WO2005103340A1 - 複合箔及びその製造方法、並びに該複合箔を用いた集電体、非水電解液二次電池用電極及び非水電解液二次電池 - Google Patents
複合箔及びその製造方法、並びに該複合箔を用いた集電体、非水電解液二次電池用電極及び非水電解液二次電池 Download PDFInfo
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- WO2005103340A1 WO2005103340A1 PCT/JP2005/007400 JP2005007400W WO2005103340A1 WO 2005103340 A1 WO2005103340 A1 WO 2005103340A1 JP 2005007400 W JP2005007400 W JP 2005007400W WO 2005103340 A1 WO2005103340 A1 WO 2005103340A1
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- Prior art keywords
- cobalt
- copper foil
- foil
- composite
- composite foil
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Classifications
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- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
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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
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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
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- 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 composite foil and a method of manufacturing the same.
- the present invention also relates to a current collector using the composite foil, an electrode for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery.
- Copper foil is used as a negative electrode current collector for this lithium ion secondary battery.
- this copper foil it is possible to use an electrolytic copper foil or a rolled copper foil.
- the negative electrode active material a carbon material, particularly graphitic carbon, is used, but higher capacity silicon, tin or their alloys are newly proposed.
- the negative electrode is formed, for example, by applying or sticking an active material to a current collector.
- the copper foil used as this negative electrode current collector is subjected to heat treatment at a temperature of about 400 ° C. for 10 hours or longer, as described in Patent Document 1, by coating or sticking an active material on the surface, etc. It is common to carry out an operation to carry the active material on the surface.
- a copper foil power collector layer, a silver interlayer laminated on one side or both sides of the collector layer, and silicon, Sn or the like laminated thereon are provided.
- the negative electrode for a lithium battery constituted of the active material layer which also has these alloying powers the Cu of the current collector layer and the element of the intermediate layer are compatible with each other at the interface between the current collector layer and the intermediate layer.
- An alloy phase is formed, and at the interface between the intermediate layer and the active material layer, an alloy phase in which elements of the intermediate layer and silicon, Sn or their alloys of the active material layer are compatible is formed.
- Negative electrode for lithium batteries is described.
- Patent Document 2 an intermediate layer is provided between the current collector layer and the active material layer to improve the adhesion between the layers and to prolong the charge and discharge life.
- Patent Document 3 is an electrode for a lithium secondary battery in which an active material film capable of absorbing and releasing lithium electrochemically or chemically is deposited on a current collector.
- Patent Document 1 describes a conductive metal foil having a surface roughness Ra of 0.2 m or more as a current collector, active material particles including Ge and Z or a Ge alloy, and copper or copper.
- an electrode for a lithium secondary battery obtained by sintering a mixture of conductive metal powder such as a copper alloy on a surface of a current collector in a nonoxidizing atmosphere.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2002-260637
- Patent Document 2 Japanese Patent Application Laid-Open No. 2004-22306
- Patent Document 3 Japanese Patent Application Laid-Open No. 2003-7305
- the active material When the active material is supported on the surface of the copper foil by heat treatment at about 400 ° C. while under pressure, ordinary electrolytic copper foil and rolled copper foil recrystallize and a softening phenomenon occurs. As a result, the tensile strength of the copper foil decreases and the elongation rate increases.
- the active material constituting the negative electrode material of the secondary battery always expands and contracts when performing charge and discharge, and the stress due to the expansion and contraction is applied to the copper foil constituting the current collector layer. It will be done.
- the tensile strength decreases due to heating, and the copper foil with a large elongation rate plastically deforms in a stretched state following the expansion behavior of the active material, and can not follow the shrinkage behavior. It will be in a shaped state.
- the negative electrode current collector of the non-aqueous electrolyte secondary battery is deformed, the charge / discharge characteristics are degraded as a result, the rated current defined in the standard can not be output, and the battery life is shortened.
- Patent Document 2 describes that a current collector layer and an active material layer are Although the purpose is to provide an intermediate layer and its purpose is to extend the charge and discharge life, Patent Document 2 is to prevent the reduction in tensile strength after heat treatment at a high temperature of the copper foil constituting the current collector. High, not to impart charge and discharge characteristics.
- Patent Document 3 defines the characteristics and physical properties of the current collector, thereby suppressing the occurrence of deformation such as wrinkles in the current collector due to charge and discharge, and the volume per volume of the lithium secondary battery. Although the energy density is increased, Patent Document 3 does not impart high charge / discharge characteristics by preventing a decrease in tensile strength after heat treatment at a high temperature of the copper foil constituting the current collector. .
- Patent Document 1 uses a conductive metal foil having a certain surface roughness Ra or more as a current collector, and a layer of a mixture of specific active material particles and conductive metal powder on the current collector surface. Power is obtained to obtain high discharge capacity and excellent charge and discharge cycles by sintering. This Patent Document 1 also prevents the decrease in tensile strength after heat treatment at high temperature of the copper foil constituting the current collector. High, not to impart charge and discharge characteristics.
- the present inventors have found that it is difficult to satisfy the required characteristics of the market with copper foil alone because of the physical properties and physical properties of copper, and the composite foil as described below By adopting the constitution of the above, it was conceived that a composite foil having high tensile strength can be obtained even after heat treatment at high temperature.
- the composite foil according to the present invention a method for producing the same, a current collector capable of imparting high charge / discharge characteristics, an electrode for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery are provided. It is in.
- the present inventors as a result of intensive studies to solve the above problems, have found that the above objects can be achieved by forming a specific metal or alloy layer on the surface of a copper foil.
- the composite foil according to the present invention is a composite foil according to any one of (1) or (2) shown below.
- the composite foil according to the present invention is formed by forming a displacement of a cobalt plating layer or a nickel-cobalt alloy plating layer 3 on the surface of a copper foil.
- a displacement of a cobalt plating layer or a nickel-cobalt alloy plating layer 3 is described as the surface!
- the above-mentioned matting layer is formed on one side of the copper foil
- the above-mentioned matting layer is formed on both sides of the copper foil. Describe in the meaning that includes. This is because the same effect can be obtained on one side or both sides.
- FIG. 1 exemplarily shows a state in which the plating layer is provided on both sides of the copper foil.
- the reason for providing either the cobalt plating layer or the nickel-cobalt alloy plated layer (hereinafter referred to as "different metal layer”) on both sides of the copper foil 2 is that they have excellent heat resistance characteristics, 400 ° CX When heating is performed for about 10 hours, softening occurs and the reduction in tensile strength when viewed as the entire composite foil is effectively suppressed, and it is easy to set the tensile strength after heating to 50 kgfZm 2 or more. It is. Also, the reason why the dissimilar metal layer is provided on both sides of the copper foil is that if it is provided on one side, a curling phenomenon occurs in which the copper foil curls up and is wound, resulting in a lack of gringing properties. Furthermore, the presence of a film excellent in acid resistance such as cobalt on both surfaces can prevent acid corrosion of the copper foil itself.
- the copper foil referred to herein it is possible to use an electrolytic copper foil or a rolled copper foil, and it is preferable to use one having a nominal thickness of 7 m to 35 m.
- the copper foil used for the negative electrode current collector of the non-aqueous electrolyte solution secondary battery tends to be thinner along with the demand for smaller and lighter batteries.
- the composite foil which concerns on this invention it considered as 7 micrometers-35 micrometers in consideration of providing a dissimilar metal layer in the surface. If the nominal thickness of the copper foil is less than 7 ⁇ m, it will be difficult to form the dissimilar metal layer continuously on the surface using the copper foil surface treatment device, and the product yield will dramatically deteriorate. is there. On the other hand, when the nominal thickness of the copper foil exceeds 35 ⁇ m, the thickness of the composite foil provided with the dissimilar metal layer is not preferable because the thickness exceeds the proper thickness required for the current copper foil for current collector.
- the thickness of the dissimilar metal layer is preferably 0.5 ⁇ m to 5.0 ⁇ m! /. If the thickness of the tack layer is less than 0.5 m, a tensile strength to counter the expansion behavior of the active material during charge and discharge as a non-aqueous electrolyte secondary battery can not be expected. Meanwhile, the above dissimilar metals Even if the layer thickness exceeds 3.O / zm, the tensile strength value does not improve significantly, and only relatively large amounts of relatively expensive components such as nickel and cobalt are used. is there. However, in order to secure more stable mechanical strength in consideration of process variations etc., it is preferable to control the production with the upper limit thickness of the above-mentioned dissimilar metal layer set to 5.0 m. .
- the thickness of the dissimilar metal layer provided on the surface of the rough surface and the surface of the glossy surface it is preferable to make the thickness of the dissimilar metal layer provided on the surface of the rough surface and the surface of the glossy surface different. This is to prevent the occurrence of the curling phenomenon described above. For example, if a dissimilar metal layer of 2. thickness is provided on the shiny side of a 12 m nominal thickness electrolytic copper foil, a cobalt layer of 3.5 m thickness etc. will be provided on the rough side.
- the thickness of the dissimilar metal layer provided on the glossy surface side is t (m)
- the thickness of the dissimilar metal layer provided on the rough surface side is t + O.5 ( ⁇ !)
- t + 1.2 (m) It is preferable to If the thickness force of the dissimilar metal layer provided on the rough surface side is less than t + O. 5 (m), the effect of suppressing the curling phenomenon can not be obtained, and t + 1.2 (/ ⁇ ) is exceeded.
- the tendency for curling which is the reverse of that of the original copper foil, tends to occur.
- the composite foil of the above-mentioned type also exhibits sufficient anti-softening performance when heated at 400 ° CX for about 10 hours, and exhibits a tensile strength of 50 kgfZ mm 2 or more. And, even when heat treatment at temperatures exceeding 400 ° C. is assumed, the cobalt plating layer or the nickel-cobalt alloy plated layer has good anti-softening properties in which mutual diffusion with the copper foil layer hardly occurs even compared to nickel. Demonstrate.
- Fig. 4 shows a cross-sectional observation photograph by an optical microscope before heating of the composite copper foil in which only the hard nickel layer is formed
- Fig. 5 shows a cross-sectional observation photograph by an optical microscope after heating at 400 ° CX for 10 hours. Comparing FIG. 4 with FIG. 5, in the cross-sectional observation photograph after heating, a void-like shape is observed inside the copper foil (the location indicated by the arrow in FIG. 5). This void is considered to be generated by the Kirkendall effect in which the boundary between the hard nickel plating layer and the copper foil layer is moved by mutual diffusion by heating.
- the production of the composite foil provided with the cobalt layer according to the present invention is characterized in that the copper foil is immersed in a cobalt electrolytic plating bath of the following composition, and electrolytic plating is performed under the following electrolytic conditions to form a cobalt plating layer. It is a thing.
- Various methods can be used to perform condensation. For example, a) Using cobalt sulfate, the concentration is 5 to 30 gZl, the concentration is 3 to 50 g of trisodium nitrate, and the solution temperature is 20 to 50.
- the above-mentioned cobalt plating solution contains a coagulant at a concentration of 0.05 g zl to 0.3 g zl.
- copper foil is an electrolytic copper foil or a rolled copper foil, It is preferable that the thickness is 7 micrometers-35 micrometers. Furthermore, it is preferable that the thickness of the above-mentioned cobalt plating layer be 0.5 / ⁇ -5. 0 m.
- the copper foil is immersed in a nickel-cobalt alloy electrolytic plating bath of the following composition, and electrolytic plating is carried out under the following electrolytic conditions.
- electrolytic plating is carried out under the following electrolytic conditions.
- various plating conditions can be adopted to perform plating of cobalt-cobalt alloy. For example, 80 to 180 g / l sulfuric acid-conoreto, 80 to 120 g / l sulfuric acid, 20 to 40 g / l boric acid, 10 to 15 g Zl potassium chloride, 0.1 to 15 g Zl sodium dihydrogen phosphate, liquid Temperature 30-50.
- the above-mentioned nickel-cobalt alloy plating solution contains sodium formate at a concentration of 25 gZl to 50 gZl.
- copper foil is an electrolytic copper foil or a rolled copper foil, It is preferable that the thickness is 7 micrometers-35 micrometers. Furthermore, it is preferable that the thickness of the above-mentioned cobalt-nickel alloy plated layer be 0.5 m to 5.0 m. Yes.
- the current collector referred to here is one using the composite foil according to the present invention, and it is preferable to use the composite foil according to the present invention.
- This current collector has high resistance to the expansion and contraction behavior during charge and discharge of the active material supported on the surface because of the high tensile strength obtained by the excellent anti-softening property of the composite foil after high temperature heating. This makes it possible to extend the life of the current collector that constitutes the negative electrode of the non-aqueous electrolyte secondary battery. That is, the composite foil according to the present invention is suitable for use as a current collector constituting the negative electrode of a non-aqueous electrolyte secondary battery, and the active material is supported and the length of the current collector thereafter is long. Allows life extension.
- the electrode for a non-aqueous electrolyte secondary battery according to the present invention is formed using the above current collector in combination with a known active material. Noinda and others are also used as needed.
- an electrode obtained by coating, plating, sputtering or vacuum deposition of silicon, tin or an alloy of these as an active material on the above current collector has a high charge / discharge capacity.
- the above electrode is used as a negative electrode, and known anode materials, electrolytic solutions and the like can be used.
- lithium cobaltate, lithium manganate and the like are used as the anode material
- propylene carbonate, ethylene carbonate and the like are used as the electrolyte.
- the composite foil provided with the cobalt plating layer or the nickel-cobalt alloy plating layer according to the present invention has a high tensile strength of 50 kgfZ mm 2 or more even after heat treatment at a high temperature, for example, 400 ° CX for about 10 hours. Even when heated at temperatures above C, they exhibit very good tensile strength.
- a plating film excellent in anti-softening property after high temperature heating can be formed on the surface of a copper foil, and the production can also be stably performed with high yield.
- the above composite foil has high tensile strength after long-time heating at high temperature, it is suitable to be used as a current collector of the electrode of the non-aqueous electrolyte secondary battery, and for charging and discharging of the secondary battery. It can cope with the accompanying expansion and contraction, and as a result, a high quality non-aqueous electrolyte secondary battery can be obtained, and excellent charge and discharge characteristics and long battery life can be achieved.
- a composite electrolytic plating bath of the above-mentioned composition For the production of a composite foil comprising a cobalt layer, it is preferable to adopt a composite electrolytic plating bath of the above-mentioned composition. This is because a cobalt plating layer which is most excellent in anti-softening property after high temperature heating can be obtained.
- a cobalt sulfate electrolytic plating bath to which a coagulant is added is employed for producing a composite foil having a cobalt layer, using a cobalt sulfate electrolytic solution described below.
- the concentration of CoSO ⁇ 7 ⁇ be 120 gZl to 200 gZl.
- H BO serves as a buffer.
- concentration of H BO is 25 g
- the liquid temperature can be in the range of 20 ° C. to 50 ° C.
- the lower the liquid temperature the higher the tensile strength.
- the solution temperature is less than 20 ° C, the cobalt deposition rate will be low, and the industrial productivity will not be satisfied.
- the tensile strength tends to be a steady value saturated.
- it is set as the solution of the above-mentioned composition It is the best and stable tensile strength to adopt pH 2-5. Thus, it is possible to obtain a film having a tackiness.
- the flocculant referred to here may be one commercially available as a flocculant, but it is particularly preferable to use one containing an acrylamide polymer as a main agent. Then, this flocculant is used to control the deposition rate of cobalt and to improve the film thickness uniformity of the coating, and is added so as to be from 0.5 gzl to 0.3 gzl in the plating bath.
- the aggregating agent is less than 0.05 g / l, it can not contribute to the improvement of the film thickness uniformity of the cobalt plating film, and even if the aggregating agent is increased in excess of 0.3 g / l, it is rather cobalt cobalt plating. The film thickness uniformity of the film is degraded.
- a nickel-cobalt alloy electrolytic plating bath of the above-mentioned composition it is preferred to employ a nickel-cobalt alloy electrolytic plating bath of the above-mentioned composition. This is because a nickel-cobalt alloy plated layer most excellent in anti-softening properties after high temperature heating can be obtained.
- the nickel-cobalt-alloy electrolytic plating bath used in the present invention adopts a composition in which sulfuric acid cobalt is added to the Watt bath composition when nickel plating is performed. Therefore, a very simple and stable electrolytic solution capable of solution liquid composition is adopted.
- the NiSO ⁇ 6 ⁇ concentration in the nickel-cobalt alloy electrolytic plating bath is lOOgZl.
- H BO plays a role as a buffer, and the concentration of H BO is
- the thickness is out of this range, the strength of the nickel complex alloy plated layer itself is insufficient, and the film thickness uniformity of the plating layer is also impaired.
- the liquid temperature can be in the range of 20 ° C. to 50 ° C. Also in the case of the nickel-cobalt alloy plating layer, the lower the liquid temperature, the higher the tensile strength tends to be. However, when the liquid temperature is less than 20 ° C., the deposition rate of the nickel-cobalt alloy decreases, and the industrial productivity is not satisfied. On the other hand, when the liquid temperature is around 50 ° C., the tensile strength tends to be a steady value with saturation. And if it is set as the solution of the above-mentioned composition, pH 2-5 will be able to obtain the most suitable and stable Mekki coating with stable tensile strength.
- sodium formate HCOONa
- This sodium formate is known to be used when a hexavalent chromium ion is formed as a trivalent chromium ion and a chromium plating layer is deposited as an amorphous layer to obtain high hardness. Therefore, when used to form the nickel-cobalt alloy plated layer according to the present invention, it contributes as a reducing agent for metal ions dissolved in the plating solution, and reduces the difference in the deposition efficiency between the nickel component and the condensate component. A uniformly dispersed alloy plating layer can be obtained without uneven distribution of the two components.
- Sodium formate is preferably used in a concentration range of 25 g Zl to 50 g Zl. If the concentration of sodium formate is less than 25 g / l, the nickel component and cobalt in the alloy plating layer A uniform mixed state with the components can not be obtained, and even if an amount exceeding 50 g Zl concentration is added, a good nickel cobalt alloy plated layer can not be obtained.
- a composite foil provided with a cobalt layer was manufactured, heat treated at 400 ° C. for 10 hours, and measurement of tensile strength and elongation was performed.
- the electrolytic copper foil (thickness 12 / ⁇ , VLP foil, manufactured by Mitsui Mining & Smelting Co., Ltd.) is immersed in a cobalt sulfate electrolytic plating bath of the following composition, and electrolytic plating is carried out under the following electrolytic conditions.
- a 2 m-thick, 3 m-thick cone-like laminated layer was formed on the rough surface and a rough surface, to prepare a 17 m-thick composite foil.
- a composite foil provided with a cobalt-nickel alloy layer was manufactured, heat-treated at 400 ° CX 10 hours, and measurement of tensile strength and elongation was performed.
- the electrodeposited copper foil (12 m in thickness, VLP foil, manufactured by Mitsui Mining & Smelting Co., Ltd.) is immersed in a cobalt-nickel alloy electrolytic plating bath of the following composition, and electrolytic plating is performed under the following electrolytic conditions.
- Cobalt-Nickel plating layer 2 ⁇ m thick and 3 m thick on rough surface on a glossy surface, 17 m thick composite foil was prepared.
- Example 1 the tensile strength and the elongation after heating at 400 ° C. for 10 hours in a vacuum were evaluated for the composite foil provided with the obtained cobalt-nickel alloy layer. The results are shown in Table 1.
- a composite foil provided with a copper-nickel alloy plated layer on both sides of an electrodeposited copper foil was manufactured and compared with the above example.
- an electrolytic copper foil (12 m in thickness, VLP foil, manufactured by Mitsui Mining & Smelting Co., Ltd.) is immersed in a copper-nickel alloy electrolytic plating bath of the following composition, and electrolytic plating is performed under the following electrolytic conditions.
- a 2 m thick shiny surface and a 3 m thick copper-nickel plating layer were formed on the rough surface to prepare a 17 m thick composite foil.
- Example 1 or Example 2 has extremely high tensile strength even after heat treatment, as compared with Comparative Example 1 in which the electrodeposited copper foil is used as it is. Ru. And, in Comparative Example 2, in spite of forming the plating layer on both sides of the copper foil, it is understood that the tensile strength after the heat treatment is largely reduced.
- the composite foil according to the present invention can maintain high tensile strength even after heat treatment at high temperature. And, by using this composite foil as a current collector of an electrode for a non-aqueous electrolyte secondary battery, it is possible to cope with expansion and contraction associated with charge and discharge of the secondary battery, and it is obtained as a result thereof High charge and discharge characteristics can be imparted to non-aqueous electrolyte secondary batteries Ru. In addition, the composite foil can be stably produced with high yield by the production method of the present invention.
- FIG. 1 is a schematic cross-sectional view of a composite foil according to the present invention.
- FIG. 2 is an optical micrograph of a cross section of the composite foil according to the present invention in a normal state (before heating).
- FIG. 3 is an optical micrograph of a cross section of the composite foil according to the present invention after heating (400 ° C. ⁇ 10 hours).
- FIG. 4 is an optical micrograph of a cross section of a composite foil with only a hard nickel layer only (before heating).
- FIG. 5 is an optical micrograph of a cross section of a composite foil having only a hard nickel layer after heating (400 ° C. ⁇ 10 hours).
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- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Electroplating Methods And Accessories (AREA)
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Abstract
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Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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JP2004123482 | 2004-04-19 | ||
JP2004-123482 | 2004-04-19 | ||
JP2004143779 | 2004-05-13 | ||
JP2004-143779 | 2004-05-13 | ||
JP2004203964A JP4438541B2 (ja) | 2004-04-19 | 2004-07-09 | 非水電解液二次電池の負極集電体用の複合箔及びその製造方法、並びに該複合箔を用いた負極集電体、非水電解液二次電池用電極及び非水電解液二次電池 |
JP2004-203964 | 2004-07-09 |
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WO2008053464A2 (en) * | 2006-11-01 | 2008-05-08 | Bar-Ilan University | Nickel-cobalt alloys as current collectors and conductive interconnects and deposition thereof on transparent conductive oxides |
CN102024941A (zh) * | 2010-11-06 | 2011-04-20 | 合肥国轩高科动力能源有限公司 | 锂离子电池负极集流体铜箔的表面处理方法 |
WO2014057804A1 (ja) * | 2012-10-12 | 2014-04-17 | 三井金属鉱業株式会社 | 表面処理銅箔、表面処理銅箔の製造方法、負極集電体及び非水系二次電池の負極材 |
JP2016223018A (ja) * | 2016-08-23 | 2016-12-28 | 三井金属鉱業株式会社 | 表面処理銅箔、負極集電体及び非水系二次電池の負極材 |
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JP5499446B2 (ja) * | 2008-06-05 | 2014-05-21 | ソニー株式会社 | 負極集電体、負極および二次電池 |
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JP2013069684A (ja) * | 2011-09-09 | 2013-04-18 | Hitachi Cable Ltd | リチウムイオン二次電池用負極集電銅箔、リチウムイオン二次電池用負極、リチウムイオン二次電池及びリチウムイオン二次電池用負極集電銅箔の製造方法 |
JP5918623B2 (ja) | 2012-05-17 | 2016-05-18 | 株式会社Shカッパープロダクツ | リチウムイオン二次電池用負極集電銅箔の製造方法、リチウムイオン二次電池用負極の製造方法、及びリチウムイオン二次電池の製造方法 |
KR102101046B1 (ko) | 2012-05-22 | 2020-04-14 | 미쓰이금속광업주식회사 | 구리박, 부극 집전체 및 비수계 2차 전지의 부극재 |
JP6573312B2 (ja) * | 2015-06-22 | 2019-09-11 | 日産自動車株式会社 | リチウムイオン二次電池用集電体 |
JP7148555B2 (ja) * | 2018-01-31 | 2022-10-05 | 東洋鋼鈑株式会社 | 電磁波シールド材および電磁波シールド材の製造方法 |
JP7085394B2 (ja) * | 2018-04-13 | 2022-06-16 | 東洋鋼鈑株式会社 | 積層電解箔 |
CN108823622A (zh) * | 2018-06-29 | 2018-11-16 | 桑顿新能源科技有限公司 | 一种用于锂电池的负极极耳材料及其制造方法 |
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JPH08130006A (ja) * | 1994-10-27 | 1996-05-21 | Mitsubishi Cable Ind Ltd | 負極、その製造方法及びLi二次電池 |
JPH11307102A (ja) * | 1998-04-24 | 1999-11-05 | Hitachi Ltd | リチウム二次電池とその製造法 |
JP2001291940A (ja) * | 2000-04-05 | 2001-10-19 | Nikko Materials Co Ltd | 銅張り積層板 |
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- 2004-07-09 JP JP2004203964A patent/JP4438541B2/ja not_active Expired - Fee Related
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- 2005-04-18 WO PCT/JP2005/007400 patent/WO2005103340A1/ja active Application Filing
- 2005-04-18 TW TW094112247A patent/TW200604386A/zh unknown
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JPH08130006A (ja) * | 1994-10-27 | 1996-05-21 | Mitsubishi Cable Ind Ltd | 負極、その製造方法及びLi二次電池 |
JPH11307102A (ja) * | 1998-04-24 | 1999-11-05 | Hitachi Ltd | リチウム二次電池とその製造法 |
JP2001291940A (ja) * | 2000-04-05 | 2001-10-19 | Nikko Materials Co Ltd | 銅張り積層板 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008053464A2 (en) * | 2006-11-01 | 2008-05-08 | Bar-Ilan University | Nickel-cobalt alloys as current collectors and conductive interconnects and deposition thereof on transparent conductive oxides |
WO2008053464A3 (en) * | 2006-11-01 | 2009-08-27 | Bar-Ilan University | Nickel-cobalt alloys as current collectors and conductive interconnects and deposition thereof on transparent conductive oxides |
US9064985B2 (en) | 2006-11-01 | 2015-06-23 | Bar-Ilan University | Nickel-cobalt alloys as current collectors and conductive interconnects and deposition thereof on transparent conductive oxides |
CN102024941A (zh) * | 2010-11-06 | 2011-04-20 | 合肥国轩高科动力能源有限公司 | 锂离子电池负极集流体铜箔的表面处理方法 |
WO2014057804A1 (ja) * | 2012-10-12 | 2014-04-17 | 三井金属鉱業株式会社 | 表面処理銅箔、表面処理銅箔の製造方法、負極集電体及び非水系二次電池の負極材 |
JP2016223018A (ja) * | 2016-08-23 | 2016-12-28 | 三井金属鉱業株式会社 | 表面処理銅箔、負極集電体及び非水系二次電池の負極材 |
Also Published As
Publication number | Publication date |
---|---|
JP2005350761A (ja) | 2005-12-22 |
JP4438541B2 (ja) | 2010-03-24 |
TW200604386A (en) | 2006-02-01 |
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