JPH04206344A - Manufacture of lead accumulator anode plate - Google Patents
Manufacture of lead accumulator anode plateInfo
- Publication number
- JPH04206344A JPH04206344A JP2333738A JP33373890A JPH04206344A JP H04206344 A JPH04206344 A JP H04206344A JP 2333738 A JP2333738 A JP 2333738A JP 33373890 A JP33373890 A JP 33373890A JP H04206344 A JPH04206344 A JP H04206344A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- pbo2
- anode plate
- powder
- layer
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 239000002142 lead-calcium alloy Substances 0.000 claims description 10
- 239000006183 anode active material Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 15
- 239000011149 active material Substances 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 238000007789 sealing Methods 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 3
- 238000007605 air drying Methods 0.000 abstract description 2
- 239000011888 foil Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 229910006531 α-PbO2 Inorganic materials 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 13
- 229910000978 Pb alloy Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 229910006529 α-PbO Inorganic materials 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
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
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は鉛電池用陽極板の製造方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing an anode plate for a lead-acid battery.
（従来の技術）
従来の鉛電池陽極板にはペースト式およびクラッド式が
ある。前者は、鉛合金から成る格子体に鉛粉を希硫酸で
練った鉛ペーストを塗布し、希硫酸中で化成するもので
ある。後者は鉛合金から成る芯金の周りに鉛粉、鉛丹な
どの鉛酸化物を充填し、希硫酸中で化成するものである
。上記二種類の方法が鉛電池陽極板の主な製造方法であ
る。(Prior Art) Conventional lead battery anode plates include paste type and clad type. In the former method, a lead paste made by kneading lead powder with dilute sulfuric acid is applied to a grid made of a lead alloy, and then chemically formed in the dilute sulfuric acid. The latter is a method in which lead powder, lead oxide such as red lead is filled around a core metal made of a lead alloy, and the material is chemically formed in dilute sulfuric acid. The above two methods are the main methods for producing lead battery anode plates.
近年、鉛電池のシール化、さらに小型化が行なわれてい
る中で、主として採用されている陽極板はペースト式極
板である。しかし、シール化、小型化さらに薄型化が強
く要求されている中で従来のペースト式極板ではこれら
の要求に答えることができなくなっている。In recent years, lead batteries have been made more sealed and more compact, and the anode plates that are mainly used are paste-type plates. However, with the strong demand for sealing, miniaturization, and thinning, conventional paste-type electrode plates are no longer able to meet these demands.
そこで、あらかしめ作製したＰｂＯ□粉末を鉛あるいは
鉛合金の基板にスクリーン印刷などによって塗布するな
どの方法が考えられ、種々試みられている。Therefore, various methods have been considered, such as applying pre-prepared PbO□ powder onto a lead or lead alloy substrate by screen printing or the like, and various attempts have been made.
（発明が解決しようとする問題点）
しかし、上記方法の問題点は塗布したＰｂＯ２粉末と鉛
あるいは鉛合金基板との密着性が得られず、充放電を繰
り返すうちに両者が剥離したり、両者の界面に硫酸が侵
入して鉛あるいは鉛合金基板の表面が不動体化し、充放
電できなくなること。さらに、このような鉛電池では基
本的に鉛あるいは鉛−カルシウム系合金の基板を用いて
いるために、鉛−カルシウム系合金を基体に用いる鉛電
池に特有の深い放電による早期の容量劣化が起こる。従
来この問題に対して、活物質を厚くし劣化の部位となる
基体表面と活′＃ＩＪ質との界面を保護するなどの方法
が取られているが、薄型化を要求されているこのような
電池では上記のような方法は取れない。(Problems to be Solved by the Invention) However, the problem with the above method is that adhesiveness between the applied PbO2 powder and the lead or lead alloy substrate cannot be obtained, and during repeated charging and discharging, both may peel off or The surface of the lead or lead alloy substrate becomes immobile due to sulfuric acid entering the interface, making charging and discharging impossible. Furthermore, since these lead batteries basically use a substrate made of lead or a lead-calcium alloy, early capacity deterioration occurs due to deep discharge, which is typical of lead-acid batteries that use lead-calcium alloys as the substrate. . Conventionally, methods have been taken to solve this problem, such as thickening the active material and protecting the interface between the substrate surface and the active IJ material, which is the site of deterioration. The above method cannot be used with batteries.
本発明はこれらの問題点を解決し、シール化、小型化お
よび薄型化の強い要求に答えることができる鉛電池陽極
板の製造方法を提供するものである。The present invention solves these problems and provides a method for manufacturing a lead battery anode plate that can meet the strong demands for sealing, miniaturization, and thinning.
（問題点を解決するだめの手段）
上記問題点を解決するために本発明では以下のような手
段を講しることとした。(Means to Solve the Problems) In order to solve the above problems, the present invention takes the following measures.
（１）電解によって鉛あるいは鉛−カルシウム系合金基
板の表面にα−Ｐｂ０２の層を形成する。(1) A layer of α-Pb02 is formed on the surface of a lead or lead-calcium alloy substrate by electrolysis.
（２） これに塗布するＰｂＯ□の粉末を、スズを含
む鉛塩浴中からの電析によって調製する。(2) PbO□ powder to be applied to this is prepared by electrodeposition from a lead salt bath containing tin.
（作用）
電解によって鉛あるいは鉛−カルシウム系合金基板の表
面にα−Ｐｂ０２の層を形成することによって、これに
塗布するＰｂＯ□の粉末との馴染み、密着性の向上を図
ると同時に、鉛あるいは鉛−カルシウム系合金基板と活
物質との実質的な界面を鉛あるいは鉛−カルシウム系合
金基板の内部、すなわち、電解によって形成した緻密な
α−ＰｂＯ□層の内側に持ってくることによって、この
部位への硫酸の侵入などによる鉛あるいは鉛−カルシウ
ム系合金基板と活物質との界面の不働態化を防止する。(Function) By forming a layer of α-Pb02 on the surface of a lead or lead-calcium alloy substrate by electrolysis, it is possible to improve the compatibility and adhesion with the PbO□ powder applied thereto, and at the same time This can be achieved by bringing the substantial interface between the lead-calcium alloy substrate and the active material inside the lead or lead-calcium alloy substrate, that is, inside the dense α-PbO□ layer formed by electrolysis. This prevents the interface between the lead or lead-calcium alloy substrate and the active material from becoming passivated due to sulfuric acid entering the site.
さらに、活物質となるＰｂＯ□粉末を、スズを含む鉛塩
浴中からの電析によって調製することによってＰｂＯ２
の結晶中に必要量のスズを極めて均一に添加することが
でき、この添加されたスズは鉛−あるいは鉛−カルシウ
ム系合金基板を用いる鉛電池に特有な深い放電を繰り返
すことによる容量の急激な低下を防止する。しかし、従
来のスズの添加方法は、たとえば、ペースト式極板の作
製において鉛粉を希硫酸で練るときに二酸化スズの粉末
を一緒に練る込むなどの方法である。この方法の問題点
はスズを二酸化スズの粉末の形で添加するので所期の効
果を得るためには多量に添加をしなければならないこと
、また、ＰｂＯ□はＰｂＯから固相反応によって、ある
いは、ｐｂｓｏ、から形成されるが、２固相反応によっ
て形成される場合ＰｂＯ□ｂＯ□へのスズの侵入は不可
能であり、ｐｂｓｏ、から形成される場合も溶解・析出
によるＰｂＯ２の形成はｐｂｓｏ４結晶の極近傍で起こ
るために、ＰｂＯ□ｂＯ□に二酸化スズ粉末の溶解によ
ってスズを効率良く均一に供給することは不可能である
。Furthermore, by preparing PbO□ powder as an active material by electrodeposition from a lead salt bath containing tin, PbO2
The required amount of tin can be added extremely uniformly into the crystal, and this added tin prevents the rapid increase in capacity due to repeated deep discharges that are characteristic of lead batteries that use lead- or lead-calcium alloy substrates. Prevent decline. However, the conventional method of adding tin is, for example, when lead powder is kneaded with dilute sulfuric acid in the production of a paste-type electrode plate, tin dioxide powder is kneaded together with the lead powder. The problem with this method is that tin is added in the form of tin dioxide powder, so it must be added in large quantities to obtain the desired effect, and PbO□ is produced from PbO through a solid phase reaction or , pbso, but when it is formed by two solid-phase reactions, it is impossible for tin to enter PbO Since this occurs very close to the crystal, it is impossible to efficiently and uniformly supply tin by dissolving tin dioxide powder into PbO□bO□.
本発明によるＰｂＯ□粉末の調製方法によって上記スズ
の添加に関する問題点は著しく改善され、サイクルサー
ビス中全般に亘ってスズ添加による弊害は全くないこと
を確認した。このように本発明によって著しく改善され
る理由は、ＰｂＯ２結晶を、スズを添加した鉛塩浴とい
う本来非常に均一である溶液中から形成することにより
、スズが少量であってもこれがＰｂＯ□結晶格結晶格子
−に侵入するためであると考えられる。The method for preparing PbO□ powder according to the present invention has significantly improved the above-mentioned problems regarding the addition of tin, and it has been confirmed that there are no adverse effects caused by the addition of tin throughout the cycle service. The reason for this remarkable improvement in the present invention is that by forming PbO2 crystals from a lead salt bath to which tin is added, which is originally a very homogeneous solution, even if the tin content is small, the PbO2 crystals are This is thought to be due to the intrusion into the crystal lattice.
（実施例） 以下に、本発明の一実施例についてのべる。(Example) An embodiment of the present invention will be described below.
第１図は、本発明によって作製した鉛電池用陽極板の断
面を模式的に示したものである。FIG. 1 schematically shows a cross section of an anode plate for a lead battery produced according to the present invention.
鉛基板１には、Ｐｂ−Ｃａ系合金すなわちＣａを０．８
ｉｍｔ、χ含む鉛合金のフォイル、厚さ０．０５ｍｍを
用いた。α−ＰｂＯ□層２は、水酸化ナトリウムを約２
５ｇ／Ｅ含むアルカリ性浴中で以下の条件で電解酸化す
ることによって形成した。The lead substrate 1 contains a Pb-Ca alloy, that is, Ca of 0.8
A lead alloy foil containing imt and χ and having a thickness of 0.05 mm was used. α-PbO□ layer 2 contains about 2 ml of sodium hydroxide.
It was formed by electrolytic oxidation in an alkaline bath containing 5 g/E under the following conditions.
浴の温度： ２５ ’Ｃ
電流密度：２ヰｍＡ／ｃｍ２
通電時間；４８ｈ
また、活物質層３を形成するために必要なＰｂＯ□粉末
は、以下の組成の浴中で白金板表面に電析させることに
よって調製した。Bath temperature: 25'C Current density: 2ヰmA/cm2 Current application time: 48h In addition, the PbO□ powder required to form the active material layer 3 was electrodeposited on the surface of the platinum plate in a bath with the following composition. It was prepared by
浴組成：硝酸鉛 −−−−一−−・−ｍ−−−・・ １
０ｇ／ １硝酸−一−−−−−−−・−９０ｍ ｌ ／
β硫酸スズ
ｌＸｌ０−’ ｗｔ−％
電析の条件は、以下のごとくである
浴の温度：２５°Ｃ
電流密度： １０ｍＡ／ｃｍ２
電析によって調製したＰｂＯ、粉末をα−ＰｂＯ□層２
を形成した鉛基板１上に塗布するために、これにポリテ
トラフルオロエチレンの含有量が約１ｗｔ・％になるよ
うにポリテトラフルオロエチレンディスバージョンを加
え、ペースト状とした。塗布量は、ＰｂＯ□粉末とじて
約２０ｍｇ／ｃｍ”である。Bath composition: Lead nitrate ------1--・-m----・・ 1
0g/1 nitric acid-1--90ml/
β tin sulfate l
In order to apply it onto the lead substrate 1 on which a polytetrafluoroethylene was formed, polytetrafluoroethylene dispersion was added thereto so that the polytetrafluoroethylene content was approximately 1 wt.%, and a paste was prepared. The coating amount is approximately 20 mg/cm'' as PbO□ powder.
塗布後、ローラーによるプレス、風乾を行なって第１図
にその断面を示したような陽極板を作製した。After coating, pressing with a roller and air drying were performed to produce an anode plate as shown in cross section in FIG.
これを５０ｍｍＸ ５０ｍｍに裁断し、これと十分に大
きな容量を持つペースト式陰極板との間にガラス不織布
を介して単位電池を組み立て、遊離する液がないように
比重１．３２０（２０°Ｃ）の電解液を注入し、以下に
示す条件で充放電試験を行なったところ、第２図に示す
結果が得られた。This was cut to 50 mm x 50 mm, and a unit battery was assembled between this and a paste-type cathode plate with a sufficiently large capacity via a glass nonwoven fabric, with a specific gravity of 1.320 (20°C) so that no liquid would be released. When an electrolytic solution was injected and a charge/discharge test was conducted under the conditions shown below, the results shown in FIG. 2 were obtained.
放電：２５ｍ八 （放電終止電圧１．７０Ｖ）充電＝２
５ｍ八 （放電電気量の１３０％）同図中には、比較と
して鉛基板にスズを含まないＰｂＯ２の粉末を同量塗布
しただけの従来の陽極板Ａの性能を示した。本発明の陽
極板Ｂによって、深い放電の繰り返しに対する陽極板の
性能が著しく向上していることがわかる。Discharge: 25m8 (discharge end voltage 1.70V) Charge = 2
5m8 (130% of the amount of discharged electricity) For comparison, the performance of a conventional anode plate A, in which the same amount of tin-free PbO2 powder was applied to a lead substrate, is shown. It can be seen that the anode plate B of the present invention significantly improves the performance of the anode plate against repeated deep discharges.
（発明の効果）
本発明によって、鉛基板と活物質の剥離、両者の界面へ
の硫酸の侵入による鉛基板表面の不働態化などの問題が
な（なり、スズをＰｂＯ□結晶中に効率良く、均一に侵
入させること乙こよって深い放電の繰り返しに対する陽
極板の性能を著しく向上させることができた。(Effects of the Invention) The present invention eliminates problems such as peeling off of the lead substrate and active material and passivation of the lead substrate surface due to sulfuric acid entering the interface between the two, and effectively injects tin into the PbO crystal. By uniformly infiltrating the anode plate, it was possible to significantly improve the performance of the anode plate against repeated deep discharges.
本発明による鉛電池用陽極板は鉛電池のシール化、小型
化および薄型化の強い要求に十分に耐え得るものである
。The anode plate for lead batteries according to the present invention can fully meet the strong demands for sealing, miniaturization, and thinning of lead batteries.
、 第１図は本発明による鉛電池用陽極板の要部断面図
、第２図は本発明による鉛電池用陽極板を用いた単位電
池の充放電サイクル特性図である。, FIG. 1 is a cross-sectional view of a main part of the anode plate for a lead battery according to the present invention, and FIG. 2 is a charge/discharge cycle characteristic diagram of a unit battery using the anode plate for a lead battery according to the present invention.
Claims (1)
鉛塩浴からの電析によって調製し、これを鉛あるいは鉛
−カルシウム系合金基板上に塗布してなる鉛電池用陽極
板において、上記電析ＰｂＯ＿２中にスズを含み、上記
鉛あるいは鉛−カルシウム系合金基板の表面に予めα−
ＰｂＯ＿２層を形成させることを特徴とする鉛電池用陽
極板の製造方法。In an anode plate for a lead battery, lead dioxide (PbO_2), which is an anode active material for a lead battery, is prepared by electrodeposition from a lead salt bath and coated on a lead or lead-calcium alloy substrate. The PbO_2 contains tin, and the surface of the lead or lead-calcium alloy substrate has α-
A method for manufacturing an anode plate for a lead battery, characterized by forming a PbO_2 layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2333738A JPH04206344A (en) | 1990-11-30 | 1990-11-30 | Manufacture of lead accumulator anode plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2333738A JPH04206344A (en) | 1990-11-30 | 1990-11-30 | Manufacture of lead accumulator anode plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04206344A true JPH04206344A (en) | 1992-07-28 |
Family
ID=18269403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2333738A Pending JPH04206344A (en) | 1990-11-30 | 1990-11-30 | Manufacture of lead accumulator anode plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04206344A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9666547B2 (en) | 2002-10-08 | 2017-05-30 | Honeywell International Inc. | Method of refining solder materials |
-
1990
- 1990-11-30 JP JP2333738A patent/JPH04206344A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9666547B2 (en) | 2002-10-08 | 2017-05-30 | Honeywell International Inc. | Method of refining solder materials |
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