JPH05343093A - Sealed lead acid battery - Google Patents
Sealed lead acid batteryInfo
- Publication number
- JPH05343093A JPH05343093A JP4176163A JP17616392A JPH05343093A JP H05343093 A JPH05343093 A JP H05343093A JP 4176163 A JP4176163 A JP 4176163A JP 17616392 A JP17616392 A JP 17616392A JP H05343093 A JPH05343093 A JP H05343093A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- powder
- acid
- pores
- 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.)
- Pending
Links
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は密閉形鉛蓄電池の改良に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved sealed lead acid battery.
【０００２】[0002]
【従来の技術とその課題】電池の充電中に発生する酸素
ガスを負極で吸収するいわゆる酸素サイクルを利用した
密閉形鉛蓄電池には、リテ−ナ式とゲル式の二種類があ
る。リテ−ナ式は正極板と負極板との間に微細ガラス繊
維を素材とするマット状セパレ−タ（ガラスセパレ−
タ）を挿入し、これで電池の充放電に必要な硫酸電解液
の保持と両極の隔離を行っており、無保守、無漏液、ポ
ジションフリ−などの特徴を生かして、近年ポ−タブル
機器、コ−ドレス機器、コンピュ−タ−のバックアップ
電源をはじめ、大型の据置用電池や自動車のエンジン始
動用にも使用されるようになってきた。2. Description of the Related Art There are two types of sealed lead-acid batteries, a retainer type and a gel type, for a sealed lead-acid battery which utilizes a so-called oxygen cycle in which an oxygen gas generated during charging of the battery is absorbed by a negative electrode. The retainer type is a mat-like separator (glass separator) made of fine glass fibers between the positive electrode plate and the negative electrode plate.
Is installed to hold the sulfuric acid electrolyte necessary for battery charging / discharging and to separate the electrodes from each other. Taking advantage of features such as no maintenance, no leakage, and position free, it is portable in recent years. It has come to be used not only as a backup power source for equipment, cordless equipment, and computers, but also as a large stationary battery and for starting the engine of automobiles.
【０００３】しかし、ガラスセパレ−タは特殊な方法で
製造される直径１ミクロン前後の極細ガラス繊維を抄造
してマット状としたもので、一般的に用いられている鉛
蓄電池用のセパレ−タに比してかなり高価なことや、目
標の電池性能を得るためには極板群を強く圧迫して電槽
内に組み込まなければならないので電池の組立が困難と
なり、必然的に電池の製造コストが高くなるという欠点
があった。However, the glass separator is a matt made of extra fine glass fibers having a diameter of about 1 micron manufactured by a special method, and is used as a separator for a generally used lead storage battery. It is considerably expensive in comparison, and it is difficult to assemble the battery because it is necessary to strongly press the electrode plate group and install it in the battery case in order to obtain the target battery performance. It had the drawback of being expensive.
【０００４】また、リテ−ナ式密閉形鉛蓄電池は、実質
的に正、負極板間に挿入したガラスセパレ−タに硫酸電
解液を保持できるだけであるから電池の充放電に関与で
きる電解液量が少なく、電解液が豊富に存在する開放形
の一般的な鉛蓄電池に比べると電池容量、とくに低率放
電容量が劣るという欠点があった。Further, in the retainer type sealed lead-acid battery, the sulfuric acid electrolytic solution can be substantially held in the glass separator inserted between the positive and negative electrode plates, so that the amount of electrolytic solution which can be involved in charging and discharging of the battery is small. There is a drawback that the battery capacity, particularly the low rate discharge capacity, is inferior compared to the general open type lead acid battery, which is small and has abundant electrolyte.
【０００５】一方、ゲル式は硫酸電解液をコロイド状シ
リカや水ガラスによってゲル化した密閉形鉛蓄電池であ
るが、硫酸が離しょうしたり硫酸イオンの移動が悪いた
めに性能的にやはり問題があった。On the other hand, the gel type is a sealed lead acid battery in which a sulfuric acid electrolytic solution is gelled with colloidal silica or water glass, but there is still a problem in terms of performance due to the separation of sulfuric acid and the poor migration of sulfate ions. there were.
【０００６】そこで上記欠点を解消するために、鉛蓄電
池活物質に比して多孔度が高く比表面積の大きな粉体を
直接正、負極板間および極板群の周囲に配置し、この粉
体に電池の充放電に必要な硫酸電解液を保持させた構造
であって、上述したリテーナ式でもなくゲル式でもない
密閉形鉛蓄電池が提案されている。Therefore, in order to solve the above-mentioned drawbacks, a powder having a higher porosity and a larger specific surface area than that of a lead storage battery active material is directly arranged between the positive and negative electrode plates and around the electrode group, and the powder is formed. In addition, there is proposed a sealed lead acid battery having a structure in which a sulfuric acid electrolytic solution necessary for charging and discharging the battery is held and which is neither the retainer type nor the gel type described above.
【０００７】しかし、このような粉体を電解液保持体と
する密閉形鉛蓄電池では次のような問題点があった。す
なわち、複数のセルからなるモノブロック形の電池に粉
体を充填する場合、充填量を一定にする方が粉体の充填
がやりやすいし、注液量も一定にできるので都合がよい
わけであるが、セルごとに電槽の内容積が異なるので、
粉体を電槽内に充満させると充填量が一定にならず、さ
らに電槽内に粉体を充満させると電池が重くなり、注液
に長時間を要するという問題もあった。However, the sealed lead-acid battery using such powder as the electrolyte holder has the following problems. That is, when the powder is filled in a monoblock battery composed of a plurality of cells, it is convenient to make the filling amount constant because the powder filling is easy and the liquid injection amount can be made constant. However, because the internal volume of the battery case is different for each cell,
When the powder is filled in the battery case, the filling amount is not constant, and when the battery is filled in the battery container, the battery becomes heavy and it takes a long time to inject the liquid.
【０００８】また、一定量の粉体を各セルに充填すると
電槽内の上部に空間ができてしまうセルが生ずることに
なる。電池内に空間ができると、注液や初充電の際に粉
体が移動して極板間に充填した粉体層に空洞が生じ、期
待した電池性能が得られなくなる。Further, if a certain amount of powder is filled in each cell, a cell will be created in which a space is formed in the upper part of the battery case. If a space is created in the battery, the powder moves during the liquid injection or the initial charge, and a cavity is created in the powder layer filled between the electrode plates, so that the expected battery performance cannot be obtained.
【０００９】そこで、極板間および極板群の周囲に充填
した粉体の上部に合成樹脂を現場発泡させて連続気泡を
有する耐酸性プラスチックフォームを配置することによ
って電槽内に充填した粉体の移動を防止することを提案
した。Therefore, the powder filled in the battery case by arranging the acid-resistant plastic foam having open cells by in-situ foaming the synthetic resin on the powder filled between the electrode plates and around the electrode plate group. Proposed to prevent the movement of.
【００１０】しかし、このままでは現場発泡したプラス
チックフォームの表面にスキン層と呼ばれる比較的多孔
性に乏しい層が形成され、電解液の注入に長時間を要す
るという欠点があった。本発明は電解液の保持体として
粉体を使用した密閉形鉛蓄電池の上記課題を解決する手
段を提供するものである。However, if it is left as it is, a relatively poorly porous layer called a skin layer is formed on the surface of the in-situ foamed plastic foam, and it takes a long time to inject the electrolytic solution. The present invention provides means for solving the above problems of a sealed lead-acid battery that uses powder as a holder for an electrolytic solution.
【００１１】[0011]
【課題を解決するための手段】本発明は、極板間および
極板群の周囲に充填した粉体の上部に合成樹脂を現場発
泡させて連続気泡を有する耐酸性プラスチックフォーム
を配置し、このプラスチックフォームを貫通して上下方
向に細孔を設けることによって上記課題を解決した密閉
形鉛蓄電池を提供せんとするものである。SUMMARY OF THE INVENTION According to the present invention, an acid-resistant plastic foam having open cells is formed by in-situ foaming a synthetic resin on the upper part of the powder filled between the electrode plates and around the electrode plate group. It is intended to provide a sealed lead-acid battery that solves the above-mentioned problems by providing a vertical hole through a plastic foam.
【００１２】[0012]
【実施例】図１は本発明による密閉形鉛蓄電池を自動車
用電池に適用した場合の一実施例を示す概略図である。
図２はその要部側面図である。図において、１はアンチ
モンフリーの鉛合金またはアンチモンを少量含む鉛合金
からなる格子に正極ペーストを充填した正極板である。FIG. 1 is a schematic view showing an embodiment in which the sealed lead acid battery according to the present invention is applied to a battery for automobiles.
FIG. 2 is a side view of the main part. In the figure, reference numeral 1 denotes a positive electrode plate in which a positive electrode paste is filled in a grid made of an antimony-free lead alloy or a lead alloy containing a small amount of antimony.
【００１３】アンチモンフリーの鉛合金としては、Ca
0.05〜0.12wt% 、Sn 0.2 〜1.0wt%を含む一般的な鉛カ
ルシウム系合金が使用できる。電解液保持体としてアン
チモンを吸着する特性がある含水二酸化珪素を使用すれ
ば鉛アンチモン系合金でもよい。As an antimony-free lead alloy, Ca is
A general lead calcium alloy containing 0.05 to 0.12 wt% and Sn 0.2 to 1.0 wt% can be used. A lead antimony-based alloy may be used as long as hydrous silicon dioxide having a property of adsorbing antimony is used as the electrolytic solution holder.
【００１４】鉛アンチモン合金のアンチモン含有量とし
ては Sb 0.7 〜2.0wt%、とくに0.7〜1.5 重量％ が好
ましく、アンチモン以外の金属として砒素 As を 0.1〜
0.3wt%、錫 Sn を 0.01 〜0.5wt% を添加する。核化剤
としてセレンSeやイオウS を極少量添加すれば格子の鋳
造性や耐食性を改善できる。The antimony content of the lead antimony alloy is preferably Sb 0.7 to 2.0 wt%, particularly 0.7 to 1.5 wt%, and arsenic As is 0.1 to 0.5 as a metal other than antimony.
Add 0.3wt%, tin Sn 0.01-0.5wt%. Adding a very small amount of selenium Se or sulfur S as a nucleating agent can improve the castability and corrosion resistance of the lattice.
【００１５】正極格子に充填する正極ペーストは鉛粉を
希硫酸と混練して調製する一般的なペーストも使用可能
であるが、正極板の化成性や電池性能の向上を図るため
には、鉛粉に鉛丹（Pb3 Ｏ4 ）を混入するのが好まし
い。As the positive electrode paste to be filled in the positive electrode grid, a general paste prepared by kneading lead powder with dilute sulfuric acid can be used, but in order to improve the chemical conversion property of the positive electrode plate and the battery performance, It is preferable to mix lead powder (Pb 3 O 4 ) in the powder.
【００１６】負極板２はアンチモンフリーの鉛合金を用
いた格子にリグニンや硫酸バリウムなどの防縮剤を添加
した通常の負極ペーストを充填して製造する。負極格子
の鉛合金は Ca 0.05〜0.12wt% 、 Sn 0.001 〜0.5wt%を
含む一般的な鉛カルシウム系合金が使用できる。The negative electrode plate 2 is manufactured by filling an ordinary negative electrode paste prepared by adding a shrink preventive agent such as lignin or barium sulfate to a lattice made of an antimony-free lead alloy. As the lead alloy for the negative electrode grid, a general lead calcium alloy containing Ca 0.05 to 0.12 wt% and Sn 0.001 to 0.5 wt% can be used.
【００１７】上述した正極および負極格子は鋳造したも
のや鉛合金シートを展開したエキスパンド格子あるいは
打ち抜き格子などいずれも使用可能である。なお、ペー
ストを充填した極板は30〜50℃の部屋で熟成してから使
用する。正極板の熟成は電池性能上とくに重要である。The positive and negative electrode grids described above may be cast, expanded grids obtained by expanding a lead alloy sheet, punched grids, or the like. The paste-filled electrode plate should be aged in a room at 30 to 50 ° C before use. Aging of the positive electrode plate is particularly important for battery performance.
【００１８】３は正極板と負極板との間に挿入した合成
セパレータである。厚みが薄く多孔性でかつ電気抵抗の
低いセパレータであればいずれも使用できるが、孔径の
小さすぎるセパレータは酸素ガスが透過しにくく、負極
による酸素吸収反応を妨げるので好ましくない。また、
正、負極板間に粉体を充填するためには、両極間に隙間
を設ける必要があり、その目的のためには、波付きセパ
レータやエンボスセパレータなど表面に凹凸を設けたセ
パレータを使用するのが都合がよい。Reference numeral 3 is a synthetic separator inserted between the positive electrode plate and the negative electrode plate. Any separator having a small thickness and porosity and low electric resistance can be used, but a separator having an excessively small pore size is not preferable because oxygen gas hardly permeates and the oxygen absorption reaction by the negative electrode is hindered. Also,
In order to fill the powder between the positive and negative electrode plates, it is necessary to provide a gap between the two electrodes, and for that purpose, a separator with unevenness such as a corrugated separator or an embossed separator is used. Is convenient.
【００１９】なお、後述する粉体を電解液保持体として
使用すれば、極間の粉体層がセパレータとしての機能も
有するので、このような場合にはセパレータの使用を省
略することが可能である。If the powder to be described later is used as an electrolytic solution holder, the powder layer between the electrodes also has a function as a separator. In such a case, the use of the separator can be omitted. is there.
【００２０】上述した正極板、負極板およびセパレータ
とを積み重ね、正、負極板それぞれ別々に溶接して極板
群を作製し電槽４に挿入する。従来のガラスセパレータ
を用いたものでは、極板群を強く圧迫しなければならな
いので電槽への挿入が非常に困難であったが、本発明で
は極板群を圧迫する必要がないので挿入は容易である。
極板群を電槽に挿入したのち、セル間の接続を行う。図
において５はストラップ、６はセル間接続部、７は極柱
である。The positive electrode plate, the negative electrode plate, and the separator described above are stacked, and the positive and negative electrode plates are separately welded to produce an electrode plate group, which is inserted into the battery case 4. In the one using the conventional glass separator, it was very difficult to insert the electrode plate group into the battery case because it had to be strongly pressed, but in the present invention it is not necessary to press the electrode plate group so that the insertion is not possible. It's easy.
After inserting the electrode group into the battery case, the cells are connected. In the figure, 5 is a strap, 6 is an inter-cell connecting portion, and 7 is a pole.
【００２１】上述したようにしてセル間を接続したの
ち、電槽４の上部から粉体１３の一定量を各セルに供給
し、電池に振動を加えながら正、負極板間や極板群の周
囲に充填する。After connecting the cells as described above, a fixed amount of the powder 13 is supplied to each cell from the upper part of the battery case 4, and the positive and negative electrode plates and the electrode plate group are connected while vibrating the battery. Fill around.
【００２２】電解液保持体としての粉体は、充填した状
態での多孔度が高く、耐酸性があって電解液吸収力の優
れた流動性の高いものがよく、本実施例では、一次粒子
径が10〜40ミリミクロン、比表面積１５０〜２００ｍ2
／ｇの含水二酸化珪素（ＳｉＯ2 ・ｎＨ2 Ｏ）の微細粒
子が凝集して５０〜２００ミクロンの二次粒子を形成し
ている顆粒状の粉体であって、安息角が３０〜３５度の
流動性のよい粉体を用いた。It is preferable that the powder as the electrolytic solution holder has a high porosity in the filled state, has acid resistance and excellent fluidity of the electrolytic solution and has high fluidity. Diameter 10-40 mm, specific surface area 150-200 m 2
/ G of hydrous silicon dioxide (SiO 2 · nH 2 O) fine particles are aggregated to form secondary particles of 50 to 200 μm, and the angle of repose is 30 to 35 degrees. The powder having good fluidity was used.
【００２３】このように流動性に優れた粉体であれば、
電槽内への粉体の充填は重力加速度2 〜4G、振幅1 〜2m
m の振動をかければ短時間で密に充填でき、充填後の粉
体はガラスセパレータに匹敵する９０％近い多孔度を有
している。粉体１３の充填量は、本実施例では図１およ
び図２に示したようにストラップ５が埋没する高さまで
充填したが、少なくとも正極板１および負極板２がちょ
うど粉体層に埋没するような量であればよい。If the powder has excellent fluidity as described above,
Gravity acceleration of 2 to 4 G and amplitude of 1 to 2 m for filling powder in the battery case
If a vibration of m 3 is applied, it can be densely packed in a short time, and the powder after filling has a porosity close to 90%, which is comparable to that of a glass separator. In the present embodiment, the amount of the powder 13 filled was such that the strap 5 was buried as shown in FIGS. 1 and 2, but at least the positive electrode plate 1 and the negative electrode plate 2 were just buried in the powder layer. Any amount will do.
【００２４】このようにして粉体を充填したのち、耐酸
性のある発泡性の合成樹脂を粉体１３の上面に注入して
発泡させ、粉体１３の上部に耐酸性のある連続気泡を有
するプラスチックフォーム１２の層を形成し、粉体１３
を固定する。この時、プラスチックフォーム１２は発泡
前と比較して体積で１０〜４０倍に膨張するので、発泡
に際しては電槽４の上面から図３に示すような発泡治具
１４を各セルに挿入し、プラスチックフォーム１２が粉
体１３を圧迫しながら形成されるようにするのが望まし
く、これによってプラスチックフォーム１２と粉体１３
との間に空洞がなくなり、注液や初充電の際に粉体１３
が移動して極板間に充填した粉体層に空洞が生じて期待
した性能が得られないという問題が解決された。After the powder is filled in this way, an acid-resistant foamable synthetic resin is injected onto the upper surface of the powder 13 to cause foaming, so that the upper part of the powder 13 has acid-resistant open cells. Form a layer of plastic foam 12 and powder 13
To fix. At this time, since the plastic foam 12 expands 10 to 40 times in volume as compared with that before foaming, at the time of foaming, a foaming jig 14 as shown in FIG. It is desirable that the plastic foam 12 is formed by pressing the powder 13 so that the plastic foam 12 and the powder 13 can be formed.
There are no cavities between the
However, the problem that the expected performance cannot be obtained due to the movement of particles and the formation of cavities in the powder layer filled between the electrode plates was solved.
【００２５】このプラスチックフォーム１２は、粉体を
固定するという機能の他に、電池に注液する際や初充電
中あるいは使用時の充電で発生するガスを外部に逃がす
ことができなければならないので、気体や液体は通過し
粉体は通過しない大きさの孔を有する耐酸性のある連続
気泡を有するものでなくてはならない。In addition to the function of fixing the powder, the plastic foam 12 must be able to release the gas generated during the liquid injection into the battery, the initial charging or the charging during use to the outside. It must have acid-resistant open cells with pores of a size that allows gas or liquid to pass but not powder.
【００２６】本実施例では低温発泡型の発泡フェノール
を用いたが、表面には内部よりも多孔性に乏しいスキン
層が形成された。このスキン層を通して電解液や電池内
で発生したガスが効率よく移動できるように電池上部か
ら細い金属線で粉体１３上に配置したプラスチックフォ
ーム１２を貫通するように細孔１５を設けた。In this example, low temperature foaming phenol was used, but a skin layer having a lower porosity than the inside was formed on the surface. In order to efficiently move the electrolytic solution and the gas generated in the battery through the skin layer, fine holes 15 are provided so as to penetrate the plastic foam 12 arranged on the powder 13 from above the battery with a thin metal wire.
【００２７】この細孔１５は直径が０．５ｍｍよりも小
さくなければならない。これよりも大きな細孔では、電
解液の注入時や充電中のガス発生時に電池内部からプラ
スチックフォーム１２の上部に粉体１３が吹き出し、電
池内部に空隙が生じてしまう。The pores 15 must have a diameter smaller than 0.5 mm. If the pores are larger than this, the powder 13 blows from the inside of the battery to the upper part of the plastic foam 12 at the time of injecting the electrolytic solution or generating gas during charging, resulting in a void inside the battery.
【００２８】このようにしてプラスチックフォーム１２
で粉体１３を固定し、細孔１５を設けたのち電槽蓋８を
電槽４に溶着し、装着口９に排気栓１０を装着し排気弁
１１をとりつけて電池ができあがる。In this way, the plastic foam 12
The powder 13 is fixed with, the pores 15 are provided, then the battery case lid 8 is welded to the battery case 4, the exhaust plug 10 is attached to the attachment port 9, and the exhaust valve 11 is attached to complete the battery.
【００２９】次に本発明による密閉形鉛蓄電池の電解液
注入に要した時間、初期性能試験および寿命試験を行っ
た結果について説明する。試験に供した電池は12Ｖの自
動車用密閉形鉛蓄電池で、公称容量は25Ahである。表１
に試験結果を示す。なお、寿命試験は次の条件で行っ
た。 定電圧寿命試験条件：周囲温度 40℃ 放電 25A で4 分 充電 14.8V で10分（MAX 電流25A ）Next, the results of the time required for the injection of the electrolytic solution and the initial performance test and the life test of the sealed lead acid battery according to the present invention will be described. The battery used for the test is a 12V sealed lead-acid battery for automobiles, which has a nominal capacity of 25Ah. Table 1
The test results are shown in. The life test was conducted under the following conditions. Constant voltage life test condition: Ambient temperature 40 ° C Discharge 25A for 4 minutes Charge 14.8V for 10 minutes (MAX current 25A)
【００３０】[0030]
【表１】 [Table 1]
【００３１】( ) 内は5 秒目電圧 Ａは粉体を電解液保持体とし正極格子合金にPb-0.1％Ca
-0.5％Snを用い、粉体上部にプラスチックフォームを配
置し、さらに細孔を設けた本発明品で、Ｂは電池Ａと同
様にして組立てプラスチックフォームに細孔を設けなか
った電池である。ＣはＡと同じ正極格子合金を用いたリ
テーナ式の従来品である。負極はいずれもPb-0.7％Ca-
0.5％Snの鉛カルシウム合金格子とした。The voltage in the parentheses is for the 5th second. The voltage A is Pb-0.1% Ca for the positive electrode grid alloy with the powder as the electrolyte holding body.
-0.5% Sn is a product of the present invention in which a plastic foam is arranged on the upper portion of the powder and further has pores, and B is a battery which is assembled in the same manner as the battery A and has no plastic foam. C is a retainer type conventional product using the same positive electrode grid alloy as A. Both negative electrodes are Pb-0.7% Ca-
A lead-calcium alloy lattice of 0.5% Sn was used.
【００３２】本実験例から明らかなように、本発明品Ａ
は注液に要する時間がプラスチックフォームに細孔を設
けていない電池よりも大幅に短縮することができ、従来
のリテーナ式と比べても大差ない時間で注入することが
できた。さらに初期性能は５時間率容量、150A放電容量
とも本発明品Ａが電池Ｂよりも優れており、従来のリテ
ーナ式Ｃよりも大幅に性能が向上した。As is clear from this experimental example, the product A of the present invention
The time required for injecting the liquid could be significantly shortened as compared with the battery in which the plastic foam had no pores, and it was possible to inject in a time not much different from the conventional retainer type. Further, in the initial performance, the product A of the present invention is superior to the battery B in both the 5-hour rate capacity and the discharge capacity of 150 A, and the performance is significantly improved as compared with the conventional retainer type C.
【００３３】これは本発明品Ａおよび電池Ｂはリテーナ
式に比べ電解液量が多いことおよび正極ペーストに鉛丹
を混入することによって正極板の化成性が向上したから
であると思われる。さらに、本発明品ではプラスチック
フォームに細孔を設けて電解液やガスの移動を効率よく
おこなえるようにしたために、極板間の充填した粉体中
にガスが滞溜することがなくなり、電池Ｂに比べても電
解液を多く保持できたことによるものと思われる。It is considered that this is because the products A and B of the present invention have a larger amount of electrolytic solution than the retainer type, and the conversion of the positive electrode plate improves the chemical conversion of the positive electrode plate. Further, in the product of the present invention, since the plastic foam is provided with pores so that the electrolyte solution and the gas can be efficiently moved, the gas is not accumulated in the powder filled between the electrode plates, and the battery B It is thought that this is because the electrolyte solution was retained in a larger amount than the above.
【００３４】寿命試験は上述した充放電を１サイクルと
して500 サイクル毎にコールドクランキング電流（274
A）で放電し、30秒目電圧が7.2Vに低下した時点を寿命
とした。その結果、本発明品Ａおよび電池Ｂは従来のリ
テーナ式Ｃに比べて２倍以上の優れた性能が得られ、本
発明品は電池Ｂよりもさらに寿命性能に優れていた。こ
れは、本発明品Ａは寿命試験中の電解液の減少量が最も
少なく、プラスチックフォームに細孔を設けることによ
って電解液やガスの移動が効率的になって、電池内に充
填した粉体に保持される電解液が偏在することなく、ガ
スの移動の通路も均一化し、これにより優れた密閉反応
効率を有しているものと思われる。In the life test, the cold cranking current (274
It was discharged at A), and the life was defined as the time when the voltage dropped to 7.2V at 30 seconds. As a result, the product A of the present invention and the battery B were more than twice as good as those of the conventional retainer type C, and the product of the present invention was further excellent in life performance than the battery B. This is because the product A of the present invention has the least decrease in the amount of the electrolytic solution during the life test, and the pores are provided in the plastic foam to efficiently move the electrolytic solution and the gas, and the powder filled in the battery is obtained. It is considered that the electrolyte retained in the sample is not unevenly distributed and the passage for gas movement is made uniform, which results in excellent sealing reaction efficiency.
【００３５】寿命試験後に電池を解体して観察すると、
従来のガラスセパレータを用いた密閉形鉛蓄電池では正
極格子の腐食が著しく、正極板は原型をとどめないほど
に劣化していたのに対して、本発明品Ａは充填した粉体
によって極板がしっかりと固定されているため、その変
形はわずかであった。このようなことも本発明品の寿命
性能が優れていた理由の１つであると思われる。When the battery is disassembled and observed after the life test,
In a conventional sealed lead-acid battery using a glass separator, the positive electrode grid is significantly corroded, and the positive electrode plate is deteriorated to the extent that the prototype cannot be retained. Since it was firmly fixed, its deformation was slight. It is considered that this is also one of the reasons why the life performance of the product of the present invention was excellent.
【００３６】上述したように本発明による密閉形鉛蓄電
池は、比表面積の大きな微細一次粒子に電解液を保持さ
せるとともに、それが凝集した比較的粗大な二次粒子が
密接して生じる間隙をガス通路するという新規な密閉形
鉛電池の考え方に基づいて、従来のガラスセパレータを
使用するリテーナ式密閉形鉛電池を上回る電池性能と優
れた密閉反応効率を得ることができた。As described above, in the sealed lead-acid battery according to the present invention, the electrolytic solution is held by the fine primary particles having a large specific surface area, and the agglomerates of the relatively coarse secondary particles are closely contacted with each other to form a gas. Based on the concept of a new sealed lead-acid battery that uses a passage, it was possible to obtain battery performance and superior sealed reaction efficiency superior to those of the retainer-type sealed lead-acid battery using a conventional glass separator.
【００３７】このように粉体を電解液の保持体とする密
閉形鉛蓄電池には、本実施例で示した含水二酸化珪素粉
体以外にも珪酸カルシウムの板状結晶のように、一次粒
子が微細で比表面積および多孔度が大きく、それが凝集
して二次粒子を形成し、かつ耐酸性と親水性を有する粉
体でればいずれも使用が可能である。As described above, in the sealed lead-acid battery using the powder as a support for the electrolytic solution, primary particles such as plate crystals of calcium silicate other than the hydrous silicon dioxide powder shown in this embodiment are contained. Any fine powder having a large specific surface area and porosity, which aggregates to form secondary particles, and has acid resistance and hydrophilicity can be used.
【００３８】また、二次粒子が壊れ易い粉体の場合は適
当なバインダーを使用することができる。さらに、極板
群の圧迫をする必要が無いので電池の組立が容易にな
り、かつ使用材料が安価なため電池の製造コストを大幅
に低減することができた。If the secondary particles are powders which are easily broken, a suitable binder can be used. Further, since it is not necessary to press the electrode plate group, the battery can be easily assembled, and the manufacturing cost of the battery can be significantly reduced because the material used is inexpensive.
【００３９】さらに、従来のリテーナ式密閉鉛蓄電池で
は極板群のストラップ部が露出しているので、電池が高
温で充放電されるような条件で使用されると、負極スト
ラップ部で腐食が起こる場合があった。しかし、本発明
による密閉形鉛蓄電池では、極板群全体が粉体層あるい
はプラスチックフォームに埋没しているためこのような
使用条件下でも腐食が起こらないのは大きな利点の１つ
である。さらにプラスチックフォームに上下方向に貫通
する細孔を設けることによって電解液の注入を容易にす
ることができ、かつ電池使用時の電解液やガスの移動を
効率的に行えるために電解液量が増えるとともに密閉反
応効率も向上し優れた寿命性能を発揮できる。Further, since the strap portion of the electrode plate group is exposed in the conventional retainer-type sealed lead-acid battery, the negative electrode strap portion is corroded when the battery is used under conditions where the battery is charged and discharged at high temperature. There were cases. However, in the sealed lead-acid battery according to the present invention, since the whole electrode plate group is buried in the powder layer or the plastic foam, it is one of the great advantages that corrosion does not occur even under such a use condition. Further, by providing pores that penetrate the plastic foam in the vertical direction, it is possible to facilitate the injection of the electrolytic solution and to increase the amount of the electrolytic solution because the electrolytic solution and gas can be efficiently moved during use of the battery. At the same time, the sealing reaction efficiency is improved and excellent life performance can be exhibited.
【００４０】なお、本発明は実施例に示した以外にも種
々の態様が考えられる。例えば、本発明をチューブラー
式の鉛蓄電池に適用すれば、容易に密閉形鉛蓄電池を製
造することができる。The present invention is conceivable in various modes other than those shown in the embodiments. For example, if the present invention is applied to a tubular lead-acid battery, a sealed lead-acid battery can be easily manufactured.
【００４１】従来チューブラー式の鉛蓄電池は、その正
極板がフラットでない構造からガラスセパレータを使用
することができず、したがって専らゲル式の密閉電池し
か製造できなかったため寿命が短いという重大な欠点が
あったが、本発明に基づいて製造すれば電池の製造が簡
略化されるばかりでなく、優れた寿命性能のチューブラ
ー式密閉形鉛蓄電池の得られることがわかった。The conventional tubular lead-acid battery has a serious drawback that the glass separator cannot be used because the positive electrode plate is not flat, and therefore only the gel-type sealed battery can be manufactured, so that the life is short. However, it was found that the production of the battery according to the present invention not only simplifies the production of the battery but also provides a tubular sealed lead-acid battery having excellent life performance.
【００４２】[0042]
【発明の効果】上述したように本発明密閉形鉛蓄電池
は、セル毎の電槽内容積のバラツキに応じて粉体充填量
や注液量を変える必要がなく、一定量の粉体を充填し、
注液量も一定とし、充填した粉体の上部に発泡させた耐
酸性プラスチックフォームを配置し、このプラスチック
フォームに上下方向の貫通細孔を設けるという構成であ
るから、注液に長時間を要せず、製造が容易で安定した
一定特性の電池が得られ、その工業的価値は大きい。As described above, in the sealed lead acid battery of the present invention, it is not necessary to change the powder filling amount and the liquid injection amount according to the variation in the cell inner volume of each cell, and a fixed amount of powder is filled. Then
It takes a long time to inject, because the amount of liquid to be injected is constant, the foamed acid-resistant plastic foam is placed on top of the filled powder, and vertical through holes are provided in this plastic foam. In addition, a battery having constant characteristics that is easy to manufacture and stable can be obtained, and its industrial value is great.
【図１】本発明による密閉形鉛蓄電池の概略図FIG. 1 is a schematic view of a sealed lead-acid battery according to the present invention.
【図２】本発明による密閉形鉛蓄電池の要部側面図FIG. 2 is a side view of a main part of a sealed lead acid battery according to the present invention.
【図３】本発明電池の製造に用いる発泡治具の配置を示
す概略図FIG. 3 is a schematic view showing the arrangement of a foaming jig used for manufacturing the battery of the present invention.
１ 正極板 ２ 負極板 ３ セパレータ ４ 電槽 ５ ストラップ ６ セル間接続部 ７ 極柱 ８ 電槽ふた ９ 装着口 10 排気栓 11 排気弁 12 プラスチックフォーム 13 粉体 14 発泡治具 15 細孔 1 Positive electrode plate 2 Negative electrode plate 3 Separator 4 Battery case 5 Strap 6 Cell-to-cell connection part 7 Electrode column 8 Battery case lid 9 Mounting port 10 Exhaust plug 11 Exhaust valve 12 Plastic foam 13 Powder 14 Foaming jig 15 Pore
Claims (1)
子を形成する流動性の高い顆粒状の粉体を電解液保持体
とする密閉形鉛蓄電池において、前記粉体を極板間およ
び極板群の周囲に充填し、充填した粉体の上部に現場発
泡させた連続気泡を有する耐酸性プラスチックフォーム
を配置し、該プラスチックフォームを貫通して上下方向
に細孔を設けたことを特徴とする密閉形鉛蓄電池。1. A sealed lead-acid battery using, as an electrolyte solution holder, granular powder having high fluidity, in which fine primary particles are aggregated to form coarse secondary particles. And that around the electrode plate group, the acid-resistant plastic foam having in-situ foamed open cells is placed on the top of the filled powder, and vertical pores are formed through the plastic foam. Characteristic sealed lead acid battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4176163A JPH05343093A (en) | 1992-06-09 | 1992-06-09 | Sealed lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4176163A JPH05343093A (en) | 1992-06-09 | 1992-06-09 | Sealed lead acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05343093A true JPH05343093A (en) | 1993-12-24 |
Family
ID=16008770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4176163A Pending JPH05343093A (en) | 1992-06-09 | 1992-06-09 | Sealed lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05343093A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007220841A (en) * | 2006-02-16 | 2007-08-30 | Mitsubishi Electric Corp | Electric double layer capacitor |
-
1992
- 1992-06-09 JP JP4176163A patent/JPH05343093A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007220841A (en) * | 2006-02-16 | 2007-08-30 | Mitsubishi Electric Corp | Electric double layer capacitor |
| JP4593493B2 (en) * | 2006-02-16 | 2010-12-08 | 三菱電機株式会社 | Electric double layer capacitor |
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