JPH0249348A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH0249348A JPH0249348A JP63246788A JP24678888A JPH0249348A JP H0249348 A JPH0249348 A JP H0249348A JP 63246788 A JP63246788 A JP 63246788A JP 24678888 A JP24678888 A JP 24678888A JP H0249348 A JPH0249348 A JP H0249348A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- fibers
- weight
- glass
- fiber
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 31
- 239000003365 glass fiber Substances 0.000 claims abstract description 50
- 239000000835 fiber Substances 0.000 claims abstract description 45
- 239000004760 aramid Substances 0.000 claims abstract description 20
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 20
- 238000007789 sealing Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 25
- 238000010521 absorption reaction Methods 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229920002994 synthetic fiber Polymers 0.000 description 5
- 239000012209 synthetic fiber Substances 0.000 description 5
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- 229920000271 Kevlar® Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012790 adhesive layer Substances 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
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment 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
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は密閉形鉛蓄電池に係り、特に吸液性、保液性が
良好であると共に、著しく高い強度を有するセパレータ
を用いた、長寿命で高容量の廉価な密閉形鉛蓄電池に関
する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a sealed lead-acid battery, in particular a battery with a long life using a separator that has good liquid absorption and liquid retention properties and extremely high strength. and related to high-capacity, inexpensive sealed lead-acid batteries.
［従来の技術］
蓄電池の陽極の形式としては、従来よりペースト式極板
とクラッド式極板とが知られている。近年、蓄電池につ
いてその密閉化が試みられつつあり、ペースト式密閉形
鉛蓄電池は極板間に平均直径１μｍ以下の微細ガラス繊
維を主体とするセパレータを介在させ、このセパレータ
に電解液を吸収させることにより流動する電解液をなく
し、充電終期に正極で発生する酸素ガスをセパレータ内
の空隙を通じて負極に移動せしめ負極活物質と反応させ
ることによって密閉化するように構成されている。[Prior Art] Paste-type electrode plates and clad-type electrode plates have been known as types of anodes for storage batteries. In recent years, attempts have been made to seal storage batteries, and paste-type sealed lead-acid batteries have a separator mainly made of fine glass fibers with an average diameter of 1 μm or less interposed between the electrode plates, and the electrolyte is absorbed by this separator. This eliminates the flowing electrolyte and allows the oxygen gas generated at the positive electrode at the end of charging to move to the negative electrode through the gaps in the separator and react with the negative electrode active material, thereby sealing the battery.
このような蓄電池用に用いられるガラス繊維を含んでな
る蓄電池用セパレータとしては、■ ガラス短繊維を主
体とするもの、
■ ガラス短繊維とアクリル等の合成繊維を混合、成形
したもの、
などが知られている。As storage battery separators containing glass fibers used in storage batteries, there are two types of separators that are known: ■ those mainly made of short glass fibers, and ■ those made by mixing and molding short glass fibers with synthetic fibers such as acrylic. It is being
■のガラス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。バインダを使用した場合には、
たとえ２〜３％程度の少量使用であっても、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、吸液速度が著しく低下
し、セパレータの保液性や吸液性が悪くなる。これに対
し、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、電池特性の面で最も好適であるが、繊維のからみ力
と繊維表面の化学反応による接着の効果とによりシート
形状を保持するものであるため、高速の電池組立工程に
適用するには強度不足であり、電池の生産性が低く、高
価な密閉形鉛蓄電池にならざるを得ない。As for the glass fiber-based materials mentioned in (2), there are those that use a binder such as a liquid adhesive, and those that do not use such a binder. If you use a binder,
Even if it is used in a small amount of 2 to 3%, its adhesive effect will improve strength and hardness, but the volume expansion due to liquid absorption will be inhibited by the binder, and the liquid absorption rate will decrease significantly, causing the liquid retention of the separator. The properties and liquid absorption become worse. On the other hand, those that do not use binders can freely expand in volume by absorbing liquid, have the best electrolyte retention and absorption properties, and are the most suitable in terms of battery characteristics. Because the sheet shape is maintained by the entanglement force and the adhesion effect caused by the chemical reaction on the fiber surface, it is insufficient in strength to be applied to high-speed battery assembly processes, resulting in low battery productivity and expensive sealed types. It has no choice but to become a lead-acid battery.
■のアクリル等の合成繊維が混入されてなるセパレータ
は、機械的特性に優れている反面、合成繊維がガラス繊
維に比べて親木性が低いところから、硫酸液の吸液性並
びに保液性が劣るという欠点を有している。Separators mixed with synthetic fibers such as acrylic have excellent mechanical properties, but because synthetic fibers are less wood-friendly than glass fibers, they have poor absorption and retention properties for sulfuric acid solutions. It has the disadvantage of being inferior.
このようなことから、より安価な密閉形鉛蓄電池を得る
ために電池性能を損なうことなく、強度、硬度を向上さ
せる技術の出現が強く望まれていた。For this reason, there has been a strong desire for a technology to improve strength and hardness without impairing battery performance in order to obtain a cheaper sealed lead-acid battery.
［発明が解決しようとする課題］
従来の密閉形鉛蓄電池に用いるセパレータは、主体材料
であるガラス繊維が、引張強度は大きい反面剪断応力は
弱いため、一般にセパレータと極板とを組合せる場合、
第２図に示す如く、剪断応力Ｆが働きセパレータ１と極
板２との接点Ａ、 Ｂにおいて、セパレータ１が破断す
るという問題があった。セパレータ１の接点Ａ、Ｂでの
破断は、正・負両極板間が短絡する危険性が高くなるこ
とを意味しているため、従来、このような破断が生じな
いように極めてゆっくり丁寧に組立てることが強いられ
ていた。このようなことから、得られる密閉形鉛蓄電池
は高価にならざるを得ないという欠点があった。[Problems to be Solved by the Invention] The main material of separators used in conventional sealed lead-acid batteries is glass fiber, which has high tensile strength but low shear stress.
As shown in FIG. 2, there was a problem in that the separator 1 was broken at the contact points A and B between the separator 1 and the electrode plate 2 due to the shear stress F. Breakage at contacts A and B of separator 1 means that there is a high risk of a short circuit between the positive and negative electrode plates, so conventionally the assembly was done extremely slowly and carefully to avoid such breakage. I was forced to do that. For this reason, the resulting sealed lead-acid battery has the drawback of being expensive.
従来、蓄電池用セパレータの引張強度や硬さを向上させ
る技術については種々研究がなされているが、正・負両
極板間の短絡防止のために剪断強度を改良する技術につ
いては何ら提案がなされていない。このようなことから
、高い生産性、即ち高速で正・負両極板をセパレータを
介して重ね合わせても、極板の端部で短絡することがな
いような、高い剪断強度を有する蓄電池用セパレータを
用いて、これを高速で重ね合わせて廉価な密閉形鉛蓄電
池とすることが望まれていた。Various studies have been conducted on techniques to improve the tensile strength and hardness of separators for storage batteries, but no proposals have been made on techniques to improve shear strength in order to prevent short circuits between positive and negative electrode plates. do not have. For this reason, a separator for storage batteries with high productivity, that is, a high shear strength that prevents short circuits at the ends of the electrode plates even when the positive and negative electrode plates are overlapped with the separator interposed at high speed. It has been desired to stack these at high speed to create an inexpensive sealed lead-acid battery.
本発明は上記従来の問題点を解決し、保液性、吸液性に
優れ、しかも、強度及び硬度が改善され、とりわけ剪断
強度が著しく高いセパレータを用いて、長寿命で高容量
の密閉形鉛蓄電池を廉価に提供することを目的とする。The present invention solves the above-mentioned conventional problems, and uses a separator that has excellent liquid retention and absorption properties, improved strength and hardness, and especially extremely high shear strength, and is capable of producing a sealed type with a long life and high capacity. The aim is to provide lead-acid batteries at low prices.
［課題を解決するための手段］
本発明の密閉形鉛蓄電池は、ガラス繊維を主体とし、芳
香族ポリアミド繊維をセパレータを構成する繊維全量の
０．１〜１５重量％含んでなるセパレータを極板間に配
したことを特徴とする。[Means for Solving the Problems] The sealed lead-acid battery of the present invention includes a separator mainly composed of glass fibers and containing aromatic polyamide fibers in an amount of 0.1 to 15% by weight based on the total amount of fibers constituting the separator. It is characterized by being placed in between.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の密閉型鉛蓄電池に用いるセパレータを構成する
繊維成分はガラス繊維と芳香族ポリアミド繊維である。The fiber components constituting the separator used in the sealed lead-acid battery of the present invention are glass fiber and aromatic polyamide fiber.
本発明において用いる芳香族ポリアミド繊維としては、
繊維直径１．０〜４０μｍ、ｉａ維長さ０．５〜２５ｍ
ｍ、とりわけ繊維直径１０〜２０μｍ、平均繊維長さ２
ｍｍ程度のものが好ましく、例えば「ケブラー■」 （
デュポン社製）等を用いることができる。The aromatic polyamide fiber used in the present invention includes:
Fiber diameter 1.0-40μm, ia fiber length 0.5-25m
m, especially fiber diameter 10-20 μm, average fiber length 2
It is preferable to use something about mm in diameter, such as “Kevlar■” (
(manufactured by DuPont), etc. can be used.
本発明にかかるセパレータにおいて、このような芳香族
ポリアミド繊維の含有量は全繊維量の０．１〜１５重量
％とする。芳香族ポリアミド繊維の含有量が０．１重量
％未満では本発明による十分な剪断強度の改善効果が得
られず、高速で正・負両極板を積み重ねるとその間が短
絡する。In the separator according to the present invention, the content of such aromatic polyamide fibers is 0.1 to 15% by weight of the total amount of fibers. If the aromatic polyamide fiber content is less than 0.1% by weight, the present invention cannot sufficiently improve the shear strength, and if the positive and negative electrode plates are stacked at high speed, a short circuit will occur between them.
逆に、芳香族ポリアミド繊維の含有量が１５重量％を超
えると吸液性、保液性が低下して電池の容量が小さくな
り、また引張強度も低下することとなる上に、コスト高
となり好ましくない。好ましい芳香族ポリアミド！ａ維
の含有量はセパレータの全繊維量の０．５〜１２重量％
、特に好ましくは１．０〜１０重量％である。On the other hand, if the aromatic polyamide fiber content exceeds 15% by weight, the liquid absorption and retention properties will decrease, resulting in a decrease in battery capacity, a decrease in tensile strength, and an increase in cost. Undesirable. Preferred aromatic polyamide! The content of A fiber is 0.5 to 12% by weight of the total fiber amount of the separator.
, particularly preferably from 1.0 to 10% by weight.
ガラス繊維としては、耐酸性が良好な含アルカリガラス
繊維が好ましい。含アルカリ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繊維同
志が接着される。As the glass fiber, alkali-containing glass fiber with good acid resistance is preferable. When alkali-containing glass fibers are used, a water glass-like substance is generated on the surface of the glass fibers during the papermaking process of the manufacturing process, and the fibers are adhered to each other by the adhesiveness of this water glass-like substance.
ガラス繊維は、平均直径１μｍ以下の微細な直径のもの
を主体とするものが好ましく、全量がこの微細なガラス
繊維であっても良い。また、この平均直径１μｍ以下の
細径ガラス繊維を主体とし、平均直径１０〜３０μｍの
大径のガラス繊維８〜３５重量％及び平均直径１μｍを
超え１０μｍ未満の中細径のガラス繊維５〜３０重量％
を含むものであるものも好適である。中細径、大径のガ
ラス繊維は微細なものに比べ安価であり、特に大径のガ
ラス繊維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。It is preferable that the glass fibers mainly consist of fine glass fibers with an average diameter of 1 μm or less, and the entire amount may be made of such fine glass fibers. In addition, mainly composed of small glass fibers with an average diameter of 1 μm or less, 8 to 35% by weight of large glass fibers with an average diameter of 10 to 30 μm, and 5 to 30% by weight of medium and small glass fibers with an average diameter of more than 1 μm and less than 10 μm. weight%
Those containing the following are also suitable. Medium-thin and large-diameter glass fibers are cheaper than fine ones, and large-diameter glass fibers in particular have the advantage of being used in combination to improve the tensile strength of the separator.
微細なガラス繊維の好ましい平均直径は０．５〜１．０
μｍ、より好ましくは０．６〜０．９μｍである。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。The preferred average diameter of the fine glass fibers is 0.5 to 1.0
μm, more preferably 0.6 to 0.9 μm. 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.
この微細なガラス繊維の好ましい含有量は、ガラス繊維
重量の６０重量％以上であり、とりわけ６５重量％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、電池の容量が小さくなるからで
ある。The content of the fine glass fibers is preferably 60% by weight or more, particularly preferably 65% by weight or more based on the weight of the glass fibers. This is because if the content is less than 60% by weight, the liquid absorption and liquid retention properties will be insufficient and the capacity of the battery will be reduced.
このような微細なガラス繊維は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 fine 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を用いる場合、その好ましい平均直
径は２．０〜５．０μｍ、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１０．０〜２５．０３ｉｉ％とす
るのが好ましい。When medium-sized glass fibers are used, the preferred average diameter is 2.0 to 5.0 μm, especially 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 25.03ii%.
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.
大径のガラス繊維を用いる場合、その好ましい平均直径
は１０〜２０μｍ、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１
０μｍ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。If large diameter glass fibers are used, their preferred average diameter is between 10 and 20 μm, especially between 12 and 19 μm. Further, the content is preferably 8 to 35% by weight, particularly 10 to 30% by weight based on the weight of the glass fibers. average diameter is 1
If the average diameter is smaller than 0 μm or the content is less than 8% by weight, the tensile strength improvement effect will be small, and if the average diameter exceeds 20 μm or the content is more than 35% by weight, the liquid absorption property of the separator will decrease. , the liquid retention becomes smaller.
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.
本発明の密閉形鉛蓄電池に用いるセパレータを構成する
ガラス繊維は、含アルカリ珪酸塩ガラス組成のものが、
その表面に水ガラスを形成して接着性を発現するところ
から好ましい。そして、このうちでも耐酸性の良好なも
のが好適に使用される。この耐酸性の程度は、平均繊維
径１μ以下のガラス繊維の状態で、・ＪＩＳＣ−２２０
２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。また、このようなガラス繊維の組成としては
重量比で６０〜７５％のＳｉＯ２及び８〜２０％のＲ２
０（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
％）その他に例えばＣａｂ、ＭｇＯ，Ｂ２０３ Ａｕ
２０３、ＺｎＯ，Ｆｅ２Ｏ３などの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塩
ガラスの一例を次の第１表に示す。The glass fibers constituting the separator used in the sealed lead-acid battery of the present invention have an alkali-containing silicate glass composition.
It is preferable because it forms water glass on its surface and exhibits adhesive properties. Among these, those with good acid resistance are preferably used. This degree of acid resistance is determined according to JISC-222 in the state of glass fiber with an average fiber diameter of 1μ or less.
It is desirable that the weight loss is 2% or less when measured according to 2. The composition of such glass fibers is 60-75% SiO2 and 8-20% R2 by weight.
0 (alkali metal oxides such as Na20 and K2O),
Mainly contained, but 5i02+R20 is 75-90
%) In addition, for example, Cab, MgO, B203 Au
Examples include those containing one or more of 203, ZnO, and Fe2O3. An example of a preferable alkali-containing silicate glass is shown in Table 1 below.
第１表
本発明の密閉形鉛蓄電池に用いるセパレータを製造する
には、まず通常の合成繊維を配合したセパレータの製造
方法と同様の方法によって繊維の抄造体を製造する。即
ち、ガラス繊維として含アルカリ珪酸塩ガラス繊維を用
いる場合には、ガラス繊維と芳香族ポリアミド繊維とを
、例えばｐＨ値２．５〜３．０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８０〜１８０℃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
し、また芳香族ポリアミド繊維同志あるいは芳香族ポリ
アミド繊維とガラス繊維とを該芳香族ポリアミド繊維の
熱融着により接着することによって得ることができる。Table 1 To manufacture the separator used in the sealed lead-acid battery of the present invention, a fiber paper product is first manufactured by a method similar to that used for manufacturing separators containing ordinary synthetic fibers. That is, when using alkali-containing silicate glass fibers as the glass fibers, the glass fibers and aromatic polyamide fibers are placed in water maintained at a pH value of 2.5 to 3.0 for a certain period of time, for example, 5 to 3.0. The glass fibers are dispersed for 20 minutes using a water jet dispersion machine, etc., and then wet-formed to form an adhesive layer, perhaps a water glass layer, on the surface of the glass fibers. Glass fibers are bonded to each other by water glass on their surfaces by heating, and aromatic polyamide fibers are bonded to each other or aromatic polyamide fibers and glass fibers are bonded by heat fusion of the aromatic polyamide fibers. be able to.
通常、このようにして湿式抄造された抄造体は、ドラム
ドライヤに沿わせて乾燥され製品とされる。Usually, the paper product produced by wet paper making in this manner is dried along a drum dryer to form a product.
このようにして得られるセパレータ自体の厚さは密閉形
鉛蓄電池の正・負両極板の間隔と同じか千〇％であるこ
とが好ましく、通常は０．３〜３ｍｍであることが好ま
しい。The thickness of the separator itself obtained in this manner is preferably the same as or 1,000% of the distance between the positive and negative electrode plates of a sealed lead-acid battery, and is usually preferably 0.3 to 3 mm.
なお、繊維を水中に分散あるいは抄造工程において、水
ガラスを添加し、接着作用を助長させることも可能であ
る。水ガラス以外にも、類似の無機系接着剤を用いるこ
ともできる。このようなものとしては、Ｓｔ １ｐａｐ
７００ （セントラル硝子■製、商品名）等が挙げられ
る。その他、分散にあたり、分散剤を使用しても良い。It is also possible to add water glass during the dispersion of fibers in water or during the papermaking process to promote adhesion. In addition to water glass, similar inorganic adhesives can also be used. Such as St 1pap
700 (manufactured by Central Glass ■, trade name). In addition, a dispersant may be used for dispersion.
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ｏ、ｏｏｓ〜１０
ｆｉｉ％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。Further, by spraying a dialkyl sulfosuccinate onto a wet-processed fiber paper product, for example, a fiber paper product on a paper-making conveyor, o, oos to 10
By attaching the dialkyl sulfosuccinate in an amount of 5%, 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.
［作用コ
芳香族ポリアミド繊維は他の合成繊維に比し、著しく高
い剪断強度を有する繊維であるため、比較的少量の使用
で、セパレータの強度、硬度とりわけ剪断強度を著しく
向上させ、しかも保液性、吸液性、耐酸性等を損なうこ
とがない。従って、このようなセパレータを用いた本発
明の密閉形鉛蓄電池は、長寿命で高容量であり、高速で
正・負両極板を積み重ねることが可能であり、生産性が
高く廉価なものとすることができる。[Effects] Aromatic polyamide fibers have significantly higher shear strength than other synthetic fibers, so using a relatively small amount can significantly improve the strength, hardness, and especially shear strength of the separator, and also improve liquid retention. properties, liquid absorption, acid resistance, etc. Therefore, the sealed lead-acid battery of the present invention using such a separator has a long life and high capacity, can stack positive and negative electrode plates at high speed, and is highly productive and inexpensive. be able to.
［実施例］ 以下実施例について説明する。[Example] Examples will be described below.
実施例１
第２表に示す配合の構成繊維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ｐ
Ｈを２．８とし約１０分間保持した。次いで抄造を行い
、１６０℃に加熱してマット状の蓄電池用セパレータを
製造し、その諸特性を測定した。結果を第２表に示す。Example 1 The constituent fibers of the composition shown in Table 2 were put into water, stirred and dispersed using a water jet disperser, and sulfuric acid was added to reduce the pH of the water.
H was set to 2.8 and held for about 10 minutes. Next, papermaking was carried out and heated to 160°C to produce a mat-like separator for storage batteries, and its various properties were measured. The results are shown in Table 2.
また、これら５種類のセパレータの中から、Ｎｏ、３及
びＮｏ、４を選び、本発明による密閉形鉛蓄電池Ａ及び
従来の密閉形鉛蓄電池Ｂを作製した。なお正・負両極板
間の間隙は０．９ｍｍであり、電槽に挿入する時に極板
にかかる圧力は５５ ｋ ｇ／ｄｒｎ”であって、積み
重ねる速度は従来を１００とした時に５倍の５００とし
た。得られた蓄電池の公称容量は１２Ｖ−５Ａｈ／１０
ＨＲであり、その特性は第３表の通りであった。Further, from among these five types of separators, No. 3 and No. 4 were selected to produce a sealed lead-acid battery A according to the present invention and a conventional sealed lead-acid battery B. The gap between the positive and negative electrode plates is 0.9 mm, the pressure applied to the electrode plates when inserted into the battery case is 55 kg/drn'', and the stacking speed is 5 times faster than the conventional one when compared to 100. 500.The nominal capacity of the obtained storage battery was 12V-5Ah/10
HR, and its properties are as shown in Table 3.
第２表
※１ 平均直径０．８μｍガラス繊維
※２ ケブラー■＃２９（デュポン社製）平均繊維長さ
２ｍｍ繊維直径 １０〜２０μｍ
第 ３
表
中１．２５Ａで２時間放電、０．５Ａで６時間充電を１
サイクルとして充放電を繰り返した時、初期の容量の５
０％まで低下する迄のサイクル数
第２表に示す通り、本発明の密閉形鉛蓄電池に用いる芳
香族ポリアミド繊維を含むセパレータは、従来のガラス
繊維から構成されるセパレータ（Ｎｏ、４）と同様に優
れた吸液性、保液性を有し、その他の特性についても同
様に高特性を維持するものである上に、その剪断強度は
著しく高い。一方、芳香族ポリアミド繊維を２０重量％
と多量に配合したセパレータ（Ｎｏ、５）では、吸液性
が低下し好ましくない。Table 2 *1 Average diameter 0.8 μm Glass fiber *2 Kevlar ■ #29 (manufactured by DuPont) Average fiber length 2 mm Fiber diameter 10-20 μm Table 3 Discharge at 1.25 A for 2 hours, 6 at 0.5 A Charge for 1 hour
When charging and discharging are repeated as a cycle, the initial capacity of 5
Number of cycles required to decrease to 0% As shown in Table 2, the separator containing aromatic polyamide fiber used in the sealed lead-acid battery of the present invention is similar to the conventional separator made of glass fiber (No. 4). It has excellent liquid absorption and liquid retention properties, maintains other properties that are similarly high, and has extremely high shear strength. On the other hand, 20% by weight of aromatic polyamide fiber
In the separator (No. 5) containing a large amount of the compound, the liquid absorbency decreases, which is not preferable.
従って、第３表からも明らかなように、本発明の密閉形
鉛蓄電池（Ａ）は従来のセパレータを用いたもの（Ｂ）
と同等あるいはそれ以上の容量を有し、その上、高速で
正・負両極板を積み重ねても極板端部で破断し、短絡す
ることがなく長い寿命を発揮する。そして、従来よりも
乱暴に扱っても短絡することがないので高速で正・負両
極板を積み重ねることが可能になり、より廉価な密閉形
鉛蓄電池となる。なお、第３表のＢの寿命性能が大きく
バラライているのは、組立時に生じていた極板端部の小
さな破断部で充放電を繰り返すことによって短絡が発生
したためである。Therefore, as is clear from Table 3, the sealed lead-acid battery (A) of the present invention is different from the one using the conventional separator (B).
It has a capacity equal to or greater than that of 1, and has a long life without breaking at the ends of the plates and causing short circuits even when both positive and negative plates are stacked at high speed. Furthermore, since it does not cause short circuits even when handled roughly than conventional batteries, it becomes possible to stack positive and negative polar plates at high speed, resulting in a cheaper sealed lead-acid battery. The reason why the life performance of B in Table 3 varies widely is that a short circuit occurred due to repeated charging and discharging at a small fracture at the end of the electrode plate that occurred during assembly.
なお、第２表に示される実施例及び比較例における特性
値の測定法は次の通りである。The method of measuring the characteristic values in the Examples and Comparative Examples shown in Table 2 is as follows.
■ 厚さ（ｍ＋）
試料をその厚み方向に２０ｋｇ／ｄｍ’の荷重で押圧し
た状態で測定する。 （ＪＩＳＣ−２２０２）■ ０１
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 (m+) Measure the sample while pressing it with a load of 20 kg/dm' in the thickness direction. (JISC-2202) ■ 01
Dimension (g/crn") This is the value obtained by dividing the sample weight by the sample area.
■ 密度（ｇ／ｃｍ’）
試料（重量Ｗ）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／ （ｓ ＸＴ） （ｇ ／ｃｒｎ’）
で与えられる値で表わす。■ Density (g/cm') Sample (weight W) 10 cm x 10 cm area (S)
When the thickness of the sample when a load of 20 kg is applied to is T, the formula: w/ (s XT) (g / crn')
It is expressed by the value given by .
■ 引張強度 （ｇ７１５ｍｍ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（ｇ）を求め、厚さ（ｍｍ）で除して、幅１５
＋ｎｍ、厚さ１ ｍｍ当りの値で表示する。■ Tensile strength (g715mm width) Find the external force (g) when pulling both ends of a 15mm wide sample and it cuts it, divide by the thickness (mm), and calculate the width 15mm.
+nm, expressed as value per 1 mm thickness.
■ 剪断強度 （ｇ）
第３図（ａ）（側面図）及び第３図（ｂ）（平面図）に
示す如く、鉄板１１、剪断用治具１２、試料１３、アル
ミニウム板１４、鉄板１５及び重り１６を組み立て、鉄
板１１及び１５に配線し、試料１３が切れたらブザーが
鳴るようにセットする。重り１６を増して行き、試料１
３が切れブザーが鳴った時点の荷重（重り１６、アルミ
ニウム板１４、鉄板１５の合計型ｆｆ１）で表す。■ Shear strength (g) As shown in Figure 3 (a) (side view) and Figure 3 (b) (plan view), the steel plate 11, shearing jig 12, sample 13, aluminum plate 14, iron plate 15, and Assemble the weight 16, wire it to the iron plates 11 and 15, and set it so that a buzzer will sound when the sample 13 is cut. Increase the weight 16, sample 1
It is expressed as the load (total type ff1 of weight 16, aluminum plate 14, and iron plate 15) at the time when 3 is cut and the buzzer sounds.
なお、測定に用いた各部材の仕様は下記の通りである。The specifications of each member used in the measurement are as follows.
鉄板１１．１５ ： ４ｃｍｘ５ｃｍ、重さ８０ｇ剪断
用治具：第３図（Ｃ）（正面図）に示す厚み５．０ｍｍ
の超硬標準バイト用
チップの頂角ＲをけずってＲをな
くしたもの。Iron plate 11.15: 4cm x 5cm, weight 80g Shearing jig: Thickness 5.0mm as shown in Figure 3 (C) (front view)
This is a carbide standard bit tip with the apex angle R removed.
アルミニウム板１４：４ｃｍｘ５ｃｍ。Aluminum plate 14: 4cm x 5cm.
重さ ５ｇ
■ 保液性（ｇ−水／ ｃ ｃ−セパレータ）試料に水
を飽和するまで含ませ、次いでその試料を５分間空中に
吊して置く。しかる後、試料の重量を測定して試料中に
含まれる水の量を算出し、この水の量を試料の体積で除
して得られる値。Weight: 5 g ■ Liquid retention (g-water/cc-separator) Immerse the sample in water until it is saturated, and then suspend the sample in the air for 5 minutes. After that, the weight of the sample is measured to calculate the amount of water contained in the sample, and this value is obtained by dividing the amount of water by the volume 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、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 (mm/5 minutes) Determine 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.
■ 耐酸性（％）
８０℃に保った比Ｉ１１．２の硫酸液中に５時間浸漬し
たときの重量減を測定し、減量を元の重量で徐して百分
比に換算する。(2) Acid resistance (%) Measure the weight loss when immersed in a sulfuric acid solution with a ratio I11.2 maintained at 80°C for 5 hours, divide the weight loss by the original weight, and convert it into a percentage.
■ 灼熱原料（％）
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。■ Burning raw material (%) Heat the sample in air to 600°C until the weight becomes constant, and calculate the weight loss by dividing the weight of the original sample.
参考例１
有機繊維及びその配合割合を種々変えて、実施例１のＮ
０９１と同様にして得られたセパレータの剪断強度を実
施例１と同様にして測定し、配合割合との関係を第１図
に示した。Reference Example 1 N of Example 1 was prepared by varying the organic fibers and their blending ratios.
The shear strength of the separator obtained in the same manner as 091 was measured in the same manner as in Example 1, and the relationship with the blending ratio is shown in FIG.
第１図より、芳香族ポリアミド繊維は、他の有機繊維に
比し、著しく優れた剪断強度の向上作用を有することが
明らかである。From FIG. 1, it is clear that aromatic polyamide fibers have a significantly superior effect of improving shear strength compared to other organic fibers.
［発明の効果コ
以上詳述した通り、本発明の密閉形鉛蓄電池は、そのセ
パレータに芳香族ポリアミド繊維を配合してなるもので
あって、芳香族ポリアミド繊維により、その比較的少な
い配合量で、極めて優れた補強効果が奏され、機械的強
度とりわけ剪断強度の極めて高いものであり、高速で正
・負両極板間に挿入しても破断したり短絡したりするこ
とがない。しかも、吸液性、保液性、耐酸性等について
も損なわれることがないので、高い容量と長い寿命の密
閉形鉛蓄電池が提供され、また、生産性が高いので極め
て庶価なものである。[Effects of the Invention] As detailed above, the sealed lead-acid battery of the present invention has aromatic polyamide fibers blended into its separator. It has an extremely excellent reinforcing effect, has extremely high mechanical strength, especially shear strength, and will not break or short circuit even when inserted between the positive and negative electrode plates at high speed. Moreover, it does not impair liquid absorption, liquid retention, acid resistance, etc., making it possible to provide a sealed lead-acid battery with high capacity and long life.In addition, it is highly productive and therefore extremely inexpensive. .
第１図は参考例１の結果を示すグラフである。
第２図はセパレータと極板との組合せ工程を示す断面図
である。第３図（ａ）〜（Ｃ）は剪断強度の測定方法を
示す図であって、第３図（ａ）は側面図、第３図（ｂ）
は剪断治具の配置を示す平面図、第３図（Ｃ）は剪断治
具の正面図である。
１・・・セパレータ、 ２・・・極板。
代理人 弁理士 重 野 剛
第１図
第２図
第３図
有機繊維配合割合（重量’／、）FIG. 1 is a graph showing the results of Reference Example 1. FIG. 2 is a sectional view showing the process of assembling the separator and the electrode plate. Figures 3(a) to (C) are diagrams showing the method of measuring shear strength, with Figure 3(a) being a side view and Figure 3(b) being a side view.
3 is a plan view showing the arrangement of the shearing jig, and FIG. 3(C) is a front view of the shearing jig. 1...Separator, 2...Electrode plate. Agent Patent Attorney Tsuyoshi Shigeno Figure 1 Figure 2 Figure 3 Organic fiber blending ratio (weight'/)
Claims (1)
香族ポリアミド繊維をセパレータを構成する繊維全量の
０．１〜１５重量％含んでなるセパレータを極板間に配
したことを特徴とする密閉形鉛蓄電池。(1) Sealing characterized by having a separator mainly composed of glass fibers with an average diameter of 1 μm or less and containing 0.1 to 15% by weight of aromatic polyamide fibers based on the total amount of fibers constituting the separator, disposed between the electrode plates. lead-acid battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63246788A JP2632716B2 (en) | 1988-05-19 | 1988-09-30 | Sealed lead-acid battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-122812 | 1988-05-19 | ||
| JP12281288 | 1988-05-19 | ||
| JP63246788A JP2632716B2 (en) | 1988-05-19 | 1988-09-30 | Sealed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0249348A true JPH0249348A (en) | 1990-02-19 |
| JP2632716B2 JP2632716B2 (en) | 1997-07-23 |
Family
ID=26459868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63246788A Expired - Fee Related JP2632716B2 (en) | 1988-05-19 | 1988-09-30 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2632716B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002305847A (en) * | 2001-04-02 | 2002-10-18 | Nidec Shibaura Corp | Motor |
| JP2003017030A (en) * | 2001-06-28 | 2003-01-17 | Nippon Sheet Glass Co Ltd | Separator for sealed lead-acid battery and sealed lead- acid battery |
| JP2003308819A (en) * | 2002-04-17 | 2003-10-31 | Nippon Muki Co Ltd | Separator for sealed lead storage battery, its manufacturing method, and sealed lead storage battery |
| US10177360B2 (en) | 2014-11-21 | 2019-01-08 | Hollingsworth & Vose Company | Battery separators with controlled pore structure |
| WO2022107334A1 (en) * | 2020-11-20 | 2022-05-27 | 日本板硝子株式会社 | Lead storage battery separator |
-
1988
- 1988-09-30 JP JP63246788A patent/JP2632716B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002305847A (en) * | 2001-04-02 | 2002-10-18 | Nidec Shibaura Corp | Motor |
| JP2003017030A (en) * | 2001-06-28 | 2003-01-17 | Nippon Sheet Glass Co Ltd | Separator for sealed lead-acid battery and sealed lead- acid battery |
| JP2003308819A (en) * | 2002-04-17 | 2003-10-31 | Nippon Muki Co Ltd | Separator for sealed lead storage battery, its manufacturing method, and sealed lead storage battery |
| US10177360B2 (en) | 2014-11-21 | 2019-01-08 | Hollingsworth & Vose Company | Battery separators with controlled pore structure |
| US11239531B2 (en) | 2014-11-21 | 2022-02-01 | Hollingsworth & Vose Company | Battery separators with controlled pore structure |
| WO2022107334A1 (en) * | 2020-11-20 | 2022-05-27 | 日本板硝子株式会社 | Lead storage battery separator |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2632716B2 (en) | 1997-07-23 |
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