JP5929000B2 - Method for producing porous aluminum foil - Google Patents

Description

  The present invention relates to a method for producing a porous aluminum foil.

It is a well-known fact that lithium-ion secondary batteries with large energy density and no significant reduction in discharge capacity are used as the power source for mobile tools such as mobile phones and laptop computers. With the downsizing of tools, there is a demand for miniaturization of lithium ion secondary batteries attached to the tools. In addition, with the advancement of technologies such as hybrid vehicles and solar power generation from the viewpoint of global warming prevention measures, new applications of supercapacitors with large energy density such as electric double layer capacitors, redox capacitors and lithium ion capacitors will be developed. Accelerating, and further higher energy density is required.
An electricity storage device such as a lithium ion secondary battery or a supercapacitor has a positive electrode and a negative electrode made of polyolefin 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 has a structure that is arranged through a separator consisting of. 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, and each shape is a current collector. In general, an active material is applied to the surface of the material and formed into a sheet shape. In addition to applying a large voltage to each electrode, it is immersed in an organic electrolyte containing a highly corrosive fluorine-containing compound, so that the material of the positive electrode current collector is particularly excellent in electrical conductivity and resistance. It is required to be excellent in corrosiveness. Under such circumstances, as the material of the positive electrode current collector, aluminum that is a good electrical conductor and has excellent corrosion resistance by forming a passive film on the surface is adopted as the material of the positive electrode current collector. (Examples of the material for the negative electrode current collector include copper and nickel).

  As one of the methods for downsizing and increasing the energy density of an electricity storage device, a metal member used as a current collector constituting an electrode molded into a sheet shape is made porous, and the metal member is made available by using pores. A method of reducing the thickness by compressing or supporting an active material in pores has been considered. From this viewpoint, the present inventors have proposed an aluminum porous material obtained by removing the porous substrate after forming an aluminum film on the surface of the porous substrate by electroaluminum plating in Patent Document 1. ing. However, it is more desirable if the aluminum member can be made porous by a simpler method.

JP 2010-232171 A

  Then, this invention aims at providing the simple manufacturing method of the porous aluminum foil as a porous aluminum member.

The present inventor has been energetically researching aluminum electroplating technology, and as a result of the research, developed a method using a plating solution prepared by dissolving aluminum halide in dialkyl sulfone. (Japanese Patent Laid-Open No. 2008-31551). Then, when this inventor tried manufacture of the aluminum foil by the electrolytic method using this plating solution, this plating solution has the advantage that hydrogen chloride gas is hard to generate | occur | produce during a plating process, and 8A / dm < ² > or more. Although stable plating treatment is possible even when a current density is applied, there is an advantage that the film forming speed is fast, but the aluminum film formed on the surface of the base material is hard and poor in ductility. It was found that a phenomenon such as tearing occurred when peeling. Therefore, as a result of intensive studies to solve this problem, it was found that a high purity aluminum foil with high ductility can be obtained at a higher film formation rate by adding a predetermined nitrogen-containing compound to the plating solution. (International Publication No. 2011/001932). Furthermore, when the present inventor further researched, when the aluminum foil thus obtained was heat-treated at a predetermined temperature, a number of pores were generated unexpectedly inside the foil, making the foil porous. Found that you can.

The manufacturing method of the porous aluminum foil of the present invention completed based on the above knowledge is as described in claim 1, (1) dialkyl sulfone, (2) aluminum halide, and (3) ammonium halide, Primary amine hydrohalide, secondary amine hydrohalide, tertiary amine hydrohalide, general formula: R ¹ R ² R ³ R ⁴ N · X (R ^{1 to} R ⁴ are the same or Differently from an alkyl group, and X represents a counter anion for a quaternary ammonium cation) by an electrolytic method using a plating solution containing at least one nitrogen-containing compound selected from the group consisting of quaternary ammonium salts. After forming an aluminum film on the surface of the material, the film is peeled off from the base material to obtain an aluminum foil. Wherein the allowed to produce pores inside the foil by performing heat treatment at a temperature range of 50 to 700 ° C..

  ADVANTAGE OF THE INVENTION According to this invention, the simple manufacturing method of porous aluminum foil can be provided.

It is a result of cross-sectional observation of the aluminum foil before heat processing in Example 1. It is the result of cross-sectional observation of the aluminum foil after heat processing. It is a result of the cross-sectional observation of the aluminum foil after the heat processing in Example 2. It is a result of cross-sectional observation of the rolled aluminum foil before the heat processing in Comparative Example 3. It is a result of cross-sectional observation of the rolled aluminum foil after the heat treatment.

The method for producing the porous aluminum foil of the present invention comprises (1) dialkyl sulfone, (2) aluminum halide, and (3) ammonium halide, a primary amine hydrogen halide salt, and a secondary amine hydrogen halide. Salt, tertiary amine hydrogen halide salt, general formula: R ¹ R ² R ³ R ⁴ N · X (R ^{1 to} R ⁴ are the same or different, alkyl group, X represents counter anion for quaternary ammonium cation) The aluminum film is formed on the surface of the base material by an electrolytic method using a plating solution containing at least one nitrogen-containing compound selected from the group consisting of quaternary ammonium salts represented by the following formula: To obtain an aluminum foil, and heat treatment is performed on the obtained aluminum foil in a temperature range of 350 to 700 ° C. It is characterized in that allowed to produce a vacancy part.

  The dialkyl sulfone contained in the plating solution used in the method for producing the porous aluminum foil of the present invention has 1 to 6 carbon atoms in the alkyl group such as dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dihexyl sulfone, and methyl ethyl sulfone. Examples thereof (which may be linear or branched) can be exemplified, but dimethyl sulfone can be preferably employed from the viewpoint of good electrical conductivity and availability.

  Examples of the aluminum halide include aluminum chloride and aluminum bromide, but from the viewpoint of minimizing the amount of moisture contained in the plating solution which is a factor that hinders the precipitation of aluminum. The halide is preferably anhydrous.

Examples of the ammonium halide that can be employed as the nitrogen-containing compound include ammonium chloride and ammonium bromide. In addition, as primary amine to tertiary amine, the carbon number of alkyl groups such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, hexylamine, methylethylamine, etc. 1 to 6 (which may be linear or branched) can be exemplified. Examples of the hydrogen halide include hydrogen chloride and hydrogen bromide. R in a quaternary ammonium 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 an alkyl group, X represents a counter anion for a quaternary ammonium cation) Examples of the alkyl group represented by ^{1 to} R ⁴ include those having 1 to 6 carbon atoms (which may be linear or branched) such as a methyl group, an ethyl group, a propyl group, and a hexyl group. Examples of X include halide ions such as chlorine ions, bromine ions and iodine ions, as well as BF ₄ ⁻ and PF ₆ ⁻ . Specific examples of the compound include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, and tetraethylammonium tetrafluoride. Suitable nitrogen-containing compounds include hydrochlorides of tertiary amines such as trimethylamine hydrochloride in terms of facilitating the production of high-purity aluminum foil having a high ductility at a high film formation rate.

  The blending ratio of the dialkyl sulfone, the aluminum halide, and the nitrogen-containing compound is, for example, preferably 1.5 to 4.0 mol, more preferably 2.0 to 3.5 mol for the aluminum halide with respect to 10 mol of the dialkyl sulfone. . The nitrogen-containing compound is preferably 0.001 to 2.0 mol, more preferably 0.005 to 1.5 mol. If the blending amount of aluminum halide is less than 1.5 moles relative to 10 moles of dialkyl sulfone, the formed aluminum film may be darkened (a phenomenon called burning), or the film formation efficiency may be lowered. On the other hand, if it exceeds 4.0 moles, the plating solution may become too hot and decompose due to excessively high resistance of the plating solution. In addition, the effect of blending when the blending amount of the nitrogen-containing compound is less than 0.001 mole with respect to 10 moles of dialkyl sulfone, that is, realization of the plating treatment with high current density application based on the improvement of the electrical conductivity of the plating solution While it may be difficult to obtain effects such as improving the film formation rate, improving the purity of the aluminum foil, and improving ductility, the composition of the plating solution will change essentially when it exceeds 2.0 moles. There is a risk that aluminum will not precipitate.

Examples of the electroplating conditions include a plating solution temperature of 80 to 110 ° C. and an applied current density of ² to 15 A / dm ² . The lower limit of the temperature of the plating solution should be determined in consideration of the melting point of the plating solution, desirably 85 ° C., more desirably 95 ° C. Processing is no longer possible). On the other hand, when the temperature of the plating solution exceeds 110 ° C., the reaction between the aluminum coating formed on the surface of the substrate and the plating solution is activated, and the purity is lowered by incorporating a large amount of impurities into the aluminum coating. There is a fear. Further, while the applied current density is deposited efficiency falls below 2A / dm ² may be reduced, stable plating ductility or not be performed degradation and the cause of the nitrogen-containing compound exceeds 15A / dm ² There is a risk that a high-purity aluminum foil that is rich cannot be obtained. Applied current density 3~12A / dm ² is preferred. A notable advantage of the plating solution used in the method for producing an aluminum foil of the present invention is that a stable plating process can be performed even when a current density of 10 A / dm ² or more is applied. It is in a point that can be done. The time for the plating treatment depends on the desired thickness of the aluminum foil, the temperature of the plating solution, the applied current density, etc., but is usually 1 to 300 minutes (in consideration of production efficiency, 1 to 30 minutes is desirable. ). The plating treatment environment is desirably a dry atmosphere from the viewpoint of preventing the deterioration of the plating solution and extending its life.

  Examples of the substrate (cathode) for forming the aluminum coating include a stainless plate, a titanium plate, an aluminum plate, a nickel plate, and the like. Usually, in order to facilitate the peeling of the aluminum coating from the base material, it is desirable that the surface of the base material be as smooth as possible by performing mirror finishing or the like. The aluminum film formed on the surface has a feature that it can be easily peeled off even if such processing is not performed on the substrate (the reason is not necessarily clear, but the aluminum film is formed on the surface of the substrate). It is presumed that S and Cl derived from the plating solution are concentrated near the surface of the aluminum coating on the side in contact with the base material). In addition, as a material of an anode, aluminum can be illustrated, for example. The aluminum film can be peeled off from the substrate batchwise, or the aluminum film can be formed and peeled continuously using a cathode drum (for example, Japanese Patent Laid-Open No. 6-93490). Prior to peeling off the aluminum coating from the base material, it is desirable to dry it after washing with water to remove the plating solution adhering to the surface of the base material on which the aluminum coating is formed.

  In the method for producing a porous aluminum foil of the present invention, the aluminum foil obtained as described above is heat-treated in a temperature range of 350 to 700 ° C., and voids are generated inside the foil to make the foil porous. Qualify. The reason why pores are generated inside the aluminum foil by heat treatment is not necessarily clear, but it is because the components of the plating solution taken into the coating vaporize when the aluminum coating is formed on the surface of the substrate. It is assumed that there is. The temperature range of heat treatment for aluminum foil is defined as 350 to 700 ° C. If the temperature falls below 350 ° C., voids cannot be generated inside the foil, or it takes more time than necessary to generate it. On the other hand, if the temperature exceeds 700 ° C., the aluminum foil may be melted. By performing heat treatment on the aluminum foil in a temperature range of 350 to 700 ° C., for example, voids are effectively generated inside the foil without causing melting of the aluminum foil in a treatment time of 10 seconds to 3 hours, for example. Can do. The heat treatment for the aluminum foil may be performed, for example, in an air atmosphere, a reduced pressure atmosphere, or an inert gas atmosphere using argon gas or nitrogen gas.

  The porous aluminum foil produced by the method for producing a porous aluminum foil of the present invention is compressed by utilizing pores generated inside the foil in order to reduce the size and increase the energy density of the electricity storage device. It is expected to be used as a current collector for an electricity storage device that can be reduced in thickness or loaded with active material in pores. The thickness of the porous aluminum foil is preferably 5 to 200 μm. If the thickness is less than 5 μm, the strength may be insufficient for use as a current collector or the like, while if it exceeds 200 μm, the thickness may be too thick to be difficult to use as a current collector or the like. The porous aluminum foil manufactured by the method for manufacturing a porous aluminum foil of the present invention may be subjected to chemical processing such as machining such as punching or etching. If the processing holes penetrating the front and back of the foil and unevenness are provided on the surface of the foil by performing such treatment, it is possible to further increase the porosity of the foil in combination with the voids generated inside the foil. it can.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is limited to this and is not interpreted.

Example 1:
Dimethylsulfone, anhydrous aluminum chloride, and trimethylamine hydrochloride were mixed at a molar ratio of 10: 3: 0.05 and dissolved at 110 ° C. to prepare an electrolytic aluminum plating solution. An aluminum plate with a purity of 99.99 mass% is used as the anode, and a titanium plate is used as the cathode (base material for forming the aluminum coating). The plating solution is kept at 95 ° C. at an applied current density of 10 A / dm ² and stirred at 300 rpm. The electroplating process was carried out for 17 minutes while stirring at a speed. After 17 minutes, the titanium plate with the aluminum film formed on the surface is taken out of the plating solution, washed with water and dried, and then tweezers interposed between the aluminum film and the titanium plate are slid along the titanium plate from the end. The aluminum film was easily peeled from the titanium plate and an aluminum foil was obtained. The aluminum foil thus obtained was heat-treated at 550 ° C. for 1 hour in an air atmosphere. The results of observing the cross section of the aluminum foil before and after heat treatment with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd., the same shall apply hereinafter) are shown in FIGS. 1 and 2, respectively. As is clear from FIGS. 1 and 2, by heat-treating the aluminum foil, a large number of pores having a size of about 0.05 to 3 μm were generated inside the foil. The porous aluminum foil had a thickness of about 25 μm.

Example 2:
Dimethylsulfone, anhydrous aluminum chloride, and trimethylamine hydrochloride are mixed at a molar ratio of 10: 3: 0.01 to prepare a plating solution, the applied current density is set to 5 A / dm ^2, and the plating processing time is set. A heat-treated aluminum foil having a thickness of about 25 μm was obtained in the same manner as in Example 1 except that the heat treatment was performed at 350 ° C. for 26 minutes. FIG. 3 shows the result of observing the cross section with a scanning electron microscope. As is apparent from FIG. 3, this aluminum foil had a large number of pores formed therein.

Example 3:
Same as Example 2 except that dimethylsulfone, anhydrous aluminum chloride, and trimethylamine hydrochloride are mixed at a molar ratio of 10: 3: 0.005 to prepare a plating solution and the plating time is 6 minutes. Thus, an aluminum foil subjected to heat treatment having a thickness of about 5 μm was obtained. When the cross section was observed with a scanning electron microscope, many holes were present in the foil.

Example 4:
A heat-treated aluminum foil having a thickness of about 200 μm was obtained in the same manner as in Example 2 except that the plating time was 210 minutes and the heat treatment was performed at 700 ° C. for 10 seconds. When the cross section was observed with a scanning electron microscope, many holes were present in the foil.

Comparative Example 1:
Except performing heat processing at 300 degreeC, it carried out similarly to Example 2, and obtained the aluminum foil which performed heat processing whose thickness is about 25 micrometers. When the cross section was observed with a scanning electron microscope, there were no pores inside the foil.

Comparative Example 2:
An attempt was made to obtain an aluminum foil that was heat treated in the same manner as in Example 2 except that the heat treatment was performed at 750 ° C. for 12 seconds, but the foil melted by the heat treatment, and the shape of the foil was maintained after the heat treatment. There wasn't.

Comparative Example 3:
A commercially available rolled aluminum foil (manufactured by Nihon Foil Co., Ltd.) having a thickness of 25 μm was heat-treated at 500 ° C. for 1 hour in an air atmosphere. The results of observing the cross section of the rolled aluminum foil before and after heat treatment with a scanning electron microscope are shown in FIGS. 4 and 5, respectively. As apparent from FIGS. 4 and 5, even when the rolled aluminum foil was heat-treated, crystal grains were enlarged (recrystallized), and voids were not generated inside the foil.

The present invention has industrial applicability in that a simple method for producing a porous aluminum foil can be provided.

Claims (1)

(1) dialkyl sulfone, (2) aluminum halide, and (3) ammonium halide, primary amine hydrogen halide salt, secondary amine hydrogen halide salt, tertiary amine hydrogen halide salt, general A group consisting of a quaternary ammonium salt represented by the formula: R ¹ R ² R ³ R ⁴ N · X (R ^{1 to} R ⁴ are the same or different and an alkyl group, X represents a counter anion with respect to a quaternary ammonium cation) An aluminum film was formed on the surface of the substrate by an electrolytic method using a plating solution containing at least one nitrogen-containing compound selected from the following, and then the film was peeled from the substrate to obtain an aluminum foil. The aluminum foil is heat-treated in a temperature range of 350 to 700 ° C., thereby generating voids in the foil. Method of manufacturing quality aluminum foil.