JPH01241753A - Sealed type clad type lead storage battery - Google Patents
Sealed type clad type lead storage batteryInfo
- Publication number
- JPH01241753A JPH01241753A JP63069015A JP6901588A JPH01241753A JP H01241753 A JPH01241753 A JP H01241753A JP 63069015 A JP63069015 A JP 63069015A JP 6901588 A JP6901588 A JP 6901588A JP H01241753 A JPH01241753 A JP H01241753A
- Authority
- JP
- Japan
- Prior art keywords
- antimony
- positive electrode
- lead
- active substance
- electrode active
- 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
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 46
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910045601 alloy Inorganic materials 0.000 claims abstract 2
- 239000000956 alloy Substances 0.000 claims abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011245 gel electrolyte Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000978 Pb alloy Inorganic materials 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 6
- 229910002056 binary alloy Inorganic materials 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002142 lead-calcium alloy Substances 0.000 description 4
- 229910001245 Sb alloy Inorganic materials 0.000 description 3
- 239000002140 antimony alloy Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for 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
- H01M10/06—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は深い充放電を繰り返し行う、いわゆるサイクル
サービス用途で使用される密閉式鉛蓄電池の改良に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to improvements in sealed lead-acid batteries used in so-called cycle service applications in which deep charging and discharging are repeated.
従来の技術とその課題
密閉式ｊ９蓄電池は深い放電を含む充放電サイクルでは
著しく寿命が短くなることが知られている。Prior art and its problems It is known that sealed J9 storage batteries have a significantly shortened lifespan during charge/discharge cycles that include deep discharge.
これは密閉式鉛蓄電池ではアンチモンを含有しない格子
体が使用されており、この様な格子体を用いた正極板の
深放電での耐久性が著しく劣るためである。一方、アン
チモンを含有する格子体を使用すれば、深放電での耐久
性には問題はないが正極格子体から溶出するアンチモン
のために負極板の水素過電圧が低下し、水素発生による
電解液（水）の分解のなめ、寿命が短くなるという開門
が起こる。このなめフォークリフト用などの深い充放電
が繰り返される用途に対して満足な寿命性能を有する密
閉形電池はいまだ無いというのが現状である。This is because sealed lead-acid batteries use lattice bodies that do not contain antimony, and the durability of positive electrode plates using such lattice bodies during deep discharge is significantly inferior. On the other hand, if a lattice containing antimony is used, there is no problem with durability in deep discharge, but the hydrogen overvoltage of the negative electrode plate decreases due to the antimony eluted from the positive electrode lattice, and the electrolyte (due to hydrogen generation) Water) decomposes, leading to a shortened lifespan. The current situation is that there is currently no sealed battery that has a satisfactory lifespan for applications where deep charging and discharging are repeated, such as for forklifts.
課題を解決するための手段
本発明は正極格子体に低濃度のアンチモンを含有する鉛
合金を使用し、かつ該格子体を取り囲む活物質層を厚く
することによって、上記したような従来の問題点を解消
し、深い放電を含む充放電サイクルでの寿命性能の優れ
た密閉式鉛蓄電池を提供しようとするものである。Means for Solving the Problems The present invention solves the above-mentioned conventional problems by using a lead alloy containing a low concentration of antimony in the positive electrode grid and increasing the thickness of the active material layer surrounding the grid. The purpose of the present invention is to provide a sealed lead-acid battery that has excellent service life performance in charge-discharge cycles including deep discharge.
作用
負極の水素過電圧の低下は既に述べたようにアンチモン
に起因するものであるが、これは次のような現ゑによる
ものである。正極格子体が腐食されると、その格子体中
のアンチモンも酸化アンチモンとなる。この酸化アンチ
モンは希硫酸に溶解し易く、３価や５価のイオンや化合
物となって格子体近傍の電解液中に存在する。これらは
拡散や泳動によって正極活物質中のボア内を通ってバル
クの電解液に達し、ついには負極板に到達してその表面
に電析する。これが水素過電圧を低下させる原因となる
。しかるに正極活物質である二酸化鉛はアンチモンを吸
着し、アンチモンの負極板への移動を阻止する作用があ
る。したがって格子体からのアンチモンの溶出を抑える
と共に、正極活物質層を厚くすることにより正極活物質
がアンチモンを吸着する能力を増やせば即ちアンチモン
の溶出量より正極活物質によるアンチモンの吸着能力を
大きくすれば負極板へアンチモンが到達することを阻止
でき水素過電圧を低下させることはない。As mentioned above, the decrease in hydrogen overvoltage of the working negative electrode is caused by antimony, and this is due to the following circumstances. When the positive electrode lattice is corroded, the antimony in the lattice also turns into antimony oxide. This antimony oxide is easily dissolved in dilute sulfuric acid, and exists in the electrolytic solution near the lattice body as trivalent or pentavalent ions or compounds. These particles pass through the bore in the positive electrode active material by diffusion and migration, reach the bulk electrolyte, and finally reach the negative electrode plate and are deposited on its surface. This causes the hydrogen overvoltage to decrease. However, lead dioxide, which is a positive electrode active material, has the effect of adsorbing antimony and preventing antimony from migrating to the negative electrode plate. Therefore, by suppressing the elution of antimony from the lattice and increasing the thickness of the positive electrode active material layer, the antimony adsorption ability of the positive electrode active material can be made larger than the amount of antimony eluted. This prevents antimony from reaching the negative electrode plate and does not reduce the hydrogen overvoltage.
実施例
そこで、正極活物Ｍ層厚や正極格子体中のアンチモン濃
度と寿命性能との関係について次のような実験を行った
。Example The following experiment was conducted to examine the relationship between the thickness of the positive electrode active material M layer, the antimony concentration in the positive electrode lattice, and the life performance.
実＠１．アンチモンの濃度が３．Ｏｗｔ％の釦−アンチ
モン合金格子体を用いて活物質層厚が２．７゜２．９
、３．１ 、３．３ 、３．５および３．７ｖｙのクラ
ッド式正極板を常法に従い製作し、これと鉛−カルシウ
ム合金格子体から成る負極板とを用いて電池を構成した
。これにシリカ微粒子と希硫酸とから成るゲル状電解液
を注入し、ゲルタイプの密閉形電池として試験に供した
。試験は電池を１．７０Ｖまで放電し、その後２．４０
Ｖの定電圧で充電するという条件で行い、それぞれの電
池の放電容量が初期の８０％に達するまで充放電を繰り
返した。また、この時点で電池を解体し、負極活物質中
のアンチモンの濃度を分析した。放電容量が初期の８０
％に達した時点のサイクル数や負極活物質中のアンチモ
ン濃度と正極活物質層厚との関係を第１図に示す。Fruit @1. The concentration of antimony is 3. Using Owt% button-antimony alloy lattice, the active material layer thickness is 2.7°2.9
, 3.1, 3.3, 3.5, and 3.7vy were manufactured according to a conventional method, and a battery was constructed using these and a negative electrode plate made of a lead-calcium alloy lattice. A gel electrolyte consisting of fine silica particles and dilute sulfuric acid was injected into this, and the battery was tested as a gel-type sealed battery. The test was to discharge the battery to 1.70V and then to 2.40V.
Charging was carried out under the condition of charging at a constant voltage of V, and charging and discharging were repeated until the discharge capacity of each battery reached 80% of the initial value. At this point, the battery was disassembled and the concentration of antimony in the negative electrode active material was analyzed. The initial discharge capacity is 80
%, the relationship between the number of cycles, the antimony concentration in the negative electrode active material, and the thickness of the positive electrode active material layer is shown in FIG.
第１図から、正極活物質層厚が２．７〜３．１１１＋１
の範囲では、活物質層が厚くなるに従って寿命は長くな
るが、寿命に達した時点での負極活物質中のアンチモン
濃度はほぼ一定（約１４０ｐｐｌ）であることがわかる
、この結果は負極活物質中のアンチモン濃度が１４０ｐ
ｐｎ程度まで高くなると、アンチモンのために負極板の
水素過電圧が著しく低下し、充電効率の低下と水素発生
による電解液°の分解のなめ、寿命が短くなったことを
示している。実際、これらの電池では減液量が著しく大
であった。すなわち、これらの電池では負極板へのアン
チモンの析出により短寿命となったといえる。From Figure 1, the positive electrode active material layer thickness is 2.7 to 3.111+1
It can be seen that in the range of The antimony concentration inside is 140p.
When the temperature rises to about pn, the hydrogen overvoltage of the negative electrode plate decreases significantly due to antimony, indicating a decrease in charging efficiency and decomposition of the electrolyte due to hydrogen generation, resulting in a shortened lifespan. In fact, the amount of liquid loss in these batteries was significantly large. In other words, it can be said that the lifespan of these batteries was shortened due to the precipitation of antimony on the negative electrode plate.
一方、正極活物質層厚が３．３ｎＩｍ以上の範囲では寿
命に達した時点での負極活物質中のアンチモン濃度は、
１４０ｐｐｎに達しておらず、３．１ｎｍ以下の場合に
比べて著しく少なく寿命性能も良い、すなわち、格子体
のアンチモン濃度が３．Ｏｗｔ％の場合には正極活’Ｉ
’！ＩＮ質層厚を３．３ Ｉｎ以上にすることにより、
負極板へのアンチモンの析出を阻止できた結果、クラッ
ド式電池本来の寿命特性を発揮でき、長寿命を達成し得
たと考えられる。On the other hand, when the positive electrode active material layer thickness is in a range of 3.3 nIm or more, the antimony concentration in the negative electrode active material at the end of its life is
The antimony concentration of the lattice body is less than 140 ppn, which is significantly lower than that of 3.1 nm or less, and the lifetime performance is also good. In the case of Owt%, the positive electrode active 'I
'! By setting the IN layer thickness to 3.3 In or more,
It is thought that as a result of being able to prevent the precipitation of antimony on the negative electrode plate, the original life characteristics of a clad type battery could be exhibited and a long life could be achieved.
実Ｉｌ＆！２ 、次にアンチモン濃度が１．０ 、２．
０ 。Really &! 2, then the antimony concentration is 1.0, 2.
0.
３．０ 、４．０および５．０ｗｔ％の鉛−アンチモン
合金格子体を用いて活物質層厚が３０３１１１のクラッ
ド式正極板を常法に従い製作し、これと鉛−カルシウム
合金格子体から成る負極板とを用いて電池を構成した。A clad positive electrode plate with an active material layer thickness of 303111 was manufactured using a lead-antimony alloy grid of 3.0, 4.0, and 5.0 wt% according to a conventional method, and was composed of this and a lead-calcium alloy grid. A battery was constructed using the negative electrode plate.
これにシリカ微粒子と希硫酸とから成るゲル状電解液を
注入し、ゲルタイプの密閉形電池として、実験１と同様
の試験を行った。放電容量が初期の８０％に達した時点
のサイクル数やその時点における負極活物質中のアンチ
モン濃度と格子中のアンチモン濃度との関係を第２図に
示す。A gel electrolyte consisting of fine silica particles and dilute sulfuric acid was injected into this, and the same test as in Experiment 1 was conducted as a gel type sealed battery. FIG. 2 shows the number of cycles at which the discharge capacity reached 80% of the initial value and the relationship between the antimony concentration in the negative electrode active material and the antimony concentration in the lattice at that point.
なお、第２図には比敦のために正極に鉛−カルシウム合
金格子体すなわちアンチモンを含まない格子体を用いた
ゲルタイプの密閉電池の結果も併せて示す。For comparison purposes, FIG. 2 also shows the results of a gel-type sealed battery using a lead-calcium alloy lattice, that is, a lattice containing no antimony, for the positive electrode.
この図から、格子体中のアンチモンの濃度が１〜３ｗｔ
％の範囲ではアンチモンの濃度が高くなるほど寿命は長
くなるのに対し、３ｗｔ％を超えると逆に寿命が短くな
るのがわかる。格子体中のアンチモンの濃度が３ｗｔ％
を超える電池では寿命となった時点の負極活物質中の濃
度は１４０ｐｐｎを超えており、これが寿命の原因と考
えられる。この結果は活物質層厚を３．３１にしてら格
子体中のアンチモン濃度が３．０ｗｔ％を超えておれば
その効果のないことを示している。また、鉛−カルシウ
ム合金格子体と鉛−アンチモン合金格子体とを比較する
と、格子体中のアンチモン濃度が１〜３ｗｔ％の範囲で
あれば寿命性能は明らかに後者の方が著しく潰れている
。From this figure, the concentration of antimony in the lattice is 1 to 3 wt.
% range, the higher the antimony concentration, the longer the lifespan becomes, whereas when it exceeds 3wt%, the lifespan becomes shorter. The concentration of antimony in the lattice is 3wt%
In batteries exceeding 140 ppn, the concentration in the negative electrode active material at the end of its life exceeds 140 ppn, which is considered to be the cause of the short life. This result shows that if the active material layer thickness is 3.31 and the antimony concentration in the lattice exceeds 3.0 wt%, there is no effect. Further, when comparing a lead-calcium alloy lattice body and a lead-antimony alloy lattice body, it is clear that the latter has a significantly lower life performance when the antimony concentration in the lattice body is in the range of 1 to 3 wt%.
これらの実験から、正極格子体のアンチモン濃度を１〜
３ｗｔ％とし、かつ、正極活物質層厚を３．３＋ｕａ以
上とすることにより、深い放電を含む充放電に対して優
れた寿命性能が得られることがわかる。なお、本実施例
では鉛−アンチモン三元合金を例にとって説明したが、
一般に鉛電池の格子体に添加される元素、例えばスズや
ヒ素などの元素が少量含まれているような格子体におい
ても本発明による効果は変わることはない。From these experiments, it was found that the antimony concentration in the positive electrode lattice was 1 to 1.
It can be seen that by setting the positive electrode active material layer thickness to 3 wt % and setting the thickness of the positive electrode active material layer to 3.3+ua or more, excellent life performance can be obtained for charging and discharging including deep discharge. In addition, in this example, explanation was given using a lead-antimony ternary alloy as an example.
The effects of the present invention do not change even in a lattice body containing a small amount of elements that are generally added to the lattice body of a lead-acid battery, such as tin or arsenic.
発明の効果
以上述べたように本発明密閉式クラッド式鉛蓄電池では
深い放電を含む充放電を繰り返すような用途で使用して
も優れたサイクル寿命が得られるという利点を有する。Effects of the Invention As described above, the sealed clad lead-acid battery of the present invention has the advantage of providing excellent cycle life even when used in applications that involve repeated charging and discharging, including deep discharge.
第１図は寿命サイクル数およびその時点における負極活
物質中のアンチモン濃度と正極活物質層厚との関係を示
す図、第２図は寿命サイクル数およびその時点における
負極活物質中のアンチモン濃度と正極格子体中のアンチ
モン濃度との関係を示す図である。
健ｒなゴ クーし茎
、。
ｏ ｇ （′ ； 品電柘脂Ｖ戸ｉ中
ｆ＞７〉子もン去Ｒｇｙヮ、チ己６ｐ龜ｒ丁丁 ’７ｔ
Ｌ政Figure 1 shows the relationship between the number of life cycles, the antimony concentration in the negative electrode active material at that point, and the layer thickness of the positive electrode active material, and Figure 2 shows the relationship between the number of life cycles and the antimony concentration in the negative electrode active material at that point. FIG. 3 is a diagram showing the relationship with antimony concentration in a positive electrode lattice body. A healthy stem
,. o g (';品矘fatVtoi中f>7〉子もん Ｇａｎｄｒｏｒｄｄａ, Chichi 6p龜r dingding '7t
L government
Claims (1)
解液を用いたクラッド式鉛蓄電池において、正極格子体
に１．０〜３．０重量％のアンチモンを含有する鉛二元
または鉛多元合金を使用し、かつ該正極格子体を取り囲
む活物質層の厚さを３０３ｍｍ以上にすることを特徴と
する密閉形クラッド式鉛蓄電池。1. In a clad lead-acid battery using a gel electrolyte consisting of silica particles and dilute sulfuric acid, the positive electrode grid contains lead binary or lead multi-component containing 1.0 to 3.0% by weight of antimony. A sealed clad lead-acid battery characterized by using an alloy and having an active material layer surrounding the positive electrode grid having a thickness of 303 mm or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63069015A JPH0787095B2 (en) | 1988-03-23 | 1988-03-23 | Sealed clad lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63069015A JPH0787095B2 (en) | 1988-03-23 | 1988-03-23 | Sealed clad lead acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01241753A true JPH01241753A (en) | 1989-09-26 |
| JPH0787095B2 JPH0787095B2 (en) | 1995-09-20 |
Family
ID=13390341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63069015A Expired - Lifetime JPH0787095B2 (en) | 1988-03-23 | 1988-03-23 | Sealed clad lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0787095B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0579863U (en) * | 1992-03-30 | 1993-10-29 | 株式会社ユアサコーポレーション | Clad sealed lead acid battery |
-
1988
- 1988-03-23 JP JP63069015A patent/JPH0787095B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0579863U (en) * | 1992-03-30 | 1993-10-29 | 株式会社ユアサコーポレーション | Clad sealed lead acid battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0787095B2 (en) | 1995-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5556720A (en) | Sealed zinc secondary battery and zinc electrode therefor | |
| JP4444373B2 (en) | Lead-acid battery paste having a tin compound and its production and use | |
| JP2017004963A (en) | Control valve type lead-acid storage battery | |
| US3639176A (en) | Zinc electrode containing an additive to reduce gassing at the zinc electrode in a heat sterilized silver-zinc alkaline battery | |
| JPH10188963A (en) | Sealed lead-acid battery | |
| JPH01241753A (en) | Sealed type clad type lead storage battery | |
| US3580740A (en) | Zinc electrode containing lead sulfide to reduce gassing at the zinc electrode in heat sterilized silver zinc alkaline battery | |
| JPH042060A (en) | Sealed type lead acid battery | |
| KR870000967B1 (en) | Sealed deep-cycle lead acid battery | |
| JPH01241752A (en) | Sealed type clad type lead storage battery | |
| JP2995780B2 (en) | Sealed lead-acid battery | |
| JPH0542114B2 (en) | ||
| JPH06283191A (en) | Sealed lead-acid battery | |
| JP2958791B2 (en) | Sealed lead-acid battery | |
| JPH01149376A (en) | Sealed lead-acid battery | |
| JPS6142868A (en) | Nonaqueous electrolyte battery | |
| JPH10106576A (en) | Sealed lead-acid battery | |
| JPS58123658A (en) | Sealed lead storage battery | |
| JPH05314983A (en) | Manufacture of alkaline storage battery | |
| JPH06283190A (en) | Sealed lead-acid battery | |
| JPH02119054A (en) | Sealed lead-acid battery | |
| JPH10106572A (en) | Sealed lead-acid battery | |
| JPH0676814A (en) | Negative electrode plate for sealed lead-acid battery | |
| JPH04337256A (en) | Sealed lead-acid battery | |
| JPS62208566A (en) | Sealed lead-acid battery |