JPH0562430B2 - - Google Patents
Info
- Publication number
- JPH0562430B2 JPH0562430B2 JP60007264A JP726485A JPH0562430B2 JP H0562430 B2 JPH0562430 B2 JP H0562430B2 JP 60007264 A JP60007264 A JP 60007264A JP 726485 A JP726485 A JP 726485A JP H0562430 B2 JPH0562430 B2 JP H0562430B2
- Authority
- JP
- Japan
- Prior art keywords
- active material
- substrate
- alkaline solution
- sintered
- nickel
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 28
- 239000011149 active material Substances 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000012670 alkaline solution Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 7
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001661 cadmium Chemical class 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical group [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical group [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005979 thermal decomposition reaction 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
-
- 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〉
この発明は焼結式極板の製造方法に関し、詳し
くは、ニツケル焼結基板に保持された金属塩をア
ルカリ置換処理することでニツケル焼結基板中に
前記金属の水酸化物を主成分とする活物質を充填
する方法において、アルカリ置換処理に用いるア
ルカリ液の組成を改良することで活物質の充填効
率向上等を図つたものに関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for manufacturing a sintered electrode plate, and more specifically, the present invention relates to a method for manufacturing a sintered electrode plate, and more specifically, the invention relates to a method for manufacturing a sintered electrode plate. The present invention relates to a method for filling a substrate with an active material containing the metal hydroxide as a main component, in which the filling efficiency of the active material is improved by improving the composition of the alkaline solution used in the alkali replacement treatment.
〈従来の技術〉
アルカリ蓄電池、例えばニツケル・カドミウム
電池に用いられる焼結式カドミウム極板として
は、一般に多孔性金属板にカーボニルニツケル等
の金属粉末を焼結して得たニツケル焼結基板に水
酸化カドミウムを主成分とする活物質を充填して
得たものが知られている。ニツケル焼結基板にこ
のような活物質を充填する方法としては、例えば
特開昭58−198857号公報に開示されているよう
に、ニツケル焼結基板を硝酸カドミウムの如きカ
ドミウム塩の水溶液中に浸漬して基板中にカドミ
ウム塩を含浸せしめ、次いでニツケル焼結基板に
保持されたカドミウム塩をアルカリ置換、熱分
解、電解等の方法により水酸化物に置換する方法
が用いられている。そして、このような充填操作
を数回繰返すことによつてニツケル焼結基板に所
定量の活物質を確保している。<Prior art> Sintered cadmium electrode plates used in alkaline storage batteries, such as nickel-cadmium batteries, are generally made by sintering a nickel sintered substrate obtained by sintering metal powder such as carbonyl nickel onto a porous metal plate, and then applying water to the nickel sintered substrate. It is known that the material is filled with an active material whose main component is cadmium oxide. As a method for filling a nickel sintered substrate with such an active material, for example, as disclosed in Japanese Patent Laid-Open No. 198857/1985, the nickel sintered substrate is immersed in an aqueous solution of a cadmium salt such as cadmium nitrate. A method is used in which the substrate is impregnated with cadmium salt, and then the cadmium salt held in the nickel sintered substrate is replaced with hydroxide by a method such as alkali substitution, thermal decomposition, or electrolysis. By repeating this filling operation several times, a predetermined amount of active material is secured in the nickel sintered substrate.
〈発明が解決しようとする問題点〉
ところで、一般に広く行なわれているアルカリ
置換による方法においては、苛性ソーダ、苛性カ
リ等のアルカリ液中に例えば硝酸カドミウムを含
浸したニツケル焼結基板を浸漬し、
Cd（NO3）2＋2OH-
→Cd（OH）2＋2NO3 -
なる反応によつて基板中の硝酸カドミウムを水酸
化カドミウムに置換している。しかしながら、こ
の方法には高温下においてニツケル焼結基板に含
浸されているカドミウムがアルカリ液中に溶け出
してしまうという問題がある。そして、アルカリ
液中に溶け出すカドミウムの溶解量は濃度として
は僅かではあるが、アルカリ置換処理を工業的に
大量のアルカリ液を用いて行なう場合はニツケル
焼結基板の活物質含浸量がかなり低下し、このた
め１回の充填操作による活物質充填量もその分少
なくなつてしまうという結果を招く。<Problems to be Solved by the Invention> By the way, in the generally widely used method of alkali substitution, a nickel sintered substrate impregnated with, for example, cadmium nitrate is immersed in an alkaline solution such as caustic soda or caustic potash. Cadmium nitrate in the substrate is replaced with cadmium hydroxide through the reaction NO 3 ) 2 +2OH - →Cd(OH) 2 +2NO 3 - . However, this method has a problem in that cadmium impregnated into the nickel sintered substrate dissolves into the alkaline solution at high temperatures. Although the amount of cadmium dissolved in the alkaline solution is small in terms of concentration, when alkali replacement treatment is carried out industrially using a large amount of alkaline solution, the amount of active material impregnated into the nickel sintered substrate decreases considerably. However, this results in the amount of active material filled in one filling operation being reduced accordingly.
一方、アルカリ液を繰り返し用いてアルカリ置
換をおこなう場合には、アルカリ液中にCd2+が
飽和した後はCd2+の溶解量が少なくなるために
上記のように活物質含浸量低下という問題はなく
なる。しかしながらこの場合には、アルカリ液中
のOH-濃度が漸次減少し、一方、NO3 -濃度が漸
次増加するために、同じアルカリ液をアルカリ置
換処理用として使用できる回数には自ずと限度が
あり、この限度を超えて用いるとアルカリ置換能
力が低下してしまうという不都合が生じる。従つ
て、アルカリ置換処理工程において使用限度を超
えたアルカリ液は廃棄して新しいアルカリ液に取
替なければならず、このように新しいアルカリ液
を用いた場合にはCd2+の溶解により再び基板の
活物質含浸量低下が起こつてしまう。このため、
アルカリ液を繰り返し用いる場合には、ニツケル
焼結基板の活物質含浸量にバラツキが生じ、１回
の充填操作あたりの活物質充填量を揃えることが
困難になるという問題がある。 On the other hand, when alkaline replacement is performed by repeatedly using an alkaline solution, the amount of Cd 2+ dissolved decreases after the alkaline solution becomes saturated, resulting in the problem of a decrease in the amount of active material impregnated as described above. will disappear. However, in this case, the OH - concentration in the alkaline solution gradually decreases, while the NO 3 - concentration gradually increases, so there is a natural limit to the number of times the same alkali solution can be used for alkali replacement treatment. When used in excess of this limit, there arises the disadvantage that the alkali replacement ability is reduced. Therefore, in the alkaline replacement treatment process, the alkaline solution that exceeds the usage limit must be discarded and replaced with new alkaline solution.If new alkaline solution is used in this way, the Cd 2+ will dissolve and the substrate will be regenerated. A decrease in the amount of active material impregnated occurs. For this reason,
When an alkaline solution is repeatedly used, there is a problem in that the amount of active material impregnated into the nickel sintered substrate varies, making it difficult to equalize the amount of active material filled in each filling operation.
〈問題点を解決するための手段〉
この発明の焼結式極板の製造方法は、ニツケル
焼結基板に保持された金属塩をアルカリ液中でア
ルカリ置換処理することでニツケル焼結基板中に
前記金属の水酸化物を主成分とする活物質を充填
する焼結式電極の製造方法において、アルカリ液
中に前記金属を溶解飽和させた状態で前記アルカ
リ置換処理を行なうことを要旨とする。<Means for Solving the Problems> The method for manufacturing a sintered electrode plate of the present invention is to carry out alkali substitution treatment on the metal salt held on the nickel sintered substrate in an alkaline solution, thereby dissolving the metal salt in the nickel sintered substrate. In the method for manufacturing a sintered electrode filled with an active material whose main component is a hydroxide of the metal, the alkali substitution treatment is performed in a state where the metal is dissolved and saturated in an alkaline solution.
〈作用〉
上記手段により、アルカリ置換処理工程におい
てニツケル焼結基板からの活物質を形成する金属
の溶出は常に抑えられる。この結果、基板の活物
質含浸量低下を防止できると共に、活物質含浸量
のバラツキをなくすことができる。<Function> With the above means, the elution of the metal forming the active material from the nickel sintered substrate is always suppressed in the alkali replacement treatment step. As a result, it is possible to prevent a decrease in the amount of active material impregnated into the substrate, and also to eliminate variations in the amount of active material impregnated.
〈実施例〉
公知の方法によつて製造したニツケル焼結基板
を溶融硝酸カドミウム浴に一定時間浸漬して基板
に硝酸カドミウムを含浸した後、この基板を
Cd2+が飽和（約120ppm）沈澱された80℃苛性ソ
ーダ30％溶液に約60分間浸漬し、爾後、水洗、乾
燥して本発明に係る焼結式カドミウム基板（極板
１）を作つた。<Example> A nickel sintered substrate manufactured by a known method was immersed in a molten cadmium nitrate bath for a certain period of time to impregnate the substrate with cadmium nitrate.
It was immersed for about 60 minutes in a 30% caustic soda solution at 80° C. in which Cd 2+ was saturated (about 120 ppm) precipitated, then washed with water and dried to produce a sintered cadmium substrate (electrode plate 1) according to the present invention.
同じように溶融硝酸カドミウム浴浸漬による硝
酸カドミウムの含浸を行なつたニツケル焼結基板
を、Cd2+を全く溶解していない80℃苛性ソーダ
30％溶液に約60分間浸漬、爾後、水洗、乾燥して
従来方法による焼結式カドミウム極板（極板２）
を作つた。 A nickel sintered substrate impregnated with cadmium nitrate by immersion in a molten cadmium nitrate bath was soaked in 80°C caustic soda without any Cd 2+ dissolved therein.
Immersed in a 30% solution for about 60 minutes, then washed with water, dried and sintered using the conventional method (Plate 2)
I made it.
以上のようにして得た極板１，２のそれぞれに
ついて含浸処理前の基板重量とアルカリ置換処理
後の極板重量との差、即ち活物質の充填重量ｇを
測定した結果を下表に示す。尚、下表の値は１回
の充填操作により得られた極板１ｍ×１ｍ×0.60
mm体積あたりの活物質充填重量である。 The table below shows the difference between the substrate weight before impregnation treatment and the electrode plate weight after alkali replacement treatment, that is, the filling weight of the active material in g, for each of electrode plates 1 and 2 obtained as described above. . In addition, the values in the table below are for the electrode plate 1m x 1m x 0.60 obtained by one filling operation.
It is the active material filling weight per mm volume.
極板１ 250ｇ
極板２ 235ｇ
尚、上記実施例では焼結式カドミウム極板につ
いて述べたが、焼結式ニツケル極板においても同
様な効果が得られることは明らかである。 Plate 1: 250 g Plate 2: 235 g In the above embodiment, a sintered cadmium electrode plate was described, but it is clear that similar effects can be obtained with a sintered nickel electrode plate.
〈発明の効果〉
以上のように、この発明の焼結式極板の製造方
法は、金属塩を保持したニツケル焼結基板を、前
記金属を溶解飽和させた状態のアルカリ液中でア
ルカリ置換処理するものであり、このような手段
を用いることにより基板からアルカリ液中への前
記金属の溶出は常に抑えられるから、従来の製造
方法のようにアルカリ置換処理により基板の活物
質含浸量が低下したり、活物質含浸量がバラつく
といつた不都合を確実に解消することができ、こ
のような不都合に起因する活物質充填量の低下及
びバラツキをなくすことができる。また、１回の
充填操作による活物質充填量を増大できて充填効
率が向上する結果、充填操作の回数を減らすこと
ができるので製造工程の煩雑さをかなり解消する
ことができるという利点もあり、その工業的価値
は大なるものである。<Effects of the Invention> As described above, the method for producing a sintered electrode plate of the present invention involves subjecting a sintered nickel substrate holding a metal salt to an alkali substitution treatment in an alkaline solution in which the metal is saturated with the dissolved metal. By using such means, the elution of the metal from the substrate into the alkaline solution is always suppressed, so that the amount of active material impregnated into the substrate is reduced by alkali substitution treatment unlike in conventional manufacturing methods. Inconveniences such as variations in the amount of active material impregnated can be reliably eliminated, and reductions and variations in the amount of active material filled due to such inconveniences can be eliminated. In addition, it is possible to increase the amount of active material filled in one filling operation, improving filling efficiency, and as a result, the number of filling operations can be reduced, which has the advantage that the complexity of the manufacturing process can be significantly reduced. Its industrial value is great.
Claims (1)
カリ液中でアルカリ置換処理することで前記ニツ
ケル焼結基板中に前記金属の水酸化物を主成分と
する活物質を充填する焼結式電極の製造方法にお
いて、前記アルカリ液中に前記金属を溶解飽和さ
せた状態で前記アルカリ置換処理を行なうことを
特徴とする焼結式極板の製造方法。1. A sintered electrode in which the metal salt held on the nickel sintered substrate is subjected to alkali substitution treatment in an alkaline solution to fill the nickel sintered substrate with an active material whose main component is the hydroxide of the metal. A method for manufacturing a sintered electrode plate, characterized in that the alkali replacement treatment is performed in a state where the metal is dissolved and saturated in the alkaline solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60007264A JPS61168868A (en) | 1985-01-18 | 1985-01-18 | Manufacture of sintered electrode plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60007264A JPS61168868A (en) | 1985-01-18 | 1985-01-18 | Manufacture of sintered electrode plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61168868A JPS61168868A (en) | 1986-07-30 |
| JPH0562430B2 true JPH0562430B2 (en) | 1993-09-08 |
Family
ID=11661168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60007264A Granted JPS61168868A (en) | 1985-01-18 | 1985-01-18 | Manufacture of sintered electrode plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61168868A (en) |
-
1985
- 1985-01-18 JP JP60007264A patent/JPS61168868A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61168868A (en) | 1986-07-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |