JP2006140074A - Negative electrode active material for lead-acid battery, and lead-acid battery using it - Google Patents
Negative electrode active material for lead-acid battery, and lead-acid battery using it Download PDFInfo
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Abstract
Description
本発明は、鉛蓄電池の改良に関するもので、特に負極活物質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 active material.
近年、高容量の鉛蓄電池は、携帯用電子機器、非常用電源装置あるいは電気自動車などの電源として、その需要が増大してきており、種々の試みがなされている。鉛蓄電池の高容量化は、特許文献2に開示されたような、正、負極板を薄くして極板の枚数を増加させること、格子体に充填する活物質の密度を小さくして多孔性にすること、といった手段、あるいは特許文献1に開示されたような、負極活物質にカーボン等を添加して負極活物質の利用率を向上させて負極板の充電受入性能を向上させること、といった手段によって行われてきた。
上記した、正、負極板を薄くして極板の枚数を増加させることは、それによって格子体も薄くしなければならず、腐食によって格子体の強度が早期に低下するという問題があり、格子体に充填する活物質の密度を小さくして多孔性にすることは、充放電の反復や振動によって活物質の軟化や脱落が生じやすいという問題があって、いずれも鉛蓄電池の寿命性能が低下する原因を有していた。また、負極活物質に炭素粉末を添加して負極活物質の利用率を向上させて負極板の充電受入性能を向上させることは、活物質量の減少につながるという問題や、1CA以上の大電流での充電に対しては十分な効果が得られないという問題があって、高容量化には限界があった。 Increasing the number of electrode plates by thinning the positive and negative plates described above has a problem that the lattice body must also be thinned, and the strength of the lattice body is lowered early due to corrosion. Reducing the density of the active material that fills the body to make it porous has the problem that the active material is likely to soften or fall off due to repeated charge / discharge and vibration, both of which reduce the life performance of lead-acid batteries. Had a cause to do. Moreover, adding carbon powder to the negative electrode active material to improve the utilization rate of the negative electrode active material to improve the charge receiving performance of the negative electrode plate leads to a problem that the amount of active material is reduced, and a large current of 1 CA or more. There was a problem that sufficient effects could not be obtained for charging with a battery, and there was a limit to increasing the capacity.
本発明は、上記の問題に鑑みてなされたものであり、寿命性能を損なうことがなく、活物質量の減少につながることのない、高容量の鉛蓄電池を提供することを課題とする。 This invention is made | formed in view of said problem, and makes it a subject to provide the high capacity lead acid battery which does not lead to the reduction | decrease in the amount of active materials, without impairing lifetime performance.
上記課題を解決するため、本発明は、キノン構造を有したキノン物質、または前記キノン物質を重合させたキノンポリマーが鉛粉に添加されてなることを特徴とする鉛蓄電池用負極活物質(請求項1)であり、前記キノン物質またはキノンポリマーは、添加量が、鉛粉に対して、0.01質量%以上、0.03質量%以下(請求項2)であり、前記キノン物質が、ベンゾキノン、アントラキノン、ナフトキノンあるいはそれらの誘導体(請求項3)であることを特徴とする。また、本発明は、前記のいずれか一項に記載の負極活物質を用いた鉛蓄電池(請求項4)である。 In order to solve the above-mentioned problems, the present invention provides a negative electrode active material for a lead-acid battery, wherein a quinone material having a quinone structure or a quinone polymer obtained by polymerizing the quinone material is added to lead powder (claim) The quinone substance or quinone polymer is added in an amount of 0.01% by mass or more and 0.03% by mass or less (Claim 2) with respect to the lead powder, It is characterized by being benzoquinone, anthraquinone, naphthoquinone or a derivative thereof (Claim 3). Moreover, this invention is a lead acid battery (Claim 4) using the negative electrode active material as described in any one of said.
本発明は、上記した鉛蓄電池用負極活物質、あるいは前記負極活物質を用いた鉛蓄電池であるから、寿命性能を損なうことがなく、活物質量の減少につながることのない、高容量の鉛蓄電池を提供するのに寄与することができる。 Since the present invention is the above-described negative electrode active material for lead-acid batteries, or a lead-acid battery using the negative electrode active material, it does not impair the life performance and does not lead to a decrease in the amount of active material. It can contribute to providing a storage battery.
上記した鉛蓄電池用負極活物質、すなわちキノン構造を有したキノン物質、または前記キノン物質を重合させたキノンポリマーを鉛粉に添加すると、キノン構造のC=O部が活物質表面に吸着し、充放電を反復させることによって進行する負極活物質の収縮、すなわち比表面積の低下を抑制することができる、と考えられる。 When the above-described negative electrode active material for a lead storage battery, that is, a quinone material having a quinone structure, or a quinone polymer obtained by polymerizing the quinone material is added to the lead powder, the C = O part of the quinone structure is adsorbed on the active material surface, It is thought that the shrinkage of the negative electrode active material, that is, the decrease in the specific surface area can be suppressed by repeating charge and discharge.
以下、本発明を、その実施の形態によって説明する。 Hereinafter, the present invention will be described based on embodiments thereof.
本実施形態に係る鉛蓄電池を以下のように作製した。すなわち、キノン物質Aとして、化1に示したベンゾキノン、キノン物質Bとして化2に示したナフトキノン、キノン物質Cとして化3に示したアントラキノン、および前記キノン物質Cにアミノ基を導入した誘導体を重合させたキノンポリマーDを準備し、これらに化4に示した基本構造のリグニンを鉛粉に対して0.25質量%、硫酸バリウムを鉛粉に対して1.0質量%、活物質補強材としてのポリプロピレン樹脂の短繊維(平均長さ2〜5m)を鉛粉に対して0.03質量%添加し、鉛粉とともに混合した後、希硫酸と水を加えて練り合わせて負極活物質ペーストを調製した。前記鉛粉としては公知の方法で作製したものを用いた。このように調製した負極活物質ペーストは、キノン物質A、B、CおよびキノンポリマーDを、鉛粉に対して、それぞれ0.01質量%、0.02質量%、0.03質量%、0.04質量%および0.05質量%の5種類として、20種類準備した。同様に、前記鉛粉、リグニン、硫酸バリウムおよび活物質補強材のみで従来の負極活物質ペーストを調製して準備した。 The lead storage battery according to the present embodiment was produced as follows. Specifically, benzoquinone shown in Chemical Formula 1 as quinone substance A, naphthoquinone shown in Chemical formula 2 as quinone substance B, anthraquinone shown in Chemical formula 3 as quinone substance C, and a derivative in which an amino group is introduced into quinone substance C are polymerized. Quinone polymer D prepared, lignin having the basic structure shown in Chemical Formula 4 is 0.25% by mass with respect to the lead powder, barium sulfate is 1.0% by mass with respect to the lead powder, and an active material reinforcing material After adding 0.03% by mass of polypropylene fiber short fibers (average length of 2 to 5 m) to the lead powder and mixing with the lead powder, the mixture is mixed with dilute sulfuric acid and water, and the negative electrode active material paste is prepared. Prepared. As the lead powder, a powder prepared by a known method was used. In the negative electrode active material paste thus prepared, the quinone substances A, B, C and the quinone polymer D are each 0.01% by mass, 0.02% by mass, 0.03% by mass, 0% with respect to the lead powder. 20 types were prepared as five types of 0.04 mass% and 0.05 mass%. Similarly, a conventional negative electrode active material paste was prepared and prepared using only the lead powder, lignin, barium sulfate and the active material reinforcing material.
次に、上記した各負極活物質ペーストを、Pb−0.07重量%Ca−1.5重量%Sn合金から製造したエキスパンド格子体に充填し、熟成、乾燥して未化成の負極板を作成した。そして、この未化成の負極板を4枚、公知の方法で作製した未化成のペースト式正極板を3枚準備し、正、負極板間にポリエチレンからなるセパレータを介在させて積層して極板群とした。そして、各極板群をポリプロピレン製の電槽内に配置し、電槽内に20℃の比重が1.28の希硫酸からなる電解液を注液し、公知の条件で電槽化成を行って本発明に係る鉛蓄電池a、b、cおよびdと従来例の鉛蓄電池を5個ずつ完成させた。このようにして得られた鉛蓄電池は、公称容量が27Ah、正極板の寸法が縦115mm、横103mm、厚さ1.5mmであった。なお、本発明に係る鉛蓄電池a、b、cおよびdは、各々前述したキノン物質A、B、CおよびキノンポリマーDを負極活物質ペースト中に含むものに対応している。 Next, each of the negative electrode active material pastes described above is filled in an expanded lattice produced from a Pb-0.07 wt% Ca-1.5 wt% Sn alloy, and aged and dried to produce an unformed negative electrode plate. did. Then, four unformed negative electrode plates and three unformed paste type positive electrode plates prepared by a known method are prepared, and laminated with a separator made of polyethylene interposed between the positive and negative electrode plates. Grouped. Each electrode plate group is placed in a polypropylene battery case, and an electrolytic solution made of dilute sulfuric acid having a specific gravity of 1.28 at 20 ° C. is poured into the battery case, and the battery case is formed under known conditions. The lead storage batteries a, b, c and d according to the present invention and five conventional lead storage batteries were completed. The lead storage battery thus obtained had a nominal capacity of 27 Ah, a positive electrode plate dimension of 115 mm in length, 103 mm in width, and 1.5 mm in thickness. The lead storage batteries a, b, c and d according to the present invention correspond to those containing the quinone substances A, B, C and quinone polymer D in the negative electrode active material paste, respectively.
次に、前述した本発明に係る鉛蓄電池および従来例の鉛蓄電池をサイクル寿命試験に供し、各キノン物質A、B、CおよびキノンポリマーDの添加量とサイクル寿命数との関係を図1に示す。なお、試験条件は、25℃の周囲温度下で、25Aの定電流で4分間の放電を行った後、14.4Vの定電圧で最大充電電流を25Aとして10分間の充電を行い、その後、272Aの定電流で判定放電を行い、30秒目の電圧が7.2Vを下回ったところを寿命とした。図1は、このようにして寿命に至るまでに反復できたサイクル数の最高値を、従来例の鉛蓄電池で反復できたサイクル数の最高値を100として示している。 Next, the lead storage battery according to the present invention described above and the lead storage battery of the conventional example are subjected to a cycle life test, and the relationship between the amount of each quinone substance A, B, C and quinone polymer D added and the number of cycle lives is shown in FIG. Show. The test conditions were as follows: discharge at a constant current of 25 A for 4 minutes at an ambient temperature of 25 ° C., then charge at a constant voltage of 14.4 V for 10 minutes with a maximum charge current of 25 A, and then Judgment discharge was performed at a constant current of 272 A, and the lifetime was determined when the voltage at 30 seconds was lower than 7.2 V. FIG. 1 shows the maximum value of the number of cycles that can be repeated until the end of the life in this way, and the maximum value of the number of cycles that can be repeated in the conventional lead-acid battery as 100.
図1の結果より、本発明の鉛蓄電池は、各キノン物質A、B、CおよびキノンポリマーDの添加量が0.01質量%以上、0.03質量%以下にするのが好ましい、と言える。なお、キノン物質を添加した場合とキノンポリマーを添加した場合との作用効果上の差異としてはキノン構造のC=O部の多少によることが考えられる。 From the results of FIG. 1, it can be said that the lead storage battery of the present invention preferably has an addition amount of each quinone substance A, B, C and quinone polymer D of 0.01 mass% or more and 0.03 mass% or less. . In addition, it is considered that the difference in action and effect between the case where the quinone substance is added and the case where the quinone polymer is added is due to some of the C═O part of the quinone structure.
次に、上記したサイクル寿命試験の終了後、すべての電池を解体し、それぞれの負極板で、BET法によって負極活物質の比表面積を分析し、結果を表1に示す。なお、表1は従来例の鉛蓄電池における比表面積の最高値を100として示している。 Next, after the above cycle life test was completed, all the batteries were disassembled, and the specific surface area of the negative electrode active material was analyzed by the BET method with each negative electrode plate. The results are shown in Table 1. Table 1 shows the maximum specific surface area of the conventional lead-acid battery as 100.
表1の結果より、従来例の鉛蓄電池における負極板の比表面積に対し、本発明に係る鉛蓄電池における負極板の比表面積は大きくなっていることがわかる。このことから、キノン物質やキノンポリマーの添加によって、負極活物質の収縮が抑制され、比表面積の低下が抑制されている、と言える。 From the results in Table 1, it can be seen that the specific surface area of the negative electrode plate in the lead storage battery according to the present invention is larger than the specific surface area of the negative electrode plate in the conventional lead storage battery. From this, it can be said that the addition of the quinone substance or the quinone polymer suppresses the shrinkage of the negative electrode active material and suppresses the decrease in the specific surface area.
上記したキノン物質A、B、Cは官能基や側鎖をもたない基本的なキノン類であったが、アミノ基、クロロ基あるいはアルキル基が導入された誘導体であってもよい。たとえば、ナフトキノンの誘導体としてはフィロキノン、メナキノン、メナジオンなどのビタミンK類があり、ベンゾキノンの誘導体としてはプラストキノンがあり、アントラキノンの誘導体としてはアミノジヒドロキシアントラキノンがあり、いずれも上記したキノン物質A、BおよびCと同様に使用できる。これらのことは、キノンポリマーDについても同様である。 The quinone substances A, B, and C described above are basic quinones having no functional group or side chain, but may be a derivative into which an amino group, a chloro group, or an alkyl group is introduced. For example, naphthoquinone derivatives include vitamin Ks such as phylloquinone, menaquinone, and menadione, benzoquinone derivatives include plastoquinone, and anthraquinone derivatives include aminodihydroxyanthraquinone. And C can be used. The same applies to the quinone polymer D.
また、上記した実施形態では、キノン物質CのキノンポリマーDについてのみ説明したが、キノン物質A、Bのキノンポリマーであっても、キノンポリマーDと同様の構造であることから、実質的に同様の効果が得られるものと考えられる。 In the above-described embodiment, only the quinone polymer D of the quinone substance C has been described. However, since the quinone polymers of the quinone substances A and B have the same structure as the quinone polymer D, they are substantially the same. It is thought that the effect of is obtained.
上記した実施形態は、自動車用電池等に用いられる液式鉛蓄電池についてのものであるが、コンシューマー用や据置用に用いられる制御弁式鉛蓄電池についても同様の結果が得られた。すなわち、制御弁式鉛蓄電池として、2V、7Ahの電池について、65℃の周囲温度下でフロート充電寿命試験に供した後、解体して負極活物質の比表面積を分析したところ、従来例と比較して比表面積の低下が抑えられていることがわかった。このことから、制御弁式鉛蓄電池においても、キノン物質やキノンポリマーの添加によって、負極活物質の収縮が抑制されていることが考えられる。このように、本発明は、鉛蓄電池の種類や形式に関わらずに、その効果が発揮できるものであり、その試験方法も、実施形態以外の方法によってもよい。 Although the above-described embodiment is for a liquid type lead acid battery used for an automobile battery or the like, similar results were obtained for a control valve type lead acid battery used for consumer use or stationary use. That is, as a control valve type lead-acid battery, a 2V, 7Ah battery was subjected to a float charge life test at an ambient temperature of 65 ° C., then disassembled and analyzed for the specific surface area of the negative electrode active material. Thus, it was found that the decrease in specific surface area was suppressed. From this, also in the control valve type lead-acid battery, it is considered that the shrinkage of the negative electrode active material is suppressed by the addition of the quinone material or the quinone polymer. As described above, the present invention can exhibit the effect regardless of the type and form of the lead storage battery, and the test method may be a method other than the embodiment.
上述した如く、本発明は、負極活物質の収縮が抑制できる長寿命の鉛蓄電池を提供するのに寄与できるから、産業上の利用可能性が大である。 As described above, since the present invention can contribute to providing a long-life lead-acid battery capable of suppressing the shrinkage of the negative electrode active material, the industrial applicability is great.
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JP2006172921A (en) * | 2004-12-16 | 2006-06-29 | Osaka Univ | Lead acid storage battery and negative electrode and negative electrode active material used for it |
JPWO2014156511A1 (en) * | 2013-03-28 | 2017-02-16 | 国立大学法人東北大学 | Power storage device and electrode material thereof |
JPWO2020241882A1 (en) * | 2019-05-31 | 2020-12-03 | ||
WO2023200305A1 (en) * | 2022-04-15 | 2023-10-19 | 주식회사 엘지에너지솔루션 | Negative electrode and secondary battery comprising same |
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JPS62216169A (en) * | 1986-01-15 | 1987-09-22 | ユナイテッド キングドム アトミック エナ↓−ヂイ オ↓−ソリテイ | Electrochemical battery |
JP2000340233A (en) * | 1999-05-26 | 2000-12-08 | Tokai Carbon Co Ltd | Additive for led-acid battery |
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JPS55155476A (en) * | 1979-05-23 | 1980-12-03 | Dn Khim T | Enclosed leaddacid storage battery |
JPS62216169A (en) * | 1986-01-15 | 1987-09-22 | ユナイテッド キングドム アトミック エナ↓−ヂイ オ↓−ソリテイ | Electrochemical battery |
JP2000340233A (en) * | 1999-05-26 | 2000-12-08 | Tokai Carbon Co Ltd | Additive for led-acid battery |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2006172921A (en) * | 2004-12-16 | 2006-06-29 | Osaka Univ | Lead acid storage battery and negative electrode and negative electrode active material used for it |
JPWO2014156511A1 (en) * | 2013-03-28 | 2017-02-16 | 国立大学法人東北大学 | Power storage device and electrode material thereof |
KR101834623B1 (en) | 2013-03-28 | 2018-03-05 | 도호쿠 다이가쿠 | Electricity storage device and electrode material therefor |
JPWO2020241882A1 (en) * | 2019-05-31 | 2020-12-03 | ||
JP7173322B2 (en) | 2019-05-31 | 2022-11-16 | 株式会社Gsユアサ | lead acid battery |
WO2023200305A1 (en) * | 2022-04-15 | 2023-10-19 | 주식회사 엘지에너지솔루션 | Negative electrode and secondary battery comprising same |
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