EP0245201A1 - Anode pour l'électrolyse - Google Patents

Anode pour l'électrolyse Download PDF

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Publication number
EP0245201A1
EP0245201A1 EP87810254A EP87810254A EP0245201A1 EP 0245201 A1 EP0245201 A1 EP 0245201A1 EP 87810254 A EP87810254 A EP 87810254A EP 87810254 A EP87810254 A EP 87810254A EP 0245201 A1 EP0245201 A1 EP 0245201A1
Authority
EP
European Patent Office
Prior art keywords
substrate
titanium
anode
framework
electrochemically active
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
Application number
EP87810254A
Other languages
German (de)
English (en)
Other versions
EP0245201B1 (fr
Inventor
Heiner Dr. Debrodt
Petra Kluger
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.)
Novartis AG
Original Assignee
Ciba Geigy AG
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
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0245201A1 publication Critical patent/EP0245201A1/fr
Application granted granted Critical
Publication of EP0245201B1 publication Critical patent/EP0245201B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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

  • the invention relates to an anode for aqueous electrolysis, consisting of a framework which is resistant to the electrolyte and the electrolysis products, a porous substrate containing titanium which is firmly connected to the framework and electrochemically active substances which are distributed in the pores of the substrate.
  • metal anodes In chlor-alkali electrolysis and other electrolyses with aqueous electrolytes, metal anodes have been used for some time, which essentially contain a framework or a base made of a passivable metal, on which one or more electrochemically active substances are firmly anchored. Usually, because of its availability and the comparatively low price, titanium scaffolds are used which are resistant to the electrolyte and the electrolysis products.
  • Preferred electrochemically active substances are oxides of platinum group metals, alone or in mixtures with other metal oxides, spinels, perovskites and other mixed oxides. Coatings that do not contain platinum metal oxides have also become known for special electrolyses.
  • the service life of the coated anodes is essentially determined by the resistance of the electrochemically active coating, which also depends on the resistance in contact with mercury, depending on the type of substance and the electrolysis conditions, the adhesion to the metal structure and in chlor-alkali electrolysis in mercury cells.
  • Numerous proposals have been published for extending the anode service life, which secure the active substance against damage caused by short circuit, improve their anchoring on the titanium framework and ultimately provide the largest possible amount of the electrochemically active substance. These proposals have in common porous support layers or substrates that are firmly attached to the framework and absorb the electrochemically active substance.
  • the porous substrate is a better primer than the more or less smooth surface of the framework, it protects the active substance in the event of short circuits, and its absorption capacity can be adapted to the needs of electrolysis in a wide range via the porosity and thickness of the substrate.
  • the substrate consists of various titanium oxides, which are applied to the anode frame in an amount of 100 to 6000 g / m 2 by flame or plasma spraying.
  • Oxides of the composition TiO 2-x should behave particularly advantageously, with 0.1>x> 0.
  • the porous substrate is impregnated with salts of the solution containing platinum metals, which are thermally decomposed after evaporation of the solvent. It is also known to apply the electrochemically active substance together with oxides, nitrides, phosphides, borides or carbides of a metal from the group of passivatable metals, preferably with titanium oxide, to the surface of the anode structure in a single operation (EP-OS 0 058 832 ).
  • Another anode has a substrate which, in addition to titanium oxides, contains oxides of other non-noble metals, such as niobium oxide or nickel oxide (DE-OS 32 08 835). Compounds of at least one element of the platinum group are added to the substrate applied by flame spraying. Finally, a substrate is known which consists of a sintered layer of titanium oxides of the composition TiO x , with 0.25 ⁇ x ⁇ 1.50 (DE-OS 24 12 828). The porous substrate known from DE-OS 20 35 212, sintered onto the support frame, is made of metallic titanium.
  • the invention relates to an anode for aqueous electrolysis, consisting of a framework which is resistant to the electrolyte and the electrolysis products, a porous substrate containing titanium connected to the framework and electrochemically active substances which are distributed in the pores of the substrate, characterized in that porous titanium-containing substrate with a metal from the group chromium, nickel is doped.
  • the invention is based on the surprising finding that, under the conditions of aqueous electrolysis, titanium doped with chromium and / or nickel also transports the current in the anodic direction, even if it does not contain any electrochemically active substances.
  • the passivation is greatly reduced compared to substrates made of titanium or other passivable metals or valve metals. Anodic metal dissolutions are practically not observed.
  • the character of the layer according to the invention is comparable to that of a noble metal.
  • the proportion of the doping elements added to the titanium can e.g. 0.5 to 40% by weight and is preferably 2 to 20% by weight, especially 2 to 10% by weight.
  • the effect of the doping is small below approximately 2%, and above 20%, partial doping of the doping metals can occur under the conditions of oxygen-developing anodes.
  • chromium and / or nickel in the form of fine powders can be mixed with powdered titanium and the mixture can be applied to the framework, for example by flame spraying. Under these conditions, mixed crystals of titanium and the doping metal are only formed to a limited extent.
  • the powder mixture mixed with a temporary binder is sprayed or brushed onto the framework and a porous sintered layer firmly connected to the framework is formed by heating in an inert atmosphere.
  • Mixed crystals can form to a large extent during sintering, but are thermodynamically unstable at room temperature and therefore disintegrate on cooling.
  • the functionality of the doped substrates is practically independent of the different manufacturing processes.
  • the thickness of the substrate is preferably 0.2 to 1 mm.
  • the porosity can be, for example, 20 to 60% by volume, in particular 30 to 50% by volume. With an average porosity of approx. 40% by volume, the substrate has a holding capacity for the electrochemically active substances, which is appropriate for the known aqueous electrolysis.
  • the substrate can be impregnated with solutions or suspensions containing these substances.
  • the type of electrochemically active substances used is determined in a known manner by the electrolysis conditions. Suitable metals include platinum metals, oxides of platinum metals, spinels, perovskites, ⁇ -manganese dioxide alone or in mixtures.
  • Anodes according to the invention are particularly suitable for chloralkali electrolysis and for electrolysis in which oxygen is generated anodically.
  • the anodes have a long service life and their reactivation is particularly simple, since obviously no oxides which do not conduct electricity are formed during the electrolysis.
  • the anode is reactivated by introducing electrochemically active substances into the porous substrate.
  • Example 1 Titanium sheets are degreased, sandblasted and coated with a fine-grained mixture of titanium and chrome powder.
  • the mixture contains 9% by weight of chromium and 91% by weight of titanium (maximum grain size 0.1 mm) and is made into an injectable paste with an aqueous tylose solution.
  • a 0.5 mm thick layer is applied to the sheets with a gravity cup gun; the sheets are dried at room temperature and, by heating to 1200 ° C. in argon, a porous substrate layer is adhered to the sheets, the porosity of which is approximately 25% by volume.
  • titanium sheets without substrates and titanium sheets with undoped substrate layers made of porous sintered titanium were coated with the same amounts of the electrochemically active substances and the service life of the anodes was measured in 20% sulfuric acid at room temperature under the same conditions.
  • Example 2 An approximately 0.4 mm thick substrate layer of doped titanium is applied to titanium sheets by flame spraying a mixture containing 9% by weight of nickel and 91% by weight of titanium powder. The grain size of the powder is less than 0.05 mm. As described in Example 1, the substrate layers are impregnated with solutions a, b and c and tested in comparison with anodes which contain the same amount of electrochemically active substances but no substrate or no doped substrate.
  • Example 3 The passivation rate of different anodes, which have no coatings with electrochemically active substances, is measured in 20% sulfuric acid at room temperature and a current density of 0.2 kA / m2. Passivation is indicated by an increase in cell voltage to 10 V.

Landscapes

  • 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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Secondary Cells (AREA)
EP87810254A 1986-04-25 1987-04-22 Anode pour l'électrolyse Expired - Lifetime EP0245201B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863613997 DE3613997A1 (de) 1986-04-25 1986-04-25 Anode fuer elektrolytische prozesse
DE3613997 1986-04-25

Publications (2)

Publication Number Publication Date
EP0245201A1 true EP0245201A1 (fr) 1987-11-11
EP0245201B1 EP0245201B1 (fr) 1991-05-22

Family

ID=6299502

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87810254A Expired - Lifetime EP0245201B1 (fr) 1986-04-25 1987-04-22 Anode pour l'électrolyse

Country Status (5)

Country Link
US (1) US4849085A (fr)
EP (1) EP0245201B1 (fr)
JP (1) JPS62270790A (fr)
DE (2) DE3613997A1 (fr)
NO (1) NO166496C (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5314601A (en) * 1989-06-30 1994-05-24 Eltech Systems Corporation Electrodes of improved service life
US5324407A (en) * 1989-06-30 1994-06-28 Eltech Systems Corporation Substrate of improved plasma sprayed surface morphology and its use as an electrode in an electrolytic cell
US5879817A (en) * 1994-02-15 1999-03-09 Eltech Systems Corporation Reinforced concrete structure
US5964993A (en) * 1996-12-19 1999-10-12 Implanted Biosystems Inc. Glucose sensor
US5914026A (en) * 1997-01-06 1999-06-22 Implanted Biosystems Inc. Implantable sensor employing an auxiliary electrode
US20030010649A1 (en) * 2001-07-16 2003-01-16 Waite Michael D. Inert anode for electrochemical process
EP1850412A1 (fr) * 2006-04-26 2007-10-31 Technical University of Denmark Un retêvement multicouche

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1812522A1 (de) * 1968-12-04 1970-06-18 Basf Ag Verfahren zur Herstellung von Anoden fuer die Chloralkalielektrolyse
GB1233590A (fr) * 1967-08-16 1971-05-26
FR2098464A1 (fr) * 1970-07-16 1972-03-10 Conradty Fa C
FR2215268A1 (fr) * 1973-01-26 1974-08-23 Electronor Corp
FR2216021A1 (en) * 1973-02-02 1974-08-30 Sigri Elektrographit Gmbh Porous electrodes for electrolytic cells - with a non-passivatable metal coating
US4138510A (en) * 1973-09-27 1979-02-06 Firma C. Conradty Metal anode for electrochemical processing and method of making same
US4140615A (en) * 1977-03-28 1979-02-20 Olin Corporation Cell and process for electrolyzing aqueous solutions using a porous anode separator

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926773A (en) * 1970-07-16 1975-12-16 Conradty Fa C Metal anode for electrochemical processes and method of making same
DE2300422C3 (de) * 1973-01-05 1981-10-15 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung einer Elektrode
US4013525A (en) * 1973-09-24 1977-03-22 Imperial Chemical Industries Limited Electrolytic cells
DE2405010C3 (de) * 1974-02-02 1982-08-05 Sigri Elektrographit Gmbh, 8901 Meitingen Sinter-Elektrode für elektrochemische Prozesse und Verfahren zum Herstellen der Elektrode
DD137365A5 (de) * 1976-03-31 1979-08-29 Diamond Shamrock Techn Elektrode
JPS5544514A (en) * 1978-09-22 1980-03-28 Permelec Electrode Ltd Electrode for electrolysis and production thereof
DE3106587C2 (de) * 1981-02-21 1987-01-02 Heraeus Elektroden GmbH, 6450 Hanau Elektrode und deren Verwendung
JPS6017834B2 (ja) * 1981-03-11 1985-05-07 昭和電工株式会社 不溶性電極をそなえた電気化学的装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1233590A (fr) * 1967-08-16 1971-05-26
DE1812522A1 (de) * 1968-12-04 1970-06-18 Basf Ag Verfahren zur Herstellung von Anoden fuer die Chloralkalielektrolyse
FR2098464A1 (fr) * 1970-07-16 1972-03-10 Conradty Fa C
FR2215268A1 (fr) * 1973-01-26 1974-08-23 Electronor Corp
FR2216021A1 (en) * 1973-02-02 1974-08-30 Sigri Elektrographit Gmbh Porous electrodes for electrolytic cells - with a non-passivatable metal coating
US4138510A (en) * 1973-09-27 1979-02-06 Firma C. Conradty Metal anode for electrochemical processing and method of making same
US4140615A (en) * 1977-03-28 1979-02-20 Olin Corporation Cell and process for electrolyzing aqueous solutions using a porous anode separator

Also Published As

Publication number Publication date
EP0245201B1 (fr) 1991-05-22
NO166496B (no) 1991-04-22
DE3613997A1 (de) 1987-10-29
US4849085A (en) 1989-07-18
DE3770193D1 (de) 1991-06-27
NO871717D0 (no) 1987-04-24
NO871717L (no) 1987-10-26
NO166496C (no) 1991-07-31
JPS62270790A (ja) 1987-11-25

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