WO2018060773A1 - 二次電池 - Google Patents
二次電池 Download PDFInfo
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- WO2018060773A1 WO2018060773A1 PCT/IB2017/001380 IB2017001380W WO2018060773A1 WO 2018060773 A1 WO2018060773 A1 WO 2018060773A1 IB 2017001380 W IB2017001380 W IB 2017001380W WO 2018060773 A1 WO2018060773 A1 WO 2018060773A1
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- WIPO (PCT)
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- electrode active
- active material
- material layer
- negative electrode
- adhesive
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
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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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a secondary battery in which the area of the negative electrode active material layer is larger than the area of the positive electrode active material layer.
- the secondary battery includes a power generation element.
- the power generation element includes a positive electrode plate in which a positive electrode active material layer is disposed on at least one surface of a first current collector, and a negative electrode active material layer.
- a negative electrode plate having an area larger than that of the material layer and disposed on at least one surface of the second current collector.
- the positive electrode plate and the negative electrode plate are laminated with a positive electrode active material layer and a negative electrode active material layer facing each other with a separator interposed therebetween (see Patent Document 1).
- the negative electrode plate includes a facing portion facing the positive electrode active material layer with the separator interposed therebetween, and a non-facing portion located on the outer periphery of the facing portion and not facing the positive electrode active material layer with the separator interposed therebetween.
- the power generation capacity of the battery having the above-described configuration varies depending on the facing area between the positive electrode active material layer and the negative electrode active material layer.
- the areas of the positive electrode active material layer and the negative electrode active material layer are the same, the opposing areas of the positive electrode active material layer and the negative electrode active material layer are relative to each other in the direction crossing the stacking direction. Can be changed by shifting the position. Therefore, even when the positive electrode active material layer and the negative electrode active material layer are relatively displaced, the facing area between the positive electrode active material layer and the negative electrode active material layer is kept constant to suppress fluctuations in power generation capacity. Therefore, the negative electrode active material layer has a larger area than the positive electrode active material layer.
- the opposing portion of the negative electrode plate expands and contracts due to charge and discharge.
- the non-opposing portion of the negative electrode plate contributes less to charging / discharging than the opposing portion, and the expansion / contraction dimension is also small compared to the opposing portion.
- the expansion / contraction dimension generated in the negative electrode plate with expansion and contraction of the negative electrode active material layer is not uniform over the entire negative electrode plate, and thus wrinkles are generated at the outer peripheral edge of the negative electrode plate.
- the soot generated at the outer peripheral edge of the negative electrode plate extends toward the opposing portion of the negative electrode plate, that is, the site that reacts as an electrode, by repeating charge and discharge. If soot reaches the site that reacts as an electrode, the distance between the electrodes becomes non-uniform and the reaction is localized, resulting in deterioration of battery performance and cycle life, so that soot is generated on the outer peripheral edge of the negative electrode plate. It is demanded to suppress this.
- the above-described problem is not limited to the case where silicon is used for the negative electrode active material, and may occur as long as the negative electrode active material layer expands and contracts with use.
- the present invention has been made to solve the above-described problems, and suppresses wrinkles from occurring on the outer peripheral edge of the negative electrode plate due to expansion and contraction of the negative electrode active material layer with use. Therefore, an object is to provide a secondary battery capable of preventing performance degradation and cycle life degradation.
- a secondary battery of the present invention includes a positive electrode plate having a positive electrode active material layer disposed on at least one surface of a first current collector, a negative electrode active material layer, and a positive electrode active material layer.
- the positive electrode active material layer and the negative electrode active material layer are opposed to each other with a separator holding the electrolyte sandwiched between a negative electrode plate having an area larger than that of the negative electrode plate disposed on at least one surface of the second current collector In this state, the power generation element is laminated.
- the negative electrode plate is located on the opposite portion facing the positive electrode active material layer with the separator interposed therebetween, and on the outer periphery of the opposite portion, and on the positive electrode active material layer with the separator interposed therebetween.
- the negative electrode plate and the separator are bonded via an adhesive layer, and in the adhesive layer, the second non-opposing portion is bonded to the separator than the bonding strength of the first bonding portion that bonds the opposing portion to the separator.
- the adhesive strength of the bonded part is greater.
- FIG. 1 is a perspective view of a secondary battery according to an embodiment. It is sectional drawing which follows the 2-2 line of FIG. It is sectional drawing which shows the principal part of the cross section which follows the 3-3 line of FIG. It is a top view of the electric power generation element of the secondary battery which concerns on embodiment. It is a schematic sectional drawing which shows a mode that a 1st adhesion part is formed. It is a schematic sectional drawing which shows a mode that a 2nd adhesion part is formed. It is sectional drawing corresponding to FIG. 3 which shows the principal part of the secondary battery which concerns on the other modification of embodiment.
- the secondary battery 100 will be described with reference to FIGS.
- a nonaqueous electrolyte secondary battery more specifically, a lithium ion secondary battery will be described as an example.
- FIG. 1 is a perspective view of a secondary battery 100 according to the present embodiment.
- FIG. 2 is a cross-sectional view taken along line 2-2 of FIG.
- FIG. 3 is a cross-sectional view showing a main part of a cross section taken along line 3-3 in FIG.
- FIG. 4 is a plan view of the power generation element 110 of the secondary battery 100.
- FIG. 5A is a schematic cross-sectional view showing a state of forming the first adhesive portion 45a
- FIG. 5B is a schematic cross-sectional view showing a state of forming the second adhesive portion 45b.
- a secondary battery 100 according to the present embodiment is roughly described.
- a positive electrode plate in which a positive electrode active material layer 12 is disposed on both surfaces 11 a and 11 b of a first current collector 11.
- the power generation element 110 is formed by stacking the positive electrode active material layer 12 and the negative electrode active material layer 22 facing each other with the separator 30 interposed therebetween.
- the negative electrode plate 20 is opposed to the positive electrode active material layer 12 with the separator 30 in between, and the non-opposite portion 20a is located on the outer periphery of the opposed portion 20a and does not face the positive electrode active material layer 12 with the separator 30 in between. And an opposing portion 20b.
- the negative electrode plate 20 and the separator 30 are bonded via a second adhesive layer 45 (corresponding to an adhesive layer), and in the second adhesive layer 45, the first adhesive portion 45a that adheres the facing portion 20a to the separator 30.
- the bonding strength of the second bonding portion 45b that bonds the non-facing portion 20b to the separator 30 is greater than the bonding strength.
- the secondary battery 100 further includes an exterior member 120 that houses the power generation element 110 together with the electrolytic solution.
- power generation element 110 is formed by laminating positive electrode plate 10 and negative electrode plate 20 with positive electrode active material layer 12 and negative electrode active material layer 22, which will be described later, facing separator 30. Do it.
- the power generation element 110 is accommodated in the exterior member 120 in a state where the positive electrode plate 10 and the negative electrode plate 20 are stacked with the separator 30 interposed therebetween.
- electrolyte solution is not specifically limited, A conventionally well-known thing can be utilized suitably.
- an electrolyte solution using a liquid electrolyte is used as the electrolyte solution, but an electrolyte solution using a gel electrolyte may be used.
- the liquid electrolyte is a solution in which a lithium salt as a supporting salt is dissolved in a solvent.
- the kind of solvent is not specifically limited, For example, conventionally well-known things, such as a dimethyl carbonate (DMC), can be used suitably.
- DMC dimethyl carbonate
- the exterior member 120 accommodates the power generation element 110 together with the electrolytic solution.
- the exterior member 120 is composed of a laminate sheet having a three-layer structure.
- the first layer corresponds to a heat-fusible resin and is formed using, for example, polyethylene (PE), ionomer, or ethylene vinyl acetate (EVA).
- the first layer material is adjacent to the negative electrode plate 20.
- the second layer corresponds to a metal foil formed, for example, an Al foil or Ni foil.
- the third layer corresponds to a resinous film and is formed using, for example, rigid polyethylene terephthalate (PET) or nylon.
- PET polyethylene terephthalate
- the third layer material is adjacent to the positive electrode plate 10.
- the positive electrode plate 10 includes a positive electrode active material layer 12 disposed on both surfaces 11 a and 11 b of a first current collector 11.
- the first current collector 11 has a thin film shape.
- the material which comprises the 1st electrical power collector 11 is not specifically limited, For example, it can be set as aluminum.
- a positive electrode tab 13 for charging / discharging is connected to the first current collector 11.
- the thickness of the first current collector 11 is not particularly limited, but is about 1 to 100 ⁇ m, for example.
- the positive electrode active material layer 12 includes a positive electrode active material.
- the kind of positive electrode active material is not specifically limited, For example, it can be set as LiNiCoAlO2.
- the positive electrode active material layer 12 is disposed over the entire surfaces 11 a and 11 b of the first current collector 11.
- the arrangement of the positive electrode active material layer 12 is such that the positive electrode plate 10 and the negative electrode plate 20 are stacked via the separator 30, and the positive electrode active material layer 12 and the negative electrode active material layer 22 are sandwiched between the separators 30. Is not particularly limited as long as they can face each other.
- the thickness of the positive electrode active material layer 12 is not particularly limited, but is, for example, about 1 ⁇ m to 100 ⁇ m. Although the method in particular of controlling the thickness of the positive electrode active material layer 12 is not restrict
- the positive electrode active material layer 12 is formed by applying the positive electrode slurry on the both surfaces 11 a and 11 b of the first current collector 11 and drying the first positive electrode active material layer 12. It forms on both surfaces 11a and 11b of the current collector 11. The dried positive electrode active material layer 12 is pressed from both sides of the first current collector 11 while being bonded to the both surfaces 11 a and 11 b of the first current collector 11.
- the positive electrode slurry contains a positive electrode active material, a conductive additive, a binder, and a viscosity adjusting solvent.
- a positive electrode active material LiNiCoAlO 2 is used at a ratio of 90 wt%.
- a conductive additive acetylene black is used at a ratio of 5 wt%.
- a binder PVDF is used at a ratio of 5 wt%.
- the negative electrode plate 20 is configured by disposing a negative electrode active material layer 22 on both surfaces 21 a and 21 b of a second current collector 21.
- the second current collector 21 has a thin film shape.
- the material which comprises the 2nd electrical power collector 21 is not specifically limited, For example, it can be set as copper.
- a negative electrode tab 23 for charging / discharging is connected to the second current collector 21.
- the thickness of the second current collector 21 is not particularly limited, but is, for example, about 1 to 100 ⁇ m.
- the area of the negative electrode active material layer 22 is larger than the area of the positive electrode active material layer 12.
- the facing area between the positive electrode active material layer 12 and the negative electrode active material layer 22 can be maintained constant. Therefore, it is possible to suppress a change in power generation capacity due to a change in the facing area between the positive electrode active material layer 12 and the negative electrode active material layer 22.
- the negative electrode active material layer 22 contains a negative electrode active material. At least one of the negative electrode active materials is selected from the group consisting of silicon simple substance (Si), silicon alloy, and silicon oxide.
- the negative electrode active material layer 22 can be thinned by using the above-described material for the negative electrode active material. As a result, the negative electrode plate 20 can be reduced in size and capacity, and the secondary battery 100 can be reduced in size and capacity.
- the thickness of the negative electrode active material layer 22 is not particularly limited, but is, for example, about 1 ⁇ m to 100 ⁇ m. Although the method for controlling the thickness of the negative electrode active material layer 22 is not particularly limited, a method similar to the method for controlling the thickness of the positive electrode active material layer 12 can be used.
- the negative electrode slurry can contain, for example, a negative electrode active material, a conductive additive, a binder, and a viscosity adjusting solvent.
- a negative electrode active material for example, a mixture of 80 wt% silicon alloy as a negative electrode active material, 5 wt% acetylene black as a conductive additive, and 15 wt% polyimide as a binder can be used.
- NMP can be used as a solvent for adjusting the viscosity of the slurry.
- the type of the separator 30 is not particularly limited as long as the electrolyte contained in the electrolytic solution can be retained, and a conventionally known one can be appropriately used.
- a porous sheet separator or a nonwoven fabric separator made of a polymer or fiber that absorbs and holds the electrolyte contained in the electrolytic solution can be used.
- the thickness of the separator 30 is not particularly limited, but is, for example, about 1 to 50 ⁇ m.
- ⁇ Adhesive layer> The positive electrode plate 10 and the separator 30 are bonded via a first adhesive layer 40, and the negative electrode plate 20 and the separator 30 are bonded via a second adhesive layer 45.
- the first adhesive layer 40 is disposed between the positive electrode active material layer 12 and the separator 30, and adheres the positive electrode plate 10 and the separator 30 by bonding the positive electrode active material layer 12 and the separator 30.
- the second adhesive layer 45 is disposed between the negative electrode active material layer 22 and the separator 30, and adheres the negative electrode plate 20 and the separator 30 by bonding the negative electrode active material layer 22 and the separator 30.
- the thickness of the 1st contact bonding layer 40 is not specifically limited, For example, it is about 100 nm-500 nm.
- the thickness of the second adhesive layer 45 is not limited, but is, for example, about 100 nm to 500 nm.
- the material constituting the first adhesive layer 40 is not limited as long as the positive electrode active material layer 12 and the separator 30 can be bonded.
- the material constituting the second adhesive layer 45 is not limited as long as the negative electrode active material layer 22 and the separator 30 can be bonded.
- Examples of materials constituting the first adhesive layer 40 and the second adhesive layer 45 include olefin resins such as polyethylene (PE) and polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), and polyethernitrile (PEN).
- olefin resins such as polyethylene (PE) and polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), and polyethernitrile (PEN).
- Polyacrylonitrile PAN
- polyimide PI
- polyamide PA
- polyamideimide PAI
- CMC carboxymethylcellulose
- PVC polyvinyl chloride
- SBR styrene-butadiene Rubber
- isoprene rubber butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene copolymer, styrene / butadiene / styrene block copolymer and hydrogenated products thereof, styrene / isoprene / styrene block
- Thermoplastic polymers such as copolymers and hydrogenated products thereof, polyvinylidene fluoride (PVdF), polyvinylidene fluoride (having some carboxyl groups in the side chain), polyvinylidene fluoride-hexafluoropropylene (PVdF-H
- polyvinylidene fluoride polyimide, styrene / butadiene rubber, carboxymethyl cellulose, polypropylene, polytetrafluoroethylene, polyacrylonitrile, and polyamide as materials constituting the first adhesive layer 40 and the second adhesive layer 45.
- the materials described above as the material constituting the first adhesive layer 40 and the material constituting the second adhesive layer 45 are excellent in heat resistance and are stable at both the oxidation potential and the reduction potential.
- the material constituting the first adhesive layer 40 and the material constituting the second adhesive layer 45 for example, polyvinylidene fluoride (PVdF), (meth) acrylic resin, olefin resin, etc. Since it is strong against any potential on the reduction side, it can be suitably used for both the first adhesive layer 40 and the second adhesive layer 45.
- PVdF polyvinylidene fluoride
- (meth) acrylic resin olefin resin, etc. Since it is strong against any potential on the reduction side, it can be suitably used for both the first adhesive layer 40 and the second adhesive layer 45.
- the material constituting the first adhesive layer 40 and the material constituting the second adhesive layer 45 PTFE or the like is strong in oxidation potential, and therefore the first active material layer 12 and the separator 30 are bonded to each other. It is preferable to use it as a material constituting the adhesive layer 40.
- SBR or the like adheres to the negative electrode active material layer 22 and the separator 30 because of its strong reduction potential. It is preferable to use it as a material constituting the second adhesive layer 45.
- the materials described above as the material constituting the first adhesive layer 40 and the material constituting the second adhesive layer 45 may be used alone or in combination of two or more.
- the first adhesive layer 40 is disposed at a portion of the surface 30 a facing the positive electrode active material layer 12 in the separator 30 that faces the positive electrode active material layer 12.
- the arrangement of the first adhesive layer 40 is not particularly limited as long as the positive electrode active material layer 12 and the separator 30 can be bonded.
- the first adhesive layer 40 may be disposed over the entire surface 30 a facing the positive electrode active material layer 12 in the separator 30.
- the second adhesive layer 45 is also disposed at a portion of the surface 30 b facing the negative electrode active material layer 22 in the separator 30 that faces the negative electrode active material layer 22.
- the arrangement of the second adhesive layer 45 is not particularly limited as long as the negative electrode active material layer 22 and the separator 30 can be bonded.
- the second adhesive layer 45 may be disposed over the entire surface 30 b facing the negative electrode active material layer 22 in the separator 30.
- the negative electrode plate 20 is located on the outer periphery of the facing portion 20 a that faces the positive electrode active material layer 12 with the separator 30 interposed therebetween, and on the outer periphery of the facing portion 20 a.
- the second adhesive layer 45 includes a first adhesive part 45a that adheres the opposing part 20a to the separator 30, and a second adhesive part 45b that adheres the non-opposing part 20b to the separator 30.
- the 1st adhesion part 45a is arranged between separator 30 and counter part 20a.
- the second adhesive portion 45b is disposed between the separator 30 and the non-facing portion 20b.
- the adhesive strength of the second adhesive portion 45b is greater than the adhesive strength of the first adhesive portion 45a.
- the method for evaluating the adhesive strength is not particularly limited as long as the evaluation of the adhesive strength of the first adhesive portion 45a and the adhesive strength of the second adhesive portion 45b are performed by the same evaluation method.
- a method described in JIS K6854-1 (90-degree peeling test) or K6854-2 (180-degree peeling test) can be used as a method for evaluating the adhesive strength.
- the negative electrode plate 20 expands and contracts, but the expansion / contraction dimension (the size of expansion / contraction) is not uniform throughout the negative electrode plate 20.
- the facing portion 20a of the negative electrode plate 20 expands and contracts with the exchange of ions with the positive electrode plate 10 by charging and discharging.
- the non-facing portion 20b of the negative electrode plate 20 has less exchange of ions with the positive electrode plate 10 and has a small contribution to charging / discharging, and therefore has a smaller expansion / contraction dimension than the facing portion 20a.
- the expansion of the negative electrode active material layer 22 in the non-facing portion 20b of the negative electrode plate 20 during charging is smaller than the expansion of the negative electrode active material layer 22 in the facing portion 20a.
- the negative electrode plate 20 in the non-facing portion 20b is stretched by the second current collector 21 being stretched by applying tension as the facing portion 20a is stretched.
- the negative electrode plate 20 in the facing portion 20a shrinks due to the shrinkage of the negative electrode active material layer 22, but the negative electrode plate 20 in the non-facing portion 20b has little shrinkage of the negative electrode active material layer 22 and is almost reduced. Do not reduce.
- the secondary battery 100 since the adhesive force of the second adhesive portion 45b is larger than the adhesive force of the first adhesive portion 45a, expansion / contraction of the non-opposing portion 20b is suppressed more than the opposing portion 20a. Thus, the expansion / contraction dimension of the non-facing portion 20b can be reduced. Thereby, the tension
- the adhesive strength of the second adhesive portion 45b is not particularly limited as long as it is greater than the adhesive strength of the first adhesive portion 45a.
- the ratio between the adhesive strength of the first adhesive portion 45a and the adhesive strength of the second adhesive portion 45b is used. May be 0.02 ⁇ (adhesive strength of the first adhesive portion 45a / adhesive strength of the second adhesive portion 45b) ⁇ 0.5.
- the ratio of the adhesive strength of the first adhesive portion 45a to the adhesive strength of the second adhesive portion 45b can be set within a range between 1: 2 and 1:50.
- the average particle diameter of the material constituting the second adhesive portion 45b is larger than the average particle diameter of the material constituting the first adhesive portion 45a.
- the average particle diameter means an average particle diameter of a material that generates an adhesive force among materials constituting the second adhesive layer 45.
- PVdF polyvinylidene fluoride
- PVdF polyvinylidene fluoride
- two or more kinds of materials are used in combination as the material constituting the second adhesive layer 45, it means the average particle diameter for all of these materials.
- the first adhesive portion 45a is bonded by a simple method of varying the average particle size.
- the bonding strength of the second bonding portion 45b can be made larger than the strength.
- the average particle diameter of the material constituting the first adhesive portion 45a and the average particle diameter of the material constituting the second adhesive portion 45b are such that the adhesive strength of the second adhesive portion 45b is larger than the adhesive strength of the first adhesive portion 45a. As long as it is not particularly limited. For example, when polyvinylidene fluoride (PVdF) is used as the material constituting the second adhesive layer 45, the average particle diameter of the material constituting the first adhesive portion 45a is 1 ⁇ m, and the material constituting the first adhesive portion 45a The average particle size can be 0.1 ⁇ m.
- the calculation method of the average particle diameter of the material forming the first bonding portion 45a and the average particle diameter of the material forming the second bonding portion 45b are the same as the calculation method of the average particle diameter of the material forming the first bonding portion 45a.
- the calculation method of the average particle diameter of the material which comprises the 2 adhesion part 45b is the same, it is not limited.
- the average particle diameter of the material constituting the first adhesive portion 45a and the average particle diameter of the material constituting the second adhesive portion 45b for example, a 50% cumulative particle diameter from the small particle diameter side by the laser diffraction / scattering method is used. be able to.
- the formation method of the 1st adhesion part 45a and the 2nd adhesion part 45b is not specifically limited, For example, it can form by the following procedures.
- the positive electrode plate 10 and the negative electrode plate 20 do not face the negative electrode active material layer 22 when stacked via the separator 30.
- a release paper M having the same thickness as that of the first adhesive portion 45a is disposed at the site.
- the material which comprises the 1st adhesion part 45a is applied toward 30b. Thereby, the 1st adhesion part 45a is formed on surface 30b.
- the release paper M is peeled off, and a material constituting the second adhesive portion 45b is applied to a portion that does not face the negative electrode active material layer 22 when the positive electrode plate 10 and the negative electrode plate 20 are laminated via the separator 30. To do. Thereby, as shown to FIG. 5B, the 2nd adhesion part 45b is formed on the surface 30b.
- the secondary battery 100 is repeatedly charged and discharged as a driving power source or auxiliary power source for a motor of a vehicle such as a fuel cell vehicle and a hybrid electric vehicle.
- a driving power source or auxiliary power source for a motor of a vehicle such as a fuel cell vehicle and a hybrid electric vehicle.
- the volume of the negative electrode active material contained in the negative electrode active material layer 22 changes, and the negative electrode active material layer 22 expands and contracts.
- the bonding strength of the second bonding portion 45b that bonds the non-facing portion 20b of the negative electrode plate 20 to the separator 30 is that of the first bonding portion 45a that bonds the facing portion 20a to the separator 30. Greater than adhesive strength.
- the expansion-contraction dimension of the non-opposing part 20b can be made small, suppressing the expansion-contraction of the non-opposing part 20b rather than the opposing part 20a. Therefore, it is possible to suppress a change in the tension of the non-facing portion 20b due to the difference in expansion / contraction dimension between the facing portion 20a and the non-facing portion 20b. Therefore, it is possible to suppress wrinkles from occurring at the outer peripheral edge of the negative electrode plate 20 due to the expansion and contraction of the negative electrode active material layer 22.
- the secondary battery 100 includes a positive electrode plate 10 in which a positive electrode active material layer 12 is disposed on both surfaces 11 a and 11 b of a first current collector 11, and a negative electrode active material layer 22.
- the positive electrode active material layer 12 and the negative electrode active material layer 12 are sandwiched between the negative electrode plate 20 having an area larger than 12 and disposed on both surfaces 21a and 21b of the second current collector 21 with the separator 30 holding the electrolyte therebetween.
- the power generation element 110 is formed by stacking the material layers 22 facing each other.
- the negative electrode plate 20 is opposed to the positive electrode active material layer 12 with the separator 30 in between, and the non-opposite portion 20a is located on the outer periphery of the opposed portion 20a and does not face the positive electrode active material layer 12 with the separator 30 in between. And an opposing portion 20b.
- the negative electrode plate 20 and the separator 30 are bonded via a second adhesive layer 45, and the separator has a higher adhesive strength than the first adhesive portion 45 a that bonds the facing portion 20 a to the separator 30 in the second adhesive layer 45.
- the bonding strength of the second bonding portion 45 b that bonds the non-opposing portion 20 b to 30 is greater.
- the bonding strength of the second bonding portion 45b that bonds the non-facing portion 20b of the negative electrode plate 20 and the separator 30 is such that the facing portion 20a of the negative electrode plate 20 and the separator 30 are bonded. It is larger than the bonding strength of the first bonding portion 45a to be bonded.
- the expansion-contraction dimension of the non-opposing part 20b can be made small, suppressing the expansion-contraction of the non-opposing part 20b rather than the opposing part 20a. Therefore, it is possible to suppress a change in the tension of the non-facing portion 20b due to the difference in expansion / contraction dimension between the facing portion 20a and the non-facing portion 20b. Therefore, it is possible to suppress wrinkles from occurring at the outer peripheral edge of the negative electrode plate 20 due to the expansion and contraction of the negative electrode active material layer 22. Accordingly, it is possible to provide a secondary battery capable of preventing performance degradation and cycle life reduction.
- the adhesive strength of the second adhesive portion 45b can be made higher than the adhesive strength of the first adhesive portion 45a by a simple method of varying the average particle diameter. Therefore, the secondary battery can be easily manufactured.
- the secondary battery 100 is a lithium ion secondary battery, and at least one of the negative electrode active materials included in the negative electrode active material layer 22 is selected from the group consisting of silicon, a silicon alloy, and silicon oxide. Selected.
- the secondary battery 100 since the negative electrode active material layer 22 can be made thin, the negative electrode plate 20 can be reduced in size and increased in capacity. Therefore, the secondary battery 100 can be reduced in size and increased in capacity.
- the basis weight of the material constituting the second adhesive portion 45b may be larger than the basis weight of the material constituting the first adhesive portion 45a.
- the “weight per unit area” means a mass per unit area of the second adhesive layer 45 of a material that generates an adhesive force among materials constituting the second adhesive layer 45.
- the adhesive strength of the second adhesive layer 45 increases as the basis weight increases. That is, according to the secondary battery according to this modification, the adhesive strength of the second adhesive portion 45b can be made larger than the adhesive strength of the first adhesive portion 45a by a simple method of varying the basis weight. Therefore, the secondary battery 100 can be easily manufactured.
- the basis weight of the material constituting the second adhesive portion 45b is not particularly limited as long as it is larger than the basis weight of the material constituting the first adhesive portion 45a.
- the basis weight of the first adhesive portion 45a is 5 mg / cm 2 and the basis weight of the second adhesive portion 45b is 20 mg / cm 2. can do.
- the method of making the basis weight of the first adhesive portion 45a different from the basis weight of the second adhesive portion 45b is not particularly limited.
- the second adhesive layer 45 is configured on the surface 30a facing the negative electrode active material layer 22 in the separator 30.
- the basis weight can be varied by adjusting the time for applying the material. That is, the basis weight can be made different by making the time for applying the material forming the first bonding portion 45a different from the time for applying the material forming the second bonding portion 45b. The longer the application time, the greater the basis weight.
- the adhesive strength of the second adhesive portion 45b can be made higher than the adhesive strength of the first adhesive portion 45a by a simple method of varying the basis weight. Therefore, the secondary battery can be easily manufactured.
- the 2nd adhesion part 45b may be provided with non-ion permeability.
- the negative electrode active material layer 22 of the non-opposing portion 20b of the negative electrode plate 20 is covered with a member having non-ion permeability, the negative electrode active material layer 22 of the non-opposing portion 20b that does not function as an electrode and the electrolytic solution are formed. It can prevent that electrolyte solution is consumed by contact. Thereby, since electrolyte solution can be used effectively, the quantity of electrolyte solution with which secondary battery 100 is filled can be reduced. Therefore, the secondary battery 100 can be further miniaturized and the manufacturing cost can be reduced.
- the method for providing the second adhesive portion 45b with non-ion permeability is not particularly limited.
- the second adhesive portion 45b is provided with non-ion permeability by reducing the porosity of the second adhesive portion 45b.
- the porosity can be adjusted, for example, by applying a dispersion solution such as polyvinylidene fluoride (PVdF) to the separator 30 and then changing the drying conditions (drying temperature, drying time, etc.). The longer the temperature and the higher the drying temperature, the smaller the porosity.
- PVdF polyvinylidene fluoride
- Modification 3 In the above-described embodiment, Modification Example 1 and Modification Example 2, the material constituting the first adhesive portion 45a and the material constituting the second adhesive portion 45b are the same. However, the material forming the first bonding portion 45a may be different from the material forming the second bonding portion 45b.
- the adhesive strength of the second adhesive portion 45b can be made larger than the adhesive strength of the first adhesive portion 45a by a simple method of different materials. Therefore, the secondary battery can be easily manufactured.
- the combination of the material constituting the first adhesive portion 45a and the material constituting the second adhesive portion 45b is not particularly limited as long as the adhesive strength of the second adhesive portion 45b is larger than the adhesive strength of the first adhesive portion 45a.
- a polyvinylidene fluoride (PVdF) dispersion solution is used as a material constituting the first adhesive portion 45a, and ceramic particles and an acrylic binder are substituted with N-methyl-2-pyrrolidone (NMP) as a material constituting the second adhesive portion 45b.
- NMP N-methyl-2-pyrrolidone
- the positive electrode active material layer 12 is disposed on both surfaces 11a and 11b of the first current collector 11, and the negative electrode active material layer is disposed on both surfaces 21a and 21b of the second current collector 21.
- a so-called non-hyperbolic secondary battery in which 22 is arranged has been described as an example.
- the positive electrode active material layer 12 is disposed on one surface 11a (21a) of the first current collector 11 (second current collector 21) and the one surface 11a (21a). It is also possible to apply the present invention to a so-called hyperbolic secondary battery in which the negative electrode active material layer 22 is disposed on the other surfaces 11b and 21b opposite to each other.
- the first current collector 11 and the second current collector 21 may have the same structure.
- the material which comprises the 1st electrical power collector 11 and the material which comprises the 2nd electrical power collector 21 are not specifically limited, A conventionally well-known thing can be used.
- the material constituting the first current collector 11 and the material constituting the second current collector 21 are, for example, aluminum foil, stainless steel (SUS) foil, clad material of nickel and aluminum, clad material of copper and aluminum, SUS, It may be an aluminum clad material or a plating material of a combination of these metals.
- a current collector in which a metal surface is coated with aluminum may be used.
- a so-called composite current collector in which two or more metal foils are bonded together may be used.
- the secondary battery has been described through the embodiment and the modified example thereof.
- the present invention is not limited to the configuration described in the embodiment and the modified example, and is appropriately changed based on the description of the claims. Is possible.
- the present invention can be applied regardless of the type of the secondary battery, the type of the active material, the type of the electrolyte, etc., as long as it is a secondary battery in which the negative electrode active material layer expands and contracts with use.
- the secondary battery of the type in which the positive electrode tab 13 and the negative electrode tab 23 are taken out from one side of the secondary battery 100 has been described as an example.
- the present invention can also be applied to a secondary battery in which the positive electrode tab is taken out from one side of the secondary battery and the negative electrode tab is taken out from the other side.
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Abstract
Description
図2および図3を参照して、発電要素110は、セパレータ30を挟んで後述する正極活物質層12と負極活物質層22とが対向した状態で、正極板10と負極板20とを積層してなる。
電解液の種類は特に限定されず、従来公知のものを適宜利用することができる。本実施形態では、電解液として、液体電解質を用いたものを使用するが、ゲル電解質を用いた電解液を使用してもよい。
外装部材120は、発電要素110を電解液とともに収容する。
正極板10は、第1集電体11の両面11a、11b上に正極活物質層12を配置してなる。
負極板20は、第2集電体21の両面21a、21b上に負極活物質層22を配置してなる。
セパレータ30は、電解液に含まれる電解質を保持する。
正極板10とセパレータ30とは、第1接着層40を介して接着されており、負極板20とセパレータ30とは、第2接着層45を介して接着されている。
図3および図4を参照して、負極板20は、セパレータ30を挟んで正極活物質層12に対向している対向部20aと、対向部20aの外周に位置し、セパレータ30を挟んで正極活物質層12に対向していない非対向部20bと、を備える。
本実施形態に係る二次電池100は、燃料電池車およびハイブリッド電気自動車等の車両のモータ等の駆動用電源や補助電源として充放電が繰り返しなされる。充放電によって、負極活物質層22に含まれる負極活物質の体積が変化して負極活物質層22が膨張収縮する。
本実施形態に係る二次電池100は、第1集電体11の両面11a、11b上に正極活物質層12を配置してなる正極板10と、負極活物質層22を、正極活物質層12の面積よりも大きな面積をもって、第2集電体21の両面21a、21b上に配置してなる負極板20とを、電解質を保持するセパレータ30を挟んで、正極活物質層12と負極活物質層22とが対向した状態で積層してなる発電要素110を有する。負極板20は、セパレータ30を挟んで正極活物質層12に対向している対向部20aと、対向部20aの外周に位置し、セパレータ30を挟んで正極活物質層12に対向していない非対向部20bと、を備える。負極板20とセパレータ30とは、第2接着層45を介して接着されており、第2接着層45において、セパレータ30に対向部20aを接着する第1接着部45aの接着強度よりも、セパレータ30に非対向部20bを接着する第2接着部45bの接着強度の方が大きい。
上述した実施形態では、第1接着部45aを構成する材料よりも第2接着部45bを構成する材料の平均粒径を小さくすることにより、第1接着部45aの接着強度よりも第2接着部45bの接着強度を大きくした。しかしながら、第2接着部45bの接着強度を第2接着部45bの接着強度よりも大きくする方法は特に限定されない。
また、第2接着部45bは、非イオン透過性を備えてもよい。
また、上述した実施形態並びに改変例1および改変例2では、第1接着部45aを構成する材料と第2接着部45bを構成する材料とは同じだった。しかしながら、第1接着部45aを構成する材料と第2接着部45bを構成する材料とは異なっていてもよい。
さらに、上述した実施形態および改変例では、第1集電体11の両面11a、11bに正極活物質層12が配置されるとともに、第2集電体21の両面21a、21bに負極活物質層22が配置された、いわゆる非双曲型の二次電池を例に説明した。
11 第1集電体、
11a、21a 面(一方の面)、
11b、21b 面、
12 正極活物質層、
20 負極板、
20a 対向部、
20b 非対向部、
21 第2集電体、
22 負極活物質層、
30 セパレータ、
40 第1接着層、
45 第2接着層(接着層)、
45a 第1接着部、
45b 第2接着部、
100 二次電池、
110 発電要素、
120 外装部材、
M 剥離紙。
Claims (6)
- 第1集電体の少なくとも一方の面上に正極活物質層を配置してなる正極板と、負極活物質層を、前記正極活物質層の面積よりも大きな面積をもって、第2集電体の少なくとも一方の面上に配置してなる負極板とを、電解質を保持するセパレータを挟んで、前記正極活物質層と前記負極活物質層とが対向した状態で積層してなる発電要素を有し、
前記負極板は、前記セパレータを挟んで前記正極活物質層に対向している対向部と、前記対向部の外周に位置し、前記セパレータを挟んで前記正極活物質層に対向していない非対向部と、を備え、
前記負極板と前記セパレータとは、接着層を介して接着されており、
前記接着層において、前記セパレータに前記対向部を接着する第1接着部の接着強度よりも、前記セパレータに前記非対向部を接着する第2接着部の接着強度の方が大きい、二次電池。 - 前記第2接着部を構成する材料の平均粒径は、前記第1接着部を構成する材料の平均粒径よりも小さい、請求項1に記載の二次電池。
- 前記第2接着部を構成する材料の目付量は、前記第1接着部を構成する材料の目付量よりも大きい、請求項1または請求項2に記載の二次電池。
- 前記第1接着部を構成する材料と前記第2接着部を構成する材料とは異なる、請求項1~3のいずれか1項に記載の二次電池。
- 前記第2接着部は、非イオン透過性を備える、請求項4に記載の二次電池。
- リチウムイオン二次電池であり、
前記負極活物質層に含まれる負極活物質の少なくとも1種は、シリコン、シリコン合金およびシリコン酸化物からなる群から選択される、請求項1~5のいずれか1項に記載の二次電池。
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KR1020197008174A KR102071835B1 (ko) | 2016-09-29 | 2017-09-28 | 이차 전지 |
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EP3859863A4 (en) * | 2018-09-28 | 2022-06-22 | Zeon Corporation | SECONDARY BATTERY AND METHOD OF MANUFACTURE THEREOF |
JP7380581B2 (ja) | 2018-09-28 | 2023-11-15 | 日本ゼオン株式会社 | 二次電池およびその製造方法 |
CN112655106B (zh) * | 2018-09-28 | 2024-06-21 | 日本瑞翁株式会社 | 二次电池及其制造方法 |
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US10651448B2 (en) | 2020-05-12 |
EP3522263B1 (en) | 2020-08-26 |
MY175433A (en) | 2020-06-25 |
JP6757415B2 (ja) | 2020-09-16 |
KR102071835B1 (ko) | 2020-01-30 |
CN109792089A (zh) | 2019-05-21 |
CN109792089B (zh) | 2020-07-14 |
EP3522263A4 (en) | 2019-08-07 |
EP3522263A1 (en) | 2019-08-07 |
KR20190040295A (ko) | 2019-04-17 |
US20190221808A1 (en) | 2019-07-18 |
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