JP4855666B2 - Battery separator - Google Patents
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- JP4855666B2 JP4855666B2 JP2004292366A JP2004292366A JP4855666B2 JP 4855666 B2 JP4855666 B2 JP 4855666B2 JP 2004292366 A JP2004292366 A JP 2004292366A JP 2004292366 A JP2004292366 A JP 2004292366A JP 4855666 B2 JP4855666 B2 JP 4855666B2
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- Prior art keywords
- polyethylene naphthalate
- fiber
- pulp
- battery
- fibers
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- -1 polyethylene naphthalate Polymers 0.000 claims abstract description 53
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims abstract description 39
- 239000011112 polyethylene naphthalate Substances 0.000 claims abstract description 39
- 239000000835 fiber Substances 0.000 claims description 57
- 239000004745 nonwoven fabric Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000004760 aramid Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 229920003235 aromatic polyamide Polymers 0.000 claims description 6
- 239000004744 fabric Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract 1
- 229920006231 aramid fiber Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920000561 Twaron Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000004762 twaron Substances 0.000 description 2
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- IALYRRCKADPTAG-UHFFFAOYSA-N C1(=CC=C(C=C1)CO)CO.C(C(CO)(C)C)O Chemical compound C1(=CC=C(C=C1)CO)CO.C(C(CO)(C)C)O IALYRRCKADPTAG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Separators (AREA)
Abstract
Description
本発明は、電池用セパレータに関する。さらに詳しくは、リチウムイオン、ニッケル−水素などの二次電池、あるいは電気二重層キャパシタ用の電池用セパレータに関する。 The present invention relates to a battery separator. More specifically, the present invention relates to a battery separator for a secondary battery such as lithium ion or nickel-hydrogen or an electric double layer capacitor.
各種の分離膜や、電池用セパレータ、電解コンデンサー用セパレータ、キャパシタ用セパレータ、ポリマー電池用セパレータなどには、従来、ポリオレフィン、特にポリプロピレン不織布が使用されている。特に、リチウムイオン電池（一次、二次）においては、有機溶媒に不溶で電解質や電解活物質に安定なセパレータとして多用されている。このようなセパレータは、通常のリチウムイオン電池には十分に使用できるものである。しかしながら、例えば、ハイレート放電特性が必要な電動工具用ニッケル−カドミウム電池などにおいては、使用条件によっては電池温度が１８０℃以上に達することがあるため、融点が１６０〜１８０℃のポリプロピレン繊維を使用したセパレータは、溶融変形するなどして、電池寿命を短くすることがあった。 Conventionally, polyolefins, particularly polypropylene nonwoven fabrics, have been used for various separation membranes, battery separators, electrolytic capacitor separators, capacitor separators, polymer battery separators, and the like. In particular, lithium ion batteries (primary and secondary) are frequently used as separators that are insoluble in organic solvents and stable to electrolytes and electrolytic active materials. Such a separator can be sufficiently used for a normal lithium ion battery. However, for example, in nickel-cadmium batteries for electric tools that require high-rate discharge characteristics, the battery temperature may reach 180 ° C. or higher depending on use conditions, and therefore, polypropylene fibers having a melting point of 160 to 180 ° C. are used. In some cases, the separator may be melted and deformed to shorten the battery life.
そこで、セパレータの耐熱性、および強度を向上させる目的で、アラミド繊維などの耐熱性有機繊維を混抄した不織布からなるセパレータで上記した従来の欠点を解消することが報告されている（特許文献１：特開２０００−１００４０９号公報、特許文献２：特開２００２−１５１０４３号公報、特許文献３：特開２００２−２５２１４７号公報）。このことから、耐熱性と強度を併せ持つアラミド繊維、ポリパラフェニレンベンゾビスオキサゾール繊維も同様に電池用セパレータの材料として有用であると考えられる。しかし、アラミド繊維やポリパラフェニレンベンゾビスオキサゾール繊維は、価格が高くコスト面で不利である。また、製造方法に起因するイオン性不純物の含有量が多いため、使用時に電極を被毒して容量の低下、および内部抵抗の上昇をもたらし、その結果電池寿命が低下するという問題がある。
本発明は、ポリエチレンナフタレート繊維の優れた特性、すなわち高強力、高耐熱性、高純度を生かし、安価で、かつ優れた耐久性を持つ電池用セパレータを提供しようとするものである。 An object of the present invention is to provide a battery separator that uses the excellent properties of polyethylene naphthalate fibers, that is, high strength, high heat resistance, and high purity, is inexpensive, and has excellent durability.
本発明は、ポリエチレンナフタレート繊維とポリエチレンナフタレートパルプまたはアラミドパルプとからなり、かつポリエチレンナフタレート繊維と上記パルプとの重量比が４０／６０〜９５／５である不織布で構成されていることを特徴とする電池用セパレータに関する。
上記不織布は、ポリエチレンナフタレート短繊維とポリエチレンナフタレートパルプまたはアラミドパルプとから湿式法により形成された不織布が好ましい。
また、この不織布中に存在する平均細孔の孔径は、好ましくは０．０１〜５μｍである。
The present invention is composed of a nonwoven fabric composed of polyethylene naphthalate fiber and polyethylene naphthalate pulp or aramid pulp, and having a weight ratio of polyethylene naphthalate fiber to the above pulp of 40/60 to 95/5. The present invention relates to a battery separator.
The nonwoven fabric is preferably a nonwoven fabric formed from a polyethylene naphthalate short fiber and polyethylene naphthalate pulp or aramid pulp by a wet method .
Moreover, the pore diameter of the average pores present in the nonwoven fabric is preferably 0.01 to 5 μm.
本発明によれば、ポリエチレンナフタレート繊維の優れた耐熱性、高強力、高純度を生かし、優れた耐久性を持つ電池用セパレータを比較的安価に提供される。 According to the present invention, a battery separator having excellent durability is provided at a relatively low cost by utilizing the excellent heat resistance, high strength, and high purity of polyethylene naphthalate fiber.
本発明においては、電池用セパレータとして、ポリエチレンナフタレート繊維とポリエチレンナフタレートパルプまたはアラミドパルプとからなり、かつポリエチレンナフタレート繊維と上記パルプとの重量比が４０／６０〜９５／５である不織布を使用する。
In the present invention, as the battery separator , a non-woven fabric made of polyethylene naphthalate fiber and polyethylene naphthalate pulp or aramid pulp and having a weight ratio of polyethylene naphthalate fiber to the above pulp of 40/60 to 95/5 is used. use.
ここで、ポリエチレンナフタレート繊維とは、ポリエチレン−２，６−ナフタレート（ＰＥＮ）に代表されるポリエチレンナフタレートポリマーを通常の紡糸延伸法に供することにより得られた繊維であり、該ポリエチレンナフタレートは、エチレン−２，６−ナフタレート単位を９０モル％以上含んでいればよく、１０モル％以下の割合で適当な第３成分を含む重合体であっても差し支えない。 Here, the polyethylene naphthalate fiber is a fiber obtained by subjecting a polyethylene naphthalate polymer represented by polyethylene-2,6-naphthalate (PEN) to an ordinary spinning drawing method, and the polyethylene naphthalate is The polymer may contain 90% by mole or more of an ethylene-2,6-naphthalate unit, and may be a polymer containing an appropriate third component at a ratio of 10% by mole or less.
一般に、ポリエチレン−２，６−ナフタレートは、ナフタレン−２，６−ジカルボン酸またはそのエステル形成性誘導体を触媒の存在下適当な反応条件のもとにエチレングリコールと縮重合させることにより合成することができる。この際、ポリエチレン−２，６−ナフタレートの重合完結前に、１種または２種以上の第３成分を添加すれば、共重合体が合成される。 In general, polyethylene-2,6-naphthalate can be synthesized by polycondensation of naphthalene-2,6-dicarboxylic acid or an ester-forming derivative thereof with ethylene glycol in the presence of a catalyst under appropriate reaction conditions. it can. At this time, if one or more third components are added before the completion of the polymerization of polyethylene-2,6-naphthalate, a copolymer is synthesized.
適当な第３成分としては、２個のエステル形成性官能基を有する化合物；例えばコハク酸、アジピン酸、セバシン酸、ダイマー酸などの脂肪族ジカルボン酸；ヘキサヒドロテレフタル酸などの脂環族ジカルボン酸；フタル酸、イソフタル酸、ナフタレン−２，７−ジカルボン酸、ジフェニルジカルボン酸などの芳香族ジカルボン酸；ジフェニルエーテルジカルボン酸、ジフェニルスルホンジカルボン酸、ジフェノキシエタンジカルボン酸、３，５−ジカルボキシベンゼンスルホン酸ナトリウムなどのジカルボン酸；グリコール酸、ｐ−オキシ安息香酸ｐ−オキシエトキシ安息香酸などのオキシカルボン酸；トリメチレングリコール、ジエチレングリコール、テトラメチレングリコール、ヘキサメチレングリコール、ネオペンチレングリコール、ｐ−キシリレングリコール、１，４−シクロヘキサンジメタノール、ビスフェノールＡ、ｐ，ｐ’−ジヒドロキシジフェニルスルホン、１，４−ビス（β−ヒドロキシエトキシ）ベンゼン、２，２−ビス（ｐ−β−ヒドロキシエトキシフェニル）プロパンなどが挙げられる。 Suitable third components include compounds having two ester-forming functional groups; for example, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and dimer acid; and alicyclic dicarboxylic acids such as hexahydroterephthalic acid Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, naphthalene-2,7-dicarboxylic acid, diphenyldicarboxylic acid; diphenyl ether dicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, 3,5-dicarboxybenzenesulfonic acid Dicarboxylic acid such as sodium; Glycolic acid, p-oxybenzoic acid, oxycarboxylic acid such as p-oxyethoxybenzoic acid; trimethylene glycol, diethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentylene glycol p-xylylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, p, p′-dihydroxydiphenylsulfone, 1,4-bis (β-hydroxyethoxy) benzene, 2,2-bis (p-β-hydroxy) And ethoxyphenyl) propane.
上記ポリエチレンナフタレート中には、二酸化チタンなどの艶消剤やリン酸、亜リン酸
およびそれらのエステルなどの安定剤が含まれていてよいことはいうまでもない。
Needless to say, the polyethylene naphthalate may contain a matting agent such as titanium dioxide and a stabilizer such as phosphoric acid, phosphorous acid and esters thereof.
また、ポリエチレンナフタレートの固有粘度は、０．６５ｄＬ／ｇ以上、特に０．７〜１．０ｄＬ／ｇの範囲であることが好ましい。ここでいう固有粘度は、ポリマーあるいは延伸前の未延伸糸をフェノールとオルトジクロロベンゼンとの混合溶媒に（容量比６：４）に溶解し、３５℃で測定した粘度から求めた値である。固有粘度が０．６５ｄＬ／ｇ未満では、補強用繊維として要求される高強度、高タフネスな糸質の繊維を得難くなる。一方、１．０ｄＬ／ｇを超える場合には、紡糸工程が不良となりやすく、実用上望ましくない。 The intrinsic viscosity of polyethylene naphthalate is preferably 0.65 dL / g or more, particularly preferably in the range of 0.7 to 1.0 dL / g. The intrinsic viscosity here is a value obtained from the viscosity measured at 35 ° C. by dissolving the polymer or undrawn yarn before drawing in a mixed solvent of phenol and orthodichlorobenzene (volume ratio 6: 4). When the intrinsic viscosity is less than 0.65 dL / g, it is difficult to obtain high-strength and high-toughness yarn-like fibers required as reinforcing fibers. On the other hand, if it exceeds 1.0 dL / g, the spinning process tends to be poor, which is undesirable in practice.
上記ポリエチレンナフタレート繊維は、その単繊維繊度、フィラメント数、断面形状、繊維物性、微細構造などには特に限定を受けるものではなく、目的に応じて適宜選択設定すればよい。 The polyethylene naphthalate fiber is not particularly limited in terms of the single fiber fineness, the number of filaments, the cross-sectional shape, the fiber physical properties, the fine structure, etc., and may be appropriately selected and set according to the purpose.
本発明のセパレータは、上記のようなポリエチレンナフタレート繊維と上記パルプとを含む布帛からなる。この布帛の中でも、繊維が三次元的に配置することができ、電解液の保持性により優れている不織布が好ましい。
The separator of this invention consists of a fabric containing the above polyethylene naphthalate fiber and the said pulp . Among these fabrics, a nonwoven fabric in which the fibers can be arranged three-dimensionally and is superior in electrolyte retention is preferable.
上記不織布の形態には特に限定はなく、スパンレース不織布、スパンボンド不織布、メルトブロー不織布および湿式不織布であってもよい。不織布を構成する繊維にポリエチレンナフタレート繊維が５０重量％以上含まれていればよく、その他の糸については、ポリエチレンナフタレート繊維が本来有する特性を損なわない範囲で、ポリエチレン繊維、ポリプロピレン繊維などのポリオレフィン繊維、ポリアミド繊維、アラミド繊維、ポリパラフェニレンベンゾビスオキサゾール繊維などのポリベンザゾール繊維などを混合できる。
また、上記不織布には、上記繊維のほか、該繊維を結合させるためのバインダーやパルプなどが含まれていても良い。
There is no limitation in the form of the said nonwoven fabric, A spunlace nonwoven fabric, a spun bond nonwoven fabric, a melt blown nonwoven fabric, and a wet nonwoven fabric may be sufficient. As long as the fibers constituting the nonwoven fabric contain at least 50% by weight of polyethylene naphthalate fibers, other yarns are polyolefins such as polyethylene fibers and polypropylene fibers as long as the properties inherent to the polyethylene naphthalate fibers are not impaired. Fibers, polyamide fibers, aramid fibers, polybenzazole fibers such as polyparaphenylenebenzobisoxazole fibers, and the like can be mixed.
Moreover, the said nonwoven fabric may contain the binder, pulp, etc. for couple | bonding this fiber other than the said fiber.
本発明に用いられる不織布は、上記ポリエチレンナフタレート繊維から、湿式法あるいは乾式法により製造される。当該繊維の繊維長は、湿式法により繊維ウエブを形成する場合には、１〜２５ｍｍ長程度の繊維を使用し、カード法やエアレイ法などの乾式法により繊維ウエブを形成する場合には、２５〜１１０ｍｍ長程度の繊維を使用する。 The nonwoven fabric used in the present invention is produced from the polyethylene naphthalate fiber by a wet method or a dry method. The fiber length of the fiber is about 1 to 25 mm when a fiber web is formed by a wet method, and 25 when a fiber web is formed by a dry method such as a card method or an air lay method. Use fibers with a length of ~ 110 mm.
上記不織布を製造する方法には、上記のように特に制限はなく、従来公知の乾式法、湿式法などが任意に採用できるが、中でも、ポリエチレンナフタレート繊維、およびポリエチレンナフタレート繊維をディスクリファイナーにて叩解して得たパルプを水中に分散させ、スラリーを作成した後、該スラリーを使用して抄紙し、加圧脱水後に乾燥させ、さらに、ユニバーサルカレンダー装置などによりカレンダー処理を行う方法などが好ましく例示される。 The method for producing the non-woven fabric is not particularly limited as described above, and a conventionally known dry method, wet method, etc. can be arbitrarily employed. Among them, polyethylene naphthalate fiber and polyethylene naphthalate fiber are used as disc refiners. It is preferable to disperse the pulp obtained by beating in water and create a slurry, and then to make a paper using the slurry, to dry after pressure dehydration, and to carry out a calendar treatment with a universal calendar device, etc. Illustrated.
この場合、ポリエチレンナフタレート繊維の繊維長は、上記のように、通常、１〜２５ｍｍ、好ましくは２〜１２ｍｍ、また、パルプの平均繊維長は、通常、０．５〜３．５ｍｍ、好ましくは１．０〜３．０ｍｍである。また、ポリエチレンナフタレート繊維とポリエチレンナフタレートパルプの重量比は、好ましくは４０／６０〜９５／５程度である。
なお、ポリエチレンナフタレートパルプに代えて、アラミドパルプを用いることもできる。
In this case, the fiber length of the polyethylene naphthalate fiber is usually 1 to 25 mm, preferably 2 to 12 mm as described above, and the average fiber length of the pulp is usually 0.5 to 3.5 mm, preferably 1.0 to 3.0 mm. The weight ratio of the polyethylene naphthalate fibers and polyethylene naphthalate pulp is good Mashiku is about 40 / 60-95 / 5.
In addition, it can replace with a polyethylene naphthalate pulp and can also use an aramid pulp.
ここで、上記カレンダー処理条件としては、温度が８０〜２００℃、好ましくは１２０〜１８０℃、線圧が１０〜４００ｄａＮ／ｃｍ、好ましくは５０〜２００ｄａＮ／ｃｍである。 Here, the calendering conditions are a temperature of 80 to 200 ° C., preferably 120 to 180 ° C., and a linear pressure of 10 to 400 daN / cm, preferably 50 to 200 daN / cm.
このようにして得られる本発明のセパレータの坪量は、通常、５〜１００ｇ／ｍ2、好ましくは１０〜５０ｇ／ｍ２である。坪量が５ｇ／ｍ２未満であると引張強さが不足する場合があり、一方１００ｇ／ｍ2を超えると厚さが厚くなり過ぎて、電池の高容量化が困難となる。 The basis weight of the separator of the present invention thus obtained is usually 5 to 100 g / m 2 , preferably 10 to 50 g / m 2 . If the basis weight is less than 5 g / m 2 , the tensile strength may be insufficient. On the other hand, if the basis weight exceeds 100 g / m 2 , the thickness becomes too thick, making it difficult to increase the capacity of the battery.
ここで、上記不織布中に存在する細孔の平均径は、好ましくは０．０１〜５μｍ、さらに好ましくは０．０５〜３μｍである。細孔径が上記範囲を外れる場合は、電解液保持性、充放電特性が従来よりも低下するため好ましくない。細孔径を上記の範囲にするには、坪量を大きくする、パルプの混合比率を多くするなどの方法があるが、充放電特性を維持する為には後者の方法がより好ましい。 Here, the average diameter of the pores present in the nonwoven fabric is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm. When the pore diameter is out of the above range, the electrolytic solution retention and charge / discharge characteristics are deteriorated as compared with the conventional case, which is not preferable. In order to make the pore diameter within the above range, there are methods such as increasing the basis weight and increasing the mixing ratio of the pulp, but the latter method is more preferable in order to maintain the charge / discharge characteristics.
このような不織布を用いて製造された電池用セパレータは、耐熱性に優れ、イオン性不純物も少ないので、充放電特性および電池寿命に優れた電池用セパレータを提供できる。 Since the battery separator manufactured using such a nonwoven fabric is excellent in heat resistance and has few ionic impurities, a battery separator excellent in charge / discharge characteristics and battery life can be provided.
以下、実施例により本発明をさらに詳細に説明する。なお、実施例で用いた試験片の評価方法は、下記のとおりである。
（１）耐熱性
１８０℃のオーブン５分間保持した後、外観および熱処理前後の収縮率から耐熱性を評価した。
（２）平均細孔径
パームポロメーター（ポーラスマテリアルズ社製）を用い、バブルポイント法に基づく平均細孔径を測定した。
（３）イオン性不純物濃度
試験片２ｇとイオン交換水５０ｍｌとを密閉容器に封入し、１２０℃のオートクレーブ中で２４時間抽出を行った。
次いで、抽出した水のみ分離し、イオンクロマトグラフにてカチオン型不純物（Ｎａ、Ｋ、Ｍｇ、Ｃａ）の総量を測定し、イオン性不純物濃度とした。
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the evaluation method of the test piece used in the Example is as follows.
(1) Heat resistance After holding the oven at 180 ° C for 5 minutes, the heat resistance was evaluated from the appearance and the shrinkage before and after the heat treatment.
(2) Average pore diameter The average pore diameter based on the bubble point method was measured using a palm porometer (manufactured by Porous Materials).
(3) Concentration of ionic impurities 2 g of the test piece and 50 ml of ion-exchanged water were sealed in a sealed container and extracted in an autoclave at 120 ° C. for 24 hours.
Subsequently, only the extracted water was separated, and the total amount of cationic impurities (Na, K, Mg, Ca) was measured by an ion chromatograph to obtain an ionic impurity concentration.
実施例１
単糸繊度１．６５ｄｔｅｘ、繊維長３ｍｍのポリエチレンナフタレート繊維（帝人テクノプロダクツ（株）製「テオネックス」）、および、上記繊維をディスクリファイナーにて叩解し、カナディアンスタンダードフリーネスを５００ｍｌとしたパルプ（繊維長：２．３ｍｍ）を、繊維／パルプ（重量比）＝８０／２０となるように水中に分散させ、繊維濃度が０．１５重量％であるスラリーを作成した。
次に、タッピー式角型抄紙機を用い、該スラリーを使用して抄紙し、軽く加圧脱水後に温度１１０℃で乾燥させ、さらに、ユニバーサルカレンダー装置で温度：１５０〜１７０℃、線圧力：１９６ｄａＮ／ｃｍ（２００ｋｇ／ｃｍ）、カレンダー速度：４ｍ／分の条件でカレンダー処理を行い、坪量２５ｇ／ｍ２のポリエチレンナフタレートシートを作成した。
このシートを用いて得られた電池用セパレータについて、上記（１）〜（３）の測定法にて評価した諸特性は、表１に示すとおりであった。
Example 1
Polyethylene naphthalate fiber having a single yarn fineness of 1.65 dtex and a fiber length of 3 mm (“Teonex” manufactured by Teijin Techno Products Co., Ltd.) (Length: 2.3 mm) was dispersed in water so that fiber / pulp (weight ratio) = 80/20, and a slurry having a fiber concentration of 0.15% by weight was prepared.
Next, a paper is made using the slurry using a tappy type square paper machine, lightly dehydrated under pressure and dried at a temperature of 110 ° C., and further, temperature: 150 to 170 ° C., linear pressure: 196 daN using a universal calendar device. / Cm (200 kg / cm), calendar speed: The calendar process was performed on the condition of 4 m / min, and the polyethylene naphthalate sheet | seat of 25 g / m < 2 > of basic weight was created.
Various characteristics of the battery separator obtained using this sheet were evaluated by the measurement methods (1) to (3) as shown in Table 1.
実施例２
実施例１において、ポリエチレンナフタレートパルプの代わりに、アラミド繊維パルプ（テイジントワロン（株）製「トワロンパルプ１０９５」）を用いた以外は、実施例１と同様に行い、電池用セパレータを作成した。
この電池用セパレータについて、上記（１）〜（３）の測定法にて評価した諸特性は、表１に示すとおりであった。
Example 2
A battery separator was produced in the same manner as in Example 1 except that aramid fiber pulp (“Twaron Pulp 1095” manufactured by Teijin Towaron Co., Ltd.) was used instead of polyethylene naphthalate pulp.
Various characteristics of the battery separator evaluated by the measuring methods (1) to (3) were as shown in Table 1.
比較例１
実施例１において、ポリエチレンナフタレート繊維の代わりに、アラミド繊維（テイジントワロン（株）製「トワロン」）を用いた以外は、実施例１と同様に行い、電池用セパレータを作成した。
この電池用セパレータについて上記（１）〜（３）の測定法にて評価した諸特性は、表１に示すとおりであった。
Comparative Example 1
In Example 1, a battery separator was prepared in the same manner as in Example 1 except that aramid fiber (“Twaron” manufactured by Teijin Towaron Co., Ltd.) was used instead of polyethylene naphthalate fiber.
Various characteristics of this battery separator evaluated by the measuring methods (1) to (3) were as shown in Table 1.
比較例２
実施例１において使用した繊維、パルプの全てを、ポリエチレンパルプ（三井石油化学工業（株）製「ＳＷＰ（登録商標）Ｅ４００」）に置き換えた以外は、実施例１と同様に行い、シートを作成した。
この紙について上記（１）〜（３）の測定法にて評価した諸特性は、表１に示すとおりであった。
Comparative Example 2
A sheet was prepared in the same manner as in Example 1 except that all of the fibers and pulp used in Example 1 were replaced with polyethylene pulp ("SWP (registered trademark) E400" manufactured by Mitsui Petrochemical Co., Ltd.). did.
Various properties of this paper evaluated by the measuring methods (1) to (3) were as shown in Table 1.
本発明の電池用セパレータは、ポリエチレンナフタレート繊維を５０重量％以上含む布帛から構成されている。このポリエチレンナフタレート繊維は、アラミド繊維やポリパラフェニレンベンゾビスオキサゾール繊維に比べて安価であり、またポリエチレン繊維やポリプロピレン繊維などのポリオレフィン繊維に比べて高強度、高耐熱性であり、かつイオン性不純物の濃度が小さい。このため、本発明の電池用セパレータを用いた電池は、放電特性および電池寿命に優れており、リチウムイオン、ニッケル−カドミウムなどの二次電池、あるいは電気二重層キャパシタなどの電池のセパレータとして有用である。
The battery separator of the present invention is composed of a fabric containing 50% by weight or more of polyethylene naphthalate fiber. This polyethylene naphthalate fiber is cheaper than aramid fiber and polyparaphenylene benzobisoxazole fiber, and has higher strength and higher heat resistance than polyolefin fiber such as polyethylene fiber and polypropylene fiber, and ionic impurities The concentration of is small. Therefore, the battery using the battery separator of the present invention has excellent discharge characteristics and battery life, and is useful as a battery separator for secondary batteries such as lithium ion and nickel-cadmium, or electric double layer capacitors. is there.
Claims (3)
The battery separator according to claim 1 or 2, wherein the average pores present in the nonwoven fabric have a pore diameter of 0.01 to 5 µm.
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| JP4273545B2 (en) * | 1998-07-31 | 2009-06-03 | パナソニック株式会社 | Board mounting battery mounting device |
| JPH11329393A (en) * | 1998-05-18 | 1999-11-30 | Yuasa Corp | Nonwoven cloth for battery separator and battery using it |
| JP2000112282A (en) * | 1998-10-08 | 2000-04-21 | Du Pont Teijin Advanced Paper Kk | Cleaning paper, its production and image forming device provided with the same in electrophotographic device for color |
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