JP5408726B2 - 電気化学素子用セパレータおよび電気化学素子 - Google Patents
電気化学素子用セパレータおよび電気化学素子 Download PDFInfo
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- JP5408726B2 JP5408726B2 JP2010054079A JP2010054079A JP5408726B2 JP 5408726 B2 JP5408726 B2 JP 5408726B2 JP 2010054079 A JP2010054079 A JP 2010054079A JP 2010054079 A JP2010054079 A JP 2010054079A JP 5408726 B2 JP5408726 B2 JP 5408726B2
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- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000011242 organic-inorganic particle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
Description
P = 100−(Σai/ρi)×(m/t) (1)
ここで、前記式中、ai:質量%で表した成分iの比率、ρi:成分iの密度(g/cm3)、m:セパレータの単位面積あたりの質量(g/cm2)、t:セパレータの厚み(cm)である。
2)とし、tを多孔質層(I)の厚み(cm)とすることで、前記(1)式を用いて多孔
質層(I)の空孔率:P(%)を求めることもできる。この方法により求められる多孔質
層(I)の空孔率は、30〜70%であることが好ましい。
多孔質層(I)を構成するための微多孔膜として、PE製電池用微多孔膜(厚み12μm、空孔率40%)を用意した。なお、このPE製電池用微多孔膜について、前記の方法により測定したTD方向における最初の応力ピークのピークトップ温度は、131℃であった。
LDPE(融点110℃、一次粒子径6μm)600gを120℃で溶融し、これにベーマイト粉末(粒状、平均粒径0.6μm)を2000g加えて混合、冷却後、スタンプミルで予備粉砕した。これを更に湿式でビーズミルにより解砕し、平均粒径が1.1μmのPE被覆フィラーを作製した。
アイオノマー微粒子のディスパージョンを使用しなかった以外は、実施例1と同様にして多孔質層(II)形成用スラリーを調製し、これを用いた以外は実施例1と同様にして、厚みが2.6μmの多孔質層(II)を有するセパレータを作製した。
実施例1、2および比較例1のセパレータを、それぞれ10×10cmに切り出し、130℃の恒温槽内に1時間放置した。恒温槽から取り出した後、透気度(JIS P 8117に準拠したガーレー式透気度計)を測定した。透気度上昇率は、恒温槽での放置前後の値から、下記式によって算出した。
透気度上昇率(%)
= 100×(130℃1時間放置後の透気度)/(恒温槽投入前の透気度)
実施例1、2および比較例1のセパレータを、それぞれ10×10cmに切り出して市販の封筒に収め、130℃に設定した恒温槽内に1時間放置した。その後、各セパレータを恒温槽から取り出し、多孔質層(I)を構成する微多孔膜のTD方向における寸法を測定し、これらの値と恒温槽での放置前の寸法とから、下記式によって熱収縮率を算出した。
熱収縮率(%) = 100×(10−x)/10
[なお、前記式中、xは130℃に設定した恒温槽内で1時間放置した後のセパレータにおける多孔質層(I)を構成する微多孔膜のTD方向の寸法(cm)である。]
Claims (8)
- 正極、負極およびセパレータを重ねて巻回した巻回電極体を有する電気化学素子の前記セパレータに使用され、熱可塑性樹脂を主体とし、MD方向とTD方向とを有する微多孔膜からなる多孔質層(I)と、耐熱温度が150℃以上のフィラーを主体として含む多孔質層(II)とを有する電気化学素子用セパレータであって、
前記電気化学素子用セパレータは、そのTD方向が前記巻回電極体の巻回方向に直交する方向となるように配されるものであり、
前記多孔質層(II)は、熱機械分析により測定される、5℃/minの昇温速度で室温から200℃まで昇温した際に得られる温度−応力曲線より求められる、多孔質層(I)を構成する前記微多孔膜のTD方向における最初の応力ピークのピークトップ温度よりも、低い温度に融点を有するポリオレフィンを含有することを特徴とする電気化学素子用セパレータ。 - 多孔質層(II)における前記ポリオレフィンの含有比率が、多孔質層(II)の構成成分の全体積中、5体積%以上である請求項1に記載の電気化学素子用セパレータ。
- 多孔質層(II)に含まれるフィラーの少なくとも一部が板状粒子である請求項1または2に記載の電気化学素子用セパレータ。
- 多孔質層(II)に含まれるフィラーの少なくとも一部が、一次粒子が凝集した二次粒子構造を有している請求項1〜3のいずれかに記載の電気化学素子用セパレータ。
- 多孔質層(II)に含まれるフィラーが、アルミナ、シリカおよびベーマイトよりなる群から選択される少なくとも1種の粒子である請求項1〜4のいずれかに記載の電気化学素子用セパレータ。
- 多孔質層(II)に含まれる前記ポリオレフィンが粒子状である請求項1〜5のいずれかに記載の電気化学素子用セパレータ。
- 多孔質層(I)に含まれる熱可塑性樹脂の融点が、110〜150℃である請求項1〜6のいずれかに記載の電気化学素子用セパレータ。
- 正極、負極およびセパレータを重ねて巻回した巻回電極体と、非水電解液とを有する電気化学素子であって、
前記セパレータが、請求項1〜7のいずれかに記載の電気化学素子用セパレータであり、 前記セパレータのTD方向が、前記巻回電極体の巻回方向に直交する方向となるように配されていることを特徴とする電気化学素子。
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