JPH0559548B2 - - Google Patents
Info
- Publication number
- JPH0559548B2 JPH0559548B2 JP61164332A JP16433286A JPH0559548B2 JP H0559548 B2 JPH0559548 B2 JP H0559548B2 JP 61164332 A JP61164332 A JP 61164332A JP 16433286 A JP16433286 A JP 16433286A JP H0559548 B2 JPH0559548 B2 JP H0559548B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- antimony
- alloy
- copper
- cadmium
- 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 - Lifetime
Links
- 229910052787 antimony Inorganic materials 0.000 claims description 13
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 239000002141 low-antimony alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000003483 aging Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000002142 lead-calcium alloy Substances 0.000 description 2
- IMFPZOKVUGBHGF-UHFFFAOYSA-N [Cd].[As]#[Sn] Chemical compound [Cd].[As]#[Sn] IMFPZOKVUGBHGF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Description
産業上の利用分野
本発明は鉛蓄電池に係り、特に自動車用のメン
テナンスフリー（以下、MFという）鉛蓄電池に
関するものである。
従来技術とその問題点
近年、鉛蓄電池の市場では、補水の手間を省け
ること、及び自己放電量が少なく注液状態で長期
保存が可能なこと等の利点よりMF（保守不要）
電池の要求が強まつている。
従来、上記MF電池の格子体合金には、鉛−カ
ルシウム合金或はアンチモン含有量が3wt％以下
の鉛−低アンチモン合金が用いられている。しか
し、鉛−カルシウム合金を正極板の格子体に用い
た場合には、比較的深い放電を行なう条件下にお
けるサイクル寿命（以下、深放電サイクル寿命と
いう）が短いという欠点がある。
この欠点を解消する目的で、アンチモン含有量
が3wt％以下の鉛−低アンチモン合金として0.5〜
3.0wt％のアンチモン、0.05〜0.5wt％のヒ素、
0.01〜0.3wt％のカドミウム、0.01〜1.0wt％の錫
と残部鉛よりなる鉛合金が使用されている。しか
し、該鉛合金を用いた場合には、格子体にクラツ
クが発生しやすくなるという欠点がある。また、
該格子体を用いた電池は、従来のアンチモン含有
量が4wt％以上の電池に比べて深放電サイクル寿
命が低下するという欠点があつた。
発明の目的
本発明は、上記組成の鉛−低アンチモン合金を
用いた格子体に発生するクラツクを防止し且つ該
格子体を用いた鉛蓄電池の深放電サイクル寿命を
改善することを目的とするものである。
発明の構成
本発明の第１は、0.5〜3.0wt％のアンチモン、
0.05〜0.5wt％のヒ素、0.01〜0.3wt％のカドミウ
ム、0.01〜1.0wt％の錫、0.01〜0.07wt％の銅と残
部鉛よりなる鉛合金格子体を用いる鉛蓄電池であ
る。
本発明の第２は、0.5〜3.0wt％のアンチモン、
0.05〜0.5wt％のヒ素、0.01〜0.3wt％のカドミウ
ム、0.01〜1.0wt％の錫、0.01〜0.07wt％の銅、
0.01〜0.2wt％のビスマスと残部鉛よりなる鉛合
金格子体を用いる鉛蓄電池である。
鉛蓄電池をMF化するためには、アンチモン含
有量が3wt％以下の鉛−低アンチモン合金よりな
る格子体を用いる必要がある。しかし、アンチモ
ン含有量が3wt％以下になると通常の鋳造法では
凝固時にクラツクが発生しやすくなる。これは凝
固温度範囲（凝固開始から終了までの温度）が大
きく、結晶がデンドライト状に成長し、結晶間の
未凝固部への溶湯の供給が十分行なわれないため
に起こる。種々の実験の結果、0.01〜0.07wt％の
銅の添加により上記クラツクの発生が防止できる
ことが判明した。これは銅の添加によりデンドラ
イトの成長が抑えられ、微細な結晶組織となるた
めクラツクの発生がなくなると考えられる。しか
し、銅の添加量が0.01〜0.07wt％以外の範囲では
効果がない。また、銅と共に0.01〜0.2wt％のビ
スマスを添加しても同様の効果がある。
時効硬化を促進するためには、0.05〜0.5wt％
のヒ素の添加が有効である。ヒ素の添加量が
0.05wt％未満では時効硬化はあまり生じない。ヒ
素の添加量が0.5wt％を越えると、不均一相の形
成により機械的強度が低下する。
合金の強度を向上させるには、0.01〜0.3wt％
のカドミウムの添加が有効である。カドミウムの
添加量が0.01wt％未満では効果がない。カドミウ
ムの添加量が0.3wt％を越えると、電池使用時に
カドミウムが負極板上に析出してデンドライト状
の結晶を成長させ、セパレータの貫通シヨートの
原因となる。
格子体の鋳造性をよくするためには、0.01〜
1.0wt％の錫の添加が有効である。錫の添加量が
0.01〜1.0wt％以外の範囲では効果がない。
実施例
本発明の実施例を詳述する。鉛−アンチモン−
ヒ素−カドミウム−錫よりなる鉛合金に0.01〜
0.07wt％の銅及び0.01〜0.2wt％のビスマスを添
加した鉛合金よりなる格子体を鋳造し、該格子体
を正極板に用いて、、36B20R形電池を試作し、
JIS寿命試験を行なつた。その結果を第１表に示
す。
第１表より明らかな如く、格子体合金に0.01〜
0.07wt％の銅を添加することにより、格子体に発
生するクラツクを防止できる。また、該格子体を
用いた電池は従来のアンチモン含有量が4wt％以
上の電池に比べて深放電サイクル寿命が改善され
ていることがわかる。
また、格子体合金に銅と共に0.01〜0.2wt
INDUSTRIAL APPLICATION FIELD The present invention relates to lead-acid batteries, and particularly to maintenance-free (hereinafter referred to as MF) lead-acid batteries for automobiles. Conventional technology and its problems Recently, in the market for lead-acid batteries, MF (maintenance-free) has been gaining popularity due to its advantages such as saving the trouble of refilling with water, low self-discharge, and being able to be stored for a long time in an injected state.
Demand for batteries is increasing. Conventionally, a lead-calcium alloy or a lead-low antimony alloy with an antimony content of 3 wt% or less has been used for the lattice alloy of the MF battery. However, when a lead-calcium alloy is used for the grid of the positive electrode plate, there is a drawback that the cycle life under conditions of relatively deep discharge (hereinafter referred to as deep discharge cycle life) is short. In order to eliminate this drawback, we developed a lead-low antimony alloy with an antimony content of 3wt% or less.
3.0wt% antimony, 0.05-0.5wt% arsenic,
A lead alloy consisting of 0.01 to 0.3 wt% cadmium, 0.01 to 1.0 wt% tin, and the balance lead is used. However, when the lead alloy is used, there is a drawback that cracks are likely to occur in the grid. Also,
Batteries using this lattice have a disadvantage in that their deep discharge cycle life is reduced compared to conventional batteries with an antimony content of 4 wt% or more. Purpose of the Invention The object of the present invention is to prevent cracks occurring in a lattice using a lead-low antimony alloy having the above composition, and to improve the deep discharge cycle life of a lead-acid battery using the lattice. It is. Structure of the Invention The first aspect of the present invention is that 0.5 to 3.0 wt% of antimony,
This is a lead-acid battery that uses a lead alloy grid consisting of 0.05 to 0.5 wt% arsenic, 0.01 to 0.3 wt% cadmium, 0.01 to 1.0 wt% tin, 0.01 to 0.07 wt% copper, and the balance lead. The second aspect of the present invention is 0.5 to 3.0 wt% antimony,
0.05-0.5wt% arsenic, 0.01-0.3wt% cadmium, 0.01-1.0wt% tin, 0.01-0.07wt% copper,
This is a lead-acid battery that uses a lead alloy grid consisting of 0.01 to 0.2 wt% bismuth and the balance lead. In order to convert a lead-acid battery to MF, it is necessary to use a lattice made of a lead-low antimony alloy with an antimony content of 3 wt% or less. However, when the antimony content is less than 3 wt%, cracks tend to occur during solidification using normal casting methods. This occurs because the solidification temperature range (temperature from the start to the end of solidification) is wide, the crystals grow in a dendrite shape, and molten metal is not sufficiently supplied to the unsolidified areas between the crystals. As a result of various experiments, it has been found that the above-mentioned cracks can be prevented by adding 0.01 to 0.07 wt% of copper. This is thought to be due to the addition of copper, which suppresses the growth of dendrites and creates a fine crystal structure, which eliminates the occurrence of cracks. However, there is no effect when the amount of copper added is outside the range of 0.01 to 0.07 wt%. Further, a similar effect can be obtained by adding 0.01 to 0.2 wt% of bismuth together with copper. To promote age hardening, 0.05~0.5wt%
Addition of arsenic is effective. The amount of arsenic added
At less than 0.05wt%, age hardening does not occur much. When the amount of arsenic added exceeds 0.5 wt%, the mechanical strength decreases due to the formation of a heterogeneous phase. 0.01~0.3wt% to improve the strength of the alloy
Addition of cadmium is effective. There is no effect if the amount of cadmium added is less than 0.01wt%. If the amount of cadmium added exceeds 0.3 wt%, cadmium will precipitate on the negative electrode plate during battery use, causing dendrite-like crystals to grow and causing shoots through the separator. In order to improve the castability of the lattice body, it is necessary to
Addition of 1.0wt% tin is effective. The amount of tin added is
It has no effect in a range other than 0.01-1.0wt%. Examples Examples of the present invention will be described in detail. Lead - antimony -
0.01 to lead alloy consisting of arsenic-cadmium-tin
A lattice body made of a lead alloy to which 0.07 wt% copper and 0.01 to 0.2 wt% bismuth was added was cast, and a 36B20R type battery was prototyped by using the lattice body as a positive electrode plate.
JIS life test was conducted. The results are shown in Table 1. As is clear from Table 1, 0.01~
By adding 0.07wt% copper, cracks occurring in the grid can be prevented. Furthermore, it can be seen that the deep discharge cycle life of the battery using the lattice body is improved compared to the conventional battery with an antimony content of 4 wt% or more. Also, 0.01~0.2wt with copper in lattice alloy
【表】
％のビスマスを添加することにより、格子体に発
生するクラツクを防止できると共に深放電サイク
ル寿命を更に改善できることがわかる。
発明の効果
本発明はその特許請求の範囲に記載した通りの
構成であるため、下記の効果がある。
(1) 格子体に発生するクラツクを防止できる。
(2) 深放電サイクル寿命が改善される。
(3) アンチモン含有量が3.0wt％以下であるため、
メンテナンスフリーである。[Table] It can be seen that by adding % bismuth, cracks occurring in the grid can be prevented and the deep discharge cycle life can be further improved. Effects of the Invention Since the present invention has the configuration as described in the claims, it has the following effects. (1) Cracks that occur in the grid can be prevented. (2) Deep discharge cycle life is improved. (3) Since the antimony content is 3.0wt% or less,
Maintenance free.
Claims (1)
ヒ素、0.01〜0.3wt％のカドミウム、0.01〜1.0wt
％の錫、0.01〜0.07wt％の銅と残部鉛よりなる鉛
合金格子体を用いることを特徴とする鉛蓄電池。 ２ 0.5〜3.0wt％のアンチモン、0.05〜0.5wt％の
ヒ素、0.01〜0.3wt％のカドミウム、0.01〜1.0wt
％の錫、0.01〜0.07wt％の銅、0.01〜0.2wt％のビ
スマスと残部鉛よりなる鉛合金格子体を用いるこ
とを特徴とする鉛蓄電池。[Claims] 1 0.5-3.0wt% antimony, 0.05-0.5wt% arsenic, 0.01-0.3wt% cadmium, 0.01-1.0wt
A lead-acid battery characterized by using a lead alloy lattice body consisting of % tin, 0.01 to 0.07 wt% copper, and the balance lead. 2 0.5-3.0wt% antimony, 0.05-0.5wt% arsenic, 0.01-0.3wt% cadmium, 0.01-1.0wt
A lead-acid battery characterized by using a lead alloy lattice body consisting of % tin, 0.01 to 0.07 wt% copper, 0.01 to 0.2 wt% bismuth, and the balance lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61164332A JPS6319768A (en) | 1986-07-11 | 1986-07-11 | Lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61164332A JPS6319768A (en) | 1986-07-11 | 1986-07-11 | Lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6319768A JPS6319768A (en) | 1988-01-27 |
| JPH0559548B2 true JPH0559548B2 (en) | 1993-08-31 |
Family
ID=15791159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61164332A Granted JPS6319768A (en) | 1986-07-11 | 1986-07-11 | Lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6319768A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2127124B1 (en) * | 1997-01-22 | 2000-01-01 | Tudor Acumulador | POSITIVE ELECTRODE AND LEAD ACCUMULATOR SPECIAL FOR USE IN HIGH TEMPERATURES. |
| CN101805836B (en) * | 2010-04-27 | 2011-08-24 | 天能电池(芜湖)有限公司 | Preparation method of Pb-Sb-Cd alloy used for positive plate of battery |
-
1986
- 1986-07-11 JP JP61164332A patent/JPS6319768A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6319768A (en) | 1988-01-27 |
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