JPH11329420A - Manufacture of lead-acid battery - Google Patents
Manufacture of lead-acid batteryInfo
- Publication number
- JPH11329420A JPH11329420A JP10129884A JP12988498A JPH11329420A JP H11329420 A JPH11329420 A JP H11329420A JP 10129884 A JP10129884 A JP 10129884A JP 12988498 A JP12988498 A JP 12988498A JP H11329420 A JPH11329420 A JP H11329420A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- active material
- sulfuric acid
- lignin
- negative electrode
- 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.)
- Granted
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
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分類】本発明は鉛蓄電池の製造方
法、特にペースト式極板を用いた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 method for manufacturing a lead storage battery, and more particularly to a lead storage battery using a paste type electrode plate.
【０００２】[0002]
【従来の技術】一般に、鉛蓄電池には鉛と鉛酸化物とか
らなる鉛粉と水と希硫酸を主成分とし、これにポリエス
テル樹脂等の合成樹脂の短繊維などを含有させた活物質
ペーストを鋳造格子や連続多孔体に充填し、必要に応じ
て極板の形状に切断し、熟成乾燥して極板とするペース
ト式極板が多用されている。この極板は、更にセパレー
タと組み合わされて極板群に構成され、電槽に組み込ま
れた後、希硫酸を加えて化成充電されることにより電池
としての機能することになる。2. Description of the Related Art In general, a lead-acid battery has an active material paste containing lead powder composed of lead and lead oxide, water and dilute sulfuric acid as main components, and containing short fibers of synthetic resin such as polyester resin. Is filled into a casting grid or a continuous porous body, cut into the shape of an electrode plate if necessary, and aged and dried to form an electrode plate. The electrode plate is further combined with a separator to form an electrode plate group. After being assembled in a battery case, the electrode plate is charged with formation by adding dilute sulfuric acid to function as a battery.
【０００３】このようなペ−スト式極板、特に負極板に
は、上記した原料のほかに硫酸バリウム、カーボン及び
リグニンなどの添加剤を活物質の収縮防止剤として添加
して作製される。そして、その製造方法は、先ず鉛粉中
に上記添加剤を加え、混合分散させた後、水および希硫
酸を添加し混練することにより活物質ペーストとし格子
に充填していた。これは、混練初期に添加剤を加えるこ
とにより、添加剤の分散性を良くし、均質なペーストを
作製するためである。[0003] Such a paste type electrode plate, particularly a negative electrode plate, is produced by adding additives such as barium sulfate, carbon and lignin as an active material shrinkage preventing agent in addition to the above-mentioned raw materials. In the production method, first, the above-mentioned additive is added to lead powder, mixed and dispersed, and then water and dilute sulfuric acid are added and kneaded to fill the grid as an active material paste. This is to improve the dispersibility of the additive and to prepare a uniform paste by adding the additive at the beginning of kneading.
【０００４】[0004]
【発明が解決しようとする課題】ところが、このように
作製した活物質ペーストを用いた鉛蓄電池は深い充放電
と定電圧充電からなる充放電サイクルをくり返すと寿命
が短くなる傾向があることがわかった。特にこの傾向
は、正負極格子体に鉛−カルシウム−錫系合金を使用し
た場合に顕著であることがわかった。However, a lead-acid battery using the active material paste thus produced tends to have a shorter life when repeated charge / discharge cycles consisting of deep charge / discharge and constant voltage charge are repeated. all right. In particular, it has been found that this tendency is remarkable when a lead-calcium-tin alloy is used for the positive and negative electrode lattices.
【０００５】本発明は上記課題を解決するものであり、
深い放電と定電圧充電をくり返した場合での鉛蓄電池の
サイクル寿命の低下を抑制することを目的とするもので
ある。[0005] The present invention is to solve the above problems,
It is an object of the present invention to suppress a decrease in the cycle life of a lead storage battery when deep discharge and constant voltage charging are repeated.
【０００６】[0006]
【課題を解決するための手段】本発明は上記目的を達成
するために、鉛酸化物粉末と希硫酸と少なくともリグニ
ンを含む添加物とを混練し活物質ペーストをつくる工程
と、この活物質ペーストを格子体に充填し極板をつくる
工程と、この極板を熟成乾燥する工程とを含み、活物質
ペーストをつくる工程において希硫酸の添加後にリグニ
ンを添加する構成の製造方法とするものである。According to the present invention, there is provided a process for kneading a lead oxide powder, dilute sulfuric acid and an additive containing at least lignin to form an active material paste. And a step of aging and drying this electrode plate in a lattice body, and adding lignin after addition of dilute sulfuric acid in the step of making an active material paste. .
【０００７】また、上記製造方法によって作成された極
板を鉛−カルシウム−錫系合金からなる格子体に充填し
た負極板を備えた構成とするものである。[0007] The present invention is also provided with a negative electrode plate in which the electrode plate prepared by the above manufacturing method is filled in a lattice made of a lead-calcium-tin alloy.
【０００８】[0008]
【発明の実施の形態】鉛蓄電池の活物質原料として鉛お
よび鉛酸化物の混合粉体（以下、鉛粉）に水を投入し混
練を行う。この混練は鉛粉と水とが均一に混合されるま
で行われる。この後、鉛粉と水との混練物に希硫酸を滴
下投入しながら混練を行う。この鉛粉と水および希硫酸
との混練物が均一に混練された時点で、リグニンを混練
物に添加し、負極用の活物質ペ−ストとするものであ
る。BEST MODE FOR CARRYING OUT THE INVENTION Water is charged into a mixed powder of lead and lead oxide (hereinafter referred to as "lead powder") as a raw material for an active material of a lead storage battery and kneaded. This kneading is performed until the lead powder and water are uniformly mixed. Thereafter, kneading is performed while dilute sulfuric acid is dropped into the kneaded product of lead powder and water. When the kneaded product of the lead powder, water and dilute sulfuric acid is uniformly kneaded, lignin is added to the kneaded product to form an active material paste for a negative electrode.
【０００９】ここで、鉛−カルシウム合金、鉛−カルシ
ウム−錫合金等の鉛−カルシウム系合金からなる正負極
格子を備えた鉛蓄電池において、本発明の寿命低下を抑
制する効果が特に顕著である。また、一般に負極活物質
用ペ−ストとして硫酸バリウム、カ−ボン、ポリエステ
ル樹脂等の合成繊維等を添加することが行われており、
これらの添加物を必要に応じて添加することが望まし
い。Here, in a lead-acid battery provided with a positive / negative electrode grid made of a lead-calcium alloy such as a lead-calcium alloy or a lead-calcium-tin alloy, the effect of suppressing the shortening of the life of the present invention is particularly remarkable. . In addition, barium sulfate, carbon, synthetic fibers such as polyester resin and the like are generally added as a paste for a negative electrode active material,
It is desirable to add these additives as needed.
【００１０】[0010]
【実施例】以下に実施例により本発明の実施形態を説明
する。本発明の実施例として、鉛粉１ｋｇおよびポリエ
ステル繊維２ｇに対して水１００ｃｍ3を添加し混合
し、次に比重１．５０の希硫酸５０ｃｍ3を徐々に滴下
し、加えながら混練し、ペースト状とした。その後、添
加剤として硫酸バリウム５ｇ，カーボン５ｇ，リグニン
３ｇを混ぜてペースト状とした。この場合、混練時間の
中でペーストの温度が６０℃以上にならないようにし
た。The embodiments of the present invention will be described below with reference to examples. As an example of the present invention, 100 cm 3 of water was added to 1 kg of lead powder and 2 g of polyester fiber, mixed, and then 50 cm 3 of dilute sulfuric acid having a specific gravity of 1.50 was gradually dropped, and kneaded while adding the mixture. And Thereafter, 5 g of barium sulfate, 5 g of carbon, and 3 g of lignin were mixed as additives to form a paste. In this case, the temperature of the paste was prevented from reaching 60 ° C. or more during the kneading time.
【００１１】次に従来例として、鉛粉１ｋｇに対してポ
リエステル繊維２ｇ，硫酸バリウム５ｇ，カーボン５
ｇ，リグニン３ｇの割合で混ぜ、十分に撹拌し混合した
後１００ｃｍ3の水を添加し更に混合した。その後、比
重１．５０の希硫酸５０ｃｍ3を徐々に滴下し加えなが
ら温度が６０℃以上にならないように混練しながらペー
スト状とした。Next, as a conventional example, 2 g of polyester fiber, 5 g of barium sulfate, and 5 g of carbon were added to 1 kg of lead powder.
g and lignin at a ratio of 3 g, sufficiently stirred and mixed, and then 100 cm 3 of water was added and further mixed. Thereafter, 50 cm 3 of dilute sulfuric acid having a specific gravity of 1.50 was gradually added dropwise, and kneaded so that the temperature did not rise to 60 ° C. or higher, to form a paste.
【００１２】これらのペーストを鉛−カルシウム−錫合
金からなるエキスパンド格子体に充填し熟成乾燥して負
極未化成板を得た。これら各負極板と、格子体にやはり
鉛−カルシウム−錫合金を用い定法により作製した正極
板とを用いて、セル当たり正極５枚／負極６枚からなる
５時間率公称容量４８Ａｈの鉛蓄電池を各６個づつ作製
した。These pastes were filled into an expanded lattice made of a lead-calcium-tin alloy, aged and dried to obtain an unformed negative electrode plate. Using each of these negative electrode plates and a positive electrode plate also produced by a conventional method using a lead-calcium-tin alloy for the lattice, a lead-acid battery having a nominal capacity of 48 Ah with 5 hour rate and 6 negative electrodes per cell was prepared. Six each were produced.
【００１３】これらの電池を環境温度４０℃にて次のよ
うな放電深度が４０％と非常に深くなるような放電およ
び定電圧充電をくり返す条件下で寿命試験を行い評価を
実施した。１サイクルの放電は２０Ａで１時間おこな
い、充電は１４．８Ｖ（最大電流２５Ａ）で２時間おこ
なった。評価は４０サイクル毎に３００Ａ放電し、３０
秒目の電圧を測定し、この３０秒目の電圧が７．２Ｖを
下回った時点を寿命とした。寿命試験の結果を表１に示
す。These batteries were subjected to a life test under the conditions of repeating the discharge and constant voltage charging at an environmental temperature of 40 ° C. at the following depth of discharge as extremely deep as 40%, and evaluated. One cycle of discharging was performed at 20 A for 1 hour, and charging was performed at 14.8 V (maximum current 25 A) for 2 hours. The evaluation was 300 A discharge every 40 cycles, and 30 discharges.
The voltage at the second was measured, and the point in time when the voltage at the 30 second became lower than 7.2 V was defined as the life. Table 1 shows the results of the life test.
【００１４】[0014]
【表１】 [Table 1]
【００１５】寿命特性は表１から明らかなように、本実
施例のほうが著しく良好であった。寿命試験後の電池分
解の結果、劣化原因はほとんどの電池が正極活物質の軟
化による格子からの脱落であった。この結果は上記の劣
化原因と一見全く関連がないような結果であるが、詳細
に調査すると従来例では寿命試験１サイクル毎に充電電
気量が放電電気量の１０４％であるのに対して本実施例
では１０７％と約３％ほど充電電気量が多く、その差の
繰り返しが正極活物質の軟化の進行を早め、寿命サイク
ルの違いとなって現れたものと考えられる。As is clear from Table 1, the life characteristics of this embodiment were significantly better. As a result of disassembly of the battery after the life test, the cause of the deterioration was that most of the batteries fell off the grid due to softening of the positive electrode active material. Although this result is apparently completely unrelated to the above-mentioned cause of deterioration, a detailed investigation reveals that in the conventional example, the amount of charged electricity is 104% of the amount of discharged electricity in each cycle of the life test. In the example, it is considered that the amount of charged electricity is as large as about 107% and about 3%, and the repetition of the difference hastened the progress of softening of the positive electrode active material, resulting in a difference in life cycle.
【００１６】充電電気量の違いは、有機化合物であるリ
グニンが最初から添加されていると、硫酸滴下時に硫酸
に直接接触することにより変成されるのに対し、硫酸滴
下後にリグニンを添加した場合、硫酸は既に鉛粉と反応
しペーストはアルカリ性領域の塩基性硫酸鉛になってお
り、硫酸滴下の直接の影響を受けないためと考えられ
る。[0016] The difference in the amount of charged electricity is that when lignin, which is an organic compound, is added from the beginning, it is denatured by direct contact with sulfuric acid when sulfuric acid is dropped, whereas when lignin is added after sulfuric acid is dropped, It is considered that sulfuric acid has already reacted with lead powder and the paste has become basic lead sulfate in the alkaline region, and is not directly affected by the dropping of sulfuric acid.
【００１７】なお、本実施例の負極用ペーストの効果は
正負極に鉛−カルシウム−錫合金を用いた場合に特に顕
著であるが、その原因が負極活物質中に存在する添加剤
（リグニン）の影響であることを考え合わせれば、その
他の合金系の組合せの電池でも効果が推定でき、この合
金系に限定されるものではない。The effect of the paste for a negative electrode of this embodiment is particularly remarkable when a lead-calcium-tin alloy is used for the positive and negative electrodes. The cause is an additive (lignin) present in the negative electrode active material. Considering the effect of the above, the effect can be estimated even with a battery of another combination of alloys, and the present invention is not limited to this alloy.
【００１８】[0018]
【発明の効果】以上のように本発明によれば、定電圧で
充電し深い放電をくり返す充放電を行っても、寿命特性
の劣化抑制を大きく向上させることができるものであ
る。As described above, according to the present invention, even when charge and discharge are repeated at a constant voltage and deep discharge is repeated, the suppression of deterioration of the life characteristics can be greatly improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石井 輝秋 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Teruaki Ishii 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (2)
ニンを含む添加物とを混練し活物質ペーストをつくる工
程と、この活物質ペーストを格子体に充填し極板をつく
る工程と、この極板を熟成乾燥する工程とを含む鉛蓄電
池の製造方法であって、活物質ペーストをつくる工程に
おいて希硫酸の添加後にリグニンを添加することを特徴
とする鉛蓄電池の製造方法。1. A step of kneading a lead oxide powder, diluted sulfuric acid and an additive containing at least lignin to form an active material paste, a step of filling the grid with the active material paste to form an electrode plate, and A method for producing a lead-acid battery, comprising the step of aging and drying a plate, wherein lignin is added after adding dilute sulfuric acid in the step of forming an active material paste.
用いられ、かつ負極には希硫酸の添加後にリグニンを添
加し混練した活物質ペーストが用いられたことを特徴と
する鉛蓄電池。2. A lead-acid battery wherein a lead-calcium alloy is used for a grid of an electrode plate and an active material paste obtained by adding lignin and kneading after adding dilute sulfuric acid is used for a negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12988498A JP4441934B2 (en) | 1998-05-13 | 1998-05-13 | Method for producing lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12988498A JP4441934B2 (en) | 1998-05-13 | 1998-05-13 | Method for producing lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11329420A true JPH11329420A (en) | 1999-11-30 |
| JP4441934B2 JP4441934B2 (en) | 2010-03-31 |
Family
ID=15020729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12988498A Expired - Fee Related JP4441934B2 (en) | 1998-05-13 | 1998-05-13 | Method for producing lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4441934B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331256C (en) * | 2005-03-11 | 2007-08-08 | 风帆股份有限公司 | High-temperature resistant accumulator positive electrode lead plaster and method for preparing same |
| WO2009052124A1 (en) * | 2007-10-19 | 2009-04-23 | Axion Power International, Inc. | Electrode with reduced resistance grid and hybrid energy storage device having same |
| US7881042B2 (en) | 2006-10-26 | 2011-02-01 | Axion Power International, Inc. | Cell assembly for an energy storage device with activated carbon electrodes |
| US8202653B2 (en) | 2006-10-23 | 2012-06-19 | Axion Power International, Inc. | Electrode with reduced resistance grid and hybrid energy storage device having same |
| US8347468B2 (en) | 2008-12-12 | 2013-01-08 | Axion Power International Inc. | Method of making a current collector |
-
1998
- 1998-05-13 JP JP12988498A patent/JP4441934B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331256C (en) * | 2005-03-11 | 2007-08-08 | 风帆股份有限公司 | High-temperature resistant accumulator positive electrode lead plaster and method for preparing same |
| US8202653B2 (en) | 2006-10-23 | 2012-06-19 | Axion Power International, Inc. | Electrode with reduced resistance grid and hybrid energy storage device having same |
| US7881042B2 (en) | 2006-10-26 | 2011-02-01 | Axion Power International, Inc. | Cell assembly for an energy storage device with activated carbon electrodes |
| WO2009052124A1 (en) * | 2007-10-19 | 2009-04-23 | Axion Power International, Inc. | Electrode with reduced resistance grid and hybrid energy storage device having same |
| KR101505230B1 (en) * | 2007-10-19 | 2015-03-23 | 액시온 파워 인터네셔널, 인크. | Electrode with reduced resistance grid and hybrid energy storage device having same |
| US8347468B2 (en) | 2008-12-12 | 2013-01-08 | Axion Power International Inc. | Method of making a current collector |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4441934B2 (en) | 2010-03-31 |
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