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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21B—ROLLING OF METAL
  • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
  • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21B—ROLLING OF METAL
  • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
  • B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
  • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
  • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • 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
• • 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

Definitions

• the present invention relates to an aluminum hard foil for a battery current collector used as a positive electrode current collector of a lithium ion secondary battery.
• lithium ion secondary batteries have been used as power sources for mobile tools such as mobile phones and notebook computers.
• the electrode material of such a lithium ion secondary battery is formed of a positive electrode material, a separator, and a negative electrode material.
• the positive electrode material is manufactured by applying an active material such as LiCoO 2 having a thickness of about 100 ⁇ m to both sides of an aluminum foil for collector (or aluminum alloy foil) having a thickness of about 15 ⁇ m. Drying is performed to remove the solvent, and pressure bonding for increasing the density of the active material is performed, and the process is performed through a slitting and cutting process.
• an active material such as LiCoO 2 having a thickness of about 100 ⁇ m
• an aluminum foil for collector or aluminum alloy foil having a thickness of about 15 ⁇ m. Drying is performed to remove the solvent, and pressure bonding for increasing the density of the active material is performed, and the process is performed through a slitting and cutting process.
• a high-purity aluminum foil material as shown in Patent Document 1
• a high strength aluminum alloy foil is directed.
• the tensile strength is 172 to 185 MPa and the elongation value is 1.4 to 1.7%.
• aluminum alloy foil having a tensile strength of 270 to 279 MPa and an elongation value of 1.3 to 1.8% by adding Mn such as 3003 alloy is commercially available. Growth has been directed.
• Patent Document 2 proposes the following proposal. That is, when a hard active material is used, when it is housed in a battery case, the electrode material wound (bent) in a spiral shape tends to be easily broken at a portion having a small radius. Therefore, in the Al-Mn alloy foil, by increasing the Cu content and performing intermediate annealing under predetermined conditions using a continuous annealing furnace at a predetermined plate thickness during cold rolling, the strength of 280 to 380 MPa is obtained. Proposals for improving the bending resistance have been made. In addition, for example, Patent Document 3 proposes that Mg, Co, Zr, W, or the like is added to an aluminum alloy foil to obtain a strength of 240 to 400 MPa to obtain elongation and corrosion resistance.
• Non-Patent Document 2 as a general characteristic, 1085, which is pure aluminum, has a conductivity of 61.5% IACS, which is higher than that of Mn-added 3003 alloy (48.5%). Low value). Due to such high conductivity, pure aluminum foil desirable for use in electrical components is still widely used.
• the electrical conductivity varies depending on the alloy element and the tempering (processing rate), and as disclosed in Non-Patent Document 3, with a thickness of 6 mm or more, a high-purity 1070 material or the like is 62 (soft (O) material). In the case of 300% alloy, 61% for hard (H18) material, 50% for soft material and 40% for hard material. That is, in the Mn-based alloy, the electrical conductivity is greatly lowered by processing.
• Japanese Patent Laid-Open No. 11-162470 (paragraph 0023) Japanese Unexamined Patent Publication No. 2008-150651 (paragraphs 0003, 0005 to 0007) Japanese Unexamined Patent Publication No. 2009-64560 (paragraphs 0016 to 0029)
• the conventional aluminum foil and aluminum alloy foil have the following problems.
• elongation ductility
• foil thickness decreases. This is also clearly shown in Non-Patent Document 1.
• the alloy foil material added with a large amount of Mn for high strength has a problem that it is not desirable for use as a battery after assembly because it has a large electric resistance as clearly shown in Non-Patent Document 2. .
• the present invention has been made in view of the above problems, and it is an object of the present invention to provide an aluminum hard foil for a battery current collector having a certain degree of strength, excellent elongation, and low electrical resistance. To do.
• the present inventors have examined the following matters.
• Mg, Mn, Cu or the like may be added, and it is also used for the proposal in the prior art.
• no means for increasing the ductility (elongation) of the thin hard foil has been known.
• pure aluminum foil and 8021 alloy foil have high electrical conductivity but are insufficient in terms of strength and elongation.
• the material structure before rolling the finished foil is changed to a subgrain structure by controlling solid solution / precipitation in the material manufacturing process and controlling the foil rolling conditions. It was known that thin foils with few holes could be manufactured. Since the elongation of this microstructure is relatively high, it was considered that if the subgrains can be finely controlled, high ductility can be obtained even if the strength is relatively high.
• the material structure of the foil is often observed with a transmission electron microscope or the like, but only local information can be obtained, and observation has not been made over the entire cross section of the foil having a thickness of around 15 ⁇ m. Therefore, as a result of earnest research on the influence of various factors on the elongation of the hard foil, it is presumed that the size of the grain (subgrain) in the thickness direction and the rolling direction correlates with the elongation.
• the present invention has been achieved by newly establishing the observation conditions. That is, it was clarified that the subgrain diameter (thickness direction and rolling direction) in the cross section was non-uniform in any state of the hard foil.
• the present inventors have heretofore found that the subgrains in the thickness direction and the rolling direction have a large size, resulting in uneven deformation and low elongation, and the thickness direction and the rolling direction.
• the size of the subgrains By controlling the size of the subgrains to be small, it was found that uniform deformation is possible by tensile deformation or the like and high elongation is obtained, and the present invention was completed.
• Subgrains have also been studied to grow and form from a thinned layer by rolling the grain size during intermediate annealing, and in order to form subgrains with a small size in the thickness direction and the rolling direction, intermediate annealing is used. It was also found that controlling the number of crystal grains and the solid solution state is a necessary condition.
• the present inventors measured the electrical conductivity in an actual foil, and the actual electrical conductivity is different from the numerical values described in Non-Patent Documents 1 and 2 due to the fact that it is a thin hard foil. I found out that it was lower.
• alloy foils Al purity: less than 99.0% by mass
• the present invention is pure aluminum for reducing and suppressing electrical resistance. In this category, high strength and high elongation were measured.
• the aluminum hard foil for a battery current collector according to the present invention contains Fe: 0.2 to 1.3% by mass, Cu: 0.01 to 0.5% by mass Si: Suppressed to 0.2% by mass or less, the balance is made of Al and inevitable impurities, the purity is 98.0% by mass or more, and the size of the subgrain is 0.8 ⁇ m or less in the thickness direction. It is characterized by being 45 ⁇ m or less in the direction.
• the aluminum hard foil for battery current collector according to the present invention is the aluminum hard foil for battery current collector according to claim 1, which is manufactured by single rolling, has a thickness of 9 to 20 ⁇ m, and has a tensile strength. It is preferable that the thickness is 220 MPa or more and the elongation is 3.0% or more.
• the aluminum hard foil for battery current collector according to the present invention is the aluminum hard foil for battery current collector according to claim 1 manufactured by polymerization rolling, and has a thickness of 5 to 20 ⁇ m and a tensile strength. The thickness is preferably 215 MPa or more and the elongation is 1.0% or more.
• the strength of the aluminum foil is improved and the tensile strength is reduced.
• the electrical conductivity of 55% or more is obtained by making Cu content 0.5 mass% or less, and it has sufficient characteristics as a battery current collector.
• the Al—Fe-based intermetallic compound does not easily become a coarse ⁇ -Al—Fe—Si-based intermetallic compound, so that the elongation does not decrease and the crystal grain size is reduced. Is not coarse, and a sufficient number of subgrains can be obtained in the thickness direction. Further, by setting the thickness to 9 to 20 ⁇ m (in the case of single rolling) and 5 to 20 ⁇ m (in the case of polymerization rolling), an aluminum foil suitable for battery current collector can be obtained.
• the size of the subgrains in the thickness direction is 0.8 ⁇ m or less and the rolling direction is 45 ⁇ m or less, so that the elongation of the aluminum foil is improved, and in the case of single rolling, the elongation is 3.0% or more. In this case, it becomes 1.0% or more, which is sufficient for aluminum.
• the aluminum hard foil for battery collectors according to the present invention further contains one or more of Mn: 0.5% by mass or less and Mg: 0.05% by mass or less.
• the strength can be increased by adding at least one of Mn and Mg.
• the elongation does not decrease by adding Mn to a predetermined amount or less, and the elongation and conductivity may decrease by adding Mg to a predetermined amount or less. Absent.
• the aluminum hard foil for a battery current collector according to the present invention preferably has a conductivity of 55% (IACS) or more. According to such a structure, the efficiency of a battery improves at the time of use as a battery.
• the aluminum hard foil for a battery current collector according to the present invention has a high strength as pure aluminum even if it is a thin wall of 9 to 20 ⁇ m (in the case of single rolling) and 5 to 20 ⁇ m (in the case of polymerization rolling).
• the electric resistance is low, the capacity of the lithium ion secondary battery can be increased.
• the elongation is excellent, it is possible to prevent the foil from being broken in the manufacturing process of the electrode material, and it is possible to prevent the trouble that the production line is stopped.
• the aluminum foil according to the present invention contains a predetermined amount of Fe and Cu, suppresses Si to a predetermined amount or less, and the balance is made of Al and inevitable impurities.
• the thickness of the aluminum foil is 9 to 20 ⁇ m (in the case of single rolling), 5 to 20 ⁇ m (in the case of polymerization rolling), the subgrain size in the thickness direction is 0.8 ⁇ m or less, and the size in the rolling direction is 45 ⁇ m.
• the tensile strength is 220 MPa or more when manufactured by single rolling, 215 MPa or more when manufactured by polymerization rolling, and the elongation is 3.0% or more when manufactured by single rolling. When manufactured, it is specified to be 1.0% or more.
• the aluminum foil may contain a predetermined amount of one or more of Mn and Mg. And the electrical conductivity of aluminum foil will be 55% or more. Each configuration will be described below.
• Fe 0.2 to 1.3% by mass
• Fe is an element added for grain refinement during intermediate annealing, strength improvement by solid solution strengthening, and further stabilization of subgrains.
• the Fe content is less than 0.2% by mass, the crystal grain size becomes coarse, and it is not sufficiently refined in the thickness direction and the rolling direction, and it is difficult to obtain sufficient strength.
• the Fe content exceeds 1.3 mass%, electrical conductivity will fall. Therefore, the Fe content is 0.2 to 1.3% by mass.
• Cu 0.01 to 0.5% by mass
• Cu is an element added for improving the strength by solid solution strengthening. If it is less than 0.01% by mass, the strength is insufficient. If it exceeds 0.5 mass%, the elongation decreases. Since about half of the added amount of Cu enters the second phase such as a crystallized product or dispersed particles, the conductivity is higher than when adding the same amount of Mn.
• Si 0.2% by mass or less
• Si is an element that is easily mixed as an inevitable impurity.
• the Si content exceeds 0.2% by mass, the Al—Fe-based intermetallic compound tends to be a coarse ⁇ -Al—Fe—Si-based intermetallic compound, and elongation is difficult to obtain.
• the Si content is 0.2% by mass or less.
• Si may be 0% by mass.
• Mn 0.5% by mass or less
• Mn is also an element desirable for improving the strength, and may be added. However, if it exceeds 0.5 mass%, the electrical conductivity will decrease. Therefore, the Mn content when added is 0.5% by mass or less.
• Mg 0.05% by mass or less
• Mg is also a desirable element for improving the strength, and may be added. However, when it exceeds 0.05 mass%, elongation will fall. In addition, the conductivity decreases. Therefore, the Mg content when added is 0.05% by mass or less.
• Cr, Zr, V may be added for crystal grain refinement, but the content of Cr, Zr, V when added is 0.5 mass% or less in order to avoid a decrease in conductivity. Is desirable.
• the components of the aluminum foil are composed of Al and inevitable impurities. And the purity of aluminum is 98.0 mass% or more.
• Zn is allowed to be contained up to 0.1% by mass. If the Zn content exceeds 0.1% by mass, the corrosion resistance deteriorates.
• Ga, Ni, and the like within a normally known range contained in the metal and the intermediate alloy are allowed to contain up to 0.05% by mass.
• the aluminum foil should be as thin as possible, but it is difficult to produce a high strength foil of less than 9 ⁇ m by single rolling, and less than 5 ⁇ m by polymerization rolling. It is difficult to produce a high strength foil. On the other hand, if it exceeds 20 ⁇ m, a large amount of electrode material cannot be put in a case having a predetermined volume, and the battery capacity is lowered. Therefore, the thickness of the aluminum foil is 9-20 ⁇ m for the single rolled foil and 5-20 ⁇ m for the polymerized rolled foil.
• the subgrain size should be 0.8 ⁇ m or less in the thickness direction and in the rolling direction. It is necessary to be 45 ⁇ m or less. If the size is larger than that, the aluminum foil cannot be sufficiently stretched. Further, the smaller the subgrain size, the better.
• the lower limit is not particularly limited.
• the aluminum foil is cut to about 5 ⁇ 10 mm, and the cut foil is pasted on a thin plate substrate using a conductive tape so that the foil is slightly protruded.
• this foil portion is cut with a FIB (Focused Ion Beam) apparatus so that a parallel section can be observed.
• the resin filling method that is frequently used, the resin part is charged up during SEM (scanning electron microscope) observation, and measurement is difficult.
• an observation magnification is set to ⁇ 2000 with an SEM, and EBSD (Electron Back Scatter Diffraction) analysis is performed to obtain an orientation mapping image.
• Measurement may be performed in 10 fields per sample. Since the observation is usually performed from the surface, the analysis software automatically displays an orientation mapping image of the ND plane viewed from the surface. In this analysis, the observation is a parallel section (RD-TD plane), and the rotation operation is performed so as to obtain an orientation mapping image of the ND plane viewed from the RD-ND plane. Then, the subgrain size is calculated by the line segment method from the obtained orientation mapping image. Specifically, it is as follows.
• the subgrain has an inclination angle between crystal grains of 0 to 15 °, and a boundary having an inclination angle of less than 15 ° and a boundary having an inclination angle of 15 ° or more can be displayed by color on the orientation mapping in an angle-differentiated manner. Based on this matter, the tilt angle and color between crystal grains are determined with the naked eye from the orientation mapping image (orientation mapping diagram), and the size of the subgrain is measured.
• the tensile strength 220 MPa or more (in the case of single rolling), 215 MPa or more (in the case of polymerization rolling)
• the tensile strength of the aluminum foil produced by polymerization rolling may be 215 MPa or more. Therefore, the tensile strength is 220 MPa or more (in the case of single rolling) and 215 MPa or more (in the case of polymerization rolling).
• Tensile strength and elongation were measured by cutting out a strip-shaped test piece of 15 mm width x about 200 mm length from the center of the width direction of the aluminum foil so that the tensile direction was parallel to the rolling direction, and scoring the distance between chucks of 100 mm. It is implemented as a distance. The elongation is calculated from the displacement of the crosshead. The number of tests is 5 times for each material. The values of tensile strength and elongation are average values of three times excluding the maximum and minimum values among the five times. For the test, Tensilon Universal Tester Model: RTC-1225A manufactured by Orientec Co., Ltd. can be used.
• Equation (1) 1.7241 is the volume resistivity [ ⁇ ⁇ cm] of standard annealed copper, A is the sample cross-sectional area [cm 2 ], and L is the length of the measurement part [cm 2 ].
• the method for producing the aluminum foil is that the aluminum ingot is subjected to homogenization heat treatment and hot rolling by a regular method, followed by cold rolling under a predetermined condition, intermediate annealing as necessary, and then cold rolling, It is to perform foil rolling.
• the foil rolling is generally performed by either single rolling or superposition rolling.
• the polymerization rolling is a method in which two aluminum foils are stacked and supplied to a roll in the final pass and rolled.
• Single rolling is a process in which a single aluminum foil is supplied to a roll and rolled until the final pass.
• intermediate annealing In aluminum foil, in order to reduce the size of the subgrain, intermediate annealing is not performed, or intermediate annealing is rapidly heated and rapidly cooled by continuous annealing (CAL), so that the crystal grain size during intermediate annealing is made fine. It is preferable. Therefore, it is preferable that the cold working rate (cold rolling rate) from hot rolling to intermediate annealing is high, and a cold rolling rate of 30% or more is preferable. In order to improve the strength, it is preferable to set the cold rolling rate to 30% or more. If the cold rolling rate until the intermediate annealing exceeds 85%, the effect is saturated and it is not economical, so 85% or less is preferable. However, when the intermediate annealing is performed by batch annealing, the recrystallized grain size at the time of intermediate annealing becomes coarse, and the elongation is lowered as compared with the case where the intermediate annealing is not performed.
• CAL continuous annealing
• the cold rolling rate after intermediate annealing that is, the final aluminum after intermediate annealing
• the total cold rolling ratio until the foil (final product) is made is preferably 98.5% or more, and for that purpose, the thickness during intermediate annealing is preferably 1 mm or more.
• the plate thickness during the intermediate annealing is preferably 1 mm or more.
• the strength becomes too high and foil rolling tends to be difficult, so 2 mm or less is preferable.
• the work hardening is small at a foil thickness of about 100 ⁇ m or less even if the absolute value of the strength is high. Further, in order to promote subgraining by foil rolling, it is necessary to raise the temperature to some extent, and the temperature is set to about 40 to 100 ° C. after coil winding. When there is no temperature rise during foil rolling, it is difficult to refine crystal grains by subgraining.
• the homogenization heat treatment is performed under conditions where the soaking temperature is 350 ° C. or higher and 560 ° C. or lower.
• the soaking temperature is less than 350 ° C., homogenization is insufficient and the elongation of the aluminum foil is lowered.
• the soaking temperature exceeds 560 ° C., the dispersed particles are coarsely and sparsely distributed, the grain boundary pinning force is reduced, fine crystal grains are not obtained, and the elongation of the aluminum foil is reduced.
• the lower temperature side is desirable in the range of the soaking temperature of 350 ° C. or higher and 560 ° C. or lower.
• the recrystallized grain size is made fine, and the subgrain size of the foil is 0.8 ⁇ m or less in the thickness direction and 45 ⁇ m or less in the rolling direction, so that annealing is performed in a continuous annealing furnace.
• annealing temperature (attainment temperature) is 380 degreeC or more and 550 degrees C or less, and holding time is 1 minute or less.
• the annealing temperature is less than 380 ° C., recrystallization does not proceed sufficiently, the subgrain size increases, and the degree of solid solution becomes insufficient.
• the temperature exceeds 550 ° C. the effects of recrystallization and solid solution are saturated and the surface appearance tends to deteriorate.
• the temperature raising / lowering rate may be within the range of conventional methods in continuous annealing, but in batch annealing, precipitation proceeds during heating, and subgrains coalesce and become coarse during foil rolling. Will progress. In addition, the degree of work hardening is insufficient and the strength decreases.
• the temperature increase rate is 1 to 100 ° C./second
• the temperature decrease rate is 1 to 500 ° C./second.
• the heating rate is 20 to 60 ° C./hour
• the cooling rate is arbitrarily applied to furnace cooling, standing cooling, forced air cooling, etc., and these conditions are followed. And although it is preferable that holding time is long for solid solution, since it is a continuous annealing furnace, holding over 1 minute is economically inferior because the line speed becomes remarkably slow.
• the size of the subgrains in the thickness direction and the rolling direction can be controlled by the component range, the number of crystal grains during intermediate annealing, and the solid solution state.
• Example preparation Aluminum having the composition shown in Table 1 was melted and cast into an ingot, and the ingot was chamfered, and then subjected to a homogenizing heat treatment at a temperature of 360 to 550 ° C. for 2 to 4 hours. The homogenized ingot was subjected to hot rolling and further cold rolling, followed by intermediate annealing, and then cold rolled to a predetermined thickness to obtain an aluminum foil.
• the conditions for intermediate annealing and cold rolling are as shown in Table 1.
• CAL continuous annealing
• the rate of temperature increase is 10 ° C./second and the rate of temperature decrease is 20 ° C./second.
• BATCH batch annealing
• the rate of temperature increase is 40 ° C./hour, the rate of temperature decrease.
• the total cold rolling rate is an approximate value.
• Table 1 shows the component composition, characteristics, and production conditions when an aluminum foil was produced by single rolling and polymerization rolling. In the table, those not satisfying the scope of the present invention and those not satisfying the production conditions are indicated by underlining the numerical values. Moreover, in Table 1, the thickness of the plate after hot rolling is described as hot-rolled end thickness, and the thickness of the plate before intermediate annealing is described as intermediate annealing thickness.
• the size of the subgrains in the thickness direction and the rolling direction of the aluminum foil was measured by the following method.
• the aluminum foil was cut to about 5 ⁇ 10 mm, and this cut foil was attached to a thin plate substrate using a conductive tape so that the foil was slightly protruding.
• this foil portion was cut with a FIB (Focused Ion Beam) apparatus so that a parallel section could be observed.
• FIB Flucused Ion Beam
• the analysis software automatically displays an orientation mapping image of the ND plane viewed from the surface.
• the observation was a parallel section (RD-TD plane), and the rotation operation was performed so that an orientation mapping image of the ND plane viewed from the RD-ND plane was obtained.
• the subgrain size was calculated by the line segment method. The results are shown in Table 1.
• a region surrounded by an inclination angle of 15 ° or less between crystal grains is subgrain, and subgrains having the same crystal orientation have the same color.
• the relationship between color and crystal orientation is shown in the color code.
• the tilt angle between the subgrains is 0 to 15 °, but the boundary of the tilt angle 0 to 15 ° can be displayed as a line on the orientation mapping.
• the size of the subgrain was measured by the naked eye judgment of the orientation mapping diagram. Note that the location where the crystal grains exist is a minute region, and the size of the subgrain varies depending on the location, but in the measurement of the size, the largest size subgrain was measured here.
• the acceptance standard of tensile strength was 220 MPa or more, and the acceptance standard of elongation was 3.0% or more.
• the acceptance criteria for tensile strength was 215 MPa or more, and the acceptance criteria for elongation was 1.0% or more.
• No. 1 is an invention example. Since 1 to 14 satisfy the scope of the present invention, the strength and elongation were excellent, and the conductivity was 55% or more.
• the subgrain size was not less than the upper limit value, the soaking temperature was too high, the pinning force of the dispersed particles could not be obtained, and the crystal grains of the foil were not refined, so the elongation was inferior.
• the subgrain size was not less than the upper limit, and the soaking temperature was too low, resulting in insufficient homogenization and poor elongation.
• the intermediate annealing was a batch type, fine crystal grains were not obtained at the time of intermediate annealing, and subgrains were grown and coalesced at the time of foil rolling, and a fine subgrain structure was not obtained. Also, the degree of work hardening was insufficient. For these reasons, the tensile strength (tensile strength) was low, the strength was inferior, the subgrain size exceeded the upper limit value, and the elongation was inferior.
• the aluminum hard foil for a battery current collector according to the present invention has a high strength as pure aluminum even if it is a thin wall of 9 to 20 ⁇ m (in the case of single rolling) and 5 to 20 ⁇ m (in the case of polymerization rolling).
• the electric resistance is low, the capacity of the lithium ion secondary battery can be increased.
• the elongation is excellent, it is possible to prevent the foil from being broken in the manufacturing process of the electrode material, and it is possible to prevent the trouble that the production line is stopped.

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