JPH10106574A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH10106574A JPH10106574A JP8281903A JP28190396A JPH10106574A JP H10106574 A JPH10106574 A JP H10106574A JP 8281903 A JP8281903 A JP 8281903A JP 28190396 A JP28190396 A JP 28190396A JP H10106574 A JPH10106574 A JP H10106574A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- electrode active
- antimony
- added
- 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
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は正極格子にＰｂ−Ｃ
ａ系合金を用いた密閉形鉛蓄電池の寿命性能の向上に関
するもので、特に正極活物質へのアンチモン又はその化
合物の添加により正極活物質の劣化を防いで密閉形鉛蓄
電池の寿命性能の向上と安定化を図ることを目的とする
ものである。[0001] The present invention relates to a Pb-C
The present invention relates to the improvement of the life performance of a sealed lead-acid battery using an a-based alloy, and particularly to the improvement of the life performance of a sealed lead-acid battery by preventing the deterioration of the cathode active material by adding antimony or its compound to the cathode active material. The purpose is to achieve stabilization.
【０００２】[0002]
【従来の技術】密閉形鉛蓄電池には、現在最も広く使わ
れている、微細ガラスマットセパレータを正、負極板に
当接したリテーナ式電池と、古くからヨーロッパを中心
に用いられている、電解液をコロイダルシリカでゲル化
したゲル式電池と、近年開発が進められている、顆粒状
のシリカを極板間および極板群の周囲に充填し、そのシ
リカに電解液を含浸させたた顆粒シリカ式電池とがあ
る。2. Description of the Related Art There are two types of sealed lead-acid batteries, the most widely used at present, a retainer type battery in which a fine glass mat separator is in contact with positive and negative electrodes, and an electrolytic type which has been used mainly in Europe since ancient times. A gel battery in which the liquid is gelled with colloidal silica, and a granule in which granular silica, which has been recently developed, is filled between the electrodes and around the electrode group, and the silica is impregnated with an electrolytic solution. There is a silica type battery.
【０００３】これらの密閉電池は、正極にＰｂ−Ｃａ系
合金格子を用いており、そのためサイクル寿命が、従来
のＳｂ合金格子を用いた液式電池に比べると、かなり短
いことが知られている。この原因の一つは正極格子／活
物質界面に硫酸鉛層（いわゆるバリヤー層）が生成する
からである。[0003] These sealed batteries use a Pb-Ca-based alloy grid for the positive electrode, and therefore, are known to have a much shorter cycle life than liquid batteries using a conventional Sb alloy grid. . One of the causes is that a lead sulfate layer (so-called barrier layer) is formed at the positive electrode lattice / active material interface.
【０００４】その対策の一つとして古くから正極活物質
に微量のアンチモンを添加するという技術がある。以下
にその例を示す。As one of the countermeasures, there is a technique for adding a trace amount of antimony to a positive electrode active material for a long time. An example is shown below.
【０００５】（１）特開昭54-114729 ：正極活物質にＳ
ｂ2 Ｏ3 を０．０５％以下添加。(1) JP-A-54-114729: S is used as the positive electrode active material
b 2 O 3 is added at 0.05% or less.
【０００６】（２）特開昭58-209865 ：正極板をＳｂ2
Ｏ3 溶液に浸漬または正極板にＳｂ2Ｏ3 を吹き付け
る。(2) JP-A-58-209865: The positive electrode plate is made of Sb 2
Immerse in an O 3 solution or spray Sb 2 O 3 on the positive electrode plate.
【０００７】（３）特開昭61-142666 ：カルシウム格子
を用いた電池の正極活物質にＳｂ2 Ｏ3 を添加。(3) JP-A-61-142666: Sb 2 O 3 is added to the positive electrode active material of a battery using a calcium lattice.
【０００８】（４）特開昭61-126551 ：低Ｓｂ格子を用
いた電池の正極活物質にＳｂ2 Ｏ3 を添加。(4) JP-A-61-126551: Sb 2 O 3 is added to a positive electrode active material of a battery using a low Sb lattice.
【０００９】（５）特開平1-200558：密閉電池の正極活
物質に０．０５〜０．５％のアンチモン粉末とシリカ粉
末とを添加。(5) JP-A-1-200558: 0.05 to 0.5% of antimony powder and silica powder are added to the positive electrode active material of a sealed battery.
【００１０】（６）特開平3-276561：０．０５％〜１％
のアンチモン又はアンチモン酸化物を添加。(6) JP-A-3-276561: 0.05% to 1%
Add antimony or antimony oxide.
【００１１】[0011]
【発明が解決しようとする課題】以上のような技術はあ
るものの、実際に上記アンチモン又はアンチモン酸化物
を添加すると、性能向上する場合もあれば、かえって寿
命性能が悪くなる場合もあった。この原因を調査したと
ころ、早期に容量低下した電池ではアンチモンが負極板
に析出して充電効率が低下し硫酸鉛が多く蓄積してい
た。また統計的に調査したところ、この現象は活物質の
密度の低い正極板に多く見られた。Although the above-described techniques exist, there are cases where the performance is improved by actually adding the above-mentioned antimony or antimony oxide, and the life performance is rather deteriorated in some cases. When the cause was investigated, antimony was deposited on the negative electrode plate in the battery whose capacity was reduced early, the charging efficiency was reduced, and a large amount of lead sulfate was accumulated. In addition, according to a statistical investigation, this phenomenon was frequently observed in a positive electrode plate having a low active material density.
【００１２】[0012]
【課題を解決するための手段】本発明は、０．００５〜
１％のアンチモンを正極活物質に添加して、電池の寿命
性能を向上させることにあり、我々の種々の試験結果に
よれば、正極格子にＰｂ−Ｃａ系合金を用いた密閉形鉛
蓄電池において、正極活物質にアンチモンあるいはアン
チモン化合物を添加して、Ｓｂ量として正極活物質重量
当たり０．００５％以上１．０％以下存在させるととも
に、この正極活物質の密度が化成後の状態で３．７５g/
cc以上であることを特徴とする密閉形鉛蓄電池にある。SUMMARY OF THE INVENTION The present invention provides a method for producing
In order to improve the life performance of the battery by adding 1% of antimony to the positive electrode active material, according to our various test results, in a sealed lead-acid battery using a Pb-Ca-based alloy for the positive electrode grid, 2. Antimony or an antimony compound is added to the positive electrode active material so that the Sb content is 0.005% or more and 1.0% or less per weight of the positive electrode active material, and the density of this positive electrode active material is 3. 75g /
cc or more.
【００１３】[0013]
【発明の実施の形態】本発明による密閉形鉛蓄電池は、
正極格子にＰｂ−Ｃａ系合金を用いた密閉形鉛蓄電池の
正極活物質中にアンチモンを一定量存在するように添加
するとともに、この正極活物質の密度が化成後の状態で
３．７５g/cc以上になるようにする。このようにするこ
とにより、正極活物質の劣化（軟化）が防止され、密閉
形鉛蓄電池の寿命性能を著しく改善することができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS A sealed lead-acid battery according to the present invention
Antimony is added so as to be present in a certain amount in the positive electrode active material of a sealed lead-acid battery using a Pb-Ca-based alloy for the positive electrode lattice, and the density of the positive electrode active material is 3.75 g / cc in a state after formation. So that By doing so, the deterioration (softening) of the positive electrode active material is prevented, and the life performance of the sealed lead-acid battery can be significantly improved.
【００１４】[0014]
【実施例】以下に本発明の一実施例について説明する。An embodiment of the present invention will be described below.
【００１５】ペースト練膏に用いる比重１．４０の希硫
酸中に硫酸アンチモンを入れ、約５０KHZ の周波数の超
音波を付与し、粉砕・分散させた硫酸アンチモン溶液
を、活物質重量当り０．００１％（Ｂ）、０．００５％
（Ｃ）、０．０１％（Ｄ）、０．０５％（Ｅ）、０．１
％（Ｆ）、１％（Ｇ）、３％（Ｈ）添加したペーストを
Ｐｂ−０．１％Ｃａ−１．５％Ｓｎ合金からなる格子に
充填し２．４ｍｍ厚さの正極板を製作する。なお、これ
は活物質密度の異なる５種類のペースト（化成後の活物
質密度：３．４，３．７５，４．０，４．５，５．０，
ｇ／ｃｃ）に上記７種類の量のアンチモンを添加して、
計３５種類の正極板を製作した。Antimony sulfate was added to dilute sulfuric acid having a specific gravity of 1.40 used for the paste paste, and ultrasonic waves having a frequency of about 50 KHZ were applied thereto. % (B), 0.005%
(C), 0.01% (D), 0.05% (E), 0.1
% (F), 1% (G), and 3% (H) are added to a grid made of a Pb-0.1% Ca-1.5% Sn alloy to produce a 2.4 mm thick positive plate. I do. Note that this is because of five types of pastes having different active material densities (active material densities after chemical formation: 3.4, 3.75, 4.0, 4.5, 5.0,
g / cc) with the above seven types of antimony,
A total of 35 types of positive electrode plates were manufactured.
【００１６】この正極板１０枚と１．７ｍｍ厚さのペー
スト式負極板１１枚と微細ガラスマットセパレータとか
ら、約６３Ａｈ（３ｈＲ）−１２Ｖのリテーナ式密閉電
池を通常の製法にならって製作した。From the ten positive electrode plates, the eleven paste-type negative electrode plates having a thickness of 1.7 mm, and the fine glass mat separator, about 63 Ah (3 hR) -12 V sealed closed-cell batteries were manufactured according to a normal manufacturing method. .
【００１７】なお、硫酸アンチモンを添加していない従
来の標準極板を用いた電池（Ａ）も併せて製作した。こ
れらの電池は常法に従って所定の注液を行なった後、電
槽化成を実施し、電池を完成させた。まず、１／３ＣＡ
放電初期容量を測定した後、寿命試験を行った。寿命試
験は４０℃で、１／３ＣＡ電流で定格の８０％を放電し
た後、定電圧−定電流方式で充電するという一般的な条
件で行った。A battery (A) using a conventional standard electrode plate to which antimony sulfate was not added was also manufactured. These batteries were subjected to a prescribed injection according to a conventional method, and then subjected to battery case formation to complete the batteries. First, 1 / 3CA
After measuring the initial discharge capacity, a life test was performed. The life test was performed under the general conditions of discharging at 80% of the rated current at 40 ° C. with a ℃ CA current, and then charging by a constant voltage-constant current method.
【００１８】まず、初期容量は活物質密度と比例してい
たが、Ｓｂ添加量による差はなかった。寿命性能はその
結果を図１に示すが、Ｓｂ添加量が０．００５〜１％の
場合、特に正極活物質密度が３．７５ｇ／ｃｃ以上の場
合に著しい向上が見られた。電槽化成後に同一構成の別
電池の解体を行って、負極板に析出しているアンチモン
量を分析した。結果を図２に示すが、活物質密度が３．
７５ｇ／ｃｃ以下の極板を用いた場合は負極板へのアン
チモン析出量が多かった。First, the initial capacity was proportional to the active material density, but there was no difference depending on the amount of Sb added. The results of the life performance are shown in FIG. 1, and when the amount of Sb added was 0.005 to 1%, particularly when the positive electrode active material density was 3.75 g / cc or more, a remarkable improvement was observed. After battery case formation, another battery having the same configuration was disassembled, and the amount of antimony deposited on the negative electrode plate was analyzed. FIG. 2 shows the results.
When an electrode plate of 75 g / cc or less was used, the amount of antimony deposited on the negative electrode plate was large.
【００１９】この結果から分かるように正極活物質密度
が低いと添加したアンチモンが電解液中に溶出し、その
後負極板に析出してかえって寿命性能を低下させること
が分かる。正極活物質であるＰｂＯ2 はアンチモンを吸
着する能力があることがわかっているので、添加したア
ンチモンを正極板の中に捕らえておくには、正極板はア
ンチモン添加量に適した活物質密度を有している必要が
ある。As can be seen from the results, when the density of the positive electrode active material is low, the added antimony elutes into the electrolytic solution, and then precipitates on the negative electrode plate, thereby deteriorating the life performance. Since it is known that PbO 2 as a positive electrode active material has the ability to adsorb antimony, in order to keep the added antimony in the positive electrode plate, the positive electrode plate must have an active material density suitable for the amount of antimony added. Must have.
【００２０】なお、本実施例では、硫酸中に硫酸アンチ
モンを分散、添加したが、ペースト練膏液の一つである
水に添加してもその効果には大差はなかった。また、ア
ンチモンとして硫酸アンチモンを用いたが、アンチモン
金属や３酸化アンチモンを同様に添加して試験しても結
果には大差なかった。In this example, antimony sulfate was dispersed and added in sulfuric acid. However, even if it was added to water which is one of the paste plaster solutions, the effect was not so different. In addition, although antimony sulfate was used as antimony, the results did not differ significantly even when antimony metal or antimony trioxide was similarly added and tested.
【００２１】[0021]
【発明の効果】以上述べたように、本発明は正極活物質
に０．００５〜１％のアンチモンあるいはアンチモン化
合物を添加するとともに、活物質密度を３．７５ｇ／ｃ
ｃ以上にした正極板を用いることにより密閉形鉛蓄電池
の寿命性能が著しく改善されるもので、密閉形鉛蓄電池
の実用化という見地から、その工業的価値はきわめて大
きい。As described above, according to the present invention, 0.005 to 1% of antimony or an antimony compound is added to the positive electrode active material, and the active material density is 3.75 g / c.
By using a positive electrode plate having a value of c or more, the life performance of the sealed lead-acid battery is remarkably improved. From the standpoint of practical use of the sealed lead-acid battery, its industrial value is extremely large.
【図１】アンチモン添加量、正極活物質密度と寿命性能
との関係を示す特性図FIG. 1 is a characteristic diagram showing a relationship between antimony addition amount, positive electrode active material density and life performance.
【図２】アンチモン添加量、正極活物質密度と負極板に
析出していたアンチモン量との関係を示す特性図FIG. 2 is a characteristic diagram showing the relationship between the amount of antimony added, the positive electrode active material density, and the amount of antimony deposited on the negative electrode plate.
Claims (1)
閉形鉛蓄電池であって、正極活物質にアンチモンあるい
はアンチモン化合物を添加して、Ｓｂ量として正極活物
質重量当たり０．００５％以上１．０％以下存在させる
とともに、該正極活物質の密度が化成後の状態で３．７
５g/cc以上であることを特徴とする密閉形鉛蓄電池。1. A sealed lead-acid battery using a Pb-Ca-based alloy for a positive electrode grid, wherein antimony or an antimony compound is added to a positive electrode active material, and the amount of Sb is 0.005% or more per weight of the positive electrode active material. 1.0% or less and the density of the positive electrode active material is 3.7 in a state after chemical formation.
A sealed lead-acid battery characterized by being at least 5 g / cc.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8281903A JPH10106574A (en) | 1996-10-02 | 1996-10-02 | Sealed lead-acid battery |
| US08/943,011 US6284411B1 (en) | 1996-10-02 | 1997-10-02 | Valve regulated type battery and producing method thereof |
| EP97117173A EP0834946B1 (en) | 1996-10-02 | 1997-10-02 | Valve regulated type lead-acid battery and producing method thereof |
| DE69715336T DE69715336T2 (en) | 1996-10-02 | 1997-10-02 | Valve-controlled lead-acid battery and process for its manufacture |
| CN97118952A CN1104748C (en) | 1996-10-02 | 1997-10-05 | Enclosed lead accumulator and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8281903A JPH10106574A (en) | 1996-10-02 | 1996-10-02 | Sealed lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10106574A true JPH10106574A (en) | 1998-04-24 |
Family
ID=17645574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8281903A Pending JPH10106574A (en) | 1996-10-02 | 1996-10-02 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10106574A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005216741A (en) * | 2004-01-30 | 2005-08-11 | Furukawa Battery Co Ltd:The | Cathode plate for sealed lead-acid storage battery, and sealed lead-acid storage battery using the above cathode plate |
-
1996
- 1996-10-02 JP JP8281903A patent/JPH10106574A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005216741A (en) * | 2004-01-30 | 2005-08-11 | Furukawa Battery Co Ltd:The | Cathode plate for sealed lead-acid storage battery, and sealed lead-acid storage battery using the above cathode plate |
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