JP4938640B2 - separator - Google Patents
separator Download PDFInfo
- Publication number
- JP4938640B2 JP4938640B2 JP2007337260A JP2007337260A JP4938640B2 JP 4938640 B2 JP4938640 B2 JP 4938640B2 JP 2007337260 A JP2007337260 A JP 2007337260A JP 2007337260 A JP2007337260 A JP 2007337260A JP 4938640 B2 JP4938640 B2 JP 4938640B2
- Authority
- JP
- Japan
- Prior art keywords
- separator
- nonwoven fabric
- fiber
- fibers
- fiber diameter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000835 fiber Substances 0.000 claims description 101
- 239000004745 nonwoven fabric Substances 0.000 claims description 49
- 239000003990 capacitor Substances 0.000 claims description 24
- 238000009826 distribution Methods 0.000 claims description 15
- 229920003043 Cellulose fiber Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- -1 alkylene glycol Chemical compound 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000004627 regenerated cellulose Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 238000003490 calendering Methods 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000433 Lyocell Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric 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)
Description
本発明は、内部抵抗が低く、耐電圧性に優れたセパレーターに関する。 The present invention relates to a separator having low internal resistance and excellent voltage resistance.
近年、電子材料の低消費電力化に伴い、コンデンサや電池（以下、コンデンサ等と称することがある）は、内部抵抗の低いものが求められている。これらの特性を出すためには、コンデンサ等の構成部品である電極や電解液、そして電極間を仕切るセパレーターの改良が必要となる。この中でセパレーターの改良例としては、例えば溶剤紡糸セルロースを主体成分とする電解紙などがある（特許文献１参照）。 In recent years, with a reduction in power consumption of electronic materials, capacitors and batteries (hereinafter sometimes referred to as capacitors) are required to have low internal resistance. In order to obtain these characteristics, it is necessary to improve the electrodes and electrolytes, which are components such as capacitors, and the separator that partitions the electrodes. Among these, as an improved example of the separator, there is, for example, electrolytic paper mainly composed of solvent-spun cellulose (see Patent Document 1).
特許文献１によれば、叩解可能な溶剤紡糸セルロース繊維からなる叩解可能な原料を使用した緻密性とイオン透過性の双方を充足する新規なセパレーターを用いることによって、ショート不良の低減、内部抵抗の低減等の諸特性を高いレベルで改善すると共に、高体積エネルギー密度化を実現するコンデンサが得られるとある。 According to Patent Document 1, by using a new separator that satisfies both denseness and ion permeability using a bevelable solvent-spun cellulose fiber, it is possible to reduce short-circuit defects and reduce internal resistance. It is said that a capacitor capable of improving various characteristics such as reduction at a high level and realizing high volume energy density can be obtained.
しかしながら、叩解可能な原料を使用する場合、セパレーターを構成する繊維の繊維径が不均一であることから、部分的な抵抗の増大によって、内部抵抗が上昇したり、耐電圧性が低下して漏れ電流が増加したりする。 However, when using a material that can be beaten, the fiber diameter of the fibers constituting the separator is non-uniform, so that the internal resistance may increase due to a partial increase in resistance, or the withstand voltage may decrease and leak. The current increases.
また一般的な抄紙法によって作られるセパレーターは、原料のスラリーを均一分散させるために界面活性剤を用いる事が多い。また繊維の脱落防止や、引張強力をコンデンサ製造時の張力に耐えうるようにするため、バインダー等で繊維同士を接着している場合もある。しかしこれら界面活性剤やバインダーは、コンデンサ等の製造時に繊維間あるいは繊維内部へ電解液が含浸するのを阻害させる要因となる。また使用していく中で徐々に電解液中に溶出する事から電解液を汚染してしまい、内部抵抗上昇の要因となる。更には、部分的な繊維の脱落によりピンホールが発生する事で耐電圧性が低下し、漏れ電流が増加する。 Further, a separator made by a general paper making method often uses a surfactant to uniformly disperse a raw material slurry. In some cases, the fibers are bonded to each other with a binder or the like in order to prevent the fibers from falling off or to have a tensile strength that can withstand the tension at the time of manufacturing the capacitor. However, these surfactants and binders are factors that impede the impregnation of the electrolyte between the fibers or inside the fibers during the production of capacitors and the like. In addition, since it gradually elutes into the electrolyte during use, it contaminates the electrolyte and causes an increase in internal resistance. Furthermore, withstand voltage resistance is reduced due to the occurrence of pinholes due to partial fiber dropping, and leakage current increases.
バインダーを用いない長繊維不織布を用いたセパレーター及びコンデンサとしては、銅アンモニアレーヨンから成る平均直径２０μｍ以下のセルロース系長繊維で構成した織布または不織布から成るセパレーターおよびそれを用いたコンデンサがある（特許文献２参照）。 Separators and capacitors using long-fiber non-woven fabric that does not use a binder include separators made of woven or non-woven fabric made of cellulose-based long fibers made of copper ammonia rayon and having an average diameter of 20 μm or less, and capacitors using the same (patents). Reference 2).
しかしながら、湿式スパンボンド法で製造されるセルロース系長繊維不織布は、繊維配列に異方性があり、一般的には抄紙法のような緻密なウエブを形成することは困難である。このため密度や目付を特許文献２記載の範囲まで下げてしまうと、セパレーターの隔離性能がはたせず、耐電圧性が低下して、漏れ電流が増加したり、コンデンサのエージング工程時に電気的なショートが発生したりする。
このため、内部抵抗が低く、かつ耐電圧性に優れたセパレーターが求められていた。
However, cellulose-based long fiber nonwoven fabrics produced by the wet spunbond method have anisotropy in fiber arrangement, and it is generally difficult to form a dense web as in the papermaking method. For this reason, if the density or basis weight is lowered to the range described in Patent Document 2, the separator's isolation performance will not be achieved, the withstand voltage will be reduced, the leakage current will increase, and the electrical capacity will be increased during the aging process of the capacitor. A short circuit may occur.
For this reason, a separator having low internal resistance and excellent voltage resistance has been demanded.
本発明の課題は、上記従来技術の問題点を解決し、内部抵抗が低く、かつ耐電圧性に優れたセパレーターを提供することである。 An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a separator having low internal resistance and excellent voltage resistance.
上記課題を達成するために、本発明は下記の発明を提供する。
（１）セルロース系繊維不織布から構成されたコンデンサまたは電池用セパレーターにおいて、前記不織布の嵩密度が０．４〜１．１ｇ／ｃｍ3であり、かつ、前記不織布を構成する繊維の平均繊維径および繊維径分布率がそれぞれ０．５〜８．０μｍおよび４０％以下であることを特徴とするコンデンサまたは電池用セパレーター。
（２）前記不織布が長繊維である事を特徴とする請求項１に記載のコンデンサまたは電池用セパレーター。
In order to achieve the above object, the present invention provides the following inventions.
(1) In a capacitor or battery separator composed of a cellulosic fiber nonwoven fabric, the nonwoven fabric has a bulk density of 0.4 to 1.1 g / cm 3 , and an average fiber diameter of fibers constituting the nonwoven fabric and A capacitor or battery separator, wherein the fiber diameter distribution ratio is 0.5 to 8.0 μm and 40% or less, respectively.
(2) The capacitor or battery separator according to claim 1, wherein the nonwoven fabric is a long fiber.
本発明によれば、内部抵抗が低く、かつ耐電圧性に優れたセパレーターが得られる。 According to the present invention, a separator having low internal resistance and excellent voltage resistance can be obtained.
本発明におけるセルロース系繊維とは、麻、綿等の天然セルロース繊維、キュプラ、ビスコースレーヨン、ポリノジックレーヨン等の再生セルロース繊維およびリヨセルなどの精製セルロース繊維などであるが、好ましくは、繊維径を均一に制御できる再生セルロース繊維および精製セルロース繊維であり、更に好ましくは再生セルロース連続長繊維（例えば旭化成せんい株式会社製のキュプラ不織布「ベンリーゼ（登録商標）」）である。 Cellulosic fibers in the present invention include natural cellulose fibers such as hemp and cotton, regenerated cellulose fibers such as cupra, viscose rayon and polynosic rayon, and purified cellulose fibers such as lyocell, but preferably have a uniform fiber diameter. Regenerated cellulose fibers and refined cellulose fibers that can be controlled to a high degree, and more preferably regenerated cellulose continuous long fibers (for example, cupra nonwoven fabric “Benlyse (registered trademark)” manufactured by Asahi Kasei Fibers Corporation).
本発明のセルロース系繊維不織布とは、主としてセルロース系繊維からなる。セルロース系繊維１００％であってもよく、製品に組み込まれた際、内部抵抗の増大や耐電圧性の低下が起こらない程度に、本発明の構成要件を満たす範囲で、ポリエステル等の合成繊維を混用しても良い。この場合には、本発明における不織布中のセルロース系繊維の含有量は５０重量％以上が好ましく、より好ましくは７５重量％以上である。 The cellulose fiber nonwoven fabric of the present invention is mainly composed of cellulosic fibers. 100% cellulosic fiber may be used, and when incorporated into a product, synthetic fibers such as polyester are used within a range that satisfies the constitutional requirements of the present invention to such an extent that an increase in internal resistance and a decrease in voltage resistance do not occur. You may mix. In this case, the content of the cellulosic fibers in the nonwoven fabric in the present invention is preferably 50% by weight or more, more preferably 75% by weight or more.
本発明のセルロース系繊維不織布の構造は、少なくとも片側表面においてセルロース繊維が面積率５０％以上で存在することが好ましく、更に好ましくは７５％以上である。ここでいう面積率とは表面に存在するセルロース系繊維の面積比率であり、例えば合成繊維と複合されている場合、セルロース系繊維が染色され、合成繊維が染色されない染料で構造体を染色し、表面積に対する染色部分の面積を画像解析等によって求めることができる。また必要に応じて例えば、両面が主にセルロース系繊維で中央部が主に合成繊維で構成された３層構造の構造体であってもよい。 In the structure of the cellulose fiber nonwoven fabric of the present invention, the cellulose fibers are preferably present at an area ratio of 50% or more, more preferably 75% or more on at least one surface. The area ratio referred to here is the area ratio of the cellulosic fibers present on the surface. For example, when compounded with synthetic fibers, the cellulosic fibers are dyed, and the structure is dyed with a dye that does not dye the synthetic fibers, The area of the stained portion relative to the surface area can be obtained by image analysis or the like. Further, for example, a three-layer structure in which both surfaces are mainly composed of cellulosic fibers and the central portion is mainly composed of synthetic fibers may be used as necessary.
本発明の不織布の製造方法は特に限定されないが、好ましくは界面活性剤やバインダーを使用せずに製造可能なスパンボンド法であり、更に好ましくは湿式スパンボンド法である。また不織布を複合する場合、複合方法も特に限定されないが、好ましくは電解液へ溶出するようなバインダーを用いない、高圧流体による複合やエンボス等による圧着が良い。 Although the manufacturing method of the nonwoven fabric of this invention is not specifically limited, Preferably it is the spun bond method which can be manufactured without using surfactant and a binder, More preferably, it is a wet spun bond method. When the nonwoven fabric is composited, the composite method is not particularly limited, but preferably a binder that elutes into the electrolytic solution is not used, and the composite by high-pressure fluid or pressure bonding by embossing is good.
本発明における平均繊維径とは、不織布の表面を走査型電子顕微鏡（日立製作所製 Ｓ−３５００Ｎ）により倍率２００倍にて撮影し、その写真から無作為に５０箇所選択して測定した繊維径（ｎ＝５０）の平均値である。 The average fiber diameter in the present invention refers to a fiber diameter (measured by randomly selecting 50 spots from a photograph of the surface of a nonwoven fabric with a scanning electron microscope (S-3500N manufactured by Hitachi, Ltd.) at a magnification of 200 times. n = 50).
本発明における不織布を構成する繊維の平均繊維径は、一般的な前記製造方法で作る場合においては、セパレーターの内部抵抗を低くし、かつ緻密性を上げることによって耐電圧性を高めるという観点から、０．５〜８．０μｍであることが必要であり、好ましくは１．０〜４．９μｍ、更に好ましくは２．０〜４．９μｍである。０．５μｍ未満になると、繊維の単糸強度が弱くなり、コンデンサや電池の製造時等に電極のアルミ箔との摩擦等によって容易に繊維が脱落し、短絡の原因となる。８．０μｍを超えると、ベンリーゼなどのスパンボンド法の場合、繊維の集積斑によってピンホールが発生し易くなり、耐電圧性が低下する。また、セパレーターに含浸された電解液中の電荷の通路が長くなると、内部抵抗が増大するため、通路を阻害する物質（本ケースでは繊維）の表面積は小さいほうがよい。 In the case where the average fiber diameter of the fibers constituting the nonwoven fabric in the present invention is produced by the general production method, from the viewpoint of increasing the voltage resistance by reducing the internal resistance of the separator and increasing the density, It is necessary to be 0.5 to 8.0 μm, preferably 1.0 to 4.9 μm, and more preferably 2.0 to 4.9 μm. When the thickness is less than 0.5 μm, the single yarn strength of the fiber becomes weak, and the fiber easily falls off due to friction with the aluminum foil of the electrode during the manufacture of a capacitor or battery, etc., causing a short circuit. When the thickness exceeds 8.0 μm, in the case of a spunbond method such as Benize, pinholes are likely to be generated due to fiber accumulation spots, and the voltage resistance decreases. Further, when the charge passage in the electrolyte impregnated in the separator becomes longer, the internal resistance increases. Therefore, the surface area of the substance that obstructs the passage (fiber in this case) is better.
本発明における繊維径分布率とは、下式（１）に示す繊維径の不均一性を言う。
繊維径分布率＝（σ／Ｘ）×１００・・・・（１）
（式中、Ｘは平均繊維径であり、σは標準偏差である。）
ここで繊維の標準偏差は、平均繊維径と同様に走査型電子顕微鏡にて測定した５０箇所における標準偏差である。
The fiber diameter distribution rate in the present invention refers to the nonuniformity of the fiber diameter shown in the following formula (1).
Fiber diameter distribution rate = (σ / X) × 100 (1)
(In the formula, X is an average fiber diameter, and σ is a standard deviation.)
Here, the standard deviation of the fiber is the standard deviation at 50 points measured with a scanning electron microscope in the same manner as the average fiber diameter.
繊維径分布率が高くなるほど、繊維径は不均一である。繊維径の不均一な繊維が多数存在すると、繊維密度の高い部分と繊維密度の低い部分が生じ、繊維密度の高い部分では内部抵抗が増大し、繊維密度の低い部分では耐電圧性が悪化し、漏れ電流が増加する。
本発明において繊維径分布率は、内部抵抗の増大や耐電圧性の悪化を防ぐと言う観点から、４０％以下である事が必要であり、より好ましくは３５％以下、更に好ましくは３０％以下である。また、製造コスト等との兼ね合いから３％以下にするのは困難である。
The higher the fiber diameter distribution rate, the more uneven the fiber diameter. If there are many fibers with non-uniform fiber diameters, there will be a part with high fiber density and a part with low fiber density, the internal resistance will increase at the part with high fiber density, and the withstand voltage will deteriorate at the part with low fiber density. , Leakage current increases.
In the present invention, the fiber diameter distribution ratio is required to be 40% or less, more preferably 35% or less, still more preferably 30% or less, from the viewpoint of preventing an increase in internal resistance and deterioration of voltage resistance. It is. Moreover, it is difficult to make it 3% or less in view of the manufacturing cost and the like.
本発明における嵩密度とは、不織布内の空隙を含めた体積で不織布の重量を除した値を言う。本発明においては不織布の嵩密度は、内部抵抗を極度に増大させずに所望の耐電圧性を高めるという観点から、０．４〜１．１ｇ／ｃｍ3である事を必要とするが、より好ましくは０．５〜０．８ｇ／ｃｍ3である。嵩密度が０．４ｇ／ｃｍ3より小さいと耐電圧性が低下し、１．１ｇ／ｃｍ3より大きいと内部抵抗が大きくなる。 The bulk density in the present invention refers to a value obtained by dividing the weight of the nonwoven fabric by the volume including voids in the nonwoven fabric. In the present invention, the bulk density of the nonwoven fabric needs to be 0.4 to 1.1 g / cm 3 from the viewpoint of increasing a desired voltage resistance without extremely increasing the internal resistance, Preferably it is 0.5-0.8 g / cm < 3 >. When the bulk density is less than 0.4 g / cm 3 , the voltage resistance decreases, and when it is greater than 1.1 g / cm 3 , the internal resistance increases.
セルロース系繊維不織布の繊維軸方向の密度は、繊維間の緻密性が高いものであれば、特に限定されない。 The density in the fiber axis direction of the cellulosic fiber nonwoven fabric is not particularly limited as long as the density between fibers is high.
本発明における長繊維とは平均繊維長が２８ｍｍ以上のものを言うが、好ましくは平均繊維長３５ｍｍ以上、更に好ましくは繊維が切断されずに連続的に繋がっている連続長繊維である。平均繊維長が２８ｍｍ未満の短繊維は漏れ電流増加の原因となる繊維の脱落が発生し易いので好ましくない。 The long fiber in the present invention means a fiber having an average fiber length of 28 mm or more, preferably an average fiber length of 35 mm or more, and more preferably a continuous long fiber that is continuously connected without being cut. Short fibers having an average fiber length of less than 28 mm are not preferable because fibers are likely to fall off causing an increase in leakage current.
本発明におけるセルロース系繊維不織布は、長繊維１００％であることが好ましいが、セパレーターの構造によっては、漏れ電流増加の原因となる繊維の脱落が発生しない程度に、本発明の構成要件を満たす短繊維を混用してもよい。但しこの場合には、短繊維の含有量は５０重量％未満であることが好ましく、より好ましくは２５重量％未満である。また短繊維を混用した場合の不織布の構造は、短繊維の脱落を防止すると言う観点から、長繊維／短繊維／長繊維の３層構造の構造体とすることが好ましい。 The cellulose fiber nonwoven fabric in the present invention is preferably 100% long fiber, but depending on the structure of the separator, a short fiber that satisfies the constituent requirements of the present invention to the extent that the fiber that causes an increase in leakage current does not occur. Fibers may be mixed. However, in this case, the content of the short fibers is preferably less than 50% by weight, more preferably less than 25% by weight. In addition, the structure of the nonwoven fabric when the short fibers are mixed is preferably a three-layer structure of long fibers / short fibers / long fibers from the viewpoint of preventing the short fibers from falling off.
本発明における不織布の平均孔径は、所望の性能が得られる範囲であれば特に限定されるものではないが、好ましくはＪＩＳ Ｋ−３８３２（バブルポイント法）の試験にて０．３〜２０μｍであり、更に好ましくは０．３〜１０μｍである。 The average pore diameter of the nonwoven fabric in the present invention is not particularly limited as long as desired performance is obtained, but is preferably 0.3 to 20 μm in a test of JIS K-3832 (bubble point method). More preferably, the thickness is 0.3 to 10 μm.
本発明における不織布の厚みは、所望の性能が得られる範囲であれば特に限定されるものではないが、好ましくは１０〜１００μｍであり、より好ましくは２０〜７０μｍであり、更に好ましくは２５〜６０μｍである。 The thickness of the nonwoven fabric in the present invention is not particularly limited as long as desired performance can be obtained, but is preferably 10 to 100 μm, more preferably 20 to 70 μm, and further preferably 25 to 60 μm. It is.
本発明において不織布の目付は、所望の内部抵抗と耐電圧性が得られる範囲であれば特に限定されるものではないが、好ましくは８〜５０ｇ／ｍ2、より好ましくは１０〜３０ｇ／ｍ2である。 In the present invention, the basis weight of the nonwoven fabric is not particularly limited as long as desired internal resistance and voltage resistance can be obtained, but is preferably 8 to 50 g / m 2 , more preferably 10 to 30 g / m 2. It is.
本発明のセパレーターは、前記繊維径、繊維径分布率および嵩密度を適切にコントロールすることにより、内部抵抗を低下させ、耐電圧性を高めている。このため、上記嵩密度を得るため、必要に応じて不織布を複数枚積層させたり、カレンダーなどでプレスさせたりすることができる。この場合、積層枚数は、内部抵抗を必要以上に増大させないという観点から、１０枚未満であることが好ましい。より好ましくは５枚未満であり、更に好ましくは３枚未満である。 In the separator of the present invention, by appropriately controlling the fiber diameter, fiber diameter distribution rate, and bulk density, the internal resistance is lowered and the voltage resistance is increased. For this reason, in order to obtain the above-mentioned bulk density, a plurality of nonwoven fabrics can be laminated or pressed with a calendar or the like as necessary. In this case, the number of stacked layers is preferably less than 10 from the viewpoint of not increasing the internal resistance more than necessary. More preferably, it is less than 5, more preferably less than 3.
また、カレンダーによるプレスは、所望の嵩密度が得られるものであれば、その装置並びに線圧およびロール温度等の加工条件については特に限定されるものではないが、好ましいロールの材質は、ＡＳＴＭ−Ｄ２２４０ショアＤ硬度が７５以上の樹脂、あるいは金属製である。プレス圧力は好ましくは線圧が１０〜１０００Ｎ／ｍｍであり、更に好ましくは５０〜５００Ｎ／ｍｍである。ロール温度は好ましくは１０〜８０℃である。 The calender press is not particularly limited as long as a desired bulk density can be obtained, and the processing conditions such as the linear pressure and roll temperature are not particularly limited, but the preferred roll material is ASTM- D2240 Shore D hardness is 75 or more resin or metal. The pressing pressure is preferably a linear pressure of 10 to 1000 N / mm, and more preferably 50 to 500 N / mm. The roll temperature is preferably 10 to 80 ° C.
本発明のセパレーターは、どのようなコンデンサ及び電池にも用いることができるが、電気二重層コンデンサ、電解コンデンサおよびリチウムイオン電池に好適に用いられ、電解コンデンサおよび電気二重層コンデンサに特に好適に用いられる。 The separator of the present invention can be used for any capacitors and batteries, but is preferably used for electric double layer capacitors, electrolytic capacitors and lithium ion batteries, and particularly preferably used for electrolytic capacitors and electric double layer capacitors. .
本発明において、セパレーターに含浸させる電解液の種類については、セパレーターに対し悪影響を与えないものであれば特に制限はされない。例えば、１，４−ブタンジオール、グリセリン、ポリオキシアルキレンポリオール、フラン系、スルホラン系、カーボネート系、ラクトン系、イミダゾリジノン系およびアルキレングリコール系を用いることができる。これらの中でもアルキレングリコール系およびラクトン系が好ましい。アルキレングリコール系としてはエチレングリコールおよびプロピレングリコールが特に好ましく、ラクトン系としてはγ−ブチロラクトンが特に好ましい。 In the present invention, the type of electrolyte solution impregnated in the separator is not particularly limited as long as it does not adversely affect the separator. For example, 1,4-butanediol, glycerin, polyoxyalkylene polyol, furan, sulfolane, carbonate, lactone, imidazolidinone, and alkylene glycol can be used. Among these, alkylene glycol type and lactone type are preferable. As the alkylene glycol system, ethylene glycol and propylene glycol are particularly preferable, and as the lactone system, γ-butyrolactone is particularly preferable.
また、前記電解液には、無機酸、有機酸、無機酸塩、有機酸塩、アンモニウム塩、アミン塩、四級アンモニウム塩またはアミジン系塩等を電解液の性能向上のために適宜付加することができる。
また本発明のセパレーターにおいて、本発明の目的を損なわない限りセパレーターに更に追加的に付与することができる各種の機能付加を任意に行うことができる。
In addition, an inorganic acid, an organic acid, an inorganic acid salt, an organic acid salt, an ammonium salt, an amine salt, a quaternary ammonium salt, an amidine salt, or the like is appropriately added to the electrolytic solution in order to improve the performance of the electrolytic solution. Can do.
Moreover, in the separator of this invention, unless the objective of this invention is impaired, the various function addition which can be further provided to a separator can be performed arbitrarily.
以下、本発明を実施例および比較例により具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。また実施例および比較例中の各種評価は、下記のようにして行った。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited only to these Examples. Various evaluations in Examples and Comparative Examples were performed as follows.
（１）目付
０．０５ｍ2以上の面積の不織布を１０５℃で一定重量になるまで乾燥後、２０℃および６５％ＲＨの恒温室に１６時間以上放置した後、重量を測定し、１ｍ2当たりの重量を求めた（単位はｇ／ｍ2）。
（２）厚み
ＪＩＳ−Ｌ１０９６の厚み試験にて荷重を１．９６ｋＰａに設定して測定した（単位はμｍ）。
（３）嵩密度
上記目付および厚みから、目付／厚みにて算出した（単位はｇ／ｃｍ3）。
（４）平均繊維径
前記の通りである（単位はμｍ）。
（５）繊維径分布率
前記式（１）を用いて算出した。
(1) the mass per unit area 0.05m dried 2 or more the area of the nonwoven fabric to a constant weight at 105 ° C., allowed to stand in a thermostatic chamber of RH 20 ° C. and 65% for 16 hours or more, and weighed, 1 m 2 per Was determined (unit: g / m 2 ).
(2) Thickness Measured by setting the load to 1.96 kPa in the thickness test of JIS-L1096 (unit: μm).
(3) Bulk density Based on the basis weight and thickness, the bulk density was calculated as basis weight / thickness (unit: g / cm 3 ).
(4) Average fiber diameter As described above (unit: μm).
(5) Fiber diameter distribution rate It calculated using said Formula (1).
（６）内部抵抗
エチレングリコール１００部にて作製した電解液に直径４０ｍｍのサンプル不織布を浸漬させた後、減圧下で１時間脱気を行う。脱気後のサンプルを２つの電極（白金黒付けした直径３８ｍｍの円板形状のもの）の間に挿入し、１２ｃＮの荷重を両電極間にかけ両電極間にセパレーターを固定する。次に、２０℃の温度および１００ｋＨｚの周波数でＬＣＲメータを用いて両電極間の電気抵抗を測定する（単位はΩ）。得られた測定値から、サンプル不織布を挿入せずに測定しておいたブランク値を差し引いて、サンプル不織布の内部抵抗とした。
(6) Internal resistance After a sample nonwoven fabric having a diameter of 40 mm is immersed in an electrolytic solution prepared with 100 parts of ethylene glycol, deaeration is performed for 1 hour under reduced pressure. The sample after deaeration is inserted between two electrodes (platinum-plated 38 mm diameter disk-shaped), a load of 12 cN is applied between both electrodes, and the separator is fixed between both electrodes. Next, the electrical resistance between both electrodes is measured using an LCR meter at a temperature of 20 ° C. and a frequency of 100 kHz (unit: Ω). The blank value measured without inserting the sample nonwoven fabric was subtracted from the obtained measured value to obtain the internal resistance of the sample nonwoven fabric.
（７）耐電圧性
セパレーターの固定までは、上記内部抵抗の評価方法と同様に実施する。次に二枚の電極を各々クリップではさみ、電極間に１０Ｖの直流電圧を耐電圧試験装置（菊水電子工業株式会社製 ＴＯＳ５０５１Ａ）にて印加する。この際の漏れ電流値を測定し、漏れ電流の値で耐電圧性を評価する（単位はｍＡ）。
(7) Voltage resistance Until the separator is fixed, it is carried out in the same manner as the evaluation method for internal resistance. Next, the two electrodes are each sandwiched between clips, and a DC voltage of 10 V is applied between the electrodes with a withstand voltage test apparatus (TOS5051A manufactured by Kikusui Electronics Corporation). The leakage current value at this time is measured, and the voltage resistance is evaluated based on the leakage current value (unit: mA).
（８）総合評価
上記（６）および（７）の項目を総合的に判断し、下記のように総合評価した。
◎：非常に優れている。
○：優れている。
×：不適である。
(8) Comprehensive evaluation The above items (6) and (7) were comprehensively judged and comprehensively evaluated as follows.
A: Very good.
○: Excellent.
X: unsuitable.
［実施例１］
特開２００５−１２０５１９号公報の実施例１に従って再生セルロース連続長繊維不織布を作製した。但し、目付１４．０ｇ／ｍ2、厚み４３μｍ、平均繊維径３．６μｍおよび繊維径分布率３６％の不織布が得られるように、原液の吐出量、紡水温度、ネットスピード、ネット振動数および高圧水流交絡条件を変更した。
[Example 1]
A regenerated cellulose continuous long-fiber nonwoven fabric was prepared according to Example 1 of JP-A-2005-120519. However, in order to obtain a nonwoven fabric having a basis weight of 14.0 g / m 2 , a thickness of 43 μm, an average fiber diameter of 3.6 μm, and a fiber diameter distribution rate of 36%, the discharge rate of the stock solution, spinning temperature, net speed, net frequency and The high pressure hydroentanglement conditions were changed.
得られた不織布を、上部および下部のロールとしてＡＳＴＭ−Ｄ２２４０ショアＤ硬度が９５の樹脂製ロールを有するカレンダー加工機にて、所望の厚みおよび嵩密度になるようにカレンダー処理して、セパレーターを作製した。
得られたセパレーターの評価結果を表１に示したが、内部抵抗が極めて低く、漏れ電流の小さい耐電圧性に優れたセパレーターであった。
The obtained nonwoven fabric is calendered to a desired thickness and bulk density by a calendering machine having a roll made of resin having ASTM-D2240 Shore D hardness of 95 as upper and lower rolls to produce a separator. did.
The evaluation results of the obtained separator are shown in Table 1. The separator was extremely low in internal resistance, small in leakage current, and excellent in voltage resistance.
［実施例２］
目付１８．０ｇ／ｍ2、厚み５７μｍ、平均繊維径４．６μｍおよび繊維径分布率２８％の不織布が得られるように、原液の吐出量、紡水温度、ネットスピード、ネット振動数および高圧水流交絡条件を変更したことを除いて、実施例１と同様に再生セルロース連続長繊維不織布を作製した。
[Example 2]
In order to obtain a nonwoven fabric having a basis weight of 18.0 g / m 2 , a thickness of 57 μm, an average fiber diameter of 4.6 μm, and a fiber diameter distribution rate of 28%, the discharge amount of raw liquid, spinning temperature, net speed, net frequency and high-pressure water flow A regenerated cellulose continuous long-fiber nonwoven fabric was produced in the same manner as in Example 1 except that the confounding conditions were changed.
得られた不織布を用いて、実施例１と同様にセパレーターを作製し、その評価を行なった。結果を表１に示したが、内部抵抗が極めて低く、漏れ電流の極めて小さい耐電圧性に優れたセパレーターであった。 Using the obtained non-woven fabric, a separator was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 1. As a result, the separator was excellent in voltage resistance with extremely low internal resistance and very low leakage current.
［実施例３］
目付２２．０ｇ／ｍ2、厚み６７μｍ、平均繊維径４．９μｍおよび繊維径分布率３２％の不織布が得られるように、原液の吐出量、紡水温度、ネットスピード、ネット振動数および高圧水流交絡条件を変更したことを除いて、実施例１と同様に再生セルロース連続長繊維不織布を作製した。
[Example 3]
In order to obtain a nonwoven fabric having a basis weight of 22.0 g / m 2 , a thickness of 67 μm, an average fiber diameter of 4.9 μm and a fiber diameter distribution rate of 32%, the discharge rate of the stock solution, the spinning temperature, the net speed, the net frequency and the high-pressure water flow A regenerated cellulose continuous long-fiber nonwoven fabric was produced in the same manner as in Example 1 except that the confounding conditions were changed.
得られた不織布を用いて、実施例１と同様にセパレーターを作製し、その評価を行なった。結果を表１に示したが、内部抵抗が極めて低く、漏れ電流の極めて小さい耐電圧性に優れたセパレーターであった。 Using the obtained non-woven fabric, a separator was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 1. As a result, the separator was excellent in voltage resistance with extremely low internal resistance and very low leakage current.
［実施例４］
目付３０．０ｇ／ｍ2、厚み９６μｍ、平均繊維径５．８μｍおよび繊維径分布率３６％の不織布が得られるように、原液の吐出量、紡水温度、ネットスピード、ネット振動数および高圧水流交絡条件を変更したことを除いて、実施例１と同様に再生セルロース連続長繊維不織布を作製した。
[Example 4]
In order to obtain a nonwoven fabric having a basis weight of 30.0 g / m 2 , a thickness of 96 μm, an average fiber diameter of 5.8 μm, and a fiber diameter distribution rate of 36%, the discharge amount of the stock solution, the spinning temperature, the net speed, the net frequency and the high-pressure water flow A regenerated cellulose continuous long-fiber nonwoven fabric was produced in the same manner as in Example 1 except that the confounding conditions were changed.
得られた不織布を用いて、実施例１と同様にセパレーターを作製し、その評価を行なった。結果を表１に示したが、内部抵抗が極めて低く、漏れ電流の極めて小さい耐電圧性に優れたセパレーターであった。 Using the obtained non-woven fabric, a separator was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 1. As a result, the separator was excellent in voltage resistance with extremely low internal resistance and very low leakage current.
［比較例１］
溶剤紡糸セルロース繊維（レンチング社製：商品名リヨセル）を叩解し、得られた平均繊維径８．０μｍおよび繊維径分布率６０％の叩解された繊維を、ポリオキシエチレンアルキルエーテル１％溶液中に入れ、十分均一に繊維を分散させスラリーを作製した。得られたスラリーを抄紙機で抄紙して、目付２２．０ｇ／ｍ2および厚み４０μｍのセパレーターを作製して、実施例１と同様に評価した。評価結果を表１に示したが、セパレーターの内部抵抗は高く、また漏れ電流の大きな耐電圧性の悪いセパレーターであり、電気的ショートも発生してしまった。
[Comparative Example 1]
Solvent-spun cellulose fiber (manufactured by Lenzing Co., Ltd .: trade name Lyocell) was beaten, and the obtained beaten fiber having an average fiber diameter of 8.0 μm and a fiber diameter distribution rate of 60% was placed in a 1% solution of polyoxyethylene alkyl ether. Then, the fibers were sufficiently uniformly dispersed to prepare a slurry. The obtained slurry was made with a paper machine to produce a separator having a basis weight of 22.0 g / m 2 and a thickness of 40 μm, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1. As a result, the separator had a high internal resistance, a large leakage current, a poor voltage resistance, and an electrical short circuit occurred.
［比較例２］
目付６．０ｇ／ｍ2、厚み３０μｍ、平均繊維径５．０μｍ、嵩密度０．２ｇ／ｃｍ3および繊維径分布率３８％の再生セルロース連続長繊維不織布をカレンダー加工せずにそのまま用い、セパレーターを作製した。評価結果を表１に示したが、内部抵抗は極めて低いが、漏れ電流が大きい耐電圧性の悪いものであった。電気的ショートも発生してしまった。
[Comparative Example 2]
A separator made of a continuous cellulose continuous fiber nonwoven fabric having a basis weight of 6.0 g / m 2 , a thickness of 30 μm, an average fiber diameter of 5.0 μm, a bulk density of 0.2 g / cm 3 and a fiber diameter distribution rate of 38% is used as it is without calendering. Was made. The evaluation results are shown in Table 1. Although the internal resistance was extremely low, the leakage current was large and the voltage resistance was poor. An electrical short circuit has also occurred.
［比較例３］
カレンダー加工によりセパレーターの嵩密度を１．１６ｇ／ｃｍ3にしたことを除いて、実施例３と同様にセパレーターを作製した。得られたセパレーターの評価結果を表１に示したが、漏れ電流が極めて小さく耐電圧性は優れていたが、内部抵抗が極めて大きいセパレーターであった。
[Comparative Example 3]
A separator was produced in the same manner as in Example 3 except that the bulk density of the separator was 1.16 g / cm 3 by calendering. The evaluation results of the obtained separator are shown in Table 1. Although the leakage current was extremely small and the voltage resistance was excellent, the separator had a very large internal resistance.
［比較例４］
目付１４．０ｇ／ｍ2、厚み７０μｍ、平均繊維径１２μｍおよび繊維径分布率３６％の不織布が得られるように、原液の吐出量、紡水温度、ネットスピード、ネット振動数および高圧水流交絡条件を変更したことを除いて、実施例１と同様に再生セルロース連続長繊維不織布を作製した。
[Comparative Example 4]
In order to obtain a nonwoven fabric having a basis weight of 14.0 g / m 2 , a thickness of 70 μm, an average fiber diameter of 12 μm, and a fiber diameter distribution rate of 36%, the discharge rate of the stock solution, the spinning temperature, the net speed, the net frequency, and the high-pressure hydroentanglement conditions A regenerated cellulose continuous long-fiber nonwoven fabric was produced in the same manner as in Example 1 except that was changed.
得られた不織布を用いて、実施例１と同様にセパレーターを作製し、その評価を行なった。結果を表１に示したが、内部抵抗は極めて低いが、漏れ電流が大きい耐電圧性の悪いセパレーターであった。電気的ショートも発生してしまった。 Using the obtained non-woven fabric, a separator was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 1. Although the internal resistance was extremely low, the separator had a large leakage current and poor voltage resistance. An electrical short circuit has also occurred.
本発明のコンデンサまたは電池用セパレーターは、内部抵抗が小さく、かつ耐電圧性に優れたセパレーターであり、特に、電解コンデンサおよび電気二重層コンデンサに好適に用いられる。 The capacitor or battery separator of the present invention is a separator having low internal resistance and excellent voltage resistance, and is particularly suitably used for electrolytic capacitors and electric double layer capacitors.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007337260A JP4938640B2 (en) | 2007-12-27 | 2007-12-27 | separator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007337260A JP4938640B2 (en) | 2007-12-27 | 2007-12-27 | separator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009158811A JP2009158811A (en) | 2009-07-16 |
| JP4938640B2 true JP4938640B2 (en) | 2012-05-23 |
Family
ID=40962486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007337260A Expired - Fee Related JP4938640B2 (en) | 2007-12-27 | 2007-12-27 | separator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4938640B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5413583B2 (en) * | 2009-07-27 | 2014-02-12 | エルナー株式会社 | Electrolytic capacitor |
| JP5844067B2 (en) * | 2011-05-02 | 2016-01-13 | 株式会社ダイセル | Non-woven fiber laminate, method for producing the same, and separator |
| CN103329310B (en) * | 2011-10-13 | 2016-09-21 | 特种东海制纸株式会社 | Micro-porous film and manufacture method thereof |
| WO2013054884A1 (en) | 2011-10-13 | 2013-04-18 | 特種東海製紙株式会社 | Microporous membrane and manufacturing method therefor |
| RU2013134483A (en) | 2011-10-13 | 2015-01-27 | Токусю Токай Пейпер Ко., Лтд. | POROUS MEMBRANE AND METHOD FOR PRODUCING IT |
| KR101331481B1 (en) | 2011-10-13 | 2013-11-20 | 도쿠슈 도카이 세이시 가부시키가이샤 | Separator for electrochemical device and process for preparing the same |
| JP6412805B2 (en) | 2015-01-16 | 2018-10-24 | ニッポン高度紙工業株式会社 | Separator and aluminum electrolytic capacitor |
| CN108140491B (en) * | 2015-09-29 | 2020-04-10 | 日本高度纸工业株式会社 | Separator for electrochemical element and electrochemical element |
| CN108318366B (en) * | 2017-12-26 | 2020-07-24 | 中国电子科技集团公司第十八研究所 | Method for simulating battery electro-hydraulic distribution and combined clamp |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2692126B2 (en) * | 1988-04-20 | 1997-12-17 | 松下電器産業株式会社 | Electrolytic capacitor |
| JPH01293608A (en) * | 1988-05-23 | 1989-11-27 | Matsushita Electric Ind Co Ltd | Electrolytic capacitor |
| JP2000003834A (en) * | 1998-06-16 | 2000-01-07 | Nippon Kodoshi Corp | Electric double-layer capacitor |
| JP4776876B2 (en) * | 2003-09-30 | 2011-09-21 | 日本バイリーン株式会社 | Battery separator and battery equipped with the same |
| JP2005120535A (en) * | 2003-10-20 | 2005-05-12 | Tapyrus Co Ltd | Liquid crystal polyester melt blow nonwoven fabric and method for producing the same |
| JP4740034B2 (en) * | 2006-05-23 | 2011-08-03 | 株式会社巴川製紙所 | Electrochemical element separator |
-
2007
- 2007-12-27 JP JP2007337260A patent/JP4938640B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009158811A (en) | 2009-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4938640B2 (en) | separator | |
| JP4244294B2 (en) | Separator for electrochemical device and manufacturing method thereof | |
| CN106537537B (en) | Electrical storage device partition and the electrical storage device for using the partition | |
| KR102662350B1 (en) | Separator for electrochemical devices and electrochemical devices | |
| JP6412805B2 (en) | Separator and aluminum electrolytic capacitor | |
| CN113106786A (en) | Multilayer composite solid and semi-solid electrolytic capacitor diaphragm paper and preparation method and application thereof | |
| JP4869875B2 (en) | Separator for condenser | |
| JP2007067389A (en) | Separator for electrochemical element | |
| KR101827617B1 (en) | Separator for electric double layer capacitors, and electric double layer capacitor | |
| JP5876373B2 (en) | Electrochemical element separator and electrochemical element using the same | |
| JP2014056953A (en) | Separator for capacitor and capacitor | |
| JP2015088703A (en) | Separator for capacitors, and capacitor using the same | |
| KR20200089672A (en) | Separators and electrochemical devices for electrochemical devices | |
| JP2016171166A (en) | Separator for electricity storage device and electricity storage device using the separator | |
| JP3971905B2 (en) | Separator for electrochemical device and method for producing the same | |
| JP2010239028A (en) | Separator for electric storage device | |
| JP2011210680A (en) | Separator for battery | |
| CN109952666B (en) | Thin, high density nonwoven separator for energy storage devices and method of making same | |
| WO2017170065A1 (en) | Separator for electrochemical element and electrochemical element | |
| JP2008098291A (en) | Separator for capacitor | |
| JP2020088024A (en) | Solid electrolytic capacitor or hybrid separator for electrolytic capacitor, and solid electrolytic or hybrid electrolytic capacitor which is arranged by use thereof | |
| JP2001084986A (en) | Nonwoven fabric for alkaline storage battery separator and manufacturing method therefor | |
| JP2015053315A (en) | Method of manufacturing separator for capacitor, separator for capacitor and capacitor | |
| JP7273497B2 (en) | Separator for solid electrolytic capacitor or hybrid electrolytic capacitor and solid electrolytic capacitor or hybrid electrolytic capacitor using the same | |
| JP2016178246A (en) | Separator for solid electrolytic capacitor, solid electrolytic capacitor, and manufacturing method of separator for solid electrolytic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20101201 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120110 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120131 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120223 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150302 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |