JP6979847B2 - Exterior materials for power storage devices and power storage devices - Google Patents

Exterior materials for power storage devices and power storage devices Download PDF

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JP6979847B2
JP6979847B2 JP2017200064A JP2017200064A JP6979847B2 JP 6979847 B2 JP6979847 B2 JP 6979847B2 JP 2017200064 A JP2017200064 A JP 2017200064A JP 2017200064 A JP2017200064 A JP 2017200064A JP 6979847 B2 JP6979847 B2 JP 6979847B2
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power storage
storage device
exterior material
polyamide resin
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JP2019075260A (en
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圭太郎 川北
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Showa Denko Packaging Co Ltd
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Priority to TW107129820A priority patent/TWI787336B/en
Priority to CN201811045725.7A priority patent/CN109671875B/en
Priority to CN202310433594.4A priority patent/CN116345027A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—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
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only 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
    • H01M50/116—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
    • B32B15/043—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 metal
    • 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
    • B32B15/088—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 polyamides
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (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)

Description

本発明は、スマートフォン、タブレット等の携帯機器に使用される電池やコンデンサ、ハイブリッド自動車、電気自動車、風力発電、太陽光発電、夜間電気の蓄電用に使用される電池やコンデンサ等の蓄電デバイス用の外装材および該外装材で外装された蓄電デバイスに関する。 The present invention is for storage devices such as batteries and capacitors used in portable devices such as smartphones and tablets, hybrid vehicles, electric vehicles, wind power generation, solar power generation, and nighttime electricity storage. The present invention relates to an exterior material and a power storage device exteriorized by the exterior material.

なお、本明細書および特許請求の範囲において、「融解熱分布曲線」とは、熱流束型ＤＳＣ（示差走査熱量計）を用いて最初の昇温（first run）で測定される、温度を横軸、熱流を縦軸にした融解熱分布曲線を意味する。 In the present specification and the scope of the patent claim, the "heat distribution curve of fusion" means the temperature measured at the first run using a heat flux type DSC (differential scanning calorimetry). It means a heat distribution curve with the axis and heat flow on the vertical axis.

リチウムイオン２次電池は、例えばノートパソコン、ビデオカメラ、携帯電話等の電源として広く用いられている。このリチウムイオン２次電池としては、電池本体部（正極、負極及び電解質を含む本体部）の周囲を外装材で包囲した構成のものが用いられている。このような外装材としては、例えば、延伸ポリアミド系樹脂からなる最外層、アルミニウム箔等からなるバリア層、熱融着性樹脂からなる最内層がこの順に積層された構成のものが公知である（特許文献１参照）。 Lithium-ion secondary batteries are widely used as a power source for, for example, notebook computers, video cameras, mobile phones and the like. As the lithium ion secondary battery, a battery having a structure in which the periphery of the battery main body (main body including the positive electrode, the negative electrode and the electrolyte) is surrounded by an exterior material is used. As such an exterior material, for example, a structure in which an outermost layer made of a stretched polyamide resin, a barrier layer made of an aluminum foil or the like, and an innermost layer made of a heat-sealing resin are laminated in this order is known (). See Patent Document 1).

そして、電池は、電池本体部が一対の外装材で挟み込まれて前記一対の外装材の相互の内側層の周縁部同士が熱融着接合（ヒートシール）されることによって封止されて構成されている。このようなヒートシール接合で十分に封止されることで、電解液の漏出を防止できる。 The battery is configured by sandwiching the battery main body with a pair of exterior materials and heat-sealing the peripheral edges of the inner layers of the pair of exterior materials to each other. ing. By sufficiently sealing with such a heat-sealed joint, leakage of the electrolytic solution can be prevented.

特開２００１−９３４８２号公報（請求項１、３等）Japanese Unexamined Patent Publication No. 2001-93482 (claims 1, 3, etc.)

ところで、上記構成の外装材で最外層を構成するポリアミド樹脂は、深絞り成形した際の成形深さをより深くできる上に、耐突き刺し性にも優れているという利点がある一方で、融点が低く、低融解成分が多いため、２００℃以上の高温度でヒートシールを行った際にこのポリアミド樹脂層（最外層）がシールバーに付着してしまうというシール不良が起こるために生産性が悪いという問題があった。 By the way, the polyamide resin constituting the outermost layer of the exterior material having the above-mentioned structure has an advantage that the molding depth at the time of deep drawing can be deepened and also has excellent piercing resistance, but has a melting point. Since it is low and has a large amount of low melting components, productivity is poor due to sealing defects such as the polyamide resin layer (outermost layer) adhering to the seal bar when heat sealing is performed at a high temperature of 200 ° C or higher. There was a problem.

このようなシール不良の発生を防止するためにポリアミド樹脂層の外面にさらにポリエステル樹脂層を積層する構成も検討されたが、コスト増大を来すし、成形性が低下するという問題があった。 In order to prevent the occurrence of such sealing defects, a configuration in which a polyester resin layer is further laminated on the outer surface of the polyamide resin layer has been studied, but there is a problem that the cost increases and the moldability deteriorates.

また、シールバーに付着するのを防止するべくシールバーの表面にフッ素樹脂コーティングを施したりされているが、フッ素樹脂コーティングを行うことにより熱伝導率が低下して、ヒートシール工程のサイクル時間が増大する上に、ヒートシール温度をより高温に設定しなければならなくなるという問題があった。 In addition, a fluororesin coating is applied to the surface of the seal bar to prevent it from adhering to the seal bar. However, the fluororesin coating reduces the thermal conductivity and the cycle time of the heat seal process. In addition to the increase, there is a problem that the heat seal temperature must be set to a higher temperature.

本発明は、かかる技術的背景に鑑みてなされたものであって、ヒートシールを行う際に外装材の外側層のポリアミド樹脂がシールバーに付着するのを抑止できて生産性を向上させることのできる蓄電デバイス用外装材および該外装材で外装された蓄電デバイスを提供することを目的とする。 The present invention has been made in view of the above technical background, and can prevent the polyamide resin on the outer layer of the exterior material from adhering to the seal bar when heat-sealing, thereby improving productivity. It is an object of the present invention to provide an exterior material for a power storage device that can be used and a power storage device that is covered with the exterior material.

前記目的を達成するために、本発明は以下の手段を提供する。 In order to achieve the above object, the present invention provides the following means.

［１］外側層としてのポリアミド樹脂層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層と、を含む蓄電デバイス用外装材であって、
前記ポリアミド樹脂は、示差走査熱量測定で得られる融解熱分布曲線において、該融解熱分布曲線とベースラインとで取り囲まれる全体の面積を「Ｘ」とし、２１０℃〜２２０℃の範囲における融解熱分布曲線とベースラインとの間の面積を「Ｙ」としたとき、０≦Ｙ／Ｘ≦０．３０の関係式を満たしているポリアミド樹脂であることを特徴とする蓄電デバイス用外装材。 [1] An exterior material for a power storage device including a polyamide resin layer as an outer layer, a heat-sealing resin layer as an inner layer, and a metal foil layer arranged between both layers.
In the heat of fusion distribution curve obtained by differential scanning calorimetry, the entire area surrounded by the heat of fusion distribution curve and the baseline is "X", and the heat of fusion is distributed in the range of 210 ° C to 220 ° C. An exterior material for a power storage device, which is a polyamide resin satisfying the relational expression of 0 ≦ Y / X ≦ 0.30 when the area between the curve and the baseline is “Y”.

［２］前記ポリアミド樹脂は、示差走査熱量測定で得られる融解熱分布曲線において、該融解熱分布曲線とベースラインとで取り囲まれる全体の面積を「Ｘ」とし、２１０℃〜２１５℃の範囲における融解熱分布曲線とベースラインとの間の面積を「Ｗ」としたとき、０≦Ｗ／Ｘ≦０．１０の関係式を満たしているポリアミド樹脂である前項１に記載の蓄電デバイス用外装材。 [2] In the heat of fusion distribution curve obtained by differential scanning calorimetry, the entire area surrounded by the heat of fusion distribution curve and the baseline is defined as "X", and the polyamide resin is in the range of 210 ° C to 215 ° C. The exterior material for a power storage device according to item 1 above, which is a polyamide resin satisfying the relational expression of 0 ≦ W / X ≦ 0.10. When the area between the heat of fusion distribution curve and the baseline is “W”. ..

［３］蓄電デバイス本体部と、
前項１または２に記載の蓄電デバイス用外装材を含む外装部材とを備え、
前記蓄電デバイス本体部が、前記外装部材で外装されていることを特徴とする蓄電デバイス。 [3] The main body of the power storage device and
It is provided with an exterior member including the exterior material for the power storage device according to the above item 1 or 2.
A power storage device characterized in that the power storage device main body is covered with the exterior member.

［１］の発明では、外側層として０≦Ｙ／Ｘ≦０．３０の関係式を満たしているポリアミド樹脂が用いられているから、外装材のヒートシールを行う際に外装材の外側層のポリアミド樹脂がシールバーに付着するのを抑止できて生産性を向上させることができる。 In the invention of [1], since the polyamide resin satisfying the relational expression of 0 ≦ Y / X ≦ 0.30 is used as the outer layer, the outer layer of the exterior material is heat-sealed when the exterior material is heat-sealed. It is possible to prevent the polyamide resin from adhering to the seal bar and improve productivity.

［２］の発明では、外側層として更に０≦Ｗ／Ｘ≦０．１０の関係式を満たしているポリアミド樹脂が用いられているから、外装材のヒートシールを行う際に外装材の外側層のポリアミド樹脂がシールバーに付着するのをより一層抑止できて生産性をさらに向上させることができる。 In the invention of [2], since the polyamide resin satisfying the relational expression of 0 ≦ W / X ≦ 0.10 is further used as the outer layer, the outer layer of the exterior material is used when the exterior material is heat-sealed. The polyamide resin of No. 1 can be further suppressed from adhering to the seal bar, and the productivity can be further improved.

［３］の発明では、上記構成の蓄電デバイス用外装材を含む外装部材で外装されているので、生産性に優れた蓄電デバイスが提供される。 In the invention of [3], since the exterior is covered with the exterior member including the exterior material for the energy storage device having the above configuration, the energy storage device having excellent productivity is provided.

本発明に係る蓄電デバイス用外装材の一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of the exterior material for a power storage device which concerns on this invention. 本発明に係る蓄電デバイスの一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of the power storage device which concerns on this invention. 図２の蓄電デバイスを構成する外装材（平面状のもの）、蓄電デバイス本体部及び外装ケース（立体形状に成形された成形体）をヒートシールする前の分離した状態で示す斜視図である。FIG. 2 is a perspective view showing an exterior material (planar shape) constituting the power storage device, a power storage device main body, and an exterior case (molded body molded into a three-dimensional shape) in a separated state before heat sealing. 実施例２で使用したナイロンＢについて熱流束型ＤＳＣを用いて最初の昇温で測定された融解熱分布曲線を示すグラフである。この融解熱分布曲線から、ナイロンＢの（Ｙ／Ｘ）値が０．１９であることがわかる。It is a graph which shows the fusion heat distribution curve measured by the heat flux type DSC for the nylon B used in Example 2 at the first temperature rise. From this heat of fusion distribution curve, it can be seen that the (Y / X) value of nylon B is 0.19. 比較例１で使用したナイロンＤについて熱流束型ＤＳＣを用いて最初の昇温で測定された融解熱分布曲線を示すグラフである。この融解熱分布曲線から、ナイロンＤの（Ｙ／Ｘ）値が０．４３であることがわかる。It is a graph which shows the fusion heat distribution curve measured by the heat flux type DSC for the nylon D used in the comparative example 1 at the first temperature rise. From this heat of fusion distribution curve, it can be seen that the (Y / X) value of nylon D is 0.43.

本発明に係る蓄電デバイス用外装材１の一実施形態を図１に示す。この蓄電デバイス用外装材１は、リチウムイオン２次電池ケース用として用いられるものである。 FIG. 1 shows an embodiment of the exterior material 1 for a power storage device according to the present invention. The exterior material 1 for a power storage device is used for a lithium ion secondary battery case.

前記蓄電デバイス用外装材１は、金属箔層４の一方の面に第１接着剤層５を介してポリアミド樹脂層（外側層）２が積層一体化されると共に、前記金属箔層４の他方の面に第２接着剤層６を介して熱融着性樹脂層（内側層）３が積層一体化された構成からなる。 In the exterior material 1 for a power storage device, the polyamide resin layer (outer layer) 2 is laminated and integrated on one surface of the metal foil layer 4 via the first adhesive layer 5, and the other of the metal foil layer 4 is laminated. The heat-bondable resin layer (inner layer) 3 is laminated and integrated on the surface of the surface via the second adhesive layer 6.

本発明に係る蓄電デバイス用外装材１では、前記ポリアミド樹脂層（外側層）２は、示差走査熱量測定で得られる融解熱分布曲線において、該融解熱分布曲線とベースラインとで取り囲まれる全体の面積を「Ｘ」とし、２１０℃〜２２０℃の範囲における融解熱分布曲線とベースラインとの間の面積を「Ｙ」としたとき、０≦Ｙ／Ｘ≦０．３０の関係式を満たしているポリアミド樹脂で構成される。このように外側層２として、０≦Ｙ／Ｘ≦０．３０の関係式を満たしているポリアミド樹脂が用いられていることにより、外装材１のヒートシールを行う際に外装材の外側層２のポリアミド樹脂がシールバーに付着するのを抑止できて生産性を向上させることができる。 In the exterior material 1 for a power storage device according to the present invention, the polyamide resin layer (outer layer) 2 is surrounded by the heat of fusion distribution curve and the baseline in the heat of fusion distribution curve obtained by differential scanning calorimetry. When the area is "X" and the area between the heat of fusion distribution curve and the baseline in the range of 210 ° C to 220 ° C is "Y", the relational expression of 0≤Y / X≤0.30 is satisfied. It is composed of a polyamide resin. As described above, since the polyamide resin satisfying the relational expression of 0 ≦ Y / X ≦ 0.30 is used as the outer layer 2, the outer layer 2 of the exterior material 2 is used when the exterior material 1 is heat-sealed. It is possible to prevent the polyamide resin from adhering to the seal bar and improve productivity.

また、前記ポリアミド樹脂層（外側層）２は、示差走査熱量測定で得られる融解熱分布曲線において、該融解熱分布曲線とベースラインとで取り囲まれる全体の面積を「Ｘ」とし、２１０℃〜２１５℃の範囲における融解熱分布曲線とベースラインとの間の面積を「Ｗ」としたとき、０≦Ｗ／Ｘ≦０．１０の関係式を満たしているポリアミド樹脂で構成されるのが好ましい。この場合には、外装材のヒートシールを行う際に外装材の外側層２のポリアミド樹脂がシールバーに付着するのをより一層抑止できて生産性をさらに向上させることができる。 Further, in the heat of fusion distribution curve obtained by differential scanning calorimetry, the entire area surrounded by the heat of fusion distribution curve and the baseline of the polyamide resin layer (outer layer) 2 is "X", and the temperature is from 210 ° C. to 210 ° C. When the area between the heat of fusion distribution curve and the baseline in the range of 215 ° C. is "W", it is preferably composed of a polyamide resin satisfying the relational expression of 0 ≦ W / X ≦ 0.10. .. In this case, when the exterior material is heat-sealed, the polyamide resin of the outer layer 2 of the exterior material can be further suppressed from adhering to the seal bar, and the productivity can be further improved.

前記ポリアミド樹脂層２を構成するポリアミド樹脂としては、前記「０≦Ｙ／Ｘ≦０．３０」の関係式を満たしているポリアミド樹脂であればよく、例えば、前記関係式を満たす６ナイロンフィルム、６，６ナイロンフィルム、ＭＸＤナイロンフィルムなどが挙げられる。前記ポリアミド樹脂層２は、単層で形成されていても良いし、複層で形成されていても良い。 The polyamide resin constituting the polyamide resin layer 2 may be any polyamide resin satisfying the relational expression "0≤Y / X≤0.30", and for example, a 6 nylon film satisfying the relational expression. Examples thereof include 6,6 nylon films and MXD nylon films. The polyamide resin layer 2 may be formed of a single layer or a plurality of layers.

前記ポリアミド樹脂層２の厚さは、８μｍ〜５０μｍであるのが好ましい。上記好適下限値以上に設定することで外装材として十分な強度を確保できると共に、上記好適上限値以下に設定することで張り出し成形、絞り成形等の成形時の応力を小さくできて成形性を向上させることができる。中でも、前記ポリアミド樹脂層２の厚さは、１２μｍ〜２５μｍであるのが特に好ましい。 The thickness of the polyamide resin layer 2 is preferably 8 μm to 50 μm. By setting it to the above-mentioned suitable lower limit value or more, sufficient strength as an exterior material can be secured, and by setting it to the above-mentioned suitable upper limit value or less, stress during forming such as overhang molding and draw forming can be reduced and formability is improved. Can be made to. Above all, the thickness of the polyamide resin layer 2 is particularly preferably 12 μm to 25 μm.

前記熱融着性樹脂層（内側層）３は、リチウムイオン二次電池等で用いられる腐食性の強い電解液などに対しても優れた耐薬品性を具備させると共に、外装材にヒートシール性を付与する役割を担うものである。 The heat-sealing resin layer (inner layer) 3 has excellent chemical resistance to a highly corrosive electrolytic solution used in a lithium ion secondary battery or the like, and has heat-sealing properties for the exterior material. It plays the role of granting.

前記熱融着性樹脂層３としては、特に限定されるものではないが、熱融着性樹脂無延伸フィルム層であるのが好ましい。前記熱融着性樹脂層無延伸フィルム層３は、特に限定されるものではないが、ポリエチレン、ポリプロピレン、オレフィン系共重合体、これらの酸変性物およびアイオノマーからなる群より選ばれた少なくとも１種の熱融着性樹脂からなる無延伸フィルムにより構成されるのが好ましい。なお、前記熱融着性樹脂層３は、単層であってもよいし、複層であってもよい。 The heat-sealing resin layer 3 is not particularly limited, but is preferably a heat-sealing resin non-stretched film layer. The heat-bondable resin layer non-stretched film layer 3 is not particularly limited, but is at least one selected from the group consisting of polyethylene, polypropylene, olefin-based copolymers, acid-modified products thereof, and ionomers. It is preferably composed of a non-stretched film made of the heat-sealing resin of. The heat-sealing resin layer 3 may be a single layer or a plurality of layers.

前記熱融着性樹脂層３の厚さは、１０μｍ〜８０μｍに設定されるのが好ましい。１０μｍ以上とすることでピンホールの発生を十分に防止できると共に、８０μｍ以下に設定することで樹脂使用量を低減できてコスト低減を図り得る。中でも、前記熱融着性樹脂層３の厚さは２５μｍ〜５０μｍに設定されるのが特に好ましい。 The thickness of the heat-sealing resin layer 3 is preferably set to 10 μm to 80 μm. By setting it to 10 μm or more, the occurrence of pinholes can be sufficiently prevented, and by setting it to 80 μm or less, the amount of resin used can be reduced and the cost can be reduced. Above all, it is particularly preferable that the thickness of the heat-sealing resin layer 3 is set to 25 μm to 50 μm.

前記熱融着性樹脂層３に滑剤を含有せしめてもよい。前記滑剤としては、特に限定されるものではないが、脂肪酸アミドが好適に用いられる。前記脂肪酸アミドとしては、特に限定されるものではないが、例えば、飽和脂肪酸アミド、不飽和脂肪酸アミド、置換アミド、メチロールアミド、飽和脂肪酸ビスアミド、不飽和脂肪酸ビスアミド、脂肪酸エステルアミド、芳香族系ビスアミド等が挙げられる。 The lubricant may be contained in the heat-sealing resin layer 3. The lubricant is not particularly limited, but a fatty acid amide is preferably used. The fatty acid amide is not particularly limited, but for example, saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylol amide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, fatty acid ester amide, aromatic bisamide and the like. Can be mentioned.

前記金属箔層４は、外装材１に酸素や水分の侵入を阻止するガスバリア性を付与する役割を担うものである。前記金属箔層４としては、特に限定されるものではないが、例えば、アルミニウム箔、ＳＵＳ箔（ステンレス箔）、銅箔等が挙げられ、アルミニウム箔が一般的に用いられる。前記金属箔層４の厚さは、５μｍ〜５０μｍであるのが好ましい。５μｍ以上であることで金属箔を製造する際の圧延時のピンホール発生を防止できると共に、５０μｍ以下であることで張り出し成形、絞り成形等の成形時の応力を小さくできて成形性を向上させることができる。中でも、前記金属箔層４の厚さは、１０μｍ〜４０μｍであるのが特に好ましい。 The metal foil layer 4 plays a role of imparting a gas barrier property to prevent the intrusion of oxygen and moisture into the exterior material 1. The metal foil layer 4 is not particularly limited, and examples thereof include aluminum foil, SUS foil (stainless foil), copper foil, and the like, and aluminum foil is generally used. The thickness of the metal foil layer 4 is preferably 5 μm to 50 μm. When it is 5 μm or more, it is possible to prevent the occurrence of pinholes during rolling when manufacturing a metal foil, and when it is 50 μm or less, it is possible to reduce the stress during forming such as overhang forming and draw forming, and improve the formability. be able to. Above all, the thickness of the metal foil layer 4 is particularly preferably 10 μm to 40 μm.

前記金属箔層４は、少なくとも内側の面（第２接着剤層６側の面）に化成処理が施されているのが好ましい。このような化成処理が施されていることによって内容物（電池の電解液等）による金属箔表面の腐食を十分に防止できる。例えば次のような処理をすることによって金属箔に化成処理を施す。即ち、例えば、脱脂処理を行った金属箔の表面に、
１）リン酸と、
クロム酸と、
フッ化物の金属塩及びフッ化物の非金属塩からなる群より選ばれる少なくとも１種の化合物と、を含む混合物の水溶液
２）リン酸と、
アクリル系樹脂、キトサン誘導体樹脂及びフェノール系樹脂からなる群より選ばれる少なくとも１種の樹脂と、
クロム酸及びクロム（III）塩からなる群より選ばれる少なくとも１種の化合物と、を含む混合物の水溶液
３）リン酸と、
アクリル系樹脂、キトサン誘導体樹脂及びフェノール系樹脂からなる群より選ばれる少なくとも１種の樹脂と、
クロム酸及びクロム（III）塩からなる群より選ばれる少なくとも１種の化合物と、
フッ化物の金属塩及びフッ化物の非金属塩からなる群より選ばれる少なくとも１種の化合物と、を含む混合物の水溶液
上記１）〜３）のうちのいずれかの水溶液を塗工した後、乾燥することにより、化成処理を施す。 It is preferable that at least the inner surface (the surface on the second adhesive layer 6 side) of the metal foil layer 4 is subjected to chemical conversion treatment. By performing such a chemical conversion treatment, it is possible to sufficiently prevent corrosion of the metal foil surface due to the contents (electrolyte solution of the battery, etc.). For example, the metal foil is subjected to chemical conversion treatment by performing the following treatment. That is, for example, on the surface of a metal foil that has been degreased,
1) Phosphoric acid and
With chromic acid,
An aqueous solution of a mixture containing at least one compound selected from the group consisting of a metal salt of fluoride and a non-metal salt of fluoride 2) Phosphoric acid.
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins, and
An aqueous solution of a mixture containing at least one compound selected from the group consisting of chromic acid and a chromium (III) salt 3) phosphoric acid.
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins, and
At least one compound selected from the group consisting of chromic acid and chromium (III) salt, and
An aqueous solution of a mixture containing at least one compound selected from the group consisting of a metal salt of fluoride and a non-metal salt of fluoride An aqueous solution of any one of 1) to 3) above is applied and then dried. By doing so, the chemical conversion process is performed.

前記化成皮膜は、クロム付着量（片面当たり）として０．１ｍｇ／ｍ2〜５０ｍｇ／ｍ2が好ましく、特に２ｍｇ／ｍ2〜２０ｍｇ／ｍ2が好ましい。 The conversion coating, chromium coating weight preferably is 0.1mg / m 2 ~50mg / m 2 as a (per one surface), in particular 2mg / m 2 ~20mg / m 2 preferred.

前記第１接着剤層５としては、特に限定されるものではないが、例えば、ポリウレタン接着剤層、ポリエステルポリウレタン接着剤層、ポリエーテルポリウレタン接着剤層等が挙げられる。前記第１接着剤層５の厚さは、１μｍ〜５μｍに設定されるのが好ましい。中でも、外装材の薄膜化、軽量化の観点から、前記第１接着剤層５の厚さは、１μｍ〜３μｍに設定されるのが特に好ましい。 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. Above all, from the viewpoint of thinning and weight reduction of the exterior material, it is particularly preferable that the thickness of the first adhesive layer 5 is set to 1 μm to 3 μm.

前記第２接着剤層６としては、特に限定されるものではないが、例えば、上記第１接着剤層５として例示したものも使用できるが、電解液による膨潤の少ないポリオレフィン系接着剤を使用するのが好ましい。前記第２接着剤層６の厚さは、１μｍ〜５μｍに設定されるのが好ましい。中でも、外装材の薄膜化、軽量化の観点から、前記第２接着剤層６の厚さは、１μｍ〜３μｍに設定されるのが特に好ましい。 The second adhesive layer 6 is not particularly limited, and for example, the one exemplified as the first adhesive layer 5 can be used, but a polyolefin-based adhesive with less swelling due to the electrolytic solution is used. Is preferable. The thickness of the second adhesive layer 6 is preferably set to 1 μm to 5 μm. Above all, from the viewpoint of thinning and weight reduction of the exterior material, it is particularly preferable that the thickness of the second adhesive layer 6 is set to 1 μm to 3 μm.

本発明の蓄電デバイス用外装材１を成形（深絞り成形、張り出し成形等）することにより、外装ケース（電池ケース等）１０を得ることができる（図３参照）。なお、本発明の外装材１は、成形に供されずにそのまま使用することもできる（図３参照）。 By molding (deep drawing molding, overhang molding, etc.) the exterior material 1 for a power storage device of the present invention, an exterior case (battery case, etc.) 10 can be obtained (see FIG. 3). The exterior material 1 of the present invention can be used as it is without being subjected to molding (see FIG. 3).

本発明の蓄電デバイス用外装材１を用いて構成された蓄電デバイス３０の一実施形態を図２に示す。この蓄電デバイス３０は、リチウムイオン２次電池である。本実施形態では、図２、３に示すように、外装材１を成形して得られた外装ケース１０と、平面状の外装材１とにより外装部材１５が構成されている。しかして、本発明の外装材１を成形して得られた外装ケース１０の収容凹部内に、略直方体形状の蓄電デバイス本体部（電気化学素子等）３１が収容され、該蓄電デバイス本体部３１の上に、本発明の外装材１が成形されることなくその熱融着性樹脂層３側を内方（下側）にして配置され、該平面状外装材１の熱融着性樹脂層３の周縁部と、前記外装ケース１０のフランジ部（封止用周縁部）２９の熱融着性樹脂層３とがヒートシールによりシール接合されて封止されることによって、本発明の蓄電デバイス３０が構成されている（図２、３参照）。なお、前記外装ケース１０の収容凹部の内側の表面は、熱融着性樹脂層３になっており、収容凹部の外面が基材層（外側層）２になっている（図３参照）。 FIG. 2 shows an embodiment of the power storage device 30 configured by using the exterior material 1 for the power storage device of the present invention. The power storage device 30 is a lithium ion secondary battery. In the present embodiment, as shown in FIGS. 2 and 3, the exterior member 15 is composed of the exterior case 10 obtained by molding the exterior material 1 and the flat exterior material 1. The storage device main body (electrochemical element or the like) 31 having a substantially rectangular shape is housed in the storage recess of the exterior case 10 obtained by molding the exterior material 1 of the present invention. The exterior material 1 of the present invention is arranged on the surface with the heat-sealing resin layer 3 side facing inward (lower side) without being molded, and the heat-sealing resin layer of the planar exterior material 1 is arranged. The power storage device of the present invention is sealed by sealing and sealing the peripheral edge portion 3 and the heat-sealing resin layer 3 of the flange portion (sealing peripheral edge portion) 29 of the outer case 10 by heat sealing. 30 is configured (see FIGS. 2 and 3). The inner surface of the accommodating recess of the outer case 10 is a heat-sealing resin layer 3, and the outer surface of the accommodating recess is a base material layer (outer layer) 2 (see FIG. 3).

図２において、３９は、前記外装材１の周縁部と、前記外装ケース１０のフランジ部（封止用周縁部）２９とが接合（溶着）されたヒートシール部である。なお、前記蓄電デバイス３０において、蓄電デバイス本体部３１に接続されたタブリードの先端部が、外装部材１５の外部に導出されているが、図示は省略している。 In FIG. 2, 39 is a heat-sealed portion in which the peripheral edge portion of the exterior material 1 and the flange portion (sealing peripheral edge portion) 29 of the exterior case 10 are joined (welded). In the power storage device 30, the tip of the tab lead connected to the power storage device main body 31 is led out to the outside of the exterior member 15, but the illustration is omitted.

前記蓄電デバイス本体部３１としては、特に限定されるものではないが、例えば、電池本体部、キャパシタ本体部、コンデンサ本体部等が挙げられる。 The power storage device main body 31 is not particularly limited, and examples thereof include a battery main body, a capacitor main body, and a capacitor main body.

前記ヒートシール部３９の幅は、０．５ｍｍ以上に設定するのが好ましい。０．５ｍｍ以上とすることで封止を確実に行うことができる。中でも、前記ヒートシール部３９の幅は、３ｍｍ〜１５ｍｍに設定するのが好ましい。 The width of the heat seal portion 39 is preferably set to 0.5 mm or more. By setting the thickness to 0.5 mm or more, sealing can be reliably performed. Above all, the width of the heat seal portion 39 is preferably set to 3 mm to 15 mm.

なお、上記実施形態では、外装部材１５が、外装材１を成形して得られた外装ケース１０と、平面状の外装材１と、からなる構成であったが（図２、３参照）、特にこのような組み合わせに限定されるものではなく、例えば、外装部材１５が、一対の平面状の外装材１からなる構成であってもよいし、或いは、一対の外装ケース１０からなる構成であってもよい。 In the above embodiment, the exterior member 15 is composed of an exterior case 10 obtained by molding the exterior material 1 and a flat exterior material 1 (see FIGS. 2 and 3). The combination is not particularly limited, and for example, the exterior member 15 may be composed of a pair of flat exterior materials 1, or may be composed of a pair of exterior cases 10. You may.

次に、本発明の具体的実施例について説明するが、本発明はこれら実施例のものに特に限定されるものではない。 Next, specific examples of the present invention will be described, but the present invention is not particularly limited to those of these examples.

＜原材料＞
［ナイロンＡ］…ＤＳＣ測定により得られた融解熱分布曲線より算出した「Ｙ／Ｘ」が０．１７であり、「Ｗ／Ｘ」が０．０３である６−ナイロン
［ナイロンＢ］…ＤＳＣ測定により得られた融解熱分布曲線（図４参照）より算出した「Ｙ／Ｘ」が０．１９であり、「Ｗ／Ｘ」が０．０５である６−ナイロン
［ナイロンＣ］…ＤＳＣ測定により得られた融解熱分布曲線より算出した「Ｙ／Ｘ」が０．２８であり、「Ｗ／Ｘ」が０．１１である６−ナイロン
［ナイロンＤ］…ＤＳＣ測定により得られた融解熱分布曲線（図５参照）より算出した「Ｙ／Ｘ」が０．４３であり、「Ｗ／Ｘ」が０．１１である６−ナイロン
［ナイロンＥ］…ＤＳＣ測定により得られた融解熱分布曲線より算出した「Ｙ／Ｘ」が０．４７であり、「Ｗ／Ｘ」が０．１２である６−ナイロン
［ナイロンＦ］…ＤＳＣ測定により得られた融解熱分布曲線より算出した「Ｙ／Ｘ」が０．４７であり、「Ｗ／Ｘ」が０．１５である６−ナイロン。 <Raw materials>
[Nylon A] ... "Y / X" calculated from the heat distribution curve of melting obtained by DSC measurement is 0.17, and "W / X" is 0.03. 6-Nylon [Nylon B] ... DSC 6-Nylon [nylon C] ... DSC measurement in which "Y / X" is 0.19 and "W / X" is 0.05 calculated from the melting heat distribution curve (see FIG. 4) obtained by the measurement. 6-Nylon [nylon D], where "Y / X" is 0.28 and "W / X" is 0.11 calculated from the heat of fusion distribution curve obtained by DSC measurement. "Y / X" calculated from the distribution curve (see FIG. 5) is 0.43, and "W / X" is 0.11. 6-nylon [nylon E] ... Melting heat distribution obtained by DSC measurement. "Y / X" calculated from the curve is 0.47, and "W / X" is 0.12. 6-nylon [nylon F] ... "Y" calculated from the heat distribution curve obtained by DSC measurement. 6-Nylon with "/ X" of 0.47 and "W / X" of 0.15.

＜示差走査熱量測定（ＤＳＣ）による融解熱分布曲線等の計測方法＞
上記のナイロンＡ〜Ｆの融解熱分布曲線は、熱流束型ＤＳＣ（示差走査熱量計）を用いて、試料量：１．０ｇ〜１．５ｇ、窒素雰囲気下（窒素流量：５０ｍＬ／分）、昇温速度：１０℃／分の条件で最初の昇温（３０℃〜２８０℃）での融解熱分布曲線を計測した。次に、得られた融解熱分布曲線から、ピーク曲線とベースラインとで取り囲まれる全体のピーク面積Ｘを求め、２１０℃〜２２０℃の範囲における融解熱分布曲線とベースラインとの間の面積Ｙを求め、２１０℃〜２１５℃の範囲における融解熱分布曲線とベースラインとの間の面積Ｗを求めて、「Ｙ／Ｘ」の値及び「Ｗ／Ｘ」の値を求めた。前記熱流束型ＤＳＣとして、ティー・エイ・インスツルメント社製「Discovery DSC2500型 示差走査熱量計」を使用した。 <Measurement method of fusion heat distribution curve, etc. by differential scanning calorimetry (DSC)>
The above-mentioned fusion heat distribution curves of nylons A to F are obtained by using a heat flux type DSC (differential scanning calorimetry), sample amount: 1.0 g to 1.5 g, under a nitrogen atmosphere (nitrogen flow rate: 50 mL / min). The heat of fusion distribution curve at the first temperature rise (30 ° C to 280 ° C) was measured under the condition of temperature rise rate: 10 ° C./min. Next, from the obtained heat of fusion distribution curve, the total peak area X surrounded by the peak curve and the baseline is obtained, and the area Y between the heat of fusion distribution curve and the baseline in the range of 210 ° C to 220 ° C. The area W between the heat of fusion distribution curve and the baseline in the range of 210 ° C to 215 ° C was obtained, and the value of "Y / X" and the value of "W / X" were obtained. As the heat flux type DSC, a "Discovery DSC2500 type differential scanning calorimeter" manufactured by TA Instruments Co., Ltd. was used.

＜実施例１＞
厚さ３５μｍのアルミニウム箔４の両面に、リン酸、ポリアクリル酸（アクリル系樹脂）、クロム(III)塩化合物、水、アルコールからなる化成処理液を塗布した後、１８０℃で乾燥を行って、化成皮膜を形成した。この化成皮膜のクロム付着量は片面当たり１０ｍｇ／ｍ2であった。 <Example 1>
A chemical conversion treatment solution consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol was applied to both sides of an aluminum foil 4 having a thickness of 35 μm, and then dried at 180 ° C. , Formed a chemical conversion film. The amount of chromium adhered to this chemical conversion film was 10 mg / m 2 per side.

次に、前記化成処理済みアルミニウム箔４の一方の面に、２液硬化型のウレタン系接着剤５を介して厚さ１５μｍの二軸延伸ナイロンＡフィルム２をドライラミネートした（貼り合わせた）。次いでアルミニウム箔４の他方の面に、無水マレイン酸変性ポリプロピレン接着剤６を介して厚さ３０μｍの未延伸ポリプロピレンフィルム（熱融着性樹脂層）３を貼り合わせた後、４０℃環境下で５日間放置することによって、図１に示す蓄電デバイス用外装材１を得た。 Next, a biaxially stretched nylon A film 2 having a thickness of 15 μm was dry-laminated (bonded) on one surface of the chemical conversion-treated aluminum foil 4 via a two-component curable urethane-based adhesive 5. Next, an unstretched polypropylene film (heat-fused resin layer) 3 having a thickness of 30 μm was attached to the other surface of the aluminum foil 4 via a maleic anhydride-modified polypropylene adhesive 6, and then 5 in an environment of 40 ° C. By leaving it for a day, the exterior material 1 for a power storage device shown in FIG. 1 was obtained.

＜実施例２＞
外側層のポリアミド樹脂として、ナイロンＡに代えて、ナイロンＢを用いた以外は、実施例１と同様にして、図１に示す構成の蓄電デバイス用外装材１を得た。 <Example 2>
An exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1 except that nylon B was used instead of nylon A as the polyamide resin for the outer layer.

＜実施例３＞
外側層のポリアミド樹脂として、ナイロンＡに代えて、ナイロンＣを用いた以外は、実施例１と同様にして、図１に示す構成の蓄電デバイス用外装材１を得た。 <Example 3>
An exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1 except that nylon C was used instead of nylon A as the polyamide resin for the outer layer.

＜比較例１＞
外側層のポリアミド樹脂として、ナイロンＡに代えて、ナイロンＤを用いた以外は、実施例１と同様にして、蓄電デバイス用外装材を得た。 <Comparative Example 1>
An exterior material for a power storage device was obtained in the same manner as in Example 1 except that nylon D was used instead of nylon A as the polyamide resin for the outer layer.

＜比較例２＞
外側層のポリアミド樹脂として、ナイロンＡに代えて、ナイロンＥを用いた以外は、実施例１と同様にして、蓄電デバイス用外装材を得た。 <Comparative Example 2>
An exterior material for a power storage device was obtained in the same manner as in Example 1 except that nylon E was used instead of nylon A as the polyamide resin for the outer layer.

＜比較例３＞
外側層のポリアミド樹脂として、ナイロンＡに代えて、ナイロンＦを用いた以外は、実施例１と同様にして、蓄電デバイス用外装材を得た。 <Comparative Example 3>
An exterior material for a power storage device was obtained in the same manner as in Example 1 except that nylon F was used instead of nylon A as the polyamide resin for the outer layer.

Figure 0006979847
Figure 0006979847

上記のようにして得られた各蓄電デバイス用外装材について下記評価法に基づいて評価を行った。その結果を表１に示す。 The exterior materials for each power storage device obtained as described above were evaluated based on the following evaluation methods. The results are shown in Table 1.

＜シールバーへの付着防止性評価法＞
得られた蓄電デバイス用外装材を長さ１００ｍｍ×幅５０ｍｍの矩形状に切り出した試料を５枚準備し、それぞれ長さ方向の２等分位置で内側に折り返して内側層の周縁部同士を重ね合わせて、これを以下の各温度×０．２ＭＰａ×３秒のシール条件で一対のヒートシールバーで挟圧してヒートシールした。前記各温度は、１９８℃、２００℃、２０３℃、２０５℃、２１０℃である。シールバーを離間させた際に外装材の外側層がシールバーに付着するか否か等を確認して下記判定基準に基づいて付着防止性を評価した。
（判定基準）
「○」…外装材の外側層はシールバーに全く付着しない
「△」…外装材の外側層は一旦付着するものの、外装材の自重によりシールバーから離れる
「×」…外装材の外側層はシールバーに付着する。 <Evaluation method for preventing adhesion to seal bars>
Five samples of the obtained exterior material for a power storage device cut into a rectangular shape having a length of 100 mm and a width of 50 mm were prepared, and each was folded inward at a position divided into two equal parts in the length direction, and the peripheral edges of the inner layers were overlapped with each other. In addition, this was heat-sealed by sandwiching it with a pair of heat seal bars under the following sealing conditions of each temperature × 0.2 MPa × 3 seconds. The respective temperatures are 198 ° C, 200 ° C, 203 ° C, 205 ° C, and 210 ° C. It was confirmed whether or not the outer layer of the exterior material adhered to the seal bar when the seal bars were separated, and the adhesion prevention property was evaluated based on the following criteria.
(criterion)
"○" ... The outer layer of the exterior material does not adhere to the seal bar at all "△" ... The outer layer of the exterior material adheres once, but separates from the seal bar due to the weight of the exterior material "×" ... The outer layer of the exterior material Adheres to the seal bar.

表１から明らかなように、本発明の実施例１〜３の蓄電デバイス用外装材は、２０５℃の温度でヒートシールを行っても外装材の外側層はシールバーに全く付着しないので、シール不良を起こすことがなく、ヒートシール工程の生産性を向上させることができる。 As is clear from Table 1, the exterior materials for power storage devices of Examples 1 to 3 of the present invention are sealed because the outer layer of the exterior material does not adhere to the seal bar at all even if heat sealing is performed at a temperature of 205 ° C. It is possible to improve the productivity of the heat sealing process without causing defects.

これに対し、比較例１〜３の蓄電デバイス用外装材は、２０５℃の温度でヒートシールを行った際に外装材の外側層はシールバーに付着し、シール不良を起こした（生産性が良好でない）。 On the other hand, in the exterior materials for power storage devices of Comparative Examples 1 to 3, the outer layer of the exterior material adhered to the seal bar when heat-sealing was performed at a temperature of 205 ° C., causing a sealing failure (productivity was improved). Not good).

本発明に係る蓄電デバイス用外装材は、具体例として、例えば、
・リチウム２次電池（リチウムイオン電池、リチウムポリマー電池等）などの蓄電デバイス
・リチウムイオンキャパシタ
・電気２重層コンデンサ
等の各種蓄電デバイスの外装材として用いられる。また、本発明に係る蓄電デバイスは、上記例示した蓄電デバイスの他、全固体電池も含む。 As a specific example, the exterior material for a power storage device according to the present invention is, for example,
-Used as an exterior material for various power storage devices such as power storage devices such as lithium secondary batteries (lithium ion batteries, lithium polymer batteries, etc.), lithium ion capacitors, and electric double-layer capacitors. Further, the power storage device according to the present invention includes an all-solid-state battery in addition to the power storage device exemplified above.

１…蓄電デバイス用外装材
２…ポリアミド樹脂層（外側層）
３…熱融着性樹脂層（内側層）
４…金属箔層
１０…外装ケース
１５…外装部材
３０…蓄電デバイス
３１…蓄電デバイス本体部 1 ... Exterior material for power storage device 2 ... Polyamide resin layer (outer layer)
3 ... Heat-sealing resin layer (inner layer)
4 ... Metal foil layer 10 ... Exterior case 15 ... Exterior member 30 ... Power storage device 31 ... Power storage device main body

Claims (2)

外側層としてのポリアミド樹脂層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層と、を含む蓄電デバイス用外装材であって、
前記ポリアミド樹脂は、示差走査熱量測定で得られる融解熱分布曲線において、該融解熱分布曲線とベースラインとで取り囲まれる全体の面積を「Ｘ」とし、２１０℃〜２２０℃の範囲における融解熱分布曲線とベースラインとの間の面積を「Ｙ」としたとき、０≦Ｙ／Ｘ≦０．３０の関係式を満たしているポリアミド樹脂であり、
前記ポリアミド樹脂は、示差走査熱量測定で得られる融解熱分布曲線において、２１０℃〜２１５℃の範囲における融解熱分布曲線とベースラインとの間の面積を「Ｗ」としたとき、０≦Ｗ／Ｘ≦０．１０の関係式を満たしているポリアミド樹脂であり、
前記ポリアミド樹脂は、示差走査熱量測定で得られる融解熱分布曲線において、熱量ピーク値が−２．５Ｗ／ｇ〜−３．０Ｗ／ｇの範囲にあり、
前記ポリアミド樹脂は、６−ナイロンであることを特徴とする蓄電デバイス用外装材。 An exterior material for a power storage device including a polyamide resin layer as an outer layer, a heat-sealing resin layer as an inner layer, and a metal foil layer arranged between both layers.
In the heat of fusion distribution curve obtained by differential scanning calorimetry, the entire area surrounded by the heat of fusion distribution curve and the baseline is "X", and the heat of fusion is distributed in the range of 210 ° C to 220 ° C. when the area between the curve and the base line was evaluated as "Y", Ri polyamide resin der meet the relation of 0 ≦ Y / X ≦ 0.30,
The polyamide resin has 0 ≦ W / when the area between the heat of fusion distribution curve and the baseline in the range of 210 ° C. to 215 ° C. is “W” in the heat of fusion distribution curve obtained by differential scanning calorimetry. It is a polyamide resin satisfying the relational expression of X ≦ 0.10.
The polyamide resin has a calorific value in the range of −2.5 W / g to −3.0 W / g in the heat of fusion distribution curve obtained by differential scanning calorimetry.
The polyamide resin is an exterior material for a power storage device, characterized in that it is 6-nylon. 蓄電デバイス本体部と、
請求項１に記載の蓄電デバイス用外装材を含む外装部材とを備え、
前記蓄電デバイス本体部が、前記外装部材で外装されていることを特徴とする蓄電デバイス。 The main body of the power storage device and
An exterior member including the exterior material for a power storage device according to claim 1 is provided.
A power storage device characterized in that the power storage device main body is covered with the exterior member.
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