WO2012105143A1 - Feuille d'alliage d'aluminium pour un boîtier de batterie ayant une bonne aptitude au moulage et une bonne aptitude au soudage - Google Patents

Feuille d'alliage d'aluminium pour un boîtier de batterie ayant une bonne aptitude au moulage et une bonne aptitude au soudage Download PDF

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WO2012105143A1
WO2012105143A1 PCT/JP2011/080110 JP2011080110W WO2012105143A1 WO 2012105143 A1 WO2012105143 A1 WO 2012105143A1 JP 2011080110 W JP2011080110 W JP 2011080110W WO 2012105143 A1 WO2012105143 A1 WO 2012105143A1
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mass
aluminum alloy
less
cold
weldability
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PCT/JP2011/080110
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English (en)
Japanese (ja)
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鈴木　健太
堀　久司
圭治 金森
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日本軽金属株式会社
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Priority to KR1020157026078A priority Critical patent/KR20150116902A/ko
Priority to KR1020137019976A priority patent/KR20130109224A/ko
Priority to CN201180055949.6A priority patent/CN103261461B/zh
Publication of WO2012105143A1 publication Critical patent/WO2012105143A1/fr

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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/20—Bonding
    • B23K26/32—Bonding taking account of the properties of the material involved
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • 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 a high-strength aluminum alloy plate excellent in formability and laser weldability, which is used for a secondary battery container such as a lithium ion battery.
  • Al-Mn 3000 series alloys are relatively excellent in strength, formability, and laser weldability, and are therefore used as materials for manufacturing secondary battery containers such as lithium ion batteries. Yes. After forming into a desired shape, it is hermetically sealed by laser welding and used with a secondary battery container. Development has been made on an aluminum alloy plate for a secondary battery container, which is based on an existing 3000 series alloy together with the 3000 series alloy and has further improved strength and formability.
  • the composition of the aluminum alloy plate is as follows: Si: 0.10 to 0.60 mass%, Fe: 0.20 to 0.60 mass%, Cu: 0.10 to 0.70 mass% , Mn: 0.60 to 1.50 mass%, Mg: 0.20 to 1.20 mass%, Zr: more than 0.12 and less than 0.20 mass%, Ti: 0.05 to 0.25 mass% B: 0.0010 to 0.02% by mass, the balance being Al and inevitable impurities, and 45 ° ear ratio in the rolling direction in a cylindrical container deep drawing method is 4 to 7%.
  • An aluminum alloy plate for rectangular cross-section battery containers is described.
  • JP 2010-126804 A Mn: 0.8% by mass or more and 1.8% by mass or less, Mg: more than 0.6% by mass and 1.2% by mass or less, Cu: more than 0.5% by mass 1.5% by mass or less, Fe as an impurity is regulated to 0.5% by mass or less, Si is controlled to 0.3% by mass or less, and has a composition consisting of the balance Al and inevitable impurities, ⁇ 001 ⁇
  • the ratio (C / S) of the orientation density C in the ⁇ 100> orientation to the orientation density S in the ⁇ 123 ⁇ ⁇ 634> orientation is 0.65 or more and 1.5 or less, and the tensile strength after the final cold rolling. Describes an aluminum alloy plate for a prismatic battery container having a thickness of 250 MPa to 330 MPa and an elongation of 1% or more.
  • an aluminum alloy plate based on a 3000 series alloy and improved in its composition may have insufficient weld penetration depth, which may cause abnormal beading and a problem in laser weldability. Yes.
  • Japanese Patent Application Laid-Open No. 2009-127075 discloses an aluminum alloy material for pulse laser welding and a battery case that can prevent the occurrence of abnormal parts by pulse laser welding of an A1000 series aluminum material and can form a uniform good weld.
  • Ti which has been added to suppress the coarsening of crystal grains in the casting process, has an adverse effect on the welded portion, and an abnormal portion is formed when A1000 series aluminum is welded by pulse laser welding.
  • Ti contained in pure aluminum should be regulated to less than 0.01% by mass.
  • Japanese Patent Application Laid-Open No. 2003-7260 discloses Mn: 0.3 to 1.5 mass%, Fe: 1.0 There has been proposed an aluminum alloy plate for a secondary battery case comprising more than 1.8% by mass, the balance Al and inevitable impurities. Further, Cu: 0.1 to 0.8% by mass and / or Mg: more than 0.10 to 1.0% by mass, and / or Cr: 0.05 to 0.2% by mass and / or Zr: 0.0. It may contain from 05 to 0.2% by mass. However, no detailed study has been made on weldability.
  • the 1000 series has a problem that the weldability is stable (the number of abnormal beads is small) and the formability is excellent but the strength is low. Therefore, as the size of the lithium ion battery is increased, it is expected that high strength characteristics are required, and there is a problem in applying the 1000 series aluminum material as it is.
  • a 3000 series alloy plate provides strength and deep penetration depth, it has a tendency to have inferior formability and a large number of abnormal beads compared to a 1000 series alloy plate.
  • a 1000 series alloy plate is excellent in formability and the number of abnormal beads decreases, but there is a concern that the strength is insufficient.
  • the present invention has been devised to solve such problems, has high strength applicable to large-sized lithium ion battery containers, is excellent in moldability, and further has laser weldability. Is intended to provide an excellent Al—Fe-based aluminum alloy sheet.
  • the aluminum alloy plate for battery case having excellent formability and weldability according to the present invention is provided with Fe: 0.3 to 1.5 mass%, Mn: 0.3 to 1.0 mass%.
  • the material When the material is cold-rolled, it exhibits an elongation value of 2% or more and a tensile strength of 160 MPa or more. Moreover, when it is set as a cold-rolled annealing material, the elongation value of 20% or more and the tensile strength of 130 MPa or more shall be exhibited.
  • the aluminum alloy plate of the present invention has high strength, excellent formability, and excellent laser weldability. Therefore, a secondary battery container that is excellent in sealing performance and capable of suppressing swelling can be manufactured at low cost. Can be manufactured.
  • a cold-rolled material in the case of a cold-rolled material, it has an elongation value of 2% or more and a tensile strength of 160 MPa or more.
  • a cold-rolled annealing material when used, not only the tensile strength of 130 MPa or more but also the elongation value is 20% or more. And exhibits excellent moldability.
  • FIG. 1 is a conceptual diagram for explaining a method for measuring / evaluating the number of abnormal beads, and is a graph showing (A) a top view of a weld bead and (B) a change in bead width along the bead length direction. It is a conceptual diagram explaining the measurement / evaluation method of a penetration depth, (A) The top view and (B) sectional drawing of a weld bead.
  • Secondary batteries are manufactured by putting an electrode body in a container and then sealing it with a lid by welding or the like.
  • a secondary battery when charging, the temperature inside the container may rise and the pressure inside the container may increase. For this reason, if the strength of the material forming the container is low, there is a problem that the produced container is greatly swollen. Therefore, a material having high strength is required as a material to be used. Further, since a press method is generally used as a method for forming a container, the material itself is required to have excellent press formability.
  • a welding method is used as a method of sealing with a lid, it is also required to have excellent weldability.
  • a laser welding method is used as a welding method for manufacturing a secondary battery container or the like.
  • the weld bead width increases, the penetration depth tends to increase. For this reason, the weld bead width is locally wide at the abnormal bead portion and the penetration depth is deep, and if it is severe, penetration of the melted portion or the like occurs, leading to deterioration in battery performance and reliability.
  • the present inventors have intensively studied to obtain an aluminum alloy plate having high strength and excellent press formability, as well as excellent laser weldability through investigation of the number of abnormal beads generated in the weld and the penetration depth in the weld. Again, the present invention has been reached. The contents will be described below.
  • Fe 0.3 to 1.5% by mass Fe is an essential element for increasing the strength of the aluminum alloy plate and ensuring the penetration depth in laser welding. If the Fe content is less than 0.3% by mass, the strength of the aluminum alloy plate is lowered, and the penetration depth during laser welding is reduced, which is not preferable. When the Fe content exceeds 1.5% by mass, coarse intermetallic compounds such as Al— (Fe ⁇ Mn) —Si and Al 6 Fe crystallize during ingot casting, and formability in the final plate is reduced. These intermetallic compounds tend to evaporate during laser welding as compared to the Al matrix, and the number of abnormal beads increases and weldability decreases, which is not preferable.
  • the Fe content is in the range of 0.3 to 1.5% by mass.
  • a more preferable Fe content is in the range of 0.5 to 1.5% by mass.
  • a more preferable Fe content is in the range of 0.7 to 1.5% by mass.
  • Mn 0.3 to 1.0% by mass
  • Mn is an essential element for increasing the strength of the aluminum alloy plate and ensuring the penetration depth in laser welding. If the Mn content is less than 0.3% by mass, the strength of the aluminum alloy plate is lowered, and the penetration depth during laser welding is reduced, which is not preferable.
  • Mn content exceeds 1.0% by mass coarse intermetallic compounds such as Al— (Fe ⁇ Mn) —Si and Al 6 Mn crystallize during ingot casting, and formability in the final plate is reduced. These intermetallic compounds tend to evaporate during laser welding as compared to the Al matrix, and the number of abnormal beads increases and weldability decreases, which is not preferable.
  • the Mn content is in the range of 0.3 to 1.0% by mass.
  • a more preferable Mn content is in the range of 0.3 to 0.8% by mass.
  • a more preferable Mn content is in the range of 0.4 to 0.7% by mass.
  • Ti acts as a crystal grain refining agent during ingot casting and can prevent casting cracks.
  • Ti may be added alone, but when coexisting with B, a more powerful grain refinement effect can be expected, so addition with a rod hardener such as Al-5% Ti-1% B There may be.
  • the Ti content is less than 0.002% by mass, the effect of refining at the time of ingot casting is insufficient, which may cause casting cracks, which is not preferable.
  • the Ti content exceeds 0.20% by mass, a coarse intermetallic compound such as TiAl 3 is crystallized during ingot casting, which is not preferable.
  • the Ti content is in the range of 0.002 to 0.20 mass%.
  • a more preferable Ti content is in the range of 0.002 to 0.15 mass%.
  • a more preferable Ti content is in the range of 0.005 to 0.10% by mass.
  • Zr 0.05-0.20 mass% Zr, like Ti, acts as a grain refiner during ingot casting and can prevent casting cracks. Further, when Ti and Zr coexist, cracking at the time of solidification of the weld bead portion accompanied by rapid solidification is prevented, and the speed of pulse laser welding can be increased. When Ti, Zr, and B coexist, the effect of preventing the occurrence of cracks during solidification of the weld bead portion accompanied by rapid solidification becomes more remarkable.
  • the Zr content exceeds 0.20% by mass, a coarse intermetallic compound such as ZrAl 3 is crystallized at the time of ingot casting, which is not preferable. If the Zr content is less than 0.05% by mass, sufficient effects cannot be obtained. Therefore, the preferred Zr content is 0.05 to 0.20% by mass. A more preferable Zr content is in the range of 0.07 to 0.20 mass%. A more preferable Zr content is in the range of 0.07 to 0.18% by mass.
  • B 0.0005 to 0.10% by mass B, like Ti and Zr, acts as a crystal grain refining agent during ingot casting and can prevent casting cracks. For this reason, it contains as needed.
  • the preferable B content is 0.0005 to 0.10% by mass.
  • a more preferable B content is in the range of 0.001 to 0.05 mass%.
  • a more preferable B content is in the range of 0.001 to 0.01% by mass.
  • Cu content 0.2 to 1.0% by mass Cu precipitates in the Al matrix together with Mg as a CuMgAl 2 phase, thereby increasing the strength of the aluminum alloy plate. If the Cu content is less than 0.2% by mass, the increase in strength is insufficient, which is not preferable. On the other hand, when the Cu content exceeds 1.0% by mass, the formability of the final plate is lowered, which is not preferable.
  • the Cu content is in the range of 0.2 to 1.0% by mass.
  • a more preferable Cu content is in the range of 0.2 to 0.9% by mass.
  • a more preferable Cu content is in the range of 0.2 to 0.8% by mass.
  • Mg content 0.2 to 1.0 mass% Mg precipitates in the Al matrix together with Cu as a CuMgAl 2 phase, thereby increasing the strength of the aluminum alloy plate. If the Mg content is less than 0.2% by mass, the increase in strength is insufficient, which is not preferable. On the other hand, if the Mg content exceeds 1.0% by mass, an oxide film is generated during laser welding and weldability is lowered, which is not preferable.
  • the Mg content is in the range of 0.2 to 1.0% by mass.
  • a more preferable Mg content is in the range of 0.2 to 0.9% by mass.
  • a more preferable Mg content is in the range of 0.2 to 0.8% by mass.
  • Si content as an inevitable impurity less than 0.30% by mass
  • the content of Si as an inevitable impurity is preferably limited to less than 0.30% by mass.
  • coarse intermetallic compounds such as Al— (Fe ⁇ Mn) —Si are crystallized at the time of ingot casting, and formability is deteriorated.
  • a more preferable Si content is less than 0.25% by mass. Further preferable Si content is less than 0.20 mass%.
  • the Si content is less than 0.20% by mass, properties such as formability and weldability do not deteriorate.
  • Mn / Fe mass ratio 0.2 to 1.0 If the Mn / Fe ratio is less than 0.2 within the range of the Fe and Mn contents within the scope of the present invention, the penetration depth during laser welding decreases, which is not preferable. If the Mn / Fe ratio exceeds 1.0 within the range of Fe and Mn contents within the scope of the present invention, the number of abnormal beads increases, which is not preferable.
  • the mass ratio of Mn / Fe affects the type and amount of intermetallic compounds that crystallize during ingot casting. For example, it is also well known that when the Mn / Fe mass ratio increases, the number of Al 6 Mn intermetallic compounds increases.
  • intermetallic compounds such as Al 6 Mn tend to evaporate and are unstable during laser welding as compared to intermetallic compounds such as Al—Fe—Si, Al 6 Fe, and Al 3 Fe. For this reason, when Mn / Fe ratio exceeds 1.0, it is thought that the number of abnormal beads at the time of laser welding increases and weldability deteriorates.
  • Mn increases the thermal resistance of the material by being dissolved in an Al matrix
  • Mn is an element more important than Fe in securing the penetration depth during laser welding. For this reason, it is thought that the penetration depth at the time of laser welding is insufficient when the Mn / Fe ratio is less than 0.2.
  • Tensile strength and elongation value Cold-rolled material: Elongation value of 2% or more, Tensile strength of 160 MPa or more Cold-rolled annealed material: Elongation value of 20% or more, and tensile strength of 130 MPa or more Al-Fe-based aluminum
  • the strength of the material can be known from the tensile strength when the tensile test is conducted, and the formability can be known from the elongation value at the tensile test.
  • the elongation value is 2% or more in the cold-rolled material
  • a material having a tensile strength of 160 MPa or more is suitable for a cold-rolled annealed material, and an elongation value of 20% or more and a tensile strength of 130 MPa or more are suitable.
  • the number of second phase particles having an equivalent circle diameter of 5 ⁇ m or more in the metal structure is less than 500 / mm 2
  • the above-mentioned characteristics are that the metal structure of the Al—Fe-based aluminum alloy plate having the specific chemical composition is finely adjusted.
  • the number of second phase particles having an equivalent circle diameter of 5 ⁇ m or more in the metal structure may be less than 500 / mm 2 .
  • the metal structure there is no difference in the metal structure between the cold rolled material and the cold rolled annealed material. If it has the metal structure as described above, it exhibits an elongation value of 2% or more and a tensile strength of 160 MPa or more in the cold-rolled material, and 20% or more in the cold-rolled annealed material. It exhibits an elongation value and a tensile strength of 130 MPa or more.
  • the flux is appropriately charged and stirred, and further, if necessary, degassing in the furnace using a lance or the like, Hold the sedation to separate the soot from the surface of the melt.
  • the molten aluminum alloy melted in the melting furnace may be cast after it is once transferred to the holding furnace, but may be cast directly from the melting furnace.
  • a more desirable sedation time is 45 minutes or more.
  • ⁇ In-line degassing and filtering may be used as necessary.
  • In-line degassing is mainly of a type in which an inert gas or the like is blown into a molten aluminum from a rotating rotor, and hydrogen gas in the molten metal is diffused and removed in bubbles of the inert gas.
  • nitrogen gas is used as the inert gas, it is important to control the dew point to, for example, ⁇ 60 ° C. or lower.
  • the amount of hydrogen gas in the ingot is preferably reduced to 0.20 cc / 100 g or less.
  • hydrogen gas that is supersaturated in the ingot is deposited during laser welding after forming the final plate, depending on the conditions of the homogenization treatment before the hot rolling process, and a large number of blown gases are blown into the beads. In some cases, holes are generated. For this reason, the more preferable amount of hydrogen gas in the ingot is 0.15 cc / 100 g or less.
  • the cast ingot is manufactured by semi-continuous casting (DC casting).
  • DC casting semi-continuous casting
  • the solidification cooling rate at the center portion of the ingot is about 1 ° C./sec.
  • a relatively coarse intermetallic compound such as Al— (Fe ⁇ Mn) —Si is formed in the aluminum alloy at the center of the ingot.
  • crystallize from the molten metal there is a tendency to crystallize from the molten metal.
  • the casting speed in semi-continuous casting depends on the width and thickness of the ingot, it is usually 50 to 70 mm / min in consideration of productivity.
  • the flow rate of molten aluminum depends on the degassing conditions such as the flow rate of the inert gas. The smaller the (supply amount), the better the degassing efficiency in the tank, and it is possible to reduce the amount of hydrogen gas in the ingot.
  • a more desirable casting speed is 30 to 40 mm / min.
  • productivity is lowered, which is not desirable.
  • the casting speed is slower, the slope of the sump (solid phase / liquid phase interface) in the ingot becomes gentler, and casting cracks can be prevented.
  • Homogenization treatment is performed on an ingot obtained by casting by a semi-continuous casting method at 420 to 600 ° C. for 1 hour or longer .
  • the homogenization process is a process in which the ingot is kept at a high temperature to facilitate rolling, and casting segregation and elimination of residual stress inside the ingot are performed.
  • it is necessary to hold at a holding temperature of 420 to 600 ° C. for 1 hour or longer.
  • it is also a process for dissolving the transition elements constituting the intermetallic compound crystallized during casting to some extent in the matrix.
  • the holding temperature is too low or the holding temperature is short, the solid solution of the transition element or the like does not progress, the recrystallized grains become rough, and the appearance skin after DI molding may not be finished cleanly.
  • the holding temperature is too high, eutectic parts such as CuMgAl 2 which is the microscopic final solidified part of the ingot may melt, so-called burning may occur.
  • a more preferable homogenization temperature is 420 to 590 ° C.
  • the ingot held at a high temperature for a predetermined time in the hot rolling process is suspended by a crane after homogenization and brought to the hot rolling mill. Depending on the type of hot rolling mill, it is usually how many times.
  • the sheet is hot-rolled by such a rolling pass and wound on a roll as a hot rolled sheet having a predetermined thickness, for example, about 4 to 8 mm.
  • the roll on which the hot rolled sheet is wound is passed through a cold rolling machine and usually subjected to several passes of cold rolling.
  • an intermediate annealing treatment is performed as necessary.
  • the intermediate annealing is also a softening treatment, but depending on the material, a cold rolling roll may be inserted into the batch furnace and kept at a temperature of 300 to 450 ° C. for 1 hour or longer.
  • the holding temperature is lower than 300 ° C., softening is not promoted, and when the holding temperature exceeds 450 ° C., the processing cost increases.
  • the intermediate annealing can also serve as a solution treatment if it is maintained within a temperature of, for example, 450 ° C. to 550 ° C. within 15 seconds by a continuous annealing furnace and then rapidly cooled.
  • a temperature of, for example, 450 ° C. to 550 ° C. within 15 seconds by a continuous annealing furnace and then rapidly cooled.
  • the holding temperature is lower than 450 ° C., softening is not promoted, and when the holding temperature exceeds 550 ° C., burning may occur.
  • the final annealing performed after the final cold rolling may be, for example, a batch process in which an annealing furnace is maintained at a temperature of 400 to 500 ° C. for 1 hour or longer. If it is kept at a temperature of 550 ° C. within 15 seconds and then cooled rapidly, it can also serve as a solution treatment.
  • final annealing is not necessarily essential in the present invention, but it is desirable to make the final plate as soft as possible in view of formability in normal DI molding. Considering the moldability in the mold forming process, it is desirable to use an annealed material or a solution treated material.
  • the material is provided as cold rolled.
  • the final cold rolling rate is preferably in the range of 50 to 90%. If the final cold rolling rate is within this range, the average recrystallized grains in the final plate after annealing can be set to 20 to 100 ⁇ m, the elongation value can be set to 20% or more, and the appearance skin after molding can be finished beautifully. be able to. A more preferable final cold rolling rate is in the range of 60 to 90%.
  • the final cold rolling ratio when the material is cold rolled without being subjected to final annealing is preferably in the range of 5 to 40%. If the ironing process increases during DI molding, it is necessary to provide a final plate that is slightly harder than the annealed material. If the final cold rolling rate is less than 5%, depending on the composition, it becomes difficult to make the tensile strength of the final plate 160 MPa or more. If the final cold rolling rate exceeds 40%, the final plate depends on the composition. It is difficult to make the elongation value at 2% or more.
  • the elongation value in the final plate can be 2% or more and the tensile strength can be 160 MPa or more while cold rolling.
  • a more preferable final cold rolling rate is in the range of 10 to 30%.
  • An aluminum alloy plate for a secondary battery container can be obtained through the normal steps as described above.
  • the ingot was chamfered by 2 mm after cutting the hot water to a thickness of 26 mm.
  • This ingot is inserted into an electric heating furnace, heated to 430 ° C. at a temperature rising rate of 100 ° C./hr, homogenized at 430 ° C. ⁇ 1 hour, and subsequently heated to a thickness of 6 mm with a hot rolling mill. It hot-rolled until it became.
  • the cold-rolled sheet having a thickness of 1.25 mm was obtained by subjecting this hot-rolled sheet to cold rolling.
  • the cold-rolled sheet was inserted into an annealer, and after annealing at 390 ° C. for 1 hour, the annealed sheet was taken out from the annealer and air-cooled. Next, this annealed plate was cold-rolled to obtain a cold-rolled plate having a thickness of 1.0 mm.
  • the final cold rolling rate in this case was 20%.
  • the cold-rolled annealed plate was cold-rolled without subjecting the hot-rolled plate to intermediate annealing to obtain a 1 mm cold-rolled plate.
  • the final cold rolling rate in this case was 83.3%.
  • the cold-rolled sheet was inserted into the annealer, and after annealing at 390 ° C. for 1 hour, the cold-rolled sheet was taken out from the annealer and air-cooled.
  • test material having an elongation value of 2% or more was defined as good moldability ( ⁇ ), and the test material that was less than 2% was defined as poor moldability ( ⁇ ).
  • good moldability ⁇
  • poor moldability ⁇
  • test material having an elongation value of 20% or more was considered as good moldability ( ⁇ ), and the test material that was less than 20% was considered as poor moldability ( ⁇ ). did.
  • the evaluation results are shown in Table 3.
  • the final plate obtained was subjected to pulsed laser irradiation to evaluate laser weldability.
  • LUMONICS YAG laser welder JK701 under conditions of frequency 37.5 Hz, welding speed 450 mm / min, energy per pulse 6.0 J, shield gas (nitrogen) flow rate 1.5 (L / min), Two plates of the test material were butted without gaps between the end portions, and pulse laser welding having a total length of 120 mm was performed along the portion.
  • the width of the round molten bead formed by each pulse formed along the weld line having a length of 60 mm was continuously measured at intervals of 0.05 mm in the welding direction, and a length of 10 mm (1
  • the “average weld bead width” for each section) was calculated, and the number of locations showing bead widths that deviated by 1.1 or more from the “average weld bead width” in each section was counted. This count was totaled for 60 mm (6 sections) to obtain the number of abnormal beads of the specimen.
  • test material having an abnormal bead number of less than 10 was evaluated as being good (O), and the test material having an abnormal bead number of 10 or more was being evaluated as having an abnormal bead number evaluation (x). did.
  • the evaluation results are shown in Table 2 for the cold-rolled materials and in Table 3 for the cold-rolled annealed plates.
  • the intermetallic compound crystallized at the time of casting is heated to a high temperature by heating by pulse laser irradiation, dissolved in aluminum, and immediately after that, the molten bead is quenched, and elements such as Fe, Mn, and Si constituting the intermetallic compound becomes a supersaturated solid solution in the Al matrix.
  • the area of only the Al matrix in which no intermetallic compound is observed in the cross section is a molten part, and by measuring the maximum depth from the surface of the final plate of the area, The penetration depth can be measured.
  • the penetration depth of 5 sections was measured for one specimen, and the average value was defined as the penetration depth ( ⁇ m) in the specimen.
  • the cross section of the above-described abnormal bead is not subject to measurement.
  • a specimen having a penetration depth of 220 ⁇ m or more was regarded as good penetration evaluation ( ⁇ ), and a specimen having a penetration depth of less than 220 ⁇ m was regarded as poor penetration depth evaluation ( ⁇ ).
  • the evaluation results are shown in Table 2 for the cold-rolled materials and in Table 3 for the cold-rolled annealed plates.
  • the Mn content is as high as 1.27% by mass
  • the Mn / Fe ratio is 2.59, which is outside the range of the present invention
  • the penetration depth evaluation is good ( ⁇ )
  • the moldability is good ( ⁇ ).
  • the abnormal bead number was poorly evaluated (x).
  • Examples 11 to 15 in Table 3 showing the evaluation results of the cold-rolled annealed materials are annealed materials within the composition range of the present invention, both of laser weldability (abnormal bead number evaluation, penetration depth evaluation) and formability. All were good ( ⁇ ).
  • the Mn content is as high as 1.27% by mass, the Mn / Fe ratio is 2.59, which is out of the range of the present invention, the penetration depth evaluation is good ( ⁇ ), and the moldability is good ( ⁇ ).
  • the abnormal bead number was poorly evaluated (x).
  • Comparative Example 16 had a high Si content of 0.5% by mass and was outside the scope of the present invention.
  • the penetration depth evaluation was good ( ⁇ ) and the abnormal bead number evaluation was good ( ⁇ ). (X).
  • Measurement of the number of second phase particles in the metal structure A longitudinal section parallel to the rolling direction of the obtained final plate (section perpendicular to the LT direction) is cut out, embedded in a thermoplastic resin and mirror-polished, and the metal structure is observed. went. The micro metallographic structure is photographed with an optical microscope (area per field of view; 0.0334 mm 2 , 10 fields of view of each sample), image analysis of the photograph is performed, and the second phase with a circle equivalent diameter of 5 ⁇ m or more per unit area The number of particles was measured.
  • the number of second phase particles having a circle-equivalent diameter of 5 ⁇ m or more in the metal structure needs to be less than 500 particles / mm 2 .
  • the number of second phase particles having an equivalent circle diameter of 5 ⁇ m or more in the metal structure needs to be less than 500 particles / mm 2 .
  • an Al—Fe-based aluminum alloy plate having high strength applicable to a large-sized lithium ion battery container, excellent in formability, and excellent in laser weldability.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

La présente invention concerne une feuille d'alliage d'aluminium à base d'Al-Fe ayant une résistance suffisamment élevée pour une application en tant que grand contenant de batterie lithium-ion, ainsi qu'une bonne aptitude au moulage et une bonne aptitude au soudage au laser. La feuille d'alliage d'aluminium laminée à froid a un allongement de 2 % ou plus et une résistance à la traction de 160 MPa ou plus, et a : une composition chimique comprenant de 0,3 à 1,5 % en masse de Fe, de 0,3 à 1,0 % en masse de Mn, de 0,2 à 1,0 % en masse de Cu, de 0,2 à 1,0 % en masse de Mg, de 0,002 à 0,20 % en masse de Ti et de 0,05 à 0,20 % en masse de Zr, la composition chimique présentant un rapport massique Mn/Fe de 0,2 à 1,0, le reste comprenant Al et les impuretés inévitables, de telles impuretés inévitables comprenant moins de 0,30 % en masse de Si ; et une structure métallographique dans laquelle le nombre de particules de seconde phase ayant un diamètre de cercle équivalent de 5 µm ou plus est inférieur à 500/mm². En variante, la feuille d'alliage d'aluminium est un matériau recuit laminé à froid, ayant un allongement de 20 % ou plus et une résistance à la traction de 130 MPa ou plus.
PCT/JP2011/080110 2011-02-02 2011-12-26 Feuille d'alliage d'aluminium pour un boîtier de batterie ayant une bonne aptitude au moulage et une bonne aptitude au soudage WO2012105143A1 (fr)

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KR1020137019976A KR20130109224A (ko) 2011-02-02 2011-12-26 성형성 및 용접성이 우수한 전지 케이스용 알루미늄 합금판
CN201180055949.6A CN103261461B (zh) 2011-02-02 2011-12-26 成形性和焊接性优异的电池壳体用铝合金板

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CN102925758A (zh) * 2012-10-25 2013-02-13 苏州有色金属研究院有限公司 锂离子电池壳用铝合金
EP2835436A4 (fr) * 2012-10-12 2016-03-23 Nippon Light Metal Co Tôle en alliage d'aluminium pour bac de batterie, présentant une aptitude au moulage, une dissipation thermique et une soudabilité excellentes

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CN103911527B (zh) * 2014-03-31 2016-09-14 绍兴安卡汽车配件有限公司 一种锂离子电池外壳用铝合金及其制备方法
JP6176393B2 (ja) * 2014-04-09 2017-08-09 日本軽金属株式会社 曲げ加工性と形状凍結性に優れた高強度アルミニウム合金板
CN107755578B (zh) * 2017-10-27 2019-05-07 中铝东南材料院（福建）科技有限公司 一种新能源汽车电池铝箱的冲制方法
CN108486428A (zh) * 2018-04-29 2018-09-04 安徽福斯特汽车部件有限公司 一种制备复合强化合金的方法
CN112708811B (zh) * 2020-12-17 2021-09-24 广东和胜工业铝材股份有限公司 一种铝合金及其制备方法和应用

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JP5725345B2 (ja) 2015-05-27
TWI476979B (zh) 2015-03-11
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