JP6411606B1 - Recycling method for sealed lead-acid battery - Google Patents
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
【課題】実用的に十分な回復率を容易に達成する。
【解決手段】劣化蓄電池の各セルごとに所定濃度の電解液を注入し、ベース電流と方形波のパルス電流とを重畳する充電電流により再生処理を施す。
【選択図】図１A practically sufficient recovery rate is easily achieved.
An electrolyte solution having a predetermined concentration is injected into each cell of a deteriorated storage battery, and a regeneration process is performed by a charging current that superimposes a base current and a square-wave pulse current.
[Selection] Figure 1
Description
この発明は、制御弁式鉛蓄電池などの密閉形鉛蓄電池を再生し、再使用するための密閉形鉛蓄電池の再生処理方法に関する。 The present invention relates to a method for regenerating a sealed lead-acid battery for regenerating and reusing a sealed lead-acid battery such as a control valve type lead-acid battery.
パルス電流を使用して劣化蓄電池を電気的に再生する再生処理方法が提案され、実用されている（特許文献１）。 A regeneration processing method for electrically regenerating a deteriorated storage battery using a pulse current has been proposed and put into practical use (Patent Document 1).
従来の再生処理方法は、たとえば直流のベース電流に方形波のパルス電流を重畳して充電電流とし、このような充電電流を利用して周期的に休止期間を挟みながら通電することにより、劣化した鉛蓄電池を効果的に再生することができる。なお、パルス電流は、ベース電流の数倍程度の波高値とし、パルス周波数１〜５kHz 程度、デューティ５０％未満に設定することが好ましい。 The conventional regeneration processing method has deteriorated, for example, by superimposing a square-wave pulse current on a DC base current to form a charging current, and using such charging current to energize periodically with a pause period between them. The lead acid battery can be effectively regenerated. The pulse current is preferably set to a crest value several times the base current, set to a pulse frequency of about 1 to 5 kHz and a duty of less than 50%.
かかる従来技術によるときは、劣化蓄電池が通常のベント形鉛蓄電池であるときはよいとしても、劣化蓄電池が制御弁式鉛蓄電池などの密閉形鉛蓄電池であるときは、再生処理後の電池容量が小さく、十分な回復率（定格容量に対する再生処理後の電池容量の割合をいう、以下同じ）が得られないという問題があった。 According to such prior art, even if the deteriorated storage battery is a normal bent lead acid battery, when the deteriorated storage battery is a sealed lead acid battery such as a control valve type lead acid battery, the battery capacity after regeneration processing is There was a problem that it was small and a sufficient recovery rate (the ratio of the battery capacity after regeneration treatment to the rated capacity, hereinafter the same) could not be obtained.
そこで、この発明の目的は、再生処理に先き立って各セルに所定濃度の電解液を注入することによって、実用的に十分な回復率を容易に達成することができる密閉形鉛蓄電池の再生処理方法を提供することにある。 Accordingly, an object of the present invention is to regenerate a sealed lead-acid battery that can easily achieve a practically sufficient recovery rate by injecting an electrolyte of a predetermined concentration into each cell prior to the regeneration process. It is to provide a processing method.
かかる目的を達成するためのこの発明の構成は、劣化蓄電池の各セルごとに劣化蓄電池の満充電相当の濃度の電解液を注入し、ベース電流と方形波のパルス電流とを重畳する充電電流により再生処理を施すことをその要旨とする。 In order to achieve this object, the configuration of the present invention uses a charging current that superimposes a base current and a square-wave pulse current by injecting an electrolyte solution at a concentration equivalent to the full charge of the deteriorated storage battery for each cell of the deteriorated storage battery. The gist is to apply the reproduction process.
また、電解液の注入から再生処理の開始までの間に所定の待ち時間を設けてもよく、電解液の注入に先き立って劣化蓄電池を放電させてもよい。 Further, a predetermined waiting time may be provided between the injection of the electrolytic solution and the start of the regeneration process, and the deteriorated storage battery may be discharged prior to the injection of the electrolytic solution.
かかる発明の構成によるときは、劣化蓄電池は、たとえば制御弁式鉛蓄電池であっても、回復率７０〜８０％以上の実用レベルをほぼ確実に達成することができる。なお、再生処理後の回復率は、非常用電源用の据置式の用途向けでは８０％以上、自動車や電気車などの一般用途向けでは７０％以上であれば、十分実用的である。また、電解液の注入量は、各セルごとに、電槽底部の突部（いわゆる「くら」）上に支持されている極板の下端部を浸す程度とするのがよい。 According to the configuration of the present invention, even if the deterioration storage battery is, for example, a control valve type lead storage battery, a practical level with a recovery rate of 70 to 80% or more can be almost certainly achieved. It should be noted that the recovery rate after the regeneration process is sufficiently practical if it is 80% or more for stationary applications for emergency power supplies and 70% or more for general applications such as automobiles and electric cars. Moreover, the injection amount of the electrolytic solution is preferably set so as to immerse the lower end portion of the electrode plate supported on the protruding portion (so-called “kura”) at the bottom of the battery case for each cell.
各セルに注入する電解液の濃度は、劣化蓄電池の満充電相当とするのがよく、鉛蓄電池については、比重１．２８０の稀硫酸を用いる。なお、精製水を注入したり、劣化蓄電池の５０％充電相当の濃度の電解液（比重１．２００の稀硫酸）を注入したりしても、いずれも約２０〜３０％前後程度の低い回復率しか実現できないことが少なくない。 The concentration of the electrolytic solution injected into each cell should be equivalent to the full charge of the deteriorated storage battery, and dilute sulfuric acid having a specific gravity of 1.280 is used for the lead storage battery. Even if purified water is injected or an electrolyte solution having a concentration equivalent to 50% charge of a deteriorated storage battery (diluted sulfuric acid having a specific gravity of 1.200) is injected, the recovery is as low as about 20 to 30%. Often, only the rate can be realized.
電解液の注入から所定の待ち時間が経過すると、電解液が極板上に浸潤し、その後の再生処理により回復率を向上させることができる。なお、このときの待ち時間は、約１時間程度で十分である。 When a predetermined waiting time elapses from the injection of the electrolytic solution, the electrolytic solution infiltrates on the electrode plate, and the recovery rate can be improved by a subsequent regeneration process. In addition, about 1 hour is sufficient for the waiting time at this time.
電解液の注入に先き立って劣化蓄電池を放電させることにより、極板上に局部的な過充電状態の部位が発生することを防止し、再生処理中に過大な温度上昇を生じたりする可能性を最小にすることができる。なお、このときの放電処理は、劣化蓄電池の端子電圧が放電終止電圧に低下するまで継続するものとする。 Discharge the degraded storage battery prior to injecting the electrolyte to prevent the occurrence of localized overcharged sites on the electrode plate, resulting in excessive temperature rise during the regeneration process Sex can be minimized. In addition, the discharge process at this time shall be continued until the terminal voltage of a deterioration storage battery falls to a discharge end voltage.
以下、図面を以って発明の実施の形態を説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
密閉形鉛蓄電池の再生処理方法は、たとえば図１のフローチャートに従って実施する。ただし、以下の説明において、劣化蓄電池は、(株)ＧＳユアサ製の制御弁式鉛蓄電池ＳＥＢ６５（定格電圧１２Ｖ、５時間率定格容量６５Ａｈ）を例示する。
The regeneration processing method for the sealed lead-acid battery is performed according to the flowchart of FIG. However, in the following description, the deterioration storage battery exemplifies a control valve type lead storage battery SEB65 (rated
劣化蓄電池は、まず、受入検査において、再生処理可能であるか否かを判定する（図１のステップ（１）、以下、単に（１）のように記す）。すなわち、劣化蓄電池は、電槽の割れや膨らみ、端子部の脱落・変形などがなく、内部抵抗値がたとえば３５ｍΩ未満のものを再生処理可能として選別し、それ以外は、再生処理不能として廃棄する。また、劣化蓄電池の端子電圧を併せて測定し、端子電圧が定格電圧１２Ｖ以上の劣化蓄電池を放電可能とみなし（２）、その電池を放電させる（３）。放電処理は、５時間率定格容量６５Ａｈの定格放電電流１３Ａ以下の適当な定電流により、端子電圧が放電終止電圧１０．２Ｖに低下するまで放電させる。 First, in the acceptance inspection, the deteriorated storage battery determines whether or not it can be regenerated (step (1) in FIG. 1, hereinafter simply referred to as (1)). In other words, deteriorated storage batteries are selected as those that are free from cracking and swelling of the battery case, dropout / deformation of the terminal part, and having an internal resistance value of, for example, less than 35 mΩ, and are discarded as those that cannot be recycled. . Further, the terminal voltage of the deteriorated storage battery is also measured, and the deteriorated storage battery having a terminal voltage of 12V or higher is regarded as dischargeable (2), and the battery is discharged (3). In the discharge treatment, discharging is performed until the terminal voltage is lowered to a discharge end voltage of 10.2 V with an appropriate constant current of a rated discharge current of 13 A or less with a 5-hour rate rated capacity of 65 Ah.
次に、劣化蓄電池の各セルごとに所定量の電解液を注入する（４）。電解液は、劣化蓄電池の満充電相当の濃度の比重１．２８０の稀硫酸とし、電槽底部の「くら」上の各極板の下端部を浸すように、たとえば各セルごとに４０ccを注入する。なお、電解液は、たとえば劣化蓄電池の制御弁の上端の排気栓を一時的に取り外して注入することができる。電解液を注入したら、各極板上に電解液を浸潤させるために、約１時間程度の待ち時間の経過を静止して待つ（５）。 Next, a predetermined amount of electrolyte is injected into each cell of the deteriorated storage battery (4). The electrolyte is dilute sulfuric acid with a specific gravity of 1.280, which is equivalent to the full charge of the deteriorated storage battery. For example, 40 cc is injected into each cell so as to immerse the lower end of each plate on the bottom of the battery case. To do. The electrolyte can be injected, for example, by temporarily removing the exhaust plug at the upper end of the control valve of the deteriorated storage battery. After injecting the electrolyte solution, in order to infiltrate the electrolyte solution on each electrode plate, the waiting time of about 1 hour is stopped and waited (5).
その後、再生処理を実施する（６）。再生処理は、特許第３７２３７９５号公報に開示されている手順に準じ、たとえば直流のベース電流５Ａと方形波のパルス電流２５Ａ（波高値）とを重畳して充電電流とする。ただし、パルス電流は、デューティ３０％、パルス周波数２kHz とし、充電電流は、５分間の充電期間ごとに１分間の休止期間を周期的に挟みながら、たとえば１０〜３０時間程度のあらかじめ定める設定時間だけ通電を続行する。なお、再生処理中に過大な温度上昇を示したり、所定の充電電流値が流れなくなったり、再生初期の端子電圧が異常に高いもの等は、処理を中止するものとする。 Thereafter, reproduction processing is performed (6). The regeneration process is performed in accordance with the procedure disclosed in Japanese Patent No. 3723895, for example, by superimposing a DC base current 5A and a square wave pulse current 25A (crest value) to obtain a charging current. However, the pulse current is set to a duty of 30% and the pulse frequency is 2 kHz, and the charging current is set for a predetermined set time of, for example, about 10 to 30 hours while periodically interposing a pause period of 1 minute every 5 minutes of charging period. Continue energization. It should be noted that the processing is stopped if the temperature rises excessively during the regeneration process, a predetermined charging current value stops flowing, or the terminal voltage at the initial stage of the regeneration is abnormally high.
再生処理が完了した劣化蓄電池は、通常の充電処理の後、容量試験により再生処理後の電池容量、回復率を確認する（７）。なお、電池容量、回復率は、たとえば定格放電電流１３Ａにより放電終止電圧１０．５Ｖまで放電させて確認するものとする。ただし、一般用途向けでは回復率７０％以上、非常用電源向けでは回復率８０％以上を再生合格品とする。そこで、再生合格品のみを満充電状態に仕上充電して（８）、出荷する。 After the regeneration process is completed, the deteriorated storage battery is confirmed by a capacity test after the normal charge process (7). The battery capacity and the recovery rate are confirmed by discharging to a final discharge voltage of 10.5 V with a rated discharge current 13A, for example. However, a recovery rate of 70% or more for general use and a recovery rate of 80% or more for emergency power supplies are acceptable. Therefore, only the products that have passed the regeneration are finished charged to a fully charged state (8) and shipped.
劣化蓄電池ＳＥＢ６５の再生処理結果データの一例を図２〜図４に示す。 An example of the regeneration process result data of the deteriorated storage battery SEB65 is shown in FIGS.
図２は、受入検査時の劣化蓄電池の内部抵抗値、端子電圧の実測データである。これらの劣化蓄電池は、いずれも再生処理可能であるが、放電不可であると判定された。 FIG. 2 shows measured data of the internal resistance value and terminal voltage of the deteriorated storage battery at the time of acceptance inspection. Any of these deteriorated storage batteries can be regenerated, but it was determined that they cannot be discharged.
図２の劣化蓄電池に対し、図１のステップ（４）〜（７）を適用したときの再生処理結果を図３に示す。これによれば、再生処理後の電池容量、回復率は、それぞれ５９．０〜７２．０Ａｈ（平均６５．６Ａｈ）、回復率９０．８〜１１０．８％（平均１００．９％）が達成されていることが分かる。なお、図３には、再生処理後の内部抵抗値、端子電圧が併せて表示されている。 FIG. 3 shows the result of the regeneration process when steps (4) to (7) in FIG. 1 are applied to the deteriorated storage battery in FIG. According to this, the battery capacity and the recovery rate after the regeneration processing are achieved 59.0-72.0 Ah (average 65.6 Ah) and recovery rate 90.8-110.8% (average 100.9%), respectively. You can see that. FIG. 3 also shows the internal resistance value and the terminal voltage after the regeneration process.
一方、図２の劣化蓄電池に対し、図１のステップ（４）、（５）を省略し、各セルごとに電解液を注入しない場合の再生処理結果を図４に示す。これによれば、再生処理後の回復率は、最良でも４０．０％（平均２６．７％）しか達成できなかった。 On the other hand, with respect to the deteriorated storage battery of FIG. 2, steps (4) and (5) of FIG. 1 are omitted, and the results of the regeneration process when the electrolyte is not injected into each cell are shown in FIG. According to this, the recovery rate after the regeneration process was only 40.0% (average 26.7%) at best.
なお、具体的なデータは省略するが、図１のステップ（４）において、各セルごとに精製水を注入したとき、５０％充電相当の比重１．２００の稀硫酸を注入したときの再生処理後の回復率は、それぞれ最良でも２５．２％（平均２０．７％）、３６．３％（平均３２．２％）であった。 Although specific data is omitted, in step (4) of FIG. 1, when purified water is injected into each cell, regeneration processing is performed when diluted sulfuric acid having a specific gravity of 1.200 equivalent to 50% charge is injected. The subsequent recovery rates were 25.2% (average 20.7%) and 36.3% (average 32.2%) at best.
以上によれば、劣化蓄電池の各セルごとに、劣化蓄電池の満充電相当の電解液を所定量注入することにより、再生処理後の電池容量、回復率を顕著に向上させ得ることが分かる。また、この発明は、ＳＥＢ６５以外の他の定格電圧、定格容量の制御弁式鉛蓄電池や、その他の密閉形鉛蓄電池に対しても適用可能である。 According to the above, it can be seen that the battery capacity and the recovery rate after the regeneration process can be remarkably improved by injecting a predetermined amount of an electrolyte corresponding to the full charge of the deteriorated storage battery for each cell of the deteriorated storage battery. The present invention can also be applied to control valve type lead-acid batteries of other rated voltage and rated capacity other than SEB65, and other sealed lead-acid batteries.
この発明は、再生処理用の充電電流を通電するに先き立って各セルごとに所定濃度の電解液を注入するだけで実用的に十分な回復率を容易に達成することができ、一般用途向け、非常用電源向けなどの任意の用途の密閉形鉛蓄電池に対し、広く好適に適用することができる。
特許出願人 株式会社 ＢＲＳ
The present invention can easily achieve a practically sufficient recovery rate by simply injecting a predetermined concentration of electrolyte into each cell prior to supplying a charging current for regeneration treatment. The present invention can be widely and suitably applied to sealed lead-acid batteries for arbitrary uses such as for power supplies and emergency power supplies.
Patent Applicant BRS Inc.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0193066A (en) * | 1987-10-02 | 1989-04-12 | Shin Kobe Electric Mach Co Ltd | Manufacture of sealed lead-acid battery |
| JP2000040537A (en) * | 1998-07-24 | 2000-02-08 | Tec:Kk | Recycling method for lead-acid battery |
| JP3723795B2 (en) * | 2002-10-08 | 2005-12-07 | 武次 西田 | Recycling method for lead acid battery |
| JP2008108511A (en) * | 2006-10-24 | 2008-05-08 | Kanji Hosokawa | Lead-acid battery electrolyte |
| JP2011233262A (en) * | 2010-04-23 | 2011-11-17 | Masstech Corp | Method of reproducing shield type lead-acid battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0193066A (en) * | 1987-10-02 | 1989-04-12 | Shin Kobe Electric Mach Co Ltd | Manufacture of sealed lead-acid battery |
| JP2000040537A (en) * | 1998-07-24 | 2000-02-08 | Tec:Kk | Recycling method for lead-acid battery |
| JP3723795B2 (en) * | 2002-10-08 | 2005-12-07 | 武次 西田 | Recycling method for lead acid battery |
| JP2008108511A (en) * | 2006-10-24 | 2008-05-08 | Kanji Hosokawa | Lead-acid battery electrolyte |
| JP2011233262A (en) * | 2010-04-23 | 2011-11-17 | Masstech Corp | Method of reproducing shield type lead-acid battery |
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