WO2018220954A1 - 蓄電デバイス用部材、その製造方法及び蓄電デバイス - Google Patents
蓄電デバイス用部材、その製造方法及び蓄電デバイス Download PDFInfo
- Publication number
- WO2018220954A1 WO2018220954A1 PCT/JP2018/010949 JP2018010949W WO2018220954A1 WO 2018220954 A1 WO2018220954 A1 WO 2018220954A1 JP 2018010949 W JP2018010949 W JP 2018010949W WO 2018220954 A1 WO2018220954 A1 WO 2018220954A1
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- WIPO (PCT)
- Prior art keywords
- fluororesin
- resin layer
- storage device
- electricity storage
- base material
- Prior art date
Links
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Images
Classifications
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a member for an electricity storage device, a manufacturing method thereof, and an electricity storage device.
- This application claims priority based on Japanese Patent Application No. 2017-110096, which is a Japanese patent application filed on June 2, 2017. All the descriptions described in the Japanese patent application are incorporated herein by reference.
- ⁇ ⁇ ⁇ ⁇ Lithium ion secondary batteries are used as power sources for electronic devices.
- power storage devices other than secondary batteries such as electric double layer capacitors, have been developed.
- a secondary battery typically has a configuration in which an electrode group including a positive electrode and a negative electrode is accommodated in a bag-shaped exterior body such as an aluminum laminate film, and tab leads are arranged from the inside to the exterior of the exterior body (patent) Reference 1).
- the tab lead is mainly composed of a metal base material that transfers power between the positive electrode or negative electrode of the electrode group and an external member.
- the bag-shaped exterior body generally includes a metal film-like substrate. In order to insulate the base material of the exterior body and the base material of the tab lead, both are joined via a resin resin layer provided on each. Further, by providing such a resin layer, the electrode group can be sealed in the exterior body in a state where the exterior body is formed in a bag shape.
- polyolefin such as polypropylene is generally used.
- a resin layer is required to be sufficiently adhered to a metal base material.
- a polyolefin resin layer is usually laminated on a base material via an acid-modified polyolefin.
- One embodiment of the present invention made to solve the above problems is a member for an electricity storage device including a base material containing a metal as a main component and a resin layer laminated on the base material, wherein the resin layer is It is an electricity storage device member containing a cross-linked fluororesin.
- One embodiment of the present invention is a method for manufacturing a member for an electricity storage device including a step of laminating a layer containing a fluororesin on a base material containing a metal as a main component, and a step of irradiating the layer containing the fluororesin with ionizing radiation. is there.
- One embodiment of the present invention includes a positive electrode, a negative electrode, an electrolyte, an exterior body that houses the positive electrode, the negative electrode, and the electrolyte, one end exposed from the exterior body, and the other end that is the positive electrode or the negative electrode
- An electricity storage device including a connected tab lead, wherein the exterior body and the tab lead are heat-sealed, and at least one of the exterior body and the tab lead is an electricity storage device that is a member for the electricity storage device.
- FIG. 1 is a perspective view showing a secondary battery according to the first embodiment of the electricity storage device of the present invention.
- FIG. 2 is a partial cross-sectional view of the secondary battery of FIG.
- FIG. 3 is a partial cross-sectional view showing a tab lead according to a second embodiment of the member for an electricity storage device of the present invention.
- FIG. 4 is a partial cross-sectional view showing a secondary battery according to the third embodiment of the electricity storage device of the present invention.
- the resin layer is required to have durability against an electrolytic solution, that is, chemical resistance, heat resistance, flame retardancy, strength, and the like, in addition to heat-fusibility and adhesion to the above-described base material.
- an electrolytic solution that is, chemical resistance, heat resistance, flame retardancy, strength, and the like
- the electrolyte solution is likely to leak out from the heat-sealed interface or the interface between the base material and the resin layer.
- demands related to heat resistance and the like are increasing due to the increasing current and voltage of power storage devices, including power storage devices for electric vehicles.
- the present invention has been made based on the above-described circumstances, and has a member for an electricity storage device having good heat resistance and flame retardancy, a method for producing such a member for an electricity storage device, and such an electricity storage device. It aims at providing an electrical storage device provided with the member for use.
- the present invention provides an electricity storage device member comprising a resin layer having good heat resistance and flame retardancy, a method for producing such an electricity storage device member, and an electricity storage device comprising such an electricity storage device member. Can do.
- An electricity storage device member is an electricity storage device member including a base material containing a metal as a main component and a resin layer laminated on the base material, wherein the resin layer is crosslinked. Contains fluororesin. In the present specification, “crosslinked” indicates that a three-dimensional crosslinked structure is formed.
- the resin layer contains a cross-linked fluororesin, the heat resistance and chemical resistance are good, and the occurrence of liquid leakage is suppressed. Moreover, this crosslinked fluororesin is excellent in flame retardancy.
- the member for an electricity storage device is excellent in the heat resistance, flame retardancy, etc. of the resin layer. Therefore, the electricity storage device has a high operating temperature and is expected to be used in a severe environment, for example, an electricity storage device for an electric vehicle. It is suitable as a member to be used. Furthermore, the power storage device using the power storage device member is highly safe when an unforeseen abnormal situation such as heat generation occurs.
- the “main component” refers to a component having the highest content on a mass basis, and is preferably a component that is contained by 50% by mass or more.
- the electricity storage device member preferably has a chemical bond between the fluororesin and the surface of the substrate.
- the adhesiveness of a base material and a resin layer can be improved, for example, even when the impact by dropping etc. is added, a liquid leak can be suppressed and safety
- security can be ensured.
- the power storage device member does not require a surface roughening treatment or an adhesive in the manufacturing process, and can increase productivity.
- “Chemical bond” refers to a covalent bond, an ionic bond, and a hydrogen bond.
- the resin layer is a heat fusion layer.
- the “thermal fusion layer” refers to a layer that is thermally fused with another resin layer by a thermal fusion treatment.
- the resin layer of the power storage device member that is, the heat fusion layer may be softened and thermally fused, or the other resin layer to be bonded may be softened and thermally fused. You may wear it. In the latter case, the heat fusion layer of the power storage device member may be one that does not substantially soften during heat fusion.
- the resin layer preferably contains a cloth or filler, and the linear expansion coefficient of the resin layer is preferably 1 ⁇ 10 ⁇ 7 / K or more and 40 ⁇ 10 ⁇ 6 / K or less.
- the linear expansion coefficient becomes small, and the thermal expansion coefficient of the resin layer and the thermal expansion coefficient of the base material containing a metal as a main component can be brought close to each other.
- peeling strength ie, the adhesiveness between layers, can be raised more by suppressing generation
- the substrate and the resin layer containing the fluororesin are temporarily fixed by a press or the like, and when ionizing radiation irradiation for crosslinking is performed, the difference between the linear expansion coefficient before irradiation and the substrate and resin layer There may be a minute gap between the two. Therefore, by adding filler or cloth to the resin layer in this way, the thermal expansion coefficient of the resin layer and the thermal expansion coefficient of the base material are brought close to each other, thereby suppressing the generation of the void due to the difference in the linear expansion coefficient. be able to. Furthermore, by including a cloth or filler in the resin layer, the tensile strength at break can be improved, and safety, durability, and the like can be improved.
- linear expansion coefficient is a rate at which the length of an object expands when the temperature rises by 1 ° C., and is an average value from 20 ° C. to 150 ° C.
- This “linear expansion coefficient” can be measured according to JIS-K-7197 (2012) “Test method for linear expansion coefficient by thermomechanical analysis of plastics”.
- the electricity storage device member is laminated on the surface of the resin layer opposite to the base, and further includes a coating layer containing a fluororesin, and the fluororesin contained in the coating layer is a non-crosslinked fluororesin, or A fluororesin having a lower melting point than that of a cross-linked fluororesin is preferred.
- the cross-linked fluororesin is preferably a tetrafluoroethylene / hexafluoropropylene copolymer (FEP).
- FEP has a lower melting point than other fluororesins and high fluidity at about 300 ° C. Therefore, by using FEP for the resin layer, the heat fusion temperature can be lowered or the heat fusion treatment time can be shortened.
- the fluororesin contained in the coating layer is FEP.
- FEP is a preferred resin among fluororesins from the viewpoint of heat-fusibility.
- the peel strength between the resin layer and the substrate is preferably 0.1 N / cm or more and 100 N / cm or less.
- the peel strength is an index indicating the degree of cross-linking of the fluororesin in the resin layer. Therefore, when the peel strength is 0.1 N / cm or more, it can be said that moderate crosslinking occurs, and the heat resistance and chemical resistance are further increased.
- peel strength between the resin layer and the substrate is 100 N / cm or less, it can be said that the resin layer is in a crosslinked state that is softened to some extent by heating.
- peel strength means peel strength obtained by a test method in accordance with “Adhesive—Peel Adhesive Strength Test Method—Part 2: 180 ° Peel” of JIS-K-6854-2 (1999). Means.
- the ten-point average roughness (R Z ) of the surface of the base material in the region where the resin layer is laminated is preferably 0.001 ⁇ m or more and 10 ⁇ m or less.
- the smoothness of the surface of the base material in the region where the resin layer is laminated is high, the thickness of the resin layer may be uniform, and the occurrence of dielectric breakdown and migration can be suppressed. . Thereby, heat-fusibility and chemical resistance can also be improved.
- the surface smoothness of the base material is high in this way, it is not necessary to perform a roughening treatment such as etching, and productivity can be improved.
- “ten-point average roughness (Rz)” is measured according to JIS-B-0601 (2001) with a cutoff value ( ⁇ c) of 2.5 mm and an evaluation length (l) of 12.5 mm. Value.
- the member for an electricity storage device is preferably a tab lead or an exterior body.
- the advantages of the present invention such as heat resistance and flame retardancy can be more effectively enjoyed.
- the method for manufacturing a member for an electricity storage device includes a step of laminating a layer containing a fluororesin on a base material containing metal as a main component, and a step of irradiating the layer containing the fluororesin with ionizing radiation. Prepare.
- the fluororesin in the irradiated layer is cross-linked, and a chemical bond between the fluororesin and the metal in the substrate may also occur. Therefore, according to the said manufacturing method, the member for electrical storage devices provided with the resin layer which is favorable in heat resistance and a flame retardance, and is excellent also in adhesiveness with a base material can be manufactured.
- An electricity storage device includes a positive electrode, a negative electrode, an electrolytic solution, an exterior body containing the positive electrode, the negative electrode, and the electrolytic solution, one end exposed from the exterior body, and the other end of the positive electrode or
- An electricity storage device including a tab lead connected to a negative electrode, wherein the exterior body and the tab lead are thermally fused, and at least one of the exterior body and the tab lead is the electricity storage device member.
- the electricity storage device since at least one of the outer package and the tab lead is the electricity storage device member, the heat resistance and flame retardancy of the resin layer are good. Therefore, the power storage device can maintain good quality even in severe environments such as high temperatures or when used at high voltage and high current.
- the electricity storage device further includes a heat fusion film interposed between the outer package and the tab lead, and the heat fusion film is a non-crosslinked fluororesin or a fluororesin having a melting point lower than that of the crosslinked fluororesin It is preferable to contain.
- a heat-sealing film containing a non-cross-linked fluororesin or a fluororesin having a melting point lower than that of the cross-linked fluororesin is interposed between the outer package and the tab lead. Wearability can be improved.
- the secondary battery 10 shown in FIGS. 1 and 2 includes a plate-shaped positive electrode, a plate-shaped negative electrode and an electrolyte solution (not shown), an outer package 11, and tab leads 12 and 12 '.
- a positive electrode and a negative electrode are laminated via a separator to form a laminated electrode group.
- the laminated electrode group and the electrolytic solution are housed in a sealed state in the exterior body 11.
- the laminated electrode group is immersed in the electrolytic solution.
- the exterior body 11 is formed from a laminated film as will be described later.
- the sealing portion 13 around the two laminated films or the folded one laminated film is heat-sealed, so that the sealed state is achieved.
- the tab lead 12 is disposed so that one end is exposed from the exterior body 11 and the other end is connected to the positive electrode in the exterior body 11.
- the tab lead 12 ′ is arranged so that one end is exposed from the exterior body 11 and the other end is connected to the negative electrode in the exterior body 11.
- An intermediate portion of the tab leads 12 and 12 ′ is sandwiched between laminated films as the outer package 11, and the outer package 11 and the tab leads 12 and 12 ′ are heat-sealed at this portion.
- the positive electrode and the negative electrode are typically a laminate in which an active material layer containing an active material is laminated on the surface of a current collector such as a metal foil.
- the shape of the positive electrode and the negative electrode is usually a plate shape, but may be other than a plate shape.
- the separator is usually an insulating and porous sheet. This separator is impregnated with an electrolytic solution.
- the exterior body 11 that is an embodiment of the electricity storage device member of the present invention includes a base material 15, a resin layer 16 laminated on the inner surface side of the base material 15, and the base material 15. And an outer layer 17 laminated on the outer surface side. That is, the exterior body 11 is a laminated film in which the resin layer 16, the base material 15, and the outer layer 17 are laminated in this order. Moreover, the exterior body 11 is a container which accommodates a positive electrode, a negative electrode, a separator, and electrolyte solution in the sealed state as mentioned above.
- the substrate 15 is in the form of a film and is usually a metal foil. That is, the base material 15 has a metal as a main component. Examples of the metal include aluminum, copper, and stainless steel.
- the base material 15 is substantially made of metal, but may contain additives other than metal.
- the upper limit of the ten-point average roughness (R Z ) of the inner surface of the substrate 15, that is, the region where the resin layer 16 is laminated is preferably 10 ⁇ m and more preferably 5 ⁇ m.
- the arithmetic average roughness (Ra) of the inner surface of the base material 15 is preferably 0.001 ⁇ m, more preferably 0.01 ⁇ m, further preferably 0.1 ⁇ m, and still more preferably 0.3 ⁇ m.
- the resin layer 16 is directly laminated on the inner surface of the base material 15.
- the resin layer 16 is a layer containing a cross-linked fluororesin.
- the resin layer 16 may contain other optional components in addition to the fluororesin.
- the resin layer 16 is a heat fusion layer having heat fusion properties.
- the fluororesin is an organic group in which at least one hydrogen atom bonded to a carbon atom in the main chain constituting the structural unit of the polymer chain has a fluorine atom or a fluorine atom (hereinafter also referred to as “fluorine atom-containing group”). The one replaced with.
- the fluorine atom-containing group is a group in which at least one hydrogen atom in a linear, branched or cyclic organic group is substituted with a fluorine atom.
- a fluoroalkyl group, a fluoroalkoxy group, a fluoropolyether group, etc. Can be mentioned.
- Fluoroalkyl group means an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and includes a “perfluoroalkyl group”. Specifically, a “fluoroalkyl group” is a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms, and all hydrogen atoms other than one hydrogen atom at the end of the alkyl group are substituted with fluorine atoms. Group and the like.
- the “fluoroalkoxy group” means an alkoxy group in which at least one hydrogen atom is substituted with a fluorine atom, and includes a “perfluoroalkoxy group”.
- a “fluoroalkoxy group” is a group in which all hydrogen atoms of an alkoxy group are substituted with fluorine atoms, and all hydrogen atoms other than one hydrogen atom at the end of the alkoxy group are substituted with fluorine atoms. Group and the like.
- the “fluoropolyether group” is a monovalent group having a plurality of alkylene oxide chains as repeating units and having an alkyl group or a hydrogen atom at the terminal, and the alkylene oxide chain and / or the terminal alkyl group or A monovalent group having a group in which at least one hydrogen atom in a hydrogen atom is substituted with a fluorine atom.
- “Fluoropolyether group” includes “perfluoropolyether group” having a plurality of perfluoroalkylene oxide chains as repeating units.
- a fluororesin is a polymer compound having a fluorine atom in the molecule.
- the fluororesin include tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoro.
- Dioxol copolymer TFE / PDD
- PCTFE polychlorotrifluoroethylene
- ECTFE chlorotrifluoroethylene-ethylene copolymer
- PVDF polyvinylidene fluoride
- PVF polyvinyl fluoride
- VDF-HFP copolymer vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer
- VDF-HFP-TFE copolymer VDF-HFP-TFE copolymer
- fluororesins tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE), and tetrafluoroethylene-perfluorodiode.
- FEP tetrafluoroethylene / hexafluoropropylene copolymer
- PFA tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer
- PTFE polytetrafluoroethylene
- tetrafluoroethylene-perfluorodiode tetrafluoroethylene-perfluorodiode.
- a xol copolymer (TFE / PDD) is preferred, and FEP is more preferred.
- FEP it is possible to improve the heat-fusibility as described above.
- the fluororesin in the resin layer 16 is crosslinked, but specifically, it is preferable that the carbon atoms of the main chain of the fluororesin are covalently bonded. Thus, when the fluororesin is cross-linked, good chemical resistance and heat resistance can be exhibited.
- the outer package 11 preferably has a chemical bond between the fluororesin in the resin layer 16 and the surface of the substrate 15. Specifically, it is preferable that the carbon atom of the main chain of the fluororesin and the atom present on the surface of the substrate 15 are covalently bonded or ionically bonded. Examples of the atoms present on the surface of the substrate 15 include metal atoms or other atoms that are the main components of the substrate 15. In addition, a coupling agent may be contained in the resin layer 16, and the fluororesin and atoms present on the surface of the base material 15 may be chemically bonded via the coupling agent.
- X-ray photoelectron spectroscopy also referred to as XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis)
- X-ray photoelectron spectroscopy measures the energy distribution of photoelectrons emitted by irradiating a sample with X-rays, and subtracts this value from the energy of the irradiated X-rays to calculate the binding energy of electrons. Since the binding energy of electrons is a value inherent to the element and its electronic state, the element and chemical bond in the sample can be identified from this value. In particular, when a hard X-ray such as spring-8 is used, it becomes possible to analyze a depth of about 20 nm, so that chemical bonds at the interface can be analyzed.
- the melting point of the cross-linked fluororesin of the resin layer 16 is preferably, for example, 250 ° C. or higher and 350 ° C. or lower. When the melting point of the fluororesin is in the above range, it is possible to achieve both good heat-fusibility and heat resistance.
- a method of cross-linking the fluororesin of the resin layer 16 and forming a chemical bond between the fluororesin and the surface of the substrate 15 for example, a method of irradiating ionizing radiation in the molten state of oxygen-free and fluororesin This can be done by generating a fluorine radical.
- the ionizing radiation irradiation method will be described in detail in the manufacturing method described later.
- the lower limit of the peel strength between the resin layer 16 and the substrate 15 is preferably 0.1 N / cm, more preferably 0.3 N / cm, still more preferably 1 N / cm, still more preferably 5 N / cm, and 10 N / cm. cm is even more preferable.
- this peel strength is related to the degree of crosslinking of the fluororesin as described above. Therefore, when the peel strength is equal to or higher than the lower limit, it can be said that sufficient cross-linking has occurred in the fluororesin, and chemical resistance and heat resistance can be further improved.
- the upper limit of the peel strength is preferably 100 N / cm, and more preferably 80 N / cm.
- the peel strength between the resin layer 16 and the substrate 15 is not more than the above upper limit, the crosslinking remains at an appropriate level, and the heat-fusibility can be improved.
- the lower limit of the content of the fluororesin in the resin layer 16 is preferably 50% by mass, more preferably 70% by mass, further preferably 90% by mass, and particularly preferably 99% by mass. By making content of the fluororesin in the resin layer 16 more than the said minimum, chemical resistance and heat resistance can be improved more.
- the content of the fluororesin in the resin layer 16 may be 100% by mass. However, when the resin layer 16 contains a cloth or filler described later, the content of the fluororesin in all components other than the cloth and filler in the resin layer 16 is preferably in the above range.
- the resin layer 16 preferably contains a cloth or a filler.
- the cloth can be defined as, for example, a woven fabric, a fabric, or the like in which fibers are woven.
- the cloth include resin cloth, metal cloth, ceramics, glass cloth, LCP cloth, and the like, and LCP cloth and glass cloth are preferable.
- the filler include a resin filler, a metal filler, a ceramic filler, and a glass filler. Heat resistance, tensile strength, and the like can be increased by including a cloth or filler in the resin layer 16, and more preferably including a cloth.
- the resin layer 16 may be a layer in which a cloth is impregnated with a fluororesin.
- the content of the cloth or filler in the resin layer 16 may be, for example, 10% by mass or more and 90% by mass or less. Moreover, when the cloth is contained, the average thickness of the cloth with respect to the average thickness of the resin layer 16 can be 10% or more and 90% or less.
- Examples of other components that may be contained in the resin layer 16 include resins other than cross-linked fluororesins, coupling agents, flame retardants, antioxidants, and plasticizers.
- Examples of the resin other than the cross-linked fluororesin include thermoplastic resins such as polyethylene and polypropylene.
- the upper limit of the linear expansion coefficient of the resin layer 16 may be, for example, 200 ⁇ 10 ⁇ 6 / K, but is preferably 40 ⁇ 10 ⁇ 6 / K, and more preferably 30 ⁇ 10 ⁇ 6 / K.
- the linear expansion coefficient of aluminum is 24 ⁇ 10 ⁇ 6 / K
- the linear expansion coefficient of copper is 17 ⁇ 10 ⁇ 6 / K.
- the linear expansion coefficient of the resin layer 16 can be made small by making the resin layer 16 contain a cloth or a filler.
- the lower limit of the linear expansion coefficient of the resin layer 16 can be set to 10 ⁇ 10 ⁇ 6 / K, for example.
- the lower limit of the linear expansion coefficient of the resin layer 16 is preferably 1 ⁇ 10 ⁇ 7 / K. If the linear expansion coefficient of the resin layer 16 is less than 1 ⁇ 10 ⁇ 7 / K, the processability of the resin layer 16 may be impaired. This is because the difference in linear expansion coefficient between the base material 15 mainly composed of metal and the resin layer 16 is increased.
- average thickness of the resin layer 16 are 1 micrometer or more and 200 micrometers or less. By setting the average thickness of the resin layer 16 within the above range, it is possible to ensure sufficient heat-fusibility and insulation.
- the outer layer 17 has a function as a protective layer for protecting the outer surface of the substrate 15.
- the outer layer 17 usually has a resin as a main component.
- the resin forming the outer layer 17 include polyethylene terephthalate (PET) and polyamide.
- PET polyethylene terephthalate
- a resin having a melting point higher than that of the cross-linked fluororesin contained in the resin layer 16 can be used.
- Teb lead 12, 12 ' As shown in FIG. 2, the tab leads 12 and 12 ′ that are one embodiment of the member for an electricity storage device of the present invention include a base material 18 and a resin layer 19 laminated on the base material 18.
- the base material 18 has a strip shape.
- the substrate 18 is usually a metal foil. That is, the base material 18 has a metal as a main component.
- the base 18 in the tab lead 12 on the positive electrode side is preferably formed from aluminum or an aluminum alloy. Although a high potential is applied to the positive electrode side, when the substrate 18 is formed of aluminum or an aluminum alloy, dissolution in the electrolytic solution can be suppressed.
- the base 18 in the tab lead 12 'on the negative electrode side is preferably made of copper, nickel, aluminum, alloys thereof, or the like.
- the base material 18 is substantially made of metal, but may contain additives other than metal.
- the structure of the tab lead 12 on the positive electrode side and the structure of the tab lead 12 ′ on the negative electrode side can be the same except for a suitable material of the substrate 18.
- the size of the substrate 18 is not particularly limited, and is appropriately set according to the size and use of the secondary battery 10 itself.
- the average thickness of the base material 18 can be set to, for example, 0.05 mm or more and 0.5 mm.
- the length of the base material 18 can be set to, for example, 20 mm or more and 100 mm.
- the width of the substrate 18 can be 2 mm or more and 80 mm. The width of the substrate 18 may be longer than the length of the substrate 18.
- the ten-point average roughness (R Z ) of the central portion in the length direction of the substrate 18, that is, the region where the resin layer 19 is laminated, is the same as that described above as the value of the substrate 15 of the exterior body 11 described above. It can be.
- the resin layer 19 is not laminated
- One end 18 a of the base material 18 is exposed from the exterior body 11.
- the other end 18 b of the base 18 of the tab lead 12 on the positive electrode side is connected to a positive electrode (not shown) by a lead wire 14.
- the other end 18b of the base 18 of the tab lead 12 'on the negative electrode side is similarly connected to a negative electrode (not shown) by the lead wire 14.
- the resin layer 19 covers the entire surface of the central portion in the length direction of the belt-like base material 18. That is, the resin layer 19 is laminated not only on the front surface and the back surface but also on a pair of side surfaces in the central portion of the substrate 18. The resin layer 19 is directly laminated on the base material 18.
- the resin layer 19 includes a cross-linked fluororesin.
- the resin layer 19 may contain other optional components in addition to the fluororesin.
- the resin layer 19 is a heat fusion layer having heat fusion properties.
- the crosslinked fluororesin contained in the resin layer 19 is the same as that described above as the crosslinked fluororesin contained in the resin layer 16 of the exterior body 11.
- the tab leads 12 and 12 ′ also preferably have a chemical bond between the cross-linked fluororesin contained in the resin layer 19 and the surface of the base material 18, similarly to the outer package 11.
- the preferred form of the resin layer 19 and the preferred form relating to the relationship between the resin layer 19 and the base material 18 are the preferred form of the resin layer 16 of the exterior body 11 and the resin layer 16 and the base material 15 described above. It is the same as that of the suitable form which concerns on this relationship.
- the average thickness of the resin layer 19 in the tab leads 12 and 12 ′ can be set to, for example, 1 ⁇ m to 200 ⁇ m. By setting the average thickness of the resin layer 19 within the above range, it is possible to ensure sufficient heat-fusibility and insulation.
- one end of the tab leads 12, 12 ′ that is, one end 18 a of the base material 18 is disposed in a state exposed from the exterior body 11, and is sealed by the exterior body 11.
- the tab leads 12 and 12 ′ are arranged so that the resin layer 16 of the outer package 11 and the resin layer 19 of the tab leads 12 and 12 ′ are in direct contact with each other.
- the resin layers 16 in the seal portion 13 of the exterior body 11 and the resin layers 16 of the exterior body 11 and the resin layers 19 of the tab leads 12 and 12 ′ Heat-sealed.
- the positive electrode, the negative electrode, and the separator which are the laminated electrode group immersed in the electrolytic solution, can be sealed in the outer package 11.
- the resin layer 16 of the outer package 11 and the resin layer 19 of the tab leads 12, 12 ′ contain a cross-linked fluororesin, the heat resistance, flame resistance, and chemical resistance of these resin layers Good properties.
- these resin layers have high adhesiveness with a base material.
- both the heat-sealing resin layer 16 and the resin layer 19 contain a fluororesin, that is, the same kind of resin, the heat-sealing property is excellent.
- the secondary battery 10 including the exterior body 11 and the tab leads 12 and 12 ′ is excellent in safety because the occurrence of liquid leakage is suppressed even in a severe environment.
- the secondary battery 10 including the exterior body 11 and the tab leads 12 and 12 ' can be used for the same application as that of a conventional power storage device, but in particular, an application used at a high current and a high voltage, for example, an electric vehicle. It can be suitably used as a power storage device.
- ⁇ Method for Manufacturing Member for Power Storage Device (Exterior Body 11 and Tab Leads 12, 12 ′)>
- a method for manufacturing a member for an electricity storage device according to an embodiment of the present invention is as follows. A step of laminating a layer containing a fluororesin on a metal-based substrate, and a step of irradiating the layer containing the fluororesin with ionizing radiation.
- a lamination process is a process of laminating
- a method of laminating a layer containing a substantially uncrosslinked fluororesin on the surface of the substrate while melt extrusion molding, a method of laminating a substrate and a layer containing a substantially uncrosslinked fluororesin, etc. can be done by.
- the layer containing a fluororesin can also be laminated
- An irradiation process is performed by irradiating ionizing radiation with respect to the laminated body of a base material and the layer containing a fluororesin from the surface side of the layer containing a fluororesin.
- the resin layer is formed only on one side as in the case of the outer package 11, it is only necessary to irradiate ionizing radiation only from one side.
- the resin layer is formed on the entire periphery like the tab lead 12, the entire periphery is irradiated with ionizing radiation.
- the laminate In this irradiation, the laminate is placed in an oxygen-free atmosphere, specifically an atmosphere having an oxygen concentration of 100 ppm or less, and irradiated with ionizing radiation while the fluororesin is melted. As a result, the fluororesin is crosslinked, and a chemical bond is generated between the fluororesin and the substrate.
- the oxygen-free atmosphere is more preferably 10 ppm or less. If the oxygen concentration is high, the main chain of the fluororesin may be broken by irradiation with ionizing radiation.
- the temperature at which the fluororesin is melted is preferably a temperature that is 0 ° C. or more and less than 30 ° C. higher than the melting point of the fluororesin. When the fluororesin is heated to a temperature higher than the melting point by 30 ° C. or more, the thermal decomposition of the fluororesin is promoted and the material properties may be deteriorated.
- a method for reducing the oxygen concentration there is a method such as vacuum using an inert gas such as nitrogen.
- the ionizing radiation for example, ⁇ -ray, electron beam, X-ray, neutron beam, high-energy ion beam and the like can be used.
- the irradiation dose of ionizing radiation is preferably 0.01 kGy or more and 2000 kGy or less, and more preferably 1 kGy or more and 500 kGy or less.
- the irradiation dose is less than the above lower limit, the crosslinking reaction of the fluororesin may not proceed sufficiently.
- the above upper limit is exceeded, the fluororesin may be easily decomposed.
- a crosslinking reaction may advance too much and heat fusibility may fall.
- the manufacturing of the exterior body 11 includes a step of laminating the outer layer 17 on one surface of the base material 15.
- This lamination can be performed by a known method such as lamination.
- the lamination of the outer layer may be performed before the irradiation step or after the irradiation step.
- the tab lead 22 as the second embodiment shown in FIG. 3 includes a base material 28, a resin layer 29 laminated on the base material 28, and a coating layer 30 laminated on the resin layer 29.
- the base material 28 is the same as the base material 18 in the tab leads 12, 12 ′ of the secondary battery 10 of FIG.
- the resin layer 29 and the coating layer 30 are laminated on the base material 28 in this order. That is, the coating layer 30 is laminated on the surface of the resin layer 29 opposite to the base 28.
- the tab lead 22 is different from the tab leads 12 and 12 ′ in FIG. 2 in that a coating layer 30 is further laminated on the resin layer 29.
- the resin layer 29 is directly laminated on the base material 28.
- the resin layer 29 is a layer containing a cross-linked fluororesin, and the resin layer 19 of the tab leads 12 and 12 ′ in FIG. 2 can be employed as it is.
- the covering layer 30 is directly laminated on the outer surface of the resin layer 29.
- the covering layer 30 includes a fluororesin.
- the fluororesin contained in the coating layer 30 is a non-crosslinked fluororesin or a fluororesin having a lower melting point than the crosslinked fluororesin in the resin layer 29.
- An example of the fluororesin having a lower melting point than that of the cross-linked fluororesin is a fluororesin that has not been cross-linked.
- Specific examples include FEP, PFA, PTFE, TFE / PDD and the like that are not crosslinked, that is, substantially not having a crosslinked structure. FEP and PFA are preferable, and FEP is more preferable.
- fusing point of these fluororesins 250 to 350 degreeC is preferable, for example.
- the fluororesin in coating layer 30 As a minimum of content of the fluororesin in coating layer 30, 50 mass% is preferred, 70 mass% is more preferred, 90 mass% is still more preferred, and 99 mass% is especially preferred.
- the content of the fluororesin in the coating layer 30 may be 100% by mass.
- the covering layer 30 can be laminated, for example, by laminating a film or sheet containing a non-crosslinked fluororesin or a fluororesin having a melting point lower than that of the crosslinked fluororesin on the resin layer 29.
- the coating layer 30 of the tab lead 22 is easily softened or melted by heat as compared with the resin layer 29 containing a cross-linked fluororesin, and also has good heat-fusibility to the fluororesin layer. Have. That is, the coating layer 30 functions as a good heat fusion layer. Therefore, for example, when the tab lead 22 is used in place of the tab lead 12 in the secondary battery 10 of FIG. 2, the thermal fusion between the tab lead 22 and the outer package 11 can be further improved. Moreover, since the coating layer 30 is a layer containing a fluororesin, good chemical resistance, flame retardancy, heat resistance, and the like are ensured.
- Secondary Battery 40> A secondary battery 40 according to the third embodiment shown in FIG.
- the secondary battery 40 has a heat-sealing film 41 interposed between the outer package 11 and the tab lead 12.
- the secondary battery 40 is the same as the secondary battery 10 of FIGS. 1 and 2 described above except that it has a heat-sealing film 41. Therefore, except for the heat-sealing film 41, the same reference numerals as those of the secondary battery 10 are given and the description thereof is omitted.
- the heat sealing film 41 includes a non-crosslinked fluororesin or a fluororesin having a melting point lower than that of the crosslinked fluororesin contained in the resin layers 16 and 19.
- a fluororesin film can be adopted.
- the fluororesin having a melting point lower than that of the cross-linked fluororesin include non-crosslinked fluororesins exemplified as the fluororesin included in the coating layer 30 of the tab lead 22 of the second embodiment.
- the heat-sealing film 41 is easily softened against heat, and also has good heat-sealing properties with respect to these resin layers 16 and 19. Have Therefore, according to the secondary battery 40, the heat-fusibility between the tab lead 12 and the outer package 11 can be further improved. Moreover, since the heat sealing
- the secondary battery has been described as an example of the power storage device, but the present invention can also be adopted in power storage devices other than the secondary battery.
- Examples of such an electricity storage device include an electric double layer capacitor.
- both the outer package and the tab lead are configured to be the members for the electricity storage device of the present invention, but one of the outer package and the tab lead may be a conventional one. That is, the resin layer in one of the outer package and the tab lead may not contain a cross-linked fluororesin.
- the resin layer can be formed from a known thermoplastic resin such as an uncrosslinked fluororesin, polyolefin, polyphenylene sulfide, or polyether ether ketone. Moreover, it is good also as a structure which laminated
- the member for an electricity storage device of the present invention may have a layer other than the base material, the resin layer, and the coating layer.
- the electricity storage device member of the present invention is not limited to the outer package and the tab lead.
- the member for an electricity storage device of the present invention can be employed for packing of an electricity storage device.
- Example 1 An aluminum foil (A1085, thickness 50 ⁇ m) was prepared as a substrate. The ten-point average roughness (Rz) of the substrate surface was 1 ⁇ m. FEP was applied to this base material with an average film thickness of 50 ⁇ m. Next, in a nitrogen atmosphere at 300 ° C. and an oxygen concentration of 10 ppm or less, the FEP on the substrate was irradiated with ionizing radiation at 300 kGy to crosslink the FEP.
- Rz ten-point average roughness
- Example 1 a non-crosslinked FEP film having an average film thickness of 12 ⁇ m was laminated on the surface of the crosslinked FEP layer. This lamination was performed by heat fusion at a temperature of 280 ° C., a pressure of 10 MPa, and a holding time of 30 minutes. Thus, a member of Example 1 having a structure of base material (aluminum) / resin layer (crosslinked FEP) / covering layer (non-crosslinked FEP) was obtained. In addition, the said resin layer was produced separately by the single layer for evaluation. The same applies to other examples and comparative examples.
- Example 2 The member of Example 2 in the same manner as in Example 1 except that the resin layer was a layer containing glass cloth (IPC standard style # 1015, average thickness of 15 ⁇ m) in the center of the FEP having an average film thickness of 50 ⁇ m. Got. That is, the resin layer of Example 2 is a layer in which glass cloth is impregnated with FEP.
- Example 3 A member of Example 3 was obtained in the same manner as in Example 1 except that the coating layer (non-crosslinked FEP) was not laminated.
- Example 3 with the exception of using a copper plate (C1020, thickness 500 ⁇ m) with a 10-point average roughness (Rz) of the surface as the substrate and cross-linking PFA instead of FEP as the resin layer Similarly, a member of Example 4 was obtained.
- Example 3 with the exception of using an aluminum plate (A1050, thickness 500 ⁇ m) with a 10-point average roughness (Rz) of the surface as the substrate and cross-linking PTFE instead of FEP as the resin layer Similarly, the member of Example 5 was obtained.
- Example 6 is the same as Example 3 except that a nickel foil (rolled foil, nickel 99.9%, thickness 20 ⁇ m) having a 10-point average roughness (Rz) of the surface of 1 ⁇ m was used as the substrate. A member was obtained.
- ⁇ Comparative Example 1> The same procedure as in Example 1 was performed except that ionizing radiation was not applied to the FEP on the substrate. A member in which the resin layer and the substrate were integrated could not be obtained.
- ⁇ Comparative example 2> A polypropylene resin layer was laminated on the base material used in Example 1 using maleic anhydride-modified polypropylene as an adhesive to obtain a member of Comparative Example 2.
- the peel strength of the member after heat fusion was measured at a peel speed of 50 mm / min. The measurement results are shown in Table 1. Table 1 also shows the fused counterpart member. In addition, about Example 3, since heat fusion did not occur in 10 seconds, it was heat-sealed by weighting for 3 minutes. However, since the fusion time was too long, part of the surface was thermally deformed. (Heat-resistant) Further, as an evaluation of heat resistance, the member after heat fusion was left at a high temperature of 150 ° C. for 30 minutes to evaluate the presence or absence of peeling. The case where peeling did not occur was designated as A, and the case where peeling occurred was designated as B. These evaluation results are shown in Table 1.
- the electricity storage device member of the present invention can be suitably used as a tab lead or an exterior body of an electricity storage device such as a secondary battery or a capacitor.
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Abstract
Description
上記樹脂層には、熱融着性や上述した基材との密着性の他、電解液に対する耐久性、すなわち耐薬品性や、耐熱性、難燃性、強度などが要求される。耐薬品性や耐熱性が不十分である場合、熱融着した界面や基材と樹脂層との界面などから電解液の漏出が生じやすくなるといった不都合がある。特に、電気自動車用の蓄電デバイスを初めとして、蓄電デバイスの大電流化及び高電圧化が進んでいることなどから、耐熱性等に係る要求は高まってきている。
[本開示の効果]
本発明は、良好な耐熱性及び難燃性を有する樹脂層を備える蓄電デバイス用部材、このような蓄電デバイス用部材の製造方法、並びにこのような蓄電デバイス用部材を備える蓄電デバイスを提供することができる。
[本発明の実施形態の説明]
本発明の一態様に係る蓄電デバイス用部材は、金属を主成分とする基材、及びこの基材に積層される樹脂層を備える蓄電デバイス用部材であって、上記樹脂層が、架橋されたフッ素樹脂を含む。本明細書において「架橋された」とは、三次元架橋構造が形成されていることを示す。
[本発明の実施形態の詳細]
<第1実施形態:二次電池10>
以下、本発明の蓄電デバイスの第1実施形態としての二次電池について、適宜図面を参照しつつ詳説する。また、この二次電池に備わる、本発明の蓄電デバイス用部材の一実施形態としての外装体及びタブリードについてもあわせて説明する。
(外装体11)
本発明の蓄電デバイス用部材の一実施形態である外装体11は、図2に示すように、基材15と、この基材15の内面側に積層される樹脂層16と、基材15の外面側に積層される外層17とを備える。すなわち、外装体11は、樹脂層16、基材15及び外層17がこの順に積層されてなる積層フィルムである。また、外装体11は、上述のように、正極、負極、セパレータ及び電解液を密封状態で収容する容器である。
(タブリード12、12’)
本発明の蓄電デバイス用部材の一実施形態であるタブリード12、12’は、図2に示すように、基材18と、この基材18に積層される樹脂層19を備える。
(利点)
当該二次電池10においては、外装体11の樹脂層16及びタブリード12、12’の樹脂層19が、架橋されたフッ素樹脂を含むため、これらの樹脂層の耐熱性、難燃性及び耐薬品性が良好である。また、これらの樹脂層は、基材との高い密着性を有する。さらに、熱融着する樹脂層16及び樹脂層19が、共にフッ素樹脂を含む、すなわち同種の樹脂を含むことからも、熱融着性に優れる。従って、当該外装体11及びタブリード12、12’を備える二次電池10は、厳しい環境下においても液漏れの発生が抑制され、安全性に優れる。当該外装体11及びタブリード12、12’を備える二次電池10は、従来の蓄電デバイスと同様の用途に使用することができるが、特に、大電流及び高電圧で使用される用途、例えば電気自動車用の蓄電デバイスとして好適に用いることができる。
<蓄電デバイス用部材(外装体11及びタブリード12、12’)の製造方法>
本発明の一実施形態に係る蓄電デバイス用部材の製造方法は、
金属を主成分とする基材にフッ素樹脂を含む層を積層する工程、及び
上記フッ素樹脂を含む層に電離放射線を照射する工程
を備える。
(積層工程)
積層工程は、基材にフッ素樹脂を含む層を積層する工程である。この積層は、例えば実質的に未架橋のフッ素樹脂を含む層を溶融押出成形しつつ基材表面に積層する方法、基材と実質的に未架橋のフッ素樹脂を含む層とをラミネートする方法等によって行うことができる。また、粉状のフッ素樹脂を用いた粉体塗装によってフッ素樹脂を含む層を積層することもできる。
(照射工程)
照射工程は、基材とフッ素樹脂を含む層との積層体に対し、フッ素樹脂を含む層の表面側から電離放射線を照射することで行われる。外装体11のように樹脂層が片面にのみ形成される場合は、一方の面側からのみ電離放射線を照射すればよい。タブリード12のように全周に樹脂層が形成される場合は、全周に電離放射線を照射する。
<第2実施形態:蓄電デバイス用部材(タブリード22)>
図3に示す第2実施形態としてのタブリード22は、基材28と、この基材28に積層される樹脂層29と、樹脂層29に積層される被覆層30とを備える。基材28は、図2の二次電池10のタブリード12、12’における基材18と同様である。
<第3実施形態:二次電池40>
図4に示す第3実施形態としての二次電池40は、外装体11とタブリード12との間に介在する熱融着フィルム41を有する。この二次電池40は、熱融着フィルム41を有すること以外は、上述した図1、2の二次電池10と同様である。従って、熱融着フィルム41以外は、二次電池10と同一番号を付して説明を省略する。
<その他の実施形態>
今回開示された実施の形態は全ての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記実施形態の構成に限定されるものではなく、特許請求の範囲によって示され、請求の範囲と均等の意味及び範囲内での全ての変更が含まれることが意図される。
<実施例1>
基材として、アルミニウム箔(A1085、厚さ50μm)を用意した。この基材表面の十点平均粗さ(Rz)は、1μmであった。この基材に、FEPを平均膜厚50μmで塗工した。次いで、300℃、酸素濃度10ppm以下の窒素雰囲気下において、上記基材上のFEPに対して300kGyで電離放射線照射し、FEPを架橋させた。次いで、架橋したFEPの層の表面に、平均膜厚12μmの非架橋のFEP膜を積層させた。この積層は、温度280℃、圧力10MPa、保持時間30分での熱融着により行った。これにより、基材(アルミニウム)/樹脂層(架橋FEP)/被覆層(非架橋FEP)の構造を有する実施例1の部材を得た。なお、評価のために、別途上記樹脂層を単層で作製した。他の実施例及び比較例も同様である。
<実施例2>
樹脂層を、平均膜厚50μmのFEPの中央部にガラスクロス(IPC規格スタイル#1015、平均厚み15μm)を含有させた層としたこと以外は、実施例1と同様にして実施例2の部材を得た。すなわち、この実施例2の樹脂層は、ガラスクロスにFEPが含浸した層である。
<実施例3>
被覆層(非架橋FEP)を積層しなかったこと以外は実施例1と同様にして実施例3の部材を得た。
<実施例4>
基材として表面の十点平均粗さ(Rz)が3μmの銅板(C1020、厚さ500μm)を用いたこと、及び樹脂層としてFEPの代わりにPFAを架橋させたこと以外は、実施例3と同様にして実施例4の部材を得た。
<実施例5>
基材として表面の十点平均粗さ(Rz)が2μmのアルミニウム板(A1050、厚さ500μm)を用いたこと、及び樹脂層としてFEPの代わりにPTFEを架橋させたこと以外は実施例3と同様にして、実施例5の部材を得た。
<実施例6>
基材として表面の十点平均粗さ(Rz)が1μmのニッケル箔(圧延箔、ニッケル99.9%、厚さ20μm)を用いたこと以外は実施例3と同様にして、実施例6の部材を得た。
<比較例1>
基材上のFEPに対して電離放射線照射を行わなかったこと以外は実施例1と同様にした。樹脂層と基材とが一体化した部材を得ることができなかった。
<比較例2>
実施例1で用いた基材に対して、接着剤として無水マレイン酸変性ポリプロピレンを用いてポリプロピレンの樹脂層を積層し、比較例2の部材を得た。
[評価]
(線膨張率、引張破断強さ及び難燃性)
得られた各実施例及び比較例における樹脂層について、線膨張率及び引張破断強さを測定した。これらの測定結果、及び樹脂層に用いた樹脂のUL94規格の難燃レベルを表1に示す。
(剥離強度)
得られた部材の最表層同士を重ね合わせ320℃、1kgfで10秒間加重することにより、熱融着させた。なお、最表層とは、非架橋FEP等の被覆層が積層されているものは被覆層を指し、被覆層が積層されていないものについては架橋FEP等の樹脂層を指す。熱融着後の部材について、剥離速度50mm/minで剥離強度を測定した。測定結果を表1に示す。また、表1には、融着させた相手部材をあわせて示す。なお、実施例3については、10秒では熱融着が生じなかったため、3分間加重することにより熱融着させた。但し、融着時間が長すぎたため、表面の一部が熱変形した。
(耐熱性)
また、耐熱性の評価として、熱融着後の部材を150℃の高温下に30分放置し、剥離の有無を評価した。剥離が生じなかったものをA、剥離が生じたものをBとした。これらの評価結果を表1に示す。
Claims (13)
- 金属を主成分とする基材、及びこの基材に積層される樹脂層を備える蓄電デバイス用部材であって、
上記樹脂層が、架橋されたフッ素樹脂を含む蓄電デバイス用部材。 - 上記フッ素樹脂と上記基材の表面との間に化学結合を有している請求項1に記載の蓄電デバイス用部材。
- 上記樹脂層が、熱融着層である請求項1又は請求項2に記載の蓄電デバイス用部材。
- 上記樹脂層が、クロス又はフィラーを含有し、
上記樹脂層の線膨張率が、1×10-7/K以上40×10-6/K以下である請求項1、請求項2又は請求項3に記載の蓄電デバイス用部材。 - 上記樹脂層の上記基材とは反対の面側に積層され、フッ素樹脂を含む被覆層をさらに備え、
上記被覆層に含まれるフッ素樹脂が、非架橋フッ素樹脂、又は上記架橋されたフッ素樹脂よりも融点の低いフッ素樹脂である請求項1から請求項4のいずれか1項に記載の蓄電デバイス用部材。 - 上記架橋されたフッ素樹脂が、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体である請求項1から請求項5のいずれか1項に記載の蓄電デバイス用部材。
- 上記被覆層に含まれるフッ素樹脂が、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体である請求項5に記載の蓄電デバイス用部材。
- 上記樹脂層と上記基材との剥離強度が、0.1N/cm以上100N/cm以下である請求項1から請求項7のいずれか1項に記載の蓄電デバイス用部材。
- 上記樹脂層が積層されている領域における上記基材の表面の十点平均粗さ(RZ)が、0.001μm以上10μm以下である請求項1から請求項8のいずれか1項に記載の蓄電デバイス用部材。
- タブリード又は外装体である請求項1から請求項9のいずれか1項に記載の蓄電デバイス用部材。
- 金属を主成分とする基材にフッ素樹脂を含む層を積層する工程、及び
上記フッ素樹脂を含む層に電離放射線を照射する工程
を備える蓄電デバイス用部材の製造方法。 - 正極と、
負極と、
電解液と、
上記正極、上記負極、及び上記電解液を収納する外装体と、
一端が上記外装体から露出し、他端が上記正極又は負極と接続されているタブリードと を備え、
上記外装体とタブリードとが熱融着されている蓄電デバイスであって、
上記外装体及びタブリードの少なくとも一方が、請求項1から請求項9のいずれか1項に記載の蓄電デバイス用部材である蓄電デバイス。 - 上記外装体とタブリードとの間に介在する熱融着フィルムをさらに備え、
上記熱融着フィルムが、非架橋フッ素樹脂、又は架橋されたフッ素樹脂よりも融点の低いフッ素樹脂を含む請求項12に記載の蓄電デバイス。
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Also Published As
Publication number | Publication date |
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JP7101338B2 (ja) | 2022-07-15 |
EP3633756A1 (en) | 2020-04-08 |
US20200119317A1 (en) | 2020-04-16 |
CN110678998A (zh) | 2020-01-10 |
JPWO2018220954A1 (ja) | 2020-04-23 |
EP3633756A4 (en) | 2021-02-24 |
CN110678998B (zh) | 2022-06-17 |
US11552356B2 (en) | 2023-01-10 |
KR20200015899A (ko) | 2020-02-13 |
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