JP2009087628A - Adhesive sheet for sealing flat electrochemical cell metal terminal - Google Patents

Adhesive sheet for sealing flat electrochemical cell metal terminal Download PDF

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JP2009087628A
JP2009087628A JP2007253877A JP2007253877A JP2009087628A JP 2009087628 A JP2009087628 A JP 2009087628A JP 2007253877 A JP2007253877 A JP 2007253877A JP 2007253877 A JP2007253877 A JP 2007253877A JP 2009087628 A JP2009087628 A JP 2009087628A
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metal terminal
electrochemical cell
adhesive sheet
metal
acid
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JP5169112B2 (en
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Yoichi Mochizuki
洋一 望月
Masataka Okushita
正隆 奥下
Hirohisa Akita
裕久 秋田
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Dai Nippon Printing Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive sheet for sealing flat electrochemical cell metal terminals which can stably seal a packaging body by preventing short-circuit between a barrier layer made of a metal foil of aluminum or the like in the packaging body and the metal terminals, and have strong interlayer adhesion strength (hereafter, called as laminate strength) and have less possibility for deterioration of battery performance caused by invasion of moisture, wherein the metal terminals connected respectively with a positive electrode and a negative electrode are sandwiched and sealed in an outward protruding state by the inner layers of peripheral edge thermally-bonding sections of the packaging body, with the inner layers thereof provided at least with a polyolefin resin (general polyolefin resin) having a thermal adhesive property and the barrier layer made of the metal foil. <P>SOLUTION: In the adhesive sheet 1 for sealing the flat electrochemical cell metal terminals, an insulating particle dispersed layer 2 made of an acid-modified polyolefin containing dispersed insulating particles is covered with an acid-modified polyolefin resin 3 having adhesiveness with the inner layer and the metal terminals. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、電池やキャパシタに代表される、電解質（液体や固体電解質）を収納した扁平型電気化学セル本体を包装する包装材料に関し、さらに詳しくは、扁平型電気化学セル本体を包装する包装体と前記扁平型電気化学セル本体の正極および負極の各々に接続されて前記包装体の外部に突設される金属端子との間に介在させて、前記包装体と前記金属端子および前記包装体同士を接着する扁平型電気化学セル金属端子部密封用接着性シートに関するものである。   The present invention relates to a packaging material for packaging a flat electrochemical cell body containing an electrolyte (liquid or solid electrolyte), represented by a battery or a capacitor, and more specifically, a packaging body for packaging a flat electrochemical cell body. And between the positive electrode and the negative electrode of the flat electrochemical cell main body and a metal terminal protruding from the package body, the package body, the metal terminal, and the package body The present invention relates to an adhesive sheet for sealing a flat electrochemical cell metal terminal part.

扁平型電気化学セルの一つとしてリチウム電池が挙げられる。リチウム電池は、リチウム２次電池ともいわれ、電解質として固体高分子、ゲル状高分子、液体などからなり、リチウムイオンの移動で起電する電池であって、正極・負極活物質が高分子ポリマーからなるものを含むものである。リチウム２次電池の構成は、正極集電材（アルミニウム）／正極活性物質層（金属酸化物、カーボンブラック、金属硫化物、電解液、ポリアクリロニトリル等の高分子正極材料）／電解質（プロピレンカーボネート、エチレンカーボネート、炭酸ジメチル、エチルメチルカーボネート等のカーボネート系電解液、リチウム塩からなる無機固体電解質、ゲル電解質）／負極活性物質層（リチウム金属、合金、カーボン、電解液、ポリアクリロニトリルなどの高分子負極材料）／負極集電材（銅）からなるリチウム電池本体およびそれらを包装する包装体等からなる。リチウム２次電池の用途としては、パソコン、携帯端末（携帯電話、ＰＤＡ等）、ビデオカメラ、電気自動車、エネルギー貯蔵用蓄電池、ロボット、衛星等に用いられる。なお、本明細書においては、前記正極集電材と正極活性物質層とを正極、前記負極集電材と負極活性物質層とを負極と呼称する。   One of the flat electrochemical cells is a lithium battery. A lithium battery is also called a lithium secondary battery, which is a battery made of a solid polymer, a gel polymer, a liquid, etc. as an electrolyte, and is activated by the movement of lithium ions. Is included. The configuration of the lithium secondary battery is as follows: positive electrode current collector (aluminum) / positive electrode active material layer (polymeric positive electrode material such as metal oxide, carbon black, metal sulfide, electrolyte, polyacrylonitrile) / electrolyte (propylene carbonate, ethylene Carbonate electrolyte such as carbonate, dimethyl carbonate, ethylmethyl carbonate, inorganic solid electrolyte composed of lithium salt, gel electrolyte) / negative electrode active substance layer (lithium metal, alloy, carbon, electrolyte, polyacrylonitrile, etc. polymer negative electrode material ) / A lithium battery main body made of a negative electrode current collector (copper) and a packaging body for packaging them. Lithium secondary batteries are used for personal computers, portable terminals (cell phones, PDAs, etc.), video cameras, electric vehicles, energy storage batteries, robots, satellites, and the like. In the present specification, the positive electrode current collector and the positive electrode active material layer are referred to as a positive electrode, and the negative electrode current collector and the negative electrode active material layer are referred to as a negative electrode.

前記リチウム電池の包装体としては、金属をプレス加工して円筒状ないし直方体状に容器化した金属製缶、あるいは、プラスチックフィルム、アルミニウム等の金属箔を積層した積層体を袋状等に加工した袋体（以下、包装体と呼称する）などが用いられている。   As the package of the lithium battery, a metal can formed by pressing a metal into a cylindrical or rectangular parallelepiped container, or a laminate in which a metal foil such as a plastic film or aluminum is laminated is processed into a bag shape or the like. A bag body (hereinafter referred to as a packaging body) or the like is used.

ところで、金属製缶からなる包装体はリジッドであり、これにより電池自体の形状が決められるために、たとえば、これを携帯電話に用いる場合には、携帯電話本体の寸法が電池の形状で決り、携帯電話の形状を自由に設計することができないといった問題があり、柔軟性を有するために携帯電話本体の形状をある程度自由に設計できることから前記包装体が用いられる傾向にある。さらにまた、前記包装体が用いられる傾向にある理由としては、電池が高温下で使用されて内部圧力が異常に高まった場合、金属製缶からなる包装体は、爆発、発火が起こるまで包装体が耐えるために危険であるといった問題があるのに対して、熱接着部で密封される前記包装体は前記熱接着部が剥離して内部圧力を逃がす安全弁の働きをするために電池としての機能は失われるものの金属製缶からなる包装体に比べて爆発、発火の危険性を少なくすることができるためでもある。   By the way, since the package made of a metal can is rigid, and the shape of the battery itself is thereby determined, for example, when this is used for a mobile phone, the size of the mobile phone body is determined by the shape of the battery, There is a problem that the shape of the mobile phone cannot be freely designed, and the packaging body tends to be used because the shape of the mobile phone body can be freely designed to some extent because it has flexibility. Furthermore, the reason why the package tends to be used is that, when the battery is used at a high temperature and the internal pressure is abnormally increased, the package made of a metal can is packaged until explosion or ignition occurs. However, the package that is sealed at the heat-bonding part functions as a battery to act as a safety valve that releases the internal pressure by peeling off the heat-bonding part. Although it is lost, the risk of explosion and ignition can be reduced compared to a package made of metal cans.

前記包装体としては、リチウム電池としての必要な物性、加工性、経済性等から、図２に示すように少なくとも基材層Ａ１、アルミニウム等の金属箔からなるバリアー層Ａ２、熱接着性樹脂層Ａ３を積層した積層体Ａが用いられ、この積層体Ａを図３（ａ）に示すように袋状〔図３（ａ）上はピロータイプの包装袋であるが三方タイプ、四方タイプ等の包装袋であってもよい〕に加工して前記リチウム電池本体およびこれの正極および負極との各々に接続された金属端子３１を外側に突出した状態で収納し、開口部を熱接着して密封するなり、あるいは、この積層体Ａを図４（ａ）に示すように前記熱接着性樹脂層が内側に位置するようにプレス成形して凹部を形成し、この凹部に前記リチウム電池本体およびこれの正極および負極との各々に接続された金属端子３１を外側に突出した状態で収納すると共に別途用意したシート状の前記積層体Ａ（図示せず）の前記熱接着性樹脂層が前記凹部側に位置するようにして前記凹部を被覆すると共に周縁を熱接着して密封することにより図３（ｂ）、あるいは、図４（ｂ）に示すリチウム電池１０として用いられている。なお、符号Ｓは熱接着部を示す。   As the package, in view of necessary physical properties, workability, economy, etc. as a lithium battery, as shown in FIG. 2, at least a base layer A1, a barrier layer A2 made of a metal foil such as aluminum, a heat-adhesive resin layer A laminated body A in which A3 is laminated is used, and this laminated body A is formed into a bag shape as shown in FIG. 3 (a). The metal terminal 31 connected to each of the lithium battery main body and the positive electrode and the negative electrode of the lithium battery main body and protruding to the outside is stored and the opening is thermally bonded and sealed. Alternatively, as shown in FIG. 4 (a), the laminate A is press-molded so that the heat-adhesive resin layer is located on the inside to form a recess, and the lithium battery main body and the same are formed in the recess. Each with positive and negative electrodes The connected metal terminals 31 are stored in a state of protruding outward, and the recesses are arranged so that the thermally adhesive resin layer of the sheet-like laminate A (not shown) prepared separately is located on the recess side. And the peripheral edge is thermally bonded and sealed to be used as the lithium battery 10 shown in FIG. 3 (b) or FIG. 4 (b). Reference sign S indicates a thermal bonding portion.

前記包装体（前記積層体Ａ）を構成する前記熱接着性樹脂層Ａ３としては、前記熱接着性樹脂層Ａ３同士の熱接着性と共に前記リチウム電池本体から前記包装体の外部に突設される金属端子３１との熱接着性が求められ、金属との接着性に優れる酸変性ポリオレフィン系樹脂、たとえば、不飽和カルボン酸でグラフト変性したポリオレフィン樹脂、エチレンないしプロピレンとアクリル酸、または、メタクリル酸との共重合体、あるいは、金属架橋ポリオレフィン樹脂などが用いられていた。   The thermal adhesive resin layer A3 constituting the package (the laminated body A) is projected from the lithium battery main body to the outside of the package together with the thermal adhesiveness between the thermal adhesive resin layers A3. An acid-modified polyolefin resin that requires thermal adhesion to the metal terminal 31 and is excellent in adhesion to metal, such as polyolefin resin graft-modified with unsaturated carboxylic acid, ethylene or propylene and acrylic acid, or methacrylic acid Copolymers or metal cross-linked polyolefin resins have been used.

しかしながら、前記包装体（前記積層体Ａ）を構成する前記熱接着性樹脂層Ａ３に前記酸変性ポリオレフィン系樹脂を用いると、一般的なポリオレフィン系樹脂（炭素と水素とからなる直鎖状あるいは分枝鎖状のオレフィン系樹脂を意味し、以下一般ポリオレフィン系樹脂と呼称する）と比較して滑り性が悪く、袋状に加工する際にシワが入るといった問題やプレス成形して凹部を形成する際にピンホールやクラックが発生する虞があるといった問題があり、これに代わるものとして前記熱接着性樹脂層Ａ３には一般ポリオレフィン系樹脂を用い、この一般ポリオレフィン系樹脂と前記金属端子３１との両方に熱接着可能な上記したような酸変性ポリオレフィン系樹脂の単層ないしこれを少なくとも一方の表層に形成した複層からなるリチウム電池金属端子部密封用接着性シート（以下、接着性シートと呼称する場合がある）を前記金属端子と前記熱接着性樹脂層との間に介在させて熱接着して密封する方法が採用されるようになってきた。   However, when the acid-modified polyolefin-based resin is used for the heat-adhesive resin layer A3 constituting the package (the laminate A), a general polyolefin-based resin (a linear or divided resin composed of carbon and hydrogen) is used. This refers to a branched olefin-based resin, which is referred to as a general polyolefin-based resin, and is less slippery and wrinkles when processed into a bag, or press-molded to form a recess. There is a problem that pinholes and cracks may occur at the time. As an alternative, a general polyolefin-based resin is used for the heat-adhesive resin layer A3. Lithium consisting of a single layer of the above-mentioned acid-modified polyolefin resin that can be thermally bonded to both or a multilayer formed of at least one surface layer thereof A method is adopted in which an adhesive sheet for sealing a battery metal terminal part (hereinafter sometimes referred to as an adhesive sheet) is interposed between the metal terminal and the heat-adhesive resin layer and thermally bonded. It has come to be.

具体的に説明すると、図５に示すように電解質を注入する前のリチウム電池本体３０は前記リチウム電池本体３０から前記包装体の外部に突設される金属端子３１〔図３（ｂ）、図４（ｂ）参照〕とからなり、たとえば、該金属端子３１の両面に上記した酸変性ポリオレフィン系樹脂単層からなる金属端子部密封用接着性シート１’が仮着シールにより固定される。そして、プレス成形して凹部を形成した図４（ａ）に示す積層体Ａの前記凹部に前記リチウム電池本体３０を収納すると共に、別途用意したシート状の前記積層体Ａ（図示せず）で前記凹部を被覆して前記リチウム電池本体３０の前記金属端子３１を備える周縁を含む３つの周縁を熱接着して後に１つの未接着部の周縁から電解質を注入し、その後に前記未接着部を熱接着して密封することにより図４（ｂ）に示すリチウム電池１０となる。   More specifically, as shown in FIG. 5, the lithium battery body 30 before the electrolyte is injected is a metal terminal 31 protruding from the lithium battery body 30 to the outside of the package [FIG. 3 (b), FIG. 4 (b)], for example, the metal terminal portion sealing adhesive sheet 1 ′ composed of the above-mentioned acid-modified polyolefin resin single layer is fixed to both surfaces of the metal terminal 31 by temporary sealing. Then, the lithium battery main body 30 is housed in the concave portion of the laminate A shown in FIG. 4 (a) formed by press molding, and the laminate A (not shown) prepared separately is used. The three peripheral edges including the peripheral edge provided with the metal terminal 31 of the lithium battery main body 30 covering the concave portion are thermally bonded, and then an electrolyte is injected from the peripheral edge of one non-adhered part. The lithium battery 10 shown in FIG. 4B is obtained by thermal bonding and sealing.

ところで、前記リチウム電池１０の前記金属端子３１は前記接着性シート１’を備えた部位で前記包装体（前記積層体Ａ）に挟持された状態で熱接着されるが、前記金属端子３１はその厚さが少なくとも５０μｍ程度、巾としては少なくとも２．５ｍｍ程度あり、前記金属端子３１の両側部の空隙を前記接着性シート１’と前記包装体（前記積層体Ａ）の前記熱接着性樹脂層Ａ３で埋めて密封状態を確保するためには熱接着するための熱と圧力が必要となるが、これにより前記接着性シート１’と前記包装体（前記積層体Ａ）の前記熱接着性樹脂層Ａ３とが加圧部の外に押出されて前記加圧部が薄肉となり、また、一般に金属端子の両側端部には小幅に裁断するときに数μｍ〜数十μｍのバリが発生しており、これが原因となり前記包装体（前記積層体Ａ）のアルミニウム等の金属箔からなるバリアー層Ａ２と前記金属端子３１とが接触して短絡するという問題があった。   By the way, although the said metal terminal 31 of the said lithium battery 10 is heat-bonded in the state clamped by the said package (the said laminated body A) in the site | part provided with the said adhesive sheet 1 ', the said metal terminal 31 is the The thickness is at least about 50 μm, the width is at least about 2.5 mm, and the thermal adhesive resin layer of the adhesive sheet 1 ′ and the package (the laminate A) is formed in the gaps on both sides of the metal terminal 31. In order to fill with A3 and secure a sealed state, heat and pressure for thermal bonding are required, and as a result, the thermal adhesive resin of the adhesive sheet 1 ′ and the package (the laminate A) The layer A3 is extruded out of the pressurizing part, and the pressurizing part becomes thin, and generally, burrs of several μm to several tens of μm are generated at both ends of the metal terminal when cutting to a small width. And this causes the packaging A barrier layer A2 comprising a metal foil such as aluminum in the laminate A) and the metal terminal 31 has a problem that a short circuit in contact.

また、この問題を改善するため、前記金属端子３１の両面に用いる前記接着性シート１’として、耐熱性樹脂フィルムの両面を、電池包装材の内面フィルムにヒートシール可能なフィルムで被覆した３層構成の積層フィルムからなる電池端子用被覆材（上記、金属端子部密封用接着性シートに対応。）が提案されている（例えば、特許文献１参照）。しかしながら、特許文献１記載の電池端子用被覆材を用いた場合には、上記した短絡するという現象は酸変性ポリオレフィン系樹脂単層のものに比べて良化するが、耐熱性樹脂フィルムと、電池包装材の内面フィルムにヒートシール可能なフィルムとの層間接着強度が充分ではなく、電池要素が異常発熱し電池内部でガスが発生し電池の内圧が上昇した場合、金属端子取出部での電池包装材と金属端子とを剥離する応力により、前記耐熱性樹脂フィルムと電池包装材の内面フィルムにヒートシール可能なフィルムとの界面で剥離するという虞があった。なお、上記問題は、リチウム電池本体を収納したリチウム電池以外に、キャパシタ、電気二重層キャパシタを収納した場合にも同様の問題が生じる。
特開２０００−２０８１１２号公報 Moreover, in order to improve this problem, as said adhesive sheet 1 'used on both surfaces of the said metal terminal 31, 3 layers which coat | covered both surfaces of the heat resistant resin film with the film which can be heat-sealed to the inner surface film of a battery packaging material. A battery terminal covering material (corresponding to the above-mentioned adhesive sheet for sealing a metal terminal portion) made of a laminated film having a structure has been proposed (see, for example, Patent Document 1). However, when the covering material for battery terminals described in Patent Document 1 is used, the phenomenon of short-circuiting described above is improved as compared with that of an acid-modified polyolefin resin single layer, but a heat-resistant resin film and a battery If the inner layer film of the packaging material does not have sufficient interlayer adhesion strength with the heat-sealable film, the battery element abnormally heats up, gas is generated inside the battery, and the internal pressure of the battery rises, the battery packaging at the metal terminal extraction part Due to the stress that peels the material and the metal terminal, there is a risk of peeling at the interface between the heat-resistant resin film and the film that can be heat sealed to the inner film of the battery packaging material. Note that the above problem also occurs when a capacitor and an electric double layer capacitor are housed in addition to the lithium battery housing the lithium battery body.
JP 2000-208112 A

そこで本発明は、上記問題に鑑みてなされたものであって、正極および負極の各々に接続された金属端子を外側に突出した状態で挟持して周縁熱接着部で密封した内層に熱接着性を有するポリオレフィン系樹脂（一般ポリオレフィン系樹脂）と金属箔からなるバリアー層とを少なくとも備えた包装体において、前記包装体のアルミニウム等の金属箔からなるバリアー層と金属端子との短絡を防止して安定した状態で密封することができると共に、層間接着強度（以下、ラミネート強度と呼称する）の強く、水分の浸入による電池性能の低下の虞の低い扁平型電気化学セル金属端子部密封用接着性シートを提供することである。   Therefore, the present invention has been made in view of the above-described problem, in which a metal terminal connected to each of a positive electrode and a negative electrode is sandwiched in a state of protruding outward and is thermally bonded to an inner layer sealed by a peripheral heat bonding portion. In a package including at least a polyolefin resin (general polyolefin resin) having a barrier layer made of metal foil and a barrier layer made of metal foil such as aluminum of the package to prevent a short circuit Flat type electrochemical cell metal terminal sealing adhesiveness that can be sealed in a stable state, has high interlayer adhesion strength (hereinafter referred to as laminate strength), and is less likely to degrade battery performance due to moisture ingress. Is to provide a sheet.

上記課題を解決するため、請求項１の発明は、熱接着性を有するポリオレフィン系樹脂からなる内層と金属箔からなるバリアー層とを少なくとも備えた包装材により、正極および負極を備えた電気化学素子を収納すると共に前記正極および負極に各々接続された金属端子を外側に突出した状態で挟持して周縁熱接着部で密封した扁平型電気化学セルの金属端子取出部における前記内層と前記金属端子との間に介在させる扁平型電気化学セル金属端子部密封用接着性シートであって、該扁平型電気化学セル金属端子部密封用接着性シートは絶縁性粒子が分散した酸変性ポリオレフィン系樹脂からなる絶縁性粒子分散層を前記内層及び金属端子と接着性を有する酸変性ポリオレフィン系樹脂で被覆したものであることを特徴とする扁平型電気化学セル金属端子部密封用接着性シート。
このように構成することにより、包装体のアルミニウム等の金属箔からなるバリアー層と金属端子との短絡を防止して安定した状態で密封することができると共に、層間接着強度（以下、ラミネート強度と呼称する）の強い扁平型電池化学セル金属端子部密封用接着性シートを得ることができ、電池要素が異常発熱し電池内部でガスが発生し電池の内圧が上昇した場合においても、金属端子取出部での電池包装材と金属端子とを剥離する応力により、耐熱性樹脂フィルムと電池包装材の内面フィルムにヒートシール可能なフィルムとの界面で剥離するという現象を防ぎ安全性の高い扁平型電気化学セルを提供することができる。 In order to solve the above-mentioned problems, the invention of claim 1 is an electrochemical device comprising a positive electrode and a negative electrode by a packaging material comprising at least an inner layer made of a polyolefin resin having thermal adhesion and a barrier layer made of a metal foil. The inner layer and the metal terminal in the metal terminal extraction part of the flat electrochemical cell sandwiched in a state where the metal terminal connected to the positive electrode and the negative electrode protrudes to the outside and sealed by the peripheral heat bonding part A flat type electrochemical cell metal terminal part sealing adhesive sheet interposed between the two, wherein the flat type electrochemical cell metal terminal part sealing adhesive sheet is made of an acid-modified polyolefin resin in which insulating particles are dispersed. A flat electrochemical system characterized in that an insulating particle dispersion layer is coated with an acid-modified polyolefin resin having adhesiveness with the inner layer and the metal terminal. Le metal terminal portion sealing adhesive sheet.
By comprising in this way, the barrier layer which consists of metal foils, such as aluminum of a package, and the metal terminal can be prevented from short circuit and can be sealed in a stable state, and the interlayer adhesive strength (hereinafter referred to as laminate strength and Flat battery chemical cell metal terminal sealing adhesive sheet can be obtained, and even if the battery element abnormally generates heat, gas is generated inside the battery, and the internal pressure of the battery rises, the metal terminal can be removed. The flat-type electricity with high safety prevents the phenomenon of peeling at the interface between the heat-resistant resin film and the inner film of the battery packaging material and the heat-sealable film due to the stress that separates the battery packaging material from the metal terminal A chemical cell can be provided.

請求項２の発明は、請求項１記載の扁平型電気化学セル金属端子部密封用接着シートにおいて、前記内層を形成するポリオレフィン系樹脂がポリプロピレンからなり、前記酸変性ポリオレフィン系樹脂が不飽和カルボン酸でグラフト変性したポリプロピレンであることを特徴とするものである。このように構成することにより、金属端子取出部から接着シートの端面を通して水蒸気が、扁平型電気化学セルの内部に浸入することを防止することができ、安全性の極めて高い扁平電気化学セルを得ることができる。   The invention according to claim 2 is the flat electrochemical cell metal terminal sealing adhesive sheet according to claim 1, wherein the polyolefin resin forming the inner layer is made of polypropylene, and the acid-modified polyolefin resin is an unsaturated carboxylic acid. It is characterized by being a polypropylene modified by grafting. By comprising in this way, it can prevent that water vapor | steam penetrate | invades into the inside of a flat type electrochemical cell through the end surface of an adhesive sheet from a metal terminal extraction part, and obtains a highly safe flat electrochemical cell. be able to.

請求項３記載の発明は、正極及び負極を備えた電気化学素子を収納し、前記正極及び負極の各々に接続された金属端子を突出するように挟持して周縁熱接着部で密封した内層に熱接着性を有するポリオレフィン系樹脂と金属箔からなるバリアー層とを少なくとも備えた包装体からなる扁平型電気化学セルにおいて、前記包装体の前記周縁熱接着部の前記内層と前記金属端子との間に請求項１または２記載の扁平型電気化学セル金属端子部密封用接着シートを介在させたことを特徴とする。このように構成することにより、絶縁性や密封性に優れると共に水蒸気バリヤー性においても優れた、高性能な扁平型電気化学セルとすることができる。   The invention according to claim 3 is an inner layer that houses an electrochemical device including a positive electrode and a negative electrode, sandwiches a metal terminal connected to each of the positive electrode and the negative electrode so as to protrude, and is sealed by a peripheral heat bonding portion. In a flat electrochemical cell comprising a package having at least a polyolefin resin having thermal adhesiveness and a barrier layer made of a metal foil, between the inner layer of the peripheral heat-bonded portion of the package and the metal terminal The flat electrochemical cell metal terminal part sealing adhesive sheet according to claim 1 or 2 is interposed. By comprising in this way, it can be set as the high performance flat type electrochemical cell which was excellent in insulation and sealing performance, and was excellent also in water vapor | steam barrier property.

本発明は、従来問題であった、包装体のアルミニウム等の金属箔からなるバリアー層と金属端子との短絡を防止することができるとともに、密封性及び水蒸気バリアー性にも優れた層間強度（ラミネート強度）の強い扁平型電気化学セル金属端子部密封接着シートを提供することができる。   The present invention can prevent a short circuit between a barrier layer made of a metal foil such as aluminum of a package and a metal terminal, which has been a problem in the past, and also has an interlayer strength (laminate) excellent in sealing property and water vapor barrier property. A flat electrochemical cell metal terminal part sealing adhesive sheet having high strength can be provided.

最初に本発明に供する扁平型電気化学セルの包装体について説明する。前記包装体としては、図２に示す、少なくとも基材層Ａ１、アルミニウム等の金属箔からなるバリアー層Ａ２、一般ポリオレフィン系樹脂からなる熱接着性樹脂層Ａ３を積層した積層体Ａが用いられ、前記基材層Ａ１としては二軸延伸ポリエステルフィルムや二軸延伸ナイロンフィルム、あるいは、これらの積層体を挙げることができ、その厚さとしては概ね６〜３０μｍ程度である。また、前記バリアー層Ａ２としては、アルミニウムやニッケル、ステンレスなどの金属箔を挙げることができ、その厚さとしては概ね１５〜８０μｍ程度である。また、前記熱接着性樹脂層Ａ３を形成する一般ポリオレフィン系樹脂としては、低密度ポリエチレン，中密度ポリエチレン，高密度ポリエチレン，線状低密度ポリエチレン，エチレン−ブテン共重合体等のエチレン系樹脂、ホモポリプロピレン，エチレン−プロピレン共重合体，エチレン−プロピレン−ブテン共重合体等のプロピレン系樹脂の単体ないし混合物を挙げることができ、その厚さとしては概ね２０〜１００μｍである。   First, a flat electrochemical cell package for use in the present invention will be described. As the package, a laminate A in which at least a base material layer A1, a barrier layer A2 made of a metal foil such as aluminum, and a heat-adhesive resin layer A3 made of a general polyolefin resin are laminated, as shown in FIG. Examples of the base material layer A1 include a biaxially stretched polyester film, a biaxially stretched nylon film, and a laminate thereof, and the thickness is about 6 to 30 μm. Examples of the barrier layer A2 include metal foils such as aluminum, nickel, and stainless steel, and the thickness is approximately 15 to 80 μm. Examples of the general polyolefin resin forming the heat-adhesive resin layer A3 include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-butene copolymer, and other ethylene-based resins. A propylene resin such as polypropylene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer may be used alone or as a mixture, and the thickness is generally 20 to 100 μm.

次に、上記の本発明について、図面等を用いて以下に詳述するが、扁平型電気化学セル電池の形態等は従来技術で説明した形態と同じであり、従来技術の図を用いて説明するものとする。
図１は本発明にかかる扁平型電気化学セル金属端子部密封用接着性シートの代表的な層構成を図解的に示す図、図２は扁平型電気化学セルに用いる包装体の基本的な層構成を図解的に示す図、図３は扁平型電気化学セルに用いる包装体の一実施例を説明する図、図４は扁平型電気化学セルの用いる包装体の他の実施例を説明する図、図５は扁平型電気化学セルの金属端子部に用いる金属端子部密封用接着性シートの設け方の一例を説明する図であり、図中の１，１’は扁平型電気化学セル金属端子部密封用接着性シート、２は絶縁性粒子分散層、３は酸変性ポリオレフィン層、１０は扁平型電気化学セル、３０は扁平型電気化学セル本体、３１は金属端子、Ａは積層体、Ａ１は基材層、Ａ２は金属箔からなるバリアー層、Ａ３は熱接着性樹脂層をそれぞれ示す。 Next, the present invention will be described in detail below with reference to the drawings and the like, but the form of the flat electrochemical cell battery is the same as the form described in the prior art, and will be explained using the drawings of the prior art. It shall be.
FIG. 1 is a diagram schematically showing a typical layer structure of an adhesive sheet for sealing a flat electrochemical cell metal terminal according to the present invention, and FIG. 2 is a basic layer of a package used in the flat electrochemical cell. FIG. 3 is a diagram illustrating the configuration, FIG. 3 is a diagram illustrating an embodiment of a package used in a flat electrochemical cell, and FIG. 4 is a diagram illustrating another embodiment of the package used in the flat electrochemical cell. FIG. 5 is a diagram for explaining an example of a method for providing an adhesive sheet for sealing a metal terminal portion used for a metal terminal portion of a flat electrochemical cell, and 1 and 1 ′ in the drawing are flat electrochemical cell metal terminals. Partially sealing adhesive sheet, 2 is an insulating particle dispersion layer, 3 is an acid-modified polyolefin layer, 10 is a flat electrochemical cell, 30 is a flat electrochemical cell body, 31 is a metal terminal, A is a laminate, A1 Is a base material layer, A2 is a barrier layer made of metal foil, and A3 is a thermoadhesive resin layer Respectively.

図１は本発明にかかる扁平型電気化学セル金属端子部密封用接着性シートの層構成を図解的に示す図であって、金属端子部密封用接着性シート１は、絶縁性粒子が分布した酸変性ポリオレフィン樹脂からなる絶縁性粒子分散層２に熱接着性樹脂層A3（内層に対応）及び金属端子３１と接着性を有する酸変性ポリオレフィン系樹脂３が積層され両面が被覆された構成のものである。   FIG. 1 is a diagram schematically showing a layer structure of a flat electrochemical cell metal terminal part sealing adhesive sheet according to the present invention, in which a metal terminal part sealing adhesive sheet 1 is distributed with insulating particles. A structure in which an insulating particle dispersion layer 2 made of an acid-modified polyolefin resin is laminated with a heat-adhesive resin layer A3 (corresponding to the inner layer) and an acid-modified polyolefin-based resin 3 having adhesiveness to the metal terminal 31 and coated on both sides. It is.

次に、絶縁性粒子分散層について説明する。従来技術の項で説明したように、扁平型電気化学セル金属端子部密封用接着性シート（接着性シートと呼称する場合もある）１は、扁平型電気化学セル１０の周縁熱接着部において金属端子３１と外装フィルム（積層体Ａに対応）との間に介在し熱接着され、熱接着時の熱（１６０〜１９０℃）と圧力（１．０〜２．０ＭＰａ）により溶融し押し潰されない耐熱性と電解液に対する耐性が必要とされる。絶縁性粒子分散層２は、酸変性ポリオレフィン樹脂層中に絶縁性粒子が均一に分散されているため、絶縁性粒子分散層２を酸変性ポリオレフィン系樹脂で被覆した接着シートを金属端子と外装フィルムとの間に介在し熱接着した場合、絶縁性粒子が熱で溶融しないために熱接着時の熱と圧力により溶融し押し潰され金属端子と外装フィルム中の金属層とが接触し短絡することを防止することができる。また、絶縁性粒子分散層２の両面に絶縁性粒子分散層２を構成する酸変性ポリオレフィン系樹脂と同一の樹脂を溶融押出しにより積層しているため、絶縁性粒子分散層２と酸変性ポリオレフィン樹脂層との間が強固に接着し、電池内部での内圧上昇時においても接着シートの層間で剥離することを防止することができる。   Next, the insulating particle dispersion layer will be described. As described in the section of the prior art, the flat electrochemical cell metal terminal sealing adhesive sheet (sometimes referred to as an adhesive sheet) 1 is a metal at the peripheral thermal bonding portion of the flat electrochemical cell 10. It is interposed between the terminal 31 and the exterior film (corresponding to the laminated body A) and thermally bonded, and is not melted and crushed by heat (160 to 190 ° C.) and pressure (1.0 to 2.0 MPa) at the time of thermal bonding. Heat resistance and resistance to electrolytes are required. Since the insulating particle dispersion layer 2 has the insulating particles uniformly dispersed in the acid-modified polyolefin resin layer, the adhesive sheet in which the insulating particle dispersion layer 2 is coated with the acid-modified polyolefin resin is used as a metal terminal and an exterior film. If the insulating particles do not melt with heat, the metal particles are melted and crushed by the heat and pressure at the time of thermal bonding, and the metal terminal and the metal layer in the exterior film contact and short circuit. Can be prevented. In addition, since the same resin as the acid-modified polyolefin resin constituting the insulating particle dispersion layer 2 is laminated on both surfaces of the insulating particle dispersion layer 2 by melt extrusion, the insulating particle dispersion layer 2 and the acid-modified polyolefin resin are laminated. It is possible to prevent adhesion between the layers of the adhesive sheet even when the internal pressure rises inside the battery.

次に、絶縁性粒子分散層２の両面に酸変性ポリオレフィン系樹脂３を塗布し両面を被覆する方法について説明する。まず、絶縁性粒子分散層２を繰り出し、シートの片面に溶融状態の酸変性ポリオレフィン系樹脂を押出しコートした後、前記シートの他方の面に溶融状態の酸変性ポリオレフィン系樹脂を押出しコートにより積層して形成される。   Next, a method for coating the both surfaces of the insulating particle dispersion layer 2 by applying the acid-modified polyolefin resin 3 on both surfaces will be described. First, the insulating particle dispersion layer 2 is fed out, and a molten acid-modified polyolefin resin is extrusion coated on one surface of the sheet, and then a molten acid modified polyolefin resin is laminated on the other surface of the sheet by extrusion coating. Formed.

次に、前記酸変性ポリオレフィン系樹脂３について説明する。前記酸変性ポリオレフィン系樹脂３は前記金属端子３１（図５参照）および包装体の内層である一般ポリオレフィン系樹脂からなる前記熱接着性樹脂層Ａ３（図２参照）と熱接着するために設ける層であり、前記熱接着性樹脂層Ａ３（図２参照）に用いる樹脂種により適宜選択して用いる必要があるが、従来技術の項で説明した酸変性ポリオレフィン系樹脂を用いることができ、再度例示するならば、不飽和カルボン酸でグラフト変性したポリオレフィン樹脂、エチレンないしプロピレンとアクリル酸、または、メタクリル酸との共重合体、あるいは、金属架橋ポリオレフィン樹脂等であり、必要に応じてブテン成分、エチレン−プロピレン−ブテン共重合体、非晶質のエチレン−プロピレン共重合体、プロピレン−α−オレフィン共重合体、オレフィン系エラストマー等を５％以上添加してもよいものである。なお、防湿性、耐熱性を考慮すると、不飽和カルボン酸でグラフト変性したポリオレフィン樹脂、特に不飽和カルボン酸でグラフト変性したポリプロピレン樹脂が好ましい。また、前述した異常状発熱、内圧上昇による耐久性を考慮すると、１２０℃以下に融点を有さないオレフィン系エラストマーを添加した樹脂が好適である。また、前記酸変性ポリオレフィン層４は、上記した酸変性ポリオレフィン系樹脂をＴダイ押出機から前記繊維質シートあるいは多孔質シート２上に加熱溶融押出しすることにより形成するものである。前記酸変性ポリオレフィン層３の厚さとしては、１０μｍ以上であり、好ましくは２０〜６０μｍである。１０μｍ未満では、押出し溶融樹脂の熱量が不足するために十分なラミネート強度が得られず、シール痩せにより酸変性ポリオレフィン系樹脂が強度不足となるなどの理由で、十分なシール強度を得ることができず、５０μｍ超では接着性シートの総厚が増し、端面からの水蒸気バリアー性が低下すると共にコスト対効果（ラミネート強度、シール強度）において顕著な向上効果が見られない。   Next, the acid-modified polyolefin resin 3 will be described. The acid-modified polyolefin-based resin 3 is a layer provided for thermal bonding with the metal terminal 31 (see FIG. 5) and the heat-adhesive resin layer A3 (see FIG. 2) made of a general polyolefin-based resin that is an inner layer of a package. The acid-modified polyolefin resin described in the section of the prior art can be used, although it is necessary to select and use it appropriately depending on the type of resin used for the thermal adhesive resin layer A3 (see FIG. 2). For example, a polyolefin resin graft-modified with an unsaturated carboxylic acid, a copolymer of ethylene or propylene and acrylic acid, or a methacrylic acid, or a metal-crosslinked polyolefin resin. If necessary, a butene component, ethylene -Propylene-butene copolymer, amorphous ethylene-propylene copolymer, propylene-α-olefin copolymer In which the olefin-based elastomer may be added more than 5%. In consideration of moisture resistance and heat resistance, a polyolefin resin graft-modified with an unsaturated carboxylic acid, particularly a polypropylene resin graft-modified with an unsaturated carboxylic acid is preferred. Further, considering the above-described abnormal heat generation and durability due to an increase in internal pressure, a resin added with an olefin-based elastomer having no melting point at 120 ° C. or lower is suitable. The acid-modified polyolefin layer 4 is formed by heat-melting and extruding the acid-modified polyolefin resin described above onto the fibrous sheet or porous sheet 2 from a T-die extruder. The acid-modified polyolefin layer 3 has a thickness of 10 μm or more, preferably 20 to 60 μm. If it is less than 10 μm, sufficient heat strength of the extruded molten resin is insufficient, so that sufficient laminate strength cannot be obtained, and sufficient strength can be obtained due to insufficient strength of the acid-modified polyolefin resin due to seal thinness. On the other hand, if it exceeds 50 μm, the total thickness of the adhesive sheet increases, the water vapor barrier property from the end face decreases, and no significant improvement in cost effectiveness (laminate strength, seal strength) is observed.

また、前記酸変性ポリオレフィン系樹脂３は、必要に応じて顔料を添加して着色層としてもよいものである。これに用いる顔料としては、無機系の各種顔料を用いることができるが、一般に電池の内部に使用されている材料であり、電解液に対する溶出の虞がなく、また、着色効果が大きく接着性を阻害しない程度の添加量で充分な着色効果を得られると共に熱で溶融することがなく添加した樹脂の見かけの溶融粘度を高くすることができ、熱接着時（シール時）に加圧部が薄肉となることを防止してシール強度の低下を防ぐことができるなどの理由から、上記充填剤で例示した炭素（カーボン、グラファイト）が好ましく、その添加量としては、たとえば、平均粒径が約０．０３μｍのカーボンブラックを使用した場合、樹脂１００重量部に対して０．０５〜０．３重量部、好ましく０．１〜０．２重量部である。このように前記酸変性ポリオレフィン層４を着色層とすることにより、前記接着性シート１の有無をセンサーで検知容易なもの、あるいは、目視で検査容易なものとすることができる。なお、前記充填剤含有層と前記着色層とは、同じ酸変性ポリオレフィン系樹脂であってもよいが、異なる酸変性ポリオレフィン系樹脂とするのが酸変性ポリオレフィン系樹脂の熱接着性を阻害しない意味から好ましい。   The acid-modified polyolefin resin 3 may be a colored layer by adding a pigment as necessary. As the pigment used for this, various inorganic pigments can be used, but it is a material generally used in the battery, there is no possibility of elution to the electrolyte, and the coloring effect is large and the adhesiveness is high. A sufficient coloring effect can be obtained with an addition amount that does not hinder, and the apparent melt viscosity of the added resin can be increased without melting by heat, and the pressure part is thin during thermal bonding (sealing) For example, carbon (carbon, graphite) exemplified as the filler is preferable, and for example, the average particle size is about 0. When 0.03 μm carbon black is used, it is 0.05 to 0.3 parts by weight, preferably 0.1 to 0.2 parts by weight, based on 100 parts by weight of the resin. Thus, by using the acid-modified polyolefin layer 4 as a colored layer, the presence or absence of the adhesive sheet 1 can be easily detected by a sensor, or can be easily inspected visually. The filler-containing layer and the colored layer may be the same acid-modified polyolefin resin, but different acid-modified polyolefin resins mean that the thermal adhesiveness of the acid-modified polyolefin resin is not hindered. To preferred.

次に、絶縁性粒子分散層２に分散させる絶縁性粒子について説明する。絶縁性粒子の平均粒系としては、０．１〜３５μｍ、好ましくは５．０〜３０μｍ、さらに好ましくは１０〜２５μｍの範囲のものであって、その含有量としては、絶縁性粒子を添加する樹脂１００重量部に対して５〜３０重量部、好ましくは１０〜２０重量部である。この理由としては、絶縁性粒子が０．１μｍ未満の場合、絶縁性粒子を添加する樹脂１００重量部に対して絶縁性粒子を３０重量部超含有させないと包装体の金属箔からなるバリアー層と金属端子のバリとの短絡を防止することができない。また、絶縁性粒子の平均粒系が３５μｍ超の場合、絶縁性粒子含有量を比較的少なくしないと絶縁性粒子を添加した樹脂層の製膜が困難となる。   Next, the insulating particles dispersed in the insulating particle dispersion layer 2 will be described. The average particle system of the insulating particles is in the range of 0.1 to 35 μm, preferably 5.0 to 30 μm, and more preferably 10 to 25 μm. The amount is 5 to 30 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the resin. The reason for this is that when the insulating particles are less than 0.1 μm, the barrier layer made of the metal foil of the package must contain 30 parts by weight of the insulating particles with respect to 100 parts by weight of the resin to which the insulating particles are added. It is impossible to prevent a short circuit between the metal terminal and the burr. When the average particle size of the insulating particles is more than 35 μm, it is difficult to form a resin layer to which the insulating particles are added unless the insulating particle content is relatively reduced.

前記絶縁性粒子としては、無機系、有機系のいずれも用いることができ、無機系絶縁性粒子としては、酸化アルミニウム、酸化ケイ素、酸化マグネシウム、酸化ジルコニウム、酸化チタン、珪酸ジルコニウム、炭酸カルシウム等を挙げることができ、有機系絶縁性粒子としては、フッ素樹脂、フェノール樹脂、ユリア樹脂、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、ナイロン等を挙げることができ、形状の安定性、剛性、内容物耐性の点から酸化アルミニウム、酸化ケイ素、フッ素樹脂、アクリル樹脂が好ましく、特にこの中でも酸化アルミニウム、酸化ケイ素が熱変形し難くスペーサーとしての効果が高い事及びコスト対効果の点から好ましい。前記絶縁性粒子の絶縁性粒子を添加する樹脂への混合方法としては、予めバンバリーミキサー等で両者をメルトブレンドし、マスターバッチ化したものを所定の混合比にする方法、あるいは、絶縁性粒子を添加する樹脂層を形成する樹脂との直接混合方法のいずれであっても良いものである。   As the insulating particles, either inorganic or organic particles can be used. As the inorganic insulating particles, aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, zirconium silicate, calcium carbonate, etc. can be used. Examples of the organic insulating particles include fluororesin, phenol resin, urea resin, epoxy resin, acrylic resin, polyester resin, nylon, etc., which have shape stability, rigidity, and content resistance. Aluminum oxide, silicon oxide, fluororesin, and acrylic resin are preferable from the standpoint, and among these, aluminum oxide and silicon oxide are particularly preferable because they are difficult to thermally deform and have high effects as spacers and cost effectiveness. As a method of mixing the insulating particles into the resin to which the insulating particles are added, a method in which both are previously melt-blended with a Banbury mixer and the master batch is made into a predetermined mixing ratio, or the insulating particles are used. Any of the direct mixing methods with the resin for forming the resin layer to be added may be used.

次に、本発明について、以下に実施例を挙げてさらに詳しく説明する。
（扁平型電気化学セル用積層体の作成）
予め、フェノール樹脂、フッ化クロム（三価）化合物、リン酸の３成分からなる化成処理液で両面を化成処理（リン酸クロメート処理）したアルミニウム箔（４０μｍ厚さ）の一方の面と２５μｍ厚さの二軸延伸ナイロンフィルムとをウレタン系接着剤を介して積層し、前記アルミニウム箔の他方の面と３０μｍ厚さの未延伸ポリプロピレンフィルムとを酸変性ポリプロピレン樹脂（不飽和カルボン酸でグラフト変性したポリプロピレン）でサンドイッチラミネーションすると共に、熱風により前記酸変性ポリエチレン樹脂の軟化点以上の温度に加熱して実施例に供する積層体を作製した。
（扁平型電気化学セル金属端子部密封用接着シートの作成） Next, the present invention will be described in more detail with reference to the following examples.
(Creation of laminated body for flat electrochemical cell)
One side of an aluminum foil (thickness 40 μm) and a thickness of 25 μm that have been subjected to chemical conversion treatment (phosphate chromate treatment) on both sides with a chemical conversion treatment solution consisting of three components of phenol resin, chromium fluoride (trivalent) compound and phosphoric acid in advance. The biaxially stretched nylon film is laminated via a urethane adhesive, and the other surface of the aluminum foil and the unstretched polypropylene film having a thickness of 30 μm are graft-modified with an acid-modified polypropylene resin (unsaturated carboxylic acid). (Laminated polypropylene) and heated to a temperature equal to or higher than the softening point of the acid-modified polyethylene resin with hot air to prepare a laminate for use in the examples.
(Creation of adhesive sheet for sealing flat electrochemical cell metal terminals)

（実施例１）酸変性ポリプロピレン樹脂〔不飽和カルボン酸でグラフト変性したポリプロピレン、以下ＰＰａと呼称する〕１００重量部に対して平均粒径２０μｍの酸化アルミニウムを１５重量部ブレンドしてマスターバッチ化した樹脂とＰＰａとを周知の共押出法で３層共押出しして、ＰＰａ２０μｍ／ＰＰａ（酸化アルミニウム含有）６０μｍ／ＰＰａ２０μｍの積層フィルムを作成した。   (Example 1) Acid-modified polypropylene resin [polypropylene graft-modified with unsaturated carboxylic acid, hereinafter referred to as PPa] 15 parts by weight of aluminum oxide having an average particle diameter of 20 μm was blended with 100 parts by weight to form a master batch. Three layers of resin and PPa were coextruded by a known coextrusion method to produce a laminated film of PPa 20 μm / PPa (containing aluminum oxide) 60 μm / PPa 20 μm.

（比較例１）両面コロナ放電処理を施したＰＥＴ（１２μｍ）の一方の面にイソシアネート系の接着促進剤を固形分として５０ｍｇ／ｍ2塗布すると共にマレイン酸変性ポリプロピレン（以下、ＰＰａと呼称する）をＴダイ押出機で４４μｍ厚さに押出し塗布し、その後にＰＥＴ（１２μｍ）の他方の面にマレイン酸変性ポリプロピレンをＴダイ押出機で４４μｍ厚さに押出し塗布し、その後４５℃で７２時間エージング処理をして比較例１の接着性シートを得た。 (Comparative Example 1) An isocyanate-based adhesion promoter as a solid content of 50 mg / m 2 was applied to one surface of PET (12 μm) subjected to double-sided corona discharge treatment and maleic acid-modified polypropylene (hereinafter referred to as PPa). Was extruded and coated to a thickness of 44 μm with a T-die extruder, and then maleic acid-modified polypropylene was extruded and coated to a thickness of 44 μm with a T-die extruder on the other side of PET (12 μm), and then aged at 45 ° C. for 72 hours. The adhesive sheet of Comparative Example 1 was obtained by processing.

上記で作製した実施例１及び比較例１の接着性シートを用いて、初期ラミネート強度および電解液に浸漬後のラミネート強度（耐電解液ラミネート強度）、初期シール強度及び電解液封入後のシール強度（耐電解液シール強度）、絶縁性、水蒸気バリアー性、耐熱収縮性、洩れの有無（上記した方法）を下記の評価方法にて評価し、その結果を纏めて表１に示した。   Using the adhesive sheets of Example 1 and Comparative Example 1 prepared above, initial laminate strength, laminate strength after immersion in electrolyte (electrolytic solution laminate strength), initial seal strength, and seal strength after electrolyte solution encapsulation The following evaluation methods evaluated (electrolytic solution seal strength), insulation, water vapor barrier properties, heat shrinkage resistance, and presence / absence of leakage (the above-described method), and the results are summarized in Table 1.

（１）初期ラミネート強度：接着性シートを１５ｍｍ幅に裁断し、酢酸エチルを接着界面に塗布しながら端面より部分剥離した後、テンシロンにて引張り速度５０ｍｍ／分で測定し、その時の平均強度を測定値とした。なお、部分剥離する際に、樹脂層間で凝集破壊しフィルム破れが発生しラミネート強度を測定できないものについては剥離不可とした。
（２）耐電解液ラミネート強度：接着性シートを３０×７０ｍｍの矩形状に裁断し、これを電解液（１モル／リットルの６フッ化リン酸リチウム溶液）に６０℃、７日間ドブ漬けした後に取出して両端を７．５ｍｍずつトリミングして１５×７０ｍｍとしたものを上記した初期ラミネート強度と同様に部分剥離して後、テンシロンにて引張り速度５０ｍｍ／分で測定し、その時の平均強度を測定値とした。なお、部分剥離する際に、樹脂層間で凝集破壊しフィルム破れが発生しラミネート強度を測定できないものについては剥離不可とした。 (1) Initial laminate strength: The adhesive sheet was cut to a width of 15 mm, partially peeled from the end face while applying ethyl acetate to the adhesive interface, then measured with a Tensilon at a pulling speed of 50 mm / min, and the average strength at that time was The measured value was used. In the case of partial peeling, the film was broken due to cohesive failure between the resin layers and the laminate strength could not be measured.
(2) Electrolytic solution laminating strength: The adhesive sheet was cut into a 30 × 70 mm rectangular shape, and this was immersed in an electrolytic solution (1 mol / liter lithium hexafluorophosphate solution) at 60 ° C. for 7 days. After taking out later and trimming both ends by 7.5 mm to 15 × 70 mm, after partially peeling in the same manner as the initial laminate strength described above, the tensile strength was measured with a Tensilon at 50 mm / min, and the average strength at that time was The measured value was used. In the case of partial peeling, the film was broken due to cohesive failure between the resin layers and the laminate strength could not be measured.

（３）初期シール強度：幅が４ｍｍ、長さが３０ｍｍ、厚さが１００μｍのリン酸クロメート処理を施したアルミニウム箔（金属端子）を２枚の接着性シート（幅８ｍｍ、長さ１５ｍｍ）の間に挟持した状態で、アルミニウム箔の長さ方向に直交する方向に２５ｍｍ幅の熱板でシール（シール条件：１９０℃、０．５ＭＰａ、３秒を２回）してアルミニウム金属端子の表裏を２枚の接着性シートで挟持したサンプル（以下、接着性シート付き金属端子サンプルという）を作成した。上記で作成した包装体となる積層体を裁断して６０×７５ｍｍの積層体テストサンプルを２枚作成しシーラントフィルム面同士が対向するように重ね合わせると共に、６０ｍｍ長さの端辺側に上記で作成した接着性シート付き金属端子サンプルを挿入し、前記接着性シート付き金属端子サンプルを挿入した端辺を熱板でシール（シール条件：１９０℃、１．０ＭＰａ、３秒）した後、アルミニウム端子に沿って断裁し、アルミニウム箔の両面に接着性シート及び積層体が一体化された幅４ｍｍ、長さ３０ｍｍの初期シール強度測定用サンプルを作成した。この初期シール強度測定用サンプルの金属端子両面の積層体それぞれを冶具に固定し、オートグラフにて引張り速度３００ｍｍ／分でシール強度を測定し、その時の平均強度を測定値とし、得られた測定値を１５ｍｍ幅当たりのシール強度に換算し初期シール強度を得た。
（４）耐電解液シール強度：上記で作成した包装体となる積層体を裁断して６０×７５ｍｍの積層体テストサンプルを２枚作成しシーラントフィルム面同士が対向するように重ね合わせると共に、６０ｍｍ長さの端辺側に上記で作成した接着性シート付き金属端子サンプルを挿入し、前記接着性シート付き金属端子サンプルを挿入した端辺、対向する両端辺および前記接着性シート付き金属端子サンプルを挿入した端辺に対向する端辺を熱板でそれぞれシール（シール条件：１９０℃、１．０ＭＰａ、３秒）して、前記接着性シート付き金属端子サンプルを挿入した端辺及び該端辺と対向する端辺に７ｍｍ幅の熱接着部を形成すると共に、前記接着性シート付き金属端子サンプルを挿入した端辺に直交する対向する両端辺に１０ｍｍ幅の熱接着部を形成して四方シール包装袋を作成した。なお、包装袋内には、１ｇの電解液〔６フッ化リン酸リチウムを混合液〔エチレンカーボネート／ジエチルカーボネート／ジメチルカーボネート＝１／１／１（容積比）に溶解し、１モル／リットルの６フッ化リン酸リチウム溶液としたもの〕を封入した。その後、前記接着性シート付き金属端子サンプルを挿入した端辺熱接着部が下となるように包装袋を６０℃、９０％ＲＨの恒温恒湿槽に７日間保管した後、取出した包装袋をアルミニウム端子に沿って断裁し、アルミニウム箔の両面に接着性シート及び積層体が一体化された幅４ｍｍ、長さ３０ｍｍの耐電解液シール強度測定用サンプルを作成した。この耐電解液シール強度測定用サンプルの金属端子両面の積層体それぞれを冶具に固定し、オートグラフにて引張り速度３００ｍｍ／分でシール強度を測定し、その時の平均強度を測定値とし、得られた測定値を１５ｍｍ幅当たりのシール強度に換算し耐電解液シール強度を得た。
（５）絶縁性：上記で作製した包装体となる積層体および接着性シートを裁断して６０ｍｍ角のテストサンプルを作製し、前記積層体のシーラントフィルム面同士を対向して前記積層体を配置すると共に、幅が４ｍｍ、長さが８０ｍｍ、厚さが１００μｍのニッケル箔（金属端子）を２枚の接着性シートの間に挟持した状態で前記積層体間に挿入すると共に前記ニッケル箔と前記積層体のアルミニウム箔にテスターの端子を接続し、この状態で前記ニッケル箔の長さ方向に直交する方向に７ｍｍ幅の熱板でシール（シール条件：１９０℃、１．０ＭＰａ）して、前記ニッケル箔と前記積層体のアルミニウム箔とが短絡するまでの時間を測定し、１２０秒以上を絶縁性優良として◎印で示し、８秒未満を絶縁性に劣るとして×印で示した。
（６）洩れの有無：上記で作製した包装体となる積層体を裁断して６０×１６０ｍｍの積層体テストサンプルを作製すると共に、接着性シートを裁断して１５×６０ｍｍの接着性シートテストサンプルを作製した。前記積層体テストサンプルを前記積層体のシーラントフィルム面同士が対向するように２つ折りすると共に６０ｍｍ長さの端辺側に幅が４ｍｍ、長さが２０ｍｍ、厚さが１００μｍの硝酸洗浄処理したニッケル箔（金属端子）と同寸法のリン酸クロメート処理を施したアルミニウム箔（金属端子）とを接触しないように離した状態で平行に２枚の接着性シートの間に挟持した状態で挿入し、３つの端辺を熱板でシール（シール条件：１９０℃、１．０ＭＰａ、３秒）して、７ｍｍ幅の熱接着部を有する三方シール包装袋を作製した。なお、包装袋内には、３ｇの電解液〔６フッ化リン酸リチウムを混合液〔エチレンカーボネート／ジエチルカーボネート／ジメチルカーボネート＝１／１／１（容積比）に溶解し、１モル／リットルの６フッ化リン酸リチウム溶液としたもの〕を封入した。その後、この包装袋を６０℃恒温槽に７日間保管して、金属端子および接着性シートからの電解液洩れの有無を目視で評価した。 (3) Initial sealing strength: An aluminum foil (metal terminal) treated with phosphoric acid chromate having a width of 4 mm, a length of 30 mm, and a thickness of 100 μm is composed of two adhesive sheets (width 8 mm, length 15 mm). While sandwiched between them, seal with a hot plate of 25 mm width in a direction orthogonal to the length direction of the aluminum foil (sealing conditions: 190 ° C., 0.5 MPa, 3 seconds twice) A sample sandwiched between two adhesive sheets (hereinafter referred to as a metal terminal sample with an adhesive sheet) was prepared. Cut the laminated body to be the above-mentioned packaging body to produce two 60 × 75 mm laminated body test samples and superimpose them so that the sealant film surfaces face each other, and on the end side of 60 mm length as described above After inserting the prepared metal terminal sample with an adhesive sheet and sealing the edge with the metal sheet sample with the adhesive sheet with a hot plate (sealing conditions: 190 ° C., 1.0 MPa, 3 seconds), an aluminum terminal And an initial seal strength measurement sample having a width of 4 mm and a length of 30 mm, in which the adhesive sheet and the laminate were integrated on both surfaces of the aluminum foil, was prepared. Each of the laminates on both sides of the metal terminal of the sample for initial seal strength measurement is fixed to a jig, and the seal strength is measured with an autograph at a pulling speed of 300 mm / min. The value was converted into a seal strength per 15 mm width to obtain an initial seal strength.
(4) Electrolyte-resistant seal strength: Cut the laminated body to be the above-prepared packaging body to produce two 60 × 75 mm laminated body test samples and superimpose them so that the sealant film faces face each other, and 60 mm Insert the metal sheet sample with an adhesive sheet prepared above on the end side of the length, and insert the metal terminal sample with the adhesive sheet, the opposite end sides, and the metal terminal sample with the adhesive sheet. The edge opposite to the inserted edge is sealed with a hot plate (sealing conditions: 190 ° C., 1.0 MPa, 3 seconds), and the edge inserted with the metal terminal sample with the adhesive sheet and the edge A heat-bonding portion having a width of 7 mm is formed on the opposite end sides, and a heat-welding portion having a width of 10 mm is formed on both opposite sides orthogonal to the end side where the metal terminal sample with the adhesive sheet is inserted. We have created a four-side sealed packaging bag to form a part. In the packaging bag, 1 g of an electrolytic solution [lithium hexafluorophosphate was dissolved in a mixed solution [ethylene carbonate / diethyl carbonate / dimethyl carbonate = 1/1/1 (volume ratio) and 1 mol / liter What was made into a lithium hexafluorophosphate solution] was sealed. Then, after storing the packaging bag in a constant temperature and humidity chamber at 60 ° C. and 90% RH for 7 days so that the edge thermal bonding part into which the metal terminal sample with the adhesive sheet is inserted is below, The sample was cut along an aluminum terminal, and a 4 mm wide and 30 mm long anti-electrolytic solution sealing strength measurement sample in which an adhesive sheet and a laminate were integrated on both sides of an aluminum foil was prepared. Each of the laminates on both sides of the metal terminal of the sample for measuring anti-electrolytic solution seal strength is fixed to a jig, and the seal strength is measured with an autograph at a pulling speed of 300 mm / min, and the average strength at that time is taken as a measured value. The measured value was converted into seal strength per 15 mm width to obtain anti-electrolytic solution seal strength.
(5) Insulation: The laminate and the adhesive sheet to be produced as above are cut to prepare a 60 mm square test sample, and the laminate is disposed with the sealant film surfaces of the laminate facing each other. In addition, a nickel foil (metal terminal) having a width of 4 mm, a length of 80 mm, and a thickness of 100 μm is inserted between the laminates in a state of being sandwiched between two adhesive sheets, and the nickel foil and the A tester terminal is connected to the aluminum foil of the laminated body, and in this state, sealed with a 7 mm wide hot plate in a direction orthogonal to the length direction of the nickel foil (sealing conditions: 190 ° C., 1.0 MPa), The time until the nickel foil and the aluminum foil of the laminate were short-circuited was measured, and 120 seconds or more were indicated by ◎ as excellent insulation, and less than 8 seconds were indicated by x as inferior in insulation.
(6) Presence / absence of leakage: The laminate produced as the above-mentioned package is cut to produce a 60 × 160 mm laminate test sample, and the adhesive sheet is cut to obtain a 15 × 60 mm adhesive sheet test sample. Was made. The laminate test sample is folded in two so that the sealant film surfaces of the laminate face each other, and the nitric acid-cleaned nickel having a width of 4 mm, a length of 20 mm, and a thickness of 100 μm on the end side of the 60 mm length Insert the foil (metal terminal) and the aluminum foil (metal terminal) treated with phosphoric acid chromate with the same dimensions in a state of being sandwiched between two adhesive sheets in a state where they are separated so as not to contact, Three end sides were sealed with a hot plate (sealing conditions: 190 ° C., 1.0 MPa, 3 seconds) to prepare a three-side sealed packaging bag having a 7 mm-wide heat-bonded portion. In the packaging bag, 3 g of electrolytic solution [lithium hexafluorophosphate was dissolved in a mixed solution [ethylene carbonate / diethyl carbonate / dimethyl carbonate = 1/1/1 (volume ratio) and 1 mol / liter What was made into a lithium hexafluorophosphate solution] was sealed. Then, this packaging bag was stored for 7 days in a 60 degreeC thermostat, and the presence or absence of the electrolyte solution leakage from a metal terminal and an adhesive sheet was evaluated visually.

Figure 2009087628
Figure 2009087628

表１からも明らかように、実施例１及び比較例１の接着性シートは、初期ラミネート強度において優れた性能を示した。しかし、電解液浸漬後のラミネート強度（耐電解液ラミネート強度）において、比較例１はラミネート強度の低下が見られたのに対し、実施例１はラミネート強度の低下が見られなかった。一方、実施例１及び比較例１の接着性シートは、初期シール強度及び電解液封入後のシール強度（耐電解液シール強度）共に高いシール強度を示した。これに対し、比較例１の接着性シートは、初期シール強度が低く、電解液浸漬後のシール強度（耐電解液シール強度）がさらに低下した結果が得られた。また、絶縁性においては、実施例１及び比較例１ともに優れていた。
以上のことから、実施例１の接着性シートは、ラミネート強度及びシール強度ともに高く、電解液浸漬前後の層間強度（ラミネート強度）の低下がなく、電解液封入保管後においても金属端子を挟持した熱接着部でのシール強度の低下がなく、密封性が非常に優れていることが判る。 As is clear from Table 1, the adhesive sheets of Example 1 and Comparative Example 1 showed excellent performance in initial laminate strength. However, in the laminate strength after electrolytic solution immersion (electrolytic solution laminate strength), Comparative Example 1 showed a decrease in laminate strength, whereas Example 1 showed no decrease in laminate strength. On the other hand, the adhesive sheets of Example 1 and Comparative Example 1 showed high seal strength both in the initial seal strength and the seal strength after electrolytic solution encapsulation (electrolytic solution seal strength). On the other hand, the adhesive sheet of Comparative Example 1 had a low initial seal strength, and the result that the seal strength after electrolytic solution immersion (electrolytic solution seal strength) was further reduced was obtained. Moreover, in Example 1, both Example 1 and Comparative Example 1 were excellent.
From the above, the adhesive sheet of Example 1 is high in both the laminate strength and the seal strength, there is no decrease in the interlayer strength before and after immersion in the electrolyte (laminate strength), and the metal terminal is sandwiched even after the electrolyte is sealed and stored. It can be seen that there is no decrease in the sealing strength at the heat-bonded portion, and the sealing performance is very excellent.

本発明にかかる扁平型電気化学セル金属端子部密封用接着性シートの代表的な層構成を図解的に示す図。The figure which shows typically the typical layer structure of the adhesive sheet for flat electrochemical cell metal terminal part sealing concerning this invention. 扁平型電気化学セルに用いる包装体の基本的な層構成を図解的に示す図。The figure which shows the basic layer structure of the package used for a flat type electrochemical cell schematically. 扁平型電気化学セルに用いる包装体の一実施例を説明する図。The figure explaining one Example of the package used for a flat type electrochemical cell. 図４は扁平型電気化学セルに用いる包装体の他の実施例を説明する図FIG. 4 is a diagram for explaining another embodiment of a package used for a flat electrochemical cell. 図５は扁平型電気化学セルの金属端子部に用いる金属端子部密封用接着性シートの設け方の一例を説明する図。FIG. 5 is a view for explaining an example of a method for providing a metal terminal portion sealing adhesive sheet used for a metal terminal portion of a flat electrochemical cell.

符号の説明Explanation of symbols

１，１’ 扁平型電気化学セル金属端子部密封用接着性シート
２ 絶縁性粒子分散層
３ 酸変性ポリオレフィン層
１０ 扁平型電気化学セル
３０ 扁平型電気化学セル本体
３１ 金属端子
Ａ 積層体
Ａ１ 基材層
Ａ２ 金属箔からなるバリアー層
Ａ３ 熱接着性樹脂層 1,1 'flat electrochemical cell metal terminal sealing adhesive sheet 2 insulating particle dispersion layer 3 acid-modified polyolefin layer 10 flat electrochemical cell 30 flat electrochemical cell body 31 metal terminal A laminate A1 substrate Layer A2 Barrier layer made of metal foil A3 Thermal adhesive resin layer

Claims (3)

熱接着性を有するポリオレフィン系樹脂からなる内層と金属箔からなるバリアー層とを少なくとも備えた包装材により、正極および負極を備えた電気化学素子を収納すると共に前記正極および負極に各々接続された金属端子を外側に突出した状態で挟持して周縁熱接着部で密封した扁平型電気化学セルの金属端子取出部における前記内層と前記金属端子との間に介在させる扁平型電気化学セル金属端子部密封用接着性シートであって、該扁平型電気化学セル金属端子部密封用接着性シートは絶縁性粒子が分散した酸変性ポリオレフィン系樹脂からなる絶縁性粒子分散層を前記内層及び金属端子と接着性を有する酸変性ポリオレフィン系樹脂で被覆したものであることを特徴とする扁平型電気化学セル金属端子部密封用接着性シート。 A packaging material having at least an inner layer made of a polyolefin-based resin having thermal adhesion and a barrier layer made of a metal foil, and containing an electrochemical element having a positive electrode and a negative electrode, and a metal connected to the positive electrode and the negative electrode, respectively Flat electrochemical cell metal terminal portion sealed between the inner layer and the metal terminal in the metal terminal extraction portion of a flat electrochemical cell sandwiched in a state where the terminal protrudes outward and sealed by a peripheral thermal bonding portion The adhesive sheet for sealing a flat electrochemical cell metal terminal part has an insulating particle dispersed layer made of an acid-modified polyolefin resin in which insulating particles are dispersed, and is adhesive to the inner layer and the metal terminal. An adhesive sheet for sealing a flat electrochemical cell metal terminal part, characterized in that it is coated with an acid-modified polyolefin resin containing 前記内層を形成するポリオレフィン系樹脂がポリプロピレンからなり、前記酸変性ポリオレフィン系樹脂が不飽和カルボン酸でグラフト変性したポリプロピレンであることを特徴とする請求項１記載の扁平型電気化学セル金属端子部密封用接着性シート。 2. The flat electrochemical cell metal terminal sealing according to claim 1, wherein the polyolefin resin forming the inner layer is made of polypropylene, and the acid-modified polyolefin resin is polypropylene graft-modified with an unsaturated carboxylic acid. Adhesive sheet. 正極及び負極を備えた電気化学素子を収納し、前記正極及び負極の各々に接続された金属端子を突出するように挟持して周縁熱接着部で密封した内層に熱接着性を有するポリオレフィン系樹脂と金属箔からなるバリアー層とを少なくとも備えた包装体からなる扁平型電気化学セルにおいて、前記包装体の前記周縁熱接着部の前記内層と前記金属端子との間に請求項１または２記載の扁平型電気化学セル金属端子部密封用接着シートを介在させた扁平型電気化学セル。 A polyolefin-based resin that contains an electrochemical element including a positive electrode and a negative electrode, has a metal terminal connected to each of the positive electrode and the negative electrode so as to protrude, and is sealed by a peripheral heat-bonding portion, and has a thermal adhesive property The flat electrochemical cell which consists of a package provided with at least a barrier layer made of metal foil, The gap between the inner layer and the metal terminal of the peripheral heat bonding part of the package according to claim 1 or 2 Flat type electrochemical cell Flat type electrochemical cell with an adhesive sheet for sealing metal terminals.
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WO2011016506A1 (en) * 2009-08-07 2011-02-10 大日本印刷株式会社 Packaging material for electrochemical cells
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JP2014123445A (en) * 2012-12-20 2014-07-03 Okura Ind Co Ltd Contraction free heat seal tape for bonding battery lead terminal
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US20150308808A1 (en) * 2014-04-23 2015-10-29 Amita Technologies Inc Ltd. Recognition method for a battery cell package and structure thereof
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000173558A (en) * 1998-12-04 2000-06-23 Tokai Rubber Ind Ltd Thin battery bag body
JP2000208109A (en) * 1999-01-13 2000-07-28 Tokai Rubber Ind Ltd Thin battery bag
JP2003007265A (en) * 2001-06-20 2003-01-10 Dainippon Printing Co Ltd Film for lead wire of battery and packaging material for battery using the same
JP2004095543A (en) * 2002-08-06 2004-03-25 Dainippon Printing Co Ltd Adhesive film for sealing lithium battery metal terminal part
JP2005174825A (en) * 2003-12-12 2005-06-30 Dainippon Printing Co Ltd Adhesive film for sealing lithium battery metallic terminal part and lithium battery using the same
JP2007157412A (en) * 2005-12-02 2007-06-21 Dainippon Printing Co Ltd Lithium ion cell tab and its manufacturing method, and lithium ion cell using the tab
JP2008004430A (en) * 2006-06-23 2008-01-10 Fujimori Kogyo Co Ltd Insulating film
JP2008016337A (en) * 2006-07-06 2008-01-24 Showa Denko Packaging Co Ltd Lead wire covering film material for battery, and film-covered lead wire for battery

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000173558A (en) * 1998-12-04 2000-06-23 Tokai Rubber Ind Ltd Thin battery bag body
JP2000208109A (en) * 1999-01-13 2000-07-28 Tokai Rubber Ind Ltd Thin battery bag
JP2003007265A (en) * 2001-06-20 2003-01-10 Dainippon Printing Co Ltd Film for lead wire of battery and packaging material for battery using the same
JP2004095543A (en) * 2002-08-06 2004-03-25 Dainippon Printing Co Ltd Adhesive film for sealing lithium battery metal terminal part
JP2005174825A (en) * 2003-12-12 2005-06-30 Dainippon Printing Co Ltd Adhesive film for sealing lithium battery metallic terminal part and lithium battery using the same
JP2007157412A (en) * 2005-12-02 2007-06-21 Dainippon Printing Co Ltd Lithium ion cell tab and its manufacturing method, and lithium ion cell using the tab
JP2008004430A (en) * 2006-06-23 2008-01-10 Fujimori Kogyo Co Ltd Insulating film
JP2008016337A (en) * 2006-07-06 2008-01-24 Showa Denko Packaging Co Ltd Lead wire covering film material for battery, and film-covered lead wire for battery

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10177350B2 (en) 2009-08-07 2019-01-08 Dai Nippon Printing Co., Ltd. Electrochemical cell packaging material for housing an electrochemical cell body
CN102473866A (en) * 2009-08-07 2012-05-23 大日本印刷株式会社 Packaging material for electrochemical cells
KR101320011B1 (en) * 2009-08-07 2013-10-18 다이니폰 인사츠 가부시키가이샤 Packaging material for electrochemical cells
US9806303B2 (en) 2009-08-07 2017-10-31 Dai Nippon Printing Co., Ltd. Electrochemical cell packaging material for housing an electrochemical cell body
CN104282852A (en) * 2009-08-07 2015-01-14 大日本印刷株式会社 Packaging material for electrochemical cells
WO2011016506A1 (en) * 2009-08-07 2011-02-10 大日本印刷株式会社 Packaging material for electrochemical cells
US9831476B2 (en) 2009-08-07 2017-11-28 Dai Nippon Printing Co., Ltd. Electrochemical cell packaging material for housing an electrochemical cell body
US9312520B2 (en) 2009-08-07 2016-04-12 Dai Nippon Printing Co., Ltd. Electrochemical cell packaging material
JP2012033324A (en) * 2010-07-29 2012-02-16 Dainippon Printing Co Ltd Packaging material for electrochemical cell
EP2772958A4 (en) * 2011-10-25 2015-06-17 Dainippon Printing Co Ltd Packaging material for electrochemical cell
US10614962B2 (en) 2011-10-25 2020-04-07 Dai Nippon Printing Co., Ltd. Packaging material for electrochemical cell
EP3154102A1 (en) * 2011-10-25 2017-04-12 Dai Nippon Printing Co., Ltd. Packaging material for electrochemical cell
JP2014123445A (en) * 2012-12-20 2014-07-03 Okura Ind Co Ltd Contraction free heat seal tape for bonding battery lead terminal
JP2015141832A (en) * 2014-01-29 2015-08-03 凸版印刷株式会社 Terminal film for electricity storage device and electricity storage device
JP2015139960A (en) * 2014-01-29 2015-08-03 凸版印刷株式会社 Terminal film for electricity-storing device, and electricity-storing device
US9726480B2 (en) * 2014-04-23 2017-08-08 Amita Technologies Inc Ltd. Recognition method for a battery cell package and structure thereof
US20150308808A1 (en) * 2014-04-23 2015-10-29 Amita Technologies Inc Ltd. Recognition method for a battery cell package and structure thereof
JP2015215960A (en) * 2014-05-08 2015-12-03 凸版印刷株式会社 Terminal film for power storage device, and power storage device
JP2017120790A (en) * 2015-12-29 2017-07-06 大日本印刷株式会社 Adhesive film for tightly sealing metal terminal portion of electricity storage device
CN105762321A (en) * 2016-04-29 2016-07-13 廖雪光 Adhesive film for lithium battery plate lug
CN114597602A (en) * 2020-12-04 2022-06-07 比亚迪股份有限公司 Laminated tab for soft package battery and preparation method thereof

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