JP2000200598A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JP2000200598A JP2000200598A JP11000558A JP55899A JP2000200598A JP 2000200598 A JP2000200598 A JP 2000200598A JP 11000558 A JP11000558 A JP 11000558A JP 55899 A JP55899 A JP 55899A JP 2000200598 A JP2000200598 A JP 2000200598A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lead
- acid battery
- bismuth
- 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.)
- 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
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
(57)【要約】
【課題】密閉形鉛蓄電池の充放電サイクル寿命特性を向
上させる。
【解決手段】正極活物質中にビスマスと、アンチモン、
砒素又は錫のうちで少なくとも１種類以上を存在させ
る。ビスマスの添加量として0.001〜１wt.%、アンチモ
ンの添加量として0.01〜１wt.%、砒素の添加量として0.
001〜0.5wt.%、錫の添加量として0.001〜3wt.%とする。
[PROBLEMS] To improve the charge / discharge cycle life characteristics of a sealed lead-acid battery. SOLUTION: Bismuth, antimony,
At least one of arsenic and tin is present. Bismuth is added in an amount of 0.001-1 wt.%, Antimony is added in an amount of 0.01-1 wt.%, And arsenic is added in an amount of 0.1.
001 to 0.5 wt.%, And the amount of tin to be added is 0.001 to 3 wt.%.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、密閉形鉛蓄電池の
充放電サイクル寿命性能の向上に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvement of charge / discharge cycle life of a sealed lead-acid battery.
【０００２】[0002]
【従来の技術】密閉形鉛蓄電池のメンテナンス・フリー
特性の向上や、充放電サイクル寿命性能の向上に関する
要求は、ますます厳しくなっている。一般に鉛蓄電池に
おいて、正極格子に鉛−アンチモン合金を使用すると、
以下に示すような問題点がある。2. Description of the Related Art Demands for improving the maintenance-free characteristics of a sealed lead-acid battery and for improving the charge-discharge cycle life performance are becoming increasingly severe. In general, in lead-acid batteries, when a lead-antimony alloy is used for the positive electrode grid,
There are the following problems.
【０００３】鉛蓄電池の充放電を繰り返すうちに、正極
格子から溶出したアンチモンイオンが負極に析出し、負
極における水素過電圧を低下させ、電解液中の水の電気
分解が起こりやすくなる。その結果、電解液の減液量が
増大するため、頻繁に精製水の補給が必要となる。すな
わち、メンテナンス・フリー特性が低下するという問題
点である。また、正極格子に鉛−アンチモン合金を使用
すると、自己放電量を増大させたり、充電効率を低下さ
せるなどの問題点も指摘されている。[0003] As charge and discharge of the lead-acid battery are repeated, antimony ions eluted from the positive electrode grid are deposited on the negative electrode, reduce the hydrogen overvoltage at the negative electrode, and the electrolysis of water in the electrolytic solution easily occurs. As a result, the amount of electrolyte solution reduced increases, and frequent replenishment of purified water is required. That is, there is a problem that the maintenance-free characteristics are reduced. In addition, when a lead-antimony alloy is used for the positive electrode grid, problems such as an increase in the amount of self-discharge and a decrease in charging efficiency have been pointed out.
【０００４】そこで、メンテナンス・フリー特性の向上
という面から、密閉形鉛蓄電池の正極格子として、鉛−
カルシウム合金の使用が必須となっている。しかしなが
ら、正極格子に鉛−カルシウム合金を使用した場合に
は、鉛−アンチモン合金を使用した場合に比べて、充放
電サイクル寿命が短いという問題点がある。この原因
は、正極格子に鉛−カルシウム合金を使用すると、鉛−
アンチモン合金を使用した場合に比べて、充放電によっ
て正極活物質が軟化しやすいためと考えられている。そ
して、一酸化鉛を主成分とする鉛粉に鉛丹を添加して作
製するペースト式正極を用いた場合において、この傾向
が著しいことが明らかになっている。[0004] Therefore, from the viewpoint of improving the maintenance-free characteristics, a positive electrode grid of a sealed lead-acid battery is used as a positive electrode grid.
The use of calcium alloys has become mandatory. However, when a lead-calcium alloy is used for the positive electrode grid, there is a problem that the charge / discharge cycle life is shorter than when a lead-antimony alloy is used. The cause is that when a lead-calcium alloy is used for the positive electrode grid,
It is considered that the positive electrode active material is easily softened by charge and discharge as compared with the case where an antimony alloy is used. And it is clear that this tendency is remarkable when a paste-type positive electrode produced by adding lead red to lead powder mainly containing lead monoxide is used.
【０００５】前記した問題点を解決する手段として、特
公平８−８１０３号公報には正極活物質中にビスマスを
添加する手法が開示されている。しかしながら、密閉形
鉛蓄電池の正極格子として鉛−カルシウム合金を用いた
場合には、正極活物質にビスマスを添加する手段のみで
は、充放電サイクル寿命性能に大きな効果が得られない
ことが明らかになった。As means for solving the above-mentioned problems, Japanese Patent Publication No. 8-8103 discloses a method of adding bismuth to a positive electrode active material. However, when a lead-calcium alloy is used as the positive electrode grid of a sealed lead-acid battery, it is clear that only a means of adding bismuth to the positive electrode active material does not have a significant effect on the charge-discharge cycle life performance. Was.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、正極
格子として鉛−カルシウム合金を使用した密閉形鉛蓄電
池において、充放電サイクル寿命性能を向上させること
である。SUMMARY OF THE INVENTION An object of the present invention is to improve the charge-discharge cycle life performance of a sealed lead-acid battery using a lead-calcium alloy as a positive electrode grid.
【０００７】[0007]
【課題を解決するための手段】上記した問題点を解決す
る手段として、第一の発明は、正極格子として鉛−カル
シウム合金を使用し、正極、負極をリテーナを介して積
層して作製する極板群を用いた密閉形鉛蓄電池におい
て、前記正極の活物質中にビスマスを0.001〜１wt.%、
アンチモンを0.01〜１wt.%存在させたことを特徴として
いる。Means for Solving the Problems As means for solving the above-mentioned problems, a first invention uses a lead-calcium alloy as a positive electrode grid, and laminates a positive electrode and a negative electrode via a retainer. In a sealed lead-acid battery using a plate group, bismuth in the active material of the positive electrode is 0.001 to 1 wt.%,
It is characterized in that antimony is present in an amount of 0.01 to 1 wt.%.
【０００８】第二の発明は、正極格子として鉛−カルシ
ウム合金を使用し、正極、負極をリテーナを介して積層
して作製する極板群を用いた密閉形鉛蓄電池において、
前記正極の活物質中にビスマスを0.001〜１wt.%、砒素
を0.001〜0.5wt.%存在させたことを特徴としている。A second invention is a sealed lead-acid battery using a lead-calcium alloy as a positive electrode grid and an electrode plate manufactured by stacking a positive electrode and a negative electrode via a retainer.
Bismuth is present in the active material of the positive electrode in an amount of 0.001 to 1 wt.%, And arsenic is present in an amount of 0.001 to 0.5 wt.%.
【０００９】第三の発明は、正極格子として鉛−カルシ
ウム合金を使用し、正極、負極をリテーナを介して積層
して作製する極板群を用いた密閉形鉛蓄電池において、
前記正極の活物質中にビスマスを0.001〜１wt.%、錫を
0.001〜3wt.%存在させたことを特徴としている。A third aspect of the present invention relates to a sealed lead-acid battery using a lead-calcium alloy as a positive electrode grid, and an electrode group manufactured by laminating a positive electrode and a negative electrode via a retainer.
Bismuth in the active material of the positive electrode is 0.001 to 1 wt.%, Tin is
It is characterized by having 0.001 to 3 wt.%.
【００１０】[0010]
【発明の実施の形態】本発明では、正極格子に鉛−カル
シウム合金を使用した密閉形鉛蓄電池の正極活物質中
に、所定量のビスマスと共に、アンチモン、砒素、錫の
少なくとも１種類以上の元素を所定量存在させた。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a predetermined amount of bismuth and at least one or more elements of antimony, arsenic, and tin are contained in a positive electrode active material of a sealed lead-acid battery using a lead-calcium alloy for a positive electrode grid. Was present in a predetermined amount.
【００１１】[0011]
【実施例】本発明の一実施例について示す。 （実施例１）一酸化鉛を主成分とする鉛粉に鉛丹を15w
t.%混合して、混合鉛粉を作製する。この混合鉛粉に、
後述する図１に示す量のビスマスとアンチモンとを0.00
1〜3wt.%添加した。なお、これら元素の添加は三酸化ビ
スマス（Bi2O3）の粉末と、三酸化アンチモン（Sb2O3）
の粉末とを前記混合鉛粉に加える手法を用いた。これら
の粉末を混合した後、水と硫酸とを加えて混練してペー
スト状活物質を作成する。このペースト状活物質を従来
の手法により、鉛−0.06wt.%カルシウム−2wt.%錫合金
の正極格子に充填し、熟成、乾燥して未化成の正極板を
作成した。この正極板と従来の手法により作製した負極
板とを、リテーナを介して積層して極板群を組み、該極
板群を電槽に挿入し、蓋を付けて組み立てた後、電槽化
成をして2V-15Ahの密閉形鉛蓄電池を作成した。An embodiment of the present invention will be described. (Example 1) Lead powder containing lead monoxide as a main component was mixed with 15w
By mixing t.%, a mixed lead powder is prepared. In this mixed lead powder,
Bismuth and antimony in the amounts shown in FIG.
1-3 wt.% Was added. The addition of these elements is based on bismuth trioxide (Bi 2 O 3 ) powder and antimony trioxide (Sb 2 O 3 )
Was added to the mixed lead powder. After mixing these powders, water and sulfuric acid are added and kneaded to prepare a paste-like active material. This paste-like active material was filled in a positive electrode grid of lead-0.06 wt.% Calcium-2 wt.% Tin alloy by a conventional method, aged and dried to prepare an unformed positive electrode plate. The positive electrode plate and the negative electrode plate manufactured by the conventional method are laminated via a retainer to form an electrode plate group, the electrode plate group is inserted into a battery case, and a lid is attached. To produce a 2V-15Ah sealed lead-acid battery.
【００１２】作製した密閉形鉛蓄電池は、3.75Aの電流
値で3時間放電した後、放電量の110%を4時間かけて定電
流充電する方式で、充放電サイクル寿命試験を行った。
50サイクルごとに3.75Aの電流値で1.75Vまで放電し、初
期の放電容量の75%になったサイクル数を密閉形鉛蓄電
池の寿命とした。図１に正極活物質中のビスマス及びア
ンチモンの添加量と寿命サイクル数の関係を示す。図１
より、ビスマスを0.001〜1wt.%添加するとともに、さら
にアンチモンを0.001〜1wt.%添加することにより、密閉
形鉛蓄電池の充放電サイクル寿命性能が向上する。The manufactured sealed lead-acid battery was subjected to a charge / discharge cycle life test in a method of discharging at a current value of 3.75 A for 3 hours and then charging 110% of the discharged amount at a constant current for 4 hours.
The battery was discharged to 1.75 V at a current value of 3.75 A every 50 cycles, and the number of cycles at which the initial discharge capacity reached 75% was defined as the life of the sealed lead-acid battery. FIG. 1 shows the relationship between the amounts of bismuth and antimony in the positive electrode active material and the number of life cycles. FIG.
By adding 0.001 to 1 wt.% Of bismuth and further adding 0.001 to 1 wt.% Of antimony, the charge / discharge cycle life performance of the sealed lead-acid battery is improved.
【００１３】（実施例２）前記した混合鉛粉にビスマス
を0.01wt.%と、砒素を0.001〜3wt.%添加した。なお、こ
れらの元素の添加は三酸化ビスマス（Bi2O3）の粉末
と、三酸化二砒素（As2O3）の粉末とを加える手法を用
いた。その他の密閉形鉛蓄電池の作製条件や、充放電サ
イクル寿命試験は、前記（実施例１）と同様である。正
極活物質中のビスマス及び砒素の添加量と寿命サイクル
数の関係を図２に示す。図２より、ビスマスを0.01wt.%
添加するとともに、さらに砒素を0.001〜0.5wt.%添加す
ることにより密閉形鉛蓄電池の充放電サイクル寿命性能
が向上する。(Example 2) Bismuth was added to the above-mentioned mixed lead powder in an amount of 0.01 wt.% And arsenic in an amount of 0.001 to 3 wt.%. In addition, the addition of these elements used a technique of adding a powder of bismuth trioxide (Bi 2 O 3 ) and a powder of diarsenic trioxide (As 2 O 3 ). The other manufacturing conditions of the sealed lead-acid battery and the charge / discharge cycle life test are the same as in the above (Example 1). FIG. 2 shows the relationship between the added amount of bismuth and arsenic in the positive electrode active material and the number of life cycles. As shown in FIG.
By adding 0.001 to 0.5 wt.% Of arsenic, the charge / discharge cycle life of the sealed lead-acid battery is improved.
【００１４】（実施例３）前記した混合鉛粉にビスマス
を0.01wt.%と、錫を0.001〜5wt.%添加した。なお、これ
らの元素の添加は三酸化ビスマス（Bi2O3）の粉末と、
二酸化錫（SnO2）の粉末とを加える手法を用いた。その
他の密閉形鉛蓄電池の作製条件や、充放電サイクル寿命
試験は、前記（実施例１）と同様である。正極活物質中
のビスマス及び錫の添加量と寿命サイクル数の関係を図
３に示す。図３より、ビスマスを0.01wt.%添加するとと
もに、さらに錫を0.001〜3wt.%添加することにより密閉
形鉛蓄電池の充放電サイクル寿命性能が向上する。Example 3 Bismuth was added to the above-mentioned mixed lead powder in an amount of 0.01 wt.% And tin was added in an amount of 0.001 to 5 wt.%. The addition of these elements is based on bismuth trioxide (Bi 2 O 3 ) powder,
A technique of adding tin dioxide (SnO 2 ) powder was used. The other manufacturing conditions of the sealed lead-acid battery and the charge / discharge cycle life test are the same as in the above (Example 1). FIG. 3 shows the relationship between the amounts of bismuth and tin added to the positive electrode active material and the number of life cycles. As shown in FIG. 3, the addition of 0.01 wt.% Of bismuth and the addition of 0.001 to 3 wt.% Of tin improve the charge-discharge cycle life performance of the sealed lead-acid battery.
【００１５】なお、今回はビスマス、アンチモン、砒素
または錫の酸化物を添加剤として用いたが、これらの硫
酸塩や金属粉末等を添加した場合においても同様の効果
が得られた。また、これらの粉末をペースト状活物質の
練合時に添加する方法を用いた場合でも、同様の効果が
得られた。また、正極の活物質中にビスマスと、アンチ
モン、砒素又は錫のうち２種類以上の元素が前記した添
加量、存在していても同様の効果が得られた。In this case, an oxide of bismuth, antimony, arsenic or tin was used as an additive, but the same effect was obtained when these sulfates, metal powders and the like were added. The same effect was obtained even when the method of adding these powders at the time of kneading the paste-like active material was used. The same effect was obtained even when bismuth and two or more elements of antimony, arsenic or tin were present in the active material of the positive electrode in the above-described amounts and amounts.
【００１６】[0016]
【発明の効果】本発明は、正極の活物質中に所定量のビ
スマスと共に、アンチモン、砒素又は錫のうちで少なく
とも一種類以上を所定量存在させたことによって、密閉
形鉛蓄電池の寿命性能が大幅に向上する点で優れてい
る。According to the present invention, the life performance of a sealed lead-acid battery is improved by allowing a predetermined amount of at least one of antimony, arsenic and tin to be present together with a predetermined amount of bismuth in the active material of the positive electrode. It is excellent in that it greatly improves.
【図１】正極活物質中のビスマス及びアンチモンの添加
量と寿命サイクル数の関係である。FIG. 1 shows the relationship between the amounts of bismuth and antimony added to a positive electrode active material and the number of life cycles.
【図２】正極活物質中のビスマス及び砒素の添加量と寿
命サイクル数の関係である。FIG. 2 shows the relationship between the added amount of bismuth and arsenic in the positive electrode active material and the number of life cycles.
【図３】正極活物質中のビスマス及び錫の添加量と寿命
サイクル数の関係である。FIG. 3 shows the relationship between the amounts of bismuth and tin added to the positive electrode active material and the number of life cycles.
フロントページの続き Ｆターム(参考） 5H003 AA04 BB04 BD04 5H016 AA02 AA05 EE01 HH01 5H017 AA01 AS10 CC05 EE03 HH01 5H028 AA01 AA05 EE01 FF04 HH01Continuation of the front page F term (reference) 5H003 AA04 BB04 BD04 5H016 AA02 AA05 EE01 HH01 5H017 AA01 AS10 CC05 EE03 HH01 5H028 AA01 AA05 EE01 FF04 HH01
Claims (3)
し、正極、負極をリテーナを介して積層して作製する極
板群を用いた密閉形鉛蓄電池において、前記正極の活物
質中にビスマスを0.001〜１wt.%、アンチモンを0.01〜
１wt.%存在させたことを特徴とする密閉形鉛蓄電池。In a sealed lead-acid battery using a lead-calcium alloy as a positive electrode grid and an electrode group produced by laminating a positive electrode and a negative electrode via a retainer, bismuth is contained in an active material of the positive electrode. 0.001-1 wt.%, Antimony 0.01-
A sealed lead-acid battery characterized by being present at 1 wt.%.
し、正極、負極をリテーナを介して積層して作製する極
板群を用いた密閉形鉛蓄電池において、前記正極の活物
質中にビスマスを0.001〜１wt.%、砒素を0.001〜0.5wt.
%存在させたことを特徴とする密閉形鉛蓄電池。2. A sealed lead-acid battery using a lead-calcium alloy as a positive electrode grid and an electrode plate manufactured by laminating a positive electrode and a negative electrode via a retainer, wherein bismuth is contained in an active material of the positive electrode. 0.001-1 wt.%, Arsenic 0.001-0.5 wt.%
% A sealed lead-acid battery characterized by being present.
し、正極、負極をリテーナを介して積層して作製する極
板群を用いた密閉形鉛蓄電池において、前記正極の活物
質中にビスマスを0.001〜１wt.%、錫を0.001〜3wt.%存
在させたことを特徴とする密閉形鉛蓄電池。3. A sealed lead-acid battery using a lead-calcium alloy as a positive electrode grid and an electrode plate manufactured by laminating a positive electrode and a negative electrode via a retainer, wherein bismuth is contained in an active material of the positive electrode. A sealed lead-acid battery characterized by having 0.001 to 1 wt.% And tin being present at 0.001 to 3 wt.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11000558A JP2000200598A (en) | 1999-01-05 | 1999-01-05 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11000558A JP2000200598A (en) | 1999-01-05 | 1999-01-05 | Sealed lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000200598A true JP2000200598A (en) | 2000-07-18 |
Family
ID=11477066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11000558A Pending JP2000200598A (en) | 1999-01-05 | 1999-01-05 | Sealed lead-acid battery |
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| Country | Link |
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| JP (1) | JP2000200598A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004047201A1 (en) * | 2002-11-15 | 2004-06-03 | Gs Yuasa Corporation | Positive plate for lead storage battery and lead storage battery |
| JP2005347145A (en) * | 2004-06-04 | 2005-12-15 | Furukawa Battery Co Ltd:The | Lead acid battery |
| JP2006086039A (en) * | 2004-09-16 | 2006-03-30 | Furukawa Battery Co Ltd:The | Lead-acid storage battery |
| WO2007036979A1 (en) * | 2005-09-27 | 2007-04-05 | The Furukawa Battery Co., Ltd. | Lead storage battery and process for producing the same |
| JP2013140677A (en) * | 2011-12-28 | 2013-07-18 | Gs Yuasa Corp | Liquid lead-acid battery and battery system using the same |
-
1999
- 1999-01-05 JP JP11000558A patent/JP2000200598A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004047201A1 (en) * | 2002-11-15 | 2004-06-03 | Gs Yuasa Corporation | Positive plate for lead storage battery and lead storage battery |
| CN1326262C (en) * | 2002-11-15 | 2007-07-11 | 株式会社杰士汤浅 | positive plate for lead-acid battery and lead-acid battery |
| JP2005347145A (en) * | 2004-06-04 | 2005-12-15 | Furukawa Battery Co Ltd:The | Lead acid battery |
| JP2006086039A (en) * | 2004-09-16 | 2006-03-30 | Furukawa Battery Co Ltd:The | Lead-acid storage battery |
| WO2007036979A1 (en) * | 2005-09-27 | 2007-04-05 | The Furukawa Battery Co., Ltd. | Lead storage battery and process for producing the same |
| JPWO2007036979A1 (en) * | 2005-09-27 | 2009-04-02 | 古河電池株式会社 | Lead-acid battery and method for producing lead-acid battery |
| AU2005336806B2 (en) * | 2005-09-27 | 2010-09-09 | The Furukawa Battery Co., Ltd. | Lead storage battery and process for producing the same |
| JP4799560B2 (en) * | 2005-09-27 | 2011-10-26 | 古河電池株式会社 | Lead-acid battery and method for producing lead-acid battery |
| US8771871B2 (en) | 2005-09-27 | 2014-07-08 | The Furukawa Battery Co., Ltd. | Lead storage battery and manufacturing method of the same |
| JP2013140677A (en) * | 2011-12-28 | 2013-07-18 | Gs Yuasa Corp | Liquid lead-acid battery and battery system using the same |
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