JP7160217B2 - 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス - Google Patents
蓄電デバイス用外装材、その製造方法、及び蓄電デバイス Download PDFInfo
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- JP7160217B2 JP7160217B2 JP2021567670A JP2021567670A JP7160217B2 JP 7160217 B2 JP7160217 B2 JP 7160217B2 JP 2021567670 A JP2021567670 A JP 2021567670A JP 2021567670 A JP2021567670 A JP 2021567670A JP 7160217 B2 JP7160217 B2 JP 7160217B2
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Description
少なくとも、基材層、バリア層、及び熱融着性樹脂層をこの順に備える積層体から構成されており、
前記バリア層は、Si:0.5質量%以下、Fe:0.2質量%以上2.0質量%以下、Mg:0.1質量%以上5.0質量%以下の組成を満たすアルミニウム合金箔を含む、蓄電デバイス用外装材。
本開示の蓄電デバイス用外装材10は、例えば図1から図4に示すように、少なくとも、基材層1、バリア層3、及び熱融着性樹脂層4をこの順に備える積層体から構成されている。蓄電デバイス用外装材10において、基材層1が最外層側になり、熱融着性樹脂層4は最内層になる。蓄電デバイス用外装材10と蓄電デバイス素子を用いて蓄電デバイスを組み立てる際に、蓄電デバイス用外装材10の熱融着性樹脂層4同士を対向させた状態で、周縁部を熱融着させることによって形成された空間に、蓄電デバイス素子が収容される。
[基材層1]
本開示において、基材層1は、蓄電デバイス用外装材の基材としての機能を発揮させることなどを目的として設けられる層である。基材層1は、蓄電デバイス用外装材の外層側に位置する。
本開示の蓄電デバイス用外装材において、接着剤層2は、基材層1とバリア層3との接着性を高めることを目的として、必要に応じて、これらの間に設けられる層である。
着色層は、基材層1とバリア層3との間に必要に応じて設けられる層である(図示を省略する)。接着剤層2を有する場合には、基材層1と接着剤層2との間、接着剤層2とバリア層3との間に着色層を設けてもよい。また、基材層1の外側に着色層を設けてもよい。着色層を設けることにより、蓄電デバイス用外装材を着色することができる。
蓄電デバイス用外装材において、バリア層3は、少なくとも水分の浸入を抑止する層である。
Si:0.1質量%以上0.5質量%以下、Fe:0.2質量%以上2.0質量%以下、Mg:0.1質量%以上5.0質量%以下、Mn:0.05質量%以上0.1質量%以下、Cu:0.0質量%以上0.1質量%以下、Cr:0.0質量%以上0.1質量%以下、Zr:0.0質量%以上0.1質量%以下であり、その他の不可避不純物が、個々に0.05質量%以下かつ合計で0.15質量%以下であり、残部がAlである。
Si:0.1質量%以上0.5質量%以下、Fe:0.2質量%以上2.0質量%以下、Mg:0.1質量%以上5.0質量%以下、Mn:0.1質量%、Cu:0.0質量%、Cr:0.0質量%、Zr:0.0質量%であり、その他の不可避不純物が、個々に0.05質量%以下かつ合計で0.15質量%以下であり、残部がAlであることがより好ましい。また、アルミニウム合金箔は、Si:0.5質量%以下、Fe:0.2質量%以上2.0質量%以下、Mg:0.1質量%以上5.0質量%以下、Mn:0.1質量%、Cu:0.0質量%、Cr:0.0質量%、Zr:0.0質量%であり、その他の不可避不純物が、個々に0.05質量%以下かつ合計で0.15質量%以下であり、残部がAlである。
本開示の蓄電デバイス用外装材において、熱融着性樹脂層4は、最内層に該当し、蓄電デバイスの組み立て時に熱融着性樹脂層同士が熱融着して蓄電デバイス素子を密封する機能を発揮する層(シーラント層)である。
ポリオレフィンや、前記のポリオレフィンにアクリル酸若しくはメタクリル酸等の極性分子を共重合させた共重合体、又は、架橋ポリオレフィン等の重合体等も使用できる。また、酸変性に使用される酸成分としては、例えば、マレイン酸、アクリル酸、イタコン酸、クロトン酸、無水マレイン酸、無水イタコン酸等のカルボン酸またはその無水物が挙げられる。
本開示の蓄電デバイス用外装材において、接着層5は、バリア層3(又は耐酸性皮膜)と熱融着性樹脂層4を強固に接着させるために、これらの間に必要に応じて設けられる層である。
本開示の蓄電デバイス用外装材は、意匠性、耐電解液性、耐傷性、成形性などの向上の少なくとも一つを目的として、必要に応じて、基材層1の上(基材層1のバリア層3とは反対側)に、表面被覆層6を備えていてもよい。表面被覆層6は、蓄電デバイス用外装材を用いて蓄電デバイスを組み立てた時に、蓄電デバイス用外装材の最外層側に位置する層である。
蓄電デバイス用外装材の製造方法については、本開示の蓄電デバイス用外装材が備える各層を積層させた積層体が得られる限り、特に制限されず、少なくとも、基材層1、バリア層3、及び熱融着性樹脂4がこの順となるように積層する工程を備える方法が挙げられる。前記の通り、バリア層3としては、前述した所定の組成を満たすアルミニウム合金箔を用いることができる。
本開示の蓄電デバイス用外装材は、正極、負極、電解質等の蓄電デバイス素子を密封して収容するための包装体に使用される。すなわち、本開示の蓄電デバイス用外装材によって形成された包装体中に、少なくとも正極、負極、及び電解質を備えた蓄電デバイス素子を収容して、蓄電デバイスとすることができる。
<アルミニウム合金箔の製造>
表1に示す各組成(残部はAlおよびその他の不可避不純物)からなるアルミニウム合金の鋳塊を用意し、同表に示す条件で均質化処理を施した後、仕上がり温度330℃での熱間圧延にて厚さ3mmの板材とした。その後、冷間圧延、中間焼鈍、最終冷間圧延を経て、厚み40μm、幅1200mmのアルミニウム合金箔の試料を作製した。なお、中間焼鈍の方法については表1に示した。実施例8のCAL焼鈍は、昇温速度:40℃/秒、加熱温度:460℃、保持時間:1秒、冷却速度:40℃/秒の条件で行った。表1の冷間圧延の項目では、中間焼鈍直前の板厚および前記板厚までの冷間圧延率を示している。
引張強さ、伸びのいずれも引張試験にて測定した。引張試験は、JIS Z2241:2011(ISO 6892-1を基とする)に準拠し、圧延方向に対して0°方向の伸びを測定できるように、JIS5号試験片を試料から採取し、万能引張試験機(島津製作所社製 AGS-X 10kN)で引張り速度2mm/minにて試験を行った。伸び率の算出について以下の通りである。まず試験前に試験片長手中央に試験片垂直方向に2本の線を標点距離である50mm間隔でマークする。試験後にアルミニウム合金箔の破断面をつき合わせてマーク間距離を測定し、そこから標点距離(50mm)を引いた伸び量(mm)を、標点間距離(50mm)で除して伸び率(%)を求めた。なお、アルミニウム合金箔の伸びは、破断時の全伸び(伸び計の弾性伸びと塑性伸びとを合わせたもの)であり、伸び計標点距離に対する百分率で表したものである。
基材層としてポリエチレンテレフタレートフィルム(12μm)/接着剤層(2液硬化型ウレタン接着剤(ポリオール化合物と芳香族イソシアネート化合物)、厚さ3μm)/二軸延伸ナイロンフィルム(厚さ15μm)が順に積層された積層フィルムを用意した。次に、基材層の二軸延伸ナイロンフィルム(厚さ15μm)の上に、両面に耐酸性皮膜を形成した前記のアルミニウム合金箔(表1の組成を有し、厚さ40μm)からなるバリア層をドライラミネート法により積層させた。具体的には、両面に耐酸性皮膜(クロメート処理によって形成された皮膜であり、クロム量が30mg/m2)を形成したアルミニウム合金箔の一方面に、2液硬化型ウレタン接着剤(ポリオール化合物と芳香族イソシアネート化合物)を塗布し、アルミニウム合金箔上に接着剤層(硬化後の厚み3μm)を形成した。次いで、アルミニウム合金箔上の接着剤層と二軸延伸ナイロンフィルムを積層した後、エージング処理を実施することにより、基材層/接着剤層/バリア層の積層体を作製した。次に、得られた積層体のバリア層の上に、接着層としての無水マレイン酸変性ポリプロピレン(厚さ40μm)と、熱融着性樹脂層としてのポリプロピレン(厚さ40μm)とを共押出しすることにより、バリア層上に接着層/熱融着性樹脂層を積層させた。次に、得られた積層体をエージングし、加熱することにより、ポリエチレンテレフタレートフィルム(12μm)/接着剤層(3μm)/二軸延伸ナイロンフィルム(15μm)/接着剤層(3μm)/バリア層(40μm)/接着層(40μm)/熱融着性樹脂層(40μm)がこの順に積層された蓄電デバイス用外装材を得た。
上記で得られた各蓄電デバイス用外装材を長さ(MD)90mm×幅(TD)150mmの長方形に裁断して試験サンプルとした。蓄電デバイス用外装材のMDが、アルミニウム合金箔の圧延方向(RD)に対応し、蓄電デバイス用外装材のTDが、アルミニウム合金箔のTDに対応する。試験サンプルを25℃の環境下にて、31.6mm(MD)×54.5mm(TD)の矩形状の口径を有する成形金型(雌型、表面は、JIS B 0659-1:2002附属書1(参考) 比較用表面粗さ標準片の表2に規定される、最大高さ粗さ(Rzの呼び値)が3.2μmである。コーナーR2.0mm、稜線R1.0mm)と、これに対応した成形金型(雄型、表面は、JIS B 0659-1:2002附属書1(参考) 比較用表面粗さ標準片の表2に規定される、最大高さ粗さ(Rzの呼び値)が1.6μmである。コーナーR2.0mm、稜線R1.0mm)を用いて、押さえ圧(面圧)0.25MPaで0.5mmの成形深さから0.5mm単位で成形深さを変えて、それぞれ10個のサンプルについて冷間成形(引き込み1段成形)を行った。このとき、雄型側に熱融着性樹脂層側が位置するよう、雌型上に試験サンプルを載置して成形をおこなった。また、雄型及び雌型のクリアランスは、0.3mmとした。冷間成形後のサンプルについて、暗室の中にてペンライトで光を当てて、光の透過によって、アルミニウム合金箔にピンホールやクラックが生じているか否かを確認した。アルミニウム合金箔にピンホール、クラックが10個のサンプル全てにおいて発生しない最も深い成形深さを限界成形深さPmmとした。限界成形深さが4.0mm以上であった場合を評価A、3.0mm以下であった場合を評価Cとした。結果を表2に示す。
実施例1~20及び比較例1~8で使用した各アルミニウム合金箔を、長さ45mm×幅15mmの長方形に裁断した。次に、アルミニウム合金箔の表面及び裏面の一方の面に1cmφの露出部が形成されるように、アルミニウム合金箔の表面及び裏面に長さ50mm×幅20mmの長方形のポリエチレンフィルムをアルミニウム合金箔に重ねて熱溶着し取付け被覆して、試験サンプルとした。なお、試験サンプルにおける耐腐食性の評価は、アルミニウム合金箔ALが露出した1cmφの部分で行い、試験サンプルの電解液に浸漬されない端部については、作用極に接続するために露出させた。次に、図5の模式図に示すように、試験サンプルALを作用極、金属リチウムLi(直径15mm×厚み0.35mmの円盤状)を対極にセットし、電解液(1mol/lのLiPF6と、エチレンカーボネート、ジエチルカーボネート及びジメチルカーボネート(容量比1:1:1)の混合液とからなる)に浸漬させた。この状態で、20℃の環境下、電圧0.1Vで1時間印加した後、アルミニウム合金箔の表面を観察した。図8(比較例1)のように表面が腐食したものを評価C、図7(実施例1)のように変化しなかったものを評価Aとし、結果を表2に示す。腐食したアルミニウム合金箔表面はリチウムとの化合物が生成し、体積膨張により表面が盛り上がっている様子が観察される。
項1. 少なくとも、基材層、バリア層、及び熱融着性樹脂層をこの順に備える積層体から構成されており、
前記バリア層は、Si:0.5質量%以下、Fe:0.2質量%以上2.0質量%以下、Mg:0.1質量%以上5.0質量%以下の組成を満たすアルミニウム合金箔を含む、蓄電デバイス用外装材。
項2. 前記アルミニウム合金箔の組成は、Mn:0.1質量%以下を満たす、項1に記載の蓄電デバイス用外装材。
項3. 前記アルミニウム合金箔は、JIS Z2241:2011の規定に準拠して、JIS5号試験片について測定される、引張強さが100MPa以上であり、伸びが10%以上である、項1又は2に記載の蓄電デバイス用外装材。
項4. 少なくとも正極、負極、及び電解質を備えた蓄電デバイス素子が、項1~3のいずれか1項に記載の蓄電デバイス用外装材により形成された包装体中に収容されている、蓄電デバイス。
項5. 少なくとも、基材層、バリア層、及び熱融着性樹脂層がこの順となるように積層して積層体を得る工程を備えており、
前記バリア層は、Si:0.5質量%以下、Fe:0.2質量%以上2.0質量%以下、Mg:0.1質量%以上5.0質量%以下の組成を満たすアルミニウム合金箔を含む、蓄電デバイス用外装材の製造方法。
2 接着剤層
3 バリア層
4 熱融着性樹脂層
5 接着層
6 表面被覆層
10 蓄電デバイス用外装材
Claims (5)
- 少なくとも、基材層、バリア層、及び熱融着性樹脂層をこの順に備える積層体から構成されており、
前記バリア層は、Si:0.5質量%以下、Fe:0.2質量%以上2.0質量%以下、Mg:0.1質量%以上5.0質量%以下の組成を満たし、残部がアルミニウム及び不可避不純物からなるアルミニウム合金箔であって、
前記アルミニウム合金箔中の、Si,Fe,Mg,及びAl以外の成分である不可避不純物の含有率が、個々に0.10質量%以下かつ合計で0.40質量%以下である、蓄電デバイス用外装材。 - 前記アルミニウム合金箔の組成は、Mn:0.1質量%以下を満たす、請求項1に記載の蓄電デバイス用外装材。
- 前記アルミニウム合金箔は、JIS Z2241:2011の規定に準拠して、JIS5号試験片について測定される、引張強さが100MPa以上であり、伸びが10%以上である、請求項1又は2に記載の蓄電デバイス用外装材。
- 少なくとも正極、負極、及び電解質を備えた蓄電デバイス素子が、請求項1~3のいずれか1項に記載の蓄電デバイス用外装材により形成された包装体中に収容されている、蓄電デバイス。
- 少なくとも、基材層、バリア層、及び熱融着性樹脂層がこの順となるように積層して積層体を得る工程を備えており、
前記バリア層は、Si:0.5質量%以下、Fe:0.2質量%以上2.0質量%以下、Mg:0.1質量%以上5.0質量%以下の組成を満たし、残部がアルミニウム及び不可避不純物からなるアルミニウム合金箔であって、
前記アルミニウム合金箔中の、Si,Fe,Mg,及びAl以外の成分である不可避不純物の含有率が、個々に0.10質量%以下かつ合計で0.40質量%以下である、蓄電デバイス用外装材の製造方法。
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CN111653694B (zh) * | 2020-05-21 | 2021-08-06 | 上海恩捷新材料科技有限公司 | 一种电池装置用外包装材料及电池 |
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JP7230798B2 (ja) * | 2017-02-24 | 2023-03-01 | 株式会社Gsユアサ | 非水電解質蓄電素子及びその製造方法 |
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JP2005343105A (ja) | 2004-06-07 | 2005-12-15 | Sumitomo Light Metal Ind Ltd | アルミニウムラミネート材 |
JP2007073402A (ja) | 2005-09-08 | 2007-03-22 | Sumitomo Light Metal Ind Ltd | 電池外装用アルミラミネート構成物 |
JP2015165476A (ja) | 2014-03-03 | 2015-09-17 | 大日本印刷株式会社 | 電池用包装材料 |
WO2017188396A1 (ja) | 2016-04-27 | 2017-11-02 | 大日本印刷株式会社 | 電池用包装材料、その製造方法、電池及びその製造方法 |
JP2018168449A (ja) | 2017-03-30 | 2018-11-01 | 株式会社Uacj | アルミニウム合金軟質箔およびその製造方法並びに二次電池用外装材 |
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EP4084029A1 (en) | 2022-11-02 |
JPWO2021132562A1 (ja) | 2021-07-01 |
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WO2021132562A1 (ja) | 2021-07-01 |
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