WO2011040464A1 - Électrode pour la production d'hydrogène et procédé d'électrolyse - Google Patents

Électrode pour la production d'hydrogène et procédé d'électrolyse Download PDF

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Publication number
WO2011040464A1
WO2011040464A1 PCT/JP2010/066945 JP2010066945W WO2011040464A1 WO 2011040464 A1 WO2011040464 A1 WO 2011040464A1 JP 2010066945 W JP2010066945 W JP 2010066945W WO 2011040464 A1 WO2011040464 A1 WO 2011040464A1
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Prior art keywords
electrode
cerium
platinum
hydrogen generation
metal
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PCT/JP2010/066945
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English (en)
Japanese (ja)
Inventor
裕樹 井本
学 長瀬
富彦 山本
信次 山内
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ダイソー株式会社
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Priority to CN2010800248774A priority Critical patent/CN102471905A/zh
Priority to JP2011534274A priority patent/JPWO2011040464A1/ja
Publication of WO2011040464A1 publication Critical patent/WO2011040464A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—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
    • C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • 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

Definitions

  • the present invention relates to an electrolysis process accompanied by hydrogen generation, mainly a cathode used for ion exchange membrane salt electrolysis, that is, an electrode for hydrogen generation, and an electrolysis method involving hydrogen generation using this electrode.
  • the overvoltage of the electrode can be reduced to about 50 mV under normal operating conditions by coating the insoluble electrode with a platinum group oxide in terms of the anode, and further improvements and improvements can be expected. Reached no level.
  • a heterogeneous mixture of platinum group oxide and nickel oxide was formed on the conductive metal as the electrode active material, and the noble metal oxide and nickel metal were composite plated to increase low overvoltage and durability.
  • ruthenium chloride, palladium chloride, and ruthenium oxide are coated on a conductive substrate, coated and fired in the air, and then electrolessly plated with nickel, thereby improving the coating strength, or a metal substrate
  • An electrode active material layer mainly composed of ruthenium oxide is formed thereon, and a porous and low-active protective layer is further formed on the surface to improve the durability of the electrode.
  • a coating layer composed of a ruthenium oxide formed by pyrolysis, nickel, and a rare earth metal having a hydrogen storage capacity is formed on a metal substrate, and against a reverse current when the electrolytic cell is stopped.
  • a coating layer composed of a ruthenium oxide formed by pyrolysis, nickel, and a rare earth metal having a hydrogen storage capacity is formed on a metal substrate, and against a reverse current when the electrolytic cell is stopped.
  • Patent Document 2 uses a composite oxide of platinum and cerium as an electrode active material layer. Adopted to increase the resistance to poisoning of iron. Further, Patent Document 3 proposes a highly active and highly poisonous resistant cathode made of a platinum group metal having an oxide film for protecting a nickel base, an oxide thereof or a hydroxide-lanthanum metal oxide or hydroxide. Yes.
  • An object of the present invention is to provide an electrode for hydrogen generation that can suppress an increase in electrolysis voltage even when the electrolysis current density is high, and an electrolysis method with low energy cost using the electrode.
  • the present inventors consider that it is indispensable to reduce the cathode overvoltage by using a platinum group metal as the electrode active material on the surface of the electrode substrate, and various kinds of materials including the platinum group metal as the electrode active material.
  • the characteristics of the electrode for hydrogen generation using the above mixture were investigated from various angles.
  • the present inventors have found a very interesting fact. The details are as follows.
  • Patent Document 2 describes a hydrogen generation electrode itself in which an electrode active material made of a mixture of a cerium-based material and a platinum-based material is coated on the surface of an electrode substrate.
  • the ratio of the cerium-based material to the platinum-based material in the electrode active material in the electrode for hydrogen generation described in Patent Document 2 is platinum-rich in terms of a metal-converted molar ratio from the viewpoint of lowering the hydrogen generation overvoltage, that is, platinum.
  • the amount is considerably larger than the amount of cerium.
  • the tendency to increase the hydrogen generation overvoltage does not change as the electrolysis current density increases.
  • the degree of increase in the hydrogen generation overvoltage accompanying the increase in the electrolysis current density that is, the dependence of the hydrogen generation overvoltage on the electrolysis current density decreases as the amount of cerium increases and the amount of platinum decreases.
  • a platinum-rich electrode active material with a large amount of platinum in the mixture of the cerium-based material and the platinum-based material In the high electrolysis current region where the electrolysis current exceeds several kA / m 2 , the cerium-based material and the cerium-based material
  • An electrode having a cerium-rich electrode active material with a large amount of cerium has a lower hydrogen generation overvoltage than an electrode having a platinum-rich electrode active material with a large amount of platinum in the platinum-based material mixture.
  • the turning point that the electrode having the cerium-rich electrode active material surpasses the electrode having the platinum-rich electrode active material in terms of hydrogen generation overvoltage is 6 kA / m 2 or more in terms of electrolytic current, which is more reliable.
  • the electrode for hydrogen generation of the present invention has been completed based on such knowledge, and contains cerium-platinum containing at least one of cerium metal, cerium oxide or cerium hydroxide and platinum metal on a conductive metal.
  • the composition of the electrode active material is such that the molar fraction of platinum is 15 to 30 mol% and the molar fraction of cerium is 70 to 85 mol in terms of metal.
  • % cerium is obtained by a rich condition of the cathode current density is from 6 kA / m 2 to 14 kA / m 2, preferably by using the conditions from 8 kA / m 2 to 14 kA / m 2, a conventional platinum Compared to using a hydrogen generation electrode with a rich cerium-platinum mixture based electrode active material, the hydrogen generation overvoltage is suppressed to a lower level and the electrolysis energy cost is reduced. It is possible.
  • the electrolytic process of the present invention using the above electrode for hydrogen generation as a cathode and the conditions of cathode current density in an alkaline aqueous solution is from 6 kA / m 2 to 14 kA / m 2, preferably 14 kA / m from 8 kA / m 2 Electrolysis with hydrogen generation is performed under the conditions up to 2, and the hydrogen generation overvoltage is suppressed to a small level compared with the case of using a conventional electrode for generating hydrogen having a platinum-rich cerium-platinum electrode active material. Electrolytic energy cost can be reduced.
  • the proportion of platinum and cerium in the electrode active material coated on the conductive metal is adjusted so that the molar fraction of platinum is 15 to 30 mol% and the molar amount of cerium.
  • the reason why the fraction is 70 to 85 mol% is as follows.
  • the electrode activity increases, but in high current density electrolysis, the hydrogen generation overvoltage tends to increase at the cathode. If the platinum mole fraction is extremely high compared to the cerium mole fraction, then a reduction in resistance to iron poisoning becomes a problem prior to discussing cathodic overvoltage. On the other hand, when the mole fraction of platinum is less than 15 mole% and the cerium fraction is greater than 85 mole%, the electrode activity becomes very low, and the effect of suppressing the increase in cathode overvoltage is reduced regardless of the electrolytic current density. .
  • a particularly desirable mole fraction of platinum is 20 to 25 mole percent, and a particularly desirable mole fraction of cerium is 75 to 80 mole percent.
  • the electrolysis current in the electrolysis operation using the electrode for hydrogen generation of the present invention is 6 kA / m in cathode current density.
  • To 14 kA / m 2 is preferred, and 8 kA / m 2 to 14 kA / m 2 is particularly preferred, because in this high current density region, an electrode having a cerium-rich electrode active material is used. This is because an electrode having a platinum-rich electrode active material surpasses in terms of hydrogen generation overvoltage. However, even if an electrode having a cerium-rich electrode active material is superior in terms of hydrogen generation overvoltage, the tendency of the hydrogen generation overvoltage to increase as the cathode current density increases does not change, so that it exceeds 14 kA / m 2. In an extremely high current density region, an increase in hydrogen generation overvoltage becomes a problem.
  • the amount of hydrogen generated from the electrode becomes very large, and it is considered that the generated hydrogen gas stays on the electrode surface.
  • cerium oxide is easily wetted with an aqueous alkali solution, and that when the proportion of cerium is large, the wettability of the electrolyte is increased, and the escape of the generated hydrogen gas from the electrode surface is accelerated.
  • the cerium oxide since the cerium oxide is partially converted into a hydroxide in the alkaline aqueous solution, it may also be affected by the improved hydrophilicity of the electrode itself.
  • the electrode for hydrogen generation of the present invention has a cerium-platinum mixture based electrode active material on a conductive metal, and the composition of the electrode active material is 15-30 mol% of platinum in terms of metal, cerium. Therefore, when hydrogen is generated in an alkaline aqueous solution as a cathode, an increase in cathode overvoltage can be suppressed at a high current density. Energy costs can be reduced. Moreover, productivity can be improved by the highly efficient high current density operation. Furthermore, since the amount of platinum in the electrode active material is limited and the amount of cerium is increased, the poisoning resistance to iron in the electrolytic solution is also excellent.
  • the electrolysis method of the present invention suppresses an increase in cathode overvoltage by using a hydrogen generation electrode having the cerium-rich electrode active material as a cathode and generating hydrogen at a high current density in an alkaline aqueous solution.
  • the cost of electrolytic energy can be reduced.
  • productivity can be improved by the highly efficient high current density operation.
  • the amount of platinum in the electrode active material is limited and the amount of cerium is increased, it is excellent in poisoning resistance against iron in the electrolytic solution, and the electrolytic energy cost can be reduced also in this respect.
  • FIG. 6 is a graph showing the degree of influence of the platinum-cerium ratio in the electrode active material on the hydrogen generation electrode on the dependence of the hydrogen generation overvoltage on the electrolysis current density.
  • an electrode for hydrogen generation is produced in which a conductive metal serving as a substrate of an electrode is coated with a cerium-platinum mixture based cerium-rich electrode active material.
  • the shape of the electrode base metal is preferably expanded metal, punching metal, interdigital, rod-like, plate-like or net-like metal, and the surface of the metal base may be oxidized. Expanded metal and punched metal plates are particularly preferred.
  • the expanded metal plate preferably has an LW of 4 to 40 mm and a thickness of 0.5 to 6 mm.
  • the punching metal may have a staggered arrangement of 45, 60, and 90 degrees openings, and the ratio of the opening area to the total area is 5 to 85%, and the hole diameter of the opening is preferably 1.5 to 25 mm, particularly 2 to 10 mm. .
  • a micromesh having a much smaller opening area than the expanded metal or punching metal or a woven mesh made of a thin conductive metal wire is used.
  • the LW is preferably 1 to 4 mm and the thickness is preferably 0.1 to 0.5 mm.
  • the woven mesh a wire having a diameter of 0.05 to 0.5 mm is used, but a diameter of 0.1 to 0.25 mm is more preferable.
  • the electrode active material is coated on both sides, but the current density is opposite to the anode. Since the display is generally performed by the current amount per area of the entire surface of one side (including the hole portion) of the cathode, the display method is also adopted in the description of the present invention.
  • the thermal decomposition method As the electrode active substance coating method, a conventionally used thermal decomposition method, powder sintering method, or the like can be applied, but the thermal decomposition method is preferable. That is, a metal salt solution constituting the electrode active substance is applied, dried, and heat-treated in air at a temperature of 350 ° C. to 550 ° C. Application, drying, and heating operations are performed several to several tens of times to form a necessary amount of the electrode active layer.
  • the platinum metal salt chloroplatinic acid and dinitrodiamineplatinum are used, and as the cerium metal salt, cerium carbonate, cerium oxalate, cerium sulfate, and cerium nitrate are used. In particular, cerium nitrate can be suitably used as an aqueous nitric acid solution.
  • Platinum metal includes those obtained by heat-treating a platinum-containing compound in air at a temperature of 350 ° C. to 550 ° C.
  • the ratio of platinum and cerium in the electrode active material is such that the molar fraction of platinum in terms of metal is 15 to 30 mol%, the molar fraction of cerium is 70 to 85 mol%, more preferably the molar fraction of platinum.
  • the rate is 20 to 25 mol%, and the molar fraction of cerium is 75 to 80 mol%.
  • the ion exchange membrane salt electrolysis industry operates at an electrolytic current density of 3 kA / m 2 to 5 kA / m 2 , but when the current density is low, the higher the proportion of platinum in the electrode active material, the more hydrogen The generated overvoltage is small.
  • the electrolysis current density is increased from 6 kA / m 2 to 14 kA / m 2 , more certainly from 8 kA / m 2 to 14 kA / m 2 , on the contrary, a phenomenon in which the overvoltage suddenly increases is observed.
  • the proportion of cerium oxide is large, the hydrogen generation overvoltage increases when the current density is low, but the increase in overvoltage is small even when the current density increases.
  • the electrode having the cerium-rich electrode active material is superior in terms of hydrogen generation overvoltage than the electrode having the platinum-rich electrode active material.
  • Example 1-1 (Production of electrode 1)
  • an expanded metal plate made of nickel metal LW: 8.0, SW: 3.6, ST: 1.2 mm
  • the dimensions of the expanded metal plate are 20 mm ⁇ 20 mm ⁇ 1.2 mm thick.
  • a nickel round bar having a diameter of 1.5 mm and a length of 80 mm was welded to the expanded metal plate to obtain a power supply lead for energization.
  • the expanded metal surface of the base was blasted at a pressure of 0.3 MPa using No. 100 alundum.
  • the expanded metal plate was degreased by ultrasonic cleaning in acetone and then etched at 30 ° C. for 1 hour using a 10 wt% hydrochloric acid aqueous solution.
  • the etched expanded metal plate was washed in running water all day and night.
  • An aqueous solution containing 6 wt% nitric acid was prepared by dissolving chloroplatinic acid hexahydrate and cerium nitrate hexahydrate so that the molar ratio of platinum: cerium was 25:75 as a coating solution for the electrode active substance.
  • the amount of platinum metal in the coating solution is 7.5 g / L.
  • This coating solution was applied to both surfaces of the expanded metal, dried at 100 ° C. for 10 minutes, and further baked in an electric furnace maintained at 450 ° C. for 20 minutes. This electrode active substance coating operation (coating, drying, heating) was repeated 10 times to produce “Electrode 1”.
  • Example 1-2 (Overvoltage measurement) The 20 mm ⁇ 20 mm expanded part of the “electrode 1” produced in Example 1 was left as the cathode and the other part was sealed as the cathode. A 30 mm ⁇ 30 mm ⁇ 1 mm thick nickel plate was used as the anode, and a 32 wt% sodium hydroxide aqueous solution was used as the electrolytic solution, and an electrolytic test was performed under the conditions of a distance of 2 cm between the cathode and the anode and a temperature of 80 ° C.
  • a part of the platinum wire covered with a tube made of PFA resin (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer) was exposed and adhered to the cathode to obtain a reference electrode. Care was taken not to contact the exposed portion of the platinum wire with the cathode.
  • the cathode hydrogen generation overvoltage was measured by the constant current method, and the error due to the liquid resistance was corrected from the voltage drop at the time of current interruption by the current interrupter method.
  • the relationship between the electrolytic current density and the hydrogen generation overvoltage, that is, the dependence of the hydrogen generation overvoltage on the electrolytic current density is shown in Table 1 and FIG.
  • the current density is 20 mm x 20 mm.
  • the value divided by (400 mm 2 ) was used.
  • Example 2 (Production of electrode 2 and measurement of overvoltage) The same surface treatment as in Example 1 was performed using an expanded metal made of nickel metal similar to that in Example 1 and a power supply lead as the electrode substrate.
  • An aqueous solution containing 6 wt% nitric acid was prepared by dissolving platinum dinitrodiamminate and cerium nitrate hexahydrate so that the molar ratio of platinum: cerium was 20:80 as a coating solution for the electrode active substance.
  • the amount of platinum metal in the coating solution is 7.5 g / L.
  • the prepared coating solution was applied on both sides of the expanded metal, dried at 100 ° C. for 10 minutes, and then baked in an electric furnace maintained at 470 ° C. for 20 minutes.
  • This electrode active substance coating operation (coating, drying, heating) was repeated 10 times to produce “electrode 2”.
  • the dependence of the hydrogen generation overvoltage on the “electrode 2” depending on the electrolytic current density was measured and is shown in Table 1 and FIG.
  • An aqueous solution containing 6 wt% nitric acid was prepared by dissolving chloroplatinic acid hexahydrate and cerium nitrate hexahydrate so that the molar ratio of platinum: cerium was 50:50 as a coating solution for the electrode active material.
  • the amount of platinum metal in the coating solution is 7.5 g / L.
  • the prepared coating solution was applied on both sides of the expanded metal, dried at 100 ° C. for 10 minutes, and then baked in an electric furnace maintained at 450 ° C. for 20 minutes. This electrode active substance coating operation (coating, drying, heating) was repeated 10 times to produce “electrode 3”.
  • the dependency of the hydrogen generation overvoltage on the “electrode 3” depending on the electrolytic current density was measured and is shown in Table 1 and FIG.
  • the “electrode 3” which is a comparative example of the present application has a low overvoltage in a range where the electrolysis current density is small, but the overvoltage becomes very high as the electrolysis current density increases.
  • “electrode 1” and “electrode 2”, which are examples of the present invention have a low dependence of the overvoltage on the electrolytic current density, and the overvoltage is stable. As a result, in the range where the electrolysis current density is small, the overvoltage is lower than that of “electrode 3”, but the electrolysis current density is 5 kA / m 2 and the three overvoltages are almost the same.
  • Electrode 1 When “Electrode 1” and “Electrode 2” are compared, “Electrode 2” with a small amount of platinum and a large amount of cerium has a lower hydrogen generation overvoltage in a high electrolysis current density region.
  • electrode 3 which is a comparative example of the present application has the same platinum amount and cerium amount in the electrode active material, and is a platinum rich material described in, for example, Patent Document 2 which is a conventional example (platinum amount is about twice the cerium amount).
  • the amount of platinum in the electrode active material is smaller and the amount of cerium is larger than the electrode having the electrode active material of
  • the overvoltage is lower than that of “electrode 3” in the region where the electrolysis current density is small, but in the region where the electrolysis current density is large Becomes higher than “electrode 3”.
  • the electrode for hydrogen generation of the present invention is extremely cerium-rich, with the amount of cerium in the electrode active material being about 3 to 4 times the amount of platinum as seen in “Electrode 1” and “Electrode 2”. Needless to say, the poisoning resistance to iron in the electrolyte is very high.
  • the electrode for hydrogen generation of the present invention can be used in an electrolysis process accompanied by hydrogen generation, mainly in salt exchange electrolysis using an ion exchange membrane method, and enables high electrolysis current density operation with low energy cost.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

L'invention porte sur une cathode destinée à être utilisée dans une opération d'électrolyse accompagnée du dégagement d'hydrogène, principalement pour une utilisation dans l'électrolyse de saumure dans un procédé à membrane échangeuse d'ion, dans lequel l'accroissement de la tension d'électrolyse peut être empêché même lorsque la densité de courant d'électrolyse est élevée, et le coût en énergie peut être réduit. L'invention porte spécifiquement sur une électrode destinée à être utilisée dans la production d'hydrogène, qui comprend un métal électroconducteur et une matière active d'électrode qui recouvre le métal électroconducteur, et comprend au moins un élément choisi parmi le cérium métallique, un oxyde de cérium et un hydroxyde de cérium, et le platine métallique, la matière active de l'électrode possédant une composition extrêmement riche en cérium telle que les fractions molaires de platine et de cérium sont de 15 à 30 mol% et 70 à 85 mol% respectivement, en terme de teneur en métaux.
PCT/JP2010/066945 2009-09-29 2010-09-29 Électrode pour la production d'hydrogène et procédé d'électrolyse WO2011040464A1 (fr)

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CN2010800248774A CN102471905A (zh) 2009-09-29 2010-09-29 析氢电极及电解方法
JP2011534274A JPWO2011040464A1 (ja) 2009-09-29 2010-09-29 水素発生用電極及び電解方法

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Cited By (2)

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CN103695959A (zh) * 2013-09-12 2014-04-02 西北工业大学 一种多级孔Ni(OH)2/NiCu析氢电极及其制备方法
US11396709B2 (en) 2017-08-11 2022-07-26 Lg Chem, Ltd. Electrode for electrolysis and preparation method thereof

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CN106934188B (zh) * 2015-12-24 2019-06-25 北京有色金属研究总院 一种析氢电极材料合金成分的筛选方法
CN106186204B (zh) * 2016-07-05 2019-03-15 宋玉琴 含铈的电解用电极及其制备方法
CN109234760B (zh) * 2018-10-31 2020-12-25 北京化工大学 一种活性阴极及其制备方法和应用

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JP4115575B2 (ja) * 1998-02-18 2008-07-09 ペルメレック電極株式会社 活性化陰極
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103695959A (zh) * 2013-09-12 2014-04-02 西北工业大学 一种多级孔Ni(OH)2/NiCu析氢电极及其制备方法
CN103695959B (zh) * 2013-09-12 2016-02-03 西北工业大学 一种多级孔Ni(OH)2/NiCu析氢电极及其制备方法
US11396709B2 (en) 2017-08-11 2022-07-26 Lg Chem, Ltd. Electrode for electrolysis and preparation method thereof

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