JPH10294113A - Positive electrode plate for sealed lead-acid battery - Google Patents
Positive electrode plate for sealed lead-acid batteryInfo
- Publication number
- JPH10294113A JPH10294113A JP9116223A JP11622397A JPH10294113A JP H10294113 A JPH10294113 A JP H10294113A JP 9116223 A JP9116223 A JP 9116223A JP 11622397 A JP11622397 A JP 11622397A JP H10294113 A JPH10294113 A JP H10294113A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- electrode plate
- positive electrode
- active material
- grid
- 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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、密閉型鉛蓄電池用
正極板の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a positive electrode plate for a sealed lead-acid battery.
【０００２】[0002]
【従来の技術】電池の充電中に発生する酸素ガスを負極
板で吸収するいわゆる酸素サイクルを利用した密閉型鉛
蓄電池には、現在リテーナ式と呼ばれている方式が一般
的に採用されている。リテーナ式は正極板と負極板との
間に挿入した微細なガラス繊維を素材とするマット状セ
パレータ（ガラスセパレータ）で電池の充放電に必要な
硫酸電解液の保持と両極の隔離を行う方式である。2. Description of the Related Art In a sealed lead-acid battery utilizing a so-called oxygen cycle in which oxygen gas generated during charging of a battery is absorbed by a negative electrode plate, a system which is currently called a retainer type is generally employed. . The retainer type is a mat type separator (glass separator) made of fine glass fiber inserted between the positive electrode plate and the negative electrode plate, which holds the sulfuric acid electrolyte necessary for battery charging and discharging and separates both electrodes. is there.
【０００３】そして、無保守、無漏液、ポジションフリ
ーなどの特徴を活かして、ポータブル機器、コンピュー
タのバックアップ電源、また大型の据置用途に用いられ
ている。近年無停電電源装置（以下ＵＰＳと記す）に用
いられる密閉型鉛蓄電池は、トリクル充電され、期待寿
命が３年程度であったものが、５年以上の長寿命化を要
求されるようになってきた。その正極格子には、Ｐｂ−
Ｃａ−Ｓｎ系合金が使用されている。寿命性能向上のた
め格子に用いられる合金は種々検討がなされてきたが、
正極板の活物質に使用する鉛粉は高純度のものが良いと
され、ＪＩＳＨ ２０１５ に規定されている特種の純
鉛を用いている。Utilizing features such as maintenance-free, liquid-free, and position-free, they are used for portable equipment, backup power supplies for computers, and large stationary applications. In recent years, sealed lead-acid batteries used in uninterruptible power supplies (hereinafter referred to as UPS) have been trickle charged and have an expected life of about 3 years, but have been required to have a longer life of 5 years or more. Have been. The positive grid has Pb-
A Ca—Sn based alloy is used. Various studies have been made on alloys used for lattices to improve life performance,
The lead powder used as the active material of the positive electrode plate is preferably of high purity, and a special type of pure lead specified in JIS H2015 is used.
【０００４】[0004]
【発明が解決しようとする課題】この用途で用いられる
密閉型鉛蓄電池の性能劣化原因は、正極板の活物質が格
子から浮き上がり、活物質と格子の密着性が損なわれる
ため導電性が低下することにある。The performance deterioration of the sealed lead-acid battery used in this application is caused by the fact that the active material of the positive electrode plate floats up from the grid and the adhesion between the active material and the grid is impaired, so that the conductivity is reduced. It is in.
【０００５】[0005]
【課題を解決するための手段】第一の発明は、Ｐｂ−Ｃ
ａ系合金格子を用いた密閉型鉛蓄電池において、Ｐｂ−
Ｂａ系合金から作製した鉛粉を原料に用いることを特徴
とするものであり、第二の発明は、格子合金中のＣａ量
が０．０４〜０．１重量％であることを特徴とし、第三
の発明は、Ｂａ含有量が０．００１〜０．０１重量％で
あるＰｂ−Ｂａ系合金をもちいたことを特徴とするもの
である。Means for Solving the Problems The first invention is a Pb-C
In a sealed lead-acid battery using an a-based alloy lattice, Pb-
A lead powder produced from a Ba-based alloy is used as a raw material. The second invention is characterized in that the Ca content in the lattice alloy is 0.04 to 0.1% by weight, The third invention is characterized by using a Pb-Ba alloy having a Ba content of 0.001 to 0.01% by weight.
【０００６】[0006]
【実施例】以下、本発明を実施例に基づいて説明する。
鉛粉の原料となる鉛を、ＪＩＳＨ ２０１５ に規定さ
れている特種の純鉛を溶融し、純度９９％のＢａ試薬を
所定量添加することで製作した。この合金から製作した
鉛粉を希硫酸で練膏し、ペーストとしたのち、各種鉛合
金格子に充填し、正極板とした。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
Lead as a raw material of lead powder was produced by melting a special type of pure lead specified in JIS 2015 and adding a predetermined amount of a Ba reagent having a purity of 99%. Lead powder produced from this alloy was pulverized with dilute sulfuric acid to form a paste, and then filled into various lead alloy lattices to form a positive electrode plate.
【０００７】セパレータには、ガラス繊維の平均直径約
１μｍ、多孔度約９４％の通常使用されているものを用
い、２０ｋｇ／ｄｍ2の荷重下で、厚さが１．５ｍｍの
ものを使用した。負極板、電解液についても従来のもの
を使用し２Ｖ８Ａｈの密閉型鉛蓄電池を製作した。電槽
化成を行ったのち容量評価試験を２サイクル行い、トリ
クル寿命試験に供した。トリクル寿命試験は、加速のた
め温度を５０℃として行った。試験に用いた電池番号と
正極板の内容を表１に示す。As the separator, a commonly used glass fiber having an average diameter of about 1 μm and a porosity of about 94% was used, and a separator having a thickness of 1.5 mm under a load of 20 kg / dm 2 was used. . A sealed lead-acid battery of 2V8Ah was manufactured using a conventional negative electrode plate and electrolyte. After performing battery case formation, a capacity evaluation test was performed for two cycles and subjected to a trickle life test. The trickle life test was performed at a temperature of 50 ° C. for acceleration. Table 1 shows the battery numbers and the contents of the positive electrode plates used in the test.
【０００８】[0008]
【表１】 試験条件 容量評価試験（２５℃） 放電 ８Ａ 終止電圧１．７Ｖ 充電 ０．８Ａ×（放電電気量の１３５％） トリクル試験条件（５０℃） トリクル電圧 ２．３Ｖ／セル ３ヶ月毎に 容量評価試験 初期の容量評価試験の２サイクル目の放電持続時間とＢ
a添加量の関係を図１に示す。図に示したように鉛粉中
にＢaを添加したことによる悪影響は認められず、逆に
放電持続時間は伸びる傾向が認められた。格子合金種の
影響は、認められなかった。トリクル寿命試験の結果を
図２に示す。図に示したように、従来のＢａを添加して
いない鉛粉で製作した正極板を用いた電池（電池Ｎｏ．
１，５，９）は、約１年で寿命となった。これに対しＢ
ａを０．００１〜０．０１重量％を含む鉛粉で製作し、
格子合金のＣａ量が０．０４重量％の電池（電池Ｎｏ．
２，３）と、格子合金のＣａ量が０．１０重量％の電池
（電池Ｎｏ．６，７）では、約１８〜２４ヶ月で寿命と
なり、寿命が大幅に向上した。これらの電池を試験後に
解体すると、活物質は軟化していたが、格子と活物質の
密着性は良好であった。このことが寿命が増大したこと
の原因と思われる。Ｂａの量を０．０５重量％添加した
電池（電池Ｎｏ．４，８，１２）では、初期の放電容量
は増加したものの途中からの容量低下が大きく、寿命性
能の向上にはあまり効果がなかった。０．０５重量％の
Ｂａを添加した電池の活物質は、試験後に調査すると、
若干軟化気味であった。従来、負極に０．２〜０．５重
量％添加しているＢａＳＯ4を正極活物質に誤って混入
すると、活物質が軟化し性能が劣化すると言われいる
が、０．０５重量％程度でもこの悪影響が認められた。
０．１３重量％Ｃａの格子合金を用いた電池（電池Ｎ
ｏ．１１）では、途中から容量低下を起こし、１５ヶ月
目の容量確認試験では、放電持続時間が著しく短くなっ
た。この電池を試験終了後に解体調査すると、正極格子
の伸びが他に比べて大きかった。Ｂａが活物質中に存在
すると、活物質が柔らかくなることで格子の伸びに対応
し、格子と活物質の界面の密着性が保たれ、寿命性能が
向上するものと考えられるが、格子の伸びが大きすぎる
と、対応しきれず、Ｃａ添加量を増やしすぎると逆に悪
影響がでてしまったものと思われる。[Table 1] Test conditions Capacity evaluation test (25 ° C) Discharge 8A Final voltage 1.7V Charge 0.8A x (135% of the amount of discharged electricity) Trickle test conditions (50 ° C) Trickle voltage 2.3V / cell Every 3 months Capacity evaluation test Discharge duration and B in the second cycle of the initial capacity evaluation test
FIG. 1 shows the relationship between the amounts of addition. As shown in the figure, no adverse effect was observed due to the addition of Ba to the lead powder, and conversely, the discharge duration time tended to increase. No effect of the lattice alloy type was observed. FIG. 2 shows the result of the trickle life test. As shown in the figure, a battery using a conventional positive electrode plate made of lead powder without adding Ba (battery No. 1).
1, 5, 9) had a life of about one year. On the other hand, B
a made of lead powder containing 0.001 to 0.01% by weight,
Batteries having a lattice alloy Ca content of 0.04% by weight (Battery No.
2, 3) and the battery (battery Nos. 6, 7) in which the Ca content of the lattice alloy was 0.10% by weight, the life was extended in about 18 to 24 months, and the life was greatly improved. When these batteries were disassembled after the test, the active material was softened, but the adhesion between the grid and the active material was good. This seems to be the cause of the increased life. In the batteries (Battery Nos. 4, 8, and 12) to which 0.05% by weight of Ba was added, although the initial discharge capacity was increased, the capacity was reduced from the middle, but was not so effective in improving the life performance. Was. When the active material of the battery to which 0.05% by weight of Ba was added was examined after the test,
It was slightly softening. Conventionally, it has been said that if BaSO 4 added to the negative electrode in an amount of 0.2 to 0.5% by weight is erroneously mixed into the positive electrode active material, the active material is softened and the performance is deteriorated. This adverse effect was observed.
A battery using a 0.13 wt% Ca lattice alloy (Battery N
o. In the case of 11), the capacity was reduced halfway, and in the capacity check test at the 15th month, the discharge duration time was significantly shortened. When the battery was disassembled and inspected after completion of the test, the positive electrode lattice had a larger elongation than the others. When Ba is present in the active material, it is considered that the active material is softened to cope with the elongation of the lattice, the adhesion between the lattice and the active material is maintained, and the life performance is improved. Is too large, it seems impossible to cope with it. Conversely, if the added amount of Ca is excessively increased, adverse effects appear to have occurred.
【０００９】従来の高純度の鉛粉を使用し、ペーストと
するときにＢａＳＯ4の粉末を添加することでも上記効
果を期待できるが、量産の場合一度に数百Ｋｇ単位で練
膏するためペースト中でＢａが均一に拡散せず、極板毎
に性能が安定しなくなる問題がある。本発明のようにＢ
ａを含む鉛粉を使用すれば、このような問題の発生を抑
えることができる。The above effect can be expected by using conventional high-purity lead powder and adding BaSO 4 powder when forming the paste. However, in mass production, paste is applied in units of several hundred kg at a time. There is a problem that Ba does not diffuse uniformly in the inside, and the performance becomes unstable for each electrode plate. B as in the present invention
The use of a lead powder containing a can suppress the occurrence of such a problem.
【００１０】[0010]
【発明の効果】以上詳述したようにＰｂ−Ｃａ系合金格
子を用いた密閉型鉛蓄電池において、Ｐｂ−Ｂａ系合金
から製作した鉛粉を原料とした活物質を使用した正極板
を用いることで、トリクル寿命性能の優れた密閉型鉛蓄
電池を製造することが可能になった。As described in detail above, in a sealed lead-acid battery using a Pb-Ca-based alloy lattice, a positive electrode plate using an active material made of a lead powder manufactured from a Pb-Ba-based alloy is used. Thus, a sealed lead-acid battery having excellent trickle life performance can be manufactured.
【図１】初期性能を示す図である。FIG. 1 is a diagram showing initial performance.
【図２】トリクル寿命特性を示す図である。FIG. 2 is a diagram showing a trickle life characteristic.
Claims (3)
電池において、Ｐｂ−Ｂａ系合金から製作した鉛粉を原
料に用いることを特徴とする密閉型鉛蓄電池用正極板。1. A positive electrode plate for a sealed lead-acid battery, wherein a lead powder produced from a Pb-Ba-based alloy is used as a raw material in a sealed lead-acid battery using a Pb-Ca-based alloy lattice.
重量％であることを特徴とする請求項１記載の密閉型鉛
蓄電池用正極板。2. The method according to claim 2, wherein the amount of Ca in the lattice alloy is 0.04 to 0.1.
2. The positive electrode plate for a sealed lead-acid battery according to claim 1, wherein the content is by weight. 3.
であるＰｂ−Ｂａ系合金から製作した鉛粉を用いたこと
を特徴とする請求項１又は２記載の密閉型鉛蓄電池用正
極板。3. The content of Ba is 0.001 to 0.01% by weight.
The positive electrode plate for a sealed lead-acid battery according to claim 1 or 2, wherein a lead powder produced from a Pb-Ba alloy is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9116223A JPH10294113A (en) | 1997-04-17 | 1997-04-17 | Positive electrode plate for sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9116223A JPH10294113A (en) | 1997-04-17 | 1997-04-17 | Positive electrode plate for sealed lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10294113A true JPH10294113A (en) | 1998-11-04 |
Family
ID=14681884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9116223A Pending JPH10294113A (en) | 1997-04-17 | 1997-04-17 | Positive electrode plate for sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10294113A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004104244A1 (en) | 2003-05-26 | 2004-12-02 | The Furukawa Battery Co., Ltd. | Lead-based alloy for lead-acid battery grid |
| US7862931B2 (en) | 2002-04-18 | 2011-01-04 | The Furukawa Battery Co., Ltd. | Lead-based alloy for lead-acid battery, substrate for lead-acid battery and lead-acid battery |
| JP2011258531A (en) * | 2010-06-11 | 2011-12-22 | Gs Yuasa Corp | Lead-acid storage battery |
| CN110600815A (en) * | 2019-09-20 | 2019-12-20 | 南阳师范学院 | Rolled lead-acid storage battery and preparation method and application thereof |
-
1997
- 1997-04-17 JP JP9116223A patent/JPH10294113A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7862931B2 (en) | 2002-04-18 | 2011-01-04 | The Furukawa Battery Co., Ltd. | Lead-based alloy for lead-acid battery, substrate for lead-acid battery and lead-acid battery |
| WO2004104244A1 (en) | 2003-05-26 | 2004-12-02 | The Furukawa Battery Co., Ltd. | Lead-based alloy for lead-acid battery grid |
| AU2003292555B2 (en) * | 2003-05-26 | 2006-10-12 | The Furukawa Battery Co., Ltd. | Lead-based alloy for lead-acid battery grid |
| JP2011258531A (en) * | 2010-06-11 | 2011-12-22 | Gs Yuasa Corp | Lead-acid storage battery |
| CN110600815A (en) * | 2019-09-20 | 2019-12-20 | 南阳师范学院 | Rolled lead-acid storage battery and preparation method and application thereof |
| CN110600815B (en) * | 2019-09-20 | 2020-10-09 | 南阳师范学院 | Rolled lead-acid storage battery and preparation method and application thereof |
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