JP4000613B2 - Manufacturing method of sealed lead-acid battery - Google Patents
Manufacturing method of sealed lead-acid battery Download PDFInfo
- Publication number
- JP4000613B2 JP4000613B2 JP02219897A JP2219897A JP4000613B2 JP 4000613 B2 JP4000613 B2 JP 4000613B2 JP 02219897 A JP02219897 A JP 02219897A JP 2219897 A JP2219897 A JP 2219897A JP 4000613 B2 JP4000613 B2 JP 4000613B2
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- Prior art keywords
- battery
- oil
- negative electrode
- sealed lead
- acid
- Prior art date
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Links
- 239000002253 acid Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000006183 anode active material Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 29
- 235000019198 oils Nutrition 0.000 description 29
- 239000000654 additive Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 239000010692 aromatic oil Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 229910014474 Ca-Sn Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は密閉形鉛蓄電池の製造法の改良に関するものである。
【０００２】
【従来の技術】
マルチメディア時代といわれる近年、これに対応した光通信網のインフラ整備が急速に進んでいる。光通信ファイバーは大量の通信能力を持つ半面、配線点で光信号を電話、パーソナルコンピュータなどの情報端末向けの電気信号に変換する必要がある。この変換器には停電時のバックアップ用の非常用電源が欠かせないが、これらは電柱上など屋外に設置されて使用されることが多い。したがって、この種のバックアップ用電源に用いられている密閉形鉛蓄電池のおかれている温度環境は非常に厳しく、特に夏場のような高温環境下では蓄電池のフロート充電中に電解液の電気分解によるドライアップや熱逸走が起こり、蓄電池の機能がそこなわれることがあった。
【０００３】
【発明が解決しようとする課題】
フロート充電中におこるドライアップとは電解液中の水分が電気分解によって失われ、電池の放電容量が低下する現象で、熱逸走とは温度上昇にともなって充電電流が増加し、充電電流の増加に伴って電池が異常に発熱し最終的にはドライアップをともなって電池が機能しなくなる現象である。これらの現象、特に熱逸走は６０℃以上の高温下で長期間使用された場合に起こりやすい現象であるが、７０℃以上の高温下では比較的短時間でもその兆候がみられる。そこで、上記のような過酷な環境下でも使用に耐えうる電池の開発が要求されていた。
【０００４】
この種の現象が起こりにくい密閉形鉛蓄電池とは、すなわち高温下においてもフロート充電電流の増加が少ない蓄電池であるが、従来の技術だけではこのような電池を得ることは困難であった。
【０００５】
なお、温度上昇によって充電電流が増加するのは電解液の分解による正極での酸素発生量の増大と、密閉反応効率の向上にともなう負極での酸素吸収反応速度の増加との相乗効果によるものである。また、上記反応熱と充電電流の増加にともなうジュール熱の発生速度が電池の熱放散速度よりも大きくなると電池温度が周囲温度以上に上昇し、その温度上昇によって充電電流が増加し、さらなる電池温度の上昇を招くという悪循環を繰り返し、ついには熱逸走に至ることになることが知られている。
【０００６】
【課題を解決するための手段】
本発明は上記課題を解決するもので、未化成の正および負極板を用いて電池を作製した後、電池に電解液を注液して通電することにより、これらの極板群を電槽内において化成する、いわゆる電槽化成法で製造される密閉形鉛蓄電池であって、オイルが添加された負極活物質を用いたことを特徴とするもので、これによって高温下でもフロート充電電流の増加がみられない、安定した電池性能を有する密閉形鉛蓄電池を提供するものである。前記密閉形鉛蓄電池は、オイルが添加された負極活物質を備える未化成の負極板と未化成の正極板とを用いて電池を作成する工程と、前記電池に希硫酸を注液して化成する工程とを備えた製造方法により得ることができる。
【０００７】
【発明の実施の形態】
本発明による密閉形鉛蓄電池は、未化成の正および負極板を用いて電池を作製した後、電池に所定の希硫酸を注液して通電することにより、これらの極板群を電槽内において化成する、いわゆる電槽化成法で製造される密閉形鉛蓄電池であって、オイルが添加された負極活物質を用いたことを特徴とするものである。なお、オイルの添加は負極ペーストを混練作製する際に添加したが、添加量としては０．０５〜１ｗｔ％が好ましい。オイルの種類としては動物油系および植物油系の適用も可能ではあるが、パラフィン油系、ナフテン油系、オレフィン油系、芳香油系およびシリコン油系が好ましい。また、市販のオイルには各種添加剤が用いられているが、通常用いられている潤滑油添加剤および防錆油添加剤が適当量含まれているものを使用することができる。
【０００８】
【実施例】
以下、本発明を実施例に基づいて説明する。
【０００９】
ＰｂーＣａーＳｎ系合金製の正および負極格子に鉛蓄電池用の正および負極ペーストをそれぞれ充填し熟成、乾燥をほどこし、未化成の正負極板を得た。なお、ここで用いた負極ペーストは次のようにして作製した。
【００１０】
ボールミル式鉛粉に硫酸バリウム、リグニンスルホン酸、カーボンブラックを適量添加し、乾式混合の後、所定量の水および比重１．４の希硫酸を順次投入して練合した。硫酸バリウム量としては０．１％〜２％、リグニンスルホン酸量としては０．０５〜１％、カーボン量としては０．０５〜２％を用いることができる。その後、このペーストにオイルを０〜１％添加して再び練合し表１に示す６種類のペーストを作製した。
【００１１】
【表１】
【００１２】
【表２】
【００１３】
次にこれらの電池の２０ｈＲ（時間率）放電容量および高率（３８Ａ）放電容量を測定し、その後、熱逸走試験に供した。熱逸走試験とは周囲温度を変えて定電圧充電を行ない、充電電流および電池温度を測定し、定電圧充電中の充電電流が安定値を示さずに次第に増加し、それにともなう発熱によって電池温度が周囲温度よりも１０℃以上高くなった時点を熱逸走状態と判断して試験を打ち切った。なお、充電電圧は通常のフロート充電時に用いられている２．２７５Ｖ／セルとし、周囲温度（気相中）は最初６０℃とし、その後２．５℃づつ温度を上げて実施した。試験期間は各温度とも１週間とした。
【００１４】
これら電池の２０ｈＲ放電容量（２５℃）、高率放電容量（２５℃）、および熱逸走を起こした周囲温度（熱逸走温度）を表３に示す。電槽化成品、タンク化成品ともにオイルの添加量が１％以下であれば２０ｈＲ放電容量および高率放電容量ともに大きな違いはないが、オイルの添加量が増えるにしたがって特に高率放電容量の低下が大きくなることから、これよりも添加量を増やすことは好ましくないと考えられる。また、電槽化成品においてオイルを０．０５％以上添加した本発明による電池（〓２〜６）は熱逸走温度が７７．５℃以上であり従来品に比べて優れた熱逸走特性を示した。
【００１５】
【表３】
【００１６】
オイルを添加したタンク化成品（〓８〜１２）の熱逸走温度は本発明品に比べて低いが、タンク化成後の電解液にはオイルを吸着したカーボンブラックが浮遊していたことから考えてオイルの一部が化成中に負極活物質から脱離したためと思われる。
【００１７】
なお、ここで用いたオイルはパラフィン系炭化水素の基油に各種添加剤を混合した市販のメカニックオイルである。オイルの種類としては動物油系および植物油系の適用も可能ではあるが、耐酸性等に優れているパラフィン系、ナフテン系およびオレフィン系のいわゆる石油系のほか、芳香油系およびシリコン油系が好ましい。また、上述したように市販のオイルには各種添加剤が用いられているが、通常用いられている潤滑油添加剤および防錆油添加剤が適当量含まれているものを使用することができる。
【００１８】
また、従来のタンク化成用負極板の活物質添加剤として用いられているオイルは化成・水洗・乾燥（真空乾燥）後の負極活物質（海綿状金属鉛）の大気中酸化を防ぐために添加されるものであり、本発明のように耐熱逸走特性の向上を目的として用いられているものではない。したがって、従来には電槽化成用の負極活物質添加剤としてオイルを用いることはなく、上記タンク化成の技術は本発明とは何ら関係ない。
【００１９】
【発明の効果】
以上、実施例で述べたように、本発明による、オイルが添加された負極活物質を備える未化成の負極板と未化成の正極板とを用いて電池を作成する工程と、前記電池に希硫酸を注液して化成する工程とを備えたことを特徴とする製造方法によって得られた密閉型鉛蓄電池は、フロート充電使用中の熱逸走が起こり難く、安定した電池性能を長期間維持できる等、その工業的価値は大なるものである[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an improved manufacturing method of a sealed lead-acid battery.
[0002]
[Prior art]
In recent years, called the multimedia era, infrastructure development of optical communication networks corresponding to this has been rapidly progressing. The optical communication fiber has a large amount of communication capability, but it is necessary to convert an optical signal into an electric signal for information terminals such as a telephone and a personal computer at a wiring point. This converter requires an emergency power source for backup during power outages, but these are often used outdoors such as on utility poles. Therefore, the temperature environment where the sealed lead-acid battery used for this type of backup power supply is very harsh, especially in high-temperature environments such as in summer, due to electrolysis of the electrolyte during float charging of the battery. Dry-up and thermal runaway occurred, and the function of the storage battery was sometimes lost.
[0003]
[Problems to be solved by the invention]
Dry-up during float charging is a phenomenon in which the water in the electrolyte is lost due to electrolysis and the discharge capacity of the battery decreases. Thermal runaway increases the charging current as the temperature rises, increasing the charging current. This is a phenomenon in which the battery abnormally generates heat, and eventually the battery does not function with dry-up. These phenomena, particularly thermal escape, are likely to occur when used for a long period of time at a high temperature of 60 ° C. or higher. However, at high temperatures of 70 ° C. or higher, the signs are observed even in a relatively short time. Therefore, there has been a demand for the development of a battery that can withstand use even in the harsh environment as described above.
[0004]
A sealed lead-acid battery in which this kind of phenomenon is unlikely to occur is a battery with a small increase in float charging current even at high temperatures, but it has been difficult to obtain such a battery only with the conventional technology.
[0005]
The increase in charging current due to temperature rise is due to a synergistic effect of the increase in oxygen generation rate at the positive electrode due to decomposition of the electrolyte and the increase in oxygen absorption reaction rate at the negative electrode as the sealing reaction efficiency is improved. is there. In addition, when the generation rate of Joule heat accompanying the increase in the reaction heat and the charging current becomes larger than the heat dissipation rate of the battery, the battery temperature rises to the ambient temperature or higher, and the charging current increases due to the temperature rise, and further battery temperature It is known that the vicious cycle of incurring the rise will eventually lead to a thermal runaway.
[0006]
[Means for Solving the Problems]
The present invention solves the above-mentioned problems. After producing a battery using unformed positive and negative electrode plates, an electrolytic solution is injected into the battery and energized, thereby bringing these electrode plate groups into the battery case. Is a sealed lead-acid battery manufactured by the so-called battery case formation method, characterized by using a negative electrode active material to which oil is added, thereby increasing the float charging current even at high temperatures It is an object of the present invention to provide a sealed lead-acid battery having stable battery performance in which no stagnation is observed. The sealed lead-acid battery includes a step of producing a battery using an unformed negative electrode plate and a non-formed positive electrode plate each having an anode active material to which oil is added; and a chemical conversion process by injecting dilute sulfuric acid into the battery. It can obtain by the manufacturing method provided with the process to do.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The sealed lead-acid battery according to the present invention is manufactured by using unformed positive and negative electrode plates, and then injecting a predetermined dilute sulfuric acid into the battery and energizing the battery, thereby bringing these electrode plate groups into the battery case. A sealed lead-acid battery produced by the so-called battery case formation method, which is formed by using a negative electrode active material to which oil is added. The oil was added when the negative electrode paste was kneaded. The addition amount is preferably 0.05 to 1 wt%. As the kind of oil, animal oil type and vegetable oil type can be applied, but paraffin oil type, naphthenic oil type, olefin oil type, aromatic oil type and silicone oil type are preferable. Various additives are used in commercially available oils, and those containing appropriate amounts of commonly used lubricating oil additives and rust preventive oil additives can be used.
[0008]
【Example】
Hereinafter, the present invention will be described based on examples.
[0009]
The positive and negative electrode grids made of Pb—Ca—Sn alloy were filled with positive and negative electrode pastes for lead storage batteries, respectively, and aged and dried to obtain unformed positive and negative electrode plates. In addition, the negative electrode paste used here was produced as follows.
[0010]
Appropriate amounts of barium sulfate, lignin sulfonic acid, and carbon black were added to the ball mill type lead powder. After dry mixing, a predetermined amount of water and a diluted sulfuric acid having a specific gravity of 1.4 were sequentially added and kneaded. The amount of barium sulfate may be 0.1% to 2%, the amount of lignin sulfonic acid may be 0.05 to 1%, and the amount of carbon may be 0.05 to 2%. Thereafter, 0 to 1% of oil was added to this paste and kneaded again to prepare six types of paste shown in Table 1.
[0011]
[Table 1]
[0012]
[Table 2]
[0013]
Next, 20 hR (hour rate) discharge capacity and high rate (38 A) discharge capacity of these batteries were measured, and then subjected to a thermal escape test. The thermal runaway test is a constant voltage charge at different ambient temperatures, the charge current and battery temperature are measured, and the charge current during constant voltage charge gradually increases without showing a stable value. The point of time when the temperature became higher by 10 ° C. or more than the ambient temperature was judged as a thermal escape state, and the test was terminated. The charging voltage was 2.275 V / cell used during normal float charging, the ambient temperature (in the gas phase) was initially 60 ° C., and then the temperature was increased by 2.5 ° C. The test period was one week for each temperature.
[0014]
Table 3 shows the 20 hR discharge capacity (25 ° C.), the high rate discharge capacity (25 ° C.), and the ambient temperature (thermal escape temperature) at which thermal escape occurred. If the amount of oil added is less than 1% for both battery case chemicals and tank chemicals, there is no significant difference between the 20 hR discharge capacity and the high rate discharge capacity. However, as the amount of oil added increases, the high rate discharge capacity decreases particularly. Therefore, it is considered that it is not preferable to increase the addition amount. In addition, the battery according to the present invention (〓 2 to 6) to which 0.05% or more of oil is added in the battery case chemical product has a thermal escape temperature of 77.5 ° C or higher and exhibits excellent thermal escape characteristics compared to conventional products. It was.
[0015]
[Table 3]
[0016]
Although the thermal escape temperature of the tank chemical product (〓8-12) added with oil is lower than that of the present invention product, the carbon black adsorbing oil was floating in the electrolyte after the chemical tank formation. This is probably because part of the oil was detached from the negative electrode active material during chemical conversion.
[0017]
The oil used here is a commercially available mechanic oil obtained by mixing various additives with a base oil of paraffinic hydrocarbon. Animal oils and vegetable oils can be used as the kind of oil, but paraffinic, naphthenic and olefinic so-called petroleum oils that are excellent in acid resistance and the like, aromatic oil oils and silicon oil oils are preferred. Further, as described above, various additives are used in commercially available oils, but those containing appropriate amounts of commonly used lubricating oil additives and rust preventive oil additives can be used. .
[0018]
Oil used as an active material additive for conventional negative electrode plates for tank formation is added to prevent oxidation of the negative electrode active material (spongy metal lead) in the atmosphere after chemical conversion, water washing and drying (vacuum drying). However, it is not used for the purpose of improving the heat-resistant escape characteristics as in the present invention. Therefore, conventionally, no oil is used as a negative electrode active material additive for battery case formation, and the tank formation technique has nothing to do with the present invention.
[0019]
【The invention's effect】
As described above, as described in the embodiments, a process for producing a battery using an unformed negative electrode plate having an anode-added negative electrode active material and an unformed positive electrode plate according to the present invention, The sealed lead-acid battery obtained by the manufacturing method characterized by comprising a step of injecting sulfuric acid to form chemicals is unlikely to cause thermal escape during use of float charging, and can maintain stable battery performance for a long period of time. Etc., its industrial value is great
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02219897A JP4000613B2 (en) | 1997-01-20 | 1997-01-20 | Manufacturing method of sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02219897A JP4000613B2 (en) | 1997-01-20 | 1997-01-20 | Manufacturing method of sealed lead-acid battery |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH10208745A JPH10208745A (en) | 1998-08-07 |
| JPH10208745A5 JPH10208745A5 (en) | 2004-12-16 |
| JP4000613B2 true JP4000613B2 (en) | 2007-10-31 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02219897A Expired - Lifetime JP4000613B2 (en) | 1997-01-20 | 1997-01-20 | Manufacturing method of sealed lead-acid battery |
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| Country | Link |
|---|---|
| JP (1) | JP4000613B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4904658B2 (en) * | 2002-12-09 | 2012-03-28 | 株式会社Ｇｓユアサ | Method for producing lead-acid battery |
| JP4812386B2 (en) * | 2005-09-30 | 2011-11-09 | 古河電池株式会社 | Method for producing lead-acid battery |
| JP2013048082A (en) * | 2011-07-25 | 2013-03-07 | Gs Yuasa Corp | Lead acid battery |
| WO2018199125A1 (en) * | 2017-04-28 | 2018-11-01 | 株式会社Ｇｓユアサ | Lead acid battery |
-
1997
- 1997-01-20 JP JP02219897A patent/JP4000613B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10208745A (en) | 1998-08-07 |
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