WO2018066645A1 - Cell exterior member laminate sheet - Google Patents

Cell exterior member laminate sheet Download PDF

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Publication number
WO2018066645A1
WO2018066645A1 PCT/JP2017/036269 JP2017036269W WO2018066645A1 WO 2018066645 A1 WO2018066645 A1 WO 2018066645A1 JP 2017036269 W JP2017036269 W JP 2017036269W WO 2018066645 A1 WO2018066645 A1 WO 2018066645A1
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WIPO (PCT)
Prior art keywords
silicone rubber
cell
rubber layer
metal foil
layer
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PCT/JP2017/036269
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French (fr)
Japanese (ja)
Inventor
萩乃 藤田
充由 斉藤
Original Assignee
東洋製罐グループホールディングス株式会社
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Publication of WO2018066645A1 publication Critical patent/WO2018066645A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/68—Containers, packaging elements or packages, specially adapted for particular articles or materials for machines, engines or vehicles in assembled or dismantled form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/08—Housing; Encapsulation
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a laminated sheet used as a cell outer package of an electric device such as a battery (for example, a lithium ion battery), a capacitor, and an electric double layer capacitor, and more specifically, heat resistance, flame resistance, and cold resistance.
  • the present invention relates to a laminated sheet capable of providing a cell outer package having a property, chemical resistance (electrolytic resistance), gas permeation resistance (gas barrier property), and the like.
  • the electrical device as described above is configured by hermetically housing a cell in which an electrolyte is sandwiched between a pair of electrode substrates (a positive electrode and a negative electrode) in an exterior body, and is hermetically accommodated in the exterior body. And one or a plurality of such cells.
  • lithium ion batteries (lithium ion secondary batteries) are widely used as batteries for mobile phones, smartphones, laptop computers, etc. because of their high energy density, high voltage easily, high capacity and long life. Yes. Lithium ion batteries are also used as batteries for auxiliary power units (APUs) that supply compressed air, hydraulic pressure, and electric power to various parts of an aircraft. And the exterior body in which the cell which forms the lithium ion battery mentioned above is hermetically stored is required to have heat resistance, flame retardancy, cold resistance, chemical resistance, gas permeability resistance, and the like.
  • Patent Document 1 discloses a cell body formed of a laminate including a base material layer, an adhesive layer (chemical conversion treatment layer), aluminum, a chemical conversion treatment layer, an adhesive layer, and a heat seal layer.
  • a base material layer a material that can be bonded to the heat seal layer.
  • Patent Document 2 discloses a cell outer package that is formed by sequentially laminating a base material layer, a metal foil layer subjected to chemical conversion treatment on the surface, an acid-modified polyolefin layer, and a thermal adhesive resin layer. Proposed.
  • the acid-modified polyolefin layer has a melting point of 145 ° C. to 165 ° C.
  • the heat-adhesive resin layer is made of polypropylene.
  • an object of the present invention is to provide a laminated sheet capable of forming a cell outer package having excellent heat resistance, flame resistance, cold resistance, chemical resistance, gas permeability resistance, and the like.
  • the present invention has a metal foil and a silicone rubber layer laminated on one surface of the metal foil, and the silicone rubber layer is used as an inner surface.
  • a laminated sheet is provided.
  • the silicone rubber layer is laminated on the surface of the metal foil with a silicone paint, (2)
  • the silicone rubber layer has a thickness of 20 ⁇ m or more, (3) the silicone rubber layer has a thickness of 50 to 200 ⁇ m; Is preferred.
  • an electrical device in which a cell having a structure in which the laminated sheet is used as an outer package and an electrolyte is sandwiched between a pair of electrode substrates inside the outer package.
  • a plurality of the cells are hermetically sealed; (5) the electrical device is a battery, in particular a lithium ion battery, Is preferred.
  • the metal foil and the silicone rubber layer are laminated and the silicone rubber layer is used as the inner surface, so that it has excellent heat resistance, flame resistance, cold resistance, chemical resistance And has high mechanical strength, and can be suitably used as a cell outer package of various electric devices, particularly as a cell outer package of a lithium ion battery.
  • the schematic front view which shows the electric device provided with the cell sealed and accommodated in the exterior body.
  • the schematic sectional drawing which shows the laminated structure of the laminated sheet for cell exterior bodies of this invention.
  • the figure which shows the process which seals and accommodates a cell in the lamination sheet of this invention to make an electrical device.
  • this electric device P is, for example, a lithium ion battery, and a cell 2 is accommodated in an exterior body 1 and is sealed at a peripheral edge portion (seal portion) 3 for use.
  • the cell 2 has a structure in which an electrolyte is filled and sandwiched between a pair of electrodes (a positive electrode and a negative electrode), and a tab 2a serving as an electrode terminal is formed from the electrode. , 2b protrudes.
  • the electric device P is a lithium ion battery, characteristics such as heat resistance, flame retardancy, cold resistance, chemical resistance, and gas permeability resistance are required as described above.
  • the exterior body 1 is formed using the laminated sheet S shown in FIG. 2, and includes a metal foil 4 such as an aluminum foil and a silicone rubber layer 5 provided on one surface of the metal foil 4.
  • a metal foil 4 such as an aluminum foil
  • a silicone rubber layer 5 provided on one surface of the metal foil 4.
  • the silicone rubber layer 5 becomes the inner surface and faces the cell 2.
  • the silicone rubber layer 5 is laminated by thermally bonding a silicone rubber sheet 7 to the metal foil 4 through a silicone paint layer 6.
  • the above metal foil 4 naturally has gas permeation resistance and the like.
  • the silicone rubber layer 5 can be used in a temperature range of ⁇ 55 ° C. to 300 ° C., for example, and is excellent in heat resistance, flame retardancy, cold resistance, chemical resistance, and the like as compared with an olefin resin.
  • the exterior body 1 formed from the above laminated sheet S is, as the exterior body 1 of the lithium ion battery P, gas permeation resistance, heat resistance against heat generation, flame resistance against ignition, and cold resistance under low temperature conditions. It becomes possible to have sex.
  • the thickness of the silicone rubber layer 5 in the laminated sheet S is set to 20 ⁇ m or more, preferably 20 to 1000 ⁇ m, more preferably 50 to 200 ⁇ m. That is, by forming the silicone rubber layer 5 as thick as above, the above-described excellent heat resistance, flame retardancy, cold resistance, chemical resistance, and the like can be more effectively exhibited. For example, when the thickness of the silicone rubber layer 5 is thinner than the above thickness, the effects brought about by the heat resistance, flame retardancy, cold resistance, chemical resistance, etc. of the silicone rubber layer 5 are reduced. On the other hand, when the thickness of the silicone rubber layer 5 is increased, no particular effect is produced, which is disadvantageous in terms of cost.
  • a silicone rubber having good heat resistance, flame retardancy, cold resistance, chemical resistance and the like is a cured product of polyalkylsiloxane, which is a silicone polymer having a dense structure in which branching is introduced into the SiO chain.
  • polyalkylsiloxane which is a silicone polymer having a dense structure in which branching is introduced into the SiO chain.
  • the adhesiveness to the metal foil 4 is low, and it is not easy to increase the thickness of such a silicone rubber layer.
  • a silicone rubber sheet is laminated on an aluminum foil, it is necessary to set the thickness of the silicone rubber sheet to be quite thin.
  • the silicone rubber layer 5 of the thickness mentioned above on the metal foil 4 contains many vinyl groups and a crosslinking agent (For example, the polyfunctional silane compound etc. which contain a hydroxyl group as a functional group) Is applied to the metal foil 4 and appropriately heated and crosslinked to form a thin silicone coating layer 6, and then the crosslinked silicone coating layer 6 is coated with A metal foil is obtained by pressing a thick silicone rubber sheet 7 made of an uncrosslinked pasty silicone rubber containing a large amount of vinyl groups and sequentially mixing a retarder and a crosslinker, and integrating with the silicone paint layer 6. A silicone rubber layer 5 firmly adhered and laminated to 4 can be formed.
  • a crosslinking agent for example, the polyfunctional silane compound etc. which contain a hydroxyl group as a functional group
  • the thickness of the silicone paint applied on the metal foil 4 is generally about 0.05 to 2.0 ⁇ m in dry film thickness, and the thickness of the silicone rubber layer 5 obtained by cross-linking and integrating the silicone rubber sheet 7 thereon. Is set to be in the above-described range.
  • the silicone paint layer 6 is integrated with the silicone rubber sheet 7, the thickness of the silicone paint layer 6 in a state where the silicone rubber layer 5 is formed cannot be calculated.
  • the presence of the silicone paint layer 6 can be grasped. That is, when the carbon atom concentration in the silicone rubber layer 5 is measured by XPS, the carbon atom concentration in the vicinity of the interface on the metal foil 4 side is considerably higher than the measurement value in the vicinity of the surface on the opposite side. It can be recognized that the silicone rubber layer 7 is laminated on the metal foil 4 by the silicone paint layer 6.
  • the high carbon atom concentration in the vicinity of the interface on the metal foil 4 side means that the silicone rubber layer 5 is rich in flexibility in the vicinity of the interface with the metal foil 4 and follows the metal foil 4. This indicates that the metal foil 4 is firmly attached to the metal foil 4.
  • the laminated sheet S of the present invention in which the thick silicone rubber layer 5 is formed on the metal foil 4 is excellent in heat resistance, flame retardancy, cold resistance, chemical resistance, gas permeability resistance, and the like.
  • the cell 2 is preferably used as a cell outer package in which the cells 2 are hermetically accommodated, particularly as an outer package of an electric device such as a lithium ion battery.
  • FIG. 3 shows a process of manufacturing various electric devices P by sealing the cells 2 in the outer package 1 made of the laminated sheet S of the present invention.
  • a unit of a predetermined electrical device is placed on the silicone rubber layer 5 (omitted in FIG. 3) of the laminated sheet S of the present invention.
  • a suitable number of cells 2 are placed (FIG. 3a).
  • the laminated sheet S is overlaid and covered so that the silicone rubber layer 5 faces, and in this state, the two laminated sheets S that are overlaid are bonded together, whereby the cell 2 is hermetically accommodated. An electrical device can be obtained.
  • the adhesion of the two laminated sheets S is usually performed by adhering the peripheral edge portions 3 of the individual cells 2, whereby the peripheral edge portions 3 of the respective cells 2 are held in a sealed state.
  • Adhesion at the peripheral edge 3 of the cell 2 was performed by previously forming the silicone paint layer 6 on the portion to be the peripheral edge 3 of the silicone rubber layer 5 of each laminated sheet S using the above-described silicone paint. This can be done by pressing and laminating the two laminated sheets S.
  • the metal foil 4 can also be heated by high frequency induction heating to a temperature at which the performance degradation of the cell 2 does not occur.
  • the peripheral edge 3 of the cell 2 is selectively heated by forming a cut line that does not deteriorate the barrier performance in the metal foil 4 and performing high frequency induction heating, for example, preventing heating of the electrode substrate or the like. can do.
  • a laminated sheet facing each other by performing an aging treatment that is heated to a temperature that does not cause degradation in the performance of the cell 2 if necessary. It is preferable that the silicone rubber layers 5 of S are cross-linked and firmly bonded. Further, instead of such an aging treatment, it is also possible to firmly bond the silicone rubber layers 5 to each other by UV irradiation and UV crosslinking.
  • the cells 2 can be hermetically accommodated while avoiding direct heating of the cells 2 as much as possible.
  • An electrical device configured by sealingly storing cells as described above is preferably used as, for example, a battery, particularly a lithium ion battery.
  • a battery particularly a lithium ion battery.
  • the specification of the cell 2 can be changed as appropriate to use it as a capacitor, an electric double layer capacitor, or the like.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Mechanical Engineering (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Packaging Of Machine Parts And Wound Products (AREA)

Abstract

A cell exterior member laminate sheet comprises a metal foil, and a silicone rubber layer laminated on one surface of the metal foil, characterized in that the silicone rubber layer is used as an inner surface.

Description

セル外装体用積層シートLaminated sheet for cell exterior body
　本発明は、電池（例えばリチウムイオン電池）、キャパシタ、電気二重層キャパシタ等の電気デバイスのセル外装体として使用される積層シートに関するものであり、より詳細には、耐熱性、難燃性、耐寒性、耐薬品性（耐電解性）、耐ガス透過性（ガスバリヤー性）等を有するセル外装体を提供できる積層シートに関する。
　上記のような電気デバイスは、一対の電極基板（正極及び負極）の間に電解質が挟持されているセルを外装体に密封収容することにより構成されており、外装体に密封収容されているセルを一単位とし、このようなセルを一または複数個を備えている。 The present invention relates to a laminated sheet used as a cell outer package of an electric device such as a battery (for example, a lithium ion battery), a capacitor, and an electric double layer capacitor, and more specifically, heat resistance, flame resistance, and cold resistance. The present invention relates to a laminated sheet capable of providing a cell outer package having a property, chemical resistance (electrolytic resistance), gas permeation resistance (gas barrier property), and the like.
The electrical device as described above is configured by hermetically housing a cell in which an electrolyte is sandwiched between a pair of electrode substrates (a positive electrode and a negative electrode) in an exterior body, and is hermetically accommodated in the exterior body. And one or a plurality of such cells.
　近年、リチウムイオン電池（リチウムイオン二次電池）はエネルギー密度が高く、容易に高電圧が得られ、大容量、長寿命であるため、携帯電話やスマートフォン、ノートパソコン等のバッテリーとして広く使用されている。また、リチウムイオン電池は、航空機の各部に圧縮空気や油圧、電力を供給する補助動力装置（ＡＰＵ）用のバッテリーとしても使用されている。
　そして、前述したリチウムイオン電池を形成するセルが密封収納される外装体には、耐熱性、難燃性、耐寒性、耐薬品性、耐ガス透過性等が要求される。 In recent years, lithium ion batteries (lithium ion secondary batteries) are widely used as batteries for mobile phones, smartphones, laptop computers, etc. because of their high energy density, high voltage easily, high capacity and long life. Yes. Lithium ion batteries are also used as batteries for auxiliary power units (APUs) that supply compressed air, hydraulic pressure, and electric power to various parts of an aircraft.
And the exterior body in which the cell which forms the lithium ion battery mentioned above is hermetically stored is required to have heat resistance, flame retardancy, cold resistance, chemical resistance, gas permeability resistance, and the like.
　前述したリチウムイオン電池のセル外装体として、特許文献１には、基材層、接着層（化成処理層）、アルミニウム、化成処理層、接着層、ヒートシール層からなる積層体により形成されたものが提案されている。この外装体では、複数のセルの周縁部が、それぞれヒートシールにより密封される。従って、上記積層体の基材層は、ヒートシール層と接着できる材質のものから形成されている。 As the above-described cell exterior body of a lithium ion battery, Patent Document 1 discloses a cell body formed of a laminate including a base material layer, an adhesive layer (chemical conversion treatment layer), aluminum, a chemical conversion treatment layer, an adhesive layer, and a heat seal layer. Has been proposed. In this exterior body, the peripheral parts of the plurality of cells are sealed by heat sealing. Therefore, the base material layer of the laminate is formed of a material that can be bonded to the heat seal layer.
　また、特許文献２には、基材層と、表面に化成処理が施された金属箔層と、酸変性ポリオレフィン層と、熱接着性樹脂層とを順次積層して構成されたセル外装体が提案されている。かかる外装体では、酸変性ポリオレフィン層が、１４５℃～１６５℃の融点を有するものであり、熱接着性樹脂層が、ポリプロピレンにより形成されている。 Patent Document 2 discloses a cell outer package that is formed by sequentially laminating a base material layer, a metal foil layer subjected to chemical conversion treatment on the surface, an acid-modified polyolefin layer, and a thermal adhesive resin layer. Proposed. In such an outer package, the acid-modified polyolefin layer has a melting point of 145 ° C. to 165 ° C., and the heat-adhesive resin layer is made of polypropylene.
特開２００３－２４２９４２号JP 2003-242942 A 特開２０１０－０８６７４４号JP 2010-086744 A
　しかしながら、特許文献１及び２のセル外装体では、耐熱性が低いオレフィン樹脂が用いられており、リチウムイオン電池の外装体に要求される発熱に対する耐熱性（断熱性）や発火に対する難燃性が不十分である。
　また、前述した航空機の補助動力装置（ＡＰＵ）用のリチウムイオン電池の外装体では、低温環境下（上空等）での振動等に耐え得る強度が要求され、さらには、耐寒性も備えていなければならない。 However, in the cell exterior bodies of Patent Documents 1 and 2, an olefin resin having low heat resistance is used, and heat resistance (heat insulation) against heat generation required for the exterior body of a lithium ion battery and flame resistance against ignition are exhibited. It is insufficient.
In addition, the above-described outer package of a lithium ion battery for an aircraft auxiliary power unit (APU) is required to have a strength that can withstand vibrations in a low-temperature environment (such as the sky), and must also have cold resistance. I must.
　従って、本発明の目的は、優れた耐熱性、難燃性、耐寒性、耐薬品性、耐ガス透過性等を有するセル外装体を形成し得る積層シートを提供することにある。 Therefore, an object of the present invention is to provide a laminated sheet capable of forming a cell outer package having excellent heat resistance, flame resistance, cold resistance, chemical resistance, gas permeability resistance, and the like.
　本発明によれば、金属箔と、前記金属箔の一方の面に積層されたシリコーンゴム層とを有しており、前記シリコーンゴム層を内面として使用されることを特徴とするセル外装体用積層シートが提供される。 According to the present invention, it has a metal foil and a silicone rubber layer laminated on one surface of the metal foil, and the silicone rubber layer is used as an inner surface. A laminated sheet is provided.
　本発明のセル外装体用堰シートにおいては、
（１）前記シリコーンゴム層が、シリコーン塗料により前記金属箔の表面に積層されていること、
（２）前記シリコーンゴム層は、２０μｍ以上の厚みを有すること、
（３）前記シリコーンゴム層は、５０～２００μｍの厚みを有すること、
が好適である。 In the weir sheet for cell exterior body of the present invention,
(1) The silicone rubber layer is laminated on the surface of the metal foil with a silicone paint,
(2) The silicone rubber layer has a thickness of 20 μm or more,
(3) the silicone rubber layer has a thickness of 50 to 200 μm;
Is preferred.
　本発明によれば、また、上記の積層シートを外装体とし、該外装体の内部に、一対の電極基板の間に電解質が挟持されている構造のセルが、密封収容されている電気デバイスが提供される。
　かかる電気デバイスにおいては、
（４）前記セルが、複数密封収容されていること、
（５）該電気デバイスが電池、特にリチウムイオン電池であること、
が好適である。 According to the present invention, there is also provided an electrical device in which a cell having a structure in which the laminated sheet is used as an outer package and an electrolyte is sandwiched between a pair of electrode substrates inside the outer package. Provided.
In such an electrical device,
(4) a plurality of the cells are hermetically sealed;
(5) the electrical device is a battery, in particular a lithium ion battery,
Is preferred.
　本発明のセル外装体用積層シートでは、金属箔とシリコーンゴム層とが積層されており、且つシリコーンゴム層を内面として使用されるため、優れた耐熱性、難燃性、耐寒性、耐薬品性、耐ガス透過性等を有し、さらには機械的強度も高く、各種の電気デバイスのセル外装体として、特にリチウムイオン電池のセル外装体として好適に用いることができる。 In the laminated sheet for cell outer packaging body of the present invention, the metal foil and the silicone rubber layer are laminated and the silicone rubber layer is used as the inner surface, so that it has excellent heat resistance, flame resistance, cold resistance, chemical resistance And has high mechanical strength, and can be suitably used as a cell outer package of various electric devices, particularly as a cell outer package of a lithium ion battery.
外装体に密封収容されているセルを備えた電気デバイスを示す概略正面図。The schematic front view which shows the electric device provided with the cell sealed and accommodated in the exterior body. 本発明のセル外装体用積層シートの積層構造を示す概略断面図。The schematic sectional drawing which shows the laminated structure of the laminated sheet for cell exterior bodies of this invention. 本発明の積層シートにセルを密封収容して電気デバイスとするプロセスを示す図。The figure which shows the process which seals and accommodates a cell in the lamination sheet of this invention to make an electrical device.
　以下、本発明のセル外装体用積層シートを、添付図面に示す具体例に基づいて説明する。
　図１に示すように、この電気デバイスＰは、例えばリチウムイオン電池であり、外装体１には、セル２が収納され、その周縁部（シール部）３で密封されて使用に供される。
　ところで、セル２は、図示されていないが、一対の電極（正極及び負極）の間に電解質が充填されて挟持されている構造を有するものであり、その電極からは、電極端子となるタブ２ａ，２ｂが突出している。
　この電気デバイスＰがリチウムイオン電池である場合には、前述したように耐熱性、難燃性、耐寒性、耐薬品性、耐ガス透過性等といった特性が求められる。 Hereinafter, the laminated sheet for cell exterior bodies of this invention is demonstrated based on the specific example shown to an accompanying drawing.
As shown in FIG. 1, this electric device P is, for example, a lithium ion battery, and a cell 2 is accommodated in an exterior body 1 and is sealed at a peripheral edge portion (seal portion) 3 for use.
By the way, although not shown, the cell 2 has a structure in which an electrolyte is filled and sandwiched between a pair of electrodes (a positive electrode and a negative electrode), and a tab 2a serving as an electrode terminal is formed from the electrode. , 2b protrudes.
When the electric device P is a lithium ion battery, characteristics such as heat resistance, flame retardancy, cold resistance, chemical resistance, and gas permeability resistance are required as described above.
　上記の外装体１は、図２に示す積層シートＳを用いて形成されるものであり、アルミ箔等の金属箔４と、金属箔４の一方の面に設けられたシリコーンゴム層５とからなり、シリコーンゴム層５が内面となり、セル２に対面するようになっている。
　このシリコーンゴム層５は、シリコーン塗料層６を介してシリコーンゴムシート７を金属箔４に熱接着することにより積層される。 The exterior body 1 is formed using the laminated sheet S shown in FIG. 2, and includes a metal foil 4 such as an aluminum foil and a silicone rubber layer 5 provided on one surface of the metal foil 4. Thus, the silicone rubber layer 5 becomes the inner surface and faces the cell 2.
The silicone rubber layer 5 is laminated by thermally bonding a silicone rubber sheet 7 to the metal foil 4 through a silicone paint layer 6.
　上記の金属箔４は、当然のことながら、耐ガス透過性等を有する。一方、シリコーンゴム層５は、例えば、－５５℃～３００℃の温度域で使用でき、オレフィン系樹脂などと比較して耐熱性、難燃性、耐寒性、耐薬品性等に優れている。このため、上記の積層シートＳから形成される外装体１は、リチウムイオン電池Ｐの外装体１として、耐ガス透過性、発熱に対する耐熱性、発火等に対する難燃性、低温状況下での耐寒性を備えることが可能となる。 The above metal foil 4 naturally has gas permeation resistance and the like. On the other hand, the silicone rubber layer 5 can be used in a temperature range of −55 ° C. to 300 ° C., for example, and is excellent in heat resistance, flame retardancy, cold resistance, chemical resistance, and the like as compared with an olefin resin. For this reason, the exterior body 1 formed from the above laminated sheet S is, as the exterior body 1 of the lithium ion battery P, gas permeation resistance, heat resistance against heat generation, flame resistance against ignition, and cold resistance under low temperature conditions. It becomes possible to have sex.
　本発明において、上記積層シートＳにおけるシリコーンゴム層５の厚みは２０μｍ以上、好ましくは２０～１０００μｍ、より好ましくは５０～２００μｍの範囲に設定するのが好ましい。即ち、シリコーンゴム層５を、このように厚く形成することにより、前述した優れた耐熱性、難燃性、耐寒性、耐薬品性等をより一層、有効に発揮することができる。
　例えば、シリコーンゴム層５の厚みが、前記厚みよりも薄いと、シリコーンゴム層５の耐熱性、難燃性、耐寒性、耐薬品性等によりもたらされる効果が低減してしまう。一方、シリコーンゴム層５の厚みが厚くなると、格別の効果が生じることはなく、コストの点で不利となる。 In the present invention, the thickness of the silicone rubber layer 5 in the laminated sheet S is set to 20 μm or more, preferably 20 to 1000 μm, more preferably 50 to 200 μm. That is, by forming the silicone rubber layer 5 as thick as above, the above-described excellent heat resistance, flame retardancy, cold resistance, chemical resistance, and the like can be more effectively exhibited.
For example, when the thickness of the silicone rubber layer 5 is thinner than the above thickness, the effects brought about by the heat resistance, flame retardancy, cold resistance, chemical resistance, etc. of the silicone rubber layer 5 are reduced. On the other hand, when the thickness of the silicone rubber layer 5 is increased, no particular effect is produced, which is disadvantageous in terms of cost.
　ところで、耐熱性、難燃性、耐寒性、耐薬品性等の良好なシリコーンゴムは、ポリアルキルシロキサンの硬化物であり、ＳｉＯ連鎖に枝分かれが導入されて緻密となった構造を有するシリコーンポリマーからなるものであるが、一般に、金属箔４に対する接着性が低く、このようなシリコーンゴム層の厚みを厚くすることは容易ではない。例えば、通常、アルミ箔にシリコーンゴムシートを積層する場合、シリコーンゴムシートの厚みは、かなり薄く設定しておくことが必要である。 By the way, a silicone rubber having good heat resistance, flame retardancy, cold resistance, chemical resistance and the like is a cured product of polyalkylsiloxane, which is a silicone polymer having a dense structure in which branching is introduced into the SiO chain. In general, however, the adhesiveness to the metal foil 4 is low, and it is not easy to increase the thickness of such a silicone rubber layer. For example, normally, when a silicone rubber sheet is laminated on an aluminum foil, it is necessary to set the thickness of the silicone rubber sheet to be quite thin.
　このため、本発明の積層シートＳでは、上述した厚みのシリコーンゴム層５を金属箔４に積層するため、ビニル基を多く含み、架橋剤（例えば水酸基を官能基として含む多官能シラン化合物など）が混合されているシリコーン塗料（溶剤系塗料）を、金属箔４に塗布し、適宜加熱し、架橋させて薄いシリコーン塗料層６を形成し、この後、この架橋させたシリコーン塗料層６に、ビニル基を多く含み、遅延剤、架橋剤を順次混合した未架橋のペースト状シリコーンゴムから形成された厚みの厚いシリコーンゴムシート７を押圧し、シリコーン塗料層６と一体化することにより、金属箔４にしっかりと密着積層されたシリコーンゴム層５を形成することができる。 For this reason, in the lamination sheet S of this invention, in order to laminate | stack the silicone rubber layer 5 of the thickness mentioned above on the metal foil 4, it contains many vinyl groups and a crosslinking agent (For example, the polyfunctional silane compound etc. which contain a hydroxyl group as a functional group) Is applied to the metal foil 4 and appropriately heated and crosslinked to form a thin silicone coating layer 6, and then the crosslinked silicone coating layer 6 is coated with A metal foil is obtained by pressing a thick silicone rubber sheet 7 made of an uncrosslinked pasty silicone rubber containing a large amount of vinyl groups and sequentially mixing a retarder and a crosslinker, and integrating with the silicone paint layer 6. A silicone rubber layer 5 firmly adhered and laminated to 4 can be formed.
　金属箔４上に塗布するシリコーン塗料の厚みは、一般に、乾燥膜厚で０．０５～２．０μｍ程度とし、この上にシリコーンゴムシート７を架橋して積層一体化したシリコーンゴム層５の厚みが、前述した範囲となるように設定される。 The thickness of the silicone paint applied on the metal foil 4 is generally about 0.05 to 2.0 μm in dry film thickness, and the thickness of the silicone rubber layer 5 obtained by cross-linking and integrating the silicone rubber sheet 7 thereon. Is set to be in the above-described range.
　尚、シリコーン塗料層６は、シリコーンゴムシート７と一体化しているため、シリコーンゴム層５が形成されている状態でのシリコーン塗料層６の厚みを算出することはできないが、ＸＰＳ等により、シリコーンゴム層５の炭素原子の分布状態を測定することにより、シリコーン塗料層６の存在を把握することができる。即ち、シリコーンゴム層５中の炭素原子濃度をＸＰＳにより測定すると、金属箔４側の界面近傍での炭素原子濃度が、反対側の表面近傍での測定値よりもかなり高い値となることから、シリコーン塗料層６によりシリコーンゴムシート７が金属箔４上に積層されたものであることを認識することができる。また、金属箔４側の界面近傍での炭素原子濃度が高いことは、金属箔４との界面近傍部分において、シリコーンゴム層５が可撓性に富んでおり、金属箔４に対しての追随性が高く、金属箔４にしっかりと密着していることを示している。 In addition, since the silicone paint layer 6 is integrated with the silicone rubber sheet 7, the thickness of the silicone paint layer 6 in a state where the silicone rubber layer 5 is formed cannot be calculated. By measuring the carbon atom distribution state of the rubber layer 5, the presence of the silicone paint layer 6 can be grasped. That is, when the carbon atom concentration in the silicone rubber layer 5 is measured by XPS, the carbon atom concentration in the vicinity of the interface on the metal foil 4 side is considerably higher than the measurement value in the vicinity of the surface on the opposite side. It can be recognized that the silicone rubber layer 7 is laminated on the metal foil 4 by the silicone paint layer 6. In addition, the high carbon atom concentration in the vicinity of the interface on the metal foil 4 side means that the silicone rubber layer 5 is rich in flexibility in the vicinity of the interface with the metal foil 4 and follows the metal foil 4. This indicates that the metal foil 4 is firmly attached to the metal foil 4.
　このようにして金属箔４に、厚みの厚いシリコーンゴム層５が形成されている本発明の積層シートＳは、耐熱性、難燃性、耐寒性、耐薬品性、耐ガス透過性等に優れ、セル２が密封収容されたセル外装体として、特にリチウム
イオン電池等の電気デバイスの外装体として好適に使用される。 Thus, the laminated sheet S of the present invention in which the thick silicone rubber layer 5 is formed on the metal foil 4 is excellent in heat resistance, flame retardancy, cold resistance, chemical resistance, gas permeability resistance, and the like. The cell 2 is preferably used as a cell outer package in which the cells 2 are hermetically accommodated, particularly as an outer package of an electric device such as a lithium ion battery.
　図３には、本発明の積層シートＳからなる外装体１にセル２を密封収容させ、各種電気デバイスＰを作製するプロセスが示されている。 FIG. 3 shows a process of manufacturing various electric devices P by sealing the cells 2 in the outer package 1 made of the laminated sheet S of the present invention.
　図３を参照して、セル２を外装体１に収容密封するには、先ず、本発明の積層シートＳのシリコーンゴム層５（図３において省略）上に、所定の電気デバイスの一単位となるセル２を、適宜の数、載置する（図３ａ）。勿論、電気デバイスが一のセル２からなるものであれば、載置されるセル２は一つでよい。
　次いで、その上方から、シリコーンゴム層５が対面するように、積層シートＳを重ね合わせて覆い、この状態で、重ね合わされた２枚の積層シートＳを接着することにより、セル２が密封収容された電気デバイスを得ることができる。 Referring to FIG. 3, in order to accommodate and seal the cell 2 in the outer package 1, first, a unit of a predetermined electrical device is placed on the silicone rubber layer 5 (omitted in FIG. 3) of the laminated sheet S of the present invention. A suitable number of cells 2 are placed (FIG. 3a). Of course, if the electric device is composed of one cell 2, only one cell 2 may be placed.
Next, from above, the laminated sheet S is overlaid and covered so that the silicone rubber layer 5 faces, and in this state, the two laminated sheets S that are overlaid are bonded together, whereby the cell 2 is hermetically accommodated. An electrical device can be obtained.
　２枚の積層シートＳの接着は、通常、個々のセル２の周縁部３を接着することにより行われ、これにより、それぞれのセル２の周縁部３が密封された状態に保持される。 The adhesion of the two laminated sheets S is usually performed by adhering the peripheral edge portions 3 of the individual cells 2, whereby the peripheral edge portions 3 of the respective cells 2 are held in a sealed state.
　セル２の周縁部３での接着は、各積層シートＳのシリコーンゴム層５の周縁部３となる部分に、前述したシリコーン塗料を用いて予めシリコーン塗料層６を形成しておき、重ね合わされた２枚の積層シートＳを押圧して圧着させることにより行うことができる。この際、セル２の性能低下等が生じない程度の温度に、高周波誘導加熱により金属箔４を加熱することもできる。この場合、金属箔４にバリア性能が落ちない程度のカットラインを形成して高周波誘導加熱を実施することにより、セル２の周縁部３を選択的に加熱し、例えば電極基板などの加熱を防止することができる。 Adhesion at the peripheral edge 3 of the cell 2 was performed by previously forming the silicone paint layer 6 on the portion to be the peripheral edge 3 of the silicone rubber layer 5 of each laminated sheet S using the above-described silicone paint. This can be done by pressing and laminating the two laminated sheets S. At this time, the metal foil 4 can also be heated by high frequency induction heating to a temperature at which the performance degradation of the cell 2 does not occur. In this case, the peripheral edge 3 of the cell 2 is selectively heated by forming a cut line that does not deteriorate the barrier performance in the metal foil 4 and performing high frequency induction heating, for example, preventing heating of the electrode substrate or the like. can do.
　さらに、上記のようにセル２の周縁部３を接着して後、必要により、セル２の性能低下等が生じない程度の温度に加熱するエージング処理を行うことにより、互いに対面している積層シートＳのシリコーンゴム層５同士を架橋結合させ、しっかりと接合することが好適である。また、このようなエージング処理の代わりに、紫外線を照射し、ＵＶ架橋によりシリコーンゴム層５同士をしっかりと結合させることもできる。 Furthermore, after bonding the peripheral portion 3 of the cell 2 as described above, a laminated sheet facing each other by performing an aging treatment that is heated to a temperature that does not cause degradation in the performance of the cell 2 if necessary. It is preferable that the silicone rubber layers 5 of S are cross-linked and firmly bonded. Further, instead of such an aging treatment, it is also possible to firmly bond the silicone rubber layers 5 to each other by UV irradiation and UV crosslinking.
　このように、上述した本発明の積層シートＳをセル２が収容された外装体１として使用することにより、セル２の直接加熱を可及的に回避してセル２を密封収容することができる。 Thus, by using the laminated sheet S of the present invention described above as the exterior body 1 in which the cells 2 are accommodated, the cells 2 can be hermetically accommodated while avoiding direct heating of the cells 2 as much as possible. .
　上記のようにしてセルが密封収容されて構成される電気デバイスは、例えば、電池、特にリチウムイオン電池として好適に使用される。勿論、セル２の仕様を適宜変更し、キャパシタ、電気二重層キャパシタ等としても使用することができる。 An electrical device configured by sealingly storing cells as described above is preferably used as, for example, a battery, particularly a lithium ion battery. Of course, the specification of the cell 2 can be changed as appropriate to use it as a capacitor, an electric double layer capacitor, or the like.
　以上、本発明の実施形態について説明述したが、具体的な構成はこれらの実施形態に限定されるものではない。 The embodiments of the present invention have been described above, but the specific configuration is not limited to these embodiments.
　１：外装体
　２：セル
　３：周縁部（シール部）
　４：金属箔
　５：シリコーンゴム層
　６：シリコーン塗料層
　７：シリコーンゴムシート
　Ｐ：電気デバイス
　Ｓ：積層シート 1: Exterior body 2: Cell 3: Peripheral part (seal part)
4: Metal foil 5: Silicone rubber layer 6: Silicone paint layer 7: Silicone rubber sheet P: Electrical device S: Laminated sheet

Claims (7)

  1. 　金属箔と、前記金属箔の一方の面に積層されたシリコーンゴム層とを有しており、前記シリコーンゴム層を内面として使用されることを特徴とするセル外装体用積層シート。 A laminated sheet for cell exterior bodies, comprising a metal foil and a silicone rubber layer laminated on one surface of the metal foil, wherein the silicone rubber layer is used as an inner surface.
  2. 　前記シリコーンゴム層が、シリコーン塗料により前記金属箔の表面に積層されている請求項１に記載のセル外装体用積層シート。 The laminated sheet for cell exterior bodies according to claim 1, wherein the silicone rubber layer is laminated on the surface of the metal foil with a silicone paint.
  3. 　前記シリコーンゴム層は、２０μｍ以上の厚みを有する請求項１に記載のセル外装体用積層シート。 The laminated sheet for a cell outer package according to claim 1, wherein the silicone rubber layer has a thickness of 20 µm or more.
  4. 　前記シリコーンゴム層は、５０～２００μｍの厚みを有する請求項３に記載のセル外装体用積層シート。 The laminated sheet for a cell outer package according to claim 3, wherein the silicone rubber layer has a thickness of 50 to 200 µm.
  5. 　請求項１に記載の積層シートを外装体とし、該外装体の内部に、一対の電極基板の間に電解質が挟持されている構造のセルが、密封収容されている電気デバイス。 An electrical device in which a cell having a structure in which the laminated sheet according to claim 1 is used as an exterior body and an electrolyte is sandwiched between a pair of electrode substrates is sealed inside the exterior body.
  6. 　前記セルが、複数密封収容されている請求項５に記載の電気デバイス。 The electric device according to claim 5, wherein a plurality of the cells are hermetically sealed.
  7. 　電池である請求項５に記載の電気デバイス。 The electric device according to claim 5, wherein the electric device is a battery.
PCT/JP2017/036269 2016-10-07 2017-10-05 Cell exterior member laminate sheet WO2018066645A1 (en)

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JP2018115319A (en) * 2017-01-13 2018-07-26 積水化学工業株式会社 Thermally expandable fire-resistant sheet and use thereof in battery
EP3886197A4 (en) * 2018-11-21 2022-08-03 LG Electronics Inc. Lead tab for secondary battery, manufacturing apparatus thereof, and secondary battery comprising same

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JP5989846B1 (en) * 2015-04-10 2016-09-07 東洋製罐グループホールディングス株式会社 Heat resistant laminated sheet

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JP2000173564A (en) * 1998-12-03 2000-06-23 Tokai Rubber Ind Ltd Thin battery bag body
JP2005063775A (en) * 2003-08-08 2005-03-10 Nissan Motor Co Ltd Bipolar battery, battery pack, composite battery pack, and vehicle using battery pack or composite battery pack
JP5989846B1 (en) * 2015-04-10 2016-09-07 東洋製罐グループホールディングス株式会社 Heat resistant laminated sheet

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Publication number Priority date Publication date Assignee Title
JP2018115319A (en) * 2017-01-13 2018-07-26 積水化学工業株式会社 Thermally expandable fire-resistant sheet and use thereof in battery
JP7168323B2 (en) 2017-01-13 2022-11-09 積水化学工業株式会社 Heat-expandable fire-resistant sheet and use of the heat-expandable fire-resistant sheet in battery
EP3886197A4 (en) * 2018-11-21 2022-08-03 LG Electronics Inc. Lead tab for secondary battery, manufacturing apparatus thereof, and secondary battery comprising same

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