JPS63248058A - Lead-acid battery - Google Patents
Lead-acid batteryInfo
- Publication number
- JPS63248058A JPS63248058A JP62079712A JP7971287A JPS63248058A JP S63248058 A JPS63248058 A JP S63248058A JP 62079712 A JP62079712 A JP 62079712A JP 7971287 A JP7971287 A JP 7971287A JP S63248058 A JPS63248058 A JP S63248058A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- carbon fiber
- acid battery
- grown carbon
- vapor
- 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.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 18
- 239000002134 carbon nanofiber Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 229910000464 lead oxide Inorganic materials 0.000 abstract description 5
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001947 vapour-phase growth Methods 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 229920000049 Carbon (fiber) Polymers 0.000 abstract 4
- 239000004917 carbon fiber Substances 0.000 abstract 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 4
- 239000012808 vapor phase Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RGJOEKWQDUBAIZ-IBOSZNHHSA-N CoASH Chemical compound O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCS)O[C@H]1N1C2=NC=NC(N)=C2N=C1 RGJOEKWQDUBAIZ-IBOSZNHHSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- 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、初期性能纜優れ、かつ寿命性能にも優れた鉛
蓄電池に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a lead-acid battery that has excellent initial performance and excellent life performance.
（従来の技術）
一般に、鉛蓄電池は正電極の劣化によって寿命が尽きる
場合が多いため、正電極の改善が重要な課題になってい
る。このため、従来より、寿命性能を改善する手段とし
て、正極板の厚みを大きくしたり、例えば、ペースト式
鉛蓄電池ではペースト密度を高くする方法がとらｈてい
る。しかし、この方法では鉛蓄電池の初期性能が低下し
てしまう問題が生じ、寿命性能、初期性能共に良好な鉛
蓄電池をえることは困難であった。(Prior Art) Generally, the life of lead-acid batteries often ends due to deterioration of the positive electrode, so improvement of the positive electrode has become an important issue. For this reason, conventional methods for improving life performance include increasing the thickness of the positive electrode plate and, for example, increasing the paste density in paste type lead-acid batteries. However, this method poses a problem in that the initial performance of the lead-acid battery deteriorates, and it is difficult to obtain a lead-acid battery that has good life performance and initial performance.
（発明が解決しようとする問題点）
初期性能の改善策としては、従来、正極板に黒鉛を添加
する方法が提案されて来たが、その効果は十分なもので
はなく種々の研究がなお続けられている。(Problem to be solved by the invention) As a measure to improve the initial performance, a method of adding graphite to the positive electrode plate has been proposed in the past, but the effect is not sufficient and various studies are still being conducted. It is being
本発明者等は、これまで、新しい炭素材料として、気相
成長法炭素繊維の開発並びにこの素材の電極反応につい
て基礎的研究を進めていたが、本繊維が特異な充放電現
象を示すことを見出し、さらに検討の結果、鉛蓄電池の
正極板に添加すると鉛蓄電池の性能を大幅に改善するこ
とを見出したが、更に鋭意検討を重ねたところ、正極板
の製造過程で良好な操作性を有し、かつ電池性能にも一
層改善効果を示す本発明に到達することが出来た。The present inventors have been conducting basic research on the development of vapor-grown carbon fiber as a new carbon material and the electrode reaction of this material, but discovered that this fiber exhibits a unique charge-discharge phenomenon. As a result of further investigation, we found that adding it to the positive electrode plate of a lead-acid battery significantly improves the performance of the lead-acid battery.However, after further investigation, we found that it was possible to improve operability during the manufacturing process of the positive electrode plate. However, we were able to arrive at the present invention which further improves battery performance.
（問題点を解決するための手段）
すなわち、本発明は、酸性官能基を３〜５００μｅｑ／
ｇ有する気相成長法炭素繊維を含有した正極板を備える
ことを特徴とする鉛蓄電池である。(Means for solving the problem) That is, the present invention provides acidic functional groups in an amount of 3 to 500 μeq/
The present invention is a lead-acid battery characterized by comprising a positive electrode plate containing vapor-grown carbon fiber having the following properties.
本発明でいう、気相成長法炭素繊維とは、炭化水素など
の炭素源・を、触媒の存在下に加熱して気、相成長させ
て作られる繊維状の炭素質の物質、これを粉砕したシ切
断したシした種々の形態の炭素質物質、あるいは、これ
らを加熱処理した炭素質物質であり、気相成長法炭素繊
維は、電子顕微鏡で観察すると、芯の部分と、これを取
巻く、−見して、年輪状の炭素層からなる特異な形状の
繊維及びこれが粉砕、破砕などの加工を受けたものであ
る。また、気相成長法炭素繊維は、好ましくは、直径が
０．０１〜４μｍ、特に０．０１〜２μｍ、最も好まし
くは、０．０２〜１μｍであり、繊維の長さは特に制限
はないが、一般には、２０００μｍ以下であり、更に短
く破砕や切断あるいは粉砕された粒状や不定形状の物で
ある。また、気相成長法炭素繊維は、炭素の純度が高く
、一般に、９８．５４以上、特に、９９％以上、最も好
ましくは９９．５％以上である。In the present invention, vapor-grown carbon fiber refers to a fibrous carbonaceous material that is produced by heating a carbon source such as a hydrocarbon in the presence of a catalyst to cause vapor phase growth, and is pulverized. It is a carbonaceous material in various forms that has been cut and cut, or a carbonaceous material that has been heat-treated.When observed with an electron microscope, vapor-grown carbon fibers show a core part and surrounding parts. - It is a fiber with a unique shape consisting of a tree-ring-like carbon layer, which has been subjected to processing such as crushing and crushing. Further, the vapor grown carbon fiber preferably has a diameter of 0.01 to 4 μm, particularly 0.01 to 2 μm, most preferably 0.02 to 1 μm, and the length of the fiber is not particularly limited. Generally, the particle size is 2000 μm or less, and it is crushed, cut, or pulverized to have a granular or irregular shape. Further, the vapor grown carbon fiber has a high carbon purity, generally 98.54 or higher, particularly 99% or higher, and most preferably 99.5% or higher.
また、気相成長法炭素繊維は、易黒鉛化性の炭素質物質
である。また、気相成長法炭素繊維は、Ｘ線解析による
構造解析により、その格子定数は７．１〜６．８８の範
囲、好ましくは、７，０６〜６．８９０範囲である。Further, the vapor grown carbon fiber is a graphitizable carbonaceous material. Further, the vapor grown carbon fiber has a lattice constant in the range of 7.1 to 6.88, preferably in the range of 7.06 to 6.890, as determined by structural analysis using X-ray analysis.
本発明において気相成長法炭素繊維は、酸性官能基を３
〜５００μｓ ｑ ／ ｇ有することが特徴であり、酸
性官能基の量は好ましくは１０〜４５０μｅｑ／ｇ、特
に２０〜３５０μｓｑ／ｇの範囲である。酸性官能基の
量がこの範囲であると、正極板の作成時、金属鉛や酸化
鉛と混合する段階で極めて作業性に優れるばかりでなく
、分散性も良く、更に、電池性能も改善される。In the present invention, the vapor grown carbon fiber has 3 acidic functional groups.
The amount of acidic functional groups is preferably in the range of 10 to 450 μeq/g, especially 20 to 350 μeq/g. When the amount of acidic functional groups is within this range, not only is workability excellent at the stage of mixing with metal lead or lead oxide when creating a positive electrode plate, but also dispersibility is good, and battery performance is also improved. .
本発明において、酸性官能基を有する気相成長法炭素繊
維の製造方法としては、気相成長法炭素繊維を酸化する
方法が最も一般的であシ、その他、プラズマ法、グラフ
ト法等も用いられ得る。In the present invention, as a method for producing vapor grown carbon fibers having acidic functional groups, the most common method is to oxidize vapor grown carbon fibers, and other methods such as plasma methods and grafting methods are also used. obtain.
本発明において、酸性官能基を有する気相成長法炭素繊
維を含有した正極板は、上記の気相成長法炭素繊維が正
極板の構成成分として存在し、その量が、正極板に用い
られる酸化鉛１００重量部に対して少なくとも０．０１
重量部存在している正極板である。一般には、酸化鉛１
００重量部に対して酸性官能基を有する気相成長法炭素
繊維の量は００５ 重量部以上が好ましく、特に、０．
１重量部以上、最も好ましくは、０．２重量部以上１０
重量部以下である。In the present invention, the positive electrode plate containing vapor-grown carbon fibers having acidic functional groups is such that the above-mentioned vapor-grown carbon fibers are present as a constituent of the positive electrode plate, and the amount of the vapor-grown carbon fibers is determined by the amount of oxidation used in the positive electrode plate. At least 0.01 per 100 parts by weight of lead
% by weight of the positive electrode plate. Generally, lead oxide 1
The amount of the vapor grown carbon fiber having an acidic functional group is preferably 0.005 parts by weight or more, particularly 0.00 parts by weight.
1 part by weight or more, most preferably 0.2 part by weight or more10
Parts by weight or less.
本発明において、酸性官能基を有する気相成長法炭素繊
維の効果は、鉛蓄電池の製造時の作業性の改善の他に、
鉛蓄電池の初期性能、特に、正極活物質の利用率を大幅
に高め、正電極の劣化抑制にも寄与する所にあり、特に
、気相成長法炭素繊維が極めて微細な状態で用いられる
場合にその効果が著しく好ましい。In the present invention, the effects of vapor grown carbon fibers having acidic functional groups include, in addition to improving workability during the production of lead-acid batteries,
It greatly increases the initial performance of lead-acid batteries, especially the utilization rate of the positive electrode active material, and also contributes to suppressing deterioration of the positive electrode, especially when vapor-grown carbon fiber is used in an extremely fine state. The effect is extremely favorable.
本発明の鉛蓄電池は、以上のように、酸性官能基を有す
る気相成長法炭素繊維を含有した正極板を備えている事
を特徴としている。As described above, the lead-acid battery of the present invention is characterized by being equipped with a positive electrode plate containing vapor grown carbon fibers having acidic functional groups.
（実施例） 以下、本発明を実施例によシ説明する。(Example) The present invention will be explained below using examples.
実施例１
直径が０．１〜０．４μｍの気相成長法炭素繊維（トリ
スアセチルアセトナト鉄とベンゼンを１４００℃の加熱
空間に導入し浮遊状態で合成した、炭素層ｉｃ＋９．ｓ
％、格子定数７．０４）を酸素１％含有ガスで酸化し、
酸性官能基の量が１２８μｅｑ／ｇの気相成長法炭素繊
維を得、これをゼールミルで粉砕し、電子顕微鏡で観察
して実質的に最長７μｍ以下の気相成長法炭素繊維を得
た。この酸性官能基を有する気相成長法炭素繊維を用い
たペースト式正極板について鉛蓄電池の性能評価を行っ
た。Example 1 Vapor-grown carbon fiber with a diameter of 0.1 to 0.4 μm (trisacetylacetonate iron and benzene were introduced into a heating space at 1400°C and synthesized in a floating state, a carbon layer IC+9.s)
%, lattice constant 7.04) is oxidized with a gas containing 1% oxygen,
Vapor grown carbon fibers having an amount of acidic functional groups of 128 μeq/g were obtained, which were pulverized in a Zeel mill and observed under an electron microscope to obtain vapor grown carbon fibers having a length of substantially 7 μm or less. The performance of a lead-acid battery was evaluated using a paste-type positive electrode plate using this vapor-grown carbon fiber having acidic functional groups.
練膏工程の前Ｋ、鉛粉末３０％、残部酸化鉛よシなる鉛
粉に、上記の酸性官能基を有する気相成長法炭素繊維を
１．０ ％添加してあらかじめ良く混合し、公知の方法
によシペースト密度約４．６ｇ／ｃｒｉｔの硬質正極ペ
ーストを調製した。これを厚み３ｎの鉛合金格子に充填
し、熟成、化成の各工程を経て正極板を作製した。この
際、酸性官能基を有する気相成長法炭素繊維は鉛や酸化
鉛との混合、分散性に優れ、作業性良く良好な正極ペー
ストおよび正蓮板が作成できた。この正極板とガラスマ
ット付きのセパレータ、負極板を組合わせ鉛蓄電池を組
立てた。なお、比較のため、本発明囚に対し、気相成長
法炭素繊維を添加しない場合（Ｂ）、従来の天然黒鉛を
１俤添加した場合（０についても同様にして鉛蓄電池を
組立て試験した。この様にして得られた公称容量５０Ａ
ｈの鉛蓄電池を５ｈｒ放電した場合の初期性能の試験結
果を第１表に示す。Before the gluing process, 1.0% of the above vapor grown carbon fiber having an acidic functional group was added to lead powder consisting of 30% lead powder and the balance being lead oxide, and the mixture was well mixed in advance. A hard cathode paste with a paste density of about 4.6 g/crit was prepared by the method. This was filled into a lead alloy grid having a thickness of 3 nm, and a positive electrode plate was produced through the steps of aging and chemical formation. At this time, the vapor-grown carbon fibers having acidic functional groups had excellent mixing and dispersibility with lead and lead oxide, and good positive electrode paste and positive lotus plate were produced with good workability. A lead-acid battery was assembled by combining this positive electrode plate, a separator with a glass mat, and a negative electrode plate. For comparison, lead-acid batteries were assembled and tested in the same manner for the present invention in which no vapor grown carbon fiber was added (B) and in which one layer of conventional natural graphite was added (0). Nominal capacity 50A obtained in this way
Table 1 shows the test results of the initial performance when a lead-acid battery of 5 hours was discharged for 5 hours.
また、寿命性能に就いては、４００サイクル時点に於け
る５ｈｒ容量で比較を行った。その結果を第１表の寿命
性能の欄に記賊した。In addition, regarding life performance, comparison was made using 5 hr capacity at 400 cycles. The results are recorded in the column of life performance in Table 1.
実施例２
繊維の直径が０．０５〜０．３μｍの気相成長法炭素繊
維（炭素含ｉ９９．６係、格子定数６．９９）をｉ−ル
ミルで粉砕し、電顕で観察して実質的に最長３μｍ以下
の気相成長法炭素繊維を得、これを酸素０．５係有する
ガスで酸化し酸性官能基量９７μｅｑ／ｇを有する気相
成長法炭素繊維を得た。この気相成長法炭素繊維を用い
たペースト式正極板について、実施例１と同様に鉛蓄電
池の性能評価を行った。Example 2 Vapor-grown carbon fibers (carbon content i99.6, lattice constant 6.99) with a fiber diameter of 0.05 to 0.3 μm were pulverized with an i-luminium mill, and observed with an electron microscope to determine whether the fibers were A vapor grown carbon fiber having a maximum length of 3 μm or less was obtained, and this was oxidized with a gas containing 0.5 μm of oxygen to obtain a vapor grown carbon fiber having an acidic functional group content of 97 μeq/g. Regarding the paste-type positive electrode plate using this vapor-grown carbon fiber, performance evaluation of a lead-acid battery was performed in the same manner as in Example 1.
この際、酸性官能基を有する気相成長法炭素繊維の添加
量は、０．９係とした。At this time, the amount of the vapor grown carbon fiber having acidic functional groups added was set to 0.9.
試験結果を第１表のの）に示した。The test results are shown in Table 1.
以上のように、本発明によれば初期性能、寿命性能とも
に極めて良好な鉛蓄電池が得られ、工業的に有用である
。As described above, according to the present invention, a lead-acid battery with extremely good initial performance and lifetime performance can be obtained, and is industrially useful.
第 １ 表
（発明の効果）
本発明の鉛蓄電池は、従来の電池に比べ初期の放電特性
に優れ、かつ、電池寿命が長く工業的に極めて有用であ
る。Table 1 (Effects of the Invention) The lead-acid battery of the present invention has excellent initial discharge characteristics compared to conventional batteries, has a long battery life, and is extremely useful industrially.
Claims (1)
素繊維を含有した正極板を備えることを特徴とする鉛蓄
電池A lead-acid battery comprising a positive electrode plate containing vapor-grown carbon fiber having 3 to 500 μeq/g of acidic functional groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62079712A JPS63248058A (en) | 1987-04-02 | 1987-04-02 | Lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62079712A JPS63248058A (en) | 1987-04-02 | 1987-04-02 | Lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63248058A true JPS63248058A (en) | 1988-10-14 |
Family
ID=13697819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62079712A Pending JPS63248058A (en) | 1987-04-02 | 1987-04-02 | Lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63248058A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0233859A (en) * | 1988-07-21 | 1990-02-05 | Yuasa Battery Co Ltd | Lead-acid battery |
| JPH02177260A (en) * | 1988-07-27 | 1990-07-10 | Yuasa Battery Co Ltd | Closed type lead accumulator |
-
1987
- 1987-04-02 JP JP62079712A patent/JPS63248058A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0233859A (en) * | 1988-07-21 | 1990-02-05 | Yuasa Battery Co Ltd | Lead-acid battery |
| JPH02177260A (en) * | 1988-07-27 | 1990-07-10 | Yuasa Battery Co Ltd | Closed type lead accumulator |
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