JP4365662B2 - Separator for electronic parts - Google Patents
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- JP4365662B2 JP4365662B2 JP2003359099A JP2003359099A JP4365662B2 JP 4365662 B2 JP4365662 B2 JP 4365662B2 JP 2003359099 A JP2003359099 A JP 2003359099A JP 2003359099 A JP2003359099 A JP 2003359099A JP 4365662 B2 JP4365662 B2 JP 4365662B2
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- JP
- Japan
- Prior art keywords
- separator
- vinylidene fluoride
- fine particles
- electronic component
- fluoride homopolymer
- Prior art date
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 47
- 229920001519 homopolymer Polymers 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 38
- 239000010419 fine particle Substances 0.000 claims description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 239000003990 capacitor Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 230000035699 permeability Effects 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 description 46
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- -1 fluoroalkyl vinyl ether Chemical compound 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- CGBYBGVMDAPUIH-ARJAWSKDSA-N dimethylmaleic acid Chemical compound OC(=O)C(/C)=C(/C)C(O)=O CGBYBGVMDAPUIH-ARJAWSKDSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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)
- Secondary Cells (AREA)
Description
本発明は、例えば、リチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ、電気二重層キャパシタなどの電子部品に使用されるセパレータに関するものである。 The present invention relates to a separator used for electronic parts such as a lithium ion secondary battery, a polymer lithium secondary battery, an aluminum electrolytic capacitor, and an electric double layer capacitor.
近年、産業用、民生用のいずれにおいても電気・電子機器の需要が増加している上に、ハイブリッド自動車が開発されたことにより、それらに搭載される電子部品、例えば、リチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ、電気二重層キャパシタなどの需要が著しく増加している。電気・電子機器は長寿命化、高機能化が日進月歩で進行しており、電子部品においても長寿命化、高機能化が要求されている。 In recent years, the demand for electrical and electronic equipment has increased for both industrial and consumer use, and the development of hybrid vehicles has led to the development of electronic components such as lithium ion secondary batteries, Demand for polymer lithium secondary batteries, aluminum electrolytic capacitors, electric double layer capacitors, etc. has increased significantly. Electrical and electronic devices have long life and high functionality, and electronic components are required to have long life and high functionality.
電子部品のうち、ポリマーリチウム二次電池は、正極、多孔質電解質膜（セパレータ）、負極の順に捲回もしくは積層された電極体に駆動用電解液が含浸され、アルミニウムケースにより封止されたものである。ここで、正極は、活物質とリチウム含有酸化物とポリフッ化ビニリデン等のバインダとが１−メチル−２−ピロリドン等の中で混合され、アルミニウム製集電体上にシート化されたものである。また、負極は、リチウムイオンを吸蔵放出し得る炭素質材料とポリフッ化ビニリデン等のバインダとが１−メチル−２−ピロリドン等の中で混合され、銅製集電体上にシート化されたものである。 Among the electronic components, the polymer lithium secondary battery is obtained by impregnating a driving electrolyte in an electrode body wound or laminated in the order of a positive electrode, a porous electrolyte membrane (separator), and a negative electrode, and sealed with an aluminum case It is. Here, the positive electrode is obtained by mixing an active material, a lithium-containing oxide, and a binder such as polyvinylidene fluoride in 1-methyl-2-pyrrolidone and the like, and forming a sheet on an aluminum current collector. . In addition, the negative electrode is a sheet in which a carbonaceous material capable of occluding and releasing lithium ions and a binder such as polyvinylidene fluoride are mixed in 1-methyl-2-pyrrolidone or the like and formed on a copper current collector. is there.
アルミニウム電解コンデンサは、駆動用電解液が含浸された電極体が、アルミニウムケースおよび封口体により封止され、短絡しないように正極リードと負極リードとがアルミニウムケースまたは封口体を貫通して外部に引き出されたのものであって、電極体は、エッチングした後に化成処理が施されて誘電体皮膜を形成したアルミニウム製正極箔と、エッチングされたアルミニウム製負極箔とがセパレータを介して捲回もしくは積層されたものである。
電気二重層キャパシタは、駆動用電解液が含浸された電極体が、アルミニウムケースおよび封口体により封止され、短絡しないように正極リードと負極リードとがアルミニウムケースまたは封口体を貫通して外部に引き出されたものであって、電極体は、活性炭と導電剤とバインダとを混錬したものがアルミニウム製正極、負極各集電極の両面に貼り付けられ、セパレータを介して捲回もしくは積層されたものである。
In an aluminum electrolytic capacitor, an electrode body impregnated with a driving electrolyte is sealed with an aluminum case and a sealing body, and a positive electrode lead and a negative electrode lead pass through the aluminum case or the sealing body and are pulled out to prevent short circuit. The electrode body was subjected to chemical conversion treatment after etching, and an aluminum positive foil having a dielectric film formed thereon and an etched aluminum negative foil was wound or laminated via a separator Is.
In an electric double layer capacitor, an electrode body impregnated with a driving electrolyte is sealed with an aluminum case and a sealing body, and a positive electrode lead and a negative electrode lead penetrate the aluminum case or the sealing body to the outside so as not to be short-circuited. The electrode body was obtained by kneading activated carbon, a conductive agent, and a binder, which was affixed to both surfaces of the aluminum positive electrode and the negative electrode, and was wound or laminated via a separator. Is.
従来、上記電子部品のセパレータとしては、例えば、ポリエチレンオキシド、ポリフッ化ビニリデン、ポリアクリロニトリル、ポリメタクリル酸メチル、ポリスチレンなどからなる多孔質膜、電気絶縁紙等が使用されていた。これら従来のセパレータについては、例えば、特許文献１〜５に記載されている。
しかしながら、従来のセパレータは、製造時や、これを用いた電子部品の組み立て時に切れたり、欠損したりすることがあった。そのため、作業性、製造効率が低かった上に、電子部品内部においては微小短絡の発生原因となり、その信頼性を損ねていた。
製造効率の改善や微小短絡防止のためには、セパレータの低多孔度化、膜厚の厚手化が考えられるが、どちらの場合も電池特性の低下に繋がってしまうので採用されていない。
本発明は、上記事情に鑑みてなされたものであり、作業性、生産性、信頼性に優れ、しかも電池特性に優れた電子部品用セパレータを提供することを目的とする。
However, the conventional separator may be cut or missing at the time of manufacturing or when assembling an electronic component using the separator. For this reason, workability and manufacturing efficiency are low, and a short circuit is caused inside the electronic component, which deteriorates the reliability.
In order to improve manufacturing efficiency and prevent micro short-circuits, it is conceivable to reduce the porosity of the separator and increase the thickness of the separator. However, in either case, it is not adopted because it leads to deterioration of battery characteristics.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an electronic component separator that is excellent in workability, productivity, and reliability, and also excellent in battery characteristics.
本発明の電子部品用セパレータは、フッ化ビニリデンホモポリマーを含む樹脂からなる多孔質膜であり、引張伸度が３０％〜２００％であり、前記多孔質膜の内部及び／又は表面に、架橋されたポリアクリロニトリル、架橋されたポリメタクリル酸メチルから選ばれる少なくとも１種類以上の微粒子が分散していることを特徴とする。
本発明の電子部品用セパレータは、密度が０．９ｇ／ｃｍ３以下であることが好ましい。また、透気度が１００秒／１００ｃｃ以下であることが好ましい。
Electronic component separator of the present invention is a porous film made of a resin containing a vinylidene fluoride homopolymer, a tensile elongation of 30% to 200% der is, the internal and / or surface of the porous membrane, It is characterized in that at least one kind of fine particles selected from cross-linked polyacrylonitrile and cross-linked polymethyl methacrylate are dispersed .
The separator for electronic parts of the present invention preferably has a density of 0.9 g / cm 3 or less. The air permeability is preferably 100 seconds / 100 cc or less.
前記微粒子は、前記多孔質膜に単分散していることが好ましい。
前記微粒子の粒径が、前記多孔質膜の膜厚の１％〜４０％の範囲にあることが好ましい。また、微粒子量は、前記樹脂の質量に対して２０質量％〜１００質量％であることが好ましい。
前記微粒子は、吸油量が２００ｍｌ／１００ｇ以下であることが好ましい。
The fine particles are preferably monodispersed in the porous membrane.
The particle diameter of the fine particles is preferably in the range of 1% to 40% of the thickness of the porous film. Moreover, it is preferable that the amount of fine particles is 20 mass%-100 mass% with respect to the mass of the said resin.
The fine particles preferably have an oil absorption of 200 ml / 100 g or less.
本発明の電子部品用セパレータは、リチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ、又は電気二重層キャパシタに備えられて好適に用いられる。 The separator for electronic components of the present invention is suitably used by being provided in a lithium ion secondary battery, a polymer lithium secondary battery, an aluminum electrolytic capacitor, or an electric double layer capacitor.
本発明の電子部品用セパレータは、特定の範囲の引張強度を有するので、セパレータの製造や電子部品の組み立てに際して切れたり、欠損したりすることがない。したがって、作業性、製造効率が高い上に、電子部品内部における微小短絡の発生が抑えられ、信頼性が向上する。すなわち、このセパレータは作業性、生産性、信頼性に優れ、しかも電池特性に優れている。そして、このセパレータが備えられたリチウム二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ、電気二重層キャパシタは長寿命化、高機能化を達成できる。 Since the separator for electronic components of the present invention has a specific range of tensile strength, the separator is not cut or broken when the separator is manufactured or the electronic component is assembled. Therefore, workability and manufacturing efficiency are high, and the occurrence of a minute short circuit inside the electronic component is suppressed, and the reliability is improved. That is, this separator is excellent in workability, productivity, and reliability, and also excellent in battery characteristics. The lithium secondary battery, polymer lithium secondary battery, aluminum electrolytic capacitor, and electric double layer capacitor provided with this separator can achieve a long life and high functionality.
以下、本発明を詳細に説明する。
本発明の電子部品用セパレータ（以下、「セパレータ」と称する。）は、フッ化ビニリデンホモポリマーを含む樹脂からなる多孔質膜である。
本発明に用いられるフッ化ビニリデンホモポリマーは、フッ化ビニリデンモノマーの付加重合反応によって得ることができ、その重合方法としては、例えば、ラジカル重合、カチオン重合、アニオン重合、光・放射線重合、懸濁重合法、乳化重合法、塊状重合法などを挙げることができる。
フッ化ビニリデンホモポリマーを含む樹脂からなるセパレータは、多孔質構造を有しているので、電子部品において電解液中のイオン伝導性が高くなり、内部抵抗が小さくなる。なお、セパレータが多孔質構造でない場合では、電子部品において電解液中のイオン伝導性がセパレータによって阻害され内部抵抗が著しく大きくなる。
Hereinafter, the present invention will be described in detail.
The separator for electronic parts of the present invention (hereinafter referred to as “separator”) is a porous film made of a resin containing vinylidene fluoride homopolymer.
The vinylidene fluoride homopolymer used in the present invention can be obtained by addition polymerization reaction of vinylidene fluoride monomer. Examples of the polymerization method include radical polymerization, cationic polymerization, anionic polymerization, light / radiation polymerization, suspension Examples thereof include a polymerization method, an emulsion polymerization method, and a bulk polymerization method.
Since the separator made of a resin containing vinylidene fluoride homopolymer has a porous structure, the ionic conductivity in the electrolytic solution in the electronic component is increased, and the internal resistance is decreased. In the case where the separator has no porous structure, the ionic conductivity in the electrolytic solution in the electronic component is hindered by the separator, and the internal resistance is remarkably increased.
前記樹脂には、フッ化ビニリデンコポリマー（以下、フッ化ビニリデンコポリマーと称する。）をさらに含有させてもよい。
フッ化ビニリデンコポリマーは、上記フッ化ビニリデンホモポリマーと同様な重合方法で、フッ化ビニリデンモノマーと他のモノマーとを共重合させて得ることができる。
他のモノマーとしては、例えばエチレン、プロピレン等の炭化水素単量体、フッ化ビニル、３フッ化エチレン、３フッ化塩化エチレン、４フッ化エチレン、６フッ化プロピレン、フルオロアルキルビニルエーテル等の含フッ素単量体、マレイン酸モノメチル、シトラコン酸モノメチル等のカルボキシル基含有単量体、またはアリルグリシジルエーテル、クロトン酸グリシジルエステル等のエポキシ基含有ビニル単量体、などが挙げられる。これらの中でも特に、４フッ化エチレン又は６フッ化プロピレンを用いると、フッ化ビニリデンコポリマーを用いた場合のセパレータの耐熱性や電極との密着性が良好であるため好ましい。
本発明で用いられるフッ化ビニリデンホモポリマー及びフッ化ビニリデンコポリマーの好適な分子量は、質量平均分子量において１０万〜１００万である。
また、フッ化ビニリデンコポリマーが、多孔質膜を成す前記樹脂１００質量％に対して５質量％〜３０質量％の範囲であることが、セパレータの耐熱性や電極との密着性を良好に保持するために好ましい。
前記樹脂は、フッ化ビニリデンホモポリマー、フッ化ビニリデンコポリマー以外の樹脂を含有してもよいが、セパレータの強度を安定して発現させるために、含有しない方が好ましい。
The resin may further contain a vinylidene fluoride copolymer (hereinafter referred to as a vinylidene fluoride copolymer).
The vinylidene fluoride copolymer can be obtained by copolymerizing a vinylidene fluoride monomer and another monomer by the same polymerization method as that of the vinylidene fluoride homopolymer.
Examples of other monomers include hydrocarbon monomers such as ethylene and propylene, and fluorine-containing materials such as vinyl fluoride, ethylene trifluoride, ethylene trifluoride, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether. Examples thereof include monomers, carboxyl group-containing monomers such as monomethyl maleate and monomethyl citraconic acid, and epoxy group-containing vinyl monomers such as allyl glycidyl ether and glycidyl crotonic acid ester. Among these, it is particularly preferable to use ethylene tetrafluoride or propylene hexafluoride because the heat resistance of the separator and the adhesion to the electrode are good when the vinylidene fluoride copolymer is used.
The preferred molecular weight of the vinylidene fluoride homopolymer and the vinylidene fluoride copolymer used in the present invention is 100,000 to 1,000,000 in terms of mass average molecular weight.
Further, the vinylidene fluoride copolymer is in the range of 5% by mass to 30% by mass with respect to 100% by mass of the resin forming the porous film, so that the heat resistance of the separator and the adhesiveness with the electrode are favorably maintained. Therefore, it is preferable.
The resin may contain a resin other than the vinylidene fluoride homopolymer and the vinylidene fluoride copolymer, but it is preferably not contained in order to stably develop the strength of the separator.
本発明の電子部品用セパレータの引張伸度は、３０％〜２００％である。
引張伸度が３０％未満であると、電池製造時のテンションによりセパレータに亀裂が入ってしまう。また、セパレータを用いて作製した電子部品の初回充放電（エージング）に際しては、リチウムイオン等の蓄積に伴って電極が伸縮するが、引張伸度が３０％未満であると、この電極の伸縮にセパレータが絶えられなくて破断し、電子部品内で短絡が起こってしまう。引張伸度が２００％を越えると、電池製造時のテンションによりセパレータが伸びてしまい、幅方向の寸法が縮んでしまったり、セパレータの厚みや物性の変化を生じてしまう。
前記引張伸度は、好ましくは５０％〜１００％である。
ここで、引張伸度は、引張試験器（例えば、ＯＲＩＥＮＴＥＣ社製 「テンシロン」ＵＣＴ−５００）を用いて測定される。
セパレータを成す多孔質膜を試料として、この試料を長さ２０ｍｍ、幅１０ｍｍに切断して試験片とする。そして、２５℃、６５％ＲＨ環境下において、試料の測定長さが１０ｍｍになるように、即ち試験片の両端からそれぞれ５ｍｍの部分を固定具で固定するようにして試験器にセッティングし、引張速度５０ｍｍ／ｍｉｎで試料を引っ張り、試料が切断されるまでの長さを測定する。そして、次の式により引張伸度を求める。
引張伸度（％）＝［切断された時の長さ（ｍｍ）−１０／１０］×１００
The tensile elongation of the separator for electronic parts of the present invention is 30% to 200%.
If the tensile elongation is less than 30%, the separator cracks due to the tension during battery production. In addition, during the initial charge / discharge (aging) of an electronic component manufactured using a separator, the electrode expands and contracts as lithium ions accumulate, but if the tensile elongation is less than 30%, the electrode expands and contracts. The separator is not continuous and breaks, causing a short circuit in the electronic component. If the tensile elongation exceeds 200%, the separator is stretched due to the tension during battery production, and the dimension in the width direction is reduced, or the thickness and physical properties of the separator are changed.
The tensile elongation is preferably 50% to 100%.
Here, the tensile elongation is measured using a tensile tester (for example, “Tensilon” UCT-500 manufactured by ORIENTEC).
Using the porous membrane forming the separator as a sample, the sample is cut into a length of 20 mm and a width of 10 mm to obtain a test piece. Then, in an environment of 25 ° C. and 65% RH, the sample is set to a tester so that the measurement length is 10 mm, that is, each part of 5 mm from both ends of the test piece is fixed with a fixture. The sample is pulled at a speed of 50 mm / min, and the length until the sample is cut is measured. Then, the tensile elongation is obtained by the following formula.
Tensile elongation (%) = [Length when cut (mm) −10/10] × 100
本発明における多孔質膜においては、該多孔質膜に形成された多数の孔が互いに連通していることによって、その一方の面と他方の面とが通じているが、ここで、孔各々の径は膜厚より小さいことが、セパレータの機械的強度を得るために好ましい。
セパレータの空隙率は３０％〜９０％の範囲内であることが好ましい。空隙率が３０％未満であると、電解液保持量が少なすぎたり、イオン伝導性の低下によるインピーダンスの上昇が生じたりすることがある。一方、９０％を超えると、セパレータ強度の低下による作業性の悪化が懸念される。
ここでいう空隙率は、坪量Ｍ（ｇ／ｃｍ２）、厚さＴ（μｍ）、密度Ｄ（ｇ／ｃｍ３）を用いて次式により求められる。
空隙率（％）＝［１−（Ｍ／Ｔ）／Ｄ］×１００
In the porous membrane of the present invention, a large number of holes formed in the porous membrane communicate with each other, so that one surface and the other surface communicate with each other. The diameter is preferably smaller than the film thickness in order to obtain the mechanical strength of the separator.
It is preferable that the separator has a porosity of 30% to 90%. If the porosity is less than 30%, the amount of electrolyte retained may be too small, or the impedance may increase due to a decrease in ionic conductivity. On the other hand, when it exceeds 90%, there is a concern that workability may deteriorate due to a decrease in separator strength.
The porosity here is calculated | required by following Formula using basis weight M (g / cm < 2 >), thickness T (micrometer), and density D (g / cm < 3 >).
Porosity (%) = [1- (M / T) / D] × 100
本発明のセパレータは、密度が０．９ｇ／ｃｍ３以下であることが好ましい。
０．９ｇ／ｃｍ３ を超えると、電解液保持量が少なすぎたり、イオン伝導性の低下によるインピーダンスの上昇が著しくなったりすることがある。即ち、密度が０．９ｇ／ｃｍ３以下であれば、製造時、使用時における破損防止の効果を発揮すると共に、電池の内部抵抗を、電池特性（伝導特性）を良好に発現する程度に低くすることができる。
前記密度は、０．３ｇ／ｃｍ３〜０．９ｇ／ｃｍ３であることがさらに好ましい。
密度が０．３ｇ／ｃｍ３以上であれば、電池製造時のテンションにより亀裂が入ることや、電池作製後の初回充放電（エージング）の際の電極の伸縮に絶えられなくて破断し、短絡が発生してしまうことを、さらに安定して防止することができる。
ここで、密度は、ＪＩＳ Ｐ ８１１８「紙及び板紙−厚さ及び密度の試験方法」に基づいて測定される。
The separator of the present invention preferably has a density of 0.9 g / cm 3 or less.
If it exceeds 0.9 g / cm 3 , the amount of electrolyte retained may be too small, or the impedance may increase significantly due to a decrease in ionic conductivity. That is, if the density is 0.9 g / cm 3 or less, the effect of preventing breakage during production and use is exhibited, and the internal resistance of the battery is low enough to express battery characteristics (conducting characteristics) well. can do.
The density is more preferably a 0.3g / cm 3 ~0.9g / cm 3 .
If the density is 0.3 g / cm 3 or more, cracks may occur due to the tension during battery manufacture, and the electrode will not break due to the expansion and contraction of the electrode during the first charge / discharge (aging) after the battery is manufactured. Can be more stably prevented.
Here, the density is measured based on JIS P 8118 “Paper and paperboard—Test method for thickness and density”.
セパレータの透気度は１００秒／１００ｃｃ以下であることが好ましい。セパレータの透気度が１００秒／１００ｃより高くなると、イオン伝導性の低下によるインピーダンスの上昇が著しくなることがある。
セパレータの透気度は、５０秒／１００ｃｃ以下であることがさらに好ましい。
ここで、透気度は、ＪＩＳ Ｐ ８１１７に基づくガーレー試験機法によるものである。
The air permeability of the separator is preferably 100 seconds / 100 cc or less. When the air permeability of the separator is higher than 100 seconds / 100c, an increase in impedance due to a decrease in ion conductivity may be significant.
The air permeability of the separator is more preferably 50 seconds / 100 cc or less.
Here, the air permeability is based on the Gurley tester method based on JIS P 8117.
セパレータの厚さは１０μｍ〜５０μｍが好ましく、１５μｍ〜３５μｍであることがさらに好ましい。
セパレータの厚さが１０μｍ未満であると、強度の低下による作業性の低下や微小短絡の発生が懸念され、５０μｍを超えると、内部抵抗が大きくなることがある。
The thickness of the separator is preferably 10 μm to 50 μm, and more preferably 15 μm to 35 μm.
When the thickness of the separator is less than 10 μm, there is a concern that the workability is reduced due to a decrease in strength and the occurrence of a micro short circuit. When the thickness exceeds 50 μm, the internal resistance may increase.
本発明の電子部品用セパレータの製造方法について一例を挙げる。この例は、多孔質膜を構成する前記樹脂がフッ化ビニリデンホモポリマーからなる例である。なお、本発明の電子部品用セパレータの製造方法はこの例のみに限定されるものではなく、他の製造方法で製造することも可能である。
この製造方法では、まず、フッ化ビニリデンホモポリマーを、フッ化ビニリデンホモポリマーが溶解する溶媒（以下、これを良溶媒という）に分散・溶解させて樹脂溶液を調製する。
ここで、フッ化ビニリデンコポリマーをさらに含有させてもよい。
良溶媒としては、例えば、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、１−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルスルホキシド等が挙げられる。
フッ化ビニリデンホモポリマーを良溶媒に分散・溶解させる際には、市販の攪拌機を使用することができる。この分散・溶解において、フッ化ビニリデンホモポリマーは良溶媒に室温で容易に溶解するので、特に加熱する必要はない。また、フッ化ビニリデンホモポリマーの濃度については、得られるセパレータの特性を考慮して適宜変更される。
An example is given about the manufacturing method of the separator for electronic components of this invention. In this example, the resin constituting the porous film is made of a vinylidene fluoride homopolymer. In addition, the manufacturing method of the separator for electronic components of this invention is not limited only to this example, It is also possible to manufacture with another manufacturing method.
In this production method, first, a resin solution is prepared by dispersing and dissolving a vinylidene fluoride homopolymer in a solvent in which the vinylidene fluoride homopolymer is dissolved (hereinafter referred to as a good solvent).
Here, you may further contain a vinylidene fluoride copolymer.
Examples of the good solvent include N, N-dimethylacetamide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, N, N-dimethylsulfoxide and the like.
When the vinylidene fluoride homopolymer is dispersed and dissolved in a good solvent, a commercially available stirrer can be used. In this dispersion / dissolution, the vinylidene fluoride homopolymer is easily dissolved in a good solvent at room temperature, and thus does not need to be heated. Further, the concentration of the vinylidene fluoride homopolymer is appropriately changed in consideration of the characteristics of the obtained separator.
ついで、フッ化ビニリデンホモポリマーが溶解しない（以下、これを貧溶媒という）を添加する。
貧溶媒としては、その沸点が良溶媒の沸点より高いものが選ばれる。このような貧溶媒としては、例えば、フタル酸ジブチル、エチレングリコール、ジエチレングリコール、グリセリン等が挙げられる。
このようにして得られた樹脂溶液を、樹脂フィルム又は各種ガラス等の基体上に塗布又はキャスティングしてシート状の皮膜を得る。
そして、この皮膜を乾燥し、溶媒を蒸発させて多孔性のフッ化ビニリデンホモポリマー膜を形成し、これを基体から剥離してセパレータを得る。
樹脂溶液が塗布又はキャスティングされる基体をなす樹脂フィルムとしては、例えば、ポリオレフィンフィルム、ポリエステルフィルム、ポリテトラフルオロエチレンフィルム等が挙げられる。また、基体は、離型処理、易接着処理などの表面処理を施したものでもよく、塗布方法により適宜選択すれば良い。
基体上に樹脂溶液を塗布する際には、ディップコート法、スプレーコート法、ロールコート法、ドクターブレード法、グラビアコート法、スクリーン印刷法等を採用できる。
Then, a vinylidene fluoride homopolymer that does not dissolve (hereinafter referred to as a poor solvent) is added.
As the poor solvent, one having a boiling point higher than that of the good solvent is selected. Examples of such a poor solvent include dibutyl phthalate, ethylene glycol, diethylene glycol, glycerin and the like.
The resin solution thus obtained is applied or cast on a substrate such as a resin film or various types of glass to obtain a sheet-like film.
Then, this film is dried and the solvent is evaporated to form a porous vinylidene fluoride homopolymer film, which is peeled from the substrate to obtain a separator.
Examples of the resin film that forms the substrate on which the resin solution is applied or cast include a polyolefin film, a polyester film, and a polytetrafluoroethylene film. The substrate may be subjected to a surface treatment such as a mold release treatment or an easy adhesion treatment, and may be appropriately selected depending on the coating method.
When the resin solution is applied onto the substrate, a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a gravure coating method, a screen printing method, or the like can be employed.
引張伸度が３０％〜２００％であるセパレータを得るためには、上記製造方法において、溶媒を乾操により蒸発させる際の温度、風量、時間を適宜変更すればよい。高い温度を急激に加えると、良溶媒と貧溶媒が同時に蒸発してセパレータがゴム状になりやすく、引張伸度が大きいものが得られる。一方、低い温度を長時間加えた場合では、良溶媒が全て蒸発した後に貧溶媒が蒸発するため、切れやすく引張伸度が小さいものが得られる。 In order to obtain a separator having a tensile elongation of 30% to 200%, the temperature, air volume, and time for evaporating the solvent by dry operation in the above production method may be appropriately changed. When a high temperature is applied rapidly, the good solvent and the poor solvent are evaporated at the same time, and the separator tends to become rubbery, and a material having a high tensile elongation can be obtained. On the other hand, when a low temperature is applied for a long time, the poor solvent evaporates after all the good solvent evaporates.
なお、本発明のセパレータにおいては、前記多孔質膜の内部及び／又は表面に微粒子が分散していることが好ましい。
上記のように微粒子が分散していると、この微粒子がバインダとしての機能を果たすので、電池特性を低下させることなく、引張強度を制御し、突き刺し強度、圧縮強度を向上させることができる。そのため、製造時に切れたり、欠損したりする頻度を、さらに減少させることができ、作業性、製造効率が高い上に、電子部品内部における微小短絡の発生が抑えられ、信頼性が向上する。
前記微粒子としては特に制限はないが、架橋されたポリアクリロニトリル、架橋されたポリメタクリル酸メチルから選ばれる少なくとも1種類以上であることが好ましい。微粒子が上記のものであれば、セパレータの強度をより高めることができる。また、架橋されていれば、樹脂をフィルム化する前段階での塗料化の際に溶媒に溶解することを防止できる。架橋されていない場合には、微粒子が溶解してしまうので、多孔質膜に微粒子を分散させることが困難になることがある。
ここで、架橋されたポリアクリロニトリル、架橋されたポリメタクリル酸メチルとしては、ポリアクリロニトリル、ポリメタクリル酸メチルを公知の架橋方法によって架橋したものを用いることができる。
In the separator of the present invention, it is preferable that fine particles are dispersed inside and / or on the surface of the porous membrane.
When the fine particles are dispersed as described above, the fine particles serve as a binder, so that the tensile strength can be controlled and the piercing strength and the compressive strength can be improved without deteriorating the battery characteristics. Therefore, the frequency of cutting or chipping at the time of manufacturing can be further reduced, and the workability and manufacturing efficiency are high, and the occurrence of a micro short circuit inside the electronic component is suppressed, and the reliability is improved.
The fine particles are not particularly limited, but are preferably at least one selected from cross-linked polyacrylonitrile and cross-linked polymethyl methacrylate. If the fine particles are as described above, the strength of the separator can be further increased. Moreover, if it has bridge | crosslinked, it can prevent melt | dissolving in a solvent in the case of the coating-formation in the step before film-forming resin. If not cross-linked, the fine particles dissolve, and it may be difficult to disperse the fine particles in the porous membrane.
Here, as the crosslinked polyacrylonitrile and the crosslinked polymethyl methacrylate, those obtained by crosslinking polyacrylonitrile and polymethyl methacrylate by a known crosslinking method can be used.
また、微粒子は多孔質膜に単分散していることが好ましい。微粒子が多孔質膜に単分散していれば、凝集体を形成することがなく、セパレータ内部で微粒子の密度に偏りがなくなり、均一な特性のセパレータが得られる。ここで、単分散とは、各微粒子が互いに接触せずに分散していることをいう。 The fine particles are preferably monodispersed in the porous film. If the fine particles are monodispersed in the porous film, aggregates are not formed, the density of the fine particles is not biased inside the separator, and a separator having uniform characteristics can be obtained. Here, monodispersed means that the fine particles are dispersed without contacting each other.
微粒子の粒径は、多孔質膜の膜厚の１％〜４０％の範囲にあることが好ましい。微粒子の粒径が多孔質膜の膜厚の１％未満であると、引張強度、圧縮強度を向上させることが難しく、４０％を超えると引張強度が低下することがある。
微粒子量は、多孔質膜を構成する前記樹脂の質量の２０質量％〜１００質量％であることが好ましい。微粒子量が多孔質膜を構成する樹脂質量の２０質量％未満であると、微粒子を分散させた効果が十分に発揮されないおそれがあり、１００質量％を超えると、微粒子が多孔質膜を構成する樹脂のバインダとしての効果が弱くなって引張強度が低下することがある。
微粒子の吸油量は２００ｍｌ／１００ｇ以下であることが好ましい。微粒子の吸油量が２００ｍｌ／１００ｇを超えると、樹脂をフィルム化する前段階での塗料化の際に微粒子が溶媒を吸着してしまい塗料化が困難になることがある。
ここで、吸油量とは、ＪＩＳ Ｋ ５１０１に準拠した値である。
The particle diameter of the fine particles is preferably in the range of 1% to 40% of the thickness of the porous film. If the particle size of the fine particles is less than 1% of the thickness of the porous membrane, it is difficult to improve the tensile strength and compressive strength, and if it exceeds 40%, the tensile strength may be lowered.
The amount of fine particles is preferably 20% by mass to 100% by mass of the mass of the resin constituting the porous membrane. If the amount of fine particles is less than 20% by mass of the resin constituting the porous film, the effect of dispersing the fine particles may not be sufficiently exhibited. If the amount exceeds 100% by mass, the fine particles constitute the porous film. The effect of the resin as a binder may be weakened and the tensile strength may be reduced.
The oil absorption of the fine particles is preferably 200 ml / 100 g or less. If the oil absorption amount of the fine particles exceeds 200 ml / 100 g, the fine particles may adsorb the solvent when the resin is made into a coating before forming a film, and it may be difficult to make the paint.
Here, the oil absorption is a value based on JIS K 5101.
以上説明したセパレータは、特定の範囲の引張強度を有するので、製造時や電子部品の組み立て時に切れたり、欠損したりすることがなく、作業性、製造効率が高い上に、電子部品内部における微小短絡の発生が抑えられ、信頼性が向上する。すなわち、このセパレータは作業性、生産性、信頼性に優れ、しかも電池特性に優れている。
このようなセパレータは、リチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ、電気二重層キャパシタに好適に備えられる。
このセパレータが備えられたリチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ、電気二重層キャパシタは長寿命化、高機能化される。
Since the separator described above has a specific range of tensile strength, it will not be cut or broken during manufacture or assembly of electronic components, and it has high workability and high manufacturing efficiency. The occurrence of a short circuit is suppressed and the reliability is improved. That is, this separator is excellent in workability, productivity, and reliability, and also excellent in battery characteristics.
Such a separator is suitably provided in lithium ion secondary batteries, polymer lithium secondary batteries, aluminum electrolytic capacitors, and electric double layer capacitors.
The lithium ion secondary battery, polymer lithium secondary battery, aluminum electrolytic capacitor, and electric double layer capacitor provided with this separator have a long life and high functionality.
（実施例１）
フッ化ビニリデンホモポリマーを１−メチル−２−ピロリドン（以下ＮＭＰと記す）からなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が１０質量％になるように樹脂溶液を調製した。
次いで、この樹脂溶液をポリエチレンテレフタレートフィルム（以下ＰＥＴフィルムと記す）からなる基体上にキャストし、乾燥温度７０℃の条件下で、風量１００ｍ３／ｍｉｎで５分間送風して溶媒を蒸発させることにより多孔質膜を形成させ、多孔質膜をＰＥＴフィルムから剥離してセパレータとした。
このセパレータは、厚さ４０μｍ、引張伸度３１％、密度０．３ｇ／ｃｍ３であった。
(Example 1)
A vinylidene fluoride homopolymer is dissolved in a good solvent composed of 1-methyl-2-pyrrolidone (hereinafter referred to as NMP), a poor solvent composed of dibutyl phthalate is added, and the vinylidene fluoride homopolymer component becomes 10% by mass. A resin solution was prepared as follows.
Next, the resin solution is cast on a substrate made of a polyethylene terephthalate film (hereinafter referred to as PET film), and the solvent is evaporated by blowing air for 5 minutes at an air flow rate of 100 m 3 / min under the condition of a drying temperature of 70 ° C. A porous membrane was formed, and the porous membrane was peeled from the PET film to obtain a separator.
This separator had a thickness of 40 μm, a tensile elongation of 31%, and a density of 0.3 g / cm 3 .
（実施例２）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が６質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を８０℃とした以外は実施例１と同様の方法でセパレータを得た。
得られたセパレータは、厚さ２５μｍ、引張伸度３３％、密度０．７ｇ／ｃｍ３であった。
（実施例３）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が８質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を７５℃とした以外は実施例１と同様の方法でセパレータを得た。得られたセパレータは、厚さ３０μｍ、引張伸度５１％、密度０．３ｇ／ｃｍ３であった。
(Example 2)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, a poor solvent composed of dibutyl phthalate was added, and a resin solution was prepared so that the vinylidene fluoride homopolymer component was 6% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 80 ° C.
The obtained separator had a thickness of 25 μm, a tensile elongation of 33%, and a density of 0.7 g / cm 3 .
(Example 3)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, and a poor solvent composed of dibutyl phthalate was added to prepare a resin solution so that the vinylidene fluoride homopolymer component was 8% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 75 ° C. The obtained separator had a thickness of 30 μm, a tensile elongation of 51%, and a density of 0.3 g / cm 3 .
（実施例４）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が８質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を７５℃、風量を１５０ｍ３／ｍｉｎとした以外は、実施例１と同様の方法でセパレータを得た。得られたセパレータは、厚さ３０μｍ、引張伸度５５％、密度０．６ｇ／ｃｍ３であった。
（実施例５）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が６質量％になるように樹脂溶液を調製した。
次いで、風量を２００ｍ３／ｍｉｎとした以外は実施例１と同様の方法でセパレータを得た。得られたセパレータは、厚さ２５μｍ、引張伸度１１０％、密度０．３ｇ／ｃｍ３であった。
(Example 4)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, and a poor solvent composed of dibutyl phthalate was added to prepare a resin solution so that the vinylidene fluoride homopolymer component was 8% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 75 ° C. and the air volume was 150 m 3 / min. The obtained separator had a thickness of 30 μm, a tensile elongation of 55%, and a density of 0.6 g / cm 3 .
(Example 5)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, a poor solvent composed of dibutyl phthalate was added, and a resin solution was prepared so that the vinylidene fluoride homopolymer component was 6% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the air volume was 200 m 3 / min. The obtained separator had a thickness of 25 μm, a tensile elongation of 110%, and a density of 0.3 g / cm 3 .
（実施例６）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が９質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を８５℃とした以外は実施例１と同様の方法でセパレータを得た。得られたセパレータは、厚さ３５μｍ、引張伸度１０３％、密度０．９ｇ／ｃｍ３であった。
（実施例７）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が５質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を８５℃、風量を３００ｍ３／ｍｉｎとした以外は実施例１と同様の方法でセパレータを得た。得られたセパレータは、厚さ２０μｍ、引張伸度１２０％、密度１．０ｇ／ｃｍ３であった。
（実施例８）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が８質量％になるように樹脂溶液を調製した。
次いで、風量を２００ｍ３／ｍｉｎとした以外は実施例１と同様の方法でセパレータを得た。得られたセパレータは、厚さ３０μｍ、引張伸度１９６％、密度０．３ｇ／ｃｍ３であった。
（実施例９）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が５質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を７５℃、風量を２００ｍ３／ｍｉｎとした以外は実施例１と同様にセパレータを得た。得られたセパレータは、厚さ２０μｍ、引張伸度１９１％、密度０．９ｇ／ｃｍ３であった。
（実施例１０）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が４質量％になるように樹脂溶液を調製した。
引き続き、前記樹脂溶液に、粒径が１．５μｍで吸油量が５０ｍｌ／１００ｇの架橋されたポリアクリロニトリルからなる微粒子を、フッ化ビニリデンホモポリマーの質量に対して４０質量％になるように加え、混合した。
次いで、乾燥温度を１００℃、風量を２００ｍ３／ｍｉｎとした以外は実施例１と同様にセパレータを得た。得られたセパレータは、厚さ１５μｍ、引張伸度８４％、密度１．０ｇ／ｃｍ３であった。また、得られたセパレータにおいて、微粒子は、多孔質膜の内部及び表面に分散していた。
(Example 6)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, and a poor solvent composed of dibutyl phthalate was added to prepare a resin solution so that the vinylidene fluoride homopolymer component was 9% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 85 ° C. The obtained separator had a thickness of 35 μm, a tensile elongation of 103%, and a density of 0.9 g / cm 3 .
(Example 7)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, and a poor solvent composed of dibutyl phthalate was added to prepare a resin solution so that the vinylidene fluoride homopolymer component was 5% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 85 ° C. and the air volume was 300 m 3 / min. The obtained separator had a thickness of 20 μm, a tensile elongation of 120%, and a density of 1.0 g / cm 3 .
(Example 8)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, and a poor solvent composed of dibutyl phthalate was added to prepare a resin solution so that the vinylidene fluoride homopolymer component was 8% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the air volume was 200 m 3 / min. The obtained separator had a thickness of 30 μm, a tensile elongation of 196%, and a density of 0.3 g / cm 3 .
Example 9
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, and a poor solvent composed of dibutyl phthalate was added to prepare a resin solution so that the vinylidene fluoride homopolymer component was 5% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 75 ° C. and the air volume was 200 m 3 / min. The obtained separator had a thickness of 20 μm, a tensile elongation of 191%, and a density of 0.9 g / cm 3 .
(Example 10)
The vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, and a poor solvent composed of dibutyl phthalate was added to prepare a resin solution so that the vinylidene fluoride homopolymer component was 4% by mass.
Subsequently, fine particles of crosslinked polyacrylonitrile having a particle size of 1.5 μm and an oil absorption of 50 ml / 100 g are added to the resin solution so as to be 40% by mass with respect to the mass of the vinylidene fluoride homopolymer, Mixed.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 100 ° C. and the air volume was 200 m 3 / min. The obtained separator had a thickness of 15 μm, a tensile elongation of 84%, and a density of 1.0 g / cm 3 . In the obtained separator, the fine particles were dispersed inside and on the surface of the porous membrane.
（比較例１）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が８質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を５０℃、風量を５０ｍ３／ｍｉｎとした以外は実施例１と同様にセパレータを得た。得られたセパレータは厚さ３０μｍ、引張伸度８％、密度０．７ｇ／ｃｍ３であった。
（比較例２）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が６質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を５０℃、風量を７０ｍ３／ｍｉｎとした以外は実施例１と同様にセパレータを得た。得られたセパレータは厚さ２５μｍ、引張伸度１７％、密度０．６ｇ／ｃｍ３であった。
（比較例３）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が９質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を１５０℃、風量を３００ｍ３／ｍｉｎとした以外は実施例１と同様にセパレータを得た。得られたセパレータは厚さ３５μｍ、引張伸度３３５％、密度０．６ｇ／ｃｍ３であった。
（比較例４）
フッ化ビニリデンホモポリマーをＮＭＰからなる良溶媒に溶解し、フタル酸ジブチルからなる貧溶媒を添加して、フッ化ビニリデンホモポリマー成分が６質量％になるように樹脂溶液を調製した。
次いで、乾燥温度を１５０℃、風量を４００ｍ３／ｍｉｎとした以外は実施例１と同様にセパレータを得た。得られたセパレータは厚さ２５μｍ、引張伸度３２１％、密度１．０ｇ／ｃｍ３であった。
(Comparative Example 1)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, and a poor solvent composed of dibutyl phthalate was added to prepare a resin solution so that the vinylidene fluoride homopolymer component was 8% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 50 ° C. and the air volume was 50 m 3 / min. The obtained separator had a thickness of 30 μm, a tensile elongation of 8%, and a density of 0.7 g / cm 3 .
(Comparative Example 2)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, a poor solvent composed of dibutyl phthalate was added, and a resin solution was prepared so that the vinylidene fluoride homopolymer component was 6% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 50 ° C. and the air volume was 70 m 3 / min. The obtained separator had a thickness of 25 μm, a tensile elongation of 17%, and a density of 0.6 g / cm 3 .
(Comparative Example 3)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, and a poor solvent composed of dibutyl phthalate was added to prepare a resin solution so that the vinylidene fluoride homopolymer component was 9% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 150 ° C. and the air volume was 300 m 3 / min. The obtained separator had a thickness of 35 μm, a tensile elongation of 335%, and a density of 0.6 g / cm 3 .
(Comparative Example 4)
A vinylidene fluoride homopolymer was dissolved in a good solvent composed of NMP, a poor solvent composed of dibutyl phthalate was added, and a resin solution was prepared so that the vinylidene fluoride homopolymer component was 6% by mass.
Next, a separator was obtained in the same manner as in Example 1 except that the drying temperature was 150 ° C. and the air volume was 400 m 3 / min. The obtained separator had a thickness of 25 μm, a tensile elongation of 321%, and a density of 1.0 g / cm 3 .
＜電池組立歩留まり＞
上記１４種の電子部品用セパレータと電極を組み立てて円筒型セルを作製した際の製品歩留まりを確認した。その結果を表１に示す。
なお、円筒型セルの作製においては、下記の電極を用いた。
［使用電極］（宝泉株式会社製）
正極集電体：アルミニウム箔（２０μｍ）、電極材 コバルト酸リチウム
負極集電体：銅箔（１０μｍ）、電極材 天然グラファイト
<Battery assembly yield>
The product yield was confirmed when the above-described 14 types of electronic component separators and electrodes were assembled to produce a cylindrical cell. The results are shown in Table 1.
In the production of the cylindrical cell, the following electrodes were used.
[Electrode used] (made by Hosen Co., Ltd.)
Positive electrode current collector: Aluminum foil (20 μm), electrode material Lithium cobaltate negative electrode current collector: Copper foil (10 μm), electrode material Natural graphite
上記表１に示されるように、実施例１〜１１は、いずれも電池組立時の歩留まりが良好であった。一方、セパレータの引張伸度が３０％未満もしくは２００％より大きい比較例１〜４では、電池組立時の歩留まりが極端に悪くなった。 As shown in Table 1 above, all of Examples 1 to 11 had good yields during battery assembly. On the other hand, in Comparative Examples 1 to 4 in which the tensile elongation of the separator was less than 30% or greater than 200%, the yield at the time of battery assembly was extremely deteriorated.
＜１０日後保持電圧＞
上記で作製した円筒型セルを４．２Ｖまで充電し、１０日間放置後の円筒型セルの保持電圧を下記の条件で測定して、１０日間放置による電圧低下を評価した。その結果を表２に示す。
測定環境：２０℃ ５０％ＲＨ
電気化学測定装置：ｓｏｌａｒｔｒｏｎ社製 「ＳＩ １２８７ １２５５Ｂ」
<Holding voltage after 10 days>
The cylindrical cell produced above was charged to 4.2 V, the holding voltage of the cylindrical cell after being left for 10 days was measured under the following conditions, and the voltage drop due to being left for 10 days was evaluated. The results are shown in Table 2.
Measurement environment: 20 ° C 50% RH
Electrochemical measuring device: “SI 1287 1255B” manufactured by solartron
上記表２に示されるように、実施例１〜１１は、いずれも１０日間放置されても良好に４．２Ｖ付近の電圧を保持していた。
一方、引張伸度が３０％未満もしくは２００％より大きい比較例１〜４では、円筒型セルが１０日間良好に電圧を保持することができなかった。このことは、電池製造時にかかるストレス、もしくは充電時の電極の収縮に対応しきれずにセパレータに欠損を生じ、電池内で微小短絡が発生したためと推定される。
As shown in Table 2 above, all of Examples 1 to 11 satisfactorily maintained a voltage in the vicinity of 4.2 V even when left for 10 days.
On the other hand, in Comparative Examples 1 to 4 where the tensile elongation was less than 30% or greater than 200%, the cylindrical cell could not hold the voltage well for 10 days. This is presumably because the separator was deficient without being able to cope with the stress applied during battery manufacture or the contraction of the electrode during charging, and a micro short circuit occurred within the battery.
＜イオン伝導度＞
上記実施例１〜１０で作製した円筒型セルについて、イオン伝導度を測定することにより電池特性を評価した。
イオン伝導度は、電気化学測定装置（ｓｏｌａｒｔｒｏｎ社製 「ＳＩ １２８７ １２５５Ｂ」）を使用し、交流インピーダンス法により測定した。結果を表３に示す。ここで、イオン伝導度の数値が大きいほど、電池特性が優れていることを示す。
<Ionic conductivity>
About the cylindrical cell produced in the said Examples 1-10, the battery characteristic was evaluated by measuring ionic conductivity.
The ionic conductivity was measured by an alternating current impedance method using an electrochemical measuring device (“SI 1287 1255B” manufactured by solartron). The results are shown in Table 3. Here, it shows that a battery characteristic is excellent, so that the numerical value of ion conductivity is large.
上記表３に示されるように、実施例で得られたセパレータはいずれも良好な電池特性を示したが、密度が０．９ｇ／ｃｍ３以下、透気度が１００秒／１００ｃｃ以下であった実施例１〜６、８〜９のセパレータは、イオン伝導度が高く、セパレータとして特に電池特性に優れたものであった。 As shown in Table 3, the separators obtained in the examples all showed good battery characteristics, but the density was 0.9 g / cm 3 or less and the air permeability was 100 seconds / 100 cc or less. The separators of Examples 1 to 6 and 8 to 9 had high ionic conductivity, and were particularly excellent in battery characteristics as separators.
以上から明らかなように、実施例では、電池組立歩留まり、１０日後保持電圧、電池特性が、いずれも良好であった。しかし、セパレータの引張伸度を３０％未満又は２００％超とした比較例１〜４では、電池組立歩留まり、１０日後保持電圧がいずれも不良となった。 As is clear from the above, in the examples, the battery assembly yield, the retention voltage after 10 days, and the battery characteristics were all good. However, in Comparative Examples 1 to 4 in which the tensile elongation of the separator was less than 30% or more than 200%, the battery assembly yield and the retention voltage after 10 days were all poor.
本発明の電子部品用セパレータが備えられたリチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ、電気二重層キャパシタは長寿命化、高機能化されたものであるから、ハイブリッド自動車、パーソナルコンピュータ、携帯電話、携帯情報端末（ＰＤＡ）等において好適に用いられる。
The lithium ion secondary battery, polymer lithium secondary battery, aluminum electrolytic capacitor, and electric double layer capacitor provided with the separator for electronic parts of the present invention have a long life and high functionality. It is preferably used in computers, mobile phones, personal digital assistants (PDAs) and the like.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10002719B2 (en) | 2014-04-21 | 2018-06-19 | Lg Chem, Ltd. | Separator having binder layer, and electrochemical device comprising the separator and method of preparing the separator |
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| JP2006351365A (en) * | 2005-06-16 | 2006-12-28 | Tomoegawa Paper Co Ltd | Separator for electronic components, and the electronic component |
| JP5891655B2 (en) | 2010-08-30 | 2016-03-23 | ソニー株式会社 | Nonaqueous electrolyte battery, nonaqueous electrolyte battery manufacturing method, insulating material, insulating material manufacturing method, battery pack, electronic device, electric vehicle, power storage device, and power system |
| US20140141314A1 (en) * | 2011-07-01 | 2014-05-22 | Zeon Corporation | Porous membrane for secondary batteries, method for producing same, and use of same |
| WO2023190189A1 (en) * | 2022-03-30 | 2023-10-05 | 日本ケミコン株式会社 | Winding electrolytic capacitor |
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| US10002719B2 (en) | 2014-04-21 | 2018-06-19 | Lg Chem, Ltd. | Separator having binder layer, and electrochemical device comprising the separator and method of preparing the separator |
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