JP3511949B2 - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JP3511949B2 JP3511949B2 JP20469899A JP20469899A JP3511949B2 JP 3511949 B2 JP3511949 B2 JP 3511949B2 JP 20469899 A JP20469899 A JP 20469899A JP 20469899 A JP20469899 A JP 20469899A JP 3511949 B2 JP3511949 B2 JP 3511949B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- active material
- lead
- paste
- acid battery
- 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.)
- Expired - Lifetime
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
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、密閉形鉛蓄電池に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealed lead-acid battery.
【０００２】[0002]
【従来の技術】密閉形鉛蓄電池は、安価で信頼性が高い
という特徴を有するため、非常用電源や無停電電源装置
などに広く使用されている。これらの密閉形鉛蓄電池に
は、ペースト式正極板とペースト式負極板との間にガラ
ス繊維製のリテーナに電解液を染み込ませて使用するリ
テーナ方式が主に採用されており、その軽量化が強く要
求されている。なお、密閉形鉛蓄電池を軽量化するに
は、正極板や負極板に用いられている鉛を構成材料とす
る活物質や集電体の重量を減らすことが有効である。2. Description of the Related Art Sealed lead-acid batteries are widely used for emergency power supplies and uninterruptible power supplies because of their features of low cost and high reliability. These sealed lead-acid batteries mainly use a retainer method that uses a glass fiber retainer soaked with an electrolyte between a paste-type positive electrode plate and a paste-type negative electrode plate to reduce the weight. Highly required. In order to reduce the weight of the sealed lead-acid battery, it is effective to reduce the weight of the active material and the current collector containing lead used for the positive electrode plate and the negative electrode plate.
【０００３】負極板に用いられている負極活物質量は、
正極活物質量に比べて過剰に充填するのが一般的であ
る。すなわち、従来は、負極活物質量を正極活物質量に
比べて過剰に充填しないと、充分な密閉形鉛蓄電池の放
電特性や、充電時におけるガス吸収性能が得られないと
いう問題点があった。The amount of the negative electrode active material used in the negative electrode plate is as follows:
It is common to charge more than the amount of the positive electrode active material. That is, conventionally, there has been a problem that unless the amount of the negative electrode active material is excessively filled as compared with the amount of the positive electrode active material, sufficient discharge characteristics of the sealed lead-acid battery and gas absorption performance at the time of charging cannot be obtained. .
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記した課題
を解決するものであり、密閉形鉛蓄電池の負極活物質量
を低減することによって、その充放電特性を低下させる
ことなく軽量化をすることである。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is intended to reduce the weight of a sealed lead-acid battery without deteriorating its charge / discharge characteristics by reducing the amount of a negative electrode active material. That is.
【０００５】[0005]
【課題を解決するための手段】上記した課題を解決する
ために、第一の発明では、鉛合金製の格子体にペースト
状活物質を充填して作製する未化成のペースト式負極板
を用い、電槽化成をして作成する密閉形鉛蓄電池におい
て、前記電槽化成後のペースト式負極板の活物質は、1
〜6μｍの細孔径の容積が0.01〜0.03ml/gであり、10μ
ｍ以上の細孔径の容積が0.02〜0.15ml/gであることを特
徴とし、第二の発明では、前記ペースト状活物質中の水
分量が、10.2〜12.0wt.%であることを特徴とし、第三の
発明では、前記未化成のペースト式負極板は、活物質中
の硫酸鉛量が12〜16wt.%であることを特徴としている。Means for Solving the Problems In order to solve the above-mentioned problems, the first invention uses an unformed paste-type negative electrode plate produced by filling a lead-like lattice with a paste-like active material. In a sealed lead-acid battery prepared by battery case formation, the active material of the paste type negative electrode plate after the battery case formation is 1
~ 6μm pore size volume is 0.01-0.03ml / g, 10μ
m or more, the volume of the pore diameter is 0.02 to 0.15 ml / g, and in the second invention, the water content in the pasty active material is 10.2 to 12.0 wt.%. The third invention is characterized in that the unformed paste-type negative electrode plate has an amount of lead sulfate in the active material of 12 to 16 wt.%.
【０００６】[0006]
【発明の実施の形態】以下に、本発明の実施の形態につ
いて説明する。
１．密閉形鉛蓄電池の作成w
140mm ラl65mm ラt2.5mmのPb-Ca-Sn合金製の格子体に、
後述する仕様の負極用ペースト状活物質を摺り切り充填
した後、40℃、相対湿度98%以上の環境で24h熟成後乾燥
して、未化成の負極板を作製する。Embodiments of the present invention will be described below. 1. Creation of sealed lead-acid battery w 140mm la l 65mm la t 2.5mm Pb-Ca-Sn alloy grid,
After the negative electrode paste active material having the specifications described below is cut and filled, it is aged for 24 hours in an environment of 40 ° C. and a relative humidity of 98% or more, and then dried to produce an unformed negative electrode plate.
【０００７】前記未化成負極板の活物質を取り出して重
量を測定する。前記活物質を粉砕し、硝酸と過酸化水素
水の混合溶液で溶解し、沈殿物である白色の硫酸鉛の粉
末をろ過する。このろ過物を、ろ紙と共に坩堝内に入れ
電気炉で焼成し、焼成後の粉末の重量を測定する方法で
硫酸鉛量を測定した。The active material of the unformed negative electrode plate is taken out and weighed. The active material is pulverized, dissolved in a mixed solution of nitric acid and hydrogen peroxide solution, and the precipitate of white lead sulfate powder is filtered. The filtrate was put in a crucible together with filter paper, fired in an electric furnace, and the amount of lead sulfate was measured by a method of measuring the weight of the fired powder.
【０００８】従来から使用しているペースト式正極板２
枚と、上記したペースト式負極板3枚とをガラス繊維製
の不織布よりなるリテーナを介して積層して電極群と
し、該電極群をＡＢＳ製の電槽に組み込み、電解液を注
入して電槽化成した後に、密閉して公称容量が2V-30Ah
の密閉形鉛蓄電池を作成する。[0008] Paste-type positive electrode plate 2 conventionally used
And the three paste-type negative electrode plates described above are laminated via a retainer made of a nonwoven fabric made of glass fiber to form an electrode group. The electrode group is incorporated in an ABS battery case, and an electrolyte is injected to inject an electrolyte. After forming the tank, it is sealed and the nominal capacity is 2V-30Ah
To create a sealed lead-acid battery.
【０００９】２．負極活物質の細孔径の測定
電槽化成後の密閉形鉛蓄電池を解体して負極活物質を取
り出して水洗し、60℃で48時間乾燥する。乾燥した負極
活物質の細孔径は、水銀圧入式のポロシメータ（AUTOPO
RE2-9220型、島津製作所（株）製）で測定した。測定さ
れた負極活物質の細孔径と細孔体積との関係を示す曲線
（一般にこの曲線は、積分型の細孔分布曲線と呼ばれて
いる）を用いて、1〜6μｍ及び10μｍ以上の細孔径につ
いて、単位重量当たりの容積(ml/g)を算出した。[0009] 2. Measurement of Pore Diameter of Negative Electrode Active Material After the formation of the battery case, the sealed lead-acid battery is disassembled, the negative electrode active material is taken out, washed with water, and dried at 60 ° C. for 48 hours. The pore size of the dried negative electrode active material is determined using a mercury intrusion porosimeter (AUTOPO
RE2-9220, manufactured by Shimadzu Corporation). Using a curve showing the relationship between the measured pore diameter and pore volume of the negative electrode active material (generally, this curve is called an integral pore distribution curve), the fineness of 1 to 6 μm and 10 μm or more is used. For the pore size, the volume per unit weight (ml / g) was calculated.
【００１０】３．負極活物質の利用率測定
電槽化成後の密閉形鉛蓄電池を解体して正極板及び負極
板を取り出し、該正極板２枚、負極板１枚を用いた、負
極板容量で規制される試験用セルを作製し、0.5Aで2時
間充電し、1Aで放電（終止電圧1.8V）して負極板の容量
を測定した。そして、負極板の活物質量から計算される
理論容量と、前記試験用セルの放電容量から活物質の利
用率を算出した。[0010] 3. Utilization rate measurement of negative electrode active material A sealed lead-acid battery after battery formation was disassembled, a positive electrode plate and a negative electrode plate were taken out, and a test using two positive electrode plates and one negative electrode plate, which was regulated by the negative electrode plate capacity. A cell was prepared, charged at 0.5 A for 2 hours, discharged at 1 A (final voltage 1.8 V), and the capacity of the negative electrode plate was measured. Then, the utilization rate of the active material was calculated from the theoretical capacity calculated from the amount of the active material of the negative electrode plate and the discharge capacity of the test cell.
【００１１】４．初期の放電容量及びトリクル電流測定
電槽化成後の密閉形鉛蓄電池は、周囲温度が25±2℃
で、0.1CA(3A)の定電流で終止電圧1.8V/セルまで放電し
て初期の放電時間を測定した。そして、65℃の恒温槽に
入れ、2.23Ｖ/セルの定電圧充電（制限電流：9A）を行
い、５日後におけるトリクル電流値を測定した。4. Initial discharge capacity and trickle current measurement Ambient temperature of sealed lead-acid battery after formation of battery case is 25 ± 2 ℃
Then, the battery was discharged to a final voltage of 1.8 V / cell at a constant current of 0.1 CA (3 A), and an initial discharge time was measured. Then, it was placed in a constant temperature bath at 65 ° C., charged at a constant voltage of 2.23 V / cell (limited current: 9 A), and the trickle current value after 5 days was measured.
【００１２】[0012]
【実施例】以下に本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００１３】（比較例１）一酸化鉛を主成分とする鉛粉
3kgと、前記鉛粉重量に対して硫酸バリウム0.5wt.%、リ
グニン0.2wt .%を混ぜ合わせた後、水300mlと濃度35wt.
%の希硫酸300mlとを加えて混練して負極用ペースト状活
物質を作製する。この負極用ペースト状活物質を用い
て、上記した手法で密閉形鉛蓄電池を作製して試験し
た。Comparative Example 1 Lead Powder Containing Lead Monoxide as a Main Component
3 kg, barium sulfate 0.5 wt.% And lignin 0.2 wt.% Based on the weight of the lead powder were mixed, and then 300 ml of water and a concentration of 35 wt.
Then, 300 ml of diluted sulfuric acid is added and kneaded to prepare a paste-like active material for a negative electrode. Using this paste active material for a negative electrode, a sealed lead-acid battery was produced by the above-described method and tested.
【００１４】（実施例１）一酸化鉛を主成分とする鉛粉
3kgと、前記鉛粉重量に対して硫酸バリウム0.5wt.%、リ
グニン0.2wt.%を混ぜ合わせた後、水250mlと濃度35wt.%
の希硫酸360mlとを加えて混練して負極用ペースト状活
物質を作製する。この負極用ペースト状活物質を用い
て、上記した手法で密閉形鉛蓄電池を作製して試験し
た。(Example 1) Lead powder containing lead monoxide as a main component
3 kg, barium sulfate 0.5 wt.% Based on the weight of the lead powder, lignin 0.2 wt.% After mixing, water 250 ml and concentration 35 wt.%
And 360 ml of diluted sulfuric acid is added and kneaded to prepare a paste-like active material for a negative electrode. Using this paste active material for a negative electrode, a sealed lead-acid battery was produced by the above-described method and tested.
【００１５】（実施例２）一酸化鉛を主成分とする鉛粉
3kgと、前記鉛粉重量に対して硫酸バリウム0.5wt.%、リ
グニン0.2wt .%を混ぜ合わせた後、水210mlと濃度35wt.
%の希硫酸420mlとを加えて混練して負極用ペースト状活
物質を作製する。この負極用ペースト状活物質を用い
て、上記した手法で密閉形鉛蓄電池を作製して試験し
た。(Example 2) Lead powder containing lead monoxide as a main component
After mixing 3 kg and barium sulfate 0.5 wt.% And lignin 0.2 wt.% With respect to the weight of the lead powder, 210 ml of water and a concentration of 35 wt.
Then, 420 ml of diluted sulfuric acid is added and kneaded to prepare a paste active material for a negative electrode. Using this paste active material for a negative electrode, a sealed lead-acid battery was produced by the above-described method and tested.
【００１６】（実施例３）一酸化鉛を主成分とする鉛粉
3kgと、前記鉛粉重量に対して硫酸バリウム0.5wt.%、リ
グニン0.2wt %を混ぜ合わせた後、水170mlと濃度35wt.%
の希硫酸470mlとを加えて混練して負極用ペースト状活
物質を作製する。この負極用ペースト状活物質を用い
て、上記した手法で密閉形鉛蓄電池を作製して試験し
た。(Example 3) Lead powder containing lead monoxide as a main component
3 kg, barium sulfate 0.5 wt.% Based on the weight of the lead powder, lignin 0.2 wt%, and then mixed with 170 ml of water and a concentration of 35 wt.%
And 470 ml of diluted sulfuric acid are added and kneaded to prepare a paste active material for a negative electrode. Using this paste active material for a negative electrode, a sealed lead-acid battery was produced by the above-described method and tested.
【００１７】（比較例２）一酸化鉛を主成分とする鉛粉
3kgと、前記鉛粉重量に対して硫酸バリウム0.5wt.%、リ
グニン0.2wt.%を混ぜ合わせた後、水100mlと濃度35wt.%
の希硫酸710mlとを加えて混練して負極用ペースト状活
物質を作製する。この負極用ペースト状活物質を用い
て、上記した手法で密閉形鉛蓄電池を作製して試験し
た。Comparative Example 2 Lead Powder Mainly Containing Lead Monoxide
3 kg, barium sulfate 0.5 wt.% Based on the weight of the lead powder, lignin 0.2 wt.%, And then mixed with 100 ml of water and a concentration of 35 wt.%
And 710 ml of diluted sulfuric acid, and kneaded to prepare a paste active material for a negative electrode. Using this paste active material for a negative electrode, a sealed lead-acid battery was produced by the above-described method and tested.
【００１８】表１より、負極用ペースト状活物質中の水
分量や、未化成負極板中の硫酸鉛量を増加させると、１
〜６μｍの細孔径の容積は減少し、10μｍ以上の細孔径
の容積は大きくなる傾向を示すとともに、１枚当たりの
負極板重量が軽量化することがわかる。一方、負極活物
質の利用率や放電容量は（実施例２）が最も高く、ピー
ク値を示している。すなわち、負極活物質を多孔質化し
すぎると導電性が失われるためと考えられる。また、ペ
ースト中の硫酸鉛量や水分量を増加させるとトリクル電
流が小さくなる傾向にあり、好ましい傾向を示してい
る。From Table 1, it can be seen that the water content in the paste active material for the negative electrode and the lead sulfate content in the unformed negative electrode plate were increased.
It can be seen that the volume of pore diameters of ６6 μm decreases, the volume of pore diameters of 10 μm or more tends to increase, and the weight of the negative electrode plate per sheet decreases. On the other hand, the utilization rate and the discharge capacity of the negative electrode active material (Example 2) are the highest and show peak values. That is, it is considered that the conductivity is lost if the anode active material is made too porous. In addition, when the amount of lead sulfate or the amount of water in the paste is increased, the trickle current tends to decrease, which is preferable.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【発明の効果】上述したように、本発明を用いることに
よって、密閉形鉛蓄電池の充放電特性を低下させること
なく負極活物質の重量を低減できる。したがって、負極
板の軽量化が達成できるとともに、活物質に使用する鉛
粉量も低減できるため低コスト化が可能になり、工業的
価値は非常に大きいものである。As described above, by using the present invention, the weight of the negative electrode active material can be reduced without lowering the charge / discharge characteristics of the sealed lead-acid battery. Therefore, the weight of the negative electrode plate can be reduced, and the amount of lead powder used for the active material can be reduced, so that the cost can be reduced, and the industrial value is extremely large.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平10−270028（ＪＰ，Ａ) 特開 平５−205732（ＪＰ，Ａ) 特開 平10−69900（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/14 H01M 4/62 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-10-270028 (JP, A) JP-A-5-205732 (JP, A) JP-A-10-69900 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01M 4/14 H01M 4/62
Claims (3)
填して作製する未化成のペースト式負極板を用い、電槽
化成をして作成する密閉形鉛蓄電池において、前記電槽
化成後のペースト式負極板の活物質は、1〜6μｍの細孔
径の容積が0.01〜0.03ml/gであり、10μｍ以上の細孔径
の容積が0.02〜0.15ml/gであることを特徴とする密閉形
鉛蓄電池。1. A sealed lead-acid battery produced by filling an unformed paste-type negative electrode plate prepared by filling a paste-like active material into a grid made of a lead alloy and forming a battery case, wherein the battery case formation is performed. The active material of the subsequent paste-type negative electrode plate is characterized in that the volume of the pore diameter of 1 to 6 μm is 0.01 to 0.03 ml / g, and the volume of the pore diameter of 10 μm or more is 0.02 to 0.15 ml / g. Sealed lead-acid battery.
〜12.0wt.%であることを特徴とする請求項１記載の密閉
形鉛蓄電池。2. The method according to claim 1, wherein the amount of water in the paste-like active material is 10.2.
2. The sealed lead-acid battery according to claim 1, wherein the content of the lead-acid battery is about 12.0 wt.
中の硫酸鉛量が12〜16wt.%であることを特徴とする請求
項１記載の密閉形鉛蓄電池。3. The sealed lead-acid battery according to claim 1, wherein the unformed paste-type negative electrode plate has an amount of lead sulfate in the active material of 12 to 16% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20469899A JP3511949B2 (en) | 1999-07-19 | 1999-07-19 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20469899A JP3511949B2 (en) | 1999-07-19 | 1999-07-19 | Sealed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001035485A JP2001035485A (en) | 2001-02-09 |
| JP3511949B2 true JP3511949B2 (en) | 2004-03-29 |
Family
ID=16494840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20469899A Expired - Lifetime JP3511949B2 (en) | 1999-07-19 | 1999-07-19 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3511949B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11367906B2 (en) | 2018-05-23 | 2022-06-21 | Gs Yuasa International Ltd. | Lead-acid battery |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4012790B2 (en) | 2002-09-06 | 2007-11-21 | 矢崎総業株式会社 | Power supply harness protector mounting structure |
| JP6176180B2 (en) | 2013-07-19 | 2017-08-09 | 株式会社Ｇｓユアサ | Liquid lead acid battery and idling stop vehicle using liquid lead acid battery |
| EP3525269B1 (en) * | 2016-10-07 | 2021-04-07 | Showa Denko Materials Co., Ltd. | Cladding tube, clad electrode, lead storage battery, production method for these, and electric car |
| CN111868979A (en) * | 2018-03-19 | 2020-10-30 | 株式会社杰士汤浅国际 | Lead-acid battery |
-
1999
- 1999-07-19 JP JP20469899A patent/JP3511949B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11367906B2 (en) | 2018-05-23 | 2022-06-21 | Gs Yuasa International Ltd. | Lead-acid battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001035485A (en) | 2001-02-09 |
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