WO2006137302A1 - Fuel cell, catalyst thereof, and electrode thereof - Google Patents

Abstract

Disclosed is a low-cost catalyst for fuel cells which exhibits excellent catalytic activity and could be an alternative for noble metal catalysts such as platinum catalysts. Also disclosed are an electrode for fuel cells which uses such a catalyst for fuel cells, and a fuel cell. Specifically disclosed is a catalyst for fuel cells containing one or more elements selected from the group consisting of tellurium (Te), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os) and iridium (Ir) as active ingredients. Also specifically disclosed is a catalyst for fuel cells obtained by causing the active ingredients to adhere a carbonaceous base. Further specifically disclosed are an electrode for fuel cells containing such a catalyst for fuel cells, and a fuel cell using such an electrode for fuel cells.

Description

 Specification

 Fuel cell, its catalyst and its electrode

 Field of Invention

 TECHNICAL FIELD [0001] The present invention relates to a fuel cell catalyst, a method for producing the same, a fuel cell electrode and a fuel cell using the fuel cell catalyst.

 Background of the Invention

 [0002] In recent years, in order to further improve energy efficiency and solve environmental problems, attempts have been made to clean exhaust gas by using a fuel cell as a power source for an automobile. There is interest. In particular, the development of a polymer electrolyte fuel cell (PEFC) as a fuel cell for fuel vehicles (FCHV) is rapidly progressing.

 [0003] A fuel cell is a power generator that supplies fuel to an anode and oxidant to a power sword, takes out the potential difference between the anode and cathode as a voltage, and supplies it to a load. Hydrogen is used as the anode fuel. In general, oxygen in the air is used as the oxidizing agent. A fuel cell is composed of an anode electrode, a force sword electrode, and an electrolyte sandwiched between them. In a polymer electrolyte fuel cell, an ion exchange membrane is used as an electrolyte. Specifically, an electrolyte membrane / electrode assembly in which a catalyst layer is formed on both surfaces of an ion exchange membrane as an electrolyte, and an anode gas diffusion layer and a force sword gas diffusion layer are integrally formed on the outside of the catalyst layer. However, a unit cell consisting of a barrier plate, an electrolyte membrane Z electrode assembly, and a barrier plate laminate is formed by stacking tens to hundreds of cells so that a desired voltage can be obtained according to the application. Has been.

In such a fuel cell, when hydrogen reaches the anode catalyst layer, protons and electrons are generated by an electrochemical reaction process. Protons generated here move sequentially in the electrolyte and reach the force sword. On the other hand, the electrons are sent to the force sword via an external load. In the force sword catalyst layer, electrons sent via an external load, oxygen in the air as an oxidant, and protons that have moved through the electrolyte are combined by an electrochemical reaction process to bind water. Generate. [0005] Conventionally, as a catalyst for such a fuel cell, both a power sword and an anode are mainly made of a noble metal such as platinum, which is expensive and has a problem in terms of resources. It is considerably larger than the amount of platinum used in exhaust gas purification catalysts for gasoline cars that generate the same power.

 [0006] Therefore, in order to commercialize a fuel cell, it can be used at low cost and practically, instead of a catalyst mainly composed of noble metals such as platinum, which is problematic in terms of price and resources. The development of the catalyst is one of the essential issues.

 [0007] The following document 1 describes that an alloy composed of platinum element and an additive element such as tellurium element is used as a catalyst for a fuel cell.

 2 Considered. However, in this document, Group VIII elements are limited to Pt, and ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir) are not disclosed at all.

 References 2 and 3 describe a catalyst composed of ruthenium element and tellurene element, but only the catalyst having a ruthenium element and tellurium element ratio of Ru / Te = l / 0.055 is disclosed. Thus, catalysts with a tellurium element ratio greater than 0.055 are not disclosed at all, and no suggestions are given.

 Reference 4 does not disclose the specific values of x and y that RuxTey discloses. Since the synthesis method is the same as in Non-Patent Document 1, only Ru Te has been studied.

 1 0.055

 It is speculated that.

 References 5 and 6 disclose Mo Ru Te, Mo Rh Te, and Mo Os Te forces S. Force

 4 2 8 5 1 8 5.4 0.6 8

 Desirably, the abundance ratio of transition metals (Ru, Rh, Os) other than Te element and Mo is in a specific region.

 Reference 1 Japanese Patent Laid-Open No. 10-92441

 Reference 2 Electrochimica Acta 47, 2002, 3807-3814

 Reference 3 Journal of Physical Chemistry B 106 (7), 2002, 1670-1676 Reference 4 Nuclear Instruments & Methods in Physics Research, Section A: Accelerators, Spectrometers, Detectors, and Associated Equipment, 448 (1-2),

2000, 323-326. Reference 5 Journal of Applied Electrochemistry 25 (11), 1995, 1004-1008 Reference 6 J Chim Phys Phys Chim Biol 93 (4), 1996, 702-710

 Although it is known that platinum and tellurium alloys can be used as fuel cell catalysts, as described in the above document 1, this fuel cell catalyst is expensive and has problems in terms of resources. Therefore, it is impossible to solve the problem of developing a catalyst for a fuel cell that can be used practically at low cost instead of a catalyst mainly composed of noble metals such as platinum.

 Summary of the Invention

 [0008] The present invention provides a fuel cell catalyst that exhibits an excellent catalytic action that is inexpensive and can be substituted for a noble metal catalyst such as platinum, and a fuel cell electrode and a fuel cell using the fuel cell catalyst. The purpose is to provide.

 [0009] The fuel cell catalyst of the first aspect is selected from the group consisting of tellurium (Te), ruthenium (Ru), rhodium h), palladium (Pd), osmium (Os), and iridium (Ir). When at least one element M is included and the composition is expressed as M Te, 0 · 2 <Χ <4.

 1 X

 It is a sign.

 [0010] The fuel cell catalyst of the second aspect is selected from the group consisting of tellurium (Te), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir). When at least one element L is included and the composition is expressed as L Ru Te, 0.2 and X, and 0 <Y

 Υ 1 X

 It is characterized by ≤ 10.

[0011] The fuel cell electrode material of the third aspect and the fuel cell electrode of the fourth aspect

 It has a catalyst of 1 or 2nd aspect.

[0012] The fuel cell of the fifth aspect has the electrode of the fourth aspect.

 Detailed description

[0013] As a result of diligent investigations in view of the above situation, the present inventors have replaced a noble metal catalyst such as platinum with high catalytic activity by using an alloy or compound composed of a Group VIII element such as ruthenium and ternore. It has been found that a fuel cell catalyst having practical utility can be obtained. Further, it has been found that by attaching this to a substrate, a fuel cell catalyst can be obtained that is practical and can be substituted for a noble metal catalyst such as platinum, which is cheaper and has higher catalytic activity. The present invention has been completed based on such knowledge, and the gist thereof is as follows. [I] tellurium (Te) and at least one element M selected from the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir), A fuel cell catalyst characterized by 0.2 <X <4 when the composition is expressed as MTe.

 1 X

 [2] The fuel cell catalyst according to [1], wherein 1 <X.

 [3] A fuel cell catalyst according to [1], substantially consisting of Te and Ru.

 [4] A fuel cell catalyst according to [1], which contains RuTe.

 2

 [5] including tellurium (Te), ruthenium (Ru), and at least one element L selected from the group consisting of rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir) When the composition is expressed as L Ru Te, the fuel is characterized by 0.2 and X, and 0 <Y≤10

Υ 1 X

Battery catalyst.

 [6] The fuel cell catalyst according to [1], further comprising a substrate on which Te and elemental metal are deposited.

 [7] A fuel cell catalyst according to [5], further comprising a substrate on which Te, Ru and element L are deposited.

 [8] The fuel cell catalyst according to [6], wherein the substrate is a carbon-based substrate.

[9] The fuel cell catalyst according to [7], wherein the substrate is a carbon-based substrate.

[10] A fuel cell catalyst according to [1], wherein the fuel cell is a solid polymer fuel cell.

 [I I] A fuel cell catalyst according to [5], wherein the fuel cell is a polymer electrolyte fuel cell.

 [12] A fuel cell electrode material comprising an ion exchange membrane and a fuel cell catalyst layer according to [1] formed on the ion exchange membrane.

 [13] A fuel cell electrode material comprising an ion exchange membrane and a fuel cell catalyst layer according to [5] formed on the ion exchange membrane.

 [14] A fuel cell electrode material having an electrode gas diffusion layer and a fuel cell catalyst layer according to [1] formed on the electrode gas diffusion layer.

[15] An electrode material for a fuel cell, comprising an electrode gas diffusion layer, and a fuel cell catalyst layer according to [5] formed on the electrode gas diffusion layer. [16] An electrode material for a fuel cell comprising a transfer film and a fuel cell catalyst layer according to [1] formed on the transfer film.

 [17] An electrode material for a fuel cell, comprising: a transfer film; and a fuel cell catalyst layer according to [5] formed on the transfer film.

 [18] A fuel cell electrode comprising the fuel cell catalyst according to [1].

[19] A fuel cell electrode comprising the fuel cell catalyst according to [5].

[20] A fuel cell using the fuel cell electrode according to [18].

[21] A fuel cell using the fuel cell electrode according to [19].

 [22] A fuel cell according to [20], wherein the fuel cell is a polymer electrolyte fuel cell.

 [23] The fuel cell according to [21], wherein the fuel cell is a polymer electrolyte fuel cell.

 [24] A method for producing a fuel cell catalyst according to [8], comprising: mixing a carbon-based substrate, a Te precursor and an element M precursor; and activating the precursor. A method for producing a fuel cell catalyst, comprising:

 [25] A method for producing a fuel cell catalyst according to [9], comprising: mixing a carbon-based substrate, a Te precursor, a Ru precursor, and an element L precursor; and And a step of activating the fuel cell catalyst.

[26] A method for producing a fuel cell catalyst according to [8], comprising a step of mixing a carbon-based substrate and the fuel cell catalyst according to [1]. A method for producing a catalyst.

 [27] A method for producing a fuel cell catalyst according to [9], comprising a step of mixing a carbon-based substrate and the fuel cell catalyst according to [5]. A method for producing a catalyst.

 [28] The method for producing a fuel cell catalyst according to [24], further comprising a step of depositing a transition metal on a carbon-based substrate.

[29] The method for producing a fuel cell catalyst according to [25], further comprising the step of depositing a transition metal on a carbon-based substrate. [30] The method for producing a fuel cell catalyst according to [26], further comprising the step of depositing a transition metal on the carbon-based substrate.

 [31] The method for producing a fuel cell catalyst according to [27], further comprising a step of depositing a transition metal on a carbon-based substrate.

 [32] A fuel cell stack containing the fuel cell catalyst according to [1].

 [33] A fuel cell stack containing the fuel cell catalyst according to [5].

 [34] A fuel cell system including the fuel cell stack according to [32].

 [35] A fuel cell system including the fuel cell stack according to [33].

[0015] According to the present invention, it can be replaced with a noble metal catalyst such as platinum, which is expensive and problematic in terms of resources, has a good catalytic action, and can be synthesized inexpensively and safely. Provided are a fuel cell catalyst, a fuel cell electrode and a fuel cell using the fuel cell catalyst.

 [0016] According to the present invention, since a fuel cell using an inexpensive fuel cell catalyst is provided, expansion and practical application of the fuel cell to a fuel vehicle, a fixed cogeneration system, etc. are promoted. The

 Hereinafter, the force S for explaining the present invention in more detail, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

 [0018] [Catalyst for fuel cell]

 The fuel cell catalyst according to the first aspect of the present invention contains tellurium (Te), and further comprises ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir). The value of X when expressed as M Te, including one or more elements M selected from 0.2 <X <4

 1 X

 It is. In the description of the first embodiment, Te and element M may be collectively referred to as an active ingredient.

[0019] The fuel cell catalyst according to the second aspect of the present invention includes tellurium (Te), ruthenium (Ru), and optionally contained rhodium (Rh), palladium (Pd), osmium (Os), And one or more elements selected from the group consisting of iridium (I r) and the value of X when expressed as L Ru Te

 Y 1 X

 However, X> 0.2 and the value of Y is 0 <y≤10. In the description of the second embodiment, Te, Ru, and element L may be collectively referred to as an active component.

[0020] In any of the embodiments, the fuel cell catalyst of the present invention comprises only an active component. In addition, other transition metals may be included. The active ingredient may be applied to the substrate.

 [0021] In the following, one or more elements selected from the group consisting of elements represented by M, namely ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir) are used. The above elements are sometimes referred to as “Group VIII metals”. One or more elements L selected from the group consisting of rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir) may be referred to as “Group VIII metals other than Ru”.

 [0022] In addition, a catalyst for a fuel cell in which the active component is not deposited on the substrate and is substantially composed only of the active component is referred to as "essential catalyst", and the active component is deposited on the substrate. The deposited fuel cell catalyst is sometimes referred to as an “adhered catalyst”.

 [0023] <Active ingredient>

 Next, the abundance ratio of tellurium (Te) element and group VIII metal element (M) in the active component of the fuel cell catalyst of the first embodiment will be described. When the composition of the active ingredient is described as M Te, X>

 1 X

 0.2, particularly preferably X> 1, X <4, preferably X <3, more preferably X <2.5. Ternore element abundance ratio X force S, below this range, the activity becomes low, and even if it exceeds this range, it becomes difficult to achieve activity. Two or more Group VIII metal elements (M) may be used. M Te is the ratio of the total number of group VIII metal elements M to the number of tellurium elements Te

1 X

 Represents a rate.

 [0024] The abundance ratio of tellurium (Te) element, ruthenium (Ru) element, and Group VIII metal (L) other than Ru in the active component of the fuel cell catalyst of the second embodiment will be described below. When the composition of the active ingredient of the second aspect is described as L Ru Te, X is X> 0.2, preferably X> 1.

 Y 1 X

 In general, X is 20, preferably X is 15, more preferably X is 10, more preferably X is 5, and particularly preferably X is 3. If the abundance ratio of tellurium is below this range, the activity will be low, and even if it exceeds this range, it will be difficult to achieve activity.

[0025] Y is 0 <Y≤10, preferably 0 <Υ≤5, more preferably 0 <Υ≤3. Two or more Group VIII metal elements (L) other than Ru may be used. L Ru Te is a group VIII gold other than Ru

 Y 1 X

It represents the ratio of the total number of elements of the genus element L, the number of ruthenium elements (Ru), and the number of tellurium elements (Te). [0026] In both the first and second embodiments, the abundance ratio of each element in the catalyst is determined according to a conventional method. The catalyst is weighed and then decomposed by alkali melting, and the volume is adjusted after adding the acid. It can be quantified by inductively coupled plasma optical emission spectrometry.

 [0027] In any embodiment, the tellurium content in the active ingredient is usually 5% or more, more preferably 6% or more, still more preferably 10% or more, usually 9% by weight relative to the whole active ingredient. It is 6% or less, preferably 95% or less, more preferably 93% or less, still more preferably 90% or less, and most preferably 87% or less. If the tellurium content in the active ingredient is below this range, the activity will be low, and even if it exceeds this range immediately, it will be difficult to produce the activity.

[0028] In the first and second embodiments, the total content of Group VIII metals in the active ingredient, that is, ruthenium, rhodium, palladium, osmium, and iridium, is usually 1 ° / ο with respect to the whole active ingredient Above, preferably 5. / ₀ or more, more preferably 7. / ₀ or more, more preferably 10% or more, more preferably 13. / ₀ or more, usually 95% or less, preferably 90% or less, more preferably 88% or less, and still more preferably 85% or less. If the content of the Group VIII metal in the active ingredient is below this range, the activity will be low, and even if it exceeds this range, it will be difficult to produce the activity.

 [0029] In the first and second embodiments, the active ingredient may contain one kind of Group VIII metal alone, or may contain two or more kinds. The active ingredient preferably contains ruthenium or oral dimethyl as the group VIII metal, particularly preferably ruthenium as the group VIII metal.

 [0030] It should be noted that the active ingredient can also contain ingredients other than tellurium elements and Group VIII metals in a range that does not impair the effects of the present invention.

 [0031] In the active ingredients of the first and second embodiments, tellurium may be Te element TeO,

 2

Oxides such as TeO, oxo acids such as H TeO and H TeO, chlorides such as TeCl and TeBr, etc.

3 2 3 6 6 2 2

 These inorganic compounds and organic compounds such as teropen fene may be used. Group VIII metals can also be combined with organic compounds as well as inorganic compounds such as metal elements, oxides, and chlorides. For example, ruthenium may be Ru element such as RuO, RuO

 2 Oxides, chlorides such as RuCl · χΗ や, inorganic compounds such as Ru (N〇) (NO), Ru (acac) and

 3 2 3 3 3

You may take the form couple | bonded with organic compounds, such as Ru (CO).

 3 12

[0032] The tellurium component and the group VIII metal component constituting the active component may be present without any bond, or may be present with a bond. These exist with bonds In the case where the elements are directly bonded to each other, the active component may be one having a so-called alloy form.

[0033] Specific examples of active ingredients having an alloy form include RuTe, RuTe, RuTe, OsTe, RhTe, RhTe, RhTe, RhTe, RhTe, IrTe, IrTe, PdTe, PdTe , Pd

Te, Pd Te, Pd Te, Pd Te, Pd Te, Pd Te, Pd Te, Pd Te, Pd Te, Pd Te, Pd Te, etc. Among them, RuTe, RuTe, Ru Te are particularly preferred. Force S is preferred. It may be in the form of an alloy in which tellurium and two or more elements of the vm group metal are combined.

 [0034] The existence form 0 of the element in the active ingredient can be specified by X-ray diffraction (XRD). That is, for example, the presence form of an element can be specified by irradiating an active ingredient deposited on a substrate described later with X-rays (Cu_K filaments) and observing the diffraction spectrum thereof.

[0035] Examples of the measurement apparatus and measurement conditions include, but are not limited to, the following.

[0036] Measuring apparatus

 Powder X-ray analyzer / PANalytical PW1700

 Measurement condition

 X-ray output (Cu—Κα): 40kV, 30mA

 Scanning axis: Θ / 2 Θ

 Measurement range (2 Θ): 3. 0 ° to 90.0.

 Measuring Mote: Continuous

 Reading width: 0.05 °

 Strike speed: 3.0 ° / min

 DS, SS, RS: 1 °, 1 °, 0.20mm

[0037] Specifically, RuTe has a peak of 2 Θ (± 0.3 °) of X-ray diffraction as 21.808 °, 27.

920 °, 31. 287 °, 32. 716 °, 43. 369 °, 45. 203 °, 48. 322 °, 51. 509 °, 53. 981 °, 56. 910 °, 68. 565 °, etc. 21.767 °, 26. 18 9 °, 27. 877 °, 31. 249 °, 32. 658 ° 33. 847 °, 36. 719 °, 39. 822 °, 43. 30 Those giving characteristic peaks such as 8 °, 44. 377 °, 45. 177 °, 45. 801 °, 48. 244 °, 50. 117 °, 50. 661 °, 51. 42 6 °, etc. 857 °, 31. 271 °, 34. 344 °, 39. 873 °, 47. 123 °, 49. 353 °, 51. 532 °, 53. 614 °, 57. 636 °, 65. 236 °, 67. Those giving characteristic peaks such as 032 °, 68.881 °, 72.414 °, 77.547 °, 80.922 °, 82.608 °, 85.948 °, etc.

<Pure catalyst shape>

 There is no particular limitation on the shape of the pure catalyst made of the active component not deposited on the substrate, but it is most generally particulate. The average particle size of the particulate pure catalyst is usually 100 zm or less, preferably lOOOnm or less, more preferably 500 nm or less, particularly 300 nm or less, usually 0.5 nm or more, preferably 1. Onm or more, more preferably 2. Above Onm. If the particle size of the pure catalyst is less than this range, it becomes unstable and becomes deactivated, and if it exceeds this range, it becomes difficult to obtain high activity.

 [0039] The average particle diameter of the pure catalyst is determined by unifying the direction in which the length of the particle diameter is measured with a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The length is measured and shown as an average value.

 [0040] <Substrate>

 The deposition catalyst has a substrate and an active component deposited and held on the substrate. In order to electrically connect the active component, the substrate preferably has high conductivity.

[0041] The substrate is preferably a carbon-based substrate having high conductivity.

 [0042] The carbon-based substrate is not particularly limited, and may be, for example, carbon black, carbon nanotube, carbon nanohorn, carbon nanocluster, fullerene, pyrolytic carbon, activated carbon or the like. The carbon-based substrate may be vapor grown carbon fiber (Vapor Grown Carbon Fiber: hereafter may be abbreviated as “VGCF”), especially by heat treatment to increase electrical conductivity. VGCF has suitable elasticity and is suitable.

[0043] Among these carbon-based substrates, carbon black is industrially advantageous in terms of conductivity, availability, and cost. Examples of carbon black include channel black, furnace black, thermal black, acetylene black, oil furnace black, and gas furnace black. These carbon-based substrates can be used alone Can be used in combination of two or more.

[0044] The specific surface area of the substrate is not particularly limited, but is usually 5 m ² / g or more, preferably 100 m ² / g or more, more preferably 150 m ² / g or more, usually 5000 m ² / g or less, preferably Is preferably 2000 m ² / g or less. If this specific surface area is too small, the effective area for depositing the active ingredient will be reduced, and the catalytic field will not be sufficiently obtained as the reaction field is reduced. In addition, when the specific surface area is excessively large, the pore diameter of the substrate may be small, and even if an active component is deposited in the small pores, sufficient catalytic activity cannot be obtained. The specific surface area of the substrate is measured by the BET method.

 [0045] The form of the substrate is not particularly limited, but the most commonly used is a powder form.

 <Adhesion of active ingredient to substrate>

 In the present invention, the state in which the active ingredient is adhered to the substrate refers to a state in which both are in contact with each other so as to obtain electrical conductivity between the active component and the substrate. Accordingly, the active ingredient can be applied to the substrate simply by mixing the active ingredient and the base. However, as described later, after mixing the active ingredient supply compound and the substrate, the mixture is calcined. It is preferable to deposit. Alternatively, the substrate and the active component may be mixed and then fired. Hereinafter, the state in which the active ingredient supply compound or the active ingredient is mixed with the substrate and then fired and the active ingredient is deposited is referred to as “supporting”.

 [0047] The shape of the active ingredient attached to the substrate is not particularly limited, but the most common is a particulate form. The particulate active ingredient has an average particle size of usually 100 / m or less, preferably 1000 or less, more preferably 500 or less, and most preferably 300 or less, usually 0.5 nm or more, preferably 1. Onm Above, more preferably 2. Onm or more is desirable. If the particle size of the active ingredient is below this range, it becomes unstable and becomes inactive, and if it exceeds this range, it becomes difficult to obtain high activity.

 [0048] The average particle diameter of the active ingredient deposited on the substrate is standardized in the direction in which the particle length is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Then, the particle length in the direction is measured, and the average value is shown.

[0049] In order to deposit an active ingredient having such a small average particle diameter on a substrate, the following What is necessary is just to devise the manufacturing method. In particular, it is preferable to control the crystal growth state by lowering the firing temperature after mixing the substrate and the active component and shortening the firing time.

[0050] The weight ratio of the active ingredient shows the deposition ratio to the substrate of the active ingredient Z (active ingredient + substrate), such is limited to a particular record, but usually 10_ ⁵ or more, preferably 0.001 or more More preferably, it is 0.01 or more, particularly 0.05 or more, usually 0.95 or less, preferably 0.4 or less, and more preferably 0.3 or less. If the deposition ratio of the active ingredient is less than this range, the desired activity cannot be obtained, and if it exceeds this range, the activity improvement effect due to deposition is less likely to occur.

 [0051] <Other catalyst components>

 In the present invention, a transition metal may be further deposited on the substrate as long as the effects of the present invention are not impaired.

 [0052] This transition metal (hereinafter sometimes referred to as “other catalyst component”) is an element belonging to the fourth to sixth periods of groups IIIA to VIIA, VIII, and IB of the periodic table. , Titanium (Ti), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Konolt (Co), Nickel (Ni), Copper (Cu), Yttrium (Y), Zirconium (Zr), Niobium (Nb), Molybdenum (Mo), Lanthanum (La), Palladium (Eu), Gold (Au), Cerium (Ce), Tantanole (Ta), Tungsten (W), Rhenium (Re) , Praseodymium (Pr), neodymium (Nd). Transition metals have the following electrochemical equilibrium formula

 Oxidized body + ne— = reduced form

 It is desirable that the standard electrode potential E ° (25 ° C) in the aqueous solution is positive. This is because elution due to oxidation is difficult to occur as a natural property of metals, and there is little deterioration of the catalyst due to it. Specific examples of such transition metals include gold and silver.

 [0053] However, in order to make the catalyst more industrially advantageous, it is better to reduce the number of expensive catalyst components in the above.

[0054] Platinum (Pt) can be used in combination as a transition metal. Platinum is expensive, so it is desirable to add a small amount. In the case of adding platinum, specifically, the weight ratio of the total Z active component of the platinum component is usually 0.001 or more, preferably 0.01 or more, and more preferably 0.00. It is 05 or more, usually 0.4 or less, preferably 0.3 or less, and more preferably 0.2 or less.

[0055] The following shows the electrochemical equilibrium equation of main transition metals and the standard electrode potential E ° (25 ° C).

[0056] [Table 1]

[0057] These transition metals as other catalyst components may be used alone or in combination of two or more.

 [0058] Specific examples in which the transition metal and the active component are used in combination include the following i) V).

 i) The active ingredient is mixed with other catalyst components to the substrate.

 ii) Other catalyst components are supported on the substrate together with the active components.

 iii) The active component supported on the substrate is mixed with other catalyst components.

 iv) The other catalyst component supported on the other substrate is mixed with the active component.

 V) The other catalyst component supported on the other substrate is mixed with the active component supported on the substrate.

[0059] The weight ratio of the total Z active components of the transition metals is usually 0.001 or more, preferably 0.01 or more. In particular, it is 0.05 or more, usually 0.5 or less, preferably 0.4 or less, and more preferably 0.3 or less. If this weight ratio is less than this range, it is difficult to obtain the desired activity.

[0060] The transition metal is preferably in the form of powder. The average particle size of this powder is usually lOOOnm or less, preferably 500 nm or less, more preferably 300 nm or less, and usually 0.5 nm or more. If the average particle size is below this range, the catalyst becomes unstable and the catalyst becomes inactive, and if it exceeds this range, it is difficult to obtain high activity.

[0061] Note that, in the fuel cell catalyst of the present invention, a metal component other than the transition metal element is present.

Included in amounts of several weight percent or less based on the weight of the active ingredient.

[0062] A catalyst containing an active component and a transition metal, in particular, a catalyst having an active component and a transition metal supported on a substrate has high catalytic activity. This is presumably because the transition metal functions as a co-catalyst for the active ingredient and the activity is improved.

<Manufacture of pure catalyst>

 The method for synthesizing the pure catalyst according to the first embodiment composed only of the active component not deposited on the substrate can be carried out by any known method without particular limitation.

[0064] For example, an element supply compound serving as an active ingredient, that is, a precursor of the active ingredient, is dissolved or dispersed in a solvent such as water at a predetermined molar ratio, and after filtration or evaporation of the solvent, as necessary. And a step of activating the precursor (for example, reduction treatment).

[0065] The precursor of each element is not particularly limited as long as it can be thermally decomposed. Tellurium precursors include tellurium powder (Te), halides such as TeCl, TeBr, TeCl,

Inorganic salts such as oxides such as TeO and TeO and oxoacids such as H TeO and H TeO

[0066] In addition, precursors of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir) include halides, oxides, inorganic salts, and organic acid salts thereof. In addition to the above, a compound that binds to an organic compound, and the like can be given. Specific examples of ruthenium compounds include RuCl · χΗ 0, halides such as RuBr, Ru (SO), Ru (N〇) (NO) K RuO ·

Inorganic salts such as HO, organic acid salts such as Ru (OCH CO), ruthenium acetyl acetylate

2 2 3 4

And organic compounds such as (Ru (acac)). Rhodium compounds include RhCl · χΗ〇, Halides such as RhBr, inorganic salts such as KRh (SO) · 12Η O, Rh (NO) · 2Η O, R

3 4 2 2 3 3 2

 Organic salts such as h (○ CH CO) are listed. PdCl, PdC as palladium compounds

 3 3 2

 1 · 2Η〇, Halides such as PdF, PdCl, K PdCl, K PdCl, Pd (NO), etc.

2 2 2 4 2 4 2 6 3 2 Organic salts such as organic salt and Pd (〇CH CO). Osminium compounds include Os

 3 2

 Halides such as C1, K 2 OsCl, and oxides such as ○ s ○. Iridium compounds

3 2 6 2

 For example, halides such as IrCl and IrBr, oxides such as IrO, and inorganic salts such as Ir (SO)

 3 3 2 4 2

 Is mentioned.

 [0067] These precursors may be used singly or in combination of two or more.

[0068] To produce a pure RuTe catalyst, for example, RuCl or Ru (acac) and H TeO are desired.

 X 3 3 6 6 molar ratio (H TeO molar ratio relative to RuCl, Ru (acac) etc. is usually 0.2 or more, preferably

 3 3 6 6

 1 or more, usually 10 or less, preferably 4 or less) and dissolved in water for a predetermined time (usually 10 minutes or more, preferably 30 minutes or more, usually 50 hours or less, preferably 30 hours or less). ) After standing, if necessary, at a predetermined temperature (usually 60 ° C or higher, preferably 100 ° C or higher, usually 300 ° C or lower, preferably 200 ° C or lower) for a predetermined time (usually 10 minutes or longer, (Preferably 30 minutes or more, usually 50 hours or less, preferably 30 hours or less) Heat or reflux, and then obtain a precipitate with an evaporator. This is air-dried at room temperature, and then in an inert gas atmosphere such as nitrogen or argon for a predetermined time (usually 10 minutes or more, preferably 30 minutes or more, usually 50 hours or less, preferably 30 hours or less), a predetermined temperature (usually 100 ° C or higher, preferably 200 ° C or higher, usually 1000 ° C or lower, preferably 800 ° C or lower). Then, for a predetermined time (usually 10 minutes or more, preferably 30 minutes or more, usually 50 hours or less, preferably 30 hours or less), a predetermined temperature (usually 100 ° C or more, preferably 200 ° C or more, more preferably 300 The hydrogen concentration in an inert gas that can be mixed with an inert gas such as nitrogen or Ar under a flow of hydrogen (° C or higher, usually 1000 ° C or lower, preferably 800 ° C or lower) 1% or more, preferably 10% or more, 100% or less, or 80./o or less). Thereby, an active component containing Ru and Te, that is, a pure catalyst can be obtained.

[0069] Pure catalysts other than RuTe can be produced in the same manner.

 X

[0070] Thereafter, in an inert gas atmosphere having a low oxygen concentration (for example, an oxygen concentration of about 5 wt% or less, especially about 2 wt% or less) for a predetermined time (usually several tens of minutes or more, preferably 30 Minutes or less In addition, a passivation treatment may be performed to form a passive film by treatment at a predetermined temperature (usually around room temperature) usually for 10 hours or less, particularly 5 hours or less.

 <Manufacture of a coated catalyst>

 The deposition catalyst of the second embodiment is produced by depositing an active component on a substrate. Here, the active component may be applied to the substrate by, for example, a loading method in which the active component or a precursor of the active component is mixed and baked with the substrate, a mixing method in which the active component and the substrate are simply mixed, and other impregnations. It can carry out by well-known methods, such as a method, a precipitation method, an adsorption method.

 [0072] For example, in the deposited catalyst, the precursor of each element is dissolved or dispersed in a solvent such as an aqueous solution at a desired molar ratio, and the substrate is impregnated with the substrate, or the substrate is immersed in the solution. Thereafter, the precursor is deposited on the substrate by filtering or distilling off the solvent, and if necessary, a step of activating the precursor of the active component (for example, reduction treatment) is performed. As the active component precursor, the same compounds as those used in the production of the pure catalyst can be used. Among them, the ruthenium precursor is RuCl · χΗ 0 ac) Ru (NO) (NO)

 3 2, Ru (ac

 As a ternole precursor with 3 and 3 3 being preferred, H TeO is preferred.

 6 6

 [0073] An example of a method for producing a deposition catalyst containing Ru and Te as active components will be described below. RuCl

 3 or the mixing ratio of Ru (acac) and H TeO depending on the desired molar ratio (RuCl, Ru (acac)

 The molar ratio of H TeO to 3 6 6 3 3 etc. is usually 0.2 or more, preferably 1 or more, usually 10 or less, preferably

 6 6

It is preferably dissolved in water at 4 or less), and a predetermined amount of a substrate such as carbon black is mixed with this, and a predetermined time (usually 10 minutes or more, preferably 30 minutes or more, usually 50 hours or less, preferably 30 hours or less). )put. It should be noted that ultrasonic treatment may be performed when left unattended. Next, if necessary, the temperature is usually 60 ° C or higher, preferably 100 ° C or higher, usually 300 ° C or lower, preferably 200 ° C or lower, for a predetermined time (usually 10 minutes or longer, preferably 30 ° C). Min., Usually 50 hours or less, preferably 30 hours or less). Heat or reflux. Then, the precipitate is obtained by filtration or evaporator. This is air dried at room temperature. Next, under an inert gas atmosphere such as nitrogen or argon for a predetermined time (usually 10 minutes or more, preferably 30 minutes or more, usually 50 hours or less, preferably 30 hours or less), a predetermined temperature (usually 100 ° C or more, preferably After drying at 200 ° C or higher, usually 1000 ° C or lower, preferably 800 ° C or lower, and then for a predetermined time (usually 10 minutes or longer, preferably 30 minutes or longer, usually 50 hours or shorter, preferably 30 hours or shorter) ) At a constant temperature (usually 100 ° C or higher, preferably 200 ° C or higher, more preferably 300 ° C or higher, usually 1000 ° C or lower, preferably 800 ° C or lower) under an air stream containing hydrogen (such as nitrogen or Ar) There is no particular limitation on the hydrogen concentration in the inert gas that can be mixed with the above inert gas, but it is heated at 1% or more, preferably 10% or more, 100% or less, or 80% or less. As a result, an adherent catalyst in which an active component containing Ru and Te is supported on a substrate is obtained.

 [0074] After that, in an inert gas atmosphere with a low oxygen concentration (for example, an oxygen concentration of about 5 wt% or less, especially about 2 wt% or less) for a predetermined time (usually several tens of minutes, preferably 30 minutes). The passivation treatment can be performed to form a passive film by treatment at a predetermined temperature (usually around room temperature) usually for 10 hours or less, particularly 5 hours or less.

 [0075] Further, the active ingredient can be applied to the substrate by preparing the active ingredient in advance by the above-mentioned known method, mixing it with a substrate, and kneading the mixture in a mortar or the like. This mixing may be dry or wet, but is preferably wet mixed using a medium such as water and then dried at about 100 to 200 ° C.

 [0076] Among the above-described catalyst production methods, a support method in which a carbon-based substrate and an active component and a precursor selected from active component precursors are mixed and then calcined is preferable. This calcination can improve the activity of the resulting catalyst. The reason why the activity can be improved by firing in this way is not necessarily clear, but since the active component is deposited on the carbon-based substrate, sintering of the active component is suppressed during firing. It is presumed that the activity is enhanced.

 [0077] When the above-mentioned transition metal is applied to the substrate together with the active component, the transition metal may be added before or after the active component deposition step, which may be performed simultaneously with the active component deposition step. It may be deposited. Here, the “active component deposition step” includes the entire process from the addition of the active component precursor to the provision of the active component, that is, the process for depositing the active component.

[0078] Examples of the transition metal precursor for depositing the transition metal on the substrate include oxides, inorganic acid salts such as nitrates, sulfates, and carbonates, organic acid salts such as acetates, and halides. Hydrides, carbonyl compounds, ammine compounds, olefin coordination compounds, phosphine coordination compounds or phosphite coordination compounds. These can be used alone or in combination. You may use the above together.

 [0079] In order to deposit the transition metal together with the active component on the substrate, for example, the transition of chloride or the like to the catalyst in which the active component containing Ru and Te synthesized by the above-described method is supported on the substrate. The solution in which the metal compound is dissolved is added and allowed to stand for a predetermined time (usually 10 minutes or more, preferably 30 minutes or more, usually 50 hours or less, preferably 30 hours or less), and then the solvent is distilled off with an evaporator. In this case, ultrasonic treatment may be performed. Next, the hydrogen concentration in the inert gas that can be mixed with an inert gas such as nitrogen or Ar is not particularly limited, but it is 1% or more, preferably 10% or more, 100% % Or less or 80% or less) at a predetermined temperature (usually 100 ° C or higher, preferably 150 ° C or higher, usually 800 ° C or lower, preferably 500 ° C or lower) for a predetermined time (usually 10 minutes) (Above, preferably 30 minutes or more, usually 50 hours or less, preferably 30 hours or less). As a result, it is possible to obtain a deposited catalyst in which an active component containing Ru and Te and a transition metal are both supported on a substrate.

 [0080] Thereafter, in an inert gas atmosphere having a low oxygen concentration (for example, an oxygen concentration of about 5 wt% or less, especially about 2 wt% or less) for a predetermined time (usually several tens of minutes, preferably 30 minutes). The passivation treatment can be performed to form a passive film by treatment at a predetermined temperature (usually around room temperature) usually for 10 hours or less, particularly 5 hours or less.

 [0081] The transition metal as described above may be used as it is by mixing it with the substrate on which the active component is applied, or may be used by mixing the active component with the substrate on which the transition metal is applied. good.

 [Electrode for fuel cell and fuel cell]

 The fuel cell electrode of the present invention contains the above-described fuel cell catalyst of the present invention. The fuel cell of the present invention uses such a fuel cell electrode of the present invention.

In the fuel cell according to the present invention, as described above, the fuel is supplied to the anode, the oxidant is supplied to the power sword, the potential difference between the anode and the power sword is taken out as a voltage, and the power is supplied to the load. This power generation device includes an anode electrode, a force sword electrode, and an electrolyte sandwiched therebetween. In a polymer electrolyte fuel cell, an ion exchange membrane is used as an electrolyte. Solid polymer fuel cells include both PEFC fuel cells that use hydrogen as the fuel and direct methanol fuel cells (DMFC) that use methanol and water. [0084] In the case of a PEFC type fuel cell in which a catalyst layer is formed on both surfaces of an ion exchange membrane as an electrolyte and a gas diffusion layer is formed outside the catalyst layer, an anode gas diffusion layer and a force sword gas diffusion layer An electrolyte membrane / electrode assembly in which is integrally formed is used. In the case of a D MFC type fuel cell, an electrolyte membrane / electrode assembly in which a methanol aqueous solution current collector and a force sword gas diffusion layer are integrally formed is used. In the electrolyte membrane Z electrode assembly, a partition plate is disposed on the diffusion layer side, and a plurality of unit cells including the partition plate, the electrolyte membrane Z electrode assembly, and the partition plate are stacked until a desired voltage corresponding to the application is obtained. To form a fuel cell stack. Normally, several tens of cells and several hundred cells are stacked to form a fuel cell stack.

 [0085] As the catalyst for forming the catalyst layer of the electrolyte membrane / electrode assembly, the fuel cell catalyst described in the first and second embodiments described above is used.

 [0086] An ion exchange membrane as an electrolyte is only required to have a cation exchange capacity, but it is practically desired to withstand an oxidation-reduction atmosphere at a temperature of about 80 to 100 ° C, which is the operating temperature of the fuel cell. Therefore, perfluoroalkylsulfonic acid resins are exclusively used. Specific examples include perfluoroalkyl sulfonic acid resin membranes such as Nafion (registered trademark manufactured by DuPont), Flemion (registered trademark manufactured by Asahi Glass Co., Ltd.), Aciplex (registered trademark manufactured by Asahi Kasei Co., Ltd.), and the like.

 [0087] The ion exchange membrane preferably has a thickness of about 10 μΐη or more and about several hundreds μ。η or less. In order to reduce the electric resistance, it is desirable to make the ion exchange membrane thinner. Taking naphtho ions as an example, a force that often uses naphthion 115 with a thickness of about 120 / im is being developed. Electrolyte membranes with a thickness of 30 to 50 zm are being developed. I can do it.

[0088] The diffusion layer of the PEFC type fuel cell supplies hydrogen at the anode and air at the power sword, and also has a function as a current collector for taking out the generated voltage. Therefore, the diffusion layer is preferably made of a material that is an excellent electronic conductor and that allows both hydrogen and air gases to flow and withstand the working atmosphere. As a material constituting the anode gas diffusion layer and the force sword gas diffusion layer, a carbon porous body such as carbon paper or carbon cloth having a thickness of usually about 100 to 500 zm, preferably about 100 to 200 zm is used. DMFC type Similarly, the material of the methanol aqueous solution current collector of the fuel cell is selected so that the methanol aqueous solution circulates and can withstand the use atmosphere, and the thickness is usually about 100 to 500 μΐη, preferably about 100 to 200 μm. Carbon porous materials such as carbon paper and carbon cloth are used.

 [0089] When the electrolyte membrane / electrode assembly is used in a fuel cell, a partition plate made of a material such as carbon, or in some cases, stainless steel or titanium is usually used so that hydrogen and air do not mix behind it. However, it is common to use a partition plate in which grooves for the purpose of uniform and stable supply of hydrogen and air are formed.

 [0090] The method for producing the electrolyte membrane / electrode assembly of the fuel cell of the present invention is not particularly limited, and examples thereof include the following methods.

 Next, an example of a method for forming the force sword side catalyst layer and the anode side catalyst layer on the ion exchange membrane will be described. First, the fuel cell catalyst of the first or second embodiment is put in a suitable container, and a Nafion solution (concentration 5 wt%, manufactured by Aldrich) in which NaPoion (registered trademark) of DuPont is dissolved, alcohol, water, etc. A catalyst slurry is prepared by dispersing in a medium. In this case, it is more preferable to apply ultrasonic vibration in order to promote the dispersion well. The concentration of the fuel cell catalyst of the present invention in this catalyst slurry is preferably about 1 to 50 g / L in order to obtain the desired dispersibility. Of course, a binder such as polytetrafluoroethylene (PTFE) can be added to the slurry in the range of 3 to 30% by weight for the purpose of providing water repellency or preventing the catalyst layer from peeling off. Is possible. In addition, when the contents are agglomerated to make a paste, the alcohol has 2 to 5 carbon atoms such as ethanol or isopropyl alcohol, preferably a lower alcohol having about 2 to 4 carbon atoms, or 2 to 5 carbon atoms such as ethylene glycol, preferably A polyhydric alcohol having about 2 to 4 carbon atoms can be added to the water so as to have a ratio of 0.25 to 1.0, and can be aggregated.

 [0092] The catalyst slurry thus obtained is deposited on an ion exchange membrane, a gas diffusion electrode material or a transfer film, and then dried to form a force sword side catalyst layer and an anode side catalyst layer.

[0093] Specifically, the force sword side catalyst layer and the anode side catalyst layer are respectively formed on the ion exchange membrane or the gas diffusion electrode material by one of the following methods a) to d). a) Spray the catalyst slurry on the ion exchange membrane to be used and dry it.

 b) Spray the catalyst slurry on a gas diffusion electrode material such as carbon paper and dry. c) Spray catalyst slurry onto a transfer film material such as tetrafluoroethylene-hexafluoropropylene copolymer (FEP) film (development treatment) and dry it. The catalyst layer is transferred by appropriately pressing the surface onto a desired ion exchange membrane such as naphthion.

 d) As in c), after spreading the catalyst slurry on the FEP film, cover the slurry with a gas diffusion electrode material such as bonbon paper and dry.

[0094] In both the force sword-side catalyst layer and the anode-side catalyst layer, the amount of active ingredient attached (amount per unit area) is usually 0. OlmgZcm ² or more, preferably 0.1 lmg / cm ² or more, usually lg / cm. ^{It is 2} or less, preferably 20 mg / cm ² or less, and most preferably 10 mg / cm ² or less. If the amount of the active component attached is less than this range, sufficient catalytic activity cannot be obtained, and if it is more than this range, it is difficult to form an electrolyte membrane / electrode assembly.

 [0095] After the catalyst layer is formed on the ion exchange membrane, the catalyst layer that may be laminated with the anode gas diffusion layer material or the force sword gas diffusion layer material is formed on the anode gas diffusion layer material or the force sword gas diffusion layer material. After forming, it may be laminated with an ion exchange membrane. The laminate is preliminarily pressure-molded and then pressure-heat-molded with a press to obtain an electrolyte membrane / electrode assembly. In this joined body, the above-described force sword-side catalyst layer is formed on one surface of the ion-exchange membrane, the anode-side catalyst layer is formed on the opposite surface of the ion-exchange membrane, The gas diffusion layers constituting the anode and the force sword are laminated on the outside.

 [0096] When the laminate is preliminarily pressure-molded, it is preferable to set the temperature and pressure to be lower than the conditions of the main molding within a range in which the collapse of the catalyst layer is prevented. This is because the catalyst particles and the porous body for the gas diffusion layer do not cause compressive fracture.

[0097] The fuel cell system for PEFC of the present invention includes a fuel cell stack that obtains an electromotive force by an electrochemical reaction, a compressor that supplies compressed air as an oxygen-containing gas, and hydrogen as a fuel gas at a high pressure. It has a hydrogen cylinder to store in a compressed state. Other catalyst that burns exhaust hydrogen and exhaust air that was not used for power generation in the fuel cell stack A combustor may be provided as needed. Also, hydrogen may be supplied by reforming reaction such as methanol, natural gas or methane. In this case, the fuel cell system uses a methanol tank, a natural gas or methane tank, a water tank, a methanol / water mixer, an evaporator for evaporating methanol aqueous solution, etc., and a reforming reaction instead of a hydrogen cylinder. Equipped with a reformer to perform. Furthermore, a carbon monoxide reduction device may be provided in order to prevent poisoning of the fuel cell due to carbon monoxide contained in the hydrogen gas after the reforming reaction.

 In addition, the DMFC fuel cell system of the present invention includes a fuel cell stack that obtains an electromotive force by an electrochemical reaction, a compressor that supplies compressed air as an oxygen-containing gas, and a methanol aqueous solution container that is a fuel. Prepare. The aqueous methanol solution is sent to the anode electrode of the fuel cell stack by a feed pump. Further, the aqueous methanol solution may be heated and vaporized by an evaporator in advance and then supplied to the anode electrode. In addition, methanol aqueous solution that was not used for power generation in the fuel cell stack can be recovered and returned to the methanol aqueous solution container. The methanol aqueous solution may be collected using a gas-liquid separator when necessary. Example

 Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0100] In the following Examples and Comparative Examples, XRD analysis of the prepared catalysts was performed under the following conditions.

 [Powder XRD analysis]

 measuring device

 Powder X-ray analyzer / PANalytical PW1700

 Measurement condition

 X-ray output (Cu_K): 40kV, 30mA

 Stroke axis: Θ / 2 Θ

 Measurement range (2 Θ): 3. 0 ° to 90.0.

 Measuring Mote: Continuous

 Reading width: 0.05 °

Scanning speed: 3.0 ° / min DS, SS, RS: 1 °, 1 °, 0 · 20mm

[0101] In the following examples and comparative examples, the performance (catalytic activity) of the produced force sword electrode was measured by the following cyclic voltammetry (CV) measurement.

[0102] [CV measurement]

 Cyclic voltammetry (CV) measurement was performed under conditions where oxygen was not rate-controlled while using a plug that could maintain the sealing property of the electrolytic cell, publishing nitrogen or air in the electrolyte. The measurement conditions are as follows.

 Electrolyte: 1. OM H SO aqueous solution

 twenty four

 Strike speed: 5mVZ seconds

 Strike range: 100-700mV

 Counter electrode: Pt

 Reference electrode: Standard hydrogen electrode (SHE)

[0103] When the electrode potential is scanned in the direction of force lOOmV with respect to the standard hydrogen electrode, it is between the working electrode and the Pt counter electrode.

4H ⁺ + 0 + 4e— → 2H〇

 It can be seen that the oxygen reduction current due to. Measure the current value flowing at 400mV (SHE standard) when scanning in the base direction, and convert the measured current value into the current value per unit weight (lg) of the active ingredient contained in the catalyst. Evaluated.

 [0104] In the following examples, measurement cannot be performed if the catalyst activity is too high. Therefore, for convenience of measurement, the electrode is prepared by diluting the electrode so that the ratio of the active component in the substrate-coated catalyst is small. However, the preferred range of the active ingredient ratio and the amount of active ingredient supported on the electrode for actual electrode production are as described above.

 [0105] [Comparative Example 1]

 (Synthesis of RuTe (X = 4.77) catalyst)

 X

 Ru (acac), that is, ruthenium acetylase, so that the molar ratio of Ru and Te is 1:10.

 Three

 0.788 g of tonate and 4.545 g of telluric acid (manufactured by Sanwa Chemical Co., Ltd.) in carbon black (VULCAN

XC-72R (manufactured by Cabot, specific surface area (BET) 254 mVg)) 0.8 g was physically mixed in a mortar to obtain a mixture. This mixture was heated from room temperature to 300 ° C for 20 minutes at a flow rate of 3 L / hr of hydrogen, The temperature was raised from 300 ° C to 500 ° C over 3 hours. Thereafter, it was kept at 500 ° C. for ² hours and then cooled to room temperature. Finally, the catalyst was produced by leaving it in a nitrogen atmosphere containing 1% oxygen for 2 hours to passivate it. This catalyst was analyzed by XRD analysis using RuTe (value of 2Θ, 21.

 2

 757. , 26.202 °, 27.901 °, 31.294 °, 32.677 °, 33.897. , 36.791 °, 39.858. , 4 3.352 °, 44.444 °, 45.209 °, 45.900 °, 48.304 °, 51.491 °, 53.912 °, 56.906 °, 59.005 °, 59.902 °, 68.508. , 72.957 °, 78.340 °, 80.853. , 82.115 °, 85.902. And Te (values of 2Θ, peaks at 23.037 °, 27.556 °, 38.261 °, 40.451 °, 49.6 09 °, 62.808 °, 63.709 °). It was.

<Creation of force sword electrode>

 The resulting RuTe, Te and CB-containing catalyst and separately prepared carbon black (VULCA

 2

N XC — 72R (manufactured by Cabot, specific surface area (BET) 254 m ² / g)) was mixed in a mortar. The total content of Ru and Te in this mixture is 0.01778 weight ⁰ /. Met. After mixing 28.27 mg of this mixture with 5 mL of ethanol and thoroughly stirring with an ultrasonic cleaner, the total amount of Ru and Te deposited with microsyringe (calculated assuming that Ru and Te elements are not volatilized. Calculated below. The same was applied to the glassy carbon electrode, which is the working electrode, so that it was 72.41 ng / cm ² . Next, a 5% Nafion (registered trademark) solution (alcohol solution, manufactured by Aldrich Chemical Co., Ltd.) was dropped, dried by standing, and further dried under vacuum to obtain a force sword electrode.

 [0107] The force sword electrode was subjected to CV measurement, and the evaluation results of the catalyst activity are shown in Table 2.

 It is unknown whether the active species is Ru Te or Ru itself that interacts with Te.

 1 X

 Therefore, both the total activity per unit weight of Ru and Te and the activity per unit weight of Ru are described.

 [0108] The Te / Ru ratios of Examples 1, 7, 10 and Comparative Examples 1, 2 were determined according to a conventional method by weighing the catalyst and then decomposing it by melting with alkali, adding the acid, and then adjusting the volume. It was determined by inductively coupled plasma optical emission spectrometry.

[0109] In Examples 2 to 6, 8, 9 and Comparative Example 3, it was assumed that Ru and Te elements were volatilized and were not blown off during the heating overheat treatment under hydrogen flow, and Ru in the electrode The total supported amount of Te and Te, the supported amount of Ru in the electrode, and the catalytic activity were calculated. [0110] [Example 1]

 (Synthesis of RuTe (X = 2) catalyst)

 X

 Except that the amount of telluric acid (manufactured by Sanwa Chemical) in Comparative Example 1 was changed from 4.545 g to 1.818 g so that the molar ratio of Ru and Te was 1: 4, it was exactly the same as Comparative Example 1. The catalyst was prepared by this method. This compound was analyzed by XRD analysis using RuTe (value of 2Θ, 21.788 °, 26.203 °, 27.90

 2

 2 °, 31.293 °, 32.694 °, 33.892 °, 39.850 °, 43.350 °, 44.412 °, 45.207 °, 45.

842. , 48.300 °, 51.459 °, 53.949 °, 56.906 °, 58.999. , 59.814 °, 60.295 °, 6

8.500. , 72.995 °, 73.543 °, 76.072 °, 78.303 °, 80.849 °, 82.402 °, 85.404 °

, 85.901 ° peak).

[0111] <Creation of force sword electrode>

 Except that the obtained catalyst was used, the total adhesion amount of Ru and Te was reduced in the same manner as in Comparative Example 1.

A force sword electrode was prepared so as to be 2.15 ngZcm ² and evaluated in the same manner, and the results are shown in Table 2.

[0112] [Example 2]

 <Synthesis of RuTe (X = 2) catalyst using Ru chloride>

 X

 Ru (acac), 0.7888g in Comparative Example 1 so that the charged molar ratio of Ru and Te is 1: 2.

 Three

 Telluric acid (manufactured by Sanwa Chemical Co., Ltd.) Instead of 4.545 g, use ruthenium chloride (water-containing product, ruthenium content 42% by weight, NE Chemcat) 0 · 476g and telluric acid (manufactured by Sanwa Chemical Co., Ltd.) 0 · 909g They were dissolved in 50 ml of water. Carbon black (VULCAN XC-72) 0.8g was added so that 1 11 / (1 11 + 〇8) = 20% by weight, and sonicated for 1 hour at room temperature. Thereafter, the solvent was distilled off with an evaporator, and the obtained residue was dried at 300 ° C. for 3 hours under an argon stream. Then, cool to room temperature, hydrogen at a flow rate of 3LZhr at room temperature, etc. to 300 ° C for 20 minutes, 300. C force, et al. 800. The temperature increased to 33 C. Thereafter, it was kept at 800 ° C. for 2 hours and then cooled to room temperature. Finally, it was left to passivate in a nitrogen atmosphere containing 1% oxygen for 2 hours.

[0113] This compound was confirmed to contain RuTe by XRD analysis (the value of 2Θ was 21.

 2

991. , 26.258 °, 28.044 °, 31.396. , 32.757 °, 34.449 °, 39.996 °, 43.546 °, 4 5.441 °, 47.248 °, 48.448 °, 51.603 °, 53.703 °, 57.095 °, 60.344 °, 65.341 ° , 66.506 °, 68.697 °, 73.156 °, 78.402 °, 81.098 °, 82.696. , Gave a peak at 86.052 °).

[0114] <Creation of force sword electrode>

 Except for the obtained RuTe-containing catalyst ZCB, Ru and T were prepared in the same manner as in Comparative Example 1.

 2

A force sword electrode was prepared so that the total adhesion amount of e was 19 ngZcm ² , the same evaluation was performed, and the results are shown in Table 2.

[0115] [Example 3]

 <Synthesis of RuTe (χ = 2) catalyst using nitric acid-based Ru>

 X

 Comparative example 1 of Ru (acac), 0.7888 g

 Three

 Instead of 3.72% Ru (N ○) (NO) aqueous solution 5.37g and telluric acid (manufactured by Sanwa Chemical Co., Ltd.) 0.909g

 3 3

 Used to dissolve them in 50 ml of water. Carbon black (VULCAN XC-72) 0.8g was put in it so that 1 ^ 7 11 + 〇8) = 20% by weight, and ultrasonic treatment was performed for 1 hour at room temperature. Thereafter, the solvent was distilled off with an evaporator, and the obtained residue was dried at 300 ° C. for 3 hours under an argon stream. After cooling to room temperature, the temperature was increased from room temperature to 300 ° C for 20 minutes at a flow rate of 3 L / hr of hydrogen, 300 ° C force to 650 ° C for 3 hours. Thereafter, it was kept at 650 ° C. for 2 hours, and then cooled to room temperature. Finally, it was left to passivate in a nitrogen atmosphere containing 1% oxygen for 2 hours.

[0116] This compound was confirmed to contain RuTe by XRD analysis (the value of 2Θ was 21.

 2

 755. 27.893 °, 31.250 °, 32.694 °, 34.342 °, 39.850 °, 43.351 °, 45.251 °, 4 7.108. , 48.260 °, 51.499 °, 53.643 °, 56.949 °, 57.611. , 65.204 °, 67.049 °, 68.804 °, 77.549 °, 80.907 °, 82.558 °, 85.950 °).

[0117] <Creation of force sword electrode>

 Except for the obtained RuTe-containing catalyst ZCB, Ru and T were prepared in the same manner as in Comparative Example 1.

 2

A force sword electrode was prepared so that the total adhesion amount of e was 19 ngZcm ² , the same evaluation was performed, and the results are shown in Table 2.

[0118] [Example 4]

 <Example of heat treatment temperature of 500 ° C in Example 2>

A catalyst was synthesized in the same manner as in Example 2 except that the RuTe synthetic heat treatment temperature was 500 ° C. [0119] That is, Ru (acac), 0.7 in Comparative Example 1 was adjusted so that the charged molar ratio of Ru and Te was 1: 2.

 Three

Instead of 888g and telluric acid (manufactured by Sanwa Chemical) 4.545g, ruthenium chloride (water-containing product, ruthenium content 42% by weight, NE Chemcat) 0 · 476g and telluric acid (manufactured by Sanwa Chemical) 0 · Using 909 g, they were dissolved in 50 ml of water. Carbon black (VULCAN XC-72) 0.8 g was added so that 1 1/1 + 〇8) = 20% by weight, and sonicated for 1 hour at room temperature. Thereafter, the solvent was distilled off with an evaporator, and the obtained residue was dried at 300 ° C. for 3 hours in an argon stream. Then, it was cooled to room temperature, heated at a flow rate of 3 LZhr of hydrogen from room temperature to 300 ° C for 20 minutes, and heated from 300 ° C to 500 ° C for 3 hours. Thereafter, it was kept at 500 ° C. for 2 hours and then cooled to room temperature. Finally, it was passivated by leaving it in a nitrogen atmosphere containing 1% oxygen for 2 hours.

[0120] This compound was confirmed to contain RuTe by XRD analysis (the value of 2Θ was 21.

 695. , 27.855 °, 31.302. 32.741 °, 39.905 °, 43.448 °, 45.889 °, 48.300 °, 51.457 °, 53.998 °, 57.199 °, 58.848 °, 65.247 °, 68.357. , 73.096 °, 78.150 °, 82.486 °, 85.749 °, 85.954. Gave a peak).

[0121] <Creation of force sword electrode>

A force sword electrode was prepared in the same manner as in Comparative Example 1 except that the obtained RuTe-containing catalyst / CB was used so that the total adhesion amount of Ru and Te was 95 ng / cm ^2, and evaluation was performed in the same manner. The results are shown in Table 2.

[0122] [Example 5]

 <Example in which the heat treatment temperature is 350 ° C in Example 2>

 A catalyst was synthesized in the same manner as in Example 2 except that the RuTe synthetic heat treatment temperature was 350 ° C.

 2

 [0123] That is, Ru (acac), 0.7 in Comparative Example 1 was adjusted so that the charged molar ratio of Ru and Te was 1: 2.

 Three

Instead of 888 g and telluric acid (manufactured by Sanwa Chemical Co., Ltd.) 4.545 g, ruthenium chloride (water-containing product, ruthenium content 42% by weight, NE Chemcat Co., Ltd.) 0.476 g and telluric acid (manufactured by Sanwa Chemical Co., Ltd.) 0. Using 909 g, they were dissolved in 50 ml of water. Carbon black (VULCAN XC-72) 0.8 g was added so that 1 1/1 + 〇8) = 20% by weight, and sonicated for 1 hour at room temperature. Thereafter, the solvent was distilled off with an evaporator, and the obtained residue was dried at 300 ° C. for 3 hours in an argon stream. Then, cool to room temperature and flow of hydrogen 3LZhr. The temperature was raised from room temperature to 300 ° C for 20 minutes and 300 ° C force to 350 ° C for 3 hours. Thereafter, it was kept at 350 ° C. for 2 hours and then cooled to room temperature. Finally, it was passivated by leaving it in a nitrogen atmosphere containing 1% oxygen for 2 hours.

[0124] This compound was confirmed to contain RuTe by XRD analysis (the value of 2Θ was 27.

 850. , 28.155 °, 31.447 °, 32.449 °, 39.763 °, 43.700 °, 48.254 °, 57.108 °).

[0125] <Creation of force sword electrode>

A force sword electrode was prepared by the same method as in Comparative Example 1 except that the obtained RuTe-containing catalyst / CB was used, so that the total adhesion amount of Ru and Te was 19 ngZcm ^2. The results are shown in Table 2.

[0126] [Example 6]

 <Example of heat treatment temperature of 650 ° C in Example 2>

 (Synthesis of RuTe / carbon black (CB) catalyst)

 A catalyst was synthesized in the same manner as in Example 2 except that the RuTe synthetic heat treatment temperature was 650 ° C.

 2

 [0127] That is, Ru (acac), 0.7 in Comparative Example 1 was adjusted so that the charged molar ratio of Ru and Te was 1: 2.

Instead of 888g and telluric acid (manufactured by Sanwa Chemical) 4.545g, ruthenium chloride (water-containing product, ruthenium content 42% by weight, NE Chemcat) 0 · 476g and telluric acid (manufactured by Sanwa Chemical) 0 · Using 909 g, they were dissolved in 50 ml of water. Carbon black (VULCAN XC-72R) 0.8 g was added so that 1¾1 / (1 11 +0 8) = 20% by weight, and sonicated for 1 hour at room temperature. Thereafter, the solvent was distilled off with an evaporator, and the obtained residue was dried at 300 ° C. for 3 hours under an argon stream. After cooling to room temperature, the temperature was raised from room temperature to 300 ° C for 20 minutes at a flow rate of 3 L / hr of hydrogen, from 300 ° C to 650 ° C for 3 hours. After that, it was kept at 650 ° C. for 2 hours and then cooled to room temperature. Finally, it was passivated by leaving it in a nitrogen atmosphere containing 1% oxygen for 2 hours.

[0128] This compound was confirmed to contain RuTe by XRD analysis (the value of 2Θ was 21.

899. , 26.355 °, 27.951 °, 31.304 °, 32.753 °, 34.350 °, 39.949 °, 43.403 °, 4 5.300. , 47.220 °, 48.307 °, 51.595. , 53.702 °, 56.909 °, 59.946 °, 65.347 °, 68.598 °, 73.103 °, 78.302 °, 82.505 °, and 85.996 °). <Creation of force sword electrode>

 Other than using the obtained RuTe-containing catalyst / CB, Ru and Te were prepared in the same manner as in Comparative Example 1.

 2

A force sword electrode was prepared so that the total amount of adhesion was 19 ng / cm ² and evaluated in the same manner. The results are shown in Table 2.

 This force sword electrode was used for CV measurement, and the evaluation results of catalyst activity are shown in Table 2.

[0130] [Example 7]

 (Synthesis of RuTe (X = 2. 11) catalyst>

 X

 Except that the amount of telluric acid (manufactured by Sanwa Chemical) in Comparative Example 1 was changed from 4.545 g to 0.909 g so that the molar ratio of Ru and Te was 1: 2, it was exactly the same as Comparative Example 1. The catalyst was prepared by this method. This compound was analyzed by XRD analysis using RuTe (value of 2Θ, 21.507 °, 27.805 °, 31.30

 2

 0. , 32.743 °, 40.041 °, 43.498 °, 45.356 °, 48.246 °, 51.441 °, 54.002 °, 57.057. , 59.850 °, 65.306 °, 68.306. , 73.347 °, 82.394 °, 85.753 °, and 86.095 °).

[0131] <Creation of force sword electrode>

Obtained are except that using the catalyst, Comparative Example 1. Table of results performed to create a force cathode electrode so that the total adhesion amount force 9 ng / cm ² of Ru and Te, evaluated as the same manner as 2 It was shown to.

 [0132] [Example 8]

 (Synthesis of RuTe (X = l) catalyst)

 X

 Except that the amount of telluric acid (manufactured by Sanwa Kagaku) in Comparative Example 1 was changed from 4.545 g to 0.4545 g so that the molar ratio of Ru and Te was 1: 1, it was exactly the same as Comparative Example 1. The catalyst was prepared by the method. This compound was analyzed by XRD analysis using RuTe (value of 2Θ, 21.901 °, 27.945 °, 31.

 2

 300. , 32.655 °, 40.047 °, 48.153 °, 51.594 °, 53.695. , 65.170. , 73.212 °, 8 2.447 °) and Ru (values of 2Θ, 38.449 °, 43.550 °, 57.199 °, 68.542 °, 78.451 °, 85.997 °) It was confirmed.

<Creation of force sword electrode>

Obtained are except that using the catalyst, Comparative Example 1. Table of results performed to create a force cathode electrode so that the total adhesion amount force S1 2.02NgZcm ² of Ru and Te, evaluated as the same manner as 2 In Indicated.

 [Example 9]

 (Synthesis of RuTe (X = 0.5) catalyst)

 x

 A catalyst was prepared in the same manner as in Example 8, except that the amount of telluric acid was changed to 0.227 g in Example 8 so that the charged molar ratio of Ru and Te was 1: 0.5. This compound was analyzed by XRD analysis with RuTe (value of 2Θ, 21.846 °, 26.107 °, 27.907 °, 31.300., 32.745

 2

 . , 34.047 °, 39.897 °, 43.501 °, 45.244 °, 48.304 °, 51.590 °, 53.572 °, 54.0 03 °, 57.041 °, 68.555. , 72.953 ° and 82.364 °) and Ru (2 Θ, 3 8.705 °, 44.025 °, 78.394 ° and 85.950 °).

 <Creation of force sword electrode>

 Except that the obtained RuTe-containing catalyst ZCB was used, Ru and

 2

A force sword electrode was prepared so that the total adhesion amount of Te was 12 ng / cm ^2, and evaluation was performed in the same manner. The results are shown in Table 2.

[Example 10]

 (Synthesis of RuTe (X = 0.24) catalyst>

 X

 Except that the amount of telluric acid (manufactured by Sanwa Chemical) in Comparative Example 1 was changed from 4.545 g to 0.0909 g so that the molar ratio of Ru and Te was 1: 0.2, it was exactly the same as Comparative Example 1. The catalyst was prepared by this method. This compound was analyzed by XRD analysis using RuTe (value of 2Θ, 27.920 °, 31.298

 2

 . , 32.512. And Ru (values of 2Θ, which gave peaks at 38.440 °, 42.205 °, 43.999 °, 69.351 °, 78.497 °, 84.630 °).

[0137] <Creation of force sword electrode>

 Except for using the obtained RuTe-containing catalyst / CB, Ru and

 2

A force sword electrode was prepared so that the total adhesion amount of Te was 6.66 ngZcm ^2, and evaluation was performed in the same manner. The results are shown in Table 2.

[Comparative Example 2]

 (Synthesis of RuTe (X = 0.12) catalyst>

 X

Telluric acid (comparable with tritium) in Comparative Example 1 was adjusted so that the molar ratio of Ru and Te was 1: 0.055. The catalyst was prepared in exactly the same manner as in Comparative Example 1, except that the amount of (made by Wako Chemical) was changed from 4.545 g to 0.0250 g.

<Creation of force sword electrode>

Obtained other is using the catalyst, Comparative Example 1. Table of results performed to create a force cathode electrode such that the total amount of adhered Ru and Te is 5.6 8NgZcm ^2, evaluated as the same manner as 2 It was shown to.

 [0140] [Comparative Example 3]

 Te metal (manufactured by NE Chemcat) 0.299g and Ru (CO) (manufactured by Aldrich) 0.5

 3 12

 After adding g to m_Xylene 50ml and heating to 139 ° C under reflux condition for 20 hours under N, reaction

 2

 The liquid was filtered to obtain a black powder. Next, this powder was washed with jetyl ether and air-dried to prepare a catalyst.

[0141] <Creation of force sword electrode>

Except for using the obtained catalyst, a force sword electrode was prepared by the same method as in Comparative Example 1 so that the total adhesion amount of Ru and Te was 5.75 ng / cm ^2. Shown in Table 2

[0142] [Table 2]

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on June 23, 2005 (Japanese Patent Application No. 2005-183682), which is incorporated by reference in its entirety.

Claims

The scope of the claims

 [I] Tellurium (Te),

 At least one element M selected from the group consisting of noretenum (Ru), rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir);

 When the composition is expressed as M Te, it is 0.2 <X <4.

 1 X

 catalyst.

 [2] The fuel cell catalyst according to claim 1, wherein 1 <X.

 [3] The fuel cell catalyst according to claim 1, substantially consisting of Te and Ru.

 [4] A fuel cell catalyst according to claim 1, comprising RuTe.

 2

 [5] Tellurium (Te),

 Ruthenium (RU),

 Group power consisting of rhodium (Rh), palladium (Pd), osmium (Os), and iridium (Ir)

 When the composition is expressed as L Ru Te, it is 0.2 and X, and 0 <Y≤10.

 Υ 1 X

 Fuel cell catalyst.

 [6] The fuel cell catalyst according to claim 1, further comprising a substrate on which Te and elemental metal are deposited.

 7. The fuel cell catalyst according to claim 5, further comprising a substrate on which Te, Ru and element L are deposited.

8. The fuel cell catalyst according to claim 6, wherein the substrate is a carbon-based substrate.

9. The fuel cell catalyst according to claim 7, wherein the substrate is a carbon-based substrate.

10. The fuel cell catalyst according to claim 1, wherein the fuel cell is a polymer electrolyte fuel cell.

 [II] The fuel cell catalyst according to claim 5, wherein the fuel cell is a polymer electrolyte fuel cell.

 [12] an ion exchange membrane;

A fuel cell electrode material comprising the fuel cell catalyst layer of claim 1 formed on the ion exchange membrane.

[13] an ion exchange membrane;

 6. A fuel cell electrode material comprising the fuel cell catalyst layer of claim 5 formed on the ion exchange membrane.

 14. A fuel cell electrode material comprising an electrode gas diffusion layer and the fuel cell catalyst layer of claim 1 formed on the electrode gas diffusion layer.

15. A fuel cell electrode material comprising an electrode gas diffusion layer and the fuel cell catalyst layer of claim 5 formed on the electrode gas diffusion layer.

16. A fuel cell electrode material comprising a transfer film and the fuel cell catalyst layer according to claim 1 formed on the transfer film.

[17] An electrode material for a fuel cell, comprising: a transfer film; and the fuel cell catalyst layer according to claim 5 formed on the transfer film.

18. A fuel cell electrode comprising the fuel cell catalyst according to claim 1.

[19] A fuel cell electrode comprising the fuel cell catalyst according to [5].

20. A fuel cell using the fuel cell electrode according to claim 18.

21. A fuel cell using the fuel cell electrode according to claim 19.

 22. The fuel cell according to claim 20, wherein the fuel cell is a polymer electrolyte fuel cell.

 23. The fuel cell according to claim 21, wherein the fuel cell is a polymer electrolyte fuel cell.

 [24] A method for producing the fuel cell catalyst according to claim 8,

 Mixing a carbon-based substrate, a precursor of Te and a precursor of element M;

 Activating the precursor; and

 The manufacturing method of the catalyst for fuel cells characterized by having.

[25] A method for producing the fuel cell catalyst according to claim 9,

 A step of mixing a carbon-based substrate, a precursor of Te, a precursor of Ru, and a precursor of element L, and a step of activating the precursor

 The manufacturing method of the catalyst for fuel cells characterized by having.

[26] A method for producing a fuel cell catalyst according to claim 8, comprising: a carbon-based substrate; and A method for producing a fuel cell catalyst, comprising a step of mixing the fuel cell catalyst according to 1.

 [27] A method for producing the fuel cell catalyst according to claim 9, comprising a step of mixing the carbon-based substrate and the fuel cell catalyst according to claim 5. A method for producing a catalyst.

 28. The method for producing a fuel cell catalyst according to claim 24, further comprising a step of depositing a transition metal on the carbon-based substrate.

29. The method for producing a fuel cell catalyst according to claim 25, further comprising a step of depositing a transition metal on the carbon-based substrate.

30. The method for producing a fuel cell catalyst according to claim 26, further comprising a step of depositing a transition metal on the carbon-based substrate.

31. The method for producing a fuel cell catalyst according to claim 27, further comprising a step of depositing a transition metal on the carbon-based substrate.

32. A fuel cell stack containing the fuel cell catalyst according to claim 1.

[33] A fuel cell stack comprising the fuel cell catalyst according to claim 5.

34. A fuel cell system comprising the fuel cell stack according to claim 32.

35. A fuel cell system comprising the fuel cell stack according to claim 33.