JP7186878B2 - 多孔性分離膜及びこれを含むリチウム二次電池 - Google Patents
多孔性分離膜及びこれを含むリチウム二次電池 Download PDFInfo
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Description
本発明の一側面による多孔性分離膜は、複数の板形無機物粒子、及び前記板形無機物粒子表面の一部または全部に位置して前記板形無機物粒子の間を連結及び固定させる第1バインダー高分子を含む多孔質層;及び前記多孔質層のいずれか一面に形成された金属層を含む。
本発明の一側面によるリチウム二次電池は、正極、負極、前記正極及び負極の間に介在されたセパレーターを含み、前記セパレーターが前述した本発明の一実施例による多孔性分離膜である。
[実施例1]
<多孔性分離膜の製造>
PVdF-HFP高分子バインダー(Arkema社LBG Grade)と無機粒子(アルミナ、チセラ社NW-710グレード(Grade)、アスペクト比(aspect ratio)=67)を2:8の割合で混合した後、N-メチル-2-ピロリドン(NMP)溶媒に固形分濃度40%で混合してコーティング溶液を準備した。
正極活物質として機能するLiCoO2を96.7重量部、導電剤として機能するグラファイトを1.3重量部、結合剤として機能するポリフッ化ビニリデン(PVdF)を2.0重量部混合して正極合剤を調剤した。得られた正極合剤を溶媒として機能する1-メチル-2-ピロリドンに分散させることによって正極合剤スラリーを調剤した。このスラリーを厚さ20μmのアルミニウムホイルの両面にそれぞれコーティング、乾燥、及び圧搾して正極を製造した。
PVdF-HFP高分子バインダー(Arkema社LBG Grade)とBaSrTiO3を1:9の割合で混合した後、N-メチル-2-ピロリドン(NMP)溶媒に固形分濃度20wt%で混合してコーティング溶液を準備した。前記コーティング溶液を前記実施例1で製造した多孔性分離膜の表面の中で金属層が形成されていない他面に前記実施例1と同様の方法でコーティングして多孔性分離膜を製造したことを除いて、実施例1と同様の方法でリチウム二次電池を製造した。
PVdF-HFP高分子バインダー(Arkema社LBG Grade)と無機粒子(アルミナ、チセラ社NW-710 Grade)を1:9の割合で混合し、金属層を形成しないことを除いて、実施例1と同様の方法でリチウム二次電池を製造した。
多孔性分離膜でオプトドット(Optodot)社のCSP20製品を使用したことを除いて、実施例1と同様の方法でリチウム二次電池を製造した。
金属層を形成しないことを除いて、実施例1と同様の方法でリチウム二次電池を製造した。
ピーエヌイー・ソリューション(PNE SOLUTION)社のSmall Cell cycler装置を利用して、充電は0.2Cの定電流(CC)で4.25VになるまでCC充電し、以後4.25Vの定電圧(CV)で1C対比5%の電流カット-オフ(Cut-off)で1回充電し、以後0.5Cの定電流で3Vになるまで放電してこれを1サイクルとし、このようなサイクルを繰り返して行う。
対流式オーブン(Convection oven)を使用して150度の温度で分離膜を30分間露出させ、露出前後の分離膜面積を測定して収縮率を計算する方法で分離膜の高温安定性を調べた。
Claims (12)
- 複数の板形無機物粒子、及び前記板形無機物粒子の表面の一部または全部に位置して前記板形無機物粒子の間を連結及び固定させる第1バインダー高分子のみからなる多孔質層、及び
前記多孔質層のいずれか一面に形成された金属層、を含み、
前記板形無機物粒子のアスペクト比が5ないし100である、多孔性分離膜。 - 前記多孔質層の他面に形成されたセラミックスコーティング層をさらに含む、請求項1に記載の多孔性分離膜。
- 前記板形無機物粒子は、アルミナ、シリカ、ジルコニア、二酸化チタン、マグネシア、セリア、酸化イットリウム、酸化亜鉛、酸化鉄、バリウムチタン酸化物、アルミナ-シリカ複合酸化物、またはこれらの中で2以上の混合物である、請求項1又は2に記載の多孔性分離膜。
- 前記板形無機物粒子のアスペクト比が50ないし100である、請求項1から3の何れか一項に記載の多孔性分離膜。
- 前記金属層は、リチウムと反応してLixM(x=1ないし2.25)の合金(alloy)を形成することができる金属(M)を含む、請求項1から4の何れか一項に記載の多孔性分離膜。
- 前記金属層は、Al、In、Au、Ni及びMgからなる群から選択されるいずれか一つ以上の金属を含む、請求項1から5の何れか一項に記載の多孔性分離膜。
- 前記金属層は、0.01ないし1μmの厚さを有する、請求項1から6の何れか一項に記載の多孔性分離膜。
- 前記セラミックスコーティング層は誘電率が20ないし1000である、請求項2に記載の多孔性分離膜。
- 前記セラミックスコーティング層は、HfO2、ZrO2、BaSrTiO3及びPbLaZrTiO3からなる群から選択されるいずれか一つ以上の無機物粒子を含む、請求項2又は8に記載の多孔性分離膜。
- 正極、負極及び前記正極と負極の間に介在された分離膜を含むリチウム二次電池において、前記分離膜が請求項1に記載の多孔性分離膜である、リチウム二次電池。
- 前記負極と前記多孔性分離膜の金属層が当接する、請求項10に記載のリチウム二次電池。
- 前記リチウム二次電池は、負極内でリチウム金属またはリチウム合金を含むことを特徴とする、請求項10又は11に記載のリチウム二次電池。
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KR1020180122101A KR102388261B1 (ko) | 2018-10-12 | 2018-10-12 | 다공성 분리막 및 이를 포함하는 리튬 이차 전지 |
KR10-2018-0122101 | 2018-10-12 | ||
PCT/KR2019/013361 WO2020076121A1 (ko) | 2018-10-12 | 2019-10-11 | 다공성 분리막 및 이를 포함하는 리튬 이차 전지 |
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US20070190408A1 (en) | 2006-02-16 | 2007-08-16 | Kaoru Inoue | Separator and method of manufacturing non-aqueous electrolyte secondary battery using the same |
JP2009064566A (ja) | 2007-09-04 | 2009-03-26 | Hitachi Maxell Ltd | 電池用セパレータおよび非水電解質電池 |
JP2015519686A (ja) | 2012-04-10 | 2015-07-09 | カリフォルニア インスティチュート オブ テクノロジー | 電気化学システムの新規セパレータ |
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JP5148360B2 (ja) * | 2005-12-08 | 2013-02-20 | 日立マクセル株式会社 | セパレータ用多孔質基体、電気化学素子用セパレータ、電極および電気化学素子 |
JP5657856B2 (ja) * | 2007-01-29 | 2015-01-21 | 日立マクセル株式会社 | 多孔質膜、電池用セパレータおよびリチウム二次電池 |
WO2009151054A1 (ja) * | 2008-06-09 | 2009-12-17 | 日立マクセル株式会社 | セパレータ用多孔質膜、電池用セパレータ、電池用電極およびそれらの製造方法、ならびにリチウム二次電池 |
US9786888B2 (en) * | 2010-01-13 | 2017-10-10 | Sony Corporation | Separator and nonaqueous electrolyte battery |
TWI557969B (zh) * | 2011-10-21 | 2016-11-11 | 帝人股份有限公司 | 非水系蓄電池用分隔器及非水系蓄電池 |
JP5930387B2 (ja) * | 2012-04-16 | 2016-06-08 | 株式会社Gsユアサ | 蓄電素子 |
KR101724009B1 (ko) * | 2013-08-14 | 2017-04-06 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
KR101723994B1 (ko) | 2014-02-21 | 2017-04-06 | 주식회사 포스코 | 분리막, 분리막의 제조 방법, 이를 포함하는 리튬 폴리머 이차 전지, 및 이를 이용한 리튬 폴리머 이차 전지의 제조 방법 |
EP3327853A1 (en) * | 2016-11-29 | 2018-05-30 | Robert Bosch Gmbh | Method and circuit arrangement for pre-indication of dendrite formation in an electrode assembly of a battery cell and battery cell |
KR101985378B1 (ko) | 2017-05-02 | 2019-06-10 | 주식회사 레이 | 치아 촬영용 엑스레이 촬영기 |
CN107275550B (zh) * | 2017-06-20 | 2020-07-07 | 深圳市星源材质科技股份有限公司 | 一种陶瓷和聚合物复合涂覆锂离子隔膜及其制备方法 |
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US20070190408A1 (en) | 2006-02-16 | 2007-08-16 | Kaoru Inoue | Separator and method of manufacturing non-aqueous electrolyte secondary battery using the same |
JP2009064566A (ja) | 2007-09-04 | 2009-03-26 | Hitachi Maxell Ltd | 電池用セパレータおよび非水電解質電池 |
JP2015519686A (ja) | 2012-04-10 | 2015-07-09 | カリフォルニア インスティチュート オブ テクノロジー | 電気化学システムの新規セパレータ |
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WO2020076121A1 (ko) | 2020-04-16 |
US20220052421A1 (en) | 2022-02-17 |
JP2021534562A (ja) | 2021-12-09 |
ES2955565T3 (es) | 2023-12-04 |
KR102388261B1 (ko) | 2022-04-18 |
KR20200041691A (ko) | 2020-04-22 |
HUE062820T2 (hu) | 2023-12-28 |
EP3828959A4 (en) | 2021-11-10 |
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