CN104797725A - Aluminum-alloy foil - Google Patents

Aluminum-alloy foil Download PDF

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Publication number
CN104797725A
CN104797725A CN201380060970.4A CN201380060970A CN104797725A CN 104797725 A CN104797725 A CN 104797725A CN 201380060970 A CN201380060970 A CN 201380060970A CN 104797725 A CN104797725 A CN 104797725A
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alloy foil
paper tinsel
less
solid solution
alloy
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CN104797725B (en
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田中宏树
本居徹也
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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
    • 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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

By mass, this aluminum-alloy foil contains 0.1-0.6% silicon and 0.2-1.5% iron, with the sum of the silicon content and the iron content being greater than or equal to 0.48% and the remainder comprising aluminum and unavoidable impurities. The amount of silicon in solid solution is at least 700 ppm by mass, and the amount of iron in solid solution is at least 150 ppm by mass. This aluminum-alloy foil is at most 20 [mu]m thick and exhibits a tensile strength of at least 220 MPa. The resistivity of this aluminum-alloy foil, measured in liquid nitrogen, is between 0.45 and 0.7 [mu][Omega].cm, inclusive.

Description

Alloy foil
Technical field
The present invention relates to a kind of alloy foil.
Background technology
In the past, alloy foil was used in various field, and in recent years, from thin and have the viewpoints such as electroconductibility, alloy foil is used in the Electrical storage devicess such as such as lithium ion battery, double layer capacitor, lithium-ion capacitor by the current collector as electrode etc.Specifically, such as, in patent documentation 1,2, disclose by following manufacturing process manufacture as the lithium ion cell positive in Electrical storage devices.On a face of the alloy foil as current collector, coating comprises the layer of positive active material and tackiness agent, makes it dry.Afterwards, carry out the rolling for improving positive active material density and the stickiness with paper tinsel, thus manufacture positive pole.
As above-mentioned alloy foil, such as, Patent Document 3 discloses a kind of alloy foil for lithium ion battery: it is by containing Si:0.01 ~ 0.60 quality %, Fe:0.2 ~ 1.0 quality %, Cu:0.05 ~ 0.50 quality %, Mn:0.5 ~ 1.5 quality %, remainder is that Al and inevitable impurity are formed, its tensile strength is more than 240MPa, n value is more than 0.1.
In addition, as the prior art document of the application, also have other 2 sections.In patent documentation 4, the alloy foil that although disclosed is not for lithium ion battery, but disclose a kind of like this alloy foil for porous processing: it is by containing Si:0.05 ~ 0.30 quality %, Fe:0.15 ~ 0.60 quality %, Cu:0.01 ~ 0.20 quality %, remainder is that Al and inevitable impurity are formed, and its tensile strength is 186 ~ 212N/mm 2left and right, paper tinsel thickness is 30 μm ~ about 100 μm.
And, in patent documentation 5, disclose a kind of alloy foil for paper tinsel material: it is by containing Fe:0.1 ~ 2.5 quality % and Si:0.01 ~ 0.5% quality %, remainder is Al and inevitable impurity composition, and the Fe content of its solid solution is at more than 200pm, is not made by hot rolling by cold rolling.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-234277 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-67220 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2011-26656 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2006-283114 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2008-223075 publication
Summary of the invention
The problem to be solved in the present invention
But alloy foil in the past has problems in the following areas.That is, as mentioned above, when manufacturing Electrical storage devices etc. and using the parts of paper tinsel, because the alloy foils such as rolling can be compressed power.Therefore, alloy foil needs to have enough intensity, can not there is unnecessary distortion or breakage relative to such force of compression.In recent years, requiring the further thin-walled property of paper tinsel, in order to tackle this requirement, also needing the high strength of paper tinsel.
As the exemplary process of the high strength for realizing paper tinsel, there is the method for adjustment al alloy component.But only adjust alloying constituent merely, owing to the addition of the alloying constituent beyond Al, the ratio resistance of paper tinsel can be made to increase, electroconductibility reduces.So, there is such problem in alloy foil in the past: be difficult to neither lose electroconductibility significantly, can realize high strength again.
The present invention, in view of above-mentioned background, provides a kind of alloy foil, and this alloy foil can not lose electroconductibility significantly, can realize high strength again.
The method of dealing with problems
The alloy foil of an embodiment of the invention, it is characterized in that, the chemical composition of this alloy foil is by coming containing more than Si:0.1% less than 0.6% by quality %, more than Fe:0.2% less than 1.5%, and Si content and Fe content add up to more than 0.48%, remainder is that Al and inevitable impurity are formed, paper tinsel thickness is less than 20 μm, the solid solution capacity of Si is more than 700 quality ppm, the solid solution capacity of Fe is more than 150 quality ppm, tensile strength is more than 220MPa, the ratio resistance measured in liquid nitrogen is 0.45 μ more than Ω cm 0.7 μ below Ω cm.
Invention effect
Above-mentioned alloy foil, owing to having above-mentioned specific formation, can not lose electroconductibility significantly, can realize high strength again.Therefore, above-mentioned alloy foil, even if such as when the electrode etc. manufacturing Electrical storage devices use apply force of compression by rolling etc. during the parts of paper tinsel, also can suppress unnecessary viscous deformation, also easily realize the thin-walled property of paper tinsel.And, even if above-mentioned alloy foil also can not lose electroconductibility under improving intensity significantly, good electroconductibility can be guaranteed.Therefore, if above-mentioned alloy foil is such as used as the current collector of electrode in the Electrical storage devices of lithium ion battery etc., the densification of Electrical storage devices can be contributed to, high energy quantizes.
Accompanying drawing explanation
Fig. 1 is the explanatory view be described for roughly step when measuring Si solid solution capacity, Fe solid solution capacity in embodiment.
Embodiment
The meaning of the specified chemical composition (unit is quality %, only economizes slightly " % " in following chemical composition illustrates) in above-mentioned alloy foil and restriction reason are as mentioned below.
More than Si:0.1% less than 0.6
Si is the bioelement for realizing improving paper tinsel intensity.When manufacturing paper tinsel, if the temperature of aluminium alloy is more than 350 DEG C, then Si and Fe of solid solution easily separates out as Al-Fe-Si based compound, can reduce the work hardening of cold rolling thus, easily reduces paper tinsel intensity.Therefore, preferably, be not performed for more than the process that homogenizes under the high temperature of 350 DEG C when manufacturing paper tinsel, and carry out hot rolling under condition below 350 DEG C.In order to improve paper tinsel intensity under this condition, reducing the ratio resistance of paper tinsel thus guaranteeing its electroconductibility, needing to make Si content more than 0.1% less than 0.6%.If Si is containing quantity not sufficient 0.1%, then the ratio resistance of paper tinsel reduces, but the intensity of paper tinsel does not improve.If Si amount is more than 0.6%, be then difficult to improve paper tinsel intensity further, easily form the thick single-phase particle of Si, the problem of pin hole, paper tinsel cracking easily occurs when paper tinsel thickness is below 20 μm.Si content can be preferably more than 0.12%.Si content can be preferably less than 0.4%.
More than Fe:0.2% less than 1.5%
Fe is the bioelement for realizing improving paper tinsel intensity inferior to Si, if the temperature of aluminium alloy is more than 350 DEG C when manufacturing paper tinsel, then Si and Fe of solid solution easily separates out as Al-Fe-Si based compound, can reduce the work hardening of cold rolling thus, easily reduces paper tinsel intensity.Therefore, preferably, be not performed for more than the process that homogenizes under the high temperature of 350 DEG C when manufacturing paper tinsel, and carry out hot rolling under condition below 350 DEG C.In order to improve paper tinsel intensity under this condition, reducing the ratio resistance of paper tinsel thus guaranteeing its electroconductibility, needing to make Fe content more than 0.2% less than 1.5%.If Fe content is lower than 0.2%, then the ratio resistance of paper tinsel reduces, but the intensity of paper tinsel does not improve.If Fe content is higher than 1.5%, be then difficult to improve paper tinsel intensity further, and form thick Al-Fe system crystallisate when casting.As mentioned above, not to aluminium alloy ingot bar homogenize under the high temperature more than 350 DEG C process when, the Al-Fe system crystallisate formed during casting remains in final paper tinsel thickness with thick form.Therefore, the problem of pin hole, paper tinsel cracking is easily there is when paper tinsel thickness is below 20 μm.And adding necessary above Fe, is also the reason that manufacturing cost increases.Fe content can be preferably more than 0.30%.Fe content can be preferably less than 1.2%, is more preferably less than 1.0%, and more preferably less than 0.80%.
Si content and Fe content add up to: more than 0.48%
The total (using " Si+Fe measures " to represent below) of Si content and Fe content guarantee in the tensile strength of more than 220MPa most important.If Si+Fe quantity not sufficient 0.48%, the tensile strength of more than 220MPa cannot be obtained, and be difficult to realize high strength.Being easy to from the view point of Si+Fe amount the tensile strength guaranteeing more than 220MPa, being preferably more than 0.49%, being more preferably more than 0.5%, is preferably more than 0.52% further.Further, consider the upper limit etc. of above-mentioned Si content, Fe content, Si+Fe amount can be less than 1.6%, preferably less than 1.4%, is more preferably less than 1.2%.
Above-mentioned chemical composition, by quality %, can contain more than Cu:0.01% less than 0.25% further.In this case meaning and restriction reason are as mentioned below.
More than Cu:0.01% less than 0.25%
Cu is the element contributing to improving paper tinsel intensity.In order to obtain this effect, Cu content is preferably made to be more than 0.01%.In addition, also can containing the Cu less than 0.01% as inevitable impurity.On the other hand, if Cu content is excessive, paper tinsel intensity increases.But ratio resistance also can increase.Therefore Cu content is preferably made to be less than 0.25%.Cu content can be preferably more than 0.02%.Cu content can be preferably less than 0.18%.
In above-mentioned chemical composition, as inevitable impurity, can containing elements such as Mn, Mg, Cr, Zn, Ni, Ga, V, Ti.But, if excessively containing Mn, Mg, then the ratio resistance of paper tinsel probably can be increased, and reduces electric conductivity.Therefore, preferably making Mn content be less than 0.01%, Mg content is less than 0.01%.Because other elements such as Cr, Zn, Ni, Ga, V, Ti compare the element being unfavorable for increasing ratio resistance, preferably make each constituent content all below 0.05%.In addition, if all inevitable impurity adds up to amount below 0.15%, because there is no substantial impact so be allow to electroconductibility, high strength.
In above-mentioned alloy foil, paper tinsel thickness is less than 20 μm.If paper tinsel thickness is more than 20 μm, then can not tackle the thin-walled property (paper tinsel thickness calibration size reduces (gauge down)) of the paper tinsel extensively required in recent years.Above-mentioned alloy foil, because paper tinsel thickness is below 20 μm, such as, requires particularly suitable in the current collector purposes of higher Electrical storage devices electrode at the thin-walled property for paper tinsel.In above-mentioned alloy foil, from viewpoints such as thin-walled property, the miniaturizations that can contribute to Electrical storage devices, paper tinsel thickness can be preferably less than 20 μm, can be more preferably less than 19 μm, can more preferably less than 18 μm, further can be preferably less than 17 μm.On the other hand, such as, from viewpoints such as the easy handlings when manufacturing the parts of use paper tinsel of electrode etc. of Electrical storage devices, paper tinsel thickness can be preferably more than 8 μm, can be more preferably more than 9 μm, can more preferably more than 10 μm.
In above-mentioned alloy foil, the solid solution capacity of Si is the solid solution capacity of more than 700 quality ppm, Fe is more than 150 quality ppm.If the solid solution capacity of Si less than 150 quality ppm, then can not realize the high strength of tensile strength at more than 220MPa less than the solid solution capacity of 700 quality ppm, Fe.From the view point of above-mentioned guarantee high strength, the solid solution capacity of Si, is preferably more than 720 quality ppm, is more preferably more than 740 quality ppm, more preferably 760 quality ppm.Further, the solid solution capacity of Si, preferably higher numerical value.But in actual manufacture, from the view point of the speed of cooling etc. during ingot bar, its upper limit is 1000 quality ppm.On the other hand, from the view point of above-mentioned guarantee high strength, the solid solution capacity of Fe, is preferably more than 170 quality ppm, is more preferably more than 190 quality ppm, more preferably more than 200 quality ppm.Further, the solid solution capacity of Fe, preferably higher numerical value.But in actual manufacture, from the view point of the speed of cooling etc. during ingot bar, its upper limit is 500 quality ppm.
The solid solution capacity of above-mentioned Si, the solid solution capacity of above-mentioned Fe, substantially, measure by following methods.That is, use hot phenol to dissolve extraction method, obtain the Al-Fe based compound as residue that it contains in the test piece gathered from alloy foil, Al-Fe-Si based compound.Then, dissolve extraction method by this hot phenol Si, Fe are dissolved out from above-mentioned residue, and carry out quantitative analysis by ICP emission spectrometry (ICP), obtain the Si amount of precipitation separated out as above-claimed cpd, Fe amount of precipitation.Further, use dissolving with hydrochloric acid extraction method, in the test piece gathered from aluminium gold paper tinsel, obtain the single-phase particle of its Si as residue contained.Then, dissolve above-mentioned residue by this dissolving with hydrochloric acid extraction method, carry out quantitative analysis by ICP, obtain the Si amount of precipitation separated out as the single-phase particle of Si.Then, using the Si amount of precipitation of being dissolved Si amount of precipitation that extraction method obtains by hot phenol and obtained by dissolving with hydrochloric acid extraction method and as the total amount of precipitation of Si.Further, Fe amount of precipitation that extraction method obtains will be dissolved by hot phenol as the total amount of precipitation of Fe.Then, the Si composition analysis value of alloy foil is deducted value that the total amount of precipitation of Si obtains as Si solid solution capacity.Further, the Fe composition analysis value of alloy foil is deducted the value of the total amount of precipitation of Fe as Fe solid solution capacity.
In above-mentioned alloy foil, tensile strength is more than 220MPa.If tensile strength is less than 220MPa, the said high strength of the application cannot be reached.Tensile strength is preferably more than 223Mpa, is more preferably more than 225Mpa, more preferably more than 230Mpa.Further, can consider to determine that the upper limit of tensile strength obtains the suitableeest scope with the balance of ratio resistance.Such as, tensile strength can be controlled in below 340Mpa.Further, tensile strength is the numerical value measured according to JIS (Japanese Industrial Standards) Z2241.
In above-mentioned alloy foil, ratio resistance is 0.45 μ more than Ω cm 0.7 μ below Ω cm.Further, above-mentioned ratio resistance is the numerical value measured in liquid nitrogen.In liquid nitrogen, measure ratio resistance is to eliminate the impact measuring envrionment temperature.
The solid solution capacity of the Si of ratio resistance and alloying constituent, Fe is correlated with.Ratio resistance is in above-mentioned scope, neither can lose electroconductibility significantly, can high strength be realized again.If ratio resistance is less than 0.45 μ Ω cm, is then difficult to work hardening when manufacturing paper tinsel, and is difficult to make tensile strength reach more than 220MPa.Ratio resistance can be preferably 0.50 μ more than Ω cm, is more preferably 0.55 μ more than Ω cm.On the other hand, if ratio resistance uprises, be then easy to work hardening when manufacturing paper tinsel, and be easy to realize high strength.But, can be observed the tendency that electroconductibility declines.Therefore, ratio resistance can be made to be 0.7 μ Ω about cm, to be namely considered to about 60% of the ratio resistance of 3003 line aluminium alloy paper tinsels of the higher alloy foil of strength ratio.Ratio resistance can be preferably 0.69 μ below Ω cm, can be more preferably 0.68 μ below Ω cm.Further, according to JIS H0505, ratio resistance can be measured by Kelvin double bridge method.
Above-mentioned alloy foil, the current collector that can be used as Electrical storage devices electrode uses.In this case, the alloy foil as current collector is attached with electrode active material on the surface.Specifically, in this case, on the surface of alloy foil, be coated with the layer containing electrode active material, apply force of compression by rolling etc. after the drying.Even if in this case, above-mentioned alloy foil is also difficult to produce unnecessary viscous deformation because of force of compression, and therefore electrode active material is difficult to peel off, and, good electroconductibility can be guaranteed.Further, due to the paper tinsel excellent strength of above-mentioned alloy foil, be therefore also easy to the thin-walled property requirement tackling paper tinsel, therefore, in this case, the densification of the Electrical storage devices of lithium ion battery etc. can be conducive to, high energy quantizes.
Above-mentioned alloy foil, such as, can manufacture according to following describing.That is, by after carrying out hot rolling to the aluminium alloy ingot bar formed by above-mentioned specific chemical composition, carry out the cold rolling comprising paper tinsel rolling, thus obtain above-mentioned alloy foil.
Now, not to aluminium alloy ingot bar be performed for more than under the high temperature of 350 DEG C homogenizing process and carry out hot rolling.Hot rolling after the temperature being heated to less than 350 DEG C, when hot rolling is started, hot rolling midway and hot rolling at the end of temperature be all less than 350 DEG C.Arrive the hold-time after the beginning temperature of hot rolling, from the view point of being easy to the precipitation etc. suppressing Al-Fe-Si based compound, within can being set to 12 hours.In addition, hot rolling can carry out once, also can carry out finish rolling system after roughing system, is divided into and carries out for several times.
In addition, cold rolling is not annealed in midway, and makes paper tinsel thickness below 20 μm.If carry out Process Annealing, the precipitation of Al-Fe-Si based compound can be promoted, work hardening when reducing cold rolling and cause the reduction of paper tinsel intensity.In addition, according to the reason same with Process Annealing, preferably do not carry out yet cold rolling terminate after final annealing.From realizing the high strength viewpoint of tensile strength at more than 220MPa, in the cold rolling comprising paper tinsel rolling, final rolling rate can be preferably more than 95%, is more preferably more than 96%, and more preferably more than 97%.Final rolling rate is the value calculated by 100 × (the paper tinsel thickness of the alloy foil after the plate thickness-final cold rolling of the hot rolling making sheet before cold rolling)/(plate thickness of the hot rolling making sheet before cold rolling).
Embodiment
Below the alloy foil involved by embodiment is described.
Embodiment 1
By using the aluminium alloy of the chemical composition shown in semicontinuous casting method his-and-hers watches 1 carry out ingot bar and cut, thus get out aluminium alloy ingot bar.In addition, in the aluminium alloy of the chemical composition shown in table 1, alloy A ~ H is the aluminium alloy of the chemical composition being suitable for embodiment, and alloy I ~ O is the aluminium alloy of the chemical composition as comparative example.
Table 1
To above-mentioned ready aluminium alloy ingot bar, do not carry out homogenizing process and carrying out hot rolling, obtain the hot rolling making sheet that thickness is 2mm.Now, hot rolling is made as the roughing system and finish rolling system of carrying out continuously.Further, in above-mentioned hot rolling, by by for the aluminium alloy ingot bar before roughing system, heat with 330 DEG C and keep 6 hours, thus making the beginning temperature of roughing (the beginning temperature of hot rolling) be 330 DEG C.Further, make the end temp of roughing (the midway temperature of hot rolling) be 310 DEG C, the end temp (end temp of hot rolling) of finish rolling is 270 DEG C.In this such example, be not only beginning temperature and the end temp of above-mentioned hot rolling, and the midway temperature of hot rolling and the end temp of roughing, the beginning temperature of namely finish rolling is also less than 330 DEG C.
Then, after falling back room temperature, do not carry out annealing in midway and repeatedly carry out comprising the cold rolling of paper tinsel rolling, obtaining the alloy foil that paper tinsel thickness is 12 μm.And, final rolling rate in above-mentioned cold rolling is, 100 × (the paper tinsel thickness 12 μm of the alloy foil after the cold rolling of the plate thickness 2000 μm of the hot rolling making sheet before cold rolling-final)/(plate thickness of the hot rolling making sheet before cold rolling 2000 μm)=99.4%.
Then, using the alloy foil that obtains as test materials, its tensile strength, yield strength and unit elongation, ratio resistance (resistivity), Si solid solution capacity and Fe solid solution capacity is measured.Specifically, tensile strength, yield strength and unit elongation, according to JIS Z2241, are chosen JIS5 test piece and are measured under n=2 from test materials.Ratio resistance, according to JIS H0505, adopts Kelvin double bridge method to measure.In addition, in order to eliminate the impact of envrionment temperature, being determined in liquid nitrogen of ratio resistance is carried out.
The mensuration of Si solid solution capacity and Fe solid solution capacity, carries out according to following steps.Be described with reference to Fig. 1.In FIG, describe and dissolve the residue that extraction method obtains and the residue obtained by dissolving with hydrochloric acid extraction method by by hot phenol, analyze the method for total amount of precipitation of the total amount of precipitation of Si in alloy foil, Fe.And, the analytical procedure of Si amount of precipitation, Fe amount of precipitation can with reference to academic documents " assistant rattan; spring: light metal association the 68th Spring Meeting speech summary; (1985); 55 ", academic documents " village pine, loose tail, little Song etc.: light metal association the 76th Spring Meeting speech summary; (1989), 51. ".
First, the explanation of dissolving extraction method about hot phenol is carried out.The test piece (S10) of 2g is chosen from alloy foil.Further, test piece is the small pieces cut out from alloy foil, adds up to and weighs 2g.Then, the beaker adding 50ml phenol is placed on hot plate, after 170 DEG C ~ 180 DEG C heating phenol, drop into test piece and make it dissolve (S11).Then, the beaker adding above-mentioned solution taken down from hot-plate and cool (S12).Then, in order to prevent solidification, in the solution of above-mentioned cooling, phenylcarbinol (S13) is added.Then, the above-mentioned solution that with the addition of phenylcarbinol is filtered (S14) by the film filter (0.1 μm, aperture) of tetrafluoroethylene, obtains Al-Fe based compound, the Al-Fe-Si based compound (S15) as residue.Then, with 10%-NaOH solution by Si from after this is dissolved dissolved the residue that extraction method obtains by hot phenol, then use chloroazotic acid (volume ratio is concentrated hydrochloric acid: concentrated nitric acid=3:1) to be dissolved by Fe, obtain the mixed solution containing Si, the Fe dissolved.Then, quantitative analysis (S16) is carried out by ICP emission spectrometry (ICP).Thus, the Si amount of precipitation, the Fe amount of precipitation that obtain separating out as Al-Fe based compound, Al-Fe-Si based compound is obtained.
Then, the explanation about dissolving with hydrochloric acid extraction method is carried out.The test piece (S20) of 2g is chosen from alloy foil.Further, test piece is chosen according to mode similar to the above.Then, in the beaker adding 120mLHCl (volume ratio is concentrated hydrochloric acid: water=1:1), drop into test piece and at room temperature dissolve, then adding 2 ~ 3 hydrogen peroxide H 2o 2(S21).Then, above-mentioned solution is filtered (S24) by the film filter (0.1 μm, aperture) of tetrafluoroethylene, obtains the single-phase particle of Si (S25) as residue.Then, after the residue 10%-NaOH solubilize that this is obtained by dissolving with hydrochloric acid extraction method, mix with above-mentioned chloroazotic acid, be acidified to pH1 ~ 2.Then, by ICP emission spectrometry (ICP), quantitative analysis (S26) is carried out to this solution.Thus, the Si amount of precipitation separated out as the single-phase particle of Si is obtained.
Then, using dissolved Si amount of precipitation that extraction method obtains by above-mentioned hot phenol and obtained by dissolving with hydrochloric acid extraction method Si amount of precipitation sum as the total amount of precipitation of Si.Further, Fe amount of precipitation that extraction method obtains will be dissolved by above-mentioned hot phenol as the total amount of precipitation of Fe.Then, the Si composition analysis value of alloy foil is deducted value that the total amount of precipitation of Si obtains as Si solid solution capacity.Further, the Fe composition analysis value of alloy foil is deducted value that the total amount of precipitation of Fe obtains as Fe solid solution capacity.
In addition, in order to investigate paper tinsel rolling conditions, throw light on from the back side of test materials, by also investigating in the lump with or without the generation situation of light leak to pin hole.Above result is as shown in table 2.
Table 2
As shown in these results, test materials C1 is owing to employing the alloy I that Si+Fe content is 0.47%, and tensile strength is low to moderate less than 220MPa.
Test materials C2 employs Si containing quantity not sufficient 0.1%, the Fe alloy J containing quantity not sufficient 0.2%, and Si solid solution capacity less than 700 quality ppm, Fe solid solution capacity less than 150 quality ppm.Therefore, test materials C2, tensile strength is low to moderate less than 220MPa.
Test materials C3, owing to employing the alloy K of Si content more than 0.6%, defines the single-phase particle of thick Si, thereby produces pin hole.
Test materials C4 employs the alloy L of Fe containing quantity not sufficient 0.2%, and Fe solid solution capacity is less than 150 quality ppm.Therefore, test materials C3, tensile strength is low to moderate less than 220MPa.
Test materials C5, owing to employing the alloy M of Fe content more than 1.5%, defines thick Al-Fe system particle, thereby produces pin hole.
On the other hand, test materials E1 ~ E8, become by the alloy A containing above-mentioned specified chemical composition ~ H-shaped, paper tinsel thickness is less than 20 μm, and the solid solution capacity of Si is the solid solution capacity of more than 700 quality ppm, Fe is more than 150 quality ppm, and tensile strength is more than 220MPa.And test materials E1 ~ E8, the ratio resistance measured in liquid nitrogen is 0.45 μ more than Ω cm 0.7 μ below Ω cm.As can be known from the results, test materials E1 ~ E8 not only achieves the high strength of tensile strength at more than 220MPa, and electroconductibility is not very large decline also.
Thus, according to this example, can provide a kind of alloy foil, this alloy foil did not both lose electroconductibility significantly, can realize high strength again.Further, above-mentioned alloy foil, even if also have high strength after realizing thin-walled property, thus can avoid pin hole, paper tinsel problems of crack.
Embodiment 2
By using the aluminium alloy A of the chemical composition shown in semicontinuous casting method his-and-hers watches 1 carry out ingot bar and cut, thus get out aluminium alloy ingot bar.Further, by using 1050 alloys (alloy N) of the alloy in the past shown in semicontinuous casting method his-and-hers watches 1,3003 alloys (ALLOY O) carry out ingot bar and cut, thus get out the aluminium alloy ingot bar as comparing in the lump.
Use above-mentioned ready aluminium alloy ingot bar, produce with the manufacturing condition shown in table 3 alloy foil that paper tinsel thickness is 12 μm.Further, cold rolling in table 3, starts after being certainly down to room temperature.To the alloy foil obtained, similarly to Example 1, measure its tensile strength, yield strength and unit elongation, ratio resistance (resistivity), Si solid solution capacity and Fe solid solution capacity, and investigate paper tinsel rolling conditions (pin hole occurring with or without generation).During its result is as shown in table 4.
Table 3
Table 4
As shown in table 4, due to test materials C6 ~ C8, when hot rolling, the beginning temperature of hot rolling is more than 350 DEG C, facilitate the formation of Al-Fe-Si based compound, make Si solid solution capacity less than 700 quality ppm, Fe solid solution capacity less than 150 quality ppm, tensile strength is low to moderate less than 220MPa.
Test materials C9 carries out homogenizing processing with 520 DEG C and makes before hot rolling starts.Therefore, test materials C9 facilitates the formation of Al-Fe-Si based compound, and make Si solid solution capacity less than 700 quality ppm, Fe solid solution capacity less than 150 quality ppm, tensile strength is low to moderate less than 220MPa.
Test materials C10, the beginning temperature of its hot rolling is 340 DEG C.But, in the way of cold rolling, carry out Process Annealing when plate thickness is 1mm with 380 DEG C and make.Therefore, test materials C10 facilitates the formation of Al-Fe-Si based compound, and make Si solid solution capacity less than 700 quality ppm, Fe solid solution capacity less than 150 quality ppm, tensile strength is low to moderate less than 220MPa.
Test materials C11, C12 are 1050 alloys (alloy N) using alloy in the past, 3003 alloys (ALLOY O), and make with process of carrying out under the high temperature of 520 DEG C more than 350 DEG C homogenizing before hot rolling starts further.Because the chemical composition of test materials C11 is identical with 1050 alloys (alloy N) of alloy in the past, its tensile strength is low to moderate less than 220MPa.Because the chemical composition of test materials C12 is identical with 3003 alloys (ALLOY O) of alloy in the past, its ratio resistance is up to 1.2 μ more than Ω cm, and electroconductibility is poor.
On the other hand, test materials E9, E10, formed by the alloy A containing above-mentioned specific chemical composition, paper tinsel thickness is less than 20 μm, and the solid solution capacity of Si is the solid solution capacity of more than 700 quality ppm, Fe is more than 150ppm quality, and tensile strength is more than 220MPa.Further, test materials E9, E10, the ratio resistance measured in liquid nitrogen is 0.45 μ more than Ω cm 0.7 μ below Ω cm.As can be known from the results, test materials E9, E10 not only achieve the high strength of tensile strength at more than 220MPa, and electroconductibility is not very large decline also.
Therefore, according to this example, can provide a kind of alloy foil, this alloy foil did not both lose electroconductibility significantly, can realize high strength again.
Although be illustrated embodiment above, the present invention is not limited to above-described embodiment, can carry out various distortion in the scope not damaging purport of the present invention.

Claims (3)

1. an alloy foil, is characterized in that, comprising:
Its chemical composition is by containing more than Si:0.1% less than 0.6%, more than Fe:0.2% less than 1.5% by mass%, and Si content and Fe content are aggregated in more than 0.48%, and remainder is that Al and inevitable impurity are formed;
Paper tinsel thickness is less than 20 μm;
The solid solution capacity of Si is that the solid solution capacity of more than 700 quality ppm, Fe is at more than 150 quality ppm;
Tensile strength is more than 220MPa;
The ratio resistance measured in liquid nitrogen is 0.45 μ more than Ω cm 0.7 μ below Ω cm.
2. alloy foil according to claim 1, is characterized in that, described chemical composition is come further containing more than Cu:0.01% less than 0.25% by quality %.
3. alloy foil according to claim 1, is characterized in that, described alloy foil is used for the current collector of Electrical storage devices electrode.
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