WO2019214243A1 - Feuille d'aluminium en alliage 1100 pour batterie au lithium et sa méthode de fabrication - Google Patents

Feuille d'aluminium en alliage 1100 pour batterie au lithium et sa méthode de fabrication Download PDF

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Publication number
WO2019214243A1
WO2019214243A1 PCT/CN2018/122457 CN2018122457W WO2019214243A1 WO 2019214243 A1 WO2019214243 A1 WO 2019214243A1 CN 2018122457 W CN2018122457 W CN 2018122457W WO 2019214243 A1 WO2019214243 A1 WO 2019214243A1
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WIPO (PCT)
Prior art keywords
aluminum foil
lithium battery
rolling
alloy
thickness
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PCT/CN2018/122457
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English (en)
Chinese (zh)
Inventor
张全成
袁婷
章建华
吴永新
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江苏常铝铝业股份有限公司
常熟理工学院
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Application filed by 江苏常铝铝业股份有限公司, 常熟理工学院 filed Critical 江苏常铝铝业股份有限公司
Publication of WO2019214243A1 publication Critical patent/WO2019214243A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • 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

Definitions

  • the present application relates to an aluminum foil and a method of manufacturing the same, and more particularly to a 1100 alloy aluminum foil for a lithium battery and a method of manufacturing the same.
  • the aluminum foil for lithium battery requires high dimensional accuracy, a clean surface, uniformity, and scratch-free defects, balanced plate shape, extremely thin thickness, and high tensile strength and elongation.
  • the aluminum foil for lithium battery is currently used as the pure aluminum alloy grades such as 1070, 1235 and 1200. The thickness is usually 12 to 25 ⁇ m and is delivered in the H18 state. The tensile strength is generally only close to 200 MPa, and the elongation of the high elongation product is high.
  • the surface of the aluminum foil is more oily, the surface wetting tension can only be maintained within 30 dyne, and the yield is low.
  • the aluminum foil for lithium batteries is gradually thinned, the need for tensile strength, elongation and surface quality is also increased.
  • the aluminum foil for the existing lithium battery can satisfy the requirement of thinning while satisfying the aluminum content of 99%, and therefore many products are currently added with alloying elements to improve the mechanical properties.
  • the aluminum foil products for batteries have higher requirements on electrical conductivity due to the particularity of their performance requirements. At present, the strengthening mechanism of aluminum alloy solid solution, fine crystal and work hardening is harmful to its electrical conductivity.
  • the object of the present application is to provide a 1100 alloy aluminum foil for a lithium battery, which can effectively improve tensile strength and elongation while maintaining high electrical conductivity while thinning aluminum foil for lithium battery. And high surface quality.
  • Another object of the present application is to provide a method for producing a 1100 alloy aluminum foil for a lithium battery.
  • a 1100 alloy aluminum foil for a lithium battery comprises the following mass percentage components: Fe: 0.4 to 0.5%, Si: 0.1 to 0.2%, Cu: 0.1 to 0.15%, Ti: 0.01 to 0.02%, Sc: 0.03 to 0.07%, Ce: 0.03 to 0.07%, Mn: ⁇ 0.01%, Mg: ⁇ 0.005%, Zn: ⁇ 0.005%, and Al ⁇ 99.1%, wherein Fe+Si ⁇ 0.65%, Fe/ Si is 2.0 to 4.0.
  • the 1100 alloy aluminum foil for lithium battery has a thickness of 0.008 to 0.015 mm, a tensile strength of 220 to 260 MPa, and an elongation of 3 to 5%.
  • the invention relates to a method for manufacturing a 1100 alloy aluminum foil for a lithium battery, comprising the following process steps: (1) smelting: adding raw materials of each element to a melting furnace according to the composition of the alloy, and smelting to obtain an alloy ingot; (2) Hot rolling: after milling, the alloy ingot is hot rolled to obtain a hot rolled billet; (3) rough rolling: the hot rolled billet described in the step (2) is placed on a cold rolling mill for cold rough rolling to obtain a coarse (4) recrystallization annealing: intermediate recrystallization annealing of the rough rolling billet to obtain a recrystallized and annealed rolled sheet; (5) medium rolling: further cold rolling of the recrystallization annealing sheet Obtaining an aluminum foil roll; (6) stress relief annealing: performing intermediate stress relief annealing on the intermediate rolled aluminum foil roll; (7) performing cold finishing rolling on the intermediate stress relief annealed aluminum foil roll to a lithium battery The required thickness of the aluminum foil is then cut into aluminum foil
  • the smelting preparation conditions are: a smelting temperature of 750 to 780 ° C, a refining temperature of 740 to 760 ° C, and a casting temperature of 695 to 705 ° C.
  • the thickness of the hot rolled billet is 6.5 to 8.5 mm.
  • the rough rolling stock has a thickness of 2.0 to 2.8 mm.
  • the temperature during recrystallization annealing is 400 to 430 ° C, and the holding time is 9 to 12 hours.
  • the thickness of the aluminum foil roll is 0.4 to 0.6 mm.
  • the temperature during the stress relief annealing is 210 to 230 ° C, and the holding time is 12 to 15 hours.
  • the application has the advantages that the present application controls the Fe and Si contents, so that the second phase is mainly in the form of ⁇ (Al 3 Fe 3 Si) phase, the addition has a certain strengthening effect, and the conductivity is It damages the smaller Cu element and increases the two rare earth elements, Sc and Ce.
  • the rare earth-containing second phase Al 3 Sc and Al 11 Ce 3 can strengthen the grain boundary and inhibit the specific Fe/Si content ratio.
  • the recrystallized grain grows and improves the high temperature stability of the foil.
  • the rare earth element effectively improves the existence and distribution of Fe and Si elements, and inhibits the hard and brittle ⁇ (Al 9 Fe 2 Si 2 ) phase and the Fe 3 Al phase.
  • the formation of the pinhole of the finished product is greatly reduced, thereby significantly improving the mechanical properties, electrical conductivity and yield of the 1100 series aluminum foil.
  • the finished product has a tensile strength of 240 to 260 MPa, an elongation of 3.5% to 5%, a conductivity of 32 to 35 Ms/m, and a surface wetting tension of ⁇ 30 dyne.
  • the 1100 alloy aluminum foil for lithium battery is produced according to the following production process steps: (1) smelting: according to the mass percentage component: Fe: 0.5%, Si: 0.15%, Cu: 0.1%, Ti: 0.01%, Sc: 0.03%, Ce : 0.04%, Mn: 0.007%, Mg: 0.005%, Zn: 0.002%, the balance is Al, the raw materials of each element are added to the melting furnace, and the alloy ingot is obtained by smelting, the melting temperature is 760 ° C, and the refining temperature is 740 ° C. The casting temperature is 700 °C.
  • Rough rolling The hot rolled billet was placed on a cold rolling mill for cold rough rolling to obtain a rough rolled billet having a thickness of 2.6 mm.
  • Recrystallization annealing Intermediate recrystallization annealing was performed on the rough rolled billet to obtain a recrystallized and annealed rolled sheet having a temperature of 420 ° C and a holding time of 10 hours.
  • Medium rolling The rolled sheet after recrystallization annealing was further subjected to straight rolling to obtain an aluminum foil roll, and the thickness was controlled to 0.6 mm.
  • the 1100 alloy aluminum foil for lithium battery is produced according to the following production process steps: (1) smelting: according to the mass percentage component: Fe: 0.4%, Si: 0.1%, Cu: 0.12%, Ti: 0.01%, Sc: 0.03%, Ce : 0.07%, Mn: 0.005%, Mg: 0.003%, Zn: 0.003%, the balance is Al, the raw materials of each element are added to the melting furnace, and the alloy ingot is obtained by smelting, the melting temperature is 765 ° C, and the refining temperature is 760 ° C. The casting temperature is 705 °C.
  • Rough rolling The hot rolled billet was placed on a cold rolling mill for cold rough rolling to obtain a rough rolled billet, and the thickness was controlled to 2.5 mm.
  • Recrystallization annealing Intermediate recrystallization annealing was performed on the rough rolled billet to obtain a recrystallized and annealed rolled sheet having a temperature of 400 ° C and a holding time of 9 hours.
  • Medium rolling The rolled sheet after recrystallization annealing was further subjected to straight rolling to obtain an aluminum foil roll, and the thickness was controlled to 0.5 mm.
  • the 1100 alloy aluminum foil for lithium battery is produced according to the following production process steps: (1) smelting: according to the mass percentage component: Fe: 0.4%, Si: 0.1%, Cu: 0.13%, Ti: 0.015%, Sc: 0.07%, Ce : 0.03%, Mn: 0.006%, Mg: 0.003%, Zn: 0.005%, and the rest is Al.
  • the raw materials of each element are added to a melting furnace to obtain an alloy ingot, the melting temperature is 750 ° C, and the refining temperature is 750 ° C.
  • the casting temperature is 705 °C.
  • Hot rolling After milling the surface, the alloy ingot was hot rolled to obtain a hot rolled billet, and the thickness was controlled to 6.5 mm.
  • Rough rolling The hot rolled billet is placed on a cold rolling mill for cold rough rolling to obtain a rough rolled billet, and the thickness is controlled to be 2.2 mm.
  • Recrystallization annealing Intermediate recrystallization annealing was performed on the rough rolled billet to obtain a recrystallized and annealed rolled sheet having a temperature of 430 ° C and a holding time of 10 hours.
  • Medium rolling The rolled sheet after recrystallization annealing was further subjected to straight rolling to obtain an aluminum foil roll, and the thickness was controlled to 0.4 mm.
  • the 1100 alloy aluminum foil for lithium battery is produced according to the following production process steps: (1) smelting: according to the mass percentage component: Fe: 0.44%, Si: 0.18%, Cu: 0.15%, Ti: 0.018%, Sc: 0.05%, Ce : 0.05%, Mn: 0.007%, Mg: 0.003%, Zn: 0.002%, the balance is Al, the raw materials of each element are added to the melting furnace, and the alloy ingot is obtained by smelting, the melting temperature is 780 ° C, and the refining temperature is 740 ° C. The casting temperature was 695 °C.
  • Rough rolling The hot rolled billet was placed on a cold rolling mill for cold rough rolling to obtain a rough rolled billet having a thickness of 2.8 mm.
  • Recrystallization annealing Intermediate recrystallization annealing was performed on the rough rolled billet to obtain a recrystallized and annealed rolled sheet having a temperature of 420 ° C and a holding time of 12 hours.
  • Medium rolling The rolled sheet after recrystallization annealing was further subjected to straight rolling to obtain an aluminum foil roll, and the thickness was controlled to 0.5 mm.
  • the 1100 alloy aluminum foil for lithium battery is produced according to the following production process steps: (1) smelting: according to the mass percentage component: Fe: 0.48%, Si: 0.12%, Cu: 0.12%, Ti: 0.02%, Sc: 0.04%, Ce : 0.05%, Mn: 0.008%, Mg: 0.002%, Zn: 0.004%, the balance is Al, the raw materials of each element are added to the melting furnace, and the alloy ingot is obtained by smelting, the melting temperature is 780 ° C, and the refining temperature is 740 ° C. The casting temperature was 695 °C.
  • Rough rolling The hot rolled billet was placed on a cold rolling mill for cold rough rolling to obtain a rough rolled billet having a thickness of 2.8 mm.
  • Recrystallization annealing Intermediate recrystallization annealing was performed on the rough rolled billet to obtain a recrystallized and annealed rolled sheet having a temperature of 420 ° C and a holding time of 12 hours.
  • Medium rolling The rolled sheet after recrystallization annealing was further subjected to straight rolling to obtain an aluminum foil roll, and the thickness was controlled to 0.5 mm.
  • the 1100 alloy aluminum foil for lithium battery is produced according to the following production process steps: (1) smelting: according to the mass percentage component: Fe: 0.5%, Si: 0.13%, Cu: 0.12%, Ti: 0.013%, Sc: 0.03%, Ce : 0.04%, Mn: 0.006%, Mg: 0.005%, Zn: 0.004%, the balance is Al, the raw materials of each element are added to the melting furnace, and the alloy ingot is obtained by smelting, the melting temperature is 780 ° C, and the refining temperature is 740 ° C. The casting temperature was 695 °C.
  • Rough rolling The hot rolled billet was placed on a cold rolling mill for cold rough rolling to obtain a rough rolled billet having a thickness of 2.8 mm.
  • Recrystallization annealing Intermediate recrystallization annealing was performed on the rough rolled billet to obtain a recrystallized and annealed rolled sheet having a temperature of 420 ° C and a holding time of 12 hours.
  • Medium rolling The rolled sheet after recrystallization annealing was further subjected to straight rolling to obtain an aluminum foil roll, and the thickness was controlled to 0.5 mm.
  • 1100 alloy aluminum foil is produced according to the following production process steps: (1) smelting: according to the mass percentage components: Fe: 0.5%, Si: 0.10%, Cu: 0.12%, Ti: 0.013%, Sc: 0.03%, Ce: 0.04% Mn: 0.006%, Mg: 0.005%, Zn: 0.004%, the balance is Al, the raw materials of each element are added to the melting furnace, and the alloy ingot is obtained by smelting, the melting temperature is 780 ° C, the refining temperature is 740 ° C, and the casting temperature It is 695 °C. (2) Hot rolling: After milling, the alloy ingot was hot rolled to obtain a hot rolled billet having a thickness of 7.0 mm.
  • Rough rolling The hot rolled billet was placed on a cold rolling mill for cold rough rolling to obtain a rough rolled billet having a thickness of 2.8 mm.
  • Recrystallization annealing Intermediate recrystallization annealing was performed on the rough rolled billet to obtain a recrystallized and annealed rolled sheet having a temperature of 420 ° C and a holding time of 12 hours.
  • Medium rolling The rolled sheet after recrystallization annealing was further subjected to straight rolling to obtain an aluminum foil roll, and the thickness was controlled to 0.5 mm.
  • 1100 alloy aluminum foil is produced according to the following production process steps: (1) smelting: according to mass percentage components: Fe: 0.5%, Si: 0.15%, Cu: 0.1%, Ti: 0.01%, Sc: 0.01%, Ce: 0.01% Mn: 0.007%, Mg: 0.005%, Zn: 0.002%, the balance is Al, the raw materials of each element are added to the melting furnace, and the alloy ingot is obtained by smelting, the melting temperature is 760 ° C, the refining temperature is 740 ° C, and the casting temperature It is 700 °C. (2) Hot rolling: After milling, the alloy ingot was hot rolled to obtain a hot rolled billet, and the thickness was controlled to be 8.0 mm.
  • Rough rolling The hot rolled billet was placed on a cold rolling mill for cold rough rolling to obtain a rough rolled billet having a thickness of 2.6 mm.
  • Recrystallization annealing Intermediate recrystallization annealing was performed on the rough rolled billet to obtain a recrystallized and annealed rolled sheet having a temperature of 420 ° C and a holding time of 10 hours.
  • Medium rolling The rolled sheet after recrystallization annealing was further subjected to straight rolling to obtain an aluminum foil roll, and the thickness was controlled to 0.6 mm.
  • 1100 alloy aluminum foil is produced according to the following production process steps: (1) smelting: according to the mass percentage components: Fe: 0.3%, Si: 0.2%, Cu: 0.13%, Ti: 0.015%, Sc: 0.07%, Ce: 0.03% Mn: 0.006%, Mg: 0.003%, Zn: 0.005%, and the rest is Al. The raw materials of each element are added to the melting furnace to obtain an alloy ingot, the melting temperature is 750 ° C, the refining temperature is 750 ° C, and the casting temperature is obtained. It is 705 °C. (2) Hot rolling: After milling the surface, the alloy ingot was hot rolled to obtain a hot rolled billet, and the thickness was controlled to 6.5 mm.
  • Rough rolling The hot rolled billet is placed on a cold rolling mill for cold rough rolling to obtain a rough rolled billet, and the thickness is controlled to be 2.2 mm.
  • Recrystallization annealing Intermediate recrystallization annealing was performed on the rough rolled billet to obtain a recrystallized and annealed rolled sheet having a temperature of 430 ° C and a holding time of 10 hours.
  • Medium rolling The rolled sheet after recrystallization annealing was further subjected to straight rolling to obtain an aluminum foil roll, and the thickness was controlled to 0.4 mm.

Abstract

L'invention concerne une feuille d'aluminium en alliage 1100 pour une batterie au lithium, caractérisée en ce qu'elle comprend les constituants suivants en pourcentage en masse : 0,4 % à 0,5 % de Fe, 0,1 % à 0,2 % de Si, 0,1 % à 0,15 % de Cu, 0,01 % à 0,02 % de Ti, 0,03 % à 0,07 % de Sc, 0,03 % à 0,07 % de Ce, ≤ 0,01 % de Mn, ≤ 0,005 % de Mg, ≤ 0,005 % de Zn et ≥ 99,2 % d'Al, où Fe + Si ≤ 0,65 % et Fe/Si va de 2,0 à 4,0. Dans la présente invention, la régulation et le contrôle du rapport des éléments dans l'alliage 1100, associés à un traitement aux terres rares, permettent d'améliorer le rendement et les indices de performance mécanique d'une feuille d'aluminium hautement conductrice pour batterie au lithium. Un produit de matériau fini a une résistance à la traction pouvant aller de 220 à 260 MPa, un allongement qui peut aller de 3 % à 5 %, une conductivité électrique de 32 à 35 Ms/m et une tension de mouillage de surface supérieure ou égale à 30 dynes.
PCT/CN2018/122457 2018-05-11 2018-12-20 Feuille d'aluminium en alliage 1100 pour batterie au lithium et sa méthode de fabrication WO2019214243A1 (fr)

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CN201810445755.0 2018-05-11
CN201810445755.0A CN108315606B (zh) 2018-05-11 2018-05-11 一种锂电池用1100合金铝箔及其制造方法

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CN113564425A (zh) * 2021-08-09 2021-10-29 江苏鼎胜新能源材料股份有限公司 一种1n00锂电池用铝箔及其制备方法
RU2813495C1 (ru) * 2023-10-11 2024-02-12 Общество с ограниченной ответственностью "Институт легких материалов и технологий" Сплав на основе алюминия и изделие из него

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CN115652115A (zh) * 2022-11-01 2023-01-31 江苏万顺新富瑞科技有限公司 一种高延伸率1100合金电池铝箔生产工艺

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RU2813495C1 (ru) * 2023-10-11 2024-02-12 Общество с ограниченной ответственностью "Институт легких материалов и технологий" Сплав на основе алюминия и изделие из него

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