JPH02152165A - Manufacture of substrate for cathode of lead-acid battery - Google Patents
Manufacture of substrate for cathode of lead-acid batteryInfo
- Publication number
- JPH02152165A JPH02152165A JP63306514A JP30651488A JPH02152165A JP H02152165 A JPH02152165 A JP H02152165A JP 63306514 A JP63306514 A JP 63306514A JP 30651488 A JP30651488 A JP 30651488A JP H02152165 A JPH02152165 A JP H02152165A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- substrate
- layer
- alloy
- tin
- 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
- 239000000758 substrate Substances 0.000 title claims abstract description 60
- 239000002253 acid Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910007116 SnPb Inorganic materials 0.000 claims description 2
- 238000007600 charging Methods 0.000 abstract description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010410 layer Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 6
- 230000002427 irreversible effect Effects 0.000 abstract 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- 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、メインテナンスフリー形、バイポーラ形など
の鉛蓄電池の陽極用基板に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a substrate for an anode of a lead-acid battery such as a maintenance-free type or a bipolar type.
従来の鉛蓄電池の陽極板は、鉛又は鉛合金の基板、多く
の場合、格子状の多孔基板に陽極活物質を充填塗着して
成るものであるが、これを鉛蓄電池に用いた場合、過放
電後長期間放置されると、充電性能が低下し、遂には使
用不可能となる欠点があった。The anode plate of a conventional lead-acid battery is made of a lead or lead alloy substrate, often a grid-like porous substrate filled with an anode active material, but when used in a lead-acid battery, If left for a long time after over-discharging, the charging performance deteriorates and the battery becomes unusable.
この欠点を解消するため、種々の試みかなされているが
、その中に鉛格子基板を本体とし、その表面にＳｎＯ２
の塗膜を形成して成る陽・傾用格子基板が提案されてい
る。そのＳｎＯ２の塗膜の形成方法は、鉛格子基板を本
体とし、その表面にスズ酸のゲル溶液を均一な層に塗布
形成し、次でこれを加熱、脱水することにより、その基
板表面にＳｎＯ２塗膜を生成せしめる方法である。Various attempts have been made to eliminate this drawback, but one of them is a lead lattice substrate as the main body and SnO2 on the surface.
A positive/tilted grating substrate formed with a coating film has been proposed. The SnO2 coating film is formed by using a lead lattice substrate as the main body, coating the surface with a stannic acid gel solution in a uniform layer, and then heating and dehydrating it. This is a method of forming a coating film.
従来の鉛格子基板本体にＳｎＯ，被膜を上記の方法で形
成するときは、その過放電後長期間放電後の充電性能は
向上するが、所定の充電容量を得るまでに比較的時間が
か−り又、充放電の繰り返しで該ＳｎＯ２塗膜は、比較
的容易に剥離する傾向がある。When SnO and a coating are formed on the conventional lead lattice substrate body by the above method, the charging performance after over-discharging and long-term discharging is improved, but it takes a relatively long time to obtain a predetermined charging capacity. Furthermore, the SnO2 coating tends to peel off relatively easily after repeated charging and discharging.
本発明は、上記従来の課題を改善し、過放電後長期間放
電後の充電性能を向上し、又、堅牢且つ導電性の良好な
５ｎＯ２−Ｓｎ −ＳｎＰｂの複合被膜を基板本体の表
面に形成された鉛蓄電池の陽極用基板の製造法を提供す
るもので、鉛又は鉛合金基板本体の表面にＳｎの被膜を
形成し、次でこれを加熱することを特徴とする。The present invention improves the above-mentioned conventional problems, improves the charging performance after long-term discharge after over-discharge, and forms a strong and conductive composite film of 5nO2-Sn-SnPb on the surface of the substrate body. The present invention provides a method for manufacturing a substrate for an anode of a lead-acid battery, which is characterized by forming a Sn coating on the surface of a lead or lead alloy substrate body, and then heating this.
鉛又は鉛合金基板本体の表面にＳｎの被膜を形成した後
、これを加熱するときはそのＳｎ被膜の表面はＳｎＯ２
に酸化すると同時に、その内側はＳｎ層のま−残り、そ
の一部は基板本体内に浸透し、又その界面は、該本体の
表面のｐｂとの合金を形成した該基板本体と一体の堅牢
な複合被膜に形成される。After forming a Sn film on the surface of the lead or lead alloy substrate body, when heating it, the surface of the Sn film becomes SnO2.
At the same time, the Sn layer remains on the inside, a part of which penetrates into the substrate body, and the interface forms a solid layer integral with the substrate body that has formed an alloy with the PB on the surface of the body. Formed into a composite film.
このようにして製造された本発明の該陽極用基板を鉛蓄
電池の陽極板として用いるときは、該電池を過放電して
も、本発明の前記被膜によりその基板本体の表面と活物
質の界面に従来生成される不可塑性のＰｔ１ＳＯ４など
の高インピーダンス層の形成は抑止され、長時間放置後
の充電性を向上するばかりでなく、所定容Ｍまでの充電
時間の短縮をもたらすと共に、基板本体にＳｎ、ｐｂの
金属相互で結着しているので５基体本体に強固に密着し
て居り、剥離が防止される堅牢な被膜を提供し使用寿命
が延長する。When the anode substrate of the present invention manufactured in this way is used as an anode plate of a lead-acid battery, even if the battery is over-discharged, the coating of the present invention provides a barrier between the surface of the substrate body and the active material. The formation of a high impedance layer such as non-plastic Pt1SO4 that is conventionally generated in the substrate is suppressed, which not only improves the charging performance after being left for a long time, but also shortens the charging time to the specified volume M. Since the Sn and PB metals are bonded to each other, it firmly adheres to the 5-substrate body, providing a robust coating that prevents peeling and extending its service life.
次に本発明の実施例につき説明する。 Next, examples of the present invention will be described.
自動車、二輪車などの鉛蓄電池用の通常の陽極板やバイ
ポーラ鉛蓄電池の陽極板には、その基板として鋳造方式
、打ち抜き方式、エキスバンド方式などにより活物質充
填用の多数の孔を設けた鉛又は鉛合金基板、或いは囲枠
に囲まれた方形の活物質充填用四部を設けた鉛又は鉛合
金基板かあるが、以下には、多数の活物質充填用孔を設
けた多孔基板、一般には、格子状多孔基板の製造法を例
として説明する。Ordinary anode plates for lead-acid batteries such as automobiles and motorcycles, and anode plates for bipolar lead-acid batteries, are made of lead or a substrate with a large number of holes for filling the active material by casting, punching, expanding, etc. There are lead alloy substrates, or lead or lead alloy substrates provided with four rectangular parts for filling active material surrounded by a surrounding frame, but the following are porous substrates provided with a large number of holes for filling active material, generally: A method for manufacturing a lattice-shaped porous substrate will be explained as an example.
先ず、Ｐｂ−５ｎ−Ｃａ合金（Ｃａ０．０５１％、Ｓｎ
Ｏ，５１％、残部Ｐｂ）を材料とし、鋳造法により、
又は肉薄の該鉛合金圧延素板を打ち抜き又はエキスバン
ド方式により、格子基板本体を作成する。First, Pb-5n-Ca alloy (Ca0.051%, Sn
O, 51%, balance Pb) was used as the material, and by casting method,
Alternatively, the lattice substrate body is created by punching or expanding the thin rolled lead alloy blank.
次でその表面にＳｎメッキ処理を施す。メッキ処理は、
電解メッキでもよいが、電解メッキ設備などの設備、並
びに製造コストに徴し、無電解メッキ処理が好ましい。Next, the surface is subjected to Sn plating treatment. The plating process is
Although electrolytic plating may be used, electroless plating is preferred in terms of equipment such as electrolytic plating equipment and manufacturing costs.
その１例は、０．０５Ｍ濃度の塩酸水溶液に該格子基板
本体を浸漬し、表面処理を行い、水洗乾燥後、Ｓｎメッ
キ浴に浸漬する。そのメッキ浴は例えば、０．ＯＩＭＨ
Ｃｌ、Ｉ Ｍｏｌ／Ｊ） ５ｎＣ１□の水溶液から成る
。このメッキ浴に１分間浸漬した後水洗する。In one example, the grid substrate body is immersed in a 0.05M hydrochloric acid aqueous solution to perform surface treatment, washed with water and dried, and then immersed in an Sn plating bath. The plating bath is, for example, 0. OIMH
Cl, I Mol/J) Consists of an aqueous solution of 5nC1□. After being immersed in this plating bath for 1 minute, it is washed with water.
然るときは、その表面にＳｎメッキ被膜が生成する。次
でこれを水洗後、２８０’Ｃの電気炉で３０分間熱処理
して本発明の陽極用鉛格子基板を得る。この基板本体の
表面の被膜につき、ＥＰＨＡによるＳｎの線分析を行っ
た所、その被膜の表面は５ｎ０２が形成されて居り、そ
の内側は、Ｓｎとｐｂ−８ｎの合金とから成る金属層が
認められ、且つその基板本体の内部にまでｓｎが浸透し
ていることが認められた。In this case, a Sn plating film is formed on the surface. Next, this is washed with water and then heat treated in an electric furnace at 280'C for 30 minutes to obtain a lead grid substrate for an anode of the present invention. When line analysis of Sn was performed on the surface of the substrate main body using EPHA, it was found that 5n02 was formed on the surface of the film, and a metal layer consisting of an alloy of Sn and PB-8N was found on the inside. It was also observed that sn had penetrated into the inside of the substrate body.
上記の鉛合金を材料とし、鋳造法により作製した格子基
板本体に上記の拳法の被膜形成処理を施して製造した本
発明の陽極用格子基板をＡとし、上記の鉛合金の肉薄圧
延板をエキスバンド方式により作製した格子基板本体に
、上記の拳法の被膜形成処理を施してＶ造した本発明の
陽極用基板をＢとし、比較のため、上記の鉛合金の肉薄
圧延板をエキスバンド方式により作製した格子基板本体
に、スズ酸（Ｉ＋、（０）１）２ ）のゲル溶液を塗布
し、その一定の厚さの塗布層を形成した後、加熱、脱水
して該格子基板本体の表面に５ｎ０２被膜を形成した陽
極用基板をＣとし、又、基板本体表面を無処理の従来の
鋳造法により作成し格子基板をＸとし、基板本体表面を
無処理の従来のエキスバンド方式により作成した格子基
板をＢ′とした。The lattice substrate for an anode of the present invention manufactured by applying the above-mentioned Kempo film forming treatment to the lattice substrate main body produced by the casting method using the above-mentioned lead alloy as a material is referred to as A, and the thin rolled plate of the above-mentioned lead alloy is extracted. B is the anode substrate of the present invention, which is made by applying the above-mentioned Kempo film forming treatment to the lattice substrate body produced by the band method to form a V shape. A gel solution of stannic acid (I+, (0)1)2) is applied to the fabricated grid substrate body to form a coating layer of a certain thickness, and then heated and dehydrated to coat the surface of the grid substrate body. The anode substrate on which a 5n02 film was formed was designated as C, and the surface of the substrate body was created by the conventional casting method without treatment, and the lattice substrate was designated as X, and the surface of the substrate body was created by the conventional expansion method without treatment. The grating substrate was designated as B'.
これら夫々の格子基板Ａ、Ｂ、Ｃ，λ、Ｂ′に常法によ
り陽極活物質を同量均一に充填し、化成し、水洗、乾燥
して夫々の陽極板を多数枚作成し、これらを使用して公
称容ｉ ４０Ａｈ／ Ｓ ＨＲの鉛蓄電池を夫々作成し
、その夫々について過放電放置試験を実施した。試験榮
件は、各電池をＳＨＲ放電後、消費電力１０Ｗのランプ
を点灯させ４０°Ｃ１１４日間放電させ、更に開路状態
で４０°Ｃ１１４日間放置し、その後、２５℃において
回復充電として、定電圧充電（１６，ＯＶ、Ｈａｘ電流
２５Ａ）を４０分間実施した。Each of these lattice substrates A, B, C, λ, and B' is uniformly filled with the same amount of anode active material by a conventional method, chemically formed, washed with water, and dried to produce a large number of each anode plate. Lead-acid batteries with a nominal capacity of 40 Ah/S HR were prepared using the above-described method, and an over-discharge storage test was conducted on each of the lead-acid batteries. The test conditions were: after SHR discharging each battery, a lamp with a power consumption of 10 W was turned on, and the battery was discharged for 114 days at 40°C, and then left open at 40°C for 114 days, and then at 25°C as a recovery charge, and constant voltage charging was performed. (16, OV, Hax current 25A) was carried out for 40 minutes.
その結果を添付図面に示す。図面は、充電々気量と充電
時間との関係を示し、鎖国より明らかなように、本発明
の陽極用基板Ａ及びＢを使用した電池の回復充電性へ及
びＢ１は、無処理基板を使用した電池の回復充電性ん及
びＢ１よりはもとより従来の改善型である基板を使用し
た電池のそれよりも著しく向上していることが確３、召
された。The results are shown in the attached drawings. The drawing shows the relationship between charging capacity and charging time, and as is clear from the isolation, the recovery chargeability of batteries using the anode substrates A and B of the present invention, and B1 using an untreated substrate. It was confirmed that the recovery and charging performance of the battery was significantly improved not only over B1 but also over that of the battery using the conventional improved type substrate.
この充放電は多数回繰り返した後、夫々の電池を解体し
、その夫々の陽極用格子基板を観察しな所、基板Ｃの５
ｎ０２被膜に部分的な亀裂や剥離が認められたが、本発
明の基板Ａ及びＢの被膜は全く異常が認められなかった
。After repeating this charging and discharging many times, each battery was disassembled and each anode grid substrate was observed.
Partial cracks and peeling were observed in the n02 coating, but no abnormalities were observed in the coatings of substrates A and B of the present invention.
このように本発明によるときは、鉛又鉛合金の基板を本
体とし、その表面にＳｎの被膜を形成後、これに加熱処
理を施したので、これを陽極板とし電池に組み込み使用
するときは、その電池の放電放置後の回復充電性は著し
く向上し、電池寿命の延長をもたらず等の効果を有する
。As described above, according to the present invention, the main body is a lead or lead alloy substrate, and after forming a Sn coating on the surface, it is heat-treated, so that when it is used as an anode plate and incorporated into a battery. , the recovery and charging performance of the battery after being left to discharge is significantly improved, and the battery life is not extended.
この場合、Ｓｎの被膜をメッキで行い、次でこれを加熱
するときは、基板本体と一体の堅牢な半導電乃至導電性
被膜を形成し得られる効果を有する。In this case, when the Sn coating is formed by plating and then heated, it has the effect of forming a robust semiconductive or conductive coating that is integrated with the substrate body.
図面は本発明の基板を使用した陽極板と従来の基板を使
用した陽極板を夫々組み込んだ人々の電池の回復充電性
の比較グラフを示す。The figure shows a comparison graph of the recovery chargeability of people's batteries incorporating an anode plate using the substrate of the present invention and an anode plate using a conventional substrate, respectively.
Claims (1)
、次でこれを加熱することを特徴とする鉛蓄電池の陽極
用基板の製造法。 ２、鉛又は鉛合金基板本体の表面にＳｎメッキの被膜を
形成し、次でこれを加熱し該Ｓｎ被膜の表面をＳｎＯ＿
２に形成すると共に、その内側層をＳｎ及びＳｎＰｂ合
金から成る該基板本体表面と一体の金属層に形成せしめ
ることを特徴とする請求項１に記載の鉛蓄電池の陽極用
基板の製造法。[Claims] 1. A method for producing a substrate for an anode of a lead-acid battery, which comprises forming a Sn coating on the surface of a lead or lead alloy substrate body, and then heating the coating. 2. Form a Sn plating film on the surface of the lead or lead alloy substrate body, then heat it and change the surface of the Sn film to SnO_
2. The method of manufacturing a substrate for an anode of a lead-acid battery according to claim 1, wherein the inner layer is formed as a metal layer made of Sn and SnPb alloy and integral with the surface of the substrate main body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63306514A JPH02152165A (en) | 1988-12-03 | 1988-12-03 | Manufacture of substrate for cathode of lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63306514A JPH02152165A (en) | 1988-12-03 | 1988-12-03 | Manufacture of substrate for cathode of lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02152165A true JPH02152165A (en) | 1990-06-12 |
Family
ID=17957944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63306514A Pending JPH02152165A (en) | 1988-12-03 | 1988-12-03 | Manufacture of substrate for cathode of lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02152165A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04292862A (en) * | 1991-03-20 | 1992-10-16 | Shin Kobe Electric Mach Co Ltd | Manufacture of electrode base for lead storage battery |
| JP2006093047A (en) * | 2004-09-27 | 2006-04-06 | Furukawa Battery Co Ltd:The | Lead acid battery |
| JP2017069123A (en) * | 2015-10-01 | 2017-04-06 | 日立化成株式会社 | Punched lattice for lead acid battery, positive electrode for lead acid battery, and lead acid battery using the same |
-
1988
- 1988-12-03 JP JP63306514A patent/JPH02152165A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04292862A (en) * | 1991-03-20 | 1992-10-16 | Shin Kobe Electric Mach Co Ltd | Manufacture of electrode base for lead storage battery |
| JP2006093047A (en) * | 2004-09-27 | 2006-04-06 | Furukawa Battery Co Ltd:The | Lead acid battery |
| JP2017069123A (en) * | 2015-10-01 | 2017-04-06 | 日立化成株式会社 | Punched lattice for lead acid battery, positive electrode for lead acid battery, and lead acid battery using the same |
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