JPS63211574A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPS63211574A JPS63211574A JP62041971A JP4197187A JPS63211574A JP S63211574 A JPS63211574 A JP S63211574A JP 62041971 A JP62041971 A JP 62041971A JP 4197187 A JP4197187 A JP 4197187A JP S63211574 A JPS63211574 A JP S63211574A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- battery
- sulfuric acid
- grid
- sealed lead
- 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.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 claims abstract description 8
- 229910000882 Ca alloy Inorganic materials 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003365 glass fiber Substances 0.000 claims abstract description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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
Abstract
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。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a sealed lead-acid battery, and more particularly to improving characteristics after being left in an intermittent overdischarge state.
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。BACKGROUND OF THE INVENTION Conventional sealed lead-acid batteries of this type often cannot be charged if accidentally over-discharged, and lack simplicity. Therefore, as a countermeasure, a mechanism (undercut) to prevent over-discharging and a charging warning display mechanism were added to the device, but this increased the cost of the device.
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, additive alloy components in the positive electrode alloy,
Various proposals have been made, including additives for electrolytes.
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。Problems to be Solved by the Invention Particularly when using a sealed lead-acid battery without an undercut or charge warning mechanism, it is easy to become over-discharged if it is discharged intermittently, and if left in this state When this happens, the PB of the positive electrode lattice easily dissolves in the near-neutral electrolyte, and upon charging, the PB ions dissolved in the electrolyte undergo an oxidation reaction and become PbO2, which forms the interface between the positive electrode active material and the lattice. This causes cracks to form between the cathode active material and the cathode active material.
これを繰り返すと徐々に正極格子体は金属鉛からＰｂＯ
２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。As this process is repeated, the positive electrode grid gradually changes from metallic lead to PbO.
2, and finally it all turns into PbO2, causing a corrosion phenomenon, and if it is used as a storage battery as soon as it is used, it will change to PbO2 for several months to 1.
There was a problem that it could not be used within a year.
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−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／を含まないＰｂ−Ｃ
ａ合金で構成し、負極格子体はアンチモンを含まないＰ
ｂ−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 provides a sealed lead-acid battery in which a separator, a positive electrode plate, and a negative electrode plate mainly made of glass fiber are impregnated with an electrolyte, and there is no flowing electrolyte. 5% by weight
Pb-C containing the above tin and not containing antimony
a alloy, and the negative electrode grid is made of P that does not contain antimony.
The above-mentioned problems are solved by a structure made of a b-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.
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０．３１５０９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。Function In this way, the corrosion resistance is improved by containing 1.5 weight or more of Sn in the positive electrode lattice body, and by impregnating and retaining the electrolytic solution containing sulfuric acid at a ratio of 0.31509 or more per 1 g of the positive electrode active material. It is possible to prevent corrosion of the positive electrode grid due to repeated charging and neglect after intermittent overdischarge, and 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。Example Examples of the present invention will be described below.
正極格子体は錫を１．６重量％以上含有し、かつアンチ
モノを含まない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１１”４す０．３５
Ｃ１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．ａＡｈである。The positive electrode grid is made of a Pb-Ca alloy containing 1.6% by weight or more of tin and free of antimony, and is filled with a paste made of 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. The separator mainly uses a mat made of glass fiber, with two positive electrode plates and three negative electrode plates.
The positive electrode active material amount is 11”4×0.35.
An electrolytic solution containing sulfuric acid at a ratio of C1 was injected, and the battery was bonded and sealed to form a sealed lead-acid battery with a two-cell configuration. This battery has a voltage of 4V and a 10 hour rate capacity of 3. It is aah.
正極格子体中の錫の量をＯ，Ｓ重量％、１．１５重量％
、１．６重量％及び正極活物質量１ｇ当りの硫酸の比率
を０．３００＃、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 amount of tin in the positive electrode grid is O,S weight%, 1.15 weight%
, 1.6% by weight and the ratio of sulfuric acid per 1g of positive electrode active material were selected to be 0.300#, 0.325g, and 0.350g, and other storage batteries were constructed and compared with the same configuration as in the example.
以上によシ構成した蓄電池を０．６３Ω／４Ｖ定抵抗に
て図に示すごとく、３分間放電させ、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１ｏ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）。As shown in the figure, the storage battery configured as above is discharged for 3 minutes with a constant resistance of 0.63Ω/4V, and then left for 7 days. After the terminal voltage reaches 0.5V or less, Leave it for 7 days. Thereafter, the battery is charged at a constant current until the terminal voltage reaches 4.9V. This is 1
After 10 cycles of intermittent overdischarge and standing cycles, the storage battery was disassembled and the state of the positive electrode grid was observed. The number of corrosion occurrences observed is shown in the table below (
6 samples each).
正極格子体が腐食した蓄電池は、すべて金属鉛がＰｂｏ
２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 all storage batteries with corroded positive electrode grids, the metal lead is Pbo.
2, and cracks were formed between the active material and the lattice, and the active material itself had a brownish color that contained a large amount of lead sulfate.
従って上表によれば、正極格子中の錫量が１．６重量−
以上であり、かつ、正極活物質１１ｉ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 lattice is 1.6 weight -
or more, and 0.350 g per 11i of positive electrode active material
By using an electrolytic solution containing sulfuric acid in the above ratio, corrosion of the positive electrode grid due to intermittent over-discharge cycles 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
、簡匣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 due to intermittent overdischarge storage cycles, improve long-term reliability, and provide a sealed lead-acid battery that can be used easily. This can also result in lower costs.
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 is a diagram showing an intermittent overdischarge leaving cycle of the battery in this example.
Claims (1)
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。It is a sealed lead-acid battery without a flowing electrolyte, in which a separator made of glass fiber, a positive electrode plate, and a negative electrode plate are impregnated with an electrolyte, and the positive electrode grid contains 1.5% by weight or more of tin and antimony. The negative electrode grid is made of a Pb-Ca alloy that does not contain antimony, and the negative electrode grid is 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. Sealed lead acid battery.
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 true JPS63211574A (en) | 1988-09-02 |
| JP2523585B2 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) |
Cited By (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
Cited By (3)
| 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 |
| JPWO2014076883A1 (en) * | 2012-11-13 | 2017-01-05 | パナソニック株式会社 | Lead-acid battery for auxiliary equipment in hybrid vehicles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2523585B2 (en) | 1996-08-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |