EP0153356A1 - Fabrication d'anodes degageant de l'hydrogene avec une base metallique filmogene et un revetement d'oxyde catalytique comportant du ruthenium - Google Patents

Fabrication d'anodes degageant de l'hydrogene avec une base metallique filmogene et un revetement d'oxyde catalytique comportant du ruthenium

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Publication number
EP0153356A1
EP0153356A1 EP84903061A EP84903061A EP0153356A1 EP 0153356 A1 EP0153356 A1 EP 0153356A1 EP 84903061 A EP84903061 A EP 84903061A EP 84903061 A EP84903061 A EP 84903061A EP 0153356 A1 EP0153356 A1 EP 0153356A1
Authority
EP
European Patent Office
Prior art keywords
anode
coating
ruthenium
oxide
layers
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.)
Withdrawn
Application number
EP84903061A
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German (de)
English (en)
Inventor
Jean Hinden
Jean Pierre Waefler
Michael Katz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eltech Systems Corp
Original Assignee
Eltech Systems Corp
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Filing date
Publication date
Application filed by Eltech Systems Corp filed Critical Eltech Systems Corp
Publication of EP0153356A1 publication Critical patent/EP0153356A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • 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
    • C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide

Definitions

  • the present invention generally relates to catalytic oxygen evolving anodes, and more particularly to a method of manufacturing a dimensionally stable, oxygen evolving anode which comprises an anode base of film-forming metal with a catalytic oxide coating containing ruthenium, and which may be applied for example in processes for electrowinning metals from acid electrolytes.
  • Oxygen evolving anodes are subject to particularly severe oxidative attack and corrosion due to anodically evolved oxygen and corrosive electrolytes.
  • An industrially acceptable oxygen evolving anode must thus be adequately protected from oxidation by anodically evolved oxygen, in order to be able to ensure stable operation and a sufficiently long industrial service life to allow the anode cost to be economically justified for industrial applications of oxygen evolving anodes.
  • OMPI - , WIPO _ Metal electrowinning cells are generally operated with a low current density in order to ensure uniform electrodeposition of metal on the cathode, and thus require a very large anode surface area.
  • the value of the metal product obtained on the cathode is moreover relatively low with respect to the area of the electrodes, so that the anode cost is particularly critical and must be restricted accordingly, so as to be economically justified for electrowinning.
  • Lead or lead alloy anodes have been widely used in processes for electrowinning metals from sulphate solutions, but they nevertheless have important limitations, such as a high oxygen overvoltage and loss of the anode material leading to contamination of the metal product obtained on the cathode.
  • Anodes of lead-silver alloy provide a certain decrease of the oxygen overvoltage and improvement of the current efficiency, but they still have the said limitations as a whole.
  • Known titanium anodes with an outer coating of manganese dioxide or lead dioxide have a high oxygen overpotential and do not provide an adequate energy economy and long-term service life to justify their use in most industrial applications of oxygen evolving anodes, and more particularly where conventional lead anodes are currently used. It has been proposed to provide coated titanium anodes with a protective intermediate comprising platinum group metal, but this is nevertheless insufficient to provide an adequate service life for most industrial applications of oxygen evolving anodes.
  • Titanium is a film-forming metal which exhibits outstanding corrosion resistance under anodic operating conditions, due to its ability to anodically form a stable surface oxide film which effectively protects the underlying titanium metal from corrosion, but is electrically insulating.
  • Dimensionally stable anodes thus generally comprise a titanium base provided with a catalytic coating which allows anode operation at a reduced potential and at the same time protects the underlying titanium from oxidation.
  • any part of the titanium base which is exposed to the electrolyte is rapidly passivated and thus effectively protected by localized formation of a stable, insulating anodic surface oxide film on the part thus exposed.
  • the catalytic coating In order to provide an operative anode structure, the catalytic coating must be permanently applied and electrically connected to the titanium base, and must itself exhibit adequate conductivity, catalytic activity, and stabilty to be able to ensure satisfactory, stable, long-term industrial operation of the anode.
  • suitable anode coating materials must be selected and applied in a suitable manner to the anode base.
  • ruthenium provides excellent catalytic activity for oxygen evolution, but lacks adequate stability and tends to form volatile RuO under oxygen evolving conditions. Consequently, ruthenium must be applied and stabilized in a suitable manner in order to allow it to effectively catalyze oxygen evolution at a reduced potential for prolonged periods. This constitutes a particularly critical technical problem underlying the present invention.
  • Ruthenium was for the first time successfully applied by H.Beer to produce dimensionally stable chlorine anodes with a mixed oxide coating of the type described more particularly in Example 1 of in U.S. Pat. 3,632,498, which combines the high stability of rutile TiO- with the excellent electrocatalytic properties of RuO- for chlorine evolution. Said mixed oxide at the same time provides an increased oxygen potential, and thereby increases the selectivity of the coating for producing chlorine as opposed to oxygen.
  • Example 8 of this patent relates to a titanium anode with a coating comprising iridiu oxide and manganese oxide.
  • This anode is said to be suited for the preparation of per-compounds, thus presumably has a relatively high oxygen potential for this purpose, and would for that reason seem unsuitable for most industrial applications of oxygen evolving anodes.
  • U.S. Patent No. 4,289,591 relates to a method of generating oxygen which comprises providing a catalytic cathode and a catalytic oxygen evolving anode respectively bonded to opposite surfaces of a solid polymer electrolyte ion transporting membrane, a catalyst comprising ruthenium oxide and manganese oxide being provided at the anode.
  • This catalyst is produced by a modified Adams method which comprises mixing ruthenium and manganese salts, incorporating an excess of sodium nitrate, fusing the mixture at 500°C for three hours, washing and drying the residue to provide ruthenium oxide-manganese oxide powder, which is then bonded to said solid polymer electrolyte ion transport membrane.
  • the described modified Adams method serves to produce a finely divided catalyst powder which is formed of a solid solution of ruthenium oxide with a minor amount of manganese oxide, and is bonded to said solid polymer electrolyte membrane.
  • Such a composite membrane/electrode structure is nevertheless unsuitable for electrolytic processes such as electrowinning zinc or copper for example, which involve no separation by a membrane between the anodes and the cathodes. It is well known to those skilled in the art that the manufacture of a complete, operative anode structure having a catalytic oxide coating consolidated with a film-forming metal base is quite problematic and that very slight modifications in the manufacturing conditions can drastically affect anode performance in industrial practice.
  • catalytic anodes comprising ruthenium undergo a notable rise in the oxygen potential during operation as oxygen evolving anodes. This constitutes a major obstacle to the effective use of the excellent electrocatalytic properties of ruthenium in oxygen evolving anodes, which is a major problem underlying the present invention.
  • a main object of the invention is to allow dimensionally stable, oxygen evolving anodes which comprises an anode base of film-forming metal with a catalytic oxide coating containing ruthenium to be produced in a simple and economical manner.
  • Another object of the invention is to provide a method of manufacturing such dimensionally stable anodes which allows ruthenium to be applied as efficiently as possible to maintain a reduced potential, significant energy savings, and an extended service life as an oxygen evolving anode.
  • a further object of the invention is to manufacture such dimensionally stable anodes which may be applied more particularly as oxygen evolving anodes in processes for electrowinning metals from acid electrolytes. The invention provides the manufacturing method set forth in the claims with a view to meeting the above objects as far as possible.
  • an oxygen evolving anode according to the invention must comprise a minimum proportion of manganese in order to be able to ensure an adequate anode life under oxygen evolving conditions.
  • the coating composition must be selected within the range corresponding to RuO- and MnO,, in a mole ratio from 1:1 to 1:9, and preferably between 1:2 and 1:4, in order to be able to maintain a low, practically constant oxygen potential and to ensure a high anode life under oxygen evolving conditions.
  • the proportion of manganese in the oxide coating may moreover be considerably increased within said range, without notably increasing the oxygen potential, while the anode life under oxygen evolving conditions may be significantly increased when the proportion of manganese in the oxide coating is increased towards its upper limit within said range.
  • the number of oxide layers applied according to the invention is important with regard to the anode life. It must be more particularly selected from the range between 6 and 35 layers, preferably between about 10 and about 20 layers, namely according to the selected coating composition and the total ruthenium loading applied in each case. This loading lies within the range from 4 to 20, preferably about 6 to about 12 grams of ruthenium per square meter of the anode base surface. Said loading should be selected from case to case according to the compostion of the coating produced according to the invention.
  • stable oxide coatings with a high proportion of manganese may be advantageously produced in the composition range according to the invention by applying a relatively low ruthenium loading of 4 to 8 g/m in 10 to 20 layers.
  • oxide coatings with a minimum proportion of manganese corresponding to the 1:1 mole ratio of the composition range according to the invention, should be produced with a higher ruthenium loading
  • the ruthenium and manganese compounds contained in the coating solution which is applied according to the invention should be completely dissolved in the in order to ensure a uniform, ultrafine mixture of ruthenium and manganese throughout the oxide coating obtained by thermal conversion.
  • the invention was successfully carried out with ruthenium chloride and manganese nitrate or manganese oxalate.
  • Coating solutions were successfully applied according to the invention which comprisied an aqueous solvent or an organic solvent, more particularly ethanol, or butanol.
  • Concentrated hydrochloric acid was also included in an amount corresponding to about 4% - 15% by weight of the coating solution, which likewise provided a good coating.
  • the thermal decomposition temperatures of the ruthenium and manganese compounds used to produce an oxide coating according to the invention differ considerably, so that they must be subjected to heat treatment at a temperature which is specially selected so as to be suitable to ensure their simultaneous conversion into a satisfactory, uniform oxide coating. It has been experimentally established that heat treatment at a temperature of about 400 ⁇ C is essential in order to to ensure a satisfactory coating according to the invention, whereas it was found that significantly higher or lower temperatures, above 420 ⁇ C, or below 380 ⁇ C, does not provide a satisfactory coating.
  • the following examples illustrate different modes of carrying out the invention.
  • Titanium anodes comprising a catalytic Ru-Mn oxide coating with a composition corresponding to a 50 RuO ⁇ /50 MnO- mole ratio were manufactured in the following manner.
  • a homogeneous coating solution of ruthenium chloride and manganese nitrate dissolved in water in a mole ratio 1:1 was prepared with the following composition by weight: 10.5 % RuCl aq.(40% Ru); 10.5 % Mn(NO ) .4 H-0; 4.7 % HC1 (10 N); 74.3 % H 2 0.
  • Titanium coupons (100x20xlmm) were pretreated by sandblasting and etching in boiling 15% HC1 for 30 minutes.
  • the coating solution was successively applied with a brush in 10 layers to the pretreated titanium coupons. Each applied layer of solution was dried for 5 minutes in air at 100 ⁇ C and the resulting dried layer was heat treated at 400 ⁇ C for 10 minutes in a stream of air, whereby the metal salts are thermally decomposed and converted to oxide.
  • Another anode (S28) was similarly produced , except that manganese oxalate was used in this case to replace manganese nitrate previously used. This anode (S28) exhibited an
  • Titanium anodes with a catalytic Ru-Mn-Co oxide coating were prepared under the conditions described in Example 1, except that a solution of ruthenium chloride, manganese nitrate and cobalt nitrate dissolved in water was prepared with the following composition by weight:
  • Ru 8 g/m and an overall composition corresponding to RuO-, MnO-, and Co-oxide in a mole ratio of 50:45:5.
  • One such anode was operated at 500 A/m 2 in 150 gpl
  • Titanium anodes with a catalytic Ru-Mn oxide coating containing dispersed anatase Ti0 2 powder of submicronic particle size were produced as described in Example 1, in the following manner.
  • the coating solution used in this case comprised ruthenium chloride and manganese nitrate dissolved in a 50 Ru/50 Mn mole ratio in n-butyl alcohol, further contained anatase ⁇ i ⁇ P owder uniformly dispersed throughout the solution, and had the following composition by weight: 12.6% RuCl 3 aq.(40% Ru); 12.2% Mn(N0 3 ) 2 »4 H 2 0; 3.9% dispersed anatase Ti0 2 powder; 71.3% BuOH.
  • 150 gpl H 2 S0- had an initial oxygen potential of 1.53 V vs. NHE, and operated at 1.63 V vs. NHE after 23 months.
  • Titanium anodes with a catalytic Ru-Mn oxide coating containing dispersed titanium metal powder with a particle size of 20 to 40 microns were produced as follows.
  • the coating solution used in this case comprised ruthenium chloride and manganese nitrate dissolved in a 1:1 mole ratio in water, further contained titanium metal powder uniformly dispersed throughout the solution, and had the following overall composition by weight: 10.3% RuCl 3 aq.(40% Ru); 10.1% Mn(N0 3 ) 2 .4H 2 0; 2% dispersed Ti powder ; 4.6% HC1 (ION); 73% H 2 0.
  • This solution was applied in 7 layers and converted to oxide as described in Example 1, so as to produce an oxide coating containing uniformly dispersed titanium powder, which was
  • Ru0 2 :Mn0 2 (but containing no dispersed Ti).
  • Titanium anodes comprising a catalytic Ru-Mn oxide coating with an overall composition corresponding to RuO_ and
  • a coating solution of ruthenium chloride and manganese nitrate dissolved in a mole ratio of 30:70 in 1-butyl alcohol was prepared with the following composition by weight:
  • Titanium coupons (100x20xlmm) were pretreated by sandblasting, treating in 1,1,1-trichlorethane for 10 minutes, and etching in oxalic acid at 80 ⁇ C for 6 hours.
  • the coating solution was successively applied with a brush in
  • each applied layer of solution was dried for 10 minutes in air at 120*C, and each dried layer was heat treated at 400"C for 10 minutes in a stream of air, whereby the metal salts are thermally decomposed and converted to oxide.
  • Another anode (Bl) was similarly produced, but by applying 13 layers of the same coating solution, so as to produce a
  • Another anode (B4) was similarly produced, but by applying 30 layers of the same solution, so as to obtain a coating with a
  • the coating solution used in this case comprised dissolved ruthenium chloride and dispersed Mn0 2 powder, and had the following composition by weight: 12.7 % RuCl 3 aq.(40 % Ru); 10.0 % dispersed beta-Mn0 2 powder (mean size 40 microns); 5.3 % HC1 (10 N); 72 % n-butyl alcohol.
  • the comparative anode (Q42), thus obtained with a coating applied in 5 layers with a composition corresponding to 30 Ru0 2 and 70 Mn0 2 (powder) and a loading of Ru 8 g/m , exhibited an accelerated test life of 60 hours at 7500A/m .
  • this comparative anode (Q42) having a coating with the same overall composition as B2, but containing MnO- powder which is preformed and dispersed, exihibits an accelerated test life of 60 hours at 7500A/m ,
  • RuO- and Mn0_ in a mole ratio of 30:70 is moreover about twice as high as the 85-90 hours obtained with the anodes (S46) and (S48) of Example 1 which had a Ru-Mn oxide coating
  • This comparison shows the particular significance of manufacturing a Ru-Mn oxide coating according to the method of the present invention, namely by applying a major amount of manganese oxide which is simultaneously formed in situ with a minor amount of ruthenium oxide.
  • Titanium anodes comprising a catalytic Ru-Mn oxide coating with a composition corresponding to RuO. and MnO_ in a mole ratio of 14:86 were manufactured in the following manner.
  • a coating solution containing ruthenium chloride and manganese nitrate dissolved in a mole ratio 1:6 in 1-butyl alcohol was prepared with the composition by weight: 8.3% RuCl 3 aq.(40% Ru); 48.1% Mn(N0 3 ) 2 «4 H 2 0 43.6% butanol.
  • Titanium coupons (100x20xlmm) were pretreated by sandblasting treating in 1,1,1-trichlorethane for 10 minutes and etching in oxalic acid at 80°C for 6 hours.
  • the coating solution was successively applied with a brush in 22 layers to the pretreated titanium coupons, each applied layer of solution was dried for 10 minutes in air at 120°C, and the resulting dried layer was heat treated at 400 # C for 10 minutes in a stream of air, whereby the metal salts are thermally decomposed and converted to oxide.
  • the oxide coating thus
  • Another anode (E2) was produced by applying 16 layers of the
  • a further anode (E3) was produced by applying 28 layers of
  • the accelerated test life measured in the present tests should thus correspond to a considerably longer service life during normal operation at a lower anode current 2 density, such as for example 200 A/m , which is typically applied in processes for electrowinning copper from a sulphate electrolyte.
  • Titanium anodes comprising a catalytic Ru-Mn oxide coating with a composition corresponding to Ru0 2 and Mn0 2 in a mole ratio of 1:4 were manufactured in the following manner.
  • a coating solution comprising ruthenium chloride and manganese nitrate dissolved in a mole ratio 1:4 in 1-butyl alcohol was prepared with the composition by weight: 9.5% RuCl 3 aq.(40% Ru); 36.8% Mn( 0 3 ) 2 .4H 2 O; 53.7% butanol.
  • This coating solution was successiveively applied, dried, and converted to an oxide coating under the conditions previously described.
  • Another anode (C4) similarly produced but by applying 30 layers of the same solution with a total loading of
  • Titanium anodes with oxide coatings comprising different amounts of ruthenium and/or manganese were prepared and tested in the following manner.
  • Titanium coupons (100x20xlmm) were pretreated by sandblasting, treating in 1,1,1-trichlorethane for 10 minutes, and etching in oxalic acid at 80 ⁇ C for 6 hours.
  • a comparative anode RulOO with a Ru-oxide coating (100 % Ru0 2 ) was prepared by:
  • An anode Ru90 was similarly provided with a Ru-Mn oxide coating having a composition corresponding to a Ru0 2 : Mn0 2 mole ratio of 9:1 by applying in this case 9 layers of a coating solution with the composition by weight: 0.926 g RuCl 3 aq.(40% Ru); 0.103 g Mn(N0 3 ) 2 .4H 2 O 5.5 g ethanol; and 0.25 ml HCl (ION), and then drying and heat treating each applied layer in the same manner as described in steps (b) and (c) above.
  • An anode M5 was similarly provided with an Ru-Mn oxide coating having a composition corresponding to a 80 RuO 2 :20 MnO_ mole ratio by applying in this case 7 layers of a coating solution with the composition by weight: 0.721 g RuCl 3 aq.(40% Ru); 0.180 g Mn(N0 3 ) 2 .4H 2 O; 5.9 g ethanol; and 0.25 ml HCl (ION), and then drying and heat treating each applied layer as described in steps (b) and (c) above.
  • An anode M8 was similarly provided with a Ru-Mn oxide coating having a composition corresponding to a 50 RuO 2 :50 Mn0 2 mole ratio, but by applying in this case 8 layers of a coating solution with the composition by weight: 0.684 g RuCl 3 aq.(40% Ru); 0.680 g Mn(N0 3 ) 2 .4H 2 O; 3.6 g ethanol; and 0.25 ml HCl (10 N), and then drying and heat treating each layer as described in (b) and (c) above.
  • An anode M4 was similarly provided with a Ru-Mn oxide coating having a composition corresponding to a 30 RuO-:70 MnO- mole ratio, but by applying in this case 7 layers of a coating solution with the composition by weight: 1.074 g RuCl 3 aq.(40 % Ru); 2.419 g Mn(N0 3 ) 2 .4H 2 O; 3.6 g ethanol; and 0.25 ml HCl (ION), and then drying and heat treating each layer as described in (b) and (c) above.
  • An anode M13 was similarly provided with a Ru-Mn oxide coating having a composition corresponding to a 14 Ru0 2 :86 Mn0 2 mole ratio, but by applying in this case 11 layers of a coating solution with the composition by weight: 0.537 g RuCl 3 aq.(40 % Ru); 3.127 g Mn(N0 3 ) 2 .4H 2 O 2.835 g ethanol; and 0.25 ml HCl (ION), and then drying and heat treating each layer as described in (b) and (c) above.
  • Another comparative anode MnlOO was similarly provided with a
  • Mn-oxide coating (Mn0 2 ), but by applying in this case 11 layers of a solution with the composition by weight:
  • the invention may be used for the production of dimensionally stable anodes for industrial applications of catalytic oxygen evolving anodes where restriction of the anode costs is an essential requirement.
  • Anodes produced by the invention may be more particularly applied in processes for electrowinning metals such as copper and zinc from sulphate electrolytes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Catalysts (AREA)

Abstract

Procédé de fabrication d'anodes de dimensions stables dégageant de l'oxygène avec une base de titane et un revêtement d'oxyde catalytique produit à partir d'une solution de revêtement contenant des composés de Ru et de Mn dans des concentrations correspondant à un rapport molaire de RuO2 par rapport au MnO2 allant de 1/1 à 1/9. La solution est appliquée et séchée, puis elle est soumise à un traitement thermique dans l'air à 400oC, de manière à produire un revêtement d'oxyde comportant de 6 à 35 couches avec une charge totale de Ru = 4 à 20 g/m2. Un essai accéléré dans l'acide sulfurique d'anodes dont la fabrication respecte ces fourchettes révèle un faible potentiel d'oxygène pendant un fonctionnement prolongé en tant qu'anode dégageant de l'oxygène.
EP84903061A 1983-08-18 1984-08-02 Fabrication d'anodes degageant de l'hydrogene avec une base metallique filmogene et un revetement d'oxyde catalytique comportant du ruthenium Withdrawn EP0153356A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP83810368 1983-08-18
EP83810368 1983-08-18

Publications (1)

Publication Number Publication Date
EP0153356A1 true EP0153356A1 (fr) 1985-09-04

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP84903061A Withdrawn EP0153356A1 (fr) 1983-08-18 1984-08-02 Fabrication d'anodes degageant de l'hydrogene avec une base metallique filmogene et un revetement d'oxyde catalytique comportant du ruthenium
EP84810391A Withdrawn EP0135475A1 (fr) 1983-08-18 1984-08-08 Fabrication d'anodes pour le dégagement d'oxygène présentant une base en métal filmogène et un revêtement d'oxyde catalyseur comprenant du ruthénium

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Application Number Title Priority Date Filing Date
EP84810391A Withdrawn EP0135475A1 (fr) 1983-08-18 1984-08-08 Fabrication d'anodes pour le dégagement d'oxygène présentant une base en métal filmogène et un revêtement d'oxyde catalyseur comprenant du ruthénium

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EP (2) EP0153356A1 (fr)
JP (1) JPH0689470B2 (fr)
WO (1) WO1985000838A1 (fr)

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JP3124848B2 (ja) * 1992-11-11 2001-01-15 ペルメレック電極株式会社 金属箔の電解による製造方法
DE102010030293A1 (de) 2010-06-21 2011-12-22 Bayer Materialscience Ag Elektrode für die elektrolytische Chlorgewinnung
ITMI20110735A1 (it) 2011-05-03 2012-11-04 Industrie De Nora Spa Elettrodo per processi elettrolitici e metodo per il suo ottenimento
JP5700696B2 (ja) * 2012-04-12 2015-04-15 日本電信電話株式会社 リチウム空気二次電池
DE102013202144A1 (de) * 2013-02-08 2014-08-14 Bayer Materialscience Ag Elektrokatalysator, Elektrodenbeschichtung und Elektrode zur Herstellung von Chlor
CN103887528B (zh) * 2014-03-04 2016-07-13 成都达艾斯电子有限公司 锂空气电池用MnO2-RuO2/C催化剂及其制备方法
EP3465808B1 (fr) * 2016-06-07 2021-09-22 Cornell University Composés d'oxydes métalliques mixtes et compositions électrocatalytiques, dispositifs et procédés les utilisant
CN107245729B (zh) * 2017-06-21 2018-12-25 昆明理工大学 锰电积用碳纤维基梯度复合阳极材料及其制备方法
CN116573731B (zh) * 2023-06-09 2024-02-09 中国标准化研究院 同时去除焦化生化出水中总氰和多环芳烃的方法及系统

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US3775284A (en) * 1970-03-23 1973-11-27 J Bennett Non-passivating barrier layer electrodes
JPS5214716A (en) * 1975-07-21 1977-02-03 Mitsubishi Gas Chem Co Inc Process for preparation of alkali metlalformates
US4214970A (en) * 1979-01-15 1980-07-29 Diamond Shamrock Technologies, S.A. Novel electrocatalytic electrodes
FR2479272A1 (fr) * 1980-03-28 1981-10-02 Kubasov Vladimir Electrode pour processus electrochimiques et procede de fabrication de ladite electrode
GB2084189B (en) * 1980-08-18 1983-11-02 Diamond Shamrock Corp Coated catalytic electrode for electrochemical processes
CA1190185A (fr) * 1980-08-18 1985-07-09 Michael Katz Electrode enrobee avec couche protectrice intermediaire en polymere conducteur sur assise conductrice

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Publication number Publication date
WO1985000838A1 (fr) 1985-02-28
EP0135475A1 (fr) 1985-03-27
JPS60502214A (ja) 1985-12-19
JPH0689470B2 (ja) 1994-11-09

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