CN104797725B - Aluminum-alloy foil - Google Patents
Aluminum-alloy foil Download PDFInfo
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- CN104797725B CN104797725B CN201380060970.4A CN201380060970A CN104797725B CN 104797725 B CN104797725 B CN 104797725B CN 201380060970 A CN201380060970 A CN 201380060970A CN 104797725 B CN104797725 B CN 104797725B
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- alloy foil
- paper tinsel
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- alloy
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- 239000011888 foil Substances 0.000 title claims abstract description 65
- 229910000838 Al alloy Inorganic materials 0.000 title abstract description 25
- 239000006104 solid solution Substances 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 84
- 239000000956 alloy Substances 0.000 claims description 84
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 3
- 239000010703 silicon Substances 0.000 abstract 3
- 238000012360 testing method Methods 0.000 description 33
- 238000005098 hot rolling Methods 0.000 description 29
- 238000001556 precipitation Methods 0.000 description 28
- 239000000463 material Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000005097 cold rolling Methods 0.000 description 18
- 238000005096 rolling process Methods 0.000 description 16
- 238000000605 extraction Methods 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 229910018191 Al—Fe—Si Inorganic materials 0.000 description 10
- 239000002210 silicon-based material Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910018084 Al-Fe Inorganic materials 0.000 description 6
- 229910018192 Al—Fe Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009749 continuous casting Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- -1 aluminium gold Chemical compound 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241000345998 Calamus manan Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (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
Technical field
The present invention relates to a kind of alloy foil.
Background technology
In the past, alloy foil was used in various fields, in recent years, from the viewpoint such as thin and conductive, aluminium
Alloy Foil is filled by collector as electrode etc. in electric power storages such as such as lithium ion battery, double layer capacitor, lithium-ion capacitors
Used in putting.Specifically, for example in patent document 1,2, to disclose and be used as electric power storage by what following manufacturing process was manufactured
Lithium ion cell positive in device.To on a face of the alloy foil as collector coating comprising positive active material with
And the layer of adhesive, it is allowed to drying.Afterwards, carry out rolling for improving positive active material density and with the stickiness of paper tinsel
System, so as to manufacture positive pole.
As above-mentioned alloy foil, for example, Patent Document 3 discloses a kind of aluminium alloy for lithium ion battery
Paper tinsel：It is by containing Si：0.01~0.60 mass %, Fe：0.2~1.0 mass %, Cu：0.05~0.50 mass %, Mn：0.5~
1.5 mass %, remainder is formed for Al and inevitable impurity, and its tensile strength is more than 240MPa, and n values are
More than 0.1.
In addition, as the prior art literature of the application, it is also other 2.In patent document 4, although disclosed
The alloy foil of lithium ion battery is not intended to, but discloses such a for the alloy foil of porous processing：It is by containing
There is Si：0.05~0.30 mass %, Fe：0.15~0.60 mass %, Cu：0.01~0.20 mass %, remainder be Al with
And inevitably impurity is formed, its tensile strength is 186~212N/mm2Left and right, paper tinsel thickness is 30 μm~100 μm or so.
And, in patent document 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% mass %, remainder is Al and inevitable impurity is constituted, and its solid solution
Fe contents in more than 200pm, do not pass through cold rolling by hot rolling and be made.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-234277 publications
Patent document 2：Japanese Unexamined Patent Publication 11-67220 publications
Patent document 3：Japanese Unexamined Patent Publication 2011-26656 publications
Patent document 4：Japanese Unexamined Patent Publication 2006-283114 publications
Patent document 5：Japanese Unexamined Patent Publication 2008-223075 publications
The content of the invention
The problem to be solved in the present invention
But, there is problem in the following areas in conventional alloy foil.That is, as described above, making in manufacture electrical storage device etc.
During with the part of paper tinsel, because the alloy foils such as rolling can be subject to compression stress.Therefore, alloy foil is needed with enough intensity,
So that unnecessary deformation or breakage will not occur relative to such compression stress.In recent years, it is desirable to the further thin-walled property of paper tinsel, it is
Tackle this requirement, it is also desirable to the high intensity of paper tinsel.
As the exemplary process of the high intensity for realizing paper tinsel, there is the method for adjustment al alloy component.But, only singly
If pure adjustment alloying component, due to the addition of the alloying component beyond Al, can increase the ratio resistance of paper tinsel, electric conductivity reduction.
So, conventional alloy foil there are problems that such：It is difficult to neither significantly lose electric conductivity, high intensity can be realized again
Change.
The present invention is in view of above-mentioned background, there is provided a kind of alloy foil, the alloy foil can not significantly lose electric conductivity,
High intensity can be realized again.
The method of solve problem
The alloy foil of an embodiment of the invention, it is characterised in that the chemical composition of the alloy foil is by by matter
Amount % contains Si to count：Less than more than 0.1% 0.6%, Fe：Less than more than 0.2% 1.5%, and Si contents and the conjunction of Fe contents
More than 0.48% is calculated as, remainder is formed for Al and inevitable impurity, paper tinsel thickness is less than 20 μm, the solid solution of Si
It is more than 700 mass ppm to measure, and the solid solution capacity of Fe is more than 150 mass ppm, and tensile strength is more than 220MPa, is surveyed in liquid nitrogen
Fixed ratio resistance is below the μ Ω cm of more than 0.45 μ Ω cm 0.7.
Invention effect
Above-mentioned alloy foil can be realized due to above-mentioned specific composition, can not significantly lose electric conductivity
High intensity.Therefore, above-mentioned alloy foil, though for example manufacture electrode etc. of electrical storage device using paper tinsel part when pass through
In the case that rolling etc. is to apply compression stress, can also suppress unnecessary plastic deformation, be also easy to realize the thin-walled property of paper tinsel.And
And, even if above-mentioned alloy foil also will not significantly lose electric conductivity under improving intensity, it can be ensured that good electric conductivity.Cause
This, if the collector using above-mentioned alloy foil for example as electrode in the electrical storage device of lithium ion battery etc. is used, can help
Densification, high energy in electrical storage device quantify.
Brief description of the drawings
Fig. 1 is the explanatory diagram illustrated for substantially step when Si solid solution capacities, Fe solid solution capacities are determined in embodiment.
Specific embodiment
(unit is quality %, is only saved in following chemical composition explanation specified chemical composition in above-mentioned alloy foil
Meaning slightly " % ") and restriction reason are as mentioned below.
Si：Less than more than 0.1% 0.6
Si is the essential elements for realizing improving paper tinsel intensity.When paper tinsel is manufactured, if the temperature of aluminium alloy is more than 350 DEG C,
Then the Si and Fe of solid solution are easily separated out as Al-Fe-Si based compounds, thus can reduce the processing hardening of cold rolling, easily
Reduce paper tinsel intensity.It is therefore preferred that the homogenize process not being performed for more than when paper tinsel is manufactured at a high temperature of 350 DEG C, and 350
Hot rolling is carried out under conditions of below DEG C.In order to improve paper tinsel intensity under this condition, the ratio resistance of paper tinsel is reduced so that it is guaranteed that it is led
Electrically, it is necessary to make Si contents less than 0.6% more than 0.1%.If Si contents are less than 0.1%, the ratio resistance reduction of paper tinsel, but
The intensity of paper tinsel is not improved.If Si amounts are more than 0.6%, it is difficult to further improve paper tinsel intensity, easily forms thick Si
Single-phase particle, pin hole, the problem of paper tinsel cracking are susceptible to when paper tinsel thickness is below 20 μm.Si contents preferably for 0.12% with
On.Si contents are preferably less than 0.4%.
Fe：Less than more than 0.2% 1.5%
Fe is the essential elements for realizing improving paper tinsel intensity inferior to Si, if the temperature of aluminium alloy exceedes when paper tinsel is manufactured
350 DEG C, then the Si and Fe of solid solution easily as the precipitation of Al-Fe-Si based compounds, harden by the processing that thus can reduce cold rolling
Property, it is easily reduced paper tinsel intensity.It is therefore preferred that the homogenize process not being performed for more than when paper tinsel is manufactured at a high temperature of 350 DEG C,
And below 350 DEG C under conditions of carry out hot rolling.In order to improve paper tinsel intensity under this condition, the ratio resistance of paper tinsel is reduced so as to really
Its electric conductivity is protected, it is necessary to make Fe contents less than 1.5% more than 0.2%.If Fe contents are less than 0.2%, the ratio resistance of paper tinsel drops
It is low, but the intensity of paper tinsel is not improved.If Fe contents are higher than 1.5%, it is difficult to further improve paper tinsel intensity, and the shape in casting
Into thick Al-Fe systems crystal.As described above, not homogenized at a high temperature of more than 350 DEG C to aluminium alloy ingot bar
In the case for the treatment of, the Al-Fe systems crystal formed during casting is remained in final paper tinsel thickness with thick form.Therefore,
Pin hole, the problem of paper tinsel cracking are susceptible to when paper tinsel thickness is below 20 μm.And, the necessary Fe above of addition is also manufacture
The reason for cost increases.Fe contents are preferably more than 0.30%.Fe contents are preferably less than 1.2%, more preferably 1.0%
Hereinafter, more preferably less than 0.80%.
Si contents add up to Fe contents：More than 0.48%
Si contents are ensuring the tensile strength of more than 220MPa with total (" Si+Fe amounts " used below is represented) of Fe contents
Aspect is most important.If Si+Fe is measured less than 0.48%, it is impossible to is obtained the tensile strength of more than 220MPa, and is difficult to height
Intensity.Measured from Si+Fe and be easy to from the viewpoint of the tensile strength for ensuring more than 220MPa, preferably more than 0.49%, it is more excellent
Elect more than 0.5% as, be further preferably more than 0.52%.Also, in view of above-mentioned Si contents, upper limit of Fe contents etc., Si+
Fe amounts can be less than 1.6%, preferably less than 1.4%, more preferably less than 1.2%.
Above-mentioned chemical composition, by quality %, can further contain Cu：Less than more than 0.01% 0.25%.In this case
Meaning and restriction reason as mentioned below.
Cu：Less than more than 0.01% 0.25%
Cu contributes to improve the element of paper tinsel intensity.In order to obtain the effect, Cu contents are preferably made to be more than 0.01%.
Alternatively, it is also possible to containing the Cu less than 0.01% as inevitable impurity.On the other hand, the paper tinsel intensity if Cu contents are excessive
Increase.But ratio resistance can also increase.It is therefore preferred to make Cu contents be less than 0.25%.Cu contents preferably for 0.02% with
On.Cu contents are preferably less than 0.18%.
In above-mentioned chemical composition, as inevitable impurity, the units such as Mn, Mg, Cr, Zn, Ni, Ga, V, Ti can be contained
Element.But, if excessively containing Mn, Mg, can probably increase the ratio resistance of paper tinsel, and reduce conductance.It is therefore preferred that containing Mn
Measure is that less than 0.01%, Mg contents are less than 0.01%.Because the other elements such as Cr, Zn, Ni, Ga, V, Ti are than being less favorable for
Increase the element of ratio resistance, preferably make each element content below 0.05%.In addition, all inevitably impurity adds up to
If amount is below 0.15%, because there is no substantial influence on electric conductivity, high intensity being allowed.
In above-mentioned alloy foil, paper tinsel thickness is less than 20 μm.If paper tinsel thickness is more than 20 μm, can not tackle in recent years
The thin-walled property (paper tinsel thickness calibration size reduction (gauge down)) of the paper tinsel for requiring extensively.Above-mentioned alloy foil, due to paper tinsel thickness
Below 20 μm, for example, particularly suitable in the collector purposes of the electrical storage device electrode higher of the thin-walled property requirement for paper tinsel.
In above-mentioned alloy foil, from viewpoints such as thin-walled property, the miniaturizations that can help to electrical storage device, paper tinsel thickness is preferably
Can be more preferably less than 18 μm less than 20 μm, it may be more preferable to be less than 19 μm, can still more preferably be less than 17 μm.
On the other hand, for example, from viewpoints such as the easily operated property when the part of the use paper tinsel of electrode etc. of electrical storage device is manufactured,
Paper tinsel thickness is preferably more than 8 μm, it may be more preferable to is more than 9 μm, can be more preferably more than 10 μm.
In above-mentioned alloy foil, the solid solution capacity of Si is more than 700 mass ppm, and the solid solution capacity of Fe is 150 mass ppm
More than.If solid solution capacity of the solid solution capacity of Si less than 700 mass ppm, Fe can not then realize that tensile strength exists less than 150 mass ppm
The high intensity of more than 220MPa.From from the viewpoint of above-mentioned guarantee high intensity, the solid solution capacity of Si, preferably 720 mass ppm
More than, more preferably more than 740 mass ppm, more preferably 760 mass ppm.Also, the solid solution capacity of Si is preferably higher
Numerical value.But, in actual manufacture, from ingot bar when cooling velocity etc. from the viewpoint of, 1000 mass ppm are limited to thereon.It is another
Aspect, from from the viewpoint of above-mentioned guarantee high intensity, the solid solution capacity of Fe, preferably more than 170 mass ppm, more preferably 190
More than quality ppm, more preferably more than 200 mass ppm.Also, the solid solution capacity of Fe, numerical value preferably higher.But, it is real
In the manufacture of border, from ingot bar when cooling velocity etc. from the viewpoint of, 500 mass ppm are limited to thereon.
The solid solution capacity of the solid solution capacity of above-mentioned Si, above-mentioned Fe, substantially, can be measured by the following method.That is, heat is used
Phenol dissolves extraction method, and its Al-Fe based compound as residue for containing is obtained in the test piece gathered from alloy foil,
Al-Fe-Si based compounds.Then, dissolve extraction method by the hot phenol to be dissolved out Si, Fe from above-mentioned residue, and lead to
Crossing ICP emission spectrometry (ICP) carries out quantitative analysis, obtains the Si separated out as above-claimed cpd
Amount of precipitation, Fe amount of precipitations.Also, dissolving with hydrochloric acid extraction method is used, its work for containing is obtained in the test piece gathered from aluminium gold paper tinsel
It is the single-phase particles of the Si of residue.Then, above-mentioned residue is dissolved by the dissolving with hydrochloric acid extraction method, quantitative analysis is carried out by ICP,
Obtain the Si amount of precipitations separated out as the single-phase particles of Si.Then, will by hot phenol dissolve the Si amount of precipitations that obtain of extraction method and
By obtain Si amount of precipitations of dissolving with hydrochloric acid extraction method and it is used as the total amount of precipitations of Si.Also, will be dissolved by hot phenol and extracted
The Fe amount of precipitations that method is obtained are used as the total amount of precipitations of Fe.Then, the Si constituent analysis values of alloy foil are subtracted into the total amount of precipitations of Si to obtain
The value for arriving is used as Si solid solution capacities.Also, the Fe constituent analysis values of alloy foil are subtracted the value of the total amount of precipitations of Fe as Fe solid solutions
Amount.
In above-mentioned alloy foil, tensile strength is more than 220MPa.It is unable to reach if tensile strength is less than 220MPa
High intensity described in the application.Tensile strength is preferably more than 223Mpa, more preferably more than 225Mpa, more preferably
More than 230Mpa.And, it is contemplated that determine that the upper limit of tensile strength obtains most suitable scope with the balance of ratio resistance.For example, tension
Intensity controlled system is in below 340Mpa.Also, tensile strength is the numerical value according to JIS (Japanese Industrial Standards) Z2241 measurements.
In above-mentioned alloy foil, ratio resistance is below the μ Ω cm of more than 0.45 μ Ω cm 0.7.Also, it is above-mentioned than electricity
Resistance is the numerical value determined in liquid nitrogen.It is to eliminate the influence of determination of the environment temperature that ratio resistance is determined in liquid nitrogen.
The solid solution capacity of the Si of ratio resistance and alloying component, Fe is related.Ratio resistance within the above range in the case of, can be both
Electric conductivity is not lost significantly, and high intensity can be realized again.If ratio resistance is difficult to less than 0.45 μ Ω cm when paper tinsel is manufactured
Processing hardening, and be difficult to make tensile strength reach more than 220MPa.Ratio resistance is preferably more than 0.50 μ Ω cm, more excellent
Elect as more than 0.55 μ Ω cm.On the other hand, if ratio resistance is uprised, the hardening easy to process when paper tinsel is manufactured, and it is easy to real
Existing high intensity.But, the tendency of electric conductivity decline can be observed.Therefore, ratio resistance can be made to be 0.7 μ Ω cm or so, i.e. quilt
It is considered about the 60% of the ratio resistance of 3003 line aluminium alloy paper tinsels of intensity alloy foil higher.Ratio resistance is preferably 0.69
Below μ Ω cm, it may be more preferable to be below 0.68 μ Ω cm.Also, can be surveyed by double bridge method according to JIS H0505
Amount ratio resistance.
Above-mentioned alloy foil, can use as the collector of electrical storage device electrode.In this case, as collector
Alloy foil is attached with electrode active material on surface.Specifically, in this case, on the surface of alloy foil, apply
The layer containing electrode active material is covered with, compression stress is applied by rolling etc. after the drying.Even if in this case, above-mentioned aluminium
Alloy Foil is also difficult to produce unnecessary plastic deformation because of compression stress, therefore electrode active material is difficult to peel off, furthermore, it is possible to
Ensure good electric conductivity.Also, due to the paper tinsel excellent strength of above-mentioned alloy foil, thus be also easy to tackle paper tinsel thin-walled property will
Ask, therefore, in this case, the densification of the electrical storage device of lithium ion battery etc., high energy can be conducive to quantify.
Above-mentioned alloy foil, for example can be according to manufacture described below.That is, can be by by above-mentioned specific chemical composition shape
Into aluminium alloy ingot bar carry out hot rolling after, carry out comprising paper tinsel rolling cold rolling, so as to obtain above-mentioned alloy foil.
Now, the homogenize process at a high temperature of 350 DEG C are not performed for more than to aluminium alloy ingot bar and carry out hot rolling.
Hot rolling since being heated to after less than 350 DEG C of temperature, when starting hot rolling, hot rolling midway and hot rolling at the end of
Temperature is all less than 350 DEG C.Reach hot rolling started temperature after retention time, from be easy to suppress Al-Fe-Si based compounds
Precipitation etc. from the viewpoint of, can be set within 12 hours.Additionally, hot rolling can be carried out once, also can be laggard in roughing system
Row finish rolling system, be divided into is carried out for several times.
In addition, cold rolling is not annealed in midway, and make paper tinsel thickness below 20 μm.If carrying out Process Annealing, can promote
Enter the precipitation of Al-Fe-Si based compounds, processing hardening when reducing cold rolling and cause the reduction of paper tinsel intensity.Additionally, root
According to it is same with Process Annealing the reasons why, do not carry out the final annealing after cold rolling terminates preferably yet.From realizing that tensile strength exists
The high intensity viewpoint of more than 220MPa is set out, in the cold rolling rolled comprising paper tinsel final rolling rate preferably for 95% with
On, more preferably more than 96%, more preferably more than 97%.Final rolling rate is by the 100 × (hot rolling before cold rolling
The paper tinsel thickness of the alloy foil after the plate thickness-final cold rolling system of plate)/(plate thickness of the hot rolling making sheet before cold rolling) calculating
The value for going out.
Embodiment
The alloy foil involved by embodiment is illustrated below.
Embodiment 1
Ingot bar to the aluminium alloy of the chemical composition shown in table 1 is carried out by using semi-continuous casting method and is cut, so that
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 change for being adapted for carrying out example
The aluminium alloy for studying point, alloy I~O is the aluminium alloy as the chemical composition of comparative example.
Table 1
To above-mentioned ready aluminium alloy ingot bar, do not carry out homogenize process and carry out hot rolling, it is 2mm's to obtain thickness
Hot rolling making sheet.Now, hot rolling is made as the roughing system and finish rolling system being carried out continuously.Also, in above-mentioned hot rolling, by will be for thick
Aluminium alloy ingot bar before rolling, heated and kept with 330 DEG C 6 hours so that the started temperature of roughing (hot rolling is opened
Beginning temperature) it is 330 DEG C.Also, make the end temp (the midway temperature of hot rolling) of roughing be 310 DEG C, the end of finish rolling
Temperature (end temp of hot rolling) is 270 DEG C.In such this example, the started temperature and knot of above-mentioned hot rolling are not only
Shu Wendu, and hot rolling midway temperature be roughing end temp, that is, finish rolling started temperature also be 330 DEG C
Below.
Then, after dropping back to room temperature, do not annealed in midway and the cold rolling comprising paper tinsel rolling is repeated, obtained paper tinsel thick
Spend the alloy foil for 12 μm.Also, the final rolling rate in above-mentioned cold rolling is, 100 × (the hot rolling making sheet before cold rolling
2000 μm of plate thickness-final cold rolling after alloy foil 12 μm of paper tinsel thickness)/(plate of the hot rolling making sheet before cold rolling
2000 μm of thickness)=99.4%.
Then, the alloy foil that will be obtained as test material, determine its tensile strength, yield strength and elongation percentage,
Ratio resistance (resistivity), Si solid solution capacities and Fe solid solution capacities.Specifically, tensile strength, yield strength and elongation percentage are according to JIS
Z2241, selection JIS5 test pieces are measured under n=2 from test material.Ratio resistance foundation JIS H0505, using both arms
Bridge method is measured.In addition, the influence in order to eliminate environment temperature, the measure of ratio resistance is carried out in liquid nitrogen.
The measure of Si solid solution capacities and Fe solid solution capacities, follows the steps below.Reference picture 1 is illustrated.In Fig. 1,
The residue by being obtained by hot phenol dissolving extraction method and the residue obtained by dissolving with hydrochloric acid extraction method are described, is analyzed
The total amount of precipitations of Si, the method for total amount of precipitation of Fe in alloy foil.Also, Si amount of precipitations, the analysis method of Fe amount of precipitations can
With reference to academic documents " assistant rattan, spring：The 68th Spring Meeting speech summary of light metal association, (1985), 55 ", academic documents " village
Pine, loose tail, little Song etc.：The 76th Spring Meeting speech summary of light metal association, (1989), 51. ".
First, carry out being dissolved on hot phenol the explanation of extraction method.The test piece (S10) of 2g is chosen from alloy foil.And
And, test piece is the small pieces cut out from alloy foil, adds up to and weighs 2g.Then, the beaker of 50ml phenol will be added to be placed on to add
On hot plate, after heating phenol with 170 DEG C~180 DEG C, input test piece makes its dissolving (S11).Then, the burning of above-mentioned solution will be added
Cup is taken down and is cooled down (S12) from heating plate.Then, in order to prevent solidification, phenmethylol is added in the solution of above-mentioned cooling
(S13).Then, the above-mentioned solution that with the addition of phenmethylol is filtered by the film filter (0.1 μm of aperture) of polytetrafluoroethylene (PTFE)
(S14) Al-Fe based compounds, the Al-Fe-Si based compounds (S15) as residue, are obtained.Then, 10%-NaOH solution is used
By Si from this after being dissolved during hot phenol dissolves the residue that obtains of extraction method, then (volume ratio is concentrated hydrochloric acid with chloroazotic acid：Concentrated nitric acid
=3:1) Fe is dissolved, obtains the mixed liquor of Si, Fe containing dissolving.Then, by inductively coupled plasma atomic emission
Analytic approach (ICP) carries out quantitative analysis (S16).Thus, obtain and obtain as Al-Fe based compounds, Al-Fe-Si based compounds
The Si amount of precipitations of precipitation, Fe amount of precipitations.
Then, the explanation on dissolving with hydrochloric acid extraction method is carried out.The test piece (S20) of 2g is chosen from alloy foil.Also,
Test piece is chosen according to mode similar to the above.Then, 120mLHCl is added, (volume ratio is concentrated hydrochloric acid：Water=1：1) burning
Test piece is put into cup and is dissolved at room temperature, add 2~3 drop hydrogen peroxide H2O2(S21).Then, by above-mentioned solution by poly-
The film filter (0.1 μm of aperture) filtering (S24) of tetrafluoroethene, obtains as the single-phase particles of the Si (S25) of residue.Then,
By this after the residue that dissolving with hydrochloric acid extraction method is obtained is dissolved with 10%-NaOH solution, mix with above-mentioned chloroazotic acid, be acidified to
PH1~2.Then, quantitative analysis (S26) is carried out to the solution by ICP emission spectrometry (ICP).
Thus, the Si amount of precipitations separated out as the single-phase particles of Si are obtained.
Then, obtained by the Si amount of precipitations obtained by above-mentioned hot phenol dissolving extraction method and by dissolving with hydrochloric acid extraction method
Si amount of precipitations sum as the total amount of precipitations of Si.Also, the Fe amount of precipitations work that extraction method is obtained will be dissolved by above-mentioned hot phenol
It is the total amount of precipitations of Fe.Then, the Si constituent analysis values of alloy foil are subtracted value that the total amount of precipitations of Si obtain as Si solid solution capacities.
Also, the Fe constituent analysis values of alloy foil are subtracted value that the total amount of precipitations of Fe obtain as Fe solid solution capacities.
Additionally, in order to investigate paper tinsel rolling conditions, be illuminated from the back side of test material, by whetheing there is light leak to pin hole
Generation situation is also investigated in the lump.Result above is as shown in table 2.
Table 2
As shown in these results, test material C1 is due to using the alloy I that Si+Fe contents are 0.47%, tensile strength
As little as less than 220MPa.
Test material C2 has used alloy J of the Si contents less than 0.1%, Fe contents less than 0.2%, and Si solid solution capacities are not enough
700 mass ppm, Fe solid solution capacities are less than 150 mass ppm.Therefore, test material C2, tensile strength is as little as less than 220MPa.
Test material C3 forms the single-phase particles of thick Si due to having used alloy K of the Si contents more than 0.6%, by
This generates pin hole.
Test material C4 has used alloy L of the Fe contents less than 0.2%, and Fe solid solution capacities less than 150 mass ppm.Therefore,
Test material C3, tensile strength is as little as less than 220MPa.
Test material C5 forms thick Al-Fe systems particle due to having used alloy M of the Fe contents more than 1.5%, by
This generates pin hole.
On the other hand, test material E1~E8, by the alloy A~H-shaped containing above-mentioned specified chemical composition into paper tinsel is thick
It is less than 20 μm to spend, and the solid solution capacity of Si is more than 700 mass ppm, and the solid solution capacity of Fe is more than 150 mass ppm, and tensile strength is
More than 220MPa.And, test material E1~E8, the ratio resistance determined in liquid nitrogen is more than 0.45 μ Ω cm 0.7 μ
Below Ω cm.As can be known from the results, test material E1~E8 not only realizes high intensity of the tensile strength in more than 220MPa,
Electric conductivity is also without very big decline.
Thus, according to this example, it is possible to provide a kind of alloy foil, the alloy foil does not both lose electric conductivity significantly, and
High intensity can be realized.Also, above-mentioned alloy foil, even if also there is high intensity after due to realizing thin-walled property, such that it is able to
Avoid pin hole, paper tinsel problems of crack.
Embodiment 2
Ingot bar to the aluminium alloy A of the chemical composition shown in table 1 is carried out by using semi-continuous casting method and is cut, so that accurate
Get aluminium alloy ingot bar ready.Also, by using semi-continuous casting method to 1050 alloy (alloys of the conventional alloy shown in table 1
N), 3003 alloys (alloy O) carry out ingot bar and cut, so as to be ready in the lump as the aluminium alloy ingot bar for comparing.
Using above-mentioned ready aluminium alloy ingot bar, the aluminium that paper tinsel thickness is 12 μm is produced with the manufacturing condition shown in table 3
Alloy Foil.Also, the cold rolling in table 3, since being down to after room temperature.To the alloy foil for obtaining, similarly to Example 1
Ground, determines its tensile strength, yield strength and elongation percentage, ratio resistance (resistivity), Si solid solution capacities and Fe solid solution capacities, and adjust
Look into paper tinsel rolling conditions (whether there is generation and pin hole occurs).During its result is as shown in table 4.
Table 3
Table 4
As shown in table 4, due to test material C6~C8, in hot rolling, the started temperature of hot rolling promotes more than 350 DEG C
The formation of Al-Fe-Si based compounds, makes the Si solid solution capacities less than 700 mass ppm, Fe solid solution capacities less than 150 mass ppm, tension
Intensity is as little as less than 220MPa.
Test material C9 carries out homogenize process and is made before hot rolling starts with 520 DEG C.Therefore, test material C9
The formation of Al-Fe-Si based compounds is promoted, makes Si solid solution capacities less than 700 mass ppm, Fe solid solution capacities less than 150 mass ppm,
Tensile strength is as little as less than 220MPa.
Test material C10, the started temperature of its hot rolling is 340 DEG C.But, in the way of cold rolling, it is in plate thickness
It is made so that 380 DEG C carry out Process Annealing during 1mm.Therefore, test material C10 promotes the formation of Al-Fe-Si based compounds,
Make Si solid solution capacities less than 700 mass ppm, Fe solid solution capacities less than 150 mass ppm, tensile strength is as little as less than 220MPa.
Test material C11, C12 are 1050 alloys (alloy N) for using conventional alloy, and 3003 alloys (alloy O) go forward side by side one
Step carries out what homogenize process were made at a high temperature of before hot rolling starts with 520 DEG C more than 350 DEG C.Due to test material
The chemical composition of C11 is identical with 1050 alloys (alloy N) of conventional alloy, and its tensile strength is as little as less than 220MPa.Due to examination
The chemical composition for testing material C 12 is identical with 3003 alloys (alloy O) of conventional alloy, its ratio resistance be up to 1.2 μ Ω cm with
On, electric conductivity is poor.
On the other hand, test material E9, E10, forms by the alloy A containing above-mentioned specific chemical composition, and paper tinsel is thick
It is less than 20 μm to spend, and the solid solution capacity of Si is more than 700 mass ppm, and the solid solution capacity of Fe is for more than 150ppm mass, tensile strength is
More than 220MPa.Also, test material E9, E10, the ratio resistance determined in liquid nitrogen are more than 0.45 μ Ω cm 0.7 μ
Below Ω cm.As can be known from the results, test material E9, E10 not only realize high intensity of the tensile strength in more than 220MPa,
Electric conductivity is also without very big decline.
Therefore, according to this example, it is possible to provide a kind of alloy foil, the alloy foil does not both lose electric conductivity significantly, and
High intensity can be realized.
Although being illustrated to embodiment above, the present invention is not limited to above-described embodiment, is not damaging this
Various modifications can be carried out in the range of the purport of invention.
Claims (3)
1. a kind of alloy foil, it is characterised in that including：
Its chemical composition contains Si by based on quality %：Less than more than 0.1% 0.6%, Fe:Less than more than 0.2% 1.5%, and
And Si contents are aggregated in more than 0.48% with Fe contents, remainder is formed for Al and inevitable impurity；
Paper tinsel thickness is less than 20 μm；
The solid solution capacity of Si is more than 700 mass ppm, and the solid solution capacity of Fe is in more than 150 mass ppm；
Tensile strength is more than 220MPa；
The ratio resistance determined in liquid nitrogen is below the μ Ω cm of more than 0.45 μ Ω cm 0.7.
2. alloy foil according to claim 1, it is characterised in that the chemical composition by quality % come based on further contain
There is Cu：Less than more than 0.01% 0.25%.
3. alloy foil according to claim 1, it is characterised in that the alloy foil is used for the collection of electrical storage device electrode
Electric body.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012263918A JP5959423B2 (en) | 2012-12-03 | 2012-12-03 | Aluminum alloy foil |
| JP2012-263918 | 2012-12-03 | ||
| PCT/JP2013/080890 WO2014087827A1 (en) | 2012-12-03 | 2013-11-15 | Aluminum-alloy foil |
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| CN104797725B true CN104797725B (en) | 2017-05-24 |
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| JP (1) | JP5959423B2 (en) |
| KR (1) | KR20150086481A (en) |
| CN (1) | CN104797725B (en) |
| DE (1) | DE112013005772T5 (en) |
| MY (1) | MY170531A (en) |
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| KR20160075604A (en) * | 2013-10-25 | 2016-06-29 | 가부시키가이샤 유에이씨제이 | Aluminum alloy foil for electrode current collector, and method for producing same |
| JP6431314B2 (en) * | 2014-08-13 | 2018-11-28 | 三菱アルミニウム株式会社 | Method for producing aluminum alloy foil |
| JP6431315B2 (en) * | 2014-08-14 | 2018-11-28 | 三菱アルミニウム株式会社 | Aluminum alloy foil and method for producing the same |
| US20190024218A1 (en) * | 2016-02-01 | 2019-01-24 | Uacj Corporation | Aluminum alloy foil and manufacturing method thereof |
| KR20180123520A (en) * | 2016-03-11 | 2018-11-16 | 가부시키가이샤 유에이씨제이 | Aluminum alloy foil |
| JP2017166027A (en) * | 2016-03-16 | 2017-09-21 | 株式会社Uacj | Aluminum alloy foil |
| 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 |
| PL3714077T3 (en) * | 2017-11-21 | 2024-05-20 | Speira Gmbh | Battery electrode foil for the production of lithium-ion accumulators |
| CN108149172B (en) * | 2017-12-26 | 2019-11-01 | 湖南科技大学 | A kind of processing method of fine grain cubic texture corrosion fatigue resistant aluminum alloy plate materials |
| JP6730382B2 (en) * | 2018-08-13 | 2020-07-29 | 三菱アルミニウム株式会社 | Aluminum foil for battery current collector and method of manufacturing the same |
| CN111044598A (en) * | 2018-11-28 | 2020-04-21 | 东莞东阳光科研发有限公司 | Method for measuring solid precipitation amount and solid solubility of alloying metal elements in aluminum foil |
| JP7216571B2 (en) * | 2019-02-26 | 2023-02-01 | 東洋アルミニウム株式会社 | Aluminum alloy foil and its manufacturing method |
| CN111519050B (en) * | 2020-04-13 | 2021-10-22 | 江苏中基复合材料有限公司 | Aluminum foil for low-pinhole high-finish electronic tag and production process thereof |
| CN114277286B (en) * | 2021-12-29 | 2022-08-02 | 江苏鼎胜新能源材料股份有限公司 | High-tensile-strength and high-extensibility aluminum foil for power lithium battery and preparation method thereof |
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| JP5495694B2 (en) * | 2009-09-30 | 2014-05-21 | 株式会社Ｕａｃｊ製箔 | Aluminum alloy foil for lithium ion secondary battery and method for producing the same |
| JP5591583B2 (en) * | 2010-05-14 | 2014-09-17 | 株式会社Ｕａｃｊ | Aluminum alloy foil for lithium-ion battery electrode current collector |
| JP5639398B2 (en) * | 2010-07-16 | 2014-12-10 | 株式会社神戸製鋼所 | Aluminum hard foil for battery current collector |
| JP2012224927A (en) * | 2011-04-21 | 2012-11-15 | Mitsubishi Alum Co Ltd | Aluminum alloy foil for positive electrode current collector of lithium ion battery, and method for manufacturing the same |
| JP5848672B2 (en) * | 2011-06-07 | 2016-01-27 | 株式会社Uacj | Method for producing aluminum alloy foil and aluminum alloy foil |
| KR102045000B1 (en) * | 2012-03-29 | 2019-11-14 | 가부시키가이샤 유에이씨제이 | Aluminum alloy foil for electrode current collector and method for manufacturing same |
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| WO2014087827A1 (en) | 2014-06-12 |
| CN104797725A (en) | 2015-07-22 |
| JP2014109057A (en) | 2014-06-12 |
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