TW201841410A - Exterior material for use in power storage device and power storage device without pinholes or cracks even if it is bent - Google Patents
Exterior material for use in power storage device and power storage device without pinholes or cracks even if it is bent Download PDFInfo
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- TW201841410A TW201841410A TW107107944A TW107107944A TW201841410A TW 201841410 A TW201841410 A TW 201841410A TW 107107944 A TW107107944 A TW 107107944A TW 107107944 A TW107107944 A TW 107107944A TW 201841410 A TW201841410 A TW 201841410A
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Classifications
-
- 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
-
- 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- 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
- B32B15/08—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 synthetic resin
- B32B15/09—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 synthetic resin comprising polyesters
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- 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
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- 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
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/133—Thickness
-
- 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
- H01M50/183—Sealing members
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/10—Batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Laminated Bodies (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Mounting, Suspending (AREA)
- Secondary Cells (AREA)
Abstract
Description
本發明係關於智慧型手機、觸控面板等之攜帶機器所使用之電池或電容器、混合動力汽車、電動汽車、風力發電、太陽能發電、夜間電氣之蓄電所使用的電池或電容器等之蓄電裝置用之外裝材及該外裝材所外裝之蓄電裝置。 The present invention relates to power storage devices such as batteries or capacitors used in portable devices such as smart phones and touch panels, hybrid vehicles, electric vehicles, wind power, solar power, and night-time electrical power storage. Exterior packaging materials and power storage devices mounted on the exterior packaging materials.
近年來，將各種資訊儲存於IC卡、信用卡等之卡片中之技術已日漸進步。為了交換如此資訊量多之卡片內之資訊，需要極大之電力。傳統上，係使用利用RFID標籤等之磁束者，惟無法得到充分之電力量。 In recent years, the technology of storing various information in IC cards, credit cards, etc. has been gradually improved. In order to exchange information in such a large amount of information, great power is required. Traditionally, those who use magnetic beams such as RFID tags have not been able to obtain a sufficient amount of power.
為了交換資訊量多之卡片內之資訊，需要可得到充分電力量之薄型電池。製造薄型電池時，由於係薄型之要求，故無法使用金屬罐等之厚外裝材，且由於係薄型之要求，故配置於內部之電池元件(電極板、隔板等)必須設計為薄型，藉由如此之薄型化難以確保作為電池元件之充分強度，有降低此等電池元件彎折耐性之問題。 In order to exchange information in a card with a large amount of information, a thin battery that can obtain a sufficient amount of power is needed. When manufacturing thin batteries, it is not possible to use thick exterior materials such as metal cans because of the requirements for thinness, and because of the requirements for thinness, the battery elements (electrode plates, separators, etc.) arranged inside must be designed to be thin, With such a reduction in thickness, it is difficult to ensure sufficient strength as a battery element, and there is a problem in that these battery elements have reduced bending resistance.
專利文獻1，記載一種搭載薄型電池之電子裝置，其係藉由規定薄型電池內部之集電體全體之厚度與搭載薄型電池之電子裝置側之厚度的關係，從而使其即使受到彎曲變形，搭載電池亦不會發生斷線等之機 能降低。亦即，專利文獻1，記載一種搭載薄型電池之電子裝置，其係搭載有片狀之電極群及薄型電池；前述片狀之電極群係具備：正極、負極、及介在前述正極與前述負極之間之電解質層；前述薄型電池係具備：密閉前述電極群之外裝體；前述電極群之厚度h、從前述電極群之上面至搭載薄型電池之電子裝置上面為止之距離H1、及從前述電極群下面至搭載薄型電池之電子裝置下面為止之距離H2，係滿足10≦H1/h，且10≦H2/h之關係(參照專利文獻之圖6等)。 Patent Document 1 describes an electronic device equipped with a thin battery. The relationship between the thickness of the entire current collector inside the thin battery and the thickness of the side of the electronic device on which the thin battery is mounted is specified so that it can be mounted even if it is bent and deformed. The function of the battery is not reduced, such as disconnection. That is, Patent Document 1 describes an electronic device equipped with a thin battery, which is equipped with a sheet-shaped electrode group and a thin battery; the sheet-shaped electrode group includes a positive electrode, a negative electrode, and an electrode interposed between the positive electrode and the negative electrode. The thin battery system includes: an outer body that hermetically seals the electrode group; a thickness h of the electrode group, a distance H1 from the top of the electrode group to the top of the electronic device on which the thin battery is mounted, and the electrode The distance H2 from the bottom of the group to the bottom of the electronic device on which the thin battery is mounted satisfies the relationship of 10 ≦ H1 / h and 10 ≦ H2 / h (refer to FIG. 6 in the patent document).
【專利文獻1】 日本特開2013-161691號公報 [Patent Document 1] Japanese Patent Application Publication No. 2013-161691
然而，上述傳統技術，為了防止在彎曲變形時，發生因搭載之薄型電池導致之機能降低，從而係符合規定薄型電池之集電體全體之厚度與搭載之電子裝置側之厚度之關係者，並非係規定薄型電池本身之構成或構造而實現解決課題者。亦即，為了解決課題，存在對於搭載電池之卡片等之電子裝置側之構成或構造產生限制之問題。 However, in order to prevent the reduction of the function caused by the thin battery mounted during the bending deformation, the above-mentioned conventional technology is related to the thickness of the entire current collector of the thin battery and the thickness of the side of the mounted electronic device, which is not in compliance with the regulations. It is a person who defines the structure or structure of the thin battery itself to achieve the problem. That is, in order to solve the problem, there is a problem that the configuration or structure of the electronic device side on which a card or the like on which a battery is mounted is restricted.
本發明，係鑑於相關技術背景所成者，目的在於提供一種蓄電裝置用外裝材，其即使受到彎折等彎曲變形，外裝材仍不會產生針孔或 裂痕等，彎曲耐性優異。 The present invention has been made in view of the related technical background, and an object thereof is to provide an exterior material for a power storage device, which is free from pinholes or cracks even when subjected to bending deformation such as bending, and has excellent bending resistance.
本申請人，進行深入研究，以設計一種電池等之蓄電裝置用之外裝材本身之構成或構造而提供彎曲耐性優異者，從而完成本發明。亦即，為了達成前述目的，本發明提供以下之手段。 The applicant has conducted intensive studies to design a structure or structure of an exterior material itself for a power storage device such as a battery, and to provide a person with excellent bending resistance, thereby completing the present invention. That is, in order to achieve the aforementioned object, the present invention provides the following means.
[1]一種蓄電裝置用外裝材，其係包含由耐熱性樹脂薄膜所成之基材層、內側層之密封層、及配置於前述基材層與前述密封層之間之金屬箔層，其特徵係構成前述基材層之耐熱性樹脂薄膜，係楊氏模數為2.5GPa~4.5GPa之耐熱性樹脂薄膜；前述基材層之厚度，係前述金屬箔層之厚度之1.5倍~3.0倍。 [1] An exterior material for a power storage device, comprising a base material layer made of a heat-resistant resin film, a sealing layer on an inner layer, and a metal foil layer disposed between the base material layer and the sealing layer, Its characteristics are the heat-resistant resin film constituting the aforementioned substrate layer, and the heat-resistant resin film having a Young's modulus of 2.5 GPa to 4.5 GPa; the thickness of the aforementioned substrate layer is 1.5 to 3.0 times the thickness of the aforementioned metal foil layer Times.
[2]如前項1所記載之蓄電裝置用外裝材，其中，前述金屬箔層之厚度係5μm~35μm。 [2] The exterior material for a power storage device according to the item 1, wherein a thickness of the metal foil layer is 5 μm to 35 μm.
[3]如前項1或2所記載之蓄電裝置用外裝材，其中，構成前述基材層之耐熱性樹脂薄膜，係聚酯樹脂薄膜。 [3] The exterior material for a power storage device according to the above item 1 or 2, wherein the heat-resistant resin film constituting the base material layer is a polyester resin film.
[4]如前項1~3中任一項所記載之蓄電裝置用外裝材，其中，前述蓄電裝置用外裝材之厚度係70μm~120μm。 [4] The exterior material for a power storage device according to any one of items 1 to 3, wherein a thickness of the exterior material for a power storage device is 70 μm to 120 μm.
[5]一種蓄電裝置用外裝外殼，其特徵係由前項1~4中任一項所記載之蓄電裝置用外裝材之成形體所成。 [5] An exterior case for a power storage device, characterized by being formed from a molded body of an exterior material for a power storage device according to any one of 1 to 4 above.
[6]一種蓄電裝置，其特徵係具備：蓄電裝置本體部、 由前項1~4中任一項所記載之蓄電裝置用外裝材及/或前項5所記載之蓄電裝置用外裝外殼所成之外裝部材；且前述蓄電裝置本體部，係由前述外裝部材所外裝。 [6] A power storage device, comprising: a power storage device main body; the exterior material for a power storage device according to any one of the preceding paragraphs 1 to 4; and / or the exterior casing for a power storage device as described in the preceding paragraph 5. The exterior parts are provided; and the main body of the power storage device is covered by the exterior parts.
根據[1]之發明，由於構成基材層之耐熱性樹脂薄膜，係使用楊氏模數為2.5GPa~4.5GPa者，故可提供一種蓄電裝置用外裝材，其耐彎折性等之彎曲耐性(彎曲回復力)優異，即使受到彎折等，外裝材仍不會產生針孔或裂痕等。此外，由於構成基材層之耐熱性樹脂薄膜之楊氏模數為4.5GPa以下，故可確保作為蓄電裝置用外裝材有良好之成形性。此外，由於基材層之厚度，係金屬箔層之厚度之1.5倍~3.0倍，故可提供一種蓄電裝置用外裝材，其外裝材之厚度即使係薄型構成(例如60μm~90μm之厚度)，耐彎折性等之彎曲耐性(彎曲回復力)亦優異。此外，此蓄電裝置用外裝材，對於沖孔強度等之機械強度(物理強度)亦優異。 According to the invention of [1], since the heat-resistant resin film constituting the base material layer uses a Young's modulus of 2.5 GPa to 4.5 GPa, it is possible to provide an exterior material for a power storage device, which is resistant to bending, etc. It is excellent in bending resistance (bending restoring force), and even if it is bent, the exterior material does not have pinholes or cracks. In addition, since the Young's modulus of the heat-resistant resin film constituting the base material layer is 4.5 GPa or less, good moldability can be ensured as an exterior material for a power storage device. In addition, since the thickness of the base material layer is 1.5 to 3.0 times the thickness of the metal foil layer, an exterior material for a power storage device can be provided. The thickness of the exterior material can be a thin structure (for example, a thickness of 60 μm to 90 μm). ) And bending resistance (bending recovery force) such as bending resistance. In addition, this exterior material for a power storage device is also excellent in mechanical strength (physical strength) such as punching strength.
根據[2]之發明，由於金屬箔層之厚度係5μm~35μm，故可提供一種蓄電裝置用外裝材，其具進一步優異之耐彎折性等之彎曲耐性(彎曲回復力)。 According to the invention of [2], since the thickness of the metal foil layer is 5 μm to 35 μm, it is possible to provide an exterior material for a power storage device having further excellent bending resistance (bending resistance) such as bending resistance.
根據[3]之發明，可提供一種蓄電裝置用外裝材，其耐水性等之耐候性優異。 According to the invention of [3], it is possible to provide an exterior material for a power storage device, which is excellent in weather resistance such as water resistance.
根據[4]之發明，可提升蓄電裝置用外裝材之熱密封性(熱密封性)。 According to the invention of [4], the heat-sealing property (heat-sealing property) of an exterior material for a power storage device can be improved.
根據[5]之發明，可提供一種蓄電裝置用外裝外殼，其耐彎 折性等之彎曲耐性(彎曲回復力)優異，且即使受到彎折等，外裝材仍不會產生針孔或裂痕等。此外，即使外裝外殼之厚度係薄型構成(例如60μm~90μm之厚度)，耐彎折性等之彎曲耐性(彎曲回復力)亦優異。此外，此外裝外殼，對於沖孔強度等之機械強度(物理強度)亦優異。 According to the invention of [5], it is possible to provide an exterior casing for a power storage device, which is excellent in bending resistance (bending recovery force) such as bending resistance, and the exterior material does not have pinholes or Cracks, etc. In addition, even if the thickness of the exterior case is a thin structure (for example, a thickness of 60 μm to 90 μm), bending resistance (bending recovery force) such as bending resistance is excellent. In addition, the outer casing is also excellent in mechanical strength (physical strength) such as punching strength.
根據[6]之發明，由於係由耐彎折性等之彎曲耐性(彎曲回復力)優異之蓄電裝置用外裝材所外裝，故可提供一種蓄電裝置，其即使受到彎折等，外裝材仍不會產生針孔或裂痕等。 According to the invention of [6], since the exterior is made of an exterior material for a power storage device that is excellent in bending resistance (bending recovery force) such as bending resistance, it is possible to provide a power storage device that can be bent, etc. There are still no pinholes or cracks in the material.
1‧‧‧蓄電裝置用外裝材 1‧‧‧ Exterior materials for power storage devices
2‧‧‧基材層(外側層) 2‧‧‧ substrate layer (outer layer)
3‧‧‧密封層(內側層) 3‧‧‧Sealing layer (inner layer)
4‧‧‧金屬箔層 4‧‧‧ metal foil layer
20‧‧‧蓄電裝置 20‧‧‧ Power storage device
【圖1】表示本發明之蓄電裝置用外裝材之一實施形態之斷面圖。 Fig. 1 is a sectional view showing an embodiment of an exterior material for a power storage device according to the present invention.
【圖2】表示使用本發明之蓄電裝置用外裝材所構成之蓄電裝置之一實施形態之斷面圖。 FIG. 2 is a cross-sectional view showing an embodiment of a power storage device constructed using the exterior material for a power storage device of the present invention.
本發明之蓄電裝置用外裝材1之一實施形態如圖1所示。此蓄電裝置用外裝材1，係作為鋰離子蓄電池外殼用而使用者。亦即，前述蓄電裝置用外裝材1，例如，進行深絞伸成形、鼓脹成形等之成形而作為蓄電池之外殼等使用。 An embodiment of an exterior material 1 for a power storage device according to the present invention is shown in FIG. 1. This exterior material 1 for a power storage device is intended for use as a lithium ion battery case. That is, the above-mentioned exterior material 1 for a power storage device is used, for example, as a case for a storage battery by forming such as deep draw drawing, inflation forming, or the like.
前述蓄電裝置用外裝材1，係由金屬箔層4之一側的面介由第1接著劑層5與耐熱性樹脂薄膜層(外側層；基材層)2積層一體化，且前述金屬箔層4之另一側的面介由第2接著劑層6與熱熔性樹脂層(內側層；密封層)3 積層一體化之構成所成。 The exterior material 1 for a power storage device is formed by laminating and integrating a heat-resistant resin film layer (outer layer; base material layer) 2 with a first adhesive layer 5 through a surface on one side of the metal foil layer 4 and the metal The surface on the other side of the foil layer 4 is formed by laminating and integrating the second adhesive layer 6 and the hot-melt resin layer (inner layer; sealing layer) 3.
本發明之蓄電裝置用外裝材1中，構成前述基材層2之耐熱性樹脂薄膜，係楊氏模數為2.5GPa~4.5GPa之耐熱性樹脂薄膜，前述基材層2之厚度，係前述金屬箔層4之厚度的1.5倍~3.0倍之構成。本發明中，構成基材層2之耐熱性樹脂薄膜，係使用楊氏模數為2.5GPa~4.5GPa之耐熱性樹脂薄膜，故可提供一種蓄電裝置用外裝材，其耐彎折性等之彎曲耐性(彎曲回復力)優異，即使受到彎折、曲折等，外裝材仍不會產生針孔或裂痕等。因此，即使受到彎折、曲折等，仍可防止蓄電裝置中斷路或液體洩漏。此外，由於構成基材層2之耐熱性樹脂薄膜之楊氏模數為4.5GPa以下，故在成形為蓄電裝置用外裝材1時可確保良好之成形性。此外，由於基材層2之厚度，係金屬箔層4之厚度之1.5倍~3.0倍，故可提供一種蓄電裝置用外裝材1，其即使外裝材之總厚度係薄型構成(例如60μm~90μm之厚度)，耐彎折性等之彎曲耐性(彎曲回復力)仍優異。 In the exterior material 1 for a power storage device of the present invention, the heat-resistant resin film constituting the base material layer 2 is a heat-resistant resin film having a Young's modulus of 2.5 GPa to 4.5 GPa, and the thickness of the base material layer 2 is The metal foil layer 4 has a thickness of 1.5 to 3.0 times. In the present invention, the heat-resistant resin film constituting the base material layer 2 is a heat-resistant resin film having a Young's modulus of 2.5 GPa to 4.5 GPa. Therefore, an exterior material for a power storage device can be provided, which has resistance to bending, etc. It has excellent bending resistance (bending restoring force), and even if it is subjected to bending, zigzag, etc., the exterior material does not have pinholes or cracks. Therefore, even if it is subjected to bending, tortuosity, etc., it is possible to prevent the power storage device from being interrupted or leaking liquid. In addition, since the Young's modulus of the heat-resistant resin film constituting the base material layer 2 is 4.5 GPa or less, good moldability can be ensured when molding into the exterior material 1 for a power storage device. In addition, since the thickness of the base material layer 2 is 1.5 to 3.0 times the thickness of the metal foil layer 4, it is possible to provide an exterior material 1 for a power storage device, even if the total thickness of the exterior material is a thin structure (e.g., 60 μm). ~ 90 μm thickness), bending resistance (bending resistance) such as bending resistance is still excellent.
構成前述基材層2之耐熱性樹脂薄膜之楊氏模數若小於2.5GPa時，耐彎折性等之彎曲耐性會降低。此外，構成前述基材層2之耐熱性樹脂薄膜之楊氏模數若超過4.5GPa時，進行大角度之彎曲會有外裝材產生針孔或裂痕等之問題。其中，構成前述基材層2之耐熱性樹脂薄膜之楊氏模數，係在3.0GPa~4.0GPa之範圍內為佳。 When the Young's modulus of the heat-resistant resin film constituting the base material layer 2 is less than 2.5 GPa, bending resistance such as bending resistance is reduced. In addition, if the Young's modulus of the heat-resistant resin film constituting the base material layer 2 exceeds 4.5 GPa, bending at a large angle may cause problems such as pinholes or cracks in the exterior material. Among them, the Young's modulus of the heat-resistant resin film constituting the base material layer 2 is preferably in a range of 3.0 GPa to 4.0 GPa.
前述基材層2之厚度，若未達前述金屬箔層4之厚度之1.5倍時，會有因外裝材之彎曲而容易發生外裝材之強度降低之問題。此外，前述基材層2之厚度，若超過前述金屬箔層4之厚度之3.0倍時，會有因外裝材之彎曲導致外裝材之屏障性容易降低之問題。其中，前述基材層2之厚度， 係前述金屬箔層4之厚度之2.0倍~2.7倍為佳。 If the thickness of the base material layer 2 is less than 1.5 times the thickness of the metal foil layer 4, there is a problem that the strength of the exterior material is liable to decrease due to the bending of the exterior material. In addition, if the thickness of the substrate layer 2 exceeds 3.0 times the thickness of the metal foil layer 4, there is a problem that the barrier property of the exterior material is liable to decrease due to bending of the exterior material. The thickness of the substrate layer 2 is preferably 2.0 to 2.7 times the thickness of the metal foil layer 4.
構成前述基材層(外側層)2之耐熱性樹脂，係使用不因將外裝材熱密封時之熱密封溫度而熔融之耐熱性樹脂。前述耐熱性樹脂，係使用具有較構成熱熔性樹脂層(密封層)3之熱熔性樹脂之熔點高10℃以上之熔點的耐熱性樹脂為佳，使用具有較熱熔性樹脂之熔點高20℃以上之熔點的耐熱性樹脂特佳。 The heat-resistant resin constituting the base material layer (outer layer) 2 is a heat-resistant resin that does not melt due to the heat-sealing temperature when heat-sealing the exterior material. The heat-resistant resin is preferably a heat-resistant resin having a melting point higher than that of the hot-melt resin constituting the hot-melt resin layer (sealing layer) 3 by 10 ° C. or higher, and has a higher melting point than the hot-melt resin. A heat-resistant resin having a melting point of 20 ° C or higher is particularly preferred.
前述耐熱性樹脂薄膜層(基材層)2，並無特別限定，可列舉例如：尼龍薄膜等之聚醯胺薄膜、聚酯薄膜、聚烯烴薄膜、聚碳酸酯薄膜等，理想使用此等之延伸薄膜。其中，前述耐熱性樹脂薄膜2，使用二軸延伸聚對苯二甲酸丁二酯(PBT)薄膜、二軸延伸聚對苯二甲酸乙二酯(PET)薄膜、二軸延伸聚萘二甲酸乙二醇酯(PEN)薄膜等之二軸延伸聚酯薄膜特佳。前述尼龍薄膜，並無特別限定，可列舉例如：6尼龍薄膜、6，6尼龍薄膜、MXD尼龍薄膜等。又，前述耐熱性樹脂薄膜層2，可由單層形成，抑或，例如由聚酯薄膜/聚醯胺薄膜所成複層(PET薄膜/尼龍薄膜所成複層等)形成亦可。前述例示之複層構成中，係將聚酯薄膜配置於較聚醯胺薄膜外側為佳，相同地，將PET薄膜配置於較尼龍薄膜外側為佳。 The heat-resistant resin film layer (base material layer) 2 is not particularly limited, and examples thereof include polyamide films such as nylon films, polyester films, polyolefin films, and polycarbonate films. Stretch film. The heat-resistant resin film 2 includes a biaxially-stretched polybutylene terephthalate (PBT) film, a biaxially-stretched polyethylene terephthalate (PET) film, and a biaxially-stretched polyethylene naphthalate. Biaxially oriented polyester films such as glycol ester (PEN) films are particularly preferred. The nylon film is not particularly limited, and examples thereof include 6 nylon films, 6,6 nylon films, and MXD nylon films. The heat-resistant resin film layer 2 may be formed of a single layer or, for example, a multilayer formed of a polyester film / polyamide film (such as a multilayer formed of a PET film / nylon film). In the above-mentioned exemplified multi-layer structure, it is preferable that the polyester film is disposed on the outer side of the polyamide film, and similarly, the PET film is disposed on the outer side of the nylon film.
前述耐熱性樹脂薄膜層(基材層)2之厚度，係設定在9μm~100μm為佳。藉由設定在上述理想之下限值以上，可確保作為外裝材具充分之強度，且藉由設定在上述理想之上限值以下，可縮小進行鼓脹成形、絞伸成形等成形時之應力而可提升成形性。其中，前述耐熱性樹脂薄膜層(基材層)2之厚度，係設定在25μm~60μm特佳。 The thickness of the heat-resistant resin film layer (base material layer) 2 is preferably set to 9 μm to 100 μm. By setting it above the above ideal lower limit value, sufficient strength can be ensured as an exterior material, and by setting it below the above ideal upper limit value, it is possible to reduce stress during forming such as bulging forming and strand forming. It can improve formability. The thickness of the heat-resistant resin film layer (base material layer) 2 is particularly preferably set to 25 μm to 60 μm.
前述密封層(熱熔性樹脂層)(內側層)3，對於鋰離子蓄電池等 中所使用之腐蝕性強的電解液等亦具備優異的耐藥品性，並擔負將熱密封性賦予至外裝材之角色。 The aforementioned sealing layer (hot-melt resin layer) (inner layer) 3 also has excellent chemical resistance to highly corrosive electrolytes used in lithium-ion batteries and the like, and is responsible for imparting heat-sealing properties to the exterior Role of wood.
前述熱熔性樹脂層3，並無特別限定，係熱熔性樹脂無延伸薄膜層為佳。前述熱熔性樹脂無延伸薄膜層3，並無特別限定，惟由選自聚乙烯、聚丙烯、烯烴系共聚物、此等之酸變性物及離聚物所成群中至少1種之熱熔性樹脂所成之無延伸薄膜所構成為佳。又，前述熱熔性樹脂層3，可係單層，亦可係複層。 The hot-melt resin layer 3 is not particularly limited, and it is preferred that the hot-melt resin has no stretched film layer. The hot-melt resin has no stretched film layer 3, and is not particularly limited, but is made of at least one kind of heat selected from the group consisting of polyethylene, polypropylene, olefin-based copolymers, acid-denatured products, and ionomers. A non-stretched film made of a molten resin is preferred. The hot-melt resin layer 3 may be a single layer or a multi-layer.
其中，前述熱熔性樹脂層3，其構成係指少包含3層積層構造，該3層積層構造係於包含含有彈性體成分之烯烴系樹脂之中間層之兩面，積層含有烯烴系樹脂之被覆層的構成，且前述中間層，係具備前述彈性體成分為島狀之海島構造之構成為佳。 Among them, the above-mentioned hot-melt resin layer 3 has a structure including three layers of laminated structure, which are formed on both sides of an intermediate layer containing an olefin-based resin containing an elastomer component, and the layer contains a coating of an olefin-based resin. The structure of the layer and the intermediate layer is preferably a structure having an island structure with an island-like elastomer component.
含有前述彈性體成分之烯烴系樹脂，可係於烯烴系樹脂中添加(配合)彈性體之構成，亦可係將烯烴系樹脂骨架與彈性體成分化學性結合而成之彈性體變性烯烴系樹脂。又，前述「彈性體」之詞，係用於意指包含橡膠成分。 The olefin-based resin containing the above-mentioned elastomer component may be formed by adding (compounding) an elastomer to the olefin-based resin, or may be an elastomer-modified olefin-based resin obtained by chemically combining an olefin-based resin skeleton with an elastomer component. . The term "elastomer" is used to mean that it contains a rubber component.
前述熱熔性樹脂層3之厚度，係設定在20μm~80μm為佳。藉由設定在20μm以上可充分防止針孔的發生，且藉由設定在80μm以下可減少樹脂使用量而可實現成本降低。其中，前述熱熔性樹脂層3之厚度係設定在20μm~40μm特佳。 The thickness of the hot-melt resin layer 3 is preferably set to 20 μm to 80 μm. The setting of 20 μm or more can sufficiently prevent the occurrence of pinholes, and the setting of 80 μm or less can reduce the amount of resin used and achieve cost reduction. The thickness of the hot-melt resin layer 3 is particularly preferably set to 20 μm to 40 μm.
又，於蓄電裝置用外裝材1進行成形時，為了提升成形性，較佳係在前述熱熔性樹脂層3中含有潤滑劑。前述潤滑劑，並無特別限定，可列舉例如：飽和脂肪酸醯胺、不飽和脂肪酸醯胺、置換醯胺、羥甲基醯 胺、飽和脂肪酸二醯胺、不飽和脂肪酸二醯胺、脂肪酸酯醯胺、芳香族系二醯胺等。 In addition, when forming the exterior material 1 for a power storage device, in order to improve the moldability, it is preferable to include a lubricant in the hot-melt resin layer 3. The lubricant is not particularly limited, and examples thereof include saturated fatty acid amidoamine, unsaturated fatty acid amidoamine, substituted amidine, methylolamine, saturated fatty acid diamine, unsaturated fatty acid diamine, and fatty acid ester. Amidoamine, aromatic diamine and the like.
前述金屬箔層4，係擔負賦予外裝材1阻止氧或水分之侵入之氣體屏障性之角色。前述金屬箔層4，並無特別限定，可列舉例如：鋁箔、SUS箔(不鏽鋼箔)、銅箔、鎳箔等，一般係使用鋁箔。前述金屬箔層4之厚度，係5μm~35μm為佳。藉由為5μm以上可防止在製造金屬箔中之壓延時之針孔產生，且藉由為35μm以下可縮小鼓脹成形、絞伸成形等之成形時的應力而可提升成形性。其中，前述金屬箔層4之厚度，係9μm~25μm為特佳。 The metal foil layer 4 plays a role of providing a gas barrier property to the exterior material 1 to prevent the intrusion of oxygen or moisture. The metal foil layer 4 is not particularly limited, and examples thereof include aluminum foil, SUS foil (stainless steel foil), copper foil, and nickel foil. Generally, aluminum foil is used. The thickness of the metal foil layer 4 is preferably 5 μm to 35 μm. With a thickness of 5 μm or more, pinholes that prevent pressure delay in the production of metal foils can be prevented, and 35 μm or less can reduce the stress at the time of forming such as bulging and stretch forming to improve formability. The thickness of the metal foil layer 4 is particularly preferably 9 μm to 25 μm.
前述金屬箔層4，係至少於內側之面(第2接著劑層6側之面)施以化成處理為佳。藉由施以如此之化成處理，可充分防止因內容物(電池之電解液等)所導致之金屬箔表面之腐蝕。例如藉由下述之處理可對於金屬箔施以化成處理。亦即，例如，在進行脫脂處理的金屬箔表面上，藉由塗工下述1)~3)之中任一者之水溶液後，乾燥，從而施加化成處理：1)含有磷酸、鉻酸、及選自氟化物之金屬鹽及氟化物之非金屬鹽所成群中至少1種之化合物的混合物之水溶液；2)含有磷酸、選自丙烯酸系樹脂、殼聚醣衍生物樹脂及酚醛系樹脂所成群中至少1種之樹脂、及選自鉻酸及鉻(III)鹽所成群中至少1種之化合物的混合物之水溶液。3)含有磷酸、 選自丙烯酸系樹脂、殼聚醣衍生物樹脂及酚醛系樹脂所成群中至少1種之樹脂、選自鉻酸及鉻(III)鹽所成群中至少1種之化合物、及選自氟化物之金屬鹽及氟化物之非金屬鹽所成群中至少1種之化合物的混合物之水溶液。 It is preferable that the metal foil layer 4 is chemically treated at least on the inner surface (the surface on the second adhesive layer 6 side). By applying such a chemical conversion treatment, it is possible to sufficiently prevent the corrosion of the surface of the metal foil caused by the contents (the electrolyte of the battery, etc.). For example, the metal foil may be subjected to a chemical conversion treatment by the following treatment. That is, for example, on the surface of the metal foil subjected to degreasing treatment, an aqueous solution of any one of the following 1) to 3) is applied and then dried to perform a chemical conversion treatment: 1) containing phosphoric acid, chromic acid, And an aqueous solution of a mixture of at least one compound selected from the group consisting of metal salts of fluorides and non-metal salts of fluorides; 2) containing phosphoric acid, selected from acrylic resins, chitosan derivative resins, and phenolic resins An aqueous solution of a mixture of at least one resin in the group and at least one compound selected from the group consisting of chromic acid and chromium (III) salt. 3) Phosphoric acid, a resin selected from the group consisting of acrylic resins, chitosan derivative resins, and phenol resins, and at least one compound selected from the group consisting of chromic acid and chromium (III) salts And an aqueous solution of a mixture of at least one compound selected from the group consisting of metal salts of fluorides and non-metal salts of fluorides.
前述化成皮膜，其鉻附著量(單面)為0.1mg/m2~50mg/m2為佳，2mg/m2~20mg/m2為特佳。 In the aforementioned chemical conversion film, the chromium adhesion amount (one side) is preferably 0.1 mg / m 2 to 50 mg / m 2 , and 2 mg / m 2 to 20 mg / m 2 is particularly preferred.
前述第1接著劑層5，並無特別限定，可列舉例如，聚胺酯接著劑層、聚酯聚胺酯接著劑層、聚醚聚胺酯接著劑層等。前述第1接著劑層5之厚度，係設定在1μm~5μm為佳。其中，根據外裝材之薄膜化、輕量化之觀點，前述第1接著劑層5之厚度，係設定在1μm~3μm特佳。 The first adhesive layer 5 is not particularly limited, and examples thereof include a polyurethane adhesive layer, a polyester polyurethane adhesive layer, and a polyether polyurethane adhesive layer. The thickness of the first adhesive layer 5 is preferably set to 1 μm to 5 μm. Among them, from the viewpoint of thinning and reducing the weight of the exterior material, the thickness of the first adhesive layer 5 is particularly preferably set to 1 μm to 3 μm.
前述第2接著劑層6，並無特別限定，例如，亦可使用上述第1接著劑層5所例示者，惟使用因電解液導致之膨潤現象較少之聚烯烴系接著劑為佳。前述第2接著劑層6之厚度，係設定在1μm~5μm為佳。其中，根據外裝材之薄膜化、輕量化之觀點，前述第2接著劑層6之厚度，係設定在1μm~3μm特佳。 The second adhesive layer 6 is not particularly limited. For example, the first adhesive layer 5 may be exemplified, but a polyolefin-based adhesive having less swelling due to the electrolytic solution is preferably used. The thickness of the second adhesive layer 6 is preferably set to 1 μm to 5 μm. Among them, from the viewpoint of thinning and lightening the exterior material, the thickness of the second adhesive layer 6 is particularly preferably set to 1 μm to 3 μm.
本發明之蓄電裝置用外裝材1之厚度，係設定在70μm~120μm為佳，其中，係設定在80μm~110μm特佳。 The thickness of the exterior material 1 for a power storage device of the present invention is preferably set to 70 μm to 120 μm, and particularly, it is set to 80 μm to 110 μm.
本發明之蓄電裝置用外裝材1中，亦可於前述耐熱性樹脂薄膜層(基材層)2之更外側(與金屬箔層4側為相反側之面)積層1或複數之其他層。 In the exterior material 1 for a power storage device of the present invention, one or a plurality of other layers may be laminated on the outer side of the heat-resistant resin film layer (base material layer) 2 (the surface opposite to the metal foil layer 4 side). .
藉由將本發明之蓄電裝置用外裝材1進行成形(深絞伸成 形、鼓脹成形等)，可得到成形外殼(電池外殼等)。又，本發明之蓄電裝置用外裝材1，亦可不進行成形而直接使用。 By molding the exterior material 1 for a power storage device of the present invention (deep drawing, bulging, etc.), a molded case (battery case, etc.) can be obtained. The exterior material 1 for a power storage device of the present invention may be used without being formed.
使用本發明之外裝材1所構成之蓄電裝置20之一實施形態如圖2所示。此蓄電裝置20，係鋰離子蓄電池。 An embodiment of a power storage device 20 constructed using the exterior material 1 of the present invention is shown in FIG. 2. The power storage device 20 is a lithium-ion battery.
前述電池20，係具備：電解質21、接片22、未進行成形之平面狀之前述外裝材1、具有將前述外裝材1進行成形所得之收容凹部11b之成形外殼11(參照圖2)。藉由前述電解質21及前述接片22構成蓄電裝置本體部19。 The battery 20 includes an electrolyte 21, a tab 22, the unformed planar exterior material 1, and a molded case 11 having a receiving recess 11b obtained by molding the exterior material 1 (see FIG. 2). . The power storage device body 19 is configured by the electrolyte 21 and the tabs 22.
藉由在前述成形外殼11之收容凹部11b內收容前述電解質21及前述接片22之一部分，將前述平面狀之外裝材1配置於該成形外殼11之上，將該外裝材1之周緣部(之內側層3)與前述成形外殼11之密封用周緣部11a(之內側層3)進行熱密封而接合，形成熱密封部(熱密封部)，從而構成前述電池20。又，前述接片22之前端部，係導出於外部(參照圖2)。 By storing a part of the electrolyte 21 and the tab 22 in the receiving recess 11 b of the molded case 11, the planar exterior material 1 is disposed on the molded case 11, and the periphery of the exterior material 1 is arranged. The inner portion (inner layer 3) and the sealing peripheral edge portion 11a (inner layer 3) of the molded case 11 are heat-sealed and joined to form a heat-sealed portion (heat-sealed portion), thereby constituting the battery 20 described above. In addition, the front end portion of the tab 22 is led out to the outside (see FIG. 2).
接著，說明本發明之具體實施例，惟本發明並非特別限定為此等實施例者。 Next, specific embodiments of the present invention will be described, but the present invention is not particularly limited to those embodiments.
<實施例1> <Example 1>
在厚度25μm之鋁箔(金屬箔)4的兩面，塗佈由磷酸、聚丙烯酸(丙烯酸系樹脂)、鉻(III)鹽化合物、水、乙醇所成的化成處理液後，以180℃進行乾燥，從而形成化成皮膜。此化成皮膜之鉻附著量係每面10mg/m2。 On both sides of an aluminum foil (metal foil) 4 having a thickness of 25 μm, a chemical conversion treatment solution made of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and ethanol was applied, and dried at 180 ° C. Thereby, a chemical film is formed. The amount of chromium attached to the formed film was 10 mg / m 2 per side.
接著，在前述完成化成處理之鋁箔4之一側的面，介由2液硬 化型之胺基甲酸酯系接著劑(外側接著劑)5將厚度50μm之二軸延伸聚對苯二甲酸乙二酯(PET)樹脂薄膜(基材層用薄膜)2乾式層壓(貼合)。此二軸延伸聚對苯二甲酸乙二酯(PET)樹脂薄膜之楊氏模數，係4.0GPa。 Next, a biaxially-stretched polyethylene terephthalate having a thickness of 50 μm was passed through a two-liquid curing type urethane-based adhesive (outside adhesive) 5 on one side of the aluminum foil 4 that had undergone the chemical conversion treatment. Diester (PET) resin film (film for base layer) 2 dry lamination (lamination). The Young's modulus of this biaxially stretched polyethylene terephthalate (PET) resin film is 4.0 GPa.
接著，介由2液硬化型之胺基甲酸酯系接著劑(內側接著劑)6，將厚度30μm之無延伸聚丙烯薄膜(密封薄膜層)3之一側的面與前述乾式層壓後之鋁箔4之另一側的面重合，藉由將其包夾於橡膠壓料輥、加熱至100℃之層壓輥之間壓著而乾式層壓，之後，在50℃下養護(加熱)5天，從而得到圖1所示構成之總厚度111μm之蓄電裝置用外裝材1。 Next, one side of the non-stretched polypropylene film (sealing film layer) 3 having a thickness of 30 μm was laminated with the dry type through a two-liquid curing type urethane-based adhesive (inside adhesive) 6. The other side of the aluminum foil 4 was overlapped, dry-laminated by sandwiching it between a rubber nip roll and a laminating roll heated to 100 ° C, and then cured (heated) at 50 ° C. For 5 days, an exterior material 1 for a power storage device having a total thickness of 111 μm as shown in FIG. 1 was obtained.
<實施例2> <Example 2>
除了金屬箔4係使用20μm之鋁箔，外裝材之總厚度係106μm以外，其他皆與實施例1相同，得到圖1所示之蓄電裝置用外裝材1。 Except that the metal foil 4 is an aluminum foil with a thickness of 20 μm and the total thickness of the exterior material is 106 μm, it is the same as in Example 1 to obtain an exterior material 1 for a power storage device shown in FIG. 1.
<實施例3> <Example 3>
除了基材層用薄膜2，係使用厚度38μm之二軸延伸PET樹脂薄膜，金屬箔4係使用20μm之鋁箔，外裝材之總厚度係94μm以外，其他皆與實施例1相同，得到圖1所示之蓄電裝置用外裝材1。 Except for the film 2 for the base material layer, which is a biaxially stretched PET resin film with a thickness of 38 μm, the metal foil 4 is an aluminum foil with a thickness of 20 μm, and the total thickness of the exterior material is 94 μm. The exterior material 1 for a power storage device shown.
<實施例4> <Example 4>
除了基材層用薄膜2，係使用厚度38μm之二軸延伸PET樹脂薄膜，金屬箔4係使用厚度20μm之鋁箔，密封薄膜3係使用厚度20μm之無延伸聚丙烯薄膜，外裝材之總厚度係84μm以外，其他皆與實施例1相同，得到圖1所示之蓄電裝置用外裝材1。 Except for the film 2 for the substrate layer, a biaxially stretched PET resin film with a thickness of 38 μm is used, the metal foil 4 is an aluminum foil with a thickness of 20 μm, and the sealing film 3 is a non-stretched polypropylene film with a thickness of 20 μm. The total thickness of the exterior Except for the case of 84 μm, everything was the same as in Example 1, and an exterior material 1 for a power storage device shown in FIG. 1 was obtained.
<實施例5> <Example 5>
除了基材層用薄膜2，係使用厚度30μm之二軸延伸PET樹脂薄膜/厚度 20μm之二軸延伸尼龍薄膜之共押出積層薄膜(配置為較PET樹脂薄膜外側)，金屬箔4係使用20μm之鋁箔，外裝材之總厚度係109μm以外，其他皆與實施例1相同，得到圖1所示之蓄電裝置用外裝材1。 Except for the film 2 for the base material layer, a coextruded laminated film using a biaxially stretched PET resin film with a thickness of 30 μm / biaxially stretched nylon film with a thickness of 20 μm (configured to be outside the PET resin film), and a metal foil 4 using a 20 μm The total thickness of the aluminum foil and the exterior material was 109 μm, and the rest were the same as those in Example 1 to obtain the exterior material 1 for a power storage device shown in FIG. 1.
<實施例6> <Example 6>
除了基材層用薄膜2，係使用厚度20μm之二軸延伸PET樹脂薄膜/厚度30μm之二軸延伸尼龍薄膜之共押出積層薄膜(配置為較PET樹脂薄膜外側)，金屬箔4係使用20μm之鋁箔，外裝材之總厚度係109μm以外，其他皆與實施例1相同，得到圖1所示之蓄電裝置用外裝材1。 Except for the film 2 for the substrate layer, a coextruded laminated film using a biaxially stretched PET resin film with a thickness of 20 μm / a biaxially stretched nylon film with a thickness of 30 μm (configured to be outside the PET resin film), and a metal foil 4 using a 20 μm The total thickness of the aluminum foil and the exterior material was 109 μm, and the rest were the same as those in Example 1 to obtain the exterior material 1 for a power storage device shown in FIG. 1.
<實施例7> <Example 7>
除了基材層用薄膜2，係使用厚度40μm之二軸延伸尼龍薄膜，金屬箔4係使用25μm之鋁箔，密封薄膜3係使用厚度40μm之無延伸聚丙烯薄膜，外裝材之總厚度係111μm以外，其他皆與實施例1相同，得到圖1所示之蓄電裝置用外裝材1。 Except for the film 2 for the base layer, a biaxially stretched nylon film with a thickness of 40 μm is used, the metal foil 4 is an aluminum foil with a thickness of 25 μm, the sealing film 3 is a non-stretched polypropylene film with a thickness of 40 μm, and the total thickness of the exterior material is 111 μm Other than that, it was the same as Example 1, and the exterior material 1 for electrical storage devices shown in FIG. 1 was obtained.
<比較例1> <Comparative example 1>
除了基材層用薄膜，係使用厚度25μm之二軸延伸尼龍薄膜，金屬箔係使用40μm之鋁箔，密封薄膜係使用厚度40μm之無延伸聚丙烯薄膜，外裝材之總厚度係111μm以外，其他皆與實施例1相同，得到蓄電裝置用外裝材。 Except for the film for the base material layer, a biaxially stretched nylon film with a thickness of 25 μm is used, the aluminum foil is a 40 μm metal foil, the unstretched polypropylene film with a thickness of 40 μm is used for the sealing film, and the total thickness of the exterior material is 111 μm. In the same manner as in Example 1, an exterior material for a power storage device was obtained.
<比較例2> <Comparative example 2>
除了基材層用薄膜，係使用厚度15μm之二軸延伸尼龍薄膜，金屬箔係使用35μm之鋁箔，外裝材之總厚度係86μm以外，其他皆與實施例1相同，得到蓄電裝置用外裝材。 Except for the film for the substrate layer, a biaxially stretched nylon film with a thickness of 15 μm, an aluminum foil with a thickness of 35 μm, and a total thickness of the exterior material of 86 μm were used. material.
<比較例3> <Comparative example 3>
除了基材層用薄膜，係使用厚度12μm之二軸延伸PET樹脂薄膜，金屬箔係使用30μm之鋁箔，密封薄膜係使用厚度25μm之無延伸聚丙烯薄膜，外裝材之總厚度係73μm以外，其他皆與實施例1相同，得到蓄電裝置用外裝材。 Except for the film for the substrate layer, a biaxially stretched PET resin film with a thickness of 12 μm, an aluminum foil with a thickness of 30 μm, a non-stretched polypropylene film with a thickness of 25 μm, and a total thickness of the exterior material are 73 μm. Otherwise, it was the same as Example 1, and obtained the exterior material for electrical storage devices.
<比較例4> <Comparative Example 4>
除了基材層用薄膜，係使用厚度6μm之二軸延伸PET樹脂薄膜，金屬箔係使用20μm之鋁箔，密封薄膜係使用厚度20μm之無延伸聚丙烯薄膜，外裝材之總厚度係52μm以外，其他皆與實施例1相同，得到蓄電裝置用外裝材。 Except for the film for the base material layer, a biaxially stretched PET resin film with a thickness of 6 μm is used. The aluminum foil is 20 μm for the metal foil. The non-stretched polypropylene film with a thickness of 20 μm is used for the sealing film. The total thickness of the exterior material is 52 μm. Otherwise, it was the same as Example 1, and obtained the exterior material for electrical storage devices.
<比較例5> <Comparative example 5>
除了基材層用薄膜，係使用厚度10μm之二軸延伸PET樹脂薄膜/厚度40μm之二軸延伸尼龍薄膜之共押出積層薄膜(配置為較PET樹脂薄膜外側)，金屬箔係使用20μm之鋁箔，外裝材之總厚度係109μm以外，其他皆與實施例1相同，得到蓄電裝置用外裝材。 Except for the film for the substrate layer, a biaxially stretched PET resin film with a thickness of 10 μm / a biaxially stretched nylon film with a thickness of 40 μm is co-extruded a laminated film (configured more than the outside of the PET resin film). The metal foil is an aluminum foil with a thickness of 20 μm. The total thickness of the exterior material was other than 109 μm, and the rest were the same as in Example 1 to obtain an exterior material for a power storage device.
<比較例6> <Comparative Example 6>
除了基材層用薄膜，係使用楊氏模數為4.8GPa之厚度50μm之二軸延伸PET樹脂薄膜(與實施例1所使用之二軸延伸PET樹脂薄膜之低聚物含有率相異，楊氏模數亦相異)以外，其他皆與實施例1相同，得到蓄電裝置用外裝材。 Except for the film for the substrate layer, a biaxially stretched PET resin film having a Young's modulus of 4.8 GPa and a thickness of 50 μm was used (the oligomer content of the biaxially stretched PET resin film used in Example 1 was different from Except for the Modulus of Modulus, the rest were the same as in Example 1 to obtain an exterior material for a power storage device.
<比較例7> <Comparative Example 7>
除了基材層用薄膜，係使用厚度55μm之二軸延伸PET樹脂薄膜，金屬箔係使用15μm之鋁箔，外裝材之總厚度係106μm以外，其他皆與實施例1相同，得到蓄電裝置用外裝材。 Except for the film for the substrate layer, a biaxially stretched PET resin film with a thickness of 55 μm, an aluminum foil with a thickness of 15 μm, and a total thickness of the exterior material of 106 μm were used. Loading material.
<楊氏模數之測定方法> <Method for measuring Young's modulus>
對於在蓄電裝置用外裝材之製造中所使用之積層前之各基材層用薄 膜，以JIS K7127(1999)為基準，在試料長度100mm，試料寬15mm，評點間距離50mm，引伸速度200mm/分之條件下，使用引伸試驗機對於試料片(基材層用薄膜之試料片)進行引伸測定所得「應力-應變曲線(SS曲線)」算出楊氏模數(單位：GPa)。前述應力-應變曲線中「直線部分之接線之傾斜」為楊氏模數。引伸試驗機係使用島津製作所製之「Strograph(AGS-5kNX)」。前述「楊氏模數」之詞，係與ASTM-D-882定義之楊氏模數同義。 For the film for each base material layer before the lamination used in the manufacture of exterior materials for power storage devices, based on JIS K7127 (1999), the sample length is 100 mm, the sample width is 15 mm, the distance between the comments is 50 mm, and the extension speed is 200 mm. Under the condition of 1 / min, the "stress-strain curve (SS curve)" obtained by performing an extension measurement on a sample piece (a sample piece of a film for a substrate layer) using an extension tester was used to calculate a Young's modulus (unit: GPa). The “tilt of the straight line connection” in the aforementioned stress-strain curve is the Young's modulus. The extension tester used "Strograph (AGS-5kNX)" manufactured by Shimadzu Corporation. The term "Young's modulus" is synonymous with the Young's modulus as defined in ASTM-D-882.
又，實施例5、6及比較例5，基材層用薄膜係使用積層薄膜，此時，係在積層薄膜狀態下測定上述楊氏模數。 In Examples 5, 6 and Comparative Example 5, a laminated film was used as the film for the base material layer. In this case, the Young's modulus was measured in the state of the laminated film.
<耐彎折性評估法> <Bend resistance evaluation method>
關於各蓄電裝置用外裝材，個別準備2枚下述尺寸之試驗片，根據JIS P8115(2001年)之耐折強度試驗法進行彎折試驗。 For each exterior material for a power storage device, two test pieces of the following sizes were individually prepared, and a bending test was performed in accordance with the flexural strength test method of JIS P8115 (2001).
試驗機器：MIT TYPE FOLDING ENDURANCE TESTER(東洋精機製作所公司製) Test equipment: MIT TYPE FOLDING ENDURANCE TESTER (manufactured by Toyo Seiki Seisakusho)
試驗片尺寸：10mm寬×150mm長 Test piece size: 10mm wide × 150mm long
荷重：1.75kg Load: 1.75kg
彎折速度：175往返/分(「彎折回復原狀」計數為1往返) Bending speed: 175 round trips / minute ("Bending return to original state" counts as 1 round trip)
彎折角度：90° Bending angle: 90 °
彎折前端半徑：0.5R Bending front radius: 0.5R
彎折次數：750次、1500次 Bending times: 750 times, 1500 times
以上述之試驗條件等，對於其中一者之試驗片進行750次之彎折試驗，另一者之試驗片進行1500次之彎折試驗，以肉眼觀察個別之試驗後之蓄電裝置用外裝材之狀態，並根據下述判定基準進行評估。 Based on the test conditions described above, one of the test pieces was subjected to a bending test of 750 times, and the other test piece was subjected to a bending test of 1,500 times. The exterior materials for the power storage device after the individual tests were observed with the naked eye The condition is evaluated based on the following judgment criteria.
(判定基準) (Judgment criteria)
「◎」…外裝材未見針孔、裂痕等之缺陷部。 "◎" ... There are no defective parts such as pinholes or cracks in the exterior material.
「○」…雖彎曲位置可見薄皺摺痕，但外裝材未見針孔、裂痕等之缺陷部。 "○" ... Although thin wrinkles are visible in the bending position, there are no defective parts such as pinholes and cracks in the exterior.
「△」…發生以下3種現象中至少1以上之現象。 "△" ... At least one of the following three phenomena occurs.
．外裝材之金屬箔層發生破裂 ． The metal foil layer of the exterior material is cracked
．基材層發生針孔 ． Pinholes in the substrate layer
．密封層發生針孔 ． Pinhole
「×」…外裝材產生破斷。 "×" ... The exterior material is broken.
由表1可明顯得知，本發明之實施例1~7之蓄電裝置用外裝材，雖係薄型之外裝材，但耐彎折性優異。 It is clear from Table 1 that although the exterior materials for power storage devices according to Examples 1 to 7 of the present invention are thin exterior materials, they have excellent bending resistance.
相對於此，脫離本發明之規定範圍之比較例1~7，耐彎折性差劣。 On the other hand, Comparative Examples 1 to 7 which deviate from the prescribed range of the present invention have poor bending resistance.
本發明之蓄電裝置用外裝材，作為具體例，係可用於例如： As a specific example, the exterior material for a power storage device of the present invention can be used, for example:
．鋰蓄電池(鋰離子電池、鋰聚物電池等)等之蓄電裝置 ． Power storage devices such as lithium batteries (lithium ion batteries, lithium polymer batteries, etc.)
．鋰離子電容器 ． Lithium ion capacitor
．雙電層電容器 ． Electric double layer capacitor
．全固體電池 ． All solid battery
等之各種蓄電裝置之外裝材。此外，本發明之蓄電裝置用外裝材，即使厚度係薄型構成，耐彎折性等之彎曲耐性仍優異，故可合適地作為薄型電池(卡片型電池等)用之外裝材。 And other external storage materials. In addition, the exterior material for a power storage device of the present invention is excellent in bending resistance such as bending resistance even if the thickness is a thin structure, and thus can be suitably used as an exterior material for a thin battery (card-type battery, etc.).
此外，本發明之蓄電裝置，可列舉例如上述例示之各種蓄電裝置等。其中，可合適地作為薄型電池(卡片型電池等)。 Examples of the power storage device of the present invention include the various power storage devices exemplified above. Among these, it is suitable as a thin battery (card-type battery, etc.).
本申請案，係伴隨著在2017年3月9日提出申請的日本專利申請案的特願2017-44851號的優先權主張，其揭示內容直接構成本申請案的一部分。 The present application is a priority claim accompanying Japanese Patent Application No. 2017-44851 filed on March 9, 2017, and the disclosure thereof directly forms part of the present application.
在此所使用的用語及說明，係用以說明本發明的實施形態所使用，但本發明並不限定於此。在本發明所請求的範圍內的各種變形亦應 被理解為係可被接受的。 The terms and descriptions used herein are used to describe embodiments of the present invention, but the present invention is not limited thereto. Various modifications within the scope of the present invention should also be construed as acceptable.
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| JP2017044851A JP6932523B2 (en) | 2017-03-09 | 2017-03-09 | Exterior materials for power storage devices and power storage devices |
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| JP7234635B2 (en) * | 2019-01-08 | 2023-03-08 | 凸版印刷株式会社 | Exterior materials for power storage devices |
| KR102308471B1 (en) * | 2019-05-08 | 2021-10-05 | 에스케이씨 주식회사 | Polyester film and flexible display apparatus comprising same |
| JP7408979B2 (en) * | 2019-09-26 | 2024-01-09 | 大日本印刷株式会社 | Packaging materials and pouches |
| JP2021054418A (en) * | 2019-09-26 | 2021-04-08 | 大日本印刷株式会社 | Packaging material and pouch |
| DE112021006466T5 (en) * | 2020-12-16 | 2023-10-05 | Resonac Packaging Corporation | Housing for energy storage device and energy storage device |
| JP7332072B1 (en) | 2021-10-07 | 2023-08-23 | 大日本印刷株式会社 | Exterior material for power storage device, manufacturing method thereof, and power storage device |
| JP2023150121A (en) * | 2022-03-31 | 2023-10-16 | 凸版印刷株式会社 | Sheath material for all-solid battery, and all-solid battery |
| WO2024040134A1 (en) * | 2022-08-18 | 2024-02-22 | Ocella, Inc. | Flexible packaging for use in energy storage devices, and method of manufacture thereof |
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| JP4374960B2 (en) * | 2003-09-19 | 2009-12-02 | 凸版印刷株式会社 | Exterior materials for lithium-ion batteries |
| TWI501446B (en) * | 2010-09-08 | 2015-09-21 | Toppan Printing Co Ltd | Exterior material for lithium-ion battery |
| JP5845413B2 (en) | 2012-02-07 | 2016-01-20 | パナソニックＩｐマネジメント株式会社 | Electronic device with thin battery |
| JP6015194B2 (en) * | 2012-07-25 | 2016-10-26 | 油化電子株式会社 | Battery exterior laminate film and method for producing the same |
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| JP6519209B2 (en) * | 2015-02-04 | 2019-05-29 | 凸版印刷株式会社 | Storage material for power storage device |
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| JP6554348B2 (en) * | 2015-07-13 | 2019-07-31 | 昭和電工パッケージング株式会社 | Exterior material for storage device and storage device |
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