• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention provides an electrode having a coating made of electrocatalytic ceramic materials on substantially incompatible metal substrates, by resorting to the use of an anchoring pre-coating or interlayer, applied over the metal substrate advantageously by galvanic electrodeposition, said pre-coating generally consisting of an inert metallic matrix containing particles of a ceramic material which preferably is compatible or even isomorphous with respect to the ceramic material constituting the superficial or external electrocatalytic coating. Adhesion to the metal substrate and electrical conductivity through the coating result thereby greatly improved. Further, the electrolysis of sodium chloride in cells provided with the electrode of the present invention is more efficient and less problematic.
    公开号:SU1530102A3
    申请号:SU853971971
    申请日:1985-11-04
    公开日:1989-12-15
    发明作者:Пеллегри Альберто
    申请人:Оронцио Де Нора Импианти Элеттрокимичи С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to electrodes for electrochemical processes and can be used in the electrolysis of alkali metal halides.
    The aim of the invention is to increase the service life of the cathode.
    The goal is achieved due to the fact that in the cathode containing an electrically conductive substrate, an intermediate layer and an electrocatalytic coating, the intermediate layer consists of a metal selected from the group of nickel, iron, copper, chromium, silver, cobalt, or their alloy and contains dispersed in it particles of oxide or mixed oxides of ruthenium, iridium, titanium, tantalum, hafnium, niobium and cerium in an amount of 3-15 wt., particle size 0.2-30 μm, and the thickness of the intermediate layer 2-30 μm. The electrocatalytic coating is applied in the amount of 2-20 g7 m2.
    Example 1. Several samples of nets made of Ni + debris wire with a diameter of 0.1 mm are subjected to steam degreasing and washing in solution containing 15% hydrochloric acid for about 60 s. These nickel meshes are used as substrates for electrodeposition from a coating bath having the following composition, g / l: nickel sulfate 200; hloSP
    WITH

    cm
    3130
    REED nickel 50; boric acid 0; powder mixed with ruthenium oxides and with a ratio between metals of 10: 1-10.
    The bath has a temperature of approximately 50 mA / cm current density, powdered particles of mixed oxides have an average diameter of about 2 microns, a minimum diameter of 0.5 microns, and a maximum diameter of 6 microns.
    The powder is maintained as a suspension in a bath due to mechanical agitation and electroplating lasts about 20 minutes.
    The thickness of the adhered precoat applied is about 15 microns and about 10% of the coating contains mixed oxide particles uniformly distributed throughout the nickel matrix.
    The mixed oxide particles on the surface of the precoat are only partially coated with nickel. Thus, some part of the surface 25 Contains uncoated particles or surfaces. Nickel coating is dendritic.
    After rinsing in deionized water and drying to the surface of one of,. the coated samples are applied to an aqueous solution of the composition: ruthenium chloride (on metal) 10 g; titanium chloride (by metal) 1 g; hydrogen peroxide aqueous solution 50 aqueous solution
    hydrochloric acid 150 cm.
    After drying at 60 ° C for about 10 minutes, the sample is heated in an oven in an air atmosphere for 10 minutes, and the device is cooled to room temperature.
    Using a scanning microscopy method, it has been established that a surface oxide layer is formed, which is determined by X-ray diffraction as a solid solution of ruthenium oxide and titanium.
    The thickness of the surface oxide coating is about 2 µm, and the amount determined by weighing is about k g / m2 of the surface.
    On other samples coated with an adherent pre-coat or intermediate layer deposited by electroplating, the molding process of the mixed oxide surface coating is repeated 3 times, thereby forming a surface ceramic coating of about 12 g / m
    d
    with
    about
    five
    ,
    five
    0
    five
    ABOUT
    024
    Electrodes thus manufactured are tested as cathodes for hydrogen evolution in a 35% solution of caustic soda (KaOH) at 80 ° C and with a change in current density from 500 A / m2 to 5000 A / m. For each sample obtained, a Tafel dependence is constructed. For the purpose of comparison, a sample was tested as a cathode under the same conditions, which was only bonded with a preliminary coating or an intermediate layer deposited by electroplating.
    The electrode coated with 12 g / m of oxide has a voltage relative to a calomel electrode of comparison 1.175 E (SCK) at 500 A / m and a Tafel slope of approximately 35 mV / decade of current.
    The electrode with a surface coating (only A g / m2) has a voltage relative to the calomel electrode of comparison I, l80 V (SCE) at 500 A / m2.
    The comparative electrode without a surface oxide coating has a voltage relative to a calomel reference electrode of 1,205 V (SCE) at 500 A / m and a Tafel slope of approximately 85 mV / decade of current.
    For the sake of comparison, mixed ruthenium-titanium oxide in a ceramic coating is applied to an intermediate nickel grid in the same way as to obtain electrodes in accordance with the invention, but without first applying a galvanic pre-coating or intermediate layer on the substrate. An oxide coating of about 6 g / m is formed.
    When tested under similar conditions, this electrode has a voltage relative to a calomel reference electrode of about 1.85 V (SCE) at 500 A / m and a Tafel inclination of about 5C mV / decade of current.
    Although the catalytic activity as a result is almost the same when compared with the electrodes made in accordance with the invention, very poor adhesion is observed. Shaking the power of the coated surface is sufficient to cause removal of the applied ceramic material.
    In contrast, the surface coating of the electrode in accordance with the invention is well adhesively bonded and has (ligh resistance to tearing it away when
    515
    this resistance by the adhesive tape method.
    EXAMPLE 2. Electrodes are manufactured in the same manner as in Example 1, but using other materials.
    Table B, Table 1 shows the results obtained on different electrodes under the same test conditions as in Example 1.
    EXAMPLE 3t Electrodes in accordance with Example 2 are used as cathodes in laboratory electrolysis cells equipped with Nafipn (R) cation-exchange membranes, supplied by KI Du Tont de nemours, and titanium anodes coated with a coating of a mixture of ruthenium oxides. and titanium.
    An aqueous solution of 200 g / l sodium chloride is loaded into the anode compartment of the electrolysis cell, and deionized water is poured into the cathode compartment, the concentration of NaOl is maintained at about 35%. . The current density is about 200 A / m, the operating temperature is in the range of 85 - 95 ° C.
    I- the first comparative cell, the cathode is made of nickel and is not treated, while in the second comparative cell the cathode is made of nickel coated only with an adherent precoat or intermediate layer containing a nickel matrix containing 2% of ruthenium oxide particles.
    The voltage in a cell equipped with cathodes manufactured in accordance with the invention is about 0.2 V less than in the first comparative cell and about 0.06 V less than in the second comparative cell.
    After 3000 hours of operation, the voltage in a cell equipped with electrodes manufactured in accordance with the invention did not actually change, the difference with respect to the first comparative cell decreased to approximately 0.12 V, while the difference with respect to the second comparative cell increased to approximately 0.1 V, Cathodes in accordance with the invention
    five
    five
    ABOUT
    Q 5
    l
    five
    026
    The alloy was unchanged, while the untreated nickel cathode, as well as the nickel cathode, covered only with a preliminary layer or an intermediate layer, electroplated, looked black from the precipitated sediment, which, according to the analysis, consists of iron and iron oxide .
    Table 2 shows data on four types of cathodes, made with consideration of the parameters of the present invention.
    All samples were thermally decomposed as in Example 1 to form a surface mixed oxide and tested under the conditions of Example 1. The first three samples show high catalytic activity and good adhesion of the coating to the substrate. The fourth sample has a higher voltage.
    Thus, the cathode for electrochemical processes of this invention is characterized by high adhesion of the coating to the substrate, so that its service life while maintaining a large catalytic activity is much more known.
    权利要求:
    Claims (2)
    [1]
    1.Katbd for electrochemical processes, containing an electrically conductive substrate of iron, nickel, copper, silver, cobalt or stainless steel, an intermediate layer and an electrocatalytic coating of oxide or mixture of ruthenium oxide, iridium and titanium, characterized in that
    In order to increase the service life of the cathode, the intermediate layer is made of a metal selected from the group: nickel, iron, copper, chromium, silver, cobalt, or their alloys and contains dispersed in it particles of oxide or mixed ruthenium, iridium, titanium, tantalum , hafni, niobium and cerium in the amount of 3-15 May. o, and the particle size is 0.2-30 µm, and the thickness of the intermediate layer is 2-ES micrometer.
    [2]
    2. The cathode according to claim 1, characterized in that it contains an electrocatalytic coating in the amount of 2-20 g / m2.
    Table 1
    0.1-0.3 8-12
    ten
    Compiled by N. Chilikin Editor 0. The Experts Tehred L. Serdyukov Proofreader M. Pojo
    Order 7767/59
    Circulation 605
    VNI.IPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab, d.
    Production and Publishing Combine Patent, Uzhgorod, Gagarin st., 101
    25-32 30-38 30 35 8 12
    Subscription
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    JPS5511753B2|1976-12-24|1980-03-27|
    US4222828A|1978-06-06|1980-09-16|Akzo N.V.|Process for electro-codepositing inorganic particles and a metal on a surface|
    US4100049A|1977-07-11|1978-07-11|Diamond Shamrock Corporation|Coated cathode for electrolysis cells|
    JPS6015713B2|1977-11-18|1985-04-20|Showa Denko Kk|
    US4235695A|1977-12-09|1980-11-25|Diamond Shamrock Technologies S.A.|Novel electrodes and their use|
    JPS5948872B2|1978-02-20|1984-11-29|Kurorin Engineers Kk|
    JPS54112785A|1978-02-24|1979-09-03|Asahi Glass Co Ltd|Electrode and manufacture thereof|
    JPS55500123A|1978-03-28|1980-03-06|
    FR2421156B1|1978-03-30|1982-06-04|Commissariat Energie Atomique|
    US4157943A|1978-07-14|1979-06-12|The International Nickel Company, Inc.|Composite electrode for electrolytic processes|
    RO76965A2|1979-10-09|1981-08-30|Combinatul Chimic,Ro|ELECTRODE WITH SEMICONDUCTOR ELECTROCATALYTIC CERAMIC SURFACES AND METHOD FOR OBTAINING|
    US4421626A|1979-12-17|1983-12-20|Occidental Chemical Corporation|Binding layer for low overvoltage hydrogen cathodes|
    EP0031948B1|1979-12-26|1986-10-15|Asahi Kasei Kogyo Kabushiki Kaisha|A hydrogen-evolution electrode|
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    US4455211A|1983-04-11|1984-06-19|Aluminum Company Of America|Composition suitable for inert electrode|MX169643B|1985-04-12|1993-07-16|Oronzio De Nora Impianti|ELECTRODE FOR ELECTROCHEMICAL PROCESSES, PROCEDURE FOR ITS PRODUCTION AND ELECTROLYSIS TANK CONTAINING SUCH ELECTRODE|
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    US5035789A|1990-05-29|1991-07-30|The Dow Chemical Company|Electrocatalytic cathodes and methods of preparation|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT8483633A|IT1208128B|1984-11-07|1984-11-07|ELECTRODE FOR USE IN ELECTROCHEMICAL CELLS, PROCEDURE FOR ITS PREPARATION AND USE IN THE ELECTROLYSIS OF DISODIUM CHLORIDE.|
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