CN102978484B - 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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- CN102978484B CN102978484B CN201210501437.4A CN201210501437A CN102978484B CN 102978484 B CN102978484 B CN 102978484B CN 201210501437 A CN201210501437 A CN 201210501437A CN 102978484 B CN102978484 B CN 102978484B
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- 239000000956 alloy Substances 0.000 title claims abstract description 70
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 68
- 229910018084 Al-Fe Inorganic materials 0.000 title claims abstract description 14
- 229910018192 Al—Fe Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000005098 hot rolling Methods 0.000 claims abstract description 13
- 238000005266 casting Methods 0.000 claims abstract description 6
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000009413 insulation Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- 238000005275 alloying Methods 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003466 welding Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005097 cold rolling Methods 0.000 abstract 1
- 229910000838 Al alloy Inorganic materials 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 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
- 230000035515 penetration Effects 0.000 description 3
- 238000001556 precipitation Methods 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011148 porous material Substances 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
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 electromobile lithium ion power cell case Al-Fe alloy sheets and preparation method thereof, belongs to aluminum alloy processing technology field.
Background technology
State Council about energy-conservation with new-energy automobile industrial development planning (2012-2020) in point out, with the main strategic orientation that pure electric drive makes the transition for new-energy automobile development and automotive industry, current emphasis advances pure electric automobile and plug-in hybrid-power automobile industrialization.By 2015, pure electric automobile and plug-in hybrid-power automobile add up 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 more than 5,000,000.Pure electric automobile and plug-in hybrid-power automobile substantially all use lithium ion battery as propulsion source.
The aluminium alloy being specifically designed to lithium ion battery of electric automobile shell at present is still in out research and development initial period.For the consideration of alloy reliability, current driving force battery case widely uses AA1050 and AA3003 alloy.But above-mentioned alloy has certain problem: (1) material is softer, collide by external force in packaging and transportation or easily cause faucal and plane deformation after extruding; (2) easily there is pore in Laser Welding, and gas leakage quality fraction defective is higher.
Number of patent application be 200880123084.0 application discloses a kind of pulse laser welding aluminum alloy material and battery case, by being controlled by Ti content to control at below 6ppm at below 0.1wt%, B content in A1000 line aluminium alloy, the formation of the local anomaly weldpool when pulsed laser welding can be prevented.
Number of patent application be 201110083279.0 application discloses a kind of aluminum alloy plate for battery box and cell box, by element adjustment restriction alloy in intermetallic compound distribution, make sheet material have good stamping formabilily and laser weldability.But no requirement is not done to weldpool homogeneity.
By the understanding to power lithium-ion battery manufacturers, for raising vehicle safety angle, and battery increase-volume is to the thinning requirement of shell, and needing the higher and laser welding of intensity can better aluminum alloy plate materials.
Aluminium alloy, to the high-reflectivity of laser and the high thermal conductivity of self, makes aluminium alloy be obtain darker weldpool to need higher energy density when laser welding.High energy density laser is while increase fusion penetration, and also can bring disadvantageous effect, namely weldpool homogeneity can decline.In addition, in order to improve the intensity of aluminium alloy, reinforced alloys element add the laser weldability that also can be unfavorable for alloy.
How while raising intensity of aluminum alloy, keeping good laser weldability, especially pulse laser weldpool homogeneity, is the critical problem run in the exploitation of current power battery case aluminum alloy materials.
Summary of the invention
The object of this invention is to provide a kind of Al-Fe alloy plate for shell of power battery and preparation method thereof, the sheet alloy of preparation has good mechanical property, pulsed laser welding performance (weldpool has good uniformity) and stamping formabilily, can meet the requirement of power battery case.
Object of the present invention is achieved through the following technical solutions:
A kind of Al-Fe alloy plate for shell of power battery, the mass percentage of its composition is: Fe:0.9 ~ 1.6wt%, Si:0.08 ~ 0.2wt%, and surplus is Al and inevitable impurity; In the alloy of sheet metal thickness direction, length is greater than the area occupation ratio containing Fe intermetallic compound of 1 μm more than 5%.
Further, above-mentioned a kind of Al-Fe alloy plate for shell of power battery, described alloying constituent also contains: at least one element in the Mg of the Mn of below 0.6wt%, the Cu of below 0.5wt%, below 0.5wt%; In the alloy of sheet metal thickness direction, length is greater than the area occupation ratio containing Fe intermetallic compound of 1 μm more than 5%.
Further, above-mentioned a kind of Al-Fe alloy plate for shell of power battery, described alloying constituent also contains: at least one element in Ti, B element, and total content is less than 0.1wt%; In the alloy of sheet metal thickness direction, length is greater than the area occupation ratio containing Fe intermetallic compound of 1 μm more than 5%.
A preparation method for Al-Fe alloy plate for shell of power battery, first founding goes out ingot casting, is warmed up to 560 ~ 600 DEG C of insulation more than 1h, then cools to 450 ~ 520 DEG C and be incubated more than 2h, then carry out hot rolling to the alloy cast ingot that founding goes out; Hot-rolled sheet is cold rolled to and needs thickness, to the cold-reduced sheet obtained at 350 ~ 420 DEG C of annealing more than 1h, air cooling after sheet material annealing; Wherein, speed when intensification or cooling is not higher than 100 DEG C/h.
The substantive distinguishing features that technical solution of the present invention is outstanding and significant progress are mainly reflected in:
1. by controlling alloying constituent, adopting science preparation method, making the Fe intermetallic compound area occupation ratio that contains in Al-Fe alloy reach more than 5%; Containing increasing of Fe intermetallic compound quantity, improve sheet alloy to the specific absorption of laser, while weldpool fusion penetration is increased, ensure that the homogeneity of weldpool;
2. Mn, Mg, Cu wherein the adding of a kind of element, the solid solubility of alloy can be increased, improve the compressive strength of alloy strength and battery case; And adding of Mn can form Al(FeMn with Fe, Si) Si compound, increase compound amounts;
3. the sheet alloy prepared has good mechanical property, pulsed laser welding performance (weldpool has good uniformity) and stamping formabilily, can meet the requirement of power battery case.
Embodiment
Al-Fe alloy phase has higher mechanical property for 1xxx alloy, and laser weldability is suitable.Mn, Mg, Cu wherein the adding of a kind of element, the solid solubility of alloy can be increased, improve the compressive strength of alloy strength and battery case.And adding of Mn can form Al(FeMn with Fe, Si) Si compound, increase compound amounts.
By controlling alloying constituent, adopting science preparation method, making the Fe intermetallic compound area occupation ratio that contains in Al-Fe alloy reach more than 5%.Containing increasing of Fe intermetallic compound quantity, improve sheet alloy to the specific absorption of laser, while weldpool fusion penetration is increased, ensure that the homogeneity of weldpool.Containing Fe intermetallic compound area occupation ratio hour in alloy, not obvious on the specific absorption impact improving laser; When area occupation ratio is too much, thick compound is many can increase sheet material forming tearing tendency.Preferable range is 7 ~ 17%.
Fe: can form intermetallic compound with the element of Al, Mn, Si, increases the quantity containing Fe intermetallic compound.When Fe content is lower, alloy intensity contribution is inadequate, and in alloy, compound amounts is less.When Fe content is too much, thick intermetallic compound can be formed, be unfavorable for the performance of sheet material.Preferable range is 0.9 ~ 1.39wt%.
Si: be solid-solution in alloy the intensity being conducive to improving sheet material, be also conducive to the increase of compound amounts.Si content controls 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: be solid-solution in alloy the intensity or creep properties that are conducive to improving sheet material, intermetallic compound can be formed with the element of Al, Fe, Si, increase the quantity containing Fe intermetallic compound.During Mn too high levels, easily form thick intermetallic compound, be unfavorable for the performance of alloy.Below preferable range 0.6wt%.
Cu: be conducive to carrying heavy alloyed intensity or creep properties.During Cu too high levels, welding crack can be made to produce tendency and to increase.Preferable range is below 0.5wt%.
Mg: be conducive to putting forward heavy alloyed intensity and plasticity.During Mg too high levels, splash when can cause laser welding and increase, affect the homogeneity of weldpool.Preferable range is below 0.5wt%.
Ti, B: can crystal grain thinning, suppress casting crack.When content is too much, can laser weldability be affected, can manufacturing cost be increased simultaneously.
The ingot homogenization technique of alloy sheets of the present invention is: ingot casting is warmed up to 560 ~ 600 DEG C of insulation more than 1h, then cools to 450 ~ 520 DEG C and be incubated more than 2h, then carry out hot rolling, speed when heating or cooling is not higher than 100 DEG C/h.Heating and thermal insulation within the scope of 560 ~ 600 DEG C, can make intermetallic compound fuse fully, reduce the quantity of large size intermetallic compound.With the speed cooling not higher than 100 DEG C, be conducive to the precipitation containing Fe intermetallic compound, increase the quantity containing Fe intermetallic compound.Homogenization temperature is lower, and the compound fusing formed in castingprocesses is insufficient; Temperature is too high, easily occurs coarsening compound.Soaking time is short, is unfavorable for fusing or the precipitation of compound.Heat up or rate of temperature fall too fast time, be unfavorable for fusing or the precipitation of compound too.
embodiment 1
Founding go out table 1 to alloy 1
#, alloy cast ingot is incubated 2h with the temperature rise rate of 50 DEG C/h from room temperature to 580 DEG C, then cools to 490 DEG C of insulation 2h with the speed of 50 DEG C/h, then carry out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, to cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 380 DEG C of insulation 1h, finally obtains the sheet material needed.
embodiment 2
Founding go out table 1 to alloy 2
#, alloy cast ingot is incubated 4h with the temperature rise rate of 60 DEG C/h from room temperature to 560 DEG C, then cools to 450 DEG C of insulation 2h with the speed of 60 DEG C/h, then carry out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, to cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 350 DEG C of insulation 2h, finally obtains the sheet material needed.
embodiment 3
Founding go out table 1 to alloy 3
#, alloy cast ingot is incubated 1h with the temperature rise rate of 40 DEG C/h from room temperature to 590 DEG C, then cools to 480 DEG C of insulation 2h with the speed of 40 DEG C/h, then carry out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, to cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 380 DEG C of insulation 1h, finally obtains the sheet material needed.To cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 420 DEG C of insulation 1h, finally obtain the sheet material needed.
embodiment 4
Founding go out table 1 to alloy 4
#, alloy cast ingot is incubated 1h with the temperature rise rate of 50 DEG C/h from room temperature to 600 DEG C, then cools to 520 DEG C of insulation 2h with the speed of 20 DEG C/h, then carry out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, to cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 380 DEG C of insulation 1h, finally obtains the sheet material needed.
comparative example 1
Founding go out table 1 to alloy 5
#, alloy cast ingot is incubated 2h with the temperature rise rate of 50 DEG C/h from room temperature to 580 DEG C, then cools to 490 DEG C of insulation 2h with the speed of 50 DEG C/h, then carry out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, to cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 380 DEG C of insulation 1h, finally obtains the sheet material needed.
comparative example 2
Founding go out table 1 to alloy 6
#, alloy cast ingot is incubated 2h with the temperature rise rate of 50 DEG C/h from room temperature to 580 DEG C, then cools to 490 DEG C of insulation 2h with the speed of 50 DEG C/h, then carry out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, to cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 380 DEG C of insulation 1h, finally obtains the sheet material needed.
comparative example 3
Founding go out table 1 to alloy 7
#, alloy cast ingot is incubated 2h with the temperature rise rate of 50 DEG C/h from room temperature to 580 DEG C, then cools to 490 DEG C of insulation 2h with the speed of 50 DEG C/h, then carry out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, to cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 380 DEG C of insulation 1h, finally obtains the sheet material needed.
comparative example 4
Founding go out table 1 to alloy 8
#, alloy cast ingot is incubated 2h with the temperature rise rate of 50 DEG C/h from room temperature to 580 DEG C, then cools to 490 DEG C of insulation 2h with the speed of 50 DEG C/h, then carry out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, to cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 380 DEG C of insulation 1h, finally obtains the sheet material needed.
comparative example 5
Founding go out table 1 to alloy 9
#, alloy cast ingot is incubated 0.5h with the temperature rise rate of 150 DEG C/h from room temperature to 620 DEG C, then cools to 490 DEG C of insulation 0.1h with the speed of 150 DEG C/h, then carry out hot rolling; Again hot-rolled sheet is cold rolled to 1.3mm thickness, to cold-reduced sheet with air cooling after the ramp of 30 DEG C/h to 380 DEG C of insulation 1h, finally obtains the sheet material needed.
Table 1 gives chemical composition and the homogenization process parameter of several embodiment and comparative example alloy.
Table 1
Table 2 gives in several embodiment and comparative example alloy containing Fe intermetallic compound area occupation ratio, mechanical property and pulsed laser welding results of property.
Table 2
Remarks: 1) by observation by light microscope weldpool surface, that weldpool does not have crackle is " O ", and what crackle occurred 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 be greater than 300 μm for " O ", be less than 300 μm be greater than 140 μm be " △ ", be less than 140 μm be "×".
Can be compared by table 1 and table 2, the present invention, by controlling alloying constituent, adopts science preparation method, on the basis ensureing alloy higher-strength, improves the laser weldability of alloy.
Below be only embody rule example of the present invention, protection scope of the present invention is not constituted any limitation.The technical scheme that all employing equivalents or equivalence are replaced and formed, all drops within rights protection scope of the present invention.
Claims (1)
1. a preparation method for Al-Fe alloy plate for shell of power battery, it is characterized in that the mass percentage of its composition is: Fe:0.9 ~ 1.6wt%, Si:0.08 ~ 0.2wt%, surplus is Al and inevitable impurity; Described alloying constituent also contains: at least one element in the Mg of the Mn of below 0.6wt%, the Cu of below 0.5wt%, below 0.5wt%; Described alloying constituent also contains: at least one element in Ti, B element, and total content is less than 0.1wt%; In the alloy of sheet metal thickness direction, length is greater than the area occupation ratio containing Fe intermetallic compound of 1 μm more than 5%; First founding goes out ingot casting, is warmed up to 560 ~ 600 DEG C of insulation more than 1h, then cools to 450 ~ 520 DEG C and be incubated more than 2h, then carry out hot rolling to the alloy cast ingot that founding goes out; Hot-rolled sheet is cold rolled to and needs thickness, to the cold-reduced sheet obtained at 350 ~ 420 DEG C of annealing more than 1h, air cooling after sheet material annealing; Wherein, speed when intensification or cooling is not higher than 100 DEG C/h.
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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 |
| EP3167089B1 (en) * | 2014-07-09 | 2017-12-06 | Hydro Aluminium Rolled Products GmbH | The use of an aluminium alloy, in particular an aluminium flat product of this alloy for an aluminum-polymer composite |
| CN107400807A (en) * | 2017-07-25 | 2017-11-28 | 杨仲彬 | A kind of power battery case aluminium alloy and its processing method |
| JP6780664B2 (en) * | 2017-12-05 | 2020-11-04 | 日本軽金属株式会社 | Aluminum alloy plate for battery lid for molding of integrated circular explosion-proof valve and its manufacturing method |
| JP6614293B1 (en) * | 2018-08-23 | 2019-12-04 | 日本軽金属株式会社 | Aluminum alloy plate for battery lid for integral explosion-proof valve molding and manufacturing method thereof |
| CN111500899B (en) * | 2020-04-23 | 2022-03-04 | 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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| JP2008111159A (en) * | 2006-10-31 | 2008-05-15 | Sumitomo Light Metal Ind Ltd | Aluminum alloy sheet for battery case and manufacturing method therefor |
| JP5019374B2 (en) * | 2007-08-29 | 2012-09-05 | 住友軽金属工業株式会社 | Aluminum alloy plate for battery case lid with excellent laser weldability |
| KR101321666B1 (en) * | 2011-02-01 | 2013-10-23 | 가부시키가이샤 고베 세이코쇼 | Alluminum alloy plate for battery case and battery case |
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Effective date of registration: 20170930 Address after: 471000 Henan Province, Luoyang city high tech Development Zone middle Ling Road Patentee after: China Nonferrous Metals Processing Technology Co., Ltd. Address before: Suzhou City, Jiangsu Province, Shen Hu Road Park 215021 No. 200 Patentee before: Suzhou Non-ferrous Metal academy Co., Ltd. |