JP2523585B2 - Sealed lead acid battery - Google Patents
Sealed lead acid batteryInfo
- Publication number
- JP2523585B2 JP2523585B2 JP62041971A JP4197187A JP2523585B2 JP 2523585 B2 JP2523585 B2 JP 2523585B2 JP 62041971 A JP62041971 A JP 62041971A JP 4197187 A JP4197187 A JP 4197187A JP 2523585 B2 JP2523585 B2 JP 2523585B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- sealed lead
- acid battery
- active material
- electrolytic solution
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は密閉形鉛蓄電池に関するもので、特に間欠過
放電放置後の特性向上に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealed lead-acid battery, and more particularly, to improvement of characteristics after being left without intermittent over-discharge.
従来の技術 従来のこの種の密閉形鉛蓄電池は、誤って過放電され
ると充電できないことが多く、簡便さに欠けていた。従
ってその対策として機器に過放電させないような機構
（アンダーカット）や、充電予告表示機構などが付加さ
れたが、そのために機器のコストが上昇していた。2. Description of the Related Art Conventional sealed lead-acid batteries of this type cannot be charged when they are accidentally over-discharged, and lack in convenience. Therefore, as a countermeasure, a mechanism (undercut) for preventing the device from being over-discharged, a charge advance notice display mechanism, and the like were added, but the cost of the device was increased because of that.
また、電池においては、正極合金中の添加合金成分
や、電解液の添加剤など種々提案されていた。In addition, in batteries, various proposals have been made regarding additive alloy components in positive electrode alloys, additives for electrolytic solutions, and the like.
発明が解決しようとする問題点 特に、機器にアンダーカットや、充電予告機構などが
なく密閉形鉛蓄電池を使用する場合、間欠的に放電され
ると過放電状態になり易く、さらにこの状態で放置され
ると、中性に近い電解液中に正極格子のPbが溶解し易く
なり、充電すると電解液中に溶解したPbイオンが酸化反
応により、PbO2となって正極活物質と格子体との界面に
生成し、正極活物質との間に亀裂が生じてしまう。これ
を繰り返すと徐々に正極格子体は金属鉛からPbO2に変化
し、ついにはすべてPbO2になり、腐食現象を生じ、蓄電
池として使用開始から早いと数ケ月から１年以内で使用
できないという問題があった。Problems to be Solved by the Invention In particular, when a sealed lead-acid battery without an undercut or charge advance notice mechanism is used in the device, if it is intermittently discharged, it is likely to be in an over-discharged state and left in this state. If so, Pb of the positive electrode lattice is easily dissolved in a near-neutral electrolyte solution, and when charged, the Pb ions dissolved in the electrolyte solution undergo an oxidation reaction to become PbO 2 and become a positive electrode active material and the lattice body. It is generated at the interface and a crack is generated between the active material and the positive electrode active material. When this process is repeated, the positive electrode grid gradually changes from metallic lead to PbO 2 and finally all becomes PbO 2 , causing a corrosion phenomenon, and it is not possible to use it as a storage battery within a few months to a year early. was there.
問題点を解決するための手段 本発明は主としてガラス繊維で抄造したセパレータ、
正極板及び負極板に電解液を含浸保持させ流動電解液の
ない密閉形鉛蓄電池において、正極格子体は1.5重量％
以上の錫を含有し、かつアンチモンを含まないPb−Ca合
金で構成し、負極格子体はアンチモンを含まないPb−Ca
合金で構成するとともに正極活物質量1g当り0.350g以上
の比率で硫酸を含む電解液を含浸保持させた構成によ
り、上記問題点を解決するものである。Means for Solving the Problems The present invention is mainly a separator made of glass fiber,
In a sealed lead-acid battery in which the positive electrode plate and the negative electrode plate are impregnated and held with an electrolytic solution and there is no flowing electrolytic solution, the positive electrode grid is 1.5% by weight.
The Pb-Ca alloy containing the above tin and containing no antimony, the negative electrode lattice is Pb-Ca containing no antimony.
The above-mentioned problems are solved by using an alloy and impregnating and holding an electrolytic solution containing sulfuric acid at a ratio of 0.350 g or more per 1 g of the positive electrode active material.
作用 このように正極格子体中のSnを1.5重量％以上含有さ
せ耐食性を向上させるとともに、正極活物質量1g当り0.
350g以上の比率で硫酸を含む電解液を含浸保持させるこ
とにより、間欠過放電後の放置と、充電との繰り返しに
よる正極格子の腐食を防止させ、密閉形鉛蓄電池の特性
を向上させることができる。Effect As described above, the content of Sn in the positive electrode grid of 1.5% by weight or more improves the corrosion resistance, and the amount of the positive electrode active material is 0.
By impregnating and holding an electrolytic solution containing sulfuric acid at a ratio of 350 g or more, it is possible to prevent corrosion of the positive electrode grid due to repeated charging and discharging after being left after intermittent overdischarge, and it is possible to improve the characteristics of the sealed lead acid battery. .
実 施 例 以下本発明の実施例について説明する。EXAMPLES Examples of the present invention will be described below.
正極格子体は錫を1.5重量％以上含有し、かつアンチ
モンを含まないPb−Ca合金で構成し、これに酸化鉛，希
硫酸よりなるペーストを充填して正極板とする。負極格
子体はアンチモンを含まないPb−Ca合金で構成し、酸化
鉛，希硫酸，硫酸バリウムなどからなるペーストを充填
して負極板とする。セパレータは主としてガラス繊維で
抄造したマットを用い、正極板２枚，負極板３枚で極板
群を構成し、正極活物質量1g当り0.350gの比率の硫酸を
含む電解液を注入し、接着，封口を行い、２セル構成の
密閉形鉛蓄電池とした。この電池は、電圧4V,10時間率
容量3.8Ahである。正極格子体中の錫の量を0.8重量％,
1.15重量％、1.5重量％及び正極活物質量1g当りの硫酸
の比率を0.300g,0.325g,0.350gに選択し、その他は実施
例と同一構成にした蓄電池を構成し比較した。The positive electrode grid body is made of a Pb-Ca alloy containing tin in an amount of 1.5% by weight or more and containing no antimony, and the paste is filled with lead oxide and dilute sulfuric acid to form a positive electrode plate. The negative electrode grid is made of a Pb-Ca alloy that does not contain antimony, and is filled with a paste made of lead oxide, dilute sulfuric acid, barium sulfate, etc. to form a negative electrode plate. As the separator, a mat mainly made of glass fiber is used, and a positive electrode plate is composed of two positive electrode plates and three negative electrode plates, and an electrolytic solution containing sulfuric acid at a ratio of 0.350 g per 1 g of positive electrode active material is injected and bonded. After sealing, a sealed lead-acid battery with a 2-cell configuration was made. This battery has a voltage of 4 V and a 10-hour rate capacity of 3.8 Ah. The amount of tin in the positive electrode grid is 0.8% by weight,
1.15 wt% and 1.5 wt%, and the ratio of sulfuric acid per 1 g of the positive electrode active material was selected to 0.300 g, 0.325 g, and 0.350 g, and the other configurations were the same as those of the examples, and comparison was made.
以上により構成した蓄電池を0.53Ω/4V定抵抗にて図
に示すごとく、３分間放置させ、その後７日間放置する
サイクルを繰り返し、端子電圧が0.5V以下に到達したの
ち、さらに、７日間放置する。そののち定電流にて端子
電圧が4.9Vになるまで充電する。これを１サイクルとし
た間欠過放電放置サイクルを行い10サイクル繰り返した
とき、蓄電池を分解し、正極格子体の状態を観察した。
観察による腐食発生数を下表に示した（試料は各６
個）。The storage battery configured as described above is left to stand for 3 minutes at a constant resistance of 0.53Ω / 4V as shown in the figure, and then left for 7 days. The cycle is repeated until the terminal voltage reaches 0.5V or less, then left for 7 days. . After that, charge with constant current until the terminal voltage becomes 4.9V. When the cycle of intermittent over-discharge was set as one cycle and the cycle was repeated 10 times, the storage battery was disassembled and the state of the positive electrode grid was observed.
The number of corrosion occurrences by observation is shown in the table below.
Individual).
正極格子体が腐食した蓄電池は、すべて金属鉛がPbO2
に変化し、さらに活物質格子体との間には亀裂が生じ、
活物質自体は多量の硫酸鉛を含んだ色相である茶かっ色
となっていた。 In a storage battery with a corroded positive electrode grid, all lead metal is PbO 2
To a crack between the active material lattice and
The active material itself had a brownish brown color, which was a hue containing a large amount of lead sulfate.
従って上表によれば、正極格子中の錫量が1.5重量％
以上であり、かつ、正極活物質1g当り0.350g以上の比率
で硫酸を含む電解液で構成すれば、間欠過放電放置サイ
クルによる正極格子の腐食は防止することができる。Therefore, according to the above table, the amount of tin in the positive electrode grid is 1.5% by weight.
If the electrolyte solution contains sulfuric acid at a ratio of 0.350 g or more per 1 g of the positive electrode active material, corrosion of the positive electrode grid due to the intermittent overdischarge leaving cycle can be prevented.
発明の効果 本発明によれば、間欠過放電放置サイクルによる正極
格子体の腐食を防止することができ、長期信頼性が向上
し、簡便に使用できる密閉形鉛蓄電池を提供でき、さら
に、機器のコスト低下も生じせしめることができる。EFFECTS OF THE INVENTION According to the present invention, it is possible to prevent corrosion of the positive electrode grid body due to the intermittent overdischarge leaving cycle, long-term reliability is improved, and it is possible to provide a sealed lead acid battery that can be easily used, and further, Cost reduction can also occur.
図は、本実施例における電池の間欠過放電放置サイクル
を示す図である。The figure shows the intermittent over-discharge leaving cycle of the battery in this example.
Claims (1)
タ、正極板及び負極板に電解液を含浸保持させた流動電
解液のない密閉形鉛蓄電池であって、正極格子体は1.5
重量％以上の錫を含みかつアンチモンを含まないPb−Ca
合金で構成し、負極格子体はアンチモンを含まないPb−
Ca合金で構成し、かつ正極活物質量1g当り0.350g以上の
比率で硫酸を含む電解液を含浸保持させた密閉形鉛蓄電
池。1. A sealed lead-acid battery without a flowing electrolyte, in which a separator mainly made of glass fiber, a positive electrode plate and a negative electrode plate are impregnated with an electrolytic solution and held, and the positive electrode grid has a thickness of 1.5.
Pb-Ca containing more than wt% tin and no antimony
It is composed of an alloy, and the negative electrode grid is made of Pb-
A sealed lead-acid battery made of Ca alloy and impregnated with an electrolytic solution containing sulfuric acid at a ratio of 0.350 g or more per 1 g of positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62041971A JP2523585B2 (en) | 1987-02-25 | 1987-02-25 | Sealed lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62041971A JP2523585B2 (en) | 1987-02-25 | 1987-02-25 | Sealed lead acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63211574A JPS63211574A (en) | 1988-09-02 |
| JP2523585B2 true JP2523585B2 (en) | 1996-08-14 |
Family
ID=12623080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62041971A Expired - Lifetime JP2523585B2 (en) | 1987-02-25 | 1987-02-25 | Sealed lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2523585B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63298979A (en) * | 1987-05-28 | 1988-12-06 | Yuasa Battery Co Ltd | Sealed lead-acid battery |
| WO2014076883A1 (en) * | 2012-11-13 | 2014-05-22 | パナソニック株式会社 | Lead-acid cell |
-
1987
- 1987-02-25 JP JP62041971A patent/JP2523585B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63211574A (en) | 1988-09-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |