CN104769141A - Aluminium alloy foil - Google Patents
Aluminium alloy foil Download PDFInfo
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- CN104769141A CN104769141A CN201380056002.6A CN201380056002A CN104769141A CN 104769141 A CN104769141 A CN 104769141A CN 201380056002 A CN201380056002 A CN 201380056002A CN 104769141 A CN104769141 A CN 104769141A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C21/00—Alloys based on aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- 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
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- 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
- C22F1/043—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 of alloys with silicon as the next major constituent
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- 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
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Abstract
An aluminium alloy foil which has a chemical composition containing, in mass %, Si:0.1-0.6% inclusive, and Fe:0.2-1.0% inclusive, and a remainder comprising Al and inevitable impurities, and which has a foil thickness of 20[mu]m or less. If a boundary which has an orientation difference of 5 DEG +-0.2 DEG with an adjacent crystal orientation measurement point is specified as a crystal grain boundary, the surface area ratio of subgrain having a grain size of 2[mu]m or less is 40% or more. The aluminium alloy foil has a tensile strength of 210 MPa or more, and a specific resistance, measured in liquid nitrogen, of 0.45-0.7[mu][Omega]cm inclusive.
Description
Technical field
The present invention relates to a kind of alloy foil.
Background technology
In the past, alloy foil was used in various field.In recent years, from thin and have the viewpoints such as electroconductibility, alloy foil is used by as current collectoies such as secondary cell or double layer capacitor etc. such as such as lithium ion batteries.Specifically, in the case of li-ion batteries, disclosed in patent documentation 1, patent documentation 2, the layer of positive active material and tackiness agent is comprised by coating on a face of the alloy foil as current collector, after making its drying, carry out the rolling of the density for improving positive active material and the stickiness with paper tinsel, thus manufacture positive pole.
As above-mentioned alloy foil, such as Patent Document 3 discloses a kind of like this alloy foil of 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, in patent documentation 4, although the alloy foil of disclosed is not lithium ion battery, but disclose a kind of like this alloy foil of 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.
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
Summary of the invention
But alloy foil in the past has problems in the following areas.That is, as mentioned above, when manufacturing battery electrode 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 problem, expecting to improve intensity further.
As the representational method 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 become large, and electroconductibility reduces.Like this, there is such problem in alloy foil in the past: be difficult to realize namely to lose electroconductibility significantly, can improve intensity further again.
The present invention, in view of above-mentioned background, provides a kind of alloy foil, and this alloy foil can realize namely can not losing electroconductibility significantly, can improve intensity further again.
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%, more than Fe:0.2% less than 1.0% by quality %, and remainder is that Al and inevitable impurity are formed; Paper tinsel thickness is less than 20 μm; When the border by the misorientation between adjacent crystalline orientation measurement point being 5 ° ± 0.2 ° is defined as crystal boundary, grain-size is the area ratio of the subgrain of less than 2 μm is more than 40%; Tensile strength is more than 210MPa; The ratio resistance measured in liquid nitrogen is 0.45 μ more than Ω cm 0.7 μ below Ω cm.
Because above-mentioned alloy foil has above-mentioned specific feature, therefore, it is possible to realize namely to lose electroconductibility significantly, intensity can be improved further again.Because above-mentioned alloy foil can give play to enough intensity by improving intensity further, even if when therefore such as applying force of compression when manufacturing the parts of the use paper tinsels such as battery electrode by rolling etc., also can suppress unnecessary viscous deformation, also easily realize the thin-walled property of paper tinsel.And above-mentioned alloy foil, even if improve its intensity also can not lose electroconductibility significantly, can guarantee good electroconductibility.Therefore, if above-mentioned alloy foil is such as used as the current collector of the electrode in the secondary cells such as lithium ion battery, the densification of battery can be contributed to, high energy quantizes.
Accompanying drawing explanation
Fig. 1 is for the test materials E11 in embodiment 1, and the grain-size measured by SEM/EBSD method is the schematic diagram of the result of the area ratio of the subgrain of less than 2 μm.
Fig. 2 is for the test materials C1 in embodiment 1, and the grain-size measured by SEM/EBSD method is the schematic diagram of the result of the area ratio of the subgrain of less than 2 μm.
Embodiment
Specific chemical composition in above-mentioned alloy foil (unit is quality %, following to the explanation of chemical composition in only economize slightly " % ") meaning and limit reason 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 can separate out as Al-Fe-Si based compound, thus, can reduce work hardening during cold rolling, easily reduces paper tinsel intensity.Therefore, preferably, the Homogenization Treatments under high temperature is not carried out when manufacturing paper tinsel, and carry out hot rolling under condition below 350 DEG C, but in order to improve paper tinsel intensity under this condition, reducing the ratio resistance of paper tinsel and guaranteeing electroconductibility, being necessary to make Si content be less than more than 0.1% 0.6%.If Si, containing quantity not sufficient 0.1%, although can reduce the ratio resistance of paper tinsel, can not improve the intensity of paper tinsel.If Si content is more than 0.6%, be then difficult to improve paper tinsel intensity further, and the single-phase particle of thick Si can be formed, 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 1.0%
Fe is the bioelement for realizing improving paper tinsel intensity inferior to Si.When manufacturing paper tinsel, if the temperature of aluminium alloy is more than 350 DEG C, then Si and Fe of solid solution can separate out as Al-Fe-Si based compound, can reduce work hardening during cold rolling, easily reduces paper tinsel intensity.Therefore, preferably, the Homogenization Treatments under the high temperature of 350 DEG C is not performed for more than when manufacturing paper tinsel, and carry out hot rolling under condition below 350 DEG C, but in order to improve paper tinsel intensity under this condition, reduce the ratio resistance of paper tinsel and guarantee electroconductibility, being necessary to make Fe content be less than more than 0.2% 1.0%.If Fe, containing quantity not sufficient 0.2%, although can reduce the ratio resistance of paper tinsel, can not improve the intensity of paper tinsel.If Fe content is more than 1.0%, be then difficult to improve paper tinsel intensity further, and thick Al-Fe system crystallisate can be formed when casting.As mentioned above, when not carrying out Homogenization Treatments to aluminium alloy ingot bar with the high temperature more than 350 DEG C, the Al-Fe system crystallisate formed during casting can keep thick state to remain in final paper tinsel thickness.Therefore, the problem of pin hole, paper tinsel cracking is easily there is when paper tinsel thickness is below 20 μm.And, exceed and add the reason that Fe also can become manufacturing cost increase necessarily.Fe content can be preferably more than 0.30%.Fe content can be preferably less than 0.80%.
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, although the intensity of paper tinsel can be increased, also ratio resistance can be increased.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 likely 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, the content of each element is therefore preferably made to be respectively less than 0.05%.In addition, if the total content of whole inevitable impurity is less than 0.15%, due to raising or the electroconductibility of paper tinsel intensity substantially can not be affected, be therefore admissible.
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 often required in recent years.Above-mentioned alloy foil is less than 20 μm due to its paper tinsel thickness, is therefore particularly suitable for the current collector the purposes such as thin-walled property of paper tinsel being required to higher battery electrode.From thin-walled property, can be conducive to the viewpoints such as miniaturization such as battery, the paper tinsel thickness of above-mentioned alloy foil can be preferably less than 20 μm, is more preferably less than 19 μm, more preferably less than 18 μm, is further preferably less than 17 μm.On the other hand, such as, from viewpoints such as the easy handlings manufactured when manufacturing battery etc. when using the parts of paper tinsel, paper tinsel thickness can be preferably more than 8 μm, is more preferably more than 9 μm, more preferably more than 10 μm.
In above-mentioned alloy foil, when the border by the misorientation between adjacent crystalline orientation measurement point being 5 ° ± 0.2 ° is defined as crystal boundary, grain-size is the area ratio of the subgrain of less than 2 μm is more than 40%.Specifically, by using scanning electronic microscope/Electron Back-Scattered Diffraction (Electron Back ScatterDiffraction) method (SEM/EBSD method), with the step-length of 0.1 μm (distance between crystalline orientation measurement point) to 900 μm of paper tinsel surface
2region analyze, be that crystal boundary is regarded on the border of 5 ° ± 0.2 ° as by the misorientation between adjacent crystalline orientation measurement point, calculate the ratio (%) of grain-size shared by the area of the subgrain of less than 2 μm in the area of above-mentioned measured zone, thus the area ratio of above-mentioned subgrain can be obtained.
If the area ratio of above-mentioned subgrain is less than 40%, then can reduce the tensile strength of paper tinsel, and reduce the intensity of paper tinsel.From the view point of further improving intensity, the area ratio of above-mentioned subgrain can be preferably more than 45%, is more preferably more than 50%, and more preferably more than 55%.In addition, although the value of the area ratio of above-mentioned subgrain is more high better, can be 100% ideally, from the view point of in actual manufacture, its upper limit can be less than 80%.
In above-mentioned alloy foil, its tensile strength is more than 210MPa.When tensile strength is less than 210MPa, then not talkative is the further raising achieving intensity.And, when tensile strength is less than 210MPa, such as, when carrying out thin-walled property, when force of compression being applied to paper tinsel by rolling etc., easily produce unnecessary viscous deformation.Above-mentioned tensile strength can be preferably more than 213MPa, is more preferably more than 215MPa, more preferably more than 220MPa.In addition, although do not limit especially the upper limit of tensile strength, can consider that the balance etc. of itself and ratio resistance decides optimal scope.Tensile strength can be such as about 330MPa or below.In addition, tensile strength is the 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.In addition, above-mentioned ratio resistance is the value measured in liquid nitrogen.In liquid nitrogen, measure ratio resistance is impact in order to eliminate measures ambient temperature.
Ratio resistance is relevant to the solid solution capacity of Si, Fe of alloying constituent.When ratio resistance is in above-mentioned scope, namely easy realization can not lose electroconductibility significantly, can improve intensity further again.If ratio resistance is less than 0.45 μ Ω cm, is then difficult to the raising being realized intensity by work hardening when manufacturing paper tinsel, is difficult to make tensile strength be more than 210MPa.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, although realize the raising of intensity by work hardening when manufacturing paper tinsel, can be observed the tendency that ratio resistance rises, electroconductibility declines.Therefore, ratio resistance can be made to be about 60% of the ratio resistance of the 3003 line aluminium alloy paper tinsels being considered to the higher alloy foil of strength ratio, i.e. 0.7 μ Ω about cm.Ratio resistance can be preferably 0.69 μ below Ω cm, is more preferably 0.68 μ below Ω cm.In addition, according to JIS H0505, ratio resistance can be measured by Kelvin double bridge method.
Above-mentioned alloy foil can be used for the current collector of battery electrode.In this case, the surface of the alloy foil as current collector is attached with electrode active material.Specifically, in this case, on the surface of alloy foil, the layer of coating containing electrode active material, applies force of compression by rolling etc. after the drying.Even under these circumstances, above-mentioned alloy foil is also difficult to because force of compression produces unnecessary viscous deformation, and therefore electrode active material is difficult to peel off, and, good electroconductibility can also be guaranteed.And, because above-mentioned alloy foil has paper tinsel intensity, be therefore also easy to the thin-walled property requirement tackling paper tinsel.Therefore, in this case, the densification of the secondary cells such as lithium ion battery etc. can be conducive to, high energy quantizes.
Such as can according to the above-mentioned alloy foil of following such manufacture.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, the Homogenization Treatments under high temperature do not carried out to aluminium alloy ingot bar and carry out hot rolling.Hot rolling after the temperature being heated to less than 350 DEG C, temperature when can hot rolling be started, in the way of hot rolling and at the end of hot rolling is all less than 350 DEG C.Although the hold-time later to the beginning temperature reaching hot rolling, there is no particular limitation, suppress the viewpoints such as the precipitation of Al-Fe-Si based compound, within can being set to 12 hours from easy.In addition, hot rolling can carry out once, also can carry out finish rolling etc. after roughing system, is divided into and carries out for several times.
And cold rolling is not annealed in midway, and makes paper tinsel thickness be less than 20 μm.If this is because anneal in midway, the precipitation of Al-Fe-Si based compound can be promoted, work hardening when can reduce cold rolling and cause the reduction of paper tinsel intensity.In addition, according to the reason identical with Process Annealing, preferably do not carry out yet cold rolling terminate after final annealing.From viewpoints such as raising paper tinsel intensity, the final rolling rate of cold rolling can be preferably more than 90%, is more preferably more than 95%.Final rolling rate be by 100 × value that calculates of (the paper tinsel thickness of the alloy foil after the cold rolling of the plate thickness of the hot rolling making sheet before cold rolling-final)/(plate thickness of the hot rolling making sheet before cold rolling).And, be in the paper tinsel rolling of less than 200 μm at thickness, can to the temperature of the paper tinsel before paper tinsel rolling and rolling rate, roll speed, adjusted by the cooling etc. of ROLLING OIL, make temperature during paper tinsel rolling be less than 120 DEG C.This is because easily making above-mentioned grain-size be the area ratio of the subgrain of less than 2 μm is more than 40%.
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 ~ K is the aluminium alloy of the chemical composition being suitable for embodiment, and alloy L ~ Q is the aluminium alloy of the chemical composition as comparative example.
[table 1]
Homogenization Treatments do not implemented to the aluminium alloy ingot bar of above-mentioned preparation and hot rolling is carried out to it, obtaining the hot rolling making sheet that thickness is 2mm.Now, hot rolling carries out roughing system and finish rolling system continuously.In addition, in above-mentioned hot rolling, by 350 DEG C being heated to by the aluminium alloy ingot bar before roughing system and keeps 6 hours thus make the beginning temperature of roughing (the beginning temperature of hot rolling) be 350 DEG C.And the end temp (the midway temperature of hot rolling) making roughing is 320 DEG C, makes the end temp of finish rolling (end temp of hot rolling) be 278 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 350 DEG C.
Then, 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.Now, in the paper tinsel rolling process below 200 μm, the end temp of paper tinsel rolling is all adjusted to less than 120 DEG C.In addition, the final rolling rate of above-mentioned cold rolling be 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 obtained alloy foil as test materials, the area ratio that its tensile strength, yield strength and unit elongation, ratio resistance (resistivity), grain-size are the subgrain of less than 2 μm is measured.Specifically, according to JIS Z2241, from test materials, JIS5 test piece is gathered to measure tensile strength, yield strength and unit elongation.According to JIS H0505, Kelvin double bridge method is used to measure ratio resistance.In addition, in order to eliminate the impact of envrionment temperature, the measurement of ratio resistance is carried out in liquid nitrogen.After specimen surface is finally processed with electropolishing (in the perchloric acid ethanol being cooled to-5 DEG C, carrying out the electropolishing of 10V-90 second), use SEM/EBSD method, with the step-length of 0.1 μm to specimen surface 900 μm
2region analyze, be that crystal boundary is regarded on the border of 5 ° ± 0.2 ° as by the misorientation between adjacent crystalline orientation measurement point, calculate the ratio (%) of the area of grain-size shared by the subgrain of less than 2 μm in the area of above-mentioned measured zone, thus obtain the area ratio that grain-size is the subgrain of less than 2 μm.And, in order to investigate paper tinsel rolling conditions, from the back side illuminaton light of test materials, by investigating the generation situation of pin hole in the lump with or without light leak.Show the result in table 2.And in FIG, show for test materials E11, use SEM/EBSD method is the result that the area ratio of the subgrain of less than 2 μm is measured to grain-size.In fig. 2, show for test materials C1, use SEM/EBSD method is the result that the area ratio of the subgrain of less than 2 μm is measured to grain-size.In two figure, grain-size is the subgrain of less than 2 μm is the part represented by grey.In addition, test materials E1 ~ E11 is embodiment, and test materials C1 ~ C4 is comparative example.
[table 2]
As shown in these results, test materials C1 employs the alloy L that Si contains quantity not sufficient 0.1%, Fe contains quantity not sufficient 0.2%, and grain-size is that the area ratio of the subgrain of less than 2 μm is low to moderate 25%.Therefore, test materials C1 can not be further enhanced the effect of intensity, and its tensile strength is low to moderate less than 210MPa.
Because test materials C2 employs the alloy M of Si content more than 0.6%, because which form the single-phase particle of thick Si, thereby produce pin hole.
Test materials C3 employs the alloy N of Fe containing quantity not sufficient 0.2%, and grain-size is that the area ratio of the subgrain of less than 2 μm is low to moderate less than 40%.Therefore, test materials C3 can not be further enhanced the effect of intensity, and its tensile strength is low to moderate less than 210MPa.
Because test materials C4 employs the ALLOY O of Fe content more than 1.0%, because which form thick Al-Fe system particle, thereby produce pin hole.
On the other hand, test materials E1 ~ E11 is formed by the alloy A containing above-mentioned specific chemical composition ~ K, and paper tinsel thickness is less than 20 μm, and grain-size is the area ratio of the subgrain of less than 2 μm is more than 40%, and tensile strength is more than 210MPa.And the ratio resistance that test materials E1 ~ E11 measures in liquid nitrogen is 0.45 μ more than Ω cm 0.7 μ below Ω cm, and known electroconductibility does not reduce significantly.
Therefore, according to this example, can provide a kind of alloy foil, this alloy foil can realize namely can not losing electroconductibility significantly, can improve intensity further again.Can think and why can obtain such alloy foil, be that when making paper tinsel thickness be below 20 μm, the reply of tissue is slow, presents tiny subgrain tissue, thus enhances effect because at the cold rolling carrying out more than 95%.And, even if above-mentioned alloy foil implements thin-walled property also have high strength, pin hole, paper tinsel problems of crack can also be avoided.
(embodiment 2)
By using the aluminium alloy B 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.And, by using 1050 alloys (alloy P), 3003 alloys (alloy Q) of the alloy in the past shown in semicontinuous casting method his-and-hers watches 1 carry out ingot bar and cut, get out the aluminium alloy ingot bar as comparing in the lump.
Use above-mentioned ready aluminium alloy ingot bar, under the manufacturing condition shown in table 3, produce the alloy foil that paper tinsel thickness is 12 μm.To the alloy foil of gained, similarly to Example 1, measure its tensile strength, yield strength and unit elongation, area ratio that ratio resistance (resistivity), grain-size are the subgrain of less than 2 μm, and investigate paper tinsel rolling conditions (with or without generation pin hole).The results are shown in table 4.In addition, test materials E12, E13 are embodiment, and test materials C5 ~ C12 is comparative example.
[table 3]
[table 4]
As shown in table 4, exceeded 350 DEG C because the hot rolling of test materials C5 ~ C7 when hot rolling starts temperature, therefore grain-size be the area ratio of the subgrain of less than 2 μm less than 40%, tensile strength is low to moderate less than 210MPa.
Test materials C8 has carried out Homogenization Treatments and has produced before hot rolling starts at 520 DEG C.Therefore, in test materials C8, define Al-Fe-Si based compound, the solid solution capacity of Si, Fe reduces, grain-size be the area ratio of the subgrain of less than 2 μm less than 40%, tensile strength is low to moderate less than 210MPa.
Test materials C9 is in the way of cold rolling, carries out Process Annealing produce when thickness of slab is 1mm at 380 DEG C.Therefore, in test materials C9, facilitate the precipitation of Al-Fe-Si based compound, grain-size be the area ratio of the subgrain of less than 2 μm less than 40%, tensile strength is low to moderate less than 210MPa.
Test materials C10 cold rolling end temp is during fabrication 130 DEG C.Therefore, in test materials C10, grain-size be the area ratio of the subgrain of less than 2 μm less than 40%, tensile strength is low to moderate less than 210MPa.
Test materials C11, C12 are 1050 alloys (alloy P), 3003 alloys (alloy Q) that use alloy in the past, and before hot rolling starts, carry out Homogenization Treatments under the high temperature of 500 DEG C more than 350 DEG C further and produce.Therefore, because the chemical composition of test materials C11 is identical with 1050 alloys (alloy P) of alloy in the past, so its tensile strength does not reach 210MPa, and grain-size is that the area ratio of the subgrain of less than 2 μm is also less than 40%.Because the chemical composition of test materials C12 is identical with 3003 alloys (alloy Q) of alloy in the past, therefore its ratio resistance is very up to 1.2 μ more than Ω cm, and poorly conductive.
On the other hand, test materials E12, E13 are formed by the alloy B containing above-mentioned specific chemical composition, and paper tinsel thickness is less than 20 μm, and grain-size is the area of the subgrain of less than 2 μm is more than 40%, and tensile strength is more than 210MPa.In addition, the ratio resistance that test materials E12, E13 measure in liquid nitrogen is 0.45 μ more than Ω cm 0.7 μ below Ω cm, and known electroconductibility does not reduce significantly.
Therefore, according to this example, can provide a kind of alloy foil, this alloy foil can realize namely can not losing electroconductibility significantly, can improve intensity further 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 coming containing more than Si:0.1% less than 0.6%, more than Fe:0.2% less than 1.0% by quality %, and remainder is that Al and inevitable impurity are formed;
Paper tinsel thickness is less than 20 μm;
When the border by the misorientation between adjacent crystalline orientation measurement point being 5 ° ± 0.2 ° is defined as crystal boundary, grain-size is the area ratio of the subgrain of less than 2 μm is more than 40%;
Tensile strength is more than 210MPa;
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. the alloy foil according to claims 1 or 2, is characterized in that,
Described alloy foil is used for the current collector of battery electrode.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-239312 | 2012-10-30 | ||
| JP2012239312A JP5959405B2 (en) | 2012-10-30 | 2012-10-30 | Aluminum alloy foil |
| PCT/JP2013/075077 WO2014069119A1 (en) | 2012-10-30 | 2013-09-18 | Aluminium alloy foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104769141A true CN104769141A (en) | 2015-07-08 |
| CN104769141B CN104769141B (en) | 2017-05-03 |
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| CN201380056002.6A Expired - Fee Related CN104769141B (en) | 2012-10-30 | 2013-09-18 | Aluminium alloy foil |
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| Country | Link |
|---|---|
| JP (1) | JP5959405B2 (en) |
| KR (1) | KR20150070201A (en) |
| CN (1) | CN104769141B (en) |
| DE (1) | DE112013005208T5 (en) |
| MY (1) | MY182959A (en) |
| WO (1) | WO2014069119A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388766A (en) * | 2014-11-27 | 2015-03-04 | 广西南南铝箔有限责任公司 | Production method of aluminum foil for lithium-ion battery |
| CN108779519A (en) * | 2016-03-11 | 2018-11-09 | 株式会社Uacj | Alloy foil |
| CN109252072A (en) * | 2018-10-15 | 2019-01-22 | 威海海鑫新材料有限公司 | A kind of high-precision aluminum foil stock and its preparation process |
| CN110016591A (en) * | 2019-04-09 | 2019-07-16 | 上海华峰铝业股份有限公司 | A kind of high conductivity collector alloy foil and its manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6631051B2 (en) * | 2015-06-30 | 2020-01-15 | 住友電気工業株式会社 | Lead conductor and power storage device |
| JP6769727B2 (en) * | 2016-04-07 | 2020-10-14 | 三菱アルミニウム株式会社 | Aluminum alloy foil for battery current collector and its manufacturing method |
| JP6973414B2 (en) | 2016-12-28 | 2021-11-24 | 大日本印刷株式会社 | Aluminum alloy foil for battery packaging materials, battery packaging materials, and batteries |
| CN107217181B (en) * | 2017-06-08 | 2018-10-02 | 合肥工业大学 | A kind of preparation method of high-strength Al-Si castings wrought alloy |
| JP6461249B2 (en) * | 2017-07-06 | 2019-01-30 | 三菱アルミニウム株式会社 | Aluminum alloy foil and method for producing aluminum alloy foil |
| CN111601904B (en) * | 2017-11-21 | 2023-01-10 | 斯佩拉有限公司 | Electrode foil for producing battery of lithium ion accumulator |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012021205A (en) * | 2010-07-16 | 2012-02-02 | Kobe Steel Ltd | Hardened aluminum foil for battery collector |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4644020B2 (en) * | 2005-03-31 | 2011-03-02 | 株式会社神戸製鋼所 | Aluminum foil for perforating and method for producing the same |
| JP5664084B2 (en) * | 2010-09-30 | 2015-02-04 | 株式会社三洋物産 | Game machine |
| US8527497B2 (en) * | 2010-12-30 | 2013-09-03 | Facebook, Inc. | Composite term index for graph data |
| JP5848672B2 (en) * | 2011-06-07 | 2016-01-27 | 株式会社Uacj | Method for producing aluminum alloy foil and aluminum alloy foil |
| JP2013146369A (en) * | 2012-01-19 | 2013-08-01 | T K Kikaku:Kk | Device for retarding aging |
| JP6055814B2 (en) * | 2012-03-29 | 2016-12-27 | 株式会社Uacj | Aluminum alloy foil for electrode current collector and method for producing the same |
-
2012
- 2012-10-30 JP JP2012239312A patent/JP5959405B2/en not_active Expired - Fee Related
-
2013
- 2013-09-18 MY MYPI2015701320A patent/MY182959A/en unknown
- 2013-09-18 DE DE112013005208.3T patent/DE112013005208T5/en not_active Withdrawn
- 2013-09-18 CN CN201380056002.6A patent/CN104769141B/en not_active Expired - Fee Related
- 2013-09-18 WO PCT/JP2013/075077 patent/WO2014069119A1/en active Application Filing
- 2013-09-18 KR KR1020157011234A patent/KR20150070201A/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012021205A (en) * | 2010-07-16 | 2012-02-02 | Kobe Steel Ltd | Hardened aluminum foil for battery collector |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388766A (en) * | 2014-11-27 | 2015-03-04 | 广西南南铝箔有限责任公司 | Production method of aluminum foil for lithium-ion battery |
| CN104388766B (en) * | 2014-11-27 | 2017-01-11 | 广西南南铝箔有限责任公司 | Production method of aluminum foil for lithium-ion battery |
| CN108779519A (en) * | 2016-03-11 | 2018-11-09 | 株式会社Uacj | Alloy foil |
| US11255001B2 (en) | 2016-03-11 | 2022-02-22 | Uacj Corporation | Aluminum-alloy foil |
| CN109252072A (en) * | 2018-10-15 | 2019-01-22 | 威海海鑫新材料有限公司 | A kind of high-precision aluminum foil stock and its preparation process |
| CN110016591A (en) * | 2019-04-09 | 2019-07-16 | 上海华峰铝业股份有限公司 | A kind of high conductivity collector alloy foil and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104769141B (en) | 2017-05-03 |
| JP5959405B2 (en) | 2016-08-02 |
| KR20150070201A (en) | 2015-06-24 |
| DE112013005208T5 (en) | 2015-09-03 |
| JP2014088598A (en) | 2014-05-15 |
| WO2014069119A1 (en) | 2014-05-08 |
| MY182959A (en) | 2021-02-05 |
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