JP2982555B2 - Method for manufacturing positive electrode plate of paste type lead battery - Google Patents
Method for manufacturing positive electrode plate of paste type lead batteryInfo
- Publication number
- JP2982555B2 JP2982555B2 JP5126410A JP12641093A JP2982555B2 JP 2982555 B2 JP2982555 B2 JP 2982555B2 JP 5126410 A JP5126410 A JP 5126410A JP 12641093 A JP12641093 A JP 12641093A JP 2982555 B2 JP2982555 B2 JP 2982555B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- electrode plate
- paste
- positive electrode
- sulfuric acid
- 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 - Lifetime
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
【０００１】[0001]
【産業上の利用分野】本発明は、ペースト式鉛電池正極
板の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a positive electrode plate of a paste type lead battery.
【０００２】[0002]
【従来の技術】一般に、ペースト式鉛電池の正極板は、
一酸化鉛を主体とする鉛酸化物、いわゆる鉛粉を水およ
び希硫酸で混練することによってペーストを調製し、こ
れを鉛あるいは鉛合金から成る格子体に塗布した後、熟
成、乾燥、化成することによって製造されている。ここ
で、一酸化鉛を主体とする鉛酸化物、いわゆる鉛粉に鉛
丹を混ぜてペーストを調製すると、化成効率が高くなる
ことが一般に知られている。しかし、以下に示す種々の
理由によって、ペースト式鉛電池の正極板には現在ほと
んど鉛丹の使用が見られない。2. Description of the Related Art Generally, the positive electrode plate of a paste type lead battery is
A paste is prepared by kneading lead oxide mainly composed of lead monoxide, so-called lead powder, with water and dilute sulfuric acid, and applying this to a grid made of lead or a lead alloy, followed by aging, drying and chemical formation. It is manufactured by. Here, it is generally known that when a paste is prepared by mixing lead oxide with lead oxide mainly composed of lead monoxide, so-called lead powder, the formation efficiency is increased. However, for the following various reasons, almost no lead tin is used in the positive electrode plate of the paste type lead battery at present.
【０００３】鉛丹を混合すると、活物質粒子間の結合
力が低下するため、化成中に剥離しやすく、また、サイ
クルサービスにおける正極板の寿命が短くなる。 鉛丹を混合すると、熟成、乾燥後の未化成活物質の強
度が低下し、ハンドリング時に未化活物質が脱落し易く
なる。 鉛丹を混ぜることによって化成効率を大幅に改善する
ためには、その混合率を、全鉛酸化物の２０％以上とす
る必要があり、原料の大幅なコストアップとなる。 なお、鉛丹の混合による正極板の寿命特性の低下に関し
ては、その改善策として、主原料となる一酸化鉛に一部
斜方晶系のものを用いるなどの方法（特開昭６４−８９
２６２号公報）が知られているが、化成効率を大幅に改
善し、かつ、上記問題点を解決するための鉛丹の有効な
混合方法については、これまでほとんど知られていな
い。[0003] When lead tin is mixed, the bonding force between the active material particles is reduced, so that the active material particles are easily peeled off during chemical formation, and the life of the positive electrode plate in cycle service is shortened. When lead ginseng is mixed, the strength of the unconverted active material after aging and drying is reduced, and the unconverted active material is easily dropped off during handling. In order to significantly improve the conversion efficiency by mixing lead red, the mixing ratio must be 20% or more of the total lead oxide, resulting in a significant increase in the cost of the raw material. Regarding the reduction of the life characteristics of the positive electrode plate due to the mixing of lead red, as a measure for improvement, a method such as using a partially orthorhombic lead monoxide as a main raw material (Japanese Patent Laid-Open No. 64-89)
No. 262) is known, but an effective method of mixing leadtan for greatly improving the formation efficiency and solving the above problems has not been known so far.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、鉛丹の混合
方法によって、上記種々の問題点を解決し、活物質、未
化活物質の強度向上と鉛丹の有効利用を図るものであ
る。SUMMARY OF THE INVENTION The present invention solves the above-mentioned various problems by a method for mixing lead red, and aims at improving the strength of the active material and the unactivated active material and effectively using the lead. .
【０００５】[0005]
【課題を解決するための手段】上記問題点を解決するた
め、本発明では、まず、水に鉛丹を分散させた後、希硫
酸を添加し、鉛丹と硫酸の反応を完了させた後、このス
ラリー状物質を一酸化鉛を主体とする鉛酸化物に加え、
混練することとした。In order to solve the above problems, according to the present invention, first, after dispersing red lead in water, dilute sulfuric acid is added to complete the reaction between lead red and sulfuric acid. , Adding this slurry-like substance to lead oxide mainly composed of lead monoxide,
It was decided to knead.
【０００６】[0006]
【作用】以下に本発明の作用について述べる。まず、従
来のペースト調製方法、すなわち、一酸化鉛を主体とす
る鉛酸化物、いわゆる鉛粉と鉛丹との混合物を水および
希硫酸によって混練するという方法によってペーストを
調製すると、添加した硫酸はほとんど全て一酸化鉛と反
応し、反応生成物として三塩基性硫酸鉛を生じる。すな
わち、鉛丹は、ほとんど硫酸と反応せずにそのままペー
スト中に残留する。そして、この鉛丹は、化成するとき
注入される電解液すなわち希硫酸と反応して二酸化鉛と
硫酸鉛を生成する。電解液すなわち希硫酸と反応するこ
とによって生成する硫酸鉛は、非常に大きな結晶であ
る。この大きな結晶は極板内部に歪みを生じさせ、活物
質粒子間の結合力を低下させていると考えられる。ま
た、化成効率を向上させる二酸化鉛の生成は、主とし
て、電解液と未化活物質が接している極板の表面近くで
起こり、極板の内部の鉛丹は硫酸と十分に反応できない
ために、そのまま鉛丹として残り有効に利用されないこ
とになる。The operation of the present invention will be described below. First, when the paste is prepared by a conventional paste preparation method, that is, a method of kneading a mixture of lead oxide and lead red lead mainly composed of lead monoxide with water and dilute sulfuric acid, the added sulfuric acid is Reacts almost all with lead monoxide to produce tribasic lead sulfate as a reaction product. That is, the lead red remains almost in the paste without reacting with sulfuric acid. Then, the lead redwood reacts with an electrolytic solution injected during chemical formation, that is, dilute sulfuric acid, to generate lead dioxide and lead sulfate. Lead sulfate produced by reacting with an electrolytic solution, that is, dilute sulfuric acid, is a very large crystal. It is considered that this large crystal causes a strain inside the electrode plate and reduces the bonding force between the active material particles. Also, the generation of lead dioxide, which improves the conversion efficiency, occurs mainly near the surface of the electrode plate where the electrolyte and the unactivated active material are in contact, and the lead tin inside the electrode plate cannot react sufficiently with sulfuric acid. However, it will remain as lead and will not be used effectively.
【０００７】例えば、鉛丹と希硫酸を直接混合して鉛丹
スラリーとし、この鉛丹スラリーと鉛粉とを混練する方
法（特開平５−１３０７４号公報）が知られているが、
鉛丹の粉末に希硫酸を直接混合する際に発熱し、反応生
成物が粒状に硬く凝集して化成時に均一な反応および反
応生成物を得ることができず、その結果正極活物質間の
結合力が低下するので、サイクルサービスにおける正極
板の寿命が短くなる。これに対し、本発明によれば、ま
ず、水に鉛丹を分散させた後、これに希硫酸を添加し、
このスラリー状物質を一酸化鉛を主体とする鉛酸化物に
加え、混練することから、従来法と異なり、以下のよう
な特徴がある。 For example, leadtan and dilute sulfuric acid are directly mixed to produce
Slurry and kneading this lead-tan slurry with lead powder
The method (JP-A-5-13074) is known,
When dilute sulfuric acid is directly mixed with leadtan powder, it generates heat and
The product is hard and agglomerated in a granular form and uniform reaction and
Reaction product cannot be obtained, and as a result,
Positive electrode in cycle service as binding force decreases
The life of the plate is shortened. On the other hand, according to the present invention, first, after dispersing lead red in water, dilute sulfuric acid is added thereto,
Since this slurry-like substance is added to lead oxide mainly composed of lead monoxide and kneaded, the following features are different from the conventional method.
【０００８】まず初めに、水に鉛丹を分散させること
が重要で、これに希硫酸を添加することによって、鉛丹
と希硫酸の反応を均一に行うことができ、鉛丹と希硫酸
の反応によって生成した硫酸鉛は、一酸化鉛を主体とす
る鉛酸化物、いわゆる鉛粉と混練されることによって、
これと反応し、ペースト中に三塩基性硫酸鉛を均一に生
成する。鉛丹と希硫酸の反応によって生成した二酸化
鉛は、スラリー状物質として一酸化鉛を主体とする鉛酸
化物、いわゆる鉛粉に加えて混練されることによって、
ペースト中に更に均一に分散される。 [0008] First, disperse the lead in water
Is important, and by adding dilute sulfuric acid,
The reaction between dilute sulfuric acid and lead sulfuric acid can be performed uniformly, and lead sulfate generated by the reaction between lead tin and dilute sulfuric acid is kneaded with lead oxide mainly composed of lead monoxide, so-called lead powder,
Reacts with this to uniformly produce tribasic lead sulfate in the paste.
To achieve. Lead dioxide produced by the reaction of lead tin and dilute sulfuric acid is kneaded in addition to lead oxide mainly composed of lead monoxide as a slurry substance , so-called lead powder,
More evenly dispersed in the paste .
【０００９】上記によって、化成時に電解液が注入さ
れたとき、鉛丹と硫酸の反応による大きな硫酸鉛の生成
がないため、従来、化成中に生じていた極板内部の歪み
を取り除くことができる。したがって、剥離などによっ
て活物質粒子間の結合力が損なわれることがなく、活物
質粒子間の結合力を保持することができる。また、上記
によって、鉛丹から生成する二酸化鉛をペースト中に
均一に分散させることができるため、これによって、鉛
丹、言い換えれば二酸化鉛を極めて有効に化成効率の向
上に対して利用することができる。As described above, when an electrolytic solution is injected during chemical formation, there is no generation of large lead sulfate due to the reaction between lead and sulfuric acid, so that distortion inside the electrode plate, which has conventionally occurred during chemical formation, can be eliminated. . Therefore, the bonding force between the active material particles is not impaired by peeling or the like, and the bonding force between the active material particles can be maintained. In addition, since the above allows lead dioxide generated from red lead to be uniformly dispersed in the paste, lead red, in other words, lead dioxide can be extremely effectively used for improving the formation efficiency. it can.
【００１０】[0010]
【実施例】以下に本発明の実施例について述べる。ま
ず、水１８５ｍｌに鉛丹０．４５ｋｇ（混合率１５％）
を十分に分散させる。続いて、希硫酸（比重：１．２６
０ ａｔ２０℃）３７５ｍｌを加える。このとき、本実
施例では、反応温度が４０〜４５℃になるように冷却お
よび希硫酸投入速度の制御を行った。次に、このスラリ
ー状物質を酸化度７５％の鉛粉２．５５ｋｇに加えなが
ら混練を行い、ペーストを調製した。このペーストを鉛
−アンチモン系合金から成る格子体に塗布し、常法にし
たがって熟成、乾燥を行い、未化成極板を得た。なお、
格子体は自動車用鉛電池３６Ｂ２０型用のものとした。
この未化成極板を用いて３６Ｂ２０型の単電池を組み立
てた。Embodiments of the present invention will be described below. First, 0.45 kg of lead red in 185 ml of water (mixing ratio 15%)
Is sufficiently dispersed. Subsequently, dilute sulfuric acid (specific gravity: 1.26
(0 at 20 ° C.). At this time, in the present example, the cooling and the dilute sulfuric acid introduction rate were controlled so that the reaction temperature was 40 to 45 ° C. Next, kneading was performed while adding this slurry-like substance to 2.55 kg of lead powder having an oxidation degree of 75% to prepare a paste. This paste was applied to a grid made of a lead-antimony alloy, aged and dried according to a conventional method to obtain an unformed electrode plate. In addition,
The grid body was for a lead battery for automobiles 36B20 type.
Using this unformed electrode plate, a 36B20 type cell was assembled.
【００１１】図１は、上記未化成極板を化成したときの
化成効率を示したものである。比較データは、鉛丹０．
６ｋｇ（混合率２０％）と酸化度７５％の鉛粉２．５５
ｋｇの混合物を、従来法に従って混練することによって
調製したペーストを用いた場合である。化成は、通電電
流０．３ＣＡ、電解液比重１．１５（２０℃）、周囲温
度４０℃で行った。なお、本発明による正極板に剥離は
全く観察されなかった。従来法による正極板において
は、表面に一部、剥離、ふくれが認められた。図１より
本発明による正極板は鉛丹の混合率が従来法によるもの
より少ないにもかかわらず化成効率が良いことがわか
る。図２は、組み立てた３６Ｂ２０型の単電池を用い
て、ＪＩＳ規格に定める重負荷寿命試験を行ったときの
結果である。比較データは、鉛丹０．６ｋｇと酸化度７
５％の鉛粉２．４ｋｇの混合物を、従来法に従って混練
することによって調製したペーストを用いた場合、およ
び、酸化度７５％の鉛粉のみから調製したペーストを用
いた場合である。FIG. 1 shows the formation efficiency when the unformed electrode plate is formed. The comparison data is for lead red 0.1.
6 kg (mixing ratio 20%) and lead powder 2.55 with an oxidation degree of 75%
In this case, a paste prepared by kneading a kg of a mixture according to a conventional method is used. The formation was performed at an energizing current of 0.3 CA, a specific gravity of the electrolytic solution of 1.15 (20 ° C.), and an ambient temperature of 40 ° C. No peeling was observed on the positive electrode plate according to the present invention. In the positive electrode plate according to the conventional method, peeling and blistering were partially observed on the surface. From FIG. 1, it can be seen that the positive electrode plate according to the present invention has a good conversion efficiency despite the fact that the mixing ratio of lead red is lower than that of the conventional method. FIG. 2 shows the results when a heavy load life test defined in JIS standard was performed using the assembled 36B20 type cell. The comparison data is 0.6kg of lead red and oxidation degree 7
A paste prepared by kneading a 2.4 kg mixture of 5% lead powder according to a conventional method is used, and a paste prepared from only lead powder having an oxidation degree of 75% is used.
【００１２】[0012]
【発明の効果】本発明によれば、混合する鉛丹を有効に
利用することができ、かつ、活物質粒子間の結合力を保
持することができる。したがって、図１、図２に示した
ごとく、従来法より化成効率を向上させることができ、
かつ、鉛丹を混合することによる、サイクルサービスに
おける正極板の寿命低下を防止することができる。According to the present invention, the mixed lead can be effectively used, and the bonding force between the active material particles can be maintained. Therefore, as shown in FIGS. 1 and 2, the formation efficiency can be improved as compared with the conventional method.
Further, it is possible to prevent the life of the positive electrode plate from being shortened in the cycle service due to the mixing of the lead.
【００１３】さらに、鉛丹はペースト中に二酸化鉛とし
て存在するため、熟成中、格子体表面がこれによって酸
化され易く、格子体と活物質の密着性が改善される。さ
らに又鉛丹の添加が少量で十分な効果が発揮される。Further, since lead red is present as lead dioxide in the paste, the surface of the lattice is easily oxidized by this during aging, and the adhesion between the lattice and the active material is improved. Furthermore, a sufficient effect is exhibited by adding a small amount of lead.
【図１】本発明による正極板の化成効率を示した図であ
る。FIG. 1 is a diagram showing the formation efficiency of a positive electrode plate according to the present invention.
【図２】本発明による正極板を用いた３６Ｂ２０型の単
電池のＪＩＳ規格に定める重負荷寿命試験の結果であ
る。FIG. 2 shows the results of a heavy load life test defined by JIS standards for a 36B20 type cell using a positive electrode plate according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 4/16,4/20 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 6 , DB name) H01M 4 / 16,4 / 20
Claims (1)
によってペーストを調製し、これを鉛あるいは鉛合金か
ら成る格子体に塗布するペースト式鉛電池正極板の製造
方法において、まず、水に鉛丹を分散させた後、希硫酸
を添加し、このスラリー状物質を一酸化鉛を主体とする
鉛酸化物に加え、混練することを特徴とするペースト式
鉛電池正極板の製造方法。1. A method for producing a paste-type lead battery positive electrode plate in which a paste is prepared by kneading a lead oxide with water and dilute sulfuric acid, and the paste is applied to a grid made of lead or a lead alloy. A method for producing a positive electrode plate for a paste-type lead battery, comprising adding dilute sulfuric acid, dispersing lead tin to the mixture, adding the slurry-like substance to a lead oxide mainly composed of lead monoxide, and kneading the mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5126410A JP2982555B2 (en) | 1993-05-28 | 1993-05-28 | Method for manufacturing positive electrode plate of paste type lead battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5126410A JP2982555B2 (en) | 1993-05-28 | 1993-05-28 | Method for manufacturing positive electrode plate of paste type lead battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06338316A JPH06338316A (en) | 1994-12-06 |
| JP2982555B2 true JP2982555B2 (en) | 1999-11-22 |
Family
ID=14934475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5126410A Expired - Lifetime JP2982555B2 (en) | 1993-05-28 | 1993-05-28 | Method for manufacturing positive electrode plate of paste type lead battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2982555B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3188288A4 (en) * | 2014-08-08 | 2018-03-07 | Hitachi Chemical Company, Ltd. | Positive electrode plate for lead storage battery, and lead storage battery using same |
-
1993
- 1993-05-28 JP JP5126410A patent/JP2982555B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06338316A (en) | 1994-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0592028B1 (en) | Method of forming lead-acid battery electrode | |
| CN1957491B (en) | Battery paste additive and method for producing battery plates | |
| WO2006055859A2 (en) | Additives and modified tetrabasic sulfate crystal positive plates for lead acid batteries | |
| JP2982555B2 (en) | Method for manufacturing positive electrode plate of paste type lead battery | |
| CN111048777B (en) | High-porosity EVF series lead storage battery positive electrode lead plaster and plaster mixing method thereof | |
| CN115806281A (en) | Lithium manganese iron phosphate composite material, preparation method thereof and battery | |
| JP2000048814A (en) | Positive electrode plate for lead-acid battery | |
| JPH07122269A (en) | Manufacture of positive plate for paste type lead battery | |
| JP2004055417A (en) | Manufacturing method of pasty active material for positive electrode and lead storage battery using it | |
| JP3107242B2 (en) | Lead storage battery | |
| JPH09289015A (en) | Manufacture of electrode plate for lead-acid battery | |
| JPH0676815A (en) | Positive electrode plate for lead-acid battery and manufacture thereof | |
| JPH07120529B2 (en) | Method of manufacturing anode plate for lead acid battery | |
| JP2773312B2 (en) | Manufacturing method of positive electrode plate for lead-acid battery | |
| JP2949767B2 (en) | Lead battery manufacturing method | |
| JP2000048812A (en) | Positive electrode plate for lead-acid battery | |
| JPH07235300A (en) | Manufacture of paste type positive plate for lead-acid battery | |
| JP2847791B2 (en) | Manufacturing method of nickel cadmium storage battery | |
| CN111009657A (en) | Lead-antimony oxide and preparation method and application thereof | |
| JPS6351351B2 (en) | ||
| JP2000182615A (en) | Lead-acid battery | |
| JP2773313B2 (en) | Manufacturing method of lead storage battery | |
| CN116706020A (en) | Lithium iron manganese phosphate positive electrode material and preparation method thereof | |
| JPS63269456A (en) | Manufacture of electrode for lead battery | |
| JP2002042798A (en) | Method for manufacturing positive electrode plate for lead-acid battery added with minium |