Methods for manufacturing electrochemical sensors, and related electrochemical sensors

Patent metadata

Field	Value
Publication number	US-11635404-B2
Application number	US-202016840102-A
Country	US
Kind code	B2
Filing date	Apr 3, 2020
Priority date	Apr 4, 2019
Publication date	Apr 25, 2023
Grant date	Apr 25, 2023

Abstract

Methods for manufacturing an electrochemical sensor include forming at least one electrode by printing at least one conductive ink on a surface of at least one substrate. The conductive ink may comprise, e.g., a platinum-group metal, another transition-group metal with a high-temperature melting point, a conductive ceramic material, glass-like carbon, or a combination thereof. The electrochemical sensor may be free of another material over the at least one electrode. An electrochemical sensor, formed according to such methods, may be configured for use in harsh environments (e.g., a molten salt environment). Electrodes of the electrochemical sensor comprise conductive material formed from a printed, conductive ink. In some embodiments, at least a portion of the electrochemical sensor is free of silver, gold, copper, silicon, and polymer materials, such portion being that which is to be exposed to the harsh environment during use of the electrochemical sensor.

First claim

What is claimed is:

1. A method for manufacturing an electrochemical sensor, comprising:
forming at least one working electrode on at least one substrate, comprising printing at least one conductive ink on a surface of the at least one substrate, the at least one working electrode free of silver, gold, copper, silicon, and polymer materials and at least a portion of the at least one substrate, to be inserted into a molten salt environment during use of the electrochemical sensor, being free of silver, gold, copper, silicon, and polymer materials,
forming at least one counter electrode on at least one substrate, comprising printing at least one other conductive ink on the surface or another surface of the at least one substrate, the at least one counter electrode free of silver, gold, copper, silicon, and polymer materials, and
forming at least one reference electrode free of silver, gold, copper, silicon, and polymer materials on the at least one substrate.

2. The method of claim 1 , wherein forming the at least one working electrode on the at least one substrate comprises printing all of the at least one working electrode of the electrochemical sensor on one of the at least one substrate.

3. The method of claim 1 , wherein forming the at least one working electrode on the at least one substrate comprises printing the at least one conductive ink on a surface of at least one substrate comprising a ceramic material.

4. The method of claim 1 , wherein forming the at least one working electrode on the at least one substrate comprises printing the at least one conductive ink on a surface of at least one substrate comprising one or more of a ceramic material, sapphire, or quartz.

5. The method of claim 1 , wherein the printing comprises inkjet printing the at least one conductive ink on the surface of the at least one substrate.

6. The method of claim 1 , wherein the printing comprises aerosol jet printing the at least one conductive ink on the surface of the at least one substrate.

7. The method of claim 1 , further comprising, after forming the at least one working electrode on the at least one substrate, submerging at least a portion of the at least one working electrode and the at least one substrate within a molten salt.

8. The method of claim 1 , wherein forming at least one working electrode on at least one substrate comprises printing the at least one conductive ink on the surface of the at least one substrate to form the at least one working electrode to have a width of less than about 100 μm.

9. Au electrochemical sensor for use in a molten salt environment, the electrochemical sensor comprising:
a working electrode on at least one substrate, the working electrode comprising a conductive material; and
a counter electrode on the at least one substrate, the counter electrode comprising another conductive material,
wherein:
at least a portion of the electrochemical sensor, to be inserted into a molten salt environment during use of the electrochemical sensor, is free of silver, gold, copper, silicon, and polymer materials; and
the electrochemical sensor further comprises a reference electrode on the at least one substrate.

10. The electrochemical sensor of claim 9 , wherein reference electrode at least partially laterally circumscribes the working electrode.

11. The electrochemical sensor of claim 10 , wherein:
the working electrode and the reference electrode are disposed on a first substrate of the at least one substrate; and
the counter electrode is disposed on a second substrate of the at least one substrate.

12. The electrochemical sensor of claim 9 , wherein a greatest outer dimension of the electrochemical sensor is less than about 1000 μm.

13. The electrochemical sensor of claim 9 , wherein the at least one substrate is substantially circular.

14. The electrochemical sensor of claim 9 , wherein at least one of the conductive material or the other conductive material has a perovskite crystal structure.

15. The electrochemical sensor of claim 9 , wherein the conductive material is not covered by another material.

16. An electrochemical sensor for use in a molten salt environment, the electrochemical sensor comprising:
a working electrode on at least one substrate, the working electrode comprising a conductive material; and
a counter electrode on the at least one substrate, the counter electrode comprising another conductive material,
wherein at least a portion of the electrochemical sensor, to be inserted into a molten salt environment during use of the electrochemical sensor, is free of silver, gold, copper, silicon, and polymer materials; and
wherein a greatest outer dimension of the electrochemical sensor is less than about 1000 μm.

17. The electrochemical sensor of claim 16 , wherein the at least one substrate is free of silicon.

18. The electrochemical sensor of claim 16 , wherein:
the working electrode comprises a distal portion extending to an edge of the at least one substrate; and
the counter electrode comprises another distal portion extending to the edge or another edge of the at least one substrate.

19. The electrochemical sensor of claim 16 , wherein the conductive material and the other conductive material comprise one or more of:
a transition-group metal with a melting point greater than about 400° C.;
a conductive ceramic material;
vitreous carbon; or
a combination of any of the foregoing.

20. The electrochemical sensor of claim 16 , wherein the at least one substrate comprises one or more of a ceramic material, sapphire, or quartz.

21. The electrochemical sensor of claim 16 , wherein the working electrode and the counter electrode have a fixed position relative to one another.

Assignees

• Battelle Energy Alliance Llc

Inventors

• Shaltry Michael R
• Tripathy Prabhat K
• Estrada David

Classifications

• G01N27/4166

  measuring a particular property of an electrolyte · CPC title

• G01N27/403

  Cells and electrode assemblies · CPC title

• G01N33/205

  in liquid state, e.g. molten metals · CPC title

• G01N27/30 Primary

  Electrodes, e.g. test electrodes; Half-cells (G01N27/414 takes precedence) · CPC title

• G01N27/3272 Primary

  Test elements therefor, i.e. disposable laminated substrates with electrodes, reagent and channels (optical biosensors G01N33/52) · CPC title