NON-NOBLE METAL BASED ELECTRO-CATALYST COMPOSITIONS FOR PROTON EXCHANGE MEMBRANE BASED WATER ELECTROLYSIS AND METHODS OF MAKING

• US 20200131651A1
• Filed: 09/04/2019
• Published: 04/30/2020
• Est. Priority Date: 08/08/2012
• Status: Active Grant

• Current Assignee: University of Pittsburgh of The Commonwealth System of Higher Education
• Original Assignee: University of Pittsburgh of The Commonwealth System of Higher Education
• Inventors: KUMTA, PRASHANT N., KADAKIA, KARAN SANDEEP, DATTA, MONI KANCHAN, VELIKOKHATNYI, OLEG, JAMPANI HANUMANTHA, PRASHANTH
• Granted Patent: US 11,230,775 B2
• Time in Patent Office: Days
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C25B 1/04 by electrolysis of water
• CPC Class Codes: C25B 11/051 Electrodes formed of electrocatalysts on a substrate or carrier
• CPC Class Codes: C25B 11/093 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
• CPC Class Codes: C25B 9/73 of the filter-press type
• CPC Class Codes: H01M 4/881 Electrolytic membranes
• CPC Class Codes: H01M 4/8828 Coating with slurry or ink
• CPC Class Codes: H01M 4/9016 Oxides, hydroxides or oxygenated metallic salts
• CPC Class Codes: H01M 4/9075 Catalytic material supported on carriers, e.g. powder carriers H01M4/8807, H01M4/881, H01M4/8814, H01M4/925 take precedence
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

The invention provides electro-catalyst compositions for an anode electrode of an acid mediated proton exchange membrane-based water electrolysis system. The compositions include a noble metal component selected from the group consisting of iridium oxide, ruthenium oxide, rhenium oxide and mixtures thereof, and a non-noble metal component selected from the group consisting of tantalum oxide, tin oxide, niobium oxide, titanium oxide, tungsten oxide, molybdenum oxide, yttrium oxide, scandium oxide, cooper oxide, zirconium oxide, nickel oxide and mixtures thereof. Further, the non-noble metal component can include a dopant. The dopant can be at least one element selected from Groups III, V, VI and VII of the Periodic Table. The compositions can be prepared using any solution based methods involving a surfactant approach or a sol gel approach. Further, the compositions are prepared using noble metal and non-noble metal precursors. Furthermore, a thin film containing the compositions can be deposited onto a substrate to form the anode electrode.

Claims

1. A method of preparing an electro-catalyst composition for an anode electrode in a proton exchange membrane-based water electrolysis system, comprising:

preparing a surfactant solution;

preparing a non-noble metal precursor solution;

combining the non-noble metal precursor solution and the surfactant solution to form a first precipitate;

separating and drying the first precipitate to form a non-noble metal oxide powder;

preparing a noble metal precursor solution;

combining the non-noble metal oxide powder with the noble metal precursor solution to form a mixture; and

separating and drying the mixture to form the electro-catalyst composition of a general formula (a);

N_xM_1-xO₂,  

 

(a)

wherein N is iridium, ruthenium, rhenium or mixtures or combinations thereof, M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof, and x is a value from greater than zero to 99% based on weight of the composition,

wherein the resulting electro-catalyst composition is a complete oxide alloy or a complete solid solution, and

wherein the resulting electro-catalyst composition exhibits an electronic structure that mimics a noble metal oxide electro-catalyst composition absent of a non-noble metal.

2. The method of claim 1, wherein the electro-catalyst composition has a general formula (b):

Ir_1-x-ySn_xM_yO₂,  

 

(b)

wherein M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof, each of x and y is independently a value from greater than zero to 99%, and x+y is less than or equal to 99% based on weight of the composition.

3. The method of claim 1, wherein the electro-catalyst composition has a general formula (c):

Ir_1-2xSn_xM_xO₂,  

 

(c)

wherein M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof, and x is a value from greater than zero to 49.5% based on weight of the composition.

4. The method of claim 1, further comprising doping the non-noble metal oxide powder with a dopant precursor selected from the group consisting of at least one element from Groups III, V, VI and VII of the Periodic Table to form a doped non-noble metal oxide powder.

5. The method of claim 4, wherein the electro-catalyst composition has a general formula (d):

N_xM_1-xO₂;

D,  

 

(d)

wherein N is iridium, ruthenium, rhenium or mixtures or combinations thereof, M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof;

D is at least one element from Groups III, V, VI and VII of the Periodic Table; and

x is a value from greater than zero to 99% based on weight of the composition.

6. The method of claim 4, wherein the electro-catalyst composition has a general formula (e):

Ir_1-x-ySn_xM_yO₂;

D,  

 

(e)

wherein M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof, D is at least one element from Groups III, V, VI and VII of the Periodic Table, each of x and y is independently a value from greater than zero to 99%, and x+y is less than or equal to 99% based on weight of the composition.

7. The method of claim 4, wherein the electro-catalyst composition has a general formula (f):

Ir_1-2xSn_xM_xO₂;

D,  

 

(f)

wherein M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof;

D is at least one element from Groups III, V, VI and VII of the Periodic Table; and

x is a value from greater than zero to 49.5% based on weight of the composition.

8. A method for preparing an electro-catalyst composition for an anode electrode in a proton exchange membrane-based water electrolysis system, comprising:

preparing a non-noble metal precursor solution;

forming a first precipitate from the non-noble metal precursor solution;

separating the first precipitate;

dispersing the first precipitate in solvent to form a sol gel;

drying the sol gel to form a non-noble metal oxide powder;

preparing a noble metal precursor solution;

combining the non-noble metal oxide powder with the noble metal precursor solution to form a mixture; and

separating and drying the mixture to form the electro-catalyst composition of a general formula (g);

N_xM_1-xO₂,  

 

(g)

wherein N is iridium, ruthenium, rhenium or mixtures or combinations thereof, M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof, and x is a value from greater than zero to 99% based on weight of the composition,

wherein the resulting electro-catalyst composition is a complete oxide alloy or a complete solid solution, and

wherein the resulting electro-catalyst composition exhibits an electronic structure that mimics a noble metal oxide electro-catalyst composition absent of a non-noble metal.

9. The method of claim 8, wherein the electro-catalyst composition has a general formula (h):

Ir_1-x-ySn_xM_yO₂,  

 

(h)

wherein M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof, each of x and y is independently a value from greater than zero to 99%, and x+y is less than or equal to 99% based on weight of the composition.

10. The method of claim 8, wherein the electro-catalyst composition has a general formula (i):

Ir_1-2xSn_xM_xO₂,  

 

(i)

wherein M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof, and x is a value from greater than zero to 49.5% based on weight of the composition.

11. The method of claim 8, further comprising doping the non-noble metal oxide powder with a dopant precursor selected from the group consisting of at least one element from Groups III, V, VI and VII of the Periodic Table to form a doped non-noble metal oxide powder.

12. The method of claim 11, wherein the electro-catalyst composition has a general formula (j):

N_xM_1-xO₂;

D,  

 

(j)

wherein N is iridium, ruthenium, rhenium or mixtures or combinations thereof, M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof;

D is at least one element from Groups III, V, VI and VII of the Periodic Table; and

x is a value from greater than zero to 99% based on weight of the composition.

13. the method of claim 11, wherein the electro-catalyst composition has a general formula (k):

Ir_1-x-ySn_xM_yO₂;

D,  

 

(k)

wherein M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof, D is at least one element from Groups III, V, VI and VII of the Periodic Table, each of x and y is independently a value from greater than zero to 99%, and x+y is less than or equal to 99% based on weight of the composition.

14. The method of claim 11, wherein the electro-catalyst composition has a general formula (l):

Ir_1-2xSn_xM_xO₂;

D,  

 

(l)

wherein M is tin, niobium, tantalum, titanium, tungsten, molybdenum, yttrium, scandium, copper, zirconium, nickel or mixtures or combinations thereof;

D is at least one element from Groups III, V, VI and VII of the Periodic Table; and

x is a value from greater than zero to 49.5% based on weight of the composition.