JP2005251429A - METAL FOIL WITH Al ALLOY CARRIER OPENING AND MANUFACTURING METHOD OF THE SAME, ELECTRODE FOR SECONDARY BATTERY SEPARATED FROM THE METAL FOIL WITH Al ALLOY CARRIER OPENING AND INCLUDING THE METAL FOIL WITH THE OPENING, AND SECONDARY BATTERY - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal foil with Al alloy carrier opening having many opening parts forming a three dimensional reticulated structure having uniformly distributed fine cavities, a simple manufacturing method of the same with small number of processes, and an electrode for a secondary battery separated from the metal foil with Al alloy carrier opening and including the metal foil with the opening. <P>SOLUTION: On the metal foil with Al alloy carrier opening can be obtained, a uniform protrusion parts are formed on a contact face of the carrier and the metal foil by etching Al. The metal foil is formed on the carrier by gradual growth and stretch of metal particles with the electric charge concentration part of the protrusion part as an electrodeposition center of the metal particle, as a result, the metal foil with Al alloy carrier opening can be obtained. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a perforated metal foil having a large number of holes and a method for producing the same. Moreover, this invention relates to the electrode for secondary batteries containing a perforated metal foil provided with such many holes, and a secondary battery.

  In recent years, the demand for high-capacity secondary batteries as power sources for portable electronic devices such as portable PCs and video cameras, or power sources for electric vehicles has increased. Development and commercialization are progressing rapidly.

  Now, there has been proposed a current collector made of a porous metal foil that can be used as a current collector for this Li-ion secondary battery and has a three-dimensional network structure in which the communicating holes in the thickness direction of the foil are formed. (See Patent Documents 1, 2, 3, and 4).

  In particular, according to the invention of the current collector made of the porous metal foil proposed in Patent Document 3 or 4, the following advantages are brought about. First, it is possible to control the aperture ratio and the aperture diameter of the porous metal foil that forms the three-dimensional network structure. Secondly, the capacity of the non-aqueous electrolyte secondary battery can be increased by sufficiently ensuring the flow path of the electrolyte in the porous metal foil. Third, it is possible to effectively prevent the active material from falling out of the electrode due to insertion or extraction of Li and improve cycle characteristics.

Hereinafter, with reference to FIG. 10 and FIG. 11, a method for producing a current collector made of a porous metal foil proposed in Patent Document 4 as a representative example of the conventional example, particularly a negative electrode for a non-aqueous electrolyte secondary battery Is briefly explained.
10, (a) First, carrier foil 1 is prepared, and (b) a thin release layer 2 is formed on one surface of carrier foil 1. (C) A metal material having a low Li compound forming ability is electroplated thereon to form one current collecting surface layer 3a, and (d) active material particles are formed on the current collecting surface layer 3a. The active material layer 4 is formed by applying a conductive slurry containing, and (e) electroplating a metal material having a low Li compound forming ability on the active material to form the other current collecting surface layer 3b. Then, (f) the carrier foil 1 is peeled and separated from the negative electrode 10 at the interface between the one current collecting surface layer 3 a and the peeling layer 2 together with the peeling layer 2. 10 is a schematic diagram, the current collecting surface layers 3a and 3b are clearly distinguished from the active material layer 4, and are shown as if the negative electrode 10 has a three-layer structure. Actually, however, as shown in FIG. 11, the constituent materials of the surface layers 3a and 3b penetrate into the active material 4, and the surface layers 3a and 3b are in communication with each other. The negative electrode 10 of the present embodiment thus obtained is used together with a known positive electrode, separator, and non-aqueous electrolyte to constitute a non-aqueous electrolyte secondary battery.

Now, a thin release layer 2 is formed on one surface of the carrier foil 1, and this release layer 2 is formed of a nitrogen compound, a sulfur compound, a nitrogen-containing compound, a mixture of a sulfur-containing compound and metal fine particles, or It is formed by chromate treatment or Ni plating treatment. Then, by performing electroplating on the release layer 2, fine voids 7 (see FIG. 11) that are unevenly distributed in the surface layer 3a are formed. Further, the active material layer 4 is formed by applying a conductive slurry thereon, but the surface to be applied has a high surface roughness due to the uneven mat surface. By the way, since this slurry contains active material particles, conductive carbon material particles, a binder, a diluting solvent, and the like, a layer like the active material layer 4 indicated by reference numeral 4 in FIG. These inclusions are contained non-uniformly in the interior of the container. Therefore, when the coating film of the slurry is further dried to form the active material layer 4 and further electroplating is performed on the active material layer 4, the surface layer 3b is formed, and the material constituting the surface layer 3b is the active material. It permeates over the entire thickness direction of the layer 4, and the surface layers 3a and 3b communicate with each other. Furthermore, a large number of non-uniformly distributed fine voids 7 are also formed in the surface layer 3b.
JP-A-8-236120 International Publication WO00 / 15875 Japanese Patent Application No. 2003-360938 Japanese Patent Application No. 2003-403528

  By the way, when the volume of the negative electrode 10 expands due to occlusion of Li during charging due to the presence of the fine gap 7, the stress generated in the negative electrode 10 due to the volume expansion is relieved. The fine voids 7 are formed unevenly inside the negative electrode 10. For this reason, the stress is generated unevenly inside the negative electrode 10, and as a result, the stability of the performance of the negative electrode 10 and its life may be adversely affected. Furthermore, as described above with reference to FIG. 10, the manufacturing method proposed in Patent Document 4 has a large number of steps.

  Accordingly, an object of the present invention is to provide a perforated metal foil with an Al alloy carrier having a plurality of holes forming a three-dimensional network structure having a plurality of uniformly distributed fine voids by a simple manufacturing method with fewer steps. Another object of the present invention is to provide a current collector for a secondary battery including a metal foil separated from a perforated metal foil with an Al alloy carrier and a method for producing the same.

  In such a situation, the present inventors made extensive studies, and as a result, created a current collector as a perforated metal foil having a large number of holes forming a three-dimensional network structure having a plurality of uniformly distributed fine voids. The following methods were discovered.

  First, the surface of the carrier foil made of an Al alloy containing dispersed precipitates such as Al and Fe and Si is alkali degreased, and simultaneously with the degreasing treatment, the surface of the carrier foil is etched by etching Al on the surface. To make it protrude evenly. Then, when electroplating is applied to the surface of the carrier foil, the growth of metal particles starts with the dispersed precipitation portion as the core of electrodeposition, and the grown metal particles are connected to each other as the core of electrodeposition, so that the perforated metal A foil is formed on the carrier foil to form a perforated metal foil with an Al alloy carrier. Further, by peeling the metal foil from the carrier foil, a perforated metal foil having a plurality of holes having a three-dimensional network structure having a plurality of uniformly distributed fine voids is obtained. This perforated metal foil is suitably used as a current collector for a secondary battery, particularly as a current collector for a non-aqueous electrolyte secondary battery.

  The means for solving the problem will be specifically described below. In the present invention, the “thickness” or “film thickness” of the degreased / etched carrier foil and the metal foil electrodeposited thereon is determined from the weight of a certain area of the obtained metal foil. The average thickness or the average film thickness converted by the so-called gravimetric method. Since the carrier foil and metal foil also have irregularities on the surface, when measuring the film thickness locally, some parts are 1 μm and other parts are 5 μm, so measure the “thickness” or “film thickness” of these foils This is the most suitable measurement method.

<Perforated metal foil with Al alloy carrier>
The present invention (1) is a perforated metal foil with an Al alloy carrier provided with a perforated metal foil layer on the surface of the Al alloy foil, and the perforated metal foil layer electrodeposits metal on the surface of the Al alloy carrier. And the metal foil layer is a perforated metal foil layer having a large number of holes extending from the one surface to the other surface. Metal foil.

  A suitable material for the Al alloy foil is a JIS standard 1N30 Al alloy (Al> 99.30%, Fe + Si <0.7%) (note that the lower limit of the Fe + Si concentration is Fe + Si> 0.01%). Preferably Fe + Si> 0.1%). This Al alloy has Al as a main component in the alloy, and Fe and Si are uniformly dispersed in Al as a dispersion precipitation portion. However, in order to solve the problem of the present invention, the different elements other than Al contained in the Al alloy are not limited to Fe and Si.

  This Al alloy foil is preferably long and can be wound up, and has a flat surface when stretched from the wound state. “Foil” includes the concept of a plate-like member. Therefore, in the present invention, the Al alloy foil can be rephrased as an Al alloy plate. In addition, the wound type is particularly suitable for a mass production scale, and the plate type is particularly suitable for production of a batch scale (for example, a trial production stage).

  In addition, the Al alloy foil is required to have a certain thickness because it requires a sufficient and sufficient strength as a carrier for assembling a metal foil as a current collector to a secondary battery while taking into account the thickness reduced by etching. Is necessary. Therefore, a thickness of 10 μm to 100 μm is preferable. If the thickness is less than 10 μm, the strength for supporting the metal foil as a carrier is not satisfied, and there is a risk that bending or wrinkling may occur before or during assembly to the manufacturing process or the secondary battery. On the other hand, the thicker the Al alloy foil is, the more difficult it is to gradually separate the metal foil from the Al alloy foil.

  In addition, it is preferable to protect the surface of the Al alloy foil so that the surface is not damaged until the manufacturing process is started. If there is damage on the surface from the beginning, the history of damage is traced in the subsequent steps (see FIGS. 1 and 2) of the step (a) (degreasing / etching step), and thus the metal foil is not uniformly deposited. This is because there is a risk of becoming.

  Furthermore, since Cu foil or Ni foil is always supported by the Al alloy carrier until immediately before the assembly to the secondary battery, it is not damaged until immediately before the assembly. Further, since the Al alloy carrier has a certain strength, it is easy to perform manual assembly, and automation of the assembly during the secondary battery manufacturing process can be easily performed. In particular, since Cu foil or Ni foil is extremely thin and weak in strength, it is always supported by an Al alloy carrier, which brings various advantages for producing high-quality Cu foil or Ni foil efficiently and with high yield.

  The metal foil layer is formed by electrodepositing a metal on the surface of the Al alloy carrier, and the metal foil layer has a large number of holes extending from the one surface to the other surface. Since it is a perforated metal foil layer, the hole density in the metal layer can be increased. Furthermore, since there are a large number of pores having holes suitable for bringing the Li electrolyte into contact with the active material, the Li electrolyte can be brought into contact with the active material side efficiently.

The present invention (2) is a perforated metal foil with an Al alloy carrier of the present invention (1),
The contact surface of the Al alloy carrier with the metal foil layer has protrusions that are uniformly dispersed in the plane and is a perforated metal foil with an Al alloy carrier. In the present application, “uniformly dispersed” means that a certain number of protrusions are dispersed per unit area. Specifically, 10 ³ pieces / mm ² to 10 ⁵ pieces / mm ² , that is, 10 ³ pieces to 10 ⁵ pieces of protrusions exist on the metal foil with a unit area of 1 mm ² .

  The present invention (3) is a perforated metal foil with an Al alloy carrier according to the present invention (2), wherein the protruding portion is formed by degreasing the Al alloy foil and simultaneously etching the Al portion in the Al alloy. It is a perforated metal foil with an Al alloy carrier characterized by being.

  The present invention (4) is a perforated metal foil with an Al alloy carrier according to the present invention (2) or the present invention (3), wherein the protrusion on the Al alloy carrier side of the protrusion is an Al alloy foil. A perforated metal foil with an Al alloy carrier, characterized in that it is an element that is dispersed and precipitated.

  According to any one of the present inventions (2) to (4) described above with reference to FIG. 3, (the dotted line portion is etched by etching of the Al alloy foil 10 (FIG. 3A)). A dispersion precipitate portion such as Fe and Si appears on the surface of the Al alloy foil (FIG. 3B), and the metal particles 15 preferentially precipitate on the dispersion precipitate portion such as Fe and Si (FIG. 3C). )), And then the preferentially dispersed metal particles grow, and further, the metal film expands while the grown metal particles and the metal particles are connected via the grain boundary (FIG. 3 (d)). . At this time, pores are formed between the metal particles, and in the macro, they are gradually filled, but microscopically there are micropores between the metal particles, and the presence of these micropores causes the metal foil to be removed from one side. A perforated metal foil is provided having a number of holes leading to the other surface.

  The present invention (5) is a perforated metal foil with an Al alloy carrier according to any one of the present invention (1) to the present invention (4), wherein the thickness of the perforated metal foil is 1 μm to 10 μm. This is a perforated metal foil with an Al alloy carrier.

  According to the present invention (5), a perforated portion can be uniformly formed in a perforated metal foil with an Al alloy carrier, and a metal foil that is extremely thin as a current collector for a secondary battery can be provided. . In addition, the thickness of this metal foil is 1 micrometer-10 micrometers, Preferably it is 2 micrometers-5 micrometers.

  The present invention (6) is a perforated metal foil with an Al alloy carrier according to any one of the present invention (1) to the present invention (5), wherein the thickness of the carrier foil is 10 μm to 100 μm. This is a perforated metal foil with an Al alloy carrier.

  According to the present invention (6), it is possible to secure sufficient etching margin in the Al alloy carrier to etch the Al alloy, facilitating transportation and transportation of the metal foil on the carrier without damaging the metal foil, In addition, it is possible to provide a perforated metal foil with an Al alloy carrier that can easily assemble the metal foil to the secondary battery body.

  The present invention (7) is a hole with an Al alloy carrier, characterized in that the metal foil of the perforated metal foil with an Al alloy carrier according to any one of the present invention (1) to the present invention (6) is a Cu foil or a Ni foil. Open metal foil.

  According to the present invention (7), it is possible to provide a current collector including a metal foil of Cu or Ni, which is a metal material having high conductivity and advantageous in terms of cost. Particularly in the case of Ni foil, the antirust treatment after the plating treatment is unnecessary, and the number of manufacturing steps can be reduced.

<Current collector>
The present invention (8) is a current collector for an electrode for a secondary battery, and the current collector is a perforated metal foil with an Al alloy carrier according to any one of the present invention (1) to the present invention (7). Current collector.

  According to the present invention (8), since there is an Al passive oxide film at the interface between the Al alloy carrier and the perforated metal foil without requiring a special step for providing a release layer, the oxide film As a boundary surface, the perforated metal foil can be easily peeled from the Al alloy carrier, and the peeled perforated metal foil can be provided as a current collector.

<Electrode for secondary battery>
The present invention (9) is an electrode for a secondary battery provided with the current collector of the present invention (8).

This invention (10) is the electrode for secondary batteries of this invention (9), Comprising: The electrode for secondary batteries provided with the active material plating layer of Sn or Sn alloy on the electrical power collector of this invention (8) .

<Secondary battery>
This invention (11) is a secondary battery provided with the electrode for secondary batteries in any one of this invention (9) to this invention (10).

  According to the present invention (9) to the present invention (11), the metal foil layer according to the present invention is formed by electrodepositing a metal on the surface of an Al alloy carrier. And the metal foil layer is a perforated metal foil layer having a large number of holes leading from the one surface to the other surface. When the Li electrolyte solution permeates through a large number of holes extending from one surface to the other surface and comes into contact with the active material, it is possible to easily store or desorb Li.

<Method for producing perforated metal foil with Al alloy carrier>
The present invention (13) is a method for producing a perforated metal foil with an Al alloy carrier comprising a metal foil layer on the surface of an Al alloy foil including the following steps a to c, wherein the metal foil layer is an Al alloy carrier. A metal foil layer is formed by electrodepositing a metal on the surface of the metal, and a perforated metal foil layer having a large number of holes extending from the one surface to the other surface is manufactured. It is a perforated metal foil manufacturing method.
Step a. A degreasing / etching step for etching the Al part of the carrier foil while degreasing the surface of the Al alloy foil,
Step b. A water washing step of washing the etched Al alloy foil, and a step c. An electroplating step of depositing metal on the surface of the Al alloy foil after the water washing;

  According to the present invention (13), it is possible to manufacture a perforated metal foil layer having a large number of holes that are etched simultaneously with degreasing and communicate from one surface to the other surface on the Al alloy carrier. In addition, after etching, unetched portions such as Fe and Si appear uniformly on the surface of the Al alloy carrier as protrusions, and metal deposits on the charge concentration portions of the protrusions, and then the metal particles are successively connected. A perforated metal foil layer can be formed. In step b, it is preferable to wash with pure water.

<Method for producing perforated Cu foil with Al alloy carrier>
The present invention (14) is a method for producing a perforated metal foil with an Al alloy carrier comprising a Cu foil layer on the surface of an Al alloy foil including the following steps a to c, wherein the Cu foil layer is an Al alloy carrier. With an Al alloy carrier, characterized by producing a perforated Cu foil layer having a large number of holes extending from the one surface to the other surface. It is a perforated Cu foil manufacturing method.
Step a. For carrier foils with a certain size of Al alloy (for example, 10 cm × 12 cm for prototype scale, 20 cm × 400 m for mass production scale, etc.), NaOH is 15 g / L to 45 g / L, and Rochelle salt is 25 g / L to 65 g / L. And an alkaline degreasing solution having Na ₂ CO ₃ of 25 g / L to 65 g / L, and a soaking time of 10 seconds to 300 seconds at a liquid temperature of 20 ° C. to 60 ° C., 1 μm / min to 1.5 μm / min. Degreasing and etching process to perform degreasing and etching process at an etching rate of
Step b. A water washing step of washing the carrier foil in which the Al is dissolved,
Step c. Plating with CuSO ₄ concentration of 150 g / L to 350 g / L, H ₂ SO ₄ concentration of 50 g / L to 250 g / L, bath temperature of 20 ° C. to 60 ° C., and current density of 2 A / dm ^{2 to} 50 A / dm ² An electroplating step in which Cu is electrodeposited on any surface of the carrier foil for 10 seconds to 300 seconds under manufacturing conditions;
Step d. A water washing step of electrodepositing Cu to wash the Al alloy carrier foil; and a step e. Rust prevention step of immersing the above-mentioned perforated metal foil with Al alloy carrier plated with Cu in 0.1 g / L to 5 g / L of benzotriazole (BTA) solution, and subjecting the perforated metal foil with Al alloy carrier to rust prevention treatment .

  According to the present invention (14), a Cu foil having a film structure similar to that of the present invention (13) is provided, and a perforated Cu foil subjected to a rust prevention treatment is provided, and the corrosion of the Cu foil after the plating treatment is provided. Is prevented.

<Method for producing perforated Ni foil with Al alloy carrier>
The present invention (15) is a method for producing a perforated metal foil with an Al alloy carrier comprising a Ni foil layer on the surface of an Al alloy foil comprising the following steps a to c, wherein the Ni foil layer is an Al alloy carrier. With an Al alloy carrier, characterized by producing a perforated Ni foil layer having a large number of holes extending from one surface to the other surface. It is a perforated metal foil manufacturing method.
Step a. For the Al alloy carrier foil, an alkaline degreasing solution in which NaOH is 15 g / L to 45 g / L, Rochelle salt is 25 g / L to 65 g / L, and Na ₂ CO ₃ is 25 g / L to 65 g / L is used. A degreasing and etching process in which degreasing and etching are performed at an etching rate of 1 μ / min to 1.5 μ / min at a temperature of 20 ° C. to 60 ° C. for an immersion time of 10 seconds to 300 seconds;
Step b. A water washing step of washing the carrier foil in which the Al is dissolved,
Step c. NiSO ₄ · 6H ₂ O concentration is 150 g / L to 300 g / L, NiCl ₂ concentration is 50 g / L to 250 g / L, and H ₃ BO ₃ concentration is 30 g / L to 40 g / L, and the bath temperature is 30 ° C. to 70 ° C. An electroplating step in which Ni is electrodeposited on any surface of the carrier foil under the plating manufacturing conditions of ° C. and a current density of 1 A / dm ^{2 to} 40 A / dm ² .

  According to the present invention (15), a perforated Ni foil having a film structure similar to that of the present invention (13) is provided. Moreover, according to this invention (15), a rust prevention process process like a Cu foil process is not required.

  The present invention (16) is a method for producing a perforated metal foil with an Al alloy carrier according to any one of the present invention (13) to the present invention (15), wherein the contact surface of the Al alloy carrier with the metal foil layer is The metal particles for forming the metal foil layer begin to deposit uniformly on the protrusions, corners, and edges of the protrusions that are uniformly dispersed in the plane. This is a perforated metal foil with an Al alloy carrier.

  The present invention (17) is a method for producing a perforated metal foil with an Al alloy carrier according to any one of the present invention (13) to the present invention (16), wherein the uniformly deposited metal particles are used as the core of electrodeposition. A perforated metal foil with an Al alloy carrier, wherein a perforated metal foil layer is formed in the thickness direction by uniformly and sequentially depositing metal particles of the metal foil layer on the core. .

  According to the present invention (16) and the present invention (17), a perforated metal foil with an Al alloy carrier similar to the present invention (13) can be provided.

  A perforated metal foil with an Al alloy carrier having a large number of holes according to the present invention and a method for manufacturing the same are provided with an Al alloy carrier having a large number of holes having a three-dimensional network structure having a plurality of uniformly distributed fine voids. A perforated metal foil is provided. Furthermore, there is provided a perforated metal foil with an Al alloy carrier that makes it easy to transport and carry the metal foil without damaging the metal foil, and makes it easy to assemble the metal foil to the secondary battery body. . Furthermore, the present invention provides a method for manufacturing a perforated metal foil with an Al alloy carrier, which has a large number of holes that can greatly reduce the number of manufacturing steps as compared with conventional manufacturing methods.

  The best mode for producing a perforated metal foil with an Al alloy carrier having a large number of holes according to the present invention will be described below with reference to FIGS.

  1 and 2 are flowcharts for explaining a method for producing a perforated metal foil with an Al alloy carrier (in producing the metal foil, FIG. 1 is a case of Cu plating, and FIG. 2 is a Ni plating). This is a flowchart in the case of. The manufacturing method in the case of Cu plating prepares Al alloy foil used as an Al alloy carrier, a process (a) (degreasing and etching process), a process (b) (water washing process), a process (c) (Cu plating), It is a method including a step (d) (water washing step), a step (e) (rust prevention treatment step), and a step (f) (drying step). In addition, although process (a) performs alkali degreasing, since Al is an amphoteric metal, it is also a degreasing and etching process which also etches Al simultaneously.

In addition, as shown in FIG. 2 (in the case of Ni plating), when using a metal that does not easily corrode such as Ni as an electrodeposition metal for electroplating, the step (e) shown in FIG. 1 (rust prevention) The processing step) is omitted.

  Hereinafter, a method for producing a perforated metal foil with an Al alloy carrier will be described step by step with reference to FIGS. (Note that the description of the steps that overlap in FIGS. 1 and 2 is omitted with reference to FIG. 2.)

In step (a), degreasing and etching of the Al alloy foil is performed. The conditions of the degreasing liquid are as follows.
Bath composition:
NaOH; 15 g / L to 45 g / L
Rochelle salt; 25 g / L to 65 g / L
Na ₂ CO ₃ ; 25 g / L to 65 g / L
Liquid temperature: 20 ° C to 60 ° C, preferably 30 ° C to 50 ° C
Processing time: 10 seconds to 300 seconds Degreasing / etching speed: 1 μm / min to 1.5 μm / min

  Here, the degreasing / etching step will be described with reference to FIGS. FIG. 4 is an SEM photographic image showing the relationship between the degreasing / etching time and the surface state of the Al alloy foil. The upper row is an SEM photographic image at a magnification of 500 times and the lower row at a magnification of 10,000 times. Furthermore, it is a SEM photograph image of degreasing and etching processing time 0, 30, 60, and 180 seconds in order from the left. As shown in FIG. 4, protrusions appear because the Al part is etched by the degreasing / etching process, and as the degreasing / etching process time increases, the etching amount of the Al part increases, and the protrusions gradually increase on the surface of the Al alloy foil. I understand that.

  FIG. 5A shows an observation image by EPMA and an element distribution state showing the surface state of the Al alloy foil after 3 minutes of degreasing / etching treatment. From FIG. 5A, it can be seen that the projecting portion is composed of elements such as Fe and Si.

  FIG. 5B shows an EPMA observation image and an element distribution state after slightly performing Cu electrodeposition on the surface of the Al alloy foil after the degreasing / etching process. This is to observe the effect of etching by treatment on the subsequent electrodeposition of Cu. More specifically, FIG. 5B shows the surface state of the Al alloy foil when the Cu film thickness reaches 0.1 μm, that is, at the initial stage of Cu electrodeposition. By comparing the leftmost COMPO observation image and the rightmost Cu observation image in FIG. 5B, it can be seen that Cu is electrodeposited with the protruding portion as a base point.

In this degreasing / etching step a, when Al is etched and dissolved by the reaction of the following formula (1) until Al becomes supersaturated in the degreasing solution, Al ₂ O is obtained by the reaction of formula (3) via formula (2). ₃ · 3H 2 _O will be generated (ref. "aluminum surface technology Handbook" Light Metal Shuppan Co., Ltd.). The Al ₂ O ₃ remains on the surface of the Al alloy foil, thereby obstructing the etching process on the surface of the Al alloy foil. Further, the Al ₂ O ₃ contaminates the degreasing liquid in the degreasing / etching tank, so that Al ₂ O ₃ is generated. It is not preferable to be done. Therefore, it is necessary to pay attention to the bath management under the condition of the degreasing solution so that the etching of Al with NaOH becomes supersaturated and Al ₂ O ₃ is not generated.
2Al + 2NaOH + 2H ₂ O → 2NaAlO ₂ + 3H ₂ (1)
2NaAlO ₂ + 4H ₂ O → 2NaOH + 2Al (OH) ₃ (2)
2Al (OH) ₃ → Al ₂ O ₃ .3H ₂ O (3)

  Returning to FIG. 1 again, step (b) of the manufacturing method will be described.

  Next, in the step (b), after the degreasing / etching process of the Al alloy foil is completed in the step (a), water washing (preferably using pure water) is performed with running water at room temperature for 60 seconds. At this time, bubbling or ultrasonic cleaning may be performed in the cleaning tank. In addition, a plurality of tanks are installed in cascade so as not to bring the degreasing solution into the plating solution tank of step (c) as much as possible (for example, three tanks are cascaded in series) to perform the final cleaning from the rough cleaning. May be. This is because it is desirable to completely remove the etching reaction product as much as possible in order to perform electrodeposition at the time of electroplating in the next step (c), and to further extend the life of the plating bath as much as possible.

  Next, in step (c), the Al alloy foil degreased and etched in step (b) is immersed in a Cu bath (in the case of FIG. 1) or Ni bath (in the case of FIG. 2) having the following composition, Electrodeposition of Cu or Ni is performed on the surface of the Al alloy foil.

The bath composition at the time of the plating is as follows.
1) Cu plating bath (CuSO ₄ bath)
_{CuSO 4 · 5H 2 O; 150g} / L~350g / L
H ₂ SO ₄ ; 50 g / L to 250 g / L
2) Ni plating bath (watt bath)
_{NiSO 4 · 6H 2 O; 150g} / L~300g / L
NiCl ₂ · 6H ₂ O; 50 g / L to 250 g / L
H ₃ BO ₃ ; 30 g / L to 40 g / L

The type of plating bath is not limited to the above. For example, a Cu pyrophosphate bath can be used for Cu plating, while a Ni sulfamate bath can be used for Ni plating. When performing electrodeposition of Cu, the current density is 2 A / dm ^{2 to} 50 A / dm ² , and more preferably 10 A / dm ^{2 to} 30 A / dm ² . An insoluble electrode (DSE) is used for the anode. A DC power source is used as the power source.

  Under these conditions, Cu or Ni is electrodeposited on the surface of the Al alloy until the film thickness becomes 1 μm to 10 μm to obtain a perforated metal foil with an Al alloy carrier.

Here, referring to the light transmission photograph of FIG. 6, when the perforated metal foil layer is a Cu foil, how the hole is formed depends on the washing time of the underlying Al carrier and the film thickness of the Cu foil. It will be described whether a suitable Cu foil is formed.

  According to FIG. 6A, it is understood that the non-uniformity of Cu electrodeposition is improved by extending the water washing time of the Al carrier after degreasing and etching from 15 seconds to 60 seconds.

  Further, considering the light transmission photograph of FIG. 6B, light transmission is observed up to a film thickness of Cu foil of 7 μm. However, when the film thickness of the Cu foil reaches 9 μm, no light transmission is observed. It can be seen that the hole penetrating from one surface of the Cu foil to the other surface disappears linearly at a film thickness of 9 μm and is no longer in a mesh shape in which light can be transmitted. Thereby, in Cu foil with a film thickness of 9 micrometers or more, it is thought that Li occludes or occludes in the form that a hole meanders or branches.

  Furthermore, with reference to FIG. 7, the process of generating the above-described perforated Cu foil or Ni foil with an Al alloy carrier will be described. Fe, Si appearing on the surface of the Al alloy foil by the degreasing / etching treatment of the prepared Al alloy foil. The metal particles (Cu or Ni) are preferentially deposited on the dispersed precipitation portion such as (FIG. 7A), and then the preferentially dispersed metal particles are further grown (FIGS. 7B and 7C). In addition, metal particles continue to grow on the newly grown metal particles (FIGS. 7D to 7F). At this time, pores are formed between the metal particles and gradually fill, but microscopically there are micropores between the metal particles (Fig. 7 (g) and Fig. 7 (h)). Thus, a perforated metal foil provided with a large number of holes through which the metal foil leads from one surface to the other surface is obtained.

  Returning again to FIG.

Next, in the step (d), the perforated Cu foil with the Al alloy carrier is washed with water for 30 seconds (preferably using pure water), and in step e, it is immersed in a 1 g / L benzotriazole solution for 10 seconds to prevent it. Apply rust treatment. And the perforated Cu foil with an Al alloy carrier subjected to the rust prevention treatment in the step (f) is dried in the air.

When the Ni foil is manufactured as a metal foil, the manufacturing process flow shown in FIG. 2 is used for the processes other than the rust prevention process, but the Ni surface has a passive film. This is because it is easily formed in the atmosphere and corrosion does not proceed like Cu. The current density during Ni electrodeposition is 1 A / dm ^{2 to} 40 A / dm ² , and more preferably 5 A / dm ^{2 to} 20 A / dm ² . The bath temperature is 30 ° C to 70 ° C, more preferably 40 ° C to 60 ° C. A Ni electrode is used for the anode. The power supply uses a DC power supply. The film thickness of the obtained Ni foil is 1 μm to 10 μm. Ni plating is performed under the above conditions (step (c)), and pure water cleaning is performed for 30 seconds (step (d)). And it is made to dry in air | atmosphere (process (f)).

  As mentioned above, according to embodiment which concerns on this invention, by peeling Cu foil or Ni foil from the obtained perforated Cu foil with an Al alloy carrier or perforated Ni foil with an Al alloy carrier, ultrathinness of 1 μm to 10 μm is obtained. Cu foil or ultrathin Ni foil is obtained. Here, when a thin metal foil is used as an electrode current collector as in the present invention, the electrode support used by a thick foil current collector having a thickness of more than 10 μm as conventionally used is used. I don't have enough roles. Rather, it can also be said to be an electrode surface layer having a current collecting function. It should be noted that in this respect it is distinguished from conventional thick foil current collectors.

  In addition, when peeling Cu foil or Ni foil from perforated Cu foil with Al alloy carrier or perforated Ni foil with Al alloy carrier, according to the prior art, the peeling layer is artificially separated from the carrier and Cu foil or Ni foil. (See the peeling layer 2 in FIG. 10 and FIG. 11 of Patent Document 4), but in the present invention, since the carrier is made of an Al alloy foil, the step a (degreasing / etching step) to the step The Al surface is easily passivated immediately before c (electroplating step) to form an oxide film, and this oxide film functions as a release layer. Therefore, the manufacturing method according to the present invention does not require a step of producing a release layer, and the number of steps can be reduced as compared with the number of steps by the manufacturing method of the prior art.

  Furthermore, according to the embodiment of the present invention, the Cu foil or Ni foil is always supported by the Al alloy carrier until just before the assembly to the secondary battery, so that the ultra thin Cu foil or the ultra thin Ni foil is just before the assembly. Will not be damaged until. Further, since the Al alloy carrier has a certain strength, it is easy to assemble manually, and the assembly can be easily automated during the secondary battery electrode manufacturing process. In particular, since the Cu foil or Ni foil is extremely thin and weak as described above, being supported by the Al alloy carrier brings various advantages.

<Manufacture of perforated Cu foil with Al alloy carrier>
In Example 1, Cu was used as the metal of the perforated metal foil with an Al alloy carrier. Example 1 will be described below.
First, an Al alloy foil (JIS standard 1N30 (see above)) having a thickness of 40 μm was prepared.
a) Degreasing and etching process:
About Al alloy foil used as a carrier, degreasing and etching were performed in a degreasing solution having the following liquid composition at a liquid temperature of 40 ° C. for 150 seconds.
Liquid composition NaOH; 30 g / L
Rochelle salt; 46 g / L
Na ₂ CO ₃ ; 46 g / L

b) Water washing process:
Thereafter, the degreased and etched Al alloy foil was subjected to pure water cleaning treatment at room temperature for 60 seconds.

c) Electroplating process:
Next, Cu was electrodeposited on the Al alloy foil washed with pure water in a Cu plating bath under the following plating conditions so that the plating thickness was 5 μm. Note that an insoluble electrode (DSE) was used as the anode electrode, and a DC power source was used as the power source.
Bath composition _{CuSO 4 · 5H 2 O; 216g} / L
H ₂ SO ₄ ; 192 g / L
Current density: 20 A / dm ²
Bath temperature: 40 ° C

d) Water washing process:
Then, the pure water washing process for 30 second was performed at room temperature about Al alloy foil (Al alloy carrier-attached perforated metal foil) with which the said Cu plating was given.
e) Rust prevention treatment process:
It was immersed in the benzotriazole solution having the concentration of 1 g / L for 10 seconds, and the perforated metal foil with an Al alloy carrier was subjected to a rust prevention treatment.
f) Drying process:
The perforated Cu foil with an Al alloy carrier subjected to rust prevention treatment was dried in the air.

  FIG. 8 shows (a) a light transmission photographic image and (b) an SEM photographic image of a perforated Cu foil with an Al alloy carrier obtained in the above steps a to f. It can be seen from FIG. 8A that light is uniformly transmitted and from FIG. 8B, Cu particles constituting the Cu foil are uniformly distributed. Accordingly, it has been found that a hole extending from one surface to the other surface exists between adjacent Cu particles in the Cu foil layer.

<Manufacture of negative electrode for secondary battery>
Using an alloy powder having an average particle size (D ₅₀ = 1.5 μm) having a composition of Si 80 wt% -Ni 20 wt% as an active material, active material: Ni powder: acetylene black: PVdF = 60: 34: 1 : The slurry was prepared so as to have a mixing ratio of 5, and the slurry was applied to the Cu foil surface side of the perforated Cu foil with Al alloy carrier so that the film thickness was 15 μm, and the coating film was formed on the Cu foil surface the (Incidentally, D ₅₀ is 50% by weight cumulative particle size measured by a laser diffraction scattering particle size distribution measuring method. forth.).

  Further, under the same conditions as described above, 5 μm of Cu plating was applied on the coating film, and an Al alloy carrier was peeled off to produce a negative electrode (the side on which the Cu plating was applied was referred to as “coating plating side”. The back side of the “coating plating side” is referred to as the “carrier peeling side”). At this time, it is preferable to adjust the plating conditions so that a hole leading to the active material layer is opened on the surface on the coating plating side.

<Manufacture of positive electrode for secondary battery>
The positive electrode is prepared by suspending a positive electrode active material and, if necessary, a conductive agent and a binder in a suitable solvent to produce a positive electrode mixture, applying it to a current collector, then drying, roll rolling, pressing It is obtained by processing, and further cutting and punching.

<Manufacture of non-aqueous electrolyte>
In the case of a Li ion secondary battery, the nonaqueous electrolytic solution is prepared by a solution obtained by dissolving a Li salt as a supporting electrolyte in an organic solvent. The Li salts, for _{example, LiClO 4, LiAlCL 4, LiPF} 6, LiAsF 6, LiSbF 6, LiSCN, LiCl, LiBr, LiI, LiCF 3 SO 3, or _LiC 4 _F 9 SO ₃ and the like are applicable. Specifically, a mixed solution (1: 1 volume ratio) of LiPF ₆ / ethylene carbonate and diethyl carbonate was used as the nonaqueous electrolytic solution.

  FIG. 9 is a graph showing the charge / discharge characteristics of the Li ion secondary battery provided with the negative electrode. FIG. 9 (a) shows the charge / discharge characteristics on the carrier peeling side, and FIG. 9 (b). Indicates charge / discharge characteristics on the coating plating side. Considering both graphs of FIGS. 9A and 9B, almost similar curves are obtained. From this result, it was found that a passage which is a perforated portion through which the Li electrolyte passes was formed on both the carrier peeling side and the coating plating side, and a sufficient capacity as a battery was obtained.

<Manufacture of perforated Ni foil with Al alloy carrier>
In Example 2, Ni was used as the metal of the perforated metal foil with an Al alloy carrier. Example 2 will be described below.
First, an Al alloy foil (JIS standard 1N30 (see above)) 40 μm was prepared.
a) Degreasing and etching process:
About the Al alloy foil used as a carrier, degreasing and etching were performed for 150 seconds at a liquid temperature of 40 ° C. in a degreasing liquid having the following liquid composition.
Liquid composition NaOH; 30 g / L
Rochelle salt; 46 g / L
Na ₂ CO ₃ ; 46 g / L

b) Water washing process:
Thereafter, the degreased and etched Al alloy foil was subjected to pure water cleaning treatment at room temperature for 60 seconds.

c) Electroplating process:
Next, Ni was electrodeposited on the Al alloy foil washed with pure water in a Ni plating bath under the following plating conditions so that the plating thickness was 5 μm. The anode electrode was a Ni electrode and the power source was a DC power source.
Bath composition _{NiSO 4 · 6H 2 O; 250g} / L
NiCl ₂ · 6H ₂ O; 45 g / L
H ₃ BO ₃ ; 30 g / L
Current density: 10 A / dm ²
Bath temperature: 50 ° C

d) Water washing process:
Thereafter, the Ni-plated Al alloy foil (perforated metal foil with Al alloy carrier) was subjected to a pure water cleaning treatment at room temperature for 30 seconds.
e) Drying process:
The perforated metal foil with an Al alloy carrier was dried in the air.

<Manufacture of negative electrode for secondary battery>
Using an alloy powder having an average particle size (D ₅₀ = 1.5 μm) having a composition of Si 80 wt% -Ni 20 wt% as an active material, active material: Ni powder: acetylene black: PVdF = 60: 34: 1 : a slurry was prepared so that the mixing ratio of 5, the film thickness was formed slurry was applied onto a Ni foil side of the perforated Ni foil with Al alloy carrier coating to be 15 [mu] m (Note D ₅₀ is a laser 50% weight cumulative particle size by diffraction scattering particle size distribution measurement method).

  Furthermore, under the same conditions as described above, Ni plating 5 μm was applied on the coating film, and the Al alloy carrier was peeled off to produce a negative electrode (the side on which the Ni plating was applied is referred to as “coating plating side”, The back side of this “coating plating side” is referred to as the “carrier peeling side”). At this time, it is preferable to adjust the plating conditions so that a hole leading to the active material layer is opened on the surface on the coating plating side.

<Manufacture of positive electrode for secondary battery>
On the other hand, the positive electrode is prepared by suspending a positive electrode active material and, if necessary, a conductive agent and a binder in an appropriate solvent to produce a positive electrode mixture, applying this to a current collector, then drying and rolling. It is obtained by performing press working, and further cutting and punching.

<Manufacture of non-aqueous electrolyte>
In the case of a Li ion secondary battery, the non-aqueous electrolyte is prepared by a solution obtained by dissolving a Li salt that is a supporting electrolyte in an organic solvent. As the Li salt, those enumerated in the item of production of the above-mentioned perforated Cu foil with an Al alloy carrier can be similarly applied. Specifically, a mixed solution (1: 1 volume ratio) of LiPF ₆ / ethylene carbonate and diethyl carbonate was used as the nonaqueous electrolytic solution.

  The same good results as in FIG. 9 were obtained from the charge / discharge characteristics of the Li ion secondary battery provided with the negative electrode thus prepared. From this result, a passage through which the Li electrolyte passed was formed on both the carrier peeling side and the coating plating side, and a sufficient capacity as a non-aqueous electrolyte secondary battery was obtained.

<Modified example of forming method of active material layer>
The formation method of the active material layer is not limited to the paste application of the active material particles as described above. For example, when a conductive metal such as Sn is used as the active material, the active material layer can be formed by electroplating. In the case of Sn, a plating bath having a composition described in ordinary literature, that is, a well-known one by those skilled in the art can be used. In general, a tin sulfate bath, a pyrophosphoric acid bath, a borofluoride bath, or the like can be used. Among these, an example of the bath composition and electrolysis conditions of the tin sulfate bath is shown below.
Bath composition SnSO ₄ ; 50 g / L
H ₂ SO ₄ ; 100 g / L
Cresol sulfonic acid; 80 g / L
Current density: 5 A / dm ²
Bath temperature: 25 ° C

An Sn alloy can also be used. In this case, by including a metal that does not alloy with Li in the Sn alloy, the expansion and contraction during the charge / discharge reaction of the alloy film can be limited, and as a result. As a result, the charge / discharge cycle can be increased. In the case of an Sn alloy, a plating bath having a composition described in ordinary literatures, that is, a well-known one can be used. Generally, a cyan bath, a pyrophosphoric acid bath, a borofluoride bath, etc. Can be used. Among these, an example of the bath composition and electrolysis conditions of the cyanide bath is shown below.
Bath composition CuCN; 35 g / L
_{Na 2 SnO 3 · 3H 2 0} ; 60g / L
NaCN; 25 g / L
Current density: 5 A / dm ²
Bath temperature: 65 ° C

  Further, by introducing P or B into the alloy film, it is possible to distort the crystal lattice and make it easier to occlude or desorb Li.

  After forming the active material layer, electroplating a conductive metal such as Cu or Ni that is difficult to alloy with Li can form a surface on the side of the coating plating to prevent the active material from falling off.

  In this case, a series of processes from the formation of the perforated metal foil on the Al alloy foil to the formation of the active material layer to the formation of the surface coating layer can be preferably performed in an in-line plating process.

The present invention can be applied as a perforated metal foil with an Al alloy carrier that can be used as a current collector of a non-aqueous electrolyte secondary battery such as a Li ion secondary battery. Moreover, the negative electrode which provided the active material on the metal foil of this invention is suitable as a negative electrode for secondary batteries.

It is a flowchart of the manufacturing process of perforated Cu foil with an Al alloy carrier. It is a flowchart of the manufacturing process of perforated Ni foil with an Al alloy carrier. It is a conceptual diagram which shows the formation process of perforated metal foil with an Al alloy carrier. It is a SEM photographic image showing the time-dependent change by degreasing and etching time of the surface of Al alloy foil, and is a figure for explaining the difference in the surface by degreasing and etching time. (A) Observation image and element distribution state by EPMA showing elements appearing on the surface after etching the surface of the Al alloy foil for 3 minutes, (b) Surface obtained by electrodepositing 0.1 μm Cu particles on the surface It is an observation image and element distribution state by EPMA showing the state corresponding to each element. (A) It is a light transmission photograph for demonstrating the light transmission difference of Cu foil with a film thickness of 5 micrometers at the time of changing the water washing time after a degreasing and an etching process about the surface of Al alloy foil. (B) A light transmission photograph for explaining the difference in light transmission when the film thickness of Cu is changed when the surface of the Al alloy foil is degreased and etched for 180 seconds and the subsequent water washing time is 60 seconds. is there. It is a figure explaining the process in which Cu precipitates on the Al alloy foil surface and forms a Cu film | membrane about the perforated Cu foil with an Al alloy carrier which concerns on this invention ((a)-(h)). It is a figure which shows the light transmission photograph (a) and SEM photograph (b) of a 5-micrometer perforated Cu foil formed on the Al alloy foil surface about the perforated Cu foil with an Al alloy carrier which concerns on this invention. It is a graph which shows the charge / discharge characteristic of the negative electrode produced using the perforated Cu foil with an Al alloy carrier according to the present invention ((a) characteristics on the Al alloy carrier peeling side; (b) characteristics on the coating plating side) It is a conceptual diagram of the manufacturing process of the conventional electrode for secondary batteries. It is a conceptual diagram of the electrode for secondary batteries comprised on the conventional carrier foil.

Claims (16)

A perforated metal foil with an Al alloy carrier comprising a perforated metal foil layer on the surface of the Al alloy foil,
The perforated metal foil layer is formed by electrodepositing a metal on the surface of an Al alloy carrier, and the perforated metal foil layer has a large number of holes that lead from the one surface to the other surface. A perforated metal foil with an Al alloy carrier, comprising: A perforated metal foil with an Al alloy carrier according to claim 1,
The contact surface of the Al alloy carrier with the metal foil layer has protrusions that are uniformly dispersed in the plane and has a perforated metal foil with an Al alloy carrier. A perforated metal foil with an Al alloy carrier according to claim 2,
The projecting portion is formed by degreasing the Al alloy foil and simultaneously etching the Al portion in the Al alloy. A perforated metal foil with an Al alloy carrier according to claim 2 or claim 3,
The projecting portion on the Al alloy carrier side of the projecting portion is a dispersed and precipitated element other than Al contained in the Al alloy foil. A perforated metal foil with an Al alloy carrier according to any one of claims 1 to 4,
A perforated metal foil with an Al alloy carrier, wherein the perforated metal foil has a thickness of 1 μm to 10 μm. A perforated metal foil with an Al alloy carrier according to any one of claims 1 to 5,
A perforated metal foil with an Al alloy carrier, wherein the carrier foil has a thickness of 10 μm to 100 μm. A perforated metal foil with an Al alloy carrier, characterized in that the metal foil of the perforated metal foil with an Al alloy carrier according to any one of claims 1 to 6 is a Cu foil or a Ni foil. A current collector for a secondary battery electrode, wherein the current collector is a perforated metal foil with an Al alloy carrier according to any one of claims 1 to 7. The electrode for secondary batteries provided with the electrical power collector of Claim 8. The secondary battery electrode according to claim 9, wherein the current collector according to claim 8 is provided with an Sn or Sn alloy active material plating layer. The secondary battery provided with the electrode for secondary batteries in any one of Claims 9-10. A method for producing a perforated metal foil with an Al alloy carrier comprising a metal foil layer on the surface of an Al alloy foil including the following steps a to c,
The metal foil layer is formed by electrodepositing a metal on the surface of an Al alloy carrier, and manufacturing a perforated metal foil layer having a large number of holes extending from the one surface to the other surface. A method for producing a perforated metal foil with an Al alloy carrier, characterized in that:
Step a. A degreasing / etching step for etching the Al portion of the carrier foil while degreasing the surface of the carrier foil made of an Al alloy
Step b. A water washing step of washing the etched carrier foil, and a step c. An electroplating step of depositing metal on the surface of the carrier foil after washing with water; A method for producing a perforated Cu foil with an Al alloy carrier comprising a Cu foil layer on the surface of an Al alloy foil including the following steps a to e,
The Cu foil layer is formed by electrodepositing Cu on the surface of an Al alloy carrier, and manufacturing a perforated Cu foil layer having a large number of holes extending from the one surface to the other surface. A method for producing a perforated Cu foil with an Al alloy carrier.
Step a. Using an alkaline degreasing solution in which NaOH is 15 g / L to 45 g / L, Rochelle salt is 25 g / L to 65 g / L, and Na ₂ CO ₃ is 25 g / L to 65 g / L, the liquid temperature is 20 ° C. to 60 ° C. A degreasing / etching step for performing degreasing and etching treatment on an Al alloy carrier foil having a thickness of 10 μm to 100 μm, with an immersion time of 10 seconds to 300 seconds,
Step b. A water washing step of washing the Al alloy carrier foil subjected to the degreasing and etching processes,
Step c. CuSO ₄ .5H ₂ O concentration is 150 g / L to 350 g / L, H ₂ SO ₄ concentration is 50 g / L to 250 g / L, bath temperature is 20 ° C. to 60 ° C., and current density is 2 A / dm ^{2 to} 50 A /. an electroplating step of electrodepositing Cu on the surface of the Al alloy carrier foil subjected to the degreasing and etching treatment for 10 seconds to 300 seconds under the condition of dm ² ;
Step d. A water washing step of washing the Cu-plated Al alloy carrier foil, and a step e. A rust-preventing step for carrying out a rust-preventing treatment by immersing the cleaned Cu-plated Al alloy carrier foil in a benzotriazole solution having a concentration of 0.1 g / L to 5 g / L. A method for producing a perforated Ni foil with an Al alloy carrier comprising a Ni foil layer on the surface of an Al alloy foil including the following steps a to c,
The Ni foil layer is formed by electrodepositing Ni on the surface of an Al alloy carrier, and a perforated Ni foil layer having a large number of holes extending from the one surface to the other surface is manufactured. A method for producing a perforated Ni foil with an Al alloy carrier, characterized in that:
Step a. For a carrier foil having an Al alloy thickness of 10 μm to 100 μm, NaOH is 15 g / L to 45 g / L, Rochelle salt is 25 g / L to 65 g / L, and Na ₂ CO ₃ is 25 g / L to 65 g / L. A degreasing / etching step of performing degreasing and etching treatment in an alkaline degreasing solution at a liquid temperature of 20 ° C. to 60 ° C. for an immersion time of 10 seconds to 300 seconds;
Step b. A water washing step of washing the Al alloy carrier foil subjected to the degreasing and etching processes,
Step c. NiSO ₄ · 6H ₂ O concentration is 150 g / L to 300 g / L, NiCl ₂ · 6H ₂ O concentration is 50 g / L to 250 g / L, and H ₃ BO ₃ concentration is 30 g / L to 40 g / L, and the bath temperature is An electroplating step of depositing Ni on the surface of the carrier foil under plating production conditions of 30 ° C. to 70 ° C. and a current density of 1 A / dm ^{2 to} 40 A / dm ² . A method for producing a perforated metal foil with an Al alloy carrier according to any one of claims 12 to 14,
On the contact surface of the Al alloy carrier with the metal foil layer, the metal against the charge concentration portions such as the protrusions, corners, and edges of the protrusions that are uniformly dispersed in the plane. A perforated metal foil with an Al alloy carrier, wherein metal particles for forming a foil layer begin to be uniformly electrodeposited. A method for producing a perforated metal foil with an Al alloy carrier according to any one of claims 12 to 15,
Using the uniformly deposited metal particles as the core of electrodeposition, the metal particles of the metal foil layer are uniformly deposited and grown on the core successively to form a perforated metal foil layer. A perforated metal foil with an Al alloy carrier.