WO2005108647A1 - キャリア箔付き多孔質金属箔及びその製造方法 - Google Patents
キャリア箔付き多孔質金属箔及びその製造方法 Download PDFInfo
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- WO2005108647A1 WO2005108647A1 PCT/JP2005/008195 JP2005008195W WO2005108647A1 WO 2005108647 A1 WO2005108647 A1 WO 2005108647A1 JP 2005008195 W JP2005008195 W JP 2005008195W WO 2005108647 A1 WO2005108647 A1 WO 2005108647A1
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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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/10—Moulds; Masks; Masterforms
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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
- H01M4/0438—Processes of manufacture in general by electrochemical processing
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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
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- Porous metal foil with carrier foil and method for producing the same are Porous metal foil with carrier foil and method for producing the same
- the present invention relates to a porous metal foil with a carrier foil and a method for producing the same.
- the present invention also relates to a method for producing a negative electrode for a non-aqueous electrolyte secondary battery.
- Porous metal foils are widely used, for example, as current collectors for batteries and as carriers for catalysts.
- the method for producing this kind of porous metal foil includes, for example, (a) forming an insulating film of a desired shape on the electrode surface and applying electrolytic plating thereon, so that a portion corresponding to the film is applied to the electrode; A method for producing a porous metal foil in such a way that prayer does not occur, (b) a method for sintering a fibrous or granular metal into a porous sintered body, and (c) a method for producing a metal by rolling or electrolytic plating. After the foil is manufactured, there is a method of punching and punching holes.
- a method for producing a porous metal foil by electrolytic plating for example, a metal substrate to be electrodeposited is roughened by sandblasting, chemical etching, electrolytic etching, machining, or the like. Roughly spray the insulating paint on the rough surface, or provide an insulating coating or oxide film on the entire surface, and remove the coating such as wire brush and puff partially and incompletely.
- a method of producing a metal foil by applying electrolytic plating later is known (see Patent Document 1). By peeling the obtained metal foil from the substrate, a porous body can be obtained.
- the electrode plate surface is subjected to hydrophobic treatment by adsorption of a carboxylic acid having a hydrophobic group, coupling using a higher alcohol salt and a metal, or coating of fluorinated titanium, and the like.
- a method of producing a metal foil by performing electrolytic plating is known (see Patent Document 2). In this method, hydrogen bubbles generated on the electrode plate surface during electroplating remain on the electrode plate surface, so that contact with the electrolyte becomes insufficient and electrodeposition does not occur at that portion. We are using.
- Patent Document 1 Japanese Patent Application Laid-Open No. 50-141540
- Patent Document 2 JP-A-5-23760 [0006] With any of the above techniques, the metal foil obtained thereby is porous, but it is not easy to increase the strength. Also, it is not easy to improve the efficiency of electrodeposition by applying an insulating substance to the electrode surface. Furthermore, in the technique described in Patent Document 1, it is essential to roughen the electrode surface, and therefore, a roughening treatment of the electrode is required prior to electroplating, which complicates the manufacturing process. In addition, since the metal foil is thin and stiff, it is not easy to handle and process it alone.
- an object of the present invention is to provide a porous metal foil and a method for producing the same, which can solve the above-mentioned various disadvantages of the related art.
- the present invention has a porous metal foil layer formed by electrolytic plating on a conductive carrier foil, and further includes a bonding interface layer formed between the two by using a conductive polymer.
- the object has been achieved by providing a porous metal foil with a carrier foil, characterized in that the metal foil has a carrier foil.
- the present invention is also a method for producing the porous metal foil with a carrier foil
- a method for producing a porous metal foil with a carrier foil comprising applying a coating liquid containing the conductive polymer to one surface of the carrier foil, and forming the metal foil thereon by electrolysis.
- the present invention is obtained by peeling the porous metal foil from the porous metal foil with a carrier foil, and the conductive polymer is attached to one surface of the porous metal foil layer.
- the present invention provides a porous metal foil characterized by the following.
- the negative electrode for a non-aqueous electrolyte secondary battery comprising the porous metal foil with a carrier foil, and a porous metal foil obtained by peeling the porous metal foil. It is intended to provide a non-aqueous electrolyte secondary battery comprising a negative electrode.
- the present invention includes a pair of current collecting surface layers whose surfaces are in contact with the electrolytic solution, and an active material layer containing active material particles having a high ability to form a lithium compound interposed between the surface layers.
- a coating solution containing a conductive polymer is applied to one surface of the carrier foil, and a metal material having a low ability to form a lithium compound is electroplated thereon to form one current-collecting surface layer.
- a conductive slurry containing particles of an active material is applied on the surface layer for power application to form an active material layer, and a metal material having a low ability to form a lithium compound is electrolytically deposited on the active material layer to form an active material layer.
- FIGS. 1 (a) to 1 (d) are process diagrams showing a method for producing a porous metal foil of the present invention.
- FIG. 2 is a schematic diagram showing a structure of a negative electrode for a non-aqueous electrolyte secondary battery provided with the metal foil of the present invention.
- FIG. 3 (a) and FIG. 3 (b) are diagrams showing charging characteristics of the negative electrode obtained in Example 1.
- FIG. 4 (a) and FIG. 4 (b) are diagrams showing charging characteristics of the negative electrode obtained in Comparative Example 1.
- FIG. 5 is a scanning electron micrograph of the surface state of the first metal foil in the negative electrode obtained in Example 2.
- the porous metal foil with a carrier foil of the present invention has a three-layer structure having a porous metal foil layer on the carrier foil and a bonding interface layer between the two.
- the bonding interface layer is in direct contact with each of the carrier foil and the porous metal foil layer (hereinafter simply referred to as metal foil or porous metal foil).
- the metal foil is formed by electrolytic plating.
- the metal foil is porous with many micropores.
- the metal foil has both a fine hole penetrating the metal foil in the thickness direction and a fine hole closing in the middle.
- the micropores referred to in the present invention mean micropores penetrating the metal foil in the thickness direction. However, this does not exclude a metal foil having micropores closed in the present invention. Also, it does not mean that such a metal foil is preferable.
- the thickness of the metal foil is not particularly limited, and an appropriate thickness is selected depending on the specific use.
- it is used as an electrode material for a non-aqueous electrolyte secondary battery shown in FIG.
- the thickness is 2 to 20 ⁇ m, more preferably 3 to 10 ⁇ m.
- the metal foil can be composed of various metal materials.
- a metal foil containing at least one metal of Cu, Ni, Co, Fe, Cr, Sn, Zn, In, Ag and Au can be used. That is, it is possible to constitute a simple substance of these metals, an alloy of two or more of these metals, or a metal foil containing other elements in addition to them.
- Cu, Ni, Co, Fe, Cr, and Au force must also be composed. Low reactivity with lithium Force is also preferred.
- the carrier foil is used as a support for producing a porous metal foil.
- the produced porous metal foil is supported before use or during processing, and is used to improve the handleability of the metal foil.
- the carrier foil has such a strength that no swelling or the like occurs in the manufacturing process of the metal foil and in the processing and transporting processes after the manufacturing! /, Prefer to,. Therefore, the carrier foil preferably has a thickness of about 10 to 50 ⁇ m.
- a conductive foil is used as the carrier foil.
- the carrier foil need not be made of metal as long as it has conductivity.
- using a metal carrier foil has the advantage that the carrier foil can be melted and made and recycled after the production of the porous metal foil.
- the carrier foil is composed of at least one metal selected from the group consisting of Cu, Ni, Co, Fe, Cr, Sn, Zn, In, Ag, Au, Al and Ti. , Prefer to,.
- the carrier foil for example, foils manufactured by various methods such as a rolled foil and an electrolytic foil can be used without any particular limitation.
- the present invention does not necessarily require that the surface of the carrier foil is roughened.
- the surface of the carrier foil has a certain degree of unevenness from the viewpoint of controlling the pore diameter ⁇ existence density of the fine pores.
- Each surface of the rolled foil is smooth due to the manufacturing method.
- the electrolytic foil has a rough surface on one side and a smooth surface on the other side. The rough surface is a deposition surface when producing an electrolytic foil.
- the rough surface of the electrolytic foil If is used as an electrodeposition surface, the labor for separately performing a roughening treatment on the carrier foil can be omitted, which is convenient.
- its surface roughness Ra should be 0.05 to 5 m, particularly 0.2 to 0.8 / zm, and should have a desired diameter and existing density. It is preferable because holes can be easily formed.
- a bonding interface layer of both foils is interposed.
- the bonding interface layer is formed by applying and drying a coating solution containing a conductive polymer.
- the bonding interface layer is used for forming desired micropores in the metal foil and for imparting desired strength and flexibility to the metal foil after peeling from the carrier foil.
- the carrier foil is an electrolytic foil, it is preferable that, of the surface of the carrier foil, a surface in contact with a bonding interface is a deposition surface when the electrolytic foil is manufactured.
- the conductive polymer constituting the bonding interface layer a conventionally known polymer whose type is not particularly limited can be used.
- a conventionally known polymer whose type is not particularly limited can be used.
- PVDf polypyridene-fluoride
- PEO polyethylene oxide
- PAN polyacryl-tolyl
- PMMA polymethyl methacrylate
- the conductive polymer which is not related to the specific use of the porous metal foil is preferably a fluorine-containing conductive polymer. This is because the fluorine-containing polymer has high thermal and chemical stability and excellent mechanical strength.
- poly (pyridene fluoride) which is a fluorine-containing polymer having lithium ion conductivity.
- the bonding interface layer formed using the conductive polymer may be present continuously over the entire area between the carrier foil and the porous metal foil with a thickness sufficient to completely separate the carrier foil and the porous metal foil. . Or it may exist discontinuously between both foils.
- the amount of the conductive polymer in the bonding interface layer is determined from the viewpoint of forming desired micropores in the porous metal foil and imparting desired strength and flexibility to the porous metal foil after peeling from the carrier foil. The appropriate amount is determined.
- the metal foil may be peeled off the carrier foil after a predetermined application to the metal foil is completed. Or for metal foil The metal foil and carrier foil may be peeled off immediately before performing the predetermined processing. As a result, the thickness is thin and the stiffness is weak, and the handling and properties of the metal foil are remarkably improved.
- the porous metal foil with the carrier foil of the present embodiment has a peeled porous metal foil on one surface of which a conductive polymer derived from a bonding interface layer is adhered. This adhesion imparts the desired strength and flexibility to the metal foil.
- the conductive polymer may be continuously coated over the entire surface of the porous metal foil, or may be discontinuously coated in an island shape. According to the study of the present inventors, it has been found that the strength and flexibility of the metal foil can be improved only by the conductive polymer covering one surface of the porous metal foil discontinuously in an island shape.
- a carrier foil 1 is prepared as shown in FIG.
- the carrier foil 1 is also an electrolytic foil, as shown in the figure, the carrier foil 1 has a rough surface la on one side and a smooth surface lb on the other side. Of these surfaces, it is preferable to use the rough surface la as the electrodeposition surface for the reason described above.
- a release agent is applied to one surface of the carrier foil 1 to perform a release treatment.
- the release agent is preferably applied to the rough surface la of the carrier foil 1.
- the release agent is used to successfully release the metal foil from the carrier foil 1 in a release step described later.
- the peeling treatment is performed by, for example, a chrome plating treatment, a nickel plating treatment, a lead plating treatment, a chromate treatment, or the like.
- a release treatment using a release agent made of an organic compound can also be performed.
- the organic compound it is particularly preferable to use a nitrogen-containing compound or a sulfur-containing compound.
- nitrogen-containing conjugates examples include benzotriazole (BTA), carboxybenzotriazole (CBTA), tolyltriazole ( ⁇ ), ⁇ ′, N′-bis (benzotriazolylmethyl) urea (BTD-U) And triazole-based compounds such as 3-amino-1H-1,2,4-triazole ( ⁇ ).
- the sulfur-containing compound examples include mercaptobenzothiazole ( ⁇ ), thiocyanuric acid (TCA), and 2-benzimidazolthiol (BIT).
- the releasability depends on the concentration of the release agent and the amount applied. Can control.
- the step of applying the release agent is performed only in order to successfully release the metal foil from the carrier foil 1 in the release step described below. Therefore, even if this step is omitted, a metal foil having fine holes can be formed.
- a coating liquid containing a conductive polymer is applied and dried to form a coating film 2.
- the surface to which the coating liquid is applied may be subjected to a release treatment with a release agent.
- the coating liquid is formed by dissolving a conductive polymer in a volatile organic solvent.
- a conductive polymer in a volatile organic solvent.
- N-methylpyrrolidinone can be used as the organic solvent.
- the coating liquid is applied to the rough surface la of the carrier foil 1, so that it is likely to accumulate in the concave portions on the rough surface la.
- the thickness of the coating film 2 becomes uneven. That is, the thickness of the coating film corresponding to the concave portion of the rough surface is large, and the thickness of the coating film corresponding to the convex portion is small.
- a large number of fine holes are formed as shown in FIG. 1 (c) by utilizing the unevenness of the thickness of the coating film 2.
- the mechanism by which the porous metal foil is formed on the carrier foil 1 is considered as follows.
- the carrier foil 1 on which the coating film 2 is formed is subjected to an electrolytic plating process, and a metal foil 3 is formed on the coating film 2 as shown in FIG.
- the conductive polymer that forms the coating has electronic conductivity, though not as much as metal. Therefore, the coating 2 has different electron conductivity depending on its thickness.
- Micropores 4 are formed. In other words, the portion where the electrodeposition rate is low, in other words, the thickness of the coating film 2 and the portion tend to become the micropores 4.
- the fineness can also be controlled by the concentration of the conductive polymer contained in the coating liquid.
- the pore diameter of hole 4 divided by the existing density can be controlled. For example, when the concentration of the conductive polymer is low, the pore size tends to decrease, and the existing density also tends to decrease. Conversely, when the concentration of the conductive polymer is high, the pore size tends to increase.
- the concentration of the conductive polymer in the coating liquid is not only a dominant factor of the pore diameter of the micropores / existence density, but also a dominant factor of the strength and flexibility of the obtained metal foil. Also. For example, as the concentration of the conductive polymer increases, the strength / flexibility of the obtained metal foil tends to increase. From these various viewpoints, the concentration of the conductive polymer in the coating liquid is preferably 0.05 to 5% by weight, particularly preferably 1 to 3% by weight.
- the fine holes 4 are drawn so as to correspond to the thick portions of the coating film 2.
- the plating bath and the plating conditions for forming the metal foil 3 are appropriately selected according to the constituent material of the metal foil.
- a Watt bath or a sulfamic acid bath having the following composition can be used as a plating bath.
- the bath temperature is preferably about 40 to 70 ° C, and the current density is preferably about 0.5 to 20 AZdm2!
- the metal foil 3 is manufactured by the above-described method, it is easy to freely control the hole diameter ⁇ existing density of the fine holes 4. In addition, it is easy to freely control the strength and flexibility of the metal foil.
- the metal foil is always deposited on a new surface, that is, on the surface of the carrier foil which is replaced at each production. As a result, the state of the surface can always be kept constant, so that it is possible to precisely control the pore diameter / existence density, strength and flexibility.
- the surface on which the metal foil is electrodeposited is always the same surface, that is, the peripheral surface of the drum force sword body, so that the state of the surface changes with time.
- the metal foil 3 obtained in this manner has a force depending on manufacturing conditions, preferably 0.01 to 200.
- the metal foil 3 having the micropores 4 in this range is used, for example, as a material for an electrode of a nonaqueous electrolyte secondary battery shown in FIG. 2 described later, the flow of the nonaqueous electrolyte can be maintained while maintaining the strength of the metal foil 3. Can be sufficiently secured. Further, it is possible to effectively prevent the active material from falling off due to the absorption and desorption of lithium.
- micropores 4 having the above diameter, connexion and the site of the metal foil 3 throat Mitechi, in an area of 1cm 2 LOOOO pieces, in particular 500 to 8000 pieces, especially 1000 It is preferred to be present at a density of ⁇ 6000.
- the method for measuring the pore diameter ⁇ existing density of the micropores 4 will be described in Examples described later.
- the metal foil in the porous metal foil with a carrier foil obtained by the above method is subjected to a desired process in a state of being adhered to the carrier foil.
- the metal foil 3 may be peeled off from the carrier foil 1 and subjected to desired processing.
- the metal foil thus obtained is used, for example, as a material for an electrode of a battery, a carrier for a catalyst in various chemical reactions, and a filter for gas or liquid.
- it is suitably used as a material for electrodes for non-aqueous electrolyte secondary batteries, particularly as a material for negative electrodes.
- FIG. 2 schematically shows the structure of a negative electrode 6 for a non-aqueous electrolyte secondary battery including a metal foil obtained by peeling from a porous metal foil with a carrier foil manufactured according to the present invention. ing.
- the negative electrode 6 is configured such that an active material layer 5 containing particles 7 of a negative electrode active material is sandwiched between a pair of metal foils 3a and 3b. Many fine holes are formed in each of the metal foils 3a and 3b. The method for forming the fine holes will be described later. According to the negative electrode 6, the flow path of the electrolyte is sufficiently ensured through the many fine holes formed in the metal foils 3 a and 3 b, so that the capacity of the nonaqueous electrolyte secondary battery is increased.
- the negative electrode 6 shown in FIG. 2 has an advantage that the active material layer needs to be formed only on one surface of the metal foil. This also contributes to the improvement of the energy density described later.
- the material forming the metal foils 3a and 3b penetrates over the entire area of the active material layer 5 in the thickness direction. It is preferable that the active material particles 7 exist in the permeated material. As a result, the adhesion between the active material layer 5 and the metal foils 3a and 3b becomes strong, and the active material is further prevented from falling off. In addition, since the conductive material is ensured between the metal foils 3a and 3b and the active material through the material penetrated into the active material layer 5, an electrically isolated active material is generated. The generation of an electrically isolated active material deep in the layer 5 is effectively prevented, and the current collecting function is maintained.
- the life of the negative electrode can be prolonged. This is particularly advantageous when a material such as a silicon-based material, which is a semiconductor and has poor electron conductivity, is used as the active material.
- the material constituting the metal foils 3a and 3b existing in the active material layer 5 penetrates the active material layer 5 in the thickness direction.
- the metal foils 3a and 3b are electrically conducted through the material, and the electron conductivity of the entire negative electrode 6 is further increased. That is, the negative electrode 6 has a current collecting function as a whole of the negative electrode.
- the fact that the material constituting the metal foils 3a and 3b penetrates over the entire area in the thickness direction of the active material layer 5 and the two metal foils are connected to each other can be determined by electron microscope mapping using the material as a measurement target. .
- the active material is activated by the anchor effect.
- the material constituting the metal foils 3a and 3b enter the micropores so as not to completely fill the micropores, from the viewpoint of ensuring the flow of the electrolytic solution. A preferred method for permeating the material constituting the metal foils 3a and 3b into the active material layer will be described later.
- the active material layer 5 is sandwiched between the pair of metal foils 3a and 3b, so that particles of the active material are absorbed and desorbed by lithium. Even after repeated expansion and contraction, it is difficult to fall off the negative electrode 2. Further, the adhesion between the active material layer 5 and the metal foils 3a and 3b is improved by the above-described anchor effect. As a result, the cycle characteristics are improved. Since the metal foils 3a and 3b have a small thickness, the energy density per unit volume and unit weight can be increased.
- the negative electrode active material for example, particles of an alloy containing Si or Sn, which are high-capacity active materials, are preferably used.
- the average particle diameter D of the active material particles is 0.1 to 30 / ⁇ , which is preferable.
- the active material layer 5 containing such active material particles has a thickness of 10 to 80 ⁇ m, preferably 20 to 50 ⁇ m. By doing so, the capacity and the energy density of the battery can be increased.
- the negative electrode 6 shown in FIG. 2 can be manufactured by using the above-described method for manufacturing a porous metal foil with a carrier foil. For example, first carry out the method shown in Fig. 1 (a) to 1 (c). A porous metal foil with a metal foil is manufactured. This is used as one metal foil 3a. Next, the active material layer 5 is formed on the metal foil 3a in a state where the metal foil 3a is not peeled off by the carrier foil force. The active material layer 5 is formed by applying a paste containing, for example, particles of an active material or particles of a conductive material.
- a carbonaceous material for example, acetylene bran having an average particle diameter D
- H is applied in a thickness of 0.001 to m. This operation is for forming a large number of fine holes in the other metal foil 3b.
- the constituent material of the metal foil is electrodeposited by electrolysis to form the other metal foil 3b.
- the plating solution penetrates into the active material layer 5 and reaches the interface between the active material layer 5 and the metal foil 3a, under which the electrolytic plating is performed.
- the inside of the active material layer 5 (mouth) the outer surface side of the active material layer 5 (that is, the surface in contact with the plating liquid, and (c) the inner surface side of the active material layer 5 (that is, the metal)
- the metal material is deposited on the surface facing the foil 3a).
- the metal foil 3b is formed, and the material constituting the metal foil 3b penetrates the entire active material layer 5 in the thickness direction to reach the metal foil 3a. Part of it enters a part of the fine hole of the metal foil 3a.
- the metal foil 3a manufactured first is also peeled off the carrier foil. Thereby, the negative electrode 6 shown in FIG. 2 is obtained.
- the negative electrode 6 thus obtained has substantially the same electrode characteristics on each surface. That is, each of the metal foils 3a and 3b has substantially the same size and the same density of micropores.
- the conductive polymer is adhered to the outer surface of the metal foil 3a.
- the negative electrode 6 is used together with a known positive electrode, a separator, and a non-aqueous electrolyte to form a non-aqueous electrolyte secondary battery.
- the positive electrode is prepared by suspending a positive electrode active material and, if necessary, a conductive agent and a binder in an appropriate solvent to prepare a positive electrode mixture, applying the mixture to a current collector, drying the mixture, rolling, pressing, and Obtained by cutting and punching.
- the positive electrode active material a conventionally known positive electrode active material such as a lithium nickel composite oxide, a lithium manganese composite oxide, a lithium cobalt composite oxide, and the like are used.
- the separator a synthetic resin nonwoven fabric, a polyethylene or polypropylene porous film, or the like is preferably used.
- the non-aqueous electrolyte is a solution in which a lithium salt as a supporting electrolyte is dissolved in an organic solvent.
- lithium salts include LiCIO, Li A1C1, LiPF, LiAsF, LiSbF, LiSCN, LiCl, LiBr ⁇ Lil, LiCF SO, LiC F
- the copper carrier foil (thickness: 35 ⁇ m) obtained by the electrolysis was acid-washed at room temperature for 30 seconds. Subsequently, pure water washing was performed at room temperature for 30 seconds. Next, the carrier foil was immersed in a 3.5 g Zl CBTA solution kept at 40 ° C for 30 seconds. Thereby, a peeling treatment was performed. After the peeling treatment, the solution strength was also raised, and the substrate was washed with pure water for 15 seconds.
- the carrier foil was immersed in a Watt bath having the following bath composition to perform electroplating. Thereby, a first metal foil having a nickel strength was formed on the coating film.
- the current density was 5 AZdm 2 , the bath temperature was 50 ° C, and the pH was 5.
- a nickel electrode was used for the anode.
- the power supply used was a DC power supply.
- the metal foil was formed to a thickness of 5 m. After lifting from the plating bath, the substrate was washed with pure water for 30 seconds and dried in the air. Thus, a porous metal foil with a carrier foil was obtained.
- a slurry containing particles of the negative electrode active material was applied on a metal foil so as to have a film thickness to form an active material layer.
- the composition of the slurry is as follows: active material: Ni powder: a
- a carbonaceous material (acetylene black) having an average particle diameter D force of S40 nm is included.
- One coat was applied to a thickness of 0.5 m. Subsequently, electrolytic plating was performed on this coating film under the same electrolytic conditions as described above to form a second metal foil having a nickel strength. Metal foil was formed to a thickness of 3 ⁇ m.
- the first metal foil and the carrier foil were peeled off to obtain a negative electrode for a non-aqueous electrolyte secondary battery in which an active material layer was sandwiched between a pair of metal foils.
- the negative electrode had polyvinylidene fluoride adhered to the outer surface of the first metal foil.
- Example 2 instead of the watt bath used in Example 1, an H 2 SO 3 / CuSO-based plating bath was used.
- First and second metal foils having copper strength were formed.
- the composition of the plating bath is CuSO power 3 ⁇ 450gZl
- the H SO was 70 gZl. Current density was 5AZdm 2. Other than this, the same as in Example 1
- the copper carrier foil (thickness: 35 ⁇ m) obtained by the electrolysis was acid-washed at room temperature for 30 seconds. Subsequently, pure water washing was performed at room temperature for 30 seconds. Next, the carrier foil was subjected to a peeling treatment in the same manner as in Example 1. Next, the carrier foil was immersed in a watt bath having the same bath composition as in Example 1 to perform electroplating to form a first metal foil made of nickel color.
- the electrolysis conditions were the same as in Example 1.
- a slurry containing particles of the negative electrode active material was applied on the first metal foil to a thickness of 15 / zm to form an active material layer. The same active material and slurry as in Example 1 were used.
- Electrolytic plating was performed on the active material layer under the same conditions as in Example 1 to form a second metal foil made of nickel copper.
- the metal foil was formed to a thickness of 3 m.
- the first metal foil and the carrier foil were peeled off to obtain a negative electrode for a non-aqueous electrolyte secondary battery in which an active material layer was sandwiched between a pair of metal foils.
- LiPF as non-aqueous electrolyte
- a non-aqueous electrolyte secondary battery was fabricated by a conventional method using a mixed solution of Z-ethylene carbonate and getyl carbonate (1: 1 volume ratio). Using this battery, evaluation was performed under charging conditions of 0.2 mA and a voltage range of 0 to 2.8 V.
- the photograph was subjected to image analysis to determine the diameter and density of the micropores.
- the negative electrode of Example 1 had a sufficient capacity on both the carrier foil peeling side and the coated side. It can be seen that is obtained. This means that in the negative electrode of Example 1, the electrolyte was sufficiently supplied to the active material layer through the first and second metal foils. On the other hand, in the negative electrode of Comparative Example 1, it was found that sufficient capacity was obtained on both the carrier foil peeling side and the coating-coated side, and it was not found. This means that in the negative electrode of Comparative Example 1, the electrolyte was sufficiently supplied to the active material layer through the first and second metal foils.
- the first metal foil (metal foil manufactured according to the manufacturing method of the present invention) obtained in Example 1 has fine pores. It can be seen that it has the same tensile strength as the first metal foil obtained in Comparative Example 1 having no micropores of the same thickness. High tensile strength is also obtained for the first metal foil obtained in Example 2.
- FIG. 5 shows a scanning electron micrograph of the surface state of the first metal foil in the negative electrode obtained in Example 2. As is clear from this photographic power, it can be seen that many fine holes are formed in the first metal foil.
- the metal foil is thin and has low stiffness and is not easy to handle. Since the metal foil is attached to the carrier foil, the handleability of the metal foil is good. become. In particular, since the metal foil is porous, it has low strength and is easily broken, but according to the present invention, such inconvenience is unlikely to occur. In addition, the porous metal foil from which the carrier foil has also been peeled has high strength and high flexibility since the conductive polymer is attached to one surface thereof. Further, according to the method for producing a porous metal foil with a carrier foil of the present invention, the diameter of the micropores formed in the metal foil divided by the existing density can be freely controlled.
- the negative electrode manufactured by the manufacturing method of the present invention since the flow path of the electrolyte is sufficiently ensured, the capacity of the nonaqueous electrolyte secondary battery is increased, and the active material absorbs and desorbs lithium. The loss of electrode force due to storage is effectively prevented, and the cycle characteristics are improved.
Abstract
Description
Claims
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JP2004137824A JP4298578B2 (ja) | 2004-05-06 | 2004-05-06 | キャリア箔付き多孔質金属箔及びその製造方法 |
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Cited By (2)
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CN110637385A (zh) * | 2017-05-18 | 2019-12-31 | 富士胶片株式会社 | 穿孔金属箔、穿孔金属箔的制造方法、二次电池用负极及二次电池用正极 |
CN113036086A (zh) * | 2019-12-24 | 2021-06-25 | 广州方邦电子股份有限公司 | 一种电池极片的制备方法、电池极片及锂电池 |
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CN102762777B (zh) | 2009-12-04 | 2015-12-02 | 三井金属矿业株式会社 | 多孔金属箔及其制备方法 |
CN102820451A (zh) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | 负极极片及其制备方法、锂离子电池及其制备方法 |
WO2022138295A1 (ja) * | 2020-12-25 | 2022-06-30 | Tdk株式会社 | 積層体、リチウムイオン二次電池用の負極集電体、及びリチウムイオン二次電池用の負極 |
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JPS53106644A (en) * | 1977-03-02 | 1978-09-16 | Toppan Printing Co Ltd | Preparation of relief metal foil |
JPH08225986A (ja) * | 1995-02-22 | 1996-09-03 | Achilles Corp | 電着方法とその装置 |
JPH0945334A (ja) * | 1995-07-26 | 1997-02-14 | Katayama Tokushu Kogyo Kk | リチウム二次電池極板用基材、該基材を用いた極板および該極板を用いた二次電池 |
JP2001256968A (ja) * | 2000-03-13 | 2001-09-21 | Mitsui Mining & Smelting Co Ltd | 非水電解質二次電池用負極材料およびその製造方法 |
JP2004139768A (ja) * | 2002-10-16 | 2004-05-13 | Hitachi Maxell Ltd | 多孔質薄膜電極と、これを負極とするリチウム二次電池 |
JP2005129264A (ja) * | 2003-10-21 | 2005-05-19 | Mitsui Mining & Smelting Co Ltd | 多孔質金属箔及びその製造方法 |
JP2005197217A (ja) * | 2003-12-10 | 2005-07-21 | Mitsui Mining & Smelting Co Ltd | 非水電解液二次電池用負極 |
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- 2004-05-06 JP JP2004137824A patent/JP4298578B2/ja not_active Expired - Fee Related
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2005
- 2005-04-28 WO PCT/JP2005/008195 patent/WO2005108647A1/ja active Application Filing
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JPS53106644A (en) * | 1977-03-02 | 1978-09-16 | Toppan Printing Co Ltd | Preparation of relief metal foil |
JPH08225986A (ja) * | 1995-02-22 | 1996-09-03 | Achilles Corp | 電着方法とその装置 |
JPH0945334A (ja) * | 1995-07-26 | 1997-02-14 | Katayama Tokushu Kogyo Kk | リチウム二次電池極板用基材、該基材を用いた極板および該極板を用いた二次電池 |
JP2001256968A (ja) * | 2000-03-13 | 2001-09-21 | Mitsui Mining & Smelting Co Ltd | 非水電解質二次電池用負極材料およびその製造方法 |
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JP2005129264A (ja) * | 2003-10-21 | 2005-05-19 | Mitsui Mining & Smelting Co Ltd | 多孔質金属箔及びその製造方法 |
JP2005197217A (ja) * | 2003-12-10 | 2005-07-21 | Mitsui Mining & Smelting Co Ltd | 非水電解液二次電池用負極 |
Cited By (2)
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CN110637385A (zh) * | 2017-05-18 | 2019-12-31 | 富士胶片株式会社 | 穿孔金属箔、穿孔金属箔的制造方法、二次电池用负极及二次电池用正极 |
CN113036086A (zh) * | 2019-12-24 | 2021-06-25 | 广州方邦电子股份有限公司 | 一种电池极片的制备方法、电池极片及锂电池 |
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