CN104364401A - Aluminum alloy foil and method for producing same, molded package material, secondary battery, and pharmaceutical packaging container - Google Patents

Aluminum alloy foil and method for producing same, molded package material, secondary battery, and pharmaceutical packaging container Download PDF

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Publication number
CN104364401A
CN104364401A CN201380021238.6A CN201380021238A CN104364401A CN 104364401 A CN104364401 A CN 104364401A CN 201380021238 A CN201380021238 A CN 201380021238A CN 104364401 A CN104364401 A CN 104364401A
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alloy foil
degree
directions
cold rolling
wrapping body
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CN104364401B (en
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石雅和
铃木觉
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Nippon Foil Manufacturing Co Ltd
UACJ Corp
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UACJ Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
    • B65D75/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
    • B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D83/00—Containers or packages with special means for dispensing contents
    • B65D83/04—Containers or packages with special means for dispensing contents for dispensing annular, disc-shaped, or spherical or like small articles, e.g. tablets or pills
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Wrappers (AREA)
  • Metal Rolling (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention provides an aluminum alloy foil with good formability. The aluminum alloy foil of the present invention contains Fe: 0.8 to 2.0 mass%, Si: 0.05 to 0.2 mass%, Cu: 0.0025 to 0.2 mass%, and the balance of Al and inevitable impurities, wherein the aluminum alloy foil has a Cube orientation density of 5 or more and an R orientation density of 50 or less in crystal orientation on the surface thereof, and the aluminum alloy foil has an average crystal grain size of 7 to 20 μm.

Description

Alloy foil and manufacture method, shaping wrapping body material, secondary cell, pharmaceuticals packaging vessel
Technical field
The present invention relates to the alloy foil and manufacture method, shaping wrapping body material, secondary cell, pharmaceuticals packaging vessel with high formability.
Background technology
The PTP (being packed by pressure) that is known as the shaping wrapping body material of packaging pharmaceuticals, often takes the form of being packed by combination container and covering material.Containers demand can carry out drawing and forming, and in conventional stick pack body, container adopts the molding of the resin molding of plastic film such as polypropylene etc.Particularly, require the tablet etc. of the content of water vapor barrier property when keeping, be often used as the complex body of aluminium foil high for barrier and resin molding being fitted with single or double.In recent years, pharmaceuticals had various form, size, and the wrapping body packing it also mates with these forms, also needed till now to be deeper shaped.
On the other hand, as the exterior material of the shaping wrapping body material of secondary cell, in order to give water vapor barrier property, also adopt the material of the structure of the complex body had alloy foil two sides laminating resin molding.In recent years, along with the miniaturization of the electronicss such as mobile communication equipment, subnotebook PC, earphone stereo, pick up camera, the secondary cell of the lithium-ion secondary cell that sheet is slim etc., more and more paid attention to as its drive source, the charging capacity of energy life-time service or high output are required to secondary cell.For this reason, the structure of the element be made up of the electrode of battery, separating part (separator) becomes complicated/multiple stratification, and more and more requirement can be shaped under the exacting terms of darker recess shaping etc.
Particularly, in the exterior material of the slim lithium-ion secondary cell of sheet, carry out making the angle cylinder drawing and forming that the radius R in the shoulder of contoured recess corner and bight is less, forming height is darker.Its result, the loading level that can be contained in the electrode materials in contoured recess increases, and can improve cell container further.At present, the exterior material for lithium-ion secondary cell requires higher plasticity, also requires higher plasticity for the alloy foil forming exterior material.
Generally speaking, as shown in Figure 2, in the wrapping body 1 of shaping, at a surface layer folded laminating hot sealing layer 9 of exterior material main body 8, in another surface layer folded laminating synthetic resins masking 10.As shown in Figure 1, in order to receive the duplexer of positive electrode collector 2 grade, wrapping body 1 is configured as that its central part becomes recess, periphery becomes par.Thus, exterior material main body 8, hot sealing layer 9 and synthetic resins masking 10 need to adopt the good material of plasticity.
In the past, as exterior material main body 8, be applicable to adopting moisture, air etc. difficult through and the tinsel had excellent formability, particularly alloy foil, so that can not detrimentally affect be produced to the quality of content.As this alloy foil, mainly adopt the composition etc. of regulation in JIS1100,3003,8079 or 8021.
Such as, as exterior material main body 8, motion has thickness to be 20 ~ 60 μm, is all the aluminium foil (patent documentation 1) of more than 11% relative to rolling direction along the elongation in 0 degree, 45 degree, 90 degree direction.In addition, similarly as exterior material main body 8, motion has and is 0.8 ~ 2.0% containing Fe, is 0.02 ~ 0.05% containing Cu, is the alloy foil that the erosion resistance of 0.03 ~ 0.1% is outstanding containing Si.(patent documentation 2).
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Unexamined Patent Publication 2005-163077 publication
[patent documentation 2] Japanese Patent No. 4799903 publications
Summary of the invention
[inventing problem to be solved]
But, in the prior art that above-mentioned document is recorded, the characteristic of the forming height high as the nearest exterior material for PTP, lithium-ion secondary cell etc. that is difficult to meet the demands fully.
The first, in the alloy foil of patent documentation 1, when carrying out as formed the so harsh angle cylinder drawing and forming of darker recess, have break in its periphery generation of contoured recess, the situation of pin hole.Namely, if formed machining alloy foil being implemented to more shallow recess is just no problem, but use alloy foil to be shaped darker recess at the central part of wrapping body in order to the capacity increasing content, then have easily to produce at the particularly recess of exterior material main body and the boundary portion of par and break, become moisture, air etc. easily through, the such shortcoming of dysgenic wrapping body is produced to the quality of content.Particularly, when using as secondary cell exterior material purposes, if moisture, air permeable, then become generate hydrofluoric acid because reacting with the ionogen of inside battery, environment that inside battery is easily corroded.
And then, in the alloy foil of patent documentation 1, in order to improve plasticity, to make relative to the elongation values in 0 degree, 45 degree, 90 degree direction of rolling direction be more than 11%, but for the tensile strength relative to above-mentioned each rolling direction, the value of 0.2% yield strength is larger, due to when angle cylinder drawing and forming, increase the resistance of the material of inflow from flange part, therefore can not improve forming height.
The second, in the alloy foil of patent documentation 2, control the number of alloy compositions and intermetallic compound to improve erosion resistance and intensity, but for raising plasticity, the physical property only controlling these is not enough.
The present invention conceives in view of the foregoing, its object is to provide the alloy foil and manufacture method, shaping wrapping body material, secondary cell, pharmaceuticals packaging vessel with the good plasticity solving above-mentioned problem.
[for solving the technical scheme of problem]
The present inventor is studied the alloy foil used as profile wrappers, found that and limit component and the alloy foil obtained in suitably scope, shaping wrapping body material, secondary cell, pharmaceuticals packaging vessel is outstanding especially, and find in the manufacturing process of above-mentioned alloy foil by controlling homogenize treatment temp and the intermediate anneal temperature of ingot bar, and then from the cold rolling rate after hot rolling before process annealing and from after process annealing to becoming the thick cold rolling rate of last paper tinsel, stablize and reliably obtain above-mentioned outstanding alloy foil, thus reach the present invention.
Namely, according to the present invention, a kind of alloy foil is provided, it contains Fe:0.8 ~ 2.0mass%, Si:0.05 ~ 0.2mass%, Cu:0.0025 ~ 0.2mass%, remainder is made up of Al and inevitable impurity, in above-mentioned alloy foil, on the crystalline orientation on above-mentioned alloy foil surface, Cube orientation density (Orientation density) is more than 5, R orientation density is less than 50, and the average crystallite particle diameter of above-mentioned alloy foil is 7 ~ 20 μm.
According to this alloy foil, due on the composition of alloy foil and the crystalline orientation on surface, Cube orientation density and R orientation density and average crystal grain footpath meet specific condition, so can obtain the alloy foil with good plasticity.
Particularly, above-mentioned alloy foil further preferably, relative to 0 of rolling direction degree, in the respective tensile strength TS in 45 degree, 90 degree directions and 0.2% yield strength YS, the value of the TS on 45 degree of directions × (TS/YS) is 200N/mm in above-mentioned alloy foil 2above, the absolute value of the difference of TS × (TS/YS) in 0 degree of direction and 45 degree of directions is 30N/mm 2below, the absolute value of the difference of TS × (TS/YS) in 45 degree of directions and 90 degree of directions is 30N/mm 2below.
By such regulation, alloy foil of the present invention improves the ultimate deformation ability of alloy foil, and can suppress the generation of the micro-cracks etc. at the angle cylinder drawing and forming initial stage, therefore, it is possible to raising forming height.In addition, due to the resistance from the material of flange part inflow during minimizing angle cylinder drawing and forming, therefore, it is possible to improve forming height.
In addition, according to the present invention, the shaping wrapping body material possessing above-mentioned alloy foil is preferably provided.According to this shaping wrapping body material, owing to adopting, there is the alloy foil of above-mentioned good plasticity, therefore can improve forming height, and to be shaped darker recess as the shaping wrapping body material of secondary cell exterior material etc.Its result, increases the amount that can be contained in contoured recess, thus can improve capacity further.
In addition, according to the present invention, the secondary cell adopting above-mentioned shaping wrapping body material is preferably provided.According to this secondary cell, owing to adopting the shaping wrapping body material with above-mentioned darker contoured recess, so increase the loading level of the battery material of the electrode materials that can be contained in the contoured recess of secondary cell exterior material etc., contribute to improving cell container etc. further, the high performance of secondary cell can be contributed to.
In addition, according to the present invention, the pharmaceuticals packaging vessel adopting above-mentioned shaping wrapping body material is preferably provided.According to this pharmaceuticals packaging vessel, owing to adopting the shaping wrapping body material with above-mentioned darker contoured recess, therefore can be contained in the contoured recess of pharmaceuticals packaging vessel, therefore the saturation of pharmaceuticals, the degree of freedom of shape screening can be improved further.
In addition, according to the present invention, a kind of manufacture method of above-mentioned alloy foil is provided, comprising: the aluminium alloy ingot bar that Fe:0.8 ~ 2.0mass%, Si:0.05 ~ 0.2mass%, Cu:0.0025 ~ 0.2mass%, remainder are made up of Al and inevitable impurity, less than the 620 DEG C maintenance operations of more than 1 hour that homogenize more than 500 DEG C; After this homogenizes maintenance, implement hot rolling and cold rolling operation; In the midway that this is cold rolling, implement the operation of the process annealing that less than 450 DEG C keep more than 300 DEG C; The cold rolling rate after this hot rolling before this process annealing is made to be less than 85% implement cold rolling operation; Make after this process annealing to become last paper tinsel thick cold rolling rate be less than more than 80% 93% implement cold rolling operation; And the operation of described alloy foil is obtained at this cold rolling rear enforcement final annealing.
According to the manufacture method of this alloy foil, due to the aluminium alloy ingot bar of specific operation process specific composition, so following whole (1)-(3) can be met, and can reliably obtain the alloy foil with high formability.
(1) the average crystallite particle diameter of alloy foil;
(2) the crystalline orientation density on alloy foil surface;
(3) relative to the strength balance in 0 degree, 45 degree, 90 degree direction of rolling direction.
[invention effect]
Alloy foil of the present invention, because the orientation density of the regulation of average crystallite particle diameter, aluminium alloy obtains optimum control, so the alloy foil being suitable for requiring the shaping wrapping body material of high plasticity as lithium-ion secondary cell, pharmaceuticals packaging vessel etc. can be provided.
Accompanying drawing explanation
Fig. 1 is the schematic sectional view of an example of the internal structure that the lithium-ion secondary cell that sheet is slim is shown.
Fig. 2 is the schematic sectional view of the general example of the exterior material that secondary cell is shown.
[embodiment]
(1) composition of alloy foil
In the present embodiment, the amount of Fe that alloy foil comprises is 0.8 ~ 2.0mass%.If the amount of Fe is less than 0.8mass%, then tensile strength TS and 0.2% yield strength YS together declines, and therefore diminishes relative to the value of TS × (TS/YS) in 45 degree of directions of above-mentioned rolling direction, and the plasticity of alloy foil declines.In addition, if the amount of Fe is more than 2.0mass%, then easily forms huge intermetallic compound when casting, easily becoming the starting point of breaking during the cylinder drawing experiments of angle, therefore plasticity declines.From the viewpoint of intensity, preferred more than the 1.1mass% of the amount as this Fe, below 1.6mass%.As the amount of this Fe, be such as 0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0mass%, also can be in the scope between any 2 values of this illustrative numerical value.
In the present embodiment, the amount of Si that alloy foil comprises is 0.05 ~ 0.2mass%.If the amount of Si is less than 0.05mass%, then tensile strength TS and 0.2% yield strength YS declines, and therefore diminishes relative to the value of TS × (TS/YS) in 45 degree of directions of above-mentioned rolling direction, and plasticity declines.In addition, highly purified matrix metal (Al) is used to be uneconomic.On the other hand, if the amount of Si is more than 0.2mass%, then the crystallisate size in alloy foil becomes large, and the number of crystallisate reduces.Its result, because the average crystallite particle diameter after final annealing becomes large, so the shaping easily uneven when being formed, thus reduces the plasticity of alloy foil.The amount of Si, from particularly preferably more than 0.06mass%, below 0.1mass% the viewpoint in intensity and average crystal grain footpath.As the amount of this Si, be such as 0.05,0.06,0.07,0.08,0.09,0.10,0.11,0.12,0.13,0.14,0.15,0.16,0.17,0.18,0.19,0.20mass%, also can be in the scope between any 2 values of this illustrative numerical value.
In the present embodiment, the amount of Cu that alloy foil comprises is 0.0025 ~ 0.2mass%.The intensity of alloy foil is improved by adding Cu.If the amount of Cu is less than 0.0025mass%, then tensile strength TS and 0.2% yield strength YS reduces respectively, diminishes relative to the value of TS × (TS/YS) in 45 degree of directions of above-mentioned rolling direction, thus the plasticity of alloy foil declines.In addition, if the amount of Cu is more than 0.2mass%, then the Cube orientation density on alloy foil surface declines, and therefore the plasticity of alloy foil declines.The amount of Cu, from the viewpoint of the crystalline orientation on intensity and alloy foil surface, particularly preferably more than 0.005mass%, below 0.05mass%.As the amount of this Cu, be such as 0.0025,0.0100,0.0150,0.0200,0.0250,0.0300,0.0350,0.0400,0.0500,0.0600,0.0700,0.0800,0.0900,0.1000,0.1100,0.1200,0.1300,0.1400,0.1500,0.1600,0.1700,0.1800,0.1900,0.2000mass%, also can be in the scope between any 2 values of this illustrative numerical value.
In the present embodiment, the inevitable impurity that alloy foil comprises is respectively below 0.05mass%, amounts to below 0.15mass%.Particularly, if the inevitable impurity of Ti, Mn, Mg, Zn etc. is respectively for 0.05mass% and altogether more than 0.15mass%, then sclerosis when rolling is comparatively large, easily produces the slight crack in calendering.
(2) physical property of alloy foil
In the present embodiment, the average crystallite particle diameter after the final annealing in alloy foil is more than 7 μm, less than 20 μm.Preferably more than 10 μm, less than 18 μm.This average crystallite particle diameter, such as, be 7,8,9,10,11,12,13,14,15,16,17,18,19,20 μm, also can be in the scope between any 2 of this illustrative numerical value.
In addition, the average crystallite particle diameter in alloy foil can be measured by existing method, such as, can adopt the process of chopping to measure.The so-called process of chopping has several crystal grain in index line segment, asks line segment divided by the method for the size of this number.
The average crystallite particle diameter of the alloy foil after final annealing receives the impact of amount of element and various conditions when manufacturing of adding greatly.Particularly be subject to the impact of the amount of added Fe and Si, the cold rolling rate after process annealing to last paper tinsel is thick and final annealing condition to a great extent.In order to obtain the average crystallite particle diameter of above-mentioned record, need the Addition ofelements amount and the manufacturing condition that adjust these aptly.Average crystallite particle diameter when being less than 7 μm due to alloy foil is meticulous, the increasing amount of 0.2% yield strength YS is larger than tensile strength TS, therefore reduce relative to the value of TS × (TS/YS) in 45 degree of directions of rolling direction, the plasticity of alloy foil declines.On the other hand, if the average crystallite particle diameter of alloy foil is more than 20 μm, then the number of the crystal grain shared by thickness of slab cross-sectional direction is few, therefore easily causes the localization of distortion, thus the plasticity of alloy foil declines.
In the present embodiment, after the final anneal, the Cube orientation density on paper tinsel surface is more than 5, R orientation density is less than 50 to alloy foil.It is further preferred that after the final anneal, the Cube orientation density on paper tinsel surface is less than 30 with more than 7, R orientation density.
In addition, the numerical value of Cube orientation density and R orientation density all represents the multiple for random crystalline orientation density.
Cube orientation is so that {, for representing orientation, R orientation is so that { 123} < 634 > is for representing orientation for 001} < 100 >.When measuring the crystalline orientation density on alloy foil surface, measure that { 100}, { 110}, { the incomplete pole graph of 111} carries out three-dimensional crystals orientation parsing (ODF) and investigates based on these.In addition, in these parsing, to the test portion with random crystalline orientation made by aluminium powder form be measured and the data that obtain as to { 100}, { 110}, { the normalization file used when 111} pole graph is resolved, by this to obtain various orientation density to the multiple of the test portion with random orientation.In addition in the present invention, crystalline orientation density all resolves (ODF) based on three-dimensional crystals orientation.
If the Cube orientation density on alloy foil surface be less than 5 and R orientation density more than 50, then the initial stage when angle cylinder drawing and forming easily forms small fracture etc. at shoulder, therefore alloy foil plasticity decline.As Cube orientation density, be such as 5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29, more than 30, also can be in the scope between any 2 of this illustrative numerical value.In addition, as R orientation density, such as, be 50,45,40,35,30,25,20,15,10,9,8,7,6,5,4,3,2, less than 1, also can be in the scope between any 2 values of this illustrative numerical value.
The alloy foil of present embodiment, does not almost have material to flow into from flange part at the initial stage of angle cylinder drawing and forming, forms shoulder by the convex forming mode of drum.Particularly, as required the lithium-ion secondary cell of high cell container, when the radius R of shoulder is formed smaller, local gross distortion is become for shoulder, easily produces the defect of micro-cracks etc., therefore often with this defect for starting point causes fracture.That is, at the initial stage of the angle cylinder drawing and forming of formation shoulder, reduce the generation of the micro-cracks formed when drum is convex to be shaped etc., this is very important to improving forming height.
By carrying out optimization to the Cube orientation density on alloy foil surface and R orientation density, the ultimate deformation ability of alloy foil is improved thus, therefore there is the alloy foil surface the local convex shaping of drum is such to produce in the deformation processing of larger strain, be difficult to the effect occurring with necking down the plasticity instability being representative.Its result, can suppress the generation of the micro-cracks etc. at the angle cylinder drawing and forming initial stage being formed with shoulder, therefore can improve forming height.
At this, carry out describing to the meaning of TS × (TS/YS) formula.(TS/YS) value is the ratio of the 0.2% yield strength YS for tensile strength TS, the present inventor finds that more large than the value of the regulation region that can obtain being out of shape uniformly of this value is more, during the cylinder drawing and forming of angle, material easily flows into flange part, and tensile strength TS is higher more improves resistance to breaking property.That is, for the mechanical characteristics desired by the alloy foil that can use in the present embodiment, the material that preferably tensile strength TS is high, 0.2% yield strength YS is low in the scope rationalized.The value of this (TS/YS) is multiplied the value of the tensile strength TS corresponding with resistance to disruptive force and TS × (TS/YS), can be used as in present embodiment very high with the correlationship of forming height, represent angle cylinder drawing and forming test in one of the index of plasticity.Among 0 degree, 45 degree, 90 degree directions of the rolling direction relative to alloy foil, TS × (TS/YS) being difficult to 45 degree of directions of the rolling direction flowed in angle flange part during the cylinder drawing and forming of angle relative to material is higher, and the forming height of alloy foil is also more good.
In the present embodiment, alloy foil preferably relative in the tensile strength TS in 0 degree, 45 degree, 90 degree direction of rolling direction and 0.2% yield strength YS, meets 200N/mm relative to the value of TS × (TS/YS) in 45 degree of directions of rolling direction 2above.Be more preferably 210N/mm 2above.Relative to the value of TS × (TS/YS) in 45 degree of directions of rolling direction, be such as 200,201,202,203,204,205,206,207,208,209,210,215,220,230,240,250N/mm 2, also can be in the scope between any 2 values of this illustrative numerical value.
200N/mm is less than relative to the value of the TS in 45 of rolling direction degree of directions × (TS/YS) in the alloy foil of present embodiment 2time, be difficult to the plasticity improving alloy foil.In the angle cylinder drawing and forming test of the thinner profile wrappers of thickness of slab as in the present embodiment, along with forming height uprises, the angle flange part of corner becomes the inflow resistance reducing lip deforms and material and becomes large, thus becomes material and be difficult to flow into.Particularly, in angle flange part when angle cylinder drawing and forming, with compared with the 0 degree of direction of rolling direction being equivalent to straight flange direction or short side direction or 90 degree of directions, become relative to the material in 45 degree of directions of rolling direction and be difficult to flow into, therefore effectively can increase the material influx in 45 degree of directions relative to rolling direction.
In addition, about the measurement relevant with 0.2% yield strength YS to the tensile strength TS in 0 degree, 45 degree, 90 degree direction of the rolling direction relative to alloy foil in present embodiment, known method can be adopted.
In the present embodiment, alloy foil is preferably relative to the absolute value of the difference of 0 degree of direction of rolling direction and TS × (TS/YS) in 45 degree of directions and meet 30N/mm respectively relative to the absolute value of the difference of 45 degree of directions of rolling direction and TS × (TS/YS) in 90 degree of directions 2below.Be more preferably 10N/mm 2below.Relative to 0 of rolling direction degree of direction and the absolute value of difference of TS × (TS/YS) in 45 degree of directions or the absolute value of the difference of TS × (TS/YS) in 45 degree of directions and 90 degree of directions in alloy foil in present embodiment, be such as 30,25,20,15,10,9,8,7,6,5,4,3,2,1,0N/mm 2, also can be in the scope between any 2 values of this illustrative numerical value.
Because material becomes and is difficult to flow in the cylinder drawing and forming hour angle flange part of angle, particularly increase material along relative to the influx in 45 degree of directions of rolling direction, and make also there is no the difference of absolute value as well relative to material influx on 0 degree of direction of rolling direction and 90 degree of directions as far as possible.
For this reason, make relative to 0 degree of direction of rolling direction and 45 degree of directions, as far as possible little relative to the absolute value of the difference of 45 degree of directions of rolling direction and the material influx in 90 degree of directions, this has larger effect concerning the plasticity improving alloy foil.If relative to the absolute value of the difference of 0 degree of direction of rolling direction and the absolute value of difference of TS × (TS/YS) in 45 degree of directions and 45 degree of directions relative to rolling direction and TS × (TS/YS) relative to 90 degree of directions of rolling direction respectively more than 30N/mm 2, then when angle cylinder drawing and forming, material, to the inflow balance deterioration of flange part, therefore has the situation that the plasticity of alloy foil declines.
In the present embodiment, the elongation of alloy foil adjusts aptly by changing average crystallite particle diameter, intensity etc., and the plasticity of higher value then alloy foil also becomes better.Specifically, if in alloy foil relative to 0 of rolling direction degree, the elongation values in 45 degree, 90 degree directions is all more than 17%, then the plasticity of alloy foil becomes good, is therefore preferred.Be more preferably all more than 20% relative to the elongation values in 0 degree, 45 degree, 90 degree direction of rolling direction.
In the present embodiment, the thickness of alloy foil is arbitrary value, can be suitable for adjustment according to purposes, formation condition etc., but, be generally preferably 10 ~ 100 μm.When manufacturing thickness and being less than the alloy foil of 10 μm, easily there is the slight crack etc. when pin hole or calendering, thus easily reduce production efficiency.In addition, if the thickness of alloy foil is more than 100 μm, then the thickness of wrapping body entirety becomes blocked up, is difficult to the miniaturization seeking getable formation wrapping body, therefore not preferred.
(3) manufacture method of alloy foil
Alloy foil is in the present embodiment manufactured by following operation: will containing Fe:0.8 ~ 2.0mass%, Si:0.05 ~ 0.2mass%, Cu:0.0025 ~ 0.2mass%, remainder by Al and the inevitable aluminium alloy ingot bar that forms of impurity, more than 500 DEG C, less than the 620 DEG C maintenance operations of more than 1 hour that homogenize; After this homogenizes maintenance, implement hot rolling and cold rolling operation; In the midway that this is cold rolling, implement the operation of the process annealing that less than 450 DEG C keep more than 300 DEG C; The cold rolling rate after this hot rolling before process annealing is made to be less than 85% implement cold rolling operation; Make after this process annealing to become last paper tinsel thick cold rolling rate be more than 80%, less than 93% implement cold rolling operation; And the operation of above-mentioned alloy foil is obtained at this cold rolling rear enforcement final annealing.Below, the manufacture method with regard to the alloy foil in present embodiment is described in detail.
The manufacture method of the alloy foil in present embodiment, preferably after melting has the aluminium alloy of above-mentioned composition, obtains ingot bar according to D.C.casting method.After this, aluminium alloy ingot bar is homogenized process.This process that homogenizes be more than 500 DEG C, less than 620 DEG C keep more than 1 hour.After this homogenizes process, start hot rolling.Homogenizing in process, the basis that the size of Fe class precipitate is increased makes it comparatively to distribute with dredging, thus the effect reducing Fe solid solution capacity can be expected.
When homogenize process condition be less than 500 DEG C and be less than 1 hour hold-time, because Fe class precipitate can not coarsening fully, therefore the precipitate of the Fe class that Fe solid solution capacity is high, small is also many, therefore 0.2% yield strength uprises, in the tensile strength TS and 0.2% yield strength YS in 45 degree of directions relative to rolling direction, the TS × value of (TS/YS) becomes and is less than 200N/mm 2, the plasticity of alloy foil declines, therefore not preferred.In addition, the segregation formed when casting existed in ingot bar can not also be eliminated fully.
If homogenize, the temperature of process is more than 620 DEG C, then have the situation of ingot bar melting partly, not preferred in manufacture.In addition, the few hydrogen be mixed into when casting overflows surface and easily expands in material surface generation, therefore not preferred.Make it the viewpoint of comparatively dredging distribution from the size increasing Fe class precipitate, about the treatment temp that homogenizes, be preferably more than 550 DEG C, less than 620 DEG C, be more preferably more than 580 DEG C, less than 615 DEG C.The temperature processed that homogenizes is such as 550,560,570,580,590,600,610,615,620 DEG C, also can be in the scope between any 2 values of this illustrative numerical value.
In addition about the hold-time homogenized, be preferably more than 2 hours, be more preferably more than 5 hours.In addition the hold-time homogenized is such as more than 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 hour, also can be in the scope between any 2 values of this illustrative numerical value.
After the above-mentioned process that homogenizes, start hot rolling after aluminium alloy ingot bar is cooled to more than 400 DEG C, less than 500 DEG C and also can.By implementing this cooling, reducing Fe solid solution capacity while the size of Al-Fe class precipitate is increased, thus 0.2% yield strength of alloy foil can be reduced.When the beginning temperature of hot rolling is less than 400 DEG C, the amount of precipitation of small Al-Fe class precipitate becomes too much and 0.2% yield strength improves, in the tensile strength TS and 0.2% yield strength YS in 45 degree of directions relative to above-mentioned rolling direction, the TS × value of (TS/YS) becomes and is less than 200N/mm 2, the plasticity of alloy foil declines, therefore not preferred.If the beginning temperature of hot rolling is more than 500 DEG C, the Fe amount being then solid-solution in alloy foil increases, therefore 0.2% yield strength uprises, and in the tensile strength TS and 0.2% yield strength YS in 45 degree of directions relative to above-mentioned rolling direction, the TS × value of (TS/YS) becomes and is less than 200N/mm 2, the plasticity of alloy foil declines, therefore not preferred.From the viewpoint making the size of Fe class precipitate increase, the beginning temperature of hot rolling is more preferably more than 400 DEG C, less than 450 DEG C.The beginning temperature of hot rolling, such as, be 400,410,425,450,475,500 DEG C, also can be in the scope between any 2 values of this illustrative numerical value.
Because wish to make aluminium alloy plate to try one's best recrystallize during hot rolling, so the end temp of hot rolling is preferably 250 ~ 400 DEG C.From needing the viewpoint making the aluminium alloy plate recrystallize after hot rolling more reliably, recommend to be more preferably more than 300 DEG C, less than 400 DEG C.The end temp of hot rolling, such as, be 250,260,270,280,290,300,310,320,330,340,350,360,370,380,390,400 DEG C, also can be in the scope between any 2 values of this illustrative numerical value.And then, after above-mentioned hot rolling, implement cold rolling to obtained aluminium alloy plate.This is cold rolling can be undertaken by known method, does not limit especially.
The manufacture method of the alloy foil in present embodiment, need carrying out above-mentioned cold rolling midway to aluminium alloy plate, more than 300 DEG C, less than 450 DEG C are carried out process annealing.Improve the viewpoint of calenderability from making aluminium alloy plate recrystallize, the temperature of process annealing is preferably more than 320 DEG C, less than 400 DEG C.The temperature of process annealing, such as, be 300,310,320,330,340,350,360,370,380,390,400,410,420,430,440,450 DEG C, also can be in the scope between any 2 values of this illustrative numerical value.
When the temperature of process annealing is less than 300 DEG C, during final annealing, the crystal grain of alloy foil easily becomes coarsening, can hinder the homogeneity of distortion, has the situation reducing forming height, therefore not preferred.
In addition, if the temperature of process annealing is more than 450 DEG C, then Fe solid solution capacity increases, thus 0.2% yield strength increases, therefore, in the tensile strength TS and 0.2% yield strength YS in 45 degree of directions relative to above-mentioned rolling direction, the TS × value of (TS/YS) becomes and is less than 200N/mm 2, the plasticity of getable alloy foil declines, therefore not preferred.
By implementing process annealing, make aluminium alloy plate recrystallize to reach the object improving calenderability.The enforcement time for process annealing does not limit especially, but is preferably more than 1 hour to make it recrystallize.Be more preferably more than 4 hours.The enforcement time of process annealing is such as more than 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 hour, also can be in the scope between any 2 values of this illustrative numerical value.
In addition, when not implementing process annealing in cold rolling operation, from after hot rolling to become last paper tinsel thick cold rolling rate become large, in the crystalline orientation of therefore alloy foil after the final anneal, desired Cube orientation density and R orientation density can not be obtained, the plasticity of alloy foil declines, therefore not preferred.
The manufacture method of alloy foil in the present embodiment, to the aluminium alloy plate obtained by above-mentioned hot rolling, make the cold rolling rate after above-mentioned hot rolling before above-mentioned process annealing be less than 85% implement cold rolling.If from the cold rolling rate after hot rolling before process annealing more than 85% implement cold rolling, in the recrystallize set tissue of then alloy foil after the final anneal, can not obtain desired Cube orientation density and R orientation density, ultimate deformation ability declines, therefore not preferred.Such as, producing in the deformation processing of larger strain on alloy foil surface as the convex shaping of local drum, producing the plasticity instability as with necking down being representative, having the situation that the plasticity of alloy foil declines.Also have take into account hot rolling terminate thickness of slab and after process annealing is implemented to become last paper tinsel thick the situation of cold rolling rate, but importantly reduce the cold rolling rate after hot rolling before process annealing.Cold rolling rate after hot rolling before process annealing is such as 50,55,60,65,70,75,80, less than 85%, also can be in the scope between any 2 values of this illustrative numerical value.
The manufacture method of alloy foil in the present embodiment, make the cold rolling rate after above-mentioned process annealing to last paper tinsel is thick be more than 80%, less than 93% implement cold rolling.From the cold rolling rate after process annealing to last paper tinsel is thick to the crystalline orientation on the average crystallite particle diameter of the alloy foil after final annealing, alloy foil surface, have an impact relative to the strength balance in 0 degree, 45 degree, 90 degree direction of rolling direction.When above-mentioned cold rolling rate is less than 80%, the crystal grain of the alloy foil after final annealing becomes large, the plasticity of alloy foil decline and and not preferred.On the other hand, if above-mentioned cold rolling rate is more than 93%, average crystallite particle diameter then after final annealing brings impact to by granular the increasing amount of 0.2% yield strength YS, and diminish relative to the value of the TS in 45 of rolling direction degree of directions × (TS/YS) in alloy foil and the plasticity of alloy foil declines, therefore not preferred.And then, by increasing from the cold rolling rate after process annealing to last paper tinsel is thick, obtain desired Cube orientation density and the R orientation density on the alloy foil surface after final annealing, therefore in alloy foil relative in the strength balance of 0 of rolling direction degree, 45 degree, 90 degree, be greater than 45 degree of directions and 90 degree of directions relative to the intensity in 0 degree of direction of rolling direction.Its result, only become large relative to the value of TS × (TS/YS) in 0 degree of direction of rolling direction, become large relative to the difference of 0 degree of direction of rolling direction and TS × (TS/YS) in 45 degree of directions, thus the plasticity of alloy foil declines, therefore not preferred.From the cold rolling rate after process annealing to last paper tinsel is thick, be such as 80.0,81.0,82.0,83.0,84.0,85.0,86.0,87.0,88.0,89.0,90.0,91.0,92.0,93.0%, also can be in the scope between any 2 values of this illustrative numerical value.
After cold rolling end, preferably implement final annealing thus make alloy foil become soft paper tinsel completely.From making it recrystallize completely and the viewpoint making ROLLING OIL volatilize completely, the condition optimization of final annealing carries out more than 5 hours at 200 ~ 400 DEG C.More preferably carry out more than 20 hours at 250 ~ 350 DEG C.As the temperature of final annealing, be such as 200,210,220,230,240,250,260,270,280,290,300,310,320,330,340,350,360,370,380,390,400 DEG C, also can be in the scope between any 2 values of this illustrative numerical value.As the time of final annealing, such as, be more than 5,10,20,30,40,50,60,70,80,90,100,110,120,130,140,150 hours, also can be in the scope between any 2 values of this illustrative numerical value.
When the temperature of final annealing is less than 200 DEG C, due to can not perfect recrystallization, so there be the situation that can not obtain desired paper tinsel.In addition, if the temperature of final annealing is more than 400 DEG C, then the situation that in annealing, crystallization is had the plasticity of alloy foil to decline by coarsening, therefore not preferred.Hold-time when final annealing is when being less than 5 hours, ROLLING OIL during paper tinsel calendering can not be volatilized fully, therefore the situation that paper tinsel wettability of the surface reduces is had, particularly when using the alloy foil of present embodiment as shaping wrapping body material, have the situation that the adaptation of carrying out stacked resin molding with alloy foil easily reduces.
Heat-up rate during final annealing does not limit especially, but, preferably implements at 50 DEG C/below hr.If heat-up rate during final annealing is more than 50 DEG C/hr, then a part for crystal grain is by coarsening, therefore easily uneven when angle cylinder drawing and forming distortion, thus has the situation that the plasticity of alloy foil declines.From the viewpoint of the size of the average crystallite particle diameter of alloy foil, heat-up rate during final annealing is preferably 40 DEG C/below hr.Heat-up rate during final annealing is such as 50,45,40,35,30,25,20,15,10 DEG C/below hr, also can be in the scope between any 2 values of this illustrative numerical value.
< shaping wrapping body material >
Alloy foil in the present embodiment, can be suitably used as shaping wrapping body material.The shaping wrapping body material told about in this specification sheets, refer to the alloy foil formed machining of present embodiment be such as secondary cell, PTP with etc. various packagings, as packaged part, pharmaceuticals can be listed, lithium-ion secondary cell material (comprises electrode materials, separating part, electrolytic solution etc.) etc.
Shaping wrapping body material in the present embodiment, because the alloy foil in employing present embodiment, so secondary cell, the shaping wrapping body material of pharmaceuticals packaging vessel and exterior material can be used in aptly, can contribute to improving as the high performance of secondary cell, the use degree of freedom of pharmaceuticals.
Below, use accompanying drawing, the shaping wrapping body material in present embodiment is described in detail.Embodiment in following shaping wrapping body material, is example, is not defined.
Fig. 1 is the schematic sectional view of an example of the internal structure that the lithium-ion secondary cell that sheet is slim is shown.In addition, Fig. 2 is the schematic sectional view of the general example of the exterior material that secondary cell is shown.
Shaping wrapping body material 1 in present embodiment, also can be alloy foil 8 monomer in present embodiment or be made up of the multilayer of the alloy foil 8 comprised in present embodiment, do not limit especially, but when multilayer, need at least possess alloy foil as integrant.Specifically, as shown in Figure 2, the structure stacking gradually synthetic resins masking 10, alloy foil 8, hot sealing layer 9 can be illustrated, but stepped construction is not limited especially.
In order to improve the plasticity of shaping wrapping body material 1 further, or in order to protect the alloy foil 8 of the main body main raw as wrapping body, or can print, synthetic resins masking 10 is stacked and be fitted in the one side of alloy foil 8.As this synthetic resins masking 10, polyester film, nylon membrane etc. can be adopted.The shaping wrapping body material 1 of present embodiment, can be used as secondary cell, pharmaceuticals packaging vessel, particularly, when as secondary cell, the shaping wrapping body material 1 of present embodiment can be used as secondary cell exterior material and use.At this moment need the heating, radiating treatment etc. of carrying out the various battery components of accommodating in exterior material, therefore preferably adopt heat-resistance polyester film as synthetic resins masking 10.
Hot sealing layer 9 is for sealing the end 7 of wrapping body.As hot sealing layer 9, known heatmeltable synthetic resins can be adopted.Particularly, as long as outstanding with the stickiness of alloy foil 8 that adopts in present embodiment, content can be protected, such as non-extended polypropylene screen, two axle extended polypropylene films, maleated polyolefin is preferably adopted.
When shaping wrapping body material 1 is in the present embodiment multilayer, as long as use the alloy foil 8 of present embodiment to be just not particularly limited, as long as and meet plasticity, cementability etc., the adaptability of content is not just particularly limited to.Such as, can by the one side of usual method at alloy foil 8, carry non-extended polypropylene screen across cementability epithelium and crimp, after this alloy foil 8 of laminating and this non-extended polypropylene screen, at the another side adhesive-applying of this alloy foil 8, carry synthetic resins masking 10 thereon and fit.
Above-mentioned alloy foil 8 and the crimping of polypropylene screen are generally carry out in a heated state.Heating condition is not particularly limited, normally about 160 ~ 240 DEG C.Further, crimping condition is not particularly limited, and usually, pressure is 0.5 ~ 2kg/cm 2, the time is about 0.5 ~ 3 second.
In addition, as the caking agent of synthetic resins masking 10, can known material be adopted, such as, can adopt carbamates caking agent etc.
Shaping wrapping body material in the present embodiment, can be shaped by known method, be not particularly limited for formation method, but is suitable for especially being used in drawing and forming.At this, use shaping wrapping body material 1 of the present embodiment, as the example of method obtaining wrapping body, shaping wrapping body material 1 is cut to desired size and obtains the wrapping material of desired shape, drawing and forming is implemented to these wrapping material, become recess to make central part, periphery becomes par, and hot sealing layer 9 side becomes inner face.Use 2 wrapping material implementing drawing and forming, to make recess toward each other, and the mode making the hot sealing layer 9 of periphery against each other is bonding.In addition, retain a part, the heat-sealing of other periphery is sealed, thus obtains wrapping body.If for secondary cell exterior material is used, then by receiving positive electrode collector 2, positive pole 3, isolated material 4, negative pole 5, negative electrode collector 6 at central part and then manufacturing secondary cell by electrolysis immersion stain, and, to make the lead-in wire extended from secondary cell main body draw outside mode, can manufacture according to the known method such as again sack heat-sealing being sealed.
Secondary cell according to the present embodiment, owing to adopting the shaping wrapping body material 1 possessing the alloy foil 8 with above-mentioned good plasticity, so the more deep drawing making recess more deeply wait than ever is shaped become good, the secondary cell exterior material that collecting amount is many can be formed, therefore can obtain having the charging capacity or the high secondary cell exported that can bear long-time use.
Adopt the shaping wrapping body material 1 in present embodiment, when obtaining pharmaceuticals packaging vessel, manufacturing process also can adopt above-mentioned method.Such as, if PTP use, then receive medicine (tablet, capsule etc.) and pharmaceuticals packaging vessel can be used as.Pharmaceuticals packaging vessel of the present invention can manufacture by known method, is not particularly limited manufacture method.
According to this pharmaceuticals packaging vessel, owing to adopting the shaping wrapping body material 1 possessing the alloy foil 8 with above-mentioned good plasticity, so the deep drawing under severe conditions that can carry out angle drawing and forming etc. is shaped, can seek to reduce shaping wrapping body material 1.In addition, according to this pharmaceuticals packaging vessel, because the average crystallite particle diameter of alloy foil is little, so be difficult to uneven distortion when deep drawing is shaped, the slight crack of molding in bight is also few, therefore water vapour is difficult to invade in shaping wrapping body material 1 from outside, requires the long-term quality control aspect of the tablet of the content intercepting water vapour etc. when being better than keeping.
Above, describe the present invention, but only otherwise exceed main idea of the present invention, can adopt above-mentioned beyond various formation.
Such as, be secondary cell in above-mentioned embodiment with or pharmaceuticals wrapping shaping wrapping body material 1, but be not particularly limited to, the packaging purposes and using as other also can.Such as, also can with the shaping wrapping body material for primary cell, instead of secondary cell.Like this, the deep drawing that recess waits than ever is more deeply shaped and becomes good, can form the primary cell exterior material that collecting amount is many, therefore can obtain having the charging capacity or the high primary cell exported that can bear long-time use.
Embodiment
[embodiment]
Below, illustrate that the present invention's step of going forward side by side is described with experimental example, but the present invention is not limited to these experimental examples.
Prepare to have the aluminium ingot bar of composition that table 1 is recorded, the process that homogenizes that enforcement table 1 is recorded, cooling, hot rolling, cold rolling, paper tinsel roll and final annealing, obtain the alloy foil of thickness 40 μm.Measure tensile strength TS, the 0.2% yield strength YS of 0 degree, 45 degree, 90 degree relative to rolling direction and the elongation of the alloy foil obtained, calculate the value of TS × (TS/YS), the results are shown in table 2.And the average crystallite particle diameter of alloy foil and the crystalline orientation density on alloy foil surface are similarly also shown in table 2.In addition, the laminated composite material of the battery exterior material that trial-production simulation is actual, is also shown in Table 2 the result that angle cylinder drawing and forming is tested.
About the tensile strength TS of alloy foil, the strip test portion sheet utilizing width to be 10mm, jaw separation is from being 50mm, tension test is carried out with the speed of draw speed 10mm/min, measure the maximum load about strip test portion sheet, calculate stress divided by the cross-sectional area of original test portion as tensile strength.In addition, about 0.2% yield strength YS, this straight line in the Hookean region represented with straight line from the cardinal principle of the initial stage positive rise of distance load elongation curve figure, the value of permanent strain of 0.2% draws parallel lines, obtains and the point of above-mentioned curve intersection, the value being namely equivalent to the point of the Qu Fudian of steel etc.In addition, about elongation, with the measuring method same with during tensile strength, jaw separation when being ruptured by strip test portion sheet, from when being set to L (mm), calculates with ((L-50)/50) × 100.
Then, in order to which kind of degree the deep drawability of the shaping wrapping body material testing the alloy foil using experimental example to relate to reaches, following experiment has been carried out.In the one side of each alloy foil that example by experiment obtains, the organic solution be made up of maleic anhydride modified polypropylene 15 weight part and toluene 85 weight part of coating median size 6 ~ 8 μm, 200 DEG C, dry under the condition in 20 seconds, obtain the cementability epithelium of thickness 2 μm.Secondly, at temperature 200 DEG C, pressure 2kg/cm 2, second time 1 crimping condition under, cementability epithelial surfaces crimping and the polypropylene screen of coating thickness 40 μm.Finally, to the another side (surface of squeeze film of not fitting) of alloy foil, 2 axles across carbamates caking agent coating thickness 25 μm extend nylon, thus obtain shaping wrapping body material.
From above-mentioned profile wrappers, cut off with the size of 120mm × 100mm, as the sample of angle cylinder drawing and forming test.Adopt length 60mm, width 40mm, shoulder R and bight R to be the punch press of 1.5mm, implement angle cylinder drawing and forming test with the wrinkle resistant power of 300kgf.Forming height uprises with 0.5mm scale from 1.0mm, carries out the above-mentioned angle cylinder drawing and forming test of 5 times at each forming height, and by there is not pin hole in whole 5 times, the maximum forming height of slight crack is shown in table 2.
In addition, the following average crystallite particle diameter measuring alloy foil.Utilize 20 capacity % persalt+80 capacity % alcohol mixed solutions of less than 5 DEG C, after with voltage 20V electrolytic polishing being carried out to obtained each alloy foil, carry out washing, dry, then, in the mixing solutions of 50 capacity % phosphoric acid+47 capacity % methyl alcohol+3 capacity % hydrofluoric acid below 25 DEG C, after forming anodic oxide coating with voltage 20V, apply polarized light with opticmicroscope, observe crystal grain, and be shot for photo.From the photo of shooting, utilize the process of chopping, measure average crystallite particle diameter.The process of chopping, is have several crystal grain in certain line segment of number, obtains with the method for this number divided by the size of line segment.Each average crystallite particle diameter is shown in Table 2.
X-ray diffraction device is used to measure the crystalline orientation density on alloy foil surface, according to Shu Erci (Schultz) reflection method of X-ray diffraction, measure that { 100}, { 110}, { the incomplete pole graph of 111} carries out three-dimensional crystals orientation parsing (ODF) and investigated based on these.In this these parsing external, the test portion with random crystalline orientation that made by aluminium powder form will be measured and the data that obtain, as to { 100}, { 110}, { the normalization file used when 111} pole graph is resolved, thus with to having the multiple of test portion of random orientation to obtain various orientation density.In this external experimental example, crystalline orientation density all resolves (ODF) based on three-dimensional crystals orientation.
At this, Cube orientation is so that {, for representing orientation, R orientation is so that { 123} < 634 > is for representing orientation for 001} < 100 >.Moreover, usually have that to have the orientation of certain angle discrete with the above-mentioned center that is oriented to, in this experimental example, get the maximum orientation density in 15 ° of rotating ranges around above-mentioned orientation, respectively as the typical value of above-mentioned orientation density.
[table 1]
[table 2]
As can be known from the above results, in the alloy foil that experimental example 1 ~ 21,28,29 and 31 relates to, the orientation density of average crystallite particle diameter, alloy foil is controlled, therefore, compared with the alloy foil 22 ~ 27,30,32 ~ 39 related to experimental example, illustrate that the forming height of angle cylinder drawing and forming test is high, plasticity is outstanding.Thus, the alloy foil of known experimental example 1 ~ 21,28,29 and 31 and the shaping wrapping body material that obtains, can carry out deep drawing shaping well, be suitable for packing the thicker content of thickness.In addition, in the alloy foil that experimental example 1 ~ 21 relates to, be also controlled as the best relative to the strength balance in 0 degree, 45 degree, 90 degree direction of rolling direction, therefore illustrate that the forming height of angle cylinder drawing and forming test is higher, plasticity is outstanding.On the other hand, in the alloy foil that experimental example 22 ~ 27,30,32 ~ 39 relates to, obviously learn that the forming height of angle cylinder drawing and forming test is low, plasticity is bad.Thus, adopt the alloy foil that relates to of experimental example 22 ~ 27,30,32 ~ 39 and the shaping wrapping body material that obtains, deep drawing shaping can not be carried out well, be not suitable for packing the thicker content of thickness.
In addition, as can be known from the above results, due to the aluminium alloy ingot bar of specific operation process specific composition, so compared with the alloy foil 22 ~ 39 related to experimental example, the alloy foil that experimental example 1 ~ 21 relates to illustrates that the forming height of angle cylinder drawing and forming test is high, plasticity is outstanding.Thus, the shaping wrapping body material that the alloy foil that known experimental example 1 ~ 21 relates to obtains, can carry out drawing and forming well, is applicable to the content that packaging thickness is thicker.
In experimental example 22, attach Si amount few, the value of the TS therefore on 45 degree of directions × (TS/YS) is low, and when angle cylinder drawing experiments, material is difficult to flow into flange part, thus does not improve forming height.
In experimental example 23, attach Si amount many, the value of the TS therefore not only on 45 degree of directions × (TS/YS) is low, and average crystallite particle diameter also becomes large, thus does not improve forming height.
In experimental example 24, attach Fe amount few, the value of the TS therefore not only on 45 degree of directions × (TS/YS) is low, and average crystallite particle diameter also becomes large, thus does not improve forming height.
In experimental example 25, attach Fe amount many, therefore crystal grain is small, and the value of the TS not only on 45 degree of directions × (TS/YS) is low, and R orientation density uprises, thus does not improve forming height.
In experimental example 26, attach Cu amount few, the value of the TS therefore on 45 degree directions × (TS/YS) is low, material is difficult to inflow flange part, thus do not improve forming height.
In experimental example 27, attach Cu amount many, therefore the Cube orientation density on alloy foil surface is low, thus does not improve forming height.
In experimental example 28, the treatment temp that homogenizes is low, and the value of the TS therefore on 45 degree of directions × (TS/YS) is low, when angle cylinder drawing experiments, material is difficult to flow into flange part, thus does not improve forming height.
In experimental example 29, the hold-time homogenized when processing is short, and the value of the TS therefore on 45 degree of directions × (TS/YS) is low, and when angle cylinder drawing experiments, material is difficult to flow into flange part, thus the raising of forming height is few.
In experimental example 30, intermediate anneal temperature is low, and the value of the TS therefore not only on 45 degree of directions × (TS/YS) is low, and average crystallite particle diameter also becomes large, thus does not improve forming height.
In experimental example 31, intermediate anneal temperature is high, and the value of the TS therefore in 45 degree of directions × (TS/YS) is low, and when angle cylinder drawing experiments, material is difficult to flow into flange part, thus the raising of forming height is few.
In experimental example 32, do not implement process annealing, therefore crystal grain is small, the value of the TS in 45 degree of directions × (TS/YS) is low, Cube orientation density is few, R orientation density uprises, and the difference of the TS in 0 degree of direction and 45 degree of directions × (TS/YS), 45 degree of directions and 90 degree of directions the difference of TS × (TS/YS) also become large, therefore do not improve forming height.
In experimental example 33, large from the cold rolling rate after hot rolling before process annealing, therefore there is small fracture in the Cube orientation density on the alloy foil surface initial stage that is few, angle cylinder drawing experiments, therefore do not improve forming height.
In experimental example 34, from after process annealing to become last paper tinsel thick cold rolling rate few, the value of the TS therefore not only on 45 degree of directions × (TS/YS) is low, and average crystallite particle diameter also becomes large, thus does not improve forming height.
In experimental example 35, from after process annealing to become last paper tinsel thick cold rolling rate large, the value of the TS therefore not only on 45 degree of directions × (TS/YS) is low, and Cube orientation density is few, R orientation density uprises, and then the difference of the TS in 0 degree of direction and 45 degree of directions × (TS/YS) becomes large, thus do not improve forming height.
In experimental example 36, the value of the TS on 45 degree of directions × (TS/YS) is low, and alloy foil is recrystallize not, thus forming height declines.
In experimental example 37, the value of the TS not only on 45 degree of directions × (TS/YS) is low, and average crystallite particle diameter also becomes large, thus does not improve forming height.
In experimental example 38, the value of the TS not only on 45 degree of directions × (TS/YS) is low, and average crystallite particle diameter also becomes large, thus does not improve forming height.
In experimental example 39, the value of the TS on 45 degree of directions × (TS/YS) is low, and alloy foil is recrystallize not, thus forming height declines.
[nomenclature]
1 exterior material (shaping wrapping body material)
2 positive electrode collectors
3 positive poles
4 isolated materials (separating part)
5 negative poles
6 negative electrode collectors
The end of 7 exterior materials
8 exterior material main bodys (alloy foil)
9 hot sealing layers
10 synthetic resins maskings

Claims (7)

1. an alloy foil, it contains Fe:0.8 ~ 2.0mass%, Si:0.05 ~ 0.2mass%, Cu:0.0025 ~ 0.2mass%, and remainder is made up of Al and inevitable impurity,
In described alloy foil, on the crystalline orientation on described alloy foil surface, Cube orientation density is more than 5, R orientation density is less than 50,
The average crystallite particle diameter of described alloy foil is 7 ~ 20 μm.
2. alloy foil according to claim 1, wherein,
In described alloy foil relative to 0 of rolling direction degree, in the respective tensile strength TS in 45 degree, 90 degree directions and 0.2% yield strength YS,
The value of the TS on 45 degree of directions × (TS/YS) is 200N/mm 2above,
The absolute value of the difference of TS × (TS/YS) in 0 degree of direction and 45 degree of directions is 30N/mm 2below,
The absolute value of the difference of TS × (TS/YS) in 45 degree of directions and 90 degree of directions is 30N/mm 2below.
3. a shaping wrapping body material, it possesses alloy foil as claimed in claim 1 or 2.
4. shaping wrapping body material according to claim 3, wherein,
Described shaping wrapping body material also possesses:
Be layered in the synthetic resins masking of the side of described alloy foil, and
Be layered in the hot sealing layer of the opposite side of described alloy foil.
5. a secondary cell, it uses shaping wrapping body material as claimed in claim 4.
6. a pharmaceuticals packaging vessel, it uses shaping wrapping body material as claimed in claim 4.
7. manufacture a method for alloy foil as claimed in claim 1 or 2, it comprises:
By the aluminium alloy ingot bar that Fe:0.8 ~ 2.0mass%, Si:0.05 ~ 0.2mass%, Cu:0.0025 ~ 0.2mass%, remainder are made up of Al and inevitable impurity, less than the 620 DEG C maintenance operations of more than 1 hour that homogenize more than 500 DEG C;
After this homogenizes maintenance, implement hot rolling and cold rolling operation;
In the midway that this is cold rolling, implement the operation of the process annealing that less than 450 DEG C keep more than 300 DEG C;
The cold rolling rate after this hot rolling before this process annealing is made to be less than 85% implement cold rolling operation;
Make after this process annealing to become last paper tinsel thick cold rolling rate be less than more than 80% 93% implement cold rolling operation; And
The operation of described alloy foil is obtained at this cold rolling rear enforcement final annealing.
CN201380021238.6A 2012-05-11 2013-04-26 Aluminum alloy foil and method for producing same, molded package material, secondary battery, and pharmaceutical packaging container Active CN104364401B (en)

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