WO2014112619A1 - Feuille de cuivre, anode pour batterie lithium-ion, et batterie rechargeable lithium-ion - Google Patents

Feuille de cuivre, anode pour batterie lithium-ion, et batterie rechargeable lithium-ion Download PDF

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Publication number
WO2014112619A1
WO2014112619A1 PCT/JP2014/050942 JP2014050942W WO2014112619A1 WO 2014112619 A1 WO2014112619 A1 WO 2014112619A1 JP 2014050942 W JP2014050942 W JP 2014050942W WO 2014112619 A1 WO2014112619 A1 WO 2014112619A1
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Prior art keywords
copper foil
copper
copper layer
lithium ion
tensile strength
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PCT/JP2014/050942
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English (en)
Japanese (ja)
Inventor
健作 篠崎
鈴木　昭利
季実子 藤澤
健 繪面
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古河電気工業株式会社
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Priority to JP2014526317A priority Critical patent/JPWO2014112619A1/ja
Publication of WO2014112619A1 publication Critical patent/WO2014112619A1/fr

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    • 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
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • 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 relates to a copper foil, a negative electrode for a lithium ion secondary battery using the copper foil, and a lithium ion secondary battery using the copper foil, and in particular, mechanical strength (tensile strength) suitable for a negative electrode for a lithium ion secondary battery. And a copper foil having hardness, a negative electrode for a lithium ion secondary battery using the same, and a lithium ion secondary battery using the same.
  • next-generation negative electrode active materials having charge / discharge capacities far exceeding the theoretical capacity of carbon materials has been promoted as negative electrode active materials for lithium ion secondary batteries.
  • a material containing a metal that can be alloyed with lithium (Li) such as silicon (Si), germanium (Ge), or tin (Sn) is expected.
  • these materials when Si, Sn, or the like is used as an active material, these materials have a large volume change due to insertion / extraction of Li during charge / discharge, and thus maintain a good adhesion state between the current collector and the active material It is difficult.
  • these materials have a very large volume change rate due to Li insertion and desorption, and are repeatedly expanded and contracted by the charge / discharge cycle, so that the active material particles are pulverized or desorbed. Has the disadvantage of being very large.
  • Patent Document 1 has a rough surface with a rough surface roughness Rz of 2.0 ⁇ m or less and a uniform low roughness as an optimal copper foil for a negative electrode current collector for a secondary battery, at 180 ° C.
  • a low rough surface electrolytic copper foil having an elongation of 10.0% or more is described.
  • the above-mentioned electrolytic copper foil is obtained by using a sulfuric acid-copper sulfate aqueous solution as an electrolytic solution and adding polyethyleneimine or a derivative thereof, a sulfonate salt of an active organic sulfur compound, and chloride ions.
  • the rough surface roughness Rz of the electrolytic copper foil is 2.5 ⁇ m or less, and the tensile strength at 25 ° C. measured within 20 minutes from the completion of electrodeposition is 820 MPa or more.
  • An electrolytic copper foil is described in which the rate of decrease in tensile strength at 25 ° C. measured after 300 minutes from the completion of electrodeposition with respect to tensile strength at 25 ° C. measured within 20 minutes from the completion time is 10% or less. .
  • the electrolytic copper foil is obtained by adding hydroxyethyl cellulose, polyethyleneimine, sulfonic acid salt of active organic sulfur compound, acetylene glycol, and chloride ion using sulfuric acid-copper sulfate aqueous solution as an electrolytic solution.
  • Patent Document 3 discloses an electrodeposited copper foil having a grain structure having no columnar grains and twin boundaries and having an average grain size of up to 10 ⁇ m, and the grain structure is substantially uniform and randomly.
  • a controlled low profile electrodeposited copper foil is described which is an oriented grain structure.
  • This electrodeposited copper foil has a maximum tensile strength at 23 ° C. of 87,000 to 120,000 psi (600 MPa to 827 MPa) and a maximum tensile strength at 180 ° C. of 25,000 to 35,000 psi (172 MPa to 172 MPa). 241 MPa).
  • Patent Documents 1 to 3 have a high mechanical strength in a normal state, and the mechanical strength hardly changes even when heated at around 180 ° C.
  • a foil is heated at about 300 ° C., it is annealed and recrystallization proceeds, so that it softens rapidly and the mechanical strength decreases.
  • Patent Documents 4 and 5 describe a method of producing an electrolytic copper foil with an electrolytic solution in which W is added to a sulfuric acid-copper sulfate electrolytic solution, and further glue and chlorine ions are added. It is described that it is possible to manufacture a copper foil having a hot elongation rate of 3% or more, a rough surface having a large roughness, and less pinholes.
  • the copper foil produced by adding the above W has a high mechanical strength (tensile strength) at room temperature (RT), but the mechanical strength cannot be maintained when heat-treated at 300 ° C. for 1 hour. As a result of analyzing this copper foil, it was found that W was not co-deposited in the electrodeposited copper.
  • Patent Document 6 describes a current collector having a surface layer portion that is easily plastically deformed on the surface of the current collector. Among them, it is described that the surface layer portion preferably has a Vickers hardness of 200 or less, preferably 160 or less. In Patent Document 6, it is described as a current collector having a surface layer portion that is easily plastically deformed on the surface of the current collector, but in reality, the plastic deformation of the surface is not sufficient, and the shape of the active material is limited. Need arises. In Patent Document 6, the above problem is solved by increasing the roughness of the surface layer of the current collector, forming the active material layer into columnar particles, and providing voids between the active materials. Of course, the battery capacity can be reduced by providing a gap between the active materials, but when current flows locally, stress is concentrated on a part of the active material and the current collector, resulting in deterioration of cycle characteristics. A problem occurs.
  • the negative electrode current collector of a lithium ion secondary battery is made using the above-mentioned conventional copper foil, if the mechanical strength (tensile strength) of the copper foil is low, press working in the electrode forming process of the lithium ion secondary battery There are disadvantages that can easily lead to wrinkles. Moreover, when the mechanical strength (tensile strength) of the copper foil is low, there is a disadvantage that wrinkles easily occur as the secondary battery is repeatedly charged and discharged. In addition, when the hardness of the copper foil is high, for example, a carbon-based or Si-based negative electrode active material is difficult to bite into the copper foil, the adhesion between the active material and the copper foil tends to be low, and the battery capacity and cycle characteristics are reduced.
  • Japanese Patent No. 4120806 Japanese Patent No. 4273309 Japanese Patent No. 3,270,637 Japanese Patent No. 3238278 JP-A-9-67693 JP 2008-98157 A
  • the object of the present invention is to provide mechanical strength (tensile strength) and surface hardness that are difficult to cause wrinkles and deformation during pressing and charging / discharging and that can maintain high adhesion between the negative electrode active material and the copper foil. It is intended to provide a copper foil having a negative electrode for a lithium ion secondary battery excellent in cycle characteristics using the copper foil and a lithium ion secondary battery using the same.
  • the present inventor has mechanical strength (see FIG. 5) that is resistant to wrinkles even during press working and charge / discharge, and that can maintain high adhesion between a carbon-based and Si-based negative electrode active material and copper foil ( We have succeeded in developing a copper foil having tensile strength and surface hardness.
  • the copper foil according to the present invention includes a first copper layer having a tensile strength of 550 MPa or more at room temperature, and a second copper layer having a lower hardness than the first copper layer on at least one surface of the first copper layer.
  • the copper foil of the present invention preferably has a total thickness of 7 to 12 ⁇ m including the first copper layer and the second copper layer.
  • the thickness of the second copper layer is preferably 0.3 to 3 ⁇ m.
  • the thickness of the first copper layer is equal to or greater than the thickness of the second copper layer.
  • the copper foil of the present invention preferably has a Young's modulus at room temperature of the first copper layer of 75 to 130 GPa.
  • the copper foil of the present invention preferably has a tensile strength at room temperature of 500 MPa or more.
  • the copper foil of the present invention preferably has a Young's modulus at room temperature of 70 to 120 GPa.
  • the copper foil of the present invention preferably has a surface hardness of 180 to 370 mgf / ⁇ m 2 at room temperature.
  • the copper foil of the present invention preferably has a tensile strength of 400 MPa or more measured at room temperature after heat treatment at 300 ° C. for 1 hour.
  • the copper foil of the present invention preferably has a Young's modulus of 65 GPa or more measured at room temperature after heat treatment at 300 ° C. for 1 hour.
  • the negative electrode for a lithium ion secondary battery of the present invention is a negative electrode using the copper foil described above as a current collector.
  • the negative electrode for a lithium ion secondary battery described above is used as the negative electrode.
  • the copper foil of the present invention by providing a second copper layer having a lower hardness than the first copper layer on at least one surface of the first copper layer having a tensile strength of 550 MPa or more at room temperature, Copper having mechanical strength (tensile strength) and surface hardness that is resistant to wrinkles even during press working and charging and discharging, and that can maintain high adhesion between carbon-based and Si-based negative electrode active materials and copper foil.
  • a foil can be provided.
  • the negative electrode for a lithium ion secondary battery of the present invention is a current collector constituting the negative electrode, and is not easily wrinkled at the time of pressing and charging / discharging, and a carbon-based and Si-based negative electrode active material and a copper foil Since the copper foil which has the mechanical strength (tensile strength) and hardness which hold
  • the lithium ion secondary battery of the present invention can provide a battery having excellent charge / discharge characteristics by using the negative electrode.
  • the copper foil according to this embodiment includes a first copper layer having a tensile strength of 550 MPa or more at room temperature, a second copper layer having a lower hardness than the first copper layer provided on at least one surface of the first copper layer, Have
  • an electrolytic copper foil including an electrolytic copper alloy foil, the same applies hereinafter
  • a rolled copper foil including a rolled copper alloy foil, the same applies hereinafter
  • the second copper layer can be formed on the surface of the first copper layer by any method such as electrolytic treatment such as electrolytic plating, electroless treatment such as sputtering or chemical vapor deposition, and lamination (cladding). it can.
  • the first copper layer is a copper layer having a tensile strength of 550 MPa or more at room temperature
  • the second copper layer is a copper layer having a lower hardness than the first copper layer.
  • the copper foil of this embodiment preferably has a smooth surface, and Ra is preferably 1.0 ⁇ m or less and Rz is preferably 4.0 ⁇ m or less (JIS B 0601: 1994). If the surface of the copper foil has large irregularities, the contact area of the active material is reduced, or the active material cannot enter the valleys of the irregularities, and the adhesion between the active material and the copper foil is likely to decrease, and the cycle characteristics are improved. It is because it falls.
  • the first copper layer is preferably made of an electrolytic copper alloy foil or a rolled copper alloy foil containing at least tungsten (W) or molybdenum (Mo).
  • a copper foil containing at least tungsten or molybdenum By using a copper foil containing at least tungsten or molybdenum, a tensile strength at room temperature of 550 MPa or more can be realized.
  • the first copper layer is not limited to the above-described electrolytic copper alloy foil containing tungsten or molybdenum, and may be used as long as the electrolytic copper foil has a tensile strength at room temperature of 550 MPa or more. It is.
  • the total thickness of the copper foil including the first copper layer and the second copper layer is preferably 7 to 12 ⁇ m. If the thickness is less than 7 ⁇ m, the handleability of the copper foil is lowered, and if it exceeds 12 ⁇ m, the energy density is lowered and it is not suitable for the negative electrode current collector for lithium ion secondary batteries.
  • other foil thicknesses can be used.
  • the thickness per one side of the second copper layer provided on the surface of the first copper layer is 0.3 to 3 ⁇ m. Is preferred. This is because if the thickness is less than 0.3 ⁇ m, the hardness of the surface of the copper foil may be inappropriate, and if it exceeds 3 ⁇ m, there is almost no effect of improving the adhesion to the active material. For this reason, the thickness of the second copper layer provided on one side of the first copper layer is practically 3 ⁇ m or less. In order to obtain the maximum effect of the present invention, the thickness of the second copper layer is preferably thinner than the thickness of the first copper layer.
  • It can be set as the structure which balanced the mechanical strength (tensile strength) and surface hardness of copper foil because the thickness of a 1st copper layer is more than the thickness of a 2nd copper layer.
  • the Young's modulus of the first copper layer at room temperature is preferably 75 to 130 GPa. This is because when the Young's modulus is less than 75 GPa, even if the breaking strength (tensile strength) of the copper foil is high, the copper foil is easily deformed by a low stress, and the cycle characteristics are liable to deteriorate when the current collector is used. Moreover, when the copper foil whose Young's modulus is higher than 130 GPa is used as a negative electrode (current collector), Breakage may occur in the current collector (copper foil) due to stress applied by expansion of the active material during charging, and the above range is preferable. Note that the Young's modulus of the copper layer in which the thickness of the first copper layer is equal to or greater than the thickness of the second copper layer greatly contributes to the Young's modulus of the first copper layer. Is desirable.
  • the tensile strength of the copper foil is preferably 500 MPa or more at room temperature.
  • the Young's modulus of the copper foil is preferably 70 to 120 GPa at room temperature.
  • the hardness of the surface layer of the copper foil at room temperature is preferably 180 to 370 mgf / ⁇ m 2 .
  • the copper foil of this embodiment has the above mechanical strength (tensile strength) and hardness, so that it is difficult for wrinkles to occur during press working when forming a negative electrode using the copper foil as a current collector. Even when charging and discharging the negative electrode, it is difficult for soot to enter, and high adhesion can be maintained between the carbon-based or Si-based negative electrode active material and the copper foil (current collector).
  • the copper foil of this embodiment preferably has a tensile strength of 400 MPa or more measured at room temperature after heat treatment at 300 ° C. for 1 hour.
  • the copper foil of the present embodiment preferably has a Young's modulus of 65 GPa or more measured at room temperature after heat treatment at 300 ° C. for 1 hour. This is because when the Young's modulus of the copper foil is lower than 65 GPa, the copper foil is deformed by stress generated by expansion of the active material during charging, and the negative electrode may be short-circuited with the positive electrode.
  • another metal layer, oxide layer, or organic layer may be appropriately interposed. It can. It is also effective to appropriately provide another metal layer, oxide layer, organic material layer, or the like on the surface of the second copper layer.
  • the 1st copper layer of the copper foil of this embodiment can be manufactured by the electroplating using the plating bath which added the below-mentioned various additives, for example in the following copper plating bath basic composition and plating conditions.
  • Copper plating bath basic composition and plating conditions for first copper foil foil Copper concentration: 50 to 100 g / l Sulfuric acid concentration: 40-100g / l Liquid temperature: 40-70 ° C Current density: 35-60 A / dm 2
  • Chlorine, tungsten (W) or molybdenum (Mo) is added to the above copper plating bath basic composition.
  • W or Mo is contained in the copper foil, and the first copper foil that becomes the first copper layer having high mechanical strength (tensile strength) can be formed.
  • the concentration of W or Mo may be added in excess of the above upper limit, but even if the concentration exceeds the upper limit, the influence on the improvement of the mechanical strength (tensile strength) of the first copper foil is small.
  • the above is preferably set as the upper limit.
  • Additive (B) Chlorine (Cl), an organic additive, and a metal (W) are added to the above copper plating bath basic composition.
  • thioureas for example, thiourea (TU), ethylenethiourea (ETU), and tetramethylthiourea (TMTU) can be used.
  • a first copper layer made of copper containing W and having high mechanical strength (tensile strength) can be formed.
  • Additive (C) Chlorine (Cl) and an organic additive are added to the above copper plating bath basic composition.
  • thioureas for example, thiourea (TU), ethylenethiourea (ETU), and tetramethylthiourea (TMTU) can be used.
  • glue may be added.
  • a rolled copper foil for example as a 1st copper layer of the copper foil which concerns on this embodiment.
  • a copper foil containing 0.03% of Zr with respect to Cu can be used.
  • a copper foil having a tensile strength of 550 MPa or more at room temperature can be appropriately used even if it is manufactured by a method other than the above.
  • the second copper layer of the copper foil according to this embodiment can be formed on at least one surface of the first copper layer by, for example, electrolytic treatment under the following copper plating bath basic composition and plating conditions.
  • Copper plating bath composition and plating conditions for the second copper foil foil Copper concentration: 50 to 100 g / l Sulfuric acid concentration: 40-100g / l Liquid temperature: 40-70 ° C Current density: 35-60 A / dm 2
  • the second copper layer formed on at least one surface of the first copper layer can be provided by, for example, electroless treatment such as sputtering or chemical vapor deposition, or lamination (cladding).
  • the thickness of the copper foil of this embodiment is 7 to 12 ⁇ m for the entire copper foil including the first copper layer and the second copper layer for the current collector of the lithium ion secondary battery.
  • the thickness of the layer is preferably 0.3 to 3 ⁇ m, and the thickness of the first copper layer is preferably equal to or greater than the thickness of the second copper layer.
  • this is not the case when used for applications such as printed wiring boards and suspensions.
  • the volume of the active material changes to three times or more due to charge / discharge.
  • the tensile strength is high, but there is a disadvantage that the elongation is small.
  • the negative electrode incorporated in the lithium ion secondary battery that is, the collector heated and pressurized after applying the active material, has a tensile strength of 400 MPa or more and can follow the volume change of the active material. It is desirable that the 0.2% proof stress is 340 MPa or more and the Young's modulus is 65 GPa or more.
  • a copper foil having a tensile strength of 650 MPa or more generally has a brittle property.
  • the present inventors for example, form a first copper layer having a tensile strength of 550 MPa or more at room temperature and a second copper layer with a thickness of 0.3 to 3 ⁇ m on at least one surface, and have a surface hardness of 180 ⁇ m.
  • the brittleness of the copper foil can be overcome, and a copper foil suitable for the negative electrode current collector of a lithium ion secondary battery using carbon-based and Si-based active materials can be produced. , And got the knowledge.
  • the second copper layer has a hardness lower than that of the first copper layer and the thickness is set to 0.3 to 3 ⁇ m, and is applied to the surface of the second copper layer and heated under pressure at 300 ° C. for 1 hour.
  • the Si-based active material to be treated can be made to penetrate into the surface of the second copper layer, and even if the hardness of the first copper layer is high, the second copper layer having a lower hardness is Si-based, etc. This is considered to be because the volume change of the active material can be followed.
  • the copper foil surface since the hardness of the copper foil surface (2nd copper layer surface) which contacts an active material is low when it press-processes in order to set it as the negative electrode of a lithium ion secondary battery, the copper foil surface is Due to the processing pressure, it deforms along the shape of the active material, improves the adhesion between the active material and the copper foil, and increases the contact area, so that a negative electrode with high conductivity can be obtained.
  • the surface of the rolled copper foil is processed to be hardened, and the second copper layer is provided as described above so that the surface hardness at room temperature is 180 to 370 mgf / ⁇ m 2 .
  • a foil can be created and the same effects as described above can be obtained.
  • the present embodiment relates to a lithium ion secondary battery.
  • the negative electrode for a lithium ion secondary battery according to this embodiment uses the copper foil of the first embodiment as a negative electrode current collector.
  • a negative electrode using the copper foil as a negative electrode current collector is a negative electrode for a lithium ion secondary battery.
  • the copper foil constituting the negative electrode is resistant to wrinkles during press working and charge / discharge, and maintains high adhesion between the negative electrode active material such as Si and the copper foil. Since it has mechanical strength (tensile strength) and hardness, it can provide a negative electrode for a lithium ion secondary battery that is particularly excellent in charge / discharge characteristics and a lithium ion secondary battery using the same.
  • first copper layer Examples 1 to 23 Using the copper plating bath having the composition shown in Table 1, the first copper layer according to Examples 1 to 9 was produced by the method of adding the additive (A). In addition, using the copper plating bath having the composition shown in Table 1, the first copper layer according to Examples 10 to 17 was prepared by the method of adding the additive (B). In addition, using the copper plating bath having the composition shown in Table 1, the first copper layer according to Examples 18 to 22 was produced by the method of adding the additive (C). Moreover, the Example using the rolled copper foil shown in Table 1 as a 1st copper layer was made into Example 23. FIG.
  • Table 1 summarizes the tensile strength (MPa), Young's modulus (GPa), hardness (nanoindenter hardness, mgf / ⁇ m 2 ), and standard deviation ( ⁇ ) thereof at room temperature for each of the above examples.
  • MPa tensile strength
  • GPa Young's modulus
  • ⁇ standard deviation
  • Comparative Examples 1 to 10 Formation of Comparative Examples 1 to 10 First copper layers according to Comparative Examples 1 to 3 were produced by the method of adding the additive (A) shown in the above table. Further, first copper layers according to Comparative Examples 4 to 7 were prepared by the method of adding the additive (B) shown in the table. Moreover, the 1st copper layer which concerns on the comparative examples 8 and 9 was produced by the method of adding the additive (C) shown to a table
  • TPC tough pitch copper
  • Table 1 summarizes the tensile strength (MPa), Young's modulus (GPa), hardness (nanoindenter hardness, mgf / ⁇ m 2 ), and standard deviation ( ⁇ ) of each of the comparative examples.
  • MPa tensile strength
  • GPa Young's modulus
  • ⁇ standard deviation
  • the tensile strength of the first copper foil at room temperature was 550 MPa or more, but in Comparative Examples 1 to 10, the tensile strength was less than 550 MPa.
  • second copper foil second copper layer
  • assembly of lithium ion secondary battery Examples 24 to 34 The surface of the first copper foil selected from Examples 1 to 23 is subjected to electrolytic plating according to a copper plating bath and a plating condition for the second copper foil having the following composition, or by electroless plating or a second copper by a clad method. Layers were formed as Examples 24 to 34, and mechanical characteristics and the like were measured. A lithium ion secondary battery using the copper foil as a negative electrode was assembled, and the battery characteristics were measured. Table 2 shows the thickness ( ⁇ m) of the first copper layer and the thickness ( ⁇ m) of the second copper layer.
  • Copper plating bath composition and plating conditions when forming the second copper foil by electrolytic plating Copper concentration: 50 to 100 g / l Sulfuric acid concentration: 40-100g / l Liquid temperature: 40-70 ° C Current density: 35-60 A / dm 2
  • plating was performed using a plating solution OPC-700 manufactured by Okuno Pharmaceutical Co., Ltd. until a predetermined foil thickness was obtained.
  • ⁇ Nanoindenter hardness is measured using an ultra-fine indentation hardness tester ENT-2100 manufactured by Elionix Co., Ltd. The measurement was performed at room temperature at a tensile speed of 10 mm / min. -Tensile strength and 0.2% proof stress were measured based on IPC-TM-650, and surface roughness was measured according to JIS B 0601: 1994. In general, Vickers hardness is often used for measuring the hardness of a metal material. However, as described in JIS Z2244, the minimum thickness of a sample is determined to be 1.5 times or more of the diagonal of the depression, The measurement of thin copper foil as in the present invention is not suitable because the foil is torn.
  • the copper foil of the two-layer structure is affected by the strength of the first layer (center material) as in the present invention. Since it was difficult to measure the hardness, the measurement was performed using a nanoindenter.
  • the active material adhesion in a roll press under a pressing condition of a linear pressure of 500 kg / cm and 130 to 150 ° C. and the deformation of the foil were examined.
  • the active material was continuously applied to one side of the current collector.
  • pressure is applied to the coated portion of the active material during pressing, and pressure is not applied to the uncoated portion during pressing, so that the thickness of the coated portion is reduced and deformation occurs.
  • the active material adhesion was good, and no deformation of the foil was observed.
  • the evaluation of the adhesion of the active material is performed by a 90-degree peel test, where ⁇ indicates that the active material layer is agglomerated and broken, and part of the active material layer remains on the surface of the current collector. ⁇ , and what completely peeled off at the interface was marked with ⁇ .
  • deformation of the foil after pressing is less than 1 mm (0.1%) when the deformation of the coated part is less than 1 mm (0.1%) relative to 1 m of the uncoated part. 0.3%) or more were evaluated as x, and the evaluation results are shown in Table 2.
  • Comparative examples 11-14 By using the same electrolytic plating or electroless plating as in Examples 24 to 34, the first copper foil (first copper layer) selected from Examples 1 to 23 or Comparative Examples 1 to 10 was subjected to the second copper under the conditions shown in Table 2. A layer was formed to prepare a copper foil, and Comparative Examples 11 to 14 were obtained. Here, the comparative example 11 does not form the second copper layer. About each comparative example, while measuring a mechanical characteristic etc., the lithium ion secondary battery which uses this copper foil as a negative electrode was assembled, and the battery characteristic was measured. Table 2 shows the thickness ( ⁇ m) of the first copper layer and the thickness of the second copper layer.
  • Comparative Examples 11 to 14 the active material adhesion in a roll press under a pressing condition of a linear pressure of 500 kg / cm and 130 to 150 ° C., and deformation of the foil were examined. In all of Comparative Examples 11 to 14, there was a defect in either the active material adhesion or the deformation of the foil (indicated by x in Table 2).
  • Table 2 also shows the capacity retention ratio during charging and discharging when using a Si—C-based active material.
  • the capacity maintenance rate during 50 cycles of charge and discharge was confirmed at a charge and discharge rate of 0.2 C using a hybrid active material of Si and C blended to 2500 mAh / g.
  • the electrodes were prepared by baking at 300 ° C. using a polyimide binder manufactured by Hitachi Chemical as the binder. If the capacity retention rate after 50 cycles is 70% or more, it is practical, but more preferably 80% or more.
  • the overall tensile strength of the copper foils having the first copper layer and the second copper layer of Examples 24 to 33 was 500 MPa or more at room temperature. Further, the entire Young's modulus of the copper foil having the first copper layer and the second copper layer of Examples 24 to 33 was 70 to 120 GPa at room temperature. In addition, the nanoindenter hardness of the surface of the second copper layer of the copper foil having the first copper layer and the second copper layer in Examples 24 to 34 was 180 to 370 mgf / ⁇ m 2 . Further, the overall tensile strength of the copper foils having the first copper layer and the second copper layer of Examples 24 to 34 was 400 MPa or more as measured at room temperature after heat treatment at 300 ° C. for 1 hour.
  • the total Young's modulus of the copper foils having the first copper layer and the second copper layer of Examples 24 to 34 was 65 GPa or more as measured at room temperature after heat treatment at 300 ° C. for 1 hour. Further, as shown in Table 2, the samples of Examples 24 to 34 were evaluated to have a capacity retention rate of 50% or more or 70% or more after 50 cycles. As described above, Examples 24 to 34 were copper foils having good adhesion to the active material, no wrinkles when the active material was mounted, and good battery characteristics.
  • Comparative Example 11 is a sample that does not have a second copper layer, and since the surface hardness (nanoindenter hardness) was high, the adhesion with the active material was inferior, and The discharge characteristics could not be satisfied.
  • Comparative Examples 12 to 14 have low tensile strength and Young's modulus at room temperature, low tensile strength and Young's modulus even after heat treatment at 300 ° C. for 1 hour, and the foil fills the foil when the active material is mounted and satisfies charge / discharge characteristics. I could't. Further, as shown in Table 2, the capacity retention rate after 50 cycles was evaluated to be less than 70% in all of Comparative Examples 11 to 14.
  • the active material adhesion is good and the foil is not deformed. High adhesion between the substance and the copper foil can be maintained, and a copper foil having mechanical strength (tensile strength) and hardness can be provided.

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Abstract

Le problème décrit par l'invention est de fournir une feuille de cuivre qui ne se plisse pas facilement au moment du travail à la presse ou au moment de la charge ou de la décharge, qui est capable de maintenir un haut niveau d'adhésion aux matériaux actifs d'anode à base de carbone et à base de Si, et qui offre une bonne résistance mécanique (résistance à la traction) et une bonne dureté, ainsi qu'une anode pour batterie lithium-ion l'utilisant, et une batterie rechargeable lithium-ion l'utilisant. La solution de l'invention concerne une feuille de cuivre qui comprend une première couche de cuivre avec une résistance à la traction d'au moins 550 MPa et une deuxième couche de cuivre qui est située sur au moins un côté de la première couche de cuivre et qui a une dureté inférieure à celle de la première couche de cuivre. La résistance à la traction de la feuille de cuivre mesurée à température ambiante après une heure de traitement thermique à 300 °C est d'au moins 400 MPa.
PCT/JP2014/050942 2013-01-18 2014-01-20 Feuille de cuivre, anode pour batterie lithium-ion, et batterie rechargeable lithium-ion WO2014112619A1 (fr)

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KR102040073B1 (ko) * 2018-10-16 2019-11-04 장 춘 페트로케미컬 컴퍼니 리미티드 전해 동박, 이를 포함하는 전극 및 이를 포함하는 리튬 이온 배터리
CN112993261A (zh) * 2019-12-12 2021-06-18 陕西铭硕新能源科技有限公司 一种高比能量超低温电池导电集流体处理方法
CN114784222A (zh) * 2021-03-29 2022-07-22 宁德新能源科技有限公司 电化学装置和电子装置

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CN111455414A (zh) * 2020-03-09 2020-07-28 深圳市惟华电子科技有限公司 一种用于生产渐变式电解铜箔的添加剂

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CN108183237A (zh) * 2017-11-29 2018-06-19 合肥国轩高科动力能源有限公司 一种硅基负极材料用量子点水系涂层铜箔及其制备方法
CN108183237B (zh) * 2017-11-29 2020-11-06 合肥国轩高科动力能源有限公司 一种硅基负极材料用量子点水系涂层铜箔及其制备方法
KR102040073B1 (ko) * 2018-10-16 2019-11-04 장 춘 페트로케미컬 컴퍼니 리미티드 전해 동박, 이를 포함하는 전극 및 이를 포함하는 리튬 이온 배터리
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CN114784222A (zh) * 2021-03-29 2022-07-22 宁德新能源科技有限公司 电化学装置和电子装置
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