Electrode

Patent metadata

Field	Value
Publication number	US-11326266-B2
Application number	US-201615761127-A
Country	US
Kind code	B2
Filing date	Sep 22, 2016
Priority date	Sep 25, 2015
Publication date	May 10, 2022
Grant date	May 10, 2022

Abstract

An electrode (10) is disclosed. The electrode (10) comprises an electrode substrate (20). A layer of TiOx (30, 40) with a total thickness in the range of between 40-200 μm is present on at least one surface of the electrode substrate (20) and a porosity of layer of TiOx (30, 40) is below 15%. An electro-catalytic layer (50) comprising oxides of ruthenium and cerium according comprising at least 50 molar % ruthenium oxides is present on layer of TiOx (30, 40) and wherein x is in the range 1-2 for the layer of TiOx. A process for the manufacture of the electrode (10) is disclosed as are uses thereof.

First claim

What is claimed is:

1. A cathode comprising:
a cathode substrate that is titanium and has at least one surface;
at least one layer of TiO x with a total thickness of from 40 to 200 μm and wherein the at least one layer of TiO x is disposed on and in direct contact with the at least one surface of the cathode substrate, wherein a porosity of the at least one layer of TiO x is below 15%; and
an electro-catalytic layer comprising oxides of ruthenium and cerium comprising ruthenium oxide in an amount of from 50 to 95 molar % and cerium oxide in an amount of from 5 to 25 molar %, the electro-catalytic layer being disposed on and in direct contact with the at least one layer of TiO x ,
wherein x is from 1 to 2 for the at least one layer of TiO x ;
wherein said at least one layer of TiO x comprises a single layer being at least 40 μm or two or more layers of TiO x where each layer of TiO x is at least 20 μm; and
where the cathode is resilient to hydrogen diffusing to the cathode substrate during use thereof in an electrolytic process.

2. The cathode according to claim 1 , wherein the at least one layer of TiO x comprises at least 50 molar % TiO x and the cathode is devoid of cracking.

3. The cathode according to claim 1 , wherein the at least one layer of TiO x includes a first layer of TiO x and a second layer of TiO x with the first layer of TiO x having a porosity lower than the second layer of TiO x .

4. The cathode according to claim 1 , wherein the at least one layer of TiOx includes a first layer of TiO x and a second layer of TiO x , and a thickness of the first layer of TiOx is from 20 to 120 μm and a thickness of the second layer of TiOx is from 20 to 120 μm such that the total thickness of the first layer of TiO x and second layer of TiO x does not exceed 200 μm.

5. The cathode according to claim 1 , wherein the at least one layer of TiO x comprises oxides of chromium.

6. The cathode according to claim 1 , wherein x is from 1.6 to 1.9 for the at least one layer of TiO x .

7. The cathode according to claim 1 , wherein the electro-catalytic layer provides a ruthenium content of from 2 to 25 g/m2.

8. The cathode according to claim 1 , wherein at least 95% of the ruthenium from the electro-catalytic layer penetrates the at least one layer of TiO x to no more than 30% of a total thickness of the at least one layer of TiO x .

9. An electrolytic process comprising the step of electrolytically generating hydrogen gas at the cathode of claim 1 .

10. A process of manufacturing an cathode that is resilient to hydrogen diffusing to the cathode substrate during use thereof in an electrolytic process, the process comprising the steps of:
i) providing a cathode substrate that is titanium and that has at least one surface;
ii) coating the at least one surface of the cathode substrate by plasma spraying to form at least one layer of TiO x with a total thickness of from 40 to 200 μm and wherein the at least one layer of TiO x is disposed on and in direct contact with the at least one surface of the cathode substrate to provide a porosity of the at least one layer of TiO x of below 15%; and
iii) forming an electro-catalytic layer comprising oxides of ruthenium and cerium comprising ruthenium oxide in an amount of from 50 to 95 molar % and cerium oxide in an amount of from 5 to 25 molar %, the electro-catalytic layer being disposed on and in direct contact with the at least one layer of TiO x , wherein x is from 1 to 2 for the at least one layer of TiO x and wherein the at least one layer of TiO x comprises a single layer being at least 40 μm or two or more layers of TiO x where each layer of TiO x is at least 20 μm.

11. The process according to claim 10 , wherein the at least one surface of the cathode substrate is roughened to provide an R a value of from 1 to 6 μm prior to step ii).

12. The process according to claim 10 , wherein forming the electro-catalytic layer on the at least one layer of TiO x comprises a heating step and a thermolysis step of a combination of ruthenium and cerium compounds.

13. The process according to claim 12 , wherein the heating step is carried out for a time of from 5 to 15 minutes at a temperature of from 70 to 100° C.

14. The process according to claim 12 , wherein the thermolysis step is carried out for a time of from 10 to 15 minutes at a temperature of from 450 to 550° C.

15. The cathode of claim 1 wherein the at least one layer of TiO x includes a first layer of TiO x and a second layer of TiO x , and a thickness of the first layer is from 35 to 65 μm and a thickness of the second layer is from 35 to 100 μm.

16. The cathode of claim 15 wherein the porosity of the second layer is from 3 to 21%.

17. The cathode of claim 16 wherein x is from 1.6 to 1.9 for the first and second layers of TiO x .

18. The cathode of claim 1 comprising from 10 to 15 g/cm 2 ruthenium and wherein
the at least one layer of TiO x includes a first layer of TiO x and a second layer of TiO x , and a thickness of the first layer is from 35 to 65 μm and a thickness of the second layer is from 35 to 100 μm;
the porosity of the second layer is from 3 to 21%; and
x is from 1.6 to 1.9 for the first and second layers of TiO x .

19. The cathode of claim 1 , wherein the electro-catalytic layer consists of ruthenium oxide in an amount of from 50 to 95 molar %, cerium oxide in an amount of from 5 to 25 molar % and any one of titanium, zirconium and lanthanum or any combination thereof.

20. The cathode of claim 1 , wherein the electro-catalytic layer comprises ruthenium oxide in an amount of from 75 to 90 molar % and cerium oxide in an amount of from 10 to 25 molar %.

21. The cathode of claim 1 , wherein the cathode substrate is titanium selected from Commercially Pure Grade 1 Titanium, Commercially Pure Grade 2 Titanium, Commercially Pure Grade 4 Titanium, Commercially Pure Grade 7 Titanium, Commercially Pure Grade 11 Titanium and Commercially Pure Grade 12 Titanium.

22. The cathode of claim 3 wherein the at least one layer of TiO x includes a first layer of TiO x and a second layer of TiO x disposed on and in direct contact with the first layer, wherein the first and second layers have a total thickness of from 70 to 160 μm and wherein the first and second layers are disposed on and in direct contact with the at least one surface of the cathode substrate wherein a porosity of the first layer is from 2 to 5% and is the same or lowers than a porosity of the second layer.

23. The method according to claim 9 , wherein the cathode is disposed in a chlorate cell that is polarised to a current density of between 0.8 to 5 kA/m2.

24. The method according to claim 9 , wherein the cathode is disposed in a chlorate cell that is polarised to a current density of between 2 to 3 kA/m2.

Assignees

• Akzo Nobel Chemicals Int Bv
• Nouryon Chemicals Int Bv

Inventors

• Rosvall Magnus
• Amerio Ezio
• Gustavsson John
• Holmin Susanne
• Bergman Lars-Erik

Classifications

• Y02E60/50

  Fuel cells · CPC title

• Y02E60/36

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

• C25B11/051

  Electrodes formed of electrocatalysts on a substrate or carrier · CPC title

• C25C7/02

  Electrodes (consumable anodes for the refining the metals C25C1/00 - C25C5/00); Connections thereof · CPC title

• C25B11/093 Primary

  at least one noble metal or noble metal oxide and at least one non-noble metal oxide · CPC title