JPH0554881A - Lead-acid battery positive electrode plate and manufacture thereof - Google Patents
Lead-acid battery positive electrode plate and manufacture thereofInfo
- Publication number
- JPH0554881A JPH0554881A JP3212019A JP21201991A JPH0554881A JP H0554881 A JPH0554881 A JP H0554881A JP 3212019 A JP3212019 A JP 3212019A JP 21201991 A JP21201991 A JP 21201991A JP H0554881 A JPH0554881 A JP H0554881A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- tin
- antimony
- positive electrode
- 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.)
- Granted
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
Abstract
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 composed of 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 variations and a method for producing 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, in particular, a sealed lead-acid battery, the positive electrode plate is made of a Pb-Ca-based alloy containing substantially no Sb or only a small amount of Sb. A cast grid or expanded metal grid was filled with a paste obtained by kneading lead powder as the main component and dilute sulfuric acid, and aged and dried to produce an unformed positive electrode plate. In addition, the unformed negative plate also
Usually, a lead storage battery, which is manufactured by a similar manufacturing method using a grid made of a Pb-Ca alloy containing substantially no Sb and is assembled by an unformed positive and negative electrode plate, is first charged by battery formation or the like to obtain a battery. Was completed. A lead storage battery using a grid made of a Pb-Ca-based alloy for a positive electrode plate has very little decrease in the amount of electrolytic solution due to charge and discharge, and has excellent maintenance-free characteristics. This is an indispensable technology for absorption-type sealed lead-acid batteries. However, there is a problem that the active material of the positive electrode plate is softened by repeated charging / discharging accompanied by deep discharge, and finally the active material of the positive electrode plate is deteriorated such as falling off, resulting in a rapid decrease in battery capacity.
【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。As a measure for improving such a problem, much research has been conducted on a lead alloy composition for a lattice, a method for producing a lattice, an additive to a positive electrode active material and the like.
【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 and dilute sulfuric acid, Proposals have been made to suppress such a rapid capacity decrease.
【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
By using a positive electrode plate filled with a paste obtained by kneading lead powder to which tin oxide is added and dilute sulfuric acid in a lattice made of a Pb-Ca-based alloy such as -Ca-Sn alloy, deep discharge is generated. A rapid decrease in capacity during charge / discharge cycles is suppressed. Such a suppressing 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, a dense PbSO 4 layer that forms a passivation phenomenon is formed at the interface between the lattice and the active material, which is closely related to the charge acceptance characteristics in constant voltage charging that is widely used for charging lead acid batteries. It is considered that the tin content hinders the formation. However, if the tin content in the paste is not uniform, the above-mentioned effects may vary, and battery characteristics may not be substantially improved.
【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。The present invention eliminates the above-mentioned drawbacks by a simple and effective means. Specifically, as in the prior art, a small amount of solid tin oxide powder is added to lead powder. Addition,
Use a paste that is harmless to the battery without mixing, and is added in small amounts in the form of a water-soluble tin sulphate aqueous solution that is added dropwise or sprayed, and then mixed with diluted 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 addition of tin to lead powder is effective at about 0.2% or more as the tin content in the positive electrode active material. It was necessary to preliminarily mix the lead powder and the tin oxide powder for a long time. This is because tin oxide is a solid and the addition amount is relatively small. Therefore, in the present invention, the additive in the form of a water-soluble tin sulfate aqueous solution, which is harmless to the battery, is dropped or sprayed and mixed and dispersed little by little to the lead powder. Even when mixed, the distribution of tin content is uniform, and the effect is very small.
It greatly contributes 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。EXAMPLES Examples 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。0.02 mol / l was added to lead powder obtained by a conventional method.
The SnSO 4 aqueous solution dissolved in the above concentration was sprayed to an amount corresponding to 1 mol% of tin content based on the lead content in the lead powder, and mixed little by little, and then mixed with a predetermined amount of dilute sulfuric acid. The paste obtained by kneading with Pb-Ca-S
An n-alloy cast 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 on the same scale as the present invention with the tin content of the lead powder, the same kneader and the same mixing and kneading conditions were 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 individual cells each having a nominal capacity of 20 Ah at a 20-hour rate were manufactured.
In order to understand the characteristics of the positive electrode plate, the prototype battery has a larger negative electrode capacity than ordinary products so that the discharge capacity of the battery is regulated by the positive electrode capacity. It was used. After being charged for the first time by battery case formation, it was discharged to 1.75 V at a constant current of 5 hours, 2.
A cycle test was performed in which charging was repeated at a constant voltage of 45 V for 8 hours. The frequency distribution of the discharge capacity ratio with respect to the nominal capacities of the both in the 5th cycle is shown in FIGS. 1 and 2. The discharge capacity ratio of the battery of the conventional example shown in FIG. 1 varies from 102 to 112%, and the statistical dispersion spreads to the range of 5.69, while 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 dispersion was 0.76, which was 4.93 higher than that of the battery according to the conventional example. From the above results, it is clear that the batteries according to the examples of the present invention have less variation in the effect of tin content than the batteries according to the conventional example. Although the results are not shown, the SnO of the conventional example
Instead of the above, a paste obtained by crushing SnSO 4 crystals, adding and mixing to lead powder, and then kneading with dilute sulfuric acid was also examined. The discharge capacity ratios of the batteries according to the example of the present invention and the conventional example and The statistical variance was at an intermediate level.
Therefore, the dispersion due to the addition and mixing of the tin content 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 distribution. In the examples, SnSO 4 as the first salt was shown, but Sn (SO 4 ) 2 as the second salt was used.
There was no difference in the effect. Addition amount of tin is 1mo
I showed about 1%, but the range of 0.1-3.0mol% is effective, less than 0.1mol% is not effective, and 3.0mol%
If it exceeds%, the characteristics will rather deteriorate. The tin sulfate can be previously dissolved in dilute sulfuric acid depending on the addition amount. In this case, it is not necessary to add tin sulfate in the form of an aqueous solution to lead powder in advance, and a paste obtained by directly kneading lead powder and dilute sulfuric acid in which tin sulfate is previously dissolved has the same effect. Is played. Further, in the example, the grid was filled with the paste, and immediately aged and dried to obtain an unformed positive electrode plate,
Depending on the paste formulation, even if the paste is filled and then subjected to an immersing treatment, followed by aging and drying, it does not depart from the gist of the present invention. Furthermore, in the examples, a cast lattice made of a Pb-Ca-Sn alloy containing substantially no Sb has been described, but an expanded metal lattice made of the same alloy and, for example, Pb-Ca alloy, Pb-Ca-Sn.
Pb-Ca alloy plate such as alloy, Pb on both sides or one side
A similar effect can be obtained in the case of a lattice in which Sb is slightly scattered on the lattice surface, such as an expanded metal lattice using a clad plate in which a Pb alloy foil containing Sb such as -Sn-Sb alloy is rolled and integrated. ..
【００１１】[0011]
【発明の効果】以上詳述したように、鉛粉に、所定量の
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 in detail above, the lead powder is mixed with a predetermined amount of tin sulfate in the form of an aqueous solution or a dilute sulfuric acid solution, and the distribution of tin content in the paste containing lead powder as the main component is adjusted. By uniforming the discharge capacity in a short time, it is possible to obtain a maintenance-free lead acid battery, in particular, a sealed lead acid battery, which can improve the discharge capacity while reducing the variation.
【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 with respect 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 with respect to a nominal capacity according to an embodiment of the present invention.
Claims (5)
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、鉛粉に所定量の錫の硫酸塩水溶液を滴下または噴
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およびその製造法。1. A grid of a lead-calcium alloy containing substantially no antimony or only a small amount of antimony, and a predetermined amount of a tin sulfate aqueous solution is added dropwise or atomized to lead powder to form a small amount. A positive electrode plate for a lead storage battery filled with a paste obtained by mixing and dispersing while adding and kneading these mixtures and dilute sulfuric acid, and a method for producing the same.
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、鉛粉と予め所定量の錫の硫酸塩を溶解させた希硫
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
正極板およびその製造法。2. A lattice made of a lead-calcium alloy containing substantially no antimony or little antimony and lead powder and diluted sulfuric acid prepared by dissolving a predetermined amount of tin sulfate in advance. A positive electrode plate for a lead storage battery filled with the paste obtained by the combination and a method for producing the same.
硫酸塩の錫分の量が０．１〜３．０mol％の範囲である
請求項１および２記載の鉛蓄電池用正極板およびその製
造法。3. The lead-acid battery according to claim 1, wherein the tin content of the tin sulfate to be added is in the range of 0.1 to 3.0 mol% based on the lead content in the lead powder. Positive electrode plate and manufacturing method thereof.
−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１，２または３記載の鉛蓄電池用正極板。4. The lead storage battery according to claim 1, wherein the grid made of a lead-calcium alloy is a lead-calcium-tin alloy and is a cast grid or an expanded metal grid containing substantially no antimony. Positive plate.
−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１，２または３記載の鉛蓄電池用正極板。5. A lead-calcium alloy lattice is provided on both or one side of a lead-calcium alloy plate such as a lead-calcium alloy or a lead-calcium-tin alloy, and antimony such as a lead-tin-antimony alloy. The positive electrode plate for a lead storage battery according to claim 1, which is an expanded metal grid using a clad plate obtained by rolling and integrating a lead alloy foil containing a.
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 true JPH0554881A (en) | 1993-03-05 |
| JP3178015B2 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 (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0849816A1 (en) * | 1996-12-19 | 1998-06-24 | Japan Storage Battery Company Limited | Lead-acid battery and producing method thereof |
| US6154927A (en) * | 1997-03-14 | 2000-12-05 | Togo Seisakusyo Corp. | Hinge |
| EP0931360A4 (en) * | 1996-09-20 | 2000-12-06 | Bolder Technologies Corp | Lead acid cell paste having tin compounds and method of manufacturing and using same |
| JP2002164080A (en) * | 2000-11-27 | 2002-06-07 | Matsushita Electric Ind Co Ltd | Lead-acid battery |
| EP2263276A2 (en) * | 2008-04-08 | 2010-12-22 | 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09293209A (en) * | 1996-04-26 | 1997-11-11 | Fujitsu Ltd | Thin film magnetic head and magnetic recorder and production of thin film magnetic head |
-
1991
- 1991-08-23 JP JP21201991A patent/JP3178015B2/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0931360A4 (en) * | 1996-09-20 | 2000-12-06 | Bolder Technologies Corp | Lead acid cell paste having tin compounds and method of manufacturing and using same |
| JP2001501019A (en) * | 1996-09-20 | 2001-01-23 | ボルダー テクノロジーズ コーポレイション | Lead-acid battery paste containing tin compound and method for producing and using the same |
| EP0849816A1 (en) * | 1996-12-19 | 1998-06-24 | Japan Storage Battery Company Limited | Lead-acid battery and producing method thereof |
| US6154927A (en) * | 1997-03-14 | 2000-12-05 | Togo Seisakusyo Corp. | Hinge |
| JP2002164080A (en) * | 2000-11-27 | 2002-06-07 | Matsushita Electric Ind Co Ltd | Lead-acid battery |
| CN102027618A (en) * | 2008-04-08 | 2011-04-20 | 特洛伊电池公司 | Flooded lead-acid battery and method of making the same |
| EP2263276A2 (en) * | 2008-04-08 | 2010-12-22 | Trojan Battery Company | Flooded lead-acid battery and method of making the same |
| EP2263276A4 (en) * | 2008-04-08 | 2011-08-17 | Trojan Battery Co | Flooded lead-acid battery and method of making the same |
| US8404382B2 (en) | 2008-04-08 | 2013-03-26 | Trojan Battery Company | Flooded lead-acid battery and method of making the same |
| US8722249B2 (en) | 2008-04-08 | 2014-05-13 | Trojan Battery Company | Flooded lead-acid battery and method of making the same |
| US9728772B2 (en) | 2008-04-08 | 2017-08-08 | Trojan Battery Company, Llc | 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 |
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| Publication number | Publication date |
|---|---|
| JP3178015B2 (en) | 2001-06-18 |
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| LAPS | Cancellation because of no payment of annual fees |