JPS6051786B2 - sealed lead acid battery - Google Patents
sealed lead acid batteryInfo
- Publication number
- JPS6051786B2 JPS6051786B2 JP53106780A JP10678078A JPS6051786B2 JP S6051786 B2 JPS6051786 B2 JP S6051786B2 JP 53106780 A JP53106780 A JP 53106780A JP 10678078 A JP10678078 A JP 10678078A JP S6051786 B2 JPS6051786 B2 JP S6051786B2
- Authority
- JP
- Japan
- Prior art keywords
- lattice
- weight
- alloy
- acid battery
- 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.)
- Expired
Links
- 239000002253 acid Substances 0.000 title claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000011245 gel electrolyte Substances 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910000882 Ca alloy Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002637 fluid replacement therapy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Description
【発明の詳細な説明】
本発明は電解質の少い密閉形鉛蓄電池の改良に関するも
ので、深い放電時及び過充電時の容量低下を防ぐととも
に耐食性、格子硬度に優れた陽極板格子合金としてＰｂ
−Ａｇ−Ｃｕ−Ｂｉ合金を使用することを特徴としたも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the improvement of a sealed lead-acid battery with a small amount of electrolyte, and uses Pb as an anode plate lattice alloy that prevents capacity reduction during deep discharge and overcharging, and has excellent corrosion resistance and lattice hardness.
-Ag-Cu-Bi alloy is used.
従来、この種の密閉形鉛蓄電池には、自己放電が少なく
補液等の保守がいらないことが要求され、そのため格子
合金として主としてＰｂ−Ｃａ合金が使用されてきた。Hitherto, this type of sealed lead-acid battery has been required to have little self-discharge and require no maintenance such as fluid replacement, and for this reason, a Pb--Ca alloy has been mainly used as the lattice alloy.
一方、この種の電池は深い放電の用途が多いにもかかわ
らずＰｂ−Ｃａ合金格子を使用した蓄電池は深い放電時
に陽極板格子と活物質との間に不働態被膜が生じて充電
が困難になり、容量低下を起こしたり充電不能になる欠
点があつた。また、比較的高率での過充電時には、陽極
板格子の周辺に高抵抗物質が生成し液減少が少ない割に
内部抵抗が上昇し、容量の低下が起こると同時に充電中
の水分解が著しくなつて液減少を促進するため電解液の
少ないこの種の蓄電池にとつて寿命を縮める等の問題が
あつた。このため実用上は過放電保護回路及び過充電保
護回路が必要となり、これらの付帯機器費用の蓄電池の
費用に対する比率が大きいものになつて、実用面でその
経済性が半減されていた。本発明は上記のＰｂ−Ｃａ合
金格子を陽極板格子として使用した蓄電池の欠点を除去
するものてある。On the other hand, although this type of battery is often used for deep discharge, storage batteries using Pb-Ca alloy lattices are difficult to charge due to the formation of a passive film between the anode plate lattice and the active material during deep discharge. However, there were drawbacks such as a decrease in capacity and an inability to charge the battery. In addition, when overcharging at a relatively high rate, high-resistance substances are generated around the anode plate grid, and the internal resistance increases despite the small amount of liquid loss, causing a decrease in capacity and, at the same time, significant water decomposition during charging. This type of storage battery, which has a small amount of electrolyte, has problems such as a shortened lifespan because the electrolyte decreases rapidly over time. For this reason, an over-discharge protection circuit and an over-charge protection circuit are required in practice, and the cost of these ancillary equipment has become a large proportion of the cost of the storage battery, halving its economic efficiency in practical terms. The present invention eliminates the drawbacks of storage batteries using the above-mentioned Pb--Ca alloy grid as the anode plate grid.
すなわち、陽極板格子として、適量、例えは０．０１〜
１．０重量％の銀、０．００１〜０．０１重量％の銅、
０．００１〜０．００５重量％のビスマスを鉛に添加し
たＰｂ−Ａｇ−Ｃｕ−Ｂｉ合金を用い、これに酸化鉛と
希硫酸とからなるペーストを充填し、陽極板とする。That is, as an anode plate grid, an appropriate amount, for example 0.01~
1.0% by weight silver, 0.001-0.01% by weight copper,
A Pb-Ag-Cu-Bi alloy in which 0.001 to 0.005% by weight of bismuth is added to lead is used, and a paste consisting of lead oxide and dilute sulfuric acid is filled into this to form an anode plate.
一方、少量、例えば０、μｓ重量％のカルシウムを鉛に
添加したＰｂ−Ｃａ合金格子に、同様に、酸化鉛、硫酸
バリウム及び希硫酸からなるペーストを充填し陰極板と
する。これらを希硫酸中て化成したのち、陽極板、陰極
板及びセパレータを組み合ノわせ、無水硅酸を水に分散
させたものと濃硫酸からなるゲル状電解質を注入して電
池を構成する。陽極板格子を構成するＰｂ−Ａｇ−Ｃｕ
−Ｂｉ合金において銀の作用は格子の耐食性を向上し、
陽極格子から銀が溶出し陰極活物質上に析出することに
５より陰極における酸素ガスの吸収能を高める効果があ
り、その添加量は最低０．０１重量％含有しておればよ
く、これ以上の量とすればさらに効果が著しいが、１重
量％よりも多量使用する場合には陽極板より溶出泳動し
た銀が陰極板上に析出することによる自己放電が著しく
増大する。また合金の価格が高価となり工業上実用性を
失うものである。銅の作用は格子の耐食性を向上させる
ことで、銀と同時に存在して一層の効果がある。その添
加量が０．００１重量％よりも少量では効果が薄く、ま
た０．０１重量％よりも多量になるとその効果は、飽和
状態に達する。またビスマスの作用は格子の硬度を増大
させることである。その添加量が０．００１重量％より
も少量では効果が薄く、また０．００５重量％よりも多
量になるとその効果は飽和状態に達する。本発明はＰｂ
−Ａｇ−Ｃｕ−Ｂ１合金からなる陽極板格子と、量的に
少ない電解質との組み合わせに特徴を持つものである。On the other hand, a Pb--Ca alloy lattice in which a small amount, for example, 0 μs weight % of calcium is added to lead, is similarly filled with a paste consisting of lead oxide, barium sulfate, and dilute sulfuric acid to form a cathode plate. After chemically converting these in dilute sulfuric acid, the anode plate, cathode plate, and separator are combined, and a gel electrolyte consisting of silicic anhydride dispersed in water and concentrated sulfuric acid is injected to form a battery. Pb-Ag-Cu constituting the anode plate lattice
- In Bi alloys, the action of silver improves the corrosion resistance of the lattice,
Silver is eluted from the anode lattice and precipitated on the cathode active material, which has the effect of increasing the oxygen gas absorption capacity at the cathode, and the amount added should be at least 0.01% by weight, and no more than 0.01% by weight is sufficient. If the amount is more than 1% by weight, the effect will be even more remarkable, but if the amount is more than 1% by weight, self-discharge will increase significantly due to the silver eluted from the anode plate depositing on the cathode plate. Moreover, the price of the alloy becomes high, making it impractical industrially. The effect of copper is to improve the corrosion resistance of the lattice, which is even more effective when present at the same time as silver. If the amount added is less than 0.001% by weight, the effect will be weak, and if the amount added is more than 0.01% by weight, the effect will reach a saturated state. The action of bismuth is also to increase the hardness of the lattice. If the amount added is less than 0.001% by weight, the effect will be weak, and if the amount added is more than 0.005% by weight, the effect will reach a saturated state. The present invention is based on Pb
It is characterized by the combination of an anode plate lattice made of -Ag-Cu-B1 alloy and a relatively small amount of electrolyte.
以下、本発明の実施例を６Ｖ，．３Ａ１１の電池につい
て、（１）深い放電の場合と、（２）過充電の場合とに
分けて詳述する。Examples of the present invention will be described below with 6V, . The 3A11 battery will be described in detail in two cases: (1) deep discharge and (2) overcharge.
（１）深い放電の場合
深い放電をしてから開路放置しておいた後の定電流定電
圧による充電特性を第１図に示す。(1) In the case of deep discharge FIG. 1 shows the charging characteristics with constant current and constant voltage after deep discharge and leaving the circuit open.
従来品イは本発明品口に比べて充電々流が流れにくく充
電が困難になつている。この傾向はさ２らに放置すると
一層顕著になつてくる。また回復容量と放電後における
放置期間との関係を示したのが第２図であり、本発明品
口は従来品イよりも回復性が良いことが明らかである。
これは、この種の蓄電池では活物質に対する３電解質の
量が少ないために、深い放電をすると急激に酸性度が減
少するため、従来品においては格子と活物質問に不動態
被膜か生成し易いのに対して本発明品はそのような不働
態被膜の生成が無いからである。Compared to the product of the present invention, the conventional product A has a difficult charging current and is difficult to charge. This tendency becomes even more noticeable if left untreated. Further, FIG. 2 shows the relationship between the recovery capacity and the standing period after discharge, and it is clear that the product of the present invention has better recovery properties than the conventional product.
This is because in this type of storage battery, the amount of 3 electrolytes relative to the active material is small, so the acidity decreases rapidly when deep discharge occurs, and in conventional products, a passive film tends to form on the lattice and active material. In contrast, the product of the present invention does not generate such a passive film.
３（２）過充電の場合第３図は
０．１７Ｃで連続過充電した時の結果を示す。3(2) Overcharging Figure 3 shows the results of continuous overcharging at 0.17C.
従来品イは早い時期に容量が低下する。これは陽極板格
子の周辺に高抵抗物質が生成し易く、内部抵抗が増大す
ると同時に充電々圧も高くなり、量的に少ない電解質中
での水分解が起こり易く、液減少が著しくなり、容量劣
化が促進されるためである。一方、本発明品口において
は、このような高抵抗物質は生成せず、また、充電中に
陽極板より溶出、泳動し、陰極板に析出した銀がガス消
失触媒として作用し、陰極板活物質の酸素ガス吸収を良
くするため、液減少も少なく長期にわたり容量を維持す
ることにより、従来品より優れている。またゲル状電解
質の代わりに陽、陰極板内およびこの極板間ならびにそ
の周辺に配置した多孔性隔離材、例えば吸液性ガラスマ
ットにのみ希硫酸を保持ぜしめた電解液量の少ない構成
をもつ電池においても、上記と同様の結果が得られた。
また、０．１重量％の銀と鉛よりなる格子の引つ張り強
度が３ｋ９／ｄに対し、さらに０．０１重量％の銅、０
．００５重量％のビスマスを添加した合金よりなる格子
は硬度が高く、その引つ張り強度は４ｋ９／Ｗｌｎにな
るという結果が得られ、ペーストの格子への塗着も良好
に行なえる利点がある。上述のごとく、本発明は従来の
密閉形鉛蓄電池こおける欠点を改善し、しかも付帯する
過放電及ｆ過充電保護回路を必要とせず、したがつて、
電東システムとして安価なものが得られる利点があ３。Conventional product A loses capacity quickly. This is because high-resistance substances tend to form around the anode plate lattice, which increases the internal resistance and at the same time increases the charging pressure.Water decomposition in the electrolyte, which is small in quantity, tends to occur, resulting in a significant decrease in liquid capacity. This is because deterioration is accelerated. On the other hand, in the product of the present invention, such high-resistance substances are not generated, and silver that is eluted and migrated from the anode plate during charging and deposited on the cathode plate acts as a gas dissipation catalyst and activates the cathode plate. Because the material absorbs oxygen gas better, it is superior to conventional products by reducing liquid loss and maintaining capacity over a long period of time. In addition, instead of a gel electrolyte, a structure with a small amount of electrolyte in which dilute sulfuric acid is retained only in a porous isolation material placed inside the positive and negative electrode plates, between the plates, and around them, such as a liquid-absorbing glass mat, is used. The same results as above were obtained for the battery containing the same.
Furthermore, while the tensile strength of the lattice made of 0.1% by weight of silver and lead is 3k9/d, the tensile strength of the lattice made of 0.1% by weight of copper and lead is 3k9/d.
．． A grid made of an alloy containing 0.005% by weight of bismuth has a high hardness and a tensile strength of 4k9/Wln, and has the advantage that paste can be applied well to the grid. As mentioned above, the present invention improves the drawbacks of conventional sealed lead-acid batteries, and does not require an accompanying over-discharge and over-charge protection circuit.
There is an advantage that the Dento system is inexpensive.3.
′！図面の簡単な説明
第１図は本発明の実施例における鉛蓄電池の深）放電を
した後の充電特性を示す図、第２図は放ｔ後における放
置期間と回復容量との関係を示す１、第３図は過充電の
際の放電持続時間、内部抵ｔ１液減少量を示す図である
。′! BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing the charging characteristics after deep discharge of a lead-acid battery according to an embodiment of the present invention, and Figure 2 is a diagram showing the relationship between the standing period and recovery capacity after discharge. , FIG. 3 is a diagram showing the discharge duration and the amount of decrease in the internal resistance t1 during overcharging.
Claims (1)
この両極板間及びその周辺に配置した多孔性隔離材のみ
に電解質を保持させ、前記陽極板の格子を０．０１〜１
重量％のＡｇ、０．００１〜０．０１重量％のＣｕ、０
．００１〜０．００５重量％のＢｉを含有し残部がＰｂ
からなるＰｂ−Ａｇ−Ｃｕ−Ｂｉ合金で構成したことを
特徴とする密閉形鉛蓄電池。1. Either a gel electrolyte is provided, or the electrolyte is retained only in a porous separator placed within the positive and negative electrode plates and between and around the positive and negative electrode plates, and the lattice of the anode plate is 0.01 to 1.
wt% Ag, 0.001-0.01 wt% Cu, 0
．． Contains 001 to 0.005% by weight of Bi with the balance being Pb
A sealed lead acid battery comprising a Pb-Ag-Cu-Bi alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53106780A JPS6051786B2 (en) | 1978-08-30 | 1978-08-30 | sealed lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53106780A JPS6051786B2 (en) | 1978-08-30 | 1978-08-30 | sealed lead acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5532389A JPS5532389A (en) | 1980-03-07 |
| JPS6051786B2 true JPS6051786B2 (en) | 1985-11-15 |
Family
ID=14442412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53106780A Expired JPS6051786B2 (en) | 1978-08-30 | 1978-08-30 | sealed lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6051786B2 (en) |
-
1978
- 1978-08-30 JP JP53106780A patent/JPS6051786B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5532389A (en) | 1980-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH10188963A (en) | Sealed lead-acid battery | |
| JPS6051786B2 (en) | sealed lead acid battery | |
| JPS5894770A (en) | Leakage-less closed type lead battery | |
| GB1329974A (en) | Electric storage batteries | |
| JPS63148556A (en) | Paste type lead acid battery | |
| JP2720689B2 (en) | Lead storage battery | |
| JPS63152871A (en) | sealed lead acid battery | |
| JPS5889781A (en) | Sealed lead-acid battery | |
| JP3185300B2 (en) | Sealed lead-acid battery | |
| JP2809634B2 (en) | Manufacturing method of sealed lead-acid battery | |
| JP2553598B2 (en) | Sealed lead acid battery | |
| JP4742424B2 (en) | Control valve type lead acid battery | |
| JP3102000B2 (en) | Lead storage battery | |
| JPH0414758A (en) | Lead-acid accumulator | |
| JP2518090B2 (en) | Lead acid battery | |
| JPH03145061A (en) | Lead-acid battery | |
| JPS588558B2 (en) | Positive electrode grid for lead-acid batteries | |
| JPH01183068A (en) | Lead-acid battery | |
| JPS58158874A (en) | Lead storage battery | |
| JPH0548586B2 (en) | ||
| JPH10106576A (en) | Sealed lead-acid battery | |
| JPH01143147A (en) | Lead storage battery | |
| JPH0450713B2 (en) | ||
| JPH0770318B2 (en) | Lead acid battery | |
| JPS63187572A (en) | sealed lead acid battery |