JP5524761B2 - PtRu-based alloy catalyst for fuel cell, method for producing the same, membrane electrode assembly for fuel cell, and fuel cell - Google Patents

Description

  The present invention provides a PtRu-based alloy catalyst for a fuel cell that exhibits high durability even during long-term load fluctuations in the fuel cell, and a method for producing the same, and a membrane for a fuel cell using the PtRu-based alloy catalyst The present invention relates to an electrode assembly and a fuel cell.

  In addition to the recent rise in crude oil prices, rapid economic development in China, India and other countries has led to global problems of fossil fuel depletion and carbon dioxide emissions. For this reason, research and development of fuel cells, lithium-ion batteries, biofuels, solar cells, etc. are being actively carried out for the de-oiling. A direct methanol fuel cell (DMFC) using methanol as an anode fuel is used for a fuel cell that uses a proton conductive film typified by Nafion (registered trademark) and can generate power in an atmosphere of normal temperature and pressure. And a polymer polymer fuel cell (PEFC) using hydrogen gas as an anode fuel.

  DMFC, which uses methanol as the anode fuel, has a theoretical volumetric energy density about 10 times that of lithium-ion batteries, and the power generation system is simple and can be downsized. It is expected to be used as an emergency power supply for portable devices, as a charger for notebook computers, portable music players, and mobile phones.

The DMFC uses methanol as a fuel, and sandwiches a membrane electrode assembly composed of an anode catalyst layer / proton conductive film / cathode catalyst layer between conductive gas diffusion layers, and a current collector plate provided on the anode and cathode electrodes This is a battery system connected to an external circuit. When methanol, which is a liquid fuel, is supplied to the anode catalyst layer side of the DMFC, the methanol is oxidized and converted into carbon dioxide (CO ₂ ) by a chemical reaction represented by the following formula (1), and protons (H ⁺ ) and electrons ( e ^-) and is generated.
_{CH 3 OH + H 2 O =} CO 2 + 6H + + 6e - (1)

The protons and electrons generated by this reaction generate water (H ₂ O) by the reaction of oxygen gas supplied to the cathode catalyst layer and the following formula (2).
O ₂ + 4H ⁺ + 4e ⁻ = 2H ₂ O (2)

Therefore, the reaction of the following formula (3) proceeds as a whole battery, and electrons generated at this time can be taken out by an external circuit to obtain electric energy.
_{CH 3 OH + 3 / 2O 2} = CO 2 + 2H 2 O (3)

Although Pt (platinum) was used as the anode catalyst of the initial DMFC, when Pt alone was used as the anode catalyst, as shown in the following formula (4), carbon monoxide ( There was a problem that CO) was chemically adsorbed on the surface of the Pt catalyst, and the Pt catalyst was poisoned and deactivated.
_{Pt + CH 3 OH = Pt-} CO + 4H + + 4e - (4)

In order to solve this problem, at present, a catalyst made of PtRu (platinum-ruthenium) is generally used as an anode catalyst of PEFC using a reformed hydrogen gas containing DMFC and a small amount of CO ( For example, Patent Document 1). Ru (ruthenium) has high hydrophilicity and reacts with water as shown in the following formula (5) to produce Ru-OH.
_{Ru + H 2 O = Ru-} OH + H + + e - (5)

The produced Ru—OH quickly oxidizes CO adsorbed on the Pt surface to CO ₂ according to the following formula (6).
Pt-CO + Ru-OH
= CO ₂ + H ⁺ + e ⁻ + Pt + Ru (6)

  However, there are still many unclear points about the reaction mechanism of the PtRu alloy catalyst, and even when such an alloy catalyst is used in large quantities, the oxidation reaction of methanol is slow and it is difficult to obtain a high output. Although the theoretical voltage of DMFC is 1.21V, even when the PtRu alloy catalyst is used, the activation energy of the methanol oxidation reaction is large and the overvoltage of the oxidation reaction is large, so the effective voltage is much lower than the theoretical voltage. ing.

  In addition, since Pt and PtRu alloy catalysts currently used in DMFC and PEFC as practical catalysts are rare metals and are very expensive, it is an essential task to reduce the amount of catalyst used.

  As a means for solving such a problem, for example, by reducing the diameter of the catalyst particles and increasing the specific surface area of the catalyst, the activity per unit mass of the catalyst (hereinafter referred to as “mass activity”) is increased, thereby the catalyst. Attempts have been made to reduce the amount used (Patent Documents 2 and 3).

JP 2003-308849 A JP 2006-277792 A JP 2007-190454 A

  While the techniques described in Patent Document 2 and Patent Document 3 have a certain effect in improving the mass activity of the catalyst particles, when the particle diameter of the catalyst particles is reduced, the surface energy increases and Aggregation and coarsening are likely to occur, and catalyst particles are likely to be eluted. Therefore, a catalyst having catalyst particles with a small particle diameter has high initial performance, but its activity tends to decrease with the passage of time of use, and there is still room for improvement in terms of durability.

  Therefore, in PtRu-based alloy catalysts for fuel cells, the development of technology that enhances durability so that desired battery performance can be maintained over a long period of time while increasing activity so that the amount of catalyst particles used can be reduced. Is required.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a highly active PtRu-based alloy catalyst for a fuel cell that exhibits high durability even in a long-term load fluctuation in the fuel cell, and a method for producing the same. The present invention also provides a fuel cell membrane electrode assembly and a fuel cell using the PtRu-based alloy catalyst.

The PtRu-based alloy catalyst for a fuel cell of the present invention that can achieve the above-mentioned object is one in which PtRu-based alloy catalyst particles containing at least Pt, Ru, and P are supported on a carrier, and the PtRu-based alloy catalyst The particles are obtained by heat treatment in a non-oxidizing atmosphere in a state of being supported on a support, and the average particle diameter of the PtRu-based alloy catalyst particles is greater than 10 nm and less than 20 nm, and the PtRu-based particles The specific surface area of the alloy catalyst particles is 30 to 100 m ² / g, and the ratio of Pt and Ru in the whole catalyst is 30:70 to 70:30 in terms of atomic ratio.

  The method for producing a PtRu-based alloy catalyst for a fuel cell according to the present invention comprises at least Pt, Ru and P are reduced and deposited on the surface of the support, and PtRu-based alloy catalyst particles containing at least Pt, Ru and P are supported on the support. And a step of heat-treating the PtRu-based alloy catalyst particles supported on the support in a non-oxidizing atmosphere.

  Furthermore, the fuel cell membrane electrode assembly of the present invention comprises an anode catalyst layer, a cathode catalyst layer, and a fuel cell membrane electrode assembly having a proton conductive film disposed between the anode catalyst layer and the cathode catalyst layer. The PtRu alloy catalyst for fuel cells of the present invention is used as the catalyst for the anode catalyst layer.

  The fuel cell of the present invention is characterized by having the fuel cell membrane electrode assembly of the present invention.

  According to the present invention, it is possible to provide a PtRu-based alloy catalyst for a fuel cell that exhibits high durability even during long-term load fluctuations in the fuel cell, and a method for producing the same. Moreover, according to the membrane electrode assembly for a fuel cell of the present invention, a fuel cell having excellent battery characteristics and capable of maintaining the battery characteristics over a long period can be configured. Furthermore, the fuel cell of the present invention has excellent battery characteristics and can maintain the battery characteristics over a long period of time.

It is a graph showing the methanol oxidation activity change in the durability test of the PtRu-based alloy catalysts of Examples 1 and 2 and Comparative Example 1. It is a graph showing the change of the electrochemical surface area before and behind a durability test of the PtRu type | system | group alloy catalyst particle | grains which concern on the PtRu type | system | group alloy catalyst of Example 1, 2 and the comparative example 1. FIG. 6 is a graph showing an evaluation of mass activity for methanol oxidation reactions of PtRu-based alloy catalysts of Examples 1 and 2 and Comparative Example 1. FIG. 4 is a transmission electron micrograph of the dispersion state of the PtRu-based alloy catalyst particles according to the PtRu-based alloy catalysts of Examples 1 and 2 and Comparative Example 1 on the support surface.

  As described above, in a PtRu alloy catalyst having a structure in which PtRu alloy catalyst particles are supported on a carrier, the catalyst specific surface area is improved by reducing the diameter of the catalyst particles, thereby improving the catalyst mass activity and battery performance. Can be made. However, if the catalyst particle diameter is reduced, the surface energy of the catalyst particles increases, and the catalyst particles are liable to be aggregated and coarsened. As a result, the catalyst activity is likely to be deteriorated. On the other hand, if the catalyst particles can be enlarged while improving the activity per unit area of the catalyst (hereinafter referred to as “area activity”), the substantial mass activity of the catalyst can be maintained, and the catalyst particles can be aggregated and coarsened. And the durability of the catalyst can be improved.

  However, in the conventional catalyst and its manufacturing method, even if the diameter of the catalyst particles is increased, the area activity of the catalyst cannot be improved, and only the effective specific surface area of the catalyst is reduced, resulting in the mass of the catalyst. A decrease in activity occurred. Therefore, it has been difficult to obtain a PtRu-based alloy catalyst that has a desired catalytic activity and that can constitute a fuel cell having good battery characteristics and durability.

  As a result of intensive studies, the present inventors have conducted heat treatment in a non-oxidizing atmosphere in a state where fine PtRu-based alloy catalyst particles containing at least Pt, Ru, and P are supported on a carrier, thereby obtaining a catalyst. It was found that the particle morphology can be adjusted to an average particle size and specific surface area that can suppress aggregation and coarsening even if the reaction for power generation of the fuel cell is continued, and the area activity of the catalyst can be increased. The invention has been completed.

  The PtRu-based alloy catalyst for fuel cells of the present invention (hereinafter sometimes simply referred to as “catalyst”) is configured by supporting PtRu-based alloy catalyst particles containing at least Pt, Ru and P on a carrier. In the catalyst of the present invention, the active center is Pt, and Ru plays a role of increasing the CO poisoning resistance of the catalyst by the Bi-functional mechanism. Further, P has a function of making the PtRu-based alloy catalyst fine particles, and the PtRu-based alloy catalyst particles at the stage of reduction precipitation on the support surface are in a fine form (H. Daimon and Y. Kurube, Catal.Today, 2006, 111, p.182). In the present invention, such fine PtRu-based alloy catalyst particles are heat-treated in a non-oxidizing atmosphere, whereby the morphology of the PtRu-based alloy catalyst particles can be controlled.

  The PtRu-based alloy catalyst particles according to the catalyst of the present invention are particles composed of an alloy containing at least Pt, Ru and P. Since Ru atoms are arranged in the vicinity of the Pt atoms, the CO coverage of Pt by Ru is reduced. Since the action of suppressing poison functions effectively, it has high activity.

  In the PtRu-based alloy catalyst particles according to the catalyst of the present invention, the average particle diameter is made larger than 10 nm from the viewpoint of suppressing particle aggregation and coarsening due to the reaction and enhancing the durability of the catalyst. However, if the particle diameter of the PtRu-based alloy catalyst particles is too large, the reaction surface area decreases, which may cause a decrease in catalyst activity and a desired performance may not be obtained. Therefore, the average particle size of the PtRu-based alloy catalyst particles is less than 20 nm and preferably 15 nm or less.

  The average particle diameter of the PtRu-based alloy catalyst particles referred to in this specification is an average value of the particle diameters of 100 PtRu-based alloy fine particles that can be observed at a magnification of 1,000,000 using a transmission electron microscope (TEM).

Moreover, the specific surface area of the PtRu-based alloy catalyst particles according to the catalyst of the present invention is 30 m ² / g or more from the viewpoint of increasing the mass activity of the catalyst. However, if the specific surface area of the PtRu-based alloy catalyst particles is too large, the particle diameter is usually small, and the effect of improving the area activity of the catalyst cannot be ensured, and the durability of the catalyst cannot be increased. Therefore, the specific surface area of the PtRu-based alloy catalyst particles is 100 m ² / g or less.

  The specific surface area of the PtRu-based alloy catalyst particles referred to in this specification is a value measured by a CO pulse adsorption method.

  In the PtRu-based alloy catalyst particles according to the catalyst of the present invention, from the viewpoint of suppressing CO poisoning on the Pt surface as described above, the ratio of Pt and Ru in the whole catalyst is 30:70 to 70:30 in terms of atomic ratio. It is preferable that it is 40: 60-60: 40.

  In addition, the amount of P in the PtRu-based alloy catalyst particles according to the catalyst of the present invention is preferably 1 atomic% or more from the viewpoint of better ensuring the effect of finely forming the catalyst particles by P. However, since the effect is saturated even if the amount of P in the PtRu-based alloy catalyst particles is too large, the amount of P in the PtRu-based alloy catalyst particles is preferably 20 atomic% or less.

  In the PtRu-based alloy catalyst particles according to the catalyst of the present invention, for example, the balance other than P may be Pt and Ru (however, it may contain inevitable impurities).

  The catalyst of the present invention includes a step of reducing and precipitating at least Pt, Ru and P on the surface of the support, and supporting the PtRu-based alloy catalyst particles containing at least Pt, Ru and P on the support, and a PtRu system supported on the support. The alloy catalyst particles can be produced by the method of the present invention having a step of heat-treating in a non-oxidizing atmosphere.

  The step of reducing and precipitating at least Pt, Ru, and P on the surface of the support and supporting the PtRu-based alloy catalyst particles on the support preferably includes, for example, the following steps (1) to (3).

  In step (1), a support material, a Pt source, a Ru source, a complexing agent and hypophosphorous acid or hypophosphite are added to water to prepare a solution ( The raw materials are dispersed without dissolving).

As the Pt supply source (hereinafter referred to as “Pt precursor”), hexachloroplatinic acid (H ₂ PtCl ₆ ) is preferably used because it is particularly inexpensive. Further, potassium hexachloroplatinate (K ₂ PtCl ₆ ), platinum tetrachloride (H ₂ PtCl ₄ ), potassium tetrachloroplatinate (K ₂ PtCl ₄ ) and the like can also be used as the Pt precursor. These Pt precursors may be used alone or in combination of two or more.

As the Ru supply source (hereinafter referred to as “Ru precursor”), ruthenium chloride (RuCl ₃ ) is preferably used because it is particularly inexpensive. Further, ruthenium nitrate [Ru (NO ₃ ) ₃ ] can also be used as the Ru precursor. These Ru precursors may be used alone or in combination of two or more.

  As described above, in the PtRu-based alloy catalyst particles, an atomic arrangement in which Pt atoms and Ru atoms are sufficiently mixed and Pt atoms and Ru atoms are adjacent to each other is desired. In the aqueous chemical reduction synthesis method, an obstacle to the mixing of atoms is a reduction potential difference existing between Pt ions and Ru ions. Therefore, it is preferable to add a complexing agent to the solution prepared in the step (1) to reduce the reduction potential difference.

  As the complexing agent, citric acid, succinic acid, malic acid, tartaric acid, maleic acid, nitrilotriacetic acid, and salts thereof are preferable. Only 1 type of these may be used for a complexing agent, and 2 or more types may be used together.

  The complexing agent added to the solution undergoes ligand substitution with a complex in which chlorine ions or the like are coordinated to Pt ions and Ru ions in the solution, and changes to a new complex. The complexing agent is a multidentate ligand containing two or more carboxyl groups, and forms a chelate complex. By this chelate complex formation, the stability of the complex increases and the reduction potential of Pt ions and Ru ions decreases. At this time, the degree of stabilization (absolute value of reduction of the reduction potential) is greater in the Pt chelate complex than in the Ru chelate complex. As a result, the reduction potential difference between the two chelate complexes is reduced as compared with the complex coordinated with the original chloride ions. By reducing this reduction potential difference, preferential reduction of Pt is suppressed, and a catalyst structure in which Pt atoms and Ru atoms are sufficiently mixed and close can be obtained. Therefore, it becomes possible to arrange Ru atoms in the vicinity of the Pt atoms, and the action of suppressing the CO poisoning of Pt by Ru functions effectively, and PtRu-based alloy catalyst particles having high activity can be obtained. .

  The amount of the complexing agent added to the solution is 0.01 to the total number of moles of noble metal ions (Pt ions and Ru ions) in the solution from the viewpoint of forming a more stable Pt chelate complex and Ru chelate complex. It is preferable to make it more than twice. However, if the amount of the complexing agent added to the solution is too large, the stability of the complex due to the chelate effect is too high, and the reduction efficiency of Pt ions and Ru ions may be reduced. Therefore, the amount of the complexing agent added to the solution is preferably 4.0 times or less with respect to the total number of moles of noble metal ions in the solution.

As the carrier material used in the step (1), for example, carbon having a specific surface area of about ²⁰ to 1000 m ² / g is preferable, and specifically, carbon black, acetylene black, carbon nanotube and the like are preferable. In consideration of the oxidation of the carrier, carbon that has been heat-treated in a non-oxidizing atmosphere and has an increased graphite component can also be preferably used.

  The catalyst loading ratio (the amount of PtRu-based alloy catalyst particles in a total of 100% by weight of the PtRu-based alloy catalyst particles and the carrier) is preferably 50 to 80% by weight. In order to promote the diffusion of the reactant by reducing the thickness of the electrode, it is advantageous that the loading ratio is higher, so 60-80% by mass is more preferable. Therefore, it is preferable to use the carrier material in an amount such that the catalyst has the loading rate.

  Hypophosphorous acid or hypophosphite added to the solution serves as a supply source of P in the alloy catalyst particles, and has the effect of making the catalyst particles fine as described above. Therefore, the PtRu-based alloy catalyst particles deposited on the surface of the support become fine particles having a small particle size. By heat-treating them in a non-oxidizing atmosphere, the average particle size and specific surface area of the PtRu-based alloy catalyst particles are set to the above values. Can be adjusted. Further, hypophosphorous acid or hypophosphite is a reducing agent in the reduction precipitation reaction when PtRu-based alloy catalyst particles containing at least Pt, Ru and P are reduced and precipitated on the support surface in the step (2) described later. Also works.

  In addition to the hypophosphorous acid or hypophosphite, another reducing agent may be added to the solution prepared in the step (1). Examples of such a reducing agent include sodium borohydride, formalin, hydrazine and the like.

  The amount of the reducing agent used should satisfy the minimum stoichiometric ratio that can reduce Pt and Ru, but if it is too much, precipitation reduction occurs in the solution, and there is a possibility that the reduction may not be possible due to decomposition of the bath. Therefore, it is preferable to be 10 times or less with respect to the total number of moles of Pt and Ru. However, among the reducing agents, the amount of hypophosphorous acid or hypophosphite in the solution prepared in step (1) is such that the amount of P in the PtRu-based alloy catalyst particles is the above amount in the produced catalyst. It is more preferable to adjust so.

  In the step (1), it is preferable that a predetermined time or more elapses after the complexing agent is added to the solution containing the Pt precursor and the Ru precursor. For example, when hexachloroplatinic acid is used as the Pt precursor, this Pt precursor is a complex coordinated with chlorine ions. Even if a complexing agent is added to the solution containing this, the chloride ion coordination is performed. It has been found that the ligand substitution reaction with the child is slow (T. Onodera, S. Suzuki, Y. Takamori and H. Daimon, Appl. Cata. A, gen, 2010, vol. 379, p. 69). ). As described above, in order to obtain highly active PtRu-based alloy catalyst particles in which Pt atoms and Ru atoms are sufficiently mixed, a stable chelate complex is formed by adding the complexing agent, and Pt ions and Ru ions It is necessary to reduce the reduction potential difference existing between the two. Therefore, when the Pt precursor is a chloride such as hexachloroplatinic acid, after adding a complexing agent to the solution, the chloride ion and these complexing agents are sufficiently substituted, so that a certain period of time should elapse. Is recommended. Thereby, even when the substitution reaction rate is slow, the ligand substitution reaction can be sufficiently advanced to form a stable complex. As a result, the reduction potential difference existing between Pt ions and Ru ions can be reduced, and Pt atoms and Ru atoms can be sufficiently mixed to synthesize adjacent PtRu-based alloy catalyst particles.

  The time elapsed after adding the complexing agent to the solution containing the Pt precursor and the Ru precursor is preferably 1 hour or longer, more preferably 12 hours or longer, and still more preferably 24 hours or longer.

  In the step (2), the solution prepared in the step (1) is heated to cause Pt, Ru and P to be reduced and deposited on the surface of the support, and the PtRu-based alloy catalyst particles are supported on the support. The heating temperature of the solution is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and preferably 90 ° C. or lower in order to fully exhibit the ability of the reducing agent. .

In the step (2), the pH of the solution is adjusted to an appropriate value. The solubility product of Ru ³⁺ ions and hydroxide ions is as extremely low as 1 × 10 ⁻³⁸ [mol / l] ^{4. When} the pH of the solution is set to the alkali side, a precipitate of Ru (OH) ₃ is generated. However, when a complexing agent that forms a chelate is added to the solution, the complex is stabilized. Therefore, even when the pH of the solution is in the alkaline region, the formation of hydroxide is suppressed and stabilized. A synthetic system can be constructed. Of course, in the method of the present invention, PtRu-based alloy catalyst particles can be synthesized even when the pH of the solution is in the acidic region where no precipitate of hydroxide is generated.

  The time for heating the solution in the step (2) is preferably, for example, 1 hour or longer, and preferably 10 hours or shorter from the viewpoint of improving productivity.

  In the step (3), the PtRu alloy catalyst synthesized in the step (2) is washed and dried. First, the PtRu-based alloy catalyst is taken out from the solution obtained through the step (2) by filtration or the like, washed with, for example, water (ion-exchanged water or the like), and the washed PtRu-based alloy catalyst is dried. . For drying, for example, an oven or the like may be used, and the drying conditions are preferably 100 ° C. or lower (more preferably about 70 to 80 ° C.) and until drying (specifically, about 12 to 24 hours). do it.

  Subsequently, the PtRu-based alloy catalyst obtained through the step (3), that is, the PtRu-based alloy catalyst particles supported on the carrier is heat-treated in a non-oxidizing atmosphere. By this heat treatment, the average particle diameter and specific surface area of the PtRu-based alloy catalyst particles can be adjusted to the above-mentioned values, so that the durability of the catalyst can be enhanced and the area activity of the catalyst can be enhanced.

  The reason why the area activity of the catalyst is improved by heat treatment in a non-oxidizing atmosphere is considered as follows. Thermodynamic mixing heat of Pt and Ru (easy mixing of Pt atoms and Ru atoms) is −1 kJ / mol. Here, the mixing heat of Pt and Pt and the mixing heat of Ru and Ru are determined to be 0 kJ / mol. On the other hand, the heat of mixing of Pt and P is −26 kJ / mol, and the heat of mixing of Ru and P is −22 kJ / mol. These values of heat of mixing indicate that P can intervene between the metal bonds of Pt—Pt, Ru—Ru and Pt—Ru in the PtRu alloy catalyst of the present invention in which P coexists. From this, in the vicinity of the catalyst surface, separation of the Pt atomic group (cluster) and the Ru atomic group is promoted by the coexistence of P, and the Bi-functional mechanism shown in the above formulas (4) to (6) is further increased. It is considered that the area activity of methanol oxidation is increased as compared with a normal PtRu alloy catalyst.

  Examples of the non-oxidizing gas for making the heat treatment system non-oxidizing atmosphere include hydrogen gas, nitrogen gas, and argon gas. The system for performing the heat treatment may contain only one of these non-oxidizing gases (pure hydrogen gas, pure nitrogen gas, pure argon gas), or two or more (nitrogen gas containing hydrogen, Argon gas containing hydrogen and the like may be contained, but it is particularly preferable to perform heat treatment in a system containing pure hydrogen gas.

  The heat treatment temperature is preferably 650 ° C. or higher, more preferably 700 ° C. or higher, from the viewpoint of enhancing the area activity of the catalyst and controlling the form of the PtRu-based alloy catalyst particles to ensure good durability. preferable. That is, if the heat treatment temperature is too low, for example, the average particle diameter of the PtRu-based alloy catalyst particles tends to be smaller than the above value, and there is a possibility that good durability cannot be ensured.

  However, if the heat treatment temperature is too high, the PtRu-based alloy catalyst particles are likely to agglomerate and coarsen, the effective catalyst specific surface area decreases, and the desired characteristics may not be obtained. Therefore, the heat treatment temperature is preferably 1000 ° C. or lower, and more preferably 950 ° C. or lower.

  The heat treatment time is preferably, for example, 10 minutes to 1 hour.

  The PtRu-based alloy catalyst (the catalyst of the present invention) produced by the method of the present invention is used as a catalyst for an anode catalyst layer of a membrane electrode assembly for fuel cells (DMFC and PEFC).

  That is, the fuel cell membrane electrode assembly of the present invention uses the PtRu-based alloy catalyst for fuel cells of the present invention as the catalyst for the anode catalyst layer, and other configurations and structures are not particularly limited. In addition, it is possible to apply a configuration and a structure adopted in a membrane electrode assembly of conventionally known fuel cells (DMFC and PEFC).

  The fuel cell of the present invention only needs to have the fuel cell membrane electrode assembly of the present invention, and the other configurations and structures are not particularly limited, and a conventionally known fuel cell (DMFC) And the structure and structure adopted in PEFC) can be applied.

  The fuel cell membrane electrode assembly of the present invention has a specific surface area smaller than that of the conventional catalyst and uses a catalyst having relatively large particles, but has high mass activity and durability. Since the catalyst is used, an anode layer having high durability can be manufactured. Therefore, the fuel cell of the present invention having such a membrane electrode assembly has high durability and good battery characteristics.

  Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.

Example 1
DL-tartaric acid: 0.1 mmol as a complexing agent was added to a mixed aqueous solution of hexachloroplatinic acid hexahydrate: 1.69 mmol and ruthenium (III) chloride hydrate: 1.69 mmol, and ion-exchanged water Was added to adjust the whole to 300 ml to prepare an aqueous solution. After stirring the aqueous solution at room temperature for 30 minutes, 0.5 g of Ketjen Black EC powder, which is a carbon black carrier, was added and dispersed. Thereafter, 6.8 mmol of hypophosphorous acid, which is a reducing agent and a P supply source, is added to the above-mentioned solution in which the carrier is dispersed to make the total solution volume 1000 ml, and 2N aqueous sodium hydroxide solution is further added dropwise. After adjusting the pH of the solution to 2, the solution was stirred at a bath temperature of 90 ° C., and PtRu-based alloy catalyst particles were reduced and deposited on the surface of the carbon black support. The ratio of Pt and Ru in the whole PtRu-based alloy catalyst thus obtained was 50:50 (atomic ratio).

  The PtRu-based alloy catalyst was removed from the solution after completion of the reaction by filtration, washed and dried, and then heat-treated at 900 ° C. for 10 minutes in pure hydrogen to obtain the PtRu-based alloy catalyst of Example 1.

Example 2
A PtRu-based alloy catalyst was produced in the same manner as in Example 1 except that the heat treatment temperature in pure hydrogen was changed to 700 ° C.

Comparative Example 1
A PtRu-based alloy catalyst was produced in the same manner as in Example 1 except that heat treatment in pure hydrogen was not performed.

  For the PtRu-based alloy catalysts of Examples 1 and 2 and Comparative Example 1, composition analysis by fluorescent X-ray analysis (XRF), measurement of the average particle diameter of PtRu-based alloy catalyst particles by transmission electron microscope (TEM) observation, and CO pulse The specific surface area of the PtRu-based alloy catalyst particles was measured by adsorption measurement. These results are shown in Table 1.

  Further, standard three-electrode cells were assembled using the PtRu-based alloy catalysts of Examples 1 and 2 and Comparative Example 1, and the catalyst characteristics before and after the durability test were evaluated. These evaluation results are shown in FIG. 1 and FIG.

  First, 20 μl of a PtRu-based alloy catalyst dispersed at 2 mg / ml in pure water was taken with a micropipette, applied onto a glassy carbon electrode, dried, and then an ion conductive polymer dispersion [Aldrich Co. A product obtained by applying 5 μl of “Nafion (registered trademark)” manufactured and drying was used as a working electrode. A Pt line was prepared for the counter electrode, and an Ag / AgCl electrode was prepared for the reference electrode. Then, these working electrode, counter electrode, and reference electrode are immersed in a 0.5 mol / l sulfuric acid aqueous solution to form a three-electrode cell in a potential scanning range of 0.03 V to 0.6 V at a potential scanning speed of 5 mV. Cyclic voltammetry (CV) measurement was performed to evaluate the electrochemical surface area of the PtRu alloy catalyst before the durability test.

  In addition, 20 vol. % Methanol was added, and a linear sweep voltammetry (LSV) measurement was performed at 35 ° C. in a nitrogen atmosphere at a potential scanning speed of 5 mV / s to measure the methanol oxidation activity of the PtRu-based alloy catalyst before the durability test. .

  Next, the working electrode, counter electrode and reference electrode used for measuring the methanol oxidation activity of the PtRu-based alloy catalyst before the durability test were immersed in a 0.5 mol / l sulfuric acid aqueous solution to form a three-electrode cell. A durability test was performed in which a potential application cycle in which a voltage was swept at a rate of 1000 mV / s in a range of 1 V to 0.7 V was performed for 1000 cycles.

  Then, CV measurement is performed on the 3-electrode cell after the durability test at a potential scanning speed of 5 mV in a potential scanning range of 0.03 V to 0.6 V, and the electrochemical surface area of the PtRu alloy catalyst after the durability test is determined. evaluated.

  In addition, 20 vol. % Methanol was added, LSV measurement was performed at 35 ° C. in a nitrogen atmosphere at a potential scanning speed of 5 mV / s, and the methanol oxidation activity of the PtRu-based alloy catalyst after the durability test was measured.

  FIG. 1 is a graph showing the methanol oxidation activity of each PtRu-based alloy catalyst in the durability test. The horizontal axis represents the number of potential application cycles, and the vertical axis represents “change in methanol oxidation activity” before the durability test. The relative value is shown when the methanol oxidation activity is 100%. FIG. 2 is a graph showing the electrochemical surface area of each PtRu-based alloy catalyst before and after the durability test. The vertical axis indicates “surface area change” before and after the durability test evaluated by CV measurement. The electrochemical surface area of each catalyst is shown as a relative value when the value before the durability test is 100%.

  As shown in FIG. 1 and Table 1, the PtRu-based alloy catalyst of Comparative Example 1 that has not been heat-treated in a non-oxidizing atmosphere and has PtRu-based alloy catalyst particles having a small average particle size and a large specific surface area is durable. Assuming that the methanol oxidation activity before the durability test is 100, the methanol oxidation activity after the durability test (the number of potential application cycles is 1000) is 70, and a 30% decrease is observed.

  On the other hand, the PtRu-based alloy catalysts of Examples 1 and 2 having PtRu-based alloy catalyst particles having an appropriate average particle diameter and specific surface area, which were heat-treated in pure hydrogen gas, had methanol oxidation activity before the durability test. When 100 is 100, the methanol oxidation activity after the durability test is 90 and 85, respectively, which is higher than that of the catalyst of Comparative Example 1.

  In addition, as shown in FIG. 2, the PtRu-based alloy catalyst of Comparative Example 1 that has not been heat-treated in a non-oxidizing atmosphere has an electrical surface after the durability test with respect to the electrochemical surface area 100 before the durability test. The chemical surface area is 50, reduced in half.

  In contrast, the PtRu-based alloy catalysts of Examples 1 and 2 that were heat-treated in pure hydrogen gas had an electrochemical surface area after the durability test with respect to the electrochemical surface area 100 before the durability test, They are 95 and 90, respectively. Therefore, it can be seen that due to the effect of increasing the particle size of the catalyst particles by the heat treatment, the catalyst particles are stabilized, and the electrochemical surface area of the catalyst is hardly reduced even after the durability test, and the reaction surface area is maintained.

  FIG. 3 is a graph showing the mass activity for the methanol oxidation reaction evaluated for the PtRu-based alloy catalysts of Example 1 and Comparative Example 1 in the same manner as the evaluation of the methanol oxidation activity before the durability test. ing. In the graph of FIG. 3, the horizontal axis indicates the potential, and the vertical axis indicates the current density due to the methanol oxidation reaction (methanol oxidation current per 1 mg of PtRu-based alloy catalyst particles). This means that the catalyst has a high methanol oxidation activity.

  In the catalyst of Example 1 subjected to heat treatment at 900 ° C. in pure hydrogen gas, the mass activity at 0.5 V has a current density (that is, mass activity) of 50 mA / mg. The catalyst of Example 1 is a comparative example having catalyst particles with a large specific surface area that is not heat-treated in a non-oxidizing atmosphere, even though the catalyst particle diameter is increased by heat treatment and the specific surface area is decreased. It can be seen that the methanol oxidation activity is equal to or higher than the current density of 48 mA / mg in the catalyst No. 1.

  The average particle diameter of the PtRu-based alloy catalyst particles relating to the catalyst is 2.5 nm in Comparative Example 1 and 14.9 nm in Example 1, and the geometric specific surface area of the catalyst particles is compared with the catalyst of Example 1. It is reduced to about 1/6 of the catalyst of Example 1. Accordingly, the fact that the catalyst of Example 1 and the catalyst of Comparative Example 1 exhibit the same methanol oxidation activity means that the area activity of the catalyst of Example 1 is about 6 times that of the catalyst of Comparative Example 1. Represents.

  FIG. 4 shows the results of TEM observation of the dispersion state of the PtRu-based alloy catalyst particles on the support surface of the PtRu-based alloy catalysts of Examples 1 and 2 and Comparative Example 1. In addition, the scale (white line) in the photograph in FIG. 4 represents 10 nm.

  In the PtRu-based alloy catalysts of Examples 1 and 2 that were heat-treated in pure hydrogen gas, an increase in the particle size of the PtRu-based alloy catalyst particles was observed compared to the catalyst of Comparative Example 1, but It can be seen that the dispersed state is maintained in the same state as the catalyst of Comparative Example 1.

Claims (7)

A PtRu-based alloy catalyst for a fuel cell in which PtRu-based alloy catalyst particles containing at least Pt, Ru and P are supported on a carrier,
The PtRu-based alloy catalyst particles are obtained by being heat-treated in a non-oxidizing atmosphere while being supported on a support,
The average particle diameter of the PtRu-based alloy catalyst particles is larger than 10 nm and smaller than 20 nm,
The PtRu-based alloy catalyst particles have a specific surface area of 30 to 100 m ² / g,
The ratio of Pt and Ru in the entire catalyst, by atomic ratio, 30: 70-70: Ri 30 der,
The PtRu alloy the amount of P in the catalyst particles, 1-20 atomic% der Rukoto fuel cell PtRu alloy catalyst according to claim.   2. The PtRu-based alloy for fuel cells according to claim 1, wherein the support is at least one selected from the group consisting of carbon black, acetylene black, carbon nanotubes, and carbon that has been heat-treated in a non-oxidizing atmosphere and has an increased graphite component. catalyst. A method for producing a PtRu-based alloy catalyst for a fuel cell according to claim 1 or 2,
Reducing and precipitating at least Pt, Ru and P on the support surface, and supporting PtRu-based alloy catalyst particles containing at least Pt, Ru and P on the support;
A method for producing a PtRu-based alloy catalyst for a fuel cell, comprising a step of heat-treating PtRu-based alloy catalyst particles supported on a support in a non-oxidizing atmosphere. The PtRu-based alloy for fuel cells according to claim 3 , wherein the heat treatment in a non-oxidizing atmosphere is performed in an atmosphere containing hydrogen gas, nitrogen gas, nitrogen gas containing hydrogen, argon gas, or argon gas containing hydrogen. A method for producing a catalyst. The method for producing a PtRu-based alloy catalyst for a fuel cell according to claim 3 or 4 , wherein a heat treatment temperature in a non-oxidizing atmosphere is 650 to 1000 ° C. A fuel cell membrane electrode assembly having an anode catalyst layer, a cathode catalyst layer, and a proton conductive film disposed between the anode catalyst layer and the cathode catalyst layer,
A membrane electrode assembly for a fuel cell, wherein the PtRu-based alloy catalyst for a fuel cell according to claim 1 or 2 is used as the catalyst for the anode catalyst layer. A fuel cell comprising the fuel cell membrane electrode assembly according to claim 6 .