Oxygen evolution reaction electrode catalyst assembly comprising dendritic nickel foam, its use and a method to produce said assembly

Patent metadata

Field	Value
Publication number	US-12258667-B2
Application number	US-202218701701-A
Country	US
Kind code	B2
Filing date	Oct 3, 2022
Priority date	Oct 18, 2021
Publication date	Mar 25, 2025
Grant date	Mar 25, 2025

Abstract

The present disclosure relates to a method to produce an oxygen evolution reaction electrode catalyst assembly comprising a dendritic nickel foam. The method is remarkable in that it comprises the steps of (a) providing a dendritic nickel foam material; (b) etching the dendritic nickel foam material by placing it in a etch solution being an acidic aqueous solution or an aqueous solution of metal chloride and recovering an etched dendritic nickel foam with nickel dendrites showing a chimney-like structure.

First claim

The invention claimed is:

1. A method to produce an oxygen evolution reaction electrode catalyst assembly comprising a dendritic nickel foam; the method is characterized in that it comprises the steps
(a) providing a dendritic nickel foam material being a nickel foam that shows a dendrite morphology evidenced by scanning electron microscopy with nickel dendrites forming a nickel dendrites layer;
(b) etching the dendritic nickel foam material by placing it in a etch solution having a pH ranging from 1.0 to 4.0 and being an aqueous acidic solution or an aqueous solution of metal chloride, and recovering an etched dendritic nickel foam with nickel dendrites showing a chimney-like structure that is porous with three levels of porosity and shows pores of a first type having an average pore size diameter ranging from 20.0 μm to 50.0 μm as determined by scanning electron microscopy, pores of a second type having an average pore size diameter ranging from 1.0 to 5.0 μm as determined by scanning electron microscopy, and pores of a third type having an average pore size diameter ranging from 0.1 μm to 1.0 μm as determined by scanning electron microscopy; and
(c) of addition of one or more transition metals, wherein step (c) comprises a step (c1) of galvanic exchange reaction or a step (c2) of electrodeposition or both steps c1) of galvanic exchange reaction and step (c2) of electrodeposition.

2. The method according to claim 1 is characterised in that the etching step (b) is performed in a etch solution for a time ranging from 1 to 60 minutes.

3. The method according to claim 1 is characterised in that the etching step (b) is performed in a etch solution having a pH ranging from 1.8 to 2.5 for a time ranging from 1 to 15 minutes.

4. The method according to claim 1 is characterised in that step (a) comprises providing nickel foam followed by a step of electrodeposition of nickel on said nickel foam to obtain a dendritic nickel foam.

5. The method according to claim 1 is characterised in that step (a) comprises providing a dendritic nickel foam selected to have a double-layer capacitance of at least 2.0 mF as determined by cyclic voltammetry in the range between +0.95 V and +1.05 V versus RHE.

6. The method according to claim 1 is characterised in that step (c) of addition of one or more transition metals comprises the step (c1) of doping the etched dendritic nickel foam with one or more transition metals via a galvanic exchange reaction and recovering a Me-doped dendritic nickel foam with Me-doped nickel dendrites showing a chimney-like structure.

7. The method according to claim 6 is characterised in that in step (c1) using a galvanic exchange reaction, the etched dendritic nickel foam is doped with one or more transition metals selected from Fe, Cr, Co, Cu, V, Mn, Mo, Pt, W and any mixture thereof.

8. The method according to claim 1 is characterized in that the method further comprises a step (c2) of electrodeposition on the etched dendritic nickel foam of a metallic catalyst comprising one or more transition metals selected from Fe, Cr, Co, Cu, V, Mn, Mo, Ni, Pt, W and any mixture thereof.

9. The method according to claim 8 is characterized in that the metallic catalyst is a multi-metallic catalyst and comprises Ni and Fe and at least one additional metal selected from Cr, Co, Cu, V, Mn, Mo, Pt, W and any mixture thereof.

10. The method according to claim 8 is characterized in that the metallic catalyst is a multi-metallic catalyst and in that step (c2) is followed by a step (d) of leaching to decrease the content of at least one transition metal of the multi-metallic catalyst.

11. The method according to claim 1 is characterized in that the etched dendritic nickel foam with nickel dendrites showing a chimney-like structure recovered in step (b) is porous and shows pores of a fourth type having an average pore size diameter ranging from 100 μm to 1000 μm as determined by scanning electron microscopy; with preference ranging from 200 to 800 μm.

12. An oxygen evolution reaction electrode catalyst assembly is characterized in that it comprises an etched dendritic nickel foam with nickel dendrites showing a chimney-like structure forming an etched nickel dendrites layer being porous with three levels of porosity and showing pores of a first type having an average pore size diameter ranging from 20.0 μm to 50.0 μm as determined by scanning electron microscopy, pores of a second type having an average pore size diameter ranging from 1.0 to 5.0 μm as determined by scanning electron microscopy, and pores of a third type having an average pore size diameter ranging from 0.1 μm to 1.0 μm as determined by scanning electron microscopy;
and in that the etched dendritic nickel foam is doped with one or more transition metals selected from Fe, Cr, Co, Cu, V, Mn, Mo, Pt, W and any mixture thereof.

13. The oxygen evolution reaction electrode catalyst assembly according to claim 12 characterized in that the one or more doping transition metals are present at a content ranging from 5 to 30 at. % as analysed by EDX.

14. An oxygen evolution reaction electrode catalyst assembly comprising a metallic catalyst and a support, with the metallic catalyst being deposited on the support, the electrode catalyst assembly is characterized in that the support is an etched dendritic nickel foam with nickel dendrites showing a chimney-like structure forming an etched nickel dendrites layer being porous with three levels of porosity and show pores of a first type having an average pore size diameter ranging from 20.0 μm to 50.0 μm as determined by scanning electron microscopy, pores of a second type having an average pore size diameter ranging from 1.0 to 5.0 μm as determined by scanning electron microscopy, and pores of a third type having an average pore size diameter ranging from 0.1 μm to 1.0 μm as determined by scanning electron microscopy; and in that the metallic catalyst comprises one or more transition metals selected from Fe, Cr, Co, Cu, V, Mn, Mo, Ni, Pt, W and any mixture thereof.

15. The oxygen evolution reaction electrode catalyst assembly according to claim 14 is characterized in that the metallic catalyst is a multi-metallic catalyst and is or comprises Fe and Ni.

16. The oxygen evolution reaction electrode catalyst assembly according to claim 14 is characterized in that the metallic catalyst is a multi-metallic catalyst and is or comprises Fe, Ni and one or more transition metals selected from Cr, Co, Cu, V, Mn, Mo, Pt, W and any mixture thereof.

17. The oxygen evolution reaction electrode catalyst assembly of claim 14 is characterized in that it shows pores of a fourth type having an average pore size diameter ranging from 100 μm to 1000 μm as determined by scanning electron microscopy.

18. The oxygen evolution reaction electrode catalyst assembly according to claim 14 is characterized in that the pores of a third type have an average pore size diameter ranging from 0.1 μm to 0.6 μm as determined by scanning electron microscopy.

19. The oxygen evolution reaction electrode catalyst assembly according to claim 14 is characterized in that it shows overpotential values below 310 mV at a current density of 100 mA cm -2 at pH 14 and in 1.0 M electrolyte solution.

20. The oxygen evolution reaction electrode catalyst assembly according to claim 14 is characterized in that shows a Tafel slope of at most 30 mV decade as determined by chronopotentiometry measurements conducted in an aqueous 1 M solution of KOH.

Assignees

• Totalenergies Onetech
• College France

Inventors

• Peugeot Adèle
• Fontecave Marc
• Creissen Charles
• Schreiber Moritz Wilhelm

Classifications

• C25B1/04 Primary

  by electrolysis of water · CPC title

• C25B11/061

  Metal or alloy · CPC title

• C25B11/089

  Alloys · CPC title

• Y02E60/36

  Hydrogen production from non-carbon containing sources, e.g. by water electrolysis · CPC title

• C25B11/042

  Electrodes formed of a single material · CPC title