EP3842571A1 - Anode de synthèse électrolytique et procédé de production de gaz fluoré - Google Patents

Anode de synthèse électrolytique et procédé de production de gaz fluoré Download PDF

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EP3842571A1
EP3842571A1 EP19851407.7A EP19851407A EP3842571A1 EP 3842571 A1 EP3842571 A1 EP 3842571A1 EP 19851407 A EP19851407 A EP 19851407A EP 3842571 A1 EP3842571 A1 EP 3842571A1
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Prior art keywords
anode
electrolytic
mass
iron
carbon
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EP3842571B1 (fr
EP3842571A4 (fr
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Yohsuke Fukuchi
Shinya Oguro
Hiroshi Kobayashi
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Resonac Corp
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Showa Denko KK
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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
    • C25B11/042—Electrodes formed of a single material
    • C25B11/046—Alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
    • 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
    • C25B1/24—Halogens or compounds thereof
    • C25B1/245—Fluorine; Compounds thereof
    • 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
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • 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
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • 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
    • C25B11/083—Diamond
    • 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
    • C25B11/089—Alloys

Definitions

  • the present invention relates to an anode for electrolytically synthesizing fluorine gas or a fluorine containing compound and a method for electrolytically synthesizing fluorine gas or a fluorine containing compound.
  • Fluorine gas and a fluorine containing compound can be synthesized by electrolyzing (electrolytic synthesis) an electrolytic solution containing fluoride ions.
  • electrolyzing electrolytic synthesis
  • a carbon electrode has been generally used as an anode.
  • the use of the carbon electrode has posed a problem that a voltage of an electrolytic cell required to obtain a predetermined current becomes a high voltage exceeding 12 V even when electrolyzed with an extremely low current density in some cases. This phenomenon is referred to as an anode effect.
  • a cause of the occurrence of the anode effect is as follows.
  • fluorine gas generated on the surface of the anode reacts with the carbon forming the anode, and therefore a coating film having a covalently bonded carbon-fluorine bond is formed on the surface of the anode.
  • the coating film have insulation properties and poor wettability with the electrolytic solution, and therefore a current is difficult to flow to the anode, so that the anode effect occurs. Then, when the anode effect progresses, continuous electrolysis becomes impossible in some cases.
  • a metal electrode as the anode has posed a problem that the metal electrode is dissolved or a problem that, due to the formation of an insulating coating film containing oxide or fluoride on the surface of the metal electrode, a current is difficult to flow, so that the power consumption increases in some cases.
  • the present invention can electrolytically synthesize fluorine gas or a fluorine containing compound with a low power consumption while suppressing electrolytic resistance.
  • FIG. 1 is a cross-sectional view illustrating an electrolytic device virtually cut along a plane orthogonal to and parallel in the vertical direction to the plate surfaces of an anode for electrolytic synthesis 3 and cathodes for electrolytic synthesis 5 of the electrolytic device.
  • FIG. 2 is a cross-sectional view illustrating the electrolytic device virtually cut along a plane parallel to and parallel in the vertical direction to the plate surfaces of the anode for electrolytic synthesis 3 and the cathodes for electrolytic synthesis 5 of the electrolytic device.
  • the electrolytic device illustrated in FIGS. 1 , 2 includes an electrolytic cell 1 in which an electrolytic solution 10 is stored and the anode for electrolytic synthesis 3 and the cathodes for electrolytic synthesis 5 arranged in the electrolytic cell 1 and immersed in the electrolytic solution 10.
  • the inside of the electrolytic cell 1 is partitioned into an anode chamber 12 and a cathode chamber 14 by a cylindrical partition 7 extending downward in the vertical direction from a lid 1a of the electrolytic cell 1. More specifically, an inner region surrounded by the cylindrical partition 7 is the anode chamber 12 and a region outside the cylindrical partition 7 is the cathode chamber 14.
  • the anode for electrolytic synthesis 3 is not limited in shape and may have a columnar shape and, in this example, has a plate shape.
  • the anode for electrolytic synthesis 3 is arranged in the anode chamber 12 such that the plate surfaces thereof are parallel to each other in the vertical direction.
  • the cathodes for electrolytic synthesis 5 have a plate shape and are arranged in the cathode chamber 14 such that the plate surfaces thereof are parallel to the plate surfaces of the anode for electrolytic synthesis 3 and the two cathodes for electrolytic synthesis 5, 5 interpose the anode for electrolytic synthesis 3 therebetween.
  • cooling units for cooling the cathodes for electrolytic synthesis 5, 5 and the electrolytic solution 10 are mounted on the plate surfaces opposite to the plate surfaces facing the anode for electrolytic synthesis 3 among both the front and rear plate surfaces of the cathodes for electrolytic synthesis 5, 5.
  • a cooling pipe 16 in which a cooling fluid flows is mounted as the cooling unit on each of the cathodes for electrolytic synthesis 5, 5.
  • the anode for electrolytic synthesis 3 is an electrode including an anode substrate 31 formed of a metallic material and a carbonaceous layer 33 formed of a carbonaceous material and arranged on the surface of the anode substrate 31 as illustrated in FIG. 3 .
  • the metallic material forming the anode substrate 31 is an iron-based alloy containing iron and nickel.
  • the iron-based alloy may be an alloy containing iron, nickel, and inevitable impurities or may be an alloy containing iron, nickel, and the other alloy components.
  • the iron-based alloy in the present invention means an alloy containing iron as a main component, i.e., an alloy in which the content of iron among alloy components is the highest.
  • the electrical resistance of metal is far lower than the electrical resistance of carbon and is one several tenths to one several hundredths of the electrical resistance of carbon. Therefore, when a metal substrate is adopted as a substrate of the anode for electrolytic synthesis 3 (anode substrate 31), electrolytic resistance in electrolytic synthesis can be made low.
  • an iron-based alloy having a specific alloy composition is used for the metallic material forming the anode substrate 31, the electrolytic resistance of the carbonaceous layer 33 arranged on the surface of the anode substrate 31 can be suppressed to a low level.
  • fluorine gas or a fluorine containing compound can be electrolytically synthesized with a low power consumption while suppressing the electrolytic resistance.
  • the anode for electrolytic synthesis 3 of this embodiment is hard to cause the breakage by electrolysis, and therefore can perform stable electrolytic synthesis.
  • the maintenance frequency can be sharply reduced.
  • a carbonaceous layer can be formed on the surface. Therefore, insofar as the anode substrate does not disappear, the anode can be continuously used by forming the carbonaceous layer on the surface.
  • fluorine containing compounds such as uranium hexafluoride (UF 6 ), sulfur hexafluoride (SF 6 ), carbon tetrafluoride (CF 4 ), and nitrogen trifluoride
  • UF 6 uranium hexafluoride
  • SF 6 sulfur hexafluoride
  • CF 4 carbon tetrafluoride
  • nitrogen trifluoride can also be chemically synthesized using the electrolytically synthesized fluorine gas as a starting material.
  • the fluorine gas or the fluorine containing compounds, such as uranium hexafluoride, sulfur hexafluoride, carbon tetrafluoride, and nitrogen trifluoride are useful in the nuclear industry field, the semiconductor industry field, the pharmaceutical and agrochemical field, the consumer product field, and the like.
  • the carbonaceous material forming the carbonaceous layer 33 is not particularly limited insofar as the material contains carbon.
  • Examples of the carbon contained in the carbonaceous layer 33 include crystalline carbon, such as diamond and graphite, amorphous carbon, such as carbon black, carbon nanotube, graphene, diamond-like carbon, and the like.
  • the carbonaceous material forming the carbonaceous layer 33 may be a material containing only carbon or may be a material containing a mixture of carbon and other components (for example, mixture of carbon and metal or a mixture of carbon and ceramic).
  • the carbonaceous material is the mixture of carbon and metal
  • the metal may be metal (iron, nickel, cobalt, and the like) contained in the metallic material forming the anode substrate 31.
  • the carbon content in the carbonaceous material is preferably higher than the carbon content in the metallic material forming the anode substrate 31 and less than 100 mass%.
  • the carbon content in the carbonaceous material is preferably more than 0 mass% and less than 100 mass%.
  • the carbon content in the carbonaceous material is preferably more than 1.5 mass% and less than 100 mass%.
  • the nickel content in the iron-based alloy containing iron and nickel is not particularly limited and is preferably set to 32 mass% or more and 40 mass% or less and more preferably set to 34 mass% or more and 38 mass% or less in order to suppress the electrolytic resistance of the carbonaceous layer 33 to a lower level.
  • an iron-based alloy containing iron, nickel, and cobalt is also usable.
  • the iron-based alloy may be an alloy containing iron, nickel, cobalt, and inevitable impurities or may be an alloy containing iron, nickel, cobalt, and the other alloy components.
  • the nickel content in the iron-based alloy containing iron, nickel, and cobalt is not particularly limited and is preferably set to 30 mass% or more and 38 mass% or less and more preferably set to 31 mass% or more and 35 mass% or less in order to suppress the electrolytic resistance of the carbonaceous layer 33 to a lower level.
  • the cobalt content in the iron-based alloy containing iron, nickel, and cobalt is not particularly limited and is preferably set to 3 mass% or more and 12 mass% or less and more preferably set to 4 mass% or more and 7 mass% or less in order to suppress the electrolytic resistance of the carbonaceous layer 33 to a lower level.
  • an iron-based alloy containing iron, nickel, cobalt, and carbon is also usable.
  • the iron-based alloy may be an alloy containing iron, nickel, cobalt, carbon, and inevitable impurities or may be an alloy containing iron, nickel, cobalt, carbon, and the other alloy components.
  • the nickel content in the iron-based alloy containing iron, nickel, cobalt, and carbon is not particularly limited and is preferably set to 20 mass% or more and 36 mass% or less and more preferably set to 21 mass% or more and 28 mass% or less in order to suppress the electrolytic resistance of the carbonaceous layer 33 to a lower level.
  • the cobalt content in the iron-based alloy containing iron, nickel, cobalt, and carbon is not particularly limited and is preferably set to 3 mass% or more and 20 mass% or less and more preferably set to 6 mass% or more and 16 mass% or less in order to suppress the electrolytic resistance of the carbonaceous layer 33 to a lower level.
  • the carbon content in the iron-based alloy containing iron, nickel, cobalt, and carbon is not particularly limited and is preferably set to 0.01 mass% or more and 1.5 mass% or less and more preferably set to 0.5 mass% or more and 1.0 mass% or less in order to suppress the electrolytic resistance of the carbonaceous layer 33 to a lower level.
  • the carbonaceous layer 33 may have a single layer structure illustrated in FIG. 3 or may have a double layer structure illustrated in FIG. 4 . More specifically, the carbonaceous layer 33 may contain an inner layer 331 in contact with the anode substrate 31 and an outer layer 332 outside the inner layer 331.
  • the inner layer 331 is a layer in which at least one of metals (iron, nickel, cobalt, and the like) constituting the iron-based alloy forming the anode substrate 31 and carbon coexist and the outer layer 332 is a layer formed of carbon.
  • the inner layer 331 contains metal and carbon constituting the iron-based alloy forming the anode substrate 31 as described above.
  • the carbon content in the inner layer 331 is preferably higher than the carbon content in the metallic material forming the anode substrate 31 and less than 100 mass%.
  • the carbon content in the inner layer 331 is preferably more than 0 mass% and less than 100 mass%.
  • the carbon content in the inner layer 331 is preferably more than 1.5 mass% and less than 100 mass%.
  • a method for forming the carbonaceous layer 33 on the surface of the anode substrate 31 is not particularly limited. In a case of the carbonaceous layer 33 having the single layer structure illustrated in FIG. 3 , a method including forming the carbonaceous layer 33 on the surface of the anode substrate 31 and a method including modifying a top layer portion of the anode substrate 31 and forming the carbonaceous layer 33 are mentioned.
  • Examples of the film formation method include, for example, vacuum deposition methods typified by a resistance heating deposition method and an electron beam deposition method and dry film formation methods, such as a sputtering method, an ion plating method, a hot filament chemical vapor deposition (CVD) method, a microwave plasma CVD method, a plasma arc jet CVD method, and a plasma ion implantation method. It is preferable to form the carbonaceous layer 33 under a condition where the temperature of the anode substrate 31 is a temperature lower than 450°C.
  • Examples of the modification method include an ion implantation method using hydrocarbon-based gas or the like, for example.
  • a method can be adopted, for example, which includes forming the inner layer 331 on the surface of the anode substrate 31 while continuously changing the composition ratio of metal and carbon using the dry film formation methods described above, and then forming the outer layer 332 on the inner layer 331.
  • a method can be adopted, for example, which includes implanting carbon ions into the top layer portion of the anode substrate 31 by the ion implantation method using hydrocarbon-based gas or the like to modify the top layer portion, forming the inner layer 331 in which the composition ratio of metal and carbon continuously changes, and then forming the outer layer 332 on the inner layer 331 by the dry film formation methods described above.
  • a metal electrode is usable and an electrode containing iron is usable, for example.
  • a molten salt is usable and, for example, molten potassium fluoride (KF) containing hydrogen fluoride (HF) is usable.
  • KF molten potassium fluoride
  • HF hydrogen fluoride
  • the anode gas is accumulated in space above the liquid level of the electrolytic solution 10 in the anode chamber 12.
  • the cathode gas is accumulated in space above the liquid level of the electrolytic solution 10 in the cathode chamber 14. Since the space above the liquid level of the electrolytic solution 10 is partitioned by the partition 7 into space in the anode chamber 12 and space in the cathode chamber 14, the anode gas and the cathode gas are not mixed.
  • the anode chamber 12 is provided with an exhaust port 21 discharging the anode gas generated in the anode for electrolytic synthesis 3 from the inside of the anode chamber 12 to the outside of the electrolytic cell 1.
  • the cathode chamber 14 is provided with an exhaust port 23 discharging the cathode gas generated in the cathodes for electrolytic synthesis 5, 5 from the inside of the cathode chamber 14 to the outside of the electrolytic cell 1.
  • a material of an electrolytic cell performing electrolytic synthesis is not particularly limited, it is preferable to use copper, soft steel, Monel (Trademark), nickel alloy, fluororesin, and the like from the viewpoint of corrosion resistance.
  • an anode chamber where the anode for electrolytic synthesis is arranged and a cathode chamber where the cathode for electrolytic synthesis is arranged is entirely or partially partitioned by a partition, a diaphragm, or the like as in the electrolytic device illustrated in FIGS. 1 , 2 .
  • an electrolytic solution used when the fluorine gas is electrolytically synthesized is described.
  • a mixed molten salt of hydrogen fluoride and potassium fluoride is usable as the electrolytic solution.
  • the molar ratio of the hydrogen fluoride and the potassium fluoride in this electrolytic solution can be set to 1.5 to 2.5:1, for example.
  • a mixed molten salt of hydrogen fluoride and cesium fluoride (CsF) and a mixed molten salt of hydrogen fluoride, potassium fluoride, and cesium fluoride are also usable as the electrolytic solution.
  • the composition ratio of the electrolytic solution containing cesium fluoride may be set as follows. More specifically, the molar ratio of the cesium fluoride and the hydrogen fluoride in the electrolytic solution may be set to 1:1.0 to 4.0. The molar ratio of the cesium fluoride, the hydrogen fluoride, and the potassium fluoride in the electrolytic solution may be set to 1:1.5 to 4.0:0.01 to 1.0.
  • an example of an electrolytic solution used when the fluorine containing compound is electrolytically synthesized is described.
  • a mixed molten salt of a compound having a chemical structure before fluorination of a fluorine containing compound to be synthesized, hydrogen fluoride, and potassium fluoride is usable as the electrolytic solution.
  • the electrolytic synthesis may be performed by forming the compound having the chemical structure before fluorination into a gaseous state, and then blowing the compound formed into the gaseous state into a mixed molten salt of hydrogen fluoride and potassium fluoride or the electrolytic synthesis may be performed using an electrolytic solution in which the compound having the chemical structure before fluorination is dissolved into a mixed molten salt of hydrogen fluoride and potassium fluoride .
  • the compound having the chemical structure before fluorination reacts with fluorine gas generated in a reaction in the anode for electrolytic synthesis to be a fluorine containing compound.
  • a mixed molten salt of hydrogen fluoride and ammonium fluoride (NH 4 F) or a mixed molten salt of hydrogen fluoride, potassium fluoride, and ammonium fluoride is usable as the electrolytic solution.
  • the molar ratio of the hydrogen fluoride and the ammonium fluoride in the electrolytic solution can be set to 1.5 to 2.5:1, for example.
  • the hydrogen fluoride generally contains moisture in a proportion of 0.1 mass% or more and 5 mass% or less.
  • the hydrogen fluoride may be used for the electrolytic solution after the moisture contained in the hydrogen fluoride is reduced to 3 mass% or less by a method described in JP 7-2515 A , for example.
  • the shape of the anode for electrolytic synthesis is not particularly limited and can be freely selected from a plate shape, a mesh shape, a punching plate shape, a rounded plate-like shape, a shape by which generated bubbles are guided to the rear surface of an electrode, a three-dimensional structure considering the circulation of an electrolytic solution, and the like because the anode substrate is formed of a metallic material.
  • a metal electrode is usable as the cathode for electrolytic synthesis.
  • the types of the metal forming the metal electrode include iron, copper, nickel, and Monel (Trademark) , for example.
  • the shape of the cathode for electrolytic synthesis is the same as the shape of the anode for electrolytic synthesis.
  • Granular graphite "SIGRAFINE (Registered Trademark) ABR" manufactured by SGL Carbon was processed into a plate 2 cm in length, 1 cm in width, and 0.5 cm in thickness, a metal bar for power supply was attached thereto, and then masking was applied such that the electrode surface was formed into a rectangular shape 1 cm in length and 1 cm in width to be used as an electrode.
  • An electrolytic device having a similar configuration to that of the electrolytic device illustrated in FIGS. 1 , 2 was produced using the electrode as an anode and using a Monel (trademark) plate as a cathode.
  • a corrosion potential of nickel was used.
  • a mixed molten salt (KF ⁇ 2HF) of potassium fluoride and hydrogen fluoride was used as an electrolytic solution.
  • Constant voltage electrolysis was performed such that the potential of the anode was constant at 6 V based on the corrosion potential of nickel to electrolytically synthesize fluorine gas.
  • the current at this time was 0.148 A and the apparent current density was 0.148 A/cm 2 .
  • Electrolytic synthesis was performed in the same manner as in Comparative Example 1, except forming a conductive diamond coating film by a thermal CVD method on the surface of the anode.
  • the current at this time was 0.260 A and the apparent current density was 0.260 A/cm 2 .
  • Electrolytic synthesis was performed in the same manner as in Comparative Example 2, except performing constant current electrolysis instead of the constant voltage electrolysis .
  • the current was 0.148 A and the current density was 0.148 A/cm 2 .
  • the voltage of the anode based on the reference electrode at this time was 5.23 V.
  • the anode used in Example 1 includes an anode substrate formed of a metallic material and a carbonaceous layer formed of a carbonaceous material and arranged on the surface of the anode substrate.
  • the metallic material forming the anode substrate was an iron-based alloy containing iron, nickel, and cobalt.
  • the iron content was 63.5 mass%
  • the nickel content was 31.5 mass%
  • the cobalt content was 5.0 mass%.
  • the dimension of the anode substrate is 2 cm in length, 1 cm in width, and 1 mm in thickness. Masking was applied such that the electrode surface was formed into a rectangular shape 1 cm in length and 1 cm in width.
  • the carbonaceous layer arranged on the surface of the anode substrate has a double layer structure containing an inner layer and an outer layer.
  • the analysis using X-ray photoelectron spectroscopy (XPS) shows that the inner layer is a layer containing carbon and metal (iron, nickel, cobalt) and the outer layer is a diamond-like carbon layer substantially containing only carbon.
  • the inner layer is formed by implanting carbon ions into a top layer portion of the anode substrate by a plasma ion implantation method to modify the top layer portion.
  • the outer layer is formed by laminating carbon on the inner layer by the plasma ion implantation method.
  • the current in the constant voltage electrolysis was 0.454 A and the apparent current density was 0.454 A/cm 2 .
  • a value of the electrolytic resistance of the anode is approximately half of that in Comparative Example 2, which shows that the electrolytic resistance of the anode dramatically decreases.
  • Electrolytic synthesis was performed in the same manner as in 1, except using an anode substrate formed of nickel.
  • the current at this time was 0.27 A and the apparent current density was 0.27 A/cm 2 .
  • Electrolytic synthesis was performed in the same manner as in 1, except using the anode substrate formed of iron.
  • the current at this time was 0.24 A and the apparent current density was 0.24 A/cm 2 .
  • Electrolytic synthesis was performed in the same manner as in 1, except performing constant current electrolysis instead of the constant voltage electrolysis.
  • the current is 0.148 A and the current density is 0.148 A/cm 2 .
  • the voltage of the anode based on the reference electrode at this time was 4.60 V.
  • the constant current electrolysis was performed at the same current for further 500 hours while supplying hydrogen fluoride.
  • the voltage did not change, the current efficiency of the generation of fluorine gas was 99%, and no deteriorations were observed on the surface of the anode after the completion of the electrolysis.
  • Electrolytic synthesis was performed in the same manner as in Example 1, except that the metallic material forming the anode substrate was an iron-based alloy containing iron, nickel, and cobalt, the iron content was 61.8 mass%, the nickel content was 32.0 mass%, and the cobalt content was 6.2 mass%.
  • the current at this time was 0.472 A and the apparent current density was 0.472 A/cm 2 .
  • Electrolytic synthesis was performed in the same manner as in Example 1, except that the metallic material forming the anode substrate was an iron-based alloy containing iron, nickel, and cobalt, the iron content was 52.0 mass%, the nickel content was 38.0 mass%, and the cobalt content was 10.0 mass%.
  • the current at this time was 0.411 A and the apparent current density was 0.411 A/cm 2 .
  • Electrolytic synthesis was performed in the same manner as in Example 1, except that the metallic material forming the anode substrate was an iron-based alloy containing iron and nickel, the iron content was 65.0 mass%, and the nickel content was 35.0 mass%.
  • the current at this time was 0.373 A and the apparent current density was 0.373 A/cm 2 .
  • Electrolytic synthesis was performed in the same manner as in Example 1, except that the metallic material forming the anode substrate was an iron-based alloy containing iron, nickel, cobalt, and carbon, the iron content was 61.2 mass%, the nickel content was 30.0 mass%, the cobalt content was 8.0 mass%, and the carbon content was 0.8 mass%.
  • the current at this time was 0.448 A and the apparent current density was 0.448 A/cm 2 .
  • Electrolytic synthesis was performed in the same manner as in 1, except that the carbonaceous layer arranged on the surface of the anode substrate was a diamond-like carbon layer having a single layer structure formed by a plasma CVD method.
  • the current at this time was 0.432 A and the apparent current density was 0.432 A/cm 2 .
  • Examples 1 to 7 used the anodes in which the anode substrate was formed of the iron-based alloy containing iron and nickel and the carbonaceous layer was provided on the surface of the anode substrate, and therefore were able to stably reduce the resistance in the constant voltage electrolysis as compared with Comparative Examples 1, 2 using the carbon anodes and Comparative Examples 4, 5 using the metal anodes. Further, it was found that, when the anode substrate was formed of the iron-based alloy containing iron, nickel, and cobalt, the resistance in the constant current electrolysis can also be reduced as compared with Comparative Example 3 using the carbon anode.

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EP19851407.7A 2018-08-23 2019-07-29 Anode de synthèse électrolytique et procédé de production de gaz fluoré Active EP3842571B1 (fr)

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EP4427931A4 (fr) * 2021-11-04 2025-12-03 Stratifié et électrode pour électrolyse
KR102773888B1 (ko) * 2023-01-04 2025-02-27 문형철 내부식성 및 전기전도도가 향상된 삼불화질소 가스 생산용 니켈전극 및 그 제조방법
CN119980324B (zh) * 2023-11-10 2025-12-26 万华化学集团股份有限公司 一种铁基复合阳极制备方法及其在电化学合成己二腈中的应用

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US20210310138A1 (en) 2021-10-07
EP3842571B1 (fr) 2025-01-22
KR20210024139A (ko) 2021-03-04
CN112513336A (zh) 2021-03-16
TWI714202B (zh) 2020-12-21
CN112513336B (zh) 2024-03-19
TW202016358A (zh) 2020-05-01
JP7310824B2 (ja) 2023-07-19
EP3842571A4 (fr) 2021-10-13
KR102503370B1 (ko) 2023-02-24
WO2020039853A1 (fr) 2020-02-27
JPWO2020039853A1 (ja) 2021-08-12

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