JP4798972B2 - Control valve type lead-acid battery for standby - Google Patents
Control valve type lead-acid battery for standby Download PDFInfo
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Description
本発明は、低温高率放電特性に優れ、かつスタンバイ使用における浮動充電電流が少なく正極格子が腐食し難い、長寿命のスタンバイ用制御弁式鉛蓄電池に関する。 The present invention relates to a long-life control valve type lead-acid battery for standby which is excellent in low-temperature high-rate discharge characteristics, has a small floating charging current in standby use and hardly corrodes a positive electrode grid.
従来のスタンバイ用制御弁式鉛蓄電池は、負極と正極の活物質の質量比（負／正）が０．９〜１．１、負極活物質の密度が４．１〜４．２ｇ／ｃｍ３であり、低温高率放電特性などの電池特性は優れるものの、非常用電源等のスタンバイ使用において浮動充電電流が流れ易く、この電流は一部が腐食電流となり、この腐食電流が多いときは正極格子の腐食が顕著になり電池寿命が低下した。この腐食による寿命低下を、正極格子を厚くして改善するのは原料コストおよびエネルギー密度の点で不利である。長寿命の密閉形鉛蓄電池として、ペースト式負極板の活物質中にカーボンまたはグラファイトを０．４〜４．０質量％含有させたものが提案されている（特許文献１）。 The conventional control valve type lead-acid battery for standby has a mass ratio (negative / positive) of the negative electrode to the positive electrode active material of 0.9 to 1.1, and the density of the negative electrode active material of 4.1 to 4.2 g / cm 3. Although the battery characteristics such as low-temperature high-rate discharge characteristics are excellent, floating charging current easily flows in standby use such as an emergency power supply. As a result, the battery life decreased. It is disadvantageous in terms of raw material cost and energy density to improve the life reduction due to corrosion by increasing the thickness of the positive electrode grid. As a long-life sealed lead-acid battery, 0.4 to 4 .4 of carbon or graphite is contained in the active material of the paste type negative electrode plate . One containing 0 % by mass has been proposed (Patent Document 1).
本発明は、低温高率放電特性に優れ、かつスタンバイ使用における浮動充電電流が少なく正極格子が腐食し難い、長寿命のスタンバイ用制御弁式鉛蓄電池の提供を目的とする。 It is an object of the present invention to provide a long-life standby control valve type lead-acid battery that is excellent in low-temperature high-rate discharge characteristics, has a small floating charging current in standby use, and does not corrode the positive grid.
請求項１記載発明は、負極活物質の密度が３．５〜４．０ｇ／ｃｍ ３ であり、負極活物質と正極活物質の質量比（負／正）が０．５０〜０．８０（ただし、０．７５〜０．８０を除く）であり、さらに負極活物質中にカーボンが０．１０質量％以下含有されていることを特徴とするスタンバイ用制御弁式鉛蓄電池である。 According to the first aspect of the present invention, the density of the negative electrode active material is 3.5 to 4.0 g / cm 3 , and the mass ratio (negative / positive) of the negative electrode active material to the positive electrode active material is 0.5 0 to 0.8. 0 (excluding 0.75-0.8 0), and that it is contained more carbon 0.1 0 wt% or less in the negative electrode active material in the standby control valve type lead-acid battery, characterized in is there.
本発明のスタンバイ用制御弁式鉛蓄電池は、負極活物質と正極活物質の質量比（負／正）を０．５０〜０．８０（ただし、０．７５〜０．８０を除く）に小さく規定したので、スタンバイ使用における浮動充電電流が減少して正極格子の腐食が防止され、長寿命である。また負極活物質の密度を３．５〜４．０ｇ／ｃｍ３と小さく規定したので負極活物質の利用率が高くなり、従って正極活物質量に対する負極活物質量を減らしても、低温高率放電特性は従来品と同等に維持される。また、前記負極活物質中にカーボンを、０．１質量％以下含有させることにより、さらに低温高率放電特性が向上する。 Standby for valve-regulated lead-acid battery of the present invention, the weight ratio of the negative electrode active material and the positive electrode active material (negative / positive) 0.5 0 to 0.8 0 (excluding 0.75-0.8 0 ), The floating charging current in standby use is reduced, corrosion of the positive grid is prevented, and the life is long. Further, since the density of the negative electrode active material is regulated to be as small as 3.5 to 4.0 g / cm 3 , the utilization factor of the negative electrode active material is increased. Therefore, even if the amount of the negative electrode active material relative to the amount of the positive electrode active material is reduced, Discharge characteristics are maintained at the same level as conventional products. Moreover, the low-temperature high-rate discharge characteristics are further improved by containing 0.1% by mass or less of carbon in the negative electrode active material.
本発明のスタンバイ用制御弁式鉛蓄電池では、スタンバイ使用における浮動充電電流が少ないので、正極格子の腐食が抑制される。従って正極格子を厚くする必要がなく、低コスト、高エネルギー密度が達成される。 In the control valve type lead storage battery for standby according to the present invention, the floating charging current in standby use is small, so that corrosion of the positive electrode grid is suppressed. Therefore, it is not necessary to increase the thickness of the positive electrode lattice, and low cost and high energy density are achieved.
請求項１記載発明は、負極活物質と正極活物質の質量比（負／正）を小さく規定することによりスタンバイ使用における浮動充電電流を減少させ、それにより正極格子の腐食を抑制し、前記質量比を小さく規定したことによる低温高率放電特性の低下は、負極活物質密度を低く規定して負極の活物質利用率を高めて抑制したスタンバイ用制御弁式鉛蓄電池である。また、前記負極活物質中にカーボンを含有させて導電性を高め低温高率放電特性を高めたスタンバイ用制御弁式鉛蓄電池である。 The invention according to claim 1 reduces the floating charging current in standby use by defining the mass ratio (negative / positive) of the negative electrode active material and the positive electrode active material to be small, thereby suppressing the corrosion of the positive electrode grid and the mass. The decrease in the low-temperature, high-rate discharge characteristics due to the specified ratio is a control valve type lead-acid battery for standby that suppresses the active material utilization rate of the negative electrode by lowering the negative electrode active material density. In addition, the negative electrode active material is a standby control valve type lead-acid battery in which carbon is contained in the negative electrode active material to increase conductivity and to improve low-temperature high-rate discharge characteristics.
本発明において、負極活物質と正極活物質の質量比（負／正）を０．５０〜０．８０（ただし、０．７５〜０．８０を除く）に規定する理由は、前記質量比が０．５０未満では低温高率放電特性が低下し、０．８０を超えると浮動充電電流が増加して正極格子が腐食し易くなるためである。 The reason for defining the in the present invention, the mass ratio of the negative electrode active material and the positive electrode active material (negative / positive) 0.5 0 to 0.8 0 (excluding 0.75-0.8 0), the the mass ratio is less than 0.5 0 reduces the low-temperature high-rate discharge characteristics is because the floating charge current exceeds 0.8 0 tends to positive grid corrodes to increase.
本発明において、負極活物質中に含有させるカーボンは負極の導電性を高めて、さらに低温高率放電特性を向上させる。ただし、前記カーボンの含有量を０．１質量％以下に規定する理由は、０．１０質量％を超えると浮動充電電流が増加して正極格子が腐食し易くなるためである。 In the present invention, the carbon contained in the negative electrode active material enhances the conductivity of the negative electrode and further improves the low-temperature high-rate discharge characteristics. However, the reason for defining the content of the carbon below 0.1 wt% is because floating charge current exceeds 0.1 0 wt% tends to positive grid corrodes to increase.
本発明において、前記カーボンの形状は粉状でも繊維状でもよい。また前記カーボンをグラファイトに代えても同様の効果が得られる。 In the present invention, the shape of the carbon may be powder or fiber. The same effect can be obtained even if the carbon is replaced with graphite.
本発明において、負極活物質の密度を３．５〜４．０ｇ／ｃｍ３に規定する理由は、負極活物質の密度が３．５ｇ／ｃｍ３未満では密度が低過ぎて活物質内の空孔が多くなり水素過電圧が下がり浮動充電電流が増加するためである。また４．０ｇ／ｃｍ３を超えると負極活物質の利用率が低下し十分な低温高率放電特性が得られないためである。 In the present invention, the density of the anode active material reasons specified in 3.5~4.0g / cm 3, the density of the negative electrode active material density is less than 3.5 g / cm 3 are low over assistant engineer the active material This is because the number of holes increases, the hydrogen overvoltage decreases, and the floating charging current increases. On the other hand , if it exceeds 4.0 g / cm 3 , the utilization factor of the negative electrode active material is lowered and sufficient low-temperature high-rate discharge characteristics cannot be obtained.
以下に本発明を実施例により具体的に説明する。
参考例１：Ｐｂ−Ｃａ−Ｓｎ合金の正極格子と負極格子にそれぞれペースト状正極活物質とカーボンを含有しないペースト状負極活物質を塗布充填し、４０℃、相対湿度９８％の大気中で２４時間熟成し、次いで２４時間乾燥させて未化成の正極板および負極板を作製した。前記ペースト状負極活物質中はカーボンを添加しないものを用いた。前記負極板の活物質密度、および負極板と正極板の活物質の質量比は本発明規定値内で種々に変化させた。
Hereinafter, the present invention will be described specifically by way of examples.
Reference Example 1: A positive electrode lattice and a negative electrode lattice of a Pb—Ca—Sn alloy were coated and filled with a paste-like positive electrode active material and a paste-like negative electrode active material not containing carbon , respectively. Aging was carried out for a period of time, followed by drying for 24 hours to produce an unformed positive electrode plate and negative electrode plate. The paste-like negative electrode active material in the using of no added carbon. The active material density of the negative electrode plate and the mass ratio of the active material of the negative electrode plate to the positive electrode plate were variously changed within the specified values of the present invention.
負極活物質密度と活物質の質量比（負／正）の組み合わせは、負極活物質密度が低いと利用率が向上し、正極に対する負極の活物質量は少なくなり、質量比（負／正）は小さくなるようにした。逆に、負極活物質密度が高いと利用率が低下し、正極に対する負極の活物質量は多くなり、質量比は大きくなるようにした。 The combination of the negative electrode active material density and the mass ratio (negative / positive) of the active material is improved when the negative electrode active material density is low, and the amount of the negative electrode active material with respect to the positive electrode is reduced, and the mass ratio (negative / positive). Was made smaller. On the contrary, when the negative electrode active material density is high, the utilization factor is reduced, the amount of the active material of the negative electrode with respect to the positive electrode is increased, and the mass ratio is increased.
次に、前記未化成の正極板３枚と負極板４枚をガラス繊維製のリテーナを介在させて交互に積層して極板群とし、これをＡＢＳ製電槽に組み込み、電槽内に比重１．２１（２０℃）の希硫酸を注入したのち、充電量２３０％、化成時間４８Ｈ、周囲温度２５℃の条件で電槽化成を行ってスタンバイ用制御弁式鉛蓄電池を製造した。 Next, the three unformed positive electrode plates and the four negative electrode plates are alternately laminated with a glass fiber retainer interposed therebetween to form an electrode plate group. After injecting 1.21 (20 ° C.) dilute sulfuric acid, the battery was formed under the conditions of a charge amount of 230%, a formation time of 48H, and an ambient temperature of 25 ° C. to produce a standby control valve type lead-acid battery.
得られたスタンバイ用制御弁式鉛蓄電池について、低温高率放電特性を−５℃の３ＣＡ放電容量により調べた。終止電圧は１．６Ｖ／セルとした。またスタンバイ使用における浮動充電電流（６０℃）を調べた。 About the obtained control valve type lead acid battery for standby, the low temperature high rate discharge characteristic was investigated by 3CA discharge capacity of -5 degreeC. The final voltage was 1.6 V / cell. Further, the floating charging current (60 ° C.) in standby use was examined.
実施例１：負極活物質中にカーボンを含有させた他は参考例１と同じ方法によりスタンバイ用制御弁式鉛蓄電池を製造し、参考例１と同じ調査を行った。 Example 1 A control valve lead storage battery for standby was manufactured in the same manner as in Reference Example 1 except that carbon was contained in the negative electrode active material, and the same investigation as in Reference Example 1 was performed.
従来例１：負極活物質密度および活物質の質量比（負／正）を従来のスタンバイ用制御弁式鉛蓄電池の範囲とした他は参考例１と同じ方法によりスタンバイ用制御弁式鉛蓄電池を製造し、参考例１と同じ調査を行った。 Conventional Example 1: negative electrode active material density and weight ratio of the active material (negative / positive) conventional except that a standby control valve-range lead-acid batteries for standby valve-regulated lead-acid battery in the same manner as in Reference Example 1 The same investigation as in Reference Example 1 was conducted.
比較例１：負極活物質密度および活物質の質量比（負／正）を共に本発明規定値外とした他は参考例１と同じ方法によりスタンバイ用制御弁式鉛蓄電池を製造し、参考例１と同じ調査を行った。 Comparative Example 1: Mass ratio of the negative electrode active material density and the active material (negative / positive) except that together with the present invention defined value outside the manufactures for standby valve-regulated lead-acid battery in the same manner as in Reference Example 1, Reference Example The same investigation as 1 was conducted.
比較例２：負極活物質密度および活物質の質量比（負／正）は本発明規定値内とし、カーボン含有量を本発明規定値外とした他は参考例１と同じ方法によりスタンバイ用制御弁式鉛蓄電池を製造し、参考例１と同じ調査を行った。 Comparative Example 2: Control for standby by the same method as in Reference Example 1 except that the negative electrode active material density and the mass ratio (negative / positive) of the active material are within the specified values of the present invention, and the carbon content is out of the specified values of the present invention. A valve-type lead-acid battery was manufactured, and the same investigation as in Reference Example 1 was performed.
比較例３：負極活物質密度を本発明規定値外とし、活物質の質量比（負／正）を本発明規定値内とした他は参考例１と同じ方法によりスタンバイ用制御弁式鉛蓄電池(Ｎｏ．１２、１３)を製造し、参考例１と同じ調査を行った。また、負極活物質密度を本発明規定値内とし、活物質の質量比（負／正）を本発明規定値外とした他は参考例１と同じ方法によりスタンバイ用制御弁式鉛蓄電池(Ｎｏ．１４、１５)を製造し、参考例１と同じ調査を行った。 Comparative Example 3: negative electrode active material density and the invention specified value outside the mass ratio of the active material (negative / positive) of the present invention except that the inside specified value for standby valve-regulated lead-acid battery in the same manner as in Reference Example 1 (Nos. 12, 13) were manufactured and the same investigation as in Reference Example 1 was performed. Further, the control valve type lead-acid storage battery for standby (No.) was prepared in the same manner as in Reference Example 1 except that the negative electrode active material density was within the specified value of the present invention and the mass ratio (negative / positive) of the active material was outside the specified value of the present invention. 14 and 15 ) and the same investigation as in Reference Example 1 was conducted.
参考例１、実施例１、従来例１、比較例１〜３の調査結果を表１に示した。３ＣＡ容量（−５℃）と浮動充電電流は従来例１のＮｏ．６を１００としたときの比率（％）で示した。 Table 1 shows the investigation results of Reference Example 1, Example 1, Conventional Example 1, and Comparative Examples 1 to 3. The 3CA capacity (−5 ° C.) and the floating charging current are No. It is shown as a ratio (%) where 6 is 100.
表１から明らかなように、参考例１のＮｏ．１〜３はいずれも従来例１に較べて、３ＣＡ（−５℃）容量が高く、かつ浮動充電電流が少なく正極格子の腐食が起き難いものであった。また、カーボンを適量含有する実施例１（本発明例）のＮｏ．４、５は３ＣＡ容量（−５℃）が大幅に向上した。 As is clear from Table 1 , No. 1 in Reference Example 1 was obtained . 1 to 3 were higher in 3CA (−5 ° C.) capacity than in Conventional Example 1, had a small floating charging current, and did not easily corrode the positive grid. Moreover, No. 1 of Example 1 (example of the present invention) containing an appropriate amount of carbon. In 4 and 5, the 3CA capacity (−5 ° C.) was greatly improved.
これに対し、比較例１のＮｏ．８は正極に対する負極活物質量が少ないため、３ＣＡ容量（−５℃）が低く、Ｎｏ．９は正極に対する負極活物質量が多いため、浮動充電電流が増加した。Ｎｏ．１０は負極活物質密度が高く、負極活物質量も少ないため、３ＣＡ容量（−５℃）が低下した。比較例２のＮｏ．１１は負極活物質のカーボン量が多いため、浮動充電電流が増加した。 On the other hand, No. 1 of Comparative Example 1 was used. Since No. 8 has a small amount of negative electrode active material relative to the positive electrode , the 3CA capacity (−5 ° C.) is low. 9 had a large amount of negative electrode active material relative to the positive electrode, and therefore the floating charging current increased. No. No. 10 had a high negative electrode active material density and a small amount of negative electrode active material, so the 3CA capacity (−5 ° C.) decreased. No. of Comparative Example 2 Since No. 11 had a large amount of carbon in the negative electrode active material , the floating charging current increased.
比較例３のＮｏ．１２は、３ＣＡ容量（−５℃）および浮動充電電流の効果が従来と比較して多少の改善が認められるが十分ではない。Ｎｏ．１３は負極活物質密度が高く利用率が低いため、３ＣＡ容量（−５℃）が低下した。Ｎｏ．１４は正極に対する負極活物質量が少ないため、３ＣＡ容量（−５℃）が低下した。Ｎｏ．１５は正極に対する負極活物質量が多いため、浮動充電電流が増加した。 No. of Comparative Example 3 12, the effect of the 3CA capacity (−5 ° C.) and the floating charging current is slightly improved as compared with the conventional case , but is not sufficient. No. Since No. 13 has a high negative electrode active material density and a low utilization factor , the 3CA capacity (−5 ° C.) decreased. No. Since 14 had a small amount of the negative electrode active material relative to the positive electrode , the 3CA capacity (−5 ° C.) decreased. No. No. 15 had a large amount of negative electrode active material relative to the positive electrode, and therefore the floating charging current increased.
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| JP5138391B2 (en) * | 2008-01-15 | 2013-02-06 | 古河電池株式会社 | Control valve type lead acid battery |
| JP5637503B2 (en) * | 2011-09-27 | 2014-12-10 | 株式会社Ｇｓユアサ | Lead acid battery |
| JP6597308B2 (en) * | 2013-11-29 | 2019-10-30 | 株式会社Ｇｓユアサ | Retainer type lead acid battery |
| CN104681879B (en) * | 2013-11-29 | 2020-07-10 | 株式会社杰士汤浅国际 | Lead-acid battery |
| JP5708959B2 (en) * | 2014-09-08 | 2015-04-30 | 株式会社Ｇｓユアサ | Lead acid battery |
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| CN107408702B (en) * | 2015-03-30 | 2020-07-14 | 株式会社杰士汤浅国际 | Lead-acid battery |
| JP6503869B2 (en) * | 2015-05-08 | 2019-04-24 | 日立化成株式会社 | Control valve type lead storage battery and method of manufacturing the same |
| JP6781365B2 (en) * | 2015-10-23 | 2020-11-04 | 昭和電工マテリアルズ株式会社 | Lead-acid battery |
| JP6830615B2 (en) * | 2019-07-10 | 2021-02-17 | 株式会社Ｇｓユアサ | Control valve type lead acid battery |
| JP6791326B2 (en) * | 2019-09-04 | 2020-11-25 | 昭和電工マテリアルズ株式会社 | Lead-acid battery |
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| CA1179013A (en) * | 1980-10-03 | 1984-12-04 | Purushothama Rao | Sealed, maintenance-free, lead-acid batteries for float applications |
| JPS57124866A (en) * | 1981-01-26 | 1982-08-03 | Matsushita Electric Ind Co Ltd | Closed type lead storage battery |
| JPH0244658A (en) * | 1988-08-04 | 1990-02-14 | Yuasa Battery Co Ltd | Sealed lead-acid battery |
| JPH04296464A (en) * | 1991-03-26 | 1992-10-20 | Shin Kobe Electric Mach Co Ltd | Sealed-type lead-acid battery |
| JPH07240227A (en) * | 1994-02-25 | 1995-09-12 | Shin Kobe Electric Mach Co Ltd | Sealed lead-acid battery |
| JPH08339819A (en) * | 1995-06-09 | 1996-12-24 | Matsushita Electric Ind Co Ltd | Sealed lead-acid battery |
| JPH09283147A (en) * | 1996-04-19 | 1997-10-31 | Yuasa Corp | Sealed lead-acid battery and manufacture thereof |
| JP2002042794A (en) * | 2000-07-27 | 2002-02-08 | Shin Kobe Electric Mach Co Ltd | Sealed lead-acid battery |
| JP2002343360A (en) * | 2001-05-15 | 2002-11-29 | Shin Kobe Electric Mach Co Ltd | Control valve type lead storage battery |
| JP4221963B2 (en) * | 2002-07-12 | 2009-02-12 | パナソニック株式会社 | Control valve type lead acid battery |
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