JP2002216773A - Positive electrode collector for lead acid battery and lead acid battery using the same - Google Patents

Positive electrode collector for lead acid battery and lead acid battery using the same

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Publication number
JP2002216773A
JP2002216773A JP2001008314A JP2001008314A JP2002216773A JP 2002216773 A JP2002216773 A JP 2002216773A JP 2001008314 A JP2001008314 A JP 2001008314A JP 2001008314 A JP2001008314 A JP 2001008314A JP 2002216773 A JP2002216773 A JP 2002216773A
Authority
JP
Japan
Prior art keywords
current collector
positive electrode
lead
surface layer
electrode current
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.)
Pending
Application number
JP2001008314A
Other languages
Japanese (ja)
Inventor
Yuichi Okada
祐一 岡田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Storage Battery Co Ltd
Original Assignee
Japan Storage Battery Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan Storage Battery Co Ltd filed Critical Japan Storage Battery Co Ltd
Priority to JP2001008314A priority Critical patent/JP2002216773A/en
Publication of JP2002216773A publication Critical patent/JP2002216773A/en
Pending legal-status Critical Current

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Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a lead acid battery having self-discharging and electrolyte reducing characteristic equal to a case using a Pb-Ca alloy collector for a positive electrode and improved life performance. SOLUTION: This positive electrode collector for the lead acid battery comprises a surface layer provided on part of the surface of a lead alloy or lead base material containing no Sb, the surface layer being a tin alloy layer containing one or more metal selected from alkaline metals and alkaline earth metals. The alkaline metal and/or the alkaline earth metal in the surface layer is 0.1-10 wt.%. The thickness of the surface layer is 1 μm or more an the thickness of the base material is 10% or less.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、鉛蓄電池に関す
る。
[0001] The present invention relates to a lead storage battery.

【0002】[0002]

【従来の技術】従来、鉛蓄電池における正極板の集電体
にはPb−Sb系合金が用いられてきた。しかし、この
合金を用いた電池は自己放電や電解液の減少が大きく、
メンテナンスフリータイプの電池や密閉型電池に使用す
ることは困難であった。そこで、自己放電や電解液の減
液を抑制し、メンテナンスフリー化を図るために、たと
えばCaを0.04〜0.12wt%含むPb−Ca系
合金などのSbを含まない鉛合金が用いられるようにな
ってきた。
2. Description of the Related Art Conventionally, a Pb-Sb alloy has been used as a current collector of a positive electrode plate in a lead storage battery. However, batteries using this alloy have a large self-discharge and decrease in electrolyte,
It has been difficult to use it for maintenance-free batteries and sealed batteries. Therefore, in order to suppress self-discharge and electrolyte reduction, and achieve maintenance-free operation, a lead alloy containing no Sb, such as a Pb-Ca-based alloy containing 0.04 to 0.12 wt% of Ca, is used. It has become.

【0003】[0003]

【発明が解決しようとする課題】しかし、正極集電体に
Sbを含まない鉛合金を用いた電池は、Pb−Sb系合
金を用いた電池よりも早期に容量が低下することがあ
る。この原因として、正極集電体と活物質との密着性が
悪くなる、または集電体に放電しやすい腐食層が形成さ
れる、などが考えられるが、いずれにしてもSbを含ま
ない正極集電体を用いた電池では、集電体の腐食層が放
電して集電体と活物質との界面に不働態層が形成されや
すく、活物質が充分放電できなくなるという問題があ
る。
However, the capacity of a battery using a lead alloy containing no Sb for the positive electrode current collector may decrease earlier than the capacity of a battery using a Pb-Sb alloy. This may be due to poor adhesion between the positive electrode current collector and the active material, or the formation of a corrosive layer that easily discharges on the current collector. In a battery using a current collector, there is a problem that a corrosive layer of the current collector is discharged and a passive layer is easily formed at an interface between the current collector and the active material, and the active material cannot be sufficiently discharged.

【0004】したがって、Sbを含まない鉛合金を正極
集電体に用いた電池の寿命性能を向上させるためには、
正極集電体と活物質との密着性を改善する、または放電
しにくい腐食層を形成させることが有効であると考えら
れる。この改善のための1つの方法として、Pb−Ca
系合金正極集電体の表面にPb−Sb系合金層を形成さ
せることが提案されている(特開昭63−148557
号公報)。
Therefore, in order to improve the life performance of a battery using a lead alloy containing no Sb for the positive electrode current collector,
It is considered effective to improve the adhesion between the positive electrode current collector and the active material or to form a corrosion layer that is difficult to discharge. As one method for this improvement, Pb-Ca
It has been proposed to form a Pb-Sb-based alloy layer on the surface of a system-based alloy positive electrode current collector (JP-A-63-148557).
No.).

【0005】この方法を用いれば、早期に容量が低下す
ることを防止でき、かつ減液もPb−Sb系合金の集電
体を用いたものに比べて改善されることが知られてい
る。しかし、この方法でも、集電体表面のみとはいえS
bを用いているために、Sbが電解液に溶出して負極に
析出し、水素過電圧を低下させるため、Pb−Ca系合
金集電体と同等には自己放電や減液を抑えることができ
ないという問題があった。特に、定電圧で充電される用
途の電池にこの方法を用いると、熱逸走や電解液の涸渇
(ドライアウト)が生じて早期に寿命に達するという問
題があった。
[0005] It is known that the use of this method can prevent the capacity from being reduced at an early stage, and the liquid reduction can be improved as compared with the case using a current collector of a Pb-Sb-based alloy. However, even with this method, the S
Since b is used, Sb elutes in the electrolytic solution and precipitates on the negative electrode to reduce the hydrogen overvoltage, so that self-discharge and liquid reduction cannot be suppressed as well as the Pb-Ca-based alloy current collector. There was a problem. In particular, when this method is used for a battery that is charged at a constant voltage, there is a problem in that thermal runaway and depletion (dryout) of the electrolyte solution occur and the life of the battery is quickly reached.

【0006】本発明の課題は、自己放電や電解液の減少
をPb−Ca系合金集電体を用いた場合と同等に抑え、
なおかつ活物質と正極集電体表面に生成する腐食層との
密着性、または腐食層の組成を改善して集電体と活物質
との界面に不働態層が形成されるのを防ぎ、寿命性能を
向上させた鉛蓄電池を提供することにある。
[0006] An object of the present invention is to suppress self-discharge and decrease in electrolyte solution as well as when a Pb-Ca-based alloy current collector is used.
In addition, by improving the adhesion between the active material and the corroded layer formed on the surface of the positive electrode current collector, or by improving the composition of the corroded layer, a passive layer is prevented from being formed at the interface between the current collector and the active material. It is to provide a lead storage battery with improved performance.

【0007】[0007]

【課題を解決するための手段】上記課題を解決するた
め、請求項1に記載の発明の鉛蓄電池用正極集電体で
は、基材の表面の一部に表面層を有する鉛蓄電池用正極
集電体であって、前記基材がSbを含まない鉛合金また
は鉛であり、前記表面層がアルカリ金属およびアルカリ
土類金属から選択された金属の1以上を含むスズ合金層
であることを特徴とする。
According to a first aspect of the present invention, there is provided a positive electrode current collector for a lead storage battery having a surface layer on a part of the surface of a substrate. An electrical conductor, wherein the base material is a lead alloy or lead not containing Sb, and the surface layer is a tin alloy layer containing one or more metals selected from alkali metals and alkaline earth metals. And

【0008】請求項2に記載の発明の鉛蓄電池用正極集
電体では、請求項1に記載の発明において、上記表面層
中のアルカリ金属および/またはアルカリ土類金属量が
0.1〜10wt%であることを特徴とする。
[0008] In the positive electrode current collector for a lead storage battery according to the second aspect of the present invention, the amount of alkali metal and / or alkaline earth metal in the surface layer is 0.1 to 10 wt. %.

【0009】請求項3に記載の発明の鉛蓄電池用正極集
電体では、請求項1、または2に記載の発明において、
上記表面層の厚みが1μm以上であり、かつ基材の厚み
の10%以下であることを特徴とする。請求項4に記載
の発明の鉛蓄電池用正極集電体では、請求項1、2、ま
たは3に記載の発明において、集電体の集電耳部のう
ち、少なくとも溶接されてストラップと一体化する部分
には上記表面層を有しないことを特徴とする。
In the positive electrode current collector for a lead storage battery according to the third aspect of the present invention, in the first or second aspect of the invention,
The thickness of the surface layer is 1 μm or more and 10% or less of the thickness of the substrate. According to a fourth aspect of the present invention, in the positive electrode current collector for a lead storage battery, at least one of the current collecting ears of the current collector is welded to be integrated with the strap. It is characterized in that the surface layer does not have the surface layer.

【0010】請求項5に記載の発明の鉛蓄電池用正極集
電体では、請求項1、2、3、または5に記載の発明に
おいて、集電体がエキスパンド加工または打ち抜き加工
されてなる格子またはシート状であることを特徴とす
る。
According to a fifth aspect of the present invention, there is provided a positive electrode current collector for a lead storage battery according to the first, second, third, or fifth aspect, wherein the current collector is expanded or stamped. It is characterized by being sheet-shaped.

【0011】請求項6に記載の発明の鉛蓄電池用正極集
電体では、請求項5に記載の発明において、Sbを含ま
ない鉛合金もしくは鉛の板の一面または両面に、アルカ
リ金属およびアルカリ土類金属から選択された金属の1
以上を含むスズ合金のシートを重ね合わせたものを圧延
することにより一体化された鉛合金シートから加工され
てなることを特徴とする。そして、請求項7に記載の発
明の鉛蓄電池では、請求項1、2、3、4、5、または
6に記載の正極集電体を用いたことを特徴とする。
According to a sixth aspect of the present invention, there is provided a positive electrode current collector for a lead storage battery according to the fifth aspect, wherein one or both surfaces of a lead alloy or lead plate containing no Sb are provided with an alkali metal and an alkaline earth. One of the metals selected from the class of metals
It is characterized by being processed from an integrated lead alloy sheet by rolling a stack of tin alloy sheets including the above. A lead storage battery according to a seventh aspect of the present invention uses the positive electrode current collector according to the first, second, third, fourth, fifth, or sixth aspect.

【0012】[0012]

【発明の実施の形態】以下に、本発明の好ましい実施の
形態を説明するが、本発明は以下の説明に限定されるも
のではない。本発明は、Sbを含まない鉛合金からなる
正極集電体の基材表面にアルカリ金属またはアルカリ土
類金属の少なくとも1種以上を含むスズ合金層を設ける
ことを特徴とするものである。なお、本発明のスズ合金
とは、Sbを積極的に含んでいないものをいう。
DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below, but the present invention is not limited to the following description. The present invention is characterized in that a tin alloy layer containing at least one of an alkali metal and an alkaline earth metal is provided on a substrate surface of a positive electrode current collector made of a lead alloy containing no Sb. In addition, the tin alloy of the present invention means an alloy that does not actively contain Sb.

【0013】正極集電体表面にアルカリ金属またはアル
カリ土類金属の少なくとも1種以上を含むスズ合金層を
設けることによって、正極活物質と正極集電体との密着
性や正極集電体腐食層の形態や組成を改善することがで
き、集電体と活物質との界面に不働態層が形成されるの
を防ぐことができる。アルカリ金属またはアルカリ土類
金属の含有量は0.1〜10wt%の範囲が好ましい。
また、これらの2種類以上を組み合わせた場合も同様の
効果が得られる。
By providing a tin alloy layer containing at least one of an alkali metal and an alkaline earth metal on the surface of the positive electrode current collector, the adhesion between the positive electrode active material and the positive electrode current collector and the positive electrode current collector corrosion layer Can be improved, and the formation of a passive layer at the interface between the current collector and the active material can be prevented. The content of the alkali metal or alkaline earth metal is preferably in the range of 0.1 to 10% by weight.
Similar effects can be obtained when two or more of these are combined.

【0014】表面層に含まれるアルカリ金属またはアル
カリ土類金属は、表面層が腐食して電解液中に溶出して
も負極に析出して負極の水素過電圧を低下させることが
ない。また、スズはSbに比べて水素過電圧が高いた
め、自己放電や電解液の減少を抑えることができる。
The alkali metal or alkaline earth metal contained in the surface layer is not deposited on the negative electrode even if the surface layer is corroded and eluted in the electrolytic solution, and does not lower the hydrogen overvoltage of the negative electrode. Further, since tin has a higher hydrogen overvoltage than Sb, it is possible to suppress self-discharge and a decrease in electrolyte solution.

【0015】基材とは、集電体を形成する母材となる部
分である。材質はSbを含まない合金である。ここで
「Sbを含まない」とは、積極的に含まないという意味
であって、例えば不純物としてでも含有しておれば、本
発明から除かれるというものではない。また、Sbを含
まない鉛合金とは特に限定されるものではないが、純
鉛、Caを含有するPb−Ca系合金、Snを含有する
Pb−Sn系合金などがある。CaやSnの量として
は、Caは0.12wt%以下、Snは3wt%以下が
好ましい。また、Al、Ag、Se、Bi等、鉛合金の
特性を改善するために従来から添加されて用いられる元
素を含有する鉛合金も同様に好ましい。
The base material is a portion serving as a base material for forming a current collector. The material is an alloy containing no Sb. Here, “does not contain Sb” means that it is not contained positively, and is not excluded from the present invention if it is contained as an impurity, for example. The lead alloy containing no Sb is not particularly limited, but includes pure lead, a Pb-Ca-based alloy containing Ca, a Pb-Sn-based alloy containing Sn, and the like. As the amounts of Ca and Sn, Ca is preferably 0.12% by weight or less, and Sn is preferably 3% by weight or less. Further, a lead alloy containing an element conventionally added and used to improve the properties of the lead alloy, such as Al, Ag, Se, and Bi, is also preferable.

【0016】合金表面層の厚みはあまり薄いと効果が小
さく、反対に厚すぎるとコストが高くなる等の問題が生
じるため、1μm以上で、かつ、集電体基材の厚みの1
0%以下の厚みであることが望ましい。合金表面層が集
電体を覆う部分は、少なすぎると効果が小さく、また、
全面を覆ってしまうとかえって極板の化成性が損なわれ
るため、集電体全体の見かけ表面積の1/10以上、2
/3以下が覆われていることが好ましい。また、集電体
の集電耳部に該表面層を設けると、ストラップと集電耳
との溶接部が腐食しやすくなるため、溶接されてストラ
ップと一体化する部分には該表面層をもうけない方がよ
い。
If the thickness of the alloy surface layer is too small, the effect is small. On the other hand, if the thickness is too large, problems such as an increase in cost arise. Therefore, the thickness is 1 μm or more and the thickness of the current collector base material is 1
The thickness is desirably 0% or less. The portion where the alloy surface layer covers the current collector has a small effect if it is too small, and
If the entire surface of the current collector is covered, the chemical properties of the electrode plate will be impaired.
/ 3 or less is preferably covered. Further, if the surface layer is provided on the current collecting ear portion of the current collector, a welded portion between the strap and the current collecting ear is easily corroded. Therefore, the surface layer is provided on a portion which is welded and integrated with the strap. Better not.

【0017】集電体の形態は特に限定されるものではな
いが、生産性や加工性の点からエキスパンド格子、打ち
抜き格子またはシート状が好ましい。
The form of the current collector is not particularly limited, but is preferably an expanded lattice, a punched lattice or a sheet from the viewpoint of productivity and workability.

【0018】[0018]

【実施例】以下、本発明の実施例について説明する。Embodiments of the present invention will be described below.

【0019】(実施例1)鉛合金基材上に、上記表面層
を設けた集電体の一例として、エキスパンド格子に適用
した場合について述べる。
(Example 1) A case where the present invention is applied to an expanded lattice as an example of a current collector having the above surface layer provided on a lead alloy base material will be described.

【0020】まず、基材である厚み10mmのPb−
0.07wt%Ca−1.3wt%Sn合金の連続鋳造
板の表面(片面)に、厚み0.1mmのSn−Li、S
n−Na、Sn−K、Sn−Mg、Sn−Ca、Sn−
Sr、Sn−Ba合金シートを重ね合わせ、圧延ローラ
で圧延することによって一体化された厚み1.0mmの
圧延シートを作製した。これによって、基材の片面に厚
さ約10μmのSn−アルカリ金属またはアルカリ土類
金属合金表面層を有する圧延シートを作製した。この圧
延シートを図1、2に示す。表面層のスズ合金への各元
素の添加量は0.5wt%とした。
First, Pb-
On a surface (one side) of a continuous cast plate of 0.07 wt% Ca-1.3 wt% Sn alloy, a 0.1 mm thick Sn-Li, S
n-Na, Sn-K, Sn-Mg, Sn-Ca, Sn-
The Sr and Sn-Ba alloy sheets were overlapped and rolled by a rolling roller to produce an integrated rolled sheet having a thickness of 1.0 mm. As a result, a rolled sheet having a Sn-alkali metal or alkaline earth metal alloy surface layer having a thickness of about 10 μm on one surface of the substrate was produced. This rolled sheet is shown in FIGS. The amount of each element added to the tin alloy of the surface layer was 0.5 wt%.

【0021】次に、作製した圧延シートをレシプロ式エ
キスパンド機を用いて網目状に展開して格子とした。こ
れらの格子に、鉛粉と希硫酸とを練合して製作したペー
ストを充填し、熟成、乾燥して正極板を作製した。これ
らの正極板5枚と、厚み1.0mmのPb−0.07w
t%Ca−1.3wt%Sn合金圧延シートをレシプロ
式エキスパンド機を用いて網目状に展開した格子に、リ
グニンスルホン酸、BaSOおよびカーボンを混合し
た鉛粉と希硫酸とを練合して製作したペーストを充填
し、熟成、乾燥して作製した負極板6枚とを微細ガラス
繊維セパレータを介して交互に積層し、極板群を形成し
た。これらの極板群を電槽に挿入し、希硫酸を所定量注
液して化成し、2V30Ahの密閉型鉛蓄電池を製作し
た。
Next, the produced rolled sheet was developed into a grid using a reciprocating expander to form a lattice. These lattices were filled with a paste produced by kneading lead powder and dilute sulfuric acid, aging and drying to produce a positive electrode plate. Five of these positive electrode plates and a 1.0 mm thick Pb-0.07w
The t% Ca-1.3wt% Sn alloy rolled sheet in a grid obtained by expanding in a network form using a reciprocating expanding machine, lignin sulfonic acid, and kneading the and lead were mixed BaSO 4 and carbon powder dilute sulfuric acid The prepared paste was filled, aged and dried, and six negative electrode plates were alternately laminated via a fine glass fiber separator to form an electrode plate group. These electrode plates were inserted into a battery case, and a predetermined amount of diluted sulfuric acid was injected to form a battery, thereby producing a sealed lead-acid battery of 2V30Ah.

【0022】これらの電池を放電は10A(1/3C
A)で1時間、充電は電池電圧が2.45Vに達するま
で10Aの定電流で充電し、2.45Vに達した後は電
池電圧が2.45Vを維持して充電するという方式で1
0時間、温度は40℃という条件でサイクル寿命試験を
実施し、50サイクル毎に10A(1/3CA)で容量
試験をおこなった。比較のため、基材表面に上記表面層
を有しない格子、Pb−5.0wt%Sb合金の表面層
を形成させた格子およびSnのみの表面層を形成させた
格子についても同様に作製し試験に供した。試験に供し
た電池の一覧とその試験結果を表1に示す。
These batteries were discharged at 10 A (1/3 C
In A), charging is performed at a constant current of 10 A until the battery voltage reaches 2.45 V for 1 hour, and after the battery voltage reaches 2.45 V, charging is performed while maintaining the battery voltage at 2.45 V.
A cycle life test was performed at 0 hours and a temperature of 40 ° C., and a capacity test was performed at 10 A (1 / CA) every 50 cycles. For comparison, a lattice having no surface layer on the substrate surface, a lattice having a Pb-5.0 wt% Sb alloy surface layer formed thereon, and a lattice having a Sn only surface layer formed thereon were also manufactured and tested. Was served. Table 1 shows a list of batteries subjected to the test and the test results.

【0023】[0023]

【表1】 [Table 1]

【0024】上記表面層を有しない圧延シートからなる
格子を用いて作製した従来の電池(A)および基材にS
nの表面層を形成させた格子を用いて作製した電池
(J)よりも、本発明によるアルカリ金属またはアルカ
リ土類金属を含む表面層を有する格子を用いて作製した
電池(C〜I)の方が寿命が長く、Pb−Sb合金層を
有する格子を用いた電池(B)と同等以上の寿命性能を
示した。さらに、寿命試験中における各電池の減液量を
比較すると、本発明になる格子を用いて作製した電池
(C〜I)は、表面層を有しない電池と同等で、Pb−
Sb合金を用いた電池のそれよりも非常に少なく、良好
であった。
A conventional battery (A) manufactured using a grid made of a rolled sheet having no surface layer and a substrate
Batteries (C to I) prepared using a grid having a surface layer containing an alkali metal or an alkaline earth metal according to the present invention, as compared with a battery (J) prepared using a grid formed with an n surface layer. The battery had a longer life, and exhibited a life performance equal to or higher than that of the battery (B) using the grid having the Pb-Sb alloy layer. Furthermore, comparing the amount of liquid reduction of each battery during the life test, the batteries (C to I) produced using the grid according to the present invention are equivalent to the batteries having no surface layer, and Pb-
It was much smaller and better than that of the battery using the Sb alloy.

【0025】なお、本実施例ではアルカリ金属またはア
ルカリ土類金属を1種類添加した場合について示した
が、これらを2種類以上組み合わせた場合も同様の効果
が得られる。
In this embodiment, the case where one kind of alkali metal or alkaline earth metal is added is shown, but the same effect can be obtained when two or more kinds of these are combined.

【0026】(実施例2)前記表面層中のアルカリ金属
およびアルカリ土類金属の含有量を変えて実施例1と同
様の方法で製作したエキスパンド格子を用いて、2V3
0Ahの密閉型鉛蓄電池を製作し、実施例1と同様の条
件でサイクル寿命試験をおこなった。各添加元素の添加
量と寿命サイクル数との関係を図3〜7に示す。
Example 2 Using an expanded grating manufactured in the same manner as in Example 1 except that the content of the alkali metal and alkaline earth metal in the surface layer was changed, 2V3
A sealed lead-acid battery of 0 Ah was manufactured, and a cycle life test was performed under the same conditions as in Example 1. 3 to 7 show the relationship between the amount of each additive element and the number of life cycles.

【0027】この結果からわかるように、表面層の合金
としてSn−Ca合金を用いた場合、Ca量が0.1〜
10wt%の領域で寿命性能の向上が著しいことがわか
る。また、表面層の合金としてSn−K合金、Sn−M
g合金、Sn−Sr合金、Sn−Ba合金を用いた場合
にも、0.1〜10wt%の領域で同様の効果が得られ
た。
As can be seen from the results, when the Sn—Ca alloy is used as the alloy of the surface layer, the amount of Ca is 0.1 to 0.1%.
It can be seen that the life performance is significantly improved in the region of 10 wt%. In addition, Sn-K alloy, Sn-M
Similar effects were obtained in the range of 0.1 to 10% by weight when the g alloy, Sn—Sr alloy, and Sn—Ba alloy were used.

【0028】なお、本実施例ではアルカリ金属またはア
ルカリ土類金属を1種類添加した場合について示した
が、これらを2種類以上組み合わせた場合も同様の効果
が得られる。
Although the present embodiment shows the case where one kind of alkali metal or alkaline earth metal is added, the same effect can be obtained when two or more kinds of these are combined.

【0029】[0029]

【発明の効果】以上、本発明を用いることによって、自
己放電や電解液の減少をPb−Ca系合金集電体を用い
た場合と同等に抑えたまま寿命性能の優れた鉛蓄電池を
得ることができる。
As described above, by using the present invention, it is possible to obtain a lead-acid battery having excellent life performance while suppressing self-discharge and reduction of the electrolytic solution to the same level as when using a Pb-Ca-based alloy current collector. Can be.

【図面の簡単な説明】[Brief description of the drawings]

【図1】本発明にかかる集電体を作製するための圧延シ
ートの一例を示す斜視図。
FIG. 1 is a perspective view showing an example of a rolled sheet for producing a current collector according to the present invention.

【図2】本発明にかかる集電体を作製するための圧延シ
ートの一例を示す断面図。
FIG. 2 is a sectional view showing an example of a rolled sheet for producing a current collector according to the present invention.

【図3】表面層のCa含有量と寿命性能との関係を示す
図。
FIG. 3 is a graph showing the relationship between the Ca content of the surface layer and the life performance.

【図4】表面層のK含有量と寿命性能との関係を示す
図。
FIG. 4 is a diagram showing the relationship between the K content of the surface layer and the life performance.

【図5】表面層のMg含有量と寿命性能との関係を示す
図。
FIG. 5 is a view showing the relationship between the Mg content of the surface layer and the life performance.

【図6】表面層のSr含有量と寿命性能との関係を示す
図。
FIG. 6 is a diagram showing the relationship between the Sr content of the surface layer and the life performance.

【図7】表面層のBa含有量と寿命性能との関係を示す
図。
FIG. 7 is a view showing the relationship between the Ba content of the surface layer and the life performance.

【符号の説明】[Explanation of symbols]

1 表面層 2 基材 1 surface layer 2 base material

Claims (7)

【特許請求の範囲】[Claims] 【請求項1】 基材の表面の一部に表面層を有する鉛蓄
電池用正極集電体であって、前記基材がSbを含まない
鉛合金または鉛であり、前記表面層がアルカリ金属およ
びアルカリ土類金属から選択された金属の1以上を含む
スズ合金層であることを特徴とする鉛蓄電池用正極集電
体。
1. A positive electrode current collector for a lead storage battery having a surface layer on a part of the surface of a base material, wherein the base material is a lead alloy or lead not containing Sb, and the surface layer is made of an alkali metal and A positive electrode current collector for a lead-acid battery, comprising a tin alloy layer containing at least one metal selected from alkaline earth metals.
【請求項2】 上記表面層中のアルカリ金属および/ま
たはアルカリ土類金属量が0.1〜10wt%であるこ
とを特徴とする請求項1に記載の鉛蓄電池用正極集電
体。
2. The positive electrode current collector for a lead storage battery according to claim 1, wherein the amount of the alkali metal and / or alkaline earth metal in the surface layer is 0.1 to 10% by weight.
【請求項3】 上記表面層の厚みが1μm以上であり、
かつ基材の厚みの10%以下であることを特徴とする請
求項1、または2に記載の鉛蓄電池用正極集電体。
3. The thickness of the surface layer is 1 μm or more,
The positive electrode current collector for a lead-acid battery according to claim 1 or 2, wherein the thickness is 10% or less of the thickness of the base material.
【請求項4】 正極集電体の集電耳部のうち、少なくと
も溶接されてストラップと一体化する部分には上記表面
層を有しないことを特徴とする請求項1、2、または3
に記載の鉛蓄電池用正極集電体。
4. The current collector ear portion of the positive electrode current collector does not have the surface layer at least in a portion which is welded and integrated with the strap.
4. The positive electrode current collector for a lead storage battery according to claim 1.
【請求項5】 正極集電体がエキスパンド加工または打
ち抜き加工されてなる格子またはシート状であることを
特徴とする請求項1、2、3、または4に記載の鉛蓄電
池用正極集電体。
5. The positive electrode current collector for a lead storage battery according to claim 1, wherein the positive electrode current collector is in the form of a lattice or a sheet obtained by expanding or punching.
【請求項6】 Sbを含まない鉛合金もしくは鉛の板の
一面または両面に、アルカリ金属およびアルカリ土類金
属から選択された金属の1以上を含むスズ合金のシート
を重ね合わせたものを圧延することにより一体化された
鉛合金シートから加工されてなることを特徴とする請求
項5に記載の鉛蓄電池用正極集電体。
6. A roll obtained by superposing a sheet of a tin alloy containing one or more metals selected from alkali metals and alkaline earth metals on one or both sides of a lead alloy or lead plate not containing Sb. The positive electrode current collector for a lead storage battery according to claim 5, wherein the positive electrode current collector is processed from a lead alloy sheet integrated by the above.
【請求項7】 請求項1、2、3、4、5、または6に
記載の正極集電体を用いた鉛蓄電池。
7. A lead-acid battery using the positive electrode current collector according to claim 1, 2, 3, 4, 5, or 6.
JP2001008314A 2001-01-16 2001-01-16 Positive electrode collector for lead acid battery and lead acid battery using the same Pending JP2002216773A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2001008314A JP2002216773A (en) 2001-01-16 2001-01-16 Positive electrode collector for lead acid battery and lead acid battery using the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2001008314A JP2002216773A (en) 2001-01-16 2001-01-16 Positive electrode collector for lead acid battery and lead acid battery using the same

Publications (1)

Publication Number Publication Date
JP2002216773A true JP2002216773A (en) 2002-08-02

Family

ID=18875949

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2001008314A Pending JP2002216773A (en) 2001-01-16 2001-01-16 Positive electrode collector for lead acid battery and lead acid battery using the same

Country Status (1)

Country Link
JP (1) JP2002216773A (en)

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