Carbon material for catalyst carrier of polymer electrolyte fuel cell and method of producing the same

Patent metadata

Field	Value
Publication number	US-12057589-B2
Application number	US-201817280134-A
Country	US
Kind code	B2
Filing date	Sep 28, 2018
Priority date	Sep 28, 2018
Publication date	Aug 6, 2024
Grant date	Aug 6, 2024

Abstract

Provided are a carbon material for a catalyst carrier of a polymer electrolyte fuel cell, the carbon material being a porous carbon material and simultaneously satisfying (1) an intensity ratio (I 750 /I peak ) of an intensity at 750° C. (I 750 ) and a peak intensity in a vicinity of 690° C. (I peak ) is 0.10 or less; (2) a BET specific surface area is from 400 to 1,500 m 2 /g; (3) an integrated pore volume V 2-10 of a pore diameter of from 2 to 10 nm is from 0.4 to 1.5 mL/g; and (4) a nitrogen gas adsorption amount V macro at a relative pressure of from 0.95 to 0.99 in the nitrogen gas adsorption isotherm is from 300 to 1,200 cc(STP)/g, as well as a method of producing the same.

First claim

What is claimed is:

1. A carbon material for a catalyst carrier of a polymer electrolyte fuel cell, the carbon material being a porous carbon material and simultaneously satisfying (1), (2), (3) and (4) below:
(1) an intensity ratio (I 750 /I peak ) of an intensity at 750° C. (I 750 ) and a peak intensity in a vicinity of 690° C. (I peak ), in a derivative thermogravimetric curve (DTG) obtained by a thermogravimetric analysis when a temperature is raised at a rate of 10° C./min under an air atmosphere, is 0.10 or less;
(2) a BET specific surface area, determined by BET analysis of a nitrogen gas adsorption isotherm, is from 400 to 1,500 m 2 /g;
(3) an integrated pore volume V 2-10 of a pore diameter of from 2 to 10 nm, determined by analysis of the nitrogen gas adsorption isotherm using Dollimore-Heal method, is from 0.4 to 1.5 mL/g; and
(4) a nitrogen gas adsorption amount V macro at a relative pressure of from 0.95 to 0.99 in the nitrogen gas adsorption isotherm is from 300 to 1,200 cc(STP)/g.

2. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1 , wherein a residual weight ratio of a graphitized product at 750° C. in the thermogravimetric analysis when the temperature is raised at a rate of 10° C./min under an air atmosphere is 3% or less.

3. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1 , wherein a half width ΔG of a G-band detected in a range of from 1,550 to 1,650 cm −1 in a Raman spectroscopic spectrum is from 50 to 70 cm −1 .

4. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1 , wherein the V 2-10 is from 0.5 to 1.0 mL/g.

5. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1 , comprising a three-dimensional dendritic structure in which a rod-shaped body or an annular body is three-dimensionally branched.

6. A method of producing a carbon material for a catalyst carrier of a polymer electrolyte fuel cell, the method comprising:
a silver acetylide production step of blowing an acetylene gas into a reaction solution consisting of an aqueous ammonia solution of silver nitrate, to synthesize a silver acetylide;
a decomposition step of allowing an autolysis explosive reaction of the silver acetylide, to obtain a carbon material intermediate;
a silver removal step of bringing the carbon material intermediate into contact with a dilute nitric acid, to remove silver from the carbon material intermediate;
a cleaning treatment step of bringing the carbon material intermediate, from which silver has been removed, into contact with an oxidizing agent solution, to clean the carbon material intermediate; and
a heat treatment step of heat-treating the cleaned carbon material intermediate at a temperature of from 1,400 to 2,200° C. in a vacuum or in an inert gas atmosphere, to obtain a carbon material for a catalyst carrier,
wherein at least one selected from the group consisting of a permanganate solution and a hydrogen peroxide solution is used as the oxidizing agent solution.

7. The method according to claim 6 , wherein the carbon material is a porous carbon material.

8. The method according to claim 7 , wherein the carbon material simultaneously satisfies (1), (2), (3) and (4) below:
(1) an intensity ratio (I 750 /I peak ) of an intensity at 750° C. (I 750 ) and a peak intensity in a vicinity of 690° C. (I peak ), in a derivative thermogravimetric curve (DTG) obtained by a thermogravimetric analysis when a temperature is raised at a rate of 10° C./min under an air atmosphere, is 0.10 or less;
(2) a BET specific surface area, determined by BET analysis of a nitrogen gas adsorption isotherm, is from 400 to 1,500 m 2 /g;
(3) an integrated pore volume V 2-10 of a pore diameter of from 2 to 10 nm, determined by analysis of the nitrogen gas adsorption isotherm using Dollimore-Heal method, is from 0.4 to 1.5 mL/g; and
(4) a nitrogen gas adsorption amount V macro at a relative pressure of from 0.95 to 0.99 in the nitrogen gas adsorption isotherm is from 300 to 1,200 cc(STP)/g.

9. The method accordingly to claim 8 , wherein a residual weight ratio of a graphitized product at 750° C. in the thermogravimetric analysis when the temperature is raised at a rate of 10° C./min under an air atmosphere is 3% or less.

10. The method accordingly to claim 8 , wherein a half width ΔG of a G-band detected in a range of from 1,550 to 1,650 cm −1 in a Raman spectroscopic spectrum is from 50 to 70 cm −1 .

11. The method accordingly to claim 8 , wherein the V 2-10 is from 0.5 to 1.0 mL/g.

12. The method accordingly to claim 8 , further comprising a three-dimensional dendritic structure in which a rod-shaped body or an annular body is three-dimensionally branched.

13. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1 , wherein the BET specific surface area, determined by BET analysis of a nitrogen gas adsorption isotherm, is from 500 to 1,400 m 2 /g.

14. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1 , the intensity ratio is 0.09 or less.

15. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1 , wherein the nitrogen gas adsorption isotherm is from 300 to 800 cc(STP)/g.

16. The carbon material for a catalyst carrier of a polymer electrolyte fuel cell according to claim 1 , wherein the residual weight ratio of the graphitized product at 750° C. in the thermogravimetric analysis when the temperature is raised at a rate of 10° C./min under an air atmosphere is 2% or less.

17. The method accordingly to claim 8 , wherein the BET specific surface area, determined by BET analysis of a nitrogen gas adsorption isotherm, is from 500 to 1,400 m 2 /g.

18. The method accordingly to claim 8 , wherein the intensity ratio is 0.09 or less.

19. The method accordingly to claim 8 , wherein the nitrogen gas adsorption isotherm is from 300 to 800 cc(STP)/g.

20. The method accordingly to claim 8 , wherein the residual weight ratio of the graphitized product at 750° C. in the thermogravimetric analysis when the temperature is raised at a rate of 10° C./min under an air atmosphere is 2% or less.

Assignees

• Nippon Steel Chemical & Mat Co Ltd

Inventors

• Iijima Takashi
• Tadokoro Kenichiro
• Hiyoshi Masataka
• Furukawa Shinya
• Komura Tomoko
• Masaki Kazuyoshi
• Hayashida Hiroyuki
• Tada wakana

Classifications

• H01M2008/1095

  Fuel cells with polymeric electrolytes · CPC title

• C01P2006/40

  Electric properties · CPC title

• C01P2006/16

  Pore diameter · CPC title

• C01P2006/14

  Pore volume · CPC title

• C01P2006/12

  Surface area · CPC title