JP2014001460A - Apparatus and method for manufacturing electrolytic aluminum foil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for manufacturing an electrolytic aluminum foil, which prevents the aluminum foil from having uneven thickness due to drops of dew condensation products of alkyl sulfone in the apparatus.SOLUTION: In an apparatus for manufacturing an electrolytic aluminum foil, aluminum to be a foil is deposited on the surface of a cathode drum 1c while turning the cathode drum. The apparatus includes: a plating bath 1b for storing plating liquid in which the cathode drum and an anode plate 1d are soaked; a lid part 1a arranged on the plating bath so as to cover the upper part of the plating liquid; and a gas supply port 1g arranged in the lid part so that inert gas can be supplied. When depositing the aluminum foil, inert gas between the plating liquid and the lid part is kept at a temperature of 110°C or higher.

Description

  The present invention relates to an electrolytic aluminum foil manufacturing apparatus. More specifically, an apparatus for producing an aluminum foil by an electrolytic method that can be used for a positive electrode current collector of an electricity storage device in a lithium ion secondary battery or a super capacitor (such as an electric double layer capacitor, a redox capacitor, or a lithium ion capacitor), and And an electrolytic aluminum foil manufacturing method.

  It is a well-known fact that lithium-ion secondary batteries that have a large energy density and do not have a significant decrease in discharge capacity are used for the power supply of mobile tools such as mobile phones and laptop computers. With the miniaturization of mobile tools, further miniaturization is required for the lithium ion secondary batteries attached thereto. In addition, from the viewpoint of measures to prevent global warming, new applications of supercapacitors with high energy density, such as electric double layer capacitors and redox capacitors, will be developed with the development of technologies such as hybrid vehicles and solar power generation. Accelerating, and further higher energy density is required.

An electricity storage device such as a lithium ion secondary battery or a supercapacitor has, for example, a positive electrode and a negative electrode in an organic electrolyte containing a fluorine-containing compound such as LiPF ₆ or NR ₄ .BF ₄ (R is an alkyl group) as an electrolyte. It consists of a structure arranged via a separator made of polyolefin or the like. The positive electrode is composed of a positive electrode active material such as LiCoO ₂ (lithium cobaltate) and activated carbon, and a positive electrode current collector, and the negative electrode is composed of a negative electrode active material such as graphite and activated carbon, and a negative electrode current collector. In general, an active material is applied to the surface of a current collector and formed into a sheet shape. In addition to applying a large voltage to each electrode, it is highly corrosive and is immersed in an organic electrolyte containing a fluorine-containing compound, so the material of the positive electrode current collector is particularly excellent in electrical conductivity, It is required to have excellent corrosion resistance. For these reasons, aluminum is currently used as the material for the positive electrode current collector, which has an electrical conductivity of almost 100% and has a passive film formed on the surface and excellent corrosion resistance. (Copper and nickel are used as the material for the negative electrode current collector).

  As one of means for reducing the size and increasing the energy density of an electricity storage device, there is a method of thinning a current collector constituting an electrode molded into a sheet shape. At present, an aluminum foil having a thickness of about 15 to 20 μm manufactured by a rolling method is generally used for the positive electrode current collector. By reducing the thickness of the aluminum foil, the above object can be achieved. Can be achieved. However, in the rolling method, it is difficult to make the aluminum foil thinner on an industrial production scale.

Therefore, as an aluminum foil manufacturing method that replaces the rolling method, a method of manufacturing an aluminum foil by an electrolytic method is conceivable. Patent Document 1 includes (1) dialkyl sulfone (2) aluminum halide, and (3) ammonium halide, hydrogen halide salt of primary amine, hydrogen halide salt of secondary amine, halogen of tertiary amine Hydride salt, represented by the general formula: R ¹ R ² R ³ R ⁴ N · X (R ^{1 to} R ⁴ are the same or different and are alkyl groups, X represents a counter anion for a quaternary ammonium cation), Forming an aluminum film on the surface of the substrate by an electrolytic method using a plating solution containing at least one nitrogen-containing compound selected from the group consisting of tetraammonium salts, and then peeling the film from the substrate A featured aluminum foil manufacturing method is disclosed. In paragraph 0016 of Patent Document 1, it is described that Patent Document 2 can be used to continuously form and peel an aluminum film using a cathode drum.

  Patent Document 3 discloses a method for producing an aluminum plating film, in which an object to be plated is immersed and energized in a plating bath in which an aluminum halide is dissolved in alkylsulfone. FIG. 1 of Patent Document 3 shows an outline of the plating apparatus. A plating vessel is used so that the plating solution does not take in moisture in the atmosphere, and the plating solution is heated while flowing dry nitrogen. An apparatus for plating is described.

International Publication 2011/001932 Pamphlet JP 06-093490 A JP 2008-031551 A

  With reference to the above prior art, the present applicant examined the continuous formation and peeling of an aluminum film using a plating solution in which an aluminum halide is dissolved in an alkylsulfone and a cathode drum. FIG. 5 is a schematic view of an electrolytic aluminum foil manufacturing apparatus 5 devised based on the prior art.

  The apparatus 5 stores the plating solution L in the plating tank 5B having the lid 5A, and the cathode drum 5C partially immersed in the plating solution L, and the entire surface immersed in the plating solution L facing the cathode drum 5C. By energizing between the anode plate 5D thus formed, an aluminum plating film to be an aluminum foil F is formed on the cathode drum 5C. The aluminum foil F is continuously formed on the rotating cathode drum 5C, then peeled off from the surface of the cathode drum 5C, guided to the guide roll 5E, and formed in the gap between the lid 5A and the plating tank 5B. From the outlet 5F, it is pulled out in the direction of the arrow outside the device 5. The lid 5A above the plating solution L is provided with a gas supply port 5G. By introducing dry nitrogen G ′ into the apparatus 5 from the gas supply port 5G, deterioration of the plating solution L is prevented. Then, the plating solution L is heated to the optimum plating solution temperature for the heater 5I connected to the heater power source 5H. In FIG. 5, the illustration of the power source for applying a voltage between the cathode drum 5C and the anode plate 5D, the circulation / filtration mechanism for the plating solution L, and the like is omitted.

  The present applicant confirmed that the aluminum foil F was produced by the apparatus 5, and it was found that the aluminum foil F having a locally non-uniform thickness is produced in the configuration of the apparatus 5. Such a phenomenon is caused by heating the plating solution L in the apparatus 5 and evaporating the alkyl sulfone, which is a solvent of the plating solution L, to form a dew condensation A inside the lid 5A. This is caused by dropping on the surface of the drum 5C. That is, since the condensed matter A contains almost no aluminum halide or other additive as a solute of the plating solution L, if the condensed matter A falls on the cathode drum 5C or on the cathode drum 5C, the aluminum foil The solute concentration of the plating solution L related to the formation of F is locally reduced, and the thickness of aluminum formed on the surface of the cathode drum 5C is locally reduced.

  SUMMARY OF THE INVENTION The present invention solves the above-described problems, and prevents an aluminum foil thickness non-uniformity from occurring due to the fall of condensed alkylsulfone in the apparatus, and an electrolytic aluminum foil manufacturing apparatus and electrolytic aluminum A foil manufacturing method is provided.

  In the present invention, a cathode drum and an anode plate are arranged to face each other through an electrolytic aluminum plating solution in which at least an aluminum halide is dissolved in alkylsulfone, and the cathode drum is rotated by connecting a power source between both electrodes and energizing. In the electrolytic aluminum foil manufacturing apparatus for depositing aluminum serving as a foil on the surface of the cathode drum, the plating tank storing the plating solution in which the cathode drum and the anode plate are immersed is covered with the plating solution. A lid provided on the plating tank; and a gas supply port arranged to be able to supply an inert gas to the lid; and when depositing the aluminum foil, The inert gas between the lids is kept at 110 ° C. or higher.

The electrolytic aluminum foil manufacturing apparatus of the present invention is preferably supplied with the inert gas heated from the gas supply port.
Moreover, the electrolytic aluminum foil manufacturing apparatus of this invention can be set as the structure provided with the heating mechanism which can heat the said inert gas through the said cover part or the said plating tank.
Further, a plurality of the gas supply ports may be opened in the axial direction of the cathode drum, or may be elongated in the axial direction of the cathode drum.
Further, the gas supply port may be a nozzle capable of ejecting the inert gas in one direction.
The nozzle may be arranged to be able to eject the inert gas in the cathode drum direction.

  In the present invention, the cathode drum and the anode plate are arranged to face each other through an electrolytic aluminum plating solution in which at least an aluminum halide is dissolved in alkylsulfone, and the cathode drum is rotated by connecting the electrodes to a power source and energizing the cathode drum. In the electrolytic aluminum foil manufacturing method of depositing aluminum as a foil on the surface of the cathode drum, the plating tank storing the plating solution in which the cathode drum and the anode plate are immersed is covered with the plating bath. And using a manufacturing apparatus having a lid portion arranged on the plating tank and a gas supply port arranged to be able to supply an inert gas to the lid portion, the plating solution and the lid portion The aluminum foil is deposited while keeping the inert gas at 110 ° C. or higher.

It is preferable to supply the inert gas while maintaining the plating solution at 100 ° C to 110 ° C.
As the plating solution, one containing (1) dialkyl sulfone, (2) aluminum halide, and (3) nitrogen-containing compound can be used.
The nitrogen-containing compound includes ammonium halide, hydrogen halide salt of primary amine, hydrogen halide salt of secondary amine, hydrogen halide salt of tertiary amine, general formula: R ¹ R ² R ³ R ⁴ N · At least one selected from the group consisting of quaternary ammonium salts represented by X (R ^{1 to} R ⁴ are the same or different alkyl groups, X is a counter anion for a quaternary ammonium cation) can be used.

  In the electrolytic aluminum foil manufacturing apparatus of the present invention, since the heated inert gas is introduced into the apparatus, the alkylsulfone as the solvent evaporates from the plating solution, and it is difficult to form dew condensation in the apparatus. In addition, the preferable aspect and the effect of the said electrolytic aluminum foil manufacturing apparatus are demonstrated in detail below.

It is a perspective view which shows schematic structure of the electrolytic aluminum foil manufacturing apparatus of the 1st embodiment of this invention. It is sectional drawing seen from the cathode drum axial direction of the apparatus of FIG. It is a figure which shows the example of the ceiling part which can employ | adopt the apparatus of FIG. It is a figure which shows the example of the nozzle which can employ | adopt the apparatus of FIG. It is a figure explaining the problem of a prior art.

  Embodiments of an electrolytic aluminum foil production apparatus according to the present invention will be described below with reference to the drawings.

  A schematic configuration of the electrolytic aluminum foil manufacturing apparatus is shown in a perspective view of FIG. 1 and a cross-sectional view of FIG. An electrolytic aluminum foil manufacturing apparatus 1 (hereinafter may be abbreviated as apparatus 1) includes a lid 1A, a plating tank 1B, a cathode drum 1C, an anode plate 1D, a gas supply port 1G, a ceiling 1K, and a DC power supply (not shown). As a preferable configuration, a guide roll 1E, a heater power source 1H, a heater 1I, a plating solution circulation device 1J, a stirring flow guide 1M, and a stirring blade 1N are provided. In FIG. 1, illustration of the heater power source 1H, the heater 1I, and the plating solution circulating apparatus 1J in FIG. 2 is omitted.

  With respect to the electrolytic aluminum foil manufacturing apparatus 1 shown in FIGS. 1 and 2, details of components constituting the apparatus and details of an aluminum foil manufacturing process using the apparatus will be described below. The pre-process of the process will be described later together with the operation procedure of the apparatus.

  In the apparatus 1, a plating solution L is stored in a plating tank 1B having a lid 1A, and a part of the cathode drum 1C immersed in the plating solution L is disposed opposite to the surface of the cathode drum 1C. The anode plate 1D immersed in the plating solution L is connected to a DC power source (not shown) and energized to rotate the cathode drum 1C in the direction of the arrow, while the aluminum plating serving as the aluminum foil F on the cathode drum 1C. A film is deposited. During energization, the plating solution L is stirred by the rotation of the stirring blade 1N, and the flow of the plating solution L is generated between the cathode drum 1C and the anode plate 1D by the stirring flow guide 1M. The aluminum plating film to be the aluminum foil F is continuously formed on the surface of the rotating cathode drum 1C, then peeled off from the surface of the cathode drum 1C, guided to the guide roll 1E, and a lid formed on the side surface of the apparatus 1 It is pulled out in the direction of the arrow outside the apparatus 1 from a foil drawing port 1F formed in the gap between 1A and the plating tank 1B. Above the plating solution L, a ceiling portion 1K having a substantially cylindrical inner surface is provided so as to cover the upper portion of the cathode drum 1C at a predetermined distance from the cathode drum 1C. Even if it evaporates and dew condensation occurs, the dew condensation does not fall in the vicinity of the cathode drum 1C or on the cathode drum 1C. A preferable interval between the cathode drum 1C and the ceiling 1K is about 100 to 200 mm when the diameter of the cathode drum 1C is about 150 mm. A dry heated inert gas G is introduced from a gas supply port 1G provided in the ceiling portion 1K so as to prevent deterioration of the plating solution L and condensation of alkylsulfone. The introduced gas is discharged from the foil outlet 1F as will be described later. The plating solution L is heated by the heater 1I connected to the heater power source 1H, and is circulated and filtered by the plating solution circulation device 1J.

As the plating solution L, a plating solution in which an aluminum halide is dissolved in an alkylsulfone solvent as disclosed in Patent Document 3 can be used. Here, as the alkylsulfone, a dialkylsulfone as disclosed in Patent Document 1 may be used, and specifically, dimethylsulfone or the like may be used. As the aluminum halide, specifically, ammonium chloride or the like can be used. Further, as other additives, ammonium halide, hydrogen halide salt of primary amine, hydrogen halide salt of secondary amine, hydrogen halide salt of tertiary amine, general formula: R ¹ R ² R ³ R ⁴ Add at least one nitrogen-containing compound selected from the group consisting of quaternary ammonium salts represented by N · X (R ^{1 to} R ⁴ are the same or different alkyl groups, X is a counter anion for a quaternary ammonium cation) You can also The plating solution L is a solid material at room temperature, and is heated to a high temperature of 60 to 140 ° C. by the heater I and used for the production of the aluminum foil F in a liquid state.

  The lid 1A is disposed on the plating tank 1B in order to prevent evaporation of the solvent alkylsulfone from the plating solution L, and at the same time, has an effect of keeping the inside of the apparatus 1 warm. The part where the lid 1A and the plating tank 1B open to the outside is only the part for introducing the heated inert gas G and the foil outlet 1F, and the heated inert gas G is introduced into the apparatus 1 and discharged from the foil outlet 1F. By continuing to do so, the inside of the apparatus 1 can always be kept at a high temperature of 110 ° C. or higher.

  In the apparatus 1, the inside of the apparatus 1 is heated to 110 ° C. or more by heating the plating solution L by the heater 1I. However, the heating in the apparatus 1 is not necessarily related to this method. For example, a heating mechanism such as a rubber heater may be disposed around the lid 1A and the plating tank 1B, and the inside of the apparatus 1 may be heated via the lid 1A and the plating tank 1B.

  The ceiling portion 1K is provided in the shape of a substantially cylindrical inner surface above the plating solution L so as to cover the upper portion of the cathode drum 1C at a predetermined distance from the cathode drum 1C. As will be described later, a dry heated inert gas G is introduced into the apparatus 1, and a dry high-temperature atmosphere is formed between the plating solution L and the cathode drum 1C and the ceiling portion 1K. As a result, the cathode drum 1C and the ceiling portion 1K are heated and are not easily dewed. By providing the ceiling portion 1K having such a shape, the alkylsulfone as a solvent evaporates from the plating solution L and the ceiling is temporarily removed. Even if the dew condensation occurs on the surface of the portion 1K, the dew condensate travels along the inner surface of the ceiling portion 1K curved in the shape of the inner circumferential surface of the cylinder and falls to the plating solution L at a distance from the cathode drum 1C. That is, since the condensation of alkyl sulfone can be prevented from falling onto the plating solution L near the surface of the cathode drum 1C and in the vicinity of the cathode drum 1C, it is a very effective structure for manufacturing the aluminum foil F having a uniform thickness. .

  In the apparatus 1, the ceiling 1 </ b> K is disposed inside the lid 1 </ b> A. However, the ceiling 1 </ b> A is also provided with a thickness so that the inside is formed into a cylindrical inner peripheral surface, thereby serving as the lid 1 </ b> A. It can also be 1K. In this case, if the heater is disposed inside the lid portion 1A having a thickness to heat the ceiling portion 1K, the alkylsulfone is less likely to condense on the ceiling portion 1K, and the ceiling portion 1K that is preferable for preventing condensation can be obtained. .

  Further, the surface of the ceiling portion 1K is made smooth so that even if alkylsulfone forms a dew condensation, it quickly flows on the surface of the ceiling portion having a cylindrical inner peripheral surface and falls to the plating solution L. Is preferred. Moreover, you may give a groove process to the direction where the dew condensation on the surface of the ceiling part 1K flows so that a dew condensation may flow easily.

  Furthermore, the ceiling portion 1K does not necessarily have the shape of a cylindrical inner peripheral surface as shown in FIG. 2, for example, as shown in FIG. The ceiling portion 1K ′ having an inclined surface structure in which dew condensation flows down in two directions may be used, or as shown in FIG. 3B, the ceiling portion 1K ′ having an inclined surface structure in which dew condensation flows down in one direction. It may be '. In any case, the condensate formed on the surface of the ceiling portion 1K ′ (1K ″) so that the inclined surface is lowered toward the outer peripheral direction of the lid portion 1B, that is, in the direction away from the cathode drum 1C. Preferably flows and falls away from the cathode drum 1C. Since the space between the cylindrical inner peripheral ceiling 1K shown in FIG. 2 and the cathode drum 1C can be narrowed, the heated inert gas G introduced from the gas supply port 1G has a smooth flow. Since the cathode drum 1C is heated by the heat of the gas and the effect of keeping the inside of the apparatus 1 warm is increased, it can be said that the ceiling portion is more preferable.

  In addition, the said structure which concerns on the shape of a ceiling part which is effective in prevention of fall of a dew condensation thing is widely applicable to a plating apparatus irrespective of the presence or absence and form of the structure which concerns on introduction | transduction of a heating inert gas.

  The cathode drum 1C is a cathode drum having a cylindrical shape similar to that used in a general electrolytic copper foil manufacturing apparatus. Aluminum is continuously deposited on the outer peripheral surface of the cylinder, and the aluminum is deposited on the cathode drum. The aluminum foil F is obtained by peeling from the surface of 1C. For the outer peripheral surface of the cylindrical cathode drum 1C, it is preferable to use a material that is easily energized and from which the deposited aluminum is easily peeled off. For example, titanium is preferably used. Further, the surface of the cathode drum 1C is preferably a smooth surface in order to make the thickness of the aluminum foil F uniform, but in order to produce the aluminum foil F having a large specific surface area, for example, the surface has a number of dimples. Fine irregularities on the order of μm may be provided. Furthermore, a heating mechanism such as a heater may be provided in the cathode drum 1C in order to prevent heat from escaping through the cathode drum 1C and the temperature of the cathode drum 1C or the plating solution L from falling. The cathode drum 1C is attached to the apparatus 1 so as to be connected to a driving unit (not shown) (for example, a stepping motor) provided in the axial direction of the drum so as to be rotated at a speed of about 0.1 ° to 5 ° per minute. It is done.

  The anode plate 1D is obtained by processing a pure aluminum plate into a curved surface in accordance with the curvature of the surface of the cathode drum 1C, and the surface of the anode plate 1D is disposed so as to face the surface of the cathode drum 1C at substantially equal intervals. Yes. Such a shape and arrangement can make the current density between the cathode drum 1C and the anode plate 1D uniform, and is preferable for obtaining a uniform aluminum foil F. The cathode drum 1C and the anode plate 1D are connected to a DC power source (not shown) and energized. Except for the surface of the anode plate 1D, the metal portion that is in the same potential as the anode plate 1D and contacts the plating solution L is electrically It will be in a state where it is easily eroded by the plating solution L chemically. Therefore, it is preferable to protect the metal surface with a fluorine-based resin coating or the like.

  In the apparatus 1, the flow of the plating solution L is generated between the cathode drum 1 </ b> C and the anode plate 1 </ b> D by rotating the stirring blade 1 </ b> N, stirring the plating solution L, and rectifying by the stirring flow guide 1 </ b> M. The stirring of the plating solution L is not necessarily limited to this. For example, in the apparatus 1, the plating solution L is circulated and filtered by the plating solution circulation device 1J. The flow of the plating solution L flowing out from the plating solution circulation device 1J is directly between the cathode drum 1C and the anode plate 1D. It is also possible to form a flow of the plating solution L. Forming a flow of the plating solution L between the cathode drum 1C and the anode plate 1D is important for depositing homogeneous aluminum on the surface of the cathode drum 1C.

  The gas supply port 1G is a gas introduction port for introducing the heated inert gas G dried into the apparatus 1 from the outside. When the ceiling portion 1K is provided on the inner surface of the lid portion 1A like the device 1 separately from the lid portion 1A, the gas supply port 1G is opened on the wall surface of the lid portion 1A, and the lid portion 1A and the ceiling portion are opened. It is also possible to introduce a heated inert gas G between 1K and let the gas flow out from the gap between the lid 1A and the ceiling 1K and supply it to the inside of the apparatus 1, but the cathode drum 1C and the ceiling 1K Since the gas flow smoothly circulates along the cathode drum 1C when the heating inert gas G is passed between them, the effect of keeping the inside of the apparatus 1 warm by heating the cathode drum 1C by the heat of the gas is enhanced. . Therefore, the gas supply port 1G is preferably opened from the side surface of the lid 1A to the ceiling 1K.

  Further, the gas supply port 1G can be provided at a certain point of the ceiling 1K, for example, as a circular opening, but a plurality of openings along the axial direction of the cylindrical cathode drum 1C. It is preferable to provide a gas supply port 1G having an elongated slit shape as shown in FIG. With this configuration, the heated inert gas G introduced from the gas supply port 1G can be circulated more smoothly along the surface of the cathode drum 1C, so that the temperature distribution of the inert gas in the apparatus 1 is more uniform. And the effect of further preventing the condensation of the alkyl sulfone can be obtained.

  Furthermore, the portion of the ceiling 1K where the gas supply port 1G is opened tends to cause condensation of the alkylsulfone evaporated from the plating solution L, increasing the risk of condensation falling on the plating solution L or the cathode drum 1C. In order to avoid this, a heating mechanism such as a heater may be provided in the vicinity of the gas supply port 1G so that the alkylsulfone is less likely to condense in the vicinity of the gas supply port 1G.

  The gas supply port 1G may have a nozzle shape that allows the heated inert gas G to be ejected in one direction. In this case, the heated inert gas G may be ejected in the direction of the cathode drum 1C as shown in FIG. 4A, or the direction along the cylindrical inner peripheral surface of the ceiling 1K as shown in FIG. 4B. May be ejected. As shown in FIG. 4A, when the heated inert gas G is ejected from the nozzle 1P substantially perpendicularly in the direction of the cathode drum 1C, the air flow of the heated inert gas that collides with the cathode drum 1C is the surface of the cathode drum 1C. Therefore, even if the condensation of alkyl sulfone falls on the cathode drum 1C, it is blown off and hardly adheres. Note that the ejection angle can be changed as appropriate in addition to the vertical, in view of the degree of condensation. Further, as shown in FIG. 4B, when the heated inert gas G is ejected from the nozzle 1P along the cylindrical inner peripheral surface of the ceiling 1K, the condensation of alkyl sulfone adhering to the ceiling 1K is cylindrical. Since it becomes easy to flow down along the inner surface of the ceiling portion 1K having the inner peripheral surface, an effect of preventing the liquid from falling onto the plating solution L on the cathode drum 1C or in the vicinity of the cathode drum 1C is obtained. 4B shows a nozzle 1P-shaped gas supply port 1G that ejects the heating inert gas G downward along the inner surface of the ceiling portion 1K. At the same time, the gas supply port 1G is heated downward along the inner surface of the ceiling portion 1K. If the nozzle-shaped gas supply port 1G for injecting the inert gas G is also provided so that the heated inert gas G flows along the entire inner surface of the ceiling portion 1K, the dew condensation is caused to flow down on the entire inner surface of the ceiling portion 1K. Since an effect is acquired, it becomes much more preferable for the condensation prevention of alkyl sulfone.

  The heating inert gas G may be any inert gas that can prevent the plating solution from being oxidized, and argon gas or nitrogen gas can be used. Further, since the plating solution L has a characteristic that it easily deteriorates even when it absorbs moisture, it is necessary to use an inert gas that has been dried after removing moisture. The heated inert gas G is a gas heated to about 110 to 140 ° C., which is equal to or higher than the temperature of the plating solution L, in order to prevent the alkyl sulfone from condensing on the inner surface of the ceiling 1K. It is preferable to use it. Here, the temperature and flow rate of the heated inert gas G to be introduced are adjusted while monitoring the atmospheric temperature so that the atmospheric temperature in the apparatus 1 is maintained at the same level or higher as the temperature of the plating solution L. Is preferred.

  The operation of the electrolytic aluminum foil manufacturing apparatus 1 will be described. First, as a pre-process, the bath of the plating solution L will be described. A solid alkylsulfone, an aluminum halide, and an ammonium halide weighed in an appropriate amount in a plating tank 1B that has been confirmed to be free of moisture such as water droplets. Add additives such as. Thereafter, the lid 1A is closed, and a dry inert gas is introduced from the gas supply port 1G without allowing the heater power supply 1H to be switched on and left for several hours. At this time, the inert gas does not need to be heated. This operation is to remove moisture adhering to the drug surface and the apparatus. Aluminum halides easily absorb moisture, and when moisture is taken into the plating solution L, hydrogen may be generated by energization. In order to avoid the danger of hydrogen explosion, the introduction of such inert gas should be done.

  Thereafter, the heater power source 1H is turned on, the inert gas introduced from the gas supply port 1G is heated to form the heated inert gas G, and the solid chemical that becomes the plating solution L is dissolved. If it can be confirmed that the chemical has dissolved into the plating solution L, the stirring blade 1N is rotated to agitate the plating solution L, and the plating solution circulation device 1J is operated to start circulation / filtration of the plating solution. Here, the temperature control of the plating solution L is important so that the plating solution L in a liquid state does not boil. For example, when dimethyl sulfone is used as the alkyl sulfone, the plating solution will boil at about 120 ° C., so it is necessary to adjust the output of the heater power supply 1H and maintain the temperature of the plating solution L at 100 ° C. to 110 ° C. There is. In this case, the temperature of the heated inert gas G is preferably set to 110 ° C. to 115 ° C., which is the same as or slightly higher than the temperature of the plating solution L. In order to bathe the plating solution L, it is preferable that the plating solution L be circulated and stirred for 30 minutes to 1 hour at a minimum.

  After completion of the bathing, while the cathode drum 1C is rotated, electricity is passed between the cathode drum 1C and the anode plate 1D to deposit aluminum on the outer peripheral surface of the cathode drum 1C. After separating the deposited aluminum end from the outer peripheral surface of the cathode drum 1C, the aluminum foil F is obtained by pulling it out of the apparatus 1 from the foil outlet 1F through the guide roll 1E. The number of revolutions of the cathode drum 1C and the plating current density can be arbitrarily set according to the thickness and quality of the aluminum foil F.

DESCRIPTION OF SYMBOLS 1,5: Electrolytic aluminum manufacturing apparatus 1A, 5A: Cover part 1B, 5B: Plating tank 1C, 5C: Cathode drum 1D, 5D: Anode plate 1E, 5E: Guide roll 1F, 5F: Foil extraction port 1G, 5G: Gas Supply port 1H, 5H: Heater power supply 1I, 5I: Heater 1J: Plating solution circulation device 1K: Ceiling part 1M: Stirring flow guide 1N: Stirring blade 1P: Nozzle A: Condensate F: Aluminum foil G: Heating inert gas L : Plating solution

Claims (10)

The cathode drum and the anode plate are arranged to face each other through an electrolytic aluminum plating solution in which at least an aluminum halide is dissolved in an alkylsulfone, and the cathode drum is rotated while the cathode drum is rotated while the cathode drum is rotated. In an electrolytic aluminum foil manufacturing apparatus for depositing aluminum as a foil on the surface,
A plating tank for storing the plating solution in which the cathode drum and the anode plate are immersed, a lid part disposed on the plating tank so as to cover the upper part of the plating solution, and an inert gas in the lid part A gas supply port arranged to be able to supply
And when depositing the said aluminum foil, the inert gas between the said plating solution and the said cover part is maintained at 110 degreeC or more, The electrolytic aluminum foil manufacturing apparatus characterized by the above-mentioned.   The apparatus for producing electrolytic aluminum foil according to claim 1, wherein the heated inert gas is supplied from the gas supply port.   The electrolytic aluminum foil manufacturing apparatus according to claim 1, further comprising a heating mechanism capable of heating the inert gas via the lid or the plating tank.   4. The gas supply port according to claim 1, wherein a plurality of the gas supply ports are opened in the axial direction of the cathode drum, or are elongated and opened in a slit shape in the axial direction of the cathode drum. The electrolytic aluminum foil manufacturing apparatus described in 1.   The apparatus for producing electrolytic aluminum foil according to any one of claims 1 to 4, wherein the gas supply port is a nozzle capable of ejecting the inert gas in one direction.   6. The electrolytic aluminum foil manufacturing apparatus according to claim 5, wherein the nozzle is disposed so as to be able to eject the inert gas in the cathode drum direction. The cathode drum and the anode plate are arranged to face each other through an electrolytic aluminum plating solution in which at least an aluminum halide is dissolved in an alkylsulfone, and the cathode drum is rotated while the cathode drum is rotated while the cathode drum is rotated. In the electrolytic aluminum foil manufacturing method of depositing aluminum to be a foil on the surface,
A plating tank for storing the plating solution in which the cathode drum and the anode plate are immersed, a lid part disposed on the plating tank so as to cover the upper part of the plating solution, and an inert gas in the lid part Using a manufacturing apparatus having a gas supply port arranged to be able to supply
The method for producing an electrolytic aluminum foil, comprising depositing the aluminum foil while maintaining the inert gas between the plating solution and the lid at 110 ° C or higher.   The method for producing an electrolytic aluminum foil according to claim 7, wherein the inert gas is supplied in a state where the plating solution is maintained at 100C to 110C.   The method for producing an electrolytic aluminum foil according to claim 7 or 8, wherein the plating solution includes (1) a dialkyl sulfone, (2) an aluminum halide, and (3) a nitrogen-containing compound. The nitrogen-containing compound includes ammonium halide, hydrogen halide salt of primary amine, hydrogen halide salt of secondary amine, hydrogen halide salt of tertiary amine, general formula: R ¹ R ² R ³ R ⁴ N · It is at least one selected from the group consisting of quaternary ammonium salts represented by X (R ^{1 to} R ⁴ are the same or different alkyl groups, X is a counter anion for a quaternary ammonium cation) The method for producing an electrolytic aluminum foil according to claim 9.

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