JP5088656B2 - Negative electrode for lead-acid battery and lead-acid battery using the same - Google Patents

Negative electrode for lead-acid battery and lead-acid battery using the same Download PDF

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JP5088656B2
JP5088656B2 JP2006081814A JP2006081814A JP5088656B2 JP 5088656 B2 JP5088656 B2 JP 5088656B2 JP 2006081814 A JP2006081814 A JP 2006081814A JP 2006081814 A JP2006081814 A JP 2006081814A JP 5088656 B2 JP5088656 B2 JP 5088656B2
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lignin
lead
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acid battery
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郁美 元井
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GS Yuasa International Ltd
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    • 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
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Description

本発明は、鉛蓄電池の改良に関するものであり、特に負極の添加剤の改良に関するものである。   The present invention relates to an improvement of a lead storage battery, and more particularly to an improvement of an additive for a negative electrode.

鉛蓄電池は、その安定した品質や高度の信頼性、適度の経済性から、自動車等のエンジン始動用を始め、コンシューマー用、据置用など、様々な用途で使用されている。
ところが、鉛蓄電池の負極活物質は放電生成物から充電生成物に変化する際に収縮するために、活物質粒子の表面積が小さくなり、鉛蓄電池で充放電を繰り返すと負極活物質層内の導電性が低下して、鉛蓄電池の放電特性が低下したり、寿命が短くなるという問題があった。そこで、負極活物質にリグニン化合物からなる表面積低下防止剤を添加して、鉛蓄電池の放電特性やサイクル寿命を向上させることが行われている。その際に、リグニン化合物中に含まれる−ＣＯＯＨ、−ＳＯ3Ｈ等の官能基による水素過電圧の低下を防止し、電池の充電受入れ性を向上させた発明も公知である（特許文献１参照）。
特開平９−７６３０号公報 Lead-acid batteries are used in various applications such as starting engines for automobiles, consumers, and stationary because of their stable quality, high reliability, and moderate economy.
However, since the negative electrode active material of a lead storage battery contracts when it changes from a discharge product to a charge product, the surface area of the active material particles becomes small, and if charge and discharge are repeated in a lead storage battery, the conductivity in the negative electrode active material layer is reduced. However, there is a problem that the discharge characteristics of the lead storage battery are deteriorated and the life is shortened. In view of this, a surface area reduction inhibitor made of a lignin compound is added to the negative electrode active material to improve the discharge characteristics and cycle life of the lead-acid battery. In this case, an invention that prevents a decrease in hydrogen overvoltage due to a functional group such as —COOH or —SO 3 H contained in the lignin compound and improves battery charge acceptance is also known (see Patent Document 1). .
Japanese Patent Laid-Open No. 9-7630

また、リグニンとともに脂肪酸を添加したり、特殊なリグニンを使用して、鉛蓄電池のドライアップや熱逸走を防止する発明も公知である（特許文献２及び３参照）。
特開平１０−２０８７４６号公報 特開２００２−１１７８５６号公報 Moreover, the invention which prevents the dry-up and thermal escape of a lead storage battery by adding a fatty acid with lignin or using special lignin is also known (see Patent Documents 2 and 3).
JP-A-10-208746 JP 2002-117856 A

しかしながら、従来のカルボキシル基を僅かしか含まないリグニンを含有した負極を用いた鉛蓄電池では、充放電サイクルの経過による負極の比表面積の低下を十分に防止することができず、サイクル寿命の向上も十分ではないという問題があった。   However, the conventional lead-acid battery using a negative electrode containing lignin containing only a few carboxyl groups cannot sufficiently prevent a decrease in the specific surface area of the negative electrode due to the progress of the charge / discharge cycle, and the cycle life is also improved. There was a problem that it was not enough.

本発明は、上記の問題に鑑みてなされたものであり、従来のカルボキシル基を僅かしか含まないリグニンを含有した負極を用いた鉛蓄電池に比べて、充放電サイクルの経過による負極の比表面積の低下が少ないリグニンを含有した鉛蓄電池用負極及びそれを用いたサイクル寿命の向上した鉛蓄電池を提供すること、更には、サイクル寿命の向上に加えて、活物質を脆弱化させることなく放電容量を大きくできる鉛蓄電池を提供することを課題とする。   The present invention has been made in view of the above problems, and compared with the conventional lead-acid battery using a negative electrode containing a lignin that contains only a few carboxyl groups, the specific surface area of the negative electrode due to the progress of the charge / discharge cycle. To provide a negative electrode for a lead storage battery containing lignin with little decrease and a lead storage battery with improved cycle life using the same, and in addition to improving the cycle life, the discharge capacity can be reduced without weakening the active material. It is an object to provide a lead-acid battery that can be enlarged.

上記課題を解決するために、本発明は、以下の手段を採用するものである。
（１）リグニンが含有された鉛蓄電池用負極において、前記リグニンは、分子内の一部のＣ6−Ｃ3基本構造のベンゼン環を解裂してカルボキシル基を導入したリグニンであることを特徴とする鉛蓄電池用負極である。
（２）前記リグニンは、分子内の一部にキノン構造を有するリグニンであることを特徴とする前記（１）に記載の鉛蓄電池用負極である。
（３）前記キノン構造は、Ｃ6−Ｃ3基本構造ののうち解裂していないベンゼン環にメチレンを介して導入されていることを特徴とする前記（２）の鉛蓄電池用負極である。
（４）前記キノン構造は、ベンゾキノン、ナフトキノン、アントラキノン又はそれらの誘導体の構造であることを特徴とする前記（３）の鉛蓄電池用負極である。
（５）前記リグニンは、前記キノン構造の比がＣ6−Ｃ3基本構造に対して０．０５以上０．２以下のリグニンであることを特徴とする前記（２）〜（４）のいずれか一項の鉛蓄電池用負極である。
（６）前記リグニンは、Ｃ6−Ｃ3基本構造のベンゼン環に対する、解裂されてカルボキシル基を導入されたベンゼン環の比は０．１以上、０．３以下のリグニンであることを特徴とする前記（１）〜（５）のいずれか一項の鉛蓄電池用負極である。
（７）前記リグニンの含有量が、鉛粉に対して０．１質量％以上、０．６質量％以下であることを特徴とする前記（１）〜（６）のいずれか一項の鉛蓄電池用負極である。
（８）前記（１）〜（７）のいずれか一項のリグニンが含有された負極を用いたことを特徴とする鉛蓄電池である。 In order to solve the above-described problems, the present invention employs the following means.
(1) In a negative electrode for a lead storage battery containing lignin, the lignin is a lignin in which a carboxyl group is introduced by cleaving a part of the benzene ring of the C 6 -C 3 basic structure in the molecule. It is a negative electrode for lead acid batteries.
(2) The lead acid battery negative electrode according to (1), wherein the lignin is a lignin having a quinone structure in a part of the molecule.
(3) The negative electrode for a lead-acid battery according to (2), wherein the quinone structure is introduced into a benzene ring that is not cleaved in the C 6 -C 3 basic structure via methylene. .
(4) The lead-acid battery negative electrode according to (3), wherein the quinone structure is a structure of benzoquinone, naphthoquinone, anthraquinone, or a derivative thereof.
(5) Any of the above (2) to (4) , wherein the lignin is a lignin having a quinone structure ratio of 0.05 to 0.2 with respect to the C 6 -C 3 basic structure. A negative electrode for a lead storage battery according to claim 1.
(6) The above lignin is a lignin having a ratio of a benzene ring having a carboxyl group introduced by cleavage to a benzene ring having a C 6 -C 3 basic structure of 0.1 or more and 0.3 or less. The lead-acid battery negative electrode according to any one of (1) to (5) .
(7) The lead according to any one of (1) to (6), wherein the content of the lignin is 0.1% by mass or more and 0.6% by mass or less based on the lead powder. It is a negative electrode for storage batteries.
(8) A lead-acid battery using a negative electrode containing the lignin according to any one of (1) to (7).

本発明は、鉛蓄電池用負極に特定のカルボキシル基を導入したリグニンを含有させたことにより、充放電サイクルの経過による負極の比表面積の低下が少なくなり、鉛蓄電池のサイクル寿命が向上するという効果を奏し、更に、そのリグニンが分子内の一部にキノン構造を有する場合には、活物質を脆弱化させることなく放電容量を最も効率良く抽出できるという効果も奏する。   The present invention has the effect of reducing the decrease in the specific surface area of the negative electrode due to the progress of the charge / discharge cycle and improving the cycle life of the lead storage battery by including the lignin introduced with a specific carboxyl group in the negative electrode for the lead storage battery. Further, when the lignin has a quinone structure in a part of the molecule, the discharge capacity can be extracted most efficiently without weakening the active material.

以下、本発明の実施形態について説明する。
本発明においては、分子内の一部に、次の（化１）に示すようなカルボキシル基を導入したリグニン、又は、分子内の一部に次の（化２）に示すようなカルボキシル基及びキノン構造を導入したリグニンを使用するのが好ましい。 Hereinafter, embodiments of the present invention will be described.
In the present invention, a lignin introduced with a carboxyl group as shown in the following (Chemical Formula 1) in a part of the molecule, or a carboxyl group as shown in the following (Chemical Formula 2) in a part of the molecule and It is preferable to use lignin into which a quinone structure is introduced.

但し、Ｒ1及びＲ2は、ＳＯ3Ｈ、Ｈ、ＯＨ、ＣＯＯＨ、Ｃ6Ｈ5、Ｒ3Ｃ6Ｈ4、（Ｒ3）2Ｃ6Ｈ3、又は（Ｒ3）3Ｃ6Ｈ2であり、Ｒ3は、ＯＨ、ＣＯＯＨ、又はＳＯ3Ｈ等の官能基であり、それぞれ、Ｈは、Ｎａ、Ｍｇ、Ｃａに置換されてもよい。Ｑは、ベンゾキノン、ナフトキノン、アントラキノン等のキノン類、又はそれらの誘導体である。 However, R 1 and R 2, SO 3 H, H, OH , COOH, C 6 H 5, R 3 C 6 H 4, (R 3) 2 C 6 H 3, or (R 3) 3 C 6 H 2 and R 3 is a functional group such as OH, COOH, or SO 3 H, and H may be substituted with Na, Mg, or Ca, respectively. Q is a quinone such as benzoquinone, naphthoquinone or anthraquinone, or a derivative thereof.

上記のリグニンは、以下のようにして製造した。
（化１）に示すリグニンは、市販のリグニン２０ｇを３００ｍｌの水に入れ、３％のオゾンを含む酸素ガスを流量５００ｍｌ／ｍｉｎ．で、１５０分間バブリングさせた後、エーテル溶媒中に滴下させて沈殿させ、乾燥させて得た。
このとき、オゾンにより酸化されて一部のベンゼン環が解裂してカルボキシル基が導入された（化１）に示すリグニンが得られ、解裂していないＣ6−Ｃ3基本構造のベンゼン環が残存した。カルボキシル基の導入量はオゾンを含む酸素ガスのバブリング時間を変更することによって調整した。 The above lignin was produced as follows.
The lignin shown in (Chemical Formula 1) was obtained by putting 20 g of commercially available lignin in 300 ml of water and supplying oxygen gas containing 3% ozone at a flow rate of 500 ml / min. Then, after bubbling for 150 minutes, it was dropped into an ether solvent, precipitated, and dried.
At this time, the lignin shown in (Chemical Formula 1) in which a benzene ring was cleaved by oxidation by ozone and a carboxyl group was introduced was obtained, and the benzene ring having a C 6 -C 3 basic structure that was not cleaved. Remained. The amount of carboxyl group introduced was adjusted by changing the bubbling time of oxygen gas containing ozone.

（化２）に示すリグニンは、上記のようにして得た分子内の一部にカルボキシル基が導入されたリグニン２０ｇに３５％のホルムアルデヒド溶液１１ｍｌを加えたものと、前記Ｑで示した０．１２ｍｏｌ．相当のキノン類に水２００ｍｌを加えたものとを混合してアルカリ性に調整し、１５０℃の加圧下（たとえばオートクレーブ内）で、２時間反応させた後、脱塩、乾燥させて得た。
このとき、Ｑは、残存した解裂していないＣ6−Ｃ3基本構造のベンゼン環に導入された。キノン類の導入量は、混合するキノン量を変更することによって調整した。また、これらのキノン類の導入された量については、ＩＲ及びＵＶの測定によって確認した。 The lignin shown in (Chemical Formula 2) is obtained by adding 11 ml of a 35% formaldehyde solution to 20 g of lignin having a carboxyl group introduced into a part of the molecule obtained as described above, and the value of 0. 12 mol. The mixture was adjusted to alkalinity by mixing a corresponding quinone with 200 ml of water, reacted for 2 hours under a pressure of 150 ° C. (for example, in an autoclave), then desalted and dried.
At this time, Q was introduced into the remaining uncleaved C 6 -C 3 basic structure benzene ring. The amount of quinones introduced was adjusted by changing the amount of quinone to be mixed. The amount of these quinones introduced was confirmed by IR and UV measurements.

上記（化１）に示すように、本発明において使用するリグニンは、鉛と配位しやすいＣ＝Ｏと親水性の高いＯＨとを共に含むカルボキシル基を、ベンゼン環の解裂によって２個導入したことによって、これらのリグニンを含有した鉛蓄電池用負極について、Ｃ＝Ｏによる分散性とＯＨによる親水性の向上が実現でき、比表面積の増大が実現できた。また、前記リグニンは、上記したキノン構造を有していれば、そのＣ＝Ｏによっても分散性の向上が可能となる。   As shown in the above (Chemical Formula 1), the lignin used in the present invention introduces two carboxyl groups containing both C═O, which is easily coordinated with lead, and highly hydrophilic OH, by cleavage of the benzene ring. As a result, with respect to the negative electrode for a lead storage battery containing these lignins, dispersibility by C = O and hydrophilicity by OH could be realized, and an increase in specific surface area could be realized. In addition, if the lignin has the quinone structure described above, the dispersibility can be improved even by its C═O.

リグニンは、Ｃ6−Ｃ6基本構造のベンゼン環に対する、解裂されてカルボキシル基を導入されたベンゼン環の比が０．１以上、０．３以下のリグニンであることが好ましい。
この比が０．１未満では、負極の比表面積の低下の抑制、鉛蓄電池のサイクル寿命の向上の効果が十分に発揮されない。
この比が０．３を超えると、上記の効果が飽和するとともに、水素過電圧が低下して充電の妨げとなる。 The lignin is preferably a lignin having a ratio of a benzene ring into which a carboxyl group is introduced by cleavage to a benzene ring having a C 6 -C 6 basic structure of 0.1 to 0.3.
If this ratio is less than 0.1, the effects of suppressing the decrease in the specific surface area of the negative electrode and improving the cycle life of the lead storage battery are not sufficiently exhibited.
When this ratio exceeds 0.3, the above effect is saturated, and the hydrogen overvoltage is lowered to hinder charging.

さらに、前記リグニンは、キノン構造を有する場合、そのキノン構造の比がＣ6−Ｃ3基本構造に対して０．０５以上０．２以下であることが好ましい。
キノン構造に含まれるＣ＝Ｏは、その錯形成による働きから、放電時に鉛イオンを取り込む作用があり、比表面積低下の抑制だけでなく、放電特性にも影響を及ぼすことがわかっている。
このため、キノン構造の比が０．０５未満では、負極の比表面積低下の抑制や放電特性向上の効果が十分に発揮されない。
また、この比が０．２を超えると、活物質の反応サイトが増大しすぎることによって、活物質の脆弱化を招き、寿命特性が低下してしまう。 Furthermore, when the lignin has a quinone structure, the ratio of the quinone structure is preferably 0.05 or more and 0.2 or less with respect to the C 6 -C 3 basic structure.
It has been found that C═O contained in the quinone structure has an effect of taking in lead ions at the time of discharge due to its complex formation, and not only suppresses a decrease in specific surface area but also affects discharge characteristics.
For this reason, when the ratio of the quinone structure is less than 0.05, the effect of suppressing the decrease in the specific surface area of the negative electrode or improving the discharge characteristics is not sufficiently exhibited.
On the other hand, when this ratio exceeds 0.2, the active material reaction sites increase excessively, leading to weakening of the active material, resulting in deterioration of life characteristics.

リグニンの含有量は、鉛粉に対して０．１質量％以上、０．６質量％以下であることが好ましい。
この含有量が０．１質量％未満では、負極の比表面積の低下の抑制、鉛蓄電池のサイクル寿命の向上の効果が十分に発揮されない。
この含有量が０．６質量％を超えると、上記の効果が飽和するとともに、物理吸着が原因となって充放電の妨げとなる。
なお、鉛粉に対するリグニン含有量が０．２質量％の場合、既化成活物質内に含まれているリグニンは、およそ０．１６質量％であった。従って、リグニンの含有量は、活物質量に対して、０．０８質量％以上、０．４８質量％以下であることが好ましいといえる。 The lignin content is preferably 0.1% by mass or more and 0.6% by mass or less based on the lead powder.
If this content is less than 0.1% by mass, the effects of suppressing the decrease in the specific surface area of the negative electrode and improving the cycle life of the lead-acid battery are not sufficiently exhibited.
When this content exceeds 0.6% by mass, the above effect is saturated, and physical adsorption prevents charging / discharging.
In addition, when the lignin content with respect to lead powder was 0.2 mass%, the lignin contained in the already formed active material was about 0.16 mass%. Therefore, it can be said that the content of lignin is preferably 0.08% by mass or more and 0.48% by mass or less with respect to the amount of active material.

上記（化１）のＲ1がＳＯ3Ｈ、Ｒ2がＯＨであり、Ｃ6−Ｃ6基本構造のベンゼン環に対する、解裂されてカルボキシル基を導入されたベンゼン環の比が０．３のリグニンを用意した。
次に、鉛粉と、該鉛粉に対して上記リグニン０．２質量％と、鉛粉に対して硫酸バリウム１．０質量％と、鉛粉に対してポリプロピレン樹脂からなる短繊維の活物質補強材０．０３質量％を撹拌混合した後、希硫酸と水で練合して本発明の活物質ペーストを作製した。 In the above (Chemical Formula 1), R 1 is SO 3 H, R 2 is OH, and the ratio of the benzene ring having a C 6 -C 6 basic structure into which a carboxyl group is cleaved and introduced is 0.3. The lignin was prepared.
Next, lead powder, 0.2% by mass of the above lignin with respect to the lead powder, 1.0% by mass of barium sulfate with respect to the lead powder, and a short fiber active material made of polypropylene resin with respect to the lead powder After stirring and mixing 0.03% by mass of the reinforcing material, the active material paste of the present invention was prepared by kneading with dilute sulfuric acid and water.

この活物質ペーストを格子体からなる集電体に充填してから、熟成、乾燥を行って未化成の負極板を得た。次に、この未化成の負極板と公知の未化成のペースト式正極板とを、ポリエチレンセパレータを介し、積層して極板群を作った。次に、各極板群をポリプロピレン製の電槽内に配置した。その後、電槽内に比重１．２８（２０℃）の希硫酸を主体とする電解液を注液し、電槽化成を行って本発明鉛蓄電池を完成した。
なお、上記鉛蓄電池は、縦１１５ｍｍ、横１０３ｍｍ、厚さ２．３ｍｍの正極板５枚、縦１１５ｍｍ、横１０３ｍｍ、厚さ１．８ｍｍの負極板６枚から構成され、電圧２Ｖ、３時間率容量３１．５Ａｈのものであった。 The active material paste was filled in a current collector made of a lattice, and then aged and dried to obtain an unformed negative electrode plate. Next, this unformed negative electrode plate and a known unformed pasted positive electrode plate were laminated via a polyethylene separator to form an electrode plate group. Next, each electrode plate group was placed in a battery case made of polypropylene. Thereafter, an electrolytic solution mainly composed of dilute sulfuric acid having a specific gravity of 1.28 (20 ° C.) was poured into the battery case, and the battery case was formed to complete the lead-acid battery of the present invention.
The lead storage battery is composed of five positive plates 115 mm long, 103 mm wide, 2.3 mm thick, and six negative plates 115 mm long, 103 mm wide, 1.8 mm thick, with a voltage of 2 V and a 3 hour rate. The capacity was 31.5 Ah.

（比較例）
従来から使用されているリグノスルホン酸を前記鉛粉、硫酸バリウム、活物質補強材と共に撹拌混合した後、希硫酸と水で練合して従来の活物質ペーストを得た以外は、実施例１と同様にして、従来鉛蓄電池を作製した。 (Comparative example)
Example 1 except that the conventionally used lignosulfonic acid was stirred and mixed with the lead powder, barium sulfate, and active material reinforcing material, and then kneaded with dilute sulfuric acid and water to obtain a conventional active material paste. In the same manner, a conventional lead-acid battery was produced.

前記の本発明鉛蓄電池及び従来鉛蓄電池を充放電サイクル寿命試験に供した。
充放電サイクル寿命試験の条件は、周囲温度：２５℃、放電：１０．５Ａ、２．４時間、充電：１段目を８．７５Ａで２．４Ｖに達するまで、２段目を１．７５Ａで総充電量が放電量の１１５％になるまでとした。５０サイクル毎、あるいは放電時の電圧が１．６５Ｖに低下したところで容量試験を行って、３時間率容量が定格容量の８０％（２５．２Ａｈ）以下に低下したところを寿命とした。 The lead storage battery of the present invention and the conventional lead storage battery were subjected to a charge / discharge cycle life test.
The conditions of the charge / discharge cycle life test are as follows: ambient temperature: 25 ° C., discharge: 10.5 A, 2.4 hours, charge: the first stage reaches 1.75 A until it reaches 2.4 V at 8.75 A. The total charge amount was 115% of the discharge amount. A capacity test was performed every 50 cycles or when the voltage during discharge dropped to 1.65 V, and the life when the 3-hour rate capacity dropped to 80% (25.2 Ah) or less of the rated capacity was determined.

充放電サイクル寿命試験の結果、従来鉛蓄電池は、６００サイクルで寿命に達したのに対し、本発明鉛蓄電池は、８００サイクルまで寿命が延長できた。   As a result of the charge / discharge cycle life test, the conventional lead storage battery reached the end of its life in 600 cycles, whereas the lead storage battery of the present invention was able to extend the life up to 800 cycles.

充放電サイクル寿命試験の１、１０、４００、６００、８００サイクルの各時点で電池を解体し、１サイクル後の負極の比表面積（ｍ2／ｇ）を１．０として各サイクルでの負極の比表面積を割合で示した。
その測定の結果、負極の比表面積は、従来鉛蓄電池が、１．０（１サイクル）、０．６（１０サイクル）、０．５（４００サイクル）、０．３（６００サイクル）であったのに対し、本発明鉛蓄電池は、１．０（１サイクル）、０．８（１０サイクル）、０．７（４００サイクル）、０．７（６００サイクル）、０．５（８００サイクル）であり、負極の比表面積の低下が少ないことが確認された。 The battery was disassembled at each time point of 1, 10, 400, 600, and 800 cycles of the charge / discharge cycle life test, and the specific surface area (m 2 / g) of the negative electrode after one cycle was set to 1.0. The specific surface area is shown as a percentage.
As a result of the measurement, the specific surface area of the negative electrode was 1.0 (1 cycle), 0.6 (10 cycles), 0.5 (400 cycles), and 0.3 (600 cycles) for conventional lead-acid batteries. In contrast, the lead-acid battery of the present invention is 1.0 (1 cycle), 0.8 (10 cycles), 0.7 (400 cycles), 0.7 (600 cycles), 0.5 (800 cycles). It was confirmed that there was little decrease in the specific surface area of the negative electrode.

上記（化２）のＲ1がＨ、Ｒ2がＳＯ3Ｈであり、Ｃ6−Ｃ3基本構造のベンゼン環に対する、解裂されてカルボキシル基を導入されたベンゼン環の比が０．２であり、Ｃ6−Ｃ3基本構造に対して導入されたキノン構造の比が０．０１、０．０５、０．１、０．１５、０．２、０．２５のリグニンａ〜ｆを用意した。
次に、鉛粉と、該鉛粉に対して上記各リグニン０．２質量％と、鉛粉に対して硫酸バリウム１．０質量％と、鉛粉に対してポリプロピレン樹脂からなる短繊維の活物質補強材０．０３質量％を撹拌混合した後、水と希硫酸で練合してリグニンａ〜ｆを含有した活物質ペーストを作製した。 In the above (Chemical Formula 2), R 1 is H, R 2 is SO 3 H, and the ratio of the benzene ring having a C 6 -C 3 basic structure into which a carboxyl group is cleaved and introduced is 0.2. Lignin a to f having a quinone structure ratio of 0.01, 0.05, 0.1, 0.15, 0.2, 0.25 introduced to the C 6 -C 3 basic structure Prepared.
Next, lead powder, 0.2% by mass of each lignin with respect to the lead powder, 1.0% by mass of barium sulfate with respect to the lead powder, and the activity of short fibers made of polypropylene resin with respect to the lead powder. 0.03% by mass of the material reinforcing material was stirred and mixed, and then kneaded with water and dilute sulfuric acid to prepare an active material paste containing lignin a to f.

これらの各活物質ペーストを格子体からなる集電体に充填してから、熟成、乾燥を行って、それぞれリグニンａ〜ｆを含有した未化成の負極板を得た。次に、実施例１と同様の方法で本発明鉛蓄電池Ａ〜Ｆ（リグニンａ〜ｆを含有した本発明の負極板を備えた鉛蓄電池が、それぞれ、本発明鉛蓄電池Ａ〜Ｆに対応する。）を完成した。   Each active material paste was filled in a current collector made of a lattice, and then aged and dried to obtain unformed negative electrode plates each containing lignin a to f. Next, the lead storage batteries A to F of the present invention (the lead storage batteries including the negative electrode plate of the present invention containing lignin a to f correspond to the lead storage batteries A to F of the present invention in the same manner as in Example 1, respectively. .) Completed.

この本発明鉛蓄電池Ａ〜Ｆ及び前記の比較例で作製した従来鉛蓄電池を、実施例１と同様の条件で、充放電サイクル寿命試験に供した。   The lead acid batteries A to F of the present invention and the conventional lead acid battery produced in the above comparative example were subjected to a charge / discharge cycle life test under the same conditions as in Example 1.

充放電サイクル寿命試験の結果、従来鉛蓄電池は、６００サイクルで寿命に達したのに対し、本発明鉛蓄電池Ａ〜Ｆのうち、導入されたキノン構造の比がＣ6−Ｃ3基本構造に対して０．０５以上０．２以下のリグニンを用いたＢ〜Ｅで、図１に示すように８００サイクル以上まで寿命が延長できた。 As a result of the charge / discharge cycle life test, the conventional lead storage battery has reached the end of its life in 600 cycles, but among the lead storage batteries A to F of the present invention, the ratio of the introduced quinone structure is C 6 -C 3 basic structure. On the other hand, with B to E using lignin of 0.05 or more and 0.2 or less, the life could be extended to 800 cycles or more as shown in FIG.

充放電サイクル寿命試験の１、１０、４００、６００、８００サイクルの各時点で電池を解体し、１サイクル後の負極の比表面積を１．０として各サイクルでの負極の比表面積の割合を図２に示す。
その結果、負極の比表面積は、従来鉛蓄電池、本発明鉛蓄電池共にサイクル数の増加に伴って、徐々に減少する傾向であったが、その減少する割合は、本発明鉛蓄電池の場合で小さくなっていることが確認できた。なお、容量は、従来鉛蓄電池の初期容量を１．０として各サイクルでの容量を割合で示した。 The battery is disassembled at each time point of the charge / discharge cycle life test at 1, 10, 400, 600, and 800 cycles, and the specific surface area of the negative electrode in each cycle is shown in FIG. It is shown in 2.
As a result, the specific surface area of the negative electrode tended to gradually decrease with the increase in the number of cycles for both the conventional lead storage battery and the lead storage battery of the present invention, but the decreasing ratio was small in the case of the lead storage battery of the present invention. It was confirmed that In addition, the capacity | capacitance showed the capacity | capacitance in each cycle in the ratio by making 1.0 the initial capacity of the conventional lead storage battery.

充放電サイクル寿命試験の２００サイクル毎の容量試験の結果を図３に示す。
その結果、本発明鉛蓄電池の容量は、同じ活物質量にも関わらず、従来鉛蓄電池の容量に比べ、初期から大きくなっており、そのうち、導入されたキノン構造の比がＣ6−Ｃ3基本構造に対して０．０５以上０．２以下のリグニンを用いたＢ〜Ｅで、容量の低下が小さくなっていることが確認できた。 The results of the capacity test every 200 cycles of the charge / discharge cycle life test are shown in FIG.
As a result, the capacity of the lead-acid battery of the present invention is larger from the beginning than the capacity of the conventional lead-acid battery despite the same amount of active material, and the ratio of the introduced quinone structure is C 6 -C 3. It was confirmed that the decrease in capacity was small in B to E using lignin of 0.05 to 0.2 with respect to the basic structure.

上記の実施例で述べた本発明による効果は、鉛蓄電池の形式や試験方法によって変わるものではなく、本発明の負極は、各種鉛蓄電池、各種用途に使用できるものであり、実施例に限定されるものでない。   The effects of the present invention described in the above embodiments do not vary depending on the type or test method of the lead storage battery, and the negative electrode of the present invention can be used for various lead storage batteries and various applications, and is limited to the embodiments. It is not something.

従来鉛蓄電池（比較例）と本発明鉛蓄電池の寿命サイクル数を示す図である。It is a figure which shows the life cycle number of a conventional lead acid battery (comparative example) and this invention lead acid battery. 従来鉛蓄電池（比較例）の１サイクル後の比表面積を１．０とした場合の本発明鉛蓄電池の比表面積の割合を示す図である。It is a figure which shows the ratio of the specific surface area of this invention lead storage battery when the specific surface area after 1 cycle of the conventional lead storage battery (comparative example) is 1.0. 従来鉛蓄電池（比較例）の初期容量を１．０とした場合の本発明鉛蓄電池の容量の割合を示す図である。It is a figure which shows the ratio of the capacity | capacitance of this invention lead storage battery when the initial capacity of the conventional lead storage battery (comparative example) is 1.0.

Claims (8)

リグニンが含有された鉛蓄電池用負極において、前記リグニンは、分子内の一部のＣ6−Ｃ3基本構造のベンゼン環を解裂してカルボキシル基を導入したリグニンであることを特徴とする鉛蓄電池用負極。 A lead-acid battery negative electrode containing lignin, wherein the lignin is a lignin in which a carboxyl group is introduced by cleaving a benzene ring of a part of a C 6 -C 3 basic structure in the molecule. Negative electrode for storage battery. 前記リグニンは、分子内の一部にキノン構造を有するリグニンであることを特徴とする請求項１に記載の鉛蓄電池用負極。   The negative electrode for a lead storage battery according to claim 1, wherein the lignin is a lignin having a quinone structure in a part of the molecule. 前記キノン構造は、Ｃ6−Ｃ3基本構造のうち解裂していないベンゼン環にメチレンを介して導入されて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。 3. The negative electrode for a lead storage battery according to claim 2, wherein the quinone structure is introduced into a benzene ring which is not cleaved in a C 6 -C 3 basic structure via methylene. 前記キノン構造は、ベンゾキノン、ナフトキノン、アントラキノン又はそれらの誘導体の構造であることを特徴とする請求項３に記載の鉛蓄電池用負極。   The negative electrode for a lead storage battery according to claim 3, wherein the quinone structure is a structure of benzoquinone, naphthoquinone, anthraquinone, or a derivative thereof. 前記リグニンは、前記キノン構造の比がＣ6−Ｃ3基本構造に対して０．０５以上０．２以下のリグニンであることを特徴とする請求項２〜４のいずれか一項に記載の鉛蓄電池用負極。 The lignin is a lignin having a ratio of the quinone structure of 0.05 to 0.2 with respect to the C 6 -C 3 basic structure, according to any one of claims 2 to 4 . Negative electrode for lead acid battery. 前記リグニンは、Ｃ6−Ｃ3基本構造のベンゼン環に対する、解裂されてカルボキシル基を導入されたベンゼン環の比が０．１以上、０．３以下のリグニンであることを特徴とする請求項１〜５のいずれか一項に記載の鉛蓄電池用負極。 The lignin is a lignin having a ratio of a benzene ring into which a carboxyl group is introduced by cleavage to a benzene ring having a C 6 -C 3 basic structure in a range of 0.1 to 0.3. the negative electrode for a lead acid battery according to any one of claims 1-5. 前記リグニンの含有量が、鉛粉に対して０．１質量％以上、０．６質量％以下であることを特徴とする請求項１〜６のいずれか一項に記載の鉛蓄電池用負極。   Content of the said lignin is 0.1 to 0.6 mass% with respect to lead powder, The negative electrode for lead acid batteries as described in any one of Claims 1-6 characterized by the above-mentioned. 請求項１〜７のいずれか一項に記載のリグニンが含有された負極を用いたことを特徴とする鉛蓄電池。   The lead acid battery using the negative electrode containing the lignin as described in any one of Claims 1-7.
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