JPS6380472A - Separator for battery - Google Patents
Separator for batteryInfo
- Publication number
- JPS6380472A JPS6380472A JP61224616A JP22461686A JPS6380472A JP S6380472 A JPS6380472 A JP S6380472A JP 61224616 A JP61224616 A JP 61224616A JP 22461686 A JP22461686 A JP 22461686A JP S6380472 A JPS6380472 A JP S6380472A
- Authority
- JP
- Japan
- Prior art keywords
- glass fiber
- softening point
- separator
- glass
- glass fibers
- 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
- 239000003365 glass fiber Substances 0.000 claims abstract description 108
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims description 29
- 239000007788 liquid Substances 0.000 abstract description 36
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000003466 welding Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 26
- 239000000835 fiber Substances 0.000 description 25
- 238000010521 absorption reaction Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000004927 fusion Effects 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000005368 silicate glass Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000007499 fusion processing Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 230000035936 sexual power Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
- H01M50/437—Glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は蓄電池用セパレータに係り、特に実質的にガラ
ス繊維のみからなる蓄電池用セパレータに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a separator for a storage battery, and more particularly to a separator for a storage battery consisting essentially only of glass fibers.
［従来の技術］
ガラス繊維を含んでなる蓄電池用セパレータとしては、
既に種々のタイプのものが提案され実用化されているが
、これを大別すると次の３種預となる。即ち、
■ ガラス短ｉａ Ｋ、Ｉを主体とするもの、■ ガラ
ス短！ａ維と合成ｉａ維を混合、成形したもの、
■ ガラス短ｔａ維に粉体を保持させたもの、である。[Prior art] As a separator for storage batteries containing glass fiber,
Various types have already been proposed and put into practical use, but they can be broadly classified into the following three types. That is, ■ glass short ia K, I are the main body, ■ glass short! (1) A mixture of A fiber and synthetic IA fiber and molding; (2) A powder held in short glass Ta fiber;
このうち、■のガラスｌａ ｉ、ｉと粉体との混抄物か
らなるものとしては、例えば特開昭５８−２０６０４６
号に記載されるものがあるが、このものは吸液性は良好
であるものの、粉体がセノ＼レータから剥離、脱落し易
く、また、引張強度も小さいという問題がある。Among these, the one made of a mixture of glass la i, i and powder is disclosed in Japanese Patent Application Laid-Open No. 58-206046, for example.
Although this product has good liquid absorption properties, it has problems in that the powder easily peels off and falls off from the ceno\lator and its tensile strength is low.
一方、■のガラス短繊維と合成繊維とを混抄したものと
しては、特開昭４９−３８１２６号、特開昭５４−２２
５３１号、特開昭５６−９９９６８号、特開昭５３−１
３６６３２号及び特公昭５８−６６３号に記載のものが
あるが、これらは機械的強度（引張強さ及び剛性等）が
高いため、蓄電池組立作業を行ない易いという長所を有
するものの、吸液性、保液性に劣る、系内に有機物が存
在することから電池寿命が短い、という欠点を有する。On the other hand, JP-A-49-38126 and JP-A-54-22 are a mixture of short glass fibers and synthetic fibers.
No. 531, JP-A-56-99968, JP-A-53-1
There are products described in Japanese Patent Publication No. 36632 and Japanese Patent Publication No. 58-663, but these have high mechanical strength (tensile strength, rigidity, etc.) and have the advantage of being easy to assemble the storage battery, but they do not have liquid absorbency, It has the disadvantages of poor liquid retention and short battery life due to the presence of organic matter in the system.
一方、■のガラス短繊維を主体とするものとしては、液
体接着剤等のバインダを使用したものと、これらのバイ
ンダを使用しないものとがある。On the other hand, as for the type (2) mainly made of short glass fibers, there are those that use a binder such as a liquid adhesive and those that do not use such a binder.
［発明が解決しようとする問題点］
ガラス繊維を主体とするセパレータのうち、バインダを
使用しないものは、液の吸収による自由な体積膨張が可
能で、電解液の保液性、吸液性が最も良く、電池特性の
面で好適であるが、反面、この種のセパレータは単にガ
ラス繊維同志の水ガラス化と絡みの力のみで賦形されて
いるため、強度や硬度が低く、機械を使用した電池組立
作業には十分に耐えることができず、作業能率が悪いと
いう不都合がある。[Problems to be solved by the invention] Among separators mainly made of glass fiber, those that do not use a binder can freely expand in volume by absorbing liquid, and have excellent liquid retention and absorption properties for electrolyte. This type of separator is the best in terms of battery characteristics, but on the other hand, this type of separator is formed simply by the force of water vitrification and entanglement of glass fibers, so it has low strength and hardness, and it is difficult to use machines. This has the disadvantage that it cannot sufficiently withstand heavy battery assembly work, resulting in poor work efficiency.
これに対し、バインダを使用した場合には、その接着効
果により強度、硬度は向上されるが、液吸収による体積
膨張がバインダにより阻害され、セパレータの保液性や
吸液性が悪くなる。しかも液筒溶性のバインダでは、電
解液中に溶は出し、電池性能低下の原因となるという問
題があり、その他耐酸化性の面からも好ましいものとは
いえない。On the other hand, when a binder is used, the strength and hardness are improved due to its adhesive effect, but the binder inhibits volumetric expansion due to liquid absorption, resulting in poor liquid retention and liquid absorption properties of the separator. Moreover, a liquid cylinder-soluble binder has the problem that it dissolves into the electrolytic solution, causing a decrease in battery performance, and is not preferable from the viewpoint of oxidation resistance.
このような問題点を解消する、強度、硬度も良好である
と共に、保液性、吸液性にも優れた蓄電池用セパレータ
として、本出願人は実質的にガラス繊維のみから構成さ
れる蓄電池用セパレータであって、ガラス繊維同志が熱
融着されている蓄電池用セパレータにつき、先に特許出
願した（特願昭６１−９４０８３．以下、「先願」とい
う。）。In order to solve these problems, the applicant has developed a separator for storage batteries that has good strength and hardness as well as excellent liquid retention and absorption properties, and has developed a separator for storage batteries that is made essentially only of glass fiber. We previously filed a patent application for a separator for storage batteries in which glass fibers are heat-sealed together (Japanese Patent Application No. 61-94083 (hereinafter referred to as the "prior application")).
先願に係る蓄電池用セパレータは、実質的にガラスｉｎ
ｆ、Ｉのみからなり、有ｍｉａ維やバインダを用いな
いため極めて吸液性、保液性に優れたものとなる上に、
セパレータを構成するガラス繊維は熱融着により互いに
接着されているため、その強度、硬度は著しく高い。The storage battery separator according to the prior application is substantially made of glass in
Since it is composed only of F and I and does not use mia fibers or binders, it has extremely excellent liquid absorbing and liquid retaining properties, and
Since the glass fibers constituting the separator are bonded together by heat fusion, their strength and hardness are extremely high.
しかしながら、実質的にガラスｌｌ１ｔｎのみからなる
セパレータにおいて、セパレータを２１成するガラスｉ
、Ｘ１ｌｆ、（Ｉをその特性を損うことなく ｆａ ｉ
（ｔの表面のガラスを溶かして熱融着させ、所望の強度
を得ることができる加熱温度、時間等の範囲が狭い範囲
に限られているために、加熱温度や時間等の熱融着条件
のＲ密なコントロールが必要となり、熱融着処理が難し
いという問題がある。However, in a separator made essentially only of glass ll1tn, the glass i that forms the separator 21
, X1lf, (I without losing its properties fa i
(Since the range of heating temperature, time, etc. that can melt and heat-seal the glass on the surface of t and obtain the desired strength is limited to a narrow range, the heat-sealing conditions such as heating temperature and time There is a problem in that precise control of R is required and heat fusion processing is difficult.
［問題点を解決するための手段］
本発明は上記先願に基いてなされたものであって、保液
性、吸液性、強度等が共に優れる実質的にガラス繊維の
みからなる蓄電池用セパレータであって、極めて容易に
製造することが可能な蓄電池用セパレータを提供するも
のであり、実質的にガラス繊維のみから構成される蓄電
池用セパレータであって、主体とするガラス短繊維の軟
化点よりも５０〜４００℃低い軟化点の低軟化点ガラス
短繊維が全ガラス繊維の３〜２０瓜量％混合され、かつ
、ガラス繊維同志が熱融着されてなることを特徴とする
蓄電池用セパレータ、を要旨とするものである。[Means for Solving the Problems] The present invention has been made based on the above-mentioned prior application, and provides a separator for storage batteries that is substantially made only of glass fiber and has excellent liquid retention, liquid absorption, and strength. The purpose of the present invention is to provide a storage battery separator that can be manufactured extremely easily, and is a storage battery separator that is substantially made only of glass fibers, and that has a temperature lower than the softening point of the main short glass fibers. A separator for a storage battery, characterized in that low softening point short glass fibers having a softening point lower than 50 to 400° C. are mixed in an amount of 3 to 20% of the total glass fibers, and the glass fibers are heat fused together. The main points are as follows.
以下本発明につき更に詳細に説明する。The present invention will be explained in more detail below.
本発明の蓄電池用セパレータは、主体とするガラス繊維
と該主体ガラス繊維の軟化点より５０〜４００℃低い軟
化点の低軟化点ガラス繊維３〜２０重量％とから構成さ
れている。The separator for a storage battery of the present invention is composed of glass fiber as the main component and 3 to 20% by weight of low softening point glass fiber whose softening point is 50 to 400°C lower than the softening point of the main glass fiber.
本発明において、セパレータを＋ｉ成する主体ガラスＩ
ａ維及び低融点ガラスｌａ維の組成としては、特に制限
はないが、好ましくは含アルカリ珪酸塩ガラス繊維を用
いるのが望ましい。即ち、含アルカリ珪酸塩ガラス繊維
を用いると、製造工程の抄造工程でガラス繊維の表面に
水ガラス状物質が生成し、この水ガラス状物質の粘着性
によって１ａ維同志がより良好に接着される。本発明に
おいては、含アルカリ珪酸塩ガラス１ａ維のうちでも、
蓄電池に使用されることから、耐酸性の良好なものが好
適に使用される。この耐酸性の程度は、平均繊維径１ｍ
μ以下のガラスｌａ ｆａの状態で、ＪＩＳＣ−２２０
２に従フて測定した場合の重量減が２％以下であるのが
望ましい。また、このようなガラスｉａ維の組成として
は重量比で６０〜７５％の５ｉ０２及び８〜２０％のＲ
２０（Ｎａ２０゜Ｋ２Ｏなどのアルカリ金属酸化物）を
主として含有しくただし５ｉ０２＋Ｒ２０は７５〜９０
零）、その他に例えばＣａＯｌＭｇＯ，Ｂ２Ｏ３、Ａｕ
２０３ 、ＺｎＯ，Ｆｅ２Ｏ３などの１ ｆｆｆｌ又は
２種以上を含んだものが挙げられる。含アルカリ珪酸塩
ガラスは、その組成を変えることにより、容易にその軟
化点を変えることができ、主体ガラス繊維及び低軟化点
ガラス繊維を提供することができる。例えば、成分のう
ち、５ｉ０２を減らし、その分Ｃａｂ％ＭｇＯ１Ｂ ２
０３ 、Ｎ ａ ２０等を増すことにより軟化点を下げ
ることができる。In the present invention, the main glass I forming the separator +i
There are no particular restrictions on the composition of the A fibers and the low melting point glass LA fibers, but it is preferable to use alkali-containing silicate glass fibers. That is, when alkali-containing silicate glass fiber is used, a water glass-like substance is generated on the surface of the glass fiber during the papermaking process of the manufacturing process, and the 1a fibers are better adhered to each other by the adhesiveness of this water glass-like substance. . In the present invention, among the alkali-containing silicate glass 1a fibers,
Since it is used in storage batteries, those with good acid resistance are preferably used. This degree of acid resistance is based on an average fiber diameter of 1 m.
In the state of glass la fa below μ, JISC-2220
It is desirable that the weight loss when measured according to 2 is 2% or less. In addition, the composition of such glass IA fiber is 5i02 of 60 to 75% and R of 8 to 20% by weight.
20 (alkali metal oxides such as Na20°K2O), but 5i02+R20 is 75-90
0), others such as CaOlMgO, B2O3, Au
203, ZnO, Fe2O3, etc., or two or more thereof. The softening point of alkali-containing silicate glass can be easily changed by changing its composition, and main glass fibers and low softening point glass fibers can be provided. For example, by reducing 5i02 among the components, Cab%MgO1B2
03, N a 20, etc., the softening point can be lowered.
このような好ましい含アルカリ珪酸塩の主体ガラス繊維
の組成及び低融点ガラス繊維の組成の例を第１表に示す
。Table 1 shows examples of the composition of such preferable alkali-containing silicate-based glass fibers and the compositions of low-melting point glass fibers.
第 １ 表。Table 1.
一方、本発明の蓄電池用セパレータを構成するガラス繊
維は、主体ガラス繊維及び低軟化点ガラス繊維のいずれ
のｆａ維も、平均直径１０〜３０μｍの大径のガラスｉ
ｎ 維ｏ〜３５ＩＩＩ量％、平均直径２μｍを超え１０
μｍ未満の中細径のガラス繊ｆ、Ｉ ０〜３０重量％、
残部平均直径２μｍ以下の細径ガラス１ａ維を含むもの
であることが好ましい。On the other hand, the glass fibers constituting the storage battery separator of the present invention include both main glass fibers and low softening point glass fibers, which are large-diameter glass fibers with an average diameter of 10 to 30 μm.
n Fiber o ~ 35III amount%, average diameter exceeding 2 μm 10
Medium-thin diameter glass fiber f of less than μm, I 0 to 30% by weight,
It is preferable that the remaining portion contains small-diameter glass la fibers having an average diameter of 2 μm or less.
このような中細径、大径のガラス繊維は細径ガラス１ａ
維に比べ安価であり、特に太径のガラスｉａ ｉ（Ｉは
これを併用することによりセパレータの引張強さを向上
させることができるという利点がある。Such medium-sized and large-diameter glass fibers are called small-diameter glass 1a.
It is cheaper than glass fibers, and especially large-diameter glass ia i (I) has the advantage that the tensile strength of the separator can be improved by using it in combination.
細径のガラス１ａｉａの好ましい平均直径は０．５〜１
．０μｍ、より好ましくは０．６〜０．９μｍである。The preferred average diameter of the small diameter glass 1aia is 0.5 to 1
．． It is 0 μm, more preferably 0.6 to 0.9 μm.
直径が１．０μｍを超えるとセパレータの孔径が大きく
なり、逆に０．５μｍよりも小さくなるとその製造コス
トが高価となる。If the diameter exceeds 1.0 μm, the pore size of the separator becomes large, and conversely, if the diameter is smaller than 0.5 μm, the manufacturing cost becomes high.
この細径のガラス繊維の好ましい含有量は、ガラス繊維
重量の６０ｆｉｉ％以上であり、とりわけ６５！１ｆｆ
ｉ％以上が特に好ましい。含有量が６０重量％よりも少
ないと吸液性、保液性が不足し易くなるからである。The preferred content of this small diameter glass fiber is 60% or more of the weight of the glass fiber, especially 65!1ff
i% or more is particularly preferred. This is because if the content is less than 60% by weight, liquid absorption and liquid retention properties tend to be insufficient.
又、この細径のガラス！ａｉａの平均長さは好ましくは
７〜５ Ｑ ｍ ｍ 、より好ましくは１０〜４０ｍｍ
である。平均長さが１０ｍｍよりも短くなるとセパレー
タの強度が小さくなり、５０ｍｍよりも長くなると抄造
時に水中へ均一に分散するのが困難になる。Also, this thin glass! The average length of aia is preferably 7 to 5 Qmm, more preferably 10 to 40mm
It is. If the average length is shorter than 10 mm, the strength of the separator will be reduced, and if it is longer than 50 mm, it will be difficult to uniformly disperse the separator in water during papermaking.
このような細径のガラス繊維はＦＡ法（火炎法）、遠心
法その他のガラス短繊維製造法によって製造できる。Such small-diameter glass fibers can be manufactured by the FA method (flame method), centrifugation method, or other short glass fiber manufacturing methods.
なお本発明においてガラス繊維の平均直径は、試料の３
ケ所について電子顕微鏡で写真撮影し、それぞれ２０本
の繊維についてその直径を０．１μｍ単位で測定し、こ
れらの平均値をとることにより計算される。In addition, in the present invention, the average diameter of the glass fibers is 3
It is calculated by taking a photograph of each part using an electron microscope, measuring the diameter of each 20 fibers in units of 0.1 μm, and taking the average value of these.
中細径のガラス繊維中用いる場合、その好ましい平均直
径は２．０〜５．０μｍ５とりわけ３．０〜４．０μｍ
である。また、含有量はガラス繊維重量の５．０〜３０
．０重量％、とりわけ１０．０〜２５．０ｉ量％とする
のが好ましい。When used in medium and small diameter glass fibers, the preferred average diameter is 2.0 to 5.0 μm, particularly 3.0 to 4.0 μm.
It is. In addition, the content is 5.0 to 30 of the glass fiber weight.
．． It is preferably 0% by weight, especially 10.0 to 25.0% by weight.
中細径のガラス繊維の配合により細径ガラス繊維量を減
らすことができ、コスト的に有利となる。By blending glass fibers with medium and small diameters, the amount of small-diameter glass fibers can be reduced, which is advantageous in terms of cost.
なお、この中細径のガラス繊維の長さは７〜５０ｍｍと
りわけ１０〜４０ｍｍが好ましい。The length of this medium-thin diameter glass fiber is preferably 7 to 50 mm, particularly preferably 10 to 40 mm.
太径のガラスｉａ ｉａを用いる場合、その好ましい平
均直径は１０〜２０μｍ１とりわけ１２〜１９μｍであ
る。また、含有量はガラス繊維重量の８〜３５重量％、
とりわけ１０〜３０重量％とするのが好ましい。平均直
径が１０μｍよりも小さいと、あるいは含有量が８重量
％よりも少ないと、引張強さ改善効果が小さくなり、平
均直径が２０μｍを超えると、あるいは含有量が３５重
量％を超えるとセパレータの吸液性、保液性が小さくな
る。この大径のガラス繊維の長さは５〜８０ｍｍとりわ
け６〜４０ｍｍが好ましい。When using large-diameter glass ia ia, its preferred average diameter is 10 to 20 μm, particularly 12 to 19 μm. In addition, the content is 8 to 35% by weight of the glass fiber weight,
In particular, it is preferably 10 to 30% by weight. When the average diameter is smaller than 10 μm or the content is less than 8% by weight, the tensile strength improvement effect becomes small, and when the average diameter exceeds 20 μm or the content exceeds 35% by weight, the separator Liquid absorption and liquid retention are reduced. The length of this large diameter glass fiber is preferably 5 to 80 mm, particularly 6 to 40 mm.
本発明の蓄電池用セパレータは、好適には、前述のよう
な組成の細径、中細、大径の含アルカリ珪酸塩ガラス繊
維が、湿式抄造により絡み合わされると共に、好ましく
は低軟化点ガラス繊維のみが加熱により軟化ないし溶解
されることにより、特別な接着剤なしに相互に熱融着さ
れている、実質的にガラス繊維のみからなるものである
。The separator for a storage battery of the present invention is preferably made by intertwining small, medium, and large diameter alkali-containing silicate glass fibers having the composition as described above by wet papermaking, and preferably using low softening point glass fibers. It consists essentially only of glass fibers, which are heat-sealed to each other without any special adhesive by being softened or melted by heating.
即ち、本発明においては、好ましくは、加熱による熱融
着により、主体ガラスｌｌｌ維は殆ど軟化ないし溶解さ
せることなく、低軟化点ガラス繊維のみを軟化ないし溶
解させ、軟化ないし溶解した低軟化点ガラス繊維により
ガラスｍｆａ同志を接着する。That is, in the present invention, preferably, only the low softening point glass fibers are softened or melted by thermal fusion by heating without softening or melting the main glass fibers, and the softened or melted low softening point glass fibers are softened or melted. Glass mfa pieces are bonded together using fibers.
このために、熱融着時の加熱温度は主体ガラス繊維と低
軟化点ガラス繊維の中間の温度で行うのが好ましい。し
かして、この加熱温度コントロールの面から、主体ガラ
ス繊維中維軟化点ガラス繊維との軟化点の差があまりに
小さ過ぎると不利である。また、両ガラスＩａ ｆａの
軟化点の差があまりに大き過ぎると、両ガラス繊維の組
成や物性等の違いが大きく開きすぎるために得られるセ
パレータに悪影響を及ぼす可能性がでてくる。このため
、本発明においては、低軟化点ガラス繊維中ｉａ維ラス
１ｎｉｎの軟化点よりも５０〜４００℃、好ましくは６
０〜２００℃低い軟化点を有するものとする。For this reason, it is preferable that the heating temperature during thermal fusion be carried out at an intermediate temperature between the main glass fiber and the low softening point glass fiber. However, from the viewpoint of heating temperature control, it is disadvantageous if the difference in softening point between the main glass fiber and the softening point glass fiber is too small. Furthermore, if the difference in softening point between the two glasses Ia and fa is too large, the difference in composition, physical properties, etc. between the two glass fibers will be too large, which may adversely affect the resulting separator. Therefore, in the present invention, the softening point is 50 to 400° C., preferably 6
It shall have a softening point 0 to 200°C lower.
また、加熱による熱融着処理により軟化ないし溶解する
低軟化点ガラス繊維の割合があまりに少な過ぎると、得
られるセパレータに十分な強度が得られず、逆に多過ぎ
ると、保液性、吸液性を低下させる原因となる。このた
め、本発明においては、低軟化点ガラス繊維の割合を全
ガラスｉａ維の３〜２０重量％、好ましくは７〜１８重
量％とする。In addition, if the proportion of low softening point glass fibers that soften or dissolve during thermal fusing treatment by heating is too small, the obtained separator will not have sufficient strength; It causes a decrease in sexual performance. Therefore, in the present invention, the proportion of low softening point glass fibers is 3 to 20% by weight, preferably 7 to 18% by weight of the total glass IA fibers.
このような本発明の蓄電池用セパレータを製造するには
、主体ガラス繊維及び低軟化点ガラス繊維を所望の割合
に配合して混抄して製造すれば良い。In order to manufacture such a separator for a storage battery according to the present invention, the main glass fiber and the low softening point glass fiber may be blended in a desired ratio and mixed and then manufactured.
なお、ガラス繊維はネット上に抄紙されるのであるが、
その際、離解機内のｐＨ及び／又は抄造タンク内のｐＨ
を約３未満例えば２．５程度とするのが好ましい、この
ような酸性域で離解及び／又は湿式抄造することにより
、ガラス繊維の表面に水ガラスの接着層を形成せしめ、
ついでこれを所定温度例えば８０〜１６０℃に加熱する
ことにより、ガラス繊維をその表面の水ガラスによって
相互に接着することが可能となる。Furthermore, glass fiber is made into paper online,
At that time, the pH in the disintegrator and/or the pH in the papermaking tank
is preferably less than about 3, for example about 2.5, by disintegrating and/or wet papermaking in such an acidic region, forming an adhesive layer of water glass on the surface of the glass fiber,
Then, by heating this to a predetermined temperature, for example, 80 to 160°C, the glass fibers can be bonded to each other by the water glass on the surface.
即ち、セパレータを構成するガラス繊維が含アルカリ珪
酸塩ガラス組成を有するものであれば、ガラス繊維中の
アルカリ成分及びシリカ成分が、ｐＨ２，５程度の酸性
域で分散のための水と反応し水ガラス層がガラス繊維表
面に形成され、この水ガラス層が接着剤として作用しガ
ラス繊維が相互に強固に接着される。That is, if the glass fibers constituting the separator have an alkali-containing silicate glass composition, the alkali components and silica components in the glass fibers will react with water for dispersion in an acidic range of about pH 2.5, causing the water to dissolve. A glass layer is formed on the surface of the glass fibers, and this water glass layer acts as an adhesive to firmly adhere the glass fibers to each other.
通常、このようにして湿式抄造されたガラス繊維抄造体
は、ドラムドライヤに沿わせて乾燥され製品とされるが
、本発明のセパレータの製造においては、得られた抄造
体を乾燥後、主体ガラス繊維の軟化点と低軟化点ガラス
ｉｎ 維の軟化点との中間の温度で高温加熱することに
より好ましくは低軟化点ガラス繊維のみを溶融させて、
ガラス繊維同志を熱融着する。この加熱処理時間はガラ
ス繊維組成等によっても異なるが、長ずざるとセパレー
タの吸液性が低下する原因となり、逆に短すぎると熱融
着が不十分となる。通常は、加熱時間は１〜５分間程度
、好ましくは２〜３分間程度が適当である。加熱は、ガ
ラス繊維同志は熱融着されて強固に接着し、セパレータ
の硬度及び強度は大幅に向上されるが、吸液性が悪くな
らない程度とする。Normally, the glass fiber paper product wet-formed in this way is dried along a drum dryer to produce a product, but in the production of the separator of the present invention, after drying the resulting paper product, the main glass Preferably, only the low softening point glass fibers are melted by heating at a high temperature between the softening point of the fibers and the softening point of the low softening point glass fibers,
Heat-seal the glass fibers together. This heat treatment time varies depending on the glass fiber composition, etc., but if it is too long, the liquid absorption properties of the separator will decrease, and if it is too short, heat fusion will be insufficient. Usually, the appropriate heating time is about 1 to 5 minutes, preferably about 2 to 3 minutes. The heating is carried out to an extent that the glass fibers are thermally fused and firmly adhered to each other, and the hardness and strength of the separator are greatly improved, but the liquid absorption property is not deteriorated.
なお、本発明のセパレータの製造にあたっては、前述の
乾燥のための加熱をこの熱融着のための高温加熱で兼ね
て行ない乾燥処理を省略しても良く、また予め乾燥処理
した後熱融着処理しても良い。In addition, in manufacturing the separator of the present invention, the drying process may be omitted by performing the above-mentioned heating for drying at the same time as high-temperature heating for this thermal bonding, or the drying process may be performed in advance and then the thermal bonding is performed. It may be processed.
また、抄造にあたり、繊維を水中に分散させるに際し分
散剤を使用しても良い。Furthermore, a dispersant may be used to disperse fibers in water during papermaking.
本発明のセパレータ自体の厚さは、使用される＠電池に
よって異なるが、−Ｍには、０．３〜３ｍｍであること
が好ましい。The thickness of the separator itself of the present invention varies depending on the battery used, but -M is preferably 0.3 to 3 mm.
このようにして得られる本発明の蓄電池用セパレータは
、その密度が０．１６±ｏ、ｏ３ｇ／ａｍ’、引張強さ
が４００ｇ／１５ｍｍ幅Ｘ １ ｍｍ厚以上、座屈強度
が３０ ｇ ／ １０ ｍ ｍ幅Ｘ１ｍｍ厚以上である
ことが好ましい。The storage battery separator of the present invention thus obtained has a density of 0.16±o, o3g/am', a tensile strength of 400g/15mm width x 1mm thickness or more, and a buckling strength of 30g/10 It is preferable that the width is mm width x 1 mm thickness or more.
［作用コ
本発明の蓄電池用セパレータは、実質的にガラス繊維の
みからなり、有機繊維やバインダを用いないため極めて
吸液性、保液性に優れたものとなる。また、セパレータ
の強度向上のために通常使用される有機繊維やその他の
接着剤は、セパレータの耐酸性を弱めることがあるのに
対し、本発明の如く、ガラス繊維よりなるセパレータは
、極めて優れた耐酸性を有するものとなる。[Function] The storage battery separator of the present invention is made essentially only of glass fibers and does not use organic fibers or binders, so it has extremely excellent liquid absorption and liquid retention properties. In addition, organic fibers and other adhesives that are normally used to improve the strength of separators can weaken the acid resistance of the separator, but the separator made of glass fiber as in the present invention has extremely excellent properties. It has acid resistance.
また、本発明においては、セパレータを構成するガラス
繊維は熱融着により互いに接着されているため、その強
度、硬度は著しく向上される。Further, in the present invention, since the glass fibers constituting the separator are bonded to each other by heat fusion, the strength and hardness of the separator are significantly improved.
しかも、この熱融着に際し、主体ガラスｉｎ 維は溶解
せず、低軟化点ガラス繊維のみを軟化、溶解する加熱温
度、加熱時間は、幅広い範囲から選定することができる
ため、本発明の蓄電池用セパレータは厳密な条件コント
ロールを要することなく、容易に製造することが可能で
ある。Furthermore, during this thermal fusion, the heating temperature and heating time can be selected from a wide range to soften and melt only the low softening point glass fibers without melting the main glass fibers. Separators can be easily manufactured without requiring strict control of conditions.
［実施例］ 以下実施例及び比較例について説明する。[Example] Examples and comparative examples will be described below.
実施例１〜３、比較例１〜４
第２表に示す配合の構成繊維を水中に没入して水流型分
散機により攪拌して分散させ、更に硫酸を加えて水のｐ
Ｈを２．７とし約１０分間保持した。次いで抄造を行な
い１５０℃に加熱して乾燥した後、比較例１以外は第２
表に示す条件で高温加熱することによりガラス繊維を熱
融着させて、マット状の蓄電池用セパレータを製造した
。Examples 1 to 3, Comparative Examples 1 to 4 The constituent fibers having the compositions shown in Table 2 were immersed in water, stirred and dispersed using a water jet dispersion machine, and sulfuric acid was added to reduce the pH of the water.
H was set to 2.7 and held for about 10 minutes. Next, papermaking was carried out and after heating and drying at 150°C, the second
Glass fibers were thermally fused by heating at high temperatures under the conditions shown in the table to produce a mat-like separator for storage batteries.
このセパレータの灼熱減量、吸液速度、引張強さ、座屈
強度、加圧下の保液性について測定した結果を第２表に
示す。Table 2 shows the results of measurements of the separator's loss on ignition, liquid absorption rate, tensile strength, buckling strength, and liquid retention under pressure.
第２表より、下記のことが明らかである。From Table 2, the following is clear.
即ち、ガラス繊維Ａのみからなるセパレータでは、高温
加熱による熱融着処理を行わない場合（比較例１）と同
様に熱融着処理の加熱温度が６３０℃と低い場合（比較
例２）にも、十分な強度が得られない、また、熱融着処
理の加熱温度が６７０℃と高い場合には強度は向上する
ものの吸液性が低下する。ガラス繊維Ａのみからなるセ
パレータでは、良い結果が得られるものは６５０℃の加
熱温度で熱融着処理を行フたもの（比較例３）のみで、
適切な処理条件の範囲は極めて狭く、条件コントロール
が難しいことがわかる。In other words, a separator made only of glass fiber A can be used when the heating temperature of the heat fusion process is as low as 630°C (Comparative Example 2) as well as when the heat fusion process by high temperature heating is not performed (Comparative Example 1). However, if the heating temperature of the heat fusion treatment is as high as 670° C., the strength will be improved but the liquid absorbency will be lowered. Among separators made only of glass fiber A, the only one that gave good results was one that was heat-fused at a heating temperature of 650°C (Comparative Example 3).
It can be seen that the range of appropriate processing conditions is extremely narrow, making it difficult to control the conditions.
これに対し、本発明に係るガラス繊維Ａを主体とし、ガ
ラス繊維Ｂの低軟化点ガラスを併用したセパレータでは
、５６０℃（実施例１）、５８０℃（実施例２）、６０
０℃（実施例３）と幅広い加熱温度による熱融着処理に
よっても、常に、優れた吸液性、保液性が得られ、その
引張強さや座屈強度についても、良好な結果を得ること
ができる。On the other hand, in the separator based on glass fiber A according to the present invention, which also uses low softening point glass as glass fiber B, the
Excellent liquid absorption and liquid retention properties were always obtained even through heat fusion treatment at a heating temperature as wide as 0°C (Example 3), and good results were also obtained in terms of tensile strength and buckling strength. Can be done.
なお、第２表中＊１〜＊２の繊維は次の通りである。The fibers marked *1 and *2 in Table 2 are as follows.
中１ ガラス繊維Ａ：組成冨第１表のＡ平均直径＝０．
８μｍ
中２ ガラス織ｆａＢ：組成＝第１表のＢ平均直径壬０
．８μｍ
また、実施例及び比較例における各種特性値の測定法は
次の通りである。Medium 1 Glass fiber A: Composition of A average diameter in Table 1 = 0.
8 μm Medium 2 Glass woven faB: Composition = B average diameter in Table 1 0
．． 8 μm In addition, the methods for measuring various characteristic values in Examples and Comparative Examples are as follows.
■ 厚さくｍｍ）
試料をその厚み方向に２０ ｋ ｇ ／ ｄ ｍ”の荷
重で押圧した状態で測定する。（ＪＩＳＣ−２２０２）
■ 目ｆ寸（ｇ／ｃｒｎ’）
試料重量を試料面積で除して得られる値である。■ Thickness (mm) Measure with the sample pressed in the thickness direction with a load of 20 kg/dm. (JISC-2202)
■ Measuring size (g/crn') This is the value obtained by dividing the sample weight by the sample area.
■ 密度（ｇ／ｃｒｎ’）
試料（重１Ｗ）１０ ｃｍｘ １０ ｃｍの面積（Ｓ）
に２０ｋｇの荷重を加えた時の試料の厚さをＴとした時
に、式：Ｗ／ （ＳｘＴ）（ｇ／ｃ ｍ’ ）で与えら
れる値で表わす。■ Density (g/crn') Area of sample (weight 1W) 10 cm x 10 cm (S)
It is expressed as a value given by the formula: W/(SxT)(g/cm'), where T is the thickness of the sample when a load of 20 kg is applied to the sample.
■ 灼熱減量（％）
試料を空気中で６００℃に恒量となるまで加熱し、その
減量分を元の試料重量で除して求める。■ Loss on ignition (%) Heat the sample in air to 600°C until it reaches a constant weight, and calculate the loss by dividing the weight by the original weight of the sample.
■ 吸液速度（ｍ ｍ ／ ５分）
試料を垂直にしてその下部を比重１．３の希硫酸液に浸
漬し、５分後に経時的に上昇する液位を測定することに
より求める。■Liquid absorption rate (m m / 5 minutes) It is determined by holding the sample vertically and immersing its lower part in a dilute sulfuric acid solution with a specific gravity of 1.3, and measuring the rise in the liquid level over time after 5 minutes.
■ 引張強さくｇ／１５ｍｍ幅）
幅１５ｍｍの試料の両端を引張り、それが切断するとき
の外力の値を求め、厚さで除して幅１５ｍｍ、厚さｉｎ
ｍ当りの値（ｇ）で表示する。■ Tensile strength g/15mm width) Pull both ends of a 15mm wide sample, find the value of the external force when it breaks, and divide it by the thickness to obtain a width of 15mm and a thickness of in
It is expressed as the value per m (g).
■ 座屈強度（ｇ／１０ｍｍ幅）
幅５０ｍｍ、長さ１００ｍｍの試料を準備し、長さの上
方５０ｍｍ分をホルダで挟み、下方５０ｍｍは付き出て
いるように保持し、試料の下方先端を秤に接触させ、ホ
ルダを静かに下降させることにより試料を秤に押し付け
、座屈したときの荷！ＩＩ（ｇ）を求める。そして、幅
１０ｍｍ、厚さ１ｍｍ当りの値に換算して表示する。■ Buckling strength (g/10mm width) Prepare a sample with a width of 50mm and a length of 100mm, hold the upper 50mm of the length with a holder, hold it so that the lower 50mm sticks out, and hold the lower tip of the sample. When the sample is pressed against the scale by contacting the scale and gently lowering the holder, the load when buckled! Find II(g). Then, the values are converted and displayed per 10 mm width and 1 mm thickness.
■ 加圧下保液性（ｇ／ｃｃ）
２０ ｋ ｇ／ｄｍ”加重での厚さが１ｍｍで寸法が１
０ｃｍｘｌＯｃｍの試料に水を含ませ、厚さ方向に２０
ｋｇの加重を加えた時の試料中の含水量（ｇ）を求め、
これを試料の体積（ＣＣ）で除した値で示す。■ Liquid retention under pressure (g/cc) 20kg g/dm" Thickness under load is 1mm and dimensions are 1
A sample of 0 cm
Determine the water content (g) in the sample when applying a weight of kg,
This is expressed as the value divided by the sample volume (CC).
［発明の効果］
以上詳述した通り、本発明の蓄電池用セパレータは、実
質的にガラス繊維のみから構成されるものであって、主
体ガラス繊維の軟化点より５０〜４００℃低い軟化点の
低軟化点ガラス繊維が全ガラス繊維の３〜２０！ｉ量％
混抄され、かつ、ガラスｉＪｌ維同志が熱融着されてな
るものであり、■ ガラスｉｎ ｉｎのみよりなること
から、吸液性、保液性が良好で、特に加圧下における保
液性に優れる。また、耐酸化性にも優れる。[Effects of the Invention] As detailed above, the storage battery separator of the present invention is composed essentially only of glass fibers, and has a low softening point of 50 to 400°C lower than the softening point of the main glass fiber. The softening point of glass fiber is 3-20 of all glass fiber! i amount%
It is made by mixing paper and heat-sealing glass iJl fibers, and ■ Since it is made only of glass in, it has good liquid absorption and liquid retention properties, especially excellent liquid retention property under pressure. . It also has excellent oxidation resistance.
■ 熱融着によりガラス繊維は安定に扱者されているた
め、高い強度及び硬度を得ることができる。■ Glass fibers are stabilized by heat fusion, so high strength and hardness can be obtained.
等の優れた効果を有する。It has excellent effects such as
しかも、その製造に当っては、厳密な熱融着処理条件の
コントロールを要さず、極めて高特性なセパレータを容
易かつ効率的に製造することができる。Moreover, in its production, a separator with extremely high properties can be easily and efficiently produced without requiring strict control of heat-sealing treatment conditions.
このような本発明のセパレータによれば、高性能の蓄電
池を優れた作業性のもとに製造することができ、その工
業的有用性は極めて高い。According to the separator of the present invention, a high-performance storage battery can be manufactured with excellent workability, and its industrial utility is extremely high.
Claims (6)
セパレータであって、主体とするガラス繊維の軟化点よ
りも５０〜４００℃低い軟化点の低軟化点ガラス繊維が
全ガラス繊維の３〜２０重量％混合され、かつ、ガラス
繊維同志が熱融着されてなることを特徴とする蓄電池用
セパレータ。(1) A separator for a storage battery consisting essentially only of glass fibers, in which low softening point glass fibers with a softening point 50 to 400 degrees Celsius lower than the softening point of the main glass fibers account for 3 to 30% of the total glass fibers. A separator for a storage battery, characterized in that the glass fibers are mixed at 20% by weight and are thermally fused together.
軟化点との中間の温度で加熱して熱融着してなる特許請
求の範囲第１項に記載の蓄電池用セパレータ。(2) The separator for a storage battery according to claim 1, which is thermally fused by heating at a temperature intermediate between the softening point of the main glass fiber and the softening point of the low softening point glass fiber.
量％、平均直径２μｍを超え１０μｍ未満のガラス繊維
０〜３０重量％、残部平均直径２μｍ以下のガラス繊維
より構成される特許請求の範囲第１項又は第２項に記載
の蓄電池用セパレータ。(3) 0 to 35% by weight of glass fibers with an average diameter of 10 to 30 μm, 0 to 30% by weight of glass fibers with an average diameter of more than 2 μm and less than 10 μm, and the remainder consisting of glass fibers with an average diameter of 2 μm or less The storage battery separator according to item 1 or 2.
許請求の範囲第１項ないし第３項のいずれか１項に記載
の蓄電池用セパレータ。(4) The storage battery separator according to any one of claims 1 to 3, which has a density of 0.16±0.03 g/cm^3.
である特許請求の範囲第１項ないし第４項のいずれか１
項に記載の蓄電池用セパレータ。(5) Any one of claims 1 to 4, which has a tensile strength of 400 g/15 mm width x 1 mm thickness or more.
A separator for storage batteries as described in .
ある特許請求の範囲第１項ないし第５項のいずれか１項
に記載の蓄電池用セパレータ。(6) The separator for a storage battery according to any one of claims 1 to 5, which has a buckling strength of 30 g/10 mm width x 1 mm thickness or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61224616A JP2546240B2 (en) | 1986-09-22 | 1986-09-22 | Storage battery separator and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61224616A JP2546240B2 (en) | 1986-09-22 | 1986-09-22 | Storage battery separator and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6380472A true JPS6380472A (en) | 1988-04-11 |
| JP2546240B2 JP2546240B2 (en) | 1996-10-23 |
Family
ID=16816504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61224616A Expired - Fee Related JP2546240B2 (en) | 1986-09-22 | 1986-09-22 | Storage battery separator and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2546240B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007212028A (en) * | 2006-02-08 | 2007-08-23 | Fujikura Ltd | Heat pipe |
| DE102014218779A1 (en) * | 2014-09-18 | 2016-03-24 | Robert Bosch Gmbh | Separator with glass shut-down effect |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180145298A1 (en) * | 2016-11-23 | 2018-05-24 | Hollingsworth & Vose Company | Battery separators and related methods |
| US10135051B2 (en) | 2016-12-15 | 2018-11-20 | Hollingsworth & Vose Company | Battery components comprising fibers |
-
1986
- 1986-09-22 JP JP61224616A patent/JP2546240B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007212028A (en) * | 2006-02-08 | 2007-08-23 | Fujikura Ltd | Heat pipe |
| DE102014218779A1 (en) * | 2014-09-18 | 2016-03-24 | Robert Bosch Gmbh | Separator with glass shut-down effect |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2546240B2 (en) | 1996-10-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |