JPH02163392A - Production of electrode - Google Patents
Production of electrodeInfo
- Publication number
- JPH02163392A JPH02163392A JP63314969A JP31496988A JPH02163392A JP H02163392 A JPH02163392 A JP H02163392A JP 63314969 A JP63314969 A JP 63314969A JP 31496988 A JP31496988 A JP 31496988A JP H02163392 A JPH02163392 A JP H02163392A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- iron
- sulfur
- base material
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000007747 plating Methods 0.000 claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 52
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 70
- 229910052742 iron Inorganic materials 0.000 abstract description 35
- 238000005868 electrolysis reaction Methods 0.000 abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 16
- 239000001257 hydrogen Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 16
- 150000003839 salts Chemical class 0.000 abstract description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000010828 elution Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000005341 cation exchange Methods 0.000 description 5
- 239000003014 ion exchange membrane Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は電極の製造法に関するものであり、さらに詳し
くは、硫L′、lを含むニッケルメッキ彼覆電暎の製造
法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing an electrode, and more particularly, to a method for manufacturing a nickel-plated electrode containing sulfur L', l. .
これらの電極は、種々の電気化学装置における電極とし
て適用可能なものであるが、特に工業用電解用電極、例
えば水電解用電極や食塩電解用電極としての用途に適し
、高耐久性を示すものであ[従来の技術]
水電解や食塩゛iは解等の工業電解の分野において、’
ia解電圧電圧減は重要な課題である。特に、新規なプ
ロセスとして注1」されている陽イオン交換膜食塩電解
技術に於ては、電解電圧の低減を目的とし、陰極の水素
過電圧を低下するため、6四の低水素過電圧陰極か開発
されている。These electrodes can be used as electrodes in various electrochemical devices, but are particularly suitable for use as industrial electrolysis electrodes, such as water electrolysis electrodes and salt electrolysis electrodes, and exhibit high durability. [Prior art] In the field of industrial electrolysis such as water electrolysis and salt solution, '
IA electrolytic voltage voltage reduction is an important issue. In particular, in the cation exchange membrane salt electrolysis technology, which is noted as a new process, 64 low hydrogen overvoltage cathodes were developed to reduce the electrolytic voltage and the hydrogen overvoltage of the cathode. has been done.
低水素過電圧陰極の製造法の一つとして、?IS極基)
t」上に電気メツキ法により硫黄を含むニッケルを彼覆
した電極の製造法は既に公知であり、持分I+/(25
−2305号、不発明石°らの出願である特開昭57−
19388号、同57−114678号などか提案され
ている。As one of the manufacturing methods of low hydrogen overvoltage cathode? IS polar group)
A method for manufacturing an electrode in which sulfur-containing nickel is coated on top of nickel by electroplating is already known.
-2305, Japanese Patent Application Laid-Open No. 1983-1980, filed by Fukaiishi et al.
No. 19388, No. 57-114678, etc. have been proposed.
これらの硫黄を含むニッケルメッキ;成田を−Uする電
照は、経済的な手法でir?られるものであり、既に実
用化されている例もある。しかしながら、これらの肢覆
電極では、電極基材として用いる金属話祠との関係で新
たな問題を生しることがある。These sulfur-containing nickel platings; Narita-U electricity is an economical way to IR? There are examples that have already been put into practical use. However, these limb-covering electrodes may cause new problems in relation to the metal wire used as the electrode base material.
すなわち、金属はカソード方向に分極されていれば、カ
ソード防食を受けることは良く知られた現象であり、金
属の示す水素過″rに圧は、その過電正分だけ、その金
属をカソード防食しているので、水素過゛電圧を低下さ
せる場合は電極乱祠として用いる金属基材の腐食を考慮
する必要がある。In other words, it is a well-known phenomenon that if a metal is polarized in the cathodic direction, it will undergo cathodic protection, and the hydrogen overpressure exhibited by a metal will cathodically protect the metal by the positive amount of the overcharge. Therefore, when reducing the hydrogen overvoltage, it is necessary to take into account the corrosion of the metal base material used as the electrode abrasion.
例えば、鉄からなる試打上に上記のような低水素通゛ト
ヒ圧を示す波膜を被覆した場合、水素過電圧を低下させ
た割合だけ鉄の溶解、腐食という問題が生じ、電極や電
解槽の寿命の短縮及び製品1″lJf性アルカリの品質
低下、陽イオン交換膜の性能劣化′、9深刻な問題を引
き起こすことになる。For example, if a test shot made of iron is coated with a corrugated film exhibiting low hydrogen permeation pressure as described above, the problem of melting and corrosion of the iron will occur to the extent that the hydrogen overvoltage is reduced, and the electrodes and electrolytic cell will be damaged. This will cause serious problems such as a shortened service life, a deterioration in the quality of the product 1''lJf alkali, and a deterioration in the performance of the cation exchange membrane.
ところで、陽イオン交換膜食塩電解法において、現在実
施されている方法は大別すると二つに分れる。一つは従
来、水銀法等で使用されていた電解槽を廃棄して新しく
新設した新規なイオン交換膜電解法であり、今一つは従
来、水銀法、アスベスト隔膜法等で使用されていた電解
槽をそのまま有効利用している改良イオン交換膜電解法
である。By the way, in the cation exchange membrane salt electrolysis method, the methods currently in use can be roughly divided into two. One is a new ion exchange membrane electrolysis method in which the electrolytic cells previously used in the mercury method, etc. were discarded and a new one was installed, and the other is the electrolytic cell previously used in the mercury method, asbestos diaphragm method, etc. This is an improved ion exchange membrane electrolysis method that effectively utilizes the
改良イオン交換脱法の電解槽は、そのほとんどが鉄から
なる陰極及び陰極缶体が用いられている。The electrolytic cell using the improved ion exchange desorption method uses a cathode and cathode case made mostly of iron.
従って、改良イオン交換膜電解法においても、電解電圧
の低減が重要な課題であるとして、通常の(1(水素過
電圧電極を陰極として装着すると、陰極基祠、陰極室1
5体を構成する鉄が溶解、腐食してしまうという問題が
生じる。Therefore, even in the improved ion-exchange membrane electrolysis method, reducing the electrolysis voltage is an important issue.
The problem arises that the iron that makes up the five bodies melts and corrodes.
[本発明が解決しようとする課題]
本発明の1]的は、低水素過電圧特性を示し、優れた耐
久性を示す電極の製造法、特に鉄からなる電極基)」を
用いる場合においても適用することのできる製造法を提
IJ(することにある。[Problems to be Solved by the Present Invention] Aim of the present invention is to provide a method for manufacturing an electrode that exhibits low hydrogen overvoltage characteristics and excellent durability, especially applicable even when using an electrode group made of iron. The goal is to propose a manufacturing method that can produce IJ.
[課題を解決するための手段]
本発明者は上記課題を解決するために、硫黄を含むニッ
ケルメッキ被覆電極に関し、特にメツキ条件と得られる
電極の電極特性に関し鋭意検討を重ねた結果、p112
以下のニッケル塩及び可溶性含硫黄化合物を含むニッケ
ルメッキ浴を用いて、電極基村上に硫黄を含むニッケル
メッキを施すことにより、低水素過電圧を示し、かつ劣
化の少ない耐久性に優れた′電照が得られることを見出
し本発明を完成するに至った。[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have conducted intensive studies regarding sulfur-containing nickel plating coated electrodes, particularly regarding the plating conditions and the electrode characteristics of the obtained electrodes, and have found that p.
By applying sulfur-containing nickel plating to the electrode base Murakami using a nickel plating bath containing the following nickel salts and soluble sulfur-containing compounds, it is possible to achieve low hydrogen overvoltage and excellent durability with little deterioration. The present invention was completed based on the discovery that the following can be obtained.
以下、本発明の詳細な説明する。本発明において用いら
れる硫黄を含むニッケルメッキ浴としては、塩化ニッケ
ル、硫酸ニッケル、スルファミン酸ニッケルなどの可溶
性のニッケル塩と可溶性の硫し′1?化合物か含まれる
メツキ浴が挙げられ、可溶性1〆ε黄化合物としては、
チオシアン酸塩、チオ尿素又は硫黄の酸化数が5以下の
、亜硫酸、重亜硫酸、チオ硫酸、亜ジチオン酸のオキシ
酸塩などを例示することができる。史に、強固な優れた
耐久性を示す活性ニッケルメッキ波膜を得るために、ニ
ッケルメッキ浴にアンモニウムイオンを加えてもよい。The present invention will be explained in detail below. The sulfur-containing nickel plating bath used in the present invention includes soluble nickel salts such as nickel chloride, nickel sulfate, and nickel sulfamate; Examples of soluble 1〆ε yellow compounds include:
Examples include thiocyanate, thiourea, and sulfurous acid, bisulfite, thiosulfuric acid, and dithionite oxyacid salts in which the oxidation number of sulfur is 5 or less. Historically, ammonium ions may be added to the nickel plating bath to obtain active nickel plated wave membranes that are strong and exhibit excellent durability.
本発明の1“ヒ四の製造法においては、メツキ浴のpl
lを2以下に維持することが必要であり、このことによ
り、11)られる電iは低い水素過電圧を示し、かつ耐
久性の優れたものとなる。In the manufacturing method of 1" of the present invention, the pl of the plating bath is
It is necessary to maintain l to 2 or less, and thereby 11) the generated electricity i exhibits a low hydrogen overvoltage and has excellent durability.
例えば、鉄基材を’;u W )Is祠として用い、本
発明の方法により得られた電極は、鉄基材に比較し、1
00〜150mv低い水素過電圧を示す。For example, an electrode obtained by the method of the present invention using an iron base material as a '; u W )Is shrine has a
00-150mv low hydrogen overvoltage.
ツ考として、本発明者がΔIII定した鉄の溶出速度の
電位依存性を第1図に示す。測定に用いた系は、一般的
な食塩電解の条件として採用される32%N a OI
f水溶液中、9 [1°Cの条件である。第1図に示す
とおり、上記の11111定により鉄の溶出速度は明確
な電位依存性を示すことがわかった。更に、鉄の溶出速
度の電位依存性は−1,Ov付近に明確な変曲点をaし
、−1,OV付近より電位が低下すると、鉄の溶出速J
Uは著しく減少し、はとんど問題とならない量となるこ
とがイ〕かった。従って、−役の食塩電解の条件では、
鉄陰極の電位は−1,15V程度であるために、鉄の溶
出は問題とならないが、更に100〜150mvの範囲
で電位を上Rさせ、過電圧を低下せしめても鉄の溶出は
抑制できることがわかった。As a consideration, FIG. 1 shows the potential dependence of the iron elution rate determined by the present inventor as ΔIII. The system used for the measurement was 32% Na OI, which is used as a general salt electrolysis condition.
f in aqueous solution at 9[1°C]. As shown in FIG. 1, it was found that the iron elution rate showed a clear voltage dependence based on the above 11111 constant. Furthermore, the potential dependence of the iron elution rate has a clear inflection point near -1,Ov, and as the potential decreases from around -1,OV, the iron elution rate J
The amount of U decreased significantly, and it became an amount that hardly caused any problems. Therefore, under the negative salt electrolysis conditions,
Since the potential of the iron cathode is about -1.15 V, iron elution is not a problem, but iron elution can be suppressed even if the potential is further increased in the range of 100 to 150 mV and the overvoltage is lowered. Understood.
すなわち、上記の鉄基)イに比較し100〜L50 m
V低い水素過電圧とは、基材を痛めないで、水素過電圧
が低下できる1直である。That is, compared to the above iron base) A, 100 to L50 m
V low hydrogen overvoltage is one shift in which the hydrogen overvoltage can be lowered without damaging the base material.
一方、pl+が2を越えるメツキ浴を用いて、基材上に
Kt mを含むニッケルメッキ浴を施してi+iられる
′電極の過電圧はより低くなり、例えば電極基材として
鉄を用いた場合は鉄の溶解が無視できなくなる。On the other hand, if a nickel plating bath containing Ktm is applied to the base material using a plating bath with pl+ exceeding 2, the overvoltage of the i+i' electrode will be lower; for example, if iron is used as the electrode base material, The dissolution of can no longer be ignored.
本発明において用いられるメツキ浴のpl+は種々の方
法で1周整しjするが、例えばpl+が大きい場合、塩
酸、疏酸などの酸を適宜メツキ浴に添加することなどに
より調整できる。The pl+ of the plating bath used in the present invention is adjusted once by various methods. For example, if pl+ is large, it can be adjusted by adding an acid such as hydrochloric acid or saccharic acid to the plating bath as appropriate.
その他のメツキ条件は適宜選択することができるか、例
えばメツキ温度は室温から90℃の温度範囲、メツキ時
の電流密度は061^1d112〜【0^/dlI2の
範囲を採用することができる。Other plating conditions may be selected as appropriate; for example, the plating temperature may range from room temperature to 90° C., and the current density during plating may range from 061^1d112 to 0^/dlI2.
本発明に用いる電極基材としては、金属又は導電性を(
−+−す樹脂又はセラミックスなど任意の導電性基祠が
用いられるが、本発明は特に鉄や鉄を主体とした合金を
基材として用いる場合にも−a効である。また、電極基
材の形状は、平板、メツシュ状、多孔状などいかなる形
状のものでもよいが、+2L電流密度での気体発生電極
として用いる場合は、特にエキスバンドメタル、パンチ
ングメタル、金網状の形状のものなどが用いられる。As the electrode base material used in the present invention, metal or conductive material (
-+- Any conductive base material such as resin or ceramics can be used, but the -a effect is particularly applicable to the present invention when iron or an alloy mainly composed of iron is used as the base material. The shape of the electrode base material may be any shape such as a flat plate, mesh shape, porous shape, etc., but when used as a gas generating electrode at +2L current density, expanded metal, punched metal, or wire mesh shape is particularly suitable. These are used.
更に、本発明の電極の製造法においては、上記の電極基
材上にあらかじめ適当な前処理を施したものを用いるこ
とらできる。この適当な前処理とは、例えばステンレス
表面の不動態被膜の除去法として公知の塩酸酸性ニッケ
ルメッキ浴を用いるストライクニッケルメッキ処理や、
基材の1liiJ食性向上のために施す通常のニッケル
メッキ、あるいは、基祠及び硫黄を含むニッケルメッキ
の両名と優れた密着性を示す下地のニッケルメッキなど
が含まれる。Furthermore, in the electrode manufacturing method of the present invention, the above-mentioned electrode base material can be used which has been subjected to an appropriate pretreatment. This appropriate pretreatment includes, for example, strike nickel plating treatment using a hydrochloric acid acidic nickel plating bath, which is a known method for removing passive films on stainless steel surfaces;
This includes ordinary nickel plating applied to improve the eating quality of the base material, or base nickel plating that exhibits excellent adhesion to both the base material and sulfur-containing nickel plating.
[発明の効果]
以上述べたとおり、本発明の方法により得られた電極は
、種々の電気化学装置における電極として適用ri工能
なものであり、特に工業用電解用電極、例えば水電解用
電極や食塩電解用電極としての用途に通するものとなる
。また、陰極、陰極缶体などの陰極+i〜を成部材が鉄
又は鉄を主体としてなる合金を用いる場合に特に有効で
あり、鉄基祠を病めることなく、100〜1.50mv
低い水素過電圧を与え、これに1fい100〜l 50
n v低い電解電圧を与えることかできるものとなる
。更に、この電極は高耐久性を示すものであり、その工
業的価値は極めて大きいものとなる。[Effects of the Invention] As described above, the electrode obtained by the method of the present invention can be applied as an electrode in various electrochemical devices, and is particularly useful as an electrode for industrial electrolysis, such as an electrode for water electrolysis. It can also be used as an electrode for salt electrolysis. In addition, it is particularly effective when using iron or an alloy mainly composed of iron or an iron-based alloy for cathodes, cathode cans, etc.
Give a low hydrogen overvoltage and add 1f to 100 to 50
It becomes possible to give an electrolytic voltage as low as nv. Furthermore, this electrode exhibits high durability, and its industrial value is extremely large.
[実施例]
以下、本発明の実施例を述べるか、本発明はこれらにI
XR定されるものではない。[Examples] Hereinafter, examples of the present invention will be described, or the present invention will be described below.
XR is not determined.
表1
硫黄を含むニッケルメッキ条件
くメツキ浴組成〉
・塩化ニッケル 1.2mol/トチオ尿素
0.4−〇!/1・塩化アンモニウム
1.owol/Iくメッキ条1牛〉
・電流密度 IA/(+112 ・温度 0
0℃−pH1,5−メツキ時間 211r
実施例1、比較例1〜2
実施例1として4X7.5efflの大きさで、゛小極
形状か6メツシユの鉄の金網状の電極基tA上に、表1
で示した条件を用いてニッケルメッキを行い゛、−ヒ極
を作製した。なお、建浴後のpHは約4.2であり、塩
酸を添加することによりpuを1.5まで低下させた。Table 1 Nickel plating conditions including sulfur plating bath composition> Nickel chloride 1.2 mol/tothiourea
0.4-〇! /1.Ammonium chloride
1. owol/I plated strip 1 cow> ・Current density IA/(+112 ・Temperature 0
0°C - pH 1,5 - Plating time 211r Example 1, Comparative Examples 1 to 2 As Example 1, on an iron wire mesh electrode base tA with a size of 4 x 7.5 effl and a small pole shape or 6 meshes, Table 1
Nickel plating was performed using the conditions shown in , and a negative electrode was produced. Note that the pH after bath preparation was approximately 4.2, and the pu was lowered to 1.5 by adding hydrochloric acid.
また、比較例1として、表1のメツキ浴を用い、メツキ
浴のpl+を低下させず、plH゜2とした以外は実施
例1と同一の条件でメツキした電極を得、比較例2とし
て全くニッケルメッキを施していない鉄製の金網状電極
を得た。これらの1は極を鉄性缶体に取り付け、陽イオ
ン交換膜を使用し、陽画として]1上に、I? u 0
2− ’l’ I 02彼膜をUするI)SAタイプの
エキスバンドメタルを用いて、表2の条件で食塩水を電
解した。In addition, as Comparative Example 1, an electrode was obtained which was plated under the same conditions as Example 1 except that the plating bath shown in Table 1 was used and the pl+ of the plating bath was not lowered and the plH° was set to 2. A wire mesh electrode made of iron without nickel plating was obtained. These 1 attach the pole to a ferrous can body, use a cation exchange membrane, and as a positive image] 1 on the I? u 0
2-'l'I02Using the membrane I) Saline solution was electrolyzed under the conditions shown in Table 2 using SA type extract band metal.
表2
表3
食塩電解条件
・陽髄室N+tCIi農度 230g/l・陰極室h
lt011iG度 32vL%Na011・電流l+
i度 2LIA/ds2
・/AA度 90℃ ・陽、陰極間距離 2I(
陽イオン交換膜は、陽極室側に押しつけて固シ↓ゴしt
二)
実施例1.比・咬例1〜2でiすられた電極を陰極とし
て用いた電解槽の電解電圧、陰極の電位(V vs、5
lIIE)、鉄缶体の電(n<V vs、5IIIE)
、苛性ソーダ中の鉄濃度の値を表3に示す。Table 2 Table 3 Salt electrolysis conditions, cathode chamber N + tCIi agricultural rate 230 g/l, cathode chamber h
lt011iG degree 32vL%Na011・Current l+
i degree 2LIA/ds2 ・/AA degree 90℃ ・Distance between positive and cathode 2I (
Press the cation exchange membrane against the anode chamber side and press firmly.
2) Example 1. Electrolysis voltage of the electrolytic cell using the electrode rubbed in Examples 1 and 2 as the cathode, potential of the cathode (V vs, 5
lIIE), electricity of iron can body (n<V vs, 5IIIE)
Table 3 shows the iron concentration values in caustic soda.
表′うより、本発明の方法で得られた電極は、比較例2
で得た鉄陰極に比較して、150mv ’電解電圧を紙
上させ、また苛性ソーダ中の鉄濃度は、比較例2−(−
jJた鉄陰極とほば同一のレベル内に抑制されたことが
イ)かる。一方、比較例1でj:#た1lilfflは
、表3に示すとおり極めて低い過電圧を示し、比較例2
で117た鉄陰極に比較し、250mV低い電、うl電
圧を与えたが、苛性ソーダ中の鉄濃度は、7.5ppm
と高く、鉄の溶解、114食の問題が生じた。From the table, it can be seen that the electrode obtained by the method of the present invention was in Comparative Example 2.
Compared to the iron cathode obtained in Comparative Example 2-(-
A) It can be seen that the irradiance was suppressed to almost the same level as the iron cathode. On the other hand, j:#1lilffl in Comparative Example 1 showed an extremely low overvoltage as shown in Table 3, and Comparative Example 2
It gave a 250 mV lower voltage than the iron cathode with 117, but the iron concentration in the caustic soda was 7.5 ppm.
This caused problems with iron dissolution and 114 meals.
実施例2.比較例3
1、.1tnX 1.3m、高さ約0.8mの内容積を
もつ鉄からなる陰極室缶体を以下のような手法によりニ
ッケルメッキを施した。なお、本電解槽は、従来アスベ
スト隔膜法食塩電解槽をイオン交換脱法に転換した、い
わゆる改良型イオン交換膜食塩電解めであり、陰極形状
は実施例1と同様な金網状電極である。Example 2. Comparative Example 3 1. A cathode chamber body made of iron and having an internal volume of 1 tn×1.3 m and a height of about 0.8 m was nickel plated by the following method. This electrolytic cell is a so-called improved ion-exchange membrane brine electrolysis cell, which is a conventional asbestos diaphragm salt electrolytic cell converted to an ion-exchange desorption method, and the cathode shape is a wire mesh electrode similar to that of Example 1.
まず、鉄製の陰極室内面を塩酸により酸処理を行い、水
洗後、表4に示した条件で下地ニッケルメッキを行い、
その後、表5に示した条件で硫f1?を含むニッケルメ
ッキを行った。First, the inner surface of the iron cathode chamber was acid-treated with hydrochloric acid, and after washing with water, the base nickel plating was performed under the conditions shown in Table 4.
After that, under the conditions shown in Table 5, sulfur f1? Nickel plating including
人4
下地ニッケルメッキ条件
くメツキ浴、t11成〉
・塩化ニッケル 1.2mol/l・塩化アン
モニウム 1.Omol/lくメツキ条件〉
パ屯流密度 2A/d■ ・温度
・pH4,0・メツキ時間
40℃
0.511r
表5
硫黄を含むニッケルメッキ条件
くメソ午浴組成〉
・塩化ニッケル 0.5講OI/トチオ尿素
0.3mol/1・塩化アンモニウム
1.oraol/1くメツキ条件〉
” ia (AE ’t% lx 2A/dm
’ 温度 411 ’C+)H1,0・メツキ時
間 2!!t・このようにして’A遺した陰極及び陰極
室を有する電解槽に、DSA陽睡を取り付け、実施例1
と同一の条件で食塩電解を行った。なお、比・咬のため
全くニッケルメッキをしていない鉄の金網状陰極を用い
て同一の条件で電解を行った(比較例3)。Person 4 Base nickel plating conditions Plating bath, t11> ・Nickel chloride 1.2 mol/l ・Ammonium chloride 1. Omol/l plating conditions> Paton flow density 2A/d■ ・Temperature・pH 4.0・Plating time 40℃ 0.511r Table 5 Mesobath composition under sulfur-containing nickel plating conditions> ・Nickel chloride 0.5 parts OI/Tothiourea
0.3mol/1・Ammonium chloride
1. oraol/1 pixel condition> ” ia (AE 't% lx 2A/dm
' Temperature 411 'C+) H1,0・Plating time 2! ! T. In this way, the DSA solar cell was attached to the electrolytic cell having the cathode and the cathode chamber left in 'A', and Example 1
Salt electrolysis was performed under the same conditions. Note that electrolysis was carried out under the same conditions using an iron wire mesh cathode that was not plated with nickel at all for reasons of comparison (Comparative Example 3).
表6に゛−゛I解漕における電解電圧及び苛性ソーダ中
の鉄濃度の経時変化を示す。Table 6 shows the changes over time in the electrolytic voltage and iron concentration in caustic soda in the ``--'' cell.
表6
極の電解電、圧は1年間はとんど一定であり、耐久性の
優れた電極であった。Table 6 The electrolytic voltage and pressure of the electrode remained almost constant for one year, indicating that the electrode had excellent durability.
第1図は、32% N1tOII水溶液中で90℃の条
件での鉄の溶出速度の電位依7r性を示す図である。FIG. 1 is a diagram showing the potential dependence of the iron elution rate in a 32% N1tOII aqueous solution at 90°C.
Claims (1)
を含むニッケルメッキ浴を用いて、電極基H上に硫黄を
含むニッケルメッキを施すことを特徴とする電極の製造
法。(1) A method for producing an electrode, which comprises applying nickel plating containing sulfur onto the electrode base H using a nickel plating bath containing a nickel salt and a soluble sulfur-containing compound having a pH of 2 or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63314969A JPH02163392A (en) | 1988-12-15 | 1988-12-15 | Production of electrode |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63314969A JPH02163392A (en) | 1988-12-15 | 1988-12-15 | Production of electrode |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02163392A true JPH02163392A (en) | 1990-06-22 |
Family
ID=18059846
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63314969A Pending JPH02163392A (en) | 1988-12-15 | 1988-12-15 | Production of electrode |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02163392A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010047804A (en) * | 2008-08-21 | 2010-03-04 | Murata Mfg Co Ltd | Porous body, and manufacturing method thereof |
CN101781787A (en) * | 2010-03-31 | 2010-07-21 | 金昌市宇恒镍网有限公司 | Production technology for extra-width printing nickel screen and electrical nickel-plating bath |
CN102071441A (en) * | 2010-12-20 | 2011-05-25 | 中南大学 | Method for preparing material containing sulfur and nickel |
-
1988
- 1988-12-15 JP JP63314969A patent/JPH02163392A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010047804A (en) * | 2008-08-21 | 2010-03-04 | Murata Mfg Co Ltd | Porous body, and manufacturing method thereof |
CN101781787A (en) * | 2010-03-31 | 2010-07-21 | 金昌市宇恒镍网有限公司 | Production technology for extra-width printing nickel screen and electrical nickel-plating bath |
CN102071441A (en) * | 2010-12-20 | 2011-05-25 | 中南大学 | Method for preparing material containing sulfur and nickel |
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