JP4271756B2 - Battery adhesive or adhesive or adhesive tape sheet - Google Patents

Battery adhesive or adhesive or adhesive tape sheet Download PDF

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Publication number
JP4271756B2
JP4271756B2 JP34242498A JP34242498A JP4271756B2 JP 4271756 B2 JP4271756 B2 JP 4271756B2 JP 34242498 A JP34242498 A JP 34242498A JP 34242498 A JP34242498 A JP 34242498A JP 4271756 B2 JP4271756 B2 JP 4271756B2
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Japan
Prior art keywords
adhesive
pressure
sensitive adhesive
battery
sheet
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JP34242498A
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Japanese (ja)
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JP2000173621A (en
Inventor
正 寺島
正一 谷本
敏光 奥野
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Nitto Denko Corp
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Nitto Denko Corp
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Adhesives Or Adhesive Processes (AREA)
  • Secondary Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Adhesive Tapes (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、電池内部、特に電池電解液に接する又は接する可能性のある部分に好適に用いることができる電池用接着剤又は粘着剤もしくは粘着テープ・シート(以下、これらをまとめて単に接着剤もしくは粘着テープということがある。)に関する。
【0002】
【発明が解決しようとする課題】
電池内部には、その製造工程上、接着剤や粘着テープが多用されており、これらの構成材料は、主に被着体との接着性などを考慮して選択されている。
特にリチウム塩を支持電解質として用いる非水電解液系の電池系内においては、通常、水分を供与する素材の使用は好まれない。 これは、水分を供与する素材が電池系内に存在すると電解液中のリチウム塩に作用して、フッ化物あるいはオキシフッ化物が形成され、電池の内圧上昇や電池部材の腐食等を引き起こすためとされている。
しかし最近、このフッ化物あるいはオキシフッ化物が形成されることにより、電極集電体の劣化を抑制する効果が報告されている。 これは例えば、正極の集電体として多く用いられているアルミ金属において、電池系内でフッ化物あるいはオキシフッ化物によりその表面に不動態皮膜が形成され、酸化雰囲気下においても安定化するためであると考えられている。
本来、電解液中に残存する微量水分や電池組み立て工程において混入する微量水分によってもフッ化物あるいはオキシフッ化物が形成されるが、これらの水分量は常に安定なものではなく、結果として形成されるフッ化物あるいはオキシフッ化物量も一定ではなかった。
また、LiCF3SO3やLi(CF3SO2)2Nに代表されるフッ素含有有機系の電解質は安定なC-F結合から構成され、他の無機系の電解質に比べて安定していることから、形成するフッ化物やオキシフッ化物量が少なくなるとされている。
【0003】
【課題を解決するための手段】
そこで本発明者らは、安定的にフッ化物あるいはオキシフッ化物を形成させるため、水分を供与する能力がある素材を電池系内で使用することを検討した。 水分を供与する能力を有する素材は多くあるが、電池系内で使用する部材のほとんどは電池反応系に関与するものであり、容量の関係上、電池系内に電池反応系に関与する以外の部材を水分を供与する目的のために持ち込むことは好まれない。
ここで電池系内には、その組み立て工程の効率化のために、多くの接着剤及び粘着テープが用いられているが、多くは仮止めなど組み立て後はその役割を終えるものが多い。
そこで本発明者らは、これら接着剤や粘着テープに水分を供与する能力を与えることにより、特別に電池系内に部材を添加することなく、安定にフッ化物あるいはオキシフッ物を形成させることができることを見出し、本発明に至ったものである。
【0004】
即ち本発明は、リチウム塩を支持電解質とする非水電解液系の電池系内に用いられる接着剤又は粘着剤、もしくはこれらが基材に設けられた粘着テープ・シートであって、該接着剤又は粘着剤もしくは粘着テープ・シートの含水率が0.1wt%以上であり、水分を供与可能であることを特徴とする電池用粘着テープ・シートを提供する。
【0005】
【発明の実施の形態】
本発明の電池用接着剤又は粘着剤に用いる具体的な構成材料は、それらを電池系内に使用した際に水分を供与できるものである限り特に限定されないが、例えばアクリル酸などの官能基を含有するアクリル系接着剤又は粘着剤が好ましく、より具体的には、例えばアクリル酸ブチル、アクリル酸2−エチルヘキシルなどのアクリル主モノマーとアクリル酸、アクリル酸ヒドロキシルエチルなどの官能基含有モノマーとの共重合体をイソシアネートなどの架橋剤で架橋したものが挙げられる。
また、カルボキシル基やヒドロキシル基などの官能基を持つ粘着付与樹脂、例えば、ロジン系、テルペン−フェノール系、フェノール系などの粘着付与樹脂を配合したゴム系接着剤又は粘着剤なども好ましい。
【0006】
また本発明は、基材の少なくとも片面に粘着剤層を設けた粘着テープ・シートが水分供与可能なものも提供する。 この場合、粘着テープとして水分供与可能であればよく、例えば上記の水分供与可能な粘着剤を用いる場合の基材は特に限定されず、例えば、ポリプロピレン、ポリイミド、ポリフェニレンサルファイド、ポリエチレンテレフタレート、ポリビニルアルコール、エチレン−アクリル酸共重合体、エチレン−メタクリル酸共重合体などの無延伸あるいは延伸樹脂フィルムが挙げられる。 本発明においては、特にポリマーの構造中にカルボキシル基やヒドロキシル基をもつポリビニルアルコール、エチレン−アクリル酸共重合体、エチレン−メタクリル酸共重合体などの樹脂フィルムは吸水性が高いため好ましく、これらを用いる場合は、粘着剤は特に限定されない。
【0007】
なお、本発明の電池用接着剤もしくは粘着テープの水分供与可能性、及び電池系内への水分供与によるフッ化物又はオキシフッ化物の形成は、それぞれ後述の実施例における含水率、及び電解液発色試験にて評価することができる。本発明における接着剤又は粘着テープの含水率(wt%)は、通常0.1以上、好ましくは0.15以上が水分供与性の点から望ましい。
【0008】
【実施例】
以下、本発明を実施例によりさらに詳しく説明するが、本発明はこれらに何ら限定されるものではない。
実施例1〜6、比較例1〜2
表1及び2に示す組成の粘着剤及び粘着テープを得、これらの含水率、接着力、電解液変色性を以下の方法で評価し、その結果を併せて表1及び2に示す。
【0009】
【表1】

Figure 0004271756
【0010】
【表2】
Figure 0004271756
【0011】
〔含水率〕
23℃、65%RHの環境下に放置した各サンプルについて、加熱気化装置にて水分を150℃で加熱気化させて、電量滴定式水分測定装置にて水分量を定量した。
【0012】
〔接着力〕
延伸ポリプロピレン(OPP)フィルム(厚さ30μm)に、得られた接着剤又は粘着剤を30μm厚で塗布したものを、ステンレス板に貼り合わせ、フィルムを180°ピールにて引き剥がした時の荷重を測定した。
【0013】
〔電解液変色性(電解液発色試験)〕
溶媒(電解液)としての、エチレンカーボネート(EC):ジメチルカーボネート(DMC):ジエチルカーボネート(DEC)=1:1:1(体積比)に、溶質(電解質)として6フッ化リン酸リチウム(LiPF6 )を1mol/dm3 添加してなる電解液に、十分に乾燥したサンプルを、アルゴン置換した環境下でサンプル:電解液=1:200(重量比)にて添加、密閉した。 そして60℃にて1週間保存後、電解液の発色度合いをサンプルを添加していない電解液をブランクとして、目視にて比較した。
【0014】
【発明の効果】
本発明の電池用接着剤又は粘着剤もしくは粘着テープ・シートは、それらに本来要求される接着及び粘着特性を満たしながら、かつ電池系内で水分を供与できるため、結果的に電池特性に悪影響を及ぼさないという効果があり、特性及び信頼性の高い電池を作成できるという利点がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a battery adhesive, a pressure-sensitive adhesive, or a pressure-sensitive adhesive tape sheet that can be suitably used for the inside of a battery, in particular, a portion that is in contact with or possibly in contact with a battery electrolyte. It may be called adhesive tape.)
[0002]
[Problems to be solved by the invention]
Adhesives and pressure-sensitive adhesive tapes are frequently used in the battery in the manufacturing process, and these constituent materials are selected mainly in consideration of adhesion to an adherend.
In particular, in a non-aqueous electrolyte battery system using a lithium salt as a supporting electrolyte, it is generally not preferred to use a material that provides moisture. This is because, if a material that provides moisture is present in the battery system, it acts on the lithium salt in the electrolyte, and fluoride or oxyfluoride is formed, causing an increase in the internal pressure of the battery and corrosion of the battery member. ing.
However, recently, the effect of suppressing the deterioration of the electrode current collector by the formation of this fluoride or oxyfluoride has been reported. This is because, for example, in an aluminum metal often used as a current collector for a positive electrode, a passive film is formed on the surface of the battery system by fluoride or oxyfluoride and is stabilized even in an oxidizing atmosphere. It is believed that.
Originally, fluoride or oxyfluoride is also formed by a trace amount of moisture remaining in the electrolyte solution or a trace amount of moisture mixed in the battery assembly process, but the amount of moisture is not always stable, and the resulting fluoride is formed. The amount of fluoride or oxyfluoride was not constant.
In addition, fluorine-containing organic electrolytes typified by LiCF 3 SO 3 and Li (CF 3 SO 2 ) 2 N are composed of stable CF bonds and are more stable than other inorganic electrolytes. The amount of fluoride and oxyfluoride formed is said to be reduced.
[0003]
[Means for Solving the Problems]
Therefore, the present inventors examined the use of a material capable of supplying moisture in the battery system in order to stably form fluoride or oxyfluoride. There are many materials that have the ability to donate moisture, but most of the members used in the battery system are involved in the battery reaction system, and in terms of capacity, other than those involved in the battery reaction system. It is not preferred to bring the part for the purpose of providing moisture.
Here, many adhesives and adhesive tapes are used in the battery system in order to improve the efficiency of the assembly process, but many of them end their roles after assembly, such as temporary fixing.
Therefore, the present inventors are able to stably form fluoride or oxyfluoride by adding the ability to supply moisture to these adhesives and pressure-sensitive adhesive tapes without specially adding members to the battery system. And the present invention has been achieved.
[0004]
That is, the present invention relates to an adhesive or pressure-sensitive adhesive used in a non-aqueous electrolyte battery system using a lithium salt as a supporting electrolyte, or a pressure-sensitive adhesive tape sheet provided with these on a base material. Alternatively, the pressure-sensitive adhesive or pressure-sensitive adhesive tape sheet has a moisture content of 0.1 wt% or more and can provide moisture, and a battery pressure-sensitive adhesive tape sheet is provided.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The specific constituent materials used for the battery adhesive or pressure-sensitive adhesive of the present invention are not particularly limited as long as they can provide moisture when they are used in the battery system. For example, a functional group such as acrylic acid is added. The acrylic adhesive or pressure-sensitive adhesive contained is preferable. More specifically, for example, a co-polymerization of an acrylic main monomer such as butyl acrylate or 2-ethylhexyl acrylate with a functional group-containing monomer such as acrylic acid or hydroxylethyl acrylate. What crosslinked the polymer with crosslinking agents, such as isocyanate, is mentioned.
Further, a tackifier resin having a functional group such as a carboxyl group or a hydroxyl group, for example, a rubber adhesive or a pressure-sensitive adhesive containing a rosin-based, terpene-phenol-based, phenol-based tackifying resin, or the like is also preferable.
[0006]
The present invention also provides a pressure-sensitive adhesive tape / sheet provided with a pressure-sensitive adhesive layer on at least one side of a substrate, which can provide moisture. In this case, it is sufficient if moisture can be provided as the pressure-sensitive adhesive tape. For example, the base material in the case of using the above-mentioned pressure-sensitive adhesive capable of providing water is not particularly limited. For example, polypropylene, polyimide, polyphenylene sulfide, polyethylene terephthalate, polyvinyl alcohol, Non-stretched or stretched resin films such as ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer are exemplified. In the present invention, resin films such as polyvinyl alcohol, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer having a carboxyl group or a hydroxyl group in the polymer structure are particularly preferred because of their high water absorption. When used, the pressure-sensitive adhesive is not particularly limited.
[0007]
It should be noted that the water supply possibility of the battery adhesive or pressure-sensitive adhesive tape of the present invention and the formation of fluoride or oxyfluoride by supplying water into the battery system are the moisture content and electrolyte color development test in the examples described later, respectively. Can be evaluated. The water content (wt%) of the adhesive or pressure-sensitive adhesive tape in the present invention is usually 0.1 or more, preferably 0.15 or more from the viewpoint of water donating property.
[0008]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these at all.
Examples 1-6, Comparative Examples 1-2
The pressure-sensitive adhesives and pressure-sensitive adhesive tapes having the compositions shown in Tables 1 and 2 were obtained, their water content, adhesive strength, and electrolytic solution discoloration were evaluated by the following methods. The results are also shown in Tables 1 and 2.
[0009]
[Table 1]
Figure 0004271756
[0010]
[Table 2]
Figure 0004271756
[0011]
[Moisture content]
About each sample left to stand in the environment of 23 degreeC and 65% RH, the water | moisture content was heated and vaporized at 150 degreeC with the heating vaporizer, and the moisture content was quantified with the coulometric titration type moisture measuring device.
[0012]
[Adhesive strength]
A stretched polypropylene (OPP) film (thickness 30 μm) with the obtained adhesive or pressure-sensitive adhesive applied at a thickness of 30 μm is bonded to a stainless steel plate, and the load when the film is peeled off at 180 ° peel is applied. It was measured.
[0013]
[Electrolyte discoloration (electrolyte color development test)]
Ethylene carbonate (EC): dimethyl carbonate (DMC): diethyl carbonate (DEC) = 1: 1: 1 (volume ratio) as a solvent (electrolyte), lithium hexafluorophosphate (LiPF) as a solute (electrolyte) 6 ) was added to the electrolyte obtained by adding 1 mol / dm 3 , and a sufficiently dried sample was added and sealed in a sample: electrolyte = 1: 200 (weight ratio) in an argon-substituted environment. Then, after storage at 60 ° C. for 1 week, the degree of coloration of the electrolytic solution was compared visually with an electrolytic solution to which no sample was added as a blank.
[0014]
【The invention's effect】
The battery adhesive or pressure-sensitive adhesive or pressure-sensitive adhesive tape sheet of the present invention can provide moisture in the battery system while satisfying the adhesion and pressure-sensitive adhesive properties originally required for the battery, resulting in adversely affecting the battery characteristics. There is an advantage that a battery having high characteristics and reliability can be produced.

Claims (4)

リチウム塩を支持電解質とする非水電解液系の電池系内に用いられる接着剤又は粘着剤、もしくはこれらが基材に設けられた粘着テープ・シートであって、該接着剤又は粘着剤もしくは粘着テープ・シートの含水率が0.1wt%以上であり、水分を供与可能であることを特徴とする電池用粘着テープ・シート。 An adhesive or pressure-sensitive adhesive used in a non-aqueous electrolyte battery system using a lithium salt as a supporting electrolyte, or a pressure-sensitive adhesive tape or sheet provided on a base material, the adhesive or pressure-sensitive adhesive or pressure-sensitive adhesive A battery pressure-sensitive adhesive tape and sheet , wherein the moisture content of the tape and sheet is 0.1 wt% or more and water can be provided . 請求項1記載の接着剤又は粘着剤が、アクリル系であることを特徴とする電池用粘着テープ・シートThe pressure-sensitive adhesive tape or sheet for batteries, wherein the adhesive or pressure-sensitive adhesive according to claim 1 is acrylic. 請求項1記載の接着剤又は粘着剤が、カルボキシル基又は/及びヒドロキシル基を持つ樹脂が配合されたものであることを特徴とする電池用粘着テープ・シートThe adhesive tape or sheet according to claim 1, wherein a resin having a carboxyl group or / and a hydroxyl group is blended. 請求項1記載の粘着テープ・シートの基材が、カルボキシル基又は/及びヒドロキシル基を持つ樹脂フィルムであることを特徴とする電池用粘着テープ・シート。  The adhesive tape sheet for batteries, wherein the substrate of the adhesive tape sheet according to claim 1 is a resin film having a carboxyl group or / and a hydroxyl group.
JP34242498A 1998-12-02 1998-12-02 Battery adhesive or adhesive or adhesive tape sheet Expired - Lifetime JP4271756B2 (en)

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4780843B2 (en) * 2001-03-01 2011-09-28 日東電工株式会社 Acrylic adhesive or adhesive for lithium secondary batteries
US7318984B2 (en) * 2002-05-17 2008-01-15 Nitto Denko Corporation Adhesive composition-supporting separator for battery and electrode/separator laminate obtained by using the same
US8124277B2 (en) 2006-08-29 2012-02-28 Unitika Ltd. Binder for electrode formation, slurry for electrode formation using the binder, electrode using the slurry, rechargeable battery using the electrode, and capacitor using the electrode
KR101781645B1 (en) 2011-04-20 2017-09-25 닛토덴코 가부시키가이샤 Pressure-sensitive adhesive tape for electrochemical device
JP2012226991A (en) * 2011-04-20 2012-11-15 Nitto Denko Corp Adhesive tape for electrochemical device
JP5632325B2 (en) * 2011-04-20 2014-11-26 日東電工株式会社 Adhesive tape for electrochemical devices
JP2013064086A (en) * 2011-09-20 2013-04-11 Nitto Denko Corp Self-adhesive tape for battery
TWI520404B (en) 2013-02-15 2016-02-01 Lg化學股份有限公司 Electrode assembly and polymer secondary battery cell including the same
CN104221201B (en) * 2013-02-15 2016-08-31 株式会社Lg化学 Electrode assemblies and include the polymer secondary battery unit of this electrode assemblies
JP6967339B2 (en) 2016-09-06 2021-11-17 日東電工株式会社 Adhesive tape for battery exterior

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