WO2015146490A1 - 酸素還元触媒及びその製造方法 - Google Patents
酸素還元触媒及びその製造方法 Download PDFInfo
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- WO2015146490A1 WO2015146490A1 PCT/JP2015/055966 JP2015055966W WO2015146490A1 WO 2015146490 A1 WO2015146490 A1 WO 2015146490A1 JP 2015055966 W JP2015055966 W JP 2015055966W WO 2015146490 A1 WO2015146490 A1 WO 2015146490A1
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- oxygen reduction
- oxide
- reduction catalyst
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- conductive oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- 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
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to an oxygen reduction catalyst that promotes an oxygen reduction reaction in an aqueous solution, and more particularly to an oxygen reduction catalyst used for an air electrode of an electrochemical device such as a fuel cell or an air cell, and a method for producing the same.
- Fuel cells and air cells are electrochemical energy devices that extract, as electric energy, energy generated by a chemical reaction between a compound serving as a fuel and a negative electrode active material using oxygen in the air as an oxidant.
- Fuel cells and air batteries have a higher theoretical energy capacity than secondary batteries such as Li-ion batteries, and are used as power sources for automobiles, stationary distributed power sources for homes and factories, or power sources for portable electronic devices. Can be used.
- an electrochemical reaction that reduces oxygen occurs on the oxygen electrode side of fuel cells and air cells.
- the oxygen reduction reaction does not easily proceed at a relatively low temperature, and can generally be promoted by a noble metal catalyst such as platinum (Pt).
- Pt platinum
- the energy conversion efficiency of fuel cells and air cells is still not sufficient.
- a noble metal catalyst mainly composed of a noble metal such as Pt is expensive, which increases the price of the entire fuel cell and air battery system and prevents its widespread use. Therefore, it is desired to develop an inexpensive catalyst that does not use a noble metal such as platinum and has a high oxygen reduction ability.
- Known catalysts that do not contain Pt include organometallic complexes, nitrogenated carbons, transition metal chalcogenides, transition metal carbonides, transition metal nitrides, etc., all of which are insufficient in terms of catalyst activity and durability. There is no performance superior to Pt-based catalysts.
- Non-Patent Documents 1 and 2 disclose that some of the transition metal oxides of Group 4 and Group 5 elements are active against oxygen reduction reaction. Further, in Non-Patent Document 3 and Patent Document 1, it is pointed out that a part of the structural defect may function as an active point of the oxygen reduction reaction. Furthermore, Non-Patent Documents 4 and 5 and Patent Document 1 disclose that conductive carbon or the like is imparted at the time of electrode configuration.
- the oxygen reduction reaction on the air electrode catalyst of a fuel cell or air cell is a reaction that involves electron transfer from the electrode. Therefore, in order to obtain good oxygen reduction catalyst performance, the reaction of the electron from the electrode to the catalyst is effective. It is necessary to move quickly to the vicinity of the point. In addition, it is necessary that oxygen and protons as reactants are promptly delivered to the reaction active point.
- the transition metal oxides of Group 4 and Group 5 elements described in Non-Patent Documents 1 to 3 and Patent Document 1 generally have an insulating electronic state, and thus have poor conductivity and react quickly. It is difficult. For this reason, when the battery is operated at a low current value, although a relatively high performance is exhibited, there is a problem that the operating voltage decreases in a high current region.
- Non-Patent Documents 4 and 5 and Patent Document 1 make it difficult to construct and control an effective electron conduction path in the vicinity of the active point at the nano level, and the performance remains low.
- the introduction of a large amount of conductive carbon hinders the supply of oxygen to the catalyst active site, and can improve the oxygen reduction performance by providing both conductivity and effective transport of oxygen. It has been demanded.
- Patent Document 2 oxygen defects are introduced into the transition metal oxide, or oxygen defects are introduced into the transition metal oxide, and a part of oxygen atoms is replaced with nitrogen atoms.
- a technique for improving the surface conductivity is disclosed.
- oxygen reduction performance is improved by arrange
- Non-Patent Document 6 discloses that a solution obtained by dissolving NbCl 5 and TiCl 4 in ethanol is dropped into mesoporous C 3 N 4 and infiltrated, followed by firing to decompose C 3 N 4.
- a technique for producing niobium-added titanium oxide (TiO 2 : Nb) by forming nitride nanoparticles and then oxidizing the nitride is disclosed.
- the niobium-doped titanium oxide (TiO 2 : Nb) is described as being useful as a platinum substitute catalyst because it is stable and maintains good conductivity even after oxidation.
- the present invention has been made in view of such problems, and an object thereof is to provide a novel oxygen reduction catalyst having good stability and high oxygen reduction performance.
- the inventors of the present invention have used a conductive oxide that is more stable with respect to carbon as a base material, and on the surface that should function as an active point for the oxygen reduction reaction of the conductive oxide, By providing an oxide of at least one transition metal selected from the group consisting of Ti, Zr, Nb, and Ta having voids, the stability of the oxygen reduction catalyst and the oxygen reduction performance are improved. I found it.
- the present invention provides a conductive oxide and at least one selected from the group consisting of Ti, Zr, Nb and Ta having oxygen vacancies provided on at least the surface of the conductive oxide.
- An oxygen reduction catalyst comprising an oxide of at least one kind of transition metal.
- the transition metal oxide when the transition metal oxide satisfies 0 ⁇ x ⁇ 0.2, TiO 2-x , ZrO 2-x , NbO 2-x , or It is represented by TaO 2-x .
- the oxygen reduction catalyst according to the present invention is an oxide of at least one transition metal selected from the group consisting of Ti, Zr, Nb and Ta.
- the conductive oxide is Ti 4 O 7 , Ti 3 O 5 , Ti 2 O 3 , TiO, Ti 3 O 2 , ZrO, NbO or TaO. It is.
- the oxygen reduction catalyst according to the present invention is formed by combining the conductive oxide and the transition metal oxide.
- the present invention is a fuel cell using the oxygen reduction catalyst of the present invention as an air electrode.
- the present invention is an air battery using the oxygen reduction catalyst of the present invention as an air electrode.
- the conductive oxide is 50 to 95% by mass, and the oxide selected from the group consisting of oxides of Ti, Zr, Nb, and Ta is 5 to 50% by mass.
- the method for producing an oxygen reduction catalyst according to the present invention includes a step of performing heat treatment at 800 to 1300 ° C. in an inert gas atmosphere of 1 to 100% hydrogen after mixing so as to be supported on at least the surface of a conductive oxide. .
- a novel oxygen reduction catalyst having good stability and high oxygen reduction performance can be provided.
- the oxygen reduction catalyst according to this embodiment includes at least one selected from the group consisting of a conductive oxide and Ti, Zr, Nb, and Ta having oxygen vacancies provided on at least the surface of the conductive oxide. And oxides of more than one kind of transition metal.
- the conductive oxide can function as a base material, and has good stability with respect to a material such as carbon while having conductivity.
- the oxygen The vacancies function effectively as active sites for the oxygen reduction reaction.
- a conductive oxide becomes a conduction pathway and can improve oxygen reduction performance. Furthermore, in the present invention, since Ti, Zr, Nb and Ta which are Group 4 and Group 5 elements are used as transition metal oxides, oxygen vacancies functioning as active sites for oxygen reduction reaction can be easily formed. Manufacturing efficiency is improved.
- the oxygen reduction catalyst according to the present embodiment is TiO 2-x , ZrO 2-x , NbO 2-x , or TaO 2-x when the transition metal oxide satisfies 0 ⁇ x ⁇ 0.2.
- the oxide represented may be sufficient.
- oxides of Ti, Zr, Nb, and Ta there are higher-order TiO 2 , ZrO 2 , Nb 2 O 5 , and Ta 2 O 5 , which are insulators.
- oxides of Ti, Zr, Nb and Ta there are low-order Ti 4 O 7 , ZrO, NbO and TaO, which are conductive, but when used as an oxygen reduction catalyst, oxygen and Since it reacts and the reaction ends there, no oxygen reduction reaction takes place.
- these low-order Ti 4 O 7 , ZrO, NbO, and TaO have low oxygen reduction activity. Therefore, in this embodiment, these higher-order TiO 2 , ZrO 2 , Nb 2 O 5 , Ta 2 O 5 and lower-order Ti 4 O 7 , ZrO, NbO, TaO are intermediate oxides.
- An oxide (0 ⁇ x ⁇ 0.2) represented by TiO 2-x , ZrO 2-x , NbO 2-x , or TaO 2-x is used. Since the oxide is not a high-order oxide such as TiO 2 , ZrO 2 , Nb 2 O 5 , and Ta 2 O 5 , it functions as an active point for the oxygen reduction reaction while having a certain degree of conductivity. Since oxygen vacancies are provided, oxygen reduction reactivity is improved.
- the transition metal oxides of Ti, Zr, Nb, and Ta having oxygen vacancies are those in which oxygen atoms are lost from the highest oxide state of transition metals of Ti, Zr, Nb, and Ta.
- the amount of oxygen vacancies can be calculated by elemental analysis or the like by an inert gas melting infrared absorption method, whereby the presence or absence of oxygen vacancies can also be determined.
- transition metal oxide having oxygen vacancies the characteristics of the oxygen reduction catalyst when Ti, Zr, Nb, and Ta transition metal oxides are used alone are compared.
- transition metal oxides having oxygen vacancies (1) Ti oxide or Zr oxide, (2) Nb oxide, and (3) Ta oxide have better activity in this order. can get. Further, (1) Ta oxide, (2) Nb oxide, (3) Zr oxide, and (4) Ti oxide are obtained in the order of better stability.
- the oxygen reduction catalyst according to the present embodiment is preferably small in order to increase the reaction surface area with respect to the size of the transition metal oxide, and is preferably in the range of 1 nm to 100 nm, for example.
- the conductive oxide of the oxygen reduction catalyst according to the present embodiment is not particularly limited.
- ITO indium / tin oxide
- ATO antimony / tin oxide
- perovskite type oxidation such as LaCoO 3 and LaNiO 3
- Various generally known conductive oxides such as materials can be used.
- the conductive oxide may be an oxide of at least one transition metal selected from the group consisting of Ti, Zr, Nb, and Ta.
- the conductive oxide can function as a base material, but the oxide having oxygen vacancies provided on at least the surface of the conductive oxide is Ti.
- the oxide can be manufactured at a time. For this reason, manufacturing efficiency can be improved. Further, when manufactured in this manner at once, the conductive oxide and the oxide having oxygen vacancies can be combined, and the oxygen reduction performance can be further improved.
- the oxygen reduction catalyst according to this embodiment may be formed by simultaneously forming a conductive oxide and an oxide of a transition metal having oxygen vacancies in this way, and the conductive oxide and oxygen vacancies may be combined. After preparing separately the transition metal oxide having a transition metal oxide, a transition metal oxide having oxygen vacancies may be provided on at least the surface of the conductive oxide.
- the conductive oxide may be Ti 4 O 7 , Ti 3 O 5 , Ti 2 O 3 , TiO, Ti 3 O 2 , ZrO, NbO, or TaO. According to such a configuration, the conductivity of the conductive oxide functioning as a base material is increased, and the oxygen reduction performance can be further improved.
- a single substance can be used as the conductive oxide, or a plurality of substances can be mixed and used.
- a single substance can be used as the transition metal oxide having oxygen vacancies, and a plurality of substances can be mixed and used.
- the combination of the conductive oxide and the oxygen reduction catalyst is not particularly limited, but a combination of those containing the same kind of elements is more preferable. According to such a configuration, it becomes difficult to form a boundary between the conductive oxide and the oxygen reduction catalyst provided on the surface thereof, and a better composite structure is obtained, so that the oxygen reduction performance is further improved.
- the oxygen reduction catalyst is also composed mainly of an oxide of Ti.
- the oxygen reduction catalyst is mainly composed of an oxide of Zr.
- the oxygen reduction catalyst is mainly composed of an oxide of Nb.
- the oxygen reduction catalyst is composed mainly of Ta oxide.
- the form of forming the conductive oxide is not particularly limited, and may be, for example, a plate shape, a spherical shape, a fiber shape, a layer shape, a porous shape, or the like.
- the oxide having oxygen vacancies may be provided not only on the surface of the conductive oxide but also inside. When the conductive oxide is formed into a porous shape, it is preferable that an oxide having oxygen vacancies is also provided on the surface of each hole.
- an oxide selected from the group consisting of (1) a conductive oxide and (2) an oxide of Ti, Zr, Nb, and Ta is prepared.
- (1) conductive oxide is prepared in an amount of 50 to 95% by mass
- (2) an oxide selected from the group consisting of oxides of Ti, Zr, Nb, and Ta is prepared in an amount of 5 to 50% by mass.
- the oxide selected from the group consisting of oxides of Ti, Zr, Nb and Ta is mixed for 1 to 10 hours so that it is supported on at least the surface of the conductive oxide.
- the conductive oxide and at least one or more transition metals selected from the group consisting of Ti, Zr, Nb, and Ta having oxygen vacancies provided on at least the surface of the conductive oxide An oxygen reduction catalyst containing the oxide of is obtained.
- the conductive oxide that is the base material of the oxygen reduction catalyst obtained after the heat treatment is Ti 4 O 7 , Ti 3 O 5 , Ti 2 O 3 , TiO, Ti 3 O 2 or the like.
- the conductive oxide that becomes the base material of the oxygen reduction catalyst obtained after the heat treatment is ZrO or the like.
- Nb 2 O 5 is used as the conductive oxide
- the conductive oxide serving as a base material of the oxygen reduction catalyst obtained after the heat treatment is NbO or the like.
- Ta 2 O 5 is used as the conductive oxide
- the conductive oxide that becomes the base material of the oxygen reduction catalyst obtained after the heat treatment is TaO or the like.
- the oxide selected from the group consisting of oxides of Ti, Zr, Nb and Ta determines the oxide of transition metal having oxygen vacancies.
- ZrO 2 the transition metal oxide having oxygen vacancies becomes ZrO 2-x .
- Nb 2 O 5 the transition metal oxide having oxygen vacancies becomes NbO 2-x .
- Ta 2 O 5 the transition metal oxide having oxygen vacancies becomes TaO 2-x .
- the composite resulting from the oxide selected from the group consisting of (2) Ti, Zr, Nb and Ta oxides is supported on (1) the conductive oxide by mixing with a ball mill or the like.
- (1) TiO 2 is mixed at 50 to 95% by mass
- (2) Nb 2 O 5 is mixed at 5 to 50% by mass
- a ball mill or the like to form a composite of TiO 2 and TiNbO.
- the compound is supported.
- NbO 2-x which is an oxide of a transition metal having oxygen vacancies
- the NbO 2-x notation here is the composite oxide TiNbO that is formed as the active point.
- the metal oxide locally has the highest oxidation number. It shows a lower state.
- heat treatment is performed in an inert gas atmosphere of 1 to 100% hydrogen, the oxygen partial pressure is reduced, so that oxygen vacancies are satisfactorily provided in the transition metal oxide. Can do.
- An air electrode can be produced using the oxygen reduction catalyst according to the present embodiment.
- the air electrode can be used for a fuel cell or an air cell.
- an electrolytic solution for the fuel cell an electrolytic solution having any properties of an acidic solution, an alkaline solution, a neutral solution, and an organic solvent can be used. It does not restrict
- the electrolytic solution and the negative electrode active material are not particularly limited.
- it can also be utilized as an air electrode of a Li air battery using a substance containing Li as a negative electrode.
- TiO 2 particle size: 100 nm, manufactured by Soekawa Chemical Co., Ltd.
- Nb 2 O 5 particle size: 1 ⁇ m, manufactured by High Purity Chemical Laboratory
- Ta 2 O 5 particle size: 10 nm, manufactured by High Purity Chemical Laboratory
- ZrO 2 particle size: 20 nm, TECNAN
- Fritsch Corp. equipped with zirconia balls is prepared.
- PLP-7 planetary ball mill premium line made for mixing for 3 hours. Subsequently, calcination was performed at 1050 ° C.
- XPS measurement For each oxygen reduction catalyst after calcination at 1050 ° C. for 40 hours prepared in the Examples, XPS measurement was performed with an XPS measurement apparatus (ULVAC-PHI, model PHI Quantum-2000). The measurement results are shown in FIGS.
- Oxygen reducing ability evaluation test 1 a three-electrode cell saturated with nitrogen at an electrolyte of 0.1 mol / dm 3 H 2 SO 4 and a temperature of 30 ⁇ 5 ° C. was prepared.
- the reference electrode was a reversible hydrogen electrode (RHE) and the counter electrode was a glassy carbon plate.
- RHE reversible hydrogen electrode
- CV cyclic voltammetry
- FIG. 2 shows the relationship between the current and potential of ORR (oxygen reduction reaction) per unit mass including the catalyst support, using the calculation results. According to FIG. 2, no current flowed in the catalyst before the oxide heat treatment, regardless of the type of element. Moreover, all after baking are 0.9Vvs. It can be seen that oxygen reduction has already started from RHE and the activity is high.
- any element (Nb, Zr, Ta) is more peaked than a void-free oxide (Nb 2 O 5 , ZrO 2 , Ta 2 O 5 ). Has shifted to the lower energy side, indicating that it is in a reduced state.
- Oxygen reducing ability evaluation test 2 Of the above examples, using the oxygen reduction catalyst prepared with TiO 2 and Nb 2 O 5 (the oxygen reduction catalyst of (4) in FIG. 2), evaluation similar to the oxygen reduction ability evaluation test 1 was performed twice. (1st, 2nd) and the oxygen reduction current density i ORR was calculated.
- FIG. 6 shows the relationship between the current and potential of ORR (oxygen reduction reaction) per unit mass including the catalyst support, using the calculation results. According to FIG. 6, the starting potential when using an oxygen reduction catalyst made of TiO 2 and Nb 2 O 5 is 1.1 V, and when Pt is used as an oxygen reduction catalyst (starting potential 1.05 V). The result was better than that.
- Oxygen reducing ability evaluation test 3 Among the above examples, for an oxygen reduction catalyst prepared with TiO 2 and Nb 2 O 5 (the oxygen reduction catalyst of (4) in FIG. 2), the start / stop test was performed, and the electrolyte was 0.1 mol / dm 3 of H 2. SO 4 , 30 ° C. (assuming room temperature), test voltage 1.0 to 1.5 Vvs. 20,000 cycles were performed using RHE and a triangular wave with a potential scanning speed of 500 mV / s. Next, for the oxygen reduction catalyst, the same evaluation as in the oxygen reduction ability evaluation test 1 was performed for the samples after 0 cycle and 20000 cycles, and the oxygen reduction current density i ORR was calculated. Using the calculation results, FIG. 7 shows the relationship between the current and potential of ORR (oxygen reduction reaction) per unit mass including the catalyst support. According to FIG. 7, it can be seen that the oxygen reduction ability of the oxygen reduction catalyst is not deteriorated even after 20000 cycles.
- ORR oxygen reduction reaction
- Oxygen reducing ability evaluation test 4 for an oxygen reduction catalyst prepared with TiO 2 and Nb 2 O 5 (the oxygen reduction catalyst of (4) in FIG. 2), the start / stop test was performed, and the electrolyte was 0.1 mol / dm 3 of H 2. SO 4 , 80 ° C. (assuming actual fuel cell operating conditions), test voltage 1.0-1.5 Vvs. 20,000 cycles were performed using RHE and a triangular wave with a potential scanning speed of 500 mV / s.
- FIG. 8 shows the relationship between the ORR (oxygen reduction reaction) current and the amount of electricity for each cycle including the catalyst carrier, using the calculation results. According to FIG. 8, it can be seen that the activity is almost constant in the samples after each cycle, and the amount of electricity is hardly changed between the samples after each cycle.
- Oxygen reducing ability evaluation test 5 for an oxygen reduction catalyst prepared with TiO 2 and Nb 2 O 5 (the oxygen reduction catalyst of (4) in FIG. 2), the start / stop test was performed, and the electrolyte was 0.1 mol / dm 3 of H 2. SO 4 , 80 ° C. (assuming actual fuel cell operating conditions), test voltage 1.0-1.5 Vvs. 20,000 cycles were performed using RHE and a triangular wave with a potential scanning speed of 500 mV / s. Next, the oxygen reduction catalyst was subjected to the same evaluation as in the oxygen reduction ability evaluation test 1 for the samples after 0 cycle, 5000 cycles, 10000 cycles, and 20000 cycles, and the oxygen reduction current density i ORR was calculated. FIG.
- FIG. 9 shows that 0.7 Vvs.
- the relationship of the ratio of the oxygen reduction current density at each cycle to the oxygen reduction current density at the 0th cycle in RHE is shown. According to FIG. 9, it can be seen that the catalytic performance of the oxygen reduction catalyst of the example does not deteriorate even if the number of cycles is increased with respect to the oxygen reduction current density at the 0th cycle (0.7 V vs. RHE).
- Oxygen reducing ability evaluation test 6 the oxygen reduction catalyst prepared with TiO 2 and Nb 2 O 5 (the oxygen reduction catalyst of (4) in FIG. 2) was subjected to a load response test, and the electrolyte was 0.1 mol / dm 3 of H 2. SO 4 , 80 ° C. (assuming actual fuel cell operating conditions), test voltage 0.6-1.0 Vvs. 20,000 cycles were performed using a RHE and a rectangular wave having a voltage holding time of 3 seconds. Next, the oxygen reduction catalyst was subjected to the same evaluation as in the oxygen reduction ability evaluation test 1 for the samples after 0 cycle, 1000 cycle, 2500 cycle, 5000 cycle, 10000 cycle, and 20000 cycle. ORR was calculated. FIG.
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Abstract
Description
本実施形態に係る酸素還元触媒は、導電性酸化物と、導電性酸化物の少なくとも表面に設けられた、酸素空孔を有する、Ti、Zr、Nb及びTaからなる群から選択された少なくとも1種以上の遷移金属の酸化物とを含む。本実施形態に係る酸素還元触媒において、導電性酸化物は母材として機能することができ、導電性を有しつつ、カーボンのような材料に対して安定性が良好である。また、導電性酸化物の少なくとも表面に、酸素空孔を有する、Ti、Zr、Nb及びTaからなる群から選択された少なくとも1種以上の遷移金属の酸化物が設けられているため、当該酸素空孔が酸素還元反応の活性点として有効に機能する。そして、当該活性点である酸素空孔の近傍に上記導電性酸化物が存在するため、導電性酸化物が伝導経路となり、酸素還元性能を向上させることができる。さらに、本発明では遷移金属の酸化物として、4属、5属元素であるTi、Zr、Nb及びTaを用いているため、酸素還元反応の活性点として機能する酸素空孔を形成し易く、製造効率が良好となる。
次に、本実施形態に係る酸素還元触媒の製造方法について説明する。まず、(1)導電性酸化物、及び、(2)Ti、Zr、Nb及びTaの酸化物からなる群から選択された酸化物を準備する。次に、(1)導電性酸化物が50~95質量%、(2)Ti、Zr、Nb及びTaの酸化物からなる群から選択された酸化物が5~50質量%となるように調合した後、ボールミル等を用いて、Ti、Zr、Nb及びTaの酸化物からなる群から選択された酸化物が、導電性酸化物の少なくとも表面に担持するように1~10時間混合する。続いて、1~100%水素の不活性ガス雰囲気下で、1~50時間、800~1300℃の熱処理を行い、上記混合物の還元処理を行う。このようにして、導電性酸化物と、導電性酸化物の少なくとも表面に設けられた、酸素空孔を有する、Ti、Zr、Nb及びTaからなる群から選択された少なくとも1種以上の遷移金属の酸化物とを含む酸素還元触媒が得られる。
本実施形態に係る酸素還元触媒を用いて空気極を作製することができる。当該空気極は、燃料電池や空気電池に用いることができる。該燃料電池の電解液としては、酸性溶液、アルカリ溶液、中性溶液、有機系溶媒のいかなる性質をもつ電解液も使用することができる。燃料電池の燃料としては特に制限されず、水素、メタノール又は水素化合物等を用いることができる。空気電池の場合も同様に電解液や負極活物質は特に限定されない。また、Liを含む物質を負極とするLi空気電池の空気極として利用することもできる。
実施例で作製した各酸素還元触媒について、ボールミル後且つ熱処理前のもの(焼成前と表記)、及び、40時間で1050℃の焼成後のもの(40hと表記)について、それぞれ、XRD(Ultima IV X-RAY DIFFRACTION METER、Rigaku社製)を用いて粉末X線回折の測定を行った。測定結果を図1に示す。粉末X線回折の測定により、(2)としてZrO2を用いたものについてZrO2-x構造を含む複合酸化物相が形成されていることが確認された。また、(2)としてNb2O5を用いたものについてNbO2-x構造を含む酸化物相が形成されていることが確認された。また、(2)としてTa2O5を用いたものについてTaO2-x構造を含む酸化物相が形成されていることが確認された。また、TiO2のみを用いたものについてTiO2-x構造を持つ酸化物相が形成されていることが確認された。
実施例で作製した40時間で1050℃の焼成後の各酸素還元触媒について、XPS測定装置(アルバック-ファイ社、型式PHI Quantum-2000)にてXPS測定を行った。測定結果を図3~5に示す。
上記実施例で作製した各酸素還元触媒について、酸化物熱処理前のものと、40時間熱処理後のものとを、それぞれ10mg採取し、5質量%ナフィオン(登録商標)16.6μLと1-ヘキサノール溶液428.4μLの混合溶液に加えて、触媒インクを調製した。次に、触媒インクを超音波処理により分散した後、鏡面処理したグラッシーカーボン(GC、φ5.2mm、東海カーボン社製)に担体を含んだ触媒担体量0.15mgを目安に滴下し、60℃の恒温槽で乾燥して作用極とした。
次に、酸素還元能評価試験1として、電解質を0.1mol/dm3のH2SO4とし、温度を30±5℃とし、窒素で飽和した三電極式セルを準備した。参照極を可逆水素電極(RHE)、対極をグラッシーカーボンプレートとした。前処理として酸素雰囲気でCyclic Voltammetry(CV)を走査速度150mV/s、0.05~1.2Vvs.RHEの範囲で300サイクル行った。その後、Slow Scan Voltammetry (SSV)を走査速度5mV/s、0.2~1.2Vvs.RHEの範囲で酸素、窒素雰囲気にてそれぞれ3サイクル行った。3サイクル目のSSVから得た酸素雰囲気の電流密度から窒素雰囲気でのバックグラウンドの電流密度を引いて酸素還元電流密度iORRを算出した。算出結果を用いて、図2に、触媒の担体を含む単位質量当たりのORR(酸素還元反応)の電流と電位との関係を示す。図2によれば、酸化物熱処理前の触媒では、元素の種類によらず、どれも同様に電流が流れなかった。また、焼成後のものは、いずれも0.9Vvs.RHEから既に酸素還元し始めており、活性が高いことがわかる。また、特にTiO2+Nb2O5の組み合わせで作製した酸素還元触媒を用いたものが最も酸素還元能が高いことがわかった。
また、図2によれば、熱処理を行うことで混合物全体に複合化が行われて、酸素空孔を有する遷移金属の酸化物が少なくとも導電性酸化物であるTi4O7の表面に生成していることがわかる。これは、酸素還元反応は触媒表面でしか起こり得ず、図2のように触媒能を持つことそのものが、活性点(酸素空孔)が表面にあることを示しているためである。
さらに、図3~5によれば、各酸素還元触媒において、いずれの元素(Nb、Zr、Ta)も空孔のない酸化物(Nb2O5、ZrO2、Ta2O5)よりもピークが低エネルギー側にシフトしており、還元状態にあることを示した。
上記実施例のうち、TiO2とNb2O5とで作製した酸素還元触媒(図2の(4)の酸素還元触媒)を用いて、上記酸素還元能評価試験1と同様の評価を2回行い(1st、2nd)、酸素還元電流密度iORRを算出した。算出結果を用いて、図6に、触媒の担体を含む単位質量当たりのORR(酸素還元反応)の電流と電位との関係を示す。
図6によれば、TiO2とNb2O5とで作製した酸素還元触媒を用いたときの開始電位が1.1Vとなり、Ptを酸素還元触媒として用いた場合(開始電位1.05V)に比べて良好な結果となった。
上記実施例のうち、TiO2とNb2O5とで作製した酸素還元触媒(図2の(4)の酸素還元触媒)について、起動停止試験を、電解質を0.1mol/dm3のH2SO4とし、30℃(室温を想定)、試験電圧1.0~1.5Vvs.RHE、電位走査速度500mV/sの三角波を用いて20000サイクル行った。次に、当該酸素還元触媒について、上記酸素還元能評価試験1と同様の評価を0サイクル、20000サイクル後のサンプルについてそれぞれ行い、酸素還元電流密度iORRを算出した。算出結果を用いて、図7に、触媒の担体を含む単位質量当たりのORR(酸素還元反応)の電流と電位との関係を示す。
図7によれば、20000サイクル後であっても酸素還元触媒の酸素還元能が劣化していないことがわかる。
上記実施例のうち、TiO2とNb2O5とで作製した酸素還元触媒(図2の(4)の酸素還元触媒)について、起動停止試験を、電解質を0.1mol/dm3のH2SO4とし、80℃(実際の燃料電池の操業条件を想定)、試験電圧1.0~1.5Vvs.RHE、電位走査速度500mV/sの三角波を用いて20000サイクル行った。次に、当該酸素還元触媒について、上記酸素還元能評価試験1と同様の評価を0サイクル、3000サイクル、5000サイクル、10000サイクル、20000サイクル後のサンプルについてそれぞれ行い、酸素還元電流密度iORRを算出した。算出結果を用いて、図8に、触媒の担体を含む各サイクルに対するORR(酸素還元反応)の電流と電気量との関係を示す。
図8によれば、活性は各サイクル後のサンプルでほぼ一定であり、電気量も各サイクル後のサンプル間でほとんど変わらないことがわかる。
上記実施例のうち、TiO2とNb2O5とで作製した酸素還元触媒(図2の(4)の酸素還元触媒)について、起動停止試験を、電解質を0.1mol/dm3のH2SO4とし、80℃(実際の燃料電池の操業条件を想定)、試験電圧1.0~1.5Vvs.RHE、電位走査速度500mV/sの三角波を用いて20000サイクル行った。次に、当該酸素還元触媒について、上記酸素還元能評価試験1と同様の評価を0サイクル、5000サイクル、10000サイクル、20000サイクル後のサンプルについてそれぞれ行い、酸素還元電流密度iORRを算出した。図9に、触媒の担体を含む各サイクルにおける、0.7Vvs.RHEにおける0サイクル時の酸素還元電流密度に対する、各サイクル時の酸素還元電流密度の比の関係を示す。
図9によれば、0サイクル目の酸素還元電流密度(0.7Vvs.RHE)に対して、サイクルが増えても、実施例の酸素還元触媒の触媒能は劣化しないことがわかる。
上記実施例のうち、TiO2とNb2O5とで作製した酸素還元触媒(図2の(4)の酸素還元触媒)について、負荷応答試験を、電解質を0.1mol/dm3のH2SO4とし、80℃(実際の燃料電池の操業条件を想定)、試験電圧0.6~1.0Vvs.RHE、それぞれの電圧保持時間3秒の矩形波を用いて20000サイクル行った。次に、当該酸素還元触媒について、上記酸素還元能評価試験1と同様の評価を0サイクル、1000サイクル、2500サイクル、5000サイクル、10000サイクル、20000サイクル後のサンプルについてそれぞれ行い、酸素還元電流密度iORRを算出した。図10に、触媒の担体を含む各サイクルに対する0.7Vvs.RHEにおける0サイクル時の酸素還元電流密度に対する、各サイクル時の酸素還元電流密度の比を示す。
図10によれば、0サイクル目の酸素還元電流密度(0.7Vvs.RHE)に対して、サイクルが増えても、実施例の酸素還元触媒の触媒能は劣化しないことがわかる。
Claims (8)
- 導電性酸化物と、
前記導電性酸化物の少なくとも表面に設けられた、酸素空孔を有する、Ti、Zr、Nb及びTaからなる群から選択された少なくとも1種以上の遷移金属の酸化物と、
を含む酸素還元触媒。 - 前記遷移金属の酸化物が、0<x≦0.2としたとき、TiO2-x、ZrO2-x、NbO2-x、又は、TaO2-xで表される請求項1に記載の酸素還元触媒。
- 前記導電性酸化物が、Ti、Zr、Nb及びTaからなる群から選択された少なくとも1種以上の遷移金属の酸化物である請求項1又は2に記載の酸素還元触媒。
- 前記導電性酸化物が、Ti4O7、Ti3O5、Ti2O3、TiO、Ti3O2、ZrO、NbO又はTaOである請求項3に記載の酸素還元触媒。
- 前記導電性酸化物と前記遷移金属の酸化物とが複合化されて形成されている請求項3又は4に記載の酸素還元触媒。
- 請求項1~5のいずれか一項に記載の酸素還元触媒を空気極として用いた燃料電池。
- 請求項1~5のいずれか一項に記載の酸素還元触媒を空気極として用いた空気電池。
- 導電性酸化物を50~95質量%に対し、Ti、Zr、Nb及びTaの酸化物からなる群から選択された酸化物を5~50質量%を前記導電性酸化物の少なくとも表面に担持させるように混合した後、1~100%水素の不活性ガス雰囲気下で800~1300℃の熱処理を行う工程を含む請求項1~5のいずれか一項に記載の酸素還元触媒の製造方法。
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DE112015001452T5 (de) | 2016-12-29 |
CA2943737C (en) | 2019-09-03 |
JP6570515B2 (ja) | 2019-09-04 |
CN106132535B (zh) | 2018-10-19 |
US10050282B2 (en) | 2018-08-14 |
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