WO2015098058A1 - Électrode pour la production d'hydrogène, procédé pour la production de celle-ci et procédé d'électrolyse utilisant celle-ci - Google Patents

Électrode pour la production d'hydrogène, procédé pour la production de celle-ci et procédé d'électrolyse utilisant celle-ci Download PDF

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WO2015098058A1
WO2015098058A1 PCT/JP2014/006324 JP2014006324W WO2015098058A1 WO 2015098058 A1 WO2015098058 A1 WO 2015098058A1 JP 2014006324 W JP2014006324 W JP 2014006324W WO 2015098058 A1 WO2015098058 A1 WO 2015098058A1
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electrode
platinum
hydrogen
catalyst layer
nickel
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今井　順一
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東ソー株式会社
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys

Definitions

  • the present invention relates to an electrode for hydrogen generation used for electrolysis of water or electrolysis of an aqueous alkali metal chloride solution such as salt, a method for producing the same, and an electrolysis method using the same.
  • the energy saving means is to substantially reduce the electrolysis voltage composed of theoretical decomposition voltage, liquid resistance, diaphragm resistance, anode overvoltage, cathode overvoltage, and the like.
  • the overvoltage value depends on the electrode catalyst material and the morphology of the electrode surface, many researches and developments have been conducted on the improvement thereof.
  • a dimensional stability electrode having a low anode overvoltage and excellent durability [for example, a DSE electrode manufactured by Permerek Electrode Co., Ltd. ( Registered trademark)] has been completed and has already been used in a wide range of electrolytic industries including the salt electrolysis industry.
  • the means for reducing the hydrogen overvoltage is to increase the activity of the supported catalyst and increase the reaction specific surface area.
  • a metal mixture, metal alloy, metal oxide or A highly active catalyst made of a mixture of these is supported, and the increase in specific surface area is improved by the supporting method.
  • the main supporting method is an electrodeposition of catalyst components from a bath in which catalyst components and metal salts are dissolved.
  • Plating method dispersion plating method in which catalyst components are electrophoretically deposited from a bath in which a catalyst material is dispersed in a metal salt solution, spraying method in which a molten catalyst material is directly sprayed onto a substrate, and a metal salt solution is applied.
  • the pyrolysis method which bakes is mentioned.
  • the deformation of the electrode due to plating stress and the exfoliation of the support are likely to occur, and the activity of these base metals is low, so the activity is improved by alloying the base metal This alone is not sufficient as an effect of reducing the hydrogen overvoltage.
  • Patent Document 2 an alloy layer composed of nickel and molybdenum supported by an arc ion plating method is disclosed (Patent Document 2), but the initial hydrogen overvoltage is sufficiently low, but the hydrogen overvoltage rise in long-term electrolysis operation, so-called durability is disclosed. There was a problem.
  • an electrode for hydrogen generation made of a ternary alloy selected from nickel and / or cobalt, a component selected from aluminum, zinc, magnesium and silicon and a noble metal such as platinum is disclosed (Patent Document 3).
  • This electrode elutes and removes a component selected from aluminum, zinc, magnesium, and silicon from the three-component alloy, and uses the Raney-type nickel and / or Raney-type cobalt catalyst as the hydrogen generating electrode. Therefore, by adding a trace amount of noble metal component less than 0.4 in molar ratio, durability is improved by preventing deterioration of electrode activity due to nickel and / or cobalt changing to nickel hydroxide or cobalt hydroxide. Is intended.
  • Patent Document 3 describes that even if the molar ratio of the noble metal component is 0.4 or more, there is no effect of reducing the hydrogen generation overvoltage.
  • Patent Document 4 discloses a condition sufficient to oxidize a metal compound after coating and drying a mixed solution of a platinum group metal compound and a metal compound such as Ni, that is, in an oxidizing air current such as air or oxygen and There has been proposed a method for producing an electrode made of a mixed oxide or composite oxide of platinum group metal oxide and Ni oxide by heat treatment at a high temperature.
  • Example 3 of Patent Document 4 platinum, nickel, and ruthenium prepared by applying a mixed solution of chloroplatinic acid, nickel chloride, and ruthenium chloride to a nickel base material, drying, and then thermally decomposing at 470-480 ° C.
  • An electrode for hydrogen generation coated with an oxide is disclosed, and when converted from an actual absolute reproducibility voltage by thermodynamic calculation described in Patent Document 4 to an overvoltage, the overvoltage in the first week is sufficiently satisfied as 42 mV.
  • the overvoltage increases with the progress of electrolysis, and the hydrogen generation overvoltage at the 6th week is 87 mV, and after the 11th week is 97 mV. Therefore, when used at a current density of 5 kA / m 2 or more, the overvoltage is expected to be 100 mV or more at least, and there is a problem to be improved.
  • Patent Document 5 includes a noble metal deposit made of one kind of noble metal or a mixture or alloy of two or more kinds of noble metals, and one kind or two or more kinds of base metals such as Ni in the noble metal deposit.
  • an electrode for hydrogen generation in which a deposit is deposited on a conductive substrate such as Ni.
  • these hydrogen generating electrodes have a problem that they are easily poisoned by impurities such as iron in the electrolytic solution (Patent Document 6).
  • a hydrogen generating electrode supporting a noble metal and having a low hydrogen overvoltage has been proposed.
  • the hydrogen generating electrode supporting platinum is used to reduce the amount of iron ions present in the electrolyte.
  • it is susceptible to poisoning, and the hydrogen overvoltage rises even at a very low concentration of iron ions of 1 ppm or less. Therefore, in the electrolysis industry of alkaline metal chloride aqueous solutions where iron ions are likely to be mixed into the electrolyte. Further improvements to the use of are being considered.
  • the iron ion concentration of 0.5 ppm or less is found to be able to prevent the precipitation of iron, using a low hydrogen overvoltage cathode, while maintaining the iron ion concentration in the catholyte to 0.5 ppm or less
  • An electrolysis method of an alkaline metal chloride aqueous solution to be electrolyzed has been proposed (Patent Document 6).
  • an electrode for hydrogen generation that is sensitively affected by poisoning to iron ions can be used in the electrolysis industry of an alkali metal chloride aqueous solution.
  • Patent Document 6 it is necessary to use a material such as high Ni-based stainless steel or Ni at least at a portion that is positively polarized in the portion in contact with the catholyte, or to pass an anticorrosion current when stopped. There was a problem that was necessary and should be improved from an economic point of view.
  • Patent Document 8 a hydrogen generation electrode in which a catalyst containing platinum and ruthenium and at least one of gold or silver, or a catalyst containing organic polymer particles is supported on a conductive substrate.
  • the electrode for hydrogen generation has an excellent characteristic in that the increase in overvoltage is negligible even when iron ions are present in the catholyte, and the amount of energy used for the electrolysis of the alkali metal chloride aqueous solution can be reduced.
  • An electrode for hydrogen generation having However, platinum, gold, and silver are all expensive materials, and when polytetrafluoroethylene is included in them, the cost becomes even more expensive. Therefore, there was still a problem to be improved from an economic viewpoint.
  • an electrode for hydrogen generation using a catalyst composed of platinum and cerium has been proposed (Patent Document 9).
  • the electrode for hydrogen generation comprising the platinum and cerium catalyst has a low overvoltage and the influence of iron ions is suppressed, and exhibits excellent performance as a hydrogen generation electrode for electrolysis of an aqueous alkali metal chloride solution.
  • an electrode for hydrogen generation using a catalyst layer made of platinum, cerium, and palladium has been proposed (Patent Document 10).
  • the hydrogen generation electrode using the platinum, cerium, and palladium catalyst has a hydrogen overvoltage lower by about 20 mV than the hydrogen generation electrode using the platinum and cerium-only catalyst. It has.
  • Patent Documents 11 and 12 an electrode for hydrogen generation using a catalyst layer in which four components of lanthanum and ruthenium are essential in addition to platinum and cerium has been proposed (Patent Documents 11 and 12).
  • the hydrogen generation electrode using the platinum and the catalyst made of cerium, lanthanum, and ruthenium has a hydrogen overvoltage equivalent to or 5 mV lower than the hydrogen generation electrode using the catalyst made only of platinum and cerium, and 1 Even when electrolysis is stopped for 1 hour per day, the hydrogen overvoltage does not change even after 10 days of continuous electrolysis, the catalyst is not consumed, and there is no deposit on the electrode surface.
  • a catalyst layer prepared using a ruthenium nitrate and lanthanum carboxylate coating material, a mixture of a ruthenium compound and a cerium compound is present in the presence of oxalic acid.
  • a cathode for hydrogen generation containing a composition obtained by pyrolysis under the following conditions (Patent Document 14), and a plating layer of nickel and ruthenium oxide is formed by electrolytic plating in a nickel plating bath containing ruthenium oxide;
  • An electrode for hydrogen generation (Patent Document 15) in which a layer made of a metal or metal oxide of cerium and lanthanum is laminated by thermal decomposition.
  • Patent Document 16 As an electrode for hydrogen generation that is less affected by iron ion poisoning, a platinum alloy composed of one kind of metal selected from the group consisting of nickel, cobalt, copper, silver and iron, or a non-transition metal element and platinum. A hydrogen generating electrode made of a crystalline material has been proposed (Patent Document 16).
  • the electrode for hydrogen generation combines the characteristics of hydrogen overvoltage, anti-poisoning performance against iron ions in the catholyte, and sufficient durability for industrial use that requires starting and stopping, and has industrially satisfactory characteristics. An electrode for hydrogen generation has not been obtained.
  • the purpose of the present invention is that it can be used in water or alkali metal chloride aqueous solution electrolysis industry, etc., and the hydrogen overvoltage is sufficiently low and there is no influence of poisoning by iron ions.
  • a hydrogen generating electrode excellent in durability without an increase in hydrogen overvoltage or dropping of the support a method for producing the hydrogen generating electrode, and an electrolysis method using the hydrogen generating electrode as a cathode. Or it is to reduce the power consumption of the alkali metal chloride aqueous solution electrolysis industry or the like.
  • the present invention relates to an electrode for hydrogen generation in which a catalyst layer mainly composed of platinum, nickel and palladium or a catalyst layer mainly composed of platinum, nickel and ruthenium is supported on a conductive substrate. is there. That is, the present invention resides in the following [1] to [10].
  • An electrode for hydrogen generation in which a catalyst layer mainly composed of platinum, nickel and palladium or a catalyst layer mainly composed of platinum, nickel and ruthenium is supported on a conductive substrate.
  • An electrode for hydrogen generation in which a catalyst layer made of platinum, nickel and palladium or a catalyst layer made of platinum, nickel and ruthenium is supported on a conductive substrate is, for example, a platinum compound solution on a conductive substrate. And a nickel compound solution and a palladium compound solution or a platinum compound solution, a nickel compound solution and a ruthenium compound solution, dried at a temperature of 200 ° C. or lower, and then thermally decomposed at a temperature of 200 ° C. or higher and 700 ° C. or lower.
  • the catalyst layer obtained by reduction treatment is mainly composed of an alloy of platinum, nickel and palladium, or an alloy of platinum, nickel and ruthenium.
  • the catalyst layer has excellent performance as an electrode for hydrogen generation.
  • the content of palladium in the catalyst layer made of platinum, nickel and palladium is preferably in the range of 1 mol% to 55 mol%, the hydrogen overvoltage is further lower, and the iron poisoning resistance is excellent. Therefore, it is more preferable that the palladium content in the catalyst layer is 4 to 48 mol%, the nickel content is 48 to 4 mol%, and the balance is platinum.
  • the ruthenium content in the catalyst layer composed of platinum, nickel and ruthenium is preferably in the range of 1 mol% to 55 mol%, and preferably 1 mol% to 33 mol. A range of less than or equal to mol% is preferable, and since not only the hydrogen overvoltage is low but also excellent in reverse current resistance, the ruthenium content in the catalyst layer is 20 to 50 mol%, the nickel content is 40 to 25 mol%, The balance is preferably platinum, and the ruthenium content in the catalyst layer is preferably 20 to 32 mol%, the nickel content is preferably 40 to 34 mol%, and the balance is preferably platinum.
  • the reduction treatment is preferably electrochemical reduction, and more preferably electrochemical reduction when electrolyzing water or an aqueous alkali metal chloride solution.
  • Examples of the conductive substrate used in the present invention include nickel, iron, copper, titanium, and stainless steel alloy, and nickel having excellent corrosion resistance against an alkaline solution is particularly preferable.
  • the shape of the conductive substrate is not particularly limited, and may generally be a shape that matches the electrode of the electrolytic cell. For example, a flat plate, a curved plate, or the like can be used.
  • the conductive base material used in the present invention is preferably a perforated plate, and for example, expanded metal, punch metal, net, or the like can be used.
  • the method for producing an electrode for hydrogen generation according to the present invention can be any method as long as a catalyst layer made of platinum, nickel and palladium or a catalyst layer made of platinum, nickel and ruthenium can be supported on a conductive substrate.
  • a simple manufacturing method may be used.
  • an electroplating method, a dispersion plating method, a thermal spraying method, a thermal decomposition method, an arc ion plating method, or the like can be used.
  • the present invention provides hydrogen generation on which a catalyst layer made of platinum, nickel and palladium or a catalyst layer made of platinum, nickel and palladium is supported on a conductive substrate. It is not possible to manufacture a working electrode.
  • the present invention provides a specific method for producing a hydrogen generation electrode carrying a catalyst layer made of platinum, nickel and palladium or a catalyst layer made of platinum, nickel and ruthenium on a conductive substrate.
  • the thermal decomposition method will be described as an example.
  • the thermal decomposition method referred to in the present invention means that a platinum compound solution and a nickel compound solution and a palladium compound solution, or a platinum compound solution, a nickel compound solution and a ruthenium compound solution are applied on a substrate, dried, and thermally decomposed. A series of operations to be performed.
  • the surface roughening means is not particularly limited, and a known method such as sand blasting, etching with oxalic acid or hydrochloric acid solution, washing with water and drying can be used.
  • chloroplatinic acid As the platinum compound used in the method for producing an electrode for hydrogen generation according to the present invention, chloroplatinic acid, dinitrodiamine platinum or the like can be used.
  • dinitrodiammine platinum that forms an ammine complex because the crystallite diameter of the platinum alloy after the reduction treatment can be reduced to, for example, 200 angstroms or less to increase the reaction specific surface area.
  • the thermal decomposition temperature of the dinitrodiamine platinum is as high as about 550 ° C., so that aggregation of platinum during thermal decomposition is suppressed, and a film in which platinum, nickel and palladium are uniformly mixed after thermal decomposition, or platinum and It is presumed that a film in which nickel and ruthenium are uniformly mixed is obtained, and an alloy having a fine crystallite diameter is obtained by reduction treatment.
  • the nickel compound and the palladium compound used in the production method of the present invention, or the nickel compound and the ruthenium compound used in the production method of the present invention are not particularly limited, and nitrates, sulfates, chlorides, carbonates, acetates, A sulfamate or the like can be used.
  • a solvent for dissolving the platinum compound and the nickel compound and the palladium compound or the platinum compound, the nickel compound and the ruthenium compound, in order to increase the surface area of the support those which can completely dissolve these raw materials are used.
  • water or an inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid or acetic acid solution, and an organic solvent such as methanol, ethanol, propanol or butanol, or a mixture thereof can be used.
  • the pH of the coating solution may be adjusted and used for the purpose of suppressing dissolution of the base metal in the coating solution, and a complex salt such as lysine or citric acid may be added to increase the surface area of the support, and nickel and Palladium or nickel and ruthenium may be complexed.
  • a complex salt such as lysine or citric acid may be added to increase the surface area of the support, and nickel and Palladium or nickel and ruthenium may be complexed.
  • the method of applying the compound solution to the conductive base material is a platinum compound solution and a nickel compound solution and a palladium compound solution, or a platinum compound solution, a nickel compound solution, and a ruthenium compound solution separately using a brush or the like.
  • all known methods such as a spray method and a dip coating method can be suitably used.
  • the drying temperature after coating may be 5 to 60 minutes at a temperature of 200 ° C. or lower, and a drying temperature of 150 ° C. or lower is preferable.
  • the thermal decomposition temperature after drying may be in the range of more than 200 ° C. and not more than 700 ° C. for 5 to 60 minutes, but preferably more than 350 ° C. and not more than 500 ° C.
  • the thermal decomposition temperature of dinitrodiamine platinum is 550 ° C., and by performing thermal decomposition at 500 ° C. or less, platinum sintering is suppressed and hydrogen overvoltage is further reduced.
  • a working electrode can be obtained.
  • the above series of operations of application, drying, and thermal decomposition is repeated once or several times.
  • the number of times of repeating the pyrolysis operation is not particularly limited, but in order to obtain a low hydrogen overvoltage, an alloy mainly composed of platinum, nickel and palladium after reduction treatment or an alloy mainly composed of platinum, nickel and ruthenium is used. It is preferable to repeat the pyrolysis operation until the loading amount is 0.5 g / m 2 or more, and it is more preferable to repeat the pyrolysis operation until 1 g / m 2 or more.
  • a reduction treatment is performed for the purpose of reducing and alloying the support (catalyst layer precursor) to a metallic state.
  • the reduction treatment method is not particularly limited, but a chemical reduction method by contact with a substance having a strong reducing power such as hydrazine, formic acid or oxalic acid, or a low reduction potential is given to platinum, nickel and palladium, or platinum, nickel and ruthenium.
  • An electrochemical reduction method can be used.
  • the electrochemical reduction method is a method for applying a potential necessary for reduction of a support (catalyst layer precursor) made of platinum, nickel and palladium, or a support made of platinum, nickel and ruthenium (catalyst layer precursor).
  • a support catalyst layer precursor
  • platinum, nickel and palladium or a support made of platinum, nickel and ruthenium (catalyst layer precursor).
  • Standard electrode potentials of platinum and nickel and palladium in aqueous solution or platinum, nickel and ruthenium in aqueous solution have already been disclosed ("Electrochemical Handbook" 5th edition, Maruzen Publishing, pp. 92-95) and required for reduction Such potential can be estimated from the standard electrode potential.
  • the electrochemical reduction method converts the support (catalyst layer precursor) after pyrolysis to a metal state while performing electrolysis. This is convenient because reduction and alloying can be carried out, and it is not necessary to carry out the above-mentioned support reduction treatment separately from electrolysis.
  • This electrochemical reduction treatment is usually performed by an electrochemical reduction treatment in water or an aqueous alkali metal chloride solution.
  • the electrode for hydrogen generation of the present invention thus obtained can be used as an electrode for hydrogen generation in electrolysis of an aqueous solution of alkali metal chloride such as water or sodium chloride, and a low hydrogen overvoltage can be obtained.
  • Low overvoltage characteristics can be maintained stably for a long time without any special measures not to incorporate iron ions, and the catalyst will not peel off or fall off during a stop or restart operation, that is, hydrogen overvoltage performance and durability It is an excellent electrode for hydrogen generation.
  • the required energy of the electrolysis industry can be easily reduced simply by changing the electrode for hydrogen generation to the electrode for hydrogen generation provided by the present invention. It becomes possible.
  • alkali metal chloride aqueous solution such as water or salt
  • water generating electrode as a cathode
  • salt electrolysis in which hydrogen gas and an aqueous alkali metal hydroxide solution are generated from the cathode and oxygen gas or chlorine gas is generated from the anode, is a typical example of the electrolysis industry.
  • a cation exchange membrane is preferably used in terms of current efficiency and energy efficiency due to low electrolytic cell voltage.
  • the electrode for hydrogen generation in which a catalyst layer mainly composed of platinum, nickel and palladium or a catalyst layer mainly composed of platinum, nickel and palladium is supported on the conductive substrate of the present invention is a low hydrogen
  • the hydrogen generating electrode of the present invention obtained in this way may increase the hydrogen overvoltage due to poisoning of iron ions in the electrolyte, which has been regarded as a disadvantage of conventional platinum-based catalysts.
  • the catalyst does not peel or fall off due to the reverse current flowing during the electrolysis operation or during the stop / start operation.
  • the low hydrogen overvoltage characteristic inherent in platinum can be stably maintained over a long period of time, and in particular, water or alkali that is forced to contain iron in the catholyte and reverse current that flows several times a year during shutdown and restart.
  • the energy required for the electrolysis industry of metal aqueous solutions can be greatly reduced.
  • FIG. 3 is an X-ray diffraction chart of the hydrogen generation electrode of Example 1.
  • FIG. 6 is a diagram showing an X-ray diffraction chart of a hydrogen generating electrode of Example 6.
  • the value was taken as the overvoltage rise value due to iron poisoning, and the iron poisoning resistance evaluation was carried out with this overvoltage rise value.
  • Reverse current tolerance evaluation After measuring the hydrogen overvoltage by the above method, in 0.5 M sodium sulfate, Pt as the counter electrode, saturated calomel electrode as the reference electrode, scanning potential -1.0 V to 0.6 V vs SCE, scanning speed 50 mV / s, initial potential Perform cyclic voltammetry under the conditions of 0.1 V vs SCE, 250 cycles, measure the hydrogen overvoltage again by the above method, determine the difference from the previously measured hydrogen overvoltage, and use this value as the overvoltage increase due to the reverse current. The reverse current tolerance was evaluated based on this overvoltage rise value.
  • the hydrogen overvoltage measured by the above method and the one obtained by performing cyclic voltammetry measurement after the hydrogen overvoltage measurement by the above method and again measuring the hydrogen overvoltage were dissolved in aqua regia, and the ICP emission spectrometer (Perkin The load was determined using Elmer's model optima 3000), and the rate of change in the amount of platinum was determined from these values, which was used as the residual rate of platinum due to the reverse current.
  • Example 1 Nickel expanded mesh (5.0 ⁇ 5.0 cm) was used as the conductive substrate, and as a roughening treatment, etching was performed at a temperature of 50 ° C. for 15 minutes using a 10 wt% hydrochloric acid solution, followed by washing with water and drying.
  • this coating solution was applied to the entire surface of the nickel expanded mesh using a brush, dried at 80 ° C. for 15 minutes in a hot air drier, and then used in a box-type muffle furnace (Advantech Toyo model KM-600, internal volume 27 L). And pyrolyzed at 500 ° C. for 15 minutes under air flow. This series of operations was repeated 5 times.
  • the electrode for hydrogen generation obtained as described above was subjected to the conditions of Ni, temperature 88 ° C., current density 6.0 kA / m 2 at the counter electrode, using an electrolytic solution (capacity: about 1 L) of a 32 wt% sodium hydroxide aqueous solution. After water electrolysis for 10 minutes, the hydrogen generating electrode is taken out, dried, and the X-ray diffraction chart when the X-ray diffraction is performed is shown in FIG.
  • reference numeral 1 is a peak attributed to the substrate (nickel)
  • reference numeral 2 is a peak attributed to the alloy (platinum-nickel-palladium alloy)
  • reference numeral 3 is a peak attributed to NiO.
  • Example 2-5 In Example 1, an electrode was produced in the same manner as in Example 1 except that the composition of platinum, nickel and palladium was changed to the composition shown in Table 1, respectively.
  • Example 2 when the hydrogen overvoltage was measured, the hydrogen overvoltage was 80.3 mV, and the overvoltage increase due to iron poisoning was 19.9 mV, the overvoltage increase due to the reverse current was 7.8 mV, and the platinum overvoltage due to the reverse current was The residual rate was 100%.
  • Table 1 The results are shown in Table 1.
  • Example 3 when the hydrogen overvoltage was measured, the hydrogen overvoltage was 72.8 mV, the overvoltage increase due to iron poisoning was 18.3 mV, the overvoltage increase due to the reverse current was 10.2 mV, and the platinum overvoltage due to the reverse current was The residual rate was 100%.
  • Table 1 The results are shown in Table 1.
  • Example 4 when the hydrogen overvoltage measurement was performed, the hydrogen overvoltage was 70.3 mV, the overvoltage increase due to iron poisoning was 12.1 mV, the overvoltage increase due to the reverse current was 12.1 mV, and the platinum overvoltage due to the reverse current was The residual rate was 86%.
  • Table 1 The results are shown in Table 1.
  • Example 5 when the hydrogen overvoltage measurement was performed, the hydrogen overvoltage was 77.5 mV, the overvoltage increase due to iron poisoning was 9.1 mV, the overvoltage increase due to the reverse current was 5.4 mV, and the platinum overvoltage due to the reverse current was The residual rate was 90%.
  • Table 1 The results are shown in Table 1.
  • Example 1 Comparative Example 1 In Example 1, except that a coating solution containing 50 mol% platinum and 50 mol% nickel was prepared using a dinitrodiammine platinum nitrate solution, nickel nitrate hexahydrate and water, and this was applied. An electrode was produced in the same manner as in 1.
  • Example 2 In Example 1, except that a coating solution containing 50 mol% platinum and 50 mol% palladium was prepared using dinitrodiammine platinum nitrate solution, palladium nitrate dihydrate and water, and this was applied. An electrode was produced in the same manner as in 1.
  • the hydrogen overvoltage is lower than the hydrogen overvoltage in the range of the comparative example.
  • the amount of overvoltage increase due to iron poisoning and the amount of overvoltage increase due to the reverse current are compared. The value is lower than the result in Example 1. Therefore, it was shown that the hydrogen generating electrode of the present invention has excellent hydrogen overvoltage performance, iron poisoning and durability against reverse current.
  • the supported electrode for hydrogen generation is preferably Example 4 and Example 5.
  • the Pd content is 4 to 48 mol%
  • Ni is 48 to 4 mol%
  • the balance is Pt.
  • the electrode for hydrogen generation in which the catalyst layer having a certain composition is supported is preferably Example 1 and Example 3, and the Pd content is 20 to 32 mol%, Ni is 40 to 40%.
  • a hydrogen generating electrode in which a catalyst layer having a composition of 34 mol% and the balance being Pt is supported is preferable.
  • Example 6 An electrode was produced in the same manner as in Example 1 except that a nitric acid solution of ruthenium nitrate (manufactured by Tanaka Kikinzoku) was used instead of palladium nitrate dihydrate (manufactured by Kojima Chemical).
  • the electrode for hydrogen generation obtained as described above was subjected to the conditions of Ni, temperature 88 ° C., current density 6.0 kA / m 2 at the counter electrode, using an electrolytic solution (capacity: about 1 L) of a 32 wt% sodium hydroxide aqueous solution. After water electrolysis for 10 minutes, the hydrogen generating electrode is taken out, dried, and the X-ray diffraction chart when the X-ray diffraction is performed is shown in FIG. In FIG.
  • reference numeral 1 is a peak attributed to the substrate (nickel)
  • reference numeral 2 is a peak attributed to the alloy (platinum-nickel-ruthenium alloy)
  • reference numeral 3 is a peak attributed to NiO
  • reference numeral 4 is attributed to RuO 2 . It is a peak.
  • Example 7-9 an electrode was produced in the same manner as in Example 6 except that the compositions of platinum, nickel and ruthenium were changed to the compositions shown in Table 2, respectively.
  • Example 7 when the hydrogen overvoltage was measured, the hydrogen overvoltage was 75.7 mV, the overvoltage increase due to iron poisoning was 13.3 mV, and the overvoltage increase due to the reverse current was 15.9 mV.
  • Table 2 The results are shown in Table 2.
  • Example 8 when the hydrogen overvoltage was measured, the hydrogen overvoltage was 79.0 mV, the amount of overvoltage increase due to iron poisoning was 14.1 mV, and the amount of overvoltage increase due to reverse current was 26.2 mV.
  • Table 2 The results are shown in Table 2.
  • Example 9 when the hydrogen overvoltage was measured, the hydrogen overvoltage was 73.2 mV, the overvoltage increase due to iron poisoning was 16.0 mV, and the overvoltage increase due to the reverse current was 12.4 mV.
  • Table 2 The results are shown in Table 2.
  • Example 6 a coating solution containing 50 mol% platinum and 50 mol% nickel was prepared using a dinitrodiammine platinum nitrate solution, nickel nitrate hexahydrate and water, and this example was applied. An electrode was produced in the same manner as in 6.
  • Example 6 a coating solution containing 50 mol% platinum and 50 mol% ruthenium was prepared using a dinitrodiammine platinum nitric acid solution, a ruthenium nitrate nitric acid solution, and water. An electrode was produced in the same manner as described above.
  • the hydrogen overvoltage is lower than the hydrogen overvoltage in the range of the comparative example.
  • iron The amount of increase in overvoltage due to poisoning was lower than the result in Comparative Example 3, and in Example 6-7, the value of overvoltage increase due to reverse current was lower than the result in Comparative Example 3.
  • the platinum residual ratio of Example 6 was higher than that of Comparative Example 3. Therefore, it is shown in Table 2 that the hydrogen generating electrode of the present invention has excellent hydrogen overvoltage performance, iron poisoning and durability against reverse current.
  • Examples 6 to 7 and Example 9 having a low hydrogen overvoltage are preferable, and a catalyst layer having a composition in which the content of ruthenium is 20 to 50 mol%, Ni is 40 to 34 mol%, and the balance is Pt is supported.
  • An electrode for hydrogen generation is preferred.
  • the electrode for hydrogen generation of the present invention can be used for electrolysis of water or electrolysis of an aqueous solution of alkali metal chloride such as sodium chloride, and has the potential to be used in a wide range of electrolysis industries for the first time.
  • alkali metal chloride such as sodium chloride
  • Peak attributed to substrate (nickel) 2 Peak attributed to alloy (platinum-nickel-palladium alloy or platinum-nickel-ruthenium alloy) 3: Peak attributed to NiO 4: Peak attributed to RuO 2

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Abstract

La présente invention se rapporte à une électrode pour la production d'hydrogène, qu'il est possible d'utiliser dans des industries telles que l'électrolyse de l'eau ou de solutions aqueuses de chlorures de métaux alcalins, qui a une surtension d'hydrogène suffisamment basse, qui de plus est insensible à l'empoisonnement dû aux ions fer, qui en outre ne subit pas d'augmentation de la surtension d'hydrogène ou de perte de matériau supporté pendant le fonctionnement ou pendant le démarrage ou l'arrêt et qui a une durabilité exceptionnelle, l'électrode pour la production d'hydrogène comprenant une couche de catalyseur dans laquelle les composants principaux sont le platine, le nickel et le palladium ou une couche de catalyseur dans laquelle les composants principaux sont le platine, le nickel et le ruthénium, supportée sur un matériau de base électroconducteur. L'invention se rapporte également à un procédé de production pour l'électrode pour la production d'hydrogène, dans lequel un précurseur de couche de catalyseur est formé sur un matériau de base électroconducteur et ensuite un traitement de réduction est effectué, ce qui forme la couche de catalyseur ; et à un procédé d'électrolyse dans lequel, l'électrode pour la production d'hydrogène étant utilisée en tant que cathode dans une cuve d'électrolyse dans laquelle l'anode est disposée de l'autre côté d'une membrane barrière par rapport à celle-ci, de l'eau ou une solution aqueuse de chlorure de métal alcalin est soumise à une électrolyse et de l'hydrogène gazeux et une solution aqueuse d'hydroxyde de métal alcalin sont produits à partir de la cathode, alors que de l'oxygène gazeux et du chlore gazeux sont produits à partir de l'anode. La hauteur de la puissance consommée est réduite par ce procédé d'électrolyse.
PCT/JP2014/006324 2013-12-26 2014-12-18 Électrode pour la production d'hydrogène, procédé pour la production de celle-ci et procédé d'électrolyse utilisant celle-ci WO2015098058A1 (fr)

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JP2013-270495 2013-12-26
JP2013-270496 2013-12-26
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9816190B2 (en) 2014-12-15 2017-11-14 JOI Scientific, Inc. Energy extraction system and methods
US10047445B2 (en) 2014-12-15 2018-08-14 JOI Scientific, Inc. Hydrogen generation system
WO2018151228A1 (fr) 2017-02-15 2018-08-23 旭化成株式会社 Électrode négative, son procédé de fabrication, cellule électrolytique l'utilisant et procédé de production d'hydrogène
WO2018174281A1 (fr) 2017-03-23 2018-09-27 旭化成株式会社 Système et procédé d'électrolyse d'eau, et procédé de production d'hydrogène
US10214820B2 (en) 2014-12-15 2019-02-26 JOI Scientific, Inc. Hydrogen generation system with a controllable reactive circuit and associated methods
WO2020110527A1 (fr) * 2018-11-27 2020-06-04 株式会社大阪ソーダ Électrode de génération d'hydrogène, son procédé de production et procédé de production d'hydrogène
JP2022531603A (ja) * 2020-01-09 2022-07-07 エルジー・ケム・リミテッド 電気分解用電極
KR20220165779A (ko) 2020-05-15 2022-12-15 아사히 가세이 가부시키가이샤 전해 시스템 및 그 사용 방법
CN115522211A (zh) * 2022-05-16 2022-12-27 中山大学 一种Ni/Mo/Ru复合材料的制备方法及其在电解水制氢的应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62501219A (ja) * 1984-12-14 1987-05-14 オロンジオ・ド・ノラ・イムピアンチ・エレットロキミシ・ソシエタ・ペル・アジオニ 電極の製造法と電気化学プロセスにおける電極の使用
JPH04231491A (ja) * 1990-05-29 1992-08-20 Dow Chem Co:The 電気触媒陰極およびその製造法
JPH0790664A (ja) * 1993-09-22 1995-04-04 Chlorine Eng Corp Ltd 低水素過電圧陰極とその製造方法
JP2005330575A (ja) * 2004-04-23 2005-12-02 Tosoh Corp 水素発生用電極およびその製造方法並びにこれを用いた電解方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62501219A (ja) * 1984-12-14 1987-05-14 オロンジオ・ド・ノラ・イムピアンチ・エレットロキミシ・ソシエタ・ペル・アジオニ 電極の製造法と電気化学プロセスにおける電極の使用
JPH04231491A (ja) * 1990-05-29 1992-08-20 Dow Chem Co:The 電気触媒陰極およびその製造法
JPH0790664A (ja) * 1993-09-22 1995-04-04 Chlorine Eng Corp Ltd 低水素過電圧陰極とその製造方法
JP2005330575A (ja) * 2004-04-23 2005-12-02 Tosoh Corp 水素発生用電極およびその製造方法並びにこれを用いた電解方法

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9816190B2 (en) 2014-12-15 2017-11-14 JOI Scientific, Inc. Energy extraction system and methods
US10047445B2 (en) 2014-12-15 2018-08-14 JOI Scientific, Inc. Hydrogen generation system
US10214820B2 (en) 2014-12-15 2019-02-26 JOI Scientific, Inc. Hydrogen generation system with a controllable reactive circuit and associated methods
WO2018151228A1 (fr) 2017-02-15 2018-08-23 旭化成株式会社 Électrode négative, son procédé de fabrication, cellule électrolytique l'utilisant et procédé de production d'hydrogène
EP3591095A2 (fr) 2017-02-15 2020-01-08 Asahi Kasei Kabushiki Kaisha Cathode, son procédé de production, électrolyseur l'utilisant et procédé de production d'hydrogène
WO2018174281A1 (fr) 2017-03-23 2018-09-27 旭化成株式会社 Système et procédé d'électrolyse d'eau, et procédé de production d'hydrogène
WO2020110527A1 (fr) * 2018-11-27 2020-06-04 株式会社大阪ソーダ Électrode de génération d'hydrogène, son procédé de production et procédé de production d'hydrogène
CN113166958A (zh) * 2018-11-27 2021-07-23 株式会社大阪曹達 氢产生用电极、其制造方法、以及氢的制造方法
JPWO2020110527A1 (ja) * 2018-11-27 2021-10-14 株式会社大阪ソーダ 水素発生用電極、その製造方法、及び水素の製造方法
JP2022531603A (ja) * 2020-01-09 2022-07-07 エルジー・ケム・リミテッド 電気分解用電極
JP7324310B2 (ja) 2020-01-09 2023-08-09 エルジー・ケム・リミテッド 電気分解用電極
KR20220165779A (ko) 2020-05-15 2022-12-15 아사히 가세이 가부시키가이샤 전해 시스템 및 그 사용 방법
CN115522211A (zh) * 2022-05-16 2022-12-27 中山大学 一种Ni/Mo/Ru复合材料的制备方法及其在电解水制氢的应用

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