JPH06333593A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH06333593A JPH06333593A JP5141527A JP14152793A JPH06333593A JP H06333593 A JPH06333593 A JP H06333593A JP 5141527 A JP5141527 A JP 5141527A JP 14152793 A JP14152793 A JP 14152793A JP H06333593 A JPH06333593 A JP H06333593A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- porous
- active material
- electrode plate
- electrode active
- 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
-
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は酸素ガスまたは水素ガス
サイクルによる密閉形鉛蓄電池の改良に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement of a sealed lead acid battery using an oxygen gas or hydrogen gas cycle.
【０００２】[0002]
【従来の技術とその課題】酸素ガスまたは水素ガスサイ
クルによる密閉形鉛蓄電池は電解液を直径約１ミクロン
（μｍ）の極細ガラス繊維からなるマット状セパレータ
（リテーナマット）と正極板および負極板に含浸、保持
させたものが広く実用化されている。この種の電池は補
水ができない構造であるが、自己放電や過放電による水
素ガスおよび酸素ガスの発生ならびに電槽壁面を透過し
て外部へ逃げる水蒸気のために水が減少し、セパレータ
に含まれる電解液量が少なくなって、いわゆるドライア
ップのため、充放電時の抵抗が増大して劣化する。2. Description of the Related Art A sealed lead-acid battery using an oxygen gas or hydrogen gas cycle uses an electrolyte solution as a mat-like separator (retainer mat) made of ultrafine glass fibers having a diameter of about 1 micron (μm), a positive electrode plate and a negative electrode plate. Those that have been impregnated and retained have been widely put into practical use. This type of battery has a structure that cannot be replenished with water, but water is reduced due to the generation of hydrogen gas and oxygen gas due to self-discharge and over-discharge, and the water vapor that permeates the wall of the battery case and escapes to the outside, and is contained in the separator. Since the amount of the electrolytic solution decreases and so-called dry-up occurs, the resistance during charging and discharging increases and deteriorates.
【０００３】従来から商品化されているリテーナ式密閉
電池の、正極活物質、負極活物質およびセパレータの、
希硫酸電解液に対する吸液性の順序は次の通りである。The positive electrode active material, the negative electrode active material, and the separator of the retainer type sealed battery which has been commercialized in the past,
The order of liquid absorption with respect to the dilute sulfuric acid electrolytic solution is as follows.
【０００４】正極活物質＞負極活物質＞セパレータ この順序は、電池内に注入する電解液量を少なくして、
各部分が保持する液量を測定することによって判る。実
測値では、液量を８０％に減少させたとき、各部分の多
孔容積を１００としてそこに保持される液量は、正極活
物質では９５％、負極活物質では８５％、セパレータで
は７０％であった。Positive electrode active material> negative electrode active material> separator In this order, the amount of electrolyte injected into the battery is reduced,
It can be found by measuring the amount of liquid held by each part. According to the measured values, when the liquid amount is reduced to 80%, the liquid amount retained in each portion with the porous volume of 100 is 95% in the positive electrode active material, 85% in the negative electrode active material, and 70% in the separator. Met.
【０００５】セパレータのドライアップによる電池性能
の劣化を防止するために、極板群の周囲に存在する電池
内空間に多孔充填体を配置し、そこに電解液を保持させ
ておく試みがある。この多孔充填体としては、シリカ粉
末あるいは、セパレータと同一材料のガラス繊維が試み
られた。この場合の吸液性の順序は、前者では多孔充填
体と正極活物質とはほぼ同じであり、 多孔充填体および正極活物質＞負極活物質＞セパレータ となり、後者は 正極活物質＞負極活物質＞セパレータ＝多孔充填体 となる。In order to prevent the deterioration of the battery performance due to the dry-up of the separator, there has been an attempt to arrange a porous filler in the space inside the battery existing around the electrode plate group and hold the electrolytic solution therein. As the porous filler, silica powder or glass fiber made of the same material as the separator has been tried. In this case, the order of liquid absorption is almost the same in the former as the porous packing and the positive electrode active material: porous packing and positive electrode active material> negative electrode active material> separator, and the latter is positive electrode active material> negative electrode active material. > Separator = porous packing.
【０００６】したがって、電解液が減少したときにドラ
イアップする部分は、両者共に吸液性が最も小さなセパ
レータであって、セパレータのドライアップによる電池
性能の劣化を防ぐ目的では効果が少なかった。Therefore, the portions that dry up when the amount of the electrolytic solution decreases are both the separators having the smallest liquid absorbability, and the effect is small for the purpose of preventing the deterioration of the battery performance due to the dry up of the separators.
【０００７】本発明は、酸素サイクル反応を利用した密
閉形鉛蓄電池において、各多孔性部分の吸液性を系統的
に種々変えて実験した結果、セパレータのドライアップ
による劣化を解消することを可能にしたものである。According to the present invention, in a sealed lead-acid battery utilizing an oxygen cycle reaction, the liquid absorption of each porous portion was systematically changed variously, and as a result, the deterioration of the separator due to dry-up can be eliminated. It is the one.
【０００８】[0008]
【課題を解決するための手段】本発明は、多孔充填体は
極板群の周囲、すなわち極板群の側部および下部の電槽
内空間の大部分と極板群上部の電槽内空間の少なくとも
一部分に充填・配置し、電解液に対する吸液性が多孔充
填体、負極活物質、セパレータの順に、前者を小さく後
者を大きくするとともに、電解液はそれらの多孔体の孔
内に含浸させるか、または一部だけを流動液として存在
させるものである。According to the present invention, a porous filler is provided around the electrode plate group, that is, most of the inner space of the battery case at the side and lower portions of the electrode plate group and the space inside the battery container above the electrode plate group. At least a part of the porous electrolyte, and the electrolyte absorbency against the electrolyte is increased in order of the porous filler, the negative electrode active material and the separator in order of the former and the latter, and the electrolyte is impregnated into the pores of the porous material. Alternatively, only a part of the liquid is present as a fluid.
【０００９】[0009]
【作用】正極活物質および負極活物質は電解液中の硫酸
と電気化学的に反応して、起電反応を起こしている。セ
パレータは正および負極板の間でイオンを電導し、起電
反応を支えている。多孔充填体は、不完全な密閉反応や
自己放電ならびに電槽壁面からのガスの透過で失われた
水による電解液の減少に対して、それ自体が保持してい
る電解液を排出することで、活物質やセパレータが保持
する電解液量の減少を補償している。また、セパレータ
の吸液性が、負極活物質の吸液性よりも大きくて、多孔
内のガス相の割合は、負極活物質の方がセパレータより
も大きい。これは、負極活物質が多量の酸素ガスと接触
して密閉反応が良好であるとともに、充放電電流はセパ
レータ内を小さな抵抗で流れることを意味している。The positive electrode active material and the negative electrode active material electrochemically react with sulfuric acid in the electrolytic solution to cause an electromotive reaction. The separator conducts ions between the positive and negative plates to support the electromotive reaction. The porous packing discharges the electrolytic solution that it holds against the incomplete closed reaction, self-discharge, and the decrease in electrolytic solution due to water lost due to gas permeation from the wall surface of the battery case. It compensates for the decrease in the amount of electrolytic solution held by the active material and the separator. Further, the liquid absorbing property of the separator is larger than that of the negative electrode active material, and the ratio of the gas phase in the pores is larger in the negative electrode active material than in the separator. This means that the negative electrode active material comes into contact with a large amount of oxygen gas and the sealing reaction is good, and the charge / discharge current flows in the separator with a small resistance.
【００１０】なお、各材料の吸液性は、そのものと希硫
酸電解液との濡れの大小、孔の形状と大小およびその分
布によって決まる。したがって単純に平均孔径や表面積
の大小で表現することはできない。各部分の吸液性の大
小の比較は、実際にそれらを密着させて、例えば電池の
状態に組立てて、所定の少ない液量の電解液を含浸さ
せ、各部分の表面張力の大小によって電解液が分配され
分布した後、各部分を分離して、それぞれに含まれる液
量を測定する必要がある。The liquid absorbability of each material is determined by the size of wetting between itself and the dilute sulfuric acid electrolyte, the shape and size of the holes, and their distribution. Therefore, it cannot be expressed simply by the size of the average pore size or surface area. To compare the size of the liquid absorption of each part, the actual adhesion of them, for example, assembling them into a battery state, impregnation with a predetermined small amount of electrolyte, and the size of the surface tension of each part It is necessary to separate each part and to measure the amount of liquid contained in each part after being distributed and distributed.
【００１１】[0011]
【実施例】正極板および負極板は、常法にしたがって一
定の条件で製作した。活物質の表面積は正極は６．５ｍ
2 ／g 、負極は０．７ｍ2 ／g であった。セパレータ
は、原料となるガラス繊維の平均直径を０．９μｍから
０．２μｍまで変えて抄紙し、電解液の吸液性の大小を
変えた。表面積は１．８〜１８ｍ2 ／g である。多孔充
填体は、セパレータと同じ材質からなるガラス繊維を用
い、平均直径を３μｍから０．５μｍまで変えて、これ
を電池内の極板群周囲の空所に手で充填した。電解液量
は電池を倒置して滴下しない量を保持させた。Example A positive electrode plate and a negative electrode plate were manufactured under a fixed condition according to a conventional method. The surface area of the active material is 6.5 m for the positive electrode
2 / g, the negative electrode was 0.7 m 2 / g. For the separator, paper was made by changing the average diameter of the glass fiber as a raw material from 0.9 μm to 0.2 μm, and the size of the electrolyte absorbing property was changed. The surface area is 1.8-18 m 2 / g. As the porous filler, glass fibers made of the same material as the separator were used, the average diameter was changed from 3 μm to 0.5 μm, and this was manually filled in the space around the electrode plate group in the battery. The amount of the electrolytic solution was set such that the battery was inverted and not dropped.
【００１２】定格容量６．０Ａh の小型密閉電池で放電
は５ hＲ電流で３h 、充電は５ hＲ電流の３／４の電流
で５h という充放電サイクル試験を行ない、放電の量と
電池重量の減少量とを調べた。供試電池の内容とサイク
ル寿命試験の結果とを表１に示す。A small sealed battery having a rated capacity of 6.0 Ah was subjected to a charge / discharge cycle test of discharging at 5 hR current for 3 h and charging at 3/4 of 5 hR current for 5 h to reduce the amount of discharge and battery weight. I checked the quantity. Table 1 shows the contents of the test battery and the result of the cycle life test.
【００１３】[0013]
【表１】 この実験結果から、多孔充填体の吸液性がセパレータの
それよりも大きなものが優れており、特に吸液性の順序
が セパレータ＞負極活物質＞多孔充填体 のものがサイクル寿命が優れており、減液量も少ないこ
とが判る。多孔充填体の吸液性がセパレータよりも大き
い電池は性能が特に悪い。[Table 1] From the results of this experiment, it is found that the porous packing material having a larger liquid absorption property than the separator is superior, and particularly the liquid absorption property of separator> negative electrode active material> porous packing material has a superior cycle life. It can be seen that the amount of liquid reduction is also small. A battery in which the liquid absorption of the porous filler is larger than that of the separator has particularly poor performance.
【００１４】この実験では比較を簡単にするためにセパ
レータと多孔充填体のいずれも細いガラス繊維を用い
た。しかし、吸液性の大きなセパレータとしては、細い
ガラス繊維からなるマットにシリカ微粉末を付着、保持
させてもよい。また、表面積が５０ｍ2 ／g 以上のシリ
カ微粉末を造粒あるいは凝集させた顆粒状シリカを極板
間だけに充填するか、あるいは顆粒状シリカを少量のバ
インダーでシート状に成形したものを用いてもよい。顆
粒状シリカを用いるとセパレータの吸液性は正極活物質
のそれと同じか、またはそれ以上になる。In this experiment, thin glass fibers were used for both the separator and the porous packing for the purpose of simplifying the comparison. However, as a separator having a large liquid absorbing property, silica fine powder may be attached and held on a mat made of thin glass fibers. Further, the granular silica obtained by granulating or aggregating fine silica powder having a surface area of 50 m 2 / g or more is filled only between the electrode plates, or the granular silica is formed into a sheet with a small amount of binder. May be. When granular silica is used, the liquid absorbency of the separator is the same as or higher than that of the positive electrode active material.
【００１５】多孔充填体としては、吸液性を小さくする
ために、ガラスよりも親水性の劣るプラスチック繊維あ
るいは、セパレータよりも直径の大きなガラス繊維を必
要に応じて切断して充填するか、バインダーで成形して
挿入してもよい。また、シリカ、アルミナ、ガラスなど
の無機材料からなる粗粉、あるいはポリエチレン、ポリ
プロピレン、ポリスチレンなどのプラスチックからなる
粗粉あるいはペレット、さらにこれらの材料からなる発
泡体を充填して、多孔充填体とすることもできる。これ
らの無機およびプラスチック粉末は所定の形状に成形し
て、極板群周囲の空所に設置してもよい。いずれの場合
でも、多孔充填体はセパレータと接触あるいは密着し
て、両者の間で保持している液が移動可能でなければな
らない。As the porous filler, in order to reduce the liquid absorbency, a plastic fiber having a hydrophilicity lower than that of glass or a glass fiber having a diameter larger than that of the separator is cut and filled as necessary, or a binder. You may shape and insert in. Further, coarse powder made of an inorganic material such as silica, alumina, or glass, or coarse powder or pellets made of a plastic such as polyethylene, polypropylene, or polystyrene, or a foam made of these materials is filled to form a porous filler. You can also These inorganic and plastic powders may be molded into a predetermined shape and placed in a space around the electrode plate group. In any case, the porous packing material must be in contact with or in close contact with the separator so that the liquid held between them can be moved.
【００１６】[0016]
【発明の効果】本発明は極板群の周囲に多孔充填体を充
填・配置するとともに、多孔充填体の電解液に対する吸
液性をセパレータのそれより小さくしたこと、さらに電
解液に対する吸液性を大きい順にセパレータ、負極活物
質、多孔充填体となるようにすることによって、電解液
が減少したときにもセパレータのドライアップを防ぎ、
寿命性能に優れた密閉形鉛蓄電池を製造することが可能
となり、その工業的価値ははなはだ大なものである。EFFECTS OF THE INVENTION According to the present invention, the porous packing is filled and arranged around the electrode plate group, and the liquid absorption of the porous packing is smaller than that of the separator. By increasing the order of the separator, the negative electrode active material, and the porous packing material, it is possible to prevent the separator from drying up even when the electrolytic solution decreases.
It becomes possible to manufacture a sealed lead-acid battery with excellent life performance, and its industrial value is enormous.
Claims (2)
ものであり、該多孔体は正極活物質、セパレータ、負極
活物質および多孔充填体であり、セパレータは正極板お
よび負極板の間に配置されて両者の短絡を防ぐとともに
電解液を保持してイオン電導にあずかる機能を有するも
のであり、該多孔充填体は極板群の周囲、すなわち極板
群の側部および下部の電槽内空間の大部分と極板群上部
の電槽内空間の少なくとも一部分に充填・配置されたも
のであり、多孔充填体の電解液に対する吸液性がセパレ
ータの吸液性よりも小さなものであり、電解液は該多孔
体の孔内に含浸されるか、または一部だけが流動液とし
て存在することを特徴とする酸素ガスまたは水素ガスサ
イクルによる密閉形鉛蓄電池。1. A cell having at least the following porous body in a cell, wherein the porous body is a positive electrode active material, a separator, a negative electrode active material and a porous filler, and the separator is disposed between the positive electrode plate and the negative electrode plate. It has a function of preventing short-circuiting of both and holding the electrolytic solution and participating in ionic conduction, and the porous packing has a large circumference of the electrode plate group, that is, a large space inside the battery cell in the side and lower parts of the electrode plate group. Part and at least a part of the inner space of the battery case above the electrode plate group are filled and arranged, and the liquid absorbency of the porous filler to the electrolytic solution is smaller than that of the separator, and the electrolytic solution is A sealed lead acid battery by an oxygen gas or hydrogen gas cycle, characterized in that it is impregnated into the pores of the porous body or only a part thereof is present as a fluid.
充填体、負極活物質、セパレータの順で、前者が小さく
後者が大きな請求項１に記載の密閉形鉛蓄電池。2. The sealed lead-acid battery according to claim 1, wherein the porous body has a liquid absorbing property for an electrolytic solution in the order of the porous filler, the negative electrode active material, and the separator, the former being smaller and the latter being larger.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05141527A JP3118718B2 (en) | 1993-05-20 | 1993-05-20 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05141527A JP3118718B2 (en) | 1993-05-20 | 1993-05-20 | Sealed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06333593A true JPH06333593A (en) | 1994-12-02 |
| JP3118718B2 JP3118718B2 (en) | 2000-12-18 |
Family
ID=15294046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05141527A Expired - Lifetime JP3118718B2 (en) | 1993-05-20 | 1993-05-20 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3118718B2 (en) |
-
1993
- 1993-05-20 JP JP05141527A patent/JP3118718B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3118718B2 (en) | 2000-12-18 |
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