JPS5923457A - Enclosed lead storage battery - Google Patents

Abstract

PURPOSE:To enhance the preservation characteristic of an enclosed storage battery by making a liquid-holding separator, which is interposed between a positive and a negative plate, by packing glass fiber with high water content into an elastic porous structure made of an acid-proof synthetic resin. CONSTITUTION:A liquid-holding separator 3 is formed by packing glass fibers with a mean diameter of 0.1-10mum into a porous spongy structure which is made of an acid-proof synthetic resin, has a porosity of 80-98% and continuous air holes with a mean hole diameter of 100mum. After the separators 3 are interposed between positive and negative plates 1 and 2 which are formed by packing active materials into grids before formation is performed, the thus assembled body is inserted into a battery jar by applying pressure, thereby constituting a sealed lead storage battery. Owing to such constitution, even after the battery is left over a long period, there is no possibility that any deformation is caused by a reduced constitutional pressure of the plate group which might be caused by the contraction of the separator 3. As a result, capacity reduction caused by self discharge as well as restoration of the capacity reduction can be improved. Consequently, the preservation characteristic of the battery can be enhanced.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、密閉形鉛蓄電池に関するもので、特にその保
液性セパレータの改良に関するものである〇 従来例の構成とその問題点 ２ページ 密閉形鉛蓄電池は、充電時において正極板で発生する酸
素ガスを負極板に吸収させることによって電槽外部への
ガスの散逸を防ぐような、いわゆる酸素サイクル構造に
なっている。また、安全性を考慮して電槽内の圧力があ
る一定の値以上になると開弁する安全弁が設けられてい
る。この電池のセパレータには、含水率の高い直径０．
１〜１０μｍ程度のガラス繊維を主成分とする材料を抄
造したものが従来から広く使用されており、このセパレ
ータが電解液の大部分を保持し、電解液が流動して外部
に溢液するのを防止している。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a sealed lead-acid battery, and in particular to an improvement of its liquid-retentive separator. A storage battery has a so-called oxygen cycle structure in which oxygen gas generated at the positive electrode plate during charging is absorbed by the negative electrode plate, thereby preventing the gas from dissipating to the outside of the battery case. Furthermore, in consideration of safety, a safety valve is provided that opens when the pressure inside the battery case exceeds a certain value. The separator of this battery has a diameter of 0.5 mm and has a high water content.
Separators made from a material whose main component is glass fibers of about 1 to 10 μm have been widely used, and this separator holds most of the electrolyte and prevents the electrolyte from flowing and spilling outside. is prevented.

以上の構造から、密閉形鉛蓄電池は溢液する心配がない
ため、ポータプル機器等の電源として広く用いられてい
る。しかし、この電池は、長期間保存すると電槽及び安
全弁から水が蒸発し、それによって電解液が減少する不
都合がある。この電解液の減少が電池の内部抵抗を増加
させ、保存特性、特に電池を長期間保持した後の残存容
量、およびその後充電した際の回復容量を低下させる原
因となっていることが判明した。このことは、長３ペー
ジ 期間保存した後の電池に、保存中に減少した重量と同量
の蒸留水を注水すると、内部抵抗が保存前とほぼ同じ値
にまで低下し、回復容量も保存前にまで回復することが
ら容易に推測できる。Because of the above structure, sealed lead-acid batteries are widely used as power sources for portable devices and the like because there is no risk of leakage. However, when this battery is stored for a long period of time, water evaporates from the battery case and the safety valve, which causes the electrolyte to decrease. It has been found that this decrease in electrolyte increases the internal resistance of the battery, which causes a decrease in storage characteristics, particularly the remaining capacity after long-term storage of the battery, and the recovery capacity upon subsequent charging. This means that if a battery that has been stored for a long period of time is filled with distilled water in an amount equal to the weight lost during storage, the internal resistance will drop to almost the same value as before storage, and the recovered capacity will also increase. It can be easily inferred that it will recover to .

以」二の保存特性の低下は、次の様に説明することがで
きる。このタイプの密閉形鉛蓄電池は、セパレータが電
解液の大部分を保持しているため、電極反応が効率よく
進行するには、セパレータと極板が密着していて、電極
反応に必要な硫酸をセパレータから極板に絶えず供給す
ることが必要である。そこで、極板とセパレークが密着
するように極板群は圧力（群圧）をかけた状態で電槽内
に挿入されている。しかし、従来の極めて柔らかいガラ
ス繊維を主成分とした抄造セパレータは、長期間に亘る
保存中に、初期に持っていた弾力性が低下する上に、先
に述べたような水の蒸発で電解液が減ることによってセ
パレータ自身の体積が収縮してしまい、群圧が低下する
のである。以上の様な原因で群圧が低下すると、セパレ
ータと極板間の密着性が悪くなるため、電池の内部抵抗
が増加し、同時にセパレータから極板への硫酸の供給が
困難になるため、保存特性が著しく低下する。The second deterioration in storage properties can be explained as follows. In this type of sealed lead-acid battery, the separator holds most of the electrolyte, so in order for the electrode reaction to proceed efficiently, the separator and the electrode plate must be in close contact with each other to absorb the sulfuric acid necessary for the electrode reaction. It is necessary to constantly supply the plates from the separator. Therefore, the electrode plate group is inserted into the battery case under pressure (group pressure) so that the electrode plate and the separator are in close contact with each other. However, when conventional paper-made separators mainly made of extremely soft glass fiber lose their initial elasticity during long-term storage, they also lose the electrolyte due to water evaporation as mentioned above. As a result, the volume of the separator itself contracts and the group pressure decreases. When the group pressure decreases due to the reasons mentioned above, the adhesion between the separator and the electrode plates deteriorates, which increases the internal resistance of the battery. At the same time, it becomes difficult to supply sulfuric acid from the separator to the electrode plates, so storage Characteristics deteriorate significantly.

発明の目的 本発明は、セパレータを改良して、極板とセパレータで
構成される群の構成圧力（群圧）が、長期間保存しても
低下しに＜＜シ、これによって密閉形鉛電池の保存特性
の低下を抑制することを目的とする。Purpose of the Invention The present invention aims to improve the separator so that the constituent pressure (group pressure) of the group consisting of the electrode plates and the separator does not decrease even after long-term storage. The purpose is to suppress the deterioration of the storage properties of.

発明の構成 本発明は、正、負極板間に介在させる保液性のセパレー
タとして、耐酸性合成樹脂からなる弾力性を有する多孔
構造体内部に、含水率の高いガラス繊維を抄き込んだ構
成のセパレータを用いることを特徴とする。Structure of the Invention The present invention has a structure in which glass fiber with a high water content is inserted into an elastic porous structure made of acid-resistant synthetic resin as a liquid-retentive separator interposed between positive and negative electrode plates. It is characterized by using a separator of

本発明のセパレータは、構造的強度は弾力性のある耐酸
性合成樹脂で保っているので、長期保存中にセパレータ
が収縮してしまうことはなく、一方、電解液の保持は内
部の含水率の高いガラス繊維によって従来と同程度に維
持される。The structural strength of the separator of the present invention is maintained by an elastic acid-resistant synthetic resin, so the separator will not shrink during long-term storage. Maintained at the same level as before by high glass fiber.

ここに用いるガラス繊維の直径は０．１〜１０μｍ５ペ
ージ が適当であり、このガラス繊維の直径以上の径の孔を多
数持つ耐酸性合成樹脂からなる多孔構造体、特に連続気
孔を有するスポンジ状多孔体内に前述のガラス繊維を抄
き込むことによって容易にセパレータを作製することが
できる。々お、耐酸性合成樹脂多孔体の多孔度は、約８
０〜９８チが適当であり、ｓｏ％以下では内部に抄き込
むことのできるガラス繊維量が少なくなり、十分な電解
液を保持できなくなる。一方、９８チ以上では、耐酸性
合成樹脂の構造強度が低下してしまうので不適当である
。また、抄き込むガラス繊維の量は１００〜１６０ｇ／
ｍ’　　が適当である。The appropriate diameter of the glass fiber used here is 0.1 to 10 μm, and a porous structure made of acid-resistant synthetic resin that has many pores with a diameter larger than the diameter of the glass fiber, especially a sponge-like porous structure with continuous pores. A separator can be easily produced by inserting the above-mentioned glass fiber into the body. The porosity of the acid-resistant synthetic resin porous material is approximately 8.
A value of 0 to 98 cm is appropriate, and if it is less than so %, the amount of glass fiber that can be drawn into the interior will decrease, making it impossible to hold a sufficient amount of electrolyte. On the other hand, if it is 98 inches or more, it is inappropriate because the structural strength of the acid-resistant synthetic resin will decrease. In addition, the amount of glass fiber to be drawn is 100 to 160g/
m' is appropriate.

上記のセパレータを使用することによって、電池の保存
特性はかなり向上する。しかし、長期保存中に水が蒸発
して全体的に電解液が減少してし゛まうので、保存前に
比べて回復容量が低下する。By using the above separator, the storage properties of the battery are considerably improved. However, during long-term storage, water evaporates and the electrolyte decreases overall, so the recovery capacity decreases compared to before storage.

これは群圧が極板にかかつていても、疎水性の合成樹脂
が極板に付着するためで、従来のガラス繊維を主成分と
した抄造セパレータに比べればわずかであるが、保水率
が低下することに起因してい６ベージ る〇 そこで、水の蒸発によって多少電解液が減少しても、セ
パレータと極板の界面に電解液を確保するために、上記
セパレータの極板に接する側に、含水率の高い抄造ガラ
ス繊維マントを重ねた構造のセパレータとすることによ
り、さらに保存特性を向上することができる。This is because the hydrophobic synthetic resin adheres to the electrode plates even if the group pressure is present on the electrode plates, and the water retention rate decreases, although it is only slightly compared to conventional paper separators made mainly of glass fiber. Therefore, in order to secure the electrolyte at the interface between the separator and the electrode plate, even if the electrolyte decreases to some extent due to water evaporation, on the side of the separator in contact with the electrode plate, By using a separator with a structure in which paper-made glass fiber cloaks with high moisture content are layered, the storage characteristics can be further improved.

実施例の説明 極板は、大きさ縦４０　ｍｍ　、巾３０ｍで、厚さは正
極３．０趣、負極２．１晒　のそれぞれ格子に活物質を
充填し化成したものを使用した。DESCRIPTION OF EXAMPLES The electrode plates used were 40 mm long and 30 m wide, and had a positive electrode thickness of 3.0 mm and a negative electrode of 2.1 mm thickness, each having a lattice filled with an active material and chemically formed.

壕だ、セパレータとしては、多孔度８０％、平均孔径１
００μｍ１厚さ２．５咽の連続気孔を有するスポンジ状
の多孔構造体に、平均径約Ｏ８７μｍのガラス繊維を１
３ｏ＆／ｍ’の割合で抄き込んだ厚さ約２．５藺のもの
を用いた。It's a trench, and as a separator, the porosity is 80% and the average pore diameter is 1.
Glass fibers with an average diameter of about 87 μm were placed in a sponge-like porous structure with continuous pores of 2.5 μm in thickness.
A material with a thickness of about 2.5 mm and made at a ratio of 3 o&/m' was used.

このセパレータと前記の正極２枚、負極３枚とで第１図
のような極板群を構成した０図において、１は正極、２
は負極、３はセパレータである。この極板群は、電槽内
で約２０　ｋｙ　／　ｄｉの圧力がか７ページ かるように挿入されている。In Figure 0, where this separator, the two positive electrodes and three negative electrodes described above constitute an electrode plate group as shown in Figure 1, 1 is the positive electrode, 2 is the positive electrode, and 2 is the positive electrode.
is a negative electrode, and 3 is a separator. This electrode group was inserted in the battery case so that a pressure of about 20 ky/di was applied.

上記の電池をＡとし、比較例として、平均径約○、Ｔμ
ｍのガラス繊維を抄造したセパレータを用いた電池をＢ
とする。The above battery is designated as A, and as a comparative example, the average diameter is approximately ○, Tμ
A battery using a separator made of glass fiber of
shall be.

電池Ａでは、４ｏ″Ｃで６ケ月間放置した後でも、セパ
レータの収縮によって群構成圧が低下してし１うことが
ないので、極板群は変形せずに、電槽内での群構成圧は
約２０　ｋｙ　／　ａｍ”を維持している。In battery A, even after being left at 4o''C for 6 months, the group composition pressure does not decrease due to the contraction of the separator, so the electrode group does not deform and the group in the battery case remains intact. The construction pressure is maintained at approximately 20 ky/am.

ところが、従来のセパレータを用いた電池Ｂでは、同じ
保存期間中にセパレータが収縮してしまうため、第２図
に示すように、群が変形し、群構成圧はほとんど○ｋｙ
　／　ａｍ２となってし１つだ。However, in battery B that uses a conventional separator, the separator shrinks during the same storage period, so the group deforms as shown in Figure 2, and the group composition pressure is almost ○ky.
/ am2 is now one.

また、電池Ａのセパレータと構成は同様である厚さ約０
．２５ｍｍの抄紙体をそれぞれ重ね合わせた・セパレー
タを使用して電池Ｃを構成した。この電池の群構成圧は
、電池Ａと同様に保存期間中にほとんど減少せず約１９
ｋｑ／ｄ、ｊであった。Also, the structure is similar to that of the battery A separator, and the thickness is approximately 0.
．． Battery C was constructed using a separator in which 25 mm paper sheets were stacked on top of each other. The group composition pressure of this battery, like battery A, hardly decreased during the storage period and was approximately 19
kq/d,j.

次に電池Ａ−Ｃの初期容量と、４０°Ｃで６力月保存後
の残存容量及び回復容量の比較を次表に示す。なお、容
量は２０’Ｃにおいて０゜８Ａの定電流放電をして求め
た。Next, the following table shows a comparison of the initial capacity of batteries A-C, and the remaining capacity and recovered capacity after storage at 40°C for 6 months. The capacity was determined by constant current discharge at 0°8A at 20'C.

発明の効果 以上のように、本発明によれば、電池の保存中の自己放
電による容量低下とその後の回復性を改善することがで
き、保存特性の優れた密閉形鉛蓄電池が得られる。Effects of the Invention As described above, according to the present invention, capacity reduction due to self-discharge during battery storage and subsequent recovery can be improved, and a sealed lead-acid battery with excellent storage characteristics can be obtained.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は実施例に用いた極板群の縦断面図、第２図は従
来のセパレータを使用した電池の保存後の極板群の縦断
面図である。 １・・・・・・正極板、２・・・・・・負極板、３・・
・・・・セ９ページ パレータ。 代理人の氏名　弁理士　中　尾　敏　男　ほか１名第１
図 第２図FIG. 1 is a longitudinal cross-sectional view of the electrode plate group used in the example, and FIG. 2 is a longitudinal cross-sectional view of the electrode plate group after storage of a battery using a conventional separator. 1... Positive electrode plate, 2... Negative electrode plate, 3...
・・・Se9 page palate. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Figure 2

Claims (1)

【特許請求の範囲】[Claims] （１）正極と負極と、両電極間に介在した保液性のセパ
レータとを有し、前記セパレータが、弾力性を有する耐
酸性合成樹脂よりなる多孔構造体にガラス繊維を抄き込
んで構成された密閉形鉛へ硼χ。 第１項記載の密閉形鉛蓄電池。 （′４　前記セパレータが、さらにガラス繊維からなる
セパレータ層を有する特許請求の範囲第１項記載の密閉
形鉛蓄電池。(1) It has a positive electrode, a negative electrode, and a liquid-retaining separator interposed between the two electrodes, and the separator is constructed by inserting glass fiber into a porous structure made of elastic acid-resistant synthetic resin. sealed sealed lead. The sealed lead-acid battery described in paragraph 1. ('4) The sealed lead-acid battery according to claim 1, wherein the separator further has a separator layer made of glass fiber.