Fuel cell catalyst and fuel cell

• US 7,125,822 B2
• Filed: 08/12/2003
• Issued: 10/24/2006
• Est. Priority Date: 08/12/2002
• Status: Expired due to Term

• Current Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Original Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Inventors: Yonetsu, Maki, Onodera, Shinichi, Ohzu, Hideyuki, Nakano, Yoshihiko, Suenaga, Seiichi, Mei, Wu
• Primary Examiner(s): Ryan, Patrick Joseph
• Assistant Examiner(s): Austin, Melissa
• Application Number:
  US10/638,351
• Publication Number:
  US 20040072061A1
• Time in Patent Office: 1,169 Days
• Field of Search: 429/231.8, 429/44, 502/180, 502/185, 502/202, 502/207, 502/208, 502/213, 502/305, 502/313, 502/321, 502/324, 502/325, 502/326, 502/334, 502/339, 502/349, 502/350, 502/353, 502/355, 502/439, 420/466
• US Class Current: 502/339
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 23/40 of the platinum group metals
• CPC Class Codes: B01J 23/89 combined with noble metals
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 35/393 Metal or metal oxide crystallite size
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/612 less than 10 m2/g
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: H01M 4/8605 Porous electrodes
• CPC Class Codes: H01M 4/921 Alloys or mixtures with metallic elements
• CPC Class Codes: H01M 4/926 on carbon or graphite
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

This invention provides a fuel cell catalyst including a carbon support containing at least one first element selected from the group consisting of B, N, and P, and catalyst particles supported on the carbon support, wherein the catalyst particles include at least one of platinum particles and alloy particles containing Pt and an element A, and the element A contains at least one element selected from the group consisting of platinum group elements and period 4 to 6 transition metal elements.

Claims

1. A fuel cell catalyst comprising:

a carbon support in which a carbon atom is substituted with a first element consisting of N and/or P; and

catalyst particles supported on the carbon support,

wherein the catalyst particles include at least one of platinum particles and alloy particles containing Pt and an element A, and the element A contains at least one element selected from the group consisting of platinum group elements, period 4 to 6 transition metal elements, and Sn.

2. A catalyst according to claim 1, wherein a content of said at least one first element in the carbon support is 0.1 wt % to 20 wt %.

3. A catalyst according to claim 1, wherein the element A is at least one element selected from the group consisting of Ru, Ir, Os, W, V, Mo, Sn, and Re.

4. A catalyst according to claim 1, wherein an average particle size of the catalyst particles is 1 nm to 100 nm.

5. A catalyst according to claim 1, wherein the catalyst particles are the alloy particles, the element A is at least one element selected from the group consisting of Ru, Ir, Os, W, V, Mo, Sn, Re, Pd, and Rh, the alloy particle satisfies

Y₁>

Y₂ 

 

(1)

where Y₁ is the number of Pt atoms when the number of atoms of the element A on a surface of the alloy particle is 1, Y₁ is larger than 1, and Y₂ is the number of Pt atoms when the number of atoms of the element A in an interior of the alloy particle is 1.

6. A catalyst according to claim 1, wherein the catalyst particles are the alloy particles, the element A is at least element selected from the group consisting of Ru, Ir, Os, W, V, Mo, Sn, Re, Pd, and Rh, the alloy particle satisfies

Y₁>

Y₃ 

 

(2)

where Y₁ is the number of Pt atoms when the number of atoms of the element A on a surface of the alloy particle is 1, Y₁ is larger than 1, and Y₃ is the total number of Pt atoms when the total number of atoms of the element A of the alloy particle is 1.

7. A fuel cell catalyst, comprising:

a carbon support containing at least one element selected from the group consisting of B, N, and P; and

alloy particles supported on the carbon support and containing an element A and Pt and,

wherein the element A is at least one element selected from the group consisting of W, V, Mo, and Sn

wherein the alloy particle satisfies

Y₁Y₃ 

 

(2)

where Y₁ is the number of Pt atoms when the number of atoms of the element A on a surface of the alloy particle is 1, Y₁ is larger than 1, and Y₃ is the total number of Pt atoms when the total number of atoms of the element A of the alloy particle is 1.

19. A catalyst according to claim 7, wherein the alloy particles comprise core particles formed of the element A and a Pt layer formed on surfaces of the core particles.

8. A fuel cell catalyst comprising:

composite material including

a support containing at least one of an oxide represented by formula (3) below and a composite oxide represented by formula (4) below;

M_xO_y 

 

(3)

M_xO_y-M′

_aO_b 

 

(4)

wherein elements M and M′

can be the same or different, and each of the elements M and M′

is at least one element selected from the group consisting of Si, Ti, Al, Zr, Ge, Re, V, Mn, W, Mo, and Sn;

catalyst particles supported on the support and having an average particle size of 1/10 or less of an average particles size of the support; and

a carbon material extending from the catalyst particles and formed of at least one of carbon fiber and carbon tube, a length of carbon fiber and the carbon tube is equal to or larger than the average particle size of the catalyst particles.

9. A catalyst according to claim 8, wherein an average diameter of each of the carbon fiber and carbon tube is 1 nm to 5,000 nm.

10. A catalyst according to claim 8, wherein the oxide is at least one oxide selected from the group consisting of SiO₂, Al₂O₃, WO₃, MoO₃, SnO₂, TiO₂, ZrO₂, and SnO₂, and the composite oxide is at least one composite oxide selected from the group consisting of SiO₂—

Al₂O₃, SiO₂—

B₂O₃, SiO₂—

WO₃, SiO₂—

P₂O₅, SiO₂—

MoO₃, SiO₂—

RuO₂, SiO₂—

Ir₂O₃, SiO₂—

PtO₂, SiO₂—

Rh₂O₃, SiO₂—

PdO, SiO₂—

ZrO₂, SiO₂—

TiO₂, SiO₂—

Hf₂O₃, SiO₂—

SnO₂, SiO₂—

Al₂O₃—

P₂O₅, SiO₂—

TiO₂—

P₂—

O₅, and SiO₂—

WO₃—

P₂O₅.

11. A catalyst according to claim 8, wherein the catalyst particles include at least one of platinum particles and alloy particles containing Pt and an element A, and the element A is at least one element selected from the group consisting of platinum group elements and period 4 to 6 transition metal elements.

12. A catalyst according to claim 8, wherein the average particle size of the support is 1 μ

m or less, and the carbon fiber and the carbon tube have an average diameter of 1 nm to 5,000 nm.

13. A catalyst according to claim 8, wherein the fuel cell catalyst is an anode catalyst.

14. A fuel cell comprising:

a cathode electrode,

an anode electrode, and

an electrolyte layer provided between the cathode electrode and anode electrode,

wherein at least one of the cathode electrode and anode electrode comprises;

composite material including;

a support containing at least one of an oxide represented by formula (3) below and a composite oxide represented by formula (4) below;

M_xO_y 

 

(3)

M_xO_y-M′

_aO_b 

 

(4)

wherein elements M and M′

can be the same or different, and each of the elements M and M′

is at least one element selected from the group consisting of Si, Ti, Al, Zr, Ge, Re, V, Mn, W, Mo, and Sn;

catalyst particles supported on the support and having an average particle size of 1/10 or less of an average particle size of the support; and

a carbon material extending from the catalyst particles and formed of at least one of carbon fiber and carbon tube, a length of the carbon fiber and the carbon tube is equal to or larger than the average particle size of the catalyst particles.

15. A fuel cell catalyst comprising:

composite material including

a support containing at least one of an oxide represented by formula (3) below and a composite oxide represented by formula (4) below;

M_xO_y 

 

(3)

M_xO_y-M′

_aO_b 

 

(4)

wherein elements M and M′

can be the same or different, and each of the elements M and M′

is at least one element selected from the group consisting of Si, Ti, Al, Zr, Ge, Re, V, Mn, W, Mo, and Sn;

a carbon material supported on the support and formed of at least one of carbon fiber and carbon tube having a diameter smaller than that of the support; and

catalyst particles formed on the carbon material,

wherein an average particle size of the catalyst particles is 1/10 or less of an average particle size of the support, and a length of the carbon fiber and the carbon tube is equal to or larger than the average particle size of the catalyst particles.

16. A catalyst according to claim 15, wherein the average particle size of the support is 1 μ

m or less, and the carbon fiber and the carbon tube have an average diameter of 1 nm to 5,000 nm.

17. A catalyst according to claim 15, wherein the fuel cell catalyst is a cathode catalyst.

18. A fuel cell comprising composite material which comprises

a cathode electrode,

an anode electrode, and

an electrolyte layer provided between the cathode electrode and anode electrode,

wherein at least one of the cathode electrode and anode electrode comprises:

a support containing at least one of an oxide represented by formula (3) below and a composite oxide represented by formula (4) below;

M_xO_y 

 

(3)

M_xO_y-M′

_aO_b 

 

(4)

wherein elements M and M′

can be the same or different, and each of the elements M and M′

is at least one element selected from the group consisting of Si, Ti, Al, Zr, Ge, Re, V, Mn, W, Mo, and Sn,

a carbon material supported on the support and formed of carbon fiber and/or carbon tube having a diameter smaller than that of the support; and

catalyst particles formed on the carbon material,

wherein an average particles size of the catalyst particles is 1/10 or less an average particle size of the support, and a length of the carbon fiber and the carbon tube is equal to or larger than the average particle size of the catalyst particles.