JP2003059766A - Separator for electrochemical element and manufacturing method thereof - Google Patents
Separator for electrochemical element and manufacturing method thereofInfo
- Publication number
- JP2003059766A JP2003059766A JP2001249795A JP2001249795A JP2003059766A JP 2003059766 A JP2003059766 A JP 2003059766A JP 2001249795 A JP2001249795 A JP 2001249795A JP 2001249795 A JP2001249795 A JP 2001249795A JP 2003059766 A JP2003059766 A JP 2003059766A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- fiber
- wholly aromatic
- fibers
- electrochemical
- 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.)
- Granted
Links
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
- Cell Separators (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性、電解液保
持性、耐電極性に優れる電気化学素子用セパレーターに
関するものである。本発明における電気化学素子とは、
一次電池、二次電池、電解コンデンサー、電気二重層キ
ャパシターなどを指す。これらの電気化学素子に用いら
れる電解液は水溶液系、有機電解液系の何れでも良い。TECHNICAL FIELD The present invention relates to a separator for an electrochemical element, which is excellent in heat resistance, electrolyte retention and electrode resistance. The electrochemical element in the present invention is
Refers to primary batteries, secondary batteries, electrolytic capacitors, electric double layer capacitors, etc. The electrolytic solution used in these electrochemical devices may be either an aqueous solution type or an organic electrolytic solution type.
【０００２】[0002]
【従来の技術】各種電池や電気二重層キャパシターなど
の電気化学素子に用いられるセパレーターに要求される
最も重要な特性として電解液保持性が挙げられる。この
電解液保持性が低い場合には、電気化学素子の内部抵抗
が高くなってしまい、その結果、電気化学素子の容量不
足、電圧低下、短寿命化などの問題が生じる。2. Description of the Related Art The most important characteristic required for separators used in electrochemical devices such as various batteries and electric double layer capacitors is electrolyte retention. If the electrolyte holding property is low, the internal resistance of the electrochemical element becomes high, resulting in problems such as insufficient capacity, voltage drop, and shortened life of the electrochemical element.
【０００３】本発明者らは、特開平９−２７３１１号公
報において、ガス透過性および電解液保持性に優れ、ピ
ンホールがなく、内部短絡を防止することができる電池
セパレーター用不織布を提供することを目的とし、少な
くとも一部が繊維径１μｍ以下にフィブリル化された有
機繊維を含有してなり、且つ透気度が１００ｍｍＨｇ以
上である電池セパレーター用不織布を開示している。The inventors of the present invention have disclosed in JP-A-9-27311 a non-woven fabric for a battery separator which is excellent in gas permeability and electrolyte retaining property, has no pinholes and can prevent internal short circuit. For this purpose, a non-woven fabric for a battery separator is disclosed, which comprises at least a part of fibrillated organic fibers having a fiber diameter of 1 μm or less and has an air permeability of 100 mmHg or more.
【０００４】電解コンデンサーや電気二重層キャパシタ
ーなどは、電極の活性を上げる目的で、電極とセパレー
ターを一緒に巻き付けた状態または積層した状態で１５
０℃以上の高温で数時間〜１日程度処理することが一般
に行われている。最近では処理温度がますます高くなる
傾向にある。そのため、ポリオレフィンの多孔質体では
溶融してしまい、セルロース繊維からなる多孔質体では
炭化するため、これらの素材以外のセパレーターが要望
されている。Electrolytic capacitors, electric double-layer capacitors, etc., have a structure in which the electrode and the separator are wound together or laminated to increase the activity of the electrode.
It is generally performed at a high temperature of 0 ° C. or higher for several hours to about one day. Recently, the processing temperature tends to become higher and higher. Therefore, a porous body made of polyolefin is melted and a porous body made of cellulose fiber is carbonized. Therefore, a separator other than these materials is desired.
【０００５】また、電気化学素子の電極表面は、電解液
や電圧との関係によって、一方の極で強い酸化力が発生
し、他方の極で強い還元力が発生するため、電極と接触
しているセパレーター表面に存在する繊維が酸化または
還元されてしまい、電気化学素子の性能を劣化させてし
まう場合がある。例えば、ポリアミド繊維は比較的酸に
弱いため、酸化されやすく、ポリエステル繊維は比較的
アルカリに弱く、還元されやすい傾向がある。そのた
め、電極の極性に対する耐性を備えた繊維を選択する必
要がある。Further, the electrode surface of the electrochemical element is in contact with the electrode because a strong oxidizing force is generated at one pole and a strong reducing force is generated at the other pole due to the relationship with the electrolytic solution and voltage. The fibers present on the surface of the existing separator may be oxidized or reduced to deteriorate the performance of the electrochemical device. For example, polyamide fibers are relatively vulnerable to acid and are therefore susceptible to oxidation, while polyester fibers are relatively vulnerable to alkalis and tend to be reduced. Therefore, it is necessary to select a fiber having resistance to the polarity of the electrode.
【０００６】以上の理由から耐熱性、電解液保持性、耐
電極性の３つの特性に優れるセパレーターが求められて
いる。From the above reasons, there is a demand for a separator excellent in three characteristics, that is, heat resistance, electrolyte retention and electrode resistance.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、従来技術に
見られる上記問題点を解決するものである。即ち、本発
明の目的は、耐熱性、電解液保持性、耐電極性に優れる
電気化学素子用セパレーターを提供することにある。SUMMARY OF THE INVENTION The present invention solves the above problems found in the prior art. That is, an object of the present invention is to provide a separator for an electrochemical element, which is excellent in heat resistance, electrolyte retention, and electrode resistance.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記問題
点を解決するため鋭意検討した結果、耐熱性に優れる有
機繊維を含有してなる湿式不織布について、表裏面の繊
維構成を変える検討を重ねた結果、耐熱性、電解液保持
性、耐電極性の３特性に優れる電気化学素子用セパレー
ターを実現できることを見出し、本発明に至ったもので
ある。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have studied a method of changing the fiber structure of the front and back surfaces of a wet type nonwoven fabric containing an organic fiber having excellent heat resistance. As a result of repeating the above, it was found that a separator for an electrochemical element having excellent three properties of heat resistance, electrolyte retaining property and electrode resistance can be realized, and the present invention has been completed.
【０００９】即ち本発明は、表面に全芳香族ポリエステ
ル繊維が１０％以上存在し、反対側表面に全芳香族ポリ
アミド繊維が１０％以上存在する湿式不織布からなるこ
とを特徴とする電気化学素子用セパレーターである。That is, the present invention comprises a wet non-woven fabric having 10% or more of wholly aromatic polyester fibers on the surface and 10% or more of 10% or more wholly aromatic polyamide fibers on the opposite surface. It is a separator.
【００１０】本発明においては、全芳香族ポリエステル
繊維および全芳香族ポリアミド繊維の少なくとも一部が
繊維径１μｍ以下にフィブリル化されてなることが好ま
しい。In the present invention, it is preferable that at least a part of the wholly aromatic polyester fiber and the wholly aromatic polyamide fiber is fibrillated to have a fiber diameter of 1 μm or less.
【００１１】本発明は、全芳香族ポリエステル繊維を１
０％以上含有する層と全芳香族ポリアミド繊維を１０％
以上含有する層を抄き合わせて製造することを特徴とす
る電気化学素子用セパレーターの製造方法である。The present invention provides a wholly aromatic polyester fiber 1
Layer containing 0% or more and wholly aromatic polyamide fiber 10%
A method for producing a separator for an electrochemical element, which comprises producing the layers containing the above by combining them.
【００１２】本発明の電気化学素子用セパレーターの製
造方法としては、１５０℃〜２５０℃で熱処理すること
が好ましい。In the method for producing the separator for electrochemical device of the present invention, heat treatment at 150 ° C. to 250 ° C. is preferable.
【００１３】[0013]
【発明の実施の形態】以下、本発明の電気化学素子用セ
パレーターおよびその製造方法について詳細に説明す
る。BEST MODE FOR CARRYING OUT THE INVENTION The separator for an electrochemical device of the present invention and the method for producing the same will be described in detail below.
【００１４】本発明における電気化学素子とは、マンガ
ン乾電池、アルカリマンガン電池、酸化銀電池、リチウ
ム電池、鉛蓄電池、ニッケル−カドミウム蓄電池、ニッ
ケル−水素蓄電池、ニッケル−亜鉛蓄電池、酸化銀−亜
鉛蓄電池、リチウムイオン電池、リチウムポリマー電
池、各種のゲル電解質電池、亜鉛−空気蓄電池、鉄−空
気蓄電池、アルミニウム−空気蓄電池、燃料電池、太陽
電池、ナトリウム硫黄電池、ポリアセン電池、電解コン
デンサ、電気二重層キャパシタ（電気二重層コンデンサ
ともいう）などを指す。ここで、コンデンサまたはキャ
パシタとは、対向する２つの電極間に誘電体または電気
二重層を挟んだ形で構成されてなる蓄電機能を有するも
のである。前者はアルミ電解コンデンサやタンタル電解
コンデンサが挙げら、後者は電気二重層キャパシタが挙
げられる。電気二重層キャパシタの電極としては、一対
の分極性電極、片方が分極性電極でもう片方が非分極性
電極の組み合わせの何れでも良い。The electrochemical device in the present invention means a manganese dry battery, an alkali manganese battery, a silver oxide battery, a lithium battery, a lead storage battery, a nickel-cadmium storage battery, a nickel-hydrogen storage battery, a nickel-zinc storage battery, a silver oxide-zinc storage battery, Lithium ion batteries, lithium polymer batteries, various gel electrolyte batteries, zinc-air storage batteries, iron-air storage batteries, aluminum-air storage batteries, fuel cells, solar cells, sodium-sulfur batteries, polyacene batteries, electrolytic capacitors, electric double layer capacitors ( Also called electric double layer capacitor) etc. Here, the capacitor or the capacitor has a function of storing electricity, which is formed by sandwiching a dielectric or an electric double layer between two electrodes facing each other. The former includes aluminum electrolytic capacitors and tantalum electrolytic capacitors, and the latter includes electric double layer capacitors. The electrodes of the electric double layer capacitor may be a pair of polarizable electrodes, one of which is a polarizable electrode and the other of which is a non-polarizable electrode in combination.
【００１５】本発明に用いられる全芳香族ポリエステル
繊維とは、全芳香族ポリエステル樹脂を溶融紡糸したも
のである。全芳香族ポリエステル樹脂としては、芳香族
ジオール、芳香族ジカルボン酸、芳香族ヒドロキシカル
ボン酸の３つのモノマーを組み合わせて、組成比を変え
て合成される。例えばｐ−ヒドロキシ安息香酸と２−ヒ
ドロキシ−６−ナフトエ酸との共重合体が挙げられる
が、これらに限定されるものではない。全芳香族ポリエ
ステル繊維は、一般的に融点が２８０℃以上で耐熱性に
優れるため好ましい。The wholly aromatic polyester fiber used in the present invention is a wholly aromatic polyester resin melt-spun. The wholly aromatic polyester resin is synthesized by combining three monomers of an aromatic diol, an aromatic dicarboxylic acid and an aromatic hydroxycarboxylic acid and changing the composition ratio. Examples thereof include a copolymer of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, but the copolymer is not limited thereto. The wholly aromatic polyester fiber is preferable because it generally has a melting point of 280 ° C. or higher and is excellent in heat resistance.
【００１６】本発明に用いられる全芳香族ポリアミド繊
維は、全芳香族ポリアミド樹脂を紡糸してなるものであ
る。全芳香族ポリアミド繊維の中でも耐熱性に優れるパ
ラアラミド繊維が好ましい。パラアラミド繊維として
は、ポリ−ｐ−フェニレンテレフタルアミド、ポリ−ｐ
−ベンズアミド、ポリ−ｐ−アミドヒドラジド、ポリ−
ｐ−フェニレンテレフタルアミド−３，４−ジフェニル
エーテルテレフタルアミドなどを紡糸して繊維化したも
のが挙げられるが、これらに限定されるものではない。The wholly aromatic polyamide fiber used in the present invention is obtained by spinning a wholly aromatic polyamide resin. Among the wholly aromatic polyamide fibers, para-aramid fiber having excellent heat resistance is preferable. Para-aramid fibers include poly-p-phenylene terephthalamide and poly-p.
-Benzamide, poly-p-amide hydrazide, poly-
Examples thereof include those obtained by spinning p-phenylene terephthalamide-3,4-diphenyl ether terephthalamide and the like into fibers, but are not limited thereto.
【００１７】本発明の電気化学素子用セパレーターは、
表面に全芳香族ポリエステル繊維が１０％以上存在し、
反対側表面に全芳香族ポリアミド繊維が１０％以上存在
することを特徴とする。電気化学素子用セパレーターの
各表面に各繊維が１０％以上存在することによって、耐
熱性に優れる電気化学素子用セパレーターが得られる。The electrochemical device separator of the present invention comprises:
10% or more of wholly aromatic polyester fibers are present on the surface,
It is characterized in that 10% or more of wholly aromatic polyamide fibers are present on the opposite surface. By having 10% or more of each fiber on each surface of the separator for electrochemical device, a separator for electrochemical device having excellent heat resistance can be obtained.
【００１８】本発明における全芳香族ポリエステル繊維
および全芳香族ポリアミド繊維の繊度としては、０．０
５ｄｔｅｘ〜５ｄｔｅｘが好ましく、０．０５ｄｔｅｘ
〜３ｄｔｅｘがより好ましい。The fineness of the wholly aromatic polyester fiber and the wholly aromatic polyamide fiber in the present invention is 0.0
5dtex-5dtex are preferable, and 0.05dtex
3 dtex is more preferable.
【００１９】本発明における全芳香族ポリエステル繊維
および全芳香族ポリアミドは、少なくとも一部が繊維径
１μｍ以下にフィブリル化されてなることが好ましい。
両繊維のフィブリル化は、少なくとも高圧ホモジナイザ
ーを用いて行い、主に繊維軸と平行な方向に非常に細か
く分割された部分を持ち、少なくとも一部が繊維径１μ
ｍ以下の状態を指す。少なくとも高圧ホモジナイザーを
用いてという意味は、高圧ホモジナイザーだけを用いて
も良いし、高圧ホモジナイザーとそれ以外の装置、例え
ば、リファイナー、ビーター、摩砕装置などを組み合わ
せて用いても良いということである。高圧ホモジナイザ
ーを用いてフィブリル化された有機繊維は、繊維径分布
が相対的に狭く、均一性が高い特徴を有する。繊維径は
電子顕微鏡観察により確認することができる。全芳香族
ポリエステル繊維および全芳香族ポリアミド繊維の少な
くとも一部が繊維径１μｍ以下にフィブリル化されてな
ることによって、該繊維の比表面積が増大するため、電
気化学素子用セパレーターの耐熱性と電解液保持性がさ
らに向上する利点がある。At least a part of the wholly aromatic polyester fiber and the wholly aromatic polyamide in the present invention is preferably fibrillated to have a fiber diameter of 1 μm or less.
Fibrillation of both fibers is performed using at least a high-pressure homogenizer, and it has a very finely divided portion mainly in the direction parallel to the fiber axis, and at least a portion has a fiber diameter of 1 μm.
Indicates a state of m or less. The use of at least a high-pressure homogenizer means that only a high-pressure homogenizer may be used, or a high-pressure homogenizer and other devices such as a refiner, a beater, and a grinding device may be used in combination. The organic fibers fibrillated using a high-pressure homogenizer have characteristics that the fiber diameter distribution is relatively narrow and the uniformity is high. The fiber diameter can be confirmed by observation with an electron microscope. Since at least a part of the wholly aromatic polyester fiber and the wholly aromatic polyamide fiber is fibrillated to have a fiber diameter of 1 μm or less, the specific surface area of the fiber is increased, so that the heat resistance of the separator for electrochemical element and the electrolytic solution are increased. There is an advantage that the holding property is further improved.
【００２０】本発明においては、高圧ホモジナイザーを
用いずに、例えば、リファイナー単独、ビーター単独、
摩砕装置単独、あるいはこれら装置を組み合わせて用い
て微細化された有機繊維のことをパルプと定義して明確
に区別する。また、本発明におけるフィブリルは、フィ
ブリッドとも異なる。フィブリッドとは、米国特許第５
８３３８０７号明細書や米国特許第５０２６４５６号明
細書に明記されているように、平均長さ０．２ｍｍ〜１
ｍｍ、長さと巾のアスペクト比が５：１〜１０：１のフ
ィルム状粒子で繊維状ではない。本発明におけるフィブ
リルは、少なくとも一部が、すなわち分割された部分が
繊維径１μｍ以下であれば良い。フィブリル化の程度の
目安としては、長さと巾のアスペクト比が２０：１〜１
０００００：１、カナダ標準形濾水度が０ｍｌ〜５００
ｍｌである。In the present invention, without using a high-pressure homogenizer, for example, refiner alone, beater alone,
Finely divided organic fibers using a grinding device alone or in combination with these devices are defined as pulp and are clearly distinguished. Further, the fibril in the present invention is also different from the fibril. Fibrid means US Patent No. 5
As specified in 833807 and U.S. Pat. No. 5,026,456, an average length of 0.2 mm to 1
mm, a film-like particle having an aspect ratio of length to width of 5: 1 to 10: 1 and not fibrous. At least a part of the fibrils in the present invention, that is, the divided parts may have a fiber diameter of 1 μm or less. As a measure of the degree of fibrillation, the aspect ratio of length and width is 20: 1 to 1
00000: 1, Canadian Standard Freeness 0ml ~ 500
ml.
【００２１】本発明における高圧ホモジナイザーとは、
対象物に少なくとも１０ｋｇ／ｃｍ 2以上、好ましくは
２００〜１０００ｋｇ／ｃｍ2、さらに好ましくは４０
０〜１０００ｋｇ／ｃｍ2の圧力を加えてオリフィスを
通過させ、急速に減圧、減速させることにより生じる剪
断力をもって対象物を微細化することができる装置であ
る。有機繊維の場合は、この剪断力によって、主として
繊維軸と平行な方向に引き裂き、ほぐすような力として
与えられ、次第にフィブリル化する。具体的には、有機
繊維を繊維長５ｍｍ以下、好ましくは３ｍｍ以下に切断
したものを原料とし、これを水に分散させて懸濁液とす
る。懸濁液の濃度は質量百分率で最大２５％、好ましく
は１〜１０％であり、さらに好ましくは、１〜２％であ
る。この懸濁液を高圧ホモジナイザーに導入し、少なく
とも１０ｋｇ／ｃｍ2、好ましくは２００〜１０００ｋ
ｇ／ｃｍ2、さらに好ましくは４００〜１０００ｋｇ／
ｃｍ2の圧力を加え、この操作を数回〜数十回繰り返し
高圧ホモジナイザーに通過させる。場合によって、界面
活性剤など薬品を添加して処理しても良い。The high-pressure homogenizer in the present invention means
At least 10 kg / cm on the object 2Or more, preferably
200-1000kg / cm2, And more preferably 40
0-1000kg / cm2The pressure to apply the orifice
The shear generated by passing it through and rapidly depressurizing and decelerating
A device that can miniaturize an object with breaking force
It In the case of organic fibers, this shear force mainly
Tear in the direction parallel to the fiber axis, and as a loosening force
Given, gradually fibrillate. Specifically, organic
Cuts fibers to a fiber length of 5 mm or less, preferably 3 mm or less
Made into a raw material, disperse this in water to make a suspension
It The concentration of the suspension is up to 25% by mass, preferably
Is 1 to 10%, and more preferably 1 to 2%.
It Introduce this suspension into a high pressure homogenizer and reduce
Both 10 kg / cm2, Preferably 200-1000k
g / cm2And more preferably 400 to 1000 kg /
cm2Apply pressure and repeat this operation several times to several tens of times.
Pass through high pressure homogenizer. In some cases, the interface
A chemical such as an activator may be added for treatment.
【００２２】本発明の電気化学素子用セパレーターは、
全芳香族ポリエステル繊維および全芳香族ポリアミド繊
維以外にも、ポリエステル、アクリル、ポリオレフィ
ン、ポリビニルアルコール、エチレン−ビニルアルコー
ル共重合体、ポリアミド（ＰＡ）、ポリイミド（Ｐ
Ｉ）、ポリアミドイミド（ＰＡＩ）、ポリエーテルケト
ン（ＰＥＫ）、ポリエーテルエーテルケトン（ＰＥＥ
Ｋ）、ポリエーテルサルフォン（ＰＥＳ）、ポリフェニ
レンスルフィド（ＰＰＳ）、ポリベンズイミダゾール
（ＰＢＩ）などからなる単繊維、複合繊維、これらの中
から２種以上を組み合わせてなる分割型複合繊維を含有
しても良い。The electrochemical device separator of the present invention comprises:
In addition to wholly aromatic polyester fibers and wholly aromatic polyamide fibers, polyester, acrylic, polyolefin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyamide (PA), polyimide (P
I), polyamideimide (PAI), polyetherketone (PEK), polyetheretherketone (PEE)
K), polyether sulfone (PES), polyphenylene sulfide (PPS), polybenzimidazole (PBI), etc. monofilament, conjugate fiber, split type conjugate fiber composed of a combination of two or more of these. May be.
【００２３】これらの有機繊維の繊維長としては、１〜
３０ｍｍが好ましく、１〜１０ｍｍがより好ましい。繊
維長が１ｍｍより短いと、フィブリル化繊維の捕捉能が
低下し、３０ｍｍより長くなると繊維同士がよれて電気
化学素子用セパレーターの厚みむらが生じやすくなる。
繊維径は０．０５ｄｔｅｘ〜３ｄｔｅｘが好ましい。The fiber length of these organic fibers is from 1 to
30 mm is preferable and 1-10 mm is more preferable. When the fiber length is shorter than 1 mm, the ability to capture the fibrillated fibers is lowered, and when the fiber length is longer than 30 mm, the fibers are twisted with each other and the thickness unevenness of the separator for electrochemical device is likely to occur.
The fiber diameter is preferably 0.05 dtex to 3 dtex.
【００２４】本発明の電気化学素子用セパレーターは、
フィブリル化セルロース繊維やバクテリアセルロースを
含有しても良い。これらの繊維は、水素結合により自他
繊維との接着力が強いため、引張強度や突刺強度など機
械的強度に優れる電気化学素子用セパレーターが得られ
る。The electrochemical device separator of the present invention comprises:
It may contain fibrillated cellulose fibers or bacterial cellulose. Since these fibers have a strong adhesive force with self-other fibers due to hydrogen bonding, a separator for an electrochemical element having excellent mechanical strength such as tensile strength and puncture strength can be obtained.
【００２５】ここで、フィブリル化セルロース繊維と
は、リンターをはじめとする各種パルプ、リント、溶剤
紡糸セルロースなどを原料とし、少なくとも高圧ホモジ
ナイザーを用いて主に繊維軸と平行な方向に分割、微細
化されて製造されたものを指し、セルロース繊維１本１
本のほとんどが繊維径１μｍ以下で、平均繊維長が２ｍ
ｍ以下、好ましくは１ｍｍ以下である。高圧ホモジナイ
ザーだけでフィブリル化されたものでも良いが、高圧ホ
モジナイザーとその他の装置、例えばリファイナー、ビ
ーター、摩砕装置などを組み合わせて処理し、フィブリ
ル化されたものでも良い。Here, the fibrillated cellulose fiber is made from various pulps such as linter, lint, and solvent-spun cellulose as raw materials, and is divided into at least a high-pressure homogenizer mainly in the direction parallel to the fiber axis to be finely divided. Refers to those manufactured and manufactured, and 1 cellulosic fiber 1
Most of the books have a fiber diameter of 1 μm or less and an average fiber length of 2 m.
m or less, preferably 1 mm or less. It may be fibrillated only by a high-pressure homogenizer, or may be fibrillated by treating it with a combination of a high-pressure homogenizer and other devices such as a refiner, a beater and a grinding device.
【００２６】本発明における電気化学素子用セパレータ
ー中のフィブリル化セルロース繊維の含有量は８％以下
が好ましい。フィブリル化セルロース繊維は、他の繊維
に絡みつくため、繊維間の結合力を強め、結果として電
気化学素子用セパレーターの引張強度が強くなる。さら
にフィブリル化セルロース繊維が水素結合による自己結
着力により膜を形成する場合には、電気化学素子用セパ
レーターにピンホールができにくくなり、電極活物質の
貫通防止効果が高まるだけでなく、電気化学素子用セパ
レーターの突刺強度も強くなる。The content of fibrillated cellulose fibers in the separator for electrochemical device in the present invention is preferably 8% or less. Since the fibrillated cellulose fiber is entangled with other fibers, the binding force between the fibers is strengthened, and as a result, the tensile strength of the separator for electrochemical device is increased. Furthermore, when the fibrillated cellulose fibers form a film by the self-bonding force due to hydrogen bonding, it becomes difficult to form pinholes in the separator for the electrochemical element, and not only the effect of preventing penetration of the electrode active material is enhanced, but also the electrochemical element. The piercing strength of the separator will be stronger.
【００２７】本発明におけるバクテリアセルロースと
は、微生物が産生するバクテリアセルロースのことを指
す。バクテリアセルロースは、非常に微細な繊維である
ため、わずかな配合量でも、繊維間の結合力が強くな
り、引張強度の強い電気化学素子用セパレーターが得ら
れる。本発明における電気化学素子用セパレーター中の
バクテリアセルロースの配合量としては８％以下が好ま
しい。The bacterial cellulose in the present invention refers to bacterial cellulose produced by microorganisms. Bacterial cellulose is a very fine fiber, so even with a small blending amount, the binding force between fibers becomes strong, and a separator for an electrochemical element having high tensile strength can be obtained. The blending amount of bacterial cellulose in the separator for electrochemical device in the present invention is preferably 8% or less.
【００２８】本発明の電気化学素子用セパレーターは、
さらにガラス繊維、マイクロガラス繊維、アルミナ繊
維、アルミナ・シリカ繊維、ロックウール、セラミック
ス繊維、各種ウィスカなどの無機繊維を含有しても良
い。これら無機繊維は、水溶液系電解液、有機電解液の
何れに対しても濡れ性が良好なため、無機繊維を含有し
ない場合よりも優れた電解液保持性が得られるだけでな
く、電気化学素子用セパレーターの熱収縮が抑制される
ため、電極同士の短絡が起こりにくく、電気化学素子の
製造歩留りが高くなる効果も併せ持つ。本発明の電気化
学素子用セパレーター中の無機繊維の含有量としては、
３０％以下が好ましく、２０％以下がより好ましい。含
有量が３０％より多くなると、電気化学素子用セパレー
ターの耐折強度が弱くなりやすい。The electrochemical device separator of the present invention comprises:
Further, inorganic fibers such as glass fibers, micro glass fibers, alumina fibers, alumina / silica fibers, rock wool, ceramics fibers and various whiskers may be contained. Since these inorganic fibers have good wettability with both aqueous electrolytic solutions and organic electrolytic solutions, not only can they retain electrolytes better than when they do not contain inorganic fibers, but they also have electrochemical elements. Since the heat shrinkage of the separator for use is suppressed, short-circuiting between electrodes is less likely to occur, and the manufacturing yield of the electrochemical device is also increased. The content of the inorganic fiber in the separator for electrochemical device of the present invention,
30% or less is preferable and 20% or less is more preferable. If the content is more than 30%, the folding endurance of the electrochemical device separator is likely to be weak.
【００２９】本発明における電気化学素子用セパレータ
ーの製造方法は、全芳香族ポリエステル繊維を１０％以
上含有する層と全芳香族ポリアミド繊維を１０％以上含
有する層を抄き合わせることを特徴とする。抄き合わせ
に用いる抄紙機としては、長網抄紙機、円網抄紙機、傾
斜型抄紙機の中から同種または異種の抄紙機を組み合わ
せたコンビネーションマシンが挙げられる。The method for producing a separator for an electrochemical element in the present invention is characterized in that a layer containing 10% or more of wholly aromatic polyester fiber and a layer containing 10% or more of wholly aromatic polyamide fiber are combined. . Examples of the paper machine used for papermaking include a combination machine in which the same kind or different kinds of paper machines are combined from fourdrinier paper machines, cylinder paper machines, and inclined paper machines.
【００３０】湿式抄紙法は、通常、繊維を固形分濃度が
０．１〜５％程度になるように分散助剤、増粘剤などを
用いて水中に均一に分散してスラリーとし、さらにスラ
リー中に水を追加し、固形分濃度を０．１〜０．００１
％に希釈して希薄水性スラリーとし、これを抄紙機を用
いてシート化するものである。In the wet papermaking method, fibers are usually uniformly dispersed in water using a dispersion aid, a thickener or the like so that the solid content concentration is about 0.1 to 5% to form a slurry, and further a slurry is prepared. Add water to adjust the solid concentration to 0.1-0.001.
% To make a dilute aqueous slurry, which is sheeted using a paper machine.
【００３１】本発明における電気化学素子用セパレータ
ーの坪量は、特に制限はないが、５〜１００ｇ／ｍ2が
好ましく、１０〜５０ｇ／ｍ2がさらに好ましく用いら
れる。The basis weight of the electrochemical device for separator of the present invention is not particularly limited but is preferably 5 to 100 g / m 2, is used more preferably 10 to 50 g / m 2.
【００３２】本発明における電気化学素子用セパレータ
ーの厚みは、特に制限はないが、電気化学素子が小型化
できること、収容できる電極面積を大きくでき容量を稼
げる点から薄い方が好ましい。具体的には電池組立時に
破断しない程度の強度を持ち、ピンホールが無く、高い
均一性を備える厚みとして１０〜２００μｍが好ましく
用いられ、２０〜１００μｍがより好ましく用いられ
る。１０μｍ未満では、電気化学素子の製造時の短絡不
良率が増加するため好ましくない。一方、２００μｍよ
り厚くなると、電気化学素子に収納できる電極面積が減
少するため電気化学素子の容量が低いものになる。The thickness of the separator for an electrochemical element in the present invention is not particularly limited, but it is preferable that it is thin from the viewpoint that the electrochemical element can be downsized and the electrode area that can be accommodated can be increased to increase the capacity. Specifically, the thickness is 10 to 200 μm, preferably 20 to 100 μm, which has strength enough not to break during battery assembly, has no pinhole, and has high uniformity. If it is less than 10 μm, the short-circuit failure rate at the time of manufacturing the electrochemical element increases, which is not preferable. On the other hand, if the thickness is more than 200 μm, the area of the electrode that can be accommodated in the electrochemical device decreases, and the capacity of the electrochemical device becomes low.
【００３３】本発明の電気化学素子用セパレーターの厚
みが所望の厚みよりも厚い場合には二次加工処理により
厚みを薄くする必要がある。この二次加工処理として
は、スーパーカレンダー、マシンカレンダー、熱カレン
ダー、ソフトカレンダー、熱ソフトカレンダーなどのカ
レンダーを用いてカレンダー処理を施して厚み調整が行
われる。なるべく電解液保持性を損なわないようにする
ため、加熱しないでカレンダー処理を行うことがより好
ましい。When the thickness of the electrochemical device separator of the present invention is thicker than the desired thickness, it is necessary to reduce the thickness by secondary processing. As the secondary processing, calendering is performed using a calendar such as a super calendar, a machine calendar, a thermal calendar, a soft calendar, and a thermal soft calendar to adjust the thickness. It is more preferable to carry out calendering without heating so as not to impair the electrolyte holding property as much as possible.
【００３４】本発明において加圧処理または加圧熱処理
することにより、電気化学素子用セパレーターの表面平
滑性が向上するため電極との密着性が良くなり、電極と
の巻回時に電極と電気化学素子用セパレーター間にずれ
や空隙が生じにくくなる。In the present invention, the pressure treatment or the pressure heat treatment improves the surface smoothness of the separator for an electrochemical element, thereby improving the adhesion to the electrode and, when winding the electrode and the electrochemical element. Gaps and voids between separators are less likely to occur.
【００３５】本発明の電気化学素子用セパレーターの強
度が弱く、電気化学素子組立時の巻回性に問題が生じる
場合には、予め電気化学素子用セパレーターを１５０〜
２５０℃、より好ましくは１８０℃〜２５０℃で熱処理
することが好ましい。予め高温で熱処理することによっ
て、電気化学素子用セパレーターを構成する有機繊維の
一部が軟化、溶融して自他繊維と融着するため、セパレ
ーターの耐熱寸法安定性が向上する。そのため、セパレ
ーターを電極と一緒に高温処理してもセパレーターが熱
収縮しにくく、電極同士が接触する事故を防止すること
ができる。熱処理することによってセパレーターの引張
強度や突刺強度が向上するため、電極と一緒に巻回する
際にセパレーターの破断や貫通事故が生じにくくなり、
電気化学素子の生産効率と歩留りが向上する。When the separator for an electrochemical element of the present invention is weak in strength and causes a problem in the winding property at the time of assembling the electrochemical element, the separator for an electrochemical element is preliminarily 150-150.
It is preferable to perform heat treatment at 250 ° C, more preferably 180 ° C to 250 ° C. By preliminarily performing heat treatment at a high temperature, a part of the organic fibers constituting the separator for an electrochemical element are softened and melted and fused with the self-other fibers, so that the heat resistant dimensional stability of the separator is improved. Therefore, even if the separator and the electrodes are treated at a high temperature, the separator is less likely to undergo thermal contraction, and it is possible to prevent accidents where the electrodes contact each other. Since the tensile strength and puncture strength of the separator are improved by heat treatment, the separator is less likely to break or penetrate when wound together with the electrode,
The production efficiency and yield of electrochemical devices are improved.
【００３６】本発明における熱処理の具体的な方法とし
ては、１５０〜２５０℃、より好ましくは１８０℃〜２
５０℃に加熱したロールに電気化学素子用セパレーター
の少なくとも片面、好ましくは両面を接触させて、連続
処理することが挙げられる。熱処理時間が長い程、熱処
理効果が大きいため、少なくとも片面で５秒以上接触さ
せて両面を処理することが好ましい。A specific method of heat treatment in the present invention is 150 to 250 ° C., more preferably 180 to 2 ° C.
At least one surface of the separator for electrochemical device, preferably both surfaces, may be contacted with a roll heated to 50 ° C. for continuous treatment. The longer the heat treatment time is, the greater the heat treatment effect is. Therefore, it is preferable to contact both surfaces for at least 5 seconds to treat both surfaces.
【００３７】活性炭や活性炭素繊維を電極活物質として
用いる電気化学素子の場合、セパレーター内に不純物が
あると、活性炭や活性炭素繊維が不純物を吸着してしま
い、その結果、活性炭や活性炭素繊維の細孔が潰れた
り、比表面積が減少し、電気化学素子の容量が理論値よ
りも大幅に低下する場合がある。湿式不織布には、湿式
抄紙時に用いられる界面活性剤や消泡剤などの添加薬品
が微量ではあるが付着していることが多く、湿式不織布
を電気化学素子用セパレーターとして用いる場合、これ
らの付着物が活性炭や活性炭素繊維に吸着して容量が低
下する場合がある。湿式不織布を１５０℃〜２５０℃で
熱処理することによって、これらの付着物が揮発して除
去される効果もある。１５０℃より低い温度では、これ
ら付着物が揮発しにくい。In the case of an electrochemical element using activated carbon or activated carbon fiber as an electrode active material, if impurities are present in the separator, the activated carbon or activated carbon fiber will adsorb the impurities, and as a result, activated carbon or activated carbon fiber The pores may be crushed, the specific surface area may be reduced, and the capacity of the electrochemical device may be significantly reduced from the theoretical value. Additives such as surfactants and defoaming agents used during wet papermaking are often attached to wet non-woven fabrics even though they are trace amounts, and when the wet non-woven fabric is used as a separator for electrochemical devices, these adhered substances May be adsorbed on activated carbon or activated carbon fiber to reduce the capacity. By heat-treating the wet-laid nonwoven fabric at 150 ° C. to 250 ° C., there is also an effect that these deposits are volatilized and removed. At temperatures lower than 150 ° C, these deposits are less likely to volatilize.
【００３８】[0038]
【実施例】以下、実施例により本発明を詳しく説明する
が、本発明の内容は実施例に限定されるものではない。The present invention will be described in detail below with reference to examples, but the contents of the present invention are not limited to the examples.
【００３９】＜スラリー１の調製＞平均繊維長０．５ｍ
ｍで、少なくとも一部が繊維径１μｍ以下にフィブリル
化された全芳香族ポリエステル繊維４０％、繊度０．１
ｄｔｅｘ、繊維長３ｍｍのポリエステル繊維３０％、芯
部に融点２５５℃のポリエステル、鞘部に融点１１０℃
の変性ポリエステル繊維を配した芯鞘複合繊維（繊度１
ｄｔｅｘ、繊維長３ｍｍ）３０％の配合比で分散助剤と
ともにパルパーを用いて水中に分散させた。これを水で
所定濃度に希釈してスラリー１を調製した。<Preparation of Slurry 1> Average fiber length 0.5 m
m, at least part of which is fibrillated to a fiber diameter of 1 μm or less, 40% wholly aromatic polyester fiber, fineness 0.1
dtex, 30% polyester fiber with a fiber length of 3 mm, polyester with a melting point of 255 ° C in the core, 110 ° C in the sheath
Core-sheath composite fiber with modified polyester fiber (fineness 1
(dtex, fiber length 3 mm) A dispersion ratio of 30% was used to disperse in water using a pulper. Slurry 1 was prepared by diluting this with water to a predetermined concentration.
【００４０】＜スラリー２の調製＞平均繊維長０．６ｍ
ｍで、少なくとも一部が繊維径１μｍ以下にフィブリル
化された全芳香族ポリアミド繊維３０％、繊度０．１ｄ
ｔｅｘ、繊維長３ｍｍのポリエステル繊維３０％、繊度
０．４ｄｔｅｘ、繊維長３ｍｍのポリエステル繊維１０
％、芯部に融点２５５℃のポリエステル、鞘部に融点１
１０℃の変性ポリエステル繊維を配した芯鞘複合繊維
（繊度１ｄｔｅｘ、繊維長３ｍｍ）３０％の配合比で分
散助剤とともにパルパーを用いて水中に分散させた。こ
れを水で所定濃度に希釈してスラリー２を調製した。<Preparation of slurry 2> Average fiber length 0.6 m
m, at least part of which is fibrillated to a fiber diameter of 1 μm or less, 30% wholly aromatic polyamide fiber, fineness 0.1d
tex, 30% polyester fiber having a fiber length of 3 mm, fineness 0.4 dtex, polyester fiber having a fiber length of 3 mm 10
%, Polyester with a melting point of 255 ° C. in the core, melting point 1 in the sheath
A core-sheath composite fiber having a modified polyester fiber at 10 ° C. (fineness 1 dtex, fiber length 3 mm) was dispersed in water with a dispersion aid at a compounding ratio of 30% using a pulper. Slurry 2 was prepared by diluting this with water to a predetermined concentration.
【００４１】＜スラリー３の調製＞平均繊維長０．７ｍ
ｍで、少なくとも一部が繊維径１μｍ以下にフィブリル
化された全芳香族ポリエステル繊維１０％、繊度０．１
ｄｔｅｘ、繊維長３ｍｍのポリエステル繊維３０％、繊
度０．４ｄｔｅｘ、繊維長３ｍｍのポリエステル繊維２
５％、芯部に融点２５５℃のポリエステル、鞘部に融点
１１０℃の変性ポリエステル繊維を配した芯鞘複合繊維
（繊度１ｄｔｅｘ、繊維長３ｍｍ）３０％、フィブリル
化セルロース繊維５％の配合比で分散助剤とともにパル
パーを用いて水中に分散させた。これを水で所定濃度に
希釈してスラリー３を調製した。<Preparation of Slurry 3> Average fiber length 0.7 m
m, at least part of which is fibrillated to a fiber diameter of 1 μm or less, 10% wholly aromatic polyester fiber, fineness 0.1
30% polyester fiber with a dtex of 3 mm and a fineness of 0.4 dtex and a polyester fiber of 3 mm with a fiber length of 2 mm
5%, core-sheath composite fiber (polyester having a melting point of 255 ° C. in the core portion and modified polyester fiber having a melting point of 110 ° C. in the sheath portion, fineness 1 dtex, fiber length 3 mm) 30%, fibrillated cellulose fiber 5% It was dispersed in water using a pulper together with a dispersion aid. This was diluted with water to a predetermined concentration to prepare Slurry 3.
【００４２】＜スラリー４の調製＞平均繊維長０．４ｍ
ｍで、少なくとも一部が繊維径１μｍ以下にフィブリル
化された全芳香族ポリアミド繊維１０％、繊度０．１ｄ
ｔｅｘ、繊維長３ｍｍのポリエステル繊維２５％、繊度
０．４ｄｔｅｘ、繊維長３ｍｍのポリエステル繊維２０
％、芯部に融点２５５℃のポリエステル、鞘部に融点１
１０℃の変性ポリエステル繊維を配した芯鞘複合繊維
（繊度１ｄｔｅｘ、繊維長３ｍｍ）３０％、平均繊維径
０．３μｍのマイクロガラス繊維１５％の配合比で分散
助剤とともにパルパーを用いて水中に分散させた。これ
を水で所定濃度に希釈してスラリー４を調製した。<Preparation of slurry 4> Average fiber length 0.4 m
m, at least part of which is fibrillated to a fiber diameter of 1 μm or less, 10% wholly aromatic polyamide fiber, fineness 0.1d
tex, 25% polyester fiber having a fiber length of 3 mm, fineness 0.4 dtex, polyester fiber 20 having a fiber length of 3 mm
%, Polyester with a melting point of 255 ° C. in the core, melting point 1 in the sheath
30% core-sheath composite fibers with a modified polyester fiber of 10 ° C. (fineness 1 dtex, fiber length 3 mm) and micro glass fibers 15% with an average fiber diameter of 0.3 μm were mixed in water using a pulper together with a dispersion aid. Dispersed. This was diluted with water to a predetermined concentration to prepare Slurry 4.
【００４３】＜スラリー５の調製＞全芳香族ポリエステ
ル繊維（繊度１ｄｔｅｘ、繊維長３ｍｍ）３０％、繊度
０．１ｄｔｅｘ、繊維長３ｍｍのポリエステル繊維４０
％、繊度０．４ｄｔｅｘ、繊維長３ｍｍのポリエステル
繊維２２％、バクテリアセルロース８％の配合比で分散
助剤とともにパルパーを用いて水中に分散させた。これ
を水で所定濃度に希釈してスラリー５を調製した。<Preparation of Slurry 5> 30% of wholly aromatic polyester fiber (fineness 1 dtex, fiber length 3 mm), fineness 0.1 dtex, fiber length 3 mm polyester fiber 40
%, A fineness of 0.4 dtex, a polyester fiber having a fiber length of 3 mm, 22%, and a bacterial cellulose, 8%, were dispersed in water using a pulper together with a dispersion aid. This was diluted with water to a predetermined concentration to prepare Slurry 5.
【００４４】＜スラリー６の調製＞平均繊維長０．７ｍ
ｍで、少なくとも一部が繊維径１μｍ以下にフィブリル
化された全芳香族ポリエステル繊維５％、繊度０．１ｄ
ｔｅｘ、繊維長３ｍｍのポリエステル繊維３５％、繊度
０．４ｄｔｅｘ、繊維長３ｍｍのポリエステル繊維３０
％、芯部に融点２５５℃のポリエステル、鞘部に融点１
１０℃の変性ポリエステル繊維を配した芯鞘複合繊維
（繊度１ｄｔｅｘ、繊維長３ｍｍ）３０％の配合比で分
散助剤とともにパルパーを用いて水中に分散させた。こ
れを水で所定濃度に希釈してスラリー６を調製した。<Preparation of Slurry 6> Average fiber length 0.7 m
m, at least part of which is fibrillated to a fiber diameter of 1 μm or less, 5% wholly aromatic polyester fiber, fineness 0.1d
tex, 35% polyester fiber having a fiber length of 3 mm, fineness 0.4 dtex, fiber length 30 mm, polyester fiber 30
%, Polyester with a melting point of 255 ° C. in the core, melting point 1 in the sheath
A core-sheath composite fiber having a modified polyester fiber at 10 ° C. (fineness 1 dtex, fiber length 3 mm) was dispersed in water with a dispersion aid at a compounding ratio of 30% using a pulper. This was diluted with water to a predetermined concentration to prepare Slurry 6.
【００４５】＜スラリー７の調製＞平均繊維長０．４ｍ
ｍで、少なくとも一部が繊維径１μｍ以下にフィブリル
化された全芳香族ポリアミド繊維５％、繊度０．１ｄｔ
ｅｘ、繊維長３ｍｍのポリエステル繊維３５％、繊度
０．４ｄｔｅｘ、繊維長３ｍｍのポリエステル繊維３０
％、芯部に融点２５５℃のポリエステル、鞘部に融点１
１０℃の変性ポリエステル繊維を配した芯鞘複合繊維
（繊度１ｄｔｅｘ、繊維長３ｍｍ）３０％の配合比で分
散助剤とともにパルパーを用いて水中に分散させた。こ
れを水で所定濃度に希釈してスラリー７を調製した。<Preparation of slurry 7> Average fiber length 0.4 m
m, at least a part of which is fibrillated to a fiber diameter of 1 μm or less, 5% of wholly aromatic polyamide fiber, fineness of 0.1 dt
ex, 35% polyester fiber having a fiber length of 3 mm, fineness 0.4 dtex, polyester fiber 30 having a fiber length of 3 mm
%, Polyester with a melting point of 255 ° C. in the core, melting point 1 in the sheath
A core-sheath composite fiber having a modified polyester fiber at 10 ° C. (fineness 1 dtex, fiber length 3 mm) was dispersed in water with a dispersion aid at a compounding ratio of 30% using a pulper. This was diluted with water to a predetermined concentration to prepare slurry 7.
【００４６】実施例１
傾斜型／円網コンビネーション抄紙機を用い、スラリー
１を傾斜ワイヤーへ、スラリー２を円網へ移送し、傾斜
側で坪量８ｇ／ｍ2、円網側で坪量８ｇ／ｍ2にして抄き
合わせし、坪量１６ｇ／ｍ2の湿式不織布を作製した。
次いで、１５０℃に加熱した直径１．２ｍのドラムロー
ル２本に速度１０ｍ／ｍｉｎで該不織布の両面を接触さ
せて熱処理し、坪量１６．４ｇ／ｍ2、厚み４４μｍの
電気化学素子用セパレーター１とした。Example 1 Using an inclined type / cylinder combination paper machine, slurry 1 was transferred to an inclined wire and slurry 2 was transferred to a cylinder, and the basis weight was 8 g / m 2 on the slope side and 8 g on the cylinder side. / M 2 and papermaking was performed to prepare a wet type nonwoven fabric having a basis weight of 16 g / m 2 .
Then, both sides of the nonwoven fabric are contacted with two drum rolls having a diameter of 1.2 m and heated at 150 ° C. at a speed of 10 m / min to heat-treat, and a separator for electrochemical device having a basis weight of 16.4 g / m 2 and a thickness of 44 μm. It was set to 1.
【００４７】実施例２
円網２連式の抄紙機を用い、スラリー１から坪量８ｇ／
ｍ2、スラリー４から坪量１０ｇ／ｍ2で抄き合わせし、
坪量１８ｇ／ｍ2の湿式不織布を作製した。次いで、１
８０℃に加熱した直径１．２ｍのドラムロール２本に速
度２０ｍ／ｍｉｎで該不織布の両面を接触させて熱処理
し、坪量１８．５ｇ／ｍ2、厚み５５μｍの電気化学素
子用セパレーター２とした。Example 2 Using a double-cylinder paper machine, slurry 1 to basis weight 8 g /
m 2 , from Slurry 4 with a basis weight of 10 g / m 2 ,
A wet type nonwoven fabric having a basis weight of 18 g / m 2 was prepared. Then 1
Both sides of the non-woven fabric were heat-treated by contacting two drum rolls having a diameter of 1.2 m and heated at 80 ° C. at a speed of 20 m / min, and a separator 2 for electrochemical device having a basis weight of 18.5 g / m 2 and a thickness of 55 μm was used. did.
【００４８】実施例３
長網／ 円網コンビネーション抄紙機を用い、スラリー
２を長網へ、スラリー３を円網へ移送し、長網側で坪量
８ｇ／ｍ2、円網側で坪量１０ｇ／ｍ2で抄き合わせし、
坪量１８ｇ／ｍ2の湿式不織布を作製した。次いで、２
００℃に加熱した直径１．２ｍのドラムロール２本に速
度２０ｍ／ｍｉｎで該不織布の両面を接触させて熱処理
し、坪量１９ｇ／ｍ2、厚み５６μｍの電気化学素子用
セパレーター３とした。Example 3 Using a fourdrinier / cylinder combination paper machine, slurry 2 was transferred to a fourdrinth and slurry 3 was transferred to a fourdrinier, and the basis weight was 8 g / m 2 on the fourdrinier side and the basis weight was on the netted side. Papermaking at 10 g / m 2 ,
A wet type nonwoven fabric having a basis weight of 18 g / m 2 was prepared. Then 2
Both sides of the nonwoven fabric were brought into contact with two 1.2 m diameter drum rolls heated to 00 ° C. at a speed of 20 m / min to heat-treat them to obtain a separator 3 for electrochemical device having a basis weight of 19 g / m 2 and a thickness of 56 μm.
【００４９】実施例４
円網２連式の抄紙機を用い、スラリー３から坪量１０ｇ
／ｍ2、スラリー４から坪量１０ｇ／ｍ2で抄き合わせ
し、坪量２０ｇ／ｍ2の湿式不織布を作製した。次い
で、２４０℃に加熱した直径１．２ｍのドラムロール２
本に速度３０ｍ／ｍｉｎで該不織布の両面を接触させて
熱処理し、坪量２１ｇ／ｍ2、厚み６３μｍの電気化学
素子用セパレーター４とした。Example 4 Using a twin cylinder paper machine, slurry 3 to basis weight 10 g
/ M 2, and the combined paper making from the slurry 4 at a basis weight 10 g / m 2, to prepare a wet-laid nonwoven fabric having a basis weight of 20 g / m 2. Next, a drum roll 2 heated to 240 ° C. and having a diameter of 1.2 m
Both sides of the nonwoven fabric were brought into contact with a book at a speed of 30 m / min and heat-treated to obtain a separator 4 for electrochemical device having a basis weight of 21 g / m 2 and a thickness of 63 μm.
【００５０】実施例５
熱処理をしなかった以外は実施例１と同様にして、坪量
１６ｇ／ｍ2、厚み４１μｍの電気化学素子用セパレー
ター５とした。Example 5 A separator 5 for electrochemical device having a basis weight of 16 g / m 2 and a thickness of 41 μm was obtained in the same manner as in Example 1 except that heat treatment was not carried out.
【００５１】実施例６
円網２連式の抄紙機を用い、スラリー２から坪量１０ｇ
／ｍ2、スラリー５から坪量１４ｇ／ｍ2で抄き合わせ
し、坪量２４ｇ／ｍ2の湿式不織布を作製した。次い
で、２１０℃に加熱した直径１．２ｍのドラムロール２
本に速度２０ｍ／ｍｉｎで該不織布の両面を接触させて
熱処理し、坪量２４．５ｇ／ｍ2、厚み７５μｍの電気
化学素子用セパレーター６とした。Example 6 Using a twin cylinder paper machine, slurry 2 to basis weight 10 g
/ M 2 and the slurry 5 were combined with each other at a basis weight of 14 g / m 2 to prepare a wet type nonwoven fabric having a basis weight of 24 g / m 2 . Then, a drum roll 2 heated to 210 ° C. and having a diameter of 1.2 m
Both sides of the non-woven fabric were brought into contact with a book at a speed of 20 m / min and heat-treated to obtain a separator 6 for electrochemical device having a basis weight of 24.5 g / m 2 and a thickness of 75 μm.
【００５２】比較例１
円網２連式の抄紙機を用い、スラリー２から坪量８ｇ／
ｍ2、スラリー４から坪量１０ｇ／ｍ2で抄き合わせし、
坪量１８ｇ／ｍ2の湿式不織布を作製した。次いで、２
００℃に加熱した直径１．２ｍのドラムロール２本に速
度２０ｍ／ｍｉｎで該不織布の両面を接触させて熱処理
し、坪量１８．５ｇ／ｍ2、厚み５６μｍの電気化学素
子用セパレーター７とした。Comparative Example 1 Using a double-cylinder paper machine, slurry 2 to basis weight 8 g /
m 2 , from Slurry 4 with a basis weight of 10 g / m 2 ,
A wet type nonwoven fabric having a basis weight of 18 g / m 2 was prepared. Then 2
Both sides of the non-woven fabric were heat-treated by contacting two drum rolls having a diameter of 1.2 m heated to 00 ° C. at a speed of 20 m / min, and a separator 7 for electrochemical device having a basis weight of 18.5 g / m 2 and a thickness of 56 μm was obtained. did.
【００５３】比較例２
円網２連式の抄紙機を用い、スラリー１から坪量８ｇ／
ｍ2、スラリー３から坪量１０ｇ／ｍ2で抄き合わせし、
坪量１８ｇ／ｍ2の湿式不織布を作製した。次いで、２
００℃に加熱した直径１．２ｍのドラムロール２本に速
度２０ｍ／ｍｉｎで該不織布の両面を接触させて熱処理
し、坪量１８．５ｇ／ｍ2、厚み５６μｍの電気化学素
子用セパレーター８とした。Comparative Example 2 Using a double cylinder type paper machine, slurry 1 to basis weight 8 g /
m 2 , from Slurry 3 with a basis weight of 10 g / m 2 ,
A wet type nonwoven fabric having a basis weight of 18 g / m 2 was prepared. Then 2
Both sides of the nonwoven fabric were contacted with two drum rolls having a diameter of 1.2 m and heated at 00 ° C. at a speed of 20 m / min to heat-treat, and a separator 8 for electrochemical device having a basis weight of 18.5 g / m 2 and a thickness of 56 μm was used. did.
【００５４】比較例３
円網２連式の抄紙機を用いて、スラリー６から坪量９ｇ
／ｍ2、スラリー７から坪量９ｇ／ｍ2で抄き合わせし、
坪量１８ｇ／ｍ2の湿式不織布を作製した。次いで、２
００℃に加熱した直径１．２ｍのドラムロール２本に速
度２０ｍ／ｍｉｎで該不織布の両面を接触させて熱処理
し、坪量１８．５ｇ／ｍ2、厚み５６μｍの電気化学素
子用セパレーター９とした。Comparative Example 3 Using a twin cylinder paper machine, from slurry 6 to basis weight 9 g
/ M 2 and the slurries 7 are combined with a basis weight of 9 g / m 2 ,
A wet type nonwoven fabric having a basis weight of 18 g / m 2 was prepared. Then 2
Both sides of the non-woven fabric were contacted with two drum rolls having a diameter of 1.2 m and heated at 00 ° C. at a speed of 20 m / min to heat-treat, and a separator 9 for electrochemical device having a basis weight of 18.5 g / m 2 and a thickness of 56 μm was prepared. did.
【００５５】＜電気化学素子の作製＞電極活物質として
活性炭８５％、導電材としてカーボンブラック７％、結
着材としてポリテトラフルオロエチレン８％を混練して
厚み０．２ｍｍのシート状電極を作製した。これを厚み
５０μｍのアルミニウム箔の両面に導電性接着剤を用い
て接着させ、圧延して有効電極面積５５ｍｍ×５０ｍ
ｍ、集電体面積１０ｍｍ×４０ｍｍの電極を作製した。
この電極を正極および負極として用いた。実施例１〜６
および比較例１〜３で作製した電気化学素子セパレータ
ーを介して正極と負極を交互に積層していき、正極と負
極が２０枚ずつになるまで積層し素子を作製した。正極
側および負極側の最外層には何れもセパレーターを配し
た。この素子をアルミニウム製ケースに収納した。次い
で、ケースに取り付けられた正極端子および負極端子に
正極リードおよび負極リードを溶接した後、電解液注液
口を残してケースを封口した。この素子を収納したケー
スごと２００℃に３時間加熱し乾燥処理した。次いで、
このケース内に電解液を注入し、注液口を密栓して電気
二重層キャパシタ、すなわち電気化学素子を作製し、そ
れぞれを電気化学素子１〜９とした。ここで、電気化学
素子用セパレーター１〜６および９については、正極側
に全芳香族ポリアミド繊維含有層、負極側に全芳香族ポ
リエステル繊維含有層が接するように配置した。電解液
には、プロピレンカーボネートに１．５ｍｏｌ／ｌにな
るように（Ｃ2Ｈ5）3（ＣＨ3）ＮＢＦ4を溶解させたも
のを用いた。<Preparation of Electrochemical Element> 85% of activated carbon as an electrode active material, 7% of carbon black as a conductive material, and 8% of polytetrafluoroethylene as a binder were kneaded to prepare a sheet electrode having a thickness of 0.2 mm. did. This is adhered to both sides of an aluminum foil having a thickness of 50 μm by using a conductive adhesive and rolled to obtain an effective electrode area 55 mm × 50 m.
m, and an electrode having a current collector area of 10 mm × 40 mm was produced.
This electrode was used as a positive electrode and a negative electrode. Examples 1-6
Then, the positive electrode and the negative electrode were alternately laminated through the electrochemical device separators produced in Comparative Examples 1 to 3, and the positive electrode and the negative electrode were laminated until the number of the positive electrode and the negative electrode became 20 sheets each to produce an element. A separator was placed on each of the outermost layers on the positive electrode side and the negative electrode side. This element was housed in an aluminum case. Then, after the positive electrode lead and the negative electrode lead were welded to the positive electrode terminal and the negative electrode terminal attached to the case, the case was sealed leaving the electrolyte solution injection port. The case containing this element was heated at 200 ° C. for 3 hours and dried. Then
An electrolytic solution was injected into the case, and the injection port was tightly closed to produce electric double layer capacitors, that is, electrochemical elements, which were referred to as electrochemical elements 1 to 9, respectively. Here, the separators for electrochemical devices 1 to 6 and 9 were arranged so that the wholly aromatic polyamide fiber-containing layer was in contact with the positive electrode side and the wholly aromatic polyester fiber-containing layer was in contact with the negative electrode side. As the electrolytic solution, a solution prepared by dissolving (C 2 H 5 ) 3 (CH 3 ) NBF 4 in propylene carbonate at a concentration of 1.5 mol / l was used.
【００５６】電気化学素子用セパレーター１〜９および
電気化学素子１〜９について、下記の試験方法により測
定し、その結果を下記表１に示した。The electrochemical device separators 1 to 9 and the electrochemical devices 1 to 9 were measured by the following test methods, and the results are shown in Table 1 below.
【００５７】＜熱収縮率＞１５ｃｍ×１０ｃｍの大きさ
に切り取った各セパレーター試料をアルミニウム板に載
せ、縦方向に直角な２辺をクリップで挟んで固定し、２
００℃に設定した恒温乾燥器の中に３時間静置した。横
方向の寸法を計り、元の寸法に対する収縮による寸法変
化の割合を求め、熱収縮率（％）とした。<Heat Shrinkage> Each separator sample cut into a size of 15 cm × 10 cm was placed on an aluminum plate, and two sides perpendicular to the vertical direction were clamped and fixed to each other.
It was left standing in a constant temperature dryer set at 00 ° C for 3 hours. The dimension in the lateral direction was measured, the ratio of the dimensional change due to the shrinkage with respect to the original dimension was determined, and the result was the heat shrinkage rate (%).
【００５８】＜引張強度＞各セパレーター試料を、抄紙
方向に平行になるように５０ｍｍ巾に１０本切りそろ
え、引張試験機を用いて引張強度を測定し、平均値を求
めた。<Tensile Strength> Ten separator samples of each width were cut in a width of 50 mm so as to be parallel to the papermaking direction, and the tensile strength was measured using a tensile tester to obtain an average value.
【００５９】＜電解液保液率＞１５ｃｍ×１０ｃｍの大
きさに切り取ったセパレーター試料を２００℃で３時間
乾燥処理した直後の重量（Ｗ1）を計測し、次いでセパ
レーター試料を電解液に１分間浸漬した後、ピンセット
で該試料を取り出し、つるした。電解液が垂れなくなっ
たところで該試料の重量（Ｗ2）を計測した。下記の数
式１より、セパレーターの自重に対する電解液保液率
（％）を求めた。電解液としては、プロピレンカーボネ
ートに１．５ｍｏｌ／ｌになるように（Ｃ2Ｈ5）3（Ｃ
Ｈ3）ＮＢＦ 4を溶解させたものを用いた。<Retention rate of electrolytic solution> 15 cm × 10 cm large
Separator sample cut into pieces at 200 ° C for 3 hours
Weight immediately after drying (W1), Then separate
After immersing the vibrator sample in the electrolyte for 1 minute, tweezers
The sample was taken out and suspended. Electrolyte does not drip
By the way, the weight of the sample (W2) Was measured. The number below
From Equation 1, the electrolyte retention rate against the dead weight of the separator
(%) Was calculated. As the electrolyte, propylene carbonate
To 1.5 mol / l (C2HFive)3(C
H3) NBF FourWhat was melt | dissolved was used.
【００６０】[0060]
【数１】 電解液保液率（％）＝（Ｗ2−Ｗ1）／Ｗ3×１００[Formula 1] Electrolytic solution retention rate (%) = (W 2 −W 1 ) / W 3 × 100
【００６１】＜内部短絡不良率＞電気化学素子１〜９に
２．５Ｖの直流電圧を７２時間印加した後、２．５Ｖま
で充電し、充電直後のもれ電流を計測し、１０ｍＡ以上
ももれ電流が観測されたものを内部短絡不良と見なし、
１００固当たりの内部短絡不良率を示した。<Internal Short-Circuit Defect Ratio> After applying a DC voltage of 2.5 V to the electrochemical devices 1 to 72 for 72 hours, the device was charged to 2.5 V and the leakage current immediately after charging was measured. It is considered that an internal short circuit failure is caused by the observed current.
The internal short circuit failure rate per 100 solids was shown.
【００６２】＜容量変化率＞電気化学素子１〜９につい
て、７０℃、２．５Ｖ印加状態で１０００時間経過後の
容量変化率を求めた。容量変化率が小さい程、寿命が長
いことを意味する。<Capacity Change Rate> With respect to the electrochemical devices 1 to 9, the capacity change rate after 1000 hours at 70 ° C. and 2.5 V applied was determined. The smaller the rate of change in capacity, the longer the life.
【００６３】[0063]
【表１】 [Table 1]
【００６４】評価：表１の結果から明らかなように、本
発明における実施例１〜６で作製した電気化学素子用セ
パレーターは、表面に全芳香族ポリエステル繊維が１０
％以上存在し、反対側表面に全芳香族ポリアミド繊維が
１０％以上存在する湿式不織布からなるため、耐熱性お
よび電解液保持性に優れていた。また、電気化学素子１
〜６は、電極の極性に対応した配置で電気化学素子用セ
パレーターを具備してなるため、容量変化率が小さく、
優れていた。Evaluation: As is clear from the results in Table 1, the electrochemical device separators produced in Examples 1 to 6 of the present invention contained 10 wholly aromatic polyester fibers on the surface.
% Or more and 10% or more of wholly aromatic polyamide fibers on the opposite surface, it was excellent in heat resistance and electrolyte retention. In addition, the electrochemical device 1
Since Nos. 6 to 6 are provided with the separators for electrochemical elements in an arrangement corresponding to the polarities of the electrodes, the rate of change in capacity is small,
Was excellent.
【００６５】実施例１〜６で作製した電気化学素子用セ
パレーターは、全芳香族ポリエステル繊維および全芳香
族ポリアミド繊維の少なくとも一部が繊維径１μｍ以下
にフィブリル化されてなるため、緻密で内部短絡するこ
とがなかったが、実施例６で作製した電気化学素子用セ
パレーターの片面は、フィブリル化繊維を含有しないた
め、細孔がやや大きく、該セパレーターを具備してなる
電気化学素子６は、内部短絡する場合があった。The electrochemical device separators prepared in Examples 1 to 6 were dense and internal short-circuited because at least a part of the wholly aromatic polyester fibers and the wholly aromatic polyamide fibers were fibrillated to a fiber diameter of 1 μm or less. However, since one side of the electrochemical device separator prepared in Example 6 does not contain fibrillated fibers, the pores are rather large, and the electrochemical device 6 including the separator is There was a case where it short-circuited.
【００６６】実施例５で作製した電気化学素子用セパレ
ーターは、熱処理されていないため、引張強度が弱めで
あった。The electrochemical element separator produced in Example 5 was not heat-treated, and thus had a weak tensile strength.
【００６７】一方、比較例１で作製した電気化学素子用
セパレーターは、両面に全芳香族ポリアミド繊維を含有
してなるため、該セパレーターを具備してなる電気化学
素子７は、容量変化率がやや大きくなった。On the other hand, since the separator for electrochemical device manufactured in Comparative Example 1 contains wholly aromatic polyamide fibers on both sides, the electrochemical device 7 equipped with the separator has a capacity change rate slightly. It got bigger.
【００６８】比較例２で作製した電気化学素子用セパレ
ーターは、両面に全芳香族ポリエステル繊維を含有して
なるため、該セパレーターを具備してなる電気化学素子
８は、容量変化率がやや大きくなった。Since the electrochemical device separator prepared in Comparative Example 2 contains wholly aromatic polyester fibers on both sides, the electrochemical device 8 equipped with the separator has a slightly large capacity change rate. It was
【００６９】比較例３で作製した電気化学素子用セパレ
ーターは、全芳香族ポリエステル繊維と全芳香族ポリア
ミド繊維の含有量がそれぞれ５％であるため、耐熱性と
電解液保持性がやや劣っていた。さらにセパレーターは
粗く、内部短絡不良率が高く、該セパレーターを具備し
てなる電気化学素子９は、容量変化率が大きくなった。The electrochemical device separator prepared in Comparative Example 3 was slightly inferior in heat resistance and electrolyte retention because the total aromatic polyester fiber content and total aromatic polyamide fiber content were 5% each. . Further, the separator was rough, and the internal short circuit failure rate was high, and the electrochemical element 9 including the separator had a large capacity change rate.
Claims (4)
％以上存在し、反対側表面に全芳香族ポリアミド繊維が
１０％以上存在する湿式不織布からなることを特徴とす
る電気化学素子用セパレーター。1. Ten percent wholly aromatic polyester fibers are provided on the surface.
% Or more and 10% or more of wholly aromatic polyamide fibers are present on the opposite surface of the wet nonwoven fabric.
族ポリアミド繊維の少なくとも一部が繊維径１μｍ以下
にフィブリル化されてなることを特徴とする請求項１に
記載の電気化学素子用セパレーター。2. The separator for an electrochemical element according to claim 1, wherein at least a part of the wholly aromatic polyester fiber and the wholly aromatic polyamide fiber is fibrillated to have a fiber diameter of 1 μm or less.
含有する層と全芳香族ポリアミド繊維を１０％以上含有
する層を抄き合わせて製造することを特徴とする電気化
学素子用セパレーターの製造方法。3. A method for producing a separator for an electrochemical element, which comprises producing a layer containing 10% or more of wholly aromatic polyester fiber and a layer containing 10% or more of wholly aromatic polyamide fiber by combining them. .
特徴とする請求項３記載の電気化学素子用セパレーター
の製造方法。4. The method for producing a separator for an electrochemical element according to claim 3, wherein the heat treatment is performed at 150 ° C. to 250 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001249795A JP3971905B2 (en) | 2001-08-21 | 2001-08-21 | Separator for electrochemical device and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001249795A JP3971905B2 (en) | 2001-08-21 | 2001-08-21 | Separator for electrochemical device and method for producing the same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2003059766A true JP2003059766A (en) | 2003-02-28 |
| JP2003059766A5 JP2003059766A5 (en) | 2005-05-19 |
| JP3971905B2 JP3971905B2 (en) | 2007-09-05 |
Family
ID=19078740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001249795A Expired - Fee Related JP3971905B2 (en) | 2001-08-21 | 2001-08-21 | Separator for electrochemical device and method for producing the same |
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| Country | Link |
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| JP (1) | JP3971905B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003217976A (en) * | 2002-01-22 | 2003-07-31 | Japan Vilene Co Ltd | Electric double-layer capacitor and separator for the same |
| WO2005057689A1 (en) * | 2003-12-11 | 2005-06-23 | Dupont Teijin Advanced Papers, Ltd. | Heat resistant separator and electric electronic component employing it |
| JP2007103474A (en) * | 2005-09-30 | 2007-04-19 | Nippon Sheet Glass Co Ltd | Electric double layer capacitor and separator therefor |
| JP2007250405A (en) * | 2006-03-17 | 2007-09-27 | Nissan Motor Co Ltd | Bipolar secondary battery |
| JPWO2005088011A1 (en) * | 2004-03-12 | 2008-01-31 | 三菱製紙株式会社 | Heat resistant nonwoven fabric |
| JP2008186707A (en) * | 2007-01-30 | 2008-08-14 | Tomoegawa Paper Co Ltd | Separator for electrochemical element |
| JP2010010037A (en) * | 2008-06-30 | 2010-01-14 | Sumitomo Chemical Co Ltd | Sodium secondary battery |
| JP2011091457A (en) * | 2004-08-25 | 2011-05-06 | Sanyo Electric Co Ltd | Method of manufacturing solid electrolytic capacitor |
| WO2011081914A2 (en) * | 2009-12-15 | 2011-07-07 | E. I. Du Pont De Nemours And Company | Method for increasing the strength and solvent resistance of polyimide nanowebs |
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|---|---|---|---|---|
| JPH0927311A (en) * | 1995-05-09 | 1997-01-28 | Mitsubishi Paper Mills Ltd | Nonwoven fabric for battery separator |
| JP2000331665A (en) * | 1999-05-21 | 2000-11-30 | Oji Paper Co Ltd | Separator for alkali-manganese battery |
| JP2001040597A (en) * | 1999-07-22 | 2001-02-13 | Toray Ind Inc | Hydrophilic nonwoven fabric, battery separator and battery |
-
2001
- 2001-08-21 JP JP2001249795A patent/JP3971905B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0927311A (en) * | 1995-05-09 | 1997-01-28 | Mitsubishi Paper Mills Ltd | Nonwoven fabric for battery separator |
| JP2000331665A (en) * | 1999-05-21 | 2000-11-30 | Oji Paper Co Ltd | Separator for alkali-manganese battery |
| JP2001040597A (en) * | 1999-07-22 | 2001-02-13 | Toray Ind Inc | Hydrophilic nonwoven fabric, battery separator and battery |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003217976A (en) * | 2002-01-22 | 2003-07-31 | Japan Vilene Co Ltd | Electric double-layer capacitor and separator for the same |
| JPWO2005057689A1 (en) * | 2003-12-11 | 2007-07-05 | デュポン帝人アドバンスドペーパー株式会社 | Heat-resistant separator and electrical and electronic parts using the same |
| WO2005057689A1 (en) * | 2003-12-11 | 2005-06-23 | Dupont Teijin Advanced Papers, Ltd. | Heat resistant separator and electric electronic component employing it |
| US20110126401A1 (en) * | 2004-03-12 | 2011-06-02 | Takahiro Tsukuda | Heat-resistant nonwoven fabric |
| JPWO2005088011A1 (en) * | 2004-03-12 | 2008-01-31 | 三菱製紙株式会社 | Heat resistant nonwoven fabric |
| JP4739186B2 (en) * | 2004-03-12 | 2011-08-03 | 三菱製紙株式会社 | Heat resistant nonwoven fabric |
| JP2011091457A (en) * | 2004-08-25 | 2011-05-06 | Sanyo Electric Co Ltd | Method of manufacturing solid electrolytic capacitor |
| JP2007103474A (en) * | 2005-09-30 | 2007-04-19 | Nippon Sheet Glass Co Ltd | Electric double layer capacitor and separator therefor |
| JP2007250405A (en) * | 2006-03-17 | 2007-09-27 | Nissan Motor Co Ltd | Bipolar secondary battery |
| JP2008186707A (en) * | 2007-01-30 | 2008-08-14 | Tomoegawa Paper Co Ltd | Separator for electrochemical element |
| JP2010010037A (en) * | 2008-06-30 | 2010-01-14 | Sumitomo Chemical Co Ltd | Sodium secondary battery |
| WO2011081914A2 (en) * | 2009-12-15 | 2011-07-07 | E. I. Du Pont De Nemours And Company | Method for increasing the strength and solvent resistance of polyimide nanowebs |
| WO2011081914A3 (en) * | 2009-12-15 | 2011-10-06 | E. I. Du Pont De Nemours And Company | Method for increasing the strength and solvent resistance of polyimide nanowebs |
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