JPS63252361A - Plate for lead-acid battery and its manufacture - Google Patents
Plate for lead-acid battery and its manufactureInfo
- Publication number
- JPS63252361A JPS63252361A JP62086057A JP8605787A JPS63252361A JP S63252361 A JPS63252361 A JP S63252361A JP 62086057 A JP62086057 A JP 62086057A JP 8605787 A JP8605787 A JP 8605787A JP S63252361 A JPS63252361 A JP S63252361A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- alloy
- tin
- calcium
- base material
- 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
- 239000002253 acid Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000463 material Substances 0.000 claims abstract description 22
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002142 lead-calcium alloy Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 5
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 10
- 239000000956 alloy Substances 0.000 abstract description 10
- 239000011149 active material Substances 0.000 abstract description 8
- 229910002058 ternary alloy Inorganic materials 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process 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)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、鉛蓄電池用極板およびその製造法に関するも
のであり、とくに、高温での高負荷サイクル寿命特性の
向上をはかるものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an electrode plate for a lead-acid battery and a method for manufacturing the same, and in particular aims to improve high load cycle life characteristics at high temperatures.
従来の技術
従来から鉛蓄電池用格子体には鉛−アンチモン合金を用
いた鋳造式格子が利用されていた０しかしながら、格子
中のアンチモンは自己放電を促進し、液減りも増加する
欠点があった。そこで、アンチモンを含まない新しい合
金として、鉛−カルシウム系合金が開発された。この鉛
−カルシウム系合金は一般に鉛−カルシウム−錫の三元
合金が採用されている。また、格子製造法として連続高
効率製法のエキスパンド格子が開発された。これは鉛−
カルシウム系合金の連続シートラっくり、エキスパンド
加工するものである。Conventional technology Cast-type grids made of lead-antimony alloy have been used as grids for lead-acid batteries. However, the antimony in the grids has the drawback of promoting self-discharge and increasing liquid loss. . Therefore, a lead-calcium alloy was developed as a new alloy that does not contain antimony. This lead-calcium alloy is generally a ternary alloy of lead-calcium-tin. In addition, an expanded lattice manufacturing method using a continuous high-efficiency method was developed. This is lead-
This is a continuous sheet of calcium-based alloy that is processed to expand.
鉛−カルシウム系合金を適用した鉛蓄電池は減液性能等
に優れたメンテナンス・フリー電池として使用されてい
る。また、欠点とされていた過放電放置後の充電回復性
を改善するために、鉛−カルシウム系合金格子の表面に
鉛−錫合金層を形成させる方式が開発された。Lead-acid batteries made of lead-calcium alloys are used as maintenance-free batteries with excellent liquid reduction performance. Furthermore, in order to improve the charge recovery after over-discharging, which had been considered a drawback, a method was developed in which a lead-tin alloy layer was formed on the surface of a lead-calcium alloy lattice.
発明が解決しようとする問題点
鉛−カルシウム系合金を格子に用いたメンテナンス・フ
リー電池は、一般に深い放電を含むサイクル特性が短か
い傾向にあり、とくに高温下での深い充放電サイクル寿
命が欠点とされている。Problems to be Solved by the Invention Maintenance-free batteries that use lead-calcium alloys in their grids generally tend to have short cycle characteristics, including deep discharge, and are particularly disadvantageous in their deep charge/discharge cycle life at high temperatures. It is said that
そこで、本発明は鉛−カルシウム系合金格子の高温下で
の長寿命化をはかるものである。Therefore, the present invention aims to extend the life of a lead-calcium alloy lattice at high temperatures.
問題点を解決するための手段
本発明は鉛−カルシウム系合金の母材上に鉛−銀一錫合
金層を形成したシートを格子素材として用いることによ
り、高温下での長寿命化をはかるものである。Means for Solving the Problems The present invention aims to extend the life under high temperatures by using a sheet with a lead-silver-tin alloy layer formed on a lead-calcium alloy base material as a grid material. It is.
母材の鉛−カルシウム系合金は、重量比で０．０３〜０
．１５％のカルシウムと１．０％以下の錫を含み残部が
鉛である鉛−カルシウム−錫の三元合金であジ、表面層
の合金は重量比で０．０１〜２，０％の銀と０．６〜１
０チの錫、残部が鉛である鉛−銀一錫合金である。The base metal lead-calcium alloy has a weight ratio of 0.03 to 0.
．． It is a lead-calcium-tin ternary alloy containing 15% calcium and 1.0% or less tin, the balance being lead, and the surface layer alloy is 0.01 to 2.0% silver by weight. and 0.6-1
It is a lead-silver-tin alloy with 0% tin and the balance lead.
また、格子表面層に異種合金層を形成させる方法として
、鉛−カルシウム系合金の母材上に厚みが母材よりも薄
い鉛−銀一錫合金シー１−重ね合わせて、冷間圧延によ
り一体化することを特徴とするものである。In addition, as a method for forming a dissimilar alloy layer on the lattice surface layer, a lead-silver-tin alloy sheet 1, which is thinner than the base material, is stacked on a lead-calcium alloy base material and integrated by cold rolling. It is characterized by the fact that it becomes
なお、鉛−銀一錫合金層を母材の両面に重ね合わせて三
層のシートにすると、よジ一層効果がある。Note that if the lead-silver-tin alloy layer is superimposed on both sides of the base material to form a three-layer sheet, the distortion effect will be even more effective.
作用
鉛−カルシウム系合金のエキスパンド格子を用いた鉛蓄
電池は、７０’Ｃ以上の高温下で充放電サイクルを繰り
返し行なうと、格子表面が酸化腐食により、極板の変形
を生じ易くなる。また、鉛−カルシウム系合金格子の酸
化層は緻密であり、格子と剥離しやすい傾向にある。こ
のような物性から、サイクル数が進むと、格子と活物質
との密着性が損なわれ、寿命になると考えられている。When a lead-acid battery using an expanded lattice of a lead-calcium alloy is repeatedly charged and discharged at a high temperature of 70'C or higher, the lattice surface tends to undergo oxidation corrosion, causing deformation of the electrode plate. Furthermore, the oxide layer of the lead-calcium alloy lattice is dense and tends to separate from the lattice. Based on these physical properties, it is thought that as the number of cycles increases, the adhesion between the lattice and the active material is impaired, leading to the end of its life.
そこで、本発明のように格子合金の表面層に鉛−銀一錫
の三元合金層を有する格子を用いると、格子と活物質と
の密着性が保たｎる几め、高温下での寿命向上がはから
ｎると考えら詐る。しかし、その詳細な機構は明らかで
ない。また、鉛−銀の二元合金を用いた場合、高温下で
の耐食性が改善できるが、深い放電を含む高負荷での格
子と活物質との密着性を保つ効果はほとんど認められな
かった。本発明のように鉛−銀一錫の三元合金を用いる
と、腐食酸化層が多孔性を有する傾向が認められた。そ
して、酸化層が活物質化するとともに初期の活物質との
接続が維持さｎるものと推定される。したがって、本発
明は鉛−カルシウム系合金の母材上に、鉛−銀一錫の三
元合金層を形成させることに特徴がある。Therefore, if a lattice having a ternary alloy layer of lead-silver and tin is used as the surface layer of the lattice alloy as in the present invention, the adhesion between the lattice and the active material can be maintained, and the lattice can be used under high temperatures. It is a lie to think that lifespan will be improved. However, the detailed mechanism is not clear. Furthermore, when a lead-silver binary alloy is used, corrosion resistance at high temperatures can be improved, but almost no effect on maintaining adhesion between the lattice and the active material under high loads including deep discharge was observed. When a ternary lead-silver-tin alloy was used as in the present invention, a tendency for the corroded oxidized layer to have porosity was observed. It is estimated that as the oxide layer becomes an active material, the connection with the initial active material is maintained. Therefore, the present invention is characterized in that a ternary alloy layer of lead-silver and tin is formed on a base material of lead-calcium alloy.
実施例 以下、本発明の詳細を実施例で示す。Example Hereinafter, details of the present invention will be shown in Examples.
鉛−０，０７％カルシウム−０，３％錫の三元合金を母
材として、厚み１ｏ謹、幅８０ｍ＋の連続鋳造体（以下
スラブと称す）をつくシ、このスラブ上に鉛−０，６％
銀−５５，ｏ％錫合金製の箔（厚み０．１鰭２幅６０職
）を重ね合わせて、圧延ローラを通過させて、冷間圧延
により厚み１．０ｍになるまで圧延し、母材と箔を一体
化した鉛合金シートをつくった。Using a ternary alloy of lead-0.07% calcium-0.3% tin as a base material, a continuous cast body (hereinafter referred to as a slab) with a thickness of 10m and a width of 80m+ is made. 6%
Foils made of silver-55, o% tin alloy (thickness: 0.1 fin, 2 width: 60 mm) were overlapped and passed through rolling rollers, and cold rolled to a thickness of 1.0 m. We created a lead alloy sheet that integrates and foil.
この鉛合金シートの両端から切断目をつけるレシプロ式
カッターでエキスパンド加工し、引き続き活物質となる
鉛ペーストを充填して正極板をつくった。同時に、母材
の鉛−カルシウム−錫合金だけを用いて、従来例の正極
板をつくった。This lead alloy sheet was expanded using a reciprocating cutter that made cuts from both ends, and then filled with lead paste as an active material to create a positive electrode plate. At the same time, a conventional positive electrode plate was made using only the lead-calcium-tin alloy as the base material.
これらの正極板と通常の負極板を組み合わせて、本発明
の電池ム、比較例の電池Ｂをつくった。By combining these positive electrode plates and a normal negative electrode plate, a battery according to the present invention and a battery B as a comparative example were made.
この人、Ｂの電池を用い、７０’Ｃの雰囲気中で充放電
サイクル試験を行なり几。放電は２ｏムで１時間、充電
は１４．８Ｖで最大電流２０人で６時間行ない、この充
放電を１サイクルとして、２５サイクルおきに３００人
で３０秒間放電し、３０秒０の電圧が７．２ｖ以下にな
ったときを寿命としたＯ
図にサイクル寿命試験結果を示す。図から明らかなよう
に、本発明の電池人は、比較例Ｂよりも優れた寿命性能
が得られた。寿命になった電池を分解した結果、格子の
腐食はサイクル数に比例して、本発明の極板の方が太き
かった。したがって、本発明は格子の耐食性向上をはか
るものではなく、格子と活物質との密着性を保つ働きが
あると思われる。しかし、極板断面の観察などからは明
確な知見は得られていない。This person conducted a charge/discharge cycle test using B's battery in an atmosphere of 70'C. Discharging was performed at 2 ohm for 1 hour, and charging was performed at 14.8 V with a maximum current of 20 people for 6 hours. This charge and discharge was considered as one cycle, and 300 people discharged for 30 seconds every 25 cycles, and the voltage at 0 for 30 seconds was 7. The cycle life test results are shown in the figure. As is clear from the figure, the battery of the present invention had better life performance than Comparative Example B. As a result of disassembling the battery at the end of its service life, the corrosion of the grid was proportional to the number of cycles, and the plate of the present invention was found to be thicker. Therefore, the present invention does not aim to improve the corrosion resistance of the lattice, but seems to have a function of maintaining the adhesion between the lattice and the active material. However, no clear findings have been obtained from observations of the cross sections of the electrode plates.
尚、実施例では母材の上部に鉛−銀一錫合金層を形成さ
せた例について示したが母材の上下両面に形成させると
さらに効果全発揮できる。In the embodiment, an example was shown in which a lead-silver-tin alloy layer was formed on the upper part of the base material, but the full effect can be obtained by forming it on both the upper and lower surfaces of the base material.
また、銀の量が０．０１チ未満で、錫の量が０．５多未
満では十分な効果が得られなかった。逆に銀が２．０％
を越えて、錫が１０％を越えると合金箔が母材と一体化
しにくくなり、実用上好ましくなく、材料コスト面でも
高価になるので工業的にも好ましくない。Further, if the amount of silver was less than 0.01 inch and the amount of tin was less than 0.5 inch, sufficient effects could not be obtained. On the other hand, silver is 2.0%
If the content of tin exceeds 10%, it becomes difficult for the alloy foil to integrate with the base material, which is not desirable from a practical standpoint, and the material cost becomes expensive, which is also not desirable from an industrial standpoint.
発明の効果
上記した様に本発明は、鉛−カルシウム系合金を格子に
用いたメンテナンス・フリー電池の高温長寿命電池を発
明した。その工業的価値は太きい０Effects of the Invention As described above, the present invention has invented a maintenance-free, high-temperature, long-life battery using a lead-calcium alloy for the grid. Its industrial value is 0
図は本発明の極板を用いた鉛蓄電池の寿命性能を示す図
である。
ム・・・・・・本発明の電池、Ｂ・・・・・・比較例の
電池。The figure is a diagram showing the life performance of a lead-acid battery using the electrode plate of the present invention. M: Battery of the present invention; B: Battery of comparative example.
Claims (4)
に鉛−銀−錫合金属を形成したシートの穿孔板を格子に
用いることを特徴とした鉛蓄電池用極板。(1) An electrode plate for a lead-acid battery, characterized in that a perforated sheet plate made of a lead-calcium alloy as a base material and a lead-silver-tin alloy formed on the surface of the base material is used as a grid.
．０重量％、錫の含有量０．６〜１０重量％で残部が鉛
である特許請求の範囲第１項記載の鉛蓄電池用極板。(2) The lead alloy metal on the surface of the base material has a silver content of 0.01 to 2
．． The electrode plate for a lead-acid battery according to claim 1, wherein the content of tin is 0.6 to 10% by weight, and the balance is lead.
１５重量％のカルシウムと１．０重量％以下の錫を含み
残部が鉛からなる鉛−カルシウム−錫合金である特許請
求の範囲第１項記載の鉛蓄電池用極板。(3) The lead-calcium alloy of the base material is 0.03 to 0.
The electrode plate for a lead-acid battery according to claim 1, which is a lead-calcium-tin alloy containing 15% by weight of calcium and 1.0% by weight or less of tin, with the balance being lead.
からなりしかも厚みが母材よりも薄いシートを重ね合わ
せ、冷間圧延して一体化したシートを素材とし、これを
エキスパンド加工した格子体にペーストを充填する鉛蓄
電池用極板の製造法。(4) A sheet made of a lead-silver-tin alloy that is thinner than the base material is layered on a base material of a lead-calcium alloy, and then cold-rolled to form an integrated sheet, which is then expanded. A method for manufacturing electrode plates for lead-acid batteries, in which a processed grid is filled with paste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62086057A JPS63252361A (en) | 1987-04-08 | 1987-04-08 | Plate for lead-acid battery and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62086057A JPS63252361A (en) | 1987-04-08 | 1987-04-08 | Plate for lead-acid battery and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63252361A true JPS63252361A (en) | 1988-10-19 |
Family
ID=13876064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62086057A Pending JPS63252361A (en) | 1987-04-08 | 1987-04-08 | Plate for lead-acid battery and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63252361A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2654263A1 (en) * | 1989-11-06 | 1991-05-10 | Magneti Marelli Spa | LEAD ACCUMULATOR BATTERY, PARTICULARLY FOR STARTING MOTOR VEHICLE ENDOTHERMIC ENGINES. |
-
1987
- 1987-04-08 JP JP62086057A patent/JPS63252361A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2654263A1 (en) * | 1989-11-06 | 1991-05-10 | Magneti Marelli Spa | LEAD ACCUMULATOR BATTERY, PARTICULARLY FOR STARTING MOTOR VEHICLE ENDOTHERMIC ENGINES. |
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