JP3178015B2 - Positive electrode plate for lead storage battery and method for producing the same - Google Patents
Positive electrode plate for lead storage battery and method for producing the sameInfo
- Publication number
- JP3178015B2 JP3178015B2 JP21201991A JP21201991A JP3178015B2 JP 3178015 B2 JP3178015 B2 JP 3178015B2 JP 21201991 A JP21201991 A JP 21201991A JP 21201991 A JP21201991 A JP 21201991A JP 3178015 B2 JP3178015 B2 JP 3178015B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- tin
- positive electrode
- electrode plate
- alloy
- 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.)
- Expired - Fee Related
Links
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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ペースト式極板で構成
されるメンテナンスフリー鉛蓄電池、特に密閉形鉛蓄電
池をばらつきなく放電容量を向上させる正極板およびそ
の製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a maintenance-free lead-acid battery comprising a paste-type electrode plate, and more particularly to a positive electrode plate for improving the discharge capacity of a sealed lead-acid battery without variation, and a method of manufacturing the same.
【０００２】[0002]
【従来の技術】従来、ペースト式極板で構成されるメン
テナンスフリー鉛蓄電池、特に密閉形鉛蓄電池におい
て、正極板はＳｂを実質的に含まないか、または僅かし
か含まないＰｂ−Ｃａ系合金からなる鋳造格子またはエ
キスパンドメタル格子に、主成分である鉛粉と希硫酸と
を練合して得られるペーストを充填し、熟成，乾燥して
未化成正極板を作製していた。また、未化成負極板も、
通常、Ｓｂを実質的に全く含まないＰｂ−Ｃａ合金から
なる格子を用い、同様な製造法で作製し、未化成正負極
板によって組み立てられた鉛蓄電池を電槽化成等によっ
て初充電して電池を完成していた。Ｐｂ−Ｃａ系合金か
らなる格子を正極板に用いた鉛蓄電池は、充放電による
電解液量の減少が極めて少なくメンテナンスフリー特性
が非常に優れており、特に電解液量を少なく規制してい
る負極吸収式の密閉形鉛蓄電池においては、不可欠の技
術である。しかしながら深い放電を伴う充放電を繰り返
すことによって、正極板の活物質が軟化して、ついには
脱落する等正極板の劣化により、電池容量が急激に低下
してしまう問題があった。2. Description of the Related Art Conventionally, in a maintenance-free lead-acid battery composed of a paste type electrode plate, particularly a sealed lead-acid battery, the positive electrode plate is made of a Pb-Ca alloy containing substantially no or little Sb. A cast grid or expanded metal grid is filled with a paste obtained by kneading lead powder and dilute sulfuric acid, which are main components, and aged and dried to prepare an unformed positive electrode plate. Also, unformed negative electrode plate,
Normally, a lead-acid battery manufactured by the same manufacturing method using a grid made of a Pb-Ca alloy containing substantially no Sb, and initially assembled by an unformed positive / negative electrode plate is first charged by a battery case or the like, and the battery is charged. Was completed. A lead-acid battery using a grid made of a Pb-Ca-based alloy as a positive electrode plate has a very low maintenance-free characteristic in which the amount of electrolyte solution is extremely small due to charge and discharge, and in particular, a negative electrode in which the amount of electrolyte solution is regulated to be small. This is an indispensable technology for absorption type lead storage batteries. However, there has been a problem that the active material of the positive electrode plate is softened by repeated charge / discharge accompanied by deep discharge, and the active material of the positive electrode plate eventually falls off.
【０００３】このような問題点の改良策として、格子用
鉛合金組成や格子の製造法や正極活物質への添加剤等多
くの研究がなされてきた。[0003] As a measure for resolving such problems, many studies have been made on a lead alloy composition for a lattice, a method for producing a lattice, and an additive to a positive electrode active material.
【０００４】例えば特開昭６１−２７７１５８で示され
るように、鉛粉と錫酸化物粉末との混合物と希硫酸とを
練合して得られたペーストを充填した正極板を用いるこ
とにより、前記したような急激な容量低下を抑制する提
案がなされている。For example, as shown in JP-A-61-277158, by using a positive electrode plate filled with a paste obtained by kneading a mixture of lead powder and tin oxide powder with dilute sulfuric acid, Proposals have been made to suppress such a rapid decrease in capacity.
【０００５】[0005]
【発明が解決しようとする課題】前述したように、Ｐｂ
−Ｃａ−Ｓｎ合金等のＰｂ−Ｃａ系合金からなる格子に
錫酸化物を添加した鉛粉と希硫酸とを練合して得られる
ペーストを充填した正極板を用いることにより、深い放
電を伴う充放電サイクルでの急激な容量低下が抑制され
る。このような抑制効果は、正極活物質になる鉛粉中に
添加された錫酸化物の錫分によるものである。すなわ
ち、鉛蓄電池の充電に広く使用される定電圧充電におけ
る充電受け入れ特性とも密接な関係をもつ、格子と活物
質との界面に形成され、不働態化現象の原因となる緻密
なＰｂＳＯ4層の生成を、錫分が阻害することによると
考えられる。しかしながら、ペースト中の錫分の分布が
均一でないと、前記効果にばらつきが生じ、電池特性を
実質的に充分改良できない場合があった。As described above, Pb
Deep discharge is caused by using a positive electrode plate filled with a paste obtained by kneading a lead powder obtained by kneading a lead powder obtained by adding tin oxide and dilute sulfuric acid to a lattice made of a Pb-Ca alloy such as a -Ca-Sn alloy. A rapid decrease in capacity in the charge / discharge cycle is suppressed. Such a suppression effect is due to the tin content of the tin oxide added to the lead powder that becomes the positive electrode active material. That is, the dense PbSO 4 layer formed at the interface between the lattice and the active material, which is closely related to the charge receiving characteristic in constant voltage charging widely used for charging lead storage batteries, and causing a passivation phenomenon. It is believed that the formation was due to tin inhibition. However, when the distribution of the tin content in the paste is not uniform, the effects described above vary, and the battery characteristics may not be substantially sufficiently improved in some cases.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記欠点を簡
易かつ有効な手段で除去したもので、具体的には、従来
のように、鉛粉に微量の固体状の錫酸化物粉末を添加，
混合せずに、電池に無害で、水溶性の錫の硫酸塩水溶液
の状態で、滴下または噴霧状にして少量ずつ添加しなが
ら予備混合したのち、希硫酸と練合して得られるペース
トを使用することによって目的を達成したものである。According to the present invention, the above-mentioned drawbacks are eliminated by simple and effective means. More specifically, a small amount of solid tin oxide powder is added to lead powder as in the prior art. Addition,
Without mixing, use a paste obtained by preliminarily mixing in a water-soluble aqueous solution of tin sulfate, which is harmless to the battery and added dropwise little by little, and then kneaded with dilute sulfuric acid. The purpose was achieved by doing.
【０００７】[0007]
【作用】鉛粉への錫分の添加は、正極活物質中の錫分と
して、約０．２％程度またはそれ以上で有効とされてい
るが、ばらつきが少なく効果を奏させるためには、鉛粉
と錫酸化物粉末との予備混合を長時間実施する必要があ
った。これは、錫酸化物が固体であり、かつ添加量とし
て相対的に少ないことによる。そこで、本発明は、電池
に無害で、かつ水溶性の錫の硫酸塩水溶液の状態の添加
剤を、滴下または噴霧状にして、鉛粉に少量ずつ添加し
ながら混合分散させるので、短時間の混合でも錫分の分
布が均一で、その効果もばらつきが非常に小さくなり、
電池特性の改良に資するところ大なるものである。The effect of adding tin to the lead powder is effective at about 0.2% or more of the tin in the positive electrode active material. Premixing of the lead powder and the tin oxide powder had to be performed for a long time. This is because the tin oxide is solid and has a relatively small amount of addition. Therefore, the present invention is harmless to the battery, and in the form of a water-soluble aqueous solution of tin sulfate, added dropwise or sprayed, and added to the lead powder little by little and mixed and dispersed. Even when mixed, the distribution of tin is uniform, and the effect is very small,
This is a great contribution to the improvement of battery characteristics.
【０００８】[0008]
【実施例】本発明の実施例について以下説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below.
【０００９】常法で得られた鉛粉に、０．０２mol／ｌ
の濃度に溶解したＳｎＳＯ4水溶液を、鉛粉中の鉛分を
基準にして錫分が１mol％に相当する量まで噴霧状にし
て少量ずつ添加しながら１０分間混合したのち、所定量
の希硫酸と練合して得られたペーストをＰｂ−Ｃａ−Ｓ
ｎ合金鋳造格子に充填し、熟成，乾燥して未化成正極板
を得る。[0009] 0.02 mol / l of lead powder obtained by a conventional method
The SnSO 4 aqueous solution dissolved in a concentration of 1% by weight was sprayed to an amount corresponding to 1 mol% of tin based on the lead in the lead powder, and the mixture was added little by little for 10 minutes. Paste obtained by kneading with Pb-Ca-S
The n-alloy casting grid is filled, aged and dried to obtain an unformed positive electrode plate.
【００１０】比較のために、本発明と同じ規模で、鉛粉
への錫分の添加率で、同一練合機で、混合および練合条
件を同じにして得た鉛粉とＳｎＯ粉末との混合物による
ペーストを充填した従来法による正極板も作製した。本
発明実施例および従来例による正極板を用い、２０時間
率での公称容量２０Ahの単電池を各５０セル試作した。
試作電池は正極板の特性を把握するために、電池の放電
容量が正極容量で規制されるように、通常の製品より負
極容量を大きくし、正極板以外は、両者とも同じ種類お
よび条件の部材を使用した。電槽化成によって初充電し
たのち、５時間率定電流で１．７５Ｖまで放電し、２．
４５Ｖ定電圧で８時間充電を繰り返すサイクル試験を行
なった。５サイクル目の両者の公称容量に対する放電容
量比率の度数分布を図１および図２に示す。図１に示さ
れる従来例の電池の放電容量比率は１０２〜１１２％と
ばらつき、統計学的分散が５．６９の範囲に広がってい
るのに対し、図２に示される本発明の実施例による電池
においては、放電容量比率は１０５〜１０９％とばらつ
きが小さく、統計学的分散は０．７６であり、従来例に
よる電池の場合より４．９３向上した。以上の結果か
ら、本発明の実施例による電池は、従来例による電池よ
り、錫分による効果がばらつきが小さいことが明らかで
ある。なお、結果は図示しなかったが、従来例のＳｎＯ
の替りに、ＳｎＳＯ4結晶を粉砕して鉛粉に添加混合し
たのち、希硫酸で練合して得たペーストについても検討
したが、本発明による実施例と従来例による電池の放電
容量比率および統計学的分散とも中間的水準であった。
したがって、鉛粉への錫分の添加混合による分散はＳｎ
ＳＯ4水溶液を用いることが分布の均一性に有効である
ことが理解できる。なお、実施例においては、第一塩の
ＳｎＳＯ4について示したが、第二塩のＳｎ（ＳＯ4）2
も効果に何等差異は生じなかった。錫分の添加量は１mo
l％について示したが、０．１〜３．０mol％の範囲が有
効で、０．１mol％未満では効果を奏し得ず、３．０mol
％を越えると却って特性が劣化してしまう。錫の硫酸塩
は、添加量によって、希硫酸中に予め溶解できる。この
場合は、錫の硫酸塩を水溶液の形で、鉛粉へ予め添加混
合する必要はなく、鉛粉と錫の硫酸塩を予め溶解した希
硫酸とを直接練合したペーストによっても同等の効果を
奏するものである。また、実施例では格子にペーストを
充填し、直ちに熟成，乾燥して未化成正極板を得たが、
ペースト処方によっては、ペースト充填後浸酸処理を施
したのち、熟成，乾燥しても、本発明の主旨を逸脱する
ものではない。さらに、実施例では、Ｓｂを実質的に全
く含まないＰｂ−Ｃａ−Ｓｎ合金からなる鋳造格子につ
いて説明したが、同じ合金からなるエキスパンドメタル
格子および例えば、Ｐｂ−Ｃａ合金，Ｐｂ−Ｃａ−Ｓｎ
合金等のＰｂ−Ｃａ系合金板の両面または片面に、Ｐｂ
−Ｓｎ−Ｓｂ合金のようなＳｂを含むＰｂ合金箔を圧延
一体化したクラッド板を用いたエキスパンドメタル格子
のように、格子表面に僅かにＳｂが点在する格子の場合
も同様な効果を奏する。For comparison, a lead powder and a SnO powder obtained by using the same kneader under the same mixing and kneading conditions at the same scale as that of the present invention at the tin addition rate to the lead powder are used. A conventional positive electrode plate filled with a paste of the mixture was also prepared. Using the positive electrode plates according to the examples of the present invention and the conventional example, 50 cells each having a nominal capacity of 20 Ah at a rate of 20 hours were prototyped.
In order to grasp the characteristics of the positive electrode plate, the prototype battery has a larger negative electrode capacity than a normal product so that the discharge capacity of the battery is regulated by the positive electrode capacity. It was used. After the initial charge by battery case formation, the battery was discharged to 1.75 V at a constant current of 5 hours.
A cycle test in which charging was repeated at a constant voltage of 45 V for 8 hours was performed. The frequency distribution of the ratio of the discharge capacity to the nominal capacity in the fifth cycle is shown in FIG. 1 and FIG. The discharge capacity ratio of the battery of the conventional example shown in FIG. 1 varies from 102 to 112%, and the statistical variance is widened to 5.69, whereas the discharge capacity ratio according to the embodiment of the present invention shown in FIG. In the battery, the discharge capacity ratio was as small as 105 to 109%, and the statistical variance was 0.76, which was 4.93 higher than that of the battery according to the conventional example. From the above results, it is apparent that the effect of tin content in the battery according to the example of the present invention is smaller than that in the battery according to the conventional example. Although the results are not shown, the conventional SnO
Instead, the paste obtained by pulverizing SnSO 4 crystals, adding the mixture to lead powder, and kneading with dilute sulfuric acid was also examined. The statistical variance was also at an intermediate level.
Therefore, the dispersion due to the addition and mixing of tin to the lead powder is Sn
It can be understood that the use of the SO 4 aqueous solution is effective for the uniformity of the distribution. In the examples, the first salt SnSO 4 is shown, but the second salt Sn (SO 4 ) 2
No difference was found in the effect. The amount of tin added is 1mo
1%, it is effective in the range of 0.1 to 3.0 mol%, and if less than 0.1 mol%, no effect can be obtained.
%, The characteristics are rather deteriorated. Tin sulfate can be previously dissolved in dilute sulfuric acid depending on the amount of tin added. In this case, it is not necessary to add and mix tin sulfate in advance in the form of an aqueous solution to the lead powder, and the same effect can be obtained by directly kneading the lead powder with dilute sulfuric acid in which tin sulfate is previously dissolved. Is played. In the example, the grid was filled with the paste, immediately aged and dried to obtain an unformed positive electrode plate.
Depending on the paste formulation, even after the paste is filled and subjected to an acid treatment, aging and drying do not depart from the gist of the present invention. Further, in the embodiment, the casting lattice made of the Pb-Ca-Sn alloy containing substantially no Sb was described. However, the expanded metal lattice made of the same alloy and, for example, the Pb-Ca alloy, Pb-Ca-Sn
Pb-Ca based alloy plate such as alloy
Similar effects can be obtained in the case of a grid in which Sb is slightly scattered on the grid surface, such as an expanded metal grid using a clad plate obtained by rolling and integrating a Pb alloy foil containing Sb such as an Sn-Sb alloy. .
【００１１】[0011]
【発明の効果】以上詳述したように、鉛粉に、鉛粉中の
鉛分を基準にして錫分の量が０．１〜３．０ｍｏｌ％の
範囲となる錫の硫酸塩を水溶液または希硫酸溶液の形で
混合し、鉛粉を主成分とするペースト中の錫分の分布を
短時間に均一にすることによって、放電容量をばらつき
を小さくしつつ向上し得るメンテナンスフリー鉛蓄電
池、特に密閉形鉛蓄電池を得ることができる。As described above in detail, according to the present invention, the lead powder, in Namariko
The amount of tin is 0.1 to 3.0 mol% based on the lead.
The range of tin sulfate in the range is mixed in the form of an aqueous solution or dilute sulfuric acid solution, and the distribution of tin in the paste containing lead powder as a main component is made uniform in a short time to reduce the variation in discharge capacity. It is possible to obtain a maintenance-free lead-acid battery, particularly a sealed lead-acid battery, which can be improved while being improved.
【図１】従来例による公称容量に対する放電容量比率の
度数分布図FIG. 1 is a frequency distribution diagram of a discharge capacity ratio to a nominal capacity according to a conventional example.
【図２】本発明の実施例による公称容量に対する放電容
量比率の度数分布図FIG. 2 is a frequency distribution diagram of a discharge capacity ratio to a nominal capacity according to an embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−277158（ＪＰ，Ａ) 特開 昭62−24557（ＪＰ，Ａ) 特開 平４−196059（ＪＰ，Ａ) 特開 平４−206150（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/14 - 4/20 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-277158 (JP, A) JP-A-62-24557 (JP, A) JP-A-4-196059 (JP, A) JP-A-Heisei 4- 206150 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) H01M 4/14-4/20
Claims (6)
または僅かしか含まない鉛−カルシウム系合金からなる
格子に、鉛粉中の鉛分を基準にして錫分の量が０．１〜
３．０ｍｏｌ％の範囲となる錫の硫酸塩水溶液を鉛粉に
滴下または噴霧状にして少量ずつ添加しながら混合、分
散させたのち、これらの混合物と希硫酸とを練合して得
られたペーストを充填した鉛蓄電池用正極板。(1) containing substantially no antimony;
Or, in a grid made of a lead-calcium alloy containing only a small amount, the amount of tin is 0.1 to 10% based on the lead in the lead powder.
An aqueous solution of tin sulfate in a range of 3.0 mol% is added dropwise or sprayed to the lead powder while being added little by little, mixed and dispersed, and then kneaded with the mixture. Positive electrode plate for lead-acid batteries filled with the paste obtained by the above.
または僅かしか含まない鉛−カルシウム系合金からなる
格子に、鉛粉と鉛粉中の鉛分を基準にして錫分の量が
０．１〜３．０ｍｏｌ％の範囲となる錫の硫酸塩を予め
溶解させた希硫酸とを練合して得られたペーストをを充
填した鉛蓄電池用正極板。2. Antimony is substantially not contained at all,
Alternatively, a grid made of a lead-calcium alloy containing only a small amount contains lead powder and the amount of tin based on the lead in the lead powder.
A positive electrode plate for a lead storage battery filled with a paste obtained by kneading dilute sulfuric acid in which tin sulfate in a range of 0.1 to 3.0 mol% is previously dissolved.
または僅かしか含まない鉛−カルシウム系合金からなる
格子に、鉛粉中の鉛分を基準にして錫分の量が０．１〜
３．０ｍｏｌ％の範囲となる錫の硫酸塩水溶液を鉛粉に
滴下または噴霧状にして少量ずつ添加しながら混合、分
散させたのち、これらの混合物と希硫酸とを練合して得
られたペーストを充填した鉛蓄電池用正極板の製造法。3. Antimony is substantially not contained at all,
Or, in a grid made of a lead-calcium alloy containing only a small amount, the amount of tin is 0.1 to 10% based on the lead in the lead powder.
An aqueous solution of tin sulfate in a range of 3.0 mol% is added dropwise or sprayed to the lead powder while being added little by little, mixed and dispersed, and then kneaded with the mixture. Of producing a positive electrode plate for a lead storage battery filled with the paste obtained by the above method.
または僅かしか含まない鉛−カルシウム系合金からなる
格子に、鉛粉と鉛粉中の鉛分を基準にして錫分の量が
０．１〜３．０ｍｏｌ％の範囲となる錫の硫酸塩を予め
溶解させた希硫酸とを練合して得られたペーストをを充
填した鉛蓄電池用正極板の製造法。4. Antimony is substantially not contained at all,
Alternatively, a grid made of a lead-calcium alloy containing only a small amount contains lead powder and the amount of tin based on the lead in the lead powder.
A method for producing a positive electrode plate for a lead-acid battery, which is filled with a paste obtained by kneading dilute sulfuric acid in which tin sulfate in a range of 0.1 to 3.0 mol% is previously dissolved.
鉛−カルシウム−錫合金で、アンチモンを実質的に全く
含まない鋳造格子またはエキスパンドメタル格子である
請求項１または２に記載の鉛蓄電池用正極板。5. A lattice comprising a lead-calcium alloy,
The positive electrode plate for a lead storage battery according to claim 1 or 2, wherein the positive electrode plate is a cast lattice or an expanded metal lattice that is a lead-calcium-tin alloy and contains substantially no antimony.
鉛−カルシウム合金または鉛−カルシウム−錫合金等の
鉛−カルシウム系合金板の両面または片面に、鉛−錫−
アンチモン合金のようにアンチモンを含む鉛合金箔を圧
延一体化したクラッド板を用いたエキスパンドメタル格
子である請求項１または２に記載の鉛蓄電池用正極板。6. A lattice comprising a lead-calcium alloy,
Lead-tin-based alloy sheets such as lead-calcium alloy or lead-calcium-tin alloy,
The positive electrode plate for a lead storage battery according to claim 1 or 2, which is an expanded metal lattice using a clad plate obtained by rolling and integrating a lead alloy foil containing antimony such as an antimony alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21201991A JP3178015B2 (en) | 1991-08-23 | 1991-08-23 | Positive electrode plate for lead storage battery and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21201991A JP3178015B2 (en) | 1991-08-23 | 1991-08-23 | Positive electrode plate for lead storage battery and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0554881A JPH0554881A (en) | 1993-03-05 |
| JP3178015B2 true JP3178015B2 (en) | 2001-06-18 |
Family
ID=16615533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21201991A Expired - Fee Related JP3178015B2 (en) | 1991-08-23 | 1991-08-23 | Positive electrode plate for lead storage battery and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3178015B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073253C (en) * | 1996-04-26 | 2001-10-17 | 富士通株式会社 | Thin film inductive head, method for fabricating the same and magnetic writing/reading drive |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5820639A (en) * | 1996-09-20 | 1998-10-13 | Bolder Technologies Corporation | Method of manufacturing lead acid cell paste having tin compounds |
| EP0849816B1 (en) * | 1996-12-19 | 2006-09-27 | GS Yuasa Corporation | Lead-acid battery and producing method thereof |
| JP3228694B2 (en) * | 1997-03-14 | 2001-11-12 | 株式会社東郷製作所 | Hinge structure |
| JP4815665B2 (en) * | 2000-11-27 | 2011-11-16 | パナソニック株式会社 | Lead acid battery |
| US8404382B2 (en) * | 2008-04-08 | 2013-03-26 | Trojan Battery Company | Flooded lead-acid battery and method of making the same |
| US10319990B2 (en) | 2016-08-05 | 2019-06-11 | Trojan Battery Ireland Ltd. | Coated lead acid battery electrode plates; method for making coated electrode plates and lead acid batteries containing coated electrode plates |
| CN109921101A (en) * | 2019-03-05 | 2019-06-21 | 风帆有限责任公司 | A kind of lead-acid accumulator and preparation method thereof with superior low temperature starting performance |
-
1991
- 1991-08-23 JP JP21201991A patent/JP3178015B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073253C (en) * | 1996-04-26 | 2001-10-17 | 富士通株式会社 | Thin film inductive head, method for fabricating the same and magnetic writing/reading drive |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0554881A (en) | 1993-03-05 |
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