JP2773313B2 - Manufacturing method of lead storage battery - Google Patents
Manufacturing method of lead storage batteryInfo
- Publication number
- JP2773313B2 JP2773313B2 JP1283238A JP28323889A JP2773313B2 JP 2773313 B2 JP2773313 B2 JP 2773313B2 JP 1283238 A JP1283238 A JP 1283238A JP 28323889 A JP28323889 A JP 28323889A JP 2773313 B2 JP2773313 B2 JP 2773313B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lead
- lattice
- positive electrode
- electrode plate
- 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
- 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
-
- 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
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)
- 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。Description: TECHNICAL FIELD The present invention relates to a method for manufacturing a lead storage battery.
従来の技術 鉛蓄電池に用いる極板は赤色リサージ〔以下PbO（RE
D）という〕等の酸化鉛粉と金属鉛粉を水および硫酸で
混練したペーストを鉛合金からなる格子体に充填したの
ち、それを熟成乾燥したものを化成して作られる。2. Description of the Related Art The electrode plate used for a lead-acid battery is a red litharge [PbO (RE)
D)], a paste obtained by kneading lead oxide powder and metallic lead powder with water and sulfuric acid is filled in a grid made of a lead alloy, and then aged and dried to be chemically formed.
ここで用いられる格子体は、かっては鉛合金を鋳造す
ることにより作られていたが、最近ではより生産性の高
い方法として鉛合金の圧延シートをエキスパンド加工す
ることにより得られるエキスパンド格子が用いられるよ
うになってきている。The lattice body used here was once made by casting a lead alloy, but recently an expanded lattice obtained by expanding a rolled sheet of a lead alloy is used as a more productive method. It is becoming.
このエキスパンド加工により格子を製造する場合、圧
延シートの機械的強度を高くするため合金にはもっぱら
Pb−Ca−Sn合金が使用される。When a grid is manufactured by this expanding process, the alloy is exclusively used to increase the mechanical strength of the rolled sheet.
Pb-Ca-Sn alloy is used.
このエキスパンド格子の形状の一例を第１図に示す。
エキスパンドに展開された菱形のます目の角度ｋは、通
常100〜120゜の間である。（100゜より鋭角であるとエ
キスパンド展開時に骨が切断する等の問題を生ずる。） エキスパンド格子は、このような形状をしているため
図中ｈ方向の機械的強度ｗ方向よりも弱く伸び易い。ま
たエキスパンド格子に用いられるPb−Ca−Sn合金は正極
に使用され酸化されると生成物となるPbO2と強固に接着
すると性質をもつ。FIG. 1 shows an example of the shape of the expanded grating.
The angle k of the squares of the expanded diamond is usually between 100 and 120 °. (If the angle is more than 100 °, there is a problem that the bone is cut during expansion.) The expanded lattice has such a shape and is weaker than the mechanical strength w direction h in the figure and is easily elongated. . Further, the Pb-Ca-Sn alloy used for the expanded lattice has a property of being used as a positive electrode and firmly adhering to PbO 2 which is a product when oxidized.
発明が解決しようとする課題 このような特性をもつエキスパンド格子を正極に使用
した場合次のような問題を生ずる。Problems to be Solved by the Invention When the expanded lattice having such characteristics is used for the positive electrode, the following problems occur.
活物質の充放電による膨張，収縮のためエキスパン
ド格子がｈ方向に伸ばされ格子と物質とのあいだにわず
かの亀裂を生じ電池性能が低下する。Due to expansion and contraction due to charge and discharge of the active material, the expanded lattice is elongated in the h direction, and a slight crack is generated between the lattice and the material to lower the battery performance.
の状態に近い状態で充放電が行なわれると格子近
傍付近が選択的に充放電される。そのため格子の酸化が
進行する。その生産物であるPbO2は母材と堅固にくっつ
いており、しかもPbO2になるときに体積膨張する。この
ため格子はさらに変形され、格子と活物質の結合状態は
悪化し、電池の性能は低下する。When charge / discharge is performed in a state close to the above state, the vicinity of the lattice is selectively charged / discharged. Therefore, oxidation of the lattice proceeds. The product, PbO 2, is firmly attached to the base material and expands in volume when it becomes PbO 2 . For this reason, the lattice is further deformed, the bonding state between the lattice and the active material is deteriorated, and the performance of the battery is reduced.
課題を解決するための手段 本発明はこのような課題を解決するものであり、その
方法は化成時にのみ体積膨張が大きくなり、その後の充
放電では活物質の体積変化の少ない活物質の構造を作る
ものである。Means for Solving the Problems The present invention is to solve such problems, and the method is to increase the volume expansion only during chemical formation, and to reduce the volume of the active material during the subsequent charge and discharge. To make.
その具体的方法は、第１に原料としてPbO（RED），金
属鉛，黄色リサージ〔以下PbO（YELLOW）とよぶ〕およ
び鉛丹からなる混合粉末を用い、これと水および希硫酸
を混練してペースト状としてエキスパンド格子に充填し
たのち、温度80℃〜95℃，湿度90％以上の雰囲気中で熟
成乾燥してその後電池に組込まれた状態で化成する（電
槽化成）ものである。上記方法で電槽化成を行うと化成
後の正極板のｈ方向ののびが大きく６〜８％にも達す
る。First, a mixed powder of PbO (RED), metallic lead, yellow litharge (hereinafter referred to as PbO (YELLOW)) and lead red is used as a raw material, and this is kneaded with water and dilute sulfuric acid. After filling the expanded lattice as a paste, it is aged and dried in an atmosphere at a temperature of 80 ° C. to 95 ° C. and a humidity of 90% or more, and then formed into a battery (former battery formation). When the battery case is formed by the above method, the positive electrode plate after formation has a large h-direction spread of 6 to 8%.
このため、第２に化成前の正極板の高さを負極板とく
らべて６％から８％低くした状態で電池を組みたてたの
ち電槽化成を行なう。本方法により実質的に使用状態で
正負極の高さを同一とすることができる。Therefore, second, the battery is assembled in a state where the height of the positive electrode plate before formation is 6% to 8% lower than that of the negative electrode plate, and then the battery case formation is performed. According to this method, the heights of the positive and negative electrodes can be made substantially the same in a used state.
作用 PbO（RED），金属鉛,PbO（YELLOW）および鉛丹からな
る混合粉末と水および稀硫酸を混練してペーストとし、
これを格子体に充填して、温度80〜95℃，湿度90％以上
の条件下で熟成乾燥すると、熟成乾燥中の化学変化によ
り４塩基性硫酸鉛を多量を含んだ未化成板ができる。
（通常は温度70℃以下で熟成乾燥され、この場合は３塩
基性硫酸鉛を多量に含む）。Action A mixed powder consisting of PbO (RED), metallic lead, PbO (YELLOW) and lead red, and water and dilute sulfuric acid are kneaded to form a paste.
This is filled in a lattice, and aged and dried under the conditions of a temperature of 80 to 95 ° C. and a humidity of 90% or more, an unformed plate containing a large amount of tetrabasic lead sulfate is formed due to a chemical change during the aging and drying.
(It is usually aged and dried at a temperature of 70 ° C. or less, in which case a large amount of tribasic lead sulfate is contained).
このように４塩基性硫酸鉛を多量に含んだ未化成板を
化成すなわち電界酸化して二酸化鉛にしたときは、従来
の３塩基性硫酸鉛を多量に含んだ未化成板を化成したと
きにくらべて活物質の著しい体積膨張が生じることを見
いだした。As described above, when an unformed plate containing a large amount of tetrabasic lead sulfate is formed, that is, electrolytically oxidized to lead dioxide, a conventional unformed plate containing a large amount of tribasic lead sulfate is formed. It has been found that remarkable volume expansion of the active material occurs.
その結果エキスパンド格子は格子強度の弱いｈ方向に
化成後に伸びを生ずる。この活物質の膨張による伸びは
化成時に著しいが、その後の充放電によるのびは従来と
くらべて少ない。これは充放電による活物質の膨張が少
なくなることと、極板は耳部１で固定されているため、
伸びを抑制する力がこの部分で働くためである。As a result, the expanded lattice elongates after formation in the h direction where the lattice strength is weak. Although the elongation due to the expansion of the active material is remarkable at the time of chemical formation, the extension due to subsequent charging and discharging is smaller than in the past. This is because the expansion of the active material due to charging and discharging is reduced, and the electrode plate is fixed at the ear 1,
This is because the force for suppressing elongation works in this part.
したがって膨張しようとする活物質と変形を抑制され
た格子とが互いに相手を押し合うような力がはたらき、
格子と活物質の接触は寿命末期まで良好になり問題点
およびが解決される。Therefore, the force that the active material that is about to expand and the lattice whose deformation is suppressed works against each other works,
The contact between the lattice and the active material is improved until the end of the life, and the problem and the problem are solved.
耳部１により極板がｈ方向へ伸びるのを抑制する力
は、したがって極板，セパレータ等の極板群を電槽内に
組みつけたのち化成する、いわゆる電槽化成にはじめて
生ずるものであり、あらかじめ化成した極板を極板群に
組みつける方法ではこの力は大きくなく、したがって本
発明の効果も顕著には期待できない。The force which suppresses the extension of the electrode plate in the h direction by the ear portion 1 is first generated in the so-called battery case formation, which is performed after the electrode plate group such as the electrode plate and the separator is assembled in the battery case. However, in the method of assembling the electrode plate formed in advance into the electrode group, this force is not large, and therefore the effect of the present invention cannot be expected remarkably.
実 施 例 次に本発明について実施例により説明する。EXAMPLES Next, the present invention will be described with reference to examples.
鉛および鉛酸化物からなる混合粉末1kgに対し水100c.
c.および比重1.60の硫酸60c.c.を加え混練しペーストと
し、これをPb−Ca−Sn合金からなるエキスパンド格子に
充填し温度85℃，湿度90％で20時間熟成乾燥し正極未化
成板とした。これをａとする。このときのエキスパンド
格子は縦110mm,横100mm,重量30.0gであった。混合粉末
の組成は鉛丹20重量％，金属鉛15重量％,PbO（YELLOW）
５重量％，残部PbO（RED）とした。100 kg of water per 1 kg of mixed powder consisting of lead and lead oxide.
c. and sulfuric acid 60 c.c. having a specific gravity of 1.60 were added and kneaded to form a paste. The paste was filled into an expanded lattice made of a Pb-Ca-Sn alloy, aged at 85 ° C. and 90% humidity for 20 hours, and dried for 20 hours. And Let this be a. The expanded grid at this time was 110 mm long, 100 mm wide and 30.0 g in weight. The composition of the mixed powder is 20% by weight of lead red, 15% by weight of metallic lead, PbO (YELLOW)
The content was 5% by weight and the balance was PbO (RED).
このようなペーストおよび熟成乾燥条件により、正極
未化成板ａ中に４塩基性硫酸鉛を主体とする成分を生成
させた。Under such paste and aging and drying conditions, a component mainly composed of tetrabasic lead sulfate was produced in the positive electrode unformed plate a.
一方比較のために同一条件でペースト充填した極板を
温度60℃，湿度70％で20時間熟成乾燥し正極未化成板ｂ
を作成した。これの主成分は３塩基性硫酸鉛であった。On the other hand, for comparison, the electrode plate filled with the paste under the same conditions is aged at a temperature of 60 ° C. and a humidity of 70% for 20 hours and dried, and the positive electrode unformed plate
It was created. The main component was tribasic lead sulfate.
さらに比較のためにａの極板を電池を組みたてる前に
化成を行った正極板を用意した。これをｃとする。Further, for comparison, a positive electrode plate which had been subjected to chemical conversion before preparing the battery with the electrode plate a was prepared. This is assumed to be c.
さらに比較のために用いたエキスパンド格子と同一寸
法，同一重量のPb−Ca−Sn合金からなる鋳造格子を用い
てａと同じ方法で正極未化成板ｄを作製した。Further, an unformed positive electrode plate d was prepared in the same manner as in a, using a cast lattice made of a Pb-Ca-Sn alloy having the same dimensions and the same weight as the expanded lattice used for comparison.
最後に縦102mm,横100mm,重量30.0gのエキスパンド格
子を用いてａと同条件で正極未化成板ｅを作成した。Finally, a positive electrode unformed plate e was prepared under the same conditions as in a using an expanded lattice having a length of 102 mm, a width of 100 mm and a weight of 30.0 g.
これらの正極板を用いて常法により５時間率容量28Ah
の自動車用鉛蓄電池を作製した。これらの電池をそれぞ
れの極板a,b,c,d,eに対応し、A,B,C,D,Eとする。なおA,
B,D,Eについては電槽化成を行い、Ｃについては正負極
とも化成した極板を使用し、電池組立後初充電を行っ
た。Using these positive electrode plates, 5 hour rate capacity 28Ah
Was manufactured. These batteries correspond to the respective plates a, b, c, d, and e and are designated as A, B, C, D, and E. A,
For B, D, and E, a battery case was formed, and for C, first formed after the battery was assembled, using positive and negative electrode plates.
これらの電池についてSAE J240にもとづく寿命試験を
行った。この結果を第２図に示す。These batteries were subjected to a life test based on SAE J240. The result is shown in FIG.
従来電池に相当する電池Ｂにくらべ本発明による電池
Ａでは第２図より約30％程寿命特性が改善されているこ
とがわかる。FIG. 2 shows that the life characteristics of the battery A according to the present invention are improved by about 30% as compared with the battery B corresponding to the conventional battery.
この電池Ａと電池Ｂについて化成時およびSAE寿命試
験中の正極板のｈ方向ののびを示したものが第３図であ
る。FIG. 3 shows the h-direction spread of the positive electrode plates of the batteries A and B during the formation and during the SAE life test.
本発明による電池Ａの極板ａののびは化成が終了した
時点ですでに約７％にも達しており、その後寿命試験中
ののびは従来電池Ｂの極板ｂにくらべて極めて少ないも
のとなる。The extension of the electrode a of the battery A according to the present invention has already reached about 7% at the end of the formation, and the extension during the life test after that is extremely small as compared with the electrode b of the conventional battery B. Become.
これは化成したときの化学変化による体積膨張が著し
いことを示しており、この活物質の膨張により格子と活
物質の界面が常に圧迫されて密着することができる。こ
れは格子のｈ方向ののびが耳部で規制されるために、よ
り効果的になると推定される。This indicates that volume expansion due to chemical change during chemical formation is remarkable, and the interface between the lattice and the active material is constantly pressed by the expansion of the active material, so that close contact can be achieved. This is presumed to be more effective because the expansion of the grid in the h direction is restricted by the ears.
あらかじめ電池外部で化成を行なった電池Ｃの場合、
既にｈ方向にのびた極板を極板群に組立てるため、格子
耳部で格子ののびを規制する力は電池Ａにくらべ大きく
はない。In the case of battery C, which has been formed outside the battery in advance,
Since the electrode plates that have already been extended in the h direction are assembled into the electrode plate group, the force that restricts the grid from extending at the grid ears is not greater than that of the battery A.
電池Ｃの寿命はＡにくらべ20％低いが、これはＣは上
記格子ののびを規制する力が弱いことが原因していると
考えられる。The life of the battery C is 20% shorter than that of the battery A, which is considered to be due to the fact that C has a weak force for regulating the lattice growth.
電池Ａではこのように従来電池より寿命向上が図られ
たが2500サイクルと3000サイクルの間でｈ方向に正極板
が伸びて陰極部と接し内部短絡をおこし寿命がつきた状
態となった。As described above, the life of the battery A was improved over that of the conventional battery. However, between 2500 and 3000 cycles, the positive electrode plate extended in the h direction and came into contact with the cathode to cause an internal short circuit, resulting in a state where the life was extended.
電池Ｅはこの点を改善しあらかじめ正極のｈ方向寸法
すなわち高さを低くし陰極板に対し約７％短かくしたも
のである。寿命試験中に内部短絡することもなくさらに
寿命を改善することができた。The battery E is improved in this point, and the dimension of the positive electrode in the h direction, that is, the height is reduced in advance to make it about 7% shorter than the cathode plate. The life could be further improved without an internal short circuit during the life test.
電池Ｄは鋳造格子を用いた場合であるが、格子重量を
エキスパンド格子と同じ30gと軽量なものを使用した。The battery D was a case using a cast grid, but a battery having a grid weight as light as 30 g as the expanded grid was used.
このとき、極板ｄは電槽化成後ｈ方向,w方向にほぼ等
方的にのび樽状に変形した。それとともに格子強度が活
物質の膨張する力に抗しきれずに部分的に切断した。At this time, the electrode plate d was substantially isotropically deformed into a barrel shape in the h and w directions after the formation of the battery case. At the same time, it was partially cut without the lattice strength being able to withstand the expanding force of the active material.
そのために寿命特性もきわめて短かいものとなった。
この点を改善するためには格子重量を増し、格子強度を
向上する必要があり、格子重量の増加が必然的なものと
なってしまう。As a result, the life characteristics were also very short.
In order to improve this point, it is necessary to increase the grid weight and the grid strength, and the grid weight is inevitably increased.
発明の効果 以上のべたように本発明は、鉛蓄電池の正極において
膨張しやすい活物質を用い活物質の膨張する力を特定方
向の伸びという形で吸収するのにすぐれた形状および材
質的特性をもつエキスパンド格子と組合せ、さらにこの
伸びを制限するような力がはたらくよう電池を組みたて
るようにしたものである。Effect of the Invention As described above, the present invention uses an active material that easily expands in the positive electrode of a lead-acid battery, and has an excellent shape and material characteristics for absorbing the expanding force of the active material in the form of elongation in a specific direction. The battery is assembled in such a way that it works in combination with the expanded grid, and that a force that limits this elongation works.
その結果、従来とくらべ寿命特性が従来品比約50％増
加することができ、その工業的価値は大きい。As a result, the life characteristics can be increased by about 50% as compared with the conventional product, and its industrial value is great.
第１図は一般的なエキスパンド格子の形状、第２図は本
発明の鉛蓄電池製造法によって作った電池および比較品
のSAE J240による寿命試験結果、第３図は本発明の電池
と比較従来品の正極板の伸びを示したものである。 １……格子耳部、２……格子本体。FIG. 1 shows the shape of a general expanded grid, FIG. 2 shows the results of a life test by SAE J240 of a battery and a comparative product made by the lead-acid battery manufacturing method of the present invention, and FIG. 1 shows the elongation of the positive electrode plate. 1 ... Lattice ears, 2 ... Lattice body.
───────────────────────────────────────────────────── 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 (2)
色リサージ〔PbO（YELLOW）〕および鉛丹からなる混合
粉末と水および稀硫酸を混練してペーストとし、これを
エキスパンド格子に充填したのち、温度80〜95℃，湿度
90％以上の雰囲気中で熟成乾燥し正極末化成板を作成
し、その後電池に組込んだ状態で化成することを特徴と
した鉛蓄電池の製造法。1. A mixed powder of red litharge [PbO (RED)], metallic lead, yellow litharge [PbO (YELLOW)] and lead red, and water and dilute sulfuric acid are kneaded to form a paste, which is filled in an expanded lattice. After that, temperature 80 ~ 95 ℃, humidity
A method for producing a lead-acid battery, characterized in that it is aged and dried in an atmosphere of 90% or more to prepare a positive electrode chemical conversion plate, and then formed and assembled into a battery.
らべて６％から８％低くした状態で電池を組みたてたの
ち化成することを特徴とした特許請求の範囲第１項記載
の鉛蓄電池の製造法。2. The method according to claim 1, wherein the battery is assembled in a state where the height of the positive electrode plate before formation is 6% to 8% lower than the height of the negative electrode plate, and then the formation is performed. 2. A method for producing a lead storage battery according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1283238A JP2773313B2 (en) | 1989-10-30 | 1989-10-30 | Manufacturing method of lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1283238A JP2773313B2 (en) | 1989-10-30 | 1989-10-30 | Manufacturing method of lead storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03145057A JPH03145057A (en) | 1991-06-20 |
| JP2773313B2 true JP2773313B2 (en) | 1998-07-09 |
Family
ID=17662881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1283238A Expired - Fee Related JP2773313B2 (en) | 1989-10-30 | 1989-10-30 | Manufacturing method of lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2773313B2 (en) |
-
1989
- 1989-10-30 JP JP1283238A patent/JP2773313B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03145057A (en) | 1991-06-20 |
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