JPH11156995A - Clad plate, battery case using it, and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an Al.Cu clad plate capable of precisely molding a desired shape without slipping out of place or peeling of joined Al sheet and Cu sheet even if deep drawing is applied, and to provide a battery case using it and manufacturing method of those. SOLUTION: A genuine Al sheet 2 and a genuine Cu sheet 4 are integrally joined with a genuine Ni thin layer 6 having 0.3-15 μm thickness therebetween. A battery case 8 is formed by drawing a cladded sheet 1 into a cylindrical shape having the bottom. The genuine Ni thin layer 6 having 20 μm thickness is coated on one surface of the genuine Cu sheet 4 by deposition, and the surface of the thin layer 6 is pressed by a wire brush 7 for activating and forming fine recessed and projected lines. And then, the genuine Al sheet 2 is placed thereon for applying contact bonding and rolling through a pair of rolls with a processing rate of 50%, so that the thickness of the genuine Ni thin layer 6 is 10 μm. After the rolling process, diffusing annealing is performed at a temperature of 200-600 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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]

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.

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.

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]

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]

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.

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.

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.

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.

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.

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.

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] 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]

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.

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.

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.

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.

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.

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.

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.

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.

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]

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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]

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.

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.

[Brief description of the drawings]

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.

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.

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.

4 (A) to 4 (D) are partial cross-sectional views schematically showing each manufacturing process of the clad plate of FIG. 2 (A).

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.

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.

FIG. 7 is a schematic diagram showing the state of the Erichsen test.

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.

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.

[Explanation of symbols]

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)

[Claims] 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. 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: 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. 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. 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. 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. 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. 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. 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.