Composite proton conducting electrolyte with improved additives for fuel cells

Patent metadata

Field	Value
Publication number	US-9391337-B2
Application number	US-201514855789-A
Country	US
Kind code	B2
Filing date	Sep 16, 2015
Priority date	Nov 10, 2009
Publication date	Jul 12, 2016
Grant date	Jul 12, 2016

Abstract

Additives can be used to prepare polymer electrolyte for membrane electrode assemblies in polymer electrolyte fuel cells in order to improve both durability and performance. The additives are chemical complexes comprising certain metal and organic ligand components.

First claim

The invention claimed is:

1. A membrane electrode assembly for a solid polymer electrolyte fuel cell comprising
an anode catalyst layer,
a membrane electrolyte,
a cathode catalyst layer, and
a proton conducting composite polymer electrolyte comprising a proton conducting ionomer and an amount of a metal-ligand complex additive wherein:
the metal in the complex is selected from the group consisting of metals, metal alloys, metal oxides, metal salts and combinations thereof; and
the ligand in the complex comprises a molecule or polymer thereof wherein the chemical structure of the molecule is selected from the group consisting of:

wherein R 1 , R 3 and R 4 are selected from the group consisting of H, CH 3 (CH 2 ) n , CH 3 (CH 2 ) n O, CF 3 (CF 2 ) n , CF 3 (CF 2 ) n O, COOH, PO(OH) 2 , SO 3 H, NH 2 , OH, and

wherein X is H, COOH, PO(OH) 2 or SO 3 H and n is an integer from
0 to 10; and wherein R 2 is selected from the group consisting of CH 3 (CH 2 ) n , CH 3 (CH 2 ) n O, CF 3 (CF 2 ) n , CF 3 (CF 2 ) n O, COOH, PO(OH) 2 , SO 3 H, NH 2 , OH, and

wherein X is H, COOH, PO(OH) 2 or SO 3 H and n is an integer from 0 to 10.

2. The membrane electrode assembly of claim 1 wherein the metal in the complex comprises Mn, Ce, Co, Fe, Cu, Pd, Pt, Pt supported on carbon, Pt—Co, or an ion thereof.

3. The membrane electrode assembly of claim 1 wherein R 1 is an amino or phenyl group.

4. The membrane electrode assembly of claim 1 wherein R 2 is an amino or phenyl group.

5. The membrane electrode assembly of claim 1 wherein the ligand is bathophenanthroline, 1,10-phenanthroline-5-amino, or terpyridine.

6. The membrane electrode assembly of claim 5 wherein the metal is Ce, Mn, Pt, or Pt supported on carbon.

7. The membrane electrode assembly of claim 1 wherein the molar ratio of metal to ligand in the complex is from about 1:1 to 1:5.

8. The membrane electrode assembly of claim 1 wherein the amount of the metal-ligand complex additive in the composite polymer electrolyte is greater than or about 0.5% by weight of the proton conducting ionomer.

9. The membrane electrode assembly of claim 8 wherein the amount of the metal-ligand complex additive in the composite polymer electrolyte is from about 0.5% to about 1% by weight of the proton conducting ionomer.

10. The membrane electrode assembly of claim 1 wherein the proton conducting ionomer is perfluorosulfonic acid ionomer or hydrocarbon ionomer.

11. The membrane electrode assembly of claim 1 wherein the cathode catalyst layer comprises the composite polymer electrolyte.

12. A solid polymer electrolyte fuel cell comprising a membrane electrode assembly comprising:
an anode catalyst layer,
a membrane electrolyte,
a cathode catalyst layer, and
a proton conducting composite polymer electrolyte comprising a proton conducting ionomer and an amount of a metal-ligand complex additive wherein:
the metal in the complex is selected from the group consisting of metals, metal alloys, metal oxides, metal salts and combinations thereof; and
the ligand in the complex comprises a molecule or polymer thereof wherein the chemical structure of the molecule is selected from the group consisting of:

wherein R 1 , R 3 and R 4 are selected from the group consisting of H, CH 3 (CH 2 ) n , CH 3 (CH 2 ) n O, CF 3 (CF 2 ) n , CF 3 (CF 2 ) n O, COOH, PO(OH) 2 , SO 3 H, NH 2 , OH, and

wherein X is H, COOH, PO(OH) 2 or SO 3 H and n is an integer from
0 to 10; and wherein R 2 is selected from the group consisting of CH 3 (CH 2 ) n , CH 3 (CH 2 ) n O, CF 3 (CF 2 ) n , CF 3 (CF 2 ) n O, COOH, PO(OH) 2 , SO 3 H, NH 2 , OH, and

wherein X is H, COOH, PO(OH) 2 or SO 3 H and n is an integer from 0 to 10.

Assignees

• Daimler Ag
• Ford Motor Co

Inventors

• Wang Keping
• Yang Yunsong
• Li Jing

Classifications

• Y02E60/50

  Fuel cells · CPC title

• H01M8/1023 Primary

  having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes · CPC title

• H01M8/1039

  halogenated, e.g. sulfonated polyvinylidene fluorides · CPC title

• H01M2250/10

  Fuel cells in stationary systems, e.g. emergency power source in plant · CPC title

• H01M2250/20

  Fuel cells in motive systems, e.g. vehicle, ship, plane · CPC title