WO2012117627A1 - Feuille d'alliage d'aluminium pour collecteurs de courant d'électrode de batterie au lithium-ion et son procédé de production - Google Patents

Feuille d'alliage d'aluminium pour collecteurs de courant d'électrode de batterie au lithium-ion et son procédé de production Download PDF

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Publication number
WO2012117627A1
WO2012117627A1 PCT/JP2011/077000 JP2011077000W WO2012117627A1 WO 2012117627 A1 WO2012117627 A1 WO 2012117627A1 JP 2011077000 W JP2011077000 W JP 2011077000W WO 2012117627 A1 WO2012117627 A1 WO 2012117627A1
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WO
WIPO (PCT)
Prior art keywords
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aluminum alloy
alloy foil
lithium ion
ion battery
Prior art date
Application number
PCT/JP2011/077000
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English (en)
Japanese (ja)
Inventor
田中　宏樹
Original Assignee
住友軽金属工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 住友軽金属工業株式会社 filed Critical 住友軽金属工業株式会社
Publication of WO2012117627A1 publication Critical patent/WO2012117627A1/fr

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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
    • 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
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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

Definitions

  • the present invention is a high-strength and highly conductive lithium ion suitably used for an electrode current collector of a lithium ion secondary battery (hereinafter simply referred to as a lithium ion battery) used in a mobile phone, a notebook personal computer, etc.
  • the present invention relates to an aluminum alloy foil for a battery electrode current collector and a method for producing the same.
  • the lithium ion battery electrode current collector is composed of an electrode plate group in which a positive electrode and a negative electrode are wound with a separator interposed therebetween, and this is inserted into a battery case.
  • the battery case has a cylindrical shape and a square shape, and a current collector is prepared according to the shape of the case. After inserting the current collector, a non-aqueous electrolyte is injected and sealed.
  • the positive electrode active material lithium cobaltate, a lithium nickel composite compound or the like is used, and as the negative electrode active material, a carbon material capable of adsorbing and desorbing lithium ions such as coke and graphite is used.
  • These positive electrode active materials or negative electrode active materials are stirred and mixed with a binder using polyvinylidene fluoride, etc., applied to the aluminum foil of the positive electrode or the copper foil of the negative electrode, dried and rolled, and heat-treated during or before and after rolling.
  • Patent Document 1 To improve the adsorptive power, cut into a predetermined size and formed into a sheet shape, and used as an electrode of a lithium ion secondary battery.
  • the aluminum foil for the positive electrode current collector in order to suppress the softening and strength reduction of the aluminum foil by heating in the drying process after the application of the positive electrode active material, and to prevent deformation of the aluminum foil in the rolling process, Mn and Cu are used.
  • the contained aluminum alloy foil is used (Patent Document 2).
  • JP 2007-234277 A Japanese Patent Laid-Open No. 11-67220
  • the present invention has been made as a result of repeated tests and studies on the relationship between the component composition, strength, electrical resistance and battery characteristics in order to solve the above-described conventional problems in the aluminum foil for a positive electrode current collector of a lithium ion battery. It is an object of the present invention to provide an aluminum alloy foil for a lithium ion battery electrode current collector that exhibits higher strength and lower electrical resistance than conventional materials, and a method for producing the same.
  • an aluminum alloy foil for a lithium ion battery electrode current collector has Mn: 0.4% (mass%, the same applies hereinafter) to less than 0.8%, Mg: 0.3 %: 0.8% or less, Si: 0.4% or less (excluding 0%, the same shall apply hereinafter), Fe: 0.8% or less, Ti: 0.05% or less, Mn and Mg contained It satisfies the relationship of Mn% + 4 ⁇ Mg% ⁇ 3.2% with respect to the amount, has a composition composed of the balance Al and inevitable impurities, has a tensile strength of 300 MPa or more, and a specific resistance value at room temperature of 3.7 ⁇ cm or less It is characterized by being.
  • the aluminum alloy foil for a lithium ion battery electrode current collector according to claim 2 is characterized in that in claim 1, the aluminum alloy foil further contains Cu: 0.02% to 0.3%.
  • a method for producing an aluminum alloy foil for a lithium ion battery electrode current collector according to claim 3 is a method for producing an aluminum alloy foil according to claim 1 or 2, wherein the composition according to claim 1 or 2 is used.
  • An ingot of an aluminum alloy having an aluminum alloy is homogenized according to a conventional method, then subjected to hot rolling and cold rolling, and a final cold rolling reduction rate after performing an intermediate heat treatment with recrystallization in the cold rolling is 85%. It is the above.
  • an aluminum alloy foil for a lithium ion battery electrode current collector that is particularly suitable for a positive electrode material.
  • the aluminum alloy foil does not cause a decrease in strength even when heated in the drying process at the time of manufacturing the positive electrode plate, and has sufficient strength not to be deformed even in the rolling process, and also has a sufficiently low electrical resistance. High density and high energy can be achieved.
  • Mn The dissolved Mn functions to improve the strength of the foil. Moreover, although the strength fall in the drying process at the time of positive electrode plate manufacture is suppressed, since solid solution Mn raises a specific resistance, it is desirable that there is little content from an electroconductive viewpoint.
  • the preferable content of Mn is in the range of 0.4% or more and less than 0.8%. If the content is less than 0.4%, sufficient strength cannot be obtained. Since the value exceeds 3.7 ⁇ cm, it is not preferable. A more preferable content range of Mn is 0.5% or more and 0.7% or less.
  • Mg functions to improve the strength together with Mn, and the specific resistance increases with the addition of Mg.
  • the preferable content of Mg is in the range of 0.3% to 0.8%, and if it is less than 0.3%, the strength is insufficient.
  • a more preferable content range of Mg is 0.4% or more and 0.7% or less.
  • the specific resistance of the aluminum alloy foil is required to be 3.7 ⁇ cm or less.
  • Mg the influence of Mg on the specific resistance
  • the relationship between the Mg content and the Mn content must satisfy the following formula. Mn% + 4 ⁇ Mg% ⁇ 3.2%
  • Si forms an Al—Mn—Si based compound during homogenization treatment or hot rolling, and reduces the solid solution amount of Mn.
  • a preferable content of Si is 0.4% or less. In order to keep the amount of Si even lower, it is necessary to use high purity bullion, which increases costs.
  • a more preferable content range of Si considering both cost and performance is 0.15% or more and 0.35% or less.
  • Fe forms an Al—Mn—Fe-based compound at the time of casting, and reduces the solid solution amount of Mn.
  • Al—Mn—Fe based compounds have a size of about 1 to 10 ⁇ m and do not contribute to strength. If the Fe content exceeds 0.8%, the solid solution amount of Mn decreases, and a predetermined strength cannot be obtained.
  • coarse Al—Mn—Fe-based crystals are easily formed during casting, causing pinholes during foil rolling. In order to prevent the formation of coarse crystals, it is necessary to adjust the blending amount so that (Fe% + Mn%) is 1.4% or less in consideration of the addition of Mg. In order to keep the amount of Fe low, it is necessary to use high-purity bullion, which increases costs. Therefore, a more preferable range of Fe in consideration of both cost and performance is 0.4% or more and 0.7% or less. .
  • Ti is added to refine the ingot structure. Ti increases the specific resistance even in a small amount, but if it exceeds 0.05%, it may cause pinholes during foil rolling. The same effect can be obtained by adding B together with Ti. For the same reason, the content of B in the aluminum alloy foil is preferably 0.01% or less.
  • Cu functions to improve strength.
  • the preferable content of Cu is in the range of 0.02% to 0.3%, and if it is less than 0.02%, the strength improvement effect is not sufficient.
  • Cu has less influence on the increase in specific resistance than Mn, but if it exceeds 0.3%, the strength increases but the specific resistance also increases, which is not preferable. In addition, cracks are likely to occur during casting, making it difficult to manufacture on a mass production scale.
  • a more preferable content range of Cu is 0.03% or more and 0.15% or less.
  • Zn 0.1% or less, Cr, Ni, Ga, V, and other elements individually 0.05% or less, if the total is 0.15% or less, the characteristics of the present invention are affected. None do.
  • the tensile strength has a sufficient strength of 300 MPa or more in order to prevent deformation in the rolling process.
  • the manufacturing process of the aluminum alloy foil of the present invention will be described.
  • the aluminum alloy having the above composition is melted and cast to form a predetermined slab, and the obtained slab (ingot) is homogenized according to a conventional method, followed by hot rolling.
  • a lithium ion battery electrode current collector it is necessary to finish the foil material with a thickness of 20 ⁇ m or less, and cold rolling to such a thin foil without performing an intermediate heat treatment from a hot rolled plate is due to work hardening. Difficult for mass production due to increased strength. Therefore, cold rolling is performed by performing an intermediate heat treatment accompanied by recrystallization during rolling. In this case, in order to obtain a predetermined strength, it is necessary to set the final cold rolling rate after performing the intermediate heat treatment accompanied by recrystallization in cold rolling to 85% or more.
  • Example 1 Aluminum alloys (A to K) having the composition shown in Table 1 were melted and ingot-formed by a semi-continuous casting method, and the resulting ingot was homogenized at a temperature of 480 ° C. for 5 hours, and then a temperature of 450 to 260 ° C. Hot rolling was performed in the range to obtain a hot rolled plate having a thickness of 3 mm. After cold-rolling the hot-rolled sheet to a thickness of 0.5 mm, an intermediate heat treatment is performed using a rapid heating furnace at a temperature of 400 ° C. for 1 minute and cooling at a cooling rate of 20 ° C./s After the heat treatment, cold rolling was repeated to obtain 15 ⁇ m aluminum alloy foils (test materials 1 to 11). The cold rolling rate at this time was 97%. In addition, about the conventional material (test material 11) (alloy: 3003 alloy), the foil material was created in the same process except performing the homogenization process for 5 hours at the temperature of 600 degreeC.
  • the test materials 1 to 5 according to the present invention have a tensile strength of 300 MPa or more and a specific resistance at room temperature of 3.7 ⁇ cm or less, which is higher than that of the conventional material (test material 11) 3003 alloy foil. The strength is high and the specific resistance is reduced.
  • test materials 6 to 10 outside the conditions of the present invention were inferior in either tensile strength or specific resistance. That is, since the test material 6 had a large amount of Mn, the specific resistance was high. Since the test material 7 had (Mn% + 4 ⁇ Mg%) larger than 3.2%, the specific resistance value was high.
  • the test material 8 had a small amount of Mn, the tensile strength was less than 300 MPa.
  • the test material 9 had a large amount of Fe, and an Al—Mn—Fe-based compound was produced during casting to reduce the solid solution amount of Mn. Therefore, the tensile strength was less than 300 MPa.
  • the test material 10 had a large amount of Si and a decreased amount of Mn solid solution, and the amount of Mg was small, the tensile strength was less than 300 MPa.
  • the test material 11 shows the characteristics of a conventional 3003 alloy foil, the tensile strength is less than 300 MPa, and the specific resistance exceeds 3.7 ⁇ cm.
  • Example 2 Using alloy E ingoted in Example 1, homogenization treatment, hot rolling and cold rolling were performed under the same conditions as in the production of test materials 1 to 10 in Example 1, and only the final cold rolling rate was changed. An aluminum alloy foil having a thickness of 15 ⁇ m was manufactured, and the obtained alloy foil (test material) was measured for tensile properties and specific resistance at room temperature (25 ° C.) in the same manner as in Example 1. The results are shown in Table 3.
  • test materials 12 to 14 according to the present invention exhibited characteristics of a tensile strength of 300 MPa or more and a specific resistance at room temperature of 3.7 ⁇ cm or less.
  • test materials 15 to 17 had a tensile strength lower than 300 MPa because the final cold rolling rate was less than 85%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

L'invention porte sur une feuille d'alliage d'aluminium pour des collecteurs de courant d'électrode de batterie au lithium-ion qui présente une résistance élevée et une faible résistance électrique et qui est caractérisée en ce que : elle a une composition contenant du Mn en quantité supérieure ou égale à 0,4 % et inférieure à 0,8 %, du Mg en quantité supérieure ou égale à 0,3 % et inférieure ou égale à 0,8 %, du Si en quantité inférieure ou égale à 0,4 %, du Fe en quantité inférieure ou égale à 0,8 % et du Ti en quantité inférieure ou égale à 0,5 % ; elle satisfait à la relation [(% de Mn) + 4 x (% de Mg) ≤ 3,2 %] en ce qui concerne les quantités de Mn et de Mg contenus dans celle-ci ; et elle comprend de l'Al et des impuretés inévitables constituant le reste de celle-ci ; sa résistance à la traction étant supérieure ou égale à 300 MPa ; et sa valeur de résistance spécifique à température ambiante étant inférieure ou égale à 3,7 μΩ•cm.
PCT/JP2011/077000 2011-02-28 2011-11-24 Feuille d'alliage d'aluminium pour collecteurs de courant d'électrode de batterie au lithium-ion et son procédé de production WO2012117627A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011041154A JP2012177171A (ja) 2011-02-28 2011-02-28 リチウムイオン電池電極集電体用アルミニウム合金箔およびその製造方法
JP2011-041154 2011-02-28

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WO2012117627A1 true WO2012117627A1 (fr) 2012-09-07

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110943226A (zh) * 2019-04-28 2020-03-31 宁德时代新能源科技股份有限公司 正极集流体、正极极片及电化学装置
CN112941374A (zh) * 2021-02-26 2021-06-11 永杰新材料股份有限公司 一种电池铝箔及其加工方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5945148B2 (ja) * 2012-04-13 2016-07-05 三菱アルミニウム株式会社 リチウムイオン二次電池正極集電体用アルミニウム合金箔及びそれを用いたリチウムイオン二次電池
JP6435588B2 (ja) * 2013-07-08 2018-12-12 三菱アルミニウム株式会社 リチウムイオン二次電池正極集電体用アルミニウム合金箔

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004332106A (ja) * 2003-04-15 2004-11-25 Nippon Light Metal Co Ltd プレス成形性および連続抵抗スポット溶接性に優れたアルミニウム合金板およびその製造方法
JP2008150651A (ja) * 2006-12-15 2008-07-03 Mitsubishi Alum Co Ltd 耐折り曲げ性に優れたリチウムイオン電池電極材用アルミニウム合金箔およびその製造方法
JP2009064560A (ja) * 2006-08-29 2009-03-26 Toyo Aluminium Kk 集電体用アルミニウム合金箔

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004332106A (ja) * 2003-04-15 2004-11-25 Nippon Light Metal Co Ltd プレス成形性および連続抵抗スポット溶接性に優れたアルミニウム合金板およびその製造方法
JP2009064560A (ja) * 2006-08-29 2009-03-26 Toyo Aluminium Kk 集電体用アルミニウム合金箔
JP2008150651A (ja) * 2006-12-15 2008-07-03 Mitsubishi Alum Co Ltd 耐折り曲げ性に優れたリチウムイオン電池電極材用アルミニウム合金箔およびその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110943226A (zh) * 2019-04-28 2020-03-31 宁德时代新能源科技股份有限公司 正极集流体、正极极片及电化学装置
CN112941374A (zh) * 2021-02-26 2021-06-11 永杰新材料股份有限公司 一种电池铝箔及其加工方法

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