JP6294803B2 - Lithium ion battery separator - Google Patents
Lithium ion battery separator Download PDFInfo
- Publication number
- JP6294803B2 JP6294803B2 JP2014208950A JP2014208950A JP6294803B2 JP 6294803 B2 JP6294803 B2 JP 6294803B2 JP 2014208950 A JP2014208950 A JP 2014208950A JP 2014208950 A JP2014208950 A JP 2014208950A JP 6294803 B2 JP6294803 B2 JP 6294803B2
- Authority
- JP
- Japan
- Prior art keywords
- ratio
- separator
- layer
- inorganic pigment
- coating liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 20
- 239000000835 fiber Substances 0.000 claims description 90
- 239000011777 magnesium Substances 0.000 claims description 82
- 239000001023 inorganic pigment Substances 0.000 claims description 63
- 239000004745 nonwoven fabric Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 31
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000576 coating method Methods 0.000 description 82
- 239000011248 coating agent Substances 0.000 description 78
- 239000007788 liquid Substances 0.000 description 68
- 238000000034 method Methods 0.000 description 35
- 239000000049 pigment Substances 0.000 description 29
- -1 polyethylene Polymers 0.000 description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- 229920000433 Lyocell Polymers 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007500 overflow downdraw method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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
Landscapes
- Cell Separators (AREA)
Description
本発明は、リチウムイオン電池用セパレータに関する。 The present invention relates to a separator for a lithium ion battery.
リチウムイオン電池（「電池」と記す場合がある）には、極板間の接触を防ぐためのリチウムイオン電池用セパレータ（「セパレータ」と記す場合がある）が用いられている。 Lithium ion batteries (sometimes referred to as “batteries”) use lithium ion battery separators (sometimes referred to as “separators”) to prevent contact between electrode plates.
セパレータとして従来用いられているポリエチレン又はポリプロピレンからなる多孔性フィルムは、耐熱性が低く、安全上重大な問題を抱えている。すなわち、多孔性フィルムをセパレータとして用いた電池は、内部短絡等の原因で電池内部の局部的な発熱が生じた場合、発熱部位周辺のセパレータが収縮して内部短絡が更に拡大し、暴走的に発熱して発火・破裂等の重大な事象に至ることがある。 A porous film made of polyethylene or polypropylene conventionally used as a separator has low heat resistance and has a serious safety problem. In other words, in the case of a battery using a porous film as a separator, when local heat generation occurs inside the battery due to an internal short circuit or the like, the separator around the heat generation site contracts and the internal short circuit further expands, causing a runaway The product may generate heat and cause serious events such as ignition and rupture.
このような問題に対し、ポリエチレンテレフタレート（ＰＥＴ）等の耐熱性の高い繊維からなる不織布にアルミナ等の無機顔料を含有してなる層（「顔料含有層」と記す場合がある）が形成されてなるセパレータが提案されている（例えば、特許文献１〜４参照）。しかし、このセパレータでは、顔料含有層が極板の電位に曝されることで、電気化学反応の生成物が生じ、電池特性、特にサイクル特性を悪化させるという問題があった。また、無機顔料含有層が薄い場合には、セパレータにピンホールが発生し、内部短絡が生じるという問題があった。 For such a problem, a layer containing an inorganic pigment such as alumina is formed on a non-woven fabric made of highly heat-resistant fibers such as polyethylene terephthalate (PET) (sometimes referred to as “pigment-containing layer”). Have been proposed (see, for example, Patent Documents 1 to 4). However, in this separator, the pigment-containing layer is exposed to the potential of the electrode plate, so that a product of an electrochemical reaction is generated, and the battery characteristics, particularly the cycle characteristics, are deteriorated. Further, when the inorganic pigment-containing layer is thin, there is a problem that pinholes are generated in the separator and an internal short circuit occurs.
本発明の課題は、リチウムイオン電池用セパレータに関し、セパレータのピンホールが少なく、該セパレータを用いた電池の安全性が高く、かつ電池のサイクル特性が良好になるセパレータを提供することである。 The subject of this invention is related to the separator for lithium ion batteries, and is providing the separator with few pinholes of a separator, the safety | security of the battery using this separator being high, and the cycling characteristics of a battery being favorable.
上記課題を解決するための手段は以下のとおりである。 Means for solving the above problems are as follows.
（１）不織布基材に無機顔料を付与してなるリチウムイオン電池用セパレータにおいて、
該セパレータが、無機顔料を主体としてなる層、無機顔料と基材繊維が混在してなる層、基材繊維を主体としてなる層がこの順に重なって構成されており、
無機顔料を主体としてなる層として、無機顔料としてマグネシウム（Ｍｇ）化合物を含有してなるＭ層を有し、
且つ無機顔料を主体としてなる層側の面のエネルギー分散Ｘ線分光法によるＭｇ及び炭素（Ｃ）の強度ピーク値の比（Ｍｇ／Ｃ比）が４．０以上であることを特徴とするリチウムイオン電池用セパレータ。
(1) In a separator for a lithium ion battery obtained by adding an inorganic pigment to a nonwoven fabric substrate,
The separator is composed of a layer mainly composed of an inorganic pigment, a layer formed by mixing an inorganic pigment and a base fiber, and a layer mainly composed of a base fiber in this order.
As a layer mainly composed of inorganic pigment, it has an M layer containing a magnesium (Mg) compound as an inorganic pigment,
The ratio of Mg and carbon (C) intensity peak values (Mg / C ratio) by energy dispersive X-ray spectroscopy on the layer side surface mainly composed of inorganic pigment is 4.0 or more. Separator for ion battery.
（２）基材繊維を主体としてなる層側の面のエネルギー分散Ｘ線分光法によるＭｇ及びＣの強度ピーク値の比（Ｍｇ／Ｃ比）が１．０×１０−１以上１．０未満である上記（１）記載のリチウムイオン電池用セパレータ。 (2) Ratio of Mg and C intensity peak values (Mg / C ratio) of 1.0 × 10 −1 or more and less than 1.0 by energy dispersive X-ray spectroscopy on the surface of the layer side mainly composed of the base fiber The separator for a lithium ion battery according to the above (1).
（３）無機顔料を主体としてなる層として、無機顔料としてアルミニウム（Ａｌ）化合物を含有してなるＡ層を更に有し、
且つ無機顔料を主体としてなる層側の面のエネルギー分散Ｘ線分光法によるＭｇ及びＡｌの強度ピーク値の比（Ｍｇ／Ａｌ比）が２０以上であり、
基材繊維を主体としてなる層側の面のエネルギー分散Ｘ線分光法によるＭｇ及びＡｌの強度ピーク値の比（Ｍｇ／Ａｌ比）が１．０×１０−２以上１．０未満である上記（１）記載のリチウムイオン電池用セパレータ。
(3) The layer mainly composed of an inorganic pigment further includes an A layer containing an aluminum (Al) compound as an inorganic pigment,
And the ratio of Mg and Al intensity peak value (Mg / Al ratio) by energy dispersive X-ray spectroscopy of the layer side surface mainly composed of inorganic pigment is 20 or more,
The ratio of the intensity peak values of Mg and Al (Mg / Al ratio) by the energy dispersive X-ray spectroscopy on the layer side surface mainly composed of the base fiber is 1.0 × 10 −2 or more and less than 1.0 (1) The separator for lithium ion batteries as described.
（４）基材繊維を主体としてなる層側の面のエネルギー分散Ｘ線分光法によるＡｌ及びＣの強度ピーク値の比（Ａｌ／Ｃ比）が１．０×１０−２以上１．０未満である上記（３）記載のリチウムイオン電池用セパレータ。 (4) Ratio of Al and C intensity peak values (Al / C ratio) of 1.0 × 10 −2 or more and less than 1.0 by energy dispersive X-ray spectroscopy on the surface of the layer side mainly composed of the base fiber The separator for a lithium ion battery according to the above (3).
本発明によれば、ピンホールが少ないリチウムイオン電池用セパレータが得られ、該セパレータを用いた電池の安全性が高く、かつ電池のサイクル特性が良好になるという効果が得られる。 According to the present invention, a lithium ion battery separator with few pinholes can be obtained, and the effects of high battery safety using the separator and good battery cycle characteristics can be obtained.
本発明のリチウムイオン電池用セパレータ（１）は、不織布基材に無機顔料を付与してなるセパレータであり、無機顔料を主体としてなる層（「顔料主体層」と記す場合がある）、無機顔料と基材繊維が混在してなる層（「混在層」と記す場合がある）、基材繊維を主体としてなる層（「繊維主体層」と記す場合がある）がこの順に重なって構成されているセパレータである。また、顔料主体層として、無機顔料としてマグネシウム（Ｍｇ）化合物を含有してなるＭ層を有し、且つ顔料主体層側の面のエネルギー分散Ｘ線分光法（Ｅｎｅｒｇｙ Ｄｉｓｐｅｒｓｉｖｅ ｘ−ｒａｙ Ｓｐｅｃｔｒｏｓｃｏｐｙ、ＥＤＳ）によるＭｇ及び炭素（Ｃ）の強度ピーク値の比（Ｍｇ／Ｃ比）が４．０以上であることを特徴とするセパレータである。さらに、本発明のセパレータ（２）のように、繊維主体層側の面のＥＤＳによるＭｇ／Ｃ比が１．０×１０−１以上１．０未満であることが好ましい。このセパレータ用いた電池は、安全性が高く、サイクル特性が良好になるという効果が達成できる。 The lithium ion battery separator (1) of the present invention is a separator formed by applying an inorganic pigment to a nonwoven fabric substrate, and is a layer mainly composed of an inorganic pigment (sometimes referred to as a “pigment main layer”), an inorganic pigment And a layer composed of a mixture of base fibers (sometimes referred to as a “mixed layer”) and a layer composed mainly of base fibers (may be referred to as a “fiber main layer”). It is a separator. In addition, the pigment main layer has an M layer containing a magnesium (Mg) compound as an inorganic pigment, and energy dispersive x-ray spectroscopy (EDS) on the surface of the pigment main layer side (Energy Dispersive x-ray Spectroscopy, EDS) The separator is characterized in that the ratio of Mg and carbon (C) strength peak values (Mg / C ratio) by 4.0 is 4.0 or more. Further, like the separator (2) of the present invention, it is preferable that the Mg / C ratio by EDS of the surface on the fiber main layer side is 1.0 × 10 −1 or more and less than 1.0. The battery using this separator can achieve the effects of high safety and good cycle characteristics.
本発明のセパレータ（３）は、顔料主体層として、無機顔料としてアルミニウム（Ａｌ）化合物を含有してなるＡ層を更に有し、且つ顔料主体層側の面のＥＤＳによるＭｇ及びＡｌの強度ピーク値の比（Ｍｇ／Ａｌ比）が２０以上であり、繊維主体層側の面のＥＤＳによるＭｇ／Ａｌ比が１．０×１０−２以上１．０未満であるセパレータである。また、本発明のセパレータ（４）のように、繊維主体層側の面のＥＤＳによるＡｌ及びＣの強度ピーク値の比（Ａｌ／Ｃ比）が１．０×１０−２以上１．０未満であることが好ましい。このセパレータでは、ピンホールが少ないという効果を達成することができる。 The separator (3) of the present invention further has an A layer containing an aluminum (Al) compound as an inorganic pigment as a pigment main layer, and intensity peaks of Mg and Al by EDS on the surface of the pigment main layer side. The separator has a value ratio (Mg / Al ratio) of 20 or more and an Mg / Al ratio of 1.0 × 10 −2 or more and less than 1.0 by EDS on the surface of the fiber main layer side. Further, as in the separator (4) of the present invention, the ratio of Al and C intensity peaks (Al / C ratio) by EDS on the fiber main layer side surface is 1.0 × 10 −2 or more and less than 1.0. It is preferable that This separator can achieve the effect that there are few pinholes.
エネルギー分散Ｘ線分光法（ＥＤＳ）とは、試料表面に電子線を照射し、その際に発生する原子固有の特性Ｘ線をエネルギー分散型検出器にて検出して、そのエネルギーと強度から、試料表面を構成する元素と濃度を調べる元素分析手法である。このエネルギー分散Ｘ線分光法を用いた分析装置としては、電界放射型走査電子顕微鏡（日本電子（ＪＥＯＬ）製、装置名：ＪＳＭ−０６７００Ｆ）などが挙げられる。本発明において、ＥＤＳによるＭｇ／Ｃ比、Ｍｇ／Ａｌ比、Ａｌ／Ｃ比は、ＪＳＭ−０６７００Ｆを使用して加速電圧１０ｋＶ、倍率４０倍の視野を３箇所測定し、得られたＭｇ、Ａｌ及びＣ由来の特性Ｘ線のピーク強度（特性Ｘ線のカウント数）の比の平均値により求めた。 Energy dispersive X-ray spectroscopy (EDS) is a method of irradiating a sample surface with an electron beam, detecting characteristic X-rays peculiar to atoms generated at that time with an energy dispersive detector, This is an elemental analysis method for examining the elements and concentration of the sample surface. Examples of the analyzer using this energy dispersive X-ray spectroscopy include a field emission scanning electron microscope (manufactured by JEOL, apparatus name: JSM-06700F). In the present invention, the Mg / C ratio, Mg / Al ratio, and Al / C ratio by EDS were measured at three locations with an acceleration voltage of 10 kV and a magnification of 40 times using JSM-06700F. And the average value of the ratios of the peak intensities (characteristic X-ray counts) of characteristic X rays derived from C.
不織布基材を形成する基材繊維としては、ポリプロピレン（Ｐｏｌｙｐｒｏｐｙｌｅｎｅ）、ポリエチレン（Ｐｏｌｙｅｔｈｙｌｅｎｅ）等のポリオレフィン（Ｐｏｌｙｏｌｅｆｉｎ）；ポリエチレンテレフタレート（Ｐｏｌｙｅｔｈｙｌｅｎｅ Ｔｅｒｅｐｈｔｈａｌａｔｅ、ＰＥＴ）、ポリエチレンイソフタレート（Ｐｏｌｙｅｔｈｙｌｅｎｅ Ｉｓｏｐｈｔｈａｌａｔｅ）、ポリエチレンナフタレート（Ｐｏｌｙｅｔｈｙｌｅｎｅ Ｎａｐｈｔｈａｌａｔｅ）等のポリエステル（Ｐｏｌｙｅｓｔｅｒ）；ポリアクリロニトリル（Ｐｏｌｙａｃｒｙｌｏｎｉｔｒｉｌｅ）等のアクリル（Ａｃｒｙｌ）；６，６ナイロン（６，６Ｎｙｌｏｎ）、６ナイロン（６Ｎｙｌｏｎ）等のポリアミド（Ｐｏｌｙａｍｉｄｅ）等の各種合成繊維が挙げられる。また、木材パルプ、麻パルプ、コットンパルプ等の各種セルロースパルプ；レーヨン（Ｒａｙｏｎ）、リヨセル（Ｌｙｏｃｅｌｌ）等のセルロース系再生繊維等が挙げられる。これらの中で、耐熱性、低吸湿性等の理由から、ポリエステル及びポリプロピレンの群から選ばれる少なくとも１種の合成繊維を基材繊維として含有してなる不織布基材が好ましい。 Examples of the base fiber forming the nonwoven fabric base include polyolefin (polypropylene) such as polypropylene (polypropylene) and polyethylene (polyethylene); polyethylene terephthalate (polyethylene terephthalate, PET), polyethylene isophthalate (polyethylene isophthalate) Various synthetic fibers such as polyester such as Naphthalate; acrylic such as polyacrylonitrile; acrylic such as 6,6 nylon, and nylon such as 6 nylon. . Moreover, various cellulose pulps, such as wood pulp, hemp pulp, and cotton pulp; Cellulosic reproduction | regeneration fiber, such as Rayon (Lyon) and Lyocell (Lyocell), etc. are mentioned. Among these, a nonwoven fabric base material containing at least one synthetic fiber selected from the group of polyester and polypropylene as a base fiber is preferable for reasons such as heat resistance and low hygroscopicity.
基材繊維の好ましい繊維径は、塗工液の物性にも依存するが、１〜８μｍの範囲にあることが好ましい。 Although the preferable fiber diameter of a base fiber is dependent also on the physical property of a coating liquid, it is preferable to exist in the range of 1-8 micrometers.
本発明のセパレータは、不織布基材の片面に無機顔料を含む液（「塗工液」と記す場合がある）を付与して、無機顔料を含有してなる層が形成されることによって得られる。塗工液は、少なくとも無機顔料としてＭｇ化合物を含む。 The separator of the present invention is obtained by forming a layer containing an inorganic pigment by applying a liquid containing an inorganic pigment (sometimes referred to as “coating liquid”) to one side of a nonwoven fabric substrate. . The coating solution contains at least an Mg compound as an inorganic pigment.
Ｍｇ化合物としては、水酸化マグネシウム、酸化マグネシウム、炭酸マグネシウム等のＭｇ化合物を用いることができる。また、Ａｌ化合物としては、α−アルミナ、β−アルミナ、γ−アルミナ等のアルミナ（Ａｌｕｍｉｎａ、Ａｌｕｍｉｎｉｕｍ ｏｘｉｄｅ）；ベーマイト（Ｂｏｅｈｍｉｔｅ）等のアルミナ水和物等を用いることができる。これらの中でも、リチウムイオン電池に用いられる電解質に対する安定性が高い点で、Ｍｇ化合物では水酸化マグネシウム、Ａｌ化合物の中ではアルミナ水和物が好ましく用いられる。 As the Mg compound, Mg compounds such as magnesium hydroxide, magnesium oxide, and magnesium carbonate can be used. As the Al compound, alumina such as α-alumina, β-alumina, and γ-alumina, and alumina hydrate such as boehmite can be used. Among these, magnesium hydroxide is preferably used as the Mg compound, and alumina hydrate is preferably used as the Al compound because of its high stability to the electrolyte used in the lithium ion battery.
塗工液はバインダー樹脂を含むことができる。バインダー樹脂としては、スチレン−ブタジエン樹脂；（メタ）アクリル酸エステル樹脂；ポリフッ化ビニリデン等のフッ素樹脂等；各種の合成樹脂を用いることができる。バインダー樹脂の使用量は、無機顔料に対して０．１〜３０質量％であることが好ましい。 The coating liquid can contain a binder resin. As the binder resin, styrene-butadiene resin; (meth) acrylic ester resin; fluorine resin such as polyvinylidene fluoride; and various synthetic resins can be used. It is preferable that the usage-amount of binder resin is 0.1-30 mass% with respect to an inorganic pigment.
塗工液には、無機顔料の分散を補助する目的で分散剤を使用することができる。分散剤は一般的に無機顔料の分散剤として入手できるものであれば何れを用いても良いが、好ましくはポリカルボン酸型高分子界面活性剤である。分散剤の使用量は、無機顔料に対して０．０１〜２質量％であることが好ましい。 In the coating liquid, a dispersant can be used for the purpose of assisting the dispersion of the inorganic pigment. Any dispersant can be used as long as it is generally available as a dispersant for inorganic pigments, but a polycarboxylic acid type polymer surfactant is preferred. It is preferable that the usage-amount of a dispersing agent is 0.01-2 mass% with respect to an inorganic pigment.
本発明において、基材繊維を構成する元素は、主に、炭素（Ｃ）、酸素（Ｏ）である。また、セパレータ（１）及び（２）を構成する元素は、主に、マグネシウム（Ｍｇ）、炭素（Ｃ）及び酸素（Ｏ）であり、セパレータ（３）及び（４）を構成する元素は、主に、マグネシウム（Ｍｇ）、アルミニウム（Ａｌ）、炭素（Ｃ）及び酸素（Ｏ）である。 In the present invention, the elements constituting the base fiber are mainly carbon (C) and oxygen (O). The elements constituting the separators (1) and (2) are mainly magnesium (Mg), carbon (C) and oxygen (O), and the elements constituting the separators (3) and (4) are Mainly magnesium (Mg), aluminum (Al), carbon (C) and oxygen (O).
顔料主体層側の面のＭｇ／Ｃ比が４．０以上であるということは、基材繊維の露出がほとんどなく、無機顔料で覆われている状態を示す。基材繊維の露出を無くすことで、ピンホールの発生を抑制し、内部短絡を抑制することができる。さらに、Ｍｇ／Ｃ比を高くすることで、初期充電時に負極から発生するリチウムデンドライトによる微小内部短絡の抑制が可能となる。Ｍｇ／Ｃ比は５以上であることがより好ましく、８以上であることが更に好ましく、１０以上であることが特に好ましく、３０以上であることが最も好ましい。顔料主体層側の面のＭｇ／Ｃ比が高いほど、４．３Ｖ以上の電圧での充電でも微小短絡が起き難くなるため、好ましい。 That the Mg / C ratio of the surface on the pigment main layer side is 4.0 or more indicates that the base fiber is hardly exposed and is covered with an inorganic pigment. By eliminating the exposure of the base fiber, the occurrence of pinholes can be suppressed and internal short circuit can be suppressed. Further, by increasing the Mg / C ratio, it is possible to suppress a minute internal short circuit due to lithium dendrite generated from the negative electrode during initial charging. The Mg / C ratio is more preferably 5 or more, still more preferably 8 or more, particularly preferably 10 or more, and most preferably 30 or more. A higher Mg / C ratio on the surface of the pigment main layer side is preferable because a minute short circuit hardly occurs even when charging at a voltage of 4.3 V or higher.
繊維主体層側の面のＭｇ／Ｃ比が１．０×１０−１以上１．０未満であることは、その面のほとんどが基材繊維からなるが、一部無機顔料が存在していることを示す。繊維主体層が存在しない場合又は繊維主体層側の面のＭｇ／Ｃ比が１．０以上である場合、電池の特性、特にサイクル特性が悪化する場合がある。これは、セパレータが電極電位に直接曝されるために生じる電気化学反応により生じた分解生成物の影響であると考えられる。また、繊維主体層の厚みが２μｍ以上であることが、サイクル特性において、特に好ましい。一方、繊維主体層側の面のＭｇ／Ｃ比が１．０×１０−１未満である場合も、電池特性が悪化する場合がある。これは、極僅かに無機顔料が浸み出して、無機顔料が露出した部分だけで、リチウムイオンが伝導し易くなるためと考えられる。 The fact that the Mg / C ratio of the surface on the fiber main layer side is 1.0 × 10 −1 or more and less than 1.0 means that most of the surface is made of substrate fibers, but some inorganic pigments are present. It shows that. When the fiber main layer is not present or when the Mg / C ratio of the surface on the fiber main layer side is 1.0 or more, battery characteristics, particularly cycle characteristics, may be deteriorated. This is considered to be an influence of the decomposition product produced by the electrochemical reaction that occurs because the separator is directly exposed to the electrode potential. In addition, it is particularly preferable in terms of cycle characteristics that the thickness of the fiber main layer is 2 μm or more. On the other hand, when the Mg / C ratio of the surface on the fiber main layer side is less than 1.0 × 10 −1 , battery characteristics may be deteriorated. This is presumably because the inorganic pigment oozes out very slightly and lithium ions are easily conducted only at the exposed portion of the inorganic pigment.
顔料主体層側の面のＭｇ／Ａｌ比が２０以上であるということは、不織布基材上のＡ層がＭ層で覆われている状態を示す。Ａｌ化合物の露出を無くすことで、ピンホールの発生を抑制することができる。さらに、Ｍｇ／Ａｌ比を高くすることで、ピンホールによる初期充電時に負極から発生するリチウムデンドライトによる微小内部短絡の抑制が可能となる。Ｍｇ／Ａｌ比が３０以上である場合、ピンホールの発生による微小内部短絡がより起き難くなるため、より好ましい。 That the Mg / Al ratio of the surface on the pigment main layer side is 20 or more indicates a state in which the A layer on the nonwoven fabric substrate is covered with the M layer. By eliminating the exposure of the Al compound, the generation of pinholes can be suppressed. Further, by increasing the Mg / Al ratio, it is possible to suppress a minute internal short circuit due to lithium dendrite generated from the negative electrode during initial charging by pinholes. A Mg / Al ratio of 30 or more is more preferable because a minute internal short circuit due to the generation of pinholes is less likely to occur.
一方、繊維主体層側の面のＭｇ／Ａｌ比が１．０×１０−２以上１．０未満であることは、繊維主体層側の面に存在している無機顔料のほとんどがＡｌ化合物であることを示す。本発明において、繊維主体層側の面のＭｇ／Ａｌ比が１．０以上である場合、Ａ層上にＭ層を形成した際に、Ｍ層がＡ層を覆いきれず、ピンホールを抑制できない場合がある。繊維主体層側の面のＭｇ／Ａｌ比が１．０×１０−２未満である場合も、ピンホールが悪化する場合がある。これは、極僅かにＭｇ化合物が浸み出したことで、ピンホールの抑制効果が低下するためと考えられる。 On the other hand, the Mg / Al ratio of the fiber main layer side surface is 1.0 × 10 −2 or more and less than 1.0 is that most of the inorganic pigments existing on the fiber main layer side surface are Al compounds. It shows that there is. In the present invention, when the Mg / Al ratio on the surface of the fiber main layer side is 1.0 or more, when the M layer is formed on the A layer, the M layer cannot cover the A layer and suppress pinholes. There are cases where it is not possible. Even when the Mg / Al ratio on the surface of the fiber main layer side is less than 1.0 × 10 −2 , pinholes may be deteriorated. This is thought to be due to the fact that the Mg compound oozes out very slightly, which reduces the pinhole suppression effect.
一方、繊維主体層側の面のＡｌ／Ｃ比が１．０×１０−２以上１．０未満であることは、その面のほとんどが基材繊維からなるが、一部無機顔料が存在していることを示す。繊維主体層側の面のＡｌ／Ｃ比が１．０以上である場合、電池の特性、特にサイクル特性が悪化する場合がある。これは、Ａ層が電極電位に直接曝されるために生じる電気化学反応により生じた分解生成物の影響であると考えられる。一方、繊維主体層側の面のＡｌ／Ｃ比が１．０×１０−２未満である場合も、電池特性が悪化する場合がある。これは、極僅かに無機顔料が浸み出して、無機顔料が露出した部分だけで、リチウムイオンが伝導し易くなるためと考えられる。 On the other hand, the Al / C ratio of the surface on the fiber main layer side is 1.0 × 10 −2 or more and less than 1.0 means that most of the surface is made of base fiber, but some inorganic pigments exist. Indicates that When the Al / C ratio on the surface of the fiber main layer side is 1.0 or more, battery characteristics, particularly cycle characteristics, may be deteriorated. This is considered to be an influence of the decomposition product produced by the electrochemical reaction which occurs because the A layer is directly exposed to the electrode potential. On the other hand, when the Al / C ratio of the surface on the fiber main layer side is less than 1.0 × 10 −2 , battery characteristics may be deteriorated. This is presumably because the inorganic pigment oozes out very slightly and lithium ions are easily conducted only at the exposed portion of the inorganic pigment.
また、混在層における無機顔料の存在比率が、顔料主体層側から繊維主体層側へと向けて、連続的又は段階的に減少することで、これを用いた電池のサイクル特性が特に良好なセパレータになり好ましい。更に好ましくは、混在層における深さ１／４の部分における無機顔料の存在比率が、混在層の深さ３／４の部分における無機顔料の存在比率の１．５倍以上であることで、これを用いた電池のサイクル特性が特に良好なセパレータになる。これは、混在層の繊維主体層に近い部分における無機顔料の存在比率が大きすぎる（無機顔料の含有率が高すぎる）と、サイクル特性を低下させるような作用があるためと推定される。 In addition, the existence ratio of the inorganic pigment in the mixed layer decreases continuously or stepwise from the pigment main layer side to the fiber main layer side, so that the cycle characteristics of the battery using this are particularly good. This is preferable. More preferably, the abundance ratio of the inorganic pigment in the 1/4 portion of the mixed layer is 1.5 times or more than the abundance ratio of the inorganic pigment in the 3/4 depth portion of the mixed layer. The separator using the battery has particularly good cycle characteristics. It is presumed that this is because the presence of the inorganic pigment in the portion of the mixed layer close to the fiber main layer is too large (the content of the inorganic pigment is too high), and the cycle characteristics are lowered.
なお、本発明における「深さ」について説明する。まず、顔料主体層、混在層、繊維主体層における「深さ」を説明する。各層において、「長さ」で表した「深さ」とは、各層における表面又は隣接する層との境界面を「深さ０（零）」としたときの、反対面方向への距離Ｌ１である。各層において、「割合」で表した「深さ」とは、各層の全厚Ｌ２に対する距離Ｌ１の割合（Ｌ１／Ｌ２）である。 The “depth” in the present invention will be described. First, “depth” in the pigment main layer, the mixed layer, and the fiber main layer will be described. In each layer, the “depth” expressed by “length” is a distance L1 in the opposite surface direction when the surface of each layer or a boundary surface with an adjacent layer is set to “depth 0 (zero)”. is there. In each layer, “depth” expressed as “ratio” is a ratio (L1 / L2) of the distance L1 to the total thickness L2 of each layer.
次に、セパレータ又は不織布基材における「深さ」を説明する。セパレータ又は不織布基材において、「長さ」で表した「深さ」とは、セパレータ又は不織布基材の一方の表面を「深さ０（零）」としたときの、反対面方向への距離Ｌ３である。セパレータ又は不織布基材において、「割合」で表した「深さ」とは、セパレータ又は不織布基材の全厚Ｌ４に対する距離Ｌ３の割合（Ｌ３／Ｌ４）である。 Next, the “depth” in the separator or the nonwoven fabric substrate will be described. In a separator or non-woven fabric substrate, “depth” expressed in “length” means the distance in the opposite direction when one surface of the separator or non-woven fabric substrate is set to “depth 0 (zero)” L3. In the separator or nonwoven fabric substrate, the “depth” expressed in “ratio” is the ratio of the distance L3 to the total thickness L4 of the separator or nonwoven fabric substrate (L3 / L4).
「無機顔料を主体としてなる層（顔料主体層）」とは、セパレータの断面を観察した場合に、無機顔料の存在比率が４／１を超える領域である。「基材繊維を主体としてなる層（繊維主体層）」とは、セパレータの断面を観察した場合に、無機顔料の存在比率が１／４を下回る（１／４未満の）領域である。また、「無機顔料と基材繊維が混在してなる層（混在層）」とは、セパレータの断面を観察した場合に、無機顔料の存在比率が、１／４以上、４／１以下の領域である。 The “layer mainly composed of inorganic pigment (pigment-based layer)” is a region where the abundance ratio of the inorganic pigment exceeds 4/1 when the cross section of the separator is observed. The “layer mainly composed of substrate fibers (fiber-based layer)” is a region where the abundance ratio of the inorganic pigment is less than 1/4 (less than 1/4) when the cross section of the separator is observed. In addition, “a layer in which inorganic pigment and base fiber are mixed (mixed layer)” is a region where the abundance ratio of the inorganic pigment is 1/4 or more and 4/1 or less when the cross section of the separator is observed. It is.
本発明における無機顔料の存在比率とは、無機顔料／基材繊維の体積比率のことを言う。走査型電子顕微鏡（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ、ＳＥＭ）を用いてセパレータの断面の一定深さを直線状に走査した場合に、「無機顔料と同定される部分の長さ」／「基材繊維と同定される部分の長さ」で算出することができる。無機顔料又は基材繊維において、他方が含まない特有の元素又は両者が共通に含むが、その含有率が大きく異なる元素がある場合には、エネルギー分散Ｘ線分光法（ＥＤＳ）で材料の同定を行うことができる。 In the present invention, the abundance ratio of the inorganic pigment refers to the volume ratio of the inorganic pigment / substrate fiber. When a scanning electron microscope (Scanning Electron Microscope, SEM) is used to scan a constant depth of the cross-section of the separator in a straight line, “the length of the portion identified as an inorganic pigment” / “the substrate fiber is identified. It can be calculated by “the length of the part”. In the inorganic pigment or base fiber, if there is a special element that does not contain the other element or both, but the element content is significantly different, the material is identified by energy dispersive X-ray spectroscopy (EDS) It can be carried out.
本発明のセパレータは、次のようにして製造することができる。すなわち、不織布基材の表面に、無機顔料を含む塗工液を付与し、塗工液の少なくとも一部を不織布基材の内部に浸透した状態で乾燥させる。セパレータ（１）及び（２）では、不織布基材の表面に、Ｍｇ化合物を含む塗工液を付与し、乾燥させる。セパレータ（３）及び（４）では、不織布基材の表面に、Ａｌ化合物を含む塗工液を付与し、乾燥させ、さらにＭｇ化合物を含む塗工液を付与し、乾燥させる。 The separator of the present invention can be manufactured as follows. That is, a coating liquid containing an inorganic pigment is applied to the surface of the nonwoven fabric base, and at least a part of the coating liquid is dried while penetrating into the nonwoven fabric base. In separators (1) and (2), a coating liquid containing an Mg compound is applied to the surface of the nonwoven fabric substrate and dried. In the separators (3) and (4), a coating liquid containing an Al compound is applied to the surface of the nonwoven fabric substrate and dried, and a coating liquid containing an Mg compound is further applied and dried.
塗工時に、塗工液の浸透深さを、不織布基材の厚みの１／４以上、（不織布基材の厚み−２）μｍ以下にすることが好ましい。また、塗工液の一部が不織布基材の裏面側に一部浸み出すように、塗工液の浸透深さを調整することで、Ｍｇ／Ａｌ比、Ｍｇ／Ｃ比、Ａｌ／Ｃ比を本発明の範囲に調整することができる。 At the time of coating, it is preferable that the penetration depth of the coating liquid is ¼ or more of the thickness of the nonwoven fabric substrate and (thickness of the nonwoven fabric substrate−2) μm or less. Moreover, by adjusting the penetration depth of the coating liquid so that part of the coating liquid oozes out partly on the back side of the nonwoven fabric substrate, the Mg / Al ratio, Mg / C ratio, Al / C The ratio can be adjusted within the scope of the present invention.
本発明におけるＭｇ／Ａｌ比、Ｍｇ／Ｃ比、Ａｌ／Ｃ比を調整する方法としては以下のようなものがある。 Examples of methods for adjusting the Mg / Al ratio, Mg / C ratio, and Al / C ratio in the present invention include the following.
１つ目の方法として、不織布基材を構成する基材繊維を調整する方法がある。例えば、不織布基材中の基材繊維の繊維径を増減する方法、不織布基材中の細い繊維の配合率を増減する方法、基材繊維表面に付着している油剤や湿式法にて不織布基材を形成する場合に使用する分散剤や消泡剤などの界面活性剤の量を調整する方法などが挙げられる。本発明において、基材繊維への油剤や界面活性剤等の付着量は、０．０１〜１質量％の範囲が好ましい。 As a first method, there is a method of adjusting the base fiber constituting the nonwoven fabric base material. For example, a method for increasing / decreasing the fiber diameter of the base fiber in the non-woven fabric base, a method for increasing / decreasing the blending ratio of fine fibers in the non-woven base, an oil agent adhering to the surface of the base fiber or a wet method Examples thereof include a method of adjusting the amount of a surfactant such as a dispersant and an antifoaming agent used when forming the material. In the present invention, the adhesion amount of the oil agent or surfactant to the base fiber is preferably in the range of 0.01 to 1% by mass.
２つ目の方法として、塗工液の粘度（ハイシア（ｈｉｇｈ ｓｈｅａｒ）粘度、ローシア（ｌｏｗ ｓｈｅａｒ）粘度）を調整する方法がある。塗工液の粘度を調整する方法としては、塗工液の固形分濃度を調整する方法、増粘剤を添加する方法、増粘剤の添加量を調整する方法、塗工液の温度を調整する方法等がある。本発明において、塗工液のＢ型粘度は、１０〜１００００ｍＰａ・ｓが好ましく、より好ましくは２００〜２０００ｍＰａ・ｓの範囲である。Ｂ型粘度がこの範囲であることで、本発明のセパレータを容易に得ることが可能となる。 As a second method, there is a method of adjusting the viscosity of the coating liquid (high shear viscosity, low shear viscosity). As a method of adjusting the viscosity of the coating solution, a method of adjusting the solid content concentration of the coating solution, a method of adding a thickener, a method of adjusting the addition amount of the thickener, and adjusting the temperature of the coating solution There are ways to do this. In the present invention, the B-type viscosity of the coating liquid is preferably 10 to 10,000 mPa · s, more preferably 200 to 2000 mPa · s. When the B-type viscosity is within this range, the separator of the present invention can be easily obtained.
３つ目の方法として、塗工液の表面張力を調整する方法がある。塗工液の表面張力を調整する方法としては、濡れ剤を添加する方法、濡れ剤の添加量を調整する方法、塗工液の温度を調整する方法等がある。本発明において、塗工液が水系の場合の表面張力は、３０〜７０ｍＮ／ｍが好ましく、特に４５〜６５ｍＮ／ｍが特に好ましい。水系塗工液の表面張力がこの範囲であることで、本発明のセパレータを容易に得ることが可能となる。 As a third method, there is a method of adjusting the surface tension of the coating liquid. As a method for adjusting the surface tension of the coating liquid, there are a method of adding a wetting agent, a method of adjusting the addition amount of the wetting agent, a method of adjusting the temperature of the coating liquid, and the like. In the present invention, the surface tension when the coating solution is aqueous is preferably 30 to 70 mN / m, particularly preferably 45 to 65 mN / m. When the surface tension of the aqueous coating liquid is within this range, the separator of the present invention can be easily obtained.
４つ目の方法として、無機顔料を含む塗工液を付与する場合、塗工液を圧入する方向への動圧が作用しにくい塗工方式や圧入する方向への動圧が作用しやすい塗工方式を選択する方法がある。圧入する方向への動圧が作用しにくい塗工方式の例としては、ダイ（Ｄｉｅ）塗工、カーテン（Ｃｕｒｔａｉｎ）塗工が挙げられる。圧入する方向への動圧が作用しやすい塗工方式の例としては、含浸、ブレード（Ｂｌａｄｅ）、ロッド（Ｒｏｄ）塗工等が挙げられる。両者の中間的な塗工方式の例としては、グラビア塗工が挙げられる。本発明においては、キスリバース（Ｋｉｓｓ Ｒｅｖｅｒｓｅ）方式のグラビア（Ｇｒａｖｕｒｅ）塗工が、無機顔料の浸透度合いを容易に調整できることから好ましく用いられ、特にグラビア径が１５０ｍｍ以下の小径グラビアが更に好ましく用いられる。 As a fourth method, when applying a coating liquid containing an inorganic pigment, a coating method in which the dynamic pressure in the direction of press-fitting the coating liquid is difficult to act or a dynamic pressure in the direction of press-in is likely to act. There is a method of selecting a construction method. Examples of the coating method in which the dynamic pressure in the press-fitting direction is difficult to act include die coating and curtain coating. Examples of the coating method in which dynamic pressure in the press-fitting direction is easy to act include impregnation, blade (Blade), rod (Rod) coating and the like. An example of an intermediate coating method between the two is gravure coating. In the present invention, kiss reverse gravure coating is preferably used because the degree of penetration of the inorganic pigment can be easily adjusted, and a small gravure with a gravure diameter of 150 mm or less is particularly preferred. .
５つ目の方法として、Ａ層の付与量とＭ層の付与量を調整する方法がある。セパレータ（１）及び（２）において、本発明の構成を達成するためには、Ｍ層の付与量が、絶乾質量で０．５ｇ／ｍ２以上３０ｇ／ｍ２以下であることが好ましく、１．０ｇ／ｍ２以上２０ｇ／ｍ２以下であることがより好ましい。セパレータ（３）及び（４）において、本発明の構成を達成するためには、Ａ層及びＭｇ層各々において、絶乾質量で０．５ｇ／ｍ２以上１５ｇ／ｍ２以下であることが好ましく、１．０ｇ／ｍ２以上１０ｇ／ｍ２以下であることがより好ましい。 As a fifth method, there is a method of adjusting the application amount of the A layer and the application amount of the M layer. In the separators (1) and (2), in order to achieve the configuration of the present invention, it is preferable that the amount of the M layer applied is 0.5 g / m 2 or more and 30 g / m 2 or less in terms of absolute dry mass. More preferably, it is 1.0 g / m 2 or more and 20 g / m 2 or less. In the separators (3) and (4), in order to achieve the configuration of the present invention, the layer A and the Mg layer each preferably have an absolute dry mass of 0.5 g / m 2 or more and 15 g / m 2 or less. 1.0 g / m 2 or more and 10 g / m 2 or less is more preferable.
本発明において、不織布基材は特に制限されない。基材繊維をシート状に形成する製造方法としては、スパンボンド（Ｓｐｕｎｂｏｎｄ）法、メルトブロー（Ｍｅｌｔ−Ｂｌｏｗｎ）法、静電紡糸法、湿式（Ｗｅｔ Ｌａｙｉｎｇ）法、カード（Ｃａｒｄｉｎｇ）法等の製造方法が挙げられる。これらの中でも、薄くて緻密な構造の不織布基材を得ることができるため、湿式法が好ましい。繊維間を接合する方法としては、ケミカルボンド（Ｃｈｅｍｉｃａｌ Ｂｏｎｄ）法、熱融着法等の接合方法が挙げられる。これらの中でも、表面が平滑な不織布基材が得られることから、熱融着法が好ましい。 In the present invention, the nonwoven fabric substrate is not particularly limited. Production methods for forming the base fiber into a sheet form include a spunbond method, a melt-blow method, an electrostatic spinning method, a wet layering method, a carding method, and the like. Is mentioned. Among these, a wet method is preferable because a nonwoven fabric substrate having a thin and dense structure can be obtained. Examples of a method for bonding fibers include bonding methods such as a chemical bond method and a thermal fusion method. Among these, the heat fusion method is preferable because a nonwoven fabric substrate having a smooth surface can be obtained.
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。なお、実施例において、百分率（％）及び部は、断りのない限り、全て質量基準である。また、付与量は絶乾付与量である。なお、実施例１−１〜実施例１−５、実施例２−８は参考例である。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the examples, all percentages (%) and parts are based on mass unless otherwise specified. Moreover, the application amount is the absolute dry application amount. Examples 1-1 to 1-5 and 2-8 are reference examples.
不織布基材Ａの作製
繊度０．０６ｄｔｅｘ（平均繊維径２．４μｍ）、繊維長３ｍｍの配向結晶化ポリエチレンテレフタレート（ＰＥＴ）系短繊維４０質量部と繊度０．１ｄｔｅｘ（平均繊維径３．０μｍ）、繊維長３ｍｍの配向結晶化ＰＥＴ系短繊維２０質量部と繊度０．２ｄｔｅｘ（平均繊維径４．３μｍ）、繊維長３ｍｍの単一成分型バインダー用ＰＥＴ系短繊維（軟化点１２０℃、融点２３０℃）４０質量部とをパルパーにより水中に分散し、濃度１質量％の均一な抄造用スラリーを調製した。この抄造用スラリーを、通気度２７５ｃｍ３／ｃｍ２／ｓｅｃ、組織［上網：平織、下網：畝織］の抄造ワイヤーを設置した傾斜型抄紙機にて、湿式法で抄き上げ、１３５℃のシリンダードライヤー（Ｃｙｌｉｎｄｅｒ Ｄｒｙｅｒ）によって、バインダー用ＰＥＴ系短繊維を接着させて不織布強度を発現させ、目付１２ｇ／ｍ２の不織布とした。さらに、この不織布を、誘電発熱ジャケットロール（金属製熱ロール）及び弾性ロールからなる１ニップ（ｎｉｐ）式熱カレンダーを使用して、熱ロール温度２００℃、線圧１００ｋＮ／ｍ、処理速度３０ｍ／分の条件で熱カレンダー処理し、厚み１８μｍの不織布基材Ａを作製した。
Production of Non-woven Fabric Base A Fineness 0.06 dtex (average fiber diameter 2.4 μm), oriented crystallized polyethylene terephthalate (PET) short fiber 40 mass parts with fiber length 3 mm and fineness 0.1 dtex (average fiber diameter 3.0 μm) , 20 mass parts of oriented crystallized PET short fibers with a fiber length of 3 mm, fineness of 0.2 dtex (average fiber diameter 4.3 μm), single component binder PET short fibers with a fiber length of 3 mm (softening point 120 ° C., melting point) (230 ° C.) 40 parts by mass was dispersed in water with a pulper to prepare a uniform papermaking slurry having a concentration of 1% by mass. This slurry for papermaking was made up by a wet method on an inclined paper machine equipped with a papermaking wire having an air permeability of 275 cm 3 / cm 2 / sec and a structure [upper net: plain weave, lower net: weave], 135 ° C. A cylinder dryer (Cylinder Dyer) was used to bond the PET short fibers for binder to develop the strength of the nonwoven fabric to obtain a nonwoven fabric with a basis weight of 12 g / m 2 . Further, this non-woven fabric was heated at a heat roll temperature of 200 ° C., a linear pressure of 100 kN / m, and a processing speed of 30 m / m, using a 1 nip type thermal calendar composed of a dielectric heating jacket roll (metal hot roll) and an elastic roll. Heat calendering was performed under the conditions of minutes to produce a nonwoven fabric substrate A having a thickness of 18 μm.
不織布基材Ｂの作製
繊度０．０６ｄｔｅｘ（平均繊維径２．４μｍ）、繊維長３ｍｍの配向結晶化ポリエチレンテレフタレート（ＰＥＴ）系短繊維６０質量部と繊度０．２ｄｔｅｘ（平均繊維径４．３μｍ）、繊維長３ｍｍの単一成分型バインダー用ＰＥＴ系短繊維（軟化点１２０℃、融点２３０℃）４０質量部とする以外は不織布基材Ａと同様にして、厚み１８μｍの不織布基材Ｂを作製した。不織布基材Ｂは、繊度の小さな繊維分が多いため、細孔径が小さくなり、不織布基材Ａと比較して、塗工液が浸透しにくい。
Production of Non-woven Fabric Base B Fineness 0.06 dtex (average fiber diameter 2.4 μm), oriented crystallized polyethylene terephthalate (PET) short fiber 60 mass parts with fiber length 3 mm and fineness 0.2 dtex (average fiber diameter 4.3 μm) A non-woven fabric base material B having a thickness of 18 μm is prepared in the same manner as the non-woven fabric base material A except that 40 parts by mass of a PET short fiber (softening point 120 ° C., melting point 230 ° C.) for a single-component binder having a fiber length of 3 mm is used. did. Since the nonwoven fabric base material B has a large amount of fibers with small fineness, the pore diameter is small, and the coating liquid is less likely to penetrate as compared with the nonwoven fabric base material A.
塗工液１Ａの作製
水酸化マグネシウム１００部とポリカルボン酸型高分子界面活性剤０．４部、水１２０部とを混合して十分撹拌した。次に、カルボキシメチルセルロースナトリウム塩（１質量％水溶液の２５℃におけるＢ型粘度が７０００ｍＰａ・ｓ）０．５質量％水溶液３００部及び、ガラス転移点５℃、体積平均粒子径０．２μｍのカルボキシ変性スチレンブタジエン樹脂（ＳＢＲ）エマルション（固形分濃度５０質量％）１０部を混合して十分撹拌し、塗工液１Ａを作製した。なお、塗工液１ＡのＢ型粘度は９７０ｍＰａ・ｓであった。
Preparation of Coating Liquid 1A 100 parts of magnesium hydroxide, 0.4 part of a polycarboxylic acid type polymer surfactant, and 120 parts of water were mixed and sufficiently stirred. Next, 300 parts of carboxymethylcellulose sodium salt (B-type viscosity at 25 ° C. of 1% by weight aqueous solution of 7000 mPa · s) 0.5 part by weight of aqueous solution, glass transition point 5 ° C., carboxy modified with volume average particle size 0.2 μm 10 parts of a styrene butadiene resin (SBR) emulsion (solid content concentration 50% by mass) was mixed and sufficiently stirred to prepare a coating liquid 1A. The B type viscosity of the coating liquid 1A was 970 mPa · s.
塗工液１Ｂの作製
カルボキシメチルセルロースナトリウム塩（１質量％水溶液の２５℃におけるＢ型粘度が７０００ｍＰａ・ｓ）０．５質量％水溶液３００部を１００部にした以外は、塗工液Ａと同じようにして塗工液１Ｂを作製した。なお、塗工液１ＢのＢ型粘度は２００ｍＰａ・ｓであった。
Preparation of Coating Solution 1B Carboxymethylcellulose sodium salt (B-type viscosity at 25 ° C. of 1% by weight aqueous solution is 7000 mPa · s) Same as coating solution A except that 300 parts of 0.5% by weight aqueous solution was changed to 100 parts Thus, a coating liquid 1B was produced. In addition, the B type viscosity of the coating liquid 1B was 200 mPa · s.
実施例１−１
不織布基材Ａ上に、塗工液１Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が１６ｇ／ｍ２となるように塗工後乾燥し、厚み３１μｍのセパレータを作製した。
Example 1-1
On the nonwoven fabric substrate A, the coating liquid 1A was coated with a kiss reverse gravure coater so that the absolute dry application amount was 16 g / m 2, and dried to prepare a separator having a thickness of 31 μm.
実施例１−２
不織布基材Ａ上に、塗工液１Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が８ｇ／ｍ２となるように塗工後乾燥し、さらに、同じ塗工面に再度、塗工液１Ａを、キスリバース方式のグラビアコーターにて絶乾付与量が８ｇ／ｍ２となるように塗工後乾燥し、厚み３０μｍのセパレータを作製した。
Example 1-2
On the nonwoven fabric substrate A, the coating liquid 1A is coated with a kiss reverse gravure coater so as to give an absolutely dry amount of 8 g / m 2 , dried, and then coated again on the same coated surface. The coating liquid 1A was coated with a kiss reverse type gravure coater so that the absolute dry application amount was 8 g / m 2 and then dried to prepare a separator having a thickness of 30 μm.
実施例１−３
不織布基材Ａに代えて、不織布基材Ｂを使用した以外は、実施例１−１と同様にして、厚み２８μｍのセパレータを作製した。
Example 1-3
A separator having a thickness of 28 μm was produced in the same manner as in Example 1-1 except that the nonwoven fabric substrate B was used in place of the nonwoven fabric substrate A.
実施例１−４
塗工液１Ａに代えて、塗工液１Ｂを用いた以外は、実施例１−３と同様にして、厚み２９μｍのセパレータを作製した。
Example 1-4
A separator having a thickness of 29 μm was produced in the same manner as in Example 1-3 except that the coating liquid 1B was used instead of the coating liquid 1A.
実施例１−５
キスリバース方式のグラビアコーターに代えて、含浸式コーターを用いた以外は、実施例１−１と同様にして、厚み３１μｍのセパレータを作製した。
Example 1-5
A separator having a thickness of 31 μm was produced in the same manner as in Example 1-1 except that an impregnation type coater was used instead of the kiss reverse type gravure coater.
比較例１−１
塗工液１Ａに代えて、塗工液１Ｂを用いた以外は、実施例１−１と同様にして、厚み３２μｍのセパレータを作製した。
Comparative Example 1-1
A separator having a thickness of 32 μm was produced in the same manner as in Example 1-1 except that the coating liquid 1B was used in place of the coating liquid 1A.
比較例１−２
２回目の塗工を、１回目の塗工面とは反対の面に行った以外は、実施例１−２と同様にして、厚み３２μｍのセパレータを作製した。
Comparative Example 1-2
A separator having a thickness of 32 μm was prepared in the same manner as in Example 1-2, except that the second coating was performed on the surface opposite to the first coating.
［Ｍｇ／Ｃ比］
各セパレータの表裏面におけるエネルギー分散Ｘ線分光法（ＥＤＳ）によるＭｇ及びＣの強度ピーク比（Ｍｇ／Ｃ比）を、電界放射型走査電子顕微鏡（日本電子（ＪＥＯＬ）製、装置名：ＪＳＭ−０６７００Ｆ）を使用して加速電圧１０ｋＶ、倍率４０倍の視野を３箇所測定し、得られたＭｇ及びＣ由来の特性Ｘ線のピーク強度（特性Ｘ線のカウント数）の比の平均値により求めた。
[Mg / C ratio]
The intensity peak ratio (Mg / C ratio) of Mg and C by energy dispersive X-ray spectroscopy (EDS) on the front and back surfaces of each separator was measured using a field emission scanning electron microscope (manufactured by JEOL, device name: JSM-). Measure the three fields of view with an acceleration voltage of 10 kV and a magnification of 40 times using an average of the ratio of the peak intensity (number of counts of characteristic X-rays) of characteristic X-rays derived from Mg and C. It was.
［厚み］
各セパレータの断面を、ＥＤＳを備えたＳＥＭ装置にて観察した。そして、「マグネシウム（Ｍｇ）を検出した領域」を「無機顔料」とした。「Ｍｇを検出せず、かつ実体が存在する領域」を「基材繊維」とした。「無機顔料の存在比率が４／１である深さ」を「顔料主体層と混在層の境界線」とした。「無機顔料の存在比率が１／４である深さ」を「繊維主体層と混在層の境界線」とした。
[Thickness]
The cross section of each separator was observed with an SEM apparatus equipped with EDS. The “region where magnesium (Mg) was detected” was defined as “inorganic pigment”. “A region where Mg is not detected and an entity exists” was defined as “base fiber”. The “depth at which the abundance ratio of the inorganic pigment is 4/1” was defined as “the boundary line between the pigment main layer and the mixed layer”. The “depth at which the abundance ratio of the inorganic pigment is ¼” was defined as “the boundary line between the fiber main layer and the mixed layer”.
これらの「境界線」から、「顔料主体層」、「混在層」、「繊維主体層」の厚みをそれぞれ求めた（Ｉ、II、III）。「混在層」が「顔料主体層」の反対面まで到達している場合、「繊維主体層」の厚み（III）は「０（零）」とみなした。 From these “boundary lines”, the thicknesses of “pigment main layer”, “mixed layer”, and “fiber main layer” were determined (I, II, III), respectively. When the “mixed layer” reached the opposite side of the “pigment main layer”, the thickness (III) of the “fiber main layer” was regarded as “0 (zero)”.
＜評価＞
［電池の繰り返し充放電特性］
各セパレータを用い、正極活物質がマンガン酸リチウム、負極活物質が人造黒鉛、電解液が溶媒：エチレンカーボネートとジエチルカーボネートの７／３（容量比）混合溶媒、電解質：リチウムヘキサフルオロフォスフェート（ＬｉＰＦ６、濃度：１ｍｏｌ／Ｌ）である設計容量が１００ｍＡｈのラミネート型リチウムイオン二次電池を作製した。なお、電池の組立にあたっては、セパレータの顔料主体層を負極に相対させるようにした。
<Evaluation>
[Repetitive charge / discharge characteristics of battery]
Using each separator, the positive electrode active material is lithium manganate, the negative electrode active material is artificial graphite, the electrolyte is a solvent: 7/3 (volume ratio) mixed solvent of ethylene carbonate and diethyl carbonate, electrolyte: lithium hexafluorophosphate (LiPF) 6 and a concentration of 1 mol / L), a laminate type lithium ion secondary battery having a design capacity of 100 mAh was produced. In assembling the battery, the pigment main layer of the separator was made to face the negative electrode.
その後、各電池について、「２００ｍＡ定電流充電→４．２Ｖ定電圧充電（１時間）→２００ｍＡで定電流放電→２．８Ｖになったら次のサイクル」のシーケンスにて２００サイクルの充放電を行い、［１−（２００サイクル目の放電容量／４サイクル目の放電容量）］×１００（％）として容量低下率を求めた。容量低下率が低い方が、サイクル特性が良好な電池である。 Then, charge and discharge 200 cycles in the sequence of “200 mA constant current charge → 4.2 V constant voltage charge (1 hour) → constant current discharge at 200 mA → next cycle when 2.8 V”. , [1- (discharge capacity at 200th cycle / discharge capacity at 4th cycle)] × 100 (%), the capacity reduction rate was determined. A battery having a lower capacity reduction rate has better cycle characteristics.
１：容量低下率が１０％未満
２：容量低下率が１０％以上２０％未満
３：容量低下率が２０％以上３０％未満
４：容量低下率が３０％以上４０％未満
５：容量低下率が４０％以上
1: Capacity reduction rate is less than 10% 2: Capacity reduction rate is 10% or more and less than 20% 3: Capacity reduction rate is 20% or more and less than 30% 4: Capacity reduction rate is 30% or more and less than 40% 5: Capacity reduction rate 40% or more
表１から明らかなように、顔料主体層、混在層、繊維主体層がこの順に重なって構成され、且つ顔料主体層側の面のＭｇ／Ｃ比が４．０以上である実施例１−１〜１−５のセパレータは、繰り返し充放電における容量低下率が４０％未満であり、サイクル特性が良好という効果が達成できた。これに対し、繊維主体層がない比較例１−１及び１−２のセパレータは、容量低下率が４０％以上であり、サイクル特性が悪かった。 As is apparent from Table 1, the pigment main layer, the mixed layer, and the fiber main layer are configured to overlap in this order, and the Mg / C ratio of the surface on the pigment main layer side is 4.0 or more. Example 1-1 The capacity reduction rate in repeated charge / discharge was less than 40%, and the effect that the cycle characteristics were good was achieved in the separators of ˜1-5. On the other hand, the separators of Comparative Examples 1-1 and 1-2 having no fiber main layer had a capacity reduction rate of 40% or more and poor cycle characteristics.
また、実施例１−１〜１−５のセパレータを比較すると、繊維主体層側の面のＭｇ／Ｃ比が１．０×１０−１以上１．０未満である実施例１−１〜１−４のセパレータは、繰り返し充放電における容量低下率がより小さく、サイクル特性がより良好という効果を達成できた。 Moreover, when the separators of Examples 1-1 to 1-5 are compared, Examples 1-1 to 1 in which the Mg / C ratio of the surface on the fiber main layer side is 1.0 × 10 −1 or more and less than 1.0. The separator of -4 was able to achieve the effect that the capacity reduction rate in repeated charge and discharge was smaller and the cycle characteristics were better.
塗工液２Ａの作製
ベーマイトアルミナ１００部とポリカルボン酸型高分子界面活性剤０．４部、水１２０部とを混合して十分撹拌した。次に、カルボキシメチルセルロースナトリウム塩（１質量％水溶液の２５℃におけるＢ型粘度が７０００ｍＰａ・ｓ）０．５質量％水溶液３００部及び、ガラス転移点５℃、体積平均粒子径０．２μｍのカルボキシ変性スチレン−ブタジエン樹脂（ＳＢＲ）エマルション（固形分濃度５０質量％）１０部を混合して十分撹拌し、塗工液２Ａを作製した。塗工液２ＡのＢ型粘度は１０２０ｍＰａ・ｓであった。
Preparation of coating liquid 2A 100 parts of boehmite alumina, 0.4 part of a polycarboxylic acid type polymer surfactant, and 120 parts of water were mixed and sufficiently stirred. Next, 300 parts of carboxymethylcellulose sodium salt (B-type viscosity at 25 ° C. of 1% by weight aqueous solution of 7000 mPa · s) 0.5 part by weight of aqueous solution, glass transition point 5 ° C., carboxy modified with volume average particle size 0.2 μm 10 parts of a styrene-butadiene resin (SBR) emulsion (solid content concentration 50% by mass) was mixed and sufficiently stirred to prepare a coating liquid 2A. The B-type viscosity of the coating liquid 2A was 1020 mPa · s.
塗工液２Ｂの作製
カルボキシメチルセルロースナトリウム塩（１質量％水溶液の２５℃におけるＢ型粘度が７０００ｍＰａ・ｓ）０．５質量％水溶液３００部を２００部にした以外は塗工液２Ａと同じようにして塗工液２Ｂを作製した。塗工液２ＢのＢ型粘度は５１０ｍＰａ・ｓであった。
Preparation of Coating Solution 2B Carboxymethylcellulose sodium salt (B-type viscosity at 25 ° C. of 1% by weight aqueous solution is 7000 mPa · s) Same as coating solution 2A except that 300 parts of 0.5% by weight aqueous solution was changed to 200 parts. Thus, a coating liquid 2B was produced. The B-type viscosity of the coating liquid 2B was 510 mPa · s.
塗工液２Ｃの作製
カルボキシメチルセルロースナトリウム塩（１質量％水溶液の２５℃におけるＢ型粘度が７０００ｍＰａ・ｓ）０．５質量％水溶液３００部を１００部にした以外は塗工液２Ａと同じようにして塗工液２Ｃを作製した。塗工液２ＣのＢ型粘度は２００ｍＰａ・ｓであった。
Preparation of Coating Solution 2C Carboxymethylcellulose sodium salt (B-type viscosity at 25 ° C. of 1% by weight aqueous solution is 7000 mPa · s) Same as coating solution 2A, except that 300 parts of 0.5% by weight aqueous solution was changed to 100 parts. Thus, a coating liquid 2C was produced. The B-type viscosity of the coating liquid 2C was 200 mPa · s.
塗工液２Ｄの作製
カルボキシメチルセルロースナトリウム塩（１質量％水溶液の２５℃におけるＢ型粘度が７０００ｍＰａ・ｓ）０．５質量％水溶液３００部を２００部にした以外は塗工液１Ａと同じようにして塗工液２Ｄを作製した。塗工液２ＤのＢ型粘度は４９０ｍＰａ・ｓであった。
Preparation of coating liquid 2D Carboxymethylcellulose sodium salt (B-type viscosity at 25 ° C. of 1% by weight aqueous solution is 7000 mPa · s) 0.5 parts by weight of aqueous solution was changed to 200 parts in the same manner as coating liquid 1A. Thus, a coating liquid 2D was produced. The B-type viscosity of the coating liquid 2D was 490 mPa · s.
実施例２−１
不織布基材Ｂ上に、塗工液２Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が５ｇ／ｍ２となるように塗工後乾燥し、さらに、同じ塗工面に、塗工液１Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が５ｇ／ｍ２となるように塗工後乾燥し、厚み２６μｍのセパレータを作製した。
Example 2-1
On the nonwoven fabric base material B, the coating liquid 2A is coated with a kiss reverse gravure coater so that the dryness imparting amount is 5 g / m 2 and then dried. Further, the coating liquid is coated on the same coated surface. The liquid 1A was coated and dried with a kiss reverse gravure coater so that the absolute dry application amount was 5 g / m 2 , thereby preparing a separator having a thickness of 26 μm.
実施例２−２
不織布基材Ｂ上に、塗工液２Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が５ｇ／ｍ２となるように塗工後乾燥し、さらに、同じ塗工面に、塗工液１Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が３ｇ／ｍ２となるように塗工後乾燥し、厚み２４μｍのセパレータを作製した。
Example 2-2
On the nonwoven fabric base material B, the coating liquid 2A is coated with a kiss reverse gravure coater so that the dryness imparting amount is 5 g / m 2 and then dried. Further, the coating liquid is coated on the same coated surface. The liquid 1A was coated and dried with a kiss reverse gravure coater so that the absolute dry application amount was 3 g / m 2 , thereby preparing a separator having a thickness of 24 μm.
実施例２−３
不織布基材Ｂ上に、塗工液２Ａを、キスリバース方式のグラビアコーターにて絶乾付与量が５ｇ／ｍ２となるように塗工後乾燥し、さらに、同じ塗工面に、塗工液１Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が１．０ｇ／ｍ２となるように塗工後乾燥し、厚み２２μｍのセパレータを作製した。
Example 2-3
On the non-woven fabric base B, the coating liquid 2A is coated with a kiss reverse gravure coater so that the absolute dry application amount is 5 g / m 2 and then dried. Further, the coating liquid is applied to the same coated surface. 1A was coated and dried with a kiss reverse gravure coater so that the absolute dry application amount was 1.0 g / m 2 to prepare a separator having a thickness of 22 μm.
実施例２−４
塗工液１Ａに代えて、塗工液２Ｄを用いた以外は、実施例２−１と同様にして、厚み２５μｍのセパレータを作製した。
Example 2-4
A separator having a thickness of 25 μm was prepared in the same manner as in Example 2-1, except that the coating liquid 2D was used instead of the coating liquid 1A.
実施例２−５
不織布基材Ｂ上に、塗工液２Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が２ｇ／ｍ２となるように塗工後乾燥し、さらに、同じ塗工面に、塗工液１Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が５ｇ／ｍ２となるように塗工後乾燥し、厚み２２μｍのセパレータを作製した。
Example 2-5
On the non-woven fabric base B, the coating liquid 2A is coated with a kiss reverse gravure coater so that the dryness imparting amount is 2 g / m 2 and then dried. The liquid 1A was coated and dried with a kiss reverse gravure coater so that the dryness imparting amount was 5 g / m 2 , thereby preparing a separator having a thickness of 22 μm.
実施例２−６
塗工液２Ａに代えて、塗工液２Ｂを用い、さらに塗工液１Ａに代えて、塗工液２Ｄを用いた以外は、実施例２−１と同様にして、厚み２４μｍのセパレータを作製した。
Example 2-6
A separator having a thickness of 24 μm was prepared in the same manner as in Example 2-1, except that the coating liquid 2B was used instead of the coating liquid 2A, and the coating liquid 2D was used instead of the coating liquid 1A. did.
実施例２−７
不織布基材Ａ上に、塗工液２Ｃを、キスリバース方式のグラビアコーターにて絶乾付与量が５ｇ／ｍ２となるように塗工後乾燥し、さらに、同じ塗工面に、塗工液１Ａを、キスリバース方式のグラビアコーターにて絶乾付与量が５ｇ／ｍ２となるように塗工後乾燥し、厚み２５μｍのセパレータを作製した。
Example 2-7
On the non-woven fabric substrate A, the coating liquid 2C is coated with a kiss reverse gravure coater so that the dryness imparting amount is 5 g / m 2 and then dried. Further, the coating liquid is applied to the same coated surface. 1A was coated with a kiss reverse gravure coater so as to give an absolutely dry amount of 5 g / m 2 and dried to prepare a separator having a thickness of 25 μm.
実施例２−８
不織布基材Ｂ上に、塗工液２Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が３ｇ／ｍ２となるように塗工後乾燥し、さらに、同じ塗工面に、塗工液１Ｂを、キスリバース方式のグラビアコーターにて、絶乾付与量が５ｇ／ｍ２となるように塗工後乾燥し、厚み２４μｍのセパレータを作製した。
Example 2-8
On the nonwoven fabric substrate B, the coating liquid 2A is coated with a kiss reverse gravure coater so as to give an absolute dryness of 3 g / m 2 and then dried. The liquid 1B was coated and dried with a kiss reverse gravure coater so that the absolute dry application amount was 5 g / m 2 , thereby preparing a separator having a thickness of 24 μm.
比較例２−１
不織布基材Ａ上に、塗工液２Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が１．０ｇ／ｍ２となるように塗工後乾燥し、さらに、同じ塗工面に、塗工液１Ａを、キスリバース方式のグラビアコーターにて、絶乾付与量が３ｇ／ｍ２となるように塗工後乾燥し、厚み２１μｍのセパレータを作製した。
Comparative Example 2-1
On the non-woven fabric substrate A, the coating liquid 2A is coated with a kiss reverse gravure coater so as to give an absolutely dry amount of 1.0 g / m 2 and then dried. Further, on the same coated surface, The coating liquid 1A was coated and dried with a kiss reverse gravure coater so that the absolute dry application amount was 3 g / m 2 , thereby preparing a separator having a thickness of 21 μm.
比較例２−２
不織布基材Ａ上に、塗工液２Ａを、キスリバース方式のグラビアコーターにて絶乾付与量が５ｇ／ｍ２となるように塗工後乾燥し、厚み２２μｍのセパレータを作製した。
Comparative Example 2-2
On the nonwoven fabric substrate A, the coating liquid 2A was coated and dried with a kiss reverse gravure coater so that the absolute dry application amount was 5 g / m 2 , thereby preparing a separator having a thickness of 22 μm.
＜評価＞
［Ｍｇ／Ｃ比、Ｍｇ／Ａｌ比、Ａｌ／Ｃ比］
各セパレータにおいて、顔料主体層側の面と繊維主体層側の面のＥＤＳによるＭｇ／Ａｌ比、顔料主体層側の面のＭｇ／Ｃ比、繊維主体層側の面のＡｌ／Ｃ比を、電界放射型走査電子顕微鏡（日本電子（ＪＥＯＬ）製、装置名：ＪＳＭ−０６７００Ｆ）を使用して加速電圧１０ｋＶ、倍率１００倍の視野を３箇所測定し、得られたＭｇ、Ａｌ及びＣ由来の特性Ｘ線のピーク強度（特性Ｘ線のカウント数）の比の平均値により求めた。
<Evaluation>
[Mg / C ratio, Mg / Al ratio, Al / C ratio]
In each separator, the Mg / Al ratio by the EDS of the pigment main layer side surface and the fiber main layer side surface, the Mg / C ratio of the pigment main layer side surface, the Al / C ratio of the fiber main layer side surface, Using a field emission scanning electron microscope (manufactured by JEOL (JEOL), apparatus name: JSM-06700F), three fields of view having an acceleration voltage of 10 kV and a magnification of 100 times were measured, and the resulting Mg, Al and C-derived The average value of the ratio of the peak intensity of characteristic X-rays (count of characteristic X-rays) was obtained.
［厚み］
各セパレータの断面を、ＥＤＳを備えたＳＥＭ装置にて観察した。そして、「マグネシウム（Ｍｇ）又はアルミニウム（Ａｌ）を検出した領域」を「無機顔料」とした。「Ｍｇ又はＡｌを検出せず、かつ実体が存在する領域」を「基材繊維」とした。「無機顔料の存在比率が４／１である深さ」を「顔料主体層と混在層の境界線」とした。「無機顔料の存在比率が１／４である深さ」を「繊維主体層と混在層の境界線」とした。
[Thickness]
The cross section of each separator was observed with an SEM apparatus equipped with EDS. The “region where magnesium (Mg) or aluminum (Al) was detected” was defined as “inorganic pigment”. “A region where Mg or Al is not detected and an entity exists” was defined as “base fiber”. The “depth at which the abundance ratio of the inorganic pigment is 4/1” was defined as “the boundary line between the pigment main layer and the mixed layer”. The “depth at which the abundance ratio of the inorganic pigment is ¼” was defined as “the boundary line between the fiber main layer and the mixed layer”.
これらの「境界線」から、「顔料主体層」、「混在層」、「繊維主体層」の厚みをそれぞれ求めた（Ｉ、II、III）。「混在層」が「顔料主体層」の反対面まで到達している場合、「繊維主体層」の厚み（III）は「０（零）」とみなした。 From these “boundary lines”, the thicknesses of “pigment main layer”, “mixed layer”, and “fiber main layer” were determined (I, II, III), respectively. When the “mixed layer” reached the opposite side of the “pigment main layer”, the thickness (III) of the “fiber main layer” was regarded as “0 (zero)”.
［ピンホール評価］
作製したセパレータについて、セパレータのピンホールの状態についてＡ４サイズ１枚を、透過光を用いて目視にて確認し、次の度合いで評価した。結果を表２に記した。
[Pinhole evaluation]
About the produced separator, about the state of the pinhole of a separator, one A4 size was confirmed visually using the transmitted light, and it evaluated by the following degree. The results are shown in Table 2.
１：目視でのピンホールの発生は見られない。
２：うっすらと透過光が観察される部分が存在する。
３：明らかな透過光が僅かに観察される。
４：明らかな透過光が多数観察される。
1: Generation | occurrence | production of the pinhole by visual observation is not seen.
2: There is a portion where transmitted light is observed slightly.
3: Slight clear transmitted light is observed.
4: Many clear transmitted lights are observed.
表２から明らかなように、顔料主体層、混在層、繊維主体層がこの順に重なって構成され、且つ顔料主体層側の面のＭｇ／Ｃ比が４．０以上である実施例２−１〜２−８のセパレータでは、ピンホール抑制効果が達成できた。これに対し、顔料主体層側の面のＭｇ／Ｃ比が４．０未満である比較例２−１のセパレータ及びＭｇが検出されなかった比較例２−２のセパレータでは、ピンホールが悪化する傾向が見られた。 As is clear from Table 2, the pigment main layer, the mixed layer, and the fiber main layer are overlapped in this order, and the Mg / C ratio of the surface on the pigment main layer side is 4.0 or more. With the separator of ˜2-8, the pinhole suppressing effect could be achieved. On the other hand, the pinhole deteriorates in the separator of Comparative Example 2-1 in which the Mg / C ratio on the pigment main layer side surface is less than 4.0 and the separator of Comparative Example 2-2 in which Mg was not detected. There was a trend.
実施例２−１〜２−８のセパレータを比較すると、顔料主体層側の面のＭｇ／Ａｌ比が２０以上であり、繊維主体層側の面のＭｇ／Ａｌ比が１．０×１０−２以上１．０未満である実施例２−１〜２−７のセパレータでは、繊維主体層側の面のＭｇ／Ａｌ比が１．０以上である実施例２−８のセパレータと比較して、より高いピンホール抑制効果が達成できた。 When the separators of Examples 2-1 to 2-8 are compared, the Mg / Al ratio on the surface on the pigment main layer side is 20 or more, and the Mg / Al ratio on the surface on the fiber main layer side is 1.0 × 10 −. In the separators of Examples 2-1 to 2-7 that are 2 or more and less than 1.0, compared to the separator of Example 2-8 in which the Mg / Al ratio on the fiber main layer side surface is 1.0 or more A higher pinhole suppression effect was achieved.
実施例２−１〜２−７のセパレータを比較すると、繊維主体層側の面のＡｌ／Ｃ比が１．０×１０−２以上１．０未満である実施例２−１、２−２、２−４及び２−６のセパレータでは、繊維主体層側の面のＡｌ／Ｃ比が１．０×１０−２未満である実施例２−５のセパレータ及び１．０以上である実施例２−７のセパレータと比較して、更に高いピンホール抑制効果が達成できた。また、実施例２−３のセパレータは、顔料主体層側の面のＭｇ／Ｃ比が４．１であり、繊維主体層側の面のＭｇ／Ａｌ比が１．０×１０−２であり、どちらの値も下限に近いことから、ピンホールの抑制効果が実施例２−７のセパレータと同程度であった。
Example Comparing the separator 2-1 to 2-7, Example 2-1,2- 2 Al / C ratio of the surface of the fiber-based layer side is less than 1.0 × 10 -2 1.0 in the separator of 2-4 and 2-6, is Al / C ratio of the surface of the fiber-based layer side 1.0 × 10 below -2 is example 2 5 of the separator and 1.0 above example Compared with the 2-7 separator, a higher pinhole suppression effect could be achieved. Further, in the separator of Example 2-3, the Mg / C ratio on the surface on the pigment main layer side is 4.1, and the Mg / Al ratio on the surface on the fiber main layer side is 1.0 × 10 −2 . Since both values were close to the lower limit, the effect of suppressing pinholes was almost the same as that of the separator of Example 2-7.
本発明のリチウムイオン電池用セパレータの活用例としては、リチウムイオン二次電池用セパレータ、リチウムポリマーイオン二次電池用セパレータが好適である。 As a utilization example of the separator for lithium ion batteries of the present invention, a separator for lithium ion secondary batteries and a separator for lithium polymer ion secondary batteries are suitable.
Claims (2)
該セパレータが、無機顔料を主体としてなる層、無機顔料と基材繊維が混在してなる層、基材繊維を主体としてなる層がこの順に重なって構成されており、
無機顔料を主体としてなる層として、無機顔料としてマグネシウム（Ｍｇ）化合物を含有してなるＭ層を有し、
且つ無機顔料を主体としてなる層側の面のエネルギー分散Ｘ線分光法によるＭｇ及び炭素（Ｃ）の強度ピーク値の比（Ｍｇ／Ｃ比）が４．０以上であり、
無機顔料を主体としてなる層として、無機顔料としてアルミニウム（Ａｌ）化合物を含有してなるＡ層を更に有し、
不織布基材上のＡ層がＭ層で覆われており、
且つ無機顔料を主体としてなる層側の面のエネルギー分散Ｘ線分光法によるＭｇ及びＡｌの強度ピーク値の比（Ｍｇ／Ａｌ比）が２０以上であり、
基材繊維を主体としてなる層側の面のエネルギー分散Ｘ線分光法によるＭｇ及びＡｌの強度ピーク値の比（Ｍｇ／Ａｌ比）が１．０×１０ −２ 以上１．０未満であることを特徴とするリチウムイオン電池用セパレータ。 In the lithium ion battery separator formed by applying an inorganic pigment to the nonwoven fabric substrate,
The separator is composed of a layer mainly composed of an inorganic pigment, a layer formed by mixing an inorganic pigment and a base fiber, and a layer mainly composed of a base fiber in this order.
As a layer mainly composed of inorganic pigment, it has an M layer containing a magnesium (Mg) compound as an inorganic pigment,
And the ratio of the intensity peak value of Mg and carbon by energy dispersive X-ray spectroscopy of the surface of formed of an inorganic pigment mainly layer side (C) (Mg / C ratio) Ri der of 4.0 or more,
As a layer mainly composed of inorganic pigment, it further has an A layer containing an aluminum (Al) compound as an inorganic pigment,
A layer on the nonwoven fabric substrate is covered with M layer,
And the ratio of Mg and Al intensity peak value (Mg / Al ratio) by energy dispersive X-ray spectroscopy of the layer side surface mainly composed of inorganic pigment is 20 or more,
The ratio of the intensity peak value of Mg and Al (Mg / Al ratio) Ru less than 1.0 der 1.0 × 10 -2 or more by energy dispersive X-ray spectroscopy of a layer-side surface comprising a base fiber principally The separator for lithium ion batteries characterized by the above-mentioned.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014208950A JP6294803B2 (en) | 2013-11-20 | 2014-10-10 | Lithium ion battery separator |
| CN201410669748.0A CN104659312B (en) | 2013-11-20 | 2014-11-20 | Isolator Used For Lithium Ion Battery |
| JP2018012234A JP6892399B2 (en) | 2013-11-20 | 2018-01-29 | Separator for lithium-ion batteries |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013239567 | 2013-11-20 | ||
| JP2013239567 | 2013-11-20 | ||
| JP2014078399 | 2014-04-07 | ||
| JP2014078399 | 2014-04-07 | ||
| JP2014208950A JP6294803B2 (en) | 2013-11-20 | 2014-10-10 | Lithium ion battery separator |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018012234A Division JP6892399B2 (en) | 2013-11-20 | 2018-01-29 | Separator for lithium-ion batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015207547A JP2015207547A (en) | 2015-11-19 |
| JP6294803B2 true JP6294803B2 (en) | 2018-03-14 |
Family
ID=54604178
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014208950A Active JP6294803B2 (en) | 2013-11-20 | 2014-10-10 | Lithium ion battery separator |
| JP2018012234A Active JP6892399B2 (en) | 2013-11-20 | 2018-01-29 | Separator for lithium-ion batteries |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018012234A Active JP6892399B2 (en) | 2013-11-20 | 2018-01-29 | Separator for lithium-ion batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP6294803B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102591524B1 (en) * | 2017-06-19 | 2023-10-18 | 니폰 제온 가부시키가이샤 | Composition for porous membranes for non-aqueous secondary batteries, porous membranes for non-aqueous secondary batteries, and non-aqueous secondary batteries |
| WO2019039357A1 (en) | 2017-08-21 | 2019-02-28 | 日本ゼオン株式会社 | Laminate for nonaqueous secondary batteries, method for producing same, wound body for nonaqueous secondary batteries, and method for producing nonaqueous secondary battery member |
| JP7046654B2 (en) * | 2018-03-07 | 2022-04-04 | 株式会社日本触媒 | Separator used for batteries containing zinc negative electrode and batteries containing zinc negative electrode |
| CN112106225B (en) * | 2018-08-30 | 2023-01-06 | 松下知识产权经营株式会社 | Nonaqueous electrolyte secondary battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011018590A (en) * | 2009-07-10 | 2011-01-27 | Hitachi Maxell Ltd | Slurry for insulating layer forming, separator for lithium ion secondary battery and manufacturing method thereof, and lithium ion secondary battery |
| JP5552040B2 (en) * | 2010-12-22 | 2014-07-16 | 三菱製紙株式会社 | Separator for lithium secondary battery |
| JP6018498B2 (en) * | 2012-02-09 | 2016-11-02 | 三菱製紙株式会社 | Lithium ion secondary battery separator base material, method for producing lithium ion secondary battery separator base material, and lithium ion secondary battery separator |
| JP5829552B2 (en) * | 2012-03-06 | 2015-12-09 | 三菱製紙株式会社 | Method for producing separator for metal ion secondary battery |
| JP5829557B2 (en) * | 2012-03-15 | 2015-12-09 | 三菱製紙株式会社 | Method for producing metal ion secondary battery separator |
-
2014
- 2014-10-10 JP JP2014208950A patent/JP6294803B2/en active Active
-
2018
- 2018-01-29 JP JP2018012234A patent/JP6892399B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015207547A (en) | 2015-11-19 |
| JP6892399B2 (en) | 2021-06-23 |
| JP2018085347A (en) | 2018-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6542343B2 (en) | Non-woven fabric substrate for lithium ion secondary battery separator and lithium ion secondary battery separator | |
| JP6892399B2 (en) | Separator for lithium-ion batteries | |
| JP6294989B2 (en) | Lithium ion battery separator | |
| CN107230765A (en) | Lithium ion battery separator | |
| JP6049595B2 (en) | Lithium ion battery separator | |
| JP6408810B2 (en) | Lithium secondary battery separator and method for producing lithium secondary battery separator | |
| JP6049588B2 (en) | Lithium ion battery separator | |
| CN111615765B (en) | Coating liquid for lithium ion battery separator and lithium ion battery separator | |
| JP2016009579A (en) | Separator for lithium ion secondary battery | |
| CN104659312B (en) | Isolator Used For Lithium Ion Battery | |
| JP2012190622A (en) | Separator for electrochemical element, and electrochemical element including the same | |
| JP6016512B2 (en) | Lithium secondary battery separator and lithium secondary battery | |
| JP6962924B2 (en) | Thin high-density non-woven fabric separator for energy storage equipment and its manufacturing method | |
| JP6013815B2 (en) | Lithium ion battery separator | |
| JP2013254570A (en) | Lithium ion battery separator and lithium ion battery | |
| JP2014022094A (en) | Separator for lithium ion battery | |
| JP6016466B2 (en) | Lithium ion battery separator coating liquid and lithium ion battery separator | |
| JP6018526B2 (en) | Metal ion secondary battery separator | |
| JP2013178937A (en) | Unwoven fabric for electrochemical element separator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161206 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20171019 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20171129 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180129 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180206 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180216 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6294803 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |