JP2013186958A - Method for manufacturing metal ion secondary battery separator, and metal ion secondary battery separator - Google Patents
Method for manufacturing metal ion secondary battery separator, and metal ion secondary battery separator Download PDFInfo
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- JP2013186958A JP2013186958A JP2012049134A JP2012049134A JP2013186958A JP 2013186958 A JP2013186958 A JP 2013186958A JP 2012049134 A JP2012049134 A JP 2012049134A JP 2012049134 A JP2012049134 A JP 2012049134A JP 2013186958 A JP2013186958 A JP 2013186958A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 16
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- 239000011248 coating agent Substances 0.000 claims abstract description 97
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 239000000049 pigment Substances 0.000 claims abstract description 46
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims description 30
- 238000012423 maintenance Methods 0.000 description 13
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 11
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- -1 polyethylene terephthalate Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
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- 229910001593 boehmite Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
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- 230000007423 decrease Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- 238000003860 storage Methods 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
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- 238000007600 charging Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 230000005684 electric field Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
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- 229920001296 polysiloxane Polymers 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 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
- 229920002148 Gellan gum Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
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- 229920001145 Poly(N-vinylacetamide) Polymers 0.000 description 1
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- 229920000297 Rayon Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229920002310 Welan gum Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
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- 229920001525 carrageenan Polymers 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 235000010492 gellan gum Nutrition 0.000 description 1
- 239000000216 gellan gum Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 229920005672 polyolefin resin Polymers 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- 239000002964 rayon Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 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
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
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- 235000019698 starch Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 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)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、不織布基材に顔料を担持させて成る、初期充放電効率が高く、且つ放電容量維持率に優れた二次電池用セパレータ及び安定生産可能な該二次電池用セパレータの製造方法に関するものである。 TECHNICAL FIELD The present invention relates to a secondary battery separator having a high initial charge / discharge efficiency and an excellent discharge capacity retention rate, which is formed by supporting a pigment on a nonwoven fabric substrate, and a method for producing the secondary battery separator capable of stable production. Is.
近年、ノートパソコンや携帯電話に代表される各種情報端末機器は、急激に小型化、軽量化、薄型化が成されると共に、広く普及している。また、ハイブリッド自動車、電気自動車、家庭用蓄電池なども普及しつつある。このような背景により、これらの電源又は蓄電体として高エネルギー密度の二次電池(蓄電池)の要求が高まっており、中でも、作動電圧が高く、高エネルギー密度を有する電池としてリチウムイオン二次電池、ナトリウムイオン二次電池等の金属イオンを用いたものが注目されている。 2. Description of the Related Art In recent years, various information terminal devices typified by notebook personal computers and mobile phones are rapidly becoming smaller, lighter, and thinner, and widely used. In addition, hybrid vehicles, electric vehicles, household storage batteries, and the like are becoming popular. Due to such a background, the demand for high energy density secondary batteries (storage batteries) as these power supplies or power storage units is increasing, among them, lithium ion secondary batteries as batteries having high operating voltage and high energy density, Those using metal ions such as sodium ion secondary batteries have attracted attention.
該二次電池は一般に、正極と負極の間に電気絶縁性と保液性を備えたセパレータを介装してなる電極群を、有機電界液等の非水電界液と共に容器内に収容し、密閉することで形成される。従来、二次電池用セパレータとしては、ポリオレフィン微孔膜を使用するのが一般的であった。ポリオレフィン微孔膜は、電池内部の温度が130℃近傍になった場合、溶融して微孔膜が閉塞する機能(シャットダウン機能)を持つため、短絡の際などに電池の安全性を向上させることができる。しかしながら、ポリオレフィン微孔膜は、何らかの状況によりさらに温度が上昇した場合、ポリオレフィン自体が溶融してショートし、熱暴走を引き起こす可能性が示唆されている。そのため、現在は200℃付近でも溶融及び収縮しない耐熱性セパレータが開発されている。 The secondary battery generally accommodates an electrode group having a separator having electrical insulation and liquid retention between a positive electrode and a negative electrode together with a nonaqueous electric field liquid such as an organic electric field liquid, It is formed by sealing. Conventionally, a polyolefin microporous membrane has been generally used as a secondary battery separator. Polyolefin microporous membrane has a function (shutdown function) that melts and closes the microporous membrane when the temperature inside the battery reaches around 130 ° C, thus improving battery safety in the event of a short circuit. Can do. However, it has been suggested that if the temperature of the polyolefin microporous membrane further increases due to some circumstances, the polyolefin itself may melt and short-circuit, causing thermal runaway. Therefore, a heat-resistant separator that does not melt and shrink even at around 200 ° C. has been developed at present.
耐熱性セパレータとしては、ポリエステル系繊維で構成した不織布、ポリエステル系繊維に耐熱繊維であるアラミド繊維を配合した不織布が開示されている(例えば、特許文献1〜3参照)。しかしながら、これらは孔径が大きく、内部短絡が起き、この内部短絡は電池の初期充放電効率を悪化させる。本発明において、初期充放電効率とは、放電容量を充電容量で除したものを指し、セパレータに内部短絡が生じた場合、主に充電容量が増加し、初期充放電効率が悪化することとなる。初期充放電効率の悪化は、負極上で過度の電界液の分解を誘発させるため、電界液の枯渇や、負極表面やセパレータの細孔部への分解生成物の堆積を招き、電池の充放電効率や容量低下を引き起こし、問題となる。 As a heat-resistant separator, a nonwoven fabric composed of polyester fibers and a nonwoven fabric obtained by blending polyester fibers with aramid fibers that are heat-resistant fibers are disclosed (for example, see Patent Documents 1 to 3). However, these have a large hole diameter and an internal short circuit occurs, and this internal short circuit deteriorates the initial charge / discharge efficiency of the battery. In the present invention, the initial charge / discharge efficiency refers to the value obtained by dividing the discharge capacity by the charge capacity. When an internal short circuit occurs in the separator, the charge capacity mainly increases and the initial charge / discharge efficiency deteriorates. . The deterioration of the initial charge / discharge efficiency induces excessive decomposition of the electrolysis solution on the negative electrode, leading to depletion of the electrolysis solution and the deposition of decomposition products on the negative electrode surface and the pores of the separator. This causes problems in efficiency and capacity reduction.
また、ポリオレフィン微孔膜に、ポリエステル系繊維で構成した不織布を積層させて複合化する例が記載されている(例えば、特許文献4参照)。さらに、不織布や織布に、顔料や樹脂を塗工することで担持させ、耐熱性を持たせる例が開示されている(例えば、特許文献5〜7)。しかしながら、基材として用いられる不織布は孔が大きく、表面の平滑性が低いため、塗工した際に表面のバラツキが大きく塗層が不均一となり、塗層が不均一になるとセパレータ内の電流密度にムラが生じ、局所的に負荷がかかるため、電池の放電容量維持率が悪化し易い。本発明において、放電容量維持率とは、充電容量を放電容量で除したものを指し、セパレータに局所的に負荷がかかると、主に充電容量が低下し、放電容量維持率が低下する。放電容量維持率は電池の寿命を示唆しており、これが低いものは電池の寿命が短いため、問題となる。 Moreover, the example which laminates | stacks the nonwoven fabric comprised with the polyester-type fiber on the polyolefin microporous film, and is compounded is described (for example, refer patent document 4). Furthermore, examples in which a nonwoven fabric or a woven fabric is supported by applying a pigment or a resin to impart heat resistance are disclosed (for example, Patent Documents 5 to 7). However, since the nonwoven fabric used as the base material has large pores and low surface smoothness, the coating has a large surface variation and the coating layer becomes non-uniform. When the coating layer becomes non-uniform, the current density in the separator As a result, unevenness is generated and a load is locally applied, so that the discharge capacity maintenance rate of the battery tends to deteriorate. In the present invention, the discharge capacity retention rate refers to a value obtained by dividing the charge capacity by the discharge capacity. When a load is locally applied to the separator, the charge capacity mainly decreases and the discharge capacity maintenance rate decreases. The discharge capacity maintenance rate suggests the life of the battery, and a low one is problematic because the life of the battery is short.
また、不織布基材へ顔料等を塗工する方法として、特許文献5には、印刷、圧縮、圧入、ローラ塗布、ブレード塗布、刷毛塗り、浸漬塗布、吹き付け塗布、流延塗布が記載されている。特許文献6には、引き上げ塗布、アプリケーター塗布、ダイコーター塗布等の塗布又は含浸によって塗工する方法が記載されている。特許文献7には、ダイコーター、グラビアコーター、リバースロールコーター、スクイズロールコーター、カーテンコーター、ブレードコーター、ナイフコーターなどの塗工機を用いる塗工方法が記載されている。不織布基材への塗工は、不織布の孔が大きいことから塗工後にピンホールと呼ばれる塗工欠陥が生じ易く、この塗工欠陥は内部短絡と同様に電池の初期充放電効率を悪化させる原因となり、さらに塗工の際に顔料や樹脂等の脱落も招き易いといった問題がある。 Moreover, as a method for applying a pigment or the like to a nonwoven fabric substrate, Patent Document 5 describes printing, compression, press-fitting, roller coating, blade coating, brush coating, dip coating, spray coating, and casting coating. . Patent Document 6 describes a method of coating by applying or impregnating such as pulling application, applicator application, die coater application and the like. Patent Document 7 describes a coating method using a coating machine such as a die coater, a gravure coater, a reverse roll coater, a squeeze roll coater, a curtain coater, a blade coater, or a knife coater. Coating to the nonwoven fabric substrate is likely to cause a coating defect called pinhole after coating due to the large pores of the nonwoven fabric, and this coating defect causes the initial charge / discharge efficiency of the battery to deteriorate as well as internal short circuit Furthermore, there is a problem that pigments, resins, and the like are easily dropped during coating.
本発明の課題は、特に不織布基材に顔料を担持させることで成る、初期充放電効率が高く、且つ放電容量維持率に優れた金属イオン使用の二次電池用セパレータを提供すると共に、安定生産可能な金属イオン二次電池用セパレータの製造方法を提供することである。 An object of the present invention is to provide a separator for a secondary battery using metal ions, which has a high initial charge / discharge efficiency and an excellent discharge capacity maintenance rate, and is particularly stable by supporting a pigment on a nonwoven fabric substrate. It is providing the manufacturing method of the separator for possible metal ion secondary batteries.
本発明者らは鋭意検討した結果、課題を解決することができる金属イオン二次電池用セパレータの製造方法及び金属イオン二次電池用セパレータを発明するに到った。即ち、
(1)不織布基材に顔料を含有する塗液を塗工、乾燥する工程を含む金属イオン二次電池用セパレータの製造方法において、該工程においてフィルムを用いることを特徴とする金属イオン二次電池用セパレータの製造方法、
(2)フィルムの片側の面に顔料を含有する塗液を塗工する工程、フィルムの塗工面に不織布基材を貼り合わせる工程、フィルム/顔料を含有する塗液/不織布基材から成るシートを乾燥させる工程、該シートからフィルムを剥離する工程を含む上記(1)記載の金属イオン二次電池用セパレータの製造方法、
(3)フィルムの片側の面に、顔料を含有する塗液を、乾燥前質量で30g/m2以上塗工することを含む、上記(1)又は(2)記載の金属イオン二次電池用セパレータの製造方法、
(4)上記(1)〜(3)のいずれかに記載の金属イオン二次電池用セパレータの製造方法によって製造されてなる金属イオン二次電池用セパレータ、
である。
As a result of intensive studies, the present inventors have invented a method for producing a separator for a metal ion secondary battery and a separator for a metal ion secondary battery that can solve the problem. That is,
(1) In the manufacturing method of the separator for metal ion secondary batteries including the process of apply | coating and drying the coating liquid containing a pigment on a nonwoven fabric base material, a metal ion secondary battery using a film in this process Separator manufacturing method,
(2) A step of applying a coating liquid containing a pigment on one surface of the film, a step of bonding a non-woven fabric base material to the coated surface of the film, and a sheet comprising a coating liquid containing a film / pigment / nonwoven fabric base material A method for producing a separator for a metal ion secondary battery according to the above (1), comprising a step of drying, and a step of peeling the film from the sheet;
(3) For the metal ion secondary battery according to the above (1) or (2), comprising applying a coating liquid containing a pigment to a surface of one side of the film by 30 g / m 2 or more by mass before drying. Manufacturing method of separator,
(4) A metal ion secondary battery separator produced by the method for producing a metal ion secondary battery separator according to any one of (1) to (3) above,
It is.
本発明によって、不織布基材に顔料を担持させることで成る、初期充放電効率が高く、且つ放電容量維持率に優れた金属イオン使用の二次電池用セパレータを提供することができると共に、安定生産可能な該二次電池用セパレータの製造方法を提供することができる。 According to the present invention, it is possible to provide a separator for a secondary battery using a metal ion having a high initial charge / discharge efficiency and an excellent discharge capacity maintenance rate, which is achieved by supporting a pigment on a nonwoven fabric base material, and stable production. The manufacturing method of this possible separator for secondary batteries can be provided.
以下、本発明の内容をさらに具体的に説明する。 Hereinafter, the content of the present invention will be described more specifically.
本発明において、金属イオン二次電池用セパレータ(以下、「セパレータ」と略記する場合がある)は、不織布基材に顔料を担持させることで得られ、フィルムの片側の面に顔料を含有する塗液を塗工する工程、該フィルムの塗工面に不織布基材を貼り合わせる工程、フィルム/顔料を含有する塗液/不織布基材から成るシートを乾燥させる工程、該シートからフィルムを剥離する工程より成る製造方法にて得られる。 In the present invention, a separator for a metal ion secondary battery (hereinafter sometimes abbreviated as “separator”) is obtained by supporting a pigment on a nonwoven fabric substrate, and a coating containing the pigment on one surface of the film. From the step of coating the liquid, the step of bonding the nonwoven fabric substrate to the coated surface of the film, the step of drying the sheet comprising the coating solution / nonwoven fabric substrate containing the film / pigment, and the step of peeling the film from the sheet Obtained by the manufacturing method.
図1は、本発明における金属イオン二次電池用セパレータの製造方法(以下、「製造方法」と略記する場合がある)を実施するための一実施形態に係る塗工機の概略構成を示した図であるが、本発明はこの図によってなんら制限されるものではない。 FIG. 1 shows a schematic configuration of a coating machine according to an embodiment for carrying out a method for producing a separator for a metal ion secondary battery according to the present invention (hereinafter sometimes abbreviated as “manufacturing method”). Although it is a figure, this invention is not restrict | limited at all by this figure.
図1において、帯状のフィルム1の原反は、ロール状に巻き回された、巻回体2として搭載される。巻回体2から巻き出されたフィルムは、搬送系を構成する搬送ロール11〜23で順に搬送され、巻回体3として巻き取られる。矢印25は、フィルムの走行方向を表す。 In FIG. 1, the original fabric of the strip-shaped film 1 is mounted as a wound body 2 wound in a roll shape. The film unwound from the wound body 2 is sequentially transported by the transport rolls 11 to 23 constituting the transport system, and is wound as the wound body 3. Arrow 25 represents the traveling direction of the film.
図1において、搬送ロール13と搬送ロール14との間を走行するフィルム1に向かって、ダイコーター24が設置されており、ダイコーター24にてフィルム1上に顔料を含有する塗液が塗布される。 In FIG. 1, a die coater 24 is installed toward the film 1 traveling between the transport roll 13 and the transport roll 14, and a coating liquid containing a pigment is applied on the film 1 by the die coater 24. The
図1において、帯状の不織布基材4の原反は、ロール状に巻き回された、巻回体5として搭載される。巻回体5から巻き出された不織布基材は、搬送ロール16〜17間で、タッチロール9にて顔料を含有する塗液を塗布されたフィルム1上に圧着される。不織布基材4の圧着により、フィルム/顔料を含有する塗液/不織布基材から成るシート6となった後、搬送ロール17〜21で順に搬送される。この過程で乾燥機10を通過することで、塗液は加熱乾燥され塗膜となり、その後搬送ロール22にて、シート6からフィルム1を剥離することで、セパレータ7が形成され、巻回体8として巻き取られる。矢印26は、不織布4の走行方向を表す。 In FIG. 1, the raw material of the strip-shaped nonwoven fabric base material 4 is mounted as a wound body 5 wound in a roll shape. The nonwoven fabric base material unwound from the wound body 5 is pressure-bonded on the film 1 to which the coating liquid containing the pigment is applied by the touch roll 9 between the transport rolls 16 to 17. After the nonwoven fabric substrate 4 is pressure-bonded, the sheet 6 is formed of a coating liquid / nonwoven fabric substrate containing a film / pigment, and is then sequentially conveyed by conveyance rollers 17 to 21. By passing through the dryer 10 in this process, the coating liquid is heated and dried to form a coating film, and then the separator 1 is formed by peeling the film 1 from the sheet 6 with the transport roll 22, and the wound body 8. Rolled up as The arrow 26 represents the traveling direction of the nonwoven fabric 4.
本発明の製造方法を用いることで、不織布基材表面を顔料で均一に被覆することができるため、正極と負極を良好に分離でき、且つ金属イオンの伝導性に優れたセパレータを得ることができる。本発明において、金属イオンとは、二次電池用途として用いられるものであればなんら限定されるものではないが、例えばCo、Mn、Ni、Al、Li、Ti、Fe、Nb、Na、V、Mo、Mg、Ca、K等のイオンが挙げられ、中でもLiが二次電池にした際の性能、コスト面で好ましい。 By using the production method of the present invention, the surface of the nonwoven fabric substrate can be uniformly coated with a pigment, so that a positive electrode and a negative electrode can be satisfactorily separated and a separator having excellent metal ion conductivity can be obtained. . In the present invention, the metal ion is not limited as long as it is used as a secondary battery. For example, Co, Mn, Ni, Al, Li, Ti, Fe, Nb, Na, V, Examples include ions of Mo, Mg, Ca, K, etc. Among them, Li is preferable in terms of performance and cost when a secondary battery is used.
本発明において、顔料を含有する塗液をフィルムの片側の面に塗工する方式は、なんら制限されるものではなく、ブレードコーター、バーコーター、ロールコーター、エアーナイフコーター、ダイコーター、カーテンコーター、グラビアコーター、マイクログラビアコーター、リップコーター、コンマコーター等に代表される各種方式を自由に選択することができる。不織布基材への直接塗工では、不織布に存在する大きな孔による塗液の脱落や、不織布基材の強度不足などにより、選択可能な塗工方式や塗工量に制限が生じるため好ましくない。これに対し、本発明では、不織布基材への直接塗工では不可能な塗工量であっても塗布することができ、配合設計の自由度も向上させることができる。本発明における絶乾塗工量は、特に限定されるものではないが、3〜30g/m2が好ましく、より好ましくは10〜20g/m2である。3g/m2を下回ると、不織布表面を被覆しきれず、ピンホールが生じ易くなり、30g/m2を上回ると、セパレータの内部抵抗値が高くなり過ぎる場合がある。 In the present invention, the method of coating the pigment-containing coating liquid on one side of the film is not limited at all, blade coater, bar coater, roll coater, air knife coater, die coater, curtain coater, Various systems represented by a gravure coater, a micro gravure coater, a lip coater, a comma coater and the like can be freely selected. Direct coating on the nonwoven fabric substrate is not preferable because the coating method and the coating amount that can be selected are limited due to dropping of the coating liquid due to large holes existing in the nonwoven fabric or insufficient strength of the nonwoven fabric substrate. On the other hand, in this invention, it can apply | coat even if it is a coating amount impossible by the direct coating to a nonwoven fabric base material, and the freedom degree of a compounding design can also be improved. Although the absolute dry coating amount in this invention is not specifically limited, 3-30 g / m < 2 > is preferable, More preferably, it is 10-20 g / m < 2 >. If it is less than 3 g / m 2 , the surface of the nonwoven fabric cannot be covered and pinholes are likely to occur, and if it exceeds 30 g / m 2 , the internal resistance value of the separator may become too high.
本発明において、顔料を含有する塗液をフィルムの片側の面に塗工する際の塗工量は、乾燥前質量で30g/m2以上が好ましく、より好ましくは、30g/m2以上、100g/m2未満である。30g/m2を下回るとフィルム上に均一な塗膜を形成し難く、不織布基材をフィルムの塗工面に張り合わせる際、ムラや塗工欠陥を生じ易くなる。また、100g/m2以上になるとフィルム上に形成される塗膜が厚くなり過ぎるため、不織布基材を貼り合わせ、乾燥しきるまでに塗液の流動が起こり易く、ムラが生じ易くなる。 In the present invention, the coating amount when the pigment-containing coating liquid is applied to one surface of the film is preferably 30 g / m 2 or more, more preferably 30 g / m 2 or more, 100 g in terms of the mass before drying. / M 2 or less. If it is less than 30 g / m 2 , it is difficult to form a uniform coating film on the film, and unevenness and coating defects are likely to occur when the nonwoven fabric substrate is bonded to the coating surface of the film. Moreover, since the coating film formed on a film will become thick too much when it becomes 100 g / m < 2 > or more, a non-woven fabric base material is bonded together, and a coating liquid flows easily until it finishes drying, and it becomes easy to produce a nonuniformity.
本発明に用いるフィルムの種類は、なんら制限されるものではないが、ポリエステル系樹脂フィルム、ポリエチレン系樹脂フィルムなどのポリオレフィン系樹脂フィルム、ポリ塩化ビニル系樹脂フィルム等の合成樹脂フィルム、金属箔、上質紙、中性紙、アート紙、コート紙等の紙類、合成紙、不織布等を自由に選択でき、その厚みも特に限定されるものではない。中でも、合成樹脂フィルムが好ましく、より好ましくは、耐熱性があって安価なポリエチレンテレフタレート(PET)フィルムである。また、単層フィルムだけでなく、積層フィルムを用いることもできる。さらに、離型処理についても、フッ素系の離型剤やシリコーン系の離型剤による一般的な処理方法を採用することができ、特に限定されるものではない。 The type of film used in the present invention is not limited in any way, but a polyester resin film, a polyolefin resin film such as a polyethylene resin film, a synthetic resin film such as a polyvinyl chloride resin film, a metal foil, and a fine quality Paper such as paper, neutral paper, art paper, coated paper, synthetic paper, non-woven fabric and the like can be freely selected, and the thickness thereof is not particularly limited. Among them, a synthetic resin film is preferable, and a polyethylene terephthalate (PET) film that has heat resistance and is inexpensive is more preferable. Moreover, not only a single layer film but a laminated film can also be used. Further, the mold release treatment is not particularly limited, and a general treatment method using a fluorine type mold release agent or a silicone type mold release agent can be employed.
本発明に用いる顔料を含有する塗液は、なんら制限されるものではないが、塗工性の点から顔料、バインダー、増粘剤などの混合液であることが好ましい。また、不織布基材表面を顔料が均一に被覆することが必要であることから、塗液の70質量%以上が顔料であることが好ましく、且つ塗液中のバインダー成分の増量は一般的にセパレータの内部抵抗を上昇させることから、バインダーは塗液の30質量%以下とすることが好ましく、より好ましくは、顔料が塗液の90質量%以上、バインダーが塗液の10質量%以下含まれるものである。 Although the coating liquid containing the pigment used for this invention is not restrict | limited at all, It is preferable that it is a liquid mixture of a pigment, a binder, a thickener, etc. from the point of coating property. Further, since it is necessary to uniformly coat the surface of the nonwoven fabric substrate, it is preferable that 70% by mass or more of the coating liquid is the pigment, and the increase in the binder component in the coating liquid is generally a separator. In order to increase the internal resistance of the coating liquid, the binder is preferably 30% by mass or less of the coating liquid, more preferably 90% by mass or more of the coating liquid and 10% by mass or less of the binder of the coating liquid. It is.
本発明に用いる顔料は、チタン酸カリウム、チタン酸バリウム、ホウ酸アルミニウム、硫酸マグネシウム、窒化ケイ素、炭化ケイ素、ケイ酸カルシウム、ウォラストナイト、繊維石膏、アルミナ、ベーマイト、炭酸カルシウム、酸化亜鉛などの無機顔料及び、メラミン樹脂、尿素−ホルマリン樹脂、ポリエチレン、ナイロン、スチレン系プラスチック顔料、アクリル系プラスチック顔料、炭化水素系プラスチック顔料などの有機顔料から1種以上を自由に選択できる。 Pigments used in the present invention include potassium titanate, barium titanate, aluminum borate, magnesium sulfate, silicon nitride, silicon carbide, calcium silicate, wollastonite, fiber gypsum, alumina, boehmite, calcium carbonate, zinc oxide, etc. One or more kinds can be freely selected from inorganic pigments and organic pigments such as melamine resin, urea-formalin resin, polyethylene, nylon, styrene plastic pigment, acrylic plastic pigment, and hydrocarbon plastic pigment.
本発明に用いるバインダーは、エチレン−酢酸ビニル共重合体、エチレン−エチレンアクリレート共重合体などのエチレン−アクリル酸共重合体、フッ素系ゴム、スチレン−ブタジエンゴム、ポリビニルアルコール、ポリビニルブチラール、ポリビニルピロリドン、ポリ−N−ビニルアセトアミド、架橋アクリル樹脂、ポリウレタン、エポキシ樹脂などから1種以上を自由に選択できる。 The binder used in the present invention is an ethylene-acrylic acid copolymer such as an ethylene-vinyl acetate copolymer or an ethylene-ethylene acrylate copolymer, a fluorine-based rubber, a styrene-butadiene rubber, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, One or more kinds can be freely selected from poly-N-vinylacetamide, crosslinked acrylic resin, polyurethane, epoxy resin and the like.
本発明に用いる増粘剤には、ポリエチレングリコール、ポリアクリル酸、ポリビニルアルコール、ビニルメチルエーテル−無水マレイン酸共重合体などの合成高分子、キサンタンガム、ウェランガム、ジェランガム、グアーガム、カラギーナン、セルロース誘導体、デキストリン、アルファー化デンプンなどのデンプン類などの天然多糖類、モンモリロナイト、ヘクトライトなどの粘度鉱物、ヒュームドシリカ、ヒュームドアルミナ、ヒュームドチタニアなどの無機酸化物類などから1種以上を自由に選択できる。さらに、濡れ剤、消泡剤などを、必要に応じて自由に添加することができる。 The thickener used in the present invention includes synthetic polymers such as polyethylene glycol, polyacrylic acid, polyvinyl alcohol, vinyl methyl ether-maleic anhydride copolymer, xanthan gum, welan gum, gellan gum, guar gum, carrageenan, cellulose derivative, dextrin. , Natural polysaccharides such as starches such as pregelatinized starch, viscosity minerals such as montmorillonite and hectorite, inorganic oxides such as fumed silica, fumed alumina, and fumed titania . Furthermore, a wetting agent, an antifoaming agent, etc. can be freely added as needed.
本発明において、セパレータの製造時に、フィルムの塗工面に不織布基材を貼り合わせる工程を経ることで、セパレータの初期充放電効率及び放電容量維持率を向上させることができる。フィルムへの塗工後、不織布基材を貼り合わせることで、表面平滑性の低い不織布基材に対して塗液を均一に付着させ、不織布基材表面を良好に被覆することができ、塗布ムラが少なく、且つピンホールが極少のセパレータを製造することができる。塗布ムラが生じると、セパレータの均一性が低くなり、金属イオン二次電池内にて、セパレータ中のイオン伝導性にムラが生じ、充放電を繰り返した際に局所的に金属の析出などの不具合が生じ、且つ析出した金属がデンドライト状の結晶となった場合には、内部短絡が発生し、電池容量が低下するため、電池の放電容量維持率が悪化する。また、セパレータにピンホールが存在すると、金属イオン二次電池内部で正極と負極を分離することができず、初期充放電効率が著しく低下し、問題となる。また、フィルムへの塗工後、不織布基材を貼り合わせるまでの距離は、なんら制限されるものではないが、フィルム上での塗液の流動及び不必要な乾燥を抑えられることから、10m以内であることが好ましい。 In this invention, the initial charging / discharging efficiency and discharge capacity maintenance factor of a separator can be improved by passing the process which bonds a nonwoven fabric base material to the coating surface of a film at the time of manufacture of a separator. After coating on the film, the non-woven fabric base material is pasted together, so that the coating liquid can be uniformly attached to the non-woven fabric base material with low surface smoothness, and the surface of the non-woven fabric base material can be coated satisfactorily. And a separator with few pinholes can be manufactured. When coating unevenness occurs, the uniformity of the separator is lowered, and in the metal ion secondary battery, the ionic conductivity in the separator is uneven, and defects such as local metal deposition when charging and discharging are repeated. When the deposited metal becomes a dendrite-like crystal, an internal short circuit occurs, and the battery capacity decreases, so that the discharge capacity maintenance rate of the battery deteriorates. In addition, if there is a pinhole in the separator, the positive electrode and the negative electrode cannot be separated inside the metal ion secondary battery, and the initial charge / discharge efficiency is remarkably lowered, which causes a problem. Moreover, the distance until the nonwoven fabric base material is pasted after coating on the film is not limited at all, but it is within 10 m because the flow of coating liquid on the film and unnecessary drying can be suppressed. It is preferable that
本発明に用いる該不織布基材には、平均径が0.5〜10μmである、ビニロン;ナイロン、アラミド等のポリアミド;レーヨン、リヨセル、パルプ等のセルロース;ポリエチレンテレフタレート、ポリブチレンテレフタレート、芳香族ポリエステル等のポリエステル;ポリエチレン、ポリプロピレン等のポリオレフィン;アクリル;ガラス等を用いて形成される極細糸のうち、1種もしくは2種以上を併用又は複合して形成され、孔の長径が0.1〜70μmである気孔を、全体気孔数を基準として50%以上含むものが望ましく、且つ不織布基材の厚さは9〜30μmであることが望ましいが、これらによってなんら制限されるものではない。 The nonwoven fabric substrate used in the present invention has an average diameter of 0.5 to 10 μm, vinylon; polyamide such as nylon and aramid; cellulose such as rayon, lyocell and pulp; polyethylene terephthalate, polybutylene terephthalate, aromatic polyester Polyester such as polyethylene, polyolefin such as polypropylene, acrylic, etc. Among ultrafine yarns formed using glass or the like, one or more kinds are used in combination or in combination, and the long diameter of the pore is 0.1 to 70 μm. It is desirable to contain 50% or more of the pores based on the total number of pores, and the thickness of the nonwoven fabric substrate is desirably 9 to 30 μm, but is not limited by these.
本発明において、フィルムの塗工面に不織布基材を貼り合わせる際に、圧力を掛けても良い。貼り合わせる際の圧力を調節することで、貼り合わせた際に不織布内部へ浸透する塗液の量を調節することができ、セパレータの内部抵抗と強度を調節することができる。圧力を高めると、不織布内部への塗液の浸透を増大させることができ、セパレータの強度を向上させることができる。圧力を弱めると、浸透を減少させることができ、セパレータの内部抵抗を低減させることができる。そのため、該圧力を制御することで目的に合わせたセパレータの設計を行うことができる。また、フィルムの塗工面への不織布基材の貼り合わせ方法は、なんら制限されるものではないが、フィルムの塗工面を鉛直上向きにし、この面に対して不織布基材を上方向から被せる形で貼り合わせることで、塗液の流動が抑制でき、不織布基材を貼り合わせる際の圧力制御も容易になることから、より好ましい。 In the present invention, pressure may be applied when the nonwoven fabric substrate is bonded to the coated surface of the film. By adjusting the pressure at the time of bonding, the amount of the coating liquid penetrating into the nonwoven fabric when bonded can be adjusted, and the internal resistance and strength of the separator can be adjusted. When the pressure is increased, the penetration of the coating liquid into the nonwoven fabric can be increased, and the strength of the separator can be improved. When the pressure is weakened, the penetration can be reduced and the internal resistance of the separator can be reduced. Therefore, the separator can be designed according to the purpose by controlling the pressure. In addition, the method of laminating the nonwoven fabric substrate to the coated surface of the film is not limited in any way, but the coated surface of the film is directed vertically upward and the nonwoven fabric substrate is covered from above on the surface. By laminating, the flow of the coating liquid can be suppressed, and pressure control at the time of laminating the non-woven fabric substrate is facilitated, which is more preferable.
本発明において、乾燥過程で、フィルム/顔料を含有する塗液/不織布基材から成るシートを乾燥させることで、セパレータの放電容量維持率及び初期充放電効率を向上させることができ、且つ乾燥方式選択の自由度を向上させることができる。該シートの状態で乾燥させることで、乾燥過程での塗液の濃度変化によるハジキの発生、乾燥時の機械的な振動等によって生じる液面の流動による塗布ムラの発生を抑制することができる。乾燥時のハジキはピンホールの原因となり、初期充放電効率を著しく低下させてしまう。また、塗布ムラが発生すると、金属イオン二次電池内にて、セパレータ中のイオン伝導性にムラが生じ、放電容量維持率を悪化させてしまう。該シートの乾燥方式は、特に限定されるものではないが、流動層乾燥、気流乾燥、過熱水蒸気乾燥等の対流伝熱乾燥、伝導伝熱乾燥、輻射伝熱乾燥等に代表される乾燥方式を自由に選択することができる。顔料を含有する塗液/不織布基材のみでは、乾燥時に熱風等が塗液面側に当たる乾燥方式では、乾燥過程で塗液の流動を誘発し易く、塗布ムラが生じ易くなるため、乾燥方式が限定されることになり好ましくない。 In the present invention, in the drying process, the discharge capacity maintenance rate and the initial charge / discharge efficiency of the separator can be improved by drying the sheet comprising the coating liquid / nonwoven fabric substrate containing the film / pigment, and the drying method. The degree of freedom of selection can be improved. By drying in the state of the sheet, it is possible to suppress the occurrence of repelling due to changes in the concentration of the coating liquid during the drying process, and the occurrence of coating unevenness due to liquid surface flow caused by mechanical vibration during drying. Repelling at the time of drying causes pinholes and significantly reduces the initial charge / discharge efficiency. In addition, when uneven coating occurs, uneven ion conductivity in the separator occurs in the metal ion secondary battery, which deteriorates the discharge capacity retention rate. The drying method of the sheet is not particularly limited, but drying methods represented by convective heat transfer drying such as fluidized bed drying, airflow drying, superheated steam drying, conduction heat transfer drying, radiation heat transfer drying, etc. You can choose freely. In the case of only a coating liquid / nonwoven fabric substrate containing a pigment, a drying method in which hot air or the like hits the coating liquid surface side at the time of drying tends to induce the flow of the coating liquid during the drying process, and uneven coating tends to occur. It is not preferable because it is limited.
本発明において、乾燥後の該シートからフィルムを剥離することで、塗布ムラが少なく、ピンホールが極少であり、且つ表面の平滑性が高いセパレータを製造することができる。該セパレータを金属イオン二次電池に用いると、塗布ムラが少ないことで、高い放電容量維持率を持ち、ピンホールが極少となり、短絡が抑制されることで、高い初期充放電効率を持つ金属イオン二次電池を得ることができる。且つ、該セパレータの高い平滑性のため、放電容量維持率をさらに向上させることができる。該平滑性の効果は明確ではないが、表面の平滑性が高いため、電極に対してセパレータがより均一に密着し、金属イオン二次電池内にてイオン伝導性がより均一になるため、充放電を繰り返した際に金属の析出などの不具合がより生じ難くなり、結果短絡の発生をより抑えることができるため、電池の放電容量維持率がより向上したと考えられる。 In the present invention, by separating the film from the dried sheet, it is possible to produce a separator with little coating unevenness, minimal pinholes, and high surface smoothness. When this separator is used in a metal ion secondary battery, it has a high discharge capacity maintenance rate due to less coating unevenness, pinholes are minimized, and short-circuiting is suppressed, so that metal ions with high initial charge / discharge efficiency are obtained. A secondary battery can be obtained. In addition, the discharge capacity maintenance ratio can be further improved due to the high smoothness of the separator. Although the effect of the smoothness is not clear, since the smoothness of the surface is high, the separator adheres more uniformly to the electrode, and the ion conductivity becomes more uniform in the metal ion secondary battery. When the discharge is repeated, defects such as metal deposition are less likely to occur, and as a result, the occurrence of a short circuit can be further suppressed. Therefore, it is considered that the discharge capacity maintenance rate of the battery is further improved.
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なんら限定されるものではない。なお、実施例において、%及び部はすべて質量基準である。また塗工量は絶乾塗工量である。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In Examples,% and parts are all based on mass. The coating amount is an absolutely dry coating amount.
実施例1
(1)セパレータ用塗液の作製
粒状ベーマイト(商品名:C−20、大明化学(株)製)100部をカルボキシメチルセルロース2%水溶液100部に分散し、ベーマイト分散液を作製した。この分散液に45%スチレンブタジエンラテックス10部を添加して強攪拌し、セパレータ用塗液を作製した。
Example 1
(1) Preparation of separator coating liquid 100 parts of granular boehmite (trade name: C-20, manufactured by Daimei Chemical Co., Ltd.) was dispersed in 100 parts of a 2% aqueous solution of carboxymethyl cellulose to prepare a boehmite dispersion. To this dispersion, 10 parts of 45% styrene butadiene latex was added and stirred vigorously to prepare a separator coating solution.
(2)セパレータの作製
厚み25μmのPETフィルム上に上記のセパレータ用塗液を絶乾塗工量が10g/m2となるように塗工し、その後、坪量10g/m2、厚み18μmのPET不織布基材を塗工面に貼り合わせてそのまま乾燥させ、乾燥後PETフィルムを剥離し、不織布基材に顔料を担持させたセパレータを作製した。
(2) Production of separator On the PET film having a thickness of 25 μm, the separator coating liquid was applied so that the dry coating amount was 10 g / m 2, and thereafter the basis weight was 10 g / m 2 and the thickness was 18 μm. A PET nonwoven fabric substrate was bonded to the coated surface and dried as it was, and after drying, the PET film was peeled off to produce a separator having the nonwoven fabric substrate supported with a pigment.
実施例2
実施例1の(1)セパレータ用塗液の作製において、粒状ベーマイト(商品名:C−20、大明化学(株)製)100部の代わりに、50%変性スチレンブタジエン粒子(商品名:V1004ラテックス、日本ゼオン(株)製)200部を用い、カルボキシメチルセルロース2%水溶液100部の代わりに、カルボキシメチルセルロース1.5%水溶液150部を用いた以外は実施例1と同様にして、不織布基材に顔料を担持させたセパレータを作製した。
Example 2
50% modified styrene butadiene particles (trade name: V1004 latex) instead of 100 parts of granular boehmite (trade name: C-20, manufactured by Daimei Chemical Co., Ltd.) In the same manner as in Example 1, except that 200 parts of Zeon Co., Ltd.) was used and 150 parts of 1.5% aqueous carboxymethylcellulose solution was used instead of 100 parts of 2% aqueous carboxymethylcellulose solution. A separator carrying a pigment was prepared.
実施例3
実施例1の(2)セパレータの作製において、厚み25μmPETフィルムの代わりに厚み100μmの工程紙を用いた以外は実施例1と同様にして、不織布基材に顔料を担持させたセパレータを作製した。工程紙は、グラシン紙にシリコーン系剥離剤を塗布したものを用いた。
Example 3
In the production of the separator of Example 1 (2), a separator having a nonwoven fabric substrate carrying a pigment was produced in the same manner as in Example 1 except that a process paper having a thickness of 100 μm was used instead of the 25 μm PET film. As the process paper, glassine paper coated with a silicone release agent was used.
実施例4
実施例1の(1)セパレータ用塗液の作製において、カルボキシメチルセルロース2%水溶液100部の代わりに、カルボキシメチルセルロース0.8%水溶液230部を用いた以外は実施例1と同様にして、不織布基材に顔料を担持させたセパレータを作製した。
Example 4
In the preparation of the coating liquid for separator of Example 1 (1), a non-woven fabric base was prepared in the same manner as in Example 1, except that 230 parts of carboxymethylcellulose 0.8% aqueous solution was used instead of 100 parts of carboxymethylcellulose 2% aqueous solution. A separator having a pigment supported on the material was produced.
実施例5
実施例1の(1)セパレータ用塗液の作製において、カルボキシメチルセルロース2%水溶液100部の代わりに、カルボキシメチルセルロース0.3%水溶液550部を用いた以外は実施例1と同様にして、不織布基材に顔料を担持させたセパレータを作製した。
Example 5
In the production of the separator coating liquid of Example 1 (1), a nonwoven fabric base was prepared in the same manner as in Example 1 except that 550 parts of a 0.3% aqueous solution of carboxymethylcellulose was used instead of 100 parts of a 2% aqueous solution of carboxymethylcellulose. A separator having a pigment supported on the material was produced.
実施例6
実施例1の(1)セパレータ用塗液の作製において、カルボキシメチルセルロース2%水溶液100部の代わりに、カルボキシメチルセルロース0.2%水溶液900部を用いた以外は実施例1と同様にして、不織布基材に顔料を担持させたセパレータを作製した。
Example 6
In the production of the separator coating liquid of Example 1 (1), a nonwoven fabric base was prepared in the same manner as in Example 1 except that 900 parts of carboxymethylcellulose 0.2% aqueous solution was used instead of 100 parts of carboxymethylcellulose 2% aqueous solution. A separator having a pigment supported on the material was produced.
実施例7
実施例1の(1)セパレータ用塗液の作製において、カルボキシメチルセルロース2%水溶液100部の代わりに、カルボキシメチルセルロース0.2%水溶液950部を用いた以外は実施例1と同様にして、不織布基材に顔料を担持させたセパレータを作製した。
Example 7
In the production of the separator coating liquid of Example 1 (1), a nonwoven fabric base was prepared in the same manner as in Example 1 except that 950 parts of a 0.2% aqueous solution of carboxymethylcellulose was used instead of 100 parts of a 2% aqueous solution of carboxymethylcellulose. A separator having a pigment supported on the material was produced.
比較例1
実施例1の(2)セパレータの作製において、厚み25μmのPETフィルムを用いずに、坪量10g/m2、厚み18μmのPET不織布上に、絶乾塗工量が10g/m2となるように、セパレータ用塗液を直接塗工し、乾燥させた以外は実施例1と同様にして、不織布基材に顔料を担持させたセパレータを作製した。
Comparative Example 1
In the production of the separator of Example 1 (2), without using a PET film having a thickness of 25 μm, an absolutely dry coating amount is 10 g / m 2 on a PET nonwoven fabric having a basis weight of 10 g / m 2 and a thickness of 18 μm. A separator having a non-woven fabric substrate carrying a pigment was produced in the same manner as in Example 1 except that the separator coating liquid was directly applied and dried.
比較例2
実施例1の(1)セパレータ用塗液の作製において、粒状ベーマイト(商品名:C−20、大明化学(株)製)100部の代わりに50%変性スチレンブタジエン粒子(商品名:V1004ラテックス、日本ゼオン(株)製)200部を用い、(2)セパレータの作製において、厚み25μmのPETフィルムを用いずに、坪量10g/m2、厚み18μmのPET不織布上に、絶乾塗工量が10g/m2となるようにセパレータ用塗液を直接塗工し、乾燥させた以外は実施例1と同様にして、不織布基材に顔料を担持させたセパレータを作製した。
Comparative Example 2
In the preparation of the coating liquid for separator (1) of Example 1, 50% modified styrene butadiene particles (trade name: V1004 latex) instead of 100 parts of granular boehmite (trade name: C-20, manufactured by Daimei Chemical Co., Ltd.) (2) In the production of the separator, without using a PET film with a thickness of 25 μm, a dry coating amount on a PET nonwoven fabric with a basis weight of 10 g / m 2 and a thickness of 18 μm was used. A separator having a non-woven fabric substrate carrying a pigment was produced in the same manner as in Example 1 except that the separator coating liquid was directly applied so as to be 10 g / m 2 and dried.
<正極の作製>
正極活物質であるコバルト酸リチウム80部、導電助剤であるアセチレンブラック10部、バインダーであるポリフッ化ビニリデン(PVDF)5部をN−メチル−2−ピロリドン(NMP)中に均一に混合して正極剤ペーストを作製した。このペーストを厚み20μmのアルミニウム箔上に塗工し、乾燥、カレンダー処理を行って厚み100μmの正極を作製した。さらに、この正極のアルミニウム箔の露出部にタブ付けを行った。
<Preparation of positive electrode>
80 parts of lithium cobaltate as a positive electrode active material, 10 parts of acetylene black as a conductive additive, and 5 parts of polyvinylidene fluoride (PVDF) as a binder are uniformly mixed in N-methyl-2-pyrrolidone (NMP). A positive electrode paste was prepared. This paste was applied onto an aluminum foil having a thickness of 20 μm, dried and calendered to produce a positive electrode having a thickness of 100 μm. Further, the exposed portion of the aluminum foil of the positive electrode was tabbed.
<負極の作製>
負極活物質である黒鉛90部、バインダーであるPVDF5部をNMP中に均一に混合して、負極剤ペーストを作製した。このペーストを厚み20μmの銅箔上に塗工し、乾燥、カレンダー処理を行って厚み90μmの負極を作製した。さらに、この負極の銅箔の露出部にタブ付けを行った。
<Production of negative electrode>
90 parts of graphite as a negative electrode active material and 5 parts of PVDF as a binder were uniformly mixed in NMP to prepare a negative electrode agent paste. This paste was applied onto a copper foil having a thickness of 20 μm, dried and calendered to prepare a negative electrode having a thickness of 90 μm. Further, a tab was attached to the exposed portion of the copper foil of the negative electrode.
<電池の組み立て>
上記のようにして得られた正極と負極とを、実施例1〜7、比較例1〜2で作製したセパレータを介して重ね合わせ、電極セパレータ積層体を作成した。電極セパレータ積層体をラミネートフィルム外装材内に装填し、電解質として1mol/lのLiPF6を溶解させたエチレンカーボネート/ジエチルカーボネート(体積比1/1)溶液を注入し、真空封止を行って、定格容量30mAhとなるリチウムイオン二次電池を作製した。
<Battery assembly>
The positive electrode and the negative electrode obtained as described above were superposed through the separators produced in Examples 1 to 7 and Comparative Examples 1 and 2, to prepare an electrode separator laminate. The electrode separator laminate was loaded into the laminate film exterior material, and an ethylene carbonate / diethyl carbonate (volume ratio 1/1) solution in which 1 mol / l LiPF 6 was dissolved as an electrolyte was injected, and vacuum sealing was performed. A lithium ion secondary battery having a rated capacity of 30 mAh was produced.
[初期充放電効率]
作製したリチウムイオン二次電池について、4.2Vまで1Cでの定電流充電と、4.2Vでの定電圧充電を行い、その後2.8Vまで1Cでの定電流放電を行い、放電容量/充電容量の比率を算出した。
[Initial charge / discharge efficiency]
The produced lithium ion secondary battery is subjected to constant current charging at 1 C up to 4.2 V and constant voltage charging at 4.2 V, and then constant current discharging at 1 C up to 2.8 V, and then discharge capacity / charge The volume ratio was calculated.
[放電容量維持率]
作製したリチウムイオン二次電池について、4.2Vまで1Cでの定電流充電と、4.2Vでの定電圧充電を行い、その後2.8Vまで1Cでの定電流放電を繰り返し行い、1回目に対する100回目の充電容量/放電容量の比率を算出した。
[Discharge capacity maintenance rate]
The produced lithium ion secondary battery was subjected to constant current charging at 1 C up to 4.2 V and constant voltage charging at 4.2 V, and then repeated constant current discharging at 1 C up to 2.8 V, with respect to the first time The ratio of charge capacity / discharge capacity at the 100th time was calculated.
表1から明らかなように、実施例1〜7のセパレータは比較例1〜2のセパレータと比較して、初期充放電効率に優れ放電容量維持率に優れる。また、実施例1、2、4〜7を比較すると、実施例2及び4〜7は、塗工量(乾燥前質量)が30g/m2以上であるため、実施例1と比較して、初期充放電効率に優れる。また、実施例2、4〜7を比較すると、実施例2、4〜6は、塗工量(乾燥前質量)が100g/m2未満であるため、実施例7と比較して、初期充放電効率に優れる。 As is clear from Table 1, the separators of Examples 1 to 7 are excellent in the initial charge / discharge efficiency and excellent in the discharge capacity maintenance rate as compared with the separators of Comparative Examples 1 and 2. Further, when Examples 1, 2, 4 to 7 are compared, Examples 2 and 4 to 7 have a coating amount (mass before drying) of 30 g / m 2 or more, so compared to Example 1, Excellent initial charge / discharge efficiency. Moreover, when Example 2, 4-7 is compared, since the coating amount (mass before drying) of Examples 2, 4-6 is less than 100 g / m < 2 >, compared with Example 7, it is initial charge. Excellent discharge efficiency.
1 フィルム
2 フィルムの巻回体(巻き出し側)
3 フィルムの巻回体(巻き取り側)
4 不織布基材
5 不織布の巻回体(巻き出し側)
6 フィルム/顔料を含有する塗液/不織布基材から成るシート
7 セパレータ
8 セパレータの巻回体(巻き取り側)
9 タッチロール
10 乾燥機
11 搬送ロール
12 搬送ロール
13 搬送ロール
14 搬送ロール
15 搬送ロール
16 搬送ロール
17 搬送ロール
18 搬送ロール
19 搬送ロール
20 搬送ロール
21 搬送ロール
22 搬送ロール
23 搬送ロール
24 ダイコーター
25 フィルムの走行方向を表す矢印
26 不織布基材の走行方向を表す矢印
1 Film 2 Film roll (unwinding side)
3 Film roll (winding side)
4 Nonwoven fabric base material 5 Nonwoven fabric wound body (unwinding side)
6 Film / pigment containing coating liquid / sheet made of non-woven fabric substrate 7 Separator 8 Separator roll (winding side)
9 touch roll 10 dryer 11 transport roll 12 transport roll 13 transport roll 14 transport roll 15 transport roll 16 transport roll 17 transport roll 18 transport roll 19 transport roll 20 transport roll 21 transport roll 22 transport roll 23 transport roll 24 die coater 25 film Arrow 26 representing the traveling direction of the arrow Arrow representing the traveling direction of the nonwoven fabric substrate
Claims (4)
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JP2013229118A (en) * | 2012-04-24 | 2013-11-07 | Mitsubishi Paper Mills Ltd | Method of manufacturing separator for metal ion secondary battery and separator for metal ion secondary battery |
JP2018085347A (en) * | 2013-11-20 | 2018-05-31 | 三菱製紙株式会社 | Lithium ion battery separator |
WO2019163635A1 (en) | 2018-02-20 | 2019-08-29 | 三菱製紙株式会社 | Nonwoven fabric coating machine |
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JP2013229118A (en) * | 2012-04-24 | 2013-11-07 | Mitsubishi Paper Mills Ltd | Method of manufacturing separator for metal ion secondary battery and separator for metal ion secondary battery |
JP2018085347A (en) * | 2013-11-20 | 2018-05-31 | 三菱製紙株式会社 | Lithium ion battery separator |
WO2019163635A1 (en) | 2018-02-20 | 2019-08-29 | 三菱製紙株式会社 | Nonwoven fabric coating machine |
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