JPS63190252A - Lead storage battery - Google Patents
Lead storage batteryInfo
- Publication number
- JPS63190252A JPS63190252A JP62022094A JP2209487A JPS63190252A JP S63190252 A JPS63190252 A JP S63190252A JP 62022094 A JP62022094 A JP 62022094A JP 2209487 A JP2209487 A JP 2209487A JP S63190252 A JPS63190252 A JP S63190252A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- dilute sulfuric
- sulfuric acid
- capsule
- sustained
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003094 microcapsule Substances 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 7
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 21
- 238000013268 sustained release Methods 0.000 claims description 20
- 239000012730 sustained-release form Substances 0.000 claims description 20
- 238000011084 recovery Methods 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 5
- 239000002775 capsule Substances 0.000 abstract description 4
- 239000011162 core material Substances 0.000 abstract description 4
- 238000004898 kneading Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 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
- 239000002003 electrode paste Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000009784 over-discharge test Methods 0.000 description 1
- 239000000126 substance Substances 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
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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)
- 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、特に密閉形鉛蓄電池の極板および
電解液の改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to improvements in the electrode plates and electrolytes of lead-acid batteries, particularly sealed lead-acid batteries.
従来の技術
近年、鉛蓄電池は扱いやすさと経済性の観点から自動車
用、竜業用、民生機器用として広く使われている。特に
密閉形鉛蓄電池はポータプルＶＴＲを初めとする各種ポ
ータプル機器およびＵＰＳを初めとする各種停電補償道
理など忙多く使われている。BACKGROUND OF THE INVENTION In recent years, lead-acid batteries have been widely used for automobiles, industrial equipment, and consumer equipment due to their ease of handling and economic efficiency. In particular, sealed lead-acid batteries are widely used in various portable devices such as portable VTRs and various power outage compensation systems including UPS.
従来の鉛蓄電池は正極用ペーストとして酸化鉛、希硫酸
、水からなるものを使用し、負極用ペーストとしては酸
化鉛、硫酸バリウム、添加剤、希硫酸、水からなるもの
を使用するのが一般的であり、電解液は極板中の細孔に
含まれ、放電終期には殆んどが水になってしまう。また
、電解液は希硫酸と添加剤からなるものが一般的であり
、放電末期、特に過放電放置状態になると殆んどが水に
なってしまう。Conventional lead-acid batteries generally use a positive electrode paste consisting of lead oxide, dilute sulfuric acid, and water, and a negative electrode paste consisting of lead oxide, barium sulfate, additives, dilute sulfuric acid, and water. The electrolyte is contained in the pores in the electrode plate, and most of it becomes water at the end of discharge. Further, the electrolytic solution is generally made of dilute sulfuric acid and additives, and most of it becomes water at the end of discharge, especially when left overdischarged.
発明が解決しようとする問題点
上記のように従来の鉛蓄電池は放電末期、特に過放電設
置状態になると、電解液の殆んどが水になってしまうの
で、この結果、正極格子と活物質の界面に充電困難な結
晶性硫酸鉛が生成するなど、使用後の回復性を著しく低
下させるという問題点があった。Problems to be Solved by the Invention As mentioned above, in conventional lead-acid batteries, most of the electrolyte becomes water at the end of discharge, especially in the over-discharge state, and as a result, the positive electrode grid and active material There were problems such as the formation of crystalline lead sulfate, which was difficult to charge, at the interface, which significantly reduced the recovery performance after use.
本発明は上記問題点を解決するもので、過放電放置後の
回復性を向上させることのできる鉛蓄電池を提供するこ
とを目的とするものである。The present invention solves the above-mentioned problems, and aims to provide a lead-acid battery that can improve recovery performance after being left overdischarged.
問題点を解決するための手段
上記問題点を解決するために本発明は、酸化鉛、希硫酸
、水などのほかに、内部に芯物質として希硫酸が封入さ
れた徐放性マイクロカプセルを練シ合わせたペーストを
格子に充填した極板を使うこと、あるいは電解液中に上
記と同様の徐放性マイクロカプセルを添加したものであ
る。Means for Solving the Problems In order to solve the above problems, the present invention incorporates sustained-release microcapsules in which dilute sulfuric acid is sealed as a core material in addition to lead oxide, dilute sulfuric acid, water, etc. This method uses an electrode plate whose lattice is filled with a combined paste, or adds sustained-release microcapsules similar to those described above to the electrolyte.
作用
上記構成により、徐放性マイクロカプセル中に予め充填
された希硫酸が過放電放置中に徐々に放出され、放電末
期に電解液が殆んど水になってしまうような状態はなく
なり、常に酸性度を保っため、極格子と活物質の界面に
おける充電困難な結晶性硫酸鉛の生成を防げ、鉛蓄電池
の過放電放置後の回復吟が従来より向上する。Effect With the above structure, the dilute sulfuric acid pre-filled in the sustained-release microcapsules is gradually released during over-discharging, eliminating the situation where the electrolyte becomes almost water at the end of discharge, and always By maintaining acidity, it is possible to prevent the formation of crystalline lead sulfate, which is difficult to charge, at the interface between the electrode lattice and the active material, and the recovery of lead-acid batteries after being left overdischarged is improved compared to conventional batteries.
実施例
以下本発明の鉛蓄電池の一実施例を図面に基づいて説明
する。EXAMPLE Hereinafter, an example of the lead acid battery of the present invention will be described based on the drawings.
第１図は本発明に用いた徐放性マイクロカプセルの一実
施例の構造図を示し、球形多孔質中空シリカよシなって
いる。第１図において、（１）はカプセル壁で、無水珪
酸よりなり、粒子表面の細孔径は２０〜６００ Ａの範
囲に分布している。また粒子の直径ｄは５〜５０μｍで
ある。＋２）はカプセル壁（１）の内部に封入される芯
物質で、比重１．４０の希硫酸が予め加圧充填されてい
る。FIG. 1 shows a structural diagram of one embodiment of sustained-release microcapsules used in the present invention, which are made of spherical porous hollow silica. In FIG. 1, (1) is the capsule wall, which is made of silicic anhydride, and the pore diameters on the particle surface are distributed in the range of 20 to 600 A. Moreover, the diameter d of the particles is 5 to 50 μm. +2) is a core substance sealed inside the capsule wall (1), which is filled with dilute sulfuric acid having a specific gravity of 1.40 under pressure in advance.
そして、鉛蓄電池には、酸化鉛、希硫酸、水のほかに上
記の徐放性マイクロカプセルを練り合わせた正極板用ペ
ーストをｐｂ −ｃａ−３ｎ 合金の鋳造格子に充填
した正極板と、酸化鉛、硫酸パがラム、添加剤、希硫酸
、水のほかに上記の徐放性マイクロカプセルを練り合わ
せた負極板用ペー、Ｋ）ヲＰｂ−Ｃａ−５ｎ合金の鋳造
格子に充填した負極板とを使用した。上記徐放性マイク
ロカプセルの添加量は、酸化鉛１ ｋｇに対して１ｏｏ
９とした。このように構成した正極板と９極板をマイク
ロガラス繊維のセパレータを介して重ね合わせ、電解液
として比重１．８０の希硫酸を注入して１２Ｖ、２Ａｈ
の鉛蓄電池を製作した。電解液としての希硫酸中には上
記徐放性マイクロカプセルを添加したものと添加しない
ものとの２種類を用いた。添加量は希硫酸１に９に対し
てｔｏｏ ｇとした。なお放電容量は正極板支配とした
。上記構成の鉛蓄電池の過放電放置試験の結果を第２図
を参照して説明する。The lead-acid battery has a positive electrode plate in which a cast lattice of PB-CA-3N alloy is filled with a positive electrode plate paste made by kneading the above-mentioned sustained-release microcapsules in addition to lead oxide, dilute sulfuric acid, and water, and a lead-acid battery. , a negative electrode plate prepared by kneading the above sustained release microcapsules in addition to parsulfuric acid, additives, dilute sulfuric acid, and water; K) a negative electrode plate filled in a cast grid of Pb-Ca-5n alloy; used. The amount of the sustained-release microcapsules added is 1oo per 1 kg of lead oxide.
It was set as 9. The positive electrode plate and the 9-electrode plate constructed in this way were stacked together with a microglass fiber separator in between, and dilute sulfuric acid with a specific gravity of 1.80 was injected as an electrolyte to generate a voltage of 12V and 2Ah.
produced a lead-acid battery. Two types of dilute sulfuric acid were used as the electrolytic solution: one with and without the above-mentioned sustained-release microcapsules added. The amount added was 1 to 9 to too g of dilute sulfuric acid. Note that the discharge capacity was determined to be dominated by the positive electrode plate. The results of an over-discharge storage test of the lead-acid battery having the above configuration will be explained with reference to FIG. 2.
第２図は上記鉛蓄電池を過放電放置試験したときの従来
例との比較を示す特性図である。（３）は正９極板およ
び電解液に上記徐放性マイクロカプセルを添加した例を
示す曲線、（４）は正貴極板にのみ徐放性マイクロカプ
セルを添加した例を示す曲線である。なお過放電放置試
験は周囲温度２５℃の環境で行ない、２４Ωの抵抗を接
続し、２４時間放電した。通常の終止電圧は１０．５Ｖ
と定めである。このとき、この終止電圧までの持続時間
は３．５時間であるので、２０．５時間の過放電になっ
ている。その後、抵抗を取シ除き１〜１８ケ月放置した
。そうしたのち、定電圧１４．７Ｖ、最大電流０．８Ａ
にて１６時間回復充電を行い、再び２４Ωの抵抗を接続
し、終止電圧１ｏ、ｓＶまで放電し、初期の容量と比較
して回復率を求めた。第２図に明らかなように、曲線３
．４の本実施例の鉛蓄電池の回復率は曲線６の従来例の
鉛蓄電池の回復率に比べて優秀である。特に正負極板お
よび電解液中に添加した曲＠８の場合の効果が顕著であ
る。これらについて、徐放性マイクロカプセルの効果は
次のように説明される。すなわち、徐放性マイクロカプ
セル中に予め充填された希硫酸が過放電放置中に徐々に
極板中に放出され、従来例であれば殆んどが水になって
しまう伏蝮に対し、常に酸性度を保つため、正極格子と
活物質の界面における充電困難な結晶性硫酸鉛の生成を
防げる。FIG. 2 is a characteristic diagram showing a comparison with a conventional example when the lead-acid battery was subjected to an overdischarge storage test. (3) is a curve showing an example in which the sustained-release microcapsules were added to the positive polar plate and the electrolyte, and (4) is a curve showing an example in which sustained-release microcapsules were added only to the positive noble plate. The overdischarge test was conducted at an ambient temperature of 25° C., a 24Ω resistor was connected, and the battery was discharged for 24 hours. Typical end voltage is 10.5V
It is stipulated that At this time, since the duration until this final voltage is reached is 3.5 hours, the overdischarge is 20.5 hours. Thereafter, the resistor was removed and the sample was left for 1 to 18 months. After that, constant voltage 14.7V, maximum current 0.8A
Recovery charging was carried out for 16 hours, a 24 Ω resistor was connected again, the battery was discharged to a final voltage of 1 o, sV, and the recovery rate was determined by comparing with the initial capacity. As is evident in Figure 2, curve 3
．． The recovery rate of the lead-acid battery of this embodiment shown in curve 4 is superior to that of the conventional lead-acid battery shown in curve 6. In particular, the effect in the case of Song@8 added to the positive and negative electrode plates and the electrolyte is remarkable. Regarding these, the effects of sustained-release microcapsules are explained as follows. In other words, dilute sulfuric acid pre-filled in sustained-release microcapsules is gradually released into the electrode plate during overdischarge, and in contrast to conventional methods where most of it becomes water, Maintaining acidity prevents the formation of crystalline lead sulfate, which is difficult to charge, at the interface between the positive electrode lattice and the active material.
発明の効果
以上本発明によれば、徐放性マイクロカプセルを入れる
ことによ〕、充電困難な結晶性硫酸鉛の生成を防げ、過
放電放置後の回復性を向上することができた。Effects of the Invention According to the present invention, by incorporating sustained-release microcapsules, it was possible to prevent the formation of crystalline lead sulfate, which makes charging difficult, and to improve recovery after overdischarge.
第１図は本発明に用いた徐放性マイクロカプセルの一実
施例を示す購造図、第２図は従来例と本発明実施例の過
放電放置後の回復性の比較を示す特性図である。
（１）・・・カプセル壁、（２）・・・芯物質（希硫酸
）、ｆ３１・・・正負極板および電解液に徐放性マイク
ロカプセルを添加した実施例曲線、（４）・・・正負極
板のみに徐放性マイクロカプセルを添加した実施例曲線
、（５）・・・従来例の曲線。Figure 1 is a purchasing diagram showing an example of sustained release microcapsules used in the present invention, and Figure 2 is a characteristic diagram showing a comparison of recovery properties after overdischarge of a conventional example and an example of the present invention. be. (1) Capsule wall, (2) Core material (dilute sulfuric acid), f31... Example curve in which sustained release microcapsules were added to the positive and negative electrode plates and electrolyte, (4)...・Example curve in which sustained-release microcapsules were added only to the positive and negative electrode plates, (5)...Curve of conventional example.
Claims (1)
を酸化鉛、希硫酸、水などに添加したペーストを、格子
に充填した極板を備えた鉛蓄電池。 ２、徐放性マイクロカプセルとして、直径５〜５０μｍ
の球形多孔質中空シリカを使用したことを特徴とする特
許請求の範囲第１項記載の鉛蓄電池。 ３、内部に希硫酸が封入された徐放性マイクロカプセル
を添加した電解液を備えた鉛蓄電池。 ４、徐放性マイクロカプセルとして、直径５〜５０μｍ
の球形多孔質中空シリカを使用したことを特徴とする特
許請求の範囲第３項記載の鉛蓄電池。[Scope of Claims] 1. A lead-acid battery equipped with an electrode plate whose lattice is filled with a paste made by adding sustained-release microcapsules containing dilute sulfuric acid to lead oxide, dilute sulfuric acid, water, etc. 2. As sustained release microcapsules, diameter 5-50 μm
The lead-acid battery according to claim 1, characterized in that the spherical porous hollow silica is used. 3. A lead-acid battery equipped with an electrolyte containing sustained-release microcapsules containing dilute sulfuric acid. 4. As sustained release microcapsules, diameter 5-50 μm
The lead-acid battery according to claim 3, characterized in that the spherical porous hollow silica is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62022094A JPS63190252A (en) | 1987-02-02 | 1987-02-02 | Lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62022094A JPS63190252A (en) | 1987-02-02 | 1987-02-02 | Lead storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63190252A true JPS63190252A (en) | 1988-08-05 |
Family
ID=12073287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62022094A Pending JPS63190252A (en) | 1987-02-02 | 1987-02-02 | Lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63190252A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5895732A (en) * | 1992-04-24 | 1999-04-20 | Ensci, Inc. | Battery element containing macroporous additives |
| WO2001017042A3 (en) * | 1999-09-01 | 2001-08-09 | Allan Joe Mcmenamin | An additive for a battery |
| JP2012099421A (en) * | 2010-11-05 | 2012-05-24 | Toyota Motor Corp | Ion conductor and method of producing the same, and battery and method of manufacturing the same |
| JP2012124093A (en) * | 2010-12-10 | 2012-06-28 | Toyota Motor Corp | Ionic conductor and method for manufacturing the same, and battery and method for manufacturing the same |
-
1987
- 1987-02-02 JP JP62022094A patent/JPS63190252A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5895732A (en) * | 1992-04-24 | 1999-04-20 | Ensci, Inc. | Battery element containing macroporous additives |
| WO2001017042A3 (en) * | 1999-09-01 | 2001-08-09 | Allan Joe Mcmenamin | An additive for a battery |
| JP2012099421A (en) * | 2010-11-05 | 2012-05-24 | Toyota Motor Corp | Ion conductor and method of producing the same, and battery and method of manufacturing the same |
| JP2012124093A (en) * | 2010-12-10 | 2012-06-28 | Toyota Motor Corp | Ionic conductor and method for manufacturing the same, and battery and method for manufacturing the same |
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