EP0925387B1 - Anode mit verbesserter lebensdauer und deren herstellungsverfahren - Google Patents

Anode mit verbesserter lebensdauer und deren herstellungsverfahren Download PDF

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Publication number
EP0925387B1
EP0925387B1 EP97924074A EP97924074A EP0925387B1 EP 0925387 B1 EP0925387 B1 EP 0925387B1 EP 97924074 A EP97924074 A EP 97924074A EP 97924074 A EP97924074 A EP 97924074A EP 0925387 B1 EP0925387 B1 EP 0925387B1
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EP
European Patent Office
Prior art keywords
approximately
ircl
substrate
anode
thermal decomposition
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Expired - Lifetime
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EP97924074A
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English (en)
French (fr)
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EP0925387A1 (de
Inventor
Véronique REID
Olivier Leclerc
Georgia Manoli
François CARDARELLI
André SAVALL
Christos Comninellis
Pierre Taxil
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Electricite de France SA
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Electricite de France SA
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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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
    • 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

Definitions

  • the present invention relates to an anode with improved durability for use in processes electrochemical. It also relates to the process of manufacture of this anode.
  • Electrochemical processes are experiencing many applications in very business sectors various such as mineral and organic electrosynthesis, electrometallurgy, depollution, electrodialysis, cathodic protection, treatment of polluted soils.
  • the anodes commonly used for such applications are characterized by a stable geometry resulting from high chemical and electrochemical inertia and by a constant potential during very long periods of use reaching, or even exceeding, two to three years.
  • These electrodes known as DSA® (Dimensionally Stable Anodes) have already shown their good electrochemical performance as an anode for the release of chlorine and / or oxygen.
  • These anodes consist of a metal of the “valve” type such as Ti, Ta, Nb, Zr, Sn and their alloys, covered with a layer of an electrocatalytic material composed of oxides of precious metals such as IrO 2 , PtO x , RuO 2 , optionally mixed with valve metal oxides such as SnO 2 , TiO 2 or Ta 2 O 5 .
  • valve metal is understood to mean a metal which is covered with a thin layer of protective oxide when it is oxidized (passivation) and which lets the current pass only under a cathodic potential.
  • the chlorine electrodes used in industrial processes consist of a titanium substrate covered with a mixture of metal oxides including RuO 2 which gives the material its electrocatalytic properties.
  • RuO 2 which gives the material its electrocatalytic properties.
  • the use of these electrodes is widespread on an industrial scale because of their satisfactory energy performance and their lifespan.
  • the anodes coated with RuO 2 specific for the industrial production of chlorine have poor performance as an anode for the release of oxygen in an acid medium.
  • the anodes intended for the release of oxygen in particularly in acid electrolytic medium, currently marketed consist of a substrate of titanium coated with a layer of at least one metal oxide, for example iridium oxide.
  • the electrocatalytic coating is deposited on the surface of the "valve" metal in the form of an oxide precursor, for example TaCl 5 for Ta 2 O 5 , IrCl 3 or H 2 IrCl 6 for IrO 2 .
  • an oxide precursor for example TaCl 5 for Ta 2 O 5 , IrCl 3 or H 2 IrCl 6 for IrO 2 .
  • Mixtures of these precursors are also used when it is desired to deposit layers of mixed catalytic oxides.
  • the precursor or mixture of precursors is applied in the form of a solution in an alcoholic solvent, preferably in a mixture of ethanol and isopropanol.
  • the precursor solution is deposited on the surface of the valve metal, for example with a brush, by spraying, by nebulization or by any other process known in the art.
  • the solvent is then evaporated by steaming and the electrode undergoes a heat treatment in air at the decomposition temperature of the precursor to form the corresponding metal oxide.
  • US Patent No. 3,878,083 describes for example an electrode comprising a metal base "valve", in particular titanium, on which is deposited a coating consisting of tantalum oxide and iridium oxide.
  • This coating is applied by thermal decomposition, at a temperature between 350 ° and 600 ° C., of a tantalum oxide precursor and of an iridium oxide precursor, such as TaCl 5 and IrCl respectively. 3 .
  • a TiO 2 layer is formed on the titanium substrate which is protected by an electrocatalytic oxide such as an iridium oxide and / or a tantalum oxide, thus leading to a passivation of the anode. The lifespan of such an anode is therefore not satisfactory.
  • tantalum substrate solves this problem because of its excellent resistance to chemical corrosion and its electrochemical stability.
  • the tantalum substrate has already been described, no method allows satisfactory electrocatalytic deposits of iridium oxide to be produced on tantalum.
  • the dissociation temperatures of IrCl 3 and H 2 IrCl 6 which are the usual precursors of IrO 2 , are higher than the oxidation temperature of tantalum. Therefore, the formation of tantalum oxide on the tantalum substrate appears before the formation of the catalytic oxide IrO 2 , which decreases the performance of these electrodes.
  • Test A which is an accelerated test for measuring the lifetime of the anodes, consists of carrying out electrolysis of a concentrated sulfuric acid solution using the anode to be tested, at a current density greater than 25 to 50 times the current density applied in the industrial processes.
  • the lifetimes of the anodes in these conditions are therefore shorter than durations life under normal operating conditions, which facilitates comparative study with a view to optimizing conditions anode preparation.
  • This test A is carried out as follows.
  • electrolysis is carried out of a solution of sulfuric acid at 30% by mass, the temperature of which is regulated at 80 ° C., and which is stirred continuously by a magnetic stirrer.
  • the anode has a rectangular shape (100 mm x 10 mm x 1 mm) and is inserted into heat-shrink tubing. Once the sheath is in place, a small circular opening of 0.20 cm 2 is cut out with a punch in the sheath. This is to precisely and reproducibly define the area of the active surface of the anode.
  • the distance between the two electrodes is 3 cm ( ⁇ 0.2 cm).
  • the gases released by the electrolysis of water are channeled separately to cooling tubes to limit the vesicular entrainment of sulfuric acid and avoid the risk of explosion.
  • the current density is then kept constant at this value and the potential difference between the anode and the cathode is recorded.
  • the surface mass of IrO 2 is defined as being the mass of electrocatalytic oxide IrO2 deposited as a coating per unit area of substrate.
  • the normalized service life ⁇ is thus expressed in hm 2 .g -1 .
  • a graphical representation of the potential difference U between the anode and the cathode measured during the test described above as a function of time is given in Figure 1.
  • the potential difference U increases progressively from time 0 to time t o , t o indicating the moment when the anode working current density reaches the desired constant value of 50 kA.m -2 .
  • the potential difference is then constant until time t 1 , the anode thus experiences normal operation between t o and t 1 , then after time t 1 , the potential difference increases indicating a deterioration of the anode.
  • the value of the potential difference U f U o + 2 (V) is reached at time t f .
  • the lifetime of the anode deduced from this curve is therefore equal to t f -t o .
  • the anodes object of the present invention have a normalized service life as measured by this test significantly higher than that of anodes currently used, as will emerge from the examples given below.
  • the subject of the present invention is an anode with improved longevity, characterized in that it has a standardized service life of at least 14 hm 2 .g -1 , preferably greater than 20 hm 2 .g -1 , and more preferably still greater than 25 hm 2 .g -1 , as measured by test A above and that it consists of a substrate of at least one metallic compound having an external tantalum surface, the external surface being covered with an electrocatalytic coating of iridium oxide.
  • the substrate used for the anode according to the invention may consist of tantalum only. However, in order to limit manufacturing costs, this substrate can consist of at least one metallic compound other than tantalum covered with a layer of tantalum. Compounds metals other than tantalum commonly used are chosen from copper, nickel, titanium, their alloys, steel or stainless steel.
  • This tantalum layer can be applied by any known method such as vacuum deposition, sputtering, deposition ionic, deposition from a reactive atmosphere, by co-lamination or electrochemically as described in the French patent application n ° 95 07158 not yet published in name of the Applicant Company.
  • This layer of tantalum has a thickness between 10 ⁇ m and 500 ⁇ m, preferably between 20 ⁇ m and 200 ⁇ m, more preferably between 20 ⁇ m and 100 ⁇ m.
  • the substrate used can be in the form of a plate, a hollow cylinder, a spherical particle or the like, depending on the applications envisaged for the anode.
  • the coating of iridium oxide covering the substrate is such that the surface mass of iridium oxide is greater than 4 gm -2 , preferably less than 30 gm -2 and more preferably still between 5 and 20 gm - 2 .
  • the present invention also relates to a method for manufacturing an anode as defined above, characterized in that the electrocatalytic coating of iridium oxide is produced in several layers by the thermal decomposition of iridium tetrachloride IrCl 4 previously applied as a coating on the substrate.
  • the Applicant Company had the merit of finding that by using such a mode of formation of the electrocatalytic coating, the anode does not undergo deactivation.
  • This thermal decomposition is carried out at a temperature below about 500 ° C, preferably below 475 ° C, and more preferably still between approximately 350 and 450 ° C.
  • thermal decomposition is first carried out at a temperature between around 350 ° C and 400 ° C, more preferably around 350 ° C then the temperature can be increased up to about 500 ° C, preferably up to 475 ° C and above preferably still between about 350 ° C and 450 ° C.
  • the first layers are obtained by thermal decomposition of a solution of IrCl 4 at a temperature between about 350 ° C and 400 ° C, more preferably about 350 ° C then the following layers are obtained with a temperature of thermal decomposition which has been increased and which is less than about 500 ° C.
  • the precursor IrCl 4 is deposited on the substrate in the form of a solution in an organic solvent making it possible to lower the temperature of thermal decomposition of IrCl 4 into oxide IrO 2 .
  • the solvent having this characteristic is chosen an alcoholic solvent, for example an aliphatic alcohol C 1 -C 4 such as methanol, ethanol, propanol, isopropanol, butanol 1, butanol 2, l isobutanol or tert.-butanol, or a mixture thereof.
  • a mixture of isopropanol and ethanol or isopropanol and butanol-1 is used.
  • the solvent is evaporated before carrying out the heat treatment in air.
  • step (a) above for preparing the substrate cleaning is preferably carried out using a surfactant. Sandblasting increases the surface specific substrate and chemical pickling allows to remove the insulating oxide layer which would have formed on the tantalum surface of the electrode.
  • Step (b) comprising the successive operations of applying the IrCl 4 solution, evaporating the solvent and thermal decomposition is repeated as many times as necessary to obtain the desired surface mass of oxide d 'iridium.
  • the surface mass of iridium oxide is preferably from 5 to 20 g / m 2 , of course, it can be greater, but this is disadvantageous from an economic point of view.
  • Step (b) is repeated at least 3 times, preferably at least 5 times.
  • the application of the solution of precursor is carried out for example with a brush, or by immersion, or by any other method known in the art, especially by spraying, spraying, etc.
  • the solvent can be evaporated in particular by steaming at the evaporation temperature of the solvent used.
  • the thermal decomposition of the precursor is carried out in an oven, in the air.
  • the decomposition thermal of the precursor is carried out at a temperature between about 350 and 400 ° C, more preferably about 350 ° C. Then for the following layers, preferably from the third layer, the temperature thermal decomposition is increased, it is lower at around 500 ° C, preferably below 475 ° C and more preferably still between approximately 350 and 450 ° C.
  • the final heat treatment step (c) is conducted at a temperature below about 550 ° C, preferably less than 525 ° C and more preferably still between about 450 and 500 ° C.
  • a support metal plate of 100 mm X 10 mm X 1 mm is used as substrate for the anode.
  • This plate is degreased with chloroform and then subjected to sandblasting under a pressure of 5 bar using corundum (particle size: 125 ⁇ m).
  • the plate is then rinsed in a tank of osmosis water under ultrasound for 10 minutes, subjected to a chemical pickling using hydrochloric or hydrofluoric acid then is rinsed.
  • a precursor solution is applied by immersion or with a brush.
  • the plate thus coated is steamed at 80 ° C for 5 minutes and then calcined in air in an oven at a temperature T 1 for 5 minutes.
  • n being the number of layers of the precursor solution which must be applied to obtain the desired areal mass of IrO 2 .
  • the plate is calcined in air for two hours at a temperature T 2 .
  • the anodes thus prepared are subjected to test A as described above, whereby their lifespan and their normalized service lives are determined.
  • Comparative Example 1 was repeated, except that the substrate used was NFT40 titanium and that the step of chemical pickling was conducted using hydrochloric acid at 37% at boiling point.
  • Comparative Example 1 was repeated except that the substrates used were titanium alloys such as indicated in the following Table I. Chemical pickling was carried out using concentrated hydrochloric acid 37% and 36% respectively.
  • Example 5 Manufacture of Ta / IrO 2 anodes
  • Example 6 Manufacture of Ta / IrO 2 anodes [substrate: AISI 316 L (UNS S31603) coated with Ta, precursor: IrCl 4 ].
  • Example 5 is repeated, except that one uses a stainless steel plate (316 L) covered with a tantalum layer whose thickness is indicated between parentheses in the following Table II. All anodes made in this example include 10 layers of precursor solution.
  • Example 5 according to the invention Your massive 5 4.54 115.0 25.31 10 10.77 274.2 25.46 10 12.40 343.3 27.68 15 13.81 450.0 32.59 20 20.31 528.0 26.00 25 24.08 972.0 40.36 30 31.72 473.3 14.92
  • Example 6 according to the invention 316L / Ta (23 ⁇ m) 10 9.39 363.0 38.64 316L / Ta (91 ⁇ m) 10 9.84 345.0 35.05 316L / Ta (93 ⁇ m) 10 9.07 273.0 30.08 316L / Ta (97 ⁇ m) 10 9.27 250.0 26.98 316L / Ta (98 ⁇ m 10 10.03 275.0 27.41 316L / Ta (99 ⁇ m) 10 9.27 253.0 27.30 Comparative Example 7 NF T40 (UNS R50100)

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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)
  • Battery Electrode And Active Subsutance (AREA)

Claims (12)

  1. Anode mit verbesserter Lebensdauer, dadurch gekennzeichnet, daß sie aus einem Substrat aus wenigstens einer metallischen Zusammensetzung gebildet wird, die eine äußere Oberfläche aus Tantal aufweist, wobei diese äußere Oberfläche mit einer elektrokatalytischen Beschichtung aus Iridiumoxid überzogen ist und wobei sie eine normale Lebensdauer aufweist, gemessen in einem Versuch A wie in der Beschreibung angegeben, höher als 14 h.m2.g-1, vorzugsweise höher als 20 h.m2.g-1 und noch mehr bevorzugt höher als 25 h.m2.g-1.
  2. Anode gemäß Patentanspruch 1, dadurch gekenzeichnet, daß das Substrat aus Tantal ist.
  3. Anode gemäß Patentanspruch 1, dadurch gekennzeichnet, daß die metallische Zusammensetzung aus Kupfer, Nickel, Titan, deren Legierungen, Stahl oder rostfreiem Stahl ausgewählt ist.
  4. Anode gemäß Patentanspruch 3, dadurch gekennzeichnet, daß die Schicht aus Tantal eine Dicke zwischen 10 µm und 500 µm, vorzugsweise zwischen 20 µm und 200 µm, und noch mehr bevorzugt zwischen 20 µm und 100 µm aufweist.
  5. Anode nach einem der Patentansprüche 1 bis 4, dadurch gekennzeichnet, daß die Oberflächenmasse aus Iridiumoxid, die als Beschichtung auf das Substrat aufgetragen ist, größer als 4 g.m-2 ist, vorzugsweise niedriger als 30 g.m-2, und noch mehr bevorzugt noch zwischen 5 und 20 g.m-2 liegt.
  6. Herstellungsverfahren einer Anode nach einem der Patentansprüche 1 bis 5, dadurch gekennzeichnet, daß die elektrokatalytische Beschichtung aus Iridiumoxid in mehreren Schichten durch thermische Zersetzung von Iridiumtetrachlorid IrCl4 durchgeführt wird, vorzugsweise angewandt als Beschichtung auf dem Substrat.
  7. Verfahren nach einem der Patentansprüche 1 bis 6,dadurch gekennzeichnet, daß die thermische Zersetzung von IrCl4 bei einer Temperatur ausgeführt wird, die niedriger als ca. 500° C ist, vorzugsweise niedriger als 475° C und noch mehr bevorzugt zwischen ca. 350° C und 450° C liegt.
  8. Verfahren gemäß Patentanspruch 7, dadurch gekennzeichnet, daß die thermische Zersetzung von IrCl4 zuerst bei einer Temperatur zwischen ca. 350 und 400° C durchgeführt wird, vorzugsweise ca. 350° C, um die ersten Schichten von Iridiumoxid zu bilden, und um jegliche Bildung von thermischem Tantaloxid zu vermeiden, das nicht leitfähig ist, diese Temperatur erhöht wird, bis zu einer Temperatur, die geringer als ca. 500° C ist, vorzugsweise geringer als ca. 475° C und noch mehr bevorzugt zwischen ca. 350 und 450° C ist, um die höheren Schichten aus Iridiumoxid zu bilden.
  9. Verfahren nach einem der Patentansprüche 6 und 8, dadurch gekennzeichnet, daß der Zwischenstoff IrCl4 in Form einer Lösung in einem organischen Lösungsmittel abgelagert wird, das erlaubt, die thermische Zersetzungstemperatur von IrCl4 in Oxid IrO2 zu senken, vorzugsweise in einem alkoholischen Lösungsmittel, und noch mehr bevorzugt in einem Gemisch aus Ethanol und Isopropanol, wobei das genannte Lösungsmittel vor der thermischen Zersetzung verdunstet wird.
  10. Verfahren nach einem der Patentansprüche 6 bis 9, dadurch gekennzeichnet, daß es die folgenden Schritte umfasst:
    (a) Vorbereitung des Substrates, insbesondere bestehend aus Waschen, Sandstrahlen und chemischem Beizen;
    (b) Abscheidung der Iridiumoxid-Schicht durch Einsatz der IrCl4 Lösung in einem organischen Lösungsmittel auf dem Substrat, Verdampfen des Lösungsmittels und thermische Zersetzung von IrCl4;
    (c) thermische Endbehandlung, wobei der Verfahrensschritt (b) so oft wie notwendig wiederholt wird, um die gewünschte Oberflächenmasse von Iridiumoxid zu erhalten.
  11. Verfahren gemäß Patentanspruch 10, dadurch gekennzeichnet, daß der Verfahrensschritt (b) mindestens dreimal wiederholt wird, vorzugsweise mindestens fünfmal, und daß die thermische Zersetzungstemperatur zwischen 350 und 400° C liegt, vorzugsweise bei 350° C mindestens für die zwei ersten Male, bei dem der Verfahrensschritt (b) durchgeführt wird, anschließend der Verfahrensschritt (b) wiederholt wird, wobei die thermische Zersetzungstemperatur erhöht wird, wobei diese dann niedriger als ca. 500° C ist, vorzugsweise niedriger als 475° C und noch mehr bevorzugt zwischen 350 und 450° C liegt.
  12. Verfahren gemäß Patentanspruch 10 oder 11, dadurch gekennzeichnet, daß der Verfahrensschritt (c) der thermischen Endbehandlung bei einer Temperatur geringer als ca. 550° C ausgeführt wird, vorzugsweise niedriger als 525° C, und noch mehr bevorzugt zwischen 450 und 500° C.
EP97924074A 1996-05-13 1997-05-12 Anode mit verbesserter lebensdauer und deren herstellungsverfahren Expired - Lifetime EP0925387B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9605916A FR2748495B1 (fr) 1996-05-13 1996-05-13 Anode a longevite amelioree et son procede de fabrication
FR9605916 1996-05-13
PCT/FR1997/000836 WO1997043465A1 (fr) 1996-05-13 1997-05-12 Anode a longevite amelioree et son procede de fabrication

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EP0925387A1 EP0925387A1 (de) 1999-06-30
EP0925387B1 true EP0925387B1 (de) 2000-09-20

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EP (1) EP0925387B1 (de)
DE (1) DE69703163T2 (de)
ES (1) ES2152673T3 (de)
FR (1) FR2748495B1 (de)
WO (1) WO1997043465A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2811339B1 (fr) * 2000-07-07 2003-08-29 Electricite De France Procede de preparation de materiaux metalliques pour leur utilisation comme electrodes
FR2811338B1 (fr) * 2000-11-10 2003-02-14 Electricite De France Procede de preparation de materiaux metalliques pour leur utilisation comme electrodes
WO2021117311A1 (ja) * 2019-12-13 2021-06-17 パナソニックＩｐマネジメント株式会社 電解用電極

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4257856A (en) * 1979-10-17 1981-03-24 Bell Telephone Laboratories, Incorporated Electrolytic process useful for the electrolysis of water
GB8903322D0 (en) * 1989-02-14 1989-04-05 Ici Plc Electrolytic process
DE3905082A1 (de) * 1989-02-18 1990-08-23 Bayer Ag Formstabile anoden und deren verwendung bei der herstellung von alkalidichromaten und chromsaeure
JP3044797B2 (ja) * 1991-02-04 2000-05-22 ダイソー株式会社 酸素発生用陽極の製法

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FR2748495A1 (fr) 1997-11-14
ES2152673T3 (es) 2001-02-01
EP0925387A1 (de) 1999-06-30
FR2748495B1 (fr) 1998-07-17
DE69703163T2 (de) 2001-05-17
DE69703163D1 (de) 2000-10-26
WO1997043465A1 (fr) 1997-11-20

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