JP6614307B1 - Aluminum alloy plate for battery lid for integral explosion-proof valve molding and manufacturing method thereof - Google Patents

Abstract

A battery cover aluminum alloy plate excellent in heat dissipation, moldability, and work softening, and capable of forming an integrated explosion-proof valve with less operating pressure variation and excellent repeated fatigue resistance. An aluminum alloy plate for a lid and a method for producing the same are provided. SOLUTION: Fe: 1.05-1.50 mass%, Mn: 0.15-0.70 mass%, Ti: 0.002-0.10 mass%, and B: less than 0.05 mass% And the balance is made of Al and impurities, the Fe / Mn ratio is regulated to 1.8 to 7.0, Si as impurities is less than 0.40 mass%, Cu is less than 0.03 mass%, Mg is The component composition is regulated to less than 0.05% by mass, V is less than 0.03% by mass, the conductivity is 53.0% IACS or more, the elongation value is 40% or more, and the recrystallized structure is And the tensile strength after cold rolling at a reduction rate of 90% is defined as TS90, and the tensile strength after cold rolling at a reduction rate of 95% is defined as TS95 (TS95-TS90). ) Is less than −4 MPa, and cold rolling is performed at a reduction rate of 90%. Wherein the value of elongation is 5.0% or more, integrated explosion-proof valve aluminum alloy plate for a battery lid for molding. Furthermore, the average crystal grain size of the recrystallized grains in the recrystallized structure is preferably 15 to 30 μm. [Selection figure] None

Description

  The present invention relates to an aluminum alloy plate for a battery lid for forming an integral explosion-proof valve, which is used for a lithium ion battery of a square shape, a cylindrical shape or the like and has a small operating pressure variation.

  In recent years, exhaust gas regulations for automobiles have become stricter in various countries, and the production of electric cars as environmentally friendly cars has been growing rapidly. Currently, lithium ion batteries are the mainstream of secondary batteries used in electric vehicles. There are various types of lithium-ion battery cases such as square, cylindrical, and laminate types. In the case of square and cylindrical types, aluminum alloy sheets that can achieve weight reduction are drawn and ironed (DI It is also called processing.)

As described above, a high-strength aluminum alloy plate is required as a material for a battery case, which has excellent workability and is easy to perform DI processing. Patent Document 1 contains Mn 0.8 to 2.0% (mass%, the same shall apply hereinafter), and the amount of Fe as impurities is restricted to 0.6% or less, and the amount of Si is restricted to 0.3% or less. The balance is substantially made of Al, the Mn solid solution amount is 0.75% or more, the ratio of the Mn solid solution amount to the Mn addition amount is 0.6 or more, and the proof stress is 185 to 260 N / mm ^2. There has been proposed an aluminum alloy plate for cases excellent in high-temperature blistering resistance, characterized in that it falls within the above range. According to this, especially when the temperature rises to a high temperature of about 70 to 90 ° C. and the internal pressure increases, that is, even when a high-temperature internal pressure load is applied, the aluminum alloy plate for a case is excellent in resistance to high-temperature blistering and is not easily deformed by blisters. Will be provided.

  In Patent Document 2, as the composition of the aluminum alloy plate, Si: 0.10 to 0.60 wt%, Fe: 0.20 to 0.60 wt%, Cu: 0.10 to 0.70 wt%, Mn: 0.60 to 1.50 wt%, Mg: 0.20 to 1.20 wt%, Zr: more than 0.12 and less than 0.20 wt%, Ti: 0.05 to 0.25 wt%, B: 0.0010 Aluminum for rectangular cross-section battery containers, containing 0.02 wt%, consisting of the balance Al and inevitable impurities, and having a 45 ° ear ratio in the rolling direction of 4 to 7% in the cylindrical container deep drawing method Alloy plates have been proposed. According to this, an aluminum alloy plate having a high product yield, a good rectangular DI formability of a thin plate, and an excellent pulse laser weldability is provided.

Further, Patent Document 3 contains Fe: 0.3 to 1.5 mass%, Mn: 0.3 to 1.0 mass%, Ti: 0.002 to 0.20 mass%, and Mn / Fe The mass ratio is 0.2 to 1.0, and the balance is Al and impurities. Si as an impurity is less than 0.30 mass%, Cu is less than 0.20 mass%, and Mg is less than 0.20 mass%. As a cold-rolled material having a component composition and a metal structure in which the number of second phase particles having an equivalent circle diameter of 5 μm or more is less than 500 particles / mm ² and exhibiting an elongation value of 5% or more and a tensile strength of 90 MPa or more An aluminum alloy plate for a battery case that is excellent in formability and weldability, characterized by being a material, has been proposed. According to this, since it has high strength, excellent moldability, and excellent laser weldability, it is possible to manufacture a secondary battery container that has excellent sealing performance and can suppress swelling, at low cost. There is.

  Since lithium ion batteries for automobiles are accompanied by rapid charge and discharge, they are designed with sufficient consideration for their safety. However, when a destruction accident occurs due to an unexpected situation and the internal pressure in the battery container rapidly increases, the battery container or the battery lid is provided with an explosion-proof valve because it is necessary to release the internal pressure. This explosion-proof valve needs to operate reliably, for example, when the internal pressure of the container exceeds a predetermined pressure, the valve automatically breaks.

  For example, in Patent Document 4, at least one through-hole A is provided in a battery lid or battery container of a sealed battery in which the battery lid is hermetically sealed by a method such as welding or caulking, and the through-hole A is made of metal. In a sealed battery having a safety mechanism that is closed by a thin plate and is broken by the internal pressure of the battery, the size is not larger than that of the metal thin plate, and a metal plate having at least one through-hole B is stacked on the metal thin plate, A sealed battery characterized by seam welding to a battery lid or battery container has been proposed.

  When this explosion-proof valve is provided on the battery lid, the manufacturing cost of the battery lid can be reduced by forming a lid with a so-called integrated explosion-proof valve in which the explosion-proof valve is integrally formed on the battery lid. Patent Document 5 includes Fe: 1.15 to 1.35% by mass, Mn: 0.40 to 0.60% by mass, balance Al and impurities, and Si as an impurity is 0.15% by mass or less, The composition in which Cu is controlled to 0.05% by mass or less and Mg is controlled to 0.05% by mass or less, and the maximum width of crystal grains in the direction perpendicular to the rolling direction is 100 μm or less on the rolling surface, and the average of the crystal grain widths Describes an aluminum alloy plate for battery lids characterized by having a structure of 25 μm or less. According to this, since the component composition is defined and the final annealing is performed by rapid heating and rapid cooling by using a continuous annealing furnace, there are no coarse crystal grains, and it is composed of fine crystal grains. In addition to exhibiting the desired pressure strength, the variation in pressure strength is reduced.

  Patent Document 6 contains, in mass%, Mn 0.8% to 1.5%, Si 0.6% or less, Fe 0.7% or less, Cu 0.20% or less, Zn 0.20% or less, It has a composition composed of the balance Al and inevitable impurities, the thickness of the base plate is T0, the thickness after press working is T1, and the cold working degree R (%) = [(T0−T1) / T0] × 100. When the tensile strength TS80 (MPa) when R is 80% and the tensile strength TS96 (MPa) when R is 96% are compared, (TS96-TS80) is less than 15 MPa, and TS80 is 200 MPa. An aluminum alloy sheet for a lithium ion battery sealing material is described above. According to this, work hardenability is reduced, heat treatment after press working becomes unnecessary, and an increase in the operating pressure of the explosion-proof valve can be suppressed.

JP 2002-140669 A JP 2004-197172 A JP2012-177186A JP-A-9-199088 Japanese Patent No. 5004007 Japanese Patent No. 587256

  Certainly, the 3000 series aluminum alloy plate is excellent in formability, has high strength and has characteristics as a material for a lithium ion battery container. However, an aluminum alloy plate containing Mn and Fe as essential elements and having a higher Mn content than the Fe content has a high Mn solid solution amount in the matrix, so that the work hardening by cold working becomes significant, so press working Therefore, it is not suitable as a material for a battery lid with an integral explosion-proof valve that forms a thin-walled portion.

  The battery cover with an integral explosion-proof valve is cold press-molded at a processing rate of about 90% to 95% when the thin part of the explosion-proof valve is molded. As a material, there is a demand for an aluminum alloy plate having an appropriate strength, excellent formability, and suppressed work hardening at a high processing rate. In particular, an in-vehicle lithium ion battery generates a large amount of heat internally during charging and discharging, and therefore, the internal pressure applied to the thin portion of the integrated explosion-proof valve repeatedly changes every time charging and discharging are performed. Accordingly, a material having excellent heat dissipation is required as a material to be used, and further, the thin-walled portion of the molded integral explosion-proof valve is required to have less variation in operating pressure and excellent repeated fatigue characteristics.

  By the way, there are various types of lithium ion battery cases such as a square type, a cylindrical type, and a laminated type. Since the cylindrical type has a circular cross section, the manufacturing cost is low and the internal temperature during charging and discharging is low. It is easy to make the distribution uniform. Recently, cylindrical lithium ion batteries represented by 18650 have been attracting attention as lithium ion batteries for vehicles. However, when a plurality of cylindrical lithium ion batteries are arranged in a predetermined vehicle battery pack, a gap is created, and the apparent energy density in the vehicle battery pack is reduced when fully charged. There are drawbacks. Although rectangular lithium-ion batteries are slightly more expensive to manufacture, it is possible to arrange a plurality of batteries closely in a given vehicle battery pack. There is an advantage that the energy density can be increased.

  The aluminum alloy plate for a battery lid described in Patent Document 5 contains Mn and Fe as essential elements and has a Fe content higher than the Mn content, but shows a rectangular battery lid and a rectangular explosion-proof valve. Only a round explosion-proof valve is not shown. Moreover, in the aluminum alloy plate material for a lithium ion battery sealing material described in Patent Document 6, work hardenability is reduced, heat treatment after press working is unnecessary, and an increase in operating pressure of the explosion-proof valve is suppressed. Although it can be done, there is no particular mention of variations in the operating pressure of the explosion-proof valve.

  The present invention has been made in view of the prior art as described above, and is an aluminum alloy plate for battery lids having excellent heat dissipation, formability, and work softening properties, with less variation in operating pressure, and resistance to repetition. An object of the present invention is to provide an aluminum alloy plate for a battery lid capable of forming an integral explosion-proof valve having excellent fatigue characteristics and a method for producing the same. The aluminum alloy plate for a battery lid of the present application is used as a lid of a lithium ion battery, but can be applied as a battery lid regardless of the shape of the battery container. That is, the shape of the battery cover in plan view may be any shape such as a circle, an ellipse, a rectangle, a hexagon, or a combination of an arc and a straight line such as a ground shape. . The aluminum alloy plate for a battery lid of the present application is used as a lid of a lithium ion battery, but an explosion-proof valve is integrally formed on the battery lid regardless of the shape of the battery lid. In other words, the shape of the integrated explosion-proof valve in plan view may be any shape such as a circle, an ellipse, a rectangle, a hexagon, or a combination of an arc and a straight line like a ground shape. Also good.

  In order to achieve the object, the aluminum alloy plate for battery lids for forming an integral explosion-proof valve of the present invention has an Fe: 1.05-1.50 mass%, Mn: 0.15-0.70 mass%, Ti: 0.002 to 0.10% by mass, and B: less than 0.05% by mass, the balance is made of Al and impurities, Fe / Mn ratio is regulated to 1.8 to 7.0, impurities As a component composition, Si is less than 0.40% by mass, Cu is less than 0.03% by mass, Mg is less than 0.05% by mass, and V is less than 0.03% by mass. 53.0% IACS or more, elongation value is 40% or more, has a recrystallized structure, and the tensile strength after cold rolling at a reduction rate of 90% is defined as TS90. % When the tensile strength after cold rolling is defined as TS95 (TS The value of 5-TS90) is less than -4MPa, the value of elongation after being subjected to cold rolling at a reduction rate of 90%, characterized in that 5.0% or more. Furthermore, the average crystal grain size of the recrystallized grains in the recrystallized structure is preferably 15 to 30 μm.

  Moreover, the manufacturing method of the aluminum alloy plate for battery lids for integral explosion-proof valve forming of the present invention, in order to achieve the purpose, the molten aluminum alloy having the above-described composition is formed into an ingot by a semi-continuous casting method. Casting slab casting process, homogenization process in which the ingot is subjected to a homogenization process at a holding temperature of 520 to 620 ° C. and a holding time of 1 hour or more, and after the homogenization process process, a start temperature of less than 420 to 520 ° C. A hot rolling step for hot rolling the ingot to obtain a hot rolled plate, and a cold rolling step for cold rolling the hot rolled plate to obtain a cold rolled plate, And a final annealing step of subjecting the cold-rolled sheet to final annealing in a batch furnace. Furthermore, in the said cold rolling process, the final cold rolling which is the range of 50%-95% of the final cold rolling rates is given, and in the said final annealing process, final annealing for 1 hour or more is performed at the holding temperature of 300-450 degreeC. Is preferred.

  The battery cover aluminum alloy plate for forming an integral explosion-proof valve of the present invention has a conductivity of 53.0% IACS or more, an elongation value of 40% or more, a recrystallized structure, and a reduction ratio of 90. When the tensile strength after cold rolling is defined as TS90 and the tensile strength after cold rolling at 95% reduction is defined as TS95, the value of (TS95-TS90) is −4 MPa. Since the elongation value after cold rolling at a rolling reduction of 90% is 5.0% or more, it is excellent in heat dissipation, formability, and work softening properties, and is molded integrally. The explosion-proof valve has little variation in operating pressure and has excellent repeated fatigue resistance.

A molten aluminum alloy having a predetermined composition is cast semi-continuously by a DC casting machine to form an ingot, both sides are subjected to homogenization and hot rolling, and the hot rolled sheet is wound on a roll. . The temperature of the homogenization treatment is 520 to 620 ° C. By setting the hot rolling start temperature to less than 520 ° C., solid solution of Mn and Si is absorbed by Fe-based compounds such as Al— (Fe · Mn) —Si, or Mn such as Al ₆ Mn. By precipitating the system precipitate, the amount of Mn solid solution and the amount of Si solid solution in the matrix are reduced. The hot-rolled sheet is cold-rolled to a predetermined thickness, and is softened by subjecting it to intermediate annealing at 300 to 400 ° C. in a batch furnace as necessary, and cold rolling with a final cold rolling ratio of 50% to 95% is performed. After applying, final annealing at 300 to 450 ° C. is performed in a batch furnace to obtain an annealed material (O material). Further, cold rolling may be performed to obtain a cold rolled material (H material).

  The aluminum alloy plate for battery lid for forming an integral explosion-proof valve manufactured according to the present invention has a conductivity of 53.0% IACS or more, an elongation value of 40% or more, and a recrystallized structure. The tensile strength after cold rolling at a rolling reduction of 90% is defined as TS90, and the tensile strength after cold rolling at a rolling reduction of 95% is defined as TS95 (TS95-TS90). The value is less than −4 MPa, the elongation value after cold rolling at a rolling reduction of 90% is 5.0% or more, and thus has excellent heat dissipation, formability and work softening properties, and further The explosion-proof valve that is molded in a conventional manner has little variation in the operating pressure and has excellent repeated fatigue resistance.

  Even if the conventional aluminum alloy plate for battery lids has high strength, there are many cases where defects such as microcracks occur in the molding process of an integral explosion-proof valve as a battery lid. This is considered to be because the Mn solid solution amount in the final plate is high. For this reason, it is necessary to appropriately control the ingot homogenization temperature and the hot rolling start temperature to sufficiently adjust the Mn solid solution amount. Moreover, the battery cover aluminum alloy plate for forming the integral explosion-proof valve needs to be subjected to cold working with a processing rate of about 90% to 95% to form a thin portion in the molding process of the integral explosion-proof valve, It must be excellent in moldability.

  In particular, an in-vehicle lithium ion battery generates a large amount of heat internally during charging and discharging, and therefore, the internal pressure applied to the thin portion of the integrated explosion-proof valve repeatedly changes every time charging and discharging are performed. Therefore, a material having excellent heat dissipation is required as a material to be used. Further, a molded integrated explosion-proof valve is required to have a small variation in operating pressure and excellent repeated fatigue characteristics.

As described above, in the molding process of the integral explosion-proof valve, the thin part is formed by performing cold working with a working rate of 90% to 95%. Therefore, in order to make this thin portion excellent in repeated fatigue characteristics, it has a predetermined component composition, has a recrystallized structure, is excellent in work softening property in cold working at a high working rate, and has a predetermined composition. It is necessary to provide an aluminum alloy plate for battery lids that has a high elongation value after cold rolling at a rolling reduction.
The contents will be described below.

  First, the action of each element contained in the aluminum alloy plate for battery lid for forming an integral explosion-proof valve of the present invention, the appropriate content, etc. will be described.

[Fe: 1.05-1.50 mass%]
Fe is a composition within the scope of the present invention, and Fe-based intermetallic compounds such as Al— (Fe · Mn) —Si are precipitated in the ingot during casting, and between these Fe-based metals during homogenization treatment. The compound absorbs Mn dissolved in the matrix. For this reason, Fe is an essential element.
When the Fe content is less than 1.05% by mass, the size and number of Fe-based intermetallic compounds in the ingot are reduced, thereby sufficiently reducing the Mn solid solution amount in the ingot during the homogenization treatment. I can't do that. For this reason, there is a possibility that work hardening at a high processing rate becomes remarkable for the final plate. When the Fe content exceeds 1.50% by mass, the size and number of Fe-based intermetallic compounds increase, so that the formability of the final sheet decreases and cold rolling is performed at a reduction rate of 90%. There is a possibility that the value of the elongation of less than 5.0%.
Therefore, the Fe content is in the range of 1.05-1.50 mass%. The preferable Fe content is in the range of 1.05 to 1.45% by mass. A more preferable Fe content is in the range of 1.10 to 1.45% by mass.

[Mn: 0.15 to 0.70% by mass]
Mn is an element that increases the proof stress of the aluminum alloy plate, and a part of the element is an essential element because it promotes solid solution strengthening by solid solution in the matrix.
If the Mn content is less than 0.15% by mass, the Fe / Mn ratio may exceed 7.0, the shape of the Fe-based intermetallic compound in the ingot becomes needle-like, and the reduction ratio of the final plate is 90%. The elongation value after cold rolling may be less than 5.0%. When the Mn content exceeds 0.70% by mass, the Mn solid solution amount in the ingot becomes too high, and the heat dissipation of the final plate decreases, and the elongation after cold rolling at a reduction rate of 90%. May be less than 5.0%.
Therefore, the Mn content is in the range of 0.15 to 0.70 mass%. A preferable Mn content is in a range of 0.15 to 0.65 mass%. A more preferable Mn content is in the range of 0.20 to 0.65% by mass.

[Fe / Mn ratio: 1.8 to 7.0]
Mn is an element that precipitates an Fe-based intermetallic compound such as Al- (Fe.Mn) -Si on the ingot during casting, but has the effect of making the shape of the Fe-based intermetallic compound spherical.
When the Fe / Mn ratio is less than 1.8, the effect of absorbing the Mn solid-dissolved in the matrix by the Fe-based intermetallic compound during the homogenization treatment is reduced, and the heat dissipation of the final plate is reduced. The elongation value after cold rolling at a rolling reduction of 90% may be less than 5.0%. When the Fe / Mn ratio exceeds 7.0, the effect of spheroidizing the shape of the Fe-based intermetallic compound becomes small, and the elongation value after the cold rolling of the final sheet at a rolling reduction of 90% is 5. There is a risk of being less than 0%.
Therefore, the Fe / Mn ratio is restricted to 1.8 to 7.0.

[Ti: 0.002 to 0.10% by mass]
Ti is an essential element because it acts as a grain refiner during ingot casting and can prevent casting cracks. Of course, Ti may be added alone, but by 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.
If 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. When the Ti content exceeds 0.10% by mass, the heat dissipation of the final plate decreases, and a coarse intermetallic compound such as TiAl ₃ crystallizes during ingot casting, and the final plate has a reduction rate of 90%. There exists a possibility that the value of elongation after performing cold rolling may be less than 5.0%.
Accordingly, the Ti content is in the range of 0.002 to 0.10% by mass. The preferable Ti content is in the range of 0.002 to 0.07 mass%. A more preferable Ti content is in the range of 0.005 to 0.05 mass%.
In addition, about Ti content, although the more preferable range is prescribed | regulated by reducing both a lower limit and an upper limit with respect to a preferable range, the more preferable range is independent about each of a lower limit and an upper limit. It is not necessary to apply both at the same time.

[B: less than 0.05% by mass]
B is an essential element because coexistence with Ti can be expected to produce a more powerful grain refinement effect. Similar to Ti, addition with a rod hardener such as Al-5% Ti-1% B may also be used.
When the B content is 0.05% by mass or more, although depending on the Ti content, the Ti-B compound is easily stabilized to become TiB ₂ , and the grain refinement effect is attenuated, and TiB ₂ is contained in the furnace. There is a risk of sedimentation and accumulation on the furnace bottom.
Therefore, the B content is set to a range of less than 0.05% by mass. A preferable B content is in a range of less than 0.02% by mass. A more preferable B content is in a range of less than 0.01% by mass.

[V: less than 0.03 mass%]
In the present invention, V is an impurity. When the V content is 0.03% by mass or more, a relatively large size Fe-based intermetallic compound is precipitated during casting, and the elongation value after cold rolling at a rolling reduction of 90% is 5.0. There is a risk of being less than%.
Therefore, the V content is set to a range of less than 0.03% by mass. A preferable V content is in a range of less than 0.02% by mass.

[Si: less than 0.40 mass%]
In the present invention, Si is an impurity. Si precipitates an Fe-based intermetallic compound such as Al— (Fe · Mn) —Si at the time of casting, and a part thereof is dissolved in the matrix to increase the strength of the aluminum alloy plate.
When the Si content is 0.40% by mass or more, the Si solid solution amount of the final plate becomes high, and the elongation value after cold rolling at a reduction rate of 90% is less than 5.0%. There is a fear.
Therefore, the Si content is set to a range of less than 0.40% by mass. A preferable Si content is in a range of less than 0.35% by mass. A more preferable Si content is in the range of less than 0.30% by mass.

[Cu: less than 0.03 mass%]
In the present invention, Cu is an impurity. In the present invention, if the Cu content is 0.03% by mass or more, the elongation value after cold rolling at a rolling reduction of 90% may be less than 5.0%. Therefore, the Cu content is set to a range of less than 0.03% by mass. A preferable Cu content is in a range of less than 0.02% by mass. A more preferable Cu content is in the range of less than 0.01% by mass.

[Mg: less than 0.05% by mass]
In the present invention, Mg is an impurity. In the present invention, if the Mg content is 0.05% by mass or more, the formability and heat dissipation of the final plate are reduced, and work hardening at a high processing rate becomes remarkable, and cold rolling is performed at a reduction rate of 90%. There is a possibility that the elongation value after application is less than 5.0%. Accordingly, the Mg content is set to a range of less than 0.05% by mass. The preferred Mg content is in the range of less than 0.03% by mass. A more preferable Mg content is in the range of less than 0.02% by mass.

[Other inevitable impurities]
Inevitable impurities are uncontrolled elements that are inevitably mixed in from raw metal, return material, etc., and their allowable contents are, for example, less than 0.20 mass% of Cr and 0.20 mass% of Zn Less than, less than 0.10 mass% of Ni, less than 0.05 mass% of Ga, Pb, Bi, Sn, Na, Ca, Sr, less than 0.02 mass%, respectively (for example, Co, Nb, Mo, W) each less than 0.05% by mass, and inclusion of an element outside the control within this range does not hinder the effect of the present invention.

[Conductivity: 53.0% IACS or higher]
As described above, the in-vehicle lithium ion battery has a large amount of heat generated inside during charging and discharging, and therefore, a material having excellent heat dissipation is required as a material to be used. Therefore, the conductivity (IACS%) of the final plate was adopted as an index for evaluating heat dissipation, and the conductivity was specified to be 53.0% IACS or more.

[(TS95-TS90) value: less than -4 MPa]
As described above, the aluminum alloy plate for battery lid for forming an integral explosion-proof valve is subjected to cold working at a processing rate of about 90% to 95% in forming the integral explosion-proof valve to form a thin part. It must be excellent in work softening property at a high working rate. Therefore, as an index for evaluating work softening property, the tensile strength after cold rolling at a reduction rate of 90% is defined as TS90, and the tensile strength after cold rolling at a reduction rate of 95% is defined as TS95. The value (MPa) of (TS95-TS90) when defined was adopted, and the value of (TS95-TS90) was defined to be less than -4 MPa.

[Elongation value: 40% or more]
As described above, the battery cover aluminum alloy plate for forming an integral explosion-proof valve is subjected to cold working at a processing rate of about 90% to 95% in forming the integral explosion-proof valve to form a thin portion. It must be excellent in moldability. Therefore, as an index for evaluating formability, the value of elongation when a tensile test was performed on the final plate was adopted, and the value of elongation was defined as 40% or more.

[Having a recrystallized structure]
In order to make the thin-walled portion of the integral explosion-proof valve excellent in repeated fatigue characteristics, it is necessary to provide a final plate having a predetermined component composition and having a recrystallized structure. When the metal structure of the final plate is an unrecrystallized structure, softening due to the annealing treatment is insufficient, the elongation value is low, and the formability is remarkably lowered. Further, even if the integrated explosion-proof valve can be formed, there is a risk that the operating pressure varies due to the anisotropy of the metal structure of the thin portion.
When the metal structure of the final plate is a recrystallized structure, if the average crystal grain size of the recrystallized grains exceeds 30 μm, there is a possibility that the operating pressure of the explosion-proof valve may vary, which is not preferable. If the average crystal grain size of the recrystallized grains is less than 15 μm, the heat dissipation may be lowered, which is not preferable. Therefore, the average crystal grain size of the recrystallized grains having a preferable recrystallized structure is in the range of 15 to 30 μm. The average crystal grain size of the recrystallized grains having a more preferable recrystallized structure is in the range of 15 to 25 μm.

[Elongation value after cold rolling at a rolling reduction of 90%: 5.0% or more]
As described above, since the in-vehicle lithium ion battery generates a large amount of heat internally during charging and discharging, the internal pressure applied to the thin portion of the integrated explosion-proof valve repeatedly changes every time charging and discharging are performed. For this reason, in the thin-walled part of the integrated explosion-proof valve after molding, a material having high elongation and excellent repeated fatigue characteristics is required. Therefore, as an index for evaluating the operation stability of the explosion-proof valve, the elongation value after cold rolling at a reduction ratio of 90% was adopted for the final plate, and the elongation value was defined as 5.0% or more. .

Next, an example of a method for producing an aluminum alloy plate for a battery lid for forming an integral explosion-proof valve as described above will be briefly introduced.
[Dissolution / melting process]
When the raw material is charged into the melting furnace and the predetermined melting temperature is reached, the flux is appropriately charged and stirred, and after degassing in the furnace using a lance, etc., if necessary, hold it quietly. Separate the cocoon from the surface of the melt.
In this melting / melting process, it is important to add raw materials such as a master alloy again because it is a predetermined alloy component. However, a sufficient sedation time is required until the flux and soot float and separate from the molten aluminum alloy to the molten metal surface. It is extremely important to take The sedation time is usually preferably 30 minutes or longer.

In some cases, 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.
If necessary, in-line degassing or filtering may be performed.
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. When 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.

  If there is a large amount of hydrogen gas in the ingot, porosity may occur in the final solidified part of the ingot. Therefore, the reduction rate per pass in the hot rolling process is restricted to, for example, 7% or more to crush the porosity. It is preferable to keep it. Also, the hydrogen gas that is supersaturated in the ingot is dependent on the heat treatment conditions of the cold-rolled coil, but even after press molding of the explosion-proof valve of the final plate, for example, a laser between the battery lid and the battery container In some cases, it may precipitate during welding and generate a large number of blow holes in the bead. For this reason, the more preferable amount of hydrogen gas in the ingot is 0.15 cc / 100 g or less.

[Slab casting process]
The ingot is manufactured by semi-continuous casting (DC casting). In the case of normal semi-continuous casting, since the thickness of the ingot is generally about 400 to 600 mm, the solidification cooling rate at the center portion of the ingot is about 1 ° C./sec. For this reason, particularly when an aluminum alloy melt having a high Fe and Mn content is semi-continuously cast, Al ₆ (Fe · Mn), α-Al- (Fe · Mn) -Si, etc. The relatively coarse intermetallic compound tends to crystallize from the molten aluminum alloy.

  The casting speed in the semi-continuous casting depends on the width and thickness of the ingot, but is usually 50 to 70 mm / min in consideration of productivity. However, when performing in-line degassing, considering the substantial molten metal residence time in the degassing treatment tank, the flow rate of molten aluminum (melt per unit time) 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. Although depending on the number of castings and the like, it is desirable to limit the casting speed to 30 to 50 mm / min in order to reduce the amount of hydrogen gas in the ingot. A more desirable casting speed is 30 to 40 mm / min. Of course, when the casting speed is less than 30 mm / min, productivity is lowered, which is not desirable. Needless to say, when 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 process]
The ingot obtained by casting by the semi-continuous casting method is homogenized.
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. In the present invention, it is necessary to hold at a holding temperature of 520 to 620 ° C. for 1 hour or longer. In this case, it is also a process for dissolving the transition elements constituting the intermetallic compound crystallized during casting to some extent in the matrix. When the holding temperature is too low or the holding temperature is short, the solid solution does not progress, and the appearance skin after molding may not be finished cleanly. On the other hand, if the holding temperature is too high, the eutectic portion which is the micro final solidified portion of the ingot may be melted, so-called burning may occur. A more preferable homogenization treatment temperature is 520 to 610 ° C.

[Hot rolling process]
In this way, the ingot homogenization is performed at a holding temperature of 520 to 620 ° C. with a holding time of 1 hour or more, and by setting the starting temperature of hot rolling to less than 520 ° C., the ingot is dissolved in the matrix. Mn and Si can be reduced. When the hot rolling start temperature is 520 ° C. or higher, it is difficult to reduce Mn and Si dissolved in the matrix. When the hot rolling start temperature is less than 420 ° C., the roll pressure necessary for plastic deformation during hot rolling becomes high, and the reduction rate per pass becomes too low, resulting in a reduction in productivity. Therefore, the start temperature of hot rolling is in the range of 420 to less than 520 ° C. The ingot taken out of the soaking furnace is suspended by a crane and brought to a hot rolling mill. Depending on the type of hot rolling mill, it is usually hot rolled by several rolling passes. Then, it is wound around the coil as a hot rolled plate having a predetermined thickness, for example, about 4 to 8 mm.

[Cold rolling process]
The coil on which the hot rolled sheet is wound is passed through a cold rolling machine and usually subjected to several passes of cold rolling. At this time, since work hardening occurs due to plastic strain introduced by cold rolling, an intermediate annealing treatment is performed as necessary. Usually, since the intermediate annealing is also a softening treatment, although depending on the material, a cold-rolled coil may be inserted into a batch furnace and held at a temperature of 300 to 400 ° C. for 1 hour or longer. When the holding temperature is lower than 300 ° C., softening is not promoted, and when the holding temperature exceeds 400 ° C., productivity may be lowered, which is not preferable.

[Final annealing process]
In the present invention, the final annealing step performed after the final cold rolling is preferably a batch treatment in which, for example, an annealing furnace holds the temperature at 300 to 450 ° C. for 1 hour or longer. By performing the final annealing under such conditions, the annealed plate (final plate) has a recrystallized structure in which the average crystal grain size of the recrystallized grains is 15 to 30 μm. A more preferable final annealing step is a batch treatment in which an annealing furnace holds the temperature at 300 to 400 ° C. for 1 hour or more. A more preferable final annealing step is a batch treatment in which an annealing furnace holds the temperature at 300 to 380 ° C. for 1 hour or longer. The higher the holding temperature in the annealing furnace, the higher the growth rate of the recrystallized grains, so that the average crystal grain size of the recrystallized grains increases. In any case, final annealing is essential in the present invention, and it is necessary to soften the final plate in consideration of the cold working rate of about 90% to 95% of the thin wall portion of the integral explosion-proof valve by press molding. . In addition, when performing the last annealing process by continuous annealing, since there exists a possibility that the heat dissipation of an annealing board (final board) and the operation stability of an integral explosion-proof valve may fall, it is unpreferable.

When the final annealing is performed, the final cold rolling rate is preferably in the range of 50% to 95%. A more preferable final cold rolling rate is in the range of 70% to 95%. When the final cold rolling rate is within this range, a recrystallized structure having an average crystal grain size of 15 to 30 μm is obtained by performing final annealing at a temperature of 300 to 450 ° C. for 1 hour or more. Note that the average crystal grain size of the recrystallized grains varies depending not only on the holding temperature in the annealing furnace but also on the final cold rolling rate.
By going through the normal steps as described above, an aluminum alloy plate for a battery lid for forming an integral explosion-proof valve can be obtained.

<Examples using laboratory test materials>
[Creation of sample materials]
Ingots of 16 levels (Examples 1 to 6, Comparative Examples 1 to 10) of ingots of 5 kg were inserted into # 20 crucibles, respectively, and the crucibles were heated in a small electric furnace to dissolve the ingots. Next, a lance was inserted into the molten metal, and N ₂ gas was blown in at a flow rate of 1.0 L / min for 5 minutes for degassing treatment. Thereafter, sedation for 30 minutes was performed, and the soot that floated on the surface of the molten metal was removed with a stirring rod. Next, the crucible was taken out from the small electric furnace, the molten metal was poured into a mold having an inner size of 250 × 200 × 30 mm, an ingot was produced, and Examples 1 to 6 and Comparative Examples 1 to 10 were made from the molten metal in each crucible. Each specimen was obtained. The disk samples of these test materials were subjected to composition analysis by emission spectroscopic analysis. The results are shown in Table 1.

After chamfering both sides of these ingots by 5 mm to a thickness of 20 mm, homogenization treatment at 590 ° C. × 1 hour, 480 ° C. × 1 hour is continuously performed, hot rolling is performed, A 6.0 mm hot rolled sheet was used. Thereafter, the hot-rolled sheet was cold-rolled to obtain a cold-rolled sheet having a thickness of 1.0 mm. No intermediate annealing is performed during the cold rolling process. The final cold rolling rate in this case was 83%.
Next, these cold-rolled plates (Examples 1 to 6, Comparative Examples 1 to 7, 9, and 10) were simulated by batch annealing, inserted into an annealer, and subjected to annealing treatment at 340 ° C. for 1 hour. A plate (O material) was used. For other cold rolled plates (Comparative Example 8), 425 ° C. × 10 seconds of continuous annealing was simulated, heated in a salt bath at 425 ° C. × 15 seconds, and then water-cooled to obtain the final plate (O material).

  Further, these final plates are cold-rolled to 0.1 mm and 0.05 mm for the purpose of simulating the formation of an integral explosion-proof valve and investigating work hardening characteristics, etc., and the respective reduction ratios: Cold rolled material at 90,95% was collected.

Next, various properties were measured and evaluated for each of the test materials thus obtained (final plate: 16 levels, cold rolled material: 16 levels × 2 levels each).
[Measurement of properties by tensile test]
Evaluation of the moldability of each final board obtained was performed by the elongation value (%) of the final board (O material). The evaluation of the work softening property of each final plate is that the final plate (O material) has a reduction rate of 90% from the tensile strength TS95 (MPa) after cold rolling with a reduction rate of 95%. (TS95-TS90) (MPa), which is a value obtained by subtracting the tensile strength TS90 (MPa) after cold rolling. The operation stability of the integrated explosion-proof valve was evaluated by the elongation value (%) after cold rolling with a reduction ratio of 90% on the final plate (O material). Specifically, a JIS No. 5 test piece was sampled from the obtained specimen so that the tensile direction was parallel to the rolling direction, and a tensile test was performed according to JISZ2241, and the tensile strength, 0. 2% yield strength and elongation (elongation at break) were determined. These tensile tests were performed three times for each specimen (n = 3), and the average value was calculated. Measurement results of elongation (breaking elongation) of each final plate, tensile strength after subjecting each final plate to cold rolling with a reduction rate of 90%, measurement results of elongation (breaking elongation), and reduction rate of 95% for each final plate Table 2 shows the measurement results of the tensile strength after the cold rolling.

[Measurement of conductivity with conductivity meter]
Evaluation of the thermal conductivity of each obtained final board was performed by the electrical conductivity (IACS%) of the last board (O material). Specifically, the conductivity (IACS%) was measured for each obtained final plate with a conductivity meter (AUTOSIGMA 2000, manufactured by Nippon Hocking Co., Ltd.). Table 2 shows the measurement results of the conductivity of each final plate.

When the final plate conductivity is 50.0% IACS or higher, the heat dissipation evaluation is good (◯), and when the final plate conductivity is less than 50.0% IACS, the heat dissipation evaluation is poor (×). It was.
When the elongation value of the final plate is 35.0% or more, the moldability evaluation is good (◯), and when the elongation value of the final plate is less than 35.0%, the moldability evaluation is poor (×). It was.
The value of (TS95-TS90) was less than 3 MPa, and the softening property evaluation was good (◯), and the value of (TS95-TS90) was 3 MPa or more, the processing softness evaluation was poor (x). .
The final plate has an elongation value of 4.0% or more after cold rolling with a rolling reduction of 90% is regarded as good (作 動), and the final plate is cold with a rolling reduction of 90%. The elongation value after rolling was less than 4.0% was regarded as poor operation stability evaluation (x). These evaluation results are shown in Table 2.

  Examples 1 to 6 in Table 2 showing the property evaluation results of the test materials are within the composition range of the present invention, and the final annealing is batch annealing, the conductivity of the final plate, the value of elongation of the final plate, Both the value of (TS95-TS90) and the value of elongation after cold rolling with a rolling reduction of 90% on the final plate satisfied the standard value. Specifically, in Examples 1 to 6, the conductivity of the final plate is 50.0% IACS or more, the elongation value of the final plate is 35.0% or more, and the value of (TS95-TS90) is It was less than 3 MPa, and the elongation value after subjecting the final plate to cold rolling at a reduction rate of 90% was 4.0% or more. Therefore, in Examples 1 to 6, the heat dissipation evaluation was good (◯), the moldability evaluation was good (◯), the work softening evaluation was good (◯), and the operational stability evaluation was good (◯).

  In Comparative Examples 1 to 7, 9, and 10 in Table 2, although the final annealing is batch annealing, it is out of the composition range of the present invention, the conductivity of the final plate, the value of the elongation of the final plate, (TS95-TS90) And at least one of the elongation values after subjecting the final sheet to cold rolling with a rolling reduction of 90% did not satisfy the standard value.

In Comparative Example 1, since the Fe content was too high at 1.58% by mass, the elongation value of the final plate, the value of (TS95-TS90), the elongation after cold rolling of the final plate with a reduction rate of 90% None of these values satisfied the standard value, and were a formability evaluation failure (x), a work softening evaluation failure (x), and an operational stability evaluation failure (x).
Since the comparative example 2 was too low with Fe content 0.97 mass%, the value of (TS95-TS90) did not satisfy the standard value, and the work softness evaluation evaluation was poor (x).

Since the comparative example 3 was too high with Cu content 0.04 mass%, the elongation value after performing the cold rolling of the reduction ratio 90% about the final plate did not satisfy the standard value, and the operation stability was evaluated. It was bad (x).
In Comparative Example 4, since the Mn content was too high, 0.80% by mass, the conductivity of the final plate and the elongation value after the cold rolling of the final plate with a reduction of 90% did not satisfy the standard value. The heat dissipation evaluation was poor (x) and the operation stability was poor (x).

In Comparative Example 5, since the Mg content was too high at 0.21% by mass, the conductivity of the final plate, the value of elongation of the final plate, the value of (TS95-TS90), the cold of the reduction rate of 90% for the final plate None of the elongation values after rolling did not satisfy the standard value, and the heat dissipation evaluation failure (x), the formability evaluation failure (x), the work softening evaluation failure (x), and the operational stability evaluation It was bad (x).
In Comparative Example 6, since the V content was too high at 0.04 mass%, the elongation value after cold rolling with a reduction rate of 90% on the final plate did not satisfy the standard value, and the operational stability It was poor evaluation (x).
In Comparative Example 7, since the V content was too high at 0.11% by mass, the conductivity of the final plate, and the elongation value after performing cold rolling with a reduction rate of 90% on the final plate satisfied the standard value. The heat dissipation evaluation was poor (x) and the operation stability was poor (x).
Although Comparative Example 8 is within the composition range of the present invention, since the final annealing was a salt bath annealing + water quenching process simulating continuous annealing, the conductivity of the final plate, the value of (TS95-TS90), the final None of the elongation values after cold rolling with a rolling reduction of 90% on the plate satisfy the standard values, and the heat dissipation evaluation failure (x), the work softening evaluation failure (x), and the operational stability It was poor evaluation (x).

Comparative Example 9 is an AA1050 alloy composition, and the Fe content and Mn content were too low, 0.19% by mass and 0.02% by mass, respectively, so the value of (TS95-TS90), the reduction ratio of the final plate was 90 None of the elongation values after the cold rolling of 1% did not satisfy the standard values, and the work softness evaluation failure (x) and the operational stability evaluation failure (x).
Comparative Example 10 was an AA3003 alloy composition, Fe content was too low as 0.20 mass%, Cu content and Mn content were too high as 0.14 mass% and 1.29 mass%, respectively. None of the electrical conductivity of the plate, the value of (TS95-TS90), and the value of elongation after cold rolling with a rolling reduction of 90% on the final plate did not satisfy the standard value, resulting in poor heat dissipation evaluation (× ), Poor processing softening evaluation (×), poor operation stability evaluation (×).

<Example using actual equipment>
[Creation of sample materials]
A molten metal having the composition shown in Table 3 was melted in a melting furnace, and an ingot having a width of 1200 mm, a thickness of 560 mm, and a length of 3800 mm was cast with a DC casting machine. Both sides of the ingot are chamfered, inserted into a soaking furnace, heated, and subjected to 590 ° C. × 1 hour, 480 ° C. × 1 hour of homogenization continuously, followed by hot rolling, The coil was wound as a hot rolled plate having a thickness of 7.0 mm. Thereafter, the hot-rolled sheet was cold-rolled and wound around a coil as a cold-rolled sheet having a thickness of 1.0 mm. From this cold-rolled plate, a cut plate having an appropriate size was collected.

Next, with respect to the cold-rolled sheet taken from this cut sheet, it simulated batch annealing, inserted into an annealer, and subjected to annealing treatment at 240 ° C., 340 ° C., 440 ° C. × 1 hour for the final plate (O material) and did. The other cold-rolled plates were simulated as continuous annealing at 425 ° C. × 10 seconds, heated in a salt bath at 425 ° C. × 15 seconds, and then water-cooled to obtain a final plate (O material).
Further, these final plates were cold-rolled to 0.1 mm and 0.05 mm for the purpose of simulating the formation of an integral explosion-proof valve and investigating work hardening characteristics, etc., and the reduction ratio: 90% The cold rolled material at 95% was collected.

  Next, various characteristics were measured and evaluated for each of the test materials thus obtained (final plate: 4 levels, cold rolled material: 4 levels × 2 levels each).

[Measurement of properties by tensile test]
Evaluation of the moldability of each final board obtained was performed by the elongation value (%) of the final board (O material). In addition, the evaluation of the work softening property of each final plate was performed by measuring the rolling strength of the final plate (O material) from the tensile strength TS95 (MPa) after cold rolling with a reduction rate of 95% on the final plate (O material). % Was obtained by subtracting the tensile strength TS90 (MPa) after the cold rolling (TS95-TS90) (MPa). The operation stability of the integrated explosion-proof valve was evaluated by the elongation value (%) of the tensile test after cold rolling with a reduction ratio of 90% on the final plate (O material). Specifically, a JIS No. 5 test piece was sampled from the obtained specimen so that the tensile direction was parallel to the rolling direction, and a tensile test was performed according to JISZ2241, and the tensile strength, 0. 2% yield strength and elongation (elongation at break) were determined. These tensile tests were performed three times for each specimen (n = 3), and the average value was calculated. Measurement results of the elongation (breaking elongation) of each final plate, tensile strength after subjecting each final plate to cold rolling with a reduction rate of 90%, measurement results of elongation (breaking elongation), and reduction rate of 95% for each final plate Table 4 shows the measurement results of the tensile strength after the cold rolling.

[Measurement of conductivity with conductivity meter]
Evaluation of the thermal conductivity of each obtained final board was performed by the electrical conductivity (IACS%) of the last board (O material). Specifically, the conductivity (IACS%) was measured for each obtained final plate with a conductivity meter (AUTOSIGMA 2000, manufactured by Nippon Hocking Co., Ltd.). Table 4 shows the measurement results of the conductivity of each final plate.

[Measurement of average crystal grain size of recrystallized grains]
The obtained final plate is cut out, embedded in a thermoplastic resin so that the rolled surface (L-LT surface) of the plate can be polished, mirror-polished, anodized in a borohydrofluoric acid aqueous solution, and subjected to a polarizing microscope ( The metal structure was observed with a magnification of 50). The average crystal grain size of the recrystallized grains of each final plate obtained was measured by a section method (cutting method). Measure the number of crystal grain boundaries (n) that the imaginary line crosses when drawing the imaginary line with a length of 12.1 mm in the field of view while sequentially shifting the scale of the field of view of the polarizing microscope. The average crystal grain size (μm) was calculated.
{12.1 × 10 ³ / (n−1)} (1)
This measurement was performed twice for each final plate, and an average value of the two measured values was adopted. Table 4 shows the measurement results of the average crystal grain size of the recrystallized grains of each final plate.

When the final plate conductivity is 53.0% IACS or higher, the heat dissipation evaluation is good (◯), and when the final plate conductivity is less than 53.0% IACS, the heat dissipation evaluation is poor (×). It was.
When the elongation value of the final plate is 40.0% or more, the moldability evaluation is good (◯), and when the elongation value of the final plate is less than 40.0%, the moldability evaluation is poor (×). It was.
When the value of (TS95-TS90) is less than −4 MPa, the work softening evaluation is good (◯), and when the value of (TS95-TS90) is −4 MPa or more, the work softening evaluation is poor (×) It was.
The final plate has an elongation value of 5.0% or more after cold rolling with a rolling reduction of 90% is regarded as good (評 価), and the final plate is cold with a rolling reduction of 90%. The elongation value after rolling was less than 5.0% was regarded as poor operation stability evaluation (x). These evaluation results are shown in Table 4.

  Example 51 in Table 4 showing the property evaluation results of the test materials is within the composition range of the present invention, and the final annealing is annealing annealing simulating batch annealing held at a holding temperature of 340 ° C. for 1 hour. All of the electrical conductivity of the plate, the value of the elongation of the final plate, the value of (TS95-TS90), and the value of the elongation after cold rolling with a rolling reduction of 90% were satisfied for the final plate. Specifically, in Example 51, the conductivity of the final plate is 53.0% IACS or more, the elongation value of the final plate is 40.0% or more, and the value of (TS95-TS90) is −4 MPa. The elongation value after subjecting the final plate to cold rolling with a rolling reduction of 90% was 5.0% or more. Therefore, in Example 51, the heat dissipation evaluation was good (◯), the moldability evaluation was good (◯), the work softening evaluation was good (◯), and the operational stability evaluation was good (◯). The final plate of Example 51 exhibited a recrystallized structure, and the average crystal grain size of the recrystallized grains was 16.0 μm.

  Example 52 in Table 4 showing the property evaluation results of the test materials is within the composition range of the present invention, and the final annealing is annealing annealing simulating batch annealing held at a holding temperature of 440 ° C. for 1 hour. All of the electrical conductivity of the plate, the value of the elongation of the final plate, the value of (TS95-TS90), and the value of the elongation after cold rolling with a rolling reduction of 90% were satisfied for the final plate. Specifically, in Example 52, the conductivity of the final plate is 53.0% IACS or more, the elongation value of the final plate is 40.0% or more, and the value of (TS95-TS90) is −4 MPa. The elongation value after subjecting the final plate to cold rolling with a rolling reduction of 90% was 5.0% or more. Therefore, in Example 52, the heat dissipation evaluation was good (◯), the moldability evaluation was good (◯), the work softening evaluation was good (◯), and the operational stability evaluation was good (◯). The final plate of Example 52 exhibited a recrystallized structure, and the average crystal grain size of the recrystallized grains was 29.1 μm.

  Comparative Example 53 in Table 4 showing the property evaluation results of the test materials is within the composition range of the present invention, and the final annealing is annealing annealing simulating batch annealing held at a holding temperature of 240 ° C. for 1 hour. Although the electrical conductivity of the plate and the elongation value after the cold rolling of the final plate with a rolling reduction of 90% satisfied the standard value, the elongation value of the final plate, the value of (TS95-TS90) is the standard value Did not meet. Specifically, in Comparative Example 53, the conductivity of the final plate is 53.0% IACS or more, and the elongation value after the cold rolling of the final plate with a reduction rate of 90% is 5.0% or more. However, the elongation value of the final plate was less than 40.0%, and the value of (TS95-TS90) was -4 MPa or more. Therefore, Comparative Example 53 had good heat dissipation evaluation (◯), poor moldability evaluation (×), poor work softening evaluation (×), and good operation stability evaluation (◯). Further, the final plate of Comparative Example 53 had an uncrystallized structure, no recrystallized grains were present, and the average crystal grain size could not be measured.

  Comparative Example 54 in Table 4 showing the property evaluation results of the test materials is within the composition range of the present invention, and the final annealing is a salt bath annealing simulating continuous annealing held at a holding temperature of 425 ° C. for 10 seconds, Although the elongation value of the final plate satisfied the standard value, the electrical conductivity of the final plate, the value of (TS95-TS90), and the elongation value after cold rolling with a reduction ratio of 90% on the final plate are the standards. The value was not met. Specifically, in Comparative Example 54, although the elongation value of the final plate was 40.0% or more, the conductivity of the final plate was less than 53.0% IACS, and the value of (TS95-TS90) was -4 MPa or more, and the elongation value after subjecting the final plate to cold rolling at a reduction rate of 90% was less than 5.0%. Therefore, the comparative example 54 was heat dissipation evaluation defect (x), moldability evaluation favorable ((circle)), work softening evaluation defect (x), and operation stability evaluation defect (x). The final plate of Comparative Example 54 exhibited a recrystallized structure, and the average crystal grain size of the recrystallized grains was 13.6 μm.

  From the above, having the above specific component composition, conductivity of 53.0% IACS or more, elongation value of 40% or more, recrystallized structure, and cooling at a reduction rate of 90%. The value of (TS95-TS90) when the tensile strength after cold rolling is defined as TS90 and the tensile strength after cold rolling at a reduction rate of 95% is defined as TS95 is less than -4 MPa. The one that exhibits a value of 5.0% or more after cold rolling at a rolling reduction of 90% is excellent in heat dissipation, moldability, and work softening properties, and has little variation in operating pressure. It can be seen that this is an aluminum alloy plate for a battery lid capable of forming an explosion-proof valve.

Claims (3)

  Fe: 1.05-1.50 mass%, Mn: 0.15-0.70 mass%, Ti: 0.002-0.10 mass%, and B: less than 0.05 mass%, the balance Is composed of Al and impurities, Fe / Mn ratio is regulated to 1.8 to 7.0, Si as impurities is less than 0.40 mass%, Cu is less than 0.03 mass%, Mg is 0.05 mass %, V has a component composition regulated to less than 0.03% by mass, electrical conductivity is 53.0% IACS or more, elongation value is 40% or more, and has a recrystallized structure, The value of (TS95-TS90) when the tensile strength after cold rolling at a reduction rate of 90% is defined as TS90, and the tensile strength after cold rolling at a reduction rate of 95% is defined as TS95. Is less than −4 MPa, the elongation after cold rolling at a reduction rate of 90% There, characterized in that it is 5.0% or more, an aluminum alloy plate for a battery cover for integrated explosion-proof valve molding.   2. The aluminum alloy plate for battery cover for forming an integral explosion-proof valve according to claim 1, wherein the recrystallized grains have an average crystal grain size of 15 to 30 μm. A method for producing an aluminum alloy plate for a battery lid for forming an integral explosion-proof valve according to claim 1 or 2,
A slab casting step of casting a molten aluminum alloy having the component composition according to claim 1 into an ingot by a semi-continuous casting method;
A homogenization treatment step of subjecting the ingot to a homogenization treatment at a holding temperature of 520 to 620 ° C. and a holding time of 1 hour or more;
After the homogenization treatment step, set a starting temperature of less than 420 to 520 ° C., hot rolling the ingot to obtain a hot rolled plate,
A cold rolling step of cold rolling the hot rolled plate to obtain a cold rolled plate;
See containing and a final annealing step of performing the final annealing in a batch furnace in the cold-rolled sheet,
In the cold rolling step, the final cold rolling ratio is in the range of 50% to 95%, and the final cold rolling is performed.
In the final annealing step, the final annealing for 1 hour or more is performed at a holding temperature of 300 to 450 ° C., and the method for producing an aluminum alloy plate for battery lid for integral explosion-proof valve forming.