JP2958785B2 - Manufacturing method of clad type positive plate - Google Patents
Manufacturing method of clad type positive plateInfo
- Publication number
- JP2958785B2 JP2958785B2 JP1318585A JP31858589A JP2958785B2 JP 2958785 B2 JP2958785 B2 JP 2958785B2 JP 1318585 A JP1318585 A JP 1318585A JP 31858589 A JP31858589 A JP 31858589A JP 2958785 B2 JP2958785 B2 JP 2958785B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode plate
- positive electrode
- clad
- type
- 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.)
- 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 本発明は交互充放電使用されるサイクルサービス用に
適した密閉形鉛蓄電池、特にこの種電池に用いるクラッ
ド式正極板の製造方法に関するものである。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a sealed lead-acid battery suitable for a cycle service in which charge and discharge are alternately used, and particularly to a method for producing a clad type positive electrode plate used for such a battery.
従来の技術とその課題 従来、この種密閉形鉛蓄電池においては、保水性を有
する多孔体セパレータおよび正・負極板にのみ電解液を
含浸保持させたいわゆるリテーナ式にして、正極で発生
した酸素ガスを負極へ拡散しやすくして負極と反応させ
て吸収する負極吸収式が多く採用されている。この場
合、多孔体セパレータに含浸された電解液がその作用を
十分に果たすためには、多孔体セパレータと正・負極板
が十分に密着していることが必要であり、そのため従来
のこの種密閉形鉛蓄電池においては正・負極板ともにペ
ースト式極板を使用して電池を構成していた。しかし、
正・負極板ともにペースト式極板を使用した密閉形鉛蓄
電池を、例えばフォーリフト、運搬車などの毎日深放電
と充電が繰り返し行われる交互充放電使用した場合に
は、ペースト式極板であるため、寿命が短かった。現
在、液式鉛蓄電池の長寿命化の要求に対してはクラッド
式の正極板を使用することが有効である。そのため従
来、交互充放電使用される蓄電池には正極板にクラッド
式極板、負極板にペースト式極板を使用した開放形の蓄
電池が用いられているが、この蓄電池は電解液の消失が
激しく、１週間〜10日に一度の割合で補水が必要であ
り、そのため交互充放電使用される蓄電池においても密
閉形にして無補水化することが強く要望されている。Conventional technology and its problems Conventionally, in this type of sealed lead-acid battery, a so-called retainer type in which only a porous separator having water retention and an electrolyte solution is impregnated and held on positive and negative electrode plates, and oxygen gas generated at a positive electrode is used. The negative electrode absorption type which easily diffuses to the negative electrode, reacts with the negative electrode, and absorbs it is widely used. In this case, in order for the electrolyte impregnated in the porous separator to sufficiently fulfill its function, the porous separator and the positive / negative electrode plates must be in close contact with each other. In a lead-acid battery, the battery is configured using a paste-type electrode plate for both the positive and negative electrode plates. But,
A sealed lead-acid battery using a paste-type electrode plate for both the positive and negative electrodes, for example, a forklift, a transport vehicle, etc. Therefore, the life was short. At present, it is effective to use a clad-type positive electrode plate in order to extend the life of a liquid lead storage battery. For this reason, conventionally, open-type storage batteries using a clad-type electrode plate as a positive electrode plate and a paste-type electrode plate as a negative electrode plate have been used for storage batteries that are used for alternate charge and discharge. Water replenishment is required once a week to every 10 days. Therefore, it is strongly desired that storage batteries used for alternate charge / discharge are sealed and have no water replenishment.
上記のためクラッド式正極板を用いて密閉形鉛蓄電池
を構成することが考えられたが、従来の密閉形鉛蓄電池
におけるペースト式正極板をクラッド式正極板に置き換
えるだけでは、多孔体セパレータとクラッド式正極板が
十分に密着せず、密閉形鉛蓄電池として成立しなかっ
た。即ち、第４図に示すように、クラッド式正極板１′
とペースト式負極板２との間に従来の保水性を有する多
孔体セパレータを配して圧迫を加えても、多孔体セパレ
ータ３は弾力性に富むので、ある程度クラッド式正極板
１′の面形状に沿った形となるが、クラッド式正極板
１′には安全に密着せず、クラッド式正極板１′の容量
を十分に引き出すことができなかった。For this reason, it was conceived to construct a sealed lead-acid battery using a clad-type positive electrode plate.However, simply replacing the paste-type positive electrode plate in a conventional sealed-type lead-acid battery with a clad-type positive electrode plate requires a porous separator and a clad The positive electrode plate did not adhere sufficiently, and was not realized as a sealed lead-acid battery. That is, as shown in FIG. 4, the clad type positive electrode plate 1 '
Even if a conventional porous separator having a water retention property is disposed between the paste-type negative electrode plate 2 and the paste-type negative electrode plate 2, the porous separator 3 is rich in elasticity. However, it did not adhere securely to the clad-type positive electrode plate 1 ', and the capacity of the clad-type positive electrode plate 1' could not be sufficiently drawn out.
そこで、特開昭61−232571号公報に示すような角チュ
ーブを用いた、表面が平滑なクラッド式正極板を多孔性
セパレータおよび負極板と積層してなるリテーナタイプ
の密閉電池が提案されている。また、表面が平滑なクラ
ッド式正極板を作る方法としては扁平あるいは角形のチ
ューブに鉛紛を振動により充填する方法と、特開昭62−
150653号公報に示すような通常の円柱状チューブにスラ
リー状ペーストを充填した後、押出成形する方法等が知
られている。Therefore, a sealed battery of a retainer type in which a clad-type positive electrode plate having a smooth surface is laminated with a porous separator and a negative electrode plate using a square tube as disclosed in JP-A-61-232571 has been proposed. . As a method for producing a clad-type positive electrode plate having a smooth surface, a method of filling a flat or square tube with lead powder by vibration, and a method disclosed in
There is known a method of filling a usual cylindrical tube as shown in JP-A-150653 with a slurry-like paste and extruding the same.
しかし、これらの正極板を用いた密閉形鉛蓄電池は従
来の円筒状チューブを有する液式鉛蓄電池に比べて寿命
性能が劣るという欠点があった。これはチューブ材質は
ほとんど伸びないので円筒チューブであれば使用中の活
物質の膨張がおさえられ、その体質変化が少なく、その
ため活物質粒子間の結合が比較的長期にわたって維持さ
れるのに対し、扁平あるいは角形のチューブを用いた場
合は次第に活物質体積が増加し、チューブの断面形状が
円に近くなり、結果として活物質粒子間の結合が切断さ
れて活物質の軟化を引き起こしたためと考えられる。However, the sealed lead-acid battery using these positive electrodes has a drawback that its life performance is inferior to that of a conventional liquid lead-acid battery having a cylindrical tube. This is because the tube material hardly expands, so if the tube is a cylindrical tube, the expansion of the active material during use is suppressed, the change in the constitution is small, and the bond between the active material particles is maintained for a relatively long time, If a flat or square tube is used, the volume of the active material gradually increases, and the cross-sectional shape of the tube becomes closer to a circle.As a result, the bonds between the active material particles are cut, which may cause the softening of the active material. .
また、一般に正極活物質の軟化は活物質密度が高いほ
ど起こり難いと考えられているが、振動により鉛紛をチ
ューブに充填するという従来法ではクラッド式正極板に
充填できる既化活物質密度は、せいぜい3.8g/cm3が限界
でありそれ以上の活物質密度を得るのは困難であった。In general, it is considered that the softening of the positive electrode active material is unlikely to occur as the active material density increases, but in the conventional method of filling lead powder into a tube by vibration, the density of the converted active material that can be filled in the clad positive electrode plate is as follows. However, the limit was at most 3.8 g / cm 3 , and it was difficult to obtain an active material density higher than 3.8 g / cm 3 .
課題を解決するための手段 本発明は上記欠点を除去するもので、円筒チューブを
有するクラッド式正極板に鉛紛を充填後、希硫酸に浸漬
し、ついでプレス成形して表面を平滑とすることを特徴
とし、さらに正極活物質を該プレス成形により高密度化
することを特徴とするものである。Means for Solving the Problems The present invention eliminates the above-mentioned drawbacks, and after filling lead powder into a clad-type positive electrode plate having a cylindrical tube, immersing it in dilute sulfuric acid, and then press-molding to smooth the surface. In addition, the positive electrode active material is densified by the press molding.
実施例 以下、図面を用いて本発明による密閉形鉛蓄電池を具
体的に説明する。EXAMPLES Hereinafter, a sealed lead-acid battery according to the present invention will be specifically described with reference to the drawings.
第１図は、本発明によるクラッド式正極板を示す斜視
図であり、４は極板耳、５は上部連座、６は下部連座、
７はチューブ、８はプレス成形により平滑となった部位
である。FIG. 1 is a perspective view showing a clad type positive electrode plate according to the present invention, wherein 4 is an electrode plate ear, 5 is an upper constellation, 6 is a lower constellation,
Reference numeral 7 denotes a tube, and 8 denotes a portion smoothed by press molding.
また、第２図は、本発明による正極板を用いて構成し
た密閉形鉛蓄電池極板群の要部横断面図であり、１はク
ラッド式正極板、２はペースト式負極板、３は多孔体セ
パレータで、クラッド式正極板１と多孔体セパレータ３
とが密着した構造となっている。ここで、本発明により
クラッド式正極板は円筒形チューブに鉛紛を充填した後
希硫酸に浸漬し、ついで所定の形状を保つための型ワク
に入れて150kg/dm2以上の圧力でプレス成形を行なって
作製した。別の製造方法として、円筒形チューブに鉛紛
を充填した後ただちプレス成形する方法が考えられる
が、この方法では、チューブの弾性と鉛紛の流動性のた
め成形できず、仮に成形できたとしても、後工程により
取り扱い操作によって、極板表面の平滑性が簡単に損な
われてしまい実用化は困難である。FIG. 2 is a cross-sectional view of a main part of a sealed lead-acid battery electrode group constituted by using the positive electrode plate according to the present invention, wherein 1 is a clad type positive electrode plate, 2 is a paste type negative electrode plate, and 3 is a porous type. Positive electrode plate 1 and porous separator 3
Has a close contact structure. Here, according to the present invention, the clad-type positive electrode plate is filled with lead powder in a cylindrical tube, immersed in dilute sulfuric acid, and then put into a mold for maintaining a predetermined shape and press-molded at a pressure of 150 kg / dm 2 or more. Was performed. As another manufacturing method, it is conceivable to press-mold immediately after filling the cylindrical tube with lead powder, but this method could not be formed due to the elasticity of the tube and the fluidity of the lead powder, and could be formed temporarily. However, the smoothness of the electrode plate surface is easily impaired by a handling operation in a post-process, and practical use is difficult.
さらに、本発明によるクラッド式正極板は高密度の活
物質を有することを特徴としており、鉛紛を振動により
充填するという従来の方法では約3.8g/cm3以下の既化活
物質密度しか充填できなかったのに比べ、本発明によれ
ばチューブの外周長さがほとんど変わることなく断面形
状が円から矩形もしくは長円形に変わりチューブ容積が
減少するので、3.9〜5.3g/cm3のものが得られた。これ
に対してスラリー状ペーストを充填後プレス成形すると
いう方法ではチューブの網目から該ペーストが流出して
しまうため、および、プレス後にこのような高密度活物
質を得るためには該ペーストの密度を相当に高くする必
要があり、その様なペーストは流動性乏しく充填性に欠
けるため高密度化は困難である。Furthermore, the clad type positive electrode plate according to the present invention is characterized by having a high-density active material, and the conventional method of filling lead powder by vibration only fills the activated material density of about 3.8 g / cm 3 or less. Compared to that, according to the present invention, the cross-sectional shape changes from a circle to a rectangle or an ellipse with almost no change in the outer peripheral length of the tube, and the tube volume decreases, so that 3.9 to 5.3 g / cm 3 Obtained. On the other hand, in the method of press molding after filling the slurry paste, the paste flows out from the mesh of the tube, and in order to obtain such a high-density active material after pressing, the density of the paste is reduced. It is necessary to make the paste considerably high, and it is difficult to increase the density of such paste because of poor fluidity and poor filling property.
本発明の方法によりチューブの網目からの鉛紛の流出
がほとんどなくプレス成形できたのは該成形前に希硫酸
浸漬を行うことにより該網目付近に緻密な硫酸鉛層が成
形されたためおよび鉛紛を希硫酸中に浸漬しただけでは
スラリー状ペーストほどの流動性が生じないためだと思
われる。The method of the present invention was able to press-mold with almost no outflow of lead powder from the mesh of the tube because a dense lead sulfate layer was formed in the vicinity of the mesh by diluting sulfuric acid before the formation, This is probably because immersion in dilute sulfuric acid does not produce the fluidity of a slurry paste.
次に、従来の角チューブに鉛紛を充填したクラッド式
正極板と本発明により円筒状チューブに鉛紛を充填し、
希硫酸に浸漬後プレス成形したクラッド式正極板とを正
極活物質密度を変えて製作し、第２図に示す如き極板群
構成の密閉電池Ａを製作した。Next, a conventional square tube filled with lead powder and a cylindrical tube filled with lead powder according to the present invention,
A clad type positive electrode plate which was immersed in dilute sulfuric acid and then press-molded was manufactured by changing the density of the positive electrode active material, and a sealed battery A having an electrode group structure as shown in FIG. 2 was manufactured.
これらの密閉電池Ａおよび従来の液式電池Ｂに定格容
量の75％放電を行う充放電サイクル寿命試験を行った結
果を第３図に示す。本試験によれば既化活物質密度2.9
〜3.7g/cm3の従来法による密閉電池は液式電池に比べ寿
命性能が劣ったが、3.9〜5.3g/cm3の本発明による密閉
電池は液式電池と同等以上の寿命性能を示した。なおこ
こで活物質密度を5.3g/cm3までとしたのは本発明による
製造方法ではこの程度の活物質密度が限界であったため
である。FIG. 3 shows the results of a charge / discharge cycle life test in which the sealed battery A and the conventional liquid battery B were discharged at 75% of the rated capacity. According to this test, the converted active material density was 2.9.
Sealed battery according to the conventional method of ~3.7g / cm 3 is compared life performance was inferior to the liquid type battery, the sealed battery according to the present invention 3.9~5.3g / cm 3 represents the liquid type battery equal to or higher than the life performance Was. The reason why the active material density was set to 5.3 g / cm 3 was that the active material density of this level was the limit in the production method according to the present invention.
発明の効果 以上述べたように本発明によれば、交互充放電使用さ
れるサイクルサービス用に適した密閉形鉛蓄電池を得る
ことができ、フォークリスト用などの蓄電池における無
補水化を図ることができるので、工業的価値は大きい。Effect of the Invention As described above, according to the present invention, it is possible to obtain a sealed lead-acid battery suitable for cycle service in which alternating charge and discharge are used, and to achieve no water refilling in a storage battery for a fork wrist or the like. The industrial value is great because it is possible.
第１図は本発明によるクラッド式正極板を示す斜視図、
第２図は本発明によるクラッド式正極板を用いて構成し
た密閉形鉛蓄電池極板群の要部横断面図、第３図は本発
明による平滑クラッド式正極板並びに従来の平滑クラッ
ド式正極板を用いた密閉形鉛蓄電池および従来の液式鉛
蓄電池の正極既化活物質密度とサイクル寿命性能との関
係を示す図、第４図は従来のこの種密閉形鉛蓄電池の極
板群構成の一例を示す要部断面図である。 １……クラッド式正極板、２……ペースト式負極板、 ３……多孔体セパレータ、４……極板耳、 ５……上部連座、６……下部連座、７……チューブ、 ８……プレス成形部位FIG. 1 is a perspective view showing a clad type positive plate according to the present invention,
FIG. 2 is a cross-sectional view of a main part of a sealed lead-acid battery electrode group constituted by using the clad type positive electrode plate according to the present invention. FIG. 3 is a smooth clad type positive electrode plate according to the present invention and a conventional smooth clad type positive electrode plate. Fig. 4 shows the relationship between the positive electrode activated material density and the cycle life performance of a sealed lead-acid battery using a battery and a conventional liquid lead-acid battery, and Fig. 4 shows the configuration of the electrode group of the conventional sealed lead-acid battery of this type. It is principal part sectional drawing which shows an example. DESCRIPTION OF SYMBOLS 1 ... Clad positive electrode plate, 2 ... Paste negative electrode plate, 3 ... Porous separator, 4 ... Electrode plate ear, 5 ... Upper joint, 6 ... Lower joint, 7 ... Tube, 8 ... Press forming part
Claims (1)
を充填し、希硫酸に浸漬後プレス成形により表面を平滑
にしてなることを特徴とする鉛蓄電池用クラッド式正極
板の製造方法1. A method of manufacturing a clad-type positive electrode plate for a lead-acid battery, comprising: filling a clad-type grid body provided with a tube with lead powder, immersing the powder in dilute sulfuric acid, and smoothing the surface by press molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1318585A JP2958785B2 (en) | 1989-12-07 | 1989-12-07 | Manufacturing method of clad type positive plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1318585A JP2958785B2 (en) | 1989-12-07 | 1989-12-07 | Manufacturing method of clad type positive plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03179663A JPH03179663A (en) | 1991-08-05 |
| JP2958785B2 true JP2958785B2 (en) | 1999-10-06 |
Family
ID=18100781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1318585A Expired - Fee Related JP2958785B2 (en) | 1989-12-07 | 1989-12-07 | Manufacturing method of clad type positive plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2958785B2 (en) |
-
1989
- 1989-12-07 JP JP1318585A patent/JP2958785B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03179663A (en) | 1991-08-05 |
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