JPH09147844A - Sealed lead-acid battery - Google Patents
Sealed lead-acid batteryInfo
- Publication number
- JPH09147844A JPH09147844A JP7304097A JP30409795A JPH09147844A JP H09147844 A JPH09147844 A JP H09147844A JP 7304097 A JP7304097 A JP 7304097A JP 30409795 A JP30409795 A JP 30409795A JP H09147844 A JPH09147844 A JP H09147844A
- Authority
- JP
- Japan
- Prior art keywords
- water
- lead
- water repellent
- repellent
- lattice
- 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.)
- Withdrawn
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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、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 sealed lead-acid battery.
【０００２】[0002]
【従来の技術】密閉形鉛蓄電池は、正極板の格子体に鉛
−カルシウム系合金を用いることで、自己放電，減液特
性を向上させると共に、フリーな電解液をなくし、充電
時に発生する酸素を負極板に吸収させることにより密閉
化している。2. Description of the Related Art Sealed lead-acid batteries use a lead-calcium alloy in the grid of the positive electrode plate to improve self-discharge and liquid reduction characteristics, eliminate free electrolyte, and eliminate oxygen generated during charging. Is absorbed by the negative electrode plate so as to be hermetically sealed.
【０００３】このような密閉形鉛蓄電池は、補水不要の
メンテナンスフリーな特長から、無停電電源装置等の用
途が拡大してきており、近年更なる長寿命化が望まれて
いる。Since such a sealed lead-acid battery has a maintenance-free feature that does not require replenishing water, its applications such as an uninterruptible power supply are expanding, and it has been desired in recent years to further extend its service life.
【０００４】密閉形鉛蓄電池を、通常は充電状態で維持
し、必要なときに放電するトリクル用途に使用した場合
の電池寿命の主な原因は、正極板の格子体の腐食に起因
し、格子体の伸びによる短絡や、活物質の脱落が故障の
原因となる。When a sealed lead-acid battery is normally used in a charged state and used for trickle discharge when needed, the main cause of battery life is corrosion of the positive electrode plate grid, Short-circuiting due to stretching of the body and dropping of the active material cause malfunctions.
【０００５】従来、格子体の鉛−カルシウム系合金の腐
食を防ぐには、格子体合金中のスズ濃度を増やす方法と
か、格子体の表面に耐酸化性を有するα−ＰｂＯ2 やＢ
ａＰｂＯ3 等の保護皮膜を形成する方法が知られてい
る。Conventionally, in order to prevent the corrosion of the lead-calcium alloy in the lattice, a method of increasing the tin concentration in the lattice alloy or α-PbO 2 or B having oxidation resistance on the surface of the lattice is used.
A method of forming a protective film such as aPbO3 is known.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、従来の
格子体合金中のスズ濃度を増やす方法では、格子体と活
物質との界面の密着が悪くなり、界面の剥離や活物質の
脱落等によって早期寿命となるという問題点があった。However, in the conventional method of increasing the tin concentration in the lattice alloy, the adhesion between the interface between the lattice and the active material is deteriorated, and the interface may be peeled off or the active material may fall off, resulting in an early failure. There was a problem of reaching the end of life.
【０００７】また、格子体表面に耐酸化性を有するα−
ＰｂＯ2 やＢａＰｂＯ3 等の保護皮膜を形成する方法で
は、該皮膜が徐々に酸化され効果に限界があるという問
題点があった。Further, α-, which has an oxidation resistance on the surface of the lattice,
The method of forming a protective film such as PbO2 or BaPbO3 has a problem that the film is gradually oxidized and the effect is limited.
【０００８】本発明の目的は、大幅にトリクル寿命を向
上させることができる密閉形鉛蓄電池を提供することに
ある。An object of the present invention is to provide a sealed lead acid battery which can significantly improve the trickle life.
【０００９】[0009]
【課題を解決するための手段】本発明に係る密閉形鉛蓄
電池は、鉛−カルシウム系合金からなる格子体と活物質
との界面に撥水性を有する部分が散在して設けられた正
極板を備えていることを特徴とする。A sealed lead-acid battery according to the present invention comprises a positive electrode plate provided with dispersed water-repellent portions at an interface between a grid body made of a lead-calcium alloy and an active material. It is characterized by having.
【００１０】このように正極板の鉛−カルシウム系合金
からなる格子体と活物質との界面に撥水性を有する部分
を散在して設けると、該撥水性を有する部分は電解液と
接していないため、電気的に不活性であり、酸化をほと
んど受けないので、従来のα−ＰｂＯ2 やＢａＰｂＯ3
を形成する方法に比べて安定して格子体を保護すること
ができる。更に、撥水性を有する部分と撥水性を有する
部分との間の部分も、該撥水性を有する部分の撥水作用
により電解液が到達し難く、このため格子体近傍全体が
電解液との接触から保護される。それ故、格子体の腐食
と硫酸鉛化を防止することができる。この作用は、格子
体の表面のみで起こるため、蓄電池全体の容量を低下さ
せるものではない。As described above, when the water-repellent portions are provided scattered on the interface between the active material and the grid of the lead-calcium alloy of the positive electrode plate, the water-repellent portions are not in contact with the electrolytic solution. Therefore, it is electrically inactive and hardly receives oxidation. Therefore, conventional α-PbO2 and BaPbO3 are used.
It is possible to protect the lattice more stably than the method of forming. Further, the electrolytic solution does not easily reach the portion between the water-repellent portion and the water-repellent portion due to the water-repellent action of the water-repellent portion. Protected from. Therefore, it is possible to prevent the corrosion of the grid and the conversion of lead sulfate. This action does not reduce the capacity of the entire storage battery because it occurs only on the surface of the grid.
【００１１】このような密閉形鉛蓄電池によれば、大幅
にトリクル寿命を向上させることができる。According to such a sealed lead-acid battery, the trickle life can be greatly extended.
【００１２】この場合、正極板の撥水性を有する部分
は、撥水性粒子で形成することができる。In this case, the water repellent portion of the positive electrode plate can be formed of water repellent particles.
【００１３】このように撥水性を有する部分を撥水性粒
子で形成すると、撥水性を有する部分を容易に形成する
ことができる。By forming the water-repellent portion with the water-repellent particles, the water-repellent portion can be easily formed.
【００１４】撥水性粒子は格子体に設けられた鉛メッキ
層に散在させて支持させ、隣接する撥水性粒子の間には
活物質を配置することが好ましい。It is preferable that the water-repellent particles are scattered and supported by the lead plating layer provided on the lattice, and the active material is arranged between the adjacent water-repellent particles.
【００１５】このようにすると、撥水性粒子を格子体の
表面にメッキ法で容易に設けることができる。By doing so, the water-repellent particles can be easily provided on the surface of the lattice by the plating method.
【００１６】また、撥水性粒子はバインダーと導電性粉
体との混合層として格子体に支持させることが好まし
い。The water-repellent particles are preferably supported on the lattice as a mixed layer of the binder and the conductive powder.
【００１７】このようにすると、メッキ法より高い撥水
性を容易に得ることができる。By doing so, it is possible to easily obtain higher water repellency than the plating method.
【００１８】[0018]
【発明の実施の形態】図１は、本発明に係る密閉形鉛蓄
電池における実施の形態の第１例を示したものである。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows a first example of an embodiment of a sealed lead acid battery according to the present invention.
【００１９】本例の密閉形鉛蓄電池においては、鉛−カ
ルシウム系合金からなる格子体１と活物質２との界面に
撥水性を有する部分が散在して設けられた正極板を備え
ている。該撥水性を有する部分は撥水性粒子３で形成さ
れている。本例では、撥水性粒子３は格子体１に設けら
れた鉛メッキ層４に散在させて支持されている。隣接す
る撥水性粒子３の間には活物質２が配置されている。な
お、５は電解液の到達可能範囲である。The sealed lead-acid battery of this example is provided with a positive electrode plate provided with dispersed water-repellent portions at the interface between the grid 1 made of a lead-calcium alloy and the active material 2. The water-repellent portion is formed of the water-repellent particles 3. In this example, the water-repellent particles 3 are scattered and supported by the lead-plated layer 4 provided on the grid 1. The active material 2 is arranged between the adjacent water-repellent particles 3. In addition, 5 is a reachable range of the electrolytic solution.
【００２０】このように正極板の鉛−カルシウム系合金
からなる格子体１と活物質２との界面に撥水性を有する
部分を撥水性粒子３により散在して設けると、該撥水性
を有する部分は電解液と接していないため、電気的に不
活性であり、酸化をほとんど受けないので、従来のα−
ＰｂＯ2 やＢａＰｂＯ3 を形成する方法に比べて安定し
て格子体１を保護することができる。更に、撥水性を有
する部分である撥水性粒子３と撥水性粒子３との間の部
分も、該撥水性粒子３の撥水作用により電解液が到達し
難く、このため格子体１の近傍全体が電解液との接触か
ら保護される。それ故、格子体１の腐食と硫酸鉛化を防
止することができる。この作用は、格子体１の表面のみ
で起こるため、蓄電池全体の容量を低下させるものでは
ない。When water-repellent portions are provided on the interface between the grid 1 made of the lead-calcium alloy of the positive electrode plate and the active material 2 by the water-repellent particles 3, the water-repellent portion is provided. Since it is not in contact with the electrolyte, it is electrically inactive and is hardly oxidized, so
Compared with the method of forming PbO2 or BaPbO3, the lattice 1 can be protected more stably. Further, the water-repellent particles 3 which are water-repellent parts and the part between the water-repellent particles 3 are also difficult for the electrolytic solution to reach due to the water-repellent action of the water-repellent particles 3, so that the entire vicinity of the lattice 1 is affected. Are protected from contact with the electrolyte. Therefore, it is possible to prevent corrosion of the grid 1 and lead sulfate conversion. Since this action occurs only on the surface of the grid body 1, it does not reduce the capacity of the entire storage battery.
【００２１】このような密閉形鉛蓄電池によれば、大幅
にトリクル寿命を向上させることができる。According to such a sealed lead-acid battery, the trickle life can be greatly extended.
【００２２】図２は、本発明に係る密閉形鉛蓄電池にお
ける実施の形態の第２例を示したものである。FIG. 2 shows a second example of the embodiment of the sealed lead-acid battery according to the present invention.
【００２３】本例の密閉形鉛蓄電池においては、鉛−カ
ルシウム系合金からなる格子体１と活物質２との界面に
撥水性を有する部分が散在して設けられた正極板を備え
ている。該撥水性を有する部分は、撥水性粒子３で形成
されている。本例では、撥水性粒子３はバインダーと導
電性粉体６との混合層７として格子体１に支持されてい
る。導電性粉体６としては、鉛粉や炭素粉等を用いるこ
とができる。The sealed lead-acid battery of this example is provided with a positive electrode plate provided with scattered water-repellent portions at the interface between the grid 1 made of a lead-calcium alloy and the active material 2. The water-repellent portion is formed of the water-repellent particles 3. In this example, the water-repellent particles 3 are supported by the grid body 1 as a mixed layer 7 of the binder and the conductive powder 6. As the conductive powder 6, lead powder, carbon powder or the like can be used.
【００２４】このようにして撥水性粒子３を散在させる
と、メッキ法より高い撥水性を容易に得ることができ
る。By dispersing the water-repellent particles 3 in this manner, it is possible to easily obtain higher water repellency than the plating method.
【００２５】[0025]
【実施例】まず、以下に示す５種類の格子体（本発明格
子体１，２、比較例格子体１，２，３）を準備した。EXAMPLE First, the following five types of lattices (the present invention's lattices 1, 2 and the comparative lattices 1, 2, 3) were prepared.
【００２６】（本発明格子体１）Ｐｂ−Ｃａ（0.1 ％）
−Ｓｎ（1.0 ％）の組成の格子体に、表１に示す条件で
分散メッキを行い、該分散メッキ層を介して格子体の表
面に撥水性粒子としてのポリテトラフロロエチレン（以
下、ＰＴＦＥと称する。）粒子の点在する層を形成し
た。ＰＴＦＥ粒子は平均粒子径10μｍのものを用い、カ
チオン系界面活性剤にて親水化させメッキ浴に投入し
た。(Lattice body 1 of the present invention) Pb-Ca (0.1%)
Dispersion plating was performed on a lattice having a composition of -Sn (1.0%) under the conditions shown in Table 1, and polytetrafluoroethylene (hereinafter referred to as PTFE) as water-repellent particles was formed on the surface of the lattice through the dispersion plating layer. Referred to as ".) A layer in which particles were scattered was formed. The PTFE particles used had an average particle size of 10 μm, and were made hydrophilic with a cationic surfactant and added to the plating bath.
【００２７】[0027]
【表１】 （本発明格子体２）鉛粉末及びＰＴＦＥ粒子の混合物に
シリカを主成分とした増粘剤と水及びカチオン系界面活
性剤（混合粉末30ｇに対し増粘剤１ｇ，水２ｇ，界面活
性剤0.002ｇの割合）を添加し、スラリー状になるまで
かき混ぜ、スプレーガンを用い、本発明格子体１に用い
たのを同じ組成の未処理格子体の表面に均一にＰＴＦＥ
粒子の点在する層を形成した。[Table 1] (Lattice body 2 of the present invention) Thickener containing silica as a main component in a mixture of lead powder and PTFE particles and water and cationic surfactant (1 g thickener, 2 g water, 0.002 surfactant for 30 g mixed powder). (g ratio), stirred until a slurry was formed, and a spray gun was used to uniformly apply PTFE to the surface of an untreated lattice of the same composition.
A layer of scattered particles was formed.
【００２８】（比較例格子体１）従来法の格子体中のＳ
ｎ量を増加させた場合に相当する例で、Ｐｂ−Ｃａ（0.
1 ％）−Ｓｎ（2.0 ％）の格子体を用いた。(Comparative grid 1) S in the conventional grid
In an example corresponding to the case where the amount of n is increased, Pb-Ca (0.
A 1%)-Sn (2.0%) lattice was used.
【００２９】（比較例格子体２）Ｐｂ−Ｃａ（0.1 ％）
−Ｓｎ（1.0 ％）の組成の格子体をｐＨ10の水酸化ナト
リウム中で温度25℃，陰極電流密度５Ａ／dm2 の条件で
電解酸化し、格子体の表面にα−ＰｂＯ2 層を形成し
た。形成したα−ＰｂＯ2 層の厚みは10μｍとした。(Comparative grid 2) Pb-Ca (0.1%)
A lattice of --Sn (1.0%) was electrolytically oxidized in sodium hydroxide having a pH of 10 at a temperature of 25 ° C. and a cathode current density of 5 A / dm 2 to form an α-PbO 2 layer on the surface of the lattice. The thickness of the formed .alpha.-PbO2 layer was 10 .mu.m.
【００３０】（比較例格子体３）未処理のＰｂ−Ｃａ
（0.1 ％）−Ｓｎ（1.0 ％）の組成の格子体を用いた。(Comparative grid 3) Untreated Pb-Ca
A lattice having a composition of (0.1%)-Sn (1.0%) was used.
【００３１】以上の５種類の格子体（本発明格子体１，
２、比較例格子体１，２，３）に、公知の鉛蓄電池用ペ
ーストを充填し、熟成，化成を経て正極板を得て、公知
の負極板を組み合わせ２Ｖ−５Ahの密閉形鉛蓄電池を作
製した。The above five types of lattice bodies (the lattice body 1 of the present invention 1,
2, the comparative grids 1, 2, 3) are filled with a known lead-acid battery paste, and a positive electrode plate is obtained through aging and chemical formation, and a known negative electrode plate is combined to form a sealed lead-acid battery of 2V-5Ah. It was made.
【００３２】これら５種類の密閉形鉛蓄電池（これを本
発明品１，２、比較例１，２，３と称する。）の、2.27
5 Ｖ／セル，45℃の条件でのトリクル寿命試験の結果を
図３に示す。2.27 of these five types of sealed lead-acid batteries (referred to as the products 1 and 2 of the present invention and comparative examples 1, 2 and 3)
Figure 3 shows the results of the trickle life test under the conditions of 5 V / cell and 45 ° C.
【００３３】該図３より、本発明品１，２は比較例１，
２，３と比較して、容量が同等で寿命が大幅に向上して
いることがわかる。From FIG. 3, the invention products 1 and 2 are comparative examples 1 and 2.
It can be seen that the capacities are the same and the life is greatly improved as compared with 2 and 3.
【００３４】[0034]
【発明の効果】本発明に係る密閉形鉛蓄電池は、正極板
の鉛−カルシウム系合金からなる格子体と活物質との界
面に撥水性を有する部分を散在して設けたので、撥水性
を有する部分は電解液と接していないため、電気的に不
活性であり、酸化をほとんど受けないので、従来のα−
ＰｂＯ2 やＢａＰｂＯ3 を形成する方法に比べて安定し
て格子体を保護することができる。更に、撥水性を有す
る部分と撥水性を有する部分との間の部分も、該撥水性
を有する部分の撥水作用により電解液が到達し難く、こ
のため格子体近傍全体が電解液との接触から保護でき
る。それ故、格子体の腐食と硫酸鉛化を防止することが
できる。このような密閉形鉛蓄電池によれば、大幅にト
リクル寿命を向上させることができる。EFFECTS OF THE INVENTION Since the sealed lead-acid battery according to the present invention is provided with scattered water-repellent portions at the interface between the active material and the grid of the lead-calcium alloy of the positive electrode plate, Since the part that has it is not in contact with the electrolytic solution, it is electrically inactive and is hardly oxidized, so
Compared with the method of forming PbO2 or BaPbO3, the lattice can be protected more stably. Further, the electrolytic solution does not easily reach the portion between the water-repellent portion and the water-repellent portion due to the water-repellent action of the water-repellent portion. Can be protected from Therefore, it is possible to prevent the corrosion of the grid and the conversion of lead sulfate. According to such a sealed lead acid battery, the trickle life can be significantly improved.
【００３５】該正極板の撥水性を有する部分を撥水性粒
子で形成すると、撥水性を有する部分を容易に形成する
ことができる。When the water repellent portion of the positive electrode plate is formed of water repellent particles, the water repellent portion can be easily formed.
【００３６】また、撥水性粒子は格子体に設けられた鉛
メッキ層に散在させて支持させ、隣接する撥水性粒子の
間には活物質を配置すると、撥水性粒子を格子体の表面
にメッキ法で容易に設けることができる。Further, when the water-repellent particles are scattered and supported by the lead plating layer provided on the lattice and an active material is arranged between the adjacent water-repellent particles, the water-repellent particles are plated on the surface of the lattice. It can be easily provided by law.
【００３７】また、撥水性粒子をバインダーと導電性粉
体との混合層として格子体に支持させると、メッキ法よ
り高い撥水性を容易に得ることができる。Further, when the water-repellent particles are supported on the lattice as a mixed layer of the binder and the conductive powder, the water repellency higher than the plating method can be easily obtained.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明に係る密閉形鉛蓄電池の実施の形態の第
１例における正極板の格子体−活物質界面の模式図であ
る。FIG. 1 is a schematic view of a lattice-active material interface of a positive electrode plate in a first example of an embodiment of a sealed lead-acid battery according to the present invention.
【図２】本発明に係る密閉形鉛蓄電池の実施の形態の第
２例における正極板の格子体−活物質界面の模式図であ
る。FIG. 2 is a schematic view of the lattice-active material interface of the positive electrode plate in the second example of the embodiment of the sealed lead-acid battery according to the present invention.
【図３】本発明品１，２と比較例１，２，３の密閉形鉛
蓄電池のトリクル寿命試験結果を示す図である。FIG. 3 is a view showing the results of a trickle life test of the sealed lead-acid batteries of Inventive Products 1 and 2 and Comparative Examples 1, 2, and 3.
１ 格子体 ２ 活物質 ３ 撥水性粒子 ４ 鉛メッキ層 ５ 電解液の到達可能範囲 ６ バインダーと導電性粉体 ７ 混合層 1 Lattice body 2 Active material 3 Water repellent particles 4 Lead plating layer 5 Reachable range of electrolyte 6 Binder and conductive powder 7 Mixed layer
Claims (4)
活物質との界面に撥水性を有する部分が散在して設けら
れた正極板を備えていることを特徴とする密閉形鉛蓄電
池。1. A sealed lead-acid battery comprising a positive electrode plate provided with scattered water-repellent portions at an interface between a grid body made of a lead-calcium alloy and an active material.
撥水性粒子で形成されていることを特徴とする請求項１
に記載の密閉形鉛蓄電池。2. The water repellent portion of the positive electrode plate is formed of water repellent particles.
A sealed lead-acid battery according to claim 1.
た鉛メッキ層に散在させて支持され、隣接する前記撥水
性粒子の間には前記活物質が配置されていることを特徴
とする請求項２に記載の密閉形鉛蓄電池。3. The water-repellent particles are scattered and supported by a lead-plated layer provided on the lattice, and the active material is arranged between the adjacent water-repellent particles. The sealed lead-acid battery according to claim 2.
体との混合層として前記格子体に支持されていることを
特徴とする請求項２に記載の密閉形鉛蓄電池。4. The sealed lead-acid battery according to claim 2, wherein the water-repellent particles are supported by the lattice as a mixed layer of a binder and a conductive powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7304097A JPH09147844A (en) | 1995-11-22 | 1995-11-22 | Sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7304097A JPH09147844A (en) | 1995-11-22 | 1995-11-22 | Sealed lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09147844A true JPH09147844A (en) | 1997-06-06 |
Family
ID=17928995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7304097A Withdrawn JPH09147844A (en) | 1995-11-22 | 1995-11-22 | Sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09147844A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015138658A (en) * | 2014-01-22 | 2015-07-30 | トヨタ自動車株式会社 | Method for manufacturing electrode for lithium secondary battery, and granulated material |
-
1995
- 1995-11-22 JP JP7304097A patent/JPH09147844A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015138658A (en) * | 2014-01-22 | 2015-07-30 | トヨタ自動車株式会社 | Method for manufacturing electrode for lithium secondary battery, and granulated material |
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| A300 | Withdrawal of application because of no request for examination |
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