CN103748245A - Aluminum alloy plate material for lithium ion battery cases - Google Patents
Aluminum alloy plate material for lithium ion battery cases Download PDFInfo
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- CN103748245A CN103748245A CN201180072252.XA CN201180072252A CN103748245A CN 103748245 A CN103748245 A CN 103748245A CN 201180072252 A CN201180072252 A CN 201180072252A CN 103748245 A CN103748245 A CN 103748245A
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- aluminum alloy
- alloy plate
- ion battery
- work hardening
- lithium ion
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 229910018084 Al-Fe Inorganic materials 0.000 claims abstract description 18
- 229910018192 Al—Fe Inorganic materials 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052752 metalloid Inorganic materials 0.000 claims description 13
- 150000002738 metalloids Chemical class 0.000 claims description 13
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 12
- 238000005482 strain hardening Methods 0.000 description 48
- 238000000034 method Methods 0.000 description 35
- 238000000137 annealing Methods 0.000 description 23
- 238000005097 cold rolling Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 238000005098 hot rolling Methods 0.000 description 16
- 238000004880 explosion Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- 238000003466 welding Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000003566 sealing material Substances 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 150000002737 metalloid compounds Chemical class 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910018619 Si-Fe Inorganic materials 0.000 description 1
- 229910008289 Si—Fe Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- 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
- 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
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/133—Thickness
-
- 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)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Provided is an aluminum alloy plate material for lithium ion battery cases, which is capable of lowering explosion-proof valve working pressure and has excellent laser weldability. The aluminum alloy plate material for lithium ion battery cases is characterized by containing, in mass%, 0.5-2.0% of Fe and 0.03-0.3% of Si, while limiting Cu, Mn, Mg and Zn contained as impurities respectively to 0.10% or less, with the balance made up of Al and unavoidable impurities. The aluminum alloy plate material for lithium ion battery cases is also characterized in that: Al-Fe intermetallic compounds each having a circle-equivalent diameter of 5-30 nm are distributed in the matrix at a density of 1,000 per [mu]m3 or more; and when the thickness of the original plate before cold pressing is represented by T0, the thickness after cold pressing is represented by T1, and the reduction degree (R (%)) of cold pressing is equal to [(T0-T1)/T0] 100, the difference between the tensile strength at the time when R is 70% (TS70 (MPa)) and the tensile strength at the time when R is 90% (TS90 (MPa)), namely (TS70-TS90) is more than 5 MPa.
Description
Technical field
The present invention relates to the lithium ion battery that suitable conduct utilizes in automobile, mobile telephone, digital camera etc. case material, laser welding is excellent and can reduce the lithium-ion battery shell aluminum alloy plate materials of explosion trap driving pressure.
Background technology
Lithium ion battery housing is tank body material and the stamping sealing material combination forming of aluminium sheet that aluminium sheet or iron plate drawing and forming are formed, and enclose after the internal structure bodies such as electrode, by being carried out to laser welding around, the junction surface of tank body material and sealing material makes.
In order to improve the intensity of housing, for sealing material proposed that the intensity after punch process is high, large, the requirement that can obtain high bond strength of fusion penetration during laser welding, but on the other hand, while causing lithium ion battery thermal runaway owing to overcharging etc., for lower the object of internal pressure before cell fracture, dispose explosion trap (position of the local attenuation of sheet metal thickness).
As the formation method of this explosion trap, there is the method for utilizing punch process to carry out integrally formed method, paste foil by laser welding etc. on the sealing material through perforation processing from sealing material, but there is unfavorable factor aspect cost, security in the latter, therefore, normally using the former formation method as preferred method.
As the material of sealing material, that main use is A1050 or A3003 so far.Although A1050 processing characteristics excellence, but there is the shortcoming that intensity is low and laser welding is poor after processing, on the other hand, although intensity after A3003 processing is high, laser welding is excellent, but explosion trap portion is meeting work hardening in punch process, therefore in order to regulate the driving pressure of explosion trap, need to heat-treat, thereby its cost becomes distinct issues.
In order to address these problems, as the aluminium of sealing material use, proposed the crack expansibility of explosion trap portion to carry out the Al-Mn-Si-Fe class alloy improving or improved laser welding and reduced (having removed the heat treatment step after punch process) Al-Fe-Mn class alloy etc. of work hardening.But, compared with A3003, although above-mentioned alloy material crack expansibility is improved, work hardening is minimized, and do not need the thermal treatment after punch process, but owing to existing, because work hardening causes, the hardness of explosion trap portion increases, the driving pressure of explosion trap exceedes the problem that design pressure uprises, and therefore cannot meet desired characteristic.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-037129 communique
Patent documentation 2: No. 4281727 communiques of Japanese Patent
Summary of the invention
The problem that invention will solve
In the process of inquiring at the aluminium in order to obtain the above-mentioned existing issue point that can overcome sealing material, the inventor finds, while causing the accumulation volume of dislocation to increase because of cold working, become the site of burying in oblivion of dislocation with the inconsistent fine intermetallic compound of parent phase, thereby can make to produce work hardening beyond explosion trap process zone, and only at explosion trap process zone, represent softening state.
The result of the further repetition test of the understanding of the present invention based on above-mentioned, discussion obtains, and its object is, the lithium-ion battery shell aluminum alloy plate materials that can reduce explosion trap driving pressure, while laser welding excellence is provided.
The method of dealing with problems
In order to realize above-mentioned object, 1 the lithium-ion battery shell aluminum alloy plate materials according to the present invention, it is characterized in that, by mass%, contain Fe:0.5～2.0%, Si:0.03～0.3%, Cu, Mn, Mg, Zn as impurity are controlled at respectively below 0.10%, and surplus consists of Al and inevitable impurity, and in matrix, is distributed with 1000/μ m
3above diameter of equivalent circle is compound between the Al-Fe metalloid of 5～30nm, and, the thickness that the thickness of the original sheet material before Cold Press Working is made as after T0, Cold Press Working is made as T1 and Cold Press Working degree R(%)=[(T0-T1)/T0] × 100 o'clock, tensile strength TS70(MPa when R is 70%) and the tensile strength TS90(MPa of R while being 90%) while comparing, (TS70-TS90) exceed 5MPa.In addition, in the following description, alloying constituent all represents with quality %.
According to the present invention, 2 lithium-ion battery shell aluminum alloy plate materials, is characterized in that, in described aluminum alloy plate materials of the present invention 1, also contains that Ti:0.20% is following, Zr:0.20% following, Cr:0.30% is with lower one kind or two or more element.
According to the present invention, 3 lithium-ion battery shell aluminum alloy plate materials, is characterized in that, in described aluminum alloy plate materials of the present invention 1 or 2, also contains B:5～100ppm.
The effect of invention
According to the present invention, although can there is work hardening and hardening till approximately 70% cold working degree, but because material generation work hardening under the cold working degree of explosion trap process zone more than 90% becomes difficult, thereby can provide to take into account, engage the high strength of back casing and the lithium-ion battery shell aluminum alloy plate materials that explosion trap driving pressure reduces, be especially suitable for the aluminum alloy plate materials as the sealing material of lithium ion battery.
Embodiment
Below, lithium-ion battery shell of the present invention is described by the meaning of the alloying constituent of aluminum alloy plate materials and restriction reason thereof.
Fe generates incompatible and fine Al-Fe compounds in parent phase (matrix), thereby is created in the important element of the difficult effect of high degree of finish region processing sclerosis change.And, also there is the specific absorption that improves the YAG laser using in the joint of lithium ion battery, the effect of the fusion penetration while increasing laser welding.Preferred content is in 0.5～2.0% scope, if be less than 0.5%, it is (following that the work hardening representing in high degree of finish region becomes difficult characteristic, simply be described as " work hardening becomes difficult characteristic ") and fusion penetration during laser welding all insufficient, and content is while exceeding 2.0%, owing to generating thick intermetallic compound, cause punch process to reduce.The more preferred content range of Fe is 1.0～1.8%.
Si is easy to solid solution in manufacturing process, when its content exceedes 0.3%, is just difficult to represent work hardening and becomes difficult characteristic.On the other hand, Si is the element containing as inevitable impurity in aluminium ingot, when its content being controlled at while being less than 0.03%, because using highly purified aluminium ingot to cause cost rising, therefore not preferred.Therefore, the scope that the preferred content of Si is 0.03～0.3%, preferred content range is 0.05～0.20%.
In the present invention, owing to hindering work hardening as impurity Cu, the Mn, Mg, the Zn that are easy to solid solution, become representing of difficult characteristic, therefore preferably they are controlled at respectively below 0.10%, be more preferably controlled at below 0.05%.
Based on the object that prevents from welding time fracture (miniaturization of the tissue that nucleation causes when solidifying), can add Ti, Zr, Cr, B.Preferred content is respectively below Ti:0.20%, Zr:0.20% is following, Cr:0.30% is following, the scope of B:5～100ppm, when exceeding higher limit respectively, generates thick intermetallic compound, thereby causes the reduction of punch process.
Between Al-Fe metalloid, the size of compound and distribution number are to represent work hardening to become the difficult required important key element of characteristic.In order to obtain effect of the present invention, 1000/μ m preferably distributes in matrix
3above diameter of equivalent circle is compound between the Al-Fe metalloid of 5～30nm.The intermetallic compound that diameter of equivalent circle exceedes 30nm is difficult to become the site of burying in oblivion of dislocation, for work hardening become difficult characteristic to represent impact little.Diameter of equivalent circle is that the distribution number of the particle of 5～30nm is less than 1000/μ m
3time, dislocation bury in oblivion site deficiency, thereby cause work hardening to become difficult characteristic, represent insufficient.
At lithium-ion battery shell of the present invention, with in the manufacturing process of aluminum alloy plate materials, between above-mentioned Al-Fe metalloid, the reduction of the size of compound and the control of distribution number object and Si solid solution capacity is important key element.In manufacturing process, casting can adopt known semicontinuous casting method, but ingot casting homogenize that to process be that promote compound between Al-Fe metalloid fine separated out required important procedure.
Homogenize to process and preferably the temperature province of 450～540 ℃, carry out.While being less than 450 ℃, between Al-Fe metalloid compound separate out insufficiently, while exceeding 540 ℃, between Al-Fe metalloid, compound becomes coarsening after assembling, simultaneously Fe is by solid solution again, therefore not preferred.Treatment time that homogenizes is preferably 3～24 hours.If be less than 3 hours, between Al-Fe metalloid compound separate out insufficient, if exceed 24 hours, production cost increase.By adopting the above-mentioned treatment condition that homogenize, because the fine of compound between Al-Fe metalloid separated out, therefore can realize to the raising of the strength of materials till cold working degree 0～70%.
Homogenize process after carry out hot rolling.In course of hot rolling, in order to promote that between Al-Fe metalloid, the fine of compound separated out, hot rolling is preferably 400～450 ℃ of beginnings, to 200～250 ℃ of end.When this temperature province finishes hot rolling, the tissue after hot rolling becomes non-recrystallization tissue.
For the object that improves work hardening and become difficult characteristic, preferably after hot rolling, carry out immediately process annealing.In process annealing process, using the processing deformation that imports in hot rolling as separating out site, between Al-Fe metalloid, the fine of compound separated out, and hinders work hardening simultaneously and becomes the Si that difficult characteristic represents and separate out, by reducing the solid solution capacity of Si, thereby can improve work hardening, become difficult characteristic.
Annealing temperature is preferably 260～400 ℃.When annealing temperature is less than 260 ℃, between Al-Fe metalloid compound separate out insufficiently, when annealing temperature exceedes 400 ℃, due to Si solid solution, therefore cannot fully obtain work hardening and become difficult characteristic.The rate of heating that is heated to annealing temperature is preferably 20～100 ℃/h.If rate of heating is less than 20 ℃/h, manufacturing cost does not raise, thereby preferred, if exceed 100 ℃/h, Si separate out insufficiently, thereby cannot fully obtain work hardening, become difficult characteristic.More preferred rate of heating is 30～60 ℃/h.About speed of cooling, although its on work hardening become difficult characteristic to represent impact little, due to the relation of rate of heating, must use batch furnace, therefore can carry out in stove cooling according to ordinary method.
Carry out after hot rolling, or carry out after hot rolling and process annealing, in order to obtain the thickness of slab of regulation, carry out cold rolling.About cold rolling, due to work hardening is become difficult characteristic represent impact little, therefore can carry out according to prescriptive procedure.
Cold rolling rear enforcement final annealing (being process annealing when H1n is modified).Final annealing is arranged side by side with the processing that homogenizes, and is to become the difficult required important operation of characteristic in order to obtain work hardening.The object of final annealing is, by recrystallize, impel to extend and increase, improve press formability, and as separating out site, promote that between Al-Fe metalloid, the fine of compound separated out using the processing deformation of cold rolling middle importing, make to hinder work hardening simultaneously and become the Si that difficult characteristic represents and separate out, thereby reduce the solid solution capacity of Si.
The temperature of final annealing is preferably 260～400 ℃.If annealing temperature is less than 260 ℃, insufficient, the press formability of recrystallize reduces, and causes separating out of compound between Al-Fe metalloid insufficient simultaneously.If more than 400 ℃, due to Si solid solution, cannot fully obtain work hardening and become difficult characteristic.
The rate of heating that is heated to final annealing temperature is preferably 20～100 ℃/h.If rate of heating is less than 20 ℃/h, manufacturing cost does not raise, thereby preferred, if exceed 100 ℃/h, Si separate out insufficiently, thereby cannot fully obtain work hardening, become difficult characteristic.About speed of cooling, although its on work hardening become difficult characteristic represent impact little, due to the relation of rate of heating must use batch furnace, therefore can carry out in stove cooling according to ordinary method.
Lithium-ion battery shell aluminum alloy plate materials of the present invention, according to desired strength level, after final annealing, implement cold rolling, thereby it is modified to can be used for H1n.Even when H1n is modified, also be not difficult to obtain work hardening and become difficult characteristic, but because press formability can reduce along with the minimizing of extending, therefore, consider the balance of intensity and press formability, be necessary the cold rolling rate after final annealing treatment condition, final annealing to adjust.
Embodiment
Below, by contrast embodiments of the invention and comparative example, describe, thus actual verification effect of the present invention.In addition, these embodiment only show an embodiment of the invention, and the present invention is not subject to the restriction of these embodiment.
Embodiment 1
Dissolving has the aluminium alloy (A～F) of the composition shown in table 1, by semicontinuous casting legal system, obtains the ingot casting that thickness is 500nm.After the ingot casting obtaining being carried out at 500 ℃ within 8 hours, homogenize and processing, rolling surface respectively planed and removed after 8mm, at 440 ℃, starting hot rollings subsequently, at 230 ℃, stopping hot rollings, thereby obtained the hot-rolled sheet that thickness is 5.0mm.
Secondly, cold rolling (cold rolling rate is 84%) to thickness is 0.8mm, then in the final annealing of 300 ℃ of enforcements 3 hours (rate of heating is 50 ℃/h), thereby it is modified to have made test materials 1～6(: O material).
Embodiment 2
Dissolving has the aluminium alloy (G) of the composition shown in table 1, cast similarly to Example 1, homogenize after processing, hot rolling, at 300 ℃, carry out the process annealing of 3 hours (rate of heating is 50 ℃/h), subsequently, cold rolling (cold rolling rate is 84%) to thickness is 0.8mm, implement the final annealing of 3 hours (rate of heating is 50 ℃/h) in 300 ℃ again, thereby it is modified to have made test materials 7(: O material).
Embodiment 3
Dissolving has the aluminium alloy (H) of the composition shown in table 1, cast similarly to Example 1, homogenize after processing, hot rolling, cold rolling (cold rolling rate is 36%) to thickness is 3.2mm, in 300 ℃, implement after the process annealing of 3 hours (rate of heating is 50 ℃/h) again, cold rolling (cold rolling rate is 75%) to thickness is 0.8mm, thereby it is modified to have made test materials 8(: H16 material).
Table 1
Comparative example 1
Dissolving has the aluminium alloy (I～M) of the composition shown in table 2, cast similarly to Example 1, the ingot casting obtaining is carried out at 500 ℃ within 8 hours, homogenize after processing, rolling surface is respectively planed and removed after 8mm, at 440 ℃, start hot rolling, at 230 ℃, stop hot rollings, thereby obtained the hot-rolled sheet that thickness is 5.0mm.In table 2, for the numerical value that departs from condition of the present invention, with underscore, carried out mark.
Secondly, cold rolling (cold rolling rate is 84%) to thickness is 0.8mm, then in the final annealing of 300 ℃ of enforcements 3 hours (rate of heating is 50 ℃/h), thereby it is modified to have made test materials 9～13(: O material).
Comparative example 2
Dissolving has the aluminium alloy (N) of the composition shown in table 2, cast similarly to Example 1, the ingot casting obtaining is carried out at 610 ℃ within 8 hours, homogenize after processing, implement similarly to Example 1 hot rolling, cold rolling, final annealing, thereby it is modified to have made test materials 14(: O material).
Table 2
For the test materials 1～14 being obtained by above-described embodiment 1～3, comparative example 1～2, intermetallic compound distribution number, Work Hardening Characteristic have been assessed in accordance with the following methods.The assessment result of intermetallic compound distribution number, Work Hardening Characteristic is shown in table 3.In table 3, for the numerical value that departs from condition of the present invention, with underscore, carried out mark.
Intermetallic compound distribution number object assessment: be the distribution number of the intermetallic compound of 5～30 μ m for diameter of equivalent circle, carry out quantification by transmission type microscope.By bright field image, measured the number of compound, by the area of measuring region, calculate unit volume (μ m with the thickness of sample of measuring region
3) compound number.The extinction fringe that utilization is arrived at transmission electron microscopy, calculates thickness of sample by the number of striped pattern and the product of extinction distance observed.
Work Hardening Characteristic: as aluminum alloy plate materials of the present invention, although can there is work hardening and hardening in Cold Press Working to approximately 70% degree of finish, but there is explosion trap process zone, in the Cold Press Working of 90% above degree of finish, work hardening becomes difficult material behavior, and, the thickness of the original sheet material before Cold Press Working is made as to T0, thickness after Cold Press Working is made as T1, and Cold Press Working degree R(%)=[(T0-T1)/T0] × 100 o'clock, tensile strength TS70(MPa when R is 70%) and the tensile strength TS90(MPa of R while being 90%) while comparing, there is the characteristic that (TS70-TS90) exceedes 5MPa.
About the assessment of the above-mentioned Work Hardening Characteristic of test materials, that test materials is carried out cold rolling at degree of finish 70% and 90%, for the cold rolling material obtaining, carry out tension test (JIS standard), and then obtain the tensile strength TS70(MPa of degree of finish 70%) and the tensile strength TS90(MPa of degree of finish 90%) poor, i.e. (TS70-TS90), thereby difference is exceeded to being evaluated as of 5MPa, there is work hardening and become difficult characteristic.
Table 3
As shown in table 3, test materials 1～8 of the present invention is all in matrix, to be distributed with 1000/μ m
3above diameter of equivalent circle is compound between the Al-Fe metalloid of 5～30nm, and compared with the tensile strength TS70 that is 70% with cold working degree, at cold working degree, be 90%(explosion trap process zone) tensile strength TS90 reduce by 10～20MPa, thereby there is work hardening, become difficult characteristic.
With respect to this, test materials 9 is because Si amount is many, and it is poor that therefore work hardening becomes difficult characteristic.Test materials 10 is because Fe amount is few, and therefore diameter of equivalent circle is that the distribution number of intermetallic compound of 5～30 μ m is few, and work hardening to become difficult characteristic poor.Test materials 11, because Fe amount is many, therefore generates thick intermetallic compound, and work hardening situation is serious, poor processability.Test materials 12 is because Mn amount is many, and it is poor that therefore work hardening becomes difficult characteristic.Test materials 13 is because Cu amount, Mn amount are many, and therefore work hardening situation is serious, poor processability, and work hardening to become difficult characteristic also poor.Test materials 14 is because the treatment temp that homogenizes is high, and therefore intermetallic compound becomes coarsening, causes Fe solid solution again simultaneously, and it is poor by these impacts, to have been caused work hardening to become difficult characteristic.
Claims (3)
1. lithium-ion battery shell aluminum alloy plate materials, is characterized in that,
By mass%, contain Fe:0.5～2.0%, Si:0.03～0.3%, Cu, Mn, Mg, Zn as impurity are controlled at respectively below 0.10%, surplus consists of Al and inevitable impurity, and in matrix, is distributed with 1000/μ m
3above diameter of equivalent circle is compound between the Al-Fe metalloid of 5～30nm, and, the thickness that the thickness of the original sheet material before Cold Press Working is made as after T0, Cold Press Working is made as T1 and Cold Press Working degree R(%)=[(T0-T1)/T0] × 100 o'clock, tensile strength TS70(MPa when R is 70%) and the tensile strength TS90(MPa of R while being 90%) while comparing, (TS70-TS90) exceed 5MPa.
2. lithium-ion battery shell aluminum alloy plate materials as claimed in claim 1, is characterized in that,
In described aluminum alloy plate materials, by mass%, also contain that Ti:0.20% is following, Zr:0.20% following, Cr:0.30% is with lower one kind or two or more element.
3. lithium-ion battery shell aluminum alloy plate materials as claimed in claim 1 or 2, is characterized in that,
In described aluminum alloy plate materials, by mass%, also contain B:5～100ppm.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2011/065877 WO2013008314A1 (en) | 2011-07-12 | 2011-07-12 | Aluminum alloy plate material for lithium ion battery cases |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103748245A true CN103748245A (en) | 2014-04-23 |
| CN103748245B CN103748245B (en) | 2016-02-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180072252.XA Active CN103748245B (en) | 2011-07-12 | 2011-07-12 | Lithium-ion battery shell aluminum alloy plate materials |
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| WO (1) | WO2013008314A1 (en) |
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| CN106521246A (en) * | 2016-10-10 | 2017-03-22 | 上海华峰新材料研发科技有限公司 | Material for battery shell aluminum alloy explosion-proof valve and manufacturing method thereof |
| CN106566958A (en) * | 2016-11-11 | 2017-04-19 | 安徽四翔铝业有限公司 | High-strength harmonica-shaped tube |
| CN106636767A (en) * | 2016-11-11 | 2017-05-10 | 安徽四翔铝业有限公司 | High-performance harmonica-shaped tube |
| CN108368570A (en) * | 2015-12-25 | 2018-08-03 | 株式会社Uacj | Tank body aluminium alloy plate and its manufacturing method |
| CN110106410A (en) * | 2019-04-22 | 2019-08-09 | 湖南工业大学 | A kind of novel cold stamping technology preparing Al-Cu-Mg alloy shell case and application |
| TWI700377B (en) * | 2018-08-23 | 2020-08-01 | 日商日本輕金屬股份有限公司 | Aluminum alloy plate for battery cover for forming integral explosion-proof valve and manufacturing method thereof |
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| JP6780685B2 (en) * | 2018-09-21 | 2020-11-04 | 日本軽金属株式会社 | Aluminum alloy plate for battery lid for integrated explosion-proof valve molding and its manufacturing method |
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| CN108368570A (en) * | 2015-12-25 | 2018-08-03 | 株式会社Uacj | Tank body aluminium alloy plate and its manufacturing method |
| CN106521246A (en) * | 2016-10-10 | 2017-03-22 | 上海华峰新材料研发科技有限公司 | Material for battery shell aluminum alloy explosion-proof valve and manufacturing method thereof |
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| CN106566958A (en) * | 2016-11-11 | 2017-04-19 | 安徽四翔铝业有限公司 | High-strength harmonica-shaped tube |
| CN106636767A (en) * | 2016-11-11 | 2017-05-10 | 安徽四翔铝业有限公司 | High-performance harmonica-shaped tube |
| TWI700377B (en) * | 2018-08-23 | 2020-08-01 | 日商日本輕金屬股份有限公司 | Aluminum alloy plate for battery cover for forming integral explosion-proof valve and manufacturing method thereof |
| CN110106410A (en) * | 2019-04-22 | 2019-08-09 | 湖南工业大学 | A kind of novel cold stamping technology preparing Al-Cu-Mg alloy shell case and application |
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| WO2013008314A1 (en) | 2013-01-17 |
| CN103748245B (en) | 2016-02-17 |
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