JPH0644487B2 - Paste type lead acid battery - Google Patents
Paste type lead acid batteryInfo
- Publication number
- JPH0644487B2 JPH0644487B2 JP61293982A JP29398286A JPH0644487B2 JP H0644487 B2 JPH0644487 B2 JP H0644487B2 JP 61293982 A JP61293982 A JP 61293982A JP 29398286 A JP29398286 A JP 29398286A JP H0644487 B2 JPH0644487 B2 JP H0644487B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- lead
- battery
- discharge
- lattice
- 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.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/745—Expanded metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明はペースト式鉛蓄電池に関するものであり、とく
にペースト式鉛蓄電池の格子を改善するものである。Description: TECHNICAL FIELD The present invention relates to a paste-type lead-acid battery, and more particularly to improving the grid of the paste-type lead-acid battery.
従来の技術 ペースト式鉛蓄電池の格子にはこれまで鉛（Ｐｂ）−ア
ンチモン（Ｓｂ）系合金の鋳造格子が用いられてきた。
しかし、自己放電が促進されるなどの欠点から新しい合
金として、鉛（Ｐｂ）−カルシウム（Ｃａ）系合金が開
発された。また、製造法も圧延シートを材料とし、これ
をエキスパンド加工して格子とする方式が開発された。2. Description of the Related Art Conventionally, a lead (Pb) -antimony (Sb) alloy casting grid has been used as a grid of a paste type lead storage battery.
However, a lead (Pb) -calcium (Ca) -based alloy has been developed as a new alloy due to the drawbacks such as promotion of self-discharge. In addition, as a manufacturing method, a method has been developed in which a rolled sheet is used as a material and is expanded to form a lattice.
このＰｂ−Ｃａ系合金製のエキスパンド格子を用いてメ
ンテナンスフリー化をはかった電池が普及するととも
に、その弱点にも改良が加えられてきた。たとえば、深
い放電を含むサイクル特性の向上をはかる目的として、
格子の表面にＰｂ−Ｓｂ−ヒ素（Ａｓ）合金層を形成さ
せ、格子と活物質の密着を高める手段が開発された。ま
た、Ｐｂ−Ｃａ系合金の弱点である過放電放置後の充電
回復性の向上をはかる手段として、格子表面層にスズ
（Ｓｎ）の多い層を形成させる方法が開発された。With the spread of maintenance-free batteries using this expanded lattice made of Pb-Ca alloy, improvements have been added to their weak points. For example, for the purpose of improving cycle characteristics including deep discharge,
A means for forming a Pb-Sb-arsenic (As) alloy layer on the surface of the lattice to enhance the adhesion between the lattice and the active material has been developed. In addition, a method of forming a layer containing a large amount of tin (Sn) on the lattice surface layer has been developed as a means for improving the charge recovery property after standing for over discharge, which is a weak point of the Pb-Ca alloy.
このように、Ｐｂ−Ｃａ系合金の欠点は、格子と活物質
との界面によることが多く、したがって、この界面を改
善する手段または改質方法などがこれまで検討されてき
た。As described above, the drawback of the Pb-Ca-based alloy is often due to the interface between the lattice and the active material, and therefore, means for improving the interface or a modification method have been studied so far.
発明が解決しようとする問題点 本発明はＰｂ−Ｃａ系合金を用いたメンテンナンスフリ
ータイプの鉛蓄電池の放電放置後のサイクル特性の向上
をはかるものである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention is intended to improve the cycle characteristics of a maintenance-free type lead storage battery using a Pb-Ca alloy after being left for discharge.
近年、自動車のエレクトロニクス化が進み、電池の負荷
が増えてきた。そのため、電池が放電状態になる割合が
増加するとともに、放電状態のままで放置される頻度が
多くなってきた。そこで、放電放置後においても始動性
能が確保されることが重要な性能となる。In recent years, automobiles have become more electronic, and the load on batteries has increased. Therefore, the rate at which the battery is in the discharged state has increased, and the frequency with which the battery is left in the discharged state has increased. Therefore, it is important to ensure the starting performance even after the discharge is left.
また、農業機械用などの場合、使用される期間が限られ
るので、使われた後長期間放置されて、再び使われるパ
ターンが繰り返されることになる。このとき、放電状態
で放置され、再度使用するときに充電されにくくなる場
合がある。そのため、格子表面にＳｎの多い層を形成し
て改善が図られた。しかしながら、このように放電状態
で放置されることが繰り返されると、十分な効果が得ら
れなくなる。とくに、放置後の高率放電性能の低下が大
きくなる。In addition, in the case of agricultural machinery, since the period of use is limited, the pattern that is left for a long time after being used and then used again is repeated. At this time, the battery may be left in a discharged state and may not be easily charged when used again. Therefore, a layer containing a large amount of Sn was formed on the surface of the lattice to improve the structure. However, if the discharge is repeatedly left as it is, a sufficient effect cannot be obtained. In particular, the deterioration of the high rate discharge performance after being left is large.
そこで、本発明は電池が放電状態で放置されることが繰
り返し行なわれても、その充電受入性を改善し、使用時
の電池特性とくに高率放電特性の低下を抑制することを
目的としたものである。Therefore, the present invention has an object to improve the charge acceptability of the battery even if the battery is left in a discharged state repeatedly and to suppress the deterioration of the battery characteristic, particularly the high rate discharge characteristic, during use. Is.
問題点を解決するための手段 本発明は、鉛−カルシウム系合金からなる格子体の表面
に、鉛−アンチモン−スズ合金層を直接形成したもので
ある。その具体的な構成は、Ｃａを０．０３〜１．２重
量％含んだ鉛−カルシウム系合金シートの少なくとも一
面に、鉛−２．０〜５．０重量％のアンチモン−１．０
〜５．０重量％のスズの合金箔層を直接圧着一体化した
圧延シートを素材に用い、これをエキスパンド加工して
格子としたものである。Means for Solving the Problems The present invention is one in which a lead-antimony-tin alloy layer is directly formed on the surface of a grid body made of a lead-calcium alloy. The specific constitution is as follows. At least one surface of a lead-calcium based alloy sheet containing 0.03 to 1.2% by weight of Ca, and antimony-1.0 of lead-2.0 to 5.0% by weight.
A rolled sheet in which a tin alloy foil layer of up to 5.0 wt% is directly pressure-bonded and integrated is used as a material, and this is expanded to form a lattice.
ここで母材となる鉛−カルシウム系合金シートのカルシ
ウム添加量が０．０３重量％未満ではシートの機械的強
度が小さく、作業性が悪い。また、カルシウムが１．２
重量％を超えると、シートの耐食性が著しく低下する。
したがって０．０３〜１．２重量％のカルシウム含有量
にすることが好ましい。なお、母材のシート合金が鉛−
カルシウム−スズの３元合金であってもほぼ同様な効果
がある。Here, if the amount of calcium added to the lead-calcium alloy sheet as the base material is less than 0.03% by weight, the mechanical strength of the sheet is small and the workability is poor. Also, calcium is 1.2
If it exceeds the weight percentage, the corrosion resistance of the sheet is significantly reduced.
Therefore, it is preferable to set the calcium content to 0.03 to 1.2% by weight. The base sheet alloy is lead-
Even a ternary alloy of calcium and tin has almost the same effect.
格子の表面に鉛−アンチモン−スズ合金層を直接形成す
る場合、この合金中のアンチモン含有量は、２．０〜
５．０重量％が良い。２．０重量％未満では十分な効果
は得られない。また、５．０重量％を超えると、減液量
が増加し、メンテナンスフリータイプとしての特徴が損
なわれるので好ましくない。スズの含有量は１．０重量
％以上で過放電放置後の充電回復性を向上させることが
できる。その上限はとくに限定しなくてもよいが、５重
量％を超えると合金箔としての強度が高まって、シート
表面に圧着一体化しにくくなる。さらに、スズは鉛に比
べて２０倍以上も材料費的に高いので、コスト的にはス
ズは少ない方が良い。これらを総合した結果、スズの量
は１．０〜５．０重量％が適当と思われる。When a lead-antimony-tin alloy layer is directly formed on the surface of the lattice, the antimony content in this alloy is 2.0 to
5.0% by weight is good. If it is less than 2.0% by weight, a sufficient effect cannot be obtained. On the other hand, if it exceeds 5.0% by weight, the amount of reduced liquid increases and the characteristics of the maintenance-free type are impaired, which is not preferable. When the tin content is 1.0% by weight or more, the charge recovery property after leaving for over-discharge can be improved. The upper limit is not particularly limited, but if it exceeds 5% by weight, the strength of the alloy foil increases and it becomes difficult to perform pressure bonding and integration on the sheet surface. Furthermore, since tin is 20 times more expensive than lead in terms of material cost, it is better to use less tin. As a result of combining these, it seems that the amount of tin is appropriately 1.0 to 5.0% by weight.
作用 本発明のエキスパンド加工により得られた格子が、充電
受入性の改善及び放置後の高率放電特性の低下抑制にな
ぜ効果があるのか、その詳細な機構については明らかで
ない。ただ、鉛−カルシウム系合金を用いた格子は、活
物質との界面現象に重要な作用があると考えられる。Action It is not clear why the lattice obtained by the expanding process of the present invention is effective in improving the charge acceptability and suppressing the deterioration of the high rate discharge property after being left unattended. However, it is considered that the lattice using the lead-calcium alloy has an important effect on the interfacial phenomenon with the active material.
鉛−カルシウム合金格子を用いた電池は過放電状態で長
期間放置すると充電されにくくなる。しかしこれはスズ
を多量に添加することにより改善できる。すなわち、過
放電状態で電池が放置されると、格子と活物質との界面
に不働態層が形成され、この層が障害となって充電電流
を流しても充電されなくなる。しかし電池が新しい間は
スズが存在するとこの不働態層が形成されにくくなり、
充電が容易に行なえる。しかし充放電サイクルを繰り返
し行なって、格子と活物質との密着性が低下した状態で
放電放置を行なうと、放電状態で長期間放置された後の
充電が十分なされず、放電容量は激減し、寿命となる。A battery using a lead-calcium alloy grid is less likely to be charged if left in an over-discharged state for a long time. However, this can be improved by adding a large amount of tin. That is, when the battery is left in an over-discharged state, a passivation layer is formed at the interface between the lattice and the active material, and this layer becomes an obstacle and is not charged even when a charging current is passed. However, while the battery is new, the presence of tin makes it difficult for this passivation layer to form,
Easy to charge. However, if charge and discharge cycles are repeated and discharge is left in a state where the adhesion between the grid and the active material is reduced, the charge after being left in the discharge state for a long time is not sufficient, and the discharge capacity is drastically reduced. It will be the end of life.
そこで、本発明のように格子の表面に鉛−アンチモン−
スズ合金の層を形成させることにより、充放電サイクル
を繰り返した後で放電放置をしても、十分な容量を持っ
た状態に充電できることがわかった。これは、アンチモ
ンとスズを含む合金層は充放電の繰り返しによる格子の
酸化腐食が進んでも、その腐食状態が多孔質で活物質と
の密着性を保つとともに、酸化腐食層中のスズあるいは
酸化スズが導電性を発揮するために、放電放置後の充電
によっても電子伝導ネットワークが保たれて、充電受入
性がよく、高容量を維持できるからと考えられる。Therefore, as in the present invention, lead-antimony-
It was found that by forming the tin alloy layer, it is possible to charge the battery with a sufficient capacity even if the battery is left as it is after being repeatedly charged and discharged. This is because the alloy layer containing antimony and tin has a porous corrosion state even when the oxidative corrosion of the lattice progresses due to repeated charging and discharging, and the adhesiveness with the active material is maintained. It is considered that, since it exhibits electrical conductivity, the electron conductive network is maintained even after charging after being left to discharge, the charge acceptance is good, and a high capacity can be maintained.
深い放電を含む充放電サイクル寿命の向上をはかる手段
として、格子表面層にアンチモンを多量に含んだ層を形
成させる方法は、すでに本発明者らが見い出し提案して
いる。しかし、アンモチンだけでは放電放置を繰り返し
行なった場合に高率放電特性を維持することはできなか
った。これは、充放電の繰り返しによる格子と活物質と
の密着性の低下はアンチモンで阻止抑制することができ
るが、放電放置が加わる格子と、活物質との密着性の低
下の抑制だけでは改善できないと推察される。これには
とくに、鉛−アンチモン−スズ合金を格子表面層に形成
することで効果があり、鉛−アンチモンの層と鉛−スズ
の層を別々に形成しても効果はなかった。The present inventors have already found and proposed a method for forming a layer containing a large amount of antimony on the lattice surface layer as a means for improving the charge / discharge cycle life including deep discharge. However, it was not possible to maintain the high rate discharge characteristics by repeating the discharge standing alone with anamtin. This is because antimony can prevent and suppress the decrease in the adhesion between the lattice and the active material due to repeated charging and discharging, but it cannot be improved only by suppressing the decrease in the adhesion between the lattice and the active material to which discharge is added. It is presumed that. This is particularly effective by forming a lead-antimony-tin alloy on the lattice surface layer, and forming the lead-antimony layer and the lead-tin layer separately has no effect.
このように本発明は、単にアンチモンとスズの組み合わ
せでなく、格子表面層にアンチモンとスズを共存させ、
この二つの相乗効果ですぐれた改善がはかられたもので
ある。As described above, the present invention does not simply combine antimony and tin, but makes the lattice surface layer coexist with antimony and tin.
The synergistic effect of these two results in excellent improvement.
実施例 つぎに本発明の実施例を示す。Example Next, an example of the present invention will be described.
Ｐｂ−０．０７重量％Ｃａ−２重量％Ｓｎ合金厚み１０
mm、幅７５mm、長さ１ｍの鋳造板を母材としてつくっ
た。これを母材として圧延シートをつくりエキスパンド
格子とした。Pb-0.07 wt% Ca-2 wt% Sn alloy thickness 10
mm, width 75 mm, length 1 m cast plate was made as a base material. Using this as a base material, a rolled sheet was made to form an expanded lattice.
まず、本発明による電池１として、上記の母材にＰｂ−
２．０重量％Ｓｂ−３．０重量％Ｓｎ箔を圧着した厚み
１．５mmの圧延シートをエキスパンド加工して得た格子
を用いて電池を作成した。また母材だけでつくった圧延
シートのエキスパンド加工による格子を用いて比較例の
電池２をつくった。First, as a battery 1 according to the present invention, Pb-
A battery was prepared using a grid obtained by subjecting a rolled sheet having a thickness of 1.5 mm, to which a 2.0 wt% Sb-3.0 wt% Sn foil was pressure bonded, to an expansion process. Further, a battery 2 of a comparative example was made by using a grid obtained by expanding a rolled sheet made of only the base material.
これらの両電池を５５Ｄ２３形として、５Ａで１０．５
Ｖまで放電し、１５Ｖで充電するパターンで５サイクル
くり返す毎に電池を過放電し、その後１０日間放置して
から１５Ｖで５時間充電し、−１５℃の温度下で３００
Ａ放電により６．０Ｖまで放電した。その時の持続時間
を測定した。These batteries are both 55D23 type and 5A at 10.5.
The battery is discharged to V, and the battery is over-discharged every 5 cycles in a pattern of charging at 15V, then left for 10 days, then charged at 15V for 5 hours, and stored at a temperature of -15 ° C for 300 hours.
It was discharged by A discharge to 6.0V. The duration at that time was measured.
図にその結果を示す。図から明らかなように、本発明の
電池はすぐれた寿命特性を有している。The results are shown in the figure. As is clear from the figure, the battery of the present invention has excellent life characteristics.
なお、実施例ではＰｂ−Ｓｂ−Ｓｎ合金層はシート母材
の表面層の片面だけに直接圧着した例を示したが、シー
ト母材の両面に圧着しても同様の効果は得られている。
また実施例の圧延シート母材はＰｂ−Ｃａ−Ｓｎ３元合
金を用いたが、本発明は母材がＰｂ−Ｃａの２元合金で
も十分な効果が得られており、母材中のＳｎの量は本発
明の効果には影響しない。In the examples, the Pb-Sb-Sn alloy layer is directly pressure-bonded to only one side of the surface layer of the sheet base material, but the same effect can be obtained by pressure-bonding to both sides of the sheet base material. .
Further, the rolled sheet base material of the example uses a Pb-Ca-Sn ternary alloy, but the present invention has obtained a sufficient effect even if the base material is a Pb-Ca binary alloy, and the Sn in the base material is The amount does not affect the effect of the present invention.
一方、圧着する箔の合金が、Ｐｂ−Ｓｂ合金あるいはＰ
ｂ−Ｓｎ合金だけでは、実施例に示したようなパターン
の寿命の向上には大きな効果がなく、本発明のように２
重量％以上のＳｂと１重量％以上のＳｎを共存状態で含
んだ合金層を鉛−カルシウム系合金母材上に直接形成す
ることにより顕著な差が得られる。On the other hand, the foil alloy to be crimped is Pb-Sb alloy or P
The b-Sn alloy alone does not have a great effect on the improvement of the life of the pattern as shown in the embodiment, and it is
A significant difference can be obtained by directly forming an alloy layer containing Sb in an amount of 1 wt% or more and Sn in a coexisting state on the lead-calcium alloy base material.
発明の効果 このように本発明は鉛−カルシウム系合金を格子に用い
た電池において、放電放置を繰り返すようなパターンの
寿命性能を向上させるものである。Effects of the Invention As described above, the present invention improves the life performance of a pattern in which a lead-calcium alloy is used for a grid and the pattern is repeatedly discharged and left.
また、深い充放電特性の向上もはかられ、メンテナンス
フリー性能も良好に維持できる。Further, deep charge / discharge characteristics can be improved, and maintenance-free performance can be favorably maintained.
図は本発明の鉛蓄電池の寿命特性を示す図である。 １……本発明による電池、２……比較例の電池。 The figure shows the life characteristics of the lead-acid battery of the present invention. 1 ... Battery according to the present invention, 2 ... Battery of comparative example.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 勝弘 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (56)参考文献 特開 昭61−200670（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Katsuhiro Takahashi 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A 61-200670 (JP, A)
Claims (1)
鉛−カルシウム系合金からなるシートの少なくとも一面
に、鉛−２．０〜５．０重量％のアンチモン−１．０〜
５．０重量％のスズ合金層を直接圧着一体化した圧延シ
ートをエキスパンド加工した格子を用いたことを特徴と
するペースト式鉛蓄電池。1. A sheet made of a lead-calcium alloy containing 0.03 to 1.2% by weight of calcium, and at least one surface of a sheet containing lead and 2.0 to 5.0% by weight of antimony-1.0 to 1.0% by weight.
A paste-type lead-acid battery using a grid obtained by expanding a rolled sheet in which a 5.0 wt% tin alloy layer is directly pressure-bonded and integrated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61293982A JPH0644487B2 (en) | 1986-12-10 | 1986-12-10 | Paste type lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61293982A JPH0644487B2 (en) | 1986-12-10 | 1986-12-10 | Paste type lead acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63148556A JPS63148556A (en) | 1988-06-21 |
| JPH0644487B2 true JPH0644487B2 (en) | 1994-06-08 |
Family
ID=17801712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61293982A Expired - Lifetime JPH0644487B2 (en) | 1986-12-10 | 1986-12-10 | Paste type lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0644487B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003068308A (en) * | 2001-08-27 | 2003-03-07 | Shin Kobe Electric Mach Co Ltd | Lead battery and its manufacturing method |
| CN101091282B (en) | 2005-09-27 | 2014-09-03 | 古河电池株式会社 | Lead storage battery and process for producing the same |
| JP5228601B2 (en) * | 2008-04-24 | 2013-07-03 | 新神戸電機株式会社 | Lead acid battery |
| WO2012043556A1 (en) * | 2010-09-29 | 2012-04-05 | 株式会社Ｇｓユアサ | Lead storage battery and idling stop vehicle using same |
| CN112831688B (en) * | 2020-12-30 | 2022-06-24 | 浙江铅锂智行科技有限公司 | Lead-based alloy and product thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61200670A (en) * | 1985-03-01 | 1986-09-05 | Matsushita Electric Ind Co Ltd | Grid body for lead storage battery and manufacture thereof |
-
1986
- 1986-12-10 JP JP61293982A patent/JPH0644487B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63148556A (en) | 1988-06-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |