JPH09147870A - Negative electrode plate for lead-acid battery and its manufacture - Google Patents
Negative electrode plate for lead-acid battery and its manufactureInfo
- Publication number
- JPH09147870A JPH09147870A JP7310358A JP31035895A JPH09147870A JP H09147870 A JPH09147870 A JP H09147870A JP 7310358 A JP7310358 A JP 7310358A JP 31035895 A JP31035895 A JP 31035895A JP H09147870 A JPH09147870 A JP H09147870A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- electrode plate
- negative electrode
- lead
- lignin sulfonate
- 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.)
- Withdrawn
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鉛蓄電池用負極板
及びそ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 negative electrode plate for a lead storage battery and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】一般に鉛蓄電池用負極板は活物質ペース
トを格子体等からなる集電体に充填した未乾燥極板を熟
成、乾燥して未化成極板を作り、この未化成極板を化成
して作成する。活物質ペーストは、鉛酸化物を主体とす
る鉛粉と、硫酸バリウム、カーボン等の添加物と硫酸と
水とを混練して作る。また最近では、鉛蓄電池用負極板
の低温高率放電容量及び寿命特性を向上させるために、
リグニンスルホン酸塩等の活物質の収縮を防ぐ防縮剤
（エキスパンダー）を活物質ペーストに添加している。
しかしながら、リグニンスルホン酸塩は鉛と一酸化鉛に
は吸着しやすいものの、硫酸鉛にはほとんど吸着されな
い。そのため、極板の化成初期において、電解液（希硫
酸）と一酸化鉛を主成分とする未化成活物質とが反応し
て硫酸鉛が生成されると、リグニンスルホン酸塩は硫酸
鉛に吸着されずに電解液中に溶出するという問題があっ
た。そこで、特公昭６０−４３６２６号公報に示すよう
に集電体の上にリグニンスルホン酸塩の添加量の少ない
活物質層を形成し、該活物質層の上にリグニンスルホン
酸塩の添加量の多い活物質層を形成した負極板が提案さ
れた。この負極板では、電解液と接触する極板表面のリ
グニンスルホン酸塩の添加量を多くすることによりリグ
ニンスルホン酸塩が電解液に溶出しても、一定量のリグ
ニンスルホン酸塩が確保できるようにしている。2. Description of the Related Art Generally, in a negative electrode plate for a lead storage battery, an undried electrode plate in which an active material paste is filled in a current collector made of a grid or the like is aged and dried to form an unformed electrode plate. Create by creating. The active material paste is prepared by kneading lead powder mainly containing lead oxide, additives such as barium sulfate and carbon, sulfuric acid and water. Recently, in order to improve the low temperature high rate discharge capacity and life characteristics of the negative electrode plate for lead acid batteries,
A shrink preventive agent (expander) such as lignin sulfonate that prevents the active material from shrinking is added to the active material paste.
However, although lignin sulfonate is easily adsorbed on lead and lead monoxide, it is hardly adsorbed on lead sulfate. Therefore, in the early stage of electrode plate formation, when the electrolytic solution (dilute sulfuric acid) reacts with the unformed active material whose main component is lead monoxide to produce lead sulfate, lignin sulfonate is adsorbed on lead sulfate. However, there was a problem that it was not dissolved in the electrolytic solution. Therefore, as shown in Japanese Patent Publication No. 60-43626, an active material layer containing a small amount of lignin sulfonate is formed on a current collector, and an active material layer containing a small amount of lignin sulfonate is formed on the active material layer. A negative electrode plate having many active material layers has been proposed. In this negative electrode plate, by increasing the addition amount of lignin sulfonate on the surface of the electrode plate in contact with the electrolytic solution, even if the lignin sulfonate is eluted into the electrolytic solution, a certain amount of lignin sulfonate can be secured. I have to.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、電解液
と接触する極板表面のリグニンスルホン酸塩の添加量を
多くしても、リグニンスルホン酸塩の電解液への溶出を
防ぐことができない。そのため、電池の使用に応じて低
温高率放電容量及び寿命特性が低下する。またリグニン
スルホン酸塩の添加量が多くなると、リグニンスルホン
酸塩の界面活性剤としての作用が高くなり、活物質ペー
ストが軟らかくなり、活物質ペーストを集電体に充填し
づらくなるという問題があった。また従来の負極板で
は、活物質層を２層に形成しなければならず、負極板の
製造が繁雑になるという問題があった。However, even if the addition amount of the lignin sulfonate on the surface of the electrode plate which comes into contact with the electrolyte is increased, the elution of the lignin sulfonate to the electrolyte cannot be prevented. Therefore, the low-temperature high-rate discharge capacity and the life characteristics are reduced depending on the use of the battery. When the amount of lignin sulfonate added is large, the action of the lignin sulfonate as a surfactant becomes high, the active material paste becomes soft, and it becomes difficult to fill the current collector with the active material paste. It was Further, in the conventional negative electrode plate, the active material layer has to be formed in two layers, which causes a problem that the production of the negative electrode plate becomes complicated.
【０００４】本発明の目的は、リグニンスルホン酸塩の
電解液への溶出を抑制して鉛蓄電池の低温高率放電容量
を高めることができる鉛蓄電池用負極板を提供すること
にある。An object of the present invention is to provide a negative electrode plate for a lead storage battery which can suppress the elution of lignin sulfonate into an electrolytic solution and can enhance the low temperature high rate discharge capacity of the lead storage battery.
【０００５】本発明の他の目的は、リグニンスルホン酸
塩の電解液への溶出を抑制して鉛蓄電池の寿命を延ばす
ことができる鉛蓄電池用負極板を提供することにある。Another object of the present invention is to provide a negative electrode plate for a lead storage battery, which can suppress the elution of lignin sulfonate into an electrolytic solution and extend the life of the lead storage battery.
【０００６】本発明の他の目的は、リグニンスルホン酸
塩の量を少なくして活物質ペーストを容易に集電体に充
填できる鉛蓄電池用負極板を提供することにある。Another object of the present invention is to provide a negative electrode plate for a lead storage battery in which the amount of lignin sulfonate is reduced and the active material paste can be easily filled in the current collector.
【０００７】本発明の他の目的は、リグニンスルホン酸
塩の量を少なくして活物質ペーストを容易に集電体に充
填して鉛蓄電池用負極板を製造する方法を提供すること
にある。Another object of the present invention is to provide a method for manufacturing a negative electrode plate for a lead storage battery by reducing the amount of lignin sulfonate and easily filling an active material paste in a current collector.
【０００８】本発明の更に他の目的は、リグニンスルホ
ン酸塩を含む活物質ペーストを１層に形成して鉛蓄電池
用負極板を容易に製造する方法を提供することにある。Yet another object of the present invention is to provide a method for easily manufacturing a negative electrode plate for a lead storage battery by forming an active material paste containing a lignin sulfonate in one layer.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決するため
に、本発明は、活物質にセルロース誘導体を鉛粉に対し
て０．１〜１．０重量％添加する。本発明のように、活
物質にセルロース誘導体を添加すると、添加したセルロ
ース誘導体が一酸化鉛を主成分とした未化成活物質を覆
うため、未化成活物質の硫酸との反応面積が小さくな
る。そのため、活物質が硫酸鉛化するのを抑制する。こ
れによりリグニンスルホン酸塩が活物質から脱落するの
を防いでリグニンスルホン酸塩の電解液への溶出を抑制
できる。また活物質が硫酸鉛化する際に生じる発熱も抑
制できるので、これによってもリグニンスルホン酸塩の
電解液への溶出を抑制できる。そのため、少量のリグニ
ンスルホン酸塩で電池の低温高率放電容量を高めること
ができる。またリグニンスルホン酸塩の添加量を少なく
できることにより、活物質ペーストの粘度の低下を防げ
る。そのため、活物質ペーストは集電体に充填しやすく
なる。In order to solve the above problems, in the present invention, a cellulose derivative is added to an active material in an amount of 0.1 to 1.0% by weight based on lead powder. When a cellulose derivative is added to the active material as in the present invention, the added cellulose derivative covers the unconverted active material containing lead monoxide as a main component, so that the reaction area of the unconverted active material with sulfuric acid becomes small. Therefore, the active material is prevented from being converted into lead sulfate. This can prevent the lignin sulfonate from falling off the active material and suppress the elution of the lignin sulfonate into the electrolytic solution. Further, since the heat generated when the active material is converted into lead sulfate can be suppressed, the elution of the lignin sulfonate to the electrolytic solution can also be suppressed by this. Therefore, the low temperature high rate discharge capacity of the battery can be increased with a small amount of lignin sulfonate. Further, since the amount of lignin sulfonate added can be reduced, it is possible to prevent the viscosity of the active material paste from decreasing. Therefore, the active material paste is easily filled in the current collector.
【００１０】[0010]
【発明の実施の形態】本発明は、鉛粉及びリグニンスル
ホン酸塩を含有する活物質が集電体に充填されてなる鉛
蓄電池用負極板を対象にして、活物質にセルロース誘導
体を鉛粉に対して０．１〜１．０重量％添加する。リグ
ニンスルホン酸塩は活物質の収縮を防止するものであ
り、例えば、リグニンスルホン酸ナトリウムが好まし
い。また、セルロース誘導体としてはカルボキシメチル
セルロース、メチルセルロース、ヒドロキシプロピルメ
チルセルロース及びヒドロキシエチルメチルセルロース
の少なくとも一つを用いるのが好ましい。これらのもの
を用いると電池性能への悪影響が少ない利点がある。ま
たセルロース誘導体は活物質に分散して添加されている
必要はない。例えば、活物質表面部分に偏ってセルロー
ス誘導体が添加されていてもよい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is intended for a negative electrode plate for a lead storage battery in which a current collector is filled with an active material containing lead powder and lignin sulfonate, and a cellulose derivative is added to the active material as a lead powder. 0.1 to 1.0% by weight is added. The lignin sulfonate prevents contraction of the active material, and for example, sodium lignin sulfonate is preferable. As the cellulose derivative, it is preferable to use at least one of carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose. The use of these materials has the advantage that the battery performance is not adversely affected. Further, the cellulose derivative does not need to be dispersed and added to the active material. For example, the cellulose derivative may be added biasedly to the surface portion of the active material.
【００１１】リグニンスルホン酸ナトリウム等のリグニ
ンスルホン酸塩は、鉛粉に対して０．１〜０．５重量％
添加するのが好ましい。リグニンスルホン酸塩の添加量
が０．１重量％を下回ると負極活物質の収縮を抑制でき
ない。また本発明では、リグニンスルホン酸塩の電解液
への溶出を抑制できるものの、リグニンスルホン酸塩の
添加量が０．５重量％を上回るとリグニンスルホン酸塩
は電解液に溶出してしまう。The lignin sulfonate such as sodium lignin sulfonate is 0.1 to 0.5% by weight with respect to the lead powder.
It is preferred to add. If the amount of lignin sulfonate added is less than 0.1% by weight, the negative electrode active material cannot be suppressed from shrinking. Further, in the present invention, although the elution of the lignin sulfonate into the electrolytic solution can be suppressed, the lignin sulfonate will elute into the electrolytic solution when the addition amount of the lignin sulfonate exceeds 0.5% by weight.
【００１２】なお鉛粉に対するセルロース誘導体の添加
量が０．１重量％を下回るとリグニンスルホン酸塩の電
解液への溶出を十分に抑制することができない。また添
加量が１．０重量％を上回るとセルロース誘導体が電解
液の拡散を阻害したり、活物質の電気抵抗を高めるた
め、容量が低下する。If the amount of the cellulose derivative added to the lead powder is less than 0.1% by weight, the elution of the lignin sulfonate into the electrolytic solution cannot be sufficiently suppressed. On the other hand, if the amount added exceeds 1.0% by weight, the cellulose derivative will hinder the diffusion of the electrolytic solution or increase the electrical resistance of the active material, resulting in a decrease in capacity.
【００１３】本発明の鉛蓄電池用負極板を製造するに
は、鉛粉及びリグニンスルホン酸塩を添加する活物質ペ
ーストを集電体に充填して鉛蓄電池用負極板を製造する
方法を対象にする。そして、活物質ペーストにセルロー
ス誘導体を鉛粉に対して０．１〜１．０重量％添加す
る。活物質ペーストにセルロース誘導体を添加する方法
としては、セルロース誘導体を水に溶解したセルロース
誘導体水溶液を活物質ペーストに添加してもよいし、セ
ルロース誘導体粉末を活物質ペーストに添加してもよ
い。このようにして鉛蓄電池用負極板を製造すれば、リ
グニンスルホン酸塩の添加量を少なくして、活物質ペー
ストを集電体に充填しやすくなる。またリグニンスルホ
ン酸塩を含む活物質ペーストを１層に形成して鉛蓄電池
用負極板を容易に製造できる。In order to manufacture the negative electrode plate for a lead storage battery of the present invention, a method for manufacturing a negative electrode plate for a lead storage battery by filling a current collector with an active material paste to which lead powder and lignin sulfonate are added. To do. Then, the cellulose derivative is added to the active material paste in an amount of 0.1 to 1.0% by weight based on the lead powder. As a method of adding the cellulose derivative to the active material paste, an aqueous cellulose derivative solution in which the cellulose derivative is dissolved may be added to the active material paste, or cellulose derivative powder may be added to the active material paste. When the negative electrode plate for a lead storage battery is manufactured in this manner, the amount of lignin sulfonate added is reduced, and the active material paste is easily filled in the current collector. In addition, a negative electrode plate for a lead storage battery can be easily manufactured by forming an active material paste containing a lignin sulfonate in one layer.
【００１４】また別の方法では、鉛粉及びリグニンスル
ホン酸塩を添加する活物質ペーストを集電体に充填して
鉛蓄電池用負極板を製造する方法を対象にして、活物質
ペーストを集電体に充填した後にセルロース誘導体が前
記鉛粉に対して０．１〜１．０重量％添加されるように
負極板をセルロース誘導体水溶液に浸漬する方法もあ
る。このような方法では、負極板の表面をセルロース誘
導体で十分に覆うことができ、リグニンスルホン酸塩の
電解液への溶出を防止しやすい利点がある。In another method, the active material paste is collected by filling the current collector with the active material paste to which lead powder and lignin sulfonate are added to produce a negative electrode plate for a lead storage battery. There is also a method of immersing the negative electrode plate in a cellulose derivative aqueous solution so that the cellulose derivative is added to the lead powder in an amount of 0.1 to 1.0% by weight after filling the body. Such a method has an advantage that the surface of the negative electrode plate can be sufficiently covered with the cellulose derivative and the elution of the lignin sulfonate into the electrolytic solution can be easily prevented.
【００１５】[0015]
（実施例１）本実施例の鉛蓄電池用負極板は次のように
して作った。まず、一酸化鉛を主体とする鉛粉と、所定
量の硫酸バリウム及びカーボンと、鉛粉に対して０．２
重量％のリグニンスルホン酸ナトリウムからなる防縮剤
と、カルボキシメチルセルロ６ス（ＣＭＣ）からなるセ
ルロース誘導体をイオン交換水に溶解したＣＭＣ溶液
と、硫酸とを混練して活物質ペーストを作った。なおＣ
ＭＣ溶液は、鉛粉に対してＣＭＣが０．２５重量％にな
る量を添加した。ＣＭＣとしては、ダイセル化学工業株
式会社の品番１１６０番のものを用いた。このＣＭＣは
エーテル化度０．６〜０．８であり、１重量％水溶液の
粘度が３００〜５００ cps（２５℃）である。次に活物
質ペーストを格子体からなる集電体に充填して未乾燥極
板を作った。その後、未乾燥負極板を温度５０℃湿度９
５％の雰囲気中で１８時間放置して熟成した後に、温度
５０℃の雰囲気中で１６時間放置して乾燥して未化成負
極板を作った。次に未化成負極板１枚と公知のペースト
式正極板２枚とをセパレータを介して積層して極板群を
作った。そして、極板群を一定加圧下で塩化ビニル製の
電槽内に配置してから、電槽内に比重１．２２５（２０
℃）の希硫酸からなる電解液を注液した。そして、４０
℃温度雰囲気中で２．０６Ａで１８時間通電する電槽化
成を行い鉛蓄電池内に配置された鉛蓄電池用負極板を完
成した。(Example 1) The negative electrode plate for a lead storage battery of this example was manufactured as follows. First, lead powder mainly composed of lead monoxide, a predetermined amount of barium sulfate and carbon, and 0.2% of lead powder.
An active material paste was prepared by kneading a shrink preventive agent containing sodium lignin sulfonate at a weight percentage, a CMC solution prepared by dissolving a cellulose derivative containing carboxymethylcellulose 6 (CMC) in ion-exchanged water, and sulfuric acid. Note that C
The MC solution was added in an amount such that CMC was 0.25% by weight with respect to the lead powder. As CMC, the product number 1160 of Daicel Chemical Industries, Ltd. was used. The CMC has an etherification degree of 0.6 to 0.8, and a 1 wt% aqueous solution has a viscosity of 300 to 500 cps (25 ° C.). Next, the active material paste was filled in a current collector composed of a grid to prepare an undried electrode plate. Then, the undried negative electrode plate was heated at a temperature of 50 ° C. and a humidity of 9
After leaving it to stand in a 5% atmosphere for 18 hours for aging, it was left in an atmosphere at a temperature of 50 ° C. for 16 hours and dried to prepare an unformed negative electrode plate. Next, one unformed negative electrode plate and two known paste-type positive electrode plates were laminated with a separator in between to form an electrode plate group. Then, after arranging the electrode plate group in a vinyl chloride battery case under constant pressure, the specific gravity of 1.225 (20
An electrolytic solution consisting of diluted sulfuric acid (° C.) Was injected. And 40
A negative electrode plate for a lead storage battery arranged inside the lead storage battery was completed by performing battery case formation in which a current of 2.06 A was applied for 18 hours in a temperature atmosphere of ° C.
【００１６】（比較例１）本比較例の鉛蓄電池用負極板
は活物質ペースト中にセルロース誘導体を添加せず、そ
の他は実施例１と同様にして作った。(Comparative Example 1) The negative electrode plate for a lead storage battery of this comparative example was prepared in the same manner as in Example 1 except that the cellulose derivative was not added to the active material paste.
【００１７】（比較例２）本比較例の鉛蓄電池用負極板
は、セルロース誘導体を添加せず、その他は実施例１と
同様の活物質ペースト（０．２重量％のリグニンスルホ
ン酸ナトリウムを添加したもの）を集電体上に充填して
第１活物質層を形成し、第１活物質層の上にセルロース
誘導体を添加せず、鉛粉に対して１．０重量％のリグニ
ンスルホン酸ナトリウム（第１活物質層の５倍の重量％
のリグニンスルホン酸ナトリウム）を添加し、その他は
実施例１と同様の活物質ペーストを充填して第２活物質
層を形成して未化成極板を作った。なお第１活物質層と
第２活物質層とは同じ厚みを有している。また本比較例
の鉛蓄電池用負極板は実施例１と同じ鉛粉量を有してい
る。(Comparative Example 2) The negative electrode plate for lead acid battery of this comparative example did not contain the cellulose derivative, and the other active material pastes (0.2% by weight of sodium lignin sulfonate were added) similar to those of Example 1. Of the lignin sulfonic acid of 1.0 wt% with respect to the lead powder without adding a cellulose derivative on the first active material layer. Sodium (5% by weight of the first active material layer)
Of sodium lignin sulfonate) was added, and the other active material paste was filled in the same manner as in Example 1 to form a second active material layer to form an unformed electrode plate. The first active material layer and the second active material layer have the same thickness. Moreover, the negative electrode plate for a lead storage battery of this comparative example has the same amount of lead powder as that of the first embodiment.
【００１８】[0018]
【表１】 表１には上記各負極板の活物質ペースト充填時におい
て、活物質ペーストが集電体から１mm垂れ落ちる充填不
良率が併せて示されている。なお充填不良率は、各負極
板をそれぞれ１００枚作成して調べた。本表より、リグ
ニンスルホン酸ナトリウムの添加量が多い比較例２の負
極板は、充填不良率が高く、活物質が充填しづらいのが
分る。[Table 1] Table 1 also shows the percentage of defective filling in which the active material paste droops 1 mm from the current collector when the above-mentioned negative electrode plates were filled with the active material paste. The filling failure rate was investigated by making 100 negative electrode plates. From this table, it can be seen that the negative electrode plate of Comparative Example 2 containing a large amount of sodium lignin sulfonate has a high filling failure rate and is difficult to fill with the active material.
【００１９】次に上記各負極板を用いた鉛蓄電池を用い
て試験を行った。最初に各鉛蓄電池の化成終了後の負極
活物質の比表面積を調べた。測定結果は上記表１に示さ
れている。本表より比較例１の負極板は、活物質の比表
面積が小さくなっているのが分る。これは、比較例１の
負極板では、リグニンスルホン酸ナトリウムが電解液中
に溶出してリグニンスルホン酸ナトリウムの残量が少な
くなっているからである。Next, a test was conducted using a lead storage battery using each of the above negative electrode plates. First, the specific surface area of the negative electrode active material after the formation of each lead acid battery was examined. The measurement results are shown in Table 1 above. From this table, it can be seen that the negative electrode plate of Comparative Example 1 has a small specific surface area of the active material. This is because in the negative electrode plate of Comparative Example 1, sodium ligninsulfonate was eluted in the electrolytic solution and the residual amount of sodium ligninsulfonate was reduced.
【００２０】次に各電池を−１５℃において３７．５Ａ
で放電して各電池の低温における高率放電容量を測定し
た。また各電池を２５℃において１．４Ａで放電して各
電池の常温における低率放電容量を測定した。測定結果
は上記表１に示されている。本表より実施例１の負極板
を用いた電池は少ないリグニンスルホン酸ナトリウムの
添加量で、リグニンスルホン酸ナトリウムの添加量の多
い比較例２の負極板を用いた電池と同様に容量を高めら
れるのが分る。特に低温高率放電容量を高められるのが
分る。これは実施例１の負極板では、リグニンスルホン
酸ナトリウムの電解液への溶出が抑制されて負極活物質
の比表面積が大きくなっているためである。Next, each battery was put at 37.5 A at -15 ° C.
The high rate discharge capacity at low temperature of each battery was measured. Further, each battery was discharged at 1.4 A at 25 ° C. to measure the low rate discharge capacity of each battery at room temperature. The measurement results are shown in Table 1 above. From this table, the battery using the negative electrode plate of Example 1 can increase the capacity similarly to the battery using the negative electrode plate of Comparative Example 2 with a large addition amount of sodium ligninsulfonate, with a small addition amount of sodium ligninsulfonate. I understand. In particular, it can be seen that the low temperature high rate discharge capacity can be increased. This is because in the negative electrode plate of Example 1, elution of sodium lignin sulfonate into the electrolytic solution was suppressed and the specific surface area of the negative electrode active material was increased.
【００２１】次に各電池に４０℃温度雰囲気中で２．４
７Ｖカットで最大電流６．２５Ａで４分間の定電圧充電
と４Ａで２分間の定電流放電とを繰り返すＪＩＳ軽負荷
試験による充放電を繰り返して、各電池の寿命に至る回
数（３７．５Ａ放電において、３０秒目の電圧が１．２
Ｖ以下になる回数）を測定した。測定結果は上記表１に
示されている。本表より実施例１の負極板を用いた電池
は、リグニンスルホン酸ナトリウムの添加量の多い比較
例２の負極板を用いた電池と同様に寿命を延ばせるのが
分る。これはＣＭＣが還元雰囲気の活物質中に存在して
いるため、分解、消失されにくいためである。Then, each battery was placed in an atmosphere at a temperature of 40 ° C. for 2.4.
Repeated charging / discharging by JIS light load test which repeats constant voltage charging for 4 minutes at maximum current 6.25A with 7V cut and constant current discharging for 2 minutes at 4A, and the number of times until reaching the life of each battery (37.5A discharge At 30 seconds, the voltage is 1.2
The number of times V or less) was measured. The measurement results are shown in Table 1 above. From this table, it can be seen that the battery using the negative electrode plate of Example 1 can extend the life similarly to the battery using the negative electrode plate of Comparative Example 2 in which the amount of sodium lignin sulfonate added is large. This is because CMC is present in the active material in the reducing atmosphere, and is not easily decomposed or lost.
【００２２】次に活物質の鉛粉に対するカルボキシメチ
ルセルロース（ＣＭＣ）の添加量が異なり、その他は実
施例１と同様な電池を作った。またＣＭＣの代りにメチ
ルセルロース（ＭＣ）、ヒドロキシプロピルメチルセル
ロース（ＨＰＭＣ）、ヒドロキシエチルメチルセルロー
ス（ＨＥＭＣ）、ＣＭＣ５０重量％とＭＣ５０重量％と
の混合物、ＭＣ５０重量％とＨＰＭＣ５０重量％との混
合物からなるセルロース誘導体をそれぞれ添加し、これ
らのセルロース誘導体の添加量を異ならせて、その他は
実施例１と同様な電池を作った。そして、各電池に上述
した−１５℃で３７．５Ａでの放電を行い、各電池の低
温高率放電容量を測定して、セルロース誘導体の添加量
と低温高率放電容量との関係を調べた。図１はその測定
結果を示している。本図より鉛粉に対して０．１〜１．
０重量％のセルロース誘導体を活物質に添加すると放電
容量を高められるのが分る。なお２種類以上のセルロー
ス誘導体を混合する場合には、混合比率を変えても同じ
ような効果を得ることができる。Next, a battery was prepared in the same manner as in Example 1 except that the amount of carboxymethyl cellulose (CMC) added to the lead powder of the active material was different. Instead of CMC, methylcellulose (MC), hydroxypropylmethylcellulose (HPMC), hydroxyethylmethylcellulose (HEMC), a cellulose derivative comprising a mixture of CMC 50% by weight and MC 50% by weight, a mixture of MC 50% by weight and HPMC 50% by weight. Batteries similar to those of Example 1 were manufactured by adding the respective cellulose derivatives and varying the addition amounts of these cellulose derivatives. Then, each battery was discharged at -15 ° C. at 37.5 A, the low temperature high rate discharge capacity of each battery was measured, and the relationship between the addition amount of the cellulose derivative and the low temperature high rate discharge capacity was investigated. . FIG. 1 shows the measurement result. From this figure, 0.1-1.
It can be seen that the discharge capacity can be increased by adding 0% by weight of the cellulose derivative to the active material. When two or more types of cellulose derivatives are mixed, the same effect can be obtained even if the mixing ratio is changed.
【００２３】なお本実施例では、セルロース誘導体水溶
液を活物質ペーストに添加して、活物質にセルロース誘
導体を添加したが、セルロース誘導体粉末を活物質ペー
ストに添加してもよい。また活物質ペーストを集電体に
充填した極板素材を実施例で用いたセルロース誘導体水
溶液に浸漬して活物質にセルロース誘導体を添加しても
かまわない。In this embodiment, the cellulose derivative aqueous solution is added to the active material paste and the cellulose derivative is added to the active material. However, the cellulose derivative powder may be added to the active material paste. Further, the electrode plate material in which the active material paste is filled in the current collector may be immersed in the cellulose derivative aqueous solution used in the examples to add the cellulose derivative to the active material.
【００２４】以下、明細書に記載した発明についてその
構成を示す。The structure of the invention described in the specification will be shown below.
【００２５】（１） 鉛粉及びリグニンスルホン酸ナト
リウムを含有する活物質が集電体に充填されてなる鉛蓄
電池用負極板において、前記活物質にカルボキシメチル
セルロースからなるセルロース誘導体が前記鉛粉に対し
て０．１〜１．０重量％添加され、前記リグニンスルホ
ン酸ナトリウムが前記鉛粉に対して０．１〜０．５重量
％添加されていることを特徴とする鉛蓄電池用負極板。(1) In a negative electrode plate for a lead storage battery in which a current collector is filled with an active material containing lead powder and sodium lignin sulfonate, a cellulose derivative composed of carboxymethyl cellulose is added to the lead powder as the active material. 0.1 to 0.5% by weight of the lead powder and 0.1 to 0.5% by weight of the sodium ligninsulfonate are added to the lead powder.
【００２６】（２） 鉛粉及びリグニンスルホン酸ナト
リウムを含有する活物質ペーストを集電体に充填して鉛
蓄電池用負極板を製造する方法において、カルボキシメ
チルセルロースからなるセルロース誘導体が前記鉛粉に
対して０．１〜１．０重量％添加されるようにカルボキ
シメチルセルロース水溶液を前記活物質ペーストに添加
することを特徴とする鉛蓄電池用負極板の製造方法。(2) In a method for manufacturing a negative electrode plate for a lead storage battery by filling a current collector with an active material paste containing lead powder and sodium ligninsulfonate, a cellulose derivative composed of carboxymethyl cellulose is added to the lead powder. A method for producing a negative electrode plate for a lead storage battery, which comprises adding an aqueous carboxymethyl cellulose solution to the active material paste so that 0.1 to 1.0% by weight is added.
【００２７】（３） 鉛粉及びリグニンスルホン酸ナト
リウムを含有する活物質ペーストを集電体に充填して鉛
蓄電池用負極板を製造する方法において、前記活物質ペ
ーストを前記集電体に充填した後にカルボキシメチルセ
ルロースからなるセルロース誘導体が前記鉛粉に対して
０．１〜１．０重量％添加されるように前記負極板をカ
ルボキシメチルセルロース水溶液に含浸することを特徴
とする鉛蓄電池用負極板の製造方法。(3) In a method for manufacturing a negative electrode plate for a lead storage battery by filling an active material paste containing lead powder and sodium ligninsulfonate into the current collector, the active material paste is filled in the current collector. Manufacture of a negative electrode plate for a lead storage battery, characterized in that the negative electrode plate is impregnated with an aqueous solution of carboxymethyl cellulose so that a cellulose derivative composed of carboxymethyl cellulose is added later to 0.1 to 1.0% by weight with respect to the lead powder. Method.
【００２８】[0028]
【発明の効果】本発明によれば、活物質に添加したセル
ロース誘導体が一酸化鉛を主成分とした未化成活物質を
覆うため、未化成活物質の硫酸との反応面積が小さくな
る。そのため、活物質が硫酸鉛化するのを抑制する。こ
れによりリグニンスルホン酸塩が活物質から脱落するの
を防いでリグニンスルホン酸塩の電解液への溶出を抑制
できる。また活物質が硫酸鉛化する際に生じる発熱も抑
制できるので、これによってもリグニンスルホン酸塩の
電解液への溶出を抑制できる。そのため、少量のリグニ
ンスルホン酸塩で電池の低温高率放電容量を高めること
ができる。またセルロース誘導体は還元雰囲気の活物質
中に存在するので、酸化分解等で減少しにくい。そのた
め、リグニンスルホン酸塩の電解液への溶出を長期間に
亘って抑制でき、鉛蓄電池の寿命を延ばすこともでき
る。According to the present invention, since the cellulose derivative added to the active material covers the unactivated material containing lead monoxide as a main component, the reaction area of the unactivated material with sulfuric acid becomes small. Therefore, the active material is prevented from being converted into lead sulfate. This can prevent the lignin sulfonate from falling off the active material and suppress the elution of the lignin sulfonate into the electrolytic solution. Further, since the heat generated when the active material is converted into lead sulfate can be suppressed, the elution of the lignin sulfonate to the electrolytic solution can also be suppressed by this. Therefore, the low temperature high rate discharge capacity of the battery can be increased with a small amount of lignin sulfonate. Further, since the cellulose derivative exists in the active material in the reducing atmosphere, it is hard to decrease due to oxidative decomposition or the like. Therefore, elution of the lignin sulfonate into the electrolytic solution can be suppressed for a long period of time, and the life of the lead storage battery can be extended.
【００２９】またリグニンスルホン酸塩の添加量を少な
くできることにより、活物質ペーストの粘度の低下を防
げる。そのため、活物質ペーストは集電体に充填しやす
くなる。Further, since the amount of lignin sulfonate added can be reduced, it is possible to prevent the viscosity of the active material paste from decreasing. Therefore, the active material paste is easily filled in the current collector.
【図１】 セルロース誘導体の添加量と鉛蓄電池の低温
高率放電容量との関係を示す図である。FIG. 1 is a diagram showing the relationship between the addition amount of a cellulose derivative and the low temperature high rate discharge capacity of a lead storage battery.
Claims (5)
る活物質が集電体に充填されてなる鉛蓄電池用負極板に
おいて、 前記活物質にセルロース誘導体が前記鉛粉に対して０．
１〜１．０重量％添加されていることを特徴とする鉛蓄
電池用負極板。1. A negative electrode plate for a lead storage battery, wherein a current collector is filled with an active material containing lead powder and a lignin sulfonate, wherein a cellulose derivative is contained in the active material in an amount of 0.
A negative electrode plate for a lead storage battery, wherein the negative electrode plate is added in an amount of 1 to 1.0% by weight.
対して０．１〜０．５重量％添加されていることを特徴
とする請求項１に記載の鉛蓄電池用負極板。2. The negative electrode plate for a lead storage battery according to claim 1, wherein 0.1 to 0.5% by weight of the lignin sulfonate is added to the lead powder.
メチルセルロース、メチルセルロース、ヒドロキシプロ
ピルメチルセルロース及びヒドロキシエチルメチルセル
ロースの少なくとも一つを用いることを特徴とする請求
項２に記載の鉛蓄電池用負極板。3. The negative electrode plate for a lead storage battery according to claim 2, wherein at least one of carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose and hydroxyethylmethylcellulose is used as the cellulose derivative.
る活物質ペーストを集電体に充填して鉛蓄電池用負極板
を製造する方法において、 前記活物質ペーストにセルロース誘導体を前記鉛粉に対
して０．１〜１．０重量％添加することを特徴とする鉛
蓄電池用負極板の製造方法。4. A method for manufacturing a negative electrode plate for a lead storage battery by filling a current collector with an active material paste containing lead powder and lignin sulfonate, wherein a cellulose derivative is added to the lead powder with respect to the active material paste. 0.1 to 1.0% by weight is added to the negative electrode plate for a lead storage battery.
る活物質ペーストを集電体に充填して鉛蓄電池用負極板
を製造する方法において、 前記活物質ペーストを前記集電体に充填した後にセルロ
ース誘導体が前記鉛粉に対して０．１〜１．０重量％添
加されるように前記負極板をセルロース誘導体水溶液に
浸漬することを特徴とする鉛蓄電池用負極板の製造方
法。5. A method for manufacturing a negative electrode plate for a lead storage battery by filling an active material paste containing lead powder and a lignin sulfonate into a current collector, the method comprising: filling the current collector with the active material paste. A method for producing a negative electrode plate for a lead storage battery, which comprises immersing the negative electrode plate in an aqueous solution of the cellulose derivative such that the cellulose derivative is added in an amount of 0.1 to 1.0% by weight based on the lead powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7310358A JPH09147870A (en) | 1995-11-29 | 1995-11-29 | Negative electrode plate for lead-acid battery and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7310358A JPH09147870A (en) | 1995-11-29 | 1995-11-29 | Negative electrode plate for lead-acid battery and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09147870A true JPH09147870A (en) | 1997-06-06 |
Family
ID=18004280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7310358A Withdrawn JPH09147870A (en) | 1995-11-29 | 1995-11-29 | Negative electrode plate for lead-acid battery and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09147870A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242524A (en) * | 2020-09-15 | 2021-01-19 | 骆驼集团蓄电池研究院有限公司 | Formula and preparation method of negative lead plaster for improving high and low temperature performance of lead-acid storage battery |
| KR20220042748A (en) * | 2020-09-28 | 2022-04-05 | 한국앤컴퍼니 주식회사 | Method for manufacturing electrode plate of lead acid battery with improved adhesion between active materials by adding aqueous SBR-CMC |
-
1995
- 1995-11-29 JP JP7310358A patent/JPH09147870A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242524A (en) * | 2020-09-15 | 2021-01-19 | 骆驼集团蓄电池研究院有限公司 | Formula and preparation method of negative lead plaster for improving high and low temperature performance of lead-acid storage battery |
| CN112242524B (en) * | 2020-09-15 | 2022-07-15 | 骆驼集团蓄电池研究院有限公司 | Formula and preparation method of negative lead plaster for improving high and low temperature performance of lead-acid storage battery |
| KR20220042748A (en) * | 2020-09-28 | 2022-04-05 | 한국앤컴퍼니 주식회사 | Method for manufacturing electrode plate of lead acid battery with improved adhesion between active materials by adding aqueous SBR-CMC |
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