JP2773312B2 - Manufacturing method of positive electrode plate for lead-acid battery - Google Patents
Manufacturing method of positive electrode plate for lead-acid batteryInfo
- Publication number
- JP2773312B2 JP2773312B2 JP1283237A JP28323789A JP2773312B2 JP 2773312 B2 JP2773312 B2 JP 2773312B2 JP 1283237 A JP1283237 A JP 1283237A JP 28323789 A JP28323789 A JP 28323789A JP 2773312 B2 JP2773312 B2 JP 2773312B2
- Authority
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- Japan
- Prior art keywords
- lead
- pbo
- weight
- yellow
- electrode plate
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、鉛蓄電池の製造法に関するものであり、特
にペースト式正極板の活物質利用率および寿命特性の向
上を図るものである。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lead storage battery, and more particularly to an improvement in the active material utilization rate and life characteristics of a paste-type positive electrode plate.
従来の技術 鉛蓄電池用極板は、通常金属鉛および鉛酸化物からな
る鉛粉に水および硫酸を加え、混練しペーストとし、鉛
合金格子に充填したのち定められた温度や湿度の環境下
で熟成乾燥して製造している。ここで、一般に熟成乾燥
を低温低湿の条件下で行なうと３塩基性硫酸鉛の生成
が、また高温多湿の条件下で行うと４塩基性硫酸鉛の生
成が顕著に見られる。2. Description of the Related Art Lead plates for lead-acid batteries are usually prepared by adding water and sulfuric acid to lead powder composed of metallic lead and lead oxide, kneading and forming a paste, filling the lead alloy grid, and then subjecting it to a specified temperature and humidity environment. Aged and dried. In general, when aging and drying are performed under low-temperature and low-humidity conditions, formation of tribasic lead sulfate is significantly observed, and when aging and drying are performed under high-temperature and high-humidity conditions, formation of tetrabasic lead sulfate is remarkably observed.
一般には温度80℃以上湿度85％以上で４塩基性硫酸鉛
が生成し始めてくることが良く知られている。It is well known that generally tetrabasic lead sulfate starts to be formed at a temperature of 80 ° C. or higher and a humidity of 85% or higher.
発明が解決しようとする課題 ところで、このような４塩基性硫酸鉛の生成が確かめ
られた正極板を化成した場合次のようないくつかの問題
点があった。Problems to be Solved by the Invention By the way, when the positive electrode plate in which the formation of such tetrabasic lead sulfate was confirmed was formed, there were some problems as follows.
（１） 極板の格子骨から遠いところでは硫酸鉛が化成
後も極板の内部まで残存しており、この硫酸鉛層は充放
電をくりかえしても簡単には二酸化鉛にならない。その
ためこの部分は電池の活物質とならず電池容量が期待ど
おり得られない。(1) Lead sulfate remains inside the electrode plate even after formation at a position far from the grid bone of the electrode plate, and this lead sulfate layer does not easily become lead dioxide even if charge and discharge are repeated. Therefore, this portion does not become an active material of the battery, and the battery capacity cannot be obtained as expected.
（２） 逆に格子の近傍はβPbO2の生成が顕著である。
この部分の活物質は早期に軟化脱落が進行し寿命がつき
た状態になる。(2) Conversely, βPbO 2 is remarkably generated near the lattice.
The active material in this portion undergoes softening and falling off at an early stage, and becomes a state where the life is extended.
課題を解決するための手段 本発明は、上記の如く鉛蓄電池用正極板を高温多湿下
で熟成乾燥し化成を行なったときに生じる上記課題を解
決するものである。Means for Solving the Problems The present invention solves the above-mentioned problems which occur when the positive electrode plate for a lead storage battery is aged and dried under high temperature and high humidity to form a chemical.
その手段は、一般的に鉛粉として用いられている赤色
リサージ〔以下PbO（RED）という〕および金属鉛を主成
分とした鉛粉に、新たに黄色リサージ〔以下PbO（YELLO
W）という〕および鉛丹を主成分とした粉末を加えて混
合粉末をつくる。この混合粉末に水と硫酸を加え混練し
てペーストとし、これを鉛合金からなる格子体に充填し
たのち、温度80から95℃、湿度85％以上の条件下で熟成
乾燥して正極板を製造するものである。The means is to add red litharge (hereinafter referred to as PbO (RED)), which is generally used as lead powder, and lead yellow powder [hereafter, PbO (YELLO)
W)] and a powder containing lead as a main component to make a mixed powder. Water and sulfuric acid are added to this mixed powder to form a paste, which is then kneaded to form a paste. The paste is filled in a grid made of a lead alloy, and then aged at a temperature of 80 to 95 ° C and a humidity of 85% or more to produce a positive electrode plate. Is what you do.
作用 前記問題点（１），（２）は調査の結果、次のような
原因で生じることが分った。Operation As a result of the investigation, it was found that the problems (1) and (2) were caused by the following causes.
一般に80℃以上、湿度85％以上の条件下で熟成乾燥を
行なっても生成するすべての塩基性硫酸鉛が４塩基性塩
とはならず、３塩基性塩が同じ程度含まれている。In general, even when aging and drying are performed at a temperature of 80 ° C. or more and a humidity of 85% or more, all the basic lead sulfates formed do not become 4-basic salts but contain the same amount of 3-basic salts.
また局部的に見ると格子近傍は格子の熱伝導がよいた
め、乾燥が早く進行し湿度が低下する。そのため格子近
傍の活物質は遠方にくらべ３塩基性塩の生成が多く４塩
基性塩の生成が少ない。In addition, when viewed locally, the heat conduction of the grid is good in the vicinity of the grid, so that the drying proceeds quickly and the humidity decreases. Therefore, the active material in the vicinity of the lattice generates more tribasic salt and generates less tetrabasic salt in a distance.
さて、このような正極板を化成したとき、３塩基性塩
からはβPbO2が生成し、４塩基性塩からはαPbO2が生成
する。Now, when the chemical conversion of such positive electrode plate, from 3 basic salt BetaPbO 2 is produced, ArufaPbO 2 is produced from 4 basic salts.
ところでβPbO2とαPbO2をくらべると、βPbO2は電導
度が高く電流が流れやすい。そのため化成中に電流の流
れやすいβPbO2を生じる部分、すなわち３塩基性塩が多
量に生成している部分に電流が集中する。一度このよう
な現象を生ずると４塩基性塩の結晶が大きいことも原因
となって問題点（１），（２）のような現象を生ずるこ
とになる。By the way, when compared with βPbO 2 and αPbO 2 , βPbO 2 has a high conductivity and a current easily flows. Therefore, the current concentrates on the portion where βPbO 2 , where the current easily flows during the formation, that is, the portion where a large amount of the tribasic salt is generated. Once such a phenomenon occurs, phenomena such as problems (1) and (2) occur due to the large crystals of the tetrabasic salt.
すなわち未化成極板中に３塩基性硫酸鉛と４塩基性硫
酸鉛が混在し、しかもそれぞれが格子近傍と遠方に偏在
しているのが問題点（１），（２）の原因であることが
わかった。That is, the fact that tribasic lead sulfate and tetrabasic lead sulfate are mixed in the unformed electrode plate and that they are unevenly distributed near and far from the lattice is the cause of the problems (1) and (2). I understood.
したがって４塩基性硫酸鉛を生成させる高温高湿の条
件下で、３塩基性硫酸鉛の生成を極力押え、４塩基性硫
酸鉛のみが生成する条件を見つければ、上記問題点を解
決することができる。Therefore, under the conditions of high temperature and high humidity at which tetrabasic lead sulfate is generated, the above problems can be solved by suppressing the generation of tribasic lead sulfate as much as possible and finding the conditions under which only tetrabasic lead sulfate is generated. it can.
ところで酸化鉛にはPbO（YELLOW）とPbO（RED）の２
種類があるが、PbO（YELLOW）からは４塩基性硫酸鉛
が、又PbO（RED）からは３塩基性硫酸鉛が生じやすい。By the way, lead oxide has two types: PbO (YELLOW) and PbO (RED).
PbO (YELLOW) tends to produce tetrabasic lead sulfate, and PbO (RED) tends to produce tribasic lead sulfate.
従来ペースト式鉛蓄電池の鉛粉は熟成乾燥中にペース
トが固化し互いに結着するのに金属鉛が重要な成分であ
った。この鉛粉は金属鉛を何らかの形で粉砕しながら酸
化して作られるものであるが、上記のように金属鉛分を
ある程度残す必要があるため高温で処理することができ
ず、その酸化物は470℃以下で熱力学的に安定なPbO（RE
D）とならざるをえなかった。このような鉛粉を用いて
いるかぎりにおいては高温多湿下で熟成乾燥を行っても
３塩基性塩のかなりの生成はさけられない。Conventionally, lead powder of a paste-type lead-acid battery is an important component in which lead metal solidifies during aging and drying and binds to each other. This lead powder is made by oxidizing metal lead while crushing it in some way, but it cannot be processed at high temperatures because it is necessary to leave a certain amount of metal lead as described above. Thermodynamically stable PbO (RE
D). As long as such a lead powder is used, considerable formation of a tribasic salt cannot be avoided even when aging and drying are performed under high temperature and high humidity.
ところで本発明のようにこの従来粉末にPbO（YELLO
W）を加えた粉末を用いると、先にのべたようにPbO（YE
LLOW）からは４塩基性塩が生成しやすいため高温多湿下
で熟成乾燥をすると、４塩基性塩の生成を促進すること
ができる。By the way, as in the present invention, PbO (YELLO)
When the powder to which W) is added is used, PbO (YE
LLOW), a tetrabasic salt is likely to be produced, so that aging and drying under high temperature and high humidity can promote the production of the tetrabasic salt.
一度４塩基性塩の生成が促進されると、もともと４塩
基性塩が生成され易い条件下であるためこれが核となり
益々４塩基性塩の生成を促進でき、前記（１），（２）
のような問題を生じない極板を得ることができる。Once the formation of the 4-basic salt is promoted, the formation of the 4-basic salt becomes a nucleus under the conditions under which the 4-basic salt is likely to be formed from the beginning, so that the formation of the 4-basic salt can be further promoted.
Can be obtained.
また４塩基性塩の結晶の大きさは３塩基性塩の結晶に
くらべて約100倍程度大きい。そのため極板に形成され
る孔も大きくなりその分、電解液の極板への移動が容易
になり電池容量が増大する。The size of the crystals of the tetrabasic salt is about 100 times larger than the crystals of the tribasic salt. Therefore, the hole formed in the electrode plate becomes large, and accordingly, the movement of the electrolyte to the electrode plate becomes easy, and the battery capacity increases.
なおPbO（YELLOW）のみを加えて生成した４塩基性硫
酸鉛の巨大な結晶からなる未化成板では化成中の充電効
率が悪い。An unformed plate composed of giant crystals of tetrabasic lead sulfate formed by adding only PbO (YELLOW) has poor charging efficiency during formation.
充電効率を高めるためには極板の化成を容易にする方
法として昔から広く用いられていた鉛丹を鉛粉に混入す
る方法がこの場合も化成を容易にする方法として有効で
ある。又、熟成乾燥時ペーストを固化する成分として金
属鉛分も必要となる。In order to increase the charging efficiency, a method of mixing lead tin into lead powder, which has been widely used as a method of facilitating the formation of the electrode plate, is effective as a method of facilitating the formation in this case as well. Further, a metal lead component is also required as a component for solidifying the paste during aging and drying.
PbO（YELLOW）と鉛丹を含む粉体はPbO（RED）および
金属鉛を含む前述の鉛粉を焼成することにより得られ
る。約400〜500℃の下で主に鉛丹が、又500℃以上の下
でPbO（YELLOW）が生成してくるので400〜500℃付近の
任意の温度で焼成することにより希望の組成の粉体を得
ることができる。The powder containing PbO (YELLOW) and red lead is obtained by firing the above-mentioned lead powder containing PbO (RED) and metallic lead. Platinum is produced mainly at about 400-500 ° C, and PbO (YELLOW) is produced at about 500 ° C or more. You can get the body.
実 施 例 以下実施例により本発明を説明する。EXAMPLES The present invention will be described below with reference to examples.
（実施例１） 鉛および鉛酸化物の混合粉末1Kgに対し水100c.c.およ
び比重1.60の硫酸60c.c.の割合で混練しペーストとし、
これを格子に充填後、温度85℃、湿度90％で20時間熟成
し正極未化成板を得た。混合粉末中の鉛丹量20重量％、
金属塩量15重量％とし、PbO（YELLOW）量を０〜40重量
％の範囲で変化させ、残りをPbO（RED）とした。(Example 1) 1 kg of mixed powder of lead and lead oxide was kneaded at a ratio of 100 c.c. of water and 60 c.c. of sulfuric acid having a specific gravity of 1.60 to form a paste.
After filling this in a grid, it was aged at a temperature of 85 ° C. and a humidity of 90% for 20 hours to obtain a positive electrode unformed plate. 20% by weight of lead tin in the mixed powder,
The amount of metal salt was 15% by weight, the amount of PbO (YELLOW) was changed in the range of 0 to 40% by weight, and the remainder was PbO (RED).
その未化成板中の３塩基性硫酸鉛と４塩基性硫酸鉛の
Ｘ線回折の強度を第１図に示す。これよりPbO（YELLO
W）の含有量が５重量％以上の場合、殆ど４塩基性硫酸
鉛のみが生成することがわかる。また化成後の活物質の
中央に残る硫酸鉛の白点もPbO（YELLOW）の含有量５重
量％以上で消失する。FIG. 1 shows the X-ray diffraction intensities of the tribasic lead sulfate and the tetrabasic lead sulfate in the unformed plate. PbO (YELLO)
It is understood that when the content of W) is 5% by weight or more, almost only 4-basic lead sulfate is formed. In addition, the white point of lead sulfate remaining at the center of the active material after chemical formation disappears when the content of PbO (YELLOW) is 5% by weight or more.
以上のことより混合粉末中に含まれるPbO（YELLOW）
の量は５重量％以上で本発明の効果を充分発揮する。From the above, PbO (YELLOW) contained in the mixed powder
When the amount is 5% by weight or more, the effect of the present invention is sufficiently exhibited.
（実施例２） 鉛および鉛酸化物の混合粉末中の鉛丹量を０〜60重量
％の範囲で変化させ、PbO（YELLOW）量を５重量％およ
び30重量％，金属鉛量を10重量％，残りをPbO（RED）と
し実施例１と同様に極板を作製した。(Example 2) The amount of lead in the mixed powder of lead and lead oxide was changed in the range of 0 to 60% by weight, the amount of PbO (YELLOW) was 5% by weight and 30% by weight, and the amount of metallic lead was 10% by weight. %, And the balance being PbO (RED), and an electrode plate was produced in the same manner as in Example 1.
この極板を比重1.240の硫酸浴中、2.5×10-2A/cm2の
電流密度で充電し、正極活物質1gあたり0.350Ah（化成
に必要な理論化成電気量の約1.5倍）の電気量で充電し
たときのPbO2の生成量を第２図に示す。This electrode plate is charged in a sulfuric acid bath with a specific gravity of 1.240 at a current density of 2.5 × 10 -2 A / cm 2 , and 0.350 Ah per gram of the positive electrode active material (about 1.5 times the theoretical formation electricity required for formation). FIG. 2 shows the amount of PbO 2 generated when charged by the amount.
第２図よりPbO（YELLOW）量が５重量％の場合、鉛丹
含有量20重量％以上でPbO2の生成率が80％を越えてお
り、電槽化成効率の改善が顕著であることがわかる。According to FIG. 2, when the amount of PbO (YELLOW) is 5% by weight, the production rate of PbO 2 exceeds 80% when the content of lead is 20% by weight or more, and the improvement in the battery formation efficiency is remarkable. Recognize.
（実施例３） 鉛および鉛酸化物の混合粉末中の金属鉛量を０〜30重
量％の範囲で変化させ、PbO（YELLOW）量を５および30
重量％、鉛丹量を20および40重量％、残りPbO（RED）と
し実施例１と同様の方法で極板を作製し電池とした。こ
の電池についてJISD5301に規定される寿命試験を行なっ
た。第３図はPbO（YELLOW）５重量％，鉛丹量20重量％
とした時の混合粉末中に含まれる金属鉛量と寿命回数の
関係を示したものである。(Example 3) The amount of metallic lead in the mixed powder of lead and lead oxide was changed in the range of 0 to 30% by weight, and the amount of PbO (YELLOW) was 5 and 30.
An electrode plate was prepared in the same manner as in Example 1 to obtain a battery by setting the weight%, the lead content to 20 and 40% by weight, and the remaining PbO (RED). This battery was subjected to a life test specified in JISD5301. Fig. 3 shows 5% by weight of PbO (YELLOW) and 20% by weight of lead.
2 shows the relationship between the amount of metallic lead contained in the mixed powder and the number of lifespans.
第３図に示すように金属鉛含有量が10重量％以上ある
とき、寿命回数が安定して高いレベルにあることがわか
る。As shown in FIG. 3, when the metal lead content is 10% by weight or more, it can be seen that the number of lifetimes is stably high.
また第３図には上記極板を用いた電池についての−15
℃、150A放電時の持続時間をあわせて示している。金属
鉛含有量が20重量％を越すと低温急放電持続時間の低下
が顕著である。したがって望ましい金属鉛含有量は10重
量％以上20重量％以下である。FIG. 3 shows -15 of the battery using the electrode plate.
Also shown are the duration at 150 ° C and 150A discharge. When the metal lead content exceeds 20% by weight, the low-temperature rapid discharge duration is significantly reduced. Therefore, a desirable metal lead content is 10% by weight or more and 20% by weight or less.
なお第３図はPbO（YELLOW）量５重量％，鉛丹量20重
量％の場合の結果であるが、PbO（YELLOW）量および鉛
丹量を上記の範囲で変化させても同様の傾向があり、望
ましい金属鉛含有量はやはり10重量％以上20重量％以下
であった。FIG. 3 shows the results when the PbO (YELLOW) content was 5% by weight and the lead tin content was 20% by weight. The same tendency was observed even when the PbO (YELLOW) content and the lead red content were changed within the above ranges. Yes, the desired metallic lead content was again between 10% and 20% by weight.
また第２図においてPbO（YELLOW）の量が多くなるに
従い、鉛丹量を増やしてもPbO2の生成率が低くなるが、
PbO（YELLOW）に対しての鉛丹量が重量比で1.7倍以上に
なるとこの傾向は克服できることがわかる。Also, in FIG. 2, as the amount of PbO (YELLOW) increases, the production rate of PbO 2 decreases even if the amount of lead red is increased.
It can be seen that this tendency can be overcome when the amount of lead tin with respect to PbO (YELLOW) becomes 1.7 times or more by weight.
以上のことと最適な金属含有量の最大が20重量％であ
ることを合わせると、好ましいPbO（YELLOW）および鉛
丹含有量の上限が規定される。Combining the above with the fact that the maximum of the optimum metal content is 20% by weight, the upper limit of the preferable PbO (YELLOW) and lead tin content is defined.
その値はPbO（YELLOW）量で30重量％，鉛丹量50重量
％となる。The value is 30% by weight of PbO (YELLOW) and 50% by weight of lead.
（実施例４） 鉛丹量20重量％,PbO（YELLOW）量５重量％，金属鉛量
10重量％、残部PbO（RED）の鉛および鉛酸化物の混合粉
末を用いて実施例１と同一条件で極板とし、次の条件で
熟成乾燥した。(Example 4) Lead content 20% by weight, PbO (YELLOW) content 5% by weight, metal lead content
An electrode plate was prepared under the same conditions as in Example 1 by using a mixed powder of lead and lead oxide of PbO (RED) with the balance being 10% by weight, and aged and dried under the following conditions.
の条件では４塩基硫酸塩が生成する。の条件は従
来より用いられていた熟成乾燥方法であるが、３塩基硫
酸鉛が生成する。すなわちPbO（YELLOW）が含まれてい
ても熟成条件が最適でないと４塩基性塩は生成しない。 Under these conditions, a 4-basic sulfate is formed. The condition (1) is an aging drying method conventionally used, but lead tribasic lead sulfate is produced. That is, even if PbO (YELLOW) is contained, a tetrabasic salt is not produced unless aging conditions are optimal.
これらの極板を用いて電池を製作し、５時間率で放電
した結果を第４図に示す。本発明による極板は従来の３
塩基性硫酸鉛を作る熟成乾燥法にくらべ約20％の容量増
がはかれる。A battery was manufactured using these electrode plates, and the results of discharging at a 5-hour rate are shown in FIG. The electrode plate according to the present invention is
The capacity is increased by about 20% compared with the aging drying method to make basic lead sulfate.
（実施例５） 熟成乾燥条件についてさらに詳しく温度，湿度と生成
の関係について調べた結果を表１に示す。(Example 5) Table 1 shows the results of examining the relationship between temperature, humidity, and generation in more detail regarding the aging and drying conditions.
実施例４と同一のペースト組成の極板をつくり、各温
度および各湿度で20時間熟成乾燥を行い、生じた３塩基
性硫酸鉛および４塩基性硫酸鉛のＸ線回折強度を定性的
に調べた。表１から分るように温度80℃以上，湿度85％
以上のもとで４塩基性硫酸鉛が多く生成し、３塩基性硫
酸鉛は検出されないか、されてもわずかであった。 An electrode plate having the same paste composition as that of Example 4 was prepared, aged and dried at each temperature and each humidity for 20 hours, and the X-ray diffraction intensities of the resulting tribasic lead sulfate and tetrabasic lead sulfate were qualitatively examined. Was. As can be seen from Table 1, the temperature is over 80 ℃ and the humidity is 85%
Under the above conditions, a large amount of tetrabasic lead sulfate was produced, and tribasic lead sulfate was not detected or was little.
ただし温度100℃で湿度が95％以上の場合、強度が弱
くなる傾向を示した。この原因についてははっきりしな
いが、結晶成長のしかたが異なるのかもしれない。However, when the temperature was 100 ° C and the humidity was 95% or more, the strength tended to be weak. Although the cause is not clear, the way of crystal growth may be different.
以上の結果から熟成乾燥温度は80℃以上95℃以下，湿
度は85％以上が適していると結論した。From the above results, it was concluded that the aging drying temperature is more than 80 ℃ and less than 95 ℃, and the humidity is more than 85%.
発明の効果 以上、本発明の正極板製造法によれば、熟成乾燥にお
いて４塩基性硫酸鉛を安定して生成することができ、ひ
いては従来にくらべ電池容量が大幅に向上する鉛蓄電池
を提供することができ、その工業的価値は甚だ大なるも
のがある。As described above, according to the positive electrode plate manufacturing method of the present invention, it is possible to stably produce 4-basic lead sulfate in aging and drying, and to provide a lead-acid battery that has a significantly improved battery capacity as compared with the related art. And its industrial value is immense.
第１図は混合粉末中のPbO（YELLOW）含有量と、熟成後
生じた４塩基硫酸鉛又は３塩基性硫酸鉛のＸ線回折強度
との関係を示したグラフ、第２図は鉛丹添加による電槽
化成効率向上の効果を示す図、第３図は混合粉末中の金
属鉛含有量の寿命に対する効果と低温での初期性能に対
する影響を示す図、第４図は本発明による電池と従来の
熟成乾燥による電池との性能比較を示す。FIG. 1 is a graph showing the relationship between the PbO (YELLOW) content in the mixed powder and the X-ray diffraction intensity of 4-basic lead sulfate or 3-basic lead sulfate produced after aging, and FIG. Fig. 3 shows the effect on the life of the lead metal content in the mixed powder and the effect on the initial performance at a low temperature, and Fig. 4 shows the battery according to the present invention and the conventional battery. 5 shows a performance comparison with a battery obtained by aging and drying of a battery.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−51053（ＪＰ，Ａ) 特開 昭64−89262（ＪＰ，Ａ) 特開 昭62−26766（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 4/14 H01M 4/20 H01M 4/21 H01M 4/57────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-51053 (JP, A) JP-A-64-89262 (JP, A) JP-A-62-26766 (JP, A) (58) Field (Int.Cl. 6 , DB name) H01M 4/14 H01M 4/20 H01M 4/21 H01M 4/57
Claims (6)
赤色リサージ〔PbO（RED）〕および金属鉛粉末を主成分
とする混合粉末と水および硫酸とを混合しペーストと
し、前記ペーストを鉛合金からなる格子体に充填したの
ち、温度80℃から95℃，湿度85％以上の雰囲気中で熟成
乾燥することを特徴とした鉛蓄電池用正極板の製造法。1. A yellow litharge [PbO (YELLOW)], leadtan,
A mixed powder mainly composed of red litharge [PbO (RED)] and metallic lead powder is mixed with water and sulfuric acid to form a paste, and the paste is filled in a grid made of a lead alloy. A method for producing a positive electrode plate for lead-acid batteries, characterized by aging and drying in an atmosphere at a humidity of 85% or more.
W）〕を主成分とする粉末と赤色リサージ〔PbO（RE
D）〕および金属鉛を主成分とする鉛粉とを混合するこ
とにより前記混合粉末を得ることを特徴とする特許請求
の範囲第１項記載の鉛蓄電池用正極板の製造法。2. The method of claim 2 wherein the lead red and yellow litharge [PbO (YELLO)
W)] and red litharge [PbO (RE
2. The method for producing a positive electrode plate for a lead-acid battery according to claim 1, wherein the mixed powder is obtained by mixing D)] and a lead powder containing metal lead as a main component.
が前記混合粉末に対して５重量％以上30重量％以下であ
る特許請求の範囲第１項又は第２項記載の鉛蓄電池用正
極板の製造法。3. The positive electrode for a lead-acid battery according to claim 1, wherein the content of yellow litharge [PbO (YELLOW)] is 5% by weight or more and 30% by weight or less based on the mixed powder. The method of manufacturing the board.
量％以上50重量％以下である特許請求の範囲第３項記載
の鉛蓄電池用正極板の製造法。4. The method for producing a positive electrode plate for a lead-acid battery according to claim 3, wherein the content of lead red is 20% by weight or more and 50% by weight or less based on the mixed powder.
鉛丹の割合が重量比で1.7倍以上である特許請求の範囲
第４項記載の鉛蓄電池用正極板の製造法。5. The method according to claim 4, wherein the ratio of lead red to yellow litharge [PbO (YELLOW)] is 1.7 times or more by weight.
て10重量％以上20重量％以下である特許請求の範囲第５
項記載の鉛蓄電池用正極板の製造法。6. The method according to claim 5, wherein the content of the metal lead powder is 10% by weight or more and 20% by weight or less based on the mixed powder.
4. The method for producing a positive electrode plate for a lead storage battery according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1283237A JP2773312B2 (en) | 1989-10-30 | 1989-10-30 | Manufacturing method of positive electrode plate for lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1283237A JP2773312B2 (en) | 1989-10-30 | 1989-10-30 | Manufacturing method of positive electrode plate for lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03145056A JPH03145056A (en) | 1991-06-20 |
| JP2773312B2 true JP2773312B2 (en) | 1998-07-09 |
Family
ID=17662867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1283237A Expired - Fee Related JP2773312B2 (en) | 1989-10-30 | 1989-10-30 | Manufacturing method of positive electrode plate for lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2773312B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2612978B2 (en) * | 1991-05-14 | 1997-05-21 | 株式会社ユアサコーポレーション | Method for manufacturing electrode plate for lead-acid battery |
| WO2013122132A1 (en) * | 2012-02-14 | 2013-08-22 | 新神戸電機株式会社 | Positive electrode plate for lead acid battery, method for producing said electrode plate, and lead acid battery using said positive electrode plate |
-
1989
- 1989-10-30 JP JP1283237A patent/JP2773312B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03145056A (en) | 1991-06-20 |
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