JPH0582708B2 - - Google Patents
Info
- Publication number
- JPH0582708B2 JPH0582708B2 JP60188864A JP18886485A JPH0582708B2 JP H0582708 B2 JPH0582708 B2 JP H0582708B2 JP 60188864 A JP60188864 A JP 60188864A JP 18886485 A JP18886485 A JP 18886485A JP H0582708 B2 JPH0582708 B2 JP H0582708B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- tin
- alloy
- calcium
- 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 - Lifetime
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 7
- 239000002142 lead-calcium alloy Substances 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910001887 tin oxide Inorganic materials 0.000 description 5
- 229910001128 Sn alloy Inorganic materials 0.000 description 4
- 230000005484 gravity Effects 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DPDORTBBLUCNJG-UHFFFAOYSA-N calcium tin Chemical compound [Ca].[Sn] DPDORTBBLUCNJG-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007654 immersion Methods 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003756 stirring Methods 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
- H01M4/14—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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (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−カルシウム合金からなる基体を
用いた陽極板の製造法の改良に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an improvement in the manufacturing method of an anode plate using a substrate made of a lead-calcium alloy.
従来の技術
従来所謂メンテナンスフリーバツテリー用極板
として鉛−カルシウム合金からなる基体を用いて
いるものがあるが、深放電サイクルや深放電放置
を行なえば、基体と活物質との接触界面に不働態
層が形成され、早期に容量劣化する、このような
欠点を除去するために、基体合金中に錫を添加
し、鉛−カルシウム−錫合金からなる基体を用い
ているものがある。Conventional technology Conventionally, there are so-called maintenance-free battery electrode plates that use a base made of a lead-calcium alloy, but if a deep discharge cycle or deep discharge is performed, a passive state will form at the contact interface between the base and the active material. In order to eliminate such a drawback that a layer is formed and the capacity deteriorates early, some devices add tin to the base alloy and use a base made of a lead-calcium-tin alloy.
発明が解決しようとする問題点
鉛−カルシウム−錫からなる基体を製造するに
先立だつて鉛、カルシウム、錫各々を溶融し、合
金湯を作る必要がある。この場合、錫は鉛より比
重が小さいので合金湯の上面に浮きあがり、酸
化、蒸発により合金湯中の錫が時間の経過と共に
減少し易い。このため該合金湯を用いて製造した
基体中の錫含有量は非常にバラツキの大きなもの
となる。一方、深放電サイクルや深放電放置によ
る電池容量の早期劣化防止策として鉛−カルシウ
ム合金基体の場合、１％程度の錫の添加が一般的
であり、錫の含有量がこれより低下するに伴い、
電池容量が早期に劣化する。従つて、従来法によ
つて製造される基体中の錫含有量のバラツキは電
池寿命を大きくばらつかせ、品質低下をきたす等
の欠点を有している。Problems to be Solved by the Invention Prior to manufacturing a base made of lead-calcium-tin, it is necessary to melt each of lead, calcium, and tin to create an alloy hot water. In this case, since tin has a lower specific gravity than lead, it floats to the top of the alloy bath, and the tin in the alloy bath tends to decrease over time due to oxidation and evaporation. For this reason, the tin content in substrates produced using the alloy molten metal varies greatly. On the other hand, in the case of lead-calcium alloy substrates, as a measure to prevent early deterioration of battery capacity due to deep discharge cycles or deep discharge storage, it is common to add approximately 1% tin, and as the tin content decreases ,
Battery capacity deteriorates early. Therefore, variations in tin content in substrates produced by conventional methods have disadvantages such as greatly varying battery life and deteriorating quality.
一方、活物質の軟化・脱落の防止を目的とし
て、鉛蓄電池用陽極板の活物質中に錫の酸化物を
添加することが提案されているが、鉛粉と希硫酸
とを混練してペーストを作る際、錫の酸化物を添
加すると、鉛粉に比べて錫の酸化物の比重が相当
に小さいため、錫の酸化物がペースト中に均一に
分散しない惧れがあり、また、活物質中に添加さ
れた錫の酸化物は安定な化合物であるため、鉛蓄
電池用陽極板の鉛−カルシム合金からなる基体と
活物質との接触界面における不働体層形成防止に
対しては不向きであつた。 On the other hand, it has been proposed to add tin oxide to the active material of the positive electrode plate for lead-acid batteries in order to prevent the active material from softening and falling off. When making a paste, if tin oxide is added, the specific gravity of tin oxide is considerably lower than that of lead powder, so there is a risk that the tin oxide will not be uniformly dispersed in the paste. Since the tin oxide added therein is a stable compound, it is not suitable for preventing the formation of a passive layer at the contact interface between the active material and the lead-calcium alloy base of the anode plate for lead-acid batteries. Ta.
問題点を解決するための手段
合金中に錫を添加しないで、鉛−カルシウム合
金からなる陽極基体を製造し、該基体に鉛粉等の
活物質原料を充填した後該極板を錫塩の存在する
希硫酸に浸漬するようにしたものである。Means for solving the problem: An anode substrate made of a lead-calcium alloy is manufactured without adding tin to the alloy, and after filling the substrate with an active material raw material such as lead powder, the electrode plate is treated with tin salt. It is designed to be immersed in existing dilute sulfuric acid.
作 用
希硫酸中に存在する錫塩の量は、極板を浸漬し
ない間は減少することなく一定量を保つている。
また極板を浸漬する場合、浸漬時間、浸漬温度、
液の硫酸濃度、液中の錫塩の量等の浸漬条件を一
定に保てば、極板中の錫塩の存在量はほぼ一定に
なる。Function: The amount of tin salt present in dilute sulfuric acid remains constant without decreasing while the electrode plate is not immersed.
In addition, when dipping the electrode plate, the dipping time, dipping temperature,
If immersion conditions such as the sulfuric acid concentration of the solution and the amount of tin salt in the solution are kept constant, the amount of tin salt present in the electrode plate will be approximately constant.
実施例
まず比重1.05の希硫酸１当り、錫を10ｇ添加
した陽極板浸漬用液を作つた。次に該液中にあら
かじめ鉛−カルシウム合金からなる基体（３mm
厚）に鉛粉等の活物質原料を充填した陽極板を10
分間浸漬した。この場合、液を攪拌しながら陽極
板を浸漬した。浸漬後乾燥して従来の方法で化成
し陽極板を得た。Example First, a solution for dipping an anode plate was prepared by adding 10 g of tin per 1 dilute sulfuric acid having a specific gravity of 1.05. Next, a base made of lead-calcium alloy (3 mm
The anode plate (thickness) filled with active material raw material such as lead powder is
Soaked for minutes. In this case, the anode plate was immersed while stirring the liquid. After dipping, it was dried and chemically formed using a conventional method to obtain an anode plate.
本発明による陽極と鉛−カルシウムおよび鉛−
カルシウム−錫合金からなる基体を用いた従来の
極板の寿命試験結果を図面に示す。図面の横軸は
充放電回数、縦軸は10HR容量で、従来の方法で
得た鉛−カルシウム合金基体を用いた極板の第１
回目の放電容量を100としてその比で示した。Ａ
は鉛−カルシウム合金基体からなる極板を用いた
従来の電池、Ｂ１，Ｂ２は鉛−カルシウム−錫合
金基体からなる極板を用いた従来の電池、Ｃは本
発明による極板を用いた電池である。図面に示す
ように、本発明による極板を用いた電池Ｃは、従
来の基体からなる極板を用いた電池Ｂ１，Ｂ２に
比較し、寿命特性のハラツキは無く品質が安定し
ている。更に従来の基体からなる極板を用いた電
池Ａ，Ｂ１よりも寿命特性が優れていることがわ
かる。 Anode and lead according to the invention - calcium and lead -
The drawing shows the life test results of a conventional electrode plate using a substrate made of a calcium-tin alloy. The horizontal axis of the drawing is the number of charges and discharges, and the vertical axis is the 10HR capacity.
The discharge capacity of the second discharge is set as 100 and the ratio is shown. A
B1 and B2 are conventional batteries using electrode plates made of a lead-calcium-tin alloy substrate, and C is a battery using the electrode plate according to the present invention. It is. As shown in the drawings, battery C using the electrode plate according to the present invention has stable quality with no variation in life characteristics than batteries B1 and B2 using electrode plates made of conventional substrates. Furthermore, it can be seen that the battery life characteristics are superior to those of batteries A and B1 using electrode plates made of conventional substrates.
発明の効果
上述のように、本発明により得られた陽極板
は、鉛−カルシウム−錫合金基体からなる陽極板
を用いた従来の電池と比較し、寿命性能のバラツ
キが極めて少なく、且つ最低寿命性能を向上する
ことができる等工業的価値きわめて大なるもので
ある。Effects of the Invention As described above, the anode plate obtained by the present invention has extremely little variation in life performance and has a minimum lifespan compared to conventional batteries using an anode plate made of a lead-calcium-tin alloy base. It has great industrial value as it can improve performance.
図面は本発明により得られた極板を用いた電池
と従来の基板からなる極板を用いた電池との寿命
特性比較図である。
The drawing is a comparison diagram of the life characteristics of a battery using an electrode plate obtained according to the present invention and a battery using an electrode plate made of a conventional substrate.
Claims (1)
料を充填した極板を、錫塩の存在する希硫酸に浸
漬することを特徴とする鉛蓄電池陽極板の製造
法。1. A method for producing an anode plate for a lead-acid battery, which comprises immersing an electrode plate in which a substrate made of a lead-calcium alloy is filled with an active material raw material in dilute sulfuric acid in the presence of tin salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60188864A JPS6251161A (en) | 1985-08-28 | 1985-08-28 | Manufacture of cathode plate for lead storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60188864A JPS6251161A (en) | 1985-08-28 | 1985-08-28 | Manufacture of cathode plate for lead storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6251161A JPS6251161A (en) | 1987-03-05 |
| JPH0582708B2 true JPH0582708B2 (en) | 1993-11-22 |
Family
ID=16231199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60188864A Granted JPS6251161A (en) | 1985-08-28 | 1985-08-28 | Manufacture of cathode plate for lead storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6251161A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4971431A (en) * | 1972-11-14 | 1974-07-10 | ||
| JPS5510101A (en) * | 1976-10-21 | 1980-01-24 | Aida Eng Ltd | Transfer feed unit for press |
-
1985
- 1985-08-28 JP JP60188864A patent/JPS6251161A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4971431A (en) * | 1972-11-14 | 1974-07-10 | ||
| JPS5510101A (en) * | 1976-10-21 | 1980-01-24 | Aida Eng Ltd | Transfer feed unit for press |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6251161A (en) | 1987-03-05 |
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