Solid polymer electrolyte oxygen sensor

• US 20050034987A1
• Filed: 08/12/2003
• Published: 02/17/2005
• Est. Priority Date: 08/12/2003
• Status: Active Grant

• Current Assignee: RAE Systems Incorporated (Honeywell International Inc.)
• Original Assignee: RAE Systems Incorporated (Honeywell International Inc.)
• Inventors: Hsi, Peter C., Zhou, Huafang, Sun, Hong T.
• Granted Patent: US 7,258,773 B2
• Time in Patent Office: Days
• US Class Current: 204/426
• CPC Class Codes: G01N 27/4045 for gases other than oxygen
• CPC Class Codes: G01N 27/4073 Composition or fabrication of the solid electrolyte

Abstract

An oxygen sensor includes a solid polymer electrolyte, e.g., on an acid treated Nafion membrane and uses a diffusion-limited fuel cell type reactions. The sensor avoids electrolyte leakage and avoids consumption of electrodes. In different configurations, a counter or reference electrode can be on the same or the opposite side of the electrolyte as a sensing electrode. An insert limits and controls oxygen diffusion into a sensing chamber containing the sensing electrode that catalyzes reduction of oxygen. Applying appropriate bias voltages to the reference and sensing electrodes causes an output current of the sensing electrode to be proportional to the rate of oxygen consumption based on Frick'"'"'s law under a diffusion-limited mode. The output current can be measured, e.g., using a resistor to convert the current to a voltage signal.

Claims

1. A gas sensor comprising:

a block of a solid electrolyte;

a sensing electrode in electrical contact with the block; and

a counter electrode in electrical contact with the block, wherein;

the sensing electrode catalyzes a reaction of oxygen with hydrogen ions and electrons to produce water;

a biasing of the counter electrode breaks down water to produce electrons and hydrogen ions in the block; and

a current through the sensing electrode caused by the electrons captured indicates a measured oxygen concentration.

2. The gas sensor of claim 1, further comprising a reference electrode in electrical contact with the block.

3. The sensor of claim 1, further comprising an insert between the sensing electrode and a source of a gas being measured, wherein the insert includes controls a flow of oxygen to the sensing electrode so that a diffusion rate limits a rate of the reaction at the sensing electrode.

4. The sensor of claim 3, wherein the insert includes a capillary pore that limits the flow of oxygen.

5. The sensor of claim 4, wherein the capillary pore has a diameter less than 0.1 μ

m to control oxygen diffusion.

6. The sensor of claim 3, wherein the insert comprises a gas permeable membrane.

7. The sensor of claim 1, further comprising a reservoir adjacent the block, wherein the reservoir contains water that maintains humidity in the block.

8. The sensor of claim 7, further comprising a moisture-retaining agent in the reservoir.

9. The sensor of claim 8, wherein the moisture-retaining agent comprises a polymer material or an acid.

10. The sensor of claim 9, wherein the acid comprises H₂SO₄ or H₃PO₄.

11. The sensor of claim 1, further comprising a rigid housing that encloses the block.

12. The sensor of claim 1, wherein the solid electrolyte is a protonic conductive electrolyte membrane having a thickness in the range of approximately 0.01 to 0.2 mm.

13. The sensor of claim 12, wherein the solid electrolyte comprises a perfluorinated ion-exchange polymer.

14. The sensor of claim 1, wherein the block comprises a Nafion membrane.

15. The sensor of claim 14, wherein the Nafion membrane is treated with an acid.

16. The sensor of claim 15, wherein the acid is H₃PO₄.

17. The sensor of claim 14, wherein the sensing and counter electrodes are hot-pressed on the Nafion membrane.

18. The sensor of claim 1, wherein the block comprises a protonic conductive electrolyte slice including a conducting polymer selected from a group consisting of poly(ethylene glycol), poly(ethylene oxide), and poly(propylene carbonate).

19. The sensor of claim 1, wherein the sensing electrode comprises a material selected from a group consisting of platinum, gold, ruthenium, palladium, iridium, platinum/ruthenium, platinum/iridium, platinum/palladium alloy, carbon, and platinum/carbon.

20. The sensor of claim 1, wherein the sensing electrode is made of a material that catalyzes oxygen reduction.

21. The sensor of claim 1, wherein the counter electrode comprises a noble metal selected from a group consisting of platinum and gold.

22. The sensor of claim 1, wherein the reference electrode comprises a material selected from a group consisting of platinum and Ag/AgCl.

23. The sensor of claim 1, wherein the sensing electrode is on a first surface of the block and the counter electrode is on a second surface of the block.

24. The sensor of claim 23, wherein a reference electrode is on the second surface of the block.

25. The sensor of claim 1, wherein the sensing and counter electrodes are on a first surface of the block.

26. The sensor of claim 25, wherein the sensing is circular, and the counter electrode has a ring shape that surrounds the sensing electrode.

27. The sensor of claim 26, wherein the sensing electrode has a diameter of 0.6 mm, and the counter electrode has a width of 0.2 mm.

28. The sensor of claim 25, wherein a reference electrode is on a second surface of the block.

29. The sensor of claim 25, wherein a reference electrode is on the first surface of the block.

30. The sensor of claim 1, wherein each of the sensing and counter electrodes has a diameter between 0.5 and 0.8 mm.

31. The sensor of claim 1, wherein the biasing of the sensing electrode is between −

1.0 to 1.0 voltage.

32. The sensor of claim 1, wherein the overall size of the sensor is less than about 5.0 cm³.

33. The sensor of claim 1, wherein the overall size of the sensor is less than about 1.0 cm³.

34. An oxygen sensor comprising:

a block of a solid electrolyte;

first, second, and third electrodes in electrical contact with the block;

first, second, and third terminals in electrical contact respectively with the first, second, and third electrodes, wherein the first, second, and third terminals are electrically isolated from each other to permit independent biasing of the first, second, and third electrodes; and

an electronic circuit that is connected to the first, second, and third terminals to bias the first, second, and third electrodes and measure a current indicating a target gas.

35. The sensor of claim 34, further comprising a rigid housing that forms a sensing chamber containing at least one of the first, second, and third electrodes.

36. The sensor of claim 34, further comprising a restrictor including a capillary pore that limits diffusion of oxygen into the sensing cavity.

37. The sensor of claim 34, wherein the rigid housing further comprises a reservoir in communication with the block of solid electrolyte to control water content in the solid electrolyte.

38. A button-type oxygen sensor comprising:

a block of a solid polymer electrolyte;

a first electrode on a first surface of the block;

a second electrode on a second surface of the block; and

a rigid housing including a first portion in electrical contact with the first electrode and a second portion in electrical contact with the second electrode.

39. The sensor of claim 38, further comprising insert between the block and a hole in the housing, wherein the insert includes a membrane that controls a flow of oxygen to the first electrode from the hole.

40. The sensor of claim 39, wherein the membrane allows gases to permeate to the first electrode and rejects water and dust.

41. The sensor of claim 40, wherein the membrane is made of polypropylene and polyester.

42. The sensor of claim 40, further comprising a moisture-retaining material that is within the housing.

43. The sensor of claim 42, wherein each of the block, the membrane, and the humidity containing material is disk-shaped, and elements with the housing form a stack of disk-shaped structures.

44. The sensor of claim 38, further comprising a moisture-retaining material that is within the housing containing humidity.

45. The sensor of claim 44, wherein the moisture-retaining material comprises a glass fiber paper.

46. The sensor of claim 45, wherein the moisture-retaining material further comprises an acid that absorbs water in wet environment and releases water in dry environment.

47. The sensor of claim 46, wherein the acid is a sulfuric acid.

48. The sensor of claim 38, wherein the solid polymer electrolyte is a protonic conductive electrolyte membrane having a thickness in the range of approximately 0.01 to 0.02 mm.

49. The sensor of claim 48, wherein the solid electrolyte comprises a perfluornated ion-exchange polymer.

50. The sensor of claim 48, wherein the block comprise a Nafion membrane.

51. The sensor of claim 50, wherein the Nafion membrane is treated with 85% H3PO4.

52. The sensor of claim 50, wherein the first and second electrodes are hot-pressed on the Nafion membrane.

53. The sensor of claim 38, wherein the block comprises a protonic conductive electrolyte slice including a conducting polymer.

54. The sensor of claim 38, wherein the first electrode and second electrode comprise a material selected from a group consisting of platinum, gold ruthenium, palladium, iridium/ruthenium, platinum/iridium, platinum/palladium alloy, carbon, and platinum/carbon.

55. The sensor of claim 54, wherein the first and second electrodes have a diameter between 0.5 and 0.8 mm.

56. The sensor of claim 38, wherein a bias −

0.6 voltage is applied to first electrode relative to the second electrode.

57. The sensor of claim 38, wherein the overall size of sensor is less than 1.0 cm³.

58. A method for sensing gaseous oxygen in a sample gas, comprising:

controlling a rate of diffusion of oxygen from the sample gas into a sensing chamber;

catalyzing a reaction at a first electrode that is in electrical contact with a solid electrolyte, wherein the reaction causes oxygen to capture hydrogen ions and electrons to produce water;

applying a bias voltage between a second electrode in contact with the solid electrolyte to cause a reaction that releases hydrogen ions and electrons; and

measuring a current through the first electrode that results from a reaction of the ions with oxygen in the sensing chamber.

59. The method of claim 58, wherein the hydrogen ions are released from water.

60. The method of claim 58, wherein controlling the rate of diffusion comprises employing a capillary pore to control gas entering the sensing chamber.