JPH0810589B2 - Lead acid battery - Google Patents
Lead acid batteryInfo
- Publication number
- JPH0810589B2 JPH0810589B2 JP1284241A JP28424189A JPH0810589B2 JP H0810589 B2 JPH0810589 B2 JP H0810589B2 JP 1284241 A JP1284241 A JP 1284241A JP 28424189 A JP28424189 A JP 28424189A JP H0810589 B2 JPH0810589 B2 JP H0810589B2
- Authority
- JP
- Japan
- Prior art keywords
- clad
- electrode plate
- positive electrode
- lead
- active material
- 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 - Fee Related
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
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はクラッド式の正極板と任意の負極板とを組み
合わせて構成されるクラッド式の鉛蓄電池に関するもの
である。TECHNICAL FIELD The present invention relates to a clad lead-acid battery constituted by combining a clad positive electrode plate and an arbitrary negative electrode plate.
［従来技術］ 長寿命を狙った鉛蓄電池として、クラッド式の正極板
と任意の負極板とを組み合わせたものがある。クラッド
式の正極板は、ガラス繊維や耐酸、耐酸化性を有する合
成樹脂繊維等からなる多孔性のクラッドチューブにより
正極活物質を被包した構造を有するもので、鉛合金格子
体の芯金を多孔性のクラッドチューブ内の中心に位置さ
せた状態で該チューブ内に鉛粉または鉛粉と硫酸とを混
練した鉛ペーストを充填して、希硫酸中で化成すること
により製造される。[Prior Art] As a lead-acid battery aiming at a long life, there is a lead-acid battery in which a clad-type positive electrode plate and an arbitrary negative electrode plate are combined. The clad type positive electrode plate has a structure in which the positive electrode active material is encapsulated by a porous clad tube made of glass fiber, acid resistant, synthetic resin fiber having oxidation resistance, or the like. It is manufactured by filling lead powder or a lead paste obtained by kneading lead powder and sulfuric acid in the tube in a state of being positioned at the center in a porous clad tube, and performing chemical conversion in dilute sulfuric acid.
鉛蓄電池では、充放電の繰り返しにより正極活物質が
軟化、泥状化して脱落し易くなるが、クラッド式正極板
を任意の負極板（通常はペースト式の極板）とを組み合
わせた鉛蓄電池では、クラッドチューブにより正極活物
質の脱落を防止できるため、ペースト式の正極板を用い
た場合に比べて電池の寿命の延長を図ることができる。In a lead-acid battery, the positive electrode active material softens and becomes mud-like due to repeated charging and discharging, and it is easy to fall off.However, in a lead-acid battery that combines a clad type positive electrode plate with an arbitrary negative electrode plate (usually a paste type electrode plate). Since the clad tube can prevent the positive electrode active material from falling off, the life of the battery can be extended as compared with the case where a paste type positive electrode plate is used.
クラッドチューブとしては、ガラス繊維または耐酸、
耐酸化性を有する樹脂の繊維の織布または不織布からな
るチューブを樹脂で固めたものが使用される場合と、耐
酸性を有する樹脂の不織布等からなる多孔性基材の上に
更に微孔樹脂層を形成した樹脂膜をチューブ状に形成し
たものが用いられる場合とがある。As the clad tube, glass fiber or acid resistant,
When a tube made of woven or non-woven fabric of resin fibers having oxidation resistance is solidified with resin, and when a microporous resin is formed on a porous substrate made of non-woven fabric of acid resistant resin. In some cases, a tube-shaped resin film having layers is used.
後者のクラッドチューブを製造する場合には、先ず耐
酸、耐酸化性合成樹脂の繊維の不織布等からなる多孔性
基材に、合成樹脂と揮発成分を有する種々の溶液とを混
練して得た塗布材を塗布して該塗布材の層から揮発成分
を飛ばすことにより、多孔性基材の上に無数の微孔を有
する微孔樹脂層が形成された樹脂膜を得、この樹脂膜を
チューブの形に形成することによりクラッドチューブを
得る。In the case of manufacturing the latter clad tube, first, a coating obtained by kneading a synthetic resin and various solutions having a volatile component on a porous base material made of a non-woven fabric of fibers of synthetic resin having acid resistance and oxidation resistance. By applying a material to remove volatile components from the layer of the applied material, a resin film having a microporous resin layer having innumerable micropores formed on a porous substrate is obtained. A clad tube is obtained by forming into a shape.
ガラス繊維または合成樹脂の織布または不織布を樹脂
で固めた構造のクラッドチューブを用いた場合には、ク
ラッドチューブの平均孔径が比較的大きいため、クラッ
ドチューブの孔を通して活物質が通り抜けることがあ
る。そのため、このクラッドチューブを用いた正極板を
使用する場合には、極板間の短絡を防止するために正極
板と負極板との間にセパレータを介在させる必要があ
る。When a clad tube having a structure in which glass fiber or synthetic resin woven or non-woven fabric is hardened with a resin is used, the active material may pass through the holes of the clad tube because the average diameter of the clad tube is relatively large. Therefore, when a positive electrode plate using this clad tube is used, it is necessary to interpose a separator between the positive electrode plate and the negative electrode plate in order to prevent a short circuit between the electrode plates.
これに対し、多孔性基材に微孔樹脂層を形成した樹脂
膜からなるクラッドチューブを用いた正極板では、平均
孔径が２μｍ以下であるため、活物質がクラッドチュー
ブの孔を通り抜けるのを防止することができる。したが
ってこのクラッド式正極板を用いると、正極板と負極板
とを直接当接させて極板群を構成することが可能にな
る。On the other hand, in a positive electrode plate using a clad tube made of a resin film in which a microporous resin layer is formed on a porous substrate, the average pore diameter is 2 μm or less, so that the active material is prevented from passing through the holes of the clad tube. can do. Therefore, when this clad positive electrode plate is used, it is possible to directly contact the positive electrode plate and the negative electrode plate to form an electrode plate group.
［発明が解決しようとする課題］ クラッド式正極板を用いた鉛蓄電池では、高率放電に
使用される場合に、クラッドチューブ内への電解液の拡
散が遅れて電池の上部と下部とで電解液の比重に差が生
じる、いわゆる成層化現象が生じ、特性が劣化するとい
う問題があった。この問題は特に平均孔径が小さいクラ
ッドチューブを用いる場合は顕著になる。[Problems to be Solved by the Invention] In a lead-acid battery using a clad positive electrode plate, when used for high-rate discharge, the diffusion of the electrolytic solution into the clad tube is delayed and electrolysis occurs at the upper and lower parts of the battery. There is a problem that a so-called stratification phenomenon occurs, which causes a difference in specific gravity of the liquids, and deteriorates the characteristics. This problem becomes remarkable especially when a clad tube having a small average pore size is used.
また充放電によりクラッドチューブの孔を通して僅か
でも正極活物質が排出されると、排出された活物質（Pb
O2）が負極板で還元されて、海綿状鉛が析出し、この海
綿状鉛が極板群の上部に堆積していくと、ついには極板
間短絡が生じて電池の寿命が尽きることになる。したが
ってクラッド式鉛蓄電池の寿命の延長を図るには、クラ
ッドチューブから排出される活物質の量をできるだけ少
なくすることが必要である。In addition, if the positive electrode active material is discharged through the holes of the clad tube due to charging and discharging, even if the discharged active material (Pb
O 2 ) is reduced by the negative electrode plate, spongy lead is deposited, and if this spongy lead is deposited on the upper part of the electrode plate group, eventually a short circuit occurs between the electrode plates and the battery life ends. become. Therefore, in order to extend the life of the clad lead acid battery, it is necessary to reduce the amount of the active material discharged from the clad tube as much as possible.
本発明の目的は、クラッドチューブ内に電解液を保持
させる機能を持たせることにより、従来より優れた高率
放電特性を得ることができる上に、正極活物質の排出を
抑制して寿命の延長を図ることができるようにしたクラ
ッド式の鉛蓄電池を提供することにある。An object of the present invention is to provide a function of retaining an electrolytic solution in a clad tube to obtain a high rate discharge characteristic superior to conventional ones, and at the same time suppress the discharge of a positive electrode active material to extend the life. (EN) Provided is a clad-type lead acid battery capable of achieving the above.
［課題を解決するための手段］ 本発明は、格子体の芯金が挿入されたクラッドチュー
ブ内に活物質を充填した構造を有するクラッド式正極板
を用いた鉛蓄電池において、活物質とクラッドチューブ
の内面との間にゲル状の電解液保持体を介在させたもの
である。[Means for Solving the Problems] The present invention relates to a lead storage battery using a clad-type positive electrode plate having a structure in which an active material is filled in a clad tube in which a core metal of a lattice is inserted. A gel electrolyte holding body is interposed between the inner surface and the inner surface.
［作 用］ 上記のように、正極板のクラッドチューブの内面と活
物質のと間にゲル上の電解液保持体を介在させると、正
極板内に電解液を保持することができるため、電池の上
部と下部とで電解液の比重に差が生じる成層化現象を防
止することができ、正極板全体に亘って均一な充放電反
応を行わせて高率放電特性を改善することができる。[Operation] As described above, when the electrolytic solution holder on the gel is interposed between the inner surface of the clad tube of the positive electrode plate and the active material, the electrolytic solution can be retained in the positive electrode plate, so that the battery can be retained. It is possible to prevent the stratification phenomenon in which the specific gravity of the electrolytic solution is different between the upper part and the lower part of the battery, and it is possible to improve the high-rate discharge characteristics by performing a uniform charge / discharge reaction over the entire positive electrode plate.
また正極活物質とクラッドチューブ内面との間にゲル
上の電解液保持体を介在させたことにより、クラッドチ
ューブ内の活物質を固定することができるため、クラッ
ドチューブの孔を通して活物質が排出されるのを防止す
ることができ、排出された正極活物質（PbO2）が負極板
で還元されて海綿状鉛が析出するのを抑制して、クラッ
ド式鉛蓄電池の寿命を延長することができる。Further, by interposing the electrolytic solution holder on the gel between the positive electrode active material and the inner surface of the clad tube, the active material in the clad tube can be fixed, so that the active material is discharged through the holes of the clad tube. Can be prevented, and the discharged positive electrode active material (PbO 2 ) can be prevented from being reduced by the negative electrode plate to deposit spongy lead, thereby extending the life of the clad lead acid battery. .
［実施例］ 以下、図面を参照して本発明の実施例を詳細に説明す
る。[Example] Hereinafter, an example of the present invention will be described in detail with reference to the drawings.
図面は本発明のクラッド式鉛蓄電池の一実施例の要部
の概略断面図である。同図において、１はクラッド式正
極板、２はペースト式の負極板、３は正極板１と負極板
２との間に配置されたセパレータである。正極板１と負
極板２とがセパレータ３を介して積層されて極板群が構
成され、この極板群が電解液と共に図示しない電槽内に
収納されて鉛蓄電池が構成される。The drawings are schematic cross-sectional views of the essential parts of an embodiment of the clad lead-acid battery of the present invention. In the figure, 1 is a clad type positive electrode plate, 2 is a paste type negative electrode plate, and 3 is a separator disposed between the positive electrode plate 1 and the negative electrode plate 2. A positive electrode plate 1 and a negative electrode plate 2 are laminated via a separator 3 to form an electrode plate group, and the electrode plate group is housed together with an electrolytic solution in a battery case (not shown) to form a lead acid battery.
正極板１は、クラッドチューブ101と、クラッドチュ
ーブ101内の中心に配置された芯金102を有する鉛合金格
子体と、クラッドチューブ101内に充填された正極活物
質103と、クラッドチューブ101の内面と正極活物質103
との間に介在されたゲル状の電解液保持体104とにより
構成される。クラッドチューブ101は、耐酸、耐酸化性
樹脂の繊維の不織布等からなる多孔性基材101aの上に微
孔樹脂層101bを形成した樹脂膜を、その微孔樹脂層101b
を内側にしてチューブ状に成形したものからなってい
る。The positive electrode plate 1 includes a clad tube 101, a lead alloy lattice having a cored bar 102 arranged in the center of the clad tube 101, a positive electrode active material 103 filled in the clad tube 101, and an inner surface of the clad tube 101. And positive electrode active material 103
And a gel electrolyte holding body 104 interposed between and. The clad tube 101 is a resin film in which a microporous resin layer 101b is formed on a porous substrate 101a made of a non-woven fabric of fibers of acid-resistant and oxidation-resistant resin.
It is made by forming a tube with the inside.
ゲル状電解液保持体は、電解液を保持したゲル状物質
で、この電解液保持体としては、密閉式の鉛蓄電池に用
いられているゲル状電解液と同じものを用いることがで
きる。The gel-like electrolytic solution holder is a gel-like substance that holds the electrolytic solution, and the same electrolytic solution holder as the gel-like electrolytic solution used in the sealed lead-acid battery can be used.
実施例では、ABS樹脂系練液をポリエステル不織布か
らなる多孔性基材に塗布した後、練液中の揮発成分を除
去して樹脂膜を形成した。この樹脂膜の孔径は平均で0.
7μｍ、最大で2.1μｍであった。この樹脂膜をその微孔
樹脂層101b側を内側にして巻回し、その重合部分を熱溶
着することにより、内径9mm、長さ275mmのクラッドチュ
ーブ101を製造した。In the examples, the ABS resin-based kneading liquid was applied to the porous substrate made of polyester nonwoven fabric, and then the volatile components in the kneading liquid were removed to form a resin film. The pore size of this resin film is 0 on average.
It was 7 μm and the maximum was 2.1 μm. This resin film was wound with the microporous resin layer 101b side facing inward, and the polymerized portion was heat-welded to manufacture a clad tube 101 having an inner diameter of 9 mm and a length of 275 mm.
次にこのクラッドチューブ101の内面にシリカ粒子及
びアルミナ粒子の無機酸化物を主成分としたエアロジル
を均一に保持させ、クラッドチューブ101とこのクラッ
ドチューブ内に配置された芯金102との間に活物質103を
充填し、通常の方法によりクラッド式正極板１を製造し
た。なお活物質の充填密度は、3.1g/mm3とした。Next, the inner surface of the clad tube 101 is made to uniformly hold aerosil mainly composed of an inorganic oxide of silica particles and alumina particles, and activated between the clad tube 101 and the cored bar 102 arranged in the clad tube. The material 103 was filled and the clad cathode plate 1 was manufactured by a conventional method. The packing density of the active material was 3.1 g / mm 3 .
上記のようにして製造されたクラッド式正極板１を８
枚、通常のペースト式の負極板２を９枚、セパレータ３
を８枚用いて、正極板と負極板とをセパレータを介して
積層することにより極板群を構成し、該極板群を電槽内
に収納した後注液して化成を行った。クラッドチューブ
内面に保持させたエアロジルは電解液の希硫酸を注液す
ることによりゲル状化する。The clad cathode plate 1 manufactured as described above is
Sheet, 9 pieces of normal paste type negative electrode plate 2, separator 3
8 sheets were used to form an electrode plate group by laminating a positive electrode plate and a negative electrode plate with a separator interposed therebetween, and the electrode plate group was housed in a battery case and then injected to perform chemical conversion. Aerosil retained on the inner surface of the clad tube is gelated by injecting dilute sulfuric acid as an electrolytic solution.
比較のために、従来のクラッド式正極板を用いたクラ
ッド式鉛蓄電池を用意した。For comparison, a clad lead-acid battery using a conventional clad positive electrode plate was prepared.
上記のようにして製造した本発明の一実施例のクラッ
ド式鉛蓄電池Ａと従来のクラッド式鉛蓄電池Ｂとを用い
て、30℃の環境温度において放電試験を行った。なお放
電前の補充電により電解液比重を1.280に調整した。こ
の比較試験の結果を以下の表に示す。Using the clad-type lead-acid battery A of the embodiment of the present invention and the conventional clad-type lead-acid battery B manufactured as described above, a discharge test was conducted at an environmental temperature of 30 ° C. The specific gravity of the electrolyte was adjusted to 1.280 by supplementary charging before discharge. The results of this comparative test are shown in the table below.
上記の表から明らかなように、本発明に係わるクラッ
ド式鉛蓄電池は、従来のクラッド式鉛蓄電池よりもクラ
ッドチューブの孔径が小さく、クラッドチューブ内への
電解液の拡散が遅れるにもかかわらず、従来よりも長く
放電を行うことができた。 As is clear from the above table, the clad lead-acid battery according to the present invention has a smaller pore diameter of the clad tube than the conventional clad lead-acid battery, and delays the diffusion of the electrolytic solution into the clad tube. The discharge could be performed longer than before.
また本発明に係わる鉛蓄電池は、ゲル状の電解液保持
体をクラッドチューブ内に設けた分だけ従来の鉛蓄電池
よりもクラッドチューブ内への活物質の充填量が少ない
にもかかわらず、放電容量が高くなっている。Further, the lead storage battery according to the present invention has a smaller discharge capacity than the conventional lead storage battery in which the amount of the active material filled in the clad tube is smaller than that of the conventional lead storage battery because the gel electrolyte holding body is provided in the clad tube. Is high.
以上の結果から、本発明によれば高率放電特性の向上
と、クラッド式鉛蓄電池の高容量化とを図ることが可能
であることが明らかになった。From the above results, it became clear that according to the present invention, it is possible to improve the high rate discharge characteristics and increase the capacity of the clad lead acid battery.
上記の実施例では、微孔樹脂層を形成することにより
平均孔径を小さくした樹脂膜を用いてクラッドチューブ
を形成したが、ガラス繊維の織布または不織布、或いは
耐酸、耐酸化性合成樹脂の繊維の織布または不織布によ
り形成される、平均孔径が比較的大きいクラッドチュー
ブが用いられる場合にも本発明を適用することができ
る。In the above examples, the clad tube was formed by using the resin film having a small average pore size by forming the microporous resin layer, but a woven or non-woven fabric of glass fibers, or fibers of acid-resistant and oxidation-resistant synthetic resin. The present invention can also be applied to the case where a clad tube having a relatively large average pore size, which is formed of the woven cloth or the nonwoven cloth, is used.
［発明の効果］ 以上のように、本発明によれば、クラッド式正極板の
クラッドチューブの内面と活物質との間にゲル状電解液
保持体を介在させたので、孔系が小さいクラッドチュー
ブを用いたクラッド式正極板用いても、クラッド式正極
板の活物質に十分な電解液を確保して高率放電特性を向
上させることができる利点がある。[Effects of the Invention] As described above, according to the present invention, the gel electrolyte holding body is interposed between the inner surface of the clad tube of the clad positive electrode plate and the active material, so that the clad tube having a small pore system is provided. Even if the clad type positive electrode plate using is used, there is an advantage that a sufficient electrolytic solution can be secured in the active material of the clad type positive electrode plate and the high rate discharge characteristics can be improved.
またゲル状電解液保持体によりクラッドチューブ内の
活物質を固定することができるため、充放電によりクラ
ッドチューブの孔を抜けて活物質が脱落するのを防止す
ることができる。したがってPbO2が負極板上で還元、析
出して海綿状鉛が生成されるのを抑制して電池を寿命の
延長を図ることができる。Further, since the active material in the clad tube can be fixed by the gel electrolyte holding body, it is possible to prevent the active material from falling out through the holes of the clad tube due to charge / discharge. Therefore, it is possible to suppress the reduction and precipitation of PbO 2 on the negative electrode plate to generate spongy lead, thereby extending the life of the battery.
図面は本発明のクラッド式鉛蓄電池の一実施例の要部の
概略構成を示す断面図である。 １……クラッド式正極板、101……クラッドチューブ、1
02……芯金、103……正極活物質、104……ゲル状電解液
保持体、２……負極板、３……セパレータ。The drawing is a cross-sectional view showing a schematic configuration of a main part of an embodiment of the clad lead-acid battery of the present invention. 1 …… Clad type positive plate, 101 …… Clad tube, 1
02: core metal, 103: positive electrode active material, 104: gel electrolyte holder, 2 ... negative electrode plate, 3 ... separator.
Claims (1)
ブ内に活物質を充填してなるクラッド式正極板を用いた
鉛蓄電池において、 前記活物質とクラッドチューブの内面との間にゲル状の
電解液保持体を介在させたことを特徴とする鉛蓄電池。1. A lead-acid battery using a clad positive electrode plate in which an active material is filled in a clad tube in which a core metal of a lattice is inserted, wherein a gel-like material is provided between the active material and the inner surface of the clad tube. A lead-acid battery characterized in that the electrolyte holding body of 1 is interposed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1284241A JPH0810589B2 (en) | 1989-10-31 | 1989-10-31 | Lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1284241A JPH0810589B2 (en) | 1989-10-31 | 1989-10-31 | Lead acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03147255A JPH03147255A (en) | 1991-06-24 |
| JPH0810589B2 true JPH0810589B2 (en) | 1996-01-31 |
Family
ID=17675997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1284241A Expired - Fee Related JPH0810589B2 (en) | 1989-10-31 | 1989-10-31 | Lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0810589B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG11201902950YA (en) * | 2016-10-07 | 2019-05-30 | Hitachi Chemical Co Ltd | Cladding tube, clad electrode, lead storage battery, production method for these, and electric car |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59160964A (en) * | 1983-03-04 | 1984-09-11 | Yuasa Battery Co Ltd | Storage battery |
-
1989
- 1989-10-31 JP JP1284241A patent/JPH0810589B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59160964A (en) * | 1983-03-04 | 1984-09-11 | Yuasa Battery Co Ltd | Storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03147255A (en) | 1991-06-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |