CN104838025A - Battery-case aluminium alloy plate exhibiting excellent moulding properties, heat-dissipation properties, and welding properties - Google Patents

Battery-case aluminium alloy plate exhibiting excellent moulding properties, heat-dissipation properties, and welding properties Download PDF

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Publication number
CN104838025A
CN104838025A CN201480003399.7A CN201480003399A CN104838025A CN 104838025 A CN104838025 A CN 104838025A CN 201480003399 A CN201480003399 A CN 201480003399A CN 104838025 A CN104838025 A CN 104838025A
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quality
aluminium alloy
alloy plate
cold rolling
properties
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铃木健太
大和田安志
穴见敏也
水嶋一光
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Nippon Light Metal Co Ltd
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Nippon Light Metal Co Ltd
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    • 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
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6554—Rods or plates
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Continuous Casting (AREA)
  • Metal Rolling (AREA)

Abstract

Provided is a 3000 series aluminium alloy plate which exhibits heat-dissipation characteristics applicable to large lithium ion battery containers, and which also exhibits excellent moulding properties, shape fixability, and laser welding properties. The aluminium alloy plate is a cold-rolled annealed material which has: a component composition including over 0.2 mass percent but less than 1.4 mass percent of Fe, 0.5-2.0 mass percent of Mn, over 0.2 mass percent but not more than 1.1 mass percent of Si, 0.05-1.0 mass percent of Cu, and less than 0.05 mass percent of Mg, the remainder comprising Al and impurities; a conductivity of over 45 percent IACS; a metallographic structure in which the number of second phase particles having an equivalent circular diameter of at least 2 [mu]m is less than 1800/mm2; a 0.2 percent proof stress of at least 30 MPa but less than 85 MPa; and an elongation value of at least 10 percent. Otherwise, this aluminium alloy plate is a cold-rolled material which has: a conductivity of over 45 percent IACS; a metallographic structure in which the number of second phase particles having an equivalent circular diameter of at least 2 [mu]m is less than 1800/mm2; a 0.2 percent proof stress of at least 90 MPa but less than 180 MPa; and an elongation value of at least 3 percent.

Description

The aluminium alloy plate for battery case of plasticity, thermal diffusivity and excellent weldability
Technical field
The present invention relates to the aluminium alloy plate for the plasticity of the secondary cell containers such as lithium ion battery, thermal diffusivity and excellent weldability.
Background technology
3000 of Al-Mn system is alloy because intensity, plasticity and laser welding are more excellent, is therefore used as starting material when manufacturing the secondary cell containers such as lithium ion battery gradually.Sealed by laser welding after being configured as desired shape, use as secondary cell container.Be alloy and existing 3000 by above-mentioned 3000 be based on alloy, also further developed the secondary cell container aluminium alloy plate that improve intensity and plasticity.
Such as, in patent documentation 1, describe the square-shaped battery casing aluminium alloy plate with following characteristics: the composition as aluminium alloy plate has the composition of JIS A3003 defined, earing rate is less than 8%, the median size of recrystallization grains be below 50 μm while, specific conductivity is at below 45IACS%.
On the other hand, as battery container, also developed the aluminium alloy plate for battery case that expansibility resistance is excellent when high temperature internal pressure load.In patent documentation 2, describe the aluminium alloy plate for battery case that the high temperature resistant swelling property with following characteristics is excellent: containing Mn0.8 ~ 2.0% (quality %, identical below), and be limited in less than 0.6% as the Fe amount of impurity, Si amount is limited in less than 0.3%, remainder is made up of Al and inevitable impurity, and Mn solid solution capacity more than 0.75% and the ratio of Mn solid solution capacity and Mn addition more than 0.6, and yield strength value is at 185 ~ 260N/mm 2scope in.
Further, the manufacture method of the plasticity with following characteristics and the excellent hermetic type rectangular cell aluminum alloy case material of creep resistant is described: by Al and aluminium alloy ingot bar that inevitably impurity is formed, hot rolling and cold rolling is implemented to Mn, the Si of 0.1 ~ 0.5%, Fe, the remainder of 0.3 ~ 1.0% containing 0.5 ~ 1.5% in patent documentation 3, in the temperature of above-mentioned cold rolling rear preservation more than 450 DEG C, implement the anneal being cooled to 200 DEG C with the speed of cooling of more than 1 DEG C/sec afterwards.
But, known to being that alloy to form in the aluminium alloy plate improved as substrate it using 3000, produce abnormal bead sometimes, laser welding has problems.So also developed 1000 is as the excellent secondary cell container aluminium alloy plate of the laser welding of substrate.In patent documentation 4, describe a kind of when laser welding A1000 system aluminium, that do not produce uneven especially bead, that laser welding is excellent aluminium alloy plate.Thus, Si containing 0.02 ~ 0.10 quality % in aluminium alloy plate, Fe content is limited in below 0.30 quality %, and remainder is made up of Al and inevitable impurity, and equivalent circle diameter is that the number of the intermetallic compound particles of 1.5 ~ 6.5 μm is limited in 1000 ~ 2400/mm 2.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent No. 3620955 publication
Patent documentation 2: Japanese Patent No. 3843368 publication
Patent documentation 3: Japanese Patent No. 4244252 publication
Patent documentation 4: Japanese Patent Laid-Open 2009-256754 publication
Summary of the invention
Invent technical problem to be solved
Really, although 1000 is that weldability is stablized, had excellent moldability, there is the problem that intensity is low.Therefore, in the process of the maximization of lithium ion battery, estimate also to require high-strength characteristic, also have problems during the aluminium plate that direct use 1000 is.
As mentioned above, 3000 be alloy sheets when, although expansibility resistance when can obtain intensity and high temperature internal pressure load, compared with the alloy sheets being with 1000, have the tendency that poor, the abnormal bead number of plasticity is many.In addition, in the process of the maximization of lithium ion battery, estimate that the thermal value from lithium ion battery during discharge and recharge increases, also require that heat dissipation characteristics is excellent.And, the Mn solid solution capacity of usual 3000 line aluminium alloy plates is high, as large-scale lithium ion battery container, because it becomes to be grouped into, yield strength is too high sometimes, also there is stamping rear easy generation resilient-elasticity recovery, can not stabilize to the design shape of regulation, the problem of so-called shape freezing.
The present invention is the invention proposed to solve the problem, and its objective is that providing a kind of has the heat dissipation characteristics that can be used in large-scale lithium ion battery container, and plasticity, shape freezing is excellent, the 3000 line aluminium alloy plates that laser welding is also excellent.
The technical scheme that technical solution problem adopts
The aluminium alloy plate for battery case of plasticity of the present invention, excellent weldability, in order to realize this object, has following one-tenth and to be grouped into and specific conductivity is set to more than 45%IACS; Described one-tenth is grouped into and is: containing more than 0.2 and lower than the Fe of 1.4 quality %, 0.5 ~ 2.0 quality % Mn, more than the Si of 0.2 to 1.1 quality %, the Cu of 0.05 ~ 1.0 quality %, remainder is made up of Al and impurity, and Mg is lower than 0.05 quality %.
When as cold rolled annealed material, 0.2% yield strength is at more than 30MPa and lower than 85MPa, and the round equivalent footpath in metallographic is that the second phase particles number of more than 2 μm is lower than 1800/mm 2.In addition, when as cold rolling material, 0.2% yield strength is at more than 90MPa and lower than 180MPa, and the round equivalent footpath in metallographic is that the second phase particles number of more than 2 μm is lower than 1800/mm 2.
As the manufacture method of above-mentioned cold rolled annealed material, preferably the molten aluminium alloy with above-mentioned chemical constitution is cast into the thin flat plate of 5 ~ 10mm by double belt continuous casting machine, do not implement hot rolling but directly batch on roller, implementing cold rolling to reach final thickness of slab, then implement final annealing process.
In addition, as the manufacture method of above-mentioned cold rolling material, preferably the molten aluminium alloy with above-mentioned chemical constitution is cast into the thin flat plate of 5 ~ 10mm by double belt continuous casting machine, do not implement hot rolling but directly batch on roller, cold rolling to its enforcement, under suitable thickness of slab, implement process annealing, then implement final cold rolling rate be 5 ~ 20% finally cold rolling.
The effect of invention
Because aluminium alloy plate of the present invention is while having high thermal conductivity, plasticity is also excellent, and has excellent laser welding, therefore can manufacture airtight performance with low cost excellent and improve the secondary cell container of heat dissipation characteristics.
Especially when cold rolled annealed material, due to present more than 10% elongation, embody excellent weldability while, yield strength is at more than 30MPa and lower than 85MPa, and resilient-elasticity recovery time therefore stamping is inhibited, and consequently shape freezing is also excellent.
When this external cold rolling material, due to present more than 3% elongation values, embody excellent plasticity while, yield strength is at more than 90MPa and lower than 180MPa, and resilient-elasticity recovery time therefore stamping is inhibited, and consequently shape freezing is also excellent.
Accompanying drawing explanation
Fig. 1 is the schematic diagram be described the mensuration/evaluation method of welding defects count.
Embodiment
After secondary cell passes through to put into electrode body in container, utilize welding to wait cover lid also to seal and manufacture.If in such secondary cell being used for mobile telephone etc., then when charging, the temperature of internal tank can rise sometimes.For this reason, if it is low to there is the heat conductivity of material forming container, heat dissipation characteristics is deteriorated, and then causes the problem of short service life of lithium ion battery.Therefore, as used material, require that there is high thermal conductivity.
In addition, owing to usually using impact molding as the method forming container, therefore require that the material itself used has excellent press formability.And, also estimate to will speed up the raw-material thin-walled property in large-scale lithium ion battery container from now on.Certainly, if starting material generation thin-walled property, then at stamping rear easy generation resilient-elasticity recovery, the problem being difficult to obtain the design shape specified likely becomes obvious.Therefore, require that the material self used has excellent shape freezing.
And, as the method that cover lid also seals, use welding process, therefore also require excellent weldability.And, as welding process during manufacture secondary cell container etc., adopt the situation of method of laser welding more.Because 3000 line aluminium alloy plates of the present invention have high thermal conductivity, therefore when to stamping and the container obtained and lid carry out pulse laser joint, need the energy improving each pulse, engage under harsher condition.But, if carry out laser welding under so more harsh condition, then there is the problem of welding flaw producing otch (ア ン ダ ー カ ッ ト, undercut) or be called pore on welding bead.
By the irradiation of such pulse laser, infer that the surface temperature local of the welding bead in engaging reaches the high temperature of more than 2000 DEG C.Aluminium is high reverse--bias material, about 7 one-tenth of reflected laser beam.On the other hand, be present in the second phase particles of the near surface of aluminium alloy plate, as intermetallic compounds such as Al-(FeMn)-Si, compared with the aluminium of parent phase, even if at room temperature its specific heat, thermal conductivity are also little, temperature prioritised rising.The thermal conductivity of these intermetallic compounds rises along with temperature and reduces further, and its absorptivity rises with acceleration, and only intermetallic compound is by sharply heat fused.The irradiation time of the pulsatile once of pulse laser is the very short time being called nanosecond, femtosecond.Therefore, matrix α-Al melt and when carrying out phase transition to liquid phase, evaporate because the intermetallic compounds such as Al-(FeMn)-Si arrive boiling point one step ahead, therefore volume sharply expands.
So in the present invention, cold rolled annealed material is adopted to the thin flat plate molten aluminium alloy with specified chemical composition being cast into 5 ~ 10mm by double belt continuous casting machine, do not implement hot rolling but directly batch the manufacture method on roller.When casting the thin flat plate of 5 ~ 10mm by double belt continuous casting machine, because the speed of cooling near ingot bar thickness 1/4 is about 40 ~ 200 DEG C/sec, so the thin flat plate with the metallographic that the intermetallic compounds such as Al-(FeMn)-Si slightly disperse can be obtained.Consequently, can be that the second phase particles number of 2 μm is restricted to lower than 1800/mm by the round equivalent footpath in the metallographic of most soleplate 2, the welding flaw number produced at laser weld can be reduced.
But the solid solution capacity of Mn, Si etc. under such state in matrix is too high, although so expansibility resistance when fully can guarantee high temperature internal pressure load, can forming shaped, heat conductivity difference most soleplate.So, adopt: (1) implements cold rolling to reach final thickness of slab to the roller batched, then implements the manufacture method of final annealing process; Or (2) implement cold rolling to the roller batched, under suitable thickness of slab, implement process annealing, then implement the finally cold rolling manufacture method that final cold rolling rate is 5 ~ 20%.By implementing process annealing process or final annealing process to so cold rolling coiled material, make to be solid-solubilized in Mn, Si etc. in matrix energetically diffusion absorption in intermetallic compound, reduce the solid solution capacity of Mn, Si etc., while the heat conductivity improving most soleplate, improve elongation values and also yield strength is suppressed in low-level.Consequently can be made into and there is high heat dissipation characteristics, and the aluminium alloy plate that plasticity, shape freezing are also excellent.
The present invention is by the content of regulation Fe, Mn, Si, Cu, the intermetallic compound in thin flat plate is made slightly to disperse to separate out (crystallization), the content of the Mg as impurity is suppressed in low-level, by while the welding flaw number reducing laser weld generation, cold rolling coiled material enforcement process annealing process or final annealing process are reduced to the solid solution capacity of Mn, Si etc., yield strength suppressed in low-level and improves heat conductivity, making the aluminium alloy plate of plasticity, thermal diffusivity and excellent weldability.The present inventor has carried out conscientiously studying to obtain the also excellent aluminium alloy plate of laser welding, by to the investigation about heat conductivity (specific conductivity), press formability characteristic, investigation with the welding flaw quantity produced at weld part, completes the present invention.
Below, its content is described.
First, the effect of each element contained in secondary cell container aluminium alloy plate of the present invention, suitable content etc. are described.
fe: more than 0.2 and lower than 1.4 quality %
Fe is the required element for increasing aluminium alloy plate intensity.If it is not Fe content is at below 0.2 quality %, then preferred due to the strength degradation of aluminium alloy plate.If the content of Fe is more than 1.4 quality %, then due to Al-(FeMn)-Si system, Al when thin flat plate is cast 6(FeMn) etc. thick intermetallic compound crystallization, the easy evaporation compared with α-Al matrix when laser welding of these intermetallic compounds, welding flaw quantity increases, weldability declines, thus not preferred.
Therefore, Fe content is set to more than 0.2 and lower than the scope of 1.4 quality %.Preferred Fe content is more than 0.25 and lower than the scope of 1.3 quality %.Further preferred Fe content is more than 0.3 and lower than the scope of 1.2 quality %.
mn:0.5 ~ 2.0 quality %
Mn is the required element for increasing aluminium alloy plate intensity.If it is not Mn content is lower than 0.5 quality %, then preferred due to the strength degradation of aluminium alloy plate.If the content of Mn is more than 2.0 quality %, then the Mn solid solution capacity in matrix becomes too high, and not only the heat conductivity of most soleplate declines, and yield strength also becomes too high, shape freezing declines.Further, Al-(FeMn)-Si system, Al when thin flat plate is cast 6(FeMn) etc. thick intermetallic compound crystallization, the easy evaporation compared with α-Al matrix when laser welding of these intermetallic compounds, welding flaw quantity increases, weldability declines, thus not preferred.
Therefore, Mn content is set to the scope of 0.5 ~ 2.0 quality %.Preferred Mn content is the scope of 0.5 ~ 1.9 quality %.Preferred Mn content is the scope of 0.6 ~ 1.8 quality % further.
si: more than 0.2 and at below 1.1 quality %
Si is the intensity increasing aluminium alloy plate, improves the essential element of liquation mobility when casting.If Si content is at below 0.2 quality %, then due to while the strength degradation of aluminium alloy plate liquation mobility also to decline and not preferred.If the content of Si is more than 1.1 quality %, then owing to finally solidifying the intermetallic compound crystallizations such as Al-(FeMn)-Si comparatively thick in portion when thin flat plate is cast, these intermetallic compounds are easy evaporation compared with α-Al matrix when laser welding, welding flaw quantity increases, weldability declines, thus not preferred.
Therefore, Si content is set to more than 0.2 and in the scope of below 1.1 quality %.Preferred Si content is the scope of 0.25 ~ 1.0 quality %.Preferred Si content is the scope of 0.3 ~ 1.0 quality % further.
cu:0.05 ~ 1.0 quality %
Cu is the required element for increasing aluminium alloy plate intensity.If it is not Cu content is lower than 0.05 quality %, then preferred due to the strength degradation of aluminium alloy plate.If it is not Cu content is more than 1.0 quality %, then preferred because heat conductivity and weldability decline.
Therefore, Cu content is set to the scope of 0.05 ~ 1.0 quality %.Preferred Cu content is the scope of 0.05 ~ 0.9 quality %.Preferred Cu content is the scope of 0.05 ~ 0.8 quality % further.
mg as inevitable impurity: lower than 0.05 quality %
Can also containing the Mg as inevitable impurity lower than 0.05 quality %.In the present invention, if Mg content is lower than 0.05 quality %, then the characteristic such as heat conductivity, plasticity and weldability can not decline.
other inevitable impurity
Inevitable impurity is from raw material crude metal, the impurity be inevitably mixed into returning waste material etc., their admissible content is, such as Zn is lower than 0.05 quality %, Ni is lower than 0.10 quality %, Pb, Bi, Sn, Na, Ca, Sr are respectively lower than 0.02 quality %, Ga and Ti is lower than 0.01 quality %, Nb and V is lower than 0.1 quality %, Co is lower than 0.3 quality %, other impurity are respectively lower than 0.05 quality %, even if the element contained outside control also can not harm effect of the present invention within the scope of this.
elongation values and 0.2% yield strength
cold rolled annealed material: the value of elongation be more than 10% and 0.2% yield strength at more than 30MPa and lower than 85MPa
cold rolling material: the value of elongation is more than 3% and 0.2% yield strength is low at more than 90MPa in 180MPa
In addition, when 3000 line aluminium alloy plates being applied to large-scale lithium ion battery container etc., not only need to have high heat dissipation characteristics and excellent laser welding, also need while the suitable intensity of maintenance, plasticity, shape freezing are also excellent.By shape freezing and the intensity of the known material of 0.2% yield strength when carrying out tension test, and by the known plasticity of the value of elongation during tension test.
Detailed content is recorded in embodiment described later, as the 3000 line aluminium alloy plates of the present invention being applicable to large-scale lithium ion battery container etc., for preferably there is during cold rolled annealed material elongation value more than 10% and 0.2% yield strength at more than 30MPa and lower than the characteristic of 85MPa, for preferably there is during cold rolling material elongation value more than 3% and 0.2% yield strength at more than 90MPa and lower than the characteristic of 180MPa.
specific conductivity is more than 45%IACS
Characteristic as above, manufacture there is 3000 line aluminium alloy plate that aforesaid specific one-tenth is grouped into time, by implementing process annealing process or final annealing process to cold rolling coiled material, the method reducing the solid solution capacity of Mn, the Si etc. in matrix presents.
Specifically, such as preferred by cold rolling coiled material insertion batch-type annealing furnace, heating, keeps 1 ~ 8 hour with 330 ~ 470 DEG C, implements process annealing process or final annealing process.
Like this, the process annealing process of cold rolling coiled material or final annealing processing example as by carrying out with the maintenance temperature of 330 ~ 470 DEG C, the hold-time of 1 ~ 8 time in batch-type annealing furnace, by making to be solid-solubilized in the diffusion absorptions such as Mn, the Si in matrix in the intermetallic compounds such as Al-(the FeMn)-Si slightly having disperseed when thin flat plate is cast to separate out, the solid solution capacity of Mn, Si etc. can be reduced efficiently.
In process annealing operation or final annealing operation and heating thereof, refrigerating work procedure, the intermetallic compounds such as Al-(FeMn)-Si absorb Mn, Si etc. of being solid-solubilized in matrix, and its size becomes large, and the solid solution capacity of Mn, Si etc. in matrix reduces.
The present inventor is by adopting in alloy composition scope of the present invention, double belt continuous casting machine is utilized to be cast into the thin flat plate of 5 ~ 10mm, do not implement hot rolling but directly batch the manufacture method on roller, the intermetallic compounds such as Al-(FeMn)-Si are evenly fine separated out, in process annealing operation afterwards or final annealing operation, make the solid solution capacity of Mn, the Si etc. in matrix decline efficiently, can specific conductivity be improved.
On the other hand, be in the semicontinuous casting flat board (DC casts flat board) of alloy 3000, especially at the position that portion of finally solidifying is such, become to be grouped into and different according to it, but thicker Al 6(FeMn), the intermetallic compound crystallization such as Al-(FeMn)-Si.Comparatively thick intermetallic compound like this, is easy to evaporate when the laser welding of most soleplate, is considered to the reason that welding flaw quantity increases compared with α-Al matrix.The liquation of compositing range of the present invention utilizes double belt continuous casting machine to be cast into the thin flat plate of 5 ~ 10mm by adopting by the present inventor, do not implement hot rolling but directly batch the manufacture method on roller, the intermetallic compounds such as Al-(FeMn)-Si are evenly fine separated out, makes the round equivalent footpath in the metallographic of most soleplate be that the second phase particles number of more than 2 μm is lower than 1800/mm 2, successfully make the welding flaw digital display work in laser weld reduce.
Then, the method manufacturing secondary cell container aluminium alloy plate as above is simply introduced.
melt, found
Raw material is put in smelting furnace, if reach the temperature of fusion of regulation, then suitably drops into flux stirring, then use as required spray gun etc. carry out degassed in stove after, keep tranquil, the surface of dregs from liquation be separated.
In this fusing and melting, owing to adopting the alloying constituent of regulation, so the raw material of mother alloy etc. drops into also very important again, but very importantly from molten aluminium alloy, float up to liquation face to above-mentioned flux with dregs and being separated, need the enough tranquil time.The tranquil time is typically it is desirable that the source get more than 30 minutes.
The molten aluminium alloy founded with smelting furnace according to circumstances sometimes a part be pipetted into and keep casting after in stove, also direct discharge from smelting furnace is cast sometimes.More preferably the tranquil time is more than 45 minutes.
As required, also can online degassed, pass through strainer.
About degassed online, main flow is blown into aluminum melt from rotor by rare gas element etc., the hydrogen in liquation is diffused into carry out in the bubble of rare gas element the type removed.During as rare gas element use nitrogen, importantly dew point is controlled at such as less than-60 DEG C.The amounts of hydrogen of ingot bar is preferably reduced to
Below 0.20cc/100g.
In addition, separate out during the laser welding of the hydrogen of supersaturation ground solid solution sometimes after most soleplate is shaped in ingot bar, make in bead, to produce a large amount of pores.For this reason, the amounts of hydrogen of preferred ingot bar is
Below 0.15cc/100g.
casting
Ingot bar utilizes double belt continuous casting machine, and continuous casting is the thin flat plate of 5 ~ 10mm thickness.Twin belt caster possesses and has endless belt and a pair rotating band part stood facing each other up and down, the cavity formed between this pair rotating band part and the cooling unit being arranged at aforementioned rotating band partial interior, in aforementioned cavity, supply molten metal by the nozzle be made up of refractory materials, thus cast thin flat plate continuously.
When casting the thin flat plate of 5 ~ 10mm by double belt continuous casting machine, due near ingot bar thickness 1/4 time speed of cooling be about 40 ~ 200 DEG C/sec, the thin flat plate with the metallographic that the intermetallic compounds such as Al-(FeMn)-Si slightly disperse can be obtained.
In alloy plate in compositing range of the present invention, if slab-thickness is more than 10mm, be difficult to batch on roller.In addition, if slab-thickness is lower than 5mm, then liquation is difficult to flow equably in cavity.Therefore, slab-thickness is defined as 5 ~ 10mm.Then, hot rolling process is not implemented to this thin flat plate, homogenize process, but directly batch on roller, implement cold rolling.
cold rolling process
Make the coiled material batched by cold-rolling mill, usually implement the cold rolling of several passage.Now, there is work hardening due to the viscous deformation because of cold rolling importing, therefore usually as required, in the enterprising interline anneal in modified basis of most soleplate.
In the present invention, when not carrying out final annealing described later, the process annealing process between cold rolling process is required, such as preferred by cold rolling coiled material insertion batch-type annealing furnace, heat, keep 1 ~ 8 hour with 330 ~ 470 DEG C, implement process annealing process.
Like this, through the process annealing process of cold rolling coiled material by carrying out with the maintenance temperature of 330 ~ 470 DEG C, hold-time of 1 ~ 8 hour in batch-type annealing furnace, make to be solid-solubilized in the diffusion absorptions such as Mn, the Si in matrix in the intermetallic compounds such as Al-(the FeMn)-Si slightly having disperseed when thin flat plate is cast to separate out, the solid solution capacity of Mn, Si etc. can be reduced efficiently.If keep temperature lower than 330 DEG C, then Mn, the Si etc. be solid-solubilized in matrix can not be diffused fully and absorb in intermetallic compound, fully can not reduce the solid solution capacity of Mn, Si etc.If keep temperature more than 470 DEG C, then due to coiled material cooling too spended time, productivity decline and not preferred.
In addition, if the hold-time of coiled material in the maintenance temperature of regulation was lower than 1 hour, then because the entity temperature of coiled material likely becomes uneven and not preferred.If it is not the hold-time of the coiled material during maintenance temperature specified was more than 8 hours, then preferred because productivity declines.Therefore, preferred process annealing condition is keep temperature 330 ~ 470 DEG C, the scope of 1 ~ 8 hour hold-time.
final annealing
For the coiled material being cold-rolled to final thickness of slab through cold rolling process, if also consider the plasticity in die forming operation, it is preferably made to soften in advance as far as possible, it is therefore desirable that carry out final annealing.In the present invention, when especially not carrying out process annealing in cold rolling process, final annealing is required, most soleplate must be made annealed material.
In the present invention, the final annealing carried out after finally cold rolling is such as preferred by through cold rolling and coiled material that is that reach final thickness of slab inserts in batch-type annealing furnace, heats, keeps 1 ~ 8 hour with 330 ~ 470 DEG C, implement final annealing process.
Like this, through the final annealing process of cold rolling coiled material by carrying out with the maintenance temperature of 330 ~ 470 DEG C, hold-time of 1 ~ 8 hour in batch-type annealing furnace, make to be solid-solubilized in the diffusion absorptions such as Mn, the Si in matrix in the intermetallic compounds such as Al-(the FeMn)-Si slightly having disperseed when thin flat plate is cast to separate out, the solid solution capacity of Mn, Si etc. can be reduced efficiently.If keep temperature lower than 330 DEG C, then Mn, the Si etc. be solid-solubilized in matrix can not be diffused fully and absorb in intermetallic compound, fully can not reduce the solid solution capacity of Mn, Si etc.If keep temperature more than 470 DEG C, then due to coiled material cooling too spended time, productivity decline and not preferred.
In addition, if the hold-time of coiled material during the maintenance temperature of regulation was lower than 1 hour, then because the entity temperature of coiled material likely becomes uneven and not preferred.If it is not the hold-time of the coiled material during maintenance temperature specified was more than 8 hours, then preferred because productivity declines.Therefore, preferred final annealing condition is keep temperature 330 ~ 470 DEG C, the scope of 1 ~ 8 hour hold-time.
In the present invention, final annealing can be such batch-type anneal utilizing batch-type annealing furnace to keep at temperature 330 ~ 470 DEG C 1 ~ 8 hour, if but utilize continuous annealing furnace to keep within 15 seconds at the temperature of such as 400 DEG C ~ 550 DEG C, cool rapidly afterwards, then band of can also holding concurrently carries out melt process.
No matter carry out any, in the present invention, final annealing is all not necessarily, if but also consider the plasticity in die forming operation, it is desirable to make annealed material in advance.When paying the utmost attention to physical strength relative to plasticity, by carrying out process annealing in cold rolling process, then be cold-rolled to final thickness of slab, cold rolling material is provided.
final cold rolling rate
Final cold rolling rate during enforcement final annealing is preferably in the scope of 50 ~ 90%.If final cold rolling rate is within the scope of this, then the median size of the recrystallization grain in the most soleplate after can making annealing reaches about 10 ~ 20 μm, makes the value of elongation reach more than 10%, thus can by the appearance surfaces precision work nattily after being shaped.Further preferred final cold rolling rate is the scope of 60 ~ 90%.
On the other hand, final cold rolling rate when making cold rolling material under the precursor not implementing final annealing is preferably set to the scope of 5 ~ 20%.Thinning drawing is more when DI is shaped, need to provide slightly harder than annealed material most soleplate.If final cold rolling rate is lower than 5%, although then different according to composition, the yield strength of most soleplate is difficult to reach more than 90MPa; If final cold rolling rate is more than 20%, although then different according to composition, the value of the elongation of most soleplate is difficult to reach more than 3%.
If final cold rolling rate is within the scope of this, then the value of the elongation of cold rolling most soleplate can be made to reach more than 3% and make yield strength at more than 90MPa and lower than 180MPa.Further preferred final cold rolling rate is the scope of 5 ~ 15%.
By through common operation as above, secondary cell container aluminium alloy plate can be obtained.
Embodiment
the manufacture of most soleplate
The various ingot castings of regulation are measured, fusion, be coated with each the ingot casting inserting filling 6kg (amounts to 8 for try material) in No. 20 crucibles of release materials.Inserted by these crucibles in electric furnace, at 780 DEG C, dregs are removed in fusing, then melt temperature are remained on 740 DEG C, then, insert small-sized spray gun in liquation, pass into N with flow 1.0L/ minute 2gas carries out degassed process in 10 minutes.Then, tranquil 30 minutes, remove the dregs floated on molten surface by stirring rod, then with sample spoon, disk sample is taken in composition analysis mould.
Then, use fixture to be taken out in electric furnace by crucible successively, cast aluminum liquation in the water cooling mold of inside dimension 200mm × 200mm × 16mm, make thin flat plate.Compositional analysis is carried out to each disk sample emission spectroanalysis for examination material.The results are shown in table 1,2.
[table 1]
Table 1: the one-tenth for examination material is grouped into (embodiment)
[table 2]
Table 2: the one-tenth for examination material is grouped into (comparative example)
Note) be with the value of underscore to represent that for this element be the value outside specialized range.
After the rising head of this thin flat plate is cut off, two sides is respectively implemented to the surfacing cut of 3mm, make thickness reach 10mm, homogenize process, hot rolling are not implemented to this thin flat plate, but implement cold rolling.
First implementing to be cold-rolled to final thickness of slab to cold rolled annealed material is 1.0mm.Final cold rolling rate in this situation is 90%.Final annealing is that this cold-reduced sheet is inserted annealing furnace, is heated to 430 DEG C, after carrying out the anneal of 430 DEG C × 2 hours, is cooled to room temperature with the cooling rate of 50 DEG C/h with the heat-up rate of 50 DEG C/h.It can be used as cold rolled annealed material (modified mark: zero).In addition, implement to be cold-rolled to after final thickness of slab is 1.0mm to a part for examination material (embodiment 10 ~ 12, comparative example 9 ~ 10), as final annealing, this cold-reduced sheet is inserted in annealing furnace, 330 DEG C are heated to the heat-up rate of 50 DEG C/h, after carrying out the anneal of 330 DEG C × 2 hours, be cooled to room temperature with the cooling rate of 50 DEG C/h.It can be used as cold rolled annealed material (modified mark: zero).
In addition, to cold rolling material, first implementing to be cold-rolled to thickness of slab is 1.18mm.Process annealing is that this cold-reduced sheet is inserted annealing furnace, is heated to 430 DEG C, after carrying out the anneal of 430 DEG C × 2 hours, is cooled to room temperature with the cooling rate of 50 DEG C/h with the heat-up rate of 50 DEG C/h.Then implementing to be cold-rolled to final thickness of slab is 1.0mm, it can be used as cold rolling material (modified mark: H 12).Final cold rolling rate in this situation is 15%.In addition, first implementing to be cold-rolled to thickness of slab for examination material (embodiment 22 ~ 24) to a part is 1.05mm, implement process annealing under the condition identical with above-mentioned annealing conditions after, implementing to be cold-rolled to final thickness of slab is 1.0mm, it can be used as cold rolling material (modified mark: H 12).Final cold rolling rate in this situation is 5%.
Then, to the evaluation of most soleplate (each for examination material) forming property, shape freezing and the intensity of gained thus, laser welding, heat conductivity.
the evaluation of plasticity
The plasticity evaluation of the most soleplate obtained is undertaken by the elongation (%) of tension test.
Specifically, gather JIS5 test film in the mode that draw direction is parallel with rolling direction, carry out tension test according to JISZ2241, calculate 0.2% yield strength, elongation (elongation at break).
Implement in the most soleplate of annealing afterwards cold rolling, by the value of elongation be more than 10% be designated as plasticity good (zero) for examination material, by lower than 10% be designated as plasticity bad (×) for examination material.Evaluation result is shown in table 3,4.
In cold rolling most soleplate, by the value of elongation be more than 3% be designated as plasticity good (zero) for examination material, by lower than 3% be designated as plasticity bad (×) for examination material.Evaluation result is shown in table 3,4.
the evaluation of shape freezing and intensity
The most shape freezing of soleplate obtained and the evaluation of intensity are undertaken by 0.2% yield strength (MPa) of tension test.
Implement in the most soleplate (cold rolled annealed material) of annealing afterwards cold rolling, 0.2% yield strength is more than 30MPa and is designated as shape freezing and intensity good (zero) lower than 85MPa for examination material, more than 85MPa is designated as shape freezing bad (×) for examination material.In addition, by 0.2% yield strength lower than 30MPa for examination material be designated as undercapacity (×).
In the most soleplate (cold rolling material) of direct cold rolling, 0.2% yield strength is more than 90MPa and is designated as shape freezing and intensity good (zero) lower than 180MPa for examination material, more than 180MPa is designated as shape freezing bad (×) for examination material.In addition, by 0.2% yield strength lower than 90MPa for examination material be designated as undercapacity (×).Evaluation result is shown in table 3,4.
laser Welding Condition
Pulsed laser irradiation is carried out to the most soleplate obtained, carries out the evaluation of laser welding.Use the YAG laser-beam welding machine JK701 that Lu's this company of nimonic (LUMONICS society) makes; frequency 33.0Hz, welding speed 400mm/ minute, the energy 6.5J/p of each pulse, pulse width 1.5 milliseconds, shielding gas (nitrogen) flow 15 (L/ minute) condition under, to two blocks of identical plates for examination material with end each other mode that is very close to each other, that be close to carry out the pulsed laser welding of overall length for 100mm length along this part.
the evaluation of laser welding
mensuration/the evaluation of black segmental defect
Then, as the evaluation of laser welding, the welding flaw quantity that weld part produces is determined at.First, in the welding line of above-mentioned 100mm length, the welding line of the 20mm length of removing welding start portion, using the region of remaining 80mm length as mensuration region.Welding starts neighbouring position and is removed due to instability.
Then, as shown in Figure 1 by the welding bead cross section that X ray CT inspection is formed along the welding line of length 80mm, the X ray CT image on the thickness of slab cross section parallel with welding line is obtained.Detect black segmental defect based on this X ray CT image by image editing software again, calculated the area of black segmental defect by image analysis software.The population corresponding with each round equivalent footpath is calculated by this black part defect area.
In this manual, by circle equivalent footpath be the black segmental defect of more than 0.1mm number lower than 5 be designated as welding flaw quantitative assessment good (zero) for examination material, the number being the black segmental defect of more than 0.1mm by circle equivalent footpath be more than 5 be designated as welding flaw quantitative assessment bad (×) for examination material.Evaluation result is shown in table 3,4 in the lump.
the evaluation of heat conductivity
mensuration/the evaluation of specific conductivity
Specific conductivity (IACS%) is implemented to measure with electrical conductivity meter (AUTOSIGMA 2000 Japanese Huo Jin Co., Ltd. (Japanese ホ ッ キ Application グ Co., Ltd.) system).By specific conductivity more than 45 (IACS%) be designated as specific conductivity good (zero) for examination material, by specific conductivity be 45 (IACS%) below be designated as specific conductivity bad (×) for examination material.Evaluation result is shown in table 3,4 in the lump.
The most soleplate of the embodiment 3,5,15,17 shown in his-and-hers watches 3 and the comparative example 4,8,14,18 shown in table 4, cut out the vertical section (with LT direction vertical cross section) parallel with rolling direction, thermoplastic resin is imbedded in this vertical section and carries out mirror ultrafinish, implement etching with hydrofluoric acid aqueous solution, carry out metallographicobservation.(area in every 1 visual field is 0.0334mm to carry out photograph taking with opticmicroscope to microcosmic metallographic 2, 15 visuals field are taken to each sample) and carry out the image analysis of photograph, measure per unit area (1mm 2) equivalent circle diameter be the second phase particles number of more than 3 μm.Measurement result is shown in table 5.
[table 3]
[table 4]
each evaluation for examination material
Illustrate that embodiment 1 ~ 24 in the table 3 of the evaluation result of most soleplate is for the most soleplate (cold rolled annealed material, cold rolling material) in compositing range of the present invention, the evaluation (0.2% yield strength) of laser welding evaluation (black segmental defect), shape freezing and intensity, plasticity evaluation (elongation), heat conductivity evaluation (specific conductivity) be all well (zero).Therefore, the comprehensive evaluation of embodiment 1 ~ 24 is good (zero).
Illustrate that comparative example 1 ~ 18 in the table 4 of the evaluation result of most soleplate is for the most soleplate (cold rolled annealed material, cold rolling material) outside compositing range of the present invention, in the evaluation (0.2% yield strength) of laser welding evaluation (black segmental defect), shape freezing and intensity, plasticity evaluation (elongation), heat conductivity evaluation (specific conductivity), have at least one to be evaluated as bad (×).Therefore, the comprehensive evaluation of comparative example 1 ~ 18 is bad (×).
Comparative example 1 is cold rolled annealed material, and because Si content is the low levels excessively of 0.05 quality %, therefore heat conductivity evaluates bad (×).
Comparative example 2 is cold rolled annealed material, and because Si content is the too high amount of 1.18 quality %, therefore weldability evaluates bad (×).
Comparative example 3 is cold rolled annealed material, and because Fe content is the low levels excessively of 0.06 quality %, therefore heat conductivity evaluates bad (×).
Comparative example 4 is cold rolled annealed material, and because Fe content is the too high amount of 1.50 quality %, therefore weldability evaluates bad (×).
Comparative example 5 is cold rolled annealed material, and because Cu content is the too high amount of 1.2 quality %, therefore heat conductivity evaluates bad (×), and weldability evaluates bad (×).
Comparative example 6 is cold rolled annealed material, and because Cu content is the too high amount of 1.5 quality %, therefore heat conductivity evaluates bad (×), and weldability evaluates bad (×).
Comparative example 7 is cold rolled annealed material, because Mn content is low levels, the therefore evaluation of shape freezing and intensity bad (×) excessively of 0.30 quality %.
Comparative example 8 is cold rolled annealed material, and because Mn content is the too high amount of 2.20 quality %, therefore heat conductivity evaluates bad (×), and weldability evaluates bad (×).
Comparative example 9 is cold rolled annealed material (final annealing temperature: 330 DEG C), due to the too high amount that Cu content is 1.2 quality %, therefore heat conductivity evaluates bad (×), the evaluation bad (×) of shape freezing and intensity, plasticity evaluates bad (×), weldability evaluates bad (×).
Comparative example 10 is cold rolled annealed material (final annealing temperature: 330 DEG C), due to the too high amount that Cu content is 1.5 quality %, therefore heat conductivity evaluates bad (×), the evaluation bad (×) of shape freezing and intensity, plasticity evaluates bad (×), weldability evaluates bad (×).
Comparative example 11 is cold rolling material, and because Si content is the low levels excessively of 0.05 quality %, therefore heat conductivity evaluates bad (×).
Comparative example 12 is cold rolling material, and because Si content is the too high amount of 1.18 quality %, therefore weldability evaluates bad (×).
Comparative example 13 is cold rolling material, and because Fe content is the low levels excessively of 0.06 quality %, therefore heat conductivity evaluates bad (×).
Comparative example 14 is cold rolling material, and because Fe content is the too high amount of 1.50 quality %, therefore weldability evaluates bad (×).
Comparative example 15 is cold rolling material, and because Cu content is the too high amount of 1.2 quality %, therefore heat conductivity evaluates bad (×), plasticity evaluates bad (×), weldability evaluates bad (×).
Comparative example 16 is cold rolling material, due to the too high amount that Cu content is 1.5 quality %, therefore heat conductivity evaluates bad (×), the evaluation bad (×) of shape freezing and intensity, plasticity evaluates bad (×), weldability evaluates bad (×).
Comparative example 17 is cold rolling material, because Mn content is low levels, the therefore evaluation of shape freezing and intensity bad (×) excessively of 0.30 quality %.
Comparative example 18 is cold rolling material, and because Mn content is the too high amount of 2.20 quality %, therefore heat conductivity evaluates bad (×), and weldability evaluates bad (×).
[table 5]
image analysis result
The embodiment 3,5,15,17 illustrating in the table 5 of image analysis result is the most soleplates (cold rolled annealed material, cold rolling material) in compositing range of the present invention, the image analysis of the second phase particles in metallographic as a result, circle equivalent footpath is that the second phase particles number of more than 2 μm is lower than 1800/mm 2, think the intermetallic compounds such as thicker Al-(FeMn)-Si to there is density low.In addition, comparative example 4,8,14,18 is the most soleplates (cold rolled annealed material, cold rolling material) outside compositing range of the present invention, and laser welding evaluate in the number of black segmental defect many, circle equivalent footpath is that the second phase particles number of more than 2 μm is at 1800/mm 2above, think the intermetallic compounds such as thicker Al-(FeMn)-Si to there is density high.The evaluation result of the image analysis of the second phase particles in these metallographics is not necessarily completely the same with the evaluation result of aforesaid laser welding, but at least think that the direct generational verctor producing welding flaw when laser welding is the intermetallic compound existed in metallographic, its size distribution and kind are very important.
The possibility that industry utilizes
As above, if adopt the present invention, the heat dissipation characteristics having and can be used for large-scale lithium ion battery container can be provided, and plasticity, shape freezing are excellent, the 3000 line aluminium alloy plates that laser welding is also excellent.

Claims (2)

1. an aluminium alloy plate for battery case for plasticity, thermal diffusivity and excellent weldability, is characterized in that, this aluminium alloy plate for battery case is the cold rolled annealed material with following compositions composition:
Containing more than 0.2 and lower than the Mn of the Fe of 1.4 quality %, 0.5 ~ 2.0 quality %, more than 0.2 and lower than the Si of 1.1 quality %, the Cu of 0.05 ~ 1.0 quality %, remainder is made up of Al and impurity, Mg lower than 0.05 quality %,
The specific conductivity of described cold rolled annealed material is more than 45%IACS, and the round equivalent footpath in metallographic is that the second phase particles number of more than 2 μm is lower than 1800/mm 2, 0.2% yield strength, at more than 30MPa and lower than 85MPa, presents the value of the elongation of more than 10%.
2. an aluminium alloy plate for battery case for plasticity, thermal diffusivity and excellent weldability, is characterized in that, this aluminium alloy plate for battery case is the cold rolling material with following compositions composition:
Containing more than 0.2 and lower than the Mn of the Fe of 1.4 quality %, 0.5 ~ 2.0 quality %, more than 0.2 and lower than the Si of 1.1 quality %, the Cu of 0.05 ~ 1.0 quality %, remainder is made up of Al and impurity, Mg lower than 0.05 quality %,
The specific conductivity of described cold rolling material is more than 45%IACS, and the round equivalent footpath in metallographic is that the second phase particles number of more than 2 μm is lower than 1800/mm 2, 0.2% yield strength, at more than 90MPa and lower than 180MPa, presents the value of the elongation of more than 3%.
CN201480003399.7A 2013-08-02 2014-03-18 Battery-case aluminium alloy plate exhibiting excellent moulding properties, heat-dissipation properties, and welding properties Pending CN104838025A (en)

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