JPS5882472A - Lead storage battery and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a lead storage battery with little self-discharge, excellent in a supercharge shelf characteristics and further having a characteristic of durability. CONSTITUTION:For filling up a gel-like electrolyte in pores of the positive plate it is hard to fill up the already gelatinized electrolyte so that a method of gelatinizing in the pores of the positive plate is desirable. The positive plate here to be used can be an unformed or formed plate. From the viewpoint of maintenance, however, a spot-formed plate is desirable. Said positive plate is dried and impregnated with a liquid wherein SiO2 is dispersed and SiO2 particles are fillted up in the pores of the positive plate. When the concentration of SiO2 in dispersion liquid is too high, expansion in the formed plate at the time of gel formation is big so as to cause partial destruction of the plate, while when the concentration is too weak, a full quantity of gel-like electrolyte does not generate so as to have no effect thus a solid portion of SiO2 in the dispersion liquid is desirably 5-30wt%. The positve plate impregnated with the dispersion liquid of SiO2 as it is or after drying is combined with the negative plate and a liquid- containing material to constitute a group of plates and to be put into a battery jar, then a water solution of sulphuric acid i.e. the electrolyte is injected.

Description

【発明の詳細な説明】 本発明は、正、負極板間に、ガラス繊維や合成樹脂繊維
などをマット状などにした含液材を配置し、電解液が電
池を逆向きにしても漏出しない程度に制限した液量制限
形の鉛蓄電池老関するもので自己放電、および過放電放
置後の特性を改善することを目的とする。[Detailed Description of the Invention] The present invention is characterized by arranging a liquid-containing material such as a mat of glass fiber or synthetic resin fiber between the positive and negative electrode plates, so that the electrolyte will not leak even if the battery is turned upside down. The purpose of the present invention is to improve self-discharge and characteristics after over-discharge in aging lead-acid batteries with limited liquid volume.

最近、電池に対してメンテナンスフリーであることが強
く要望されている。このため鉛蓄電池においては格子合
金組成の改良が図られ、さらに小形の鉛蓄電池において
は電解液をゲル化したり、あるいは含液材などに電解液
を含浸して電解液の漏出を抑制したり、また負極で酸素
ガスを消失させて水分の逸散を抑制したりする手段が講
じられている。特に小形の密閉鉛蓄電池においては、別
の理由から含液マットを使用しこれらにゲル状電解質の
希釈液を注入したものなどがある。Recently, there has been a strong demand for batteries to be maintenance-free. For this reason, efforts have been made to improve the lattice alloy composition of lead-acid batteries, and in small lead-acid batteries, the electrolyte is gelled, or liquid-containing materials are impregnated with the electrolyte to suppress leakage of the electrolyte. Also, measures have been taken to suppress the loss of moisture by eliminating oxygen gas at the negative electrode. Particularly in small sealed lead-acid batteries, liquid-containing mats are used for other reasons, and a dilute gel electrolyte solution is injected into these mats.

これらの含液材を使用する鉛蓄電池では通常、ガラス繊
維あるいは合成樹脂繊維あるいはこれらの混合物のマッ
トを使用するため、極板を押圧する力がゲル・状電解質
などに比較して強く、充放電１、？１ サイクル寿命が長くなるなどの長所がある。その反面、
自己放電特性や、過放電特性がゲル状電解質や液を多量
に用いる電池に比較して極端に悪い欠点があった。この
現象はマットを使用し希薄ゲルを注入した電池において
も同様に見られる。Lead-acid batteries that use these liquid-containing materials usually use a mat made of glass fiber, synthetic resin fiber, or a mixture of these, so the force that presses the electrode plate is stronger than that of a gel electrolyte, which makes charging and discharging difficult. 1.? 1. It has advantages such as a longer cycle life. On the other hand,
They had the disadvantage that their self-discharge characteristics and over-discharge characteristics were extremely poor compared to batteries that use a large amount of gel electrolyte or liquid. This phenomenon is also observed in batteries using mats and injecting dilute gel.

本発明者らは、この種マットなどの含液材を用いる液量
制中蓄電池における上記の自己放電特性及び過放電特性
に劣る原因を検討した結果、電池放置後の正極中に含有
されている電解液量が極端に少なくなっていることによ
るものであることがわかった。正極中の電解液量が少な
くなるのは、正極板の保液化力よりも含液パあるいは負
極の保液能力が高いために生じるもので、この現象は特
に温度が高くなると顕著になる。正極板中に電解質が少
なくなると、放電も充電も困難になるばかりでなく、こ
のように劣化した正極板は元の容量まで戻ることが困難
になり、いわゆる不働態化を生じる。The present inventors investigated the causes of the above-mentioned inferior self-discharge characteristics and over-discharge characteristics in liquid volume controlled medium storage batteries using liquid-containing materials such as mats, and found that It turned out that this was due to the extremely low amount of electrolyte. The amount of electrolyte in the positive electrode decreases because the liquid-retaining capacity of the liquid-containing pad or the negative electrode is higher than that of the positive electrode plate, and this phenomenon becomes particularly noticeable as the temperature rises. When the amount of electrolyte in the positive electrode plate decreases, it not only becomes difficult to discharge and charge the positive electrode plate, but also makes it difficult for the positive electrode plate deteriorated in this way to return to its original capacity, resulting in so-called passivation.

本発明は、上記に鑑み、正極板中の電解質の保持能力を
増大させることにより、前記のような従来の欠点を除去
するもので、正極板がその細孔中にＨ２ＳＯ４を含むゲ
ル状物質を含有する。ことを特徴とする。In view of the above, the present invention eliminates the above-mentioned conventional drawbacks by increasing the electrolyte retention capacity in the positive electrode plate, and the positive electrode plate contains a gel-like substance containing H2SO4 in its pores. contains. It is characterized by

のけ希薄ゲル中の液状部分のみで、ゲルを構成するコロ
イド粒子は正極板表面に残るのみであり、従って正極板
の電解質保持能力を向上することができない／。The colloidal particles that make up the gel only remain on the surface of the positive electrode plate, and the electrolyte retention ability of the positive electrode plate cannot be improved.

正極板の細孔中にゲル状電解質を充填するには、既にゲ
ル状になったものは充填が困難であるため。It is difficult to fill gel electrolyte into the pores of the positive electrode plate if it is already in a gel state.

ｊＦ極板の細孔中でゲル化する方法が好都合である。A method of gelation in the pores of the jF plate is advantageous.

ここに用いる正極板は未化成板でも乳化成板でもよいが
、ゲル状電解質の保持性の点から乳化成板が好ましい。The positive electrode plate used here may be either an unformed plate or an emulsified plate, but an emulsified plate is preferable from the viewpoint of retention of gel electrolyte.

この正極板を乾燥し、これに５ｉ０２を分散した液を含
浸し、正極板の孔中にＳ　１０２粒子を充填する。分散
液中の８１０２の濃度は高拳ぎると、ゲル生成時に正極
板中での膨張が大きく、極板の一部破壊などを引き起こ
し、希薄過ぎると充分量のゲル状電解質が生じないので
効果がなく、分散液中の８１０２固形分は５〜３０重量
％が好ましい。This positive electrode plate is dried, impregnated with a liquid in which 5i02 is dispersed, and S102 particles are filled into the holes of the positive electrode plate. If the concentration of 8102 in the dispersion is too high, the expansion in the positive electrode plate will be large during gel formation, causing partial destruction of the electrode plate, and if it is too dilute, a sufficient amount of gel-like electrolyte will not be generated, making it ineffective. The solid content of 8102 in the dispersion is preferably 5 to 30% by weight.

’　Ｓ　ｉ０２の分散液を含浸した正極板は、そのまま
あるいは乾燥′した一部、負極板及び含液材と組合せそ
のまま組立てた場合と、乾燥した後組立てた場合と７゛
は、注入硫酸濃度は前者を濃くする必要がある。The positive electrode plate impregnated with the Si02 dispersion was assembled as it was or a part of it dried, combined with the negative electrode plate and liquid-impregnated material, and assembled after drying. It is necessary to deepen the former.

以下、本発明の詳細な説明する。The present invention will be explained in detail below.

大きさ８０Ｘ２６Ｍ、厚さ３．０脇の正極板２枚と、大
きさ８０Ｘ２６履、厚さ１．６ｕの負極板３枚及び含液
材を組合せ、１０時間率電流での放電容量が３　、２Ａ
ｈの電池を試作した。なお、正極は化成後、５ｉ０２濃
度２．６％、６．０％、　１ｏ　−ｏ　％　ｓ２０．０
％、３０．０％、５０．０チの分散液に浸漬したものを
用いた。A combination of two positive electrode plates with a size of 80 x 26 m and a thickness of 3.0 mm, three negative electrode plates with a size of 80 x 26 m and a thickness of 1.6 u, and a liquid-containing material, the discharge capacity at a 10 hour rate current is 3. 2A
We made a prototype h battery. In addition, after chemical formation, the positive electrode has a 5i02 concentration of 2.6%, 6.0%, 1o -o% s20.0
%, 30.0%, and 50.0% dispersions were used.

これらの電池を０．３２Ａの電流で１５時間充電し、０
．６４Ａで放電する操作を３サイクル繰り返し、初期容
量を求めた後、充電状態とし、次のような評価をした。These batteries were charged with a current of 0.32A for 15 hours and
．． After repeating the operation of discharging at 64 A for 3 cycles and determining the initial capacity, the battery was placed in a charged state and evaluated as follows.

まず、充電状態の電池を６ｏＣの雰囲気中で１力月間放
置した後の容量を測定し、次にこの電池を０．３２Ａで
１５時間充電した後の容量を測定し自己放電率を評価し
た。その結果の例を次表に示′ｔ０ なお、比較のため、正極をＳ　ｚ　０２分散液に浸漬し
ない電池について評価した。First, the capacity of a charged battery was measured after it was left in an atmosphere at 6oC for one month, and then the capacity was measured after this battery was charged at 0.32A for 15 hours to evaluate the self-discharge rate. Examples of the results are shown in the following table. For comparison, a battery in which the positive electrode was not immersed in the S z 02 dispersion was evaluated.

表から、正極を８１０２分散液に浸漬した電池の自己放
電率は従来品に比較して少ないことがわかノ る。特にＳ　１０２分散液の固形分が６％以上になると
その効果が大きくなる。表からは固形分６０％の液に浸
漬した電池についても自己放電率が小さｂが、正極板表
面にふくれが一部生じている場合があるので、固形分は
３０チ以下が好ましい。しかし、この活物質のふくれは
外圧で押さえれば特（ｃ問題はないもめと考えられる。From the table, it can be seen that the self-discharge rate of the battery in which the positive electrode was immersed in the 8102 dispersion was lower than that of the conventional product. In particular, the effect becomes greater when the solid content of the S102 dispersion becomes 6% or more. From the table, the self-discharge rate is small even for batteries immersed in a solution with a solid content of 60% b, but some blisters may occur on the surface of the positive electrode plate, so the solid content is preferably 30 cm or less. However, if this swelling of the active material is suppressed by external pressure, it is considered that there is no problem.

次に別の充電状態の電池をｓｏＣの雰囲気中で１セル当
り４０Ωの抵抗を接続し４日間放電し、４日後抵抗を切
り離し、５ｏＣで３０日間開回路で放置した。その後室
温に戻し、１セル当り２　、４７Ｖの定電圧を２４時間
印加して充電し、次に０．６４Ａで放電する充放電をし
た。こうして過放電放置後の容量回復性を評イｍｌシた
。その結果の例を前記衣に示す。表から明らかなように
、Ｓｉｏ２１Ｍに浸漬し正極を有する電池の過放電放置
後の容量回復性は従来品に比較して優れている。Next, another battery in a charged state was discharged for 4 days by connecting a 40 Ω resistor per cell in an SOC atmosphere, and after 4 days, the resistor was disconnected and the battery was left in an open circuit at 5oC for 30 days. Thereafter, the cells were returned to room temperature, charged by applying a constant voltage of 2.47 V per cell for 24 hours, and then discharged at 0.64 A. In this way, capacity recovery after overdischarge was evaluated. An example of the results is shown in the above clothing. As is clear from the table, the capacity recovery property of the battery having the positive electrode immersed in Sio21M after being allowed to over discharge is superior to that of the conventional product.

以上のように、本発明によれば自己放電が少なく、過放
電放置特性に浸れ、さらに含液材を使用した場合の長所
である長寿命特性も備えた鉛蓄電池を得ることができる
。As described above, according to the present invention, it is possible to obtain a lead-acid battery that has little self-discharge, good over-discharge characteristics, and also has long-life characteristics, which are the advantages of using a liquid-containing material.

代理人の氏名　弁理士　中　尾　敏　男　ほか１名３３
７−Name of agent: Patent attorney Toshio Nakao and 1 other person33
7-

Claims (1)

【特許請求の範囲】 て、正極板がその細孔中に硫酸を含むゲル状物質を含有
することを特徴とする鉛蓄電池。 （２）　　Ｓ　ｉＯ２を含有する分散液を正極板に含浸
する極板群を電槽へ挿入した後硫酸水溶液を注入する工
程を有する鉛蓄電池の製造法。[Scope of Claims] A lead-acid battery characterized in that the positive electrode plate contains a gel-like substance containing sulfuric acid in its pores. (2) A method for manufacturing a lead-acid battery, which includes a step of impregnating a positive electrode plate with a dispersion containing SiO2, inserting a group of electrode plates into a battery case, and then injecting an aqueous sulfuric acid solution.