JPH03119654A - Lead-acid battery - Google Patents
Lead-acid batteryInfo
- Publication number
- JPH03119654A JPH03119654A JP1258297A JP25829789A JPH03119654A JP H03119654 A JPH03119654 A JP H03119654A JP 1258297 A JP1258297 A JP 1258297A JP 25829789 A JP25829789 A JP 25829789A JP H03119654 A JPH03119654 A JP H03119654A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- electrode active
- negative electrode
- lead
- battery
- 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
- 239000002253 acid Substances 0.000 title claims description 8
- 239000007773 negative electrode material Substances 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 238000009713 electroplating Methods 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910000978 Pb alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000126 substance Substances 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は鉛蓄電池の改良に関するものである。[Detailed description of the invention] Industrial applications The present invention relates to improvements in lead-acid batteries.
従来の技術とその課題
鉛蓄電池は動力用、移動用、据置用などの電源として広
く用いられており、低価格で高率放電に優れていること
から自動車の起動用に広く採用されている。現在自動車
起動用の鉛蓄電池には、その使用条件などから長寿命化
、耐高温特性の改善などいくつかの要求があるが、その
１つに高出力化の要求がある。Conventional technology and its challenges Lead-acid batteries are widely used as power sources for power, transportation, and stationary use, and are widely used for starting automobiles due to their low cost and excellent high-rate discharge. Currently, there are several demands on lead-acid batteries for starting automobiles, such as longer life and improved high-temperature resistance due to their usage conditions, and one of them is a demand for higher output.
一般に６セルモノブロツクの構造である自動車起動用の
鉛蓄電池の高出力化の方法としては、セル間接続方法を
改善してセル間接続部分の抵抗を小さくすること、極板
間隔を小さくして極間抵抗を小さくすること、電解液で
ある希硫酸の濃度を高くすることが考えられる。しかし
これらについては既に限界に近いところまで改善が進め
られている。もう１つの方法としては電圧特性の優れた
格子体を用いることであり、斜め棧の入った格子体や放
射線状の桟の入った格子体など形状を最適化すること、
電気伝導性のよい材料を用いることなどが考えられる。Generally speaking, methods for increasing the output of lead-acid batteries for starting automobiles, which have a 6-cell monoblock structure, include improving the inter-cell connection method to reduce the resistance at the inter-cell connections, and reducing the spacing between the electrode plates. Possible methods include reducing the resistance between the electrodes and increasing the concentration of dilute sulfuric acid, which is the electrolytic solution. However, these improvements have already reached their limits. Another method is to use a grid with excellent voltage characteristics, optimizing the shape such as a grid with diagonal bars or a grid with radial bars.
One possibility is to use a material with good electrical conductivity.
電気伝導性のよい材料としてはコスト面からも考え合わ
せると銅および銅合金が最適である。Copper and copper alloys are the most suitable materials with good electrical conductivity, considering the cost.
銅あるいは銅合金を格子体に用いる場合、その表面が露
出していると、即ち、銅あるいは銅合金の表面が直接電
解液である希硫酸と接触していると、正極に用いた場合
は銅が溶出して負極板に析出し、負極に用いた場合はそ
の露出部分において鉛ＩＦ！池の充放電反応以外の反応
が起こってしまう、即ち、充電中においては水素ガスの
発生反応が起こり負極活物質の充電が不十分になり、放
置中には負極活物質である金属鉛と局部電池を構成して
自己放電を大きくしてしまう、そのため銅あるいは調合
金製の格子体の表面に電気メツキや溶湯に浸漬するなど
して鉛あるいは鉛合金の被膜を形成して使用しなければ
ならない。When copper or copper alloy is used for the grid, if its surface is exposed, that is, if the surface of the copper or copper alloy is in direct contact with dilute sulfuric acid, which is the electrolyte, copper will be removed when used for the positive electrode. is eluted and deposited on the negative electrode plate, and when used as a negative electrode, lead IF! Reactions other than the charging and discharging reactions of the battery occur; in other words, during charging, a reaction occurs that generates hydrogen gas, resulting in insufficient charging of the negative electrode active material, and when the battery is left unused, metal lead, which is the negative electrode active material, and local This increases self-discharge in the battery structure, so it is necessary to form a lead or lead alloy coating on the surface of a grid made of copper or prepared alloy by electroplating or immersing it in molten metal. .
しかし、銅あるいは調合金製の格子体の表面に、鉛ある
いは鉛合金の被覆を形成するためには、製造工程を新た
に増加することが必要となり、格子体製造のコストアッ
プにもつながる。However, in order to form a coating of lead or a lead alloy on the surface of a grid made of copper or a prepared alloy, it is necessary to add a new manufacturing process, which also increases the cost of manufacturing the grid.
課題を解決するための手段
本発明は、上記問題を解決するもので、負極に銅格子を
用い板鉛蓄電池において、正極活物質重量に比べ負極活
物質重量を１５〜２０％多くすることによって、銅格子
表面に電気メツキや溶湯に浸漬するなどの表面処理なし
で、銅格子そのままで電池に使用することを可能にした
ものである。Means for Solving the Problems The present invention solves the above problems by increasing the weight of the negative electrode active material by 15 to 20% compared to the weight of the positive electrode active material in a plate lead-acid battery using a copper lattice for the negative electrode. This makes it possible to use the copper grid as it is in batteries without any surface treatment such as electroplating or immersion in molten metal.
実施例 以下、本発明を実施例により詳細に説明する。Example Hereinafter, the present invention will be explained in detail with reference to Examples.
第１図は本発明による鉛蓄電池用極板の製造方法の一実
施例を示す製造工程の概略図で、まず、厚み０．２ｍｍ
の銅の圧延シートを展開してエキスバンド格子を作製し
た。このエキスバンド格子に、鉛粉に希硫酸を混ぜて練
膏した通常の負極用ペーストを充填した。ペースト充填
量は、化成後の１セル当りの負極活物質重量が１セル当
りの正極活物質重量の１００ 、１１０ 、１１５ 、
１２＜１ 、１２５％となるように５種類変えて行った
。正極板には、鉛粉に希硫酸を混ぜて練膏した正極用ペ
ーストを従来の鋳造格子に充填したものを使用した０次
に、これらの正極板、負極板および通常のセパレータを
用い、１セル電池（公称容量３５Ａｈ、 ５ｈＲ）を作
製した。電池の内容を第１表に示す。FIG. 1 is a schematic diagram of the manufacturing process showing one embodiment of the method for manufacturing lead-acid battery electrode plates according to the present invention.
An expanded grid was fabricated by rolling out a rolled sheet of copper. This expanded grid was filled with a normal negative electrode paste made by mixing lead powder with dilute sulfuric acid and gluing it together. The paste filling amount is such that the weight of the negative electrode active material per cell after chemical formation is 100, 110, 115 of the weight of the positive electrode active material per cell,
Five types were changed so that 12<1, 125%. For the positive electrode plate, a conventional casting grid was filled with a positive electrode paste made by mixing lead powder with dilute sulfuric acid. A cell battery (nominal capacity 35 Ah, 5 hR) was produced. The contents of the battery are shown in Table 1.
第１表
なお、正極、負極活物質重量はセル全体の既化正極、負
極の活物質重量を意味する。In Table 1, the weights of the positive and negative electrode active materials refer to the weights of the active materials of the positive and negative electrodes of the entire cell.
通電後、５ｈＲ容量試験を２〜行い、その後次の全放電
サイクル試験を行った。After energization, two or more 5hR capacity tests were performed, and then the next full discharge cycle test was performed.
放電 電流７．ＯＡで終止電圧１．ＯＶまで充電 電流
？、ＯＡで放電量の１３０％また、全放電サイクル試験
中、電池を充電状態で放置（４５℃ｘ１６ｈ ） した
時のガス発生量を調査した。その結果を、それぞれ第１
図および第２図に示す、さらに、試験終了後に負極活物
質中に存在するα（％）を分析した結果を第２表に示す
。Discharge current7. The final voltage at OA is 1. Charge current to OV? , 130% of the discharge amount at OA.Also, the amount of gas generated when the battery was left in a charged state (45° C. x 16 hours) during the full discharge cycle test was investigated. The results are shown in the first
Further, Table 2 shows the results of analysis of α (%) present in the negative electrode active material after the test, which is shown in FIG. 2 and FIG.
第２表
なお、電池記号１の負極活物質中のＣｕ（％）は、全放
電サイクル試＠５０〜の値、その他は２００〜の値であ
る。また、全放電サイクル試験前の負極活物質中のＣｕ
（％）はＯ，Ｑｌ （％）以下である。Table 2 Note that Cu (%) in the negative electrode active material of battery symbol 1 is a value of 50~ in the full discharge cycle test, and a value of 200~ in other cases. In addition, Cu in the negative electrode active material before the full discharge cycle test
(%) is less than or equal to O,Ql (%).
第１図より、全放電サイクル寿命試験中の放電持続時間
は、負極／正極活物質重量比にあまり影響されないこと
がわかる。しかし、第２図より明らかなように全放電サ
イクル試聴中のガス発生量は著しく、負極／正極活物質
重量比に影響されることがわかる。電池ＮＯ６１は、ガ
ス発生量か５０〜で極めて多くこの時点で試験を打ち切
り解体調査した。その結果、第２表に示されるように負
極活物質中には、約０．８％の銅（Ｃｕ）が検出され、
同時に硫酸鉛も多量に蓄積していた。From FIG. 1, it can be seen that the discharge duration during the full discharge cycle life test is not significantly influenced by the negative electrode/positive electrode active material weight ratio. However, as is clear from FIG. 2, the amount of gas generated during the entire discharge cycle test is significantly influenced by the weight ratio of the negative electrode/positive electrode active material. For battery No. 61, the amount of gas generated was extremely high at 50 or more, and at this point the test was discontinued and the battery was dismantled and investigated. As a result, as shown in Table 2, approximately 0.8% copper (Cu) was detected in the negative electrode active material.
At the same time, lead sulfate was also accumulated in large quantities.
負［！／正極活物質重量比を１．１０とした電池ＮＯ，
２ではサイクルと共にガス発生量が増加する傾向があっ
た。このことは負極活物質中のαの分析値を示した第２
表からも、α量の増加が明らかに認められ、負極格子と
して用いたαが一部溶出していると思われる。negative[! /Battery NO. with positive electrode active material weight ratio of 1.10,
In No. 2, the amount of gas generated tended to increase as the cycle progressed. This shows that the second analysis of α in the negative electrode active material
From the table, an increase in the amount of α is clearly observed, and it seems that some of the α used as the negative electrode lattice is eluted.
負極／正極活物質量比を１．１５〜１゜２５とした電池
Ｎ０１３〜５は、ガス発生量は全放電サイクル試験中、
はぼ同じで第２表から明らかなように、αは殆んど検出
されなかった。電池Ｎ０１３〜５では、正極活物質重量
に対し負極活物質量が多くなっているので、放電末期に
負極の分極が少なくなり、負極格子として用いた銅の溶
解・析出が防止されたものと推察される。For batteries Nos. 013 to 5, in which the negative electrode/positive electrode active material ratio was 1.15 to 1°25, the amount of gas generated during the full discharge cycle test was
As is clear from Table 2, α was hardly detected. In batteries Nos. 013 to 5, the amount of negative electrode active material was greater than the weight of positive electrode active material, so it is assumed that the polarization of the negative electrode decreased at the end of discharge, preventing the dissolution and precipitation of the copper used as the negative electrode grid. be done.
第２表および第２図から、負極／正極活物質重量比とし
ては１．１５〜１．２５が望ましいと思われるが、負極
活物質重量を正極活物質！！量に比べて２５％も多くす
ることは、電池重量をいたずらに増加させ、電池の製作
費の増加にもつながるので実際上望ましくない、そのた
め、負極／正極活物質重量比としては１．１５〜１．２
０が妥当と考えられる。From Table 2 and Figure 2, it appears that the negative electrode/positive electrode active material weight ratio is preferably 1.15 to 1.25, but the negative electrode active material weight is different from the positive electrode active material! ! Increasing the weight by 25% is actually undesirable because it unnecessarily increases the weight of the battery and increases the manufacturing cost of the battery. Therefore, the negative electrode/positive electrode active material weight ratio should be 1.15 to 1.15. 1.2
0 is considered appropriate.
発明の効果
上述のごとく、負極格子に銅格子を用いた電池で、負極
活物質重量を正極活物質重量に比べて多くしなものは、
銅格子表面にメツキ、とぶ漬は等の表面処理をする必要
もなく、充分にその性能を発揮することができるので産
業上の価値は極めて大きいといえる。Effects of the Invention As mentioned above, a battery using a copper grid for the negative electrode grid, in which the weight of the negative electrode active material is greater than the weight of the positive electrode active material, has the following effects:
There is no need to perform surface treatments such as plating or dipping on the surface of the copper grid, and its performance can be fully demonstrated, so it can be said to have extremely great industrial value.
第１図は全放電サイクル試験における放電持続時間の変
化を示した特性図、第２図は全放電サイクル試験におけ
るガス発生量を示した特性図である。FIG. 1 is a characteristic diagram showing the change in discharge duration in the full discharge cycle test, and FIG. 2 is a characteristic diagram showing the amount of gas generated in the full discharge cycle test.
Claims (1)
質重量を正極活物質重量の１１５〜１２０％としたこと
を特徴とする鉛蓄電池。1. A lead-acid battery using a copper lattice for the negative electrode, characterized in that the weight of the negative electrode active material is 115 to 120% of the weight of the positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1258297A JP2913482B2 (en) | 1989-10-02 | 1989-10-02 | Lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1258297A JP2913482B2 (en) | 1989-10-02 | 1989-10-02 | Lead storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03119654A true JPH03119654A (en) | 1991-05-22 |
| JP2913482B2 JP2913482B2 (en) | 1999-06-28 |
Family
ID=17318305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1258297A Expired - Fee Related JP2913482B2 (en) | 1989-10-02 | 1989-10-02 | Lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2913482B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09289032A (en) * | 1996-04-22 | 1997-11-04 | Furukawa Battery Co Ltd:The | Lead-acid battery |
-
1989
- 1989-10-02 JP JP1258297A patent/JP2913482B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09289032A (en) * | 1996-04-22 | 1997-11-04 | Furukawa Battery Co Ltd:The | Lead-acid battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2913482B2 (en) | 1999-06-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |