JP2022043066A - 電池セパレータ、リチウムイオン電池、セパレータ膜、乾式微多孔質ポリマー膜 - Google Patents
電池セパレータ、リチウムイオン電池、セパレータ膜、乾式微多孔質ポリマー膜 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 229920000098 polyolefin Polymers 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims description 16
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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- H—ELECTRICITY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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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
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- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
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- Cell Separators (AREA)
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- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
本出願は、2015年11月11日に出願されたアメリカ合衆国仮特許出願シリアル番号62/253,932の優先権および利益を主張し、参照にすることにより本明細書に完全に組み入れられる。
本発明の実施例として製造されたさまざまな膜の実施例1、実施例2、および実施例3は、(以下の表1に示すように)対照比較例1よりも改良された穿刺強度および絶縁破壊(DB)における改良を示す。
図1-3の断面SEMは、カラム、ピラー、カラム状、カラム様、カラム化のまたは実質的に垂直の結晶性ポリマー構造を示し得る。結晶性ポリマーのこれらのカラムまたはピラーは、強度を高め、DBなどを改良し得る。
(ガーレー)
ガーレーは、本明細書では日本工業規格(JISガーレー)として定義され、王研(OHKEN)式透気度試験機を用いて測定される。JIS Gurleyは、100ccの空気が4.9インチの一定水圧において1平方インチのフィルムを通過するのに必要な秒単位の時間として定義される。
厚さは、Emveco Microgage 210-Aマイクロメーター厚さ試験機および試験手順ASTM D374を使用して、μm単位で測定される。
機械方向(MD)および横方向(TD)引張強度は、ASTM-882手順によるInstron Model 4201を使用して測定される。
破断時のMD伸び%は、サンプルを破断するために要する最大引張強度において測定された試験サンプルの機械方向に沿った試験サンプルの伸長のパーセントである。
破断時のTD伸び%は、サンプルを破断するために要する最大引張強度において測定された試験サンプルの横方向に沿った試験サンプルの伸長のパーセントである。
穿孔強度は、ASTM D3763に基づくInstron Model 4442を使用して測定される。測定は、微多孔膜の幅にわたって行われ、穿刺強度は、試験サンプルを穿刺するのに必要な力として定義される。
収縮率は、2枚の紙の間に試験サンプルを置き、紙の間にサンプルを挟み込んでオーブン中に吊るすことによって測定される。「105℃1時間」試験の場合、試料を105℃のオーブンに1時間入れる。オーブン内で指定の加熱時間の後、各サンプルを取り出し、両面粘着テープを使用して平らな対向面にテープで貼り付け、正確な長さと幅の測定のためにサンプルを平らにして平滑にした。収縮率は、機械方向(MD)および横方向(TD)の両方の方向で測定され、%MD収縮率および%TD収縮率として表される。
孔サイズは、Porous Materials, Inc. (PMI)から入手可能のAquaporeを使用して測定される。孔サイズは、μm単位で表される。
微多孔フィルム試料の多孔度は、ASTM法D-2873を使用して測定され、機械方向(MD)および横方向(TD)の両方で測定された、微多孔膜の空隙の百分率として定義される。
(絶縁破壊(DB))
試料の絶縁破壊が観察されるまで、セパレータ膜に電圧を印加する。強力なセパレータは高いDBを示す。セパレータ膜の不均一性は、DB値を低下させる。
圧縮弾性率は、TMA Q400および半球プローブを使用して評価された。5mm×5mmの試料を1N(568N/cm2)まで一定の速度で圧縮し、次に周囲温度にて一定速度で圧力を0Nに戻すように解放する。圧縮および回復中の寸法変化の割合は、試料の初期厚さに基づいて推定される。
混合侵入とは、カソードとアノードの材料の間に配置されたときにセパレータを通って短絡するのに必要な力である。この試験は、電池組立中にセパレータが短絡する傾向を示すために使用される。この方法の詳細は、US2010/209758に記載されている。
全てのサイクリングは定電流(CC)モードで行われた。使用される陰極は523NMCである。使用されるアノードは優れたグラファイトである。電解質は、3:7v:vEC:EMC溶媒中1MのLiPF6塩を使用した。電圧ウィンドウは3.0~4.3Vである。サイクル1~5は、C/10の充電率と放電率を有する。サイクル6-10は、C/5の充電率および放電率を有する。サイクル11-15は、C/5の充電率とC/2の放電率を有する。サイクル16-20は、C/5の充電率と1Cの放電率(充放電率容量;1Cは60分間の完全充電または放電の率である。)を有する。サイクル21-25は、C/5の充電率と5Cの放電率を有する。サイクル26-30は、C/5の充電率と10Cの放電率を有する。サイクル31-35は、C/10の充電率および放電率を有する。
Claims (13)
- それぞれのミクロ層が2μm未満の厚さを有する3層以上の乾式ポリマーミクロ層を含む乾式共伸出ポリオレフィン微多孔質セパレータサブ膜を含み、
前記乾式共伸出ポリオレフィン微多孔質セパレータサブ膜が、それぞれのミクロ層が2μm未満の厚さを有する複数の乾式ポリマーミクロ層を含む他の乾式共伸出ポリオレフィン微多孔質セパレータサブ膜に積層されている、リチウム電池用の電池セパレータ。 - 3層以上の前記乾式共伸出ポリオレフィン微多孔質セパレータサブ膜が共に積層されている請求項1に記載のリチウム電池用の電池セパレータ。
- 請求項1に記載のリチウム電池用の電池セパレータを含むリチウム電池。
- 請求項1に記載のリチウム電池用の電池セパレータを含むリチウムイオン電池。
- 請求項1に記載のリチウム電池用の電池セパレータを含むリチウムイオン二次電池。
- ミクロ膜が2μm未満の厚さを有する乾式共押出ポリマー多層ミクロ膜を1層以上含む電池セパレータであって、
前記2μm未満の厚さを有する乾式共押出ポリマー多層ミクロ膜が、ミクロ膜が2μm未満の厚さを有する他の2層以上の乾式共押出ポリマー多層ミクロ膜に積層されており、
前記電池セパレータは、改良された強度、改良されたシャットダウン、または割れの減少傾向のうち少なくとも1つの特性を有する、電池セパレータ。 - それぞれ他の乾式共押出ポリマー多層ミクロ膜である、他の乾式ポリマー膜に積層された1層以上の乾式共押出ポリマー多層ミクロ膜を含むセパレータ膜であって、
前記セパレータ膜は、改良された穿刺強度、改良されたシャットダウン、または割れの減少傾向のうち少なくとも1つの特性を有する、セパレータ膜。 - 請求項6に記載の電池セパレータを含むリチウムイオン電池。
- 請求項7に記載のセパレータ膜を含むリチウムイオン電池。
- ミクロ膜が2μm未満の厚さを有する乾式共押出微多孔質多層ミクロ膜を1層以上含む多層乾式微多孔質ポリマー膜であって、
2層以上の他の乾式ポリマー膜に積層されており、前記他の乾式ポリマー膜はそれぞれミクロ膜が2μm未満の厚さを有する乾式共押出微多孔質多層ミクロ膜を含む多層乾式微多孔質ポリマー膜である、多層乾式微多孔質ポリマー膜。 - 他の乾式共押出多層ミクロ層ポリマー膜である少なくとも1つの乾式ポリマー膜に積層された1層以上の乾式共押出多層ポリマー膜を含む、乾式微多孔質ポリマー膜。
- ポリオレフィン乾式微多孔質ポリマー膜を含む請求項10に記載の多層乾式微多孔質ポリマー膜。
- ポリオレフィン乾式微多孔質ポリマー膜を含む請求項11に記載の乾式微多孔質ポリマー膜。
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