WO2011036225A1 - Electrode for electrolytic processes with controlled crystalline structure - Google Patents

Electrode for electrolytic processes with controlled crystalline structure Download PDF

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Publication number
WO2011036225A1
WO2011036225A1 PCT/EP2010/064081 EP2010064081W WO2011036225A1 WO 2011036225 A1 WO2011036225 A1 WO 2011036225A1 EP 2010064081 W EP2010064081 W EP 2010064081W WO 2011036225 A1 WO2011036225 A1 WO 2011036225A1
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WIPO (PCT)
Prior art keywords
ruthenium
deposition
coating
electrode
electrode according
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.)
Ceased
Application number
PCT/EP2010/064081
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English (en)
French (fr)
Inventor
Christian Urgeghe
Stefania Mora
Antonio Lorenzo Antozzi
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.)
Industrie de Nora SpA
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Industrie de Nora SpA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to MX2012003517A priority Critical patent/MX2012003517A/es
Priority to EP10755197.0A priority patent/EP2480705B1/en
Priority to JP2012530263A priority patent/JP5824454B2/ja
Priority to HK12113623.4A priority patent/HK1172936B/xx
Priority to DK10755197.0T priority patent/DK2480705T3/en
Priority to CN201080042171.0A priority patent/CN102575363B/zh
Priority to KR1020127010290A priority patent/KR101742011B1/ko
Priority to BR112012006530A priority patent/BR112012006530A2/pt
Priority to CA2769824A priority patent/CA2769824C/en
Application filed by Industrie de Nora SpA filed Critical Industrie de Nora SpA
Priority to AU2010299850A priority patent/AU2010299850B2/en
Priority to EA201270451A priority patent/EA023083B1/ru
Publication of WO2011036225A1 publication Critical patent/WO2011036225A1/en
Priority to IL217859A priority patent/IL217859A/en
Priority to ZA2012/01825A priority patent/ZA201201825B/en
Priority to US13/427,153 priority patent/US9090982B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal

Definitions

  • the invention relates to an electrode for electrolytic processes and a method of manufacturing thereof.
  • electrodes consisting of a metal base (for instance made of titanium, zirconium or other valve metals, nickel , stainless steel, copper or alloys thereof) equipped with a coating based on noble metals or alloys thereof are for instance used as hydrogen-evolving cathodes in water or chlor-alkali electrolysis processes.
  • a metal base for instance made of titanium, zirconium or other valve metals, nickel , stainless steel, copper or alloys thereof
  • a coating based on noble metals or alloys thereof are for instance used as hydrogen-evolving cathodes in water or chlor-alkali electrolysis processes.
  • coatings containing ruthenium, as metal or more frequently as ruthenium oxide, optionally in admixture with valve metal oxides are particularly relevant.
  • Electrodes of such kind may for instance be produced by thermal processes, through the decomposition of precursor solutions of the metals to be deposited by suitable thermal treatments, or less frequently by galvanic electrodeposition from suitable electrolytic baths.
  • These preparation methods are capable of producing ruthenium catalysts characterised by a great variability of crystal lattice parameters, presenting a fair catalytic activity towards hydrogen evolution reaction, non perfectly correlated with the crystall ite average size.
  • the best catalysts produced by thermal decomposition of salt precursor solutions can for instance present a crystal average size of about 1 0-40 nm with a standard deviation of 2-3 nm, the relevant catalytic activity being moderately increased for samples at the lower end of the range.
  • Catalysts with these characteristics and with the usual noble metal loadings, for instance 5 to 12 g/m 2 of ruthenium expressed as metal can be capable of decreasing the reduction potential of hydrogen of 20-30 mV with respect to the best catalysts of the prior art.
  • an electrode provided with a catalytic coating having a crystallite size of 1 to 10 nm, optionally 1 to 5 nm, with a standard deviation not higher than 0.5 nm can be obtained by subjecting a metal substrate, for example a nickel substrate, to a chemical or physical vapour deposition treatment of ruthenium, wherein such deposition is suitably controlled so as to produce the desired lattice parameters.
  • a metal substrate for example a nickel substrate
  • the size of crystallites can be adjusted for instance by acting on the temperature of the metal substrate, on the degree of vacuum of the deposition process, on the energy level of an ion plasma used to bomb the substrate during the deposition phase or on several other parameters, specific of the various applicable techniques.
  • a physical vapour deposition of ruthenium is obtained by means of an IBAD technique, providing the generation of plasma at a pressure of 10 "6 -10 "3 Pa, the extraction of ruthenium ions from targets of ruthenium metal arranged in the deposition chamber under the action of plasma assisted by an ion beam and the consequent bombardment of the substrate to be treated with a beam containing ruthenium ions at an energy of 1000 to 2000 eV.
  • the IBAD deposition is of dual type, that is preceded by a step of substrate cleaning by bombardment with in situ-generated argon ions at a lower energy level (200-500 eV).
  • a physical vapour deposition of ruthenium is obtained by means of a MPS (Magnetron Plasma Sputtering) technique, providing the generation of high density plasma through the combined use of a magnetic field and a radiofrequency electric field, or by a DC Plasma Sputtering technique, providing the generation of high density plasma through the combined use of a magnetic field and modulated direct current.
  • MPS Magnetic Plasma Sputtering
  • DC Plasma Sputtering providing the generation of high density plasma through the combined use of a magnetic field and modulated direct current.
  • a physical vapour deposition of ruthenium in form of oxide for instance of non-stoichiometric dioxide characterised by particularly high catalytic activity and stability at the usual industrial electrolysis conditions, is obtained by means of a physical vapour deposition according to one of the above described methodologies carried out in the presence of a reactant gas, for instance oxygen, so as to produce the simultaneous oxidation of the deposited ruthenium.
  • a reactant gas for instance oxygen
  • a hydrogen-evolving electrode comprises a substrate coated with an intermediate catalytic coating of ruthenium dioxide which can be prepared galvanically or by thermal decomposition of salt precursors, whereon a superficial catalytic coating is appl ied consisting of crystallites of ruthenium, in metal or oxide form, having a size of 1 to 1 0 nm, more preferably 1 to 5 nm, with a standard deviation not higher than 0.5 nm, wherein such coating can be prepared by chemical or physical vapour deposition.
  • the intermediate catalytic coating has a specific loading of 5-1 2 g/m 2 of ruthenium expressed as metal and the superficial catalytic coating has a specific loading of 1 -5 g/m 2 of ruthenium expressed as metal.
  • a flattened mesh of nickel 200 of 1000 mm x 500 mm x 0.89 mm size was subjected to a blasting treatment with corundum until obtaining a controlled roughness, with an R z value of 70 ⁇ .
  • the blasted mesh was then etched in 20% boiling HCI to eliminate possible corundum residues.
  • the thus-treated mesh was loaded in a Magnetron Plasma Sputtering device of the type provided with a conditioning chamber operated at a first vacuum level (typically 10 "3 Pa) and with a deposition chamber operated at high vacuum, equipped with a ruthenium metal target; upon reaching a vacuum level of 5.10 "5 Pa in the deposition chamber, the generation of a pure Ar plasma was activated between the mesh and the chamber walls.
  • a Magnetron Plasma Sputtering device of the type provided with a conditioning chamber operated at a first vacuum level (typically 10 "3 Pa) and with a deposition chamber operated at high vacuum, equipped with a ruthenium metal target; upon reaching a vacuum level of 5.10 “5 Pa in the deposition chamber, the generation of a pure Ar plasma was activated between the mesh and the chamber walls.
  • the generation of plasma was activated between the ruthenium target (99% w/w, 200 W nominal power, zero reflected power) simultaneously feeding a 20% oxygen in argon gas mixture thereby establishing a dynamic vacuum of 10 "1 Pa: this triggered the onset of the reactive deposition of a RuO2 layer.
  • the sample holder housing the mesh was rotated to optimise the homogeneity. The deposition was repeated on the opposite side of the mesh, until obtaining a total loading of 9 g/m 2 of Ru expressed as metal.
  • a flattened mesh of nickel 200 of 1000 mm x 500 mm x 0.89 mm size was subjected to a blasting treatment with corundum until obtaining a controlled roughness, with an R z value of 70 ⁇ .
  • the blasted mesh was then etched in 20% boiling HCI to eliminate possible corundum residues.
  • the thus-treated mesh was activated with 8 g/m 2 of ruthenium, expressed as metal, by thermal decomposition of a RuCl3.3H 2 O hydroalcoholic solution acidified with HCI.
  • the solution was applied in four coats by spraying and subsequent thermal treatment in a vented oven at 480°C for 10 minutes. After the last coat, a final thermal treatment of 1 hour at the same temperature was carried out.
  • the preactivated mesh was then loaded in a Magnetron Plasma Sputtering device analogous to the one of example 1 .
  • a Magnetron Plasma Sputtering device analogous to the one of example 1 .
  • the generation of a pure Ar plasma was activated between the mesh and the chamber walls.
  • the generation of plasma was activated between the ruthenium target (99% w/w, 200 W nominal power, zero reflected power) simultaneously feeding a 20% oxygen in argon gas mixture thereby establishing a dynamic vacuum of 10 "1 Pa: this triggered the onset of the reactive deposition of a RuO 2 layer.
  • the sample holder housing the mesh was rotated to optimise the homogeneity.
  • the deposition was repeated on the opposite side of the mesh, until obtaining a total loading of 4 g/m 2 of Ru expressed as metal.
  • the ex situ measurement of crystallite size by low angle X-Ray diffraction technique showed a value of 4.0 +/- 0.5 nm.
  • a hydrogen evolution potential of -930 mV/NHE was detected in 32% caustic soda at a temperature of 90°C and at a current density of 3 kA m 2 .
  • a flattened mesh of nickel 200 of 1000 mm x 500 mm x 0.89 mm size was subjected to a blasting treatment with corundum until obtaining a controlled roughness, with an R z value of 70 ⁇ .
  • the blasted mesh was then etched in 20% boiling HCI to eliminate possible corundum residues.
  • the thus-treated mesh was activated with 12 g/m 2 of ruthenium, expressed as metal, by thermal decomposition of a RuCl3.3H 2 O hydroalcoholic solution acidified with HCI.
  • the solution was applied in five coats by spraying and subsequent thermal treatment in a vented oven at 550°C for 10 minutes. After the last coat, a final thermal treatment of 1 hour at the same temperature was carried out.
  • the ex situ measurement of crystallite size by low angle X-Ray diffraction technique showed a value of 20 +/- 2 nm.
  • a hydrogen evolution potential of -950 mV/NHE was detected in 32% caustic soda at a temperature of 90°C and at a current density of 3 kA/m 2 .
  • a flattened mesh of nickel 200 of 1000 mm x 500 mm x 0.89 mm size was subjected to a blasting treatment with corundum until obtaining a controlled roughness, with an R z value of 70 ⁇ .
  • the blasted mesh was then etched in 20% boiling HCI to eliminate possible corundum residues.
  • the thus-treated mesh was activated with 13 g/m 2 of ruthenium, expressed as metal, by thermal decomposition of a RuCl3.3H 2 O hydroalcoholic solution acidified with HCI.
  • the solution was applied in five coats by spraying and subsequent thermal treatment in a vented oven at 460°C for 10 minutes. After the last coat, a final thermal treatment of 1 hour at the same temperature was carried out.
  • a flattened mesh of nickel 200 of 1000 mm x 500 mm x 0.89 mm size was subjected to a blasting treatment with corundum until obtaining a controlled roughness, with an R z value of 70 ⁇ .
  • the blasted mesh was then etched in 20% boiling HCI to eliminate possible corundum residues.
  • the thus-treated mesh was then loaded in a Magnetron Plasma Sputtering device analogous to the one of example 1 . While reaching a vacuum condition of 5.10 "5 Pa in the deposition chamber, the temperature of the sample was brought to 450°C by means of an electric resistance; the generation of a pure Ar plasma was then activated between the mesh and the chamber walls. Upon completion of this surface cleaning phase, the generation of plasma was activated between the ruthenium target (99% w/w, 200 W nominal power, zero reflected power) simultaneously feeding a 20% oxygen in argon gas mixture thereby establishing a dynamic vacuum of 10 "1 Pa: this triggered the onset of the reactive deposition of a RuO2 layer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Catalysts (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Electrolytic Production Of Metals (AREA)
PCT/EP2010/064081 2009-09-23 2010-09-23 Electrode for electrolytic processes with controlled crystalline structure Ceased WO2011036225A1 (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
CA2769824A CA2769824C (en) 2009-09-23 2010-09-23 Electrode for electrolytic processes with controlled crystalline structure
JP2012530263A JP5824454B2 (ja) 2009-09-23 2010-09-23 制御された結晶構造を有する電解プロセス用電極
HK12113623.4A HK1172936B (en) 2009-09-23 2010-09-23 Electrode for electrolytic processes with controlled crystalline structure
DK10755197.0T DK2480705T3 (en) 2009-09-23 2010-09-23 ELECTRODE FOR ELECTROLYTIC PROCESSES WITH CONTROLLED CRYSTAL STRUCTURE
CN201080042171.0A CN102575363B (zh) 2009-09-23 2010-09-23 具有受控晶态结构的电解工艺电极
KR1020127010290A KR101742011B1 (ko) 2009-09-23 2010-09-23 제어된 결정 조직을 구비한 전기 분해 공정용 전극
BR112012006530A BR112012006530A2 (pt) 2009-09-23 2010-09-23 eletrodo para processos eletrolíticos com estrutura cristalina controlada
MX2012003517A MX2012003517A (es) 2009-09-23 2010-09-23 Electrodo para procesos electroliticos con estructura cristalina controlada.
AU2010299850A AU2010299850B2 (en) 2009-09-23 2010-09-23 Electrode for electrolytic processes with controlled crystalline structure
EP10755197.0A EP2480705B1 (en) 2009-09-23 2010-09-23 Electrode for electrolytic processes with controlled crystalline structure
EA201270451A EA023083B1 (ru) 2009-09-23 2010-09-23 Электрод для катодного выделения водорода в электролитическом процессе
IL217859A IL217859A (en) 2009-09-23 2012-01-31 Electrode for Electrolyte Processes with Controlled Crystalline Structure
ZA2012/01825A ZA201201825B (en) 2009-09-23 2012-03-13 Electrode for electrolytic processes with controlled crystalline structure
US13/427,153 US9090982B2 (en) 2009-09-23 2012-03-22 Electrode for electrolytic processes with controlled crystalline structure

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT001621A ITMI20091621A1 (it) 2009-09-23 2009-09-23 Elettrodo per processi elettrolitici con struttura cristallina controllata
ITMI2009A001621 2009-09-23

Related Child Applications (1)

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US13/427,153 Continuation US9090982B2 (en) 2009-09-23 2012-03-22 Electrode for electrolytic processes with controlled crystalline structure

Publications (1)

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WO2011036225A1 true WO2011036225A1 (en) 2011-03-31

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PCT/EP2010/064081 Ceased WO2011036225A1 (en) 2009-09-23 2010-09-23 Electrode for electrolytic processes with controlled crystalline structure

Country Status (17)

Country Link
US (1) US9090982B2 (https=)
EP (1) EP2480705B1 (https=)
JP (1) JP5824454B2 (https=)
KR (1) KR101742011B1 (https=)
CN (1) CN102575363B (https=)
AR (1) AR078442A1 (https=)
AU (1) AU2010299850B2 (https=)
BR (1) BR112012006530A2 (https=)
CA (1) CA2769824C (https=)
DK (1) DK2480705T3 (https=)
EA (1) EA023083B1 (https=)
IL (1) IL217859A (https=)
IT (1) ITMI20091621A1 (https=)
MX (1) MX2012003517A (https=)
TW (1) TWI490372B (https=)
WO (1) WO2011036225A1 (https=)
ZA (1) ZA201201825B (https=)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20122035A1 (it) * 2012-11-29 2014-05-30 Industrie De Nora Spa Elettrodo per evoluzione di ossigeno in processi elettrochimici industriali
DK3351659T3 (da) * 2015-09-18 2019-12-16 Asahi Chemical Ind Positiv elektrode til vandelektrolyse, elektrolysecelle og fremgangsmåde til at fremstille en positiv elektrode til vandelektrolyse
EP3781699B1 (en) * 2018-04-18 2024-01-17 Materion Corporation Electrodes for biosensors
CN113073336B (zh) * 2021-03-26 2022-07-08 浙江工业大学 一种RuO2泡沫镍复合电极及其制备方法和应用

Citations (2)

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