WO2017135108A1 - アルミニウム合金箔およびその製造方法 - Google Patents
アルミニウム合金箔およびその製造方法 Download PDFInfo
- Publication number
- WO2017135108A1 WO2017135108A1 PCT/JP2017/002383 JP2017002383W WO2017135108A1 WO 2017135108 A1 WO2017135108 A1 WO 2017135108A1 JP 2017002383 W JP2017002383 W JP 2017002383W WO 2017135108 A1 WO2017135108 A1 WO 2017135108A1
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- WIPO (PCT)
- Prior art keywords
- aluminum alloy
- less
- alloy foil
- foil
- orientation
- Prior art date
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- 239000011888 foil Substances 0.000 title claims abstract description 126
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 99
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 56
- 239000000126 substance Substances 0.000 claims abstract description 18
- 238000013507 mapping Methods 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 238000005098 hot rolling Methods 0.000 claims description 27
- 238000005097 cold rolling Methods 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 13
- 238000000265 homogenisation Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000002050 diffraction method Methods 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 238000001887 electron backscatter diffraction Methods 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 7
- 229910018084 Al-Fe Inorganic materials 0.000 description 6
- 229910018192 Al—Fe Inorganic materials 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910018191 Al—Fe—Si Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KFSUNTUMPUWCMW-UHFFFAOYSA-N ethanol;perchloric acid Chemical compound CCO.OCl(=O)(=O)=O KFSUNTUMPUWCMW-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
-
- 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
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to an aluminum alloy foil and a method for producing the same.
- a positive electrode is usually obtained by applying a mixture slurry containing an electrode active material to the surface of an aluminum alloy foil as a current collector, drying it, and compressing it with a press. Manufactured.
- the manufactured positive electrode is generally stored in a case in a state of being laminated with a separator and a negative electrode, or in a state of being wound in a laminated state.
- the aluminum alloy foil is heat-treated at about 100 ° C. to 160 ° C. during drying after applying the mixture slurry.
- an electrode including an aluminum alloy foil is heat-treated at a temperature of 50 ° C. to 350 ° C. for several hours so as to be accompanied by thermal modification of a binder and a thickener added to the mixture slurry.
- the technology is described.
- the aluminum alloy foil may be exposed to a high temperature state for a long time in the electrode manufacturing process.
- Patent Document 2 contains, for example, Mn: 1.0 to 1.5% by weight, Cu: 0.05 to 0.20% by weight, with the balance being Al. And an aluminum alloy foil for lithium batteries comprising impurities.
- Patent Document 3 contains Mn: 0.10 to 1.50 mass%, Fe: 0.20 to 1.50 mass%, and the total of Mn and Fe is 1.30 to 2.10 mass%. And the aluminum alloy foil which the remainder consists of Al and an inevitable impure part is disclosed.
- JP 2008-277196 A Japanese Patent Laid-Open No. 11-67220 Japanese Patent No. 5567719
- the conventional technique has the following problems. That is, the aluminum alloy foil used for the positive electrode current collector and the like in the lithium ion secondary battery is high in order to prevent breakage at the time of application of the mixture slurry and breakage at the bent portion generated at the time of winding. Strength is required.
- the heat treatment in the electrode manufacturing process reduces the strength of the aluminum alloy foil.
- the strength of the aluminum alloy foil is reduced, medium elongation is likely to occur at the time of press processing. Therefore, the occurrence of curling flaws at the time of winding, the decrease in the adhesion between the active material and the aluminum alloy foil, and the formation of slits in the subsequent process Breaking is likely to occur.
- the aluminum alloy does not have to be softened after the heat treatment. This is because the aluminum alloy foil is easily broken even when the elongation is reduced by the heat treatment. Further, in the lithium ion secondary battery, the active material expands and contracts during charging and discharging. Therefore, even after being assembled as a battery, stress is applied to the aluminum alloy foil as the current collector. Therefore, when the elongation of the aluminum alloy foil is low, the deformation due to expansion and contraction of the active material cannot be followed, and breakage is likely to occur.
- Patent Documents 2 and 3 described above there is no description regarding elongation after heat treatment, although there is a reference regarding strength after heat treatment.
- the present invention has been made in view of the above background, and intends to provide an aluminum alloy foil having high strength and elongation even after undergoing a heat treatment in an electrode manufacturing process or the like.
- the chemical component includes, by mass%, Fe: 1.0% or more and 2.0% or less, Mn: 0.05% or less, and the balance is made of Al and inevitable impurities.
- the average crystal grain size on the foil surface is 2.5 ⁇ m or less, and the ratio A ⁇ 112 ⁇ ⁇ 111> / A ⁇ 101 ⁇ ⁇ 121> of the area ratio of crystal orientation is 3.0 or more.
- a ⁇ 112 ⁇ ⁇ 111> is the total area of crystal grains whose crystal orientation is within 15 ° from ⁇ 112 ⁇ ⁇ 111> in the orientation mapping image of the foil surface by electron beam backscatter diffraction method.
- a ⁇ 101 ⁇ ⁇ 121> is a ratio with respect to the total area of the area of crystal grains whose crystal orientation is within 15 ° from ⁇ 101 ⁇ ⁇ 121> in the orientation mapping image. .
- Another aspect of the present invention is a method for producing an aluminum alloy foil in which the aluminum alloy ingot is hot rolled and then cold rolled to form a foil.
- the aluminum alloy ingot has a chemical component of mass%, Fe: 1.0% or more and 2.0% or less, Mn: 0.05% or less, and the balance consists of Al and inevitable impurities, Without homogenization before the hot rolling, The temperature during the hot rolling is 350 ° C. or less, In the method for producing an aluminum alloy foil, the cold rolling is performed without annealing in the middle, and the foil thickness is 20 ⁇ m or less.
- the aluminum alloy foil has the specific chemical component, and the ratio of the average crystal grain size and the crystal orientation area ratio on the foil surface is in the specific range. Therefore, the aluminum alloy foil has high strength and elongation even after heat treatment in an electrode manufacturing process or the like. Therefore, according to the said aluminum alloy foil, when the manufacturing process after the said heat processing and the charging / discharging of a battery are repeated etc., the fracture
- the aluminum alloy foil and the manufacturing method thereof will be described.
- Fe 1.0% or more and 2.0% or less Fe functions to improve the strength of the aluminum alloy foil and lower the softening temperature of the aluminum alloy foil. These functions can be obtained by controlling both the solid solution amount and the precipitation state of Fe, improving the strength of the aluminum alloy foil, and lowering the recrystallization temperature.
- the compound precipitated as the Al—Fe-based compound is dispersed in large numbers as Al—Fe-based fine compounds that are not compatible with the Al substrate (matrix), thereby promoting the recovery of the processed structure during the heat treatment. For this reason, even when the recrystallization temperature of the aluminum alloy foil is lowered and a heat treatment at 350 ° C. or lower is performed, a large elongation can be obtained.
- the Fe content When the Fe content is less than 1.0%, the dispersion of the Al—Fe fine compound that is not compatible with the Al substrate (matrix) becomes insufficient, and it is difficult to lower the recrystallization temperature of the aluminum alloy foil. Become. On the other hand, if the Fe content exceeds 2.0%, a coarse Al—Fe compound exceeding several hundred ⁇ m is formed during casting, which causes pinholes (holes) during foil rolling, and is a healthy foil material. Is difficult to manufacture. From the above viewpoint, the Fe content can be preferably 1.1% or more, and more preferably 1.2% or more. Further, the Fe content is preferably 1.9% or less, more preferably 1.8% or less, and even more preferably 1.7% or less.
- the Mn content is 0.05% or less.
- the Mn content is preferably 0.03% or less, and more preferably 0.01% or less.
- usually used Al bullion often contains Mn as an impurity. Therefore, in order to regulate the Mn content to less than 0.001%, high-purity metal is used. Therefore, the Mn content can be preferably 0.001% or more from the viewpoint of economy and the like.
- the chemical component can further contain at least one of Si and Cu within the range of contents shown below.
- Si 0.01 or more and 0.6% or less Si is an element that contributes to improving the strength of the aluminum alloy foil.
- the Si content can be set to 0.01% or more from the viewpoint of obtaining the strength improvement effect by addition.
- Al bullion often contains Si as an impurity. Therefore, less than 0.01% Si may be included as an inevitable impurity.
- a high-purity metal is used in order to regulate the Si content to less than 0.01%. Therefore, from the economical viewpoint, the Si content can be 0.01% or more.
- the Si content is 0.6% or less, it is easy to further improve the strength of the aluminum alloy foil, and it is difficult to form coarse Si single-phase particles.
- the Si content can be preferably 0.05% or more, and more preferably 0.1% or more. Further, the Si content can be preferably 0.5% or less, more preferably 0.4% or less.
- Cu 0.001% to 0.1%
- the Cu content can be made 0.001% or more from the viewpoint of obtaining the effect of improving the strength by the addition. Note that less than 0.001% of Cu may be included as an inevitable impurity. Moreover, in order to regulate Cu content to less than 0.001%, a high purity metal is used. Therefore, the Cu content can be made 0.001% or more also from the viewpoint of economy. On the other hand, when the Cu content is 0.1% or less, the elongation after heat treatment of the aluminum alloy foil is difficult to decrease. From the above viewpoint, the Cu content can be preferably 0.002% or more, and more preferably 0.005% or more. Moreover, Cu content can be 0.09% or less preferably, more preferably 0.08% or less.
- the chemical component may contain elements such as Cr, Ni, Zn, Mg, B, V, and Zr as inevitable impurities. These elements may deteriorate the elongation after heat treatment of the aluminum alloy foil. Therefore, it is preferable to regulate these elements to 0.02% or less and the total amount of these elements to 0.07% or less.
- the aluminum alloy foil has an average crystal grain size on the foil surface of 2.5 ⁇ m or less.
- the foil surface is the surface of the foil perpendicular to the thickness direction of the foil. If the average crystal grain size on the foil surface exceeds 2.5 ⁇ m, some crystal grains grow significantly large during the heat treatment, and the strength of the aluminum alloy foil decreases. From the viewpoint of improving the strength of the aluminum alloy foil, the average crystal grain size on the foil surface is preferably 2.4 ⁇ m or less, more preferably 2.3 ⁇ m or less, and even more preferably 2.2 ⁇ m or less. In addition, since it is so preferable that a crystal grain is finer, the minimum of the average crystal grain diameter in a foil surface is not specifically limited.
- the measuring method of the average crystal grain size is as follows.
- the foil surface of the aluminum alloy foil of the measurement sample is smoothed by electrolytic polishing.
- the smoothed foil surface is analyzed by an electron backscattering diffraction (EBSD) method with an observation magnification of 500 times by SEM, and an orientation mapping image is obtained.
- Measurement is performed for 5 fields per sample.
- a boundary having an orientation difference of 15 ° or more is defined as a crystal grain boundary
- a region surrounded by the boundary is defined as one crystal grain
- an equivalent circle diameter is calculated from the area. Is the grain size.
- the average crystal grain size is calculated as an average weighted by the area, and the average of the five fields of view is the final average crystal grain size.
- ratio A ⁇ 112 ⁇ ⁇ 111> / A ⁇ 101 ⁇ ⁇ 121> of the area ratio of the crystal orientation in a foil surface is 3.0 or more.
- the ratio of the area ratio of the crystal orientation on the foil surface is obtained by using the orientation mapping image of the foil surface described above.
- a ⁇ 112 ⁇ ⁇ 111> is a ratio with respect to the total area of crystal grains whose crystal orientation is within 15 ° from ⁇ 112 ⁇ ⁇ 111> in the orientation mapping image.
- a ⁇ 101 ⁇ ⁇ 121> is the ratio of the area of crystal grains in the above orientation mapping image whose crystal orientation is within 15 ° from ⁇ 101 ⁇ ⁇ 121> to the total area.
- a ⁇ 112 ⁇ ⁇ 111> / A ⁇ 101 ⁇ ⁇ 121> varies depending on the degree of processing of the aluminum alloy foil.
- a ⁇ 112 ⁇ ⁇ 111> / A ⁇ 101 ⁇ ⁇ 121> is less than 3.0, the accumulation of strain depending on work hardening becomes insufficient, and the crystal grains are not sufficiently refined after heat treatment. The strength of the aluminum alloy foil is reduced.
- the accumulation of strain accompanying processing is greatly affected only by cold rolling conditions after intermediate annealing.
- aluminum alloy foil is manufactured without hot annealing at a relatively low temperature, not only cold rolling but also accumulation of strain during hot rolling at low temperature Is also an important factor.
- a ⁇ 112 ⁇ ⁇ 111> / A ⁇ 101 ⁇ ⁇ 121> is preferably 3.5 or more, more preferably 4.0 or more, and still more preferably 4.5 or more, from the viewpoint of improving the strength of the aluminum alloy foil. It can be.
- the foil thickness is 20 ⁇ m or less from the viewpoint of increasing the proportion of the active material in the volume of the entire battery for the purpose of increasing the battery capacity. Good.
- the foil thickness can be preferably 18 ⁇ m or less, more preferably 15 ⁇ m or less.
- the lower limit of the foil thickness is not particularly limited, but the foil thickness can be 8 ⁇ m or more from the viewpoint of being suitable for use as a current collector.
- the aluminum alloy foil preferably has a tensile strength of 120 MPa or more from the viewpoint of ensuring the effect of preventing breakage.
- the tensile strength is a value measured according to JIS Z2241.
- the aluminum alloy foil preferably has an elongation of 6% or more from the viewpoint of ensuring the effect of preventing breakage.
- the elongation is a value measured according to JIS Z2241.
- the aluminum alloy foil can be suitably used as a current collector in, for example, a secondary battery such as a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor. More specifically, for example, when the aluminum alloy foil is used as a current collector of a lithium ion secondary battery, a mixture containing mainly an electrode active material is attached to the surface of the aluminum alloy foil as the current collector. It is done. Specifically, a mixture slurry containing an electrode active material is applied to the surface of the aluminum alloy foil, and after drying, the mixture slurry is pressed for the purpose of compacting the mixture layer and improving the adhesion to the current collector.
- a secondary battery such as a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor.
- a mixture containing mainly an electrode active material is attached to the surface of the aluminum alloy foil as the current collector. It is done. Specifically, a mixture slurry containing an electrode active material is applied to the surface of the aluminum alloy foil
- a heat treatment accompanied by thermal modification of the thickener or binder added to the mixture slurry may be performed.
- the electrode including the current collector is held for about several hours at 50 to 350 ° C. during drying or heat treatment.
- the aluminum alloy foil has high strength and elongation even after these heat treatments. When used, the electrode is unlikely to break.
- the aluminum alloy ingot made of the chemical component is hot-rolled without being homogenized.
- “no homogenization treatment” means that the heat treatment for homogenization as conventionally performed at a high temperature exceeding 350 ° C. is not actively performed before hot rolling.
- the aluminum alloy ingot is heated to 350 ° C. or lower for hot rolling, the phenomenon that homogenization occurs not a little is allowed because it hardly affects the foil strength and elongation.
- the homogenization process is performed, precipitation of solid solution elements such as Si and Fe proceeds, and the amount of these solid solutions decreases. As a result, the strength is lowered due to the reduction in the effect of solid solution hardening and the coarsening of crystal grains.
- hot rolling is performed at a temperature of 350 ° C. or lower. That is, the temperature at the time of hot rolling is set to 350 ° C. or less at the start and end of the hot rolling where temperature measurement is easy.
- the lower limit value of the temperature during hot rolling is not particularly limited, but can be set to 150 ° C. from the viewpoint of suppressing an increase in load on the rolling mill due to an increase in deformation resistance.
- the holding time after reaching the hot rolling start temperature is not particularly limited, but it is within 12 hours from the viewpoint of easily suppressing precipitation of the Al—Fe—Si compound. can do.
- the hot rolling may be performed once, or may be performed in a plurality of times, such as finish rolling after rough rolling.
- an aluminum alloy foil is obtained by cold rolling after hot rolling. At this time, annealing is not performed during the cold rolling. By performing annealing in the middle, the processing strain is released, the crystal grains are difficult to refine, and the strength after heat treatment is reduced. In addition, acceleration of precipitation of the Al—Fe—Si compound also causes a decrease in strength after the heat treatment. In addition, it is preferable not to perform the final annealing after completion
- the foil thickness after cold rolling is 20 ⁇ m or less from the viewpoint of increasing the proportion of the active material in the volume of the entire battery for the purpose of increasing the battery capacity. Is done.
- the foil thickness can be preferably 18 ⁇ m or less, more preferably 15 ⁇ m or less.
- the lower limit of the foil thickness is not particularly limited, but the foil thickness can be 8 ⁇ m or more from the viewpoint of being suitable for use as a current collector.
- the cold rolling can be performed once or a plurality of times.
- the final rolling rate in the cold rolling is preferably 95% or more, more preferably 98% or more, from the viewpoint of promoting the refinement of crystal grains.
- the final rolling rate is 100 ⁇ (plate thickness of hot rolled plate before cold rolling ⁇ foil thickness of aluminum alloy foil after final cold rolling) / (of hot rolled plate before cold rolling) It is a value calculated from (plate thickness).
- the aluminum alloy foil of the example and the manufacturing method thereof will be described below.
- Example 1 An aluminum alloy ingot was prepared by ingoting and chamfering aluminum alloys having chemical components shown in Table 1 by a semi-continuous casting method.
- alloys A to F are aluminum alloys having chemical components suitable for the examples
- alloys G to K are aluminum alloys having chemical components as comparative examples.
- the above-prepared aluminum alloy ingot was hot rolled without being homogenized to obtain a hot rolled plate having a thickness of 5.0 mm.
- hot rolling rough rolling and finish rolling were continuously performed.
- the aluminum alloy ingot before being subjected to the rough rolling is heated to 350 ° C. and held for 6 hours to set the rough rolling start temperature (hot rolling start temperature) to 350 ° C. .
- the end temperature of rough rolling was 320 ° C.
- the end temperature of finish rolling end temperature of hot rolling
- the average crystal grain size, the area ratio of crystal orientation, the tensile strength and elongation after heat treatment were measured.
- lighting was applied from the back of the test material, and the occurrence of pinholes was also investigated according to the presence or absence of light leakage.
- the average crystal grain size was determined as follows. First, an aluminum alloy foil cut into a size of 15 mm ⁇ 80 mm is measured by electrolytic polishing in an aqueous solution of perchloric acid ethanol (60% by mass of 60 ml of perchloric acid + 500 ml of ethanol) at ⁇ 7 ° C. under conditions of 10 V ⁇ 1 min. The foil surface was adjusted. The foil surface is parallel to the rolling surface. And the observation magnification was set to 500 times with SEM with respect to the adjusted surface, the analysis by an electron beam backscattering diffraction method (EBSD: Electron
- EBSD electron beam backscattering diffraction method
- a boundary having an orientation difference of 15 ° or more is defined as a crystal grain boundary, a region surrounded by the boundary is defined as one crystal grain, and an equivalent circle diameter is calculated from the area, The particle size was determined.
- the average crystal grain size was calculated as an average weighted by area, and the average of five fields of view was used as the final average crystal grain size.
- the ratio of the area ratio of the crystal orientation was determined as follows. Specifically, in the orientation mapping image obtained by the above method, the ratio of the area of crystal grains whose crystal orientation is within 15 ° from ⁇ 112 ⁇ ⁇ 111> to the total area is represented by A ⁇ 112 ⁇ ⁇ 111. > , The ratio of the area of crystal grains within the range of 15 ° from ⁇ 101 ⁇ ⁇ 121> to the total area is determined as A ⁇ 101 ⁇ ⁇ 121>, and A ⁇ 112 ⁇ ⁇ 111> / A ⁇ 101 ⁇ ⁇ 121> was calculated.
- the tensile strength and elongation after heat treatment were measured by the following methods. Specifically, the obtained aluminum alloy foil was used as a test material, which was heat-treated at 220 ° C. for 5 hours, and then measured for tensile strength and elongation. Tensile strength and elongation were measured in accordance with JIS Z2241 by collecting a JIS No. 5 test piece from the test material. In addition, the thing with the tensile strength after heat processing of 120 Mpa or more was set as the pass, and the thing below it was set as the rejection. Moreover, the thing of elongation 6% or more was set as the pass, and the thing less than it was set as the rejection. These results are summarized in Table 2.
- the test materials E1 to E6 are examples, and the test materials C1 to C5 are comparative examples.
- test material C1 used an alloy G having an Si content exceeding 0.6%, coarse Si single-phase particles were formed, and pinholes were generated due to this.
- test material C2 uses the alloy H having an Fe content of less than 1.0%, the tensile strength after the heat treatment is less than 120 MPa, and the amount of Al—Fe intermetallic compound to be dispersed is small, so that it is difficult to be softened. The growth was unacceptable.
- test material C3 had an Fe content exceeding 2.0%, a coarse compound was formed during casting, and pinholes were generated during foil rolling.
- test material C4 had a Cu content exceeding 0.1%, softening during the heat treatment hardly occurred, and the elongation after the heat treatment was less than 6%.
- test material C5 had a Mn content exceeding 0.05%, softening during the heat treatment hardly occurred, and the elongation after the heat treatment was less than 6%.
- Example 2 This example mainly investigates the temperature conditions at the time of hot rolling, the presence or absence of a homogenization treatment, the influence of intermediate annealing at the time of cold rolling, and the like.
- An aluminum alloy ingot was prepared by ingot forming and chamfering aluminum alloy A having chemical components shown in Table 1 by a semi-continuous casting method.
- Test material C8 was produced by performing a homogenization treatment at a high temperature of 520 ° C. exceeding 350 ° C. before the start of hot rolling. As a result, an Al—Fe-based compound was formed, and the solid solution amount was reduced. As a result, the effect of solid solution hardening was reduced and the crystal grains were coarsened. As a result, the strength after heat treatment was rejected.
- the test material C9 was manufactured by performing annealing at a high temperature of 380 ° C. exceeding 350 ° C. in the course of cold rolling during the cold rolling, although the temperature during hot rolling was 350 ° C. or less. It is.
- the effect of crystal grain refinement due to the accumulation of strain was weakened, and the strength after heat treatment was reduced.
- the precipitation of Al—Fe—Si compounds is promoted, and the solid solution amount of Si and Fe is reduced, which is one cause of the decrease in strength. As a result, the strength after the heat treatment was rejected.
- test materials E7 to E9 produced based on specific conditions had a tensile strength after heat treatment of 120 MPa or more and an elongation of 6% or more.
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Abstract
Description
箔面における平均結晶粒径が2.5μm以下、結晶方位の面積割合の比A{112}<111>/A{101}<121>が3.0以上である、アルミニウム合金箔にある。
但し、上記A{112}<111>は、電子線後方散乱回折法による箔面の方位マッピング像において、結晶方位が{112}<111>から15°以内の範囲にある結晶粒の面積の総面積に対する割合であり、上記A{101}<121>は、上記方位マッピング像において、結晶方位が{101}<121>から15°以内の範囲にある結晶粒の面積の総面積に対する割合である。
上記アルミニウム合金鋳塊は、化学成分が、質量%で、Fe:1.0%以上2.0%以下、Mn:0.05%以下を含有し、残部がAlおよび不可避的不純物からなり、
上記熱間圧延の前に均質化処理を行うことがなく、
上記熱間圧延時の温度は350℃以下であり、
途中で焼鈍を行うことなく上記冷間圧延を行い、箔厚を20μm以下とする、アルミニウム合金箔の製造方法にある。
Feは、アルミニウム合金箔の強度を向上させるとともに、アルミニウム合金箔の軟化温度を低下させるよう機能する。これらの機能は、Feの固溶量と析出状態の双方を制御し、アルミニウム合金箔の強度を向上させ、再結晶温度を低下させることによって得ることができる。
Mn含有量が0.05%を超えると、熱処理後の伸びが低下する。そのため、集電体として用いた場合に、充放電時の活物質の膨張収縮による変化に追随することが困難となり、破断が生じやすくなる。よって、Mn含有量を0.05%以下とする。Mn含有量は、好ましくは、0.03%以下、より好ましくは、0.01%以下であるとよい。なお、通常使用されるAl地金には不純物としてMnが含まれていることが多い。そのため、Mn含有量を0.001%未満に規制するためには、高純度地金を使用することになる。したがって、Mn含有量は、経済性などの観点から、好ましくは、0.001%以上とすることができる。
Siは、アルミニウム合金箔の強度向上に寄与する元素である。Si含有量は、添加による強度向上効果を得る観点から、0.01%以上とすることができる。なお、通常使用されるAl地金には不純物としてSiが含まれていることが多い。そのため、0.01%未満のSiは、不可避的不純物として含まれていてもよい。もっとも、Si含有量を0.01%未満に規制するためには高純度の地金を使用することになる。したがって、経済性の観点から、Si含有量は、0.01%以上とすることができる。一方、Si含有量が0.6%以下であると、アルミニウム合金箔のさらなる強度向上が図りやすくなる上、粗大なSi単相粒子が形成され難くなり、20μm以下の箔厚ではピンホールや箔切れの問題が生じ難くなる。上記の観点から、Si含有量は、好ましくは、0.05%以上、より好ましくは、0.1%以上とすることができる。また、Si含有量は、好ましくは、0.5%以下、より好ましくは、0.4%以下とすることができる。
Cuは、アルミニウム合金箔の強度向上に寄与する元素である。Cu含有量は、添加による強度向上効果を得る観点から、0.001%以上とすることができる。なお、0.001%未満のCuは、不可避的不純物として含まれていてもよい。また、Cu含有量を0.001%未満に規制するためには高純度の地金を使用することになる。したがって、経済性の観点からも、Cu含有量は、0.001%以上とすることができる。一方、Cu含有量が0.1%以下であると、アルミニウム合金箔の熱処理後の伸びが低下し難くなる。上記の観点から、Cu含有量は、好ましくは、0.002%以上、より好ましくは、0.005%以上とすることができる。また、Cu含有量は、好ましくは、0.09%以下、より好ましくは、0.08%以下とすることができる。
表1に示す化学成分のアルミニウム合金を半連続鋳造法にて造塊し、面削することによりアルミニウム合金鋳塊を準備した。なお、表1に示す化学成分のアルミニウム合金のうち、合金A~Fが実施例に適する化学成分のアルミニウム合金であり、合金G~Kが比較例としての化学成分のアルミニウム合金である。
本例は、熱間圧延時の温度条件や均質化処理の有無、冷間圧延時における途中焼鈍の影響などを主に調査したものである。
Claims (6)
- 化学成分が、質量%で、Fe:1.0%以上2.0%以下、Mn:0.05%以下を含有し、残部がAlおよび不可避的不純物からなり、
箔面における平均結晶粒径が2.5μm以下、結晶方位の面積割合の比A{112}<111>/A{101}<121>が3.0以上である、アルミニウム合金箔。
但し、上記A{112}<111>は、電子線後方散乱回折法による箔面の方位マッピング像において、結晶方位が{112}<111>から15°以内の範囲にある結晶粒の面積の総面積に対する割合であり、上記A{101}<121>は、上記方位マッピング像において、結晶方位が{101}<121>から15°以内の範囲にある結晶粒の面積の総面積に対する割合である。 - 上記化学成分が、SiおよびCuの少なくとも一方をさらに含有し、質量%で、上記Si:0.01%以上0.6%以下、上記Cu:0.01%以上0.1%以下である、請求項1に記載のアルミニウム合金箔。
- 集電体用である、請求項1または2に記載のアルミニウム合金箔。
- アルミニウム合金鋳塊を熱間圧延した後、冷間圧延することにより箔状とするアルミニウム合金箔の製造方法であって、
上記アルミニウム合金鋳塊は、化学成分が、質量%で、Fe:1.0%以上2.0%以下、Mn:0.05%以下を含有し、残部がAlおよび不可避的不純物からなり、
上記熱間圧延の前に均質化処理を行うことがなく、
上記熱間圧延時の温度は350℃以下であり、
途中で焼鈍を行うことなく上記冷間圧延を行い、箔厚を20μm以下とする、アルミニウム合金箔の製造方法。 - 上記化学成分が、SiおよびCuの少なくとも一方をさらに含有し、質量%で、上記Si:0.01%以上0.6%以下、上記Cu:0.001%以上0.1%以下である、請求項4に記載のアルミニウム合金箔の製造方法。
- 上記アルミニウム合金箔は、集電体用である、請求項4または5に記載のアルミニウム合金箔の製造方法。
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WO2012169570A1 (ja) * | 2011-06-07 | 2012-12-13 | 住友軽金属工業株式会社 | アルミニウム合金箔の製造方法およびアルミニウム合金箔 |
WO2014087827A1 (ja) * | 2012-12-03 | 2014-06-12 | 株式会社Uacj | アルミニウム合金箔 |
WO2015060300A1 (ja) * | 2013-10-25 | 2015-04-30 | 株式会社Uacj | 電極集電体用アルミニウム合金箔及びその製造方法 |
JP2016041835A (ja) * | 2014-08-14 | 2016-03-31 | 三菱アルミニウム株式会社 | アルミニウム合金箔およびその製造方法 |
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WO2014087827A1 (ja) * | 2012-12-03 | 2014-06-12 | 株式会社Uacj | アルミニウム合金箔 |
WO2015060300A1 (ja) * | 2013-10-25 | 2015-04-30 | 株式会社Uacj | 電極集電体用アルミニウム合金箔及びその製造方法 |
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WO2020175327A1 (ja) * | 2019-02-26 | 2020-09-03 | 東洋アルミニウム株式会社 | アルミニウム合金箔およびその製造方法 |
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