JP2002216741A - Lithium ion battery tab - Google Patents
Lithium ion battery tabInfo
- Publication number
- JP2002216741A JP2002216741A JP2001009706A JP2001009706A JP2002216741A JP 2002216741 A JP2002216741 A JP 2002216741A JP 2001009706 A JP2001009706 A JP 2001009706A JP 2001009706 A JP2001009706 A JP 2001009706A JP 2002216741 A JP2002216741 A JP 2002216741A
- Authority
- JP
- Japan
- Prior art keywords
- tab
- ion battery
- lithium ion
- layer
- chemical conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
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- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
- Connection Of Batteries Or Terminals (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、包装材料との安定
した密封性を示すリチウムイオン電池のタブ材に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tab material for a lithium ion battery showing stable sealing with a packaging material.
【０００２】[0002]
【従来の技術】リチウムイオン電池とは、リチウム２次
電池ともいわれ、液状、ゲル状および高分子ポリマー状
の電解質を持ち、リチウムイオンの移動で電流を発生す
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。前記リチウム２次電池の
構成は、正極集電材（アルミニウム、ニッケル）／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）／電解質層（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、エチレンメチルカーボネー
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、ゲル電解質等）／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
ル等の高分子負極材料）／負極集電材（銅、ニッケル、
ステンレス）及び、これらを包装する外装体からなる。
リチウムイオン電池の用途としては、パソコン、携帯端
末装置（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。前記リチウムイオン電池の外装体としては、金
属をプレス加工し円筒状または直方体状等に容器化した
金属製缶、あるいは、最外層アルミニウムシーラント層
から構成される多層フィルムを袋状にしたものが用いら
れていた。2. Description of the Related Art A lithium ion battery, also called a lithium secondary battery, is a battery that has a liquid, gel, and polymer electrolyte and generates an electric current by the movement of lithium ions. Substances include those composed of high-molecular polymers. The structure of the lithium secondary battery is as follows: a positive electrode current collector (aluminum, nickel) / a positive electrode active material layer (a metal positive electrode material such as a metal oxide, carbon black, a metal sulfide, an electrolytic solution, and polyacrylonitrile) / an electrolyte layer ( Carbonate-based electrolytes such as propylene carbonate, ethylene carbonate, dimethyl carbonate, and ethylene methyl carbonate; inorganic solid electrolytes composed of lithium salts; gel electrolytes; etc./negative electrode active material layer (lithium metal, alloy, carbon, electrolyte, polyacrylonitrile, etc.) Polymer anode material) / Anode current collector (copper, nickel,
(Stainless steel) and an outer package for packaging them.
Lithium-ion batteries are used for personal computers, portable terminal devices (mobile phones, PDAs, etc.), video cameras, electric vehicles, storage batteries for energy storage, robots, satellites, and the like. As the outer package of the lithium-ion battery, a metal can formed by pressing a metal into a cylindrical or rectangular parallelepiped or the like, or a multi-layer film composed of an outermost aluminum sealant layer in a bag shape is used. Had been.
【０００３】[0003]
【発明が解決しようとする課題】しかるに、リチウムイ
オン電池の外装体として次のような問題があった。金属
製缶においては、容器外壁がリジッドであるため、電池
自体の形状が決められてしまう。そのため、ハード側を
電池に合わせ設計するため、該電池を用いるハードの寸
法が電池により決定されてしまい形状の自由度がなくな
る。そこで、積層体を袋状にして、リチウムイオン電池
本体を収納するパウチタイプ、または、前記積層体をプ
レスしてエンボスタイプとした外装体は、前記金属缶の
ように、電池自体により、電池を用いるハードの形状設
計における自由度の制限は無くなるが、リチウムイオン
電池の外装体として要求される物性・機能を、十分に満
足しうる包装材料は未だ開発されていないのが現状であ
る。前記要求される物性・機能とは、高度な防湿性ある
いは表面絶縁性等であり、特に、防湿性は特に重要であ
る。リチウムイオン電池用包装材料としては、少なくと
も、基材層、バリア層、ヒートシール層からなる積層体
であり、前記各層の材質と各層の層間の接着強度がリチ
ウムイオン電池の外装体としての必要な性質に影響を与
えることが確認されている。例えば、バリア層とヒート
シール層との接着強度が不十分であると、外部から水分
の浸入の原因となり、リチウムイオン電池を形成する成
分の中の電解質と前記水分との反応により生成するフッ
化水素酸により前記バリア層であるアルミニウム面が腐
食して、バリア層とヒートシール層との間にデラミネー
ションが発生するという問題があり、この課題に対して
種々の提案がなされている。リチウムイオン電池本体を
外装体により密封する際、リチウムイオン電池本体のタ
ブ部を含む部分も確実に密封される必要がある。しか
し、従来、リチウムイオン電池用包装材料としてアルミ
ニウム、ＳＵＳ、ニッケル、Ｃｕ（ニッケルメッキ含
む）等の金属からなるタブに熱熱融着性を有するヒート
シール層の選定、または、ヒートシール層が金属に対し
て熱融着性を有しない場合には、タブのシール予定部に
接着性フィルムを介在させてヒートシールすること等は
なされていたが、リチウム電池の電解質と水分とによる
反応で生成するフッ化水素等によりタブ部表面の腐食に
よる剥離防止の対策はされていなかった。そのため、長
期にわたって、タブ部の表面が徐々に腐食して、タブ部
において、該タブ部に接着するヒートシール層または接
着性フィルム層が剥離して密封系が破壊されることがあ
った。本発明の目的は、リチウムイオン電池のタブが、
外装体または接着性フィルムと接着している部位におい
て、電解質と水分により発生するフッ化水素酸等により
腐食されることのないタブおよび耐腐食性を有するタブ
の表面層の形成方法を提供することである。However, there are the following problems as an exterior body of a lithium ion battery. In a metal can, the shape of the battery itself is determined because the outer wall of the container is rigid. Therefore, since the hardware side is designed according to the battery, the size of the hardware using the battery is determined by the battery, and the degree of freedom of the shape is lost. Therefore, the pouch type housing the lithium-ion battery body, or an exterior body made into an embossed type by pressing the stacked body, as in the case of the metal can, the battery is formed by the battery itself. Although there is no limit on the degree of freedom in designing the shape of the hardware to be used, a packaging material that sufficiently satisfies the physical properties and functions required for the exterior body of the lithium ion battery has not yet been developed. The required physical properties / functions are advanced moisture proof property or surface insulating property, and the moisture proof property is particularly important. The packaging material for a lithium ion battery is at least a laminate comprising a base material layer, a barrier layer, and a heat seal layer, and the material of each of the layers and the adhesive strength between the layers are necessary for an exterior body of the lithium ion battery. It has been found to affect properties. For example, if the adhesive strength between the barrier layer and the heat sealing layer is insufficient, it causes moisture to enter from the outside, and the fluoride generated by the reaction between the electrolyte in the components forming the lithium ion battery and the moisture. There is a problem that the aluminum surface serving as the barrier layer is corroded by hydrogen acid and delamination occurs between the barrier layer and the heat seal layer, and various proposals have been made for this problem. When the lithium ion battery main body is sealed by the outer package, it is necessary that the portion including the tab portion of the lithium ion battery main body is also securely sealed. However, conventionally, as a packaging material for a lithium ion battery, a heat seal layer having a heat-sealing property on a tab made of a metal such as aluminum, SUS, nickel, or Cu (including nickel plating) is selected, or the heat seal layer is made of a metal. In the case where it does not have heat-sealing property, heat-sealing has been performed with an adhesive film interposed in the portion to be sealed of the tab, but it is generated by the reaction between the lithium battery electrolyte and moisture. No measures have been taken to prevent peeling due to corrosion of the tab surface by hydrogen fluoride or the like. For this reason, the surface of the tab portion gradually corrodes over a long period of time, and in the tab portion, the heat seal layer or the adhesive film layer adhered to the tab portion may be peeled off to break the sealing system. An object of the present invention is that a tab of a lithium ion battery is
Provided is a method for forming a tab that is not corroded by hydrofluoric acid or the like generated by an electrolyte and moisture and a surface layer of a tab having corrosion resistance in a portion bonded to an exterior body or an adhesive film. It is.
【０００４】[0004]
【課題を解決するための手段】本発明は、少なくとも、
基材層、接着層、化成処理層１、アルミニウム、化成処
理層２、ヒートシール層からなる包装材料にリチウムイ
オン電池本体を収納し、タブを挟持する部分を含め周縁
部をヒートシールにより密封してなるリチウムイオン電
池のタブであって、また、前記化成処理がリン酸クロメ
ート処理であること、前記化成処理がＭｏ、Ｚｒ、Ｔｉ
（ノンクロム）処理であること、さらに、前記化成処理
がトリアジンチオール処理であることを含むものであ
る。さらに、少なくとも基材層、接着層、アルミニウ
ム、化成処理層、ポリオレフィン系樹脂のヒートシール
層から構成されるリチウム電池の外装体にリチウム電池
本体を挿入し、前記リチウムイオン電池の周縁部のヒー
トシールにおいて、少なくとも、ヒートシールされる部
分の表、裏面および側面に化成処理が施されている電池
タブであって、また、前記化成処理がリン酸クロメート
処理であること、前記化成処理がＭｏ、Ｚｒ、Ｔｉ（ノ
ンクロム）処理であること、さらに、前記化成処理がト
リアジンチオール処理であることを含むものである。Means for Solving the Problems The present invention provides at least:
The lithium ion battery main body is housed in a packaging material including a base material layer, an adhesive layer, a chemical conversion treatment layer 1, aluminum, a chemical conversion treatment layer 2, and a heat seal layer, and the periphery including a portion for holding the tab is hermetically sealed by heat sealing. Wherein the chemical conversion treatment is a phosphoric acid chromate treatment, and the chemical conversion treatment is Mo, Zr, Ti
(Non-chromium) treatment, and the chemical conversion treatment is a triazine thiol treatment. Furthermore, a lithium battery main body is inserted into a lithium battery exterior body composed of at least a base material layer, an adhesive layer, aluminum, a chemical conversion treatment layer, and a polyolefin-based resin heat seal layer, and heat sealing of the peripheral portion of the lithium ion battery is performed. In the above, at least the front, back and side surfaces of the portion to be heat sealed are subjected to a chemical conversion treatment, the chemical conversion treatment is a phosphoric acid chromate treatment, the chemical conversion treatment is Mo, Zr , Ti (non-chromium) treatment, and the chemical conversion treatment is a triazine thiol treatment.
【０００５】[0005]
【発明の実施の形態】図１は、本発明のリチウムイオン
電池タブおよびタブ材による化成処理方法の実施例を示
す、（ａ）リチウムイオン電池本体および外装体の斜視
図、（ｂ）Ｘ1−Ｘ1部断面図、（ｃ）Ｙ1部の拡大図、
（ｄ）リチウムイオン電池本体を外装体に収納した状態
の斜視図、（ｅ）Ｘ2−Ｘ2部での断面図、（ｆ）Ｘ2−
Ｘ2部での別の断面図である。図２は、リチウムイオン
電池のパウチタイプの外装体を説明する斜視図である。
図３は、リチウムイオン電池のエンボスタイプの外装体
を説明する斜視図である。図４は、本発明のリチウムイ
オン電池用包装材料におけるタブ部の外装体および接着
性フィルムの実施例を説明する図で、（ａ）ヒートシー
ル前の外装体、接着性フィルム、タブの位置関係を片面
シール側のみで示し、（ｂ）ヒートシール後の構成を両
面で示す断面図である。図５は、リチウムイオン電池用
包装材料とタブとの接着における接着性フィルムの装着
方法を説明する斜視図である。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an embodiment of a chemical conversion treatment method using a tab of a lithium ion battery and a tab material according to the present invention, (a) a perspective view of a lithium ion battery main body and an outer package, and (b) X 1. -X 1 part cross-sectional view, (c) Y 1 an enlarged view of part,
(D) a perspective view of a state in which the lithium ion battery main body housed in the outer body, (e) cross-sectional view at X 2 -X 2 parts, (f) X 2 -
It is another cross-sectional view at X 2 parts. FIG. 2 is a perspective view illustrating a pouch type exterior body of a lithium ion battery.
FIG. 3 is a perspective view illustrating an embossed type exterior body of the lithium ion battery. FIG. 4 is a view for explaining an embodiment of the outer package of the tab portion and the adhesive film in the packaging material for a lithium ion battery of the present invention, wherein (a) the positional relationship between the outer package, the adhesive film and the tab before heat sealing; (B) is a cross-sectional view showing the configuration after heat sealing on both sides. FIG. 5 is a perspective view illustrating a method of mounting an adhesive film in bonding a packaging material for a lithium ion battery and a tab.
【０００６】リチウムイオン電池は、リチウムイオン電
池本体を包装する外装体のタイプにより、図２に示すよ
うなパウチタイプ、また、図３に示すようなエンボスタ
イプとがある。本発明はいずれのタイプにも適用し得る
ものである。外装体５に収納されたリチウムイオン電池
本体２はその周縁を密封することにより、防湿性が付与
される。金属であるタブ部においても密封シール性が必
要であり、そのため、リチウムイオン電池用包装材料の
ヒートシール層は金属接着性フィルムとする。しかし、
金属に対して接着性を示す樹脂は、加工適性に劣ること
があり、また、そのコストも高いので、ヒートシール層
は、汎用されているポリオレフィン系の樹脂とし、該ヒ
ートシール層とタブとの間に，金属と前記リチウムイオ
ン電池用包装材料のヒートシール層との双方にヒートシ
ール性を有する接着性フィルムを介し、ヒートシールさ
れ溶着することが一般的である。タブ部は金属であるた
め、内容物である電解液中に発生するフッ化水素（Ｈ
Ｆ）で表面腐食が起こり、タブと該タブに積層されてい
る樹脂層との間で、デラミが起こり電解液が外部に漏れ
てしまうことがあった。タブとしては、厚さが５０〜２
０００μｍ、 巾 が２．５〜２０ｍｍ程度であって、そ
の材質としては、 ＡＬ、Ｃｕ（Ｎｉメッキを含む）お
よびＮｉ等である。前記、タブの材質のうち、ニッケル
は、フッ化水素酸により腐食される危険性が少なく、ア
ルミニウムが最も腐食されやすいという問題があった。
さらに、本発明者らは、タブ部に化成処理層を設けるこ
とにより、リチウムイオン電池の電解質と水分との反応
で生成するフッ化水素（化学式：ＨＦ）に起因するタブ
表面の溶解、腐食を防止し、かつタブとリチウムイオン
電池用包装材料の最内層または接着性フィルムとの接着
性（濡れ性）を向上させ、タブ部における接着力の安定
化を図る課題に対して顕著な効果のあることをみいだし
た。[0006] Lithium-ion batteries include a pouch type as shown in FIG. 2 and an embossed type as shown in FIG. 3, depending on the type of the outer package that packages the lithium-ion battery body. The present invention can be applied to any type. The lithium ion battery main body 2 housed in the exterior body 5 is provided with moisture-proof properties by sealing the periphery thereof. The tab portion made of metal also needs to have a hermetic sealing property. Therefore, the heat seal layer of the packaging material for a lithium ion battery is a metal adhesive film. But,
A resin exhibiting adhesiveness to metal may be inferior in workability and its cost is high, so the heat seal layer is a polyolefin resin which is widely used, and the heat seal layer and the tab are bonded together. In general, both the metal and the heat-sealing layer of the packaging material for a lithium ion battery are heat-sealed and welded via an adhesive film having heat-sealing properties. Since the tab portion is made of metal, hydrogen fluoride (H) generated in the electrolyte solution as the content is formed.
In F), surface corrosion occurred, delamination occurred between the tab and the resin layer laminated on the tab, and the electrolyte sometimes leaked to the outside. As a tab, the thickness is 50-2
000 μm and a width of about 2.5 to 20 mm, and its material is AL, Cu (including Ni plating), Ni or the like. Among the tab materials, nickel has a low risk of being corroded by hydrofluoric acid, and has a problem that aluminum is most easily corroded.
Furthermore, the present inventors provide a chemical conversion treatment layer on the tab portion to prevent dissolution and corrosion of the tab surface caused by hydrogen fluoride (chemical formula: HF) generated by the reaction between the electrolyte of the lithium ion battery and moisture. It has a remarkable effect on the problem of preventing adhesion and improving the adhesion (wetting property) between the tab and the innermost layer of the packaging material for a lithium ion battery or the adhesive film, and stabilizing the adhesive force at the tab portion. I found that.
【０００７】前記化成処理層（以下、耐フッ化水素層と
記載することがある）４Ｓは、図１（ａ）または図１
（ｃ）に示すように、タブ材４Ｍの表面の少なくとも、
外装体によりヒートシールされる部位に耐フッ化水素層
４Ｓを形成するもので、該耐フッ化水素層４Ｓは、前記
リチウムイオン電池用包装材料のヒートシール層または
接着性フィルムと確実にヒートシールすることができ
る。耐フッ化水素層４Ｓの形成は、例えば、リン酸クロ
ム、クロム酸等で化成処理（以下、リン酸クロメート処
理と記載する）を行なうことにより、図１（ｅ）または
図１（ｆ）に示すようにリチウムイオン電池用包装材料
の最内層１４またはタブ４に対する接着シート６とタブ
と４Ｍとの間での接着が向上することを見出し、本発明
を完成するに到った。化成処理について、さらに具体的
に説明する。本発明者らは、本発明の課題に対して効果
を奏する化成処理として、前記クロメート処理の他、少
なくともフェノール樹脂を含む樹脂成分に、モリブデ
ン、チタン、ジルコン等の金属、または金属塩を含む化
成処理が同様の効果があった。また、トリアジンチオー
ル処理等も同様に耐フッ化水素性を示すことを見出し
た。The chemical conversion treatment layer (hereinafter sometimes referred to as a hydrogen fluoride-resistant layer) 4S is formed as shown in FIG.
As shown in (c), at least the surface of the tab material 4M,
A hydrogen fluoride-resistant layer 4S is formed at a portion to be heat-sealed by the outer package, and the hydrogen-fluoride-resistant layer 4S is securely heat-sealed with the heat-sealing layer or the adhesive film of the lithium ion battery packaging material. can do. The formation of the hydrogen fluoride-resistant layer 4S is performed, for example, by performing a chemical conversion treatment (hereinafter referred to as a phosphoric acid chromate treatment) with chromium phosphate, chromic acid, or the like, as shown in FIG. As shown in the figure, it has been found that the adhesion between the adhesive sheet 6 and the tab and 4M with respect to the innermost layer 14 or the tab 4 of the packaging material for a lithium ion battery is improved, and the present invention has been completed. The chemical conversion treatment will be described more specifically. The present inventors have proposed, as a chemical conversion treatment that has an effect on the object of the present invention, in addition to the chromate treatment, a chemical component containing a metal such as molybdenum, titanium, zircon, or a metal salt at least in a resin component containing a phenolic resin. The treatment had a similar effect. In addition, it has been found that triazine thiol treatment and the like also exhibit hydrogen fluoride resistance.
【０００８】その処理方法としては、例えば、クロメー
ト処理の場合には、アルミニウム等のタブ用の金属シー
トを最終使用巾にスリッターしたタブ材の表裏面および
側面を脱脂処理する。脱脂処理は、有機溶剤、界面活性
剤、酸またはアルカリ液をコーティングまたは浸漬する
ことにより行うことができる。有機溶剤、界面活性剤、
酸、アルカリ液を乾燥した後、クロム酸塩の液を用い金
属表面を化成処理する。化成処理の方法は、前記、クロ
ム酸塩液にタブ材を浸漬する方法、タブ材にクロム酸塩
液を吹き付ける方法、ロールコート法を用いて、タブ材
にクロム酸塩液をコートする等の方法により、タブ材に
クロム酸塩液を塗布乾燥して、タブ材の表裏面および側
面を化成処理する。As a processing method, for example, in the case of a chromate treatment, the front and back surfaces and side surfaces of the tab material obtained by slitting a metal sheet for a tab such as aluminum to the final use width are degreased. The degreasing treatment can be performed by coating or dipping an organic solvent, a surfactant, an acid or an alkali solution. Organic solvents, surfactants,
After drying the acid and alkali solutions, the metal surface is subjected to a chemical conversion treatment using a chromate solution. The method of chemical conversion treatment is, for example, a method of immersing the tab material in the chromate solution, a method of spraying the chromate solution on the tab material, a method of coating the tab material with the chromate solution using a roll coating method, and the like. According to the method, a chromate solution is applied to the tab material and dried, and the front and back surfaces and side surfaces of the tab material are subjected to a chemical conversion treatment.
【０００９】タブ材は、金属シートを形成する際にその
表面に油性成分が付着することがあり、また、タブ材と
して、広い巾のシートからスリッターによって、一般に
所定の巾に断裁する際に、切断刃の保護のためにオイル
を用いる。前記脱脂は、これらの油性成分やオイルを除
去するために行なわれるものである。脱脂に用いる酸性
物質としては、塩酸、硫酸、硝酸、フッ酸、リン酸、ス
ルファミン酸などの無機酸、クエン酸、グルコン酸、シ
ュウ酸、酒石酸、ギ酸、ヒドロオキシ酢酸、ＥＤＴＡ
（エチレン・ジアミン・テトラ・アセティック・アッシ
ド）およびその誘導体、チオグリコール酸アンモニウム
等が挙げられる。また、アルカリ性物質としては、カセ
イソーダ（ＮａＯＨ）、ソーダ灰（Ｎａ２ＣＯ3）、重
曹（ＮａＨＣＯ3）、ボウ硝（Ｎａ２ＳＯ4・１０Ｈ
2Ｏ）、セスキ炭酸ソーダ（Ｎａ２ＣＯ3・ＮａＨＣＯ3
・２Ｈ2Ｏ）などのソーダ塩類、オルソケイ曹（２Ｎａ2
Ｏ・ＳIＯ2、水分１０〜４０％）、メタケイ曹（２ＮＡ
2Ｏ・Ｓ IＯ2・９Ｈ2Ｏ）、一号ケイ曹（Ｎａ2Ｏ・２ＳI
Ｏ2、水分４２〜４４％）、二号ケイ曹（Ｎａ2Ｏ・３Ｓ
IＯ2、水分６５％）等のケイ酸塩、第一リン酸ソーダ
（ＮａＨ2ＰＯ4）、ピロリン酸ソーダ（Ｎａ4Ｐ
2Ｏ7）、第二リン酸ソーダ（Ｎａ２ＨＰＯ4）、ヘキサ
メタリン酸ソーダ｛（ＮａＰＯ3）6｝、第三リン酸ソー
ダ（Ｎａ3ＰＯ4）、トリポリリン酸ソーダ（Ｎａ5Ｐ3Ｏ
10）等のリン酸塩類が挙げられる。The tab material is used when forming a metal sheet.
Oily components may adhere to the surface.
And from a wide width sheet by slitter, generally
When cutting to the specified width, use oil to protect the cutting blade.
Is used. The degreasing removes these oily components and oils.
It is done to leave. Acid used for degreasing
Substances include hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid,
Inorganic acids such as rufamic acid, citric acid, gluconic acid,
Oxalic acid, tartaric acid, formic acid, hydroxyacetic acid, EDTA
(Ethylene Diamine Tetra Athetic Assy
C) and its derivatives, ammonium thioglycolate
And the like. In addition, as an alkaline substance,
Isoda (NaOH), soda ash (Na2COThree), Heavy
Soda (NaHCOThree), Bow Nit (Na2SOFour・ 10H
TwoO), sodium sesquicarbonate (Na2COThree・ NaHCOThree
・ 2HTwoO) and soda salts, orthosilicate (2Na)Two
OSIOTwo, Moisture 10-40%), metasilicate (2NA)
TwoOS IOTwo・ 9HTwoO), No. 1 silicate (NaTwoO ・ 2SI
OTwo, Moisture 42-44%), No.2 silicate (NaTwoO ・ 3S
IOTwo, Water content 65%) etc., sodium phosphate monobasic
(NaHTwoPOFour), Sodium pyrophosphate (NaFourP
TwoO7), Sodium phosphate dibasic (Na2HPO)Four), Hex
Sodium metaphosphate (NaPOThree)6｝, Tertiary phosphate saw
Da (NaThreePOFour), Sodium tripolyphosphate (NaFivePThreeO
Ten) And the like.
【００１０】本発明のリチウムイオン電池タブ材の化成
処理方法について説明する。リン酸クロメート処理は、
タブに用いる金属シートの巻き取りを所定の巾に、スリ
ッターした後、脱脂処理をする。その後、化成処理を行
う。化成処理の方法は、少なくともタブ部における密着
部を処理できればよいが、浸漬法、シャワー法、ロール
コート法等を用いてタブ材の全周を処理することが望ま
しい。The method for chemical conversion treatment of a tab material for a lithium ion battery according to the present invention will be described. Phosphoric acid chromate treatment
After the metal sheet used for the tab is slit into a predetermined width, a degreasing process is performed. Then, a chemical conversion treatment is performed. The chemical conversion treatment method only needs to be able to treat at least the contact portion in the tab portion, but it is desirable to treat the entire periphery of the tab material by using a dipping method, a shower method, a roll coating method, or the like.
【００１１】リン酸クロメート処理は、処理液として、
フェノール樹脂、フッ化クロム（３）化合物、リン酸か
らなる水溶液を用いる。タブに、前記水溶液を塗布後、
乾燥し、さらに、皮膜温度が１８０℃以上となる温度条
件において焼付ける。クロムの塗布量は１〜１０ｍｇ/
ｍ2（乾燥重量）程度が適当である。In the phosphoric acid chromate treatment, the treatment solution is as follows:
An aqueous solution comprising a phenol resin, a chromium fluoride (3) compound, and phosphoric acid is used. After applying the aqueous solution to the tab,
It is dried and further baked under the temperature condition that the film temperature becomes 180 ° C. or more. Chromium application amount is 1-10mg /
About 2 m 2 (dry weight) is appropriate.
【００１２】本発明者らは、リチウムイオン電池の電解
質と水分との反応により生成する、フッ化水素酸（化学
式：ＨＦ）により、リチウムイオン電池用包装材料のバ
リア層であるアルミニウム表面の溶解、腐食、特に、表
面に存在する酸化アルミが溶解、腐食することを防止
し、かつアルミニウム表面の接着性（濡れ性）を向上さ
せ、積層体形成時のアルミニウムと最内層の接着力の安
定化を図る課題に対して、アルミニウム表面に耐酸性皮
膜の形成をすることが極めて効果的であることを見出
し、密封性を安定させる方法として提案してきたが、タ
ブ部においても耐フッ化水素酸皮膜として優れた性質を
発現することを見出した。The present inventors dissolve the aluminum surface, which is a barrier layer of a packaging material for lithium ion batteries, with hydrofluoric acid (chemical formula: HF) generated by the reaction between the electrolyte of lithium ion batteries and moisture. Prevents corrosion, especially the dissolution and corrosion of aluminum oxide present on the surface, improves the adhesion (wetting) of the aluminum surface, and stabilizes the adhesion between aluminum and the innermost layer when forming a laminate. We found that it is extremely effective to form an acid-resistant film on the aluminum surface to solve the problem to be solved, and we have proposed it as a method to stabilize the sealing performance. It has been found that excellent properties are exhibited.
【００１３】リチウムイオン電池のタブ材となる金属シ
ートを最終使用巾にスリッターしてタブ材とした後、そ
の表裏面および側面を脱脂した後、フェノール樹脂、フ
ッ化クロム（３）化合物、リン酸からなる水溶液を浸漬
法、シャワー法、ロールコート法等を用いてタブ材の全
周に塗布乾燥し、さらに熱風、遠近赤外線の照射等によ
り皮膜を硬化させて化成処理層を形成する。望ましい皮
膜の塗布量は、乾燥重量として、１０ｍｇ／ｍ2程度が
望ましい。After a metal sheet serving as a tab material of a lithium ion battery is slit to a final use width to form a tab material, the front and back surfaces and side surfaces thereof are degreased, and then a phenol resin, a chromium fluoride (3) compound, phosphoric acid Is coated and dried on the entire circumference of the tab material using a dipping method, a shower method, a roll coating method, or the like, and then the coating is cured by irradiation with hot air, far-near infrared rays, or the like to form a chemical conversion treatment layer. Desirable coating amount of the film is desirably about 10 mg / m 2 as a dry weight.
【００１４】リン酸クロメート処理と同様、リチウムイ
オン電池のタブ材となる金属シートを最終使用巾にスリ
ッターしてタブ材とした後、その表裏面および側面を脱
脂した後、少なくともフェノール樹脂を含む樹脂成分
に、モリブデン、チタン、ジルコン等の金属、または金
属塩を含む化成処理剤液を用い浸漬法、シャワー法、ロ
ールコート法等を用いてタブ材の全周に塗布乾燥し、さ
らに熱風、遠近赤外線の照射等により皮膜を硬化させて
化成処理層を形成する。望ましい皮膜の塗布量は、乾燥
重量として、１０ｍｇ／ｍ2程度が望ましい。Similar to the phosphoric acid chromate treatment, a metal sheet serving as a tab material of a lithium ion battery is slit to a final use width to form a tab material, and the front and back surfaces and side surfaces thereof are degreased. Using a chemical conversion agent solution containing a metal such as molybdenum, titanium, zircon, or a metal salt as a component, apply and dry the entire circumference of the tab material using a dipping method, a shower method, a roll coating method, etc. The film is cured by infrared irradiation or the like to form a chemical conversion treatment layer. Desirable coating amount of the film is desirably about 10 mg / m 2 as a dry weight.
【００１５】リチウムイオン電池のタブ材となる金属シ
ートを最終使用巾にスリッターしてタブ材とした後、そ
の表裏面および側面を脱脂した後、トリアジンチオール
含む処理液を用い電解重合することでトリアジチンチオ
ール皮膜を形成する。After a metal sheet serving as a tab material of a lithium ion battery is slit to a final use width to form a tab material, the front and rear surfaces and side surfaces thereof are degreased, and then subjected to electrolytic polymerization using a processing solution containing triazine thiol to thereby perform tripolymerization. Form an aditinthiol film.
【００１６】本発明のリチウムイオン電池タブ材方法に
おいて用いられる外装体１０の材質について説明する。
前記外装体は、図４（ａ）に示すように、少なくとも、
基材層１１、バリア層１２、ヒートシール層１４からな
り、これらの各層間を、ドライラミネート法、サンドイ
ッチラミネート法、押出ラミネート法、熱ラミネート法
等の方法でラミネートして積層する。また、図４（ｂ）
に示すように、バリア層１２とヒートシール層１４との
間に中間層１３を設けてもよい。The material of the exterior body 10 used in the tab material method for a lithium ion battery of the present invention will be described.
As shown in FIG. 4 (a), the exterior body includes at least
It consists of a base material layer 11, a barrier layer 12, and a heat seal layer 14. These layers are laminated and laminated by a method such as a dry lamination method, a sandwich lamination method, an extrusion lamination method, or a heat lamination method. FIG. 4 (b)
As shown in (1), an intermediate layer 13 may be provided between the barrier layer 12 and the heat seal layer 14.
【００１７】最外層は、延伸ポリエステル又はナイロン
フィルムからなるが、この時、ポリエステル樹脂として
は、ポリエチレンテレフタレート、ポリブチレンテレフ
タレート、ポリエチレンナフタレート、ポリブチレンナ
フタレート、共重合ポリエステル、ポリカーボネート等
が挙げられる。またナイロン樹脂としては、ポリアミド
系樹脂、すなわち、ナイロン６、ナイロン６，６、ナイ
ロン６，６とナイロン６との共重合体、ナイロン６，１
０、ポリメタキシリレンアジパミド（ＭＸＤ６）等が挙
げられる。The outermost layer is made of a stretched polyester or nylon film. At this time, examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymerized polyester and polycarbonate. Examples of the nylon resin include polyamide resins, that is, nylon 6, nylon 6,6, a copolymer of nylon 6,6 and nylon 6, nylon 6-1.
0, polymethaxylylene adipamide (MXD6) and the like.
【００１８】前記最外層は、リチウムイオン電池として
用いられる場合、ハードと直接接触する部位であるた
め、基本的に絶縁性を有する樹脂層がよい。フィルム単
体でのピンホールの存在、および加工時のピンホールの
発生等を考慮すると、最外層は６μｍ以上の厚さが必要
であり、好ましい厚さとしては１２〜３０μｍである。When the outermost layer is used as a lithium ion battery, it is a portion which is in direct contact with the hardware, and therefore, is preferably a resin layer having an insulating property. In consideration of the presence of pinholes in the film alone and the occurrence of pinholes during processing, the outermost layer needs to have a thickness of 6 μm or more, and the preferred thickness is 12 to 30 μm.
【００１９】前記最外層は耐ピンホール性および電池の
外装体とした時の絶縁性を向上させるために、積層化す
ることも可能である。最外層を積層体化する場合、最外
層が２層以上の樹脂層を少なくとも一つを含み、各層の
厚みが６μｍ以上、好ましくは、１２〜２５μｍであ
る。最外層を積層化する例としては、図示はしないが次
の１）〜８）が挙げられる。 １）延伸ポリエチレンテレフタレート／延伸ナイロン ２）延伸ナイロン／延伸延伸ポリエチレンテレフタレー
ト また、包装材料の機械適性（包装機械、加工機械の中で
の搬送の安定性）、表面保護性（耐熱性、耐電解質
性）、２次加工とてリチウムイオン電池用の外装体をエ
ンボスタイプとする際に、エンボス時の金型と最外層と
の摩擦抵抗を小さくする目的で、最外層を多層化、最外
層表面にフッ素系樹脂層、アクリル系樹脂層、シリコー
ン系樹脂層、またはこれらのブレンド物からなる樹脂層
等を設けることが好ましい。例えば、 ３）フッ素系樹脂／延伸ポリエチレンテレフタレート
（フッ素系樹脂は、フィルム状物、または液状コーティ
ング後乾燥で形成） ４）シリコーン系樹脂／延伸ポリエチレンテレフタレー
ト（シリコーン系樹脂は、フィルム状物、または液状コ
ーティング後乾燥で形成） ５）フッ素系樹脂／延伸ポリエチレンテレフタレート／
延伸ナイロン ６）シリコーン系樹脂／延伸ポリエチレンテレフタレー
ト／延伸ナイロン ７）アクリル系樹脂／延伸ナイロン（アクリル系樹脂は
フィルム状、または液状コーティング後乾燥で硬化） ８）アクリル系樹脂＋ポリシロキサングラフト系アクリ
ル樹脂／延伸ナイロン（アクリル系樹脂はフィルム状、
または液状コーティング後乾燥で硬化）The outermost layer can be laminated in order to improve the pinhole resistance and the insulation when the battery is used as an outer package. When the outermost layer is formed into a laminate, the outermost layer includes at least one resin layer of two or more layers, and each layer has a thickness of 6 µm or more, preferably 12 to 25 µm. Although not shown, examples of laminating the outermost layer include the following 1) to 8). 1) Stretched polyethylene terephthalate / stretched nylon 2) Stretched nylon / stretched stretched polyethylene terephthalate Also, the mechanical suitability of the packaging material (stability of transport in packaging machines and processing machines), surface protection (heat resistance, electrolyte resistance) ) When the exterior body for a lithium ion battery is embossed as a secondary process, the outermost layer is multi-layered to reduce the frictional resistance between the mold and the outermost layer during embossing. It is preferable to provide a fluorine-based resin layer, an acrylic-based resin layer, a silicone-based resin layer, a resin layer made of a blend thereof, or the like. For example, 3) Fluorine-based resin / stretched polyethylene terephthalate (fluorine-based resin is formed into a film or liquid coating and then dried) 4) Silicone-based resin / stretched polyethylene terephthalate (silicone-based resin is film-like or liquid 5) Fluorine resin / stretched polyethylene terephthalate /
Stretched nylon 6) Silicone resin / Stretched polyethylene terephthalate / Stretched nylon 7) Acrylic resin / Stretched nylon (Acrylic resin is cured in film form or liquid coating followed by drying) 8) Acrylic resin + polysiloxane grafted acrylic resin / Stretched nylon (acrylic resin film
Or cured by drying after liquid coating)
【００２０】リチウムイオン電池用包装材料の積層体を
形成する際の積層方法は、ドライラミネート法、熱ラミ
ネート法、押出ラミネート法、サンドイッチラミネート
法、共押出ラミネート法等を利用することができる。As the lamination method for forming the laminate of the packaging material for the lithium ion battery, a dry lamination method, a heat lamination method, an extrusion lamination method, a sandwich lamination method, a coextrusion lamination method, or the like can be used.
【００２１】リチウムイオン電池用包装材料におけるバ
リア層１２は、外装体を通して外部からリチウムイオン
電池の内部に特に水蒸気が進入することを防止するため
の層で、バリア層単体のピンホール、及び加工適性（パ
ウチ化、エンボス成形）を安定化し、かつ耐ピンホール
性をもたせるために厚さ１５μｍ以上のアルミニウム、
ニッケルなどの金属、または、無機化合物、例えば酸化
珪素、アルミナ等を蒸着したフィルム等も挙げられる
が、バリア層としては、好ましくは１５μｍ〜８０μｍ
のアルミニウムである。ピンホールの発生を減らすよう
にさらに改善し、リチウムイオン電池の外装体のタイプ
をエンボスタイプとする際、エンボス部におけるクラッ
ク等の発生のないものとするために、本発明者らは、バ
リア層として用いるアルミニウムの材質が、鉄含有量が
０．３〜９．０重量％、好ましくは０．７〜２．０重量
％とすることによって、鉄を含有していないアルミニウ
ムと比較して、アルミニウムの展延性がよく、積層体と
して折り曲げによるピンホールの発生が少なくなり、か
つ前記エンボスタイプの外装体をエンボスする時に側壁
の形成も容易にできることを見出した。前記鉄含有量が
０．３重量％未満の場合は、ピンホールの発生の防止、
エンボス成形性の改善等の効果が認められず、また、前
記アルミニウムの鉄含有量が９．０重量％を超える場合
は、アルミニウムとしての柔軟性が阻害され、積層体とし
て製袋性が悪くなる。The barrier layer 12 in the packaging material for a lithium ion battery is a layer for preventing water vapor from particularly entering the inside of the lithium ion battery from the outside through the outer package. (Pouching, embossing) to stabilize and provide pinhole resistance aluminum with a thickness of 15 μm or more;
A metal such as nickel, or an inorganic compound, for example, a film on which silicon oxide, alumina, or the like is vapor-deposited may be mentioned.
Aluminum. In order to further reduce the occurrence of pinholes and to eliminate the occurrence of cracks and the like in the embossed portion when the type of the exterior body of the lithium ion battery is embossed, the present inventors have proposed a barrier layer. When the material of aluminum used as the iron has an iron content of 0.3 to 9.0% by weight, and preferably 0.7 to 2.0% by weight, aluminum in comparison with aluminum not containing iron is used. It has been found that the extensibility of the laminate is good, the occurrence of pinholes due to bending as a laminate is reduced, and the side walls can be easily formed when embossing the embossed type exterior body. When the iron content is less than 0.3% by weight, prevention of pinhole generation,
When the effect of improving the embossability is not recognized, and when the iron content of the aluminum exceeds 9.0% by weight, the flexibility as aluminum is impaired and the bag-making properties as a laminate deteriorate. .
【００２２】また、冷間圧延で製造されるアルミニウム
は焼きなまし（いわゆる焼鈍処理）条件でその柔軟性・
腰の強さ・硬さが変化するが、本実施例で用いられるア
ルミニウムは焼きなましをしていない硬質処理品より、
焼きなましを適宜行った、柔軟性がある軟質処理品が好
ましい。また、柔軟性・腰の強さ・硬さの度合い、すな
わち焼きなましの条件は、加工適性（パウチ化、エンボ
ス適性）に合わせ適宜選定すればよい。たとえば、エン
ボス成形時のピンホールやしわを防止するためには、焼
きなましをしていない硬質アルミニウムより多少または
完全に焼きなまし処理をした軟質傾向にあるアルミニウ
ムが良好である。Further, the aluminum produced by cold rolling has its flexibility and flexibility under the conditions of annealing (so-called annealing treatment).
Although the strength and hardness of the waist change, the aluminum used in this embodiment is more rigid than the hard treated product that has not been annealed.
A soft and soft treated product which has been appropriately subjected to annealing is preferable. In addition, the degree of flexibility / strength / hardness, that is, the annealing condition may be appropriately selected in accordance with workability (pouching, embossability). For example, in order to prevent pinholes and wrinkles during embossing, it is preferable to use aluminum that has a soft tendency that has been slightly or completely annealed than hard aluminum that has not been annealed.
【００２３】さらに、本発明者らは、リチウムイオン電
池の電解質と水分とによる反応で生成する、フッ化水素
（化学式：ＨＦ）により、アルミニウム表面の溶解、腐
食、特に表面に存在する酸化アルミが溶解、腐食するこ
とを防止し、かつアルミニウム表面の接着性（濡れ性）
を向上させ、積層体形成時のアルミニウムと最内層との
接着力の安定化を図る課題に対して、アルミニウム表面
に耐酸性皮膜の形成、接着性向上処理に顕著な効果のあ
ることをみいだし提案してきた。Further, the present inventors have found that hydrogen fluoride (chemical formula: HF) generated by a reaction between the electrolyte of a lithium ion battery and moisture causes dissolution and corrosion of the aluminum surface, particularly aluminum oxide existing on the surface. Prevents dissolution and corrosion, and adhesion (wetting) of aluminum surface
Has been found to have a remarkable effect on the formation of an acid-resistant film on the aluminum surface and a treatment for improving the adhesion, in order to improve the adhesion and stabilize the adhesion between the aluminum and the innermost layer when forming the laminate. I have proposed.
【００２４】本発明におけるタブの化成処理における、
リチウムイオン電池用包装材料の最内層（ヒートシール
層）は、図１（ｅ）にし示すように、最内層同士がヒー
トシール性を有するとともに、タブを形成している金属
に対してもヒートシール性を示し、かつ、内容物により
変質、劣化しない材質を検討した結果、厚さ１０μｍ以
上、好ましくは２０〜１００μｍであって融点８０℃以
上、ビカット軟化点が７０℃以上の不飽和カルボングラ
フトポリエチレン、不飽和カルボン酸グラフトポリプロ
ピレン、不飽和カルボングラフトポリメチルペンテンな
どの不飽和カルボングラフトポリオレフィン系樹脂、金
属イオン架橋ポリエチレン、またはエチレンまたはプロ
ピレンとアクリル酸、またはメタクリル酸との共重合
物、およびこれらの変性物の少なくとも一つを含むもの
が良好な結果を示した。In the chemical conversion treatment of the tub according to the present invention,
As shown in FIG. 1 (e), the innermost layer (heat seal layer) of the packaging material for a lithium ion battery has a heat seal property between the innermost layers and also heat seals the metal forming the tab. As a result of examining a material which exhibits properties and does not deteriorate or deteriorate depending on the contents, it is found that the thickness is 10 μm or more, preferably 20 to 100 μm, the melting point is 80 ° C. or more, and the unsaturated carboxylic graft polyethylene having a Vicat softening point of 70 ° C. or more. , Unsaturated carboxylic acid-grafted polypropylene, unsaturated carboxylic acid-grafted polyolefin resin such as unsaturated carboxylic acid-grafted polymethylpentene, metal ion-crosslinked polyethylene, or copolymer of ethylene or propylene with acrylic acid, or methacrylic acid, and these Those containing at least one of the modified products showed good results .
【００２５】ヒートシール層１４には、金属接着性を持
たないポリオレフィン等を用いることもできるが、この
場合には、図１（ｆ）に示すように、電極と前記最内層
との間に前記不飽和カルボングラフトポリオレフィン、
金属架橋ポリエチレン、エチレンまたはプロピレンとア
クリル酸、またはメタクリル酸との共重合物から形成さ
れる熱接着性タブ材（厚さ１５μｍ以上、以下接着性フ
ィルムと記載する）６を用いることによって、タブ４と
外装体１０とが完全に接着され、密封することができ
る。タブ４と前記最内層１４との間に接着性フィルム６
を介在させることにより、密封性を確保することができ
る。タブ部への接着性フィルムのセット方法は、図５
（ａ）、図５（ｂ）、図５（ｃ）に示すように、タブ４
とヒートシール層１４との間に、金属とヒートシール層
との双方に対してシール性を有する接着性フィルム６を
介在させてもよいし、また、図５（ｄ）、図５（ｅ）、
図５（ｆ）に示すように、タブ４の所定の位置に巻き付
けても良い。前記接着性フィルム６としては、不飽和カ
ルボン酸グラフトポリオレフィン、金属架橋ポリエチレ
ン、エチレンまたは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からなるフィルム等を用いるこ
とができる。なお、本発明の積層体におけるヒートシー
ル層１４は、前記の樹脂からなる単層でもよいし、ま
た、前記樹脂を含む２層以上の複層としてよい。The heat seal layer 14 may be made of polyolefin or the like having no metal adhesion. In this case, as shown in FIG. 1 (f), the heat seal layer 14 is provided between the electrode and the innermost layer. Unsaturated carboxylic graft polyolefin,
By using a heat-adhesive tab material (having a thickness of 15 μm or more, hereinafter referred to as an adhesive film) 6 formed of a metal cross-linked polyethylene, a copolymer of ethylene or propylene and acrylic acid or methacrylic acid, the tab 4 And the exterior body 10 are completely adhered and can be sealed. Adhesive film 6 between tab 4 and said innermost layer 14
The sealing property can be ensured by interposing. The method for setting the adhesive film on the tab portion is shown in FIG.
(A), FIG. 5 (b), and FIG.
An adhesive film 6 having a sealing property to both the metal and the heat seal layer may be interposed between the heat seal layer 14 and the heat seal layer 14, and FIGS. 5 (d) and 5 (e). ,
As shown in FIG. 5F, the tab 4 may be wound around a predetermined position. As the adhesive film 6, an unsaturated carboxylic acid-grafted polyolefin, a metal cross-linked polyethylene, a film made of a copolymer of ethylene or propylene and acrylic acid or methacrylic acid, or the like can be used. The heat seal layer 14 in the laminate of the present invention may be a single layer made of the above resin, or may be a multilayer of two or more layers containing the resin.
【００２６】前記不飽和カルボングラフトポリオレフィ
ン系樹脂は、電極との接着性、耐熱性、耐寒性、加工適
性（パウチ化、エンボス成形性）のいずれにも適してい
る。最内層の厚さが２０μｍ未満では、電極をヒートシ
ールした時、その端部部分に隙間ができバリア性がなく
なる。また、最内層の厚さが１００μｍを超えても、ヒ
ートシール強度は変わらず、積層体としての厚さが増し
て、本発明の課題である省スペースに逆行する。また、
融点、ビカット軟化点が低い場合、耐熱性、耐寒性がな
くなりフィルム同士および電極との接着強度が低下し破
袋する。また、前記各種の不飽和カルボングラフトポリ
マーは、それぞれ単体で用いてもよいが、２種以上の樹
脂をブレンドすることでもその性質は満足される。The unsaturated carboxy-grafted polyolefin-based resin is suitable for any of adhesiveness to an electrode, heat resistance, cold resistance, and processability (pouching, embossability). When the thickness of the innermost layer is less than 20 μm, when the electrode is heat-sealed, a gap is formed at the end portion and the barrier property is lost. Further, even if the thickness of the innermost layer exceeds 100 μm, the heat seal strength does not change, and the thickness of the laminate increases, which goes against the space saving which is the object of the present invention. Also,
When the melting point and the Vicat softening point are low, the heat resistance and the cold resistance are lost, and the adhesive strength between the films and the electrodes is reduced, and the bag is broken. In addition, the above-mentioned various unsaturated carboxy-grafted polymers may be used alone, but their properties can be satisfied by blending two or more resins.
【００２７】本発明の積層体の前記各層には、適宜、製
膜性、積層化加工、最終製品２次加工（パウチ化、エン
ボス成形）適性を向上、安定化する目的のために、コロ
ナ処理、ブラスト処理、酸化処理、オゾン処理等の表面
活性化処理をしてもよい。Each of the layers of the laminate of the present invention may be subjected to corona treatment for the purpose of improving and stabilizing the film forming property, lamination processing, and suitability for the secondary processing of the final product (pouching, embossing). A surface activation treatment such as a blast treatment, an oxidation treatment, and an ozone treatment may be performed.
【００２８】本発明の積層体の最外層、バリア層、中間
層、最内層の各層を形成する、または、各層間の積層方
法等は、具体的にはＴダイ法、インフレーション法、共
押出し法等を用いて製膜することができる。必要に応じ
て、コーティング、蒸着、紫外線硬化、電子線硬化等の
方法によって２次膜を形成してもよい。また、貼り合わ
せの方法としては、ドライラミネート法、押出ラミネー
ト法、共押出ラミネート法、熱ラミネート法等の方法を
用いることができる。The outermost layer, the barrier layer, the intermediate layer, and the innermost layer of the laminate of the present invention are formed, or the method of laminating each layer is specifically a T-die method, an inflation method, a co-extrusion method, or the like. And the like can be used. If necessary, the secondary film may be formed by a method such as coating, vapor deposition, ultraviolet curing, and electron beam curing. Further, as a bonding method, a method such as a dry lamination method, an extrusion lamination method, a co-extrusion lamination method, or a heat lamination method can be used.
【００２９】前記、ドライラミネート法により貼り合わ
せを行う際には、ポリエステル系、ポリエチレンイミン
系、ポリエーテル系、シアノアクリレート系、ウレタン
系、有機チタン系、ポリエーテルウレタン系、エポキシ
系、ポリエステルウレタン系、イミド系、イソシアネー
ト系、ポリオレフィン系、シリコーン系の各種接着剤を
用いることができる。また、これらの接着層には適宜、
酸化珪素、炭酸カルシウム、亜鉛、鉛丹、亜酸化鉛、酸
化鉛、シアナミド鉛、ジンククロメート、クロム酸バリ
ウムカリウム、クロム酸バリウム亜鉛の少なくとも一つ
を含有することを特徴とした添加剤を添加することも耐
薬品性、耐有機溶剤性をさらに向上させる。特に、酸化
珪素、炭酸カルシウム、亜鉛、鉛丹、亜酸化鉛、酸化亜
鉛、シアナミド鉛、ジンククロメート、クロム酸バリウ
ムカリウム、クロム酸バリウム亜鉛などは電解液と水分
との反応で発生するフッ化水素を吸収・吸着する効果が
あり、各層、特にバリア層（アルミニウム）に対するフ
ッ化水素の腐食を防止する効果がある。When laminating by the dry laminating method, polyester-based, polyethyleneimine-based, polyether-based, cyanoacrylate-based, urethane-based, organic titanium-based, polyetherurethane-based, epoxy-based, polyester urethane-based Imide, isocyanate, polyolefin and silicone adhesives can be used. In addition, these adhesive layers may be appropriately
Add an additive characterized by containing at least one of silicon oxide, calcium carbonate, zinc, red lead, lead oxide, lead oxide, cyanamide lead, zinc chromate, barium potassium chromate, and barium zinc chromate. This further improves the chemical resistance and organic solvent resistance. In particular, silicon oxide, calcium carbonate, zinc, lead red, lead suboxide, zinc oxide, cyanamide lead, zinc chromate, barium potassium chromate, and barium zinc chromate are hydrogen fluoride generated by the reaction between electrolyte and water. And has the effect of preventing corrosion of hydrogen fluoride on each layer, particularly on the barrier layer (aluminum).
【００３０】また、前記押出ラミネート法を用いる場
合、接着する各層間の接着力を安定化する接着促進化方
法として、ポリエステル系、ポリエーテ系、ウレタン
系、ポリエーテルウレタン系、ポリエステルウレタン
系、イソシアネート系、ポリオレフィン系、ポリエチレ
ンイミン系、シアノアリレート系、有機チタン化合物
系、エポキシ系、イミド系、シリコーン系、およびこれ
らの変性物、または、混合物等の樹脂を１μｍ程度塗布
したり、オゾン処理による表面活性化処理を行うことが
できる。また、前記押出ラミネート法あるいはサーマル
ラミネート法により貼り合わせる際の樹脂として不飽和
カルボン酸グラフトポリオレフィンを用いることによっ
て、接着性とともに耐内容物性も向上する。When the extrusion laminating method is used, as an adhesion promoting method for stabilizing the adhesive force between the layers to be adhered, polyester-based, polyether-based, urethane-based, polyetherurethane-based, polyesterurethane-based, and isocyanate-based Surface activity by applying resin such as polyolefin, polyethyleneimine, cyanoarylate, organotitanium compound, epoxy, imide, silicone, and their modified products or mixture, about 1 μm, and ozone treatment Can be performed. In addition, by using an unsaturated carboxylic acid-grafted polyolefin as a resin at the time of laminating by the extrusion lamination method or the thermal lamination method, the adhesiveness and the content resistance are improved.
【００３１】[0031]
【実施例】本発明のリチウムイオン電池タブおよびタブ
材の化成処理方法について、実施例により説明する。以
下の実施例、比較例ともに共通条件は以下の通りであ
る。 （１）タブは、陽極をニッケル、陰極をアルミニウムと
し、いずれも、巾８ｍｍ、長さ５０ｍｍ、厚さ１００μ
ｍである。 （２）パウチタイプは、ピロータイプとし、パウチサイ
ズは外寸で、巾６０ｍｍ、長さ８０ｍｍとした（シール
巾はいずれも５ｍｍ）。 （３）エンボスタイプは、片面エンボスタイプとし、凹
部は３５ｍｍ×５０ｍｍ凹部の深さは３．５ｍｍ、フラ
ンジ部（シール部）の巾は５ｍｍとした。 （４）実施例におけるタブの脱脂処理および化成処理
は、リチウムイオン電池本体に装着するサイズに断裁し
たものに対して処理した。実際の製造においては、前述
のように、タブ材の金属シートをスリッターした長尺状
態で処理することができる。 ［実施例１］（パウチタイプ） １．タブ材を０．１規定の硫酸液に１０秒間浸漬してか
ら水洗いして乾燥し、フエノール樹脂、フッ化水クロム
（３）化合物、リン酸からなる水溶液中に５秒間浸漬し
て引上げ、熱風により、水分を除去した後、遠赤外線ヒ
ーターにより、皮膜温度が１９０℃に到達するまで加熱
して、リチウムイオン電池のセル端部に接合して、本体
実施例１とした。 ２．外装体を形成する積層体は、次のようにして作成し
た。アルミニウム２０μｍの片面に化成処理を施し、化
成処理していない面に延伸ポリエステルフィルム（厚さ
１６μｍ）をドライラミネート法により貼り合わせ、次
に、化成処理したアルミニウムの面、化成処理層に、酸
変性ポリプロピレンフィルム５０μｍをドライラミネー
トにより貼り合わせて得られた積層体を用いてパウチ化
して、外装体１を得た。 ３．外装体実施例１の中に、本体実施例１を収納して、
本体実施例の未シール部をタブと共にヒートシールして
検体実施例１を得た。 ［実施例２］（エンボスタイプ） １．タブ材を１．０規定の水酸化ナトリウム液に１０秒
間浸漬してから水洗いして乾燥し、フエノール樹脂、フ
ッ化水クロム（３）化合物、リン酸からなる水溶液中に
５秒間浸漬して引上げ、熱風により、水分を除去した
後、遠赤外線ヒーターにより、皮膜温度が１９０℃に到
達するまで加熱して、リチウムイオン電池のセル端部に
接合して、本体実施例２とした。 ２．アルミニウム４０μｍの両面に化成処理を施し、化
成処理した一方の面に延伸ナイロンフィルム（厚さ２５
μｍ）をドライラミネート法により貼り合わせ、次に、
化成処理したアルミニウムの他の面に、酸変性ポリプロ
ピレンを接着樹脂（厚さ１５μｍ）として、プロピレン
フィルム（密度０．９２１、厚さ３０μｍ）をサンドイ
ッチラミネートして一次積層体とした。該一次積層体
を，熱風により酸変性ポリプロピレン樹脂の軟化点以上
の温度に加熱して二次積層体とした後、エンボス成形し
て、成形しない二次積層体を蓋材として外装体実施例２
を得た。接着性フィルムとして、酸変性ポリプロピレン
１００μｍによってタブを挟持した状態として、外装体
実施例２のエンボス部の中に収納して、蓋体を被覆して
周縁をヒートシールして検体実施例２を得た。EXAMPLES The method for chemical conversion treatment of a lithium ion battery tab and a tab material according to the present invention will be described with reference to examples. The common conditions for the following examples and comparative examples are as follows. (1) The tab was made of nickel for the anode and aluminum for the cathode, each having a width of 8 mm, a length of 50 mm, and a thickness of 100 μm.
m. (2) The pouch type was a pillow type, and the pouch size was an outer dimension, a width of 60 mm and a length of 80 mm (each seal width was 5 mm). (3) The embossed type was a single-sided embossed type, the recess was 35 mm × 50 mm, the depth of the recess was 3.5 mm, and the width of the flange portion (seal portion) was 5 mm. (4) The degreasing and chemical conversion treatments of the tabs in the examples were performed on the tabs cut to a size to be mounted on the lithium ion battery body. In actual production, as described above, the metal sheet of the tab material can be processed in a slitted and long state. [Example 1] (pouch type) The tab material is immersed in a 0.1N sulfuric acid solution for 10 seconds, washed with water and dried, immersed in an aqueous solution comprising a phenol resin, a chromium fluoride (3) compound, and phosphoric acid for 5 seconds and pulled up. After removing water, heating was performed by a far-infrared heater until the film temperature reached 190 ° C., and this was joined to a cell end of a lithium ion battery to obtain main body example 1. 2. The laminate forming the exterior body was prepared as follows. A chemical conversion treatment is applied to one surface of aluminum 20 μm, and a stretched polyester film (16 μm thick) is bonded to a non-chemical conversion surface by a dry lamination method. The exterior body 1 was obtained by pouching using a laminate obtained by laminating a polypropylene film of 50 μm by dry lamination. 3. In the outer body embodiment 1, the main body embodiment 1 is stored.
The unsealed portion of the main body example was heat-sealed together with the tab to obtain a sample example 1. [Example 2] (emboss type) The tab material is immersed in a 1.0 N sodium hydroxide solution for 10 seconds, washed with water, dried, and immersed in an aqueous solution containing a phenol resin, a chromium fluoride (3) compound, and phosphoric acid for 5 seconds and pulled up. After removing water with hot air, the film was heated with a far-infrared heater until the film temperature reached 190 ° C. and joined to the cell end of the lithium ion battery to obtain a main body example 2. 2. A chemical conversion treatment was performed on both sides of aluminum 40 μm, and a stretched nylon film (thickness: 25
μm) by dry lamination, and then
On the other surface of the chemically treated aluminum, a propylene film (density 0.921, thickness 30 μm) was sandwich-laminated with an acid-modified polypropylene as an adhesive resin (thickness 15 μm) to form a primary laminate. The primary laminate was heated to a temperature equal to or higher than the softening point of the acid-modified polypropylene resin by hot air to form a secondary laminate, which was then embossed.
I got As an adhesive film, the tab was sandwiched by 100 μm of acid-modified polypropylene, and housed in the embossed portion of the outer package example 2, covered with the lid, and heat-sealed at the periphery to obtain sample example 2. Was.
【実施例３】（パウチタイプ）タブ材をアセトン中に１
０秒間浸漬してから乾燥し、フェノール樹脂、アクリル
樹脂、フッ化水素と《１》モリブデン、《２》チタン、
《３》ジルコンの金属を含む３種類の溶液にそれぞれ浸
漬し、皮膜温度が１８０℃に到達するまで加熱して、リ
チウムイオン電池のセル端部に接合して、本体実施例３
《１》《２》《３》とした。 ２．外装体を形成する積層体は、次のようにして作成し
た。アルミニウム２０μｍの片面に化成処理を施し、化
成処理していない面に延伸ポリエステルフィルム（厚さ
１６μｍ）をドライラミネート法により貼り合わせ、次
に、化成処理したアルミニウムの面、化成処理層に、酸
変性ポリプロピレンフィルム５０μｍをドライラミネー
トにより貼り合わせて得られた積層体を用いてパウチ化
して、外装体実施例３を得た。 ３．外装体実施例３の中に、本体実施例３《１》《２》
《３》を収納して、本体実施例の未シール部をタブと共
にヒートシールして検体実施例３を得た。Embodiment 3 (pouch type) A tab material is put in acetone for 1 hour.
After immersion for 0 seconds and drying, phenol resin, acrylic resin, hydrogen fluoride and << 1 >> molybdenum, << 2 >> titanium,
<< 3 >> Each of the three types of solutions containing zircon metal was immersed, heated until the coating temperature reached 180 ° C., and joined to the cell end of the lithium-ion battery to form a main body example 3.
<< 1 >><< 2 >><< 3 >>. 2. The laminate forming the exterior body was prepared as follows. A chemical conversion treatment is applied to one surface of aluminum 20 μm, and a stretched polyester film (16 μm thick) is bonded to a non-chemical conversion surface by a dry lamination method. Using a laminate obtained by laminating a polypropylene film of 50 μm by dry lamination, the laminate was pouched to obtain an outer package example 3. 3. In the exterior body embodiment 3, the main body embodiment 3 << 1 >><< 2 >>
<3> was accommodated, and the unsealed portion of the main body example was heat-sealed together with the tab to obtain Sample Example 3.
【実施例４】（エンボスタイプ） １．タブ材をアセトン中に１０秒間浸漬してから乾燥
し、フェノール樹脂、アクリル樹脂、フッ化水素と
《１》モリブデン、《２》チタン、《３》ジルコンの金
属を含む３種類の溶液にそれぞれ浸漬し、皮膜温度が１
８０℃に到達するまで加熱して、リチウムイオン電池の
セル端部に接合して、本体実施例４《１》《２》《３》
とした。した。 ２．アルミニウム４０μｍの両面に化成処理を施し、化
成処理した一方の面に延伸ナイロンフィルム（厚さ２５
μｍ）をドライラミネート法により貼り合わせ、次に、
化成処理したアルミニウムの他の面に、ＭＤＰＥをヒー
トシール層として３０μｍの厚さの溶融樹脂膜として押
出して、該溶融樹脂膜のアルミニウムとのラミネート面
をオゾン処理しながら、押出ラミネートして積層体とし
た後、ＭＤＰＥの軟化点以上に加熱して得られた積層体
を用いてエンボス成形し、蓋体は成形せずに所定のサイ
ズに断裁して外装体実施例４を得た。接着性フィルムと
して、酸変性ＬＬＤＰＥ１００μｍによってタブを挟持
した状態として、外装体４のエンボス部の中に本体実施
例４を収納して、蓋体を被覆して周縁をヒートシールし
て検体実施例４《１》《２》《３》を得た。Embodiment 4 (Emboss Type) The tab material is immersed in acetone for 10 seconds, then dried, and immersed in each of three types of solutions containing phenolic resin, acrylic resin, hydrogen fluoride and metals of <1> molybdenum, <2> titanium, and <3> zircon. And the film temperature is 1
Heat until the temperature reaches 80 ° C. and join to the cell end of the lithium-ion battery to obtain a main body example 4 << 1 >><< 2 >><< 3 >>
And did. 2. A chemical conversion treatment was performed on both sides of aluminum 40 μm, and a stretched nylon film (thickness: 25
μm) by dry lamination, and then
On the other surface of the chemically treated aluminum, MDPE was extruded as a heat-sealable layer as a molten resin film having a thickness of 30 μm, and the laminated surface of the molten resin film was extruded and laminated with ozone while being subjected to ozone treatment. After embossing using the laminate obtained by heating to the softening point of MDPE or higher, the lid was cut into a predetermined size without forming the lid to obtain an outer package example 4. Specimen Example 4 in which the main body example 4 was housed in the embossed portion of the exterior body 4 with the tab sandwiched by acid-modified LLDPE 100 μm as an adhesive film, the lid was covered, and the periphery was heat-sealed. << 1 >><< 2 >><< 3 >> were obtained.
【実施例５】（パウチタイプ） １．タブ材を０．１規定の硫酸液に１０秒間浸漬してか
ら水洗いして乾燥し、トリアジンチオール処理液内で電
解メッキ処理を行い、リチウムイオン電池のセル端部に
接合して、本体実施例５とした。 ２．外装体を形成する積層体は、次のようにして作成し
た。アルミニウム２０μｍの片面に化成処理を施し、化
成処理していない面に延伸ポリエステルフィルム（厚さ
１６μｍ）をドライラミネート法により貼り合わせ、次
に、化成処理したアルミニウムの面、化成処理層に、酸
変性ポリプロピレンフィルム５０μｍをドライラミネー
トにより貼り合わせて得られた積層体を用いてパウチ化
して、外装体実施例５を得た。 ３．外装体実施例５の中に、本体実施例５を収納して、
本体実施例の未シール部をタブと共にヒートシールして
検体実施例５を得た。Embodiment 5 (pouch type) The tab material was immersed in a 0.1N sulfuric acid solution for 10 seconds, washed with water, dried, subjected to electrolytic plating in a triazinethiol treatment solution, and joined to a cell end of a lithium ion battery. It was set to 5. 2. The laminate forming the exterior body was prepared as follows. A chemical conversion treatment is applied to one surface of aluminum 20 μm, and a stretched polyester film (16 μm thick) is bonded to a non-chemical conversion surface by a dry lamination method. Using a laminate obtained by laminating a polypropylene film of 50 μm by dry lamination, the laminate was pouched to obtain an outer package example 5. 3. In the outer body example 5, the main body example 5 is stored.
Sample No. 5 was obtained by heat-sealing the unsealed portion of the main body example together with the tab.
【実施例６】（エンボスタイプ） １．タブ材を０．１規定の硫酸液に１０秒間浸漬してか
ら水洗いして乾燥し、トリアジンチオール処理液内で電
解メッキ処理を行い、リチウムイオン電池のセル端部に
接合して、本体実施例６とした。リチウムイオン電池の
セル端部に接合して、本体実施例６とした。 ２．アルミニウム４０μｍの両面に化成処理を施し、化
成処理した一方の面に延伸ナイロンフィルム（厚さ２５
μｍ）をドライラミネート法により貼り合わせ、次に、
化成処理したアルミニウムの他の面に、ＭＤＰＥをヒー
トシール層として３０μｍの厚さの溶融樹脂膜として押
出して、該溶融樹脂膜のアルミニウムとのラミネート面
をオゾン処理しながら、押出ラミネートして積層体とし
た後、ＭＤＰＥの軟化点以上に加熱して得られた積層体
を用いてエンボス成形し、蓋体は成形せずに所定のサイ
ズに断裁して外装体実施例６を得た。接着性フィルムと
して、酸変性ＬＬＤＰＥ１００μｍによってタブを挟持
した状態として、外装体実施例６のエンボス部の中に本
体実施例６を収納して、蓋体を被覆して周縁をヒートシ
ールして検体実施例６を得た。Embodiment 6 (Emboss type) The tab material was immersed in a 0.1N sulfuric acid solution for 10 seconds, washed with water, dried, subjected to electrolytic plating in a triazinethiol treatment solution, and joined to a cell end of a lithium ion battery. 6. This was joined to the cell end of the lithium ion battery to obtain a main body example 6. 2. A chemical conversion treatment was performed on both sides of aluminum 40 μm, and a stretched nylon film (thickness: 25
μm) by dry lamination, and then
On the other surface of the chemically treated aluminum, MDPE was extruded as a heat-sealable layer as a molten resin film having a thickness of 30 μm, and the laminated surface of the molten resin film was extruded and laminated with ozone while being subjected to ozone treatment. Then, embossing was performed using the laminate obtained by heating to the softening point of MDPE or higher, and the lid was cut into a predetermined size without molding to obtain an outer package body example 6. As the adhesive film, the main body example 6 was housed in the embossed portion of the outer body example 6 with the tabs sandwiched by acid-modified LLDPE 100 μm, the lid was covered, and the periphery was heat-sealed to perform the specimen. Example 6 was obtained.
【００３２】［比較例１］（パウチタイプ） １．タブ材を０．１規定の硫酸液に１０秒間浸漬してか
ら水洗いして乾燥して、リチウムイオン電池のセル端部
に接合して、本体比較例１とした。 ２．外装体を形成する積層体は、次のようにして作成し
た。アルミニウム２０μｍの片面に化成処理を施し、化
成処理していない面に延伸ポリエステルフィルム（厚さ
１６μｍ）をドライラミネート法により貼り合わせ、次
に、化成処理したアルミニウムの面、化成処理層に、酸
変性ポリプロピレンフィルム５０μｍをドライラミネー
トにより貼り合わせて得られた積層体を用いてパウチ化
して、外装体比較例１を得た。 ３．外装体比較例１の中に、本体比較例１を収納して、
外装体比較例１の未シール部をタブとともにヒートシー
ルして検体比較例１を得た。 ［比較例２］（エンボスタイプ） １．タブ材を０．１規定の硫酸液に１０秒間浸漬してか
ら水洗いして乾燥して、リチウムイオン電池のセル端部
に接合して、本体比較例２とした。 ２．アルミニウム４０μｍの両面に化成処理を施し、化
成処理した一方の面に延伸ナイロンフィルム（厚さ２５
μｍ）をドライラミネート法により貼り合わせ、次に、
化成処理したアルミニウムの他の面に、ＭＤＰＥをヒー
トシール層として３０μｍの厚さの溶融樹脂膜として押
出して、該溶融樹脂膜のアルミニウムとのラミネート面
をオゾン処理しながら、押出ラミネートして積層体とし
た後、該積層体を、ＭＤＰＥの軟化点以上に加熱して、
得られた積層体を用いてエンボス成形し、蓋体は成形せ
ずに所定のサイズに断裁して外装体比較例２を得た。 ３．接着性フィルムとして、酸変性ＬＬＤＰＥ１００μ
ｍによってタブを挟持した状態として、外装体比較例２
のエンボス部の中に本体比較例２を収納して、蓋体を被
覆して周縁をヒートシールして検体比較例２を得た。 ＜評価方法＞Comparative Example 1 (Pouch type) The tab material was immersed in a 0.1N sulfuric acid solution for 10 seconds, washed with water, dried, and joined to the cell end of the lithium ion battery to obtain Comparative Example 1 of the main body. 2. The laminate forming the exterior body was prepared as follows. A chemical conversion treatment is applied to one surface of aluminum 20 μm, and a stretched polyester film (16 μm thick) is bonded to a non-chemical conversion surface by a dry lamination method. Using a laminate obtained by laminating a polypropylene film of 50 μm by dry lamination, the laminate was pouched to obtain an outer package comparative example 1. 3. In the exterior body comparative example 1, the main body comparative example 1 is stored,
The unsealed portion of the outer package comparative example 1 was heat-sealed together with the tab to obtain a sample comparative example 1. Comparative Example 2 (Emboss Type) The tab material was immersed in a 0.1 N sulfuric acid solution for 10 seconds, washed with water, dried, and joined to the cell end of the lithium ion battery to obtain a main body comparative example 2. 2. A chemical conversion treatment was performed on both sides of aluminum 40 μm, and a stretched nylon film (thickness: 25
μm) by dry lamination, and then
On the other surface of the chemically treated aluminum, MDPE was extruded as a heat-sealable layer as a molten resin film having a thickness of 30 μm, and the laminated surface of the molten resin film was extruded and laminated with ozone while being subjected to ozone treatment. After that, the laminate is heated above the softening point of MDPE,
The obtained laminate was embossed, and the lid was cut into a predetermined size without molding to obtain an outer package comparative example 2. 3. Acid-modified LLDPE 100μ as adhesive film
In the state where the tab is sandwiched by m, the exterior body comparative example 2
Was stored in the embossed portion of Example 1, and the lid was covered and the periphery was heat-sealed to obtain Sample Comparative Example 2. <Evaluation method>
【００３３】前記のようにして得られた各検体のタブ部
を下にして、静置し、外装体の中に、電解液（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の液に１ｍｏｌの６フッ化リン酸リ
チウムを添加）の５ｇを入れて、８５℃、３０日間の保
存テストを行い、タブ部からの内容物の漏れと漏れてい
る部位を目視によりチェックした。 ＜結果＞Each sample obtained as described above is allowed to stand with the tab portion facing down, and an electrolyte (ethylene carbonate: diethyl carbonate: dimethyl carbonate = 1: 1: 1 solution) is placed in the outer package. 5 g of 1 mol of lithium hexafluorophosphate) was added thereto, and a storage test was performed at 85 ° C. for 30 days. Leakage of the contents from the tab portion and a leaked portion were visually checked. <Result>
【００３４】実施例は、いずれも、漏れはなく、タブの
アルミニウムでの密封性は良好であった。比較例１は、
１０００検体中、４００検体において、タブの陰極（ア
ルミニウム）から液漏れがあった。また、比較例２にお
いては、１０００検体中５００検体に同様の漏れが発生
した。In each of the examples, there was no leakage and the sealability of the tab with aluminum was good. Comparative Example 1
Of the 1000 samples, 400 samples leaked from the cathode (aluminum) of the tub. In Comparative Example 2, the same leak occurred in 500 out of 1,000 samples.
【００３５】[0035]
【発明の効果】リチウムイオン電池のタブの表面に化成
処理層を設けることによって、タブと外装体との接着が
確実となり、特に、リチウムイオン電池の構成要素であ
る電解液成分と、外部からリチウムイオン電池内に浸入
した水分との反応により生成するフッ化水素酸によるタ
ブ表面の腐食、溶解を防止でき、タブ部での密封性が安
定した。By providing a chemical conversion treatment layer on the surface of the tab of the lithium ion battery, the adhesion between the tab and the outer package is ensured. In particular, the electrolyte component, which is a component of the lithium ion battery, and lithium from the outside Corrosion and dissolution of the tub surface due to hydrofluoric acid generated by the reaction with moisture entering the ion battery could be prevented, and the sealing performance at the tub portion was stabilized.
【図１】本発明のリチウムイオン電池タブおよびタブ材
による化成処理方法の実施例を示す、（ａ）リチウムイ
オン電池本体および外装体の斜視図、（ｂ）Ｘ1−Ｘ1部
断面図、（ｃ）Ｙ1部の拡大図、（ｄ）リチウムイオン
電池本体を外装体に収納した状態の斜視図、（ｅ）Ｘ2
−Ｘ2部での断面図、（ｆ）Ｘ2−Ｘ2部での別の断面図
である。FIG. 1 shows an embodiment of a chemical conversion treatment method using a tab and a tab material of a lithium ion battery of the present invention, (a) a perspective view of a lithium ion battery main body and an exterior body, (b) a cross-sectional view of X 1 -X 1 part, (c) an enlarged view of a Y 1 parts perspective view of a state where the housing (d) is a lithium ion battery main body in the outer body, (e) X 2
Sectional view taken along the -X 2 parts, is another cross-sectional view at (f) X 2 -X 2 parts.
【図２】リチウムイオン電池のパウチタイプの外装体を
説明する斜視図である。FIG. 2 is a perspective view illustrating a pouch type exterior body of a lithium ion battery.
【図３】リチウムイオン電池のエンボスタイプの外装体
を説明する斜視図である。FIG. 3 is a perspective view illustrating an embossed type exterior body of a lithium ion battery.
【図４】本発明のリチウムイオン電池用包装材料におけ
るタブ部の外装体および接着性フィルムの実施例を説明
する図で、（ａ）ヒートシール前の外装体、接着性フィ
ルム、タブの位置関係を片面シール側のみで示し、
（ｂ）ヒートシール後の構成を両面で示す断面図であ
る。FIG. 4 is a view for explaining an embodiment of an outer package of a tab portion and an adhesive film in a packaging material for a lithium ion battery of the present invention, wherein (a) a positional relationship between an outer package, an adhesive film, and a tab before heat sealing; Is shown only on the one side seal side,
(B) It is sectional drawing which shows the structure after heat sealing on both surfaces.
【図５】リチウムイオン電池用包装材料とタブとの接着
における接着性フィルムの装着方法を説明する斜視図で
ある。FIG. 5 is a perspective view for explaining a method of mounting an adhesive film in bonding a wrapping material for a lithium ion battery and a tab.
１ リチウムイオン電池 ２ リチウムイオン電池本体 ３ セル（蓄電部） ４ タブ（電極） ４Ｍ タブ材 ４Ｓ 化成処理層（タブ） ５ 外装体 ６ 接着性フィルム ７ 凹部 ８ 側壁部 ９ シール部 １０ 外装体を形成する積層体 １１ 基材層 １２ バリア層 １３ 接着樹脂層 １４ ヒートシール層 DESCRIPTION OF SYMBOLS 1 Lithium-ion battery 2 Lithium-ion battery main body 3 Cell (power storage part) 4 Tab (electrode) 4M tab material 4S Chemical conversion treatment layer (tab) 5 Package 6 Adhesive film 7 Depression 8 Side wall 9 Sealing 10 Form package Laminated body 11 base layer 12 barrier layer 13 adhesive resin layer 14 heat seal layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山田 一樹 東京都新宿区市谷加賀町一丁目１番１号 大日本印刷株式会社内 Ｆターム(参考） 4K026 AA09 AA22 AA25 BA01 BA07 BB08 BB10 CA16 CA18 CA22 CA26 CA28 CA37 CA39 EA08 5H011 AA17 CC02 CC06 CC10 DD13 EE04 FF02 GG09 HH02 5H022 AA09 BB12 BB21 CC03 CC19 EE01 EE06 EE07 KK08 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuki Yamada 1-1-1 Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo F-term in Dai Nippon Printing Co., Ltd. 4K026 AA09 AA22 AA25 BA01 BA07 BB08 BB10 CA16 CA18 CA22 CA26 CA28 CA37 CA39 EA08 5H011 AA17 CC02 CC06 CC10 DD13 EE04 FF02 GG09 HH02 5H022 AA09 BB12 BB21 CC03 CC19 EE01 EE06 EE07 KK08
Claims (8)
１、アルミニウム、化成処理層２、ヒートシール層から
なる包装材料にリチウムイオン電池本体を収納し、タブ
を挟持する部分を含め周縁部をヒートシールにより密封
してなるリチウムイオン電池のタブであって、前記リチ
ウムイオン電池の周縁部のヒートシールにおいて、少な
くとも、ヒートシールされる部分の表、裏面および側面
に化成処理が施されていることを特徴とするリチウムイ
オン電池タブ。1. A lithium ion battery main body is housed in a packaging material comprising at least a base material layer, an adhesive layer, a chemical conversion treatment layer 1, aluminum, a chemical conversion treatment layer 2, and a heat seal layer, and a periphery including a portion for holding a tab. A tab of a lithium ion battery in which a portion is sealed by heat sealing, wherein in a heat seal at a peripheral portion of the lithium ion battery, at least a front surface, a back surface, and a side surface of a portion to be heat sealed are subjected to a chemical conversion treatment. A lithium-ion battery tab.
ることを特徴とする請求項１に記載のリチウムイオン電
池タブ。2. The lithium ion battery tab according to claim 1, wherein the chemical conversion treatment is a phosphoric acid chromate treatment.
を含む樹脂成分に、モリブデン、チタン、ジルコン等の
金属、または金属塩を含む化成処理であることを特徴と
する請求項１に記載のリチウムイオン電池タブ。3. The lithium ion battery according to claim 1, wherein the chemical conversion treatment is a chemical treatment in which at least a resin component containing a phenol resin contains a metal such as molybdenum, titanium, zircon, or a metal salt. tab.
あることを特徴とする請求項１に記載のリチウムイオン
電池タブ。4. The tab according to claim 1, wherein the chemical conversion treatment is a triazine thiol treatment.
ム、化成処理層、ポリオレフィン系樹脂のヒートシール
層から構成されるリチウム電池の外装体にリチウム電池
本体を挿入し、タブを挟持する部分を含め周縁部をヒー
トシールにより密封してなるリチウムイオン電池のタブ
であって、前記リチウムイオン電池の周縁部のヒートシ
ールにおいて、少なくとも、ヒートシールされる部分の
表、裏面および側面に化成処理が施されていることを特
徴とするリチウムイオン電池タブ。5. A lithium battery body comprising at least a base layer, an adhesive layer, an aluminum, a chemical conversion treatment layer, and a heat sealing layer of a polyolefin resin, wherein a lithium battery body is inserted into the exterior body, including a portion for holding a tab. A tab of a lithium ion battery having a peripheral portion sealed by heat sealing, wherein in the heat sealing of the peripheral portion of the lithium ion battery, at least a surface, a back surface, and a side surface of a portion to be heat sealed are subjected to a chemical conversion treatment. Lithium-ion battery tabs.
ることを特徴とする請求項５に記載のリチウムイオン電
池タブ。6. The lithium ion battery tab according to claim 5, wherein the chemical conversion treatment is a phosphoric acid chromate treatment.
を含む樹脂成分に、モリブデン、チタン、ジルコン等の
金属、または金属塩を含む化成処理であることを特徴と
する請求項５に記載のリチウムイオン電池タブ。7. The lithium ion battery according to claim 5, wherein the chemical conversion treatment is a chemical conversion treatment in which at least a resin component containing a phenol resin contains a metal such as molybdenum, titanium, zircon, or a metal salt. tab.
あることを特徴とする請求項５に記載のリチウムイオン
電池タブ。8. The tab of claim 5, wherein the chemical conversion treatment is a triazine thiol treatment.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001009706A JP5082170B2 (en) | 2001-01-18 | 2001-01-18 | Lithium ion battery tab |
| CA002370490A CA2370490C (en) | 2000-04-19 | 2001-04-18 | Battery, tab of battery and method of manufacture thereof |
| US10/009,488 US6841298B2 (en) | 2000-04-19 | 2001-04-18 | Battery, tab of battery and method of manufacture thereof |
| CNB018016707A CN100530762C (en) | 2000-04-19 | 2001-04-18 | Battery, tab of battery and method of manufacture thereof |
| KR1020017016082A KR100754052B1 (en) | 2000-04-19 | 2001-04-18 | Battery, Battery Tab and Manufacturing Method Thereof |
| EP01921883.3A EP1276161B1 (en) | 2000-04-19 | 2001-04-18 | Battery, tab of battery and method of manufacture thereof |
| DK01921883.3T DK1276161T3 (en) | 2000-04-19 | 2001-04-18 | Battery, tab of the battery and growth mode of preparation thereof |
| PCT/JP2001/003321 WO2001080330A1 (en) | 2000-04-19 | 2001-04-18 | Battery, tab of battery and method of manufacture thereof |
| TW090109321A TW523948B (en) | 2000-04-19 | 2001-04-18 | Battery, tab of battery and method of manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001009706A JP5082170B2 (en) | 2001-01-18 | 2001-01-18 | Lithium ion battery tab |
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| JP5082170B2 JP5082170B2 (en) | 2012-11-28 |
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| JP2001009706A Expired - Fee Related JP5082170B2 (en) | 2000-04-19 | 2001-01-18 | Lithium ion battery tab |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003019699A1 (en) * | 2001-08-31 | 2003-03-06 | Dai Nippon Printing Co., Ltd. | Laminate for use as outer covering of battery and secondary battery |
| KR100449213B1 (en) * | 2001-02-05 | 2004-09-18 | 닛뽕덴끼 가부시끼가이샤 | Film-sealed non-aqueous electrolyte battery with improved surface-treated lead terminal |
| JP2005268038A (en) * | 2004-03-18 | 2005-09-29 | Japan Storage Battery Co Ltd | Method for manufacturing electrode lead piece, and battery using electrode lead piece |
| WO2005114765A1 (en) * | 2004-05-20 | 2005-12-01 | Seidensha Electronics Co., Ltd | Method of joining polymer battery lead tub to resin film |
| WO2006035691A1 (en) * | 2004-09-30 | 2006-04-06 | Sumitomo Electric Industries, Ltd. | Lead wire for nonaqueous electrolyte battery and nonaqueous electrolyte battery |
| JP2006128096A (en) * | 2004-09-30 | 2006-05-18 | Sumitomo Electric Ind Ltd | Non-aqueous electrolyte battery lead wire and non-aqueous electrolyte battery |
| CN1322603C (en) * | 2005-09-28 | 2007-06-20 | 吉林省巨力电池有限公司 | Method for manufacturing soft-packing lithium ion battery in natural environment |
| JP2010108901A (en) * | 2008-09-30 | 2010-05-13 | Dainippon Printing Co Ltd | Manufacturing method for battery tab, battery tab, and hoop material having same |
| JP2011216343A (en) * | 2010-03-31 | 2011-10-27 | Dainippon Printing Co Ltd | Manufacturing method of battery tab, battery tab, and hoop material equipped with it |
| JP2013004482A (en) * | 2011-06-21 | 2013-01-07 | Sumitomo Electric Ind Ltd | Lead member and method of manufacturing the same |
| KR20130039464A (en) | 2011-10-12 | 2013-04-22 | 에스케이이노베이션 주식회사 | Battery |
| US9209480B2 (en) | 2009-01-29 | 2015-12-08 | Sony Corporation | Secondary battery containing a nonaqueous electrolyte with a sulfonic anhydride and an aromatic compound |
| KR20160108807A (en) | 2015-03-06 | 2016-09-20 | (주)클라비스 | The tab lead chrome-free surface treated for secondary batteries and manufacturing method thereof |
| JP2017212216A (en) * | 2017-07-13 | 2017-11-30 | 藤森工業株式会社 | Method for manufacturing non-aqueous battery storage container provided with electrode lead wire member |
| KR102002801B1 (en) | 2018-02-13 | 2019-07-23 | (주)클라비스 | Chromeless surface treatment of lead tab for improving corrosion resistance |
| CN110556502A (en) * | 2019-09-03 | 2019-12-10 | 深圳市文壹科技有限公司 | sheet type welding attack angle manufacturing process for tabs required by power soft package lithium ion battery |
| JP7544679B2 (en) | 2020-12-22 | 2024-09-03 | 双葉電子工業株式会社 | Tab lead and non-aqueous electrolyte device |
| KR20250050738A (en) | 2023-10-06 | 2025-04-15 | 스미토모 덴키 고교 가부시키가이샤 | Lead member and nonaqueous electrolyte battery |
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| JPH115061A (en) * | 1997-04-23 | 1999-01-12 | Nkk Corp | Surface treated steel sheet with excellent corrosion resistance |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100449213B1 (en) * | 2001-02-05 | 2004-09-18 | 닛뽕덴끼 가부시끼가이샤 | Film-sealed non-aqueous electrolyte battery with improved surface-treated lead terminal |
| WO2003019699A1 (en) * | 2001-08-31 | 2003-03-06 | Dai Nippon Printing Co., Ltd. | Laminate for use as outer covering of battery and secondary battery |
| US7485393B2 (en) | 2001-08-31 | 2009-02-03 | Dai Nippon Printing Co., Ltd. | Laminate for use as outer covering of battery and secondary battery |
| JP2005268038A (en) * | 2004-03-18 | 2005-09-29 | Japan Storage Battery Co Ltd | Method for manufacturing electrode lead piece, and battery using electrode lead piece |
| WO2005114765A1 (en) * | 2004-05-20 | 2005-12-01 | Seidensha Electronics Co., Ltd | Method of joining polymer battery lead tub to resin film |
| WO2006035691A1 (en) * | 2004-09-30 | 2006-04-06 | Sumitomo Electric Industries, Ltd. | Lead wire for nonaqueous electrolyte battery and nonaqueous electrolyte battery |
| JP2006128096A (en) * | 2004-09-30 | 2006-05-18 | Sumitomo Electric Ind Ltd | Non-aqueous electrolyte battery lead wire and non-aqueous electrolyte battery |
| CN1322603C (en) * | 2005-09-28 | 2007-06-20 | 吉林省巨力电池有限公司 | Method for manufacturing soft-packing lithium ion battery in natural environment |
| JP2010108901A (en) * | 2008-09-30 | 2010-05-13 | Dainippon Printing Co Ltd | Manufacturing method for battery tab, battery tab, and hoop material having same |
| US9209480B2 (en) | 2009-01-29 | 2015-12-08 | Sony Corporation | Secondary battery containing a nonaqueous electrolyte with a sulfonic anhydride and an aromatic compound |
| JP2011216343A (en) * | 2010-03-31 | 2011-10-27 | Dainippon Printing Co Ltd | Manufacturing method of battery tab, battery tab, and hoop material equipped with it |
| JP2013004482A (en) * | 2011-06-21 | 2013-01-07 | Sumitomo Electric Ind Ltd | Lead member and method of manufacturing the same |
| KR20130039464A (en) | 2011-10-12 | 2013-04-22 | 에스케이이노베이션 주식회사 | Battery |
| KR20160108807A (en) | 2015-03-06 | 2016-09-20 | (주)클라비스 | The tab lead chrome-free surface treated for secondary batteries and manufacturing method thereof |
| JP2017212216A (en) * | 2017-07-13 | 2017-11-30 | 藤森工業株式会社 | Method for manufacturing non-aqueous battery storage container provided with electrode lead wire member |
| KR102002801B1 (en) | 2018-02-13 | 2019-07-23 | (주)클라비스 | Chromeless surface treatment of lead tab for improving corrosion resistance |
| CN110556502A (en) * | 2019-09-03 | 2019-12-10 | 深圳市文壹科技有限公司 | sheet type welding attack angle manufacturing process for tabs required by power soft package lithium ion battery |
| JP7544679B2 (en) | 2020-12-22 | 2024-09-03 | 双葉電子工業株式会社 | Tab lead and non-aqueous electrolyte device |
| KR20250050738A (en) | 2023-10-06 | 2025-04-15 | 스미토모 덴키 고교 가부시키가이샤 | Lead member and nonaqueous electrolyte battery |
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