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WO2015083383A1 - Catalyseur d'électrode pour électrolyse de l'eau, et dispositif d'électrolyse de l'eau l'utilisant - Google Patents

Catalyseur d'électrode pour électrolyse de l'eau, et dispositif d'électrolyse de l'eau l'utilisant Download PDF

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WO2015083383A1
WO2015083383A1 PCT/JP2014/006102 JP2014006102W WO2015083383A1 WO 2015083383 A1 WO2015083383 A1 WO 2015083383A1 JP 2014006102 W JP2014006102 W JP 2014006102W WO 2015083383 A1 WO2015083383 A1 WO 2015083383A1
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Prior art keywords
catalyst
water electrolysis
oxide
electrode catalyst
carrier
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Japanese (ja)
Inventor
宜裕 小澤
羽藤　一仁
健一郎 太田
顕光 石原
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Panasonic Corp
Yokohama National University NUC
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Panasonic Corp
Yokohama National University NUC
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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
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a water electrolysis electrode catalyst and a water electrolysis apparatus using this water electrolysis electrode catalyst.
  • An example of an electrochemical device used under a high potential is a water electrolysis apparatus.
  • the anode is made of platinum (Pt), iridium oxide (IrO 2 ), etc. that are stable in a wide potential range and have a high catalytic ability for the electrochemical reaction of the anode. It is used as a catalyst, and platinum or the like is used as a catalyst for the cathode.
  • noble metals such as platinum and iridium have limited resources and are expensive, conventionally, methods for reducing the amount of noble metal used and catalysts that replace noble metals have been developed.
  • Patent Document 1 discloses using a metal oxide of a non-noble metal as an electrode catalyst as an alternative to a noble metal catalyst. Specifically, an electrocatalyst containing at least one transition metal oxide as a main catalyst among ZrO 2 , Ta 2 O 5 , Nb 2 O 5, TiO 2 and the like provided with oxygen defects as a main catalyst and gold as a promoter. Is disclosed. This electrode catalyst is stable even in an acidic electrolyte, and realizes high activity by providing a promoter. It is also disclosed that these catalysts are supported on an electron conductive carrier such as carbon, iridium oxide and tungsten oxide.
  • an electron conductive carrier such as carbon, iridium oxide and tungsten oxide.
  • Patent Document 2 discloses a catalyst for water electrolysis in which iridium oxide is supported on an inorganic oxide having a high BET surface area. Specifically, a catalyst containing an inorganic oxide having a high BET specific surface area such as titania (TiO 2 ), silica (SiO 2 ), alumina (Al 2 O 3 ), and iridium oxide is disclosed. The inorganic oxide is present in an amount of less than 20% by mass with respect to the total mass of the catalyst. Patent Document 2 discloses that this catalyst exhibits a higher catalytic activity than that of iridium oxide alone.
  • the catalyst In studying an electrocatalyst for water electrolysis that is stable even under high potential (water electrolysis conditions of 1.23 V or more), the catalyst is required to have stability under high potential and catalytic activity for each electrochemical reaction. It is done. Precious metals such as platinum and iridium oxide have catalytic activity for electrochemical reaction of water electrolysis, but are limited in resources and expensive. Therefore, the catalyst is preferably a catalyst with a reduced amount of noble metal used or a non-noble metal. Further, the carrier supporting the catalyst is required to be stable at a high potential and to have high electron conductivity because electrons contributing to the reaction move in the carrier. Furthermore, for the same reason as in the case of the catalyst, it is desired that the support does not contain a noble metal element.
  • Patent Document 1 uses, as an electron conductive carrier, carbon that dissolves into CO 2 by reaction under high potential, expensive iridium oxide, and the like, and is stable even under water electrolysis conditions. Problems remain in examining the electrocatalyst for water electrolysis.
  • the catalyst disclosed in Patent Document 2 has a structure in which iridium oxide having catalytic activity is supported on a support made of an inorganic oxide.
  • iridium oxide bears the electronic conductivity of the entire catalyst. Therefore, in order to ensure electronic conductivity, the amount of inorganic oxide must be suppressed to less than 20% by mass, and as a result, the amount of expensive iridium oxide used must be increased.
  • the present invention provides an electrode catalyst for water electrolysis that is stable even at a high potential and that can exhibit sufficient catalytic activity even when the amount of noble metal is reduced or no noble metal is contained. For the purpose.
  • the oxide contained in the support can have a relatively high surface area and electron conductivity while being a non-noble metal oxide, and even at a high potential. It is stable.
  • the catalyst supported on the carrier is an oxide in which an oxygen defect serving as an active site of reaction is provided in an oxide containing at least one element selected from the group consisting of Group 4 elements and Group 5 elements. It is a catalyst and exhibits a sufficient activity for water oxidation reaction while being stable at a high potential. Therefore, the electrode catalyst for water electrolysis is stable even at a high potential, and can further exhibit sufficient catalytic activity even if the amount of noble metal is reduced or no noble metal is contained.
  • FIG. 1 Schematic sectional view showing a configuration example of a water electrolysis apparatus according to Embodiment 2 of the present invention X-ray diffraction patterns of water electrolysis electrode catalyst powders of Examples 1 to 4 and Sb-doped tin oxide (ATO) used as a support in the water electrolysis electrode catalyst powders of Examples 1 to 4 X-ray diffraction patterns of water electrolysis electrode catalyst powders of Examples 6 to 8 and Sb-doped tin oxide (ATO) used as supports in the water electrolysis electrode catalyst powders of Examples 6 to 8
  • the first aspect of the present invention is: A support containing an oxide having at least one element selected from the group consisting of Sn, Sb, Nb, Ta and Ti and having an electron conductivity; An oxide catalyst having at least one element selected from the group consisting of Group 4 elements and Group 5 elements supported on the carrier and having oxygen defects; An electrode catalyst for water electrolysis is provided.
  • the oxide contained in the support can have a relatively high surface area and electronic conductivity while being a non-noble metal oxide, and is stable even at a high potential.
  • the catalyst supported on the carrier is an oxide in which an oxygen defect serving as an active site of reaction is provided in an oxide containing at least one element selected from the group consisting of Group 4 elements and Group 5 elements. It is a catalyst and exhibits a sufficient activity for water oxidation reaction while being stable at a high potential. Therefore, the electrode catalyst for water electrolysis according to the first aspect is stable even at a high potential, and can further exhibit a sufficient catalytic activity even when the amount of noble metal is reduced or no noble metal is contained. It is.
  • the catalyst ratio of the oxide catalyst in the electrode catalyst for water electrolysis (weight of the oxide catalyst / (weight of the oxide catalyst + weight of the support)) is more than 0 wt% and not more than 42 wt%.
  • An electrode catalyst for water electrolysis is provided.
  • the catalyst ratio is 42 wt% or less, the reduction of the surface area due to the aggregation of the catalysts is reduced, and the amount of the catalyst with poor electron conductivity is reduced, so that electrical contact between the carriers and the collecting electrode is achieved.
  • the number of points increases, electrons generated by the reaction are more easily moved, and high electron conductivity can be realized.
  • the electrode catalyst for water electrolysis which concerns on a 2nd aspect can implement
  • the carrier includes Sn and an oxide having electronic conductivity.
  • An electrode catalyst for water electrolysis is provided.
  • the carrier containing Sn and an oxide having electron conductivity is likely to cause oxygen defects at the interface with the oxide catalyst. Therefore, the electrode catalyst for water electrolysis according to the third aspect can realize higher electron conductivity. Thereby, the electrode catalyst for water electrolysis which concerns on a 3rd aspect can implement
  • the carrier includes an oxide obtained by doping SnO 2 with at least one element selected from the group consisting of Sb, Nb, and Ta.
  • An electrode catalyst for water electrolysis is provided.
  • An oxide obtained by doping SnO 2 with at least one element selected from the group consisting of Sb, Nb, and Ta can maintain stable oxygen defects. Therefore, oxygen diffusion occurs at the interface between the support and the oxide catalyst, and the decrease in the amount of oxygen defects in the oxide catalyst due to the electrochemical reaction is suppressed, so that the oxide catalyst can maintain high catalytic activity for a long period of time. It becomes possible. Thereby, the electrode catalyst for water electrolysis which concerns on a 4th aspect can implement
  • the oxide catalyst further comprises at least one element selected from the group consisting of N and C; An electrode catalyst for water electrolysis is provided.
  • Examples of the electrode catalyst for water electrolysis according to the fifth aspect include a configuration example in which part of oxygen in the oxide catalyst is substituted with N (nitrogen), C (carbon), or both. According to this configuration, the oxide catalyst has an increased amount of free electrons as the trivalent nitrogen or tetravalent carbon is substituted for the divalent oxygen, so that the electron conductivity of the catalyst itself is improved. Further, as another configuration example of the electrode catalyst for water electrolysis according to the fifth aspect, carbon or a substance in which a part of carbon is substituted with nitrogen covers at least a part of the surface of the oxide catalyst. A configuration is also mentioned. In this configuration example, carbon itself or a substance in which a part of carbon is substituted with nitrogen has conductivity, so that these become an electron conduction path when the catalyst undergoes a surface reaction. Thereby, the electronic conductivity of the catalyst itself is improved.
  • the Group 4 elements are Ti and Zr; An electrode catalyst for water electrolysis is provided.
  • the oxides of Ti and Zr are stable even in acidic electrolytes, and the oxides provided with oxygen defects have activity for water oxidation reaction. Therefore, according to the electrode catalyst for water electrolysis according to the sixth aspect, higher catalytic activity can be realized.
  • the Group 5 elements are Nb and Ta, An electrode catalyst for water electrolysis is provided.
  • the oxides of Nb and Ta are stable even in an acidic electrolyte, and the oxides provided with oxygen defects have activity for water oxidation reaction. Therefore, according to the electrode catalyst for water electrolysis according to the seventh aspect, higher catalytic activity can be realized.
  • any one of the first to seventh aspects And further comprising a promoter containing at least one element selected from the group consisting of Pt, Ir, Ni and Co.
  • a promoter containing at least one element selected from the group consisting of Pt, Ir, Ni and Co.
  • a substance containing at least one element selected from the group consisting of Pt, Ir, Ni and Co has high activity for water oxidation reaction. Therefore, according to the electrode catalyst for water electrolysis according to the eighth aspect, higher catalytic activity can be realized.
  • the ninth aspect of the present invention provides An anode including the electrocatalyst for water electrolysis according to any one of the first to eighth aspects;
  • a water electrolysis apparatus comprising:
  • the water electrolysis apparatus includes the electrode catalyst for water electrolysis according to any one of the first to eighth aspects having catalytic activity for water oxidation reaction as an anode catalyst. Therefore, the water electrolysis apparatus according to the ninth aspect can improve the efficiency of the water electrolysis apparatus and the system including the water electrolysis apparatus, and can reduce the amount of noble metal or reduce the cost by not using the noble metal.
  • the electrode catalyst for water electrolysis according to the present embodiment includes a support and an oxide catalyst supported on the support.
  • the carrier includes an oxide having at least one element selected from the group consisting of Sn, Sb, Nb, Ta, and Ti and having electron conductivity (hereinafter referred to as electron conductive oxide). Yes.)
  • the electron conductive oxide is desirably an oxide containing Sn.
  • the oxide catalyst includes at least one element selected from the group consisting of Group 4 elements and Group 5 elements, and has an oxygen defect.
  • the carrier carrying the catalyst is, for example, in the form of powder.
  • the carrier of this embodiment will be described by taking the case where the carrier is a powder as an example.
  • the carrier powder Since the carrier powder is responsible for the movement of electrons involved in the electrochemical reaction on the catalyst, the carrier itself needs to have electron conductivity. In particular, when the catalyst itself has poor electronic conductivity, the carrier becomes the main electron transfer path, so the electron conductivity of the carrier is important.
  • As a method for increasing the electron conductivity of the carrier there are mainly a method of positively introducing oxygen defects into an oxide contained in the carrier and a method of doping with other elements.
  • the electrons of the metal element are surplus, and the electrons become carrier electrons, thereby improving the electron conductivity.
  • tin oxide (SnO 2 ) is contained in the carrier, two electrons are left due to oxygen deficiency.
  • the support contains an oxide containing a tetravalent element (for example, tin oxide (SnO 2 ))
  • the oxide containing a tetravalent element is at least one of pentavalent elements (Sb, Nb, Ta)
  • Sb, Nb, Ta pentavalent elements
  • the electron conductive oxide contained in the carrier of the present embodiment is an oxide containing a tetravalent element
  • the content of the pentavalent element doped in the oxide containing the tetravalent element is 0.1 to 25 at% is preferable with respect to the element, and more preferably 1 to 15 at%.
  • the obtained oxide can maintain stable oxygen defects, so that oxygen diffusion occurs at the interface between the support and the oxide catalyst.
  • the oxide catalyst can maintain high catalytic activity for a long period of time. Therefore, it is desirable that the electron conductive oxide has electron conductivity realized by doping with other elements.
  • the electron conductivity of the carrier can be measured by a four-probe method or the like by pressing the carrier powder into a pellet by pressing with a hand press or the like.
  • Electronic conductivity of the carrier is preferably 0.01 Scm -1 or more, 0.1Scm -1 or more is more preferable.
  • the electron conductivity of the carrier is, for example, 10 Scm ⁇ 1 or less.
  • the BET specific surface area of the carrier powder is preferably 10 m 2 / g or more, and more preferably 100 m 2 / g or more.
  • the BET specific surface area of the carrier powder is, for example, 500 m 2 / g or less.
  • the shape of the carrier powder is not particularly limited, and it is possible to use spherical, aggregated, spherical, columnar, and needle-shaped powders in which spheres are fused together.
  • the carrier powder in the present embodiment only needs to contain the electron conductive oxide, desirably contains 20% by mass or more of the electron conductive oxide, and more desirably contains 50% by mass or more. It is that you are.
  • the carrier powder in the present embodiment may be made of the electron conductive oxide.
  • the electron conductive oxide may be coated with a substance serving as a base material.
  • the base material made of SiO 2 , Al 2 O 3 or the like contains an oxide having at least one element selected from the group consisting of Sn, Sb, Nb, Ta, and Ti and having electron conductivity. It may be covered with an electron conductive layer.
  • the oxide catalyst in the present embodiment includes at least one element selected from the group consisting of group 4 elements and group 5 elements, and has an oxygen defect.
  • the oxygen defect contained acts as an active site of the reaction, it becomes highly active for electrochemical reaction, particularly water oxidation reaction.
  • the oxygen defects in the oxide catalyst are preferably 1 to 10 at%. Note that the amount of oxygen defects can be calculated by elemental analysis using an inert gas melting infrared absorption method, whereby the presence or absence of oxygen defects can also be determined.
  • the catalyst may have a reduced oxygen defect amount and a catalytic activity with a high potential and an electrochemical reaction in an oxidizing atmosphere at an anode or the like in a water electrolysis apparatus, for example.
  • the electrode catalyst for water electrolysis of the present embodiment it is possible to use a carrier containing an electron conductive oxide that can maintain stable oxygen defects by doping with other elements, and has oxygen defects on the carrier.
  • An oxide catalyst can be supported. According to such a configuration, oxygen diffusion occurs at the interface between the support and the oxide catalyst, and a reduction in the amount of oxygen defects in the catalyst due to the electrochemical reaction is suppressed.
  • the oxide catalyst in the present embodiment can maintain high catalytic activity for a long period of time.
  • the oxide catalyst in the present embodiment can be prepared by supporting a precursor of a catalyst derived from an organometallic compound on a support and heat-treating it.
  • the precursor becomes an oxide (oxide catalyst) while depriving oxygen on the surface of the oxide as a support. Therefore, oxygen defects occur at the interface between the oxide catalyst and the support. Due to the presence of oxygen vacancies at the interface between the oxide catalyst and the support, the electrode catalyst for water electrolysis of the present embodiment can realize high electronic conductivity.
  • a support containing tin oxide that is easily reduced and oxygen is easily released can be used for the electrode catalyst for water electrolysis of the present embodiment.
  • the electrode catalyst for water electrolysis of the present embodiment it is possible to easily generate oxygen defects at the interface between the oxide catalyst and the carrier, and as a result, high electron conductivity can be obtained. Further, the surface of the electron-conducting oxide contained in the carrier is slightly reduced, for example, by being reheated at 100 to 300 ° C. in a vacuum atmosphere or a reducing atmosphere such as hydrogen or ammonia after the heat treatment. The conductivity can be improved. Thereby, the electrode catalyst for water electrolysis of this embodiment can further improve the catalytic ability. In this case, sintering of the electrode catalyst for water electrolysis and high temperature heat treatment accompanied by a decrease in surface area are not required.
  • the oxide catalyst in the present embodiment may further contain nitrogen, carbon, or both elements of nitrogen and carbon.
  • a part of oxygen of the oxide catalyst may be substituted with nitrogen, carbon, or both, or at least a part of the surface of the oxide catalyst is substituted with nitrogen. It may be coated with a different material.
  • the electron conductivity on the catalyst surface is improved by including a part of oxygen substituted on the catalyst surface with nitrogen, or containing carbon or a substance in which a part of carbon is substituted with nitrogen in the vicinity of the catalyst surface. The electron transfer on the catalyst surface is promptly performed.
  • a method of substituting part of oxygen of the oxide catalyst with nitrogen a method of heat-treating the oxide catalyst in a nitrogen stream or an ammonia stream, urea, melamine, pyrazine, purine, bipyridine, in which ammonia is generated by thermal decomposition
  • Examples thereof include a method in which acetanilide or piperazine is premixed with an oxide catalyst and heat-treated.
  • a transition metal carbide or transition metal carbonitride is heated in a mixed gas containing oxygen, and the oxide
  • a method of depositing carbon or the like can be used.
  • the oxide catalyst is not particularly limited as long as it is supported on a carrier.
  • oxide catalyst particles may be supported on the surface of the carrier powder, or a film made of an oxide catalyst may be formed in an island shape so as to cover at least a part of the surface of the carrier powder. Good. The entire surface of the carrier powder may be covered with a film made of an oxide catalyst.
  • the oxide catalyst is desirably a finer powder from the viewpoint of the reaction area.
  • the oxide catalyst is preferably nanoparticles having a particle size of 100 nm or less, and more preferably nanoparticles having a particle size of 50 nm or less.
  • the particle size of the oxide catalyst is, for example, 1 nm or more.
  • the oxide catalyst contains a Group 4 element
  • the Group 4 element is preferably Ti and / or Zr.
  • the Group 5 element is preferably Nb and / or Ta. The oxide containing these elements is stable even in an acidic electrolyte, and the oxide provided with an oxygen defect has activity for an oxygen reduction reaction and a water oxidation reaction. Therefore, higher catalytic activity can be realized.
  • the catalyst ratio of the oxide catalyst in the electrode catalyst for water electrolysis of the present embodiment is more than 0 wt% and not more than 42 wt%. Desirably, 32 wt% or less is more desirable, 23 wt% or less is particularly desirable, and 12 wt% or less is even more desirable.
  • the catalyst ratio is 42 wt% or less (desirably 32 wt% or less)
  • the reduction in the surface area due to aggregation of the catalysts is reduced, and the amount of the catalyst with poor electron conductivity is reduced, so that the carriers and current collectors are collected.
  • the number of electrical contact points with the electrode is increased, electrons generated by the reaction are more easily moved, and high electron conductivity can be realized. Therefore, by setting the catalyst ratio within the above range, it is possible to provide an electrode catalyst for water electrolysis that can more reliably realize stability under high potential and high catalytic activity.
  • the catalyst included as the main catalyst is the oxide catalyst, but the promoter includes at least one element selected from the group consisting of Pt, Ir, Ni and Co. May further be included.
  • the promoter includes at least one element selected from the group consisting of Pt, Ir, Ni and Co. May further be included.
  • noble metals such as Pt are included not only as a main catalyst but as a cocatalyst. Therefore, when viewed as a whole water electrolysis electrode catalyst, the noble metal is used as a main catalyst. Compared with the conventional electrode catalyst for water electrolysis that is used, the amount of noble metal used can be greatly reduced while having high catalytic activity.
  • the electrode catalyst for water electrolysis of the present embodiment is composed of an oxide for both the carrier and the main catalyst, it is stable in the electrolyte even under water electrolysis conditions (1.23 V or more).
  • FIG. 1 shows a solid polymer water electrolysis apparatus 100 which is an example of the configuration of the water electrolysis apparatus of the present embodiment.
  • a water electrolysis apparatus 100 shown in FIG. 1 includes a cathode, an anode, and a solid polymer electrolyte membrane (electrolyte layer) 110 disposed between the cathode and the anode.
  • the cathode is constituted by a cathode catalyst layer 120 disposed on one surface of the solid polymer electrolyte membrane 110 and a power supply body 140-1 disposed on the cathode catalyst layer 120.
  • the anode is composed of an anode catalyst layer 130 disposed on the other surface of the solid polymer electrolyte membrane 110 and a power feeder 140-2 disposed on the anode catalyst layer 130.
  • the laminate of the cathode, the solid polymer electrolyte membrane 110 and the anode is sandwiched between a separator 150-1 provided with a fluid channel 160-1 and a separator 150-2 provided with a fluid channel 160-2.
  • 170 indicates a gasket.
  • a known catalyst such as platinum can be used as the cathode catalyst of the solid polymer water electrolysis apparatus.
  • the anode catalyst layer 130 is an electrode catalyst for water electrolysis described in Embodiment 1 instead of a catalyst conventionally used as an anode catalyst of a solid polymer water electrolysis apparatus (for example, a noble metal catalyst such as platinum or iridium oxide). Is used.
  • a catalyst conventionally used as an anode catalyst of a solid polymer water electrolysis apparatus for example, a noble metal catalyst such as platinum or iridium oxide. Is used.
  • Water is supplied from the anode-side fluid flow path 160-2, and the water oxidation reaction shown in the above reaction formula (1) occurs on the anode catalyst layer 130 to generate oxygen and hydrogen ions.
  • the cathode catalyst layer 120 hydrogen ions are supplied from the anode side through the solid polymer electrolyte membrane 110, and hydrogen is generated by the reaction shown in the above reaction formula (2).
  • the water electrolysis apparatus 100 can generate hydrogen and oxygen from water.
  • the water electrolysis apparatus 100 uses the water electrolysis electrode catalyst according to the first embodiment as an anode catalyst, the efficiency of the water electrolysis apparatus and a system including the water electrolysis apparatus can be improved and the cost can be reduced.
  • the constituent elements other than the anode catalyst layer 130 may be the corresponding known constituent elements used in the known solid polymer water electrolysis apparatus, and thus detailed description thereof is omitted here. To do.
  • the solid polymer type water electrolysis apparatus has been described as an example, but the water electrolysis apparatus of the present embodiment is not limited to this, and can be applied to various types of apparatuses that electrolyze water.
  • Tin chloride dihydrate (SnCl 2 .2H 2 O) and antimony chloride (SbCl 3 ), niobium chloride (NbCl 5 ) or tantalum chloride (TaCl 5 ) were dissolved in a solvent (ethanol). While maintaining the resulting solution at a low temperature, diluted aqueous ammonia was added to the solution, and then this was filtered. The obtained filtrate was dried at 100 ° C.
  • an oxide in which SnO 2 is doped with Sb (Sb-doped tin oxide (hereinafter referred to as ATO)) and an oxide in which SnO 2 is doped with Nb (Nb-doped) Tin oxide (hereinafter referred to as NTO) and an oxide in which Ta was doped with SnO 2 (Ta-doped tin oxide (hereinafter referred to as TTO)) were prepared.
  • the carrier produced in the example the molar ratio of the oxide of the dopant element to SnO 2 was 5 mol%.
  • the carrier made of SnO 2 used in Comparative Example 1 was prepared by using the same heat treatment using only tin chloride dihydrate.
  • An oxide catalyst containing Zr and having an oxygen defect is obtained by thermally decomposing it in the atmosphere using zirconium tetrapropoxide as an organic zirconium compound or tantalum ethoxide as an organic tantalum compound as a starting material ( ZrO 2-x catalyst) or an oxide catalyst containing Ta and having an oxygen defect (Ta 2 O 5-x catalyst) was prepared.
  • the specific method is as follows.
  • the above starting material powder was placed on an alumina boat, it was subjected to atmospheric heat treatment at a predetermined temperature (550 to 700 ° C.) in a muffle furnace to obtain an electrode catalyst powder for water electrolysis.
  • Example 1 The starting material powder using ATO as the carrier and the weight ratio of the ZrO 2-x catalyst to the water electrocatalyst electrode catalyst (oxide catalyst + carrier) of 58 wt% is described in [Method for producing electrode catalyst for water electrolysis]. It was produced using the method described above. In Example 1, an electrode catalyst powder for ZrO 2-x / ATO water electrolysis was produced by atmospheric heat treatment at 550 ° C. for 1 h.
  • Example 2 An electrode catalyst powder for ZrO 2-x / ATO water electrolysis was prepared in the same manner as in Example 1 except that the heat treatment temperature was 600 ° C.
  • Example 3 An electrode catalyst powder for ZrO 2-x / ATO water electrolysis was prepared in the same manner as in Example 1 except that the heat treatment temperature was 650 ° C.
  • Example 4 An electrode catalyst powder for ZrO 2-x / ATO water electrolysis was prepared in the same manner as in Example 1 except that the heat treatment temperature was 700 ° C.
  • Example 5 The starting material powder using ATO as the carrier and the weight ratio of the ZrO 2-x catalyst to the electrocatalyst for water electrolysis (oxide catalyst + carrier) being 42 wt% is explained in the above [Method for producing electrode catalyst for water electrolysis]. It was produced using the method described above. In Example 5, an electrode catalyst powder for ZrO 2-x / ATO water electrolysis was prepared by atmospheric heat treatment at 700 ° C. for 1 h.
  • Example 6 The starting material powder using ATO as the carrier and the weight ratio of the ZrO 2-x catalyst to the water electrocatalyst electrode catalyst (oxide catalyst + carrier) being 32 wt% is explained in the above [Method for producing electrocatalyst for water electrolysis]. It was produced using the method described above. In Example 6, an electrode catalyst powder for ZrO 2-x / ATO water electrolysis was prepared by atmospheric heat treatment at 700 ° C. for 1 h.
  • Example 7 The starting material powder using ATO as the carrier and the weight ratio of the ZrO 2-x catalyst to the water electrocatalyst electrode catalyst (oxide catalyst + carrier) being 23 wt% is described in [Method for producing electrode catalyst for water electrolysis]. It was produced using the method described above. In Example 7, an electrode catalyst powder for ZrO 2-x / ATO water electrolysis was produced by atmospheric heat treatment at 700 ° C. for 1 h.
  • Example 8 The starting material powder using ATO as the carrier and the weight ratio of the ZrO 2-x catalyst to the electrocatalyst for water electrolysis (oxide catalyst + carrier) being 12 wt% is described in [Method for preparing electrode catalyst for water electrolysis]. It was produced using the method described above. In Example 8, an electrocatalyst powder for ZrO 2-x / ATO water electrolysis was produced by atmospheric heat treatment at 700 ° C. for 1 h.
  • Example 9 The starting material powder in which NTO is used as a carrier and the weight ratio of the ZrO 2-x catalyst to the water electrocatalyst electrode catalyst (oxide catalyst + carrier) is 12 wt% is described in [Method for producing electrode catalyst for water electrolysis]. It was produced using the method described above. In Example 9, an electrode catalyst powder for ZrO 2-x / NTO water electrolysis was prepared by atmospheric heat treatment at 700 ° C. for 1 h.
  • Example 10 The starting material powder using TTO as the carrier and the weight ratio of the ZrO 2-x catalyst to the water electrocatalyst electrode catalyst (oxide catalyst + carrier) being 12 wt% is described in [Method for producing electrode catalyst for water electrolysis]. It was produced using the method described above. In Example 10, an electrode catalyst powder for ZrO 2-x / TTO water electrolysis was produced by atmospheric heat treatment at 700 ° C. for 1 h.
  • Example 11 Starting material powder using NTO as a carrier and the weight ratio of the Ta 2 O 5-x catalyst to the electrode catalyst for water electrolysis (oxide catalyst + carrier) being 12 wt% is described in [Method for producing electrode catalyst for water electrolysis]. It was produced using the method described in 1. In Example 11, an electrode catalyst powder for Ta 2 O 5-x / NTO water electrolysis was prepared by atmospheric heat treatment at 700 ° C. for 1 h.
  • Example 12 The starting material powder in which NTO is used as a carrier and the weight ratio of the ZrO 2-x catalyst to the water electrocatalyst electrode catalyst (oxide catalyst + carrier) is 12 wt% is described in [Method for producing electrode catalyst for water electrolysis]. It was produced using the method described above. In Example 12, after an atmospheric heat treatment at 700 ° C. for 1 h, a reduction heat treatment was further performed at 200 ° C. for 1 h in a 1% hydrogen atmosphere to produce an electrode catalyst powder for ZrO 2-x / NTO water electrolysis.
  • Example 13 The starting material powder in which NTO is used as a carrier and the weight ratio of the ZrO 2-x catalyst to the water electrocatalyst electrode catalyst (oxide catalyst + carrier) is 12 wt% is described in [Method for producing electrode catalyst for water electrolysis]. It was produced using the method described above. In Example 13, after carrying out atmospheric heat treatment at 700 ° C. for 1 h, the obtained material was dispersed in an IrO 2 colloid solution, and then subjected to atmospheric heat treatment at 500 ° C. for 1 h, thereby supporting 1 wt% of IrO 2 . A ZrO 2-x / NTO electrocatalyst powder for water electrolysis was produced.
  • Comparative Example 1 A starting material powder using SnO 2 as a support and having a weight ratio of the ZrO 2-x catalyst to the electrocatalyst for water electrolysis (oxide catalyst + support) of 58 wt% was obtained in the above-mentioned [Method for producing electrocatalyst for water electrolysis]. Prepared using the method described. In Comparative Example 1, an electrode catalyst powder for ZrO 2-x / SnO 2 water electrolysis was produced by atmospheric heat treatment at 550 ° C. for 1 h.
  • Electrochemical measurement was performed using a three-electrode cell.
  • the working electrode produced by the above method was used, a platinum net was used for the counter electrode, and a silver / silver chloride (Ag / AgCl, 3M NaCl) electrode was used for the reference electrode.
  • the potential is based on a silver / silver chloride electrode (Ag / AgCl).
  • As the solution a 0.1 M sulfuric acid solution degassed by argon bubbling was used, and the measurement was performed at room temperature.
  • the scanning range was 0.8 V to 1.8 V and the scanning speed was 5 mVs ⁇ 1 as activity evaluation.
  • the cyclic voltamgram was measured for 7 cycles, and the current density at 1.8 V in the 7th cycle was used for activity evaluation.
  • Table 1 shows the activity evaluation results of the water electrolysis electrode catalysts of Examples 1 to 4 and Comparative Example 1
  • Table 2 shows the activity evaluation results of the water electrolysis electrode catalysts of Examples 4 to 8
  • Table 3 shows the activity evaluation results of Example 8.
  • the activity evaluation results of the electrocatalysts for water electrolysis of ⁇ 13 are shown respectively.
  • Tables 1 to 3 also show the configurations of the electrocatalysts for water electrolysis of each example and comparative example, the catalyst ratio (wt%), the catalyst ratio (at%), and the heat treatment temperature when preparing the electrocatalyst for water electrolysis. It is shown.
  • the catalyst ratio (at%) is calculated by the number of catalyst element atoms / (the number of catalyst element atoms + the number of Sn atoms) ⁇ 100.
  • the water electrolysis electrode catalyst having a higher heat treatment temperature during the production of the water electrolysis electrode catalyst had higher activity. This is considered that the crystallinity of the catalyst due to the heat treatment temperature affects the activity.
  • the water electrolysis electrocatalysts of all Examples had higher activity than the water electrolysis electrocatalyst of Comparative Example 1 in which the carrier did not satisfy the requirements of the present invention. . This is considered to be due to the electron conductivity of the carrier. This is because tin oxide that is not doped with other elements has few oxygen defects and low electron conductivity, so that it is insufficient as an electron conduction path for electrons generated in the reaction.
  • the catalyst ratio (catalyst loading) is 42 wt% or less, the catalyst has a high activity, and this is because the decrease in the surface area due to the aggregation of the catalysts is reduced. This is because the amount of the catalyst loaded with poor properties is reduced, so that the number of electrical contact points between the carriers and the collecting electrode is increased, and electrons generated by the reaction are more easily moved.
  • Example 9 As shown in Table 3, according to the comparison of Examples 8 to 10, the activity was highest when NTO was used as the carrier, followed by ATO and then TTO. Further, according to a comparison between Example 9 and Example 11, the activity of ZrO 2-x was higher than that of Ta 2 O 5-x as a catalyst. Moreover, the activity of the electrode catalyst for water electrolysis of Example 12 subjected to the reduction treatment was greatly improved as compared with the electrode catalyst for water electrolysis of Example 9 that was not subjected to the reduction treatment. Furthermore, from the results of Example 13, it was confirmed that the activity was further improved by adding IrO 2 as a cocatalyst.
  • the electrode catalyst for water electrolysis according to the present invention has stability and high activity under a high potential. Especially in energy devices such as water electrolysis devices, it is useful in that it can lead to a significant reduction in costs by replacing a conventional electrocatalyst for water electrolysis that contains precious metals, and may promote the spread to society. .

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Abstract

La présente invention concerne un catalyseur d'électrode pour électrolyse de l'eau contenant : un support qui comprend un oxyde présentant une conductivité électronique, et au moins un type d'élément choisi dans un groupe comprenant le Sn, le Sb, le Nb, le Ta et leTi ; et un catalyseur oxyde qui comprend au moins un type d'élément choisi dans un groupe comprenant les éléments du groupe 4 et les éléments du groupe 5 et supporté par le support, et présente un défaut d'oxygène.
PCT/JP2014/006102 2013-12-06 2014-12-05 Catalyseur d'électrode pour électrolyse de l'eau, et dispositif d'électrolyse de l'eau l'utilisant Ceased WO2015083383A1 (fr)

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WO2017022499A1 (fr) * 2015-08-04 2017-02-09 三井金属鉱業株式会社 Oxyde d'étain, catalyseur d'électrode pour piles à combustible, ensemble électrode à membrane, et pile à combustible à polymère solide
JP2019006741A (ja) * 2017-06-28 2019-01-17 国立大学法人九州大学 金属錯体、及び、該金属錯体を適用する燃料電池若しくは太陽電池
US20240271298A1 (en) * 2023-01-31 2024-08-15 Robert Bosch Gmbh Electrocatalyst support material

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JP6634339B2 (ja) * 2016-05-12 2020-01-22 昭和電工株式会社 酸素還元触媒及びその製造方法
KR102320011B1 (ko) * 2017-09-25 2021-11-02 주식회사 엘지화학 전기분해용 전극의 촉매 조성물, 이의 제조방법 및 이를 이용한 전기분해용 전극의 제조방법
WO2019117199A1 (fr) * 2017-12-14 2019-06-20 国立研究開発法人理化学研究所 Oxyde de manganèse pour catalyseurs de décomposition d'eau, mélange oxyde de manganèse-carbone, matériau d'électrode composite d'oxyde de manganèse, et méthodes respectives de production de ces matériaux
CN110565109A (zh) * 2018-06-05 2019-12-13 苏州庚泽新材料科技有限公司 含有Sn-Sb-过渡金属元素的活性材料、制备方法以及含有该活性材料的臭氧发生电极
JP2020122172A (ja) * 2019-01-29 2020-08-13 国立研究開発法人理化学研究所 水電気分解用積層体及びそれを用いた水電気分解装置

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