JPH0756811B2 - Sealed lead acid battery - Google Patents
Sealed lead acid batteryInfo
- Publication number
- JPH0756811B2 JPH0756811B2 JP60176027A JP17602785A JPH0756811B2 JP H0756811 B2 JPH0756811 B2 JP H0756811B2 JP 60176027 A JP60176027 A JP 60176027A JP 17602785 A JP17602785 A JP 17602785A JP H0756811 B2 JPH0756811 B2 JP H0756811B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- sealed lead
- electrode plate
- acid battery
- electrolytic solution
- 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 - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/342—Gastight lead accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
- H01M10/10—Immobilising of electrolyte
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は極板群内にゲル状希硫酸電解液を吸収・保持し
た陰極吸収式のペースト式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 cathode absorption type paste-type sealed lead acid battery in which a gelled dilute sulfuric acid electrolyte is absorbed and held in an electrode plate group.
従来の技術とその問題点 密閉形鉛蓄電池は、充電時に正極から発生する酸素ガス
を負極で吸収する機能を持ち、電解液の漏れがない等の
特徴を持って作製された完全密閉式の電池である。この
電池の基本構成は、液式の鉛蓄電池と同一であるが、上
述した特徴を付与するために電解液に特別の工夫が施さ
れている点が大きく異なっている。即ち、電池からの電
解液の漏れを防止するため、使用する電解液の量を極板
群内に含浸させられる程度に制限し、電槽内を自由に移
動する過剰量を存在させない方法によって電解液を保持
させている。Conventional technology and its problems The sealed lead-acid battery has a function of absorbing oxygen gas generated from the positive electrode at the time of charging at the negative electrode, and is a completely sealed battery made with features such as no electrolyte leakage. Is. The basic configuration of this battery is the same as that of the liquid lead-acid battery, but is greatly different in that the electrolytic solution is specially devised to impart the above-mentioned characteristics. That is, in order to prevent the leakage of the electrolytic solution from the battery, the amount of the electrolytic solution used is limited to such an extent that it can be impregnated in the electrode plate group, and the electrolytic method is performed by a method in which an excessive amount that freely moves in the battery case does not exist. Holds the liquid.
ところで、密閉形鉛電池は、充電時に発生する酸素ガス
を電池内部で吸収することによって、液式の鉛蓄電池の
ような充電中の電解液の減少を防止し、使用中の補水等
の保守の省力化を図った電池である。従って、酸素ガス
の吸収が不良であると、電解液が減少し、やがて蓄電池
の容量低下や寿命低下につながる恐れがあり、電解液の
漏れを防ぐと共に、酸素ガスの吸収能力を高めることは
極めて重要なことである。電池内で発生する酸素ガスを
効率良く吸収させるためには、正極で発生した酸素ガス
が負極に到達し易く、また負極には酸素との反応に関わ
る部分が多数存在することが望ましい。前述したように
本発明で対象としている電池では極板群内に含ませる希
硫酸電解液の量を規制することで、解離体内に酸素ガス
の通路となる細孔を確保することが可能で、酸素ガスを
効率よく吸収させることができる。By the way, the sealed lead-acid battery absorbs the oxygen gas generated during charging inside the battery to prevent the decrease of the electrolytic solution during charging as in the liquid lead-acid battery and to prevent the maintenance of replenishing water during use. It is a battery that saves labor. Therefore, if the absorption of oxygen gas is poor, the electrolytic solution may decrease, which may eventually lead to a decrease in the capacity and life of the storage battery, and it is extremely difficult to prevent leakage of the electrolytic solution and enhance the oxygen gas absorption capacity. It's important. In order to efficiently absorb the oxygen gas generated in the battery, it is desirable that the oxygen gas generated in the positive electrode easily reach the negative electrode and that the negative electrode has a large number of portions involved in the reaction with oxygen. As described above, in the battery targeted by the present invention, by regulating the amount of dilute sulfuric acid electrolyte contained in the electrode plate group, it is possible to secure pores that serve as passages for oxygen gas in the dissociated body, Oxygen gas can be absorbed efficiently.
一方、最近になって、このような陰極吸収技術の進歩に
つれて大容量の密閉形鉛蓄電池への期待が大きくなって
きている。このような大容量、例えば100〜1000AHのペ
ースト式密閉形鉛蓄電池は、主に停電などの非常時に電
池からエネルギーを供給する用途に用いられるもので、
高い信頼性が要求される。しかし、電池が大きくなり、
大形の寸法の極板によって極板群を構成しようとする
と、極板群内に含まれた硫酸電解液の濃度に分布が生
じ、下部ほど高濃度の液が存在する「成層化現象」が顕
著になる傾向にある。成層化現象というのは、例えば充
放電サイクルによって硫酸電解質が下部へ移行し、電池
エレメントの下部の硫酸電解液の濃度が高くなり、逆に
上部のそれが低くなることを言うもので、この現象が生
じると電池の放電量は少なくなる。密閉形鉛蓄電池では
希硫酸電解液が極板群に吸収・保持されているために、
従来の液式電池にくらべると、成層化は起りにくい。通
常の液式電池では成層化が起りやすいが、その代りに、
起っても過充電を行なうと容易に解消できる特徴があ
る。しかし、本電池ではいったん成層化を生じるとそれ
を解消するのが極めて困難である。成層化が生じると容
量が低下するばかりでなく、下部の高濃度の液に接する
正極板の腐食等の進行により、寿命的にも大きな影響が
ある。したがって密閉形鉛蓄電池の設計においては、電
解液の成層化が起りにくい構造にすることが必要であ
る。On the other hand, recently, with the progress of such a cathode absorption technique, expectations for a large capacity sealed lead acid battery have been increased. Such a large capacity, for example 100 ~ 1000AH paste type sealed lead-acid battery is mainly used for the purpose of supplying energy from the battery in an emergency such as a power failure,
High reliability is required. But the battery gets bigger,
If you try to construct an electrode group with large-sized electrode plates, the concentration of the sulfuric acid electrolyte contained in the electrode group will be distributed, and there will be a "stratification phenomenon" in which the higher concentration of the liquid exists in the lower part. It tends to be noticeable. The stratification phenomenon means that, for example, the sulfuric acid electrolyte moves to the lower part by the charge / discharge cycle, the concentration of the sulfuric acid electrolyte solution at the lower part of the battery element becomes high, and conversely it becomes lower. When this occurs, the discharge amount of the battery decreases. In a sealed lead-acid battery, the dilute sulfuric acid electrolyte is absorbed and retained in the electrode plate group,
Stratification is less likely to occur compared to conventional liquid batteries. In normal liquid batteries, stratification is likely to occur, but instead,
Even if it happens, there is a feature that it can be easily resolved by overcharging. However, in this battery, once stratification occurs, it is extremely difficult to eliminate it. When stratification occurs, not only the capacity is lowered, but also the progress of corrosion of the positive electrode plate in contact with the high-concentration liquid in the lower portion has a great influence on the life. Therefore, in the design of a sealed lead-acid battery, it is necessary to have a structure in which stratification of the electrolytic solution does not easily occur.
本発明は上記した事柄に鑑み、電解液の成層化が起りに
くい陰極吸収式鉛蓄電池を提供するものである。In view of the above matters, the present invention provides a cathode absorption lead-acid battery in which stratification of an electrolytic solution is unlikely to occur.
問題点を解決するための手段 即ち、本発明は前述したように極板群自体が希硫酸電解
液を吸収・保持できるように、極細径のガラス繊維より
成る隔離体を用い、かつゲル化した半固定の希硫酸電解
液を該極板群内に吸収・保持することにより、充放電中
の電解液の成層化を防止するものである。Means for Solving the Problems That is, according to the present invention, as described above, the electrode group itself uses the separator made of the glass fiber having an extremely small diameter so that the electrode group itself can absorb and retain the dilute sulfuric acid electrolytic solution, and it is gelled. By absorbing and retaining the semi-fixed dilute sulfuric acid electrolytic solution in the electrode plate group, stratification of the electrolytic solution during charging and discharging is prevented.
実施例 以下に本発明による陰極吸収式のペースト式密閉形鉛蓄
電池の実施例について具体的に説明する。EXAMPLE An example of the cathode absorption type paste-type sealed lead-acid battery according to the present invention will be specifically described below.
集電体に活物質を充填した大形の平板状の正・負極板、
また平均径が0.7ミクロンのガラス繊維の抄紙体を隔離
体として用いて極板群を構成した。構成した電池の総高
さは約700mmである。該電池について、10時間率電流で
端子電圧が1.8V/セルまで放電し、続いて2.3V/セルで48
時間充電するサイクル試験を行なった。充電中の最大電
流は10時間率電流値に制御した。この試験時における毎
回の放電持続時間をしらべた。試験に供した電池はつぎ
のものである 電池I:従来の開放形液式電池。Large flat-plate positive and negative electrode plates filled with active material in current collector,
Moreover, the electrode plate group was constructed by using a glass fiber paper body having an average diameter of 0.7 micron as a separator. The total height of the constructed battery is about 700 mm. The battery was discharged at a terminal voltage of 1.8 V / cell at a 10-hour rate current, and then 48 V at 2.3 V / cell.
A cycle test of charging for hours was performed. The maximum current during charging was controlled to a 10-hour rate current value. The discharge duration for each test was examined. The batteries used in the test are as follows: Battery I: Conventional open-type liquid battery.
電池II:0.7ミクロンのガラス繊維から成る隔離体を用い
て極板群を構成し、これに比重1.240（20℃基準）の希
硫酸電解液を吸収・保持させた従来の密閉形鉛蓄電池。Battery II: A conventional sealed lead-acid battery that uses a separator made of 0.7 micron glass fiber to form a plate group that absorbs and holds dilute sulfuric acid electrolyte with a specific gravity of 1.240 (at 20 ° C).
電池III:電池IIと同じ極板群から成り、該極板群に、粒
子径が10〜20ミリミクロンのシリカを３重量パーセント
混合した比重1.240（20℃基準）の希硫酸電解液を吸収
・保持させた本発明電池。Battery III: Consists of the same electrode plate group as Battery II, which absorbs a dilute sulfuric acid electrolytic solution having a specific gravity of 1.240 (20 ° C. standard) in which 3% by weight of silica having a particle size of 10 to 20 mm is mixed. The battery of the present invention held.
電池IIIの製造方法について述べる。化成終了後乾燥し
た正・負極板と0.7ミクロンのガラス繊維から成る隔離
体とを用いて極板群を構成した。別に３重量パーセント
のシリカを含む、比重1.230の希硫酸を用意した。該極
板群の最大保持量をあらかじめ求めておき、この量より
もやや少ない量の該希硫酸ゾルをメスシリンダーで計量
し、これを注液口より電池内へ注入した。該電池に安全
弁をつけて密封し、しばらく放置してから公称容量に0.
1を乗じた値の電流で補充電をした。該電流は密閉反応
効率が非常に劣る値として選定した。つまりこれによっ
て、補充電によって電解液が電気分解されて生成した水
素および酸素ガスが電池外へ逸散することにより補充電
後の希硫酸電解液の比重が1.240となるようにした。A method of manufacturing Battery III will be described. After the chemical conversion was completed, a positive electrode plate and a negative electrode plate, which were dried, and a separator made of 0.7 micron glass fiber were used to form an electrode plate group. Separately, diluted sulfuric acid having a specific gravity of 1.230 and containing 3 weight percent of silica was prepared. The maximum holding amount of the electrode plate group was obtained in advance, and the dilute sulfuric acid sol in an amount slightly smaller than this amount was weighed with a graduated cylinder and injected into the battery through the liquid injection port. Attach a safety valve to the battery, seal it, leave it for a while, and then reach the nominal capacity of 0.
Supplementary charging was performed with a current value multiplied by 1. The current was selected as a value at which the closed reaction efficiency was very poor. In other words, as a result, the specific gravity of the diluted sulfuric acid electrolytic solution after supplementary charging was set to 1.240 due to the hydrogen and oxygen gas produced by electrolysis of the electrolytic solution by supplemental charging escaping out of the battery.
このように製造した電池を前述した条件で試験をした結
果を第１図に示す。充放電サイクル中の容量は電池Ｉが
最も低下が激しく、本発明による電池IIIの低下はほと
んど認められなかった。この充放電サイクル中の充電電
気量は放電電気量の110ないし115％であり、容量の低下
が充電不足によるものとは考えられない。このような容
量低下現象の原因は充電あるいは放電中に硫酸電解質が
移動することによる。従って、この試験時の該電解質の
極板群下部方向への降下は、電解液が自由な状態にある
ほど大きい。つまり、従来の開放形液式電池において成
層化が最も起りやすかったといえる。従来の密閉形鉛蓄
電池・電池IIは電池Ｉにくらべれば成層化が起り難かっ
たが、充放電サイクル中の容量低下量は無視できるもの
ではなかった。それに対して、本発明による電池IIIは
容量の低下がなく充放電サイクルを行っても液の成層化
が起らなかったことを示している。この理由は、電池II
Iでは希硫酸電解液が極細径のガラス繊維と極小径のシ
リカ粒子によって充分に捕足されており、該電解液は半
固定状態にあるためである。FIG. 1 shows the result of testing the battery thus manufactured under the above-mentioned conditions. Regarding the capacity during the charge / discharge cycle, the decrease in the battery I was the largest, and the decrease in the battery III according to the present invention was hardly observed. The amount of electricity charged during this charge / discharge cycle is 110 to 115% of the amount of electricity discharged, and it is unlikely that the decrease in capacity is due to insufficient charge. The cause of such a capacity decrease phenomenon is that the sulfuric acid electrolyte moves during charging or discharging. Therefore, the drop of the electrolyte toward the lower part of the electrode plate group during this test is larger as the electrolytic solution is in a free state. That is, it can be said that stratification is most likely to occur in the conventional open type liquid battery. In the conventional sealed lead-acid battery / battery II, stratification was less likely to occur than in the battery I, but the amount of capacity decrease during the charge / discharge cycle was not negligible. On the other hand, the battery III according to the present invention showed that the capacity did not decrease and that the liquid was not stratified even after the charge-discharge cycle. The reason for this is Battery II
This is because in I, the dilute sulfuric acid electrolytic solution is sufficiently trapped by the ultrafine glass fibers and the ultrasmall silica particles, and the electrolytic solution is in a semi-fixed state.
発明の効果 以上述べたように、本発明によれば大形の極板を用いて
も電解液の成層化を防止することができ、例えば充放電
サイクルのような苛酷な試験を行っても容量の低下を防
止することができる。そのため、極板高が高くとも安定
した性能を有する長寿命な大容量のペースト式密閉形鉛
蓄電池を提供し得る利点がある。また、比較的小形の極
板を使用する小容量シール鉛電池に本発明を使用しても
安定した性能を有する電池の実現が可能であり、産業上
極めて大きな効果が得られる。Effects of the Invention As described above, according to the present invention, it is possible to prevent stratification of the electrolytic solution even if a large-sized electrode plate is used, and the capacity can be improved even if a severe test such as a charge / discharge cycle is performed. Can be prevented. Therefore, there is an advantage that it is possible to provide a long-life and large-capacity paste-type sealed lead-acid battery having stable performance even if the electrode plate height is high. Further, even if the present invention is used for a small capacity sealed lead battery using a relatively small-sized electrode plate, a battery having stable performance can be realized, and an extremely large industrial effect can be obtained.
第１図は本発明による密閉形鉛蓄電池IIIと従来形の密
閉形鉛蓄電池IIおよび開放形鉛蓄電池Ｉの充放電サイク
ル中の容量の推移を示す。FIG. 1 shows changes in capacities of a sealed lead acid battery III according to the present invention, a conventional sealed lead acid battery II, and an open type lead acid battery I during a charge / discharge cycle.
───────────────────────────────────────────────────── フロントページの続き 審判の合議体 審判長 西 義之 審判官 小野 秀幸 審判官 相沢 旭 (56)参考文献 特開 昭56−123675（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page Judgment panel Judge Yoshiyuki Nishi Judge Judge Hideyuki Ono Judge Judge Asahi Aizawa (56) Reference JP-A-56-123675 (JP, A)
Claims (1)
とした隔離体、平板状の正極板および陰極板から成る極
板群内において、粒子径が100ミリミクロン以下のシリ
カ粒子を含んだ希硫酸電解液を極細径のガラス繊維と極
小径のシリカ粒子によって充分に捕捉された半固定状態
に均一に吸収保持させたことを特徴とする密閉形鉛蓄電
池。1. A rare plate containing silica particles having a particle diameter of 100 millimicrons or less in an electrode plate group consisting of a separator mainly composed of glass fibers having an average diameter of 5 microns or less, a flat positive electrode plate and a cathode plate. A sealed lead-acid battery characterized in that a sulfuric acid electrolyte is uniformly absorbed and held in a semi-fixed state that is sufficiently captured by ultrafine glass fibers and ultrasmall silica particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60176027A JPH0756811B2 (en) | 1985-08-09 | 1985-08-09 | Sealed lead acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60176027A JPH0756811B2 (en) | 1985-08-09 | 1985-08-09 | Sealed lead acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6237882A JPS6237882A (en) | 1987-02-18 |
| JPH0756811B2 true JPH0756811B2 (en) | 1995-06-14 |
Family
ID=16006445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60176027A Expired - Fee Related JPH0756811B2 (en) | 1985-08-09 | 1985-08-09 | Sealed lead acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0756811B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0624144B2 (en) * | 1987-03-09 | 1994-03-30 | 日本電池株式会社 | Sealed lead acid battery |
| JPH0628169B2 (en) * | 1987-03-09 | 1994-04-13 | 日本電池株式会社 | Sealed lead acid battery |
| JPH0319258U (en) * | 1989-07-07 | 1991-02-26 | ||
| JPH074771Y2 (en) * | 1989-07-07 | 1995-02-01 | 株式会社ユアサコーポレーション | Electrolyte container for storage battery |
| JPH0322357U (en) * | 1989-07-14 | 1991-03-07 | ||
| JPH0324255U (en) * | 1989-07-18 | 1991-03-13 | ||
| JPH0324254U (en) * | 1989-07-19 | 1991-03-13 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56123675A (en) * | 1980-03-04 | 1981-09-28 | Matsushita Electric Ind Co Ltd | Manufacture of closed type lead-acid battery |
| JPS5835877A (en) * | 1981-08-26 | 1983-03-02 | Yuasa Battery Co Ltd | Closed type lead battery and its production method |
-
1985
- 1985-08-09 JP JP60176027A patent/JPH0756811B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6237882A (en) | 1987-02-18 |
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| R250 | Receipt of annual fees |
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| LAPS | Cancellation because of no payment of annual fees |