Aluminum alloy foil for electrode collector and production method therefor

Abstract

An object of the present invention is to provide an aluminum alloy foil for an electrode current collector, the foil having a high strength and high strength after a drying process. The aluminum alloy foil can be manufactured at low cost. Disclosed is an aluminum alloy foil for electrode current collector, including 0.03 to 1.0% of Fe, 0.01 to 0.2% of Si, 0.0001 to 0.2% of Cu, 0.005 to 0.03% of Ti, with the rest being Al and unavoidable impurities. The aluminum alloy foil has Fe solid solution content of 200 ppm or higher, and an intermetallic compound having a maximum diameter length of 0.1 to 1.0 μm in an number density of 2.0×10.sup.4 particles/mm.sup.2 or more.

Claims

1. An aluminum alloy foil for electrode current collector, consisting of: 0.03 to 1.0 mass % (hereinafter referred to as %) of Fe, 0.01 to 0.2% of Si, 0.0001 to 0.2% of Cu, 0.005 to 0.03% of Ti, Al, and unavoidable impurities, wherein an amount of each of the unavoidable impurities is 0.02% or less, and a total amount of the unavoidable impurities is 0.15% or less; the aluminum alloy foil has Fe solid solution content of 200 ppm or higher, and an intermetallic compound having a maximum diameter length of 0.1 to 1.0 μm in a number density of 2.0×10.sup.4 particles/mm.sup.2 or more; and the aluminum alloy foil has 0.2% yield strength of 170 MPa or more.

2. A method for manufacturing the aluminum alloy foil of claim 1, comprising the steps of: forming by continuous casting an aluminum alloy sheet consisting of 0.03 to 1.0% of Fe, 0.01 to 0.2% of Si, 0.0001 to 0.2% of Cu, 0.005 to 0.03% of Ti, Al, and unavoidable impurities, an amount of each of the unavoidable impurities being 0.02% or less, and a total amount of the unavoidable impurities being 0.15% or less; and performing cold rolling followed by foil rolling without performing heat treatment to the aluminum alloy sheet to produce the aluminum alloy foil, wherein the aluminum alloy foil has Fe solid solution content of 200 ppm or higher, and an intermetallic compound having a maximum diameter length of 0.1 to 1.0 μm in a number density of 2.0×10.sup.4 particles/mm.sup.2 or more, and the aluminum alloy foil has 0.2% yield strength of 170 MPa or more.

Description

DESCRIPTION OF EMBODIMENTS

(1) <Composition of Aluminum Alloy Foil>

(2) The aluminum alloy foil for an electrode current collector according to the present invention comprises: 0.03 to 1.0% of Fe, 0.01 to 0.2% of Si, 0.01 to 0.2% of Cu, 0.005 to 0.03% of Ti, with the rest consisting of Al and unavoidable impurities.

(3) Fe is an element that increases strength by addition thereof, and 0.03 to 1.0% of Fe is included. When the additive amount of Fe is less than 0.03%, there is no contribution to the improvement in strength. In contrast, when the additive amount of Fe exceeds 1.0%, coarse intermetallic compounds of Al—Fe based compound or Al—Fe—Si based compound easily crystallize during the continuous casting, which leads to unfavorable phenomena of cut during the rolling and generation of pinholes.

(4) Si is an element that increases strength by addition thereof, and 0.01 to 0.2% of Si is included. When the additive amount of Si is less than 0.01%, there is no contribution to the improvement in strength. In addition, Si is included in a common aluminum based metal as impurities. As a result, in order to restrict the amount to less than 0.01%, a high-purity base metal should be used. This is difficult to achieve in view of economic reasons. In contrast, when the additive amount of Si exceeds 0.2%, the size of the intermetallic compound crystallized during the continuous casting becomes large, resulting in the decrease in the number of the fine intermetallic compound which contributes to the improvement in strength. Accordingly, the strength of the aluminum alloy foil decreases.

(5) Cu is an element that increases strength by addition thereof, and 0.0001 to 0.2% of Cu is included. In order to restrict the additive amount of Cu to less than 0.0001%, a high-purity base metal should be used. This is difficult to achieve in view of economic reasons. In contrast, when the additive amount of Cu exceeds 0.2%, the work hardening increases, thereby becoming prone to cut during the foil rolling.

(6) Ti is added by 0.005 to 0.03% as a crystal grain refining agent. By refining the crystal grain in the cast sheet after the continuous casting, occurrence of crack in the cast sheet can be prevented, and rolling property can be highly improved. When the amount of Ti added is less than 0.005%, the property as refining agent cannot be expressed, and the crystal grain would become coarse. Accordingly, the sheet would be prone to cuts during cold rolling and foil rolling. On the other hand, when the amount of Ti added exceeds 0.03%, coarse intermetallic compounds such as AlTi3 would be easily formed during the continuous casting, and thus the sheet would be prone to cuts during cold rolling and foil rolling.

(7) With regard to other points, a material of an embodiment of the present invention contains unavoidable impurities such as Cr, Ni, B, Zn, Mn, Mg, V, and/or Zr. An amount of each of the unavoidable impurities is preferably 0.02% or less, and a total amount thereof is preferably 0.15% or less.

(8) <Original Sheet Strength>

(9) With regard to an aluminum alloy primarily containing Fe, Si, Cu, and Ti when each of the elements are dissolved in the aluminum alloy as much as possible and the crystals of the intermetallic compound formed during the continuous casting is dispersed uniformly and finely, dislocation movement can be reduced, thereby achieving higher strength. Further, since the cooling speed is faster in the continuous casting than the semi-continuous casting and rolling, the content of the solid solution for each of the elements increase, and thus the work hardening during processing increase. Accordingly, strength of the aluminum alloy foil can be further improved by cold rolling and foil rolling.

(10) Tensile strength of an original sheet after final cold rolling is preferably 190 MPa or higher. Then, 0.2% yield strength thereof is preferably 170 MPa or higher. When the tensile strength is less than 190 MPa and the 0.2% yield strength is less than 170 MPa, the strength is insufficient. Consequently, tension imposed during application of an active material is likely to produce cuts and cracks.

(11) <Strength After Heat Treatment>

(12) A step of manufacturing a positive electrode plate includes a drying process after application of an active material so as to remove a solvent from the active material. At this drying process, heat treatment is carried out at a temperature of about 100 to 180° C. This heat treatment may cause a change in mechanical property because an aluminum alloy foil is softened. Thus, the mechanical property of the aluminum alloy foil after the heat treatment is critical. During heat treatment at 100 to 180° C., external heat energy activates dislocation and facilitates its movement. This decreases strength in the course of restoration thereof. In order to prevent the strength decrease in the course of the restoration during the heat treatment, reducing the dislocation movement by solid-solution elements or precipitates of intermetallic compound finely dispersed in the aluminum alloy is effective.

(13) In the present invention, it is preferable that the tensile strength is 180 MPa or higher and 0.2% yield strength is 160 MPa or higher after heat treatment at 120° C. for 24 hours, at 140° C. for 3 hours, or at 160° C. for 15 minutes. The strength after the heat treatment of the present invention is greatly affected by the solid solution content of Fe which is dissolved in a supersaturated manner and by the intermetallic compound which is crystallized during the continuous casting. The faster the cooling speed during the continuous casting, the more Fe is dissolved and the more the fine intermetallic compound is crystallized, thereby improving the strength after the heat treatment. When the afore-mentioned tensile strength after heat treatment is lower than 180 MPa and 0.2% yield strength is lower than 160 MPa, the aluminum alloy foil is easily deformed during the press working after the drying process. This strength is insufficient since the adhesion between the active material and the aluminum alloy foil decreases and the aluminum alloy foil becomes prone to ruptures during a slitting process.

(14) <Solid Solution Contend of Fe>

(15) The aluminum alloy foil preferably has Fe solid solution content of 200 ppm or higher. In order to dissolve 200 ppm or more of Fe, Fe dissolved in the sheet in a supersaturated manner during the continuous casting should be maintained until the final foil without performing heat treatment. Fe should be dissolved as much as possible in order to maintain the strength and the strength after the drying process after the application of an active material. When the content is less than 200 ppm, it is unfavorable since the strength and the strength after the drying process after the application of an active material decreases.

(16) <Intermetallic Compound>

(17) Intermetallic compounds having a maximum diameter length of 0.1 to 1.0 μm exist at the surface of the aluminum alloy foil, the number of such intermetallic compound being 2.0×10.sup.4 particles/mm.sup.2. These intermetallic compounds are Al—Fe based or Al—Fe—Si based, and finely precipitate during continuous casting. These fine intermetallic compounds improve the strength of the aluminum alloy foil by dispersion strengthening, while preventing the decrease in strength after the drying process after the application of an active material.

(18) When the number of the intermetallic compounds having a maximum diameter length of 0.1 μm or shorter is less than 2.0×10.sup.4 particles/mm.sup.2, contribution to the dispersion strengthening is small, and thus the strength decreases. The intermetallic compounds having a maximum diameter length of longer than 1.0 μm have small contribution to the improvement in strength, and may become a trigger point of pinholes. Therefore, it is preferable to suppress such intermetallic compound. In addition, in order to enhance the distribution of these intermetallic compounds, the shape of the intermetallic compounds becomes important. To suppress the dislocation movement during the drying process after the application of the active material, it is preferable that the aspect ratio, defined as the ratio of the long diameter of the intermetallic compound against the short diameter of the intermetallic compound is 3 or less. The number of the intermetallic compound can be counted by observing the surface of the aluminum alloy foil using scanning electron microscope (SEM). In particular, the surface of the aluminum alloy foil is subjected to electropolishing to give a mirror state. Then, the reflected electron image is observed at a magnification of 1000 times for 30 visual fields. The number of the intermetallic compound is quantified by using an image analyzing device. The longer side of the intermetallic compound observed as a dimensional shape in the visual field of the reflected electron image is defined as the maximum diameter length of the intermetallic compound.

(19) <Electrical Conductivity>

(20) Electrical conductivity is preferably 55% IACS or higher. The electrical conductivity represents a solid solution state of a solute element, particularly of Fe, Si and the like. When one use electrode current collector of the present invention for a lithium ion battery, in a case where a discharge rate exceeds 5C, which is a high current level, electrical conductivity of less than 55% IACS is not preferable because its battery capacity decrease. Note that the “1C” means a current level to complete, in one hour, the discharge from a cell having the nominal capacity value when a constant current at the current level is discharged from the cell.

(21) <Continuous Casting and Rolling>

(22) The aluminum alloy molten metal having the afore-mentioned composition is subjected to continuous casting and rolling to obtain a cast sheet. Typical continuous casting includes twin roll continuous casting and twin belt continuous casting. The twin roll continuous casting and rolling is a method which includes feeding of the aluminum alloy molten metal from a fire-resistive supply nozzle in between cooled rolls facing each other, followed by continuous casting and rolling into a thin sheet. 3C method, hunter method and the like are used in the industry. The twin belt continuous casting includes feeding the molten metal in between a pair of opposing upper and lower water-cooled circulating belts, followed by solidifying the molten metal by cooling the molten metal with the surface of the belts, thereby continuously casting and rolling into a thin sheet. The present invention may adopt either one of the twin roll continuous casting or the twin belt continuous casting, and shall not be limited to a particular manufacturing method. Here, the twin roll continuous casting requires shorter time for the cooling when compared with the twin belt continuous casting, resulting in more fine crystals of the intermetallic compound, thereby achieving aluminum alloy foil with higher performance. Hereinafter, a manufacturing method using the twin roll continuous casting as one example of the continuous casting is described.

(23) Aluminum alloy containing Fe, Si, and Cu in the range determined by the present invention is molten to give a molten metal, and is maintained in a holding furnace. Then, the molten metal goes through a conventional degas processing and passes through a filter for removing inclusion from casting. Subsequently, the molten metal is solidified and rolled with the water cooled rolls. Ti is added to the molten metal as a crystal grain refining agent, in the form of Al—Ti mother alloy, Al—Ti—B mother alloy, Al—Ti—C mother alloy and the like. Here, as the method for adding the mother alloy, addition of the mother alloy into the holding furnace may be conducted as a waffle-like block; or may be added after the degas processing or before or after passing the filter as a rod. In the present invention, any of these methods of addition can refine the crystal grain of the cast sheet after the continuous casting, and thus can prevent cracks in the cast sheet and can improve the rolling property during the cold rolling and the foil rolling.

(24) The temperature of the molten metal when casting by the twin roll continuous casting is preferably in the range of 680 to 800° C. The temperature of the molten metal is the temperature of the head box located immediately before the supply nozzle. When the temperature of the molten metal is lower than 680° C., intermetallic compound is formed in the supply nozzle and becomes mixed into the sheet ingot, thereby causing cut in the sheet during cold rolling. When the temperature of the molten metal exceeds 800° C., the aluminum alloy molten metal does not solidify sufficiently in between the rolls during the casting, and thus normal cast sheet cannot be obtained. The thickness of the cast sheet after the continuous casting is 20 mm or less. When the thickness of the sheet exceeds 20 mm, the solidifying speed during the continuous casting becomes slow, coarsening the crystals of the intermetallic compound, thereby decreasing the number of the fine intermetallic compound which contributes to the dispersion strengthening.

(25) <Process After Continuous Casting>

(26) The cast sheet obtained by the continuous casting is subjected to cold rolling followed by foil rolling to give the desired aluminum alloy foil. Heat treatment is not performed in between the cold rollings. When the heat treatment is performed, Fe which have been dissolved in a supersaturated manner during the continuous casing would partially precipitate, which leads to unfavorable decrease in strength and strength after drying process. Here, the methods for performing cold rolling and foil rolling are not limited in particular. When compared with the conventional semi-continuous casting and a conventional method which performs heat treatment after the continuous casting, the present manufacturing method can cut the manufacturing cost largely since it performs only cold rolling and foil rolling after the continuous casting.

(27) <Thickness of the Aluminum Alloy Foil>

(28) After the final cold rolling, the aluminum alloy foil should have a thickness of 6 to 30 μm. When the thickness is less than 6 μm, pin holes are likely to occur during foil rolling. This situation is not preferable. When the thickness exceeds 30 μm, the volume and weight of an electrode current collector increase and the volume and weight of an active material decrease in the same occupied space. In the case of a lithium-ion secondary battery, the above is not preferable because a battery capacity decreases.

EXAMPLES

(29) The present invention will be explained in details by referring to the following Examples 1 to 10. The Examples, however, are just examples, and thus the present invention shall not be limited to the Examples.

(30) Cast sheet with a thickness of 8 mm was prepared by the twin roll continuous casting using the aluminum alloy molten metal with the composition shown in Table 1. The cast sheet after the continuous casting was subjected to cold rolling followed by foil rolling without performing heat treatment. Accordingly, the aluminum alloy foil with the thickness of 15 μm was obtained.

(31) Regarding Comparative Examples 11 to 16, aluminum alloy foils with the thickness of 15 μm was obtained by the twin roll continuous casting with the conditions shown in Table 1, in a similar manner as the Examples. In Comparative Example 17, cast sheet with the thickness of 8 mm after the continuous casting was subjected to cold rolling until its thickness reached 3.0 mm, followed by intermediate annealing at 400° C. for 5 hours. Then, cold rolling was performed followed by foil rolling to give an aluminum alloy foil with the thickness of 15 μm. In Comparative Examples 18 and 19, ingots with the thickness of 500 mm were cast by conventional manufacturing method of semi-continuous casting. Subsequently, homogenization treatment at 500° C. for 1 hour was performed, followed by hot rolling to give an ingot sheet with the thickness of 4 mm. Then, cold rolling was performed until the thickness reached 0.8 mm, followed by intermediate annealing at 300° C. for 4 hours using a batch furnace. After the intermediate annealing, cold rolling and foil rolling were performed continuously to give the aluminum alloy foil with the thickness of 15 μm.

(32) TABLE-US-00001 TABLE 1 Heat Treatment Chemical Component (mass. %) Conditions Al and After Foil Method of Unavoidable Continuous Thickness No. Casting Si Fe Cu Ti Impurities Casting (μm) Example 1 Twin Roll 0.03 0.06 0.009 0.006 Rest No 15 2 Continuous 0.07 0.32 0.02 0.015 Rest No 15 3 Casting 0.13 0.44 0.03 0.021 Rest No 15 4 0.16 0.79 0.03 0.028 Rest No 15 5 0.01 0.06 0.16 0.008 Rest No 15 6 0.03 0.03 0.01 0.009 Rest No 15 7 0.02 0.05 0.0002 0.007 Rest No 15 8 0.19 0.68 0.09 0.014 Rest No 15 9 0.14 0.96 0.15 0.017 Rest No 15 10 0.12 0.48 0.19 0.018 Rest No 15 Comparative Example 11 Twin Roll 0.22 0.11 0.0007 0.009 Rest No 15 12 Continuous 0.02 0.01 0.0008 0.007 Rest No 15 13 Casting 0.18 1.50 0.12 0.018 Rest No 15 14 0.17 0.85 0.30 0.017 Rest No 15 15 0.15 0.36 0.02 0.001 Rest No 15 16 0.16 0.57 0.03 0.052 Rest No 15 17 0.08 0.28 0.02 0.013 Rest 400° C. × 5 h 15 18 Semi-continuous 0.03 0.06 0.009 0.007 Rest Homogenizing 15 19 Casting 0.13 0.44 0.03 0.009 Rest Treatment 15 500° C. × 1 h Intermediate Annealing 300° C. × 4 h

(33) Next, each aluminum alloy foil was used to prepare a positive electrode material for a lithium-ion secondary battery. PVDF as a binder was added to an active material primarily containing LiCoO.sub.2 to yield a positive electrode slurry. This positive electrode slurry was applied on both surfaces of the aluminum alloy foil with a width of 30 mm. Then, the resulting aluminum alloy foil was subjected to heat treatment for drying under three different conditions including 120° C. for 24 hours, 140° C. for 3 hours, and 160° C. for 15 minutes. After that, a roller press machine was used to perform compression forming to increase the density of the active material.

(34) Each aluminum alloy foil as so manufactured was used to measure and evaluate: the tensile strength, 0.2% yield strength, electrical conductivity, number of the intermetallic compound, number of cuts occurred during foil rolling, and number of pin holes; the tensile strength and 0.2% yield strength after the heat treatment at 120° C. for 24 hours; the tensile strength and 0.2% yield strength after the heat treatment at 140° C. for 3 hours; and the tensile strength and 0.2% yield strength after the heat treatment at 160° C. for 15 minutes. Table 2 shows the results. In addition, occurrence of cut during the active material application step and the occurrence of detachment of active material was observed for each positive electrode materials. Table 3 shows the results.

(35) TABLE-US-00002 TABLE 2 Number of Intermetallic Compounds Original Maximum Heating at Heating at Heating at Sheet Diameter Pin 120° C. 140° C. 160° C. Strength Solid Length 0.1 Hole for 24 Hours for 3 Hours for 15 Hours 0.2% Electrical Solution to 1.0 μm Density 0.2% 0.2% 0.2% Tensile Yield Conduc- Content (×10.sup.4 Cut (×10.sup.−3 Tensile Yield Tensile Yield Tensile Yield Strength Strength tivity of Fe particles/ During holes/ Strength Strength Strength Strength Strength Strength No. (N/mm.sup.2) (N/mm.sup.2) (% IACS) (ppm) mm.sup.2) Rolling m.sup.2) (N/mm.sup.2) (N/mm.sup.2) (N/mm.sup.2) (N/mm.sup.2) (N/mm.sup.2) (N/mm.sup.2) Example  1 209 192 60.8  256 2.3 No 0.6 206 189 207 190 207 190  2 223 195 60.1  908 2.6 No 0.6 219 192 220 193 222 193  3 250 223 57.2 1124 2.4 No 0.6 247 220 248 221 248 222  4 295 258 56.9 2268 3.4 No 0.8 290 251 292 253 293 254  5 195 173 61.0  259 2.6 No 0.3 191 170 192 171 193 172  6 199 178 61.1  203 2.2 No 0.3 195 174 196 175 197 177  7 191 172 60.7  229 2.3 No 0.3 189 169 190 170 191 172  8 278 230 56.2 1546 3.8 No 1.1 273 226 275 227 276 228  9 292 250 55.4 2147 4.1 No 0.3 288 247 289 248 290 249 10 307 266 55.9 1489 3.0 No 0.6 303 262 304 263 305 265 Compar- ative Example 11 188 167 60.2  302 1.1 No 1.4 177 153 176 154 182 161 12 173 148 60.7  23 1.3 No 0.6 157 131 162 136 168 141 13 224 187 55.7 2855 3.8 No 3.9 219 183 221 184 223 186 14 336 290 55.9 1930 3.1 Yes 1.1 332 284 333 286 335 288 15 232 201 56.3 1022 2.7 Yes 0.8 226 197 228 198 230 199 16 266 225 54.3 1344 2.8 Yes 0.8 260 221 262 223 264 224 17 188 167 59.7  59 2.1 No 0.3 163 138 171 145 176 151 18 160 141 63.8  35 0.2 No 0.3 134 112 145 121 152 133 19 176 155 60.9  39 0.5 No 0.3 142 121 156 131 163 140

(36) TABLE-US-00003 TABLE 3 Positive Electrode Material Heating at 120° C. for 24 Hours Heating at 140° C. for 3 Hours Heating at 160° C. for 15 Minutes Cut during Detachment Cut during Detachment Cut during Detachment Active-material-application of Active Active-material-application of Active Active-material-application of Active No. Step Material Step Material Step Material Example 1 No No No No No No 2 No No No No No No 3 No No No No No No 4 No No No No No No 5 No No No No No No 6 No No No No No No 7 No No No No No No 8 No No No No No No 9 No No No No No No 10 No No No No No No Comparative Example 11 Yes Yes Yes Yes No No 12 Yes Yes Yes Yes Yes Yes 13 No No No No No No 14 No No No No No No 15 No No No No No No 16 No No No No No No 17 Yes Yes Yes Yes Yes Yes 18 Yes Yes Yes Yes Yes Yes 19 Yes Yes Yes Yes Yes Yes
<Tensile Strength and 0.2% Yield Strength>

(37) The tensile strength of the aluminum alloy foil which had been cut out in a direction of the rolling was measured with an Instron tension tester AG-10kNX, manufactured by Shimadzu Corporation. The measurement was performed under conditions with a test piece size of 10 mm×100 mm, at a chuck distance of 50 mm, and at a crosshead speed of 10 mm/min. In addition, in order to simulate the drying process, heat treatment at 120° C. for 24 hours, at 140° C. for 3 hours, or at 160° C. for 15 minutes was carried out. Then, the aluminum alloy foil was cut out in a direction of the rolling. After that, the tensile strength was measured in the same manner as in the above. In addition, 0.2% yield strength was determined from a stress/strain curve.

(38) <Solid Solution Content of Fe>

(39) The solid solution content of Fe was measured as follows. 1.0 g of aluminum alloy foil and 50 mL of phenol were heated to 200° C. to dissolve the alloy, followed by addition of 100 mL of benzyl alcohol as an anti-caking agent. The intermetallic compound was separated by filtration, and the filtrate was measured by IPC atomic emission spectrometry.

(40) <Electrical Conductivity>

(41) With regard to electrical conductivity, electrical resistivity was measured by a four-terminal method, and was converted to electrical conductivity.

(42) <Particle Number of the Intermetallic Compound>

(43) The number of the intermetallic compound was counted by observing the surface of the aluminum alloy foil using scanning electron microscope (SEM). The surface of the aluminum alloy foil was subjected to electropolishing to give a mirror state. Then, the reflected electron image was observed at a magnification of 1000 times for 30 visual fields. The number of the intermetallic compound was quantified by using an image analyzing device.

(44) <Pinhole Density>

(45) A coil with a width of 0.6 m and a length of 6000 m was made from the aluminum alloy foil which was performed with foil rolling until the foil reaches a thickness of 15 μm. The number of pinholes was observed using a surface inspection machine. The number of the pinholes observed was divided by the total surface area to give the number of pinholes per 1 m.sup.2 unit area. This value was taken as the pinhole density. The pinhole density of less than 2.0×10.sup.−3 pinholes/m.sup.2 was considered acceptable and the pinhole density of 2.0×10.sup.−3 pinholes/m.sup.2 or more was determined as unacceptable.

(46) <Whether or not Cut Occurs During Active-Material-Application Step>

(47) Whether or not a cut occurred in a positive electrode material applied during an active-material-application step was visually inspected. The case without a cut was considered acceptable, and the case with a cut was determined as unacceptable.

(48) <Whether or not Active Material Detaches>

(49) The presence or absence of the active material detachment was visually inspected. When no detachment occurred, the case was considered acceptable. When at least some detachment occurred, the case was determined as unacceptable.

(50) In Examples 1 to 10, no cut occurred during the active material application step, no detachment of the active material was observed, high electrical conductivity was obtained, and thus excellent evaluation result was obtained.

(51) In Comparative Example 11, the high content of Si resulted in small number of fine intermetallic compound, insufficient strength before and after heat treatment at 120° C. for 24 hours or at 140° C. for 3 hours, thereby causing cut during the active material application step and detachment of the active material.

(52) In Comparative Example 12, the low content of Fe resulted in insufficient strength before and after heat treatment at 120° C. for 24 hours, at 140° C. for 3 hours, or at 160° C. for 15 minutes, thereby causing cut during the active material application step and detachment of the active material.

(53) In Comparative Example 13, the high content of Fe resulted in generation of many pinholes.

(54) In Comparative Example 14, the high content of Cu resulted in too high work hardening, thereby causing cut during the foil rolling.

(55) In Comparative Example 15, the low content of Ti added resulted in coarsening of the crystal grains contained in the sheet after continuous casting, thereby causing cut during the cold rolling.

(56) In Comparative Example 16, the high content of Ti added resulted in formation of many coarse intermetallic compounds, thereby causing cut during the cold rolling.

(57) In Comparative Example 17, the implementation of heat treatment to the cast sheet after the continuous casting resulted in precipitation of many Fe which was dissolved in a supersaturated manner, insufficient strength before and after heat treatment at 120° C. for 24 hours, at 140° C. for 3 hours, or at 160° C. for 15 minutes, thereby causing cut during the active material application step and detachment of the active material.

(58) In Comparative Examples 18 and 19, the adoption of semi-continuous casting resulted in insufficient strength before and after heat treatment at 120° C. for 24 hours, at 140° C. for 3 hours, or at 160° C. for 15 minutes, thereby causing cut during the active material application step and detachment of the active material.