CN102978484A - Al-Fe alloy plate for shell of power battery and preparation method thereof - Google Patents
Al-Fe alloy plate for shell of power battery and preparation method thereof Download PDFInfo
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- CN102978484A CN102978484A CN2012105014374A CN201210501437A CN102978484A CN 102978484 A CN102978484 A CN 102978484A CN 2012105014374 A CN2012105014374 A CN 2012105014374A CN 201210501437 A CN201210501437 A CN 201210501437A CN 102978484 A CN102978484 A CN 102978484A
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- 239000000956 alloy Substances 0.000 title claims abstract description 77
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 75
- 229910018084 Al-Fe Inorganic materials 0.000 title claims abstract description 17
- 229910018192 Al—Fe Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000005098 hot rolling Methods 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003466 welding Methods 0.000 abstract description 9
- 238000005266 casting Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005097 cold rolling Methods 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- 229910000838 Al alloy Inorganic materials 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000010792 warming Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005275 alloying Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229910015136 FeMn Inorganic materials 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Metal Rolling (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention provides an Al-Fe alloy plate for a shell of a power battery and a preparation method thereof. The Al-Fe alloy plate comprises the following components in percentage by mass: 0.9-1.6 percent of Fe, 0.08-0.2 percent of Si and the balance of Al and inevitable impurities, wherein the area ratio of a Fe-containing inter-metallic compound with the internal alloy length of more than 1 mu m is over 5 percent in the plate thickness direction. The preparation method comprises the following steps of: casting a cast ingot, raising the temperature of the cast alloy cast ingot to 560-600 DEG C, keeping the temperature for more than one hour, reducing the temperature to 450-520 DEG C, keeping the temperature for more than two hours, and performing hot rolling; and performing cold rolling on the hot-rolled plate to the required thickness, annealing the obtained cold-rolled plate at the temperature of 350-420 DEG C for more than one hour, and performing air cooling after the plate is annealed, wherein the speed is not more than 100 DEG C per hour during temperature rise or reduction. The alloy plate has excellent mechanical property, pulse laser welding performance and forming property, and the requirements of manufacturing the shell of the power battery are met.
Description
Technical field
The present invention relates to aluminium alloy and preparation method thereof, especially the electromobile lithium ion power cell case belongs to the aluminum alloy processing technology field with Al-Fe alloy sheets and preparation method thereof.
Background technology
State Council is about pointing out in energy-conservation and the new-energy automobile industrial development planning (2012-2020), drive as the main strategic orientation that new-energy automobile develops and automotive industry makes the transition take pure electricity, current emphasis advances pure electric automobile and plug-in hybrid-power automobile industrialization.By 2015, pure electric automobile and plug-in hybrid-power automobile accumulative total volume of production and marketing strove reaching 500,000; To the year two thousand twenty, pure electric automobile and plug-in hybrid-power automobile throughput reach 2,000,000, add up volume of production and marketing above 5,000,000.Pure electric automobile and plug-in hybrid-power automobile substantially all use lithium ion battery as propulsion source.
Be specifically designed at present the aluminium alloy that the electromobile casing of lithium ion battery uses and still be in the research and development initial period.For the consideration of alloy reliability, the current driving force battery case is widely used AA1050 and AA3003 alloy.But above-mentioned alloy has certain problem: (1) material is softer, is subjected to easily to cause faucal and plane deformation after external force collision or the extruding in packing and transportation; (2) Laser Welding is prone to pore, and gas leakage quality fraction defective is higher.
Number of patent application be 200880123084.0 Patent Application Publication a kind of pulse laser welding aluminum alloy material and battery case, in the A1000 line aluminium alloy by be controlled at Ti content below the 0.1wt%, B content is controlled at below the 6ppm, can prevent the formation of local anomaly weldpool when pulsed laser welding.
Number of patent application be 201110083279.0 Patent Application Publication a kind of aluminum alloy plate for battery box and cell box distributes by the intermetallic compound in the element adjustment restriction alloy, makes sheet material have preferably stamping performance and laser weldability.But the weldpool homogeneity is not done requirement.
By the understanding to power lithium-ion battery manufacturers, for raising ride safety of automobile angle, and the battery increase-volume need to have the higher and better aluminum alloy plate materials of laser weldability of intensity to the requirement of shell attenuate.
Aluminium alloy is to the high-reflectivity of laser and the high thermal conductivity of self, so that aluminium alloy needs higher energy density for obtaining darker weldpool when laser welding.High-energy-density laser also can bring disadvantageous effect when increasing fusion penetration, namely the weldpool homogeneity can descend.In addition, in order to improve the intensity of aluminium alloy, the adding of reinforced alloys element also can be unfavorable for the laser weldability of alloy.
How when improving intensity of aluminum alloy, keeps good laser weldability, especially pulse laser weldpool homogeneity is a critical problem that runs into during current power battery case is developed with aluminum alloy materials.
Summary of the invention
The purpose of this invention is to provide a kind of power battery case Al-Fe alloy sheets and preparation method thereof, the sheet alloy of preparation has good mechanical property, pulsed laser welding performance (weldpool has good uniformity) and stamping performance, can satisfy the requirement of power battery case.
Purpose of the present invention is achieved through the following technical solutions:
A kind of power battery case Al-Fe alloy sheets, the quality percentage composition of its composition is: Fe:0.9 ~ 1.6wt%, Si:0.08 ~ 0.2wt%, surplus is Al and inevitable impurity; In sheet metal thickness direction alloy length greater than the area occupation ratio that contains the Fe intermetallic compound of 1 μ m more than 5%.
Further, above-mentioned a kind of power battery case Al-Fe alloy sheets, described alloying constituent also contains: at least a element among the Mg below Cu, the 0.5wt% below Mn, the 0.5wt% below the 0.6wt%; In sheet metal thickness direction alloy length greater than the area occupation ratio that contains the Fe intermetallic compound of 1 μ m more than 5%.
Further, above-mentioned a kind of power battery case Al-Fe alloy sheets, described alloying constituent also contains: at least a element in Ti, the B element, and total content is less than 0.1wt%; In sheet metal thickness direction alloy length greater than the area occupation ratio that contains the Fe intermetallic compound of 1 μ m more than 5%.
A kind of power battery case is with the preparation method of Al-Fe alloy sheets, and at first founding goes out ingot casting, and the alloy cast ingot that founding is gone out is warmed up to more than 560 ~ 600 ℃ of insulation 1h, cools to 450 ~ 520 ℃ and be incubated more than the 2h again, then carries out hot rolling; Hot-rolled sheet is cold rolled to needs thickness, to the cold-reduced sheet that obtains more than 350 ~ 420 ℃ of annealing 1h, air cooling after the sheet material annealing; Wherein, heat up or the speed during cooling is not higher than 100 ℃/h.
The substantive distinguishing features that technical solution of the present invention is outstanding and significant progressive being mainly reflected in:
1. by the control alloying constituent, adopt the science preparation method, the Fe intermetallic compound area occupation ratio that contains in the Al-Fe alloy is reached more than 5%; Contain increasing of Fe intermetallic compound quantity, improve sheet alloy to the specific absorption of laser, so that the weldpool fusion penetration has guaranteed the homogeneity of weldpool when increasing;
2. wherein a kind of adding of element of Mn, Mg, Cu can increase the solid solubility of alloy, improves the compressive strength of alloy strength and battery case; And the adding of Mn can form Al(FeMn with Fe, Si) the Si compound, increase compound quantity;
3. the sheet alloy of preparation has good mechanical property, pulsed laser welding performance (weldpool has good uniformity) and stamping performance, can satisfy the requirement of power battery case.
Embodiment
The Al-Fe alloy phase has higher mechanical property for the 1xxx alloy, and laser weldability is suitable.Mn, Mg, Cu be a kind of adding of element wherein, can increase the solid solubility of alloy, improves the compressive strength of alloy strength and battery case.And the adding of Mn can form Al(FeMn with Fe, Si) the Si compound, increase compound quantity.
By the control alloying constituent, adopt the science preparation method, the Fe intermetallic compound area occupation ratio that contains in the Al-Fe alloy is reached more than 5%.Contain increasing of Fe intermetallic compound quantity, improve sheet alloy to the specific absorption of laser, so that the weldpool fusion penetration has guaranteed the homogeneity of weldpool when increasing.Contain Fe intermetallic compound area occupation ratio hour in the alloy, not obvious on the specific absorption impact that improves laser; When area occupation ratio was too much, thick compound is many can to increase the sheet material forming tearing tendency.Preferable range is 7 ~ 17%.
Fe: can form intermetallic compound with the element of Al, Mn, Si, increase the quantity that contains the Fe intermetallic compound.When Fe content was low, the contribution of alloy intensity was inadequate, and compound comparatively small amt in the alloy.When Fe content is too much, can form thick intermetallic compound, be unfavorable for the performance of sheet material.Preferable range is 0.9 ~ 1.39wt%.
Si: solid solution is conducive to improve the intensity of sheet material in alloy, also is conducive to the increase of compound quantity.The control of Si content is lower, can increase manufacturing cost.Si content is too much, and it is unfavorable that alloy is shaped, and also can worsen the laser weldability of alloy.Preferable range is 0.08 ~ 0.2wt%.
Mn: solid solution is conducive to improve intensity or the creep properties of sheet material in alloy, can form intermetallic compound with the element of Al, Fe, Si, increases the quantity that contains the Fe intermetallic compound.During the Mn too high levels, easily form thick intermetallic compound, be unfavorable for the performance of alloy.Below the preferable range 0.6wt%.
Cu: be conducive to carry heavy alloyed intensity or creep properties.During the Cu too high levels, can make welding crack produce tendency and increase.Preferable range is below the 0.5wt%.
Mg: be conducive to put forward heavy alloyed intensity and plasticity.During the Mg too high levels, splash in the time of can causing laser welding and increase, affect the homogeneity of weldpool.Preferable range is below the 0.5wt%.
Ti, B: can crystal grain thinning, suppress casting crack.When content is too much, laser weldability can be affected, manufacturing cost can be increased simultaneously.
The ingot homogenization technique of alloy sheets of the present invention is: ingot casting is warmed up to more than 560 ~ 600 ℃ of insulation 1h, cools to 450 ~ 520 ℃ and be incubated more than the 2h again, then carry out hot rolling, the speed when heating or cooling is not higher than 100 ℃/h.Heat tracing in 560 ~ 600 ℃ of scopes can make intermetallic compound fusing fully, reduces the quantity of large size intermetallic compound.Not to be higher than 100 ℃ speed cooling, be conducive to contain separating out of Fe intermetallic compound, increase the quantity that contains the Fe intermetallic compound.Homogenization temperature is lower, and the compound fusing that forms in the castingprocesses is insufficient; Excess Temperature is prone to thick compound.Soaking time is short, is unfavorable for the fusing of compound or separates out.Heat up or rate of temperature fall when too fast, be unfavorable for too the fusing of compound or separate out.
Embodiment 1
Founding go out table 1 to alloy 1
#, alloy cast ingot is warming up to 580 ℃ and be incubated 2h with the temperature rise rate of 50 ℃/h from room temperature, the speed with 50 ℃/h cools to 490 ℃ of insulation 2h again, then carries out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, cold-reduced sheet is warmed up to air cooling behind 380 ℃ of insulation 1h with the speed of 30 ℃/h, finally obtain the sheet material that needs.
Embodiment 2
Founding go out table 1 to alloy 2
#, alloy cast ingot is warming up to 560 ℃ and be incubated 4h with the temperature rise rate of 60 ℃/h from room temperature, the speed with 60 ℃/h cools to 450 ℃ of insulation 2h again, then carries out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, cold-reduced sheet is warmed up to air cooling behind 350 ℃ of insulation 2h with the speed of 30 ℃/h, finally obtain the sheet material that needs.
Embodiment 3
Founding go out table 1 to alloy 3
#, alloy cast ingot is warming up to 590 ℃ and be incubated 1h with the temperature rise rate of 40 ℃/h from room temperature, the speed with 40 ℃/h cools to 480 ℃ of insulation 2h again, then carries out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, cold-reduced sheet is warmed up to air cooling behind 380 ℃ of insulation 1h with the speed of 30 ℃/h, finally obtain the sheet material that needs.Cold-reduced sheet is warmed up to air cooling behind 420 ℃ of insulation 1h with the speed of 30 ℃/h, finally obtains the sheet material that needs.
Embodiment 4
Founding go out table 1 to alloy 4
#, alloy cast ingot is warming up to 600 ℃ and be incubated 1h with the temperature rise rate of 50 ℃/h from room temperature, the speed with 20 ℃/h cools to 520 ℃ of insulation 2h again, then carries out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, cold-reduced sheet is warmed up to air cooling behind 380 ℃ of insulation 1h with the speed of 30 ℃/h, finally obtain the sheet material that needs.
Comparative example 1
Founding go out table 1 to alloy 5
#, alloy cast ingot is warming up to 580 ℃ and be incubated 2h with the temperature rise rate of 50 ℃/h from room temperature, the speed with 50 ℃/h cools to 490 ℃ of insulation 2h again, then carries out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, cold-reduced sheet is warmed up to air cooling behind 380 ℃ of insulation 1h with the speed of 30 ℃/h, finally obtain the sheet material that needs.
Comparative example 2
Founding go out table 1 to alloy 6
#, alloy cast ingot is warming up to 580 ℃ and be incubated 2h with the temperature rise rate of 50 ℃/h from room temperature, the speed with 50 ℃/h cools to 490 ℃ of insulation 2h again, then carries out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, cold-reduced sheet is warmed up to air cooling behind 380 ℃ of insulation 1h with the speed of 30 ℃/h, finally obtain the sheet material that needs.
Comparative example 3
Founding go out table 1 to alloy 7
#, alloy cast ingot is warming up to 580 ℃ and be incubated 2h with the temperature rise rate of 50 ℃/h from room temperature, the speed with 50 ℃/h cools to 490 ℃ of insulation 2h again, then carries out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, cold-reduced sheet is warmed up to air cooling behind 380 ℃ of insulation 1h with the speed of 30 ℃/h, finally obtain the sheet material that needs.
Comparative example 4
Founding go out table 1 to alloy 8
#, alloy cast ingot is warming up to 580 ℃ and be incubated 2h with the temperature rise rate of 50 ℃/h from room temperature, the speed with 50 ℃/h cools to 490 ℃ of insulation 2h again, then carries out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, cold-reduced sheet is warmed up to air cooling behind 380 ℃ of insulation 1h with the speed of 30 ℃/h, finally obtain the sheet material that needs.
Comparative example 5
Founding go out table 1 to alloy 9
#, alloy cast ingot is warming up to 620 ℃ and be incubated 0.5h with the temperature rise rate of 150 ℃/h from room temperature, the speed with 150 ℃/h cools to 490 ℃ of insulation 0.1h again, then carries out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, cold-reduced sheet is warmed up to air cooling behind 380 ℃ of insulation 1h with the speed of 30 ℃/h, finally obtain the sheet material that needs.
Table 1 has provided chemical ingredients and the homogenization process parameter of several embodiment and comparative example alloy.
Table 1
Table 2 has provided and has contained Fe intermetallic compound area occupation ratio, mechanical property and pulsed laser welding results of property in several embodiment and the comparative example alloy.
Table 2
Remarks: 1) by observation by light microscope weldpool surface, weldpool does not have be " O " of crackle, and what crackle occured is " * ";
2) by observation by light microscope weldpool surface, that weldpool has good uniformity is " O ", and that general is " △ ", and poor is " * ";
3) by observation by light microscope weldpool cross section, the weldpool degree of depth is " O " greater than 300 μ m's, less than 300 μ m greater than 140 μ m be " △ ", less than 140 μ m is " * ".
Can be compared by table 1 and table 2, the present invention adopts the science preparation method by the control alloying constituent, on the basis that guarantees the alloy higher-strength, has improved the laser weldability of alloy.
Below only be concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the rights protection scope of the present invention.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103361521A (en) * | 2013-07-22 | 2013-10-23 | 苏州有色金属研究院有限公司 | Aluminium alloy plate with excellent laser welding performance and preparation method thereof |
JP2014227590A (en) * | 2013-05-25 | 2014-12-08 | 株式会社Uacj | Aluminum alloy sheet for cell case |
CN106536772A (en) * | 2014-07-09 | 2017-03-22 | 海德鲁铝业钢材有限公司 | Use of an aluminium alloy or of an aluminium sheet product made from an alloy of this type for an aluminium-plastic composite part |
CN107400807A (en) * | 2017-07-25 | 2017-11-28 | 杨仲彬 | A kind of power battery case aluminium alloy and its processing method |
CN110709525A (en) * | 2017-12-05 | 2020-01-17 | 日本轻金属株式会社 | Aluminum alloy plate for battery cover for forming integrated explosion-proof valve and manufacturing method thereof |
CN111500899A (en) * | 2020-04-23 | 2020-08-07 | 江苏常铝铝业集团股份有限公司 | Aluminum material containing rare earth elements for explosion-proof membrane and manufacturing method thereof |
EP3842559A4 (en) * | 2018-08-23 | 2022-06-08 | Nippon Light Metal Company, Ltd. | ALUMINUM ALLOY SHEET FOR BATTERY COVER FOR FORMING AN INTEGRATED EXPLOSION-PROOF VALVE AND METHOD OF MANUFACTURE THEREOF |
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JP2014227590A (en) * | 2013-05-25 | 2014-12-08 | 株式会社Uacj | Aluminum alloy sheet for cell case |
CN103361521B (en) * | 2013-07-22 | 2015-08-12 | 苏州有色金属研究院有限公司 | There is aluminium alloy plate of excellent laser weldability and preparation method thereof |
CN103361521A (en) * | 2013-07-22 | 2013-10-23 | 苏州有色金属研究院有限公司 | Aluminium alloy plate with excellent laser welding performance and preparation method thereof |
US10792892B2 (en) | 2014-07-09 | 2020-10-06 | Hydro Aluminium Rolled Products Gmbh | Use of an aluminium alloy or of an aluminium flat product made from an alloy of this type for an aluminium-plastic composite part |
CN106536772A (en) * | 2014-07-09 | 2017-03-22 | 海德鲁铝业钢材有限公司 | Use of an aluminium alloy or of an aluminium sheet product made from an alloy of this type for an aluminium-plastic composite part |
CN111893349A (en) * | 2014-07-09 | 2020-11-06 | 海德鲁铝业钢材有限公司 | Application of aluminum alloy or flat aluminum product composed of aluminum alloy to aluminum-plastic composite component |
CN107400807A (en) * | 2017-07-25 | 2017-11-28 | 杨仲彬 | A kind of power battery case aluminium alloy and its processing method |
CN113174514A (en) * | 2017-12-05 | 2021-07-27 | 日本轻金属株式会社 | Aluminum alloy plate for battery cover for forming integrated explosion-proof valve and manufacturing method thereof |
CN110709525A (en) * | 2017-12-05 | 2020-01-17 | 日本轻金属株式会社 | Aluminum alloy plate for battery cover for forming integrated explosion-proof valve and manufacturing method thereof |
CN110709525B (en) * | 2017-12-05 | 2022-02-01 | 日本轻金属株式会社 | Aluminum alloy plate for battery cover for forming integrated circular explosion-proof valve and manufacturing method thereof |
CN113174514B (en) * | 2017-12-05 | 2022-02-18 | 日本轻金属株式会社 | Aluminum alloy plate for battery cover for forming integral explosion-proof valve and manufacturing method thereof |
EP3842559A4 (en) * | 2018-08-23 | 2022-06-08 | Nippon Light Metal Company, Ltd. | ALUMINUM ALLOY SHEET FOR BATTERY COVER FOR FORMING AN INTEGRATED EXPLOSION-PROOF VALVE AND METHOD OF MANUFACTURE THEREOF |
CN111500899A (en) * | 2020-04-23 | 2020-08-07 | 江苏常铝铝业集团股份有限公司 | Aluminum material containing rare earth elements for explosion-proof membrane and manufacturing method thereof |
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