JP2015193233A - Coated aluminum material and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated aluminum material which comprises an aluminum material, an intervention layer and a coating layer and secures sufficient adhesion between the aluminum material and the coating layer even in producing by laminating a sheet-like aluminum layer or rolling an aluminum material in a belt form.SOLUTION: A coated aluminum material includes an aluminum material, a coating layer formed on the surface of the aluminum material and an intervention layer which is formed between the aluminum material and the coating layer and contains aluminum element and carbon element. (1) The intervention layer is formed in at least a partial region of the surface of the aluminum material and contains aluminum carbide; and (2) the coated aluminum material is provided with an irregular part in one or both sides.

Description

  The present invention relates to a coated aluminum material and a method for producing the same.

  As an electrode material for batteries, capacitors and the like, coated aluminum coated with a coating layer such as a carbon-containing layer or a dielectric layer is used.

  Conventionally, in coated aluminum, a coating layer is formed on the surface of the aluminum material, and a layer containing aluminum carbide is formed between the aluminum material and the coating layer for the purpose of improving the adhesion between the aluminum material and the coating layer. Technology is known.

  For example, in Patent Document 1, a carbon-containing layer is formed on the surface of an aluminum material, and then heated in a space containing a hydrocarbon-containing material, whereby aluminum carbide is provided between the aluminum material and the carbon-containing layer. A technique for forming an intervening layer containing a metal is disclosed. In Patent Document 2, a dielectric layer containing dielectric particles is attached to the surface of an aluminum material, and then heated in a space containing a hydrocarbon-containing substance, whereby the aluminum material and the dielectric layer are separated. A technique for forming an intervening layer containing aluminum carbide therebetween is disclosed. In the coated aluminum material of both techniques, the interposition layer enhances the adhesion between the aluminum material and the carbon-containing layer or the dielectric layer.

International Publication No. 2004/087984 Pamphlet International Publication No. 2010/109783 Pamphlet

  However, when the carbon-coated aluminum material described in Patent Document 1 is produced, there is a problem that the adhesion between the aluminum material and the carbon-containing layer is insufficient in a part of the carbon-coated aluminum material. For example, when a smooth sheet-like aluminum material is used as a base material and a plurality of aluminum materials are laminated and heat treatment is performed, the adhesion between the aluminum material and the carbon-containing layer is insufficient in the vicinity of the center of the aluminum material. there were. In addition, when a smooth strip-shaped aluminum material is used as a base material and heat treatment is performed in a roll-shaped state, the adhesion between the aluminum material and the carbon-containing layer is poor in the vicinity of the central portion in the width direction of the aluminum material. It was enough. Moreover, when the electrode structure described in Patent Document 2 was manufactured, the adhesion between the aluminum material and the dielectric layer was insufficient. In other words, when a sheet-like aluminum material is laminated, or when the aluminum material is rolled into a band shape, a part of the coated aluminum material, near the center, the dielectric layer attached to the surface of the aluminum material There was a problem of insufficient adhesion. As a result, there has been a problem that the charge / discharge characteristics, life, etc. of the secondary battery or capacitor are reduced.

  Also, it is considered to widen the aluminum material for the purpose of improving production efficiency. However, simply widening the aluminum material, as described above, the adhesion between the aluminum material and the coating layer is poor at the center in the width direction, and the coating layer in the capacitor assembly process, etc. Sometimes it peeled off. When the coating layer is peeled off from the aluminum material, the resistance value of the aluminum material increases and there is a problem that desired electrical characteristics cannot be obtained.

  The present invention is a coated aluminum material including an aluminum material, an intervening layer, and a coating layer, which is manufactured by laminating sheet-shaped aluminum materials, or when the aluminum material is rolled into a band shape and manufactured. Even if it exists, it aims at providing the covering aluminum material with which aluminum material and a coating layer are fully stuck, and its manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have found that the coated aluminum material comprising an aluminum material, an intervening layer containing an aluminum carbide, and a coating layer, in particular, the coated aluminum material has one surface or both surfaces. The present inventors have found that the above-mentioned problems can be solved when the concavo-convex portion is formed on the surface, and have completed the present invention.

  That is, this invention is the following coating | coated aluminum materials and its manufacturing method.

Item 1.
A coated aluminum material comprising: an aluminum material; a coating layer formed on a surface of the aluminum material; and an intervening layer containing an aluminum element and a carbon element formed between the aluminum material and the coating layer. And
(1) The intermediate layer is formed in at least a partial region of the surface of the aluminum material, and includes an aluminum carbide.
(2) As for the said covering aluminum material, the uneven | corrugated | grooved part is formed in the single side | surface or both surfaces,
A coated aluminum material characterized by that.

Item 2.
Item 2. The coated aluminum material according to Item 1, wherein the concavo-convex portion has a peak height from a valley of the concavo-convex portion of 1 µm to 300 µm.

Item 3.
Item 2. The coated aluminum material according to Item 1, wherein the unevenness portion has a surface roughness Ra of 0.3 µm or more and 10 µm or less.

Item 4.
The shape of the said uneven | corrugated | grooved part is a covering aluminum material in any one of said claim | item 1 -3 which is any one of a dot, a satin, a lattice, a stripe, a turtle shell, a cloth, a silk, a chirimen, a wave shape, or a crepe.

Item 5.
5. The coated aluminum material according to item 4, wherein the distance between adjacent streaky concave portions is 1 μm or more and 100 mm or less when the shape of the uneven portion is a texture, stripe, or crepe.

Item 6.
Item 5. The coated aluminum material according to Item 4, wherein when the shape of the concavo-convex portion is a dot, the distance between the adjacent dot-like concave portions is 1 μm or more and 100 mm or less.

Item 7.
The coated aluminum material according to claim 1, wherein the coating layer is a layer containing carbon or a layer containing an inorganic substance.

Item 8.
Item 7. The coated aluminum material according to any one of Items 1 to 6, wherein the coated aluminum material is used for constituting an electrode structure.

Item 9.
Item 9. The coated aluminum material according to Item 8, wherein the electrode structure is a current collector or an electrode of a capacitor.

  Item 10. Item 9. The coated aluminum material according to Item 8, wherein the electrode structure is a battery current collector or electrode.

Item 11.
A method for producing a coated aluminum material,
A coating layer forming step of forming a coating layer on the surface of the aluminum material;
A heating step of arranging and heating the coating layer forming aluminum material in a space containing a hydrocarbon-containing substance,
The covering layer forming step includes an uneven portion forming step of forming an uneven portion on one side or both sides of the aluminum material or the covering layer forming aluminum material.
A method for producing a coated aluminum material.

Item 12.
Item 12. The method for producing a coated aluminum material according to Item 11, wherein the concavo-convex portion forming step forms a concavo-convex portion having a peak height of 1 μm or more and 300 μm or less from a valley of the concavo-convex portion by embossing.

  The coated aluminum material of the present invention is a coated aluminum material including an aluminum material, an intervening layer, and a coated layer, and is manufactured by laminating sheet-shaped aluminum materials, or the aluminum material is rolled into a belt shape Even in the case of manufacturing, the aluminum material and the covering layer are sufficiently adhered.

As one form of this invention, it is sectional drawing which shows typically the cross-section of a covering aluminum material. The photograph which confirmed the surface of the sample of Example 1 of this invention with the scanning electron microscope (SEM) is shown.

  The present invention is described in detail below.

  The present invention relates to a coated aluminum material and a method for producing the same. The present invention particularly relates to a coated aluminum material used for electrodes and current collectors of various capacitors, current collectors and electrodes of various batteries, and further to a catalyst material, a heat dissipation material, a deodorizing / cleaning material, and a method for producing the same. . Specifically, the present invention relates to electrodes or electrodes used in lithium batteries, lithium ion batteries, lithium ion polymer batteries, dye-sensitized solar cells, electric double layer capacitors, electrolytic capacitors, fuel cells, solid polymer fuel cells, and the like. The present invention relates to a current collector material, a photocatalyst material, a gas decomposition catalyst material, a heat dissipation material for various electronic devices, a coated aluminum material as a material having a deodorizing action and an air cleaning action, and a method for producing the same.

  When the present inventors have laminated a smooth sheet-like coated aluminum material or wound the coated aluminum material in a roll shape to form a strip shape, the adhesiveness between the aluminum material and the coating layer is insufficient. It has been found that one of the causes is that the intervening layer formed between the material and the covering layer is not sufficiently formed.

  According to the knowledge of the present inventors, after a coating layer (for example, a layer containing carbon) is attached to the surface of the aluminum material, the aluminum is formed by heating the aluminum in the space containing the hydrocarbon-containing substance. The intervening layer containing aluminum and carbon is generated by the reaction between the element and the carbon element of the hydrocarbon-containing substance. That is, it was found that in order to generate this intervening layer, it is necessary that the aluminum material and the hydrocarbon-containing substance can be in sufficient contact.

  For example, when a gaseous material is used as the hydrocarbon-containing substance, a plurality of coated aluminum materials can be obtained by laminating a smooth sheet-shaped coated aluminum material or winding a smooth strip-shaped coated aluminum material in a roll shape. Are laminated, and this coated aluminum material is disposed in a space containing a hydrocarbon-containing substance. Then, the gas containing the hydrocarbon-containing substance passes through a slight gap between the individual coated aluminum materials and permeates from the end portion of the coated aluminum material toward the central portion, thereby forming an intervening layer.

  At this time, the gas containing the hydrocarbon-containing material easily permeates near the end of the coated aluminum material, but the gas containing the hydrocarbon-containing material permeates as the distance from the end increases near the center of the coated aluminum material. It becomes difficult to do. As a result, in the heating process in the space containing the hydrocarbon-containing substance, the hydrocarbon-containing substance cannot sufficiently come into contact with the vicinity of the center of the surface of the coated aluminum material. And it was thought that the production | generation amount of an intervening layer fell between an aluminum material and a coating layer.

  As a result of intensive studies, the present inventor has obtained the following knowledge.

  A coated aluminum material including an aluminum material, an intervening layer, and a coated layer, wherein the coated aluminum material has uneven portions on one side or both sides, so that a sheet-shaped aluminum material is laminated, or the aluminum material is wound in a roll shape Even when it is made into a strip shape, the intervening layer is sufficiently generated. That is, the coated aluminum material can sufficiently come into contact with the hydrocarbon-containing substance, the intervening layer is sufficiently generated even near the center of the surface of the coated aluminum material, and the aluminum material and the coated layer have sufficient adhesion. I found out.

  By forming uneven portions on one or both sides of the coating layer forming aluminum material, when manufacturing a large amount of the coated aluminum material at a time, the interval between the aluminum materials to be laminated can be reduced, and the aluminum materials can be arranged in a high density in a layered manner. An appropriate space is created between the aluminum materials. As a result, it is possible to efficiently produce a coated aluminum material including an aluminum material, an intervening layer, and a coating layer. In a covering aluminum material, since an intervening layer is fully generated between an aluminum material and a covering layer, the aluminum material and the covering layer are in good contact. As a result, in the coated aluminum material, the resistance value between the aluminum material and the coating layer can be reduced, and an electrode structure having a high capacitance can be manufactured using the coated aluminum material.

(1) Coated aluminum material The coated aluminum material of the present invention comprises an aluminum material, a coating layer formed on the surface of the aluminum material, an aluminum element formed between the aluminum material and the coating layer, and A covering aluminum material comprising an intervening layer containing a carbon element, wherein (1) the intervening layer is formed in at least a partial region of the surface of the aluminum material and includes an aluminum carbide; (2) the covering The aluminum material is characterized in that concave and convex portions are formed on one side or both sides.

  The intervening layer for fixing the aluminum material and the coating layer (for example, a carbon-containing layer such as carbon particles) can be grown by contacting the hydrocarbon-containing substance with aluminum in a heating process at a high temperature. Is possible. In consideration of productivity, the above treatment is usually performed in a state where a plurality of sheet-like aluminum materials are laminated or a belt-like aluminum material is wound in a roll shape. However, when the lamination degree of the aluminum material is increased by laminating, since the interval (gap) between the aluminum material and the aluminum material is eliminated or very narrow, the aluminum material and the hydrocarbon-containing substance are difficult to contact, There is a tendency that the intervening layer is hardly formed. Moreover, when the area of the aluminum material to laminate | stack becomes large, there exists a tendency for an aluminum material and a hydrocarbon containing material to become difficult to contact in the center part of an aluminum material. As a result, a portion where an intervening layer having a role of adhering the aluminum material and the hydrocarbon-containing material is not formed, and a region where the coating layer is easily peeled tends to be generated.

  The coated aluminum material of the present invention can have sufficient adhesion between the aluminum material and the coating layer by forming the concavo-convex portions on one surface or both surfaces. This is because the coating aluminum material and the hydrocarbon-containing substance can be sufficiently in contact with the central part of the coating aluminum material even in the state where a plurality of coating aluminum materials are stacked in the heating step for forming the intervening layer. This is because the carbide of aluminum in the intervening layer is sufficiently generated even near the center of the surface of the coated aluminum material.

  In the coated aluminum material, the concavo-convex portion only needs to be formed on one or both sides of the coated aluminum material.

  The aluminum material (base material) that can be used for the coated aluminum material is not particularly limited in terms of its composition. For example, a pure aluminum or aluminum alloy foil or plate can be used. Such an aluminum material preferably has an aluminum purity of 98% by mass or more as measured by the method described in JIS H2111.

  As the composition of the aluminum material, lead (Pb), silicon (Si), iron (Fe), copper (Cu), manganese (Mn), magnesium (Mg), chromium (Cr), zinc (Zn), titanium (Ti) Further, it may be an aluminum alloy to which at least one alloy element of vanadium (V), gallium (Ga), nickel (Ni) and boron (B) is added within a necessary range. In addition, the aluminum material may contain inevitable impurity elements other than the elements listed above.

  What was manufactured by a well-known method can be used for said aluminum material. For example, an aluminum ingot having the above predetermined composition is prepared, and an ingot obtained by casting the aluminum melt is appropriately homogenized. Thereafter, an aluminum foil or an aluminum plate can be obtained by subjecting the ingot to hot rolling and cold rolling. In addition, you may perform an intermediate annealing process in the range of about 150-400 degreeC in the middle of said cold rolling process.

  The thickness of the aluminum material is not particularly limited. In the case of using an aluminum foil, it is generally preferable to set the thickness within a range of about 5 to 200 μm. When an aluminum plate is used, it is preferably in the range of more than 200 μm and about 3 mm or less.

  It is preferable that the concavo-convex portion formed on the coated aluminum material is formed on the surface of the coating layer.

  Moreover, it is preferable that the uneven | corrugated | grooved part is formed in multiple numbers on the coating layer surface.

  Although the formation method of an uneven | corrugated | grooved part is not specifically limited, For example, press work, embossing, an etching process, laser processing etc. are mentioned. From the viewpoint of easy formation of the uneven portion, it is preferable to form the uneven portion by embossing.

  The height of the peak from the valley of the uneven portion in the coated aluminum material is not particularly limited, but the height of the peak from the valley of the uneven portion is preferably 1 μm or more and 300 μm or less.

  Since the height of the peaks from the valleys of the irregularities is within this range, even if a plurality of coated aluminum materials are laminated, an appropriate space is created between the coated aluminum materials. Can penetrate into the center of the coated aluminum material. As a result, the covering aluminum material and the hydrocarbon-containing substance can be sufficiently in contact with each other, and an intervening layer necessary for ensuring sufficient adhesion between the aluminum material and the covering layer can be formed.

  The height of the convex portion or the concave portion (height H in FIG. 1 described later) from the original base material is the height of the mountain from the valley of the concave and convex portion.

  In addition, the upper limit value of the height of the peak from the valley of the concavo-convex portion is not particularly limited from the viewpoint of forming the intervening layer. If the height of the peak from the valley of the uneven portion increases, the gap generated between the coated minium materials also increases, so that an intervening layer is easily formed in the central portion of the coated aluminum material. However, when the height of the peaks from the valleys of the irregularities increases, the overall thickness of the coated aluminum material also increases, and the size of the electrode structure using it increases. The upper limit of the thickness is preferably 300 μm. However, in the coated aluminum material of the present invention, it does not exclude that the height of the peak from the valley of the uneven portion exceeds 300 μm.

  If the height of the peaks from the valleys of the concavo-convex portions is less than 1 μm, the aluminum material tends not to sufficiently contact the hydrocarbon-containing substance in the heating step for forming the intervening layer. As a result, the intervening layer is not sufficiently generated, and the aluminum material and the coating layer tend not to have sufficient adhesion in the vicinity of the center portion of the surface of the coating aluminum material.

  As described above, in the coated aluminum material, the height of the peak from the valley of the uneven portion is preferably 1 μm or more and 300 μm or less, and preferably 5 μm or more and 60 μm or less.

  As a simple measuring method, the height of the peak from the valley of the uneven portion can be measured using a micrometer based on JIS B7502. Specifically, the thickness of the coated aluminum material before and after the formation of the concavo-convex portion was measured, and “(the thickness of the coated aluminum material on which the concavo-convex portion was formed) − (the thickness of the coated aluminum material before the concavo-convex portion was formed)” Can be calculated as “the height of the mountain from the valley of the uneven portion”.

  In the above measurement method, it is difficult to confirm the height from the finally obtained coated aluminum material (that is, the coated aluminum material on which the concavo-convex portion has already been formed). A confirmation method can be adopted. Specifically, it is possible to obtain a height by cutting a vertical cross section of the coated aluminum material on which the uneven portion is formed, observing the cross section with an optical microscope or an electron microscope, and measuring the height of the mountain from the valley of the uneven portion. It is.

  In the coated aluminum material of the present invention, the unevenness of the uneven portion can be specified by the surface roughness Ra (μm). In this case, the surface roughness Ra is not particularly limited, but is preferably 0.3 μm or more and 10 μm or less, and more preferably 1.0 μm or more and 4.5 μm or less. By being within this range, even if a plurality of coated aluminum materials are laminated, an appropriate space is created between the coated aluminum materials, so that the hydrocarbon-containing substance can penetrate to the center of the coated aluminum material. Is possible. As a result, the covering aluminum material and the hydrocarbon-containing substance can be sufficiently in contact with each other, and an intervening layer necessary for ensuring sufficient adhesion between the aluminum material and the covering layer can be formed. The surface roughness Ra can be measured with a surface roughness meter according to the centerline average roughness Ra of JIS B0601: 1982. The measurement length when the formed uneven portion has periodicity is measured so that the uneven portion is included for 10 cycles or more. The measurement speed is 0.3 mm / second or less.

  The surface roughness Ra is not particularly limited from the viewpoint of forming the intervening layer. If the value of the surface roughness Ra is increased, the gap generated between the coated aluminum materials is also increased, so that an intervening layer is easily formed in the central portion of the coated aluminum material. However, when the surface roughness Ra increases, the resulting coated aluminum material also increases in thickness as a whole, and the size of the electrode structure using it increases, so the upper limit of the surface roughness Ra may be 10 μm. preferable. However, in the coated aluminum material of the present invention, it is not excluded that the surface roughness Ra exceeds 10 μm. When the surface roughness Ra is less than 0.3 μm, there is a tendency that the aluminum material cannot sufficiently come into contact with the hydrocarbon-containing substance in the heating step for forming the intervening layer. As a result, the intervening layer is not sufficiently generated, and the aluminum material and the coating layer tend not to have sufficient adhesion in the vicinity of the center portion of the surface of the coating aluminum material.

  In the coated aluminum material of the present invention, in addition to the above Ra, the unevenness of the uneven portion preferably has a maximum height Rmax (μm) of 1 μm to 300 μm, and more preferably 5 μm to 60 μm. . In this case, if the value of the maximum height Rmax increases, the gap generated between the coated aluminum materials also increases, so that an intervening layer is easily formed at the center of the coated aluminum material. However, when the maximum height Rmax increases, the resulting coated aluminum material also increases in thickness as a whole, and the size of the electrode structure using it increases, so the upper limit of the maximum height Rmax may be 300 μm. preferable. However, in the coated aluminum material of the present invention, it is not excluded that the maximum height Rmax exceeds 300 μm. When the maximum height Rmax is less than 1 μm, there is a tendency that the aluminum material cannot sufficiently come into contact with the hydrocarbon-containing substance in the heating step for forming the intervening layer. As a result, the intervening layer is not sufficiently generated, and the aluminum material and the coating layer tend not to have sufficient adhesion in the vicinity of the center portion of the surface of the coating aluminum material.

  The shape of the concavo-convex portion is not particularly limited as long as the effect of the present invention is achieved. For example, the shape such as dots, satin, lattices, stripes, turtle shells, cloths, silks, chirimen, wavy or crepe is seen in plan view. Can be mentioned.

  In the coated aluminum material of the present invention, the interval between the concavo-convex parts is not particularly limited as long as the effect of the present invention is achieved, but it is preferably formed in the range of 1 μm to 100 mm, preferably 10 μm to 10 mm. Is more preferable. In the present invention, the interval between the concave and convex portions means a distance from the center of the concave portion to the center of the adjacent concave portion when the cross section of the concave and convex portion is observed.

  When the interval between the concavo-convex portions is in the range of 1 μm to 100 mm, the aluminum material (coating layer forming aluminum material) having a coating layer formed on the surface is placed in a space containing a hydrocarbon-containing substance and heated (heating) In the step), the material can be uniformly heat-treated.

  When the interval between the concavo-convex parts exceeds 100 mm, when the coated aluminum material is a thin foil, there is a tendency that the parts where the concavo-convex parts on the surface of the coated aluminum material are not formed tend to come into contact with each other. There is a tendency that a sufficient gap cannot be secured with the foil. Therefore, in the heating step, the hydrocarbon-containing substance does not sufficiently penetrate from the gap between the coated aluminum materials, and there is a tendency that the intervening layer is not sufficiently formed between the aluminum material and the coating layer. As a result, the adhesion between the aluminum material and the coating layer tends to decrease.

  When the interval between the uneven portions is less than 1 μm, it becomes difficult to form uneven portions having a surface roughness Ra of 0.3 μm or more. As a result, the aluminum material and the coating layer tend not to have sufficient adhesion in the vicinity of the center of the surface of the coated aluminum material.

  In the case where the shape of the concavo-convex portion is a texture, stripe, or crepe, the concavo-convex portion is formed in a streak shape, and the interval between adjacent streaky concavo-convex portions is preferably 1 μm to 100 mm.

  When the shape of the concavo-convex part is a dot, the interval between adjacent dot-like concavo-convex parts is preferably 1 μm to 100 mm.

  Moreover, when forming an uneven | corrugated | grooved part by embossing, if the pattern shape (uneven | corrugated shape of a cross section) of an uneven | corrugated | grooved part has an effect of this invention, it will not specifically limit, Various shapes can be employ | adopted. For example, any known pattern such as dots, satin, lattices, stripes, turtle shells, cloths, silks, chirimen, wavy or crepes can be used.

  In the coated aluminum material, the coating layer is formed on the surface of the aluminum material.

  In a covering aluminum material, it is preferable that a coating layer is a layer containing carbon or a layer containing an inorganic substance. A coating layer is formed in the single side | surface or both surfaces of an aluminum base material. The coating layer of the coated aluminum material has an action of expanding or increasing the surface area of the aluminum material.

  The layer containing carbon is not particularly limited as long as it contains carbon. For example, the carbon precursor produced | generated by thermal decomposition of the resin etc. which are mentioned later, a carbon simple substance, the compound containing carbon etc. are mentioned. Moreover, those forms are not specifically limited, A dense layer may be sufficient and shapes, such as a particulate form, a fiber form, and a whisker form, may be taken.

  The carbon precursor preferably contains at least carbon and hydrogen elements. The carbon precursor preferably further contains a component similar to graphite or a component similar to amorphous carbon.

  As carbon simple substance, activated carbon fiber, activated carbon cloth, activated carbon felt, activated carbon powder, carbon black, graphite and the like are preferable, and black ink can be used as a substance containing carbon simple substance.

  As the compound containing carbon, an inorganic carbon compound, a carbon compound such as silicon carbide, and the like are preferable. The layer containing an inorganic substance is not particularly limited as long as it contains an inorganic substance. For example, a metal simple substance, a metal oxide, a metal nitride, etc. are mentioned. The form of the inorganic material is not particularly limited, and may be a dense layer, and may have a shape such as a particle shape, a fiber shape, or a whisker shape.

  Although it does not specifically limit as a metal which comprises a metal simple substance, a metal oxide, a metal nitride etc., For example, magnesium, thorium, cadmium, tungsten, tin, iron, silver, silicon, tantalum, titanium, hafnium, aluminum, zirconium Niobium, zinc, bismuth, antimony, nickel, lithium, manganese, cobalt and the like. In particular, when the coated aluminum material of the present invention is used as an electrode structure, the metal oxide may be titanium oxide, tantalum oxide, zirconium oxide, niobium oxide, zinc oxide, zirconium oxide, tungsten oxide, aluminum oxide, or the like. More preferred.

Moreover, when using the covering aluminum material of this invention as an electrode of a secondary battery, the active material which comprises the electrode of a secondary battery can be used as an inorganic substance of the layer containing an inorganic substance. For example, when the secondary battery is a lithium ion battery, it is preferable to use a lithium-containing metal oxide as the inorganic substance. For the lithium-containing metal oxides, for example, as a general formula can be used _{LixMO 2, LixM 2 O 4,} LixMAO 4 like. Here, M is one or more transition metal elements, and examples thereof include Co, Ni, Mn, and Fe. Examples of A include P, Si, S, V, and the like. Further, when using a lithium-containing metal oxide in the present invention, the lithium-containing metal oxide is not particularly limited as long as the composition or crystal structure does not change in the heating step. Specifically, LiMPO ₄ , LiM ₂ O ₄ , LiFePO ₄ etc. can be illustrated. Among these, LiFePO ₄ is preferable as the lithium-containing metal oxide.

  The thickness of the coating layer is not particularly limited and may be appropriately set depending on the application, but is preferably 0.001 to 200 μm, more preferably 0.01 to 100 μm.

  An intervening layer described later is formed in at least a part of the surface of the aluminum material. Further, the coating layer may include aluminum carbide formed so as to extend from the surface portion of the intervening layer to the outside in the form of a fiber, a filament, a whisker, a plate, a wall, or a lump. Good. In this case, these have the effect | action which increases the surface area of a coating layer, and when used for an electrode structure, they act to raise an electrostatic capacitance.

  In the covering aluminum material, an intervening layer containing an aluminum element and a carbon element is formed between the aluminum material and the covering layer. The intervening layer includes an aluminum carbide formed in at least a partial region of the surface of the aluminum material.

  The intervening layer is obtained by heat-treating an aluminum material having a coating layer formed on the surface thereof in an atmosphere containing a hydrocarbon-containing substance.

  The intervening layer can increase the adhesion between the aluminum material and the coating layer, and can suppress the formation of a layer containing aluminum and oxygen formed between the aluminum material and the coating layer. As a result, when a coated aluminum material is used for the electrode structure, the resistance value between the aluminum material and the coating layer can be reduced, and an electrode structure having a high capacitance can be manufactured. It is.

  The intervening layer preferably contains crystallized aluminum carbide. The crystallized aluminum carbide has the effect of further improving the adhesion.

  Although the use of the coated aluminum material of the present invention is not limited, for example, it can be used for constituting an electrode structure. By constituting the electrode structure using the coated aluminum material, the charge / discharge characteristics, life, etc. of the battery or capacitor can be improved.

  The electrode structure can be used to constitute a current collector or electrode of a capacitor. When the electrode structure constitutes a capacitor, the charge / discharge characteristics, life, etc. of the capacitor can be improved. Examples of the capacitor include an electric double layer capacitor, an aluminum electrolytic capacitor, and a functional solid capacitor.

  The electrode structure may be used to configure a battery current collector and an electrode. Thereby, the internal resistance (loss resistance) of the battery can be reduced, and the charge / discharge characteristics and life of the battery can be improved. Examples of the battery include a secondary battery such as a lithium ion battery.

  The coated aluminum material of the present invention can be used as a catalyst material when the coating layer is a layer that acts as a catalyst, for example, when a layer having a photocatalytic action or gas decomposition action is used. For example, when the coating layer includes particles having photocatalytic action such as titanium oxide particles, the aluminum material and the coating layer are not fixed by the resin, and the aluminum material and the coating layer are fixed by the intervening layer. When it is fixed with resin, the resin deteriorates with time due to the photocatalytic action of the coated aluminum material itself, and the adhesion decreases. Since there is no deterioration over time, there is an advantage that the adhesion between the aluminum material and the coating layer is secured even over time.

  The coated aluminum material of the present invention can also be used as a heat dissipation material. For example, when the coating layer is a layer containing carbon having heat dissipation, it can be used for heat dissipation of various electronic devices.

  Furthermore, the coated aluminum material of the present invention can also be used for applications having a deodorizing action and an air cleaning action utilizing the adsorption action of activated carbon when the coating layer is a layer containing activated carbon or the like.

(2) Method for producing coated aluminum material The method for producing a coated aluminum material of the present invention comprises a coating layer forming step of forming a coating layer on the surface of the aluminum material, and the coating layer forming aluminum material in a space containing a hydrocarbon-containing substance. And a heating step of arranging and heating, wherein the covering layer forming step includes an uneven portion forming step of forming uneven portions on one or both sides of the covering layer forming aluminum material.

  In the manufacturing method of the covering aluminum material, the covering layer forming step includes an uneven portion forming step of forming the uneven portion on one or both sides of the covering layer forming aluminum material, so that the uneven portion is formed on one surface or both surfaces of the covering layer forming aluminum material. It is formed.

  In the heating step subsequent to the coating layer forming step, the coating layer forming aluminum material having a concavo-convex portion on one side or both sides is arranged and heated in a space containing a hydrocarbon-containing substance.

  As a result, even when a coated aluminum material is manufactured by laminating sheet-shaped coating layer forming aluminum materials, or when a coated aluminum material is manufactured by winding a belt-shaped coating layer forming aluminum material in a roll shape, the aluminum material is sufficient. It is possible to come into contact with a hydrocarbon-containing substance. As a result, the intervening layer is sufficiently generated even in the vicinity of the center of the surface of the coated aluminum material, and the aluminum material and the coated layer can have sufficient adhesion.

  The method for producing a coated aluminum material of the present invention includes a coating layer forming step of forming a coating layer on the surface of the aluminum material. Furthermore, the said coating layer formation process includes the uneven | corrugated part formation process which forms an uneven | corrugated | grooved part in the single side | surface or both surfaces of an aluminum material or a coating layer formation aluminum material.

  In the manufacturing method of the covering aluminum material of this invention, the uneven | corrugated | grooved part formation process should just be performed in the any time in a covering layer formation process. For example, the coating layer may be formed after forming the uneven portion on the aluminum material, or the uneven portion may be formed after forming the coating layer on the aluminum material.

  Especially as a coating layer formation process, if the process of forming a coating layer at least on the surface of an aluminum material and the uneven part formation process of forming an uneven part on one side or both sides of an aluminum material or a coating layer formation aluminum material are included. Although not limited, for example, (1) After forming irregularities on the surface of the aluminum material, a coating layer (a layer containing carbon or an inorganic material) is formed. (2) A coating layer is formed on the surface of the aluminum material. After that, there are three forms of forming an uneven portion, or (3) forming a coating layer having an uneven portion on the surface of an aluminum material.

  The method for forming the coating layer is not particularly limited. For example, as described later, it can be attached on the surface of an aluminum material by coating, dipping, thermocompression bonding, or the like. In the case of the above (2), if the aluminum material has an uneven portion, it tends to be difficult to uniformly apply the coating layer to the aluminum material surface as compared to the case where there is no unevenness. In this respect, it is preferable to form the uneven portion after forming the coating layer on the surface of the aluminum material.

  In this way, when one surface or both surfaces of the coating layer forming aluminum material is formed with a concavo-convex portion, the sheet-shaped coating layer forming aluminum material is produced by being laminated, or the belt-shaped coating layer forming aluminum material is rolled. Even in the case of being wound around, the aluminum material can sufficiently come into contact with the hydrocarbon-containing substance in the heating step described later. As a result, the intervening layer is sufficiently generated even near the center of the surface of the covering aluminum material, and the aluminum material and the covering layer have sufficient adhesion. As a result, in a state where a plurality of sheet-like aluminum foils are laminated or in a state of a strip-shaped aluminum material wound in a roll shape, a coated aluminum material having sufficient adhesion between the aluminum material and the coating layer is obtained. It becomes possible to manufacture.

  In the method for producing a coated aluminum material of the present invention, in the coating layer forming step, as a method for attaching the coating layer to the surface of the aluminum material, a binder, a solvent, water, or the like is used to form a slurry, a liquid, or a solid. What mixed said carbon or inorganic substance can be made to adhere on the surface of an aluminum material by application | coating, dipping, or thermocompression bonding. In addition, it does not specifically limit as a coating method, A spin coating method, a bar coating method, a flow coating method, a spray method etc. are employ | adopted suitably. After depositing the coating layer on the surface of the aluminum material, it may be dried at a temperature in the range of about 20 to 300 ° C. before the heating step.

  In the method for producing a coated aluminum material of the present invention, a binder may be used as described above in order to adhere the coating layer to the surface of the aluminum material. Binders include carboxy-modified polyolefin resin, vinyl acetate resin, vinyl chloride resin, vinyl chloride copolymer resin, vinyl alcohol resin, vinyl fluoride resin, acrylic resin, polyester resin, urethane resin, epoxy resin, urea resin, phenol resin Synthetic resins such as acrylonitrile resin, nitrocellulose resin, paraffin wax and polyethylene wax, wax or tar, and natural resins or waxes such as glue, urushi, pine resin and beeswax can be suitably used. Depending on the molecular weight and resin type, these binders may be volatilized when heated, or may remain in the coating as a carbon precursor by thermal decomposition. The binder may be diluted with water or an organic solvent to adjust the viscosity.

  In the uneven portion forming step of the method for manufacturing the coated aluminum material, it is preferably formed by embossing, and the height of the peak from the valley of the uneven portion is 1 μm or more and 300 μm or less. It is more preferable that the height of the peak from the valley of the uneven portion is 5 μm or more and 60 μm or less. The height of the peak from the valley of the uneven portion is within this range, so that even if a plurality of coating layer forming aluminum materials are laminated, the hydrocarbon-containing substance is removed from the central portion of the coating layer forming aluminum material. Can penetrate. As a result, the coating layer forming aluminum material and the hydrocarbon-containing substance can be in sufficient contact, and the intervening layer necessary to ensure sufficient adhesion between the aluminum material and the coating layer is uniformly formed on the surface of the aluminum material. can do.

  The upper limit of the height of the peak from the valley of the concavo-convex portion is not particularly limited from the viewpoint of the intervening layer formation. When the height of the peak from the valley of the uneven part increases, the finally obtained coated aluminum material also increases in thickness as a whole, and the size of the electrode structure using this also increases. The upper limit of the mountain height is preferably 300 μm. However, in the coated aluminum material of the present invention, it does not exclude that the height of the peak from the valley of the uneven portion exceeds 300 μm.

  If the height of the peaks from the valleys of the concavo-convex portions is less than 1 μm, the aluminum material tends not to sufficiently contact the hydrocarbon-containing substance in the heating step for forming the intervening layer. As a result, the intervening layer is not sufficiently generated, and the aluminum material and the coating layer tend not to have sufficient adhesion in the vicinity of the center portion of the surface of the coating aluminum material.

  In the coating layer forming step, (1) after forming the concavo-convex portion on the surface of the aluminum material, or (2) after forming the coating layer on the surface of the aluminum material, to form the concavo-convex portion, The method of the uneven portion forming step is not particularly limited. For example, known techniques such as embossing, pressing, laser processing, and etching can be used.

  When embossing is performed as a method for forming the uneven portion, the pattern shape of the uneven portion is not particularly limited. For example, a known pattern such as a dot, a satin, a lattice, a stripe, a turtle shell, a cloth, a silk, a chile, a wave, or a crepe can be employed.

  For example, when a coated aluminum material is manufactured in a roll shape, the pattern shape of the concavo-convex portion on the roll is changed to a coating layer forming aluminum material (or by passing the aluminum material between two rolls having an embossed shape on at least one side (or By transferring to the surface of the aluminum material, irregularities can be formed on the surface of the coating layer forming aluminum material (or aluminum material). The roll used for embossing may be either single-sided embossing or double-sided embossing. For example, it is possible to make double-sided embossing by suitably adopting a combination of a resin roll or a paper roll, one of which is a metal roll having an uneven portion pattern shape and the other having no uneven portion pattern shape. It is. Moreover, when manufacturing a covering aluminum material in a sheet form, embossing can be formed by sandwiching a sheet-shaped covering layer forming aluminum material (or an aluminum material) in a mold having a pattern shape of an uneven portion on at least one side. Is possible.

  In the coating layer forming step, (3) the method of forming the concavo-convex portion when forming the coating layer having the concavo-convex portion on the surface of the aluminum material is not particularly limited. For example, by forming a desired pattern on a printing plate and creating a height difference in the thickness of the coating layer formed on the surface of the aluminum material, a method for forming uneven portions, or a uniform coating layer on the entire surface of the aluminum material After applying and drying appropriately, the coating layer is again applied only to the desired portion of the coating layer forming aluminum material, thereby producing a height difference in the thickness of the coating layer formed on the surface of the aluminum material. The method of forming etc. are mentioned.

  As a method for forming the concavo-convex portion other than the embossing, a known technique such as pressing, laser processing, etching processing, or the like can be used.

  In the method for manufacturing a coated aluminum material, it is preferable that a plurality of uneven portions are formed in the uneven portion forming step. Moreover, although the shape of the unevenness is not particularly limited, it is preferably linear (striated), latticed, or spotted. For example, shapes such as dots, satin, lattices, stripes, turtle shells, fabrics, silks, chilemen, undulations, crepes, and the like can be given in plan view. Further, a shape in which a plurality of these uneven shapes are combined, or a shape in which these uneven shapes are randomly arranged may be used.

  Further, the concavo-convex portion is not necessarily formed on the entire surface of the coating layer forming aluminum material (or aluminum material). For example, the concavo-convex portion may be formed only in the central portion of the coating layer forming aluminum material (or aluminum material), or the concavo-convex portion may be formed only in the end portion.

  The manufacturing method of a covering aluminum material includes the heating process of arrange | positioning and heating a covering layer formation aluminum material in the space containing a hydrocarbon containing substance.

  In the heating step of the method for manufacturing the coated aluminum material, heating is performed in a state where the coated layer forming aluminum material is disposed in the space containing the hydrocarbon-containing substance. In this case, the coating layer-formed aluminum material may be dried in a temperature range of 20 ° C. or more and 300 ° C. or less as necessary before heating.

  The kind of hydrocarbon-containing substance used in the heating process is not particularly limited. Examples of the hydrocarbon-containing material include paraffinic hydrocarbons such as methane, ethane, propane, n-butane, isobutane and pentane, olefinic hydrocarbons such as ethylene, propylene, butene and butadiene, and acetylenes such as acetylene. Examples thereof include hydrocarbons and derivatives of these hydrocarbons. Among these hydrocarbons, paraffinic hydrocarbons such as methane, ethane, and propane are preferable because they become gaseous in the process of heating the coating layer forming aluminum material. More preferred is any one hydrocarbon among methane, ethane and propane. The most preferred hydrocarbon is methane.

  The hydrocarbon-containing substance may be used in any state such as liquid, gas, solid and the like. The hydrocarbon-containing substance may be present in the space where the coating layer forming aluminum material is present, and may be introduced into the space where the coating layer forming aluminum material is disposed by any method. For example, when the hydrocarbon-containing substance is gaseous (methane, ethane, propane, etc.), the hydrocarbon-containing substance alone or together with an inert gas is filled into the sealed space where the coating layer forming aluminum material is heated. do it. When the hydrocarbon-containing substance is liquid or solid, the hydrocarbon-containing substance may be filled alone or with an inert gas so as to be vaporized by heating in the sealed space.

  The weight ratio of the hydrocarbon-containing substance introduced into the space for heating the coating layer forming aluminum material is not particularly limited. Usually, a weight ratio in the range of about 0.1 to 50 parts by weight in terms of carbon relative to 100 parts by weight of the aluminum material is preferable, and a weight ratio in the range of about 0.5 to 30 parts by weight is more preferable.

  In the heating step, the pressure of the heating atmosphere is not particularly limited, and may be normal pressure, reduced pressure, or increased pressure. Further, the pressure adjustment may be performed at any time during the temperature rise to a certain heating temperature or during the temperature lowering from the certain heating temperature while the pressure is maintained at a certain heating temperature.

  What is necessary is just to set a heating temperature suitably according to a composition etc. of the aluminum material which is a heating object. Usually, it is preferably within a range of 450 ° C. or higher and 660 ° C. or lower, and more preferably within a range of 530 ° C. or higher and 620 ° C. or lower. By setting the heating temperature to 450 ° C. or higher, crystallized aluminum carbide can be contained in the intervening layer containing aluminum and carbon. However, in the production method of the present invention, it does not exclude heating the aluminum material on the surface of which the mixture layer is formed at a temperature lower than 450 ° C., and it is preferable to heat at a temperature exceeding 300 ° C. . Further, when the heating temperature exceeds 660 ° C., the aluminum material may be melted.

  The heating time is preferably in the range of 1 hour to 100 hours, although it depends on the heating temperature and the like.

  When the heating temperature is 400 ° C. or higher, the oxygen concentration in the heating atmosphere is preferably 1.0% by volume or lower. When the heating temperature is 400 ° C. or higher and the oxygen concentration in the heating atmosphere exceeds 1.0% by volume, the thermal oxide film on the surface of the aluminum material may be enlarged and the surface resistance value of the aluminum material may increase.

  A coating comprising an aluminum material, a coating layer formed on the surface of the aluminum material, and an intervening layer containing an aluminum element and a carbon element formed between the aluminum material and the coating layer by the above method (1) The intervening layer is formed in at least a partial region of the surface of the aluminum material and contains aluminum carbide, and (2) the coated aluminum material has an uneven portion on one side or both sides. It is possible to produce a coated aluminum material in which is formed. However, the production of the coated aluminum material of the present invention is not limited to the above method.

(3) Embodiment of coated aluminum material A specific embodiment of the coated aluminum material of the present invention will be described with reference to the drawings.

  FIG. 1 is a view showing a preferred embodiment of the coated aluminum material of the present invention.

  FIG. 1 shows a cross-sectional structure of a coated aluminum material. As an example of the aluminum material 1, a coating layer 2 is formed on the surface of an aluminum foil. An intervening layer 3 is formed between the aluminum foil 1 and the coating layer 2. The intervening layer 3 acts to increase the adhesion between the aluminum foil 1 and the coating layer 2. The intervening layer 3 contains an aluminum element and a carbon element.

  In the coated aluminum material, at least one surface has the uneven portion 4. As a result, even when a plurality of sheet-like coating layer forming aluminum materials are laminated and manufactured, or even when a belt-like coating layer forming aluminum material is rolled and manufactured, the aluminum material is sufficiently hydrocarbon-containing substance. Can be contacted. As a result, the intervening layer 3 is sufficiently formed even near the center of the surface of the coated aluminum material, and the aluminum material 1 and the coating layer 2 can have sufficient adhesion.

  On the surface of the coated aluminum material, the surface portion extends outward from the surface portion of the intervening layer 3 in the form of a fiber, a filament, a whisker, a plate, a wall, or a lump to form a surface portion 21. May be. This is formed between the intervening layer 3 and the coating layer, and includes, for example, aluminum carbide.

  In the coated aluminum material, an uneven portion is formed on at least one surface. In the coated aluminum material in which the coating layer is formed only on one side of the aluminum base material, the concavo-convex portion may be provided on the surface on the coating layer side, or only on the surface of the aluminum material on the side where the coating layer is not provided. It may be provided in both of them. In the coated aluminum material in which the coating layer is formed on both surfaces of the aluminum material, it is only necessary to have an uneven portion on at least one surface.

  The concavo-convex portion 4 is formed to have a desired height H from the valley of the concave portion 41 to the peak of the convex portion 42. Furthermore, the concavo-convex portion 4 is formed at a distance T between the concavo-convex portion 4 and the concavo-convex portion 4 adjacent to each other so as to have a desired interval.

  Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples.

(1) Examples and comparative examples
Example 1
<Coating layer forming step>
A coating solution in which 6 parts by weight of isopropyl alcohol (IPA) is added to 1 part by weight of carbon black (Mitsubishi Chemical Corporation # 2400B) on both sides of aluminum foil (JIS A1050 H-18) with a thickness of 20 μm and 500 mm square. Applied. Next, this was dried at a temperature of 100 ° C. for 10 minutes to form a coating layer containing carbon, and a coating layer-forming aluminum material was produced. The coating solution at this time was adjusted so that the coating layer thickness after drying was 1 μm on one side.

<Concavity and convexity formation process>
The coating layer-formed aluminum material was embossed so that the pressing force during embossing was adjusted and the height of the peaks was from the valleys of the uneven portions described later. The pattern shape of the concavo-convex portion is a dot, the dot type depth of the embossing roll is 55 to 60 μm, and the interval between the pattern shapes of the concavo-convex portion is 317.5 μm.

<Heating process>
In a state where 500 pieces of the coating layer-formed aluminum material after the embossing were placed in contact with each other, the aluminum material was kept in a methane gas atmosphere at a temperature of 600 ° C. for 10 hours to obtain the coated aluminum material of the present invention.

  Based on JIS B7502, for the obtained coated aluminum material, by using a micrometer, by measuring the thickness of the coated aluminum material in which the concavo-convex part was formed and the coating layer forming aluminum material before the concavo-convex part was formed The height of the mountain was calculated from the valleys of the irregularities formed on the coated aluminum material by the following formula.

Calculation formula: (thickness of the coated aluminum material on which the irregularities are formed)
-(Thickness of the coated aluminum material before the uneven portion is formed)
= (Height from the valley of the uneven part)
The results are shown in Table 1.

  Moreover, Ra (center line average roughness) and Rmax (maximum height) were measured according to JIS B0601: 1982 on the surface of the coating layer of the obtained coated aluminum material of the present invention using a surface roughness meter. The results are shown in Table 1.

  A sample was collected from the obtained coated aluminum material, and the surface of the sample was observed using a scanning electron microscope. As shown in FIG. 2, it was confirmed that uneven portions were formed on the surface of the coated aluminum material.

Example 2
<Coating layer forming step>
In the same manner as in Example 1, a coating layer-formed aluminum material was produced.

<Concavity and convexity formation process>
The coating layer-formed aluminum material was embossed by changing the applied pressure during embossing from that of Example 1 so that the height of the ridges was higher than the valleys of the uneven portions described later. The pattern shape of the concavo-convex portion is a dot, the dot type depth of the embossing roll is 55 to 60 μm, and the interval between the pattern shapes of the concavo-convex portion is 317.5 μm.

<Heating process>
A heating step was performed in the same manner as in Example 1 in a state where 500 pieces of the coating layer-formed aluminum material after embossing were brought into contact with each other to obtain the coated aluminum material of the present invention.

  Further, in the same manner as in Example 1, the height of the peak was determined from the valleys of the uneven portions, and Ra and Rmax were measured on the surface of the coating layer of the obtained coated aluminum material of the present invention. The results are shown in Table 1.

Example 3
<Coating layer forming step>
In the same manner as in Example 1, a coating layer-formed aluminum material was produced.

<Concavity and convexity formation process>
The coating layer-formed aluminum material was embossed by changing the pressure applied during embossing from that of Example 1 so that the height of the ridges was higher than the valleys of the uneven portions described later. The pattern shape of the concavo-convex portion is a dot, the dot type depth of the embossing roll is 55 to 60 μm, and the interval between the pattern shapes of the concavo-convex portion is 317.5 μm.

<Heating process>
A heating step was performed in the same manner as in Example 1 in a state where 500 pieces of the coating layer-formed aluminum material after embossing were brought into contact with each other to obtain the coated aluminum material of the present invention.

  Further, in the same manner as in Example 1, the height of the peak was determined from the valleys of the uneven portions, and Ra and Rmax were measured on the surface of the coating layer of the obtained coated aluminum material of the present invention. The results are shown in Table 1.

Example 4
<Coating layer forming step>
In the same manner as in Example 1, a coating layer-formed aluminum material was produced.

<Concavity and convexity formation process>
The coating layer-formed aluminum material was embossed by changing the pressure applied during embossing from that of Example 1 so that the height of the ridges was higher than the valleys of the uneven portions described later. The pattern shape of the concavo-convex portion is a dot, the dot type depth of the embossing roll is 55 to 60 μm, and the interval between the pattern shapes of the concavo-convex portion is 317.5 μm.

<Heating process>
A heating step was performed in the same manner as in Example 1 in a state where 500 pieces of the coating layer-formed aluminum material after embossing were brought into contact with each other to obtain the coated aluminum material of the present invention.

  Further, in the same manner as in Example 1, the height of the peak was determined from the valleys of the uneven portions, and Ra and Rmax were measured on the surface of the coating layer of the obtained coated aluminum material of the present invention. The results are shown in Table 1.

Example 5
<Coating layer forming step>
In the same manner as in Example 1, a coating layer-formed aluminum material was produced.

<Concavity and convexity formation process>
With respect to this covering layer forming aluminum material, the pattern shape of the concavo-convex part at the time of embossing is changed from the dot of Examples 1 to 4 to the satin surface, and the applied pressure is adjusted to be the height of the peak from the valley of the concavo-convex part described later And then embossed. The pattern shape of the concavo-convex part is a satin finish, the depth of the matte form of the embossing roll is 100 to 150 μm, and the interval between the pattern shapes of the concavo-convex part is random.

<Heating process>
A heating step was performed in the same manner as in Example 1 in a state where 500 pieces of the coating layer-formed aluminum material after embossing were brought into contact with each other to obtain the coated aluminum material of the present invention.

  Further, in the same manner as in Example 1, the height of the peak was determined from the valleys of the uneven portions, and Ra and Rmax were measured on the surface of the coating layer of the obtained coated aluminum material of the present invention. The results are shown in Table 1.

Example 6
<Coating layer forming step>
In the same manner as in Example 1, a coating layer-formed aluminum material was produced.

<Concavity and convexity formation process>
For this coating layer-formed aluminum material, the pattern shape of the concavo-convex part at the time of embossing is changed from the dots of Examples 1 to 4 to stripes, and the applied pressure is adjusted to be the height of the peak from the valley of the concavo-convex part to be described later And then embossed. The pattern shape of the concavo-convex portion is a stripe, the depth of the stripe type of the embossing roll is 55 to 60 μm, and the interval between the pattern shapes of the concavo-convex portion is 1 mm.

<Heating process>
A heating step was performed in the same manner as in Example 1 in a state where 500 pieces of the coating layer-formed aluminum material after embossing were brought into contact with each other to obtain the coated aluminum material of the present invention.

  Further, in the same manner as in Example 1, the height of the peak was determined from the valleys of the uneven portions, and Ra and Rmax were measured on the surface of the coating layer of the obtained coated aluminum material of the present invention. The results are shown in Table 1.

Comparative Example 1
In Example 1, a coated aluminum material was obtained in the same manner as in Example 1 except that the uneven portion forming step was not performed.

  Moreover, similarly to Example 1, based on JIS B7502, about the obtained coating aluminum material, the thickness of the coating aluminum material and the coating layer formation aluminum material before a heating process was measured using the micrometer, and the The difference was calculated. Further, Ra and Rmax were measured on the surface of the coating layer of the obtained coated aluminum material. The results are shown in Table 1.

(2) Evaluation method
Evaluation of adhesion Adhesion was evaluated by a taping method. Each evaluation sample was cut into a strip with a width of 10 mm and a length of 50 mm, and a pressure-sensitive adhesive tape having an adhesive surface with a width of 15 mm and a length of 70 mm on the surface of the carbon-containing layer (trade name “Scotch Tape” manufactured by Sumitomo 3M Limited) After pressing, the adhesive tape was peeled off and the adhesion was evaluated according to the following formula.

Adhesion (%) = {weight of carbon-containing layer after peeling (mg)
/ Weight of the carbon-containing layer before peeling (mg)} × 100
In this formula, when no peeling of the carbon-containing layer is observed, the value is 100. The results are shown in Table 1.

Quantitative analysis of intervening layer The amount of intervening layer formed was evaluated by quantitative analysis of aluminum carbide (Al ₄ C ₃ ).

From the coated aluminum material of 500 mm square obtained in Examples 1 to 6 and Comparative Example 1, the end portion (100 mm × 100 mm) and the center portion (100 mm × 100 mm) were cut out as sampling positions to obtain evaluation samples. This sample for evaluation was dissolved in a 20% aqueous sodium hydroxide solution, and the generated methane gas was collected. The generated methane gas was quantitatively analyzed using a highly sensitive gas chromatograph with a flame ionization detector. The quantified amount of methane gas was converted into the weight of aluminum carbide, and the weight per area (mg / cm ² ) on one side was calculated. Aluminum material and aluminum carbide dissolve in 20% sodium hydroxide aqueous solution, but the coating layer does not dissolve, so the amount of carbon element contained in the obtained methane gas is converted to the weight of aluminum carbide (Al ₄ C ₃ ). can do.

Performance evaluation with electric double layer capacitor <Production of electrode>
From the coated aluminum material of 500 mm square obtained in Examples 1 to 6 and Comparative Example 1, the end portion (50 mm × 10 mm) and the center portion (50 mm × 10 mm) were cut out as sampling positions, respectively, and the evaluation base sample and did.

  First, 100 parts by weight of activated carbon (Kuraray Co., Ltd. YP-50F), 5 parts by weight of acetylene black (Denka Black, Denki Kagaku Co., Ltd.), and a thickener carboxymethylcellulose (Daicel Chemical Co., Ltd. 1160) adjusted to 1.2% by weight were added to 2 parts by weight in terms of conversion were mixed. Next, 5 parts by weight of the acrylic emulsion in terms of solid content was mixed. Subsequently, distilled water was further added to obtain a solid content concentration of 25% by weight to prepare an activated carbon slurry.

  Then, apply activated carbon slurry to one side of the evaluation base sample and etched foil (JCC 20CB, conventional example) cut to the same size using an applicator, and dry at 100 ° C for 2 minutes to activate the activated carbon layer. And an evaluation sample as an electrode of an electric double layer capacitor was prepared. The thickness of the activated carbon layer after drying was 55 μm.

<Cell assembly of electric double layer capacitor>
Using each sample for evaluation produced above as an electrode of an electric double layer capacitor, a cell was assembled by the following method.

  Electrolyte solution prepared by dissolving tetraethylammonium tetrafluoroborate in propylene carbonate and adjusting the electrolyte concentration to 1.5 mol / L (trade name “1.5M TEMA-BF4 / PC” manufactured by Toyo Gosei Co., Ltd.) Prepared.

  Next, an evaluation sample was cut into a rectangular shape of 8 cm × 1 cm. And one end 3 cm of 8 cm of the cut out sample for evaluation was scraped off the activated carbon layer and the coating layer to form a 5 cm × 1 cm rectangular electrode (however, since the coating layer is not formed in the conventional example, Only the activated carbon layer was scraped off). The 3 cm portion that was scraped off was used as a tab. This rectangular electrode and separator made of 6cm x 2cm paper with a thickness of 25μm (manufactured by Japan Advanced Paper Industries Co., Ltd.) are placed in a 7.5cm x 7.5cm size laminate film in the order of electrode, separator and electrode. Laminated.

  Next, after 1 mL of the electrolyte solution was injected into the separator, the laminate film was sealed to produce a film cell.

  Next, a metal plate (material: stainless steel) is applied to the top of the film cell, pressure is applied so that the electrode in the film cell does not move, and the state is maintained to produce a film cell type electric double layer capacitor. did.

  As described above, a film cell type electric double layer capacitor was produced for each sample for evaluation, and the capacitance and internal resistance were measured by the following methods.

<Performance evaluation of electric double layer capacitor (capacitance and internal resistance)>
The film cell type electric double layer capacitor was charged to 2.5 V with a constant current of 50 mA. Thereafter, the battery was further charged for 10 minutes, and then discharged at a constant current of 10 mA. The capacitance was determined from the obtained charge / discharge characteristics. The film cell type electric double layer capacitor was charged at a constant current of 50 mA up to 2.5 V for 10 minutes and then discharged at a constant current of 500 mA. The internal resistance was determined from the obtained charge / discharge characteristics.

  Table 1 compares the characteristics of products with and without embossing.

  From the results of Table 1, the coated aluminum material of Comparative Example 1 produced almost no aluminum carbide as an intervening layer at the center.

  On the other hand, in the coated aluminum materials of Examples 1 to 6, the amount of aluminum carbide as an intervening layer increased in the central portion as compared with Comparative Example 1. Thereby, it turned out that the adhesiveness of an aluminum material and a coating layer is improved also in the center part of a covering aluminum material.

  From the results shown in Table 1, it was found that the coated aluminum materials of Examples 1 to 6 had the same capacitance and internal resistance values as those of Comparative Example 1. That is, the coated aluminum material has an uneven portion formed on at least one surface of the outermost layer, but the capacitance and internal resistance may show values equivalent to those of Comparative Example 1 in which the uneven portion is not formed. all right.

  It can be said that the coated aluminum materials of Examples 1 to 6 have little influence on the capacitance and internal resistance, and can be used as an electrode structure.

  The coated aluminum material of the present invention includes an aluminum material, a coating layer formed on the surface of the aluminum material, and an interposition including an aluminum element and a carbon element formed between the aluminum material and the coating layer. The intermediate layer is formed in at least a partial region of the surface of the aluminum material, includes aluminum carbide, and the covering aluminum material has an uneven portion on one or both sides, Even when a sheet-like aluminum material is laminated or when an aluminum material is rolled into a strip shape, the aluminum material and the covering layer are sufficiently adhered.

1: Aluminum material 2: Coating layer 3: Intervening layer 4: Uneven portion 21: Surface portion 41: Concavity 42: Convex portion
H: Height
T: Interval

Claims (12)

A coated aluminum material comprising: an aluminum material; a coating layer formed on a surface of the aluminum material; and an intervening layer containing an aluminum element and a carbon element formed between the aluminum material and the coating layer. And
(1) The intermediate layer is formed in at least a partial region of the surface of the aluminum material, and includes an aluminum carbide.
(2) As for the said covering aluminum material, the uneven | corrugated | grooved part is formed in the single side | surface or both surfaces,
A coated aluminum material characterized by that.   The said uneven | corrugated | grooved part is a covering aluminum material of Claim 1 whose height of a peak from the trough of the said uneven | corrugated | grooved part is 1 micrometer or more and 300 micrometers or less.   2. The coated aluminum material according to claim 1, wherein the unevenness portion has a surface roughness Ra of 0.3 μm or more and 10 μm or less.   The shape of the said uneven | corrugated | grooved part is a covering aluminum material in any one of Claims 1-3 which is any one of a dot, a satin, a lattice, a stripe, a turtle shell, a cloth, a silk, a chirimen, a wave shape, or a crepe.   5. The coated aluminum material according to claim 4, wherein when the uneven portion has a texture, stripe, or crepe, a distance between adjacent stripe-shaped recesses is 1 μm or more and 100 mm or less.   5. The coated aluminum material according to claim 4, wherein the distance between adjacent dot-shaped concave portions is 1 μm or more and 100 mm or less when the shape of the uneven portion is a dot.   The coated aluminum material according to claim 1, wherein the coating layer is a layer containing carbon or a layer containing an inorganic substance.   The coated aluminum material according to any one of claims 1 to 6, wherein the coated aluminum material is used for constituting an electrode structure.   The coated aluminum material according to claim 8, wherein the electrode structure is a current collector or an electrode of a capacitor.   The coated aluminum material according to claim 8, wherein the electrode structure is a battery current collector or an electrode. A method for producing a coated aluminum material,
A coating layer forming step of forming a coating layer on the surface of the aluminum material;
A heating step of arranging and heating the coating layer forming aluminum material in a space containing a hydrocarbon-containing substance,
The covering layer forming step includes an uneven portion forming step of forming an uneven portion on one side or both sides of the aluminum material or the covering layer forming aluminum material.
A method for producing a coated aluminum material.   The method for producing a coated aluminum material according to claim 11, wherein the concavo-convex portion forming step forms a concavo-convex portion having a peak height from 1 μm to 300 μm by embossing.

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