WO2014045986A1 - アルミニウム膜の製造方法及びアルミニウム箔の製造方法 - Google Patents
アルミニウム膜の製造方法及びアルミニウム箔の製造方法 Download PDFInfo
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- WO2014045986A1 WO2014045986A1 PCT/JP2013/074620 JP2013074620W WO2014045986A1 WO 2014045986 A1 WO2014045986 A1 WO 2014045986A1 JP 2013074620 W JP2013074620 W JP 2013074620W WO 2014045986 A1 WO2014045986 A1 WO 2014045986A1
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- aluminum
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- aluminum film
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- overvoltage
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
Definitions
- the present invention relates to a method for producing an aluminum film and a method for producing an aluminum foil.
- a method for forming an aluminum film on a substrate for example, (i) a vapor deposition method (PVD) represented by a vacuum deposition method, a sputtering method or a laser ablation method, (ii) a paste coating method, (iii) Examples include plating methods.
- PVD vapor deposition method represented by a vacuum deposition method, a sputtering method or a laser ablation method
- a paste coating method for example, (i) a vapor deposition method (PVD) represented by a vacuum deposition method, a sputtering method or a laser ablation method, (ii) a paste coating method, (iii) Examples include plating methods.
- an aluminum layer is formed by irradiating a raw material aluminum with an electron beam to melt and evaporate an aluminum alloy and adhere aluminum to the resin surface of a resin body having communication holes.
- an aluminum layer can be formed by, for example, vaporizing aluminum by irradiating plasma on an aluminum target and attaching aluminum to the resin surface of a resin body having communication holes.
- an aluminum layer can be formed by melting and evaporating an aluminum alloy by laser irradiation and attaching the aluminum alloy to the resin surface of a resin body having communication holes.
- Paste coating method for example, an aluminum paste in which aluminum powder, a binder (binder), and an organic solvent are mixed is used. And after apply
- This sintering may be performed once or divided into a plurality of times. For example, after applying the aluminum paste, it is possible to sinter the aluminum paste at the same time as the thermal decomposition of the resin body by heating at a low temperature to eliminate the organic solvent and then heating in a molten salt state. It is. Further, this sintering is preferably performed in a non-oxidizing atmosphere.
- (Iii) Plating method Plating aluminum in an aqueous solution is practically impossible, so aluminum is applied to the resin surface of the resin body having communication holes by a molten salt electroplating method in which aluminum is plated in molten salt. A layer can be formed. In this case, it is preferable to plate aluminum in a molten salt after conducting a conductive treatment on the resin surface in advance.
- a salt used for molten salt electroplating for example, a salt such as lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), or aluminum chloride (AlCl 3 ) can be used. Moreover, it is good also as a eutectic molten salt by mixing the salt of 2 or more components. The eutectic molten salt is advantageous in that the melting temperature can be lowered. This molten salt needs to contain aluminum ions.
- molten salt electroplating for example, a multi-component salt of AlCl 3 -XCl (X: alkali metal) -MCl x (M is an additive element selected from Cr, Mn, and transition metal elements) is used.
- X alkali metal
- M is an additive element selected from Cr, Mn, and transition metal elements
- Aluminum is plated on the surface of the substrate by melting the salt into a plating solution and immersing the substrate in this to perform electrolytic plating.
- a base material consists of a nonelectroconductive material, as a pretreatment, the base material surface will be subjected to a conductive treatment in advance.
- a conductive metal such as nickel is plated on the resin surface by electroless plating, a conductive metal such as aluminum is coated on the surface of the substrate by vacuum deposition or sputtering, or a conductive material such as carbon.
- a conductive paint containing particles may be applied.
- Patent Document 1 describes a manufacturing method by rolling aluminum foil. Specifically, as shown in FIG. 3, a strip A wound around winding / rewinding reels 1, 2, 3, 4. , B is passed through the work roll 6 of the reversible rolling mill 5 provided with the work roll 6 and the backup roll 7, and an aluminum foil can be manufactured by rolling for two or more passes.
- Aluminum foil has features such as thermal conductivity, moisture resistance, non-breathability, light weight, and light-shielding properties, so it can be used as a packaging material for various items and electrolyzed for its excellent electrical conductivity. It is generally used as a material for positive current collectors of capacitors and lithium ion batteries.
- Patent Document 2 relates to a negative electrode for a lithium secondary battery, but describes that a copper foil is electrolytically plated to provide a protrusion on the surface of the copper foil.
- a method of producing a copper foil by forming a copper plating film on a base material by electrolytic plating and then peeling the plating film from the base material is performed.
- a method of producing a copper foil by forming a copper plating film on a base material by electrolytic plating and then peeling the plating film from the base material is performed.
- copper is electrodeposited on a cathode drum that rotates in an electrolytic cell to which an electrolytic solution is supplied, and the copper foil is peeled off from the cathode drum while rotating the cathode drum, so that copper for printed wiring boards is used.
- a method of manufacturing a foil is described.
- the aluminum foil currently marketed is manufactured by the rolling method.
- the aluminum foil by the rolling method currently marketed is limited to a film thickness of about 15 ⁇ m, and in order to produce an aluminum foil with a film thickness of 5 ⁇ m to 10 ⁇ m using a rolling mill, the number of rolling processes is increased. The cost increases and it is physically impossible.
- an aluminum foil having a rough surface is used as the positive electrode current collector, a large amount of active material can be retained, so that the charge capacity and battery capacity can be further increased.
- the surface of the aluminum foil on the side in contact with the rolling roller is finished as a mirror surface, so that a large amount of active material cannot be retained even if this is used as a positive electrode current collector.
- an aluminum foil having a thin film thickness as much as possible, preferably a film thickness of 10 ⁇ m or less, and having a rough surface is required.
- an aluminum film having a desired surface roughness can be obtained by appropriately managing the plating conditions when the above (iii) plating method is used. If an aluminum film having a desired surface roughness can be formed on a substrate, it is possible to obtain an aluminum foil having a rough surface or a relatively smooth surface by separating the aluminum film from the substrate. I can do it.
- an aluminum foil is not manufactured by an electrolytic plating method, and a manufacturing method that can be obtained by controlling an aluminum film having a desired surface roughness has not been established.
- the surface roughness of the obtained film cannot be controlled to a desired surface roughness simply by forming a film on a substrate by conventional molten salt electrolysis.
- an object of the present invention is to provide a method for producing an aluminum film and a method for producing an aluminum foil such that the surface roughness of the aluminum film becomes a desired surface roughness by electrolytic plating. .
- the inventors of the present invention have made extensive studies on a method of manufacturing an aluminum foil by forming an aluminum film on a base material by a plating method using a molten salt as an electrolytic solution and separating the base material from the aluminum film. Invented.
- the present invention adopts the following configuration in order to solve the above problems.
- an aluminum film having a desired surface roughness can be produced by electrolytic plating.
- the electrolytic solution contains aluminum chloride and alkyl imidazolium chloride, or contains aluminum chloride and alkyl pyridinium chloride, and the alkyl group in the alkyl imidazolium chloride and alkyl pyridinium chloride has 1 to 5 carbon atoms.
- the arithmetic average roughness (Ra) of the surface of the aluminum film is 0.2 ⁇ m to 0.5 ⁇ m, or the ten-point average roughness (Rz) is 1 ⁇ m to 5 ⁇ m (1) to (4) The manufacturing method of the aluminum film of any one of these.
- the aluminum film having the surface roughness obtained by the present invention (5) is used as a positive electrode current collector of a lithium ion battery or the like as an aluminum foil, a large amount of active material can be retained, so that the charge capacity and battery The capacity can be further increased.
- 1,10-phenanthroline is used as the additive, aluminum is used for the reference electrode and counter electrode for overvoltage measurement, platinum is used for the working electrode, and the overvoltage is controlled to 50 mV to 120 mV (5)
- the concentration of the additive added to the molten salt can be controlled to an appropriate concentration.
- the aluminum foil which can be used conveniently as a tab lead for taking out electricity from the inside of a lithium ion battery, an electric double layer capacitor, etc. can be manufactured.
- 1,10-phenanthroline is used as the additive, aluminum is used for the reference electrode and counter electrode for overvoltage measurement, platinum is used for the working electrode, and the overvoltage is controlled to 130 mV to 170 mV (7) Or the manufacturing method of the aluminum film as described in (8).
- the concentration of the additive added to the molten salt can be controlled to an appropriate concentration.
- a method for producing an aluminum foil wherein the aluminum film obtained by the method for producing an aluminum film according to any one of (1) to (9) is separated from a substrate.
- an aluminum foil having a rough surface or an aluminum foil having a mirror surface can be produced.
- the method for producing an aluminum foil according to (10), wherein the thickness of the aluminum foil is 10 ⁇ m or less.
- an aluminum foil suitable for use as a positive electrode current collector of a lithium ion battery can be obtained by an electrolytic plating method.
- an aluminum film and an aluminum foil can be produced by electrolytic plating so that the surface roughness of the aluminum film becomes a desired surface roughness.
- the aluminum film of the present invention can be obtained by electrodepositing aluminum by performing molten salt electrolysis using a molten salt having components adjusted on a substrate.
- an organic molten salt or an inorganic molten salt can be used.
- an organic molten salt which is a eutectic salt of an organic halide and an aluminum halide can be used.
- the organic halide include imidazolium salts and pyridinium salts (such as butylpyridinium chloride (BPC)). Etc. can be used.
- an imidazolium salt is preferable, and a salt containing an imidazolium cation having an alkyl group (having 1 to 5 carbon atoms) at the 1,3-position is preferably used.
- a salt containing an imidazolium cation having an alkyl group (having 1 to 5 carbon atoms) at the 1,3-position is preferably used.
- aluminum chloride-1-ethyl-3-methylimidazolium chloride (AlCl 3 -EMIC) type molten salt is most preferably used because of its high stability and resistance to decomposition and high electrical conductivity.
- the temperature of the molten salt bath is 10 ° C to 100 ° C, preferably 25 ° C to 80 ° C, more preferably 30 ° C to 60 ° C. The higher the temperature, the wider the current density range that can be plated, and by setting it to 100 ° C. or lower, the heating cost is reduced and the decomposition of the molten salt can be suppresse
- an eutectic salt of an alkali metal halide and an aluminum halide (AlCl 3 -XCl (X: alkali metal)) can be used.
- Such an inorganic molten salt generally has a higher melting temperature than an organic salt bath such as an imidazolium salt bath, but is less restricted by environmental conditions such as moisture and oxygen, and can be put into practical use at a low cost overall.
- an additive may be added to the molten salt as described later.
- the inorganic molten salt has a high melting point, it is necessary to increase the temperature of the plating solution.
- the additive volatilizes or decomposes at a high temperature, it is preferable to use an organic molten salt that melts at a low temperature.
- the surface of the aluminum film have a surface roughness such that the arithmetic average roughness (Ra) is 0.2 ⁇ m to 0.5 ⁇ m or the ten-point average roughness (Rz) is 1 ⁇ m to 5 ⁇ m
- an additive such as benzene, xylene, pyridine, pyrazine, benzotriazole, polystyrene, 1,10-phenanthroline to the molten salt.
- the above-mentioned additive is not necessarily required, but the effect that the roughness becomes uniform can be obtained by adding the above-mentioned additive.
- 1,10-phenanthroline is particularly preferably used.
- the surface of the aluminum film is thinned with an arithmetic average roughness (Ra) of 0.2 ⁇ m to 0.5 ⁇ m or a ten-point average roughness (Rz) of 1 ⁇ m to 5 ⁇ m.
- Ra arithmetic average roughness
- Rz ten-point average roughness
- the amount of the additive added to the plating bath is preferably 0.3 g / L or less.
- the additive include benzene, xylene, pyridine, pyrazine, benzotriazole, polystyrene, 1,10-phenanthroline, and the like, which can be appropriately selected depending on the type of the molten salt.
- 1,10-phenanthroline is particularly preferably used.
- the amount of the additive added to the plating bath is preferably 0.3 g / L to 5.0 g / L. Sufficient smoothness is obtained by being 0.3 g / L or more, and sufficient plating efficiency is obtained by being 5.0 g / L or less.
- the concentration of the additive decreases as the plating progresses. Therefore, in order to make the roughness of the plating film surface uniform, it is necessary to maintain the concentration of the additive within a predetermined range. Therefore, it is necessary to monitor the concentration of the additive.
- the overvoltage is measured, and the additive is added to the molten salt so that the overvoltage is within a predetermined range based on the measured value. Monitoring may be performed continuously or at intervals.
- the overvoltage is the absolute value of the potential difference between the theoretical potential (equilibrium electrode potential) at which the aluminum electrodeposition reaction occurs and the electrode potential when the aluminum electrodeposition reaction actually starts. Since the absolute value of the potential difference reflects the concentration of the additive, the concentration of the additive can be controlled by adjusting the amount of additive added so that the overvoltage is within a predetermined range.
- AlCl 3 -EMIC is used as the molten salt
- 1,10-phenanthroline is used as the additive
- aluminum is used for the reference and counter electrodes for overvoltage measurement
- platinum is used for the working electrode.
- the relationship between overvoltage and additive concentration when measuring overvoltage is shown.
- the relationship between overvoltage and additive concentration when a material other than platinum is used for the working electrode is different from the relationship between overvoltage and additive concentration when platinum is used for the working electrode. Therefore, it is necessary to obtain the relationship between the overvoltage and the additive concentration according to the type of material used for the electrode.
- AlCl 3 -EMIC is used as a molten salt
- 1,10-phenanthroline is used as an additive
- aluminum is used as a reference electrode and a counter electrode for overvoltage measurement
- platinum is used as a working electrode
- arithmetic average roughness (Ra) Is 0.2 ⁇ m to 0.5 ⁇ m, or when it is desired to obtain an aluminum film having a surface roughness with a 10-point average roughness (Rz) of 1 ⁇ m to 5 ⁇ m, the overvoltage is 0 mV to 120 mV.
- the additive concentration is preferably used.
- it is more preferably 50 mV to 120 mV.
- the overvoltage is less than 50 mV, the above surface roughness can be obtained.
- AlCl 3 -EMIC is used as a molten salt
- 1,10-phenanthroline is used as an additive
- aluminum is used as a reference electrode and a counter electrode for overvoltage measurement
- platinum is used as a working electrode
- an aluminum film having a mirror surface is used.
- the additive concentration so that the overvoltage is 130 mV or more.
- the overvoltage exceeds 170 mV, the surface of the aluminum film starts to become black. Therefore, it is preferable to set the addition concentration so that the overvoltage value becomes 130 mV to 170 mV.
- FIG. 6 shows the relationship between overvoltage and additive concentration when AlCl 3 -EMIC is used as the molten salt and pyrazine is used as the additive.
- AlCl 3 -EMIC as the molten salt
- pyrazine as the additive
- aluminum as the reference and counter electrodes for overvoltage measurement
- platinum as the working electrode
- a mirror-finished aluminum film it is preferable to set the additive concentration so that the overvoltage value is 140 mV to 180 mV.
- the aluminum film formed on the base material can be made into an aluminum foil by removing the base material. Any material can be used as the substrate as long as it can be separated from the aluminum film in a later step.
- aluminum is selected as the substrate, since aluminum oxide is usually present on the surface of the aluminum, the adhesiveness with the aluminum film is not good, so that the aluminum film is easily peeled off.
- an aluminum foil can be obtained by removing the resin by thermal decomposition after plating.
- nickel is selected as the substrate, an aluminum foil can be obtained by dissolving and removing nickel with concentrated nitric acid.
- the thing of the endless belt form which can manufacture an aluminum foil continuously, or a drum-like thing is preferable.
- FIG. 1 shows an example of a production apparatus used for the method for producing an aluminum foil of the present invention.
- An electrolytic solution containing a molten salt is accommodated in the electrolytic cell 1.
- a cylindrical cathode drum (power supply drum) 2 is rotatably disposed in the electrolytic cell 1, and an electrolysis anode (aluminum plate) 3 is maintained along the cathode drum 2 at a substantially constant distance.
- the electrolytic solution is supplied between the cathode drum 2 and the electrolysis anode 3.
- a voltage is applied between the cathode drum 2 and the electrolysis anode 3 so that aluminum is electrodeposited from the electrolytic solution by the rectifier 11, so that the aluminum is electrodeposited on the surface of the rotating cathode drum 2, and the aluminum film Is formed.
- the drum rotates the aluminum film electrodeposited on the surface of the drum becomes thicker, and the aluminum film having a predetermined film thickness is continuously peeled from the drum to become an aluminum foil 4 and is taken up by a take-up roll 5.
- the aluminum foil 4 when the aluminum foil 4 is thin, it may be laminated with the auxiliary film 7 unwound from the auxiliary film roller 6 and taken up on the take-up roll 5.
- the electrolyte supplied between the cathode drum 2 and the electrolysis anode 3 and having the additive reduced by electrodeposition overflows from the electrolytic cell 1 and continuously returns to the recovered electrolytic cell 21 as shown in FIG. Then, the liquid is supplied to the replenishing liquid storage tank 22.
- An additive storage tank 23 is connected to the recovered electrolyte tank 21, and a supply valve 24 is controlled by a control signal from a control device 25 that sends a control signal based on an overvoltage signal to add a predetermined amount from the additive storage tank 23.
- the agent is supplied to the recovered electrolyte tank 21 to adjust the additive concentration.
- the electrolytic solution is supplied from the replenisher storage tank 22 to the electrolytic tank 1 after removing solids in the liquid by the filter 26.
- a cooling device may be provided to cool the electrolytic solution.
- an aluminum plating layer having a uniform thickness can be formed on the surface of the cathode drum 2.
- a reference electrode, a counter electrode, and a working electrode are provided in the electrolytic cell 1, and an electrochemical measurement device for a three-electrode cell is prepared.
- a voltage is applied to the working electrode with respect to the reference electrode, and a potential at which aluminum starts to be deposited, that is, a potential at which a current starts to flow is measured. What is necessary is just to obtain
- aluminum may be used for the reference electrode and the counter electrode, and platinum, glassy carbon, gold, silver, copper, nickel, etc. may be used for the working electrode.
- the relationship between overvoltage and additive concentration when a material other than platinum is used for the working electrode is different from the relationship between overvoltage and additive concentration when platinum is used for the working electrode. Therefore, it is necessary to obtain the relationship between the overvoltage and the additive concentration according to the type of material used for the electrode.
- the amount of the additive supplied to the replenisher storage tank 22 is controlled by adjusting the opening of the additive supply valve 24.
- electrolysis is performed in an inert gas atmosphere such as nitrogen or argon, and in a sealed environment. It is preferable.
- an inert gas atmosphere such as nitrogen or argon
- a lid 8 is placed on the surface of the plating bath of the electrolytic cell 1 and an inert gas 9 is bubbled from below the electrolytic cell 1 to stir the electrolytic solution and to remove moisture contained in the electrolytic solution.
- the space 10 on the liquid surface of the electrolyte is a nitrogen gas atmosphere.
- a shielding plate may be suspended on the liquid surface of the electrolytic solution to shut out the outside air, or an inert gas may be supplied from above the electrolytic cell 1.
- the temperature of the plating bath it is preferable to perform electroplating while adjusting the temperature of the plating bath to be 10 ° C. to 100 ° C.
- the temperature of the plating bath is more preferably 25 ° C. to 80 ° C., and further preferably 30 ° C. to 60 ° C.
- the material of the cathode drum 2 used in the aluminum plating method of the present invention is not particularly limited, but, for example, aluminum, copper, iron or the like can be preferably used.
- An aluminum foil having a surface roughness with an arithmetic average roughness (Ra) of 0.2 ⁇ m to 0.5 ⁇ m or a ten-point average roughness (Rz) of 1 ⁇ m to 5 ⁇ m is suitable for normal use of an aluminum foil. Besides being used, it can be suitably used as a current collector for lithium ion batteries, electrolytic capacitors, electric double layer capacitors and lithium ion capacitors.
- Mirror surface aluminum foil is suitable for use as a tab lead for taking out electricity from the inside of lithium ion batteries, electrolytic capacitors, electric double layer capacitors and lithium ion capacitors, for example, using aluminum laminate film for the exterior, in addition to the normal use of aluminum foil Can be used for
- the tab lead is welded to the current collector by ultrasonic welding or the like, but since it is preferable that the contact property is good, mirror surface aluminum foil can be used as the tab lead.
- Example 1-1 Using an electrolytic aluminum foil manufacturing apparatus as shown in FIG. 1, an aluminum cathode drum 2 having a diameter of 0.25 m is connected to the cathode side of the rectifier 11, and a counter aluminum plate (purity 99.99%) is connected to the anode side. And then plating under the following electrolysis conditions while bubbling nitrogen from the bottom of the electrolytic cell 1 at a flow rate of 5 L / min. An electrolytic aluminum foil having a thickness of 8 ⁇ m was obtained. Moreover, aluminum was used for the reference electrode and counter electrode for overvoltage measurement, and platinum was used for the working electrode. The electrolysis conditions are as follows.
- Example 1-2 Molten salt composition: 33 mol% EMIC-67 mol% AlCl 3 Additive: None Liquid temperature: 45 ° C Current density: 6 A / dm 2 (DC current) Setting overvoltage: 20mV
- Example 1-2 an aluminum foil was obtained in the same manner as in Example 1-1.
- the surface roughness of the electrolytic aluminum foil of Example 1-2 only the arithmetic average roughness was measured without specifying the measurement position.
- Example 2 Electrolyte composition: 33 mol% EMIC-67 mol% AlCl 3
- Additive 1,10-phenanthroline Liquid temperature: 45 ° C
- Current density 6 A / dm 2 (DC current)
- Setting overvoltage 90 mV to 120 mV
- an aluminum foil was obtained in the same manner as in Example 1-1, except that 1,10-phenanthroline was added as an additive and the additive concentration was set to a set overvoltage of 90 mV to 120 mV or higher. It was. When the surface roughness of the width direction center part and the width direction edge part of the obtained electrolytic aluminum foil was measured, the surface roughness was almost equal in the width direction end part and the width direction center part.
- Example 3-1 Electrolyte composition: 33 mol% EMIC-67 mol% AlCl 3
- Additive 1,10-phenanthroline Liquid temperature: 45 ° C
- Current density 6 A / dm 2 (DC current)
- Setting overvoltage 130 mV
- 1,10-phenanthroline was added as an additive, and an electrolytic aluminum foil was obtained in the same manner as in Example 1-1 except that the additive concentration was set so that the set overvoltage was 120 mV or more. It was.
- the set overvoltage is 130 mV.
- Example 3-2 Molten salt composition: 33 mol% EMIC-67 mol% AlCl 3 Additive: 1,10-phenanthroline Liquid temperature: 45 ° C Current density: 6 A / dm 2 (DC current) Setting overvoltage: 130 mV to 160 mV.
- an aluminum foil was obtained in the same manner as in Example 3-1, except that the additive concentration was set so that the set overvoltage was 130 mV to 160 mV.
- the surface roughness of the electrolytic aluminum foil of Example 3-2 only the arithmetic average roughness was measured without specifying the measurement position.
- Example 4 Electrolyte composition: 33 mol% EMIC-67 mol% AlCl 3 Additive: Pyrazine Liquid temperature: 45 ° C Current density: 6 A / dm 2 (DC current) Setting overvoltage: 140 mV to 180 mV
- an aluminum foil was obtained in the same manner as in Example 1-1, except that pyrazine was added as an additive, and the additive concentration was set to a set overvoltage of 140 mV to 180 mV. For the surface roughness of the electrolytic aluminum foil of Example 4, only the arithmetic average roughness was measured without specifying the measurement position.
- Table 1 shows the surface roughness of the aluminum foil obtained in Examples 1-1 to 4.
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Abstract
Description
真空蒸着法では、例えば、原料のアルミニウムに電子ビームを照射してアルミニウム合金を溶融・蒸発させ、連通孔を有する樹脂体の樹脂表面にアルミニウムを付着させることにより、アルミニウム層を形成することができる。スパッタリング法では、例えば、アルミニウムのターゲットにプラズマ照射してアルミニウムを気化させ、連通孔を有する樹脂体の樹脂表面にアルミニウムを付着させることにより、アルミニウム層を形成することができる。レーザアブレーション法では、例えば、レーザ照射によりアルミニウム合金を溶融・蒸発させ、連通孔を有する樹脂体の樹脂表面にアルミニウム合金を付着させることにより、アルミニウム層を形成することができる。
ペースト塗布法では、例えば、アルミニウム粉末、結着剤(バインダー)、及び有機溶剤を混合したアルミニウムペーストを用いる。そして、アルミニウムペーストを樹脂表面に塗布した後、加熱することにより、バインダーと有機溶剤とを消失させると共に、アルミニウムペーストを焼結させる。この焼結は、1回で行っても、複数回に分けて行ってもよい。例えば、アルミニウムペーストの塗布後、低温で加熱して有機溶剤を消失させた後、溶融塩に浸漬した状態で加熱することにより、樹脂体の熱分解と同時にアルミニウムペーストの焼結を行うことも可能である。また、この焼結は、非酸化性雰囲気化で行うことが好ましい。
水溶液中でアルミニウムをめっきすることは、実用上ほとんど不可能であるため、溶融塩中でアルミニウムをめっきする溶融塩電解めっき法により、連通孔を有する樹脂体の樹脂表面にアルミニウム層を形成することができる。この場合、予め樹脂表面を導電化処理した後、溶融塩中でアルミニウムをめっきすることが好ましい。
(1)溶融塩を含む電解液が供給される電解槽中で、基材上にアルミニウムを電着させてアルミニウム膜を製造する方法であって、
前記電解液におけるアルミニウムが電析する際の過電圧と前記溶融塩へ添加する添加剤の濃度との所定の関係に基づいて、前記過電圧の測定値が所望の範囲内になるように前記添加剤の濃度を調整するアルミニウム膜の製造方法。
上記本発明(1)によれば、電解めっき法によってアルミニウム膜の表面粗さが所望の表面粗さのアルミニウム膜を製造することができる。
(2)前記電解液が塩化アルミニウム及びアルキルイミダゾリウムクロリドを含むか、又は塩化アルミニウム及びアルキルピリジニウムクロリドを含み、前記アルキルイミダゾリウムクロリド及びアルキルピリジニウムクロリドにおけるアルキル基の炭素原子数が1個~5個の範囲にある(1)に記載のアルミニウム膜の製造方法。
上記本発明(2)により陰極基材上に効率的にアルミニウム膜を形成することができる。
(3)前記溶融塩へ添加する前記添加剤としてベンゼン、キシレン、ピリジン、ピラジン、ベンゾトリアゾール、ポリスチレン及び1,10-フェナントロリンよりなる群から選ばれる一種以上を添加する(1)又は(2)に記載のアルミニウム膜の製造方法。上記本発明(3)により陰極基材上に均一な粗さを有するアルミニウム膜を形成することができる。
(4)前記溶融塩が塩化アルミニウム-1-エチル-3-アルキルイミダゾリウムクロリドであり、前記添加剤が1,10-フェナントロリンである(1)から(3)のいずれか1項に記載のアルミニウム膜の製造方法。
上記本発明(4)により陰極基材上により均一な粗さを有するアルミニウム膜を形成することができる。
上記本発明(5)によって得られた表面粗さを有するアルミニウム膜をアルミニウム箔としてリチウムイオン電池等の正極集電体として用いた場合には活物質を多く保持することができるので充電容量、電池容量をより高めることができる。
(6)前記添加剤として1,10-フェナントロリンを用い、過電圧測定用の参照極及び対極にはアルミニウムを用い、作用極には白金を用いて、前記過電圧を50mV~120mVに制御する(5)に記載のアルミニウム膜の製造方法。
上記本発明(6)により溶融塩へ添加する添加剤の濃度を適切な濃度に制御することができる。
上記本発明(7)により、電解法によって鏡面を有するアルミニウム膜を製造することができる。なお、本発明でいう鏡面とは表面粗さ(算術平均粗さ:Ra)が1.0nm~20.0nmである場合をいう。また、本発明(7)では、添加剤は平滑化剤としての役割を有している。
(8)前記アルミニウム膜の厚さが0.5μm以上10μm以下である(7)に記載のアルミニウム膜の製造方法。
上記本発明(8)により、リチウムイオン電池及び電気二重層キャパシタ等の内部から電気を取り出すためのタブリードとして好適に使用できるアルミニウム箔を製造することができる。
(9)前記添加剤として1,10-フェナントロリンを用い、過電圧測定用の参照極及び対極にはアルミニウムを用い、作用極には白金を用いて、前記過電圧を130mV~170mVに制御する(7)又は(8)に記載のアルミニウム膜の製造方法。
上記本発明(9)により溶融塩へ添加する添加剤の濃度を適切な濃度に制御することができる。
上記本発明(10)により粗面を有するアルミニウム箔や鏡面を有するアルミニウム箔を製造することができる。
(11)前記アルミニウム箔の厚さが10μm以下である(10)に記載のアルミニウム箔の製造方法。
上記本発明(11)により、例えばリチウムイオン電池の正極集電体としての使用にも適したアルミニウム箔を、電解めっき法によって得ることができる。
ピリジニウム塩としてはブチルピリジニウムクロライド(BPC)等が使用できる。
但し、本発明では後述するように添加剤を溶融塩に添加する場合があるが、無機溶融塩は融点が高いため、めっき液の液温を高くする必要がある。また、高温では添加剤が揮発する可能性や分解する可能性があるため、低温で溶融する有機溶融塩を用いることが好ましい。
また、膜厚を大きくする場合には、上記の添加剤は必ずしも必要ではないが、上記の添加剤を添加することにより粗さが均一になるという効果が得られる。
溶融塩としてAlCl3-EMICを用いる場合には、特に1,10-フェナントロリンが好ましく用いられる。アルミニウム膜の表面を、算術平均粗さ(Ra)が0.2μm~0.5μmであるか、又は十点平均粗さ(Rz)が1μm~5μmである表面粗さで、膜厚を薄くする場合には、めっき浴への添加剤の添加量は、0.3g/L以下が好ましい。
添加剤としてはベンゼン、キシレン、ピリジン、ピラジン、ベンゾトリアゾール、ポリスチレン、1,10-フェナントロリン等を挙げることができ溶融塩の種類によって適宜選択することができる。
溶融塩としてAlCl3-EMICを用いる場合には、特に1,10-フェナントロリンが好ましく用いられる。アルミニウム膜を鏡面とする場合、めっき浴への添加剤の添加量は、0.3g/L~5.0g/Lが好ましい。0.3g/L以上であることにより十分な平滑性が得られ、また5.0g/L以下であることにより十分なめっき効率が得られる。
このため、添加剤の濃度をモニタリングする必要があるが、本発明では過電圧を測定し、この測定値に基づいて所定の範囲内の過電圧となるように添加剤を溶融塩に添加する。モニタリングは連続的に行なっても良く、また、インターバルを設けて行ってもよい。
そして、電解槽1中には、円筒状の陰極ドラム(給電ドラム)2が回転可能に配置されており、この陰極ドラム2に沿ってほぼ一定の距離を保って電解用陽極(アルミニウム板)3が配置されており、この陰極ドラム2と電解用陽極3との間に電解液が供給される。
過電圧の値が設定範囲外の場合は、添加剤の供給バルブ24の開度を調節して補給液貯槽22への添加剤の供給量を制御する。
図1に示す装置においては、電解槽1のめっき浴表面に蓋8をして電解槽1の下方から不活性ガス9をバブリングすることによって電解液を攪拌すると共に電解液中に含まれる水分や酸素を追い出すとともに、電解液の液面上の空間10を窒素ガス雰囲気としている。このようにすることにより、不活性ガス雰囲気に保つ空間10を狭い範囲とすることができ不活性ガスにかかるコストを下げることができる。
また、蓋8の代わりに電解液の液面に遮蔽板を浮遊させて外気をシャットアウトしてもよく、不活性ガスを電解槽1の上方から供給するようにしても良い。
また、本発明のアルミニウムのめっき方法において使用する陰極ドラム2の材料は特に限定されるものではないが、例えば、アルミニウム、銅、鉄等を好ましく用いることができる。
図1に示すような電解アルミニウム箔製造装置を使用し、アルミニウム製の直径0.25mの陰極ドラム2を整流器11の陰極側に接続し、対極のアルミニウム板(純度99.99%)を陽極側に接続して、電解槽1底部から窒素を5L/minの流量でバブリングさせながら以下の電解条件でめっきを行い、得られたアルミニウムのめっき膜を陰極ドラム2から連続的に剥離して、厚さ8μmの電解アルミニウム箔を得た。また、過電圧測定用の参照極及び対極にはアルミニウムを用い、作用極には白金を用いた。
電解条件は次の通りである。
溶融塩組成 : 33mol%EMIC-67mol%AlCl3
添加剤 : なし
液温 : 45℃
電流密度 : 6A/dm2(直流電流)
設定過電圧 : 20mV
得られた電解アルミニウム箔の幅方向中央部と幅方向端部の表面粗さを測定したところ、幅方向端部に比べ、幅方向中央部の表面粗さが大きくなっていた。
溶融塩組成 : 33mol%EMIC-67mol%AlCl3
添加剤 : なし
液温 : 45℃
電流密度 : 6A/dm2(直流電流)
設定過電圧 : 20mV
実施例1-2では、実施例1-1と同様にしてアルミニウム箔を得た。実施例1-2の電解アルミニウム箔の表面粗さについては、測定位置を特定せずに算術平均粗さのみを測定した。
電解液組成 : 33mol%EMIC-67mol%AlCl3
添加剤 : 1,10-フェナントロリン
液温 : 45℃
電流密度 : 6A/dm2(直流電流)
設定過電圧 : 90mV~120mV
実施例2では、添加剤として1,10-フェナントロリンを添加し、添加剤濃度を設定過電圧が90mV~120mV以上となるようにしたこと以外は、実施例1-1と同様にしてアルミニウム箔を得た。得られた電解アルミニウム箔の幅方向中央部と幅方向端部の表面粗さを測定したところ、幅方向端部、幅方向中央部ともに表面粗さがほぼ同等となっていた
電解液組成 : 33mol%EMIC-67mol%AlCl3
添加剤 : 1,10-フェナントロリン
液温 : 45℃
電流密度 : 6A/dm2(直流電流)
設定過電圧 : 130mV
実施例3-1では、添加剤として1,10-フェナントロリンを添加し、添加剤濃度を設定過電圧が120mV以上となるようにしたこと以外は実施例1-1と同様にして電解アルミニウム箔を得た。ここでは設定過電圧は130mVとしている。
溶融塩組成 : 33mol%EMIC-67mol%AlCl3
添加剤 : 1,10-フェナントロリン
液温 : 45℃
電流密度 : 6A/dm2(直流電流)
設定過電圧 : 130mV~160mV
実施例3-2では、添加剤濃度を設定過電圧が130mV~160mVとなるようにしたこと以外は、実施例3-1と同様にしてアルミニウム箔を得た。実施例3-2の電解アルミニウム箔の表面粗さについては、測定位置を特定せずに算術平均粗さのみを測定した。
電解液組成 : 33mol%EMIC-67mol%AlCl3
添加剤 : ピラジン
液温 : 45℃
電流密度 : 6A/dm2(直流電流)
設定過電圧 : 140mV~180mV
実施例4では、添加剤としてピラジンを添加し、添加剤濃度を設定過電圧が140mV~180mVとなるようにしたこと以外は、実施例1-1と同様にしてアルミニウム箔を得た。実施例4の電解アルミニウム箔の表面粗さについては、測定位置を特定せずに算術平均粗さのみを測定した。
実施例1-1~実施例4において得られたアルミニウム箔の表面粗さを表1に示す。
1 電解槽
2 陰極ドラム
3 電解用陽極
4 アルミニウム箔
5 巻取ロール
6 補助フィルムローラ
7 補助フィルム
8 蓋
9 不活性ガス
10 空間
11 整流器
21 回収電解液槽
22 補給液貯槽
23 添加剤貯槽
24 供給バルブ
25 制御装置
26 濾過機
(図3)
1~4 巻取・巻戻リール
5 リバーシブル圧延機
6 ワークロール
7 バックアップロール
11、12、17、18 デフレクタロール
A、B ストリップ
Claims (11)
- 溶融塩を含む電解液が供給される電解槽中で、基材上にアルミニウムを電着させてアルミニウム膜を製造する方法であって、
前記電解液におけるアルミニウムが電析する際の過電圧と前記溶融塩へ添加する添加剤の濃度との所定の関係に基づいて、前記過電圧の測定値が所望の範囲内になるように前記添加剤の濃度を調整するアルミニウム膜の製造方法。 - 前記電解液が塩化アルミニウム及びアルキルイミダゾリウムクロリドを含むか、又は塩化アルミニウム及びアルキルピリジニウムクロリドを含み、前記アルキルイミダゾリウムクロリド及びアルキルピリジニウムクロリドにおけるアルキル基の炭素原子数が1個~5個の範囲にある請求項1に記載のアルミニウム膜の製造方法。
- 前記溶融塩へ添加する前記添加剤としてベンゼン、キシレン、ピリジン、ピラジン、ベンゾトリアゾール、ポリスチレン及び1,10-フェナントロリンよりなる群から選ばれる少なくとも一種以上を添加する請求項1又は請求項2に記載のアルミニウム膜の製造方法。
- 前記溶融塩が塩化アルミニウム-1-エチル-3-アルキルイミダゾリウムクロリドであり、前記添加剤が1,10-フェナントロリンである請求項1から請求項3のいずれか1項に記載のアルミニウム膜の製造方法。
- 前記アルミニウム膜の表面の算術平均粗さ(Ra)が0.2μm~0.5μmとなるか、又は十点平均粗さ(Rz)が1μm~5μmとなる請求項1から請求項4のいずれか1項に記載のアルミニウム膜の製造方法。
- 前記添加剤として1,10-フェナントロリンを用い、過電圧測定用の参照極及び対極にはアルミニウムを用い、作用極には白金を用いて、前記過電圧を50mV~120mVに制御する請求項5に記載のアルミニウム膜の製造方法。
- 前記溶融塩に前記添加剤が添加されており、前記アルミニウム膜の表面を鏡面とする請求項1から請求項4のいずれか1項に記載のアルミニウム膜の製造方法。
- 前記アルミニウム膜の厚さが0.5μm以上10μm以下である請求項7に記載のアルミニウム箔の製造方法。
- 前記添加剤として1,10-フェナントロリンを用い、過電圧測定用の参照極及び対極にはアルミニウムを用い、作用極には白金を用いて、前記過電圧を130mV~170mVに制御する請求項7又は請求項8に記載のアルミニウム膜の製造方法。
- 請求項1から請求項9のいずれか一項に記載のアルミニウム膜の製造方法によって得られたアルミニウム膜を前記基材から分離させるアルミニウム箔の製造方法。
- 前記アルミニウム箔の厚さが10μm以下である請求項10に記載のアルミニウム箔の製造方法。
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- 2013-09-12 JP JP2014536791A patent/JP6202344B2/ja active Active
- 2013-09-12 WO PCT/JP2013/074620 patent/WO2014045986A1/ja active Application Filing
- 2013-09-12 DE DE112013004539.7T patent/DE112013004539T5/de not_active Withdrawn
- 2013-09-12 US US14/371,482 patent/US9297091B2/en active Active
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CN106460216A (zh) * | 2014-06-24 | 2017-02-22 | 住友电气工业株式会社 | 铝镀液、铝膜的制造方法以及铝多孔体 |
CN106460216B (zh) * | 2014-06-24 | 2018-05-04 | 住友电气工业株式会社 | 铝镀液、铝膜的制造方法以及铝多孔体 |
WO2016031015A1 (ja) * | 2014-08-28 | 2016-03-03 | 日本軽金属株式会社 | アルミニウム電析用イオン溶液および電析反応装置 |
JP2017048444A (ja) * | 2015-09-04 | 2017-03-09 | 住友電気工業株式会社 | アルミニウム箔及びその製造方法 |
WO2017038992A1 (ja) * | 2015-09-05 | 2017-03-09 | 株式会社Uacj | 電解アルミニウム箔の製造方法 |
JP2017048453A (ja) * | 2015-09-05 | 2017-03-09 | 株式会社Uacj | アルミニウム箔の製造方法 |
US10590555B2 (en) | 2015-09-05 | 2020-03-17 | Uacj Corporation | Method for producing electrolytic aluminum foil |
Also Published As
Publication number | Publication date |
---|---|
US20140346050A1 (en) | 2014-11-27 |
KR20150056497A (ko) | 2015-05-26 |
JP6202344B2 (ja) | 2017-09-27 |
CN104053824B (zh) | 2017-11-24 |
US9297091B2 (en) | 2016-03-29 |
CN104053824A (zh) | 2014-09-17 |
JPWO2014045986A1 (ja) | 2016-08-18 |
DE112013004539T5 (de) | 2015-05-28 |
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