FUEL CELL ELECTRODE HAVING POROUS CARBON CORE WITH MACROCYCLIC METAL CHELATES THEREON

• US 20130330658A1
• Filed: 11/14/2011
• Published: 12/12/2013
• Est. Priority Date: 11/12/2010
• Status: Active Grant

• Current Assignee: Celcibus AB
• Original Assignee: Anders Palmqvist
• Inventors: Fossum, Kjell, Palmqvist, Anders
• Granted Patent: US 10,115,971 B2
• Time in Patent Office: Days
• US Class Current: 429/532
• CPC Class Codes: B01J 2531/0216 Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• CPC Class Codes: B01J 2531/025 Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• CPC Class Codes: B01J 2531/16 Copper
• CPC Class Codes: B01J 2531/26 Zinc
• CPC Class Codes: B01J 2531/38 Lanthanides other than lanthanum
• CPC Class Codes: B01J 2531/56 Vanadium
• CPC Class Codes: B01J 2531/64 Molybdenum
• CPC Class Codes: B01J 2531/66 Tungsten
• CPC Class Codes: B01J 2531/72 Manganese
• CPC Class Codes: B01J 2531/842 Iron
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 2531/847 Nickel
• CPC Class Codes: B01J 31/1625 immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
• CPC Class Codes: B01J 31/1815 with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: B01J 31/183 with more than one complexing nitrogen atom, e.g. phenanthroline
• CPC Class Codes: H01M 4/8652 as mixture
• CPC Class Codes: H01M 4/8828 Coating with slurry or ink
• CPC Class Codes: H01M 4/9008 Organic or organo-metallic compounds
• CPC Class Codes: H01M 8/00 Fuel cells; Manufacture thereof
• CPC Class Codes: H01M 8/1004 characterised by membrane-electrode assemblies [MEA] H01M8/12 takes precedence
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention concerns a method for manufacturing of an electrocatalyst comprising a porous carbon support material, a catalytic material in the form of at least one type of metal, and macrocyclic compounds chemically bound to the carbon support and capable of forming complexes with single metal ions of said metal or metals, said method comprising the steps of: i) providing a template capable of acting as pore structure directing agent during formation of a highly porous electrically conducting templated carbon substrate, ii) mixing the template with one or several precursor substances of the catalytic material, the macrocyclic compounds and carbon, iii) exposing the mixture of the template and the precursor substances to a carbonization process during which the precursors react and transform the mixture into a carbonized template composite in which the carbon part of the composite is chemically bound to macrocyclic compounds present in complexes with the metal or metals. The invention also concerns an electrocatalyst for electrochemical reactions, a method for manufacturing of a membrane electrode assembly using such an electrocatalyst and to a fuel cell making use of such an electrocatalyst.

Claims

1. Method for manufacturing of an electrocatalyst comprising a porous carbon support material and a catalytic material of metal complexes of macrocyclic compounds chemically bound to the carbon support, said method comprising the steps of:

i) providing a template capable of acting as pore structure directing agent during formation of a highly porous electrically conducting template carbon substrate,

ii) mixing the template with one or several precursor substances of the carbon support, the macrocyclic compounds and the metal(s) in said complexes; and

,

iii) exposing the mixture of the template and the precursor substance(s) to a carbonization process during which the precursors react and transform the mixture into a carbonized template composite in which the carbon part of the composite is chemically bound to macrocyclic compounds present in complexes with the metal(s).

77. The method of claim 1 wherein the template is selected from the group consisting of porous solids and surface active molecules.

78. The method of claim 77 wherein the template is selected from the group consisting of an ordered mesoporous silica (OMS) material, a metal organic framework (MOF) material, a covalent organic framework (COF) material, a zeolitic imidazolate framework (ZOF) material, and mixtures thereof.

79. The method of claim 77 wherein the surface active molecule is a block copolymer or a surfactant.

80. The method of claim 1 further comprising the step of removing the template from the carbonized template composite.

81. The method of claim 1 wherein steps ii) and iii) are repeated.

82. The method of claim 1 wherein the precursor substance(s) is/are polymerized into a conductive polymer before step iii).

83. The method of claim 1 wherein at least one precursor of the carbon support, at least one precursor of the macrocyclic compounds and at least one metal salt are used.

84. The method of claim 1 wherein the metal(s) is(are) selected from transition metals.

85. The method of claim 1 wherein the precursor of the macrocyclic compounds comprises an amine compound that can react and form macrocyclic compounds that become chemically bound to the carbon support and capable of forming complexes with single metal ions of the metal(s).

86. The method of claim 85 wherein the amine acts as a source of both carbon and nitrogen for the final material.

87. The method of claim 85 wherein the amine compound is furfuryl amine.

88. The method of claim 1 wherein step ii) comprises including a catalyst for facilitating the carbonization process.

89. The method of claim 88 wherein the catalyst is p-toluene sulfonic acid.

90. An electrocatalyst obtained by the method of claim 1.

91. A method for manufacturing of a membrane electrode assembly (MEA) with gas diffusion layers (GDLs) suitable for use in a fuel cell, said method comprising the steps of:

i) mixing an electrocatalyst obtained by the method of claim 1 with an ionomer in the presence of a solvent,

ii) depositing the ink mixture thus obtained onto an ionomer membrane or onto a gas diffusion layer;

iii) sandwiching the ink mixture between the membrane and the gas diffusion layer, where the latter acts to provide gaseous reactants to the electrode and acts as current collector; and

iv) sandwiching the obtained sandwich structure with a second electrode with GDL onto the other side of the membrane, thus obtaining a MEA with GDLs for use in fuel cell setup.

96. Fuel cell having a first and a second electrode, wherein at least one of said electrodes comprises an electrocatalyst of claim 90 or 92.

2-76. -76. (canceled)

92. An electrocatalyst for electrochemical reactions, which electrocatalyst comprises a porous electrically conducting carbon substrate, a catalytic material in the form of at least one type of metal, macrocyclic compounds comprising carbon atoms and nitrogen, sulphur, oxygen, silicon, boron or phosphorous, which macrocyclic compounds form complexes with single metal ions of the catalytic material, wherein the metal containing macrocyclic complexes are incorporated into and integrated with said porous electrically conducting carbon substrate, and wherein said nitrogen, sulphur, oxygen, silicon, boron or phosphorous form(s) bonds on the one hand to the metal ion and on the other hand to said porous electrically conducting carbon substrate.

93. The electrocatalyst of claim 92 wherein the porous electrically conducting carbon substrate has an ordered mesoporous pore structure.

94. The electrocatalyst of claim 92 wherein the macrocyclic complexes are selected from the group consisting of N₄- and N₂-chelate compounds.

95. The electrocatalyst of claim 94 wherein the macrocyclic complexes are selected from the group consisting of metalloporphyrins, porphyrins, phthalocyanins and tetraazaannulenes.