JP4412966B2 - Lithium-ion battery element winding adhesive tape or sheet - Google Patents
Lithium-ion battery element winding adhesive tape or sheet Download PDFInfo
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- JP4412966B2 JP4412966B2 JP2003360106A JP2003360106A JP4412966B2 JP 4412966 B2 JP4412966 B2 JP 4412966B2 JP 2003360106 A JP2003360106 A JP 2003360106A JP 2003360106 A JP2003360106 A JP 2003360106A JP 4412966 B2 JP4412966 B2 JP 4412966B2
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Description
本発明は、マンガン系、コバルト系等の正極を備えたリチウムイオン電池の構成材料として使用される粘着テープ又はシート、及びこれを用いたリチウムイオン電池に関する。 The present invention relates to a pressure-sensitive adhesive tape or sheet used as a constituent material of a lithium ion battery including a manganese-based or cobalt-based positive electrode, and a lithium ion battery using the same.
従来、リチウムイオン電池は、正極箔と陰極箔とを電解紙（セパレータ紙）を介して巻回したリチウムイオン電池素子の外周に粘着テープを巻き付けて固定し、得られた巻回体を電池缶内に収納し、電解液を注入して素子に含浸させることにより作製されている。しかし、電解液を注入する際、巻回体内部の素子にまで電解液が浸透するには非常に多くの時間を有するという問題があった。この解決手段として、巻回体の下端部から電解液を浸透させる方法（例えば、特許文献１参照）や、正極箔の表面に巻回体としたときに両端部に達するスリット状の電解液案内空隙を複数個設ける方法（例えば、特許文献２参照）などが提案されている。 Conventionally, in a lithium ion battery, a positive electrode foil and a cathode foil are wound around an outer periphery of a lithium ion battery element wound with electrolytic paper (separator paper), and an adhesive tape is wound around and fixed. It is housed inside and is made by injecting an electrolyte and impregnating the element. However, when injecting the electrolytic solution, there is a problem that it takes a very long time for the electrolytic solution to penetrate into the element inside the wound body. As a means for solving this problem, a method of infiltrating the electrolytic solution from the lower end of the wound body (for example, see Patent Document 1), or a slit-shaped electrolytic solution guide that reaches both ends when the wound body is formed on the surface of the positive foil. A method of providing a plurality of voids (for example, see Patent Document 2) has been proposed.
リチウムイオン電池を構成する巻回体の外周部には、巻回体の形態を保持し、保護、絶縁するための粘着テープ（粘着絶縁テープ）が使用されており、この粘着テープの電解液の浸透性を向上させることができれば、電解液注入工程の更なる時間短縮が望める。
従って、本発明の目的は、電解液に対して高い浸透性を発揮することにより短時間で電解液を素子に含浸できると共に、十分な接着性を有するリチウムイオン電池素子巻止用粘着テープ又はシートを提供することにある。
また、本発明の目的は、上記のリチウムイオン電池素子巻止用粘着テープ又はシートを用いたリチウムイオン電池を提供することにある。
Adhesive tape (adhesive insulating tape) is used on the outer periphery of the wound body constituting the lithium ion battery to maintain, protect and insulate the form of the wound body. If the permeability can be improved, the time required for the electrolyte injection process can be further shortened.
Accordingly, an object of the present invention is to provide a lithium ion battery element winding pressure-sensitive adhesive tape or sheet having sufficient adhesiveness while impregnating the element with the electrolyte in a short time by exhibiting high permeability to the electrolyte. Is to provide.
Moreover, the objective of this invention is providing the lithium ion battery using said adhesive tape or sheet | seat for lithium ion battery element winding.
本発明者らは、上記目的を達成するため鋭意検討した結果、特定の構造からなる粘着剤層を有する粘着テープ又はシートによれば、テープの接着機能を維持しつつ電解液の浸透性が向上することにより電解液の注入にかかる時間を短縮でき、リチウムイオン電池を効率よく製造できることを見い出し、本発明を完成した。 As a result of intensive investigations to achieve the above object, the present inventors have improved the permeability of the electrolyte while maintaining the adhesive function of the tape according to the pressure-sensitive adhesive tape or sheet having a pressure-sensitive adhesive layer having a specific structure. As a result, it was found that the time required for injecting the electrolyte solution can be shortened and that a lithium ion battery can be efficiently manufactured, and the present invention has been completed.
すなわち、本発明は、基材の片面に、電解液溶媒により溶解する溶解性領域と電解液溶媒に溶解しない非溶解性領域とからなる粘着剤層を有するリチウムイオン電池素子巻止用粘着テープ又はシートを提供する。前記粘着剤層は、例えば、粘着剤層全表面の１０〜８０％の範囲が溶解性領域であり、好ましくはテープの端部に又はテープの端部に通じる様に溶解性領域が設けられている。 That is, the present invention relates to a lithium ion battery element winding adhesive tape having an adhesive layer comprising a soluble region that dissolves in an electrolyte solvent and a non-soluble region that does not dissolve in an electrolyte solvent, on one side of the substrate. Provide a sheet. The pressure-sensitive adhesive layer has, for example, a range of 10 to 80% of the entire surface of the pressure-sensitive adhesive layer, and preferably has a soluble region so as to communicate with the end of the tape or the end of the tape. Yes.
また、本発明は、素子が、上記本発明のリチウムイオン電池素子巻止用粘着テープ又はシートで巻止めされているリチウムイオン電池を提供する。 Moreover, this invention provides the lithium ion battery by which the element is wound with the adhesive tape or sheet | seat for lithium ion battery element winding of the said invention.
本発明のリチウムイオン電池素子巻止用粘着テープ又はシートによれば、特定の構成からなる粘着剤層を有するため、リチウムイオン電池の構成材料として用いた場合に、電解液に対して極めて高い浸透性を発揮して速やかに素子に含浸されるため電解液注入時間を大幅に短縮でき、しかも素子に対する巻止機能、保護機能、絶縁機能を発揮しうる十分な接着性を保持している。このような粘着テープ又はシートを用いることにより、電解液注入時間を短縮できるため、リチウムイオン電池を高い生産性で製造することができる。 According to the adhesive tape or sheet for winding a lithium ion battery element of the present invention, since it has an adhesive layer having a specific configuration, when used as a constituent material of a lithium ion battery, it has extremely high penetration into the electrolyte. Since the element is impregnated quickly and impregnated, the time for injecting the electrolyte can be greatly shortened, and sufficient adhesiveness that can exhibit a winding function, a protective function, and an insulating function for the element is maintained. By using such an adhesive tape or sheet, the electrolyte injection time can be shortened, so that a lithium ion battery can be manufactured with high productivity.
本発明のリチウムイオン電池素子巻止用粘着テープ又はシートは、基材の片面に、電解液溶媒により溶解する溶解性領域と電解液溶媒に溶解しない非溶解性領域とからなる粘着剤層を有することを特徴としている。 The lithium-ion battery element winding adhesive tape or sheet of the present invention has an adhesive layer composed of a soluble region that dissolves in an electrolyte solution solvent and an insoluble region that does not dissolve in an electrolyte solvent solution on one side of a substrate. It is characterized by that.
基材の形成材料としては、特に限定されないが、例えば、ポリエチレン、ポリプロピレン（ＰＰ）、ポリ塩化ビニル、エチレン−酢酸ビニル共重合体（ＥＶＡ）などのポリオレフィン；ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）などのポリエステル；ポリアリレート；ポリウレタン；ポリカーボネート；ポリアミド；ポリイミド（ＰＩ）；ポリフェニレンサルファイド（ＰＰＳ）；ポリ４フッ化エチレン、及びこれらの複合体等が挙げられる。なかでも、リチウムイオン電池の構成材料に用いる点で、耐熱性を有する多孔質フィルムが好ましく、特に超高分子量ポリオレフィン系多孔質フィルム（例えば、重量平均分子量５０万〜１５００万のポリオレフィンからなる多孔質フィルム）が好ましい。 Although it does not specifically limit as a forming material of a base material, For example, polyolefin, such as polyethylene, polypropylene (PP), polyvinyl chloride, ethylene-vinyl acetate copolymer (EVA); Polyethylene terephthalate (PET), polybutylene terephthalate ( Polyarylates; Polyurethanes; Polycarbonates; Polyamides; Polyimides (PI); Polyphenylene sulfides (PPS); Polytetrafluoroethylene, and composites thereof, and the like, such as polyesters such as PBT) and polyethylene naphthalate (PEN). Among them, a porous film having heat resistance is preferable in that it is used as a constituent material of a lithium ion battery, and particularly an ultra-high molecular weight polyolefin-based porous film (for example, a porous film made of polyolefin having a weight average molecular weight of 500,000 to 15 million). Film) is preferred.
本発明における基材は、片面又は両面に、粘着剤層の密着力の向上などを目的にコロナ処理やプラズマ処理などの物理的処理、下塗り剤などの化学的処理など、適宜表面処理を施してもよい。 The substrate in the present invention is appropriately subjected to surface treatment on one side or both sides, for example, physical treatment such as corona treatment or plasma treatment, chemical treatment such as primer for the purpose of improving the adhesion of the adhesive layer. Also good.
本発明の粘着テープ又はシートの主要な特徴は、電解液溶媒により溶解する溶解性領域と電解液溶媒に溶解しない非溶解性領域とからなる粘着剤層を有することにある。電解液溶媒としては、リチウムイオン電池の構成材料として慣用のものであればよく、例えば、エチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、プロピレンカーボネート等のカーボネート化合物；テトラヒドロフラン、４−メチルジオキソラン、１，２−ジメトキシエタン等のエーテル類；ヘキサメチルホスホルアミドなどのアミド類；ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＢＦ4等のフッ素含有無機酸のリチウム塩；これらの混合液等が挙げられる。 The main feature of the pressure-sensitive adhesive tape or sheet of the present invention is that it has a pressure-sensitive adhesive layer composed of a soluble region that dissolves in an electrolytic solution solvent and a non-soluble region that does not dissolve in the electrolytic solution solvent. The electrolyte solution may be any conventional solvent used as a constituent material of a lithium ion battery. For example, carbonate compounds such as ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate; tetrahydrofuran, 4-methyldioxolane, Examples include ethers such as 1,2-dimethoxyethane; amides such as hexamethylphosphoramide; lithium salts of fluorine-containing inorganic acids such as LiPF 6 , LiAsF 6 , and LiBF 4 ;
粘着剤層を構成する粘着剤としては、例えば、溶解性領域を構成する電解液溶媒に溶解する粘着剤（溶解性粘着剤）と、非溶解性領域を構成する電解液溶媒に溶解しない粘着剤（非溶解性粘着剤）とを組み合わせて用いられる。本発明において、「電解液溶媒により溶解する」とは、厚さ３０μｍの粘着剤層を基材上に設けた粘着テープを、被着体としてのステンレス板に貼り付けて電解液に３０分間浸漬したときに、電解液中で粘着テープが被着体から完全に剥離する状態を意味しており、このような粘着剤層を構成する粘着剤を「電解液溶媒により溶解する粘着剤（溶解性粘着剤）」と称している。本発明の粘着テープによれば、電解液との接触により溶解性粘着剤が溶解するため、粘着剤層が部分的に消失し、又は被着体が部分的に界面剥離を生じて粘着テープと素子との間に空隙を形成し、該空隙が電解液の浸透経路となることにより浸透性が著しく向上する。電解液の浸透経路を確保するという観点から、前記溶解性領域は、好ましくはテープ端部に、又はテープの端部に通じる様に設けられる。 Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include a pressure-sensitive adhesive (soluble pressure-sensitive adhesive) that dissolves in the electrolyte solution solvent that constitutes the soluble region and a pressure-sensitive adhesive that does not dissolve in the electrolyte solution solvent that constitutes the insoluble region. It is used in combination with (non-soluble adhesive). In the present invention, “dissolves with an electrolyte solvent” means that an adhesive tape having a 30 μm thick adhesive layer provided on a substrate is attached to a stainless steel plate as an adherend and immersed in the electrolyte for 30 minutes. Means that the pressure-sensitive adhesive tape is completely peeled off from the adherend in the electrolyte, and the pressure-sensitive adhesive constituting such a pressure-sensitive adhesive layer is expressed as “pressure-sensitive adhesive that dissolves in the electrolyte solution (solubility) It is called “adhesive”. According to the pressure-sensitive adhesive tape of the present invention, since the soluble pressure-sensitive adhesive dissolves upon contact with the electrolytic solution, the pressure-sensitive adhesive layer partially disappears, or the adherend partially causes interfacial peeling and A gap is formed between the element and the gap serves as a permeation path for the electrolyte, whereby the permeability is remarkably improved. From the viewpoint of securing a permeation path for the electrolyte, the soluble region is preferably provided at the end of the tape or so as to communicate with the end of the tape.
粘着剤層を構成する粘着剤としては、電池性能に悪影響を及ぼさないものであれば特に限定されるものではなく、例えば、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤等が挙げられる。なかでも、熱溶融性を有する粘着剤が好ましく、特にアクリル系粘着剤が好ましい。 The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited as long as it does not adversely affect battery performance, and examples thereof include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. . Especially, the adhesive which has heat melting property is preferable, and an acrylic adhesive is especially preferable.
アクリル系粘着剤としては、例えば、粘着性を与え、ガラス転移点（Ｔｇ）が比較的低いポリマーを形成しうる主モノマー、接着性や凝集力を与え、Ｔｇが比較的高いポリマーを形成しうるコモノマー、及び架橋点の形成や接着性を改良しうる官能基含有モノマー等の単量体成分を重合させたアクリル系共重合体からなる粘着剤が用いられる。 As the acrylic pressure-sensitive adhesive, for example, it is possible to form a polymer having a relatively high Tg, giving a tackiness, a main monomer capable of forming a polymer having a relatively low glass transition point (Tg), adhesiveness and cohesion. A pressure-sensitive adhesive made of an acrylic copolymer obtained by polymerizing a monomer component such as a comonomer and a functional group-containing monomer capable of improving the formation of a crosslinking point and adhesiveness is used.
前記アクリル系共重合体の主モノマーとしては、例えば、アクリル酸エチル、アクリル酸ブチル、アクリル酸アミル、アクリル酸２−エチルヘキシル、アクリル酸オクチル等のアクリル酸アルキルエステル、アクリル酸シクロヘキシル等のアクリル酸シクロアルキルエステル、アクリル酸ベンジル等のアクリル酸アラルキルエステルや、メタクリル酸ブチル、メタクリル酸２−エチルヘキシル等のメタクリル酸アルキルエステル、メタクリル酸シクロヘキシル等のメタクリル酸シクロアルキルエステル、メタクリル酸ベンジル等のメタクリル酸アラルキルエステルなどが挙げられる。コモノマーとしては、例えば、アクリル酸メチル、メタクリル酸メチル、メタクリル酸エチル、酢酸ビニル、プロピオン酸ビニル、ビニルエーテル、スチレン、アクリロニトリル、メタクリロニトリル等のビニル基含有化合物が挙げられる。 The main monomer of the acrylic copolymer includes, for example, ethyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, alkyl acrylate such as octyl acrylate, and cycloacrylate acrylate such as cyclohexyl acrylate. Aralkyl esters such as alkyl esters, benzyl acrylate, etc., alkyl methacrylates such as butyl methacrylate and 2-ethylhexyl methacrylate, cycloalkyl esters such as cyclohexyl methacrylate, and methacrylic acid aralkyl esters such as benzyl methacrylate. Etc. Examples of the comonomer include vinyl group-containing compounds such as methyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, vinyl propionate, vinyl ether, styrene, acrylonitrile, and methacrylonitrile.
前記官能基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸等のカルボキシル基含有モノマー；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、Ｎ−メチロールアクリルアミド、アリルアルコール等のヒドロキシル基含有モノマー；ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート等の３級アミノ基含有モノマー；アクリルアミド、メタクリルアミド等のアミド基含有モノマー；Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−エトキシメチル（メタ）アクリルアミド、Ｎ−ｔ−ブチルアクリルアミド、Ｎ−オクチルアクリルアミド等のＮ−置換アミド基含有モノマー；グリシジルメタクリレート等のエポキシ基含有モノマーなどが挙げられる。これらのモノマーは１種又は２種以上を混合して使用できる。 Examples of the functional group-containing monomer include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyl group-containing monomers such as acrylate, 4-hydroxybutyl (meth) acrylate, N-methylolacrylamide, and allyl alcohol; 3 such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate Secondary amino group-containing monomers; Amide group-containing monomers such as acrylamide and methacrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylic De, N- ethoxymethyl (meth) acrylamide, N-t-butyl acrylamide, N- substituted amide group-containing monomers such as N- octyl acrylamide; an epoxy group-containing monomers such as glycidyl methacrylate. These monomers can be used alone or in combination of two or more.
上記単量体成分の種類や組み合わせを適宜選択することにより、優れた粘着性、凝集性、耐久性を有するアクリル系共重合体を得ることができる。このように、粘着剤の主成分となるポリマーを適宜選択することにより、用途に応じた任意の品質、特性を有する粘着剤層を形成することができる。 By appropriately selecting the type and combination of the monomer components, an acrylic copolymer having excellent adhesiveness, cohesiveness, and durability can be obtained. Thus, the adhesive layer which has arbitrary quality and characteristics according to a use can be formed by selecting suitably the polymer used as the main ingredient of an adhesive.
粘着剤を構成するポリマーの重量平均分子量は、特に限定されないが、例えば２０万〜１５０万、好ましくは４０万〜１００万である。分子量が小さ過ぎると、粘着剤の粘着力や凝集力が劣り、分子量が大き過ぎると粘着剤が硬くなり、粘着性が不十分となって貼着の作業性が低下しやすい。ポリマーのＴｇは、特に限定されないが、−２０℃以下であるのが好ましい。Ｔｇが−２０℃を超える場合、使用温度によっては粘着剤が硬くなり、粘着性を維持できなくなる場合がある。 The weight average molecular weight of the polymer constituting the pressure-sensitive adhesive is not particularly limited, but is, for example, 200,000 to 1,500,000, preferably 400,000 to 1,000,000. If the molecular weight is too small, the adhesive force and cohesive force of the pressure-sensitive adhesive are inferior, and if the molecular weight is too large, the pressure-sensitive adhesive becomes hard and the adhesiveness becomes insufficient, so that the workability of sticking tends to decrease. The Tg of the polymer is not particularly limited, but is preferably −20 ° C. or lower. When Tg exceeds −20 ° C., the pressure-sensitive adhesive becomes hard depending on the use temperature, and the adhesiveness may not be maintained.
粘着剤は、架橋型、非架橋型のいずれのものも使用できる。架橋型の場合には、粘着剤は、上記ポリマーの他に架橋剤を含んでいてもよい。架橋剤としては、粘着剤が有する架橋性官能基の種類に応じて適宜選択でき、例えば、エポキシ系架橋剤、イソシアナート系架橋剤、金属キレート系架橋剤、金属アルコキシド系架橋剤、金属塩系架橋剤、アミン系架橋剤、ヒドラジン系架橋剤、アルデヒド系架橋剤等が挙げられる。これらの架橋剤は単独で又は２種以上組み合わせて使用できる。 As the pressure-sensitive adhesive, either a crosslinked type or a non-crosslinked type can be used. In the case of the crosslinking type, the pressure-sensitive adhesive may contain a crosslinking agent in addition to the polymer. As a crosslinking agent, it can select suitably according to the kind of the crosslinkable functional group which an adhesive has, for example, an epoxy type crosslinking agent, an isocyanate type crosslinking agent, a metal chelate type crosslinking agent, a metal alkoxide type crosslinking agent, a metal salt type Examples include a crosslinking agent, an amine-based crosslinking agent, a hydrazine-based crosslinking agent, and an aldehyde-based crosslinking agent. These crosslinking agents can be used alone or in combination of two or more.
上記架橋剤は、粘着剤を構成するポリマーの組成や分子量等に応じて、電解液溶媒に対して所望の溶解性を発揮しうる範囲で用いられる。本発明においては、粘着剤層を構成する溶解性粘着剤として架橋剤を含有しない非架橋型粘着剤が、非溶解性粘着剤として架橋剤を含有する架橋型粘着剤が、それぞれ好ましく用いられる。 The said crosslinking agent is used in the range which can exhibit desired solubility with respect to electrolyte solution solvent according to the composition, molecular weight, etc. of the polymer which comprises an adhesive. In the present invention, a non-crosslinking adhesive not containing a crosslinking agent is preferably used as the soluble adhesive constituting the adhesive layer, and a crosslinking adhesive containing a crosslinking agent as the non-soluble adhesive is preferably used.
粘着剤には、上記のほかに、必要に応じて、紫外線吸収材、粘着付与剤、軟化剤（可塑剤）、老化防止剤、安定剤、充填剤、老化防止剤、粘着付与剤、顔料、染料、シランカップリング剤等の添加剤が含まれていてもよい。粘着付与剤としては、例えば、ロジン及びその誘導体、ポリテルペン、テルペンフェノール樹脂、クマロン−インデン樹脂、石油系樹脂、スチレン樹脂、キシレン樹脂等が挙げられる。軟化剤としては、例えば、液状ポリエーテル、グリコールエステル、液状ポリテルペン、液状ポリアクリレート、フタル酸エステル、トリメリット酸エステル等が挙げられる。 In addition to the above, the pressure-sensitive adhesive includes an ultraviolet absorber, a tackifier, a softener (plasticizer), an anti-aging agent, a stabilizer, a filler, an anti-aging agent, a tackifier, a pigment, Additives such as dyes and silane coupling agents may be included. Examples of the tackifier include rosin and derivatives thereof, polyterpene, terpene phenol resin, coumarone-indene resin, petroleum resin, styrene resin, xylene resin and the like. Examples of the softening agent include liquid polyether, glycol ester, liquid polyterpene, liquid polyacrylate, phthalic acid ester, trimellitic acid ester, and the like.
粘着剤層全表面に対して溶解性領域が占める割合（面積比）は、下記式により算出される。
面積比（％）＝（ｓ／Ｓ）×１００
（式中、ｓは溶解性領域の面積、Ｓは粘着剤層全表面積を示す）
上記面積比は、例えば１０％以上８０％以下、好ましくは２０％以上７０％以下である。溶解性領域が粘着剤層全表面の１０％未満では、電解液の注入時間の短縮効果が得られにくく、８０％を超えると、粘着テープ本来の特性である粘着力が減衰し、素子に対する巻止機能、保護機能、絶縁機能が低下しやすい。粘着剤において、電解液溶媒に対する溶解性の調整は、粘着剤を構成するポリマーの架橋度、溶解性、及び粘着付与剤の種類や量等をコントロールすることにより行われる。
The ratio (area ratio) of the soluble region to the entire surface of the pressure-sensitive adhesive layer is calculated by the following formula.
Area ratio (%) = (s / S) × 100
(In the formula, s represents the area of the soluble region, and S represents the total surface area of the pressure-sensitive adhesive layer)
The area ratio is, for example, 10% to 80%, preferably 20% to 70%. If the solubility region is less than 10% of the entire surface of the pressure-sensitive adhesive layer, it is difficult to obtain the effect of shortening the injection time of the electrolytic solution, and if it exceeds 80%, the adhesive force, which is the original characteristic of the pressure-sensitive adhesive tape, is attenuated. Stop function, protection function and insulation function are likely to deteriorate. In the pressure-sensitive adhesive, the solubility in the electrolyte solution is adjusted by controlling the degree of crosslinking of the polymer constituting the pressure-sensitive adhesive, the solubility, the type and amount of the tackifier, and the like.
本発明のリチウムイオン電池素子巻止用粘着テープ又はシートは、例えば、基材の片面に、上記非溶解性粘着剤と溶解性粘着剤（例えば、架橋剤含有粘着剤と架橋剤非含有粘着剤）を交互にストライプ塗工した後、乾燥又は冷却してロールに巻き取り、所定の幅にスリットを設けることにより製造できる。粘着剤層の厚さは、特に限定されないが、例えば５〜１００μｍ程度、好ましくは５〜６０μｍ程度である。 The adhesive tape or sheet for winding a lithium ion battery element of the present invention has, for example, the above-mentioned non-soluble adhesive and soluble adhesive (for example, a crosslinking agent-containing adhesive and a crosslinking agent-free adhesive on one side of a substrate). ) Alternately, and then dried or cooled, wound on a roll, and provided with a slit having a predetermined width. Although the thickness of an adhesive layer is not specifically limited, For example, it is about 5-100 micrometers, Preferably it is about 5-60 micrometers.
本発明の粘着テープ又はシートには、必要に応じて、粘着剤を保護するため粘着剤層上に離型フィルムを積層してもよい。離型フィルムとしては、粘着テープ又はシートの分野において慣用のものを使用でき、例えば、グラシン紙のような紙材や、ポリエチレン、ポリプロピレン、ポリエステル等などの樹脂フィルムからなる支持体上に、シリコーンなどの離型剤が形成されたフィルムなどを用いることができる。 In the pressure-sensitive adhesive tape or sheet of the present invention, if necessary, a release film may be laminated on the pressure-sensitive adhesive layer in order to protect the pressure-sensitive adhesive. As the release film, those commonly used in the field of pressure-sensitive adhesive tapes or sheets can be used. For example, on a support made of a paper material such as glassine paper or a resin film such as polyethylene, polypropylene, polyester, etc. A film on which a mold release agent is formed can be used.
また、本発明の粘着テープ又はシートにおいて、テープ自背面に対する接着部分がある場合に、自背面への接着力をより強固にする目的でテープの背面側（基材側）に背面処理層を設けてもよい。背面処理層は、長鎖アルキルアクリレート共重合体、長鎖アルキルビニルエーテル共重合体、長鎖アルキルビニルエステル共重合体などの剥離処理剤を基材背面に塗布することにより形成される。背面処理層は、剥離処理剤のほかに、上記に例示の添加剤を含んでいてもよい。 In addition, in the pressure-sensitive adhesive tape or sheet of the present invention, when there is an adhesive part to the back surface of the tape, a back treatment layer is provided on the back side (base material side) of the tape for the purpose of further strengthening the adhesive force to the back surface. May be. The back treatment layer is formed by applying a release treatment agent such as a long chain alkyl acrylate copolymer, a long chain alkyl vinyl ether copolymer, or a long chain alkyl vinyl ester copolymer to the back surface of the substrate. The back surface treatment layer may contain the additives exemplified above in addition to the release treatment agent.
本発明の粘着テープ又はシートは、上記のほかに、用途に応じて１又は２以上の任意の層を設けてもよい。 In addition to the above, the pressure-sensitive adhesive tape or sheet of the present invention may be provided with one or more arbitrary layers depending on the application.
本発明のリチウムイオン電池は、素子が、上記本発明のリチウムイオン電池素子巻止用粘着テープ又はシートで巻止めされている点を特徴としている。このため、電解液注入工程において、粘着剤層が電解液と接触して溶解した部分（溶解性領域）が浸透経路となって、注入した電解液は速やかに内部へ浸透して短時間で素子に含浸させることができる。このように前記工程の作業効率が向上することにより、リチウムイオン電池を高い生産性で製造することができる。 The lithium ion battery of the present invention is characterized in that the element is fastened with the above-described pressure-sensitive adhesive tape or sheet for winding the lithium ion battery element of the present invention. For this reason, in the electrolytic solution injection process, the portion (soluble region) in which the adhesive layer is in contact with the electrolytic solution is an infiltration path, and the injected electrolytic solution quickly infiltrates into the device in a short time. Can be impregnated. Thus, the work efficiency of the said process improves, A lithium ion battery can be manufactured with high productivity.
本発明において、リチウム二次電池の構造等は特に限定されないが、一般に、リチウム二次電池は正極活物質と負極活物質と電解液とで構成される。前記正極活物質としては、例えばマンガン酸塩（マンガン酸リチウムなど）、マンガン酸化物や等のマンガン系化合物、コバルト酸塩（コバルト酸リチウムなど）、コバルト酸化物等のコバルト化合物、ニッケル酸化物等のニッケル系化合物、鉄系化合物、遷移金属硫化物などが使用される。これらの中でも、マンガン系又はコバルト系化合物が好ましい。負極活物質としては、例えば、リチウム−黒鉛層間化合物、リチウム−ソフト・カーボン層間化合物、リチウム−ハード・カーボン層間化合物などのリチウム−炭素層間化合物などが例示される。電解液としては、例えば、エチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、プロピレンカーボネート等のカーボネート化合物；テトラヒドロフラン、４−メチルジオキソラン、１，２−ジメトキシエタン等のエーテル類；ヘキサメチルホスホルアミドなどのアミド類；ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＢＦ4等のフッ素含有無機酸のリチウム塩；これらの混合液等が挙げられる。好ましい電解液には、カーボネート化合物とフッ素含有無機酸のリチウム塩との混合液などが含まれる。 In the present invention, the structure and the like of the lithium secondary battery are not particularly limited, but in general, the lithium secondary battery is composed of a positive electrode active material, a negative electrode active material, and an electrolytic solution. Examples of the positive electrode active material include manganese compounds (such as lithium manganate), manganese compounds such as manganese oxide, cobalt salts (such as lithium cobalt oxide), cobalt compounds such as cobalt oxide, nickel oxide, and the like. Nickel compounds, iron compounds, transition metal sulfides, and the like are used. Among these, manganese-based or cobalt-based compounds are preferable. Examples of the negative electrode active material include lithium-carbon intercalation compounds such as lithium-graphite intercalation compounds, lithium-soft carbon intercalation compounds, and lithium-hard carbon intercalation compounds. Examples of the electrolytic solution include carbonate compounds such as ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate; ethers such as tetrahydrofuran, 4-methyldioxolane and 1,2-dimethoxyethane; hexamethylphosphoramide Amides such as: Lithium salts of fluorine-containing inorganic acids such as LiPF 6 , LiAsF 6 , LiBF 4 ; a mixture thereof. A preferable electrolytic solution includes a mixed solution of a carbonate compound and a lithium salt of a fluorine-containing inorganic acid.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
実施例１
厚さ３０μｍの二軸延伸ポリプロピレンフィルム［基材；商品名「トレファン」、東レ（株）製］の片面に、単量体成分としてアクリル酸ブチル９０重量部とアクリル酸１０重量部とを用いたアクリル酸エステル系共重合体［重量平均分子量（Ｍｗ）５０万］１００重量部、及びトリメチロールプロパントリレンジイソシアナート（架橋剤）２重量部からなる架橋剤含有アクリル系粘着剤組成物と、該粘着剤組成物から架橋剤を除く成分で構成される架橋剤非含有アクリル系粘着剤組成物（溶解性粘着剤）とを組み合わせて用い、粘着剤層全表面の５０％が溶解性粘着剤で構成されるようにストライプ塗工し、乾燥することにより厚さ３０μｍの粘着剤層を有する粘着テープを得た。
得られた粘着テープの基材表面に、セルロースアセテート系重合体（Ｍｗ５０万）１００重量部と長鎖アルキルアクリレート系重合体（離型成分）３０重量部との混合物を塗布し、厚さ１μｍ未満の背面処理層を設けることにより、背面処理層、基材、粘着剤層がこの順に積層した粘着テープを作製した。
Example 1
90 parts by weight of butyl acrylate and 10 parts by weight of acrylic acid are used as monomer components on one side of a 30 μm-thick biaxially stretched polypropylene film [base material; trade name “Trephan”, manufactured by Toray Industries, Inc.] A crosslinking agent-containing acrylic pressure-sensitive adhesive composition comprising 100 parts by weight of an acrylic ester copolymer [weight average molecular weight (Mw) 500,000] and 2 parts by weight of trimethylolpropane tolylene diisocyanate (crosslinking agent); The pressure-sensitive adhesive composition is used in combination with a crosslinking agent-free acrylic pressure-sensitive adhesive composition (soluble pressure-sensitive adhesive) composed of components excluding the crosslinking agent, and 50% of the entire surface of the pressure-sensitive adhesive layer is soluble pressure-sensitive adhesive. The adhesive tape having a 30 μm-thick adhesive layer was obtained by coating with stripes so as to be constituted by and drying.
A mixture of 100 parts by weight of a cellulose acetate polymer (Mw 500,000) and 30 parts by weight of a long-chain alkyl acrylate polymer (release component) is applied to the surface of the base material of the obtained adhesive tape, and the thickness is less than 1 μm. By providing the back treatment layer, an adhesive tape in which the back treatment layer, the substrate, and the adhesive layer were laminated in this order was produced.
実施例２
実施例１において、架橋剤含有アクリル系粘着剤組成物の代わりに、天然ゴム（粘着剤成分）１００重量部、テルペン系樹脂（粘着付与樹脂）４０重量部、石油系樹脂（粘着付与樹脂）３０重量部、及び老化防止剤（商品名「スミライザーＮＷ」、住友化学（株）製）２重量部からなるゴム系粘着剤組成物を用いた以外は、実施例１と同様の操作を行って粘着テープを得た。
Example 2
In Example 1, instead of the crosslinker-containing acrylic pressure-sensitive adhesive composition, 100 parts by weight of natural rubber (pressure-sensitive adhesive component), 40 parts by weight of terpene-based resin (tackifying resin), and petroleum-based resin (tackifying resin) 30 Adhesion was carried out in the same manner as in Example 1 except that a rubber-based pressure-sensitive adhesive composition consisting of 2 parts by weight and an anti-aging agent (trade name “Sumilyzer NW”, manufactured by Sumitomo Chemical Co., Ltd.) was used. I got a tape.
比較例１
実施例１において、粘着剤溶液として、架橋剤非含有アクリル系粘着剤組成物を用いないで架橋剤含有アクリル系粘着剤組成物のみを用いて基材の全表面に塗工した点以外は、実施例１と同様の操作を行って粘着テープを得た。
Comparative Example 1
In Example 1, as a pressure-sensitive adhesive solution, except that the cross-linking agent-containing acrylic pressure-sensitive adhesive composition was not used and the cross-linking agent-containing acrylic pressure-sensitive adhesive composition was used only on the entire surface of the substrate, The same operation as in Example 1 was performed to obtain an adhesive tape.
評価試験
実施例及び比較例で得られた粘着テープについて以下の評価を行い、結果を表１に示した。
（接着性）
実施例及び比較例で得られた粘着テープを円筒に巻いたものを、電解液溶媒（ＬｉＰＦ6をエチレンカーボネートとジエチルカーボネートとの体積比１：２の混合溶媒に１ｍｏｌ／Ｌの濃度に溶解した溶液）に浸し、テープの剥がれ性を目視にて評価した。巻止め部の剥がれがなかった場合には「○」、剥がれがあった場合には「×」として評価し、結果を表１の「接着性」の欄に示した。
（浸透性）
実施例及び比較例で得られた各粘着テープを１０ｍｍ×１０ｍｍのサイズに切り取ってテープサンプルとし、金属板（ステンレス板）に貼り付け、該金属板を４５°に傾けた状態で、貼り付けられているテープサンプルの上部より電解液溶媒（ＬｉＰＦ6をエチレンカーボネートとジエチルカーボネートとの体積比１：２の混合溶媒に１ｍｏｌ／Ｌの濃度に溶解した溶液）をテープ表面に溢れないように垂らし、５分経過後、テープ下部からの電解液溶媒の染みだしの状況を評価した。得られた結果を表１中、「浸透性」の欄に、電解液溶媒が染みだしていた場合を「＋」、染みだしていなかった場合を「−」と示した。
Evaluation Test The following evaluations were performed on the adhesive tapes obtained in Examples and Comparative Examples, and the results are shown in Table 1.
(Adhesiveness)
Those adhesive tapes obtained in Examples and Comparative Examples were rolled into a cylindrical, electrolyte solvent (volume ratio of the LiPF 6 ethylene carbonate and diethyl carbonate was dissolved in a 1: Concentration of 1 mol / L to 2 mixture of The film was soaked in the solution, and the peelability of the tape was visually evaluated. When there was no peeling of the winding stop part, it was evaluated as “◯”, and when there was peeling off, it was evaluated as “x”, and the result is shown in the “Adhesiveness” column of Table 1.
(Penetration)
Each adhesive tape obtained in Examples and Comparative Examples is cut to a size of 10 mm × 10 mm to form a tape sample, which is attached to a metal plate (stainless steel plate), and is attached in a state where the metal plate is inclined at 45 °. An electrolyte solvent (LiPF 6 dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 2 at a concentration of 1 mol / L) is dropped from the upper part of the tape sample so as not to overflow the tape surface. After 5 minutes, the state of the electrolyte solvent oozing out from the lower part of the tape was evaluated. In Table 1, in the column of “permeability”, the obtained results are shown as “+” when the electrolyte solvent oozes out, and “−” when it does not ooze out.
表１に示されるように、実施例１，２の各粘着テープは、電解液を注入して５分後には電解液を浸透することができるため、電解液注入時間を短縮する特性と同時に、素子を巻止める接着性を有している。これに対し、比較例１の粘着テープでは、５分経過後にも電解液の浸透がみられず、電解液注入時間を短縮する特性がないことが確認された。 As shown in Table 1, each adhesive tape of Examples 1 and 2 can infiltrate the electrolyte solution 5 minutes after injecting the electrolyte solution. It has adhesiveness to wind the element. On the other hand, in the adhesive tape of Comparative Example 1, it was confirmed that the electrolyte solution did not permeate even after 5 minutes and the electrolyte injection time was not shortened.
Claims (4)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9755207B2 (en) | 2011-02-28 | 2017-09-05 | Nitto Denko Corporation | Pressure-sensitive adhesive tape for battery and battery using the pressure-sensitive adhesive tape |
Families Citing this family (14)
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| JP5417324B2 (en) * | 2008-05-13 | 2014-02-12 | 株式会社クレハ | Lithium ion battery and electrode winding body for lithium ion battery |
| JP5363836B2 (en) * | 2009-03-02 | 2013-12-11 | 日東電工株式会社 | Battery adhesive tape and battery using this battery adhesive tape |
| US8288036B2 (en) | 2009-05-18 | 2012-10-16 | Samsung Sdi Co., Ltd. | Secondary battery and method of making the secondary battery |
| KR101136254B1 (en) * | 2010-05-20 | 2012-04-19 | 삼성에스디아이 주식회사 | Secondary battery |
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| JP5798404B2 (en) * | 2010-08-31 | 2015-10-21 | 日東電工株式会社 | Adhesive tape for electrode plate protection |
| WO2012039457A1 (en) | 2010-09-22 | 2012-03-29 | 日本ゼオン株式会社 | Adhesive film for organic electrolyte accumulator devices |
| WO2012056846A1 (en) | 2010-10-27 | 2012-05-03 | 東レフィルム加工株式会社 | Secondary battery, method for manufacturing same, and thermal adhesive insulating film for secondary battery |
| CN103160226A (en) * | 2011-12-18 | 2013-06-19 | 日东电工（上海松江）有限公司 | Pressure-sensitive adhesive composition, pressure-sensitive printing ink composite and pressure-sensitive adhesive tape made thereof |
| PL3223356T3 (en) | 2014-11-18 | 2020-11-30 | Zeon Corporation | Use of double-sided tape for fixing electrode constituent body, and secondary battery |
| KR102132844B1 (en) * | 2018-07-17 | 2020-07-10 | 삼성에스디아이 주식회사 | Secondary battery |
| CN114094105A (en) * | 2021-11-23 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Battery with improved battery capacity |
-
2003
- 2003-10-21 JP JP2003360106A patent/JP4412966B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9755207B2 (en) | 2011-02-28 | 2017-09-05 | Nitto Denko Corporation | Pressure-sensitive adhesive tape for battery and battery using the pressure-sensitive adhesive tape |
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|---|---|
| JP2005126452A (en) | 2005-05-19 |
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