Non-PGM cathode catalysts for fuel cell application derived from heat treated heteroatomic amines precursors

Patent metadata

Field	Value
Publication number	US-9634331-B2
Application number	US-201214126788-A
Country	US
Kind code	B2
Filing date	Jun 15, 2012
Priority date	Jun 15, 2011
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

A method of preparing M-N—C catalysts utilizing a sacrificial support approach and inexpensive and readily available polymer precursors as the source of nitrogen and carbon is disclosed. Exemplary polymer precursors include non-porphyrin precursors with no initial catalytic activity. Examples of suitable non-catalytic non-porphyrin precursors include, but are not necessarily limited to low molecular weight precursors that form complexes with iron such as 4-aminoantipirine, phenylenediamine, hydroxysuccinimide, ethanolamine, and the like.

First claim

What is claimed is:

1. A method for producing an electrocatalytic material suitable for use in a fuel cell comprising:
providing at least two populations of sacrificial template particles wherein each population has an average particle diameter that is different from the other populations;
precipitating one or more transition metal precursors and a non-porphyrin precursor with no initial catalytic activity onto the sacrificial template particles to produce dispersed precursors;
pyrolyzing the dispersed precursors; and
removing the sacrificial template particles to produce a dispersed, self-supported, electrocatalytic material having a multimodal pore distribution.

2. The method of claim 1 wherein the non-porphyrin precursor forms a complex with iron.

3. The method of claim 1 wherein the non-porphyrin precursor is 4-aminoantipirine.

4. The method of claim 1 wherein the transition metal precursor is an iron precursor.

5. The method of claim 1 wherein the one or more transitional metal precursors is selected from the group consisting of precusors of Ce, Cr, Cu, Mo, Ni, Ru, Ta, Ti, V, W, and Zr.

6. The method of claim 1 wherein at least two different metal precursors are used resulting in a multi-metallic catalyst.

7. The method of claim 1 wherein the wherein the sacrificial template particles and non-porphyrin precursors are selected for use so as to shift the reaction mechanism of the electrocatalytic material towards the 4 e-pathway.

8. The method of claim 1 wherein the electrocatalytic material contains a population of pores having an average diameter between 20 and 60 nm and a second population of pores having an average diameter between 100 and 200 nm.

9. The method of claim 8 wherein the sacrificial template particles are formed from silica.

10. The method of claim 9 wherein each population of silica particles is formed from a different type of silica.

11. The method of claim 1 further comprising
mixing the transition metal and non-porphyrin precursors with the sacrificial template particles;
atomizing the mixture to form a powder;
collecting the powder; and
heat treating the powder.

12. A dispersed, unsupported, catalytic material substantially consisting of nitrogen and carbon from a non-porphyrin precursor with no initial catalytic activity and at least one transition metal from pyrolyzed metal precursors manufactured using the method of claim 1 .

13. A dispersed, unsupported, catalytic material substantially consisting of nitrogen and carbon from a non-porphyrin precursor with no initial catalytic activity and at least one transition metal from pyrolyzed metal precursors wherein the material comprises a first population of pores having an average diameter between 20 and 60 nm and a second population of pores having an average diameter between 100 and 200 nm.

14. The material of claim 13 further comprising a tri-modal pore distribution wherein the material comprises a first population of pores having an average diameter of less than or approximately equal to 20 nm, a second population of pores having an average diameter of between approximately 40 and 60 nm, and a third population of pores having an average diameter between 150 and 200 nm.

15. The material of claim 13 comprising multiple transition metals.

16. A method for producing an electrocatalytic material suitable for use in a fuel cell comprising:
providing sacrificial template particles;
precipitating one or more transition metal precursors and 4-aminoantipirine onto the sacrificial template particles to produce dispersed precursors;
pyrolyzing the dispersed precursors; and
removing the sacrificial template particles to produce a dispersed, self-supported, electrocatalytic material.

Assignees

• Serov Alexey
• Halevi Barr
• Artyushkova Kateryna
• Atanassov Plamen B
• Martinez Ulises A
• Stc Unm

Inventors

• Serov Alexey
• Halevi Barr
• Artyushkova Kateryna
• Atanassov Plamen B
• Martinez Ulises A

Classifications

• Y02E60/50

  Fuel cells · CPC title

• H01M4/9091

  Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state · CPC title

• H01M4/8885

  Sintering or firing · CPC title

• H01M4/8652 Primary

  as mixture · CPC title

• H01M4/9041

  Metals or alloys (H01M4/92 takes precedence) · CPC title