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EP0129231A1 - Cathode à surtension basse de l'hydrogène et procédé pour la fabrication de la cathode - Google Patents

Cathode à surtension basse de l'hydrogène et procédé pour la fabrication de la cathode Download PDF

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Publication number
EP0129231A1
EP0129231A1 EP84106905A EP84106905A EP0129231A1 EP 0129231 A1 EP0129231 A1 EP 0129231A1 EP 84106905 A EP84106905 A EP 84106905A EP 84106905 A EP84106905 A EP 84106905A EP 0129231 A1 EP0129231 A1 EP 0129231A1
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EP
European Patent Office
Prior art keywords
hydrogen overvoltage
nickel
low hydrogen
cathode
plating
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.)
Granted
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EP84106905A
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German (de)
English (en)
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EP0129231B1 (fr
Inventor
Yasushi Samejima
Minoru Shiga
Toshiji Kano
Kiyoshi Yamada
Takamichi Kishi
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Kanegafuchi Chemical Industry Co Ltd
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Kanegafuchi Chemical Industry Co Ltd
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Publication date
Priority claimed from JP58111573A external-priority patent/JPS602686A/ja
Priority claimed from JP22231383A external-priority patent/JPS60114586A/ja
Application filed by Kanegafuchi Chemical Industry Co Ltd filed Critical Kanegafuchi Chemical Industry Co Ltd
Publication of EP0129231A1 publication Critical patent/EP0129231A1/fr
Application granted granted Critical
Publication of EP0129231B1 publication Critical patent/EP0129231B1/fr
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds

Definitions

  • Electrodes obtained by spray coating an iron group cathode base with nickel or tungsten carbide powder Patent non-examined Publication No. 32832 /77
  • electrodes spray coated with cobalt and zirconium No. 36582 /77
  • electrodes comprising nickel and cobalt subjected to leaching treatment after spray coating No. 36583 /77
  • electrodes obtained by spray coating an electrode base with Raney-nickel and then leaching with alkali a - sacrificial metal contained in the coating layer No. 122887/80, electrodes obtained by spray coating of an alkali-resistant metal on a cathode base and depositing a platinum group metal on the surface thereof (Nos.
  • electrodes obtained by forming an activated layer by plating method on a cathode base e.g., electrodes obtained by dispersing a platinum group metal powder into nickel (No. 110983/79) or dispersing Raney-nickel into nickel (No. 112785/79) and so on.
  • nickel-plating bodies, copper-plating bodies and the like are normally employed and as the activated layer, it is prevailing to employ those of alkali-resistant metals designed so as to have large surface.
  • a method for electroplating a Raney alloy Patent Examined Publication Nos. 4766 /53, 6611/56, Patent Non-examined Publication No. 25275 /79
  • a method for codeposit -plating Raney-nickel Patent Non-examined Publication Nos. 68795/79, 112785/79
  • a method for depositing a Raney alloy by spray coating, sintering and the like Patent Non-examined Publication Nos.
  • electroconductive fine particles e.g., Raney-nickel etc which contain a platinum group metal and/or an oxide thereof.
  • the present invention encompasses a low hydrogen overvoltage cathode having a nickel or a nickel alloy coating layer containing electroconductive fine particles which contain a platinum group metal and /or an oxide thereof, and method for producing the same which comprises using a codeposit plating tank in which an anode and an object to be plated of a non-perforated flat structure are positioned in parallel with each other, introducing a dispersant slurry though one side of the tank to thus cause it to flow in a space formed between the anode and the object, then removing the slurry through the opposite side, whereby codeposit plating is applied to only one surface of the object.
  • the cathode of the present invention is coated in such a manner that electroconductive fine particles holding a platinum group metal and /or an oxide thereof are dispersed in nickel or a nickel alloy, and is capable of reducing hydrogen generation electric potential by 200 to 300 mV as compared with conventional iron cathodes.
  • iron, stainless steel, nickel and the like may be suitably used and further, iron coated with nickel, a nickel alloy such as Ni-Mo, Ni-W and the like may also be used.
  • nickel or nickel alloys such as Ni-No, Ni-W and the like may be suitably used and further, a mixture of nickel ' and oxides thereof may also suitably be used.
  • a platinum group metal selected from the group consisting of platinum, ruthenium, iridium, rhodium, palladium and osmium, and an oxide thereof may be used singly or in combination of two or more.
  • Electroconductive fine particles should have electroconductivity and large surface area and be superior in resistance to caustic alkali, which may be exemplified by porous nickel particles synthesized by nickel formate or nickel carbonyl, carbon particles such as activated carbon, Raney-nickel, Raney-cobalt, Raney-silver and the like.
  • Raney-nickel alloy it is necessary to leach by a known manner after formation of the coating layer. For example, adequate activity is obtained by immersing the coating layer in a 10 to 30 % aqueous caustic soda solution at 40 to 60 °C for more than one hour.
  • the electroconductive fine particles As a process for allowing the electroconductive fine particles to hold the active substance, known techniques may be employed including such as chemical plating, displacement plating, electroplating, vapor deposition, a process for making alloys by hot melting and the like.
  • the foregoing fine particles should desirably be as fine as possible, as are uniformly dispersed in nickel or a nickel alloy and supplied for coating.
  • the particle size of the fine particles should preferably be approximately 100 mesh-pass or less, more preferably 200 mesh-pass or less, through not limited in particular.
  • An amount of 0.01 % or more of a platinum group metal and /or an oxide thereof to be held by the fine particles provides cathodes having an adequate activity. An amount exceeding 50% leads to economical disadvantage.
  • the thickness of the coating layer is not specifically limited but should preferably be 800 ⁇ m or less, more preferably 400 ⁇ m or less, taking into consideration economy. With a view to keeping activity for a prolonged period of time, thickness should be at least 10 ⁇ m or more, more preferably 50 ⁇ m or more.
  • cathodes having less durability are caused by many vacant spaces present in the active portion or insufficiency of adhesion force among particles, i.e., shortage of mechanical strength
  • cathodes having high hydrogen overvoltage are caused by lack of active area actually working or activity per unit area.
  • cathodes produced by electroplating containing a sacrificial component dissolving during the electrolysis when containing the sacrificial component in great amounts to lower hydrogen overvoltage, deteriorate in mechanical strength, thereby being inferior. in durability.
  • a process for codeposit plating of Raney-nickel is characterized in that the mechanical strength of the active portion is great but it has been found through studies by the present inventors that it is still insufficient in long-term durability. That is, for the purpose of minimizing hydrogen overvoltage, the content of Raney alloy in a codeposit plating coating layer has to be increased, but the increased content of Raney-nickel results in a decrease in the mechanical strength of the active portion.
  • Raney alloy codeposit A modified process of the foregoing Raney alloy codeposit . plating method producing low hydrogen overvoltage cathodes is revealed by Patent Non-examined Publication No. 133387 /83.
  • Raney alloy and a platinum group metal are admixed in powder, with which codeposit plating is made.
  • it is not yet satisfactory though- providing cathodes which are not only stronger in the mechanical strength, but smaller in hydrogen overvoltage, as compared with the codeposit plating using Raney alloy alone. That may be because uniform codeposit plating is difficult due to the differences in particle size, specific gravity and the like between the Raney alloy and the platinum group metals.
  • the platinum group metals, different from Raney alloy shows no activity when buried in a nickel matrix.
  • the method for producing low hydrogen overvoltage cathodes by codeposit plating of the three-component alloy is characterized by using a codeposit plating tank in which an anode and an object to be plated of a non-perforated flat structure are positioned in parallel with each other, supplying a dispersant slurry through one side of the tank to thus cause it to flow in a space formed between the anode and the object, then removing the slurry through the opposite side, more preferably, recirculating the removed slurry back to a codeposit plating bath storage tank, whereby codeposit plating is applied to only one surface of the object.
  • An apparatus for codeposit plating of Raney alloy is desclosed by, for example, Patent Non-examined Publication No. 104491 /80. According to the apparatus, however, it is impossible to perform codeposit plating uniformly and firmly, in cases where a cathode is a structure of a non-perforated flat plate and only one surface is subjected to codeposit plating. That is, in conventional Raney alloy codeposit plating, a dispersant slurry is flowed in a vertical way by the use of gas, a vibrating plate, a pump and the like.
  • the present invention has been completed on the thought that if a dispersant slurry is flowed horizontally rather than vertically, contacting and colliding chances between dispersant slurry particles and an object to be plated should be enhanced to thereby improve the deposition of the particles onto the object.
  • the cathode base usable for activated cathodes of the present invention way be in any form but a non-perforated flat plate may preferably be employed.
  • a non-perforated flat plate may preferably be employed.
  • operation is often carried out for saving energy cost by reducing an anode-cathode distance to 3 mm or less, often 2 mm or less.
  • non-perforated flat plate cathodes are capable of making uniform micro- distribution of current density over the cation exchange membrane and hence very desirable.
  • formation of a coating layer may be suitably achieved by conventional techniques including such as plasma spray coating, chemical plating, electroplating and the like, if it can be attained to deposit with good adhesion force on the cathode base electroconductive fine particles holding platinum group metals and /or oxides thereof together with nickel or nickel alloys.
  • the cathodes of the present invention obtained in such a manner as aforesaid are adapted for use as electrodes which generate hydrogen gas in, for example, the electrolysis of water, alkali metal halides and the like.
  • Fig. 3 depicts a schematic representation showing an example in which codeposit plating is effected according to the present invention.
  • a dispersant is well stirred to give a uniform slurry concentration.
  • a dispersantslurry (2 ) is supplied by a pump (3 ) to a codeposit plating tank (4 ) through one side, then removed through the other side. The removed dispersant slurry is returned back to the codeposit plating bath storage tank (1 ) and recirculated between the plating bath storage tank (1 ) and the plating tank (4 ) .
  • the codeposit plating tank (4 ) is equipped with a cathode (6 ) to be plated and an anode (5 ) , both being positioned in parallel with each other, to thus form a closed codeposit plating chamber (7 ) .
  • the cathode (6 ) is, needlessly, located so that the surface to be plated faces to the inside of the chamber.
  • any known anode for use in electroplating may be used and the shape is . not specifically limited, including a flat plate, a perforated plate, a net, an aggregate of nickel tips and the like.
  • An amount of the dispersant contained in a codeposit plating coating in the present invention is variable according to the direction in which the object to be plated was placed, the concentration of the dispersant slurry, the average flow rate of the dispersant slurry within the codeposit plating chamber and the like.
  • FIG. 4 and FIG. 5 are schematic representations showing the direction in which the object to be plated are placed.
  • the object is located horizontal and faces upward, as in the case of FIG. 3.
  • the object is located vertical.
  • a preferred embodiment is to locate the object substantially horizontal to face upward, as shown by FIG. 3 and FIG. 4. It is also considered to locate the object to face downward, but in this case the same plated object as in the case of FIG. 3 and FIG. 4 can not be obtained because of a decrease in a . deposition-improving effect caused by gravity, unless the slurry concentration is higher than in the case of FIG. 3 and FIG. 4.
  • FIG. 5 An embodiment of locating the objects as shown by FIG. 5 is useful when two sheets of cathodes are produced at one time. That is, by locationnmg two objects so that the backsides of the objects are in contact with each other, two sheets of hydrogen overvoltage cathodes can be produced through one operation of codeposit plating.
  • codeposit plating should desirably be made with a higher slurry concentration.
  • the dispersant slurry should be flowed substantially horizontal in the codeposit plating tank.
  • substantially horizontal means an extent within which an increase in deposition of the dispersant particles resulting from gravity is achievable, i.e., the angle between the horizontal surface and the slurry flowing line being within 45 degrees, more preferably 30 degrees, regardless of upward or downward direction, most preferably 0 degree.
  • the dispersant slurry is normally supplied through one side of the tank and removed through the opposite other side, but it is possible for the purpose of uniformization, to flow it to a reverse direction during the operation by changing an inlet and an outlet. It is further desired to position dispersing plates at an inlet and an outlet to improve uniformization.
  • the slurry concentration should preferably be not less than 0.01 g/1 and less than 3 g /1, more preferably not less than 0.05 g /1 and less than 3 g /1. In the case of less than 0.01 g /1, only the plated object containing a dispersant in less amounts is obtained and thus showing high hydrogen overvoltage. In the case of not less than 3 g /1, the plated object contains a dispersant in greater amounts, which shows low initial hydrogen overvoltage but is poor in the mechanical strength, thus lacking in long-term durability.
  • the average flow rate of the dispersant slurry within the codeposit plating chamber should preferably be 0.05 m /sec or more, more preferably less than 10 m /sec.
  • a well-known nickel plating bath may be suitably employed, including such as watts bath, all nickel chloride bath, high nickel chloride bath and the like.
  • the particle size of the dispersant is not specifically limited, but should preferably be approximately 100-mesh pass or less, more preferably 200-mesh pass or less.
  • the dispersant may be comprised of an optional combination of a first metal selected from the group consisting of nickel, cobalt and silver, a second metal selected from the group consisting of aluminium, magnesium, zinc and tin, and a third metal selected from the group cossisting of platinum, palladium, rhodium, ruthenium, iridium and osmium.
  • the second metal is leached by being immersed in an aqueous caustic alkali solution after codeposit plating, whereby a coating layer is made porous and thus activated.
  • the content of the third metal is considered from both aspects of cost and activity, but should desirably be not higher than 50 weight %. In the case of less than 0.01 weight %, an effect of increasing activity is hardly expected.
  • Cathodes subjected to codeposit plating are stored for a prolonged period of time by being washed and dried.
  • the second metals must be leached in an aqueous caustic alkali solution. This treatment may be made either . befor or after installing of the cathodes to an electrolytic cell, but the latter is preferred.
  • cathodes used in the production of an aqueous alkali metal hydroxide solution by an ion exchange membrane process or an asbestos diaphragm process expanded metals, perforated plates or net structure cathodes have been commonly employed. Notwithstanding, according to the study made by the present inventors, it has been made clear that cathodes of non-perforated flat plates, only one surface of which is codeposit plated provide the best results, when served as cathodes used in a horizontal type ion exchange membrane electrolytic cell.
  • the present invention is capable of production of epock-making cells equipped with low hydrogen overvoltage cathodes, upsetting knowledge of persons skilled in the art that cells with non-perforated flat plate cathodes show high cell voltage (e.g., Patent Non-examined Publication No. 174477 /82, "SODA AND CHLORINE", 32, 281, 1981 ) , and therefore exceedingly valuable in the industry.
  • Nickel particles having an average particle size of 8 ⁇ m were electroplated with ruthenium to be 4 weight %.
  • the obtained nickel particles containing ruthenium and nickel particles having an average particle size of 54 ⁇ m were admixed at the proportion of 3 : 7, with which sand blasted nickel plates of 4 cm X 4 cm were subjected to plasma spray coating to be 200 ⁇ m in thickness.
  • test piece was served as a cathode
  • a DES manufactured by Permelec Electrode Company
  • - NAFION 901 manufactured by E. I. Du Pont de Nemors & Co.
  • an aqueous sodium chloride solution was electrolysed while controlling the catholyte concentration to 32 %, current density to 25 A /d m 2 and catholyte temperature to 90 °C. Hydrogen overvoltage was measured by a current interruptor method.
  • Hydrogen overvoltage of the cathode was 0.07 to 0.09 V and no degradation in performance could be observed even after continuous 1000-day operation or more.
  • FIG. 1 a change in hydrogen overvoltage was depicted.
  • Example 2 The same sand blasted nickel plates as in Example 1 were subjected to plasma spray coating with nickel particles of an 8 ⁇ m average particle size to be 200 ⁇ m in thickness.
  • test pieces were supplied for the electrolysis under the same conditions as in Example 1.
  • the test pieces showed initially hydrogen overvoltage of 0.08 to 0.09 V but each of them showed an abrupt increase after 50 to 150 days.
  • the section was observed by an electron microscope and cracks could be seen in the inside of every test piece.
  • Nickel particles of a 54 ⁇ m average particle size were applied by plasma spray coating to the same test pieces as used in Comparative Example 1 and supplied for the electrolysis under the same conditions as in Example 1.
  • Hydrogen overvoltage was 0.15 V initially but increased to 0.23 V after 50-day operation.
  • a three-component-alloy Raney-nickel comprising 48.9 weight % of nickel, 50 weight % of aluminium and 1.1 weight % of platinum were pulverized and classified.
  • the 200-mesh passed three-component Raney-nickel particles were dispersed + in a plating bath containing 300 g /1.of NiCl 2 6H 2 O and 40 g /1 of H 3 BO 3and aged with stirring for a hour.
  • Nickel plate test pieces of 4 cm X 4 cm were immersed in the foregoing plating bath and plated with stirring at 50 °C for 90 minutes. As an anode, nickel was served and 0.48 A direct current was supplied. The content of Raney-nickel was 25.6 % and the thickness of a coating was 250 ⁇ m.
  • test pieces were leached at 80 °C for 2 hours by being immersed in a 20 % aqueous caustic soda solution.
  • the activated test pieces were served as cathodes and the electrolysis was effected under the following conditions. Hydrogen overvoltage was measured by a current interruptor method.
  • the cathodes produced according to the foregoing manner showed hydrogen overvoltage ranging from 0.06 to 0.08 V and even after 800-day operation, a change in performance could not be recognized. A change in hydrogen overvoltage was shown in FIG. 2.
  • test pieces were prepared in a similar fashion to that of Example 2 excepting that a three-component-alloy Raney-nickel comprising 45 . 7 weight % of nickel, 50 weight % of aluminium and 4.3 weight % of ruthenium was employed, and the electrolysis was carried out under the same conditions.
  • Hydrogen overvoltage was between 0.07 V and 0.08 V and even after 750-day operation no degradation in performance was observed. During the period, operation was shut down five times for one week, respectively, degradation in performance could not be recognized before or after every shut-down.
  • the sand blasted test pieces of 4 cm x 4 cm were coated by plasma spray with the 200-mesh passed three-component-alloy particles obtained in Examples 2 and 3 to be 200 ⁇ m in thickness.
  • the electrolysis was effected similarly to Example 2.
  • the cathode using Al-Ni-Pt alloy showed 0.06 V hydrogen overvoltage, while the cathod using Al-Ni-Ru alloy showed 0.07 V. No degradation in performance was observed even after 650-day operation in respective case. During the period, operation was shut down 15 times for one week, respectively, a change in performance before or after every shut-down did not occur.
  • Codeposit plating was effected in a similar manner to that of Example 2, excepting that 200-mesh passed Raney-nickel comprising 50 weight % of nickel and 50 weight % of aluminium, and the electrolysis was conducted similarly to Example 2.
  • Hydrogen overvoltage was 0.10 V and increased to 0.18 V after 100-day operation. During the period, operation was shut down five times for one week, respectively, degradation of 0.01 V on an average was observed every shut-down.
  • Non-perforated flat plates of carbon steel 660 mm x 2,000 mm, were degreased, washed with an acid, and chemical plated with nickel to be 30 ⁇ m in thickness.
  • the codeposit plating bath was removed with stirring by a pump and supplied into the codeposit plating chambers through one side to flow in a horizontal way. Codeposit plating was carried out under the conditions ; temperature 50 °C, current density 3 A /d m 2 , time 90 minutes and average flow rate of the slurry within the chamber 1.0 m /sec. A plating coating thus obtained was hard and uniform in thickness.
  • the obtained plate was separated into six parts in a longitudinal way, by which the codeposit plating tank is formed substantially horizontal to allow the surface to be plated to face upward, as illustrated by FIG. 3 and FIG. 4.
  • Each part was codeposit plated in the same manner and the same conditions as in Example 5.
  • a plating coating was hard and was approximately uniform in thickness in every part.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
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EP84106905A 1983-06-20 1984-06-16 Cathode à surtension basse de l'hydrogène et procédé pour la fabrication de la cathode Expired EP0129231B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP111573/83 1983-06-20
JP58111573A JPS602686A (ja) 1983-06-20 1983-06-20 活性電極
JP22231383A JPS60114586A (ja) 1983-11-25 1983-11-25 陰極の製造法
JP222313/83 1983-11-25

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EP0129231A1 true EP0129231A1 (fr) 1984-12-27
EP0129231B1 EP0129231B1 (fr) 1988-01-27

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CA (1) CA1260427A (fr)
DE (1) DE3469042D1 (fr)
IN (1) IN161189B (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986003790A1 (fr) * 1984-12-14 1986-07-03 Oronzio De Nora Impianti Elettrochimici S.P.A. Procede de preparation d'une electrode et son utilisation dans des processus electrochimiques
DE3612790A1 (de) * 1986-04-16 1987-10-22 Sigri Gmbh Kathode fuer waesserige elektrolysen
US5035789A (en) * 1990-05-29 1991-07-30 The Dow Chemical Company Electrocatalytic cathodes and methods of preparation
US5066380A (en) * 1990-05-29 1991-11-19 The Dow Chemical Company Electrocatalytic cathodes and method of preparation
US5164062A (en) * 1990-05-29 1992-11-17 The Dow Chemical Company Electrocatalytic cathodes and method of preparation
US5227030A (en) * 1990-05-29 1993-07-13 The Dow Chemical Company Electrocatalytic cathodes and methods of preparation
WO2021148265A1 (fr) * 2020-01-24 2021-07-29 Ineos Technologies Limited Ensemble électrode et électrolyseur
CN114774967A (zh) * 2022-05-25 2022-07-22 江苏双良新能源装备有限公司 一种电解水催化网及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB991231A (en) * 1962-12-12 1965-05-05 Bbc Brown Boveri & Cie Catalyst electrode insensitive to oxidation for electrochemical processes
DE3116032A1 (de) * 1980-04-22 1982-02-18 Johnson, Matthey & Co., Ltd., London Kathode fuer elektrochemische reaktionen und verfahren zu ihrer herstellung
US4331517A (en) * 1981-04-02 1982-05-25 Ppg Industries, Inc. Method of preparing a cathode by high and low temperature electroplating of catalytic and sacrificial metals, and electrode prepared thereby

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB991231A (en) * 1962-12-12 1965-05-05 Bbc Brown Boveri & Cie Catalyst electrode insensitive to oxidation for electrochemical processes
DE3116032A1 (de) * 1980-04-22 1982-02-18 Johnson, Matthey & Co., Ltd., London Kathode fuer elektrochemische reaktionen und verfahren zu ihrer herstellung
US4331517A (en) * 1981-04-02 1982-05-25 Ppg Industries, Inc. Method of preparing a cathode by high and low temperature electroplating of catalytic and sacrificial metals, and electrode prepared thereby

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986003790A1 (fr) * 1984-12-14 1986-07-03 Oronzio De Nora Impianti Elettrochimici S.P.A. Procede de preparation d'une electrode et son utilisation dans des processus electrochimiques
DE3612790A1 (de) * 1986-04-16 1987-10-22 Sigri Gmbh Kathode fuer waesserige elektrolysen
US5035789A (en) * 1990-05-29 1991-07-30 The Dow Chemical Company Electrocatalytic cathodes and methods of preparation
US5066380A (en) * 1990-05-29 1991-11-19 The Dow Chemical Company Electrocatalytic cathodes and method of preparation
US5164062A (en) * 1990-05-29 1992-11-17 The Dow Chemical Company Electrocatalytic cathodes and method of preparation
US5227030A (en) * 1990-05-29 1993-07-13 The Dow Chemical Company Electrocatalytic cathodes and methods of preparation
WO2021148265A1 (fr) * 2020-01-24 2021-07-29 Ineos Technologies Limited Ensemble électrode et électrolyseur
CN114774967A (zh) * 2022-05-25 2022-07-22 江苏双良新能源装备有限公司 一种电解水催化网及其制备方法

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IN161189B (fr) 1987-10-17
DE3469042D1 (en) 1988-03-03
CA1260427A (fr) 1989-09-26
EP0129231B1 (fr) 1988-01-27

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