EP0344378A1 - Electrode pour la production d'oxygène et son procédé de préparation - Google Patents

Electrode pour la production d'oxygène et son procédé de préparation Download PDF

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Publication number
EP0344378A1
EP0344378A1 EP88308794A EP88308794A EP0344378A1 EP 0344378 A1 EP0344378 A1 EP 0344378A1 EP 88308794 A EP88308794 A EP 88308794A EP 88308794 A EP88308794 A EP 88308794A EP 0344378 A1 EP0344378 A1 EP 0344378A1
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EP
European Patent Office
Prior art keywords
iridium
tantalum
oxide
electrode
platinum
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
EP88308794A
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German (de)
English (en)
Other versions
EP0344378B1 (fr
Inventor
Yukio Kawashima
Hiroyuki Nakada
Kazuhide Ohe
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.)
TDK Corp
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TDK Corp
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Publication date
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Publication of EP0344378A1 publication Critical patent/EP0344378A1/fr
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Publication of EP0344378B1 publication Critical patent/EP0344378B1/fr
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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02Electrodes; Connections thereof
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091Electrodes 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
    • C25B11/093Electrodes 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 relates to a novel oxygen-generating electrode and to a method for the preparation thereof. More particularly, the invention relates to an electrode which has an excellent durability and low oxygen overvoltage for generating oxygen by the electrolytic oxidation of an aqueous solution at an anode, as well as to a method for the preparation thereof.
  • Conventional metallic electrodes widely used in the electrolytic industry include those prepared by providing a coating layer of a platinum group metal or an oxide thereof on an electroconductive substrate made of titanium metal.
  • known electrodes used as anodes for producing chlorine by the electrolysis of brine include those prepared by providing a titanium substrate with a coating layer formed from an oxide mixture of ruthenium and titanium, or an oxide mixture of ruthenium and tin (see, for example, Japanese Patent Publications 46-21884, 48-3954 and 50-11330).
  • oxygen-generating electrolytic processes require electrodes which are different from the electrodes successfully used in the electrolytic processes accompanied by the generation of chlorine.
  • an electrode for the chlorine-generating electrolysis such as the above mentioned titanium-based electrode having a coating layer of an oxide mixture of ruthenium and titanium or ruthenium and tin
  • the electrolysis must be discontinued due to the rapid corrosion of the electrode.
  • the electrodes must be specialized for the particular electrolytic processes.
  • the electrodes most widely used in oxygen-generating electrolysis are lead-based electrodes and soluble zinc anodes, although other known and usable electrodes include iridium oxide and platinum-based electrodes, iridium oxide and tin oxide-based electrodes and platinum-plated titanium electrodes.
  • An electrode having an intermediate layer provided as mentioned above is not as effective as desired when the electrode is used in an electrolytic process at a high current density because the electroconductivity of the intermediate layer is usually lower than the overcoating layer.
  • Japanese Patent Kokai 56-123388 and 56-123389 disclose an electrode having an undercoating layer containing iridium oxide and tantalum oxide on an electroconductive metal substrate and an overcoating layer of lead dioxide.
  • the undercoating layer in this electrode serves merely to improve the adhesion between the substrate surface and the overcoating layer of lead dioxide to exhibit some effectiveness in preventing corrosion due to pin holes.
  • disadvantages are cause because of the insufficient effect of preventing formation of titanium oxide and the unavoidable contamination of the electrolyte solution with lead.
  • the electrode of the present invention suitable for use in an oxygen-generating electrolytic process is an integral body composed of:
  • the above defined coating layer formed of the ternary mixture is provided with an over-coating layer of iridium oxide or a mixture of iridium oxide and a minor amount, e.g., 50% by moles or less as metals, of tantalum oxide.
  • the electrode of the invention has a basic structure in which an electroconductive substrate of a metal such as titanium is provided with a coating layer formed of a ternary mixture composed of iridium oxide, tantalum oxide and platinum in the elementary form.
  • a coating layer of a ternary mixture can be formed by coating the substrate surface with a coating solution containing an iridium compound, a tantalum compound and a platinum compound each of which decomposes on heating, followed by a heat treatment in an oxidizing atmosphere to convert the thermally decomposable iridium and tantalum compounds into the respective oxides and the platinum compound into elementary platinum.
  • the metal from which the electroconductive substrate is formed examples include so-called valve metals such as titanium, tantalum, zirconium and niobium as well as alloys of these metals.
  • the substrate is made of titanium metal.
  • the substrate shaped from these metals or alloys in an appropriate form of electrode is provided as mentioned above with a coating layer of the ternary mix­ture.
  • thermally decomposable compounds of iridium and tantalum convertible into the respective oxides include chloroiridic acid H2IrCl6 ⁇ 6H2O and tantalum halides and tantalum alkoxides, e.g., tantalum pentaethoxide Ta(OC2H5)5 and tantalum pentabutoxide Ta(OC4H9)5, respec­tively, and suitable platinum compounds include chloro­platinic acid H2PtCl6 ⁇ 6H2O.
  • the coating solution can be prepared by dissolving these compounds in a suitable organic solvent such as butyl alcohol in such a proportion as to give a coating layer of the ternary mixture in which the molar proportions of iridium oxide, tantalum oxide and elementary platinum calculated as respective metals are in the ranges from 40% to 90% for iridium, from 50% to 10% for tantalum and from 0.1% to 30% for platinum.
  • a suitable organic solvent such as butyl alcohol
  • the proportion of the tantalum oxide is too large, the overvolt­age on the electrode increases and adhesion between the substrate surface and the coating layer may be somewhat decreased.
  • the substrate coated with the coating solution is dried and subjected to heat treatment for 1 to 30 minutes at a temperature in the range from 400 to 550 °C in an oxidizing atmosphere of oxygen, such as air.
  • the atmosphere for the heat treatment is not fully oxidi­zing, the compounds of iridium and tantalum can be oxidized into the respective oxides only incompletely to leave an amount of metallic constituents badly influencing the durability of the electrode.
  • the thickness or coating amount of the coating layer is not particularly limited but it should be at least 0. 1 mg/cm2 calculated as iridium metal. When the coating amount is too small, insufficient protection of the substrate surface is obtained. If necessary, the cycle of coating with the coating solution and heat treatment to effect thermal decomposition of the metal compounds is repeated several times until the coating amount of the oxide mixture has reached the above mentioned prefered range.
  • the coating layer is formed from the ternary mixture of iridium and tantalum oxides and elementary platinum, it is preferable that the coating layer is further coated with an overcoating layer of iridium oxide optionally admixed with a minor amount of tantalum oxide in order to decrease consumption of the electrode in the electrolytic process.
  • the coating amount of the overcoating layer should be in the range from 0.02 to 5 mg/cm2 calculated as iridium metal.
  • the coating amount of the overcoating layer is too small, no desired effect as mentioned above can be obtained to affect the durability of the electrode.
  • the coating amount of the overcoating layer is too large, on the other hand, an adverse influence is that the adhesive strength of the active electrode film is decreased.
  • the procedure for providing the overcoating layer of iridium oxide, optionally, admixed with tantalum oxide is similar to the procedure for forming the ternary mixed coating layer of iridium and tantalum oxides and elementary platinum.
  • a thermally decomposable iridium compound such as chloroiridic acid and, optionally, a tantalum compound are dissolved in an organic solvent and the substrate surface provided with the undercoating layer of ternary mixture is coated with the solution, dried and subjected to a heat treatment for 1 to 30 minutes at a temperature in the range from 400 to 550 °C in an oxidizing atmosphere.
  • the cycle of coating with the solution of the metal compound or compounds and heat treatment may be repeated several times until the coating amount has reached the desired range mentioned above.
  • the molar proportion of tantalum oxide relative to the oxide mixture should not exceed 50% calculated as metals.
  • Seven coating solutions were prepared for the elec­trodes No. 1 to No. 7 each by dissolving chloroiridic acid H2IrCl6 ⁇ 6H2O, chloroplatinic acid H2PtCl6 ⁇ 6H2O and tantalum pentaethoxide Ta(OC2H5)5 in n-butyl alcohol each in such an amount that the total concentration thereof corresponded to 80 g of the metals per liter but with varied molar proportion of iridium:platinum:tantalum as metals (Ir:Pt:Ta) indicated in Table 1 below.
  • An electrode substrate made of titanium metal after an etching treatment using a hot aqueous solution of oxalic acid was coated by brushing with either one of the coating solutions prepared above and, after drying, subjected to a heat treatment at 500 °C in an electric oven into which air was blown. This procedure of coating with the coating solution, drying and a heat treatment in air was repeated several times until the coating amount of the coating layer had reached 0.05 to 10 mg/cm2 calculated as iridium metal to give 12 electrodes No. 1 to No. 12.
  • Electrodes were subjected to the measurement of the oxygen overvoltage by the potential scanning method in a 1 mole/liter aqueous solution of sulfuric acid at 30 °C with a current density of 20 A/dm2. The results are shown in Table 1. Further, the electrodes were subjected to the durability test as the anode for electrolysis of a 1 mole/liter aqueous solution of sulfuric acid at 60 °C using a platinum electrode as the cathode with a current density of 200 A/dm2 to give the results that the durability or the serviceable life was at least 2000 hours for each of the electrodes No. 1 to No. 7 while the life was between 1000 and 2000 hours for the electrode No. 11 and less than 1000 hours for the electrodes No. 8, No. 9, No.
  • Example 1 Nine titanium-made electrode substrates for electrodes No. 13 to No. 21 were coated each with either one of the coating solutions prepared in Example 1 indicated in Table 2 below to be provided with the undercoating layer of a ternary mixture in the same manner as in Example 1.
  • coating solutions for overcoating were prepared each by dissolving chloroiridic acid H2IrCl6 ⁇ 6H2O alone or chloroiridic acid and tantalum penta­butoxide Ta(OC4H9)5 or tantalum pentaethoxide Ta(OC2H5)5 in n-butyl alcohol each in such an amount that the molar ratio of iridium to tantalum as metals (Ir:Ta) was as indicated in Table 2 and the total concentration thereof corresponded to 80 g of the metals per liter.
  • the electrode bodies provided with the undercoating layer were each coated with either one of the above prepared overcoating solutions, dried and subjected to a heat treat­ment at 500 °C in an electric oven into which air was blown.
  • the procedure of coating with the coating solution, drying and a heat treatment was repeated several times to give an overcoating layer of iridium oxide or a mixture of iridium oxide and tantalum oxide in a coating amount of 0.01 to 8 mg/cm2 as iridium metal.
  • the thus prepared dually coated electrodes were sub­jected to the measurement of the oxygen overvoltage in the same manner as in Example 1 to give the results shown in Table 2. Further, they were subjected to the durability test for electrolysis in the same manner as in Example 1 to give the results that the durability or serviceable life was at least 2000 hours for each of the electrodes No. 13 to No. 18 and between 1000 and 2000 hours for each of the electrodes No. 19 to No. 21.
  • Table 2 Electrode No. Undercoating, the same as in electrode No.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP88308794A 1988-05-31 1988-09-22 Electrode pour la production d'oxygène et son procédé de préparation Expired EP0344378B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP63131374A JPH0660427B2 (ja) 1988-05-31 1988-05-31 酸素発生用電極及びその製造方法
JP131374/88 1988-05-31

Publications (2)

Publication Number Publication Date
EP0344378A1 true EP0344378A1 (fr) 1989-12-06
EP0344378B1 EP0344378B1 (fr) 1992-06-17

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EP88308794A Expired EP0344378B1 (fr) 1988-05-31 1988-09-22 Electrode pour la production d'oxygène et son procédé de préparation

Country Status (4)

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EP (1) EP0344378B1 (fr)
JP (1) JPH0660427B2 (fr)
CA (1) CA1335496C (fr)
DE (1) DE3872228T2 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2239260A (en) * 1989-12-22 1991-06-26 Tdk Corp Oxygen-generating electrolysis electrode and method for the preparation thereof
EP0531264A2 (fr) * 1991-08-30 1993-03-10 Permelec Electrode Ltd Electrode pour électrolyse
EP0545869A1 (fr) * 1991-11-28 1993-06-09 Permelec Electrode Ltd Electrode d'électrolyse
EP0560338A2 (fr) * 1992-03-11 1993-09-15 TDK Corporation Electrode pour dégagement d'oxygène
EP0715002A1 (fr) * 1994-11-30 1996-06-05 The Dow Chemical Company Solutions de revêtement stables pour la préparation de revêtements électrocatalytiques d'oxydes mixtes sur des substrats métalliques ou revêtus de métaux et anodes dimensionnellement stables obtenues à partir des ces solutions
WO2000060141A1 (fr) * 1999-04-08 2000-10-12 United States Filter Corporation Anode triple couche et son procede de fabrication
US6572758B2 (en) 2001-02-06 2003-06-03 United States Filter Corporation Electrode coating and method of use and preparation thereof
US9353448B2 (en) 2010-09-17 2016-05-31 Tanaka Kikinzoku Kogyo K.K. Electrolytic electrode, anode for electrolytic production of ozone, anode for electrolytic production of persulfuric acid and anode for electrolytic oxidation of chromium
CN116219470A (zh) * 2023-03-28 2023-06-06 广东卡沃罗氢科技有限公司 具有双层阳极涂层的膜电极及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2004277578B2 (en) * 2003-10-08 2008-07-17 Akzo Nobel N.V. Electrode
JP7396391B2 (ja) * 2022-03-31 2023-12-12 Toto株式会社 次亜塩素酸生成電極

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2099019A (en) * 1981-05-19 1982-12-01 Permelec Electrode Ltd Electrolytic electrode having high durability
GB2134544A (en) * 1983-01-31 1984-08-15 Permelec Electrode Ltd Electrolysis electrodes
EP0243302A1 (fr) * 1986-04-17 1987-10-28 Eltech Systems Corporation Eléctrode contenant du platine métallique comme catalyseur dans une pellicule superficielle et son application

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56123388A (en) * 1980-02-29 1981-09-28 Asahi Chem Ind Co Ltd Lead dioxide electrode
JPS6022074B2 (ja) * 1982-08-26 1985-05-30 ペルメレツク電極株式会社 耐久性を有する電解用電極及びその製造方法
JPS63286198A (ja) * 1987-05-19 1988-11-22 松下電器産業株式会社 スチ−ムアイロン
JP2679282B2 (ja) * 1989-08-04 1997-11-19 松下電器産業株式会社 コードレススチームアイロン
JPH03106339A (ja) * 1989-09-19 1991-05-02 Hitachi Medical Corp 磁気共鳴イメージング装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2099019A (en) * 1981-05-19 1982-12-01 Permelec Electrode Ltd Electrolytic electrode having high durability
GB2134544A (en) * 1983-01-31 1984-08-15 Permelec Electrode Ltd Electrolysis electrodes
EP0243302A1 (fr) * 1986-04-17 1987-10-28 Eltech Systems Corporation Eléctrode contenant du platine métallique comme catalyseur dans une pellicule superficielle et son application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 5, no. 204 (C-85)[876], 24th December 1981; & JP-A-56 123 388 (ASAHI KASEI KOGYO K.K.) 28-09-1981 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2656337A1 (fr) * 1989-12-22 1991-06-28 Tdk Corp Electrode generatrice d'oxygene et procede pour sa preparation.
GB2239260A (en) * 1989-12-22 1991-06-26 Tdk Corp Oxygen-generating electrolysis electrode and method for the preparation thereof
GB2239260B (en) * 1989-12-22 1994-02-16 Tdk Corp Oxygen-generating electrode and method for the preparation thereof
EP0531264A3 (fr) * 1991-08-30 1995-04-05 Permelec Electrode Ltd
EP0531264A2 (fr) * 1991-08-30 1993-03-10 Permelec Electrode Ltd Electrode pour électrolyse
EP0545869A1 (fr) * 1991-11-28 1993-06-09 Permelec Electrode Ltd Electrode d'électrolyse
US6103299A (en) * 1991-11-28 2000-08-15 Permelec Electrode Limited Method for preparing an electrode for electrolytic processes
US5354444A (en) * 1991-11-28 1994-10-11 Permelec Electrode Ltd. Electrode for electrolytic processes
EP0560338A2 (fr) * 1992-03-11 1993-09-15 TDK Corporation Electrode pour dégagement d'oxygène
EP0560338A3 (fr) * 1992-03-11 1994-01-05 Tdk Corp
EP0715002A1 (fr) * 1994-11-30 1996-06-05 The Dow Chemical Company Solutions de revêtement stables pour la préparation de revêtements électrocatalytiques d'oxydes mixtes sur des substrats métalliques ou revêtus de métaux et anodes dimensionnellement stables obtenues à partir des ces solutions
WO2000060141A1 (fr) * 1999-04-08 2000-10-12 United States Filter Corporation Anode triple couche et son procede de fabrication
US6217729B1 (en) 1999-04-08 2001-04-17 United States Filter Corporation Anode formulation and methods of manufacture
US6572758B2 (en) 2001-02-06 2003-06-03 United States Filter Corporation Electrode coating and method of use and preparation thereof
US9353448B2 (en) 2010-09-17 2016-05-31 Tanaka Kikinzoku Kogyo K.K. Electrolytic electrode, anode for electrolytic production of ozone, anode for electrolytic production of persulfuric acid and anode for electrolytic oxidation of chromium
CN116219470A (zh) * 2023-03-28 2023-06-06 广东卡沃罗氢科技有限公司 具有双层阳极涂层的膜电极及其制备方法
CN116219470B (zh) * 2023-03-28 2024-04-02 广东卡沃罗氢科技有限公司 具有双层阳极涂层的膜电极及其制备方法

Also Published As

Publication number Publication date
EP0344378B1 (fr) 1992-06-17
CA1335496C (fr) 1995-05-09
DE3872228D1 (de) 1992-07-23
DE3872228T2 (de) 1992-12-03
JPH0660427B2 (ja) 1994-08-10
JPH01301876A (ja) 1989-12-06

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