JP2017171973A - Electrode device and metal foil manufacturing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel electrode device capable of simultaneously solving a problem of sludge coating covering the surface of an anode and a problem of increasing an interelectrode distance between the electrodes of the anode and a cathode, and to provide a metal foil manufacturing method using the electrode device.SOLUTION: An electrode device which is used by being immersed in a conductive liquid includes: a barrel having an outer wall with a plurality of through holes and capable of storing a metal soluble in the liquid during energization; a shaft penetrating the interior of the barrel and having an energizable peripheral surface; and a metal feed part for feeding the metal into the barrel. The shaft rotates with respect to the barrel. The shaft includes a plurality of blades that erect from the peripheral surface toward the outer wall of the barrel and have a gap with respect to the outer wall, and preferably the interior of the barrel is partitioned into a plurality of individual chambers with respect to the circumferential direction of the shaft by the plurality of blades of the shaft.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrode device and a method for producing a metal foil using the same.

  For example, copper foil (Cu foil) or aluminum foil (Al foil) is used for current collectors of power storage devices such as lithium ion secondary batteries and supercapacitors (electric double layer capacitors, redox capacitors, lithium ion capacitors, etc.) Is done. Cu foil is produced by a rolling method or an electroplating method (electroforming method, electrolytic method). Moreover, although such Al foil was produced exclusively by the rolling method, examination which applies the electroplating method is being performed recently. In such an electroplating method, a current component immersed in a liquid (plating solution) is energized between a soluble or insoluble metal (anode) and a peripheral surface of the drum (cathode), thereby forming a metal component as an anode. A metal film (plating film) is formed on the peripheral surface of the drum serving as the cathode.

  In the above electroplating method, during energization, the soluble metal (anode) is eluted into the liquid as metal ions, and the surface is covered with a coating (sludge coating) that is considered to be an oxide as the elution progresses. Become. In addition, even when insoluble during energization, an oxidation reaction occurs on the surface of the metal (anode) in the liquid, and the same sludge film is formed by the reaction product. A metal (anode) covered with such an electrically insulating sludge film is not preferable for electrodeposition of metal because elution of metal ions into the liquid is hindered. For this reason, for example, Patent Document 1 discloses an electrode device (electroplating) having a structure in which a soluble metal plate is inserted between a prismatic zinc (anode) and a current-carrying body for the purpose of suppressing the formation of a sludge film. Anodes) have been proposed. In addition, for example, a means for adjusting the composition of the liquid so as to be suitable for the metal serving as the anode (see Patent Document 2), or the sludge coating by adjusting the structure of the Sn—Bi based metal serving as the anode to replace the Bi with Sn Means (see Patent Document 3) for suppressing the generation of are proposed.

  In addition, during energization, the anode metal has a strong tendency to elute from the side close to the cathode (drum peripheral surface) having a different polarity, so the distance between the anode (metal) and the cathode (drum peripheral surface) (electrode) (Distance between) gradually increases. An increase in the distance between the electrodes is not preferable because not only the electrolytic voltage increases and power consumption increases, but also the thickness and quality of the metal film formed on the peripheral surface of the drum are affected. Therefore, for the purpose of keeping the distance between the electrodes constant, for example, Patent Document 4 discloses a plurality of anode baskets that are attached to a rotating belt and are movable, and are filled with pellet-shaped metal particles (anode), and near the center. And an anode baffle plate with a constant distance from the cathode (distance between the electrodes), and the anode baffle plate can be energized by contacting only the specific anode basket. An electrode device (electroplating device) configured as described above has been proposed. Further, for example, in Patent Document 5, a plurality of metal plates (anodes) suspended by hooks are arranged so that the distance from the steel plate (cathode) is constant, and the consumption state of the metal plate and the distance from the steel plate ( There has been proposed an electrode device configured to detect an inter-electrode distance), extract a worn metal plate, and control to insert a new metal plate (anode).

Japanese Patent Laid-Open No. 62-294199 JP-A-4-333590 JP 2011-58076 A JP 2009-13440 A JP 2013-181207 A

  As the above-described lithium ion secondary battery is put into practical use and expanded, there is a strong demand for cost reduction by stabilizing the quality of metal foil and improving productivity. For this reason, the technical improvement related to the suppression of the generation and proper removal of the above-described anode sludge coating and the technical improvement related to the increase in the distance between the anode and the cathode are becoming more important. However, the electrode device described in Patent Document 1 cannot suppress an increase in the interelectrode distance. In addition, the means for adjusting the composition of the liquid (see Patent Document 2) and the means for adjusting the structure of the Sn-Bi metal structure (see Patent Document 3) differ in the material of the metal serving as the anode and the composition of the liquid. In some cases, it is difficult to apply, and for example, it is considered that it cannot be applied to the production of an Al foil (electrolytic Al foil) using a nonaqueous electrolytic solution (nonaqueous plating solution).

  In addition, in the electrode device described in Patent Document 4, because the metal particles (anode) are filled and stationary in the anode basket in contact with the anode baffle plate, the generation of sludge coating on the anode surface is suppressed, It is considered difficult to properly remove the generated sludge film. In the electrode device described in Patent Document 4, it is possible to insert a new anode basket by moving the rotating belt at the timing when the sludge film is formed on the surface of the anode. Even if it is not sufficiently consumed, it must be replaced, which is not practical from the viewpoint of the efficiency of use of the anode. Further, in the electrode device described in Patent Document 5, since the anode (metal plate) is suspended by the hook and is stationary, it is difficult to appropriately suppress and remove the above-described anode sludge coating. It is done. In addition, in the electrode device described in Patent Document 5, it is necessary to install a special control device that detects and controls the consumption state of the anode (metal plate) and the distance between the electrodes with the cathode (steel plate). The degree of freedom of the shape and arrangement of the cathode is extremely limited.

  An object of the present invention is to provide a novel electrode device having a structure capable of solving the above-described problem of the sludge coating covering the surface of the anode, and more preferably solving the problem of an increase in the distance between the anode and the cathode at the same time. And it is providing the manufacturing method of the novel metal foil using the same.

  The present inventor has studied an electrode structure that can sequentially arrange or supply a metal to be an anode to a certain position, and has an electrode filled with an appropriate amount of metal (metal tip or the like) to be an anode inside the barrel, The present inventors have found that the above-mentioned problems can be solved by causing mutual collision of metal (anode) by stirring inside the barrel, and have arrived at the present invention.

That is, the electrode device of the present invention is an electrode device used by being immersed in a conductive liquid, and has an outer wall having a plurality of through holes, and can store a metal that is soluble in the liquid during energization. A barrel, a shaft having a circumferential surface that can be energized through the inside of the barrel, and a metal feeding portion that feeds the metal into the barrel; and the shaft rotates with respect to the barrel. To do.
The shaft includes a plurality of blades standing from the peripheral surface toward the outer wall of the barrel and having a gap with respect to the outer wall, and the inside of the barrel is formed by the plurality of blades of the shaft. It is preferable that it is divided into a plurality of individual chambers (cells) in the circumferential direction.

In the electrode device of the present invention, the metal is preferably spherical.
Moreover, it is preferable that the said shaft has an outer cylinder provided with the said surrounding surface, and a shaft body which mounts the said outer cylinder.
Further, it is preferable that the outer cylinder is attached to the shaft body by a taper structure.

  The electrode device of the present invention described above can be used for producing a metal foil such as an Al foil by an electrolytic method. That is, the manufacturing method of the metal foil of the present invention includes the electrode device according to any one of claims 1 to 5, wherein a metal soluble in the liquid is stored in a conductive liquid during energization, A part of the peripheral surface of the drum having a different polarity with respect to the electrode device is immersed, the shaft of the electrode device is rotated, and while rotating the drum in one direction, the peripheral surface of the drum and the electrode Metal is energized between the peripheral surface of the shaft of the apparatus, a metal film containing the metal component is electrodeposited on the peripheral surface of the drum, and the metal film is peeled off from the peripheral surface of the drum. A method of forming a foil.

The metal foil manufacturing method of the present invention preferably includes a process of feeding the metal into the barrel of the electrode device during the energization.
The metal may contain 97% by mass or more of aluminum.

  According to the present invention, the sludge film formed on the surface of the anode is appropriately removed during energization, and the substantial variation in the distance between the anode and the cathode is suppressed. Therefore, by using the electrode device of the present invention, it is possible to produce a healthy and continuous metal foil by an electrolytic method.

It is a figure which shows the structural example of the electrode apparatus of this invention in part using an axial direction cross section. (A) is sectional drawing which shows the axial cross section of the position shown by line segment PP in FIG. 1 in the state which stored the metal inside the barrel, (b) is a blade | wing inside the barrel shown to (a). It is the provided modified structural example. It is a figure which shows the structural example of the electrode apparatus of this invention different from FIG. 1 using an axial direction cross section in part. It is sectional drawing which shows the axial cross section of the position shown by line segment PP in FIG. It is sectional drawing which shows the state with which the metal used as an anode was filled into the inside of the barrel shown in FIG. FIG. 6 is a cross-sectional view showing a state in which the shaft is rotated forward from the position shown in FIG. 5 by an angle corresponding to one private chamber. It is sectional drawing which shows the structural example of the electrode apparatus of this invention which has another axial cross section different from FIG. It is sectional drawing which shows the structural example of the electrode apparatus of this invention which has another axial cross section different from FIG.4 and FIG.7. It is sectional drawing which expands and shows the vicinity of one private room shown in FIG. FIG. 10 is a cross-sectional view illustrating a state in which the shaft is rotated forward from the position illustrated in FIG. 9 by an angle corresponding to one private chamber. It is a figure which shows the structural example of a shaft in part using an axial direction cross section. It is sectional drawing which shows the structural example of the shaft which has another axial cross section different from FIG. It is a figure which shows the structural example of the manufacturing apparatus of metal foil using the electrode apparatus of this invention.

The electrode device of the present invention will be described in detail with reference to the drawings as appropriate.
An example of the configuration of the electrode device of the present invention is shown in FIG. 1 using a cross section in the axial direction, and the axial cross section at the position indicated by the line segment PP in FIG. 1 is shown with the metal M stored inside the barrel 2. 2 (a) shows a modified configuration example in which the blade 3e is provided inside the barrel 2 shown in FIG. 2 (a). Further, a configuration example of the electrode device of the present invention different from the configuration shown in FIG. 1 is partially shown in FIG. Show. Further, in the configuration example shown in FIG. 4, the state in which the metal M serving as the anode is filled in the barrel 2 is shown in FIG. 5, and the shaft 3 is rotated by an angle corresponding to one individual chamber from the position shown in FIG. The state is shown in FIG. In addition, the metal M shown in each figure referred in this specification is abbreviate | omitted using hatching as a whole for convenience, and shows each metal only in part.

  The electrode device 1 shown in FIG. 1 and the electrode device 1 shown in FIG. 3 (hereinafter sometimes collectively referred to as “electrode device 1”) have resistance to the electrolyte so that they can be used by being immersed in the electrolyte. Have. The electrode device 1 has an outer wall 2b having a plurality of through holes 2a, and a barrel 2 capable of storing a metal M that is soluble in an electrolyte during energization, and a peripheral surface that can be energized through the interior of the barrel 2. A shaft 3 having 3a and a metal feeding portion 4 for feeding metal M into the barrel 2 are provided. The metal feeding section 4 has a configuration capable of feeding the metal M (individual metal) into the barrel 2 that is energized without hindering the rotation of the shaft 3. In addition, the electrode device 1 has a liquid feeding part 5 that discharges an electrolytic solution into the barrel 2.

  The shaft 3 is connected to the drive shaft 6 that rotates the shaft 3 via gears 6 a and 6 b on one end side, and rotates relative to the barrel 2 that is positioned with respect to the shaft 3 by the sliding portion 7. In addition, you may provide the drive shaft for shaft rotation in the both end side. Further, the center of rotation of the shaft 3 does not have to coincide with the axial center of the barrel 2. Moreover, it is preferable that the metal M is configured to efficiently gather on the peripheral surface 3a approaching the cathode 8 side by rotation of the shaft 3 during energization. Further, for example, the peripheral surface 3 a of the shaft 3 can be configured to rotate eccentrically inside the barrel 2 by shifting the rotation center of the shaft 3 by an appropriate amount from the axial center of the barrel 2. In addition, the barrel 2 is rotatably supported by the shaft 3 via the sliding portion 7, and although not shown in the figure, it may be fixed at both ends, or may be rotatably supported at both ends. May be.

  Further, the shaft in the present invention is one or more having a gap from the peripheral surface 3a toward the outer wall 2b of the barrel 2 and having a gap with respect to the outer wall 2b of the barrel 2, as in the shaft 3 shown in FIG. By providing the blade 3e, the internal space of the barrel 2 can be partitioned. In that case, preferably, as shown in FIG. 4, the shaft 3 is provided with a plurality of blades 3 e erected from the peripheral surface 3 a toward the outer wall 2 b of the barrel 2 and having gaps with respect to the outer wall 2 b of the barrel 2, The configuration is such that the inside of the barrel 2 is divided into a plurality of individual chambers 2d in the circumferential direction of the shaft 3 by the plurality of blades 3e. A plurality of metals M (individual metals) stored in the barrel 2 by providing blades 3e having a gap with respect to the outer wall 2b of the barrel 2 as in the shaft 3 shown in FIG. 2B or FIG. Since the blades 3e are moved so as to stir, the plurality of metals M (individual metals) can be efficiently flowed. Further, when the shaft rotates, as shown in FIGS. 2B and 5, the blade 3e moves upward while holding an appropriate amount of metal M (individual metal), so that the anode and the cathode are closer to the cathode. An appropriate amount of the metal M can be arranged to increase the electrolysis efficiency.

  Further, as shown in FIG. 5, a plurality of metals M (individual metals) can be stored in the inside of the barrel 2 shown in FIG. 2B or in the plurality of individual chambers 2d inside the barrel 2 shown in FIG. is there. The metal M (individual metal) can be filled so that the total amount of metal becomes an appropriate amount with respect to the total volume of the barrel 2 before energization. In the case of the electrode device 1 shown in FIG. 4, the number of private chambers 2 d provided in the barrel 2 is eight. In the individual chamber 2d of the barrel 2 located above the shaft 3, some of the individual metals (metal M) can be deposited on and contact the peripheral surface 3a of the shaft 3 (see FIG. 5). . Therefore, if the current is applied to the peripheral surface 3a of the shaft 3 in this state, the metal M in the individual chamber 2d can also be energized. Therefore, individual metals (metal M) filled in the individual chamber 2d of the barrel 2 are anodes. Can act as This point will be described in detail later.

  In the electrode device of the present invention, when the shaft rotates with respect to the barrel, the metal M (individual metal) stored in the barrel is moved and flows, and mutual collision occurs between adjacent individual metals. . The mutual collision of these individual metals occurs during energization, so that the surface of the individual metal M that has become the anode is able to react uniformly in a fresh state while the generated sludge coating is appropriately removed. It becomes a surface that can. Therefore, according to the electrode device of the present invention, the above-mentioned problem of the sludge film covering the surface of the anode can be solved.

  Moreover, the preferable structure which can perform the flow of each metal (metal M) mentioned above more efficiently is an electrode apparatus which has a cross-sectional structure as shown in FIG.4, FIG.7, FIG.8. For example, in the electrode device 1 shown in FIG. 4, when the shaft 3 rotates with respect to the barrel 2, the plurality of blades 3 e provided on the shaft 3 rotate. Therefore, the individual metals filled in the individual chamber 2d are moved so as to be agitated by the blades 3e, and mutual collision occurs between adjacent individual metals. Therefore, the surface of each metal M that has become an anode due to the mutual collision that occurs during energization becomes a surface that can be uniformly reacted in a fresh state while the generated sludge coating is appropriately removed.

  By the way, each metal that has become an anode inside the barrel is melted (hereinafter referred to as “electrolysis”) by energization, and its volume gradually decreases. For this reason, the distance between the electrodes of the metal M serving as the anode and the cathode increases by an amount corresponding to the volume reduction of each metal. In the electrode device according to the present invention, the metal M (individual metal) is fed into the barrel during energization by having the metal feeding portion for feeding the metal M (individual metal) into the barrel. Since replenishment can be performed, the spread of the distance between the electrodes can be suppressed. Therefore, according to the electrode device of the present invention, the problem of the sludge film covering the surface of the anode as described above can be solved, and the problem of the increase in the distance between the anode and the cathode can be solved at the same time. .

  Further, in the electrode device 1 having a cross-sectional structure in which the inside of the barrel 2 is divided into a plurality of individual chambers 2d as shown in FIG. 4, a metal M (individual metal) in the individual chamber 2d located on the side closest to the cathode. Therefore, the distance between the cathode and the cathode becomes wider than that in the other individual chambers 2d. For example, in the private chamber 2d located on the side closest to the cathode, during the energization, a metal M that is soluble in the electrolyte deposits on the energized peripheral surface 3a of the shaft 3, and the individual metals come into contact with each other. It becomes a state. When energized in this contact state, current is applied to the individual metal from the peripheral surface 3a of the shaft 3, and the electrolysis of the surface of the individual metal closest to the cathode easily proceeds, so that volume reduction is likely to occur.

In the electrode device 1 having the cross-sectional structure as shown in FIG. 4, the problem of the volume reduction of each individual metal is that each individual chamber 2 d of the electrode device 1 moves forward in the rotation direction by the rotation of the shaft 3 with respect to the barrel 2. This can be solved. Specifically, the private room 2d ₁ shown in FIG. 5 moves forward from the position closest to the surface of the cathode 8 by the rotation indicated by the arrow 3f of the shaft 3, and the next private room 2d ₂ is the cathode as shown in FIG. 8, the metal M in the next chamber 2d ₂ having no substantial volume reduction compared to the metal M ₁ instead of the metal M ₁ in the volume-reduced chamber 2d ₁ by being located on the side closest to the surface of FIG. _This can be solved because 2 can be positioned closest to the surface of the cathode 8. Therefore, by applying the electrode device 1, it is possible to suppress a substantial change in the interelectrode distance between the surface of the metal M that is the anode closest to the cathode and the surface of the cathode 8 during energization.

  When the volume of each metal (metal M) inside the barrel according to the present invention is reduced by electrolysis, a plurality of through holes are provided on the outer wall of the barrel, so that the surface area is consumed by electrolysis to be smaller than the size of the through holes. Each metal with a reduced can be naturally discharged from the through hole by gravity or the like. For example, in the electrode device 1, since the outer wall 2b of the barrel 2 is provided with a plurality of through holes 2a, individual metals that have become smaller from the through holes 2a can be discharged naturally. In addition, when the amount of individual metal (metal M) is reduced due to the above consumption or discharge, new metal M (individual metal) is supplied from the metal inlet to the inside of the barrel while controlling the amount corresponding to the amount of the reduction. can do.

  Moreover, it is preferable that the above-mentioned control regarding the metal M is sent so that, for example, in the electrode device 1, a new metal M (individual metal) is pushed into the barrel 2 through the metal feed portion 4, for example. Moreover, it is preferable to supply the new metal M (individual metal) at a position that is not close to the cathode, which is not easily affected by energization.

  In the present invention, the barrel is shaped so that the shaft can be rotated most efficiently in consideration of various conditions such as the shape, size, and mass of the metal stored in the interior and the properties and temperature of the electrolyte. Or a size. For example, in the electrode device 1 having the cross-sectional structure shown in FIG. 4, the shape of the axial cross section of the barrel is such that the outer wall shown in FIG. 4 is cylindrical and has eight individual chambers, and the outer wall shown in FIG. The outer wall may have a polygonal shape, such as a configuration including eight individual chambers, or a configuration in which the outer wall illustrated in FIG. 8 is hexagonal and includes six individual chambers. The numbers shown in FIG. 7 and FIG. 8 use the numbers shown in FIG. 4 for convenience.

  In the case of an electrode device in which the interior of the barrel is divided into a plurality of individual chambers, it is preferable that the plurality of blades provided on the shaft be set to an appropriate shape and number in consideration of the above-described conditions. Specifically, the shape of the blade may be a flat plate shape shown in FIG. 4, a curved plate shape, a corrugated plate shape, other different shapes, or a shape obtained by partially combining these shapes. Further, the number and arrangement of the blades are determined in consideration of the above-mentioned conditions, as shown in FIG. 4, by dividing the circumferential direction of the shaft 3 into eight places and arranging them evenly, or less than eight places or more than eight places. For example, it is possible to divide the distance between the blades so as to be equal, or to separate all the distances between the blades. For example, referring to the barrel 2 shown in FIG. 3, the distance between the blades around the axis can be changed by adjusting the number of blades on the right and left sides in the axial direction of the shaft 3, or the right side and the left side. The blade mounting position (blade phase) in the circumferential direction of the shaft 3 can be changed. In addition, the arrangement of the blades viewed from the axial cross section with respect to the outer wall is in consideration of the above-mentioned conditions, and is arranged in a direction perpendicular to the outer wall, an arrangement inclined around the axis, or an axial direction such as a helical axial cross section. It can also arrange so that a phase may change gradually.

Next, the behavior of the metal M stored in the private chamber 2d when the shaft 3 rotates with respect to the barrel 2 in the electrode device 1 having the cross-sectional structure shown in FIG. 4 will be described with reference to the drawings. Expanding the vicinity of Figure 5 and and private 2d ₂ inside the private 2d ₁ barrel 2 as shown in FIG. 6, 9 and 10. The numbers shown in FIGS. 9 and 10 are the same as those shown in FIGS. 5 and 6 for the sake of simplicity.

For example, in the individual chamber 2d ₁ shown in FIG. 9 located above the shaft 3 inside the barrel 2, the individual metals constituting the metal M come into contact with each other by their own weight, and contact S (hereinafter referred to as the contact shown in the figure). representing at S _1.) constitute, some of the individual metal contacts S (hereinafter in contact with the circumferential surface 3a of the shaft 3, is represented by the contact S ₀ shown in FIG.) configuration to the Yes. Individual metal positioned on the side closest to the contact point S ₁ and, according to the contact S ₀ between the individual metal in contact with the peripheral surface 3a, the farthest side or cathode 8 from the peripheral surface 3a between the above individual metal It can be set as the electrically continuous structure through the contact S. In this state, by supplying electric energy via a peripheral surface 3a of the shaft 3, to supply the electrical energy to all the individual metal through the contact S in the interior of the private 2d ₁ barrel 2 it can.

Moreover, while power and private 2d ₁ is moved to the position shown in FIG. 10 by the rotation of the shaft 3, the individual metals were in state described above (metal M) is flowing in the private room 2d ₁ by the tilt by rotating The position is continuously changed and agitated. Some of the metal M may also be moved from private 2d ₁ as indicated by arrows 3g through a gap 2e to another private. However, since the surfaces of the individual metals are in contact with each other due to their own weight, the positions can be continuously changed while rubbing each other's surfaces. Therefore, the contact S ₁ between the individual metal can be reconstructed instantaneously immediately even apart by agitation. The reconstruction of this contact is the same for the contacts S ₀ of the peripheral surface 3a. In addition, when each metal is spherical, that is, when a spherical metal is used as the metal M, the individual metals are likely to contact each other evenly, and the configuration of the above-described contact S (contact S ₁ , contact S ₀ ) is the same. It is preferable because it is performed more reliably and stably.

Further, during stirring, as described above, a sludge film by electrolysis is easily formed on the surface of each metal located on the side closest to the cathode 8. However, since the surfaces of the individual metals rub against each other due to their own weight, even if a sludge film is formed on the surface, the individual metals are immediately removed immediately. At this time, if the individual metal is spherical, that is, if the spherical metal is used as the metal M, the individual metals are likely to contact each other evenly, and the sludge coating can be removed more reliably and stably. Therefore, it is preferable. Therefore, during energization, the surface of the individual metal as the anode is held substantially fresh, electrical energy between the individual metal is stably transmitted by the contact S _1. In addition, the sludge film (sludge residue) removed from the surface of each metal is naturally discharged from the plurality of through holes 2a provided on the outer wall 2b of the barrel 2 described above. At this time, if the electrolytic solution is discharged from the liquid inlet 5 into the barrel 2, the inside of the individual chamber 2d is stirred by the electrolytic solution, and the discharge of sludge residue is promoted.

Further, as described above, when the metal M (individual metal) can be supplied to the inside of the barrel 2 during energization, the individual metal that is fresh and not consumed and the individual metal that is being consumed by electrolysis The metal M coexisting with the metal and becomes an aggregate of individual metals having various sizes (hereinafter referred to as “steady-state metal M”) is stored in the barrel 2. The flow of the metal M (individual metal) in the steady state by the stirring described above contributes to maintaining the metal ion concentration in each individual chamber 2d in a homogeneous state. Further, since each individual chamber 2d is provided with a blade 3e having a gap 2e with respect to the outer wall 2b of the barrel 2, a steady state metal M (individual) is rotated by rotation of the shaft 3 from the gap 2e to another adjacent chamber 2d. Metal) can also flow. The size of the gap 2e, for example when considering internal private 2d ₁ positioned upward as shown in FIG. 9, as an appropriate amount of metal M inside the private room 2d ₁ is stored, adjacent individual metal It is preferable to set the degree to which an excessive flow to the separate chamber 2d is suppressed (for example, about 1.1 to 2.5 times the average particle diameter of the unelectrolyzed individual metal). Therefore, the metal ion concentration as a whole is also maintained in a uniform state in the barrel 2 in which the steady state metal M is stored in the individual chambers 2d. In addition, it is preferable that each metal is spherical, that is, if a spherical metal is used as the metal M, the individual metal easily passes through the gap 2e, and the above-described flow is performed more reliably and stably. .

  Further, it is preferable that the electrolyte is discharged into the barrel 2 during energization. As a result, the electrolytic solution in the barrel 2 whose concentration has been increased by electrolysis is positively pushed out from the plurality of through holes 2a provided in the outer wall 2b, so that the space between the barrel 2 (electrode device 1) and the cathode 8 is increased. The metal ions in the electrolyte can be kept at a high concentration. In addition, during energization, the electrolyte solution is in the region in the barrel 2 facing the peripheral surface 3 a of the shaft 3 that is closest to the cathode 8 due to the rotation of the shaft 3, or the circumference of the shaft 3 that is about to approach the cathode 8. It is preferably supplied to a region in the barrel 2 that faces the surface 3a. As a result, the electrolyte solution passes through the gaps of the metal M (individual metal) in the above region, and the outer wall 2b is provided with the electrolyte solution around the metal M (individual metal) having a high concentration by electrolysis. Since the plurality of through-holes 2a are positively pushed out to the outside, the metal ions of the electrolytic solution between the barrel 2 (electrode device 1) and the cathode 8 can be kept at a higher concentration. When the electrode device 1 of the present invention having such a configuration is used as an anode, a liquid flow of an electrolytic solution having a high metal ion concentration is supplied to the cathode 8, so that stable electrolytic treatment can be performed.

  The liquid feeding part 5 for discharging the electrolytic solution into the barrel 2 is, for example, a pipe for feeding the electrolytic solution or the like attached from the axial direction of the barrel 2, and the opening thereof at one place on the side wall of the barrel 2 or By providing at a plurality of locations, the electrolytic solution may be discharged into the barrel 2 as shown by an arrow 5a in FIG. In addition, the liquid feeding section 5 draws, for example, a pipe for feeding an electrolytic solution from the axial direction of the barrel 2 into the barrel 2, and further in the axial direction at a position away from the cathode 8 such as the bottom in the barrel 2. And the opening is provided at one or a plurality of locations opposite to the peripheral surface 3a of the shaft 3 to discharge the electrolyte into the barrel 2 as shown by the arrow 5a in FIG. The discharged electrolyte may pass between the metals M (individual metals) stored at the bottom of the barrel 2.

For example, in the configuration example in which the barrel 2 is disposed below the cathode 8, the metal M stored in the individual chamber 2d inside the barrel 2 is most easily electrolyzed above the shaft 3 shown in FIG. it is in an internal position the private 2d _1. Therefore, the circumferential surface 3a of the shaft 3 corresponding to the private 2d ₁ also tends to electrolysis target. However, in this configuration example, the peripheral surface 3 a of the shaft 3 is located on the side farthest from the cathode 8 and constitutes a contact S ₀ with the metal M (individual metal). Therefore, the metal M located closer to the cathode 8 is preferentially electrolyzed, and substantial wear of the peripheral surface 3a of the shaft 3 due to electrolysis can be suppressed. In addition, the shape of the peripheral surface 3a of the shaft 3 can be, for example, an ellipse or a polygon in addition to the circular shape shown in FIG. It is preferable to select in consideration.

  The peripheral surface 3a of the shaft 3 can suppress substantial wear due to electrolysis by the above-described configuration, for example. However, when energized for a long time, the wear of the peripheral surface 3a of the shaft 3 can be avoided due to the collision of the metal M (individual metal) due to the above stirring or due to the gradually proceeding electrolysis. Absent. Therefore, in the present invention, as shown in FIG. 11, the shaft 3 preferably includes an outer cylinder 3b having a peripheral surface 3a and a shaft body 3c on which the outer cylinder 3b is mounted. With this configuration, when the peripheral surface 3a is consumed or damaged, it is only necessary to replace the outer cylinder 3b, and the shaft body 3c can be reused. Further, the outer cylinder 3b shown in FIG. 11 has a configuration in which the shaft body 3c is mounted on the cylindrical surface, and more preferably the outer cylinder 3b having the configuration shown in FIG. Since the outer cylinder 3b has a tapered structure in which the shaft body 3c is mounted on the tapered surface 3d, the outer cylinder 3b can be easily attached to and detached from the shaft body 3c. Such a tapered structure has a shape in which the outer peripheral shape of the shaft body 3c increases in diameter from one to the other in the axial direction, and the inner peripheral shape of the corresponding 3b is similar to the outer peripheral shape of the shaft body 3c in the axial direction. It has a shape in which the diameter increases from one to the other, and has a structure that combines with each other.

  Next, regarding the manufacturing method of the metal foil of the present invention using the electrode device of the present invention described above, a configuration of an apparatus (hereinafter referred to as “manufacturing apparatus”) capable of continuously manufacturing the metal foil to which the manufacturing method is applied. An example will be described with reference to the drawings as appropriate.

  The manufacturing apparatus shown in FIG. 13 is disposed so as to face the electrolytic solution 11 that is a conductive liquid, the rotating drum 12, and the peripheral surface 12a of the drum 12, and is soluble in the electrolytic solution 11 during energization. A plurality of electrode devices 1 each having a barrel 2 in which a metal M is stored are disposed in a sealed container 13. The distance between the electrode device 1 and the peripheral surface 12a of the drum 12 is set to a range in which a more efficient electrolytic state can be obtained. Moreover, it has the circulation apparatus 14 of the electrolyte solution 11, the storage tank 15 of the electrolyte solution 11, and the stirrer 16 for stirring the electrolyte solution 11 in the storage tank 15. FIG. In addition, since the electrolyte solution 11 is filled up to the liquid surface 11 a between the peripheral surface 12 a of the drum 12 and the electrode device 1, the electrode device 1 is different from the electrode devices 1 having the metal M serving as an anode. A part of the peripheral surface 12 a (corresponding to the cathode 8 shown in FIG. 5) of the drum 12 serving as a pole is immersed in the electrolytic solution 11. Further, the electrolytic solution 11 is filled up to the liquid level 11 b in the sealed container 13 and filled up to the liquid level 11 c in the storage tank 15.

  When the metal foil 10 is formed by the manufacturing apparatus described above, the drum 12 is continuously rotated in the direction indicated by the arrow 18 by the rotating shaft 12b in a state where power is appropriately supplied. At this time, in the present invention, while rotating the shaft 3 included in the plurality of electrode devices 1, current is appropriately supplied between the peripheral surface 12 a of the drum 12 and the peripheral surface 3 a of the shaft 3 of the electrode device 1, and the drum The metal film 10a containing the component of the metal M is electrodeposited on the 12 peripheral surfaces 12a. In addition, by including a process of feeding only the metal M corresponding to the volume reduction consumed by the electrolysis of the metal M stored in the barrel 2 into the interior of the barrel 2 of the electrode device 1 during energization. It is preferable to always keep the volume of the metal M serving as the anode in a stable state.

  The metal film 10 a is electrodeposited on the peripheral surface 12 a of the drum 12 by the above operation, and the metal film 10 a can be formed on the metal foil 10 by peeling from the peripheral surface 12 a of the drum 12. In this manufacturing apparatus, immediately after the metal film 10a is peeled off and formed on the metal foil 10, the front and back of the metal foil 10 is drained by the wiper 17 provided on the outlet side of the sealed container 13 in the direction indicated by the arrow 19. Can be pulled out continuously. The inside of the sealed container 13 is preferably an anaerobic dry atmosphere having a dew point of −40 degrees or less, thereby suppressing deterioration of the electrolyte solution 11 due to moisture absorption.

  In the present invention, the metal M serving as the anode may be, for example, an aluminum alloy containing 97% by mass or more of aluminum or substantially pure aluminum containing 99.9% by mass or more of aluminum. In addition, when using the aluminum alloy whose aluminum is less than 97 mass% as the metal M, it should be noted that the generation amount of the sludge film at the time of energization may increase and the electrolysis efficiency may decrease.

  Moreover, in said manufacturing apparatus, while forming the metal foil 10 continuously, the circulation apparatus 14 is comprised so that the electrolyte solution 11 may be forcedly circulated. Specifically, the circulation device 14 sucks out the electrolyte solution 11 from the storage tank 15 in the direction indicated by the arrow 20a and forcibly sends it out in the direction indicated by the arrow 20b, thereby passing between the plurality of electrode devices 1. A liquid flow of the electrolyte solution 11 toward the peripheral surface 12a of the drum 12 can be formed. Then, the liquid flow that has reached the peripheral surface 12a of the drum 12 turns in the direction along the peripheral surface 12a, moves toward the liquid surface 11a along the peripheral surface 12a, and overflows from the liquid surface 11a as indicated by an arrow 20d. . Thereafter, the overflowing electrolyte solution 11 falls to the liquid surface 11b, flows in the direction indicated by the arrow 20e, and returns to the storage tank 15. By circulating the electrolytic solution 11 by the circulation device 14 and sufficiently stirring the electrolytic solution 11 by the stirrer 16 in the storage tank 15, the electrolytic solution 11 having a uniform metal ion concentration and temperature is continuously circulated. Can do. In the circulation process of the electrolyte solution 11, it is preferable to perform flow rate control by providing a flow meter at an appropriate location in the circulation path including the circulation device 14.

  In addition, as described above, in the case of the electrode device 1 having the liquid feeding part 5 that discharges the electrolytic solution 11 into the barrel 2, in addition to the circulation of the electrolytic solution 11, the barrel 2 is fed from the liquid feeding part 5. The liquid 11 having a high metal ion concentration inside the barrel 2 is positively supplied to the periphery of the barrel 2 by the electrolytic solution 11 discharged into the interior of the drum 12, and the metal ion concentration indicated by the arrow 20 f toward the peripheral surface 12 a of the drum 12 is A liquid flow of the electrolyte solution 11 that is homogeneously high can be formed. In this case, the supply of the electrolytic solution 11 to the liquid feeding unit 5 may be, for example, a branch from the circulation device 14 or a dedicated liquid supply device (not shown).

  The electrode device of the present invention and the method for producing a metal foil using the electrode device can be used for producing a continuous metal foil by an electrolytic method.

1. 1. electrode device; Barrel, 2a. Through hole, 2b. Outer wall, 2d. Private room, 2e. 2. gap, Shaft, 3a. Peripheral surface, 3b. Outer cylinder, 3c. Shaft, 3d. Tapered surface, 3e. Feather, 3f. Arrow, 3g. Arrow, 4. 4. Metal infeed section, Liquid feeding section, 5a. Arrow, 6; Drive shaft, 6a. Gears, 6b. Gears, 7. Sliding part, 8. Cathode, 10. Metal foil, 10a. Metal film, 11. Electrolyte solution, 11a. Liquid surface, 11b. Liquid level, 11c. Liquid level, 12. Drum, 12a. Peripheral surface, 12b. Rotation axis, 13. Sealed container, 14. Circulating device, 15. Storage tank, 16. Agitator, 17. Wiper, 18. Arrow, 19. Arrows, 20a-20f. Arrow, M.M. Metal, S.M. contact

Claims (8)

An electrode device used by being immersed in a conductive liquid,
A barrel having an outer wall having a plurality of through holes, capable of storing a metal soluble in the liquid during energization, a shaft having a peripheral surface passing through the barrel and energized, and the interior of the barrel A metal feeding section for feeding the metal into
The electrode device, wherein the shaft rotates relative to the barrel. The shaft includes a plurality of blades that stand from the peripheral surface toward the outer wall of the barrel and have a gap with respect to the outer wall;
The electrode device according to claim 1, wherein the inside of the barrel is divided into a plurality of individual chambers with respect to a circumferential direction of the shaft by the plurality of blades of the shaft.   The electrode device according to claim 1, wherein the metal has a spherical shape.   The electrode device according to any one of claims 1 to 3, wherein the shaft includes an outer cylinder including the peripheral surface and a shaft body on which the outer cylinder is mounted.   The electrode device according to claim 4, wherein the outer cylinder is attached to the shaft body by a taper structure. The electrode device according to any one of claims 1 to 5, wherein a metal that is soluble in the liquid is stored in a conductive liquid during energization, and a drum circumference that is different from the electrode device. Immerse part of the surface,
While rotating the shaft of the electrode device and energizing between the peripheral surface of the drum and the peripheral surface of the shaft of the electrode device while rotating the drum in one direction,
A method for producing a metal foil, wherein a metal film containing the metal component is electrodeposited on a peripheral surface of the drum, and the metal film is formed by peeling the metal film from the peripheral surface of the drum.   The manufacturing method of the metal foil of Claim 6 including the process of sending in the said metal inside the barrel of the said electrode apparatus during the said electricity supply.   The said metal contains 97 mass% or more of aluminum, The manufacturing method of the metal foil of Claim 6 or 7.