JPH10199562A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH10199562A JPH10199562A JP9014601A JP1460197A JPH10199562A JP H10199562 A JPH10199562 A JP H10199562A JP 9014601 A JP9014601 A JP 9014601A JP 1460197 A JP1460197 A JP 1460197A JP H10199562 A JPH10199562 A JP H10199562A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- separator
- amount
- positive electrode
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は正極格子にＰｂ−Ｃ
ａ系合金格子を用いた密閉形鉛蓄電池に関するもので、
その初期性能及び寿命性能の向上、特に正極活物質への
スズ、あるいはスズ化合物の添加による寿命性能向上を
図る際の弊害を抑える具体的な方策として、セパレータ
にシリカ粉体を添加するとともに該シリカ量を３０％以
上８０％以下に適正化することにより、従来以上の長寿
命化を達成することを目的とするものである。[0001] The present invention relates to a Pb-C
a sealed lead-acid battery using an a-based alloy lattice,
As a specific measure to improve the initial performance and the life performance, and particularly to suppress the adverse effect when the life performance is improved by adding tin or a tin compound to the positive electrode active material, a silica powder is added to the separator and the silica is added. By adjusting the amount to 30% or more and 80% or less, it is intended to achieve a longer life than the conventional one.
【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がある。2. Description of the Related Art A sealed type lead-acid battery is currently most widely used, and there is a retainer type battery in which a fine glass mat separator is in contact with positive and negative plates.
【０００３】この密閉形電池は、正極にＰｂ−Ｃａ系合
金格子を用いることが多いが、この場合、サイクル寿命
が従来の正極にＳｂ合金格子を用いた液式電池のそれに
比べるとかなり短いことが知られている。また、密閉形
鉛電池は上記寿命性能の安定化を図るために活物質の利
用率を低く抑えているため、初期から液式電池に比べて
エネルギー密度がかなり低く、ＥＶ用途などへの展開を
図る上で大きな問題になっている。[0003] In this sealed battery, a Pb-Ca based alloy lattice is often used for the positive electrode. In this case, the cycle life is considerably shorter than that of a conventional liquid battery using an Sb alloy lattice for the positive electrode. It has been known. In addition, the sealed lead-acid battery has a low active material utilization rate in order to stabilize the above-mentioned life performance. Therefore, the energy density is considerably lower than that of the liquid battery from the beginning, and it is expected to be applied to EV applications. It is a big problem in planning.
【０００４】[0004]
【発明が解決しようとする課題】Ｐｂ−Ｃａ系合金を用
いる密閉形鉛電池のエネルギー密度を向上させるために
古くから多くの対策が行われている。たとえば、特開昭
５４−４９５３８には、正極活物質に硫酸スズや二酸化
スズを添加することにより、初期性能を向上させる方策
が提案されている。しかしこの方法が未だに実用化して
いないのは、我々が研究した結果、スズが正極から溶出
・負極板に析出し、負極の充電効率を低下させ、寿命性
能が低下してしまうためであることがわかった。Many measures have been taken for a long time to improve the energy density of a sealed lead battery using a Pb-Ca alloy. For example, Japanese Patent Application Laid-Open No. 54-49538 proposes a method for improving initial performance by adding tin sulfate or tin dioxide to a positive electrode active material. However, this method has not yet been put to practical use because, as a result of our research, tin elutes from the positive electrode and precipitates on the negative electrode plate, lowering the charging efficiency of the negative electrode and reducing the life performance. all right.
【０００５】[0005]
【課題を解決するための手段】本発明密閉形鉛蓄電池
は、Ｐｂ−Ｃａ系合金の正極格子を用いたリテーナ式密
閉形鉛蓄電池であって、正極活物質に金属スズあるいは
スズ化合物を正極活物質重量当たり金属スズ換算で０．
５％以上５％以下添加するとともに、３０％以上８０％
以下のシリカ粉体を含んだ微細ガラス繊維を主体とする
セパレータを電解液保持体として用いる。また、セパレ
ータ中のシリカ粉体の比表面積が５０〜５００ｍ2 ／ｇ
であることを特徴とする。SUMMARY OF THE INVENTION The sealed lead-acid battery of the present invention is a sealed lead-acid battery of the retainer type using a positive electrode grid of a Pb-Ca alloy, wherein a metal tin or tin compound is used as a positive electrode active material. 0.1 in metal tin equivalent per substance weight.
5% or more and 5% or less, and 30% or more and 80%
A separator mainly composed of fine glass fibers containing the following silica powder is used as an electrolyte holder. Further, the specific surface area of the silica powder in the separator is 50 to 500 m 2 / g.
It is characterized by being.
【０００６】[0006]
【発明の実施の形態】本発明による密閉形鉛蓄電池は、
Ｐｂ−Ｃａ系合金の正極格子を用い、正極活物質に金属
スズあるいはスズ化合物を正極活物質重量当たり金属ス
ズ換算で０．５％〜５％添加するとともに、３０％〜８
０％のシリカ粉体を含んだ微細ガラス繊維を主体とする
セパレータを電解液保持体として用いる。また、セパレ
ータ中のシリカ粉体の比表面積が５０〜５００ｍ2 ／ｇ
の範囲のものを用いる。このようにすることにより、初
期のエネルギー密度だけでなく寿命性能を著しく向上す
ることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS A sealed lead-acid battery according to the present invention
Using a positive electrode lattice of a Pb-Ca alloy, metal tin or a tin compound is added to the positive electrode active material in an amount of 0.5% to 5% in terms of metal tin per weight of the positive electrode active material, and 30% to 8%.
A separator mainly composed of fine glass fibers containing 0% silica powder is used as an electrolyte holder. Further, the specific surface area of the silica powder in the separator is 50 to 500 m 2 / g.
Use the one in the range. By doing so, not only the initial energy density but also the life performance can be significantly improved.
【０００７】種々の検討の結果、我々は、正極活物質か
ら溶出したスズは、セパレータ中のシリカ粉体に吸着さ
れやすいことを発見した。シリカは比表面積が広いため
電解液中に溶出したスズがシリカ粉体に吸着されやす
く、その結果スズが負極板に析出するのを防いだものと
思われる。As a result of various studies, we have found that tin eluted from the positive electrode active material is easily adsorbed on silica powder in the separator. It is considered that since silica has a large specific surface area, tin eluted in the electrolytic solution is easily adsorbed to the silica powder, and as a result, tin is prevented from depositing on the negative electrode plate.
【０００８】以下の実施例にその結果の一例を示す。The following example shows an example of the result.
【０００９】[0009]
【実施例】Ｐｂ−０．０８％Ｃａ−１．０％Ｓｎ合金か
らなる正極格子に、ペースト練膏時に硫酸スズ粉末を既
化活物質重量当り金属スズ換算で０．１％（Ｂ）、０．
５％（Ｃ）、１％（Ｄ）、２％（Ｅ）、５％（Ｆ）、７
％（Ｇ）添加してなるペーストを充填した２．２ｍｍ厚
さの正極板を製作した。これらの正極板１１枚と１．．
７ｍｍ厚さのペースト式負極板１２枚と比表面積が２０
０ｍ2 ／ｇのシリカ粉体を１５％（ｂ）、３０％
（ｃ）、５０％（ｄ）、８０％（ｅ）、９０％（ｆ）含
んだ微細ガラスマットセパレータとから、約６０Ａｈ
（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。EXAMPLE A tin sulfate powder was added to a positive electrode grid made of a Pb-0.08% Ca-1.0% Sn alloy at the time of paste pulverization in an amount of 0.1% (B) in terms of metal tin per weight of a converted active material. 0.
5% (C), 1% (D), 2% (E), 5% (F), 7
% (G) to produce a 2.2 mm thick positive electrode plate filled with a paste. These 11 positive plates and 1. .
12 paste-type negative electrode plates with a thickness of 7 mm and a specific surface area of 20
15% (b), 30% of 0 m 2 / g silica powder
(C), 50% (d), 80% (e), 90% (f) from the fine glass mat separator containing about 60Ah
A (3 hR) -12 V retainer-type sealed battery was manufactured according to a normal manufacturing method.
【００１０】なお、硫酸スズを添加していない従来の標
準極板を用いた電池（Ａ）、硫酸スズを添加しているが
セパレータにシリカを含んでいない従来のセパレータ
（ａ）を用いた電池も併せて製作した。これらの電池は
常法に従って所定の注液・充電を行ない、以下の試験に
供した。A battery using a conventional standard electrode plate to which tin sulfate is not added (A), and a battery using a conventional separator (a) to which tin sulfate is added but containing no silica as a separator. Was also produced. These batteries were subjected to predetermined injection and charging according to a conventional method, and subjected to the following tests.
【００１１】まず、３０℃で１／３ＣＡ放電容量を測定
した。試験結果を図１に示す。図からわかるように、硫
酸スズの添加量が５％までは、硫酸スズを０．５％以上
添加すると、容量が大きく向上していることがわかる。
なお、セパレータのシリカ量を多くすると、セパレータ
の多孔度が低下するためやや放電容量が低下したが、実
用上はほとんど問題ない程度である。First, 1/3 CA discharge capacity was measured at 30 ° C. The test results are shown in FIG. As can be seen from the figure, when the amount of tin sulfate added is up to 5%, the capacity is greatly improved by adding 0.5% or more of tin sulfate.
In addition, when the amount of silica in the separator is increased, the porosity of the separator is reduced, so that the discharge capacity is slightly reduced.
【００１２】つぎに、これらの電池を寿命試験に供し
た。寿命試験は４０℃で、１／３ＣＡ電流で定格の８０
％を放電した後、定電流で放電量の１１０％を充電する
という一般的な条件で行った。試験結果を図２に示す。Next, these batteries were subjected to a life test. Life test at 40 ° C, rated at 80 at 1/3 CA current
%, And then charged under a general condition of charging 110% of the discharge amount at a constant current. The test results are shown in FIG.
【００１３】硫酸スズを０．５％以上５％以下添加し、
セパレータ中のシリカ量を３０％以上８０％以下にした
電池では、従来の硫酸スズを添加しない電池に比べ著し
く寿命性能が優れていた。一方、正極に硫酸スズを０．
１％だけ添加した極板を用いた電池の寿命性能は、無添
加の電池と大差なかった。また、硫酸スズ添加量によら
ずセパレータ中のシリカ量を９０％にしたものは早期に
容量低下した。おそらくこの場合は、シリカを多くしす
ぎたためにセパレータにしみこんだ電解液の移動が遅く
なりすぎて電池性能に悪影響を及ぼしたものと思われ
る。[0013] Tin sulfate is added in an amount of 0.5% or more and 5% or less,
The battery in which the amount of silica in the separator was 30% or more and 80% or less had remarkably superior life performance as compared with a conventional battery in which tin sulfate was not added. On the other hand, tin sulfate was added to the positive electrode at 0.1.
The life performance of the battery using the electrode plate to which only 1% was added was not much different from the battery to which no electrode was added. In the case where the amount of silica in the separator was 90% regardless of the amount of tin sulfate added, the capacity was reduced at an early stage. Possibly, in this case, the amount of silica was too large, so that the movement of the electrolyte impregnated into the separator was too slow, which adversely affected the battery performance.
【００１４】正極活物質中の硫酸スズ量が７％と最も多
い場合にはセパレータ中のシリカ量によらず早期に容量
が低下した。寿命試験後に解体し負極板に析出していた
スズ量を調べると、硫酸スズが７％の場合にはセパレー
タ中のシリカ量によらず負極板中にスズが多量に析出し
ていた。またスズ量が５％以下の場合でもセパレータ中
のシリカ量が３０％未満の場合には多量のスズが析出し
ていた。When the amount of tin sulfate in the positive electrode active material was as high as 7%, the capacity was reduced promptly regardless of the amount of silica in the separator. When the amount of tin deposited on the negative electrode plate after disassembly after the life test was examined, a large amount of tin was deposited on the negative electrode plate regardless of the amount of silica in the separator when the amount of tin sulfate was 7%. Even when the amount of tin was 5% or less, a large amount of tin was precipitated when the amount of silica in the separator was less than 30%.
【００１５】以上のことから、正極活物質にスズを０．
５％〜５％添加して、かつシリカ粉体を３０％〜８０％
添加したセパレータを用いることにより、リテーナ式密
閉形鉛蓄電池のエネルギー密度が向上するだけでなく長
寿命化が達成できることがわかった。[0015] From the above, tin is added to the positive electrode active material in an amount of 0.1.
5% to 5% added, and 30% to 80% silica powder
It has been found that by using the added separator, not only the energy density of the sealed lead storage battery of the retainer type can be improved, but also a long life can be achieved.
【００１６】なお、本実施例ではスズとして硫酸スズを
用いたが、酸化スズを用いてもまた、金属スズを用いて
も結果に差はほとんどなかった。また、セパレータの主
成分は０．５〜５ミクロンの微細なガラス繊維である
が、これまでの試験結果から本試験の結果はセパレータ
の繊維径にはよらないこともわかっている。In this embodiment, tin sulfate was used as tin. However, there was almost no difference between tin oxide and tin metal. Although the main component of the separator is fine glass fiber of 0.5 to 5 microns, it has been found from the test results so far that the result of this test does not depend on the fiber diameter of the separator.
【００１７】また、本試験では２００ｍ2 ／ｇのシリカ
粉体を用いたが、試験の結果、５０ｍ2 ／ｇ〜５００ｍ
2 ／ｇの比表面積のシリカを用いた場合にその効果が大
きかった。５００ｍ2 ／ｇを越える比表面積のシリカ粉
体を用いると、電解液の移動がよくないせいか、容量低
下が大きくなる傾向が見られた。In this test, silica powder of 200 m 2 / g was used. As a result of the test, 50 m 2 / g to 500 m 2 / g was used.
The effect was significant when silica having a specific surface area of 2 / g was used. When a silica powder having a specific surface area of more than 500 m 2 / g was used, there was a tendency that a decrease in the capacity became large probably because the movement of the electrolytic solution was not good.
【００１８】[0018]
【発明の効果】本発明は正極格子にＰｂ−Ｃａ系合金格
子を用いた密閉形鉛蓄電池において正極活物質に０．５
％〜５％のスズあるいはスズ化合物を添加すると同時
に、５０ｍ2 ／ｇ〜５００ｍ2 ／ｇのシリカ粉体を３０
％以上８０％以下添加することにより初期のエネルギー
密度だけでなく寿命性能向上が著しく向上しており、リ
テーナ式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。According to the present invention, a sealed lead-acid battery using a Pb-Ca alloy grid as the positive grid has a positive electrode active material of 0.5%.
% To 5% at the same time the addition of tin or tin compounds, silica powder 50m 2 / g~500m 2 / g 30
% To 80%, not only the initial energy density but also the life performance is remarkably improved, and the industrial value of the retainer-type sealed lead-acid battery is extremely large from the viewpoint of practical use.
【図１】スズ添加量およびセパレータ中のシリカ量と初
期容量との関係を示す特性図FIG. 1 is a characteristic diagram showing the relationship between the amount of tin added, the amount of silica in a separator, and the initial capacity.
【図２】スズ添加量およびセパレータ中のシリカ量と寿
命性能との関係を示す特性図FIG. 2 is a characteristic diagram showing the relationship between the amount of tin added, the amount of silica in a separator, and the life performance.
Claims (2)
テーナ式密閉形鉛蓄電池であって、正極活物質に金属ス
ズあるいはスズ化合物を正極活物質重量当たり金属スズ
換算で０．５％以上５％以下添加するとともに、３０％
以上８０％以下のシリカ粉体を含んだ微細ガラス繊維を
主体とするセパレータを電解液保持体として用いたこと
を特徴とするリテーナ式密閉形鉛蓄電池。1. A closed lead-acid battery using a positive electrode grid of a Pb—Ca alloy, comprising metal tin or a tin compound as a positive electrode active material in an amount of 0.5% or more in terms of metal tin per weight of the positive electrode active material. Add 5% or less and 30%
A sealed sealed lead-acid storage battery characterized in that a separator mainly composed of fine glass fibers containing not less than 80% of silica powder is used as an electrolyte holder.
５０〜５００ｍ2 ／ｇであることを特徴とする請求項１
に記載のリテーナ式密閉形鉛蓄電池。2. The silica powder in the separator has a specific surface area of 50 to 500 m 2 / g.
The sealed lead storage battery of the retainer type described in 1.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9014601A JPH10199562A (en) | 1997-01-10 | 1997-01-10 | Sealed lead-acid battery |
| US08/995,135 US6225005B1 (en) | 1996-12-19 | 1997-12-19 | Lead-acid battery and producing method thereof |
| CNB971217416A CN1161857C (en) | 1996-12-19 | 1997-12-19 | Lead-acid battery and producing method thereof |
| DE69736735T DE69736735T2 (en) | 1996-12-19 | 1997-12-19 | Lead-acid battery and manufacturing process |
| EP97122546A EP0849816B1 (en) | 1996-12-19 | 1997-12-19 | Lead-acid battery and producing method thereof |
| US09/729,172 US6495288B2 (en) | 1996-12-19 | 2000-12-05 | Lead-acid battery having tin in positive active material and silica in separator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9014601A JPH10199562A (en) | 1997-01-10 | 1997-01-10 | Sealed lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10199562A true JPH10199562A (en) | 1998-07-31 |
Family
ID=11865721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9014601A Pending JPH10199562A (en) | 1996-12-19 | 1997-01-10 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10199562A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007104416A1 (en) * | 2006-03-15 | 2007-09-20 | P.C. Di Pompeo Catelli | Process for producing battery electrodes, electrodes produced by this process, and batteries containing such electrodes |
| JP2013048082A (en) * | 2011-07-25 | 2013-03-07 | Gs Yuasa Corp | Lead acid battery |
| JPWO2016139855A1 (en) * | 2015-03-05 | 2017-08-10 | 日立化成株式会社 | Lead acid battery |
-
1997
- 1997-01-10 JP JP9014601A patent/JPH10199562A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007104416A1 (en) * | 2006-03-15 | 2007-09-20 | P.C. Di Pompeo Catelli | Process for producing battery electrodes, electrodes produced by this process, and batteries containing such electrodes |
| JP2009529773A (en) * | 2006-03-15 | 2009-08-20 | ピ．チ．ディ ポンペオ カテッリ | Battery electrode manufacturing method, electrode manufactured by this method, and battery having such an electrode |
| JP2013048082A (en) * | 2011-07-25 | 2013-03-07 | Gs Yuasa Corp | Lead acid battery |
| JPWO2016139855A1 (en) * | 2015-03-05 | 2017-08-10 | 日立化成株式会社 | Lead acid battery |
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