JP2005347051A - Lead acid storage battery and its manufacturing method - Google Patents

Lead acid storage battery and its manufacturing method Download PDF

Info

Publication number
JP2005347051A
JP2005347051A JP2004164082A JP2004164082A JP2005347051A JP 2005347051 A JP2005347051 A JP 2005347051A JP 2004164082 A JP2004164082 A JP 2004164082A JP 2004164082 A JP2004164082 A JP 2004164082A JP 2005347051 A JP2005347051 A JP 2005347051A
Authority
JP
Japan
Prior art keywords
lead
paste
lignin
negative electrode
active material
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.)
Pending
Application number
JP2004164082A
Other languages
Japanese (ja)
Inventor
Mineki Fukuda
峰樹 福田
Tomonori Takebe
智紀 武部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Shin Kobe Electric Machinery Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shin Kobe Electric Machinery Co Ltd filed Critical Shin Kobe Electric Machinery Co Ltd
Priority to JP2004164082A priority Critical patent/JP2005347051A/en
Publication of JP2005347051A publication Critical patent/JP2005347051A/en
Pending legal-status Critical Current

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

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To prolong the lifetime of a lead acid storage battery which uses a paste type negative electrode plate that is manufactured by filling a paste-like negative electrode active material into a current collector made of lead-calcium alloy. <P>SOLUTION: Fiber of synthetic resin having a hollow structure is immersed into a saturated water solution of lignin and dried, and a hollow synthetic resin fiber impregnated with lignin is manufactured. Dilute sulfuric acid and a proper quantity of water are added into a mixture of lead powder made mainly of lead monoxide, lignin powder, the hollow synthetic resin fiber impregnated with lignin, barium sulfate powder, and cut fiber, and by kneading, a paste-like active material is formed. The paste-like active material for negative electrode formed is filled in a current collector made of lead-calcium alloy, and matured and dried, thereby a paste type negative electrode plate of no-formation is manufactured. By combining the paste type negative electrode plate manufactured and a paste type positive electrode plate used conventionally, a lead acid storage battery is manufactured. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、鉛蓄電池及びその製造方法に関するものである。   The present invention relates to a lead storage battery and a method for manufacturing the same.

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に、無停電電源装置や自動車用のバッテリーなどに広く使用がされている。最近、これらに用いられる鉛蓄電池の長寿命化が強く要求されている。   Lead storage batteries are widely used in uninterruptible power supply devices and automobile batteries because they have the feature of being inexpensive and highly reliable. Recently, there is a strong demand for extending the life of lead-acid batteries used in these.

鉛蓄電池用の電極としては、鉛粉や希硫酸を主成分とするペースト状活物質を、鉛合金製の集電体に充填して作成をするペースト式正極板やペースト式負極板が一般的に使用されている。ここで、鉛蓄電池の寿命要因の一つとして、ペースト式負極板の負極活物質の粗大化現象がある。なお、負極活物質の粗大化を抑制させる手法としては、ペースト式負極板の活物質中に、粉末状の硫酸バリウムやリグニンなどを添加する手法が一般的に行われている（例えば、特許文献１参照。）。   As a lead-acid battery electrode, a paste-type positive electrode plate or a paste-type negative electrode plate that is prepared by filling a lead alloy current collector with a pasty active material mainly composed of lead powder or dilute sulfuric acid is common. Is used. Here, as one of the life factors of the lead storage battery, there is a coarsening phenomenon of the negative electrode active material of the paste type negative electrode plate. As a technique for suppressing the coarsening of the negative electrode active material, a technique of adding powdered barium sulfate, lignin, or the like to the active material of the paste-type negative electrode plate is generally performed (for example, patent document). 1).

特願２００３−１１６８２２号Japanese Patent Application No. 2003-116822

しかしながら、従来使用されていたように、溶解性のある粉末状のリグニンを、鉛粉を主成分とする負極用のペースト状活物質に添加する手法は、以下に示すような問題点があった。すなわち、長期間にわたる鉛蓄電池の使用中において、負極活物質中のリグニンが電解液中に溶解する。その結果、負極活物質が粗大化する現象を十分に抑制することが難しいという問題点である。   However, as conventionally used, the method of adding soluble powdered lignin to the negative electrode paste active material mainly composed of lead powder has the following problems. . That is, lignin in the negative electrode active material dissolves in the electrolyte during use of the lead storage battery for a long period of time. As a result, it is difficult to sufficiently suppress the phenomenon that the negative electrode active material becomes coarse.

本発明は上記した課題を解決するものであり、負極用のペースト状活物質に添加するリグニンの仕様を改良することによって、長寿命な鉛蓄電池を提供することである。   This invention solves the above-mentioned subject, and is providing the long life lead acid battery by improving the specification of the lignin added to the paste-form active material for negative electrodes.

上記した課題を解決するために、本発明に係わる鉛蓄電池の負極活物質中には、従来から使用されている粉末状のリグニンに加えて、リグニンが含浸されている中空の合成樹脂繊維（以下において、リグニン含浸中空合成樹脂繊維と呼ぶ。）とを含有するものである。そして、粉末状のリグニンが溶解した後においても、リグニン含浸中空合成樹脂繊維から、徐々に負極活物質中にリグニンが供給されるようにしたものである。   In order to solve the above-mentioned problems, in the negative electrode active material of the lead storage battery according to the present invention, a hollow synthetic resin fiber impregnated with lignin in addition to the powdered lignin conventionally used (hereinafter referred to as the lignin) In this case, it is called a lignin-impregnated hollow synthetic resin fiber). Even after the powdered lignin is dissolved, the lignin is gradually supplied into the negative electrode active material from the lignin-impregnated hollow synthetic resin fiber.

すなわち、請求項１の発明は、鉛粉を主成分とするペースト状活物質を、鉛合金製の集電体に充填して作製をするペースト式負極板を用いる鉛蓄電池において、
前記ペースト状活物質は、リグニン粉末とリグニン含浸中空合成樹脂繊維を含有することを特徴とするものである。 That is, the invention of claim 1 is a lead storage battery using a paste-type negative electrode plate prepared by filling a paste-form active material mainly composed of lead powder into a lead alloy current collector,
The pasty active material contains lignin powder and lignin-impregnated hollow synthetic resin fiber.

請求項２の発明は、鉛粉を主成分とするペースト状活物質を、鉛合金製の集電体に充填して作製をするペースト式負極板を用いる鉛蓄電池の製造方法において、
前記ペースト状活物質は、リグニン粉末とリグニン含浸中空合成樹脂繊維を添加し、混練して製造したものであることを特徴とするものである。 The invention of claim 2 is a method for producing a lead-acid battery using a paste-type negative electrode plate prepared by filling a paste-form active material mainly composed of lead powder into a lead alloy current collector,
The pasty active material is manufactured by adding lignin powder and lignin-impregnated hollow synthetic resin fiber and kneading them.

本発明の効果として、ペースト式負極板を用いた鉛蓄電池の長寿命化をすることができる。   As an effect of the present invention, the life of a lead-acid battery using a paste-type negative electrode plate can be extended.

以下に、本発明の実施をするための最良の形態について詳細に説明をする。   Hereinafter, the best mode for carrying out the present invention will be described in detail.

１．リグニン含浸中空合成樹脂繊維の製造
中空率が２０〜４５％である中空構造をした合成樹脂製の繊維（以下において、中空合成樹脂繊維と呼ぶ。）を用いる。リグニンの飽和水溶液中に、中空合成樹脂繊維を浸して、リグニン水溶液を中空部分に含浸し、５０〜７０℃の乾燥炉中で乾燥を行い、リグニン含浸中空合成樹脂繊維を製造する。 1. Production of lignin-impregnated hollow synthetic resin fiber A synthetic resin fiber having a hollow structure with a hollowness ratio of 20 to 45% (hereinafter referred to as hollow synthetic resin fiber) is used. A hollow synthetic resin fiber is immersed in a saturated aqueous solution of lignin, the hollow portion is impregnated with the aqueous solution of lignin, and dried in a drying furnace at 50 to 70 ° C. to produce a lignin-impregnated hollow synthetic resin fiber.

２．負極板用ペースト状活物質の作製
一酸化鉛を７０〜８０質量％含む鉛粉を３ｋｇ、該鉛粉に対して、リグニン粉末を０．２質量％、本発明に係わるリグニン含浸中空合成樹脂繊維を０．２質量％、硫酸バリウム粉末を０．５質量％添加して混合物を作製する。これらの混合物に、濃度が３５質量％の希硫酸を１７３ｍｌと、適量の水とを加えて混練して、負極用のペースト状活物質を作製する。 2. Production of Paste Active Material for Negative Electrode 3 kg of lead powder containing 70 to 80% by mass of lead monoxide, 0.2% by mass of lignin powder based on the lead powder, lignin-impregnated hollow synthetic resin fiber according to the present invention 0.2% by mass and 0.5% by mass of barium sulfate powder are added to prepare a mixture. To these mixtures, 173 ml of dilute sulfuric acid having a concentration of 35 mass% and an appropriate amount of water are added and kneaded to prepare a paste-like active material for a negative electrode.

そして、ＪＩＳ規格の針入度測定装置（離合社製）を用いて、それぞれの負極用のペースト状活物質について針入度の測定を行い、上記した水の添加量を調整することによって、負極用のペースト状活物質の針入度を８０〜１２０ｍｍ−１に調整をした。 Then, using a JIS standard penetration measuring device (manufactured by Kogaisha), the penetration of each paste-like active material for the negative electrode is measured, and the amount of water added as described above is adjusted. The penetration of the pasty active material for use was adjusted to 80 to 120 mm −1 .

３．制御弁式鉛蓄電池の作製
作製した負極用のペースト状活物質を、幅が１５０ｍｍ、長さが１１０ｍｍ、厚みが２．２ｍｍの鉛−カルシウム合金製の集電体に充填し、４０℃、湿度９８％の大気中で２４時間の熟成をし、７２時間乾燥をさせて未化成のペースト式負極板を作製した。一方、ペースト式正極板は、従来から使用されているものであり、幅が１５０ｍｍ、長さが１１０ｍｍ、厚みが４．２ｍｍの鉛−カルシウム合金製の集電体にペースト状活物質を充填し、熟成・乾燥をさせたものを用いた。 3. Preparation of a control valve type lead-acid battery The prepared paste-like active material for negative electrode was filled into a lead-calcium alloy current collector having a width of 150 mm, a length of 110 mm, and a thickness of 2.2 mm, and 40 ° C., humidity It was aged for 24 hours in 98% air and dried for 72 hours to produce an unformed paste type negative electrode plate. On the other hand, the paste type positive electrode plate is conventionally used, and a paste-form active material is filled in a current collector made of lead-calcium alloy having a width of 150 mm, a length of 110 mm, and a thickness of 4.2 mm. Aged and dried product was used.

作製したペースト式負極板が４枚と、従来から使用をしているペースト式正極板が３枚とを、ガラス繊維製のリテーナを介して積層・溶接をして極板群を組み立て、該極板群をＡＢＳ製の電槽に組み込み、濃度が３０質量％の希硫酸電解液を注液し、電解液比重が１．２８０となるように電槽化成をして、公称容量（１０時間率放電容量）が３８Ａｈ−２Ｖの制御弁式鉛蓄電池を作成した。   The prepared paste type negative electrode plates and the past paste type positive electrode plates used in the past are laminated and welded through a glass fiber retainer to assemble an electrode plate group. The plate group was assembled in an ABS battery case, a 30% by weight diluted sulfuric acid electrolyte solution was injected, and the battery case was formed so that the electrolyte specific gravity was 1.280, and the nominal capacity (10 hour rate) A control valve type lead-acid battery having a discharge capacity of 38 Ah-2V was prepared.

４．制御弁式鉛蓄電池の寿命試験
作製した制御弁式鉛蓄電池は、３８Ａで放電をして（１．０ＣＡ、２５℃、放電終止電圧：１．６Ｖ）、初期の放電容量を測定して異常がないことを確認する。そして、この制御弁式鉛蓄電池を６０℃、湿度３０％の恒温恒湿槽の中で、２．２３Ｖの定電圧充電をし、６０日毎に取り出して冷却して、初期と同様の条件で放電容量試験を行った。そして、放電容量が初期の放電容量の７０％を下回った時点を寿命と判断した。 4). Control valve type lead acid battery life test The produced control valve type lead acid battery was discharged at 38 A (1.0 CA, 25 ° C., final discharge voltage: 1.6 V), and the initial discharge capacity was measured to find anomalies. Make sure there is no. The control valve type lead-acid battery is charged at a constant voltage of 2.23 V in a constant temperature and humidity chamber of 60 ° C. and 30% humidity, taken out every 60 days, cooled, and discharged under the same conditions as the initial stage. A capacity test was performed. And the time when the discharge capacity was less than 70% of the initial discharge capacity was judged as the life.

以下に、本発明の実施例について詳細に説明する。
（実施例）
一酸化鉛を７０〜８０質量％含む鉛粉を３ｋｇ、該鉛粉に対して、リグニン粉末を０．２質量％、リグニン含浸中空合成樹脂繊維を０．２質量％、硫酸バリウム粉末を０．５質量％、カットファイバーを０．２質量％添加して混合物を作製する。これらの混合物に、濃度が３５質量％の希硫酸を１７３ｍｌ、適量の水とを加えて混練して、負極用のペースト状活物質を作製した。その他の制御弁式鉛蓄電池の作製条件や寿命試験条件は、上記したものである。
（比較例）
一酸化鉛を７０〜８０質量％含む鉛粉を３ｋｇ、該鉛粉に対して、リグニン粉末を０．２質量％、硫酸バリウム粉末を０．５質量％、カットファイバーを０．２質量％添加して混合物を作製する。これらの混合物に、濃度が３５質量％の希硫酸を１７３ｍｌ、適量の水とを加えて混練して、負極用のペースト状活物質を作製した。その他の制御弁式鉛蓄電池の作製条件や寿命試験条件は、上記したものである。 Hereinafter, examples of the present invention will be described in detail.
(Example)
3 kg of lead powder containing 70 to 80% by mass of lead monoxide, 0.2% by mass of lignin powder, 0.2% by mass of lignin-impregnated hollow synthetic resin fiber, and 0.1% of barium sulfate powder with respect to the lead powder. A mixture is prepared by adding 5% by mass and 0.2% by mass of cut fiber. To these mixtures, 173 ml of dilute sulfuric acid having a concentration of 35% by mass and an appropriate amount of water were added and kneaded to prepare a paste-like active material for a negative electrode. Other control valve type lead-acid storage battery manufacturing conditions and life test conditions are as described above.
(Comparative example)
3 kg of lead powder containing 70 to 80% by mass of lead monoxide, 0.2% by mass of lignin powder, 0.5% by mass of barium sulfate powder, and 0.2% by mass of cut fiber are added to the lead powder. To make a mixture. To these mixtures, 173 ml of dilute sulfuric acid having a concentration of 35% by mass and an appropriate amount of water were added and kneaded to prepare a paste-like active material for a negative electrode. Other control valve type lead-acid storage battery manufacturing conditions and life test conditions are as described above.

これらの２種類の負極用ペースト状活物質を用いた制御弁式鉛蓄電池について、上記した手法で寿命試験を行った結果を表１に示す。表１より、本発明に係わる負極用のペースト状活物質を用いると、制御弁式鉛蓄電池を長寿命化することができる。この理由としては、粉末状のリグニンが電解液中に溶解した後においても、リグニン含浸中空合成樹脂繊維から、徐々に負極活物質中にリグニンが供給されており、負極活物質の粗大化を抑制しているためと考えられる。   Table 1 shows the results of a life test performed on the control valve type lead-acid battery using these two types of paste active material for negative electrode by the above-described method. From Table 1, when the paste-form active material for negative electrodes according to the present invention is used, the life of the control valve type lead-acid battery can be extended. The reason for this is that even after the powdered lignin is dissolved in the electrolyte, the lignin is gradually supplied from the lignin-impregnated hollow synthetic resin fiber into the negative electrode active material, thereby suppressing the coarsening of the negative electrode active material. It is thought to be because.

上記した実施例では、本発明に係わるリグニン含浸中空合成樹脂繊維を制御弁式鉛蓄電池について用いた結果について示したが、液式の鉛蓄電池の負極板に用いた場合にも、ほぼ同様の効果が得られた。   In the above-described embodiment, the result of using the lignin-impregnated hollow synthetic resin fiber according to the present invention for the control valve type lead storage battery is shown, but the same effect can be obtained when it is used for the negative electrode plate of the liquid type lead storage battery. was gotten.

Figure 2005347051
Figure 2005347051

本発明は、負極用のペースト状活物質を鉛合金製の集電体に充填して製造するペースト式負極板を用いる鉛蓄電池に使用をすることができる。
INDUSTRIAL APPLICABILITY The present invention can be used for a lead storage battery using a paste-type negative electrode plate manufactured by filling a negative electrode paste active material into a lead alloy current collector.

Claims (2)

鉛粉を主成分とするペースト状活物質を、鉛合金製の集電体に充填して作製をするペースト式負極板を用いる鉛蓄電池において、
前記ペースト状活物質は、リグニン粉末とリグニン含浸中空合成樹脂繊維を含有することを特徴とする鉛蓄電池。 In a lead storage battery using a paste-type negative electrode plate made by filling a paste-form active material mainly composed of lead powder into a lead alloy current collector,
The said paste-form active material contains a lignin powder and a lignin impregnation hollow synthetic resin fiber, The lead acid battery characterized by the above-mentioned. 鉛粉を主成分とするペースト状活物質を、鉛合金製の集電体に充填して作製をするペースト式負極板を用いる鉛蓄電池の製造方法において、
前記ペースト状活物質は、リグニン粉末とリグニン含浸中空合成樹脂繊維を添加し、混練して製造したものであることを特徴とする鉛蓄電池の製造方法。 In a method for producing a lead-acid battery using a paste-type negative electrode plate made by filling a paste-form active material mainly composed of lead powder into a lead alloy current collector,
The paste-like active material is produced by adding and kneading lignin powder and lignin-impregnated hollow synthetic resin fiber, and producing a lead acid battery.
JP2004164082A 2004-06-02 2004-06-02 Lead acid storage battery and its manufacturing method Pending JP2005347051A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004164082A JP2005347051A (en) 2004-06-02 2004-06-02 Lead acid storage battery and its manufacturing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2004164082A JP2005347051A (en) 2004-06-02 2004-06-02 Lead acid storage battery and its manufacturing method

Publications (1)

Publication Number Publication Date
JP2005347051A true JP2005347051A (en) 2005-12-15

Family

ID=35499238

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2004164082A Pending JP2005347051A (en) 2004-06-02 2004-06-02 Lead acid storage battery and its manufacturing method

Country Status (1)

Country Link
JP (1) JP2005347051A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103219512A (en) * 2013-03-25 2013-07-24 超威电源有限公司 Deep circulation storage battery container formation diachylon
JP6388094B1 (en) * 2016-12-07 2018-09-12 日立化成株式会社 Lead acid battery
CN110085844A (en) * 2019-05-13 2019-08-02 超威电源有限公司 A kind of cell negative plate mixing paste and wherein component optimal proportion method of determining range

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103219512A (en) * 2013-03-25 2013-07-24 超威电源有限公司 Deep circulation storage battery container formation diachylon
JP6388094B1 (en) * 2016-12-07 2018-09-12 日立化成株式会社 Lead acid battery
CN110085844A (en) * 2019-05-13 2019-08-02 超威电源有限公司 A kind of cell negative plate mixing paste and wherein component optimal proportion method of determining range

Similar Documents

Publication Publication Date Title
KR101775363B1 (en) Manufacturing method of active material for lead-acid battery
JP2001229920A (en) Method of manufacturing sealed lead acid battery
JP2010192257A (en) Manufacturing method of lead-acid battery, and paste type negative electrode plate for lead-acid battery
JPWO2013122132A1 (en) Positive electrode plate for lead acid battery, method for producing the electrode plate, and lead acid battery using the positive electrode plate
JP2009187776A (en) Control valve type lead-acid storage battery
JP2005347051A (en) Lead acid storage battery and its manufacturing method
JP2002141066A (en) Control valve type lead acid battery
JP2000251896A (en) Lead-acid battery and its manufacture
JP2010102922A (en) Control valve type lead-acid battery
JP2016162612A (en) Control valve type lead storage battery
JP4984430B2 (en) Method for producing paste active material for negative electrode
JP6056454B2 (en) Lead acid battery
JP2005310688A (en) Control valve type lead storage battery
JP2007294124A (en) Manufacturing method of lead-acid battery
JP2002008644A (en) Production method of positive electrode plate for lead storage battery
JP2005322503A (en) Control-valve type lead-acid storage battery and its manufacturing method
JP2001210320A (en) Lead-acid storage battery and its manufacturing method
JP2004055309A (en) Manufacturing method of pasty active material for positive electrodes, and lead storage battery using it
JP5003171B2 (en) Manufacturing method of paste type positive electrode plate
JP2004055417A (en) Manufacturing method of pasty active material for positive electrode and lead storage battery using it
JP2006202584A (en) Lead-acid battery and its manufacturing method
JP2002042794A (en) Sealed lead-acid battery
JP2001085046A (en) Sealed lead-acid battery
JP2001185151A (en) Sealed lead acid battery
JP2005044703A (en) Manufacturing method of control valve type lead storage battery