JP3094423B2 - Lead storage battery - Google Patents
Lead storage batteryInfo
- Publication number
- JP3094423B2 JP3094423B2 JP02143188A JP14318890A JP3094423B2 JP 3094423 B2 JP3094423 B2 JP 3094423B2 JP 02143188 A JP02143188 A JP 02143188A JP 14318890 A JP14318890 A JP 14318890A JP 3094423 B2 JP3094423 B2 JP 3094423B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- antimony
- electrode plate
- lattice
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、鉛蓄電池の極板群と負極活物質の添加剤に
関するものである。Description: TECHNICAL FIELD The present invention relates to an electrode group of a lead storage battery and an additive for a negative electrode active material.
従来の技術 ペースト式極板は、大別して鉛−アンチモン系合金を
鋳造により格子体として使用する方法と、鉛−カルシウ
ム系合金でシートを作成後、これを機械加工でエキスパ
ンド状にしたり、打ち抜き板として使用する方法とがあ
る。アンチモンを含んだ鉛合金は、製造上では鋳造性が
良好で格子強度を増し、特性上では過放電した長期放置
後の充電回復性に優れるものの、自己放電が多くなると
ともに電池使用中の電解液の減少が多くなるという問題
を有していた。2. Description of the Related Art Paste-type electrode plates are roughly classified into a method in which a lead-antimony alloy is used as a lattice by casting, and a method in which a sheet is formed from a lead-calcium alloy, which is then expanded into a machined shape, or a punched plate. And how to use it. Lead alloys containing antimony have good castability in production and increase lattice strength, and in terms of characteristics, have excellent charge recovery after long-term storage after overdischarge, but they have increased self-discharge and electrolyte during battery use. There is a problem that the decrease in the number of the refrigeration increases.
一方、鉛−カルシウム系合金の格子体は、電池使用中
の電解液の減少が少なくなり補水作業が不必要になるた
め、最近はこれを利用したメンテナンスフリー電池が増
加する傾向がある。On the other hand, a grid body made of a lead-calcium-based alloy reduces the amount of electrolyte solution during use of the battery and makes it unnecessary to perform water replenishment. Therefore, recently, maintenance-free batteries using the same tend to increase.
しかし正極に鉛−カルシウム系合金の格子体を用いた
場合は異常に過放電したり、そのままの状態で長期間放
置した場合は正極格子と活物質との界面に高い抵抗の不
導態膜が形成されるため、充電受入れ性能が悪くなり、
実用上から使用条件によっては充電できないことがあ
る。However, when a lead-calcium alloy lattice is used for the positive electrode, abnormal overdischarge occurs, or when left unattended for a long period of time, a high-resistance nonconductive film is formed at the interface between the positive electrode lattice and the active material. Because it is formed, the charge receiving performance deteriorates,
In practical use, charging may not be possible depending on use conditions.
したがって、正極板は、格子体のアンチモン含有量を
４重量％以下とし、鋳造性や強度の面で問題は残るもの
の、従来よりも含有量を低くした格子体を用いて自己放
電を少なくし、電池使用中の電解液減少の抑制を図り、
負極板はエキスパンド加工したり打ち抜き板にした鉛−
カルシウム系合金格子体を用い水素過電圧を上げて充電
中の電解液の電気分解を起こりにくくしてそれぞれの極
板を作成後、組み合わせて極板群として用いるハイブリ
ッド方式の電池が各々の用途に応じて使用されるように
なった。Therefore, in the positive electrode plate, the antimony content of the lattice body is set to 4% by weight or less, and although problems remain in terms of castability and strength, self-discharge is reduced by using a lattice body having a lower content than before, In order to suppress the decrease in electrolyte during battery use,
The negative electrode plate is expanded or punched lead-
After increasing the hydrogen overvoltage using a calcium-based alloy lattice to prevent electrolysis of the electrolytic solution during charging, making each electrode plate, the hybrid type battery used as a group of electrode plates according to each application Has come to be used.
発明が解決しようとする課題 しかし特に活物質自体の改良はされておらず、アンチ
モン量の低下により正極の酸素過電圧が高まることから
充電電圧が上がり、定電圧で充電されながら使用された
場合、電池の充電に寄与すべき充電電流が減少して正極
活物質が完全に充電されず、特に過放電後の充電回復性
に問題を生じる傾向があった。Problems to be Solved by the Invention However, the active material itself has not been particularly improved, and the charging voltage increases because the oxygen overvoltage of the positive electrode increases due to the decrease in the amount of antimony. The positive electrode active material was not completely charged due to a decrease in the charging current which should contribute to the charging of the battery, and there was a tendency that a problem particularly occurred in charge recovery after overdischarge.
本発明は、低アンチモン含有量の鉛−アンチモン系合
金を格子体に用いた正極板と、鉛−カルシウム系合金の
格子体を用い、かつ活物質中にバリウムまたは硫酸バリ
ウムなどのバリウム塩を添加した負極板とからなる極板
群を用いることにより、定電圧で充電された場合におい
ても過放電状態から優れた回復性を有する鉛蓄電池を提
供することを目的とする。The present invention provides a positive electrode plate using a lead-antimony-based alloy having a low antimony content as a lattice, a lead-calcium-based alloy lattice, and adding a barium salt such as barium or barium sulfate to the active material. It is an object of the present invention to provide a lead-acid battery having excellent recoverability from an overdischarged state even when charged at a constant voltage by using an electrode group including a negative electrode plate formed as described above.
課題を解決するための手段 本発明は、アンチモン含有量が４重量％以下の鉛−ア
ンチモン系合金を格子体に用いた正極板と、活物質に対
するバリウム量が３重量％以下に制限しかつ鉛−カルシ
ウム系合金の格子体を用いた負極板とを組み合わせた極
板群を用いた鉛蓄電池である。又負極活物質中に添加す
るバリウムとして硫酸バリウムを用いたことを特徴とし
た鉛蓄電池である。Means for Solving the Problems The present invention provides a positive electrode plate using a lead-antimony-based alloy having an antimony content of 4% by weight or less for a lattice, a barium content with respect to an active material of 3% by weight or less, and -A lead-acid battery using an electrode group in combination with a negative electrode plate using a lattice of a calcium-based alloy. The lead storage battery is characterized in that barium sulfate is used as barium added to the negative electrode active material.
作用 このように構成することで、過放電放置後の充電にお
ける電流の流れ、すなわち充電受入れ性をよくして優れ
た回復性をもつ鉛蓄電池とすることができる。Operation With such a configuration, it is possible to improve the flow of current in charging after leaving the battery over-discharged, that is, to improve the charge acceptability and to provide a lead storage battery having excellent recoverability.
実施例 以下、本発明の実施例を説明する。Examples Hereinafter, examples of the present invention will be described.
負極板は、鉛−カルシウム系合金としてカルシウム0.
08重量％（以下、単に％と略す）、錫0.6％、残部が鉛
であるスラブをロールで冷間圧延して厚さ0.8mmの薄板
を作成し、これを網状にエキスパンド加工して格子体を
作成する。The negative electrode plate is a lead-calcium based alloy containing calcium
08% by weight (hereinafter simply abbreviated as "%"), tin 0.6%, and the balance of lead are slabs cold rolled with rolls to produce 0.8mm thick sheets, which are expanded into a mesh to form a grid. Create
一方、活物質中に存在するバリウム量が0.5％,1％,3
％,5％になるように粒径が１μ以下の硫酸バリウムをリ
グニン系有機物とともに酸化鉛に添加し、希硫酸と練合
して得られたペーストを先の格子体に充填する。この時
片面もしくは両面にパルプを主体としたシートを貼り合
わせた後、熟成乾燥を行い未化成の負極板を作成した。On the other hand, the amount of barium present in the active material is 0.5%, 1%, 3%.
% And 5%, barium sulfate having a particle size of 1 μm or less is added to lead oxide together with lignin-based organic matter, and the paste obtained by kneading with dilute sulfuric acid is filled in the lattice. At this time, a sheet mainly composed of pulp was bonded to one or both sides, and then ripened and dried to prepare an unformed negative electrode plate.
正極板は鉛−アンチモン系合金としてアンチモン４
％、砒素0.2％、残部が鉛である格子体を鋳造により作
成し、これを用いて公知の方法により作成した。The positive electrode plate is antimony 4 as a lead-antimony alloy.
%, Arsenic 0.2%, and the balance being lead was prepared by casting, and was prepared by a known method using this.
これらの極板とセパレータとを組み合わせて１セルあ
たりの正極活物質量が500g,負極活物質は400gの極板群
を作成し、電解液の比重は1.26としてJIS規格に定めら
れた55D23形の自動車用電池により、比較試験を実施し
た。By combining these electrode plates and separators, a positive electrode active material amount of 500 g per cell and a negative electrode active material of 400 g were prepared to form an electrode plate group.The specific gravity of the electrolyte was 1.26, and the specific gravity of the 55D23 type specified in the JIS standard was 1.26. A comparative test was performed with an automotive battery.
これらの電池の過放電後の充電回復性を調べる方法と
して、12V10W電球を接続して40℃中で20日間放電させた
後、15日間開路状態で放置した。これにより電解液比重
は1.01まで低下し、過放電状態になった。As a method for examining the charge recoverability of these batteries after overdischarge, a 12V 10W bulb was connected, discharged at 40 ° C for 20 days, and left open for 15 days. As a result, the specific gravity of the electrolytic solution was reduced to 1.01, and an overdischarged state was obtained.
これらの電池を15℃で、最大電流25A,定電圧15Vで充
電した時の15分目の充電電流と、４時間充電後の状態で
−15℃雰囲気中で300Aの低温急放電を行った。その結果
を第１図と次表に示した。この結果よりバリウム含有量
３％以下では５％に比較して充電電流が多く流れ、充電
受入れ特性が良好であった。同時に表に示す−15℃,300
Aの低温急放電特性でも接続時間において優位性を示
し、過放電放置からの定電圧充電回復性に優れた電池を
得られる。These batteries were charged at 15 ° C. at a maximum current of 25 A and a constant voltage of 15 V, and were subjected to a 15 minute charge current and a low temperature rapid discharge of 300 A in a −15 ° C. atmosphere after charging for 4 hours. The results are shown in FIG. 1 and the following table. From this result, when the barium content is 3% or less, the charging current flows more than when the barium content is 5%, and the charge receiving characteristics are good. Simultaneously, at -15 ℃, 300
Even at low temperature and rapid discharge characteristics of A, the battery exhibits superiority in connection time, and a battery excellent in constant voltage charge recovery from overdischarge standing can be obtained.
このように、本発明ではアンチモン量を減らすことは
正極板の充電電位を引き上げることとなり、過放電後の
充電回復の必要性はさらに増すが、負極活物質中のバリ
ウムを減ずることで充電受入れ特性は先の理由で良い方
向に影響し、電池性能の維持が可能である。 As described above, in the present invention, reducing the amount of antimony raises the charge potential of the positive electrode plate, and the necessity of recovering the charge after overdischarge further increases, but the charge acceptance characteristics are reduced by reducing the barium in the negative electrode active material. Affects the positive direction for the above reason, and can maintain the battery performance.
さらに、負極の格子体にはカルシウム系の鉛合金シー
トをエキスパンド加工して使用したが、打ち抜き板を使
用しても何等特性状の差は認められなかった。Furthermore, although a calcium-based lead alloy sheet was expanded and used for the grid of the negative electrode, no difference in characteristics was observed even when a punched plate was used.
発明の効果 本発明は、低アンチモン含有量の鉛−アンチモン系合
金を格子体に用いた正極板と、鉛−カルシウム系合金の
格子体を用い、かつ活物質中に硫酸バリウムを添加した
負極板とからなる極板群を用いることにより、定電圧で
充電された場合においても過放電後の状態から優れた回
復性を有した鉛蓄電池を提供することができる。Effect of the Invention The present invention provides a positive electrode plate using a lead-antimony alloy having a low antimony content as a lattice, and a negative electrode plate using a lattice of a lead-calcium alloy and adding barium sulfate to an active material. By using the electrode group consisting of the following, it is possible to provide a lead-acid battery having excellent recoverability from a state after overdischarge even when charged at a constant voltage.
第１図は供試電池を15℃で最大電流25Aの定電圧15Vで充
電した時の15分目の充電電流の推移を示す図である。FIG. 1 is a diagram showing a transition of a charging current at the 15th minute when a test battery is charged at 15 ° C. at a constant voltage of 15 V with a maximum current of 25 A.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/14,4/20 H01M 4/56,4/62 H01M 10/06 - 10/12 ──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) H01M 4 / 14,4 / 20 H01M 4 / 56,4 / 62 H01M 10/06-10/12
Claims (1)
ンチモン系合金格子体をもつ正極板と、活物質中におけ
るバリウム量が３重量％以下になるようにバリウムを添
加し、かつ鉛−カルシウム系合金を用いてエキスパンド
もしくは打ち抜き加工した格子体を用いた負極板とから
なる極板群を用いた鉛蓄電池。1. A positive electrode plate having a lead-antimony-based alloy lattice having an antimony content of 4% by weight or less, barium is added so that the barium content in the active material is 3% by weight or less, and A lead-acid battery using an electrode group consisting of a negative electrode plate using a grid body expanded or stamped using a calcium-based alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02143188A JP3094423B2 (en) | 1990-05-31 | 1990-05-31 | Lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02143188A JP3094423B2 (en) | 1990-05-31 | 1990-05-31 | Lead storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0436957A JPH0436957A (en) | 1992-02-06 |
| JP3094423B2 true JP3094423B2 (en) | 2000-10-03 |
Family
ID=15332924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02143188A Expired - Lifetime JP3094423B2 (en) | 1990-05-31 | 1990-05-31 | Lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3094423B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02127286A (en) * | 1989-09-14 | 1990-05-15 | Shibasaki Seisakusho:Kk | Capping apparatus |
| JP6136080B2 (en) * | 2015-02-18 | 2017-05-31 | 株式会社Ｇｓユアサ | Lead acid battery |
| JP6115796B2 (en) * | 2015-02-18 | 2017-04-19 | 株式会社Ｇｓユアサ | Lead acid battery |
-
1990
- 1990-05-31 JP JP02143188A patent/JP3094423B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0436957A (en) | 1992-02-06 |
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