WO2012066980A1 - リチウムイオン二次電池負極集電体用の銅箔、リチウムイオン二次電池負極材及びリチウムイオン二次電池負極集電体選定方法 - Google Patents
リチウムイオン二次電池負極集電体用の銅箔、リチウムイオン二次電池負極材及びリチウムイオン二次電池負極集電体選定方法 Download PDFInfo
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- WO2012066980A1 WO2012066980A1 PCT/JP2011/075716 JP2011075716W WO2012066980A1 WO 2012066980 A1 WO2012066980 A1 WO 2012066980A1 JP 2011075716 W JP2011075716 W JP 2011075716W WO 2012066980 A1 WO2012066980 A1 WO 2012066980A1
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- negative electrode
- copper foil
- secondary battery
- ion secondary
- lithium ion
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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
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/04—Processes of manufacture in general
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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
-
- 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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- 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
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Definitions
- the present invention relates to a copper foil for a negative electrode current collector for a lithium ion secondary battery, a lithium ion secondary battery negative electrode material, and a method for selecting a negative electrode current collector for a lithium ion secondary battery. It is related with the copper foil for lithium ion secondary battery negative electrode collectors which can prevent a deformation
- Lithium ion secondary batteries in which charging and discharging are performed by moving lithium ions between a positive electrode and a negative electrode are known.
- Lithium ion secondary batteries are widely used as power sources for portable electronic devices and the like because they have a high capacity and a high energy density and are free from problems such as memory effects.
- a copper foil is used as a negative electrode current collector of a lithium ion secondary battery.
- the copper foil for example, electrolytic copper foil or rolled copper foil is used.
- a negative electrode material of a lithium ion secondary battery includes a negative electrode mixture layer including a negative electrode active material, a conductive material, a binder (binder) and the like on the surface of a copper foil as a current collector (for example, Patent Document 1).
- the negative electrode active material carbon-based materials such as graphite capable of occluding and releasing lithium ions are generally used, and in recent years, silicon-based materials that have a larger theoretical capacity than graphite-based materials And tin-based materials have been proposed as next-generation negative electrode active materials.
- the negative electrode active material exemplified above occludes / releases lithium during charge / discharge, but at that time, volume change occurs.
- the negative electrode mixture layer expands / shrinks along with the volume change of the negative electrode active material, the negative electrode mixture layer is in close contact with the surface of the current collector, so that stress is applied between the negative electrode mixture layer and the current collector. Join. If the current collector is deformed such as wrinkles due to the expansion of the current collector by repeating the charge / discharge cycle, a short circuit occurs between the positive electrode and the negative electrode, or the distance between the positive electrode and the negative electrode Changes, the uniform electrode reaction is hindered, and the charge / discharge cycle durability decreases.
- silicon-based materials and tin-based materials have a large volume change during charge / discharge, so when silicon-based materials and tin-based materials are used as negative electrode active materials, the problem is significant. It was.
- the subject of this invention is the copper foil for lithium ion secondary battery negative electrode electrical power collectors which can prevent a deformation
- the present inventors have come to solve the above problems by adopting the following copper foil and lithium ion secondary battery negative electrode material for a negative electrode of a lithium ion secondary battery. .
- the present inventors have found a method for selecting an appropriate copper foil as a negative electrode current collector for a lithium ion secondary battery.
- the copper foil for the negative electrode current collector of the lithium ion secondary battery according to the present invention has an origin of O in the load-elongation curve when a 10 mm wide test piece made of the copper foil is subjected to a tensile test, and the elongation the rate is the load when load when the E Q is P Q - the point on the growth curve when is Q, in the region L value is 0.8 or more represented by the following formula (1)
- the maximum load when the test piece is subjected to the tensile test is 30 N or more.
- the triangle OQE Q indicates a triangle having the origin O, the point Q, and the point E Q as vertices in the load-elongation rate curve.
- the region OQE Q indicates a region surrounded by the curve OQ, the line segment QE Q, and the line segment OE Q in the load-elongation rate curve.
- the L value is a value for evaluating the linearity of the load-elongation curve.
- the L value always shows 0.8 or more when the load applied to the test piece is 30 N or less. At this time, it is more preferable that the L value always shows 0.8 or more in a range where the load applied to the test piece is 40 N or less.
- the L value is also obtained when the copper foil after heat treatment at 70 ° C. to 450 ° C. is used as the test piece.
- the maximum load load is preferably 30 N or more.
- the surface roughness (Ra) of each surface of the copper foil is preferably in the range of 0.2 ⁇ m to 0.7 ⁇ m.
- the lithium ion secondary battery negative electrode material according to the present invention uses the copper foil for a lithium ion secondary battery negative electrode current collector as described above as a current collector, and includes a negative electrode active material on the surface of the current collector. A negative electrode mixture layer is provided.
- the negative electrode active material is at least one selected from the group consisting of B, Al, Ga, In, C, Si, Ge, Sn, Pb, Zn, and Ag. It is preferable to use a material containing the above elements. Among these, it is particularly preferable to use a material containing Si or Sn having a large theoretical capacity.
- the method for selecting a negative electrode current collector for a lithium ion secondary battery according to the present invention is a method for selecting a negative electrode current collector for a lithium ion secondary battery for selecting a copper foil used for a negative electrode current collector for a lithium ion secondary battery.
- the copper foil for a negative electrode current collector of a lithium ion secondary battery described in any of the above is selected as a current collector.
- the copper foil according to the present invention as a current collector for a negative electrode of a lithium ion secondary battery, a material having a large theoretical capacity, such as Si or Sn, is used as a material for occluding or alloying with lithium.
- the negative electrode mixture layer can follow the expansion / contraction of the negative electrode mixture layer even if the negative electrode mixture layer is greatly expanded / contracted due to charge / discharge. As a result, even when the charge / discharge cycle is repeated, deformation of the current collector or the like can be prevented from occurring or breaking.
- the copper foil according to the present invention as a current collector for the negative electrode of a lithium ion secondary battery, further increase in energy density and capacity of the lithium ion secondary battery can be achieved, The life of the lithium ion secondary battery can be extended.
- Example 3 is a load-elongation curve for explaining L values indicating selection criteria or characteristics of a copper foil for a negative electrode current collector of a lithium ion secondary battery according to the present invention. It is a figure which shows the load-elongation rate curve of the electrolytic copper foil manufactured in Example 1- Example 3 and a comparative example. It is the figure which plotted the L value at that time with respect to the tensile load loaded on the test piece.
- X-ray-CT image (a) obtained by photographing the cross section of the deformation evaluation cell 1-1 produced in Example 1
- X-ray CT image obtained by photographing the cross section of the deformation evaluation cell 2-1 produced in Example 2.
- X-ray-CT image (c) obtained by photographing the cross section of the deformation evaluation cell 3-1 produced in Example 3, and X-ray obtained by photographing the cross section of the deformation comparison cell 1-1 produced in the comparative example.
- -CT image (d). X-ray-CT image (a) obtained by photographing the cross section of the deformation evaluation cell 1-2 produced in Example 1, and X-ray CT image obtained by photographing the cross section of the deformation evaluation cell 2-2 produced in Example 2.
- B) X-ray-CT image (c) obtained by photographing a cross section of the deformation evaluation cell 3-2 produced in Example 3, and X-ray obtained by photographing a cross section of the deformation evaluation cell 1-2 produced in the comparative example.
- FIG. 6 is a photograph showing an external appearance of a current collector after one charge / discharge cycle of a deformation evaluation cell 3-2 produced in Example 3.
- FIG. 6 is a photograph showing the external appearance of a current collector after one charge / discharge cycle of a deformation comparison cell 1-1 produced in a comparative example.
- a lithium ion secondary battery has a wound body in which a positive electrode material and a negative electrode material formed in a long shape are integrally wound with a separator interposed in a rectangular or cylindrical casing. What is contained is generally known.
- a cell in which a set of a positive electrode material and a negative electrode material formed in a rectangular shape are opposed to each other via a separator, or a laminate cell type in which a plurality of sets of cells are laminated and covered with a laminate material is also adopted. Yes. Since lithium ions are highly reactive with water, a nonaqueous electrolytic solution is generally used as the electrolytic solution.
- Electrode reaction In the electrode reaction of a lithium ion secondary battery, lithium ions (Li +) move from the positive electrode side to the negative electrode side through the separator, and charging is performed by occlusion of lithium ions in the negative electrode mixture layer on the negative electrode side. Is done. And lithium ion is discharge
- the electrode material positive electrode material, negative electrode material
- an electrode (positive electrode, negative electrode) mainly refers to an electrode material in a state that can be accompanied by an electrode reaction, or an electrode as a component in a state assembled as a lithium ion secondary battery. .
- the positive electrode material includes a positive electrode mixture layer (or positive electrode active material layer) on at least one side of a positive electrode current collector formed in a predetermined shape.
- the positive electrode mixture layer includes a positive electrode active material, a conductive material, a binder (binder), and the like.
- a lithium transition metal composite oxide is used as the positive electrode active material.
- the lithium transition metal composite oxide include LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 2 , LiCo 0 . 5 Ni 0 . 5 O 2 , LiNi 0 . 7 Co 0 . 2 Mn 0. Such as 1 O 2, LiNi 1/3 Co 1/3 Mn 1/3 O 2 can be used.
- the positive electrode active material is not limited to these exemplified lithium transition metal composite oxides.
- a positive electrode active material can be used 1 type or in combination of 2 or more types.
- the positive electrode mixture layer is obtained by suspending the positive electrode active material, the conductive material, and the binder in an appropriate solvent to produce a positive electrode mixture, and applying this to the surface of a current collector such as an aluminum foil, After drying, it is annealed as necessary, and then manufactured through processes such as roll rolling and pressing.
- a current collector such as an aluminum foil
- acetylene black or the like can be used.
- the binder polyvinylidene fluoride or the like can be used.
- the negative electrode material comprises a negative electrode mixture layer on at least one side of a negative electrode current collector formed in a predetermined shape.
- the negative electrode mixture layer includes a negative electrode active material, a conductive material, a binder, and the like.
- a conductive material acetylene black, ketjen black, graphite or the like can be used.
- binder polyamic acid (polyimide), polyvinylidene fluoride, styrene butadiene rubber, polyethylene, ethylene propylene diene monomer, polyurethane, polyacrylic acid, polyvinyl ether, polyamide imide, or the like can be used.
- the negative electrode mixture layer is prepared by suspending a negative electrode active material, a conductive material, and a binder described below in an appropriate solvent to produce a negative electrode mixture, which is the present invention. It is applied to the surface of the current collector according to the above, dried, and then subjected to an annealing treatment as necessary, and then manufactured through processes such as roll rolling and pressing.
- the manufacturing method of the negative electrode material is not particularly limited, and can be manufactured by a sputtering method or a vapor deposition method.
- Negative electrode active material As the negative electrode active material, in the present invention, a material that occludes / releases lithium (including a material that is alloyed / dealloyed with lithium, the same applies hereinafter) is used.
- Specific examples of the negative electrode active material include materials containing at least one element selected from the group consisting of B, Al, Ga, In, C, Si, Ge, Sn, Pb, Zn, and Ag.
- the material containing at least one element selected from the group consisting of B, Al, Ga, In, C, Si, Ge, Sn, Pb, Zn, and Ag is a simple substance of each of these elements. It may be an oxide containing at least one of these elements or a nitride.
- the alloy containing these elements may be sufficient.
- Si and Sn have a higher theoretical capacity than carbon-based materials that have been used as negative electrode active materials in the past, from the viewpoint of providing a lithium ion secondary battery with higher energy density and higher capacity. It is preferable to use a material containing Si or a material containing Sn as the negative electrode active material.
- the material containing Si is a material that can occlude and release lithium (including alloying and dealloying, the same applies hereinafter) and contains Si.
- Si silicon
- silicon (Si) simple substance, silicon oxide, an alloy of silicon and other metal elements, and the like can be given. These materials can be used alone or in combination.
- the metal element that forms an alloy with silicon include one or more elements selected from the group consisting of B, Cu, Ni, Co, Cr, Fe, Ti, Pt, W, Mo, and Au. Of these metal elements, B, Cu, Ni, and Co are preferable. In particular, Cu and Ni are preferably used from the viewpoints of excellent electronic conductivity and low ability to form a lithium compound.
- the material containing Sn is a material that can occlude / release lithium, or can be alloyed / dealloyed with lithium and contains Sn.
- tin (Sn) simple substance, tin oxide, and an alloy of tin and other elements can be used.
- the metal element that forms an alloy with tin include one or more elements selected from the group consisting of Cu, Ni, Co, Cr, Fe, Ti, Pt, W, Mo, and Au. More specifically, an Sn—Co—C alloy can be cited as an alloy of tin and other elements.
- Si or Sn has a large structural change or volume change during lithium insertion / release compared with carbon-based materials such as graphite. Since the negative electrode mixture layer is formed so as to be in close contact with the surface of the current collector, when the volume of the negative electrode mixture layer expands and contracts greatly during charge / discharge, when the charge / discharge cycle is repeated, the negative electrode mixture layer and A large load is repeatedly applied to the current collector. For this reason, in a lithium ion secondary battery using Si or Sn or the like as a negative electrode active material, the current collector expands or contracts as a result of deformation such as wrinkles as compared with the case where a carbon-based material such as graphite is used as a negative electrode active material. Or easily break.
- the copper foil according to the present invention is characterized by having the mechanical characteristics described below, and is suitably used as a current collector for a negative electrode of a lithium ion secondary battery. be able to.
- the origin is O and the elongation is E in a load-elongation curve (see FIG. 1) when a test piece made of the copper foil having a width of 10 mm is subjected to a tensile test.
- the load when the load when the Q is P Q - the point on the growth curve is taken as Q in the region L value is 0.8 or more represented by the following formula (1), the test It is mentioned that the maximum load when the piece is subjected to a tensile test is 30 N or more.
- the maximum load load value when the test piece is subjected to the tensile test is referred to as “S value”.
- the triangle OQE Q indicates a triangle having the origin O, the point Q, and the point E Q as vertices in the load-elongation rate curve illustrated in FIG.
- the region OQE Q indicates a region surrounded by the curve OQ, the line segment QE Q, and the line segment OE Q in the load-elongation rate curve.
- Tensile test is performed as follows.
- the shape of the test piece is a substantially rectangular shape having a width of 10 mm.
- the distance between the gauge points was 50 mm, and the tensile speed was 5 mm / min.
- tensile strength (tensile strength) is generally employed as an index representing the mechanical strength of the copper foil.
- the tensile strength is represented by a stress (N / mm 2 ) corresponding to the maximum force applied during the test. This is a value obtained by dividing the load applied to the test piece by the cross-sectional area of the test piece.
- Tensile strength is a basic mechanical property of a material.
- the tensile strength of each copper foil shows a substantially identical value.
- the thickness of the actual current collector is better when the thick copper foil is used. Decrease. Therefore, in the present invention, a technique for expressing the mechanical characteristics of the copper foil as a current collector not by the tensile strength measured by the tensile test but by the value of the load (N) actually applied to the test piece. I found.
- the mechanical properties of the copper foil can be more appropriately defined, and the negative electrode of a lithium ion secondary battery, particularly a lithium ion secondary battery that employs Si or Sn as a negative electrode active material
- An appropriate copper foil can be selected as the current collector.
- the L value obtained according to the above equation (1) is an index representing the linearity of the load-elongation curve.
- the L value is “1”, and the linearity of the load-elongation curve is the highest.
- the load applied to the test piece is 30 N or less and the L value always shows 0.8 or more, the linearity of the load-elongation curve is high.
- the copper foil having such an L value is a load of 30 N or less, even if the elongation occurs according to the load, the copper foil returns to the original shape of the substantially original size when the load is unloaded. Can do. For this reason, by using the copper foil which concerns on this invention as a collector, even if it repeats a charging / discharging cycle, possibility that deformation
- the copper foil according to the present invention has the L value always showing 0.8 or more in a range where the load applied to the test piece is 30 N or less. Further, it is more preferable that the L value always shows 0.8 or more in a range where the load applied to the test piece is 40 N or less. When the load applied to the test piece is 30 N or less and the L value always shows 0.8 or more, the current collector is not easily damaged even if the charge / discharge cycle is repeated for the same reason as described above. The possibility of deformation is reduced.
- the L value is always 0.8 or more, there is a possibility that the current collector may be deformed even if the charge / discharge cycle is repeated. Can be lower.
- the L value is always 0.8 or more in a range where the load applied to the test piece is 40 N or less. It is more preferable to use the copper foil shown.
- the copper foil according to the present invention preferably has an elongation (%) of 0.1 to 3.5 when a load of 30 N is applied to the test piece.
- the elongation percentage (%) of the test piece when a load of 30 N is applied is less than 0.1, when the copper foil is used as a current collector, it cannot follow the expansion of the volume of the negative electrode mixture layer, The current collector may break during discharge.
- the elongation (%) when a load of 30 N is applied exceeds 3.5, the copper foil is used as a current collector, and the result is that the electrode material layer expands following the expansion of the volume of the negative electrode mixture layer. The risk of wrinkles on the current collector increases. From these viewpoints, the elongation percentage (%) is preferably 0.1 to 3.5.
- the negative electrode material after applying the negative electrode mixture layer, drying is performed for several seconds to several tens of minutes in a temperature range of about 70 ° C. to 200 ° C. in order to remove the solvent.
- a negative electrode mixture layer is applied to the surface of the current collector, and then a dehydration condensation reaction is performed to obtain polyimide from the polyamic acid.
- heat treatment is performed in a temperature range of 120 ° C. to 450 ° C. for about 0.5 hours to 5 hours. Accordingly, it is preferable that the copper foil has the above-described mechanical characteristics even after the heat treatment is performed in such a temperature range for about 0.5 to 5 hours.
- the above-mentioned mechanical properties refer to at least mechanical properties (a) among mechanical properties (a) to (c). That is, in the load-elongation curve when the tensile test was performed using the copper foil after heat treatment at 70 ° C. to 450 ° C. as a test piece, the test was performed in the region where the L value was 0.8 or more. The maximum load applied to the piece, that is, the S value is 30N or more.
- Thickness Here, as the thickness of the copper foil used as the current collector increases, the actual elongation rate of the current collector when the same load (N) is applied if the copper foil is of the same foil type. (Deformation amount) becomes smaller. For this reason, from the viewpoint of preventing deformation of the current collector, it is preferable to employ a thick copper foil. However, from the viewpoint of further reducing the size of the lithium ion secondary battery, it is more preferable that the current collector is thinner. This is because when the thickness of the current collector increases, the capacity per unit volume of the lithium ion secondary battery decreases, which is not preferable.
- the thickness of the copper foil for the negative electrode current collector of the lithium ion secondary battery according to the present invention is preferably 35 ⁇ m or less, more preferably 18 ⁇ m or less, and even more preferably 12 ⁇ m or less.
- the copper foil preferably has appropriate handling properties, and the copper foil preferably has a thickness of 6 ⁇ m or more.
- the lower limit regarding thickness will not be specifically limited.
- the surface roughness (Ra) of each surface of the copper foil for a lithium ion secondary battery negative electrode collector according to the present invention is 0.1 ⁇ m or more. Furthermore, the surface roughness (Ra) of each surface is more preferably in the range of 0.2 ⁇ m to 0.7 ⁇ m. When the surface roughness (Ra) of each surface is 0.2 ⁇ m to 0.7 ⁇ m, the adhesion to the negative electrode mixture layer can be maintained.
- the difference in surface roughness (Ra) of each surface of the copper foil is preferably 0.6 ⁇ m or less. This is because, if there is a difference in surface roughness (Ra) between one surface and the other surface, a stress difference is generated and wrinkles or the like are considered to occur.
- Electrolytic copper foil The copper foil for the negative electrode current collector of the lithium ion secondary battery according to the present invention may be a rolled copper foil or an electrolytic copper foil. However, in view of economy and production efficiency, it is preferable to use electrolytic copper foil from the viewpoint that it can be manufactured at low cost.
- the electrolytic copper foil having the above-mentioned mechanical characteristics and the like, there is one having a chlorine concentration of 40 ppm to 200 ppm contained in the electrolytic copper foil.
- the electrolytic copper foil has, for example, a copper concentration in the range of 60 g / L to 90 g / L, a sulfuric acid concentration in the range of 80 g / L to 250 g / L, and a chlorine ion content in the range of 1 ppm to 3 ppm.
- the temperature of the electrolyte solution was adjusted to 40 °C ⁇ 60 °C, 30A / dm 2 ⁇ 120A / dm 2 of the electrolysis current It can be obtained by electrolysis at a density.
- the surface roughness (Ra) of each surface is within the above range by performing a roughening treatment on one surface or both surfaces as necessary.
- the electrolytic copper foil having a certain smoothness on each surface has a more uniform film thickness, and the surface roughness (Ra) of each surface is within the above range, whereby the negative electrode mixture layer, the current collector, Can be ensured.
- the difference in surface roughness (Ra) on both sides is smaller because deformation caused by the stress difference can be prevented.
- Silane coupling agent treatment In the copper foil for the negative electrode current collector of the lithium ion secondary battery of the present invention, it is preferable to provide a silane coupling agent layer on at least the side of the copper foil on which the negative electrode mixture layer is formed. . This is because the adhesion between the copper foil and the negative electrode mixture layer can be improved by providing the silane coupling agent layer.
- silane coupling agent for example, epoxyalkoxysilane, aminoalkoxysilane, methacryloxyalkoxysilane, mercaptoalkoxysilane and the like can be used. Two or more kinds of such silane coupling agents may be used in combination.
- the silane coupling agent layer can be formed using a known method. Specifically, a silane coupling agent layer is applied to the surface of the copper foil by applying a silane coupling agent on the surface of the copper foil by dipping or spraying, and then performing drying and heat treatment as necessary. Can be formed.
- the current collector By adopting the copper foil having the characteristics described above as a current collector constituting the negative electrode material of the lithium ion secondary battery, even if the volume of the negative electrode mixture layer expands during charging, the current collector follows it. be able to. And when the volume of the negative electrode mixture layer shrinks during discharge, the current collector can return to its original shape, preventing deformation of the current collector even if the charge / discharge cycle is repeated. can do.
- Electrolytic copper foil preparation process In Example 1, the electrolytic copper foil 1 was produced as follows as copper foil for lithium ion secondary battery negative electrode electrical power collectors. In producing the electrolytic copper foil 1, an electrolytic copper foil manufacturing apparatus having a known rotating cathode was employed. An electrolyte containing 80 g / L of copper ions, 250 g / L of sulfuric acid, 2.7 ppm of chlorine ions, and 2 ppm of gelatin was continuously supplied, and the current density was 60 A / dm at a liquid temperature of 50 ° C. At 2 , electrolysis was performed to deposit copper on the surface of the rotating cathode.
- the copper foil electrodeposited on the surface of the rotating cathode was peeled off to produce an electrolytic copper foil 1 having a converted thickness of 12 ⁇ m (gauge thickness: 12 ⁇ m).
- the converted thickness is a thickness obtained from the density of copper based on the mass per unit area.
- Roughening treatment step Next, roughening treatment was performed using a commonly used roughening treatment apparatus.
- an acidic copper electrolytic solution of 8 g / L of copper ions and 200 g / L of sulfuric acid is used as the electrolytic solution, and the temperature is 35 ° C. and the current density is 25 A / dm 2. Copper particles were deposited and formed. Then, using copper sulfate ion 70 g / L, sulfuric acid 110 g / L sulfuric acid acidic copper electrolyte, adopting smooth plating conditions with a liquid temperature of 50 ° C.
- the roughening process was completed by applying a covering plating to prevent the falling off.
- the surface roughness (Ra) of the larger surface of the electrolytic copper foil 1 obtained in this step was 0.35 ⁇ m, and the roughness (Ra) of the other surface was 0.32 ⁇ m.
- the surface roughness (Ra) was measured using a stylus type surface roughness meter (trade name: SE-3500) manufactured by Kosaka Laboratory.
- SE-3500 stylus type surface roughness meter
- Silane coupling agent treatment step The silane coupling agent treatment was performed on the electrolytic copper foil 1 that had undergone the roughening treatment step.
- 3-aminopropyltrimethoxysilane was used as the silane coupling agent.
- Spray treatment was performed in a shower to form silane coupling agent layers on both sides of the electrolytic copper foil 1.
- a negative electrode mixture layer was formed on the surface of the electrolytic copper foil 1 obtained as described above as follows.
- a negative electrode mixture layer a negative electrode mixture containing a negative electrode active material, a conductive material, and a binder was prepared.
- silicon powder was used as the negative electrode active material
- acetylene black was used as the conductive material
- polyamic acid was used as the binder
- NMP N-methylpyrrolidone
- This negative electrode mixture was applied to one side of the electrolytic copper foil 1 (the surface with the larger roughness) using an applicator, dried at 200 ° C. for 2 hours to volatilize the solvent, and then the polyamic acid In order to perform the dehydration condensation reaction, annealing treatment was performed at 350 ° C. for 1 hour.
- negative electrode material 1-1 what formed the negative mix layer on the single side
- a tab made of Ni foil was attached to one side portion of the base end portion in the length direction of the electrode surface. This is designated as negative electrode material 1-1.
- a negative electrode mixture layer is formed on both surfaces of the electrolytic copper foil 1 and is formed in the same size as the negative electrode material 1-1, and from the Ni foil at the same position as the negative electrode material 1-1.
- the one provided with the tab was used as the negative electrode material 1-2.
- Example 2 in the electrolytic copper foil manufacturing step, the negative electrode was formed only on one side of the electrolytic copper foil 2 in the same manner as in Example 1 except that the converted copper foil 2 having a converted thickness of 15 ⁇ m (gauge thickness of 15 ⁇ m) was prepared.
- a negative electrode material 2-1 provided with an agent layer and a negative electrode material 2-2 provided with a negative electrode mixture layer on both surfaces of the electrolytic copper foil 2 were produced.
- the surface roughness (Ra) of the surface having the larger roughness of the electrolytic copper foil 2 produced in Example 2 is 0.36 ⁇ m
- the surface roughness (Ra) of the other surface is 0.32 ⁇ m. there were.
- Example 3 in the electrolytic copper foil manufacturing step, the negative electrode was formed only on one side of the electrolytic copper foil 3 in the same manner as in Example 1 except that the electrolytic copper foil 3 having a converted thickness of 17 ⁇ m (gauge thickness 18 ⁇ m) was prepared.
- a negative electrode material 3-1 provided with an agent layer and a negative electrode material 3-2 provided with a negative electrode mixture layer on both surfaces of the electrolytic copper foil 3 were produced.
- the surface roughness (Ra) of the surface having the larger roughness of the electrolytic copper foil 3 produced in Example 3 is 0.37 ⁇ m
- the surface roughness (Ra) of the other surface is 0.31 ⁇ m. there were.
- a double-sided smooth copper foil having a converted thickness of 15 ⁇ m was used as a comparative electrolytic copper foil for comparison with Examples 1 to 3 described above.
- the comparative electrolytic copper foil was the same as that of Example 1 except that DFF (registered trademark) series DFF15 (gauge thickness 15 ⁇ m) commercially available from Mitsui Mining & Smelting Co., Ltd. was used.
- a comparative negative electrode material 1-1 having a negative electrode mixture layer provided on only one surface and a comparative negative electrode material 1-2 having a negative electrode mixture layer provided on both surfaces of the comparative copper foil were produced.
- the surface roughness (Ra) of the surface with the larger roughness of the comparative copper foil used in this comparative example was 0.19 ⁇ m
- the surface roughness (Ra) of the other surface was 0.16 ⁇ m. It was.
- Examples 1 to 3 the electrolytic copper foils 1 to 3 used as current collectors and the deformation evaluation during charging / discharging of the comparative electrolytic copper foil, and the lithium ion secondary battery
- a deformation evaluation cell and a cycle durability evaluation cell were prepared as follows.
- a lithium metal electrode as a counter electrode of the test electrode was produced as follows.
- As the current collector the same one as the electrolytic copper foil 1 used in the negative electrode material 1-1 was cut into the same size.
- a material obtained by superimposing a lithium metal foil on the surface of the electrolytic copper foil 1 was used as a counter electrode material for deformation evaluation.
- the negative electrode material 1-1 provided with the negative electrode mixture layer only on one side is covered with a separator, and the counter electrode material is disposed so that the negative electrode mixture layer and the lithium metal foil face each other with the separator interposed therebetween. I let you. This was used as a pair of electrodes. Then, the pair of electrodes were covered with a laminate material, and the edge of the laminate material was heat-sealed, leaving an electrolyte inlet. At this time, the tab was exposed to the outside from the laminate material.
- the injection hole was heat-sealed and the lithium ion secondary battery of a 2 layer laminate structure was produced.
- a deformation evaluation cell 1-1 using the electrolytic copper foil produced in Example 1 as a current collector was obtained.
- the deformation evaluation cell 2 was obtained in the same manner as described above except that the negative electrode material 2-1 produced in Example 2 was used instead of the negative electrode material 1-1, and the electrolytic copper foil 2 was used as a current collector for the counter electrode. -1 was obtained.
- a deformation evaluation cell 3-1 was obtained in the same manner as described above except that the negative electrode material 3-1 produced in Example 3 was used and the electrolytic copper foil 3 was used as the counter electrode current collector.
- a modified comparative cell 1-1 was obtained in the same manner as described above except that the comparative negative electrode material 1-1 produced in the comparative example was used and a comparative electrolytic copper foil was used as a current collector for the counter electrode.
- the deformation evaluation cell 2-2 was made in the same manner as described above except that the negative electrode material 2-2 produced in Example 2 was used instead of the negative electrode material 1-2 and the electrolytic copper foil 2 was used as a current collector for the counter electrode.
- a deformation evaluation cell 3-2 was obtained in the same manner as above except that the electrolytic copper foil 3 was used as the negative electrode material 3-2 produced in Example 3 and the current collector for the counter electrode.
- a modified comparison cell 1-2 was obtained in the same manner as described above except that the comparative negative electrode material 1-2 produced in the comparative example and the comparative electrolytic copper foil were used as the current collector for the counter electrode.
- Cycle Durability Evaluation Cell In order to perform the cycle durability of a lithium ion secondary battery using each electrolytic copper foil as a negative electrode current collector by full cell evaluation, a negative electrode material was used as a cycle durability evaluation cell. A three-layer laminate cell for durability evaluation using each of 1-2, the negative electrode material 3-2, and the comparative negative electrode material 1-2 as a negative electrode was prepared as follows. However, the cycle durability refers to an evaluation based on the capacity maintenance rate (%) of the lithium ion secondary battery when the charge / discharge cycle is repeatedly performed.
- a positive electrode material used as a positive electrode to be paired with each negative electrode was produced as follows. Lithium manganate as the positive electrode active material, acetylene black as the conductive material, polyvinylidene fluoride as the binder, and NMP as the solvent are mixed at a mixing ratio (mass ratio) of 5.6: 6.8: 100: 102. Thus, a positive electrode mixture (slurry) was prepared. This positive electrode mixture was applied to a current collector made of aluminum foil using an applicator, dried, and then rolled and pressed to obtain a positive electrode material. The positive electrode material thus produced was cut out such that the electrode surface had a width of 29 mm and a length of 40 mm. However, a tab made of Al foil was attached to one side of the base end in the length direction of the electrode surface. This was used as a positive electrode material.
- a cycle durability evaluation cell 1 was obtained in the same manner as the method for producing a three-layer laminate cell for deformation evaluation.
- a cell 3 for evaluating cycle durability was obtained using the negative electrode material 3-2 as a negative electrode and the positive electrode material as a positive electrode.
- a cell obtained by using the comparative negative electrode material 1-2 as a negative electrode and the positive electrode material as a positive electrode was used as a durability comparison cell.
- Charge / Discharge Method 2-1 Charge / Discharge Method of Deformation Evaluation Cell Deformation Evaluation Cell 1-1 to Deformation Evaluation Cell 3-2, Deformation Comparison Cell 1-1, and Deformation Comparison Cell 1-2 produced above.
- 1 charge / discharge cycle was carried out. Charging was performed by capacity regulation, and discharging was performed by voltage regulation. Specifically, in the first cycle, charging was performed as follows. First, charging was performed under a constant current (CC) condition at a charge rate of 0.05 C until the end voltage reached 0.001 V (vs. Li / Li +). Subsequently, the battery was charged until the current value reached 0.01 C under constant voltage (CV) conditions.
- CC constant current
- CV constant voltage
- the discharge capacity is 100% when discharging is performed under constant current (CC) conditions until the end voltage becomes 1.5 V at a discharge rate of 0.05 C, and the charge rate is 0 until the capacity reaches 82.5% at this time. Charged at .05C. On the other hand, the discharge was performed at a discharge rate of 0.05 C until the final voltage reached 1.5V.
- CC constant current
- the charging from the 2nd cycle to the 5th cycle was performed under a constant current / constant voltage (CCCV) condition with a charging rate of 0.1 C and a final voltage of 4.2 V.
- the discharge was performed under a constant current (CC) condition with a discharge rate of 0.1 C and a final voltage of 3.0 V.
- the charge and discharge after the 6th cycle were carried out up to 50 cycles under the same conditions except that the charge rate was 0.5C and the discharge rate was 0.5C.
- Evaluation Method 3-1 Physical Properties (Mechanical Properties), 3-2 Deformation Evaluation after Charge / Discharge, and 3-3 Lithium Ion for the Copper Foil Prepared in Examples 1 to 3 and the Copper Foil Used in the Comparative Example Evaluation as a secondary battery negative electrode current collector was performed.
- Each evaluation method is as follows.
- electrolytic copper foils 1 to 3 used as negative electrode current collectors of lithium ion secondary batteries in Examples 1 to 3 and Comparative Examples and comparison
- the physical properties of the electrolytic copper foil for normal use and after heat treatment were evaluated.
- a tensile test was performed using each electrolytic copper foil as a test piece and using a universal testing machine (model 5582) manufactured by Instron Corporation.
- the shape of the test piece was a rectangular shape having a width of 10 mm, and the distance between the gauge points was 50 mm.
- the tensile speed was 5 mm / min.
- the maximum load load (N), tensile strength (N / mm 2 ), elongation at break (%), and S value were determined for each test piece.
- the maximum load load refers to the maximum load (N) applied to the test piece during the test.
- the tensile strength (tensile strength) has shown the value (N / mm ⁇ 2 >) which remove
- the elongation at break (%) indicates a value (%) in which the permanent elongation after the break is expressed as a percentage with respect to the distance between the original marks (50 mm).
- the electrolytic copper foil in a normal state refers to an electrolytic copper foil that is not particularly heat-treated.
- the electrolytic copper foil after heat treatment refers to the electrolytic copper foil after heat-drying at 200 ° C. for 2 hours and then annealing at 350 ° C. for 1 hour.
- each cell was disassembled, and whether or not deformation such as wrinkles occurred in electrolytic copper foil 1 to electrolytic copper foil 3 and comparative electrolytic copper foil was visually observed.
- an industrial X-ray CT scanner (TOSCANER-32250 ⁇ hd) manufactured by Toshiba IT Control System Co., Ltd. was used for taking X-ray-CT images.
- Electrolytic copper foils 1 to 3 as lithium ion secondary battery negative electrode current collectors and comparative electrolytic copper foils were evaluated. Specifically, the deformation rate (%) of each electrolytic copper foil after one charge / discharge cycle and the state of occurrence of wrinkles, and each electrolytic copper foil after heat treatment were used as test pieces, and a load of 30 N in the tensile test. On the basis of the L value at the time of loading, the capacity retention rate (%) of the lithium ion secondary battery after 50 charge / discharge cycles, and the S value of each electrolytic copper foil after the heat treatment. It was determined whether or not the copper foil was suitable as a lithium ion secondary battery negative electrode current collector.
- the deformation rate (%) of the electrolytic copper foil is the extension of the current collector in a predetermined direction (for example, the long direction) after performing one charge / discharge cycle by the above-described method for each deformation evaluation cell.
- the amount is expressed as a percentage of the original size of the current collector in the predetermined direction.
- the capacity retention rate (%) is the capacity retention rate (%) of each cell after 50 cycles of charge / discharge, (discharge capacity at 50th cycle) / (discharge capacity at 5th cycle) ⁇ 100. It was obtained by calculating.
- L value, and S value the same method as described in the method for evaluating 3-1 physical properties (mechanical characteristics) and 3-2 for evaluating deformation after charge / discharge was adopted.
- the S values of the electrolytic copper foils 1 to 3 prepared in Examples 1 to 3 are all 30 N or more after the heat treatment.
- the S value of the comparative electrolytic copper foil used in the comparative example was 19N.
- FIG. 2 shows a load-elongation curve of each test piece obtained by the tensile test for each electrolytic copper foil after the heat treatment.
- the point on the elongation curve is Q (see FIG. 1)
- the L value obtained based on the above formula (1) is plotted against the tensile load at that time.
- the electrolytic copper foils 1 to 3 prepared in Examples 1 to 3 are larger in load load than the electrolytic copper foil used as a current collector in the comparative example. Is high.
- the electrolytic copper foil used as the current collector in Examples 1 to 3 has an L value in a range where the load applied to the test piece made of each electrolytic copper foil is 30 N or less. It turns out that it is always 0.8 or more.
- FIGS. 4-2 Deformation Evaluation after Charging / Discharging X-ray-CT images obtained by photographing a cross section of each cell after performing one charging / discharging cycle for each deformation evaluation cell are shown in FIGS.
- FIG. 4 shows a cross section of each cell of the two-layer laminate cell type, (a) is a deformation evaluation cell 1-1, (b) is a deformation evaluation cell 2-1, and (c) is a cell.
- Deformation evaluation cells 3-1 and (d) show cross sections of the deformation comparison cell 1-1, respectively.
- FIG. 4 shows a cross section of each cell of the two-layer laminate cell type
- (a) is a deformation evaluation cell 1-1
- (b) is a deformation evaluation cell 2-1
- (c) is a cell.
- Deformation evaluation cells 3-1 and (d) show cross sections of the deformation comparison cell 1-1, respectively.
- FIG. 5 shows a cross section of each cell of the three-layer laminate cell type, where (a) is a deformation evaluation cell 1-2, (b) is a deformation evaluation cell 2-2, and (c) is a deformation. Evaluation cells 3-2 and (d) show cross sections of the deformation comparison cell 1-2, respectively.
- FIG. 6 one charge / discharge cycle was performed in each of the deformation evaluation cell 1-1 to the deformation evaluation cell 3-2, the deformation comparison cell 1-1, and the deformation comparison cell 1-2.
- the deformation rate (%) of each current collector is shown.
- the deformation rate after carrying out one charge / discharge cycle is extremely high in the comparative electrolytic copper foil used as the current collector in the comparative example.
- Example 1, Example 2, Example 3 The electrolytic copper foil 1 to the electrolytic copper foil 3 used in each of the above cases have the negative electrode mixture layer provided on one side (the negative electrode material 1-1, the negative electrode material 2-1, and the negative electrode material 3-1, respectively). It can be seen that in any case where the agent layer is provided (the negative electrode material 1-2, the negative electrode material 2-2 and the negative electrode material 3-2), the deformation rate decreases as the thickness increases.
- FIGS. 7 and 8 are external photographs of the current collector obtained by disassembling the cells after carrying out one charge / discharge cycle in the deformation evaluation cell 3-2 and the deformation comparison cell 1-1, respectively. Show. Referring to FIG. 7, it can be seen that the electrolytic copper foil 3 used as the negative electrode current collector in the deformation evaluation cell 3-2 has no wrinkles even when the negative electrode mixture layer is provided on both sides thereof. On the other hand, referring to FIG. 8, the comparative electrolytic copper foil used as the negative electrode current collector in the modified comparative evaluation cell 1-1 was provided with the negative electrode mixture layer only on one side. In addition, it is understood that wrinkles are generated on the entire surface when one charge / discharge cycle is performed.
- Table 2 shows the evaluation results of the electrolytic copper foil 1, the electrolytic copper foil 3 and the comparative electrolytic copper foil as the lithium ion secondary battery negative electrode current collector. Show. As shown in Table 2, in the electrolytic copper foil 1 used as the current collector in Example 1, the amount of soot generated after one charge / discharge cycle of the deformation evaluation cell 1-2 was minimal. . In addition, the durability evaluation cell 1 using the electrolytic copper foil 1 as a negative electrode current collector achieved a capacity retention rate of 90% after 50 charge / discharge cycles. As a result, it can be evaluated that the electrolytic copper foil 1 has a practically no problem level as an electrolytic copper foil for a negative electrode current collector of a lithium ion secondary battery.
- the electrolytic copper foil 3 used as the current collector in Example 3 did not generate soot after the charge / discharge cycle of the deformation evaluation cell 3-2 was performed once. Further, the durability evaluation cell 3 using the electrolytic copper foil 3 as a negative electrode current collector achieved a capacity retention rate of 92% even after 50 charge / discharge cycles. Therefore, it can be evaluated that the electrolytic copper foil 3 is very suitable as a current collector for a negative electrode current collector of a lithium ion secondary battery. On the other hand, when the comparative electrolytic copper foil was used as a current collector, wrinkles occurred on the entire surface when the charge / discharge cycle of the deformation comparison cell 1-2 was performed once. Moreover, the capacity retention rate after 50 charge / discharge cycles of the durability comparison cell was 80%.
- the copper foil according to the present invention as a current collector for a negative electrode of a lithium ion secondary battery, a material having a large theoretical capacity, such as Si or Sn, is used as a material for occluding or alloying with lithium.
- the negative electrode mixture layer can follow the expansion / contraction of the negative electrode mixture layer even if the negative electrode mixture layer is greatly expanded / contracted due to charge / discharge. As a result, even when the charge / discharge cycle is repeated, deformation of the current collector or the like can be prevented from occurring or breaking.
- the copper foil according to the present invention as a current collector for the negative electrode of a lithium ion secondary battery, further increase in energy density and capacity of the lithium ion secondary battery can be achieved, The life of the lithium ion secondary battery can be extended.
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Abstract
Description
基本構成: リチウムイオン二次電池は、長尺形状に形成された正極材と負極材とをセパレータを介在させた状態で一体的に巻回した巻回体を角型或いは円筒型の筐体内に収容したものが一般に知られている。また、矩形形状に形成された正極材と負極材とをセパレータを介して一組対向させたセル、或いは、複数組のセルを積層してラミネート材で被覆したラミネートセルタイプのものも採用されている。リチウムイオンは水との反応性が高いため、電解液は一般に非水電解溶液が採用される。
本件発明者らは、鋭意研究の結果、リチウムイオン二次電池の負極用の集電体として、以下に説明する特徴を有する銅箔を採用することにより、充放電サイクルを繰り返し行った場合でも、集電体が変形するのを防止して、リチウムイオン二次電池の電池的特性を維持することが可能になることを見出した。以下、本件発明に係るリチウムイオン二次電池負極集電体用の銅箔について説明する。
本件発明では、試験片の形状を幅が10mmの略長方形状とした。そして、標点間の距離を50mmとし、引張速度は、5mm/minとした。ここで、銅箔の機械的強度を表す指標として、一般に引張強さ(抗張力)が採用される。引張強さは、試験中に加わった最大の力に対応する応力(N/mm2)で表される。これは、試験片に負荷された荷重を試験片の断面積で割った値となる。引張強さは、材料の基本的な機械的特性である。このため、同一種類の銅箔であれば、銅箔の厚みが異なる場合であっても、各銅箔の引張強さは略同一の値を示す。しかしながら、同一種類の銅箔を集電体として用いた場合であっても、同一の荷重(N)が負荷された場合、厚みが厚い銅箔を採用した方が実際の集電体の変形量は減少する。そこで、本件発明では、引張試験により測定した引張強さではなく、試験片に対して実際に負荷される荷重(N)の値により、銅箔の集電体としての機械的特性を表現する手法を見出した。当該手法を採用することにより、銅箔の機械的特性をより適切に規定することができ、リチウムイオン二次電池、特に、負極活物質としてSi又はSn等を採用するリチウムイオン二次電池の負極集電体として適切な銅箔を選定することができる。
電解銅箔作製工程: 実施例1では、リチウムイオン二次電池負極集電体用の銅箔として、次のようにして電解銅箔1を作製した。当該電解銅箔1の作製に際しては、公知の回転陰極を有する電解銅箔製造装置を採用した。銅イオンを80g/L、硫酸を250g/L、塩素イオンを2.7ppm、ゼラチンを2ppmの量で含む電解液を連続的に供給して、液温50℃の下、電流密度が60A/dm2にて、電気分解を行い、銅を回転陰極の表面に析出させた。回転陰極の表面に電着した銅箔を剥離して換算厚さ12μm(ゲージ厚:12μm)の電解銅箔1を作製した。なお、換算厚さとは、単位面積当たりの質量に基づき、銅の密度から求めた厚さである。
以上の様にして得た電解銅箔1の表面に、次のようにして負極合剤層を形成した。まず、負極合剤層を形成するために負極活物質と、導電材と、結着剤とを含む負極合剤を調製した。本実施例では、負極活物質としてシリコン粉、導電材としてアセチレンブラック、結着剤としてポリアミック酸、溶剤としてNMP(N-メチルピロリドン)を用いた。これらを、それぞれ、100:5:15:184の混合比(質量比)で混合して負極合剤(スラリー)を調製した。この負極合剤を電解銅箔1の片面(但し、粗さが大きい方の面)に、アプリケーターを用いて塗布して、200℃で2時間乾燥させて溶剤を揮発させた後、ポリアミック酸の脱水縮合反応を行うために、350℃で1時間アニール処理を施した。
実施例1~実施例3において、集電体として用いた電解銅箔1~電解銅箔3と、比較用電解銅箔の充放電時における変形評価と、リチウムイオン二次電池を構成したときの充放電時のサイクル耐久性評価を行うために、変形評価用セルと、サイクル耐久性評価用セルをそれぞれ以下のようにして作製した。
充放電後の各電解銅箔の変形評価をハーフセル評価により行うために、変形評価用セルとして、変形評価用2層ラミネートセル及び変形評価用3層ラミネートセルをそれぞれ作製した。各変形評価用セルにおいて、上記負極材1-1~負極材3-2と、比較負極材1-1及び比較負極材1-2とをそれぞれ試験電極とした。そして、これら各試験電極の対極としてリチウム金属電極を用いた。
上記試験電極の対極としての、リチウム金属電極を次のようにして作製した。集電体は、負極材1-1で使用した電解銅箔1と同じものを同じ大きさに切り出したものを用いた。この電解銅箔1の表面にリチウム金属箔を重ねたものを、変形評価用の対極材とした。
まず、片面にのみ負極合剤層を設けた負極材1-1の両面をそれぞれセパレータで覆い、セパレータを介して負極合剤層と、リチウム金属箔とが対向するようにして上記対極材を配置させた。これを一対の電極とした。そして、この一対の電極をラミネート材で覆い、電解液の注入口を残してラミネート材の縁部をヒートシールした。このとき、ラミネート材からタブが外側に露出するようにした。そして、グローブボックス内で、注入口からラミネート材の内部に電解液を注入した後、注入口をヒートシールして2層ラミネート構造のリチウムイオン二次電池を作製した。以上により、実施例1で作製した電解銅箔を集電体として用いた変形評価用セル1-1を得た。そして、負極材1-1の代わりに、実施例2で作製した負極材2-1を用い、対極の集電体として電解銅箔2を用いた以外は上記と同様にして変形評価用セル2-1を得た。同様に、実施例3で作製した負極材3-1を用いて、対極の集電体として電解銅箔3を用いた以外は上記と同様にして変形評価用セル3-1を得た。また、比較例で作製した比較負極材1-1を用いて、対極の集電体として比較用電解銅箔を用いた以外は上記と同様にして変形比較用セル1-1を得た。
一方、両面に負極合剤層を設けた負極材1-2の両面をセパレータで覆い、セパレータを介して両面側にリチウム金属箔が対向するように上記対極材を配置させた。そして、この一対の電極を用いた以外は、変形評価用セル1-1と同様にして、3層ラミネート構造のリチウムイオン二次電池を作製した。以上により、実施例1で作成した電解銅箔を集電体として用いた変形評価用セル1-2を得た。そして、負極材1-2の代わりに実施例2で作製した負極材2-2及び対極の集電体として電解銅箔2を用いた以外は、上記と同様にして変形評価用セル2-2を得た。同様に、実施例3で作製した負極材3-2及び対極の集電体として電解銅箔3を用いた以外は、上記と同様にして、変形評価用セル3-2を得た。また、比較例で作製した比較負極材1-2及び対極の集電体として比較用電解銅箔を用いた以外は、上記と同様にして、変形比較用セル1-2を得た。
各電解銅箔を負極集電体として用いたリチウムイオン二次電池のサイクル耐久性をフルセル評価により行うために、サイクル耐久性評価用セルとして、負極材1-2、負極材3-2、比較負極材1-2のそれぞれを負極として用いた耐久性評価用の3層ラミネートセルを次のようにして作製した。但し、サイクル耐久性とは、充放電サイクルを繰り返し行ったときのリチウムイオン二次電池の容量維持率(%)にて判断する評価をいう。
まず、各負極と対にする正極として使用する正極材を次のようにして作製した。正極活物質としてマンガン酸リチウム、導電材としてアセチレンブラック、結着剤としてポリフッ化ビニリデン、溶剤としてNMPを用い、これらを5.6:6.8:100:102の混合比(質量比)で混合して正極合剤(スラリー)を調製した。この正極合剤をアルミニウム箔からなる集電体にアプリケータを用いて塗布し、乾燥した後、ロール圧延及びプレスを行って正極材を得た。このようにして作製した正極材から電極面の大きさが幅29mm、長さ40mmになるようにして切り出した。但し、電極面の長さ方向の基端部の一側部にはAl箔からなるタブを取り付けた。これを正極材とした。
そして、負極材1-2を負極とし、上記正極材を正極としてそれぞれ用いて、変形評価用の3層ラミネートセルの作製方法と同様にしてサイクル耐久性評価用セル1を得た。同様に、負極材3-2を負極とし、上記正極材を正極として用いて得たものをサイクル耐久性評価用セル3とした。さらに、比較負極材1-2を負極とし、上記正極材を正極として用いて得たものを耐久性比較用セルとした。
2-1 変形評価用セルの充放電方法
上記において作製した変形評価用セル1-1~変形評価用セル3-2と、変形比較用セル1-1及び変形比較用セル1-2とについて、1回の充放電サイクルを実施した。充電は容量規制により行い、放電は電圧規制により行った。具体的には、初回のサイクルでは、充電を次のように行った。まず、充電レート0.05Cで終止電圧が0.001V(vs.Li/Li+)になるまで定電流(CC)条件により充電した。その後、引き続き、定電圧(CV)条件により電流値が0.01Cに達するまで充電した。さらに、放電レート0.05Cで終止電圧が1.5Vになるまで定電流(CC)条件により放電した場合の放電容量を100%とし、このときの82.5%の容量になるまで充電レート0.05Cで充電した。一方、放電は、放電レート0.05Cで終止電圧が1.5Vになるまで行った。
上記において作製したサイクル耐久性評価用1、サイクル耐久性評価用セル3及び耐久性比較用セルについて、容量維持率(%)を評価するために50回の充放電サイクルを実施した。充電および放電は電圧規制により行った。各セルについて、充放電を50サイクル実施した。このとき、1サイクル目の充電は、充電レートを0.05C、終止電圧を4.2Vで定電流定電圧(CCCV)条件で実施した。また、1サイクル目の放電は、放電レート0.05C、終止電圧3.0Vで定電流(CC)条件で実施した。そして、2サイクル目から5サイクル目の充電は、充電レートを0.1C、終止電圧を4.2Vで定電流・定電圧(CCCV)条件で実施した。一方、放電は、放電レートを0.1C、終止電圧を3.0Vで定電流(CC)条件で実施した。6サイクル目以降の充放電は、充電レートを0.5Cとし、放電レートを0.5Cとした以外は同じ条件で50サイクルまで実施した。
上記実施例1~実施例3で作製した銅箔及び比較例で用いた銅箔について、3-1物性(機械的特性)、3-2充放電後の変形評価、3-3リチウムイオン二次電池負極集電体としての評価を行った。各評価方法は以下の通りである。
まず、実施例1~実施例3と比較例とにおいてリチウムイオン二次電池の負極集電体として使用した電解銅箔1~電解銅箔3及び比較用電解銅箔の常態時と熱処理後の物性を評価した。当該物性を評価するに際して、各電解銅箔を試験片として、インストロンコーポレーション社製の万能試験機(型式5582)を用いて、引張試験を行った。試験片の形状は、幅が10mmの長方形状とし、標点間の距離を50mmとした。また、引張速度は、5mm/minとした。当該引張試験において、各試験片について、最大負荷加重(N)、引張強さ(N/mm2)、破断伸び率(%)、S値を求めた。但し、最大負荷荷重とは、試験中に試験片に負荷された最大の荷重(N)を指す。また、引張強さ(抗張力)は、最大負荷荷重を試験片の断面積で除した値(N/mm2)を示している。また、破断伸び率(%)は、破断後の永久伸びを原標点間距離(50mm)に対して百分率で表した値(%)を示している。また、S値は上述した通りであり、L値が0.8以上である領域において、当該試験片を前記引張試験に供したときの最大負荷荷重値を指す。また、常態時の電解銅箔とは、特に熱処理を施していない電解銅箔を指す。また、熱処理後の電解銅箔とは、本評価においては、200℃で2時間加熱乾燥させた後、350℃で1時間アニール処理を行った後の電解銅箔を指す。
充放電後の変形評価は、次のようにして行った。変形評価用セル1-1~変形評価用セル3-2及び変形比較用セル1-1及び変形比較用セル1-2について、それぞれ上述した方法で充放電サイクルを1回実施した後、各セルの断面のX線-CT画像を得て観察した。また、各セルの断面のX線-CT画像に基づき、集電体として用いた電解銅箔1~電解銅箔3及び比較用電解銅箔の変形率(伸び率)を求めた。その後、各セルを解体して、電解銅箔1~電解銅箔3及び比較用電解銅箔に皺等の変形が生じたか否かについて目視により観察した。但し、X線-CT画像の撮影には、東芝ITコントロールシステム株式会社製の産業用X線CTスキャナ(TOSCANER-32250μhd)を用いた。
リチウムイオン二次電池負極集電体としての電解銅箔1~電解銅箔3と、比較用電解銅箔とを評価した。具体的には、充放電サイクル1回実施した後の各電解銅箔の変形率(%)及び皺の発生状態と、熱処理後の各電解銅箔を試験片とし、上記引張試験において30Nの荷重を負荷したときのL値と、充放電サイクルを50回実施した後のリチウムイオン二次電池の容量維持率(%)と、熱処理後の各電解銅箔のS値とに基づいて、各電解銅箔がリチウムイオン二次電池負極集電体として適しているか否かを判断した。
以下、各評価結果を示す。
表1に、実施例1~実施例3において集電体として用いた電解銅箔1~電解銅箔3の常態時、熱処理後の物性値を比較例で集電体として用いた比較用電解銅箔の各物性値と共に示す。
各変形評価用セルについて充放電サイクルを1回実施した後の各セルの断面を撮影したX線-CT画像を図4及び図5に示す。ここで、図4は2層ラミネートセルタイプの各セルの断面を示すものであり、(a)は変形評価用セル1-1、(b)は変形評価用セル2-1、(c)は変形評価用セル3-1、(d)は変形比較用セル1-1の断面をそれぞれ示している。一方、図5は3層ラミネートセルタイプの各セルの断面を示すものであり、(a)は変形評価用セル1-2、(b)は変形評価用セル2-2、(c)は変形評価用セル3-2、(d)は変形比較用セル1-2の断面をそれぞれ示している。
表2に、リチウムイオン二次電池負極集電体としての、電解銅箔1、電解銅箔3及び比較用電解銅箔の評価結果を示す。表2に示すように、実施例1において集電体として用いた電解銅箔1は、変形評価用セル1-2の充放電サイクルを1回行った後の皺の発生量は極小であった。また、当該電解銅箔1を負極集電体として用いた耐久性評価用セル1は、充放電サイクルを50回実施した後において90%の容量維持率を達成した。その結果、当該電解銅箔1は、リチウムイオン二次電池負極集電体用の電解銅箔として実用上問題ないレベルであると評価できる。また、実施例3において集電体として用いた電解銅箔3は、変形評価用セル3-2の充放電サイクルを1回行った後に皺が発生することはなかった。また、当該電解銅箔3を負極集電体として用いた耐久性評価用セル3は、充放電サイクルを50回行った後も92%の容量維持率を達成した。従って、当該電解銅箔3は、リチウムイオン二次電池負極集電体用の集電体として非常に好適なものであると評価できる。一方、比較用電解銅箔を集電体として用いた場合、変形比較用セル1-2の充放電サイクルを1回行うと、その表面全面に皺が発生した。また、耐久性比較用セルの充放電サイクルを50回実施した後の容量維持率は80%であった。
Claims (6)
- リチウムイオン二次電池負極集電体用の銅箔であって、
当該銅箔からなる幅10mmの試験片を引張試験に供したときの荷重-伸び率曲線において、原点をOとし、伸び率がEQのときの荷重がPQであるときの当該荷重-伸び率曲線上の点をQとしたときに、下記式(1)で表わされるL値が0.8以上である領域において、当該試験片を前記引張試験に供したときの最大負荷荷重が30N以上であることを特徴とするリチウムイオン二次電池負極集電体用の銅箔。
但し、上記式(1)において、三角形OQEQは、当該荷重-伸び率曲線において、原点Oと、点Qと、点EQとをそれぞれ頂点とする三角形を指す。また、領域OQEQは、当該荷重-伸び率曲線における曲線OQと、線分QEQと、線分OEQとにより囲まれる領域を指す。 - 前記試験片に負荷される荷重が30N以下の範囲で、前記L値が常に0.8以上を示す請求項1に記載のリチウムイオン二次電池負極集電体用の銅箔。
- 70℃~450℃で熱処理が施された後の当該銅箔を前記試験片として用いた場合にも、前記L値が0.8以上である領域において、前記最大負荷荷重が30N以上である請求項1又は請求項2に記載のリチウムイオン二次電池負極集電体用の銅箔。
- 請求項1~請求項3のいずれか一項に記載のリチウムイオン二次電池負極集電体用の銅箔を集電体とし、当該集電体の表面に負極活物質を含む負極合剤層を備えることを特徴とするリチウムイオン二次電池負極材。
- 前記負極活物質として、Si又はSnを含む材料を用いる請求項4に記載のリチウムイオン二次電池負極材。
- リチウムイオン二次電池負極集電体に用いる銅箔を選定するためのリチウムイオン二次電池負極集電体選定方法であって、
選定候補の銅箔のうち、請求項1~請求項3に記載のリチウムイオン二次電池負極集電体用の銅箔を集電体として選定することを特徴とするリチウムイオン二次電池負極集電体選定方法。
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CN103210533A (zh) | 2013-07-17 |
JP5850611B2 (ja) | 2016-02-03 |
KR20130087042A (ko) | 2013-08-05 |
US20130288122A1 (en) | 2013-10-31 |
TWI456827B (zh) | 2014-10-11 |
JP2012109122A (ja) | 2012-06-07 |
TW201222959A (en) | 2012-06-01 |
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