JPH0821418B2 - Lead acid battery - Google Patents
Lead acid batteryInfo
- Publication number
- JPH0821418B2 JPH0821418B2 JP62161710A JP16171087A JPH0821418B2 JP H0821418 B2 JPH0821418 B2 JP H0821418B2 JP 62161710 A JP62161710 A JP 62161710A JP 16171087 A JP16171087 A JP 16171087A JP H0821418 B2 JPH0821418 B2 JP H0821418B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- battery
- acid battery
- lead
- negative electrode
- 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 - Lifetime
Links
Classifications
-
- 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
- H01M10/08—Selection of materials as electrolytes
-
- 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
-
- 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)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は正極格子にPb−Sb系合金を用い、負極板子に
Pb−Ca系合金を用いた鉛蓄電池の改良、特に減液特性の
改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION Industrial Field of the Invention The present invention uses a Pb—Sb-based alloy for a positive electrode grid and uses it for a negative electrode plate.
The present invention relates to an improvement in a lead storage battery using a Pb-Ca alloy, and particularly to an improvement in liquid reduction characteristics.
従来の技術 近年、水素過電圧の高いPb−Ca系合金（以下、カルシ
ウム系合金という）の開発によって従来の液減りの多い
Pb−Sb系合金（以下、アンチモン系合金という）に代っ
てカルシウム系合金を格子に用いる２つの電池系が開発
された。すなわち正負極ともにカルシウム系合金格子を
用いるカルシウム電池と、正極には従来のアンチモン合
金格子を用い、負極にカルシウム系合金格子を用いるい
わゆるハイブリッド電池である。これらにより一旦は、
液減りやガス発生の問題を大幅に改善したかに見えた。
特にハイブリット電池では旧来のアンチモン系合金使用
電池の製造装置を活用できる点や使用目的によってはサ
イクル的な使用に魅力が残されているなど過途的にまだ
まだ使用される傾向にある。Conventional technology In recent years, due to the development of Pb-Ca-based alloys with high hydrogen overvoltage (hereinafter referred to as calcium-based alloys), the conventional liquid consumption has decreased
Two battery systems have been developed which use calcium-based alloys for the lattice instead of Pb-Sb-based alloys (hereinafter referred to as antimony-based alloys). That is, it is a so-called hybrid battery that uses a calcium-based alloy grid for both the positive and negative electrodes, a conventional antimony alloy grid for the positive electrode, and a calcium-based alloy grid for the negative electrode. With these,
It seems that the problems of liquid loss and gas generation have been greatly improved.
In particular, hybrid batteries tend to be used ephemerally because they can use conventional manufacturing equipment for batteries using antimony alloys, and depending on the purpose of use, they remain attractive for cyclic use.
発明が解決しようとする問題点 しかしながらこの電池系で再びアンチモン系電池と同
様に水素ガスの著しい発生や液減り、自己放電の問題が
発生してきた。それは、近年になってとくに自動車等の
仕様条件が都市交通状況やオプションの増加などの歴史
的変化によって電池の環境が高温化するなどにより、従
来は目立たなかった正極アンチモンの溶解と負極への析
出が促進され、一旦メンテナンスフリーとして提供され
た電池が減枯れを起こすなど新しい社会的問題を発生し
つつある。従来、基本的に負極格子内に含まれているア
ンチモンの作用を抑制するために研究されてきたアンチ
モン量を格子から減らす技術はもはや限界があり、格子
内に固溶されたアンチモンに対して作用を抑制する物質
の検討が進められている。つまり、イオンとして泳動や
拡散を行う成分に対する新しい取り組みを開始する必要
が生じてきた。すなわち、ハイブリット電池の寿命を向
上させるためのひとつの手段として、正極より溶解した
アンチモンが負極に析出しないようにするか、あるいは
負極に析出したアンチモンを水素発生反応に対して不活
性にさせることが考えられる。Problems to be Solved by the Invention However, similar to the antimony-based battery, this battery system has again suffered from a remarkable generation of hydrogen gas, a decrease in the amount of liquid, and a problem of self-discharge. In recent years, in particular, due to historical changes in specifications such as automobiles due to historical changes such as urban traffic conditions and an increase in options, the battery environment has become hot, and the positive electrode antimony, which had not been noticeable in the past, is deposited and deposited on the negative electrode. Is being promoted, and new social problems are occurring, such as the batteries once provided as maintenance-free are running out of power. Conventionally, the technology to reduce the amount of antimony, which has been basically studied to suppress the action of antimony contained in the negative electrode lattice, is already limited, and it works on the antimony dissolved in the lattice. Studies on substances that suppress the above are ongoing. In other words, it has become necessary to start a new approach to components that migrate or diffuse as ions. That is, as one means for improving the life of the hybrid battery, it is possible to prevent the dissolved antimony from the positive electrode from depositing on the negative electrode or to make the antimony deposited on the negative electrode inactive to the hydrogen generation reaction. Conceivable.
本発明はハイブリット電池の減液特性を改善し、正極
格子の腐食を小さくすることにより、長寿命の電池を提
供することが目的である。An object of the present invention is to provide a battery having a long life by improving the liquid reducing property of the hybrid battery and reducing the corrosion of the positive electrode grid.
問題点を解決するための手段 本発明は、ハイブリット電池にフェノール基、芳香族
カルボニル基、芳香族カルボキシル基、α，β−不飽和
脂肪族アルコール基、α，β−不飽和脂肪族カルボニル
基及びα，β−不飽和脂肪族カルボキシル基を有する有
機化合物のグループから選んだ少なくとも１つを電池系
内に位置させたことを特徴とする。Means for Solving the Problems The present invention provides a hybrid battery with a phenol group, an aromatic carbonyl group, an aromatic carboxyl group, an α, β-unsaturated aliphatic alcohol group, an α, β-unsaturated aliphatic carbonyl group, and At least one selected from the group of organic compounds having an α, β-unsaturated aliphatic carboxyl group is located in the battery system.
作用 このように構成することで、ハイブリット電池の減液
特性を改善するとともに、正極格子の腐食を抑制するこ
とができる。Operation With this configuration, the liquid reducing property of the hybrid battery can be improved and the corrosion of the positive electrode grid can be suppressed.
実施例 第１図は本発明を適用した一例であり、正極板１と負
極板２及びセパレータ３と希硫酸とからなり、セパレー
タ３に芳香族カルボニル基を有する有機化合物を添加し
た例である。また第２図は従来の技術を適用した例を示
す。Example FIG. 1 is an example to which the present invention is applied, which is an example in which an organic compound having an aromatic carbonyl group is added to the separator 3, which is composed of a positive electrode plate 1, a negative electrode plate 2, a separator 3 and dilute sulfuric acid. Further, FIG. 2 shows an example to which the conventional technique is applied.
ハイブリット電池は負極格子にSbを含まないため、初
期は水素過電圧が高く、優れた減液特性を示す。しかし
ながら、充放電の繰り返しにより正極格子が腐食しSbが
溶解し、負極板表面に析出する。これにより水素過電圧
が低下し、減液特性は徐々に悪くなる。Since the hybrid battery does not contain Sb in the negative electrode grid, the hydrogen overvoltage is high at the initial stage, and excellent liquid reduction characteristics are exhibited. However, repeated charging and discharging causes corrosion of the positive electrode grid, dissolution of Sb, and deposition on the surface of the negative electrode plate. As a result, the hydrogen overvoltage decreases, and the liquid reduction characteristics gradually deteriorate.
本発明を適用した場合、溶解したSb3+イオンとカルボ
ニル基の酸素とが配位結合し、Sbの水素発生に対し不活
性な形態を作る。その反応は次式に示すとおりであると
考えられる。When the present invention is applied, the dissolved Sb 3+ ion and the oxygen of the carbonyl group coordinate to form a form inactive to hydrogen generation of Sb. The reaction is considered to be as shown in the following formula.
フェノール基の例：（フェノール） 芳香族カルボニル基の例：（ベンゾアルデヒド） 芳香族カルボキシル基の例：（安息香酸） 有機化合物の添加方法についてはペーストに添加、極
板に塗布するかあるいは極板を液中に浸漬する、セパレ
ータに添加、電解液に添加のいずれの方法であってもよ
い。しかしながら、溶解したSb3+イオンが負極に析出す
る過程は電気泳動による移動が主であるので、セパレー
タに添加するのが最も効果的である。また有機化合物は
単量体であっても重合体であってもよい。Example of phenol group: (phenol) Examples of aromatic carbonyl groups: (Benzaldehyde) Examples of aromatic carboxyl groups: (benzoic acid) The method for adding the organic compound may be any of addition to a paste, coating on an electrode plate or dipping the electrode plate in a liquid, addition to a separator, or addition to an electrolytic solution. However, since the migration of dissolved Sb 3+ ions on the negative electrode is mainly due to migration by electrophoresis, it is most effective to add them to the separator. The organic compound may be a monomer or a polymer.
従来、飽和脂肪族アルデヒドなどを添加する試みがな
されているが、この物質は共役系でないために、 Ｒ−CH2−CH2−Ｃ Ｈ−Ｏ が安定に存在しない。従って、これらの物質を添加して
も減液特性を改良するには十分な効果を発揮していな
い。 Conventionally, there has been no attempt to add saturated aliphatic aldehyde.
However, since this substance is not a conjugated system, R-CH2-CH2-C H-O Does not exist stably. Therefore, adding these substances
Has not shown sufficient effect to improve the liquid reduction properties.
Yes.
しかしながら、本発明に記載する物質は共役系である
ので、Sb3+イオンと安定な化合物を作るため、負極表面
にアンチモンが析出し、これによって水素過電圧が低下
するという現象を抑制することが可能となる。However, since the substance described in the present invention is a conjugated system, it is possible to suppress the phenomenon in which antimony is deposited on the surface of the negative electrode and the hydrogen overvoltage is lowered due to the formation of a stable compound with Sb 3+ ions. Becomes
この効果をより明らかにすべく、40℃中で定電圧過充
電（14.8V/12V電池）を行い、その時の減液特性を比較
した。電池の内容としては、本発明の技術を用いた例と
してベンゾアルデヒドを添加（セパレータ中に添加、添
加量はセパレータ重量に対し、0.3wt％）した場合を電
池Ａ、従来の技術で有機化合物を全く添加しない場合の
電池Ｂについて比較試験を行った。その結果を第３図に
示す。第３図から明らかなように本発明の技術を適用し
た場合、減液が非常に抑制されていることがわかった。
上記試験が終了した後、負極板の水素発生電位を比較し
たところ、本発明の技術を適用した試料は新品に近いレ
ベルであったのに対し、従来の技術を適用した試料は貴
な電位にシフトしていた。To clarify this effect, constant voltage overcharge (14.8V / 12V battery) was performed at 40 ° C, and the liquid reduction characteristics at that time were compared. As the content of the battery, as an example using the technique of the present invention, a case where benzaldehyde is added (added in the separator, the addition amount is 0.3 wt% with respect to the separator weight) is the battery A, and the organic compound is added by the conventional technique. A comparative test was performed on Battery B, which was not added at all. FIG. 3 shows the results. As is apparent from FIG. 3, when the technique of the present invention was applied, it was found that the liquid reduction was extremely suppressed.
After the above test was completed, when the hydrogen generation potentials of the negative electrode plates were compared, the sample to which the technology of the present invention was applied was at a level close to that of a new product, whereas the sample to which the conventional technology was applied had a noble potential. It was shifting.
以上のように本発明に示す有機添加剤の効果により減
液特性が改善されることが明らかになった。As described above, it has been clarified that the liquid reducing property is improved by the effect of the organic additive shown in the present invention.
発明の効果 上記のごとく、本発明はアンチモンの負極析出による
水素過電圧の低下を防止し、ハイブリット電池の減液特
性を著しく改善することができる。EFFECTS OF THE INVENTION As described above, the present invention can prevent the hydrogen overvoltage from lowering due to the deposition of antimony on the negative electrode, and can significantly improve the liquid reduction characteristics of the hybrid battery.
第１図は本発明の技術を適用し芳香族カルボニルをセパ
レータに添加した場合の電池概略図、第２図は従来の有
機化合物を全く添加しない場合の電池概略図、第３図は
減液特性を示す比較図である。 １……正極板、２……負極板、３……セパレータ。FIG. 1 is a schematic diagram of a battery when the technique of the present invention is applied and aromatic carbonyl is added to a separator, FIG. 2 is a schematic diagram of a battery when no conventional organic compound is added, and FIG. FIG. 1 ... Positive electrode plate, 2 ... Negative electrode plate, 3 ... Separator.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｍ 10/08 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location H01M 10/08
Claims (4)
子にPb−Ca系合金を用いる鉛蓄電池において、フェノー
ル基、芳香族カルボニル基、芳香族カルボキシル基、
α，β−不飽和脂肪族アルコール基、α，β−不飽和脂
肪族アルデヒド基及びα，β−不飽和脂肪族カルボン酸
基を有する有機化合物のグループから選ばれた少なくと
も１つを電池内に有することを特徴とする鉛蓄電池。1. A lead-acid battery using a Pb—Sb alloy for a positive electrode grid and a Pb—Ca alloy for a negative electrode grid, wherein a phenol group, an aromatic carbonyl group, an aromatic carboxyl group,
At least one selected from the group of organic compounds having an α, β-unsaturated aliphatic alcohol group, an α, β-unsaturated aliphatic aldehyde group, and an α, β-unsaturated aliphatic carboxylic acid group in a battery. Lead acid battery characterized by having.
を特徴とする特許請求の範囲第１項に記載の鉛蓄電池。2. The lead-acid battery according to claim 1, wherein the organic compound is contained in the separator.
とする特許請求の範囲第１項に記載の鉛蓄電池。3. The lead storage battery according to claim 1, wherein the organic compound is contained in the electrode plate.
徴とする特許請求の範囲第１項に記載の鉛蓄電池。4. The lead acid battery according to claim 1, wherein an organic compound is contained in the electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62161710A JPH0821418B2 (en) | 1987-06-29 | 1987-06-29 | Lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62161710A JPH0821418B2 (en) | 1987-06-29 | 1987-06-29 | Lead acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS646379A JPS646379A (en) | 1989-01-10 |
| JPH0821418B2 true JPH0821418B2 (en) | 1996-03-04 |
Family
ID=15740409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62161710A Expired - Lifetime JPH0821418B2 (en) | 1987-06-29 | 1987-06-29 | Lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0821418B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170021285A (en) * | 2014-06-17 | 2017-02-27 | 오씨브이 인텔렉츄얼 캐피탈 엘엘씨 | Water loss reducing pasting mats for lead-acid batteries |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2871857B1 (en) * | 2004-06-22 | 2008-09-12 | Gilson Sas Soc Par Actions Sim | PERISTALTIC PUMP CASSETTE COMPRISING A TUBE PINCH ADJUSTING MEMBER |
| JP6814045B2 (en) | 2014-06-17 | 2021-01-13 | オーシーヴィー インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | Anti-sulfation adhesive mat for lead-acid batteries |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1009301A (en) * | 1970-08-03 | 1977-04-26 | John L. Devitt | Maintenance-free lead-acid sealed electrochemical cell with gas recombination |
| JPS477929U (en) * | 1971-02-17 | 1972-09-29 | ||
| DE2520961C2 (en) * | 1974-05-13 | 1984-02-16 | W.R. Grace & Co., 02140 Cambridge, Mass. | Lead accumulator with plastic battery separator |
| JPS586275B2 (en) * | 1977-04-28 | 1983-02-03 | 新神戸電機株式会社 | lead acid battery |
| JPS5580267A (en) * | 1978-12-11 | 1980-06-17 | Nippon Muki Kk | Isolating plate for lead storage battery |
| DE3222361C2 (en) * | 1982-06-14 | 1985-03-28 | Grace Gmbh, 2000 Norderstedt | Separators for lead-lead dioxide accumulators and process for their production |
| JPS6322063U (en) * | 1986-07-28 | 1988-02-13 |
-
1987
- 1987-06-29 JP JP62161710A patent/JPH0821418B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170021285A (en) * | 2014-06-17 | 2017-02-27 | 오씨브이 인텔렉츄얼 캐피탈 엘엘씨 | Water loss reducing pasting mats for lead-acid batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS646379A (en) | 1989-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105514504A (en) | A lead-acid battery | |
| CN1332471C (en) | Colloidal electrolyte of lead acid accumulator | |
| JP2000149981A (en) | Lead-acid battery, and additive therefor | |
| US20010000239A1 (en) | Lead-acid battery and producing method thereof | |
| CN102660697B (en) | Lead-acid battery grid alloy for power | |
| CN114976299A (en) | Wet sand electrolyte for water-based zinc ion battery, preparation method of wet sand electrolyte and water-based zinc ion battery | |
| CN114927772A (en) | Electrolyte additive, application thereof, electrolyte and water-based zinc ion battery | |
| CN102329982A (en) | Lead-antimony rare-earth positive grid alloy and preparation method thereof | |
| JPS63213264A (en) | Lead storage battery | |
| CN114899505B (en) | Acid aqueous solution zinc ion secondary battery electrolyte containing betaine additive | |
| JPH0821418B2 (en) | Lead acid battery | |
| CN107579255A (en) | A kind of positive electrode grid of lead storage battery alloy and preparation method thereof | |
| CN116231111A (en) | A new type of electrolyte additive for aqueous zinc-ion batteries | |
| JPH10189029A (en) | Manufacturing method of sealed lead-acid battery | |
| CN111418037A (en) | Aqueous electrolyte and pseudocapacitor including the same | |
| JPH11176449A (en) | Sealed lead-acid battery | |
| KR950004457B1 (en) | Lead acid battery | |
| CN113782747B (en) | High-calcium alloy for lead-acid storage battery grid and preparation method thereof | |
| JP3498560B2 (en) | Lead storage battery | |
| JP2019207786A (en) | Lead acid battery | |
| JP2553962B2 (en) | Lead plate for lead battery | |
| JP2977600B2 (en) | Lead storage battery | |
| JP2003151618A (en) | Lead-acid battery and additive for lead-acid battery | |
| JP2008152973A (en) | Lead-acid battery electrolyte, lead-acid battery negative electrode, electrolyte and / or lead-acid battery equipped with the negative electrode, and lead-acid battery additive | |
| JP3102000B2 (en) | Lead storage battery |