肉厚を厚くせざるを得なくなる。こ
のため、Ａｌ系の材料を電池用ケース等に適用しても、
大幅な軽量化を実現されていないのが現状である。Certainly, since the specific gravity of Al or its alloy is about one third of that of the Fe-based material, the weight can be significantly reduced. However, since the strength of Al or an Al alloy is considerably lower than that of an Fe-based material, in order to obtain the same strength as that of the Fe-based material, the thickness of the case or the like must be increased. Therefore, even if an Al-based material is applied to a battery case or the like,
At present, significant weight reduction has not been realized.
【０００４】一方、コンデンサ用ケースにおける導電性
や電磁波シールド特性を向上させ、且つ軽量化を図るた
め、Ａｌ系材料とＣｕ系材料とのクラッド材の適用が検
討されている。係るＡｌ・Ｃｕ系のクラッド材により所
要の強度を与えることも可能である。しかし、電子デバ
イス用ケースを得るため、Ａｌ系材料とＣｕ系材料との
クラッド材を用いて深絞り加工等の変形率の高い過酷な
加工を行うと、両材料の接合部分から互いにずれたり剥
離が生じて、一方の材料に皺やクラック等の亀裂が生じ
て破損に至るという問題があった。On the other hand, in order to improve the conductivity and electromagnetic wave shielding characteristics of the capacitor case and to reduce the weight, application of a clad material of an Al-based material and a Cu-based material has been studied. It is also possible to provide the required strength with such an Al.Cu-based cladding material. However, in order to obtain a case for an electronic device, if severe processing with a high deformation rate such as deep drawing is performed using a clad material of an Al-based material and a Cu-based material, the two materials are displaced or separated from each other at a joint portion. And there is a problem that cracks such as wrinkles and cracks occur in one of the materials, resulting in breakage.
【０００５】[0005]
【発明が解決すべき課題】本発明は、以上の従来の技術
が抱える問題点を解決し、深絞り加工等を施しても所要
の接合強度を維持し得るＡｌ系板及びＣｕ系板或いはそ
れらの合金板同士からなるクラッド板とこれを用いた電
池用ケース並びにこれらの製造方法を提供することを課
題とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and provides an Al-based plate and a Cu-based plate capable of maintaining a required bonding strength even when subjected to deep drawing or the like. It is an object of the present invention to provide a clad plate made of alloy plates of the above, a battery case using the clad plate, and a method of manufacturing these.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記の課題を
解決するため、Ａｌ系材料とＣｕ系材料との双方に対し
て親和性(馴染易さ)の高い純Ｎｉ(ニッケル)の薄層を両
者の板材間に介在させることに着想して成されたもので
ある。即ち、本発明のクラッド板は、Ｃｕ板又はＣｕ基
合金板とＡｌ板又はＡｌ基合金板とを、純Ｎｉの薄層を
介して一体に接合した、ことを特徴とする。係る３層構
造のクラッド板によれば、重量を増やすことなく、Ａｌ
系板とＣｕ系板とを強固に一体化して接合でき、深絞り
加工してもずれや剥離等が生じることを防止でき、精度
の良い成形加工を確実に行うことが可能となる。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a thin film of pure Ni (nickel) having a high affinity (compatibility) with both Al-based materials and Cu-based materials. The idea is to interpose a layer between the two plate materials. That is, the clad plate of the present invention is characterized in that a Cu plate or a Cu-based alloy plate and an Al plate or an Al-based alloy plate are integrally joined via a thin layer of pure Ni. According to such a three-layer clad plate, Al is added without increasing weight.
The base plate and the Cu base plate can be firmly integrated and joined together, and it is possible to prevent the occurrence of misalignment or peeling even when deep drawing is performed, and it is possible to reliably perform accurate forming.
【０００７】また、Ａｌ板又はＡｌ基合金板と、その両
表面に被覆した純Ｎｉの薄層と、何れかの純Ｎｉの薄層
の表面上に被覆したＣｕ板又はＣｕ基合金板とを有す
る、クラッド板も含まれる。このクラッド板によれば、
後述する電池用ケースのように一方の表面にＣｕ系板を
配置し、且つ他方の表面に純Ｎｉの薄層を被覆したＡｌ
系板を配置できるので、陰極部分と耐塩基性等の耐食性
に優れた覆い部分を両側面に併有できる。Further, an Al plate or an Al-based alloy plate, a thin layer of pure Ni coated on both surfaces thereof, and a Cu plate or a Cu-based alloy plate coated on the surface of either of the thin layers of pure Ni And a clad plate. According to this clad plate,
Al in which a Cu-based plate is disposed on one surface and a thin layer of pure Ni is coated on the other surface as in a battery case described later.
Since the system plate can be arranged, a cathode portion and a cover portion having excellent corrosion resistance such as base resistance can be provided on both side surfaces.
【０００８】更に、Ｃｕ板又はＣｕ基合金板、或いはＡ
ｌ板又はＡｌ基合金板の何れかの両表面にそれぞれ純Ｎ
ｉの薄層を介して、一対のＡｌ板又はＡｌ基合金板、或
いは一対のＣｕ板又はＣｕ基合金板を一体に接合したク
ラッド板も含まれる。これにより、Ａｌ系板又はＣｕ系
板を中心としてその両側面に純Ｎｉの薄層を介してＣｕ
系又はＡｌ系板を接合した５層構造の強固な接合構造を
有するクラッド板にでき、例えば高い電磁波シールド特
性や導電性を得ることが可能となる。Further, a Cu plate or a Cu-based alloy plate, or A
Pure N on both surfaces of either the aluminum plate or the Al-based alloy plate
A clad plate in which a pair of Al plates or an Al-based alloy plate, or a pair of Cu plates or a Cu-based alloy plate are integrally joined via a thin layer of i is also included. Thereby, the Al-based plate or the Cu-based plate is centered on both sides of the Cu-based plate with a thin layer of pure Ni therebetween.
A clad plate having a strong bonding structure of a five-layer structure obtained by bonding an Al-based plate or an Al-based plate can be obtained, and for example, high electromagnetic wave shielding characteristics and high conductivity can be obtained.
【０００９】また、本発明は、以上の各クラッド板を用
いると共に、全体が有底筒形で且つその内周面側に前記
Ｃｕ板又はＣｕ基合金板を配置した、電池用ケースも含
む。これによれば、内周面側にＣｕ系板を配置して陰極
部分を形成すると共に、外周面側にはＡｌ系板、純Ｎｉ
の薄層を被覆したＡｌ系板、又は別のＣｕ系板を一体に
した形状・寸法精度に優れた各種の電池用ケースにでき
る。尚、係るケースの形状には円筒形、又は直方体等各
種の有底筒形を適用することができる。The present invention also includes a battery case using each of the above-mentioned clad plates, and having a bottomed cylindrical shape as a whole and having the Cu plate or Cu-based alloy plate disposed on the inner peripheral surface thereof. According to this, a Cu-based plate is arranged on the inner peripheral surface side to form a cathode portion, and an Al-based plate, pure Ni
Various types of battery cases excellent in shape and dimensional accuracy in which an Al-based plate coated with a thin layer or another Cu-based plate are integrated. In addition, various bottomed cylindrical shapes such as a cylindrical shape or a rectangular parallelepiped can be applied to the shape of the case.
【００１０】一方、本発明のクラッド板の製造方法は、
Ｃｕ板又はＣｕ基合金板とＡｌ板又はＡｌ基合金板と
を、それらの間に純Ｎｉの薄層を配設して接合する、こ
とを特徴とする。これによれば、純Ｎｉの薄層を介して
Ａｌ系板及びＣｕ系板を強固に接合したクラッド板を容
易且つ確実に製造することが可能となる。また、前記Ｃ
ｕ板又はＣｕ基合金板の少なくとも一方の表面にＮｉメ
ッキにより厚さ０．３〜１５μｍの純Ｎｉの薄層を被覆
する工程と、この純Ｎｉの薄層の上にＡｌ板又はＡｌ基
合金板を圧着圧延又は爆着等により接合する工程と、を
含むクラッド板の製造方法も含まれる。この方法によれ
ば、予めＣｕ系板に薄いＮｉメッキ層を被覆した後、そ
の表面に圧着圧延等によりＡｌ系板を強固に接合して一
体化したクラッド板ができる。On the other hand, the method for producing a clad plate of the present invention comprises:
It is characterized in that a Cu plate or a Cu-based alloy plate and an Al plate or an Al-based alloy plate are joined by disposing a thin layer of pure Ni between them. According to this, it is possible to easily and reliably manufacture a clad plate in which an Al-based plate and a Cu-based plate are firmly joined via a thin layer of pure Ni. In addition, C
coating at least one surface of a u-plate or a Cu-based alloy plate with a thin layer of pure Ni having a thickness of 0.3 to 15 μm by Ni plating, and forming an Al plate or an Al-based alloy on the thin layer of pure Ni. A method of manufacturing a clad plate including a step of bonding the plate by pressure rolling, explosion bonding, or the like. According to this method, after a Cu-based plate is previously coated with a thin Ni plating layer, an Al-based plate is firmly joined to the surface of the Cu-based plate by pressure rolling or the like to form a clad plate.
【００１１】更に、前記Ａｌ板又はＡｌ基合金板の少な
くとも一方の表面にＮｉメッキにより厚さ０．３〜１５
μｍの純Ｎｉの薄層を被覆する工程と、この純Ｎｉの薄
層の何れかの表面上に前記Ｃｕ板又はＣｕ基合金板を圧
着圧延又は爆着等により接合する工程と、を含むクラッ
ド板の製造方法も含まれる。これにより、予めＡｌ系板
に薄いＮｉメッキ層を被覆した後、その表面に圧着圧延
等によりＣｕ系板を強固に接合して一体化したクラッド
板ができる。尚、上記純Ｎｉの薄層の厚さが０．３μｍ
未満になるとＡｌ系及びＣｕ系板間の接合強度が低下
し、１５μｍを超えると接合強度が飽和して純Ｎｉの薄
層が無駄になるので、これらの間における範囲の厚さと
したものである。また、Ｃｕ系板又はＡｌ系板にメッキ
された純Ｎｉの薄層に対し、予めワイヤ等によるブラシ
ッングを施して細かい凹凸面を形成しておくと、圧着圧
延等によりＡｌ系板又はＣｕ系板を一層強固に接合する
ことが可能となる。Further, at least one surface of the Al plate or the Al-based alloy plate has a thickness of 0.3 to 15 by Ni plating.
a step of coating a thin layer of pure Ni having a thickness of μm, and a step of bonding the Cu plate or the Cu-based alloy plate to any surface of the thin layer of pure Ni by pressure rolling, explosion, or the like. It also includes a method for manufacturing a plate. Thus, a clad plate is obtained in which an Al-based plate is previously coated with a thin Ni plating layer, and a Cu-based plate is firmly joined to the surface of the Al-based plate by pressure rolling or the like. The thickness of the thin layer of pure Ni is 0.3 μm.
When the thickness is less than the above, the bonding strength between the Al-based and Cu-based plates decreases, and when the thickness exceeds 15 μm, the bonding strength is saturated and a thin layer of pure Ni is wasted. . In addition, if a thin layer of pure Ni plated on a Cu-based plate or an Al-based plate is subjected to brushing with a wire or the like in advance to form a fine uneven surface, the Al-based plate or the Cu-based plate is subjected to pressure rolling or the like. Can be more firmly joined.
【００１２】更に、前記接合工程の後に、得られたクラ
ッド板に約２００〜６００℃の範囲で拡散焼鈍を施す工
程を行うクラッド板の製造方法も含まれる。これによれ
ば、Ｃｕ系板と純Ｎｉの薄層との接合面、又は純Ｎｉの
薄層とＡｌ系板の接合面に沿って、ＣｕとＮｉ間及びＮ
ｉとＡｌ間における相互拡散が行われるので、更に高い
接合強度を有するクラッド板を提供することができる。
尚、上記拡散焼鈍は、真空中又はアルゴンガス等の不活
性雰囲気中において、３００℃以上、より望ましくは５
００〜６００℃の温度範囲で行われる。従って、接合面
に沿ってＮｉＡｌ及び／又はＮｉ3Ａｌ系の脆い金属間
化合物は形成されず、接合強度の低下を防ぐことができ
る。Further, the present invention also includes a method of manufacturing a clad plate, in which a step of subjecting the obtained clad plate to diffusion annealing at a temperature in the range of about 200 to 600 ° C. after the joining step. According to this, along the joining surface between the Cu-based plate and the thin layer of pure Ni, or the joining surface between the thin layer of pure Ni and the Al-based plate, the distance between Cu and Ni and N
Since the interdiffusion is performed between i and Al, a clad plate having higher bonding strength can be provided.
The diffusion annealing is performed at a temperature of 300 ° C. or more, more preferably 5 ° C. in a vacuum or an inert atmosphere such as an argon gas.
It is performed in a temperature range of 00 to 600 ° C. Therefore, a brittle intermetallic compound of NiAl and / or Ni 3 Al is not formed along the bonding surface, and a decrease in bonding strength can be prevented.
【００１３】また、前記接合工程の後、又は前記焼鈍工
程の後において、前記クラッド板を有底筒形に絞り加工
する成形工程を行う、電池用ケースの製造方法も含まれ
る。これにより、内周面側に略均一な厚さのＣｕ系板を
陰極用として配置し、これと純Ｎｉの薄層を介して強固
に接合したＡｌ系板、純Ｎｉの薄層を被覆したＡｌ系
板、又は別のＣｕ系板を外周面側にした各種の有底筒形
の電池用ケースを確実且つ精度良く製造することができ
る。[0013] The present invention also includes a method for manufacturing a battery case, wherein after the joining step or after the annealing step, a forming step of drawing the clad plate into a bottomed cylindrical shape is performed. As a result, a Cu-based plate having a substantially uniform thickness was disposed on the inner peripheral surface side for the cathode, and an Al-based plate and a thin layer of pure Ni which were firmly bonded to this with a thin layer of pure Ni were coated. Various bottomed cylindrical battery cases having an Al-based plate or another Cu-based plate on the outer peripheral surface side can be reliably and accurately manufactured.
【００１４】[0014]
【実施の形態】以下において、本発明の実施に好適な形
態を図面と共に説明する。図１(Ａ)は、Ａｌ基合金板２
とＣｕ基合金板４とを、それらの間に厚さ１０μｍの純
Ｎｉの薄層６を介在させて一体に接合したＡｌ・Ｃｕク
ラッド板１の断面図を示す。上記Ａｌ基合金板２及びＣ
ｕ基合金板４の厚さは、共に０.１〜１.０ｍｍの範囲に
おいて用途や特性に応じて適宜選択される。Preferred embodiments of the present invention will be described below with reference to the drawings. FIG. 1A shows an Al-based alloy plate 2
FIG. 1 shows a cross-sectional view of an Al.Cu clad plate 1 in which a Cu-based alloy plate 4 and a Cu-based alloy plate 4 are integrally joined together with a thin layer 6 of pure Ni having a thickness of 10 μm interposed therebetween. Al-based alloy plate 2 and C
The thickness of the u-based alloy plate 4 is appropriately selected within the range of 0.1 to 1.0 mm in accordance with the use and characteristics.
【００１５】図１(Ｂ)は上記Ａｌ・Ｃｕクラッド板１を
絞り加工して得られた電池用ケース８を示す。この電池
用ケース８は、厚さ０．３ｍｍのＡｌ基合金板２及びＣ
ｕ基合金板４を上記純Ｎｉの薄層６を介して接合したク
ラッド板１を用い、上記Ｃｕ基合金板４が内周面側にな
るように、図示しないプレス装置を用いて深絞り加工し
て得た有底円筒状のケースである。係る深絞り加工によ
り著しい変形を受けるケース８の下隅部分８ａや周壁部
分８ｂにおいて、当該部分のＡｌ基合金板２とＣｕ基合
金板４は、互いにずれたり、クラック等の局部破損を生
じない。これは、それらの間に介在する上記純Ｎｉの薄
層６との強い親和力と共に、後述する拡散焼鈍による相
互拡散によってＣｕとＮｉ間及びＮｉとＡｌ間の相互拡
散層が各接合面に沿って形成されているためである。FIG. 1B shows a battery case 8 obtained by drawing the Al / Cu clad plate 1. The battery case 8 includes the Al-based alloy plate 2 having a thickness of 0.3 mm and the C
Using the clad plate 1 in which the u-base alloy plate 4 is joined via the pure Ni thin layer 6, deep drawing is performed using a pressing device (not shown) so that the Cu-base alloy plate 4 is on the inner peripheral surface side. It is a cylindrical case with a bottom obtained in this way. In the lower corner portion 8a and the peripheral wall portion 8b of the case 8 that are significantly deformed by such deep drawing, the Al-based alloy plate 2 and the Cu-based alloy plate 4 in the portions do not shift from each other or cause local damage such as cracks. This is because the interdiffusion layers between Cu and Ni and between Ni and Al are formed along the joint surfaces by the interdiffusion by the diffusion annealing described later, together with the strong affinity with the thin layer 6 of pure Ni interposed therebetween. This is because it is formed.
【００１６】図１(Ｃ)及び(Ｄ)は、上記Ａｌ・Ｃｕクラ
ッド板１の応用形態に関し、同(Ｃ)はＡｌ基合金板２の
両表面に純Ｎｉの薄層６，６を介して一対のＣｕ基合金
板４を接合したＡｌ・Ｃｕクラッド板１０の断面図を示
す。また、図１(Ｄ)はＣｕ基合金板４の両表面に純Ｎｉ
の薄層６，６を介して一対のＡｌ基合金板２を接合した
Ａｌ・Ｃｕクラッド板１０′の断面図を示す。これら５
層構造を有するＡｌ・Ｃｕクラッド板１０，１０′は、
比較的薄肉のＡｌ基合金板２及びＣｕ基合金板４を用い
ることにより、所望の板厚と内部の高い接合力を有する
ので、例えば上記クラッド板１０は電磁波シールド用と
して、また、クラッド板１０′は、薬液タンク用等とし
て活用することができる。FIGS. 1 (C) and 1 (D) relate to an application form of the above-mentioned Al.Cu clad plate 1, and FIG. 1 (C) shows a structure in which pure Ni thin layers 6 and 6 are provided on both surfaces of an Al-based alloy plate 2. 1 shows a cross-sectional view of an Al-Cu clad plate 10 in which a pair of Cu-based alloy plates 4 are joined. FIG. 1D shows pure Ni on both surfaces of the Cu-based alloy plate 4.
A cross-sectional view of an Al.Cu clad plate 10 'in which a pair of Al-based alloy plates 2 are joined via thin layers 6 and 6 of FIG. These 5
The Al · Cu clad plates 10 and 10 ′ having a layer structure are:
Since the relatively thin Al-based alloy plate 2 and Cu-based alloy plate 4 have a desired plate thickness and a high internal bonding force, for example, the clad plate 10 is used for electromagnetic wave shielding, 'Can be used for chemical solution tanks and the like.
【００１７】図２(Ａ)は、Ａｌ基合金板２の両表面に厚
さ１０μｍの純Ｎｉの薄層６を被覆し、その一方の薄層
６の表面上にＣｕ基合金板４を一体に接合した、Ａｌ・
Ｃｕクラッド板１′の断面図を示す。上記Ａｌ基合金板
２及びＣｕ基合金板４の厚さは、共に０.１〜１.０ｍｍ
の範囲において用途や特性に応じて適宜選択される。図
２(Ｂ)は上記クラッド板１′を絞り加工して得た電池用
ケース８′の断面図を示す。これは、クラッド板１′を
そのＣｕ基合金板４が内周面側になるよう前記同様プレ
ス装置を用いて深絞り加工した有底筒形の電池用ケース
８′である。係る深絞り加工により著しい変形を受ける
下隅部分８ａにおいて、当該部分のＣｕ基合金板４は、
クラック等の局部破損を生じず、しかもＡｌ基合金板２
と互いにずれたりしない。これも、各接合面に沿ってＣ
ｕとＮｉ間及びＮｉとＡｌ間の相互拡散層が形成されて
いるためである。FIG. 2A shows that both surfaces of an Al-based alloy plate 2 are coated with a thin layer 6 of pure Ni having a thickness of 10 μm, and a Cu-based alloy plate 4 is integrally formed on the surface of one of the thin layers 6. Al ・
The sectional view of the Cu clad plate 1 'is shown. The thicknesses of the Al-based alloy plate 2 and the Cu-based alloy plate 4 are both 0.1 to 1.0 mm.
Is appropriately selected in accordance with the application and characteristics. FIG. 2B is a sectional view of a battery case 8 'obtained by drawing the clad plate 1'. This is a bottomed cylindrical battery case 8 'obtained by subjecting the clad plate 1' to deep drawing using a pressing device in the same manner as described above so that the Cu-based alloy plate 4 is on the inner peripheral surface side. In the lower corner portion 8a which undergoes significant deformation due to such deep drawing, the Cu-based alloy plate 4 of the portion is
Al-based alloy plate 2 that does not cause local damage such as cracks
Does not shift from each other. This is also due to the C
This is because the interdiffusion layers between u and Ni and between Ni and Al are formed.
【００１８】図３(Ａ)〜(Ｄ)は、前記Ａｌ・Ｃｕクラッ
ド板１の製造方法に関する。同図(Ａ)に示す厚さ１ｍ
ｍ、板幅５０ｍｍの純Ｃｕ板４に対し、その一方の表面
に電気メッキを施し、図３(Ｂ)に示すように、厚さ約２
０μｍの純Ｎｉの薄層６を被覆する。次に、図３(Ｃ)に
示すように、この純Ｎｉの薄層６に線径０．３ｍｍのス
テンレスワイヤを放射状に植設した回転するブラシ７を
押し付けつつ、図中の矢印のように該薄層６に沿って移
動させ、純Ｎｉの薄層６の表面を清浄化して活性化する
と共に、その表面に微細な凹凸条を形成する。FIGS. 3A to 3D relate to a method of manufacturing the Al.Cu clad plate 1. FIG. 1 m thick as shown in FIG.
The pure Cu plate 4 having a thickness of 50 mm and a width of 50 mm was subjected to electroplating on one surface thereof to have a thickness of about 2 mm as shown in FIG.
A thin layer 6 of 0 μm pure Ni is coated. Next, as shown in FIG. 3 (C), while pressing a rotating brush 7 having a stainless steel wire having a wire diameter of 0.3 mm radially implanted on the thin layer 6 of pure Ni, as shown by an arrow in the figure. By moving along the thin layer 6, the surface of the pure Ni thin layer 6 is cleaned and activated, and fine irregularities are formed on the surface.
【００１９】そして、上記純Ｎｉの薄層６の表面に、図
３(Ｄ)の左方に示すように、厚さ１ｍｍ、板幅５０ｍｍ
の純Ａｌ板(純度９９％)２を添接した後、一対のロール
９，９間に押し込んで通過させる。このロール９，９間
を通す圧着圧延により、図３(Ｄ)の右方に示すように、
全体の厚さが約１ｍｍで厚さ５μｍの純Ｎｉの薄層６を
中間に有するＡｌ・Ｃｕクラッド板１が得られる。尚、
係る圧着圧延での加工(圧下)率は約５０％であった。こ
の圧着圧延されたままのＡｌ・Ｃｕクラッド板１でも、
その純Ａｌ板２及び純Ｃｕ板４と純Ｎｉの薄層６との各
接合面における親和力により、前記のような深絞り加工
を施しても、所要の形状のケース等に十分成形すること
ができる。尚、図３(Ｅ)は後述するクラッド板１の接合
強度の測定状態を示す。Then, as shown on the left side of FIG. 3D, the surface of the thin layer 6 of pure Ni is 1 mm thick and 50 mm wide.
After a pure Al plate (purity 99%) 2 is put in contact therewith, it is pushed between a pair of rolls 9 and 9 to pass therethrough. As shown in the right side of FIG.
The Al / Cu clad plate 1 having a thickness of about 1 mm and a thin layer 6 of pure Ni having a thickness of 5 μm in the middle is obtained. still,
The processing (reduction) rate in the pressure rolling was about 50%. Even with the Al.Cu clad plate 1 as pressed and rolled,
Due to the affinity at each joint surface between the pure Al plate 2 and the pure Cu plate 4 and the thin layer 6 of pure Ni, even if the above-described deep drawing is performed, it can be sufficiently formed into a case having a required shape. it can. FIG. 3E shows a measurement state of the bonding strength of the clad plate 1 described later.
【００２０】しかしながら、純Ａｌ板２及び純Ｃｕ板４
と純Ｎｉの薄層６間の接合力をより高めるため、Ａｌ・
Ｃｕクラッド板１を真空中又はアルゴンガス等の不活性
雰囲気中において、約２００〜６００℃の温度範囲で拡
散焼鈍を行うのが望ましい。係る拡散焼鈍により、純Ｎ
ｉの薄層６と純Ａｌ板２の接合面、及び純Ｃｕ板４と純
Ｎｉの薄層６との接合面に沿って、各元素同士の相互拡
散が行われる。従って、これらの拡散層によって、上記
の３つの層２,６,４を互いに一層強固に接合したＡｌ・
Ｃｕクラッド板１を得ることができる。However, the pure Al plate 2 and the pure Cu plate 4
In order to further increase the bonding force between the thin layer 6 of pure Ni and
It is desirable to perform diffusion annealing of the Cu clad plate 1 in a vacuum or an inert atmosphere such as argon gas at a temperature range of about 200 to 600 ° C. By such diffusion annealing, pure N
Inter-diffusion between the elements occurs along the joint surface between the thin layer 6 of i and the pure Al plate 2 and the joint surface between the pure Cu plate 4 and the thin layer 6 of pure Ni. Therefore, these diffusion layers make the three layers 2, 6, and 4 more firmly joined to each other.
The Cu clad plate 1 can be obtained.
【００２１】図４(Ａ)〜(Ｄ)は、前記Ａｌ・Ｃｕクラッ
ド板１′の製造方法に関する。同図(Ａ)に示す厚さ２ｍ
ｍ、板幅１００ｍｍのＡｌ合金(A3003)板２に対し、その
両表面に無電解光沢Ｎｉメッキを施し、図４(Ｂ)に示す
ように、厚さ約３μｍの純Ｎｉの薄層６を被覆する。こ
の場合、Ａｌ合金板２の全表面にＮｉメッキを被覆でき
るので、マスキングやその剥離作業を省略することがで
きる。次に、一(上)方の純Ｎｉの薄層６に前記線径０．
３ｍｍのステンレスワイヤを放射状に植設した回転ブラ
シ７を押し付け、且つ該薄層６に沿って移動して、純Ｎ
ｉの薄層６の表面を清浄化して活性化すると共に、微細
な凹凸条を形成する。FIGS. 4A to 4D relate to a method of manufacturing the Al.Cu clad plate 1 '. 2 m thick as shown in FIG.
An Al alloy (A3003) plate 2 having a width of 100 mm and a width of 100 mm was subjected to electroless glossy Ni plating on both surfaces thereof, and a thin layer 6 of pure Ni having a thickness of about 3 μm was formed as shown in FIG. Cover. In this case, the entire surface of the Al alloy plate 2 can be coated with Ni plating, so that masking and peeling operations can be omitted. Next, the wire diameter of 0.
A rotating brush 7 having a 3 mm stainless steel wire radially implanted therein is pressed and moved along the thin layer 6 to obtain pure N.
The surface of the thin layer 6 of i is cleaned and activated, and fine uneven lines are formed.
【００２２】そして、上記一方の純Ｎｉの薄層６の表面
に、図４(Ｃ)の左方に示すように、厚さ０．４ｍｍ、板
幅９０ｍｍのＣｕ(無酸素銅)板４を添接した後、一対の
ロール９，９間に押し込んで通過させる。このロール
９，９間を加工(圧下)率６７％で通す圧着圧延により、
図４(Ｄ)に示すように、全体の厚さが約０．８ｍｍで、
且つ厚さ２μｍの一対の純Ｎｉの薄層６を中間と他(下)
方の表面とに有するＡｌ・Ｃｕクラッド板１′が得られ
る。このクラッド板１′も、前記同様に拡散焼鈍を施す
ことで、各層２,６,４を互いに一層強固に接合すること
ができる。尚、下方の表面に露出する純Ｎｉの薄層６
は、これが覆っているＡｌ合金板２を塩基性雰囲気や薬
品から保護する。Then, as shown on the left side of FIG. 4C, a Cu (oxygen-free copper) plate 4 having a thickness of 0.4 mm and a width of 90 mm is provided on the surface of the one thin layer 6 of pure Ni. After being attached, it is pushed between the pair of rolls 9 and 9 to pass. By pressing and rolling, which passes between the rolls 9, 9 at a processing (reduction) rate of 67%,
As shown in FIG. 4 (D), the overall thickness is about 0.8 mm,
And a pair of pure Ni thin layers 6 having a thickness of 2 μm in the middle and the other (lower)
An Al.Cu clad plate 1 'having the other surface is obtained. By subjecting the clad plate 1 'to diffusion annealing as described above, the layers 2, 6, and 4 can be more firmly joined to each other. The thin layer 6 of pure Ni exposed on the lower surface
Protects the Al alloy plate 2 that it covers from a basic atmosphere and chemicals.
【００２３】[0023]
【実施例】ここで、より具体的な実施例について、比較
例と共に説明する。前記図３(Ａ)〜(Ｄ)の各工程を、図
３(Ｄ)での加工(圧下)率のみを１４〜６２％の間で変化
させて、前記と同じ条件により行った結果、加工率別に
６種類の実施例のＡｌ・Ｃｕクラッド板１を得た。一
方、純Ｎｉの薄層６を除いて図３(Ａ)と図３(Ｄ)の両工
程だけを、上記と同じく図３(Ｄ)での加工率のみを変化
させて、前記と同じ条件により行い、加工率別に６種類
の比較例のＡｌ・Ｃｕクラッド板を得た。EXAMPLES Here, more specific examples will be described together with comparative examples. 3 (A) to 3 (D) were performed under the same conditions as above by changing only the processing (reduction) rate in FIG. 3 (D) from 14 to 62%. Six types of Al / Cu clad plates 1 of Examples were obtained at different rates. On the other hand, except for the thin layer 6 of pure Ni, only the steps of FIGS. 3 (A) and 3 (D) were carried out under the same conditions as described above except that only the processing rate in FIG. 3 (D) was changed. According to the above, six types of comparative example Al / Cu clad plates were obtained at different processing rates.
【００２４】これら実施例及び比較例の各Ａｌ・Ｃｕク
ラッド板に対し、図３(Ｅ)に示すように、純Ｃｕ板４が
剥がれるときに必要な力をそれぞれ測定して、各々の接
合強度とした。その結果を、加工率別に図５のグラフに
示した。図５のグラフから、加工率が２０％を越える
と、実施例の各Ａｌ・Ｃｕクラッド板１の接合強度は、
同じ加工率の比較例のものより高くなり、加工率が約５
０％付近からは著しく上昇していることが判明した。こ
の結果から、実施例のＡｌ・Ｃｕクラッド板１は、純Ａ
ｌ板２と純Ｃｕ板４との間に純Ｎｉの薄層６を介在させ
たことにより、比較例のＡｌ・Ｃｕクラッド板よりも明
らかに接合強度を向上させ得たことが裏付けられた。As shown in FIG. 3 (E), the force required when the pure Cu plate 4 was peeled off was measured for each of the Al / Cu clad plates of the example and the comparative example, and the respective joint strengths were measured. And The results are shown in the graph of FIG. From the graph of FIG. 5, when the processing rate exceeds 20%, the bonding strength of each Al / Cu clad plate 1 of the example becomes:
It is higher than that of the comparative example with the same processing rate, and the processing rate is about 5
From around 0%, it was found to have increased significantly. From these results, it is clear that the Al / Cu clad plate 1 of the example is pure A
The fact that the thin layer 6 of pure Ni was interposed between the l-plate 2 and the pure Cu plate 4 proved that the bonding strength was clearly improved as compared with the Al / Cu clad plate of the comparative example.
【００２５】次に、図３(Ｄ)の圧着圧延を加工率５０％
として、前記図３(Ａ)〜(Ｄ)の各工程を前記と同じ条件
にて行い、６枚の実施例のＡｌ・Ｃｕクラッド板１を得
た。一方、純Ｎｉの薄層６を除いて図３(Ａ)と図３(Ｄ)
の両工程のみを、図３(Ｄ)の圧着圧延を上記と同じく加
工率５０％として、前記と同じ条件にて行い、６枚の比
較例のＡｌ・Ｃｕクラッド板を得た。これら実施例及び
比較例の各Ａｌ・Ｃｕクラッド板を、個別に図示しない
真空炉内に挿入し、焼鈍温度を２００〜６００℃の温度
範囲で変化させて、拡散焼鈍を施した。Next, the compression rolling shown in FIG.
3 (A) to 3 (D) were performed under the same conditions as above, and six Al / Cu clad plates 1 of the example were obtained. 3A and 3D except for the thin layer 6 of pure Ni.
Only the two steps were carried out under the same conditions as in the above, except that the compression rolling in FIG. 3D was performed at a processing rate of 50% in the same manner as described above, and six Al / Cu clad plates of comparative examples were obtained. Each of the Al and Cu clad plates of Examples and Comparative Examples was individually inserted into a vacuum furnace (not shown), and diffusion annealing was performed while changing the annealing temperature within a temperature range of 200 to 600 ° C.
【００２６】その後、各Ａｌ・Ｃｕクラッド板に対し、
前記と同じく図３(Ｅ)に示す純Ｃｕ板４を剥離すること
によりそれぞれの接合強度を測定した。その結果を、焼
鈍温度別に図６のグラフに示した。図６のグラフから、
全ての焼鈍温度において実施例の各Ａｌ・Ｃｕクラッド
板１は、比較例のものよりも高い接合強度を有し、特に
５００〜６００℃の温度領域においては顕著な上昇傾向
を示した。この結果から、拡散焼鈍を施すことにより、
各接合面に沿って拡散層が形成されるため、一層接合強
度を高められることが裏付けられた。Then, for each Al / Cu clad plate,
As in the above, the bonding strength of each of the pure Cu plates 4 shown in FIG. The results are shown in the graph of FIG. 6 according to the annealing temperature. From the graph of FIG.
At all annealing temperatures, each Al / Cu clad plate 1 of the example had higher bonding strength than that of the comparative example, and showed a remarkable tendency to increase particularly in a temperature range of 500 to 600 ° C. From this result, by performing diffusion annealing,
Since the diffusion layer is formed along each bonding surface, it is supported that the bonding strength can be further increased.
【００２７】次に、前記図４(Ａ)〜(Ｃ)の各工程を経て
得られたＡｌ・Ｃｕクラッド板１′について、更に焼鈍
温度を変化させて、図７に示すエリクセン試験を行っ
た。また、比較例としてＮｉメッキをしていないＡｌ合
金板２に前記と同じＣｕ板４を同様に圧着圧延したクラ
ッド板も用意し、同じエリクセン試験を行った。図７に
示すエリクセン試験は、上記クラッド板１′の絞り加工
性を測定する試験で、孔ｈを有するベースＢ上に周囲を
押え板ｐで押圧してクラッド板１′を拘束し、上記孔ｈ
内を所定の力で上昇して衝突する鋼球ｂにより、クラッ
ド板１′の盛り上がる高さを測定するものである。尚、
実施例及び比較例の各Ａｌ・Ｃｕクラッド板を焼鈍温度
毎に１０枚ずつ用意し、それらのエリクセン試験におけ
るエリクセン値(突出高さ)の平均値を算出した。その結
果を焼鈍温度別に図８のグラフに示した。Next, the Erichsen test shown in FIG. 7 was performed on the Al.Cu clad plate 1 'obtained through the steps of FIGS. 4A to 4C while further changing the annealing temperature. . Further, as a comparative example, a clad plate in which the same Cu plate 4 as described above was similarly pressed and rolled on an Al alloy plate 2 not plated with Ni was also prepared, and the same Erichsen test was performed. The Erichsen test shown in FIG. 7 is a test for measuring the drawability of the clad plate 1 ′. The periphery of the clad plate 1 ′ is restrained by pressing the periphery of the clad plate 1 ′ on a base B having a hole h with a holding plate p. h
The height at which the clad plate 1 'swells is measured by the steel ball b which rises and collides with the inside with a predetermined force. still,
Ten Al / Cu clad plates of Examples and Comparative Examples were prepared for each annealing temperature, and the average value of the Erichsen values (projection height) in the Erichsen test was calculated. The results are shown in the graph of FIG. 8 for each annealing temperature.
【００２８】図８のグラフから、実施例の各クラッド板
１′は、焼鈍温度の上昇と共にエリクセン値も増加し、
且つ５００℃以上で顕著に増加した。これはＡｌ合金板
２及びＣｕ板４とＮｉ薄層６との各接合面で相互に拡散
が生じたが、ＮｉＡｌ及び／又はＮｉ3Ａｌ系の脆い金
属間化合物が形成されなかったためと思われる。また、
５００℃以上でエリクセン値が顕著に増えたのは、Ｃｕ
板４の回復現象によるものと考えられる。一方、比較例
の各クラッド板は、全体として実施例よりも低く、且つ
焼鈍温度が３００℃でエリクセン値は最大となるがそれ
以上では低下していた。これは、Ａｌ合金板２とＣｕ板
４との間にＮｉ薄層６が介在していないため、その接合
面に沿って脆いＡｌ−Ｃｕ系金属間化合物の層が形成さ
れたものと思われる。この結果から、実施例のクラッド
板１′は、絞り加工に適しており、深絞り加工によって
前記電池用ケース８，８′を容易に成形できることが理
解される。From the graph of FIG. 8, it is found that the Erichsen value of each clad plate 1 'of the embodiment increases as the annealing temperature increases.
And it increased remarkably above 500 ° C. This is presumably because diffusion occurred at the joint surfaces between the Al alloy plate 2 and the Cu plate 4 and the Ni thin layer 6, but no brittle intermetallic compounds of NiAl and / or Ni 3 Al were formed. . Also,
The Erichsen value increased remarkably above 500 ° C.
This is considered to be due to the recovery phenomenon of the plate 4. On the other hand, each clad plate of the comparative example was lower than the example as a whole, and the Erichsen value became maximum at an annealing temperature of 300 ° C., but decreased at higher temperatures. This is presumably because the Ni thin layer 6 was not interposed between the Al alloy plate 2 and the Cu plate 4, so that a brittle Al-Cu intermetallic compound layer was formed along the joint surface. . From these results, it is understood that the clad plate 1 'of the embodiment is suitable for drawing, and the battery cases 8, 8' can be easily formed by deep drawing.
【００２９】本発明は、以上に説明した各形態に限定さ
れるものではない。例えば、前記Ａｌ・Ｃｕクラッド板
１，１′において、純Ａｌ板２と純Ｃｕ板４の各板厚を
互いに相違したものを用い得ることは明白である。ま
た、図９(Ａ)に示すように、Ａｌ板又はＡｌ基合金板２
の一部において、純Ｎｉの薄層６を介してＣｕ板又はＣ
ｕ基合金板４を接合したＡｌ・Ｃｕクラッド板１２とし
たり、逆に図９(Ｂ)に示すように、Ｃｕ板又はＣｕ基合
金板４の一部において、純Ｎｉの薄層６を介してＡｌ板
又はＡｌ基合金板２を接合したＡｌ・Ｃｕクラッド板１
４とすることもできる。これらのクラッド板１２，１４
は、成形加工された後のケース等の製品の構造や形状或
いは求められる特性に応じて、小さい面積側の板材を予
め必要な形状にしてから、これを大きな面積側の板材に
おける所望の位置に接合することにより、有効に活用す
ることが可能となる。The present invention is not limited to the embodiments described above. For example, in the Al.Cu clad plates 1 and 1 ', it is apparent that the pure Al plate 2 and the pure Cu plate 4 may have different thicknesses. Also, as shown in FIG. 9A, an Al plate or an Al-based alloy plate 2
In a part of the substrate, a Cu plate or C
The u-base alloy plate 4 is joined to the Al-Cu clad plate 12, or, as shown in FIG. 9B, the Cu plate or a part of the Cu-base alloy plate 4 through the thin layer 6 of pure Ni. Al-Cu clad plate 1 joined with Al plate or Al-based alloy plate 2
4 can also be used. These clad plates 12, 14
According to the structure and shape of the product such as the case after molding, or the required characteristics, the plate material on the small area side is made into a required shape in advance, and then this is placed at a desired position on the plate material on the large area side. By joining, it is possible to utilize it effectively.
【００３０】例えば、図９(Ｃ)に示すように、前記Ａｌ
・Ｃｕクラッド板１２を深絞り加工して、有底円筒形の
電池用ケース１６を成形した後、その外側になるＡｌ板
又はＡｌ基合金板２における上周縁のＡｌ板２の単独部
分をカーリング加工し、このケース１６の開口部１７の
周囲に沿ってカール部１８を形成することもできる。上
記ケース１６に関連し、前記Ａｌ・Ｃｕクラッド板１４
を深絞り加工して有底筒形のケースとし、その外側の上
周縁となるＣｕ板４の単独部分をカーリング加工して、
Ｃｕ板４のみからなるカール部１８を形成することも可
能である。更に、上記カーリング加工に際し、図示しな
い蓋板をケース１６の開口部１７上に載置して、その蓋
板の外周縁と上記Ａｌ板２又はＣｕ板４における上周縁
の単独部分を重ねた状態でカーリング加工する所謂巻き
締めを全周囲に渉り施すと、缶詰と同様な密封構造の電
池用等のケース又は容器とすることも可能である。For example, as shown in FIG.
After deep-drawing the Cu clad plate 12 to form a bottomed cylindrical battery case 16, a single portion of the outer peripheral Al plate 2 of the Al plate or the Al-based alloy plate 2 on the outside thereof is curled. The curl portion 18 can be formed along the periphery of the opening 17 of the case 16 by processing. In connection with the case 16, the Al / Cu clad plate 14
Is deep-drawn to form a bottomed cylindrical case, and a single portion of the Cu plate 4 serving as an outer peripheral edge of the case is curled,
It is also possible to form the curled portion 18 composed of only the Cu plate 4. Further, a cover plate (not shown) is placed on the opening 17 of the case 16 during the curling process, and the outer peripheral edge of the cover plate and the single portion of the upper peripheral edge of the Al plate 2 or the Cu plate 4 are overlapped. When a so-called curling process is performed over the entire periphery, a case or container for a battery or the like having a sealed structure similar to that of a can can be obtained.
【００３１】また、図９(Ｄ)は、超音波検出装置に用い
られる超音波共振子２０の断面図を示す。この超音波共
振子２０は、前記Ａｌ・Ｃｕクラッド板１(１′)を例え
ば円錐形の回転する成形型の頂部分に固定し、該成形型
と反対側のクラッド板１の頂部分から周縁に向けてロー
ラ等で押し付けつつ移動させることにより、図示のよう
な緩いテーパの中空円錐体に成形したものである。この
超音波共振子２０は、図中の矢印で示す超音波を内側面
に受けるとその強度等に応じて共振する。そして、共振
子２０の頂部分に接合した図示しない圧電素子を介して
これに接続される電気回路内で、超音波の強度等に応じ
た電流／電圧を発生させて、超音波を検出・受信するの
に用いられる。FIG. 9D is a sectional view of an ultrasonic resonator 20 used in the ultrasonic detecting device. The ultrasonic resonator 20 fixes the Al.Cu clad plate 1 (1 ') to, for example, the top of a conical rotating mold, and extends from the top to the periphery of the clad plate 1 on the opposite side of the mold. It is shaped into a hollow cone having a loose taper as shown by moving it while pressing it with a roller or the like. The ultrasonic resonator 20 resonates according to its strength when receiving an ultrasonic wave indicated by an arrow in the figure on the inner surface. Then, a current / voltage corresponding to the intensity of the ultrasonic wave is generated in an electric circuit connected thereto via a piezoelectric element (not shown) bonded to the top portion of the resonator 20 to detect and receive the ultrasonic wave. Used to do.
【００３２】従って、純Ｎｉの薄層６を介してＡｌ板又
はＡｌ基合金板２とＣｕ板又はＣｕ基合金板４を接合し
たＡｌ・Ｃｕクラッド板１，１′を用い、或いは前記拡
散焼鈍を施したクラッド板１，１′を用いることによ
り、上記超音波共振子２０は、比較的薄肉化できると共
に、各種の超音波に対し鋭敏に反応して共振現象を確実
に生じさせることが可能となる。このため、超音波検出
装置の検出能力を向上させることにも寄与でき得る。Therefore, an Al / Cu clad plate 1, 1 'in which an Al plate or an Al-based alloy plate 2 and a Cu plate or a Cu-based alloy plate 4 are joined via a thin layer 6 of pure Ni, or the diffusion annealing By using the clad plates 1 and 1 ′ subjected to the above, the ultrasonic resonator 20 can be made relatively thin, and it is possible to reliably generate a resonance phenomenon by reacting sharply to various ultrasonic waves. Becomes For this reason, it can contribute to improving the detection capability of the ultrasonic detection device.
【００３３】更に、前記Ａｌ板又はＡｌ基合金板２に
は、純度９９．０％以上の純Ａｌ系の他、Ａｌ−Ｃｕ
系、Ａｌ−Ｍｎ系(例えば前記JIS;Ａ３００３)、Ａｌ−
Ｓｉ系、Ａｌ−Ｍｇ系、Ａｌ−Ｍｇ−Ｓｉ系、及びＡｌ
−Ｚｎ系に属する各種の展伸用アルミニウム合金を適用
することも可能である。また、前記Ｃｕ板又はＣｕ基合
金板４には、純銅(燐脱酸銅、無酸素銅)の他、Ｃｕ−Ｚ
ｎ系合金(黄銅、例えばJIS;Ｃ２１００〜Ｃ２４００、
α黄銅、α＋β黄銅、特殊黄銅）、Ｃｕ−Ｓｎ系合金(青
銅、例えばJIS;ＢＣ１〜ＢＣ７、ＫＪ１〜ＫＪ４、隣青
銅)、Ｃｕ−Ｎｉ系合金(白銅、洋白、アドバンス、モネ
ルメタル等)、Ａｌ青銅、Ｂｅ銅、Ｓｉ銅、又は導電用
銅合金を適用することも可能である。尚、前記接合工程
には、圧着圧延の他、爆着を用いることも可能である。Further, the Al plate or the Al-based alloy plate 2 includes pure Al-based material having a purity of 99.0% or more,
System, Al-Mn system (for example, JIS; A3003), Al-
Si-based, Al-Mg-based, Al-Mg-Si-based, and Al
It is also possible to apply various wrought aluminum alloys belonging to the -Zn system. In addition to pure copper (phosphorous deoxidized copper and oxygen-free copper), Cu-Z
n-based alloy (brass, for example, JIS; C2100 to C2400,
α-brass, α + β-brass, special brass), Cu-Sn-based alloys (bronze, for example, JIS; BC1-BC7, KJ1-KJ4, next bronze), Cu-Ni-based alloys (white copper, nickel silver, advance, Monel metal, etc.), It is also possible to apply Al bronze, Be copper, Si copper, or a copper alloy for electric conduction. In the joining step, it is also possible to use explosion other than pressure rolling.
【００３４】[0034]
【発明の効果】以上において説明した本発明のクラッド
板は、Ａｌ系板とＣｕ系板とを純Ｎｉの薄層を介して一
体に接合したので、深絞り加工のような過酷な変形を受
けてもＡｌ系板とＣｕ系板との間でずれたり、剥離した
りせず、各種の形状の製品や部品に成形されても強固な
接合強度を維持することができる。しかも、得られる成
形品の耐久性を高めることにも寄与することが可能とな
る。また、本発明の電池用ケースは、有底筒形の内周面
に陰極となるＣｕ系板が位置し、外周面にＡｌ系板又は
その表面に被覆された純Ｎｉの薄層が位置するので、軽
量で強度もあり、且つ耐食性に優れるという利点を有す
る。The clad plate of the present invention described above is formed by joining an Al-based plate and a Cu-based plate integrally with each other via a thin layer of pure Ni. Even when the Al-based plate and the Cu-based plate are not displaced or peeled from each other, a strong bonding strength can be maintained even when molded into products and parts of various shapes. In addition, it is possible to contribute to enhancing the durability of the obtained molded product. In the battery case of the present invention, a Cu-based plate serving as a cathode is located on the inner peripheral surface of the bottomed cylindrical shape, and an Al-based plate or a thin layer of pure Ni coated on the surface is located on the outer peripheral surface. Therefore, it has the advantages of being lightweight, having strength, and having excellent corrosion resistance.
【００３５】一方、本発明のクラッド板の製造方法によ
れば、以上のようなＡｌ・Ｃｕクラッド板を比較的少な
い工数と労力により確実に提供することができる。ま
た、請求項７の製造方法によれば、Ａｌ系板にマスキン
グすることなくＮｉメッキが行え、且つＡｌ系板が露出
しないので、Ａｌが腐食し易い塩基性雰囲気や薬品等の
付近における用途において耐久性を高めることができ
る。更に、請求項８に記載の拡散焼鈍を施すことによ
り、Ａｌ系板とＣｕ系板との接合強度を一層高めること
ができる。加えて、本発明の電池用ケースの製造方法に
よれば、上記した有底筒形のケースを精度良く確実に提
供することができる。On the other hand, according to the method for manufacturing a clad plate of the present invention, the above-described Al / Cu clad plate can be reliably provided with relatively few man-hours and labor. According to the manufacturing method of the seventh aspect, Ni plating can be performed without masking the Al-based plate and the Al-based plate is not exposed, so that Al is easily corroded. Durability can be increased. Furthermore, by performing the diffusion annealing according to claim 8, the bonding strength between the Al-based plate and the Cu-based plate can be further increased. In addition, according to the method for manufacturing a battery case of the present invention, it is possible to accurately and reliably provide the above-described bottomed cylindrical case.
【図１】(Ａ)はクラッド板の１形態を示す部分断面図、
(Ｂ)はこれを成形した電池用ケースの垂直断面図、(Ｃ)
及び(Ｄ)は応用形態のクラッド板の部分断面図。FIG. 1A is a partial cross-sectional view showing one embodiment of a clad plate,
(B) is a vertical cross-sectional view of a battery case molded from the same, (C)
(D) is a partial cross-sectional view of a clad plate of an applied form.
【図２】(Ａ)は更に異なる形態のクラッド板の部分断面
図、(Ｂ)はこれを成形した電池用ケースの垂直断面図。FIG. 2A is a partial cross-sectional view of a clad plate having a further different form, and FIG. 2B is a vertical cross-sectional view of a battery case formed from the clad plate.
【図３】(Ａ)乃至(Ｄ)は図１(Ａ)のクラッド板の各製造
工程の概略を示す部分断面図、(Ｅ)はその接合強度を測
定する状態を示す概略図。3 (A) to 3 (D) are partial cross-sectional views schematically showing manufacturing steps of the clad plate of FIG. 1 (A), and FIG. 3 (E) is a schematic view showing a state in which the bonding strength is measured.
【図４】(Ａ)乃至(Ｄ)は図２(Ａ)のクラッド板の各製造
工程の概略を示す部分断面図。4 (A) to 4 (D) are partial cross-sectional views schematically showing each manufacturing process of the clad plate of FIG. 2 (A).
【図５】本発明の実施例と比較例のクラッド板における
加工率と接合強度との関係を示すグラフ。FIG. 5 is a graph showing the relationship between the working ratio and the bonding strength in the clad plates of the example of the present invention and the comparative example.
【図６】本発明の実施例と比較例のクラッド板における
焼鈍温度と接合強度との関係を示すグラフ。FIG. 6 is a graph showing the relationship between the annealing temperature and the bonding strength in the clad plates of the example of the present invention and the comparative example.
【図７】エリクセン試験の状態を示す概略図。FIG. 7 is a schematic diagram showing the state of the Erichsen test.
【図８】本発明の実施例と比較例のクラッド板における
焼鈍温度とエリクセン値との関係を示すグラフ。FIG. 8 is a graph showing a relationship between an annealing temperature and an Erichsen value in clad plates of an example of the present invention and a comparative example.
【図９】(Ａ)及び(Ｂ)は更に異なる形態のＡｌ・Ｃｕク
ラッド板の部分断面図、(Ｃ)及び(Ｄ)はこれを成形加工
したケース等の垂直断面図。FIGS. 9A and 9B are partial cross-sectional views of an Al.Cu clad plate having further different shapes, and FIGS. 9C and 9D are vertical cross-sectional views of a case or the like formed by processing the same.
１,１′，１０,１０′,１２,１４…Ａｌ・Ｃｕクラッド
板(クラッド板) ２………………………………………Ａｌ板又はＡｌ基合
金板 ４………………………………………Ｃｕ板又はＣｕ基合
金板 ６………………………………………純Ｎｉの薄層 ８，８′，１６………………………電池用ケース1,1 ', 10,10', 12,14 Al / Cu clad plate (cladded plate) 2 ... Al plate or Al-based alloy plate 4 ... ……………………………………………………………………………………………………………………………………………………………………………………………. …………… Battery case
Claims (9)
基合金板とを、純Ｎｉの薄層を介して一体に接合した、
ことを特徴とするクラッド板。1. A Cu plate or Cu-based alloy plate and an Al plate or Al
The base alloy plate was joined together via a thin layer of pure Ni,
A clad plate characterized by the above.
被覆した純Ｎｉの薄層と、何れかの純Ｎｉの薄層の表面
上に被覆したＣｕ板又はＣｕ基合金板とを有する、こと
を特徴とするクラッド板。2. An Al plate or an Al-based alloy plate, a pure Ni thin layer coated on both surfaces thereof, and a Cu plate or a Cu-based alloy plate coated on the surface of any of the pure Ni thin layers. A clad plate comprising:
はＡｌ基合金板の何れかの両表面にそれぞれ純Ｎｉの薄
層を介して、一対のＡｌ板又はＡｌ基合金板、或いは一
対のＣｕ板又はＣｕ基合金板を各々一体に接合した、 ことを特徴とするクラッド板。3. A pair of Al plates or Al-based alloy plates, or a pair of Al plates or Al-based alloy plates, on both surfaces of either a Cu plate or a Cu-based alloy plate, or an Al plate or an Al-based alloy plate via a thin layer of pure Ni. Wherein the Cu plate or the Cu-based alloy plate is integrally joined.
板を用いると共に、全体が有底筒形で且つその内周面側
に前記Ｃｕ板又はＣｕ基合金板を配置した、 ことを特徴とする電池用ケース。4. The method according to claim 1, wherein the clad plate according to any one of claims 1 to 3 is used, the whole is a bottomed cylindrical shape, and the Cu plate or Cu-based alloy plate is arranged on the inner peripheral surface side. Characteristic battery case.
基合金板とを、それらの間に純Ｎｉの薄層を配設して接
合する、 ことを特徴とするクラッド板の製造方法。5. A Cu plate or Cu-based alloy plate and an Al plate or Al
A method for manufacturing a clad plate, comprising: arranging a thin layer of pure Ni between the base alloy plate and the base alloy plate and joining them.
一方の表面にＮｉメッキにより厚さ０．３〜１５μｍの
純Ｎｉの薄層を被覆する工程と、この純Ｎｉの薄層の表
面上に前記Ａｌ板又はＡｌ基合金板を圧着圧延又は爆着
等により接合する工程と、を含むことを特徴とする請求
項５に記載のクラッド板の製造方法。6. A step of coating at least one surface of the Cu plate or the Cu-based alloy plate with a thin layer of pure Ni having a thickness of 0.3 to 15 μm by Ni plating; And bonding the Al plate or the Al-based alloy plate by pressure rolling, explosion bonding, or the like.
一方の表面にＮｉメッキにより厚さ０．３〜１５μｍの
純Ｎｉの薄層を被覆する工程と、この純Ｎｉの薄層の何
れかの表面上に前記Ｃｕ板又はＣｕ基合金板を圧着圧延
又は爆着等により接合する工程と、 を含むことを特徴とする請求項５に記載のクラッド板の
製造方法。7. A step of coating at least one surface of said Al plate or Al-based alloy plate with a thin layer of pure Ni having a thickness of 0.3 to 15 μm by Ni plating, and any one of said thin layers of pure Ni. The method for producing a clad plate according to claim 5, further comprising: bonding the Cu plate or the Cu-based alloy plate to the surface of the clad plate by pressure rolling, explosion, or the like.
記接合工程の後に、得られたクラッド板に約２００〜６
００℃の範囲で拡散焼鈍を施す工程を行う、 ことを特徴とするクラッド板の製造方法。8. The method according to claim 6, further comprising the steps of: attaching the obtained clad plate to the clad plate after the joining step;
Performing a diffusion annealing step in a temperature range of 00 ° C.
請求項８の前記焼鈍工程の後において、前記クラッド板
を有底筒形に絞り加工する成形工程を行う、 ことを特徴とする電池用ケースの製造方法。9. A forming step of drawing the clad plate into a bottomed cylindrical shape after the joining step according to claim 6 or 7, or after the annealing step according to claim 8. Manufacturing method for a battery case.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10091099A JPH11156995A (en) | 1997-09-25 | 1998-04-03 | Clad plate, battery case using it, and manufacture thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26070997 | 1997-09-25 | ||
| JP9-260709 | 1997-09-25 | ||
| JP10091099A JPH11156995A (en) | 1997-09-25 | 1998-04-03 | Clad plate, battery case using it, and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11156995A true JPH11156995A (en) | 1999-06-15 |
Family
ID=26432576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10091099A Withdrawn JPH11156995A (en) | 1997-09-25 | 1998-04-03 | Clad plate, battery case using it, and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11156995A (en) |
Cited By (18)
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|---|---|---|---|---|
| EP1204304A2 (en) * | 2000-11-01 | 2002-05-08 | Visteon Global Technologies, Inc. | Etched tri-layer metal bonding layer |
| KR100601535B1 (en) | 2004-07-28 | 2006-07-19 | 삼성에스디아이 주식회사 | Manufacturing method of outer case for battery |
| JP2007315935A (en) * | 2006-05-26 | 2007-12-06 | Neomax Material:Kk | Flaw inspection method |
| WO2011155379A1 (en) * | 2010-06-08 | 2011-12-15 | 株式会社Ｎｅｏｍａｘマテリアル | Aluminum copper clad material |
| WO2012133654A1 (en) * | 2011-03-30 | 2012-10-04 | 株式会社Ｎｅｏｍａｘマテリアル | Negative electrode terminal and cover member for lithium ion batteries, and lithium ion battery |
| JP5202772B1 (en) * | 2011-08-04 | 2013-06-05 | 株式会社Ｎｅｏｍａｘマテリアル | Battery negative terminal |
| US8802242B2 (en) | 2009-05-29 | 2014-08-12 | Neomax Materials Co., Ltd. | Clad plate |
| JP2015027697A (en) * | 2013-07-04 | 2015-02-12 | 住友金属鉱山株式会社 | CLAD MATERIAL OF Pb-FREE Zn-Al-BASED ALLOY SOLDER AND Cu- BASED BASE MATERIAL AND PRODUCTION METHOD OF THE SAME |
| JP2015128883A (en) * | 2014-01-09 | 2015-07-16 | 株式会社Ｎｅｏｍａｘマテリアル | Chassis and portable device |
| JP5830727B2 (en) * | 2010-06-10 | 2015-12-09 | 富山県 | Coupling member and manufacturing method |
| CN106784419A (en) * | 2016-12-21 | 2017-05-31 | 常熟高嘉能源科技有限公司 | A kind of corrosion-resistant dynamic lithium battery aluminum hull and preparation method thereof |
| EP3114716A4 (en) * | 2014-03-06 | 2017-07-26 | UniCell LLC | Battery cells and arrangements |
| KR20180009379A (en) * | 2015-11-24 | 2018-01-26 | 다이닛쿠 가부시키가이샤 | Lid |
| US9968012B2 (en) | 2012-10-16 | 2018-05-08 | Mitsubishi Materials Corporation | Heat-sink-attached power module substrate, heat-sink-attached power module, and method for producing heat-sink-attached power module substrate |
| US10011093B2 (en) | 2012-09-21 | 2018-07-03 | Mitsubishi Materials Corporation | Bonding structure of aluminum member and copper member |
| KR20180085456A (en) * | 2017-01-19 | 2018-07-27 | 주식회사 엘지화학 | Battery Case Comprising Clad-typed Metal Layer and Battery Cell Comprising the Same |
| KR20180128420A (en) * | 2017-03-24 | 2018-12-03 | 히타치 긴조쿠 가부시키가이샤 | Manufacturing method of clad material |
| CN113414237A (en) * | 2021-06-21 | 2021-09-21 | 西安理工大学 | Method for preparing high-performance Al-Cu-Al composite material by rolling |
-
1998
- 1998-04-03 JP JP10091099A patent/JPH11156995A/en not_active Withdrawn
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1204304A3 (en) * | 2000-11-01 | 2002-12-11 | Visteon Global Technologies, Inc. | Etched tri-layer metal bonding layer |
| EP1204304A2 (en) * | 2000-11-01 | 2002-05-08 | Visteon Global Technologies, Inc. | Etched tri-layer metal bonding layer |
| KR100601535B1 (en) | 2004-07-28 | 2006-07-19 | 삼성에스디아이 주식회사 | Manufacturing method of outer case for battery |
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