Carbon support material for solid polymer type fuel cell use and metal catalyst particle- supporting carbon material and methods of production of same

Patent metadata

Field	Value
Publication number	US-10003085-B2
Application number	US-201415103649-A
Country	US
Kind code	B2
Filing date	Dec 12, 2014
Priority date	Dec 13, 2013
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

Provided are a supporting carbon material for a solid polymer fuel cell and a metal-catalyst-particle-supporting carbon material that, when used as a carrier for a solid polymer fuel cell catalyst, have excellent power generation performance in high-humidity conditions, which are conditions in which solid polymer fuel cells are operated. A supporting carbon material for a solid polymer fuel cell and a metal-catalyst-particle-supporting carbon material characterized in being a porous carbon material, the hydrogen content being 0.004-0.010% by mass, the nitrogen adsorption BET specific surface area being 600 m 2 /g-1500 m 2 /g, and the relative intensity ratio (I D /I G ) between the peak intensity (I D ) in the range of 1200-1400 cm −1 known as the D-band and the peak intensity (I G ) in the range of 1500-1700 cm −1 known as the G-band, obtained from the Raman spectrum, being 1.0-2.0.

First claim

The invention claimed is:

1. A solid polymer type fuel cell-use carbon support material comprised of a porous carbon material with a hydrogen content of 0.004 mass % to 0.010 mass % in range, a nitrogen adsorption BET specific surface area of 600 m 2 /g to 1500 m 2 /g, and a relative intensity ratio (I D /I G ) of a peak intensity (I D ) of the range of 1200 to 1400 cm −1 called the “D-band” and a peak intensity (I G ) of the range of 1500 to 1700 cm −1 called the “G-band” of 1.0 to 2.0, wherein the peak intensities (I D ) and (I G ) are obtained from the Raman spectrum.

2. The solid polymer type fuel cell-use carbon support material according to claim 1 , wherein said hydrogen content is 0.004 mass % to 0.006 mass % and a relative intensity ratio (I D /I G ) found from the Raman spectrum is 1.4 to 2.0.

3. The solid polymer type fuel cell-use carbon support material according to claim 1 wherein said nitrogen adsorption BET specific surface area is 800 m 2 /g to 1400 m 2 /g and a relative intensity ratio (I D /I G ) found from the Raman spectrum is 1.4 to 2.0.

4. The solid polymer type fuel cell-use carbon support material according to claim 1 wherein said hydrogen content is 0.004 mass % to 0.006 mass %, said nitrogen adsorption BET specific surface area is 800 m 2 /g to 1400 m 2 /g, and the relative intensity ratio (I D /I G ) found from the Raman spectrum is 1.4 to 2.0.

5. A solid polymer type fuel cell-use metal catalyst particle-supporting carbon material comprised of the solid polymer type fuel cell-use carbon support material according to claim 1 on which metal catalyst particles of Pt alone or mainly Pt are supported.

6. A method of production of a solid polymer type fuel cell-use carbon support material according to claim 1 , said method of production of a solid polymer type fuel cell-use carbon support material comprising:
an acetylide forming step of blowing acetylene gas into a solution containing a metal or metal salt and forming a metal acetylide,
a first heat treatment step of heating said metal acetylide at 60° C. to 80° C. in temperature and preparing a metal particle-containing intermediate in which metal particles are contained,
a second heat treatment step of heating said metal particle-containing intermediate at 160° C. to 200° C. in temperature, causing metal particles to be ejected from said metal particle-containing intermediate, and obtaining a carbon material intermediate,
a washing treatment step of bringing the carbon material intermediate obtained at said second heat treatment step into contact with hot concentrated sulfuric acid and cleaning the carbon material intermediate, and
a third heat treatment step of heating the carbon material intermediate cleaned at said washing treatment step in a vacuum, in an inert gas atmosphere, or in an air atmosphere to 1000° C. to 2100° C. in temperature to obtain a carbon support material.

7. A method of production of a solid polymer type fuel cell-use metal catalyst particle-supporting carbon material comprising causing a carbon support material comprised of a porous carbon material with a hydrogen content of 0.004 mass % to 0.010 mass % in range, a nitrogen adsorption BET specific surface area of 600 m 2 /g to 1500 m 2 /g, and a relative intensity ratio (I D /I G ) of a peak intensity (I D ) of the range of 1200 to 1400 cm −1 called the “D-band” and a peak intensity (I G ) of the range of 1500 to 1700 cm −1 called the “G-band” of 1.0 to 2.0, wherein the peak intensities (I D ) and (I G ) are obtained from the Raman spectrum obtained by the method according to said claim 6 to be dispersed into a liquid dispersion medium, adding to the obtained dispersion a complex or salt of a metal mainly comprised of platinum and a reducing agent, reducing the metal ions in a liquid phase to cause the precipitation of fine metal catalyst particles mainly comprised of platinum, and supporting the precipitated metal catalyst particles on said carbon support material to thereby produce a solid polymer type fuel cell-use metal catalyst particle-supporting carbon material on which metal catalyst particles of Pt alone or mainly Pt are supported.

8. A solid polymer type fuel cell-use metal catalyst particle-supporting carbon material comprised of the solid polymer type fuel cell-use carbon support material according to claim 2 on which metal catalyst particles of Pt alone or mainly Pt are supported.

9. A solid polymer type fuel cell-use metal catalyst particle-supporting carbon material comprised of the solid polymer type fuel cell-use carbon support material according to claim 3 on which metal catalyst particles of Pt alone or mainly Pt are supported.

10. A solid polymer type fuel cell-use metal catalyst particle-supporting carbon material comprised of the solid polymer type fuel cell-use carbon support material according to claim 4 on which metal catalyst particles of Pt alone or mainly Pt are supported.

11. A method of production of a solid polymer type fuel cell-use carbon support material according to claim 2 , said method of production of a solid polymer type fuel cell-use carbon support material comprising:
an acetylide forming step of blowing acetylene gas into a solution containing a metal or metal salt and forming a metal acetylide,
a first heat treatment step of heating said metal acetylide at 60° C. to 80° C. in temperature and preparing a metal particle-containing intermediate in which metal particles are contained,
a second heat treatment step of heating said metal particle-containing intermediate at 160° C. to 200° C. in temperature, causing metal particles to be ejected from said metal particle-containing intermediate, and obtaining a carbon material intermediate,
a washing treatment step of bringing the carbon material intermediate obtained at said second heat treatment step into contact with hot concentrated sulfuric acid and cleaning the carbon material intermediate, and
a third heat treatment step of heating the carbon material intermediate cleaned at said washing treatment step in a vacuum, in an inert gas atmosphere, or in an air atmosphere to 1000° C. to 2100° C. in temperature to obtain a carbon support material.

12. A method of production of a solid polymer type fuel cell-use carbon support material according to claim 3 , said method of production of a solid polymer type fuel cell-use carbon support material comprising:
an acetylide forming step of blowing acetylene gas into a solution containing a metal or metal salt and forming a metal acetylide,
a first heat treatment step of heating said metal acetylide at 60° C. to 80° C. in temperature and preparing a metal particle-containing intermediate in which metal particles are contained,
a second heat treatment step of heating said metal particle-containing intermediate at 160° C. to 200° C. in temperature, causing metal particles to be ejected from said metal particle-containing intermediate, and obtaining a carbon material intermediate,
a washing treatment step of bringing the carbon material intermediate obtained at said second heat treatment step into contact with hot concentrated sulfuric acid and cleaning the carbon material intermediate, and
a third heat treatment step of heating the carbon material intermediate cleaned at said washing treatment step in a vacuum, in an inert gas atmosphere, or in an air atmosphere to 1000° C. to 2100° C. in temperature to obtain a carbon support material.

13. A method of production of a solid polymer type fuel cell-use carbon support material according to claim 4 , said method of production of a solid polymer type fuel cell-use carbon support material comprising:
an acetylide forming s

Assignees

• Nippon Steel & Sumitomo Metal Corp
• Nippon Steel & Sumikin Chem Co

Inventors

• Matsumoto Katsumasa
• Iijima Takashi
• Hiyoshi Masataka
• Hayashida Hiroyuki
• Mizuuchi Kazuhiko
• Kouno Takumi
• Higuchi Masakazu
• Katayama Masakazu

Classifications

• B01J31/28

  of the platinum group metals, iron group metals or copper · CPC title

• H01M4/8605

  Porous electrodes · CPC title

• H01M2008/1095

  Fuel cells with polymeric electrolytes · CPC title

• H01M4/926 Primary

  on carbon or graphite · CPC title

• H01M4/9083

  on carbon or graphite · CPC title