JP4811635B2 - Lead-acid battery and negative electrode and negative electrode active material used therefor - Google Patents

Lead-acid battery and negative electrode and negative electrode active material used therefor Download PDF

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JP4811635B2
JP4811635B2 JP2004364302A JP2004364302A JP4811635B2 JP 4811635 B2 JP4811635 B2 JP 4811635B2 JP 2004364302 A JP2004364302 A JP 2004364302A JP 2004364302 A JP2004364302 A JP 2004364302A JP 4811635 B2 JP4811635 B2 JP 4811635B2
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diaminoanthraquinone
negative electrode
lead
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信充 平井
敏宏 田中
謙吾 眞柄
努 池田
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Forestry and Forest Products Research Institute
Osaka University NUC
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Description

本発明は鉛蓄電池に関し、特に充電性能を向上させた鉛蓄電池に関するものである。   The present invention relates to a lead storage battery, and more particularly to a lead storage battery with improved charging performance.

近年、アイドリングストップ車、ハイブリッド車、ロードレベリングシステム等に用いる二次電池として、高い充電性能を発揮する二次電池の開発が要望されている。
二次電池として代表的な鉛蓄電池は、リチウムイオン蓄電池やニッケル水素蓄電池等の他の二次電池と比較して、高出力で、使用温度域が広く、リサイクル率も高く、然も低コストであるため、種々の分野に広く利用されており、充放電性能の更なる向上を図るべく種々の鉛蓄電池が提案されている。 In recent years, as a secondary battery used in an idling stop vehicle, a hybrid vehicle, a road leveling system, etc., development of a secondary battery that exhibits high charging performance has been demanded.
Lead-acid batteries, which are typical secondary batteries, have a higher output, a wider operating temperature range, a higher recycling rate, and lower costs compared to other secondary batteries such as lithium-ion batteries and nickel-metal hydride batteries. For this reason, it is widely used in various fields, and various lead storage batteries have been proposed in order to further improve the charge / discharge performance.

例えば、鉛蓄電池の低温高率放電寿命特性を向上させるべく、負極活物質にリグニンとカーボンを添加した鉛蓄電池が提案されている(特許文献１)。
又、鉛蓄電池の高率放電性能及びサイクル寿命性能を向上させるべく、負極活物質中に金属錫を含有させた鉛蓄電池が提案されている(特許文献２)。
更に、鉛蓄電池の高率充電特性や長期間放置後の充電性能を向上させるべく、負極活物質中にカルシウムを添加した鉛蓄電池が提案されている(特許文献３)。
特開平９−２１３３３６号公報 特開平５−８９８７３号公報 特開２０００−２２４４０号公報 For example, a lead storage battery in which lignin and carbon are added to a negative electrode active material has been proposed in order to improve the low temperature high rate discharge life characteristics of the lead storage battery (Patent Document 1).
Moreover, in order to improve the high rate discharge performance and cycle life performance of a lead storage battery, a lead storage battery in which metallic tin is contained in a negative electrode active material has been proposed (Patent Document 2).
Furthermore, a lead storage battery in which calcium is added to the negative electrode active material has been proposed in order to improve the high-rate charging characteristics of the lead storage battery and the charging performance after being left for a long time (Patent Document 3).
JP-A-9-213336 JP-A-5-89873 JP 2000-22440 A

しかしながら、負極活物質にリグニンとカーボンを添加した鉛蓄電池においては、カーボンの添加によって充電性能のある程度の向上は期待できるものの、カーボンの多量の添加は、水素過電圧を小さくするため、換言すれば、副反応である水素発生電流が流れるため、却って充電性能を低下させることになる。
又、負極活物質中に金属錫を含有させた鉛蓄電池や、負極活物質中にカルシウムを添加した鉛蓄電池によっても、充電性能の大幅な向上は期待できない。 However, in a lead storage battery in which lignin and carbon are added to the negative electrode active material, although a certain degree of improvement in charging performance can be expected by adding carbon, in other words, the addition of a large amount of carbon reduces the hydrogen overvoltage, in other words, Since a hydrogen generation current which is a side reaction flows, the charging performance is reduced.
In addition, a significant improvement in charging performance cannot be expected even with a lead storage battery in which metallic tin is contained in the negative electrode active material or a lead storage battery in which calcium is added to the negative electrode active material.

そこで本発明の目的は、充電性能を向上させることが出来る鉛蓄電池及びこれに用いる負極並びに負極活物質を提供することである。   Then, the objective of this invention is providing the lead acid battery which can improve charge performance, the negative electrode used for this, and a negative electrode active material.

本発明に係る鉛蓄電池は、負極を構成する活物質中又は電解液中に、ジアミノアントラキノンをその構造の少なくとも一部に含む有機分子を含有している。 The lead acid battery according to the present invention contains an organic molecule containing diaminoanthraquinone in at least a part of its structure in the active material constituting the negative electrode or in the electrolytic solution .

前記有機分子としては、１，５−ジアミノアントラキノン、１，４−ジアミノアントラキノン、２，６−ジアミノアントラキノンを採用することが出来、ジアミノアントラキノンはモノマーに限らず、ポリマーであってもよい。又、前記有機分子は、ジアミノアントラキノンをその構造の少なくとも一部に含むリグニンであってもよい。   As the organic molecule, 1,5-diaminoanthraquinone, 1,4-diaminoanthraquinone, and 2,6-diaminoanthraquinone can be employed, and the diaminoanthraquinone is not limited to a monomer but may be a polymer. The organic molecule may be a lignin containing diaminoanthraquinone in at least a part of its structure.

前記有機分子を電解液に添加する場合、その添加量は、電解液１リットルに対して６ｍｇ以上であることが好ましい。
又、前記有機分子を負極活物質に添加する場合、その添加量は、活物質の質量に対して０.１質量％以上であることが好ましい。 When the organic molecule is added to the electrolytic solution, the amount added is preferably 6 mg or more per liter of the electrolytic solution.
Moreover, when adding the said organic molecule | numerator to a negative electrode active material, it is preferable that the addition amount is 0.1 mass % or more with respect to the mass of an active material.

上記本発明の鉛蓄電池の充放電性能を、後述の如く３電極方式による充放電試験(単板試験)によって調べたところ、ジアミノアントラキノンの添加によって、放電性能を殆ど同一に維持したまま充電性能を向上させることが出来ることを確認した。   When the charge / discharge performance of the lead storage battery of the present invention was examined by a charge / discharge test (single plate test) using a three-electrode system as described below, the addition of diaminoanthraquinone improved the charge performance while maintaining almost the same discharge performance. It was confirmed that it could be improved.

鉛蓄電池におけるジアミノアントラキノンの作用については、現在のところ明らかではないが、次の様に推測される。
即ち、ジアミノアントラキノンを含有する電極は硫酸水溶液中においてアニオン及びカチオンを電極表面に捕捉する機能を有するものと考えられる。本発明の鉛蓄電池においては、負極活物質或いは電解液に添加されたジアミノアントラキノンによって、電極表面近傍の過剰なＰｂ２＋イオンが電極表面に捕捉され、この結果、Ｐｂ２＋イオン濃度が低下し、これによって放電生成物である硫酸鉛の溶解が加速されることとなり、充電性能が大幅に向上するものと推測される。 The action of diaminoanthraquinone in lead-acid batteries is not clear at present, but is presumed as follows.
That is, the electrode containing diaminoanthraquinone is considered to have a function of trapping anions and cations on the electrode surface in an aqueous sulfuric acid solution. In the lead storage battery of the present invention, excess Pb 2+ ions in the vicinity of the electrode surface are trapped on the electrode surface by the diaminoanthraquinone added to the negative electrode active material or the electrolytic solution. As a result, the Pb 2+ ion concentration decreases, As a result, the dissolution of lead sulfate, which is a discharge product, is accelerated, and it is estimated that the charging performance is greatly improved.

本発明に係る鉛蓄電池によれば、従来の鉛蓄電池よりも充電性能を大幅に向上させることが出来る。   According to the lead storage battery according to the present invention, the charging performance can be greatly improved as compared with the conventional lead storage battery.

以下、本発明の実施形態につき、図面に沿って具体的に説明する。
本発明に係る鉛蓄電池は、負極を構成する活物質中又は電解液中に、ジアミノアントラキノンをその構造の少なくとも一部に含む有機分子を含有するものである。
又、本発明に係る鉛蓄電池用負極は、その活物質中に、ジアミノアントラキノンをその構造の少なくとも一部に含む有機分子を含有するものである。 Hereinafter, embodiments of the present invention will be specifically described with reference to the drawings.
The lead acid battery which concerns on this invention contains the organic molecule which contains diaminoanthraquinone in at least one part of the structure in the active material or electrolyte solution which comprises a negative electrode.
The negative electrode for a lead storage battery according to the present invention contains an organic molecule containing diaminoanthraquinone in at least a part of its structure in the active material.

前記有機分子としては、１，５−ジアミノアントラキノン、１，４−ジアミノアントラキノン、２，６−ジアミノアントラキノンを採用することが出来、ジアミノアントラキノンはモノマーに限らず、ポリマーであってもよい。又、前記有機分子は、ジアミノアントラキノンをその構造の少なくとも一部に含むリグニンであってもよい。   As the organic molecule, 1,5-diaminoanthraquinone, 1,4-diaminoanthraquinone, and 2,6-diaminoanthraquinone can be employed, and the diaminoanthraquinone is not limited to a monomer but may be a polymer. The organic molecule may be a lignin containing diaminoanthraquinone in at least a part of its structure.

１，５−ジアミノアントラキノン、１，４−ジアミノアントラキノン、及び２，６−ジアミノアントラキノンの化学構造式をそれぞれ次の化１、化２及び化３に示す。
又、これらのジアミノアントラキノンとの比較のために、アミノ基が１つ少ない１−アミノアントラキノンの化学構造式を化４に示す。 The chemical structural formulas of 1,5-diaminoanthraquinone, 1,4-diaminoanthraquinone and 2,6-diaminoanthraquinone are shown in the following chemical formula 1, chemical formula 2 and chemical formula 3, respectively.
For comparison with these diaminoanthraquinones, the chemical structural formula of 1-aminoanthraquinone having one less amino group is shown in Chemical Formula 4.

Figure 0004811635
Figure 0004811635
Figure 0004811635
Figure 0004811635
Figure 0004811635
Figure 0004811635
Figure 0004811635
Figure 0004811635

本発明に係る鉛蓄電池、鉛蓄電池用負極或いは負極活物質によれば、後述の実施例によって実証する様に、高い放電性能を維持したまま、充電性能を従来よりも大幅に向上させることが出来る。   According to the lead storage battery, the negative electrode for a lead storage battery, or the negative electrode active material according to the present invention, as demonstrated by the examples described later, the charging performance can be significantly improved while maintaining high discharge performance. .

本発明に係る鉛蓄電池の性能を確認するべく、図４に示す試験装置を用いて、３電極方式による充放電試験(単板試験)を行なった。試験装置は図示の如く、硫酸電解液(５)中に、作用電極としての鉛電極(１)と、参照電極としての硫酸／硫酸水銀電極(２)と、対極としての二酸化鉛電極(３)とを配置し、これらの電極にポテンシオスタット(４)を接続して構成される。   In order to confirm the performance of the lead storage battery according to the present invention, a charge / discharge test (single plate test) using a three-electrode system was performed using the test apparatus shown in FIG. As shown in the figure, the test apparatus is composed of a lead electrode (1) as a working electrode, a sulfuric acid / mercury sulfate electrode (2) as a reference electrode, and a lead dioxide electrode (3) as a counter electrode in a sulfuric acid electrolyte (5). And a potentiostat (4) connected to these electrodes.

該試験装置において硫酸電解液(５)を次の５種類の硫酸水溶液に入れ替えて５回の試験を行ない、それぞれ鉛電極(鉛蓄電池の負極)についてのサイクリックボルタモグラムを得た。尚、電位走査速度は１０ｍＶ／ｍｉｎである。
本発明例１では、０.０１ｍ ｍｏｌ／リットルの１，５−ジアミノアントラキノンを溶解した脱気５ｍｏｌ／リットルの硫酸水溶液を用いた。
本発明例２では、０.０２５ｍ ｍｏｌ／リットルの１，５−ジアミノアントラキノンを溶解した脱気５ｍｏｌ／リットルの硫酸水溶液を用いた。
本発明例３では、０.１ｍ ｍｏｌ／リットルの１，５−ジアミノアントラキノンを溶解した脱気５ｍｏｌ／リットルの硫酸水溶液を用いた。
比較例１では、脱気５ｍｏｌ／リットルの硫酸水溶液を用いた。
比較例２では、０.１ｍ ｍｏｌ／リットルの１−アミノアントラキノンを溶解した脱気５ｍｏｌ／リットルの硫酸水溶液を用いた。 In the test apparatus, the sulfuric acid electrolyte solution (5) was replaced with the following five types of sulfuric acid aqueous solutions, and the test was performed five times. A cyclic voltammogram was obtained for each lead electrode (the negative electrode of the lead storage battery). The potential scanning speed is 10 mV / min.
In Inventive Example 1, a degassed 5 mol / liter sulfuric acid aqueous solution in which 0.01 mmol / liter of 1,5-diaminoanthraquinone was dissolved was used.
In Inventive Example 2, a degassed 5 mol / liter sulfuric acid aqueous solution in which 0.025 mmol / liter of 1,5-diaminoanthraquinone was dissolved was used.
In Example 3 of the present invention, a degassed 5 mol / liter sulfuric acid aqueous solution in which 0.1 mmol / liter of 1,5-diaminoanthraquinone was dissolved was used.
In Comparative Example 1, a degassed 5 mol / liter sulfuric acid aqueous solution was used.
In Comparative Example 2, a degassed 5 mol / liter sulfuric acid aqueous solution in which 0.1 mmol / liter of 1-aminoanthraquinone was dissolved was used.

図１は、１，５−ジアミノアントラキノンを添加した本発明例３についてのサイクリックボルタモグラムを実線で示し、無添加の比較例１についてのサイクリックボルタモグラムを破線で示したものである。
又、図２は、１−アミノアントラキノンを添加した比較例２についてのサイクリックボルタモグラムを実線で示し、無添加の比較例１についてのサイクリックボルタモグラムを破線で示したものである。 FIG. 1 shows a cyclic voltammogram for the inventive example 3 to which 1,5-diaminoanthraquinone was added by a solid line, and a cyclic voltammogram for the non-added comparative example 1 by a broken line.
FIG. 2 shows a cyclic voltammogram for Comparative Example 2 to which 1-aminoanthraquinone was added by a solid line, and a cyclic voltammogram for the non-added Comparative Example 1 by a broken line.

そして、本発明例１〜３、比較例１及び２について得られた５つのサイクリックボルタモグラムから、各例についての放電容量及び充電容量を求めたところ、下記表１の結果が得られた。   And when the discharge capacity and charge capacity about each example were calculated | required from five cyclic voltammograms obtained about this invention examples 1-3 and the comparative examples 1 and 2, the result of following Table 1 was obtained.

Figure 0004811635
Figure 0004811635

表中、「ＤＡＡＱ」は１，５−ジアミノアントラキノンを意味し、「ＡＡＱ」は１−アミノアントラキノンを意味する。
又、放電容量とは、サイクリックボルタモグラムのアノード走査時に得られた正の電流の時間に対する積分値(電気量)であり、充電容量とは、サイクリックボルタモグラムのカソード走査時に得られた負の電流の絶対値の時間に対する積分値(電気量)である。 In the table, “DAAQ” means 1,5-diaminoanthraquinone, and “AAQ” means 1-aminoanthraquinone.
The discharge capacity is an integral value (amount of electricity) with respect to the time of the positive current obtained during the anode scanning of the cyclic voltammogram, and the charge capacity is the negative current obtained during the cathode scanning of the cyclic voltammogram. It is an integral value (electric quantity) with respect to time of the absolute value of.

図１及び表１から明らかな様に、放電容量については、１，５−ジアミノアントラキノンを添加した本発明例１〜３と比較例１との間に大きな差異はないが、充電容量は、本発明例１〜３の方が比較例１よりも大幅に増大している。
例えば、図１に示す本発明例３を比較例１と比較した場合、比較例１においては放電容量の約３３％が未充電であったのに対し、本発明例３においては放電容量の約８％のみが未充電であったに過ぎない。この結果は、１，５−ジアミノアントラキノンの添加によって鉛蓄電池の充電速度が増大したこと、即ち充電性能が向上したことを意味している。本発明例１及び２においても同様のことが言える。 As is apparent from FIG. 1 and Table 1, the discharge capacity is not significantly different between Examples 1 to 3 of the present invention to which 1,5-diaminoanthraquinone was added and Comparative Example 1, but the charge capacity was Inventive Examples 1 to 3 are significantly larger than Comparative Example 1.
For example, when Example 3 of the present invention shown in FIG. 1 is compared with Comparative Example 1, in Comparative Example 1, about 33% of the discharge capacity was uncharged, whereas in Example 3 of the present invention, the discharge capacity was about Only 8% were uncharged. This result means that the charging speed of the lead storage battery is increased by the addition of 1,5-diaminoanthraquinone, that is, the charging performance is improved. The same can be said for Invention Examples 1 and 2.

又、図２及び表１から明らかな様に、比較例２においては、１−アミノアントラキノンの添加によって放電容量に若干の増大は見られるものの、充電容量は著しく減少しており、１−アミノアントラキノンの添加によっては、鉛蓄電池の充電性能を向上させることは出来ないと言える。   As is clear from FIG. 2 and Table 1, in Comparative Example 2, although the discharge capacity was slightly increased by the addition of 1-aminoanthraquinone, the charge capacity was remarkably reduced, and 1-aminoanthraquinone was significantly reduced. It can be said that the charging performance of the lead-acid battery cannot be improved depending on the addition of.

１，５−ジアミノアントラキノンの添加濃度と容量比(充電容量／放電容量)との関係を図３に示す。
図３から明らかな様に、１，５−ジアミノアントラキノンの濃度が零から０.０２５ｍ ｍｏｌ／リットルまで増大するにつれて、容量比は６７％から８８％に向かって急激に上昇し、濃度が０.０２５ｍ ｍｏｌ／リットルを超えると、容量比の上昇は緩やかとなり、徐々に飽和状態に近づくことになる。
従って、１，５−ジアミノアントラキノンの濃度としては０.０２５ｍ ｍｏｌ／リットル(電解液１リットル当たり約６ｍｇ)以上が好ましいと言える。 FIG. 3 shows the relationship between the added concentration of 1,5-diaminoanthraquinone and the capacity ratio (charge capacity / discharge capacity).
As is apparent from FIG. 3, as the concentration of 1,5-diaminoanthraquinone increases from zero to 0.025 mmol / liter , the volume ratio increases rapidly from 67% to 88%, and the concentration reaches 0.0. When it exceeds 025 mmol / liter , the increase in the capacity ratio becomes gradual and gradually approaches a saturated state.
Accordingly, it can be said that the concentration of 1,5-diaminoanthraquinone is preferably 0.025 mmol / liter (about 6 mg per liter of electrolyte) or more.

尚、鉛蓄電池の負極においては、水素発生などの副反応が生じることが知られているが、図１からも明らかな様に、ジアミノアントラキノンの添加によって副反応に因る電流の変化はない。   Although it is known that side reactions such as hydrogen generation occur in the negative electrode of the lead storage battery, as is apparent from FIG. 1, there is no change in current due to the side reaction due to the addition of diaminoanthraquinone.

上述の如く、３電極方式による単板試験によって鉛蓄電池の負極のみの性能を評価し、ジアミノアントラキノンの添加によって充電性能が大幅に向上することを実証したが、鉛蓄電池の充電性能は負極上での反応に律速されることが知られているため、負極及び正極を配備した実際の鉛蓄電池においても、ジアミノアントラキノンの添加によって同様に高い充電性能が得られる。   As described above, the performance of only the negative electrode of a lead-acid battery was evaluated by a single-plate test using a three-electrode system, and it was demonstrated that the charging performance was greatly improved by the addition of diaminoanthraquinone. Since it is known that it is rate-determined by this reaction, even in an actual lead storage battery provided with a negative electrode and a positive electrode, high charge performance can be obtained by adding diaminoanthraquinone as well.

又、電解液にジアミノアントラキノンを添加した構成において充電性能の向上を確認したが、負極活物質にジアミノアントラキノンを添加した構成によれば、更に高い充電性能が得られるのは言うまでもない。この場合のジアミノアントラキノンの添加量は、図３の結果から推定すると、負極活物質の質量に対して０.１質量％以上であることが好ましい。 Moreover, although the improvement of charging performance was confirmed in the configuration in which diaminoanthraquinone was added to the electrolytic solution, it goes without saying that a higher charging performance can be obtained according to the configuration in which diaminoanthraquinone is added to the negative electrode active material. In this case, the amount of diaminoanthraquinone added is preferably 0.1% by mass or more based on the mass of the negative electrode active material when estimated from the results of FIG.

又、ジアミノアントラキノンとしては、１，５−ジアミノアントラキノンについての効果を確認したが、１，４−ジアミノアントラキノン、２，６−ジアミノアントラキノン、或いはジアミノアントラキノンを含むリグニンであっても、同様にジアミノアントラキノンとしてのＰｂ２＋イオン捕捉機能を発揮するので、同様に充電性能を向上させることが出来る。 In addition, as diaminoanthraquinone, the effect on 1,5-diaminoanthraquinone was confirmed, but even in the case of lignin containing 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone, or diaminoanthraquinone, diaminoanthraquinone is similarly used. Since the Pb 2+ ion trapping function is exhibited, the charging performance can be similarly improved.

１，５−ジアミノアントラキノンを添加した場合と無添加の場合のサイクリックボルタモグラムを表わす図である。It is a figure showing the cyclic voltammogram of the case where 1, 5- diaminoanthraquinone is added and the case where it does not add. １−アミノアントラキノンを添加した場合と無添加の場合のサイクリックボルタモグラムを表わす図である。It is a figure showing the cyclic voltammogram when 1-aminoanthraquinone is added and when it is not added. １，５−ジアミノアントラキノン濃度を変化させたときの放電容量に対する充電容量の変化を表わすグラフである。It is a graph showing the change of the charge capacity with respect to the discharge capacity when the 1,5-diaminoanthraquinone concentration is changed. 試験装置の構成を示す図である。It is a figure which shows the structure of a test apparatus.

符号の説明Explanation of symbols

(１) 鉛電極
(２) 硫酸／硫酸水銀電極
(３) 二酸化鉛電極
(４) ポテンシオスタット
(５) 硫酸電解液 (1) Lead electrode
(2) Sulfuric acid / mercuric sulfate electrode
(3) Lead dioxide electrode
(4) Potentiostat
(5) Sulfuric acid electrolyte

Claims (19)

電解液中に負極及び正極を設置して構成される鉛蓄電池において、前記負極を構成する活物質に、ジアミノアントラキノンをその構造の少なくとも一部に含む有機分子を添加し、又は電解液中に、ジアミノアントラキノンをその構造の少なくとも一部に含む有機分子を含有していることを特徴とする鉛蓄電池。 In a lead storage battery configured by installing a negative electrode and a positive electrode in an electrolytic solution, an organic molecule containing diaminoanthraquinone in at least part of its structure is added to the active material constituting the negative electrode , or in the electrolytic solution, A lead-acid battery comprising an organic molecule containing diaminoanthraquinone in at least a part of its structure . 前記有機分子が１，５−ジアミノアントラキノンである請求項１に記載の鉛蓄電池。   The lead acid battery according to claim 1, wherein the organic molecule is 1,5-diaminoanthraquinone. 前記有機分子が１，４−ジアミノアントラキノンである請求項１に記載の鉛蓄電池。   The lead acid battery according to claim 1, wherein the organic molecule is 1,4-diaminoanthraquinone. 前記有機分子が２，６−ジアミノアントラキノンである請求項１に記載の鉛蓄電池。   The lead acid battery according to claim 1, wherein the organic molecule is 2,6-diaminoanthraquinone. 前記有機分子がジアミノアントラキノンのポリマーである請求項１に記載の鉛蓄電池。   The lead acid battery according to claim 1, wherein the organic molecule is a polymer of diaminoanthraquinone. 前記有機分子がジアミノアントラキノンをその構造の少なくとも一部に含むリグニンである請求項１に記載の鉛蓄電池。   The lead acid battery according to claim 1, wherein the organic molecule is lignin containing diaminoanthraquinone in at least a part of its structure. 前記有機分子の添加量が、電解液１リットルに対して６ｍｇ以上である請求項１乃至請求項５の何れかに記載の鉛蓄電池。 The lead acid battery according to any one of claims 1 to 5, wherein an addition amount of the organic molecule is 6 mg or more with respect to 1 liter of an electrolyte solution. 活物質に、ジアミノアントラキノンをその構造の少なくとも一部に含む有機分子を添加している鉛蓄電池用負極。 A negative electrode for a lead storage battery in which an organic molecule containing diaminoanthraquinone in at least a part of its structure is added to an active material . 前記有機分子が１，５−ジアミノアントラキノンである請求項８に記載の鉛蓄電池用負極。 The lead-acid battery negative electrode according to claim 8 , wherein the organic molecule is 1,5-diaminoanthraquinone. 前記有機分子が１，４−ジアミノアントラキノンである請求項８に記載の鉛蓄電池用負極。 The lead-acid battery negative electrode according to claim 8 , wherein the organic molecule is 1,4-diaminoanthraquinone. 前記有機分子が２，６−ジアミノアントラキノンである請求項８に記載の鉛蓄電池用負極。 The lead-acid battery negative electrode according to claim 8 , wherein the organic molecule is 2,6-diaminoanthraquinone. 前記有機分子がジアミノアントラキノンのポリマーである請求項８に記載の鉛蓄電池用負極。 The lead-acid battery negative electrode according to claim 8 , wherein the organic molecule is a polymer of diaminoanthraquinone. 前記有機分子がジアミノアントラキノンをその構造の少なくとも一部に含むリグニンである請求項８に記載の鉛蓄電池用負極。 The negative electrode for a lead storage battery according to claim 8 , wherein the organic molecule is lignin containing diaminoanthraquinone in at least a part of its structure. ジアミノアントラキノンをその構造の少なくとも一部に含む有機分子が添加されている鉛蓄電池用の負極活物質。 A negative electrode active material for a lead storage battery to which an organic molecule containing diaminoanthraquinone in at least a part of its structure is added . 前記有機分子が１，５−ジアミノアントラキノンである請求項１４に記載の鉛蓄電池用の負極活物質。 The negative electrode active material for a lead storage battery according to claim 14 , wherein the organic molecule is 1,5-diaminoanthraquinone. 前記有機分子が１，４−ジアミノアントラキノンである請求項１４に記載の鉛蓄電池用の負極活物質。 The negative electrode active material for a lead storage battery according to claim 14 , wherein the organic molecule is 1,4-diaminoanthraquinone. 前記有機分子が２，６−ジアミノアントラキノンである請求項１４に記載の鉛蓄電池用の負極活物質。 The negative electrode active material for a lead storage battery according to claim 14 , wherein the organic molecule is 2,6-diaminoanthraquinone. 前記有機分子がジアミノアントラキノンのポリマーである請求項１４に記載の鉛蓄電池用の負極活物質。 The negative electrode active material for a lead storage battery according to claim 14 , wherein the organic molecule is a polymer of diaminoanthraquinone. 前記有機分子がジアミノアントラキノンをその構造の少なくとも一部に含むリグニンである請求項１４に記載の鉛蓄電池用の負極活物質。 15. The negative electrode active material for a lead storage battery according to claim 14 , wherein the organic molecule is lignin containing diaminoanthraquinone in at least a part of its structure.
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