JPH09283137A - Lead-acid battery - Google Patents
Lead-acid batteryInfo
- Publication number
- JPH09283137A JPH09283137A JP8115330A JP11533096A JPH09283137A JP H09283137 A JPH09283137 A JP H09283137A JP 8115330 A JP8115330 A JP 8115330A JP 11533096 A JP11533096 A JP 11533096A JP H09283137 A JPH09283137 A JP H09283137A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- weight
- antimony
- acid battery
- 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.)
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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
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
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】鉛蓄電池は、自動車の始動・点灯用をは
じめ小容量のコンシューマー用から大容量の据置用ま
で、多くの用途で使用されている。近年、鉛蓄電池は、
放置中の自己放電抑制と使用中の電解液（希硫酸）分解
にともなう補水作業の低減化のため、種々の改良が進め
られている。その代表的なものとして、正極格子合金中
のアンチモン添加量の低減、あるいはアンチモンを含ま
ない鉛合金（鉛−カルシウム−錫系合金）を用いた正極
格子の採用が挙げられる。これらのようないわゆる低ア
ンチモン化あるいはアンチモンフリー化が進むにつれ
て、上記問題は低減されてきたものの、電解液の成層化
という新たな問題が生じてきた。このような電解液成層
化は、電池内上部の電解液比重が下部の電解液比重より
も低くなってしまうことであり、次のようにして引き起
こされることが知られている。すなわち、鉛蓄電池の電
解液中の硫酸は、放電反応によって硫酸鉛として正・負
極活物質中に析出し、充電反応によって活物質中から電
解液中に放出される。そして充電中に放出された硫酸
が、周囲の電解液よりも比重が高いために電池の下部に
移動するからである。2. Description of the Related Art Lead-acid batteries are used in many applications including starting and lighting of automobiles, small capacity consumers, and large capacity stationary applications. In recent years, lead acid batteries are
Various improvements have been made in order to suppress self-discharge during standing and to reduce the rehydration work associated with the decomposition of the electrolytic solution (dilute sulfuric acid) during use. Typical examples thereof include reducing the amount of antimony added to the positive electrode lattice alloy, or adopting a positive electrode lattice using a lead alloy (lead-calcium-tin alloy) containing no antimony. With the progress of so-called antimony reduction or antimony-free as described above, the above problem has been reduced, but a new problem of stratification of the electrolytic solution has arisen. Such electrolytic solution stratification is that the specific gravity of the electrolytic solution in the upper part of the battery becomes lower than the specific gravity of the lower solution, and is known to be caused as follows. That is, the sulfuric acid in the electrolytic solution of the lead acid battery is deposited as lead sulfate in the positive and negative electrode active materials by the discharge reaction, and is released from the active material into the electrolytic solution by the charging reaction. The sulfuric acid released during charging moves to the lower part of the battery because it has a higher specific gravity than the surrounding electrolyte solution.
【０００３】この電解液成層化は、従来、放電深度が大
きい場合、すなわち重負荷使用時だけの問題であった
が、上記のごとく近年の低アンチモン化あるいはアンチ
モンフリー化にともなって、とくに軽負荷使用時におい
ても顕著となってきた。このように、電解液が成層化す
ると、特に高比重となっている電池下部が充電され難く
なるため、低アンチモン化あるいはアンチモンフリー化
の場合では成層化の頻度が多くなる分、放電容量が極め
て早期に低下してしまう。Conventionally, this stratification of the electrolytic solution has been a problem only when the depth of discharge is large, that is, when a heavy load is used, but as described above, the antimony or the antimony-free has been adopted in recent years. It has become noticeable even during use. As described above, when the electrolytic solution is stratified, it is difficult to charge the lower part of the battery, which has a particularly high specific gravity. Therefore, in the case of low antimony or antimony free, the frequency of stratification increases, and the discharge capacity becomes extremely high. It will fall early.
【０００４】[0004]
【発明が解決しようとする課題】そこで、本発明の目的
とするところは、低アンチモン化あるいはアンチモンフ
リー化した鉛蓄電池において、重負荷、軽負荷を問わ
ず、放電容量が早期に低下することのない、極めて寿命
性能に優れた鉛蓄電池を提供するとともに、製造コスト
を大幅に削減でき、かつ鉛蓄電池のリサイクル化をも促
進できる鉛蓄電池を提供するこにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to reduce the discharge capacity of a lead storage battery with low antimony or antimony free, regardless of heavy load or light load. The present invention is to provide a lead-acid battery which has extremely excellent life performance, can significantly reduce manufacturing cost, and can also promote recycling of the lead-acid battery.
【０００５】[0005]
【課題を解決するための手段】本発明にかかる第一の発
明は、鉛蓄電池において、正又は／及び負極活物質に用
いられる鉛粉原料が、少なくとも、アンチモンを０．０
００２〜０．００２重量％、砒素を０．０００２〜０．
００２重量％、銅を０．０００５〜０．００３重量％、
銀を０．０００５〜０．００２重量％、錫を０．０００
１〜０．００３重量％、ビスマスを０．００２〜０．０
３重量％、そしてニッケルを０．０００１〜０．０００
３重量％含有した鉛合金であることを特徴とする。A first aspect of the present invention is a lead storage battery, wherein the lead powder raw material used for the positive and / or negative electrode active material contains at least 0.00 antimony.
002-0.002% by weight and arsenic 0.0002-0.
002% by weight, 0.0005 to 0.003% by weight of copper,
0.0005 to 0.002% by weight of silver and 0.000 of tin
1-0.003% by weight, bismuth 0.002-0.0
3% by weight, and 0.0001 to 0.000 of nickel
It is a lead alloy containing 3% by weight.
【０００６】第二の発明は、第一の発明に係る鉛蓄電池
において、正又は／及び負極活物質に用いられる鉛粉原
料が、鉛蓄電池スクラップなどから回収した鉛合金又は
／及び鉛化合物を還元炉中で還元した後、乾式精錬法に
よって不純物を除去した鉛合金であることを特徴とす
る。A second invention is the lead-acid battery according to the first invention, wherein the lead powder raw material used for the positive and / or negative electrode active material reduces a lead alloy or / and a lead compound recovered from lead-acid battery scrap or the like. It is a lead alloy obtained by removing impurities by a dry refining method after reduction in a furnace.
【０００７】第三の発明は、鉛蓄電池において、正又は
／及び負極活物質ペーストには、鉛粉原料の鉛比に対し
て少なくとも、アンチモンが０．０００２〜０．００２
重量％、砒素が０．０００２〜０．００２重量％、銅が
０．０００５〜０．００３重量％、銀が０．０００５〜
０．００２重量％、錫が０．０００１〜０．００３重量
％、ビスマスが０．００２〜０．０３重量％、そしてニ
ッケルが０．０００１〜０．０００３重量％含有されて
なることを特徴とする。A third invention is a lead-acid battery, wherein the positive or negative electrode active material paste contains at least 0.0002 to 0.002 antimony with respect to the lead ratio of the lead powder raw material.
% By weight, 0.0002-0.002% by weight of arsenic, 0.0005-0.003% by weight of copper, 0.0005-0.5% of silver
0.002% by weight, 0.0001 to 0.003% by weight of tin, 0.002 to 0.03% by weight of bismuth, and 0.0001 to 0.0003% by weight of nickel. To do.
【０００８】第四の発明は、第一、第二又は第三の発明
に係る鉛蓄電池において、極板の格子がアンチモンを
０．８〜３．０重量％含んでなる鉛−アンチモン系合金
又は実質的にアンチモンを含まない鉛合金であることを
特徴とする。A fourth invention is the lead-acid battery according to the first, second or third invention, wherein the grid of the electrode plate contains a lead-antimony alloy or 0.8-3.0% by weight of antimony. The lead alloy is substantially free of antimony.
【０００９】[0009]
【発明の実施の形態】本発明者らは、これまで鉛蓄電池
の正負極活物質に用いられてきた鉛粉に一種の元素ある
いは酸化物、水酸化物などの添加によって上述の性能改
善を試みてきたが、その結果は一長一短であり、必ずし
も満足のいくものではなかった。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have attempted to improve the above-mentioned performance by adding a kind of element, oxide, hydroxide or the like to lead powder which has been used as a positive and negative electrode active material for lead acid batteries. However, the results have both merits and demerits and were not always satisfactory.
【００１０】ところが、本発明者らは、複数種の元素等
の添加によってという発想に基づき鋭意研究した結果、
正又は／及び負極活物質ペーストの鉛粉原料である鉛に
少なくともアンチモン、砒素、銅、銀、錫、ビスマス、
およびニッケルを添加すると、いまだその理由は解明さ
れたわけではないので、組み合わせによる相乗効果がう
まく発揮されたとしか言いようがないが、この組み合わ
せによって寿命試験中に起こる電解液の成層化が改善で
きうることを見い出した。そして、さらに研究を重ね、
その組み合わせにおいて、各元素の割合によって成層化
の改善に大きな影響を与えることが明らかとなった。However, the inventors of the present invention have conducted diligent research based on the idea of adding plural kinds of elements and the like,
At least antimony, arsenic, copper, silver, tin, bismuth is added to lead, which is a lead powder raw material of the positive and / or negative electrode active material paste,
The addition of nickel and nickel has not been clarified yet, so it can only be said that the synergistic effect of the combination was successfully exerted, but this combination can improve the stratification of the electrolyte solution that occurs during the life test. Found out. And further research,
In the combination, it became clear that the ratio of each element had a great influence on the improvement of stratification.
【００１１】すなわち、これらの元素の量を特定するこ
とにより、極めて優れた寿命性能を有する高性能鉛蓄電
池の提供を可能にすることができる。実施例において
は、活物質ペーストの鉛粉原料である鉛合金の組成を鉛
と残部が上記元素であるものとしているが、活物質製造
時に上記元素を添加したものとしてもよい。That is, by specifying the amounts of these elements, it is possible to provide a high performance lead acid battery having extremely excellent life performance. In the examples, the composition of the lead alloy, which is the raw material of the lead powder of the active material paste, is such that lead and the balance are the above elements, but the above elements may be added during the production of the active material.
【００１２】さらに、本実施例では、正極格子合金とし
てアンチモンを１．７重量％および砒素を０．２５重量
％添加したものを用いたが、アンチモン量は比較的少な
いものほどその他の添加元素の効果が大きく、０．８〜
３重量％以下とすることが好ましい。砒素は０．１〜
０．４重量％のものが使用できる。また、鉛−アンチモ
ン系合金に一般的に用いられているセレン、硫黄等を添
加してもよい。Further, in the present embodiment, as the positive electrode grid alloy, 1.7% by weight of antimony and 0.25% by weight of arsenic were used, but if the amount of antimony is relatively small, other additive elements are added. Great effect, 0.8 ~
It is preferably 3% by weight or less. Arsenic is 0.1
0.4 wt% can be used. Further, selenium, sulfur and the like which are generally used in lead-antimony alloys may be added.
【００１３】加えて、正極格子に実質的にアンチモンを
含まない合金を用いた場合でも、上記と同様の効果が得
られる。むしろ、この場合では鉛−アンチモン系合金で
みられるような正極格子表面の腐食によるアンチモンの
溶出がないことから、アンチモン、砒素、銅、銀、錫、
ビスマス、鉄、亜鉛およびニッケルを含んだ鉛粉原料鉛
を用いることは、寿命試験中の電解液の成層化の抑制に
より一層効果がある。尚、本発明になる鉛粉原料の場
合、従来のように鉛の精製を厳しくせずともよいので、
結果として、鉛蓄電池スクラップなどから回収した鉛合
金及び鉛化合物を還元炉中で還元した後、乾式精錬法に
よって不純物を除去して得られた鉛を用いることが容易
にでき、製造コストの大幅な削減が可能となる。In addition, even when an alloy containing substantially no antimony is used for the positive electrode grid, the same effect as above can be obtained. Rather, in this case, since there is no elution of antimony due to the corrosion of the positive electrode grid surface as seen in the lead-antimony alloy, antimony, arsenic, copper, silver, tin,
Using lead powder raw material lead containing bismuth, iron, zinc and nickel is more effective in suppressing stratification of the electrolyte solution during the life test. In the case of the lead powder raw material according to the present invention, it is not necessary to strictly purify lead as in the conventional case,
As a result, it is possible to easily use the lead obtained by removing the impurities by the dry refining method after reducing the lead alloy and the lead compound recovered from the lead storage battery scrap in the reduction furnace, which leads to a large production cost. Reduction is possible.
【００１４】[0014]
【実施例】以下に本発明を実施例をもとに詳細する。EXAMPLES The present invention will be described in detail below based on examples.
【００１５】まず、従来使用されている電解精錬によっ
て製造されたＪＩＳ特種（JISH2105記載）に適合した鉛
を鉛粉原料として用いた（Ｎｏ．１）。First, lead, which has been used by conventional electrolytic refining and is compatible with the JIS special type (described in JIS H2105), was used as a lead powder raw material (No. 1).
【００１６】次に、上記電解精錬鉛にアンチモン、砒
素、銅、銀、錫、ビスマス、そしてニッケルを添加し
て、アンチモンを０．０００２重量％、砒素を０．００
０２重量％、銅を０．０００５重量％、銀を０．０００
５重量％、錫を０．０００１重量％、ビスマスを０．０
０２重量％、そしてニッケルを０．０００１重量％含有
させた本発明による鉛合金を鉛粉原料として用いた（Ｎ
ｏ．２）。Next, antimony, arsenic, copper, silver, tin, bismuth, and nickel are added to the electrolytically refined lead to add 0.0002% by weight of antimony and 0.00 of arsenic.
02% by weight, 0.0005% by weight of copper and 0.000 of silver
5% by weight, 0.0001% by weight tin, 0.0% bismuth
The lead alloy according to the present invention containing 02 wt% and 0.0001 wt% nickel was used as a lead powder raw material (N
o. 2).
【００１７】さらに、電解精錬鉛にアンチモン、砒素、
銅、銀、錫、ビスマス、そしてニッケルを添加して、ア
ンチモンを０．００２重量％、砒素を０．００２重量
％、銅を０．００３重量％、銀を０．００２重量％、錫
を０．００３重量％、ビスマスを０．０３重量％、そし
てニッケルを０．０００３重量％含有させた本発明によ
る鉛合金を鉛粉原料として用いた（Ｎｏ．３）。Furthermore, electrolytically refined lead is mixed with antimony, arsenic,
Copper, silver, tin, bismuth and nickel are added to add 0.002 wt% antimony, 0.002 wt% arsenic, 0.003 wt% copper, 0.002 wt% silver and 0 tin. The lead alloy according to the present invention containing 0.003% by weight, 0.03% by weight of bismuth, and 0.0003% by weight of nickel was used as a lead powder raw material (No. 3).
【００１８】比較のため、電解精錬鉛にアンチモン、砒
素、銅、銀、錫、ビスマス、そしてニッケルを添加し
て、アンチモンを０．００４重量％、砒素を０．００４
重量％、銅を０．００６重量％、銀を０．００５重量
％、錫を０．００６重量％、ビスマスを０．０５重量
％、そしてニッケルを０．０００５重量％含有させた本
発明による鉛合金を鉛粉原料として用いた（Ｎｏ．
４）。これら４種類の鉛粉原料である鉛の組成を表１に
示す。For comparison, antimony, arsenic, copper, silver, tin, bismuth, and nickel were added to electrolytically refined lead to 0.004% by weight of antimony and 0.004 of arsenic.
% Lead, 0.006% by weight of copper, 0.005% by weight of silver, 0.006% by weight of tin, 0.05% by weight of bismuth and 0.0005% by weight of nickel according to the invention. The alloy was used as a lead powder raw material (No.
4). Table 1 shows the composition of lead, which is the raw material for these four types of lead powder.
【００１９】[0019]
【表１】 なお、〓１の従来使用している電解精錬によって製造さ
れた鉛（ＪＩＳ特種）中のアンチモン、砒素、銅、銀、
錫、ビスマス、そしてニッケルは非常に少なく、その他
の元素として鉄と亜鉛がそれぞれ０．００００３重量
％、０．００００２重量％含まれていた。[Table 1] In addition, the antimony, arsenic, copper, silver in the lead (JIS special type) produced by the conventional electrolytic refining of 〓1
Tin, bismuth, and nickel were very small, and iron and zinc were contained as 0.00003% by weight and 0.00002% by weight, respectively, as other elements.
【００２０】そして、上記４種類の原料鉛から鉛粉を作
製した。作製された鉛粉中には、アンチモン、砒素、
銅、銀、錫、ビスマス、そしてニッケルが鉛比で原料鉛
のときと同量含まれていた。これらの鉛粉から調製され
たペーストとアンチモンを１．７重量％、砒素を０．２
５重量％含む鉛−アンチモン系合金製格子から常法によ
ってそれぞれ正極板を作製した。また、同じ鉛粉から調
製されたペーストと負極に従来使用されている鉛−カル
シウム−錫系格子からそれぞれ負極板を作製した。これ
らの正極板と負極板を組み合わせ、４種類の自動車用鉛
蓄電池５５Ｄ２３（JISD5301記載）を作製した。Then, lead powder was prepared from the above four kinds of raw material lead. In the produced lead powder, antimony, arsenic,
Copper, silver, tin, bismuth, and nickel were contained in the same lead ratio as the raw material lead. Paste prepared from these lead powders and antimony 1.7 wt%, arsenic 0.2
A positive electrode plate was prepared from a lead-antimony alloy grid containing 5% by weight by a conventional method. Also, a negative electrode plate was prepared from a paste prepared from the same lead powder and a lead-calcium-tin based grid that has been conventionally used for negative electrodes. By combining these positive electrode plates and negative electrode plates, four types of automotive lead storage batteries 55D23 (described in JIS D5301) were produced.
【００２１】これらの電池をJISD5301記載の軽負荷寿命
試験に供した。寿命試験中の３５６Ａ放電３０秒目電圧
の推移を第１図に、電解液の比重の推移を第２図に、そ
して電池の減液量を第３図にそれぞれ示す。These batteries were subjected to the light load life test described in JIS D5301. The transition of the voltage at 30 seconds after discharge of 356 A during the life test is shown in FIG. 1, the transition of the specific gravity of the electrolytic solution is shown in FIG. 2, and the liquid reduction amount of the battery is shown in FIG.
【００２２】第１図および第２図から以下のことがわか
った。すなわち、正極格子に鉛−低アンチモン系合金を
用いた場合、従来の電解精錬鉛を鉛粉原料に用いた電池
（電池Ｎｏ．１）では試験中に電解液の成層化を引き起
こし、比較的早期に寿命となったが、本発明による電池
（電池Ｎｏ．２および３）ではこれらに比べて優れた寿
命性能を示した。The following facts were found from FIGS. 1 and 2. That is, when a lead-low antimony-based alloy is used for the positive electrode grid, the battery (battery No. 1) using the conventional electrolytically refined lead as the lead powder raw material causes stratification of the electrolytic solution during the test, which is relatively early. However, the batteries according to the present invention (Batteries Nos. 2 and 3) exhibited excellent life performance as compared with these batteries.
【００２３】本発明により寿命性能が向上したのは、第
２図に示すように寿命試験中に起こる電解液の成層化が
アンチモン、砒素、銅、銀、錫、ビスマス、およびニッ
ケルの添加により抑制できたためであると考えられる。
これらの添加元素によって成層化を抑制できたのは、試
験中に負極に存在するこれら添加元素が充電中の電解液
の分解による水素ガス発生量をわずかに大きくして、発
生したガスが電解液を攪拌しながら大気中に放出される
ためである。The life performance is improved by the present invention, as shown in FIG. 2, the stratification of the electrolytic solution which occurs during the life test is suppressed by the addition of antimony, arsenic, copper, silver, tin, bismuth and nickel. This is probably because it was done.
It was possible to suppress stratification by these additional elements because these additional elements present in the negative electrode during the test slightly increased the amount of hydrogen gas generated by decomposition of the electrolytic solution during charging, and the generated gas was the electrolytic solution. This is because while being stirred, it is released into the atmosphere.
【００２４】負極に存在する添加元素は、初期から活物
質に含まれているものと試験中に正極活物質から電解液
に溶出して、負極に析出したものがあり、この成層化の
抑制は両者の影響が合わさって起こったものと考えられ
る。The additive elements present in the negative electrode include those contained in the active material from the initial stage and those eluted from the positive electrode active material into the electrolytic solution during the test and deposited on the negative electrode. It is considered that the effects of both were combined.
【００２５】しかし、これらを添加しすぎると、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
激しくなるために減液量が大きくなり、さらに電解液の
比重が上昇して、寿命に到っている（電池Ｎｏ．４）。However, if these are added too much, the hydrogen overvoltage of the negative electrode is remarkably lowered, the electrolytic solution is decomposed during overcharge violently, the amount of liquid reduction is increased, and the specific gravity of the electrolytic solution is further increased. , Has reached the end of its life (Battery No. 4).
【００２６】[0026]
【発明の効果】本発明にかかる第一の発明は、鉛蓄電池
において、正又は／及び負極活物質に用いられる鉛粉原
料が、少なくとも、アンチモンを０．０００２〜０．０
０２重量％、砒素を０．０００２〜０．００２重量％、
銅を０．０００５〜０．００３重量％、銀を０．０００
５〜０．００２重量％、錫を０．０００１〜０．００３
重量％、ビスマスを０．００２〜０．０３重量％、そし
てニッケルを０．０００１〜０．０００３重量％含有し
た鉛合金であることを特徴とする。According to the first aspect of the present invention, in the lead storage battery, the lead powder raw material used for the positive and / or negative electrode active material contains at least 0.0002 to 0.0 antimony.
02 wt%, arsenic 0.0002 to 0.002 wt%,
0.0005 to 0.003% by weight of copper and 0.000 of silver
5 to 0.002% by weight, 0.0001 to 0.003 of tin
%, Bismuth 0.002-0.03% by weight, and nickel 0.0001-0.0003% by weight, which is a lead alloy.
【００２７】第二の発明は、第一の発明に係る鉛蓄電池
において、正又は／及び負極活物質に用いられる鉛粉原
料が、鉛蓄電池スクラップなどから回収した鉛合金又は
／及び鉛化合物を還元炉中で還元した後、乾式精錬法に
よって不純物を除去した鉛合金であることを特徴とす
る。A second invention is the lead-acid battery according to the first invention, wherein the lead powder raw material used for the positive and / or negative electrode active material reduces a lead alloy or / and a lead compound recovered from lead-acid battery scrap or the like. It is a lead alloy obtained by removing impurities by a dry refining method after reduction in a furnace.
【００２８】第三の発明は、鉛蓄電池において、正又は
／及び負極活物質ペーストには、鉛粉原料の鉛比に対し
て少なくとも、アンチモンが０．０００２〜０．００２
重量％、砒素が０．０００２〜０．００２重量％、銅が
０．０００５〜０．００３重量％、銀が０．０００５〜
０．００２重量％、錫が０．０００１〜０．００３重量
％、ビスマスが０．００２〜０．０３重量％、そしてニ
ッケルが０．０００１〜０．０００３重量％含有されて
なることを特徴とする。A third aspect of the present invention is a lead-acid battery, wherein the positive and / or negative electrode active material paste contains at least 0.0002 to 0.002 antimony with respect to the lead ratio of the lead powder raw material.
% By weight, 0.0002-0.002% by weight of arsenic, 0.0005-0.003% by weight of copper, 0.0005-0.5% of silver
0.002% by weight, 0.0001 to 0.003% by weight of tin, 0.002 to 0.03% by weight of bismuth, and 0.0001 to 0.0003% by weight of nickel. To do.
【００２９】第四の発明は、第一、第二又は第三の発明
に係る鉛蓄電池において、極板の格子がアンチモンを
０．８〜３．０重量％含んでなる鉛−アンチモン系合金
又は実質的にアンチモンを含まない鉛合金であることを
特徴とする。A fourth invention is the lead-acid battery according to the first, second or third invention, wherein the grid of the electrode plate contains lead-antimony alloy or 0.8-3.0% by weight of antimony. The lead alloy is substantially free of antimony.
【００３０】本発明によれば、低アンチモン化あるいは
アンチモンフリー化した鉛蓄電池において、重負荷、軽
負荷を問わず、放電容量が早期に低下することのない、
極めて寿命性能に優れた鉛蓄電池を提供するとともに、
製造コストを大幅に削減でき、かつ鉛蓄電池のリサイク
ル化をも促進できる鉛蓄電池を提供することができる。
ゆえに、その工業的価値は極めて大である。According to the present invention, in a lead storage battery with low antimony or antimony free, the discharge capacity does not decrease early regardless of heavy load or light load.
In addition to providing lead acid batteries with extremely excellent life performance,
It is possible to provide a lead storage battery that can significantly reduce the manufacturing cost and promote recycling of the lead storage battery.
Therefore, its industrial value is extremely large.
【００３１】なお、本発明になる鉛蓄電池は、液式に限
らず、負極吸収式等のものであってもよいことはいうま
でもない。Needless to say, the lead-acid battery according to the present invention is not limited to the liquid type and may be a negative electrode absorption type or the like.
【図１】ＪＩＳ軽負荷寿命試験結果を示す図である。FIG. 1 is a diagram showing the results of a JIS light load life test.
【図２】ＪＩＳ軽負荷寿命試験における電解液比重の推
移を示す図である。FIG. 2 is a diagram showing changes in the specific gravity of an electrolyte in a JIS light load life test.
【図３】ＪＩＳ軽負荷寿命試験における減液量を示す図
である。FIG. 3 is a diagram showing a liquid reduction amount in a JIS light load life test.
Claims (4)
られる鉛粉原料が、少なくとも、アンチモンを０．００
０２〜０．００２重量％、砒素を０．０００２〜０．０
０２重量％、銅を０．０００５〜０．００３重量％、銀
を０．０００５〜０．００２重量％、錫を０．０００１
〜０．００３重量％、ビスマスを０．００２〜０．０３
重量％、そしてニッケルを０．０００１〜０．０００３
重量％含有した鉛合金であることを特徴とする鉛蓄電
池。1. The lead powder raw material used in the positive and / or negative electrode active material paste contains at least 0.00 antimony.
02-0.002% by weight, arsenic 0.0002-0.0
02% by weight, 0.0005 to 0.003% by weight of copper, 0.0005 to 0.002% by weight of silver, and 0.0001 of tin.
~ 0.003% by weight, 0.002-0.03 bismuth
% By weight, and 0.0001 to 0.0003 of nickel
A lead storage battery, which is a lead alloy containing wt%.
られる鉛粉原料が、鉛蓄電池スクラップなどから回収し
た鉛合金又は／及び鉛化合物を還元炉中で還元した後、
乾式精錬法によって不純物を除去した鉛合金であること
を特徴とする請求項１記載の鉛蓄電池。2. The lead powder raw material used for the positive and / or negative electrode active material paste, after reducing a lead alloy or / and a lead compound recovered from a lead storage battery scrap or the like in a reducing furnace,
The lead acid battery according to claim 1, which is a lead alloy from which impurities have been removed by a dry refining method.
鉛粉原料の鉛比に対して少なくとも、アンチモンが０．
０００２〜０．００２重量％、砒素が０．０００２〜
０．００２重量％、銅が０．０００５〜０．００３重量
％、銀が０．０００５〜０．００２重量％、錫が０．０
００１〜０．００３重量％、ビスマスが０．００２〜
０．０３重量％、そしてニッケルが０．０００１〜０．
０００３重量％含有されてなることを特徴とする鉛蓄電
池。3. The positive and / or negative electrode active material paste comprises:
Antimony is at least 0. 0 with respect to the lead ratio of the lead powder raw material.
0002-0.002 wt%, arsenic 0.0002-
0.002% by weight, 0.0005 to 0.003% by weight of copper, 0.0005 to 0.002% by weight of silver, 0.0% of tin
001-0.003% by weight, bismuth 0.002-
0.03% by weight, and 0.0001-0.
A lead-acid battery containing 0003% by weight.
０重量％含んでなる鉛−アンチモン系合金又は実質的に
アンチモンを含まない鉛合金であることを特徴とする請
求項１、２又は３記載の鉛蓄電池。4. The lattice of the electrode plate contains antimony in a range of 0.8-3.
The lead acid battery according to claim 1, 2 or 3, which is a lead-antimony alloy containing 0% by weight or a lead alloy containing substantially no antimony.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11533096A JP3876931B2 (en) | 1996-04-11 | 1996-04-11 | Lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11533096A JP3876931B2 (en) | 1996-04-11 | 1996-04-11 | Lead acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09283137A true JPH09283137A (en) | 1997-10-31 |
| JP3876931B2 JP3876931B2 (en) | 2007-02-07 |
Family
ID=14659899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11533096A Expired - Fee Related JP3876931B2 (en) | 1996-04-11 | 1996-04-11 | Lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3876931B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003142085A (en) * | 2001-11-02 | 2003-05-16 | Japan Storage Battery Co Ltd | Lead-acid battery |
| JP2003346888A (en) * | 2002-05-24 | 2003-12-05 | Matsushita Electric Ind Co Ltd | Lead-acid battery |
| WO2004038051A1 (en) * | 2002-10-24 | 2004-05-06 | Commonwealth Scientific And Industrial Research Organisation | Lead compositions for lead-acid batteries |
| JP2006066252A (en) * | 2004-08-27 | 2006-03-09 | Matsushita Electric Ind Co Ltd | Lead-acid storage battery |
| US7923155B2 (en) * | 2007-03-20 | 2011-04-12 | Northstar Battery Company, Llc | Lead-tin-silver-bismuth containing alloy for positive grid of lead acid batteries |
| JP2012089296A (en) * | 2010-10-18 | 2012-05-10 | Gs Yuasa Corp | Lead storage battery |
| WO2013062694A2 (en) * | 2011-09-21 | 2013-05-02 | Hollingsworth & Vose Company | Battery components with leachable metal ions and uses thereof |
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| CN110611090A (en) * | 2019-09-17 | 2019-12-24 | 广西科技大学 | Preparation method of positive active material of lead-acid storage battery |
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|---|---|---|---|---|
| JP2003142085A (en) * | 2001-11-02 | 2003-05-16 | Japan Storage Battery Co Ltd | Lead-acid battery |
| JP2003346888A (en) * | 2002-05-24 | 2003-12-05 | Matsushita Electric Ind Co Ltd | Lead-acid battery |
| JP4501330B2 (en) * | 2002-05-24 | 2010-07-14 | パナソニック株式会社 | Lead acid battery |
| WO2004038051A1 (en) * | 2002-10-24 | 2004-05-06 | Commonwealth Scientific And Industrial Research Organisation | Lead compositions for lead-acid batteries |
| JP2006066252A (en) * | 2004-08-27 | 2006-03-09 | Matsushita Electric Ind Co Ltd | Lead-acid storage battery |
| US7923155B2 (en) * | 2007-03-20 | 2011-04-12 | Northstar Battery Company, Llc | Lead-tin-silver-bismuth containing alloy for positive grid of lead acid batteries |
| US10535853B2 (en) | 2010-09-21 | 2020-01-14 | Hollingsworth & Vose Company | Glass compositions with leachable metal oxides and ions |
| JP2012089296A (en) * | 2010-10-18 | 2012-05-10 | Gs Yuasa Corp | Lead storage battery |
| WO2013062694A3 (en) * | 2011-09-21 | 2014-05-08 | Hollingsworth & Vose Company | Battery components with leachable metal ions and uses thereof |
| WO2013062694A2 (en) * | 2011-09-21 | 2013-05-02 | Hollingsworth & Vose Company | Battery components with leachable metal ions and uses thereof |
| US10637044B2 (en) | 2013-11-06 | 2020-04-28 | Northstar Battery Company, Llc | Corrosion resistant positive grid for lead-acid batteries |
| US9985276B2 (en) | 2013-11-06 | 2018-05-29 | Northstar Battery Company, Llc | Corrosion resistant positive grid for lead-acid batteries |
| CN109196688A (en) * | 2016-04-27 | 2019-01-11 | Rsr技术公司 | Lead-containing alloy and correlation technique and product |
| RU2699245C1 (en) * | 2016-04-27 | 2019-09-04 | АрЭсАр ТЕКНОЛОДЖИЗ, ИНК. | Lead-based alloy and corresponding methods and products |
| US10511022B2 (en) * | 2016-04-27 | 2019-12-17 | Rsr Technologies, Inc. | Lead-based alloy and related processes and products |
| US20170317351A1 (en) * | 2016-04-27 | 2017-11-02 | Rsr Technologies, Inc. | Lead-based alloy and related processes and products |
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| WO2022224884A1 (en) * | 2021-04-20 | 2022-10-27 | 株式会社Ｇｓユアサ | Lead storage battery |
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|---|---|
| JP3876931B2 (en) | 2007-02-07 |
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