Method for producing catalyst for fuel cells, and fuel cell containing catalyst for fuel cells produced by the production method
View Patent ↗The present invention is to provide a method for producing a catalyst for fuel cells with excellent durability, and a fuel cell comprising a catalyst for fuel cells produced by the production method. Disclosed is a method for producing a catalyst for fuel cells, the catalyst comprising fine catalyst particles, each of which comprises a palladium-containing core particle and a platinum-containing outermost layer covering the core particle, and carbon supports on which the fine catalyst particles are supported, wherein the method comprises the steps of: preparing carbon supports on which palladium-containing particles are supported; fining the carbon supports; and covering the palladium-containing particles with a platinum-containing outermost layer after the fining step.
1. A method for producing a catalyst layer for fuel cells, the catalyst layer comprising fine catalyst particles, each of which comprises a palladium-containing core particle, a carbon support on which the palladium-containing core particle is supported, and a platinum-containing outermost layer covering the palladium-containing core particle, wherein the method comprises the ordered steps of:
preparing the carbon supports on which the palladium-containing core particles are supported;
applying a solvent to the carbon supports on which the palladium-containing core particles are supported;
freeze-drying the carbon supports on which the palladium-containing core particles are supported after the applying step;
fining, by intermittently operating a homogenizer in two second cycles, the carbon supports on which the palladium-containing core particles are supported after the freeze-drying step by stirring the carbon supports on which the palladium-containing core particles are supported until the total operation time reaches 45 minutes with cooling the carbon supports by cooling water; and
covering the fined palladium-containing particles, supported on the fined carbon supports, with the platinum-containing outermost layer after the fining step,
wherein, after the fining step, the particle size distribution of the carbon supports is an approximately normal distribution.
2. The catalyst layer production method according to claim 1 , wherein, after the fining step, a mean volume diameter of the carbon supports is 1 to 20 μm.
3. The catalyst layer production method according to claim 1 , wherein, after the fining step, a standard deviation a in the particle size distribution of the carbon supports is 1 to 5 μm.
4. The catalyst layer production method according to claim 1 , wherein, after the fining step, a 90% diameter x 90 in the cumulative distribution on a volumetric basis of the carbon supports is 10 to 30 μm.
5. The catalyst layer production method according to claim 1 , wherein, after the fining step, a mean number diameter of the carbon supports is 1 to 10 μm.
6. The catalyst layer production method according to claim 1 , wherein, after the fining step, an mean area diameter of the carbon supports is 1 to 10 m.
7. The catalyst layer production method according to claim 1 , wherein the outermost layer covering step comprises at least the steps of:
covering the palladium-containing particles with a monatomic layer, and
replacing the monatomic layer with the platinum-containing outermost layer.
8. A fuel cell comprising a unit cell that contains a membrane electrode assembly comprising a polyelectrolyte membrane, an anode electrode on one surface of the membrane, the anode electrode containing at least an anode catalyst layer, and a cathode electrode on the other surface of the membrane, the cathode electrode containing at least a cathode catalyst layer,
wherein at least one of the anode and cathode catalyst layers is the catalyst layer for fuel cells produced by the production method defined by claim 1 .
9. The catalyst layer production method according to claim 1 , wherein, after the outermost layer covering step, a catalytic ink is dispersed by a milder condition than a condition of fining the carbon supports in the fining step.
10. A method for producing an electrode for fuel cells,
wherein the electrode comprises the catalyst layer for fuel cells produced by the production method defined by claim 1 .
11. The method of claim 1 , further comprising a pretreatment step of applying a potential to the palladium-containing core particles after the fining step, wherein the potential applied in the pretreatment step is less than a standard electrode potential of the palladium.
12. The catalyst production method according to claim 1 , wherein, after the fining step, a median diameter x 50 in the cumulative distribution on a volumetric basis of the carbon supports is 1 to 20 μm.
13. The catalyst production method according to claim 1 , wherein, in the preparation step, the median diameter x 50 in the cumulative distribution on a volumetric basis of the carbon supports is more than 20 μm.
14. The catalyst production method according to claim 1 , wherein the method further comprises a step of washing the fined carbon supports on which the palladium-containing core particles are supported after the fining step.
15. The catalyst production method according to claim 14 , wherein the method further comprises a step of drying the fined carbon supports on which the palladium-containing core particles are supported after the washing step.
16. The catalyst production method according to claim 14 , wherein the method further comprises a step of removing oxides from surface of the palladium-containing core particles after the washing step.
17. A method for producing a catalyst layer for fuel cells, the catalyst layer comprising fine catalyst particles, each of which comprises a palladium-containing core particle, a carbon support on which the palladium-containing core particle is supported, and a platinum-containing outermost layer covering the palladium-containing core particle, wherein the method comprises the ordered steps of:
preparing the carbon supports on which the palladium-containing core particles are supported;
applying a solvent to the carbon supports on which the palladium-containing core particles are supported;
freeze-drying the carbon supports on which the palladium-containing core particles are supported after the applying step;
fining, by intermittently operating a homogenizer in two second cycles, the carbon supports on which the palladium-containing core particles are supported after the freeze-drying step by stirring the carbon supports on which the palladium-containing core particles are supported until the total operation time reaches 15 minutes with cooling the carbon supports by cooling water at about 6° Celsius; and
covering the fined palladium-containing particles, supported on the fined carbon supports, with the platinum-containing outermost layer after the fining step,
wherein, after the fining step, the particle size distribution of the carbon supports is an approximately normal distribution and a peak of the particle size distribution is about 10 μm.