Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes
The invention provides an electrode comprising a substrate and a coating on the substrate. The coating comprises a plurality of layers, including the following layers in sequence moving outwardly from the substrate: a base layer comprising an oxide of a valve metal; a lower layer comprising an oxide of a platinum group metal and/or an oxide of a precious metal; and a mixed oxide primary layer comprising both: (i) an oxide of a platinum group metal and/or an oxide of a precious metal, and (ii) an oxide of a valve metal and/or an oxide of a group 15 metal. The base layer is devoid of any platinum group metal oxide, and the lower layer is devoid of any valve metal oxide. The present invention also provides methods of manufacturing such electrodes. Also provide are methods of using an electrochemical cell equipped with a certain multilayer coated electrode.
1. An electrode comprising:
a substrate; and
a coating on the substrate, the coating comprising a plurality of layers, the plurality of layers comprising the following in sequence moving outwardly from the substrate:
a. a base layer comprising an oxide of a valve metal, the base layer being devoid of any platinum group metal oxide;
b. a lower layer comprising an oxide of a platinum group metal and/or an oxide of a precious metal, the lower layers being devoid of any valve metal oxide;
c. a mixed oxide primary layer comprising both: (i) an oxide of a platinum group metal and/or an oxide of a precious metal, and (ii) an oxide of a valve metal and/or an oxide of a group 15 metal; and
d. an intermediate layer comprising an oxide of a platinum group metal and/or an oxide of a precious metal, the intermediate layer being devoid of any valve metal oxide.
2. The electrode of claim 1 , wherein the coating is devoid of any mixed metal oxide layer between the base layer and the lower layer.
3. The electrode of claim 1 , wherein the coating comprises five layers, including the base layer, the lower layer, and the mixed oxide primary layer, at least three of the five layers having different compositions from one another.
4. The electrode of claim 3 , wherein each of the five layers is contiguous to one or two layers of different composition.
5. The electrode of claim 1 , wherein the plurality of layers further comprises:
a. a mixed oxide upper layer comprising both: (i) an oxide of a platinum group metal and/or an oxide of a precious metal, and (ii) an oxide of a valve metal and/or an oxide of a group 15 metal, the mixed oxide upper layer being located further from the substrate than is the intermediate layer.
6. The electrode of claim 5 , wherein the coating has an exposed face that is defined by the mixed oxide upper layer.
7. The electrode of claim 1 , wherein the plurality of layers further includes a barrier layer comprising one or more valve metal oxides, the barrier layer being in contact with the substrate and beneath the base layer.
8. The electrode of claim 7 , wherein the barrier layer consists of one or more valve metal oxides.
9. The electrode of claim 5 , wherein the base layer comprises an oxide of tantalum.
10. The electrode of claim 9 , wherein the lower layer comprises an oxide of platinum.
11. The electrode of claim 10 , wherein the mixed oxide primary layer comprises both an oxide of platinum and an oxide of tantalum.
12. The electrode of claim 11 , wherein the intermediate layer comprises an oxide of platinum.
13. The electrode of claim 12 , wherein the mixed oxide upper layer comprises both an oxide of platinum and an oxide of tantalum.
14. The electrode of claim 1 , wherein the substrate comprises a valve metal.
15. The electrode of claim 14 , wherein the substrate is a titanium plate or a titanium mesh.
16. An electrode comprising:
a substrate; and
a coating on the substrate, the coating comprising
a plurality of layers,
the plurality of layers comprising the following in sequence moving outwardly from the substrate:
a. a base layer comprising an oxide of a valve metal, the base layer being devoid of any platinum group metal oxide;
b. a lower layer comprising an oxide of a platinum group metal and/or an oxide of a precious metal, the lower layers being devoid of any valve metal oxide; and
c. a mixed oxide primary layer comprising both: (i) an oxide of a platinum group metal and/or an oxide of a precious metal, and (ii) an oxide of a valve metal and/or an oxide of a group 15 metal,
wherein two of the plurality of layers, including the lower layer and an additional layer, (i) each comprise an oxide of a platinum group metal and/or an oxide of a precious metal, (ii) are each devoid of any valve metal oxide, and (iii) are separated by the mixed oxide primary layer.
17. An electrode comprising:
a substrate; and
a coating on the substrate, the coating comprising a plurality of layers, the plurality of layers comprising the following in sequence moving outwardly from the substrate:
a. a base layer comprising an oxide of a valve metal, the base layer being devoid of any platinum group metal oxide;
b. a lower layer comprising an oxide of a platinum group metal and/or an oxide of a precious metal, the lower layer being devoid of any valve metal oxide;
c. a mixed oxide primary layer comprising both: (i) an oxide of a platinum group metal and/or an oxide of a precious metal, and (ii) an oxide of a valve metal and/or an oxide of a group 15 metal;
d. an intermediate layer comprising an oxide of a platinum group metal and/or an oxide of a precious metal, the intermediate layer being devoid of any valve metal oxide; and
e. a mixed oxide upper layer comprising both: (i) an oxide of a platinum group metal and/or an oxide of a precious metal, and (ii) an oxide of a valve metal and/or an oxide of a group 15 metal.