JPS643029B2 - - Google Patents
Info
- Publication number
- JPS643029B2 JPS643029B2 JP55163869A JP16386980A JPS643029B2 JP S643029 B2 JPS643029 B2 JP S643029B2 JP 55163869 A JP55163869 A JP 55163869A JP 16386980 A JP16386980 A JP 16386980A JP S643029 B2 JPS643029 B2 JP S643029B2
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- electrolytic
- electrolysis
- current density
- active 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.)
- Expired
Links
- 239000000758 substrate Substances 0.000 claims description 44
- 238000005868 electrolysis reaction Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 230000002238 attenuated effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 239000011149 active material Substances 0.000 description 21
- 229910052759 nickel Inorganic materials 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004804 winding 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
- H01M4/28—Precipitating active material on the carrier
- H01M4/29—Precipitating active material on the carrier by electrochemical methods
-
- 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】
本発明はアルカリ蓄電池用電極、とくにニツケ
ル電極の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing electrodes for alkaline storage batteries, particularly nickel electrodes.
ニツケル電極の製造法には大別して、焼結式、
ペースト式、ポケツト式の３方式がある。 There are two main methods for manufacturing nickel electrodes: sintering method,
There are three types: paste type and pocket type.
現在、小形密閉式のニツケル・カドミウム蓄電
池に広く用いられている方法は、高価ではあつて
も高容量化、長寿命化が図れる焼結式が主体であ
る。 Currently, the method widely used for small sealed nickel-cadmium storage batteries is mainly the sintering method, which can achieve high capacity and long life, although it is expensive.
この焼結式極板における多孔性ニツケル基板へ
の活物質充填をみるに、現在では化学含浸法、熱
分解法、フライシヤー法及び陰電解法等がある。 Currently, there are chemical impregnation methods, thermal decomposition methods, Fleisher methods, and negative electrolytic methods for filling active materials into the porous nickel substrate of this sintered electrode plate.
このうち、作業工程的に及び活物質充填の所要
時間等から有利な方法は、陰電解法である。 Among these methods, the negative electrolytic method is advantageous in terms of the working process and the time required for filling the active material.
しかし陰電解法での活物質充填における一つの
問題点として、高電流密度域でのイオンの拡散不
十分による基板表面への活物質の集中的な析出が
ある。基板表面に集中的な活物質の析出が起こる
と、その後の化成工程等で基板表面に析出した活
物質の脱落が起こり、折角析出充填した活物質量
が減少して電極性能の向上には寄与しなくなる。 However, one problem in filling the active material using the negative electrolytic method is intensive precipitation of the active material on the substrate surface due to insufficient ion diffusion in the high current density region. When concentrated active material precipitation occurs on the substrate surface, the active material deposited on the substrate surface will fall off during the subsequent chemical conversion process, etc., and the amount of active material deposited and filled will decrease, contributing to improvement of electrode performance. I won't.
この基板表面における活物質の析出は定電流に
よる陰電解であつても、電解時間の経過、すなわ
ち活物質析出の進行とともに顕著となり、電解終
了時には目視判別可能な状態に至る。 Even in negative electrolysis using a constant current, the precipitation of the active material on the substrate surface becomes noticeable as the electrolysis time progresses, that is, as the active material precipitation progresses, and reaches a state that can be visually discerned at the end of the electrolysis.
本発明は、このような多孔性基板表面への活物
質の集中的な析出を改善して基板全体に効率的に
活物質を電解充填するものであり、その一つの方
策として電解液を攪拌しながら、この中に多孔性
金属基板を浸漬し連続的に移動させて陰電解し、
電解開始時に基板に流れる電解電流密度を1000〜
120ｍＡ／cm2と大きくする反面、電解時間の経過
とともに電解槽導入部から遠ざかるにつれて基板
に流れる電解電流密度を減衰させて電解終了時の
基板に流れる電解電流密度を100ｍＡ／cm2以下に
することを特徴としたものである。 The present invention improves the intensive precipitation of active material on the surface of a porous substrate and efficiently electrolytically fills the entire substrate with active material. One way to do this is to stir the electrolytic solution. Meanwhile, a porous metal substrate is immersed in this and moved continuously to perform negative electrolysis.
The electrolysis current density flowing through the substrate at the start of electrolysis is 1000~
While increasing the electrolytic current density to 120 mA/cm 2 , the electrolytic current density flowing to the substrate attenuates as it moves away from the introduction part of the electrolytic cell as the electrolysis time progresses, so that the electrolytic current density flowing to the substrate at the end of electrolysis is 100 mA/cm 2 or less. It is characterized by
以下、本発明の実施例を従来例と対比しつつ説
明する。従来、ニツケル電極の陰電解は電解槽内
の基板の複数点から給電し、基板の位置に関係な
く一定電流密度とした定電流密度をとつていたた
め、電解終了時の基板表面への活物質の集中的な
析出を防止すべく、予め電解開始時から電解電流
密度を例えば80ｍＡ／cm2と低くしていた。なおこ
の際用いた多孔性ニツケル基板は幅30mm、長さ
100mm、厚さ0.7mmに裁断されたもので、電解液に
は３モル／の硝酸ニツケル水溶液をPH２〜３に
調整し、液温を80℃保つたものを用いた。この条
件で充填理論容量密度270ｍＡ／cm2を得る場合、
バツチ方式の電解では80ｍＡ／cm2の電流密度で約
１時間半処理しなくてはならなかつた。 Hereinafter, embodiments of the present invention will be described in comparison with conventional examples. Conventionally, negative electrolysis of nickel electrodes was carried out by supplying power from multiple points on the substrate in the electrolytic cell, and maintaining a constant current density regardless of the position of the substrate. In order to prevent intensive precipitation of , the electrolytic current density was set low, for example, 80 mA/cm 2 from the start of electrolysis. The porous nickel substrate used at this time was 30 mm wide and long.
It was cut into pieces of 100 mm and 0.7 mm thick, and the electrolyte used was a 3 mol/aqueous nickel nitrate solution adjusted to pH 2 to 3 and kept at 80°C. When obtaining a filling theoretical capacity density of 270 mA/cm 2 under these conditions,
Batch electrolysis required treatment at a current density of 80 mA/cm 2 for about one and a half hours.
本発明はこのような陰電解条件において基板に
流れる電解電流密度を電解開始時に、例えば150
ｍＡ／cm2とし、基板の移動、すなわち活物質の充
填量が増大するにつれて次第に基板に流れる電解
電流密度を減衰させてゆき、目的とした量の活物
質が基板に充填された電解終了時のそれは60ｍ
Ａ／cm2の電流密度とした。 The present invention reduces the electrolysis current density flowing through the substrate under such negative electrolysis conditions to, for example, 150% at the start of electrolysis.
mA/ cm2 , and as the substrate moves, that is, the amount of active material filled increases, the electrolytic current density flowing through the substrate is gradually attenuated. That is 60m
The current density was A/cm 2 .
なお、陰電解は本例では作業性を考慮して連続
的に帯状の基板を電解槽中に浸漬して移動させる
連続法を用いた。第１図中１は電解時の対極（ア
ノード）でニツケル板等からなり、２は前記の電
解液を収容した電解槽、３は陰電解されるカソー
ドとしての多孔性ニツケル基板で、電源４により
電解槽１の導入側外部で負に帯電されている。５
は基板を送り出すコイラー、６は活物質充填剤の
基板を巻取る巻取コイラーである。 Note that in this example, in consideration of workability, a continuous method was used for negative electrolysis, in which a strip-shaped substrate was continuously immersed and moved in an electrolytic bath. In Fig. 1, 1 is a counter electrode (anode) during electrolysis, which is made of a nickel plate, etc., 2 is an electrolytic tank containing the electrolyte, and 3 is a porous nickel substrate as a cathode for negative electrolysis, which is powered by a power source 4. The outside of the introduction side of the electrolytic cell 1 is negatively charged. 5
6 is a coiler that sends out the substrate, and 6 is a winding coiler that winds up the substrate containing the active material filler.
このように電解時の２枚のニツケル板からなる
対極１を電源４の正に帯電させて、この対極間の
電解液中に浸漬させてニツケル基板３を移動させ
ると、給電体から遠ざかるにつれて基板のもつ内
部抵抗の増大に伴つてIRドロツプが生じ、電解
電流密度は基板の電解槽への導入部が最大の大き
さであり、第２図の如く、電解電流密度は基板の
移動（電解）につれて次第に減衰してゆく。この
例では電解開始時の基板に流れる電流密度を150
ｍＡ／cm2とし、終了時のそれを60ｍＡ／cm2とし
た。そして電解開始後70分で、従来と同様の極板
容量密度が得られた。 In this way, when the counter electrode 1 consisting of two nickel plates during electrolysis is positively charged by the power source 4, and the nickel substrate 3 is moved by immersing it in the electrolyte between the counter electrodes, the substrate 3 moves away from the power supply. An IR drop occurs as the internal resistance of the substrate increases, and the electrolytic current density is at its maximum at the point where the substrate is introduced into the electrolytic cell. It gradually decreases over time. In this example, the current density flowing through the substrate at the start of electrolysis is set to 150
mA/cm 2 , and the final value was 60 mA/cm 2 . 70 minutes after the start of electrolysis, the same plate capacity density as before was obtained.
第３図は電解電気量と、活物質充填量との関係
を示したもので、基板の移動に関係なく一定電流
密度としたものＡに比べ、電解開始時に基板に流
れる電解電流密度を最大とし、電解の通行に伴つ
て基板の電解電流密度を次第に減衰させた本発明
品Ｂは、活物質充填量を約10％向上させることが
できた。 Figure 3 shows the relationship between the amount of electrolytic electricity and the amount of active material filled.Compared to A, where the current density is constant regardless of the movement of the substrate, the electrolytic current density flowing through the substrate at the start of electrolysis is maximized. Inventive product B, in which the electrolytic current density in the substrate was gradually attenuated as the electrolytic flow progressed, was able to increase the amount of active material filled by about 10%.
なお陰電解に当つて電解開始時の基板の電解電
流密度は1000〜120ｍＡ／cm2とし、電解時間の経
過とともに電解電流密度を減衰させ、電解終了時
には100ｍＡ／cm2以下とするとよい。電解開始時
には極力大電流密度とすることで基板の芯材側の
良導電性と電解液の攪拌とが合いまつて、基板内
部に活物質を析出させ得るが、1000ｍＡ／cm2より
も大電流密度では基板表面への活物質析出が増大
するので避けるべきである。又120ｍＡ／cm2より
も小さな電流密度では電解時間の短縮化が十分に
達せられない。 In negative electrolysis, it is preferable that the electrolytic current density of the substrate at the start of electrolysis is 1000 to 120 mA/cm 2 , and the electrolytic current density is attenuated as the electrolysis time elapses to be 100 mA/cm 2 or less at the end of electrolysis. By setting the current density as high as possible at the start of electrolysis, the good conductivity of the core material side of the substrate and the stirring of the electrolyte can be combined, and the active material can be deposited inside the substrate, but a current higher than 1000 mA/cm 2 Density should be avoided because it increases active material precipitation on the substrate surface. Furthermore, if the current density is lower than 120 mA/cm 2 , the electrolysis time cannot be shortened sufficiently.
電解終了時の電流密度は、開始時のそれと密接
に関連するが、100ｍＡ／cm2以下、好ましくは80
〜50ｍＡ／cm2で電解を完了するのが作業性の上か
らは望ましい。 The current density at the end of electrolysis is closely related to that at the beginning, but is less than 100 mA/cm2, preferably 80 mA/ cm2 or less.
From the viewpoint of workability, it is desirable to complete the electrolysis at ~50 mA/cm 2 .
このように電解開始時の基板の電解電流密度を
大とすることで、基板の良導電性と電解液の攪拌
とがあいまつて、効率よく活物質を基板内部に析
出させることができ、基板表面への活物質付着を
抑制することができる。 In this way, by increasing the electrolysis current density of the substrate at the start of electrolysis, the good conductivity of the substrate and the stirring of the electrolyte solution are combined, and the active material can be efficiently deposited inside the substrate. It is possible to suppress adhesion of the active material to.
第１図は本発明の実施例における連続的なニツ
ケル電極の陰電解による活物質充填工程を示す略
図、第２図は電解槽中での基板の位置と電解電流
密度との関係を示す図、第３図は電解電気量と活
物質充填量との関係を示す図である。
１……電解時の対極（アノード）、２……電解
槽、３……多孔性ニツケル基板、４……電解電
源。
FIG. 1 is a schematic diagram showing the active material filling process by continuous negative electrolysis of a nickel electrode in an embodiment of the present invention, FIG. 2 is a diagram showing the relationship between the position of the substrate in the electrolytic cell and the electrolytic current density, FIG. 3 is a diagram showing the relationship between the amount of electrolytic electricity and the amount of active material filled. 1... Counter electrode (anode) during electrolysis, 2... Electrolytic tank, 3... Porous nickel substrate, 4... Electrolysis power source.
Claims (1)
れ攪拌されている活物質形成塩水溶液からなる電
解液中に浸漬し連続的に移動させて陰電解する方
法において、前記基板に電液槽導入部側で給電す
るとともに電解液を攪拌しながら電解開始時の前
記基板の電解電流密度を1000〜120ｍＡ／cm2とし、
電解槽内での前記基板の移動とともに基板の内部
抵抗増加により電解電流密度を減衰させて電解終
了時の前記基板の電解電流密度を80〜50ｍＡ／cm2
とすることを特徴とするアルカリ蓄電池用電極の
製造法。 ２ 前記電解液が、硝酸ニツケルを３モル／の
割合で溶解し、かつそのPHを１〜４、液温度を80
〜100℃に保つたものである特許請求の範囲第１
項に記載のアルカリ蓄電池用電極の製造法。[Claims] 1. A method for negative electrolysis by immersing and continuously moving a porous metal substrate in an electrolytic solution consisting of an aqueous active material-forming salt solution that is housed in an electrolytic tank and stirred. , while supplying power to the substrate on the electrolyte tank inlet side and stirring the electrolytic solution, setting the electrolytic current density of the substrate at 1000 to 120 mA/cm 2 at the start of electrolysis,
As the substrate moves within the electrolytic cell, the electrolytic current density is attenuated due to an increase in the internal resistance of the substrate, so that the electrolytic current density of the substrate at the end of electrolysis is 80 to 50 mA/cm 2
A method for producing an electrode for an alkaline storage battery, characterized by: 2 The electrolytic solution dissolves nickel nitrate at a ratio of 3 mol/mole, and has a pH of 1 to 4 and a liquid temperature of 80.
Claim 1, which is maintained at a temperature of ~100°C
A method for producing an electrode for an alkaline storage battery as described in 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55163869A JPS5788669A (en) | 1980-11-20 | 1980-11-20 | Manufacture of electrode for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55163869A JPS5788669A (en) | 1980-11-20 | 1980-11-20 | Manufacture of electrode for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5788669A JPS5788669A (en) | 1982-06-02 |
| JPS643029B2 true JPS643029B2 (en) | 1989-01-19 |
Family
ID=15782311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55163869A Granted JPS5788669A (en) | 1980-11-20 | 1980-11-20 | Manufacture of electrode for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5788669A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63105468A (en) * | 1986-10-20 | 1988-05-10 | Sanyo Electric Co Ltd | Manufacture of nickel hydroxide electrode for alkaline storage battery |
| KR101351901B1 (en) * | 2010-10-19 | 2014-01-17 | 주식회사 엘지화학 | Anode For Cable Type Secondary Battery And Preparation Method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5466430A (en) * | 1977-11-08 | 1979-05-29 | Tokyo Shibaura Electric Co | Preparation of nickel positive pole for alkaline battery |
-
1980
- 1980-11-20 JP JP55163869A patent/JPS5788669A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5788669A (en) | 1982-06-02 |
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