JP2016141833A - Method and apparatus for producing metal foil, and method and apparatus for producing battery and battery element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for producing a metal foil which hardly causes reduction in the production quantity and fluctuation in physical properties even when producing a metal foil having a different thickness or a metal foil having a specific lamination structure.SOLUTION: There are provided apparatuses 1A and 1B for producing a metal foil which comprises electrolytic tanks 11 for storing an electrolytic solution 10, an anode body 12 immersed in the electrolytic solution 10 and an endless belt which is opposed to the anode body 12 and movable along the anode body 12 or a cathode body 13 which is a plate-like body. In the apparatuses 1A and 1B, a plurality of the electrolytic tanks 11 are provided from the upstream side to the downstream side of the endless belt or the cathode body 13 which is a plate-like body and a metal is sequentially precipitated on the surface of the cathode body 13 to form a metal thin layer 20 by energization between the anode body 12 and the cathode body 13 in each of the electrolytic tanks 11 following the movement of the cathode body 13.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metal foil manufacturing apparatus and a metal foil manufacturing method, and more specifically, when manufacturing metal foils having different thicknesses or metal foils having a specific laminated structure, the production amount is decreased or the physical properties thereof are changed. TECHNICAL FIELD The present invention relates to a metal foil manufacturing apparatus that can be manufactured without causing erosion and a metal foil manufacturing method using the apparatus.

  The metal foil is obtained by thinly extending a metal having good spreadability. For example, the copper foil includes a rolled copper foil and an electrolytic copper foil. Of these, the rolled copper foil is usually produced by repeatedly rolling and annealing electrolytic copper. Moreover, the electrolytic copper foil is produced, for example, by electrodepositing copper on a rotating drum and winding it, and has an advantage that the crystal structure is dense and uniform. These are used, for example, for flexible printed wiring boards.

  To obtain an electrolytic foil (electrolytic metal foil) of iron, copper, chromium, nickel, etc., first, a predetermined electrolytic solution containing these metal ions is supplied between the insoluble cathode body and the insoluble anode body. By carrying out an electrolytic reaction, the desired metal is electrodeposited on the surface of the cathode body by a desired thickness to form a thin metal layer. Next, the thin metal layer thus formed is manufactured by peeling from the surface of the cathode body.

  More specifically, for example, electrolytic copper foil is conventionally manufactured by a drum-type foil making apparatus 101 as shown in FIG. 6, and in this drum-type foil making apparatus 101, an anode body 102 is disposed inside a plating tank (not shown). And a cathode body (drum-type cathode) 103, and the plating tank is filled with a copper sulfate plating solution or the like. In this state, when a current is passed from the anode body 102 to the drum-type cathode 103 using a rectifier (DC power supply) while rotating the cathode body (drum-type cathode) 103, a titanium drum is formed by a so-called electrolytic metal plating method. A metal foil such as copper is deposited on 105 to form a metal foil.

  The copper 104 deposited in this way is peeled off from the drum-type cathode 103, and this is subjected to a rust prevention treatment in a predetermined post-processing apparatus, and then wound up in a roll shape or cut into a predetermined dimension with a slitter. Thus, a metal foil was obtained (Patent Document 1).

  For metal foils such as copper foils manufactured as described above, for example, when used as a material for printed wiring boards, the thickness is reduced due to demands for higher circuit density, weight reduction, or multilayering. An ultra-thin product having a thickness of less than 5 μm has been demanded, and in recent years, demand for ultra-thin copper foil products and the like has increased.

  However, in the drum type foil making apparatus as described above, since the metal thin layer does not have a conveying means when it is peeled off from the drum-type cathode at the peeling point, it has an extremely thin thickness of 5 μm or less with extremely weak mechanical strength. It is difficult to remove the metal foil from the drum as a product.

  Further, in the conventional drum type foil making apparatus, the metal thin layer deposited on the drum type cathode has a stress in the direction toward the center of the circular drum, so that the metal foil as a product is removed from the drum type cathode. In order to peel and take out, a force in a direction against the stress is required. At that time, if the stress in the direction toward the center of the drum is strong, an event such as tearing occurs when the thin metal layer is peeled off from the drum, and the thinner the metal foil as the desired product, the harder it is to peel off from the drum As a result, the yield of the product decreases.

  Therefore, the present inventor uses a moving means such as a conveyor to move the flat cathode body along the anode body to deposit metal on the surface of the cathode body, and then the deposited metal is attached. Has proposed a metal foil manufacturing apparatus that can perform water washing treatment and rust prevention treatment (Patent Document 2). In addition, in this manufacturing apparatus, a metal foil is formed on the surface of the flat cathode body, so that a thin metal layer is formed in a form with as little stress as possible other than gravity. It can be peeled off by some peeling means. According to such a manufacturing apparatus, it is possible to produce a metal foil as a product effectively while suppressing a decrease in yield even with an extremely thin metal foil having extremely low mechanical strength.

JP-A-10-18076 International Publication No. 2012/176883

  By the way, as described above, for example, a metal foil used as a material for a printed wiring board is required to be extremely thin due to demands for high density, light weight, or multi-layered circuit. As the thickness of the metal foil required, the range is widened from thick to extremely thin.

  For example, when metal foils having greatly different thicknesses of 3 μm to 9 μm are to be manufactured, when the metal foil is manufactured using the manufacturing apparatus disclosed in Patent Document 2 described above, the amount of deposited metal (desired metal foil) The operation of changing the moving speed of the cathode body in the range of 1 to 3 times, the operation of changing the current density of the cathode body in the range of 1 to 3 times, and the like are necessary depending on the thickness of the It is necessary to change. However, when the manufacturing conditions are changed in this way, the production amount of the metal foil varies within a range of 1 to 3 times, and the size of the deposited metal crystals changes, so that the physical properties of the metal foil change greatly. For example, defects such as pinholes are likely to occur.

  In recent years, a metal foil having a specific laminated structure is also demanded, and it is required to produce a metal foil having a desired configuration with high production efficiency.

  The present invention has been proposed in view of the above-described circumstances, and when producing metal foils having different thicknesses or metal foils having a specific laminated structure, a decrease in production amount or a change in physical properties thereof is caused. It is an object of the present invention to provide a metal foil manufacturing apparatus that is difficult to cause and a metal foil manufacturing method using the apparatus.

  In order to solve the above-described problems, the present invention is configured as follows.

  (1) The first invention of the present invention is an electrolyzer containing an electrolytic solution, an anode body immersed in the electrolytic solution, an endless belt that faces the anode body and is movable along the anode body. Or a cathode body that is a plate-like body, and a plurality of the electrolytic cells are provided from the upstream side to the downstream side of the cathode body that is an endless belt or a plate-like body, and with the movement of the cathode body This is a metal foil manufacturing apparatus in which a thin metal layer is formed by sequentially depositing metal on the surface of the cathode body by energization between the anode body and the cathode body in each electrolytic cell.

  (2) According to a second aspect of the present invention, in the first aspect, a rectifier is independently connected to each of the plurality of electrolytic cells, and each electrolysis is performed by turning on / off the power supply of the rectifier. It is a manufacturing apparatus of the metal foil in which electricity supply in a tank is controlled.

  (3) According to a third aspect of the present invention, at least a metal foil manufacturing apparatus according to the first or second aspect of the invention is used to manufacture a long negative electrode current collector preliminary body including the metal foil. A negative electrode current collector manufacturing unit, and a state where the negative electrode current collector manufacturing unit is provided downstream of the negative electrode current collector manufacturing unit along the cathode body in the negative electrode current collector manufacturing unit, and is attached to the cathode body as a moving body And a negative electrode active material application unit that applies a negative electrode active material to the surface of the negative electrode current collector preliminary body transferred in step B.

  (4) A fourth invention of the present invention is an electrolyzer containing an electrolytic solution, an anode body immersed in the electrolytic solution, an endless belt that faces the anode body and is movable along the anode body. Or a cathode body that is a plate-like body, and a method for producing a metal foil using an apparatus comprising: an endless belt or a plate-like body; Electrolytic solution in the tank is contacted a plurality of times, and a metal thin layer is formed by sequentially depositing metal on the surface of the cathode body by energization between the anode body and the cathode body in the electrolytic tank in each of the plurality of times. It is a manufacturing method of the metal foil to form.

  (5) According to a fifth aspect of the present invention, in the fourth aspect of the invention, there is provided a method for producing a metal foil, comprising the step of continuously performing the contact of the electrolytic solution with the cathode body by the same electrolytic solution. is there.

  (6) According to a sixth aspect of the present invention, in the fourth aspect, the contact of the electrolyte solution with the cathode body a plurality of times is due to contact with a certain electrolyte solution and another electrolyte solution different from the electrolyte solution. A method for producing a metal foil including contact.

  (7) According to a seventh aspect of the present invention, in any one of the fourth to sixth aspects, the plurality of times of contact of the electrolytic solution with the cathode body is located from the upstream side to the downstream side of the cathode body. It is the manufacturing method of the metal foil performed by making the electrolyte solution in a some electrolytic vessel contact sequentially.

  (8) An eighth invention of the present invention is the metal foil manufacturing method according to any one of the fourth to seventh inventions, wherein the cathode body is moved at a constant speed.

  (9) A ninth invention of the present invention is the method for producing a metal foil according to any one of the fourth to eighth inventions, wherein the energization is performed under a condition that a current density in each of the electrolytic cells is constant. is there.

  (10) A tenth aspect of the present invention is a method for manufacturing a metal foil according to any one of the fourth to ninth aspects, wherein a long negative electrode current collector preliminary body including the metal foil is manufactured. While the negative electrode current collector preliminary body is transferred while being attached to the cathode body, a negative electrode active material is applied to the surface, and then cut to form a battery or battery element. It is a manufacturing method.

  According to the present invention, when manufacturing metal foils having different thicknesses or metal foils having a specific laminated structure, the metal foils can be manufactured without causing a decrease in production amount and variations in their physical properties.

It is a block diagram which shows the whole structure of the manufacturing apparatus of the metal foil which concerns on 1st Embodiment. It is an expanded block diagram which shows the specific structure of the electrolytic vessel in the manufacturing apparatus of metal foil. It is a block diagram which shows an example of the whole structure of a peeling apparatus. It is a block diagram which shows the whole structure of the manufacturing apparatus of the metal foil which concerns on 2nd Embodiment. It is a block diagram which shows the whole structure of the apparatus for manufacturing the negative electrode body of a battery consistently. It is a figure which shows an example of the manufacturing apparatus of the conventional metal foil.

  Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited to the following embodiment, A various change is possible in the range which does not change the summary of this invention.

<< 1. First Embodiment >>
FIG. 1 is a configuration diagram showing an overall configuration of a metal foil manufacturing apparatus 1A (also simply referred to as “manufacturing apparatus 1A”) according to the first embodiment. As shown in FIG. 1, a metal foil manufacturing apparatus 1 </ b> A includes an electrolytic bath 11 that contains an electrolytic solution, an anode body 12 that is immersed in an electrolytic solution 10 (10 a) in the electrolytic bath 11, and an anode body 12. The cathode body 13 is an endless belt or a plate-like body that is movable along the anode body 12.

  In the present embodiment, the manufacturing apparatus 1A having such a configuration is used, and the electrolytic solution 10 in the electrolytic cell 11 is moved with respect to the cathode body 13 as the cathode body 13 which is an endless belt or a plate-like body moves. Are contacted a plurality of times, and a metal is sequentially deposited on the surface of the cathode body 13 to form a thin metal layer 20 by energization between the anode body 12 and the cathode body 13 in the electrolytic cell 11 at each of the plurality of times.

Here, in the metal foil manufacturing apparatus 1A, as shown in FIG. 1, an electrolytic cell 11 containing an electrolytic solution 10 is located upstream (on the left side in FIG. 1) along a cathode body 13 which is an endless belt or a plate-like body. ) To the downstream side (right side in FIG. 1), a plurality (n) are provided. In FIG. 1, but showing an aspect of a three electrolytic cell ₁₁ 1 _{to 11} 3 (n = 3) is provided production equipment 1A, in this specification, "electrolytic cell ₁₁ 1 for a plurality of electrolytic cells 11 to 11 _n ".

In such a metal foil manufacturing apparatus 1A, in the plurality of electrolytic cells 11 _{1 to} 11 _n positioned from the upstream side to the downstream side of the cathode body 13 with the movement of the cathode body 13 which is an endless belt or a plate-like body. By sequentially bringing the electrolytic solution 10 into contact with the cathode body 13 and energizing the anode body 12, it is possible to deposit a metal on the surface of the cathode body 13 and form the thin metal layer 20.

Further, as shown in FIG. 1, the same electrolytic solution 10a is accommodated in two or more electrolytic cells 11 of a plurality of electrolytic cells 11 _{1 to} 11 _n , the cathode body 13 is moved at a constant speed, and It is possible to form a certain thin metal layer 20 _{1 to} 20 _n in each of the plurality of electrolytic cells 11 _{1 to} 11 _n by energizing each anode body 12 and cathode body 13. it can. According to such a manufacturing apparatus 1A, it is possible to easily manufacture a metal foil having a desired thickness while suppressing fluctuations in production volume and fluctuations in physical properties of deposited metal.

In the example shown in FIG. 1, two or more electrolysis of the electrolytic cell 11 ₁ to 11 ₃ are shown the embodiment where the same electrolyte solution 10a is accommodated in all of the electrolytic cell, the electrolytic cell 11 to be multiply provided The same electrolytic solution 10 may be accommodated in the tank 11.

As described above, as the aspect in which the electrolytic solution 10 in the electrolytic cell 11 is brought into contact with the cathode body 13 a plurality of times with the movement of the cathode body 13 which is an endless belt or a plate-like body, a plurality of electrolytic cells as described above. It is not limited to using 11 _{1 to} 11 _n, and a mode in which the single electrolytic cell 11 is used and the cathode body 13 is moved and repeatedly contacted may be used.

<About the device configuration>
(Electrolysis tank)
The electrolytic cell 11 serves as an electrolytic reaction field between the anode body 12 and the cathode body 13. The electrolytic tank 11 is made of a material having corrosion resistance with respect to the electrolytic solution (electrolytic metal plating solution) 10 to be used, for example, FRP (fiber reinforced plastic) and the like, and is a tank having a rectangular horizontal cross section with an open upper surface.

  An electrolytic solution 10 is accommodated in the electrolytic cell 11. Specifically, in this electrolytic cell 11, for example, an electrolytic copper plating solution such as a copper sulfate plating solution for depositing copper on the surface of the cathode body 13 by an electrolytic reaction, a nickel sulfate plating solution for depositing nickel, An electrolytic solution 10 of a predetermined type and concentration, such as an electrolytic nickel plating solution such as a nickel sulfamate plating solution, is accommodated.

For example, when a copper sulfate plating solution is used as the electrolytic copper plating solution, a known one can be used, and in particular, a copper sulfate salt containing 10 to 300 g / l and sulfuric acid at a concentration of 10 to 300 g / l is preferable. Used. Furthermore, the copper sulfate plating solution preferably contains chlorine ions (Cl ⁻ ) at a concentration of 5 to 200 ppm. The pH of the copper sulfate plating solution is usually adjusted to 2 or less (0 to 2). Also, as the nickel sulfate plating solution, a known nickel sulfate plating solution can be used. Particularly, a nickel sulfate salt containing 10 to 300 g / l and sulfuric acid at a concentration of 10 to 300 g / l is preferably used. It is done.

  In the electrolytic solution 10a in the electrolytic cell 11, for each component other than the metal to be deposited, such as copper ions and nickel ions, the components reduced by continuous plating are added to the conventional case such as addition of a replenisher as necessary. Plating can be continued by replenishing by a known method.

  In the electrolytic cell 11, a rectifier 30 that controls energization between the anode body 12 and the cathode body 13 is connected, and the energization is “ON” by turning on / off the power of the rectifier 30, or “ It is controlled to the “OFF” state.

  Moreover, in the electrolytic cell 11, as shown in the enlarged view in the location of the electrolytic cell 11 of 1 A of manufacturing apparatuses shown in FIG. 2, the pump P can be provided closely. A suction pipe 31 is connected to the suction port of the pump P and a discharge pipe 32 is connected to the discharge port, so that the electrolytic solution 10 a in the electrolytic cell 11 is injected from the side of the anode body 12 by driving the pump P. Can be. That is, the distal end of the discharge pipe 32 connected to the discharge port of the pump P can be configured to be a distributor (electrolyte outlet) 33 that contacts the side of the anode body 12. The distributor 33 moves the cathode body 13 at a predetermined speed while supplying the electrolytic solution 10a to the gap 34 between the anode body 12 and the cathode body 13 which is an endless belt or a plate-like body. An electrolysis reaction is caused by energization with 13.

As will be described in detail later, in the metal foil manufacturing apparatus 1A according to the present embodiment, a plurality (n) of electrolytic tanks 11 for accommodating the electrolytic solution 10a are provided, and each of the electrolytic tanks 11 _{1 to} 11 _n is provided. Due to the electrolytic reaction between the anode body 12 and the cathode body 13 moving at a constant speed, the thin metal layers 20 _{1 to} 20 _n are formed on the surface of the cathode body 13 above the electrolytic cells 11 _{1 to} 11 _n. They are formed sequentially. The plurality of electrolytic cells 11 _{1 to} 11 _n may be provided with the pumps P (P _{1 to} P _n ) as described above in close proximity to each other.

(Anode body)
The anode body 12 has a flat plate shape, for example, and is disposed so as to be immersed in the electrolytic solution 10a in the electrolytic cell 11 (see FIG. 2). The anode body 12 is not particularly limited as long as it is made of an insoluble material that generates oxygen without being passivated when energized. For example, an iridium oxide, lead, or the like is used. The anode body 12 is generally required to have a low oxygen generation potential. For example, a titanium surface coated with platinum, iridium oxide, or the like is used.

(Cathode body)
The cathode body 13 is disposed so as to face the anode body 12, and is an endless belt or a plate-like body that can move along the anode body 12. As described above, in the electrolytic cell 11, the cathode body 13 that is stored in a state filled with the electrolytic solution 10 a of a predetermined type and concentration is electrolyzed in the electrolytic cell 11. Contact the liquid 10a.

  The cathode body 13 which is an endless belt or a plate-like body is an insoluble one made of a material such as platinum, titanium, stainless steel (SUS) or stainless steel coated with chromium, and is made of, for example, sulfuric acid or the like in the electrolytic solution 10a. What consists of a material which has tolerance with respect to a strong acidic component etc. is preferable, and SUS is more preferable. Although it does not specifically limit as a magnitude | size of the cathode body 13, It is preferable that the width is 400-2000 mm, and it is more preferable that it is 600-1200 mm. The thickness is preferably 0.1 to 1.0 mm, and more preferably 0.2 to 0.5 mm.

  The cathode body 13, which is an endless belt or a plate-like body, is preferably moved along the anode body 12 at a constant speed. Although it does not specifically limit as a moving speed of the cathode body 13, From a viewpoint of depositing a metal efficiently on the surface, 1-7 m / min. In the range of 2 to 5 m / min. It is more preferable that it is constant within the range.

  In the cathode body 13, the distance between the anode body 12 and the anode body 12 is preferably constant at a predetermined distance. Specifically, from the viewpoint of increasing the current density, it is preferably 1 to 50 mm, more preferably 2 to 30 mm, and even more preferably 3 to 10 mm. The cathode body 13, which is an endless belt or a plate-like body, is disposed at a certain distance between the electrodes within the above-described range in relation to the anode body 12 disposed in the electrolytic cell 11, and is parallel to the anode body 12. Move to.

The energization between the anode body 12 and the cathode body 13 is preferably performed under a condition where the current density is constant in each of the plurality of electrolytic cells 11 _{1 to} 11 _n . Specifically, examples of the current density is not particularly limited, it is preferably in the range of 50~600A / dm ^2.

<About the placement of the electrolytic cell>
In 1 A of metal foil manufacturing apparatuses which concern on this Embodiment, the electrolytic cell 11 which accommodates the electrolyte solution 10a is spaced apart from the upstream side of the cathode body 13 which is an endless belt or a plate-shaped body to the downstream side. A plurality (n) are provided. For example, as shown in FIG. 1, three electrolytic cells 11 (electrolytic cells 11 _{1 to} 11 ₃ ) are provided from the upstream side to the downstream side of the cathode body 13.

In each of the electrolytic cells 11 _{1 to} 11 ₃ , the same electrolytic solution 10 (10 a) is accommodated in two or more electrolytic cells 11. In such a manufacturing apparatus 1A, the cathode body 13 which is an endless belt or a plate-like body is brought into contact with the electrolytic solution 10 (10a) in each of the electrolytic cells 11 _{1 to} 11 _{3 as the} cathode body 13 moves at a constant speed. An electrolysis reaction is caused by energization between 12 and the cathode body 13, and a metal having a desired thickness is sequentially deposited on the surface of the cathode body 13.

  Here, since the deposition amount of the plating metal due to the electrolytic reaction is defined by Faraday's law, when manufacturing metal foils having different thicknesses in the range of 3 to 9 μm, for example, in a conventional metal foil manufacturing apparatus. It is necessary to change the manufacturing conditions each time, such as (i) an operation for changing the moving speed of the cathode within a range of 1 to 3 times, or (ii) an operation for changing the current density of the cathode within a range of 1 to 3 times. there were. However, when such manufacturing conditions are changed, for example, (i) when the moving speed of the cathode is changed, the production amount of the metal foil varies within a range of 1 to 3 times, and (ii) When the current density of the cathode is changed, the size of the deposited metal crystal changes, causing a change in the physical properties of the metal foil, and defects such as pinholes are likely to occur. .

On the other hand, according to the metal foil manufacturing apparatus 1A according to the present embodiment, a plurality (n) of electrolytic cells 11 _{1 to} 11 from the upstream side to the downstream side of the cathode body 13 which is an endless belt or a plate-like body. _n is provided. In the plurality of electrolytic cells 11 _{1 to} 11 _n , the same electrolytic solution 10 (10a) is accommodated in two or more electrolytic cells 11. In this manufacturing apparatus _{1 </} b _{> A} , as the cathode body 13 moves, the cathode body 13 and the electrolytic solution in each of the electrolytic cells 11 _{1 to} 11 _n come into contact with each other to conduct electrolysis by energization between the anode body 12 and the cathode body 13. Since the reaction occurs, by moving the cathode body 13 at a constant speed and energizing, a certain amount of metal is sequentially deposited on the surface of the cathode body 13, and the thin metal layers 20 _{1 to} 20 _n having a certain thickness are formed. It is formed.

That is, for example, as shown in FIG. 1, three electrolytic cells 11 _{1 to} 11 ₃ (each electrolytic cell 11 is formed with a 3 μm thin metal layer in parallel with an endless belt or a plate-like cathode body 13. And the same electrolytic solution 10a is accommodated in the _three electrolytic cells 11 _{1 to} 11 ₃ . Then, by moving the cathode member 13 at a constant speed, also a constant when the energized with a current density, first, the first electrolytic bath is a electrolytic cell 11 ₁ at 3μm of the thin metal layer 20 ₁ is the cathode body 13 is formed on the surface, then, on the metal thin layer 20 ₁ of 3 [mu] m, the metal thin layer 20 ₂ further 3 [mu] m (the same thickness) in the electrolytic cell 11 ₂ is the second electrolytic bath is formed. Then, for example, when trying to form a 9μm thickness of the metal thin layer 20 of the further third electrolytic cell electrolytic cell 11 ₃ is provided on the downstream side, the total 6μm metal through the electrolytic cell 11 ₂ thin layer 20 (20 ₁ and 20 ₂₎ by depositing a metal by electrolytic reaction with respect to the cathode body 13 is formed, a desired to 9μm of thickness of the metal thin layer 20 ₍₂₀ 1 to 20 ₃₎ Can be made.

As described above, in the metal foil manufacturing apparatus 1A according to the present embodiment, a plurality of electrolytic cells 11 _{1 to} 11 _n are provided from the upstream side to the downstream side of the cathode body 13 which is an endless belt or a plate-like body. The electrolysis conditions of each of the electrolytic cells 11 _{1 to} 11 _n are the same, and the cathode body 13 is moved at a constant speed, whereby a thin metal layer 20 having a desired thickness corresponding to the number of electrolytic cells 11 installed on the surface. Can be easily formed. According to such a manufacturing apparatus 1A, since the thin metal layer 20 having a desired thickness can be formed by moving the cathode body 13 at a constant speed, stable production can be achieved without changing the production amount of the metal foil. It can be carried out. In addition, since the cathode body 13 can be moved at a constant speed and can be energized between the anode body 12 and the cathode body 13 under constant electrolysis conditions (current density, etc.), the deposited metal The crystal size is also constant, and physical property fluctuations of the metal foil can be effectively suppressed, and defects such as pinholes are less likely to occur.

Further, in the manufacturing apparatus 1A having such a configuration, rectifiers 30 ₁ to 30 _n are independently connected to the plurality of electrolytic cells 11 _{1 to} 11 _n , respectively, and the power sources of the rectifiers 30 ₁ to 30 _n are provided. The energization between the anode body 12 and the cathode body 13 is controlled by the ON / OFF operation. For example, determine one of the conditions electrolyzer 11 the thin metal layer 20 ₁ 3 [mu] m of the ₁ is formed on the surface of the cathode body 13 (i.e., the moving speed of the cathode body (conveyance speed), a current density of the cathode body) Then, other electrolytic cells 11 _{2 to} 11 _{n in} which similar electrolysis conditions are set are installed, and rectifiers 30 ₁ to 30 _n capable of ON / OFF control of energization to the respective electrolytic cells 11 _{1 to} 11 _n . Connect. According to this, a metal thin film having an arbitrary thickness of a multiple of 3 (μm) can be obtained by ON / OFF operation of the power supply of each rectifier 30 ₁ to 30 _n independently connected to each of the electrolytic cells 11 _{1 to} 11 _n. The layer 20 can be easily manufactured.

That is, when five of the electrolytic cell manufacturing apparatus 1A of the configuration (setting a condition where the metal thin layer of 3μm is formed) is continuously provided in the electrolytic cell 11 1 _to the electrolytic cell 11 _5, for example, the electrolytic cell 11 ₁ - after each oN the power to the electrolytic cell 11 ₃ of the three electrolytic rectifiers independently connected to tank ₃₀ 1 to 30 _3, independently to the two electrolytic cells of the electrolyzer 11 ₄ - electrolyzer 11 ₅ By turning off the respective power supplies of the rectifiers 30 ₄ to 30 ₅ connected to each other, the energization between the anode body 12 and the cathode body 13 in the electrolytic cell 11 ₁ to the electrolytic cell 11 ₃ becomes an “ON” state. Reaction occurs to form thin metal layers 20 _{1 to} 20 ₃ , and as a result, a thin metal layer 20 of 9 μm (3 μm × 3) is formed. Thus, the metal thin layer 20 having a desired thickness can be easily manufactured only by the ON / OFF operation of the power supply of the rectifier 30 independently connected to each electrolytic cell 11.

In the example indicated by FIG. 1, although all three provided with the electrolytic cell 11 ₁ to 11 ₃ illustrates an embodiment in which housing the same electrolytic solution 10a, not limited thereto, as described above What is necessary is just to accommodate the same electrolyte solution 10 in two or more electrolytic cells 11 of electrolytic cells 11 _{1 to} 11 _n provided in plurality.

Moreover, in the metal foil manufacturing apparatus 1A provided with a plurality of electrolytic cells 11 _{1 to} 11 _n , naturally, only one of the electrolytic cells 11 (for example, the electrolytic cell 11 ₁ ) is energized, and the electrolytic cell 11. Alternatively, the thin metal layer 20 may be formed only in the above.

  In the metal foil manufacturing apparatus 1A, the number of electrolytic cells 11 is not particularly limited, and is appropriately set according to a desired thickness of the thin metal layer 20 formed on the surface of the cathode body 13 as described above, for example. be able to. As an example, in one electrolytic cell 11 containing the electrolytic solution 10a, a thin metal layer 20 having a thickness of 3 μm is formed by energizing the cathode body 13 moving at a constant moving speed with a predetermined current density. In this case, when the thin metal layer 20 having a thickness of 12 μm is to be formed, the manufacturing apparatus 1A provided with at least four electrolytic cells 11 in which the electrolytic solutions 10a of the same type and concentration are accommodated can be obtained.

As shown in FIG. 1, in the metal foil manufacturing apparatus ₁ </ b> A, a water washing treatment tank 40 for performing a water washing treatment can be provided between each of the plurality of electrolytic tanks 11 _{1 to} 11 _3. . Also in this washing treatment tank 40, for example, a pump P as shown in FIG. 2 is provided in the vicinity, water is supplied to the suction port of the pump P, and a plurality of discharge pipes are connected to the discharge port. By driving this, the supplied water can be jetted toward the metal deposited on the surface of the cathode body 13, and the washing process for the deposited metal can be performed.

<Metal foil peeling>
When the metal thin layer 20 having a desired thickness is formed on the surface of the cathode body 13 which is an endless belt or a plate-like body as described above, the metal thin layer 20 attached to the cathode body 13 is peeled off, and the metal A foil X is produced.

  Peeling of the thin metal layer 20 can be performed using, for example, a peeling device 50 as shown in FIG. When the thin metal layer 20 is peeled off, it is preferable that the surface of the cathode body 13 which is an endless belt or a plate-like body is polished in advance so as to have a mirror-like shape, whereby the cathode body 13 and the metal attached to the cathode body 13 are polished. The contact area with the thin layer 20 can be reduced as much as possible, and the metal thin layer 20 can be easily peeled off.

  The peeling apparatus 50 shown in FIG. 3 includes a first nip roll 51 in the traveling path of the cathode body 13, and allows the cathode body 13 with the thin metal layer 20 to pass between the upper roll 51a and the lower roll 51b. The thin metal layer 20 is peeled from the cathode body 13 by guiding the cathode body 13 away from the thin metal layer 20 while being pressurized. The peeled thin metal layer 20 passes between the upper and lower rolls of the second nip roll 53 whose surface is coated with, for example, a fluororesin, and is taken up by a winder 52 after being evacuated. The cathode body 13 can be wound up by, for example, a winder 54, and can be used again as the cathode body 13 as it is from the viewpoint of improving productivity. The peeling device 50 is an example of a device for peeling the thin metal layer 20 formed on the cathode body 13 and is not particularly limited. Other methods for peeling the thin metal layer 20 are available. You may use the apparatus provided with.

≪2. Second Embodiment >>
FIG. 4 is a configuration diagram showing an overall configuration of a metal foil manufacturing apparatus 1B (also simply referred to as “manufacturing apparatus 1B”) according to the second embodiment. As shown in FIG. 4, the metal foil manufacturing apparatus 1 </ b> B includes an electrolytic tank 11 that contains an electrolytic solution, an anode body 12 that is immersed in an electrolytic solution 10 (10 a, 10 b) in the electrolytic tank 11, and an anode body 12. And a cathode body 13 which is an endless belt or a plate-like body movable along the anode body 12.

  In the present embodiment, using the manufacturing apparatus 1B having such a configuration, the electrolytic solution 10 in the electrolytic cell 11 is moved with respect to the cathode body 13 as the cathode body 13 which is an endless belt or a plate-like body moves. Are contacted a plurality of times, and a metal is sequentially deposited on the surface of the cathode body 13 to form a thin metal layer 20 by energization between the anode body 12 and the cathode body 13 in the electrolytic cell 11 at each of the plurality of times.

Here, in the metal foil manufacturing apparatus 1B, as shown in FIG. 4, the electrolytic cell 11 containing the electrolytic solution 10 is from the upstream side (left side of FIG. 4) of the cathode body 13 which is an endless belt or a plate-like body. A plurality (n) is provided on the downstream side (right side in FIG. 4). In addition, in FIG. 4, although the aspect of the manufacturing apparatus 1B provided with _three electrolyzers 11 _{1 to} 11 ₃ (n = 3) is shown, in this specification, “electrolyzers 11 ₁ to 11 11 _n ".

In such a metal foil manufacturing apparatus 1B, in the plurality of electrolytic cells 11 _{1 to} 11 _n positioned from the upstream side to the downstream side of the cathode body 13 as the cathode body 13 which is an endless belt or a plate-like body moves. By sequentially bringing the electrolytic solution 10 into contact with the cathode body 13 and energizing the anode body 12, it is possible to deposit a metal on the surface of the cathode body 13 and form the thin metal layer 20.

Further, in the second embodiment, in the plurality of electrolytic cells 11 _{1 to} 11 _n , the electrolytic solution 10 (10a, 10a, 10a, 10a, 11n) is different from the electrolytic solution in the other electrolytic cell 11 in at least one electrolytic cell 11. 10b), the cathode body 13 is brought into contact with the electrolyte solution 10 a plurality of times by contact with an electrolyte solution 10a and contact with another electrolyte solution 10b different from the electrolyte solution 10a. Metals can be sequentially deposited on the surface of the body 13.

More specifically, as shown in FIG. 4, in the first electrolytic cell at which the electrolytic cell 11 ₁ and the third electrolytic bath a is electrolyzer 11 _3, electrolytic copper such as copper sulfate plating solution as an electrolyte solution containing a plating solution (electrolytic solution 10a), the electrolytic cell 11 ₂ which is a second electrolytic bath, for containing the electrolytic nickel plating solution such as nickel sulfate plating solution (electrolytic solution 10b) as an electrolytic solution. In the manufacturing apparatus 1B according to the second embodiment, the contact with the electrolyte solution 10a is performed a plurality of times by the contact with a certain electrolyte solution 10a and the contact with another electrolyte solution 10b different from the electrolyte solution 10a. The metal is sequentially deposited on the surface of the cathode body 13.

  In the second embodiment, portions common to the first embodiment described above are denoted by the same reference numerals, and detailed description thereof is omitted.

As described above, as the aspect in which the electrolytic solution 10 in the electrolytic cell 11 is brought into contact with the cathode body 13 a plurality of times with the movement of the cathode body 13 which is an endless belt or a plate-like body, a plurality of electrolytic cells as described above. It is not limited to using 11 _{1 to} 11 _n, and a mode in which the single electrolytic cell 11 is used and the cathode body 13 is moved and repeatedly contacted may be used.

<About the device configuration>
(Electrolysis tank)
The electrolytic cell 11 is a place for an electrolytic reaction between the anode body 12 and the cathode body 13 and is made of a material having corrosion resistance with respect to the electrolytic solution 10. The upper surface is released and the horizontal section is rectangular. It is a tank. An electrolytic solution 10 is accommodated in the electrolytic cell 11.

In the metal foil manufacturing apparatus 1B according to the present embodiment, a plurality (n) of electrolytic tanks 11 for accommodating the electrolytic solution 10 are provided, and anode bodies 12 in the electrolytic tanks 11 _{1 to} 11 _n , A thin metal layer is sequentially formed on the surface of the cathode body 13 above each of the electrolytic cells 11 _{1 to} 11 _n by an electrolytic reaction by energization with the cathode body 13 moving at a predetermined speed. . And in this manufacturing apparatus 1B, in the electrolytic tanks 11 _{1 to} 11 _n provided in plural, the electrolytic solution 10 (10a) different from the electrolytic solution 10 (10a) in the other electrolytic tank 11 is provided in at least one electrolytic tank 11. 10b) is accommodated.

  In the electrolytic cell 11, a rectifier 30 that controls energization between the anode body 12 and the cathode body 13 is connected, and the energization is “ON” by turning on / off the power of the rectifier 30, or , “OFF” state is controlled.

(Anode body)
The anode body 12 has a flat plate shape, for example, and is disposed in the electrolytic bath 11 so as to be immersed in the electrolytic solution 10.

(Cathode body)
The cathode body 13 is disposed so as to face the anode body 12, and is an endless belt or a plate-like body that can move in parallel along the anode body 12. As described above, the electrolytic cell 11 is housed in a state filled with the electrolytic solution 10 of a predetermined type and concentration, and the cathode body 13 that moves at a predetermined speed is contained in the electrolytic cell 11. Contact the electrolytic solution 10.

  The cathode body 13, which is an endless belt or a plate-like body, moves at a predetermined speed along the anode body 12, and metal is deposited on the surface by energization with the opposing anode body 12, and the thin metal layer 20 is formed. Will be formed.

<About the placement of the electrolytic cell>
In the metal foil manufacturing apparatus 1B according to the present embodiment, the electrolytic cell 11 that stores the electrolytic solution 10 is spaced from the upstream side to the downstream side of the cathode body 13 that is an endless belt or a plate-like body. A plurality (n) are provided. In the plurality of electrolytic cells 11 _{1 to} 11 _n , as shown in FIG. 4, an electrolytic solution different from the electrolytic solution 10 (10 a) in the other electrolytic cell 11 in at least one electrolytic cell 11. 10 (10b) is accommodated.

  Here, for example, an electrolytic copper foil produced by electrolytic copper plating is used for the negative electrode current collector of a lithium ion battery. In recent years, the purpose is to increase the amount of charge, reduce the weight, and reduce the size of the battery. Therefore, it is required to reduce the thickness of the electrolytic copper foil. Specifically, a copper foil thinned to about 4 to 5 μm from the conventional thickness of about 8 μm is required. However, in this electrolytic copper foil, durability and tensile strength decrease as the thickness is reduced. Therefore, for example, when a copper foil of about 5 μm is formed, a 2 μm copper foil, a 1 μm nickel foil, and a 2 μm copper foil are used. However, it is necessary to improve the durability while keeping the electrical characteristics equal to those of the copper foil.

In this regard, according to the metal foil manufacturing apparatus 1B according to the present embodiment, a plurality (n) of electrolytic cells 11 _{1 to} 11 _n from the upstream side to the downstream side of the cathode body 13 which is an endless belt or a plate-like body. The electrolytic solution 10 (10b) different from the electrolytic solution 10 (10a) in the other electrolytic cell 11 is accommodated in at least one electrolytic cell 11. Specifically, as shown in FIG. 4, for example, from the upstream side of the cathode body 13, the first electrolytic bath is a electrolytic cell 11 ₁ and the electrolytic bath 11 ₃ a third electrolytic cell, the electrolyte electroless copper plating solution such as copper sulfate plating liquid is accommodated as 10a, in the electrolytic cell 11 ₂ which is a second electrolytic bath, electroless nickel plating solution such as nickel sulfate plating solution is contained as the electrolytic solution 10b. In this manufacturing apparatus 1B, since an electrolysis reaction is caused by energization between the anode body 12 and the cathode body 13 arranged in each electrolytic cell 11, each electrolysis is performed by moving the cathode body 13 at a predetermined speed. A certain amount of metal sequentially deposits on the surface of the cathode body 13 above the tanks 11 _{1 to} 11 _n to form thin metal layers 20 _{1 to} 20 _n having a certain thickness.

That is, for example, as shown in FIG. 4, three electrolytic cells 11 _{1 to} 11 ₃ are provided in parallel to the cathode body 13, and the cathode body 13 is moved at a predetermined speed, so that the anode body 12 and the cathode body 13 by energizing between, first, electrolytic copper layer of the first example 2μm in the electrolytic cell 11 ₁ is an electrolytic cell (20 ₁₎ is formed on the surface of the cathode body 13, then, electrolytic copper of 2μm the layer (20 ₁₎ on, 1 [mu] m layer of electroless nickel (20 ₂₎ is formed by the electrolytic cell 11 ₂ is the second electrolytic bath. Finally, in a third electrolytic bath a is electrolyzer 11 _3, formed electroless nickel layer (20 ₂₎ on, 2 [mu] m electrolytic copper layer (20 ₃₎ is formed. In this way, the electrolytic cells 11 _{1 to} 11 _n accommodating different electrolytic solutions 10a and 10b are arranged side by side, and an electrolytic reaction is sequentially generated with the moving cathode body 13 so that each of the electrolytic cells 11 _{1 to} 11 _n is caused. By forming the thin metal layers 20 _{1 to} 20 _n , a laminated metal foil having a laminated structure of, for example, “2 μm copper foil / 1 μm nickel foil / 2 μm copper foil” (indicating the lamination order) is easily manufactured. be able to.

Moreover, in the manufacturing apparatus 1B having such a configuration, rectifiers 30 ₁ to 30 _n are independently connected to the plurality of electrolytic cells 11 _{1 to} 11 _n , respectively, and the power sources of the rectifiers 30 ₁ to 30 _n are provided. The energization between the anode body 12 and the cathode body 13 is controlled by the ON / OFF operation. For example, in the manufacturing apparatus 1B provided with the _five electrolytic cells 11 _{1 to} 115 along the cathode body 13 which is an endless belt or a plate-like body, the electrolytic cell which is the first electrolytic cell from the upstream side of the cathode body 13 11 _1, and the third electrolytic bath a electrolytic cell 11 ₃ is, electrolytic copper layer having a predetermined thickness in the electrolytic bath 11 ₅ a fifth electrolytic cell _{(20 1,} 20 3, 20 ₅₎ is formed to accommodate the electrolyte 10a of that condition, and the electrolytic cell 11 ₂ which is a second electrolytic bath, electroless nickel layer having a predetermined thickness in the electrolytic cell 11 ₄ is the fourth electrolytic cell (20 _2, 20 ₄ ) it is allowed to accommodate electrolyte 10b of conditions to be formed, is connected to the electrolytic cell ₁₁ 1 to 11 ₅ to ON / OFF control rectifier ₃₀ 1 to 30 ₅ can be energized independently with respect. According to this, produced by each of the electrolytic cell ₁₁ 1 to 11 ₅ each rectifiers independently connected to ₃₀ 1 to 30 ₅ of the power ON / OFF operation, the laminated metal foil made of any layered structure in a simple can do.

That is, for example, the power of each of the rectifiers 30 ₁ to 30 ₃ connected independently to the three electrolytic cells of the electrolytic cell 11 ₁ to the electrolytic cell 11 ₃ is turned on, and the electrolytic cell 11 ₄ to the electrolytic cell 1 ₁₅ 2 By turning off the respective power supplies of the rectifiers 30 ₄ to 30 ₅ independently connected to the two electrolytic cells, the energization between the anode body 12 and the cathode body 13 in the electrolytic cells 11 ₁ to 11 ₃ is performed. As a result, an electrolytic reaction occurs and the thin metal layers 20 _{1 to} 20 ₃ are formed. As a result, a laminated structure of “copper foil / nickel foil / copper foil” (indicating the order of lamination). Metal foil can be manufactured. On the other hand, by the respective ON the power supply of the rectifier ₃₀ 1 to 30 ₅ which are connected independently to every electrolytic cell 5 of the electrolytic cell 11 ₁ to the electrolytic cell 11 _5, the electrolytic cell 11 ₁ to the electrolytic cell 11 ₅ , the energization between all the anode bodies 12 and the cathode bodies 13 is in an “ON” state, and an electrolytic reaction occurs to form the thin metal layers 20 _{1 to} 20 _5. As a result, the “copper foil / A laminated metal foil having a laminated structure of “nickel foil / copper foil / nickel foil / copper foil” (indicating the order of lamination) can be produced. Thus, a laminated metal foil having a desired laminated structure can be easily manufactured only by turning on / off the power supply of the rectifier 30 independently connected to each electrolytic cell 11.

In the metal foil manufacturing apparatus 1B, the number of electrolytic cells 11 to be installed is not particularly limited, and is appropriately set according to a desired laminated structure of the thin metal layer 20 to be sequentially formed on the surface of the cathode body 13 as described above. be able to. As an example, in the case of producing a laminated metal foil having a laminated structure of “copper foil / nickel foil / copper foil” (indicating the order of lamination), the electrolytic copper plating solution was accommodated sequentially from the upstream side of the cathode body 13. electrolytic cell 11 _1, the electrolytic cell 11 2 which is housed the electroless nickel plating solution _may be a production apparatus 1B which electroless copper plating solution electrolytic cell 11 3 is _contained, and the total of three electrolytic cells 11 provided.

As shown in FIG. 4, in the metal foil manufacturing apparatus ₁ </ b> B, a water washing treatment tank 40 for performing a water washing treatment is provided between each of the plurality of electrolytic tanks 11 _{1 to} 11 ₃ . Water washing can be performed by spraying water toward the metal deposited on the surface of the cathode body 13.

<Metal foil peeling>
When the metal thin layer 20 having a desired thickness is formed on the surface of the cathode body 13 which is an endless belt or a plate-like body as described above, the metal thin layer 20 attached to the cathode body 13 is peeled off, and the metal A foil X is produced. Peeling of the thin metal layer 20 can be performed using, for example, a peeling device 50 as shown in FIG.

≪3. Integrated production of negative electrodes constituting batteries >>
A single metal foil obtained by the production method according to the first embodiment or a laminated metal foil made of a plurality of metals obtained by the production method according to the second embodiment is a battery such as a lithium ion secondary battery. Can be suitably used as a negative electrode current collector (negative electrode current collector).

  Here, in a lithium ion secondary battery among storage batteries, it is required to thin a copper foil (metal foil) used as a negative electrode current collector. This is intended to increase the amount of charge of the battery by increasing the area while reducing the thickness of the negative electrode current collector in the capacity and mass of the same battery case.

  As described above, in the conventional electrolysis metal foil using the drum method, it is difficult to efficiently manufacture a thin foil and improve the yield due to the problem of stress. From this, for example, a copper foil for transportation called a carrier of about 18 μm is first manufactured, and a thin foil of 2 to 5 μm has been manufactured by performing copper plating on the carrier again. According to this method, although it is possible to manufacture a thin foil without any technical problem, the thin foil of 2 to 5 μm is temporarily attached to the carrier foil of about 18 μm, and the user provides the thin foil. The carrier foil was separated from the thin foil and only the thin foil was used while the carrier foil was discarded. Therefore, even if the carrier foil is scrapped and reused, there is a problem that the cost increases.

Conventionally, such a thin foil with a carrier is used only as a material for a printed wiring board, and the price is about 900 to 2000 yen per 1 m ² . Currently, the electrolytic copper foil used as the negative electrode current collector of the lithium ion battery has a foil thickness of about 8 μm and about 300 yen per 1 m ² , and provides a thin foil with a carrier at an equivalent price. It was virtually impossible.

  On the other hand, as described above, in the present embodiment, the device 1A includes the anode body 12 and the cathode body 13 which is an endless belt or a plate-like body that can move along the anode body 12. 1B is used to move the cathode body 13 which is an endless belt or a plate-like body to the cathode body 13 in contact with the electrolytic solution 10 in the electrolytic cell 11 a plurality of times and sequentially contact the surface of the cathode body 13. A thin metal layer 20 is formed by depositing metal. According to such a method, a thin metal foil can be formed efficiently and with a good yield without using a carrier foil or the like.

  And according to such a method, the negative electrode body which is a constituent material of batteries, such as a lithium ion battery, can be manufactured consistently by using metal foils, such as copper foil manufactured, as a negative electrode collector. The “negative electrode body” means a negative electrode structure constituting a battery, and a structure including a negative electrode current collector made of a metal foil and a negative electrode active material applied to the surface of the negative electrode current collector. Say.

  In addition, as described above, there is a wide demand for the structure and performance of the negative electrode current collector constituting the battery, and by using the metal foil manufactured by the metal foil manufacturing apparatuses 1A and 1B as the negative electrode current collector, The thickness and structure of the negative electrode current collector can be easily controlled, and a variety of negative electrode bodies that meet various requirements, and thus batteries can be manufactured consistently.

<About the device configuration>
FIG. 5 is a configuration diagram showing an overall configuration of an apparatus for consistently manufacturing a negative electrode body that is a battery or a battery element. Here, a laminated metal foil made of a plurality of metals is manufactured (see the second embodiment), and an apparatus (hereinafter referred to as “a negative electrode body”) that consistently manufactures a battery or a battery element using the negative electrode current collector as a negative electrode current collector. The configuration of 1C) (referred to as “battery or battery element manufacturing apparatus”) will be described as an example. In addition, in this battery or battery element manufacturing apparatus 1C, the apparatus configuration for manufacturing the laminated metal foil is the same as the configuration of the metal foil manufacturing apparatus 1B according to the second embodiment described above. The same reference numerals are assigned and detailed description is omitted.

  As illustrated in the configuration diagram of FIG. 5, the battery or battery element manufacturing apparatus 1 </ b> C includes a negative electrode current collector manufacturing unit 61 and a negative electrode active material coating unit 62. The battery or battery element manufacturing apparatus 1 </ b> C includes a moving body 70 that is an endless belt or a plate-like body made of an insoluble material such as SUS coated with platinum, titanium, SUS, or chromium. A negative electrode current collector manufacturing unit 61 and a negative electrode active material coating unit 62 are provided along the same. That is, they are integrated through the moving body 70. As shown in FIG. 5, the negative electrode current collector manufacturing unit 61 is provided on the upstream side of the moving body 70, and the negative electrode active material coating unit 62 is provided on the downstream side of the negative electrode current collector manufacturing unit 61. ing.

(Negative electrode current collector manufacturing department)
The negative electrode current collector manufacturing unit 61 manufactures a negative electrode current collector preliminary body made of a metal foil. As the negative electrode current collector, for example, a copper foil or a laminated metal foil having a configuration of copper foil / nickel foil / copper foil can be used. The negative electrode current collector manufacturing unit 61 shown in FIG. 5 shows an example of a configuration for manufacturing the negative electrode current collector preliminary body 21 made of a laminated metal foil in which copper foil / nickel foil / copper foil are laminated in this order. In addition, as the negative electrode current collector manufacturing unit 61, the metal foil manufacturing apparatus 1B according to the second embodiment described above can be applied.

  In addition, the negative electrode current collector preliminary body means a long metal foil in a state where a metal is deposited and formed on the moving body 70 in the negative electrode current collector manufacturing unit 61. As will be described in detail later, a negative electrode active material 22 is applied to the surface of the negative electrode current collector preliminary body 21 that is a long metal foil to form a negative electrode preliminary body 23, and then cut into a battery or A battery element (for example, a negative electrode body) is manufactured.

  In the negative electrode current collector manufacturing unit 61, a moving body 70 that is an endless belt or a plate-like body made of an insoluble material such as SUS becomes a cathode body (13). By energization with the anode body 12 immersed in the electrolytic solution 10 in the electrolytic cell 11 provided along the metal, metal is deposited on the surface of the moving body 70 to form the thin metal layer 20.

In the negative electrode current collector manufacturing unit 61, a plurality of electrolytic cells 11 that store the electrolytic solution 10 are provided along a moving body 70 as a cathode body. In the configuration example of FIG. 5, the copper plating solution and the electrolytic cell ₁₁ 1, 11 ₃ for accommodating the (electrolyte 10a), a nickel plating solution (electrolytic solution 10b) is one in total 3 of the electrolytic cell 11 ₂ which accommodates the mobile 70 is provided. In such a negative electrode current collector manufacturing unit 61, as the moving body 70 serving as the cathode body moves, the electrolytic solutions 10a and 10b in the electrolytic cells 11 _{1 to} 11 ₃ come into contact with the moving body 70, Metals (copper and nickel) are sequentially deposited on the surface of the moving body 70 to form thin metal layers 20 _{1 to} 20 ₃ . Specifically, according to the negative electrode current collector manufacturing unit 61 shown in FIG. 5, copper foil (thin metal layer 20 ₁ ), nickel foil (thin metal layer 20 ₂ ), and copper foil (thin metal layer 20 ₃ ) are formed. Then, a laminated metal foil having these laminated structures is formed. That is, the long negative electrode current collector preliminary body 21 is formed. According to such a method for producing a metal foil to be the negative electrode current collector preliminary body 21, a thin metal foil, that is, a negative electrode current collector preliminary body 21 is formed efficiently and with good yield without using a carrier foil or the like. can do.

  The long negative electrode current collector preliminary body 21 manufactured by the negative electrode current collector manufacturing unit 61 is attached to the moving body 70 and moves downstream (in FIG. 5) as the moving body 70 moves. In the direction of arrow F). As shown in FIG. 5, following the negative electrode current collector manufacturing unit 61, a drying facility 80 for drying the metal foil as the negative electrode current collector preliminary body 21 manufactured on the surface of the cathode body that is the moving body 70. May be provided.

(Negative electrode active material coating)
The negative electrode active material coating unit 62 is provided on the downstream side of the negative electrode current collector manufacturing unit 61 described above along the moving body 70, and has been manufactured and transferred by the negative electrode current collector manufacturing unit 61. The negative electrode active material 22 is applied to the surface of the long negative electrode current collector preliminary body 21 (metal foil). In this way, by applying the negative electrode active material 22 to the surface of the negative electrode current collector 21, a long negative electrode body preliminary body 23 is obtained. The long negative electrode body preliminary body 23 is obtained in a state of adhering to the moving body 70, and then appropriately cut into a predetermined size to form a negative electrode body that is a battery element.

  The coating method of the negative electrode active material 22 in the negative electrode active material coating unit 62 is not particularly limited. For example, a long negative electrode assembly in which a slurry containing the negative electrode active material 22 is attached to the moving body 70 is used. It can be performed by coating on the surface of the preliminary electric body 21. The slurry can be formed by kneading the negative electrode active material 22, a binder such as a resin, and a material such as a conductive aid as necessary. Moreover, as a specific method of coating, for example, the coating can be performed by a well-known method using a doctor blade method or the like, and accompanying the movement of the moving body 70 to which the negative electrode current collector preliminary body 21 is attached. Can be applied continuously.

  The negative electrode active material 22 is not particularly limited, and a known material used for a negative electrode body of a battery such as a lithium ion secondary battery can be used. For example, particles of carbon (C) -based materials such as graphite and hard carbon, Sn-containing materials, Si-containing materials, metal composite oxides, lithium nitride metal compounds, and the like can be used.

  In addition, as shown in FIG. 5, following the negative electrode active material coating part 62, the negative electrode body preliminary body 23 obtained by coating the negative electrode active material 22 on the surface of the negative electrode current collector preliminary body 21 is dried. A drying facility 81 may be provided.

  As described above, in the present embodiment, as the moving body 70 moves, the negative electrode active material 22 is applied to the long negative electrode current collector preliminary body 21 attached to the moving body 70. Therefore, the negative electrode active material 22 can be applied by conveying the moving body 70 at a constant speed, and the negative electrode active material 22 can be more uniformly applied to the negative electrode current collector preliminary body 21. Contributes to improved battery performance. In addition, since the negative body preliminary body 23 is configured by transporting the moving body 70 at a constant speed, it can be manufactured with high productivity. In addition, it is possible to work at a constant speed for the pasting of the separator 24 in the separator coating portion and the pasting of the positive electrode preliminary body 25 described below, and the battery can be manufactured with high productivity. it can.

(Separator coating part)
In the battery or battery element manufacturing apparatus 1 </ b> C, the separator coating unit 63 can be provided on the downstream side of the negative electrode active material coating unit 62.

  The separator coating part 63 is a positive electrode for the long negative electrode body preliminary body 23 obtained by applying the negative electrode active material 22 to the surface of the negative electrode current collector preliminary body 21 in the negative electrode active material coating part 62. A separator 24 for separating the body and the negative electrode body and suppressing a short circuit between both electrodes is attached. In the separator coating part 63, the separator 24 is attached to the long negative electrode preliminary body 23 attached to the moving body 70 as the moving body 70 moves. The separator 24 is not particularly limited, and for example, a separator made of a porous resin film or the like can be used.

(Laminator device)
In the battery or battery element manufacturing apparatus 1 </ b> C, a laminator device 64 may be provided on the downstream side of the separator coating portion 63 as shown in FIG. 5. In the laminator device 64, a positive electrode preliminary material obtained by applying a positive electrode active material to the surface of the positive electrode current collector through the separator 24 with respect to the long negative electrode preliminary material 23 attached to the moving body 70. The body 25 is pasted. In this way, by providing the laminator device 64 for bonding the positive electrode body preliminary body 25 to the manufactured negative electrode body preliminary body 23 on the downstream side of the battery or battery element manufacturing apparatus 1C, lithium ion secondary A battery 26 such as a secondary battery can be manufactured in an integrated manner.

  In addition, in the battery or battery element manufacturing apparatus 1C, the long negative electrode body preliminary body 23 is formed through the negative electrode active material coating unit 62 without providing the separator coating unit 63 and the laminator device 64 described above. The negative electrode body 23 ′, which is a battery element, may be formed from the long negative electrode body preliminary body 23 by cutting into a predetermined size. Further, as described above, in the battery or battery element manufacturing apparatus 1C, the separator coating unit 63 and the laminator device 64 are provided, and the laminator device 64 connects the negative electrode body preliminary body 23 and the positive electrode body preliminary body 25 to the laminator 24. A battery (electrode configuration excluding a housing and the like) can be formed by cutting to a predetermined size after bonding.

1A, the manufacturing apparatus 1C negative electrode body manufacturing apparatus 10,10a of 1B metal foil, 10b electrolyte 11, 11 ₁ to 11 _n electrolytic cell 12 anode 13 cathode body 20, 20 ₁ to 20 _n metal thin layer X metal foil 21 negative Current collector preliminary body 22 Negative electrode active material 23 Negative electrode body preliminary body 23 'Negative electrode body 24 Separator 25 Positive electrode body preliminary body 26 Battery 30, 30 ₁ to 30 _n rectifier 40 Washing treatment tank 50 Peeling device 61 Negative electrode current collector manufacturing section 62 Negative electrode active material coating part 63 Separator coating part 64 Laminator device 70 Moving body 80, 81 Drying equipment

Claims (10)

An electrolytic cell containing an electrolytic solution;
An anode body immersed in the electrolytic solution;
A cathode body that is an endless belt or a plate-like body that faces the anode body and is movable along the anode body,
A plurality of the electrolytic cells are provided from the upstream side to the downstream side of the cathode body which is an endless belt or a plate-like body,
As the cathode body moves, metal is deposited on the surface of the cathode body sequentially by energization between the anode body and the cathode body in each electrolytic cell, and a metal foil is formed. apparatus. 2. The metal foil manufacturing apparatus according to claim 1, wherein a rectifier is independently connected to each of the plurality of electrolytic cells, and energization in each of the electrolytic cells is controlled by ON / OFF of a power source of the rectifier. . at least,
A negative electrode current collector manufacturing unit that is configured by the metal foil manufacturing apparatus according to claim 1 or 2 and that manufactures a long negative electrode current collector preliminary body including the metal foil,
The negative electrode current collector, which is provided downstream of the negative electrode current collector manufacturing unit along the cathode body in the negative electrode current collector manufacturing unit, and is transferred while attached to the cathode body as a moving body A negative electrode active material coating part for coating a negative electrode active material on the surface of the preliminary body,
A battery or battery element manufacturing apparatus comprising: An electrolytic cell containing an electrolytic solution;
An anode body immersed in the electrolytic solution;
A metal foil manufacturing method using an apparatus comprising: an endless belt or a cathode body which is an endless belt or plate-like body which faces the anode body and is movable along the anode body,
With the movement of the cathode body which is an endless belt or a plate-like body, the electrolyte solution in the electrolytic cell is brought into contact with the cathode body a plurality of times,
A method for producing a metal foil, wherein a thin metal layer is formed by sequentially depositing metal on the surface of the cathode body by energization between the anode body and the cathode body in the electrolytic cell in each of the plurality of times. The method for producing a metal foil according to claim 4, wherein the contact of the electrolyte solution with the cathode body a plurality of times includes a step of continuously performing the same electrolyte solution. The method for producing a metal foil according to claim 4, wherein the contact of the electrolyte solution with the cathode body a plurality of times includes contact with a certain electrolyte solution and contact with another electrolyte solution different from the electrolyte solution. The contact of the electrolyte solution with the cathode body a plurality of times is performed by sequentially contacting the electrolyte solutions in a plurality of electrolytic cells located from the upstream side to the downstream side of the cathode body. The manufacturing method of metal foil of description. The method for producing a metal foil according to claim 4, wherein the cathode body is moved at a constant speed. The method for producing a metal foil according to any one of claims 4 to 8, wherein the energization is performed under a condition that a current density in each of the electrolytic cells is constant. A method for producing a metal foil according to any one of claims 4 to 9, wherein a long negative electrode current collector preliminary body including the metal foil is produced,
While the negative electrode current collector preliminary body is transferred while being attached to the cathode body as a moving body, a negative electrode active material is applied to the surface, and then cut to form a battery or a battery element. Battery element manufacturing method.

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