JP4531159B2

JP4531159B2 - Manufacturing method of rolled sheet for lead storage battery electrode plate

Info

Publication number: JP4531159B2
Application number: JP19901799A
Authority: JP
Inventors: 雅彦小斉; 和八川原
Original assignee: GS Yuasa International Ltd
Current assignee: GS Yuasa International Ltd
Priority date: 1999-07-13
Filing date: 1999-07-13
Publication date: 2010-08-25
Anticipated expiration: 2019-07-13
Also published as: JP2001023645A

Description

【０００１】
【発明の属する技術分野】
本発明は、鉛蓄電池の極板に用いる圧延シートの表面に鉛−アンチモン合金等の鉛合金箔を張り付けた圧延シートの製造方法に関するものである。
【０００２】
【従来の技術】
現在、鉛蓄電池は自動車用や産業用をはじめとしてあらゆる分野で用いられており、軽量化、コストダウン、メンテナンス・フリー化、長寿命化、品質の安定化等が強く求められている。
【０００３】
鉛蓄電池に用いられている格子合金は鉛−アンチモン系と鉛−カルシウム−錫系に大別できるが、特に、近年はメンテナス・フリー特性が重要視されてきており、鉛−カルシウム−錫系合金がよく使用されるようになってきた。
【０００４】
一方、鉛蓄電池用格子は、主に鋳造方式またはエキスパンド加工方式あるいは打抜き加工方式等の機械加工方式によって製造されている。
【０００５】
鋳造方式の長所は、電気抵抗が小さくなる形状などをはじめとして任意の形状の格子が形成できる、格子の周囲をとり囲む枠が形成可能なため、機械的に変形しにくい格子を作ることができる、といったことなどがあげられる。短所としては、バッチ式であるために生産性に劣る、ペースト充填などの後工程に連結した一貫ラインとすることが困難である、薄い格子の場合には鋳造やその後のハンドリングが困難であることなどである。
【０００６】
これに対し、機械加工方式では、一般に、鉛−カルシウム−錫系合金を連続鋳造して得られた厚さ５〜３０ｍｍの鉛帯を多段圧延機によって圧延シートを作製し、その圧延シートをエキスパンド加工あるいは打ち抜き加工等の機械加工を施して格子を作製するものである。機械加工方式では格子の連続生産が可能であり、ペースト充填・乾燥工程まで一貫したラインを設置できることから、鋳造方式に比べて極めて生産性が高いという特徴を持っている。さらに、高出力化や軽量化のための薄い格子の製造やその後のペースト充填等も容易である。
【０００７】
しかし、一般に鉛−カルシウム−錫系合金を正極格子に用いると、格子と活物質との密着性がよくなく、早期に容量が低下することがあり、そのため、鉛蓄電池の極板に用いる圧延シート、特に正極板用圧延シートは、充填される活物質ペーストとの密着性を高めるために、鉛−カルシウム−錫系合金の基体表面に鉛−アンチモン系合金等の鉛合金箔を張り付けることが好ましい。一般にこの種の圧延シートは、鉛−カルシウム−錫系合金を連続鋳造して得られた厚さ５〜３０ｍｍの鉛帯上に所定厚さの鉛合金箔を載置して多段圧延機によって圧延することにより圧接一体化して得られ、その後、機械加工によって鉛蓄電池極板用格子にされる。
【０００８】
【発明が解決しようとする課題】
上記鉛合金箔は、通状コイル状に巻いたフープ材として供給されるが、連続生産される圧延シート製造工程においてこのフープ材の交換は非常に困難であった。フープ材の終末部に合わせて次のフープ材の頭部を隙間無く供給することは技術的に難しく、交換作業時にフープ材の非供給部が発生してしまうために多量の不良シートを発生させてしまっていた。
【０００９】
本発明は、かかる事情に対処するためになされたものであり、鉛合金箔のつなぎ目を重ね合わせて鉛帯上に供給することにより鉛合金箔を間断なく供給した鉛蓄電池極板用圧延シートの製造方法を提供することを目的としている。
【００１０】
【課題を解決するための手段】
前記課題を解決する本発明の鉛蓄電池極板用圧延シートの製造方法は、鉛帯の表面に鉛合金箔を載置して当該鉛帯と鉛合金箔とを合わせて圧延することによって、表面層と基体との合金組成が異なる多層構造の鉛蓄電池極板用圧延シートを製造する方法において、鉛合金箔の終末部が鉛帯上に供給された時に当該終末部に次の鉛合金箔の頭部を重ね合わせて供給することを特徴とする。このように圧延される鉛帯上に供給している鉛合金箔の終末部を次の鉛合金箔の頭部と一部重ね合わせて供給し、当該合金箔と鉛帯とを合わせて圧延することにより、合金箔を間断なく供給できるので、安定した圧延シートの生産ができるようになる。
【００１１】
鉛帯厚さに対する鉛合金箔厚さの割合が０．５％以上かつ４％以下であれば、重ねしろによる厚み増大が圧延工程におよぼす影響も小さく、より安定した生産が可能となり、好ましい。
【００１２】
また、鉛帯に鉛合金箔を供給する前に、あらかじめ鉛合金箔の重ねしろを抵抗溶接することが好ましい。鉛合金箔交換の自動化が容易に可能となるからである。
【００１３】
抵抗溶接としては、特に限定されるわけではないが、スポット溶接などが好ましく、また重ねしろの全部もしくは一部（１ヶ所以上）を溶接すればよく、抵抗溶接に用いる電極の形状や鉛合金箔の厚さに合わせた最適な、印加圧力、印加電流、周波数を決めてやればよい。
【００１４】
さらに、部分的に間隔を開けて鉛合金箔を順次カシメることにより鉛帯に食い込ませるための突起を有するカシメローラで、前記鉛帯に重ね合せた鉛合金箔をカシメると同時に鉛帯に食い込ませることが好ましい。鉛合金箔を所定位置に精度よく貼り付けることができるからである。
【００１５】
鉛合金箔は、フープ状のフープ材として供給することが好ましい。取り扱いが容易だからである。
【００１６】
【発明の実施の形態】
以下、本発明を実施例を用いて説明する。
【００１７】
鉛−カルシウム−錫合金からなる厚さ２０ｍｍ、幅１３０ｍｍの鉛帯を連続鋳造機により作製し、多段式圧延機により厚さ１．０ｍｍの圧延シートを製造する圧延シート製造装置を用いて次の実験を行った。なお、当該装置の連続鋳造機と多段式圧延機の間には鉛帯上に鉛−アンチモン合金箔を供給する装置が設けられており、フープ状の鉛合金箔を用いてこの供給を行っている。
【００１８】
フープ材（鉛合金箔）が消費され、その終末部が鉛帯上に供給されたときに、図１に示すように、当該終末部２に次のフープ材の頭部３を３０ｍｍ重ね合わせて供給し、フープ材２および３と鉛帯１とを多段式圧延機で圧延した。フープ材として供給した鉛合金箔には厚さ０．１、０．２、０．４、０．６、０．８および１．０ｍｍの６種類を用いた。
また、比較のために従来のフープ材交換時の鉛合金箔の供給、載置状態を図２に示す。図２（ａ）は正常時の状態で、（ｂ）は異常時の状態である。正常時にはフープ材の終末部２と次のフープ材の頭部３が密接しており、これを圧延しても何等問題ないが、異常時には両者の間に間隙が発生しこれを圧延するとこの間隙部分には鉛−アンチモン合金層がなく、不良シートとなることがわかる。鉛合金箔は薄くて柔らかいことから、従来の生産時には定位置につなぎ目を配置することは困難で、このような不良が発生することが多かった。
【００１９】
実験結果を表１に示す。また、鉛帯に対する鉛合金箔の厚さの比率を百分率で表1中に示す。
【００２０】
【表１】

【００２１】
このように鉛帯厚さに対する鉛合金箔厚さの比率が４％以下のときは鉛合金箔を重ね合わせて供給することにより良好な圧延シートが得られた。鉛合金箔の比率が５％の場合は重ねしろ部分に相当する圧延シートが平坦にならずに波打状に変形してしまった。これは、重ねしろ部分の厚みが大きく、圧延にともなうシートの伸び率が他の部位に比べて極端に大きかったためと考えられる。本来、この種の影響は鉛合金箔の厚さが小さくても多少は現れるはずであるが、鉛帯厚さに対する鉛合金箔厚さの比率が４％以下の場合にはこの歪みを圧延シート全体に分散できたために影響がみられなかったものと考えられる。
【００２２】
鉛帯厚さに対する鉛合金箔厚さの比率の下限値は本実施例では明らかにはならなかったが、０．５％未満の場合には鉛合金箔を貼付する効果自体が低減するため貼付するメリットが少ない。
【００２３】
本実施例では厚さ２０ｍｍの鉛帯を用いたが、鉛帯の厚さを変えても、鉛合金箔厚さの比率を上述した範囲とすることにより、好ましい圧延シートの状態となり得る。
【００２４】
なお、本実施例では鉛合金箔の重ねしろを３０ｍｍとしたが、１ｍｍ程度以上の重ねしろがあれば充分で、重ねしろが３００ｍｍ以上あっても無駄なだけである。
【００２５】
また、本実施例では鉛帯上に鉛合金箔を載置しながら重ねしろを設けたが、あらかじめ鉛合金箔の重ねしろを抵抗溶接によって接続した後に鉛帯上に載置してもよい。抵抗溶接を用いる場合には重ねしろの全部もしくは一部（１ヶ所以上）を溶接すればよく、抵抗溶接に用いる電極の形状や鉛合金箔の厚さに合わせた最適な、印加圧力、印加電流、周波数を決めてやればよい。この方法を用いれば鉛合金箔のフープ材交換時の自動化も容易になる。
【００２６】
図３に示すように部分的に間隔を開けて鉛合金箔７を順次カシメることにより鉛帯に食い込ませるための突起４ａを有するカシメローラ４で、鉛合金箔の通常部分だけでなく、重ね合せた鉛合金箔もカシメると同時に鉛帯に食い込ませると、重ね合わせた鉛合金箔も所定位置により一層精度よく貼り付けることができる。
【００２７】
【発明の効果】
以上の説明から明らかなように、本発明による鉛蓄電池極板用圧延シートの製造方法によれば、鉛合金箔の交換時に鉛合金箔の終末部が鉛帯上に供給された時に当該終末部に次の鉛合金箔の頭部を重ね合わせて供給することにより鉛合金箔を間断なく貼付した鉛蓄電池極板用圧延シートが得られるので、圧延シートの生産が安定してでき、品質の向上、不良率の低減など、その工業的価値は甚だ大なるものである。
【図面の簡単な説明】
【図１】本発明の一実施形態を示すものであって、鉛合金箔のつなぎ目を示す斜視図である。
【図２】従来例を示すものであって、（ａ）は正常時の状態で、（ｂ）は異常時の状態を示すものである。
【図３】本発明の一実施形態を示すものであって、鉛帯に鉛合金箔をカシメる構成を示す部分拡大斜視図である。
【符号の説明】
１鉛帯
２フープ材（鉛合金箔）の終末部
３フープ材（鉛合金箔）の頭部
４カシメローラ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a rolled sheet in which a lead alloy foil such as a lead-antimony alloy is attached to the surface of a rolled sheet used for an electrode plate of a lead storage battery.
[0002]
[Prior art]
Currently, lead-acid batteries are used in various fields including automobiles and industrial use, and there are strong demands for weight reduction, cost reduction, maintenance-free, longer life, and quality stabilization.
[0003]
Lattice alloys used in lead-acid batteries can be broadly classified into lead-antimony and lead-calcium-tin, but in recent years, maintenance-free characteristics have been regarded as important. Lead-calcium-tin alloys Has become popular.
[0004]
On the other hand, the lead-acid battery grid is manufactured mainly by a machining method such as a casting method, an expanding method, or a punching method.
[0005]
The advantage of the casting method is that it can form a lattice of any shape, including a shape with low electrical resistance, and can form a frame that surrounds the periphery of the lattice, making it difficult to mechanically deform And so on. Disadvantages are inferior productivity due to the batch type, and it is difficult to make an integrated line connected to the subsequent process such as paste filling. In the case of a thin grid, casting and subsequent handling are difficult. Etc.
[0006]
On the other hand, in the machining method, in general, a rolled sheet is produced by a multi-stage rolling machine using a lead strip having a thickness of 5 to 30 mm obtained by continuously casting a lead-calcium-tin alloy, and the rolled sheet is expanded. The grating is produced by machining or punching. The machining method allows continuous production of lattices and has a feature that the productivity is extremely high compared to the casting method because a consistent line can be set up to the paste filling and drying process. Furthermore, it is easy to manufacture a thin grid for higher output and lighter weight, and then paste filling.
[0007]
However, in general, when a lead-calcium-tin alloy is used for the positive electrode lattice, the adhesion between the lattice and the active material is not good, and the capacity may be reduced at an early stage. Therefore, a rolled sheet used for the electrode plate of a lead storage battery. In particular, a rolled sheet for a positive electrode plate may be bonded with a lead alloy foil such as a lead-antimony alloy on the surface of a lead-calcium-tin alloy substrate in order to improve adhesion to the filled active material paste. preferable. In general, this kind of rolled sheet is rolled by a multi-stage rolling mill with a lead alloy foil having a predetermined thickness placed on a 5 to 30 mm thick lead strip obtained by continuously casting a lead-calcium-tin alloy. To obtain a lead storage battery electrode grid by machining.
[0008]
[Problems to be solved by the invention]
The lead alloy foil is supplied as a hoop material wound in a continuous coil shape, but it has been very difficult to replace the hoop material in a continuously produced rolled sheet manufacturing process. It is technically difficult to supply the head of the next hoop material without gaps in line with the end portion of the hoop material, and a non-feeding portion of the hoop material is generated during replacement work, resulting in a large amount of defective sheets. It was.
[0009]
The present invention has been made in order to cope with such a situation. A rolled sheet for a lead storage battery electrode plate in which the lead alloy foil is supplied without interruption by overlapping the joints of the lead alloy foil on the lead strip. The object is to provide a manufacturing method.
[0010]
[Means for Solving the Problems]
The method for producing a rolled sheet for a lead-acid battery electrode plate of the present invention that solves the above-mentioned problems is achieved by placing a lead alloy foil on the surface of the lead strip and rolling the lead strip and the lead alloy foil together to roll the surface. In the method of manufacturing a rolled sheet for a lead storage battery electrode plate having a multilayer structure with different alloy compositions of the layer and the substrate, when the terminal part of the lead alloy foil is supplied onto the lead strip, The head is superposed and supplied . The end part of the lead alloy foil supplied on the lead strip to be rolled in this way is supplied by partially overlapping the head of the next lead alloy foil, and the alloy foil and the lead strip are rolled together. Thus, the alloy foil can be supplied without interruption, so that a stable rolled sheet can be produced.
[0011]
If the ratio of the thickness of the lead alloy foil to the thickness of the lead strip is 0.5% or more and 4% or less, an increase in the thickness due to the overlap margin has a small influence on the rolling process, which is preferable because more stable production is possible.
[0012]
Moreover, it is preferable to resistance-weld the overlap of the lead alloy foil in advance before supplying the lead alloy foil to the lead strip. This is because the lead alloy foil replacement can be easily automated.
[0013]
The resistance welding is not particularly limited, but spot welding or the like is preferable, and all or a part (one or more) of the overlap may be welded. The shape of the electrode used for the resistance welding or the lead alloy foil The optimum applied pressure, applied current, and frequency may be determined in accordance with the thickness.
[0014]
Further, a caulking roller having protrusions for biting into the lead band by sequentially caulking the lead alloy foil with partial spacing, and simultaneously caulking the lead alloy foil superimposed on the lead band into the lead band Preferably. This is because the lead alloy foil can be attached to a predetermined position with high accuracy.
[0015]
The lead alloy foil is preferably supplied as a hoop-shaped hoop material. This is because handling is easy.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described using examples.
[0017]
Using a rolled sheet manufacturing apparatus for manufacturing a lead sheet made of a lead-calcium-tin alloy having a thickness of 20 mm and a width of 130 mm by a continuous casting machine and manufacturing a rolled sheet having a thickness of 1.0 mm by a multistage rolling mill, The experiment was conducted. A device for supplying lead-antimony alloy foil on the lead strip is provided between the continuous casting machine and the multi-stage rolling mill of the device, and this supply is performed using a hoop-shaped lead alloy foil. Yes.
[0018]
When the hoop material (lead alloy foil) is consumed and its end portion is supplied onto the lead strip, as shown in FIG. 1, the head portion 3 of the next hoop material is overlapped with the end portion 2 by 30 mm. The

hoop materials

2 and 3 and the lead strip 1 were rolled by a multi-stage rolling mill. Six types of lead alloy foils having a thickness of 0.1, 0.2, 0.4, 0.6, 0.8, and 1.0 mm were used as the hoop material.
For comparison, FIG. 2 shows the supply and placement state of a lead alloy foil when a conventional hoop material is replaced. FIG. 2A shows a normal state, and FIG. 2B shows an abnormal state. In the normal state, the end portion 2 of the hoop material and the head portion 3 of the next hoop material are in close contact with each other, and there is no problem even if this is rolled. It can be seen that there is no lead-antimony alloy layer in the part, resulting in a defective sheet. Since lead alloy foils are thin and soft, it is difficult to place joints in place during conventional production, and such defects often occur.
[0019]
The experimental results are shown in Table 1. In addition, Table 1 shows the ratio of the thickness of the lead alloy foil to the lead strip as a percentage.
[0020]
[Table 1]

[0021]
Thus, when the ratio of the lead alloy foil thickness to the lead strip thickness was 4% or less, a good rolled sheet was obtained by supplying the lead alloy foil in an overlapping manner. When the ratio of the lead alloy foil was 5%, the rolled sheet corresponding to the overlapped portion did not become flat but was deformed in a wavy shape. This is presumably because the thickness of the overlapping portion was large and the elongation percentage of the sheet accompanying rolling was extremely large compared to other parts. Originally, this kind of effect should appear to some extent even if the thickness of the lead alloy foil is small, but if the ratio of the lead alloy foil thickness to the lead strip thickness is 4% or less, this distortion is reduced to the rolled sheet. It is thought that there was no effect because it could be dispersed throughout.
[0022]
The lower limit value of the ratio of the lead alloy foil thickness to the lead strip thickness was not clarified in this example, but if it is less than 0.5%, the effect of applying the lead alloy foil itself is reduced to reduce the effect. There are few merits to do.
[0023]
In this example, a lead strip having a thickness of 20 mm was used. However, even if the lead strip thickness is changed, a preferable rolled sheet state can be obtained by setting the ratio of the lead alloy foil thickness within the above-described range.
[0024]
In this embodiment, the lead alloy foil overlap is 30 mm. However, an overlap of about 1 mm or more is sufficient, and even if the overlap is 300 mm or more, it is only useless.
[0025]
In this embodiment, the overlap is provided while the lead alloy foil is placed on the lead strip. However, the lead alloy foil may be placed on the lead strip after the overlap of the lead alloy foil is connected in advance by resistance welding. When resistance welding is used, all or a part of the overlap (one or more) may be welded, and the optimum applied pressure and applied current according to the shape of the electrode used for resistance welding and the thickness of the lead alloy foil You just have to decide the frequency. If this method is used, automation at the time of replacing the hoop material of the lead alloy foil is facilitated.
[0026]
As shown in FIG. 3, a caulking roller 4 having protrusions 4a for biting into the lead strip by sequentially caulking the lead alloy foil 7 with partial spacing, as well as the normal portion of the lead alloy foil. If the lead alloy foil is squeezed at the same time as it is squeezed into the lead strip, the superposed lead alloy foil can be attached more accurately at a predetermined position.
[0027]
【The invention's effect】
As is apparent from the above description, according to the method for manufacturing a rolled sheet for a lead storage battery electrode plate according to the present invention, when the terminal part of the lead alloy foil is supplied onto the lead strip when the lead alloy foil is replaced , the terminal part is concerned. The rolled sheet for the lead storage battery plate with the lead alloy foil attached without interruption can be obtained by supplying the following lead alloy foil heads on top of each other, enabling stable production of the rolled sheet and improving quality. The industrial value, such as the reduction of defective rate, is extremely large.
[Brief description of the drawings]
FIG. 1 is a perspective view showing a joint of lead alloy foil according to an embodiment of the present invention.
2A and 2B show a conventional example, in which FIG. 2A shows a normal state and FIG. 2B shows an abnormal state.
FIG. 3 is a partially enlarged perspective view showing an embodiment of the present invention and showing a structure in which a lead alloy foil is caulked on a lead belt.
[Explanation of symbols]
1 Lead belt 2 End portion of hoop material (lead alloy foil) 3 Head portion of hoop material (lead alloy foil) 4 Caulking roller

Claims

By rolling a lead alloy foil on the surface of the lead strip and rolling the lead strip and the lead alloy foil together, a rolled sheet for a lead storage battery electrode plate having a multilayer structure with a different alloy composition between the surface layer and the substrate is obtained. In the manufacturing method, when the terminal part of the lead alloy foil is supplied onto the lead belt, the head of the next lead alloy foil is supplied to the terminal part in a superimposed manner, and the rolled sheet for the lead storage battery electrode plate is provided. Manufacturing method.

The method for producing a rolled sheet for a lead storage battery electrode plate according to claim 1, wherein the lead alloy foil is overlapped by resistance welding in advance before the lead alloy foil is placed on the lead strip.

A caulking roller having protrusions for biting into the lead band by sequentially caulking the lead alloy foil with a partial spacing, and simultaneously caulking the lead alloy foil superimposed on the lead band into the lead band The manufacturing method of the rolling sheet for lead acid battery electrode plates of Claim 1 or 2 characterized by these.