JPH09330700A - Lead acid battery - Google Patents
Lead acid batteryInfo
- Publication number
- JPH09330700A JPH09330700A JP8168412A JP16841296A JPH09330700A JP H09330700 A JPH09330700 A JP H09330700A JP 8168412 A JP8168412 A JP 8168412A JP 16841296 A JP16841296 A JP 16841296A JP H09330700 A JPH09330700 A JP H09330700A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- corrosion
- alloy
- weight
- battery
- 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.)
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Classifications
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- 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
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Abstract
(57)【要約】
【課題】自動車用電池などのような高温環境で鉛蓄電池
が使用された際に、極板接続部（ストラップなど）で異
常腐食がみられることがあった。これは製造時に生じた
微細なクラックなどの欠陥から腐食が進行拡大していく
もので、最悪の場合にはストラップやセル間接続部が破
断し電池機能が完全になくなってしまうことがあった。
【解決手段】ニッケル含有量が０．０００２から０．０
０３重量％である鉛−錫系合金を極板接続部、セル間接
続部、極柱の少なくとも一部に用いたことを特徴とする
鉛蓄電池。
(57) [Abstract] [Problem] When a lead storage battery is used in a high temperature environment such as a battery for an automobile, abnormal corrosion may be observed in a connecting portion (strap or the like) of an electrode plate. This is because corrosion progresses and spreads due to defects such as minute cracks generated during manufacturing, and in the worst case, the strap and the cell-to-cell connecting portion may be broken and the battery function may be completely lost. A nickel content is 0.0002 to 0.0.
A lead acid battery characterized in that a lead-tin alloy of 03% by weight is used for at least a part of the electrode plate connecting portion, the inter-cell connecting portion, and the electrode column.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は鉛蓄電池の改良に関
するものである。TECHNICAL FIELD The present invention relates to an improvement of a lead storage battery.
【０００２】[0002]
【従来の技術とその課題】近年、鉛蓄電池の使用環境は
大きく変化しており、従来にはみられなかった不具合が
みられるようになってきた。例えば、自動車用電池など
のように高温環境で使用された際に、接続部（ストラッ
プなど）で異常腐食がみられることがある。これは製造
時に生じた微細なクラックなどの欠陥から腐食が進行拡
大していくもので、最悪の場合にはストラップやセル間
接続部が破断し電池機能が完全になくなってしまうこと
がある。腐食形態としては、ＰｂがＰｂＯ2 へと変化す
る正極側の腐食およびＰｂがＰｂＳＯ4 へと変化する負
極側の腐食に大別できる。2. Description of the Related Art In recent years, the environment in which lead-acid batteries have been used has changed greatly, and problems that have not been seen in the past have become apparent. For example, when used in a high temperature environment such as a battery for an automobile, abnormal corrosion may be observed at a connecting portion (strap or the like). This is because corrosion progresses and spreads due to defects such as minute cracks generated during manufacturing, and in the worst case, the strap and the cell-to-cell connecting portion may be broken and the battery function may be completely lost. Corrosion modes can be roughly classified into positive side corrosion in which Pb changes to PbO 2 and negative side corrosion in which Pb changes to PbSO 4 .
【０００３】正極腐食に関しては従来から知られている
ような酸化腐食であり、合金の改良により耐食性の改善
が可能であることがわかっている。一方負極については
還元方向であるために、従来腐食は起こらないとされて
いた。負極腐食が発生する条件は、研究の結果次の場合
であることが分かった。The positive electrode corrosion is oxidative corrosion as conventionally known, and it has been known that the corrosion resistance can be improved by improving the alloy. On the other hand, since the negative electrode is in the reducing direction, it has been conventionally said that corrosion does not occur. As a result of research, it was found that the conditions under which negative electrode corrosion occurs were as follows.
【０００４】（ａ）正極に鉛−アンチモン系合金を用い
た電池でよくみられる。(A) It is often found in batteries using a lead-antimony alloy for the positive electrode.
【０００５】（ｂ）温度が高いほど腐食が多い。(B) The higher the temperature, the more corrosion.
【０００６】（ｃ）液面から露出した部分で腐食が進行
する。(C) Corrosion progresses in the portion exposed from the liquid surface.
【０００７】（ｄ）電池の充電時 これらから腐食の原因として次のことが考えられる。(D) At the time of charging the battery From these, the following factors are considered as the cause of corrosion.
【０００８】（イ）酸素還元による腐食 液面から露出した部分では、空気中または正極から発生
した酸素、および硫酸が供給されるために次式の反応が
起こる。(B) Corrosion due to oxygen reduction In the portion exposed from the liquid surface, oxygen generated in the air or from the positive electrode and sulfuric acid are supplied, so that the reaction of the following formula occurs.
【０００９】 Ｐｂ＋１／２Ｏ2＋Ｈ2ＳＯ4→ＰｂＳＯ4＋Ｈ2Ｏ （ロ）局部電池腐食 正極に鉛−アンチモン合金を用いた電池では使用中に、
負極板やストラップなどの負極部品上に正極で溶解した
アンチモンが電析する。電析部分が液面から露出する
と、アンチモン上で水素が発生しそれにともないＰｂか
ら電子が奪われＰｂがＰｂＳＯ4 へと変化、すなわち腐
食する。Pb + 1 / 2O 2 + H 2 SO 4 → PbSO 4 + H 2 O (b) Local battery corrosion During use in a battery using a lead-antimony alloy for the positive electrode,
Antimony dissolved in the positive electrode is deposited on the negative electrode parts such as the negative electrode plate and the strap. When the electrodeposited portion is exposed from the surface of the liquid, hydrogen is generated on antimony, electrons are taken from Pb with it, and Pb changes to PbSO 4 , that is, corrosion occurs.
【００１０】（露出部分） Ｓｂ上：２Ｈ+ ＋２ｅ→Ｈ2 Ｐｂ上：Ｐｂ＋ＳＯ4 2-→ＰｂＳＯ4 ＋２ｅ 液中部分ではＰｂＳＯ4 が生成しても充電反応によりＰ
ｂへと還元されるが、露出部分では電流が流れにくいた
めに還元反応が起こりにくい。すなわち、ＰｂＳＯ4 の
生成しか反応が起こらないので腐食は次第に進行してい
くことになる。(Exposed part) On Sb: 2H + + 2e → H 2 On Pb: Pb + SO 4 2- → PbSO 4 + 2e Even if PbSO 4 is produced in the liquid part, P is generated by the charging reaction.
Although it is reduced to b, the reduction reaction does not easily occur because the current hardly flows in the exposed portion. That is, since only reaction of PbSO 4 is generated, the corrosion gradually progresses.
【００１１】実際の電池では（イ）および（ロ）の腐食
が同時に起こっているものと考えられる。負極側の腐食
生成物であるＰｂＳＯ4 は、モル容積にしてＰｂの約
２．６倍と非常に大きいために、合金のクラック内など
に生成するとくさびの様にそのクラックを押し広げ、や
がては破断にいたらしめてしまう。正極側の腐食生成物
であるＰｂＯ2 は、そのモル容積がＰｂの約１．３倍で
あることからも負極側の腐食の方が深刻な問題であるこ
とがわかる。図７に腐食された負極ストラップの模式図
を示した。液面から露出した部分の微細なクラック内部
に腐食生成物ができ、これがクラックを押し広げてい
る。この様な腐食が進行するとストラップが破断に至
る。鉛−錫系合金はその結晶粒が大きいために一旦腐食
が始まると、粒界に沿った大きなものになり破断に至り
やすい。It is considered that in the actual battery, the corrosions (a) and (b) occur simultaneously. The corrosion product on the negative electrode side, PbSO 4, is very large, about 2.6 times the molar volume of Pb, so if it is generated in the cracks of the alloy, it spreads the cracks like a wedge, and eventually. If it breaks, it will end up. Corrosion products on the positive electrode side, PbO 2, have a molar volume of about 1.3 times that of Pb, indicating that corrosion on the negative electrode side is a more serious problem. FIG. 7 shows a schematic diagram of the corroded negative electrode strap. Corrosion products are formed inside the fine cracks exposed from the liquid surface, which spread the cracks. If such corrosion progresses, the strap will be broken. Since the lead-tin alloy has large crystal grains, once corrosion starts, it becomes large along the grain boundaries and is likely to break.
【００１２】また、正極板、負極板、その他の鉛部品中
にアンチモンを全く含まない密閉式鉛蓄電池などでは腐
食は少ないが、長期間使用している内に（イ）の酸素還
元による腐食がみられる。Further, the positive electrode plate, the negative electrode plate, and other sealed lead-acid batteries which do not contain any antimony in the lead parts have little corrosion, but during long-term use, the corrosion due to the oxygen reduction of (a) may occur. Be looked at.
【００１３】このような問題点を解決するために、正極
側のみならず、露出部分の負極耐食性にも優れた合金の
開発が求められている。In order to solve such a problem, it is required to develop an alloy excellent not only in the positive electrode side but also in the corrosion resistance of the exposed portion of the negative electrode.
【００１４】[0014]
【課題を解決するための手段】本発明は上述したような
極板接続部やセル間接続部の異常腐食という問題を解決
するもので、ニッケル含有量が０．０００２から０．０
０３重量％である鉛−錫系合金を極板接続部、セル間接
続部、極柱の少なくとも一部に用いたことを特徴とする
ものである。The present invention solves the above-mentioned problem of abnormal corrosion of the electrode plate connecting portion and the cell connecting portion, and the nickel content is 0.0002 to 0.02.
It is characterized in that the lead-tin alloy of 03% by weight is used for at least a part of the electrode plate connecting portion, the cell connecting portion, and the electrode column.
【００１５】[0015]
【発明の実施の形態】極板接続部、セル間接続部、極柱
の少なくとも一部に用いる合金として鉛−錫系合金にニ
ッケルを０．０００２から０．００３重量％添加して、
以降常法によって鉛蓄電池を作製する。BEST MODE FOR CARRYING OUT THE INVENTION As an alloy used for at least a part of electrode plate connecting portions, inter-cell connecting portions, and poles, 0.0002 to 0.003% by weight of nickel is added to a lead-tin alloy,
Thereafter, a lead storage battery is manufactured by a conventional method.
【００１６】[0016]
【実施例１】以下に本発明の詳細を実施例をもとに説明
する。[Embodiment 1] Details of the present invention will be described below with reference to embodiments.
【００１７】合金の耐食性を明らかにするために試験セ
ルを用いて正極側、負極側におかれた際の腐食の程度を
調べた。In order to clarify the corrosion resistance of the alloy, the degree of corrosion when placed on the positive electrode side and the negative electrode side was examined using a test cell.
【００１８】まず、電解精錬によって製造されたＪＩＳ
特種（ＪＩＳＨ２１０５記載）の原料鉛に錫を２重量％
添加した。上記組成の鉛合金にニッケル量を０．０００
１重量％から０．００５重量％の間で変えて添加したも
のを６種類調合した。なお、比較のためにニッケルを添
加していない従来の鉛合金もそのまま用意した。このニ
ッケル無添加合金中に不純物として含まれるニッケル量
は０．００００３％であった。First, the JIS manufactured by electrolytic refining
2% by weight of tin in lead of special kind (described in JIS H2105)
Was added. 0.000 of nickel is added to the lead alloy of the above composition.
Six types of materials were prepared by changing the addition amount from 1% by weight to 0.005% by weight. For comparison, a conventional lead alloy to which nickel was not added was prepared as it was. The amount of nickel contained as impurities in this nickel-free alloy was 0.00003%.
【００１９】上記の合金より試験片（高さ１００ｍｍ、
幅３０ｍｍ、厚み２ｍｍ）を作製し、図１に示すセルを
用いて腐食試験に供した。試験セル１に比重１．３０の
硫酸３を入れ、試験片２の半分を液中に浸漬し、定電流
通電を行った。硫酸には腐食を促進させるために、アン
チモンを１０ｍｇ／リットル添加した。電流は試験片の
液中部分に対して５０ｍＡ／ｃｍ2 、試験温度は腐食を
加速するために９０℃、試験期間は２週間とした。正極
側の腐食は液中部分で起こり、負極側の腐食は前述した
理由により露出部分すなわち液面上部で起こる。試験後
の試験片は、腐食生成物を除去した後の母材の厚みを測
定し、厚み減少率を求めた。厚み減少率が大きいほど腐
食が大きいことになる。Test pieces (height 100 mm,
A width of 30 mm and a thickness of 2 mm) was prepared and subjected to a corrosion test using the cell shown in FIG. Sulfuric acid 3 having a specific gravity of 1.30 was placed in the test cell 1, half of the test piece 2 was immersed in the liquid, and constant current energization was performed. Antimony was added to sulfuric acid at 10 mg / liter in order to promote corrosion. The current was 50 mA / cm 2 with respect to the submerged portion of the test piece, the test temperature was 90 ° C. to accelerate corrosion, and the test period was 2 weeks. Corrosion on the positive electrode side occurs in the liquid portion, and corrosion on the negative electrode side occurs in the exposed portion, that is, the upper portion of the liquid surface for the reason described above. For the test pieces after the test, the thickness of the base material after the corrosion products were removed was measured, and the thickness reduction rate was obtained. The larger the thickness reduction rate, the greater the corrosion.
【００２０】試験片の合金組成を表１に示した。The alloy composition of the test piece is shown in Table 1.
【００２１】[0021]
【表１】 試験終了後、正極腐食発生部分４および負極腐食発生部
分５の母材の厚み減少率を調査した。試験結果を図２に
示した。正極側ではＮｉ量を変化させても厚み減少率は
ほとんど変化しないが、負極側では０．０００２重量％
以上で急激に減少する。このことは負極側の腐食を低減
するためにはＮｉを０．０００２％以上添加すればよい
ことを意味している。Ｎｉが負極側の腐食を低減した理
由として次のことが考えられる。[Table 1] After the test was completed, the thickness reduction rate of the base material in the positive electrode corrosion occurrence portion 4 and the negative electrode corrosion occurrence portion 5 was investigated. The test results are shown in FIG. On the positive electrode side, the thickness reduction rate hardly changes even if the amount of Ni is changed, but on the negative electrode side 0.0002% by weight
It will decrease sharply. This means that Ni can be added in an amount of 0.0002% or more in order to reduce corrosion on the negative electrode side. The following is considered as the reason why Ni reduced the corrosion on the negative electrode side.
【００２２】ａ．Ｎｉが酸素還元の触媒として働き、鉛
の酸素還元腐食を低減した。A. Ni worked as a catalyst for oxygen reduction, and reduced oxygen reduction corrosion of lead.
【００２３】ｂ．Ｎｉが鉛中に分散して、腐食されにく
い合金組織となった。B. Ni was dispersed in lead to form an alloy structure that was not easily corroded.
【００２４】次にＳｎ量の影響を調べるためにＰｂ−
０．００１％Ｎｉ合金にＳｎを０から５％添加した試験
片を作り同様の腐食試験を行った。試験結果を図３に示
した。正極ではＳｎ量を増やしていくと次第に腐食が増
え、４％を越えると急激に増加した。負極ではＳｎ量が
０．５％以上で腐食が低減し、それ以上ではあまり変化
しなかった。これらからＳｎ量は０．５から４％の範囲
が望ましいことがわかった。Next, in order to investigate the influence of the Sn amount, Pb-
A similar corrosion test was performed by making a test piece in which 0.001% Ni alloy was added with 0 to 5% Sn. The test results are shown in FIG. Corrosion of the positive electrode gradually increased as the Sn content was increased, and increased rapidly when the Sn content exceeded 4%. In the negative electrode, the corrosion was reduced when the Sn content was 0.5% or more, and did not change so much when the Sn content was more than 0.5%. From these, it was found that the Sn amount is preferably in the range of 0.5 to 4%.
【００２５】他の添加元素の影響を調べるために、Ｓｅ
量、Ａｓ量、Ａｇ量を変えた試験片を作製して同様の試
験を行った。合金はＰｂ−２．０％Ｓｎ−０．００１％
Ｎｉを基準として、それぞれの元素の添加量を変化させ
た試験片を作製した。その結果を図４、５、６に示し
た。In order to investigate the influence of other additive elements, Se
The same test was performed by preparing test pieces with different amounts, As amounts, and Ag amounts. Alloy is Pb-2.0% Sn-0.001%
Test pieces were prepared in which the amount of addition of each element was changed based on Ni. The results are shown in FIGS.
【００２６】Ｓｅ添加量の、正極側、負極側腐食に及ぼ
す影響はみられなかった。しかし、Ｓｅを添加していな
い合金では、結晶粒が大きくなるために粒界に沿った腐
食が部分的にみられた。Ｓｅを添加した合金では結晶粒
が微細化されており、粒界腐食はみられなかった。Ｓｅ
の微細化効果は０．００５重量％以上でみられるが、Ｓ
ｅの添加可能量は温度に依存しており、鉛電池部品を製
造する４００−５００℃の範囲では鉛−錫系合金の場
合、０．０４％以上Ｓｅを添加することは困難である。
Ｓｅは厳しい環境で使われる部品には添加してもよい
が、そうでない場合には添加しなくてもかまわない。従
ってＳｅを添加する際は０．００５から０．０４％の範
囲が適当である。No effect of the added amount of Se on the corrosion on the positive electrode side and the negative electrode side was observed. However, in the alloy to which Se was not added, the crystal grains became large, so that corrosion along the grain boundaries was partially observed. In the alloy to which Se was added, the crystal grains were refined and no intergranular corrosion was observed. Se
The effect of refining S is 0.005% by weight or more, but S
The amount of e that can be added depends on the temperature, and it is difficult to add Se in an amount of 0.04% or more in the case of a lead-tin alloy in the range of 400 to 500 ° C. for manufacturing a lead battery component.
Se may be added to parts used in a harsh environment, but if not, it may not be added. Therefore, when adding Se, the range of 0.005 to 0.04% is suitable.
【００２７】Ａｓ添加量の、正極側、負極側腐食に及ぼ
す影響はみられなかった。Ａｓには０．０１％以上添加
した場合に合金強度を上げる作用があるため、若干添加
しても良い。添加量が多すぎると電池の自己放電量を増
大させるので多くとも０．３％程度にすべきである。従
ってＡｓを添加する場合には０．０１から０．３％の範
囲が適当である。No effect of the amount of As added on the corrosion on the positive electrode side and the negative electrode side was observed. Since As has a function of increasing the alloy strength when added in an amount of 0.01% or more, As may be added in a small amount. If the amount added is too large, the self-discharge amount of the battery increases, so the amount should be at most 0.3%. Therefore, when As is added, the range of 0.01 to 0.3% is appropriate.
【００２８】Ａｇを０．０１％以上添加すると正極側の
腐食が大幅に低減した。負極側の腐食についてはＡｇ添
加量による差はみられなかった。Ａｇについても添加量
が多すぎると電池の自己放電量を増大させるので多くと
も０．２％程度にすべきでる。従ってＡｇを添加する場
合には０．０１から０．２％の範囲が適当である。When 0.01% or more of Ag was added, the corrosion on the positive electrode side was significantly reduced. Regarding the corrosion on the negative electrode side, no difference was observed depending on the amount of Ag added. If Ag is added too much, the self-discharge amount of the battery is increased. Therefore, Ag should be at most about 0.2%. Therefore, when Ag is added, the range of 0.01 to 0.2% is appropriate.
【００２９】[0029]
【実施例２】表２に示したそれぞれの合金（Ｐｂ−２％
Ｓｎ−Ｎｉ）をストラップ、極柱およびセル間接続部に
用いて電池を作製した。また、Ｐｂ−２％Ｓｎ−０．１
％Ａｓ−０．１％Ａｇ−０．００１％Ｎｉ−０．０１％
Ｓｅ合金についても検討した（電池Ｎｏ．８）。ストラ
ップはキャストオンストラップ（ＣＯＳ）と呼ばれる、
溶融鉛合金に極板耳を浸漬・凝固させる方法で作製し
た。Example 2 Each alloy shown in Table 2 (Pb-2%
Sn-Ni) was used for the strap, the poles, and the cell-to-cell connecting portion to manufacture a battery. In addition, Pb-2% Sn-0.1
% As-0.1% Ag-0.001% Ni-0.01%
The Se alloy was also examined (Battery No. 8). The strap is called cast on strap (COS),
It was prepared by dipping and solidifying the electrode plate ears in a molten lead alloy.
【００３０】[0030]
【表２】 正極板には鉛−アンチモン系合金格子、負極板には鉛−
カルシウム系合金格子を用いて、自動車用鉛蓄電池５５
Ｄ２３（ＪＩＳＤ５３０１記載）を作製し、電池をＪＩ
ＳＤ５３０１記載の軽負荷寿命試験に供した。その結
果、Ｎｉ量が０から０．００３％である電池Ｎｏ．１か
ら６および８はほぼ同等の寿命と減液量であったが、Ｎ
ｉ量０．００５％の電池Ｎｏ．７は減液量が非常に大き
くなり短寿命であった。これは、ニッケルを過剰に添加
したため、負極の水素過電圧が著しく低下し、過充電中
の電解液の分解が激しくなり、電池の減液量が増大し、
さらに電解液の比重が次第に上昇して寿命に到ったため
であった。[Table 2] Lead-antimony alloy grid on the positive plate, lead-on the negative plate
Automotive lead-acid battery 55 using calcium alloy grid
D23 (described in JIS D5301) was prepared and the battery was JI.
It was subjected to the light load life test described in SD5301. As a result, battery No. 1 having a Ni content of 0 to 0.003%. 1 to 6 and 8 had almost the same life and reduced amount of liquid, but N
Battery No. 1 with an amount of 0.005% In No. 7, the liquid reduction amount was very large and the life was short. This is because the nickel over-addition significantly reduced the hydrogen overvoltage of the negative electrode, the decomposition of the electrolytic solution during overcharge became violent, and the amount of liquid reduction of the battery increased,
Furthermore, the specific gravity of the electrolytic solution gradually increased to reach the end of its life.
【００３１】また、試験後の負極ストラップを調査した
ところ、電池Ｎｏ．１，２では図７で示したような亀裂
がみられたのに対し、電池Ｎｏ．３から８では全く異常
が見られなかった。また、電池Ｎｏ．８の正極ストラッ
プは他の電池よりも腐食が少ない傾向が見られた。When the negative electrode strap after the test was examined, the battery No. In Nos. 1 and 2, cracks as shown in FIG. No abnormalities were observed in 3 to 8. In addition, the battery No. The positive electrode strap of No. 8 tended to corrode less than other batteries.
【００３２】Ｎｉ添加量については実施例１、２の結果
を総合的に判断すると０．０００２から０．００３重量
％とするのが望ましいことが分かった。今回は液式鉛蓄
電池に適用した場合について述べたがこれに限定するも
のではなく、密閉型鉛蓄電池についても同様の腐食低減
効果が得られる。It was found that the amount of Ni added is preferably 0.0002 to 0.003% by weight when the results of Examples 1 and 2 are comprehensively judged. This time, the case of applying to a liquid lead storage battery was described, but the present invention is not limited to this, and the same corrosion reduction effect can be obtained for a sealed lead storage battery.
【００３３】[0033]
【発明の効果】上述したように、ニッケル含有量が０．
０００２から０．００３重量％である鉛−錫系合金を極
板接続部、セル間接続部、極柱の少なくとも一部に用い
た鉛蓄電池は極板接続部やセル間接続部の異常腐食とい
う問題を低減することができるため、工業的価値は甚だ
大なるものである。As described above, the nickel content is 0.
A lead-acid battery using a lead-tin alloy of 0002 to 0.003% by weight in at least part of the electrode plate connecting portion, the cell connecting portion, and the electrode pillar is called abnormal corrosion of the electrode plate connecting portion and the cell connecting portion. The industrial value is enormous because it can reduce problems.
【図１】試験セルを示す図FIG. 1 is a diagram showing a test cell.
【図２】Ｎｉ添加量が正極側、負極側腐食に及ぼす影響
を示す図FIG. 2 is a diagram showing the influence of the amount of added Ni on corrosion on the positive electrode side and the negative electrode side.
【図３】Ｓｎ添加量が正極側、負極側腐食に及ぼす影響
を示す図FIG. 3 is a diagram showing the effect of the amount of Sn added on corrosion on the positive electrode side and the negative electrode side.
【図４】Ｓｅ添加量が正極側、負極側腐食に及ぼす影響
を示す図FIG. 4 is a diagram showing the effect of the amount of Se added on corrosion on the positive electrode side and the negative electrode side.
【図５】Ａｓ添加量が正極側、負極側腐食に及ぼす影響
を示す図FIG. 5 is a diagram showing the influence of the addition amount of As on the positive electrode side and negative electrode side corrosion.
【図６】Ａｇ添加量が正極側、負極側腐食に及ぼす影響
を示す図FIG. 6 is a diagram showing the effect of the amount of Ag added on corrosion on the positive electrode side and the negative electrode side.
【図７】異常腐食の起こったストラップを示す図FIG. 7 is a diagram showing a strap with abnormal corrosion.
１ 試験セル ２ 試験片 ３ 硫酸（Ｓｂ：１０ｍｇ／ｌ） ４ 正極腐食発生部分 ５ 負極腐食発生部分 ６ 極板耳 ７ ストラップ ８ クラック 1 Test Cell 2 Test Piece 3 Sulfuric Acid (Sb: 10 mg / l) 4 Positive Electrode Corrosion Occurring Area 5 Negative Electrode Corrosion Occurring Area 6 Electrode Plate Ear 7 Strap 8 Crack
フロントページの続き (72)発明者 水田 治彦 京都市南区吉祥院西ノ庄猪之馬場町１番地 日本電池株式会社内 (72)発明者 安川 祥二 京都市南区吉祥院西ノ庄猪之馬場町１番地 日本電池株式会社内 (72)発明者 山中 健司 京都市南区吉祥院西ノ庄猪之馬場町１番地 日本電池株式会社内Front page continuation (72) Inventor Haruhiko Mizuta 1 Kinoshoin Nishinosho Ino No Babacho, Minami Ward, Kyoto City Japan Battery Co., Ltd. Address In Nihon Battery Co., Ltd. (72) Inventor Kenji Yamanaka No. 1 Inaba Babacho, Nishinosho, Kichijoin, Minami-ku, Kyoto City In Nihon Battery Co., Ltd.
Claims (5)
０３重量％である鉛−錫系合金を極板接続部、セル間接
続部、極柱の少なくとも一部に用いたことを特徴とする
鉛蓄電池。1. A nickel content of 0.0002 to 0.0
A lead acid battery characterized in that a lead-tin alloy of 03% by weight is used for at least a part of the electrode plate connecting portion, the inter-cell connecting portion, and the electrode column.
４重量％、残部鉛とした鉛−錫−ニッケル合金であるこ
とを特徴とする請求項１記載の鉛蓄電池。2. The lead acid battery according to claim 1, wherein the lead-tin alloy is a lead-tin-nickel alloy having a tin content of 0.5 to 4% by weight and the balance being lead.
４重量％、セレン含有量が０．００５から０．０４重量
％、残部鉛とした鉛−錫−ニッケル−セレン合金である
ことを特徴とする請求項１記載の鉛蓄電池。3. A lead-tin-nickel-selenium alloy having a tin content of 0.5 to 4% by weight, a selenium content of 0.005 to 0.04% by weight, and a balance of lead. The lead storage battery according to claim 1, wherein the lead storage battery is an alloy.
４重量％、ヒ素含有量が０．０１から０．３重量％、銀
含有量が０．０１から０．２重量％、残部鉛とした鉛−
錫−ヒ素−銀−ニッケル合金であることを特徴とする請
求項１記載の鉛蓄電池。4. The lead-tin alloy has a tin content of 0.5 to 4% by weight, an arsenic content of 0.01 to 0.3% by weight, and a silver content of 0.01 to 0.2. % By weight, balance lead
The lead-acid battery according to claim 1, which is a tin-arsenic-silver-nickel alloy.
４重量％、ヒ素含有量が０．０１から０．３重量％、銀
含有量が０．０１から０．２重量％、セレン含有量が
０．００５から０．０４重量％、残部鉛とした鉛−錫−
ヒ素−銀−ニッケル−セレン合金であることを特徴とす
る請求項１記載の鉛蓄電池。5. The lead-tin alloy has a tin content of 0.5 to 4% by weight, an arsenic content of 0.01 to 0.3% by weight, and a silver content of 0.01 to 0.2. % By weight, selenium content of 0.005 to 0.04% by weight, balance lead-lead-tin-
The lead acid battery according to claim 1, which is an arsenic-silver-nickel-selenium alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8168412A JPH09330700A (en) | 1996-06-06 | 1996-06-06 | Lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8168412A JPH09330700A (en) | 1996-06-06 | 1996-06-06 | Lead acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09330700A true JPH09330700A (en) | 1997-12-22 |
Family
ID=15867654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8168412A Pending JPH09330700A (en) | 1996-06-06 | 1996-06-06 | Lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09330700A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002093457A (en) * | 2000-07-12 | 2002-03-29 | Japan Storage Battery Co Ltd | Lead storage battery |
-
1996
- 1996-06-06 JP JP8168412A patent/JPH09330700A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002093457A (en) * | 2000-07-12 | 2002-03-29 | Japan Storage Battery Co Ltd | Lead storage battery |
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