JP2019075305A - Electrode carrier material and manufacturing method thereof, electrode material, electrode, and solid polymer fuel cell - Google Patents

Abstract

To provide an electrode carrier material that is excellent in durability and in which the ORR activity of the electrode is not easily reduced, and a manufacturing method thereof.SOLUTION: An electrode carrier material according to the present disclosure is formed of burr-like titanium suboxide. Further, a manufacturing method of the electrode carrier material according to the present disclosure includes a step of obtaining a burr-like titanium oxide, a step of coating the burr-like titanium oxide with silica, a step of reducing the burr-like titanium dioxide coated with silica and a step of removing the silica to obtain a burr-like titanium suboxide.SELECTED DRAWING: None

Description

  The present disclosure relates to a carrier material for an electrode and a method for producing the same, an electrode material, an electrode, and a polymer electrolyte fuel cell.

  A fuel cell is a device that generates electric power by electrochemically reacting a fuel such as hydrogen or alcohol with oxygen to generate a polymer electrolyte fuel cell (PEFC), a phosphoric acid fuel cell or the like depending on the electrolyte, operating temperature, etc. (PAFC), a molten carbonate fuel cell (MCFC), a solid oxide fuel cell (SOFC) and the like. Among them, PEFC is a fuel cell using a polymer membrane (ion exchange membrane) having ion conductivity as an electrolyte, and a material in which platinum is supported on a carbon carrier is generally used as an electrode material (for example, patent documents 1).

JP, 2012-17490, A

  However, in a material in which platinum is supported on a carbon support (e.g., when it is used at a high potential), the carbon support is susceptible to corrosion because the oxidation reaction of the carbon support proceeds with platinum. In addition, since a material in which platinum is supported on a carbon support is used in the air electrode (cathode) of a polymer electrolyte fuel cell, it is exposed to severe environments (acidic and oxidizing atmospheres), and therefore corrosion of the carbon support is It tends to be particularly easy to progress. Then, when the carbon support is corroded, platinum is detached from the carbon support, or aggregation or sintering of platinum occurs, so that the reaction surface area is reduced and the ORR activity (oxygen reduction reaction activity) is reduced. Thus, the carbon support has a problem that the durability is poor, and development of a support material for an electrode that replaces the carbon support has been required.

The present disclosure has been made to solve the above problems, and provides an electrode carrier material capable of producing an electrode excellent in durability and difficult to reduce the ORR activity, a method of manufacturing the same, and an electrode material. With the goal.
Another object of the present disclosure is to provide an electrode excellent in durability and difficult to reduce ORR activity, and a polymer electrolyte fuel cell having the electrode.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found that igagli-like titanium suboxide had properties suitable for use as a carrier material for electrodes, and the present invention It came to complete.

That is, the present disclosure relates to a support material for an electrode formed from titanium suboxide in the form of a gore.
In the present disclosure, a step of obtaining titanium oxide in the form of igaguri, a step of coating the titanium oxide in the form of igagri with silica, a step of reducing the titanium oxide in the form of igagri coated with the silica, and And C. removing the silica to obtain non-greasy titanium suboxide.

In addition, the present disclosure relates to an electrode material including the electrode carrier material and a noble metal supported on the electrode carrier material.
The present disclosure also relates to an electrode having a catalyst layer containing the electrode material.
Furthermore, the present disclosure relates to a polymer electrolyte fuel cell having the electrode.

According to the present disclosure, it is possible to provide a carrier material for an electrode capable of producing an electrode having excellent durability and in which the ORR activity is unlikely to be reduced, a method for producing the same, and an electrode material.
Further, according to the present disclosure, it is possible to provide an electrode which is excellent in durability and in which the ORR activity does not easily decrease, and a polymer electrolyte fuel cell having the electrode.

FIG. 2 is a cross-sectional view of a red iron-like titanium suboxide used for the electrode carrier material of the present disclosure. It is a FE-SEM image of the titanium suboxide manufactured in Example 1, and the product obtained in the middle of the manufacture. It is a X-ray-diffraction pattern of the titanium suboxide manufactured in Example 1, and the titanium oxide obtained in the middle of the manufacture. It is a polarization curve (current-potential curve) in Example 1 and comparative example 1 before an acceleration endurance test, and after performing 5000 start-and-stop imitation cycle cycles. It is a graph in Example 1 and Comparative Example 1 which shows the relationship between the cycle number of an accelerated endurance test, and the electric current when voltage is 0.8V. It is a TEM image of the working electrode of Example 1 and Comparative Example 1. It is a graph which shows ECSA before an accelerated endurance test in Example 1 and comparative example 1, and after a predetermined cycle of an accelerated endurance test.

(Carrier material for electrode and method for producing the same)
FIG. 1 shows a cross-sectional view of a red iron like titanium suboxide 1 used for the electrode carrier material of the present disclosure.
Here, in the present specification, the term "unguri-like" means a shape wrapped in a bowl-like protrusion. Specifically, as shown in FIG. 1, it means a shape having a core 2 and protrusions 3 radially extending from the core 2. Further, "titanium suboxide 1" means an oxide of titanium from which a part of oxygen is eliminated in a continuous crystal structure composed of oxygen atoms and titanium atoms.

The shape of the core portion 2 is not particularly limited, and may be a structure other than the spherical shape (for example, an ellipsoid etc.) shown in FIG.
The shape of the protrusion 3 is not particularly limited, and may be a structure (for example, a cylindrical shape) other than the conical shape shown in FIG. 1. In addition, the tip of the radially extending protrusion 3 does not have to be sharp, and may have another shape such as an arc shape or a planar shape.

The average height of the protrusions 3 is not particularly limited, but is preferably 5 to 100 nm, more preferably 10 to 80 nm. If the average height of the protrusions 3 is in the above range, the durability of the electrode is likely to be improved, and the ORR activity is less likely to be reduced.
Here, in the present specification, the “average height of the protrusions 3” refers to the height of the protrusions 3 measured from the TEM image of the surface of the titanium suboxide 1 observed by TEM (transmission electron microscope) Means the average value of It is preferable to calculate this average value from the heights of ten or more protrusions 3. Further, “the height of the protrusion 3” means the height from the core 2 to the top of the protrusion 3.

The average width of the protrusions 3 is not particularly limited, but is preferably 1 to 50 nm, more preferably 3 to 30 nm. If the average width of the protrusions 3 is in the above range, the durability of the electrode is likely to be improved, and the ORR activity is less likely to be reduced.
Here, in the present specification, the “average width of the projections 3” refers to the average of the widths of the projections 3 measured from the TEM image of the surface of the titanium suboxide 1 observed with a TEM (transmission electron microscope) It means the value. The average value is preferably calculated from the width of ten or more protrusions 3. Further, “the width of the protrusion 3” means the width at a half position of the height of the protrusion 3.

The composition of the titanium suboxide 1 is not particularly limited, in general, (wherein, n 2-10, more preferably a number of 2~8) Ti _n O _2n-1 can be represented by. Among them, titanium suboxide 1 is preferably Ti ₄ O ₇ , Ti ₅ O ₉ or a mixture thereof. With such titanium suboxide 1, the durability of the electrode is likely to be improved, so the ORR activity is unlikely to be reduced.

BET specific surface area of titanium suboxides 1 is not particularly limited, preferably 10 m ² / g or more, more preferably 20 m ² / g excess, more preferably at 25m ² / g or more and most preferably 30 m ² / g or more is there. If the BET specific surface area of titanium suboxide 1 is in the above range, the durability of the electrode is likely to be improved and the ORR activity is unlikely to be reduced. The BET specific surface area can be measured using a commercially available measuring device.

The average particle size of titanium suboxide 1 is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 8 μm, and still more preferably 0.1 to 5 μm. If the average particle diameter of titanium suboxide 1 is in the above range, the durability of the electrode is likely to be improved, and the ORR activity is unlikely to be reduced.
Here, in the present specification, the “average particle diameter of titanium suboxide 1” refers to the particle diameter of titanium suboxide 1 observed by FE-SEM (field emission scanning electron microscope) and measured from its SEM image. It means the average value. It is preferable to calculate this average value from the particle size of ten or more titanium suboxides 1.

  The iagori-like titanium suboxide 1 having the above-mentioned characteristics is provided with a step (first step) of obtaining an iagari-like titanium oxide, a step of coating the igagli-like titanium oxide with silica (a second step), and silica Manufacturing by a method including a step of reducing (S3) a reduction treatment of titanium oxide coated like in (a), and a step (a fourth step) of obtaining a titanium suboxide 1 in the shape of a sinter by removing silica it can. According to this method, it is possible to suppress sintering of the titanium oxide in the form of igagiri by covering the titanium oxide in the form of igagri with silica followed by reduction treatment, so that it is suitable for use as a carrier material for an electrode It is possible to obtain a titanium suboxide 1 in the form of raguri.

  There is no particular limitation on the method of obtaining titanium oxide in the first step, which is not particularly limited, and a known method (2 persons from Jing Sun, "Synthesizing and Comparing the Photocatalytic Properties of High Surface Area Rutile and Anatase Nanoparticles", Journal 86, No. 10, pages 1677 to 1682 (2003)). Specifically, a wet chemical method, for example, a hydrolysis reaction using an aqueous solution of titanium tetrachloride as a raw material can obtain a red oxide like titanium oxide.

There is no particular limitation on the method of coating the raguri titanium oxide with silica in the second step, and it can be carried out according to a known method. For example, titanium oxide in the form of rags may be added to and mixed with a mixture containing an alkoxysilane which is a silica source, water, an alkali and an organic solvent, and then dried.
The alkoxysilane is not particularly limited, and tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane and the like can be used. These can be used alone or in combination of two or more.

  Examples of the alkali include, but are not limited to, inorganic alkalis such as ammonia, sodium hydroxide and potassium hydroxide; inorganic alkali salts such as ammonium carbonate, ammonium hydrogencarbonate, sodium carbonate and sodium hydrogencarbonate; monomethylamine, dimethylamine and trimethylamine , Monoethylamine, diethylamine, triethylamine, pyridine, aniline, choline, tetramethyl ammonium hydroxide, organic alkalis such as guanidine; ammonium formate, ammonium acetate, ammonium monoformate formate, dimethylamine acetate, pyridine pyridine, guanidinoacetate, aniline acetate etc Organic acid alkali salts of These can be used alone or in combination of two or more.

  The organic solvent is not particularly limited, but alcohols such as methanol, ethanol, propanol and pentanol; ethers and acetals such as tetrahydrofuran and 1,4-dioxane; aldehydes such as acetaldehyde; acetone, diacetone alcohol and methyl ethyl ketone And ketones; polyhydric alcohol derivatives such as ethylene glycol, propylene glycol and diethylene glycol can be used. These can be used alone or in combination of two or more.

It is preferable that the entire surface of the titanium oxide-like titanium oxide is completely covered with silica. By performing coating in this manner, the effect of suppressing sintering of titanium oxide-like titanium oxide when the reduction treatment is performed is enhanced.
The coated state of titanium oxide like silica gel with silica can be controlled by adjusting the amount of alkoxysilane used. The amount of the alkoxysilane to be used may be appropriately adjusted according to the amount and size of the titanium oxide in the form of gogari, the type of the alkoxysilane, and the like.

In the third step, the method for reducing silica-coated titanium oxide coated in silica is not particularly limited, and firing may be performed in a reducing atmosphere.
The reducing atmosphere is not particularly limited, and examples thereof include a hydrogen atmosphere, a carbon monoxide atmosphere, and a mixed gas atmosphere of hydrogen and an inert gas. Among them, the hydrogen-rich titanium oxide can be efficiently reduced if it is in a hydrogen atmosphere.
The calcination temperature is not particularly limited as long as it is a temperature sufficient to carry out the reduction reaction. The firing temperature is preferably 400 to 1100 ° C., more preferably 500 to 1050 ° C., and still more preferably 600 to 1000 ° C., although it depends on the conditions of the reducing atmosphere (eg, concentration of hydrogen). If the firing temperature is in the above range, titanium oxide can be efficiently reduced to titanium suboxide 1.
The firing time is preferably 5 minutes to 100 hours, more preferably 30 minutes to 20 hours, and still more preferably 1 to 10 hours, depending on the conditions of the firing temperature and the reducing atmosphere.

In the fourth step, the method for removing the silica after the reduction treatment is not particularly limited, but it may be treated with a solution in which the silica is dissolved and the titanium suboxide 1 is not dissolved.
Although it does not specifically limit as a solution used for the removal of a silica, Alkaline solutions, such as aqueous solution of sodium hydroxide, are mentioned. The treatment time with this solution is not particularly limited, and may be appropriately adjusted according to the amount of silica and the like.

  The igagli-like titanium suboxide 1 produced as described above has conductivity, is resistant to corrosion even under high potential, acidic and oxidizing atmospheres, and is excellent in durability, so it is used as a carrier material for electrodes Best for

(Electrode material)
The electrode material of the present disclosure includes a support material for an electrode formed from the above-described iron goblet-like titanium suboxide 1 and a noble metal supported on the support material for an electrode. The electrode material of the present disclosure can be used as an electrode for various fuel cells, and among them, the electrode material of the present disclosure is suitable for use as an electrode for a polymer electrolyte fuel cell. Moreover, although the electrode material of this indication can be used for any of an air electrode (cathode) and a fuel electrode (anode), it is optimal for using it especially for the air electrode in which corrosion resistance is requested | required.

  The type of noble metal is not particularly limited, and those generally used in fuel cell electrodes can be used. Examples of such noble metals include platinum, palladium, ruthenium, rhodium, iridium, osmium, gold, silver and the like. Also, the noble metal is not limited to a single metal, and may be an alloy. The alloy may be an alloy of a noble metal and a metal other than the noble metal. Examples of alloys include platinum-cobalt alloys, platinum-ruthenium alloys, platinum-iridium alloys and the like. The noble metals may be used alone or in combination of two or more. When two or more noble metals are used in combination, the noble metals may be used as an alloy, may be used as a mere mixture, or may be used as a core-shell structure. Among the noble metals, platinum is preferred from the viewpoint of catalytic activity.

The electrode material of the present disclosure can be manufactured by supporting a noble metal on a carrier material for an electrode.
The method of supporting the noble metal is not particularly limited, and any method known in the art can be used. Examples of the method of supporting the noble metal include a thermal reduction method, a sputtering method, a pulsed laser deposition method, a vacuum deposition method, a plasma deposition method and the like. Among them, the plasma deposition method is preferable because fine noble metal particles can be stably supported on the titanium suboxide 1 in the form of sparkly.

  The supported amount of the noble metal (proportion of the noble metal in the electrode carrier material supporting the noble metal) is not particularly limited, but preferably 1 to 70% by mass, more preferably 3 to 50% by mass, and still more preferably 4 to 30% by mass And particularly preferably 5 to 20% by mass. If the loading amount of the precious metal is in the above range, the precious metal is less likely to agglomerate, and therefore, it is possible to suppress the decrease in the catalytic activity.

  Since the electrode material of the present disclosure has the above-described electrode carrier material, it is possible to produce an electrode which is excellent in durability and in which the ORR activity does not easily decrease.

(electrode)
The electrode of the present disclosure has a catalyst layer containing the above electrode material. Therefore, the electrode of the present disclosure is excellent in durability, and the ORR activity is unlikely to be reduced.
In the electrode of the present disclosure, the configuration (base and the like) other than the catalyst layer is not particularly limited, and a known configuration can be adopted.
Moreover, the manufacturing method of the electrode of this indication is not specifically limited except using the said electrode material, According to a well-known method, it can manufacture. For example, a catalyst ink is prepared by adding an electrode material to a solution in which an electrolyte and, if necessary, a binder are dissolved in a solvent, and mixed, and this is applied to an electrolyte membrane or a substrate for an electrode, The electrode can be produced by drying.

The application method of the catalyst ink is not particularly limited, and known methods such as a spray method, a screen printing method, a doctor blade method, a gravure printing method, and a die coating method can be used.
As a method of drying the catalyst ink, known methods such as vacuum drying, heat drying, vacuum heat drying and the like can be used.

(Polymer electrolyte fuel cell)
The polymer electrolyte fuel cell of the present disclosure has the above-described electrode.
The above-mentioned electrode can be used for either an air electrode (cathode) or a fuel electrode (anode), but it is preferable to use it for an air electrode which is required to be particularly resistant to corrosion.
The polymer electrolyte fuel cell of the present disclosure can be used in various applications such as transportation, home, and portable devices. For transportation applications, cars (cars, freight cars, motorcycles, personal beagles), ships, cogeneration systems for household use, vacuum cleaners, robots, mobile phones for mobile devices, laptop computers, electronic still cameras, PDAs, video A camera, a portable game machine, etc. are mentioned. In addition, the polymer electrolyte fuel cell of the present disclosure is a portable generator, an outdoor lighting device, a power source for industrial or household robots or other toys, a secondary battery mounted on these devices, and a capacitor. It can also be used as a power source.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not construed as being limited thereto.

Example 1
<Manufacture of ragari-like titanium suboxide (support material for electrodes)>
An aqueous solution of titanium tetrachloride (TiCl ₄ ) (a titanium (IV) solution manufactured by Wako Pure Chemical Industries, Ltd .; titanium concentration 16 to 17% by mass) is kept at a low temperature using an ice bath, and 2M titanium oxychloride (TiOCl 4) ₂ ) was prepared. Next, 10 mL of 2 M titanium oxychloride was mixed with 1 M hydrochloric acid (HCl) in an ice bath for 30 minutes to dilute to 0.3 M titanium oxychloride. The resulting solution was then transferred to an oil bath and allowed to react at 70 ° C. for 3 hours with stirring. After completion of the reaction, the precipitate was filtered, washed with water and dried to obtain titanium oxide.
Next, 1 g of titanium oxide was added to 10 mL of ethanol (manufactured by Wako Pure Chemical Industries, Ltd .; concentration 99.5 mass%), and then 1.9 mL of TEOS (manufactured by Sigma Aldrich) and 1.5 mL of an ammonia solution ( Wako Pure Chemical Industries, Ltd .; concentration: 28% by mass) was further added. Next, this suspension was stirred at room temperature for 24 hours, then filtered and dried to obtain silica (SiO ₂ ) coated titanium oxide.
Next, 0.2 g of silica-coated titanium oxide was heated at 900 ° C. for 2 hours in a pure hydrogen atmosphere for reduction treatment to obtain silica-coated titanium suboxide.
Next, silica was dissolved and removed by adding silica-coated titanium suboxide to 2 M sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and stirring at 80 ° C. for 24 hours. Thereafter, this solution was filtered, washed with water and vacuum dried to obtain titanium suboxide.

<Evaluation by FE-SEM (field emission scanning electron microscope)>
The FE-SEM image of the titanium suboxide manufactured in Example 1 and the product obtained in the middle of the manufacture was obtained using FE-SEM (made by JEOL Ltd., JSM-7100F). The results are shown in FIG. In FIG. 2, (a) is titanium oxide, (b) is silica-coated titanium oxide, (c) is silica-coated titanium suboxide, (d) is an FE-SEM image of titanium suboxide .
As shown in FIG. 2, it was confirmed that titanium oxide was in the form of gogari, and after the titanium oxide was coated with silica and subjected to reduction treatment, titanium suboxide was also brought into the form of gouguri by removing the silica.

<Evaluation by X-ray diffraction>
The X-ray diffraction pattern of the titanium suboxide produced in Example 1 and the titanium oxide obtained in the process of production was measured using an X-ray diffractometer (Ultima IV, manufactured by Rigaku Corporation). The measurement conditions were as follows.
X-ray source: Cu-Kα ray Measurement range 2θ: 20-80 °
The results are shown in FIG. In FIG. 3, (a) is a titanium oxide and (b) is an X-ray diffraction pattern of titanium suboxide.
As shown in FIG. 3, it was confirmed that titanium oxide was rutile type. Further, it was confirmed that titanium suboxide had a composition containing Ti ₄ O ₇ and Ti ₅ O ₉ .

<Measurement of average particle size>
Ten particles are selected from titanium suboxide produced in Example 1, observed by FE-SEM (Nippon Denshi Co., Ltd., JSM-7100F), the particle diameter is measured, and the average particle diameter is calculated by calculating the average value thereof. I asked for.

<Measurement of BET specific surface area>
The BET specific surface area of the titanium suboxide prepared in Example 1 was measured using BELSCORP-mini manufactured by Microtrac Bell. As a result, the BET specific surface area of titanium suboxide was 32.6 m ² / g.

<Evaluation of projections of titanium suboxide>
The surface of the titanium suboxide produced in Example 1 was observed using a TEM (manufactured by JEOL Ltd., JEM-2100F). From the obtained TEM image, heights and widths of ten protrusions were measured, and their average value was calculated. As a result, the average height was 34.25 nm and the average width was 12.51 nm.

<Manufacture of electrode material>
Platinum was vapor-deposited on the surface of the titanium suboxide in a scaly state obtained in Example 1 under vacuum under the following conditions using an arc plasma method nanoparticle forming apparatus (APD-P, manufactured by Advance Riko Co., Ltd.). The supported amount of platinum was 5% by mass.
Discharge voltage: 150V
Capacity: 1080 μF
Frequency: 3 Hz

(Comparative example 1)
Commercially available platinum-supporting carbon (TEC10E50E, manufactured by Tanaka Kikinzoku Co., Ltd.) was used as an electrode material for comparison. The amount of platinum supported on this platinum-supported carbon is 50% by mass.

<ORR activity evaluation>
A catalyst ink was prepared by adding each of the above electrode materials to a mixed solution of 600 μL of 1-hexanol and 5 μL of Nafion (registered trademark) and dispersing the resultant by ultrasonication. Next, using a glassy carbon rod (φ 5 × 10 mm, density 100%) as a substrate for a working electrode, the dispersion was applied onto the glassy carbon rod and dried overnight at room temperature to produce a working electrode.
Electrochemical measurements were performed using a three-electrode cell. The electrolyte was measured at a temperature of 30 ° C. using 0.1 mol / dm ³ of HClO ₄ . A reversible hydrogen electrode (RHE) was used as a reference electrode, and a glassy carbon plate was used as a counter electrode. As a pretreatment, cyclic voltammetry of 300 cycles was performed at a scanning rate of 150 mV / s and a range of 0.05 to 1.2 V in a nitrogen atmosphere. Thereafter, slow scan voltammetry was performed at a scanning rate of 5 mV / s and in a range of 0.2 to 1.2 V in an oxygen atmosphere and a nitrogen atmosphere, respectively. The ORR current density was calculated by taking the difference between the current density of the oxygen atmosphere and the nitrogen atmosphere.

  Next, according to the Catalyst Durability Evaluation Protocol proposed by the Fuel Cell Commercialization Promotion Council (FCCJ) ("Proposal for R & D tasks and evaluation methods for polymer electrolyte fuel cells", published in January 2011) , Accelerated endurance test. This evaluation method is a method of evaluating the degradation behavior of the electrode material by applying a potential cycle that simulates the start and stop of PEFC. Specifically, as a start-stop simulated potential cycle, the potential is scanned at 50 mV / sec from 1.0 V to 1.5 V, an acceleration test is performed with a triangular wave, and after a predetermined cycle, slow scan voltammetry is performed in the same manner as above. went.

FIG. 4 shows polarization curves (current-potential curves) before the accelerated endurance test and after 5000 start / stop simulated potential cycles.
As shown in FIG. 4, in Example 1, the polarization curve hardly changed before and after the accelerated endurance test, whereas in Comparative Example 1, the polarization curve was shifted to the low voltage side after the accelerated endurance test.

FIG. 5 is a graph showing the relationship between the number of cycles in the accelerated endurance test and the current when the voltage is 0.8V.
As shown in FIG. 5, in Example 1, the current hardly changed even if the number of cycles increased, whereas in Comparative Example 1, the current changed significantly as the number of cycles increased.

<Evaluation by TEM>
The surface of the working electrode of Example 1 and Comparative Example 1 was observed using TEM (manufactured by JEOL Ltd., JEM-2100F). The result of the TEM image is shown in FIG. Here, the working electrode after the accelerated endurance test means the working electrode after 5000 start / stop simulated potential cycles.
As shown in FIG. 6, in the working electrode of Example 1, the supported state of platinum was hardly changed before and after the accelerated durability test, and fine platinum particles were confirmed in all cases. On the other hand, in the working electrode of Comparative Example 1, it was confirmed that the platinum particles became large after the accelerated endurance test. This is considered to be the result of platinum being coarsened due to repeated dissolution and precipitation of platinum and oxidation loss of the support (carbon).
In FIG. 6, the amount of platinum confirmed in Example 1 is smaller than that in Comparative Example 1, but this is due to the difference in the amount of platinum carried.

<Evaluation by ECSA (electrochemical effective area)>
ECSA was determined before the accelerated endurance test and after a predetermined cycle of the accelerated endurance test. The results are shown in FIG.
As shown in FIG. 7, in the working electrode of Example 1, the ECSA of platinum hardly changed even when the cycle number increased, whereas in the working electrode of Comparative Example 1, the cycle number increased. ECSA decreased.

  As can be seen from the above results, according to the present disclosure, it is possible to provide an electrode carrier material capable of producing an electrode excellent in durability and difficult to reduce the ORR activity, a method for producing the same, and an electrode material. Further, according to the present disclosure, it is possible to provide an electrode which is excellent in durability and in which the ORR activity does not easily decrease, and a polymer electrolyte fuel cell having the electrode.

1 titanium suboxide 2 core 3 protrusion

Claims (16)

  A carrier material for an electrode formed from titanium suboxide in the form of a goblet.   2. The electrode carrier material according to claim 1, wherein the greasy titanium suboxide has a core and protrusions protruding radially from the core.   The electrode carrier material according to claim 2, wherein the average height of the protrusions is 5 to 100 nm. The burr-like titanium suboxide is, (wherein, n represents the number of 2~10) Ti _n O _2n-1 having a composition represented by, according to any one of claims 1 to 3 Carrier material for electrodes. The electrode support material according to claim 4, wherein the sparkling-like titanium suboxide is Ti ₄ O ₇ , Ti ₅ O ₉ or a mixture thereof. The carrier material for electrodes according to any one of claims 1 to 5, wherein a BET specific surface area of the titanium suboxide in the form of goblet is 10 m ² / g or more.   The carrier material for electrodes according to any one of claims 1 to 6, wherein an average particle diameter of the titanium carbide in the form of a goblet is 0.1 to 10 μm. Obtaining raguri-like titanium oxide;
Coating the unglazed titanium oxide with silica;
Reducing the silica-coated titanium oxide coated in the form of silica;
And C. removing the silica to obtain a titanium suboxide in the form of a goblet.   The manufacturing method of the support | carrier material for electrodes of Claim 8 in which the said ligagli-like titanium oxide is manufactured by a wet-chemical method.   The method for producing a support material for an electrode according to claim 8 or 9, wherein the silica covers the entire surface of the titanium oxide in the form of gore.   The method for producing a support material for an electrode according to any one of claims 8 to 10, wherein the silica is removed by contacting with an alkaline solution.   The electrode material containing the support material for electrodes as described in any one of Claims 1-7, and the noble metal carry | supported by the support material for electrodes.   The electrode material according to claim 12, wherein the noble metal is platinum.   An electrode comprising a catalyst layer comprising the electrode material of claim 12 or 13.   A polymer electrolyte fuel cell comprising the electrode according to claim 14.   The polymer electrolyte fuel cell according to claim 15, wherein the electrode is used as an air electrode.