JPS60225352A - Separator for storage battery - Google Patents
Separator for storage batteryInfo
- Publication number
- JPS60225352A JPS60225352A JP59081290A JP8129084A JPS60225352A JP S60225352 A JPS60225352 A JP S60225352A JP 59081290 A JP59081290 A JP 59081290A JP 8129084 A JP8129084 A JP 8129084A JP S60225352 A JPS60225352 A JP S60225352A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- fibers
- fiber
- glass
- diameter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000003860 storage Methods 0.000 title claims abstract description 25
- 239000000835 fiber Substances 0.000 claims abstract description 50
- 239000005368 silicate glass Substances 0.000 claims abstract description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims description 14
- 239000003365 glass fiber Substances 0.000 abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 19
- 239000011521 glass Substances 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 10
- 229920002994 synthetic fiber Polymers 0.000 description 10
- 239000012209 synthetic fiber Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
Description
【発明の詳細な説明】
[発明の利用分野]
本発明は蓄電池用セパレータに係り、特にガラスm維及
び合成繊維から構成された蓄電池用セパレータに関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a separator for a storage battery, and more particularly to a separator for a storage battery made of glass fiber and synthetic fiber.
[発明の背景]
カラスm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種類となる。即ち、
■ ガラス短繊維を主体とするもの、
■ ガラス短繊維と合成繊維を混合、成形したもの(例
えば特開昭49−38126)、■ ガラ“ス短繊維に
粉体を保持させたもの(例え ・ば特開昭58−20’
6’046)、
である。[Background of the Invention] As a separator for a storage battery containing glass m-fiber,
Various types have already been proposed and put into practical use, but they can be broadly classified into the following three types. Namely, 1) those mainly composed of short glass fibers, 2) those made by mixing and molding short glass fibers and synthetic fibers (e.g. Japanese Patent Application Laid-Open No. 49-38126), and 2) those in which short glass fibers hold powder ( For example, Japanese Patent Publication No. 58-20'
6'046).
このうち■のガラス短繊維を主体とするものは、繊維長
が短いこと、及び繊維が親水性であることがら細径のガ
ラス短s#Iを多量に含むようにした場合には、蓄電池
本来の基本的性能である保液性、吸液性には優れるもの
の、細径のガラス短m#が高価であるところから、これ
を成形したセパレータも高価である。さらに有機系バイ
ンダを使用せずに成形したセパレータにおいては引張強
度が弱く剛性も小さいために蓄電池組立作業を行ないに
くいという問題がある。また有機バインダを用いて成形
した場合には、蓄電池に組み込ま些て使用されていると
きに、このバインダが電解液中に溶は出し、蓄電池の性
能を劣化させるおそれがある。Among these, the one mainly composed of short glass fibers has a short fiber length and is hydrophilic, so if it contains a large amount of short glass s#I with a small diameter, it will not work properly in a storage battery. Although it has excellent liquid retention and liquid absorption properties, which are the basic properties of the glass, the small diameter glass m# is expensive, so the separator formed from it is also expensive. Furthermore, a separator formed without using an organic binder has low tensile strength and low rigidity, making it difficult to assemble a storage battery. Furthermore, when molding is performed using an organic binder, there is a risk that the binder will dissolve into the electrolyte when it is incorporated into a storage battery and used, thereby degrading the performance of the storage battery.
■のガラス短繊維と合成繊維とを混抄したものは、機械
的強度(引張強度及び剛性等)が高いため、蓄電池組立
作業を行ない易いという長所がある反面、合成繊維がガ
ラス繊維に比べて親水性が低いところから、電解液保持
特性に劣る。A mixture of short glass fibers and synthetic fibers has a high mechanical strength (tensile strength, stiffness, etc.) and has the advantage of being easier to assemble a storage battery, but synthetic fibers are more hydrophilic than glass fibers. Due to its low properties, its electrolyte retention properties are poor.
(辺のガラス繊維と粉体との混抄物においては、吸液性
は良好であるものの、粉体がセパレータから剥離、脱落
し易く、また、引張強度も小さいという問題がある。(Although the mixed material of glass fibers and powder on the side has good liquid absorption properties, there are problems in that the powder easily peels off and falls off from the separator and has low tensile strength.
[発明の目的]
本発明の目的は、上記従来技術の問題点を解消し、引張
強度及び剛性が大きいと共に、電解液の保持特性に優れ
、かつ価格も廉価となる蓄電池用セパレータを提供する
ことにある。[Object of the Invention] An object of the present invention is to provide a separator for storage batteries that solves the problems of the above-mentioned prior art, has high tensile strength and rigidity, has excellent electrolyte retention properties, and is inexpensive. It is in.
[発明の構成]
本発明は、平均直径0.5〜1.0μmの含アルカリ珪
酸塩ガラス繊維60〜90重量%、平均直径10〜20
ルmの含アルカリ珪酸塩ガラス繊#I8〜35重量%、
1.0〜1.5デニールのアクリル繊維及び/又はポリ
エステル繊維2〜7重量%、並びに0.5〜1.0デニ
ールの熱水溶解性ポリビニルアルコール繊維0.04〜
0.6重量%、が湿式混抄され、かつ加熱乾燥されてな
る蓄電池用セパレータにより上記目的を達成するもので
ある。[Structure of the Invention] The present invention comprises 60 to 90% by weight of alkali-containing silicate glass fibers with an average diameter of 0.5 to 1.0 μm, and an average diameter of 10 to 20 μm.
alkali-containing silicate glass fiber #I 8 to 35% by weight,
2 to 7% by weight of 1.0 to 1.5 denier acrylic fibers and/or polyester fibers, and 0.04 to 0.04 to 0.04 to 1.0 denier hot water-soluble polyvinyl alcohol fibers.
The above object is achieved by a separator for a storage battery which is wet-mixed with 0.6% by weight and then heated and dried.
即ち本発明の蓄電池用セパレータは次のa −dの如き
優れた特徴を有している。That is, the storage battery separator of the present invention has the following excellent features a to d.
a、平均直径0.5〜1.0gmの細径のガラス繊維を
含んでおり、保液性、吸液性に優れる。a. Contains thin glass fibers with an average diameter of 0.5 to 1.0 gm, and has excellent liquid retention and liquid absorption properties.
b、この細径のガラス繊維に、平均直径10〜20gm
の大径のガラス繊維を混入させているので、この大径の
ガラス繊維が骨格となり細径ガラス繊維がこの骨格間に
絡み合う様に配置されるようになり、引張強度及び気孔
率が向上するようになる。また大径ガラス繊維は細径ガ
ラス繊維に比べ価格が著しく低いので、セパレータの価
格も廉価なものとなる。b. This thin glass fiber has an average diameter of 10 to 20 gm.
Since large-diameter glass fibers are mixed in, the large-diameter glass fibers become a skeleton and the small-diameter glass fibers are intertwined between the skeletons, improving tensile strength and porosity. become. Furthermore, since large-diameter glass fibers are significantly lower in cost than small-diameter glass fibers, the price of the separator is also lower.
なお本発明者らが、平均直径0.91Lmの細径ガラス
繊維のみが湿式混抄され加熱、乾燥されてなるセパレー
タと、平均直径0.97Lmのガラス繊維70重量%及
び平均直径19川mの大径ガラス繊維30重量%が湿式
混抄され加熱、乾燥されてなるセパレータとについて物
性測定を行ったところ、細径ガラス繊維単味のものより
も細径ガラス繊維に大径ガラス繊維を混合したものは、
引張強度、気孔率が高く、かつ最大細孔径が小さいこと
が認められた。The present inventors have developed a separator in which only small-diameter glass fibers with an average diameter of 0.91 Lm are wet-mixed, heated and dried, and a separator in which 70% by weight of glass fibers with an average diameter of 0.97 Lm and a large one with an average diameter of 19 meters are made. When we measured the physical properties of a separator made of 30% by weight of glass fibers wet-mixed, heated and dried, we found that a separator with a mixture of small-diameter glass fibers and large-diameter glass fibers was better than one with only small-diameter glass fibers. ,
It was observed that the tensile strength and porosity were high, and the maximum pore diameter was small.
C1液保持特性に悪影響を与えない程度に少量の合成繊
維を含み、かつこの合成繊維として少量でも引張強度及
び剛性増大効果の大きいものを採用しており、機械的強
度が高く、かつ吸液性及び保液性の低下がない。Contains a small amount of synthetic fiber to the extent that it does not adversely affect the C1 liquid retention characteristics, and uses a synthetic fiber that has a large effect of increasing tensile strength and rigidity even in a small amount, and has high mechanical strength and liquid absorption. And there is no decrease in liquid retention.
即ち前述の如く、蓄電池用セパレータに合成繊維を混入
させてセパレータの機械的強度を向上させることは従来
より行なわれており、この合成繊維として耐酸性の強い
アクリル繊維等が広く用いられている。That is, as mentioned above, it has been conventionally practiced to improve the mechanical strength of the separator by mixing synthetic fibers into the separator for storage batteries, and acrylic fibers and the like with strong acid resistance are widely used as the synthetic fibers.
ところがこのアクリル繊維等の合成繊維はガラス繊維に
比べて親木性が小さく、混入量が多くなるとセパレータ
の液保持特性を低下させてしまい、逆に混入量が少量で
あれば機械的強度の改善効果が小さくなってしまう。そ
こで本発明者らはガラス繊維に少量混入させるだけでセ
パレータの機械的強一度を大幅に向上させることができ
る合成繊維について検討したところ、アクリル繊維及び
/又はポリエステル繊維に対し微量の熱水溶解性ポリビ
ニルアルコール[Iを併用したものが好適であることを
見い出した。However, synthetic fibers such as acrylic fibers have less wood-philicity than glass fibers, and if they are mixed in too much, they reduce the liquid retention properties of the separator, whereas if they are mixed in small amounts, they can improve mechanical strength. The effect becomes smaller. Therefore, the present inventors investigated synthetic fibers that can significantly improve the mechanical strength of separators by mixing a small amount with glass fibers, and found that they have a trace amount of hot water solubility compared to acrylic fibers and/or polyester fibers. It has been found that the combination of polyvinyl alcohol [I] is suitable.
d、ガラス繊維は含アルカリ珪酸塩ガラス繊維であり、
水溶性有機樹脂バインダを用いることなくガラス繊維同
志の接着が行なわれる。即ち本発明のセパレータは湿式
抄造されてなるものであるが、この抄造時に、ガラス繊
維表面に、ガラス繊維中のアルカリ珪酸塩と抄造水との
反応によって接着層恐らくは水ガラス層が生じ、この水
ガラス層によってガラス繊維同志が接合され、十分な接
合強度が発現される様になる。d, the glass fiber is an alkali-containing silicate glass fiber,
Glass fibers can be bonded together without using a water-soluble organic resin binder. That is, the separator of the present invention is formed by wet papermaking, and during this papermaking, an adhesive layer, perhaps a water glass layer, is formed on the surface of the glass fiber due to the reaction between the alkali silicate in the glass fiber and the papermaking water, and this water Glass fibers are bonded to each other by the glass layer, and sufficient bonding strength is developed.
以下本発明の構成につき更に詳細に説明する。The configuration of the present invention will be explained in more detail below.
まず繊維に関し説明する。First, fibers will be explained.
本発明のセパレータを構成する繊維は含アルカリ珪酸塩
ガラス繊維及び有機繊維である。The fibers constituting the separator of the present invention are alkali-containing silicate glass fibers and organic fibers.
含アルカリ珪酸塩ガラス繊維としては細径のもの及び大
径のものの2種類を含む、細径のガラスm#Iの平均直
径は0.5〜1.0#Lm、より好ましくは0.6〜0
.9ルmである。直径が1.0pLmを超えるとセパレ
ータの空間率が小さくなり、逆に0.5gmよりも小さ
くなるとその製造コストが高価となる。The alkali-containing silicate glass fibers include two types, small diameter ones and large diameter ones, and the average diameter of the small diameter glass m#I is 0.5 to 1.0 #Lm, more preferably 0.6 to 0
.. It is 9 m. If the diameter exceeds 1.0 pLm, the porosity of the separator becomes small, and conversely, if the diameter becomes smaller than 0.5 gm, the manufacturing cost becomes high.
この細径のガラスm#Iの含有量は、全am重量の60
〜90重量%であり、とりわけ65〜85重量%が好ま
しい。含有量が60%よりも少ないと吸液性、保液性が
不足し、逆に90%を超えるとセパレータのコストが高
価となる。The content of this small diameter glass m#I is 60% of the total am weight.
-90% by weight, particularly preferably 65-85% by weight. If the content is less than 60%, the liquid absorption and liquid retention properties will be insufficient, and if the content exceeds 90%, the cost of the separator will be high.
又、この細径のガラスjIitaの平均長さは好ましく
は7〜50mm、より好ましくは10〜40 m腸であ
る。平均長さがlO+mよりも短くなるとセパレータの
強度が小さくなり、50m層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。このような平均
直径0.5〜1.0pmの含アルカリ珪酸塩ガラス繊維
はFA法(火炎法)。Moreover, the average length of this small-diameter glass jIita is preferably 7 to 50 mm, more preferably 10 to 40 m. When the average length is shorter than 1O+m, the strength of the separator decreases, and when it is longer than 50 m layer, it becomes difficult to uniformly disperse the separator in water during papermaking. Such alkali-containing silicate glass fibers with an average diameter of 0.5 to 1.0 pm are produced using the FA method (flame method).
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
。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m錐についてその直径を0 、1 #Lm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。It can be produced by centrifugation or other short glass fiber production methods. In addition, in the present invention, the average diameter of the glass fibers is determined by taking photographs of three locations on the sample using an electron microscope, and determining the average diameter of each glass fiber at 20 mm.
It is calculated by measuring the diameter of the m-cone of a book in units of 0 and 1 #Lm and taking the average value of these measurements.
大径のガラスamとしては平均直径10〜20ILm、
好ましくは12〜19μmのものを全繊維重量の8〜3
5重量%、好ましくは10〜30%含む。平均直径が1
0.u、mよりも小さいと、あるいは含有量が8%より
も少ないと、引張強度改善効果が小ξくなり、平均直径
が2oルmを超えると、あるいは含有量が、35%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5〜80量層とりわけ6〜4
011w1が好ましい。As a large diameter glass am, the average diameter is 10 to 20 ILm,
Preferably 8 to 3 of the total fiber weight is 12 to 19 μm.
It contains 5% by weight, preferably 10-30%. average diameter is 1
0. When u and m are smaller, or when the content is less than 8%, the tensile strength improvement effect becomes small, and when the average diameter exceeds 2 olm or the content exceeds 35%, the separator The liquid absorption and liquid retention properties of the liquid are reduced. The length of this large diameter glass fiber is 5 to 80 layers, especially 6 to 4
011w1 is preferred.
ガラス繊維の組成の好適な範囲について次に説明する。A suitable range of the composition of the glass fiber will be explained next.
本発明のセパレ〜りを構成するガラス繊維は含アルカリ
珪酸塩ガラス組成のものであり、その表面に水ガラスを
形成し得るものである。又、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l#L以下のガラス繊維の状態で
JISC−2202に従って測定した場合の重量減が2
%以下であるのが望ましい。又、このようなガラス繊維
の組成としては重量比で60〜75%のSiO、及び8
〜20%のR2O(Na2o、に2oなどどのアルカリ
金属酸化物)を、主として含有しくただしS iO+
R20は75〜90%)、その他に、例えばcao、M
go、B2O2、Al2O2,ZnO,Fe2O3など
(7)1種又は2種以上を含んだものが挙げられる。尚
好ましい含アルカリ珪酸環ガラスの一例を次の第1表に
示す。The glass fibers constituting the separate material of the present invention have an alkali-containing silicate glass composition, and are capable of forming water glass on their surfaces. Furthermore, since it is used in storage batteries, those with good acid resistance are preferably used. The degree of acid resistance is determined by the weight loss of 2 when measured according to JISC-2202 using glass fibers with an average fiber diameter of 1#L or less.
% or less is desirable. In addition, the composition of such glass fiber is 60 to 75% SiO and 8% by weight.
Mainly contains ~20% R2O (alkali metal oxides such as Na2o, Ni2O, etc.), but SiO+
R20 is 75-90%), and in addition, for example, cao, M
Examples include those containing one or more of (7) such as go, B2O2, Al2O2, ZnO, Fe2O3. Examples of preferable alkali-containing silicate ring glasses are shown in Table 1 below.
第 1 表
本発明のセパレータはこのような含アルカリ珪酸塩ガラ
ス繊維の他に有機繊維として熱可塑性のアクリル繊維及
び/又はポリエステルを含む、アクリルm維及び/又は
ポリエステル繊維の混合割合はセパレータ重量の2〜7
重量%であり、とりわけ3〜6%とするのが好ましい、
これらのm維の混合割合が7重量%を超えると、繊維の
材質いかんによっては蓄電池性能に悪影響を及ぼすおそ
れがあり、2%を下回ると強度改善効果が小さくなる。Table 1 The separator of the present invention contains thermoplastic acrylic fibers and/or polyester as organic fibers in addition to such alkali-containing silicate glass fibers. 2-7
% by weight, preferably 3 to 6%,
If the mixing ratio of these m-fibers exceeds 7% by weight, depending on the material of the fibers, it may have an adverse effect on the performance of the storage battery, and if it falls below 2%, the strength improvement effect will be reduced.
なおアクリルs#l及び/又はポリエステル繊維は1.
0〜1.5デニールの、ものが用いられ、その長さは2
〜10tim程度が好ましい。Note that acrylic s#l and/or polyester fibers are 1.
0 to 1.5 denier is used, and its length is 2
~10tim is preferable.
本発明のセパレータは、有機繊維として、さらに、熱水
溶解性ポリビニルアルコールIh1sを含む。The separator of the present invention further contains hot water-soluble polyvinyl alcohol Ih1s as the organic fiber.
前述のように、アクリル繊維、ポリエステル繊!はガラ
ス繊維に比べ疎水性であるため、これらの都合量が多く
なるとセパレータの保液性、吸液性が低下するのである
が、熱水溶解性ポリビニルアルコール繊維を少量混合し
ただけてセパレータの引張強さ及び座屈強度が大幅に向
上される。そのためアクリル繊維及び/又はポリエステ
ル繊維の使用量が少なくて足り、セパレータの強度が増
大されると共に保液性、吸液性の低下が防止できるので
ある。As mentioned above, acrylic fiber, polyester fiber! is more hydrophobic than glass fiber, so if the amount of these fibers increases, the liquid retention and absorption properties of the separator will decrease, but by mixing a small amount of hot water-soluble polyvinyl alcohol fiber, the separator's tensile strength Strength and buckling strength are significantly improved. Therefore, only a small amount of acrylic fiber and/or polyester fiber is required, and the strength of the separator is increased, and a decrease in liquid retention and absorption properties can be prevented.
ポリビニルアルコール繊維の混合量はセパレータ重量の
0.04〜0.6重量%であり、とりわけ0.05〜0
.2重量%とするのが好ましい。The amount of polyvinyl alcohol fiber mixed is 0.04 to 0.6% by weight of the separator weight, especially 0.05 to 0.
.. Preferably, it is 2% by weight.
またその長さは2〜low−程度が好ましい。Moreover, the length is preferably about 2 to low.
本発明の蓄電池用セパレータは、細径及び大径の含アル
カリ珪酸塩ガラス繊維、アクリル繊維及び/又はポリエ
ステル繊維及び熱水溶解性ポリビニルアルコールtRr
aを例えばPH値を2.5〜3.5に保った水の中に一
定時間、例えば5〜20分水流型分散機等を用いて繊維
をなるべく切断せずに分散させておき、それを湿式抄造
して、該ガラス繊維の表面に接着層おそらくは水ガラス
層を形成せしめ、ついでこれを所定温度、例えば80〜
1.80℃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によって得るこ
とができる。即ち本発明のセパレータを構成するガラス
繊維は、前述のように、含アルカリ珪酸塩ガラス組成を
有するところから、ガラス中のアルカリ成分及びシリカ
成分が、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amが接着される。The separator for storage batteries of the present invention comprises small diameter and large diameter alkali-containing silicate glass fibers, acrylic fibers and/or polyester fibers, and hot water soluble polyvinyl alcohol tRr.
A is dispersed in water whose pH value is maintained at 2.5 to 3.5 for a certain period of time, for example 5 to 20 minutes, using a water jet dispersion machine, etc., without cutting the fibers as much as possible. Wet papermaking is performed to form an adhesive layer, perhaps a water glass layer, on the surface of the glass fiber, and then the paper is heated to a predetermined temperature, e.g.
It can be obtained by adhering glass fibers to each other by means of water glass on their surfaces by heating to 1.80°C. That is, since the glass fibers constituting the separator of the present invention have an alkali-containing silicate glass composition as described above, the alkali components and silica components in the glass react with water for dispersion, resulting in a water glass layer. This water glass layer is formed on the surface of the glass fiber and acts as an adhesive to bond the glass am.
なお繊維の一部として混合されたアクリル繊維及び/又
はポリエステル繊維、ポリビニルアルコール繊維も後工
程の熱処理工程(例えば乾燥工程)において成形もしく
は接着作用を発揮し、セパレータの強度を高める。Note that the acrylic fibers, polyester fibers, and polyvinyl alcohol fibers mixed as part of the fibers also exert a shaping or adhesion effect in the subsequent heat treatment step (for example, the drying step), thereby increasing the strength of the separator.
本発明のセパレータ自体の厚さは、使用される蓄電池に
よって異なるが0.3〜31m1Bであることが好まし
い。なお、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。又、湿式抄造された繊維抄造体、例えば抄
造コンベアー上にある繊維抄造体にジアルキルスルフオ
サクシネートをスプレーして、ガラス繊維に対して0.
005〜10重量%付着させることによって、ジアルキ
ルスルフオサクシネートの有する親水性によりセパレー
タの保液性を向上させることができる。ジアルキルスル
フオサクシネートを上記の如くスプレーする代わりに抄
造槽中の分散水に混入してもよい。The thickness of the separator itself of the present invention varies depending on the storage battery used, but is preferably 0.3 to 31 m1B. Note that a dispersant may be used when dispersing the fibers in water. Further, a dialkyl sulfosuccinate is sprayed onto a wet-formed fiber paper product, for example, a fiber paper product on a paper-making conveyor, so that the glass fiber has a 0.
By attaching the dialkyl sulfosuccinate in an amount of 0.005 to 10% by weight, the liquid retention property of the separator can be improved due to the hydrophilicity of the dialkyl sulfosuccinate. Instead of spraying the dialkyl sulfosuccinate as described above, it may be mixed into the dispersion water in the papermaking tank.
なおガラス短繊維にシリカ粉末、ガラス粉末等の粉体を
混入して抄紙すると最大細孔径の小さいセパレータが得
られる。しかしこのセパレータは密度が大きくなり、気
孔率が小さい。Note that if paper is made by mixing powder such as silica powder or glass powder with short glass fibers, a separator with a small maximum pore diameter can be obtained. However, this separator has a high density and a low porosity.
蓄電池用セパレータとしては、最大細孔径が小さくて気
孔率が大きく、保液性、吸液性に優れるという特性面で
の長所を具備すると共に、素材価格が廉価であり、セパ
レータ価格も安価であることが工業的に製造されるため
に重要なことである。大径(例えば平均直径が19pm
)のガラス繊維とガラス粉末とを、本発明のセパレータ
を基本的構成とするセパレータに組み合わせるようにす
れば、安価かつ性能の優れた蓄電池用セパレータが得ら
れる様になる。As a separator for storage batteries, it has the advantages of a small maximum pore diameter, high porosity, and excellent liquid retention and absorption properties, and the material price is low, and the separator price is also low. This is important for industrial production. Large diameter (e.g. average diameter 19pm)
) and glass powder are combined into a separator having the basic structure of the separator of the present invention, an inexpensive separator for storage batteries with excellent performance can be obtained.
[発明の実施例] 以下実施例について説明する。[Embodiments of the invention] Examples will be described below.
組成が第1表のAであり、平均直径0.8pm、平均長
さ10mmの細径のガラス繊維75重量部、組成が第1
表のAであり、平均直径19pm、平均長さ25mmc
7)ガラス9920重量部、太さ1.2デニールのアク
リルlag (カネボウ(株)製、商品名カネカロンS
)を長さ3mmに切断したもの4.9重量部及びポリビ
ニルアルコール繊#1(スプレ(株)製、商品名VPB
105)を長さ3 m mに切断したちの001重量部
を水中に投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PHを2.7とし約10分間保
持した0次いで抄造を叶い150℃に加熱してマット状
の蓄電池用セパレ〜りを製造した。このセパレータを構
成する各ガラス繊維及び粉末はガラス繊維の表面に形成
された水ガラスにより相互に接着されていることが観察
された。The composition is A in Table 1, and the composition is 75 parts by weight of thin glass fibers with an average diameter of 0.8 pm and an average length of 10 mm.
A in the table, average diameter 19pm, average length 25mmc
7) Acrylic lag with 9920 parts by weight of glass and 1.2 denier thickness (manufactured by Kanebo Co., Ltd., trade name: Kanekalon S)
) cut to a length of 3 mm and 4.9 parts by weight of polyvinyl alcohol fiber #1 (manufactured by Spray Co., Ltd., trade name: VPB)
105) was cut to a length of 3 mm, and 1 part by weight of 001 was poured into water, stirred and dispersed using a water jet disperser, and sulfuric acid was added to bring the pH of the water to 2.7, which was maintained for about 10 minutes. Then, the paper was formed and heated to 150° C. to produce a mat-like storage battery separate material. It was observed that each glass fiber and powder constituting this separator were bonded to each other by water glass formed on the surface of the glass fiber.
この実施例に係るセパレータの引張強度、気孔率、最大
細孔径、座屈強度について測定した結果を第2表に示す
。Table 2 shows the results of measuring the tensile strength, porosity, maximum pore diameter, and buckling strength of the separator according to this example.
また比較のために、実施例と同じ繊維素材を用い、配合
を第2表の如く変えたものについて同様の特性測定を行
なった。For comparison, the same characteristics were measured using the same fiber materials as in the examples but with different formulations as shown in Table 2.
第 2 表 これらの特性値の測定法は次の通りである。Table 2 The method for measuring these characteristic values is as follows.
(1)厚さく1鵬) 試料をその厚み方向に20kg/
drn’の荷重で押圧した状
態で測定する。(1) Thickness: 1 inch) The sample is weighed 20 kg/
Measurement is performed under pressure with a load of drn'.
(JISC−2202)
(2)密度(g/ctn’) 試料10cmX10cm
の面積(S)に20kgの荷重(W)
を加えた時の試料の厚さをT
とした時に、式:W/(SX
T) (g / ctn’)で与えられる値で表わす。(JISC-2202) (2) Density (g/ctn') Sample 10cmX10cm
When T is the thickness of the sample when a load (W) of 20 kg is applied to the area (S) of
(3)目付(g/cm’) 試料重量を試料面積で除し
て得られる値である。(3) Fabric weight (g/cm') This is a value obtained by dividing the sample weight by the sample area.
(4)引張り強さくg)幅lO履膳の試料の両端を引張
りそれが切断するときの外
力の値(g)で表示する。(4) Tensile strength (g) Indicate the external force (g) when pulling both ends of a sample with a width of lO and cutting it.
(5)気孔率(%) セパレータの密度なり、ガラス繊
維を構成するガラスの
密度をaとしたとき、
((a−b)/a) X100 (%)で表わされる。(5) Porosity (%) The density of the separator is expressed as ((ab)/a)X100 (%), where a is the density of the glass constituting the glass fibers.
(6)最大細孔径(P履)マット状試料をメタノールに
十分に浸漬した後、直径
15m5の開口を有するホルダ
に装着し、該開口を通して徐
々に空気を流す、試料から最
初に気泡が発生したときの空
気流の試料通過前後の差圧Δ
Pを検知し、次式により算出
する。(6) Maximum pore diameter (P) After fully immersing the mat-like sample in methanol, it was placed in a holder with an opening of 15 m5 in diameter, and air was gradually allowed to flow through the opening. Air bubbles were initially generated from the sample. The differential pressure ΔP of the air flow before and after passing through the sample is detected and calculated using the following formula.
最大細孔径(pLn)=に/ΔP
(k二定数)
(7)座屈強度(g) 1対の平行板間に輻lO層層、
長さ50園層の試料を幅方
向に挾み、徐々に平行板の挾
圧力を高め、座屈したときの
荷重(g)をめる。Maximum pore diameter (pLn) = /ΔP (k constant) (7) Buckling strength (g) Between a pair of parallel plates, a radial O layer,
A sample with a length of 50 layers is sandwiched in the width direction, the clamping pressure of the parallel plates is gradually increased, and the load (g) when buckled is calculated.
第2表より実施例に係る蓄電池用セパレータは、引張強
度及び座屈強度が著しく高いと共に気孔率が大きくかつ
最大細孔径が小さいことが認められる。特にポリビニル
アルコール繊維の有無だけが実質的な相違点である実施
例と比較例3を比べると、このポリビニルアルコール繊
維を混合することにより引張強さ及び座屈強度が大幅に
向上されることが認められる。From Table 2, it is recognized that the storage battery separators according to Examples have extremely high tensile strength and buckling strength, large porosity, and small maximum pore diameter. In particular, when comparing Example and Comparative Example 3, in which the only substantial difference was the presence or absence of polyvinyl alcohol fibers, it was found that the tensile strength and buckling strength were significantly improved by mixing the polyvinyl alcohol fibers. It will be done.
なお同様の試験を、第1表のB及びCのガラス−繊維に
ついて行なったところ同様の結果が得られた。When similar tests were conducted on glass fibers B and C in Table 1, similar results were obtained.
[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、引
張強度及び剛性が大きいので蓄電池の組立作業が容易で
ある。また気孔率が大きく電解液の保液量が多いと共に
、最大細孔径が小さく吸液性に優れる。さらに、大径の
ガラス繊維が細径のものに比べ低価格であるので、廉価
である。[Effects of the Invention] As detailed above, the storage battery separator of the present invention has high tensile strength and rigidity, and thus facilitates the assembly work of the storage battery. In addition, it has a large porosity and can retain a large amount of electrolyte, and has a small maximum pore diameter and excellent liquid absorption. Furthermore, since large-diameter glass fibers are cheaper than small-diameter ones, they are inexpensive.
代理人 弁理士 重 野 剛Agent: Patent attorney Tsuyoshi Shigeno
Claims (1)
繊維60〜90重量%、平均直径10〜20g、mの含
アルカリ珪酸塩ガラス繊維8〜35重量%、1.0〜1
.5デニールのアクリル繊維及び/又はポリエステル繊
維2〜7重量%、並びに0.5〜1.0デニールの熱水
溶解性ポリビニルアルコール繊mo、04〜0.6重量
%、が湿式混抄され、かつ加熱乾燥されてなることを特
徴とする蓄電池用セパレータ。(1) The following fibers, i.e. average diameter 0.5-1. OPM alkali-containing silicate glass fiber 60-90% by weight, average diameter 10-20 g, m alkali-containing silicate glass fiber 8-35% by weight, 1.0-1
.. 2 to 7% by weight of 5 denier acrylic fibers and/or polyester fibers and 0.5 to 1.0 denier hot water-soluble polyvinyl alcohol fibers MO, 04 to 0.6% by weight are wet-mixed and heated. A storage battery separator characterized by being dried.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59081290A JPS60225352A (en) | 1984-04-23 | 1984-04-23 | Separator for storage battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59081290A JPS60225352A (en) | 1984-04-23 | 1984-04-23 | Separator for storage battery |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60225352A true JPS60225352A (en) | 1985-11-09 |
JPH0427672B2 JPH0427672B2 (en) | 1992-05-12 |
Family
ID=13742247
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59081290A Granted JPS60225352A (en) | 1984-04-23 | 1984-04-23 | Separator for storage battery |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60225352A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62195850A (en) * | 1986-02-20 | 1987-08-28 | Nippon Sheet Glass Co Ltd | Separator for storage battery |
US5281498A (en) * | 1991-05-23 | 1994-01-25 | Nippon Sheet Glass Co., Ltd. | Sheet-like separator and valve regulated lead acid battery |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5563079B2 (en) | 2010-07-02 | 2014-07-30 | 日鍛バルブ株式会社 | Engine phase variable device and control device therefor |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53136632A (en) * | 1977-04-30 | 1978-11-29 | Yuasa Battery Co Ltd | Separator for storage battery |
JPS5832354A (en) * | 1981-07-27 | 1983-02-25 | Toshiba Battery Co Ltd | Battery |
JPS5971255A (en) * | 1982-10-15 | 1984-04-21 | Nippon Glass Seni Kk | Separator for storage battery |
-
1984
- 1984-04-23 JP JP59081290A patent/JPS60225352A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53136632A (en) * | 1977-04-30 | 1978-11-29 | Yuasa Battery Co Ltd | Separator for storage battery |
JPS5832354A (en) * | 1981-07-27 | 1983-02-25 | Toshiba Battery Co Ltd | Battery |
JPS5971255A (en) * | 1982-10-15 | 1984-04-21 | Nippon Glass Seni Kk | Separator for storage battery |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62195850A (en) * | 1986-02-20 | 1987-08-28 | Nippon Sheet Glass Co Ltd | Separator for storage battery |
US5281498A (en) * | 1991-05-23 | 1994-01-25 | Nippon Sheet Glass Co., Ltd. | Sheet-like separator and valve regulated lead acid battery |
Also Published As
Publication number | Publication date |
---|---|
JPH0427672B2 (en) | 1992-05-12 |
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