JP6055300B2 - Lead terminal adhesive tape that can prevent the adhesive strength from decreasing due to hydrogen fluoride - Google Patents
Lead terminal adhesive tape that can prevent the adhesive strength from decreasing due to hydrogen fluoride Download PDFInfo
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- JP6055300B2 JP6055300B2 JP2012275861A JP2012275861A JP6055300B2 JP 6055300 B2 JP6055300 B2 JP 6055300B2 JP 2012275861 A JP2012275861 A JP 2012275861A JP 2012275861 A JP2012275861 A JP 2012275861A JP 6055300 B2 JP6055300 B2 JP 6055300B2
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- 239000002390 adhesive tape Substances 0.000 title claims description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims description 25
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims description 20
- 239000000853 adhesive Substances 0.000 title description 12
- 230000001070 adhesive effect Effects 0.000 title description 12
- 230000003247 decreasing effect Effects 0.000 title 1
- 239000010410 layer Substances 0.000 claims description 102
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 68
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 32
- 239000011256 inorganic filler Substances 0.000 claims description 30
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 30
- 239000005001 laminate film Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 18
- 229920001169 thermoplastic Polymers 0.000 claims description 13
- 239000004416 thermosoftening plastic Substances 0.000 claims description 13
- 229920003002 synthetic resin Polymers 0.000 claims description 11
- 239000000057 synthetic resin Substances 0.000 claims description 11
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 230000002093 peripheral effect Effects 0.000 claims description 8
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 7
- 239000001095 magnesium carbonate Substances 0.000 claims description 7
- 229920005672 polyolefin resin Polymers 0.000 claims description 7
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 30
- 239000004743 Polypropylene Substances 0.000 description 22
- -1 polypropylene Polymers 0.000 description 20
- 239000005022 packaging material Substances 0.000 description 18
- 238000007789 sealing Methods 0.000 description 17
- 239000010408 film Substances 0.000 description 16
- 229920001155 polypropylene Polymers 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 239000011255 nonaqueous electrolyte Substances 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- CUPFNGOKRMWUOO-UHFFFAOYSA-N hydron;difluoride Chemical compound F.F CUPFNGOKRMWUOO-UHFFFAOYSA-N 0.000 description 2
- 239000003230 hygroscopic agent Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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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
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
Description
本発明は、ラミネートフィルムによって外包された電池包装体において、ラミネートフィルムからなる外包材とリード端子とを接着させる目的でこれらの間に介在させるためのリード端子接着用テープに関し、電池の電解質と水分の反応により生成したフッ化水素により電池包装体の熱接着部の強度低下を防止する機能を発揮するものである。 TECHNICAL FIELD The present invention relates to a lead terminal bonding tape for interposing between an outer packaging material made of a laminate film and a lead terminal in a battery package encased by a laminate film, and the battery electrolyte and moisture. The function which prevents the strength reduction of the heat bonding part of a battery packaging body is exhibited by the hydrogen fluoride produced | generated by this reaction.
電子機器の小型化、軽量化の要求が高まると共に、その電源として用いられるポリマー電池にも小型化、軽量化の要求が強まっていると同時に、電池には高いエネルギー密度、大きいエネルギー容量も求められている。これらの要求を満たすため、近年、ラミネートフィルムの内部に、正極、負極、セパレータおよび非水電解質が封入された非水電解質電池、例えば、薄型リチウムイオン電池の開発が行われてきた。
一方、ポリマー電池は、近年用途の拡大により出力の増大が要求され、電池寸法が大型化する傾向にあり、それにともなって電池に用いられる帯板状リード端子も大型化してきている。そのため、従来の外包材フィルムにリード端子を熱接着させる場合、高い熱接着条件が必要となり、その結果、熱可塑性樹脂の流れ出し量が大きくなってリード端子のエッジが露出し、リード端子と外包材フィルム中の金属層間の絶縁性が不十分なことにより、短絡が発生する問題が発生することがある。こうした状況の中で、リード端子接着用のテープ類が開発され使用されてきた。
As electronic devices become smaller and lighter, polymer batteries used as power sources are increasingly required to be smaller and lighter. At the same time, batteries require high energy density and large energy capacity. ing. In order to satisfy these requirements, in recent years, development of a non-aqueous electrolyte battery in which a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte are enclosed in a laminate film, for example, a thin lithium ion battery has been performed.
On the other hand, in recent years, polymer batteries are required to increase in output due to expansion of applications, and there is a tendency for battery dimensions to increase, and accordingly, strip-shaped lead terminals used for batteries are also increasing in size. Therefore, when the lead terminal is thermally bonded to the conventional outer packaging material film, a high thermal bonding condition is required. As a result, the flow-out amount of the thermoplastic resin is increased and the edge of the lead terminal is exposed, so that the lead terminal and the outer packaging material are exposed. Due to insufficient insulation between the metal layers in the film, a problem of short circuit may occur. Under such circumstances, tapes for bonding lead terminals have been developed and used.
リード端子接着用のテープ類の使用形態の一例を図２に基づいて説明する。図２は非水電解質電池の模式的縦断面図（Ａ）およびａ−ａ’断面の拡大図（Ｂ）である。非水電解質電池２０は、ラミネートフィルム２２内に正極２５、負極２６、セパレータ２７、非水電解質（図示せず）などからなる電池本体が収納され、ラミネートフィルム２２の周縁部がヒートシールされて封入されている。なお、このとき、正極２５に接続された正極リード端子２３および負極２６に接続された負極リード端子２４は、それぞれラミネートフィルム周縁部の熱接着部においてリード端子接着用テープ２１を介してラミネートフィルム２２に接着されて密閉状態で電池内部から外部に導出される。
ラミネートフィルム２２とリード端子２３、２４との間にリード端子接着用テープ２１を用いる主たる目的はラミネートフィルム２２とリード端子２３、２４との接着であるが、その他にも二つの目的がある。一つはリード端子導出部Ｘにおける密封性の向上である。リード端子接着用テープ２１はラミネートフィルム２２がヒートシールされる際に、適度に溶融してリード端子２３、２４の側面に回りこみ、ラミネートフィルム２２とリード端子２３、２４との間に生じる間隙を埋めることによりリード端子導出部Ｘにおける密封性を向上させることであり、もう一つの目的は短絡防止である。ラミネートフィルム２２を構成する層の１つであるバリアー層は、通常アルミニウム箔などの金属箔からなる為、ラミネートフィルム２２のバリアー層とリード端子２３、２４とが近接すると短絡する恐れがある。しかしながらリード端子接着用テープ２１を用いると、該端子接着用テープ２１によってラミネートフィルム２２のバリアー層とリード端子２３、２４との間隔が維持されるので、両者の近接に起因する短絡を防止できる。
An example of the usage pattern of the tapes for bonding the lead terminals will be described with reference to FIG. FIG. 2 is a schematic longitudinal sectional view (A) and an enlarged view (B) of the aa ′ section of the nonaqueous electrolyte battery. The nonaqueous electrolyte battery 20 contains a battery body made up of a positive electrode 25, a negative electrode 26, a separator 27, a nonaqueous electrolyte (not shown) and the like in a laminate film 22, and the periphery of the laminate film 22 is heat sealed and enclosed. Has been. At this time, the positive electrode lead terminal 23 connected to the positive electrode 25 and the negative electrode lead terminal 24 connected to the negative electrode 26 are respectively laminated on the laminate film 22 via the lead terminal bonding tape 21 at the thermal bonding portion at the periphery of the laminate film. And is led out from the inside of the battery in a sealed state.
The main purpose of using the lead terminal bonding tape 21 between the laminate film 22 and the lead terminals 23 and 24 is to bond the laminate film 22 and the lead terminals 23 and 24, but there are two other purposes. One is to improve the sealing performance in the lead terminal lead-out portion X. When the laminate film 22 is heat-sealed, the lead terminal bonding tape 21 melts appropriately and wraps around the side surfaces of the lead terminals 23 and 24, and creates a gap generated between the laminate film 22 and the lead terminals 23 and 24. It is to improve the sealing performance in the lead terminal lead-out portion X by filling, and another purpose is to prevent a short circuit. Since the barrier layer which is one of the layers constituting the laminate film 22 is usually made of a metal foil such as an aluminum foil, if the barrier layer of the laminate film 22 and the lead terminals 23 and 24 are close to each other, a short circuit may occur. However, when the lead terminal bonding tape 21 is used, the distance between the barrier layer of the laminate film 22 and the lead terminals 23 and 24 is maintained by the terminal bonding tape 21, so that a short circuit due to the proximity of both can be prevented.
このように、リード端子導出部Ｘの密封性を向上させるためには、ラミネートフィルム２２周縁部をヒートシールする際にリード端子接着用テープ２１が適度に溶融し、リード端子接着用テープ２１の一部がリード端子２３、２４の側面に回り込む必要がある。しかしながら端子接着用テープ２１が溶融し過ぎると、ラミネートフィルム２２のバリアー層とリード端子２３，２４との間隔が縮まるため短絡の恐れが生じる。よってリード端子接着用テープ２１は、ヒートシール時にリード端子２３、２４と接する層が適度に溶融し、中間層はあまり溶融しないものが望ましいこととなる。このような性能を具備させるために架橋処理した樹脂層を設けて溶融を調整したリード端子接着用テープが提案されている。 As described above, in order to improve the sealing performance of the lead terminal lead-out portion X, the lead terminal bonding tape 21 is appropriately melted when the periphery of the laminate film 22 is heat-sealed. The part needs to wrap around the side surfaces of the lead terminals 23 and 24. However, if the terminal bonding tape 21 is excessively melted, the distance between the barrier layer of the laminate film 22 and the lead terminals 23 and 24 is shortened, which may cause a short circuit. Therefore, it is desirable that the lead terminal bonding tape 21 is one in which the layers in contact with the lead terminals 23 and 24 are appropriately melted during heat sealing, and the intermediate layer is not melted so much. In order to provide such performance, a lead terminal bonding tape has been proposed in which a cross-linked resin layer is provided to adjust the melting.
例えば、架橋ポリオレフィン樹脂からなる架橋層と熱可塑性樹脂からなる熱可塑層を有するリード端子接着用テープがある。このリード端子接着用テープは、熱可塑層がリード端子側に、架橋層がラミネートフィルム側になるように、リード端子とラミネートフィルムとの間に介在させることによって密封性、絶縁性を発揮する。すなわち、熱可塑層はヒートシール時に溶融しやすいため、リード端子とリード端子接着用テープとの接着性はもちろん、リード端子の側面に回りこむことによりリード端子導出部における密封性を向上させる。架橋層はヒートシール時に変形し難いため、ラミネートフィルムとリード端子との間隔を保持し電池の短絡を防止する（特許文献１）。しかしながら、該端子接着用テープはラミネートフィルムと架橋層とが接するため、ラミネートフィルムと端子接着用テープとの接着性が不十分であった。 For example, there is a lead terminal bonding tape having a crosslinked layer made of a crosslinked polyolefin resin and a thermoplastic layer made of a thermoplastic resin. This lead terminal adhesive tape exhibits sealing and insulating properties by being interposed between the lead terminal and the laminate film so that the thermoplastic layer is on the lead terminal side and the crosslinked layer is on the laminate film side. That is, since the thermoplastic layer is easily melted at the time of heat sealing, not only the adhesion between the lead terminal and the lead terminal bonding tape but also the sealing performance at the lead terminal lead-out portion is improved by turning around the side surface of the lead terminal. Since the cross-linked layer is not easily deformed during heat sealing, the gap between the laminate film and the lead terminal is maintained to prevent a short circuit of the battery (Patent Document 1). However, since the terminal adhesive tape is in contact with the laminate film and the cross-linked layer, the adhesion between the laminate film and the terminal adhesive tape is insufficient.
架橋されたポリエチレン系樹脂の片面にポリプロピレン層、他の面に酸変性ポリプロピレン層が形成された多層フィルムからなるリード端子接着用テープが提供されていて、このリード端子接着用テープの製造には、予めポリエチレンフィルムを架橋後その片面にポリプロピレン、他の面に酸変性ポリプロピレン樹脂をそれぞれ押出ラミネート法を用いて積層する方法や、ポリプロピレン樹脂、ポリエチレン樹脂、酸変性ポリプロピレン樹脂を共押出して製膜し得られたフィルムを電子線架橋する方法が採用されている（特許文献２）。 A lead terminal adhesive tape comprising a multilayer film in which a polypropylene layer is formed on one side of a cross-linked polyethylene resin and an acid-modified polypropylene layer is formed on the other side is provided. It can be formed by cross-linking polyethylene film in advance and then laminating polypropylene on one side and laminating acid-modified polypropylene resin on the other side using extrusion lamination method, or coextrusion of polypropylene resin, polyethylene resin and acid-modified polypropylene resin. A method of crosslinking the obtained film with an electron beam is employed (Patent Document 2).
また、熱接着部が完全でないと水分の侵入によるシール強度が低下するため、電池内への水分の侵入を阻止するための提案がなされている。
例えば、一対の外装体間に正極と負極と非水電解質とが収容され、外装体間の周囲が熱溶着性樹脂によって封口された薄型非水電解質電池において、外装体間の周囲を第１熱溶着性樹脂で封口させると共に、この第１熱溶着性樹脂の内周側に第２熱溶着性樹脂が嵌め込まれるようにして熱溶着させ、上記の第１熱溶着性樹脂として第２熱溶着性樹脂より水分透過率が低くかつ融点が高いものを用いた非水電解質電池（特許文献３）や、サイズの増大を抑えつつ、内部への水分浸入を防止するラミネート外装体を用いた電池を提供することを目的とするラミネート外装体を用いた非水電解電池では、金属薄膜と熱接着性樹脂フィルムからなるラミネート外装体において、吸湿剤を該ラミネートで挟み、該吸湿剤の周囲が熱接着によって封止されている電池（特許文献４）が提案されている。
In addition, since the sealing strength due to the ingress of moisture is reduced unless the thermal bonding portion is perfect, proposals have been made to prevent the ingress of moisture into the battery.
For example, in a thin nonaqueous electrolyte battery in which a positive electrode, a negative electrode, and a non-aqueous electrolyte are accommodated between a pair of exterior bodies and the periphery between the exterior bodies is sealed with a heat-welding resin, the periphery between the exterior bodies is surrounded by the first heat. While sealing with a weldable resin, the second heat-weldable resin is heat-welded so that the second heat-weldable resin is fitted on the inner peripheral side of the first heat-weldable resin, and the second heat-weldable resin is used as the second heat-weldable resin. Providing non-aqueous electrolyte batteries (Patent Document 3) that have a lower water permeability and higher melting point than resins (Patent Document 3), and batteries that use laminate outer bodies that prevent moisture from entering inside while suppressing increase in size In a non-aqueous electrolytic battery using a laminate outer body intended to be used, in a laminate outer body made of a metal thin film and a heat-adhesive resin film, a hygroscopic agent is sandwiched between the laminates, and the periphery of the hygroscopic agent is bonded by thermal bonding. Sealed Cell (Patent Document 4) there are proposed.
リード端子接着用テープは、電池外包材と端子との接着を目的とするが、同時に電池外包材に含まれるバリアー層と端子との接触に起因する短絡を防止する役割も担い、３層構成で、中間層に絶縁性微粒子が配された端子接着用テープ（電池用リード線被覆フィルム材）が提案されている。ヒートシールの際に溶融しない絶縁性微粒子によってバリアー層と端子との短絡を防止し、絶縁性微粒子が配されていない内外層によって外包材と端子との接着を担保している。
また、ラミネートフィルムによって外包された電池の大きな課題としては、水分の侵入によるシール強度の低下がある。例えば、リチウムイオン電池の電解液には６フッ化リン酸リチウムが含まれているが、電池内部に水分が侵入すると、６フッ化リン酸リチウムが水分と反応してフッ化水素（フッ酸）を発生させることが知られている。フッ化水素が発生すると、端子の表面が劣化し、端子と端子接着用テープの間の接着力が低下する。端子接着用テープが剥離すると、そこから電解液が漏れて電池としての機能が失われる。そこで外包材には水分の侵入を可能な限り低下させることが要求されている。
水分の侵入を抑えるために、リード端子と接する層のみ不飽和カルボン酸でグラフト変性したポリプロピレンより成形することが提案されている。しかしながら、不飽和カルボン酸でグラフト変性したポリプロピレンの使用量を最小限に抑えたとしても、フィルム端面からの水分の侵入を完全に遮断することは難しい。これらの例のように、外部からの水分の侵入抑制については提案がなされているが、水分が包装体内に侵入した後の対処についてはあまり注意が払われてはいなかったのが現状である。
The lead terminal bonding tape is intended for bonding between the battery outer packaging material and the terminal, but at the same time also plays a role of preventing short circuit caused by contact between the barrier layer contained in the battery outer packaging material and the terminal. A terminal adhesive tape (battery lead wire covering film material) in which insulating fine particles are arranged in an intermediate layer has been proposed. The insulating fine particles that do not melt during heat sealing prevent short circuit between the barrier layer and the terminal, and the inner and outer layers on which the insulating fine particles are not disposed ensure the adhesion between the outer packaging material and the terminal.
In addition, as a major problem of the battery encased by the laminate film, there is a decrease in the sealing strength due to the intrusion of moisture. For example, the electrolyte solution of a lithium ion battery contains lithium hexafluorophosphate, but when water enters the battery, the lithium hexafluorophosphate reacts with the water to form hydrogen fluoride (hydrofluoric acid). It is known to generate When hydrogen fluoride is generated, the surface of the terminal deteriorates, and the adhesive force between the terminal and the terminal bonding tape decreases. When the tape for terminal bonding is peeled off, the electrolyte solution leaks from it and the function as a battery is lost. Therefore, the outer packaging material is required to reduce the intrusion of moisture as much as possible.
In order to suppress the penetration of moisture, it has been proposed that only the layer in contact with the lead terminal is molded from polypropylene graft-modified with an unsaturated carboxylic acid. However, even if the amount of polypropylene graft-modified with unsaturated carboxylic acid is minimized, it is difficult to completely block moisture from entering from the film end face. As in these examples, proposals have been made to suppress the entry of moisture from the outside, but the current situation is that little attention has been paid to the countermeasures after moisture has entered the package.
本発明は、電池本体の電解質による封着部の接着強度が低下することを防止するとともに、侵入した水分により起こされる６フッ化リン酸リチウムが水分と反応してフッ化水素（フッ酸）が発生しこのフッ化水素がリード端子表面の劣化、またリード端子と端子接着用テープの間の接着力を低下させる問題点を解決するものであり、リード端子接着用のテープによって電池本体を包装した包装体での大きな問題点を簡便な手段によりに解決するものである。 The present invention prevents the adhesive strength of the sealing portion of the battery body from being lowered, and lithium hexafluorophosphate caused by the invading moisture reacts with moisture to generate hydrogen fluoride (hydrofluoric acid). This hydrogen fluoride solves the problem of deterioration of the lead terminal surface and the problem of lowering the adhesive force between the lead terminal and the terminal adhesive tape, and the battery body is wrapped with the lead terminal adhesive tape. It solves a major problem in the package by simple means.
本発明は以下の技術的手段から構成される。
（１）電池外包用ラミネートフィルムと電池本体のリード端子との接着を介在するリード端子接着用テープであって、該端子接着用テープは１層以上の熱可塑性合成樹脂からなり、その内の少なくとも１層が、重質炭酸カルシウムおよび炭酸マグネシウムから選ばれる１種以上であるフッ化水素と反応する無機充填材を含有したベース樹脂層からなることを特徴とするリード端子接着用テープ。２０１６１０１２
（２）上記のベース樹脂層は、重質炭酸カルシウムおよび炭酸マグネシウムから選ばれる１種以上であるフッ化水素と反応する無機充填材を１０〜５０重量％含有する上記（１）に記載のリード端子接着用テープ。
（３）上記の重質炭酸カルシウムおよび炭酸マグネシウムから選ばれる１種以上であるフッ化水素と反応する無機充填材は、平均粒径が０．１〜１５μｍである上記（１）または（２）に記載のリード端子接着用テープ。
（４）上記のリード端子接着用テープは、中間層がベース樹脂層の三層構成であり、ベース樹脂層の内外両側にポリオレフィン系樹脂からなる接着層を有する上記（１）から（３）のいずれかに記載のリード端子接着用テープ。
（５）リード端子を有する電池本体を外包用ラミネートフィルムにより包装した電池包装体であって、該包装体の周縁熱接着部において該ラミネートフィルムの内層とリード端子との間に上記（１）から（４）のいずれかに記載のリード端子接着用テープを介在させて熱接着した周縁熱接着部を有することを特徴とする電池包装体。
The present invention comprises the following technical means.
(1) A lead terminal adhering tape that interposes adhesion between a battery outer covering laminate film and a lead terminal of a battery body, the terminal adhering tape comprising one or more layers of thermoplastic synthetic resin, One layer is composed of a base resin layer containing an inorganic filler that reacts with one or more kinds of hydrogen fluoride selected from heavy calcium carbonate and magnesium carbonate . 20161012
(2) The lead according to (1), wherein the base resin layer contains 10 to 50% by weight of an inorganic filler that reacts with hydrogen fluoride that is one or more selected from heavy calcium carbonate and magnesium carbonate. Tape for terminal bonding.
(3) The inorganic filler that reacts with one or more hydrogen fluorides selected from the above-mentioned heavy calcium carbonate and magnesium carbonate has an average particle diameter of 0.1 to 15 μm (1) or (2) A tape for bonding lead terminals as described in 1.
(4) The lead terminals adhesive tape is a three-layer structure of the intermediate layer base resin layer, the above (1) having an adhesive layer comprising a polyolefin resin in both the inside and the outside of the base resin layer (3) The lead terminal bonding tape according to any one of the above.
(5) A battery packaging body in which a battery body having a lead terminal is packaged with a laminate film for outer packaging, from the above (1) between the inner layer of the laminate film and the lead terminal at the peripheral heat bonding portion of the packaging body ( 4 ) A battery packaging body having a peripheral thermal bonding portion thermally bonded with the lead terminal bonding tape according to any one of ( 4 ) interposed therebetween.
本発明のリード端子接着用テープを使用することにより、リチウムイオン電池の電解液によって熱接着部の接着力が低下することがない。これは、例えば、電解液からフッ化水素が発生しても、フッ素元素を端子接着用テープが捕捉することに起因すると推察される。また、リード端子接着用テープの使用により熱接着部より水分が侵入することが阻止される。 By using the lead terminal bonding tape of the present invention, the adhesive force of the thermal bonding portion is not reduced by the electrolyte of the lithium ion battery. This is presumably due to the fact that even when hydrogen fluoride is generated from the electrolyte, the terminal adhesive tape captures the fluorine element. Further, the use of the lead terminal bonding tape prevents moisture from entering from the thermal bonding portion.
本発明は、電池外包用ラミネートフィルムと電池本体のリード端子との接着を介在するリード端子接着用テープであって、該端子接着用テープは１層以上の熱可塑性合成樹脂からなり、その内の少なくとも１層がフッ化水素と反応する無機質充填材を含有したベース樹脂層からなるものであり、電解質に起因する接着強度の低下が低減されていることを特徴とするリード端子接着用テープに関する。
リード端子接着用テープの少なくとも１層にフッ化水素と反応する無機質充填材を配合することにより、包装体内に侵入した水分と電解質の反応により生成したフッ化水素を無機充填材が反応し吸収することにより包装体の熱接着部の接着強度の低下が抑制される。
例えば、リード端子接着用テープを構成する１層に炭酸カルシウム（ＣａＣＯ３）を配合すると、該炭酸カルシウムはフッ化水素（ＨＦ）と反応し、フッ化水素をフッ化カルシウム（ＣａＦ２）の形でリード端子接着用テープ内に閉じ込める。そのためフッ化水素による端子表面の劣化が抑制され、更には端子と端子接着用テープの間の接着力の低下が抑制される。炭酸カルシウムの中でも「重質炭酸カルシウム」が特にフッ酸をキャッチする性能に優れている。重質炭酸カルシウムは天然の石灰石を粉砕することによって製造され、その表面が凹凸の激しい形状をしていることから表面積が大きく反応性に優れているものと推察される。
The present invention is a lead terminal bonding tape that interposes the adhesion between a laminate film for battery outer packaging and a lead terminal of a battery body, the terminal bonding tape comprising one or more layers of thermoplastic synthetic resin, The present invention relates to a tape for adhering lead terminals, wherein at least one layer is composed of a base resin layer containing an inorganic filler that reacts with hydrogen fluoride, and a decrease in adhesive strength due to an electrolyte is reduced.
By blending an inorganic filler that reacts with hydrogen fluoride into at least one layer of the lead terminal bonding tape, the inorganic filler reacts and absorbs the hydrogen fluoride produced by the reaction between the water and the electrolyte that has entered the package. Thereby, the fall of the adhesive strength of the heat bonding part of a package is suppressed.
For example, when calcium carbonate (CaCO 3 ) is blended in one layer constituting the lead terminal adhesive tape, the calcium carbonate reacts with hydrogen fluoride (HF), and the hydrogen fluoride is converted into calcium fluoride (CaF 2 ). Enclose in the lead terminal adhesive tape. Therefore, deterioration of the terminal surface due to hydrogen fluoride is suppressed, and further, a decrease in the adhesive force between the terminal and the terminal bonding tape is suppressed. Among the calcium carbonates, “heavy calcium carbonate” is particularly excellent in catching hydrofluoric acid. Heavy calcium carbonate is produced by pulverizing natural limestone, and since the surface has a highly irregular shape, it is presumed that the surface area is large and the reactivity is excellent.
［電池本体の外包材による包装、リード端子接着用テープの使用］
本発明を実施するための具体的形態について以下図面を参照してさらに説明する。
薄型ポリマー電池本体を密封した電池のリード端子付近の断面を図３に示す。図３に示すように、外側から順に表面保護層となる熱可塑性合成樹脂層３４、バリアー層となる金属箔層３５、および熱接着層となる熱可塑性合成樹脂層３６よりなる外包材３７が熱可塑性合成樹脂層３６どうしを内側にして周縁部において熱接着せられてなるものであり、リード端子２３は、内部の正極または負極にそれぞれ接続せられて外包材３７の周縁部の合わせ目から外部に取り出されている。リード端子２３は、予め周縁部から外側まで突出しかつその両側面を覆いうる大きさのリード端子接着用フィルム１０で挾まれて熱接着被覆させられている。リード端子接着用フィルム１０は、外層１１、ベース樹脂層１２および内層１３の３層の熱可塑性合成樹脂からなり、そのうちベース樹脂層１２にフッ化水素と反応する無機微粒子１４が分散含有せしめられている。外包材３７とリード端子２３は、リード端子接着用フィルム１０を介して熱接着されている。
[Packaging with battery outer packaging material, use of lead terminal adhesive tape]
Specific embodiments for carrying out the present invention will be further described below with reference to the drawings.
FIG. 3 shows a cross section near the lead terminal of the battery in which the thin polymer battery body is sealed. As shown in FIG. 3, an outer packaging material 37 composed of a thermoplastic synthetic resin layer 34 serving as a surface protective layer, a metal foil layer 35 serving as a barrier layer, and a thermoplastic synthetic resin layer 36 serving as a thermal bonding layer in order from the outside is heated. The plastic synthetic resin layers 36 are inwardly bonded to each other at the peripheral edge, and the lead terminals 23 are respectively connected to the internal positive electrode or the negative electrode, and are connected to the outer periphery from the joint of the peripheral edge of the outer packaging material 37. Has been taken out. The lead terminal 23 is preliminarily protruded from the peripheral portion to the outside and is covered with a lead terminal bonding film 10 having a size capable of covering both sides thereof and is thermally bonded. The lead terminal bonding film 10 is made of three layers of thermoplastic synthetic resin, an outer layer 11, a base resin layer 12, and an inner layer 13. Of these, inorganic fine particles 14 that react with hydrogen fluoride are dispersed and contained in the base resin layer 12. Yes. The outer packaging material 37 and the lead terminal 23 are thermally bonded via the lead terminal bonding film 10.
炭酸カルシウムなどの無機充填剤を配するベース樹脂の種類は特に限定されないが、例えば、リード端子接着テープを構成する少なくとも３層の熱可塑性合成樹脂の具体例としては、ポリエチレン、低密度ポリエチレン、高密度ポリエチレン、酸変性ポリエチレン、ブロックポリプロピレン、ランダムポリプロピレン、酸変性ポリプロピレン、アイオノマーなどの熱接着性に優れた樹脂であることが好ましい。３層は同じ熱可塑性合成樹脂でもよいし、異なる熱可塑性合成樹脂でもよい。ただし、リード端子接着用テープが単層、あるいは２層であり、炭酸カルシウムなどの無機充填材を配する層が直接端子と接する場合は、ベース樹脂として金属との接着性が良好な酸変性ポリオレフィンを選択することが好ましい。
特に、リード端子接着用テープは三層構成であることが望ましい。炭酸カルシウムなどの無機充填材を配合するベース樹脂層の内側には、リード端子との接着性が良好な内層を、外側には、外包材との接着性が良好な外層を有していることが望ましい。このような層構成とする場合は炭酸カルシウムなどの無機充填材を含有するベース樹脂は、金属端子と接することがないため、酸で変性されていないポリオレフィンから成ることが好ましい。酸で変性されていると親水性が高まり耐水性が低下し密封性が悪化するおそれがある。特に、ベース樹脂層１２はブロックポリプロピレンが好ましい。また内層１３は金属との接着性に優れる酸変性ポリオレフィンからなることが望ましい。外層１１は、外包材との接着性を考慮すると外包材３７の熱接着層３６と同一の樹脂から成ることが好ましいが、内層１３と同じ樹脂から形成されていると、リード端子接着用テープに表裏がなくなる為、電池の成形が容易になる。
The type of the base resin on which the inorganic filler such as calcium carbonate is disposed is not particularly limited. For example, specific examples of the thermoplastic synthetic resin of at least three layers constituting the lead terminal adhesive tape include polyethylene, low density polyethylene, high A resin excellent in thermal adhesiveness such as density polyethylene, acid-modified polyethylene, block polypropylene, random polypropylene, acid-modified polypropylene, and ionomer is preferable. The three layers may be the same thermoplastic synthetic resin or different thermoplastic synthetic resins. However, when the lead terminal adhesive tape is a single layer or two layers, and the layer on which an inorganic filler such as calcium carbonate is disposed is in direct contact with the terminal, the acid-modified polyolefin having good adhesion to the metal as the base resin Is preferably selected.
In particular, the lead terminal bonding tape preferably has a three-layer structure. The base resin layer that contains inorganic fillers such as calcium carbonate has an inner layer with good adhesion to the lead terminals on the inside and an outer layer with good adhesion to the outer packaging on the outside. Is desirable. In the case of such a layer structure, the base resin containing an inorganic filler such as calcium carbonate is preferably not made of a polyolefin that has not been modified with an acid because it does not contact the metal terminal. If it is modified with an acid, the hydrophilicity is increased, the water resistance is lowered, and the sealing property may be deteriorated. In particular, the base resin layer 12 is preferably block polypropylene. The inner layer 13 is preferably made of an acid-modified polyolefin having excellent adhesion to metal. The outer layer 11 is preferably made of the same resin as the thermal bonding layer 36 of the outer packaging material 37 in consideration of the adhesiveness to the outer packaging material. However, if the outer layer 11 is formed of the same resin as the inner layer 13, the outer layer 11 is formed on the lead terminal bonding tape. Since the front and back sides are eliminated, the battery can be easily molded.
［粒子の材質および粒径］
本発明で使用される無機充填材は、フッ化水素と反応する性質を持っていればいずれのものであっても使用できるが、例えば、炭酸カルシウム、炭酸マグネシウムなどの金属炭酸塩を挙げることができる。炭酸塩としては、上述のように、重炭酸カルシウムが最も好ましい。これらの無機充填剤の粒の粒径は０．１〜１５μｍが好ましい。粒径が０．１μｍ未満であると、ベース樹脂層中への均一な分散が難しくなるおそれがあり、１５μｍを超えると、無機充填材単位重量当たりの表面積が小さくなる、無機充填剤を含有するベース樹脂層の厚さを不必要に大きくしなければならなくなる等の理由により好ましくない。さらに好ましい範囲は１．０〜６．０μｍである。
ベース樹脂層は、無機充填剤を１０〜５０重量％、熱可塑性合成樹脂を９０〜５０重量％からなることが好ましい。ベース樹脂層中の無機充填剤粒子の含有割合が１０重量％未満では発生したフッ化水素を十分に反応除去することが困難となるおそれがあり、５０重量％を超えると、無機充填剤粒子を含有するベース樹脂層の強度が弱くなり、層内剥離などによる封着部のシール強度の低下のおそれがある。さらに好ましい範囲は１５〜３０重量％である。
[Particle material and particle size]
As the inorganic filler used in the present invention, any inorganic filler can be used as long as it has a property of reacting with hydrogen fluoride. Examples thereof include metal carbonates such as calcium carbonate and magnesium carbonate. it can. As described above, calcium carbonate is most preferable as the carbonate. The particle size of these inorganic filler particles is preferably 0.1 to 15 μm. If the particle size is less than 0.1 μm, it may be difficult to uniformly disperse in the base resin layer. If the particle size exceeds 15 μm, the surface area per unit weight of the inorganic filler is reduced, and an inorganic filler is contained. This is not preferable because the thickness of the base resin layer must be increased unnecessarily. A more preferable range is 1.0 to 6.0 μm.
The base resin layer preferably comprises 10 to 50% by weight of an inorganic filler and 90 to 50% by weight of a thermoplastic synthetic resin. If the content of the inorganic filler particles in the base resin layer is less than 10% by weight, it may be difficult to sufficiently remove the generated hydrogen fluoride, and if it exceeds 50% by weight, the inorganic filler particles The strength of the base resin layer to be contained is weakened, and there is a fear that the sealing strength of the sealed portion may be lowered due to peeling in the layer. A more preferred range is 15 to 30% by weight.
［炭酸カルシウム］
本発明では工業用粉体材料としての炭酸カルシウムを使用することができる。工業用の炭酸カルシウムは、石灰石、貝殻、白亜などＣａＣＯ３を主成分とする天然原料を機械的に粉砕分級した重質炭酸カルシウム、胡粉、チョークなど古くから利用されている。最近の重質炭酸カルシウムは、粉砕分級技術の進歩により、平均粒子径が１μｍ以下の製品も生産できるようになり、プラスチック、ゴム、塗料、製紙等の添加剤として利用されている。また、本発明では、化学的に製造される沈降炭酸カルシウムを使用することができる。これらは、軽微性または軽質炭酸カルシウムと呼ばれ、重質炭酸カルシウムと区別されている。沈降炭酸カルシウムは、更に一次粒子の大きさから膠質品（コロイド品、セミコロイド品）および普通品に分類され、分類の基準は、一次粒子のサイズで長径１μｍ以上の紡錘状、または柱状粒子を示すものを普通品、斜方晶型の立方体結晶をもつ微細品を辺長０．１μｍを境にしてコロイド品、セミコロイド品と称している。
例えば、炭酸カルシウムは以下のように分類されるが、いずれの製品も本発明に使用することができる。
[Calcium carbonate]
In the present invention, calcium carbonate as an industrial powder material can be used. Industrial calcium carbonate has been used for a long time, such as heavy calcium carbonate obtained by mechanically pulverizing and classifying natural raw materials mainly composed of CaCO 3 such as limestone, shells, and chalk, husk, and chalk. With the recent progress of pulverization and classification technology, heavy calcium carbonate has become capable of producing products with an average particle size of 1 μm or less, and is used as an additive for plastics, rubber, paint, papermaking and the like. In the present invention, chemically produced precipitated calcium carbonate can be used. These are called light or light calcium carbonate and are distinguished from heavy calcium carbonate. Precipitated calcium carbonate is further classified into colloidal products (colloidal and semicolloidal products) and normal products according to the size of the primary particles. What is shown is called a normal product, and a fine product having an orthorhombic cubic crystal is called a colloid product or a semi-colloid product with a side length of 0.1 μm as a boundary.
For example, calcium carbonate is classified as follows, but any product can be used in the present invention.
［炭酸カルシウム分散樹脂層（ベース樹脂層）］
無機粒子を分散したべース樹脂層１２を有し３層からなるリード端子部接着用テープ１０について説明する。リード端子部接着用テープ１０における炭酸カルシウム分散樹脂層は、上述したように、フッ化水素との反応性を有するものでなければならないが、電池の周縁熱接着部においてリード端子２３、２４と外装材との間に介在し熱接着され、熱接着時の熱（１６０〜１９０℃）と圧力（１．０〜２．０ＭＰａ）により溶融し押し潰されない耐熱性と電解液に対する耐性を有することが好ましい。ベース樹脂層１２は、例えば、ポリオレフィン樹脂層中に無機充填材粒子が均一に分散されている。このベース樹脂層１２を酸変性ポリオレフィン系樹脂で被覆したリード端子接着用フィルムを金属端子と外装フィルムとの間に介在させて熱接着した場合には、無機充填材粒子は熱で溶融しないために、ベース樹脂層１２が熱接着時の熱と圧力により溶融し押し潰されリード端子と外装フィルム中の金属層とが接触し短絡することを防止することができる。また、無機充填材粒子が分散したベース樹脂層１２の両面に酸変性ポリオレフィン系樹脂を溶融押出しにより積層すると、ベース樹脂層１２と酸変性ポリオレフィン樹脂層１１、１３との間が強固に接着し、電池内部での内圧上昇時においてもリード端子接着用テープの層間で剥離することを防止することができる。
以下、本発明を実施例に基づいて具体的に説明するが、本発明が実施例により限定されるものではない。なお、実施例２は参考例である。
[Calcium carbonate dispersed resin layer (base resin layer)]
A lead terminal bonding tape 10 having a base resin layer 12 in which inorganic particles are dispersed and having three layers will be described. As described above, the calcium carbonate-dispersed resin layer in the lead terminal adhesive tape 10 must be reactive with hydrogen fluoride. It is heat-bonded by being interposed between the materials, and has heat resistance not to be crushed and melted by heat (160 to 190 ° C.) and pressure (1.0 to 2.0 MPa) at the time of heat bonding and resistance to the electrolyte preferable. In the base resin layer 12, for example, inorganic filler particles are uniformly dispersed in a polyolefin resin layer. When the lead terminal bonding film in which the base resin layer 12 is coated with the acid-modified polyolefin resin is interposed between the metal terminal and the exterior film and thermally bonded, the inorganic filler particles are not melted by heat. It is possible to prevent the base resin layer 12 from being melted and crushed by the heat and pressure at the time of thermal bonding, and the lead terminal and the metal layer in the exterior film coming into contact with each other and short-circuiting. Further, when the acid-modified polyolefin resin is laminated by melt extrusion on both surfaces of the base resin layer 12 in which the inorganic filler particles are dispersed, the base resin layer 12 and the acid-modified polyolefin resin layers 11 and 13 are firmly bonded, Even when the internal pressure rises inside the battery, it is possible to prevent peeling between the layers of the lead terminal bonding tape.
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited by an Example. In addition, Example 2 is a reference example.
本実施例では三層構成 ［変性ＰＰ／ブロックＰＰ＋無機充填材／変性ＰＰ］ の端子接着用テープを製造した。まず、無機充填材とブロックＰＰとを１：１の割合で二軸混練機により混練してマスターバッチを作成した。その後、酸変性ＰＰを一つの押出機に、マスターバッチとブロックＰＰを１：１で混ぜ合わせたもの（即ち、無機充填材の配合割合は２５重量％となる。）をもう一つの押出機に供給し、酸変性ＰＰが内外層、マスターバッチと熱可塑性樹脂の混合物が中間層になるように、一つのフラット状ダイス（Ｔダイ）から押出すことにより三層からなるフィルムを製膜した（所謂、Ｔダイ共押出法を採用した。）。その後、フィルムを１５ｍｍのテープ状に切断し、更に１００ｍｍ幅に切断し、リード端子接着用テープとした。
なお、熱可塑性樹脂および無機充填材は以下に記載のものを選択し、表２に示した配合とした。
実施例１：重質炭酸カルシウム／平均粒径：１．８μｍ、粒形状：無定形
実施例２：合成炭酸カルシウム／平均粒径：２．０μｍ、粒形状：略立方体
比較例１：充填材添加無し
比較例２：硫酸バリウム／平均粒径０．５μｍ、粒形状：無定形
変性ＰＰ：無水マレイン酸変性ポリプロピレン
ブロックＰＰ：プロピレン系ブロック共重合体
In this example, a terminal adhesive tape having a three-layer structure [modified PP / block PP + inorganic filler / modified PP] was produced. First, a master batch was prepared by kneading the inorganic filler and the block PP at a ratio of 1: 1 with a biaxial kneader. Thereafter, the acid-modified PP is mixed in one extruder, and the master batch and the block PP mixed in a ratio of 1: 1 (that is, the blending ratio of the inorganic filler is 25% by weight) in the other extruder. A film composed of three layers is formed by extruding from one flat die (T die) so that the acid-modified PP is an inner and outer layer, and the mixture of the masterbatch and the thermoplastic resin is an intermediate layer ( The so-called T-die coextrusion method was adopted.) Thereafter, the film was cut into a tape shape of 15 mm, and further cut into a width of 100 mm to obtain a lead terminal bonding tape.
In addition, the thermoplastic resin and the inorganic filler were selected as described below, and the composition shown in Table 2 was adopted.
Example 1: Heavy calcium carbonate / average particle diameter: 1.8 μm, grain shape: amorphous Example 2: Synthetic calcium carbonate / average particle diameter: 2.0 μm, grain shape: substantially cubic Comparative example 1: Addition of filler None Comparative Example 2: Barium sulfate / average particle size 0.5 μm, particle shape: amorphous modified PP: maleic anhydride modified polypropylene block PP: propylene block copolymer
各端子接着用テープの性能については、以下の方法により評価した。
［評価１：接着力］
端子にリード端子接着用テープをヒートシールし、接着用テープで被覆したリード端子を製造した。ヒートシール直後の剥離強度と、該接着用テープ被覆端子をリチウムイオン電池の電解液中に８５℃、一週間浸漬した後の剥離強度を測定した。接着力の低下が少ない程、フッ化水素の影響を受けていないといえる。
電解液の組成は、エチレンカーボネートとジメチルカーボネートとジエチルカーボネートからなる溶媒にＬｉＰＦ６を１ｍｏｌ／Ｌの割合で添加したものである。
［評価２：フッ素元素キャッチ能力］
評価１に用いた端子接着用テープ（電解液浸漬後）の断面をＳＥＭ−ＥＤＳで元素分析した。リード端子接着用テープ内にフッ素元素が確認できたものを〇、わずかに確認できたものを△、確認できなかったものを×として評価した。
試験結果を表２に示す。重質炭酸カルシウムまたは合成炭酸カルシウムを含有させたリード端子接着用テープは、電解液中に浸漬した後にも接着力を維持していたが、重質炭酸カルシウムが非常に優れた接着力を維持した。無機充填材を使用しない場合あるいはフッ化水素とは反応し難い硫酸バリウムを含有する場合は電解液に浸漬後の熱接着部は剥離していた。電解液に浸漬した後のリード端子接着用テープの断面をＳＥＭ−ＥＤＳで元素分析した結果を図４に示す。図中のFKaがフッ素元素に起因するピークであり、OKaは酸素元素に起因するピークである。実施例１で断面にフッ素元素のピークが高いということは、フッ素元素が多量吸収されたことになる。実施例２においても、比較例２と対比すると、フッ素元素の吸収がなされていることが明らかである。
これらの試験結果から、炭酸カルシウム、特に、重質炭酸カルシウムによるフッ素元素吸収効果が確認された。
The performance of each terminal adhesive tape was evaluated by the following method.
[Evaluation 1: Adhesive strength]
The terminal was heat-sealed with a lead terminal adhesive tape to produce a lead terminal covered with the adhesive tape. The peel strength immediately after heat sealing and the peel strength after immersing the adhesive tape-coated terminal in an electrolytic solution of a lithium ion battery at 85 ° C. for one week were measured. It can be said that the smaller the decrease in adhesive strength, the less affected by hydrogen fluoride.
The composition of the electrolytic solution is obtained by adding LiPF 6 at a rate of 1 mol / L to a solvent composed of ethylene carbonate, dimethyl carbonate, and diethyl carbonate.
[Evaluation 2: Fluorine element catching ability]
The cross section of the terminal adhesive tape (after immersion in the electrolyte) used in Evaluation 1 was subjected to elemental analysis with SEM-EDS. The lead terminal adhesive tape was evaluated as ◯ when the fluorine element could be confirmed, △ when it was slightly confirmed, and x when it could not be confirmed.
The test results are shown in Table 2. Lead terminal adhesive tape containing heavy calcium carbonate or synthetic calcium carbonate maintained adhesive strength even after being immersed in the electrolyte, but heavy calcium carbonate maintained very good adhesive strength. . When the inorganic filler was not used or when barium sulfate that hardly reacts with hydrogen fluoride was contained, the heat-bonded portion after being immersed in the electrolyte was peeled off. FIG. 4 shows the result of elemental analysis of the cross section of the lead terminal bonding tape after immersion in the electrolytic solution using SEM-EDS. In the figure, FKa is a peak attributed to the fluorine element, and OKa is a peak attributed to the oxygen element. The high peak of fluorine element in the cross section in Example 1 means that a large amount of fluorine element was absorbed. In Example 2 as well, it is clear that the fluorine element is absorbed as compared with Comparative Example 2.
From these test results, the elemental fluorine absorption effect by calcium carbonate, especially heavy calcium carbonate was confirmed.
本発明は、電池外包体の封着性を確保して水分による電池本体の劣化を防止し、気密性を低下させることなく、また、リード線と外包材中の金属バリアー層とが短絡するおそれのないリード端子接着用テープを提供するものであり、本発明により、リチウム電池などの製造に当たり不良製品の発生率を大きく低減するとともに、電池を消費者などが使用している過程で、電池の故障や破壊が発生することを防ぐことができ、電池類の使用に際しての安全性の向上、使用技術分野の拡大を達成することができる。 The present invention secures the sealing property of the battery outer casing to prevent deterioration of the battery main body due to moisture, does not lower the airtightness, and may lead to a short circuit between the lead wire and the metal barrier layer in the outer packaging material. The present invention provides a tape for bonding lead terminals, and the present invention greatly reduces the incidence of defective products in the manufacture of lithium batteries and the like, while the battery is being used by consumers and the like. It is possible to prevent the occurrence of failure or destruction, and to improve the safety when using batteries, and to expand the technical field of use.
１０：リード端子接着用テープ
１１：外層
１２：ベース樹脂層
１３：内層
１４：無機充填材
２０：非水電解質電池
２１：リード端子接着用テープ
２２：ラミネートフィルム（外包材）
２３：正極リード端子
２４：負極リード端子
２５：正極
２６：負極
３４：表面保護層
３５：バリアー層（アルミニウム箔）
３６：熱接着層
３７：外包材
Ｘ：リード端子導出部
10: Lead terminal adhesive tape 11: Outer layer 12: Base resin layer 13: Inner layer 14: Inorganic filler 20: Nonaqueous electrolyte battery 21: Lead terminal adhesive tape 22: Laminate film (outer packaging material)
23: Positive electrode lead terminal 24: Negative electrode lead terminal 25: Positive electrode 26: Negative electrode 34: Surface protective layer
35: Barrier layer (aluminum foil)
36: Thermal adhesive layer 37: Outer packaging material X: Lead terminal lead-out portion
Claims (5)
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| WO2021196000A1 (en) * | 2020-03-31 | 2021-10-07 | 宁德新能源科技有限公司 | Battery cell, battery, and electronic device |
| US20230235198A1 (en) * | 2020-06-23 | 2023-07-27 | Fujimori Kogyo Co., Ltd. | Sealing Film, Electrode Lead Member, And Battery |
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| JP4580638B2 (en) * | 2003-12-12 | 2010-11-17 | 大日本印刷株式会社 | Adhesive film for sealing metal terminal of lithium battery and lithium battery using the same |
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